技术领域Technical Field
本发明涉及造纸技术领域，具体涉及一种书画纸组合物、纸浆液、手工书画纸及其制备方法。The invention relates to the technical field of papermaking, and in particular to a calligraphy and painting paper composition, pulp liquid, handmade calligraphy and painting paper and a preparation method thereof.
背景技术Background Art
传统手工书画纸与现代机械纸各有所长。一方面，传统书画纸很多是由长纤维原料手工抄造而成，现代机械化造纸尚不能完全解决长纤维连续化生产的问题；传统手工书画纸的优异润墨性优于现代机械纸，更有利于满足艺术需求。另一方面，现代机械纸可方便地根据添加助剂调节其功能，而传统书画纸定量化功能改良方法较少，所添加的纸药较为单一。Traditional handmade calligraphy and painting paper and modern mechanical paper have their own strengths. On the one hand, many traditional calligraphy and painting papers are made by hand from long-fiber raw materials, and modern mechanized papermaking cannot completely solve the problem of continuous production of long fibers; the excellent ink-wetting properties of traditional handmade calligraphy and painting paper are better than those of modern mechanical paper, which is more conducive to meeting artistic needs. On the other hand, modern mechanical paper can easily adjust its functions by adding additives, while there are fewer quantitative functional improvement methods for traditional calligraphy and painting paper, and the added paper drugs are relatively single.
目前，仍有必要进一步开发具有优异综合品质的书画纸及其制备工艺。At present, it is still necessary to further develop calligraphy and painting paper with excellent comprehensive quality and its preparation process.
发明内容Summary of the invention
基于此，本发明的目的包括提供一种书画纸组合物，利用该组合物可制成纸浆液，进一步制备得到的手工书画纸具有优异的综合品质，纸质细腻、润墨效果可控，对颜料的锁定效果提高，颜色保持效果好，纸张拉力强。本发明还提供了书画纸的制备方法，对熟化步骤进行了改进，进一步提升了书画纸的综合品质。Based on this, the purpose of the present invention includes providing a calligraphy and painting paper composition, which can be used to make a pulp liquid, and the handmade calligraphy and painting paper prepared further has excellent comprehensive quality, fine paper quality, controllable ink wetting effect, improved pigment locking effect, good color retention effect, and strong paper tensile strength. The present invention also provides a preparation method for calligraphy and painting paper, improves the aging step, and further improves the comprehensive quality of calligraphy and painting paper.
上述发明目的可以通过如下的技术方案实现。The above-mentioned object of the invention can be achieved through the following technical solutions.
第一方面，本发明提供了一种书画纸组合物，按重量份数计，包括如下组分：20～65份的皮纤维浆，20～65份的竹纤维浆，1～2份的菊粉，1～2.5份的碱性钙源，0.5～2.5份的壳聚糖，1～2份的纤维素微晶粉，0.5～2.5份的羧甲基纤维素钠，0.5～2.5份的聚乙烯亚胺以及0～3.5份的香料；其中，所述皮纤维浆中包含皮纤维和水，所述竹纤维浆中包含竹纤维和水，所述碱性钙源以CaO的重量份数份数计。In a first aspect, the present invention provides a calligraphy and painting paper composition, comprising the following components in parts by weight: 20 to 65 parts of skin fiber pulp, 20 to 65 parts of bamboo fiber pulp, 1 to 2 parts of inulin, 1 to 2.5 parts of alkaline calcium source, 0.5 to 2.5 parts of chitosan, 1 to 2 parts of cellulose microcrystalline powder, 0.5 to 2.5 parts of sodium carboxymethyl cellulose, 0.5 to 2.5 parts of polyethyleneimine and 0 to 3.5 parts of fragrance; wherein the skin fiber pulp contains skin fibers and water, the bamboo fiber pulp contains bamboo fibers and water, and the alkaline calcium source is measured in parts by weight of CaO.
在一些实施方式中，所述皮纤维的长度为1mm～10mm，所述竹纤维的长度为1mm～3mm。In some embodiments, the length of the skin fiber is 1 mm to 10 mm, and the length of the bamboo fiber is 1 mm to 3 mm.
在一些实施方式中，所述的书画纸组合物满足下组中的任一个或任意多个特征：In some embodiments, the calligraphy and painting paper composition satisfies any one or more of the following characteristics:
所述皮纤维为青檀皮纤维；The skin fiber is Pteris tannin skin fiber;
所述皮纤维浆中的皮纤维重量占比为88％～95％；The weight proportion of the skin fiber in the skin fiber pulp is 88% to 95%;
所述皮纤维浆中的含水量为5％～12％；The moisture content in the skin fiber pulp is 5% to 12%;
所述竹纤维为苦竹纤维；The bamboo fiber is bitter bamboo fiber;
所述竹纤维浆中的竹纤维重量占比为88％～95％；The weight proportion of bamboo fiber in the bamboo fiber pulp is 88% to 95%;
所述竹纤维浆中的含水量为5％～12％；The water content of the bamboo fiber pulp is 5% to 12%;
所述皮纤维和所述竹纤维的重量份数比值为0.3～3.25；The weight ratio of the skin fiber to the bamboo fiber is 0.3 to 3.25;
所述碱性钙源选自石灰和氢氧化钙中的一种或两种；The alkaline calcium source is selected from one or both of lime and calcium hydroxide;
所述壳聚糖的重均分子量为100～250kDa；The weight average molecular weight of the chitosan is 100 to 250 kDa;
所述羧甲基纤维素钠的重量份数为0.5～2.5份；The weight proportion of the sodium carboxymethyl cellulose is 0.5 to 2.5 parts;
所述羧甲基纤维素钠的重均分子量为5～20kDa；The weight average molecular weight of the sodium carboxymethyl cellulose is 5 to 20 kDa;
所述聚乙烯亚胺的重均分子量为1～10kDa；The weight average molecular weight of the polyethyleneimine is 1 to 10 kDa;
所述0～3.5份的香料至少包括0～2份的沉香粉；The 0-3.5 parts of spices include at least 0-2 parts of agarwood powder;
所述书画纸组合物的总重量份数为65～130份。The total weight of the calligraphy and painting paper composition is 65 to 130 parts.
在一些实施方式中，按重量份数计，所述书画纸组合物包括如下组分：30～55份的皮纤维浆，30～55份的竹纤维浆，1～1.6份的菊粉，1.5～2.2份的碱性钙源，1～1.6份的壳聚糖，1.4～2份的纤维素微晶粉，1.5～2.2份的羧甲基纤维素钠，1～2.2份的聚乙烯亚胺和0～2份的沉香粉。In some embodiments, the calligraphy and painting paper composition includes the following components, measured by weight: 30 to 55 parts of skin fiber pulp, 30 to 55 parts of bamboo fiber pulp, 1 to 1.6 parts of inulin, 1.5 to 2.2 parts of alkaline calcium source, 1 to 1.6 parts of chitosan, 1.4 to 2 parts of cellulose microcrystalline powder, 1.5 to 2.2 parts of sodium carboxymethyl cellulose, 1 to 2.2 parts of polyethyleneimine and 0 to 2 parts of agarwood powder.
在一些实施方式中，按重量份数计，所述书画纸组合物包括如下组分：48～52份的皮纤维浆，35～40份的竹纤维浆，1.2～1.6份的菊粉，1.8～2.2份的碱性钙源，1.4～1.6份的壳聚糖，1.4～1.6份的纤维素微晶粉，1.8～2.2份的羧甲基纤维素钠，1.8～2.2份的聚乙烯亚胺和0～1.6份的沉香粉。In some embodiments, the calligraphy and painting paper composition includes the following components, measured by weight: 48 to 52 parts of skin fiber pulp, 35 to 40 parts of bamboo fiber pulp, 1.2 to 1.6 parts of inulin, 1.8 to 2.2 parts of alkaline calcium source, 1.4 to 1.6 parts of chitosan, 1.4 to 1.6 parts of cellulose microcrystalline powder, 1.8 to 2.2 parts of sodium carboxymethyl cellulose, 1.8 to 2.2 parts of polyethyleneimine and 0 to 1.6 parts of agarwood powder.
第二方面，本发明提供了一种手工书画纸的制备方法，根据本发明第一方面所述书画纸组合物的组成提供计量的各原料；In a second aspect, the present invention provides a method for preparing handmade calligraphy and painting paper, wherein the composition of the calligraphy and painting paper composition according to the first aspect of the present invention provides metered raw materials;
所述的制备方法包括如下步骤：The preparation method comprises the following steps:
将所述皮纤维浆和所述竹纤维浆混匀，制得混合纤维浆；Mixing the leather fiber pulp and the bamboo fiber pulp to obtain mixed fiber pulp;
将所述混合纤维浆与羧甲基纤维素钠、所述碱性钙源和所述纤维素微晶粉混匀，制得混合浆A；The mixed fiber pulp is mixed with sodium carboxymethyl cellulose, the alkaline calcium source and the cellulose microcrystalline powder to obtain mixed pulp A;
将所述混合浆A与所述壳聚糖、所述聚乙烯亚胺和所述菊粉混匀，制得混合浆B；Mixing the mixed slurry A with the chitosan, the polyethyleneimine and the inulin to obtain a mixed slurry B;
将所述混合浆B与所述香料混匀，制得纸浆液；或者，以所述混合浆B作为纸浆液；The mixed pulp B is mixed with the spices to obtain pulp liquid; or the mixed pulp B is used as pulp liquid;
将所述纸浆液抄纸、脱水、干燥，制得干纸；Making paper from the pulp liquid, dehydrating and drying it to obtain dry paper;
将所述干纸以热处理方式于≥110℃下进行熟化，制得所述手工书画纸。The dry paper is cured by heat treatment at ≥110° C. to obtain the handmade calligraphy and painting paper.
在一些实施方式中，所述热处理于110～150℃下进行100～720小时。In some embodiments, the heat treatment is performed at 110-150° C. for 100-720 hours.
在一些实施方式中，所述混合浆A的pH值为8.2～8.6，所述纸浆液的pH值为7.8～8.2；In some embodiments, the pH value of the mixed pulp A is 8.2 to 8.6, and the pH value of the pulp liquid is 7.8 to 8.2;
任一个混匀步骤独立地采用搅拌方式进行，搅拌速率50～60rpm；Any mixing step is independently carried out by stirring at a stirring rate of 50 to 60 rpm;
将所述纸浆液抄纸、脱水、干燥的步骤包括：将所述纸浆液抄纸，脱水至含水量≤30％，于180～200℃干燥5～10分钟。The steps of making paper from the pulp liquid, dehydrating and drying the paper include: making paper from the pulp liquid, dehydrating the paper to a water content of ≤30%, and drying at 180-200° C. for 5-10 minutes.
第三方面，本发明提供了一种手工书画纸，采用本发明第二方面所述的制备方法制备得到。In a third aspect, the present invention provides a handmade calligraphy and painting paper, which is prepared by the preparation method described in the second aspect of the present invention.
第四方面，本发明提供了一种手工书画纸，以重量份数计，包括如下原料组分：In a fourth aspect, the present invention provides a handmade calligraphy and painting paper, comprising the following raw material components in parts by weight:
皮纤维20～65份；20-65 parts of leather fiber;
竹纤维20～65份；20-65 parts of bamboo fiber;
菊粉1～2份；1-2 parts of inulin;
碱性钙源：1～2.5份，以CaO的重量份数份数计；Alkaline calcium source: 1-2.5 parts, based on the weight of CaO;
壳聚糖0.5～2.5份；Chitosan 0.5-2.5 parts;
纤维素微晶粉1～2份；1-2 parts of cellulose microcrystalline powder;
羧甲基纤维素钠0.5～2.5份；0.5-2.5 parts of sodium carboxymethyl cellulose;
聚乙烯亚胺0.5～2.5份；以及0.5 to 2.5 parts of polyethyleneimine; and
沉香粉0～2份。0-2 parts of agarwood powder.
本发明的有益效果包括如下方面：The beneficial effects of the present invention include the following aspects:
本发明提供的书画纸组合物中的皮纤维和竹纤维通过长短纤维的搭配提供纸浆纤维，还通过各种助剂(如壳聚糖、聚乙烯亚胺、菊粉以及羧甲基纤维素钠等)引入羟基、羧基、氨基等功能性基团对纸浆纤维进行表面改性，从而使得该书画纸组合物可以制成高品质的手工书画纸，纸质细腻、润墨效果可控，对颜料的锁定效果提高，颜色保持效果好，纸张拉力强，能够保留传统书画纸的文化与艺术价值。其中，壳聚糖可发挥助留助滤作用，还可在本申请中发挥干增强剂的作用，线性的壳聚糖大分子可提供大量的氨基并使氨基充分接近纤维表面，可提高成膜能力，在纤维间架桥，而且分子链上的正电荷中心和/或羟基能够与纤维形成静电结合和/或氢键，可以改善纤维之间的结合；菊粉可结合水分子，控制水分扩散；羧甲基纤维素钠可作为稳定剂，既能起到在浆内增强作用，也能起到部分表面施胶作用。此外，聚乙烯亚胺还可作为增湿强剂及施胶增效剂，是一种带有叔氨基团的支链型聚合物，可以与细小纤维形成较强的静电结合力且对吸水性的影响小或无。The skin fiber and bamboo fiber in the calligraphy and painting paper composition provided by the present invention provide pulp fiber through the collocation of long and short fibers, and various additives (such as chitosan, polyethyleneimine, inulin and sodium carboxymethyl cellulose, etc.) are introduced to modify the surface of the pulp fiber by functional groups such as hydroxyl, carboxyl, and amino groups, so that the calligraphy and painting paper composition can be made into high-quality handmade calligraphy and painting paper, with fine paper quality, controllable ink moistening effect, improved locking effect on pigments, good color retention effect, strong paper tensile strength, and can retain the cultural and artistic value of traditional calligraphy and painting paper. Among them, chitosan can play a role in retention and filtration, and can also play the role of dry reinforcing agent in this application. The linear chitosan macromolecule can provide a large amount of amino groups and make the amino groups fully close to the fiber surface, which can improve the film-forming ability and bridge between fibers. Moreover, the positive charge center and/or hydroxyl group on the molecular chain can form electrostatic bonding and/or hydrogen bonds with the fibers, which can improve the bonding between fibers; inulin can bind water molecules to control water diffusion; sodium carboxymethyl cellulose can be used as a stabilizer, which can not only play a role in strengthening in the pulp, but also play a role in partial surface sizing. In addition, polyethyleneimine can also be used as a wetting agent and sizing enhancer. It is a branched polymer with tertiary amino groups. It can form a strong electrostatic binding force with fine fibers and has little or no effect on water absorption.
本发明提供的手工书画纸的制备方法采用包括前述具有特定组分的书画纸组合物的原料，可在较高温度(如110～150℃)下进行熟化，可以提高纤维素微晶与纸张纤维纤维素的结合作用，还能够提高石灰粉弱碱性下菊粉与羧甲基纤维素钠的协同作用，还可延缓纸张纤维素水解，延长纸张寿命，该温度条件下熟化还可以提高壳聚糖与聚乙烯亚胺与纤维、助剂的平铺效果。此外，该制备方法生产工艺简单，可采用传统生产装置，适合大规模连续化生产。The preparation method of handmade calligraphy and painting paper provided by the present invention uses raw materials including the calligraphy and painting paper composition with specific components, which can be ripened at a relatively high temperature (such as 110-150° C.), which can improve the binding effect between cellulose microcrystals and paper fiber cellulose, and can also improve the synergistic effect of inulin and sodium carboxymethyl cellulose under the weak alkalinity of lime powder, and can also delay the hydrolysis of paper cellulose and extend the life of paper. Ripening under this temperature condition can also improve the paving effect of chitosan, polyethyleneimine, fiber, and additives. In addition, the preparation method has a simple production process, can use traditional production equipment, and is suitable for large-scale continuous production.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
以下结合附图简单阐述本发明中的部分技术方案。应当理解，这些附图是为了更好地理解本发明，并不构成对本发明保护范围的限制。本领域技术人员还可以采用这些附图以外的其他方式来实施本发明，或者实施本发明中的一个或多个技术方案。The following briefly describes some technical solutions in the present invention in conjunction with the accompanying drawings. It should be understood that these drawings are for a better understanding of the present invention and do not constitute a limitation on the scope of protection of the present invention. Those skilled in the art may also implement the present invention or one or more technical solutions in the present invention in other ways other than these drawings.
图1为本发明一个实施方式中的手工书画纸的制备流程示意图。FIG. 1 is a schematic diagram of a preparation process of handmade calligraphy and painting paper in one embodiment of the present invention.
具体实施方式DETAILED DESCRIPTION
以下结合附图以及本发明的一些实施方式或实施例对本发明进行更详细的描述，这些内容是为了更好地理解本发明，但并不构成对本发明保护范围的限制。本领域技术人员还可以采用这些附图、实施方式或实施例以外的其他方式来实施本发明，或者实施本发明中的一个或多个技术方案。The present invention is described in more detail below in conjunction with the accompanying drawings and some implementation modes or examples of the present invention. These contents are for a better understanding of the present invention, but do not constitute a limitation on the protection scope of the present invention. Those skilled in the art may also implement the present invention or one or more technical solutions in the present invention in other ways than these drawings, implementation modes or examples.
除非特别说明，本文所使用的技术术语具有本发明所属技术领域的通常含义。Unless otherwise specified, the technical terms used herein have the common meanings in the technical field to which the present invention belongs.
以下对本发明中涉及的词语、短语或语句的含义进行解释。本部分的含义解释适用于本发明的全文，既适用于下文，也适用于上文。本发明中涉及引用文献时，相关术语或文字描述在引用文献中的定义也一并被引用，但是，与本发明中的定义相冲突时，以本发明中的定义为准。The meanings of the words, phrases or sentences involved in the present invention are explained below. The meanings explained in this section apply to the entire text of the present invention, both below and above. When the present invention involves references, the definitions of the relevant terms or textual descriptions in the references are also cited, but when they conflict with the definitions in the present invention, the definitions in the present invention shall prevail.
除非另外说明，本发明的上下文中涉及的词语、短语或语句具有如下含义。Unless otherwise stated, words, phrases or sentences referred to in the context of the present invention have the following meanings.
本发明中，如无其他说明，“A和/或B”表示A、B以及“A与B的组合”，或者表示A、B或“A与B的组合”，可根据所在语段描述恰当理解。In the present invention, unless otherwise specified, "A and/or B" means A, B and "a combination of A and B", or means A, B or "a combination of A and B", which can be appropriately understood according to the description in the paragraph.
本发明中，“可选地”，表示可以有，也可以无，以能够实现本发明的技术方案为选择标准。本发明中，“可选方式”，表示只要适用于本发明的技术方案，就可以用来实施本发明。In the present invention, "optionally" means that it may or may not be present, and the selection criteria are the technical solutions that can implement the present invention. In the present invention, "optional manner" means that as long as it is applicable to the technical solutions of the present invention, it can be used to implement the present invention.
本发明中，“优选(比如，prefer,preferable,preferably,preferred等)”、“较佳”、“更优选”、“更佳”、“最优选”等优选实施方式，不构成对发明的涵盖范围及保护范围的任何意义上的限制，并非用于限定本发明的范围和实施方式，仅用于提供一些实施方式作为举例。In the present invention, preferred embodiments such as “preferred (e.g., prefer, preferable, preferably, preferred, etc.)”, “preferable”, “more preferred”, “better”, and “most preferred” do not constitute any limitation on the scope of coverage and protection scope of the invention, and are not used to limit the scope and embodiments of the present invention, but are only used to provide some embodiments as examples.
本发明的描述中，对于“优选之一”、“优选方式之一”、“优选实施方式之一”、“优选例之一”、“优选例”、“在一优选的实施方式中”、“一些优选例中”、“一些优选方式中”、“优选为”、“优选”、“优选地”、“更优选”、“更优地”、“进一步优选”、“最优选”等优选方式，以及“实施方式之一”、“方式之一”、“示例”、“具体示例”、“举例如”、“作为举例”、“例如”、“比如”、“如”等示意的列举方式，同样不构成对发明的涵盖范围及保护范围的任何意义上的限制，且各方式所描述的具体特征包含于本发明的至少一个具体实施方式中。本发明中，各方式所描述的具体特征可以在任何的一个或者多个具体实施方式中以合适的方式结合。本发明中，各优选方式对应的技术特征或技术方案也可以通过任意合适的方式结合。In the description of the present invention, the preferred modes such as "one of the preferred embodiments", "one of the preferred modes", "one of the preferred embodiments", "one of the preferred examples", "preferred examples", "in a preferred embodiment", "some preferred examples", "in some preferred modes", "preferably", "preferably", "preferably", "more preferably", "more preferably", "further preferably", "most preferably", and the illustrative enumeration modes such as "one of the embodiments", "one of the modes", "example", "specific example", "for example", "as an example", "for example", "such as", "such as", etc., also do not constitute any limitation on the scope of coverage and protection scope of the invention, and the specific features described in each mode are included in at least one specific embodiment of the present invention. In the present invention, the specific features described in each mode may be combined in a suitable manner in any one or more specific embodiments. In the present invention, the technical features or technical solutions corresponding to each preferred mode may also be combined in any suitable manner.
本发明中，“其任意组合”，在数量上表示“大于1”，在涵盖范围上表示以下情形构成的组：“任意选择其中一个，或者任意选择其中至少两个构成的组”。In the present invention, "any combination thereof" means "greater than 1" in terms of quantity, and means a group consisting of the following situations in terms of coverage: "arbitrarily select one of them, or arbitrarily select a group consisting of at least two of them."
本发明中，“一个或多个”、“一种或多种”等“一或多”的描述，与“至少一个”、“至少一种”、“其组合”、“或其组合”、“及其组合”、“或其任意组合”、“及其任意组合”等具有相同含义，可以互换使用，表示数量上等于“1”或“大于1”，也即表示数量上≥2。In the present invention, the description of "one or more", "one or more" and so on have the same meaning as "at least one", "at least one", "a combination thereof", "or a combination thereof", "and combinations thereof", "or any combination thereof", "and any combination thereof", etc., and can be used interchangeably to indicate that the quantity is equal to "1" or "greater than 1", that is, it means that the quantity is ≥2.
本发明中，采用“或/和”、“和/或”表示“任意选择其一或者选择其任意合适的组合”，也表示至少其一。In the present invention, "or/and" and "and/or" are used to indicate "select any one or select any appropriate combination thereof", and also indicate at least one.
本发明所述的“通常”、“常规”、“一般”、“经常”、“往往”等方式描述的现有技术手段，也都被引用作为本发明内容的参考，如无特别说明，可视为本发明的部分技术特征的优选方式之一，且需要注意的是，不构成对发明的涵盖范围及保护范围的任何意义上的限制。The prior art means described in the present invention in such ways as “usually”, “conventional”, “general”, “frequently” and “often” are also cited as references to the contents of the present invention. Unless otherwise specified, they can be regarded as one of the preferred ways of some technical features of the present invention. It should be noted that they do not constitute any limitation on the scope of coverage and protection scope of the invention.
本发明涉及的数值范围，如无特别说明，均包括两个端点。Unless otherwise specified, the numerical range involved in the present invention includes both endpoints.
本发明中涉及的数据范围单位，如果仅在右端点后记载了单位，则表示左端点和右端点的单位是相同的，也即该单位适用于该数据范围内的任意数据。比如，5～10分钟表示左端点“5”和右端点“10”的单位都是分钟(min)。The data range units involved in the present invention, if the unit is recorded only after the right endpoint, it means that the units of the left endpoint and the right endpoint are the same, that is, the unit is applicable to any data within the data range. For example, 5-10 minutes means that the units of the left endpoint "5" and the right endpoint "10" are both minutes (min).
除非另有说明，本发明中涉及的“包括”、“含有”、“包含”、“具有”、“存在”等词语是开放式的，允许额外引入未引述的其他成员或方法步骤；相应的技术方案由相应的封闭式技术方案以及开放式范围内的其他技术方案构成。作为一种非限制性举例，“A包括a1、a2和a3”表示A至少包括a1、a2和a3，还允许包括其他的成员或方法步骤，比如a4；此外，“A包括a1、a2和a3”由封闭式技术方案“A由a1、a2和a3组成”以及相应开放式范围内的其他技术方案所构成。Unless otherwise specified, the words "include", "contain", "include", "have", "exist" and the like involved in the present invention are open-ended, and allow the additional introduction of other members or method steps that are not cited; the corresponding technical solution is composed of the corresponding closed technical solution and other technical solutions within the open scope. As a non-limiting example, "A includes a1, a2 and a3" means that A includes at least a1, a2 and a3, and is also allowed to include other members or method steps, such as a4; in addition, "A includes a1, a2 and a3" is composed of the closed technical solution "A consists of a1, a2 and a3" and other technical solutions within the corresponding open scope.
本发明中，“第一方面”、“第二方面”、“第三方面”、“第四方面”等中的“第一”、“第二”、“第三”、“第四”等仅用于描述目的，并不理解为指示、暗示或隐含知名相对重要性或数量。In the present invention, “first”, “second”, “third”, “fourth”, etc. in “first aspect”, “second aspect”, “third aspect”, “fourth aspect”, etc. are only used for descriptive purposes and are not to be understood as indicating, suggesting or implying any relative importance or quantity.
在本发明提及的所有文献及这些文献直接引用或者间接引用的文献，都在本申请中被引用作为参考，就如同每一篇文献被单独引用作为参考那样。All documents mentioned in the present invention and documents directly or indirectly cited by these documents are cited in this application as references, just as if each document was cited as a reference individually.
可以理解，在本发明范围内，本发明的上述各技术特征和在下文(包括但不限于实施例)中具体描述的各技术特征之间都可以通过任意合适的方式互相组合，从而构成新的或优选的技术方案，只要能够用于实施本发明的即可。限于篇幅，不再一一累述。前述“技术特征”可以为一个技术方案，也可以为一个技术方案的一部分。It is understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features specifically described below (including but not limited to the embodiments) can be combined with each other in any suitable manner to form a new or preferred technical solution, as long as it can be used to implement the present invention. Due to space limitations, they will not be described one by one. The aforementioned "technical features" can be a technical solution or a part of a technical solution.
在本发明的第一方面，提供了一种书画纸组合物，其包括皮纤维和竹纤维的组合，还包括菊粉、碱性钙源、壳聚糖、纤维素微晶粉、羧甲基纤维素钠和聚乙烯亚胺。In a first aspect of the present invention, a calligraphy and painting paper composition is provided, which comprises a combination of skin fiber and bamboo fiber, and further comprises inulin, an alkaline calcium source, chitosan, cellulose microcrystalline powder, sodium carboxymethyl cellulose and polyethyleneimine.
在本发明的一些实施方式中，提供了一种书画纸组合物，其包括皮纤维浆、竹纤维浆、菊粉、碱性钙源、壳聚糖、纤维素微晶粉、羧甲基纤维素钠和聚乙烯亚胺，还可以包括或不包括香料。In some embodiments of the present invention, a calligraphy and painting paper composition is provided, which includes skin fiber pulp, bamboo fiber pulp, inulin, an alkaline calcium source, chitosan, cellulose microcrystalline powder, sodium carboxymethyl cellulose and polyethyleneimine, and may or may not include spices.
在本发明的一些实施方式中，提供了一种书画纸组合物，按重量份数计，包括如下组分：20～65份的皮纤维浆，20～65份的竹纤维浆，1～2份的沉香粉，1～2份的菊粉，1～2.5份的碱性钙源，0.5～2.5份的壳聚糖，1～2份的纤维素微晶粉，0.5～2.5份的羧甲基纤维素钠，0.5～2.5份的聚乙烯亚胺，0～3.5份的香料(如0～2份的沉香粉，进一步如1～2份的沉香粉)；其中，所述皮纤维浆中包含皮纤维和水，所述竹纤维浆中包含竹纤维和水，所述碱性钙源以CaO的重量份数份数计。In some embodiments of the present invention, a calligraphy and painting paper composition is provided, comprising the following components in parts by weight: 20 to 65 parts of skin fiber pulp, 20 to 65 parts of bamboo fiber pulp, 1 to 2 parts of agarwood powder, 1 to 2 parts of inulin, 1 to 2.5 parts of alkaline calcium source, 0.5 to 2.5 parts of chitosan, 1 to 2 parts of cellulose microcrystalline powder, 0.5 to 2.5 parts of sodium carboxymethyl cellulose, 0.5 to 2.5 parts of polyethyleneimine, and 0 to 3.5 parts of spices (such as 0 to 2 parts of agarwood powder, further such as 1 to 2 parts of agarwood powder); wherein the skin fiber pulp contains skin fibers and water, the bamboo fiber pulp contains bamboo fibers and water, and the alkaline calcium source is measured in parts by weight of CaO.
本发明提供的书画纸组合物中的皮纤维和竹纤维通过长短纤维的搭配提供纸浆纤维，还通过各种助剂(如壳聚糖、聚乙烯亚胺、菊粉以及羧甲基纤维素钠等)引入羟基、羧基、氨基等功能性基团对纸浆纤维进行表面改性，从而使得该书画纸组合物可以制成高品质的手工书画纸，纸质细腻、润墨效果可控，对颜料的锁定效果提高，颜色保持效果好，纸张拉力强，能够保留传统书画纸的文化与艺术价值。其中，壳聚糖可发挥助留助滤作用，还可在本申请中发挥干增强剂的作用，线性的壳聚糖大分子可提供大量的氨基并使氨基充分接近纤维表面，可提高成膜能力，在纤维间架桥，而且分子链上的正电荷中心和/或羟基能够与纤维形成静电结合和/或氢键，可以改善纤维之间的结合；菊粉可结合水分子，控制水分扩散；羧甲基纤维素钠可作为稳定剂，既能起到在浆内增强作用，也能起到部分表面施胶作用。此外，聚乙烯亚胺还可作为增湿强剂及施胶增效剂，是一种带有叔氨基团的支链型聚合物，可以与细小纤维形成较强的静电结合力且对吸水性的影响小或无。The skin fiber and bamboo fiber in the calligraphy and painting paper composition provided by the present invention provide pulp fiber through the collocation of long and short fibers, and various additives (such as chitosan, polyethyleneimine, inulin and sodium carboxymethyl cellulose, etc.) are introduced to modify the surface of the pulp fiber by functional groups such as hydroxyl, carboxyl, and amino groups, so that the calligraphy and painting paper composition can be made into high-quality handmade calligraphy and painting paper, with fine paper quality, controllable ink moistening effect, improved locking effect on pigments, good color retention effect, strong paper tensile strength, and can retain the cultural and artistic value of traditional calligraphy and painting paper. Among them, chitosan can play a role in retention and filtration, and can also play the role of dry reinforcing agent in this application. The linear chitosan macromolecule can provide a large amount of amino groups and make the amino groups fully close to the fiber surface, which can improve the film-forming ability and bridge between fibers. Moreover, the positive charge center and/or hydroxyl group on the molecular chain can form electrostatic bonding and/or hydrogen bonds with the fibers, which can improve the bonding between fibers; inulin can bind water molecules to control water diffusion; sodium carboxymethyl cellulose can be used as a stabilizer, which can not only play a role in strengthening in the pulp, but also play a role in partial surface sizing. In addition, polyethyleneimine can also be used as a wetting agent and sizing enhancer. It is a branched polymer with tertiary amino groups. It can form a strong electrostatic binding force with fine fibers and has little or no effect on water absorption.
在本发明中，“书画纸组合物”可以为包装于一个独立体系中的混合物，也可以分装于两个或更多个的不同体系中。利用该书画纸组合物制备手工书画纸时，各组分可以在同一个步骤中使用，也可以在不同的步骤中分开使用。此外，在制备手工书画纸的过程中，该书画纸组合物中的一个或多个组分可以发生化学反应而转化为其他的组分。比如，以石灰粉形式提供的CaO加入到浆料中后，可全部或部分转化为Ca(OH)2。In the present invention, the "calligraphy and painting paper composition" can be a mixture packaged in an independent system, or it can be packaged in two or more different systems. When using the calligraphy and painting paper composition to prepare handmade calligraphy and painting paper, each component can be used in the same step or separately in different steps. In addition, during the preparation of handmade calligraphy and painting paper, one or more components in the calligraphy and painting paper composition can undergo chemical reactions and be converted into other components. For example, CaO provided in the form of lime powder can be fully or partially converted into Ca(OH)2 after being added to the slurry.
在一些实施方式中，所述书画纸组合物的总重量份数可以为45～145份，进一步可以为65～130份，还可以为下述任一种重量份数或者选自下述任两种重量份数构成的区间：45份、50份、55份、60份、65份、70份、75份、80份、85份、90份、95份、96份、97份、98份、99份、100份、101份102份、103份、104份、105份、110份、115份、120份、125份、130份、135份、140份、145份等。所述书画纸组合物的总重量份数可以选自下述任一范围：90～110份、95～105份、98～102份、99～101份等。In some embodiments, the total weight of the painting and calligraphy paper composition can be 45 to 145 parts, further can be 65 to 130 parts, can also be any of the following weight parts or selected from the interval consisting of any two of the following weight parts: 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, 100 parts, 101 parts 102 parts, 103 parts, 104 parts, 105 parts, 110 parts, 115 parts, 120 parts, 125 parts, 130 parts, 135 parts, 140 parts, 145 parts, etc. The total weight of the painting and calligraphy paper composition can be selected from any of the following ranges: 90 to 110 parts, 95 to 105 parts, 98 to 102 parts, 99 to 101 parts, etc.
在一些实施方式中，所述书画纸组合物的总重量份数为100份。In some embodiments, the total weight of the calligraphy and painting paper composition is 100 parts.
本发明使用的皮纤维是一种长纤维，拉伸强度好，韧性高，结晶度也高，有利于纸张长久保存。所述皮纤维其长度可以为但不限于1mm～10mm，还可以为1mm、2mm、3mm、4mm、5mm、6mm、7mm、8mm、9mm、10mm等中任一种长度，还可以选自上述任两种长度所构成的长度区间。The skin fiber used in the present invention is a long fiber with good tensile strength, high toughness and high crystallinity, which is conducive to the long-term preservation of paper. The length of the skin fiber can be but not limited to 1mm to 10mm, and can also be any length of 1mm, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm, 9mm, 10mm, etc., and can also be selected from the length interval formed by any two of the above lengths.
本发明中涉及“皮纤维的长度”，可以指单根皮纤维的长度，也可以指书画纸组合物中单根皮纤维的平均长度。The "length of the sheath fibers" in the present invention may refer to the length of a single sheath fiber or the average length of single sheath fibers in the calligraphy and painting paper composition.
本发明使用的竹纤维是一种短纤维，其表面具有较多的沟壑状拓扑结构，能够提供较好的锁墨与固色作用。所述竹纤维其长度可以为但不限于1mm～3mm，还可以为1mm、1.5mm、2mm、2.5mm、3mm等中任一种长度，还可以选自上述任两种长度所构成的长度区间。The bamboo fiber used in the present invention is a short fiber with a plurality of gully-shaped topological structures on its surface, which can provide a good ink locking and color fixing effect. The length of the bamboo fiber can be but not limited to 1 mm to 3 mm, and can also be any length of 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, etc., and can also be selected from the length interval formed by any two of the above lengths.
本发明中涉及“竹纤维的长度”，可以指单根竹纤维的长度，也可以指书画纸组合物中竹纤维的平均长度。The "length of bamboo fiber" in the present invention may refer to the length of a single bamboo fiber or the average length of bamboo fibers in the calligraphy and painting paper composition.
在一些实施方式中，所述皮纤维的长度为1mm～10mm，所述竹纤维的长度为1mm～3mm。所述皮纤维的长度和所述竹纤维的长度还可以分别独立地或相互组合地选自上下文中的其他长度范围或长度值。In some embodiments, the length of the skin fiber is 1 mm to 10 mm, and the length of the bamboo fiber is 1 mm to 3 mm. The length of the skin fiber and the length of the bamboo fiber can also be selected from other length ranges or length values in the context independently or in combination.
通过使用皮纤维和竹纤维的组合，可实现长纤维与短纤维的组合搭配，有利于提高纸张的结构强度和书画性能。一方面，长纤维织构结合孔隙较大，由短纤维填充后可提高纤维交织强度，从结构上提高纸张拉伸、耐折和撕裂强度；另一方面，短纤维填充可有效改变光线在织构结构中的折射与散射，从而改善颜色效果；此外，竹纤维表面粗糙度较皮纤维更多，能够锁定较多的墨或颜料颗粒，而皮纤维更易引导水分传递。较长的皮纤维和较短的竹纤维的组合搭配在调整配比的基础上，进一步调整表面粗糙程度能够进一步改善力学性能、光学性能和书画表达效果。By using a combination of skin fibers and bamboo fibers, a combination of long fibers and short fibers can be achieved, which is beneficial to improving the structural strength and calligraphy and painting performance of paper. On the one hand, the long fiber texture has a large pore size, and the filling of short fibers can improve the fiber interweaving strength, thereby improving the tensile, folding and tearing strength of the paper from a structural perspective; on the other hand, short fiber filling can effectively change the refraction and scattering of light in the texture structure, thereby improving the color effect; in addition, the surface roughness of bamboo fibers is greater than that of skin fibers, which can lock more ink or pigment particles, while skin fibers are easier to guide water transfer. The combination of longer skin fibers and shorter bamboo fibers can further improve the mechanical properties, optical properties and calligraphy and painting expression effects by further adjusting the surface roughness on the basis of adjusting the ratio.
在本发明的一些实施方式中，所述皮纤维为青檀皮纤维。相对于其他种类的皮纤维，青檀皮纤维具有更好的纤维长度和韧性，更有利于成纸强度和水分扩散。In some embodiments of the present invention, the skin fiber is Pteris tannin skin fiber. Compared with other types of skin fibers, Pteris tannin skin fiber has better fiber length and toughness, and is more conducive to paper strength and water diffusion.
在本发明的一些实施方式中，所述皮纤维浆中的皮纤维重量占比为88％～95％，具体举例如88％、89％、90％、95％等，还如下述任一种范围：88％～90％。In some embodiments of the present invention, the weight percentage of the sheath fibers in the sheath fiber pulp is 88% to 95%, specifically 88%, 89%, 90%, 95%, etc., and any of the following ranges: 88% to 90%.
在本发明的一些实施方式中，所述皮纤维浆中的含水量为5％～12％，具体举例如5％、10％、11％、12％等，还如下述任一种范围：88％～90％。In some embodiments of the present invention, the moisture content of the skin fiber pulp is 5% to 12%, specifically 5%, 10%, 11%, 12%, etc., and any of the following ranges: 88% to 90%.
在下文中，涉及书画纸组合物中某一种组分的重量份数，如无其他说明，在下述重量份数比例基础上进一步描述：20～65份的皮纤维浆，20～65份的竹纤维浆，1～2份的菊粉，1～2.5份的碱性钙源，0.5～2.5份的壳聚糖，1～2份的纤维素微晶粉，0.5～2.5份的羧甲基纤维素钠，0.5～2.5份的聚乙烯亚胺，0～2份的沉香粉以及0～1.5份的香草汁。进一步地，书画纸组合物的总重量份数可以为前述示例的范围或数值，如45～145份，进一步如65～130份，更进一步如95～105份，进一步如100份。In the following, the weight percentage of a certain component in the calligraphy and painting paper composition, unless otherwise specified, is further described based on the following weight percentage ratio: 20-65 parts of skin fiber pulp, 20-65 parts of bamboo fiber pulp, 1-2 parts of inulin, 1-2.5 parts of alkaline calcium source, 0.5-2.5 parts of chitosan, 1-2 parts of cellulose microcrystalline powder, 0.5-2.5 parts of sodium carboxymethyl cellulose, 0.5-2.5 parts of polyethyleneimine, 0-2 parts of agarwood powder and 0-1.5 parts of vanilla juice. Further, the total weight percentage of the calligraphy and painting paper composition can be the range or value of the above examples, such as 45-145 parts, further such as 65-130 parts, further such as 95-105 parts, further such as 100 parts.
在本发明的一些实施方式中，所述皮纤维浆的重量份数可以为前述的20～65份，还可以为20份、25份、30份、5份、40份、45份、50份、55份、60份、65份等中任一种重量份数，还可以选自前述任意两种重量份数所构成的区间，例如但不限于30～55份、40～55份、45～55份、48～55份、48～52份、48～50份、45～50份等。In some embodiments of the present invention, the weight proportion of the skin fiber pulp can be the aforementioned 20 to 65 parts, or any one of 20, 25, 30, 5, 40, 45, 50, 55, 60, 65, etc., and can also be selected from the interval formed by any two of the aforementioned weight proportions, for example but not limited to 30 to 55, 40 to 55, 45 to 55, 48 to 55, 48 to 52, 48 to 50, 45 to 50, etc.
在本发明的一些实施方式中，所述竹纤维浆中的竹纤维重量占比为88％～95％，具体举例如88％、89％、90％、95％等，还如下述任一种范围：88％～90％。In some embodiments of the present invention, the weight percentage of bamboo fiber in the bamboo fiber pulp is 88% to 95%, specifically 88%, 89%, 90%, 95%, etc., and any of the following ranges: 88% to 90%.
在本发明的一些实施方式中，所述竹纤维浆中的含水量为5％～12％，具体举例如5％、10％、11％、12％等，还如下述任一种范围：10％～12％等。In some embodiments of the present invention, the water content of the bamboo fiber pulp is 5% to 12%, specifically 5%, 10%, 11%, 12%, etc., and any of the following ranges: 10% to 12%, etc.
在本发明的一些实施方式中，所述竹纤维浆的重量份数可以为前述的20～65份，还可以为20份、25份、30份、5份、40份、45份、50份、55份、60份、65份等中任一种重量份数，还可以选自前述任意两种重量份数所构成的区间，例如但不限于30～55份、40～55份、45～55份、48～55份、48～52份、48～50份、45～50份等。In some embodiments of the present invention, the weight proportion of the bamboo fiber pulp can be the aforementioned 20 to 65 parts, or any one of 20, 25, 30, 5, 40, 45, 50, 55, 60, 65, etc., and can also be selected from the interval formed by any two of the aforementioned weight proportions, for example but not limited to 30 to 55, 40 to 55, 45 to 55, 48 to 55, 48 to 52, 48 to 50, 45 to 50, etc.
在本发明的一些实施方式中，所述竹纤维为苦竹纤维。与其他竹纤维相比，苦竹纤维细腻绵韧，有利于利用短纤维保持纸张韧性，达到纸张轻薄目的。In some embodiments of the present invention, the bamboo fiber is bitter bamboo fiber. Compared with other bamboo fibers, bitter bamboo fiber is fine and tough, which is conducive to using short fibers to maintain the toughness of paper and achieve the purpose of thin paper.
在本发明的一些实施方式中，所述皮纤维和所述竹纤维的重量份数比值为0.3～3.25，还可以为0.3、0.31、0.33、1/3(即三分之一)、0.35、0.4、0.45、0.5、0.51、0.55、0.6、0.65、2/3(即三分之二)、0.67、0.7、0.75、0.8、0.85、0.9、0.95、0.96、0.98、0.99、1、1.01、1.02、1.04、1.05、1.1、1.15、1.2、1.25、1.28、1.3、1.35、1.4、1.45、1.5、1.55、1.6、1.65、1.7、1.75、1.8、1.85、1.9、1.95、2、2.1、2.2、2.4、2.5、2.6、2.8、3、3.1、3.2、3.25等，还可以选自前述任意两种比值所构成的区间，例如但不限于0.31～3.25、0.3～1.5、0.3～1.4、0.33～3、(1/3)～3、4～2.5、0.5～2、(2/3)～1.5、0.9～1.1、0.95～1.05、0.98～1.02、0.99～1.01等。In some embodiments of the present invention, the weight ratio of the skin fiber to the bamboo fiber is 0.3-3.25, and can also be 0.3, 0.31, 0.33, 1/3 (i.e., one third), 0.35, 0.4, 0.45, 0.5, 0.51, 0.55, 0.6, 0.65, 2/3 (i.e., two thirds), 0.67, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 0.96, 0.98, 0.99, 1, 1.01, 1.02, 1.04, 1.05, 1.1, 1.15, 1.2, 1.25, 1.28, 1.3, 1.35, 1. 4, 1.45, 1.5, 1.55, 1.6, 1.65, 1.7, 1.75, 1.8, 1.85, 1.9, 1.95, 2, 2.1, 2.2, 2.4, 2.5, 2.6, 2.8, 3, 3.1, 3.2, 3.25, etc., and can also be selected from the interval formed by any two of the aforementioned ratios, such as but not limited to 0.31-3.25, 0.3-1.5, 0.3-1.4, 0.33-3, (1/3)-3, 4-2.5, 0.5-2, (2/3)-1.5, 0.9-1.1, 0.95-1.05, 0.98-1.02, 0.99-1.01, etc.
在本发明的一些实施方式中，所述皮纤维和所述竹纤维的重量份数相等，也即述皮纤维和所述竹纤维的重量份数比值为1。此时，具有理论上相等的重量份数，实际使用时，允许因为称量精度等因素影响具有一定的误差。比如，所述皮纤维相对于所述竹纤维的重量份数比值可以为但不限于0.9～1.1、0.95～1.05、0.98～1.02、0.99～1.01、0.995～1.005、0.999～1.001等范围内的数值。此时，更有利于发挥皮纤维和竹纤维长短搭配作用，更有利于改善力学性能、光学性能和书画表达效果。In some embodiments of the present invention, the weight proportions of the skin fiber and the bamboo fiber are equal, that is, the weight proportion ratio of the skin fiber to the bamboo fiber is 1. At this time, the weight proportions are theoretically equal, and in actual use, a certain error is allowed due to factors such as weighing accuracy. For example, the weight proportion ratio of the skin fiber to the bamboo fiber can be, but is not limited to, values within the ranges of 0.9 to 1.1, 0.95 to 1.05, 0.98 to 1.02, 0.99 to 1.01, 0.995 to 1.005, 0.999 to 1.001, etc. At this time, it is more conducive to the combination of the length of the skin fiber and the bamboo fiber, and more conducive to improving the mechanical properties, optical properties and the expression effects of calligraphy and painting.
菊粉是一种线性直链多糖，通常含有2～60个单糖单元。在本发明的书画纸组合物中，菊粉具有结合自由水的能力，可发挥控制水分扩散作用。在一些实施例中，所使用的菊粉具有50～60个单糖单元，更有利于控制水分扩散效果且对其他助剂的影响小或无。Inulin is a linear straight-chain polysaccharide, usually containing 2 to 60 monosaccharide units. In the calligraphy and painting paper composition of the present invention, inulin has the ability to bind free water and can play a role in controlling water diffusion. In some embodiments, the inulin used has 50 to 60 monosaccharide units, which is more conducive to controlling the water diffusion effect and has little or no effect on other additives.
在本发明的一些实施方式中，所述菊粉的重量份数为前述的1～2份，还可以为1份、1.2份、1.4份、1.5份、1.6份、1.8份、2份等，还可以选自前述任意两种重量份数所构成的区间，例如但不限于1.2～2份、1.4～2份、1.5～2份、1～1.6份、1～1.5份、1.2～1.6份、1.2～1.5份、1.4～1.6份、1.4～1.5份等。In some embodiments of the present invention, the weight proportion of inulin is 1 to 2 parts as mentioned above, and can also be 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, etc., and can also be selected from the interval consisting of any two of the aforementioned weight proportions, such as but not limited to 1.2 to 2 parts, 1.4 to 2 parts, 1.5 to 2 parts, 1 to 1.6 parts, 1 to 1.5 parts, 1.2 to 1.6 parts, 1.2 to 1.5 parts, 1.4 to 1.6 parts, 1.4 to 1.5 parts, etc.
在该书画纸组合物中，碱性钙源用于提供一定量的CaO。碱性钙源的非限制性示例如石灰和氢氧化钙中一种或两种。该书画纸组合物的碱性钙源可以包括石灰(主要成分为CaO)和氢氧化钙(Ca(OH)2)中的至少一种，可以为一定重量的石灰，其中的部分或全部石灰可以被等钙量的氢氧化钙所替代。作为非限制性示例，1重量份的石灰相可以按1重量份的CaO计，74重量份的氢氧化钙相可以按56重量份的CaO计。“等钙量”指相等种类的钙元素。In the calligraphy and painting paper composition, an alkaline calcium source is used to provide a certain amount of CaO. Non-limiting examples of alkaline calcium sources include one or both of lime and calcium hydroxide. The alkaline calcium source of the calligraphy and painting paper composition may include at least one of lime (the main component of which is CaO) and calcium hydroxide (Ca(OH)2 ), which may be a certain weight of lime, part or all of which may be replaced by an equal amount of calcium hydroxide. As a non-limiting example, 1 part by weight of the lime phase may be calculated as 1 part by weight of CaO, and 74 parts by weight of the calcium hydroxide phase may be calculated as 56 parts by weight of CaO. "Equal calcium amount" refers to equal types of calcium elements.
在一些实施例中，所述碱性钙源选自石灰和氢氧化钙中的一种或两种。In some embodiments, the alkaline calcium source is selected from one or both of lime and calcium hydroxide.
在本发明中，石灰可以采用石灰粉形式。氢氧化钙可以采用固体、溶液或混悬液方式。氢氧化钙可以为水合物，也可以是非水合的。In the present invention, lime can be in the form of lime powder. Calcium hydroxide can be in the form of solid, solution or suspension. Calcium hydroxide can be hydrated or non-hydrated.
本发明中，利用书画纸组合物中的碱性钙源(如石灰和/或氢氧化钙)，可在制备工艺的纤维浆料中加入碱性钙源(如石灰和/或氢氧化钙)，可以使体系pH值维持在一定的弱碱性，有利于提高羧甲基纤维素钠和菊粉的结构稳定性，例如体系pH值可以为7.0～8.5。通过加入碱性钙源(如石灰和/或氢氧化钙)，可以避免因酸化太过导致的纸张纤维素酸化降解而寿命纸张缩短。In the present invention, by using the alkaline calcium source (such as lime and/or calcium hydroxide) in the calligraphy and painting paper composition, the alkaline calcium source (such as lime and/or calcium hydroxide) can be added to the fiber slurry in the preparation process, so that the pH value of the system can be maintained at a certain weak alkalinity, which is beneficial to improve the structural stability of sodium carboxymethyl cellulose and inulin. For example, the pH value of the system can be 7.0-8.5. By adding the alkaline calcium source (such as lime and/or calcium hydroxide), the acidification and degradation of paper cellulose caused by excessive acidification can be avoided, thereby shortening the life of the paper.
在本发明的一些实施方式中，所述碱性钙源(如石灰和/或氢氧化钙)的重量份数为前述的1～2.5份，还可以为1份、1.2份、1.4份、1.5份、1.6份、1.7份、1.8份、1.9份、2份、2.1份、2.2份、2.3份、2.4份、2.5份等，还可以选自前述任意两种重量份数所构成的区间，例如但不限于1.5～2.5份、1.5～2.2份、1.5～2份、1.6～2.2份、1.6～2份、1.8～2.2份、1.8～2份、1.9～2.1份等，以碱性钙源中CaO的重量份数份数计。In some embodiments of the present invention, the weight proportion of the alkaline calcium source (such as lime and/or calcium hydroxide) is 1 to 2.5 parts as mentioned above, and may also be 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts, 2.5 parts, etc., and may also be selected from the interval consisting of any two of the aforementioned weight proportions, such as but not limited to 1.5 to 2.5 parts, 1.5 to 2.2 parts, 1.5 to 2 parts, 1.6 to 2.2 parts, 1.6 to 2 parts, 1.8 to 2.2 parts, 1.8 to 2 parts, 1.9 to 2.1 parts, etc., based on the weight proportion of CaO in the alkaline calcium source.
本发明中使用的壳聚糖具有桥联、助留助滤以及干增强剂作用，壳聚糖的线性大分子可使氨基充分接近纤维表面，可提高成膜能力，在纤维间架桥，分子链上正电荷中心和/或羟基能够与纤维形成静电结合和/或氢键，可以改善纤维之间的结合；此外，壳聚糖还可以提供氨基，尤其在纸张略有酸化的情况下，氨基可以吸附氢离子使壳聚糖分子带正电荷，一方面可起到控制酸化的作用，另一方面可以有效锁定颜料，改善书画效果。此外，壳聚糖还可以发挥一定的抑菌作用。The chitosan used in the present invention has the functions of bridging, retention and filtration aid, and dry enhancer. The linear macromolecules of chitosan can make the amino group fully close to the fiber surface, which can improve the film-forming ability, bridge between fibers, and the positive charge center and/or hydroxyl group on the molecular chain can form electrostatic bonding and/or hydrogen bonds with the fibers, which can improve the bonding between fibers; in addition, chitosan can also provide amino groups, especially when the paper is slightly acidified, the amino group can absorb hydrogen ions to make the chitosan molecules positively charged, which can control the acidification on the one hand, and effectively lock the pigment on the other hand, improving the painting and calligraphy effect. In addition, chitosan can also play a certain antibacterial effect.
在本发明的一些实施方式中，所述壳聚糖的重均分子量为100～250kDa，例如可以为下述任一种分子量，还可以选自下述任两种分子量构成的区间：100kDa、120kDa、140kDa、150kDa、160kDa、180kDa、200kDa、240kDa、250kDa等。所述壳聚糖的重均分子量还可以选自下述任一范围：100～200kDa、120～160kDa、150～180kDa、140～160kDa等。在适当的分子量范围内，随壳聚糖分子量的提高，更利于提高成膜能力。In some embodiments of the present invention, the weight average molecular weight of the chitosan is 100-250 kDa, for example, any of the following molecular weights, or an interval consisting of any two of the following molecular weights: 100 kDa, 120 kDa, 140 kDa, 150 kDa, 160 kDa, 180 kDa, 200 kDa, 240 kDa, 250 kDa, etc. The weight average molecular weight of the chitosan can also be selected from any of the following ranges: 100-200 kDa, 120-160 kDa, 150-180 kDa, 140-160 kDa, etc. Within the appropriate molecular weight range, as the molecular weight of the chitosan increases, it is more conducive to improving the film-forming ability.
在本发明的一些实施方式中，所述壳聚糖的重量份数为前述的0.5～2.5份，还可以为0.5份、0.6份、0.8份、1份、1.2份、1.4份、1.5份、1.6份、1.8份、2份、2.2份、2.4份、2.5份等，还可以选自前述任意两种重量份数所构成的区间，例如但不限于1～1.6份、1～1.5份、1.2～1.6份、1.2～1.5份、1.4～1.6份、1.4～1.5份等。In some embodiments of the present invention, the weight proportion of the chitosan is the aforementioned 0.5-2.5 parts, and can also be 0.5 parts, 0.6 parts, 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, etc., and can also be selected from the interval consisting of any two of the aforementioned weight proportions, such as but not limited to 1-1.6 parts, 1-1.5 parts, 1.2-1.6 parts, 1.2-1.5 parts, 1.4-1.6 parts, 1.4-1.5 parts, etc.
本发明中使用的纤维素微晶粉具有填充剂作用，有助于填补纤维间孔隙。此外，纤维素微晶粉具有较高的结晶度，一方面在吸附与稳定颜料方面具有优势，其次，由于纤维素在老化降解过程通常从非晶区开始，因此纤维素微晶在储存老化过程中能够保存的时间更久，有利于纸张的长久保存。The cellulose microcrystalline powder used in the present invention has a filler effect, which helps to fill the pores between fibers. In addition, the cellulose microcrystalline powder has a high degree of crystallinity, which has advantages in adsorbing and stabilizing pigments. Secondly, since the aging and degradation process of cellulose usually starts from the amorphous region, the cellulose microcrystalline can be preserved for a longer time during the storage aging process, which is conducive to the long-term preservation of paper.
该纤维素微晶粉可通过酸水解至极限聚合度而得到，为白色或近白色颗粒，粒径一般为但不限于2μm～80μm。The cellulose microcrystalline powder can be obtained by acid hydrolysis to a limit degree of polymerization and is white or nearly white particles with a particle size of generally but not limited to 2 μm to 80 μm.
在一些实施例中，所述纤维素微晶粉的D50为10μm～40μm，进一步可以为10μm～30μm。D50也称为中值粒径，指数量累计粒度分布百分数达到50％时对应的粒径，其物理意义为：粒径大于D50的颗粒占50％，粒径小于D50的颗粒也占50％。In some embodiments, the D50 of the cellulose microcrystalline powder is 10 μm to 40 μm, and can further be 10 μm to 30 μm. D50 is also called the median particle size, which refers to the particle size corresponding to when the cumulative particle size distribution percentage reaches 50%. Its physical meaning is: particles with a particle size greater than D50 account for 50%, and particles with a particle size less than D50 also account for 50%.
在本发明的一些实施方式中，所述纤维素微晶粉的重量份数为前述的1～2份，还可以为1份、1.2份、1.4份、1.5份、1.6份、1.8份、2份等，还可以选自前述任意两种重量份数所构成的区间，例如但不限于1.2～2份、1.4～2份、1.5～2份、1～1.6份、1～1.5份、1.2～1.6份、1.2～1.5份、1.4～1.6份、1.4～1.5份等。In some embodiments of the present invention, the weight proportion of the cellulose microcrystalline powder is 1 to 2 parts as mentioned above, and can also be 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, etc., and can also be selected from the interval formed by any two of the aforementioned weight proportions, for example but not limited to 1.2 to 2 parts, 1.4 to 2 parts, 1.5 to 2 parts, 1 to 1.6 parts, 1 to 1.5 parts, 1.2 to 1.6 parts, 1.2 to 1.5 parts, 1.4 to 1.6 parts, 1.4 to 1.5 parts, etc.
本发明中使用的羧甲基纤维素钠是纤维素的羧甲基化衍生物的钠盐，具有一定的吸湿性，中性或碱性时可提高体系粘度。在本发明的书画纸组合物中，羧甲基纤维素钠作为稳定剂，既能起到在浆内增强作用，也能起到部分表面施胶作用。此外，羧甲基纤维素钠还能够起到提高纤维之间交联的作用，有利于保持纸张结构稳定，可在书画装裱过程中固色，使结构不易松散。The sodium carboxymethyl cellulose used in the present invention is a sodium salt of a carboxymethylated derivative of cellulose, has a certain hygroscopicity, and can increase the viscosity of the system when it is neutral or alkaline. In the painting and calligraphy paper composition of the present invention, sodium carboxymethyl cellulose, as a stabilizer, can not only play a reinforcing role in the pulp, but also play a partial surface sizing role. In addition, sodium carboxymethyl cellulose can also play a role in increasing the cross-linking between fibers, which is beneficial to maintaining the stability of the paper structure, and can fix the color during the painting and calligraphy mounting process, so that the structure is not easy to loosen.
在一些实施方式中，使用的羧甲基纤维素钠的重均分子量为5～20kDa，例如可以为下述任一种分子量，还可以选自下述任两种分子量构成的区间：5kDa、6kDa、8kDa、10kDa、12kDa、15kDa、16kDa、18kDa、20kDa等，还可以选自下述任意合适的范围：5～10kDa、5～15kDa、8～12kDa等。In some embodiments, the weight average molecular weight of the sodium carboxymethyl cellulose used is 5 to 20 kDa, for example, it can be any of the following molecular weights, and can also be selected from the interval consisting of any two of the following molecular weights: 5 kDa, 6 kDa, 8 kDa, 10 kDa, 12 kDa, 15 kDa, 16 kDa, 18 kDa, 20 kDa, etc., and can also be selected from any of the following suitable ranges: 5 to 10 kDa, 5 to 15 kDa, 8 to 12 kDa, etc.
在本发明的一些实施方式中，所述羧甲基纤维素钠的醚化取代度为0.7～0.8(中等取代度)。羧甲基纤维素钠的醚化取代度具有本领域公知含义，本领域技术人员可以理解醚化取代度的结构。In some embodiments of the present invention, the etherification substitution degree of the sodium carboxymethyl cellulose is 0.7-0.8 (medium substitution degree). The etherification substitution degree of sodium carboxymethyl cellulose has a well-known meaning in the art, and those skilled in the art can understand the structure of the etherification substitution degree.
在本发明的一些实施方式中，所述羧甲基纤维素钠的重量份数为前述的0.5～2.5份，还可以为0.5份、0.6份、0.8份、1份、1.2份、1.4份、1.5份、1.6份、1.8份、2份、2.4份、2.5份等，还可以选自前述任意两种重量份数所构成的区间，例如但不限于0.5～2.5份、0.5～2.2份、0.5～2份、1～2.5份、1～2.2份、1～2份、1.5～2.5份、1.5～2.2份、1.5～2份、1.6～2.5份、1.6～2.2份、1.6～2份、1.8～2.5份、1.8～2.2份、1.8～2份等。In some embodiments of the present invention, the weight proportion of the sodium carboxymethyl cellulose is the aforementioned 0.5-2.5 parts, and can also be 0.5 parts, 0.6 parts, 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.4 parts, 2.5 parts, etc., and can also be selected from the interval consisting of any two of the aforementioned weight proportions, such as but not limited to 0.5-2.5 parts, 0.5-2.2 parts, 0.5-2 parts, 1-2.5 parts, 1-2.2 parts, 1-2 parts, 1.5-2.5 parts, 1.5-2.2 parts, 1.5-2 parts, 1.6-2.5 parts, 1.6-2.2 parts, 1.6-2 parts, 1.8-2.5 parts, 1.8-2.2 parts, 1.8-2 parts, etc.
本发明中使用的聚乙烯亚胺是一种带有叔氨基团的支链型聚合物，在书画纸组合物及手工书画纸的制备工艺中可以发挥分散剂、湿增强剂及施胶增效剂的作用；不仅可以交联纤维结构，还可以发挥稳定与结合其他助剂的作用。本发明中使用的聚乙烯亚胺具有直链型结构并含有叔氨基团，可以与细小纤维形成较强的静电结合力，而且对吸水性的影响小或无。在pH7～8时聚乙烯亚胺的作用效果较佳，且基本上不影响吸水性。此外，聚乙烯亚胺还可以发挥一定的抑菌作用。The polyethyleneimine used in the present invention is a branched polymer with a tertiary amino group, which can play the role of a dispersant, a wet enhancer and a sizing synergist in the preparation process of the calligraphy and painting paper composition and the handmade calligraphy and painting paper; it can not only cross-link the fiber structure, but also play the role of stabilizing and combining other auxiliary agents. The polyethyleneimine used in the present invention has a linear structure and contains a tertiary amino group, which can form a strong electrostatic binding force with fine fibers, and has little or no effect on water absorption. The effect of polyethyleneimine is better at pH 7-8, and it basically does not affect water absorption. In addition, polyethyleneimine can also play a certain antibacterial effect.
在本发明中，如无其他说明，聚乙烯亚胺的聚合度约为100，偏差可以为±5、±2等，水溶液呈碱性。聚乙烯亚胺能够与纤维素中的羟基反应并交联聚合，使纸张产生湿强度，并具有干增强作用。In the present invention, unless otherwise specified, the degree of polymerization of polyethyleneimine is about 100, the deviation may be ±5, ±2, etc., and the aqueous solution is alkaline. Polyethyleneimine can react with hydroxyl groups in cellulose and cross-link and polymerize to produce wet strength for paper and has dry strengthening effect.
在本发明的一些实施方式中，所述聚乙烯亚胺的重均分子量为1～10kDa，例如可以为下述任一种分子量，还可以选自下述任两种分子量构成的区间：1kDa、2kDa、4kDa、5kDa、6kDa、8kDa、10kDa等，还可以选自下述任意合适的范围：2～5kDa，5～8kDa，4～6kDa等。In some embodiments of the present invention, the weight-average molecular weight of the polyethyleneimine is 1 to 10 kDa, for example, it can be any of the following molecular weights, and can also be selected from the interval consisting of any two of the following molecular weights: 1 kDa, 2 kDa, 4 kDa, 5 kDa, 6 kDa, 8 kDa, 10 kDa, etc., and can also be selected from any of the following suitable ranges: 2 to 5 kDa, 5 to 8 kDa, 4 to 6 kDa, etc.
在本发明的一些实施方式中，所述聚乙烯亚胺的重量份数为前述的0.5～2.5份，还可以为0.5份、0.6份、0.8份、1份、1.2份、1.4份、1.5份、1.6份、1.8份、2份、2.2份、2.4份、2.5份等，还可以选自前述任意两种重量份数所构成的区间，例如但不限于0.5～2.2份、0.5～2份、1～2.5份、1～2.2份、1～2份、1.5～2.5份、1.5～2.2份、1.5～2份、1.6～2.5份、1.6～2.2份、1.6～2份、1.8～2.5份、1.8～2.2份、1.8～2份等。In some embodiments of the present invention, the weight proportion of the polyethyleneimine is the aforementioned 0.5-2.5 parts, and can also be 0.5 parts, 0.6 parts, 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, etc., and can also be selected from the interval consisting of any two of the aforementioned weight proportions, such as but not limited to 0.5-2.2 parts, 0.5-2 parts, 1-2.5 parts, 1-2.2 parts, 1-2 parts, 1.5-2.5 parts, 1.5-2.2 parts, 1.5-2 parts, 1.6-2.5 parts, 1.6-2.2 parts, 1.6-2 parts, 1.8-2.5 parts, 1.8-2.2 parts, 1.8-2 parts, etc.
在一些实施方式中，所述书画纸组合物中还包括香料，可以根据香料的种类选择赋予书画纸不同的香气。所述香料的重量份数可以为前述的0～3.5份，还可以为0份、0.5份、0.6份、0.8份、1份、1.2份、1.4份、1.5份、1.6份、1.8份、2份、2.2份、2.4份、2.5份、3.0份、3.5份等，还可以选自前述任意两种重量份数所构成的区间，例如但不限于0～2份、1～2份等。In some embodiments, the calligraphy and painting paper composition also includes spices, and different aromas can be given to the calligraphy and painting paper according to the type of spices. The weight proportion of the spices can be the aforementioned 0 to 3.5 parts, and can also be 0 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, 3.0 parts, 3.5 parts, etc., and can also be selected from the interval consisting of any two of the aforementioned weight proportions, such as but not limited to 0 to 2 parts, 1 to 2 parts, etc.
在一些实施例中，所述香料可以包括0～2份的沉香粉和0～1.5份的香草汁。In some embodiments, the spices may include 0-2 parts of agarwood powder and 0-1.5 parts of vanilla juice.
在一些实施例中，所述香料包括沉香粉和香草汁中的一种或多种。In some embodiments, the spices include one or more of agarwood powder and vanilla juice.
在一些实施例中，所述香料包括沉香粉。In some embodiments, the fragrance comprises agarwood powder.
在一些实施例中，所述0～3.5份的香料至少包括0～2份的沉香粉。In some embodiments, the 0-3.5 parts of spices include at least 0-2 parts of agarwood powder.
在一些实施例中，所述香料包括香草汁。In some embodiments, the flavor comprises vanilla extract.
在一些实施例中，所述香料包括沉香粉和香草汁。In some embodiments, the spices include agarwood powder and vanilla juice.
沉香是一种天然香料，其为凝脂和木纤维相互粘合形成的混合物。本发明中的书画纸组合物可以包括或不包括沉香粉。本发明中的书画纸组合物包括沉香粉时可以赋予纸张持久缓释香氛的效果，可以舒心、安神。本发明中使用的沉香粉可以优选但不限于凝脂的重量含量为0.1～0.5％。Agarwood is a natural fragrance, which is a mixture of gelatin and wood fiber bonded together. The painting and calligraphy paper composition of the present invention may include or exclude agarwood powder. When the painting and calligraphy paper composition of the present invention includes agarwood powder, it can give the paper a long-lasting and slow-release fragrance effect, which can be soothing and calming. The agarwood powder used in the present invention can preferably, but not limited to, have a weight content of gelatin of 0.1 to 0.5%.
本发明中所使用的沉香粉可以选自但不限于花香、果香、木香等型号。在一些优选例中，沉香粉为木香型号的沉香粉，此时更有利于创作与欣赏书画艺术情感的表达。The agarwood powder used in the present invention can be selected from, but not limited to, flower fragrance, fruit fragrance, wood fragrance, etc. In some preferred examples, the agarwood powder is a wood fragrance type agarwood powder, which is more conducive to the creation and appreciation of the expression of artistic emotions in calligraphy and painting.
在本发明的一些实施方式中，所述沉香粉的重量份数为前述的0～2份，还可以为0份、0.5份、1份、1.2份、1.4份、1.5份、1.6份、1.8份、2份等，还可以选自前述任意两种重量份数所构成的区间，例如但不限于1～2份、1.2～2份、1.4～2份、1.5～2份、1～1.6份、1～1.5份、1.2～1.6份、1.2～1.5份、1.4～1.6份、1.4～1.5份等。In some embodiments of the present invention, the weight proportion of the agarwood powder is the aforementioned 0-2 parts, and can also be 0 parts, 0.5 parts, 1 parts, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, etc., and can also be selected from the interval formed by any two of the aforementioned weight proportions, for example but not limited to 1-2 parts, 1.2-2 parts, 1.4-2 parts, 1.5-2 parts, 1-1.6 parts, 1-1.5 parts, 1.2-1.6 parts, 1.2-1.5 parts, 1.4-1.6 parts, 1.4-1.5 parts, etc.
在本发明的一些实施方式中，在所述书画纸组合物红，所述香草汁的重量份数为0～1.5份，还可以为0份、0.5份、0.6份、0.8份、1份、1.2份、1.4份、1.5份等，还可以选自前述任意两种重量份数所构成的区间，例如但不限于0.5～1.5份、0.5～1.2份、0.8～1.2份、0.5～1份、0.8～1份、0.9～1.1份等。In some embodiments of the present invention, in the calligraphy and painting paper composition, the weight portion of the vanilla juice is 0-1.5 parts, and can also be 0 parts, 0.5 parts, 0.6 parts, 0.8 parts, 1 parts, 1.2 parts, 1.4 parts, 1.5 parts, etc., and can also be selected from the interval formed by any two of the aforementioned weight portions, such as but not limited to 0.5-1.5 parts, 0.5-1.2 parts, 0.8-1.2 parts, 0.5-1 parts, 0.8-1 parts, 0.9-1.1 parts, etc.
在一些实施方式中，所述的书画纸组合物满足下组中的任一个或任意多个特征：In some embodiments, the calligraphy and painting paper composition satisfies any one or more of the following characteristics:
所述皮纤维为青檀皮纤维；The skin fiber is Pteris tannin skin fiber;
所述皮纤维浆中的皮纤维重量占比为88％～95％(还可以选自上下文中的任一种重量占比范围或任一种重量占比)；The weight percentage of the sheath fiber in the sheath fiber pulp is 88% to 95% (it can also be selected from any weight percentage range or any weight percentage in the context);
所述皮纤维浆中的含水量为5％～12％(还可以选自上下文中的任一种含水量范围或任一种含水量)；The moisture content of the skin fiber pulp is 5% to 12% (it can also be selected from any moisture content range or any moisture content in the context);
所述竹纤维为苦竹纤维；The bamboo fiber is bitter bamboo fiber;
所述竹纤维浆中的竹纤维重量占比为88％～95％(还可以选自上下文中的任一种重量占比范围或任一种重量占比)；The weight percentage of bamboo fiber in the bamboo fiber pulp is 88% to 95% (it can also be selected from any weight percentage range or any weight percentage in the context);
所述竹纤维浆中的含水量为5％～12％(还可以选自上下文中的任一种含水量范围或任一种含水量)；The water content of the bamboo fiber pulp is 5% to 12% (it can also be selected from any water content range or any water content in the context);
所述皮纤维和所述竹纤维的重量份数比值为0.3～3.25(还可以选自上下文中的任一种重量份数比值范围或任一种重量份数比值)；The weight ratio of the skin fiber to the bamboo fiber is 0.3 to 3.25 (can also be selected from any weight ratio range or any weight ratio in the context);
所述碱性钙源选自石灰和氢氧化钙中的一种或两种；The alkaline calcium source is selected from one or both of lime and calcium hydroxide;
所述壳聚糖的重均分子量为100～250kDa(还可以选自上下文中的任一种重均分子量范围或任一种重均分子量)；The weight average molecular weight of the chitosan is 100 to 250 kDa (can also be selected from any weight average molecular weight range or any weight average molecular weight in the context);
所述羧甲基纤维素钠的重量份数为0.5～2.5份(还可以选自上下文中的任一种重量份数范围或任一种重量份数)；The weight proportion of the sodium carboxymethyl cellulose is 0.5 to 2.5 parts (can also be selected from any weight proportion range or any weight proportion in the context);
所述羧甲基纤维素钠的重均分子量为5～20kDa(还可以选自上下文中的任一种重均分子量范围或任一种重均分子量)；The weight average molecular weight of the sodium carboxymethyl cellulose is 5 to 20 kDa (can also be selected from any weight average molecular weight range or any weight average molecular weight in the context);
所述聚乙烯亚胺的重均分子量为1～10kDa(还可以选自上下文中的任一种重均分子量范围或任一种重均分子量)；The weight average molecular weight of the polyethyleneimine is 1 to 10 kDa (can also be selected from any weight average molecular weight range or any weight average molecular weight in the context);
所述0～3.5份的香料至少包括0～2份的沉香粉(沉香粉的重量份数还可以选自上下文中的任一种重量份数范围或任一种重量份数)；The 0-3.5 parts of spices include at least 0-2 parts of agarwood powder (the weight parts of agarwood powder can also be selected from any weight parts range or any weight parts in the context);
所述书画纸组合物的总重量份数为45～145份(还可以选自上下文中的任一种总重量份数范围或任一种总重量份数，如65～130份)。The total weight of the calligraphy and painting paper composition is 45 to 145 parts (it can also be selected from any total weight range or any total weight in the context, such as 65 to 130 parts).
在本发明的一些优选实施方式中，按重量份数计，所述书画纸组合物包括如下组分：30～55份的皮纤维浆，30～55份的竹纤维浆，1～1.6份的菊粉，1.5～2.2份的碱性钙源(如石灰和氢氧化钙中的一种或多种)，1～1.6份的壳聚糖，1.4～2份的纤维素微晶粉，1.5～2.2份的羧甲基纤维素钠，和1～2.2份的聚乙烯亚胺；还可以包括0～3.5份的香料，如0～2份的沉香粉和0～1.5份的香草汁，如0～2份(进一步如1～2份，更进一步如1.2～2份)的沉香粉。香草汁的重量份数还可以如0.5～1.5份，进一步如0.5～1.2份，更进一步如0.8～1.2份。In some preferred embodiments of the present invention, the calligraphy and painting paper composition includes the following components by weight: 30-55 parts of skin fiber pulp, 30-55 parts of bamboo fiber pulp, 1-1.6 parts of inulin, 1.5-2.2 parts of alkaline calcium source (such as one or more of lime and calcium hydroxide), 1-1.6 parts of chitosan, 1.4-2 parts of cellulose microcrystalline powder, 1.5-2.2 parts of sodium carboxymethyl cellulose, and 1-2.2 parts of polyethyleneimine; it may also include 0-3.5 parts of spices, such as 0-2 parts of agarwood powder and 0-1.5 parts of vanilla juice, such as 0-2 parts (further such as 1-2 parts, further such as 1.2-2 parts) of agarwood powder. The weight of the vanilla juice may also be 0.5-1.5 parts, further such as 0.5-1.2 parts, and further such as 0.8-1.2 parts.
在本发明的一些优选实施方式中，按重量份数计，所述书画纸组合物包括如下组分：48～52份的皮纤维浆，35～40份的竹纤维浆，1.2～1.6份的菊粉，1.8～2.2份的碱性钙源(如石灰和氢氧化钙中的一种或多种)，1.4～1.6份的壳聚糖，1.4～1.6份的纤维素微晶粉，1.8～2.2份的羧甲基纤维素钠，和1.8～2.2份的聚乙烯亚胺；还可以包括0～3.5份的香料，如0～2份的沉香粉和0～1.5份的香草汁，如0～2份(进一步如1～2份，更进一步如1.2～2份，更进一步如1.2～1.6份)的沉香粉。香草汁的重量份数还可以如0.5～1.5份，进一步如0.5～1.2份，更进一步如0.8～1.2份。In some preferred embodiments of the present invention, the calligraphy and painting paper composition includes the following components by weight: 48-52 parts of skin fiber pulp, 35-40 parts of bamboo fiber pulp, 1.2-1.6 parts of inulin, 1.8-2.2 parts of alkaline calcium source (such as one or more of lime and calcium hydroxide), 1.4-1.6 parts of chitosan, 1.4-1.6 parts of cellulose microcrystalline powder, 1.8-2.2 parts of sodium carboxymethyl cellulose, and 1.8-2.2 parts of polyethyleneimine; it may also include 0-3.5 parts of spices, such as 0-2 parts of agarwood powder and 0-1.5 parts of vanilla juice, such as 0-2 parts (further such as 1-2 parts, further such as 1.2-2 parts, further such as 1.2-1.6 parts) of agarwood powder. The weight of the vanilla juice may also be 0.5-1.5 parts, further such as 0.5-1.2 parts, and further such as 0.8-1.2 parts.
在本发明的一些优选实施方式中，按重量份数计，所述书画纸组合物包括如下组分：50份的皮纤维浆，37份的竹纤维浆，1.5份的菊粉，2份的碱性钙源(如石灰和氢氧化钙中的一种或多种)，1.5份的壳聚糖，1.5份的纤维素微晶粉，2份的羧甲基纤维素钠，和2份的聚乙烯亚胺；还可以包括1.5份的沉香粉；进一步还可以包括1份的香草汁。In some preferred embodiments of the present invention, the calligraphy and painting paper composition includes the following components, measured by weight: 50 parts of skin fiber pulp, 37 parts of bamboo fiber pulp, 1.5 parts of inulin, 2 parts of alkaline calcium source (such as one or more of lime and calcium hydroxide), 1.5 parts of chitosan, 1.5 parts of cellulose microcrystalline powder, 2 parts of sodium carboxymethyl cellulose, and 2 parts of polyethyleneimine; it may also include 1.5 parts of agarwood powder; and it may further include 1 part of vanilla juice.
在本发明的一些实施例中，书画纸组合物的组成如下文的实施例1～14中任一例所示，可参阅表1和表3。In some embodiments of the present invention, the composition of the calligraphy and painting paper composition is as shown in any one of Examples 1 to 14 below, and can be found in Table 1 and Table 3.
在本发明的第二方面，本发明提供了一种手工书画纸的制备方法，可利用本发明第一方面所述的书画纸组合物制备得到。制得的手工书画纸品质高，纸质细腻、润墨效果可控，对颜料的锁定效果提高，颜色保持效果好，纸张拉力强，能够保留传统书画纸的文化与艺术价值。In the second aspect of the present invention, the present invention provides a method for preparing handmade calligraphy and painting paper, which can be prepared using the calligraphy and painting paper composition described in the first aspect of the present invention. The prepared handmade calligraphy and painting paper has high quality, fine paper texture, controllable ink wetting effect, improved pigment locking effect, good color retention effect, strong paper tensile strength, and can retain the cultural and artistic value of traditional calligraphy and painting paper.
在本发明的一些实施方式中，提供了一种手工书画纸的制备方法，其包括如下步骤：将所述书画纸组合物经混合制成纸浆液，进行抄纸、脱水、干燥、熟化，制得手工书画纸。In some embodiments of the present invention, a method for preparing handmade calligraphy and painting paper is provided, which comprises the following steps: mixing the calligraphy and painting paper composition into a pulp liquid, and performing papermaking, dehydration, drying, and ripening to obtain the handmade calligraphy and painting paper.
在本发明的一些实施方式中，于110～150℃进行熟化，进一步如110℃、115℃、120℃、125℃、130℃、135℃、140℃、145℃、150℃、155℃等中任一种温度，还可以选自上述任两种温度所构成的温度范围。于该特定高温条件下进行熟化，可以提高纤维素微晶与纸张纤维纤维素的结合作用，还能够提高石灰粉弱碱性下菊粉与羧甲基纤维素钠的协同作用，还可延缓纸张纤维素水解，延长纸张寿命，该温度条件下熟化还可以提高壳聚糖与聚乙烯亚胺与纤维、助剂的平铺效果。进一步地，熟化处理时间可以为100小时～720小时，更进一步还可以为100小时、120小时、150小时、180小时、200小时、210小时、240小时、250小时、270小时、300小时、350小时、360小时、400小时、420小时、450小时、480小时、500小时、540小时、550小时、570小时、600小时、630小时、650小时、660小时、680小时、690小时、700小时、720小时等中任一种时长，还可以选自前述任意两种时长构成的区间，例如但不限于120小时～720小时、120小时～600小时、180小时～600小时、240小时～600小时等。In some embodiments of the present invention, the aging is carried out at 110-150°C, and further any one of 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, etc., and can also be selected from the temperature range formed by any two of the above temperatures. The aging under this specific high temperature condition can improve the binding effect between cellulose microcrystals and paper fiber cellulose, and can also improve the synergistic effect of inulin and sodium carboxymethyl cellulose under the weak alkalinity of lime powder, and can also delay the hydrolysis of paper cellulose and extend the life of paper. The aging under this temperature condition can also improve the paving effect of chitosan, polyethyleneimine, fiber and additives. Further, the aging treatment time can be 100 hours to 720 hours, and further can be any one of 100 hours, 120 hours, 150 hours, 180 hours, 200 hours, 210 hours, 240 hours, 250 hours, 270 hours, 300 hours, 350 hours, 360 hours, 400 hours, 420 hours, 450 hours, 480 hours, 500 hours, 540 hours, 550 hours, 570 hours, 600 hours, 630 hours, 650 hours, 660 hours, 680 hours, 690 hours, 700 hours, 720 hours, etc., and can also be selected from an interval consisting of any two of the aforementioned time lengths, for example but not limited to 120 hours to 720 hours, 120 hours to 600 hours, 180 hours to 600 hours, 240 hours to 600 hours, etc.
在本发明的一些实施方式中，提供了一种书画纸的制备方法(可参阅图1)，根据本发明第一方面所述书画纸组合物的组成提供计量的各原料；In some embodiments of the present invention, a method for preparing calligraphy and painting paper is provided (see FIG. 1 ), wherein the composition of the calligraphy and painting paper composition according to the first aspect of the present invention provides metered raw materials;
所述的制备方法包括如下步骤：The preparation method comprises the following steps:
S100：将所述皮纤维浆和所述竹纤维浆混匀，制得混合纤维浆；S100: mixing the leather fiber pulp and the bamboo fiber pulp to obtain a mixed fiber pulp;
S200：将所述混合纤维浆与羧甲基纤维素钠、所述碱性钙源和所述纤维素微晶粉混匀，制得混合浆A；S200: mixing the mixed fiber pulp with sodium carboxymethyl cellulose, the alkaline calcium source and the cellulose microcrystalline powder to obtain a mixed pulp A;
S300：将所述混合浆A与所述壳聚糖、所述聚乙烯亚胺和所述菊粉混匀，制得混合浆B；S300: mixing the mixed slurry A with the chitosan, the polyethyleneimine and the inulin to obtain a mixed slurry B;
S400：将所述混合浆B与所述香料(非限制性示例如沉香粉)混匀，制得纸浆液；或者以所述混合浆B作为纸浆液；S400: mixing the mixed pulp B with the fragrance (non-limiting example such as agarwood powder) to obtain pulp liquid; or using the mixed pulp B as pulp liquid;
S500：将所述纸浆液抄纸、脱水、干燥，制得干纸；S500: making paper from the pulp liquid, dehydrating and drying it to obtain dry paper;
S600(高温熟化)：将所述干纸以热处理方式进行熟化，制得所述手工书画纸。如无其他说明，该热处理的温度条件为≥110℃，此时将所述干纸以热处理方式于≥110℃下进行熟化。S600 (high temperature aging): the dry paper is aging by heat treatment to obtain the handmade calligraphy and painting paper. Unless otherwise specified, the temperature condition of the heat treatment is ≥110°C. At this time, the dry paper is aging by heat treatment at ≥110°C.
采用上述的制备方法，制得的手工书画纸品质高，纸质细腻、润墨效果可控，对颜料的锁定效果提高，颜色保持效果好，纸张拉力强，能够保留传统书画纸的文化与艺术价值。此外，该制备方法生产工艺简单，可采用传统生产装置，适合大规模连续化生产。The handmade calligraphy and painting paper prepared by the above-mentioned preparation method is of high quality, fine paper quality, controllable ink wetting effect, improved pigment locking effect, good color retention effect, strong paper tensile strength, and can retain the cultural and artistic value of traditional calligraphy and painting paper. In addition, the preparation method has a simple production process, can adopt traditional production equipment, and is suitable for large-scale continuous production.
S100、S200、S300和S400所采用的上述加料顺序，有利于提高各助剂在纸张中的填充作用和自身稳定性，同时赋予纸张纤维功能化改性。The above-mentioned adding sequence adopted by S100, S200, S300 and S400 is conducive to improving the filling effect and self-stability of each additive in the paper, while giving functional modification to the paper fiber.
在本发明的一些实施方式中，所述混合浆A的pH值为8.2～8.6，例如pH8.5。In some embodiments of the present invention, the pH value of the mixed slurry A is 8.2-8.6, for example, pH 8.5.
在本发明的一些实施方式中，所述纸浆液的pH值为7.8～8.2，例如pH8.0。In some embodiments of the present invention, the pH value of the pulp slurry is 7.8-8.2, for example, pH 8.0.
在一些实施例中，所述混合浆A的pH值为8.5，所述纸浆液的pH值为8.0。In some embodiments, the pH value of the mixed pulp A is 8.5, and the pH value of the pulp liquid is 8.0.
在本发明的一些实施方式中，S100、S200、S300和S400中的任一个混匀步骤独立地采用搅拌方式进行，进一步地，搅拌速率为50～60rpm。在一些实施方式中，机械搅拌30min，搅拌速率为60转/分钟。In some embodiments of the present invention, any one of the mixing steps S100, S200, S300 and S400 is independently performed by stirring, and further, the stirring rate is 50-60 rpm. In some embodiments, the mechanical stirring is performed for 30 min at a stirring rate of 60 rpm.
在本发明的一些实施方式中，所述抄纸可以采用本领域的常规方法进行。例如，可以在纸槽中横向与纵向抄纸相互交替进行。In some embodiments of the present invention, the papermaking can be performed by conventional methods in the art. For example, the papermaking can be performed alternately in the transverse direction and the longitudinal direction in a paper trough.
在本发明的一些实施方式中，在所述脱水步骤中，脱水至含水量≤30％。在一些实施例中，采用静置脱水，进一步可以采用上层辊压配合下层真空抽吸提高脱水效率，待湿纸业含水量在30％时转到后续干燥步骤。In some embodiments of the present invention, in the dehydration step, the water content is ≤30%. In some embodiments, static dehydration is adopted, and the dehydration efficiency can be further improved by upper roller pressing and lower vacuum suction. When the moisture content of the wet paper reaches 30%, the subsequent drying step is performed.
在本发明的一些实施方式中，于180～200℃干燥5～10分钟。在一些实施例中，所述干燥在干燥板上进行，进一步地，可以在涂覆了猪油的干燥板上进行干燥，有利于揭纸时减少或避免纸张破损。In some embodiments of the present invention, the paper is dried at 180-200° C. for 5-10 minutes. In some embodiments, the drying is performed on a drying board, and further, the drying can be performed on a drying board coated with lard, which is beneficial to reduce or avoid paper damage when peeling off the paper.
在S600步骤中，进行高温熟化。可以于110～150℃进行熟化。还可参考前述的熟化条件。可进一步在如下方面提高手工书画纸的品质：纸质细腻、润墨效果可控，对颜料的锁定效果提高，颜色保持效果好，纸张拉力强。In step S600, high temperature aging is performed. The aging can be performed at 110-150°C. The aforementioned aging conditions can also be referred to. The quality of handmade calligraphy and painting paper can be further improved in the following aspects: fine paper quality, controllable ink wetting effect, improved pigment locking effect, good color retention effect, and strong paper tensile strength.
熟化过程是使助剂充分铺展的过程，分子链运动伸展能够平铺纤维表面，起到保护纤维的作用，如果温度较低，则分子链运动能力有限。The aging process is the process of fully spreading the additive. The movement and stretching of the molecular chains can flatten the fiber surface and play a role in protecting the fiber. If the temperature is low, the movement ability of the molecular chains is limited.
在本发明的一些实施方式中，所述热处理于110～150℃下进行，进一步如110℃、115℃、120℃、125℃、130℃、135℃、140℃、145℃、150℃、155℃等中任一种温度下进行热处理，还可以选自上述任两种温度所构成的温度范围(包括或不包括端点)内进行热处理。进一步地，热处理时间可以为100小时～720小时，更进一步还可以为100小时、120小时、150小时、180小时、200小时、210小时、240小时、250小时、270小时、300小时、350小时、360小时、400小时、420小时、450小时、480小时、500小时、540小时、550小时、570小时、600小时、630小时、650小时、660小时、680小时、690小时、700小时、720小时等中任一种时长，还可以选自前述任意两种时长构成的区间，例如但不限于120小时～720小时、120小时～600小时、180小时～600小时、240小时～600小时等。In some embodiments of the present invention, the heat treatment is carried out at 110-150°C, and further at any one of 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, etc., and can also be carried out within a temperature range (including or excluding the endpoints) formed by any two of the above temperatures. Further, the heat treatment time can be 100 hours to 720 hours, and further can be 100 hours, 120 hours, 150 hours, 180 hours, 200 hours, 210 hours, 240 hours, 250 hours, 270 hours, 300 hours, 350 hours, 360 hours, 400 hours, 420 hours, 450 hours, 480 hours, 500 hours, 540 hours, 550 hours, 570 hours, 600 hours, 630 hours, 650 hours, 660 hours, 680 hours, 690 hours, 700 hours, 720 hours, etc., and can also be selected from the interval consisting of any two of the aforementioned time lengths, for example but not limited to 120 hours to 720 hours, 120 hours to 600 hours, 180 hours to 600 hours, 240 hours to 600 hours, etc.
在一些实施方式中，所述热处理于110～150℃下进行100～720小时。In some embodiments, the heat treatment is performed at 110-150° C. for 100-720 hours.
制备得到的书画纸的面密度可根据GB/T451.2-2002方法测试。书画纸的面密度可以为25～40g/cm2，还可以为下述任一种面密度，或者选自下述任两种面密度构成的区间：25g/cm2、28g/cm2、30g/cm2、35g/cm2、40g/cm2等。The surface density of the prepared painting and calligraphy paper can be tested according to the method of GB/T451.2-2002. The surface density of the painting and calligraphy paper can be 25-40 g/cm2 , or any of the following surface densities, or a range consisting of any two of the following surface densities: 25 g/cm2 , 28 g/cm2 , 30 g/cm2 , 35 g/cm2 , 40 g/cm2 , etc.
制备得到的书画纸的含水量可根据GB/T462-2003方法测试。书画纸的含水量可满足≤10％，进一步可以为9.2％～10％，以质量百分比计。制备得到的书画纸的含水量还可以为下述任一种含水量，或者选自任两种含水量构成的区间(以质量百分比计)：10％、9.9％、9.8％、9.7％、9.6％、9.5％、9.4％等。制备得到的书画纸的含水量还可以选自下述任一范围：9.4％～10％。The moisture content of the prepared calligraphy and painting paper can be tested according to the GB/T462-2003 method. The moisture content of the calligraphy and painting paper can meet ≤10%, and can further be 9.2% to 10%, measured in mass percentage. The moisture content of the prepared calligraphy and painting paper can also be any of the following moisture contents, or selected from the interval consisting of any two moisture contents (measured in mass percentage): 10%, 9.9%, 9.8%, 9.7%, 9.6%, 9.5%, 9.4%, etc. The moisture content of the prepared calligraphy and painting paper can also be selected from any of the following ranges: 9.4% to 10%.
制备得到的书画纸的吸水性较佳。“纸张吸收空气中水分的平衡量”可根据GB/T461.1-2002测试，该指标的数值越大，表示吸水性越佳。该指标可以为13～20mm，例如下述任一种数值或选自下述任两种数值构成的区间：13mm、14mm、15mm、16mm、17mm、18mm、19mm、20mm等。The prepared calligraphy and painting paper has good water absorption. "The balance amount of water absorbed by the paper in the air" can be tested according to GB/T461.1-2002. The larger the value of this index, the better the water absorption. This index can be 13-20 mm, for example, any of the following values or an interval consisting of any two of the following values: 13 mm, 14 mm, 15 mm, 16 mm, 17 mm, 18 mm, 19 mm, 20 mm, etc.
制备得到的书画纸的抑菌率高，可根据FZ/T73023-2006方法测试抑菌率。抑菌率越高，表明抗菌性越好。抑菌率水平远高于AA级(≥80％)。所制书画纸的抑菌率水平可普遍高于97％。The prepared calligraphy and painting paper has a high antibacterial rate, which can be tested according to the FZ/T73023-2006 method. The higher the antibacterial rate, the better the antibacterial property. The antibacterial rate level is much higher than AA grade (≥80%). The antibacterial rate level of the prepared calligraphy and painting paper can generally be higher than 97%.
制备得到的书画纸的墨迹可控性好。可根据GB/T460-2008方法测试墨迹直径。墨迹直径越小说明纸张施胶度越高，对于墨迹可控性越好；当墨迹直径大于3.400mm时，可认定“墨迹不可控”。制备得到的书画纸的墨迹直径可以为均≤3.400mm，例如可以为2.980～3.380mm。制备得到的书画纸的抗张强度高。可根据GB-T 12914-2008方法测试书画纸的抗张强度。抗张指数越高，表明纤维强度和结合强度越高。制备得到的书画纸的抗张强度可满足≥39N·m/g，且大多可实现≥40N·m/g。The prepared calligraphy and painting paper has good controllability of ink. The ink diameter can be tested according to the GB/T460-2008 method. The smaller the ink diameter, the higher the paper sizing degree, and the better the controllability of the ink; when the ink diameter is greater than 3.400mm, it can be determined that the "ink is uncontrollable". The ink diameter of the prepared calligraphy and painting paper can be ≤3.400mm, for example, it can be 2.980-3.380mm. The prepared calligraphy and painting paper has high tensile strength. The tensile strength of calligraphy and painting paper can be tested according to the GB-T 12914-2008 method. The higher the tensile index, the higher the fiber strength and bonding strength. The tensile strength of the prepared calligraphy and painting paper can meet ≥39N·m/g, and most of them can achieve ≥40N·m/g.
制备得到的书画纸的抗张指数保留率高，纸张寿命长。可根据保存一段时间后的抗张指数的重测值与初始测试值的相对百分比计算得到抗张指数保留率。可参考下文实施例部分的测试方法，如80℃/65％RH环境保存7天后重测、计算。抗张指数保留率越高，表明纸张纤维及纤维之间仍具有一定强度，受到的老化劣化有限，一定程度上反映了纸张寿命更长。制备得到的书画纸的抗张指数保留率可满足≥89％，且大多可实现≥90％，甚至可高达98％。The prepared calligraphy and painting paper has a high tensile index retention rate and a long paper life. The tensile index retention rate can be calculated based on the relative percentage of the re-measured value of the tensile index after storage for a period of time to the initial test value. Reference may be made to the test method in the examples section below, such as re-testing and calculating after storage for 7 days in an 80°C/65%RH environment. The higher the tensile index retention rate, the more it indicates that the paper fibers and the fibers still have a certain strength, and the aging degradation is limited, which to a certain extent reflects the longer life of the paper. The tensile index retention rate of the prepared calligraphy and painting paper can meet ≥89%, and most of them can achieve ≥90%, and can even be as high as 98%.
第三方面，本发明提供了一种手工书画纸，采用本发明第二方面所述的制备方法制备得到。该手工书画纸品质高，纸质细腻、润墨效果可控，对颜料的锁定效果提高，颜色保持效果好，纸张拉力强，能够保留传统书画纸的文化与艺术价值。In a third aspect, the present invention provides a handmade calligraphy and painting paper, which is prepared by the preparation method described in the second aspect of the present invention. The handmade calligraphy and painting paper has high quality, fine paper texture, controllable ink wetting effect, improved pigment locking effect, good color retention effect, strong paper tensile strength, and can retain the cultural and artistic value of traditional calligraphy and painting paper.
第四方面，本发明提供了一种制备手工书画纸的纸浆液，采用包括本发明第一方面所述书画纸组合物的原料制备得到。In a fourth aspect, the present invention provides a pulp liquid for preparing handmade calligraphy and painting paper, which is prepared using raw materials including the calligraphy and painting paper composition described in the first aspect of the present invention.
在本发明的一些实施方式中，所述纸浆液为本发明第二方面中的任一种纸浆液。In some embodiments of the present invention, the pulp liquid is any pulp liquid in the second aspect of the present invention.
在本发明的一些实施方式中，提供了一种制备手工书画纸的纸浆液，以重量份数计，包括如下原料组分：In some embodiments of the present invention, a pulp slurry for preparing handmade calligraphy and painting paper is provided, which comprises the following raw material components in parts by weight:
皮纤维20～65份；20-65 parts of leather fiber;
竹纤维20～65份；20-65 parts of bamboo fiber;
菊粉1～2份；1-2 parts of inulin;
碱性钙源1～2.5份，以CaO的重量份数份数计；1 to 2.5 parts of alkaline calcium source, calculated by weight of CaO;
壳聚糖0.5～2.5份；Chitosan 0.5-2.5 parts;
纤维素微晶粉1～2份；1-2 parts of cellulose microcrystalline powder;
羧甲基纤维素钠0.5～2.5份；0.5-2.5 parts of sodium carboxymethyl cellulose;
聚乙烯亚胺0.5～2.5份；以及0.5 to 2.5 parts of polyethyleneimine; and
香料0～3.5份，如沉香粉0～2份，进一步如沉香粉1～2份。0-3.5 parts of spices, such as 0-2 parts of agarwood powder, and further such as 1-2 parts of agarwood powder.
该纸浆液中的各组分的种类及含量比例，还可参阅本发明的上下文。The types and content ratios of the components in the pulp liquid can also be found in the context of the present invention.
在一些实施方式中，所述纸浆液的pH值为7.8～8.2，如pH8.0。In some embodiments, the pH value of the pulp slurry is 7.8-8.2, such as pH 8.0.
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于阐述说明本发明而不用于限制本发明的范围。下列实施例中未注明更详细条件的实验方法，优先采用本发明前文中提供的条件或按照制造厂商所建议的条件，还可按照本领域常规条件(如《造纸化学品的制备和作用机理》等文献中描述的条件)。The present invention is further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In the following examples, the experimental methods for which more detailed conditions are not specified are preferably carried out under the conditions provided in the foregoing text of the present invention or under the conditions recommended by the manufacturer, and may also be carried out under conventional conditions in the art (such as the conditions described in the literature such as "Preparation and Mechanism of Action of Papermaking Chemicals").
以下各实施例和各对比例中，除非另外说明，否则百分比和份数是重量百分比和重量份数。In the following examples and comparative examples, unless otherwise specified, percentages and parts are by weight.
如无特别说明，则本发明实施例中所用的材料和试剂均可市购获得，或者采用本领域的常规方法制备得到。下例中涉及的化学试剂，如无特别说明，可自国药集团化学试剂有限公司、阿拉丁、麦克林、Sigma-Aldrich等常见厂商购得。Unless otherwise specified, the materials and reagents used in the examples of the present invention can be purchased from commercial sources or prepared using conventional methods in the art. The chemical reagents involved in the following examples, unless otherwise specified, can be purchased from common manufacturers such as Sinopharm Chemical Reagent Co., Ltd., Aladdin, Macklin, and Sigma-Aldrich.
以下各实施例和各对比例中，如无其他说明，以下各组分的来源及规格型号，或者制备方法为：In the following examples and comparative examples, unless otherwise specified, the sources and specifications of the following components, or the preparation methods are as follows:
青檀皮纤维浆：选取泾县小岭乌溪产的青檀皮，尤以生长2～3年的嫩枝青檀皮，每年的“霜降”到次年的“惊蛰”时分，对青檀枝条进行砍伐取枝条中段粗细均匀，枝丫极少的部分更佳，其纤维细长，细胞壁薄，吸墨性能好。将青檀皮在蒸锅中散开汽蒸，然后在清水池中浸泡，然后去掉外层黑皮和青皮，留黄或白色韧皮，浸石灰水后蒸煮，然后舂捣，获得青檀皮纤维浆。Pteris chinensis bark fiber pulp: Select Pteris chinensis bark produced in Wuxi, Xiaoling, Jingxian County, especially the tender Pteris chinensis bark that has grown for 2 to 3 years. Cut the Pteris chinensis branches from the "Frost Descent" of each year to the "Awakening of Insects" of the following year, and take the middle section of the branches with uniform thickness. The part with few branches is better, because its fiber is slender, the cell wall is thin, and the ink absorption performance is good. Spread the Pteris chinensis bark in a steamer and steam it, then soak it in a clear water pool, then remove the outer black skin and green skin, leaving the yellow or white bast skin, soak it in lime water, steam it, and then pound it to obtain the Pteris chinensis bark fiber pulp.
竹纤维浆：选取浙江、四川所产苦竹，把竹梢太嫩部分去除，离根部较近部分去除，只取中间均匀部分，纤维多且均匀，不去皮，剖开，在生石灰池中沤料三个月，然后用清水清洗去除杂质，然后在锅中蒸煮，捣料，获得竹纤维浆。苦竹浆味微苦，不易被虫蛀，可提高纸张保存寿命。Bamboo fiber pulp: Select bitter bamboo produced in Zhejiang and Sichuan, remove the tender part of the bamboo tip and the part close to the root, and only take the uniform part in the middle, which has more and uniform fibers. Do not peel it, split it, and ferment it in a quicklime pool for three months, then wash it with clean water to remove impurities, and then steam and pound it in a pot to obtain bamboo fiber pulp. Bitter bamboo pulp tastes slightly bitter, is not easy to be eaten by insects, and can increase the shelf life of paper.
沉香粉：市售获得，木香型。Agarwood powder: commercially available, woody type.
羧甲基纤维素钠(CMC-Na)：重均分子量10kDa，市购获得。Sodium carboxymethyl cellulose (CMC-Na): weight average molecular weight 10 kDa, commercially available.
石灰粉：市购获得，纯度99％。Lime powder: commercially available, purity 99%.
纤维素微晶粉：市购获得，纯度99.5％。Cellulose microcrystalline powder: purchased from the market, purity 99.5%.
壳聚糖：市购获得，重均分子量150kDa。Chitosan: commercially available, weight average molecular weight 150 kDa.
聚乙烯亚胺(PEI)：市购获得，重均分子量4kDa。Polyethyleneimine (PEI): commercially available, with a weight average molecular weight of 4 kDa.
菊粉：市购获得，聚合度2～60。Inulin: commercially available, degree of polymerization 2-60.
以下各实施例和各对比例中，如无其他说明，抄纸、脱水、干燥的操作条件分别为：In the following examples and comparative examples, unless otherwise specified, the operating conditions for papermaking, dehydration and drying are:
抄纸：在纸槽中横向与纵向抄纸相互交替进行；Papermaking: Papermaking is carried out alternately in the paper trough in the horizontal and vertical directions;
脱水：采用静置脱水，上层辊压配合下层真空抽吸提高脱水效率；Dehydration: static dehydration is adopted, and the upper roller pressure and the lower vacuum suction are used to improve the dehydration efficiency;
干燥：张贴在刷了猪油的干燥板上烘干，干燥温度180℃～200℃，干燥时间5～10分钟。Drying: Post it on a drying board brushed with lard and dry it at a temperature of 180℃~200℃ and a drying time of 5~10 minutes.
以下各例(实施例和对比例)中，如无其他说明，PEI指聚乙烯亚胺，CMC-Na指羧甲基纤维素钠。如无其他说明，各原料的份数指重量份数。In the following examples (embodiments and comparative examples), unless otherwise specified, PEI refers to polyethyleneimine, CMC-Na refers to sodium carboxymethylcellulose, and unless otherwise specified, the parts of each raw material refer to parts by weight.
实施例1.Example 1.
(1)将青檀皮纤维浆50份、竹纤维浆37份倒入抄造池。(1) Pour 50 parts of saffron bark fiber pulp and 37 parts of bamboo fiber pulp into a papermaking pool.
(2)向(1)所述抄造池按顺序倒入羧甲基纤维素钠2份、石灰粉2份、纤维素微晶粉1.5份，搅拌均匀。(2) Pour 2 parts of sodium carboxymethyl cellulose, 2 parts of lime powder, and 1.5 parts of cellulose microcrystalline powder into the papermaking pool described in (1) in order and stir evenly.
(2)向(2)所述抄造池按顺序倒入壳聚糖2份、聚乙烯亚胺2份、菊粉2份，搅拌均匀。(2) Pour 2 parts of chitosan, 2 parts of polyethyleneimine, and 2 parts of inulin into the papermaking pool described in (2) in order and stir evenly.
(4)向(3)所述抄造池按顺序倒入沉香粉1.5份。(4) Pour 1.5 parts of agarwood powder into the papermaking pool described in (3) in order.
(5)将步骤(4)制得的纸浆液抄纸、脱水、干燥，得到干纸页。(5) Making paper from the pulp obtained in step (4), dehydrating and drying the paper to obtain dry paper sheets.
(6)将步骤(5)所得的干纸页经过130℃热风处理360小时，即可得到熟化改良可控的混料手工书画纸。(6) The dried paper sheets obtained in step (5) are subjected to hot air treatment at 130° C. for 360 hours to obtain a mixed handmade calligraphy and painting paper with controlled aging and improvement.
实施例2.Example 2.
(1)将青檀皮纤维浆65份、竹纤维浆20份倒入抄造池。(1) Pour 65 parts of saffron bark fiber pulp and 20 parts of bamboo fiber pulp into a papermaking pool.
(2)向(1)所述抄造池按顺序倒入羧甲基纤维素钠2份、石灰粉2.5份、纤维素微晶粉2份，搅拌均匀。(2) Pour 2 parts of sodium carboxymethyl cellulose, 2.5 parts of lime powder and 2 parts of cellulose microcrystalline powder into the papermaking pool described in (1) in order and stir evenly.
(3)向(2)所述抄造池按顺序倒入壳聚糖2.5份、聚乙烯亚胺2份、菊粉2份，搅拌均匀。(3) Pour 2.5 parts of chitosan, 2 parts of polyethyleneimine, and 2 parts of inulin into the papermaking pool described in (2) in order and stir evenly.
(4)向(3)所述抄造池按顺序倒入沉香粉2份。(4) Pour 2 parts of agarwood powder into the papermaking pool described in (3) in order.
(5)将步骤(4)制得的纸浆液抄纸、脱水、干燥，得到干纸页。(5) Making paper from the pulp obtained in step (4), dehydrating and drying the paper to obtain dry paper sheets.
(6)将步骤(5)所得的干纸页经过150℃热风处理360小时，即可得到熟化改良可控的混料手工书画纸。(6) The dried paper sheets obtained in step (5) are subjected to a 150° C. hot air treatment for 360 hours to obtain a mixed handmade calligraphy and painting paper with controlled maturation and improvement.
实施例3.Example 3.
(1)将青檀皮纤维浆20份、竹纤维浆65份倒入抄造池。(1) Pour 20 parts of saffron bark fiber pulp and 65 parts of bamboo fiber pulp into a papermaking pool.
(2)向(1)所述抄造池按顺序倒入羧甲基纤维素钠2份、石灰粉2.5份、纤维素微晶粉2份，搅拌均匀。(2) Pour 2 parts of sodium carboxymethyl cellulose, 2.5 parts of lime powder and 2 parts of cellulose microcrystalline powder into the papermaking pool described in (1) in order and stir evenly.
(3)向(2)所述抄造池按顺序倒入壳聚糖2.5份、聚乙烯亚胺2份、菊粉2份，搅拌均匀。(3) Pour 2.5 parts of chitosan, 2 parts of polyethyleneimine, and 2 parts of inulin into the papermaking pool described in (2) in order and stir evenly.
(4)向(3)所述抄造池按顺序倒入沉香粉2份。(4) Pour 2 parts of agarwood powder into the papermaking pool described in (3) in order.
(5)将步骤(4)制得的纸浆液抄纸、脱水、干燥，得到干纸页。(5) Making paper from the pulp obtained in step (4), dehydrating and drying the paper to obtain dry paper sheets.
(6)将步骤(5)所得的干纸页经过120℃热风处理720小时，即可得到熟化改良可控的混料手工书画纸。(6) The dried paper sheets obtained in step (5) are subjected to a 120° C. hot air treatment for 720 hours to obtain a mixed handmade calligraphy and painting paper with controlled maturation and improvement.
实施例4.Example 4.
(1)将青檀皮纤维浆50份、竹纤维浆39份倒入抄造池。(1) Pour 50 parts of saffron bark fiber pulp and 39 parts of bamboo fiber pulp into a papermaking pool.
(2)向(1)所述抄造池按顺序倒入羧甲基纤维素钠1份、石灰粉1.5份、纤维素微晶粉1.5份，搅拌均匀。(2) Pour 1 part of sodium carboxymethyl cellulose, 1.5 parts of lime powder and 1.5 parts of cellulose microcrystalline powder into the papermaking pool described in (1) in order and stir evenly.
(3)向(2)所述抄造池按顺序倒入壳聚糖2份、聚乙烯亚胺1.5份、菊粉1.5份，搅拌均匀。(3) Pour 2 parts of chitosan, 1.5 parts of polyethyleneimine, and 1.5 parts of inulin into the papermaking pool described in (2) in order and stir evenly.
(4)向(3)所述抄造池按顺序倒入沉香粉2份。(4) Pour 2 parts of agarwood powder into the papermaking pool described in (3) in order.
(5)将步骤(4)制得的纸浆液抄纸、脱水、干燥，得到干纸页。(5) Making paper from the pulp obtained in step (4), dehydrating and drying the paper to obtain dry paper sheets.
(6)将步骤(5)所得的干纸页经过110℃热风处理720小时，即可得到熟化改良可控的混料手工书画纸。(6) The dried paper sheets obtained in step (5) are subjected to a hot air treatment at 110° C. for 720 hours to obtain a mixed handmade calligraphy and painting paper with controlled maturation and improvement.
实施例5.Example 5.
(1)将青檀皮纤维浆40份、竹纤维浆50份倒入抄造池。(1) Pour 40 parts of saffron bark fiber pulp and 50 parts of bamboo fiber pulp into a papermaking pool.
(2)向(1)所述抄造池按顺序倒入羧甲基纤维素钠1.5份、石灰粉1份、纤维素微晶粉2份，搅拌均匀。(2) Pour 1.5 parts of sodium carboxymethyl cellulose, 1 part of lime powder, and 2 parts of cellulose microcrystalline powder into the papermaking pool described in (1) in order and stir evenly.
(3)向(2)所述抄造池按顺序倒入壳聚糖0.5份、聚乙烯亚胺2份、菊粉1份，搅拌均匀。(3) Pour 0.5 parts of chitosan, 2 parts of polyethyleneimine, and 1 part of inulin into the papermaking pool described in (2) in order and stir evenly.
(4)向(3)所述抄造池按顺序倒入沉香粉2份。(4) Pour 2 parts of agarwood powder into the papermaking pool described in (3) in order.
(5)将步骤(4)制得的纸浆液抄纸、脱水、干燥，得到干纸页。(5) Making paper from the pulp obtained in step (4), dehydrating and drying the paper to obtain dry paper sheets.
(6)将步骤(5)所得的干纸页经过150℃热风处理100小时，即可得到熟化改良可控的混料手工书画纸。(6) The dried paper sheets obtained in step (5) are subjected to hot air treatment at 150° C. for 100 hours to obtain a mixed handmade calligraphy and painting paper with controlled aging and improvement.
实施例6.Example 6.
(1)将青檀皮纤维浆31份、竹纤维浆61份倒入抄造池。(1) Pour 31 parts of saffron bark fiber pulp and 61 parts of bamboo fiber pulp into a papermaking pool.
(2)向(1)所述抄造池按顺序倒入羧甲基纤维素钠2份、石灰粉1份、纤维素微晶粉1份，搅拌均匀。(2) Pour 2 parts of sodium carboxymethyl cellulose, 1 part of lime powder and 1 part of cellulose microcrystalline powder into the papermaking pool described in (1) in order and stir evenly.
(3)向(2)所述抄造池按顺序倒入壳聚糖1份、聚乙烯亚胺0.5份、菊粉1.5份，搅拌均匀。(3) Pour 1 part of chitosan, 0.5 part of polyethyleneimine, and 1.5 parts of inulin into the papermaking pool described in (2) in order and stir evenly.
(4)向(3)所述抄造池按顺序倒入沉香粉1份。(4) Pour 1 portion of agarwood powder into the papermaking pool described in (3) in order.
(5)将步骤(4)制得的纸浆液抄纸、脱水、干燥，得到干纸页。(5) Making paper from the pulp obtained in step (4), dehydrating and drying the paper to obtain dry paper sheets.
(6)将步骤(5)所得的干纸页经过130℃热风处理320小时，即可得到熟化改良可控的混料手工书画纸。(6) The dried paper sheets obtained in step (5) are subjected to hot air treatment at 130° C. for 320 hours to obtain a mixed handmade calligraphy and painting paper with controlled maturation and improvement.
实施例7.Example 7.
(1)将青檀皮纤维浆52份、竹纤维浆39份倒入抄造池。(1) Pour 52 parts of saffron bark fiber pulp and 39 parts of bamboo fiber pulp into a papermaking pool.
(2)向(1)所述抄造池按顺序倒入羧甲基纤维素钠1份、石灰粉1.5份、纤维素微晶粉1.5份，搅拌均匀。(2) Pour 1 part of sodium carboxymethyl cellulose, 1.5 parts of lime powder and 1.5 parts of cellulose microcrystalline powder into the papermaking pool described in (1) in order and stir evenly.
(3)向(2)所述抄造池按顺序倒入壳聚糖2份、聚乙烯亚胺1.5份、菊粉1.5份，搅拌均匀。(3) Pour 2 parts of chitosan, 1.5 parts of polyethyleneimine, and 1.5 parts of inulin into the papermaking pool described in (2) in order and stir evenly.
(4)将步骤(3)制得的纸浆液抄纸、脱水、干燥，得到干纸页。(4) Making paper from the pulp obtained in step (3), dehydrating and drying the paper to obtain dry paper sheets.
(5)将步骤(4)所得的干纸页经过130℃热风处理300小时，即可得到熟化改良可控的混料手工书画纸。(5) The dried paper sheets obtained in step (4) are subjected to hot air treatment at 130° C. for 300 hours to obtain a mixed handmade calligraphy and painting paper with controlled aging and improvement.
对比例1.未使用壳聚糖和聚乙烯亚胺Comparative Example 1: No chitosan and polyethyleneimine were used
(1)将青檀皮纤维浆31份、竹纤维浆61份倒入抄造池。(1) Pour 31 parts of Pteris tannin bark fiber pulp and 61 parts of bamboo fiber pulp into a papermaking pool.
(2)向(1)所述抄造池按顺序倒入羧甲基纤维素钠3份、石灰粉1.5份、纤维素微晶粉1份，搅拌均匀。(2) Pour 3 parts of sodium carboxymethyl cellulose, 1.5 parts of lime powder and 1 part of cellulose microcrystalline powder into the papermaking pool described in (1) in order and stir evenly.
(3)向(2)所述抄造池按顺序倒入菊粉1.5份，搅拌均匀。(3) Pour 1.5 parts of inulin into the papermaking pool described in (2) in order and stir evenly.
(4)向(3)所述抄造池按顺序倒入沉香粉1份。(4) Pour 1 portion of agarwood powder into the papermaking pool described in (3) in order.
(5)将步骤(4)制得的纸浆液抄纸、脱水、干燥，得到干纸页。(5) Making paper from the pulp obtained in step (4), dehydrating and drying the paper to obtain dry paper sheets.
(6)将步骤(5)所得的干纸页经过130℃热风处理320小时，即可得到熟化改良可控的混料手工书画纸。(6) The dried paper sheets obtained in step (5) are subjected to hot air treatment at 130° C. for 320 hours to obtain a mixed handmade calligraphy and painting paper with controlled maturation and improvement.
对比例2.未使用石灰、纤维素微晶粉、羧甲基纤维素钠和菊粉Comparative Example 2: No lime, cellulose microcrystalline powder, sodium carboxymethyl cellulose and inulin were used
(1)将青檀皮纤维浆31份、竹纤维浆61份倒入抄造池。(1) Pour 31 parts of Pteris tannin bark fiber pulp and 61 parts of bamboo fiber pulp into a papermaking pool.
(2)向(1)所述抄造池按顺序倒入壳聚糖4份、聚乙烯亚胺2.5份，搅拌均匀。(2) Pour 4 parts of chitosan and 2.5 parts of polyethyleneimine into the papermaking pool described in (1) in order and stir evenly.
(3)向(3)所述抄造池按顺序倒入沉香粉1.5份。(3) Pour 1.5 parts of agarwood powder into the papermaking pool described in (3) in order.
(4)将步骤(4)制得的纸浆液抄纸、脱水、干燥，得到干纸页。(4) Making paper from the pulp obtained in step (4), dehydrating and drying the paper to obtain dry paper sheets.
(5)将步骤(5)所得的干纸页经过130℃热风处理320小时，即可得到熟化改良可控的混料手工书画纸。(5) The dried paper obtained in step (5) is subjected to a hot air treatment at 130° C. for 320 hours to obtain a mixed handmade calligraphy and painting paper with controlled curing and improvement.
对比例3.未进行高温热处理Comparative Example 3: No high temperature heat treatment
(1)将青檀皮纤维浆31份、竹纤维浆61份倒入抄造池。(1) Pour 31 parts of saffron bark fiber pulp and 61 parts of bamboo fiber pulp into a papermaking pool.
(2)向(1)所述抄造池按顺序倒入羧甲基纤维素钠2份、石灰粉1份、纤维素微晶粉1份，搅拌均匀。(2) Pour 2 parts of sodium carboxymethyl cellulose, 1 part of lime powder and 1 part of cellulose microcrystalline powder into the papermaking pool described in (1) in order and stir evenly.
(3)向(2)所述抄造池按顺序倒入壳聚糖1份、聚乙烯亚胺0.5份、菊粉1.5份，搅拌均匀。(3) Pour 1 part of chitosan, 0.5 part of polyethyleneimine, and 1.5 parts of inulin into the papermaking pool described in (2) in order and stir evenly.
(4)向(3)所述抄造池按顺序倒入沉香粉1份。(4) Pour 1 portion of agarwood powder into the papermaking pool described in (3) in order.
(5)将步骤(4)制得的纸浆液抄纸、脱水、干燥，得到干纸页。(5) Making paper from the pulp obtained in step (4), dehydrating and drying the paper to obtain dry paper sheets.
(6)将步骤(5)所得的干纸页经过风干，即可得到熟化改良可控的混料手工书画纸。(6) The dried paper sheets obtained in step (5) are air-dried to obtain mixed handmade calligraphy and painting paper with controllable curing and improvement.
对比例4.采用与实施例6基本相同的方法，区别在于：步骤(1)中省略了皮纤维。Comparative Example 4: A method substantially the same as that of Example 6 was used, except that the skin fiber was omitted in step (1).
对比例5.采用与实施例6基本相同的方法，区别在于：步骤(1)中省略了竹纤维。Comparative Example 5: A method substantially the same as that of Example 6 was used, except that bamboo fiber was omitted in step (1).
对比例6.采用与实施例6基本相同的方法，区别在于：步骤(2)中省略了羧甲基纤维素钠。Comparative Example 6: A method substantially the same as that of Example 6 was used, except that sodium carboxymethyl cellulose was omitted in step (2).
对比例7.采用与实施例6基本相同的方法，区别在于：步骤(3)中省略了菊粉。Comparative Example 7: A method substantially the same as that of Example 6 was used, except that inulin was omitted in step (3).
对比例8.采用与实施例6基本相同的方法，区别在于：步骤(3)中省略了壳聚糖。Comparative Example 8: A method substantially the same as that of Example 6 was used, except that chitosan was omitted in step (3).
对比例9.采用与实施例6基本相同的方法，区别在于：步骤(3)中省略了聚乙烯亚胺。Comparative Example 9: A method substantially the same as that of Example 6 was used, except that polyethyleneimine was omitted in step (3).
对比例10.采用与实施例6基本相同的方法，区别在于：步骤(6)中熟化条件为105℃热风处理，也即采用的熟化温度略低。Comparative Example 10: A method substantially the same as that of Example 6 is adopted, except that the aging condition in step (6) is hot air treatment at 105°C, i.e., the aging temperature adopted is slightly lower.
对比例11.采用与实施例6基本相同的方法，区别在于：步骤(3)中的壳聚糖1份和聚乙烯亚胺0.5份，分别替换为阳离子淀粉1份和聚丙烯酰胺0.5份。Comparative Example 11. A method substantially the same as that of Example 6 was used, except that 1 part of chitosan and 0.5 part of polyethyleneimine in step (3) were replaced by 1 part of cationic starch and 0.5 part of polyacrylamide, respectively.
上述各实施例和各对比例的制备参数还可参阅表1。The preparation parameters of the above embodiments and comparative examples can also be found in Table 1.
表1.Table 1.
测试与分析Testing and analysis
1、书画纸面密度，根据GB/T451.2-2002方法测试“定量”(可参阅表2)，该指标表示纸张每平方米的重量。1. The surface density of calligraphy and painting paper is tested according to the "quantitative" method of GB/T451.2-2002 (see Table 2). This indicator indicates the weight of paper per square meter.
2、书画纸含水量，根据GB/T462-2003方法测试，可参阅表2“水分”。以质量百分比计。2. The moisture content of calligraphy and painting paper is tested according to the method of GB/T462-2003, and can be found in Table 2 "Moisture Content". It is measured in mass percentage.
3、书画纸吸水性，根据GB/T 461.1-2002方法测试，可参阅表2中“吸水性”指标，表示纸张吸收空气中水分的平衡量，单位mm。该指标的数值越大，表示吸水性更佳。3. The water absorption of calligraphy and painting paper is tested according to the method of GB/T 461.1-2002. Please refer to the "Water Absorption" index in Table 2, which indicates the balance amount of water absorbed by the paper in the air, in mm. The larger the value of this index, the better the water absorption.
4、书画纸抑菌率，根据FZ/T73023-2006方法测试，可参阅表2中“抑菌率”指标。抑菌率越高表明抗菌性能越好。4. The antibacterial rate of calligraphy and painting paper is tested according to the FZ/T73023-2006 method, and can be found in the "antibacterial rate" index in Table 2. The higher the antibacterial rate, the better the antibacterial performance.
5、墨迹直径是指墨迹在纸上划线时的线宽，可根据GB/T460-2008方法测试。该数值越小说明纸张施胶度越高，对于墨迹可控性越好。5. Ink diameter refers to the width of the ink line on paper, which can be tested according to GB/T460-2008 method. The smaller the value, the higher the sizing degree of the paper, and the better the controllability of the ink.
本申请中，如无其他说明，当墨迹直径大于3.400mm时认定“墨迹不可控”。In this application, unless otherwise specified, when the ink diameter is greater than 3.400 mm, it is deemed that the ink is "uncontrollable".
6、抗张指数及抗张指数保留率6. Tensile index and tensile index retention rate
抗张指数是指单位定量下单位宽度的纸张断裂前所能承受的最大张力。可根据GB-T12914-2008方法测试。抗张指数越高，表明纤维强度和结合强度越高。The tensile index refers to the maximum tension that a piece of paper per unit width can withstand before breaking under a unit basis weight. It can be tested according to the GB-T12914-2008 method. The higher the tensile index, the higher the fiber strength and bonding strength.
抗张指数保留率：将待测书画纸在80℃/65％RH环境下放置7天后，重新测试抗张指数，该重测值与制备所得抗张指数的初始测试值的相对百分比记为抗张指数保留率，可参阅表2“80℃/65％RH环境7天”。抗张指数保留率越高，表明纸张纤维及纤维之间仍具有一定强度，受到的老化劣化有限，一定程度上反映了纸张寿命更长。Tensile index retention rate: After the calligraphy and painting paper to be tested is placed in an environment of 80℃/65%RH for 7 days, the tensile index is retested. The relative percentage of the retested value to the initial test value of the prepared tensile index is recorded as the tensile index retention rate. Please refer to Table 2 "80℃/65%RH environment for 7 days". The higher the tensile index retention rate, the stronger the paper fibers are and the less deteriorated by aging, which to some extent reflects the longer life of the paper.
表2.Table 2.
根据测试结果，本发明制备得到的手工书画纸(实施例1-7)具有优异的综合品质，纸质细腻、润墨效果可控，对颜料的锁定效果提高，颜色保持效果好，纸张拉力强。According to the test results, the handmade calligraphy and painting paper (Examples 1-7) prepared by the present invention has excellent comprehensive quality, fine paper texture, controllable ink wetting effect, improved pigment locking effect, good color retention effect, and strong paper tensile strength.
此外，根据表2测试结果，可见，本发明提供的制备方法(实施例1-7)实现了手工书画纸可控熟化改良的效果，不仅可以控制润墨性能，而且具有非常好的抗菌性能，以及较大的抗张强度。In addition, according to the test results in Table 2, it can be seen that the preparation method provided by the present invention (Examples 1-7) achieves the effect of controllable maturation improvement of handmade calligraphy and painting paper, which can not only control the ink wetting performance, but also has very good antibacterial properties and greater tensile strength.
比较对比例1和各实施例，可见，添加壳聚糖与聚乙烯亚胺有助于提高纸张抑菌率，对比例1未添加壳聚糖与聚乙烯亚胺的情况下抑菌率明显下降，且墨迹直径增大不可控。Comparing Comparative Example 1 with the embodiments, it can be seen that the addition of chitosan and polyethyleneimine helps to improve the antibacterial rate of paper. In Comparative Example 1, when chitosan and polyethyleneimine were not added, the antibacterial rate was significantly reduced, and the increase in ink diameter was uncontrollable.
比较对比例2和各实施例，对比例2未添加石灰、纤维素微晶粉、CMC-Na和菊粉，抗张指数保留率剧烈下降，可见添加石灰、纤维素微晶粉、CMC-Na和菊粉有助于为纸张提供更好的保存环境，提高纸张强度保留率，进一步提高纸张保存寿命。对比例2未使用石灰、纤维素微晶粉、CMC-Na和菊粉，结果导致水分和吸水性下降，原因之一包括下述作用的缺失：纤维素微晶粉有助于填补纤维间孔隙，石灰粉能够提供弱酸碱性，提高羧甲基纤维素钠和菊粉稳定性。Comparing Comparative Example 2 with each embodiment, the tensile index retention rate of Comparative Example 2 is drastically reduced without adding lime, cellulose microcrystalline powder, CMC-Na and inulin, which shows that adding lime, cellulose microcrystalline powder, CMC-Na and inulin helps to provide a better storage environment for paper, improve the strength retention rate of paper, and further improve the storage life of paper. Comparative Example 2 does not use lime, cellulose microcrystalline powder, CMC-Na and inulin, resulting in a decrease in moisture and water absorption, one of the reasons includes the lack of the following effects: cellulose microcrystalline powder helps to fill the pores between fibers, lime powder can provide weak acidity and alkalinity, and improve the stability of sodium carboxymethyl cellulose and inulin.
比较对比例3和各实施例，对比例3未实施高温热处理，制得的书画纸吸水性和水分提高，墨迹直径变大，不可控。实施例1-7的制备方法中，均包括在特定温度下热处理的高温熟化步骤，可提高纤维素微晶与纸张纤维纤维素的结合作用，同时能够提高石灰粉弱碱性下菊粉与羧甲基纤维素钠的协同作用，且使纸张纤维素不易水解，本方法提供的制备方法中所使用的高温热处理步骤还可提高壳聚糖与聚乙烯亚胺与纤维、助剂的平铺效果。Comparing Comparative Example 3 with each embodiment, Comparative Example 3 did not implement high-temperature heat treatment, and the water absorption and moisture content of the prepared calligraphy and painting paper increased, and the ink diameter became larger and uncontrollable. The preparation methods of Examples 1-7 all include a high-temperature aging step of heat treatment at a specific temperature, which can improve the binding effect of cellulose microcrystals with paper fiber cellulose, and at the same time can improve the synergistic effect of inulin and sodium carboxymethyl cellulose under the weak alkalinity of lime powder, and make the paper cellulose difficult to hydrolyze. The high-temperature heat treatment step used in the preparation method provided by this method can also improve the paving effect of chitosan, polyethyleneimine, fiber, and additives.
对比例4未使用皮纤维，仅使用竹纤维，而竹纤维浆纸张纤维较短，不但抗张指数不高，而且在湿热老化处理后的保留率也较差。对比例5未使用竹纤维，仅使用皮纤维，虽然皮纤维较长，抗张指数较高，但结构孔隙较多，湿热老化过程中受损也较明显，湿热老化后抗张指数保留率也有下降。Comparative Example 4 does not use skin fiber, but only uses bamboo fiber. However, the bamboo fiber pulp paper fiber is relatively short, and not only the tensile index is not high, but also the retention rate after wet heat aging treatment is poor. Comparative Example 5 does not use bamboo fiber, but only uses skin fiber. Although the skin fiber is longer and has a higher tensile index, it has more structural pores and is more obviously damaged during wet heat aging. The retention rate of the tensile index also decreases after wet heat aging.
对比例6未添加羧甲基纤维素钠，对比例7未添加菊粉，纸张抗张指数及其保留率均较差。不添加羧甲基纤维素钠和菊粉，导致不能为纸张提供理想的弱碱环境，且不利于纸张纤维的强度保持。Comparative Example 6 did not add sodium carboxymethyl cellulose, and Comparative Example 7 did not add inulin, and the paper tensile index and retention rate were both poor. Without adding sodium carboxymethyl cellulose and inulin, it is impossible to provide an ideal weak alkaline environment for the paper, and it is not conducive to maintaining the strength of the paper fiber.
对比例8未添加壳聚糖，对比例9未添加聚乙烯亚胺，纸张抗张指数及其保留率均较差。这是因为，壳聚糖和聚乙烯亚胺除了起到桥联作用外，还起到增干强剂和增湿强剂的作用。Comparative Example 8 did not add chitosan, and Comparative Example 9 did not add polyethyleneimine, and the paper tensile index and retention rate were both poor. This is because chitosan and polyethyleneimine, in addition to playing a bridging role, also play the role of dry strength enhancer and wet strength enhancer.
通过各实施例与对比例的颜色效果对比结果可知，壳聚糖、聚乙烯亚胺、羧甲基纤维素钠及菊粉在氨基、羟基及羧基的协同作用提高了锁定颜料作用。而且，在上述助剂的复合作用下，书画纸不但具有良好的抗菌效果、抗拉强度、润墨、固色效果，且在老化处理后仍得到有效保持。在缺少任一组分的情况下，都会削弱上述协同技术效果。By comparing the color effects of the examples with the comparative examples, it can be seen that the synergistic effect of chitosan, polyethyleneimine, sodium carboxymethylcellulose and inulin at the amino, hydroxyl and carboxyl groups improves the pigment locking effect. Moreover, under the combined effect of the above-mentioned additives, the calligraphy and painting paper not only has good antibacterial effect, tensile strength, ink wetting and color fixing effects, but also remains effectively maintained after aging treatment. In the absence of any component, the above-mentioned synergistic technical effect will be weakened.
对比例10的熟化温度较低，助剂分子在纸张纤维表面分布不均，导致抗张指数较低，其保留率也较差，没有充分起到保护作用。The aging temperature of Comparative Example 10 is low, and the auxiliary agent molecules are unevenly distributed on the surface of the paper fiber, resulting in a low tensile index and a poor retention rate, and the protective effect is not fully played.
对比例11采用常用助剂阳离子淀粉作为增强剂，聚丙烯酰胺作为桥联剂，所得纸张纤维极易团聚，纸张薄厚不均，无法实现本发明书画纸的技术效果。而且，虽然加入阳离子淀粉和聚丙烯酰胺也能够获得一定纸张强度，但是在保留率方面表现较差。进一步表明，本发明的书画纸的优异质量是书画纸组合物中特定组分协同增效的效果，这些特定组分缺一不可，而且并非常规组分的简单组合，而是本申请发明人经过大量的实验探索后筛选得到的特殊组合。Comparative Example 11 uses the commonly used auxiliary cationic starch as a reinforcing agent and polyacrylamide as a bridging agent. The resulting paper fibers are very easy to agglomerate, and the thickness of the paper is uneven, which cannot achieve the technical effect of the calligraphy and painting paper of the present invention. Moreover, although the addition of cationic starch and polyacrylamide can also obtain a certain paper strength, the retention rate is poor. It is further shown that the excellent quality of the calligraphy and painting paper of the present invention is the synergistic effect of specific components in the calligraphy and painting paper composition. These specific components are indispensable and are not a simple combination of conventional components, but a special combination screened by the inventor of the present application after a large number of experimental explorations.
实施例8～14Embodiments 8 to 14
实施例8～14，在上述实施例1～7的基础上分别加入0.5～1.5重量份的香草汁，并调整书画纸组合物的总重量份数不变(可参阅表3)，采用前述方法对书画纸的相关项指标进行测试，包括面密度、含水量、吸水性、抑菌率、墨迹直径、抗张指数及抗张指数保留率。结果表明，实施例8～14中可以赋予书画纸独特的芳香气味，且制备得到的手工书画纸均具有优异的综合品质，纸质细腻、润墨效果可控，对颜料的锁定效果提高，颜色保持效果好，纸张拉力强。In Examples 8 to 14, 0.5 to 1.5 parts by weight of vanilla juice were added to the above Examples 1 to 7, and the total weight of the calligraphy and painting paper composition was adjusted to remain unchanged (see Table 3), and the above method was used to test the relevant indicators of the calligraphy and painting paper, including surface density, water content, water absorption, antibacterial rate, ink diameter, tensile index and tensile index retention rate. The results show that in Examples 8 to 14, the calligraphy and painting paper can be given a unique aromatic smell, and the prepared handmade calligraphy and painting paper has excellent comprehensive quality, fine paper quality, controllable ink wetting effect, improved pigment locking effect, good color retention effect, and strong paper tensile strength.
表3中各项指标的测试结果与实施例1～7类似。The test results of various indicators in Table 3 are similar to those of Examples 1 to 7.
表3.Table 3.
上述仅为本发明的部分优选实施例，本发明并不仅限于上述实施例的内容。对于本领域中的技术人员来说，在本发明技术方案的构思范围内，或者在本发明技术方案的指导、启示下，可以有各种变化、修改、替换和变型，所作的任何具有等同技术效果的变化、修改、替换和变型，均在本发明保护范围之内。凡是利用本发明说明书内容所作的等效设计或等效流程变换，或直接或间接运用在其他相关的技术领域，均同理包括在本发明的专利保护范围内。The above are only some preferred embodiments of the present invention, and the present invention is not limited to the contents of the above embodiments. For those skilled in the art, within the conceptual scope of the technical solution of the present invention, or under the guidance and inspiration of the technical solution of the present invention, there may be various changes, modifications, substitutions and variations, and any changes, modifications, substitutions and variations with equivalent technical effects are within the protection scope of the present invention. Any equivalent design or equivalent process transformation made using the contents of the present invention specification, or directly or indirectly applied in other related technical fields, are similarly included in the patent protection scope of the present invention.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310787458.5ACN116926986A (en) | 2023-06-29 | 2023-06-29 | Calligraphy and painting paper composition, paper pulp liquid, handmade calligraphy and painting paper and preparation method thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310787458.5ACN116926986A (en) | 2023-06-29 | 2023-06-29 | Calligraphy and painting paper composition, paper pulp liquid, handmade calligraphy and painting paper and preparation method thereof |
| Publication Number | Publication Date |
|---|---|
| CN116926986Atrue CN116926986A (en) | 2023-10-24 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310787458.5APendingCN116926986A (en) | 2023-06-29 | 2023-06-29 | Calligraphy and painting paper composition, paper pulp liquid, handmade calligraphy and painting paper and preparation method thereof |
| Country | Link |
|---|---|
| CN (1) | CN116926986A (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117468263A (en)* | 2023-10-27 | 2024-01-30 | 孙迪 | Archival paper based on full utilization of paper mulberry bark and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040118540A1 (en)* | 2002-12-20 | 2004-06-24 | Kimberly-Clark Worlwide, Inc. | Bicomponent strengtheninig system for paper |
| CN101589197A (en)* | 2006-11-23 | 2009-11-25 | 荷兰应用科学研究会(Tno) | Biopolymers as wet strength additives |
| CN107100029A (en)* | 2017-05-09 | 2017-08-29 | 贞丰县民族民间工艺厂 | A kind of agalloch eaglewood china picture-character paper and preparation method thereof |
| CN111041887A (en)* | 2019-12-26 | 2020-04-21 | 同曦集团有限公司 | Antibacterial, mildew-proof and moth-proof rice paper raw pulp, prepared rice paper and preparation method |
| CN111472196A (en)* | 2020-04-10 | 2020-07-31 | 浙江科技学院 | Durable manual writing and painting paper filled with micro-nano calcium and preparation method thereof |
| CN115613387A (en)* | 2022-11-11 | 2023-01-17 | 岳阳林纸股份有限公司 | Mark paper and manufacturing method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040118540A1 (en)* | 2002-12-20 | 2004-06-24 | Kimberly-Clark Worlwide, Inc. | Bicomponent strengtheninig system for paper |
| CN101589197A (en)* | 2006-11-23 | 2009-11-25 | 荷兰应用科学研究会(Tno) | Biopolymers as wet strength additives |
| CN107100029A (en)* | 2017-05-09 | 2017-08-29 | 贞丰县民族民间工艺厂 | A kind of agalloch eaglewood china picture-character paper and preparation method thereof |
| CN111041887A (en)* | 2019-12-26 | 2020-04-21 | 同曦集团有限公司 | Antibacterial, mildew-proof and moth-proof rice paper raw pulp, prepared rice paper and preparation method |
| CN111472196A (en)* | 2020-04-10 | 2020-07-31 | 浙江科技学院 | Durable manual writing and painting paper filled with micro-nano calcium and preparation method thereof |
| CN115613387A (en)* | 2022-11-11 | 2023-01-17 | 岳阳林纸股份有限公司 | Mark paper and manufacturing method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117468263A (en)* | 2023-10-27 | 2024-01-30 | 孙迪 | Archival paper based on full utilization of paper mulberry bark and preparation method thereof |
| Publication | Publication Date | Title |
|---|---|---|
| LIN et al. | Physical characteristics of surimi and bacterial cellulose composite gel | |
| BRPI1008341B1 (en) | METHOD TO PRODUCE MODIFIED NANOFIBRILLATED CELLULOSE, MODIFIED NANOFIBRILLATED CELLULOSE, USE OF MODIFIED NANOFIBRILLATED CELLULOSE, PAPER, AND, METHOD FOR MANUFACTURING PAPER | |
| CN116926986A (en) | Calligraphy and painting paper composition, paper pulp liquid, handmade calligraphy and painting paper and preparation method thereof | |
| CN102240065B (en) | Process for improving wet strength and flexibility of base slices made by slices in paper making method | |
| US12269936B2 (en) | Cellulose processing | |
| CN101747441A (en) | Preparation method of sodium carboxymethyl cellulose with high degree of substitution and high viscosity | |
| CN107212457A (en) | A kind of method for improving tobacco sheets by paper making method slurry retention and water filtering performance | |
| CN113550175B (en) | Cigarette paper, preparation method thereof and cigarette product | |
| CN113575839A (en) | Brewing type prepared dry rice noodles and preparation method thereof | |
| CN104957755B (en) | A kind of improve the method for calcium carbonate retention rate in papermaking-method reconstituted tobaccos | |
| CN105077555B (en) | A method for processing reconstituted tobacco leaves by papermaking method | |
| CN113502689A (en) | Microbial polysaccharide enhanced high-transparency filter stick forming paper and preparation method thereof | |
| CN104957749B (en) | A kind of method for improving papermaking-method reconstituted tobaccos slurry retention | |
| CN105146716B (en) | A kind of improve the method for calcium carbonate retention rate in papermaking-method reconstituted tobaccos | |
| CN110754683A (en) | A kind of raw material for heat not burn cigarette and preparation method thereof | |
| CN105686056B (en) | A water-swelling stalk product for improving the adsorption performance of reconstituted tobacco leaf filler by papermaking method, its preparation method and application | |
| EP1167434A1 (en) | Starch composition and the use thereof | |
| CN116463886B (en) | Preparation method of base paper of daily use paper of cream | |
| CN117481381A (en) | A method for preparing high strength and high uniformity tobacco sheets by rolling | |
| CN110396868A (en) | A kind of tea fragrance wrapping paper and its preparation process | |
| CN116849390A (en) | A method for compounding shredded tobacco for heated cigarettes, shredded tobacco and heated cigarettes | |
| CN104963233B (en) | The china picture-character paper of a kind of interpolation bleached bamboo pulp dregs of rice and fibre grafting agent and preparation method | |
| CN104877594A (en) | Adhesion agent for reconstituted tobacco leafs through slurry process | |
| CN104957751B (en) | A method for improving the retention rate of calcium carbonate in reconstituted tobacco leaves by papermaking | |
| CN104957756B (en) | A method for improving the retention rate of calcium carbonate in reconstituted tobacco leaves by papermaking |
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |