技术领域technical field
本发明属于织物制造技术领域，具体涉及一种用于发光织物的聚合物光纤、发光织物及其制造方法。The invention belongs to the technical field of fabric manufacturing, and in particular relates to a polymer optical fiber used for luminous fabrics, a luminous fabric and a manufacturing method thereof.
背景技术Background technique
光纤发光织物是以光纤为纱线的织物，通过对光纤维进行机械破坏、激光刻痕、弯曲等处理，使其部分传导光从侧面漏出，从而形成具有发光效果的织物。聚合物光纤(polymeropticalfiber，简写为POF)是由高折射率的聚合物材料为纤芯和低折射率的聚合物材料为包层所构成的光纤。制作POF主要的材料有两类：一类是聚甲基丙烯酸甲酯聚合物PMMA(PolymerPolymethylmethacrylate)；另一类是含氟聚合物(Perfluorinatedpolymer)。这些由聚合物或者是有机材料制备而成的细丝状可传导光功率的光纤传输线，具有柔韧、密度低、导光不导电且不产生热量等优势。利用聚合物侧发光光纤传导光路和表面发散光的原理，可将POF与普通纱线交织，制成POF发光织物。这种发光的织物具有柔韧性好、重量轻、使用持久安全、易于光源连接等优点，与LED织物相比，还具有不带电、耗能小不发热的优势，目前，该POF发光织物已经应用于服装、家纺、医用光疗等多个领域。Optical fiber light-emitting fabric is a fabric with optical fiber as yarn. Through mechanical damage, laser scoring, bending and other treatments on the optical fiber, part of the transmitted light leaks from the side, thereby forming a fabric with a luminous effect. Polymer optical fiber (POF for short) is an optical fiber composed of a polymer material with a high refractive index as the core and a polymer material with a low refractive index as the cladding. There are two main types of materials for making POF: one is polymethyl methacrylate polymer PMMA (PolymerPolymethylmethacrylate); the other is fluoropolymer (Perfluorinatedpolymer). These filament-shaped fiber transmission lines that can conduct optical power and are made of polymers or organic materials have the advantages of flexibility, low density, light conduction, non-conduction, and no heat generation. Using the principle of polymer side-emitting optical fiber to conduct light path and surface divergent light, POF can be interwoven with ordinary yarn to make POF light-emitting fabric. This luminous fabric has the advantages of good flexibility, light weight, durable and safe use, and easy light source connection. Compared with LED fabrics, it also has the advantages of no electricity, low energy consumption and no heat generation. At present, this POF luminous fabric has been applied It is used in many fields such as clothing, home textiles, and medical phototherapy.
现阶段，多数光纤发光织物都是通过将PMMA/氟树脂聚合物光纤与棉纱相交织，使用一定手段对织物中的聚合物光纤进行集束处理，并将集束后的聚合物光纤与一定光源进行耦连，形成聚合物光纤发光织物。然而，由于这些聚合物光纤的弹性和抗弯刚度较差，在编织或后续使用过程中极易断裂，使用寿命不够理想，对其应用范围造成限制。At present, most optical fiber light-emitting fabrics are made by interweaving PMMA/fluororesin polymer optical fibers with cotton yarn, using certain means to bundle the polymer optical fibers in the fabric, and coupling the bundled polymer optical fibers with a certain light source. connected to form a polymer optical fiber light-emitting fabric. However, due to the poor elasticity and bending stiffness of these polymer optical fibers, they are easily broken during braiding or subsequent use, and their service life is not ideal, which limits their application range.
发明内容Contents of the invention
针对上述问题，本发明提供一种用于发光织物的聚合物光纤以及利用该光纤与织物进行编织的方法，该聚合物光纤不易断裂，由其制成的发光织物具有高亮度且使用寿命长的特点。In view of the above problems, the present invention provides a polymer optical fiber for luminous fabric and a method of weaving the optical fiber and fabric. The polymer optical fiber is not easy to break, and the luminous fabric made of it has high brightness and long service life. features.
为解决上述技术问题，本发明采用的技术方案为：In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is:
一种聚合物光纤，包括内芯层和外芯层；其中，所述内芯层由以下重量份的原料组成：聚对苯二甲酸丁二醇酯4～6份、环氧化反式-1，4-聚异戊二烯2～4份、SBS3～5份、聚丙烯酸乙酯50～60份、丙烯酸正丁酯10～15份、聚碳酸酯8～15份、甲基丙烯酰氧基硅烷5～8份、乙烯基硅烷2～3份、芳酰基膦氧化物1～2份、2，4-二羟基二苯甲酮1～2份；所述外芯层由以下重量份的原料组成：甲基丙烯酸五氟丙酯60～65份、四氟乙烯8～10份、三氟丙基甲基环三硅氧烷7～10份、乙烯基三乙氧基硅烷5～6份、甲基丙烯酰氧基硅烷5～6份、双苯甲酰基苯基氧化膦1～2份、α-羟烷基苯酮1～2份、纳米二氧化硅6～7份。A polymer optical fiber, comprising an inner core layer and an outer core layer; wherein, the inner core layer is composed of the following raw materials in parts by weight: 4 to 6 parts of polybutylene terephthalate, epoxidized trans- 2-4 parts of 1,4-polyisoprene, 3-5 parts of SBS, 50-60 parts of polyethyl acrylate, 10-15 parts of n-butyl acrylate, 8-15 parts of polycarbonate, methacryloxy 5-8 parts of base silane, 2-3 parts of vinyl silane, 1-2 parts of aroyl phosphine oxide, 1-2 parts of 2,4-dihydroxybenzophenone; the outer core layer consists of the following parts by weight Raw material composition: 60-65 parts of pentafluoropropyl methacrylate, 8-10 parts of tetrafluoroethylene, 7-10 parts of trifluoropropylmethylcyclotrisiloxane, 5-6 parts of vinyltriethoxysilane , 5-6 parts of methacryloyloxysilane, 1-2 parts of bisbenzoylphenylphosphine oxide, 1-2 parts of α-hydroxyalkyl phenone, and 6-7 parts of nano silicon dioxide.
所述的聚对苯二甲酸丁二醇酯(PBT)属于聚酯系列，是由1，4-pbt丁二醇(1，4-Butyleneglycol)与对苯二甲酸(PTA)或者对苯二甲酸酯(DMT)聚缩合而成，并经由混炼程序制成的乳白色半透明到不透明、结晶型热塑性聚酯树脂；其主链是由每个重复单元为刚性苯环和柔性脂肪醇连接起来的饱和线性分子组成，分子的高度几何规整性和刚性部分使整个体系具有高的机械强度、突出的耐化学试剂性、耐热性和优良的电性能；且PBT分子中没有侧链，结构对称，满足紧密堆砌的要求；在整个塑料光纤的体系中PBT作为骨架提供了非常好的机械稳定性。Described polybutylene terephthalate (PBT) belongs to polyester series, is made of 1,4-pbt butanediol (1,4-Butyleneglycol) and terephthalic acid (PTA) or terephthalic acid It is a milky white translucent to opaque, crystalline thermoplastic polyester resin formed by polycondensation of ester (DMT) and produced through a mixing process; its main chain is connected by each repeating unit being a rigid benzene ring and a flexible fatty alcohol Saturated linear molecular composition, the high geometric regularity and rigid part of the molecule make the whole system have high mechanical strength, outstanding chemical resistance, heat resistance and excellent electrical properties; and there is no side chain in the PBT molecule, and the structure is symmetrical , to meet the requirements of close packing; PBT provides very good mechanical stability as a skeleton in the entire plastic optical fiber system.
所述的环氧化反式-1，4-聚异戊二烯(ETPI)，是1，4反式聚异戊二烯(TPI)经环氧改性制成，使TPI中的反式结构保留下来，从而保持了TPI优良的性能，如高硬度、生热低、耐磨性能和动态疲劳性能优良的特点；另一方面，环氧化的结果，增加了TPI分子的极性，使其亲水能力加强，从而起到降低摩擦的作用；ETPI为结晶性高聚物，分子链在晶区内有序排列，其活动性降低，具有较高的耐热氧老化性能，经环氧化后合成的ETPI，仍然有部分的TPI结晶，这些微晶分布在聚丙烯酸乙酯、丙烯酸正丁酯、聚碳酸酯和聚对苯二甲酸丁二醇酯中起到物理交联的作用。The epoxidized trans-1,4-polyisoprene (ETPI) is made from 1,4 trans polyisoprene (TPI) through epoxy modification, so that the trans in TPI The structure is preserved, thus maintaining the excellent performance of TPI, such as high hardness, low heat generation, excellent wear resistance and dynamic fatigue performance; on the other hand, the result of epoxidation increases the polarity of TPI molecules, making Its hydrophilic ability is strengthened, thereby reducing friction; ETPI is a crystalline polymer, and its molecular chains are arranged in an orderly manner in the crystal region, its activity is reduced, and it has high heat and oxygen aging resistance. The ETPI synthesized after chemical reaction still has some TPI crystallization, and these crystallites are distributed in polyethylacrylate, n-butyl acrylate, polycarbonate and polybutylene terephthalate to play the role of physical crosslinking.
所述的SBS为苯乙烯-丁二烯-苯乙烯嵌段共聚物，是一种是热塑性弹性体，其加入能够显著提升大分子链段自由改变微观构象的能力，能够有效地降低聚合物材料的脆化点，从而降低丙烯酸聚合物材料在使用中发生脆裂的几率。所述的SBS为高等分子量的SBS和低等分子量的SBS组成的混合物；其中，高等分子量的SBS重均分子量为15～20万，低等分子量的SBS重均分子量为1万～2.5万；该混合物中，高等分子量的SBS的含量为20～50重量％。SBS与丙烯酸聚合物、聚碳酸酯会形成互穿网络结构穿插在聚对苯二甲酸丁二醇酯中，不仅增加聚对苯二甲酸丁二醇酯、丙烯酸聚合物和聚碳酸酯的相容性，而且有效改善整个体系的力学性能如拉伸屈服应力、屈服伸长率等。The SBS is a styrene-butadiene-styrene block copolymer, which is a thermoplastic elastomer, and its addition can significantly improve the ability of the macromolecular segment to freely change the microscopic conformation, and can effectively reduce the polymer material. The brittle point of the acrylic polymer material reduces the probability of brittle cracking during use. The SBS is a mixture of high-molecular-weight SBS and low-molecular-weight SBS; wherein, the weight-average molecular weight of high-molecular-weight SBS is 150,000-200,000, and the weight-average molecular weight of low-molecular-weight SBS is 10,000-25,000; In the mixture, the content of high molecular weight SBS is 20-50% by weight. SBS and acrylic polymer and polycarbonate will form an interpenetrating network structure interspersed in polybutylene terephthalate, which not only increases the compatibility of polybutylene terephthalate, acrylic polymer and polycarbonate properties, and effectively improve the mechanical properties of the entire system such as tensile yield stress, yield elongation, etc.
所述的甲基丙烯酰氧基硅烷是指同时含有两种不同化学性质基团的有机硅化合物，为上述内芯层塑料光纤合成过程中聚丙烯酸乙酯、丙烯酸正丁酯、聚碳酸酯、聚对苯二甲酸丁二醇酯、ETPI、SBS的加工助剂，在加热的条件下甲基丙烯酰氧基硅烷中不饱键(-C＝C-和-C＝O-)会与聚丙烯酸乙酯、丙烯酸正丁酯、聚碳酸酯、ETPI、SBS的不饱和键如(-C＝C-)进行接枝反应，提高它们之间的相容性；而且甲基丙烯酰氧基硅烷中的硅烷会使整个体系具有更为优异的弹性、拉伸性能，可弯曲度。The methacryloxysilane refers to an organosilicon compound containing two groups with different chemical properties at the same time, which is polyethyl acrylate, n-butyl acrylate, polycarbonate, Processing aids for polybutylene terephthalate, ETPI, and SBS, unsaturated bonds (-C=C- and -C=O-) in methacryloxysilane will bond with polybutylene terephthalate under heating conditions Ethyl acrylate, n-butyl acrylate, polycarbonate, ETPI, unsaturated bonds of SBS such as (-C=C-) carry out grafting reaction to improve the compatibility between them; and methacryloxysilane The silane in will make the whole system have more excellent elasticity, tensile properties, and flexibility.
所述的芳酰基膦氧化物、2，4-二羟基二苯甲酮为光引发剂。The aroylphosphine oxide and 2,4-dihydroxybenzophenone are photoinitiators.
所述内芯层的折射率为1.51～1.55，所述外芯层的折射率为1.43～1.46。The refractive index of the inner core layer is 1.51-1.55, and the refractive index of the outer core layer is 1.43-1.46.
所述内芯层材料的制备方法包括如下步骤：The preparation method of the inner core layer material comprises the following steps:
(1)在高速混合机里添加所述聚对苯二甲酸丁二醇酯、ETPI、SBS，进行搅拌5～10min；(1) Add the polybutylene terephthalate, ETPI, and SBS in a high-speed mixer, and stir for 5 to 10 minutes;
(2)将所述聚丙烯酸乙酯、丙烯酸正丁酯、聚碳酸酯、甲基丙烯酰氧基硅烷、乙烯基硅烷、芳酰基膦氧化物、2，4-二羟基二苯甲酮加入上述高速混合机，升温至80～120℃，继续搅拌10～20min，得到预混物；(2) Add the polyethyl acrylate, n-butyl acrylate, polycarbonate, methacryloxysilane, vinyl silane, aroyl phosphine oxide, and 2,4-dihydroxybenzophenone to the above-mentioned High-speed mixer, heat up to 80-120°C, continue stirring for 10-20 minutes to obtain a premix;
(3)将所得预混物置于双螺杆挤出机中依次进行熔融共混、挤出、冷却、造粒，即得内芯层的聚合物材料；所述双螺杆挤出机的共混、挤出温度为：一区170～180℃，二区180～190℃，三区190～200℃，四区200～210℃，五区210～220℃，机头210～230℃；螺杆转速：180～220r/min，喂料速度：2～10Hz，机头压力：2～10Hz。(3) The obtained premix is placed in a twin-screw extruder and sequentially melt-blended, extruded, cooled, and granulated to obtain the polymer material of the inner core layer; the blending of the twin-screw extruder, Extrusion temperature: zone 1 170-180°C, zone 2 180-190°C, zone 3 190-200°C, zone 4 200-210°C, zone 5 210-220°C, head 210-230°C; screw speed: 180～220r/min, feeding speed: 2～10Hz, head pressure: 2～10Hz.
所述外芯层制备出纳米二氧化硅改性的塑料光纤，具有抗挠曲性强、耐磨损性好、抗冲击性强的特点；外芯层材料的制备方法包括如下步骤：The outer core layer prepares a nano-silica modified plastic optical fiber, which has the characteristics of strong flexural resistance, good wear resistance, and strong impact resistance; the preparation method of the outer core layer material includes the following steps:
(1)在高速混合机里添加所述甲基丙烯酸五氟丙酯、四氟乙烯、三氟丙基甲基环三硅氧烷、乙烯基三乙氧基硅烷、甲基丙烯酰氧基硅烷、双苯甲酰基苯基氧化膦、α-羟烷基苯酮、纳米二氧化硅，进行搅拌10～20min，升温至100～110℃后，继续搅拌20～30min，得到预混料；(1) Add the pentafluoropropyl methacrylate, tetrafluoroethylene, trifluoropropylmethylcyclotrisiloxane, vinyltriethoxysilane, methacryloxysilane in a high-speed mixer , bisbenzoylphenyl phosphine oxide, α-hydroxyalkyl phenone, and nano silicon dioxide were stirred for 10-20 minutes, and after the temperature was raised to 100-110°C, the stirring was continued for 20-30 minutes to obtain a premix;
(2)采用单螺杆挤出机对预混料进行造粒，其造粒工艺条件如下：挤出机温度：180～280℃，切粒机转速：2～10.0Hz，喂料速度：2～10.0Hz，机头压力：5～10MPa。(2) Use a single-screw extruder to granulate the premix. The granulation process conditions are as follows: extruder temperature: 180-280°C, pelletizer speed: 2-10.0Hz, feeding speed: 2- 10.0Hz, head pressure: 5 ~ 10MPa.
将上述制备内芯层聚合物材料与外芯层聚合物材料用双机头挤出机制备本发明聚合物光纤，其制造工艺如下：The polymer optical fiber of the present invention is prepared by using the polymer material of the inner core layer and the polymer material of the outer core layer prepared above with a double-head extruder, and the manufacturing process is as follows:
利用两台冲击式挤出机，其中一台挤出机垂直放置用于挤出内芯层，另一台挤出机水平放置用于挤出外芯层，加热后经过一个共挤模头，然后，再经过冷却、牵引、卷曲等步骤完成，聚合物光纤直径为0.3mm。Using two impact extruders, one extruder is placed vertically to extrude the inner core layer, and the other extruder is placed horizontally to extrude the outer core layer. After heating, it passes through a co-extrusion die, Then, after cooling, pulling, crimping and other steps, the diameter of the polymer optical fiber is 0.3mm.
将上述制备聚合物光纤用如下方法进行编织：The above prepared polymer optical fiber is braided by the following method:
取所述聚合物光纤，以及棉/腈纶85/15的混纺纱，对混纺纱进行打蜡润滑处理，降低机器与纱线间作用力对纱线的机械损伤。使用3号手摇机，机速范围设定15～100mm/s，横机机头机速为织针速度的2～3倍。The polymer optical fiber and the blended yarn of cotton/acrylic fiber 85/15 are taken, and the blended yarn is waxed and lubricated to reduce the mechanical damage to the yarn caused by the force between the machine and the yarn. Use No. 3 hand-operated machine, the machine speed range is set at 15-100mm/s, and the machine head speed of the flat knitting machine is 2-3 times of the knitting needle speed.
选用线密度为120～300Tex的混纺线作为经纱，上述聚合物光纤作为纬纱，采用5mm的高亮度蓝光LED灯作为光源，织机继续织造时，在织物两端留出一定长度的聚合物光纤以便进行集束、切割处理，通过连接件将聚合物光纤与上述LED光源连接耦合。所编制的聚合物光纤织物具有如下的规格参数，经密度(根·(10cm)-1)为250，纬密度(根·(10cm)-1)为150～300，厚度为0.5～0.72mm。Select the blended yarn with a linear density of 120-300Tex as the warp yarn, the above-mentioned polymer optical fiber as the weft yarn, and use a 5mm high-brightness blue LED light as the light source. When the loom continues to weave, leave a certain length of polymer optical fiber at both ends of the fabric to facilitate Bundling and cutting are carried out, and the polymer optical fiber is connected and coupled to the above-mentioned LED light source through a connector. The prepared polymer fiber optic fabric has the following specification parameters, the warp density (root·(10cm)-1 ) is 250, the weft density (root·(10cm)-1 ) is 150-300, and the thickness is 0.5-0.72mm.
本发明的积极有益效果：Positive beneficial effect of the present invention:
本发明聚合物光纤不易断裂，由其制成的发光织物具有高亮度且使用寿命长的特点。The polymer optical fiber of the invention is not easy to break, and the luminous fabric made of it has the characteristics of high brightness and long service life.
(1)本发明所用聚对苯二甲酸丁二醇酯(PBT)的主链是由每个重复单元为刚性苯环和柔性脂肪醇连接起来的饱和线性分子组成，分子的高度几何规整性和刚性部分使整个体系具有高的机械强度、突出的耐化学试剂性、耐热性和优良的电性能；且PBT分子中没有侧链，结构对称，满足紧密堆砌的要求；在整个塑料光纤的体系中PBT作为骨架提供了非常好的机械稳定性。(1) The main chain of polybutylene terephthalate (PBT) used in the present invention is to be that each repeating unit is the saturated linear molecule that rigid benzene ring and flexible aliphatic alcohol link together, and the high geometrical regularity of molecule and The rigid part makes the whole system have high mechanical strength, outstanding chemical resistance, heat resistance and excellent electrical properties; and there is no side chain in the PBT molecule, the structure is symmetrical, and it meets the requirements of close packing; in the whole plastic optical fiber system Medium PBT provides very good mechanical stability as a backbone.
(2)本发明所用环氧化反式-1，4-聚异戊二烯(ETPI)，是1，4反式聚异戊二烯(TPI)经环氧改性制成，使TPI中的反式结构保留下来，从而保持了TPI优良的性能，如高硬度、生热低、耐磨性能和动态疲劳性能优良的特点；另一方面，环氧化的结果，增加了TPI分子的极性，使其亲水能力加强，从而起到降低摩擦的作用；ETPI为结晶性高聚物，分子链在晶区内有序排列，其活动性降低，具有较高的耐热氧老化性能，经环氧化后合成的ETPI，仍然有部分的TPI结晶，这些微晶分布在聚丙烯酸乙酯、丙烯酸正丁酯、聚碳酸酯和聚对苯二甲酸丁二醇酯中起到物理交联的作用。(2) Epoxidized trans-1,4-polyisoprene (ETPI) used in the present invention is 1,4 trans polyisoprene (TPI) is made through epoxy modification, makes TPI The trans structure is retained, thereby maintaining the excellent performance of TPI, such as high hardness, low heat generation, excellent wear resistance and dynamic fatigue performance; on the other hand, the result of epoxidation increases the extreme ETPI is a crystalline high polymer, its molecular chains are arranged in an orderly manner in the crystal region, its mobility is reduced, and it has high heat and oxygen aging resistance. The ETPI synthesized after epoxidation still has some TPI crystallization, and these crystallites are distributed in polyethylacrylate, n-butyl acrylate, polycarbonate and polybutylene terephthalate for physical crosslinking role.
(3)本发明所用SBS与丙烯酸聚合物、聚碳酸酯会形成互穿网络结构穿插在聚对苯二甲酸丁二醇酯中，不仅增加聚对苯二甲酸丁二醇酯、丙烯酸聚合物和聚碳酸酯的相容性，而且有效改善整个体系的力学性能如拉伸屈服应力、屈服伸长率等。(3) SBS used in the present invention and acrylic acid polymer, polycarbonate can form interpenetrating network structure and intersperse in polybutylene terephthalate, not only increase polybutylene terephthalate, acrylic acid polymer and The compatibility of polycarbonate, and effectively improve the mechanical properties of the entire system such as tensile yield stress, yield elongation, etc.
(4)本发明所用甲基丙烯酰氧基硅烷，在加热的条件下甲基丙烯酰氧基硅烷中不饱键(-C＝C-和-C＝O-)会与聚丙烯酸乙酯、丙烯酸正丁酯、聚碳酸酯、ETPI、SBS的不饱和键如(-C＝C-)进行接枝反应，提高它们之间的相容性；而且甲基丙烯酰氧基硅烷中的硅烷会使整个体系具有更为优异的弹性、拉伸性能，可弯曲度。(4) For the methacryloxysilane used in the present invention, the unsaturated bonds (-C=C- and -C=O-) in the methacryloxysilane will react with polyethylacrylate, Unsaturated bonds such as (-C=C-) of n-butyl acrylate, polycarbonate, ETPI, SBS carry out grafting reaction to improve the compatibility between them; and the silane in methacryloxysilane will Make the whole system have more excellent elasticity, tensile properties, and bendability.
具体实施方式Detailed ways
以下描述用于揭露本发明以使本领域技术人员能够实现本发明。以下描述中的优选实施例只作为举例，本领域技术人员可以想到其他显而易见的变型。The following description serves to disclose the present invention to enable those skilled in the art to carry out the present invention. The preferred embodiments described below are only examples, and those skilled in the art can devise other obvious variations.
实施例1～3为聚合物光纤内芯层材料的制备方法。Embodiments 1-3 are preparation methods of polymer optical fiber inner core material.
实施例1Example 1
内芯层材料的制备方法包括如下步骤：The preparation method of inner core layer material comprises the following steps:
(1)在高速混合机里添加5重量份的聚对苯二甲酸丁二醇酯、2重量份的ETPI、3重量份的SBS，进行搅拌10min；(1) Add 5 parts by weight of polybutylene terephthalate, 2 parts by weight of ETPI, and SBS of 3 parts by weight in a high-speed mixer, and stir for 10 minutes;
(2)将60重量份的聚丙烯酸乙酯、10重量份的丙烯酸正丁酯、8重量份的聚碳酸酯、8重量份的甲基丙烯酰氧基硅烷、2重量份的乙烯基硅烷、1重量份的芳酰基膦氧化物、1重量份的2，4-二羟基二苯甲酮加入上述的高速混合机，升温至100℃，继续搅拌20min，得到预混物；(2) Polyethyl acrylate of 60 parts by weight, n-butyl acrylate of 10 parts by weight, polycarbonate of 8 parts by weight, methacryloxysilane of 8 parts by weight, vinylsilane of 2 parts by weight, Add 1 part by weight of aroylphosphine oxide and 1 part by weight of 2,4-dihydroxybenzophenone into the above-mentioned high-speed mixer, raise the temperature to 100°C, and continue stirring for 20 minutes to obtain a premix;
(3)将所得预混物置于双螺杆挤出机中进行熔融共混、挤出、冷却、造粒，即得内芯层材料，其折射率为1.53；双螺杆挤出机的共混、挤出温度为：一区180℃，二区190℃，三区200℃，四区210℃，五区220℃，机头230℃；螺杆转速220r/min，喂料速度：5Hz，机头压力：5Hz。(3) The gained premix is placed in a twin-screw extruder for melt blending, extruding, cooling, and granulation to obtain the inner core layer material with a refractive index of 1.53; the blending of the twin-screw extruder, Extrusion temperature: Zone 1 180°C, Zone 2 190°C, Zone 3 200°C, Zone 4 210°C, Zone 5 220°C, Head 230°C; Screw speed 220r/min, Feeding speed: 5Hz, Head pressure : 5Hz.
实施例2Example 2
内芯层材料的制备方法包括如下步骤：The preparation method of inner core layer material comprises the following steps:
(1)在高速混合机里添加6重量份的聚对苯二甲酸丁二醇酯、4重量份的ETPI、5重量份的SBS，进行搅拌10min；(1) Add 6 parts by weight of polybutylene terephthalate, 4 parts by weight of ETPI, and SBS of 5 parts by weight in a high-speed mixer, and stir for 10 minutes;
(2)将55重量份的聚丙烯酸乙酯、10重量份的丙烯酸正丁酯、10重量份的聚碳酸酯、6重量份的甲基丙烯酰氧基硅烷、2重量份的乙烯基硅烷、1重量份的芳酰基膦氧化物、1重量份的2，4-二羟基二苯甲酮加入上述的高速混合机，升温至120℃，继续搅拌15min，得到预混物；(2) Polyethyl acrylate of 55 parts by weight, n-butyl acrylate of 10 parts by weight, polycarbonate of 10 parts by weight, methacryloxysilane of 6 parts by weight, vinylsilane of 2 parts by weight, Add 1 part by weight of aroylphosphine oxide and 1 part by weight of 2,4-dihydroxybenzophenone into the above-mentioned high-speed mixer, raise the temperature to 120°C, and continue stirring for 15 minutes to obtain a premix;
(3)将所得预混物置于双螺杆挤出机中进行熔融共混、挤出、冷却、造粒，即得内芯层材料，其折射率为1.55；双螺杆挤出机的共混、挤出温度为：一区175℃，二区180℃，三区195℃，四区200℃，五区210℃，机头210℃；螺杆转速210r/min，喂料速度：8Hz，机头压力：8Hz。(3) The gained premix is placed in a twin-screw extruder for melt blending, extruding, cooling, and granulation to obtain the inner core layer material with a refractive index of 1.55; the blending of the twin-screw extruder, Extrusion temperature: zone 1 175°C, zone 2 180°C, zone 3 195°C, zone 4 200°C, zone 5 210°C, head 210°C; screw speed 210r/min, feeding speed: 8Hz, head pressure : 8Hz.
实施例3Example 3
内芯层材料的制备方法包括如下步骤：The preparation method of inner core layer material comprises the following steps:
(1)在高速混合机里添加4重量份的聚对苯二甲酸丁二醇酯、3重量份的ETPI、3重量份的SBS，进行搅拌10min；(1) Add 4 parts by weight of polybutylene terephthalate, 3 parts by weight of ETPI, and SBS of 3 parts by weight in a high-speed mixer, and stir for 10 minutes;
(2)将50重量份的聚丙烯酸乙酯、15重量份的丙烯酸正丁酯、15重量份的聚碳酸酯、5重量份的甲基丙烯酰氧基硅烷、3重量份的乙烯基硅烷、1重量份的芳酰基膦氧化物、2重量份的2，4-二羟基二苯甲酮加入上述的高速混合机，升温至110℃，继续搅拌20min，得到预混物；(2) Polyethyl acrylate of 50 parts by weight, n-butyl acrylate of 15 parts by weight, polycarbonate of 15 parts by weight, methacryloxysilane of 5 parts by weight, vinylsilane of 3 parts by weight, Add 1 part by weight of aroylphosphine oxide and 2 parts by weight of 2,4-dihydroxybenzophenone into the above-mentioned high-speed mixer, raise the temperature to 110°C, and continue stirring for 20 minutes to obtain a premix;
(3)将所得预混物置于双螺杆挤出机中进行熔融共混、挤出、冷却、造粒，即得内芯层材料，其折射率为1.54；双螺杆挤出机的共混、挤出温度为：一区180℃，二区185℃，三区195℃，四区210℃，五区220℃，机头220℃；螺杆转速200r/min，喂料速度：10Hz，机头压力：5Hz。(3) The gained premix is placed in a twin-screw extruder for melt blending, extruding, cooling, and granulation to obtain the inner core layer material with a refractive index of 1.54; the blending of the twin-screw extruder, Extrusion temperature: zone 1 180°C, zone 2 185°C, zone 3 195°C, zone 4 210°C, zone 5 220°C, head 220°C; screw speed 200r/min, feeding speed: 10Hz, head pressure : 5Hz.
性能测试：Performance Testing:
实施例4～5为聚合物光纤外芯层材料的制备方法。Embodiments 4-5 are preparation methods of polymer optical fiber outer core material.
实施例4Example 4
(1)在高速混合机里添加60重量份的甲基丙烯酸五氟丙酯、10重量份的四氟乙烯、10重量份的三氟丙基甲基环三硅氧烷、6重量份的乙烯基三乙氧基硅烷、6重量份的甲基丙烯酰氧基硅烷、1重量份的双苯甲酰基苯基氧化膦、1重量份的α-羟烷基苯酮、6重量份的纳米二氧化硅，搅拌10min，升温至110℃，继续搅拌30min，得到预混料；(1) Add 60 parts by weight of pentafluoropropyl methacrylate, 10 parts by weight of tetrafluoroethylene, 10 parts by weight of trifluoropropylmethylcyclotrisiloxane, 6 parts by weight of ethylene Triethoxysilane, 6 parts by weight of methacryloxysilane, 1 part by weight of bisbenzoylphenylphosphine oxide, 1 part by weight of α-hydroxyalkyl phenone, 6 parts by weight of nanometer Silicon oxide, stirred for 10 minutes, heated up to 110°C, and continued to stir for 30 minutes to obtain a premix;
(2)采用单螺杆挤出机对所得预混料进行造粒，即得外芯层材料，折射率为1.45，其造粒工艺条件如下：挤出机温度：220℃，切粒机转速：5Hz，喂料速度：5Hz，机头压力：5MPa。(2) Use a single-screw extruder to granulate the obtained premixed material to obtain the outer core layer material with a refractive index of 1.45. The granulation process conditions are as follows: extruder temperature: 220°C, pelletizer speed: 5Hz, feeding speed: 5Hz, head pressure: 5MPa.
实施例5Example 5
(1)在高速混合机里添加65重量份的甲基丙烯酸五氟丙酯、8重量份的四氟乙烯、7重量份的三氟丙基甲基环三硅氧烷、5重量份的乙烯基三乙氧基硅烷、5重量份的甲基丙烯酰氧基硅烷、2重量份的双苯甲酰基苯基氧化膦、1重量份的α-羟烷基苯酮、7重量份的纳米二氧化硅，搅拌20min，升温至100℃，继续搅拌25min，得到预混料；(1) Add 65 parts by weight of pentafluoropropyl methacrylate, 8 parts by weight of tetrafluoroethylene, 7 parts by weight of trifluoropropylmethylcyclotrisiloxane, 5 parts by weight of ethylene Triethoxysilane, 5 parts by weight of methacryloxysilane, 2 parts by weight of bisbenzoylphenyl phosphine oxide, 1 part by weight of α-hydroxyalkyl phenone, 7 parts by weight of nanometer Silicon oxide, stirred for 20 minutes, heated up to 100°C, and continued to stir for 25 minutes to obtain a premix;
(2)采用单螺杆挤出机对所得预混料进行造粒，即得外芯层材料，折射率为1.46，其造粒工艺条件如下：挤出机温度：230℃，切粒机转速：8Hz，喂料速度：8Hz，机头压力：10MPa。(2) Use a single-screw extruder to granulate the obtained premixed material to obtain the outer core layer material with a refractive index of 1.46. The granulation process conditions are as follows: extruder temperature: 230°C, pelletizer speed: 8Hz, feeding speed: 8Hz, head pressure: 10MPa.
实施例6Example 6
实施6为实施例1制备的内芯层材料与实施例4制备的外芯层材料制备出聚合物光纤的方法，将制备的内芯层材料与外芯层材料用双机头挤出机制备，其制造工艺如下：用两台冲击式挤出机，其中一台垂直放置，用于挤出内芯层，另一台挤出机水平放置用于挤出外芯层，加热后经过一个共挤模头，后经过冷却、牵引、卷曲等步骤完成，聚合物光纤直径为0.3mm。Implementation 6 is a method for preparing a polymer optical fiber from the inner core layer material prepared in Example 1 and the outer core layer material prepared in Example 4, and preparing the prepared inner core layer material and outer core layer material with a double-head extruder , the manufacturing process is as follows: use two impact extruders, one of which is placed vertically to extrude the inner core layer, and the other extruder is placed horizontally to extrude the outer core layer, after heating, it passes through a common Extrude the die head, and then complete the steps of cooling, pulling, curling, etc., and the diameter of the polymer optical fiber is 0.3mm.
实施例7～8为实施例6制备的聚合物光纤用作编织工艺。Examples 7-8 are the polymer optical fibers prepared in Example 6 used in the braiding process.
实施例7Example 7
将上述制备聚合物光纤用如下方法进行编织：The above prepared polymer optical fiber is braided by the following method:
选取上述制备的0.3mm的聚合物光纤和棉/腈纶85/15的混纺纱，在编织前对混纺纱进行打蜡润滑处理，降低机器与纱线间作用力对纱线的机械损伤。使用3号手摇机，机速范围设定50mm/s，横机机头机速为织针速度的3倍。The 0.3mm polymer optical fiber and cotton/acrylic 85/15 blended yarn prepared above were selected, and the blended yarn was waxed and lubricated before weaving to reduce the mechanical damage to the yarn caused by the force between the machine and the yarn. Use No. 3 hand-operated machine, set the machine speed range to 50mm/s, and the machine head speed of the flat knitting machine is 3 times of the knitting needle speed.
选用线密度为200Tex的混纺线作为经纱，上述0.3mm的聚合物光纤作为纬纱，采用5mm的高亮度蓝光LED灯作为光源，采用织机继续拧织造时，在织物两端留出一定长度的聚合物光纤以便进行集束、切割处理，通过连接件将聚合物光纤与上述LED光源连接耦合。所编制的聚合物光纤织物具有如下的规格参数，经密度(根·(10cm)-1)为250，纬密度(根·(10cm)-1)为230，厚度为0.62mm。。The blended yarn with a linear density of 200Tex is used as the warp yarn, the above-mentioned 0.3mm polymer optical fiber is used as the weft yarn, and a 5mm high-brightness blue LED light is used as the light source. The object optical fiber is used for bundling and cutting, and the polymer optical fiber is connected and coupled with the above-mentioned LED light source through a connector. The prepared polymer optical fiber fabric has the following specification parameters, the warp density (root·(10cm)-1 ) is 250, the weft density (root·(10cm)-1 ) is 230, and the thickness is 0.62mm. .
实施例8Example 8
将上述制备聚合物光纤用如下方法进行编织：The above prepared polymer optical fiber is braided by the following method:
选取上述制备的0.3mm的聚合物光纤和棉/腈纶85/15的混纺纱，在编织前对混纺纱进行打蜡润滑处理，降低机器与纱线间作用力对纱线的机械损伤。使用3号手摇机，机速范围设定40mm/s，横机机头机速为织针速度的2.5倍。The 0.3mm polymer optical fiber and cotton/acrylic 85/15 blended yarn prepared above were selected, and the blended yarn was waxed and lubricated before weaving to reduce the mechanical damage to the yarn caused by the force between the machine and the yarn. Use No. 3 hand-operated machine, set the machine speed range to 40mm/s, and the machine head speed of the flat knitting machine is 2.5 times of the knitting needle speed.
选用线密度为250Tex的混纺线作为经纱，上述0.3mm的聚合物光纤作为纬纱，采用5mm的高亮度蓝光LED灯作为光源，采用织机继续拧织造时，在织物两端留出一定长度的聚合物光纤以便进行集束、切割处理，通过连接件将聚合物光纤与上述LED光源连接耦合。所编制的聚合物光纤织物具有如下的规格参数，经密度(根·(10cm)-1)为250，纬密度(根·(10cm)-1)为260，厚度为0.64mm。The blended yarn with a linear density of 250Tex is used as the warp yarn, the above-mentioned 0.3mm polymer optical fiber is used as the weft yarn, and the 5mm high-brightness blue LED lamp is used as the light source. The object optical fiber is used for bundling and cutting, and the polymer optical fiber is connected and coupled with the above-mentioned LED light source through a connector. The prepared polymer optical fiber fabric has the following specification parameters, the warp density (root·(10cm)-1 ) is 250, the weft density (root·(10cm)-1 ) is 260, and the thickness is 0.64mm.
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是本发明的原理，在不脱离本发明精神和范围的前提下本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明的范围内。本发明要求的保护范围由所附的权利要求书及其等同物界定。The basic principles, main features and advantages of the present invention have been shown and described above. Those skilled in the art should understand that the present invention is not limited by the above-mentioned embodiments. What are described in the above-mentioned embodiments and the description are only the principles of the present invention. Variations and improvements, which fall within the scope of the claimed invention. The scope of protection required by the present invention is defined by the appended claims and their equivalents.
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510590599.3ACN105133084B (en) | 2015-09-10 | 2015-09-10 | Polymer optical fiber for light-emitting fabric, light-emitting fabric and manufacturing method thereof |
| CN201710947150.7ACN107881595A (en) | 2015-09-10 | 2015-09-10 | A kind of luminous fabric |
| CN201710947149.4ACN107794598A (en) | 2015-09-10 | 2015-09-10 | A kind of manufacture method of luminous fabric |
| Application Number | Priority Date | Filing Date | Title |
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| CN201510590599.3ACN105133084B (en) | 2015-09-10 | 2015-09-10 | Polymer optical fiber for light-emitting fabric, light-emitting fabric and manufacturing method thereof |
| Application Number | Title | Priority Date | Filing Date |
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| CN201710947150.7ADivisionCN107881595A (en) | 2015-09-10 | 2015-09-10 | A kind of luminous fabric |
| CN201710947149.4ADivisionCN107794598A (en) | 2015-09-10 | 2015-09-10 | A kind of manufacture method of luminous fabric |
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| CN105133084Atrue CN105133084A (en) | 2015-12-09 |
| CN105133084B CN105133084B (en) | 2017-12-26 |
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| CN201510590599.3AActiveCN105133084B (en) | 2015-09-10 | 2015-09-10 | Polymer optical fiber for light-emitting fabric, light-emitting fabric and manufacturing method thereof |
| CN201710947150.7APendingCN107881595A (en) | 2015-09-10 | 2015-09-10 | A kind of luminous fabric |
| CN201710947149.4APendingCN107794598A (en) | 2015-09-10 | 2015-09-10 | A kind of manufacture method of luminous fabric |
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| CN201710947150.7APendingCN107881595A (en) | 2015-09-10 | 2015-09-10 | A kind of luminous fabric |
| CN201710947149.4APendingCN107794598A (en) | 2015-09-10 | 2015-09-10 | A kind of manufacture method of luminous fabric |
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| CN110408161A (en)* | 2019-09-12 | 2019-11-05 | 东莞市兴茂橡塑科技有限公司 | A kind of high permeability and high elasticity material, its preparation method and application |
| CN110549705A (en)* | 2019-09-04 | 2019-12-10 | 苏州大学 | Polymer optical fiber and luminous fabric |
| CN110670169A (en)* | 2019-09-04 | 2020-01-10 | 苏州大学 | A kind of preparation method of polymer optical fiber |
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| TR01 | Transfer of patent right | Effective date of registration:20200518 Address after:221600 Jiangsu city in Xuzhou province Xiao Peixian Economic Development Zone on the south side of the road Patentee after:Xuzhou Guohong Packaging Co., Ltd. Address before:Ganquan road Shushan District of Hefei City, Anhui Province, 230000 West hillock road to the South Wild Garden commercial office building room B-1512 Patentee before:ANHUI YINGLONG INDUSTRIAL DESIGN Co.,Ltd. | |
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| PE01 | Entry into force of the registration of the contract for pledge of patent right | Denomination of invention:Polymer optical fiber for luminous fabric, luminous fabric and manufacturing method thereof Effective date of registration:20210201 Granted publication date:20171226 Pledgee:Bank of China Limited Peixian sub branch Pledgor:Xuzhou Guohong Packaging Co.,Ltd. Registration number:Y2021980000912 | |
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