技术领域Technical Field
本发明涉及热塑性聚氨酯树脂及膜，详细而言，涉及热塑性聚氨酯树脂、及包含该热塑性聚氨酯树脂的膜。The present invention relates to a thermoplastic polyurethane resin and a film, and more particularly to a thermoplastic polyurethane resin and a film comprising the thermoplastic polyurethane resin.
背景技术Background technique
热塑性聚氨酯树脂(TPU)通常为通过多异氰酸酯、高分子量多元醇及低分子量多元醇的反应得到的橡胶弹性体。热塑性聚氨酯树脂例如被成型为膜状，作为用于保护汽车的涂装面的保护膜(Paint Protection Film(PPF))等来使用。Thermoplastic polyurethane resin (TPU) is generally a rubber elastic body obtained by reacting polyisocyanate, high molecular weight polyol and low molecular weight polyol. Thermoplastic polyurethane resin is formed into a film and used as a paint protection film (PPF) for protecting the painted surface of an automobile.
作为保护膜，例如，提出了包含使多元醇及多异氰酸酯反应而得到的TPU层的多层聚氨酯保护膜，另外，提出了使用己内酯多元醇作为多元醇，进而提出了使用二环己基甲烷二异氰酸酯作为多异氰酸酯(例如，参见专利文献1。)。As a protective film, for example, a multilayer polyurethane protective film including a TPU layer obtained by reacting a polyol and a polyisocyanate has been proposed. In addition, the use of caprolactone polyol as the polyol and further the use of dicyclohexylmethane diisocyanate as the polyisocyanate have been proposed (for example, see Patent Document 1).
现有技术文献Prior art literature
专利文献Patent Literature
专利文献1：日本特表2010-505663公报Patent Document 1: Japanese Patent Publication No. 2010-505663
发明内容Summary of the invention
发明所要解决的课题Problems to be solved by the invention
另一方面，对于保护膜，根据用途，要求伸缩特性(恢复力)及耐热性。在这一点上，上述的多层聚氨酯保护膜存在耐热性不充分这样的不良情况。On the other hand, protective films are required to have stretch characteristics (restoration force) and heat resistance depending on the application. In this regard, the above-mentioned multilayer polyurethane protective films have the disadvantage of insufficient heat resistance.
本发明为兼具伸缩特性(恢复力)及耐热性的热塑性聚氨酯树脂、及包含该热塑性聚氨酯树脂的膜。The present invention provides a thermoplastic polyurethane resin having both stretching characteristics (restoring force) and heat resistance, and a film comprising the thermoplastic polyurethane resin.
用于解决课题的手段Means for solving problems
本发明[1]包括热塑性聚氨酯树脂，其包含下述反应产物：包含以60摩尔％以上99.5摩尔％以下的比例含有反式体的1,4-双(异氰酸酯基甲基)环己烷的多异氰酸酯成分、与包含于25℃为液态的非晶性聚碳酸酯二醇、及碳原子数2～6的低分子量二醇的多元醇成分的反应产物。The present invention [1] includes a thermoplastic polyurethane resin comprising the following reaction product: a polyisocyanate component comprising 1,4-bis(isocyanatomethyl)cyclohexane containing a trans isomer at a ratio of 60 mol % to 99.5 mol %; and a polyol component comprising an amorphous polycarbonate diol that is liquid at 25° C. and a low molecular weight diol having 2 to 6 carbon atoms.
本发明[2]包括上述[1]所述的热塑性聚氨酯树脂，其中，利用差示扫描量热测定法(DSC法)测得的、160℃以上时的前述热塑性聚氨酯树脂的熔融峰的热量为15J/g以下。The present invention [2] comprises the thermoplastic polyurethane resin according to the above [1], wherein the heat of the melting peak of the thermoplastic polyurethane resin at 160° C. or higher as measured by differential scanning calorimetry (DSC) is 15 J/g or less.
本发明[3]包括上述[1]或[2]所述的热塑性聚氨酯树脂，其中，利用差示扫描量热测定法(DSC法)测得的、160℃以上时的前述热塑性聚氨酯树脂的熔融峰的热量为0.1J/g以上。The present invention [3] comprises the thermoplastic polyurethane resin described in [1] or [2] above, wherein the heat of the melting peak of the thermoplastic polyurethane resin at 160° C. or higher as measured by differential scanning calorimetry (DSC) is 0.1 J/g or more.
本发明[4]包括膜，其包含上述[1]～[3]中任一项所述的热塑性聚氨酯树脂。The present invention [4] includes a film comprising the thermoplastic polyurethane resin according to any one of the above [1] to [3].
发明效果Effects of the Invention
就本发明的热塑性聚氨酯树脂及膜而言，作为原料成分，包含：包含以60摩尔％以上99.5摩尔％以下的比例含有反式体的1,4-双(异氰酸酯基甲基)环己烷的多异氰酸酯成分；和，包含于25℃为液态的非晶性聚碳酸酯二醇、及碳原子数2～6的低分子量二醇的多元醇成分。The thermoplastic polyurethane resin and film of the present invention include, as raw material components: a polyisocyanate component including 1,4-bis(isocyanatemethyl)cyclohexane containing a trans isomer at a ratio of 60 mol % to 99.5 mol %; and a polyol component including an amorphous polycarbonate diol that is liquid at 25° C. and a low molecular weight diol having 2 to 6 carbon atoms.
即，作为原料成分，使用了结晶性比较高的1,4-双(异氰酸酯基甲基)环己烷、通过硬链段使结晶性提高的低分子量二醇、和结晶性比较低的非晶性聚碳酸酯二醇。That is, as raw material components, 1,4-bis(isocyanatemethyl)cyclohexane having relatively high crystallinity, a low molecular weight diol having improved crystallinity due to a hard segment, and amorphous polycarbonate diol having relatively low crystallinity are used.
因此，本发明的热塑性聚氨酯树脂及膜能够均衡性良好地调整聚氨酯结构的凝集性，能够均衡性良好地兼具源于凝集性的高度的耐热性、和源于凝集性的低下的伸缩特性。Therefore, the thermoplastic polyurethane resin and film of the present invention can adjust the cohesion of the polyurethane structure in a well-balanced manner, and can have both high heat resistance due to the cohesion and low expansion and contraction characteristics due to the cohesion in a well-balanced manner.
具体实施方式Detailed ways
本发明的热塑性聚氨酯树脂通过使多异氰酸酯成分、与多元醇成分反应而得到。换言之，热塑性聚氨酯树脂是通过作为原料成分的多异氰酸酯成分与多元醇成分的反应得到的反应产物。The thermoplastic polyurethane resin of the present invention is obtained by reacting a polyisocyanate component with a polyol component. In other words, the thermoplastic polyurethane resin is a reaction product obtained by reacting a polyisocyanate component as a raw material component with a polyol component.
多异氰酸酯成分包含1,4-双(异氰酸酯基甲基)环己烷作为必需成分。The polyisocyanate component contains 1,4-bis(isocyanatemethyl)cyclohexane as an essential component.
1,4-双(异氰酸酯基甲基)环己烷中存在顺式-1,4-双(异氰酸酯基甲基)环己烷(以下，记为顺式1,4体。)、及反式-1,4-双(异氰酸酯基甲基)环己烷(以下，记为反式1,4体。)的立体异构体。1,4-bis(isocyanatemethyl)cyclohexane has stereoisomers of cis-1,4-bis(isocyanatemethyl)cyclohexane (hereinafter referred to as cis-1,4-isomer) and trans-1,4-bis(isocyanatemethyl)cyclohexane (hereinafter referred to as trans-1,4-isomer).
本发明中，1,4-双(异氰酸酯基甲基)环己烷以规定比例含有反式1,4体(反式体)。In the present invention, 1,4-bis(isocyanatemethyl)cyclohexane contains a trans-1,4-isomer (trans-isomer) at a predetermined ratio.
更具体而言，相对于1,4-双(异氰酸酯基甲基)环己烷的总摩尔而言，反式1,4体(反式体)的含有比例为60摩尔％以上，优选为70摩尔％以上，更优选为75摩尔％以上，进一步优选为80摩尔％以上，为99.5摩尔％以下，优选为99摩尔％以下，更优选为96摩尔％以下，进一步优选为90摩尔％以下。More specifically, the content ratio of the trans-1,4-bis(isocyanatemethyl)cyclohexane is 60 mol% or more, preferably 70 mol% or more, more preferably 75 mol% or more, and further preferably 80 mol% or more, and is 99.5 mol% or less, preferably 99 mol% or less, more preferably 96 mol% or less, and further preferably 90 mol% or less, relative to the total moles of 1,4-bis(isocyanatemethyl)cyclohexane.
换言之，1,4-双(异氰酸酯基甲基)环己烷的反式1,4体及顺式1,4体的总量为100摩尔％，因此，相对于1,4-双(异氰酸酯基甲基)环己烷的总摩尔而言，顺式1,4体(顺式体)的含有比例为0.5摩尔％以上，优选为1摩尔％以上，更优选为4摩尔％以上，进一步优选为10摩尔％以上，为40摩尔％以下，优选为30摩尔％以下，更优选为25摩尔％以下，进一步优选为20摩尔％以下。In other words, the total amount of the trans-1,4-isomer and the cis-1,4-isomer of 1,4-bis(isocyanatemethyl)cyclohexane is 100 mol %, and therefore, the content ratio of the cis-1,4-isomer (cis-isomer) relative to the total moles of 1,4-bis(isocyanatemethyl)cyclohexane is 0.5 mol % or more, preferably 1 mol % or more, more preferably 4 mol % or more, further preferably 10 mol % or more, and 40 mol % or less, preferably 30 mol % or less, more preferably 25 mol % or less, and further preferably 20 mol % or less.
若反式1,4体的含有比例为上述下限以上，则能够实现耐热性的提高。When the content ratio of the trans-1,4 isomer is not less than the above lower limit, the heat resistance can be improved.
1,4-双(异氰酸酯基甲基)环己烷可以通过例如国际公开WO2009/051114号公报、国际公开WO2019/069802号公报等中记载的方法等来制造。1,4-bis(isocyanatemethyl)cyclohexane can be produced by the method described in, for example, International Publication No. WO2009/051114 and International Publication No. WO2019/069802.
另外，对于1,4-双(异氰酸酯基甲基)环己烷而言，在不妨碍本发明的优异效果的范围内，也可以以改性物的形式制备。1,4-bis(isocyanatemethyl)cyclohexane may be prepared as a modified product within a range not impairing the excellent effects of the present invention.
作为1,4-双(异氰酸酯基甲基)环己烷的改性物，可举出例如1,4-双(异氰酸酯基甲基)环己烷的多聚物(二聚物(例如，脲二酮改性物等)、三聚物(例如，异氰脲酸酯改性物、亚氨基噁二嗪二酮改性物等)等)、缩二脲改性物(例如，通过1,4-双(异氰酸酯基甲基)环己烷与水的反应生成的缩二脲改性物等)、脲基甲酸酯改性物(例如，通过1,4-双(异氰酸酯基甲基)环己烷与1元醇或2元醇的反应生成的脲基甲酸酯改性物等)、多元醇改性物(例如，通过1,4-双(异氰酸酯基甲基)环己烷与3元醇的反应生成的多元醇改性物(加成物)等)、噁二嗪三酮改性物(例如，通过1,4-双(异氰酸酯基甲基)环己烷与二氧化碳的反应生成的噁二嗪三酮等)、碳二亚胺改性物(例如，通过1,4-双(异氰酸酯基甲基)环己烷的脱羧缩合反应生成的碳二亚胺改性物等)等。它们可以单独使用或者并用2种以上。Examples of modified products of 1,4-bis(isocyanate methyl)cyclohexane include polymers of 1,4-bis(isocyanate methyl)cyclohexane (dimers (e.g., uretdione-modified products), trimers (e.g., isocyanurate-modified products, iminooxadiazinedione-modified products), biuret-modified products (e.g., biuret-modified products produced by reaction of 1,4-bis(isocyanate methyl)cyclohexane with water), allophanate-modified products (e.g., products produced by reaction of 1,4-bis(isocyanate methyl)cyclohexane with water), and the like. Allophanate modified products produced by reaction of monohydric alcohol or dihydric alcohol, etc.), polyol modified products (for example, polyol modified products (adducts) produced by reaction of 1,4-bis(isocyanate methyl)cyclohexane and trihydric alcohol, etc.), oxadiazinetrione modified products (for example, oxadiazinetrione produced by reaction of 1,4-bis(isocyanate methyl)cyclohexane and carbon dioxide, etc.), carbodiimide modified products (for example, carbodiimide modified products produced by decarboxylation condensation reaction of 1,4-bis(isocyanate methyl)cyclohexane, etc.), etc. These can be used alone or in combination of two or more.
作为1,4-双(异氰酸酯基甲基)环己烷，优选可举出1,4-双(异氰酸酯基甲基)环己烷的单体(monomer)。As 1,4-bis(isocyanatemethyl)cyclohexane, preferably, a monomer of 1,4-bis(isocyanatemethyl)cyclohexane is used.
若多异氰酸酯成分包含上述的1,4-双(异氰酸酯基甲基)环己烷，则能够通过源于1,4-双(异氰酸酯基甲基)环己烷的对称结构的结晶性来提高热塑性聚氨酯树脂的耐热性。即，多异氰酸酯成分不含以规定比例包含反式体的1,4-双(异氰酸酯基甲基)环己烷的情况下，有时多异氰酸酯成分的结晶性不充分，热塑性聚氨酯树脂(后述)的凝集性降低，耐热性差。与此相对，若多异氰酸酯成分包含上述的1,4-双(异氰酸酯基甲基)环己烷，则源于1,4-双(异氰酸酯基甲基)环己烷的对称结构而能够提高多异氰酸酯成分的结晶性，能够提高热塑性聚氨酯树脂的凝集性，因此能够实现耐热性的提高。If the polyisocyanate component contains the above-mentioned 1,4-bis(isocyanate methyl)cyclohexane, the heat resistance of the thermoplastic polyurethane resin can be improved by the crystallinity of the symmetrical structure derived from 1,4-bis(isocyanate methyl)cyclohexane. That is, when the polyisocyanate component does not contain 1,4-bis(isocyanate methyl)cyclohexane containing a trans isomer at a predetermined ratio, the crystallinity of the polyisocyanate component is sometimes insufficient, the cohesion of the thermoplastic polyurethane resin (described later) is reduced, and the heat resistance is poor. In contrast, if the polyisocyanate component contains the above-mentioned 1,4-bis(isocyanate methyl)cyclohexane, the crystallinity of the polyisocyanate component can be improved due to the symmetrical structure of 1,4-bis(isocyanate methyl)cyclohexane, the cohesion of the thermoplastic polyurethane resin can be improved, and thus the heat resistance can be improved.
另外，对于多异氰酸酯成分而言，在不妨碍本发明的优异效果的范围内，可以含有其他多异氰酸酯(除1,4-双(异氰酸酯基甲基)环己烷以外的多异氰酸酯)作为任选成分。Furthermore, the polyisocyanate component may contain other polyisocyanates (polyisocyanates other than 1,4-bis(isocyanatemethyl)cyclohexane) as an optional component within a range not impairing the excellent effects of the present invention.
作为其他多异氰酸酯，可举出例如脂肪族多异氰酸酯、芳香族多异氰酸酯、芳香脂肪族多异氰酸酯等。As other polyisocyanates, aliphatic polyisocyanates, aromatic polyisocyanates, aromatic aliphatic polyisocyanates, etc. are mentioned, for example.
作为脂肪族多异氰酸酯，可举出例如乙二异氰酸酯、三亚甲基二异氰酸酯、四亚甲基二异氰酸酯、五亚甲基二异氰酸酯(PDI)、六亚甲基二异氰酸酯(HDI)、八亚甲基二异氰酸酯、九亚甲基二异氰酸酯、2,2’-二甲基戊烷二异氰酸酯、2,2,4-三甲基己烷二异氰酸酯、十亚甲基二异氰酸酯、丁烯二异氰酸酯、1,3-丁二烯-1,4-二异氰酸酯、2,4,4-三甲基六亚甲基二异氰酸酯、1,6,11-十一亚甲基三异氰酸酯、1,3,6-六亚甲基三异氰酸酯、1,8-二异氰酸酯基-4-异氰酸酯基甲基辛烷、2,5,7-三甲基-1,8-二异氰酸酯基-5-异氰酸酯基甲基辛烷、双(异氰酸酯基乙基)碳酸酯、双(异氰酸酯基乙基)醚、1,4-丁二醇二丙基醚-ω,ω’-二异氰酸酯、赖氨酸异氰酸酯基甲基酯、赖氨酸三异氰酸酯、2-异氰酸酯基乙基-2,6-二异氰酸酯基己酸酯、2-异氰酸酯基丙基-2,6-二异氰酸酯基己酸酯、双(4-异氰酸酯基-亚正丁基)季戊四醇、2,6-二异氰酸酯基甲基己酸酯等链状脂肪族二异氰酸酯等。Examples of the aliphatic polyisocyanate include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butylene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undemethylene triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8 -Diisocyanate-4-isocyanatemethyloctane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanatemethyloctane, bis(isocyanateethyl)carbonate, bis(isocyanateethyl)ether, 1,4-butanediol dipropyl ether-ω,ω'-diisocyanate, lysine isocyanatemethyl ester, lysine triisocyanate, 2-isocyanateethyl-2,6-diisocyanatehexanoate, 2-isocyanatepropyl-2,6-diisocyanatehexanoate, bis(4-isocyanate-n-butylene)pentaerythritol, 2,6-diisocyanatemethylhexanoate and the like chain aliphatic diisocyanates, etc.
另外，脂肪族多异氰酸酯中包括脂环族多异氰酸酯(将1,4-双(异氰酸酯基甲基)环己烷除外。)。In addition, aliphatic polyisocyanates include alicyclic polyisocyanates (excluding 1,4-bis(isocyanatemethyl)cyclohexane).
作为脂环族多异氰酸酯(将1,4-双(异氰酸酯基甲基)环己烷除外。)，可举出例如1,3-双(异氰酸酯基甲基)环己烷、异佛尔酮二异氰酸酯(IPDI)、反式,反式-、反式,顺式-、及顺式,顺式-二环己基甲烷二异氰酸酯及它们的混合物(氢化MDI、H12MDI)、1,3-或1,4-环己烷二异氰酸酯及它们的混合物、1,3-或1,4-双(异氰酸酯基乙基)环己烷、甲基环己烷二异氰酸酯、2,2’-二甲基二环己基甲烷二异氰酸酯、二聚酸二异氰酸酯、2,5-二异氰酸酯基甲基双环〔2,2,1〕-庚烷、作为其异构体的2,6-二异氰酸酯基甲基双环〔2,2,1〕-庚烷(NBDI)、2-异氰酸酯基甲基2-(3-异氰酸酯基丙基)-5-异氰酸酯基甲基双环-〔2,2,1〕-庚烷、2-异氰酸酯基甲基-2-(3-异氰酸酯基丙基)-6-异氰酸酯基甲基双环-〔2,2,1〕-庚烷、2-异氰酸酯基甲基3-(3-异氰酸酯基丙基)-5-(2-异氰酸酯基乙基)-双环-〔2,2,1〕-庚烷、2-异氰酸酯基甲基3-(3-异氰酸酯基丙基)-6-(2-异氰酸酯基乙基)-双环-〔2,2,1〕-庚烷、2-异氰酸酯基甲基2-(3-异氰酸酯基丙基)-5-(2-异氰酸酯基乙基)-双环-〔2,2,1〕-庚烷、2-异氰酸酯基甲基2-(3-异氰酸酯基丙基)-6-(2-异氰酸酯基乙基)-双环-〔2,2,1〕-庚烷等脂环族二异氰酸酯等。Examples of the alicyclic polyisocyanate (excluding 1,4-bis(isocyanatemethyl)cyclohexane) include 1,3-bis(isocyanatemethyl)cyclohexane, isophorone diisocyanate (IPDI), trans, trans-, trans, cis-, and cis, cis-dicyclohexylmethane diisocyanate, and mixtures thereof (hydrogenated MDI, H12 MDI), 1,3- or 1,4-cyclohexane diisocyanate and mixtures thereof, 1,3- or 1,4-bis(isocyanatoethyl)cyclohexane, methylcyclohexane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, dimer acid diisocyanate, 2,5-diisocyanatomethylbicyclo〔2,2,1〕-heptane, 2,6-diisocyanatomethylbicyclo〔2,2,1〕-heptane (NBDI) as its isomer, 2-isocyanatomethyl 2-(3-isocyanatopropyl)-5-isocyanatomethylbicyclo-〔2,2,1〕-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl alicyclic diisocyanates such as ester methyl bicyclo-〔2,2,1〕-heptane, 2-isocyanate methyl 3-(3-isocyanate propyl)-5-(2-isocyanate ethyl)-bicyclo-〔2,2,1〕-heptane, 2-isocyanate methyl 3-(3-isocyanate propyl)-6-(2-isocyanate ethyl)-bicyclo-〔2,2,1〕-heptane, 2-isocyanate methyl 2-(3-isocyanate propyl)-5-(2-isocyanate ethyl)-bicyclo-〔2,2,1〕-heptane, and 2-isocyanate methyl 2-(3-isocyanate propyl)-6-(2-isocyanate ethyl)-bicyclo-〔2,2,1〕-heptane.
作为芳香族多异氰酸酯，可举出例如2,4-甲苯二异氰酸酯及2,6-甲苯二异氰酸酯、以及这些甲苯二异氰酸酯的异构体混合物(TDI)、4,4’-二苯基甲烷二异氰酸酯、2,4’-二苯基甲烷二异氰酸酯及2,2’-二苯基甲烷二异氰酸酯、以及这些二苯基甲烷二异氰酸酯的任意的异构体混合物(MDI)、甲苯胺二异氰酸酯(TODI)、对苯二异氰酸酯、萘二异氰酸酯(NDI)等芳香族二异氰酸酯等。Examples of the aromatic polyisocyanate include aromatic diisocyanates such as 2,4-toluene diisocyanate and 2,6-toluene diisocyanate, and isomeric mixtures of these toluene diisocyanates (TDI), 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate and 2,2′-diphenylmethane diisocyanate, and isomeric mixtures of these diphenylmethane diisocyanates (MDI), toluidine diisocyanate (TODI), p-phenylene diisocyanate, and naphthalene diisocyanate (NDI).
作为芳香脂肪族多异氰酸酯，可举出例如1,3-或1,4-苯二甲撑二异氰酸酯或其混合物(XDI)、1,3-或1,4-四甲基苯二甲撑二异氰酸酯或其混合物(TMXDI)等芳香脂肪族二异氰酸酯等。Examples of the aromatic aliphatic polyisocyanate include aromatic aliphatic diisocyanates such as 1,3- or 1,4-xylylenediisocyanate or a mixture thereof (XDI), and 1,3- or 1,4-tetramethylxylylenediisocyanate or a mixture thereof (TMXDI).
这些其他多异氰酸酯可以单独使用或者并用2种以上。These other polyisocyanates may be used alone or in combination of two or more.
另外，对于其他多异氰酸酯而言，在不妨碍本发明的优异效果的范围内，也可以以改性物的形式制备。作为改性物，可举出例如多聚物(脲二酮改性物、异氰脲酸酯改性物、亚氨基噁二嗪二酮改性物等)、缩二脲改性物、脲基甲酸酯改性物、多元醇改性物、噁二嗪三酮改性物、碳二亚胺改性物等。它们可以单独使用或者并用2种以上。In addition, for other polyisocyanates, within the scope of not hindering the excellent effect of the present invention, it is also possible to prepare in the form of a modified product. As a modified product, for example, polymers (uretdione modified products, isocyanurate modified products, imino oxadiazinedione modified products, etc.), biuret modified products, allophanate modified products, polyol modified products, oxadiazinedione modified products, carbodiimide modified products, etc. can be enumerated. They can be used alone or in combination of more than two.
其他多异氰酸酯的含有比例可在不损害本发明的优异效果的范围内适当地选择。The content ratio of other polyisocyanates can be appropriately selected within a range that does not impair the excellent effects of the present invention.
更具体而言，相对于多异氰酸酯成分的总量而言，其他多异氰酸酯的含有比例例如低于50摩尔％，优选为30摩尔％以下，更优选为10摩尔％以下，进一步优选为5摩尔％以下，尤其优选为0摩尔％。More specifically, the content of other polyisocyanates relative to the total amount of the polyisocyanate component is, for example, less than 50 mol %, preferably 30 mol % or less, more preferably 10 mol % or less, further preferably 5 mol % or less, and particularly preferably 0 mol %.
换言之，相对于多异氰酸酯成分的总量而言，1,4-双(异氰酸酯基甲基)环己烷(包括1,4-双(异氰酸酯基甲基)环己烷的改性物。)的含有比例例如高于50摩尔％，优选为70摩尔％以上，更优选为90摩尔％以上，进一步优选为95摩尔％以上，尤其优选为100摩尔％。In other words, the content ratio of 1,4-bis(isocyanatemethyl)cyclohexane (including modified products of 1,4-bis(isocyanatemethyl)cyclohexane) relative to the total amount of the polyisocyanate component is, for example, higher than 50 mol %, preferably higher than 70 mol %, more preferably higher than 90 mol %, further preferably higher than 95 mol %, and particularly preferably 100 mol %.
即，多异氰酸酯成分优选单独含有1,4-双(异氰酸酯基甲基)环己烷。That is, the polyisocyanate component preferably contains 1,4-bis(isocyanatemethyl)cyclohexane alone.
多元醇成分为在分子中含有2个以上羟基的化合物。The polyol component is a compound containing two or more hydroxyl groups in the molecule.
多元醇成分含有分子量高于400的高分子量多元醇、和分子量为400以下的低分子量多元醇作为必需成分。The polyol component contains, as essential components, a high molecular weight polyol having a molecular weight higher than 400 and a low molecular weight polyol having a molecular weight of 400 or less.
需要说明的是，多元醇成分具有分子量分布的情况下，可采用数均分子量。另外，在这样的情况下，数均分子量可以通过基于GPC法的测定、多元醇成分的各成分的羟值及配方来确定(以下是同样的)。It should be noted that, when the polyol component has a molecular weight distribution, the number average molecular weight can be used. In addition, in such a case, the number average molecular weight can be determined by measurement based on the GPC method, the hydroxyl value of each component of the polyol component and the formulation (the same applies below).
高分子量多元醇为在分子中具有2个以上羟基、并且高于400的化合物。The high molecular weight polyol is a compound having two or more hydroxyl groups in the molecule and having a molecular weight of more than 400.
高分子量多元醇含有于25℃为液态(液体状态)的非晶性聚碳酸酯二醇作为必需成分。换言之，多元醇成分含有非晶性聚碳酸酯二醇作为必需成分。The high molecular weight polyol contains, as an essential component, an amorphous polycarbonate diol that is liquid (liquid state) at 25° C. In other words, the polyol component contains, as an essential component, an amorphous polycarbonate diol.
非晶性聚碳酸酯二醇是平均羟基数为2的非晶性聚碳酸酯多元醇。对于非晶性聚碳酸酯二醇而言，所谓非晶性，表示于25℃为液态(利用E型粘度计测定的25℃时的粘度为500000mPa·s以下)。The amorphous polycarbonate diol is an amorphous polycarbonate polyol having an average hydroxyl number of 2. The amorphous nature of the amorphous polycarbonate diol means that it is liquid at 25° C. (the viscosity at 25° C. measured by an E-type viscometer is 500,000 mPa·s or less).
非晶性聚碳酸酯二醇例如可以通过将以2元醇为引发剂的碳酸亚乙酯的开环聚合物用作为改性剂的2元醇进行改性而得到。Amorphous polycarbonate diol can be obtained, for example, by modifying a ring-opening polymer of ethylene carbonate using a divalent alcohol as an initiator with a divalent alcohol as a modifier.
在碳酸亚乙酯的开环聚合物中，关于作为引发剂的2元醇，可举出例如乙二醇、1,3-丙二醇、1,4-丁二醇(丁烷二醇)、1,5-戊二醇、1,6-己二醇、1,8-辛二醇等碳原子数2～8的直链状烷烃二醇、例如二乙二醇、三乙二醇等碳原子数4～8的直链状醚二醇等直链状2元醇等。这些2元醇可以单独使用或者并用2种以上。In the ring-opening polymer of ethylene carbonate, examples of the dihydric alcohol as an initiator include linear dihydric alcohols such as ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol (butanediol), 1,5-pentanediol, 1,6-hexanediol, and 1,8-octanediol, and linear dihydric alcohols such as linear ether diols having 4 to 8 carbon atoms such as diethylene glycol and triethylene glycol. These dihydric alcohols may be used alone or in combination of two or more.
关于作为引发剂的2元醇，优选可举出直链状2元醇，更优选可举出碳原子数2～8的直链状烷烃二醇。As the divalent alcohol as the initiator, preferably, a linear divalent alcohol is used, and more preferably, a linear alkane diol having 2 to 8 carbon atoms is used.
在碳酸亚乙酯的开环聚合物中，关于作为改性剂的2元醇，可举出例如直链状2元醇、支链状2元醇。作为直链状2元醇，可选择与上述的作为引发剂的2元醇不同种类的直链状2元醇。In the ring-opening polymer of ethylene carbonate, the dihydric alcohol as a modifier includes, for example, linear dihydric alcohols and branched dihydric alcohols. As the linear dihydric alcohol, a different type of linear dihydric alcohol from the above-mentioned dihydric alcohol as an initiator can be selected.
作为改性剂的直链状2元醇只要与作为引发剂的2元醇为不同种类即可，但优选可举出碳原子数比作为引发剂的2元醇多的直链状2元醇。更具体而言，可举出例如1,4-丁二醇、1,5-戊二醇、1,6-己二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇等碳原子数4～10的直链状烷烃二醇等。这些直链状2元醇可以单独使用或者并用2种以上。The linear diol as the modifier may be of a different type from the diol as the initiator, but preferably a linear diol having more carbon atoms than the diol as the initiator can be used. More specifically, linear alkane diols having 4 to 10 carbon atoms such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol can be used. These linear diols can be used alone or in combination of two or more.
另外，关于作为改性剂的支链状2元醇，可举出例如3-甲基-1,5-戊二醇、2-甲基-1,3-丙二醇、2,2-二甲基-1,3-丙二醇等碳原子数4～10的支链状烷烃二醇等。这些支链状2元醇可以单独使用或者并用2种以上。Examples of branched diols as modifiers include branched alkane diols having 4 to 10 carbon atoms, such as 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, and 2,2-dimethyl-1,3-propanediol. These branched diols may be used alone or in combination of two or more.
这些作为改性剂的2元醇可以单独使用或者并用2种以上。These dihydric alcohols as the modifier may be used alone or in combination of two or more.
关于作为改性剂的2元醇，优选可举出碳原子数比作为引发剂的2元醇多的直链状2元醇、或支链状2元醇，更优选可举出支链状2元醇，进一步优选可举出3-甲基-1,5-戊二醇。The dihydric alcohol as the modifier is preferably a linear dihydric alcohol or a branched dihydric alcohol having a larger number of carbon atoms than the dihydric alcohol as the initiator, more preferably a branched dihydric alcohol, and still more preferably 3-methyl-1,5-pentanediol.
需要说明的是，利用2元醇对碳酸亚乙酯的开环聚合物进行改性的方法没有特别限制，可采用已知的方法。例如，以2元醇为引发剂，利用已知的方法使碳酸亚乙酯进行开环聚合后，使所得到的开环聚合物、与作为改性剂的2元醇进一步进行共聚。It should be noted that the method for modifying the ring-opening polymer of ethylene carbonate using a dihydric alcohol is not particularly limited, and a known method can be used. For example, using a dihydric alcohol as an initiator, ethylene carbonate is subjected to ring-opening polymerization using a known method, and then the obtained ring-opening polymer is further copolymerized with a dihydric alcohol as a modifier.
这些非晶性聚碳酸酯二醇可以单独使用或者并用2种以上。即，可以使用单独种类的非晶性聚碳酸酯二醇，另外，也可以并用例如数均分子量、作为引发剂的2元醇、作为改性剂的2元醇等彼此不同的2种以上的非晶性聚碳酸酯二醇。These amorphous polycarbonate diols can be used alone or in combination of two or more. That is, a single type of amorphous polycarbonate diol can be used, and in addition, two or more amorphous polycarbonate diols different from each other such as number average molecular weight, dihydric alcohol as initiator, dihydric alcohol as modifier, etc. can also be used in combination.
从实现伸缩特性的提高的观点考虑，非晶性聚碳酸酯二醇的数均分子量(并用2种以上的情况下，为它们的混合物的平均分子量)高于400，优选为500以上，更优选为1000以上，进一步优选为1300以上，尤其优选为1500以上，例如为10000以下，优选为8000以下，更优选为5000以下，进一步优选为3000以下，尤其优选为2000以下。From the viewpoint of achieving improved stretch properties, the number average molecular weight of the amorphous polycarbonate diol (when two or more types are used, the average molecular weight of their mixture) is higher than 400, preferably 500 or more, more preferably 1000 or more, further preferably 1300 or more, and particularly preferably 1500 or more, for example, 10000 or less, preferably 8000 or less, more preferably 5000 or less, further preferably 3000 or less, and particularly preferably 2000 or less.
高分子量多元醇也可以单独含有非晶性聚碳酸酯二醇，但根据需要，也可以含有其他高分子量多元醇(除非晶性聚碳酸酯二醇以外的高分子量多元醇)。The high molecular weight polyol may contain the amorphous polycarbonate diol alone, but may contain other high molecular weight polyols (high molecular weight polyols other than the amorphous polycarbonate diol) as necessary.
即，高分子量多元醇可以含有其他高分子量多元醇(除非晶性聚碳酸酯二醇以外的高分子量多元醇)作为任选成分。That is, the high molecular weight polyol may contain other high molecular weight polyol (high molecular weight polyol other than the amorphous polycarbonate diol) as an optional component.
作为其他高分子量多元醇，可举出例如数均分子量高于400并且为10000以下的高分子量多元醇(将非晶性聚碳酸酯二醇除外。)，更具体而言，可举出结晶性聚碳酸酯多元醇、平均羟基数为3以上的非晶性聚碳酸酯多元醇、聚醚多元醇、聚酯多元醇、聚己内酯多元醇、聚氨酯多元醇等。这些其他高分子量多元醇可以单独使用或者并用2种以上。As other high molecular weight polyols, for example, high molecular weight polyols having a number average molecular weight higher than 400 and not higher than 10,000 (excluding amorphous polycarbonate diols), more specifically, crystalline polycarbonate polyols, amorphous polycarbonate polyols having an average hydroxyl number of 3 or more, polyether polyols, polyester polyols, polycaprolactone polyols, polyurethane polyols, etc. These other high molecular weight polyols may be used alone or in combination of two or more.
作为其他高分子量多元醇，优选可举出结晶性聚碳酸酯多元醇。As other high molecular weight polyols, preferably, crystalline polycarbonate polyols are mentioned.
结晶性聚碳酸酯多元醇是于25℃为固态(固体状态)的聚碳酸酯多元醇。The crystalline polycarbonate polyol is a polycarbonate polyol which is in a solid state at 25°C.
作为结晶性聚碳酸酯多元醇，可举出例如上述的以2元醇为引发剂的碳酸亚乙酯的开环聚合物等。这些结晶性聚碳酸酯多元醇可以单独使用或者并用2种以上。Examples of the crystalline polycarbonate polyol include the above-mentioned ring-opening polymer of ethylene carbonate using a divalent alcohol as an initiator, etc. These crystalline polycarbonate polyols may be used alone or in combination of two or more.
需要说明的是，以2元醇为引发剂的碳酸亚乙酯的开环聚合方法没有特别限制，可采用已知的方法。It should be noted that the method for ring-opening polymerization of ethylene carbonate using a divalent alcohol as an initiator is not particularly limited, and a known method can be used.
从实现伸缩特性及耐热性的兼得的观点考虑，结晶性聚碳酸酯多元醇的数均分子量高于400，优选为500以上，更优选为1000以上，进一步优选为1300以上，尤其优选为1500以上，例如为10000以下，优选为8000以下，更优选为5000以下，进一步优选为3000以下，尤其优选为2000以下。From the viewpoint of achieving both stretch properties and heat resistance, the number average molecular weight of the crystalline polycarbonate polyol is higher than 400, preferably 500 or more, more preferably 1000 or more, further preferably 1300 or more, particularly preferably 1500 or more, for example, 10000 or less, preferably 8000 or less, more preferably 5000 or less, further preferably 3000 or less, and particularly preferably 2000 or less.
另外，结晶性聚碳酸酯多元醇的每1分子的平均羟基数例如为1.8以上，优选为2以上，例如为4以下，优选为3以下，尤其优选为2。The average number of hydroxyl groups per molecule of the crystalline polycarbonate polyol is, for example, 1.8 or more, preferably 2 or more, for example, 4 or less, preferably 3 or less, and particularly preferably 2 or less.
其他高分子量多元醇的配合比例可在不损害本发明的优异效果的范围内适当地设定。The blending ratio of other high molecular weight polyols can be appropriately set within a range that does not impair the excellent effects of the present invention.
即，作为其他高分子量多元醇，过量使用结晶性比较高的高分子量多元醇(结晶性聚碳酸酯多元醇、聚己内酯多元醇等)时，存在凝集性变高、引起伸缩特性(恢复力)的降低的情况。That is, when an excessive amount of a high molecular weight polyol having relatively high crystallinity (crystalline polycarbonate polyol, polycaprolactone polyol, etc.) is used as other high molecular weight polyol, the cohesiveness may increase, and the stretching property (restoring force) may be reduced.
因此，其他高分子量多元醇(结晶性聚碳酸酯多元醇等)的比例可调整至能够维持优异的伸缩特性的范围。Therefore, the ratio of other high molecular weight polyols (crystalline polycarbonate polyol, etc.) can be adjusted to a range in which excellent stretching characteristics can be maintained.
更具体而言，相对于高分子量多元醇的总摩尔而言，其他高分子量多元醇(结晶性聚碳酸酯多元醇、聚己内酯多元醇等)的含有比例例如为60摩尔％以下，优选为50摩尔％以下，通常为0摩尔％以上，尤其优选为0摩尔％。More specifically, the content ratio of other high molecular weight polyols (crystalline polycarbonate polyol, polycaprolactone polyol, etc.) relative to the total moles of the high molecular weight polyol is, for example, 60 mol% or less, preferably 50 mol% or less, usually 0 mol% or more, particularly preferably 0 mol%.
换言之，相对于高分子量多元醇的总摩尔而言，非晶性聚碳酸酯二醇的含有比例例如为40摩尔％以上，优选为50摩尔％以上，通常为100摩尔％以下，尤其优选为100摩尔％。In other words, the content ratio of the amorphous polycarbonate diol relative to the total moles of the high molecular weight polyol is, for example, 40 mol % or more, preferably 50 mol % or more, and usually 100 mol % or less, particularly preferably 100 mol %.
即，高分子量多元醇尤其优选不含其他高分子量多元醇，而单独含有非晶性聚碳酸酯二醇。That is, it is particularly preferred that the high molecular weight polyol contains no other high molecular weight polyol and contains only the amorphous polycarbonate diol.
从实现伸缩特性及耐热性的兼得的观点考虑，高分子量多元醇的分子量(数均分子量)高于400，优选为500以上，更优选为1000以上，进一步优选为1300以上，尤其优选为1500以上，例如为10000以下，优选为8000以下，更优选为5000以下，进一步优选为3000以下，尤其优选为2000以下。From the viewpoint of achieving both stretch properties and heat resistance, the molecular weight (number average molecular weight) of the high molecular weight polyol is higher than 400, preferably 500 or more, more preferably 1000 or more, further preferably 1300 or more, particularly preferably 1500 or more, for example, 10000 or less, preferably 8000 or less, more preferably 5000 or less, further preferably 3000 or less, and particularly preferably 2000 or less.
低分子量多元醇是在分子中具有2个以上羟基、并且分子量为400以下、例如为50以上的化合物。The low molecular weight polyol is a compound having two or more hydroxyl groups in the molecule and having a molecular weight of 400 or less, for example, 50 or more.
低分子量多元醇含有碳原子数2～6的低分子量二醇作为必需成分。换言之，多元醇成分含有碳原子数2～6的低分子量二醇作为必需成分。The low molecular weight polyol contains, as an essential component, a low molecular weight diol having 2 to 6 carbon atoms. In other words, the polyol component contains, as an essential component, a low molecular weight diol having 2 to 6 carbon atoms.
碳原子数2～6的低分子量二醇是1分子中的碳原子数为2以上6以下、并且在1分子中具有2个羟基的分子量为400以下的化合物。The low molecular weight diol having 2 to 6 carbon atoms is a compound having 2 to 6 carbon atoms in one molecule, having two hydroxyl groups in one molecule and having a molecular weight of 400 or less.
作为碳原子数2～6的低分子量二醇，可举出例如乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇(1,4-BD)、1,3-丁二醇、1,2-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇、3-甲基-1,5-戊二醇、2,2-二甲基-1,3-丙二醇等碳原子数2～6的烷烃二醇(碳原子数2～6的亚烷基二醇)、例如二乙二醇、三乙二醇、二丙二醇等碳原子数2～6的醚二醇、例如1,4-二羟基-2-丁烯等碳原子数2～6的烯烃二醇、例如1,3-或1,4-环己二醇及它们的混合物等。它们可以单独使用或者并用2种以上。Examples of the low molecular weight diol having 2 to 6 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol (1,4-BD), 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol and other alkanediols having 2 to 6 carbon atoms (alkylene glycols having 2 to 6 carbon atoms), such as diethylene glycol, triethylene glycol, and dipropylene glycol, such ether diols having 2 to 6 carbon atoms, such as 1,4-dihydroxy-2-butene and other olefin diols, such as 1,3- or 1,4-cyclohexanediol, and mixtures thereof. These may be used alone or in combination of two or more.
碳原子数2～6的低分子量二醇中，碳原子数为2以上，优选为3以上，为6以下，优选为5以下，尤其优选为4。The low molecular weight diol having 2 to 6 carbon atoms has 2 or more, preferably 3 or more, and 6 or less, preferably 5 or less, and particularly preferably 4 carbon atoms.
碳原子数2～6的低分子量二醇的分子量例如为50以上，优选为70以上，为400以下，优选为300以下。The molecular weight of the low molecular weight diol having 2 to 6 carbon atoms is, for example, 50 or more, preferably 70 or more, and 400 or less, preferably 300 or less.
作为碳原子数2～6的低分子量二醇，从实现耐热性的提高的观点考虑，优选可举出碳原子数2～6的烷烃二醇，更优选可举出1,4-丁二醇。As the low molecular weight diol having 2 to 6 carbon atoms, preferably, from the viewpoint of achieving improvement in heat resistance, an alkane diol having 2 to 6 carbon atoms is used, and more preferably, 1,4-butanediol is used.
低分子量多元醇也可以单独含有碳原子数2～6的低分子量二醇，但根据需要，也可以含有其他低分子量多元醇(除碳原子数2～6的低分子量二醇以外的低分子量多元醇)。The low molecular weight polyol may contain a low molecular weight diol having 2 to 6 carbon atoms alone, but may contain other low molecular weight polyols (low molecular weight polyols other than the low molecular weight diol having 2 to 6 carbon atoms) as necessary.
即，低分子量多元醇可以含有其他低分子量多元醇(除碳原子数2～6的低分子量二醇以外的低分子量多元醇)作为任选成分。That is, the low molecular weight polyol may contain other low molecular weight polyols (low molecular weight polyols other than the low molecular weight diol having 2 to 6 carbon atoms) as an optional component.
其他低分子量多元醇例如可举出在分子中具有2个以上羟基、并且分子量为50以上400以下的、除碳原子数2～6的低分子量二醇以外的化合物。Examples of other low molecular weight polyols include compounds having two or more hydroxyl groups in the molecule and having a molecular weight of 50 to 400, excluding low molecular weight diols having 2 to 6 carbon atoms.
作为其他低分子量多元醇，可举出例如碳原子数7以上的低分子量二醇、3元以上的低分子量多元醇等。Examples of other low molecular weight polyols include low molecular weight diols having 7 or more carbon atoms and low molecular weight polyols having a valence of 3 or more.
作为碳原子数7以上的低分子量二醇，可举出例如1,8-辛二醇、1,9-壬二醇等碳原子数7～20的烷烃-1,2-二醇、2,6-二甲基-1-辛烯-3,8-二醇、1,3-或1,4-环己烷二甲醇及它们的混合物、氢化双酚A、双酚A等碳原子数7以上的2元醇。这些碳原子数7以上的低分子量二醇可以单独使用或者并用2种以上。Examples of the low molecular weight diol having 7 or more carbon atoms include alkane-1,2-diol having 7 to 20 carbon atoms such as 1,8-octanediol and 1,9-nonanediol, 2,6-dimethyl-1-octene-3,8-diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, and dihydric alcohol having 7 or more carbon atoms such as hydrogenated bisphenol A and bisphenol A. These low molecular weight diols having 7 or more carbon atoms may be used alone or in combination of two or more.
3元以上的低分子量多元醇是分子量为400以下、并且在1分子中具有3个以上羟基的化合物，可举出例如甘油、2-甲基-2-羟基甲基-1,3-丙二醇、2,4-二羟基-3-羟基甲基戊烷、1,2,6-己烷三醇、三羟甲基丙烷、2,2-双(羟基甲基)-3-丁醇等3元醇(低分子量三醇)、例如四羟甲基甲烷(季戊四醇)、双甘油等4元醇、例如木糖醇等5元醇、例如山梨糖醇、甘露醇、蒜糖醇、艾杜糖醇、卫矛醇、阿卓糖醇、肌醇、二季戊四醇等6元醇、例如鳄梨糖醇等7元醇、例如蔗糖等8元醇等。这些3元以上的低分子量多元醇可以单独使用或者并用2种以上。The trivalent or higher low molecular weight polyol is a compound having a molecular weight of 400 or less and having three or more hydroxyl groups in one molecule, and examples thereof include trivalent alcohols (low molecular weight triols) such as glycerol, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, trimethylolpropane, and 2,2-bis(hydroxymethyl)-3-butanol, tetravalent alcohols such as tetrahydroxymethylmethane (pentaerythritol) and diglycerol, pentavalent alcohols such as xylitol, hexavalent alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, and dipentaerythritol, heptavalent alcohols such as avocado, and octavalent alcohols such as sucrose. These trivalent or higher low molecular weight polyols may be used alone or in combination of two or more.
这些其他低分子量多元醇可以单独使用或者并用2种以上。These other low molecular weight polyols may be used alone or in combination of two or more.
其他低分子量多元醇的分子量例如为50以上，优选为70以上，为400以下，优选为300以下。The molecular weight of other low molecular weight polyols is, for example, 50 or more, preferably 70 or more, and 400 or less, preferably 300 or less.
其他低分子量多元醇的配合比例可在不损害本发明的优异效果的范围内适当地设定。The blending ratio of other low molecular weight polyols can be appropriately set within a range that does not impair the excellent effects of the present invention.
更具体而言，相对于低分子量多元醇的总量100质量份而言，其他低分子量多元醇(除碳原子数2～6的低分子量二醇以外的低分子量多元醇)的含有比例例如为50质量份以下，优选为20质量份以下，更优选为10质量份以下，尤其优选为0质量份。More specifically, the content ratio of other low molecular weight polyols (low molecular weight polyols other than low molecular weight diols having 2 to 6 carbon atoms) relative to 100 parts by mass of the total amount of the low molecular weight polyols is, for example, 50 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and particularly preferably 0 parts by mass.
换言之，相对于低分子量多元醇的总量100质量份而言，碳原子数2～6的低分子量二醇的含有比例例如为50质量份以上，优选为80质量份以上，更优选为90质量份以上，尤其优选为100质量份。In other words, the content of the low molecular weight diol having 2 to 6 carbon atoms is, for example, 50 parts by mass or more, preferably 80 parts by mass or more, more preferably 90 parts by mass or more, and particularly preferably 100 parts by mass, relative to 100 parts by mass of the total amount of the low molecular weight polyol.
即，低分子量多元醇优选不含其他低分子量多元醇(除碳原子数2～6的低分子量二醇以外的低分子量多元醇)，而单独含有碳原子数2～6的低分子量二醇。That is, the low molecular weight polyol preferably contains no other low molecular weight polyol (low molecular weight polyol other than the low molecular weight diol having 2 to 6 carbon atoms) and contains only the low molecular weight diol having 2 to 6 carbon atoms.
而且，多元醇成分如上文所述含有作为高分子量多元醇的非晶性聚碳酸酯二醇、和作为低分子量多元醇的碳原子数2～6的低分子量二醇作为必需成分，优选由非晶性聚碳酸酯二醇、和碳原子数2～6的低分子量二醇形成。As described above, the polyol component contains as essential components amorphous polycarbonate diol as a high molecular weight polyol and a low molecular weight diol having 2 to 6 carbon atoms as a low molecular weight polyol, and is preferably composed of amorphous polycarbonate diol and a low molecular weight diol having 2 to 6 carbon atoms.
多元醇成分中，关于高分子量多元醇和低分子量多元醇的含有比例，相对于它们的总量而言，高分子量多元醇例如为20摩尔％以上，优选为30摩尔％以上，例如为95摩尔％以下，优选为90摩尔％以下，更优选为70摩尔％以下，进一步优选低于50摩尔％，尤其优选为40摩尔以下。另外，低分子量多元醇例如为5摩尔％以上，优选为10摩尔％以上，更优选为30摩尔％以上，进一步优选高于50摩尔％，尤其优选为60摩尔％以上，例如为80摩尔％以下，优选为70摩尔％以下。In the polyol component, regarding the content ratio of the high molecular weight polyol and the low molecular weight polyol, the high molecular weight polyol is, for example, 20 mol% or more, preferably 30 mol% or more, for example, 95 mol% or less, preferably 90 mol% or less, more preferably 70 mol% or less, further preferably less than 50 mol%, particularly preferably 40 mol% or less, and the low molecular weight polyol is, for example, 5 mol% or more, preferably 10 mol% or more, more preferably 30 mol% or more, further preferably more than 50 mol%, particularly preferably 60 mol% or more, for example, 80 mol% or less, preferably 70 mol% or less.
而且，热塑性聚氨酯树脂可以通过使多异氰酸酯成分与多元醇成分反应而得到。Furthermore, the thermoplastic polyurethane resin can be obtained by reacting a polyisocyanate component with a polyol component.
更具体而言，该方法中，使上述的多异氰酸酯成分与上述的多元醇成分反应(反应工序)。More specifically, in this method, the above-mentioned polyisocyanate component and the above-mentioned polyol component are reacted (reaction step).
为了使上述各成分(多异氰酸酯成分、多元醇成分)反应，可采用例如一次完成法、预聚物法等已知的方法。从提高各种物性的观点考虑，优选采用预聚物法。In order to react the above-mentioned components (polyisocyanate component, polyol component), a known method such as a one-shot method and a prepolymer method can be adopted. From the viewpoint of improving various physical properties, the prepolymer method is preferably adopted.
具体而言，预聚物法中，首先，使包含1,4-双(异氰酸酯基甲基)环己烷的多异氰酸酯成分、与包含非晶性聚碳酸酯多元醇的高分子量多元醇进行反应，合成异氰酸酯基封端预聚物(预聚物合成工序)。Specifically, in the prepolymer method, first, a polyisocyanate component containing 1,4-bis(isocyanatemethyl)cyclohexane and a high molecular weight polyol containing an amorphous polycarbonate polyol are reacted to synthesize an isocyanate group-terminated prepolymer (prepolymer synthesis step).
预聚物合成工序中，通过例如本体聚合、溶液聚合等聚合方法，使多异氰酸酯成分与高分子量多元醇反应。In the prepolymer synthesis step, a polyisocyanate component and a high molecular weight polyol are reacted by a polymerization method such as bulk polymerization or solution polymerization.
本体聚合中，例如，在氮气流下，使多异氰酸酯成分与高分子量多元醇在反应温度例如为50℃以上、例如为250℃以下、优选为200℃以下的条件下进行例如0.5小时以上、例如15小时以下的反应。In bulk polymerization, for example, a polyisocyanate component and a high molecular weight polyol are reacted under a nitrogen stream at a reaction temperature of, for example, 50° C. or higher, for example, 250° C. or lower, preferably 200° C. or lower, for example, 0.5 hour or longer, for example, 15 hours or shorter.
溶液聚合中，在有机溶剂中加入多异氰酸酯成分及高分子量多元醇，在反应温度例如为50℃以上、例如为120℃以下、优选为100℃以下的条件下进行例如0.5小时以上、例如15小时以下的反应。In solution polymerization, a polyisocyanate component and a high molecular weight polyol are added to an organic solvent and reacted at a reaction temperature of, for example, 50° C. or higher, for example, 120° C. or lower, preferably 100° C. or lower, for example, 0.5 hour or higher, for example, 15 hours or lower.
作为有机溶剂，可举出例如丙酮、甲基乙基酮、甲基异丁基酮、环己酮等酮类、例如乙腈等腈类、乙酸甲酯、乙酸乙酯、乙酸丁酯、乙酸异丁酯等烷基酯类、例如正己烷、正庚烷、辛烷等脂肪族烃类、例如环己烷、甲基环己烷等脂环族烃类、例如甲苯、二甲苯、乙基苯等芳香族烃类、例如甲基溶纤剂乙酸酯、乙基溶纤剂乙酸酯、甲基卡必醇乙酸酯、乙基卡必醇乙酸酯、乙二醇乙基醚乙酸酯、丙二醇甲基醚乙酸酯、乙酸3-甲基-3-甲氧基丁酯、3-乙氧基丙酸乙酯等二醇醚酯类、例如乙醚、四氢呋喃、二氧杂环己烷等醚类、例如氯甲烷、二氯甲烷、氯仿、四氯化碳、溴甲烷、二碘甲烷、二氯乙烷等卤代脂肪族烃类、例如N-甲基吡咯烷酮、二甲基甲酰胺、N,N’-二甲基乙酰胺、二甲基亚砜、六甲基膦酰胺等极性非质子类等。Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; nitriles such as acetonitrile; alkyl esters such as methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate; aliphatic hydrocarbons such as n-hexane, n-heptane, and octane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; methyl cellosolve acetate, ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, Glycol ether esters such as ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethers such as diethyl ether, tetrahydrofuran, dioxane, halogenated aliphatic hydrocarbons such as methyl chloride, dichloromethane, chloroform, carbon tetrachloride, methyl bromide, diiodomethane, dichloroethane, polar aprotic hydrocarbons such as N-methylpyrrolidone, dimethylformamide, N,N'-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphonamide, etc., etc.
另外，上述的聚合反应中，根据需要，可以添加例如胺类、有机金属化合物等已知的氨基甲酸酯化催化剂。In the above-mentioned polymerization reaction, a known urethanization catalyst such as amines or organic metal compounds may be added as necessary.
作为胺类，可举出例如三乙基胺、三乙二胺、双-(2-二甲基氨基乙基)醚、N-甲基吗啉等叔胺类、例如四乙基氢氧化铵等季铵盐、例如咪唑、2-乙基-4-甲基咪唑等咪唑类等。Examples of the amines include tertiary amines such as triethylamine, triethylenediamine, bis-(2-dimethylaminoethyl) ether and N-methylmorpholine; quaternary ammonium salts such as tetraethylammonium hydroxide; and imidazoles such as imidazole and 2-ethyl-4-methylimidazole.
作为有机金属化合物，可举出例如乙酸锡、辛酸锡(tin octylate)、油酸锡、月桂酸锡、二丁基二乙酸锡、二甲基二月桂酸锡、二丁基二月桂酸锡、二丁基二硫醇锡、二丁基马来酸锡、二丁基二新癸酸锡、二辛基二硫醇锡、二辛基二月桂酸锡、二丁基二氯化锡等有机锡化合物、例如辛酸铅、环烷酸铅等有机铅化合物、例如环烷酸镍等有机镍化合物、例如环烷酸钴等有机钴化合物、例如辛烯酸铜等有机铜化合物、例如辛酸铋(bismuth octylate)、新癸酸铋等有机铋化合物等，优选可举出辛酸锡、辛酸铋。Examples of the organometallic compound include organic tin compounds such as tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin dithiol, dibutyltin maleate, dibutyltin dineodecanoate, dioctyltin dithiol, dioctyltin dilaurate, and dibutyltin dichloride; organic lead compounds such as lead octylate and lead naphthenate; organic nickel compounds such as nickel naphthenate; organic cobalt compounds such as cobalt naphthenate; organic copper compounds such as copper octenate; and organic bismuth compounds such as bismuth octylate and bismuth neodecanoate. Preferably, tin octylate and bismuth octylate are used.
此外，作为氨基甲酸酯化催化剂，可举出例如碳酸钾、乙酸钾、辛酸钾等钾盐。Examples of the urethanization catalyst include potassium salts such as potassium carbonate, potassium acetate, and potassium octoate.
这些氨基甲酸酯化催化剂可以单独使用或者并用2种以上。These urethanization catalysts may be used alone or in combination of two or more.
相对于多异氰酸酯成分及高分子量多元醇的总量10000质量份而言，氨基甲酸酯化催化剂的添加比例例如为0.001质量份以上，优选为0.01质量份以上，例如为1质量份以下，优选为0.5质量份以下。The addition ratio of the urethanization catalyst is, for example, 0.001 parts by mass or more, preferably 0.01 parts by mass or more, for example, 1 part by mass or less, preferably 0.5 parts by mass or less, relative to 10000 parts by mass of the total amount of the polyisocyanate component and the high molecular weight polyol.
需要说明的是，氨基甲酸酯化催化剂可以根据需要而以利用已知的催化剂稀释剂(溶剂)进行了稀释的溶液或分散液的形式添加。In addition, the urethanization catalyst can be added as a solution or dispersion diluted with a known catalyst diluent (solvent) as needed.
另外，上述聚合反应中，可以通过例如蒸馏、萃取等已知的除去手段将未反应的多异氰酸酯成分、使用了有机溶剂的情况下的有机溶剂除去。In the above-mentioned polymerization reaction, unreacted polyisocyanate components and, when an organic solvent is used, the organic solvent can be removed by known removal means such as distillation and extraction.
预聚物合成工序中，关于各成分的配合比例，以多异氰酸酯成分中的异氰酸酯基相对于高分子量多元醇中的羟基而言的当量比(异氰酸酯基/羟基)计，例如为1.3以上，优选为1.5以上，例如为20以下，优选为15以下，更优选为10以下，进一步优选为8以下。In the prepolymer synthesis step, the mixing ratio of each component is, in terms of the equivalent ratio of the isocyanate group in the polyisocyanate component to the hydroxyl group in the high molecular weight polyol (isocyanate group/hydroxyl group), for example, 1.3 or more, preferably 1.5 or more, for example, 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 8 or less.
更具体而言，关于预聚物合成工序中的各成分的配合比例，相对于高分子量多元醇100质量份而言，多异氰酸酯成分例如为5质量份以上，优选为10质量份以上，更优选为15质量份以上，例如为150质量份以下，优选为100质量份以下，更优选为90质量份以下。More specifically, regarding the mixing ratio of each component in the prepolymer synthesis step, the polyisocyanate component is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and for example, 150 parts by mass or less, preferably 100 parts by mass or less, more preferably 90 parts by mass or less, relative to 100 parts by mass of the high molecular weight polyol.
另外，预聚物合成工序中，为了调整得到的热塑性聚氨酯树脂的硬链段浓度(后述)，也可以与高分子量多元醇一起以适当的比例配合上述低分子量多元醇等。In the prepolymer synthesis step, the above-mentioned low molecular weight polyol and the like may be blended together with the high molecular weight polyol at an appropriate ratio in order to adjust the hard segment concentration (described later) of the obtained thermoplastic polyurethane resin.
而且，该方法中，使上述成分进行反应直至异氰酸酯基含有率达到例如1.0质量％以上、优选1.5质量％以上、更优选3.0质量％以上、进一步优选5.0质量％以上、例如30.0质量％以下、优选19.0质量％以下、更优选16.0质量％以下、进一步优选12.0质量％以下。由此，能够得到异氰酸酯基封端预聚物。Furthermore, in this method, the above components are reacted until the isocyanate group content reaches, for example, 1.0% by mass or more, preferably 1.5% by mass or more, more preferably 3.0% by mass or more, further preferably 5.0% by mass or more, for example, 30.0% by mass or less, preferably 19.0% by mass or less, more preferably 16.0% by mass or less, further preferably 12.0% by mass or less. Thus, an isocyanate group-terminated prepolymer can be obtained.
需要说明的是，异氰酸酯基含量(异氰酸酯基含有率)可以通过基于二正丁基胺的滴定法等已知的方法来求出。The isocyanate group content (isocyanate group content ratio) can be determined by a known method such as a titration method using di-n-butylamine.
接着，该方法中，使通过上述方式得到的异氰酸酯基封端预聚物、与包含碳原子数2～6的低分子量二醇的低分子量多元醇进行反应，得到多异氰酸酯成分与多元醇成分的反应产物(扩链工序)。Next, in this method, the isocyanate group-terminated prepolymer obtained as described above is reacted with a low molecular weight polyol containing a low molecular weight diol having 2 to 6 carbon atoms to obtain a reaction product of a polyisocyanate component and a polyol component (chain extension step).
即，该方法中，包含碳原子数2～6的低分子量二醇的低分子量多元醇为扩链剂。That is, in this method, a low molecular weight polyol including a low molecular weight diol having 2 to 6 carbon atoms serves as a chain extender.
而且，扩链工序中，通过例如上述的本体聚合、上述的溶液聚合等聚合方法，使异氰酸酯基封端预聚物与低分子量多元醇反应。In the chain extension step, the isocyanate group-terminated prepolymer is reacted with the low molecular weight polyol by a polymerization method such as the above-mentioned bulk polymerization or the above-mentioned solution polymerization.
反应温度例如为室温以上，优选为50℃以上，例如为200℃以下，优选为150℃以下，反应时间例如为5分钟以上，优选为1小时以上，例如为72小时以下，优选为48小时以下。The reaction temperature is, for example, room temperature or higher, preferably 50° C. or higher, for example, 200° C. or lower, preferably 150° C. or lower, and the reaction time is, for example, 5 minutes or higher, preferably 1 hour or higher, for example, 72 hours or lower, preferably 48 hours or lower.
另外，关于各成分的配合比例，以异氰酸酯基封端预聚物中的异氰酸酯基相对于低分子量多元醇中的羟基而言的当量比(异氰酸酯基/羟基)计，例如为0.75以上，优选为0.9以上，例如为1.3以下，优选为1.1以下。The mixing ratio of each component is, in terms of an equivalent ratio of isocyanate groups in the isocyanate-terminated prepolymer to hydroxyl groups in the low molecular weight polyol (isocyanate groups/hydroxyl groups), for example, 0.75 or more, preferably 0.9 or more, for example, 1.3 or less, preferably 1.1 or less.
更具体而言，关于扩链工序中的各成分的配合比例，相对于异氰酸酯基封端预聚物100质量份而言，低分子量多元醇例如为1.0质量份以上，优选为2.5质量份以上，更优选为3.5质量份以上，进一步优选为4.5质量份以上，尤其优选为5.5质量份以上，例如为15.0质量份以下，优选为10.0质量份以下，更优选为9.0质量份以下。More specifically, regarding the mixing ratio of each component in the chain extension step, the low molecular weight polyol is, for example, 1.0 part by mass or more, preferably 2.5 parts by mass or more, more preferably 3.5 parts by mass or more, further preferably 4.5 parts by mass or more, particularly preferably 5.5 parts by mass or more, and is, for example, 15.0 parts by mass or less, preferably 10.0 parts by mass or less, and more preferably 9.0 parts by mass or less, based on 100 parts by mass of the isocyanate group-terminated prepolymer.
另外，扩链工序中，为了调整得到的热塑性聚氨酯树脂的硬链段浓度(后述)，也可以与低分子量多元醇一起以适当的比例配合上述高分子量多元醇等。In the chain extension step, the high molecular weight polyol and the like may be blended together with the low molecular weight polyol at an appropriate ratio in order to adjust the hard segment concentration (described later) of the obtained thermoplastic polyurethane resin.
此外，该反应中，根据需要，可以添加上述的氨基甲酸酯化催化剂。氨基甲酸酯化催化剂可以配合在异氰酸酯基封端预聚物及/或低分子量多元醇中，另外，也可以在将它们混合时另行配合。Furthermore, in this reaction, the above-mentioned urethanization catalyst may be added as necessary. The urethanization catalyst may be blended in the isocyanate group-terminated prepolymer and/or the low molecular weight polyol, or may be blended separately when these are mixed.
另外，采用一次完成法作为得到上述的反应产物的方法的情况下，以多异氰酸酯成分中的异氰酸酯基相对于多元醇成分中的羟基而言的当量比(异氰酸酯基/羟基)成为例如0.9以上、优选0.95以上、更优选0.98以上、例如1.2以下、优选1.1以下、更优选1.08以下的比例，同时配合多异氰酸酯成分、和多元醇成分(包含高分子量多元醇及低分子量多元醇)，进行搅拌混合。When the one-step method is used as a method for obtaining the above-mentioned reaction product, the polyisocyanate component and the polyol component (including a high molecular weight polyol and a low molecular weight polyol) are simultaneously blended and stirred and mixed so that the equivalent ratio of the isocyanate group in the polyisocyanate component to the hydroxyl group in the polyol component (isocyanate group/hydroxyl group) is, for example, 0.9 or more, preferably 0.95 or more, more preferably 0.98 or more, for example, 1.2 or less, preferably 1.1 or less, more preferably 1.08 or less.
另外，该搅拌混合在例如非活性气体(例如，氮)气氛下，在反应温度例如为40℃以上、优选为70℃以上、例如为280℃以下、优选为260℃以下、反应时间例如为30秒以上1小时以下的条件下实施。The stirring and mixing is carried out under an inert gas (e.g., nitrogen) atmosphere, for example, at a reaction temperature of, for example, 40°C or higher, preferably 70°C or higher, for example, 280°C or lower, preferably 260°C or lower, and for a reaction time of, for example, 30 seconds or more and 1 hour or less.
另外，在搅拌混合时，根据需要，可以以适当的比例添加上述的氨基甲酸酯化催化剂、有机溶剂。Furthermore, during the stirring and mixing, the above-mentioned urethanization catalyst and organic solvent may be added in an appropriate ratio as necessary.
由此，作为反应产物，可得到热塑性聚氨酯树脂。Thereby, a thermoplastic polyurethane resin can be obtained as a reaction product.
另外，该方法中，根据需要，可以对所得到的反应产物进行热处理(热处理工序)。In this method, the obtained reaction product may be subjected to heat treatment (heat treatment step) as necessary.
热处理工序是对上述的反应产物(热处理前的反应产物(一次产物))进行热处理而得到二次产物(热处理后的反应产物)的工序。The heat treatment step is a step of heat-treating the above-mentioned reaction product (reaction product before heat treatment (primary product)) to obtain a secondary product (reaction product after heat treatment).
热处理工序中，通过将在上述反应工序中得到的一次产物于规定的热处理温度、在规定的热处理期间内静置从而进行热处理，然后根据需要进行干燥。In the heat treatment step, the primary product obtained in the above reaction step is heat treated by leaving it to stand at a predetermined heat treatment temperature for a predetermined heat treatment period, and then dried as necessary.
作为热处理温度，例如为50℃以上，优选为60℃以上，更优选为70℃以上，例如为100℃以下，优选为90℃以下。The heat treatment temperature is, for example, 50° C. or higher, preferably 60° C. or higher, more preferably 70° C. or higher, and is, for example, 100° C. or lower, preferably 90° C. or lower.
若热处理温度在上述范围内，则能够得到特别良好地兼具伸缩特性及耐热性的热塑性聚氨酯树脂。When the heat treatment temperature is within the above range, a thermoplastic polyurethane resin having particularly good elasticity and heat resistance can be obtained.
作为热处理期间，例如为3天以上，优选为4天以上，更优选为5天以上，进一步优选为6天以上，例如为10天以下，优选为9天以下，更优选为8天以下。The heat treatment period is, for example, 3 days or more, preferably 4 days or more, more preferably 5 days or more, further preferably 6 days or more, and is, for example, 10 days or less, preferably 9 days or less, more preferably 8 days or less.
若热处理期间在上述范围内，则能够得到特别良好地兼具伸缩特性及耐热性的热塑性聚氨酯树脂。When the heat treatment period is within the above range, a thermoplastic polyurethane resin having particularly good elasticity and heat resistance can be obtained.
另外，在上述的热塑性聚氨酯树脂的制造中，根据需要，可以添加例如抗氧化剂、耐热稳定剂、紫外线吸收剂、耐光稳定剂、以及防水解剂(碳二亚胺化合物等)、染料(上蓝剂等)、增塑剂、防结块剂、表面改性剂、润滑剂、脱模剂、颜料、填料、防锈剂、填充剂等添加剂。In addition, in the production of the above-mentioned thermoplastic polyurethane resin, additives such as antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, and anti-hydrolysis agents (such as carbodiimide compounds), dyes (such as bluing agents), plasticizers, anti-blocking agents, surface modifiers, lubricants, release agents, pigments, fillers, rust inhibitors, and fillers can be added as needed.
这些添加剂可以在各成分的混合时、合成时或合成后添加。These additives may be added during mixing, synthesis or after synthesis of the components.
添加添加剂的时机没有特别限制，例如，可以添加在多异氰酸酯成分中，另外，也可以添加在多元醇成分中，还可以在多异氰酸酯成分及多元醇的混合时同时添加，此外，还可以在多异氰酸酯成分及多元醇成分的混合后添加在其混合物中。There is no particular restriction on the timing of adding the additive. For example, the additive may be added to the polyisocyanate component, or to the polyol component, or added simultaneously when the polyisocyanate component and the polyol are mixed. Furthermore, the additive may be added to the mixture after the polyisocyanate component and the polyol component are mixed.
另外，添加剂的添加量没有特别限制，可根据目的及用途而适当地设定。The amount of additives added is not particularly limited and can be appropriately set depending on the purpose and use.
而且，就这样得到的热塑性聚氨酯树脂而言，作为原料成分，包含：包含以60摩尔％以上99.5摩尔％以下的比例含有反式体的1,4-双(异氰酸酯基甲基)环己烷的多异氰酸酯成分；和，包含于25℃为液态的非晶性聚碳酸酯二醇、及碳原子数2～6的低分子量二醇的多元醇成分。The thermoplastic polyurethane resin thus obtained comprises, as raw material components: a polyisocyanate component comprising 1,4-bis(isocyanatemethyl)cyclohexane containing a trans isomer at a ratio of 60 mol % to 99.5 mol %; and a polyol component comprising an amorphous polycarbonate diol which is liquid at 25° C. and a low molecular weight diol having 2 to 6 carbon atoms.
即，作为原料成分，使用了结晶性比较高的1,4-双(异氰酸酯基甲基)环己烷、通过硬链段使结晶性提高的低分子量二醇、和结晶性比较低的非晶性聚碳酸酯二醇。That is, as raw material components, 1,4-bis(isocyanatemethyl)cyclohexane having relatively high crystallinity, a low molecular weight diol having improved crystallinity due to a hard segment, and amorphous polycarbonate diol having relatively low crystallinity are used.
因此，本发明的热塑性聚氨酯树脂及膜能够均衡性良好地调整聚氨酯结构的凝集性，能够均衡性良好地兼具源于凝集性的高度的耐热性、和源于凝集性的低下的伸缩特性。Therefore, the thermoplastic polyurethane resin and film of the present invention can adjust the cohesion of the polyurethane structure in a well-balanced manner, and can have both high heat resistance due to the cohesion and low expansion and contraction characteristics due to the cohesion in a well-balanced manner.
需要说明的是，热塑性聚氨酯树脂的硬链段浓度例如为5质量％以上，优选为7质量％以上，更优选为10质量％以上，进一步优选为15质量％以上，例如为30质量％以下，优选为25质量％以下，更优选为20质量％以下。It should be noted that the hard segment concentration of the thermoplastic polyurethane resin is, for example, 5 mass % or more, preferably 7 mass % or more, more preferably 10 mass % or more, further preferably 15 mass % or more, and for example, 30 mass % or less, preferably 25 mass % or less, more preferably 20 mass % or less.
热塑性聚氨酯树脂的硬链段(通过多异氰酸酯成分与低分子量多元醇的反应形成的硬链段)浓度例如可以利用已知的方法由各成分的配合比例(装料)算出。The concentration of the hard segment (the hard segment formed by the reaction of the polyisocyanate component and the low molecular weight polyol) of the thermoplastic polyurethane resin can be calculated from the mixing ratio (charge) of each component by a known method, for example.
更具体而言，例如，采用预聚物法的情况下，硬链段浓度可以根据各成分的配合配方(装料)而由下式算出。More specifically, for example, when the prepolymer method is used, the hard segment concentration can be calculated from the following formula based on the compounding formula (charge) of each component.
[扩链剂(g)+(扩链剂(g)/扩链剂的分子量(g/mol))×多异氰酸酯成分的平均分子量(g/mol)]÷(多异氰酸酯成分(g)+多元醇成分的总质量(g))×100[chain extender (g) + (chain extender (g) / molecular weight of chain extender (g/mol)) × average molecular weight of polyisocyanate component (g/mol)] ÷ (polyisocyanate component (g) + total mass of polyol component (g)) × 100
另外，160℃以上时的热塑性聚氨酯树脂的熔融峰(吸热峰)的热量(焓变化)例如为0.1J/g以上，优选为0.5J/g以上，更优选为1.0J/g以上，进一步优选为1.5J/g以上，尤其优选为2.0J/g以上，例如为20J/g以下，优选为15J/g以下，更优选为10.5J/g以下，进一步优选为7.0J/g，进一步优选为5.0J/g以下，进一步优选为4.0J/g，尤其优选为3.0J/g以下。The heat (enthalpy change) of the melting peak (endothermic peak) of the thermoplastic polyurethane resin at 160° C. or higher is, for example, 0.1 J/g or higher, preferably 0.5 J/g or higher, more preferably 1.0 J/g or higher, further preferably 1.5 J/g or higher, and particularly preferably 2.0 J/g or higher, and is, for example, 20 J/g or lower, preferably 15 J/g or lower, more preferably 10.5 J/g or lower, further preferably 7.0 J/g, further preferably 5.0 J/g or lower, further preferably 4.0 J/g, and particularly preferably 3.0 J/g or lower.
若160℃以上时的热塑性聚氨酯树脂的熔融峰的热量超过上述下限，则热塑性聚氨酯树脂的凝集性不会过低，因此能够得到优异的耐热性。When the heat of the melting peak of the thermoplastic polyurethane resin at 160° C. or higher exceeds the above lower limit, the cohesiveness of the thermoplastic polyurethane resin will not be too low, and thus excellent heat resistance can be obtained.
另外，若160℃以上时的热塑性聚氨酯树脂的熔融峰的热量低于上述上限，则热塑性聚氨酯树脂的凝集性不会过高，因此能够得到优异的伸缩特性。When the heat of the melting peak of the thermoplastic polyurethane resin at 160° C. or higher is less than the upper limit, the cohesiveness of the thermoplastic polyurethane resin will not be too high, and thus excellent stretch characteristics can be obtained.
即，若160℃以上时的热塑性聚氨酯树脂的熔融峰的热量在上述的范围内，则能够适度调整凝集性，能够实现热塑性聚氨酯树脂的耐热性与伸缩特性的兼得。That is, if the heat of the melting peak of the thermoplastic polyurethane resin at 160° C. or higher is within the above range, the cohesiveness can be appropriately adjusted, and both the heat resistance and the stretchability of the thermoplastic polyurethane resin can be achieved.
需要说明的是，熔融峰的热量可依照后述的实施例，通过差示扫描量热测定(DSC测定)来测定。In addition, the heat|fever of a melting peak can be measured by differential scanning calorimetry (DSC measurement) according to the Example mentioned later.
另外，伸缩特性例如可通过伸长变形后的恢复力(伸缩变形后的形状复原率)来评价。The stretching property can be evaluated, for example, by the restoring force after elongation deformation (shape recovery rate after stretching deformation).
具体而言，从伸缩特性的观点考虑，热塑性聚氨酯树脂的15秒60％拉伸后的恢复力(形状复原率)例如为97.0％以上，优选为97.5％以上，更优选为98.0％以上，进一步优选为98.2％以上，通常为100.0％以下。Specifically, from the viewpoint of stretch properties, the restoring force (shape recovery rate) of the thermoplastic polyurethane resin after 60% stretching for 15 seconds is, for example, 97.0% or more, preferably 97.5% or more, more preferably 98.0% or more, further preferably 98.2% or more, and usually 100.0% or less.
需要说明的是，15秒60％拉伸后的恢复力(形状复原率)可依照后述的实施例，利用拉伸试验机等来测定。It should be noted that the restoring force (shape recovery rate) after 60% stretching for 15 seconds can be measured using a tensile testing machine or the like according to the Examples described below.
另外，更具体而言，耐热性可通过储能弹性模量(E’)来评价。In addition, more specifically, heat resistance can be evaluated by storage elastic modulus (E').
具体而言，从耐热性的观点考虑，热塑性聚氨酯树脂的80℃时的储能弹性模量(E’)例如为10×106MPa以上，优选为15×106MPa以上，更优选为20×106MPa以上，例如为50×106MPa以下，优选为40×106MPa以下，更优选为30×106MPa以下。Specifically, from the viewpoint of heat resistance, the storage elastic modulus (E') of the thermoplastic polyurethane resin at 80°C is, for example, 10×106 MPa or more, preferably 15×106 MPa or more, more preferably 20×106 MPa or more, for example, 50×106 MPa or less, preferably 40×106 MPa or less, more preferably 30×106 MPa or less.
需要说明的是，80℃时的储能弹性模量(E’)可依照后述的实施例，通过动态粘弹性测定来测定。It should be noted that the storage elastic modulus (E') at 80°C can be measured by dynamic viscoelasticity measurement in accordance with the Examples described below.
而且，可以通过例如已知的成型方法将上述的热塑性聚氨酯树脂成型(一次成型)，从而将热塑性聚氨酯树脂成型为任意的形状，能够得到包含热塑性聚氨酯树脂的成型品(一次成型品)。The thermoplastic polyurethane resin can be molded (primary molding) by, for example, a known molding method to obtain a molded product (primary molding product) containing the thermoplastic polyurethane resin by molding the thermoplastic polyurethane resin into any shape.
作为一次成型中的成型方法，可举出例如热压缩成型、注射成型、挤出成型、裁切成型、熔融纺纱成型、3D打印机成型等。它们可以单独使用或者并用2种以上。Examples of the molding method in the primary molding include heat compression molding, injection molding, extrusion molding, cutting molding, melt spinning molding, 3D printer molding, etc. These can be used alone or in combination of two or more.
作为一次成型品的形状，可举出例如粒料状、板状、纤维状、线束状、膜状、片状、管状、中空状、箱状等，优选可举出粒料状。Examples of the shape of the primary molded product include a pellet shape, a plate shape, a fiber shape, a strand shape, a film shape, a sheet shape, a tube shape, a hollow shape, and a box shape. Preferably, a pellet shape is used.
例如，作为一次成型品而得到粒料状的热塑性聚氨酯树脂的情况下，优选可以通过已知的成型方法对粒料状的热塑性聚氨酯树脂进行二次成型，得到热塑性聚氨酯树脂的二次成型品。For example, when a pelletized thermoplastic polyurethane resin is obtained as a primary molded article, the pelletized thermoplastic polyurethane resin may be preferably subjected to secondary molding by a known molding method to obtain a secondary molded article of the thermoplastic polyurethane resin.
作为二次成型中的成型方法，可举出上述的成型方法，优选可举出挤出成型。As the molding method in the secondary molding, the above-mentioned molding methods can be mentioned, and extrusion molding is preferred.
作为二次成型品的形状，可举出例如粒料状、板状、纤维状、线束状、膜状、片状、管状、中空状、箱状等，优选可举出膜状。Examples of the shape of the secondary molded product include pellets, plates, fibers, strands, films, sheets, tubes, hollows, and boxes, and preferably, a film shape is used.
即，作为热塑性聚氨酯树脂的成型品，优选可举出膜。That is, as the molded product of the thermoplastic polyurethane resin, preferably, a film is mentioned.
而且，本发明包括包含上述的热塑性聚氨酯树脂的膜。Furthermore, the present invention includes a film comprising the above-mentioned thermoplastic polyurethane resin.
即，本发明的膜是由上述的热塑性聚氨酯树脂成型的。即，本发明的膜为上述的热塑性聚氨酯树脂的成型品。That is, the film of the present invention is formed from the above-mentioned thermoplastic polyurethane resin. That is, the film of the present invention is a molded product of the above-mentioned thermoplastic polyurethane resin.
这样的膜由于包含上述的热塑性聚氨酯树脂，因此伸缩特性及耐热性优异。Since such a film contains the above-mentioned thermoplastic polyurethane resin, it is excellent in expansion and contraction characteristics and heat resistance.
因此，包含热塑性聚氨酯树脂的膜可以在要求上述各种物性的领域中合适地使用。例如，上述的膜可在汽车产业等各种产业领域中作为用于保护各种制品的涂装面的保护膜(Paint Protection Film(PPF))的基底膜等而合适地使用。Therefore, the film comprising thermoplastic polyurethane resin can be suitably used in the field requiring the above-mentioned various physical properties. For example, the above-mentioned film can be suitably used as a base film of a protective film (Paint Protection Film (PPF)) for protecting the coating surface of various products in various industrial fields such as the automobile industry.
保护膜(PPF)是用于将包含聚氨酯树脂的膜粘贴在各种制品(尤其是汽车、摩托车等)的涂装面来保护各种制品的表面的层叠膜。保护膜(PPF)例如具备包含聚酯树脂的剥离层、在该剥离层上配置的丙烯酸系粘合层、和在丙烯酸系粘合层上配置的基底膜层。另外，保护膜也可以还具备在基底膜层上配置的表面保护层。A protective film (PPF) is a laminated film used to protect the surface of various products (especially automobiles, motorcycles, etc.) by attaching a film containing a polyurethane resin to the coating surface of various products. The protective film (PPF) includes, for example, a release layer containing a polyester resin, an acrylic adhesive layer disposed on the release layer, and a base film layer disposed on the acrylic adhesive layer. In addition, the protective film may also include a surface protection layer disposed on the base film layer.
通过在这样的保护膜(PPF)中使用包含上述的热塑性聚氨酯树脂的膜作为基底膜层，能够得到优异的伸缩特性及耐热性，能够良好地保护各种制品(汽车、摩托车等)。By using a film containing the above-mentioned thermoplastic polyurethane resin as a base film layer in such a protective film (PPF), excellent stretch characteristics and heat resistance can be obtained, and various products (such as automobiles and motorcycles) can be well protected.
需要说明的是，上述的热塑性聚氨酯树脂不限定于膜，可以在要求伸缩特性及耐热性的各种产业领域中合适地使用。It should be noted that the above-mentioned thermoplastic polyurethane resin is not limited to films, but can be suitably used in various industrial fields requiring stretch characteristics and heat resistance.
更具体而言，上述的热塑性聚氨酯树脂可在例如纱、纤维(在管、紧身衣裤、鞋罩、运动服、运动用品、护具、游泳衣等中使用的纱、复合纤维)、单丝、膜(衣料用的伸缩性膜、热熔膜、创伤被覆膜等)的领域中合适地使用。More specifically, the above-mentioned thermoplastic polyurethane resin can be suitably used in the fields of, for example, yarn, fiber (yarn and composite fiber used in tubes, tights, shoe covers, sportswear, sports equipment, protective gear, swimsuits, etc.), monofilament, and film (stretchable film for clothing, hot-melt film, wound covering film, etc.).
另外，上述的热塑性聚氨酯树脂可合适地用于例如透明性硬质塑料、涂覆材料、粘合剂、粘接剂、防水材料、灌封剂、油墨、粘结剂、片材、带(例如，表带等带、例如汽车用传动皮带、各种产业用传送带(输送带)等带)、管(例如，除了医疗用管、导管等部件之外，空气管、油压管、电线管等管，例如消防软管等软管)、叶片、扬声器、传感器类、高亮度用LED封装剂、有机EL构件、太阳光发电构件、机器人构件、智能机器人构件、可穿戴构件、衣物用品、卫生用品、化妆用品、食品包装构件、运动用品、娱乐用品、医疗用品、护理用品、住宅用构件、音响构件、照明构件、枝形吊灯、室外灯、密封材料、封装材料、软塞、填充物、防振·减震·隔震构件、防音构件、日用品、杂货、缓冲器、卧具、应力吸收材料、应力缓和材料、汽车的内外装饰部件、铁道构件、航空器构件、光学构件、OA设备用构件、杂货表面保护构件、半导体封装材料、自修复材料、健康器具、眼镜透镜、玩具、电缆包皮、配线、电气通信电缆、汽车布线、计算机布线、伸缩线等工业用品、片材、膜等护理用品、运动用品、娱乐用品、各种杂货、防振·隔振材料、冲击吸收材料、光学材料、导光膜等膜、汽车部件、表面保护片材、化妆片材、转印片材、半导体保护带等带构件、高尔夫球构件、网球拍用弦线、农业用膜、壁纸、防雾赋予剂、无纺布、床垫、沙发等家具用品、胸罩、肩垫等衣物用品、纸尿布、布巾、医用胶带的缓冲材料等医疗用品、化妆品、洗脸海绵、垫等卫生用品、鞋底(外底)、中底、外壳材料等鞋用品、以及车辆用的垫、缓冲器等体压分散用品、门饰板、仪表盘、换挡手柄等用手接触的构件、电冰箱、建筑物的隔热材料、减震器等冲击吸收材料、填充材料、车辆的方向盘、汽车内部装饰构件、汽车外部装饰构件等车辆用品、化学机械抛光(CMP)垫等半导体制造用品等中。In addition, the above-mentioned thermoplastic polyurethane resin can be suitably used for transparent hard plastics, coating materials, adhesives, bonding agents, waterproof materials, potting agents, inks, adhesives, sheets, belts (for example, belts such as watch bands, belts such as automobile transmission belts, various industrial conveyor belts (conveyor belts)), tubes (for example, in addition to medical tubes, catheters and other parts, air tubes, hydraulic tubes, electric wire tubes and other tubes, such as fire hoses and other hoses), blades, speakers, sensors, high-brightness LED encapsulants, organic EL components, solar power generation components, robot components, Intelligent robot components, wearable components, clothing products, sanitary products, cosmetics, food packaging components, sports products, entertainment products, medical products, nursing products, residential components, audio components, lighting components, chandeliers, outdoor lights, sealing materials, packaging materials, soft plugs, fillers, vibration-proof, shock-absorbing, and seismic isolation components, soundproof components, daily necessities, sundries, buffers, bedding, stress absorbing materials, stress relaxation materials, automotive interior and exterior decoration parts, railway components, aircraft components, optical components, OA equipment components, sundries surface protection components, semiconductors Packaging materials, self-repairing materials, health equipment, eyeglass lenses, toys, cable sheaths, wiring, electrical communication cables, automobile wiring, computer wiring, telescopic cords and other industrial products, sheets, films and other care products, sports goods, entertainment products, various sundries, vibration-proof and vibration-isolating materials, impact-absorbing materials, optical materials, films such as light guide films, automobile parts, surface protection sheets, cosmetic sheets, transfer sheets, semiconductor protection tapes and other tape components, golf ball components, tennis racket strings, agricultural films, wallpapers, anti-fog agents, nonwoven fabrics, mattresses, sofas and other furniture products, bras , clothing products such as shoulder pads, medical products such as diapers, cloth towels, and cushioning materials for medical tapes, cosmetics, hygiene products such as face sponges and pads, shoe products such as soles (outsoles), midsoles, and shell materials, as well as body pressure dispersion products such as pads and buffers for vehicles, components that are touched by hands such as door trims, instrument panels, and shift handles, refrigerators, insulation materials for buildings, impact absorbing materials such as shock absorbers, filling materials, vehicle products such as steering wheels, automobile interior decoration components, automobile exterior decoration components, and semiconductor manufacturing products such as chemical mechanical polishing (CMP) pads.
此外，上述的成型品可合适地用于被覆材料(膜、片材、带、线、电线、金属制的旋转设备、轮、钻头等的被覆材料)、挤出成型用途(网球、羽毛球等的弦线及其集束材料等挤出成型用途)、基于微粒料化等的粉末形状的中空成型品、人造皮革、表皮、片材、被覆辊(钢铁等的被覆辊)、密封剂、辊、齿轮、球、球棒的外壳或芯材料(高尔夫球、篮球、网球、排球、垒球、棒球等的外壳或芯材料(它们可以是将聚氨酯树脂发泡成型而成的形态。))、垫、滑雪用品、长筒靴、网球用品、握柄(高尔夫球杆、两轮车等的握柄)、齿条罩、雨刮器、座垫构件、护理制品的膜、3D打印成型品、纤维增强材料(碳纤维、木质素、槿麻、纳米纤维素纤维、玻璃纤维等纤维的增强材料)、安全护目镜、太阳镜、眼镜框、滑雪镜、游泳镜、隐形眼镜、气体辅助的发泡成型品、减震器、CMP抛光垫、阻尼器(damper)、轴承、防尘罩、切削阀门(cuttingvalve)、切削辊(chipping roll)、高速旋转辊、轮胎、时钟、可穿戴带等要求伸缩特性及耐热性的用途中。In addition, the above-mentioned molded products can be suitably used for coating materials (films, sheets, belts, wires, wires, metal rotating equipment, wheels, drill bits, etc.), extrusion molding applications (tennis, badminton, etc. strings and bundled materials thereof, etc.), hollow molded products in powder form based on microgranulation, etc., artificial leather, skin, sheet, coated roller (coated roller of steel, etc.), sealants, rollers, gears, balls, bats, shells or core materials (golf balls, basketballs, tennis balls, volleyballs, softballs, baseballs, etc., shells or core materials (these may be in the form of polyurethane resin foamed and molded.)), In applications requiring expansion and contraction properties and heat resistance, such as pads, ski equipment, boots, tennis equipment, grips (for golf clubs, two-wheeled vehicles, etc.), rack covers, wipers, seat cushion components, films for care products, 3D printed products, fiber-reinforced materials (reinforced materials made of fibers such as carbon fiber, lignin, kenaf, nanocellulose fiber, and glass fiber), safety goggles, sunglasses, eyeglass frames, ski goggles, swimming goggles, contact lenses, gas-assisted foamed products, shock absorbers, CMP polishing pads, dampers, bearings, dust covers, cutting valves, chipping rolls, high-speed rotating rolls, tires, clocks, and wearable belts.
实施例Example
接下来，基于实施例及比较例来说明本发明，但本发明不受它们的限定。需要说明的是，只要没有特别说明，则“份”及“％”是以质量为基准。另外，在以下的记载中使用的配合比例(含有比例)、物性值、参数等具体的数值可以替换为在上述的“具体实施方式”中记载的、与它们对应的配合比例(含有比例)、物性值、参数等相应记载的上限值(以“以下”、“低于”的形式定义的数值)或下限值(以“以上”、“高于”的形式定义的数值)。Next, the present invention is described based on embodiments and comparative examples, but the present invention is not limited thereto. It should be noted that, unless otherwise specified, "parts" and "%" are based on mass. In addition, the specific numerical values such as the mixing ratio (containing ratio), physical property values, and parameters used in the following descriptions can be replaced by the upper limit value (numerical value defined in the form of "below", "lower than") or the lower limit value (numerical value defined in the form of "above", "higher than") recorded in the above-mentioned "specific embodiments" and corresponding to the mixing ratio (containing ratio), physical property values, and parameters.
1)原料1) Raw materials
＜多异氰酸酯成分(a)＞<Polyisocyanate component (a)>
1,4-H6XDI：利用制造例1中记载的方法合成的1,4-双(异氰酸酯基甲基)环己烷，反式体86摩尔％/顺式体14摩尔％1,4-H6 XDI: 1,4-bis(isocyanatemethyl)cyclohexane synthesized by the method described in Preparation Example 1, trans isomer 86 mol%/cis isomer 14 mol%
H12MDI：4,4’-二环己基甲烷二异氰酸酯H12 MDI: 4,4'-dicyclohexylmethane diisocyanate
＜高分子量多元醇(b)＞＜High molecular weight polyol (b)＞
b-1)UH100W：数均分子量(Mn)为1000，结晶性聚碳酸酯二醇，商品名ETERNACOLLUH-100W，平均羟基数为2，宇部兴产制b-1) UH100W: number average molecular weight (Mn) 1000, crystalline polycarbonate diol, trade name ETERNACOLLUH-100W, average hydroxyl number 2, manufactured by Ube Industries
b-2)UH200W：数均分子量(Mn)为2000，结晶性聚碳酸酯二醇，商品名ETERNACOLLUH-200W，平均羟基数为2，宇部兴产制b-2) UH200W: number average molecular weight (Mn) 2000, crystalline polycarbonate diol, trade name ETERNACOLLUH-200W, average hydroxyl number 2, manufactured by Ube Industries
b-3)UP100：数均分子量(Mn)为1000，非晶性聚碳酸酯二醇，商品名ETERNACOLLUP-100，平均羟基数为2，宇部兴产制b-3) UP100: number average molecular weight (Mn) 1000, amorphous polycarbonate diol, trade name ETERNACOLLUP-100, average hydroxyl number 2, manufactured by Ube Industries
b-4)UP200：数均分子量(Mn)为2000，非晶性聚碳酸酯二醇，商品名ETERNACOLLUP-200，平均羟基数为2，宇部兴产制b-4) UP200: number average molecular weight (Mn) 2000, amorphous polycarbonate diol, trade name ETERNACOLLUP-200, average hydroxyl number 2, manufactured by Ube Industries
b-5)C2090R：数均分子量(Mn)为2000，非晶性聚碳酸酯二醇，商品名KURARAYPOLYOL C-2090R，改性剂：3-甲基-1,5-戊二醇，平均羟基数为2，Kuraray IsopreneChemical制b-5) C2090R: number average molecular weight (Mn) 2000, amorphous polycarbonate diol, trade name KURARAY POLYOL C-2090R, modifier: 3-methyl-1,5-pentanediol, average hydroxyl number 2, manufactured by Kuraray Isoprene Chemical
b-6)210N：数均分子量(Mn)为1000，聚己内酯二醇，商品名Placcel 210N，平均羟基数为2，Daicel公司制b-6) 210N: number average molecular weight (Mn) 1000, polycaprolactone diol, trade name Placcel 210N, average hydroxyl number 2, manufactured by Daicel
b-7)220N：数均分子量(Mn)为2000，聚己内酯二醇，商品名Placcel 220N，平均羟基数为2，Daicel公司制b-7) 220N: number average molecular weight (Mn) 2000, polycaprolactone diol, trade name Placcel 220N, average hydroxyl number 2, manufactured by Daicel
＜低分子量多元醇(c)＞＜Low molecular weight polyol (c)＞
1,4-BD：1,4-丁二醇，三菱化学公司制，碳原子数(C)2～6低分子量二醇1,4-BD: 1,4-butanediol, manufactured by Mitsubishi Chemical Corporation, a low molecular weight diol with 2 to 6 carbon atoms (C).
＜氨基甲酸酯化催化剂＞＜Urethane Catalyst＞
STANOCT：辛酸锡，商品名；STANOCT，API CORPORATION制STANOCT: Tin octoate, trade name; STANOCT, manufactured by API CORPORATION
＜催化剂稀释剂＞＜Catalyst diluent＞
己二酸二异壬酯：商品名：DINA，大八化学工业公司制Diisononyl adipate: Trade name: DINA, manufactured by Daihachi Chemical Industry Co., Ltd.
＜添加剂＞＜Additives＞
抗氧化剂：受阻酚化合物，商品名；IRGANOX 245，BASF Japan Ltd.制Antioxidant: Hindered phenol compound, trade name; IRGANOX 245, manufactured by BASF Japan Ltd.
紫外线吸收剂：苯并三唑化合物，商品名；TINUVIN 234，BASF Japan Ltd.制UV absorber: Benzotriazole compound, trade name; TINUVIN 234, manufactured by BASF Japan Ltd.
耐光稳定剂：受阻胺化合物，商品名；ADK STAB LA-72，ADEKA制Light stabilizer: Hindered amine compound, trade name; ADK STAB LA-72, made by ADEKA
＜多异氰酸酯成分(a)的制造＞<Production of polyisocyanate component (a)>
合成例1 1,4-双(异氰酸酯基甲基)环己烷(1,4-H6XDI)的合成Synthesis Example 1 Synthesis of 1,4-bis(isocyanatomethyl)cyclohexane (1,4-H6 XDI)
依照国际公开WO2019/069802号公报的制造例3的记载，得到1,4-双(异氰酸酯基甲基)环己烷(1,4-H6XDI)。According to the description of Production Example 3 of International Publication No. WO2019/069802, 1,4-bis(isocyanatemethyl)cyclohexane (1,4-H6 XDI) was obtained.
所得到的1,4-H6XDI的通过气相色谱测定得到的纯度为99.9％，通过APHA测定得到的色相为5，通过13C-NMR测定得到的反式体/顺式体比为反式体86摩尔％、顺式体14摩尔％。The purity of the obtained 1,4-H6 XDI measured by gas chromatography was 99.9%, the hue measured by APHA was 5, and the trans isomer/cis isomer ratio measured by13 C-NMR was 86 mol % for the trans isomer and 14 mol % for the cis isomer.
2)热塑性聚氨酯树脂2) Thermoplastic polyurethane resin
实施例1～5及比较例1～6Examples 1 to 5 and Comparative Examples 1 to 6
按照表1中记载的配方，得到热塑性聚氨酯树脂及片材。According to the formulation described in Table 1, a thermoplastic polyurethane resin and a sheet were obtained.
更具体而言，首先，对已预先将温度调节至80℃的高分子量多元醇(b)进行测量，在氮气氛下，在80℃的油浴中，使用高速搅拌分散器，以700±50rpm进行1小时搅拌。接着，向高分子量多元醇(b)中添加IRGANOX 245(BASF公司制耐热稳定剂)、TINUVIN571(BASF公司制紫外线吸收剂)及ADK STAB LA-72(ADEKA公司制HALS)作为添加剂，在氮气氛下，在80℃的油浴中，使用高速搅拌分散器，以700±50rpm进行30分钟搅拌。关于添加剂的添加量，相对于最终的多异氰酸酯成分、高分子量多元醇及低分子量多元醇的总量100质量份而言，使IRGANOX 245(BASF公司制耐热稳定剂)为0.3质量份、TINUVIN 571(BASF公司制紫外线吸收剂)为0.4质量份、ADK STAB LA-72(ADEKA公司制HALS)为0.1质量份。More specifically, first, the high molecular weight polyol (b) whose temperature was adjusted to 80° C. in advance was measured, and stirred at 700±50 rpm for 1 hour in an oil bath at 80° C. under a nitrogen atmosphere using a high-speed stirring disperser. Next, IRGANOX 245 (a heat stabilizer manufactured by BASF), TINUVIN 571 (an ultraviolet absorber manufactured by BASF) and ADK STAB LA-72 (HALS manufactured by ADEKA) were added to the high molecular weight polyol (b) as additives, and stirred at 700±50 rpm for 30 minutes in an oil bath at 80° C. under a nitrogen atmosphere using a high-speed stirring disperser. The additives were added in an amount of 0.3 parts by mass of IRGANOX 245 (a heat stabilizer manufactured by BASF), 0.4 parts by mass of TINUVIN 571 (an ultraviolet absorber manufactured by BASF), and 0.1 parts by mass of ADK STAB LA-72 (HALS manufactured by ADEKA) relative to 100 parts by mass of the total amount of the final polyisocyanate component, the high molecular weight polyol, and the low molecular weight polyol.
接着，向所得到的混合物中添加多异氰酸酯成分(a)，进一步地，以按催化剂量(固态成分量)计成为5ppm的方式添加已预先利用己二酸二异壬酯(DINA，大八化学公司制)稀释成4质量％的辛酸锡(商品名：STANOCT，API CORPORATION公司制)。Next, the polyisocyanate component (a) was added to the obtained mixture, and tin octylate (trade name: STANOCT, manufactured by API CORPORATION) which had been diluted to 4% by mass with diisononyl adipate (DINA, manufactured by Daihachi Chemical Co., Ltd.) was added so that the catalyst amount (solid content) became 5 ppm.
接着，在80℃的油浴中，使用高速搅拌分散器，以700±50rpm对所得到的混合物进行5分钟的搅拌混合。由此，得到异氰酸酯基封端预聚物(预聚物合成工序)。Next, the obtained mixture was stirred and mixed at 700±50 rpm for 5 minutes in an oil bath at 80° C. using a high-speed stirring disperser. Thus, an isocyanate group-terminated prepolymer was obtained (prepolymer synthesis step).
接着，向所得到的异氰酸酯基封端预聚物中添加已预先测量并将温度调节至80℃的1,4-丁二醇(低分子量多元醇(c))，使用高速搅拌分散器，以700±50rpm进行搅拌，搅拌混合了3～20分钟(扩链工序)。Next, 1,4-butanediol (low molecular weight polyol (c)) which had been measured in advance and adjusted to 80° C. was added to the obtained isocyanate group-terminated prepolymer, and the mixture was stirred and mixed at 700±50 rpm for 3 to 20 minutes using a high-speed stirring disperser (chain extension step).
低分子量多元醇(c)的添加量以异氰酸酯基封端预聚物中的异氰酸酯基相对于低分子量多元醇(c)中的羟基而言的当量比(异氰酸酯基/羟基)成为1.00的方式进行了调整。The amount of the low molecular weight polyol (c) added was adjusted so that the equivalent ratio (isocyanate group/hydroxyl group) of the isocyanate group-terminated prepolymer to the hydroxyl group in the low molecular weight polyol (c) would be 1.00.
另外，一边观察放热速度，一边适当地添加上述的催化剂(经DINA稀释的辛酸锡)。In addition, the above-mentioned catalyst (tin octylate diluted with DINA) was appropriately added while observing the heat generation rate.
接着，向已预先将温度调节至150℃的Teflon(注册商标)制的桶中流入所得到的混合液，于150℃反应2小时后，进一步地，降温至100℃，继续进行20小时反应，作为反应产物，得到热塑性聚氨酯树脂(热处理前的反应产物(一次产物))。Next, the obtained mixed solution was poured into a Teflon (registered trademark) barrel whose temperature had been adjusted to 150°C in advance, and reacted at 150°C for 2 hours. The temperature was then further lowered to 100°C and the reaction was continued for 20 hours to obtain a thermoplastic polyurethane resin as a reaction product (reaction product (primary product) before heat treatment).
接着，将所得到的热塑性聚氨酯树脂从桶中取出，利用切胶机切割成骰子状，利用粉碎机将骰子状的树脂粉碎，得到粉碎粒料。接着，在80℃的烘箱中，对粉碎粒料进行7天热处理(养护、熟化)，在真空减压下，于23℃干燥12小时。由此，得到热塑性聚氨酯树脂的二次产物(热处理后的反应产物)。Next, the obtained thermoplastic polyurethane resin is taken out from the barrel, cut into dice by a rubber cutter, and the dice-shaped resin is crushed by a pulverizer to obtain crushed pellets. Next, the crushed pellets are heat-treated (cured and aged) for 7 days in an oven at 80°C, and dried at 23°C for 12 hours under vacuum. Thus, a secondary product (reaction product after heat treatment) of the thermoplastic polyurethane resin is obtained.
其后，针对所得到的粉碎粒料(二次产物)，利用单螺杆挤出机(型号：SZW40-28MG，TECHNOVEL公司制)，在螺杆转速为30rpm、料筒温度为150～250℃的范围内对线束进行挤出处理，进行切割。Thereafter, the obtained pulverized pellets (secondary product) were extruded into strands using a single screw extruder (model: SZW40-28MG, manufactured by TECHNOVEL) at a screw speed of 30 rpm and a barrel temperature of 150 to 250° C., and then cut.
由此，作为热塑性聚氨酯树脂的成型物(一次成型物)，得到粒料。In this way, pellets are obtained as a molded product (primary molded product) of the thermoplastic polyurethane resin.
其后，预先在真空减压下于80℃将粒料干燥12小时，使用单螺杆挤出机(型号：SZW40-28MG，TECHNOVEL公司制)，在转速为20rpm、料筒温度为150～250℃的范围内进行挤出成型，作为热塑性聚氨酯树脂的成型物(二次成型物)，得到厚度为150μm的膜。Thereafter, the pellets were dried at 80°C for 12 hours under vacuum reduced pressure in advance, and extrusion-molded using a single-screw extruder (model: SZW40-28MG, manufactured by TECHNOVEL) at a rotation speed of 20 rpm and a barrel temperature in the range of 150 to 250°C to obtain a film with a thickness of 150 μm as a molded product (secondary molded product) of a thermoplastic polyurethane resin.
4)评价4) Evaluation
＜伸缩特性：恢复力(形状复原率)＞＜Stretchability: Restoration force (shape recovery rate)＞
将厚度为150μm(10mm宽×10cm长)的膜设置于万能试验机Model205N(INTESCO制，标线间距离为80mm，拉伸速度为500ml/min)，使其伸长了标线间距离的60％(48mm)后，释放。A film having a thickness of 150 μm (10 mm wide×10 cm long) was placed in a universal testing machine Model 205N (manufactured by INTESCO, with a distance between markings of 80 mm and a tensile speed of 500 ml/min), stretched to 60% of the distance between markings (48 mm) and then released.
从释放起15秒后，测定标线间距离，从而测定膜的恢复力。The distance between the marking lines was measured 15 seconds after release to measure the restoring force of the film.
需要说明的是，膜的恢复力以伸长前的膜的长度相对于伸长后的膜的长度的比率(％)的形式表示，其值越高(接近100％)，则表示恢复力(形状复原率)越高。The film restoring force is expressed as a ratio (%) of the film length before extension to the film length after extension, and a higher value (closer to 100%) indicates a higher restoring force (shape recovery rate).
＜耐热性：储能弹性模量(E’)＞＜Heat resistance: Storage elastic modulus (E’)＞
使用动态粘弹性测定装置(IT Keisoku Seigyo Co.,Ltd.制，型号：DVA-220)，在测定温度为-100℃～250℃、升温速度为5℃/min、拉伸模式、标线间长度为20mm、静/动应力比为1.8、测定频率为10Hz的条件下，测定热塑性聚氨酯树脂的150μm的膜的动态粘弹性光谱。The dynamic viscoelastic spectrum of a 150 μm film of a thermoplastic polyurethane resin was measured using a dynamic viscoelasticity measuring apparatus (manufactured by IT Keisoku Seigyo Co., Ltd., model: DVA-220) at a measuring temperature of -100°C to 250°C, a heating rate of 5°C/min, a tensile mode, a length between markings of 20 mm, a static/dynamic stress ratio of 1.8, and a measuring frequency of 10 Hz.
然后，测定80℃时的储能弹性模量E’。Then, the storage elastic modulus E' at 80°C was measured.
需要说明的是，E’越高，则表示耐热性越优异。It should be noted that the higher the E', the better the heat resistance.
＜熔融热焓(单位：J/g)＞＜Melting enthalpy (unit: J/g)＞
使用差示扫描量热仪(DSC7000X，Hitachi High-Tech Science制)，如下所述地测定。The measurement was performed as follows using a differential scanning calorimeter (DSC7000X, manufactured by Hitachi High-Tech Science).
即，采集热塑性聚氨酯树脂约10mg至铝制皿中。将在该铝制皿上盖上盖子并进行曲贴而得到的产物作为测定用试样(样品)。将同样地采集氧化铝而得到的产物作为参比试样。That is, about 10 mg of thermoplastic polyurethane resin was collected in an aluminum dish, and a lid was placed on the aluminum dish and the obtained product was used as a test sample (sample). Alumina was collected in the same manner and the obtained product was used as a reference sample.
将样品及参比设置于腔室(cell)内的规定位置后，在流量为30NmL/min的氮气流下，将试样以10℃/min的速度从20℃冷却至-100℃，于该温度保持5分钟后，以10℃/min的速度升温至270℃，其后，以10℃/min的速度冷却至-70℃。After setting the sample and reference at the specified positions in the chamber (cell), the sample was cooled from 20°C to -100°C at a rate of 10°C/min under a nitrogen flow of 30NmL/min. After maintaining this temperature for 5 minutes, the temperature was increased to 270°C at a rate of 10°C/min, and then cooled to -70°C at a rate of 10°C/min.
然后，测定在从-100℃至270℃的升温中出现的峰中的、160℃以上时的吸热峰(熔融峰)的峰温度、及该峰的热量(焓变化)(J/g)。Then, among the peaks appearing during the temperature rise from -100°C to 270°C, the peak temperature of the endothermic peak (melting peak) at 160°C or higher and the calorific value (enthalpy change) (J/g) of the peak were measured.
[表1][Table 1]
表1Table 1
需要说明的是，上述发明作为本发明的示例实施方式而提供，但这只不过是示例，并不作限定性解释。对于本领域的技术人员而言是显而易见的本发明的变形例包含在所附的权利要求书内。It should be noted that the above invention is provided as an exemplary embodiment of the present invention, but this is merely an example and is not to be construed as limiting. Modifications of the present invention that are obvious to those skilled in the art are included in the appended claims.
产业上的可利用性Industrial Applicability
本发明的热塑性聚氨酯树脂及膜可在汽车产业等各种产业领域中合适地使用。The thermoplastic polyurethane resin and film of the present invention can be suitably used in various industrial fields such as the automobile industry.
| Application Number | Priority Date | Filing Date | Title |
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| JP2019-180439 | 2019-09-30 | ||
| JP2019180439 | 2019-09-30 | ||
| PCT/JP2020/036592WO2021065783A1 (en) | 2019-09-30 | 2020-09-28 | Thermoplastic polyurethane resin and film |
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| CN114375312A CN114375312A (en) | 2022-04-19 |
| CN114375312Btrue CN114375312B (en) | 2024-04-09 |
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| CN202080064318.XAActiveCN114375312B (en) | 2019-09-30 | 2020-09-28 | Thermoplastic polyurethane resin and film |
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