CN111574928A - Optical moisture-curable resin composition, adhesive for electronic parts, and adhesive for display elements - Google Patents
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Abstract
本发明的目的在于提供保存稳定性和粘接性优异的光湿气固化型树脂组合物。另外，本发明的目的在于提供使用该光湿气固化型树脂组合物而制成的电子部件用粘接剂和显示元件用粘接剂。本发明的光湿气固化型树脂组合物含有自由基聚合性化合物、湿气固化型聚氨酯树脂、光自由基聚合引发剂和除水剂。
An object of the present invention is to provide an optical moisture-curable resin composition excellent in storage stability and adhesiveness. Moreover, the objective of this invention is to provide the adhesive agent for electronic components, and the adhesive agent for display elements which were produced using this optical moisture curable resin composition. The optical moisture-curable resin composition of the present invention contains a radically polymerizable compound, a moisture-curable urethane resin, a photoradical polymerization initiator, and a water scavenger.
Description
本申请是于2016年3月25日进入中国国家阶段的国家申请号为201580001997.5(国际申请号为PCT/JP2015/051348)的、发明名称为“光湿气固化型树脂组合物、电子部件用粘接剂和显示元件用粘接剂”的申请的分案。This application is the national application number 201580001997.5 (the international application number is PCT/JP2015/051348) which entered the Chinese national phase on March 25, 2016, and the invention name is "optical moisture-curable resin composition, adhesive for electronic parts" Adhesives and Adhesives for Display Components".
技术领域technical field
本发明涉及保存稳定性和粘接性优异的光湿气固化型树脂组合物。另外，本发明涉及使用该光湿气固化型树脂组合物而制成的电子部件用粘接剂和显示元件用粘接剂。The present invention relates to an optical moisture-curable resin composition excellent in storage stability and adhesiveness. Moreover, this invention relates to the adhesive agent for electronic components, and the adhesive agent for display elements which were produced using this optical moisture curable resin composition.
背景技术Background technique
近年来，作为具有薄型、轻量、低耗电等特征的显示元件，液晶显示元件、有机EL显示元件等被广泛利用。在这些显示元件中，通常，在液晶、发光层的密封；基板、光学膜、保护膜、各种构件的粘接等中使用了光固化型树脂组合物。In recent years, liquid crystal display elements, organic EL display elements, and the like have been widely used as display elements having characteristics such as thinness, light weight, and low power consumption. In these display elements, generally, a photocurable resin composition is used for sealing of liquid crystals and light-emitting layers, and bonding of substrates, optical films, protective films, various members, and the like.
然而，在便携电话、便携游戏机等各种带显示元件的移动设备普及的现代，显示元件的小型化为最受需要的课题，作为小型化的方法，进行了将图像显示部窄边框化(以下，也称为窄边框设计)。然而，在窄边框设计中，有时在光未充分地到达的部分涂布光固化型树脂组合物，其结果是，涂布于光未到达的部分的光固化型树脂组合物存在固化变得不充分这样的问题。因此，作为即使在涂布于光未到达的部分的情况下也能够充分地固化的树脂组合物，使用了光热固化型树脂组合物，还进行了将光固化与热固化加以并用，但是，存在因高温下的加热而对元件等造成不良影响的担忧。However, in the modern age where various mobile devices with display elements such as cellular phones and portable game consoles are popularized, miniaturization of display elements has become the most demanded subject. Hereinafter, also referred to as narrow bezel design). However, in the narrow frame design, the photocurable resin composition may be applied to the portion where the light does not reach sufficiently, and as a result, the photocurable resin composition applied to the portion where the light does not reach may not be cured. enough such a question. Therefore, a photothermocurable resin composition has been used as a resin composition that can be sufficiently cured even when applied to a portion where light does not reach, and a combination of photocuring and thermal curing has been used. However, There is a concern that elements and the like may be adversely affected by heating at a high temperature.
作为不进行在高温下的加热而使树脂组合物固化的方法，在专利文献1中公开了如下方法：使用含有聚氨酯预聚物的光湿气固化型树脂组合物，并且将光固化和湿气固化并用，所述聚氨酯预聚物在分子中具有至少1个异氰酸酯基和至少1个(甲基)丙烯酰基。但是，专利文献1中公开的那样的光湿气固化型树脂组合物存在难以使保存稳定性和粘接性兼顾的问题。As a method of curing a resin composition without heating at a high temperature, Patent Document 1 discloses a method in which an optical moisture-curable resin composition containing a urethane prepolymer is used, and photocuring and moisture are When cured and used together, the polyurethane prepolymer has at least one isocyanate group and at least one (meth)acryloyl group in the molecule. However, the optical moisture-curable resin composition disclosed in Patent Document 1 has a problem in that it is difficult to achieve both storage stability and adhesiveness.
现有技术文献prior art literature
专利文献Patent Literature
专利文献1：日本特开2008-274131号公报Patent Document 1: Japanese Patent Laid-Open No. 2008-274131
发明内容SUMMARY OF THE INVENTION
发明所要解决的课题The problem to be solved by the invention
本发明的目的在于提供保存稳定性和粘接性优异的光湿气固化型树脂组合物。另外，本发明目的在于提供使用该光湿气固化型树脂组合物而制成的电子部件用粘接剂和显示元件用粘接剂。An object of the present invention is to provide an optical moisture-curable resin composition excellent in storage stability and adhesiveness. Moreover, this invention aims at providing the adhesive agent for electronic components and the adhesive agent for display elements which were produced using this optical moisture curable resin composition.
用于解决课题的手段means of solving problems
本发明的光湿气固化型树脂组合物含有自由基聚合性化合物、湿气固化型聚氨酯树脂、光自由基聚合引发剂和除水剂。The optical moisture-curable resin composition of the present invention contains a radically polymerizable compound, a moisture-curable urethane resin, a photoradical polymerization initiator, and a water scavenger.
以下，对本发明进行详述。Hereinafter, the present invention will be described in detail.
本发明人等发现，通过在含有自由基聚合性化合物、湿气固化型聚氨酯树脂和光自由基聚合引发剂的光湿气固化型树脂组合物中配合除水剂，从而能够使保存稳定性和粘接性二者提高，至此完成了本发明。The inventors of the present invention have found that storage stability and viscosity can be improved by blending a water scavenger in an optical moisture-curable resin composition containing a radically polymerizable compound, a moisture-curable urethane resin, and a photoradical polymerization initiator. Both of these properties are improved, and the present invention has been completed thus far.
本发明的光湿气固化型树脂组合物含有除水剂。The optical moisture-curable resin composition of the present invention contains a water scavenger.
上述除水剂没有特别限定，可以列举出基于物理吸附的除水剂、与水分发生化学性反应的除水剂等。The said water scavenger is not specifically limited, The water scavenger by physical adsorption, the water scavenger which chemically reacts with moisture, etc. are mentioned.
作为上述除水剂，优选使用具有选自异氰酸酯基、异硫氰酸酯基和碳二亚胺基中的至少1种基团的化合物。上述具有选自异氰酸酯基、异硫氰酸酯基和碳二亚胺基中的至少1种基团的化合物与水分的反应性高，具有防止保存时的湿气固化型聚氨酯树脂与水分的反应的作用。需要说明的是，具有氨基甲酸酯键和异氰酸酯基的化合物作为上述湿气固化型聚氨酯树脂来处理。As the above-mentioned water scavenger, a compound having at least one group selected from the group consisting of an isocyanate group, an isothiocyanate group, and a carbodiimide group is preferably used. The compound having at least one group selected from the group consisting of an isocyanate group, an isothiocyanate group, and a carbodiimide group has high reactivity with moisture and prevents the reaction of the moisture-curable polyurethane resin with moisture during storage effect. In addition, the compound which has a urethane bond and an isocyanate group is handled as the said moisture-curable polyurethane resin.
作为上述除水剂，在使用上述具有选自异氰酸酯基、异硫氰酸酯基和碳二亚胺基中的至少1种基团的化合物的情况下，需要在体系中移动并迅速与水分反应，因此优选分子量小，特别是在具有异氰酸酯基、异硫氰酸酯基的化合物的情况下，分子量的优选上限为500，更优选上限为300。另外，从加速与水分的反应速度并有效地除去水分的观点出发，优选含有具有芳香族环的异氰酸酯基、具有芳香族环的异硫氰酸酯基的化合物。需要说明的是，对于具有碳二亚胺基的化合物，没有特别限制。另外，与水分不反应的、上述具有选自异氰酸酯基、异硫氰酸酯基和碳二亚胺基中的至少1种基团的化合物有助于湿气固化型聚氨酯树脂的固化，交联密度提高，由此使所得的光湿气固化型树脂组合物的固化物的粘接性优异。As the above-mentioned water scavenger, in the case of using the above-mentioned compound having at least one group selected from the group consisting of an isocyanate group, an isothiocyanate group and a carbodiimide group, it needs to move in the system and rapidly react with moisture, Therefore, the molecular weight is preferably small, and especially in the case of a compound having an isocyanate group or an isothiocyanate group, the upper limit of the molecular weight is preferably 500, and the upper limit is more preferably 300. In addition, from the viewpoint of accelerating the reaction rate with moisture and effectively removing moisture, a compound containing an isocyanate group having an aromatic ring or an isothiocyanate group having an aromatic ring is preferable. In addition, the compound which has a carbodiimide group is not specifically limited. In addition, the compound having at least one group selected from the group consisting of an isocyanate group, an isothiocyanate group, and a carbodiimide group, which is non-reactive with moisture, contributes to curing and crosslinking of the moisture-curable polyurethane resin. As the density increases, the cured product of the optical moisture-curable resin composition obtained has excellent adhesiveness.
另外，上述具有选自异氰酸酯基、异硫氰酸酯基和碳二亚胺基中的至少1种基团的化合物的分子量的优选下限为100，更优选下限为150。In addition, the preferred lower limit of the molecular weight of the compound having at least one group selected from the group consisting of an isocyanate group, an isothiocyanate group, and a carbodiimide group is 100, and a more preferred lower limit is 150.
上述具有选自异氰酸酯基、异硫氰酸酯基和碳二亚胺基中的至少1种基团的化合物之中，优选具有异氰酸酯基的化合物。作为上述除水剂而使用具有异氰酸酯基的化合物的情况下，可以是与后述的成为湿气固化型聚氨酯树脂的原料的多异氰酸酯化合物同样的化合物，也可以不同。Among the above-mentioned compounds having at least one group selected from the group consisting of an isocyanate group, an isothiocyanate group, and a carbodiimide group, a compound having an isocyanate group is preferable. When a compound having an isocyanate group is used as the water scavenger, the same compound as the polyisocyanate compound used as a raw material of the moisture-curable polyurethane resin described later may be used, or a different compound may be used.
上述具有选自异氰酸酯基、异硫氰酸酯基和碳二亚胺基中的至少1种基团的化合物可以是单官能，也可以是多官能，从对水分具有适度的反应性的方面出发，优选2官能。The compound having at least one group selected from the group consisting of an isocyanate group, an isothiocyanate group, and a carbodiimide group may be monofunctional or polyfunctional, and from the viewpoint of having moderate reactivity to moisture , preferably bifunctional.
需要说明的是，上述具有选自异氰酸酯基、异硫氰酸酯基和碳二亚胺基中的至少1种基团的化合物是化学性地除去水分的化合物，在配合本发明的光湿气固化型树脂组合物中使用的各材料之前，也可以根据需要对各材料预先进行物理性处理(基于后述的沸石那样的其他除水剂的水分的除去)。It should be noted that the compound having at least one group selected from the group consisting of an isocyanate group, an isothiocyanate group, and a carbodiimide group described above is a compound that chemically removes water, and is used in combination with the photomoisture of the present invention. Before each material used in the curable resin composition, if necessary, each material may be subjected to physical treatment (removal of moisture by other water scavengers such as zeolite, which will be described later).
上述具有选自异氰酸酯基、异硫氰酸酯基和碳二亚胺基中的至少1种基团的化合物之中，作为具有异氰酸酯基的化合物，具体可以列举出例如异佛尔酮二异氰酸酯、2，4-甲苯二异氰酸酯、2，6-甲苯二异氰酸酯、六亚甲基二异氰酸酯、三甲基六亚甲基二异氰酸酯、二苯基甲烷-4，4’-二异氰酸酯(MDI)、氢化MDI、聚合MDI、1，5-萘二异氰酸酯(NDI)、降冰片烷二异氰酸酯、联甲苯胺二异氰酸酯、苯二亚甲基二异氰酸酯(XDI)、氢化XDI、赖氨酸二异氰酸酯、三苯基甲烷三异氰酸酯、三(异氰酸酯苯基)硫代磷酸酯、四甲基二甲苯二异氰酸酯、1，6，11-十一烷三异氰酸酯等。Among the compounds having at least one group selected from the group consisting of an isocyanate group, an isothiocyanate group, and a carbodiimide group, specific examples of the compound having an isocyanate group include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), hydrogenated MDI, polymerized MDI, 1,5-naphthalene diisocyanate (NDI), norbornane diisocyanate, toluidine diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenyl Methane triisocyanate, tris(isocyanate phenyl) phosphorothioate, tetramethylxylene diisocyanate, 1,6,11-undecanetriisocyanate, etc.
上述具有选自异氰酸酯基、异硫氰酸酯基和碳二亚胺基中的至少1种基团的化合物之中，作为具有异硫氰酸酯基的化合物，具体可以列举出例如异硫氰酸苄酯、异硫氰酸苯酯、异硫氰酸4-苯基丁酯、异硫氰酸3-苯基丙酯等。Among the compounds having at least one group selected from the group consisting of an isocyanate group, an isothiocyanate group, and a carbodiimide group, examples of the compound having an isothiocyanate group include, for example, isothiocyanate. Benzyl acid, phenyl isothiocyanate, 4-phenylbutyl isothiocyanate, 3-phenylpropyl isothiocyanate, etc.
上述具有选自异氰酸酯基、异硫氰酸酯基和碳二亚胺基中的至少1种基团的化合物之中，作为具有碳二亚胺基的化合物，具体可以列举出例如N，N-二环己基碳二亚胺、N，N-二异丙基碳二亚胺、1-乙基-3-(3-二甲基氨基丙基)碳二亚胺盐酸盐、双(2，6-二异丙基苯基)碳二亚胺等，作为市售品，例如可举出CARBODILITE LA-1(日清纺公司制)等。Among the above-mentioned compounds having at least one group selected from the group consisting of an isocyanate group, an isothiocyanate group and a carbodiimide group, specific examples of the compound having a carbodiimide group include N,N- Dicyclohexylcarbodiimide, N,N-diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, bis(2, 6-diisopropylphenyl)carbodiimide etc., as a commercial item, CARBODILITE LA-1 (made by Nisshinbo Co., Ltd.) etc. are mentioned, for example.
其中，从使交联密度提高、所得的光湿气固化型树脂组合物的固化物成为粘接性优异的固化物的效果优异的方面出发，优选具有异氰酸酯基的化合物。这些具有选自异氰酸酯基、异硫氰酸酯基和碳二亚胺基中的至少1种基团的化合物可以单独使用，也可以2种以上组合使用。Among them, compounds having an isocyanate group are preferred from the viewpoint that the crosslinking density is improved and the resulting cured product of the optical moisture-curable resin composition has an excellent effect of being a cured product excellent in adhesiveness. These compounds having at least one group selected from the group consisting of an isocyanate group, an isothiocyanate group, and a carbodiimide group may be used alone or in combination of two or more.
另外，作为上述除水剂，可以使用上述具有选自异氰酸酯基、异硫氰酸酯基和碳二亚胺基中的至少1种基团的化合物以外的其他除水剂。作为上述的其他除水剂，可以列举出例如氧化硼、氧化钙、氧化镁、氧化铬、氧化锰、氧化铁、氧化铜、氧化银、氧化铟、氧化钡、氧化铅、氧化磷、氧化锶、活性氧化铝等金属氧化物；硫酸镁、硫酸钠、硫酸镍等金属硫酸盐；氢氧化钠、氢氧化钾等金属氢氧化物；金属氢化物；铝氧化物辛酸盐等有机金属化合物；沸石类化合物、水滑石类化合物、硅胶、铝硅胶(アルミノシリカゲル)、连二亚硫酸钠、一元或多元羧酸的酸酐、丙烯酸盐、碳酰肼、抗坏血酸盐、没食子酸、烷氧基硅烷、碳纳米管、活性碳、纤维素粉末等。Moreover, as the said water scavenger, other than the compound which has at least 1 sort(s) group chosen from the said isocyanate group, an isothiocyanate group, and a carbodiimide group mentioned above can be used. Examples of the above-mentioned other water scavengers include boron oxide, calcium oxide, magnesium oxide, chromium oxide, manganese oxide, iron oxide, copper oxide, silver oxide, indium oxide, barium oxide, lead oxide, phosphorus oxide, and strontium oxide. , activated alumina and other metal oxides; magnesium sulfate, sodium sulfate, nickel sulfate and other metal sulfates; sodium hydroxide, potassium hydroxide and other metal hydroxides; metal hydrides; aluminum oxide octoate and other organometallic compounds; Zeolite-based compounds, hydrotalcite-based compounds, silica gel, aluminum silica gel (アルミノシリカゲル), sodium dithionite, anhydrides of mono- or polycarboxylic acids, acrylates, carbohydrazides, ascorbates, gallic acid, alkoxysilanes, carbon nanoparticles Tube, activated carbon, cellulose powder, etc.
这些其他除水剂可以单独使用，也可以将2种以上组合使用。另外，这些其他除水剂可以与上述具有选自异氰酸酯基、异硫氰酸酯基和碳二亚胺基中的至少1种基团的化合物组合使用。These other water-removing agents may be used alone or in combination of two or more. In addition, these other water scavengers can be used in combination with the above-mentioned compound having at least one group selected from the group consisting of an isocyanate group, an isothiocyanate group, and a carbodiimide group.
在本发明的光湿气固化型树脂组合物全体100重量份中，上述除水剂的含量的优选下限为0.05重量份，优选上限为10重量份。若上述除水剂的含量小于0.05重量份，则有时得到光湿气固化型树脂组合物的保存稳定性、粘接性差。若上述除水剂的含量大于10重量份，则湿气固化型聚氨酯树脂的固化时的交联度过度提高，变得脆硬。上述除水剂的含量的更优选下限为0.1重量份，更优选上限为5.0重量份，进一步优选下限为0.2重量份，进一步优选上限为3.0重量份，特别优选上限为1.5重量份。The preferable lower limit of the content of the water scavenger is 0.05 parts by weight and the preferable upper limit is 10 parts by weight in 100 parts by weight of the total optical moisture-curable resin composition of the present invention. When content of the said water scavenger is less than 0.05 weight part, the storage stability and adhesiveness of the optical moisture curable resin composition obtained may be inferior. When the content of the water scavenger is more than 10 parts by weight, the degree of crosslinking at the time of curing the moisture-curable urethane resin increases excessively and becomes brittle. A more preferable lower limit of the content of the water scavenger is 0.1 part by weight, a more preferable upper limit is 5.0 part by weight, a further preferable lower limit is 0.2 part by weight, a further preferable upper limit is 3.0 part by weight, and a particularly preferable upper limit is 1.5 part by weight.
本发明的光湿气固化型树脂组合物含有自由基聚合性化合物。The optical moisture-curable resin composition of the present invention contains a radically polymerizable compound.
作为上述自由基聚合性化合物，只要是分子中具有自由基反应性官能团的化合物，则没有特别限定，优选作为自由基反应性官能团而具有不饱和双键的化合物，特别是从反应性方面出发，优选具有(甲基)丙烯酰基的树脂(以下，也称作“(甲基)丙烯酸类树脂”)。The radically polymerizable compound is not particularly limited as long as it has a radical-reactive functional group in the molecule, but is preferably a compound having an unsaturated double bond as a radical-reactive functional group, especially from the viewpoint of reactivity, A resin having a (meth)acryloyl group (hereinafter, also referred to as "(meth)acrylic resin") is preferable.
需要说明的是，本说明书中，上述“(甲基)丙烯酰基”表示丙烯酰基或甲基丙烯酰基，上述“(甲基)丙烯酸类”表示丙烯酸类或甲基丙烯酸类。In addition, in this specification, the said "(meth)acryloyl group" represents an acryloyl group or a methacryloyl group, and the said "(meth)acrylic group" represents an acrylic group or a methacrylic group.
作为上述(甲基)丙烯酸类树脂，可以列举出例如通过使(甲基)丙烯酸与具有羟基的化合物反应而得到酯化合物；通过使(甲基)丙烯酸和环氧化合物反应而得到环氧(甲基)丙烯酸酯；通过使异氰酸酯与具有羟基的(甲基)丙烯酸衍生物反应而得到的氨基甲酸酯(甲基)丙烯酸酯等。Examples of the above-mentioned (meth)acrylic resin include ester compounds obtained by reacting (meth)acrylic acid with a compound having a hydroxyl group, and epoxy (meth)acrylic resins obtained by reacting (meth)acrylic acid and epoxy compounds. (meth)acrylate; urethane (meth)acrylate obtained by reacting isocyanate with a (meth)acrylic acid derivative having a hydroxyl group, and the like.
需要说明的是，本说明书中，上述“(甲基)丙烯酸酯”表示丙烯酸酯或甲基丙烯酸酯。In addition, in this specification, the said "(meth)acrylate" represents an acrylate or a methacrylate.
作为上述酯化合物中的单官能化合物，可以列举出例如N-丙烯酰氧基乙基六氢邻苯二甲酰亚胺等邻苯二甲酰亚胺丙烯酸酯类、各种酰亚胺丙烯酸酯、(甲基)丙烯酸-2-羟乙酯、(甲基)丙烯酸-2-羟丙酯、(甲基)丙烯酸-4-羟丁酯、(甲基)丙烯酸-2-羟丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸-2-甲氧基乙酯、甲氧基乙二醇(甲基)丙烯酸酯、(甲基)丙烯酸-2-乙氧基乙酯、(甲基)丙烯酸四氢糠基酯、(甲基)丙烯酸苄酯、乙基卡必醇(甲基)丙烯酸酯、(甲基)丙烯酸苯氧基乙酯、苯氧基二乙二醇(甲基)丙烯酸酯、苯氧基聚乙二醇(甲基)丙烯酸酯、甲氧基聚乙二醇(甲基)丙烯酸酯、2，2，2-三氟乙基(甲基)丙烯酸酯、2，2，3，3-四氟丙基(甲基)丙烯酸酯、1H，1H，5H-八氟戊基(甲基)丙烯酸酯、酰亚胺(甲基)丙烯酸酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸-2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸异壬酯、(甲基)丙烯酸异肉豆蔻酯、(甲基)丙烯酸-2-丁氧基乙酯、(甲基)丙烯酸-2-苯氧基乙酯、(甲基)丙烯酸双环戊烯酯、(甲基)丙烯酸异癸酯、二乙基氨基乙基(甲基)丙烯酸酯、二甲基氨基乙基(甲基)丙烯酸酯、2-(甲基)丙烯酰氧基乙基琥珀酸、2-(甲基)丙烯酰氧基乙基六氢邻苯二甲酸、2-(甲基)丙烯酰氧基乙基-2-羟丙基邻苯二甲酸酯、(甲基)丙烯酸缩水甘油酯、2-(甲基)丙烯酰氧基乙基磷酸酯等。As the monofunctional compound in the above-mentioned ester compound, for example, phthalimide acrylates such as N-acryloyloxyethylhexahydrophthalimide, and various imide acrylates can be mentioned. , (meth)acrylate-2-hydroxyethyl, (meth)acrylate-2-hydroxypropyl, (meth)acrylate-4-hydroxybutyl, (meth)acrylate-2-hydroxybutyl, ( Isobutyl meth)acrylate, tert-butyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isobornyl (meth)acrylate Esters, Cyclohexyl (Meth)acrylate, 2-Methoxyethyl (Meth)acrylate, Methoxyethylene Glycol (Meth)acrylate, 2-Ethoxyethyl (Meth)acrylate Ester, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene Alcohol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, 2,2,2-trifluoroethyl (meth) Acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, imide (meth)acrylate, ( Methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, propyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylic acid n-octyl ester, isononyl (meth)acrylate, isomyristyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate , Dicyclopentenyl (meth)acrylate, isodecyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, 2-(methyl) base) acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalic acid Diformate, glycidyl (meth)acrylate, 2-(meth)acryloyloxyethyl phosphate, and the like.
另外，作为上述酯化合物中的2官能的化合物，可以列举出例如1，4-丁二醇二(甲基)丙烯酸酯、1，3-丁二醇二(甲基)丙烯酸酯、1，6-己二醇二(甲基)丙烯酸酯、1，9-壬二醇二(甲基)丙烯酸酯、1，10-癸二醇二(甲基)丙烯酸酯、2-正丁基-2-乙基-1，3-丙二醇二(甲基)丙烯酸酯、二丙二醇二(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、环氧丙烷加成双酚A二(甲基)丙烯酸酯、环氧乙烷加成双酚A二(甲基)丙烯酸酯、环氧乙烷加成双酚F二(甲基)丙烯酸酯、二羟甲基二环戊二烯基二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、环氧乙烷改性异氰脲酸二(甲基)丙烯酸酯、2-羟基-3-(甲基)丙烯酰氧基丙基(甲基)丙烯酸酯、碳酸酯二醇二(甲基)丙烯酸酯、聚醚二醇二(甲基)丙烯酸酯、聚酯二醇二(甲基)丙烯酸酯、聚己内酯二醇二(甲基)丙烯酸酯、聚丁二烯二醇二(甲基)丙烯酸酯等。Moreover, as a bifunctional compound in the said ester compound, 1, 4- butanediol di(meth)acrylate, 1, 3- butanediol di(meth)acrylate, 1,6-butanediol di(meth)acrylate, -Hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 2-n-butyl-2- Ethyl-1,3-propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol (meth)acrylate, ethylene glycol di(meth)acrylate Meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene oxide addition bisphenol A Di(meth)acrylate, ethylene oxide addition bisphenol A di(meth)acrylate, ethylene oxide addition bisphenol F di(meth)acrylate, dimethylol dicyclopentane Alkenyl di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide modified isocyanurate di(meth)acrylate, 2-hydroxy-3-(methyl) Acryloyloxypropyl (meth)acrylate, carbonate diol di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol di(meth)acrylate, poly Caprolactone diol di(meth)acrylate, polybutadiene diol di(meth)acrylate, etc.
另外，作为上述酯化合物中的3官能以上的化合物，可以列举出例如季戊四醇三(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、环氧丙烷加成三羟甲基丙烷三(甲基)丙烯酸酯、环氧乙烷加成三羟甲基丙烷三(甲基)丙烯酸酯、己内酯改性三羟甲基丙烷三(甲基)丙烯酸酯、环氧乙烷加成异氰脲酸三(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、双三羟甲基丙烷四(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、丙三醇三(甲基)丙烯酸酯、环氧丙烷加成丙三醇三(甲基)丙烯酸酯、三(甲基)丙烯酰氧基乙基磷酸酯等。Moreover, as a trifunctional or more than trifunctional compound in the said ester compound, for example, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, propylene oxide addition trimethylolpropane is mentioned, for example Tri(meth)acrylate, ethylene oxide addition trimethylolpropane tri(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, ethylene oxide addition Isocyanurate tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate Meth)acrylate, glycerol tri(meth)acrylate, propylene oxide addition glycerol tri(meth)acrylate, tri(meth)acryloyloxyethyl phosphate and the like.
作为上述环氧(甲基)丙烯酸酯，可以列举出例如使环氧化合物和(甲基)丙烯酸按照常规方法在碱性催化剂的存在下反应而获得的环氧(甲基)丙烯酸酯等。As said epoxy (meth)acrylate, the epoxy (meth)acrylate etc. obtained by making an epoxy compound and (meth)acrylic acid react in the presence of a basic catalyst by a conventional method are mentioned, for example.
作为成为用于合成上述环氧(甲基)丙烯酸酯的原料的环氧化合物，可以列举出例如双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、2，2’-二烯丙基双酚A型环氧树脂、氢化双酚型环氧树脂、环氧丙烷加成双酚A型环氧树脂、间苯二酚型环氧树脂、联苯型环氧树脂、硫醚型环氧树脂、二苯基醚型环氧树脂、二环戊二烯型环氧树脂、萘型环氧树脂、苯酚酚醛清漆型环氧树脂、邻甲酚酚醛清漆型环氧树脂、二环戊二烯酚醛清漆型环氧树脂、联苯酚醛清漆型环氧树脂、萘酚酚醛清漆型环氧树脂、缩水甘油胺型环氧树脂、烷基多元醇型环氧树脂、橡胶改性型环氧树脂、缩水甘油酯化合物、双酚A型环硫化物树脂等。As an epoxy compound used as a raw material for synthesizing the above epoxy (meth)acrylate, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2 , 2'-diallyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type ring Oxygen resin, sulfide type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, phenol novolak type epoxy resin, o-cresol novolak type ring Oxygen resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolak type epoxy resin, glycidylamine type epoxy resin, alkyl polyol type epoxy resin, Rubber-modified epoxy resin, glycidyl ester compound, bisphenol A type episulfide resin, etc.
作为上述双酚A型环氧树脂中的市售品，可以列举出例如jER828EL、jER1001、jER1004(均为三菱化学公司制)、EPICLON 850-S(DIC公司制)等。As a commercial item among the said bisphenol A epoxy resins, jER828EL, jER1001, jER1004 (all are made by Mitsubishi Chemical Corporation), EPICLON 850-S (made by DIC Corporation), etc. are mentioned, for example.
作为上述双酚F型环氧树脂中的市售品，可以列举出例如jER806、jER4004(均为三菱化学公司制)等。As a commercial item among the said bisphenol F-type epoxy resins, jER806, jER4004 (all are the Mitsubishi Chemical Corporation make) etc. are mentioned, for example.
作为上述双酚S型环氧树脂中的市售品，可以列举出例如EPICLON EXA1514(DIC公司制)等。As what is marketed among the said bisphenol S type epoxy resins, EPICLON EXA1514 (made by DIC Corporation) etc. are mentioned, for example.
作为上述2，2’-二烯丙基双酚A型环氧树脂中的市售品，可以列举出例如RE-810NM(日本化药公司制)等。Among the above-mentioned 2,2'-diallylbisphenol A type epoxy resins, commercial products include, for example, RE-810NM (manufactured by Nippon Kayaku Co., Ltd.).
作为上述氢化双酚型环氧树脂中的市售品，可以列举出例如EPICLON EXA7015(DIC公司制)等。As a commercial item among the said hydrogenated bisphenol-type epoxy resins, EPICLON EXA7015 (made by DIC Corporation) etc. are mentioned, for example.
作为上述环氧丙烷加成双酚A型环氧树脂中的市售品，可以列举出例如EP-4000S(ADEKA公司制)等。As a commercial item among the said propylene oxide addition bisphenol A type epoxy resin, EP-4000S (made by ADEKA company) etc. are mentioned, for example.
作为上述间苯二酚型环氧树脂中的市售品，可以列举例如EX-201(NagaseChemtex公司制)等。As a commercial item among the said resorcinol-type epoxy resins, EX-201 (made by NagaseChemtex Corporation) etc. are mentioned, for example.
作为上述联苯型环氧树脂中的市售品，可以列举例如jERYX-4000H(三菱化学公司制)等。As a commercial item among the said biphenyl type epoxy resins, jERYX-4000H (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example.
作为上述硫醚型环氧树脂中的市售品，可以列举例如YSLV-50TE(新日铁住金化学公司制)等。As a commercial item among the said sulfide-type epoxy resins, YSLV-50TE (made by Nippon-Steel Sumigin Chemical Co., Ltd.) etc. is mentioned, for example.
作为上述二苯基醚型环氧树脂中的市售品，可以列举例如YSLV-80DE(新日铁住金化学公司制)等。As what is marketed among the said diphenyl ether type epoxy resins, YSLV-80DE (made by Nippon-Steel Sumigin Chemical Co., Ltd.) etc. is mentioned, for example.
作为上述二环戊二烯型环氧树脂中的市售品，可以列举例如EP-4088S(ADEKA公司制)等。As a commercial item among the said dicyclopentadiene-type epoxy resins, EP-4088S (made by ADEKA company) etc. are mentioned, for example.
作为上述萘型环氧树脂中的市售品，可以列举例如EPICLON HP4032、EPICLONEXA-4700(均为DIC公司制)等。As what is marketed among the said naphthalene-type epoxy resins, EPICLON HP4032, EPICLONEXA-4700 (all are made by DIC Corporation) etc. are mentioned, for example.
作为上述苯酚酚醛清漆型环氧树脂中的市售品，可以列举例如EPICLON N-770(DIC公司制)等。As a commercial item among the said phenol novolak-type epoxy resins, EPICLON N-770 (made by DIC Corporation) etc. are mentioned, for example.
作为上述邻甲酚酚醛清漆型环氧树脂中的市售品，可以列举例如EPICLON N-670-EXP-S(DIC公司制)等。As a commercial item among the said o-cresol novolak-type epoxy resins, EPICLON N-670-EXP-S (made by DIC Corporation) etc. are mentioned, for example.
作为上述二环戊二烯酚醛清漆型环氧树脂中的市售品，可以列举例如EPICLONHP7200(DIC公司制)等。As what is marketed among the said dicyclopentadiene novolak-type epoxy resins, EPICLON HP7200 (made by DIC Corporation) etc. are mentioned, for example.
作为上述联苯酚醛清漆型环氧树脂中的市售品，可以列举例如NC-3000P(日本化药公司制)等。As a commercial item among the said biphenyl novolak-type epoxy resins, NC-3000P (made by Nippon Kayaku Co., Ltd.) etc. are mentioned, for example.
作为上述萘酚酚醛清漆型环氧树脂中的市售品，可以列举例如ESN-165S(新日铁住金化学公司制)等。As what is marketed among the said naphthol novolak-type epoxy resins, ESN-165S (made by Nippon-Steel Sumigin Chemical Co., Ltd.) etc. is mentioned, for example.
作为上述缩水甘油胺型环氧树脂中的市售品，可以列举例如jER630(三菱化学公司制)、EPICLON 430(DIC公司制)、TETRAD-X(三菱瓦斯化学公司制)等。As a commercial item among the said glycidylamine type epoxy resins, jER630 (made by Mitsubishi Chemical Corporation), EPICLON 430 (made by DIC Corporation), TETRAD-X (made by Mitsubishi Gas Chemical Corporation), etc. are mentioned, for example.
作为上述烷基多元醇型环氧树脂中的市售品，可以列举例如ZX-1542(新日铁住金化学公司制)、EPICLON 726(DIC公司制)、EPOLIGHT80MFA(共荣社化学公司制)、DENACOLEX-611(Nagase Chemtex公司制)等。As a commercial item among the said alkyl polyol type epoxy resins, for example, ZX-1542 (made by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), EPICLON 726 (made by DIC Co., Ltd.), EPOLIGHT80MFA (made by Kyoeisha Chemical Co., Ltd.), DENACOLEX-611 (manufactured by Nagase Chemtex) and the like.
作为上述橡胶改性型环氧树脂中的市售品，可以列举例如YR-450、YR-207(均为新日铁住金化学公司制)、EPOLEAD PB(大赛璐公司制)等。As a commercial item among the said rubber-modified epoxy resins, YR-450, YR-207 (both are manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), EPOLEAD PB (made by Daicel Corporation), etc. are mentioned, for example.
作为上述缩水甘油酯化合物中的市售品，可以列举例如DENACOLEX-147(NagaseChemtex公司制)等。As a commercial item among the said glycidyl ester compounds, DENACOLEX-147 (made by Nagase Chemtex Corporation) etc. are mentioned, for example.
作为上述双酚A型环硫化物树脂中的市售品，可以列举例如jERYL-7000(三菱化学公司制)等。As a commercial item among the said bisphenol A type episulfide resin, jERYL-7000 (made by Mitsubishi Chemical Corporation) etc. are mentioned, for example.
作为上述环氧树脂中的其它市售品，可以列举例如YDC-1312、YSLV-80XY、YSLV-90CR(均为新日铁住金化学公司制)、XAC4151(旭化成公司制)、jER1031、jER1032(均为三菱化学公司制)、EXA-7120(DIC公司制)、TEPIC(日产化学公司制)等。As other commercially available products among the above epoxy resins, for example, YDC-1312, YSLV-80XY, YSLV-90CR (all manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), XAC4151 (manufactured by Asahi Kasei Corporation), jER1031, and jER1032 (all manufactured by Asahi Kasei Corporation) may be mentioned. For Mitsubishi Chemical Corporation), EXA-7120 (DIC Corporation), TEPIC (Nissan Chemical Corporation) and so on.
作为上述环氧(甲基)丙烯酸酯中的市售品，可以列举例如EBECRYL860、EBECRYL3200、EBECRYL3201、EBECRYL3412、EBECRYL3600、EBECRYL3700、EBECRYL3701、EBECRYL3702、EBECRYL3703、EBECRYL3800、EBECRYL6040、EBECRYL RDX63182(均为DAICEL-ALLNEXLTD.制)、EA-1010、EA-1020、EA-5323、EA-5520、EA-CHD、EMA-1020(均为新中村化学工业公司制)、EPOXY ESTER M-600A、EPOXY ESTER 40EM、EPOXY ESTER 70PA、EPOXY ESTER200PA、EPOXY ESTER 80MFA、EPOXY ESTER 3002M、EPOXY ESTER 3002A、EPOXY ESTER1600A、EPOXY ESTER 3000M、EPOXY ESTER 3000A、EPOXY ESTER 200EA、EPOXY ESTER 400EA(均为共荣社化学公司制)、DENACOL ACRYLATE DA-141、DENACOL ACRYLATE DA-314、DENACOL ACRYLATE DA-911(均为Nagase Chemtex公司制)等。As a commercial item among the said epoxy (meth)acrylates, for example, EBECRYL860, EBECRYL3200, EBECRYL3201, EBECRYL3412, EBECRYL3600, EBECRYL3700, EBECRYL3701, EBECRYL3702, EBECRYL3703, EBECRYL3800, EBECRYL6040, EBECRYL RDXDA63182 manufactured), EA-1010, EA-1020, EA-5323, EA-5520, EA-CHD, EMA-1020 (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), EPOXY ESTER M-600A, EPOXY ESTER 40EM, EPOXY ESTER 70PA , EPOXY ESTER200PA, EPOXY ESTER 80MFA, EPOXY ESTER 3002M, EPOXY ESTER 3002A, EPOXY ESTER1600A, EPOXY ESTER 3000M, EPOXY ESTER 3000A, EPOXY ESTER 200EA, EPOXY ESTER 400EA (all manufactured by Kyoeisha Chemical Co., Ltd.), DENACOL ACRYLATE DA-14 , DENACOL ACRYLATE DA-314, DENACOL ACRYLATE DA-911 (all manufactured by Nagase Chemtex), etc.
上述氨基甲酸酯(甲基)丙烯酸酯可以通过例如在催化剂量的锡系化合物存在下，使具有2个异氰酸酯基的化合物1当量与具有羟基的(甲基)丙烯酸衍生物2当量反应而得到。The above-mentioned urethane (meth)acrylate can be obtained by, for example, reacting 1 equivalent of a compound having two isocyanate groups with 2 equivalents of a (meth)acrylic acid derivative having a hydroxyl group in the presence of a catalytic amount of a tin-based compound. .
作为成为上述氨基甲酸酯(甲基)丙烯酸酯的原料的异氰酸酯，可以列举出例如异佛尔酮二异氰酸酯、2，4-甲苯二异氰酸酯、2，6-甲苯二异氰酸酯、六亚甲基二异氰酸酯、三甲基六亚甲基二异氰酸酯、二苯基甲烷-4，4’-二异氰酸酯(MDI)、氢化MDI、聚合MDI、1，5-萘二异氰酸酯、降冰片烷二异氰酸酯、联甲苯胺二异氰酸酯、苯二亚甲基二异氰酸酯(XDI)、氢化XDI、赖氨酸二异氰酸酯、三苯基甲烷三异氰酸酯、三(异氰酸酯苯基)硫代磷酸酯、四甲基二甲苯二异氰酸酯、1，6，11-十一烷三异氰酸酯等。Examples of the isocyanate used as a raw material for the urethane (meth)acrylate include isophorone diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and hexamethylene diisocyanate. Isocyanates, Trimethylhexamethylene Diisocyanate, Diphenylmethane-4,4'-Diisocyanate (MDI), Hydrogenated MDI, Polymeric MDI, 1,5-Naphthalene Diisocyanate, Norbornane Diisocyanate, Dimethyl Aniline diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine diisocyanate, triphenylmethane triisocyanate, tris(isocyanatophenyl) phosphorothioate, tetramethylxylene diisocyanate, 1,6,11-Undecanetriisocyanate, etc.
另外，作为上述异氰酸酯，还可以使用例如通过乙二醇、丙三醇、山梨糖醇、三羟甲基丙烷、(聚)丙二醇、碳酸酯二醇、聚醚二醇、聚酯二醇、聚己内酯二醇等多元醇与过量的异氰酸酯的反应而得到的链延长了的异氰酸酯化合物。In addition, as the above-mentioned isocyanate, for example, ethylene glycol, glycerol, sorbitol, trimethylolpropane, (poly)propylene glycol, carbonate glycol, polyether glycol, polyester glycol, poly A chain-extended isocyanate compound obtained by the reaction of a polyol such as caprolactone diol with an excess of isocyanate.
作为成为上述氨基甲酸酯(甲基)丙烯酸酯的原料的、具有羟基的(甲基)丙烯酸衍生物，可以列举出例如乙二醇、丙二醇、1，3-丙二醇、1，3-丁二醇、1，4-丁二醇、聚乙二醇等二元醇的单(甲基)丙烯酸酯、三羟甲基乙烷、三羟甲基丙烷、丙三醇等三元醇的单(甲基)丙烯酸酯或二(甲基)丙烯酸酯、双酚A型环氧(甲基)丙烯酸酯等环氧(甲基)丙烯酸酯等。As the (meth)acrylic acid derivative having a hydroxyl group used as a raw material of the above-mentioned urethane (meth)acrylate, for example, ethylene glycol, propylene glycol, 1,3-propylene glycol, and 1,3-butanediol can be mentioned. Mono(meth)acrylates of dihydric alcohols such as alcohol, 1,4-butanediol, polyethylene glycol, mono(meth)acrylates of trihydric alcohols such as trimethylolethane, trimethylolpropane, and glycerol Epoxy (meth)acrylates such as meth)acrylates, di(meth)acrylates, bisphenol A type epoxy (meth)acrylates, and the like.
作为上述氨基甲酸酯(甲基)丙烯酸酯中的市售品，可以列举出例如M-1100、M-1200、M-1210、M-1600(均为东亚合成公司制)、EBECRYL230、EBECRYL270、EBECRYL4858、EBECRYL8402、EBECRYL8411、EBECRYL8412、EBECRYL8413、EBECRYL8804、EBECRYL8803、EBECRYL8807、EBECRYL9260、EBECRYL 1290、EBECRYL5129、EBECRYL4842、EBECRYL210、EBECRYL4827、EBECRYL6700、EBECRYL220、EBECRYL2220、KRM7735、KRM-8295(均为DAICEL-ALLNEX LTD.制)、Artresin UN-9000H、Artresin UN-9000A、Artresin UN-7100、ArtresinUN一1255、Artresin UN-330、Artresin UN-3320HB、Artresin UN-1200TPK、Artresin SH-500B(均为根上工业公司制)、U-2HA、U-2PHA、U-3HA、U-4HA、U-6H、U-6LPA、U-6HA、U-10H、U-15HA、U-122A、U-122P、U-108、U-108A、U-324A、U-340A、U-340P、U-1084A、U-2061BA、UA-340P、UA-4100、UA-4000、UA-4200、UA-4400、UA-5201P、UA-7100、UA-7200、UA-W2A(均为新中村化学工业公司制)、AI-600、AH-600、AT-600、UA-101I、UA-101T、UA-306H、UA-306I、UA-306T(均为共荣社化学公司制)等。As a commercial item among the said urethane (meth)acrylate, M-1100, M-1200, M-1210, M-1600 (all are made by Toagosei Co., Ltd.), EBECRYL230, EBECRYL270, EBECRYL4858、EBECRYL8402、EBECRYL8411、EBECRYL8412、EBECRYL8413、EBECRYL8804、EBECRYL8803、EBECRYL8807、EBECRYL9260、EBECRYL 1290、EBECRYL5129、EBECRYL4842、EBECRYL210、EBECRYL4827、EBECRYL6700、EBECRYL220、EBECRYL2220、KRM7735、KRM-8295(均为DAICEL-ALLNEX LTD.制) , Artresin UN-9000H, Artresin UN-9000A, Artresin UN-7100, ArtresinUN-1255, Artresin UN-330, Artresin UN-3320HB, Artresin UN-1200TPK, Artresin SH-500B (all made by Negami Industries), U- 2HA, U-2PHA, U-3HA, U-4HA, U-6H, U-6LPA, U-6HA, U-10H, U-15HA, U-122A, U-122P, U-108, U-108A, U-324A, U-340A, U-340P, U-1084A, U-2061BA, UA-340P, UA-4100, UA-4000, UA-4200, UA-4400, UA-5201P, UA-7100, UA- 7200, UA-W2A (all are manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), AI-600, AH-600, AT-600, UA-101I, UA-101T, UA-306H, UA-306I, UA-306T (all are Kyoeisha Chemical Co., Ltd.), etc.
另外，也可以适当使用上述以外的其他自由基聚合性化合物。In addition, other radically polymerizable compounds other than those described above can also be appropriately used.
作为上述的其他自由基聚合性化合物，可以列举出例如N，N-二甲基(甲基)丙烯酰胺、N-(甲基)丙烯酰吗啉、N-羟基乙基(甲基)丙烯酰胺、N，N-二乙基(甲基)丙烯酰胺、N-异丙基(甲基)丙烯酰胺、N，N-二甲基氨基丙基(甲基)丙烯酰胺等(甲基)丙烯酰胺化合物、苯乙烯、α-甲基苯乙烯、N-吡咯烷酮、N-乙烯基己内酯等乙烯基化合物等。Examples of the above-mentioned other radically polymerizable compounds include N,N-dimethyl(meth)acrylamide, N-(meth)acryloylmorpholine, and N-hydroxyethyl(meth)acrylamide. , N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide and other (meth)acrylamides Compounds, vinyl compounds such as styrene, α-methylstyrene, N-pyrrolidone, N-vinylcaprolactone, and the like.
从调整固化性等观点出发，上述自由基聚合性化合物优选含有单官能自由基聚合性化合物和多官能自由基聚合性化合物。仅使用单官能自由基聚合性化合物时，有时所得的光湿气固化型树脂组合物的固化性差，仅使用多官能自由基聚合性化合物时，有时所得的光湿气固化型树脂组合物的粘着性差。其中，更优选组合使用作为上述单官能自由基聚合性化合物的分子中具有氮原子的化合物、和作为上述多官能自由基聚合性化合物的氨基甲酸酯(甲基)丙烯酸酯。另外，上述多官能自由基聚合性化合物优选2官能或3官能，更优选2官能。It is preferable that the said radically polymerizable compound contains a monofunctional radically polymerizable compound and a polyfunctional radically polymerizable compound from a viewpoint of sclerosis|hardenability adjustment etc.. When only a monofunctional radically polymerizable compound is used, the curability of the resulting optical moisture-curable resin composition may be poor, and when only a polyfunctional radically polymerizable compound is used, the resulting optically moisture-curable resin composition may suffer from sticking Bad sex. Among them, it is more preferable to use a compound having a nitrogen atom in the molecule as the monofunctional radically polymerizable compound and urethane (meth)acrylate as the polyfunctional radically polymerizable compound in combination. In addition, the above-mentioned polyfunctional radically polymerizable compound is preferably bifunctional or trifunctional, and more preferably bifunctional.
上述自由基聚合性化合物含有上述单官能自由基聚合性化合物和上述多官能自由基聚合性化合物时，相对于上述单官能自由基聚合性化合物和上述多官能自由基聚合性化合物的合计100重量份，上述多官能自由基聚合性化合物的含量的优选下限为2重量份，优选上限为30重量份。若上述多官能自由基聚合性化合物的含量小于2重量份，则有时所得的光湿气固化型树脂组合物的固化性差。若上述多官能自由基聚合性化合物的含量大于30重量份，则有时所得的光湿气固化型树脂组合物的粘着性差。上述多官能自由基聚合性化合物的含量的更优选下限为5重量份，更优选上限为20重量份。When the said radically polymerizable compound contains the said monofunctional radically polymerizable compound and the said polyfunctional radically polymerizable compound, with respect to the sum total of the said monofunctional radically polymerizable compound and the said polyfunctional radically polymerizable compound 100 weight part , the preferred lower limit of the content of the polyfunctional radically polymerizable compound is 2 parts by weight, and the preferred upper limit is 30 parts by weight. When content of the said polyfunctional radically polymerizable compound is less than 2 weight part, the curability of the optical moisture curable resin composition obtained may be inferior. When content of the said polyfunctional radically polymerizable compound exceeds 30 weight part, the adhesiveness of the optical moisture curable resin composition obtained may be inferior. The more preferable lower limit of content of the said polyfunctional radically polymerizable compound is 5 weight part, and a more preferable upper limit is 20 weight part.
本发明的光湿气固化型树脂组合物含有湿气固化型聚氨酯树脂。对于上述湿气固化型聚氨酯树脂而言，分子内的异氰酸酯基与空气中或被粘物中的水分反应而固化。另外，与使用具有交联性甲硅烷基的化合物等作为湿气固化成分的情况相比，所得的光湿气固化型树脂组合物的速固化性优异。The optical moisture-curable resin composition of the present invention contains a moisture-curable polyurethane resin. In the above-mentioned moisture-curable urethane resin, the isocyanate group in the molecule reacts with moisture in the air or the adherend to cure. Moreover, compared with the case where the compound etc. which have a crosslinkable silyl group are used as a moisture-curable component, the quick-curing property of the optical moisture-curable resin composition obtained is excellent.
对于上述湿气固化型聚氨酯树脂而言，1分子中可以仅含有1个异氰酸酯基，也可以含有2个以上。其中，优选在两末端具有异氰酸酯基的聚氨酯预聚物。The said moisture-curable polyurethane resin may contain only one isocyanate group in 1 molecule, and may contain two or more. Among them, a polyurethane prepolymer having isocyanate groups at both ends is preferable.
上述聚氨酯预聚物可以通过如下方法得到，即，使1分子中具有2个以上羟基的多元醇化合物、与1分子中具有2个以上的异氰酸酯基的多异氰酸酯化合物反应。The above-mentioned polyurethane prepolymer can be obtained by reacting a polyol compound having two or more hydroxyl groups in one molecule with a polyisocyanate compound having two or more isocyanate groups in one molecule.
上述多元醇化合物与多异氰酸酯化合物的反应通常在以多元醇化合物中的羟基(OH)与多异氰酸酯化合物中的异氰酸酯基(NCO)的摩尔比计为[NCO]/[OH]＝2.0～2.5的范围内进行。The reaction between the above-mentioned polyol compound and the polyisocyanate compound is usually in the range of [NCO]/[OH]=2.0 to 2.5 in terms of the molar ratio of the hydroxyl group (OH) in the polyol compound and the isocyanate group (NCO) in the polyisocyanate compound. within the range.
作为上述多元醇化合物，可以使用在聚氨酯的制造中通常使用的公知的多元醇化合物，可以列举出例如聚酯多元醇、聚醚多元醇、聚烷撑多元醇、聚碳酸酯多元醇等。这些多元醇化合物可以单独使用，也可以2种以上组合使用。As said polyol compound, the well-known polyol compound generally used for manufacture of a polyurethane can be used, For example, polyester polyol, polyether polyol, polyalkylene polyol, polycarbonate polyol, etc. are mentioned. These polyol compounds may be used alone or in combination of two or more.
作为上述聚酯多元醇，可以列举例如通过多元羧酸与多元醇的反应而得到的聚酯多元醇、将ε-己内酯开环聚合而得到的聚-ε-己内酯多元醇等。As said polyester polyol, the polyester polyol obtained by reaction of a polyhydric carboxylic acid and a polyol, the poly- (epsilon)-caprolactone polyol obtained by ring-opening polymerization of (epsilon)-caprolactone, etc. are mentioned, for example.
作为成为上述聚酯多元醇的原料的上述多元羧酸，可以列举例如对苯二甲酸、间苯二甲酸、1，5-萘二甲酸、2，6-萘二甲酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、十亚甲基二羧酸、十二亚甲基二羧酸等。Examples of the polyvalent carboxylic acid used as a raw material for the polyester polyol include terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, succinic acid, and glutaric acid. , adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid, dodecanedioic acid, etc.
作为成为上述聚酯多元醇的原料的上述多元醇，可以列举例如乙二醇、丙二醇、1，3-丙二醇、1，4-丁二醇、新戊二醇、1，5-戊二醇、1，6-己二醇、二甘醇、环己二醇等。Examples of the above-mentioned polyol used as a raw material for the above-mentioned polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, cyclohexanediol, etc.
作为上述聚醚多元醇，可以列举例如乙二醇、丙二醇、四氢呋喃、3-甲基四氢呋喃的开环聚合物、以及它们或其衍生物的无规共聚物或嵌段共聚物、双酚型的聚氧化烯改性体等。Examples of the above-mentioned polyether polyol include ring-opening polymers of ethylene glycol, propylene glycol, tetrahydrofuran, and 3-methyltetrahydrofuran, random copolymers or block copolymers of these or derivatives thereof, and bisphenol-type polymers. Polyoxyalkylene modified body, etc.
上述双酚型的聚氧化烯改性体是在双酚型分子骨架的活性氢部分上使环氧烷(例如，环氧乙烷、环氧丙烷、环氧丁烷、环氧异丁烷等)进行加成反应而得到的聚醚多元醇，可以是无规共聚物，也可以是嵌段共聚物。The above-mentioned bisphenol-type polyoxyalkylene modified product is obtained by adding an alkylene oxide (for example, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, etc.) to the active hydrogen portion of the bisphenol-type molecular skeleton. ) The polyether polyol obtained by addition reaction may be a random copolymer or a block copolymer.
上述双酚型的聚氧化烯改性体优选在双酚型分子骨架的两末端加成1种或2种以上的环氧烷。作为双酚型，没有特别限定，可以列举A型、F型、S型等，优选为双酚A型。It is preferable to add one or two or more types of alkylene oxides to both ends of the bisphenol-type molecular skeleton in the above-mentioned bisphenol-type polyoxyalkylene modified product. Although it does not specifically limit as a bisphenol type, A type, F type, S type, etc. are mentioned, Preferably it is a bisphenol A type.
作为上述聚烷撑多元醇，可以列举例如聚丁二烯多元醇、氢化聚丁二烯多元醇、氢化聚异戊二烯多元醇等。As said polyalkylene polyol, a polybutadiene polyol, hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol, etc. are mentioned, for example.
作为上述聚碳酸酯多元醇，可以列举例如聚碳酸1，6-己二醇酯多元醇、聚环己烷碳酸乙二醇酯多元醇等。As said polycarbonate polyol, polycarbonate 1, 6- hexanediol polyol, polycyclohexane ethylene carbonate polyol, etc. are mentioned, for example.
作为上述多异氰酸酯化合物，可以列举例如二苯甲烷二异氰酸酯、二苯甲烷二异氰酸酯的液状改性物、聚MDI(甲烷二异氰酸酯)、甲苯二异氰酸酯、萘-1，5-二异氰酸酯等。其中，从蒸气压、毒性低的方面、容易操作的方面出发，优选二苯甲烷二异氰酸酯及其改性物。上述多异氰酸酯基化合物可以单独使用，也可以2种以上组合使用。As said polyisocyanate compound, diphenylmethane diisocyanate, the liquid modified product of diphenylmethane diisocyanate, polyMDI (methane diisocyanate), toluene diisocyanate, naphthalene-1, 5- diisocyanate etc. are mentioned, for example. Among them, diphenylmethane diisocyanate and modified products thereof are preferred from the viewpoint of low vapor pressure and toxicity, and ease of handling. The above-mentioned polyisocyanate-based compounds may be used alone or in combination of two or more.
另外，上述湿气固化型聚氨酯树脂优选为使用具有下述式(1)所表示的结构的多元醇化合物而得到的聚氨酯树脂。通过使用具有下述式(1)所表示的结构的多元醇化合物，而能够得到粘接性优异的组合物、柔软且伸长良好的固化物，成为与上述自由基聚合性化合物的相容性优异的聚氨酯树脂。Moreover, it is preferable that the said moisture-curable urethane resin is a urethane resin obtained using the polyol compound which has a structure represented by following formula (1). By using a polyol compound having a structure represented by the following formula (1), a composition excellent in adhesiveness, a cured product having flexibility and good elongation can be obtained, and compatibility with the above-mentioned radically polymerizable compound can be obtained Excellent polyurethane resin.
其中，优选使用包含丙二醇、四氢呋喃(THF)化合物的开环聚合化合物、或具有甲基等取代基的四氢呋喃化合物的开环聚合化合物的聚醚多元醇。Among them, a polyether polyol containing a ring-opening polymerized compound of propylene glycol, a tetrahydrofuran (THF) compound, or a ring-opened polymerized compound of a tetrahydrofuran compound having a substituent such as a methyl group is preferably used.
[化1][hua 1]
式(1)中，R表示氢、甲基或乙基，n为1～10的整数，L为0～5的整数，m为1～500的整数。n优选为1～5，L优选为0～4，m优选为50～200。In formula (1), R represents hydrogen, methyl or ethyl, n is an integer of 1-10, L is an integer of 0-5, and m is an integer of 1-500. n is preferably 1-5, L is preferably 0-4, and m is preferably 50-200.
需要说明的是，L为0的情况意味着与R键合的碳直接与氧键合的情况。In addition, the case where L is 0 means the case where the carbon bonded to R is directly bonded to oxygen.
进一步，上述湿气固化型聚氨酯树脂可以具有自由基聚合性官能团。Furthermore, the said moisture-curable urethane resin may have a radically polymerizable functional group.
作为上述湿气固化型聚氨酯树脂可具有的自由基聚合性官能团，优选具有不饱和双键的基团，特别是从反应性的方面出发，更优选(甲基)丙烯酰基。As a radically polymerizable functional group which the said moisture-curable urethane resin can have, the group which has an unsaturated double bond is preferable, and a (meth)acryloyl group is more preferable especially from the viewpoint of reactivity.
需要说明的是，具有自由基聚合性官能团的湿气固化型聚氨酯树脂不包含于自由基聚合性化合物中，而是作为湿气固化型聚氨酯树脂来处理。In addition, the moisture-curable urethane resin which has a radically polymerizable functional group is not contained in a radically polymerizable compound, but is handled as a moisture-curable urethane resin.
上述湿气固化型聚氨酯树脂的重均分子量的优选下限为800，优选上限为1万。若上述湿气固化型聚氨酯树脂的重均分子量小于800，则有时交联密度变高，柔软性被损害。若上述湿气固化型聚氨酯树脂的重均分子量大于1万，则有时所得的光湿气固化型树脂组合物的涂布性差。上述湿气固化型聚氨酯树脂的重均分子量的更优选下限为2000，更优选上限为8000，进一步优选下限为3000，进一步优选上限为6000。The preferable lower limit of the weight average molecular weight of the moisture-curable polyurethane resin is 800, and the preferable upper limit is 10,000. When the weight average molecular weight of the said moisture-curable polyurethane resin is less than 800, a crosslinking density may become high and flexibility may be impaired. When the weight average molecular weight of the said moisture-curable urethane resin exceeds 10,000, the coating property of the optical moisture-curable resin composition obtained may be inferior. A more preferable lower limit of the weight average molecular weight of the moisture-curable polyurethane resin is 2,000, a more preferable upper limit is 8,000, a further preferable lower limit is 3,000, and a further preferable upper limit is 6,000.
需要说明的是，在本说明书中，上述重均分子量是利用凝胶渗透色谱法(GPC)进行测定，通过聚苯乙烯换算求得的值。作为利用GPC测定基于聚苯乙烯换算的重均分子量时的色谱柱，可以列举例如ShodexLF-804(昭和电工公司制)等。另外，作为GPC中使用的溶剂，可以列举四氢呋喃等。In addition, in this specification, the said weight average molecular weight is the value calculated|required by polystyrene conversion by measuring by gel permeation chromatography (GPC). As a column for measuring the weight average molecular weight in terms of polystyrene by GPC, for example, ShodexLF-804 (manufactured by Showa Denko Co., Ltd.) and the like can be mentioned. Moreover, tetrahydrofuran etc. are mentioned as a solvent used for GPC.
相对于上述自由基聚合性化合物和上述湿气固化型聚氨酯树脂的合计100重量份，上述湿气固化型聚氨酯树脂的含量的优选下限为20重量份，优选上限为90重量份。若上述湿气固化型聚氨酯树脂的含量小于20重量份，则有时所得的光湿气固化型树脂组合物的湿气固化性差。若上述湿气固化型聚氨酯树脂的含量大于90重量份，则有时所得的光湿气固化型树脂组合物的光固化性差。上述湿气固化型聚氨酯树脂的含量的更优选下限为30重量份，更优选上限为75重量份，进一步优选下限为41重量份，进一步优选上限为70重量份。The preferable lower limit of the content of the moisture-curable polyurethane resin is 20 parts by weight, and the preferable upper limit is 90 parts by weight, based on 100 parts by weight of the total of the radically polymerizable compound and the moisture-curable polyurethane resin. When content of the said moisture-curable urethane resin is less than 20 weight part, the moisture curability of the optical moisture-curable resin composition obtained may be inferior. When content of the said moisture-curable urethane resin exceeds 90 weight part, the photocurability of the optical moisture-curable resin composition obtained may be inferior. A more preferable lower limit of the content of the moisture-curable polyurethane resin is 30 parts by weight, a more preferable upper limit is 75 parts by weight, a still more preferable lower limit is 41 parts by weight, and a further preferable upper limit is 70 parts by weight.
本发明的光湿气固化型树脂组合物含有光自由基聚合引发剂。The optical moisture-curable resin composition of the present invention contains a photoradical polymerization initiator.
作为上述光自由基聚合引发剂，可以列举例如二苯甲酮系化合物、苯乙酮系化合物、酰基氧化膦系化合物、二茂钛系化合物、肟酯系化合物、苯偶姻醚系化合物、噻吨酮等。Examples of the above-mentioned photo-radical polymerization initiator include benzophenone-based compounds, acetophenone-based compounds, acylphosphine oxide-based compounds, titanocene-based compounds, oxime ester-based compounds, benzoin ether-based compounds, and thiocyanate-based compounds. Tonone, etc.
作为上述光自由基聚合引发剂中的市售品，可以列举例如IRGACURE184、IRGACURE369、IRGACURE379、IRGACURE651、IRGACURE784、IRGACURE819、IRGACURE907、IRGACURE2959、IRGACURE OXE01、LucirinTPO(均为BASF Japan公司制)、苯偶姻甲醚、苯偶姻乙醚、苯偶姻异丙醚(均为东京化成工业公司制)等。Examples of commercially available products among the above-mentioned photo-radical polymerization initiators include IRGACURE184, IRGACURE369, IRGACURE379, IRGACURE651, IRGACURE784, IRGACURE819, IRGACURE907, IRGACURE2959, IRGACURE OXE01, LucirinTPO (all manufactured by BASF Japan), benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether (all manufactured by Tokyo Chemical Industry Co., Ltd.), and the like.
相对于上述自由基聚合性化合物100重量份，上述光自由基聚合引发剂的含量的优选下限为0.01重量份，优选上限为10重量份。若上述光自由基聚合引发剂的含量小于0.01重量份，则有时不能够充分地使得到的光湿气固化型树脂组合物进行光固化。若上述光自由基聚合引发剂的含量大于10重量份，则有时得到的光湿气固化型树脂组合物的保存稳定性降低。上述光自由基聚合引发剂的含量的更优选下限为0.1重量份，更优选上限为5重量份。The preferable lower limit of content of the said radical photopolymerization initiator is 0.01 weight part with respect to 100 weight part of said radically polymerizable compounds, and a preferable upper limit is 10 weight part. When the content of the above-mentioned radical photopolymerization initiator is less than 0.01 part by weight, the resulting optical moisture-curable resin composition may not be sufficiently photocured. When content of the said radical photopolymerization initiator exceeds 10 weight part, the storage stability of the optical moisture curable resin composition obtained may fall. The more preferable lower limit of content of the said photoradical polymerization initiator is 0.1 weight part, and a more preferable upper limit is 5 weight part.
本发明的光湿气固化型树脂组合物还可以含有遮光剂。通过含有上述遮光剂，本发明的光湿气固化型树脂组合物的遮光性变得优异，能够防止显示元件的漏光。The optical moisture-curable resin composition of the present invention may further contain a light-shielding agent. By containing the said light-shielding agent, the light-shielding property of the optical moisture-curable resin composition of this invention becomes excellent, and the light leakage of a display element can be prevented.
需要说明的是，在本说明书中，上述“遮光剂”表示具有使可见光区域的光难以透过的能力的材料。In addition, in this specification, the said "light-shielding agent" means the material which has the capability of making it difficult to transmit light in a visible light region.
作为上述遮光剂，可以列举例如氧化铁、钛黑、苯胺黑、花青黑、富勒烯、碳黑、树脂被覆型碳黑等。另外，上述遮光剂也可以不呈黑色，只要是具有使可见光区域的光难以透过的能力的材料，二氧化硅、滑石等作为后述的填充剂被例举的材料等也包含于上述遮光剂中。其中，优选钛黑。As said light-shielding agent, iron oxide, titanium black, aniline black, cyanine black, fullerene, carbon black, resin-coated carbon black, etc. are mentioned, for example. In addition, the above-mentioned light-shielding agent does not need to be black, as long as it is a material having the ability to hardly transmit light in the visible light region, silica, talc, and the like are also included in the above-mentioned light-shielding agent. in the agent. Among them, titanium black is preferable.
上述钛黑是与相对于波长为300～800nm的光的平均透射率相比，相对于紫外线区域附近、特别是波长为370～450nm的光的透射率变高的物质。即，上述钛黑为具有通过将可见光区域的波长的光充分地遮蔽而对本发明的光湿气固化型树脂组合物赋予遮光性，另一方面使紫外线区域附近的波长的光透射的性质的遮光剂。因此，作为光自由基聚合引发剂，通过使用利用上述钛黑的透射率变高的波长(370～450nm)的光能够引发反应的物质，从而能够使本发明的光湿气固化型树脂组合物的光固化性进一步增大。此外，另一方面，作为本发明的光湿气固化型树脂组合物中含有的遮光剂，优选绝缘性高的物质，作为绝缘性高的遮光剂，也优选钛黑。The above-mentioned titanium black has a higher transmittance with respect to light having a wavelength of 370 to 450 nm in the vicinity of the ultraviolet region than the average transmittance with respect to light with a wavelength of 300 to 800 nm. That is, the above-mentioned titanium black is a light-shielding property having a property of imparting light-shielding properties to the optical moisture-curable resin composition of the present invention by sufficiently shielding light of wavelengths in the visible light region and transmitting light of wavelengths in the vicinity of the ultraviolet region. agent. Therefore, as the photoradical polymerization initiator, the optical moisture curable resin composition of the present invention can be obtained by using a substance capable of initiating a reaction by light of a wavelength (370 to 450 nm) in which the transmittance of the titanium black is increased. The photocurability is further increased. On the other hand, as the light-shielding agent contained in the optical moisture-curable resin composition of the present invention, a material with high insulating properties is preferable, and as a light-shielding agent with high insulating property, titanium black is also preferable.
上述钛黑的光学浓度(OD值)优选为3以上，更优选为4以上。另外，上述钛黑的黑色度(L值)优选为9以上，更优选11以上。上述钛黑的遮光性越高越好，上述钛黑的OD值的优选上限没有特别限定，通常为5以下。The optical density (OD value) of the titanium black is preferably 3 or more, and more preferably 4 or more. Moreover, the blackness (L value) of the said titanium black becomes like this. Preferably it is 9 or more, More preferably, it is 11 or more. The higher the light-shielding property of the titanium black, the better. The preferable upper limit of the OD value of the titanium black is not particularly limited, but is usually 5 or less.
上述钛黑即使是未经表面处理的物质，也发挥出充分的效果，还可以使用表面利用偶联剂等有机成分处理过的物质、表面利用氧化硅、氧化钛、氧化锗、氧化铝、氧化锆、氧化镁等无机成分覆盖了的物质等经表面处理后的钛黑。其中，利用有机成分处理过的钛黑在能够进一步提高绝缘性的方面优选。The above-mentioned titanium black exhibits sufficient effects even if it is not surface-treated, and it is also possible to use those whose surfaces have been treated with organic components such as coupling agents, or those whose surfaces have been treated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, or oxide. Titanium black after surface treatment of substances covered with inorganic components such as zirconium and magnesium oxide. Among them, titanium black treated with an organic component is preferable in that the insulating properties can be further improved.
另外，对于使用本发明的光湿气固化型树脂组合物而制造的显示元件而言，由于光湿气固化型树脂组合物具有充分的遮光性，因此能够实现没有光的漏出而具有高对比度，且具有优异的图像显示品质。In addition, in the display element manufactured using the optical moisture-curable resin composition of the present invention, since the optical moisture-curable resin composition has sufficient light-shielding properties, it is possible to achieve high contrast without leakage of light, And has excellent image display quality.
作为上述钛黑中的市售品，可以列举例如12S、13M、13M-C、13R-N(均为三菱综合材料株式会社制)、Tilack D(赤穗化成公司制)等。As a commercial item among the said titanium black, 12S, 13M, 13M-C, 13R-N (all are made by Mitsubishi Materials Corporation), Tilack D (made by Ako Chemicals Co., Ltd.), etc. are mentioned, for example.
上述钛黑的比表面积的优选下限为5m2/g，优选上限为40m2/g，更优选下限为10m2/g，更优选上限为25m2/g。The preferred lower limit of the specific surface area of the titanium black is 5 m 2 /g, the preferred upper limit is 40 m 2 /g, the more preferred lower limit is 10 m 2 /g, and the more preferred upper limit is 25 m 2 /g.
另外，上述钛黑的片材电阻(シ一ト抵抗)的优选下限在与树脂混合的情况下(70％配合)为109Ω/□，更优选下限为1011Ω/□。In addition, the preferable lower limit of the sheet resistance of the titanium black described above is 10 9 Ω/□ when mixed with a resin (70% blending), and a more preferable lower limit is 10 11 Ω/□.
此外，上述钛黑的体积电阻的优选下限为0.5Ω·cm，优选上限为3Ω·cm，更优选下限为1Ω·cm，更优选上限为2.5Ω·cm。Further, the lower limit of the volume resistance of the titanium black is preferably 0.5 Ω·cm, the upper limit is preferably 3 Ω·cm, the lower limit is more preferably 1 Ω·cm, and the upper limit is more preferably 2.5 Ω·cm.
本发明的光湿气固化型树脂组合物中，上述遮光剂的一次粒径根据用途而适当选择显示元件的基板间的距离以下等，优选下限为30nm，优选上限为500nm。若上述遮光剂的一次粒径小于30nm，则得到的光湿气固化型树脂组合物的粘度、触变性显著增大，操作性变差。若上述遮光剂的一次粒径大于500nm，则得到的光湿气固化型树脂组合物中的遮光剂的分散性降低，有时遮光性降低。上述遮光剂的一次粒径的更优选下限为50nm，更优选上限为200nm。In the optical moisture-curable resin composition of the present invention, the primary particle diameter of the light-shielding agent is appropriately selected according to the application, such as the distance between the substrates of the display element and the like, preferably the lower limit is 30 nm, and the preferred upper limit is 500 nm. When the primary particle diameter of the said light-shielding agent is less than 30 nm, the viscosity and thixotropy of the optical moisture curable resin composition obtained will increase remarkably, and handleability will worsen. When the primary particle diameter of the said light-shielding agent exceeds 500 nm, the dispersibility of the light-shielding agent in the optical moisture curable resin composition obtained may fall, and light-shielding property may fall. The more preferable lower limit of the primary particle diameter of the said light-shielding agent is 50 nm, and a more preferable upper limit is 200 nm.
本发明的光湿气固化型树脂组合物全体中的上述遮光剂的含量没有特别限定，优选下限为0.05重量％，优选上限为10重量％。若上述遮光剂的含量小于0.05重量％，则不能够得到充分的遮光性。若上述遮光剂的含量大于10重量％，则有可能所得的光湿气固化型树脂组合物相对于基板等的粘接性、固化后的强度降低，或描绘性降低。上述遮光剂的含量的更优选下限为0.1重量％，更优选上限为2重量％，进一步优选下限为0.3重量％，进一步优选上限为1重量％。Although content of the said light-shielding agent in the whole optical moisture-curable resin composition of this invention is not specifically limited, A preferable minimum is 0.05 weight%, and a preferable upper limit is 10 weight%. When content of the said light-shielding agent is less than 0.05 weight%, sufficient light-shielding property cannot be acquired. When content of the said light-shielding agent exceeds 10 weight%, the adhesiveness with respect to a board|substrate etc. of the optical moisture curable resin composition obtained, the intensity|strength after hardening may fall, or drawing property may fall. The more preferable lower limit of the content of the sunscreen agent is 0.1% by weight, the more preferable upper limit is 2% by weight, the more preferable lower limit is 0.3% by weight, and the more preferable upper limit is 1% by weight.
从调整得到的光湿气固化型树脂组合物的涂布性、形状保持性等的观点出发，本发明的光湿气固化型树脂组合物可以含有填充剂。通过含有上述填充剂，本发明的光湿气固化型树脂组合物成为具有优选的触变性的组合物，能够充分地保持涂布后的形状。The optical moisture-curable resin composition of the present invention may contain a filler from the viewpoint of adjusting the coatability, shape retention, etc. of the optical moisture-curable resin composition obtained. By containing the said filler, the optical moisture-curable resin composition of this invention becomes a composition which has preferable thixotropy, and can fully maintain the shape after application|coating.
上述填充剂的一次粒径的优选下限为1nm，优选上限为50nm。若上述填充剂的一次粒径小于1nm，则有时得到的光湿气固化型树脂组合物的涂布性差。若上述填充剂的一次粒径大于50nm，则有时得到的光湿气固化型树脂组合物的涂布后的形状保持性差。上述填充剂的一次粒径的更优选下限为5nm，更优选上限为30nm，进一步优选下限为10nm，进一步优选上限为20nm。The preferable lower limit of the primary particle size of the filler is 1 nm, and the preferable upper limit is 50 nm. When the primary particle diameter of the said filler is less than 1 nm, the coating property of the optical moisture curable resin composition obtained may be inferior. When the primary particle diameter of the said filler exceeds 50 nm, the shape retention after application|coating of the optical moisture curable resin composition obtained may be inferior. A more preferable lower limit of the primary particle size of the filler is 5 nm, a more preferable upper limit is 30 nm, a further preferable lower limit is 10 nm, and a further preferable upper limit is 20 nm.
需要说明的是，上述填充剂的一次粒径可以使用NICOMP 380ZLS(PARTICLESIZING SYSTEMS公司制)，使上述填充剂分散于溶剂(水、有机溶剂等)中进行测定。In addition, the primary particle diameter of the said filler can be measured by dispersing the said filler in a solvent (water, an organic solvent, etc.) using NICOMP 380ZLS (made by PARTICLESIZING SYSTEMS).
另外，上述填充剂在本发明的光湿气固化型树脂组合物中有时作为二次粒子(一次粒子多个聚集而成的粒子)而存在，这样的二次粒子的粒径的优选下限为5nm，优选上限为500nm，更优选下限为10nm，更优选上限为100nm。上述填充剂的二次粒子的粒径可以通过使用透射型电子显微镜(TEM)观察本发明的光湿气固化型树脂组合物或其固化物而进行测定。In addition, the above-mentioned filler may exist as secondary particles (particles in which a plurality of primary particles are aggregated) in the optical moisture-curable resin composition of the present invention, and the preferred lower limit of the particle diameter of such secondary particles is 5 nm. , the upper limit is preferably 500 nm, the lower limit is more preferably 10 nm, and the upper limit is more preferably 100 nm. The particle diameter of the secondary particle of the said filler can be measured by observing the optical moisture curable resin composition of this invention or its hardened|cured material using a transmission electron microscope (TEM).
作为上述填充剂，优选无机填充剂，可以列举例如二氧化硅、滑石等。其中，从得到的光湿气固化型树脂组合物成为UV光透过性优异的组合物出发，优选二氧化硅。这些填充剂可以单独使用，也可以2种以上组合使用。As said filler, an inorganic filler is preferable, for example, silica, talc, etc. are mentioned. Among them, silica is preferable because the obtained optical moisture-curable resin composition has excellent UV light transmittance. These fillers may be used alone or in combination of two or more.
上述填充剂优选进行疏水性表面处理而成。通过上述疏水性表面处理，所得的光湿气固化型树脂组合物成为涂布后的形状保持性更优异的组合物。It is preferable that the said filler is hydrophobic surface-treated. By the above-mentioned hydrophobic surface treatment, the obtained optical moisture-curable resin composition becomes a composition which is more excellent in shape retention after application.
作为上述疏水性表面处理，可以列举甲硅烷基化处理、烷基化处理、环氧化处理等。其中，从提高形状保持性的效果优异的方面出发，优选甲硅烷基化处理，更优选三甲基甲硅烷基化处理。Examples of the above-mentioned hydrophobic surface treatment include silylation treatment, alkylation treatment, epoxidation treatment, and the like. Among them, the silylation treatment is preferable, and the trimethylsilylation treatment is more preferable, since the effect of improving the shape retention is excellent.
作为对上述填充剂进行疏水性表面处理的方法，可以列举例如使用硅烷偶联剂等表面处理剂来处理填充剂的表面的方法等。As a method of performing a hydrophobic surface treatment with respect to the said filler, the method of treating the surface of a filler with a surface treatment agent, such as a silane coupling agent, etc. are mentioned, for example.
具体而言，例如，上述三甲基甲硅烷基化处理二氧化硅可以通过例如以下方法来制作：通过溶胶凝胶法等方法合成二氧化硅，在使二氧化硅流动的状态下喷雾六甲基二硅氮烷的方法；在醇、甲苯等有机溶剂中添加二氧化硅，进一步添加六甲基二硅氮烷和水后，将水和有机溶剂通过蒸发仪蒸发干燥的方法等。Specifically, for example, the above-mentioned trimethylsilylated silica can be produced by, for example, synthesizing silica by a method such as a sol-gel method, and spraying hexamethylmethane in a state in which the silica is fluidized. The method of base disilazane; the method of adding silica to an organic solvent such as alcohol and toluene, further adding hexamethyldisilazane and water, and then evaporating the water and the organic solvent to dryness through an evaporator.
在本发明的光湿气固化型树脂组合物全体100重量份中，上述填充剂的含量的优选下限为0.1重量份，优选上限为20重量份。若上述填充剂的含量小于0.1重量份，则有时所得的光湿气固化型树脂组合物的涂布后的形状保持性差。若上述填充剂的含量大于20重量份，则有时所得的光湿气固化型树脂组合物的涂布性差。上述填充剂的含量的更优选下限为0.5重量份，更优选上限为15重量份，进一步优选下限为1重量份，进一步优选上限为12重量份，特别优选下限为2重量份。In 100 parts by weight of the total optical moisture-curable resin composition of the present invention, the preferred lower limit of the content of the filler is 0.1 parts by weight, and the preferred upper limit is 20 parts by weight. When content of the said filler is less than 0.1 weight part, the shape retention after application|coating of the optical moisture curable resin composition obtained may be inferior. When content of the said filler exceeds 20 weight part, the coating property of the optical moisture curable resin composition obtained may be inferior. A more preferable lower limit of the content of the filler is 0.5 parts by weight, a more preferable upper limit is 15 parts by weight, a still more preferable lower limit is 1 part by weight, a further preferable upper limit is 12 parts by weight, and a particularly preferable lower limit is 2 parts by weight.
本发明的光湿气固化型树脂组合物根据需要还可以含有离子液体、溶剂、含金属的粒子、反应性稀释剂等添加剂。The optical moisture-curable resin composition of the present invention may further contain additives such as an ionic liquid, a solvent, metal-containing particles, and a reactive diluent, if necessary.
作为制造本发明的光湿气固化型树脂组合物的方法，可以列举例如使用均质分散器、均质混合器、万能混合器、行星式混合器、捏合机、三辊机等混合机，将自由基聚合性化合物、湿气固化型聚氨酯树脂、光自由基聚合引发剂、除水剂和根据需要添加的添加剂混合的方法等。As a method for producing the optical moisture-curable resin composition of the present invention, for example, using a mixer such as a homodisperser, a homomixer, a universal mixer, a planetary mixer, a kneader, and a three-roller can be used. A method of mixing a radically polymerizable compound, a moisture-curable urethane resin, a photoradical polymerization initiator, a water scavenger, and an additive added as needed, and the like.
本发明的光湿气固化型树脂组合物优选所含的水分量为100ppm以下。若上述水分量大于100ppm，则在保存中上述湿气固化型聚氨酯树脂与水分容易发生反应，光湿气固化型树脂组合物的保存稳定性差。上述水分量更优选80ppm以下。It is preferable that the moisture content contained in the optical moisture-curable resin composition of this invention is 100 ppm or less. When the said moisture content exceeds 100 ppm, the said moisture-curable urethane resin easily reacts with moisture during storage, and the storage stability of an optical moisture-curable resin composition is inferior. The above-mentioned moisture content is more preferably 80 ppm or less.
需要说明的是，上述水分量可以通过卡尔费休水分测定装置进行测定。In addition, the said moisture content can be measured by a Karl Fischer moisture measuring apparatus.
本发明的光湿气固化型树脂组合物的使用锥板型粘度计在25℃、1rpm的条件下测得的粘度的优选下限为50Pa·s，优选上限为500Pa·s。若上述粘度小于50Pa·s或大于500Pa·s，则将光湿气固化型树脂组合物用于电子部件用粘接剂、显示元件用粘接剂时，涂布于基板等被粘物时的操作性变差。上述粘度的更优选下限为80Pa·s，更优选上限为300Pa·s，进一步优选上限为200Pa·s。The preferable lower limit of the viscosity measured on the conditions of 25 degreeC and 1 rpm using the cone-plate viscometer of the optical moisture curable resin composition of this invention is 50 Pa*s, and a preferable upper limit is 500 Pa*s. When the above-mentioned viscosity is less than 50 Pa·s or more than 500 Pa·s, when the optical moisture curable resin composition is used for an adhesive for electronic parts or an adhesive for display elements, when it is applied to an adherend such as a substrate Operability deteriorates. A more preferable lower limit of the viscosity is 80 Pa·s, a more preferable upper limit is 300 Pa·s, and a further preferable upper limit is 200 Pa·s.
本发明的光湿气固化型树脂组合物的触变指数的优选下限为1.3，优选上限为5.0。若上述触变指数小于1.3或大于5.0，则将光湿气固化型树脂组合物用于电子部件用粘接剂、显示元件用粘接剂时，涂布于基板等被粘物时的操作性变差。上述触变指数的更优选下限为1.5，更优选上限为4.0。The preferable lower limit of the thixotropic index of the optical moisture-curable resin composition of the present invention is 1.3, and the preferable upper limit is 5.0. When the thixotropic index is less than 1.3 or more than 5.0, when the optical moisture-curable resin composition is used for an adhesive for electronic parts or an adhesive for display elements, workability when applied to an adherend such as a substrate worse. The more preferable lower limit of the said thixotropic index is 1.5, and the more preferable upper limit is 4.0.
需要说明的是，在本说明书中，上述触变指数表示使用锥板型粘度计在25℃、1rpm的条件下测得的粘度除以使用锥板型粘度计在25℃、10rpm的条件下测得的粘度而得的值。It should be noted that, in this specification, the thixotropic index means the viscosity measured using a cone and plate viscometer at 25°C and 1 rpm divided by the viscosity measured at 25°C and 10 rpm using a cone and plate viscometer. The value obtained from the viscosity.
本发明的光湿气固化型树脂组合物可以作为电子部件用粘接剂、显示元件用粘接剂而特别优选使用。使用本发明的光湿气固化型树脂组合物而制成的电子部件用粘接剂、和使用本发明的光湿气固化型树脂组合物而制成的显示元件用粘接剂也分别是本发明之一。The optical moisture-curable resin composition of this invention can be used especially suitably as an adhesive agent for electronic components, and an adhesive agent for display elements. The adhesive for electronic parts produced using the optical moisture-curable resin composition of the present invention and the adhesive for display elements produced using the optical moisture-curable resin composition of the present invention are also included in the present invention. one of the inventions.
发明效果Invention effect
根据本发明，可以提供保存稳定性和粘接性优异的光湿气固化型树脂组合物。According to the present invention, an optical moisture-curable resin composition excellent in storage stability and adhesiveness can be provided.
附图说明Description of drawings
图1(a)表示从上方观察粘接性评价用样品时的示意图，图1(b)表示从侧面观察粘接性评价用样品时的示意图。FIG. 1( a ) is a schematic diagram when the sample for adhesive evaluation is observed from above, and FIG. 1( b ) is a schematic diagram when the sample for adhesive evaluation is observed from the side.
具体实施方式Detailed ways
以下举出实施例对本发明进一步进行详细说明，但本发明并不限定于这些实施例。另外，根据本发明，能够提供使用该光湿气固化型树脂组合物而制成的电子部件用粘接剂和显示元件用粘接剂。The present invention will be described in further detail below with reference to Examples, but the present invention is not limited to these Examples. Moreover, according to this invention, the adhesive agent for electronic components and the adhesive agent for display elements which were produced using this optical moisture curable resin composition can be provided.
(合成例1(聚氨酯预聚物A的制作))(Synthesis Example 1 (Production of Polyurethane Prepolymer A))
将作为多元醇的100重量份的聚四亚甲基醚二醇(三菱化学公司制，“PTMG-2000”)、和0.01重量份的二月桂酸二丁基锡加入至500mL容量的可分离烧瓶中，在真空下(20mmHg以下)、在100℃搅拌30分钟并混合。随后设为常压，加入作为二异氰酸酯的26.5重量份的Pure MDI(日曹商事公司制)，在80℃搅拌3小时使其反应，得到聚氨酯预聚物A(重均分子量2700)。100 parts by weight of polytetramethylene ether glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG-2000") and 0.01 parts by weight of dibutyltin dilaurate as polyols were put into a separable flask having a capacity of 500 mL, Stir and mix under vacuum (below 20 mmHg) at 100°C for 30 minutes. Then, the pressure was set to normal pressure, 26.5 parts by weight of Pure MDI (manufactured by Nissho Shoji Co., Ltd.) was added as a diisocyanate, and the reaction was stirred at 80° C. for 3 hours to obtain a polyurethane prepolymer A (weight average molecular weight: 2700).
(合成例2(聚氨酯预聚物B的制作))(Synthesis Example 2 (Production of Polyurethane Prepolymer B))
将作为多元醇的100重量份的聚丙二醇(旭硝子公司制，“EXCENOL2020”)、和0.01重量份的二月桂酸二丁基锡加入至500mL容量的可分离烧瓶，在真空下(20mmHg以下)、100℃搅拌30分钟并混合。随后设为常压，加入作为二异氰酸酯的26.5重量份的Pure MDI(日曹商事公司制)，在80℃搅拌3小时使其反应，得到聚氨酯预聚物B(重均分子量2900)。100 parts by weight of polypropylene glycol (manufactured by Asahi Glass Co., Ltd., "EXCENOL 2020") and 0.01 part by weight of dibutyltin dilaurate as polyols were placed in a separable flask with a capacity of 500 mL, under vacuum (20 mmHg or less) at 100° C. Stir for 30 minutes and mix. Then, the pressure was set to normal pressure, 26.5 parts by weight of Pure MDI (manufactured by Nissho Shoji Co., Ltd.) was added as a diisocyanate, and the reaction was stirred at 80° C. for 3 hours to obtain a polyurethane prepolymer B (weight average molecular weight: 2900).
(合成例3(聚氨酯预聚物C的制作))(Synthesis Example 3 (Production of Polyurethane Prepolymer C))
在加入了与合成例1同样地得到的聚氨酯预聚物A的反应容器中，添加甲基丙烯酸羟乙酯1.3重量份、和作为阻聚剂的N-亚硝基苯基羟胺铝盐(和光纯药工业公司制，“Q-1301”)0.14重量份，在氮气流下、在80℃搅拌混合1小时，得到在分子末端具有异氰酸酯基和甲基丙烯酰基的聚氨酯预聚物C(重均分子量3100)。To the reaction vessel containing the polyurethane prepolymer A obtained in the same manner as in Synthesis Example 1, 1.3 parts by weight of hydroxyethyl methacrylate and N-nitrosophenylhydroxylamine aluminum salt (Wako) were added as a polymerization inhibitor. Pure Chemical Industries, Ltd., "Q-1301") 0.14 parts by weight, stirred and mixed at 80°C for 1 hour under nitrogen flow to obtain polyurethane prepolymer C (weight average molecular weight) having an isocyanate group and a methacryloyl group at the molecular end 3100).
(实施例1～19、比较例1、2)(Examples 1 to 19, Comparative Examples 1 and 2)
根据表1、2中记载的配合比，利用行星式搅拌装置(Thinky公司制，“ぁわとり練太郎”)将各材料搅拌后，利用陶瓷三辊机均匀混合，从而得到实施例1～19、比较例1、2的光湿气固化型树脂组合物。According to the mixing ratios described in Tables 1 and 2, each material was stirred with a planetary stirring device (manufactured by Thinky Corporation, "ぁわとりLentaro"), and then uniformly mixed with a ceramic three-roller to obtain Examples 1 to 19 , and the optical moisture-curable resin compositions of Comparative Examples 1 and 2.
需要说明的是，表1、2中的“聚氨酯预聚物A”是合成例1中记载的、在两末端具有异氰酸酯基的聚氨酯预聚物，“聚氨酯预聚物B”是合成例2中记载的、在两末端具有异氰酸酯基的聚氨酯预聚物，“聚氨酯预聚物C”是合成例3中记载的、在分子末端具有异氰酸酯基和甲基丙烯酰基的聚氨酯预聚物。In addition, "polyurethane prepolymer A" in Tables 1 and 2 is a polyurethane prepolymer described in Synthesis Example 1 and having isocyanate groups at both ends, and "polyurethane prepolymer B" is in Synthesis Example 2 The described polyurethane prepolymer having isocyanate groups at both ends, "urethane prepolymer C", is the polyurethane prepolymer described in Synthesis Example 3 and having isocyanate groups and methacryloyl groups at molecular ends.
<评价><Evaluation>
对于实施例和比较例中得到的各光湿气固化型树脂组合物进行了以下的评价。将结果示于表1、2中。The following evaluation was performed about each optical moisture-curable resin composition obtained by the Example and the comparative example. The results are shown in Tables 1 and 2.
(保存稳定性)(Storage stability)
对于实施例和比较例中得到的各光湿气固化型树脂组合物，测定在25℃保管1周时的粘度与刚制造后的初期粘度，将此时的由(25℃、保管1周后的粘度)/(初期粘度)表示的值作为粘度变化率，粘度变化率小于1.1的样品为“○”，1.1以上且小于1.5的样品为“△”，1.5以上的样品为“×”，由此评价了保存稳定性。For each optical moisture-curable resin composition obtained in the Examples and Comparative Examples, the viscosity at the time of storage at 25° C. for one week and the initial viscosity immediately after production were measured, and the values at (25° C., after storage for one week) were measured. The value represented by the viscosity)/(initial viscosity) is taken as the viscosity change rate, the sample with the viscosity change rate less than 1.1 is "○", the sample with a viscosity change rate of 1.1 or more and less than 1.5 is "△", and the sample with a viscosity change of more than 1.5 is "×". This evaluates storage stability.
需要说明的是，粘度是使用锥板型粘度计(东机产业公司制，“VISCOMETERTV-22”)，在25℃、旋转速度1rpm的条件下进行测定的。In addition, the viscosity was measured on the conditions of 25 degreeC and a rotation speed 1rpm using a cone-plate viscometer (manufactured by Toki Sangyo Co., Ltd., "VISCOMETERTV-22").
(水分量)(moisture content)
将实施例和比较例中得到的各光湿气固化型树脂组合物溶于脱水溶剂，利用卡尔费休水分计(京都电子工业公司制，“MKC-610”)测定水分量。The respective optical moisture-curable resin compositions obtained in Examples and Comparative Examples were dissolved in a dehydration solvent, and the moisture content was measured with a Karl Fischer moisture meter (manufactured by Kyoto Electronics Industries, Ltd., "MKC-610").
(粘接性)(adhesive)
使用分配装置，将实施例和比较例中得到的各光湿气固化型树脂组合物，以约2mm的宽度涂布于聚碳酸酯基板。随后，使用高压汞灯照射500mJ/cm2的紫外线，由此使光湿气固化型树脂组合物进行光固化。Each optical moisture-curable resin composition obtained in the Example and the comparative example was apply|coated to the polycarbonate board|substrate in the width|variety of about 2 mm using the distribution apparatus. Subsequently, ultraviolet rays of 500 mJ/cm 2 were irradiated using a high-pressure mercury lamp, thereby photocuring the optical moisture-curable resin composition.
随后，将玻璃板贴合于聚碳酸酯基板，并放置一晚，由此使其湿气固化，得到粘接性评价用样品。Then, by bonding a glass plate to a polycarbonate substrate, and leaving it to stand overnight, it was moisture-cured, and a sample for adhesiveness evaluation was obtained.
图1中示出了表示从上方观察粘接性评价用样品时的示意图(图1(a))、和表示从侧面观察粘接性评价用样品时的示意图(图1(b))。FIG. 1 shows a schematic diagram ( FIG. 1( a )) showing the sample for adhesive evaluation from above, and a schematic diagram ( FIG. 1( b ) ) showing the sample for adhesive evaluation from the side.
使用拉伸试验机，沿剪切方向以5mm/sec的速度拉伸，对于所制作的粘接性评价用样品，测定基材剥离时的强度。Using a tensile tester, the sample was pulled at a speed of 5 mm/sec in the shearing direction, and the strength at the time of peeling the base material was measured about the produced sample for evaluation of adhesion.
(粘着性)(adhesion)
使用分配装置，将实施例和比较例中得到的各光湿气固化型树脂组合物，以约2mm的宽度涂布于聚碳酸酯基板。随后，使用高压汞灯照射500mJ/cm2的紫外线，使光湿气固化型树脂组合物进行光固化，制作粘着性的评价用样品。对于得到的粘着性的评价用样品，使用粘着试验机(RHESCA公司制，“TAC-100”)测定粘着强度。Each optical moisture-curable resin composition obtained in the Example and the comparative example was apply|coated to the polycarbonate board|substrate in the width|variety of about 2 mm using the distribution apparatus. Then, ultraviolet rays of 500 mJ/cm 2 were irradiated using a high-pressure mercury lamp to photocure the optical moisture-curable resin composition to prepare a sample for evaluation of adhesion. The adhesive strength of the obtained sample for evaluation of adhesiveness was measured using an adhesive tester (manufactured by RHESCA, "TAC-100").
[表1][Table 1]
[表2][Table 2]
产业上的可利用性Industrial Availability
根据本发明，能够提供保存稳定性和粘接性优异的光湿气固化型树脂组合物。另外，根据本发明，能够提使用供该光湿气固化型树脂组合物而制成的电子部件用粘接剂和显示元件用粘接剂。ADVANTAGE OF THE INVENTION According to this invention, the optical moisture hardening type resin composition excellent in storage stability and adhesiveness can be provided. Moreover, according to this invention, the adhesive agent for electronic components and the adhesive agent for display elements which were produced using this optical moisture curable resin composition can be provided.
符号说明Symbol Description
1、聚碳酸酯树脂基板1. Polycarbonate resin substrate
2、光湿气固化型树脂组合物2. Optical moisture curable resin composition
3、玻璃板3. Glass plate
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| KR20220097552A (en) * | 2016-10-19 | 2022-07-07 | 세키스이가가쿠 고교가부시키가이샤 | Organic el display element sealing agent, and method for producing organic el display element sealing agent |
| TWI809045B (en) * | 2018-02-27 | 2023-07-21 | 日商味之素股份有限公司 | resin composition for sealing |
| JPWO2022114186A1 (en) * | 2020-11-30 | 2022-06-02 | ||
| KR102528349B1 (en) * | 2021-04-21 | 2023-05-03 | 주식회사 한솔케미칼 | Dual curable resin composition and adhesive for display using the same |
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