TW201319093A - Novel (meth)acrylic resin and resin composition utilizing same - Google Patents

Novel (meth)acrylic resin and resin composition utilizing same Download PDF

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TW201319093A
TW201319093A TW101123486A TW101123486A TW201319093A TW 201319093 A TW201319093 A TW 201319093A TW 101123486 A TW101123486 A TW 101123486A TW 101123486 A TW101123486 A TW 101123486A TW 201319093 A TW201319093 A TW 201319093A
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meth
resin composition
acrylic resin
liquid crystal
resin
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Kenta Sugawara
Masanori Hashimoto
Naomi Hasumi
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Nippon Kayaku Kk
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/022Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
    • C08F299/024Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/10Epoxy resins modified by unsaturated compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters
    • C08F222/1006Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106Esters of polycondensation macromers
    • C08F222/1067Esters of polycondensation macromers of alcohol terminated epoxy functional polymers, e.g. epoxy(meth)acrylates

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Epoxy Resins (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention proposes: a (meth)acrylic resin represented by formula (1); and a resin composition prepared using the (meth)acrylic resin. In the formula, the benzene ring Ar may be present or absent; a bond a represents a single bond or a double bond when the benzene ring Ar is absent; n represents an integer of 1 to 5; and R1 represents a hydrogen atom or a methyl group. The (meth)acrylic resin can be applied suitably for adhesive agents, is easy to handle, and can achieve flexibility in designing of adhesive agents and high adhesion strength of adhesive agents.

Description

新穎(甲基)丙烯酸系樹脂及使用該新穎(甲基)丙烯酸系樹脂之樹脂組成物 Novel (meth)acrylic resin and resin composition using the novel (meth)acrylic resin

本發明是關於一種新穎(甲基)丙烯酸((metha)acryl)系樹脂。更詳細而言,是關於一種(甲基)丙烯酸系樹脂,該(甲基)丙烯酸系樹脂具有對苯二酚、鄰苯二酚、或間苯二酚骨架,且其分子內具有羧基,進而,本發明提出一種適合於黏著劑用途的樹脂組成物,該樹脂組成物使用該(甲基)丙烯酸系樹脂而得到。 This invention relates to a novel (meth)acrylic resin. More specifically, it relates to a (meth)acrylic resin having a hydroquinone, a catechol, or a resorcinol skeleton, and having a carboxyl group in its molecule, and further The present invention proposes a resin composition suitable for use in an adhesive, which is obtained by using the (meth)acrylic resin.

以往,分子內具有羧基的(甲基)丙烯酸系樹脂,被廣泛運用於光阻墨水組成物中,該光阻墨水組成物是用於形成印刷配線基板的光阻圖案(專利文獻1、專利文獻2等)。此光阻墨水組成物,是使用於藉顯影而形成期望的配線圖案。較具體而言,首先,對於經切割圖案(配線)之光罩下的該(甲基)丙烯酸系樹脂組成物照射紫外線等能量線,使曝光部的(甲基)丙烯酸系樹脂的(甲基)丙烯醯基進行交聯。然後,利用未硬化的(甲基)丙烯酸系樹脂的羧基之鹼溶解性來進行鹼顯影,藉此形成固定的圖案。 Conventionally, a (meth)acrylic resin having a carboxyl group in a molecule is widely used in a resist ink composition which is a photoresist pattern for forming a printed wiring substrate (Patent Document 1 and Patent Literature) 2, etc.). This resist ink composition is used to form a desired wiring pattern by development. Specifically, the (meth)acrylic resin composition under the mask of the cut pattern (wiring) is irradiated with an energy ray such as ultraviolet rays to expose the (meth)acrylic resin of the exposed portion (methyl group). The propylene sulfhydryl group is crosslinked. Then, alkali development is carried out by utilizing the alkali solubility of the carboxyl group of the uncured (meth)acrylic resin, thereby forming a fixed pattern.

又,該(甲基)丙烯酸系樹脂,亦被使用作為黏著劑之用。例如,在專利文獻3中,是被利用作為光硬化性的牙科用黏著劑。 Moreover, this (meth)acrylic resin is also used as an adhesive. For example, in Patent Document 3, it is used as a photocurable dental adhesive.

然而,這些(甲基)丙烯酸系樹脂,是特別針對光硬 化性或硬化物在常溫附近的耐水黏著性等作為牙科用黏著劑的用途而成的設計。因此,該(甲基)丙烯酸系樹脂的作為黏著劑的用途,尚未充分地確立。 However, these (meth)acrylic resins are specifically designed for light hardening. A design in which a water-resistant adhesive such as a chemical or cured product is used as a dental adhesive in the vicinity of normal temperature. Therefore, the use of the (meth)acrylic resin as an adhesive has not been sufficiently established.

[先前技術文獻] [Previous Technical Literature] (專利文獻) (Patent Literature)

專利文獻1:日本特開昭61-243869號公報 Patent Document 1: Japanese Patent Laid-Open No. 61-243869

專利文獻2:日本特開平3-143911號公報 Patent Document 2: Japanese Patent Laid-Open No. 3-143911

專利文獻3:日本特開平5-286822號公報 Patent Document 3: Japanese Laid-Open Patent Publication No. Hei 5-286822

本發明是鑑於上述狀況而完成,是關於一種新穎(甲基)丙烯酸系樹脂,其於分子內具有羧基。亦即,本發明提出一種新穎(甲基)丙烯酸系樹脂,其適合於使用在黏著劑用途,能夠實現了處理和黏著劑的設計的自由度、黏著劑的高黏著強度。 The present invention has been made in view of the above circumstances, and relates to a novel (meth)acrylic resin having a carboxyl group in a molecule. That is, the present invention proposes a novel (meth)acrylic resin which is suitable for use in an adhesive application, and which can realize the degree of freedom in design of the treatment and the adhesive, and the high adhesion strength of the adhesive.

本發明人鑑於上述原因而專心反覆進行探討,結果發現,使酸酐等與具有對苯二酚、鄰苯二酚、或間苯二酚之類的骨架的環氧樹脂之(甲基)丙烯酸酯進行反應而得到的化合物,因為分子量較小,所以是低黏度,而且因為羧基當量(每一個羧基所相當的分子量)亦小,所以能夠提高極性,當使用作為黏著劑的構成成分時,能夠謀求實現 黏著強度的提升、和熱硬化反應的促進效果,而完成了本發明。 The inventors of the present invention have intensively conducted a discussion in view of the above-mentioned reasons, and as a result, found that an acid anhydride or the like is a (meth) acrylate of an epoxy resin having a skeleton such as hydroquinone, catechol, or resorcin. Since the compound obtained by the reaction has a small molecular weight, it has a low viscosity, and since the carboxyl group equivalent (the molecular weight corresponding to each carboxyl group) is also small, the polarity can be increased, and when a constituent component as an adhesive is used, it can be obtained. achieve The present invention has been completed by an improvement in adhesion strength and a promoting effect of a heat hardening reaction.

亦即,本發明是關於下述1)~12)。另外,本說明書中,所謂的「(甲基)丙烯酸」,是意味著「丙烯酸」及「甲基丙烯酸」之一或兩者。又,本說明書中,所謂的「(甲基)丙烯醯基」,是意味著「丙烯醯基」及「甲基丙烯醯基」之一或兩者。 That is, the present invention relates to the following 1) to 12). In the present specification, the term "(meth)acrylic acid" means one or both of "acrylic acid" and "methacrylic acid". In the present specification, the term "(meth)acryloyl group" means one or both of "acryloyl fluorenyl group" and "methacryl fluorenyl group".

1)一種(甲基)丙烯酸系樹脂,該(甲基)丙烯酸系樹脂是以下述式(1)表示, (式中,苯環Ar可存在亦可不存在,且當苯環Ar不存在時,鍵a表示單鍵或雙鍵;又,n表示1~5的整數,R1表示氫原子或甲基)。 1) A (meth)acrylic resin represented by the following formula (1), (wherein, the benzene ring Ar may or may not be present, and when the benzene ring Ar is absent, the bond a represents a single bond or a double bond; further, n represents an integer of 1 to 5, and R 1 represents a hydrogen atom or a methyl group) .

2)如上述1)所述的(甲基)丙烯酸系樹脂,其中上述式(1)中不存在苯環Ar。 2) The (meth)acrylic resin according to the above 1), wherein the benzene ring Ar is not present in the above formula (1).

3)如上述1)所述的丙烯酸系樹脂,其中上述式(1)中R1是氫原子。 3) The acrylic resin according to the above 1), wherein R 1 in the above formula (1) is a hydrogen atom.

4)一種樹脂組成物,其中含有如上述1)至3)中任一項所述的(甲基)丙烯酸系樹脂。 4) A resin composition containing the (meth)acrylic resin according to any one of the above 1) to 3).

5)如上述4)所述的樹脂組成物,其中進而含有光聚合起始劑。 5) The resin composition according to the above 4), which further contains a photopolymerization initiator.

6)如上述4)所述的樹脂組成物,其中,進而含有熱自由基聚合起始劑。 The resin composition according to the above 4), which further contains a thermal radical polymerization initiator.

7)如上述4)所述的樹脂組成物,其中進而含有無機填料。 7) The resin composition according to the above 4), which further contains an inorganic filler.

8)如上述4)所述的樹脂組成物,其中進而含有醯肼(hydrazide)化合物。 8) The resin composition according to the above 4), which further contains a hydrazide compound.

9)如上述4)所述的樹脂組成物,其中進而含有矽烷耦合劑。 9) The resin composition according to the above 4), which further contains a decane coupling agent.

10)一種電子零件用黏著劑,其使用如上述4)所述的樹脂組成物而作成。 10) An adhesive for electronic parts, which is produced by using the resin composition as described in 4) above.

11)一種液晶顯示晶胞用(liquid crystal display cell)黏著劑,其使用如上述4)所述的樹脂組成物而得到。 11) A liquid crystal display cell adhesive obtained by using the resin composition according to the above 4).

12)一種液晶顯示晶胞,其使用如上述11)所述的液晶顯示晶胞用黏著劑來黏著而作成。 12) A liquid crystal display cell which is formed by adhering a liquid crystal display cell as described in the above 11) with an adhesive.

本發明的(甲基)丙烯酸系樹脂,非常適合於使用在黏著劑用途。亦即,本發明的(甲基)丙烯酸系樹脂因為在分子內具有羧基,且進而因為羧基當量小,所以能夠實現黏著劑的黏著強度的提升、和熱硬化反應的促進效果。而且,本發明的(甲基)丙烯酸系樹脂亦具有下述特徵:因為分子量較小,所以亦易於處理,進而,當使用作為黏 著劑時亦不容易受到其他成分的黏度的限制,所以即便不使用有機溶劑等稀釋劑,亦容易進行設計。 The (meth)acrylic resin of the present invention is very suitable for use in an adhesive. In other words, since the (meth)acrylic resin of the present invention has a carboxyl group in the molecule and further has a small carboxyl group equivalent, it is possible to enhance the adhesion strength of the adhesive and the effect of promoting the thermosetting reaction. Moreover, the (meth)acrylic resin of the present invention also has the following characteristics: since the molecular weight is small, it is also easy to handle, and further, when used as a stickiness When the agent is applied, it is not easily restricted by the viscosity of other components, so that it is easy to design without using a diluent such as an organic solvent.

以下,詳細說明本發明。 Hereinafter, the present invention will be described in detail.

本發明的以上述式(1)表示的(甲基)丙烯酸系樹脂,可以藉由下述方式而獲得:在反應觸媒存在下,使0.1莫耳當量~30莫耳當量、較佳是1莫耳當量~10莫耳當量之酸酐,與以下述式(2)~(4)表示的環氧丙烯酸酯樹脂進行反應而獲得。反應溫度較佳是0℃~100℃,更佳是10℃~40℃。另外,式(2)~(4)中的n、R1,是與上述式(1)中的n及R1表示相同意思。 The (meth)acrylic resin represented by the above formula (1) of the present invention can be obtained by 0.1 mol% to 30 mol equivalents, preferably 1 in the presence of a reaction catalyst. The anhydride having a molar equivalent of ~10 moles is obtained by reacting with an epoxy acrylate resin represented by the following formulas (2) to (4). The reaction temperature is preferably from 0 ° C to 100 ° C, more preferably from 10 ° C to 40 ° C. Further, n and R 1 in the formulae (2) to (4) have the same meanings as n and R 1 in the above formula (1).

作為反應觸媒,並無特別限定,可以使用鹼等物質,但較佳是使用有機鹼。特佳是使用三級胺。又,亦可將2種以上混合使用,混合4-甲基胺基吡啶與三乙胺來使用則是特佳的態樣之一。 The reaction catalyst is not particularly limited, and a substance such as an alkali can be used, but an organic base is preferably used. It is particularly preferred to use a tertiary amine. Further, two or more kinds may be used in combination, and it is one of the particularly preferable aspects to use 4-methylaminopyridine and triethylamine.

作為酸酐,可以舉出馬來酸酐、二氫馬來酸酐(琥珀酸酐)、鄰苯二甲酸酐等。另外,使用馬來酸、二氫馬來酸(琥珀酸)、鄰苯二甲酸等來取代酸酐時,也能夠藉由適當地設計添加量,而獲得以上述式(1)表示的(甲基)丙烯酸系樹脂。 Examples of the acid anhydride include maleic anhydride, dihydromaleic anhydride (succinic anhydride), and phthalic anhydride. In addition, when maleic acid, dihydromaleic acid (succinic acid), phthalic acid or the like is used in place of the acid anhydride, the addition amount can be appropriately designed to obtain (methyl) represented by the above formula (1). ) Acrylic resin.

又,此合成中亦可使用有機溶劑來進行。作為所使用的有機溶劑,可以舉出2-丁酮和二氯甲烷等,或是亦可混合2種以上來使用。 Further, this synthesis can also be carried out using an organic solvent. The organic solvent to be used may, for example, be 2-butanone or dichloromethane, or may be used in combination of two or more.

作為本發明的(甲基)丙烯酸系樹脂,相較於對苯二酚骨架、鄰苯二酚骨架,較佳是具有間苯二酚骨架的(甲基)丙烯酸系樹脂。原因在於,相較於對苯二酚骨架,間苯二酚骨架的對稱性低,而相較於鄰苯二酚骨架,間苯二酚骨架則較易於取得、樹脂硬化反應快。又,從反應的快速性而言,相較於甲基丙烯酸系樹脂,較佳是丙烯酸系樹 脂。又,為了降低羧基當量,作為酸酐,較佳是使用馬來酸酐。 The (meth)acrylic resin of the present invention is preferably a (meth)acrylic resin having a resorcinol skeleton as compared with the hydroquinone skeleton or the catechol skeleton. The reason is that the symmetry of the resorcinol skeleton is lower than that of the hydroquinone skeleton, and the resorcinol skeleton is easier to obtain and the resin hardening reaction is faster than the catechol skeleton. Further, from the viewpoint of the rapidity of the reaction, an acrylic tree is preferred as compared with the methacrylic resin. fat. Further, in order to lower the carboxyl group equivalent, maleic anhydride is preferably used as the acid anhydride.

使用本發明的(甲基)丙烯酸系樹脂而得到的樹脂組成物,以作為黏著劑用途較為合適。此時,當將該樹脂組成物的總量設為100質量份時,(甲基)丙烯酸系樹脂的含量較佳是0.01質量份~95質量份。又,更佳是0.1質量份~90質量份,特佳是1質量份~80質量份。作為餘份,則有:光聚合起始劑、熱自由基聚合起始劑、無機填料、熱硬化劑、矽烷耦合劑等。 The resin composition obtained by using the (meth)acrylic resin of the present invention is suitably used as an adhesive. In this case, when the total amount of the resin composition is 100 parts by mass, the content of the (meth)acrylic resin is preferably from 0.01 part by mass to 95 parts by mass. Further, it is preferably from 0.1 part by mass to 90 parts by mass, particularly preferably from 1 part by mass to 80 parts by mass. As the remainder, there are a photopolymerization initiator, a thermal radical polymerization initiator, an inorganic filler, a thermosetting agent, a decane coupling agent, and the like.

作為本發明的樹脂組成物中可以含有的光聚合起始劑,只要是能因紫外線或可見光等能量線的照射而產生自由基並使連鎖聚合反應開始進行的化合物即可,並無特別限定,例如可以舉出:苯甲基二甲基縮酮、1-羥基環己基苯基酮、二乙基噻噸酮(diethylthioxanthone)、二苯甲酮、2-乙基蒽醌、2-羥基-2-甲基苯丙酮、2-甲基-[4-(甲硫基)苯基]-2-(N-嗎啉基)-1-丙烷、2,4,6-三甲基苯甲醯基二苯基氧化膦等。又,在下述使用作為液晶顯示晶胞用黏著劑的情形中,當使用在與液晶直接接觸的部分時,從液晶污染性的觀點而言,較佳是使用分子內具有(甲基)丙烯醯基的化合物,例如較適合使用2-甲基丙烯醯氧基乙基異氰酸酯與1-[4-(2-羥基乙氧基)苯基]-2-羥基-2-甲基-1-丙-1-酮的反應生成物。此化合物可用國際公開第2006/027982號記載的方法來製造而獲得。當將本發明的樹脂組成物的總量設為100質量份時,此光聚合起始劑的含量通常是0.1 質量份~10質量份,較佳是0.2質量份~5質量份。 The photopolymerization initiator which can be contained in the resin composition of the present invention is not particularly limited as long as it can generate a radical due to irradiation with an energy ray such as ultraviolet light or visible light, and the chain polymerization reaction starts. For example, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, diethyl thioxanthone, benzophenone, 2-ethyl hydrazine, 2-hydroxy-2 can be mentioned. -methylpropiophenone, 2-methyl-[4-(methylthio)phenyl]-2-(N-morpholinyl)-1-propane, 2,4,6-trimethylbenzylidene Diphenylphosphine oxide and the like. Further, in the case where the adhesive for liquid crystal display cells is used as described below, when a portion directly in contact with the liquid crystal is used, it is preferred to use (meth)acrylic acid in the molecule from the viewpoint of liquid crystal contamination. The compound of the group, for example, 2-methacryloxyethyl isocyanate and 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propene are preferably used. 1-ketone reaction product. This compound can be obtained by the method described in International Publication No. 2006/027982. When the total amount of the resin composition of the present invention is 100 parts by mass, the content of the photopolymerization initiator is usually 0.1. The mass fraction is preferably 10 parts by mass, preferably 0.2 parts by mass to 5 parts by mass.

作為本發明的樹脂組成物中可以含有的熱自由基聚合起始劑,只要是能藉由加熱而產生自由基並使連鎖聚合反應開始進行的化合物即可,並無特別限定,例如可以舉出:有機過氧化物、偶氮化合物、安息香化合物、安息香醚化合物、苯乙酮化合物、四苯基-1,2-乙二醇(benzopinacol)等,較合適為使用四苯基-1,2-乙二醇。例如,作為有機過氧化物,可以取得下述市售品:Kayamek A、Kayamek M、Kayamek R、Kayamek L、Kayamek LH、Kayamek SP-30C、Perkadox CH-50L、Perkadox BC-FF、Cadox B-40ES、Perkadox 14、Trigonox 22-70E、Trigonox 23-C70、Trigonox 121、Trigonox 121-50E、Trigonox 121-LS50E、Trigonox 21-LS50E、Trigonox 42、Trigonox 42LS、Kayaester P-70、Kayaester TMPO-70、Kayaester CND-C70、Kayaester O、Kayaester O-50E、Kayaester AN、Kayabutyl B、Perkadox 16、Kayacarbon BIC-75、Kayacarbon AIC-75(Kayaku Akzo股份有限公司製);Permek N、Permek H、Permek S、Permek F、Permek D、Permek G、Perhexa H、Perhexa HC、Perhexa TMH、Perhexa C、Perhexa V、Perhexa 22、Perhexa MC、Percure AH、Percure AL、Percure HB、Perbutyl H、Perbutyl C、Perbutyl ND、Perbutyl L、Percumyl H、Percumyl D、Peroyl IB、Peroyl IPP、Perocta ND(日油股份有限公司製)等。又,作為偶氮化合物,可以取得下述市售品:VA-044、V-070、VPE-0201、VSP-1001(和光純藥工業股份有限公 司製)等。當將本發明的樹脂組成物的總量設為100質量份時,作為該熱自由基聚合起始劑的含量較佳是0.0001質量份~10質量份,更佳是0.0005質量份~7質量份,特佳是0.001質量份~3質量份。 The thermal radical polymerization initiator which can be contained in the resin composition of the present invention is not particularly limited as long as it can generate a radical by heating and initiates a chain polymerization reaction, and is not particularly limited, and examples thereof include, for example, : organic peroxide, azo compound, benzoin compound, benzoin ether compound, acetophenone compound, tetraphenyl-1,2-ethylene glycol (benzopinacol), etc., more suitable to use tetraphenyl-1,2- Ethylene glycol. For example, as an organic peroxide, the following commercial products can be obtained: Kayamek A, Kayamek M, Kayamek R, Kayamek L, Kayamek LH, Kayamek SP-30C, Perkadox CH-50L, Perkadox BC-FF, Cadox B-40ES Perkadox 14, Trigonox 22-70E, Trigonox 23-C70, Trigonox 121, Trigonox 121-50E, Trigonox 121-LS50E, Trigonox 21-LS50E, Trigonox 42, Trigonox 42LS, Kayaester P-70, Kayaester TMPO-70, Kayaester CND -C70, Kayaester O, Kayaester O-50E, Kayaester AN, Kayabutyl B, Perkadox 16, Kayacarbon BIC-75, Kayacarbon AIC-75 (Kayaku Akzo Co., Ltd.); Permek N, Permek H, Permek S, Permek F, Permek D, Permek G, Perhexa H, Perhexa HC, Perhexa TMH, Perhexa C, Perhexa V, Perhexa 22, Perhexa MC, Percure AH, Percure AL, Percure HB, Perbutyl H, Perbutyl C, Perbutyl ND, Perbutyl L, Percumyl H , Percumyl D, Peroyl IB, Peroyl IPP, Perocta ND (manufactured by Nippon Oil Co., Ltd.), and the like. Further, as an azo compound, the following commercial products can be obtained: VA-044, V-070, VPE-0201, VSP-1001 (Wako Pure Chemical Industries Co., Ltd. System) and so on. When the total amount of the resin composition of the present invention is 100 parts by mass, the content of the thermal radical polymerization initiator is preferably 0.0001 part by mass to 10 parts by mass, more preferably 0.0005 part by mass to 7 parts by mass. It is particularly preferably 0.001 parts by mass to 3 parts by mass.

作為本發明的樹脂組成物中可以含有的無機填料,可以舉出:熔融二氧化矽、結晶二氧化矽、碳化矽、氮化矽、氮化硼、碳酸鈣、碳酸鎂、硫酸鋇、硫酸鈣、雲母、滑石、黏土、氧化鋁、氧化鎂、氧化鋯、氫氧化鋁、氫氧化鎂、矽酸鈣、矽酸鋁、矽酸鋁鋰、矽酸鋯、鈦酸鋇、玻璃纖維、碳纖維、二硫化鉬、石綿等,較佳是熔融二氧化矽、結晶二氧化矽、氮化矽、氮化硼、碳酸鈣、硫酸鋇、硫酸鈣、雲母、滑石、黏土、氧化鋁、氫氧化鋁、矽酸鈣、矽酸鋁,更佳是熔融二氧化矽、結晶二氧化矽、氧化鋁、滑石。這些無機填料,可以混合2種以上來使用。特別在使用作為下述液晶顯示晶胞用黏著劑時,其平均粒徑若過大,則在製造狹間隙的液晶顯示晶胞時,會成為上下玻璃基板貼合時無法順利形成間隙等不良情形的原因,因此以3 μm以下較適當,較佳是2 μm以下。粒徑可以藉由雷射繞射/散射式粒度分佈測定器(乾式)(股份有限公司SEISHIN企業製;LMS-30)來測定。 Examples of the inorganic filler which may be contained in the resin composition of the present invention include molten cerium oxide, crystalline cerium oxide, cerium carbide, cerium nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, and calcium sulfate. , mica, talc, clay, alumina, magnesia, zirconia, aluminum hydroxide, magnesium hydroxide, calcium citrate, aluminum silicate, lithium aluminum niobate, zirconium silicate, barium titanate, glass fiber, carbon fiber, Molybdenum disulfide, asbestos, etc., preferably molten cerium oxide, crystalline cerium oxide, cerium nitride, boron nitride, calcium carbonate, barium sulfate, calcium sulfate, mica, talc, clay, alumina, aluminum hydroxide, Calcium citrate and aluminum citrate are more preferably molten cerium oxide, crystalline cerium oxide, aluminum oxide or talc. These inorganic fillers can be used in combination of two or more kinds. In particular, when the above-mentioned liquid crystal display cell adhesive is used, if the average particle diameter is too large, when a liquid crystal display cell having a narrow gap is produced, a problem such as a gap cannot be formed smoothly when the upper and lower glass substrates are bonded together. The reason is therefore suitably 3 μm or less, preferably 2 μm or less. The particle diameter can be measured by a laser diffraction/scattering particle size distribution analyzer (dry type) (manufactured by SEISHIN Co., Ltd.; LMS-30).

當將本發明的樹脂組成物的總量設為100質量份時,上述無機填料在樹脂組成物中的含量通常是1質量份~60質量份,較佳是5質量份~60質量份,更佳是10質量份~50質量份。當無機填料的含量過少時,黏著強度降低, 而且耐濕可信度亦變差,因此吸濕後黏著強度的降低情形有時會增大。另一方面,當無機填料的含量過多時,有時會有無法形成液晶顯示晶胞的間隙的情形。 When the total amount of the resin composition of the present invention is 100 parts by mass, the content of the inorganic filler in the resin composition is usually from 1 part by mass to 60 parts by mass, preferably from 5 parts by mass to 60 parts by mass, more preferably Preferably, it is 10 parts by mass to 50 parts by mass. When the content of the inorganic filler is too small, the adhesion strength is lowered, Moreover, the reliability of moisture resistance is also deteriorated, so the decrease in the adhesive strength after moisture absorption sometimes increases. On the other hand, when the content of the inorganic filler is too large, there may be a case where a gap of the liquid crystal display unit cell cannot be formed.

作為本發明的樹脂組成物中可以含有的熱硬化劑,並無特別限定(其中,不包含上述熱自由基聚合起始劑),可以舉出多元胺類、多元酚類、醯肼化合物等,以醯肼化合物特別適合使用。例如,可以舉出下述芳香族醯肼:水楊醯肼、對苯二甲酸二醯肼、間苯二甲酸二醯肼、2,6-萘甲酸二醯肼、2,6-吡啶二醯肼、1,2,4-苯三醯肼、1,4,5,8-萘甲酸四醯肼、均苯四甲酸四醯肼等。又,若是脂肪族醯肼,則例如可舉出:甲醯肼、乙醯肼、丙酸肼、草酸二醯肼、丙二酸二醯肼、琥珀酸二醯肼、戊二酸二醯肼、己二酸二醯肼、庚二酸二醯肼、1,4-環己烷二醯肼、酒石酸二醯肼、蘋果酸二醯肼、亞胺基二乙酸二醯肼、N,N’-六亞甲基雙半卡肼(N,N’-hexamethylenebis(semicarbazide))、檸檬酸三醯肼、氮基乙酸三醯肼、環己烷三羧酸三醯肼、1,3-雙(肼基碳基乙基)-5-異丙基乙內醯脲(1,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin)等具有乙內醯脲骨架且較佳是具有纈胺酸乙內醯脲骨架(乙內醯脲環的碳原子經異丙基取代而成的骨架)的二醯肼化合物、參(1-肼基羰基甲基)異三聚氰酸酯、參(2-肼基羰基乙基)異三聚氰酸酯、參(2-肼基羰基乙基)異三聚氰酸酯、參(3-肼基羰基丙基)異三聚氰酸酯、雙(2-肼基羰基乙基)異三聚氰酸酯等。從硬化反應性與潛在性的平 衡方面而言,較佳是:間苯二甲酸二醯肼、丙二酸二醯肼、己二酸二醯肼、參(1-肼基羰基甲基)異三聚氰酸酯、參(2-肼基羰基乙基)異三聚氰酸酯、參(2-肼基羰基乙基)異三聚氰酸酯、參(3-肼基羰基丙基)異三聚氰酸酯,特佳是參(2-肼基羰基乙基)異三聚氰酸酯。作為使用這樣的熱硬化劑時的使用量,當將本發明的樹脂組成物的總量設為100質量份時,該熱硬化劑的使用量較佳是0.1質量份~20質量份,更佳是1質量份~10質量份,亦可混合2種以上來使用。 The thermosetting agent which can be contained in the resin composition of the present invention is not particularly limited (the above-mentioned thermal radical polymerization initiator is not included), and examples thereof include polyamines, polyhydric phenols, and hydrazine compounds. The ruthenium compound is particularly suitable for use. For example, the following aromatic hydrazines: salicylate, diterpene terephthalate, diammonium isophthalate, diammonium 2,6-naphthoate, 2,6-pyridine dioxime, 1,2,4-Benzenetriazine, tetrakisperylene 1,4,5,8-naphthoic acid, tetraterpene tetrabenzoic acid, and the like. Further, in the case of an aliphatic hydrazine, for example, formazan, acetamidine, cesium propionate, bismuth oxalate, diammonium malonate, diterpene succinate, diammonium glutarate may be mentioned. , diammonium adipate, dinonyl pimelate, 1,4-cyclohexane dioxime, diterpenic tartrate, diterpene malate, diimide diacetate, N, N' - N,N'-hexamethylenebis (semicarbazide), triterpene citrate, triammonium oxyacetate, triterpene Cyclohexanetricarboxylate, 1,3-double ( 1,3-bis(hydrazinocarboethyl-5-isopropylhydantoin), etc. having a carbendazim skeleton and preferably having a valeric acid a diterpene compound of a skeleton (a skeleton in which a carbon atom of an intraurethone ring is substituted with an isopropyl group), a ginseng (1-mercaptocarbonylmethyl)isocyanate, and a bis(nonylcarbonyl) group Ethyl)isomeric cyanurate, ginseng (2-mercaptocarbonylethyl)isocyanate, ginseng (3-mercaptocarbonylpropyl)isocyanate, bis(2-indenyl) Carbonyl ethyl) isomeric cyanurate or the like. From the hardening reactivity and potential level In terms of balance, it is preferred that: diammonium isophthalate, diammonium malonate, diammonium adipate, ginseng (1-mercaptocarbonylmethyl)isocyanate, ginseng ( 2-mercaptocarbonylethyl)isocyanate, ginseng (2-mercaptocarbonylethyl)isocyanate, ginseng (3-mercaptocarbonylpropyl)isocyanate, special Preferably, it is ginseng (2-mercaptocarbonylethyl)isocyanate. When the total amount of the resin composition of the present invention is 100 parts by mass, the amount of the heat curing agent used is preferably 0.1 part by mass to 20 parts by mass, more preferably It is 1 part by mass to 10 parts by mass, and may be used in combination of two or more kinds.

作為本發明的樹脂組成物中可以含有的矽烷耦合劑,可以舉出:3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-巰基丙基三甲氧基矽烷、乙烯基三甲氧基矽烷、N-(2-(乙烯基苯甲基胺基)乙基)-3-胺基丙基三甲氧基矽烷鹽酸鹽、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷等。當將本發明的樹脂組成物的總量設為100質量份時,矽烷耦合劑在樹脂組成物中所佔的含量以0.05質量份~3質量份較合適。 Examples of the decane coupling agent which may be contained in the resin composition of the present invention include 3-glycidoxypropyltrimethoxydecane and 3-glycidoxypropylmethyldimethoxydecane. 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, N-phenyl-γ-aminopropyltrimethoxy Baseline, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyltrimethoxy Decane, 3-aminopropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, vinyltrimethoxydecane, N-(2-(vinylbenzylamino)ethyl)-3 -Aminopropyltrimethoxydecane hydrochloride, 3-methacryloxypropyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane Wait. When the total amount of the resin composition of the present invention is 100 parts by mass, the content of the decane coupling agent in the resin composition is preferably 0.05 parts by mass to 3 parts by mass.

本發明的樹脂組成物中,作為其他樹脂成分,亦可以含有由選自環氧樹脂、(甲基)丙烯酸化環氧樹脂、及部分 (甲基)丙烯酸化環氧樹脂中的1種或2種以上所構成之硬化性樹脂。例如,可以舉出:環氧樹脂、環氧樹脂與(甲基)丙烯酸化環氧樹脂之混合物、(甲基)丙烯酸化環氧樹脂、部分(甲基)丙烯酸化環氧樹脂等。特別是在使用作為液晶顯示晶胞用黏著劑的情形中,當使用在與液晶直接接觸的部分時,較佳是對於液晶的污染性、溶解性低的樹脂。作為合適的環氧樹脂的例示,可以舉出:雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、雙酚F酚醛清漆型環氧樹脂、脂環式環氧樹脂、脂肪族鏈狀環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、乙內醯脲型環氧樹脂、異三聚氰酸酯型環氧樹脂、具有三酚甲烷骨架之苯酚酚醛清漆型環氧樹脂,以及其他的二官能酚類之二縮水甘油醚化物、二官能醇類之二縮水甘油醚化物、及這些物質的鹵化物、氫化物等,但並不限定於此。(甲基)丙烯醯化環氧樹脂、部分(甲基)丙烯醯化環氧樹脂,可以藉由環氧樹脂與(甲基)丙烯酸之習知反應來獲得。例如,可以藉由在環氧樹脂中添加規定當量比的(甲基)丙烯酸與觸媒(例如,苯甲基二甲基胺、三乙胺、苯甲基三甲基氯化銨、三苯基膦、三苯基銻(triphenylstibine)等)、聚合抑制劑(例如,對苯二酚單甲基醚(methoquinone)、對苯二酚、甲基對苯二酚、吩噻(phenothiazine)、二丁基羥基甲苯等),在例如80℃~110℃進行酯化反應而獲得。作為原料的環氧樹脂,並無 特別限定,較佳是2官能以上的環氧樹脂,例如:雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A酚醛清漆型環氧樹脂、雙酚F酚醛清漆型環氧樹脂、脂環式環氧樹脂、脂肪族鏈狀環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、乙內醯脲型環氧樹脂、異三聚氰酸酯型環氧樹脂、具有三酚甲烷骨架之苯酚酚醛清漆型環氧樹脂,以及其他的二官能酚類之二縮水甘油醚化物、二官能醇類之二縮水甘油醚化物、及這些物質的鹵化物、氫化物等。這些之中,從液晶污染性的觀點而言,較佳是雙酚型環氧樹脂、酚醛清漆型環氧樹脂。又,環氧基與(甲基)丙烯醯基的比率並無限定,可以從步驟適合性及液晶污染性的觀點而適當地選擇。 The resin composition of the present invention may contain, as another resin component, one or two selected from the group consisting of epoxy resins, (meth)acrylated epoxy resins, and partially (meth)acrylated epoxy resins. A curable resin composed of the above. For example, an epoxy resin, a mixture of an epoxy resin and a (meth)acrylated epoxy resin, a (meth)acrylated epoxy resin, a partial (meth)acrylated epoxy resin, etc. are mentioned. In particular, in the case of using an adhesive for a liquid crystal display cell, when a portion directly in contact with the liquid crystal is used, a resin having low contamination and solubility to liquid crystal is preferable. Examples of suitable epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, and cresol novolak type. Epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester epoxy resin, glycidylamine Epoxy resin, intramethylene urea resin, iso-cyanate epoxy resin, phenol novolak epoxy resin with trisphenol methane skeleton, and other difunctional phenolic diglycidyl The ether compound, the diglycidyl ether compound of the difunctional alcohol, and the halide or hydride of these materials are not limited thereto. A (meth) propylene oxime epoxy resin or a partial (meth) propylene oxime epoxy resin can be obtained by a conventional reaction of an epoxy resin and (meth)acrylic acid. For example, a predetermined equivalent ratio of (meth)acrylic acid to a catalyst (for example, benzyldimethylamine, triethylamine, benzyltrimethylammonium chloride, triphenyl) may be added to the epoxy resin. Phosphine, triphenylstibine, etc., polymerization inhibitors (for example, hydroquinone monomethoxide, hydroquinone, methyl hydroquinone, phenothiazine) (phenothiazine), dibutylhydroxytoluene, etc., obtained by, for example, an esterification reaction at 80 ° C to 110 ° C. The epoxy resin as a raw material is not particularly limited, and is preferably a bifunctional or higher epoxy resin such as bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, or phenol. Novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin , glycidyl ester type epoxy resin, glycidylamine type epoxy resin, ethyl uret urea type epoxy resin, iso-cyanate type epoxy resin, phenol novolak type epoxy resin having a trisphenol methane skeleton And other difunctional phenolic diglycidyl ether compounds, difunctional alcohol diglycidyl ether compounds, and halides, hydrides and the like of these materials. Among these, from the viewpoint of liquid crystal contamination, a bisphenol epoxy resin or a novolac epoxy resin is preferred. Further, the ratio of the epoxy group to the (meth) acrylonitrile group is not limited, and can be appropriately selected from the viewpoints of step suitability and liquid crystal contamination.

本發明的樹脂組成物中,亦可進而視需要而調配(甲基)丙烯酸酯之單體或寡聚物。作為這樣的單體、寡聚物,例如可以舉出:二季戊四醇與(甲基)丙烯酸之反應物、二季戊四醇己內酯與(甲基)丙烯酸之反應物等,但並無特別限制。 In the resin composition of the present invention, a monomer or oligomer of a (meth) acrylate may be further optionally added. Examples of such a monomer or oligomer include a reaction product of dipentaerythritol and (meth)acrylic acid, a reaction product of dipentaerythritol caprolactone and (meth)acrylic acid, and the like, but are not particularly limited.

本發明的樹脂組成物中,可以進而視需要而調配有機填料以及顏料、調平劑(leveling agent)、消泡劑、溶劑等添加劑。 In the resin composition of the present invention, an organic filler, an additive such as a pigment, a leveling agent, an antifoaming agent, or a solvent may be further optionally added.

作為能獲得本發明的樹脂組成物的方法的例示,有以下所示的方法。首先,對於本案發明的(甲基)丙烯酸系樹脂,將光聚合起始劑和其他的(甲基)丙烯酸系樹脂、 環氧樹脂等加熱溶解,冷卻至室溫後,混合無機填充劑、矽烷耦合劑、熱自由基聚合起始劑、熱硬化劑等,接著藉由例如三輥研磨機、混砂機、球磨機等公知的混合裝置來均勻地混合,以金屬篩網來過濾,藉此製造本發明的樹脂組成物。 As an example of a method of obtaining the resin composition of the present invention, there are the methods described below. First, as the (meth)acrylic resin of the present invention, a photopolymerization initiator and other (meth)acrylic resins, Epoxy resin or the like is dissolved by heating, and after cooling to room temperature, an inorganic filler, a decane coupling agent, a thermal radical polymerization initiator, a thermal curing agent, or the like is mixed, followed by, for example, a three-roll mill, a sand mill, a ball mill, or the like. A known mixing device is uniformly mixed and filtered with a metal mesh to thereby produce the resin composition of the present invention.

本發明的樹脂組成物,是作為電子零件用黏著劑而非常地有用。作為電子零件用黏著劑,可以舉出撓性印刷配線基板用黏著劑、TAB(Tape automated bonding,捲帶式自動接合)用黏著劑、半導體用黏著劑、各種顯示器用黏著劑等,但並不限定於此等。 The resin composition of the present invention is very useful as an adhesive for electronic parts. Examples of the adhesive for electronic components include an adhesive for a flexible printed wiring board, an adhesive for TAB (Tape automated bonding), an adhesive for a semiconductor, and various adhesives for displays. Limited to this.

又,本案發明的樹脂組成物,是作為液晶顯示晶胞用黏著劑,且特別是作為液晶密封劑而非常地有用。關於使用本發明的樹脂組成物作為液晶密封劑時的液晶顯示晶胞,於以下顯示其例示。 Further, the resin composition of the present invention is useful as an adhesive for liquid crystal display cells, and is particularly useful as a liquid crystal sealing agent. The liquid crystal display cell when the resin composition of the present invention is used as a liquid crystal sealing agent is exemplified below.

使用本案發明的液晶顯示晶胞用黏著劑所製造的液晶顯示晶胞,是將已形成規定電極的一對基板,以規定間隔而對向地配置,以本發明的液晶密封劑將周圍密封,並於其間隙中封入液晶而成。所封入的液晶種類,並無特別限定。此處,所謂的基板是由下述組合的基板所構成,該組合的基板是由玻璃、石英、塑膠、矽等所構成,且至少其中之一具有透光性。作為其製法,是在本發明的液晶密封劑中添加玻璃纖維等間隔物(間隙控制材料)之後,使用塗佈機(dispenser)、網版印刷裝置等,對該一對基板中的一基板塗佈該液晶密封劑之後,視需要而以80℃~120℃進 行暫時硬化。然後,於該液晶密封劑的堰的內側滴下液晶,在真空中與另一玻璃基板疊合,進行間隙形成(gap forming)。間隙形成後,藉由紫外線照射機對液晶密封劑部照射紫外線而使其光硬化。紫外線照射量較佳是500 mJ/cm2~6000 mJ/cm2,更佳是1000 mJ/cm2~4000 mJ/cm2。然後,視需要而以90℃~130℃硬化1~2小時,藉此可以獲得本發明的液晶顯示晶胞。以此種方式進行而獲得的本發明的液晶顯示晶胞,沒有因液晶污染所致的顯示不良情形,是黏著性、耐濕可信度優異的液晶顯示晶胞。作為間隔物,例如可以舉出玻璃纖維、二氧化矽粒子、聚合物粒子等。其直徑因目的而異,通常是2 μm~8 μm,較佳是4 μm~7 μm。相對於本發明的液晶密封劑100質量份,間隔物的使用量通常是0.1質量份~4質量份,較佳是0.5質量份~2質量份,更佳是0.9質量份~1.5質量份左右。 In the liquid crystal display cell produced by the liquid crystal display cell adhesive of the present invention, a pair of substrates on which a predetermined electrode has been formed are disposed oppositely at a predetermined interval, and the liquid crystal sealing agent of the present invention seals the periphery. And the liquid crystal is sealed in the gap. The type of liquid crystal to be enclosed is not particularly limited. Here, the substrate is composed of a substrate which is composed of glass, quartz, plastic, tantalum, or the like, and at least one of which has light transmissivity. In the liquid crystal sealing agent of the present invention, a spacer such as a glass fiber (gap control material) is added, and then a substrate of the pair of substrates is coated using a dispenser, a screen printing device, or the like. After the liquid crystal sealing agent is applied, it is temporarily hardened at 80 ° C to 120 ° C as needed. Then, liquid crystal was dropped on the inside of the crucible of the liquid crystal sealing agent, and superposed on the other glass substrate in a vacuum to perform gap forming. After the gap is formed, the liquid crystal sealing agent portion is irradiated with ultraviolet rays by an ultraviolet ray irradiator to cure the light. The ultraviolet irradiation amount is preferably 500 mJ/cm 2 to 6000 mJ/cm 2 , more preferably 1000 mJ/cm 2 to 4000 mJ/cm 2 . Then, if necessary, it is cured at 90 ° C to 130 ° C for 1 to 2 hours, whereby the liquid crystal display unit cell of the present invention can be obtained. The liquid crystal display cell of the present invention obtained in this manner has no display failure due to liquid crystal contamination, and is a liquid crystal display cell excellent in adhesion and moisture resistance. Examples of the spacer include glass fibers, cerium oxide particles, and polymer particles. The diameter varies depending on the purpose, and is usually 2 μm to 8 μm, preferably 4 μm to 7 μm. The amount of the spacer used is usually 0.1 parts by mass to 4 parts by mass, preferably 0.5 parts by mass to 2 parts by mass, more preferably 0.9 parts by mass to 1.5 parts by mass, per 100 parts by mass of the liquid crystal sealing agent of the present invention.

本發明的新穎(甲基)丙烯酸系樹脂,非常適合使用於黏著劑用途。亦即,因為其分子內具有羧基且羧基當量小,所以能夠實現黏著強度的提升、和熱硬化反應的促進效果。而且,本發明的(甲基)丙烯酸系樹脂亦具有下述特徵:因為分子量較小,所以易於處理,而且當使用作為黏著劑時亦不容易受到其他成分的黏度的限制,因此容易進行設計。又,使用本案發明的(甲基)丙烯酸系樹脂而得到的樹脂組成物,是作為電子零件用黏著劑、液晶顯示晶胞用黏著劑而非常地有用。 The novel (meth)acrylic resin of the present invention is very suitable for use in an adhesive. In other words, since the molecule has a carboxyl group and the carboxyl group equivalent is small, the adhesion strength can be improved and the thermosetting reaction can be promoted. Further, the (meth)acrylic resin of the present invention is also characterized in that it is easy to handle because of its small molecular weight, and is also less susceptible to the viscosity of other components when used as an adhesive, and thus is easy to design. In addition, the resin composition obtained by using the (meth)acrylic resin of the present invention is very useful as an adhesive for electronic components and an adhesive for liquid crystal display cells.

[實施例] [Examples]

以下,藉由合成例、實施例以更詳細地說明本發明,但本發明並不限定於此等。另外,只要無特別記載,本文中的「份」及「%」是以質量為基準。 Hereinafter, the present invention will be described in more detail by way of Synthesis Examples and Examples, but the present invention is not limited thereto. In addition, as long as there is no special record, the "parts" and "%" in this article are based on quality.

[合成例1:丙烯酸化間苯二酚二縮水甘油醚的合成] [Synthesis Example 1: Synthesis of acrylated resorcinol diglycidyl ether]

將間苯二酚二縮水甘油醚181.2 g(Nagase ChemteX股份有限公司)溶解於甲苯266.8 g,於其中加入二丁基羥基甲苯0.8 g作為聚合抑制劑,升溫至60℃。然後,加入環氧基之100%當量的丙烯酸117.5 g,進而升溫至80℃,於其中添加三甲基氯化銨亦即反應觸媒0.6 g,以98℃攪拌約30小時,而獲得反應液。將此反應液進行水洗,蒸餾去除甲苯,藉此獲得目標的間苯二酚二縮水甘油醚之環氧丙烯酸酯(丙烯酸化間苯二酚二縮水甘油醚)253 g。 181.2 g of resorcinol diglycidyl ether (Nagase ChemteX Co., Ltd.) was dissolved in 266.8 g of toluene, and 0.8 g of dibutylhydroxytoluene was added thereto as a polymerization inhibitor, and the temperature was raised to 60 °C. Then, 117.5 g of 100% equivalent of acrylic acid of epoxy group was added, and the temperature was further raised to 80 ° C, and thereto was added trimethylammonium chloride, that is, 0.6 g of a reaction catalyst, and stirred at 98 ° C for about 30 hours to obtain a reaction liquid. . This reaction liquid was washed with water, and toluene was distilled off, whereby 253 g of an epoxy acrylate (acrylated resorcinol diglycidyl ether) of the intended resorcinol diglycidyl ether was obtained.

[合成例2:丙烯酸化間苯二酚二縮水甘油醚之馬來酸酐加成物的合成] [Synthesis Example 2: Synthesis of maleic anhydride adduct of acrylated resorcinol diglycidyl ether]

加入合成例1所獲得的間苯二酚二縮水甘油醚之環氧丙烯酸酯3.66 g、4-二甲基胺基吡啶0.049 g、三乙胺6.07 g、二氯甲烷1000 ml,在室溫下攪拌使其溶解後,加入馬來酸酐11.8 g,在室溫下攪拌一晚。將所獲得的反應液以稀鹽酸清洗3次、以水清洗3次之後,蒸餾去除二氯甲烷,藉此獲得在分子內具有羧基之丙烯酸化間苯二酚二縮水甘油醚5 g。LC MS(m/z)=561(M-H)、IR 1705cm-1(COOH)。 Adding 3.66 g of epoxy acrylate of resorcinol diglycidyl ether obtained in Synthesis Example 1, 0.049 g of 4-dimethylaminopyridine, 6.07 g of triethylamine, and 1000 ml of dichloromethane at room temperature After stirring to dissolve, 11.8 g of maleic anhydride was added, and the mixture was stirred at room temperature overnight. The obtained reaction solution was washed three times with dilute hydrochloric acid and three times with water, and then dichloromethane was distilled off, whereby 5 g of acrylated resorcinol diglycidyl ether having a carboxyl group in the molecule was obtained. LC MS (m / z) = 561 (MH), IR 1705cm -1 (COOH).

(液晶滴下工法用密封劑的調製) (Modulation of sealant for liquid crystal dropping method) [實施例1] [Example 1]

以下述表1所示的比例,將合成例2所合成的本發明的丙烯酸系樹脂以90℃加熱溶解,並於其中使光聚合起始劑加熱溶解之後,冷卻至室溫,添加矽烷耦合劑、二氧化矽、熱硬化劑並攪拌之後,以三輥研磨機使其分散,以金屬篩網(635網目)來過濾,而調製成實施例1的液晶滴下工法用密封劑。 The acrylic resin of the present invention synthesized in Synthesis Example 2 was dissolved by heating at 90 ° C in the ratio shown in the following Table 1, and the photopolymerization initiator was heated and dissolved therein, and then cooled to room temperature to add a decane coupling agent. After the cerium oxide and the thermal curing agent were stirred, the mixture was dispersed in a three-roll mill and filtered through a metal mesh (635 mesh) to prepare a sealing agent for a liquid crystal dropping method of Example 1.

[比較例1~2] [Comparative Examples 1 to 2]

又,同樣地以下述表1所示的比例,將合成例1所合成的丙烯酸系樹脂以90℃加熱,並於其中使光聚合起始劑加熱溶解之後,冷卻至室溫,添加矽烷耦合劑、二氧化矽、熱硬化劑、硬化促進劑並攪拌之後,以三輥研磨機使其分散,以金屬篩網(635網目)來過濾,而調製成比較例1~2的液晶滴下工法用密封劑。 In the same manner, the acrylic resin synthesized in Synthesis Example 1 was heated at 90 ° C in the same manner, and the photopolymerization initiator was heated and dissolved therein, and then cooled to room temperature to add a decane coupling agent. After the cerium oxide, the thermal curing agent, and the hardening accelerator were stirred, the mixture was dispersed in a three-roll mill and filtered through a metal mesh (635 mesh) to prepare a liquid crystal dropping method seal of Comparative Examples 1 and 2. Agent.

試驗評估是以下述方法來實施。 The test evaluation was carried out in the following manner.

(耐濕黏著強度試驗) (moisture resistance test)

於所獲得的液晶密封劑100 g中,添加5 μm的玻璃纖維1 g來作為間隔物並混合攪拌。將此液晶密封劑塗佈於50 mm×50 mm的玻璃基板上,於該液晶密封劑上貼合1.5 mm×1.5 mm的玻璃片,藉由UV照射機來照射3000 mJ/cm2的紫外線之後,投入烤箱,以120℃使其熱硬化1小時。將此試驗片以121℃、2大氣壓、濕度100%的條件,投入壓力鍋(pressure cooker)試驗機(TPC-411:Tabai Espec股份有限公司製)12小時之後,以黏合力測試機(bond tester)(SS-30WD:西進商事股份有限公司製)來測定玻璃片的 剪切黏著強度。結果顯示於表1。 To 100 g of the obtained liquid crystal sealing agent, 1 g of 5 μm glass fiber was added as a spacer and stirred and mixed. The liquid crystal sealing agent was applied onto a glass substrate of 50 mm×50 mm, and a glass piece of 1.5 mm×1.5 mm was attached to the liquid crystal sealing agent, and after irradiating ultraviolet rays of 3000 mJ/cm 2 by a UV irradiation machine. It was put into an oven and hardened at 120 ° C for 1 hour. The test piece was placed in a pressure cooker tester (TPC-411: manufactured by Tabai Espec Co., Ltd.) at 121 ° C, 2 atm, and humidity of 100% for 12 hours, and a bond tester was used. (SS-30WD: manufactured by Sejin Trading Co., Ltd.) to measure the shear adhesion strength of the glass piece. The results are shown in Table 1.

(硬化速度試驗) (hardening speed test)

對於所獲得的液晶密封劑,以動態黏彈性率測定裝置(Rheosol-G5000,股份有限公司UBM製)來測定複數黏度(complex viscosity)。動態黏彈性率測定裝置的設定,是如同以下所述。圓錐:直徑為20 mm的平行圓錐,頻率:1 Hz,彎曲角度:3 deg.,測定溫度是以18℃/分鐘的速度自30℃升溫至120℃,然後維持於120℃。黏度到達10000 Pa.s時的時間,顯示於表1。 With respect to the obtained liquid crystal sealing agent, a complex viscosity was measured by a dynamic viscoelasticity measuring apparatus (Rheosol-G5000, manufactured by UBM Co., Ltd.). The setting of the dynamic viscoelasticity measuring device is as follows. Cone: parallel cone with a diameter of 20 mm, frequency: 1 Hz, bending angle: 3 deg., measured temperature was raised from 30 ° C to 120 ° C at a rate of 18 ° C / min, and then maintained at 120 ° C. Viscosity reaches 10,000 Pa. The time at s is shown in Table 1.

①藉由合成例2所合成。 ②藉由合成例1所合成。 ③HCIC(日本FINECHEM(股)公司製)。 ※HCIC是藉由噴射磨機微粉碎成平均粒徑1.5 μm、最大粒徑5 μm來使用。 ④Sila-Ace S-510(CHISSO(股)公司製) ⑤Admafine SEZ((股)ADMATECHS公司製) ⑥以國際公開WO2006/027982號公報所述的方法所合成。 ⑦CIC酸(四國化成(股)公司製)。 ※CIC酸是藉由噴射磨機微粉碎成平均粒徑1.5 μm、最大粒徑5 μm來使用。 1 synthesized by Synthesis Example 2. 2 Synthesized by Synthesis Example 1. 3HCIC (made by Japan FINECHEM Co., Ltd.). * HCIC is finely pulverized by a jet mill to an average particle size of 1.5 μm and a maximum particle size of 5 μm. 4Sila-Ace S-510 (manufactured by CHISSO Co., Ltd.) 5Admafine SEZ (manufactured by ADMATECHS Co., Ltd.) 6 was synthesized by the method described in International Publication WO2006/027982. 7CIC acid (manufactured by Shikoku Chemicals Co., Ltd.). * CIC acid is finely pulverized by a jet mill to an average particle size of 1.5 μm and a maximum particle size of 5 μm.

由表1的結果可知,比較例1中由於含有CIC酸,所以到達10000 Pa.s時的時間很快,但耐濕黏著強度差。並且可知,比較例2中由於不含有CIC酸,所以耐濕黏著強度高,但硬化速度慢。另一方面,在實施例1中,不使用CIC酸,到達10000 Pa.s時的時間就能夠很快,且耐濕黏著強度高。因此,本案發明的(甲基)丙烯酸系樹脂,能夠同時提高耐濕黏著強度與硬化性兩者。 From the results of Table 1, it is known that Comparative Example 1 has a CIC acid, so it reaches 10,000 Pa. The time is very fast, but the wet adhesion resistance is poor. Further, in Comparative Example 2, since the CIC acid was not contained, the moisture-resistant adhesive strength was high, but the curing rate was slow. On the other hand, in Example 1, without using CIC acid, it reached 10,000 Pa. The time in s can be fast and the moisture-resistant adhesive strength is high. Therefore, the (meth)acrylic resin of the present invention can simultaneously improve both wet adhesion resistance and hardenability.

[產業上的可利用性] [Industrial availability]

本案發明的新穎(甲基)丙烯酸系樹脂及使用該新穎(甲基)丙烯酸系樹脂之樹脂組成物,作為電子零件用黏著劑且特別是液晶密封劑而非常地有用。 The novel (meth)acrylic resin of the present invention and the resin composition using the novel (meth)acrylic resin are very useful as an adhesive for electronic components, particularly a liquid crystal sealing agent.

Claims (12)

一種(甲基)丙烯酸系樹脂,該(甲基)丙烯酸系樹脂是以下述式(1)表示, (式中,苯環Ar可存在亦可不存在,且當苯環Ar不存在時,鍵a表示單鍵或雙鍵;又,n表示1~5的整數,R1表示氫原子或甲基)。 A (meth)acrylic resin, which is represented by the following formula (1). (wherein, the benzene ring Ar may or may not be present, and when the benzene ring Ar is absent, the bond a represents a single bond or a double bond; further, n represents an integer of 1 to 5, and R 1 represents a hydrogen atom or a methyl group) . 如請求項1所述的(甲基)丙烯酸系樹脂,其中,上述式(1)中不存在苯環Ar。 The (meth)acrylic resin according to claim 1, wherein the benzene ring Ar is not present in the above formula (1). 如請求項1所述的丙烯酸系樹脂,其中,上述式(1)中,R1是氫原子。 The acrylic resin according to claim 1, wherein, in the above formula (1), R 1 is a hydrogen atom. 一種樹脂組成物,其含有如請求項1至3中任一項所述的(甲基)丙烯酸系樹脂。 A resin composition containing the (meth)acrylic resin according to any one of claims 1 to 3. 如請求項4所述的樹脂組成物,其中,進而含有光聚合起始劑。 The resin composition according to claim 4, which further contains a photopolymerization initiator. 如請求項4所述的樹脂組成物,其中,進而含有熱自由基聚合起始劑。 The resin composition according to claim 4, which further contains a thermal radical polymerization initiator. 如請求項4所述的樹脂組成物,其中,進而含有無機填料。 The resin composition according to claim 4, which further contains an inorganic filler. 如請求項4所述的樹脂組成物,其中,進而含有醯肼化合物。 The resin composition according to claim 4, which further contains a ruthenium compound. 如請求項4所述的樹脂組成物,其中,進而含有矽烷耦合劑。 The resin composition according to claim 4, which further contains a decane coupling agent. 一種電子零件用黏著劑,其使用如請求項4所述的樹脂組成物而作成。 An adhesive for electronic parts, which is produced by using the resin composition as described in claim 4. 一種液晶顯示晶胞用黏著劑,其使用如請求項4所述的樹脂組成物而得到。 An adhesive for liquid crystal display cells, which is obtained by using the resin composition as described in claim 4. 一種液晶顯示晶胞,其使用如請求項11所述的液晶顯示晶胞用黏著劑來黏著而作成。 A liquid crystal display unit cell which is formed by adhering a liquid crystal display cell as described in claim 11 with an adhesive.
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