TW201900711A - (Meth) acrylate resin and curable resin composition containing the same - Google Patents

Abstract

Provided are: a (meth)acrylate resin which exhibits high bonding strength if base materials are bonded with each other by means of this (meth)acrylate resin; and a curable resin composition which contains this (meth)acrylate resin. A (meth)acrylate resin which is obtained by reacting an epoxy resin, a modifying compound and a (meth)acrylic acid, said modifying compound being composed of one or more compounds selected from the group consisting of unsaturated aliphatic carboxylic acids (excluding (meth)acrylic acids), carboxylic acid anhydrides (excluding (meth)acrylic acid anhydrides), alcohols and thiols; and a curable resin composition which contains this (meth)acrylate resin.

Description

(Meth) acrylate resin and curable resin composition containing the same

The present invention relates to a (meth) acrylate resin and a curable resin composition containing the same.

In the method of manufacturing a liquid crystal display element, the dropping method is a method of manufacturing a panel by directly dropping liquid crystal in a closed loop of a sealant under vacuum, bonding and opening in a vacuum. This dripping method has many advantages such as a reduction in the amount of liquid crystal used and a reduction in the time required for the liquid crystal to be injected into the panel, and has become a mainstream method for manufacturing liquid crystal panels using a large substrate. In the method including the dripping method, for example, a dispenser is used to apply a sealant, and liquid crystals are dropped. After bonding, a gap is set and position alignment is performed. The sealant is hardened by energy ray hardening and / or thermal hardening.

In Patent Document 1, as a raw material of a sealant, it is proposed to improve the alignment characteristics of liquid crystals by partially modifying a bifunctional phenol novolac epoxy resin with a (meth) acrylic acid derivative. Further, in Patent Document 2, as a raw material of a sealant, it is proposed that a hydroxyl group and a glycidyl group of an ethylene glycol ring opening of an epoxy resin obtained by reacting a difunctional bisphenol A epoxy resin with ethylene glycol. After the oxidation, an epoxy resin represented by the following formula and a (meth) acrylic ester resin in which the epoxy resin is partially modified with a (meth) acrylic acid derivative.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2008-179796 796 [Patent Document 2] Japanese Patent Application Publication No. 2013-241488

[Questions to be Solved by the Invention]

According to the knowledge of the present inventors, the (meth) acrylate resins described in Patent Documents 1 and 2 have a problem in that the bonding strength is low when the substrates of the liquid crystal display element are bonded to each other. The present invention is to provide a (meth) acrylic resin and a curable resin composition containing the (meth) acrylate resin that exhibit high adhesive strength when the substrates are bonded to each other. [Means to solve the problem]

The present invention has the following constitutions. [1] A curable resin composition comprising: in a molecule, one or more bases represented by the following formula (1), and having a group selected from the group consisting of the following formula (1): A base represented by 2-1), a base represented by the following formula (2-2), and a (meth) acrylate resin of one or more of the groups formed by the base represented by the following formula (2-3), With thermosetting agents and / or polymerization initiators, [Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently hydrogen atom or methyl group, R ²¹ is alkenyl group or alkynyl group, and R ²² and R ²³ are independent alkyl group and olefin group Group, alkynyl or aryl, or R ²² and R ²³ together form a ring structure, X ¹ is an oxygen atom or a sulfur atom, R ²⁴ is an alkyl, alkenyl, alkynyl, or aryl group, but R ²¹ , R ²² and R ²³ are not vinyl or 1-methylvinyl]. [2] The curable resin composition according to [1], wherein the (meth) acrylate resin further has a group represented by formula (3), [Wherein R ⁶ is a hydrogen atom or a methyl group]. [3] A (meth) acrylate resin characterized by the following formula (5), Ar ¹ (-OA ¹ ) _n1 (5) [wherein Ar ¹ is the total number of carbon atoms and heteroatoms Is 5 or more and contains one or more n1-valent aromatic or heteroaromatic rings, n1 is 1 or more, A ¹ is an independent hydrogen atom, a group represented by the following formula (1), and the following formula (2 -1) a base, a base represented by the following formula (2-2), a base represented by the following formula (2-3), a base represented by the following formula (3), and a base represented by the following formula (4-1) Or a base represented by the following formula (4-2), but in the molecule, it has a group selected from the group represented by the formula (4-1) having the base represented by the formula (1); The base represented by) is a base represented by formula (4-2) and a base of 1 or more in the group formed by the base represented by formula (1), and has a base selected from the group consisting of a base represented by formula (2-1) A base represented by formula (2-2) or a base represented by formula (2-3) and a base represented by formula (4-1); a base represented by formula (2-1) and a base represented by formula (2 -2) the base represented by the formula and / or the base represented by the formula (2-3) the base represented by the formula (4-2); the base represented by the formula (2-1); the base represented by the formula (2-2) Of And the group represented by the formula (2-3) into the group of the above 1-yl], [Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently hydrogen atom or methyl group, R ²¹ is alkenyl or alkynyl, and R ²² and R ²³ are each Independent alkyl, alkenyl, alkynyl or aryl groups, or R ²² and R ²³ together form a ring structure, X ¹ is an oxygen atom or a sulfur atom, R ²⁴ is an alkyl, alkenyl, alkynyl or aryl group, However, R ²¹ , R ²² and R ²³ are not vinyl or 1-methylvinyl, B ¹ is an independent alkylene group, m1 is 1 or more, D ¹ is an arylene group, or an alkylene-arylene group. -Alkylene, alkylene-arylene, arylene-alkylene-arylene or group: -B ^2- (OB ² ) _m2- , B ² is an independent alkylene group, and m 2 is 0 Or 1 or more, C ¹ , C ² and C ³ are each independently a hydrogen atom, a base represented by formula (1), a base represented by formula (2-1), a base represented by formula (2-2), A base represented by formula (2-3) or a base represented by formula (3)]. [4] The curable resin composition according to [1] or [2], wherein the (meth) acrylate resin is a resin according to [3]. [5] The curable resin composition according to [1], [2], or [4], further comprising a resin selected from epoxy resins (except for epoxy resins having a (meth) acrylfluorene group), Some or all of the epoxy groups of epoxy resins are modified by modified compounds and some or all of the epoxy groups of epoxy resins are modified by (meth) acrylic modified epoxy resins. One or more resins in the group. Here, the aforementioned modified compound is selected from unsaturated carboxylic acid (except for (meth) acrylic acid) and carboxylic anhydride (except for (meth) acrylic anhydride). 1 or more compounds in the group consisting of alcohol, thiol and thiol. [6] The curable resin composition according to [1], [2], [4] or [5], which is a sealant for liquid crystal. [7] A method for producing a (meth) acrylate resin as described in [3], which includes a step of reacting an epoxy resin with a modified compound and (meth) acrylic acid; here, the aforementioned modified compound One or more compounds selected from the group consisting of unsaturated fatty acid carboxylic acids (except for (meth) acrylic acid), carboxylic anhydrides (except for (meth) acrylic anhydride), alcohols and thiols . [Effect of the invention]

According to the present invention, there is provided a (meth) acrylate resin that exhibits high adhesive strength when the substrates are bonded to each other, and a curable resin composition containing the same.

[Forms for Implementing the Invention]

Hereinafter, a preferred embodiment of the present invention will be described. [Definition of the specification] In this specification, "glycidyl" means 2,3-epoxypropyl. In the present specification, "methyl glycidyl" means 2,3-epoxy-2-methylpropyl. In this specification, "epoxy group" means including at least one of a glycidyl group and a methyl glycidyl group. In the present specification, "(meth) acrylfluorenyl" refers to a group comprising acrylfluorenyl (CH ₂ = CH ₂ -C (= O)-) and methacrylfluorenyl (CH ₂ = CH (CH ₃ ) -C (= O)-). "Substitutable" means "substituted or non-substituted".

In this specification, a numerical range indicated by "~" means a range including the numerical value described before and after "~" as the minimum and maximum values, respectively. In this specification, the amount of each component in the composition refers to the total amount of the plurality of substances present in the composition when there are a plurality of substances belonging to each component in the composition, unless otherwise specified. In the present specification, the term "step" includes not only independent steps, but when it cannot be clearly distinguished from other steps, if the intended purpose of the step is achieved, it is also included in the term.

In the present specification, the "alkyl group" is a linear or branched monovalent group in a single or a combination of other terms. The number of carbon atoms of the alkyl group is preferably from 1 to 20, more preferably from 1 to 18, more preferably from 1 to 10, and particularly preferably from 1 to 4. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and n- Nonyl, n-decyl, n-undecyl, n-dodecyl and the like.

In the present specification, the "alkylene group", alone or in combination with other terms, is a linear or branched divalent group. The number of carbon atoms of the alkylene group is preferably 1 to 20, and 1 to 8 is particularly preferable. Examples of the alkylene system include methylene, ethylene, ethylene (ethane-1,1-diyl), trimethylene, propylene (propane-1,2-diyl), and propylene (Propane-1,1-diyl), isopropylidene (propane-2,2-diyl), tetramethylene, butylene (butane-1,1-diyl), isobutylene ( 2-methylpropane-1,1-diyl), pentamethylene, 2-methylpentane-1,5-diyl, hexamethylene, 2-ethylhexane-1,6-di Group, heptamethylene, octamethylene and the like.

In the present specification, "alkenyl" is a linear or branched monovalent group, alone or in combination with other terms. The number of unsaturated bonds in the alkenyl group is preferably 1 to 5, and 1 or 2 is particularly preferable. The number of carbon atoms of the alkenyl group is preferably 2 to 20, 3 to 20 is more preferred, 3 to 15 is more preferred, and 3 to 10 is particularly preferred. When the alkenyl group includes a vinyl group or a 1-methylvinyl group, the carbon number of the alkenyl group may be 2-20, 2-15, or 2-10. Examples of the alkenyl system include vinyl, 1-methylvinyl, 1-propenyl, 2-propenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, and 2-butenyl , 3-butenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 9 -Decenyl.

In the present specification, the "alkynyl group" is a linear or branched monovalent group, alone or in combination with other terms. The number of carbon atoms of the alkynyl group is preferably 2 to 20, and 2 to 15 is particularly preferable. Examples of the alkynyl system include ethynyl, propynyl, 2-butynyl, 3-butynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 2-hexynyl, 3- Hexynyl, 4-hexynyl, 5-hexynyl and the like.

Alkyl, alkylene, alkenyl, and alkynyl may be substituted with a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom and an amine group.

In the present specification, the "aryl group", alone or in combination with other terms, is a monovalent group having a monocyclic or polycyclic aromatic ring. The aryl group preferably has 6 to 20 carbon atoms. Examples of the aryl group include phenyl, biphenyl, naphthyl, triphenyl, anthracenyl, and fluorenyl. Phenyl is preferred.

In the present specification, "arylene", alone or in combination with other terms, refers to a divalent radical having a monocyclic or polycyclic aromatic ring. The number of carbon atoms of the arylene group is preferably 6 to 20. Examples of the arylene system include phenylene, naphthyl, anthracenyl, and phenanthryl. Among them, phenylene and naphthyl are preferred.

Aryl and arylene may be substituted with a substituent. The substituent is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkylmercapto group, a cycloalkyl group, and a halogen atom. The number of carbon atoms of the alkyl group is preferably 1 to 4. The alkyl portion in the alkoxy group is preferably an alkyl group having 1 to 4 carbon atoms. Examples of the alkoxy system include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and t-butoxy. The alkyl part of the alkylcarbonyl group and the alkylthiol group preferably has an alkyl group having 1 to 4 carbon atoms. Examples of the alkylcarbonyl group include ethenyl, propionyl, 2-methylpropionyl, and butylmethyl. Examples of the alkyl mercapto system include methyl mercapto, ethyl mercapto, propyl mercapto, isopropyl mercapto, butyl mercapto, isobutyl mercapto, sec-butyl mercapto, tert-butyl mercapto, and the like. Cycloalkyl is a monocyclic or polycyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, and examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclodecyl , Cyclododecyl, adamantyl and the like.

[Curable Resin Composition] A curable resin composition comprising: a molecule represented by the following formula (1) in a molecule of 1 or more, and having a group selected from the group consisting of the following formula (2-1) (Meth) acrylate resin represented by the group represented by the following formula (2-2) and one or more of the groups formed by the group represented by the following formula (2-3), and a thermosetting agent And / or polymerization initiators, [Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently hydrogen atom or methyl group, R ²¹ is alkenyl group or alkynyl group, and R ²² and R ²³ are independent alkyl group and olefin group Group, alkynyl or aryl, or R ²² and R ²³ together form a ring structure, X ¹ is an oxygen atom or a sulfur atom, R ²⁴ is an alkyl, alkenyl, alkynyl, or aryl group, but R ²¹ , R ²² and R ²³ are not vinyl or 1-methylvinyl].

((Meth) acrylate resin) A (meth) acrylate resin is in the molecule, has a base represented by formula (1) of 1 or more, and has a group selected from the group represented by formula (2-1), A base represented by formula (2-2) and a base of 1 or more in the group formed by the base represented by formula (2-3) (hereinafter, also referred to as "the first (meth) acrylate resin") .

In addition to the group represented by the formula (1), the first (meth) acrylate resin may have a group selected from the group represented by the formula (2-1), the group represented by the formula (2-2), and A group of 1 or more in the group formed by the group represented by the formula (2-3) may have properties other than those of a (meth) acrylate resin, and may be selected from modified compounds (i.e., unsaturated) Aliphatic carboxylic acids (except for (meth) acrylic acid), carboxylic anhydrides (except for (meth) acrylic anhydride), alcohols and thiols of at least one compound in the group) are given Other features.

The base represented by formula (1), the base represented by formula (2-1), the base represented by formula (2-2), and the base represented by formula (2-3) are monovalent bases, and these The "*" in the base refers to the bonding position. For the bases represented by formula (3), the bases represented by formula (4-1), the bases represented by formula (4-2), the bases represented by formula (4-3), and the bases represented by formula (4- 4) The bases are the same.

In formula (2-2), R ²² and R ²³ that together form a ring structure mean that they form a ring structure together with a C (= O) OC ^* CH ₂ OC (= O) group bonded to R ²² and R ²³ . Here, C ^* is a carbon atom to which R ⁴ is bonded. At this time, the -R ²² R ²³ -system is not particularly limited, but may be interrupted by an alkylene group; an alkenyl group; an alkynyl group; an arylene group; a cycloalkylene group; an arylene group or a cycloalkylene group. Alkylene, alkenyl or alkynyl and the like. Here, the alkenyl and alkynyl systems can be exemplified by alkenyl and alkynyl groups in which one hydrogen atom is removed.

The first (meth) acrylate resin may further have a group represented by the following formula (3), [Wherein R ⁶ is a hydrogen atom or a methyl group].

When the first (meth) acrylate resin has a group represented by the formula (3), the first (meth) acrylate resin also has characteristics as an epoxy resin.

In the first (meth) acrylate resin, in addition to the group represented by formula (1), the group represented by formula (2-1), the group represented by formula (2-2), and the formula (2-3 The base other than the base represented by the formula (3) is arbitrary, and may be, for example, an aromatic or aliphatic base.

As the first (meth) acrylate resin, a (meth) acrylate resin (hereinafter, also referred to as "second (meth) acrylate resin") represented by the following formula (5) can be exemplified, Ar ¹ (-OA ¹ ) _n1 (5) [In the formula, the total number of carbon atoms and heteroatoms of Ar ¹ is 5 or more, and contains an n1 valence group of one or more aromatic rings or heteroaromatic rings. N1 is 1 or more, A ¹ is an independent hydrogen atom, a base represented by the following formula (1), a base represented by the following formula (2-1), a base represented by the following formula (2-2), and the following formula (2 -3) a base represented by the following formula (3), a base represented by the following formula (4-1), or a base represented by the following formula (4-2). A base represented by formula (1), a base represented by formula (4-1); a base having a base represented by formula (1), a base represented by formula (4-2), and a base represented by formula (1) A base of 1 or more in the formed group, and having a base selected from the group consisting of a base represented by formula (2-1), a base represented by formula (2-2), or a base represented by formula (2-3) A base represented by formula (4-1); a base represented by formula (2-1), a base represented by formula (2-2), and / or a base represented by formula (2 -3) the base represented by formula (4-2); the base represented by formula (2-1); the base represented by formula (2-2) and the base represented by formula (2-3) A base of 1 or more in the group formed], [Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently hydrogen atom or methyl group, R ²¹ is alkenyl or alkynyl, and R ²² and R ²³ are each Independent alkyl, alkenyl, alkynyl or aryl groups, or R ²² and R ²³ together form a ring structure, X ¹ is an oxygen atom or a sulfur atom, R ²⁴ is an alkyl, alkenyl, alkynyl or aryl group, However, R ²¹ , R ²² and R ²³ are not vinyl or 1-methylvinyl, B ¹ is an independent alkylene group, m1 is 1 or more, D ¹ is an arylene group, or an alkylene-arylene group. -Alkylene, alkylene-arylene, arylene-alkylene-arylene or group: -B ^2- (OB ² ) _m2- , B ² is an independent alkylene group, and m 2 is 0 Or 1 or more, C ¹ , C ² and C ³ are each independently a hydrogen atom, a base represented by formula (1), a base represented by formula (2-1), a base represented by formula (2-2), A base represented by formula (2-3) or a base represented by formula (3)].

In the formula (5), n1 is preferably 1 to 8, and 1 to 4 is particularly preferable.

In formula (5), the number of carbon atoms contained in Ar ¹ is 4 to 40, the number of oxygen atoms is 0 to 5, the number of nitrogen atoms is 0 to 5, the number of sulfur atoms is 0 to 5, and the ring contained in Ar ¹ The number of structures is preferably 1 to 5.

The ring structure (aromatic ring and / or heteroaromatic ring) contained in Ar ¹ may exist alone or in combination of two or more. The aforementioned ring structure may have a single ring structure or a condensed ring structure. Moreover, these ring structures may be bonded via a direct bond or a linking group, and there may be a plurality of them. Although not particularly limited, Ar ¹ is a ring structure having one or more rings as an essential group (aromatic ring and / or heteroaromatic ring) and only selected from the group consisting of a linking group 1, a linking group 2 and a substituent. It is preferable that one or more kinds of bases be formed as an arbitrary base. Here, the linking group 1 is a linker that links a plurality of ring structures, and the linking group 2 is a linker of Ar ¹ and (-OA ¹ ) in Formula (5).

Examples of the linking groups 1 and 2 include an alkylene group, an alkylidene group, an alkyleneoxy group, an ether group, an ester group, a keto group, a thioether group, and a sulfonyl group. In Formula (5), an oxygen atom bonded to Ar ¹ and a ring structure included in Ar ¹ refer to a structure that can be bonded through the linking group 2, but a ring structure system included in Ar ¹ and bonded to Ar. The oxygen atom of ¹ is preferably directly bonded. The linking group 2 is preferably an alkylene group, an alkylidene group, an alkyleneoxy group, or a keto group. As examples of the linking group 1 or 2, an alkylene-based carbon number of 1 to 4 is preferable, and an alkylidene-based carbon number of 2 to 4 is preferable.

These ring structures may have independent substituents. Examples of such a substituent include an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkylmercapto group, a cycloalkyl group, and a halogen atom.

Examples of the ring structure included in Ar ¹ include benzene ring, naphthalene ring, pyrene ring, anthracene ring, furan ring, pyrrole ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, and thiazine ring And those in which the aforementioned substituents are bonded.

Specific examples of Ar ¹ when n1 is 1 include phenyl, biphenyl, naphthyl, triphenyl, anthracenyl, and fluorenyl.

Specific examples of Ar ¹ when n1 is 2 include arylene having 6 to 20 carbon atoms, arylene having 6 to 20 carbon atoms and alkylene to carbon atom having 1 to 6 carbon atoms. Arylene group having 6 to 20 or arylene group having 6 to 20 carbon atoms -O- (R ⁵¹ -O) _m3 -Arylene group having 6 to 20 carbon atoms [where R ⁵¹ is the number of carbon atoms 1 to 8 alkylene group, m3 is an integer of 0 or 1 to 6], phenylene-isopropylidene-phenylene (remove the two hydroxyl groups from bisphenol A), phenylene-propylene Bisphenols such as methyl-phenylene (remove two hydroxyl groups from bisphenol F), methyl-phenylene-ethylene-phenylene (remove two hydroxyl groups from bisphenol AD), etc. It is preferable to remove two hydroxyl groups.

Specific examples of Ar ¹ when n1 is 3 include the following formulas. Here, * indicates the bond position.

Specific examples of Ar ¹ when n1 is 4 include the following formulas. Here, * indicates the bond position.

Specific examples of Ar ¹ when n1 is 2 or more are phenolic novolacs represented by the following formulas. [In the formula, R ⁶¹ is an independent hydrogen atom, an alkyl group having 1 to 4 carbon atoms, m4 is 0 or more, R ⁶² is an independent bonding position or a hydroxyl group, and the number of bonding positions in R ⁶² is Corresponds to the valence of Ar ¹ ].

In addition, specific examples of Ar ¹ when n1 is 5 or more include groups that remove 4 or more hydrogen atoms of aromatic carbon atoms bonded to specific examples of Ar ¹ when n1 is 1, and removal of 3 or more bonds. A group which is a hydrogen atom of an aromatic carbon atom in a specific example of Ar ¹ when n1 is 2 and an aromatic carbon atom in which an aromatic group of a specific example of Ar ¹ when n1 is 3 is removed A hydrogen atom group, or a group excluding a hydrogen atom of an aromatic carbon atom which is a specific example of Ar ¹ when n1 is 4 or more.

In formula (5), "independently" in the definition of A ¹ means that, for example, when n1 is 2 or more, a selection item (for example, A ¹ ) is independently defined in each case. That is, when n1 is 2 or more, the selection items (for example, A ¹ ) defined by the formula (5) may be different or the same. The same applies to formula (6) and the like described later.

In formula (4-1), m1 is preferably an integer of 1 to 6. In the formula (4-2), when m2 is 1 or more, an integer of 1 to 6 is preferable. A specific example of D ¹ is a specific example of Ar ¹ when n1 is 2.

<Preferred aspect> From the viewpoint of higher strength, when R ²¹ is alkenyl, the number of carbon atoms is preferably 3 to 20, 3 to 10 is more preferable, 1-propenyl, 2-propenyl 1,1-methyl-1-propenyl, 2-methyl-1-propenyl, 3-butenyl and 9-decenyl are particularly preferred. When R ²² and R ²³ are alkyl groups, 1 to 18 carbon atoms are preferred, 1 to 4 are preferred, and butyl is particularly preferred. When R ²⁴ is an alkyl group, 1 to 10 carbon atoms are preferred, 1 to 4 are preferred, and methyl is particularly preferred. When R ²⁴ is aryl, phenyl is particularly preferred. The first (meth) acrylate resin is preferably the second (meth) acrylate resin.

<Mixing amount> In the curable resin composition, the (meth) acrylate resin is preferably contained in an amount of 5 to 95 parts by weight based on 100 parts by weight of the curable resin composition, and is preferably contained in an amount of 10 to 90 parts by weight. It is more preferable to contain 20 to 80 parts by weight.

[Manufacturing method of (meth) acrylate resin] The manufacturing method of (meth) acrylate resin is not particularly limited, as long as it is a method of obtaining the first (meth) acrylate resin. The manufacturing method of a (meth) acrylic acid ester resin is a manufacturing method which includes the process of reacting an epoxy resin and a modified compound with (meth) acrylic acid, for example, Here, the said modified compound system can be selected from unsaturated fats, for example A method for producing a group of one or more compounds of a group of carboxylic acids (except (meth) acrylic acid), carboxylic anhydrides (except (meth) acrylic anhydride), alcohols, and thiols. In addition, the manufacturing method of a (meth) acrylic acid ester resin is the manufacturing method which includes the process of forming the group represented by Formula (1) by reacting the compound which has a hydroxyl group with glycidyl (meth) acrylate, for example. method. The method for producing the (meth) acrylate resin is preferably the method for producing the second (meth) acrylate resin. Hereinafter, a production method including a step of reacting a method for producing a (meth) acrylate resin with an epoxy resin, a modified compound, and (meth) acrylic acid will be described by way of example.

<Epoxy resin> The epoxy resin is not particularly limited as long as it is a resin having two or more epoxy groups in one molecule. Here, when the method for producing a (meth) acrylate resin is the second method for producing a (meth) acrylate resin, the epoxy resin may be, for example, an epoxy resin represented by the following formula (6), Formula: Ar ² (-OA ² ) _n2 (6) [In the formula, Ar ² is synonymous with Ar ¹ , n2 is synonymous with n1, and A ² is an independent hydrogen atom; a base represented by the following formula (3); the following The base represented by the formula (4-3); or the base represented by the following formula (4-4), but having 2 or more epoxy groups in the molecule], [In the formula, R ⁶ is as described above; B ³ is synonymous with B ¹ ; m 5 is synonymous with m ¹ ; R ⁸ is synonymous with R ⁷ ; D ² is synonymous with D ¹ ; C ⁴ , C ^5, and C ⁶ Are each independently a hydrogen atom or a group represented by formula (3)].

The epoxy resin represented by the formula (6) is one molecule and has an epoxy group of 2 or more, but the epoxy group is an epoxy group of the group represented by the formula (3). Therefore, when n2 is 1, A ² is a base represented by formula (4-4), and C ⁵ and C ⁶ are bases represented by formula (3).

As a method for producing the first (meth) acrylate resin, Ar ² of the epoxy resin represented by the formula (6) can be used as an arbitrary structure (for example, an aromatic or aliphatic group).

In such a molecule, the resin system having an epoxy group of 2 or more is not particularly limited, and examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and phenolic phenolic resin. Varnish type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac resin type epoxy resin, bisphenol F novolac resin type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy Resin, glycidyl ester epoxy resin, glycidylamine epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, phenolic novolac type epoxy with triphenol methane skeleton Resin, etc. In addition, diglycidyl etherate of difunctional phenols, diglycidyl etherate of difunctional alcohols, halides, hydrides, and the like can also be used.

The epoxy resin is commercially available or can be prepared according to a known method. The epoxy resin having a base represented by the formula (4-3) can be obtained by, for example, a method described in Japanese Patent Application Laid-Open No. 8-333356 or a method similar thereto. The epoxy resin having a base represented by the formula (4-4) can be obtained by, for example, a method described in Japanese Patent Application Laid-Open No. 2012-077202 and Japanese Patent Application Laid-Open No. 2013-241488, or a method similar thereto.

<Modified compounds> Modified compounds are selected from unsaturated aliphatic carboxylic acids (except (meth) acrylic acid), carboxylic anhydrides (except (meth) acrylic anhydride), alcohols, and thiols. 1 or more compounds in the formed group. The modified compounds can be used alone or in combination of two or more.

Examples of the unsaturated aliphatic carboxylic acid (except for (meth) acrylic acid) are compounds represented by the formula: R ⁴¹ -COOH [wherein, R ⁴¹ is synonymous with R ²¹ ]. By using an unsaturated aliphatic carboxylic acid (other than (meth) acrylic acid), a (meth) acrylate resin having a group represented by the formula (2-1) can be obtained. At this time, when the epoxy group of the epoxy resin represented by the formula (6) is a glycidyl group, R ³ is a hydrogen atom, and when the epoxy group of the epoxy resin represented by the formula (6) is In the case of methyl glycidyl, R ³ is a methyl group.

Examples of carboxylic acid anhydrides (except for (meth) acrylic anhydride) are: R ⁴² -C (= O) -OC (= O) -R ⁴³ [wherein R ⁴² and R ⁴³ are R ²² and R ^{23 are} synonymous]. By using a carboxylic anhydride (except for (meth) acrylic anhydride), a (meth) acrylate resin having a group represented by the formula (2-2) can be obtained. R ²² and R ²³ that form a ring structure together are formed by reaction with an epoxy group, succinic anhydride, maleic anhydride, phthalic anhydride, and other dicarboxylic anhydrides in an epoxy resin. In these cases, R ⁴ is the same as R ³ .

Examples of the alcohol and thiol system are compounds represented by the formula: R ⁴⁴ -X ² -H [wherein R ⁴⁴ is synonymous with R ²⁴ and X ² is synonymous with X ¹ ]. By using one or more compounds selected from the group consisting of alcohols and thiols, a (meth) acrylate resin having a group represented by the formula (2-3) is obtained. In this case, R ⁵ is the same as R ³ .

<(Meth) acrylic acid> (Meth) acrylic acid is one or more selected from the group consisting of acrylic acid and methacrylic acid. By reacting an epoxy group in the epoxy resin with (meth) acrylic acid, a (meth) acrylate resin having a group represented by formula (1) is obtained. At this time, when the (meth) acrylic acid is acrylic acid, R ¹ is a hydrogen atom, and when the (meth) acrylic acid is methacrylic acid, R ¹ is a methyl group. R ² is the same as R ³ .

In the obtained (meth) acrylate resin, when an epoxy group which does not react with the (meth) acrylic acid and the modified compound is present, the (meth) acrylate resin has the formula (3) base. In this case, R ⁶ is the same as R ³ .

<Reaction conditions> (1) In order to obtain (meth) acrylic resin, the reaction conditions can be appropriately applied to known conditions used for the reaction between epoxy resin and modified compounds and (meth) acrylic acid.

The reaction can be performed in the presence or absence of a basic catalyst and / or an acid catalyst. Examples of the alkaline catalyst and the acid catalyst include known alkaline catalysts and acid catalysts used in the reaction between an epoxy resin and a modified compound.

Alkaline catalysts are alkali metal hydroxides (sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (sodium carbonate, potassium carbonate, etc.), alkali metal alkoxides (sodium methoxide, etc.), and trivalent organic phosphorus Compounds and / or amine compounds are preferred. Alternatively, a polymer-supported basic catalyst in which a basic catalyst is supported on a polymer may be used.

Examples of the trivalent organic phosphorus compound include triethylphosphine, tri-n-propylphosphine, tri-n-butylphosphine-like alkylphosphines and salts thereof, triphenylphosphine, and tri-m-toluene. Arylphosphines, para- (2,6-dimethoxyphenyl) phosphines, bis [2- (diphenylphosphino) phenyl] ethers, and their salts, triphenylphosphites , Triethyl phosphite, ginseng (nonylphenyl) phosphite and the like and their salts. Examples of the salt of the trivalent organophosphorus compound include triphenylphosphine ･ ethyl bromide, triphenylphosphine ･ butyl bromide, triphenylphosphine ･ octyl bromide, and triphenylphosphine ･ decyl Bromide, triphenylphosphine, isobutyl bromide, triphenylphosphine, propyl chloride, triphenylphosphine, pentyl chloride, triphenylphosphine, hexyl bromide, and the like.

Examples of the amine compound include secondary amines such as diethanolamine, triethanolamine, dimethylbenzylamine, gins (dimethylaminomethyl) phenol, and gins (diethylaminomethyl) phenol. Tertiary amine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo [4.4.0] Dec-5-ene (Me-TBD), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), 6-dibutylamino-1,8-diazabicyclo [5.4.0] Strong bases such as undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene (DBN), 1,1,3,3-tetramethylguanidine Sex amines and their salts. Among them, 1,5,7-triazabicyclo [4.4.0] dec-5-ene (TBD) is preferred. Examples of the salt of the amine compound include benzyltrimethylammonium chloride and benzyltriethylammonium chloride.

Examples of the acid catalyst system include sulfuric acid such as sulfuric acid, trifluoromethanesulfonic acid, graphite oxide, and antimony fluoride. As the acid catalyst, a cation exchanger (for example, Amberlyst, which is a commercially available product) can be used. Acid catalysts can be used in the reaction of epoxy resins with at least one compound selected from the group consisting of alcohols and thiols.

The reaction can be carried out in the presence or absence of a solvent. For the reaction, an inert solvent such as a hydrocarbon, ether or ketone can also be used for the reaction, but when an epoxy resin is used in excess, the resin also functions as a solvent, so such solvents are unnecessary.

The reaction temperature can be appropriately set by the supplier depending on the catalyst and raw material compounds used. For example, the catalyst is an alkaline catalyst, and (meth) acrylic acid is used and selected from carboxylic acids (but other than (meth) acrylic acid) and carboxylic anhydrides (but other than (meth) acrylic anhydride) When one or more of the formed groups are used as modified compounds, the reaction temperature is preferably 60 to 120 ° C, preferably 80 to 120 ° C, more preferably 90 to 120 ° C, and particularly preferably 100 to 120 ° C. For example, when the catalyst is an acid catalyst and the alcohol is used as a modified compound, the reaction temperature is preferably 0 to 100 ° C, preferably 10 to 90 ° C, and particularly preferably 25 to 80 ° C.

The reaction amount of (meth) acrylic acid with respect to 1 equivalent of epoxy groups of the aforementioned epoxy resin is more than 0 equivalent% to 100 equivalent%, and the reaction amount of modified compounds with respect to 1 equivalent of epoxy groups is more than 0 equivalents. % Is less than 100 equivalent%, and the reaction amount relative to the total of 1 equivalent of epoxy (meth) acrylic acid and modified compound is more than 0 equivalent% and 100 equivalent% or less, preferably 10 to 90 equivalent%, more preferably 20 ~ 80 equivalent%, particularly preferably 30 ~ 70 equivalent%. In the method for producing a (meth) acrylate resin, the reaction between the epoxy group and the (meth) acrylic acid and the modified compound is performed quantitatively, so the modification rate of the obtained (meth) acrylate resin can also be determined by the ring. Oxygen equivalent is estimated.

The (meth) acrylic acid and the modified compound can be simultaneously reacted with the epoxy resin to obtain a (meth) acrylate resin. Also, by reacting an epoxy resin with a modified compound to obtain an epoxy resin partially modified by the modified compound, and by reacting an epoxy resin partially modified by the aforementioned modified compound with (meth) acrylic acid, (( (Meth) acrylic resin, which reacts the epoxy resin with (meth) acrylic acid to obtain an epoxy resin partially modified with (meth) acrylic acid, and an epoxy resin partially modified with (meth) acrylic acid and modified (Meth) acrylate resin can also be obtained by reacting the basic compounds.

Also, a (meth) acrylate resin obtained by a method for producing a (meth) acrylate resin is a resin mixture containing a resin having the same skeleton. Here, the aforementioned skeleton in the second (meth) acrylate resin is referred to as a part of Ar ¹ . Therefore, the aforementioned skeleton in the first (meth) acrylate resin is referred to as a base represented by formula (1), a base represented by formula (2-1), a base represented by formula (2-2), and The part other than the base represented by formula (2-3).

(Thermosetting agent and / or polymerization initiator) The thermosetting agent and / or the polymerization initiator can be appropriately selected depending on the components contained in the curable resin composition. By using a thermosetting agent, a curable resin composition can be made into a thermosetting resin composition. By using a polymerization initiator, the curable resin composition can be made into a radical polymerization curable, anionic polymerization curable, and / or cationic polymerization curable resin composition. The blending amount of the thermosetting agent is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, and still more preferably 5 to 25 parts by weight with respect to 100 parts by weight of the curable resin composition. With respect to 100 parts by weight of the curable resin composition, the blending amount of the polymerization initiator is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, and even more preferably 1 to 5 parts by weight.

<Heat hardener> Although the heat hardener is not particularly limited, examples of the amine heat hardener include organic acid dihydrazine compounds, amine adducts, imidazole and its derivatives, dicyandiamide, aromatic amines, and epoxy resins. Modified polyamine and polyurea, etc., with VDH (1,3-bis (hydrazinocarbonethyl) -5-isopropylhydantoin), ADH (dihydrazide adipate), UDH (7,11-octadecadiene-1,18-dicarbohydrazine) and LDH (octadecane-1,18-dicarboxylic acid dihydrazine) and other organic acids; ADEKA Corporation Commercially available polyamine compounds such as ADEKA HARDENEREH5030S are preferably commercially available amine adducts such as AJICUREPN-23, AJICUREPN-30, AJICUREMY-24, and AJICUREMY-H of Ajinomoto Fine-Techno Co., Ltd. These heat curing agents may be used alone or in combination.

<Polymerization Initiator> The polymerization initiator may be a radical polymerization initiator, an anionic polymerization initiator, and / or a cationic polymerization initiator. The polymerization initiator is a component in which a hardening component included in the curable resin composition is a source of radical generation during radical polymerization, anion generating source during anionic polymerization, and cation generating source during cation polymerization.

Examples of the radical polymerization initiator include benzoin, acetophenone, benzophenone, thioxanthone, α-fluorenyl oxime ester, phenylglyoxylic acid, benzyl ester, and azo Compounds, diphenyl sulfide compounds, fluorenyl phosphine oxide compounds, benzoin ethers, anthraquinones, organic peroxides, and the like. The radical polymerization initiator is preferably one having a low solubility in liquid crystal and having a reactive group that does not vaporize a decomposed substance upon light irradiation. In addition, as a radical polymerization initiator, a compound obtained by reacting a compound having at least two epoxy groups described in WO2012 / 077720 with dimethylaminobenzoic acid and a compound having at least two epoxy groups A polymerization initiator of a mixture of compounds obtained by reaction with hydroxythioxanthone is preferred.

Examples of the anionic polymerization initiator include imidazoles, amines, phosphines, organometallic salts, metal chlorides, and organic peroxides.

Examples of the cationic polymerization initiator system include an onium salt, an iron propadiene complex, a titanocene complex, an aluminum aryl silanol complex, a Lewis acid compound, a Bronsted acid compound, and a benzylsulfonium salt. , Thiophene salt, tetrahydrothienium salt (Thiolanium salt), benzyl ammonium, pyridine salt, hydrazine salt, carboxylic acid ester, sulfonate ester, amidoimine, amidine compound, sulfonate, sulfonylimine Class, disulfohydrazone diazomethanes, and amines.

The polymerization initiator is commercially available or can be prepared according to a known method. The radical polymerization initiator, the anionic polymerization initiator, and the cationic polymerization initiator may be used singly or in combination of two or more kinds. Depending on the desired hardening conditions (energy ray hardening and / or thermal hardening), a polymerization initiator can be used as appropriate.

(Other components) The hardenable composition may contain one selected from the group consisting of another resin (except for the first (meth) acrylate resin), a photosensitizer, a filler, and a coupling agent. The other ingredients above.

<Other resins> Another resin is not particularly limited as long as it is a resin other than the first (meth) acrylate resin, and examples thereof include conventional unsaturated groups and / or as a main agent of a liquid crystal sealant. Epoxy resins and resins that do not have either unsaturated groups or epoxy groups. Here, the "unsaturated group" means an ethylenically unsaturated group and / or an acetylene unsaturated group.

<< Resin with Unsaturated Groups> Examples of resins with unsaturated groups include (meth) acrylate compounds, aliphatic acrylamide compounds, alicyclic acrylamide compounds, and acrylamine containing aromatics. Compound, N-substituted acrylamide-based compound, diene-based polymer (for example, polybutadiene polymer, polyisoprene polymer, etc.). The functionality of the (meth) acrylate compound may be monofunctional, difunctional, or trifunctional or more.

The monofunctional (meth) acrylate compound is selected from the group consisting of hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isooctyl (methyl Base) acrylate, cyclohexyl (meth) acrylate, isofluorenyl (meth) acrylate, dicyclopentyl (meth) acrylate, cyclohexyloxyethyl (meth) acrylate, dicyclopentyl Oxyethyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, isomyristoyl (meth) acrylate, lauryl (meth) acrylate, tert-butyl ( (Meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, p-cumylphenoxyethylene glycol (meth) acrylate, and ethoxylated phenyl (meth) acrylate One or more compounds in the composition group are preferred.

The difunctional (meth) acrylate compound is selected from the group consisting of tricyclodecane dimethanol di (meth) acrylate, dimethylol dicyclopentane di (meth) acrylate, and EO 1, 6-hexanediol di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, polyester di (meth) acrylic acid Ester (for example, ARONIX M-6100, manufactured by Toa Synthesis Co., Ltd.), polyethylene glycol di (meth) acrylate (for example, 4G, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), and silicon bis (methyl) One or more compounds in the group formed by acrylate (for example, EBCRYL 350, manufactured by Daicel-allnex Co., Ltd.) are preferred. Here, "EO" means ethylene oxide, and "PO" means propylene oxide.

The polyfunctional (meth) acrylate compound that is trifunctional or higher is selected from EO modified glycerol tri (meth) acrylate (trifunctional), PO modified glycerol tri (meth) acrylate (trifunctional) , Pentaerythritol tri (meth) acrylate (trifunctional), dipentaerythritol hexa (meth) acrylate (hexafunctional) and pentaerythritol tetra (meth) acrylate (tetrafunctional) 1 or more are preferred.

Further, as the resin having an unsaturated group, epoxy resins in which all epoxy groups are modified by (meth) acrylic acid and epoxy resins in which all epoxy groups are modified by unsaturated groups can be exemplified. Modified epoxy resin.

<<< Resin having epoxy group> ＞ The resin having an epoxy group is not particularly limited as long as it has an epoxy group of 1 or more. Examples of the resin having one epoxy group include aromatic epoxy resins and aliphatic epoxy resins. Examples of the resin having an epoxy group of 2 or more include those described above as the epoxy resin. In addition, the partially modified epoxy resin in which a part of the epoxy group of the epoxy resin is modified by the modified compound can be exemplified.

＜< Unsaturated group and resin with epoxy group ＞ As an unsaturated group and resin with epoxy group, for example, part of epoxy group of epoxy resin is partially modified by compound with unsaturated group. Epoxy resin (for example, a (meth) acrylate modified epoxy resin partially modified by a (meth) acrylic compound).

＜< Resin without any unsaturated group and epoxy group ＞ As a resin system without any unsaturated group and epoxy group, all epoxy groups of epoxy resin are not included. Unsaturated modified compounds, modified epoxy resins, polyurethane resins formed from compounds containing hydroxyl groups and compounds containing isocyanate groups, etc.

＜< Recommended Additional Resin> Another resin-based epoxy resin (except for epoxy resins having a (meth) acrylic fluorenyl group), and some or all of the epoxy groups of the epoxy resin are (a Base) A modified epoxy resin modified by acrylic acid and a modified epoxy resin modified in part or all of epoxy groups of epoxy resin by modified compounds. Here, the modified compound is selected from unsaturated aliphatic A resin of one or more compounds in a group of carboxylic acid (except (meth) acrylic acid), carboxylic anhydride (except (meth) acrylic anhydride), alcohol, and thiol is preferable .

Here, the epoxy resin (except for the epoxy resin having a (meth) acrylfluorene group) is an epoxy resin that can be used as a raw material for obtaining a (meth) acrylate resin. In addition, a modified epoxy resin in which part or all of epoxy groups of the epoxy resin is modified by (meth) acrylic acid can be obtained as a (meth) acrylic acid ester by a method of producing a (meth) acrylic acid ester resin. Ingredients other than resin. Some or all of the epoxy groups of the epoxy resin are modified epoxy resin modified by a modified compound, and the modified compound is selected from unsaturated aliphatic carboxylic acid (except (meth) acrylic acid) Modified epoxy resins based on carboxylic acid anhydrides (except for (meth) acrylic anhydride), alcohols and thiols, and more than one compound in the group can be produced by (meth) acrylate resins By the method, components other than (meth) acrylate resin are obtained.

<Photosensitizer> The photo-sensitizing agent may further contain a photosensitizer in order to improve the sensitivity to light at the time of photocuring. From the viewpoint of hardenability, examples of the photosensitizer include a carbonyl compound, an organic sulfur compound, a persulfide, a redox compound, an azo and diazo compound, a halogen compound, and a photoreducible pigment. Specifically, examples of the photosensitizer include N-methylacridone and N-butylacridone derivatives such as acridone; others, α, α-diethoxyacetophenone, benzyl Groups, fluorenone, heteroanthone, urea-based compounds, and the like as examples of the polymerization initiator, there are also those who act as photosensitizers. The photosensitizers can be used alone or in combination of two or more.

<Filling material> Filling material is used for the purpose of controlling the viscosity of the hardening resin composition or improving the strength of the hardened material of the hardening resin composition, or suppressing the linear expansion, so as to improve the reliability of the hardening resin composition. Added. The filler system is not particularly limited, and examples thereof include inorganic fillers and organic fillers. Examples of the inorganic filler include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, aluminum oxide, zinc oxide, silicon dioxide, kaolin, talc, glass beads, sericite activated clay, bentonite, Aluminum nitride and silicon nitride. Examples of the organic filler system include copolymers containing polymethyl methacrylate, polystyrene, copolymers of these monomers and other monomers, polyester fine particles, polyurethane fine particles, and rubber. Fine particles and core-shell particles and the like composed of a shell containing a copolymer having a high glass transition temperature and a core of a copolymer having a low glass transition temperature. As the filler, a commercially available product can be used. Examples of commercially available products of silica particles include SEAHOSTARKE series (KE-C50, etc.). Examples of the core-shell type particle system include ZEFIACK series (F-351, etc., manufactured by Aica Industrial Co., Ltd.) and the like. The filler system can be used individually by 1 type or in combination of 2 or more types.

<Silane coupling agent> The hydrazine coupling agent is added for the purpose of further improving the adhesion strength. The silane coupling agent is not particularly limited, and examples thereof include γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatepropyltrimethoxysilane, and 3-glycidoxypropyl Trimethoxysilane and so on. Silane coupling agents can be used alone or in combination of two or more.

(Application of hardening resin composition) The hardening resin composition is preferably used as a sealant, and a sealant used in a display element, a light amount adjustment element, a variable focus element, a light modulation element, or the like is preferable. . In addition, the curable resin composition is used for a liquid crystal display (or a liquid crystal display element) including a modular display, a three-dimensional display, a head-mounted display, a projection display, and the like; a dimming filter, a dimming shutter, and an anti-glare. Anti-glare mirrors, spatial light quantity modulators, and other light quantity adjustment liquid crystal elements; variable focus liquid crystal elements such as liquid crystal lenses and optical deflectors, optical demultiplexers, phase control, polarization control, holograms, diffraction gratings , Wavelength filter, frequency filter, and other light-modulating liquid crystal elements; liquid crystal sealing agent is more preferred, liquid crystal dropping method sealing agent is particularly preferred.

The curable resin composition can be cured by being irradiated with energy rays such as ultraviolet rays, before or after being heated or by being irradiated with energy rays such as ultraviolet rays, or the like. [Example]

Hereinafter, the present invention will be described more specifically with examples, but the present invention is not limited to these examples. The resin systems used in the examples and comparative examples are manufactured as follows.

[Comparative Synthesis Example 1] Comparative (meth) acrylate resin 1 (partially methacrylated bisphenol A type epoxy resin) Hybrid bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 340.0 g, 86.1 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 500 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 100 ° C. for 6 hours. 418.0 g of a comparative (meth) acrylate resin 1 having a pale yellow transparent sticky substance was obtained.

[Synthesis Example 1] (meth) acrylate resin 1 170.0 g of mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 21.5 g of methacrylic acid (made by Tokyo Chemical Industry Co., Ltd.), 21.5 g of crotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 262 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C. for 4 hours. 201.9 g of (meth) acrylate resin 1 as a yellow transparent sticky substance was obtained.

[Synthesis Example 2] (meth) acrylate resin 2 85.0 g of mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 10.8 g of methacrylic acid (made by Tokyo Chemical Industry Co., Ltd.), 10.8 g of 3-butenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C. for 5 hours. 105.2 g of (meth) acrylate resin 2 as a yellow transparent sticky substance was obtained.

[Synthesis Example 3] (meth) acrylate resin 3 mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.8 g, 14.0 g of sorbic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C. for 5 hours. 107.6 g of a (meth) acrylate resin 3 as a yellow transparent sticky substance was obtained.

[Synthesis Example 4] (meth) acrylate resin 4 mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.8 g, 12.5 g of 3-methylcrotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C. for 5 hours. 104.1 g of (meth) acrylate resin 4 as a yellow transparent sticky substance was obtained.

[Synthesis Example 5] (meth) acrylate resin 5 mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.8 g, 23.0 g of 10-undecenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C. for 5 hours. 117.7 g of a (meth) acrylate resin 5 as a yellow transparent sticky substance was obtained.

[Synthesis Example 6] (meth) acrylate resin 6: 85.0 g of mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 10.8 g of methacrylic acid (made by Tokyo Chemical Industry Co., Ltd.), 12.5 g of 4-pentenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C. for 5 hours. 105.1 g of (meth) acrylate resin 6 as a yellow transparent sticky substance was obtained.

[Synthesis Example 7] (meth) acrylate resin 7: 85.0 g of mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 10.8 g of methacrylic acid (made by Tokyo Chemical Industry Co., Ltd.), 12.5 g of chamomile acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C for 5 hours. 107.4 g of a (meth) acrylate resin 7 as a yellow transparent sticky substance was obtained.

[Synthesis Example 8] (meth) acrylate resin 8: 170.0 g of mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 32.3 g of methacrylic acid (made by Tokyo Chemical Industry Co., Ltd.), 10.7 g of crotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 262 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C. for 5 hours. 205.2 g of a (meth) acrylate resin 8 as a yellow transparent sticky substance was obtained.

[Synthesis Example 9] (meth) acrylate resin 9: 85.0 g of mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 16.1 g of methacrylic acid (made by Tokyo Chemical Industry Co., Ltd.), 5.4 g of 3-butenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C. for 5 hours. 100.4 g of a (meth) acrylate resin 9 as a yellow transparent sticky substance was obtained.

[Synthesis Example 10] (meth) acrylate resin 10 10 mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 16.1 g, 11.5 g of 10-undecenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C. for 5 hours. 107.1 g of a (meth) acrylate resin 10 as a yellow transparent sticky substance was obtained.

[Synthesis Example 11] (meth) acrylate resin 11 mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.4 g, 16.1 g of crotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C. for 5 hours. 97.8 g of a (meth) acrylate resin 11 having a yellow transparent sticky substance was obtained.

[Synthesis Example 12] (meth) acrylate resin 12 mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.4 g, 16.1 g of 3-butenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C. for 5 hours. 101.7 g of a (meth) acrylate resin 12 as a yellow transparent sticky substance was obtained.

[Synthesis Example 13] (meth) acrylate resin 13: 85.0 g of mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 5.4 g of methacrylic acid (made by Tokyo Chemical Industry Co., Ltd.), 34.5 g of 10-undecenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C. for 6 hours. 120.1 g of a (meth) acrylate resin 13 as a yellow transparent sticky substance was obtained.

[Synthesis Example 14] (meth) acrylate resin 14 树脂 mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 16.1 g, 10.7 g of crotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C. for 7 hours. 108.5 g of a (meth) acrylate resin 14 as a yellow transparent sticky substance was obtained.

[Synthesis Example 15] (meth) acrylate resin 15: 85.0 g of mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 21.5 g of methacrylic acid (made by Tokyo Chemical Industry Co., Ltd.), 10.7 g of crotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C. for 7 hours. 112.0 g of a (meth) acrylate resin 15 having a yellow transparent sticky substance was obtained.

[Synthesis Example 16] (meth) acrylate resin 16 16 mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) 85.0 g, methacrylic acid (made by Tokyo Chemical Industry Co., Ltd.) 14.3 g, 14.3 g of crotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C. for 7 hours. 111.2 g of a (meth) acrylate resin 16 as a yellow transparent sticky substance was obtained.

[Synthesis Example 17] (meth) acrylate resin 17: 85.0 g of mixed bisphenol A epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 425.0 g of methanol (made by Kanto Chemical Co., Ltd.), and sodium methoxide ( 2.7 g (manufactured by Kanto Chemical Co., Ltd.), and after stirring at 50 ° C for 60 minutes, 50.0 g of 3% hydrochloric acid was added. After methanol was distilled under reduced pressure, 300 mL of ethyl acetate was added and washed 4 times with 300 mL of water. To the obtained organic phase, magnesium sulfate was added, and after drying, solid components were filtered off by filtration, etc., and the solvent of the obtained organic phase was distilled by distillation under reduced pressure to obtain 87.0 g of methanol as a transparent sticky substance. Partially modified epoxy resin. 79.6 g of epoxy resin partially modified with methanol, 10.8 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 116 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and stirred at 100 ° C for 2 hours . 87.3 g of a (meth) acrylate resin 17 having a yellow transparent sticky substance was obtained.

[Synthesis Example 18] (Meth) acrylate resin 18 425.0 g of 1-butanol (manufactured by Kanto Chemical Co., Ltd.) and 2.7 g of sodium methoxide (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 70 ° C. for 3 hours. The reaction mixture was cooled to 50 ° C, 85.0 g of bisphenol A epoxy resin (EXA-850CRP, manufactured by DIC Corporation) was added, and after stirring for 50 minutes, 50.0 g of 3% hydrochloric acid was added, and 1-butanol was distilled under reduced pressure. Add 300 mL of ethyl acetate and wash 4 times with 300 mL of water. To the obtained organic phase, magnesium sulfate was added, and after drying, solid components were filtered off by filtration, etc., and the solvent of the obtained organic phase was distilled by distillation under reduced pressure to obtain 81.4 g of a transparent viscous substance. -Partially modified butanol epoxy resin. 73.7 g of epoxy resin partially modified with 1-butanol, 8.4 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 102 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed at 100 ° C. Stir for 2 hours. 79.2 g of a (meth) acrylate resin 18 having a yellow transparent sticky substance was obtained.

[Synthesis Example 19] (meth) acrylate resin 19: 150.0 g of 1-decanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.2 g of sodium methoxide (manufactured by Kanto Chemical Co., Ltd.) were stirred at 70 ° C for 2 hours. . The reaction mixture was cooled to 50 ° C, 34.0 g of a bisphenol A epoxy resin (EXA-850CRP, manufactured by DIC Corporation) was added, and after stirring for 50 minutes, 40.0 g of 3% hydrochloric acid was added, 300 mL of ethyl acetate was added, and 300 mL Wash 4 times with water. Magnesium sulfate was added to the obtained organic phase, and after drying, solid components were filtered off by filtration, etc., and the solvent of the obtained organic phase was distilled by distillation under reduced pressure to obtain 41.5 g of a transparent viscous material. -Partially modified epoxy resin of decanol. 30.0 g of epoxy resin partially modified with 1-decanol, 3.1 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 37 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed at 100 ° C. Stir for 4 hours. 31.7 g of a (meth) acrylate resin 19 as a yellow transparent sticky substance was obtained.

[Synthesis Example 20] (meth) acrylate resin 20: 85.0 g of mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 11.8 g of phenol (produced by Tokyo Chemical Industry Co., Ltd.), and tribenzene 130 mg of base phosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred at 100 ° C for 15 hours. 18.8 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 ° C. for 7 hours. 102.2 g of a (meth) acrylate resin 20 having a yellow transparent sticky substance was obtained.

[Synthesis Example 21] (meth) acrylate resin 21: 85.0 g of mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 10.7 g of methacrylic acid (made by Tokyo Chemical Industry Co., Ltd.), 12.7 g of fluoric anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C. for 6 hours. 102.3 g of a (meth) acrylate resin 21 as a yellow transparent sticky substance was obtained.

[Synthesis Example 22] (meth) acrylate resin 22: 85.0 g of mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 10.7 g of methacrylic acid (made by Tokyo Chemical Industry Co., Ltd.), 19.8 g of butyric anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C. for 6 hours. 108.3 g of a (meth) acrylate resin 22 as a yellow transparent sticky substance was obtained.

[Synthesis Example 23] (meth) acrylate resin 23: 85.0 g of mixed bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 10.7 g of methacrylic acid (made by Tokyo Chemical Industry Co., Ltd.), 19.3 g of croton anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C. for 6 hours. 99.5 g of a (meth) acrylate resin 23 having a yellow transparent sticky substance was obtained.

[Reference Synthesis Example 1] Epoxy resin A (Reference Synthesis Example 1-1) Synthesis of an ethylene glycol ring opener of EXA-850CRP was placed in an eggplant flask, and 500.0 g of ethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. And 1.0 g of a 45% aqueous solution of stannous (II) fluoborate (manufactured by Morita Chemical Industry Co., Ltd.). 340.0 g of a bisphenol A type epoxy resin (EXA-850CRP, manufactured by DIC Corporation) was slowly added over 1 hour, and the mixture was stirred at 80 ° C while the addition was completed, and the mixture was stirred at 80 ° C for 1 hour. The reaction mixture was cooled to room temperature, 1 L of chloroform was added, and washed 6 times with 1 L of water. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 410.0 g of EXA-850CRP-ethylene glycol ring-opening substance as a colorless transparent sticky substance. (Reference Synthesis Example 1-2) Synthesis of epoxy resin A 400.0 g of EXA-850CRP-ethylene glycol ring-opener, 1017.0 g of epichlorohydrin (manufactured by Osaka Soda Co., Ltd.), and benzyltrimethyl chloride 51.0 g of ammonium (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to a 2 L 3-necked round bottom flask equipped with a mechanical stirrer, thermometer, temperature controller, condenser, Dean-Stark-separator and dropping funnel. Next, while stirring the mixture under a high vacuum of 70 torr, it was heated at about 50 to 55 ° C. to vigorously reflux the epichlorohydrin. 137.0 g of a 48% sodium hydroxide aqueous solution (manufactured by Kanto Chemical Co., Ltd.) was slowly added to the mixture over 2 hours. When an azeotrope is formed, the epichlorohydrin is immediately returned to the reaction system in the water / epichlorohydrin mixture while continuously stirring. After the addition was completed, stirring was continued for 3 hours. Next, the reaction mixture was cooled to room temperature, 1 L of chloroform was added, and it washed with 1 L of water 6 times. The solvent of the obtained organic phase was removed by distillation under reduced pressure to obtain 506.0 g of a pale yellow transparent viscous epoxy resin A (epoxy equivalent 228 g / eq, viscosity 27,600 mPa ･ s).

[Comparative Synthesis Example 2] Comparative (meth) acrylate resin 2 2 228.0 g of mixed epoxy resin A, 43.0 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 262 mg, and stirred at 100 ° C for 7 hours. 265.0 g of a comparative (meth) acrylate resin 2 having a yellow transparent sticky substance was obtained.

[Synthesis Example 24] (meth) acrylate resin 24: 1111 g of mixed epoxy resin A, 10.8 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.8 g of crotonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred at 100 ° C for 7 hours. 128.0 g of a (meth) acrylate resin 24 as a yellow transparent sticky substance was obtained.

[Synthesis Example 25] (meth) acrylate resin 25 Mixed epoxy resin A114.0 g, methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.8 g, 3-butenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.8 g and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 100 ° C. for 7 hours. 124.0 g of a (meth) acrylate resin 25 as a yellow transparent sticky substance was obtained.

[Synthesis Example 26] (meth) acrylate resin 26: 1111 g of mixed epoxy resin A, 10.8 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 10-undecenoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 23.0 g and 130 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 100 ° C. for 7 hours. 136.0 g of a (meth) acrylate resin 26 as a yellow transparent sticky substance was obtained.

[Production of Photopolymerization Initiator] (1) The photopolymerization initiators used in the examples and comparative examples were produced as follows. (Production of Photopolymerization Initiator 1) (2) Add 26.8 g of diglycidyl ether (denacol EX-830, manufactured by Nagase Chemical Co., Ltd.), 16.5 g of 4-dimethylaminobenzoic acid, and benzyl to the flask. 3.7 g of trimethyl ammonium chloride and 25.0 g of methyl isobutyl ketone (MIBK) were stirred at 110 ° C. for 24 hours. The reaction mixture was cooled to room temperature, dissolved in 50.0 g of chloroform, and washed 6 times with 100 mL of water. The solvent of the organic phase was distilled under reduced pressure to obtain 35.3 g of a photopolymerization initiator 1. (Production of Photopolymerization Initiator 2) 26.8 g of PEG400 diglycidyl ether (denacol EX-830, manufactured by Nagase Chemical Co., Ltd.), 2-hydroxy-9H-thioxan-9-one 22.8 were placed in a flask. g, 3.7 g of benzyltrimethylammonium chloride and 40.0 g of MIBK, and stirred at 110 ° C for 72 hours. The reaction mixture was cooled to room temperature, dissolved in 50.0 g of chloroform, and washed 6 times with 100 mL of water. The solvent of the organic phase was distilled under reduced pressure to obtain 36.2 g of a photopolymerization initiator 2.

[Examples 1 to 26 and Comparative Examples 1 to 2] The respective (meth) acrylate resins and comparative (meth) acrylate resins manufactured by the Synthesis Examples and Comparative Synthesis Examples and the photopolymerization initiators 1 and 2 Fillers; core-shell particles (ZEFIACF-351, manufactured by Aica Industrial Co., Ltd.), fillers; silicon dioxide particles (seahostarKE-C50, manufactured by Japan Catalyst Co., Ltd.); silane coupling agent; 3-epoxypropoxy Propylmethyldiethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), hardener; polyamine compound (EH-5030S, manufactured by ADEKA Corporation, active hydrogen equivalent 105 g / eq), After mixing at the blending amounts (parts by weight) shown in Tables 1 to 4 below, they were thoroughly kneaded by a 3-roll mill (C-4 3/4 × 10, manufactured by Inoue Seisakusho Co., Ltd.) to produce examples and Comparative example is a curable resin composition.

Each (meth) acrylate resin manufactured by the synthesis example and the comparative synthesis example, and the curable resin composition of an Example and a comparative example was evaluated by the following test.

[Test conditions] For (meth) acrylate resins and comparative (meth) acrylate resins, measure the epoxy equivalent and viscosity, and for photopolymerization initiators 1 and 2, measure the viscosity. Adhesive strength of the curable resin composition.

(1) Measurement of epoxy equivalent weight (WPE) 测定 Measured under the conditions described in JIS K 7236: 2001. The unit of epoxy equivalent in the table is g / eq.

(2) Viscosity measurement Measured at 25 ° C using an E-type viscometer (RE105U, manufactured by Toki Sangyo Co., Ltd.).

(3) Next, the strength was measured on an ITO substrate (403005XG-10SQ1500A, manufactured by Geomatec Co., Ltd.) after being washed with pure water, and the polyimide-based alignment solution (SUNEVERSE-7492) was dropped using an air distributor. (Manufactured by Nissan Chemical Industry Co., Ltd.) (0.4 MPa, 5.0 seconds), and then reached 5000 rpm with a spin coater in 10 seconds, and then uniformly applied while maintaining the condition for 20 seconds. After uniform coating, pre-baking (1 minute) and 230 ° C. oven on post-baking (60 minutes) on a hot plate at 85 ° C. to produce a substrate equipped with a polyimide alignment film.

Place the hardening resin composition on the 15mm × 3mm and 15mm × 21mm positions on the ITO substrate on which the 6μm spacers are spread, and the substrate (30mm × 30mm × 0.5mmt) with polyimide alignment film. The subsequent curable resin composition was spot-coated so that the diameter was in the range of 1.5 to 2.5 mmφ. After that, the substrates of the same kind (23mm × 23mm × 0.5mmt) were bonded together, and the ultraviolet rays were irradiated with an accumulated light amount of 3000mJ / cm ² (irradiation device: UVX-01224S1, manufactured by USHIO Electric Co., Ltd.) to harden them to 120 °. It was heat-hardened in an oven at 1 ° C for 1 hour to produce a hardened material test piece. Using an autostereograph (TG-2kN, manufactured by Minebea Co., Ltd.), the test piece was fixed, and a 15 mm × 25 mm position of the substrate was punched at a speed of 5 mm / min. Adhesive strength of fluorene imine substrates (PI / PI (TN)).

The epoxy equivalent and viscosity measurement results are shown in Tables 1 to 4 together with the blended composition of the curable resin composition of Examples 1 to 26 and Comparative Examples 1 to 2. In addition, Table 5 to 8 show the results of the adhesion strength measurements performed on part of the examples and comparative examples.

Claims (7)

A curable resin composition comprising, in a molecule, one or more groups represented by the following formula (1) and a group selected from the group represented by the following formula (2-1) and represented by the following formula: (2-2) A base represented by the following formula (2-3) and a (meth) acrylate resin having a base of 1 or more, and a thermosetting agent and / or a polymerization initiator , [Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently hydrogen atom or methyl group, R ²¹ is alkenyl group or alkynyl group, and R ²² and R ²³ are independent alkyl group and olefin group Group, alkynyl or aryl, or R ²² and R ²³ together form a ring structure, X ¹ is an oxygen atom or a sulfur atom, R ²⁴ is an alkyl, alkenyl, alkynyl, or aryl group, but R ²¹ , R ²² and R ²³ are not vinyl or 1-methylvinyl]. The curable resin composition according to claim 1, wherein the (meth) acrylate resin further has a group represented by formula (3), [Wherein R ⁶ is a hydrogen atom or a methyl group]. A (meth) acrylate resin characterized by the following formula (5), Ar ¹ (-OA ¹ ) _n1 (5) [wherein the total number of carbon atoms and hetero atoms in the Ar ¹ series is 5 or more And contains at least one n1-valent group of an aromatic ring or heteroaromatic ring, n1 is 1 or more, A ¹ is an independent hydrogen atom, a group represented by the following formula (1), and the following formula (2-1) A base represented by the following formula (2-2), a base represented by the following formula (2-3), a base represented by the following formula (3), a base represented by the following formula (4-1) or The group represented by the following formula (4-2), however, has a molecule selected from the group represented by the formula (4-1) having the group represented by the formula (1); the group represented by the formula (1) A base represented by the formula (4-2) and a base of 1 or more in the group formed by the base represented by the formula (1), and having a base selected from the group consisting of the base represented by the formula (2-1), The base represented by (2-2) or the base represented by formula (2-3) is the base represented by formula (4-1); the base represented by formula (2-1) and the base represented by formula (2-2) A base represented by and / or a base represented by formula (2-3), a base represented by formula (4-2); a base represented by formula (2-1); a base represented by formula (2-2), and A base of 1 or more in the group formed by the base represented by formula (2-3)], [Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently hydrogen atom or methyl group, R ²¹ is alkenyl or alkynyl, and R ²² and R ²³ are each Independent alkyl, alkenyl, alkynyl or aryl groups, or R ²² and R ²³ together form a ring structure, X ¹ is an oxygen atom or a sulfur atom, R ²⁴ is an alkyl, alkenyl, alkynyl or aryl group, However, R ²¹ , R ²² and R ²³ are not vinyl or 1-methylvinyl, B ¹ is an independent alkylene group, m1 is 1 or more, D ¹ is an arylene group, or an alkylene-arylene group. -Alkylene, alkylene-arylene, arylene-alkylene-arylene or group: -B ^2- (OB ² ) _m2- , B ² is an independent alkylene group, and m 2 is 0 Or 1 or more, C ¹ , C ² and C ³ are each independently a hydrogen atom, a base represented by formula (1), a base represented by formula (2-1), a base represented by formula (2-2), A base represented by formula (2-3) or a base represented by formula (3)]. The curable resin composition according to claim 1 or 2, wherein the (meth) acrylate resin is the resin according to claim 3. The curable resin composition of 2 or 4, further comprising a component selected from the group consisting of epoxy resins (except for epoxy resins having a (meth) acrylic fluorenyl group), and part or all of epoxy groups of fluorene epoxy resins. Modified compounds Modified epoxy resins and epoxy resins in which some or all of them are partially or wholly modified by (meth) acrylic modified epoxy resins are included here The aforementioned modified compound is one selected from the group consisting of an unsaturated carboxylic acid (except for (meth) acrylic acid), a carboxylic anhydride (except for (meth) acrylic anhydride), an alcohol, and a thiol. The above compounds. A curable resin composition of 2, 4 or 5, which is a sealant for liquid crystals. A method for producing a (meth) acrylate resin according to claim 3, comprising the step of reacting an epoxy resin with a modified compound and (meth) acrylic acid; here, the modified compound is selected from the group consisting of One or more compounds of unsaturated fatty acid carboxylic acid (except (meth) acrylic acid), carboxylic anhydride (except (meth) acrylic anhydride), alcohol and thiol.