Curable resin composition with excellent storage stability

Abstract

To provide a curable resin composition with excellent storage stability.SOLUTION: A curable resin composition according to the present invention comprises (A) a modified resin obtained by modifying part or all of epoxy groups of an epoxy resin with a modifying compound including (meth)acrylic acid and / or (meth)acrylic anhydride, and (B) at least one boron-containing compound selected from the group consisting of boric acid and boronic acid compounds.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable resin composition having excellent storage stability. [Background technology]

[0002] Unsaturated epoxy ester resins obtained by the ring-opening esterification reaction between epoxy resins and unsaturated carboxylic acids such as (meth)acrylic acid are called partially esterified epoxy resins, epoxy acrylate resins, etc., and are used as raw materials for sealants for liquid crystal display elements. In the reaction between epoxy resins and unsaturated carboxylic acids, the unsaturated carboxylic acids used as raw materials are compounds that are very susceptible to polymerization, so measures are taken to prevent gelation in the system, the generation of gel particles, and viscosity increase due to polymerization.

[0003] Patent Document 1 discloses a liquid crystal sealant containing a photocurable resin and a borate ester compound. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-115255 Summary of the Invention [Problem to be solved by the invention]

[0005] According to the findings of the present inventors, compositions containing boric acid ester compounds as described in Patent Document 1 have the problem that the storage stability of the resin composition is low.

[0006] Therefore, an object of the present invention is to provide a curable resin composition that has excellent storage stability. [Means for solving the problem]

[0007] The present invention relates to the following: [1] (A) a modified resin in which some or all of the epoxy groups in the epoxy resin have been modified with a modifying compound containing (meth)acrylic acid and / or (meth)acrylic anhydride; (B) a curable resin composition containing at least one boron-containing compound selected from the group consisting of boric acid and boronic acid compounds. [2] The curable resin composition according to claim 1, wherein the boronic acid compound is represented by the following general formula (10): [ka] [In formula (10), R is an alkyl group, a cycloalkyl group, or an aryl group.] [3] The content of the boron-containing compound relative to the weight of the modified resin is 0.1 × 10 -6 mol / g or more 100.0×10 -6 The curable resin composition according to [1] or [2], wherein the solubility is 100% by mass % or less. [4] The curable resin composition according to any one of [1] to [3], further comprising (C) a heat curing agent and / or a photopolymerization initiator. [5] The curable resin composition according to [4], which is a liquid crystal sealant. [Effects of the Invention]

[0008] According to the present invention, a curable resin composition having excellent storage stability is provided. DETAILED DESCRIPTION OF THE INVENTION

[0009] Preferred embodiments of the present invention will now be described. The term "(meth)acryloyl group" refers to an acryloyl group (CH2=CH2-C(=O)-) and / or a methacryloyl group (CH2=CH(CH3)-C(=O)-). The term "epoxy group" includes at least one of a glycidyl group and a methylglycidyl group. The term "glycidyl group" refers to a 2,3-epoxypropyl group. The term "methylglycidyl group" refers to a 2,3-epoxy-2-methylpropyl group.

[0010] In this specification, numerical ranges indicated using "to" indicate ranges that include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In this specification, when the composition contains multiple substances corresponding to each component, the amount of each component in the composition means the total amount of the multiple substances present in the composition, unless otherwise specified. In this specification, the term "process" includes not only independent processes, but also processes that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0011] In this specification, an "alkyl group", alone or in combination with other terms, is a linear or branched monovalent group. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and particularly preferably 1 to 4. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, and an n-dodecyl group.

[0012] The alkyl group may be unsubstituted or substituted with a substituent. The substituent of the alkyl group is not particularly limited, and examples thereof include an aryl group having 6 to 20 carbon atoms (particularly, a phenyl group), a halogen atom, a hydroxyl group, a mercapto group, a carboxy group, and an amino group.

[0013] As used herein, alone or in combination with other terms, an "alkylene group" is a divalent group that is linear or branched. It contains at least one of an alkylene group and an alkylidene group. The alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, an ethylidene group (ethylene-1,1-diyl group), a trimethylene group, a propylene group (propane-1,2-diyl group), a propylidene group (propane-1,1-diyl group), an isopropylidene group (propane-2,2-diyl group), a tetramethylene group, a butylidene group (butane-1,1-diyl group), an isobutylidene group (2-methylpropane-1,1-diyl group), a pentamethylene group, a 2-methylpentane-1,5-diyl group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, and a dodecamethylene group.

[0014] The alkylene group may be unsubstituted or substituted with a substituent, such as a halogen atom or an aryl group (particularly, a phenyl group).

[0015] In this specification, the term "aryl group", whether used alone or in combination with other terms, refers to a monovalent group having a monocyclic or polycyclic aromatic ring. The number of carbon atoms in the aryl group is preferably 6 to 20. Examples of the aryl group include a phenyl group, a biphenylyl group, a naphthyl group, a terphenylyl group, an anthracenyl group, and a fluorenyl group, and the phenyl group and the biphenylyl group are preferred.

[0016] The aryl group may be unsubstituted or substituted with a substituent, such as an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkylmercapto group, a cycloalkyl group, a halogen atom, a hydroxyl group, a mercapto group, a carboxy group, or an amino group.

[0017] In this specification, the term "arylene group", whether used alone or in combination with other terms, refers to a divalent group having a monocyclic or polycyclic aromatic ring. The number of carbon atoms in the arylene group is preferably 6 to 20. Examples of the arylene group include a phenylene group, a naphthylene group, an anthranylene group, and a phenanthranylene group, and the phenylene group is preferred.

[0018] The arylene group may be unsubstituted or substituted with a substituent, such as an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkylmercapto group, a cycloalkyl group, or a halogen atom.

[0019] As used herein, alone or in combination with other terms, a "cycloalkyl group" refers to a monovalent group having a monocyclic or polycyclic alicyclic group having 3 to 20 carbon atoms. Examples of cycloalkyl groups include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a cyclododecyl group, and an adamantyl group.

[0020] The cycloalkyl group may be unsubstituted or substituted with a substituent, such as an alkyl group, a halogen atom, a hydroxyl group, a mercapto group, a carboxyl group, or an amino group.

[0021] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogen atom as a substituent is preferably a fluorine atom or a chlorine atom, and particularly preferably a fluorine atom.

[0022] Examples of the alkyl moiety in the alkoxy group include the above-mentioned examples of the alkyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an i-butoxy group, a sec-butoxy group, and a tert-butoxy group.

[0023] Examples of the alkyl group in the alkylcarbonyl group and alkylmercapto group include the above-mentioned examples of the alkyl group. Examples of the alkylcarbonyl group include an acetyl group, a propanoyl group, a 2-methylpropanoyl group, and a butanoyl group. Examples of the alkylmercapto group include a methylmercapto group, an ethylmercapto group, a propylmercapto group, an i-propylmercapto group, a butylmercapto group, an i-butylmercapto group, a sec-butylmercapto group, and a tert-butylmercapto group.

[0024] [Curable resin composition] The curable resin composition contains (A) a modified resin in which some or all of the epoxy groups in the epoxy resin have been modified with a modifying compound containing (meth)acrylic acid and / or (meth)acrylic anhydride, and (B) at least one boron-containing compound selected from the group consisting of boric acid and boronic acid compounds.

[0025] [(A) Modified resin in which some or all of the epoxy groups in the epoxy resin have been modified with a modifying compound containing (meth)acrylic acid and / or (meth)acrylic anhydride] A modified resin (hereinafter also referred to as "(A) modified resin") in which some or all of the epoxy groups in an epoxy resin have been modified with a modifying compound containing (meth)acrylic acid and / or (meth)acrylic anhydride is a curable component of a curable resin composition.

[0026] (epoxy resin) Epoxy resins are raw materials for modified resins and are resins having one or more epoxy groups in the molecule. Examples of epoxy resins include epoxy resins having an aromatic ring, aliphatic epoxy resins, and alicyclic epoxy resins. Here, the aromatic ring may be a heteroaromatic ring or an aromatic ring containing no heteroatoms. The epoxy resin may also be a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, a hydantoin type epoxy resin, and / or an isocyanurate type epoxy resin.

[0027] Examples of epoxy resins having an aromatic ring include bisphenol-type epoxy resins (for example, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, and bisphenol AD-type epoxy resins), diglycidyl ethers of bifunctional phenols (for example, resorcinol-type epoxy resins), phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol A novolac-type epoxy resins, bisphenol F novolac-type epoxy resins, and phenol novolac-type epoxy resins having a triphenolmethane skeleton.

[0028] The aliphatic epoxy resin and alicyclic epoxy resin can be appropriately selected from known components.

[0029] The epoxy resin is preferably a di- or higher functional epoxy resin, particularly preferably a di- to tetra-functional epoxy resin. The epoxy resin is preferably an aromatic ring-containing epoxy resin, particularly preferably one or more selected from the group consisting of bisphenol-type epoxy resins and resorcinol-type epoxy resins.

[0030] (modified compounds) The modifying compound contains (meth)acrylic acid and / or (meth)acrylic anhydride, and is a raw material for the modified resin.

[0031] <(Meth)acrylic acid, (meth)acrylic anhydride> The (meth)acrylic acid is at least one selected from the group consisting of acrylic acid and methacrylic acid. The (meth)acrylic anhydride is at least one selected from the group consisting of acrylic anhydride and methacrylic anhydride.

[0032] <Modifying compounds other than (meth)acrylic acid and (meth)acrylic anhydride> The modifying compound may contain a compound other than (meth)acrylic acid and (meth)acrylic anhydride (hereinafter also referred to as "further modifying compound"). The further modifying compound is a compound having a group capable of reacting with an epoxy group. Examples of the further modifying compound include one or more compounds selected from the group consisting of carboxylic acids (excluding (meth)acrylic acid), carboxylic acid anhydrides (excluding (meth)acrylic anhydride), alcohols, and thiols.

[0033] <Carboxylic acids (excluding (meth)acrylic acid)> Examples of carboxylic acids (excluding (meth)acrylic acid, hereinafter simply referred to as "carboxylic acid") include aliphatic carboxylic acids and aromatic carboxylic acids. Examples of aliphatic carboxylic acids include saturated aliphatic carboxylic acids and unsaturated aliphatic carboxylic acids. The aliphatic hydrocarbon group contained in the saturated aliphatic carboxylic acid and the unsaturated aliphatic carboxylic acid may be linear, branched, or cyclic, but is preferably linear. The number of unsaturated bonds contained in the unsaturated aliphatic carboxylic acid is preferably one or two, and particularly preferably one. Here, "unsaturated bond" means an ethylenically unsaturated bond (C=C) and / or an acetylenically unsaturated bond (C≡C), and is preferably an ethylenically unsaturated bond.

[0034] The number of carboxyl groups in the carboxylic acid is not particularly limited, and the carboxylic acid may be a monocarboxylic acid having one carboxyl group in the molecule, or a polycarboxylic acid having two or more carboxyl groups in the molecule. The valence of the polycarboxylic acid is not particularly limited as long as it is divalent or greater, and divalent to tetravalent carboxylic acids are preferred, with divalent carboxylic acids being particularly preferred.

[0035] The polyvalent aliphatic carboxylic acid is preferably a polyvalent saturated aliphatic carboxylic acid. Examples of polyvalent saturated aliphatic carboxylic acids include divalent saturated aliphatic carboxylic acids such as oxalic acid (C2), succinic acid (C4), adipic acid (C6), suberic acid (C8), sebacic acid (C10), dodecanedioic acid (C12), and tetradecanedioic acid (C14). The number in parentheses indicates the number of carbon atoms in the carboxylic acid.

[0036] The monovalent aliphatic carboxylic acid is preferably a monovalent unsaturated aliphatic carboxylic acid, particularly preferably a monovalent unsaturated aliphatic carboxylic acid having one unsaturated bond. Examples of such monovalent unsaturated aliphatic carboxylic acids include crotonic acid (C4) and myristoleic acid (C14).

[0037] The aromatic carboxylic acid is not particularly limited as long as it is a carboxylic acid having an aromatic ring. Specific examples of the aromatic carboxylic acid include polyvalent aromatic carboxylic acids such as terephthalic acid and isophthalic acid, and monovalent aromatic carboxylic acids such as benzoic acid and 3-phenylpropionic acid.

[0038] <Carboxylic acid anhydrides (excluding (meth)acrylic anhydride)> Examples of carboxylic acid anhydrides (excluding (meth)acrylic acid anhydride) include monocarboxylic acid anhydrides such as acetic acid anhydride and benzoic acid anhydride; and dicarboxylic acid anhydrides such as succinic acid anhydride, maleic acid anhydride and phthalic acid anhydride.

[0039] <Alcohols and thiols> The alcohol can be appropriately selected from known components having one or more hydroxyl groups (but not phenolic hydroxyl groups) in the molecule, and the thiol can be appropriately selected from known components having one or more mercapto groups in the molecule.

[0040] <Reaction conditions> As the reaction conditions for obtaining the modified resin, known conditions used in the reaction of an epoxy resin with a modifying compound containing (meth)acrylic acid and / or (meth)acrylic anhydride can be appropriately applied.

[0041] The reaction can be carried out in the presence or absence of a basic catalyst and / or an acid catalyst. Examples of the basic catalyst and acid catalyst include known basic catalysts and acid catalysts used in the reaction of an epoxy resin, (meth)acrylic acid and / or (meth)acrylic anhydride, and a further modifying compound.

[0042] The basic catalyst is preferably an alkali metal hydroxide (sodium hydroxide, potassium hydroxide, etc.), an alkali metal carbonate (sodium carbonate, potassium carbonate, etc.), an alkali metal alkoxide (sodium methoxide, etc.), a trivalent organic phosphorus compound, and / or an amine compound. Alternatively, a polymer-supported basic catalyst, in which the basic catalyst is supported on a polymer, can also be used.

[0043] Trivalent organophosphorus compounds include alkyl phosphines such as triethylphosphine, tri-n-propylphosphine, and tri-n-butylphosphine, and their salts; aryl phosphines such as triphenylphosphine, tri-m-tolylphosphine, tris-(2,6-dimethoxyphenyl)phosphine, and bis[2-(diphenylphosphino)phenyl]ether, and their salts; and phosphite triesters such as triphenylphosphite, triethylphosphite, and tris(nonylphenyl)phosphite, and their salts. Salts of trivalent organophosphorus compounds include triphenylphosphine ethyl bromide, triphenylphosphine butyl bromide, triphenylphosphine octyl bromide, triphenylphosphine decyl bromide, triphenylphosphine isobutyl bromide, triphenylphosphine propyl chloride, triphenylphosphine pentyl chloride, and triphenylphosphine hexyl bromide.

[0044] Examples of the amine compound include secondary amines such as diethanolamine, tertiary amines such as triethanolamine, dimethylbenzylamine, trisdimethylaminomethylphenol, and trisdiethylaminomethylphenol, and strongly basic amines such as 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]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), and 1,1,3,3-tetramethylguanidine, and salts thereof. Among these, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) is preferred. Examples of the salts of amine compounds include benzyltrimethylammonium chloride and benzyltriethylammonium chloride.

[0045] Examples of the acid catalyst include sulfuric acid, sulfonic acids such as trifluoromethanesulfonic acid, graphite oxide, and antimony fluoride. Alternatively, a cation exchanger (e.g., Amberlyst, a commercially available product) may be used as the acid catalyst. The acid catalyst may be used for the reaction of an epoxy resin with one or more compounds selected from the group consisting of alcohols and thiols as further modifying compounds.

[0046] The reaction can be carried out in the presence or absence of a solvent. Inert solvents such as hydrocarbons, ethers, or ketones can be used in the reaction, but these solvents are not essential when an excess epoxy resin is used, since the resin also functions as a solvent.

[0047] The reaction temperature can be appropriately set by those skilled in the art depending on the catalyst and raw material compounds used, etc. For example, when the catalyst is a basic catalyst and the modifying compound is (meth)acrylic acid, (meth)acrylic anhydride, and the further modifying compound is one or more selected from the group consisting of carboxylic acids (excluding (meth)acrylic acid) and carboxylic acid anhydrides (excluding (meth)acrylic anhydride), the reaction temperature is preferably 60 to 120°C, more preferably 80 to 120°C, even more preferably 90 to 120°C, and particularly preferably 100 to 120°C.

[0048] The total modification ratio of the epoxy groups of the epoxy resin with the modifying compound is more than 0% and not more than 100%, preferably 10 to 90%. The ratio of the modification ratio with (meth)acrylic acid and / or (meth)acrylic anhydride to the total modification ratio of the modifying compounds may be more than 0% and not more than 100%, preferably 10 to 80%. Because the reaction between the epoxy groups and the modifying compound proceeds quantitatively, the modification ratio of the resulting modified resin can also be estimated from the epoxy equivalent. The completion of the reaction between the epoxy resin and the modifying compound can be determined by calculating the reaction ratio from the amount of the modifying compound used at the beginning of the reaction and the remaining amount of the modifying compound. At the end of the reaction, the reaction ratio is preferably 99% or more, and particularly preferably 99.9% or more.

[0049] When the modifying compound contains both (meth)acrylic acid and / or (meth)acrylic anhydride and a further modifying compound, the (meth)acrylic acid and / or (meth)acrylic anhydride and the further modifying compound may be simultaneously reacted with an epoxy resin to obtain a modified resin. Alternatively, the epoxy resin may be reacted with the further modifying compound to obtain an epoxy resin partially modified with the further modifying compound, and the epoxy resin partially modified with the further modifying compound may be reacted with (meth)acrylic acid and / or (meth)acrylic anhydride to obtain a modified resin. Alternatively, the epoxy resin may be reacted with (meth)acrylic acid and / or (meth)acrylic anhydride to obtain an epoxy resin partially modified with (meth)acrylic acid and / or (meth)acrylic anhydride, and the epoxy resin partially modified with (meth)acrylic acid and / or (meth)acrylic anhydride may be reacted with the further modifying compound to obtain a modified resin.

[0050] (modified resin) The structure of the modified resin is not particularly limited. When the epoxy resin has an aromatic ring, the resulting modified resin may be, for example, a modified resin represented by the following formula (1): Ar 1 (-OA 1 ) n1 (1) [During the ceremony, Ar 1 is an n1-valent group having a total of 5 or more carbon atoms and heteroatoms and containing one or more aromatic rings or heteroaromatic rings, n1 is 1 or greater, A 1 are independently a hydrogen atom, a group represented by the following formula (2), a group represented by the following formula (3-1), a group represented by the following formula (3-2), a group represented by the following formula (4-1), a group represented by the following formula (4-2), a group represented by the following formula (4-3), a group represented by the following formula (5-1), or a group represented by the following formula (5-2), provided that it has one or more groups selected from the group consisting of a group represented by formula (5-1) having a group represented by formula (3-1) or a group represented by formula (3-2); a group represented by formula (5-2) having a group represented by formula (3-1) or a group represented by formula (3-2); a group represented by formula (3-1); and a group represented by formula (3-2). [ka] [ka] [During the ceremony, R 1 , R 2 and R 3 are each independently a hydrogen atom or a methyl group, R 4 is an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, R 5 and R 6 are each independently an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, or R 5 and R 6 together form a ring structure, However, R 4 , R 5 and R 6 is not a vinyl group or a 1-methylvinyl group, X 1 is an oxygen atom or a sulfur atom, R 7 is an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, B 1 are independently an alkylene group, m1 is 1 or more, D 1 is an arylene group, an alkylene-arylene-alkylene group, an alkylene-arylene group, an arylene-alkylene-arylene group or the group: -B 2 -(OB 2 ) m2 - and B 2 is independently an alkylene group, m2 is 0 or 1 or more, C 1 , C 2 and C 3 are each independently a hydrogen atom, a group represented by formula (2), a group represented by formula (3-1), or a group represented by formula (3-2), * indicates the bond position.

[0051] The group represented by formula (2) corresponds to the epoxy group of an epoxy resin. The group represented by formula (3-1) corresponds to the structure formed by the reaction of an epoxy group of an epoxy resin with (meth)acrylic acid. The group represented by formula (3-2) corresponds to the structure formed by the reaction of an epoxy group of an epoxy resin with (meth)acrylic anhydride. The group represented by formula (4-1) corresponds to the structure formed by the reaction of an epoxy group of an epoxy resin with a monovalent carboxylic acid. The group represented by formula (4-2) corresponds to the structure formed by the reaction of an epoxy group of an epoxy resin with a carboxylic anhydride. The group represented by formula (4-3) corresponds to the structure formed by the reaction of an epoxy group of an epoxy resin with an alcohol or a thiol.

[0052] When the total modification ratio of the modifying compound to the epoxy groups of the epoxy resin is less than 100%, the modified resin may have, in the molecule, one or more groups selected from the group consisting of a group represented by formula (5-1) having a group represented by formula (2); a group represented by formula (5-2) having a group represented by formula (2); and a group represented by formula (2).

[0053] ·R 1 ~R 3 R 1 , R 2 and R 3 are each independently a hydrogen atom or a methyl group. When modified with acrylic acid, R 1 is a hydrogen atom. When modified with methacrylic acid, R 1 is a methyl group. When modified with acrylic anhydride, R 2 and R 3 is a hydrogen atom. When modified with methacrylic anhydride, R 2and R 3 is a methyl group.

[0054] n1 n1 is 1 or more and corresponds to the valence of the epoxy resin. n1 may be 1 to 8, 2 to 4, or 2.

[0055] ·Ar 1 Ar 1 The number of carbon atoms contained in the aryl group is 4 to 40, the number of oxygen atoms is 0 to 5, the number of nitrogen atoms is 0 to 5, and the number of sulfur atoms is 0 to 5, and Ar 1 The number of ring structures contained therein is preferably 1 to 5.

[0056] Ar 1 The ring structures (aromatic rings and heteroaromatic rings) contained in may be of one type alone or two or more types, and the ring structures may be monocyclic or fused ring structures. Furthermore, these ring structures may be present in plural, linked by a direct bond or via a linking group.

[0057] Examples of the linking group include an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 2 to 4 carbon atoms, an oxygen atom, an ester group, a keto group, a sulfur atom, and a sulfonyl group. 1 Oxygen atoms and Ar bonded to 1 The ring structure contained in Ar may be bonded via this linking group. 1 The ring structure contained in 1 It is preferable that the oxygen atom bonded to the aryl group is directly bonded to the oxygen atom bonded to the aryl group.

[0058] These ring structures may each independently have a substituent, examples of which include an alkyl group, an alkoxy group, an alkylcarbonyl group, an alkylmercapto group, a cycloalkyl group, and a halogen atom.

[0059] Ar 1Examples of the ring structure contained in the above include a benzene ring, a naphthalene ring, a fluorene ring, an anthracene ring, a furan ring, a pyrrole ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a thiazine ring, and rings having the above-mentioned substituents bonded thereto.

[0060] Ar when n1 is 1 1 Specific examples of the group include a phenyl group, a biphenylyl group, a naphthyl group, a terphenylyl group, an anthracenyl group, and a fluorenyl group.

[0061] Ar when n1 is 2 1 Specific examples of the alkylene group include an arylene group having 6 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms-an alkylene group having 1 to 6 carbon atoms-an arylene group having 6 to 20 carbon atoms, and an arylene-O-(B 3 -O) m3 - an arylene group having 6 to 20 carbon atoms (wherein B 3 is an alkylene group having 1 to 8 carbon atoms, and m3 is 0 or an integer of 1 to 6), and preferred are groups in which two hydroxyl groups have been removed from bisphenols, such as a phenylene-isopropylidene-phenylene group (a group in which two hydroxyl groups have been removed from bisphenol A), a phenylene-methylene-phenylene group (a group in which two hydroxyl groups have been removed from bisphenol F), and a phenylene-ethylidene-phenylene group (a group in which two hydroxyl groups have been removed from bisphenol AD).

[0062] Ar when n1 is 3 1 Specific examples of the formula include the following: where * indicates the bonding position. [ka]

[0063] Ar when n1 is 4 1 Specific examples of the formula include the following: where * indicates the bonding position. [ka]

[0064] Ar when n1 is 2 or more 1 A specific example of the phenol novolak is the phenol novolak represented by the following formula: [ka] [In the formula, R 8 are independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, p1 is 0 or 1 or more, and R 9 are independently a bonding position, a hydrogen atom, or a hydroxyl group, and R 9 The number of bonding positions in Ar 1 The valence of

[0065] In addition, when n1 is 5 or more, Ar 1 As a specific example, when n1 is 1, Ar 1 In the specific examples of the above, groups in which four or more hydrogen atoms bonded to aromatic carbon atoms have been removed, and Ar 1 In the specific examples of the above, groups in which three or more hydrogen atoms bonded to aromatic carbon atoms have been removed, and Ar 1 A group in which two or more hydrogen atoms bonded to aromatic carbon atoms of the specific aromatic group are removed, and Ar 1 Specific examples include groups in which one or more hydrogen atoms bonded to aromatic carbon atoms have been removed.

[0066] In formula (1), A 1 "Independently" in the definition of "n1" means, for example, when n1 is 2 or more, in each case, the options (e.g., A 1 ) is defined independently. That is, when n1 is 2 or more, the options defined in formula (1) (for example, A 1 ) may be different or the same.

[0067] In formula (5-1), m1 is preferably an integer of 1 to 6. D in formula (5-2) 1 Base:-B 2 -(OB 2 ) m2When m2 is 1 or greater, it is preferably an integer of 1 to 6. 1 As a specific example, when n1 is 2, Ar 1 Specific examples include:

[0068] When the further modifying compound contains a polycarboxylic acid, all of the carboxyl groups of the polycarboxylic acid may be involved in modifying the epoxy groups of the epoxy resin. In this case, in the modified resin, some of the epoxy groups of the epoxy resin are modified with (meth)acrylic acid and / or (meth)acrylic anhydride, and some of the epoxy groups of the epoxy resin modified with the (meth)acrylic acid and / or (meth)acrylic anhydride are modified with the polycarboxylic acid. Furthermore, the remaining carboxyl groups of the polycarboxylic acid that are not involved in the modification of the epoxy resin modify some of the epoxy groups of the further epoxy resin. Here, when the epoxy resin is an epoxy resin having an aromatic ring, such a modified resin may contain, for example, a component having a structure represented by the following formula (6):

[0069] [ka] [During the ceremony, Y 1 is an n-divalent hydrocarbon group, n2 is 2 or greater, E 1 is a group represented by the following formula (7), and the ester group in formula (7) is Y 1 binds to Ar 2 are each independently an (n3+1)-valent group having a total of 5 or more carbon atoms and heteroatoms and containing one or more aromatic rings or heteroaromatic rings, n3 is independently 1 or more, A 2are each independently a group represented by the above formula (2), a group represented by the above formula (3-1), a group represented by the above formula (3-2), a group represented by the above formula (4-1), a group represented by the above formula (4-2), or a group represented by the above formula (4-3), provided that the molecule contains a group represented by the above formula (3-1) and / or a group represented by the above formula (3-2), * indicates the bonding position. [ka]

[0070] Y 1 , n2 Y 1 is a hydrocarbon group having a valence of n2. 1 is a residue obtained by removing a carboxyl group from a polycarboxylic acid. The n2-valent hydrocarbon group may be an aliphatic group or an aromatic group. n2 is 2 or more and corresponds to the valence of the polycarboxylic acid. n2 may be 2 to 4, or may be 2. When n2 is divalent, Y 1 As for Y, which will be described later 2 n When the divalent is 3 or more, Y 1 As for Y, which will be described later 2 Examples of such groups include groups in which one or more hydrogen atoms have been removed from the above.

[0071] E 1 E 1 is a group represented by formula (7), and the ester group in formula (7) is Y 1 Binds to E 1 is a structure in which the epoxy group of an epoxy resin having an aromatic ring reacts with the carboxyl group of a polycarboxylic acid, resulting in ring-opening of the epoxy group.

[0072] ·Ar 2 , n3 Ar 2 are each independently an (n3+1) valent group having a total of 5 or more carbon atoms and heteroatoms and containing one or more aromatic or heteroaromatic rings. 2corresponds to the aromatic ring portion of the epoxy resin having an aromatic ring. 2 A specific example of this is Ar 1 In the above, the groups mentioned above can be mentioned. Each n3 is independently 1 or more, and corresponds to the “epoxy functionality number −1” of the aromatic ring-containing epoxy resin. n3 may be 1 to 3, or may be 1.

[0073] A 2 are each independently a group represented by the above formula (2), a group represented by the above formula (3-1), a group represented by the above formula (3-2), a group represented by the above formula (4-1), a group represented by the above formula (4-2), or a group represented by the above formula (4-3).

[0074] For example, when the epoxy resin is a difunctional epoxy resin and the modifying compound contains a divalent carboxylic acid as a further modifying compound, a representative structure of the modified resin is preferably represented by the following formula (8).

[0075] [ka] [During the ceremony, Y 2 is an alkylene group, an alkenylene group, or a divalent Ar 2 is synonymous with Ar 3 and Ar 4 each independently represents an arylene group, an arylene-alkylene-arylene group, or an arylene-O—(B 4 -O) m4 - an arylene group (wherein B 4 is an alkylene group, and m4 is 0 or an integer of 1 to 6; A 3 and A 4 are each independently a group represented by the above formula (2), a group represented by the above formula (3-1), a group represented by the above formula (3-2), a group represented by the above formula (4-1), a group represented by the above formula (4-2), or a group represented by the above formula (4-3), provided that the molecule contains a group represented by the above formula (3-1) and / or a group represented by the above formula (3-2).

[0076] When the total modification ratio of the modifying compound to the epoxy group of the epoxy resin is less than 100%, the structures represented by formulas (6) and (8) have in the molecule a group represented by formula (2) and a group represented by formula (3-1) and / or a group represented by formula (3-2). When the modifying compound contains a further modifying compound other than a polycarboxylic acid, the modified resin contains a group represented by formula (4-1), a group represented by formula (4-2), and / or a group represented by formula (4-3), depending on the type of the further modifying compound. And, A in formula (6) 2 (A in the above formula (8) 3 and A 4 ) includes a group represented by the above formula (4-1), a group represented by the above formula (4-2) and / or a group represented by the above formula (4-3).

[0077] Modified resins, epoxy resins, and conditions for producing modified resins other than those described above include those described in JP-A-2018-172483, JP-A-2018-172484, etc.

[0078] The (A) modified resin may be a single component or a combination of two or more components.

[0079] [(B) At least one boron-containing compound selected from the group consisting of boric acid and boronic acid compounds] At least one boron-containing compound selected from the group consisting of boric acid and boronic acid compounds (hereinafter simply referred to as "(B) boron-containing compound") is a component that improves the storage stability of (A) modified resin.

[0080] <Boric acid> Boric acid is a compound represented by the following formula (9):

[0081] [ka]

[0082] <Boronic acid compounds> A boronic acid compound is a compound in which one hydroxy group of boric acid is replaced with an organic group (a hydrocarbon group such as an alkyl group or an aryl group). Therefore, the boronic acid compound has one boron atom in the molecule. The boronic acid compound is preferably represented by the following general formula (10):

[0083] [ka] (wherein R is an alkyl group, a cycloalkyl group, or an aryl group).

[0084] From the viewpoint of solubility in the component (A), the component (B) is preferably boric acid or a boronic acid compound in which R is an aryl group. The component (B) may be one type of component or a combination of two or more types of components.

[0085] <Other ingredients> The curable resin composition may contain other components depending on its purpose, as long as the effects of the present invention are not impaired. Examples of other components include photopolymerization initiators, heat curing agents, curable resins other than component (A), silane coupling agents, fillers, polymerization inhibitors, liquid thixotropic agents, solvents, photosensitizers, reinforcing agents, colorants, stabilizers, extenders, viscosity modifiers, tackifiers, flame retardants, UV absorbers, antioxidants, discoloration inhibitors, antibacterial agents, antifungal agents, antiaging agents, antistatic agents, plasticizers, lubricants, smoothing agents, foaming agents, and mold release agents. The curable resin composition preferably further contains a photopolymerization initiator and / or a heat curing agent (C). Even when the curable resin composition further contains a photopolymerization initiator and / or a heat curing agent (C), the storage stability of the curable resin composition is improved without reducing the curability of component (A). The other components are not the aforementioned components (A) and (B).

[0086] <(C) Photopolymerization initiator and / or heat curing agent> The photopolymerization initiator is a component that can convert the curable resin composition into a photopolymerizable and curable composition. The heat curing agent is a component that can convert the curable resin composition into a heat curable composition. The photopolymerization initiator and / or heat curing agent can be appropriately selected depending on the type of curable resin (i.e., component (A)) contained in the curable resin composition and the desired curing conditions (energy ray curing and / or heat curing). Therefore, examples of component (C) include photopolymerization initiators, heat curing agents, and combinations of photopolymerization initiators and heat curing agents.

[0087] <Photopolymerization initiator> The photopolymerization initiator may be a radical polymerization initiator, an anionic polymerization initiator, and / or a cationic polymerization initiator.

[0088] Examples of radical polymerization initiators include benzoins, acetophenones, benzophenones, thioxanthones, α-acyloxime esters, phenylglyoxylates, benzils, azo compounds, diphenyl sulfide compounds, acylphosphine oxide compounds, benzoin ethers, anthraquinones, and organic peroxides. Radical polymerization initiators are preferably those that have low solubility in liquid crystals and have reactive groups that do not gasify upon exposure to light. Furthermore, as a radical polymerization initiator, a polymerization initiator that is a mixture of a polyether compound having a dialkylaminobenzoyl group and a polyether compound having a group in which one hydrogen atom has been removed from thioxanthone, as described in JP 2020-076794, is preferred. A polymerization initiator that is a mixture of a compound obtained by reacting a compound having at least two epoxy groups with dimethylaminobenzoic acid and a compound obtained by reacting a compound having at least two epoxy groups with hydroxythioxanthone is particularly preferred.

[0089] Examples of the anionic polymerization initiator include imidazoles, amines, phosphines, organic metal salts, metal chlorides, and organic peroxides.

[0090] Examples of the cationic polymerization initiator include onium salts, iron allene complexes, titanocene complexes, arylsilanol aluminum complexes, Lewis acid compounds, Bronsted acid compounds, benzylsulfonium salts, thiophenium salts, thioranium salts, benzylammonium, pyridinium salts, hydrazinium salts, carboxylic acid esters, sulfonic acid esters, amine imides, sulfone compounds, sulfonic acid esters, sulfonimides, disulfonyldiazomethanes, and amines.

[0091] The photopolymerization initiator is commercially available or can be prepared according to known methods. The photopolymerization initiator may be a single component or a combination of two or more components.

[0092] <Thermal hardener> The heat curing agent is not particularly limited, but examples thereof include amine-based heat curing agents, such as organic acid dihydrazide compounds, amine adducts, imidazole and its derivatives, dicyandiamide, aromatic amines, epoxy-modified polyamines, and polyaminoureas, and examples thereof include VDH (1,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin), ADH (adipic acid dihydrazide), UDH (7,11-octadecadiene-1,18-dicarbohydrazide), LDH (octadecane-1,18-dicarboxylic acid dihydrazide), IDH (isopropyl methyl acrylate ... Preferred examples include organic acid dihydrazides such as isophthalic dihydrazide DH (ADH-S) available from Otsuka Chemical Co., Ltd.; polyamine compounds such as Adeka Hardener EH-5030S available from ADEKA Corporation; amine adducts such as Amicure PN-23, Amicure PN-30, Amicure MY-24, and Amicure MY-H available from Ajinomoto Fine-Techno Co., Ltd.; and imidazole compounds such as 2P4MHZ-PW available from Shikoku Chemicals Corporation. The thermal curing agent may be a single component or a combination of two or more components.

[0093] <Curable resin other than component (A) (component (D))> Examples of the component (D) include (D-1) a difunctional or higher epoxy resin and (D-2) other curable resins (excluding the component (D-1)).

[0094] <(D-1) Difunctional or higher epoxy resin> The component (D-1) is not particularly limited, and examples thereof include the resins described above as epoxy resins having an aromatic ring. Examples of trifunctional and tetrafunctional epoxy resins include the epoxy resins described in JP 2012-077202 A. The number of epoxy functionalities of the component (D-1) is not particularly limited, but is preferably 2 to 4. The component (D-1) is preferably an epoxy resin having a bisphenol structure, and particularly preferably one or more selected from the group consisting of bisphenol A epoxy resins and bisphenol F epoxy resins.

[0095] <(D-2) Other curable resins> The component (D-2) is not particularly limited as long as it is a curable resin other than the components (A) and (D-1), and examples thereof include conventional resins having unsaturated groups and / or epoxy groups, resins having one epoxy group, and resins having neither unsaturated groups nor epoxy groups, which are used as the base resin of curable resin compositions. Here, "unsaturated groups" refers to ethylenically unsaturated groups and / or acetylenically unsaturated groups. The component (D-2) is appropriately selected from cationic polymerizable resins, radically polymerizable resins, and / or anionic polymerizable resins depending on the type of polymerization initiator and / or thermosetting agent contained in the curable resin composition.

[0096] Examples of resins having an unsaturated group include (meth)acrylate compounds, aliphatic acrylamide compounds, alicyclic acrylamide compounds, aromatic acrylamide compounds, N-substituted acrylamide compounds, and diene polymers (e.g., polybutadiene polymers, polyisoprene polymers, etc.). The functionality of the (meth)acrylate compound can be monofunctional, difunctional, or polyfunctional (e.g., trifunctional or higher), and is preferably difunctional or trifunctional or higher.

[0097] Preferred bifunctional (meth)acrylate compounds include one or more compounds selected from the group consisting of tricyclodecane dimethanol di(meth)acrylate, dimethylol dicyclopentane di(meth)acrylate, EO-modified 1,6-hexanediol di(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, PO-modified bisphenol A di(meth)acrylate, polyester di(meth)acrylate (e.g., ARONIX M-6100, manufactured by Toa Gosei Co., Ltd.), polyethylene glycol di(meth)acrylate (e.g., 4G, manufactured by Shin-Nakamura Chemical Co., Ltd.), and silicone di(meth)acrylate (e.g., EBEDRYL 350, manufactured by Daicel-Allnex Co., Ltd.). Here, "EO" means ethylene oxide, and "PO" means propylene oxide.

[0098] The tri- or higher functional polyfunctional (meth)acrylate compound is preferably one or more compounds 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).

[0099] Further, examples of resins having unsaturated groups include epoxy resins modified with a modifying compound in which all of the epoxy groups of the epoxy resin have unsaturated groups (excluding (meth)acrylic acid and (meth)acrylic anhydride). Resins having one epoxy group include aromatic epoxy resins and aliphatic epoxy resins. Examples of resins having neither an unsaturated group nor an epoxy group include modified epoxy resins in which all of the epoxy groups of an epoxy resin have been modified with a modifying compound having no unsaturated groups, and urethane resins formed from a hydroxyl group-containing compound and an isocyanate group-containing compound.

[0100] The (D) component may be one type or a combination of two or more types. For example, the (D) component may be a combination of one or more (D-1) components and one or more (D-2) components.

[0101] <Silane coupling agent> Examples of silane coupling agents include silane compounds having one or more reactive functional groups selected from the group consisting of epoxy groups, alkenyl groups (e.g., vinyl groups), (meth)acryloyl groups, primary or secondary amino groups, mercapto groups, isocyanato groups, ureido groups, and halogen atoms, or alkyl groups substituted with such groups, and one or more alkoxy groups, and may also have unsubstituted alkyl groups. The reactive functional groups may be bonded to the silicon atoms of the silane compounds as alkyl groups substituted with the reactive functional groups.

[0102] Specific examples of the silane coupling agent include silane compounds having an epoxy group and an alkoxy group, and optionally having an alkyl group, such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; silane compounds having an alkenyl group and an alkoxy group, and optionally having an alkyl group, such as vinyltrimethoxysilane and p-styryltrimethoxysilane; silane compounds having a (meth)acryloyl group and an alkoxy group, and optionally having an alkyl group, such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-( Examples of such silane compounds include silane compounds having a primary or secondary amino group and an alkoxy group, and optionally an alkyl group, such as N-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane; and silane compounds having one or more groups selected from the group consisting of a mercapto group, an isocyanato group, a ureido group, and a halogen atom, and one or more alkoxy groups, and optionally an alkyl group, such as 3-ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, and 3-isocyanatopropyltriethoxysilane. The silane coupling agent may be one type or a combination of two or more types.

[0103] <Filler> The filler is added for the purposes of controlling the viscosity of the curable resin composition, improving the strength of a cured product obtained by curing the curable resin composition, or improving the adhesive reliability of the curable resin composition by suppressing linear expansion, etc. Examples of the filler include inorganic fillers and organic fillers.

[0104] Examples of inorganic fillers include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, titanium oxide, alumina, zinc oxide, silicon dioxide (precipitated silica, fumed silica (fumed silica), etc.), kaolin, talc, glass beads, sericite activated clay, aluminum hydroxide, asbestos powder, copper oxide, copper hydroxide, iron oxide, lead oxide, magnesium oxide, tin oxide, carbon, mica, smectite, carbon black, bentonite, aluminum nitride, and silicon nitride. The inorganic fillers may be used alone or in combination of two or more.

[0105] Examples of organic fillers include acrylic particles, polymethyl methacrylate, polystyrene (polystyrene beads), copolymers obtained by copolymerizing the monomers constituting these (i.e., methyl methacrylate or styrene) with other monomers, polyethylene particles, polysiloxane resin particles, polyamide particles, polyester fine particles, polyurethane fine particles, and rubber fine particles (acrylic rubber particles, isoprene rubber particles). The organic filler may have a core-shell structure. The organic filler may be one type or a combination of two or more types.

[0106] The average particle size of the inorganic filler and the organic filler is not particularly limited, but is preferably 0.01 μm to 10 μm, and particularly preferably 1 μm to 5 μm. The average particle size of the inorganic filler and the organic filler can be measured using a laser diffraction particle size distribution analyzer.

[0107] Examples of the polymerization inhibitor include hydroquinone, paramethoxyphenol, and 2,6-di-t-butyl-4-cresol. Components other than those mentioned above can be appropriately selected from known components used in curable resin compositions.

[0108] The other components may each be one type or a combination of two or more types.

[0109] <Content of each ingredient> The content of the (A) modified resin is preferably 40 parts by mass or more and less than 100 parts by mass, more preferably 50 to 95 parts by mass, and particularly preferably 60 to 90 parts by mass, per 100 parts by mass of the curable resin composition. From the viewpoint of achieving both the curability and storage stability of the curable resin composition, the content of the boron-containing compound (B) relative to the weight of the modified resin (A) is 0.1 × 10 -6 mol / g or more 100.0×10 -6 mol / g or less, and preferably 0.5×10 -6 mol / g or more 50.0×10 -6 mol / g or less is more preferable, and 1.0×10 -6 mol / g or more 10.0×10 -6 It is particularly preferable that the content is mol / g or less. Note that, since the (B) boron-containing compound has one boron atom in the molecule, the above content corresponds to the content of boron atoms. The content of the photopolymerization initiator is preferably 0.1 to 10 parts by mass, particularly preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the curable resin composition. The content of the heat curing agent is preferably 0 to 50 parts by mass, more preferably 1.0 to 30 parts by mass, and particularly preferably 5.0 to 25 parts by mass, relative to 100 parts by mass of the curable resin composition. In addition to the above, the total content of other components is preferably 0 to 50 parts by mass, particularly preferably 0 to 30 parts by mass, per 100 parts by mass of the curable resin composition.

[0110] <Method for preparing curable resin composition> The curable resin composition can be produced by mixing the components.

[0111] <Curing method> The curable resin composition can be cured by irradiation with energy rays such as ultraviolet rays and by applying heat, or by applying heat before, after, or simultaneously with irradiation with energy rays such as ultraviolet rays. Thus, the curable resin composition is a photo- (energy ray) curable, heat-curable, or energy ray and heat-curable composition.

[0112] <Application> The curable resin composition has reduced solubility in liquid crystals and can prevent contamination of the liquid crystals. Therefore, the curable resin composition can be used as a liquid crystal sealant (such as a sealant for liquid crystal elements, a liquid crystal sealant for display elements, and a liquid crystal sealant for light-adjusting devices) and a sealant for various displays such as organic electroluminescence (EL). The curable resin composition may also be a liquid crystal sealant used in liquid crystal displays (or liquid crystal display elements) including modular displays, three-dimensional displays, head-mounted displays, and projection displays; light-intensity adjusting liquid crystal elements such as dimming filters, dimming shutters, anti-glare mirrors, and spatial light modulators; focus-variable liquid crystal elements such as liquid crystal lenses; and light-modulating liquid crystal elements such as optical deflectors, optical demultiplexers, phase control, polarization control, holograms, diffraction gratings, wavelength filters, and frequency filters. In the above cases, the curable resin composition serving as the liquid crystal sealant preferably further contains (C) a photopolymerization initiator and / or a thermal curing agent.

[0113] A cured product of the curable resin composition is used to seal a liquid crystal element. Therefore, the present invention also covers a liquid crystal element sealed with the curable resin composition. Examples of a method for producing a liquid crystal element include a step of applying the curable resin composition to one of two transparent substrates with electrodes using a dispenser to form a pattern of the curable resin composition, a step of dropping liquid crystal onto the entire surface within the frame of the transparent substrate and immediately laminating the other transparent substrate, and a step of curing the composition by irradiating the seal pattern portion with light such as ultraviolet light, heating the curable resin composition, or applying heat before, after, or simultaneously with irradiating the seal pattern portion with energy rays such as ultraviolet light. [Example]

[0114] Next, specific embodiments of the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0115] 1.Measurement method (1) Viscosity measurement The viscosity was measured at 25°C with a cone rotor rotation speed of 2.5 rpm or 5 rpm using an E-type viscometer (RE105U, manufactured by Toki Sangyo Co., Ltd.). (2) Storage stability (thickening rate) The resin or curable resin composition obtained in each example was stored at 40°C or 25°C, and the change in viscosity over time was measured to determine the viscosity increase rate. Viscosity increase rate (%) = (viscosity after storage at 40°C or 25°C - initial viscosity) / initial viscosity × 100

[0116] (3) NI point measurement Approximately 0.1 g of the resin obtained in each example was placed in an ampoule, and 10 times the amount of liquid crystal (MLC-6609, manufactured by Merck Ltd.) was added. The bottle was placed in a 120°C oven for 1 hour, then left to stand at room temperature (25°C; the same applies below). After returning to room temperature, the liquid crystal portion was removed and filtered through a 0.2 μm filter to obtain a liquid crystal sample for evaluation. The NI point was measured using a differential scanning calorimeter (DSC, PYRIS6, manufactured by PerkinElmer Japan Co., Ltd.) by sealing 10 mg of the liquid crystal sample for evaluation in an aluminum sample pan at a heating rate of 5°C / min. The temperature at the top of the endothermic peak was taken as the NI point. The blank was obtained by sealing 10 mg of the liquid crystal in an aluminum sample pan at a heating rate of 5°C / min. The NI point of the blank was 92.78°C. The difference between the endothermic peak top (phase transition temperature) TB of the blank and the endothermic peak top (phase transition temperature) TE of the liquid crystal for evaluation; TE-TB, was defined as the NI point change.

[0117] (4) Curability (reaction rate) The curable resin composition was sandwiched between a 25 mm × 25 mm, 0.7 mm thick LCD glass sheet on one side and a 25 mm × 25 mm, 0.1 mm thick PET film on the other side so that the thickness of the curable resin composition was 0.05 mm, and the composition was heated in an oven at 120°C for 1 hour, or exposed to 100 mW / cm UV irradiation using an ultraviolet ray irradiation device (UVX-01224S1, manufactured by Ushio Inc.). 2 The cumulative amount of light is 3,000 mJ / cm 2 After that, the sample was heated in an oven at 120°C for 1 hour to prepare a sample for measurement.

[0118] The reaction rate was measured using FT-IR (SpectrumOne, manufactured by PerkinElmer Japan Co., Ltd.), and the reaction rate (conversion rate) of the (meth)acryloyl group and the epoxy group was calculated from the peak area of ​​the (meth)acryloyl group or the epoxy group in the obtained IR spectrum.

[0119] The reaction rate was calculated using the 1630 cm -1 (or 945cm -1 ) or the decrease in the absorption peak area of ​​the epoxy group at 915 cm -1 The decrease in the absorption peak area at 1500 cm of the double bond of the benzene ring -1 The absorption peak area was calculated based on the absorption peak area shown in

[0120] (5)Solubility It was visually confirmed whether the boron compound (including (B) boron-containing compound; the same applies below) was uniformly dissolved or compatible in the resin. If the boron compound was uniformly dissolved or compatible in the resin, it was evaluated as "Good", and if the boron compound was not uniformly dissolved or compatible in the resin, it was evaluated as "Poor".

[0121] 2. Modified resin synthesis example The boron compounds used in the modified resin synthesis examples are as follows: Boric acid represented by formula (b-1) (CAS registration number: 10043-35-3) [ka] Phenylboronic acid (boronic acid compound) represented by formula (b-2) (CAS Registry Number: 98-80-6) [ka] Triphenyl borate represented by formula (b'-1) (CAS Registry Number: 1095-03-0) [ka] Tributyl borate (CAS Registry Number: 688-74-4) represented by formula (b'-2) [ka]

[0122] Comparative Synthesis Example 1: Boron Compound-Free Resin 1 (Partially Methacrylated Bisphenol A Epoxy Resin) 170.0 g of bisphenol A epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 45.2 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 262 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 43 mg of BHT (2,6-di-tert-butyl-p-cresol, manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100-115°C. The reaction rate was calculated from the amount of methacrylic acid initially added and the remaining amount of methacrylic acid. The mixture was heated and stirred until the reaction rate reached 99.9% or higher, yielding 210.0 g of a pale yellow, transparent, viscous boron compound-free resin 1. The epoxy equivalent of the resulting boron compound-free resin 1 (partially methacrylated bisphenol A epoxy resin) was 487 g / eq.

[0123] <Synthesis Example 1> Boron Compound-Containing Resin 1 170.0 g of bisphenol A epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 45.2 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 262 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), 43 mg of BHT (manufactured by Tokyo Chemical Industry Co., Ltd.), and 61.8 mg of boric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100-115°C. The reaction rate was calculated from the amount of methacrylic acid initially added and the remaining amount of methacrylic acid. The mixture was heated and stirred until the reaction rate reached 99.9% or higher, yielding 207.0 g of a pale yellow, transparent, viscous boron compound-containing resin 1. The epoxy equivalent of the resulting boron compound-containing resin 1 was 494 g / eq.

[0124] <Synthesis Example 2> Boron Compound-Containing Resin 2 170.0 g of bisphenol A epoxy resin (EXA-850CRP, manufactured by DIC Corporation), 45.2 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 262 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), 43 mg of BHT (manufactured by Tokyo Chemical Industry Co., Ltd.), and 122 mg of phenylboric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100-115°C. The reaction rate was calculated from the amount of methacrylic acid initially added and the remaining amount of methacrylic acid. The mixture was heated and stirred until the reaction rate reached 99.9% or higher, yielding 200.0 g of a pale yellow, transparent, viscous boron compound-containing resin 2. The epoxy equivalent of the resulting boron compound-containing resin 2 was 470 g / eq.

[0125] <Synthesis Example 3> Boron Compound-Containing Resin 3 A partially methacrylated bisphenol A type epoxy resin was obtained in the same manner as in Comparative Synthesis Example 1. Then, boric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in an amount shown in Table 1 to 100 parts by mass of the partially methacrylated bisphenol A type epoxy resin and mixed with stirring to obtain a boron compound-containing resin 3.

[0126] <Synthesis Example 4> Boron Compound-Containing Resin 4 A partially methacrylated bisphenol A type epoxy resin was obtained in the same manner as in Comparative Synthesis Example 1. Then, phenylboric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in an amount shown in Table 1 to 100 parts by mass of the partially methacrylated bisphenol A type epoxy resin and stirred to obtain a boron compound-containing resin 4.

[0127] Comparative Synthesis Example 2: Boron Compound-Containing Resin 5 A partially methacrylated bisphenol A type epoxy resin was obtained in the same manner as in Comparative Synthesis Example 1. Then, triphenyl borate (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred with 100 parts by mass of the partially methacrylated bisphenol A type epoxy resin in the amount shown in Table 1 to obtain a boron compound-containing resin 5.

[0128] Comparative Synthesis Example 3: Boron Compound-Containing Resin 6 A partially methacrylated bisphenol A type epoxy resin was obtained in the same manner as in Comparative Synthesis Example 1. Then, tributyl borate (manufactured by Tokyo Chemical Industry Co., Ltd., liquid at room temperature) was added in an amount shown in Table 1 to 100 parts by mass of the partially methacrylated bisphenol A type epoxy resin, and the mixture was stirred to obtain a boron compound-containing resin 6.

[0129] 4. Example of production of curable resin composition The components shown in Tables 3 to 5 were mixed and stirred in the amounts (parts by mass) shown in the tables using a planetary mixer to prepare curable resin compositions. The heat curing agents used were EH-5030S (a polyamine-based compound manufactured by ADEKA Corporation, active hydrogen equivalent: 105 g / eq), ADH-S (a hydrazide-based compound manufactured by Otsuka Chemical Co., Ltd., active hydrogen equivalent: 44 g / eq), and 2P4MHZ-PW (an imidazole-based compound manufactured by Shikoku Chemical Industries Co., Ltd.). The resulting resin compositions were stored at 25°C, and the viscosity change over time was measured. The heat curing and UV curing properties of the resulting resin compositions were also evaluated.

[0130] Photopolymerization initiator 1 and photopolymerization initiator 2 were produced according to the following method.

[0131] (1) Photopolymerization initiator 1 26.8 g (0.1 epoxy equivalent) of polyethylene glycol diglycidyl ether (EX-830, Nagase ChemteX Corporation), 16.5 g (0.1 mol) of 4-dimethylaminobenzoic acid, 3.71 g (0.02 mol) of benzyltrimethylammonium chloride, and 25 g of MIBK (methyl isobutyl ketone) were placed in a flask and stirred at 110°C for 24 hours using an oil bath. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform, and washed six times with 100 ml of water. The solvent in the organic phase was distilled off under reduced pressure, yielding 35.3 g of photopolymerization initiator 1.

[0132] (2) Photopolymerization initiator 2 26.8 g (0.1 epoxy equivalent) of polyethylene glycol diglycidyl ether (EX-830, Nagase ChemteX Corporation), 22.83 g (0.1 mol) of 2-hydroxy-9H-thioxanthen-9-one, 3.71 g (0.02 mol) of benzyltrimethylammonium chloride, and 40 g of MIBK were placed in a flask and stirred at 110°C for 72 hours using an oil bath. The reaction mixture was cooled to room temperature, dissolved in 50 g of chloroform, and washed six times with 100 ml of water. The solvent in the organic phase was distilled off under reduced pressure, yielding 36.2 g of photopolymerization initiator 2.

[0133] [Table 1]

[0134] [Table 2]

[0135] [Table 3]

[0136] [Table 4]

[0137] [Table 5]

Claims

1. (A) a modified resin in which some or all of the epoxy groups in the epoxy resin have been modified with a modifying compound containing (meth)acrylic acid and / or (meth)acrylic anhydride; (B) at least one boron-containing compound selected from the group consisting of boric acid and boronic acid compounds; A curable resin composition comprising:

2. The curable resin composition according to claim 1, wherein the boronic acid compound is represented by the following general formula (10): 【Chemistry 15】 [In the formula, R is an alkyl group, a cycloalkyl group, or an aryl group.]

3. The content of the boron compound relative to the weight of the modified resin is 0.1 × 10 －６ mol / g or more 100.0×10 －６ 2. The curable resin composition according to claim 1, wherein the curable resin composition has a viscosity of 1000 MPa or less.

4. The content of the boron compound relative to the weight of the modified resin is 0.1 × 10 －６ mol / g or more 100.0×10 －６ The curable resin composition according to claim 2 , wherein the molecular weight is 1000 mol / g or less.

5. The curable resin composition according to any one of claims 1 to 4, further comprising (C) a heat curing agent and / or a photopolymerization initiator.

6. The curable resin composition according to claim 5 , which is a liquid crystal sealing material.

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