Curable resin with excellent storage stability and its manufacturing method

Abstract

To provide a modified resin which is excellent in storage stability, and a manufacturing method of the same.SOLUTION: There are provided a production method of a carbon dioxide gas mixed and modified resin which includes the steps of: reacting an epoxy resin with a modified compound containing a (meth)acrylic acid and / or a (meth) acrylic acid anhydride, and obtaining a modified resin in which a part or all of epoxy groups of the epoxy resin is modified with the modified compound; and treating the modified resin with high concentration carbon dioxide having a carbon dioxide concentration higher than that of air, and obtaining a carbon dioxide gas mixed and modified resin, and a carbon dioxide gas mixed and modified resin having a dissolved carbon dioxide concentration of 2 mg / L or more, wherein the modified resin is a modified resin in which a part or all of epoxy groups of the epoxy resin is modified with a modified compound containing a (meth)acrylic acid and / or a (meth) acrylic acid anhydride.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable resin having excellent storage stability, and a method for producing said resin. [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 method for producing an epoxy acrylate resin by reacting an epoxy resin with acrylic acid in an inert gas atmosphere. Patent Document 2 discloses a method for producing an epoxy partially esterified product by reacting an epoxy resin with an unsaturated carboxylic acid in the presence of a tertiary amine as an addition reaction catalyst and phenothiazine as a polymerization inhibitor. Patent Document 3 discloses a method for producing an epoxy acrylate by reacting an epoxy resin with an unsaturated carboxylic acid in the presence of a trivalent organophosphorus compound catalyst in an atmosphere of a gas with an oxygen concentration of 2 to 12%, followed by introducing an oxygen-containing gas into the system as a catalyst deactivation step. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Unexamined Patent Publication No. 60-120715 [Patent Document 2] Japanese Patent Application Laid-Open No. 2004-244543 [Patent Document 3] Japanese Patent Application Laid-Open No. 2002-293876 Summary of the Invention [Problem to be solved by the invention]

[0005] According to the findings of the present inventors, the resins described in Patent Documents 1 and 2 have a problem in that the storage stability of the resin after production is low. In addition, the production method of Patent Document 3 involves treating the resin with oxygen gas after production, but still has a problem in that the storage stability is low.

[0006] Therefore, an object of the present invention is to provide a modified resin having excellent storage stability and a method for producing the same. [Means for solving the problem]

[0007] The present invention relates to the following: [1] A method for producing a carbon dioxide gas-modified resin, a step of reacting an epoxy resin with a modifying compound containing (meth)acrylic acid and / or (meth)acrylic anhydride to obtain a modified resin in which a part or all of the epoxy groups of the epoxy resin are modified with the modifying compound; a step of treating the modified resin with high-concentration carbon dioxide having a carbon dioxide concentration higher than that of air to obtain a carbon dioxide gas-incorporated modified resin; A method for producing a carbon dioxide gas-modified resin, comprising: [2] A carbon dioxide gas-mixed modified resin having a dissolved carbon dioxide concentration of 2 mg / L or more, the modified resin being a modified resin in which some or all of the epoxy groups of an epoxy resin have been modified with a modifying compound containing (meth)acrylic acid and / or (meth)acrylic anhydride. [3] The carbon dioxide-modified resin according to [2], wherein the epoxy resin has an aromatic ring. [4] A curable resin composition comprising the carbon dioxide gas-mixing modified resin of [2] or [3], and a photopolymerization initiator and / or a heat curing agent. [5] The curable resin composition of [4], which is a liquid crystal sealant. [Effects of the Invention]

[0008] According to the present invention, a modified resin having excellent storage stability and a method for producing the same are 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, the term "alkyl group", whether used alone or in combination with other terms, refers to a linear or branched monovalent group. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 18, even more preferably 1 to 10, 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] As used herein, alone or in combination with other terms, an "alkylene group" refers to a linear or branched divalent group. The alkylene group preferably has 1 to 20 carbon atoms, and particularly preferably has 1 to 8 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, an ethylidene group (ethane-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 2-ethylhexane-1,6-diyl group, a heptamethylene group, and an octamethylene group.

[0013] As used herein, alone or in combination with other terms, an "alkenyl group" refers to a linear or branched monovalent group. The number of unsaturated bonds in the alkenyl group is preferably 1 to 5, and particularly preferably 1 or 2. The alkenyl group preferably has 2 to 20 carbon atoms, more preferably 3 to 20, even more preferably 3 to 15, and particularly preferably 3 to 10. When the alkenyl group contains a vinyl group or a 1-methylvinyl group, the alkenyl group may have 2 to 20, 2 to 15, or 2 to 10 carbon atoms. Examples of the alkenyl group include a vinyl group, a 1-methylvinyl group, a 1-propenyl group, a 2-propenyl group, a 1-methyl-1-propenyl group, a 2-methyl-1-propenyl group, a 2-butenyl group, a 3-butenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, a 5-hexenyl group, and a 9-decenyl group.

[0014] As used herein, alone or in combination with other terms, an "alkynyl group" refers to a linear or branched monovalent group. The number of carbon atoms in the alkynyl group is preferably 2 to 20, and particularly preferably 2 to 15. Examples of the alkynyl group include an ethynyl group, a propargyl group, a 2-butynyl group, a 3-butynyl group, a 2-pentynyl group, a 3-pentynyl group, a 4-pentynyl group, a 2-hexynyl group, a 3-hexynyl group, a 4-hexynyl group, and a 5-hexynyl group.

[0015] The alkyl group, alkylene group, alkenyl group, and alkynyl group may be substituted with a substituent, which is not particularly limited and includes, for example, a halogen atom and an amino group.

[0016] 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, with a phenyl group being preferred.

[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, with a phenylene group and a naphthylene group being preferred.

[0018] The aryl group and the arylene group 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 alkyl group preferably has 1 to 4 carbon atoms. The alkyl moiety in the alkoxy group is preferably an alkyl group having 1 to 4 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an i-butoxy group, a sec-butoxy group, and a tert-butoxy group. The alkyl moiety in the alkylcarbonyl group and the alkylmercapto group is preferably an alkyl group having 1 to 4 carbon atoms. Examples of the alkylcarbonyl group include an acetyl group, a propanoyl group, a 2-methylpropanoyl group, and a butanoyl group. Examples of the alkyl mercapto group include a methyl mercapto group, an ethyl mercapto group, a propyl mercapto group, an i-propyl mercapto group, a butyl mercapto group, an i-butyl mercapto group, a sec-butyl mercapto group, a tert-butyl mercapto group, etc. The cycloalkyl group is a monocyclic or polycyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, and examples thereof 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, an adamantyl group, etc.

[0019] [Method for manufacturing carbon dioxide gas modified resin] In the method for producing a carbon dioxide gas-modified resin, the modified resin is a resin in which some or all of the epoxy groups of an epoxy resin have been modified with a modifying compound containing (meth)acrylic acid and / or (meth)acrylic anhydride. The method for producing a carbon dioxide gas-modified resin includes a step of reacting an epoxy resin with the modifying compound to obtain a modified resin, and a step of treating the modified resin with high-concentration carbon dioxide having a carbon dioxide concentration higher than that of air.

[0020] The carbon dioxide-modified resin obtained by the carbon dioxide-modified resin manufacturing method is the first carbon dioxide-modified resin of the present invention. The first carbon dioxide-modified resin can suppress viscosity change during storage at room temperature more than conventional resins. Therefore, the first carbon dioxide-modified resin has excellent storage stability. Therefore, the first carbon dioxide-modified resin can ease the storage conditions of the modified resin and extend the usable period as a raw material for a curable resin composition. Furthermore, when the first carbon dioxide-modified resin is used as a raw material for a curable resin composition (for example, a raw material for a liquid crystal sealant), the viscosity change of the first carbon dioxide-modified resin is small, so the range of the finished viscosity of the curable resin composition can be narrowed.

[0021] [First step: Step of obtaining modified resin] The first step in the method for producing a carbon dioxide-modified resin is to react an epoxy resin with a modifying compound containing (meth)acrylic acid and / or (meth)acrylic anhydride to obtain a modified resin. The modified resin is a resin before treatment with high-concentration carbon dioxide, as described below.

[0022] (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.

[0023] 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.

[0024] The aliphatic epoxy resin and alicyclic epoxy resin can be appropriately selected from known components.

[0025] The epoxy resin is preferably a di- or higher functional epoxy resin, and particularly preferably a di- to tetra-functional epoxy resin. The epoxy resin is preferably an epoxy resin having an aromatic ring, and is particularly preferably at least one selected from the group consisting of bisphenol-type epoxy resins and resorcinol-type epoxy resins. The epoxy resin may be one component or two or more components.

[0026] (modified compounds) The modifying compound contains (meth)acrylic acid and / or (meth)acrylic anhydride, and is a raw material for the modified resin.

[0027] <(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.

[0028] <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.

[0029] <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.

[0030] 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.

[0031] 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.

[0032] 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).

[0033] 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.

[0034] <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.

[0035] <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.

[0036] <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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] In the first step of the method for producing a carbon dioxide-modified resin, 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%. Furthermore, the ratio of modification 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%, or may be 10 to 80%. In the first step of the method for producing a carbon dioxide-modified resin, the reaction between the epoxy groups and the modifying compound proceeds quantitatively, so the modification ratio of the resulting modified resin can also be estimated from the epoxy equivalent. Furthermore, 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 modifying compound used at the beginning of the reaction and the remaining amount of modifying compound. Here, the reaction ratio at the end of the reaction is preferably 99% or more, particularly preferably 99.9% or more.

[0045] 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.

[0046] (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] TIFF0007810427000002.tif61161 [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 , C2 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.

[0047] 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.

[0048] In the first step of the method for producing a carbon dioxide gas-modified resin, 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 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).

[0049] ·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.

[0050] 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.

[0051] ·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.

[0052] 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 a linking group.

[0053] 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 bonded to Ar 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.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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).

[0058] Ar when n1 is 3 1 Specific examples of the formula include the following: where * indicates the bonding position. [ka]

[0059] Ar when n1 is 4 1 Specific examples of the formula include the following: where * indicates the bonding position. [ka]

[0060] 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

[0061] 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.

[0062] 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.

[0063] 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:

[0064] 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):

[0065] [ka] [During the ceremony, Y 1 is an n-valent hydrocarbon group, n2 is 2 or more, 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]

[0066] Y 1 , n2 Y 1 is a hydrocarbon group having a valence of n. 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.

[0067] 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.

[0068] ·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.

[0069] 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).

[0070] 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).

[0071] [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 are each independently 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).

[0072] In the first step of the method for producing a carbon dioxide gas-modified resin, when the total modification ratio of the modifying compound to the epoxy groups 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).

[0073] Modified resins, epoxy resins, modified compounds, and conditions for the reaction of epoxy resins and modified compounds other than those described above include those described in JP-A-2018-172483 and JP-A-2018-172484.

[0074] [Second step: treatment with high-concentration carbon dioxide] The second step in the method for producing a carbon dioxide gas-incorporated modified resin is a step of treating the modified resin with high-concentration carbon dioxide. The second step produces a first carbon dioxide gas-incorporated modified resin. High-concentration carbon dioxide is not particularly limited as long as it is a component containing carbon dioxide and has a higher carbon dioxide concentration than air, where the carbon dioxide concentration in air is less than 0.1%. Furthermore, high-concentration carbon dioxide may be solid, liquid, or gas. High-concentration carbon dioxide may contain components other than carbon dioxide. For example, when high-concentration carbon dioxide is a gas, gases other than carbon dioxide may be present. Examples of such gases other than carbon dioxide include nitrogen, argon, and oxygen. Furthermore, in high-concentration carbon dioxide, the carbon dioxide content (i.e., carbon dioxide concentration) is 0.1% or more, and may be 20% or more, 50% or more, 80% or more, 90% or more, or even 100%. The content may be expressed in volume % or mass % depending on the state of the high-concentration carbon dioxide.

[0075] (Treatment with high-concentration carbon dioxide) The treatment with high-concentration carbon dioxide can be any method as long as the modified resin is brought into contact with high-concentration carbon dioxide and the desired carbon dioxide-mixed modified resin is obtained. Examples of such a treatment method with high-concentration carbon dioxide include a method of stirring the modified resin in a state where the space above the liquid surface of a reaction vessel is filled with carbon dioxide, a method of contacting the modified resin with dry ice, liquefied carbon dioxide gas, or a supercritical fluid of carbon dioxide, and a method of bubbling high-concentration carbon dioxide into the modified resin. Here, bubbling refers to an operation of supplying carbon dioxide into the modified resin to generate bubbles. Known methods can be used as the bubbling method.

[0076] When the treatment with high-concentration carbon dioxide is bubbling, the flow rate of the high-concentration carbon dioxide gas during bubbling is preferably 0.1 to 50 mL / min, more preferably 0.5 to 20 mL / min, and particularly preferably 1 to 10 mL / min, per 100 g of the resin component in the modified resin. If the flow rate is equal to or higher than the lower limit of the above range, the dissolved carbon dioxide concentration can be efficiently increased, and if it is equal to or lower than the upper limit, splashing can be suppressed, resulting in excellent bubbling operability. When the treatment method with high-concentration carbon dioxide is other than bubbling, the amount of high-concentration carbon dioxide used relative to the modified resin can be appropriately set depending on the range in which the desired dissolved carbon dioxide concentration is obtained.

[0077] The treatment with high-concentration carbon dioxide may be carried out with heating, without heating, or with cooling. The temperature of the modified resin during the treatment with high-concentration carbon dioxide is preferably 10°C to 100°C, more preferably 15°C to 90°C, and particularly preferably 20°C to 80°C.

[0078] The treatment with high concentration carbon dioxide may be carried out with stirring. The time for performing the treatment with high-concentration carbon dioxide (treatment time) can be appropriately set depending on the carbon dioxide concentration of the high-concentration carbon dioxide used in the treatment, so that a first carbon dioxide-admixed modified resin with a desired dissolved carbon dioxide concentration can be obtained. For example, when the carbon dioxide concentration of the high-concentration carbon dioxide is low, a first carbon dioxide-admixed modified resin with a high dissolved carbon dioxide concentration tends to be obtained by increasing the flow rate of the high-concentration carbon dioxide gas, increasing the amount of dry ice, liquefied carbon dioxide, or carbon dioxide supercritical fluid added, or lengthening the treatment time.

[0079] [Obtained Carbon Dioxide-Modified Resin] The first carbon dioxide gas-modified resin is a modified resin containing carbon dioxide. The first carbon dioxide gas-modified resin preferably has a dissolved carbon dioxide concentration similar to that of the second carbon dioxide gas-modified resin described below.

[0080] [Second carbon dioxide-modified resin] The second carbon dioxide gas-modified resin has a dissolved carbon dioxide concentration of 2 mg / L or more. The second carbon dioxide gas-modified resin is a modified resin in which some or all of the epoxy groups of an epoxy resin have been modified with a modifying compound containing (meth)acrylic acid and / or (meth)acrylic anhydride. The second carbon dioxide-modified resin has a dissolved carbon dioxide concentration of 2 mg / L or more, and therefore has excellent storage stability (effectiveness in suppressing viscosity changes). Therefore, the content of additives such as polymerization inhibitors can be reduced in a curable resin composition containing the second carbon dioxide-modified resin. This reduces adverse effects on liquid crystallinity and curability when the curable resin composition containing the second carbon dioxide-modified resin is used in a liquid crystal sealant.

[0081] The structures of the epoxy resin, the modified compound, and the second carbon dioxide gas-modified resin, including preferred structures, are as described above in the method for producing the carbon dioxide gas-modified resin.

[0082] The second carbon dioxide-modified resin has a dissolved carbon dioxide concentration of 2 mg / L or more. The upper limit of the dissolved carbon dioxide concentration of the second carbon dioxide-modified resin is not particularly limited and can be the saturated dissolution amount of carbon dioxide in the second carbon dioxide-modified resin. If the dissolved carbon dioxide concentration of the second carbon dioxide-modified resin is less than 2 mg / L, the storage stability is poor. From the viewpoint of better storage stability, the dissolved carbon dioxide concentration of the second carbon dioxide-modified resin is preferably 2 mg / L to 300 mg / L, more preferably 15 mg / L to 300 mg / L, and particularly preferably 30 mg / L to 300 mg / L. The dissolved carbon dioxide concentration of the second carbon dioxide-modified resin can be increased, for example, by bubbling carbon dioxide through the modified resin. The dissolved carbon dioxide concentration of the second carbon dioxide-modified resin can also be decreased by leaving the second carbon dioxide-modified resin under reduced pressure. In addition, the dissolved carbon dioxide concentration of the second carbon dioxide-mixed modified resin can be adjusted by increasing or decreasing the treatment time for bubbling carbon dioxide into the modified resin or the time for which the second carbon dioxide-mixed modified resin is left under reduced pressure.

[0083] [Curable resin composition] The curable resin composition contains the above-mentioned (A) second carbon dioxide gas-mixable modified resin and (B) a photopolymerization initiator and / or a thermal curing agent.

[0084] <(A) Second carbon dioxide-modified resin> Component (A) is a second carbon dioxide gas-modified resin. Component (A) is a curable resin in the curable resin composition. Component (A), including preferred embodiments, is as described above.

[0085] <(B) 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 (B) include photopolymerization initiators, heat curing agents, and combinations of photopolymerization initiators and heat curing agents.

[0086] <Photopolymerization initiator> The photopolymerization initiator may be a radical polymerization initiator, an anionic polymerization initiator, and / or a cationic polymerization initiator.

[0087] 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.

[0088] Examples of the anionic polymerization initiator include imidazoles, amines, phosphines, organic metal salts, metal chlorides, and organic peroxides.

[0089] 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.

[0090] The photopolymerization initiator is commercially available or can be prepared according to known methods. The photopolymerization initiator may be one type or a combination of two or more types.

[0091] <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), and the like. Preferred are organic acid dihydrazides such as LDH (octadecane-1,18-dicarboxylic acid dihydrazide) and IDH (isophthalic acid dihydrazide); polyamine compounds sold by ADEKA Corporation as ADEKA Hardener EH-5030S, etc.; and amine adducts sold by Ajinomoto Fine-Techno Co., Ltd. as Amicure PN-23, Amicure PN-30, Amicure MY-24, Amicure MY-H, etc. The heat curing agent may be one type or a combination of two or more types.

[0092] <Other ingredients> The curable resin composition may contain a curable resin other than the component (A) (component (C)) and / or a component other than the component (C) (component (D)) depending on the purpose, as long as the effects of the present invention are not impaired. Examples of the component (D) include a silane coupling agent, a polymerization inhibitor, an organic filler, and an inorganic filler. Note that the components (C) and (D) are not the components (A) and (B) described above.

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

[0094] <(C-1) Difunctional or higher epoxy resin> The component (C-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 (C-1) is not particularly limited, but is preferably 2 to 4. The component (C-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. The component (C-1) may be one type or a combination of two or more types.

[0095] <(C-2) Other curable resins> The component (C-2) is not particularly limited as long as it is a curable resin other than the components (A) and (C-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 base resins for curable resin compositions. Here, "unsaturated groups" refers to ethylenically unsaturated groups and / or acetylenically unsaturated groups. The component (C-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 heat curing 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] The bifunctional (meth)acrylate compound is preferably 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 silicon di(meth)acrylate (e.g., EBECRYL 350, manufactured by Daicel-Allnex Corporation). 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. The component (C-2) may be one type or a combination of two or more types.

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

[0101] <<Other ingredients other than ingredient (C) (ingredient (D))>> Examples of the component (D) include a silane coupling agent, a polymerization inhibitor, an organic filler, and an inorganic filler.

[0102] <Silane coupling agents> 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.

[0103] 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)acrylic 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-(acrilicoxypropyl)-3-aminopropylmethyldimethoxysilane, Examples of suitable 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 mercapto groups, isocyanato groups, ureido groups, and halogen atoms, 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.

[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 component (D) may be one type or a combination of two or more types. For example, the component (D) may be a combination of one or more silane coupling agents and one or more polymerization inhibitors.

[0109] <Method for preparing curable resin composition> The curable resin composition can be produced by mixing the components.

[0110] <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.

[0111] <Application> The curable resin composition has reduced solubility in liquid crystals and can prevent contamination of the liquid crystals. Thus, the curable resin composition can be used as a liquid crystal sealant (sealant for liquid crystal elements, liquid crystal sealant for display elements, liquid crystal sealant for light-adjusting devices, etc.) 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, projection displays, etc.; 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.

[0112] 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]

[0113] 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.

[0114] 1.Measurement method (1) Dissolved carbon dioxide concentration (dissolved CO2 concentration) measurement The dissolved carbon dioxide concentration of the resin obtained in each example was measured using a carbon dioxide concentration meter (CGP-31 manufactured by DKK-TOA Corporation).

[0115] (2) Stability (storage stability) The resin or curable resin composition obtained in each example was stored at 25°C, and the change in viscosity over time was measured. (3) 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.). (4) Thickening rate Viscosity increase rate (%) = (viscosity after storage at 25°C - initial viscosity) / initial viscosity x 100

[0116] (5) NI point measurement Approximately 0.1 g of the resin obtained in each example was placed in an ampoule, and liquid crystal (MLC-6609, manufactured by Merck Ltd.) was added in an amount 10 times the amount of the resin used. The bottle was placed in a 120°C oven for 1 hour, and then left to stand at room temperature (25°C; the same applies below). After the temperature returned to room temperature, the liquid crystal portion was removed and filtered through a 0.2 μm filter to prepare 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 and heating at a rate of 5°C / min. The temperature at the top of the endothermic peak was taken as the NI point. Note that 10 mg of the liquid crystal was sealed in an aluminum sample pan and measured at a heating rate of 5°C / min, and the result was used as the blank. The NI point of the blank was 92.78°C.

[0117] 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.

[0118] (6) 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 0.5 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 UV irradiation intensity of 3000mJ / cm 2 The sample was then heated in an oven at 120°C for 1 hour to prepare a sample for measurement.

[0119] The curing rate was measured using FT-IR (SpectrumOne, manufactured by PerkinElmer Japan Co., Ltd.), and the reaction rate (conversion rate) of the (meth)acrylic group and the epoxy group was calculated from the peak area of ​​the (meth)acrylic group or the epoxy group in the obtained IR spectrum. -1 (or 945cm -1) or 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] 2. Resin synthesis example Example 1 (Carbon dioxide treatment synthesis example (1), partially methacrylated bisphenol A type epoxy resin 1) 340 g of bisphenol A epoxy resin (EXA850CRP, manufactured by DIC Corporation), 90.0 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 525 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 733 mg of BHT (2,6-di-tert-butyl-p-cresol, manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 100 to 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 a modified resin (i.e., the modified resin before carbon dioxide bubbling). The heat source was then removed from the reaction system, the temperature was lowered to 100 °C, and carbon dioxide bubbling (gas flow rate: 2 L / min per 100 g of resin component in the modified resin) was carried out for approximately 30 minutes. The gas used for carbon dioxide bubbling had a carbon dioxide concentration of 100% by volume. The temperature at the end of bubbling was 40 °C. 418.0 g of partially methacrylated bisphenol A epoxy resin 1, a carbon dioxide-modified resin, was obtained as a pale yellow, transparent, viscous substance. The epoxy equivalent of the resulting resin was 441 g / eq. The dissolved CO2 concentration was 109 mg / L.

[0121] Comparative Example 1 (Untreated Synthesis Example (1), Partially Methacrylated Bisphenol A-Type Epoxy Resin 2) In the same manner as in Example 1, a modified resin with a reaction rate of 99.9% or higher was obtained. The heat source was then removed from the reaction system, and the temperature was lowered to room temperature. 416.0 g of a pale yellow, transparent, viscous partially methacrylated bisphenol A-type epoxy resin 2 was obtained. The epoxy equivalent of the resulting resin was 441 g / eq. The dissolved CO2 concentration was 0.9 mg / L.

[0122] Comparative Example 2 (Oxygen Treatment Synthesis Example (1), Partially Methacrylated Bisphenol A-Type Epoxy Resin 3) In the same manner as in Example 1, a modified resin with a reaction rate of 99.9% or higher was obtained. The heat source was then removed from the reaction system, the temperature was lowered to 100°C, and oxygen bubbling (gas flow rate: 2 L / min per 100 g of resin component in the modified resin) was carried out for approximately 30 minutes. The gas used for oxygen bubbling had a carbon dioxide concentration of less than 0.1% by volume. The temperature at the end of bubbling was 35°C. 410.0 g of a pale yellow, transparent, viscous partially methacrylated bisphenol A-type epoxy resin 3 was obtained. The epoxy equivalent of the resulting resin was 440 g / eq. The dissolved CO2 concentration was 0.7 mg / L.

[0123] Example 2 (Carbon dioxide treatment synthesis example (2), partially methacrylated bisphenol F type epoxy resin 1) 320 g of bisphenol F epoxy resin (EXA830CRP, manufactured by DIC Corporation), 86.0 g of methacrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 525 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 690 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 a modified resin (i.e., the modified resin before CO2 bubbling). The heat source was then removed from the reaction system, the temperature was lowered to 100°C, and carbon dioxide bubbling (gas flow rate: 2 L / min per 100 g of resin component in the modified resin) was carried out for approximately 30 minutes. The gas used for carbon dioxide bubbling had a carbon dioxide concentration of 100% by volume. The temperature at the end of bubbling was 38°C. 390.0 g of partially methacrylated bisphenol F epoxy resin 1, a carbon dioxide-modified resin, was obtained as a pale yellow, transparent, viscous substance. The epoxy equivalent of the resulting resin was 420 g / eq. The dissolved CO2 concentration was 45.0 mg / L.

[0124] Comparative Example 3 (Untreated Synthesis Example (2), Partially Methacrylated Bisphenol F Epoxy Resin 2) In the same manner as in Example 2, a modified resin with a reaction rate of 99.9% or higher was obtained. The heat source was then removed from the reaction system, and the temperature was lowered to room temperature. 380.0 g of a pale yellow, transparent, viscous partially methacrylated bisphenol F-type epoxy resin 2 was obtained. The epoxy equivalent of the resulting resin was 420 g / eq. The dissolved CO2 concentration was 0.8 mg / L.

[0125] Comparative Example 4 (Oxygen Treatment Synthesis Example (2), Partially Methacrylated Bisphenol F Epoxy Resin 3) In the same manner as in Example 2, a modified resin with a reaction rate of 99.9% or higher was obtained. The heat source was then removed from the reaction system, the temperature was lowered to 100°C, and oxygen bubbling (gas flow rate: 2 L / min per 100 g of resin component in the modified resin) was performed for approximately 30 minutes. The gas used for oxygen bubbling had a carbon dioxide concentration of less than 0.1% by volume. The temperature at the end of bubbling was 33°C. 386.0 g of a pale yellow, transparent, viscous partially methacrylated bisphenol F-type epoxy resin 3 was obtained. The epoxy equivalent of the resulting resin was 421 g / eq. The dissolved CO2 concentration was 0.7 mg / L.

[0126] Example 3 (Carbon dioxide treatment synthesis example (3), partially acrylated bisphenol F epoxy resin 1) 320 g of bisphenol F epoxy resin (EXA830CRP, manufactured by DIC Corporation), 72.0 g of acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 525 mg of triphenylphosphine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 667 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 acrylic 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 a modified resin (i.e., the modified resin before CO2 bubbling). The heat source was then removed from the reaction system, the temperature was lowered to 100°C, and carbon dioxide bubbling (gas flow rate: 2 L / min per 100 g of resin component in the modified resin) was carried out for approximately 30 minutes. The gas used for carbon dioxide bubbling had a carbon dioxide concentration of 100% by volume. The temperature at the end of bubbling was 38°C. 360.0 g of partially acrylated bisphenol F epoxy resin 1, a carbon dioxide-modified resin, was obtained as a pale yellow, transparent, viscous substance. The epoxy equivalent of the resulting resin was 401 g / eq. The dissolved CO2 concentration was 38.0 mg / L.

[0127] Comparative Example 5 (Untreated Synthesis Example (3), Partially Acrylated Bisphenol F Epoxy Resin 2) In the same manner as in Example 3, a modified resin with a reaction rate of 99.9% or higher was obtained. The heat source was then removed from the reaction system, and the temperature was lowered to room temperature. 370.0 g of a pale yellow, transparent, viscous partially acrylated bisphenol F-type epoxy resin 2 was obtained. The epoxy equivalent of the resulting resin was 402 g / eq. The dissolved CO2 concentration was 0.9 mg / L.

[0128] Comparative Example 6 (Oxygen Treatment Synthesis Example (3), Partially Acrylated Bisphenol F Epoxy Resin 3) In the same manner as in Example 3, a modified resin with a reaction rate of 99.9% or higher was obtained. The heat source was then removed from the reaction system, the temperature was lowered to 100°C, and oxygen bubbling (gas flow rate: 2 L / min per 100 g of resin component in the modified resin) was performed for approximately 30 minutes. 366.0 g of a pale yellow, transparent, viscous partially acrylated bisphenol F-type epoxy resin 3 was obtained. The gas used for oxygen bubbling had a carbon dioxide concentration of less than 0.1% by volume. The temperature at the end of bubbling was 36°C. The epoxy equivalent of the resulting resin was 401 g / eq. The dissolved CO2 concentration was 0.8 mg / L.

[0129] 3. Example of production of curable resin composition The components shown in Table 2 were mixed and stirred in the amounts (parts by mass) shown in the table using a planetary mixer to obtain a curable resin composition. 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 composition was stored at 25°C, and the viscosity change over time was measured. The heat curing and UV curing properties of the resulting resin composition 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 equivalents) of polyethylene glycol diglycidyl ether (EX-830, Nagase ChemteX Corporation), 16.5 g (0.1 equivalents) of 4-dimethylaminobenzoic acid, 3.71 g (0.02 equivalents) 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 equivalents) of polyethylene glycol diglycidyl ether (EX-830, Nagase ChemteX Corporation), 22.83 g (0.1 equivalents) of 2-hydroxy-9H-thioxanthen-9-one, 3.71 g (0.02 equivalents) 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]

Claims

1. A method for producing a carbon dioxide gas-modified resin, comprising: a step of reacting an epoxy resin having an aromatic ring with a modifying compound containing (meth)acrylic acid and / or (meth)acrylic anhydride to obtain a modified resin in which a portion of the epoxy groups of the epoxy resin have been modified with the modifying compound; a step of treating the modified resin with high-concentration carbon dioxide having a carbon dioxide concentration higher than that of air to obtain a carbon dioxide gas-incorporated modified resin; wherein the treatment with high-concentration carbon dioxide is bubbling.

2. A liquid crystal sealant comprising a carbon dioxide gas-mixed modified resin and a photopolymerization initiator and / or a heat curing agent, The carbon dioxide-modified resin has a dissolved carbon dioxide concentration of 2 mg / L or more, The liquid crystal sealant, wherein the modified resin is a modified resin obtained by modifying a part of the epoxy groups of an aromatic ring-containing epoxy resin with a modifying compound containing (meth)acrylic acid and / or (meth)acrylic anhydride.

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