TWI805645B - Curable resin composition and manufacturing method thereof - Google Patents

Abstract

The present invention is a curable resin composition excellent in storage stability, curability, and cleanability, and includes a curable resin (A), a latent hardener (B) and an isocyanate compound (C). The aforementioned latent hardener Part or all of (B) can react with part or all of the isocyanate compound (C), and the aforementioned latent hardener (B) is at least one selected from the following group: (b1) carbazide (carbazide) Compounds, (b2) compounds in which imidazole compounds are added to epoxy resins, (b3) compounds in which polyamine compounds are added to at least one compound selected from the group consisting of epoxy resins, isocyanate compounds, and urea (however, ( The polyamine compounds in b3) do not include hydrazine compounds, hydrazide compounds and (b1) carbazide compounds), (b4) mixed crystals of two or more hydrazide compounds, and (b5) one or more mono- or polyamine compounds Mixed crystals with one or more hydrazide compounds, and (b6) mixed crystals with one or more imidazole compounds and one or more hydrazide compounds.

Description

Curable resin composition and manufacturing method thereof

In particular, the present invention relates to curable resin compositions that can be preferably used in liquid crystal display elements such as liquid crystal displays.

The manufacturing method of the liquid crystal display unit includes the following methods: After dropping the liquid crystal inside the dam of the sealant formed on one base material, the method of laminating another base material to manufacture the liquid crystal display unit, or setting it as The injection port part is a method of manufacturing a liquid crystal display unit by laminating the base material, injecting liquid crystal, and then sealing the injection port. Since bonding includes a step of heating, a thermosetting resin composition containing an epoxy group-containing resin as a heat-curing component is used as a sealant composition for manufacturing a liquid crystal display unit.

As a curing agent for the epoxy group-containing resin, a latent curing agent capable of reacting with epoxy groups or the like by applying heat, light, pressure, etc. is used (Patent Document 1, Patent Document 2, Patent Document 3 ). In Patent Document 2, a curable resin composition is disclosed, which contains a latent hardening method in which fine powders of epoxy groups and/or polycyanate-modified amines are surface-treated with water, polyisocyanate, and epoxy resin reactants. agent. Patent Document 3 discloses a sealing compound for a liquid crystal dropping method including a hydrazine-based curing agent coated with a compound having an isocyanate group. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-133794 [Patent Document 2] Japanese Unexamined Patent Publication No. 2010-90295 [Patent Document 3] Japanese Patent Laid-Open No. 2012-93582

[Problem to be solved by the invention]

In Patent Document 1, when a curing agent that is cured at low temperature is used, the curing reaction starts slowly even at room temperature, so there is a problem that the liquid stability is deteriorated. The latent curing agent that reacts with the isocyanate compound described in Patent Document 2 must be prepared in advance before being mixed with the curable resin. In Patent Document 3, although the storage stability of the composition has been confirmed, the curability has not been confirmed. And the sealant composition is usually filled in the syringe, coated on the substrate, and the syringe is washed with an organic solvent such as acetone and reused. If the epoxy addition hardener is used, the cleaning performance will change. bad question. Therefore, an object of the present invention is to provide a curable resin composition excellent in storage stability, curability, and cleanability. [Means to solve the problem]

The present invention has the following constitutions. [1] A curable resin composition comprising a curable resin (A), a latent hardener (B) and an isocyanate compound (C), A part or all of the aforementioned latent hardener (B) can react with a part or all of the isocyanate compound (C), The aforementioned latent hardener (B) is at least one selected from the group consisting of (b1) carbazide (carbazide) compounds, (b2) compounds added to epoxy resins with imidazole compounds, (b3) optional A compound in which a polyamine compound is added to at least one compound of the group consisting of an epoxy resin, an isocyanate compound, and a urea (however, the polyamine compound in (b3) does not include hydrazine, hydrazine compound, and (b1) carbazide compound), (b4) mixed crystals of 2 or more hydrazide compounds, (b5) mixed crystals of 1 or more mono- or polyamine compounds and 1 or more hydrazide compounds, and (b6) 1 or more imidazoles Mixed crystals of a compound and one or more hydrazine compounds. [2] The curable resin composition according to [1], wherein the isocyanate compound (C) is contained in an amount of 0.02 to 28 parts by mass based on 100 parts by mass of the latent curing agent (B). [3] The curable resin composition according to [1] or [2], further comprising a photoinitiator (D). [4] The curable resin composition according to any one of [1] to [3], which is a sealant composition for liquid crystal display elements. [5] A method for producing a curable resin composition, which is a method for producing a curable resin composition comprising a curable resin (A), a latent hardener (B) and an isocyanate compound (C), comprising A step of mixing the curable resin (A), the latent hardener (B) and the isocyanate compound (C) without pre-reacting the latent hardener (B) and the isocyanate compound (C), and The aforementioned latent hardener (B) is at least one selected from the group consisting of (b1) carbazide (carbazide) compounds, (b2) compounds added to epoxy resins with imidazole compounds, (b3) optional A compound in which a polyamine compound is added to at least one compound of the group consisting of an epoxy resin, an isocyanate compound, and a urea (however, the polyamine compound in (b3) does not include hydrazine, hydrazine compound, and (b1) carbazide compound), (b4) mixed crystals of 2 or more hydrazide compounds, (b5) mixed crystals of 1 or more mono- or polyamine compounds and 1 or more hydrazide compounds, and (b6) 1 or more imidazoles Mixed crystals of a compound and one or more hydrazine compounds. [6] A liquid crystal display panel obtained by using the curable resin composition according to any one of [1] to [4]. [7] A method of manufacturing a liquid crystal display panel, which comprises photocuring and/or thermosetting using the curable resin composition according to any one of [1] to [4] in a liquid crystal dropping method. [Invention effect]

The curable resin composition of the present invention is excellent in storage stability, curability, and cleanability.

The curable resin composition is a curable resin composition comprising a curable resin (A), a latent hardener (B) and an isocyanate compound (C), A part or all of the aforementioned latent hardener (B) can react with a part or all of the isocyanate compound (C), The aforementioned latent hardener (B) is at least one selected from the group consisting of carbazide compounds, compounds added to epoxy resins with imidazole compounds, compounds selected from epoxy resins, isocyanate compounds, and urea compounds. Compounds of polyamine compounds added to at least one compound of the group, mixed crystals of two or more kinds of hydrazide compounds, mixed crystals of one or more kinds of polyamine compounds and one or more kinds of hydrazide compounds, and one or more kinds of imidazoles Mixed crystals of a compound and one or more hydrazine compounds.

1. Hardening resin (A) Examples of the curable resin include epoxy resins and resins having at least one unsaturated bond in the molecule (excluding epoxy resins having an unsaturated bond).

[epoxy resin] As the epoxy resin, those known in the art can be used, such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, phenol novolac type epoxy resin, cresol novolak Lacquer type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester resin, glycidyl amine epoxy resin, heterocyclic epoxy resin, urethane modified epoxy resin. Among them, bisphenol A type epoxy resin and cresol novolak type epoxy resin are preferably used.

In addition, the epoxy resin may be an epoxy resin having an unsaturated bond. Such an epoxy resin having an unsaturated bond is exemplified by a partially esterified epoxy resin in which a part of epoxy groups obtained by reacting an epoxy resin with (meth)acrylic acid is modified with (meth)acrylic acid. Such resins are described in, for example, JP-A-2012-77202. As an epoxy resin having an unsaturated bond, it is preferably 10-90 equivalent % to 1 equivalent of epoxy group of epoxy resin and (meth)acrylic acid, more preferably 20-80 equivalent %, and more preferably 30-70 equivalent % %, particularly preferably a partially esterified epoxy resin obtained by reacting 40-60 equivalent % of (meth)acrylic acid. An epoxy resin may be used individually by 1 type, and may use plural types together.

Partially esterified epoxy resin can be obtained by, for example, firstly making bisphenol A type epoxy resin and acrylic acid or methacrylic acid in the presence of an alkaline catalyst according to a common method, to react carboxylic acid groups with 2 equivalents of epoxy groups at 0.9~ 1. Reaction in the form of 1 equivalent, add about 4 times the mass ratio of toluene and the same amount of water to the reaction product, stir at 60~80°C for 1 hour, let it stand, separate into an organic layer and an aqueous layer, and remove the aqueous layer. This operation is repeated 3 to 5 times, and finally the base layer is recovered and the remaining toluene is removed by vacuum distillation, and the water-soluble ionic substances are purified by a partially esterified epoxy resin that has been reduced. As a specific example of the said bisphenol-A type epoxy resin, Epicote 828, 834, 1001, 1004 (made by Mitsubishi Chemical Corporation), Epiclon 850, 860, 4055 (made by DIC Corporation), etc. are mentioned, for example. Such raw material resins are preferably resins subjected to water-soluble ionic substance reduction treatment (also referred to as "high-purification treatment"), such as EPICLON 850S (manufactured by DIC Corporation). Moreover, as an example of a partial esterification epoxy resin, PR-850CRP (made by KSM company) is mentioned.

[Resins having at least one unsaturated bond in the molecule] The resin composition may also contain a resin having at least one unsaturated bond in the molecule (except epoxy resin having an unsaturated bond). Examples of the resin having at least one unsaturated bond in the molecule include styrene derivatives, vinyl derivatives, maleimide derivatives, (meth)acrylic acid derivatives, and the like. Among them, a (meth)acrylic acid derivative having at least one (meth)acryl group in the molecule is preferably used.

Specific examples of (meth)acrylic acid derivatives include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylate, ) Alkyl (meth)acrylates such as tert-butyl acrylate; Aryl (meth)acrylates such as phenyl (meth)acrylate; Aralkyl (meth)acrylates such as benzyl (meth)acrylate (meth)acrylic acid such as methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, propoxypropyl (meth)acrylate, butoxyethyl (meth)acrylate, etc. Alkoxyalkyl esters; 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc. Hydroxyl-containing (meth)acrylates; (meth)acrylates of alicyclic alcohols such as (meth)cyclohexyl acrylate; resins with glycidyl groups modified with (meth)acrylic acid (meth)acrylic acid (also known as "epoxy (meth)acrylate"), etc. The (meth)acrylic acid used in this specification means both acrylic acid and methacrylic acid.

When an epoxy resin and a resin having at least one unsaturated bond in the molecule are used together, the blending amount of the epoxy resin and the resin having at least one unsaturated bond in the molecule can be adjusted according to the purpose of hardening the resin composition. Appropriate decision. When the resin with at least one unsaturated bond in the molecule is a (meth)acrylic acid derivative with at least one (meth)acryl group in the molecule, for 1 equivalent of epoxy group, preferably (meth)acryl 0.1-9.0 equivalents for the base, more preferably 0.3-4.0 equivalents for the (meth)acryloyl group.

2. Latent hardener (B) The latent hardener (B) is at least one selected from the following group: (b1) a carbazide compound, (b2) a compound in which an imidazole compound is added to an epoxy resin, (b3) a compound selected from an epoxy resin , a compound in which at least one compound of the group consisting of isocyanate compound and urea is added to a polyamine compound, (b4) a mixed crystal of two or more hydrazine compounds, (b5) one or more polyamine compounds and one or more (b6) Mixed crystals of one or more imidazole compounds and one or more hydrazine compounds. In addition, in (b3) a compound in which a polyamine compound is added to at least one compound selected from the group consisting of epoxy resins, isocyanate compounds, and urea, the polyamine compound does not include hydrazine compounds and (b1) Carbazide compounds.

(式中，X¹ 為C₁ ~C₁₂ 伸烷基、經1個或1個以上之O原子(氧原子)非連續中斷之C₂ ~C₁₂ 伸烷基、C₁ ~C₁₂ 伸烷基氧基羰基伸烷基、C₃ ~C₁₂ 伸環烷基、C₁ ~C₁₂ 伸烷基-C₃ ~C₁₂ 伸環烷基、C₁ ~C₁₂ 伸烷基-C₃ ~C₁₂ 伸環烷基-C₁ ~C₁₂ 伸烷基、C₃ ~C₁₂ 伸環烷基-C₁ ~C₁₂ 伸烷基-C₃ ~C₁₂ 伸環烷基、二- C₃ ~C₁₂ 環烷二基、C₆ ~C₁₄ 伸芳基、C₁ ~C₄ 伸烷基-C₆ ~C₁₄ 伸芳基-C₁ ~C₄ 伸烷基、或C₆ ~C₁₄ 伸芳基-C₁ ~C₄ 伸烷基-C₆ ~C₁₄ 伸芳基(此處，伸烷基為直鏈或分支鏈，且可經鹵素取代，C₃ ~C₁₂ 伸環烷基或C₆ ~C₁₄ 伸芳基可未經取代或可經鹵素或C₁ -C₄ 烷基取代))。

(式中，X² 為C₁ ~C₁₂ 烷基、經1個或1個以上之O原子(氧原子)非連續中斷之C₂ ~C₁₂ 烷基、C₁ ~C₁₂ 烷基氧基羰基伸烷基、C₃ ~C₁₂ 環烷基、C₁ ~C₁₂ 烷基-C₃ ~C₁₂ 環烷基、C₃ ~C₁₂ 環烷基-C₁ ~C₁₂ 伸烷基-C₃ ~C₁₂ 伸環烷基、C₆ ~C₁₄ 芳基、C₁ ~C₄ 烷基-C₆ ~C₁₄ 伸芳基、C₆ ~C₁₄ 芳基-C₁ ~C₄ 伸烷基-C₆ ~C₁₄ 伸芳基(此處，伸烷基為直鏈或分支鏈，且可經鹵素取代，C₃ ~C₁₂ 環烷基、C₃ ~C₁₂ 伸環烷基、C₆ ~C₁₄ 芳基或C₆ ~C₁₄ 伸芳基可未經取代或可經鹵素或C₁ -C₄ 烷基取代)或(甲基)丙烯醯氧基烷基)。[(b1) Carbazide Compound] Examples of the carbazide compound include a bisemicarbazide compound represented by the following formula (Ib) and a hemicarbazide compound represented by the following formula (IIb).

(In the formula, X ¹ is a C ₁ ~C ₁₂ alkylene group, a C ₂ ~C ₁₂ alkylene group, a C ₁ ~C ₁₂ alkylene group interrupted by one or more O atoms (oxygen atoms) discontinuously Oxycarbonylalkylene _, C _{3 ~} C 12cycloalkylene, C ₁ ~C _12alkylene -C ₃ ~C 12cycloalkylene, C ₁ ~C _12alkylene -C ₃ ~C ₁₂ cycloalkylene-C ₁ ~C ₁₂ alkylene, C ₃ ~C ₁₂ cycloalkylene-C ₁ ~C ₁₂ alkylene-C ₃ ~C ₁₂ cycloalkylene, di-C ₃ ~C ₁₂ cycloalkanediyl, C ₆ ~C ₁₄ aryl, C ₁ ~C ₄ aryl-C ₆ ~C ₁₄ aryl-C ₁ ~C ₄ aryl, or C ₆ ~C ₁₄ aryl -C ₁ ~C ₄ alkylene group -C ₆ ~C ₁₄ arylylene group (herein, the alkylene group is straight chain or branched chain, and can be substituted by halogen, C ₃ ~C ₁₂ cycloalkylene group or C The ₆ -C ₁₄ aryl group may be unsubstituted or may be substituted by halogen or C ₁ -C ₄ alkyl)).

(In the formula, X ² is a C ₁ ~C ₁₂ alkyl group, a C ₂ ~C ₁₂ alkyl group, a C ₁ ~C ₁₂ alkyloxy group interrupted by one or more O atoms (oxygen atoms) discontinuously Carbonyl alkylene, C ₃ ~C ₁₂ cycloalkyl, C ₁ ~C ₁₂ alkyl-C ₃ ~C ₁₂ cycloalkyl, C ₃ ~C ₁₂ cycloalkyl-C ₁ ~C ₁₂ alkylene-C ₃ ~C ₁₂ cycloalkylene, C ₆ ~C ₁₄ aryl, C ₁ ~C ₄ alkyl-C ₆ ~C ₁₄ aryl, C ₆ ~C ₁₄ aryl-C ₁ ~C ₄ alkylene -C ₆ ~C ₁₄ aryl (here, the alkyl is straight chain or branched, and can be substituted by halogen, C ₃ ~C ₁₂ cycloalkyl, C ₃ ~C ₁₂ cycloalkyl, C ₆ ~C ₁₄ aryl or C ₆ ~C ₁₄ aryl can be unsubstituted or can be substituted by halogen or C ₁ -C ₄ alkyl) or (meth)acryloxyalkyl).

In this specification, alone or in combination with other terms, "C ₁ ~C ₁₂ alkyl" is a straight chain or branched chain, which may also be substituted by halogen, or one or more O atoms (oxygen atom ) is non-continuously interrupted, preferably a straight chain. The carbon number range of the alkyl group is, for example, C ₁ ~C ₁₂ , more preferably C ₁ ~C ₈ , even more preferably C ₁ ~C ₆ , especially preferably C ₁ ~C ₄ . Specific examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl , n-dodecyl and other straight chains, isopropyl, isobutyl, second butyl, third butyl, 2-methylbutyl, isooctyl, third octyl, 2-ethyl Branched chains of hexyl, third nonyl, etc. Examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The halogen as a substituent is preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom. The number of substitutions is 1-12, preferably 1-6, more preferably 1-4, particularly preferably 1-3.

In this specification, alone or in combination with other terms, "C ₁ ~C ₁₂ alkylene" is a straight chain or branched chain, and may be substituted by halogen, or one or more NH (imine) group) or O atom (oxygen atom) non-continuously interrupted (H atom (hydrogen atom) bonded to N atom (nitrogen atom) can be substituted by amino group or C ₁ ~C ₁₂ alkylamine group), preferably straight chain. The carbon number range of the alkylene group is, for example, C ₁ ~C ₁₂ , more preferably C ₁ ~C ₈ , even more preferably C ₁ ~C ₆ , especially preferably C ₁ ~C ₄ . Specific examples thereof include methylene, ethylene, trimethylene, propylene, tetramethylene, 1-methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene Methyl, pentamethylene, 1-methyltetramethylene, 4-methyltetramethylene, hexamethylene, 5-methylpentamethylene, heptamethylene, octamethylene, Nonamethylene, Decamethylene, Undecamethylene, Dodecamethylene, etc. Examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The halogen as a substituent is preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom. The number of substitutions is 1-12, preferably 1-6, more preferably 1-4, particularly preferably 1-3.

In this specification, the carbon number of the alkyloxy or alkyleneoxy group of "C ₁ ~C ₁₂ alkyloxycarbonylalkylene" or "C ₁ ~C ₁₂ alkyleneoxycarbonylalkylene" The range is, for example, C ₁ ~C ₁₂ , more preferably C ₁ ~C ₈ , more preferably C ₁ ~C ₆ , particularly preferably C ₁ ~C ₄ . Specific examples thereof include, for example, methoxycarbonylmethylene, ethoxycarbonylmethylene, n-propoxycarbonylmethylene, n-butoxycarbonylmethylene, n-pentoxycarbonylmethylene , n-hexyloxycarbonylmethylene, n-heptyloxycarbonylmethylene, n-octyloxycarbonylmethylene, n-nonyloxycarbonylmethylene, n-decyloxycarbonylmethylene, n-undecyloxy Straight chains such as ylcarbonylmethylene, n-dodecyloxycarbonylmethylene, isopropoxycarbonylmethylene, isobutoxycarbonylmethylene, second butoxycarbonylmethylene, 3-butoxycarbonylmethylene, 2-methylbutoxycarbonylmethylene, isooctyloxycarbonylmethylene, 3-octyloxycarbonylmethylene, 2-ethylhexyloxycarbonylmethylene Branched chains such as methyl groups.

In this specification, alone or in combination with other terms, the carbon number range of "C ₃ ~C ₁₂ cycloalkyl" is for example C ₃ ~C ₁₂ , more preferably C ₃ ~C ₈ , and more preferably C ₃ ~C ₆ , particularly preferably in the range of C ₄ ~C ₆ . Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl . C ₃ -C ₁₂ cycloalkyl is preferably cyclopentyl or cyclohexyl. C ₃ -C ₁₂ cycloalkyl is unsubstituted or may be substituted by halogen or C ₁ -C ₄ alkyl, examples of halogen include fluorine atom, chlorine atom, bromine atom and iodine atom. The halogen as a substituent is preferably a fluorine atom or a chlorine atom, more preferably a chlorine atom. Examples of C ₁ -C ₄ alkyl groups as substituents include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl and third-butyl. The C ₁ -C ₄ alkyl as a substituent is preferably methyl, ethyl or n-propyl, more preferably methyl or ethyl. When having a substituent, the number of substitutions is 1 to 5, preferably 1 to 3, more preferably 1 to 2, most preferably 1.

In this specification, alone or in combination with other terms, the carbon number range of "C ₃ ~ C ₁₂ cycloalkylene" is for example C ₃ ~C ₁₂ , more preferably C ₃ ~C ₈ , and more preferably C ₃ ~C ₆ , particularly preferably in the range of C ₄ ~C ₆ . Specific examples thereof include cyclopropyl, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononyl, cyclodecylene, cyclodecylene Monoalkyl and cyclododecyl. The C ₃ -C ₁₂ cycloalkylene group is preferably a cyclopentylene group or a cyclohexylene group. The C ₃ -C ₁₂ cycloalkylene group is unsubstituted or may be substituted by halogen or C ₁ -C ₄ alkyl group, and the halogen is exemplified by fluorine atom, chlorine atom, bromine atom and iodine atom. The halogen as a substituent is preferably a fluorine atom or a chlorine atom, more preferably a chlorine atom. Examples of C ₁ -C ₄ alkyl groups as substituents include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl and third-butyl. The C ₁ -C ₄ alkyl as a substituent is preferably methyl, ethyl or n-propyl, more preferably methyl or ethyl. When having a substituent, the number of substitutions is 1 to 4, preferably 1 to 3, more preferably 1 to 2, particularly preferably 1.

In this specification, "C ₆ -C ₁₄ aryl" is a monovalent group having at least one aromatic ring alone or in combination with other terms. Specific examples thereof include, for example, phenyl, biphenyl, naphthyl, anthracenyl, and phenanthrenyl. Preferably it is phenyl, biphenyl or naphthyl, more preferably phenyl or naphthyl. The C ₆ -C ₁₄ aryl group is unsubstituted or may be substituted by a halogen or a C ₁ -C ₄ alkyl group, and the halogen is exemplified by a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The halogen as a substituent is preferably a fluorine atom or a chlorine atom, more preferably a chlorine atom. Examples of C ₁ -C ₄ alkyl groups as substituents include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl and third-butyl. The C ₁ -C ₄ alkyl as a substituent is preferably methyl, ethyl or n-propyl, more preferably methyl or ethyl. When having a substituent, the number of substitutions is 1 to 5, preferably 1 to 3, more preferably 1 to 2, particularly preferably 1.

In this specification, "C ₆ -C ₁₄ arylenyl" is a divalent group having at least one aromatic ring alone or in combination with other terms. Specific examples thereof include, for example, phenylene, naphthylene, anthracenyl, and phenanthrene. Preferably it is a phenylene group and a naphthylene group, More preferably, it is a phenylene group or a naphthylene group. The C ₆ -C ₁₄ aryl group is unsubstituted or may be substituted by halogen or C ₁ -C ₄ alkyl, and the halogen is exemplified by fluorine atom, chlorine atom, bromine atom and iodine atom. The halogen as a substituent is preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a fluorine atom or a chlorine atom. Examples of C ₁ -C ₄ alkyl groups as substituents include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl and third-butyl. The C ₁ -C ₄ alkyl as a substituent is preferably methyl, ethyl or n-propyl, more preferably methyl or ethyl. When having a substituent, the number of substitutions is 1 to 4, preferably 1 to 3, more preferably 1 to 2, particularly preferably 1.

[(b2) A compound in which an imidazole compound is added to an epoxy resin] The imidazole compound is an imidazole compound that does not have a primary amino group in the molecule. Examples of such imidazole compounds include compounds containing an imidazole ring with an unsubstituted nitrogen atom at the 1-position, such as 2-methylimidazole, 2-undecyl Imidazole, 2-octadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole grade 2-methylimidazoline; and imidazoles containing substituted nitrogen atoms at position 1 Cyclic compounds such as 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1- Cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate and 1-cyanoethyl-2-phenylimidazolium trimellitate wait. The epoxy resin among the compounds to which an imidazole compound is added to an epoxy resin is exemplified in curable resin (A). EH-5011S (made by ADEKA Co., Ltd.) and FXR-1121 (made by T&K TOKA Co., Ltd.) are mentioned as a commercial item of the compound which added the imidazole compound to an epoxy resin.

[(b3) A compound in which a polyamine compound is added to at least one compound selected from the group consisting of epoxy resins, isocyanate compounds, and urea] (polyamine compound) The polyamine compound is a compound having at least 2 primary amine groups, and is exemplified by a diamine compound having 2 primary amine groups, a triamine compound having 3 primary amine groups, and the like.

(diamine compound with 2 primary amine groups) Although it does not specifically limit as a diamine compound which has two primary amino groups, For example, aliphatic diamine, alicyclic diamine, aromatic diamine etc. are mentioned. Moreover, as a specific example of the diamine compound which has two primary amino groups, the polyamine compound represented by following formula (5a) is mentioned.

式中，L為C₁ ~C₁₂ 伸烷基、經1個或1個以上之NH(亞胺基)或O原子(氧原子)非連續中斷之C₂ ~C₁₂ 伸烷基(鍵結於N原子(氮原子)之H原子(氫原子)可經胺基或C₁ ~C₁₂ 烷基胺基取代)、C₃ ~C₁₂ 伸環烷基、C₁ ~C₁₂ 伸烷基-C₃ ~C₁₂ 伸環烷基、C₁ ~C₁₂ 伸烷基-C₃ ~C₁₂ 伸環烷基-C₁ ~C₁₂ 伸烷基、C₃ ~C₁₂ 伸環烷基-C₁ ~C₄ 伸烷基-C₃ ~C₁₂ 伸環烷基、C₆ ~C₁₄ 伸芳基、C₁ ~C₄ 伸烷基-C₆ ~C₁₄ 伸芳基、C₁ ~C₄ 伸烷基-C₆ ~C₁₄ 伸芳基-C₁ ~C₄ 伸烷基、或C₆ ~C₁₄ 伸芳基-C₁ ~C₄ 伸烷基-C₆ ~C₁₄ 伸芳基(此處，伸烷基為直鏈或分支鏈，且可經鹵素取代，C₃ ~C₁₂ 伸環烷基或C₆ ~C₁₄ 伸芳基可未經取代或可經鹵素或C₁ -C₄ 烷基取代)

In the formula, L is a C ₁ ~C ₁₂ alkylene group, a C ₂ ~C ₁₂ alkylene group (bonding group) interrupted non-continuously by one or more NH (imino groups) or O atoms (oxygen atoms). The H atom (hydrogen atom) of the N atom (nitrogen atom) can be replaced by an amino group or a C ₁ ~C ₁₂ alkylamino group), a C ₃ ~C ₁₂ cycloalkylene group, a C ₁ ~C ₁₂ alkylene group- C ₃ ~C ₁₂ cycloalkylene, C ₁ ~C ₁₂ alkylene-C ₃ ~C ₁₂ cycloalkylene-C ₁ ~C ₁₂ alkylene, C ₃ ~C ₁₂ cycloalkylene-C ₁ ~C ₄ alkylene-C ₃ ~C ₁₂ cycloalkylene, C ₆ ~C ₁₄ aryl, C ₁ ~C ₄ alkylene-C ₆ ~C ₁₄ aryl, C ₁ ~C ₄ Alkyl-C ₆ ~C ₁₄ aryl-C ₁ ~C ₄ aryl, or C ₆ ~C ₁₄ aryl-C ₁ ~C ₄ aryl-C ₆ ~C ₁₄ aryl (this , the alkylene group is straight or branched and can be substituted by halogen, and the C ₃ ~C ₁₂ cycloalkylene group or C ₆ ~C ₁₄ arylylene group can be unsubstituted or can be substituted by halogen or C ₁ -C ₄ Alkyl substitution)

Among the aromatic diamines, as the compound in which L is a C ₁ ~C ₁₂ alkylene group in the formula (5a), specific examples include ethylenediamine, propylenediamine, 1,2-diaminopropane, 1,3- Diaminopropane, 1,3-diaminobutane, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, Dodecamethylenediamine, propane-1,2-diamine, 1,2-diamino-2-methylpropane, etc.

Among the aromatic diamines, as a compound in which L in the formula (5a) is a linear or branched _C1 - _C12 alkylene compound discontinuously interrupted by one or more O atoms (oxygen atoms), Specific examples include, for example, 2,2'-oxybis(ethylamine), 1,2-bis(2-aminoethoxy)ethane, 1,11-diamino-3,6,9-tri Oxaundecane, bis(3-aminopropyl) ether, 1,4-butanediol bis(3-aminopropyl) ether, diethylene glycol bis(3-aminopropyl) ether, Ethylene glycol bis(3-aminopropyl) ether, etc.

Among the aromatic diamines, as in the formula (5a), L is a linear or branched C ₂ ~C ₁₂ alkylene (bond) discontinuously interrupted by one or more NH (imide groups) The H atom (hydrogen atom) bonded to the N atom (nitrogen atom) can be replaced by an amine group or a C ₁ ~C ₁₂ alkylamine group), specifically exemplified such as diethylenetriamine, triethylenetetramine, Tetraethylenepentamine, Pentaethylenehexamine, Tris(2-aminoethyl)amine, N,N'-bis(3-aminopropyl)ethylenediamine, bis(hexamethylene)triamine , 3,3'-diamino-N-methyldipropylamine, 3,3'-diaminodipropylamine, bis(3-aminopropyl)methylamine, etc.

Specific examples of alicyclic diamines include isobornyl diamine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, trans-1,2-diaminocyclohexane , 1,3-bis(aminomethyl)cyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,4-diamino-3,6-diethylcyclohexane, Isobornyl diamine, etc.

Specific examples of aromatic diamines include, for example, p-phenylenediamine, m-phenylenediamine, o-xylylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4'-diamine Diphenylmethane, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminotoluene, 2,4-diamino-6-[2'-methylimidazoline Base-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolinyl-(1')]-ethyl-s-triazine oxazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolinyl-(1')]-ethyl-s-triazine, 2,4-diamino- 6-[2'-Methylimidazolinyl-(1')]-ethyl-s-triazine, isocyanuric acid adducts, etc., the 1st grade of imidazolinyl substituted with a nitrogen atom at the 1-position Diamine, diaminodiphenylsulfone, etc.

Specific examples of triamine compounds having three primary amine groups include tris(4-aminophenyl)amine, tris(3-aminopropyl)amine, tris(2-aminoethyl) represented by the following formula base) amine, diethylenetriamine, triethylenetriamine, tetraethylenetriamine, tetraethylenepentamine and other polyalkylene polyamines.

The polyamine compound in (b3) does not include hydrazine (NH ₂ NH ₂ ), hydrazide compound and (b1) carbazide compound. The polyamine compound in (b3) preferably does not contain a compound having a hydrazine group (NH ₂ NH—). Here, the hydrazide compound is exemplified by the hydrazide compound described later. In addition, polyamine compounds other than (b3) include hydrazine compounds, hydrazide compounds, and (b1) carbazide compounds. However, the polyamine compound other than (b3) may also include hydrazine, hydrazide compound and (b1) carbazide compound.

(epoxy resin) As an epoxy resin in the compound which added the polyamine compound to an epoxy resin, what was illustrated in curable resin (A) is mentioned.

(isocyanate compound) As an isocyanate compound in the compound which added the polyamine compound to an isocyanate compound, what was illustrated in the isocyanate compound (C) mentioned later is mentioned.

Examples of commercially available products that are addition compounds of polyamine compounds and epoxy resins are EH-5001P, EH-4370S, EH-5015S, EH-4375S, EH-5030S, EH-5057P, and EH-4358S (the above are ADEKA shares Co., Ltd.), FXR-1020, FXR-1030, FXR-1081 (the above are made by T&K TOKA Co., Ltd.).

(better form) From the viewpoint of further improving the reactivity with the curable resin (A) and shortening the curing time, as (b3) adding a polyamine to at least one compound selected from the group consisting of epoxy resins, isocyanate compounds, and urea The compound is preferably a compound obtained by adding a polyamine compound to an isocyanate compound.

[(b4) Mixed crystals of 2 or more hydrazide compounds, (b5) Mixed crystals of 1 or more mono- or polyamine compounds and 1 or more hydrazide compounds, and (b6) 1 or more imidazole compounds and Mixed crystal of more than one hydrazine compound] Mixed crystals of two or more hydrazide compounds, mixed crystals of one or more mono- or polyamine compounds and one or more hydrazide compounds, and mixed crystals of one or more imidazole compounds and one or more hydrazide compounds It is a mixed crystal having a crystal system different from that of the individual components contained in the mixed crystal. Mixed crystals can be identified by comparing the X-ray diffraction spectrum of the mixed crystal with the X-ray diffraction spectrum of a single monomer or polyamine compound contained in the raw material contained in the mixed crystal, and confirming the presence of peaks other than those derived from the raw material existence. Examples of the hydrazide compound in these mixed crystals include those exemplified in the hydrazide compound described later. As the polyamine compound in the mixed crystal of (b5) one or more kinds of mono- or polyamine compounds and one or more kinds of hydrazine compounds, for example, the group formed from epoxy resin, isocyanate compound and urea in (b3) Examples are those in which at least one selected compound is added to a polyamine compound. Examples of (b6) mixed crystals of one or more imidazole compounds and one or more hydrazide compounds are those exemplified in (b2) Compounds in which imidazole compounds are added to epoxy resins.

(hydrazine compound) Examples of the hydrazine compound include hydrazine monobasic acid having one hydrazine group in the molecule, hydrazine dibasic acid having 2 hydrazine groups in the molecule, hydrazine tribasic acid having 3 hydrazine groups in the molecule, Polyfunctional hydrazines with more than 4 hydrazine groups in the molecule.

Specific examples of monobasic acid hydrazide include acetylhydrazine, propionate, valerate, laurate, cyclohexane hydrazine, salicylic acid hydrazide, p-hydroxybenzoic acid hydrazide, and naphthoic acid. Hydrazine, benzenesulfonylhydrazine.

Specific examples of dihydrazide dibasic acid include dihydrazide oxalate, dihydrazide malonate, dihydrazide succinate, dihydrazide adipate, dihydrazide pimelate, dihydrazide suberate, azelaic acid, Dihydrazine sebacate, dihydrazine sebacate, dihydrazine dodecanoate, dihydrazine hexadecanoate, dihydrazide isophthalate, dihydrazine terephthalate, formhydrazine, maleic acid Dihydrazine acid, Dihydrazine fumarate, Dihydrazine diglycolate, Dihydrazine tartrate, Dihydrazine malate, Dihydrazine 2,6-naphthoate, Dihydrazine 1,4-naphthoate, 4,4'-diphenylhydrazine, diglycolic acid dihydrazine hydroquinone, resorcinol diglycolic acid dihydrazine, catechol diglycolic acid dihydrazine, 4,4'-ethylene diglycolic acid dihydrazine Phenol diglycolic acid dihydrazide, 4,4'-vinylidene bisphenol diglycolic acid dihydrazide, etc.

Examples of hydrazine tribasic acid include 1,3,5-tris(2-hydrazinecarbonylalkyl)isocyanurate such as 1,3,5-tris(2-hydrazinecarbonylethyl)isocyanurate Esters etc. As polyfunctional hydrazine, polyacrylic acid hydrazine etc. are mentioned, for example.

Also, when the hydrazine compound is a combination of two or more hydrazine compounds, it is preferable that at least one of the hydrazine compounds is a dibasic acid dihydrazide, and it is especially more preferable that all the hydrazine compounds are dibasic acid dihydrazides. As a combination of hydrazine compounds in which all the hydrazine compounds are dibasic acid dihydrazides, for example, adipate dihydrazide and sebacic acid dihydrazide, adipate dihydrazide and sebacate dihydrazide , dihydrazide sebacic acid and dihydrazine sebacate, dihydrazine sebacate and dihydrazine dodecanedioic acid, etc., more preferably dihydrazine sebacate and dihydrazine A combination of hydrazines.

Mixed crystals of two or more hydrazine compounds have about 2-3 strong diffraction peaks observed between 20-25° of the Bragg angle (2θ±0.2°) in the X-ray diffraction spectrum using CuKα rays Crystal metamorphosis. Also, the hydrazine compound used in the mixed crystallization is preferably a crystalline hydrazine compound. Here, the crystalline hydrazide compound means a hydrazide compound having a peak in the range of 5.0 to 7.5° of the Bragg angle 2θ (error 2θ±0.2°) in the X-ray diffraction spectrum with respect to CuKα rays (wavelength 1.541Å) .

(composition of mixed crystals, etc.) The combination ratio of mono- or polyamine compound, imidazole compound and/or hydrazine compound used in the mixed crystallization can be appropriately determined according to various conditions such as the type of epoxy resin to be cured, the application, the required curing time or curing temperature, etc. . For example, it is preferable to use two or more compounds in combination so that one compound in all mixed crystals contains usually 1 to 99% by weight, preferably 10 to 90% by weight, more preferably 30 to 70% by weight.

(Constituents further contained in mixed crystals) The mixed crystal may further contain a metal element that can form a complex with a compound contained in the mixed crystal. It is preferable because mixed crystals containing metal elements can further enhance the effect of improving the stability of the liquid. It is preferably a mixed crystal of two or more hydrazide compounds containing a metal element that can form a complex with the hydrazide compound in the mixed crystal of two or more hydrazide compounds.

Preferred examples of metal elements are aluminum, titanium, tin, zirconium, zinc, iron, magnesium, cobalt, nickel, bismuth, molybdenum, copper, antimony, barium, boron, manganese, indium, cesium, yttrium, silicon, At least one selected from the group consisting of calcium, silver, cadmium and gold. The metal element is more preferably at least one selected from the group consisting of aluminum, titanium, tin, zirconium, zinc, iron, magnesium, cobalt, nickel, bismuth, molybdenum, copper, antimony, barium, and boron. Metal elements may be used alone or in any combination of two or more. In addition, metal elements can be used in the form of metal oxides and metal hydroxides.

The content of the metal element is preferably from 0.1 to 20.0% by mass, more preferably from 1.0 to 10.0% by mass, based on the total amount of the mixed crystal and the metal element. When the content of the metal element is 0.1-20.0% by mass relative to the total amount of the compound and the metal element contained in the mixed crystal, it is presumed that the metal element and the compound contained in the mixed crystal, such as a crystalline hydrazine compound, form a good complex thing.

(Manufacturing method of mixed crystal) The production method of mixed crystals is a method comprising the following steps: combining two or more amine compounds (that is, a combination of two or more hydrazide compounds, one or more mono- or polyamine compounds and one or more hydrazide compounds) as raw materials or a combination of one or more imidazole compounds and one or more hydrazide compounds) are heated and melted above the melting point and mixed to obtain a mixture, and the mixture is cooled and solidified. Specifically, the method for producing mixed crystals is a method comprising the following steps: combining (b4') two or more hydrazine compounds, (b5') one or more mono- or polyamine compounds (with one Combinations of the above primary mono-, di- and polyamine compounds with primary amine groups, and secondary mono-, di- and polyamine compounds with one or more secondary amine groups in the molecule) and more than one hydrazine compound, and (b6 ') two or more amine compounds selected from a group consisting of a combination of one or more imidazole compounds and one or more hydrazide compounds are heated and melted at a temperature above the melting point, mixed to obtain a mixture, and the mixture is cooled and solidified the steps.

In the heat-melting and mixing step, the temperature at which the two or more amine compounds of the raw materials are heated is not particularly limited, but is preferably a temperature at which the mixture of the two or more amine compounds of the raw materials becomes substantially liquid. The temperature at which the mixture of two or more amine compounds used as raw materials becomes substantially liquid is preferably a temperature near the melting point of the two or more amine compounds used as raw materials, for example, from a temperature about 10°C lower than the melting point to a temperature lower than the melting point. The temperature is about 10°C higher. Here, the melting point of the two or more kinds of amine compounds of the raw material means the temperature at which the melting point is the highest among the melting points of the two or more kinds of amine compounds of the raw material.

The cooling rate in the step of cooling and solidifying the molten mixture of two or more amine compounds as raw materials is preferably from 20 to 0.01°C/min, more preferably from 10 to 0.05°C/min, still more preferably from 5 to 0.1°C/min. minute. Cooling can be performed in multiple stages, for example, in two stages. For example, it can be cooled to 100-50° C. in the first stage, crystals are grown at this temperature, and cooled to room temperature in the second stage.

Also, the method for producing a mixed crystal of two or more amine compounds comprising the raw material and a mixed crystal of a metal capable of forming a complex with the amine compound of the raw material comprises making a mono- or poly-amine compound, an imidazole compound or a hydrazide compound, A step of heating, melting and mixing with a metal element that can form a complex with a mono- or polyamine compound, an imidazole compound or an hydrazide compound to obtain a mixture, a step of constant temperature treatment of the mixture, and a step of cooling the mixture to obtain a solidified body.

The steps of heating, melting and mixing to obtain a mixture and cooling the mixture to obtain a solidified body are as described above. The step of subjecting the mixture to constant temperature treatment is a step of subjecting the mixture to constant temperature treatment at a certain time and temperature. The so-called constant temperature treatment means keeping the mixture at a certain temperature (error range ±10° C.) for a certain period of time. The temperature of the constant temperature treatment is not particularly limited, but is preferably from 100 to 280°C, more preferably from 130 to 250°C. The time for constant temperature treatment is not particularly limited, and it can be set as the most suitable treatment time, for example, 0.01 to 10 hours, in accordance with the purpose of use when used as a hardener.

Furthermore, the method for producing mixed crystals preferably includes the step of pulverizing the solidified body obtained by cooling to a granular shape with an average particle diameter of 0.1 to 20.0 μm. As a pulverization method, it is preferable to pulverize the solidified body using, for example, a high-pressure pulverizer. Examples of the high-pressure mill include a cross jet mill (manufactured by Kurimoto Iron Works Co., Ltd.), a reverse jet mill (manufactured by HOSOKAWA MICRO), and a dry jet mill (Nano Jetmizer) (manufactured by AISHIN NANO TECHNOLOGY).

(Preferable aspect of latent curing agent (B)) The latent curing agent (B) preferably has a granular form. The average particle size of the latent hardener (B) is not particularly limited, but is preferably from 0.1 to 20.0 μm, more preferably from 0.2 to 10.0 μm. In addition, the average particle size can be obtained by a particle size distribution measuring device using the laser diffraction and scattering method, and the average particle size is the volume average value _D50 ( _D50 It is the measured value of the particle diameter when the cumulative volume becomes 50%, that is, the median diameter). The latent hardener (B) having a granular form can be obtained by pulverizing the latent hardener (B).

3. Isocyanate compound (C) The isocyanate compound is a compound having at least one isocyanate group (-N=C=O), and is not particularly limited, but examples thereof include monoisocyanate compounds, diisocyanate compounds, triisocyanate compounds, and tetraisocyanate compounds.

式(1a)中，X⁴ 為C₁ ~C₁₂ 烷基、經1個或1個以上之O原子(氧原子)非連續中斷之C₂ ~C₁₂ 烷基、C₁ ~C₁₂ 烷基氧基羰基伸烷基、C₃ ~C₁₂ 環烷基、C₁ ~C₁₂ 烷基-C₃ ~C₁₂ 伸環烷基、C₃ ~C₁₂ 環烷基-C₁ ~C₁₂ 伸烷基-C₃ ~C₁₂ 伸環烷基、C₆ ~C₁₄ 芳基、C₁ ~C₄ 烷基-C₆ ~C₁₄ 伸芳基、C₆ ~C₁₄ 芳基-C₁ ~C₄ 伸烷基-C₆ ~C₁₄ 伸芳基(此處，伸烷基為直鏈或分支鏈，且可經鹵素取代，C₃ ~C₁₂ 環烷基、C₃ ~C₁₂ 伸環烷基、C₆ ~C₁₄ 芳基或C₆ ~C₁₄ 伸芳基可未經取代或可經鹵素或C₁ -C₄ 烷基取代)或(甲基)丙烯醯氧基烷基。(Monoisocyanate compound) As a monoisocyanate compound, the compound represented by following formula (1a) is mentioned.

In formula (1a), X ⁴ is C ₁ ~C ₁₂ alkyl, C ₂ ~C ₁₂ alkyl, C ₁ ~C ₁₂ alkyl interrupted by one or more O atoms (oxygen atoms) discontinuously Oxycarbonyl alkylene, C ₃ ~C ₁₂ cycloalkyl, C ₁ ~C ₁₂ alkyl-C ₃ ~C ₁₂ cycloalkylene, C ₃ ~C ₁₂ cycloalkyl-C ₁ ~C ₁₂ alkylene Base-C ₃ ~C ₁₂ cycloalkylene, C ₆ ~C ₁₄ aryl, C ₁ ~C ₄ alkyl-C ₆ ~C ₁₄ aryl, C ₆ ~C ₁₄ aryl-C ₁ ~C ₄ Alkylene-C ₆ ~C ₁₄ arylylene (here, the alkylene is straight chain or branched, and can be substituted by halogen, C ₃ ~C ₁₂ cycloalkyl, C ₃ ~C ₁₂ cycloalkyl , C ₆ ~C ₁₄ aryl or C ₆ ~C ₁₄ aryl may be unsubstituted or may be substituted by halogen or C ₁ -C ₄ alkyl) or (meth)acryloxyalkyl.

式(1b)，R⁶ 表示氫原子或甲基，R⁷ 表示C₁ ~C₆ 伸烷基。R⁷ 之C₁ ~C₆ 伸烷基的碳數範圍較好為C₂ ~C₆ ，更好為C₃ ~C₆ 。The (meth)acryloxyalkyl isocyanate as a monoisocyanate compound is illustrated by the compound represented by following formula (1b).

In formula (1b), R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents a C ₁ ~C ₆ alkylene group. The carbon number range of the C ₁ -C ₆ alkylene group of R ⁷ is preferably C ₂ -C ₆ , more preferably C ₃ -C ₆ .

Specific examples of monoisocyanate compounds include methyl isocyanate, ethyl isocyanate, n-hexyl isocyanate, cyclohexyl isocyanate, 2-ethylhexyl isocyanate, phenyl isocyanate, isocyanate, Benzyl cyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, amyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, isocyanate Tributyl, ethyl isocyanatoacetate, butyl isocyanatoacetate, (S)-(-)-2-methylisocyanatopropionate, phenyl isocyanate, 1-naphthyl isocyanate, isocyanate 4-chlorophenyl ester, 4-fluorophenyl isocyanate, phenylethyl isocyanate, p-cresyl isocyanate, m-cresyl isocyanate, 3,5-dimethylphenyl isocyanate , 3-(triethoxysilyl)propyl isocyanate, etc.

Specific examples of (meth)acryloxyalkyl isocyanate include (meth)acryloxymethyl isocyanate, (meth)acryloxyethyl isocyanate, (meth)acryloxypropyl isocyanates, etc.

式(2a)中，X⁵ 為C₁ ~C₁₂ 伸烷基、經1個或1個以上之O原子(氧原子)非連續中斷之C₂ ~C₁₂ 伸烷基、C₁ ~C₁₂ 伸烷基氧基羰基伸烷基、C₃ ~C₁₂ 伸環烷基、C₁ ~C₁₂ 伸烷基-C₃ ~C₁₂ 伸環烷基、C₁ ~C₁₂ 伸烷基-C₃ ~C₁₂ 伸環烷基-C₁ ~C₁₂ 伸烷基、C₃ ~C₁₂ 伸環烷基-C₁ ~C₁₂ 伸烷基-C₃ ~C₁₂ 伸環烷基、二- C₃ ~C₁₂ 環烷二基、C₆ ~C₁₄ 伸芳基、C₁ ~C₄ 伸烷基-C₆ ~C₁₄ 伸芳基-C₁ ~C₄ 伸烷基、或C₆ ~C₁₄ 伸芳基-C₁ ~C₄ 伸烷基-C₆ ~C₁₄ 伸芳基(此處，伸烷基為直鏈或分支鏈，且可經鹵素取代，C₃ ~C₁₂ 伸環烷基或C₆ ~C₁₄ 伸芳基可未經取代或可經鹵素或C₁ -C₄ 烷基取代)。(Diisocyanate compound) As a diisocyanate compound, the compound represented by following formula (2a) is mentioned.

In formula (2a), X ⁵ is a C ₁ ~C ₁₂ alkylene group, a C ₂ ~C ₁₂ alkylene group interrupted by one or more O atoms (oxygen atoms), C ₁ ~C ₁₂ Alkylene oxycarbonyl alkylene, C ₃ ~C ₁₂ cycloalkylene, C ₁ ~C ₁₂ alkylene-C ₃ ~C ₁₂ cycloalkylene, C ₁ ~C ₁₂ alkylene-C ₃ ~C ₁₂ cycloalkylene- _{C 1} ~C ₁₂ alkylene, C ₃ ~C ₁₂ cycloalkylene-C ₁ ~C ₁₂ alkylene-C ₃ ~C ₁₂ cycloalkylene, di-C ₃ ~C ₁₂ cycloalkanediyl, C ₆ ~C ₁₄ aryl, C ₁ ~C ₄ aryl-C ₆ ~C ₁₄ aryl-C ₁ ~C ₄ aryl, or C ₆ ~C ₁₄ Arylylene-C ₁ ~C ₄ alkylene-C ₆ ~C ₁₄ arylylene (here, the alkylene is straight chain or branched, and can be substituted by halogen, C ₃ ~C ₁₂ cycloalkylene Or C ₆ ~C ₁₄ aryl groups may be unsubstituted or may be substituted by halogen or C ₁ -C ₄ alkyl).

Specific examples of diisocyanate compounds include, for example, diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), xylene diisocyanate (XDI), hydrogenated xylene diisocyanate (hydrogenated XDI), isophorone diisocyanate (IPDI), ), benzylidine diisocyanate (TPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), 2,4,4-trimethylhexamethylene diisocyanate (TMHDI), 3,5,5-Trimethylhexamethylene diisocyanate (TMHDI), 4,4'-diisocyanate 3,3'-dimethylbiphenyl, 4,4'-diisocyanate 3,3' -Dimethyldiphenylmethane, 2,2-bis(4-isocyanatophenyl)hexafluoropropane, 2,4-diisocyanatotoluene, 1,3-bis(2-isocyanato-2-propyl) Benzene, toluene-2,6-diisocyanate, 1,4-benzenediisocyanate, 1,3-benzenediisocyanate, 1,5-diisocyanatonaphthalene, etc.

式中，R² 為相同或不同，為直鏈或分支鏈的C₁ ~C₁₂ 伸烷基。(Triisocyanate Compound) As a triisocyanate compound, a compound having an isocyanurate structure, a biuret structure, or an adduct structure having an isocyanate group at the 3 terminal is exemplified. As a triisocyanate compound which has an isocyanurate structure, the compound which has an isocyanurate structure represented by following formula (3a) is mentioned.

In the formula, R ² are the same or different, and are linear or branched C ₁ -C ₁₂ alkylene groups.

式中，R³ 為相同或不同，為直鏈或分支鏈的C₁ ~C₁₂ 伸烷基。As a triisocyanate compound which has a biuret structure, the compound represented by following formula (3b) is mentioned.

In the formula, R ³ are the same or different, and are linear or branched C ₁ -C ₁₂ alkylene groups.

式中，R⁴ 為相同或不同，為直鏈或分支鏈的C₁ ~C₁₂ 伸烷基，R⁵ 為CH。Examples of the triisocyanate compound having an adduct structure include compounds represented by the following formula (3c).

In the formula, R ⁴ is the same or different, and is a linear or branched C ₁ ~ C ₁₂ alkylene group, and R ⁵ is CH.

Specific examples of the triisocyanate compound include, for example, tris(isocyanatomethyl)isocyanurate, tris(isocyanatoethyl)isocyanurate, tris(isocyanatopropyl)isocyanurate, tris(isocyanate butyl) isocyanurate, tris(isocyanatohexyl) isocyanurate, N,N'-2-paraisocyanatomethylmalonamide, N,N'-2-paraffin- Isocyanatohexylmalonamide, etc.

式中，X³ 為C₃ ~C₁₂ 環烷基-C₁ ~C₁₂ 伸烷基-C₃ ~C₁₂ 環烷基或C₆ ~C₁₄ 芳基-C₁ ~C₄ 伸烷基-C₆ ~C₁₄ 芳基(伸烷基為直鏈或分支鏈，且可經鹵素取代，C₃ ~C₁₂ 環烷基或C₆ ~C₁₄ 芳基可未經取代或可經鹵素或C₁ -C₄ 烷基取代。(Tetraisocyanate compound) As a tetraisocyanate compound, the tetravalent group derived from the compound represented by following formula (4a) is mentioned.

In the formula, X ³ is C ₃ ~C ₁₂ cycloalkyl-C ₁ ~C ₁₂ alkylene-C ₃ ~C ₁₂ cycloalkyl or C ₆ ~C ₁₄ aryl-C ₁ ~C ₄ alkylene- C ₆ ~C ₁₄ aryl (alkylene is straight chain or branched, and can be substituted by halogen, C ₃ ~C ₁₂ cycloalkyl or C ₆ ~C ₁₄ aryl can be unsubstituted or can be substituted by halogen or C ₁ -C ₄ alkyl substitution.

Moreover, tetraisocyanate silane represented by following formula (4b) is mentioned as a tetraisocyanate compound.

Specific examples of the tetraisocyanate compound include, for example, 4,4'-diphenylmethane-2,2',5,5'-tetraisocyanate, tetraisocyanate silane, and the like.

4. Manufacturing method A method for producing a curable resin composition is a method for producing a curable resin composition comprising a curable resin (A), a latent hardener (B) and an isocyanate compound (C), and includes A step of mixing the curable resin (A), the latent hardener (B), the isocyanate compound (C) and optional components without previously reacting the latent hardener (B) and the isocyanate compound (C). The mixing method can be to mix the curable resin (A) and the isocyanate compound (C) after stirring and mixing the latent hardener (B), or to mix the curable resin (A) and the latent hardener (B) after stirring , stirring and mixing the isocyanate compound (C). The temperature during mixing is near the melting point of the latent hardener (B) to be mixed or the temperature in the reactive temperature range will cause the hardening resin (A) and latent hardener (B) to react, so it is not good . And when the mixing temperature is too low, the fluidity of the resin is inhibited and it is difficult to stir. Therefore, the temperature during mixing is preferably from 0 to 40°C, more preferably from 10 to 40°C, and still more preferably from 20 to 40°C.

In the conventional production method of a curable resin composition, a latent hardener and an isocyanate compound are reacted in advance, and the surface of the latent hardener is coated with an isocyanate compound and added to the curable resin composition. However, in the present invention, the curable resin composition can be easily produced only by including the step of mixing the curable resin (A), the latent hardener (B) and the isocyanate compound (C). The reason for this is considered to be that when the curable resin (A), the latent curing agent (B) and the isocyanate compound (C) are mixed, the latent curing agent (B) has a high reactivity with the isocyanate compound (C), so the In the mixed composition, the reaction between the amine group on the surface of the latent hardener and the isocyanate compound is promoted.

5. Status of latent hardener (B) and isocyanate compound (C) As described above, the curable resin composition is prepared by mixing the curable resin (A), the latent hardener (B) and the isocyanate compound (C) without reacting the latent hardener (B) and the isocyanate compound (C) in advance. ) are produced by mixing. When the curable resin (A), latent curing agent (B) and isocyanate compound (C) were mixed in this way, it was confirmed that the amount of surface amine groups of the latent curing agent (B) decreased. Here, the amount of surface amine groups refers to the amount of amine groups existing on the surface or surface layer of the granular latent hardener (B). Therefore, part or all of the latent hardener (B) reacts with part or all of the isocyanate compound (C). Preferably, all of the latent hardener (B) reacts with all of the isocyanate compound (C). For example, when the latent hardener (B) is fully reacted, the latent hardener (B) in the curable resin composition does not contain an unreacted state, but if it is confirmed that the latent hardener (B) and the isocyanate compound ( The reactant of C) becomes the curable resin composition of the present invention. When a part or all of the latent hardener (B) reacts with a part or all of the isocyanate compound (C), at least a part of the surface of the latent hardener (B) reacts with the isocyanate compound (C). That is, since the latent hardener (B) has a high reactivity with the isocyanate compound (C), it is considered that after the latent hardener (B) is mixed with the isocyanate compound (C), the isocyanate compound (C) Added to the surface of latent hardener (B). Therefore, in the curable resin composition, the amount of surface amines in the latent curing agent (B) decreases with the passage of time.

The state of the reaction between the latent hardener (B) and the isocyanate compound (C) is presumed to be the reaction between the reactive isocyanate group in the isocyanate compound (C) and the primary amine group and/or secondary amine group of the latent hardener (B). , forming a state of urea bond, biuret bond or allophanate bond.

6. Deployment volume The curable resin composition preferably contains 1 to 100 parts by mass of the latent curing agent (B), more preferably 2 to 70 parts by mass, and more preferably 2 to 50 parts by mass, relative to 100 parts by mass of the curable resin (A). share. In addition, the curable resin composition preferably contains 0.0002 to 28 parts by mass, more preferably 0.002 to 28 parts by mass, and more preferably 0.02 to 28 parts by mass, relative to 100 parts by mass of the curable resin (A). . Such a blending ratio is preferable from the standpoint of liquid stability and hardening properties of the composition.

In addition, the curable resin composition preferably contains 0.02 to 28 parts by mass, more preferably 0.04 to 28 parts by mass, and more preferably 0.05 to 25 parts by mass of the isocyanate compound (C) relative to 100 parts by mass of the latent hardener (B). parts by mass. Such a blending ratio is preferable from the standpoint of liquid stability and hardening properties of the composition.

7. Other ingredients The curable resin composition preferably contains a photopolymerization initiator (D), and other inorganic fillers (E), organic fillers (F), and coupling agents (G) as needed, in addition to the above components.

[Photopolymerization initiator (D)] Examples of photopolymerization initiators include benzophenone, 2,2-diethoxyacetophenone, diphenamide, benzoyl isopropyl ether, benzyl dimethyl acetal, 1-hydroxycyclohexyl Phenyl ketone, thioxanthone, etc. Moreover, a commercially available photoradical polymerization initiator can also be used as a photoinitiator. Commercially available photoradical polymerization initiators are, for example, IRGACURE 907, IRGACURE 819, IRGACURE 651, IRGACURE 369, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, LUCIRIN TPO (the above are BASF JAPAN Corporation), etc.

[Inorganic filler (E)] Although it does not specifically limit as an inorganic filler, For example, spherical silica, spherical alumina, spherical titanium oxide, spherical alumina, spherical calcium carbonate etc. are mentioned, for example. Among them, spherical silicon oxide is preferable because of excellent dispersibility, adhesiveness of a sealant suitable for the liquid crystal dropping method, and excellent effect of improving the moisture resistance of a cured product.

The mixing ratio of each component of the curable resin composition is preferably 0.5 to 10 parts by mass, more preferably 0.5 to 7 parts by mass, of the photopolymerization initiator (D) relative to 100 parts by mass of the curable resin composition, More preferably, it is 0.8 to 4 parts by mass. And, with respect to 100 mass parts of curable resin compositions, the inorganic filler (E) is preferably 0-40 mass parts, more preferably 2-30 mass parts, still more preferably 3-20 mass parts. And, it is preferable that it is 0.5-3 mass % of (D) photoinitiators in the gross mass of a liquid crystal sealing compound composition. Moreover, it is preferable that it is 0-40 mass % of (E) inorganic filler in the gross mass of a liquid crystal sealing compound composition.

The curable resin composition is preferably prepared by kneading thoroughly with a coating roller, etc., paying special attention to the uniform and complete dispersion of solids such as inorganic fillers.

[Organic filler (F)] The organic filler is not particularly limited, and examples thereof include fine particles of monomers or polymers, specifically polyester fine particles, vinyl polymer fine particles, acrylic polymer fine particles, and polyurethane fine particles. Among them, an acrylic resin filler is preferred because of its excellent transparency.

[Coupling agent (G)] It does not specifically limit as a coupling agent, For example, a silane coupling agent is mentioned.

[other ingredients] The curable resin composition may contain silicone resin, urea resin, imide resin, glass, or the like as necessary, in addition to the above-mentioned resins.

In addition, in the curable resin composition, various additives such as antioxidants, ultraviolet absorbers, light stabilizers, coating improvers, thermal polymerization inhibitors, leveling agents, surfactants, and colorants can also be formulated as needed. , Preservation stabilizers, plasticizers, slip agents, inorganic particles, anti-aging agents, wettability modifiers, antistatic agents, etc.

[LCD panel] The curable resin composition can meet the diversification requirements for thinning lines and adhesiveness, and at the same time, it can exhibit the adhesive strength that can suppress peeling when cutting out the unit and installing the IC for liquid crystal driving, and can be better used for liquid crystal display panels manufacture. Therefore, it is preferable to use a curable resin composition as a sealing compound composition for liquid crystal display elements. In addition, the liquid crystal display panel includes an opposing glass substrate, a cured product of a curable resin composition adhering the opposing glass substrate, and a liquid crystal sealed with the opposing glass substrate and the cured product of the curable resin composition.

[Manufacturing method of liquid crystal display panel] A liquid crystal dropping method is known as one of the methods of manufacturing liquid crystal display elements such as a liquid crystal display unit. The liquid crystal dropping method is, for example, a method of forming a sealant frame for a liquid crystal display element on a substrate, dropping liquid crystal therein, and bonding another substrate to seal the liquid crystal to manufacture a liquid crystal display element. Recently, a curable resin composition of a combination of light and heat has been used, and after sandwiching two substrates, the curable resin composition is photocured by ultraviolet irradiation as the first stage, and then heat-cured as the second stage. . Also, a method of manufacturing a liquid crystal display unit by only photocuring a curable resin composition after dropping a liquid crystal, and a method of manufacturing a liquid crystal display unit only by thermal curing are examined. Moreover, the liquid crystal injection method is also known as one of other manufacturing methods. The liquid crystal injection method is, for example, when forming the frame of the sealant, the part that will be the liquid crystal injection port is provided, the bonded base material is thermally cured, and the liquid crystal is injected, and then the injection port is sealed with the sealant for light curing to manufacture a liquid crystal display unit. The curable resin composition is not limited to the above-mentioned manufacturing method, but can be preferably widely used in the manufacturing method of liquid crystal panels. [Example]

[Production Example 1: 1,1'-(Hexane-1,6-diyl)bis[3-(2-Aminoethyl)urea] (Addition product of polyamine and isocyanate) (Production 1) manufacturing method]

Solution A in which 17.17 g of hexamethylene diisocyanate was dissolved in 118 g of ethanol and solution B in which 61.36 g of ethylenediamine was dissolved in 150 g of ethanol were prepared. After the solution B was controlled at 25°C and stirred in the three-necked flask, the solution A was dropped at a rate of 1.4 g/min. After the solution A was dropped, the reaction solution was measured with a Fourier transform infrared spectrophotometer, and it was confirmed that there was no peak around 2250 cm ^-1 originating from the isocyanate group, and the reaction was terminated. For 1 mole of hexamethylene diisocyanate react 10 moles of ethylenediamine (the molar ratio is 1:10). After the reaction, use filter paper (No.4 manufactured by Kiriyama Co., Ltd.) to filter with a Kiriyama funnel (manufactured by Kiriyama Co., Ltd.) to remove the liquid. The obtained filtrate was washed with 100 ml of ethanol, further filtered, and dried in a vacuum oven at 50°C. Filtrate. Naturally cool to room temperature after drying, and pulverize with a high-pressure mill (trade name: Nano Jetmizer, manufactured by AISHIN NANO TECHNOLOGY Co., Ltd.) to produce the polyamine and Adduct product of isocyanate compound (hereinafter also referred to as "product 1").

[Production Example 2: Method for producing an adduct of polyamine and urea (Production 2)] 750 g (5.5 mol) of m-xylylenediamine and 50 g (0.832 mmol) of urea were fed into a 1 L pear-shaped flask, and stirred at 175° C. for 5.5 hours. Then cool to room temperature. 500 ml of THF (tetrahydrofuran) was added, stirred and filtered. The filtrate was stirred and washed with 600 ml of THF, and filtered again. Here, 2000 g of toluene was added to the obtained filtrate, and the precipitated crystal was filtered. The resulting filtrate was vacuum-dried at 50° C. and pulverized with a high-pressure mill (trade name: Nano Jetmizer, manufactured by AISHIN NANO TECHNOLOGY Co., Ltd.) to produce an adduct of polyamine and urea with an average particle diameter (median diameter) of 2.0 μm ( Hereinafter, it is also referred to as "manufacture 2").

[Production Example 3: Production method of 4,4'-hexamethylenebis(semicarbazide) (Production 3)]

Dissolution A in which 16.8 g of hexamethylene diisocyanate was dissolved in 150 g of ethanol and solution B in which 10 g of hydrazine was dissolved in 150 g of ethanol were prepared. After the solution B was stirred at 25°C, the solution A was dropped at a rate of 1.4 g/min. After the solution A was dropped, the reaction solution was measured with a Fourier transform infrared spectrophotometer, and it was confirmed that there was no peak around 2250 cm ^-1 originating from the isocyanate group, and the reaction was terminated. For 1 mole of hexamethylene diisocyanate, 2 moles of hydrazine are reacted (the molar ratio is 1:2). After the reaction, filter with a Kiriyama funnel (Kiriyama Co., Ltd. No. 4) using filter paper (Kiriyama Co., Ltd.) to remove the liquid. The obtained filtrate was washed with 50 ml of ethanol, further filtered, and dried in a vacuum oven at 50°C. Filtrate. After drying, pulverize with a high-pressure mill (trade name: Nano Jetmizer, manufactured by AISHIN NANO TECHNOLOGY Co., Ltd.) to produce a carbazide compound represented by the above chemical formula (B-2) with an average particle diameter (median diameter) of 2.1 μm (hereinafter also referred to as "Artifact 3").

[Production Example 4: Method for producing mixed crystals of two or more hydrazine compounds (Production 4)] 500 parts by mass of dihydrazine sebacate (SDH, produced by Otsuka Chemical Co., Ltd.), 500 parts by mass of dihydrazide dodecanedioate (DDH, produced by Otsuka Chemical Co., Ltd.), aluminum oxide ( AEROXIDE AluC (manufactured by Japan Aerosil Co., Ltd.) 50 parts by mass (aluminum content: 2.5 mass%) was heated at 200° C. to obtain a mixture of two crystalline hydrazine compounds dissolved in a liquid state. The mixture was subjected to constant temperature treatment at 200°C for 2 hours. Then, the mixture was transferred to a glass dish made of PYREX (registered trademark) preheated to 200°C, and set in an oven at 200°C. Next, the molten mixture is cooled to room temperature in an oven at a cooling rate of about 1.0° C./minute to obtain a solidified body. The solidified body that was completely cooled to room temperature was coarsely pulverized with a cutting mill (manufactured by Orient Corporation), and finally pulverized with a high-pressure pulverizer (trade name: Nano Jetmizer, manufactured by AISHIN NANO TECHNOLOGY Co., Ltd.) to produce an average particle size (median diameter) of 2.5 The hydrazine compound of μm (hereinafter also referred to as "manufacture 4").

[Example 1] 100 parts by mass of partially methacrylated bisphenol A epoxy resin (manufactured by KSM, PR-850CRP), 10 parts by mass of silica filler (manufactured by Nippon Shokubai Co., Ltd., SEAHOSTAR KE-C050HG) as an inorganic filler, As an organic filler, 10 parts by mass of acrylic resin filler (manufactured by AICA Industry Co., Ltd., F-351), 2 parts by mass of a photoradical initiator (manufactured by KSM Corporation, EY RESIN KR-2), and a radical polymerization inhibitor (Tokyo Kasei Kogyo Co., Ltd., BHT (dibutylhydroxytoluene) 0.15 parts by mass and silane coupling agent (Shin-Etsu Chemical Co., Ltd., KBM-403) 1.0 parts by mass, 15 parts by mass obtained in Production Example 1 as a latent hardener Product 1 and 0.1 parts by mass of hexamethylene diisocyanate as an isocyanate compound were uniformly dispersed at room temperature (25° C.) with a three-in-one motor (manufactured by IKA, trade name; RW28basic) to obtain a curable resin composition.

[Examples 2-41 and Comparative Examples 1-14] A curable resin composition was obtained in the same manner as in Example 1 except that the preparation of the curable resin composition was the preparation of Tables 1 to 5. The abbreviations in the table are as follows. PR-850CRP: Partially methacrylated bisphenol A epoxy resin (manufactured by KSM, product name PR-850CRP) 850S: Bisphenol A type epoxy resin (manufactured by DIC Corporation, product name EPICLON 850S) KE-C050HG: Silicon oxide filler (manufactured by Nippon Shokubai Co., Ltd., SEAHOSTAR KE-C050HG) F-351: Acrylic resin filler (manufactured by AICA Industry Co., Ltd., product name F-351) KR-2: photoradical initiator (manufactured by KSM Corporation, product name EY RESIN KR-2) BHT: radical polymerization inhibitor dibutylhydroxytoluene (manufactured by Tokyo Chemical Industry Co., Ltd., product name: BHT) KBM-403: Silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM-403) TPA-100: polyisocyanate of hexamethylene diisocyanate (manufactured by Asahi Kasei Co., Ltd., product name TPA-100) E402-100: Polyisocyanate of hexamethylene diisocyanate (manufactured by Asahi Kasei Co., Ltd., product name E402-100) TSE-100: Polyisocyanate of hexamethylene diisocyanate (manufactured by Asahi Kasei Co., Ltd., product name TSE-100) CURRANTS AOI: 2-isocyanatoethyl acrylate (manufactured by Showa Denko Co., Ltd., product name CURRANTS AOI) EH-5057P: Adduct of polyamine and epoxy resin (manufactured by ADEKA Co., Ltd., product name EH-5057P) EH-5030S: Adduct of polyamine and epoxy resin (manufactured by ADEKA Co., Ltd., product name EH-5030S) FXR-1020: Adduct of polyamine and epoxy resin (manufactured by T&K TOKA Co., Ltd., product name FXR-1020) EH-5011S: Adduct of imidazole and epoxy resin (manufactured by ADEKA Co., Ltd., product name EH-5011S) EH-4070S: Adduct of polyamine and epoxy resin (manufactured by ADEKA Co., Ltd., product name EH-4070S) ADH: Dihydrazine adipate (manufactured by Otsuka Chemical Co., Ltd.)

[evaluate] (storage stability at room temperature) The viscosity (within 2 hours) immediately after preparation of the resin compositions of Examples and Comparative Examples was measured as the initial viscosity. Furthermore, the viscosities of the resin compositions of Examples and Comparative Examples after being placed at 25°C for 7 days and after being placed at 25°C for 14 days were respectively measured, and the viscosity change rate (%) was calculated based on the initial viscosity. In addition, the viscosity was measured as follows. Install a 3°×R7.7 conical rotor on the RE-105U viscometer (manufactured by Toki Sangyo Co., Ltd.), set 0.15ml of the target resin composition in the conical rotor, and measure at 25°C at 2.5rpm The viscosity of the resin composition. When it exceeds the measuring range, it is called unmeasurable. Also, the standard beyond the measurement range is 1,200,000 mPa·s.

(heating storage stability) (1) Storage stability after heating at 40°C The viscosity (within 2 hours) immediately after preparation of the resin compositions of Examples and Comparative Examples was measured as the initial viscosity. Then measure the viscosity of the resin composition of the example and the comparative example after heating at 40°C for 2 hours, and then measure the viscosity after standing at 25°C for 7 days and the viscosity after standing at 25°C for 14 days, the initial viscosity is Calculate the viscosity change rate (%).

(2) Storage stability after heating at 50°C The viscosity (within 2 hours) immediately after preparation of the resin compositions of Examples and Comparative Examples was measured as the initial viscosity. Then measure the viscosity of the resin compositions of Examples and Comparative Examples after heating at 50°C for 2 hours, and then measure the viscosity after standing at 25°C for 7 days and the viscosity after standing at 25°C for 14 days, the initial viscosity is Calculate the viscosity change rate (%). In addition, the viscosity system was measured in the same manner as the liquid stability evaluation.

(Curability Test) For the resin compositions of Examples and Comparative Examples, 1) curing treatment at 120°C for 1 hour, and 2) curing at 120°C for 1 hour after UV3000mJ/ ^cm2 treatment Tablets were evaluated for curability by the following method.

Each cured sheet obtained by curing under the above-mentioned conditions was measured by an FT-IR measuring device (Spectrum one, manufactured by Perkin Elmer Co., Ltd.), and curability was evaluated. The calculation method of the epoxy hardening rate used the following formula. In the formula, the resin composition is an uncured product. The resin composition without adding isocyanate was used as a blank group, and the difference with the blank group was evaluated by ○×.

Existence area of reference peak; 1540~1480cm ^-1 (near peak 1510cm ^-1 ) Existence area of epoxy group peak: 925~895cm ^-1 (near peak 910cm ^-1 ) ○: Curing rate is 0 compared to blank group ~-20% ×: The hardening rate is less than -20% compared to the blank group

(Acetone detergency test) Use a 1ml TERUMO syringe to take 0.1ml of the unhardened resin composition of Examples and Comparative Examples, and spread it on a glass plate in a linear shape of 2cm. 200 ml of acetone was put into a 300 ml beaker, and stood up so that the composition coated on the glass slide would be immersed therein. After standing still for 5 minutes, clean the glass plate with an ultrasonic cleaning device (device name; US-20PS manufactured by SND Co., Ltd.) for 5 minutes, then take the glass plate out of the acetone bath, observe the state of the glass visually, and use the following criteria to evaluate . ×: The resin composition remains. ◯: The resin composition does not remain.

From the above results, it can be seen that the curable resin composition of the present invention has good curability, and is superior in liquid stability and acetone cleaning performance compared with the comparative example not containing isocyanate compounds. Furthermore, compared with Comparative Examples 9 to 12 in which a hydrazine-based curing agent was used as a latent curing agent, they were excellent in curability or excellent in liquid stability.

(Amount of surface amine) 5.75 parts by mass of the curable resin composition of Example 41 and 5.75 parts by mass of the curable resin composition of Comparative Example 14 were respectively dissolved in 20 parts by mass of propionitrile, suction filtered using a 1 μm membrane filter, and then 15 parts by mass of acetonitrile Rinse to clean. The filtrate was vacuum-dried at 25°C, and the obtained product from Example 41 was set as the treated product 1, and the obtained product from Comparative Example 14 was set as the processed product 2. 0.05 parts by mass of treated substances 1 and 2 were put into individual ampoules, and 20 parts by mass of a solution adjusted to 20 ppm of phenyl isocyanate with methylcyclohexane was added. Put in an ultrasonic cleaning tank (US-20PS manufactured by NSD Co., Ltd.), and disperse for 3 minutes while applying ultrasonic waves. At this point, shake the ampoule by hand to disperse. Subsequent immersion in a 70° C. hot water bath for 1 hour. Shake the ampoule by hand every 20 minutes. After immersing in a hot water bath at 70°C for 1 hour, put it into an ultrasonic cleaning tank, and shake the ampoule by hand for 3 minutes while applying ultrasonic waves to disperse. After cooling to room temperature, the supernatant liquid was taken into a syringe, and the filtrate was filtered with a 0.2 μm filter made of PTET to measure the absorbance with a spectrophotometer (V-570 manufactured by JASCO Co., Ltd.). The blank group was set as methylcyclohexane, and the absorbance at 226nm of 20ppm phenylisocyanate-methylcyclohexane solution and each sample was read. The phenyl isocyanate concentration was calculated using the phenyl isocyanate calibration line prepared in advance, and the amount of surface amine groups (mmol) per 1 g of the manufactured product 1 and the processed product 1 was calculated from the concentration decrease as the surface amine amount. As a result, it was found that the surface amine amount of the treated object 2 was 0.77 mmol/g, and the surface amine amount of the processed object 1 was 0.10 mmol/g. As a result, the treated product 1 obtained in Example 41 containing the latent hardener (B) and the isocyanate compound (C) was compared to the processed product 2 obtained in Comparative Example 14 that did not contain the isocyanate compound (C). The amount of amine is considerably reduced. Therefore, it was confirmed that by mixing the curable resin (A), the latent hardener (B) and the isocyanate compound (C), a part or all of the latent hardener (B) was mixed with a part or all of the isocyanate compound (C). Reaction, while confirming that the surface amine amount of the latent hardener (B) is reduced. Conduct such liquid stability evaluations. The results are shown in Table 5.

[產業上之可利用性]

[Industrial availability]

The curable resin composition of the present invention can be preferably used as a sealant or sealing agent for electronic parts such as liquid crystal display panels, and is industrially useful.

Claims (6)

A curable resin composition comprising only a curable resin (A), a latent hardener (B), an isocyanate compound (C), a photopolymerization initiator (D), an inorganic filler (E), an organic filler A curable resin composition comprising an agent (F), a coupling agent (G) and a radical polymerization inhibitor, wherein the latent hardener (B) contains 1 to 100 parts by mass relative to 100 parts by mass of the curable resin (A) , with respect to 100 parts by mass of the aforementioned latent hardener (B), the aforementioned isocyanate compound (C) contains 0.02 to 28 mass parts, and a part of the aforementioned latent hardener (B) has been partially or completely mixed with one of the isocyanate compounds (C). reaction, the aforementioned latent hardener (B) is at least one selected from the following group: (b1) carbazide (carbazide) compound, (b2) compound of imidazole compound added to epoxy resin, (b3) A compound in which a polyamine compound is added to at least one compound selected from the group consisting of epoxy resins, isocyanate compounds, and urea (however, the polyamine compound in (b3) does not include hydrazine, hydrazine compounds, and (b1) Carbazide compounds), (b4) mixed crystals of two or more hydrazide compounds, (b5) mixed crystals of one or more mono- or polyamine compounds and one or more hydrazide compounds, and (b6) one or more hydrazide compounds A mixed crystal of an imidazole compound and one or more hydrazine compounds. The curable resin composition according to claim 1, wherein the aforementioned latent hardener (B) is at least one selected from the following group: (b1) carbazide (carbazide) compound, (b2) compound added imidazole compound to epoxy resin, (b3) compound added polyamine compound to urea (however, the polyamine compound in (b3) does not include hydrazine and hydrazide compounds and (b1) carbazide compounds), (b5) mixed crystals of one or more mono- or polyamine compounds and one or more hydrazide compounds, and (b6) one or more imidazole compounds and one or more hydrazide compounds Mixed crystals of compounds. The curable resin composition according to claim 1 or 2 is a sealant composition for liquid crystal display elements. A method for producing a curable resin composition comprising only a curable resin (A), a latent hardener (B), an isocyanate compound (C), a photopolymerization initiator (D), and an inorganic filler (E) , A method for producing a curable resin composition comprising an organic filler (F), a coupling agent (G) and a radical polymerization inhibitor, comprising not prereacting a latent curing agent (B) and an isocyanate compound (C), and A step of mixing a curable resin (A), a latent hardener (B), an isocyanate compound (C) and a radical polymerization inhibitor, wherein the latent hardener (B) is at least one selected from the group consisting of One type: (b1) a carbazide compound, (b2) a compound obtained by adding an imidazole compound to an epoxy resin, (b3) at least one compound selected from the group consisting of an epoxy resin, an isocyanate compound, and a urea Compounds added with polyamine compounds (however, the polyamine compounds in (b3) do not include hydrazine compounds, hydrazide compounds and (b1) carbazide compounds), (b4) mixed crystals of two or more hydrazide compounds, ( b5) More than one mono- or polyamine compound and more than one acyl Mixed crystals of hydrazine compounds, and (b6) mixed crystals of one or more imidazole compounds and one or more hydrazine compounds. A liquid crystal display panel obtained by using the curable resin composition according to any one of claims 1 to 3. A method of manufacturing a liquid crystal display panel, which uses the curable resin composition according to any one of Claims 1 to 3 to perform photocuring and/or thermosetting in a liquid crystal dropping method.