KR20180095728A - Curing agent and resin composition using same - Google Patents

Abstract

The present invention relates to an epoxy resin comprising an isocyanate compound and a compound having at least one primary amino group in the molecule, obtained by the reaction of hydrazine or a polyamine compound having two or more primary amino groups in the molecule, and / A curing agent for a resin having at least one unsaturated bond in a molecule, a resin composition and a liquid crystal encapsulating composition using the same, a liquid crystal display panel, and a method for producing a liquid crystal display panel.

Description

CURING AGENT AND RESIN COMPOSITION USING SAME [

The present invention relates to an epoxy resin and / or a curing agent for a resin having at least one unsaturated bond in a molecule, and more particularly to a curing agent suitably usable for a liquid crystal display device such as a liquid crystal display, a resin composition using the same, A liquid crystal display panel, and a method of manufacturing the same.

In recent years, along with the enlargement of the display portion of the liquid crystal display and the narrowing of the frame width, the sealing agent has been thinned. Further, not only glass but also inorganic materials such as ITO electrodes and SiN films, organic materials such as alignment films and the like are adhered to the object to be bonded, thereby diversifying the adherend, and bonding of the dissimilar materials to each other becomes possible A variety of adhesive properties are required.

As sealants for bonding such dissimilar materials, sealants for liquid crystal display devices which contain a curing agent such as epoxy (meth) acrylate and a curing agent such as a thermosetting curing agent and do not contain an inorganic filler have been proposed (Patent Document 1). As the thermal epoxy curing agent used for the sealing agent for a liquid crystal display element, dihydrazide compounds such as sebacic acid dihydrazide, isophthalic acid dihydrazide and adipic acid dihydrazide, and other commercial products such as Amicure VDH, Amicure UDH All manufactured by Ajinomoto Fine Techno Co., Ltd.) and the like are exemplified.

Japanese Patent Application Laid-Open No. 2010-85712

In addition to the thinning of the sealing agent and the diversification of the adhesiveness, it is also required to improve the bonding strength to the sealing agent in order to suppress the peeling at the time of cutting the cell and the mounting of the liquid crystal cell driving IC.

Disclosure of the Invention It is an object of the present invention to provide a latent curing agent capable of satisfying the requirements of thinning of a sealing agent and diversification of adhesiveness and capable of improving the bonding strength to provide an epoxy resin and / , A resin composition using the same, and a liquid crystal encapsulating composition.

As a result of intensive investigations to solve the above problems, the present inventors have found that a compound having a urea structure in a molecule and having at least one primary amino group can be used as an epoxy resin and / or a resin having at least one unsaturated bond in a molecule It has been found that a resin composition and a liquid crystal sealing composition capable of adapting to the thinning of the sealing agent such as a liquid crystal display panel and the variety of adhesiveness as well as the bonding strength can be obtained by using the latent curing agent.

That is, the present invention is as described in [1] to [14].

[1] An epoxy resin comprising an isocyanate compound and a compound having at least one primary amino group in the molecule, obtained by the reaction of hydrazine or a polyamine compound having two or more primary amino groups in the molecule, and / To a curing agent for a resin having at least one unsaturated bond in a molecule.

[2] The compound represented by the formula (I)

(Wherein,

R ¹ is a single bond or a C ₂ to C ₁₂ alkylene (N atom (s) which is interrupted by C ₁ to C ₁₂ alkylene, one or more NH (imino groups) or O atoms H atom (hydrogen atoms) bonded to the nitrogen atom) has an amino group or a C ₁ to C ₁₂ which may be substituted with an alkylamino group), C ₃ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene -C ₁ to C ₁₂ alkylene, C ₃ to C ₁₂ cycloalkylene -C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene, C ₆ to C ₁₄ arylene, C ₁ to C ₄ alkylene -C ₆ to C ₁₄ arylene, C ₁ to C ₄ alkylene -C ₆ to C ₁₄ arylene -C ₁ to C ₄ alkylene or C ₆ to C ₁₄ arylene-C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene wherein the alkylene is linear or branched and may be substituted with halogen and C ₃ to ₁₂ Cycloalkylene or C ₆ to C ₁₄ arylene is unsubstituted or substituted by halogen or C ₁ to C ₄ alkyl,

n is 1, 2, 3 or 4,

When n is 2 or more, R ¹ is, independently of each other, the same as defined above,

when n is 1, A is a C ₁ to C ₁₂ alkyl, and one or more O atom (an oxygen atom) with a C ₂ to C ₁₂ alkyl interrupted by non-continuous, C ₂ to C ₁₂ alkyloxycarbonyl alkylene , C ₃ to C ₁₂ cycloalkyl, C ₁ to C ₁₂ alkyl-C ₃ to C ₁₂ cycloalkylene, C ₃ to C ₁₂ cycloalkyl-C ₁ to C ₁₂ alkylene-C ₃ to C ₁₂ cycloalkylene, C ₆ to C ₁₄ aryl, C ₁ to C ₄ alkyl-C ₆ to C ₁₄ arylene, C ₆ to C ₁₄ aryl-C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene, a linear or branched, and may be substituted by halogen, C ₃ to C ₁₂ cycloalkyl, C ₃ to C ₁₂ cycloalkylene, C ₆ to C ₁₄ aryl, or C ₆ to C ₁₄ arylene group is unsubstituted, or , Or is substituted by halogen or C ₁ to C ₄ alkyl), or (meth) acryloyloxyalkyl,

when n is 2, A is a C ₁ to C ₁₂ alkylene, a C ₂ to C ₁₂ alkylene which is discontinuously interrupted by one or more O atoms (oxygen atoms), a C ₁ to C ₁₂ alkylenoxycar alkylene carbonyl, C ₃ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene -C ₁ to C ₁₂ alkylene, C ₃ to C ₁₂ cycloalkylene -C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene, di-C ₃ to C ₁₂ cycloalkyl alkanediyl, C ₆ to C ₁₄ arylene, C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene-C ₁ to C ₄ alkylene, or C ₆ to C ₁₄ arylene-C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene, , Alkylene is straight-chain or branched and may be substituted with halogen, C ₃ to C ₁₂ cycloalkylene, C ₆ to C ₁₄ arylene is unsubstituted or substituted by halogen or C ₁ to C ₄ alkyl Lt; / RTI >

When n is 3, A is represented by the following formula (1)

(Wherein R ² is the same or different and is a linear or branched C ₁ to C ₁₂ alkylene), the following formula (2)

(Wherein R ³ is the same or different and is a linear or branched C ₁ to C ₁₂ alkylene) or the following formula (3)

(Wherein R ⁴ is the same or different and is a straight or branched C ₁ to C ₁₂ alkylene and R ⁵ is CH)

When n is 4, A is represented by the following formula (4)

Wherein X ³ is Si or a C ₃ to C ₁₂ cycloalkyl-C ₁ to C ₁₂ alkylene-C ₃ to C ₁₂ cycloalkyl, or a C ₆ to C ₁₄ aryl-C ₁ to C ₄ alkylene C ₆ to C ₁₄ aryl wherein the alkylene is linear or branched and is optionally substituted with 1 to 6 halogens and wherein C ₃ to C ₁₂ cycloalkyl or C ₆ to C ₁₄ aryl is unsubstituted, Or a tetravalent residue derived from a halogen or a C ₁ to C ₄ alkyl), and / or a compound having at least one primary amino group in a molecule represented by the formula And a curing agent for a resin having one unsaturated bond.

[3] A compound having at least one primary amino group in a molecule represented by the following formula (Ia)

(Wherein,

R ¹ are, independently of each other, the same as in [2]

X ¹ is C ₁ to C ₁₂ alkylene group, one or more O atoms interrupted discontinuously by (an oxygen atom) C ₂ to C ₁₂ alkylene, C ₁ to C ₁₂ alkylene-carbonyl alkylene, C ₃ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene -C ₁ to C ₁₂ alkylene, C ₃ to C ₁₂ cycloalkylene-C ₁ to C ₁₂ alkylene-C ₃ to C ₁₂ cycloalkylene, di C ₃ to C ₁₂ cycloalkanediyl, C ₆ to C ₁₄ arylene, C ₁ to C ₄ Alkylene-C ₆ to C ₁₄ arylene-C ₁ to C ₄ alkylene, or C ₆ to C ₁₄ arylene-C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene, Or branched and may be substituted with halogen and C ₃ to C ₁₂ cycloalkylene or C ₆ to C ₁₄ arylene is unsubstituted or substituted by halogen or C ₁ to C ₄ alkyl) , [2] It relates to the described hardener.

[4] A compound having at least one primary amino group in a molecule,

(Wherein,

R ¹ has the same meaning as in [2] above,

X ² is C ₁ to C ₁₂ alkyl, and one or more O atoms in (oxygen atoms) interrupted by non-consecutive C ₂ to C ₁₂ alkyl, C ₁ to C ₁₂ alkyloxycarbonyl alkylene, C ₃ to C ₁₂ cycloalkyl, C ₁ to C ₁₂ alkyl, -C ₃ to C ₁₂ cycloalkylene, C ₃ to C ₁₂ cycloalkyl, -C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene, C ₆ to C ₁₄ Aryl, C ₁ to C ₄ alkyl-C ₆ to C ₁₄ arylene, C ₆ to C ₁₄ aryl-C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene wherein the alkylene is linear or branched , and may be substituted by halogen, C ₃ to C ₁₂ cycloalkyl, C ₃ to C ₁₂ cycloalkylene, C ₆ to C ₁₄ aryl or C ₆ to C ₁₄ arylene group is either unsubstituted, or halogen or C ₁ Or (meth) acryloyloxyalkyl], which is unsubstituted or substituted with C ₁ -C ₄ alkyl.

[5] The curing agent according to any one of [1] to [4], further comprising a compound obtained by treating a compound having at least one primary amino group in the molecule with an isocyanate compound.

[6] The curing agent according to any one of [1] to [4], further comprising a compound obtained by treating a compound having at least one primary amino group in the molecule with an isocyanate compound and an epoxy resin.

[7] The curing agent according to any one of [1] to [4], further comprising a compound obtained by treating a compound having at least one primary amino group in the molecule with an isocyanate compound and a compound having a hydroxy group will be.

[8] A resin composition comprising the curing agent (A) according to any one of the above [1] to [7] and a resin (B) having an epoxy resin and / or at least one unsaturated bond.

[9] The resin composition according to [8], wherein the epoxy resin is a partially esterified epoxy resin obtained by reacting (meth) acrylic acid in an amount of 10 to 90 equivalent% based on 1 equivalent of the epoxy resin of the epoxy resin.

[10] The resin composition according to [8] or [9], wherein the total amount of the primary amino groups contained in the curing agent (A) is 0.001 to 10 equivalents based on 1 equivalent of the epoxy group of the epoxy resin.

[11] The epoxy resin composition according to any one of [1] to [11], wherein the total amount of primary amino groups contained in the curing agent (A) is 0.001 to 10 equivalents based on the total amount of one equivalent of the epoxy group of the epoxy resin and one equivalent of the unsaturated bond of the resin having at least one unsaturated bond in the molecule, To a resin composition according to any one of the above [8] to [10].

[12] A liquid crystal encapsulant composition comprising the resin composition according to any one of [8] to [11].

[13] A liquid crystal display panel obtained by using the liquid crystal sealing composition according to [12].

[14] In a liquid crystal dropping method, a method of manufacturing a liquid crystal display panel in which a liquid crystal encapsulant composition described in [12] above is used for photo-curing and then thermosetting is performed.

INDUSTRIAL APPLICABILITY According to the present invention, a sealing agent such as a liquid crystal display panel is adapted to be thinned and diversified in adhesiveness, and at the same time, an adhesive strength capable of suppressing peeling at the time of cutting a cell and mounting a liquid crystal cell driving IC Lt; / RTI >

BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is an explanatory diagram showing an embodiment for manufacturing a liquid crystal display panel using a liquid crystal sealing composition. FIG.
2 is an explanatory view for explaining a method of testing the adhesive strength of the liquid crystal sealing composition.

The numerical range indicated by using " to " in the present specification indicates a range including numerical values before and after " to " as the minimum value and the maximum value, respectively. The amount of each component in the composition refers to the total amount of the plurality of substances present in the composition, unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Quot; C _a to C _b " means that the number of carbon atoms is in the range of a to b.

[Curing agent]

The present invention relates to an epoxy resin composition containing an isocyanate compound and a compound having at least one primary amino group in the molecule, obtained by the reaction of hydrazine or a polyamine compound having two or more primary amino groups in the molecule, Or a resin curing agent having at least one unsaturated bond in the molecule. A curing agent comprising a compound having a urea structure in addition to at least one primary amino group in a molecule is dissolved in an epoxy resin and / or a resin having at least one unsaturated bond in the molecule (e.g., a (meth) acrylic resin or the like) By using it as a latent curing agent, it is possible to adapt to the thinning of the sealing agent such as a liquid crystal display panel and the diversification of adhesiveness, and to provide an adhesive capable of suppressing peeling at the time of cutting the cell and mounting the liquid crystal cell driving IC Strength can be expressed.

Since a compound obtained by reacting an isocyanate compound with hydrazine or a polyamine compound having at least two primary amino groups in the molecule has a urea structure and at least one primary amino group in the molecule, And it is presumed that the bonding strength will be higher than that of the hydrazide compound or amine compound used as a curing agent.

[Isocyanate compound]

The isocyanate compound used in the present invention is a compound having at least one isocyanate group (-N═C═O), and is not particularly limited, but a monoisocyanate compound, a diisocyanate compound, a triisocyanate compound, a tetraisocyanate compound, .

(Monoisocyanate compound)

Examples of the monoisocyanate compound include compounds represented by the following formula (1a).

In formula (1a), X ² is C ₁ to C ₁₂ alkyl, C ₂ to C ₁₂ alkyl which is discontinuously interrupted by one or more O atoms (oxygen atoms), C ₁ to C ₁₂ alkyloxycarbonylalkyl C ₃ to C ₁₂ cycloalkyl, C ₁ to C ₁₂ alkyl-C ₃ to C ₁₂ cycloalkylene, C ₃ to C ₁₂ cycloalkyl-C ₁ to C ₁₂ alkylene-C ₃ to C ₁₂ cycloalkylene , C ₆ to C ₁₄ aryl, C ₁ to C ₄ alkyl-C ₆ to C ₁₄ arylene, C ₆ to C ₁₄ aryl-C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene, Is straight or branched and may be substituted with halogen and C ₃ to C ₁₂ cycloalkyl, C ₃ to C ₁₂ cycloalkylene, C ₆ to C ₁₄ aryl, or C ₆ to C ₁₄ arylene may be unsubstituted Or is substituted by halogen or C ₁ to C ₄ alkyl), or (meth) acryloyloxyalkyl. X ² in the formula (1a) has the same meaning as A in the case where n is 1 in the formula (I).

As used herein, either alone or in combination with another term, " C ₁ to C ₁₂ alkyl " is straight-chain or branched and may be substituted with halogen, or may be substituted with one or more O atoms It may be discontinuously interrupted, and preferably it is linear. The carbon number of alkyl is in the range of C ₁ to C ₁₂ , more preferably C ₁ to C ₈ , more preferably C ₁ to C ₆ , particularly preferably C ₁ to C ₄ . Specific examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, Dodecyl and the like and those which are branched chains such as isopropyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl, isooctyl, t-octyl, 2-ethylhexyl, . 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 substituents is 1 to 12, preferably 1 to 6, more preferably 1 to 4, particularly preferably 1 to 3.

&Quot; C ₁ to C ₁₂ alkylene ", alone or in combination with other terms, is straight-chain or branched and may be substituted by halogen, or may be substituted by one or more NH (imino groups) or (H atom (hydrogen atom) bonded to the N atom (nitrogen atom) may be substituted with an amino group or a C ₁ to C ₁₂ alkylamino group), preferably, It is a straight chain. The carbon number of the alkylene is in the range of C ₁ to C ₁₂ , more preferably C ₁ to C ₈ , still more preferably C ₁ to C ₆ , particularly preferably C ₁ to C ₄ . Specific examples thereof include, for example, methylene, ethylene, trimethylene, propylene, tetramethylene, 1-methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene, pentamethylene, And examples thereof include tetramethylene, hexamethylene, 5-methylpentamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene and dodecamethylene. 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 substituents is 1 to 12, preferably 1 to 6, more preferably 1 to 4, particularly preferably 1 to 3.

In this specification, the "C ₁ to C ₁₂ alkyloxycarbonyl alkylene" or "C ₁ to C ₁₂ alkyleneoxy carbonyl alkylene" range of the carbon number of the alkyl oxy or alkyleneoxy a is C ₁ to C ₁₂ , More preferably from C ₁ to C ₈ , still more preferably from C ₁ to C ₆ , and particularly preferably from C ₁ to C ₄ . Specific examples thereof include, for example, methoxycarbonylmethylene, ethoxycarbonylmethylene, n-propoxycarbonylmethylene, n-butoxycarbonylmethylene, n-pentyloxycarbonylmethylene, n-hexyloxycarb Heptyloxycarbonylmethylene, n-octyloxycarbonylmethylene, n-nonyloxycarbonylmethylene, n-decyloxycarbonylmethylene, n-undecyloxycarbonylmethylene, n-dodecyloxycar Propylmethylmethylene, and neopentylmethylene, and straight chain such as isopropoxycarbonylmethylene, isobutoxycarbonylmethylene, sec-butoxycarbonylmethylene, t-butoxycarbonylmethylene, 2-methylbutoxycarbonylmethylene, isooctyloxy And branched chain such as carbonylmethylene, t-octyloxycarbonylmethylene, 2-ethylhexyloxycarbonylmethylene and the like.

As used herein alone or in combination with other terms, the carbon number range of " C ₃ to C ₁₂ cycloalkyl " is C ₃ to C ₁₂ , more preferably C ₃ to C ₈ , and more preferably C ₃ to C ₆ , particularly preferably C ₄ to C ₆ . Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclodecyl and cyclododecyl. C ₃ to C ₁₂ cycloalkyl is preferably cyclopentyl or cyclohexyl. The C ₃ to C ₁₂ cycloalkyl may be unsubstituted or substituted by halogen or C ₁ to C ₄ alkyl, and 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 chlorine atom. Examples of the C ₁ to C ₄ alkyl as a substituent include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and t-butyl. C ₁ -C ₄ alkyl as a substituent is preferably methyl, ethyl or n-propyl, more preferably methyl or ethyl. The number of substituents in the case of having a substituent is 1 to 5, preferably 1 to 3, more preferably 1 to 2, particularly preferably 1.

The term "C ₃ to C ₁₂ cycloalkylene" as used herein alone or in combination with another term means that the carbon number of the C ₃ to C ₁₂ cycloalkylene is C ₃ to C ₁₂ , more preferably C ₃ to C ₈ , C ₃ to C ₆ , particularly preferably C ₄ to C ₆ . Specific examples thereof include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene, cyclodecylene, cyclododecylene, and cyclododecylene. The C ₃ to C ₁₂ cycloalkylene is preferably cyclopentylene or cyclohexylene. The C ₃ to C ₁₂ cycloalkylene may be unsubstituted or substituted by halogen or C ₁ to C ₄ alkyl, and 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 chlorine atom. Examples of the C ₁ to C ₄ alkyl as a substituent include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and t-butyl. C ₁ -C ₄ alkyl as a substituent is preferably methyl, ethyl or n-propyl, more preferably methyl or ethyl. The number of substituents in the case of having a substituent is 1 to 4, preferably 1 to 3, more preferably 1 to 2, particularly preferably 1.

As used herein alone or in combination with another term, " C ₆ to C ₁₄ aryl " is a monovalent group having at least one aromatic ring. Specific examples thereof include phenyl, biphenyl, naphthyl, entanyl, phenanthrene and the like. Preferably phenyl, biphenyl or naphthyl, more preferably phenyl or naphthyl. The C ₆ to C ₁₄ aryl may be unsubstituted or substituted by halogen or C ₁ to C ₄ alkyl, and 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 chlorine atom. Examples of the C ₁ to C ₄ alkyl as a substituent include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and t-butyl. C ₁ -C ₄ alkyl as a substituent is preferably methyl, ethyl or n-propyl, more preferably methyl or ethyl. The number of substituents in the case of having a substituent is 1 to 5, preferably 1 to 3, more preferably 1 to 2, particularly preferably 1.

As used herein alone or in combination with another term, " C ₆ to C ₁₄ arylene " is a divalent group having at least one aromatic ring. Specific examples thereof include phenylene, naphthylene, anthranylene, phenanthranylene, and the like. Is preferably phenylene or naphthylene, more preferably phenylene or naphthylene. The C ₆ to C ₁₄ arylene may be unsubstituted or substituted by halogen or C ₁ to C ₄ alkyl, and 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, a chlorine atom or a bromine atom, more preferably a fluorine atom or a chlorine atom. Examples of the C ₁ to C ₄ alkyl as a substituent include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and t-butyl. C ₁ -C ₄ alkyl as a substituent is preferably methyl, ethyl or n-propyl, more preferably methyl or ethyl. The number of substituents in the case of having a substituent is 1 to 4, preferably 1 to 3, more preferably 1 to 2, particularly preferably 1.

The (meth) acryloyloxyalkyl isocyanate as the monoisocyanate compound includes a compound represented by the following formula (1b).

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

Specific examples of the monoisocyanate compound include methylisocyanate, ethylisocyanate, n-hexylisocyanate, cyclohexylisocyanate, 2-ethylhexylisocyanate, phenylisocyanate, benzylisocyanate, propylisocyanate, isopropylisocyanate, butylisocyanate, Butyl isocyanate, ethyl isocyanatocetoacetate, butyl isocyanatocetoacetate, methyl (S) - (-) - 2-isocyanatopropionate, isocyanate 1-naphthyl isocyanate 4-chlorophenyl isocyanate, 4-fluorophenyl isocyanate, phenethyl isocyanate, p-tolyl isocyanate, m-tolyl isocyanate, 3,5-dimethylphenyl isocyanate, .

Specific examples of the (meth) acryloyloxyalkyl isocyanate include (meth) acryloyloxymethyl isocyanate, (meth) acryloyloxyethyl isocyanate, and (meth) acryloyloxypropyl isocyanate. .

(Diisocyanate compound)

As the diisocyanate compound, a compound represented by the following formula (2a) can be mentioned.

In formula (2a), X ¹ is C ₁ to C ₁₂ alkylene, C ₂ to C ₁₂ alkylene which is discontinuously interrupted by one or more O atoms (oxygen atoms), C ₁ to C ₁₂ alkyleneoxy C ₁ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene-C ₃ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene-C ₃ to C ₁₂ cycloalkylene-C ₁ C ₁ to C ₁₂ alkylene, C ₃ to C ₁₂ cycloalkylene-C ₁ to C ₁₂ alkylene-C ₃ to C ₁₂ cycloalkylene, di C ₃ to C ₁₂ cycloalkanediyl, C ₆ to C ₁₄ arylene , C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene-C ₁ to C ₄ alkylene, or C ₆ to C ₁₄ arylene-C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene Wherein the alkylene is linear or branched and may be substituted with halogen and C ₃ to C ₁₂ cycloalkylene or C ₆ to C ₁₄ arylene is unsubstituted or substituted with halogen or C ₁ to C ₄ alkyl Lt; / RTI > X ¹ in the formula (2a) has the same meaning as A in the case of n in the formula (I).

Specific examples of the diisocyanate compound include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), xylene diisocyanate (XDI), hydrogenated xylene diisocyanate (hydrogenated XDI), isophorone diisocyanate Isocyanate (IPDI), tolylidine diisocyanate (TPDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), 2,4,4-trimethylhexamethylene diisocyanate (TMHDI) -Trimethylhexamethylene diisocyanate (TMHDI), 4,4'-diisocyanato-3,3'-dimethylbiphenyl, 4,4'-diisocyanato-3,3'-dimethyldiphenylmethane, 2,2 Bis (4-isocyanatophenyl) hexafluoropropane, 2,4-diisocyanatotoluene, 1,3-bis Isocyanate, 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,5-diisocyanato And the like can be talren program.

(Triisocyanate compound)

Examples of the triisocyanate compound include compounds having an isocyanurate structure, a buret structure or an adduct structure having an isocyanate group at the 3-terminal. Examples of the triisocyanate compound having an isocyanurate structure include a compound having an isocyanurate structure represented by the following formula (3a).

Wherein R ² is the same or different and is a linear or branched C ₁ to C ₁₂ alkylene.

Examples of the triisocyanate compound having a buret structure include compounds represented by the following formula (3b).

Wherein R ³ is the same or different and is a linear or branched C ₁ to C ₁₂ alkylene.

The triisocyanate compound having an adduct structure includes a compound represented by the following formula (3c).

Wherein R ⁴ is the same or different and is a linear or branched C ₁ to C ₁₂ alkylene and R ⁵ is CH.

Specific examples of the triisocyanate compound include tri (isocyanatomethyl) isocyanurate, tri (isocyanatoethyl) isocyanurate, tri (isocyanatopropyl) isocyanurate, tri (Isocyanatobutyl) isocyanurate, N, N'-2-tris-isocyanatomethylmalonic acid amide, N, N'-2-tris-iso And cyanatohexyl malonic acid amide.

(Tetraisocyanate compound)

Examples of the tetraisocyanate compound include compounds represented by the following formula (4a).

Wherein X ³ is C ₃ to C ₁₂ cycloalkyl-C ₁ to C ₁₂ alkylene-C ₃ to C ₁₂ cycloalkyl, or C ₆ to C ₁₄ aryl-C ₁ to C ₄ alkylene-C ₆ to C ₁₄ aryl (wherein alkylene is linear or branched and may be substituted with halogen, C ₃ to C ₁₂ cycloalkyl or C ₆ to C ₁₄ aryl is unsubstituted or substituted by halogen or C ₁ to C ₄ alkyl Which may be the same or different.

As the tetraisocyanate compound, tetraisocyanatosilane represented by the following formula (4b) can be mentioned.

Specific examples of the tetraisocyanate compound include 4,4'-diphenylmethane-2,2 ', 5,5'-tetraisocyanate, and tetraisocyanatosilane.

[Polyvalent amine compound]

The polyvalent amine compound is a compound having at least two primary amino groups and includes, for example, a polyvalent amine compound represented by the following formula (5a).

Wherein, L is a C ₁ to C ₁₂ alkylene group, one or more NH (imino group), or O atom to the (oxygen) it stopped discontinuously C ₂ to C ₁₂ alkylene (N atom (the nitrogen atom) (Hydrogen atom) which may be substituted by an amino group or a C ₁ to C ₁₂ alkylamino group), C ₃ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene-C ₃ to C ₁₂ cycloalkylene C ₁ to C ₁₂ alkylene-C ₃ to C ₁₂ cycloalkylene-C ₁ to C ₁₂ alkylene, C ₃ to C ₁₂ cycloalkylene-C ₁ to C ₄ alkylene-C ₃ to C ₁₂ Cycloalkylene, C ₆ to C ₁₄ arylene, C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene, C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene-C ₁ to C ₄ alkyl Or C ₆ to C ₁₄ arylene-C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene wherein the alkylene is linear or branched and may be substituted with halogen and C ₃ to C ₁₂ cycloalkylene or It is C ₆ to C ₁₄ arylene group that is unsubstituted or may be substituted with, or a halogen or C ₁ to C ₄ alkyl). L in the formula (5a) has the same meaning as R ¹ in the formula (I), the formula (Ia) and the formula (IIa).

Examples of the polyamine compound include a diamine compound having two primary amino groups and a triamine compound having three primary amino groups. The diamine compound having two primary amino groups is not particularly limited, and examples thereof include aliphatic diamines, alicyclic diamines, and aromatic diamines. Among the compounds represented by the above formula (5a), the compound wherein L is a single bond is hydrazine.

Specific examples of the compound having C ₁ to C ₁₂ alkylene in the aliphatic diamine include ethylenediamine, propylenediamine, 1,2-diaminopropane, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, Heptamethylenediamine, octamethylenediamine, dodecamethylenediamine, propane-1,2-diamine, 1,2-diamino-2-methylpropane and the like.

Among the aliphatic diamines, compounds having a linear or branched C ₂ to C ₁₂ alkylene discontinuously interrupted by one or more O atoms (oxygen atoms), specifically, 2,2 ' (2-aminoethoxy) ethane, 1,11-diamino-3,6,9-trioxandecane, bis (3-aminopropyl) ether, 1 , 4-butanediol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether and ethylene glycol bis (3-aminopropyl) ether.

Among the aliphatic diamines, linear or branched C ₂ to C ₁₂ alkylene (the H atom (hydrogen atom) bonded to the N atom (nitrogen atom)), which is discontinuously interrupted by one or more NH (imino groups) Or a C ₁ to C ₁₂ alkylamino group), and specific examples thereof include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tris ( (3-aminopropyl) ethylenediamine, bis (hexamethylene) triamine, 3,3'-diamino-N-methyldipropylamine, 3,3'- Diaminodipropylamine, bis (3-aminopropyl) methylamine, and the like.

Specific examples of the alicyclic diamine include isophoronediamine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, trans-1,2-diaminocyclohexane, 1,3- Bis (aminomethyl) cyclohexane, 4,4'-methylenebis (cyclohexylamine), and the like.

Specific examples of the aromatic diamine include aromatic diamines such as p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4'-diaminodiphenylmethane, , 5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminotoluene, and the like.

Specific examples of the triamine compound having three primary amino groups include tris (4-aminophenyl) amine, tris (3-aminopropyl) amine, tris Amine and the like.

The isocyanate compound and the hydrazine or polyhydric amine compound preferably have a hydrazine or polyhydric amine compound in an amount of 0.01 to 50 mol, more preferably 0.1 to 50 mol, and still more preferably 0.1 to 30 mol, per mol of the isocyanate compound , Particularly preferably 0.1 to 20 moles, in an organic solvent or in a knitted state (solvent-free) at a temperature of preferably -10 DEG C to 120 DEG C, more preferably -5 DEG C to 100 DEG C, 50 ° C, and particularly preferably 5 to 30 ° C.

The curing agent is preferably a compound having an isocyanate compound and a hydrazine or polyhydric amine compound in an amount of preferably 0.01 to 50 moles per 1 mole of the isocyanate group contained in the isocyanate compound and the total number of primary amino groups contained in the hydrazine or polyhydric amine compound , More preferably 0.1 mol to 50 mol, still more preferably 0.1 mol to 30 mol, and particularly preferably 0.5 mol to 20 mol.

[Curing agent]

The present invention is an epoxy resin containing a compound represented by the following formula (I) and / or a curing agent for a resin containing at least one unsaturated bond.

The curing agent of the present invention is represented by the following formula (I)

(Wherein,

R ¹ is a single bond or a C ₂ to C ₁₂ alkylene (N atom (s) which is interrupted by C ₁ to C ₁₂ alkylene, one or more NH (imino groups) or O atoms H atom (hydrogen atoms) bonded to the nitrogen atom) has an amino group or a C ₁ to C ₁₂ which may be substituted with an alkylamino group), C ₃ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene -C ₁ to C ₁₂ alkylene, C ₃ to C ₁₂ cycloalkylene -C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene, C ₆ to C ₁₄ arylene, C ₁ to C ₄ alkylene -C ₆ to C ₁₄ arylene, C ₁ to C ₄ alkylene -C ₆ to C ₁₄ arylene -C ₁ to C ₄ alkylene or C ₆ to C ₁₄ arylene-C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene wherein the alkylene is linear or branched and may be substituted with halogen and C ₃ to ₁₂ Cycloalkylene or C ₆ to C ₁₄ arylene is unsubstituted or substituted by halogen or C ₁ to C ₄ alkyl,

n is 1, 2, 3 or 4,

When n is 2 or more, R < ¹ >

when n is 1, A is a C ₁ to C ₁₂ alkyl, and one or more O atom (an oxygen atom) with a C ₂ to C ₁₂ alkyl interrupted by non-continuous, C ₂ to C ₁₂ alkyloxycarbonyl alkylene , C ₃ to C ₁₂ cycloalkyl, C ₁ to C ₁₂ alkyl-C ₃ to C ₁₂ cycloalkylene, C ₃ to C ₁₂ cycloalkyl-C ₁ to C ₁₂ alkylene-C ₃ to C ₁₂ cycloalkylene, C ₆ to C ₁₄ aryl, C ₁ to C ₄ alkyl-C ₆ to C ₁₄ arylene, C ₆ to C ₁₄ aryl-C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene, a linear or branched, and may be substituted by halogen, C ₃ to C ₁₂ cycloalkyl, C ₃ to C ₁₂ cycloalkylene, C ₆ to C ₁₄ aryl or C ₆ to C ₁₄ arylene group is either unsubstituted, Or is substituted by halogen or C ₁ to C ₄ alkyl, or (meth) acryloyloxyalkyl,

when n is 2, A is a C ₁ to C ₁₂ alkylene, a C ₂ to C ₁₂ alkylene which is discontinuously interrupted by one or more O atoms (oxygen atoms), a C ₁ to C ₁₂ alkylenoxycar alkylene carbonyl, C ₃ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene -C ₁ to C ₁₂ alkylene, C ₃ to C ₁₂ cycloalkylene -C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene, di-C ₃ to C ₁₂ cycloalkyl alkanediyl, C ₆ to C ₁₄ arylene, C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene-C ₁ to C ₄ alkylene, or C ₆ to C ₁₄ arylene-C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene, , Alkylene is linear or branched and may be substituted by halogen, and C ₃ to C ₁₂ cycloalkylene or C ₆ to C ₁₄ arylene is unsubstituted or substituted by halogen or C ₁ to C ₄ alkyl Lt; / RTI >

When n is 3, A is represented by the following formula (1)

(Wherein R ² is the same or different and is a linear or branched C ₁ to C ₁₂ alkylene), the following formula (2)

(Wherein R ³ is the same or different and is a linear or branched C ₁ to C ₁₂ alkylene) or the following formula (3)

(Wherein R ⁴ is the same or different and is a straight or branched C ₁ to C ₁₂ alkylene and R ⁵ is CH)

When n is 4, A is represented by the following formula (4)

Wherein X ³ is Si or a C ₃ to C ₁₂ cycloalkyl-C ₁ to C ₁₂ alkylene-C ₃ to C ₁₂ cycloalkyl, or a C ₆ to C ₁₄ aryl-C ₁ to C ₄ alkylene C ₆ to C ₁₄ aryl wherein the alkylene is linear or branched and optionally substituted with halogen and C ₃ to C ₁₂ cycloalkyl or C ₆ to C ₁₄ aryl is unsubstituted or substituted by halogen or C _{Is a} tetravalent residue derived from ₁ to ₄ alkyl).

The compound of the above formula (I) is a compound having at least one isocyanate group (-N = C = O) as described above, for example, the above monoisocyanate compound, the diisocyanate compound, the triisocyanate compound and the tetraisocyanate And a compound obtained by reacting at least one isocyanate compound selected from the group consisting of a hydrazine compound and a polyhydric amine compound. The compound represented by the above formula (I) is obtained by reacting the isocyanate compound with the hydrazine or polyhydric amine compound in an amount of preferably 0.01 to 50 moles, more preferably 0.1 to 1 mole of the hydrazine or polyhydric amine compound per mole of the isocyanate compound More preferably from -10 ° C to 120 ° C in an organic solvent or in a knit (no solvent), more preferably from -10 ° C to 120 ° C, such that the molar amount is from 0 to 50 mol, more preferably from 0.1 mol to 30 mol, particularly preferably from 0.1 mol to 20 mol It is preferably obtained by carrying out a reaction while controlling the temperature to -5 to 100 ° C, more preferably 0 to 50 ° C, particularly preferably 5 to 30 ° C.

The compound represented by the above formula (I) is obtained by reacting the isocyanate compound and the hydrazine or polyhydric amine compound in such an amount that the total number of primary amino groups contained in the hydrazine or polyamine compound relative to 1 mole of the isocyanate group contained in the isocyanate compound is preferably Is preferably 0.01 mol to 50 mol, more preferably 0.1 mol to 50 mol, still more preferably 0.1 mol to 30 mol, particularly preferably 0.5 mol to 20 mol, per mol of the aldehyde.

It is preferable that the present invention is an epoxy resin containing a compound represented by the following formula (Ia) and / or a curing agent for a resin containing at least one unsaturated bond among the compounds represented by the above formula (I).

The curing agent of the present invention is characterized in that the compound having at least one primary amino group in the molecule is represented by the following formula (Ia)

(Wherein,

R ¹ is, independently of each other, a single bond or a C ₂ to C ₁₂ alkylene which is interrupted by C ₁ to C ₁₂ alkylene, one or more NH (imino groups) or O atoms (oxygen atoms) (H atom (hydrogen atom) bonded to N atom (nitrogen atom) may be substituted with amino group or C ₁ to C ₁₂ alkylamino group), C ₃ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene C ₃ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene-C ₃ to C ₁₂ cycloalkylene-C ₁ to C ₁₂ alkylene, C ₃ to C ₁₂ cycloalkylene-C ₁ to C ₁₂ alkyl alkylene -C ₃ to C ₁₂ cycloalkylene, C ₆ to C ₁₄ arylene, C ₁ to C ₄ alkylene -C ₆ to C ₁₄ arylene, C ₁ to C ₄ alkylene -C ₆ to C ₁₄ arylene C ₁ to C ₄ alkylene, or C ₆ to C ₁₄ arylene-C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene wherein the alkylene is linear or branched and is substituted with halogen Capital And wherein C ₃ to C ₁₂ cycloalkylene or C ₆ to C ₁₄ arylene is unsubstituted or substituted by halogen or C ₁ to C ₄ alkyl,

X ¹ is C ₁ to C ₁₂ alkylene group, one or more O atoms interrupted discontinuously by (an oxygen atom) C ₂ to C ₁₂ alkylene, C ₁ to C ₁₂ alkylene-carbonyl alkylene, C ₃ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene -C ₁ to C ₁₂ alkylene, C ₃ to C ₁₂ cycloalkylene-C ₁ to C ₁₂ alkylene-C ₃ to C ₁₂ cycloalkylene, di C ₃ to C ₁₂ cycloalkanediyl, C ₆ to C ₁₄ arylene, C ₁ to C ₄ Alkylene-C ₆ to C ₁₄ arylene-C ₁ to C ₄ alkylene, or C ₆ to C ₁₄ arylene-C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene, Or branched and may be substituted with halogen and C ₃ to C ₁₂ cycloalkylene or C ₆ to C ₁₄ arylene is unsubstituted or substituted by halogen or C ₁ to C ₄ alkyl) Wind It is right.

X ¹ in the formula (Ia) has the same meaning as A in the case where n is 2 in the formula (I).

The compound represented by the formula (Ia) is preferably obtained by reacting the diisocyanate compound with a hydrazine or polyhydric amine compound. The diisocyanate compound and the hydrazine or polyhydric amine compound preferably have a hydrazine or polyhydric amine compound in an amount of from 0.01 to 50 mol, more preferably from 0.1 to 50 mol, and still more preferably from 0.1 to 1 mol, per mol of the diisocyanate compound Preferably from -10 ° C to 120 ° C, more preferably from -5 ° C to 100 ° C, more preferably from 0 ° C to 100 ° C, in an organic solvent or in a knit (no solvent) Deg.] C to 50 [deg.] C, particularly preferably 5 to 30 [deg.] C.

As the compound obtained by the reaction of the diisocyanate compound with, for example, tris (2-aminoethyl) amine which is a polyvalent amine compound having three primary amino groups in the molecule, there can be mentioned a compound represented by the following formula .

In the formula, X ¹ is the same meaning as X ¹ in the formula (Ia).

As the compound represented by the formula (Ia), for example,

1,1 '- [methylenebis (cyclohexane-1,4-diyl)] bis [3- (12-aminododecyl) urea]

(Methylenebis (cyclohexane-1,4-diyl)] bis [3- (2-aminoethyl) urea] (A-

1,1 '- [methylenebis (cyclohexane-1,4-diyl)] bis [3- (6-aminohexyl) urea] (A-

1,1 '- (hexane-1,6-diyl) bis [3- (12-aminododecyl) urea] (A-

1,1 '- (hexane-1,6-diyl) bis [3- (2-aminoethyl) urea] (A-

1,1 '- (hexane-1,6-diyl) bis [3- (6-aminohexyl) urea] (A-

(A-7), N, N'-hexamethylene [carbonylbis (aspartyl) -2-aminoethyl] - [carbonylbis

And the like.

Examples of the compound represented by the formula (Ia) include compounds represented by the following formulas.

It is preferable that the present invention is an epoxy resin containing a compound represented by the following formula (Ib) and / or a curing agent for a resin containing at least one unsaturated bond among the compounds represented by the above formula (I).

The curing agent of the present invention is characterized in that the compound having at least one primary amino group in the molecule is represented by the following formula (Ib)

(Wherein X ¹ has the same meaning as defined above). X ¹ in the formula (Ib) has the same meaning as A in the case of n in the formula (I).

The compound represented by the formula (Ib) is preferably obtained by reacting the diisocyanate compound with hydrazine. The diisocyanate compound and hydrazine preferably contain hydrazine in an amount of from 0.01 to 50 mol, more preferably from 0.1 to 50 mol, more preferably from 0.1 to 30 mol, particularly preferably from 0.1 to 0.5 mol, based on 1 mol of the diisocyanate compound Mol to 20 mol, preferably -10 ° C to 120 ° C, more preferably -5 ° C to 100 ° C, more preferably 0 ° C to 50 ° C, particularly preferably in an organic solvent or knit (solventless) Is preferably obtained by controlling the reaction at 5 to 30 占 폚.

As the disaccharide compound represented by the formula (Ib), for example,

4,4 '- (methylene di-1,4-cyclohexylene) bis (semicarbazide) (B-1),

4,4'-hexamethylenebis (semicarbazide) (B-2),

4,4 '- (2,2,4-trimethylhexamethylene) bis (semicarbazide) (B-3),

4,4 '- (1,3-cyclohexylenebis methylene) bis (semicarbazide) (B-4),

4,4 '- (1,3-phenylenebis methylene) bis (semicarbazide) (B-5),

4,4'-isophoronebis (semicarbazide) (B-6)

And the like.

Examples of the compound represented by the formula (Ib) include compounds represented by the following formulas.

The curing agent of the present invention is a curing agent represented by the following formula (IIa)

(Wherein,

R ¹ is a single bond or a C ₂ to C ₁₂ alkylene (N atom (s) which is interrupted by C ₁ to C ₁₂ alkylene, one or more NH (imino groups) or O atoms H atom (hydrogen atoms) bonded to the nitrogen atom) has an amino group or a C ₁ to C ₁₂ which may be substituted with an alkylamino group), C ₃ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene -C ₁ to C ₁₂ alkylene, C ₃ to C ₁₂ cycloalkylene -C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene, C ₆ to C ₁₄ arylene, C ₁ to C ₄ alkylene -C ₆ to C ₁₄ arylene, C ₁ to C ₄ alkylene -C ₆ to C ₁₄ arylene -C ₁ to C ₄ alkylene or C ₆ to C ₁₄ arylene-C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene wherein the alkylene is linear or branched and may be substituted with halogen and C ₃ to ₁₂ Cycloalkylene or C ₆ to C ₁₄ arylene is unsubstituted or substituted by halogen or C ₁ to C ₄ alkyl,

X ² is C ₁ to C ₁₂ alkyl, and one or more O atoms in (oxygen atoms) interrupted by non-consecutive C ₂ to C ₁₂ alkyl, C ₁ to C ₁₂ alkyloxycarbonyl alkylene, C ₃ to C ₁₂ cycloalkyl, C ₁ to C ₁₂ alkyl, -C ₃ to C ₁₂ cycloalkylene, C ₃ to C ₁₂ cycloalkyl, -C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkylene, C ₆ to C ₁₄ Aryl, C ₁ to C ₄ alkyl-C ₆ to C ₁₄ arylene, C ₆ to C ₁₄ aryl-C ₁ to C ₄ alkylene-C ₆ to C ₁₄ arylene wherein the alkylene is linear or branched , and may be substituted by halogen, C ₃ to C ₁₂ cycloalkyl, C ₃ to C ₁₂ cycloalkylene, C ₆ to C ₁₄ aryl or C ₆ to C ₁₄ arylene group is either unsubstituted, or halogen or C ₁ to it it is preferable to contain a compound represented by the Yes), or (meth) acryloyloxyethyl] alkyl substituted with C ₄ alkyl. X ² in the formula (IIa) has the same meaning as A in the case where n is 1 in the formula (I).

The compound represented by the formula (IIa) is preferably obtained by reacting the monoisocyanate compound with the hydrazine or polyhydric amine compound. The monoisocyanate compound and the hydrazine or polyhydric amine compound preferably have an amino group of the diamino compound in an amount of 0.1 to 50 mol, more preferably 0.1 to 30 mol, particularly preferably 1 to 5 mol, per mol of the isocyanate group of the monoisocyanate compound Preferably from -10 ° C to 120 ° C, more preferably from -5 ° C to 100 ° C, and even more preferably from 0 ° C to 50 ° C, in an organic solvent or knit (no solvent) Particularly preferably 5 to 30 占 폚.

In the formula (IIa), when R ¹ is a single bond, it is a semicarbazide compound. The semicarbazide compound is preferably a compound represented by the following formula (IIb).

Wherein X ² has the same meaning as defined above. X ² in the formula (IIb) has the same meaning as A in the case where n is 1 in the formula (I).

The compound represented by the formula (IIb) is preferably obtained by reacting the monoisocyanate compound with hydrazine. The monoisocyanate compound and hydrazine preferably contain hydrazine in an amount of preferably from 0.01 to 50 mol, more preferably from 0.1 to 50 mol, more preferably from 0.1 to 30 mol, particularly preferably from 0.1 to 0.5 mol, based on 1 mol of the monoisocyanate compound Mol to 20 mol, preferably -10 ° C to 120 ° C, more preferably -5 ° C to 100 ° C, more preferably 0 ° C to 50 ° C, particularly preferably in an organic solvent or knit (solventless) Is preferably obtained by controlling the reaction at 5 to 30 占 폚.

Examples of the compound represented by the formula (IIa) include 4- (ethyl acrylate) semicarbazide (B-7).

Examples of the compound represented by the formula (IIb) include compounds represented by the following formulas.

The curing agent of the present invention is obtained by further treating a compound having at least one primary amino group in the molecule with an isocyanate compound obtained by reacting the isocyanate compound with hydrazine or a polyamine compound having two or more primary amino groups in the molecule Is preferably a curing agent containing a compound obtained by subjecting

The curing agent includes a compound obtained by treating a compound having at least one primary amino group in the molecule with an isocyanate compound to obtain a resin composition comprising a curing agent and an epoxy resin and / or a resin having at least one unsaturated bond, And viscosity increase due to aging can be suppressed.

The isocyanate compound used in the treatment of the compound having at least one primary amino group in the molecule is not particularly limited as long as it is a compound having at least one isocyanate group. As the isocyanate compound, at least one selected from the above-described isocyanate compounds can be preferably used. The isocyanate compounds may be used singly or in combination of two or more.

The amount of the isocyanate compound to be used for treating the compound having at least one primary amino group in the molecule is not particularly limited and may be appropriately selected depending on the purpose and the like. The amount of the isocyanate compound to be used is preferably such that the number of isocyanate groups in the isocyanate compound is from 0.01 to 10 mols, more preferably from 0.02 to 5 mols when the number of amino groups in the compound having at least one primary amino group in the molecule is one mole, , And more preferably 0.05 mol to 2 mol.

Treatment of a compound having at least one primary amino group in the molecule with an isocyanate compound is preferably carried out in an organic solvent or knitted (solventless) at a temperature of preferably -10 ° C to 120 ° C, more preferably -5 ° C to 100 ° C , More preferably 10 ° C to 90 ° C, and particularly preferably 20 ° C to 80 ° C. The treatment time may be, for example, 0.1 to 100 hours, preferably 0.5 to 50 hours. The time for heating and mixing differs depending on the temperature at which the mixture is heated and blended. Since the time is shortened when the temperature is high and the time is long when the temperature is low, it is possible to select the optimum treatment time in accordance with the purpose of use when used as a curing agent .

The curing agent of the present invention is obtained by reacting a compound having at least one primary amino group in the molecule obtained by the reaction of the isocyanate compound with hydrazine or a polyamine compound having two or more primary amino groups in the molecule in the presence of an isocyanate compound and an epoxy resin It is also preferable that the curing agent is a curing agent containing a compound obtained by further treating with a curing agent.

Wherein the curing agent comprises a compound obtained by treating a compound having at least one primary amino group in the molecule with an isocyanate compound and an epoxy resin to obtain a resin composition comprising a curing agent and an epoxy resin and / or a resin having at least one unsaturated bond The liquid stability of the liquid can be improved and viscosity increase due to aging can be suppressed.

The isocyanate compound used in the treatment of the compound having at least one primary amino group in the molecule is not particularly limited as long as it is a compound having at least one isocyanate group. As the isocyanate compound, at least one selected from the above-described isocyanate compounds can be preferably used. The isocyanate compounds may be used singly or in combination of two or more.

The epoxy resin used in the treatment of the compound having at least one primary amino group in the molecule is not particularly limited as long as it is a compound having at least one epoxy group and can be appropriately selected from known epoxy resins. Examples of the epoxy resin include epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, cyclic aliphatic epoxy resin, Epoxy resin, glycidylamine-based epoxy resin, heterocyclic epoxy resin, and urethane-modified epoxy resin. Among them, bisphenol A type epoxy resin, glycidyl ester type epoxy resin and the like are preferably used. The epoxy resins may be used singly or in combination of two or more.

The amount of the isocyanate compound to be used for treating the compound having at least one primary amino group in the molecule is not particularly limited and may be appropriately selected depending on the purpose and the like. The amount of the isocyanate compound to be used is preferably such that the number of isocyanate groups in the isocyanate compound is from 0.01 to 10 mols, more preferably from 0.02 to 5 mols when the number of amino groups in the compound having at least one primary amino group in the molecule is one mole, , And more preferably 0.05 mol to 2 mol.

The amount of the epoxy resin used for treating the compound having at least one primary amino group in the molecule is not particularly limited and can be appropriately selected depending on the purpose and the like. The amount of the epoxy resin to be used is preferably such that the number of epoxy groups in the epoxy resin is 0.001 to 10 moles, more preferably 0.005 to 1 mole, when the number of amino groups in the compound having at least one primary amino group in the molecule is one mole More preferably 0.01 mol to 0.5 mol, and still more preferably 0.01 mol to 0.5 mol.

The treatment of the compound having at least one primary amino group in the molecule with an isocyanate compound and an epoxy resin is preferably carried out in an organic solvent or knitted (solventless) at a temperature of preferably -10 ° C to 120 ° C, more preferably -5 ° C Deg.] C to 100 deg. C, more preferably 10 deg. C to 90 deg. C, particularly preferably 20 deg. C to 80 deg. The treatment time may be, for example, 0.1 to 100 hours, preferably 0.5 to 50 hours. The time for heating and mixing differs depending on the temperature at which the mixture is heated and blended. Since the time is shortened when the temperature is high and the time is long when the temperature is low, it is possible to select the optimum treatment time in accordance with the purpose of use when used as a curing agent .

The curing agent of the present invention is a curing agent which is obtained by reacting the isocyanate compound with hydrazine or a compound having at least one primary amino group in the molecule obtained by the reaction of a polyamine compound having two or more primary amino groups in the molecule with an isocyanate compound and a hydroxy group Is further preferably a curing agent comprising a compound obtained by further treating a compound having a hydroxyl group.

Wherein the curing agent comprises a compound obtained by treating a compound having at least one primary amino group in the molecule with an isocyanate compound and a compound having a hydroxy group to obtain a curing agent containing an epoxy resin and / The liquid stability of the resin composition can be improved and viscosity increase due to aging can be suppressed.

The isocyanate compound used in the treatment of the compound having at least one primary amino group in the molecule is not particularly limited as long as it is a compound having at least one isocyanate group. As the isocyanate compound, at least one selected from the above-described isocyanate compounds can be preferably used. The isocyanate compounds may be used singly or in combination of two or more.

The compound having a hydroxy group used in the treatment of the compound having at least one primary amino group in the molecule is not particularly limited and may be appropriately selected from known compounds and used. Specific examples of the compound having a hydroxy group include an alcohol compound, a phenol compound, and a carboxylic acid compound. The compound having a hydroxy group may be a monofunctional compound or a polyfunctional compound.

Examples of the monoalcohol compound in the alcohol compound include alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butyl alcohol, Alcohol, 2,4-dimethyl-3-pentanol, 3-ethyl-3-pentanol, 3-methyl-3-pentanol, pentaerythritol, Methyl-3-pentanol, 2-iodoethanol, 1-methoxy-2-propanol, acetone cyanhydrin, (R) - (- (R) - (+) - 3-butyn-2-ol, 3-butyne- , (R) - (+) - 3-butyn-2-ol, ethylene cyanohydrin, 3,3-dimethyl-1-butanol, 2 3-methyl-1-butanol, (S) - (-) - 2-methyl- Butanol, DL-2-methyl-1-butanol, 2-methyl-3-butyn- (R) - (-) - 2-pentanol, 2,2,2-trifluoroethanol, 2,2,2-trichloroethanol, 2 , 2-tribromoethanol, 3-trimethylsilyl-2-propyn-1-ol, 1-bromo-2-propanol, 2-propanol, 1,3-dichloro-2-propanol, 2, 3-dibromo-2- Dimethyl-3-hexanol, 3,5-dimethyl-3-hexanol, 2-ethyl-1-butanol, 1-butanol, 2-methyl-3-buten-2-ol, 2-methyl-1-butanol, 1-octanol, 1-dodecanol, 3,7-dimethyl-1-octanol, 1-tetradecanol, 1-undecanol , 1-hexadecanol, 1-octadecanol, 1-pentadecanol, 2-octanol, 1-dococanol, 1-eicosanol, cyclohexanemethanol, cyclododecanol, Cyclohexanol, 2-ethylcyclohexanol, 4- (2-hydroxyethyl) cyclohexanol, 1-cyclohexane-1-butanol Octyl alcohol, 4-cyclohexyl cyclohexanol, 2-cyclohexyl cyclohexanol, decahydro-2-naphthol, 1-decene-3- Octanol, 4- (hydroxymethyl) cyclohexanecarboxylic acid, trans-4- (4-methylpentanoic acid) (Hydroxymethyl) cyclohexanecarboxylic acid, 4- (trifluoromethyl) cyclohexane methanol, borneol, 2- (benzyloxy) ethanol and the like.

In addition, it is also possible to use 2-methoxyethanol, diethylene glycol monomethyl ether, decaethylene glycol monomethyl ether, dodecaethylene glycol monomethyl ether, 3-methoxy-1-propanol, 1-butoxy- Monoalcohol compounds having an ether bond such as glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, and 1,4-butanediol monomethyl ether.

Examples of the diol compound include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 2,3-dimethyl-2,3-butanediol, 2,2- 1,3-propanediol, (S, S) - (+) - 2,3-butanediol, pinacol, 2,2- (S) - (+) - 1,2-propanediol, (R) - (-) - 1,2-propanediol, 1,5-pentanediol, (R) - (-) - 1,2-propanediol, 2-butyne-1,4-diol, 1,6-hexanediol, 1,8- Octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-decanediol, 1,2-tetradecanediol, 1,4-cyclohexanedimethanol, neo Pentyl glycol monol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3- (2-hydroxyethoxy) -2-butyne, diethylene glycol, tripropylene glycol, 2,2-bis (4-hydroxycyclohexyl) propane and the like .

Examples of the triol compound include 1,1,1-tris (hydroxymethyl) ethane, glycerol, 1,2,8-octanetriol and the like.

Examples of polyfunctional compounds having four or more functional groups include dipentaerythritol, diglycerol, span 20, and the like.

Examples of the monofunctional phenol compound include 4-methoxyphenol, 3-chlorophenol, 4-chlorophenol, p-cresol, m-cresol, o-cresol, 3,5-dichlorophenol, 4-iodophenol, 3-methoxyphenol, 3,5-dimethoxyphenol, 4-phenoxyphenol, 3-bromophenol, 2-bromophenol, 2-chlorophenol, -Bromophenol, 2,4-dichlorophenol, 3,4-dichlorophenol, 2,6-dimethoxyphenol, 2,6-dimethylphenol, 3,5-dimethylphenol, 2-fluorophenol, 3- 2-iodophenol, 4-methoxy-1-naphthol, 2,4,6-trichlorophenol, 4-aminophenol, 6- Chloro-1-naphthol, 2,3-dichlorophenol, 2,5-dichlorophenol, 2,4-dimethylphenol, 3,4-dimethylphenol, 2,6-difluorophenol, 3,5- Phenol, 2,6-dibromophenol, 3,5-dibromophenol, 2,4,6-trimethylphenol, 4-aminophenol hydrochloride, 4-tert-butylphenol, 4- 4-hydrox Benzenitrile, 2,4-dibromophenol, 2,3-dimethylphenol, 2,4-difluorophenol, 3,4-difluorophenol, 3,4-dimethoxyphenol, 4-hydroxybenzaldehyde, 4-isopropylphenol, 4- (methylthio) phenol, 2,4,6-tribromophenol, 2,4,6- Amino-2-naphthol, 6-amino-1-naphthol, 3-aminophenol, 1-bromo-2-naphthol, 3-bromo- 2-naphthol, 2-naphthol, 2,4-dichloro-1-naphthol, 1,6-dibromo-2-naphthol, 2,5-difluorophenol, 2,3-difluorophenol, 2-aminophenol, 5-aminophenol, 2-aminophenol, 2-aminophenol, 3-hydroxybenzenethiol, Butyl phenol, 3-cyanophenol, 3-ethoxy phenol, 3-ethyl phenol, 2-naphthol, 2-ethoxyphenol, 3-hydroxy Benzylphenol, 6-hydroxy-2-naphthonitrile, 6-hydroxy-2-naphthaldehyde, 3-isopropylphenol, 2,3,5-trimethylphenol, 2,3,6- But are not limited to, trimethylphenol, 4- (trifluoromethoxy) phenol, 4-amino-1-naphthol hydrochloride, 2-aminophenol hydrochloride, 2-tert- butylphenol, 4- Naphthol, 2,4-dibromo-1-naphthol, 3- (dimethylamino) phenol, 2-ethylphenol, 4'-hydroxyacetophenone, 4-hexylphenol, 2-hydroxybenzotrifluoride, 2-hydroxybenzenethiol, 2-isopropylphenol, 2- (methylthio) phenol, 4-amylphenol salicylaldehyde, 3-hydroxybenzotrifluoride, 2,3,5,6-tetrafluorophenol , 2,3,4-trifluorophenol, 2-chlorophenol and the like.

Examples of the phenol compound having two hydroxyl groups include 4,4'-dihydroxydiphenyl ether, 5-methoxy resorcinol, 2-methyl resorcinol, 5-methyl resorcinol monohydrate, 4-chlorocatechol, 2,2'-dihydroxydiphenyl ether, 1,3-bis (4-hydroxyphenoxy) benzene, 5-bromoresorcinol, 4 4-chlorocatechol, 4,6-dichlororesorcinol, 2-iodoresorcinol, methylhydroquinone, 4-methylcatechol, 3-methoxycatechol, methoxyhydroquinone, 4 2-ethylhexanoic acid, 2,2-dimethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,2-dimethylcyclohexanone, 3-dimethylhydroquinone, 4-fluorocatechol, 4-fluororesorcinol, 3-methylcatechol, tetrachlorohydroquinone, 4,4'-dihydroxydiphenylmethane, 3-bromocatechol, cresol Isomer mixture), bis (4- Dibromo-1,5-dihydroxynaphthalene, 3-fluorocatechol, 2,4,6-tribromorezorcinol, 2,2-bis ( Bifunctional phenol compounds such as 4-hydroxyphenyl) propane, 4,4'-ethylidene bisphenol, trimethylhydroquinone and 1,2-dihydroxynaphthalene, and monofunctional phenol compounds such as 4-hydroxybenzyl alcohol. .

Examples of the trifunctional phenol compound include 1,2,4-trihydroxybenzene, 1,8,9-trihydroxy anthracene, 5-methyl pyrogallol, 4,4 ', 4 "-trihydroxy triphenylmethane, .

Examples of the tetrafunctional phenol compound include leuco quinizarine and examples of the hexafunctional phenol compound include hexahydroxybenzene and 2,3,6,7,10,11-hexahydroxytriphenylene hydrate and the like .

Examples of the carboxylic acid compound include methoxyacetic acid, glyoxylic acid, heptanoic acid, decanoic acid, nonanoic acid, lauric acid, myristic acid, 4-methyln- octanoic acid, pimelic acid, heptadecanoic acid, Hydroxystearic acid, 2-hexyldecanoic acid, and the like, as well as mono-, di- and tri-hydroxycarboxylic acids such as benzoic acid, pentaacetic acid, Dicarboxylic acids such as carboxylic acid, azelaic acid, suberic acid, sebacic acid, (+) - camphoric acid, and dodecanedioic acid, and polycarboxylic acids having three or more functionalities such as 1,3,5-pentanetricarboxylic acid And the like.

The compounds having a hydroxy group may be used singly or in combination of two or more. Among them, it is preferable to use at least one member selected from the group consisting of an alcohol compound (preferably a diol compound) and a phenol compound.

The amount of the isocyanate compound to be used for treating the compound having at least one primary amino group in the molecule is not particularly limited and may be appropriately selected depending on the purpose and the like. The amount of the isocyanate compound to be used is preferably such that the number of isocyanate groups in the isocyanate compound is from 0.01 to 10 mols, more preferably from 0.02 to 5 mols when the number of amino groups in the compound having at least one primary amino group in the molecule is one mole, , And more preferably 0.05 mol to 2 mol.

The amount of the compound having a hydroxy group for treating a compound having at least one primary amino group in the molecule is not particularly limited and may be appropriately selected depending on the purpose and the like. The amount of the hydroxyl group-containing compound to be used is preferably such that the number of hydroxyl groups is from 0.001 to 10 moles, more preferably from 0.005 to 1 mole, per 1 mole of the compound having at least one primary amino group in the molecule , And more preferably 0.01 mol to 0.5 mol.

The treatment with an isocyanate compound and a compound having a hydroxyl group of a compound having at least one primary amino group in the molecule is preferably carried out in an organic solvent or in a knit (solventless) at a temperature of preferably -10 ° C to 120 ° C, more preferably - It is preferably carried out while controlling the temperature to 5 to 100 占 폚, more preferably 10 to 90 占 폚, particularly preferably 20 to 80 占 폚. The treatment time may be, for example, 0.1 to 100 hours, preferably 0.5 to 50 hours.

[Resin composition]

The resin composition of the present invention is a resin composition comprising a curing agent comprising a compound having at least one primary amino group in a molecule obtained by reacting the isocyanate compound with hydrazine or a polyamine compound having two or more primary amino groups in the molecule (A), and a resin (B) having at least one unsaturated bond in an epoxy resin and / or a molecule. The curing agent (A) preferably contains a compound represented by at least one kind selected from the group consisting of the above-mentioned formulas (I), (Ia), (Ib), (IIa) and (IIb) It is also preferable to include a compound, an isocyanate compound and an epoxy resin, or a compound treated with an isocyanate compound and a compound having a hydroxy group.

[Epoxy resin]

As the epoxy resin, known ones can be used, and for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, A glycidyl ester-based resin, a glycidylamine-based epoxy resin, a heterocyclic epoxy resin, and a urethane-modified epoxy resin. Among them, it is preferable to use bisphenol A type epoxy resin, cresol novolak type epoxy resin or the like. Epoxy (meth) acrylic acid modified with (meth) acrylic acid may be used as the resin having a glycidyl group. For example, it is preferable to use a partially esterified epoxy resin obtained by reacting an epoxy resin described in JP-A-2012-77202 with (meth) acrylic acid. Concretely, the amount of (meth) acrylic acid is preferably 10 to 90 equivalent%, more preferably 20 to 80 equivalent%, further preferably 30 to 70 equivalent%, particularly preferably 1 to 10 equivalent%, based on 1 equivalent of the epoxy group of the epoxy resin It is preferable to use a partially esterified epoxy resin obtained by reacting 40 to 60 equivalent% of (meth) acrylic acid. One type of epoxy resin may be used alone, or a plurality of types may be used in combination. It may also be an unsaturated bond-containing epoxy resin.

The partially esterified epoxy resin can be produced, for example, by first reacting bisphenol A type epoxy resin and acrylic acid or methacrylic acid in the presence of a basic catalyst according to a conventional method so as to have 0.9 to 1.1 equivalents of carboxylic acid groups per 2 equivalents of epoxy groups To the reaction product, about four times as much pure water as toluene in a mass ratio is added, and the mixture is stirred at 60 to 80 ° C for 1 hour. The mixture is allowed to stand to separate into an organic layer and an aqueous layer, and the aqueous layer is removed. This operation is repeated 3 to 5 times. Finally, the organic layer is recovered and the residual toluene is removed by vacuum distillation to purify the partially esterified epoxy resin obtained by reducing the water-soluble ionic material. Specific examples of the bisphenol A type epoxy resin include Epicot 828, 834, 1001 and 1004 (manufactured by Mitsubishi Chemical), Epiclon 850, 860 and 4055 (manufactured by DIC), and the like. As such a raw material resin, a resin having a water-soluble ionic material reduction treatment (hereinafter referred to as a high purity treatment) is preferably used, for example, Epiclon 850S (manufactured by DIC), and the like.

[Resins having at least one unsaturated bond in the molecule]

The resin composition may contain a resin having at least one unsaturated bond in the molecule. Examples of the resin having at least one unsaturated bond in the molecule include styrene derivatives, ethylene derivatives, maleimide derivatives, (meth) acrylic acid derivatives and the like. Among them, it is preferable to use a (meth) acrylic acid derivative having at least one (meth) acryloyl group in the molecule.

Specific examples of the (meth) acrylic acid derivatives include (meth) acrylic acid derivatives such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate and t- Alkyl esters; (Meth) acrylic acid aryl esters such as phenyl (meth) acrylate; (Meth) acrylic acid aralkyl esters such as benzyl (meth) acrylate; Alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate; (Meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-3-hydroxypropyl, (meth) acrylic acid- Methacrylic acid esters; (Meth) acrylic esters of alicyclic alcohols such as cyclohexyl (meth) acrylate, and the like. Here, (meth) acrylic acid means both acrylic acid and methacrylic acid.

When the epoxy resin and the resin having at least one unsaturated bond in the molecule are used in combination, the amount of the epoxy resin and the resin having at least one unsaturated bond in the molecule is appropriately determined depending on the purpose of the cured resin composition It is possible. When the resin having at least one unsaturated bond in the molecule is a (meth) acrylic acid derivative having at least one (meth) acryloyl group in the molecule, the amount of the (meth) acryloyl group is preferably 0.1 to 9.0 equivalents based on 1 equivalent of the epoxy group (Meth) acryloyl group is more preferably in the range of 0.3 to 4.0 equivalents.

The resin composition may contain a silicone resin, a urea resin, an imide resin, glass, and the like, if necessary, in addition to the above resin.

The resin composition may further contain additives such as antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, drawing modifiers, thermal polymerization inhibitors, leveling agents, surfactants, colorants, preservation stabilizers, plasticizers , A lubricant, a filler, an inorganic particle, an anti-aging agent, a wettability improver, and an antistatic agent.

The blending amount of the curing agent (A) and the epoxy resin and / or the resin (B) having at least one unsaturated bond in the molecule is preferably such that the total amount of the semicarbazide group or the primary amino group of the curing agent (A) Is preferably 0.001 to 10 equivalents, more preferably 0.01 to 8 equivalents, still more preferably 0.05 to 5 equivalents, particularly preferably 0.1 to 3 equivalents. When the total amount of the semicarbazide group or the primary amino group in the curing agent (A) is 0.1 to 3 equivalents based on 1 equivalent of the epoxy group of the epoxy resin, when the resin composition is contained in the sealing agent such as a liquid crystal display panel, It is possible to adapt the required thinning, diversification of adhesiveness to various adherends, and the like, and to exhibit adhesive strength that can suppress peeling at the time of cell cutting and mounting of a liquid crystal cell driving IC.

(A) and the epoxy resin (A) and / or the resin (B) having at least one unsaturated bond in the molecule, the epoxy resin (B) may be contained singly or in the form of an epoxy resin and at least one unsaturated bond (B), the total amount of the semi-carbazed group or the primary amino group of the curing agent (A) is preferably 0.0005 to 10 equivalents, more preferably 0.0005 to 10 equivalents, based on 1 equivalent of the epoxy group of the epoxy resin 0.005 to 8 equivalents, more preferably 0.025 to 5 equivalents, particularly preferably 0.05 to 3 equivalents.

When the resin (B) having at least one unsaturated bond in the molecule alone is contained, the total amount of the semicarbazide group or the primary amino group of the curing agent (A) relative to 1 equivalent of the unsaturated bond of the resin (B) Is preferably 0.0005 to 10 equivalents, more preferably 0.005 to 8 equivalents, still more preferably 0.025 to 5 equivalents, particularly preferably 0.05 to 3 equivalents. When the blending amount of the curing agent (A) relative to the resin (B) is within the above range, when the resin composition is contained in the sealing agent such as a liquid crystal display panel, the thinning required for the sealing agent and various adhesiveness to various adherends And it is also possible to exhibit an adhesive strength capable of suppressing peeling at the time of cutting the cell and mounting the liquid crystal cell driving IC.

[Liquid crystal sealing composition]

The present invention is a liquid crystal sealing composition comprising the above resin composition. The liquid crystal sealing composition comprises a resin composition comprising the curing agent (A) and an epoxy resin and / or a resin (B) having at least one unsaturated bond in the molecule, a photopolymerization initiator (C) (D).

[Photopolymerization initiator (C)]

Examples of the photopolymerization initiator include benzophenone, 2,2-diethoxyacetophenone, benzyl, benzoyl isopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, and thioxanthone. As a photopolymerization initiator, a commercially available photopolymerization initiator may be used. Examples of commercially available photo radical polymerization initiators include Irgacure 907, Irgacure 819, Irgacure 651, Irgacure 369, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Lin TPO (all manufactured by BASF Japan), and the like.

[Inorganic filler (D)]

The inorganic filler is not particularly limited and includes, for example, spherical silica, spherical alumina, spherical titanium oxide, spherical aluminum oxide, and spherical calcium carbonate. Of these, spherical silica is preferable because it is excellent in dispersibility and excellent in the adhesiveness of the sealant suitable for the liquid crystal dropping method and the effect of improving the moisture resistance of the cured product.

The mixing ratio of each component in the liquid crystal sealing composition is preferably 0.5 to 5 parts by mass, preferably 0.5 to 4 parts by mass, more preferably 0.8 to 3 parts by mass, relative to 100 parts by mass of the resin composition (C) , And (D) the inorganic filler is 0 to 40 parts by mass, preferably 2 to 30 parts by mass, and more preferably 3 to 20 parts by mass. The content of the photopolymerization initiator (C) is preferably from 0.5 to 3 mass%, and the content of the inorganic filler (D) is preferably from 0 to 40 mass% in the total mass of the liquid crystal sealing composition.

The liquid crystal encapsulant composition is preferably prepared by sufficiently kneading using a paint roll or the like in consideration of uniform and complete dispersion of solids such as an inorganic filler.

[Liquid crystal display panel]

The liquid crystal encapsulant composition of the present invention satisfies the requirements of thinning and diversification of adhesiveness and exhibits an adhesive strength capable of suppressing peeling at the time of cutting the cell and mounting the liquid crystal cell driving IC And can be suitably used for manufacturing a liquid crystal display panel.

That is, the liquid crystal display panel of the present invention comprises a glass substrate opposed to each other, a cured product of the liquid crystal sealing composition for bonding the opposed glass substrates, and a liquid crystal sealed with a cured product of the opposed glass substrate and the liquid crystal sealing composition do.

[Manufacturing method of liquid crystal display panel]

The liquid crystal display panel can be produced by performing photo-curing using the liquid crystal sealing composition of the present invention, followed by thermal curing. Fig. 1 shows an embodiment for manufacturing a liquid crystal display panel. Specifically, as shown in the cross-sectional view of FIG. 1 (a), the glass substrate 1 is used, and as shown in the sectional view of FIG. 1 (b) The liquid crystal sealing composition (2) of the present invention is applied. Subsequently, as shown in the cross-sectional view of Fig. 1 (c), the other glass substrate 4 is placed on the liquid crystal encapsulant composition 2 on one glass substrate 1 while being opposed to each other, A pair of glass substrates 1 and 4 are bonded by irradiating a light ray such as ultraviolet rays in an amount of 1,000 to 3,000 mJ to solidify the liquid crystal sealing composition 2 and thereafter, And heated at a temperature for about one hour to sufficiently cure to form a liquid crystal sealing cell 5 surrounded by a pair of glass substrates 1 and 4 and a cured liquid crystal sealing agent 2. 1 (d), the liquid crystal 6 is injected from the liquid crystal injection hole 3 in a vacuum, the liquid crystal injection hole 3 is then closed, The liquid crystal display panel 7 can be manufactured. The liquid crystal sealing composition is applied to a rubbed ITO glass substrate provided with an orientation film by dispensing, then liquid crystal is dropped on the substrate, the upper and lower substrates are joined together by a liquid dropping method (ODF method) illuminance and exposure time: If 1000mJ the case of 100mW / cm ² / 365nm, 50mJ cured by irradiating one second 50mW / cm ² / 365nm), then for example even 1 hour thermal curing in a hot air oven at 120 ℃ do.

Example

Hereinafter, the present invention will be described concretely with reference to examples, but the present invention is not limited to these examples.

[Synthesis of curing agent]

(Example 1)

(B-1) 4,4 '- (methylene di-1,4-cyclohexylene) bis (semicarbazide)

Dissolution solution A in which 13.05 g of dicyclohexylmethane-4,4'-diisocyanate was dissolved in 75 g of ethanol and dissolution solution B in which 5 g of hydrazine was dissolved in 75 g of ethanol were prepared. The dissolving solution A was added dropwise to the flask at a rate of 1.4 g / minute while stirring the solution while controlling the temperature at 25 캜. After completion of the dropwise addition of the dissolving solution A, the reaction solution was measured by a Fourier transform infrared spectrophotometer to confirm that there was no peak near 2250 cm ^-1 derived from an isocyanate group, and the reaction was terminated. (1: 2 in molar ratio) relative to 1 mole of dicyclohexylmethane-4,4'-diisocyanate.

After completion of the reaction, the filtrate was filtered with a Kiriyama funnel (Kiriyama Co., Ltd.) using a filter paper (No.4 manufactured by Kiriyama), and the obtained filtrate was washed with 50 ml of distilled water and filtered again to obtain The filtrate was dried in a vacuum oven at 50 < 0 > C.

After drying, the mixture was pulverized with a high-pressure mill (trade name: Nanojetmizer, manufactured by Aisin Nanotechnologies) to prepare a carbaded compound having an average particle diameter (median diameter) of 2.0 탆.

The average particle diameter (median diameter) was measured using a particle size distribution meter (LA-950V2, manufactured by Horiba Seisakusho).

(Example 2)

(B-2) 4,4'-hexamethylenebis (semicarbazide)

Dissolved solution A in which 16.8 g of hexamethylene diisocyanate was dissolved in 150 g of ethanol and dissolution solution B in which 10 g of hydrazine was dissolved in 150 g of ethanol were prepared. With stirring while controlling the solution B at 25 占 폚, the solution A was added dropwise at a rate of 1.4 g / min. After completion of the dropwise addition of the dissolving solution A, the reaction solution was measured by a Fourier transform infrared spectrophotometer to confirm that there was no peak near 2250 cm ^-1 derived from an isocyanate group, and the reaction was terminated. The reaction was carried out so that 2 mol (1: 2 in molar ratio) of hydrazine was obtained per 1 mol of hexamethylene diisocyanate.

After completion of the reaction, the filtrate was filtered through a Kiriyama funnel (Kiriyama) using a filter paper (No.4 manufactured by Kiriyama), and the filtrate was washed with 50 ml of ethanol and again filtered to obtain The filtrate was dried in a vacuum oven at 50 < 0 > C. After drying, the mixture was pulverized with a high-pressure mill (trade name: Nano Jet Miller, manufactured by Aisin Nanotechnologies) to prepare a carbide compound having an average particle diameter (median diameter) of 2.1 μm.

(Example 3)

(B-7) 4- (Ethyl acrylate) semicarbazide

Dissolution solution A in which 14.1 g of 2-isocyanatoethyl acrylate was dissolved in 150 g of ethanol and dissolution solution B in which 5 g of hydrazine was dissolved in 150 g of ethanol were prepared. With stirring while controlling the solution B at 25 占 폚, the solution A was added dropwise at a rate of 1.4 g / min. After completion of the dropwise addition of the dissolving solution A, the reaction solution was measured by a Fourier transform infrared spectrophotometer to confirm that there was no peak near 2250 cm ^-1 derived from an isocyanate group, and the reaction was terminated. The reaction was carried out so that 1 mole of hydrazine (1: 1 in molar ratio) was added per 1 mole of 2-isocyanatoethyl acrylate.

After completion of the reaction, the ethanol was evaporated at 50 占 폚 with an evaporator, and the purified product was measured by a Fourier transform infrared spectrophotometer to confirm that there was no peak near 3300 cm < ^-1 > derived from ethanol and a liquid carbazide compound was prepared.

(Example 4)

(B-3) 4,4 '- (2,2,4-trimethylhexamethylene) bis (semicarbazide)

10.51 g of trimethyl hexane methylene diisocyanate was dissolved in 50 g of ethanol, and dissolution solution B was prepared by dissolving 5.0 g of hydrazine in 50 g of ethanol. With stirring while controlling the solution B at 25 占 폚, the solution A was added dropwise at a rate of 1.4 g / min. After completion of the dropwise addition of the dissolving solution A, the reaction solution was measured by a Fourier transform infrared spectrophotometer to confirm that there was no peak near 2250 cm ^-1 derived from an isocyanate group, and the reaction was terminated. The reaction was carried out so that the amount of hydrazine was 2 mol (1: 2 in molar ratio) relative to 1 mol of trimethylhexamethylene diisocyanate.

After completion of the reaction, the ethanol was evaporated at 50 占 폚 with an evaporator, and the purified product was measured by a Fourier transform infrared spectrophotometer to confirm that there was no peak near 3300 cm < ^-1 > derived from ethanol and a liquid carbazide compound was prepared.

(Example 5)

(B-5) 4,4 '- (1,3-phenylenebismethylene) bis (semicarbazide)

A solution A in which 18.82 g of m-xylylene diisocyanate was dissolved in 100 g of isopropanol and a solution B in which 25.3 g of hydrazine was dissolved in 100 g of isopropanol were prepared. In a three-necked flask, while stirring the solution while controlling the solution B at 30 占 폚, the solution A was dropped at a rate of 1.4 g / min. After completion of the dropwise addition of the dissolving solution A, the reaction solution was measured by a Fourier transform infrared spectrophotometer to confirm that there was no peak near 2250 cm ^-1 derived from an isocyanate group, and the reaction was terminated. (molar ratio: 1: 5) relative to 1 mol of m-xylylene diisocyanate.

After completion of the reaction, the filtrate was filtered with a Kiriyama funnel (manufactured by Kiriyama) using a filter paper (No.4 manufactured by Kiriyama), and the filtrate was washed with 50 ml of isopropyl alcohol and again filtered , And the obtained filtrate was dried at 50 DEG C in a vacuum oven.

After drying, the mixture was pulverized with a high-pressure mill (trade name: Nano Jet Meter, manufactured by Aisin Nanotechnologies) to prepare a carbide compound having an average particle diameter (median diameter) of 2.2 μm.

(Example 6)

(B-4) 4,4 '- (1,3-cyclohexylenebis methylene) bis (semicarbazide)

Dissolution solution A in which 19.42 g of 1,3-bis (isocyanatomethyl) cyclohexane was dissolved in 100 g of isopropanol and dissolution solution B in which 25.3 g of hydrazine was dissolved in 100 g of isopropanol was prepared. In a three-necked flask, while stirring the solution while controlling the solution B at 30 占 폚, the solution A was dropped at a rate of 1.4 g / min. After completion of the dropwise addition of the dissolving solution A, the reaction solution was measured by a Fourier transform infrared spectrophotometer to confirm that there was no peak near 2250 cm ^-1 derived from an isocyanate group, and the reaction was terminated. Was reacted with 5 mol of hydrazine (1: 5 in molar ratio) relative to 1 mol of 1,3-bis (isocyanatomethyl) cyclohexane.

After completion of the reaction, the filtrate was filtered with a Kiriyama funnel (manufactured by Kiriyama) using a filter paper (No.4 manufactured by Kiriyama), and the filtrate was washed with 50 ml of isopropyl alcohol and again filtered , And the obtained filtrate was dried at 50 DEG C in a vacuum oven.

(Example 7)

(B-6) 4,4'-isophorone bis (semicarbazide)

A dissolving solution A in which 22.22 g of isophorone diisocyanate was dissolved in 100 g of ethanol and a dissolving solution B in which 25.3 g of hydrazine was dissolved in 100 g of ethanol were prepared. In a three-necked flask, while stirring the solution while controlling the solution B at 30 占 폚, the solution A was dropped at a rate of 1.4 g / min. After completion of the dropwise addition of the dissolving solution A, the reaction solution was measured by a Fourier transform infrared spectrophotometer to confirm that there was no peak near 2250 cm ^-1 derived from an isocyanate group, and the reaction was terminated. (Molar ratio: 1: 5) relative to 1 mol of isophorone diisocyanate.

After completion of the reaction, the ethanol was evaporated at 50 占 폚 with an evaporator, and the purified product was measured by a Fourier transform infrared spectrophotometer to confirm that there was no peak near 3300 cm < ^-1 > derived from ethanol and a liquid carbazide compound was prepared.

(Example 8)

(Methylenebis (cyclohexane-4,1-diyl)] bis [3- (12-aminododecyl) urea]

A dissolution solution A in which 13.6 g of dicyclohexylmethane-4,4-diisocyanate was dissolved in 79 g of ethanol and a dissolution solution B in which 20.7 g of 1,12-diaminododecane (manufactured by TCI) were dissolved in 100 g of ethanol was prepared. In a three-necked flask, while stirring the solution while controlling the solution B at 30 占 폚, the solution A was dropped at a rate of 1.4 g / min. After completion of the dropwise addition, the reaction solution was measured with a Fourier transform infrared spectrophotometer to confirm that there was no peak near 2250 cm ^-1 derived from isocyanate group, and the reaction was completed. Diaminododecane was reacted so that 2 mol (1: 2 in molar ratio) of 1,12-diaminododecane was added to 1 mol of dicyclohexylmethane-4,4-diisocyanate.

The reaction solution was poured into 500 g of water stirring to promote crystallization and allowed to stand for 1 hour and then filtered with a Kiriyama funnel (manufactured by Kiriyama) using a filter paper (No.4 manufactured by Kiriyama) The water was dried in a vacuum oven at 50 < 0 > C. After drying, the mixture was naturally cooled to room temperature and pulverized with a high-pressure pulverizer (trade name: Nano Jet Meter, Aisin Nanotechnologies) to prepare an amine compound having an average particle diameter (median diameter) of 2.5 μm.

(Example 9)

(A-3) 1,1'- [methylenebis (cyclohexane-4,1-diyl)] bis [3- (6- aminohexyl) urea]

A dissolution solution A in which 12 g of 1,6-diaminohexane (manufactured by TCI) was dissolved in 100 g of ethanol and a dissolution solution B in which 13.6 g of dicyclohexylmethane-4,4'-diisocyanate was dissolved in 79 g of ethanol were prepared. In a three-necked flask, while stirring the solution while controlling the solution B at 30 占 폚, the solution A was dropped at a rate of 1.4 g / min. After completion of the dropwise addition, the reaction solution was measured with a Fourier transform infrared spectrophotometer to confirm that there was no peak near 2250 cm ^-1 derived from isocyanate group, and the reaction was completed. Di-n-hexylmethane-4,4-diisocyanate was reacted so that the amount of 1,6-diaminohexane was 2 mol (1: 2 in molar ratio) relative to 1 mol of dicyclohexylmethane-4,4-diisocyanate.

The solvent was then distilled off under reduced pressure with a rotary evaporator. After drying, the mixture was naturally cooled to room temperature and pulverized with a high-pressure pulverizer (trade name: Nano Jet Meter, Aisin Nanotechnologies) to give an amine compound having an average particle diameter (median diameter) of 2.2 μm.

(Example 10)

(A-4) 1,1 '- (hexane-1,6-diyl) bis [3- (12-aminododecyl) urea]

A dissolution solution A in which 49.65 g of 1,12-diaminododecane (manufactured by TCI) was dissolved in 150 g of ethanol and a dissolution solution B in which 20.54 g of hexamethylene diisocyanate was dissolved in 118 g of ethanol were prepared. In a three-necked flask, while stirring the solution while controlling the solution B at 30 占 폚, the solution A was dropped at a rate of 1.4 g / min. After completion of the dropwise addition, the reaction solution was measured with a Fourier transform infrared spectrophotometer to confirm that there was no peak near 2250 cm ^-1 derived from isocyanate group, and the reaction was completed. (1 mol) of 1,12-diaminododecane to 1 mol of hexamethylene diisocyanate.

The solvent was then distilled off under reduced pressure with a rotary evaporator. After drying, the mixture was naturally cooled to room temperature and pulverized with a high-pressure mill (trade name: Nano Jet Meter, Aisin Nanotechnologies) to prepare a diamine urea compound having an average particle diameter (median diameter) of 2.1 μm.

After completion of the reaction, the filtrate was filtered through a Kiriyama funnel (manufactured by Kiriyama) using a filter paper (No.4 manufactured by Kiriyama), and the obtained filtrate was washed with 100 ml of ethanol and again filtered to obtain The filtrate was dried in a vacuum oven at 50 < 0 > C.

(Example 11)

(A-5) 1,1 '- (hexane-1,6-diyl) bis [3- (2-aminoethyl) urea]

A dissolving solution A in which 17.17 g of hexamethylene diisocyanate was dissolved in 118 g of ethanol and a dissolution solution B obtained by dissolving 61.36 g of ethylenediamine in 150 g of ethanol were prepared. While stirring the solution B while controlling the solution B at a temperature of 25 캜 in a three-necked flask, the solution A was dropped at a rate of 1.4 g / min. After completion of the dropwise addition of the dissolving solution A, the reaction solution was measured by a Fourier transform infrared spectrophotometer to confirm that there was no peak near 2250 cm ^-1 derived from an isocyanate group, and the reaction was terminated. The reaction was carried out so that 10 mol of ethylenediamine (1: 10 in molar ratio) per 1 mol of hexamethylene diisocyanate was obtained.

After completion of the reaction, the filtrate was filtered through a Kiriyama funnel (manufactured by Kiriyama) using a filter paper (No.4 manufactured by Kiriyama), and the obtained filtrate was washed with 100 ml of ethanol and again filtered to obtain The filtrate was dried in a vacuum oven at 50 < 0 > C. After drying, the mixture was naturally cooled to room temperature and pulverized with a high-pressure pulverizer (trade name: Nano Jet Meter, Aisin Nanotechnologies) to give an amine compound having an average particle diameter (median diameter) of 2.2 μm.

(Example 12)

(A-6) 1,1 '- (hexane-1,6-diyl) bis [3- (6-aminohexyl) urea]

A solution B in which 17.17 g of hexamethylene diisocyanate was dissolved in 150 g of ethanol and a solution B in which 94.9 g of 1,6-diaminohexane (manufactured by TCI) was dissolved in 118 g of ethanol was prepared. While stirring the solution B while controlling the solution B at a temperature of 25 캜 in a three-necked flask, the solution A was dropped at a rate of 1.4 g / min. After completion of the dropwise addition of the dissolving solution A, the reaction solution was measured by a Fourier transform infrared spectrophotometer to confirm that there was no peak near 2250 cm ^-1 derived from an isocyanate group, and the reaction was terminated. The reaction was carried out so that 1 mol of 1,6-diaminohexane was 10 mol (molar ratio: 1:10) relative to 1 mol of hexamethylene diisocyanate.

The solvent was then distilled off under reduced pressure with a rotary evaporator. After drying, the mixture was naturally cooled to room temperature, and pulverized with a high-pressure mill (trade name: Nano Jet Meter, Aisin Nanotechnologies) to give an amine compound having an average particle diameter (median diameter) of 2.3 μm.

(Example 13)

(A-2) 1,1'- [methylenebis (cyclohexane-4,1-diyl)] bis [3- (2-aminoethyl) urea]

A dissolution solution A in which 13.55 g of dicyclohexylmethane 4,4'-diisocyanate was dissolved in 100 g of ethanol and a dissolution solution B in which 15.5 g of ethylenediamine (manufactured by TCI) was dissolved in 79 g of ethanol was prepared. While stirring the solution B while controlling the solution B at a temperature of 25 캜 in a three-necked flask, the solution A was dropped at a rate of 1.4 g / min. After completion of the dropwise addition of the dissolving solution A, the reaction solution was measured by a Fourier transform infrared spectrophotometer to confirm that there was no peak near 2250 cm ^-1 derived from an isocyanate group, and the reaction was terminated. And reacted with 1 mole of hexamethylene diisocyanate to make 5 mole of 1,6-diaminohexane (1: 5 in mole ratio).

After completion of the reaction, the filtrate was filtered through a Kiriyama funnel (manufactured by Kiriyama) using a filter paper (No.4 manufactured by Kiriyama), and the obtained filtrate was washed with 100 ml of ethanol and again filtered to obtain The filtrate was dried in a vacuum oven at 50 < 0 > C. After drying, the mixture was naturally cooled to room temperature and pulverized with a high-pressure pulverizer (trade name: Nano Jet Meter, Aisin Nanotechnologies) to give an amine compound having an average particle diameter (median diameter) of 2.2 μm.

(Synthesis Example)

(A-5 ') 1,1' - (hexane-1,6-diyl) bis [3- (2-aminoethyl) urea]

61.36 g (1020 mmol) of ethylenediamine and 150 g of toluene were stirred in a three-necked flask, and 118.5 g (150 ml) of toluene of 17.17 g (102 mmol) of hexamethylene diisocyanate was added dropwise. The reaction time was 30 minutes and the reaction solution was controlled at 40 ° C. After completion of the dropwise addition, the reaction solution was filtered, the precipitate was washed with toluene, and then poured into water. After stirring for 1 hour, filtration was carried out, and the obtained filtrate was concentrated under reduced pressure using an evaporator to confirm the precipitate. The reacted hexamethylene diisocyanate and ethylenediamine were 10 mol of ethylenediamine (1:10 in molar ratio) relative to 1 mol of hexamethylene diisocyanate. The resulting precipitate was washed with ethanol (EtOH) and dried under reduced pressure. The obtained crystals were pulverized with a high-pressure pulverizer (trade name: Nanojetmiller, manufactured by Aisin Nanotechnologies) to produce an amine compound having an average particle diameter (median diameter) .

(Example 14)

(A-7) Synthesis of N, N'-hexamethylene [Carbonylbis (aspartyl) (2-aminoethyl)] - [carbonylbis

Dissolving solution A in which 18.3 g of hexamethylene diisocyanate (manufactured by TCI) was dissolved in 240 g of isopropanol and dissolution solution B in which 33.48 g of 1,6-hexanediamine and 18.3 g of ethylenediamine were dissolved in 72.6 g of isopropanol were prepared. While stirring the solution B while controlling the solution B at a temperature of 25 캜 in a three-necked flask, the solution A was dropped at a rate of 1.4 g / min. After completion of the dropwise addition of the dissolving solution A, the reaction solution was measured by a Fourier transform infrared spectrophotometer to confirm that there was no peak near 2250 cm ^-1 derived from an isocyanate group, and the reaction was terminated. 5 mol of ethylenediamine and 5 mol of 1,6-diaminohexane (1: 5: 5 in molar ratio) per 1 mol of hexamethylene diisocyanate.

After completion of the reaction, the filtrate was filtered through a Kiriyama funnel (Kiriyama) using a filter paper (No.4 manufactured by Kiriyama), and the obtained filtrate was washed with 100 ml of isopropanol and filtrated again to obtain The filtrate was dried in a vacuum oven at 50 < 0 > C. After drying, the mixture was naturally cooled to room temperature and pulverized with a high-pressure pulverizer (trade name: Nano Jet Meter, Aisin Nanotechnologies) to give an amine compound having an average particle diameter (median diameter) of 2.2 μm.

[Production of epoxy resin]

A partially esterified epoxy resin was prepared according to the production method described in JP-A-5-295087. Specifically, a partially esterified epoxy resin (partially methacrylated epoxy resin) was prepared as follows.

(A) High purity bisphenol A type epoxy resin: 1000 parts by mass of Epiclon-850S (manufactured by DIC), 250 parts by mass of methacrylic acid, 900 parts by mass of toluene, 2 parts by mass of triethylamine, : 2 parts by mass, and the mixture was heated and stirred at 90 占 폚 for 8 hours to obtain a partial addition reaction product.

(B) 4500 parts by mass of toluene was added to the above product (a) to prepare a dilute solution. To this, 4500 parts by mass of pure water was added, and the mixture was stirred at room temperature for 1 hour and then allowed to stand to separate and remove the aqueous layer. This cleaning operation was repeated 3 to 5 times, followed by washing with the same amount of 1N NaOH solution 3 to 5 times, and further with cleaning with the same amount of pure water 3 to 5 times, and with respect to the final washing water, The ionic conductivity was measured using a measuring instrument (manufactured by Horiba Seisakusho Co., Ltd., conductivity meter), and it was confirmed that it was 10 mu S / cm or less.

(C) The solution obtained by filtering the solution of (b) above was concentrated under reduced pressure at 70 캜 to completely remove and purify toluene to synthesize a partially methacrylated epoxy resin.

Further, a partially-acrylated epoxy resin was synthesized by the same method using acrylic acid instead of methacrylic acid in accordance with the above synthesis example.

[Preparation of liquid crystal sealing composition]

, 15 parts by mass of spherical silica (SO-C1, manufactured by ADMAPANA CORPORATION) as an inorganic filler, 15 parts by mass of F-351 (manufactured by Nippon Zeon) as an organic filler, 100 parts by mass of a photo- , 3 parts by mass of Irgacure 907 (manufactured by BASF Japan), 2 parts by mass of KBM-403 (manufactured by Shinetsu Chemical Co., Ltd.) as a silane coupling agent, and 1 part by mass of Examples 1 to 5, 8 to 12 and 14 Of the curing agent was added in an amount of 1 equivalent based on 1 equivalent of the epoxy group of the partially methacrylated epoxy resin, and the resulting mixture was uniformly dispersed with a three-one motor (trade name: RW28basic, manufactured by IKA Corporation) to obtain a liquid crystal encapsulating resin composition.

(DDH, manufactured by Otsuka Chemical Co., Ltd.), which is commercially available dodecanedioic acid hydrazide, was used as Comparative Example 1 and 1,3-bis (hydrazinocarbonylethyl) -5-iso Propyl hydantoin (Amecure VDH, manufactured by Ajinomoto Fine Techno Co., Ltd.) was used as the liquid crystal sealing composition.

[Method of Measuring Adhesive Strength]

Fig. 2 is a view for explaining a method of measuring the adhesive strength by using the liquid crystal sealing composition of Examples 1 to 5, 8 to 12, 14 and Comparative Examples 1 to 2. Fig. As shown in Fig. 2, an ITO glass 8 having a thickness of 0.5 mm and an angle of 3.0 cm (a glass (9) having a thickness of 0.5 mm and an angle of 2.3 cm with an ITO electrode film on a glass surface) was prepared. The liquid crystal sealing composition (2) was coated on the center line of the ITO glass so as to have a diameter of 1.5 to 2.0 mm and a thickness of 6.0 to 10.0 μm as a bonding surface at 9 mm from both ends, One side of a glass (9) having a side length of 2.3 cm was fitted and bonded together to prepare a test piece (10). The UV-cured liquid crystal sealing composition (2) was cured by irradiation with UV 3000 mJ (trade name: UB-031-A / BM-E1, manufactured by Igraphics Co., Ltd.) to the bonded test piece 10 and then heating at 120 ° C for 60 minutes. The point of 5 mm from the center line of the ITO glass 8 of the cured test piece 10 was pressed with an autograph (AGS manufactured by Shimadzu Corporation) to measure the adhesive strength. The results are shown in Table 1.

[Glass bonding strength with alignment film]

(Having an orientation film on the glass surface) of 0.7 mm in thickness and 3.0 cm in each side and glass (8) (having an orientation film on the glass surface) rubbed with an orientation film (SanEver SE-7492, manufactured by Nissan Chemical Industries, Ltd.) An alignment film glass 9 having the same treatment as that of the glass 8 was prepared. As shown in Fig. 2, the liquid crystal sealing composition (2) was applied as a bonding surface at a point 9 mm from both ends on the center line of the glass so as to have a diameter of 1.5 mm to 2.0 mm and a thickness of 6.0 m to 10.0 m, cm and an orientation film glass 9 having a side length of 2.3 cm were aligned with each other and bonded to each other to produce a test piece 10. The UV-cured liquid crystal sealing composition (2) was cured by irradiation with UV 3000 mJ (trade name: UB-031-A / BM-E1, manufactured by Igraphics Co., Ltd.) to the bonded test piece 10 and then heating at 120 ° C for 60 minutes. The point of 5 mm from the center line of the ITO glass 8 of the cured test piece 10 was pressed with an autograph (AGS manufactured by Shimadzu Corporation) to measure the adhesive strength.

[Orientation Test Method]

Example 11 (curing agent: A-5) and Comparative Example 1 (curing agent: DDH) the liquid crystal sealing agent composition using a dispenser to seal 4000㎛ ² cross-section, a rubbed oriented film (Mountain Avenue SE-7492 with Nissan Dispersion was applied on an ITO glass substrate (60 mm x 70 mm x 0.7 mm t) equipped with a glass substrate (manufactured by Kagaku Kogyo Co., Ltd.). Thereafter, liquid crystal (TN liquid crystal, MLC-11900-080, manufactured by Merck) was dropped on the substrate, and the upper and lower substrates were joined together by liquid crystal dropping method (ODF method) Ushio den kkisa production, illumination and exposure time: for 50mJ 50mW / cm ² / 365nm 1 second in the case of 200mJ is cured by irradiating a 4 seconds ^{50mW / cm 2/365 nm)} , hot air then 120 ℃ And then thermally cured in an oven for one hour to prepare a test cell for orientation test. In the case of an illuminance of 0 mJ, a thermocuring was performed in a hot air oven at 120 캜 for one hour in a state in which ultraviolet rays were not irradiated to the liquid crystal and the sealing agent by a light shielding mask after bonding, and a test cell for orientation test was prepared .

For the obtained panel, the alignment state of the liquid crystal at the time of sealing was confirmed. Confirmation was carried out by an optical microscope, and the polarizing plate was observed by transmission through a test cell in a state of crossed nicol. The alignment state of the corner portion and the straight line portion of the liquid crystal at an illuminance of 200 mJ and 50 mJ was observed. The evaluation criterion of the orientation of the liquid crystal was determined based on the presence or absence of orientation confusion at the time of sealing. The case where the orientation disorder was 50 m or less at the time of sealing was evaluated as " ", and the case where there was more orientation disorder was rated as " x ". The results are shown in Table 2.

As shown in Table 1, the liquid crystal encapsulant compositions using the curing agents (Examples 1 to 5, 8 to 12, and 14) of the present invention were excellent in heat resistance and durability even when the dissimilar materials such as glass and ITO glass were bonded to each other, , The bonding strength was larger than that in the case of using 2 curing agents. The orientation of the orientation film of the liquid crystal encapsulant composition of Example 11 (curing agent A-5) was satisfactory because both the illuminance of 50 mJ and the light transmittance of 200 mJ were satisfactory because the alignment disorder during sealing was 50 탆 or less. , The illuminance of 50 mJ, and the light transmittance of 200 mJ both exceeded 50 mu m. From these results, it was found that the curing agent of the present invention, the resin composition and the liquid crystal encapsulant composition using the curing agent of the present invention are suitable for the thinning and the diversification of adhesiveness required for a sealing agent used for bonding a liquid crystal display panel and the like, It was confirmed that an adhesive strength capable of suppressing peeling at the time of mounting of the liquid crystal cell driving IC was exhibited.

(Example 15)

A dissolving solution A in which 17.17 g of hexamethylene diisocyanate was dissolved in 118 g of ethanol and a dissolution solution B obtained by dissolving 61.36 g of ethylenediamine in 150 g of ethanol were prepared. While stirring the solution B while controlling the solution B at a temperature of 25 캜 in a three-necked flask, the solution A was dropped at a rate of 1.4 g / min. After completion of the dropwise addition of the dissolving solution A, the reaction solution was measured by a Fourier transform infrared spectrophotometer to confirm that there was no peak near 2250 cm ^-1 derived from an isocyanate group, and the reaction was terminated. The reaction was carried out so that 10 mol of ethylenediamine (1: 10 in molar ratio) per 1 mol of hexamethylene diisocyanate was obtained.

After completion of the reaction, the filtrate was filtered through a Kiriyama funnel (manufactured by Kiriyama) using a filter paper (No.4 manufactured by Kiriyama), and the obtained filtrate was washed with 100 ml of ethanol and again filtered to obtain The filtrate was dried in a vacuum oven at 50 < 0 > C. After drying, the mixture was naturally cooled to room temperature and pulverized with a high-pressure mill (trade name: Nanojet Meter, Aisin Nanotechnologies) to obtain an amine compound (A-5) having an average particle diameter (median diameter) of 2.2 μm.

10 g of the amine compound (A-5) obtained above and 1.36 g of hexamethylene diisocyanate were mixed in 80 ml of methylcyclohexane, and the mixture was incubated at 50 DEG C for 24 hours.

Thereafter, the treatment solution was filtered with a Kiriyama funnel (Kiriyama) using a filter paper (No.4 manufactured by Kiriyama), and desalted. The obtained filtrate was mixed with 100 ml of methylcyclohexane, and the same filtration as described above was repeated three times in total. Finally, the resultant was filtered and dried to obtain a curing agent (E-1) comprising a compound obtained by treating an amine compound with an isocyanate compound by a vacuum dryer (manufactured by ESPEC) at 50 ° C and 1 Torr for 12 hours.

10 g of the amine compound (A-5) obtained above, 1.36 g of hexamethylene diisocyanate and 1.255 g of hydrogenated bisphenol A type epoxy resin (YX8034, manufactured by JER) were mixed in 80 ml of toluene, and the mixture was incubated at 50 ° C for 24 hours .

Thereafter, the treatment solution was filtered with a Kiriyama funnel (Kiriyama) using a filter paper (No.4 manufactured by Kiriyama), and desalted. The obtained filtrate was mixed with 100 ml of toluene and the same filtration as described above was repeated three times in total. Finally, the resultant was filtered and dried to obtain a curing agent (E-2) comprising a compound obtained by treating an amine compound with an isocyanate compound and an epoxy resin at 50 ° C and 1 Torr for 12 hours in a vacuum drier (manufactured by Especa).

[Preparation of liquid crystal sealing composition]

15 parts by mass of spherical silica (SO-C1, manufactured by Admapana) as an inorganic filler, 15 parts by mass of F-351 (manufactured by Nippon Zeon Co., Ltd.) as an organic filler, 100 parts by mass of the partially methacrylated epoxy resin obtained above, , 3 parts by mass of Irgacure 907 (manufactured by BASF Japan) as a photo radical initiator, 2 parts by mass of KBM-403 (manufactured by Shinetsu Chemical Co., Ltd.) as a silane coupling agent, E-1 or E-2 Was mixed in an amount of 15 parts by mass based on 100 parts by mass of the partially methacrylated epoxy resin, and the resulting mixture was homogeneously dispersed with a three-one motor (trade name: RW28basic, manufactured by IKA Corporation) to obtain a liquid crystal encapsulating resin composition.

[evaluation]

(Stability test)

Liquid stability

The initial viscosity of the liquid crystal encapsulant composition obtained above was measured immediately after the preparation (within 2 hours). Further, the viscosity after 2 weeks at 25 占 폚 was measured, and the rate of change (% / 2 weeks) of the viscosity after 2 weeks based on the initial viscosity was calculated.

The viscosity was measured in the following manner. A 3 占 R7.7 cone rotor was set in a RE-105U type viscometer (manufactured by Ohtsu Kagaku) and 0.15 ml of a liquid crystal encapsulant composition to be a target was set in a cone rotor, and the liquid crystal sealing agent The viscosity of the composition was measured. In the case of the measurement range over, it was decided that measurement was impossible. In addition, the standard of the measurement range overflow is 1,200,000 mPa · s.

Thermal stability

The initial viscosity of the liquid crystal encapsulant composition obtained above was measured and the viscosity after 22 hours at 40 캜 was further measured to calculate the rate of change (% / 22 hours) of viscosity after 22 hours of heating based on the initial viscosity Respectively.

The results of the liquid stability and the warming solution stability are shown in Table 3.

As is clear from the results in Table 3, it was found that the isocyanate-added amine compound to which any isocyanate was added to the amine compound was small in the liquid stability and the rate of change in the stability of the warming solution, and in particular, the rate of change in the stability of the warming solution was small.

(Curing test)

The liquid crystal sealant composition (resin composition) obtained in the above, and in two conditions (only 120 ℃ 1 hour, and UV 3000mJ / cm ² 120 ℃ 1 hour after treatment) shown in Table 4 below hardened, hardened pieces obtained Was measured by FT-IR, and the curability was evaluated. The epoxy hardening rate was calculated by the following formula. The methacrylic hardening rate was calculated by replacing the peak of the epoxy group with the peak of the methacrylic group in the following formula.

Reference peak; 1540 to 1480cm ^-1 (peak top near 1510cm ^-1)

The peak of the epoxy group; 925 to 895cm ^-1 (peak top near 910cm ^-1)

The peak of the methacryl group; 1650 to 1625 cm ^-1 (near the peak top of 1635 cm ^-1 )

From the results in Table 4, no remarkable deterioration of the curability was observed even when subjected to isocyanate treatment. That is, even if subjected to isocyanate treatment, the curability is not lowered and the liquid stability can be improved.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a liquid crystal cell driving IC capable of satisfactorily satisfying an adhesive strength capable of satisfactorily suppressing peeling at the time of cutting a cell and mounting a liquid crystal cell driving IC while satisfying a demand for diversification of adhesiveness by thinning and diversification of different materials And the curing agent of the present invention, the resin composition using the same and the liquid crystal encapsulant composition can be suitably used as a sealing agent or a sealing agent for electronic parts such as a liquid crystal display panel, Do.

The disclosure of Japanese Patent Application No. 2012-155976 is hereby incorporated by reference in its entirety.

All publications, patent applications, and technical specifications described in this specification are herein incorporated by reference to the same extent as if each individual publication, patent application, and technical specification were specifically and individually indicated to be incorporated by reference .

1: glass substrate
2: liquid crystal sealing composition
3: Liquid crystal injection hole
4: glass substrate
5: Cell for liquid crystal sealing
6: liquid crystal
7: LCD panel
8: ITO glass
9: Glass
10: Specimen

Claims (10)

A liquid crystal encapsulant composition comprising a curing agent (A) and a resin composition comprising a partially esterified epoxy resin (B) obtained by reacting an epoxy resin with (meth) acrylic acid,
(Meth) acrylic acid, wherein the curing agent (A) comprises an epoxy resin and a compound having at least one primary amino group in the molecule, obtained by the reaction of a diisocyanate compound, a triisocyanate compound or a tetraisocyanate compound with hydrazine, Is a curing agent for a partially esterified epoxy resin (B)
Wherein the diisocyanate compound satisfies the following formula (2a)

Wherein X ¹ is C ₁ to C ₁₂ alkylene, C ₃ to C ₁₂ cycloalkylene, C ₁ to C ₁₂ alkylene-C ₃ to C ₁₂ cycloalkylene, or C ₆ to C ₁₄ Arylene wherein the alkylene is linear or branched and may be substituted with halogen and C ₃ to C ₁₂ cycloalkylene or C ₆ to C ₁₄ arylene is unsubstituted or substituted by halogen or C ₁ to C _{And R} < ₄ >
The triisocyanate compound is represented by the following formula (3a)

A compound having an isocyanurate structure represented by the following formula: wherein R ² is the same or different and is a linear or branched C ₁ to C ₁₂ alkylene,
(3b)

(Wherein R ³ is the same or different and is a linear or branched C ₁ to C ₁₂ alkylene), or a triisocyanate compound having a bivalent structure represented by
(3c)

[Wherein R ⁴ is the same or different and is a straight or branched C ₁ to C ₁₂ alkylene group and R ⁵ is CH 3], and is a triisocyanate compound having an adduct structure represented by the following formula
The tetraisocyanate compound is represented by the following formula (4a)

[Wherein, X ³ is C ₃ to C ₁₂ cycloalkyl, -C ₁ to C ₁₂ alkylene -C ₃ to C ₁₂ cycloalkyl, or C ₆ to C ₁₄ aryl -C ₁ to C ₄ alkylene -C ₆ to C ₁₄ aryl group (the alkylene is a linear or branched, and may be substituted by halogen, a C ₃ to C ₁₂ cycloalkyl or C ₆ to C ₁₄ aryl, or unsubstituted or halogen or C ₁ to C ₄ alkyl Or a tetravalent group derived from a compound represented by the following formula (4b)

Wherein the liquid crystal sealing composition is tetraisocyanato silane. A liquid crystal encapsulant composition comprising a curing agent (A) and a resin composition comprising a partially esterified epoxy resin (B) obtained by reacting an epoxy resin with (meth) acrylic acid,
Wherein the curing agent (A) is represented by the following formula (I)

(Wherein,
R ¹ is a single bond,
n is 2, 3 or 4,
When n is 2, A is a C ₁ to C ₁₂ alkylene, a C ₃ to C ₁₂ cycloalkylene, a C ₁ to C ₁₂ alkylene-C ₃ to C ₁₂ cycloalkylene, or a C ₆ to C ₁₄ arylene Wherein the alkylene is linear or branched and may be substituted with halogen and C ₃ to C ₁₂ cycloalkylene and C ₆ to C ₁₄ arylene are unsubstituted or substituted by halogen or C ₁ to C ₄ alkyl , ≪ / RTI >
When n is 3, A is represented by the following formula (1)

(Wherein R ² is the same or different and is a linear or branched C ₁ to C ₁₂ alkylene), the following formula (2)

(Wherein R ³ is the same or different and is a linear or branched C ₁ to C ₁₂ alkylene)

(Wherein R ⁴ is the same or different and is a straight or branched C ₁ to C ₁₂ alkylene and R ⁵ is CH)
When n is 4, A is represented by the following formula (4)

Wherein X ³ is Si or a C ₃ to C ₁₂ cycloalkyl-C ₁ to C ₁₂ alkylene-C ₃ to C ₁₂ cycloalkyl, or a C ₆ to C ₁₄ aryl-C ₁ to C ₄ alkylene C ₆ to C ₁₄ aryl wherein the alkylene is linear or branched and is optionally substituted with 1 to 6 halogens and wherein C ₃ to C ₁₂ cycloalkyl or C ₆ to C ₁₄ aryl is unsubstituted, Or a tetravalent residue derived from a halogen or a C ₁ to C ₄ alkyl), and a compound having at least one primary amino group in the molecule, Is a curing agent for a partially esterified epoxy resin (B). The liquid crystal encapsulant composition according to claim 1 or 2, further comprising a compound obtained by treating a compound having at least one primary amino group in the molecule with an isocyanate compound. The liquid crystal sealing composition according to claim 1 or 2, further comprising a compound obtained by treating a compound having at least one primary amino group in the molecule with an isocyanate compound and an epoxy resin. The liquid crystal sealing composition according to claim 1 or 2, further comprising a compound obtained by treating a compound having at least one primary amino group in the molecule with a compound having an isocyanate compound and a hydroxy group. The epoxy resin composition according to claim 1 or 2, wherein the partially esterified epoxy resin (B) obtained by reacting the epoxy resin with (meth) acrylic acid has a (meth) acrylic acid content of 10 to 90 equivalent% based on 1 equivalent of the epoxy group of the epoxy resin Wherein the epoxy resin is a partially esterified epoxy resin. The epoxy resin composition according to claim 1 or 2, wherein the total amount of the primary amino groups contained in the curing agent (A) relative to 1 equivalent of the epoxy group of the partially esterified epoxy resin (B) obtained by reacting the epoxy resin with (meth) acrylic acid is 0.001 To 10 equivalents of the liquid crystal sealing composition. The epoxy resin composition according to claim 1 or 2, which is obtained by reacting one equivalent of an epoxy group of a partially esterified epoxy resin (B) obtained by reacting an epoxy resin with (meth) acrylic acid and a partially esterified epoxy resin obtained by reacting an epoxy resin with (meth) Wherein the total amount of the primary amino groups contained in the curing agent (A) is 0.001 to 10 equivalents based on the total of one equivalent of the unsaturated bond of the liquid crystal polymer (B). A liquid crystal display panel obtained by using the liquid crystal sealing composition according to claim 1 or 2. A liquid crystal display panel manufacturing method wherein a liquid crystal sealing composition according to claim 1 or 2 is used to perform photo-curing and then thermosetting.

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