CN104428339B

CN104428339B - Curing agent and resin composition using the same

Info

Publication number: CN104428339B
Application number: CN201380036329.7A
Authority: CN
Inventors: 樱庭一郎; 渡边自由
Original assignee: Kyoritsu Chemical and Co Ltd
Current assignee: Kyoritsu Chemical and Co Ltd
Priority date: 2012-07-11
Filing date: 2013-07-01
Publication date: 2020-01-07
Anticipated expiration: 2033-07-01
Also published as: JP6031514B2; KR101931074B1; KR101894623B1; TWI573822B; CN108264631A; TW201418344A; JP6114453B2; CN104428339A; JP2017061694A; JPWO2014010446A1; CN108264631B; WO2014010446A1; KR20150036433A; KR20180095728A

Abstract

The invention provides a curing agent, a resin composition and a liquid crystal sealing agent composition using the curing agent, a liquid crystal display panel and a manufacturing method of the liquid crystal display panel, wherein the curing agent is used for an epoxy resin and/or a resin with at least 1 unsaturated bond in a molecule, and the curing agent comprises a compound with at least 1 primary amino group in the molecule, which is obtained by the reaction of an isocyanate compound and hydrazine or a polyamine compound with more than 2 primary amino groups in the molecule.

Description

Curing agent and resin composition using the same

Technical Field

The present invention relates to a curing agent for an epoxy resin and/or a resin having at least 1 unsaturated bond in the molecule, and more particularly to a curing agent which can be suitably used for a liquid crystal display element such as a liquid crystal display, a resin composition using the curing agent, a liquid crystal sealant composition, a liquid crystal display panel, and a method for producing the liquid crystal display panel.

Background

In recent years, the thinning of the sealant has been advanced with the increase in size and narrowing of the display portion of the liquid crystal display. Further, as the object to be adhered of the sealant, not only glass but also inorganic materials such as ITO electrodes and SiN films, organic materials such as alignment films, and the like are also objects to be adhered, and the objects to be adhered are diversified, and the sealant is required to have a variety of adhesiveness capable of adhering different materials to each other.

As a sealant for bonding such different materials, for example, a sealant for a liquid crystal display element containing a curable resin such as epoxy (meth) acrylate and a curing agent such as a thermal epoxy curing agent and not containing an inorganic filler has been proposed (patent document 1). As the thermal epoxy curing agent used for the sealant for liquid crystal display element, dihydrazide compounds such as sebacic dihydrazide, isophthalic dihydrazide, adipic dihydrazide and the like are mentioned, and as other commercially available products, Amicure VDH, Amicure UDH (both manufactured by Ajinomoto Fine TECHNO Co., Ltd.) and the like are mentioned.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2010-85712

Disclosure of Invention

Problems to be solved by the invention

The thinning of the sealant and the diversification of the adhesiveness mutually affect each other, and the sealant is further required to have an improved adhesive strength in order to suppress peeling at the time of cutting out the cell and at the time of mounting the IC for driving the liquid crystal cell.

The present invention addresses the problem of finding a latent curing agent that can improve the adhesive strength while satisfying the demand for thinner sealing materials and diversified adhesive properties, and to provide a curing agent for epoxy resins and/or resins having at least 1 unsaturated bond in the molecule, a resin composition using the curing agent, and a liquid crystal sealing material composition.

Means for solving the problems

The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that a resin composition and a liquid crystal sealing composition can be obtained by using a compound having a urea structure in a molecule and at least 1 primary amino group as a latent curing agent for an epoxy resin and/or a resin having at least 1 unsaturated bond in a molecule, and that the composition can be applied to the thinning of a sealing agent for a liquid crystal display panel or the like, the diversification of adhesiveness, and the improvement of adhesive strength.

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

[1] Disclosed is a curing agent for an epoxy resin and/or a resin having at least 1 unsaturated bond in the molecule, which is a curing agent for an epoxy resin and/or a resin having at least 1 unsaturated bond in the molecule, and which contains a compound having at least 1 primary amino group in the molecule, which is obtained by reacting an isocyanate compound with hydrazine or a polyamine compound having 2 or more primary amino groups in the molecule.

[2] A curing agent for an epoxy resin and/or a resin having at least 1 unsaturated bond in the molecule, which comprises a compound having at least 1 primary amino group in the molecule represented by the following formula (I),

[ CHEM 1]

[ in the formula

R¹Is a single bond, or is C₁～C₁₂Alkylene, C interrupted discontinuously by 1 or more NH (imino) or O atoms (oxygen atoms)₂～C₁₂The alkylene group (H atom (hydrogen atom) bonded to N atom (nitrogen atom)) may be substituted with amino group or C₁～C₁₂Alkylamino of (a), C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂cycloalkylene-C₁～C₁₂Alkylene radical, C₃～C₁₂cycloalkylene-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Arylene radical, C₁～C₄alkylene-C₆～C₁₄Arylene radical, C₁～C₄alkylene-C₆～C₁₄Arylene radical-C₁～C₄Alkylene, or C₆～C₁₄Arylene radical-C₁～C₄alkylene-C₆～C₁₄Arylene (here, alkylene is straight-chain or branched and may be substituted by halogen, C₃～C₁₂Cycloalkylene or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄An alkyl group, a carboxyl group,

n is 1,2, 3 or 4,

when n is 2 or more, R¹Independently of one another, have the same meaning as above;

when n is 1, A is C₁～C₁₂Alkyl, C interrupted discontinuously by 1 or more than 1O atoms (oxygen atoms)₂～C₁₂Alkyl radical, C₂～C₁₂Alkoxycarbonylalkylene group, C₃～C₁₂Cycloalkyl radical, C₁～C₁₂alkyl-C₃～C₁₂Cycloalkylene radical, C₃～C₁₂cycloalkyl-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Aryl radical, C₁～C₄alkyl-C₆～C₁₄Arylene radical, C₆～C₁₄aryl-C₁～C₄alkylene-C₆～C₁₄Arylene (here, alkylene is straight-chain or branched and may be substituted by halogen, C₃～C₁₂Cycloalkyl radical, C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Aryl, or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄Alkyl), or (meth) acryloyloxyalkyl;

when n is 2, A is C₁～C₁₂Alkylene, C interrupted discontinuously by 1 or more than 1O atoms (oxygen atoms)₂～C₁₂Alkylene radical, C₁～C₁₂Alkoxycarbonylalkylene radical, C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂cycloalkylene-C₁～C₁₂Alkylene radical, C₃～C₁₂cycloalkylene-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene, di-C₃～C₁₂Cycloalkanediyl group, C₆～C₁₄Arylene radical, C₁～C₄alkylene-C₆～C₁₄Arylene radical-C₁～C₄Alkylene, or C₆～C₁₄Arylene radical-C₁～C₄alkylene-C₆～C₁₄Arylene (here, alkylene is straight-chain or branched and may be substituted by halogen, C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄Alkyl groups);

when n is 3, A is the following formula (1), the following formula (2) or the following formula (3),

[ CHEM 2]

(in the formula, R²Identical or different, being straight-chain or branched C₁～C₁₂An alkylene group),

[ CHEM 3]

(in the formula, R³Identical or different, being straight-chain or branched C₁～C₁₂An alkylene group),

[ CHEM 4]

(in the formula, R⁴Identical or different, being straight-chain or branched C₁～C₁₂Alkylene radical, R⁵Is CH);

when n is 4, A is the following formula (4),

[ CHEM 5]

{ in formula (II), X³Is Si or is C₃～C₁₂cycloalkyl-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkyl, or C₆～C₁₄aryl-C₁～C₄alkylene-C₆～C₁₄Aryl (here, alkylene is straight-chain or branched and may be substituted with 1to 6 halogens, C₃～C₁₂Cycloalkyl or C₆～C₁₄Aryl unsubstituted or substituted by halogen or C₁～C₄Alkyl) derived 4-valent residues }.

[3] The curing agent according to [2] above, wherein the compound having at least 1 primary amino group in the molecule is represented by the following formula (Ia),

[ CHEM 6]

In the formula (I), the compound is represented by,

R¹independently of one another, have the meanings given in [2] above]The same as in (1) above, or a combination thereof,

X¹is C₁～C₁₂Alkylene, C interrupted discontinuously by 1 or more than 1O atoms (oxygen atoms)₂～C₁₂Alkylene radical, C₁～C₁₂Alkoxycarbonylalkylene radical, C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂cycloalkylene-C₁～C₁₂Alkylene radical, C₃～C₁₂cycloalkylene-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene, di-C₃～C₁₂Cycloalkanediyl group, C₆～C₁₄Arylene radical, C₁～C₄alkylene-C₆～C₁₄Arylene radical-C₁～C₄Alkylene, or C₆～C₁₄Arylene radical-C₁～C₄alkylene-C₆～C₁₄Arylene (here, alkylene is straight-chain or branched and may be substituted by halogen, C₃～C₁₂Cycloalkylene or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄Alkyl groups) are used.

[4] The curing agent according to [2] above, wherein the compound having at least 1 primary amino group in the molecule is represented by the following formula (IIa),

[ CHEM 7]

In the formula (I), the compound is represented by,

R¹the meaning of (1) and the above-mentioned [2]The same as in (1) above, wherein,

X²is C₁～C₁₂Alkyl, C interrupted discontinuously by 1 or more than 1O atoms (oxygen atoms)₂～C₁₂Alkyl radical, C₁～C₁₂Alkoxycarbonylalkylene group, C₃～C₁₂Cycloalkyl radical, C₁～C₁₂alkyl-C₃～C₁₂Cycloalkylene radical, C₃～C₁₂cycloalkyl-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Aryl radical, C₁～C₄alkyl-C₆～C₁₄Arylene radical, C₆～C₁₄aryl-C₁～C₄alkylene-C₆～C₁₄Arylene (here, alkylene is straight-chain or branched and may be substituted by halogen, C₃～C₁₂Cycloalkyl radical, C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Aryl or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄Alkyl), or (meth) acryloyloxyalkyl ].

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

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

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

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

[9] The resin composition according to the above [8], wherein the epoxy resin is a partial esterified epoxy resin obtained by reacting 1 equivalent of an epoxy group of the epoxy resin with 10 to 90 equivalent% of (meth) acrylic acid.

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

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

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

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

[14] A method for producing a liquid crystal display panel, wherein the liquid crystal sealing composition according to [12] above is used in a liquid crystal dropping process, and photocured and then thermally cured.

Effects of the invention

According to the present invention, it is possible to provide a sealant which can be applied to thinning of a sealant of a liquid crystal display panel or the like and diversification of adhesiveness, and which can exhibit an adhesive strength capable of suppressing peeling at the time of cutting out a cell, at the time of mounting a liquid crystal cell driving IC, or the like.

Drawings

Fig. 1 is an explanatory view showing one embodiment of manufacturing a liquid crystal display panel by using a liquid crystal sealant composition.

Fig. 2 is an explanatory view for explaining a method of testing the adhesive strength of the liquid crystal sealing composition.

Detailed Description

In the present specification, the numerical range indicated by the term "to" represents a range including numerical values before and after the term "to" as a minimum value and a maximum value, respectively. The amount of each component in the composition refers to the total amount of a plurality of substances present in the composition, unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. "C_a～C_bThe term "refers to a range of carbon atoms from a to b.

[ curing agent ]

The present invention relates to a curing agent for an epoxy resin and/or a resin having at least 1 unsaturated bond in the molecule, which comprises a compound having at least 1 primary amino group in the molecule obtained by the reaction of an isocyanate compound with hydrazine or with a polyamine compound having 2 or more primary amino groups in the molecule. By using a curing agent containing a compound having a urea structure in addition to at least 1 primary amino group in the molecule as a latent curing agent for an epoxy resin and/or a resin having at least 1 unsaturated bond in the molecule (e.g., (meth) acrylic resin or the like), it is possible to achieve a reduction in the wire size and a diversification in the adhesiveness of a sealant for a liquid crystal display panel or the like, and to develop an adhesive strength that can suppress peeling at the time of cutting out a cell, at the time of mounting a liquid crystal cell driving IC, or the like.

Since a compound obtained by reacting an isocyanate compound with hydrazine or a polyamine compound having 2 or more primary amino groups in the molecule has a urea structure and at least 1 primary amino group in the molecule, the hydrogen bonding strength to an adherend is improved, and the bonding strength is supposed to be improved as compared with a hydrazide compound or an amine compound which has been used as a curing agent.

[ isocyanate Compound ]

The isocyanate compound used in the present invention is a compound having at least 1 isocyanate group (-N ═ C ═ O), and is not particularly limited, and a monoisocyanate compound, a diisocyanate compound, a triisocyanate compound, a tetraisocyanate compound, and the like can be given.

(Monoisocyanate Compound)

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

[ CHEM 8]

X²-N＝C＝O···(1a)

In the formula (1a), X²Is C₁～C₁₂Alkyl, C interrupted discontinuously by 1 or more than 1O atoms (oxygen atoms)₂～C₁₂Alkyl radical, C₁～C₁₂Alkoxycarbonylalkylene group, C₃～C₁₂Cycloalkyl radical, C₁～C₁₂alkyl-C₃～C₁₂Cycloalkylene radical, C₃～C₁₂cycloalkyl-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Aryl radical, C₁～C₄alkyl-C₆～C₁₄Arylene radical, C₆～C₁₄aryl-C₁～C₄alkylene-C₆～C₁₄Arylene (here, alkylene is straight-chain or branched and may be substituted by halogen, C₃～C₁₂Cycloalkyl radical, C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Aryl, or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄Alkyl), or (meth) acryloyloxyalkyl. X in the formula (1a)²The same as A in the case where n is 1 in the formula (I).

In this specification, "C" alone or in combination with other terms₁～C₁₂The alkyl group "is a linear or branched alkyl group, may be substituted with a halogen, may be interrupted by 1 or more O atoms (oxygen atoms) discontinuously, and is preferably a linear alkyl group. The number of carbon atoms of the alkyl group is in the range of C₁～C₁₂More preferably C₁～C₈More preferably C₁～C₆And is especiallyPreferably C₁～C₄The range of (1). Specific examples thereof include straight-chain alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, and n-dodecyl, and branched-chain alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, isooctyl, tert-octyl, 2-ethylhexyl, and tert-nonyl. 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, and more preferably a fluorine atom. The number of substitution is 1to 12, preferably 1to 6, more preferably 1to 4, and particularly preferably 1to 3.

In this specification, "C" alone or in combination with other terms₁～C₁₂The alkylene group "is a linear or branched alkylene group, which may be substituted with a halogen, or may be interrupted discontinuously by 1 or more NH (imino) groups or O atoms (oxygen atoms) (H atoms (hydrogen atoms) bonded to N atoms (nitrogen atoms) may be interrupted by amino groups or C atoms₁～C₁₂Substituted with alkylamino) groups, preferably linear alkylene groups. The number of carbon atoms of the alkylene group is in the range of C₁～C₁₂More preferably C₁～C₈More preferably C₁～C₆Particularly preferably C₁～C₄The range of (1). Specific examples thereof include methylene, ethylene, trimethylene, propylene, tetramethylene, 1-methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene, pentamethylene, 1-methyltetramethylene, 4-methyltetramethylene, 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, and more preferably a fluorine atom. The number of substitution is 1to 12, preferably 1to 6, more preferably 1to 4, and particularly preferably 1to 3.

In this specification, for "C₁～C₁₂Alkoxycarbonylalkylene "or" C₁～C₁₂The range of the number of carbon atoms of the alkoxy group or alkyleneoxy group of the alkyleneoxycarbonylalkylene group "includes C₁～C₁₂More preferably C₁～C₈More preferably C₁～C₆Particularly preferably C₁～C₄The range of (1). Specific examples thereof include linear groups such as methoxycarbonylmethylene, ethoxycarbonylmethylene, n-propoxycarbonylmethylene, n-butoxycarbonylmethylene, n-pentyloxycarbonylmethylene, n-hexyloxycarbonylmethylene, n-heptyloxycarbonylmethylene, n-octyloxycarbonylmethylene, n-nonyloxycarbonylmethylene, n-decyloxycarbonylmethylene, n-undecyloxycarbonylmethylene, and n-dodecyloxycarbonylmethylene; a branched group such as isopropoxycarbonylmethylene, isobutoxycarbonylmethylene, sec-butoxycarbonylmethylene, tert-butoxycarbonylmethylene, 2-methylbutoxycarbonylmethylene, isooctyloxycarbonylmethylene, tert-octyloxycarbonylmethylene, and 2-ethylhexyloxycarbonylmethylene.

In this specification, "C" alone or in combination with other terms₃～C₁₂The range of the number of carbon atoms of the cycloalkyl group "may include C₃～C₁₂More preferably C₃～C₈More preferably C₃～C₆Particularly preferably C₄～C₆The range of (1). Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl. C₃～C₁₂Cycloalkyl is preferably cyclopentyl or cyclohexyl. C₃～C₁₂Cycloalkyl is unsubstituted or may be substituted by halogen or C₁～C₄Examples 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, and more preferably a chlorine atom. For C as a substituent₁～C₄Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. C as a substituent₁～C₄The alkyl group is preferably methylAn ethyl or n-propyl group, more preferably a methyl or ethyl group. The number of substitution when a substituent is present is 1to 5, preferably 1to 3, more preferably 1to 2, and particularly preferably 1.

In this specification, "C" alone or in combination with other terms₃～C₁₂The number of carbon atoms of the cycloalkylene group "may be in the range of: is C₃～C₁₂More preferably C₃～C₈More preferably C₃～C₆Particularly preferably C₄～C₆The range of (1). Specific examples thereof include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene, cyclodecylene, cycloundecylene and cyclododecylene. C₃～C₁₂The cycloalkylene group is preferably a cyclopentylene group or a cyclohexylene group. C₃～C₁₂Cycloalkylene is unsubstituted or may be substituted by halogen or C₁～C₄Examples 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, and more preferably a chlorine atom. For C as a substituent₁～C₄Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. C as a substituent₁～C₄The alkyl group is preferably a methyl group, an ethyl group or an n-propyl group, more preferably a methyl group or an ethyl group. The number of substitution when a substituent is present is 1to 4, preferably 1to 3, more preferably 1to 2, and particularly preferably 1.

In this specification, "C" alone or in combination with other terms₆～C₁₄Aryl "is a 1-valent group having at least 1 aromatic ring. Specific examples thereof include phenyl, biphenyl, naphthyl, anthryl, phenanthryl and the like. Preferably phenyl, biphenyl or naphthyl, more preferably phenyl or naphthyl. C₆～C₁₄Aryl is unsubstituted or may be substituted by halogen or C₁～C₄Examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Halogen as substituentIs selected from a fluorine atom or a chlorine atom, more preferably a chlorine atom. For C as a substituent₁～C₄Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. C as a substituent₁～C₄The alkyl group is preferably a methyl group, an ethyl group or an n-propyl group, more preferably a methyl group or an ethyl group. The number of substitution when a substituent is present is 1to 5, preferably 1to 3, more preferably 1to 2, and particularly preferably 1.

In this specification, "C" alone or in combination with other terms₆～C₁₄Arylene "is a 2-valent group having at least 1 aromatic ring. Specific examples thereof include phenylene, naphthylene, anthrylene, phenanthrylene and the like. Preferably, phenylene and naphthylene, and more preferably, phenylene and naphthylene. C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄Examples 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, and more preferably a fluorine atom or a chlorine atom. For C as a substituent₁～C₄Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. C as a substituent₁～C₄The alkyl group is preferably a methyl group, an ethyl group or an n-propyl group, more preferably a methyl group or an ethyl group. The number of substitution when a substituent is present is 1to 4, preferably 1to 3, more preferably 1to 2, and particularly preferably 1.

As the (meth) acryloyloxyalkyl isocyanate as the monoisocyanate compound, a compound represented by the following formula (1b) can be mentioned.

[ CHEM 9]

H₂C＝C(R⁶)-COO-R7-NCO···(1b)

In the formula (1b), R⁶Represents a hydrogen atom or a methyl group, R⁷Is represented by C₁～C₆An alkylene group. R⁷C of (A)₁～C₆The number of carbon atoms of the alkylene group is preferably in the range of C₂～C₆More preferably C₃～C₆。

Specific examples of the monoisocyanate compound include methyl isocyanate, ethyl isocyanate, n-hexyl isocyanate, cyclohexyl isocyanate, 2-ethylhexyl isocyanate, phenyl isocyanate, benzyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, heptyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, t-butyl isocyanate, isocyanatoethyl acetate, isocyanatobutyl acetate, (S) - (-) -2-isocyanatomethyl propionate, 1-naphthyl isocyanate, 4-chlorophenyl isocyanate, 4-fluorophenyl isocyanate, phenylethyl isocyanate, p-tolyl isocyanate, m-tolyl isocyanate, and 3, 5-dimethylphenyl isocyanate.

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

(diisocyanate compound)

Examples of the diisocyanate compound include compounds represented by the following formula (2 a).

[ CHEM 10]

O＝C＝N-X¹-N＝C＝O···(2a)

In the formula (2a), X¹Is C₁～C₁₂Alkylene, C interrupted discontinuously by 1 or more than 1O atoms (oxygen atoms)₂～C₁₂Alkylene radical, C₁～C₁₂Alkoxycarbonylalkylene radical, C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂cycloalkylene-C₁～C₁₂Alkylene radical, C₃～C₁₂cycloalkylene-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene, di-C₃～C₁₂Cycloalkanediyl group, C₆～C₁₄Arylene (I)Base, C₁～C₄alkylene-C₆～C₁₄Arylene radical-C₁～C₄Alkylene, or C₆～C₁₄Arylene radical-C₁～C₄alkylene-C₆～C₁₄Arylene (here, alkylene is straight-chain or branched and may be substituted by halogen, C₃～C₁₂Cycloalkylene or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄Alkyl groups). X in the formula (2a)¹The same as A in the case where n is 2 in the formula (I).

Specific examples of the diisocyanate compound include diphenylmethane diisocyanate (MDI), Tolylene Diisocyanate (TDI), Xylylene Diisocyanate (XDI), hydrogenated xylylene diisocyanate (hydrogenated XDI), isophorone diisocyanate (IPDI), tolidine diisocyanate (TPDI), Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), 2,4, 4-trimethylhexamethylene diisocyanate (TMHDI), 3,5, 5-trimethylhexamethylene diisocyanate (TMHDI), 4,4 '-diisocyanato-3, 3' -dimethylbiphenyl, 4,4 '-diisocyanato-3, 3' -dimethyldiphenylmethane, 2-bis (4-isocyanatophenyl) hexafluoropropane, 2, 4-diisocyanatotoluene, 1, 3-bis (2-isocyanato-2-propyl) benzene, tolyl-2, 6-diisocyanate, 1, 4-phenylene diisocyanate, 1, 3-phenylene diisocyanate, 1, 5-diisocyanatonaphthalene and the like.

(triisocyanate Compound)

Examples of the triisocyanate compound include compounds having an isocyanurate structure, a biuret structure, or an addition structure, each of which has an isocyanate group at the 3-terminal end. Examples of the triisocyanate compound having an isocyanurate structure include a compound having an isocyanurate structure represented by the following formula (3 a).

[ CHEM 11]

In the formula, R²Identical or different, being straight-chain or branched C₁～C₁₂An alkylene group.

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

[ CHEM 12]

In the formula, R³Identical or different, being straight-chain or branched C₁～C₁₂An alkylene group.

Examples of the triisocyanate compound having an addition structure include compounds represented by the following formula (3 c).

[ CHEM 13]

In the formula, R⁴Identical or different, being straight-chain or branched C₁～C₁₂Alkylene radical, R⁵Is CH.

Specific examples of the triisocyanate compound include tris (isocyanatomethyl) isocyanurate, tris (isocyanatoethyl) isocyanurate, tris (isocyanatopropyl) isocyanurate, tris (isocyanatobutyl) isocyanurate, tris (isocyanatohexyl) isocyanurate, N '-2-triisocyanate methylmalonamide, N' -2-triisocyanate hexylmalonamide, and the like.

(Tetraisocyanate Compound)

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

[ CHEM 14]

In the formula, X³Is composed of C₃～C₁₂cycloalkyl-C₁～C₁₂Alkylene radical-C₃～C₁₂Cycloalkyl, or C₆～C₁₄aryl-C₁～C₄alkylene-C₆～C₁₄Aryl (alkylene is straight-chain or branched and may be substituted by halogen, C₃～C₁₂Cycloalkyl or C₆～C₁₄Aryl is unsubstituted or may be substituted by halogen or C₁～C₄Alkyl) derived 4-valent groups.

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

[ CHEM 15 ]

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

[ polyamine compound ]

The polyamine compound is a compound having at least 2 primary amino groups, and examples thereof include a polyamine compound represented by the following formula (5 a).

[ CHEM 16 ]

NH₂-L-NH₂···(5a)

In the formula, L is C₁～C₁₂Alkylene, C interrupted discontinuously by 1 or more NH (imino) or O atoms (oxygen atoms)₂～C₁₂The alkylene group (H atom (hydrogen atom) bonded to N atom (nitrogen atom)) may be substituted with amino group or C₁～C₁₂Alkylamino substituted), C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂cycloalkylene-C₁～C₁₂Alkylene radical, C₃～C₁₂cycloalkylene-C₁～C₄alkylene-C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Arylene radical, C₁～C₄alkylene-C₆～C₁₄Arylene radical, C₁～C₄alkylene-C₆～C₁₄Arylene radical-C₁～C₄Alkylene, or C₆～C₁₄Arylene radical-C₁～C₄alkylene-C₆～C₁₄Arylene (here, alkylene is straight-chain or branched and may be substituted by halogen, C₃～C₁₂Cycloalkylene or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄Alkyl groups). L in the formula (5a) and R in the formulae (I), (Ia) and (IIa)¹Have the same meaning.

Examples of the polyamine compound include a diamine compound having 2 primary amino groups, a triamine compound having 3 primary amino groups, and the like. The diamine compound having 2 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), a compound wherein L is a single bond is hydrazine.

As having C in aliphatic diamines₁～C₁₂Specific examples of the compound of an alkylene group include ethylenediamine, propylenediamine, 1, 2-diaminopropane, 1, 4-butanediamine, 1, 5-pentanediamine, 1, 6-hexanediamine, 1, 7-heptanediamine, 1, 8-octanediamine, 1, 12-dodecanediamine, propane-1, 2-diamine, and 1, 2-diamino-2-methylpropane.

As the straight chain or branched C having non-continuous interruption by 1 or more O atoms (oxygen atoms) in the aliphatic diamine₂～C₁₂Specific examples of the alkylene compound of (a) include 2, 2' -oxybis (ethylamine), 1, 2-bis (2-aminoethoxy) ethane, 1, 11-diamino-3, 6, 9-trioxaundecane, bis (3-aminopropyl) ether, 1, 4-butanediol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, and ethylene glycol bis (3-aminopropyl) ether.

As the straight chain or branched C having discontinuous interruptions by 1 or more NH (imino group) in the aliphatic diamine₂～C₁₂Alkylene group (bonded to N atom (nitrogen atom))H atom (hydrogen atom) of (A) may be substituted by amino group or C₁～C₁₂Specific examples of the "alkylamino-substituted") compound include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, tris (2-aminoethyl) amine, N ' -bis (3-aminopropyl) ethylenediamine, bis (hexamethylene) triamine, 3 ' -diamino-N-methyldipropylamine, 3 ' -diaminodipropylamine, and bis (3-aminopropyl) methylamine.

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

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

Specific examples of the triamine compound having 3 primary amino groups include tris (4-aminophenyl) amine, tris (3-aminopropyl) amine, tris (2-aminoethyl) amine represented by the following formula, and the like.

[ CHEM 17 ]

The isocyanate compound and hydrazine or the polyamine compound are preferably reacted with each other in an organic solvent or without a solvent (without a solvent) at a controlled temperature, and the hydrazine or the polyamine compound is preferably 0.01 to 50 mol, more preferably 0.1 to 50 mol, further preferably 0.1 to 30 mol, and particularly preferably 0.1 to 20 mol, based on 1 mol of the isocyanate compound, and the temperature is preferably-10 to 120 ℃, more preferably-5 to 100 ℃, further preferably 0 to 50 ℃, and particularly preferably 5 to 30 ℃.

Further, it is preferable that the curing agent contains a compound obtained by reacting an isocyanate compound with hydrazine or a polyamine compound, and the total number of primary amino groups contained in the hydrazine or the polyamine compound is preferably 0.01 to 50 mol, more preferably 0.1 to 50 mol, further preferably 0.1 to 30 mol, particularly preferably 0.5 to 20 mol, based on 1 mol of the isocyanate group contained in the isocyanate compound.

[ curing agent ]

The curing agent for an epoxy resin and/or a resin having at least 1 unsaturated bond according to the present invention comprises a compound represented by the following formula (I).

The curing agent of the present invention comprises a compound represented by the following formula (I),

[ CHEM 18 ]

In the formula (I), the compound is represented by,

R¹is a single bond, or is C₁～C₁₂Alkylene, C interrupted discontinuously by 1 or more NH (imino) or O oxygen atoms (oxygen atoms)₂～C₁₂The alkylene group (H atom (hydrogen atom) bonded to N atom (nitrogen atom)) may be substituted with amino group or C₁～C₁₂Alkylamino of (a), C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂cycloalkylene-C₁～C₁₂Alkylene radical, C₃～C₁₂cycloalkylene-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Arylene radical, C₁～C₄alkylene-C₆～C₁₄Arylene radical, C₁～C₄alkylene-C₆～C₁₄Arylene radical-C₁～C₄Alkylene, or C₆～C₁₄Arylene radical-C₁～C₄alkylene-C₆～C₁₄Arylene (here, alkylene is straight-chain or branched and may be substituted by halogen, C₃～C₁₂Cycloalkylene or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄An alkyl group),

n is 1,2, 3 or 4,

when n is 2 or more, R¹Independently of one another, have the same meanings as described above.

When n is 1, A is C₁～C₁₂Alkyl, C interrupted discontinuously by 1 or more than 1O atoms (oxygen atoms)₂～C₁₂Alkyl radical, C₂～C₁₂Alkoxycarbonylalkylene group, C₃～C₁₂Cycloalkyl radical, C₁～C₁₂alkyl-C₃～C₁₂Cycloalkylene radical, C₃～C₁₂cycloalkyl-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Aryl radical, C₁～C₄alkyl-C₆～C₁₄Arylene radical, C₆～C₁₄aryl-C₁～C₄alkylene-C₆～C₁₄Arylene (here, alkylene is straight-chain or branched and may be substituted by halogen, C₃～C₁₂Cycloalkyl radical, C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Aryl or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄Alkyl), or (meth) acryloyloxyalkyl;

when n is 2, A is C₁～C₁₂Alkylene, C interrupted discontinuously by 1 or more than 1O atoms (oxygen atoms)₂～C₁₂Alkylene radical, C₁～C₁₂Alkoxycarbonylalkylene radical, C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂cycloalkylene-C₁～C₁₂Alkylene radical, C₃～C₁₂cycloalkylene-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene, di-C₃～C₁₂Cycloalkanediyl group, C₆～C₁₄Arylene radical, C₁～C₄alkylene-C₆～C₁₄Arylene radical-C₁～C₄Alkylene, or C₆～C₁₄Arylene radical-C₁～C₄alkylene-C₆～C₁₄Arylene (here, alkylene is straight-chain or branched and may be substituted by halogen, C₃～C₁₂Cycloalkylene or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄Alkyl groups);

[ CHEM 19 ]

[ CHEM 20 ]

[ CHEM 21 ]

when n is 4, A is the following formula (4),

[ CHEM 22 ]

{ in formula (II), X³Is Si or is C₃～C₁₂Cycloalkyl radicals-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkyl, or C₆～C₁₄aryl-C₁～C₄alkylene-C₆～C₁₄Aryl (here, alkylene is straight-chain or branched and may be substituted by halogen, C)₃～C₁₂Cycloalkyl or C₆～C₁₄Aryl unsubstituted or substituted by halogen or C₁～C₄Alkyl) derived 4-valent residues }.

The compounds of the above formula (I) are preferably obtained as follows: the compound having at least 1 isocyanate group (-N ═ C ═ O) is reacted with hydrazine or a polyamine compound, for example, at least one isocyanate compound selected from the group consisting of the above monoisocyanate compound, the above diisocyanate compound, the above triisocyanate compound and the above tetraisocyanate compound. The compound represented by the formula (I) is preferably obtained by reacting the isocyanate compound with the hydrazine or the polyamine compound in an organic solvent or without a solvent (without a solvent) at a controlled temperature, and the hydrazine or the polyamine compound is preferably 0.01 to 50 mol, more preferably 0.1 to 50 mol, further preferably 0.1 to 30 mol, particularly preferably 0.1 to 20 mol, based on 1 mol of the isocyanate compound, and the temperature is preferably-10 to 120 ℃, more preferably-5 to 100 ℃, further preferably 0 to 50 ℃, and particularly preferably 5 to 30 ℃.

Further, it is also preferable that the compound represented by the formula (I) is obtained by reacting an isocyanate compound with hydrazine or a polyamine compound so that the total number of primary amino groups contained in the hydrazine or the polyamine compound is preferably 0.01 to 50 mol, more preferably 0.1 to 50 mol, further preferably 0.1 to 30 mol, particularly preferably 0.5 to 20 mol, based on 1 mol of an isocyanate group contained in the isocyanate compound.

The present invention is preferably a curing agent for an epoxy resin and/or a resin having at least 1 unsaturated bond, the curing agent containing a compound represented by the following formula (Ia) among the compounds represented by the above formula (I).

In the curing agent of the present invention, the compound having at least 1 primary amino group in the molecule is preferably a compound represented by the following formula (Ia),

[ CHEM 23 ]

In the formula (I), the compound is represented by,

R¹independently of one another, is a single bond, or is C₁～C₁₂Alkylene, C interrupted discontinuously by 1 or more NH (imino) or O atoms (oxygen atoms)₂～C₁₂The alkylene group (H atom (hydrogen atom) bonded to N atom (nitrogen atom)) may be substituted with amino group or C₁～C₁₂Alkylamino of (2), C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂cycloalkylene-C₁～C₁₂Alkylene radical, C₃～C₁₂cycloalkylene-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Arylene radical, C₁～C₄alkylene-C₆～C₁₄Arylene radical, C₁～C₄alkylene-C₆～C₁₄Arylene radical-C₁～C₄Alkylene, or C₆～C₁₄Arylene radical-C₁～C₄alkylene-C₆～C₁₄Arylene (here, alkylene is straight-chain or branched and may be substituted by halogen, C₃～C₁₂Cycloalkylene or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄An alkyl group),

X in the formula (Ia)¹The same 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 hydrazine or with a polyamine compound. The reaction of the diisocyanate compound with hydrazine or with a polyamine compound is preferably carried out in an organic solvent or without a solvent (without a solvent) while controlling the temperature, and the hydrazine or polyamine compound is preferably 0.01 to 50 mol, more preferably 0.1 to 50 mol, further preferably 0.1 to 30 mol, particularly preferably 0.1 to 20 mol, and the temperature is preferably-10 to 120 ℃, more preferably-5 to 100 ℃, further preferably 0 to 50 ℃, and particularly preferably 5 to 30 ℃ based on 1 mol of the diisocyanate compound.

Examples of the compound obtained by the reaction of the diisocyanate compound with, for example, tris (2-aminoethyl) amine which is a polyamine compound having 3 primary amino groups in the molecule include compounds represented by the following formulae.

[ CHEM 24 ]

In the above formula, X¹And X in the formula (Ia)¹Have the same meaning.

Examples of the compound represented by the formula (Ia) include,

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

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

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

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

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

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

N, N' -hexamethylene [ carbonylbis (azelidinyl) -2-aminoethyl ] - [ carbonylbis (azelidinyl) -6-aminohexyl ] (A-7), etc.

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

[ CHEM 25 ]

The present invention is preferably a curing agent for an epoxy resin and/or a resin having at least 1 unsaturated bond, the curing agent containing a compound represented by the following formula (Ib) among the compounds represented by the above formula (I).

In the curing agent of the present invention, the compound having at least 1 primary amino group in the molecule is preferably a diaminourea compound represented by the following formula (Ib) (wherein X is¹The meaning is the same as above).

[ CHEM 26 ]

In the formula (Ib)X of (2)¹The same as A in the case where n is 2 in the formula (I).

The compound represented by the formula (Ib) is preferably obtained by reacting the diisocyanate compound with hydrazine. The diisocyanate compound is preferably obtained by reacting the diisocyanate compound with hydrazine in an organic solvent or without a solvent (without a solvent) while controlling the temperature, and the hydrazine is preferably 0.01 to 50 mol, more preferably 0.1 to 50 mol, further preferably 0.1 to 30 mol, and particularly preferably 0.1 to 20 mol, based on 1 mol of the diisocyanate compound, and the temperature is preferably-10 to 120 ℃, more preferably-5 to 100 ℃, further preferably 0 to 50 ℃, and particularly preferably 5 to 30 ℃.

Examples of the diaminourea compound represented by the formula (Ib) include,

4, 4' - (methylenebis-1, 4-cyclohexyl) bis (semicarbazide) (B-1),

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

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

4, 4' - (1, 3-cyclohexyldimethylene) bis (semicarbazide) (B-4),

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

4, 4' -isophorone bis (semicarbazide) (B-6), and the like.

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

[ CHEM 27 ]

The curing agent of the present invention preferably comprises the following formula (IIa),

[ CHEM 28 ]

In the formula (I), the compound is represented by,

R¹is a single bond, or is C₁～C₁₂Alkylene, C interrupted discontinuously by 1 or more NH (imino) or O atoms (oxygen atoms)₂～C₁₂The alkylene group (H atom (hydrogen atom) bonded to N atom (nitrogen atom)) may be substituted with amino group or C₁～C₁₂Alkylamino of (a), C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂cycloalkylene-C₁～C₁₂Alkylene radical, C₃～C₁₂cycloalkylene-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Arylene radical, C₁～C₄alkylene-C₆～C₁₄Arylene radical, C₁～C₄alkylene-C₆～C₁₄Arylene radical-C₁～C₄Alkylene, or C₆～C₁₄Arylene radical-C₁～C₄alkylene-C₆～C₁₄Arylene (here, alkylene is straight-chain or branched and may be substituted by halogen, C₃～C₁₂Cycloalkylene or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄An alkyl group),

X²is C₁～C₁₂Alkyl, C interrupted discontinuously by 1 or more than 1O atoms (oxygen atoms)₂～C₁₂Alkyl radical, C₁～C₁₂Alkoxycarbonylalkylene group, C₃～C₁₂Cycloalkyl radical, C₁～C₁₂alkyl-C₃～C₁₂Cycloalkylene radical, C₃～C₁₂cycloalkyl-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Aryl radical, C₁～C₄alkyl-C₆～C₁₄Arylene radical, C₆～C₁₄aryl-C₁～C₄alkylene-C₆～C₁₄Arylene (here, alkylene is straight-chain or branched and may be substituted by halogen, C₃～C₁₂Cycloalkyl radical, C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Aryl or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄Alkyl), or (meth) acryloyloxyalkyl ]. X in the formula (IIa)²The same 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 polyamine compound. The monoisocyanate compound is preferably obtained by reacting hydrazine or a polyamine compound in an organic solvent or without adding a solvent (without a solvent) while controlling the temperature, and the amino group of the diamino compound is preferably 0.1 to 50 mol, more preferably 0.1 to 30 mol, and particularly preferably 0.1 to 20 mol, based on 1 mol of the isocyanate group of the monoisocyanate compound, and the temperature is preferably-10 to 120 ℃, more preferably-5 to 100 ℃, more preferably 0 to 50 ℃, and particularly preferably 5 to 30 ℃.

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

[ CHEM 29 ]

In the formula, X²The meaning is the same as above. X in the formula (IIb)²The same 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. Preferably, the monoisocyanate compound is obtained by reacting hydrazine with 0.01 to 50 mol, more preferably 0.1 to 50 mol, further preferably 0.1 to 30 mol, particularly preferably 0.1 to 20 mol, of hydrazine, based on 1 mol of monoisocyanate compound, in an organic solvent or without a solvent (without a solvent), while controlling the temperature, preferably at a temperature of-10 to 120 ℃, more preferably-5 to 100 ℃, further preferably 0 to 50 ℃, and particularly preferably 5 to 30 ℃.

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 formulae.

[ CHEM 30 ]

The curing agent of the present invention is also preferably a curing agent comprising a compound obtained by further treating the above-mentioned isocyanate compound with hydrazine or a polyamine compound having 2 or more primary amino groups in the molecule, and a compound having at least 1 primary amino group in the molecule obtained by the reaction of the isocyanate compound with hydrazine.

The curing agent contains a compound obtained by treating a compound having at least 1 primary amino group in the molecule with an isocyanate compound, and thus the liquid stability of a resin composition containing the curing agent and an epoxy resin and/or a resin having at least 1 unsaturated bond can be improved, and the increase in viscosity with the passage of time can be suppressed.

The isocyanate compound used in the treatment of the compound having at least 1 primary amino group in the molecule is not particularly limited as long as it is a compound having at least 1 isocyanate group. As the isocyanate compound, at least one selected from the above isocyanate compounds can be preferably used. The isocyanate compound may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

The amount of the isocyanate compound to be used for treating the compound having at least 1 primary amino group in the molecule is not particularly limited and may be appropriately selected depending on the purpose and the like. When the number of amino groups of the compound having at least 1 primary amino group in the molecule is 1 mole, the isocyanate compound is preferably used in an amount such that the number of isocyanate groups of the isocyanate compound becomes 0.01 to 10 moles, more preferably 0.02 to 5 moles, and still more preferably 0.05 to 2 moles.

The treatment with the isocyanate compound of the compound having at least 1 primary amino group in the molecule is preferably carried out in an organic solvent or without a solvent (without a solvent) while controlling the temperature, and the temperature is preferably-10 to 120 ℃, more preferably-5 to 100 ℃, further preferably 10 to 90 ℃, and particularly preferably 20 to 80 ℃. The treatment time may be, for example, 0.1 to 100 hours, preferably 0.5 to 50 hours. The time for heating and mixing varies depending on the temperature for heating and mixing, and the time is shortened when the temperature is high, and the time is lengthened when the temperature is low, so that the optimum treatment time can be selected depending on the purpose of use when the curing agent is used.

The curing agent of the present invention is also preferably a curing agent comprising a compound obtained by further treating a compound having at least 1 primary amino group in the molecule obtained by the reaction of the above isocyanate compound with hydrazine or with a polyamine compound having 2 or more primary amino groups in the molecule with an isocyanate compound and an epoxy resin.

The curing agent comprises a compound obtained by treating a compound having at least 1 primary amino group in the molecule with an isocyanate compound and an epoxy resin, and thus the liquid stability of a resin composition comprising the curing agent and the epoxy resin and/or the resin having at least 1 unsaturated bond can be improved, and the increase in viscosity with the passage of time can be suppressed.

The epoxy resin used for the treatment of the compound having at least 1 primary amino group in the molecule is not particularly limited as long as it is a compound having at least 1 epoxy group, and can be appropriately selected from known epoxy resins and used. Examples of the epoxy resin include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, phenol novolac type epoxy resin, cresol-phenol novolac type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, heterocyclic type epoxy resin, urethane modified epoxy resin, and the like. Among these, bisphenol a type epoxy resins, glycidyl ester type epoxy resins, and the like are preferably used. The epoxy resin can be used alone in 1 kind, also can be combined in more than 2 kinds.

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

The treatment with the isocyanate compound and the epoxy resin of the compound having at least 1 primary amino group in the molecule is preferably carried out in an organic solvent or without a solvent (without a solvent) while controlling the temperature, and the temperature is preferably-10 to 120 ℃, more preferably-5 to 100 ℃, further preferably 10 to 90 ℃, and particularly preferably 20 to 80 ℃. The treatment time may be, for example, 0.1 to 100 hours, preferably 0.5 to 50 hours. The time for heating and mixing varies depending on the temperature for heating and mixing, and the time is shortened when the temperature is high, and the time is lengthened when the temperature is low, so that the optimum treatment time can be selected depending on the purpose of use when the curing agent is used.

The curing agent of the present invention is also preferably a curing agent comprising a compound obtained by further treating a compound having at least 1 primary amino group in the molecule obtained by the reaction of the above isocyanate compound with hydrazine or a polyamine compound having 2 or more primary amino groups in the molecule with an isocyanate compound and a compound having a hydroxyl group.

The curing agent comprises a compound obtained by treating a compound having at least 1 primary amino group in the molecule with an isocyanate compound and a compound having a hydroxyl group, and thus the liquid stability of a resin composition comprising the curing agent and an epoxy resin and/or a resin having at least 1 unsaturated bond can be improved, and the increase in viscosity with the passage of time can be suppressed.

The compound having a hydroxyl group used for the treatment of the compound having at least 1 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 hydroxyl group include an alcohol compound, a phenol compound, and a carboxylic acid compound. The compound having a hydroxyl group may be a monofunctional compound or a polyfunctional compound.

Among alcohol compounds, examples of the monohydric alcohol compound include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, t-butanol, 3-methyl-2-butanol, t-amyl alcohol, 2, 4-dimethyl-3-pentanol, 3-ethyl-3-pentanol, 3-methyl-3-pentanol, pentaerythritol, 3-pentanol, 2-propyn-1-ol, trimethylsilylcarbinol, allyl alcohol, 2-bromoethanol, 3-ethyl-2-methyl-3-pentanol, 2-iodoethanol, 1-methoxy-2-propanol, acetone cyanohydrin, (R) - (-) -1-methoxy-2-propanol, acetone cyanohydrin, and the like, 3-pentyn-1-ol, 3-butyn-2-ol, (R) - (+) -3-butyn-2-ol, (S) - (-) -3-butyn-2-ol, (R) - (+) -3-butyn-2-ol, ethylene cyanohydrin, 3-dimethyl-1-butanol, 2-difluoroethanol, methyl glycolate, 4-heptanol, 3-hexanol, 3-hexyn-1-ol, 3-methyl-1-butanol, (S) - (-) -2-methyl-1-butanol, DL-2-methyl-1-butanol, and, 2-methyl-3-butyn-2-ol, 4-methyl-4-heptanol, 2-methyl-2-pentanol, (S) - (+) -2-pentanol, (R) - (-) -2-pentanol, 2,2, 2-trifluoroethanol, 2,2, 2-trichloroethanol, 2,2, 2-tribromoethanol, 3-trimethylsilyl-2-propyn-1-ol, 1-bromo-2-propanol, 1-buten-3-ol, 2-butyn-1-ol, 1-chloro-2-propanol, cycloheptanol, cyclobutanol, 1-chloro-2-methyl-2-propanol, and mixtures thereof, 1, 3-dibromo-2-propanol, 1, 3-dichloro-2-propanol, 2, 6-dimethyl-4-heptanol, 2-dimethyl-3-hexanol, 2, 5-dimethyl-3-hexanol, 3, 5-dimethyl-3-hexanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-hexanol, 2-hexanol, hydroxyacetone, 3-methoxy-1-butanol, 2-methyl-3-buten-2-ol, 4-methyl-2-pentanol, 1-decanol, 1-nonanol, 1-octanol, 1-dodecanol, 3, 7-dimethyl-1-octanol, 1-tetradecanol, 1-undecanol, 1-hexadecanol, 1-octadecanol, 1-pentadecanol, 2-octanol, 1-docosanol, 1-eicosanol, cyclohexanemethanol, cyclododecanol, cyclohexaneethanol, 2, 5-dimethylcyclohexanol, 2-methylcyclohexanol, 1-cyclohexyl-1-butanol, 2-ethylcyclohexanol, 4- (2-hydroxyethyl) cyclohexanol, 1-cyclohexyl-1-pentanol, 9-decen-1-ol, oleyl alcohol, 4-cyclohexylcyclohexanol, 2-cyclohexylcyclohexanol, decahydro-2-naphthol, 1-decen-3-ol, 1-hexadecanol, 1-octadecanol, 1-pentadecanol, 2-octanol, 1-docosanol, 1-eicosanol, cyclod, 1-nonen-3-ol, 3, 5-dimethyl-1-adamantane methanol, 8-dimethylamino-1-octanol, 4- (hydroxymethyl) cyclohexane carboxylic acid, trans-4- (hydroxymethyl) cyclohexane carboxylic acid, 4- (trifluoromethyl) cyclohexane methanol, 2-thal alcohol, 2- (benzyloxy) ethanol, and the like.

Further, there may be mentioned monohydric alcohol compounds having an ether bond such as 2-methoxyethanol, diethylene glycol monomethyl ether, decaethylene glycol monomethyl ether, dodecaethylene glycol monomethyl ether, 3-methoxy-1-propanol, 1-butoxy-2-propanol, pentaethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, and 1, 4-butanediol monoether.

Examples of the diol compound include ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 2, 3-dimethyl-2, 3-butanediol, 2-dimethyl-1, 3-propanediol, 2-methyl-1, 3-propanediol, (S, S) - (+) -2, 3-butanediol, pinacol, 2-dimethyl-1, 3-propanediol, 1, 7-heptanediol, 1, 5-pentanediol, (S) - (+) -1, 2-propanediol, (R) - (-) -1, 2-propanediol, 1, 5-pentanediol, (S) - (+) -1, 2-propanediol, 1, 5-propanediol, and, (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, neopentyl glycol, 3, 9-bis (1, 1-dimethyl-2-hydroxyethyl) -2,4,8, 10-tetraoxaspiro [5.5] undecane, 1, 3-bis (2-hydroxyethoxy) benzene, 1, 4-bis (2-hydroxyethoxy) -2-butyne, diethylene glycol, tripropylene glycol, 2-bis (4-hydroxycyclohexyl) propane, and the like.

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

Further, examples of the 4-or higher-functional polyol compound include dipentaerythritol, diglycerin, Span 20, and the like.

Among the phenol compounds, examples of the monofunctional phenol compound include 4-methoxyphenol, 3-chlorophenol, 4-chlorophenol, p-cresol, m-cresol, o-cresol, 3, 5-dichlorophenol, o-methoxyphenol, 4-bromophenol, 2, 6-dichlorophenol, 4-fluorophenol, 4-iodophenol, 3-methoxyphenol, 3, 5-dimethoxyphenol, 4-phenoxyphenol, 3-bromophenol, 2, 4-dichlorophenol, 3, 4-dichlorophenol, 2, 6-dimethoxyphenol, 2, 6-dimethylphenol, 3, 5-dimethylphenol, 2-fluorophenol, 3-fluorophenol, 2-iodophenol, 3-iodophenol, 4-methoxy-1-naphthol, 3-fluorophenol, 3-iodophenol, 4-methoxy-1-naphthol, and the like, 2,4, 6-trichlorophenol, 4-aminophenol, 6-bromo-2-naphthol, 4-chloro-1-naphthol, 2, 3-dichlorophenol, 2, 5-dichlorophenol, 2, 4-dimethylphenol, 3, 4-dimethylphenol, 2, 6-difluorophenol, 3, 5-difluorophenol, 2, 6-dibromophenol, 3, 5-dibromophenol, 2,4, 6-trimethylphenol, 4-aminophenol hydrochloride, 4-tert-butylphenol, 4-tert-butoxyphenol, 4-hydroxybenzonitrile, 2, 4-dibromophenol, 2, 3-dimethylphenol, 2, 4-difluorophenol, 3, 4-dimethoxyphenol, 4-ethylphenol, 4-ethoxyphenol, 4-hydroxybenzaldehyde, 4-hydroxythiophenol, 4-isopropylphenol, 4- (methylthio) phenol, 2,4, 6-tribromophenol, 2,4, 6-triiodophenol, 2,3, 6-trichlorophenol, 5-amino-2-naphthol, 6-amino-1-naphthol, 3-aminophenol, 1-bromo-2-naphthol, 3-bromo-2-naphthol, 2, 4-dichloro-1-naphthol, 1, 6-dibromo-2-naphthol, 2, 5-difluorophenol, 2, 3-difluorophenol, 4-hydroxytrifluorotoluene, 3-hydroxythiophenol, pentachlorophenol, 4-propylphenol, 2,3,4, 6-tetrachlorophenol, 2,4, 5-trichlorophenol, 2-aminophenol, 5-amino-1-naphthol, 8-amino-2-naphthol, 4-tert-amylphenol, 3-tert-butylphenol, 4-sec-butylphenol, 3-cyanophenol, 3-ethoxyphenol, 3-ethylphenol, 2-ethoxyphenol, 3-hydroxybenzaldehyde, 4-benzylphenol, 6-hydroxy-2-naphthonitrile, 6-hydroxy-2-naphthoic aldehyde, 3-isopropylphenol, 2,3, 5-trimethylphenol, 2,3, 6-trimethylphenol, 4- (trifluoromethoxy) phenol, 4-amino-1-naphthol hydrochloride, sodium trichlorophenol, sodium hydroxy-2-sec-butylphenol, sodium hydroxy, 2-aminophenol hydrochloride, 2-tert-butylphenol, 4- α -cumylphenol, 2-cyanophenol, 2, 4-dibromo-1-naphthol, 3- (dimethylamino) phenol, 2-ethylphenol, 4' -hydroxyacetophenone, 4-hexylphenol, 2-hydroxytrifluoromethyl benzene, 2-hydroxythiophenyl mercaptan, 2-isopropylphenol, 2- (methylthio) phenol, 4-pentylphenol salicylaldehyde, 3-hydroxytrifluoromethyl benzene, 2,3,5, 6-tetrafluorophenol, 2,3, 4-trifluorophenol, 2-chlorophenol and the like.

Examples of the phenol compound having 2 hydroxyl groups include 4,4 '-dihydroxydiphenyl ether, 5-methoxyresorcinol, 2-methylresorcinol, 5-methylresorcinol monohydrate, 5-methylresorcinol (anhydrous), chlorohydroquinone, 4-chlorocatechol, 2' -dihydroxydiphenyl ether, 1, 3-bis (4-hydroxyphenoxy) benzene, 5-bromoresorcinol, 4-chlororesorcinol, 3-chlorocatechol, 4, 6-dichlororesorcinol, 2-iodoresorcinol, methylhydroquinone, 4-methylcatechol, 3-methoxycatechol, methoxyhydroquinone, 4-bromoresorcinol, 1, 4-bis (3-hydroxyphenoxy) benzene, 2-methylresorcinol, 2-iodoresorcinol, 4-methylhydroquinone, 3-methoxycatechol, 2-methoxyhydroquinone, 2-bromoresorcinol, 1, 4-bis (3-hydroxyphenoxy) benzene, 2-hydroxyresorcinol, and mixtures, Bromohydroquinone, 4-bromocatechol, 2, 6-dimethylhydroquinone, 2, 5-dimethylresorcinol, 2, 3-dimethylhydroquinone, 4-fluorocatechol, 4-fluororesorcinol, 3-methylcatechol, tetrachlorohydroquinone, 4' -dihydroxydiphenylmethane, 3-bromocatechol, cresol (an isomer mixture), bis (4-hydroxyphenyl) sulfide, 2, 6-dibromo-1, 5-dihydroxynaphthalene, 3-fluorocatechol, 2,4, 6-tribromoresorcinol, 2-bis (4-hydroxyphenyl) propane, 2-functional phenol compounds such as 4, 4' -ethylidenebisphenol, trimethylhydroquinone and 1, 2-dihydroxynaphthalene, and monofunctional phenol compounds such as 4-hydroxybenzyl alcohol.

Examples of the 3-functional phenol compound include 1,2, 4-trihydroxybenzene, 1,8, 9-trihydroxyanthracene, 5-methylphenidate, 4', 4 ″ -trihydroxytriphenylmethane, and the like.

Examples of the 4-functional phenol compound include 1,4,9, 10-anthracenetetraol, and examples of the 6-functional phenol compound include hexahydroxybenzene, 2,3,6,7,10, 11-hexahydroxybenzo [9,10] phenanthrene hydrate, and the like.

Examples of the carboxylic acid compound include monocarboxylic acids such as methoxyacetic acid, glyoxylic acid, heptanoic acid, decanoic acid, nonanoic acid, lauric acid, tetradecanoic acid, 4-methyl-n-octanoic acid, pimelic acid, heptadecanoic acid, 16-hydroxyhexadecanoic acid, 15-hydroxypentadecanoic acid, palmitic acid, pentadecanoic acid, stearic acid, behenic acid, eicosanoic acid, heneicosanoic acid, 12-hydroxystearic acid, and 2-hexyldecanoic acid, dicarboxylic acids such as azelaic acid, suberic acid, sebacic acid, (+) -camphoric acid, and dodecanedioic acid, and 3-or more functional polycarboxylic acids such as 1,3, 5-pentanetarboxylic acid.

The hydroxyl group-containing compounds may be used alone in 1 kind, or in combination of 2 or more kinds. Among these, at least one selected from the group consisting of an alcohol compound (preferably a diol compound) and a phenol compound is preferably used.

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

The treatment of the isocyanate compound and the hydroxyl group-containing compound with the compound having at least 1 primary amino group in the molecule is preferably carried out in an organic solvent or without a solvent (without a solvent) while controlling the temperature, and the temperature is preferably-10 to 120 ℃, more preferably-5 to 100 ℃, still more preferably 10 to 90 ℃, and particularly preferably 20 to 80 ℃. 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 comprises a curing agent (a) comprising a compound having at least 1 primary amino group in the molecule obtained by the reaction of the above isocyanate compound with hydrazine or with a polyamine compound having 2 or more primary amino groups in the molecule, and an epoxy resin and/or a resin (B) having at least 1 unsaturated bond in the molecule. The curing agent (a) preferably contains a compound represented by at least one selected from the group consisting of the above-mentioned formulae (I), (Ia), (Ib), (IIa), and (IIb), and also preferably contains a compound obtained by treating these compounds with an isocyanate compound, an isocyanate compound and an epoxy resin, or an isocyanate compound and a compound having a hydroxyl group.

[ epoxy resin ]

As the epoxy resin, known epoxy resins can be used, and examples thereof include bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, phenol novolac type epoxy resin, cresol-novolac type epoxy resin, cycloaliphatic epoxy resin, glycidyl ester type resin, glycidyl amine type epoxy resin, heterocyclic epoxy resin, urethane modified epoxy resin, and the like. Among these, bisphenol a type epoxy resins, cresol-novolac type epoxy resins, and the like are preferably used. Epoxy (meth) acrylic acid obtained by modifying a resin having a glycidyl group with (meth) acrylic acid may also be used. It is preferable to use a partially esterified epoxy resin obtained by reacting an epoxy resin described in, for example, japanese patent laid-open No. 2012-77202 with (meth) acrylic acid. Specifically, a partial esterified epoxy resin obtained by reacting (meth) acrylic acid in an amount of preferably 10 to 90 equivalent%, more preferably 20 to 80 equivalent%, further preferably 30 to 70 equivalent%, and particularly preferably 40 to 60 equivalent% based on 1 equivalent of an epoxy group of the epoxy resin is preferably used. One epoxy resin may be used alone, or two or more epoxy resins may be used in combination. Further, the epoxy resin may contain an unsaturated bond.

The partial esterified epoxy resin can be obtained by the following method: for example, first, a bisphenol a type epoxy resin is reacted with acrylic acid or methacrylic acid in the presence of a basic catalyst in a conventional manner under a condition of 0.9 to 1.1 equivalents of carboxylic acid group relative to 2 equivalents of epoxy group, toluene in an amount of about 4 times by mass and pure water in the same amount are added to the reaction product, and after stirring at 60 to 80 ℃ 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, and finally the organic layer is recovered and the residual toluene is removed by vacuum distillation, thereby purifying the partial esterified epoxy resin having been subjected to the reduction treatment of the water-soluble ionic substance. Specific examples of the bisphenol a epoxy resin include Epikote 828, 834, 1001, 1004 (manufactured by mitsubishi chemical corporation), EPICLON 850, 860, 4055 (manufactured by DIC corporation), and the like. As these raw material resins, resins subjected to a reduction treatment of water-soluble ionic substances (hereinafter referred to as a high-purity treatment), for example, EPICLON 850S (manufactured by DIC corporation), and the like are preferable.

[ resin having at least 1 unsaturated bond in the molecule ]

The resin composition may contain a resin having at least 1 unsaturated bond in the molecule. Examples of the resin having at least 1 unsaturated bond in the molecule include styrene derivatives, ethylene derivatives, maleimide derivatives, and (meth) acrylic acid derivatives. Among them, a (meth) acrylic acid derivative having at least 1 (meth) acryloyl group in the molecule is preferably used.

Specific examples of the (meth) acrylic acid derivative include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate; aryl (meth) acrylates such as phenyl (meth) acrylate; aralkyl (meth) acrylates such as benzyl (meth) acrylate; alkoxyalkyl (meth) acrylates such as methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, and the like; hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; and (meth) acrylic acid esters of alicyclic alcohols such as cyclohexyl (meth) acrylate. Here, (meth) acrylic acid means both acrylic acid and methacrylic acid.

When the epoxy resin is used in combination with a resin having at least 1 unsaturated bond in the molecule, the amount of the epoxy resin to be mixed with a resin having at least 1 unsaturated bond in the molecule can be appropriately determined depending on the purpose of the cured product obtained by curing the resin composition. When the resin having at least 1 unsaturated bond in the molecule is a (meth) acrylic acid derivative having at least 1 (meth) acryloyl group in the molecule, the amount of the (meth) acryloyl group is preferably 0.1 to 9.0 equivalents, more preferably 0.3 to 4.0 equivalents, based on 1 equivalent of the epoxy group.

The resin composition may contain, in addition to the above-mentioned resins, silicone resin, urea resin, imide resin, glass, and the like as needed.

Further, as required, various additives such as an antioxidant, an ultraviolet absorber, a light stabilizer, a silane coupling agent, a coating surface improving agent, a thermal polymerization inhibitor, a leveling agent, a surfactant, a coloring agent, a storage stabilizer, a plasticizer, a lubricant, a filler, inorganic particles, an antiaging agent, a wettability improving agent, and an antistatic agent may be blended in the resin composition.

The amount of the curing agent (a) to be mixed with the epoxy resin and/or the resin (B) having at least 1 unsaturated bond in the molecule is preferably 0.001 to 10 equivalents, more preferably 0.01 to 8 equivalents, further preferably 0.05 to 5 equivalents, and particularly preferably 0.1 to 3 equivalents of the total amount of the semicarbazide group or the primary amino group of the curing agent (a) to 1 equivalent of the epoxy resin. When the total amount of the semicarbazide group or the primary amino group of 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 a sealant for a liquid crystal display panel or the like, the adhesive strength can be obtained which can be adapted to the thinning required for the sealant, the diversification of the adhesiveness to various adherends, and the like, and can suppress the peeling at the time of cutting out a cell, at the time of mounting a liquid crystal cell driving IC, and the like.

The amount of the curing agent (a) to be mixed with the epoxy resin and/or the resin (B) having at least 1 unsaturated bond in the molecule is preferably 0.0005 to 10 equivalents, more preferably 0.005 to 8 equivalents, further preferably 0.025 to 5 equivalents, and particularly preferably 0.05 to 3 equivalents, based on 1 equivalent of the epoxy group of the epoxy resin, in the total amount of the semicarbazide group or the primary amino group of the curing agent (a) when the epoxy resin (B) is contained alone or when both the epoxy resin and the resin (B) having at least 1 unsaturated bond in the molecule are contained.

In addition, in the case of containing the resin (B) having at least 1 unsaturated bond in the molecule alone, the total amount of the semicarbazide group or the primary amino group of the curing agent (a) is preferably 0.0005 to 10 equivalents, more preferably 0.005 to 8 equivalents, further preferably 0.025 to 5 equivalents, and particularly preferably 0.05 to 3 equivalents, relative to 1 equivalent of the unsaturated bond of the resin (B). When the amount of the curing agent (a) to be mixed with the resin (B) is within the above range, when the resin composition is contained in a sealant for a liquid crystal display panel or the like, it is possible to cope with the thinning required for the sealant and the diversification of adhesiveness to various adherends, and it is also possible to exhibit an adhesive strength capable of suppressing peeling at the time of cutting out a cell, at the time of mounting a liquid crystal cell driving IC, or the like.

[ liquid Crystal sealing composition ]

The present invention relates to a liquid crystal sealing composition containing the resin composition. The liquid crystal sealing composition preferably contains a resin composition containing the curing agent (a) and an epoxy resin and/or a resin (B) having at least 1 unsaturated bond in the molecule, a photopolymerization initiator (C), and other inorganic fillers (D) used as needed.

[ photopolymerization initiator (C) ]

Examples of the photopolymerization initiator include benzophenone, 2-diethoxyacetophenone, benzil, benzoylisopropyl ether, benzoin dimethyl ether, 1-hydroxycyclohexyl phenyl ketone, and thioxanthone. As the photopolymerization initiator, a commercially available photo radical polymerization initiator can 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, and Lucirin TPO (all of which are manufactured by BASF Japan).

[ inorganic Filler (D) ]

The inorganic filler is not particularly limited, and examples thereof include spherical silica, spherical alumina, spherical titania, spherical alumina, and spherical calcium carbonate. Among them, spherical silica is preferable because of its excellent dispersibility, and its excellent effect of improving the adhesiveness of a sealant suitable for a liquid crystal dropping process and the moisture resistance of a cured product.

The mixing ratio of the components of the liquid crystal sealing composition is 0.5 to 5 parts by mass, preferably 0.5 to 4 parts by mass, more preferably 0.8 to 3 parts by mass of (C) a photopolymerization initiator and 0 to 40 parts by mass, preferably 2 to 30 parts by mass, more preferably 3 to 20 parts by mass of (D) an inorganic filler, relative to 100 parts by mass of the resin composition. In addition, the total mass of the liquid crystal sealing agent composition is preferably 0.5-3% by mass of (C) photopolymerization initiator and 0-40% by mass of (D) inorganic filler.

The liquid crystal sealing composition is produced by, in particular, taking care of uniform and complete dispersion of a solid substance such as an inorganic filler, and is preferably produced by sufficiently kneading the solid substance with a paint roll or the like.

[ liquid crystal display Panel ]

The liquid crystal sealing composition of the present invention can satisfy the demand for thinning and diversification of adhesiveness, and can exhibit an adhesive strength capable of suppressing peeling at the time of cutting out a cell, at the time of mounting a liquid crystal cell driving IC, and the like, and can be suitably used for manufacturing a liquid crystal display panel.

That is, the liquid crystal display panel of the present invention includes: the liquid crystal sealing material comprises opposed glass substrates, a cured product of the liquid crystal sealing material composition for bonding the opposed glass substrates, and a liquid crystal encapsulated by the opposed glass substrates and the cured product of the liquid crystal sealing material composition.

[ method for manufacturing liquid Crystal display Panel ]

The liquid crystal display panel can be manufactured by using the liquid crystal sealant composition of the present invention, and then performing photo-curing and thermal curing. Fig. 1 shows an embodiment of manufacturing a liquid crystal display panel. Specifically, as shown in the sectional view of fig. 1(a), a glass substrate 1 is used, and as shown in the sectional view of fig. 1(b), a liquid crystal sealing composition 2 of the present invention is applied to one glass substrate 1. Next, as shown in the cross-sectional view of fig. 1(c), another glass substrate 4 is placed on the liquid crystal sealing composition 2 on one glass substrate 1 in an opposed manner, the liquid crystal sealing composition 2 is cured by irradiating the liquid crystal sealing composition 2 with light such as ultraviolet light in an amount of 1,000 to 3,000mJ under pressure to bond the pair of

glass substrates

1,4, and thereafter, the pair of glass substrates is heated at a temperature of 100 to 120 ℃ for about 1 hour in a non-pressurized state to be sufficiently cured, thereby forming a liquid crystal-sealing cell 5 surrounded by the pair of

glass substrates

1,4 and the cured liquid crystal sealing composition 2. In this cell 5, as shown in the plan view of fig. 1(d) below, after the liquid crystal 6 is injected from the liquid crystal injection hole 3 in vacuum, the liquid crystal injection hole 3 is sealed, and the liquid crystal display panel 7 can be manufactured. Liquid crystal sealing combinationThe material may be dispensed and coated on an ITO glass substrate to which an alignment film subjected to a polishing treatment is attached, after which a liquid crystal is dropped on the substrate, the upper and lower substrates are attached by a liquid crystal dropping process (ODF process), and ultraviolet rays are irradiated to cure the substrate (for example, at 100mW/cm in the case of illuminance and irradiation time: 1000 mJ)²50mW/cm under 1 second/365 nm irradiation and 50mJ irradiation²Radiation at/365 nm for 1 second), after which it is cured, for example, in a hot air oven at 120 ℃ for 1 hour.

Examples

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[ Synthesis of curing agent ]

(example 1)

(B-1)4, 4' - (methylenebis-1, 4-cyclohexyl) bis (semicarbazide)

[ CHEM 31 ]

A solution A in which 13.05g of dicyclohexylmethane-4, 4' -diisocyanate was dissolved in 75g of ethanol and a solution B in which 5g of hydrazine was dissolved in 75g of ethanol were prepared. Solution B was placed in a flask, and solution A was added dropwise at a rate of 1.4 g/min while stirring at 25 ℃. After completion of the dropwise addition of solution A, the reaction solution was measured by Fourier transform infrared spectrophotometer to confirm 2250cm of product derived from isocyanate group^-1The reaction was terminated after the near peak disappeared. The reaction was carried out so that 1 mole of dicyclohexylmethane-4, 4' -diisocyanate and 2 moles (1: 2 in terms of molar ratio) of hydrazine were present.

After completion of the reaction, the reaction mixture was filtered through a funnel (manufactured by Kikushima corporation) using a filter paper (manufactured by Kikushima corporation, No.4), and the filtrate was removed, washed with 50ml of distilled water, further filtered, and dried in a vacuum oven at 50 ℃.

After drying, pulverization was carried out using a high-pressure pulverizer (trade name: nanojetmizer, Aishin Nano technologies CO., LTD) to produce a semicarbazide compound having an average particle diameter (median diameter) of 2.0. mu.m.

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

(example 2)

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

[ CHEM 32 ]

A solution A in which 16.8g of hexamethylene diisocyanate was dissolved in 150g of ethanol and a solution B in which 10g of hydrazine was dissolved in 150g of ethanol were prepared. While stirring solution B at 25 ℃ it was added dropwise at a rate of 1.4 g/min. After completion of the dropwise addition of solution A, the reaction solution was measured by Fourier transform infrared spectrophotometer to confirm 2250cm of product derived from isocyanate group^-1The reaction was terminated after the near peak disappeared. The reaction was carried out in such a manner that 1 mole of hydrazine was present in 2 moles (1: 2 in terms of mole ratio) relative to 1 mole of hexamethylene diisocyanate.

After completion of the reaction, the reaction mixture was filtrated with a filter paper (No. 4, manufactured by kikusho corporation) using a kikusho funnel (manufactured by kikusho corporation), liquid was removed, the obtained filtrate was washed with 50ml of ethanol, further filtrated, and the obtained filtrate was dried in a vacuum oven at 50 ℃. After drying, pulverization was carried out using a high-pressure pulverizer (trade name: nanojetmizer, Aishin Nanotechnologies CO., LTD) to produce a semicarbazide compound having an average particle diameter (median diameter) of 2.1. mu.m.

(example 3)

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

[ CHEM 33 ]

A solution A prepared by dissolving 14.1g of ethyl 2-isocyanatoacrylate in 150g of ethanol and ethanol were prepared150g of hydrazine was dissolved in 5g of the solution B. While stirring solution B at 25 ℃ it was added dropwise at a rate of 1.4 g/min. After completion of the dropwise addition of solution A, the reaction solution was measured by Fourier transform infrared spectrophotometer to confirm 2250cm of product derived from isocyanate group^-1The reaction was terminated after the near peak disappeared. The reaction was carried out so that 1 mol of hydrazine was present (1: 1 in terms of a molar ratio) based on 1 mol of ethyl 2-isocyanatoacrylate.

After completion of the reaction, ethanol was evaporated at 50 ℃ by an evaporator, and the purified product was measured by a Fourier transform infrared spectrophotometer to confirm that 3300cm was obtained from ethanol^-1The peaks near the peak disappeared to produce a liquid semicarbazide compound.

(example 4)

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

[ CHEM 34 ]

A solution A in which 10.51g of trimethylhexamethylene diisocyanate was dissolved in 50g of ethanol and a solution B in which 5.01g of hydrazine was dissolved in 50g of ethanol were prepared. While stirring solution B at 25 ℃ it was added dropwise at a rate of 1.4 g/min. After completion of the dropwise addition of the solution A, the reaction solution was measured by Fourier transform infrared spectrophotometer to confirm that 2250cm-¹The reaction was terminated after the near peak disappeared. The reaction was carried out in such a manner that 1 mole of hydrazine was present in a molar ratio of 1:2 relative to 1 mole of trimethylhexamethylene diisocyanate.

(example 5)

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

[ CHEM 35 ]

A solution a in which 18.82g of m-xylene diisocyanate was dissolved in 100g of isopropyl alcohol and a solution B in which 25.3g of hydrazine was dissolved in 100g of isopropyl alcohol were prepared. In a three-necked flask, solution A was added dropwise at a rate of 1.4 g/min while stirring solution B at 30 ℃. After completion of the dropwise addition of solution A, the reaction solution was measured by Fourier transform infrared spectrophotometer to confirm 2250cm of product derived from isocyanate group^-1The reaction was terminated after the near peak disappeared. The reaction was carried out so that 5 moles (1: 5 in terms of a molar ratio) of hydrazine were present relative to 1 mole of m-xylylene diisocyanate.

After completion of the reaction, the reaction mixture was filtrated with a filter paper (No. 4, manufactured by kikusho corporation) using a kikusho funnel (manufactured by kikusho corporation), liquid was removed, the obtained filtrate was washed with 50ml of isopropyl alcohol, further filtrated, and the obtained filtrate was dried in a vacuum oven at 50 ℃.

After drying, pulverization was carried out using a high-pressure pulverizer (trade name: nanojetmizer, Aishin Nano Technologies CO., LTD) to produce a semicarbazide compound having an average particle diameter (median diameter) of 2.2. mu.m.

(example 6)

(B-4)4, 4' - (1, 3-Cyclohexyldimethylene) bis (semicarbazide)

[ CHEM 36 ]

A solution A prepared by dissolving 19.42g of 1, 3-bis (isocyanatomethyl) cyclohexane in 100g of isopropanol and a solution B prepared by dissolving 25.3g of hydrazine in 100g of isopropanol were prepared. In a three-necked flask, solution A was added dropwise at a rate of 1.4 g/min while stirring solution B at 30 ℃. After the addition of the solution A was completed, the inverse value was measured by a Fourier transform infrared spectrophotometerReaction, confirmation of 2250cm from isocyanate group^-1The reaction was terminated after the near peak disappeared. The reaction was carried out in such a manner that 1 mole of hydrazine was present in a molar ratio of 1:5 relative to 1 mole of 1, 3-bis (isocyanatomethyl) cyclohexane.

(example 7)

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

[ CHEM 37 ]

A solution A in which 22.22g of isophorone diisocyanate was dissolved in 100g of ethanol and a solution B in which 25.3g of hydrazine was dissolved in 100g of ethanol were prepared. In a three-necked flask, solution A was added dropwise at a rate of 1.4 g/min while stirring solution B at 30 ℃. After completion of the dropwise addition of solution A, the reaction solution was measured by Fourier transform infrared spectrophotometer to confirm 2250cm of product derived from isocyanate group^-1The reaction was terminated after the near peak disappeared. The reaction was carried out so that 5 moles (1: 5 in terms of a molar ratio) of hydrazine were present with respect to 1 mole of isophorone diisocyanate.

(example 8)

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

[ CHEM 38 ]

A solution A prepared by dissolving 13.6gg of dicyclohexylmethane-4, 4-diisocyanate in 79g of ethanol and a solution B prepared by dissolving 20.7g of 1, 12-diaminododecane (manufactured by TCI) in 100g of ethanol were prepared. In a three-necked flask, solution A was added dropwise at a rate of 1.4 g/min while stirring solution B at 30 ℃. After completion of the dropwise addition, the reaction mixture was measured by Fourier transform infrared spectrophotometer to confirm 2250cm of the reaction mixture was derived from the isocyanate group^-1The reaction was terminated after the near peak disappeared. The reaction was carried out in such a manner that 1 mole of 1, 12-diaminododecane was present in an amount of 2 moles (1: 2 in terms of molar ratio) relative to 1 mole of dicyclohexylmethane-4, 4-diisocyanate.

The reaction solution was poured into 500g of water under stirring to promote crystallization, and after standing for 1 hour, the reaction solution was filtered through a Kiriki funnel (Kiriki Kaisha, manufactured by Kiriki Kaisha) using a filter paper (No. 4), and the obtained filtrate was dried at 50 ℃ in a vacuum oven. After drying, it was naturally cooled to room temperature, and pulverized by a high-pressure pulverizer (trade name: nanojetmizer, Aishin NanoTechnologies CO., LTD) to produce an amine compound having an average particle diameter (median diameter) of 2.5. mu.m.

(example 9)

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

[ CHEM 39 ]

A solution A prepared by dissolving 12g of 1, 6-diaminohexane (manufactured by TCI) in 100g of ethanol and a solution B prepared by dissolving 13.6g of dicyclohexylmethane-4, 4' -diisocyanate in 79g of ethanol were prepared. In a three-necked flask, solution A was added dropwise at a rate of 1.4 g/min while stirring solution B at 30 ℃. After completion of the dropwise addition, the reaction mixture was measured by Fourier transform infrared spectrophotometer to confirm 2250cm of the reaction mixture was derived from the isocyanate group^-1The reaction was terminated after the near peak disappeared. According to the relation to dicyclohexylMethane-4, 4-diisocyanate was reacted in an amount of 1 mol and 1, 6-diaminohexane in an amount of 2 mol (1: 2 in terms of molar ratio).

Thereafter, the solvent was distilled off under reduced pressure using a rotary evaporator. After drying, it was naturally cooled to room temperature, and pulverized by a high-pressure pulverizer (trade name: nanojetmizer, Aishin Nano Technologies CO., LTD) to produce an amine compound having an average particle diameter (median diameter) of 2.2. mu.m.

(example 10)

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

[ CHEM 40 ]

A solution A prepared by dissolving 49.65g of 1, 12-diaminododecane (TCI) in 150g of ethanol and a solution B prepared by dissolving 20.54g of hexamethylene diisocyanate in 118g of ethanol were prepared. In a three-necked flask, solution A was added dropwise at a rate of 1.4 g/min while stirring solution B at 30 ℃. After completion of the dropwise addition, the reaction mixture was measured by Fourier transform infrared spectrophotometer to confirm 2250cm of the reaction mixture was derived from the isocyanate group^-1The reaction was terminated after the near peak disappeared. The reaction was carried out in such a manner that 2 moles (1: 2 in terms of molar ratio) of 1, 12-diaminododecane were present with respect to 1 mole of hexamethylene diisocyanate.

Thereafter, the solvent was distilled off under reduced pressure using a rotary evaporator. After drying, it was naturally cooled to room temperature, and pulverized by a high-pressure pulverizer (trade name: nanojetmizer, Aishin Nano Technologies CO., LTD) to produce a diamine urea compound having an average particle diameter (median diameter) of 2.1. mu.m.

After completion of the reaction, the reaction mixture was filtrated with a filter paper (No. 4, manufactured by kikusho corporation) through a kikusho funnel (manufactured by kikusho corporation), liquid was removed, the obtained filtrate was washed with 100ml of ethanol, further filtrated, and the obtained filtrate was dried in a vacuum oven at 50 ℃.

(example 11)

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

[ CHEM 41 ]

A solution a prepared by dissolving 17.17g of hexamethylene diisocyanate in 118g of ethanol and a solution B prepared by dissolving 61.36g of ethylenediamine in 150g of ethanol were prepared. Solution B was stirred in a three-necked flask at 25 ℃ and solution A was added dropwise thereto at a rate of 1.4 g/min. After completion of the dropwise addition of solution A, the reaction solution was measured by Fourier transform infrared spectrophotometer to confirm 2250cm of product derived from isocyanate group^-1The reaction was terminated after the near peak disappeared. The reaction was carried out in such a manner that 10 moles (1: 10 in terms of mole ratio) of ethylenediamine were added to 1 mole of hexamethylene diisocyanate.

After completion of the reaction, the reaction mixture was filtrated with a filter paper (No. 4, manufactured by kikusho corporation) through a kikusho funnel (manufactured by kikusho corporation), liquid was removed, the obtained filtrate was washed with 100ml of ethanol, further filtrated, and the obtained filtrate was dried in a vacuum oven at 50 ℃. After drying, it was naturally cooled to room temperature, and pulverized by a high-pressure pulverizer (trade name: nanojetmizer, Aishin Nano Technologies CO., LTD) to produce an amine compound having an average particle diameter (median diameter) of 2.2. mu.m.

(example 12)

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

[ CHEM 42 ]

A solution A prepared by dissolving 17.17g of hexamethylene diisocyanate in 150g of ethanol and a solution B prepared by dissolving 94.9g of 1, 6-diaminohexane (TCI) in 118g of ethanol were prepared. Solution B was stirred in a three-necked flask at 25 ℃ and solution A was added dropwise thereto at a rate of 1.4 g/min. SolutionAfter the completion of the addition of the hydrolyzed solution A, the reaction mixture was measured by a Fourier transform infrared spectrophotometer to confirm that 2250cm of the reaction mixture was obtained from the isocyanate group^-1The reaction was terminated after the near peak disappeared. The reaction was carried out in such a manner that 1 mole of 1, 6-diaminohexane was 10 moles (1: 10 in terms of molar ratio) relative to 1 mole of hexamethylene diisocyanate.

Thereafter, the solvent was distilled off under reduced pressure using a rotary evaporator. After drying, it was naturally cooled to room temperature, and pulverized by a high-pressure pulverizer (trade name: nanojetmizer, Aishin Nano Technologies CO., LTD) to produce an amine compound having an average particle diameter (median diameter) of 2.3. mu.m.

(example 13)

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

[ CHEM 43 ]

A solution A prepared by dissolving 13.55g of dicyclohexylmethane 4, 4' -diisocyanate in 100g of ethanol and a solution B prepared by dissolving 15.5g of ethylenediamine (manufactured by TCI) in 79g of ethanol were prepared. Solution B was stirred in a three-necked flask at 25 ℃ and solution A was added dropwise thereto at a rate of 1.4 g/min. After completion of the dropwise addition of solution A, the reaction solution was measured by Fourier transform infrared spectrophotometer to confirm 2250cm of product derived from isocyanate group^-1The reaction was terminated after the near peak disappeared. The reaction was carried out in such a manner that 5 moles (1: 5 in terms of molar ratio) of 1, 6-diaminohexane were present relative to 1 mole of hexamethylene diisocyanate.

After completion of the reaction, the reaction mixture was filtrated with a filter paper (No. 4, manufactured by kikusho corporation) using a kikusho funnel (manufactured by kikusho corporation), liquid was removed, the obtained filtrate was washed with 100ml of ethanol, further filtrated, and the obtained filtrate was dried in a vacuum oven at 50 ℃. After drying, it was naturally cooled to room temperature, and pulverized by a high-pressure pulverizer (trade name: nanojetmizer, Aishin Nano Technologies CO., LTD) to produce an amine compound having an average particle diameter (median diameter) of 2.2. mu.m.

(Synthesis example)

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

[ CHEM 44 ]

61.36g (1020mmol) of ethylenediamine and 150g of toluene were stirred in a three-necked flask, and a solution of 17.17g (102mmol) of hexamethylene diisocyanate in 118.5g (150ml) of toluene was added dropwise. The reaction time was 30 minutes, and the reaction solution was controlled at 40 ℃. After the completion of the dropwise addition, the reaction solution was filtered, and the precipitate was washed with toluene and then poured into water. After stirring for 1 hour, the mixture was filtered, and the obtained filtrate was concentrated under reduced pressure by an evaporator to confirm a precipitate. The amount of the reacted hexamethylene diisocyanate and ethylenediamine was 10 moles (1: 10 in terms of a molar ratio) of ethylenediamine to 1 mole of hexamethylene diisocyanate. The resulting precipitate was washed with ethanol (EtOH), dried under reduced pressure, and the resulting crystals were pulverized with a high-pressure pulverizer (trade name: nanojetmizer, airfhin Nano technologies co., LTD) to produce an amine compound having an average particle diameter (median diameter) of 2.1 μm.

(example 14)

(A-7) N, N' -hexamethylene [ carbonylbis (azelidinyl) (2-aminoethyl) ] - [ carbonylbis (azelidinyl) (6-aminohexyl) ]

[ CHEM 45 ]

A solution A prepared by dissolving 18.3g of hexamethylene diisocyanate (TCI) in 240g of isopropyl alcohol and a solution B prepared by dissolving 33.48g of 1, 6-hexanediamine and 18.3g of ethylenediamine in 72.6g of isopropyl alcohol were prepared. Solution B was stirred in a three-necked flask at 25 ℃ and solution A was added dropwise thereto at a rate of 1.4 g/min. After the dropwise addition of the solution A, the reaction solution was measured by a Fourier transform infrared spectrophotometer,2250cm from the isocyanate group was observed^-1The reaction was terminated after the near peak disappeared. The reaction was carried out so that 1 mole of hexamethylene diisocyanate, 5 moles of ethylenediamine and 5 moles of 1, 6-diaminohexane (molar ratio: 1:5:5) were present.

After completion of the reaction, the reaction mixture was filtrated with a filter paper (No. 4, manufactured by kikusho corporation) through a kikusho funnel (manufactured by kikusho corporation), liquid was removed, the obtained filtrate was washed with 100ml of isopropyl alcohol, further filtrated, and the obtained filtrate was dried in a vacuum oven at 50 ℃. After drying, it was naturally cooled to room temperature, and pulverized by a high-pressure pulverizer (trade name: nanojetmizer, Aishin Nano Technologies CO., LTD) to produce an amine compound having an average particle diameter (median diameter) of 2.2. mu.m.

[ production of epoxy resin ]

The partially esterified epoxy resin was produced by the production method described in Japanese patent application laid-open No. 5-295087. Specifically, a partial esterified epoxy resin (partially methacryloylated epoxy resin) was produced as follows.

(i) High-purity bisphenol a-type epoxy resin: 1000 parts by mass of EPICLON-850S (available from DIC Co., Ltd.), 250 parts by mass of methacrylic acid, 900 parts by mass of toluene, 2 parts by mass of triethylamine and 2 parts by mass of p-methoxyphenol were mixed and stirred at 90 ℃ for 8 hours to obtain a partial addition reaction product.

(ii) 4500 parts by mass of toluene was added to the product of the above (i) to prepare a diluted solution, 4500 parts by mass of pure water was added thereto, and after stirring at room temperature for 1 hour, the mixture was allowed to stand, and the aqueous layer was separated and removed. This cleaning operation was repeated 3 to 5 times, followed by 3 to 5 times of cleaning with the same amount of 1 equivalent NaOH solution and 3 to 5 times of cleaning with the same amount of pure water alone, and the ion conductivity of the final cleaning water was measured with an ion conductivity meter (manufactured by horiba, Ltd.; conductivity meter), and it was confirmed to be 10. mu.S/cm or less.

(iii) The solution obtained by filtering the solution of (ii) was concentrated at 70 ℃ under reduced pressure, and the solution was purified by completely removing toluene, thereby synthesizing a partially methacryloylated epoxy resin.

Further, based on the above synthesis example, a partially acrylated epoxy resin was synthesized by the same method using acrylic acid instead of methacrylic acid.

[ production of liquid Crystal sealing composition ]

The above partially methacrylated epoxy resin 100 parts by weight, inorganic filler spherical silica (Admafine products, SO-C1)15 parts by weight, organic filler F-351 (Japanese Zeon products) 15 parts by weight, as a photo radical initiator Irgacure 907(BASF Japan) 3 parts by weight, silane coupling agent KBM-403 (shin-Etsu chemical industries Co., Ltd.) 2 parts by weight, and curing agents of examples 1-5, 8-12, 14 as curing agents were mixed, the amount of the curing agent was 1 equivalent based on the epoxy group 1 equivalent of the partially methacrylated epoxy resin, and the mixture was uniformly dispersed using Three-One Motor (manufactured by Three-OKA, trade name; RW28basic) to obtain a liquid crystal sealing agent resin composition.

A liquid crystal sealing composition was prepared in the same manner as in comparative example 1 except that commercially available dodecanedioic acid hydrazide (DDH, produced by Otsuka chemical Co., Ltd.) was used, and commercially available 1, 3-bis (3-hydrazine-3-oxo-propyl) -5- (1-methylethyl) hydantoin (Amicure VDH, produced by Ajinomoto Fine Techno) was used as comparative example 2.

[ method for measuring adhesive Strength ]

FIG. 2 is a diagram illustrating a method for measuring adhesive strength using the liquid crystal sealing composition of examples 1to 5, 8 to 12 and 14 and comparative examples 1to 2. As shown in FIG. 2, ITO glass 8 (having an ITO electrode film on the glass surface) having a thickness of 0.5mm and 3.0cm square and glass 9 having a thickness of 0.5mm and 2.3cm square were prepared. A test piece 10 was produced by applying a liquid crystal sealant composition 2 as an adhesive surface to a portion 9mm away from both ends of a center line of an ITO glass so as to have a diameter of 1.5 to 2.0mm and a thickness of 6.0 to 10.0 μm, and aligning 1 side of a 3.0cm square ITO glass 8 and a 2.3cm square glass 9 and bonding the two. The bonded test piece 10 was irradiated with UV 3000mJ (trade name: UB-031-A/BM-E1, manufactured by Eyegraphics) and then heated at 120 ℃ for 60 minutes to cure the liquid crystal sealing composition 2. The cured test piece 10 was subjected to punching at a point 5mm from the end of the center line of the ITO glass 8 by Autograph (AGS), and the adhesion strength was measured. The results are shown in Table 1.

[ bonding Strength of glass with alignment film ]

A glass 8 (having an alignment film on the surface of the glass) having a thickness of 0.7mm and a 3.0cm square and subjected to a polishing treatment (SUNEVER SE-7492, manufactured by Nissan chemical industries, Ltd.) and an alignment film glass 9 having a thickness of 0.7mm and a 2.3cm square and subjected to the same treatment as that of the glass 8 were prepared. As shown in fig. 2, a test piece 10 was produced by applying a liquid crystal sealing composition 2 as an adhesive surface to a portion of 9mm from both ends of the center line of the glass so as to have a diameter of 1.5mm to 2.0mm and a thickness of 6.0 μm to 10.0 μm, aligning 1 side of 3.0cm square oriented film glass 8 and 2.3cm square oriented film glass 9, and bonding the two. The bonded test piece 10 was irradiated with UV 3000mJ (trade name: UB-031-A/BM-E1, manufactured by Eyegraphics) and then heated at 120 ℃ for 60 minutes to cure the liquid crystal sealing composition 2. The cured test piece 10 was subjected to punching at a point 5mm from the end of the center line of the ITO glass 8 by Autograph (AGS), and the adhesion strength was measured.

[ orientation test method ]

An ITO glass substrate (60 mm. times.70 mm. times.0.7 mmt) to which an alignment film (サンエバー SE-7492, manufactured by Nissan chemical industries, Ltd.) having been subjected to polishing treatment was attached was coated with a seal dispenser (dispenser) so that the cross-sectional area thereof was 4000 μm²The liquid crystal sealing composition of example 11 (curing agent: A-5) and comparative example 1 (curing agent: DDH) was used for dispensing. Thereafter, liquid crystal (TN liquid crystal, MLC-11900-080, manufactured by Merck) was dropped on the substrates, the upper and lower substrates were bonded by a liquid crystal dropping process (ODF process), and ultraviolet rays were irradiated (UV irradiation apparatus: UVX-01224S1, manufactured by USHIO INC., Ltd., illuminance and irradiation time: 50mJ) at 50mW/cm²Irradiation at/365 nm for 1 second at 200mJ with a power of 50mW/cm²Irradiation at/365 nm for 4 seconds), followed by curing in a hot air oven at 120 ℃ for 1 hour, to prepare a test cell for an alignment test. In addition to this, the present invention is,when the illuminance was 0mJ, the liquid crystal and the sealant were cured by heat in a hot air oven at 120 ℃ for 1 hour after the lamination in a state where ultraviolet rays were not irradiated thereto by a mask, and a test cell for an alignment test was prepared.

The alignment state of the liquid crystal at the time of sealing was confirmed in the obtained panel. The confirmation was performed by an optical microscope, and the test cell was sandwiched between polarizing plates in a crossed nicols state and observed in a transparent manner. The alignment state of the liquid crystal at the corner and the straight line was observed at an illuminance of 200mJ or 50 mJ. The evaluation criterion of the alignment of the liquid crystal was determined based on the presence or absence of alignment disorder during sealing. The case where the alignment disorder was 50 μm or less at the time of sealing was indicated by "O", and the case where the alignment disorder was not less than this was indicated by "X". The results are shown in Table 2.

[ TABLE 1]

[ TABLE 2]

	Example 11	Comparative example 1
			Orientation (50mJ)	〇	×
Orientation (200mJ)	〇	×

As shown in Table 1, even when dissimilar materials such as glass and ITO glass are bonded to each other, the adhesive strength of the liquid crystal sealing composition using the curing agent of the present invention (examples 1to 5, 8 to 12, and 14) is higher than that of the liquid crystal sealing composition using the curing agent of comparative examples 1 and 2. The alignment disorder of the alignment film of the liquid crystal sealing composition of example 11 (curing agent a-5) was good at 50 μm or less in both sealing operations at illumination intensities of 50mJ and 200mJ, but the alignment disorder of the alignment film of comparative example 1 was more than 50 μm in both sealing operations at illumination intensities of 50mJ and 200 mJ. From the results, it was confirmed that the curing agent of the present invention, the resin composition using the same, and the liquid crystal sealing composition are suitable for thinning and diversification of adhesiveness required for a sealing agent used for bonding a liquid crystal display panel and the like, and exhibit an adhesive strength capable of suppressing peeling at the time of cutting out a cell, at the time of mounting a cell driving IC, and the like.

(example 15)

A solution a prepared by dissolving 17.17g of hexamethylene diisocyanate in 118g of ethanol and a solution B prepared by dissolving 61.36g of ethylenediamine in 150g of ethanol were prepared. Solution B was stirred in a three-necked flask at 25 ℃ and solution A was added dropwise thereto at a rate of 1.4 g/min. After completion of the dropwise addition of solution A, the reaction solution was measured by Fourier transform infrared spectrophotometer to confirm 2250cm of product derived from isocyanate group^-1The reaction was terminated after the near peak disappeared. The reaction was carried out in such a manner that 10 moles (1: 10 in terms of mole ratio) of ethylenediamine were present with respect to 1 mole of hexamethylene diisocyanate.

After completion of the reaction, the reaction mixture was filtrated with a filter paper (No. 4, manufactured by kikusho corporation) using a kikusho funnel (manufactured by kikusho corporation), liquid was removed, the obtained filtrate was washed with 100ml of ethanol, further filtrated, and the obtained filtrate was dried in a vacuum oven at 50 ℃. After drying, it was naturally cooled to room temperature, and pulverized by a high-pressure pulverizer (trade name: nanojetmizer, Aishin Nano Technologies CO., LTD) to produce an amine compound (A-5) having an average particle diameter (median diameter) of 2.2. mu.m.

10g of the amine compound (A-5) obtained above was mixed with 1.36g of hexamethylene diisocyanate in 80ml of methylcyclohexane, and the mixture was subjected to a constant temperature treatment at 50 ℃ for 24 hours.

Thereafter, the treatment solution was filtered with a filter paper (No. 4, manufactured by kikusan corporation) using a kikusan funnel (manufactured by kikusan corporation), and then subjected to liquid removal. The resulting filtrate was mixed with 100ml of methylcyclohexane, and the same filtration as described above was performed, and this operation was repeated 3 times in total. The finally collected substance was dried at 50 ℃ and 1Torr for 12 hours by a vacuum dryer (manufactured by ESPEC Co., Ltd.) to obtain a curing agent (E-1) containing a compound obtained by treating an amine compound with an isocyanate compound.

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

Thereafter, the treatment solution was filtered with a filter paper (No. 4, manufactured by kikusan corporation) using a kikusan funnel (manufactured by kikusan corporation), and then subjected to liquid removal. The resulting filtrate was mixed with 100ml of toluene, and the same filtration as described above was performed, and this operation was repeated 3 times in total. The finally collected substance was dried at 50 ℃ and 1Torr for 12 hours by a vacuum dryer (manufactured by ESPEC Co., Ltd.) to obtain a curing agent (E-2) containing a compound obtained by treating an amine compound with an isocyanate compound and an epoxy resin.

[ production of liquid Crystal sealing composition ]

The obtained partially methacrylated epoxy resin was mixed with 100 parts by mass of an inorganic filler, spherical silica (SO-C1, manufactured by Admafine corporation) 15 parts by mass, an organic filler, F-351 (manufactured by Zeon, Japan), Irgacure 907 (manufactured by BASF Japan) 3 parts by mass, a silane coupling agent, KBM-403 (manufactured by shin-Etsu chemical Co., Ltd.) 2 parts by mass, and a curing agent, E-1 or E-2, 15 parts by mass, and uniformly dispersed using Three-OneMotor (manufactured by IKA, trade name; RW28basic) to obtain a liquid crystal sealing resin composition.

[ evaluation ]

(stability test)

Stability of liquid

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

The viscosity was measured as follows. A3 ℃ XR 7.7 conical rotor was attached to an RE-105U type viscometer (manufactured by Toyobo industries Co., Ltd.), 0.15ml of the liquid crystal sealing composition was placed in the conical rotor, and the viscosity of the liquid crystal sealing composition at 25 ℃ was measured at 2.5 rpm. If the measurement range is exceeded, the measurement cannot be performed. The standard for exceeding the measurement range is 1,200,000 mPas.

Liquid heating stability

The initial viscosity of the liquid crystal sealing composition obtained above was measured, and further the viscosity after 22 hours at 40 ℃ was measured, and the change rate of the viscosity after 22 hours of heating (%/22 hours) was calculated based on the initial viscosity.

The results of liquid stability and heated liquid stability are shown in table 3.

[ TABLE 3]

As is clear from the results in table 3, the liquid stability and the rate of change in the stability of the heated liquid of the isocyanate-added amine compound obtained by adding an arbitrary isocyanate to an amine compound are small, and particularly the rate of change in the stability of the heated liquid is remarkably small.

(curing test)

Under 2 conditions (only 120 ℃ for 1 hour, and UV 3000 mJ/cm) as described in Table 4²After treatment at 120 ℃ for 1 hour), the liquid crystal sealing composition (resin composition) obtained above was subjected to curing treatment and measured by FT-IRThe obtained cured sheet was evaluated for curability. The epoxy cure rate was calculated using the following formula. The methacryl cure rate can be calculated by replacing the peak of an epoxy group in the following formula with the peak of a methacryloyl group.

[ number 1]

A reference peak; 1540-1480 cm^-1(1510 cm peak)^-1Nearby)

A peak of epoxy groups; 925-895 cm^-1(Peak 910cm^-1Nearby)

A peak of methacryloyl groups; 1650-1625 cm^-1(1635 cm Peak^-1Nearby)

[ TABLE 4]

As is clear from the results in table 4, no significant decrease in curability was observed even when the isocyanate treatment was performed. That is, even if the isocyanate treatment is performed, curability is not lowered, and liquid stability can be improved.

Industrial applicability

According to the present invention, a curing agent can be obtained which satisfies the demand for diversification of adhesiveness based on the thinning and diversification of different materials and exhibits an adhesive strength capable of sufficiently suppressing peeling at the time of cutting out a cell, at the time of mounting a liquid crystal cell driving IC, and the like.

The disclosure of japanese patent application No. 2012-155976 is incorporated in its entirety by reference into the present specification.

All documents, patent applications, and technical standards described in the present specification are incorporated by reference into the present specification to the same extent as if each document, patent application, and technical standard was specifically and individually described.

[ description of symbols ]

1 glass substrate

2 liquid crystal sealing agent composition

3 liquid crystal injection hole

4 glass substrate

5 liquid crystal sealing cell

6 liquid crystal

7 liquid crystal display panel

8 ITO glass

9 glass

10 test piece

Claims

1. A liquid crystal sealing composition comprising a resin composition containing a curing agent (A) for an epoxy resin and/or a resin having at least 1 unsaturated bond in the molecule, and an epoxy resin and/or a resin (B) having at least 1 unsaturated bond in the molecule, the curing agent containing a compound having at least 1 primary amino group in the molecule obtained by the reaction of an isocyanate compound with hydrazine or with a polyamine compound having 2 or more primary amino groups in the molecule,

the polyamine compound is represented by the following formula (5a),

NH₂-L-NH₂···(5a)

in the formula (5a), L is C₁～C₁₂Alkylene, C interrupted discontinuously by 1 or more NH (imino) or O atoms (oxygen atoms)₂～C₁₂Alkylene radical, C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂cycloalkylene-C₁～C₁₂Alkylene radical, C₃～C₁₂cycloalkylene-C₁～C₄alkylene-C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Arylene radical, C₁～C₄alkylene-C₆～C₁₄Arylene radical, C₁～C₄alkylene-C₆～C₁₄Arylene radical-C₁～C₄Alkylene, or C₆～C₁₄Arylene radical-C₁～C₄alkylene-C₆～C₁₄Arylene, in which alkylene is linear or branched and may be substituted by halogen, C₃～C₁₂Cycloalkylene or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄Alkyl, C interrupted discontinuously by 1 or more NH (imino) or O atoms (oxygen atoms)₂～C₁₂The H atom (hydrogen atom) bonded to the N atom (nitrogen atom) in the alkylene group may be substituted with an amino group or C₁～C₁₂Alkyl amino substitution;

in the case where the curing agent is obtained by reacting an isocyanate compound with hydrazine, the isocyanate compound is a monoisocyanate compound or a diisocyanate compound,

the monoisocyanate compound is a compound represented by the following formula (1a),

in the formula (1a), X²Is C₁～C₁₂Alkyl, C interrupted discontinuously by 1 or more than 1O atoms (oxygen atoms)₂～C₁₂Alkyl radical, C₁～C₁₂Alkoxycarbonylalkylene group, C₃～C₁₂Cycloalkyl radical, C₁～C₁₂alkyl-C₃～C₁₂Cycloalkylene radical, C₃～C₁₂cycloalkyl-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Aryl radical, C₁～C₄alkyl-C₆～C₁₄Arylene radical, C₆～C₁₄aryl-C₁～C₄alkylene-C₆～C₁₄Arylene, or (meth) acryloxyalkyl, where alkylene is linear or branched and may be substituted by halogen, C₃～C₁₂Cycloalkyl radical, C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Aryl, or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄An alkyl group, a carboxyl group,

the diisocyanate compound is a compound represented by the following formula (2a),

in the formula (2a), X¹Is C discontinuously interrupted by 1 or more than 1O atoms (oxygen atoms)₂～C₁₂Alkylene radical, C₁～C₁₂Alkoxycarbonylalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂cycloalkylene-C₁～C₁₂Alkylene radical, C₃～C₁₂cycloalkylene-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene, di-C₃～C₁₂Cycloalkanediyl group, C₁～C₄alkylene-C₆～C₁₄Arylene radical-C₁～C₄Alkylene, or C₆～C₁₄Arylene radical-C₁～C₄alkylene-C₆～C₁₄Arylene, in which alkylene is linear or branched and may be substituted by halogen, C₃～C₁₂Cycloalkylene or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄An alkyl group.

2. A liquid crystal sealing composition comprising a resin composition containing a curing agent (A) for an epoxy resin and/or a resin having at least 1 unsaturated bond in the molecule, and an epoxy resin and/or a resin (B) having at least 1 unsaturated bond, the curing agent comprising a compound having at least 1 primary amino group in the molecule represented by the following formula (I),

[ CHEM 46 ]

In the formula (I), the compound is shown in the specification,

R¹is a single bond, or is C₁～C₁₂Alkylene, C interrupted discontinuously by 1 or more NH or O atoms₂～C₁₂Alkylene radical, C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂cycloalkylene-C₁～C₁₂Alkylene radical, C₃～C₁₂cycloalkylene-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Arylene radical, C₁～C₄alkylene-C₆～C₁₄Arylene radical, C₁～C₄alkylene-C₆～C₁₄Arylene radical-C₁～C₄Alkylene, or C₆～C₁₄Arylene radical-C₁～C₄alkylene-C₆～C₁₄Arylene radical, wherein said C₂～C₁₂The H atom bonded to the N atom in the alkylene group may be substituted by amino or C₁～C₁₂Substituted with alkylamino; here, the alkylene group is a straight chain or branched chain, and may be substituted with halogen, C₃～C₁₂Cycloalkylene or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄An alkyl group, a carboxyl group,

n is 1 or 2, and n is a hydrogen atom,

when n is 2, R¹Independently of one another, have the same meaning as above;

when n is 1, A is C₁～C₁₂Alkyl, C interrupted discontinuously by 1 or more than 1O atom₂～C₁₂Alkyl radical, C₂～C₁₂Alkoxycarbonylalkylene group, C₃～C₁₂Cycloalkyl radical, C₁～C₁₂alkyl-C₃～C₁₂Cycloalkylene radical, C₃～C₁₂cycloalkyl-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Aryl radical, C₁～C₄alkyl-C₆～C₁₄Arylene radical, C₆～C₁₄aryl-C₁～C₄alkylene-C₆～C₁₄Arylene, or (meth) acryloxyalkyl, where alkylene is linear or branched and may be substituted by halogen, C₃～C₁₂Cycloalkyl radical, C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Aryl or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄An alkyl group;

n is 2 and R¹When all are single bonds, A is C discontinuously interrupted by 1 or more than 1O atoms₂～C₁₂Alkylene radical, C₁～C₁₂Alkoxycarbonylalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂cycloalkylene-C₁～C₁₂Alkylene radical, C₃～C₁₂cycloalkylene-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene, di-C₃～C₁₂Cycloalkanediyl group, C₁～C₄alkylene-C₆～C₁₄Arylene radical-C₁～C₄Alkylene, or C₆～C₁₄Arylene radical-C₁～C₄alkylene-C₆～C₁₄Arylene, in which alkylene is linear or branched and may be substituted by halogen, C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄An alkyl group;

n is 2 and R¹When at least one is not a single bond, A is C₁～C₁₂Alkylene, C interrupted discontinuously by 1 or more than 1O atom₂～C₁₂Alkylene radical, C₁～C₁₂Alkoxycarbonylalkylene radical, C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂cycloalkylene-C₁～C₁₂Alkylene radical, C₃～C₁₂cycloalkylene-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene, di-C₃～C₁₂Cycloalkanediyl group, C₆～C₁₄Arylene radical, C₁～C₄alkylene-C₆～C₁₄Arylene radical-C₁～C₄Alkylene, or C₆～C₁₄Arylene radical-C₁～C₄alkylene-C₆～C₁₄Arylene, in which alkylene is linear or branched and may be substituted by halogen, C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄An alkyl group.

3. The liquid crystal sealing composition according to claim 2, wherein the compound having at least 1 primary amino group in the molecule is the following formula (Ia),

[ CHEM 51 ]

In the formula (I), the compound is shown in the specification,

R¹independently of one another, have the same meaning as in claim 2,

R¹when all are single bonds, X¹Is C discontinuously interrupted by 1 or more than 1O atom₂～C₁₂Alkylene radical, C₁～C₁₂Alkoxycarbonylalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂cycloalkylene-C₁～C₁₂Alkylene radical, C₃～C₁₂cycloalkylene-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene, di-C₃～C₁₂Cycloalkanediyl group, C₁～C₄alkylene-C₆～C₁₄Arylene radical-C₁～C₄Alkylene, or C₆～C₁₄Arylene radical-C₁～C₄alkylene-C₆～C₁₄Arylene, in which alkylene is linear or branched and may be substituted by halogen, C₃～C₁₂Cycloalkylene or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄An alkyl group;

R¹when at least one is not a single bond, X¹Is C₁～C₁₂Alkylene, C interrupted discontinuously by 1 or more than 1O atom₂～C₁₂Alkylene radical, C₁～C₁₂Alkoxycarbonylalkylene radical, C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₁～C₁₂alkylene-C₃～C₁₂cycloalkylene-C₁～C₁₂Alkylene radical, C₃～C₁₂cycloalkylene-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene, di-C₃～C₁₂Cycloalkanediyl group, C₆～C₁₄Arylene radical, C₁～C₄alkylene-C₆～C₁₄Arylene radical-C₁～C₄Alkylene, or C₆～C₁₄Arylene radical-C₁～C₄alkylene-C₆～C₁₄Arylene, in which alkylene is linear or branched and may be substituted by halogen, C₃～C₁₂Cycloalkylene or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄An alkyl group.

4. The liquid crystal sealing composition according to claim 2, wherein the compound having at least 1 primary amino group in the molecule is represented by the following formula (IIa),

[ CHEM 52 ]

In the formula (I), the compound is shown in the specification,

R¹has the same meaning as in claim 2,

X²is C₁～C₁₂Alkyl, C interrupted discontinuously by 1 or more than 1O atom₂～C₁₂Alkyl radical, C₂～C₁₂Alkoxycarbonylalkylene group, C₃～C₁₂Cycloalkyl radical, C₁～C₁₂alkyl-C₃～C₁₂Cycloalkylene radical, C₃～C₁₂cycloalkyl-C₁～C₁₂alkylene-C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Aryl radical, C₁～C₄alkyl-C₆～C₁₄Arylene radical, C₆～C₁₄aryl-C₁～C₄alkylene-C₆～C₁₄Arylene, or (meth) acryloxyalkyl, where alkylene is linear or branched and may be substituted by halogen, C₃～C₁₂Cycloalkyl radical, C₃～C₁₂Cycloalkylene radical, C₆～C₁₄Aryl or C₆～C₁₄Arylene unsubstituted or substituted by halogen or C₁～C₄An alkyl group.

5. A liquid crystal sealing composition according to any one of claims 1to 4, wherein the curing agent further comprises a compound obtained by treating the compound having at least 1 primary amino group in the molecule with an isocyanate compound in an organic solvent or without a solvent at-10 ℃ to 120 ℃ for 0.1 to 100 hours.

6. A liquid crystal sealing composition as claimed in any one of claims 1to 4 wherein said curing agent further comprises a compound obtained by treating said compound having at least 1 primary amino group in the molecule with an isocyanate compound and an epoxy resin in an organic solvent or without a solvent at-10 ℃ to 120 ℃ for 0.1 to 100 hours.

7. A liquid crystal sealing composition according to any one of claims 1to 4, wherein the epoxy resin is a partial esterified epoxy resin obtained by reacting 1 equivalent of an epoxy group of the epoxy resin with 10 to 90 equivalent% of (meth) acrylic acid.

8. The liquid crystal sealing composition according to claim 5, wherein the epoxy resin is a partial esterified epoxy resin obtained by reacting 10 to 90 equivalent% of (meth) acrylic acid with respect to 1 equivalent of an epoxy group of the epoxy resin.

9. The liquid crystal sealing composition according to claim 6, wherein the epoxy resin is a partial esterified epoxy resin obtained by reacting 10 to 90 equivalent% of (meth) acrylic acid with respect to 1 equivalent of an epoxy group of the epoxy resin.

10. A liquid crystal sealing composition according to any one of claims 1to 4, wherein the total amount of primary amino groups contained in the curing agent (A) is 0.001 to 10 equivalents relative to 1 equivalent of epoxy groups of the epoxy resin.

11. The liquid crystal sealing composition according to claim 5, wherein the total amount of the primary amino groups contained in the curing agent (A) is 0.001 to 10 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin.

12. The liquid crystal sealing composition according to claim 6, wherein the total amount of the primary amino groups contained in the curing agent (A) is 0.001 to 10 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin.

13. A liquid crystal sealing composition according to any one of claims 1to 4, wherein the total amount of primary amino groups contained in the curing agent (A) is 0.001 to 10 equivalents relative to the total of 1 equivalent of epoxy groups in the epoxy resin and 1 equivalent of unsaturated bonds in the resin having at least 1 unsaturated bond in the molecule.

14. The liquid crystal sealing composition according to claim 5, wherein the total amount of the primary amino groups contained in the curing agent (A) is 0.001 to 10 equivalents relative to the total of 1 equivalent of the epoxy group of the epoxy resin and 1 equivalent of the unsaturated bond of the resin having at least 1 unsaturated bond in the molecule.

15. The liquid crystal sealing composition according to claim 6, wherein the total amount of the primary amino groups contained in the curing agent (A) is 0.001 to 10 equivalents relative to the total of 1 equivalent of the epoxy group of the epoxy resin and 1 equivalent of the unsaturated bond of the resin having at least 1 unsaturated bond in the molecule.

16. A liquid crystal display panel obtained by using the liquid crystal sealant composition according to any one of claims 1to 15.

17. A method for manufacturing a liquid crystal display panel, wherein the liquid crystal sealing composition according to any one of claims 1to 15 is used in a liquid crystal dropping process, and is photo-cured and then thermally cured.