CN104428339A - Curing agent and resin composition using same - Google Patents

Curing agent and resin composition using same Download PDF

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CN104428339A
CN104428339A CN 201380036329 CN201380036329A CN104428339A CN 104428339 A CN104428339 A CN 104428339A CN 201380036329 CN201380036329 CN 201380036329 CN 201380036329 A CN201380036329 A CN 201380036329A CN 104428339 A CN104428339 A CN 104428339A
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group
firing
ci2
alkylene
compound
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CN 201380036329
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樱庭一郎
渡边自由
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协立化学产业株式会社
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50Amines
    • C08G59/54Amino amides>

Abstract

The present invention provides: a curing agent for an epoxy resin and/or resin having at least one unsaturated bond in the molecule, the curing agent comprising a compound having at least one primary amino group in the molecule, and the compound being obtained by reacting an isocyanate compound and hydrazine or a polyvalent amine compound having two or more primary amino groups in the molecule; a resin composition and liquid crystal sealant composition using the same; a liquid crystal display panel; and a method for producing a liquid crystal display panel.

Description

固化剂和使用了该固化剂的树脂组合物 Curing agent and the use of the curing agent is a resin composition

技术领域 FIELD

[0001] 本发明涉及环氧树脂和/或分子内具有至少1个不饱和键的树脂用的固化剂,特别是涉及一种可适合用于液晶显示器等液晶显示元件的固化剂、使用了该固化剂的树脂组合物、液晶密封剂组合物、液晶显示面板及其制造方法。 [0001] The present invention relates to an epoxy resin and an inner / or molecules having at least one unsaturated bond resin curing agent, in particular, relates to a suitable for liquid crystal display, a liquid crystal display curing agent component, using the the resin composition of the curing agent, the liquid crystal sealant composition, panel and manufacturing method for a liquid crystal display.

背景技术 Background technique

[0002] 近年来,伴随液晶显示器的显示部的增大、狭额缘化,密封剂的细线化得到推进。 [0002] In recent years, a liquid crystal display of the display unit is increased, narrow frontal edge line thinning encapsulant to obtain propulsion. 另外,作为密封剂的粘接对象,被粘接对象不仅是玻璃,而且ITO电极、SiN膜等无机材料、 取向膜等有机材料等也成为被粘接对象,被粘接体变得多样化,对密封剂要求具有能够将异种材料彼此粘接的粘接性的多样化。 Further, as the adhesive objects sealant is bonded not only by a glass, and an ITO electrode, SiN film, an inorganic material, an alignment film of organic material and the like are also become the bonded objects, the adherend become diversified, having adhesiveness diversity can be of different materials bonded to each other sealant requirements.

[0003] 作为这样的将异种材料彼此粘接的密封剂,例如提出了一种液晶显示元件用密封齐U,其含有环氧(甲基)丙烯酸酯等固化性树脂、热环氧固化剂等固化剂,不含有无机填充剂(专利文献1)。 [0003] As a sealant such a dissimilar materials bonded to each other, for example, proposed a liquid crystal display element sealed together U, which contains an epoxy (meth) acrylate curable resin, thermosetting epoxy curing agent curing agent, does not contain an inorganic filler (Patent Document 1). 作为用于该液晶显示元件用密封剂的热环氧固化剂,举出了癸二酸二酰肼、间苯二甲酸二酰肼、己二酸二酰肼等二酰肼化合物,作为其他市售品,举出了Amicure VDH、AmicureUDH(均为AJINOMOTOFINETECHNO社制造)等。 As for the liquid crystal display device with a thermal epoxy curing agent sealant, include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide dihydrazide compound, as another city the sale of goods, cited Amicure VDH, AmicureUDH (both AJINOMOTOFINETECHNO Corp.) and so on.

[0004] 现有技术文献 [0004] The prior art documents

[0005] 专利文献 [0005] Patent Document

[0006] 专利文献1 :日本特开2010-85712号公报 [0006] Patent Document 1: Japanese Patent Application Laid-Open No. 2010-85712 Patent Publication

发明内容 SUMMARY

[0007] 发明所要解决的课题 [0007] The invention solves the problem

[0008] 密封剂的细线化和粘接性的多样化相互影响,为了抑制在切出单元时和安装液晶盒驱动用IC时的剥落,对密封剂进一步还要求提高粘接强度。 [0008] The thinning and adhesion of diverse sealant influence each other, in order to suppress the cutout unit and the mounting flaking when the liquid crystal cell driving IC, access to the sealant which further required to improve the bonding strength.

[0009] 本发明的课题是找到一种在满足密封剂的细线化和粘接性的多样化的要求的同时,可提高粘接强度的潜在性固化剂,来提供环氧树脂和/或分子内具有至少1个不饱和键的树脂用的固化剂、使用该固化剂的树脂组合物和液晶密封剂组合物。 [0009] The object of the present invention is to find a way to meet the requirements of the thinning and adhesion of a variety of sealant while, the latent curing agent to improve adhesion strength, to provide an epoxy resin and / or molecule having at least one unsaturated bond resin curing agent, the curing agent resin composition and the liquid crystal sealant composition.

[0010] 解决课题的手段 [0010] Solution to Problem

[0011] 本发明人为了解决上述课题而进行了反复研究,结果发现,通过以分子内具有脲结构且具有至少1个伯氨基的化合物作为环氧树脂和/或分子内具有至少1个不饱和键的树脂用的潜在性固化剂,可得到一种树脂组合物和液晶密封剂组合物,能够适应于液晶显示面板等的密封剂的细线化和粘接性的多样化、且能够提高粘接强度。 [0011] The present inventor in order to solve the above problems have been repeatedly studied and found that, by molecules having a urea structure and having at least one primary amino compounds as epoxy resin and / or molecules having at least one unsaturated latent curing agent resin bond used can be obtained a resin composition and the liquid crystal sealant composition, it can be adapted to a liquid crystal thinning and adhesion of diverse panel sealant display, and can improve adhesion bonding strength.

[0012]SP,本发明如[1]〜[14]所述。 [0012] SP, of [1] to the [14] of the present invention.

[0013] [1]涉及一种固化剂,其为环氧树脂和/或分子内具有至少1个不饱和键的树脂用的固化剂,该固化剂包含通过异氰酸酯化合物与肼或与分子内具有2个以上伯氨基的多元胺化合物的反应而得到的在分子内具有至少1个伯氨基的化合物。 [0013] [1] relates to a curing agent having at least one unsaturated bond resin curing agent to an epoxy resin and / or molecules, the curing agent comprises an isocyanate compound with hydrazine or with a intramolecularly reaction of a polyamine compound having two or more primary amino groups and obtained by having at least one compound having a primary amino group in the molecule.

[0014] [2]涉及一种固化剂,其为环氧树脂和/或分子内具有至少1个不饱和键的树脂用的固化剂,该固化剂包含下述式(I)表示的在分子内具有至少1个伯氨基的化合物, [0014] [2] relates to a curing agent having at least one unsaturated bond resin curing agent to an epoxy resin and / or molecules, the curing agent comprises represented by the following formula (I) in a molecule compound having at least one primary amino group in having,

[0015]【化1】 [0015] [Chemical Formula 1]

[0016] [0016]

Figure CN104428339AD00071

[0017]〔式中 [0017] [wherein

[0018] R1为单键,或者为C1〜C12亚烷基、被1个或1个以上的NH(亚氨基)或0原子(氧原子)非连续间断的C2〜C12亚烷基(与N原子(氮原子)键合的H原子(氢原子) 可以被氨基或C1〜C12的烷基氨基取代)、C3〜C12亚环烷基、C1〜C12亚烷基-C3〜C12亚环烷基、C1〜C12亚烷基-C3〜C12亚环烷基-C1〜C12亚烷基、C3〜C12亚环烷基-C1〜C12 亚烷基-C3〜C12亚环烷基、C6〜C14亚芳基、C1〜C4亚烷基-C6〜C14亚芳基、C1〜C4亚烷基-C6〜C14亚芳基-C1〜C4亚烷基、或者C6〜C14亚芳基-C1〜C4亚烷基-C6〜C14亚芳基(此处,亚烷基为直链或支链,可以取代有卤素,C3〜C12亚环烷基或C6〜C14亚芳基无取代、或者取代有卤素或C1〜C4烧基, [0018] R1 is a single bond, or a C1~C12 alkylene group is one or more than one of NH (imino) or 0 atom (an oxygen atom) discontinuous intermittent C2~C12 alkylene (with N atom (a nitrogen atom) bonded H atom (hydrogen atoms) may be substituted with an amino or C1~C12 alkylamino), C3~C12 cycloalkylene, C1~C12 alkylene -C3~C12 cycloalkylene group , C1~C12 alkylene -C3~C12 cycloalkylene -C1~C12 alkylene, C3~C12 cycloalkylene -C1~C12 alkylene -C3~C12 alkylene cycloalkyl, C6~C14 alkylene an aryl group, C1~C4 alkylene -C6~C14 arylene, C1~C4 alkylene -C6~C14 arylene -C1~C4 alkylene group, or C6~C14 arylene -C1~C4 alkylene alkyl -C6~C14 arylene group (here, the alkylene is a straight-chain or branched-chain, may be substituted with halogen, C3~C12 cycloalkylene or C6~C14 arylene group unsubstituted or substituted with halo or C1~C4 burn group,

[0019]η为1、2、3 或4, [0019] η 2, 3 or 4,

[0020] η为2以上时,R1相互独立,含义与上述相同; When [0020] η is 2 or more, Rl independently of one another, meaning the same as above;

[0021] η为1时,A为C1〜C12烷基、被1个或1个以上的0原子(氧原子)非连续间断的C2〜C12烷基、C2〜C12烷氧羰基亚烷基、C3〜C12环烷基、C1〜C12烷基-C3〜C12亚环烷基、C3〜C12环烧基-C1〜C12亚烧基-C3〜C12亚环烧基、C6〜C14芳基、C1〜C4烧基-C6〜 C14亚芳基、C6〜C14芳基-C1〜C4亚烷基-C6〜C14亚芳基(此处,亚烷基为直链或支链,可以取代有卤素,C3〜C12环烷基、C3〜C12亚环烷基、C6〜C14芳基、或者C6〜C14亚芳基无取代、或者取代有齒素或C1〜C4烧基)、或者(甲基)丙稀醜氧基烧基; [0021] η is 1, A is C1~C12 alkyl, one or more than one 0 atom (an oxygen atom) discontinuous intermittent C2~C12 alkyl, C2~C12 alkoxycarbonyl alkylene, C3~C12 cycloalkyl, C1~C12 alkyl -C3~C12 cycloalkylene, C3~C12 cycloalkyl burning yl -C1~C12 alkylene burn-yl -C3~C12 cycloalkylene burn group, C6~C14 aryl, C1 ~C4 burning yl -C6~ C14 arylene, C6~C14 aryl -C1~C4 alkylene -C6~C14 arylene group (here, the alkylene is a straight-chain or branched-chain, may be substituted with halogen, C3~C12 cycloalkyl, C3~C12 cycloalkylene, C6~C14 aryl, or C6~C14 arylene group unsubstituted or substituted with teeth biotin or C1~C4 burn-yl), or (meth) acrylic dilute ugly group burn-yl;

[0022] η为2时,A为C1〜C12亚烷基、被1个或1个以上的0原子(氧原子)非连续间断的C2〜C12亚烷基、C1〜C12亚烷氧羰基亚烷基、C3〜C12亚环烷基、C1〜C12亚烷基-C3〜 C12亚环烷基、C1〜C12亚烷基-C3〜C12亚环烷基-C1〜C12亚烷基、C3〜C12亚环烷基-C1〜 C12亚烧基_C3〜C12亚环烧基、_C3〜C12环烧_基、C6〜C14亚芳基J1〜C4亚烧基_C6〜 C14亚芳基-C1〜C4亚烷基、或者C6〜C14亚芳基-C1〜C4亚烷基-C6〜C14亚芳基(此处, 亚烷基为直链或支链,可以取代有卤素,C3〜C12亚环烷基、C6〜C14亚芳基无取代、或者取代有卤素或C1-C4烷基); [0022] η is 2, A is a C1~C12 alkylene group is one or more than one 0 atom (an oxygen atom) discontinuous intermittent C2~C12 alkylene, C1~C12 alkylene alkoxycarbonylimino alkyl, C3~C12 cycloalkylene, C1~C12 alkylene -C3~ C12 cycloalkylene, C1~C12 alkylene -C3~C12 cycloalkylene -C1~C12 alkylene, C3~ C12 cycloalkylene -C1~ C12 alkylene burn-yl _C3~C12 cycloalkylene burn group, _C3~C12 cycloalkyl burning _ group, C6~C14 arylene J1~C4 alkylene burn-yl _C6~ C14 arylene -C1 ~C4 alkylene group, or C6~C14 arylene -C1~C4 alkylene -C6~C14 arylene group (here, the alkylene is a straight-chain or branched-chain, may be substituted with halogen, C3~C12 alkylene cycloalkyl, C6~C14 arylene group unsubstituted or substituted with halo or C1-C4 alkyl);

[0023]η为3时,A为下述式(1)、下述式⑵或下述式(3), [0023] η is 3, A represented by the following formula (1), the following equation ⑵ or the following formula (3),

[0024]【化2】 [0024] [Chemical Formula 2]

[0025] [0025]

Figure CN104428339AD00081

[0026](式中,R2相同或不同,为直链或支链的C1〜C12亚烷基), [0026] (wherein, R2 are the same or different, linear or branched C1~C12 alkylene),

[0027]【化3】 [0027] [Chemical Formula 3]

[0028] [0028]

Figure CN104428339AD00082

[0029](式中,R3相同或不同,为直链或支链的C1〜C12亚烷基), [0029] (wherein, the same or different from R3, a linear or branched alkylene C1~C12),

[0030]【化4】 [0030] [Chemical Formula 4]

[0031] [0031]

Figure CN104428339AD00083

[0032](式中,R4相同或不同,为直链或支链的C1〜C12亚烷基,R5为CH); [0032] (wherein, R4 are the same or different, is a C1~C12 alkylene group, linear or branched, R5 is CH);

[0033]η为4时,A为下述式(4), [0033] η is 4, A represented by the following formula (4),

[0034]【化5】 [0034] [Chemical Formula 5]

[0035] [0035]

Figure CN104428339AD00084

[0036] {式中,X3为Si,或者为由C3〜C12环烷基-C1〜C12亚烷基-C3〜C12环烷基、或C6〜C14芳基-C1〜C4亚烷基-C6〜C14芳基(此处,亚烷基为直链或支链,可以取代有1〜 6个齒素,C3〜C12环烧基或C6〜C14芳基无取代、或者取代有齒素或C1〜C4烧基)衍生的4价残基}〕。 [0036] {in the formula, X3 is Si, or by C3~C12 cycloalkyl -C1~C12 alkylene -C3~C12 cycloalkyl, or C6~C14 aryl -C1~C4 alkylene -C6 ~C14 aryl group (herein, the alkylene group is a straight chain or branched chain, may be substituted with 1 ~ 6 teeth prime, C3~C12 ring burn group or C6~C14 aryl group unsubstituted or substituted with teeth biotin or C1 tetravalent residue ~C4 burn-yl)]} derived.

[0037] [3]涉及上述[2]所述的固化剂,其中,在分子内具有至少1个伯氨基的化合物为下述式(Ia), [0037] [3] relates to the above [2] of the curing agent, wherein molecules having at least one primary amino compound of the following formula (Ia),

[0038]【化6】 [0038] [Chemical Formula 6]

[0039] [0039]

Figure CN104428339AD00091

[0040]〔式中, [0040] [wherein,

[0041]R1相互独立,含义与上述[2]中的相同, [0041] R1 each independently, the same as defined above [2],

[0042] X1为C1〜C12亚烷基、被1个或1个以上的0原子(氧原子)非连续间断的C2〜 C12亚烷基、C1〜C12亚烷氧羰基亚烷基、C3〜C12亚环烷基、C1〜C12亚烷基-C3〜C12亚环烧基、C1〜C12亚烧基_C3〜C12亚环烧基-C1〜C12亚烧基、C3〜C12亚环烧基-C1〜C12亚烷基-C3〜C12亚环烷基、二C3〜C12环烷二基、C6〜C14亚芳基X1〜C4亚烷基-C6〜C14亚芳基-C1〜C4亚烷基、或C6〜C14亚芳基-C1〜C4亚烷基-C6〜C14亚芳基(此处,亚烷基为直链或支链,可以取代有卤素,C3〜C12亚环烧基或C6〜C14亚芳基无取代、或者取代有卤素或C1〜C4烧基)〕。 [0042] X1 is C1~C12 alkylene, is one or one or more 0 atoms (oxygen atom) non-continuous intermittent C2~ C12 alkylene, C1~C12 Asia alkoxycarbonyl alkylene, C3~ C12 cycloalkylene, C1~C12 alkylene -C3~C12 cycloalkylene burn group, C1~C12 alkylene burning yl _C3~C12 cycloalkylene burn group -C1~C12 alkylene burn group, C3~C12 cycloalkylene burn group -C1~C12 alkylene -C3~C12 cycloalkylene, di C3~C12 cycloalkanediyl, C6~C14 arylene X1~C4 alkylene -C6~C14 arylene -C1~C4 alkylene group, or C6~C14 arylene -C1~C4 alkylene -C6~C14 arylene group (here, the alkylene is a straight-chain or branched-chain, may be substituted with halogen, C3~C12 cycloalkylene burn group or C6~C14 arylene group unsubstituted or substituted with halo or C1~C4 burn-yl)].

[0043] [4]涉及上述[2]所述的固化剂,其中,在分子内具有至少1个伯氨基的化合物为下述式(IIa), [0043] [4] relates to a curing agent according to [2], wherein the compound having at least one primary amino group represented by the following formula (IIa) in the molecule,

[0044]【化7】 [0044] [Chemical Formula 7]

[0045] [0045]

Figure CN104428339AD00092

[0046] 〔式中, [0046] [wherein,

[0047] R1的含义与上述[2]中相同, Meaning [0047] R1 and [2] the same,

[0048] X2为C1〜C12烷基、被1个或1个以上的0原子(氧原子)非连续间断的C2〜C12 烷基、C1〜C12烷氧羰基亚烷基、C3〜C12环烷基、C1〜C12烷基-C3〜C12亚环烷基、C3〜C12 环烷基-C1〜C12亚烷基-C3〜C12亚环烷基、C6〜C14芳基、C1〜C4烷基-C6〜C14亚芳基、 C6〜C14芳基-C1〜C4亚烷基-C6〜C14亚芳基(此处,亚烷基为直链或支链,可以取代有卤素,C3〜C12环烷基、C3〜C12亚环烷基、C6〜C14芳基或C6〜C14亚芳基无取代、或者取代有齒素或C1〜C4烧基)、或者(甲基)丙稀醜氧基烧基〕。 [0048] X2 is a C1~C12 alkyl, one or more than one 0 atom (an oxygen atom) discontinuous intermittent C2~C12 alkyl, C1~C12 alkoxycarbonyl, alkylene, C3~C12 cycloalkoxy group, C1~C12 alkyl -C3~C12 cycloalkylene, C3~C12 cycloalkyl -C1~C12 alkylene -C3~C12 cycloalkylene, C6~C14 aryl, C1~C4 alkyl - C6~C14 arylene, C6~C14 aryl -C1~C4 alkylene -C6~C14 arylene group (here, the alkylene is a straight-chain or branched-chain, may be substituted with halogen, C3~C12 cycloalkoxy group, C3~C12 cycloalkylene, C6~C14 aryl, or C6~C14 arylene group unsubstituted or substituted with teeth biotin or C1~C4 burn-yl), or (meth) acrylic ugly oxy burn-yl ].

[0049] [5]涉及上述[1]〜[4]的任一项所述的固化剂,其中,该固化剂进一步包含用异氰酸酯化合物处理上述在分子内具有至少1个伯氨基的化合物而得到的化合物。 [0049] [5] relates to a curing agent according to any one of [1] to [4], wherein the curing agent further comprising processing the compound having at least one primary amino group in the molecule with an isocyanate compound obtained by compound of.

[0050] [6]涉及上述[1]〜[4]的任一项所述的固化剂,其中,该固化剂进一步包含用异氰酸酯化合物和环氧树脂处理上述在分子内具有至少1个伯氨基的化合物而得到的化合物。 [0050] [6] relates to a curing agent according to any one of [1] to [4], wherein the curing agent further comprises a treatment with an isocyanate compound and an epoxy resin described above having at least one primary amino group in the molecule compound compound obtained.

[0051] [7]涉及上述[1]〜[4]的任一项所述的固化剂,其中,该固化剂进一步包含用异氰酸酯化合物和具有羟基的化合物处理上述在分子内具有至少1个伯氨基的化合物而得到的化合物。 [0051] [7] relates to a curing agent according to any one of [1] to [4], wherein the curing agent further comprises an isocyanate compound and a compound having a hydroxyl processing as described above having at least one primary in the molecule compound an amino group is obtained.

[0052] [8]涉及一种树脂组合物,其包含上述[1]〜[7]的任一项所述的固化剂(A)、以及环氧树脂和/或具有至少1个不饱和键的树脂(B)。 [0052] [8] relates to a resin composition comprising a curing agent (A) [1] ~ [7] above any one, and an epoxy resin and / or having at least one unsaturated bond resin (B).

[0053] [9]涉及上述[8]所述的树脂组合物,其中,环氧树脂为相对于环氧树脂的环氧基1当量使10〜90当量%的(甲基)丙烯酸对其反应而得到的偏酯化环氧树脂。 [0053] [9] relates to the aforementioned [8] The resin composition, wherein the epoxy resin to the epoxy resin equivalent of epoxy group 1 that the 10 ~ 90 equivalent% of (meth) acrylic acid and its reaction obtained by partial esterification of an epoxy resin.

[0054] [10]涉及上述[8]或[9]所述的树脂组合物,其中,相对于环氧树脂的环氧基1当量,固化剂(A)所含有的伯氨基的总量为0. 001〜10当量。 [0054] [10] relates to the above [8] or [9] The resin composition, which, relative to the epoxy equivalent of epoxy group, curing agent (A) contained in the primary amino group of a total of 0. 001~10 equivalent.

[0055] [11]涉及上述[8]〜[10]的任一项所述的树脂组合物,其中,相对于环氧树脂的环氧基1当量与分子内具有至少1个不饱和键的树脂的不饱和键1当量的合计,固化剂(A) 所含有的伯氨基的总量为〇. 001〜10当量。 [0055] [11] relates to a resin composition according to any one of [8] to [10] above, wherein, with respect to the epoxy group equivalent of the molecule an epoxy resin having at least one unsaturated bond the sum of the resin an unsaturated bond 1 equivalent of the total amount of the primary amino group of the curing agent (a) contained is square. 001~10 equivalents.

[0056] [12]涉及一种液晶密封剂组合物,其含有上述[8]〜[11]的任一项所述的树脂组合物。 According to any one of the resin composition [0056] [12] relates to a liquid crystal sealant composition, comprising the above-mentioned [8] to [11].

[0057] [13]涉及一种液晶显示面板,其通过使用上述[12]所述的液晶密封剂组合物而得到。 [0057] [13] relates to a liquid crystal display panel, which is obtained by using the above-mentioned [12] The liquid crystal sealant composition according to.

[0058] [14]涉及一种液晶显示面板的制造方法,其中,在液晶滴注工艺中,使用上述 [0058] [14] relates to a method for producing a liquid crystal display panel, wherein, in the liquid crystal dropping process using the above

[12]所述的液晶密封剂组合物,进行光固化后进行热固化。 Thermally cured [12] The liquid crystal sealant composition, light cured.

[0059] 发明效果 [0059] Effect of the Invention

[0060] 根据本发明,能够适应于液晶显示面板等的密封剂的细线化和粘接性的多样化, 同时能够显现出可抑制在切出单元时和安装液晶盒驱动用IC时等的剥落的粘接强度。 [0060] According to the present invention, it can be adapted to diverse thinning and adhesion of the liquid crystal display panel or the like of the sealant, and can exhibit suppressed or the like and the cutout unit when installing the liquid crystal cell for driving the IC peeling adhesive strength.

附图说明 BRIEF DESCRIPTION

[0061] 图1为示出通过使用液晶密封剂组合物来制造液晶显示面板的一实施方式的说明图。 [0061] FIG. 1 is an explanatory diagram showing manufacturing liquid by using the liquid crystal sealant composition of an embodiment of the panel display.

[0062] 图2为对液晶密封剂组合物的粘接强度的试验方法进行说明的说明图。 [0062] FIG. 2 is an explanatory diagram for explaining a test method for adhesive strength of the liquid crystal sealant composition.

具体实施方式 Detailed ways

[0063] 本说明书中,使用"〜"所示出的数值范围表示包括"〜"的前后记载的数值分别作为最小值和最大值的范围。 [0063] the present specification, "-" shown in the numerical range indicated values ​​described before and after including the "-" respectively as the minimum and maximum values. 对于组合物中的各成分的量,在组合物中存在多种相当于各成分的物质时,只要不特别声明,则是指组合物中存在的所述多种的物质的总量。 The amount of each component in the composition, the presence of a variety of equivalent materials of each component in the composition, unless specifically stated otherwise, refers to the amount of material of said plurality of composition present. "Ca〜cb" 的记载是指碳原子数为a〜b的范围。 "Ca~cb" described refers to the number of carbon atoms in a range a~b of.

[0064][固化剂] [0064] [Curing Agent]

[0065] 本发明涉及环氧树脂和/或分子内具有至少1个不饱和键的树脂用的固化剂,该固化剂包含通过异氰酸酯化合物与肼或与分子内具有2个以上伯氨基的多元胺化合物的反应而得到的在分子内具有至少1个伯氨基的化合物。 [0065] The present invention relates to an epoxy resin and an inner / or molecules having at least one unsaturated bond resin curing agent, the curing agent comprises an isocyanate compound with hydrazine or a polyamine having two or more primary amino groups within the molecule compounds obtained by reacting the molecules have at least one primary amino compounds. 通过将包含在分子内除具有至少1 个伯氨基外还具有脲结构的化合物的固化剂用作环氧树脂和/或分子内具有至少1个不饱和键的树脂(例如(甲基)丙烯酸类树脂等)的潜在性固化剂,能够适应于液晶显示面板等的密封剂的细线化和粘接性的多样化,同时能够显现可抑制在切出单元时和安装液晶盒驱动用IC时等的剥落的粘接强度。 By including in the molecule in addition to a curing agent for epoxy compound outside the at least one primary amino group also having a urea structure and an inner / or molecules having at least one unsaturated bond in the resin (e.g., (meth) acrylic when the resin or the like) of the latent curing agent, can be adapted to a liquid crystal thinning and adhesion of diverse panel sealant display simultaneously can exhibit suppressed during cut-out unit and mounting the liquid crystal cell driving IC or the like peeling adhesive strength.

[0066] 通过异氰酸酯化合物与肼或与分子内具有2个以上伯氨基的多元胺化合物的反应而得到的化合物由于在分子内具有脲结构和至少1个伯氨基,因此与被粘接体的氢键力提高,与已用作固化剂的酰肼化合物或胺化合物相比,推测其粘接强度提高了。 Compound polyvalent amine compound [0066] The ester compound with a hydrazine or having intramolecular isocyanate having two or more primary amino groups and obtained due to having a urea structure and at least one primary amino group in the molecule, and therefore with the hydrogen bonded body binding force to improve, compared with the hydrazide compound or an amine compound is used as a curing agent, presumably adhesion strength increased.

[0067]〔异氰酸酯化合物〕 [0067] [isocyanate compound]

[0068] 本发明中使用的异氰酸酯化合物为具有至少1个异氰酸酯基(-N=C= 0)的化合物,对其没有特别限定,可以举出单异氰酸酯化合物、二异氰酸酯化合物、三异氰酸酯化合物、四异氰酸酯化合物等。 [0068] The present invention is an isocyanate compound having at least one isocyanate group (-N = C = 0) compound is not particularly limited, and may include monoisocyanate compounds, diisocyanate compounds, triisocyanate compounds, tetrakis isocyanate compounds and the like.

[0069] (单异氰酸酯化合物) [0069] (monoisocyanate compound)

[0070] 作为单异氰酸酯化合物,可以举出下述式(Ia)表示的化合物。 [0070] As the monoisocyanate compound, a compound represented by the following formula (Ia) may be mentioned.

[0071] 【化8】 [0071] [Chemical 8]

[0072] X2-N=C=O* · · (Ia) [0072] X2-N = C = O * · · (Ia)

[0073] 式(Ia)中,X2为C1-C12烷基、被1个或1个以上的0原子(氧原子)非连续间断的C2〜C12烷基、C1〜C12烷氧羰基亚烷基、C3〜C12环烷基、C1〜C12烷基-C3〜C12亚环烷基、C3〜C12环烧基-C1〜C12亚烧基-C3〜C12亚环烧基、C6〜C14芳基、C1〜C4烧基-C6〜 C14亚芳基、C6〜C14芳基-C1〜C4亚烷基-C6〜C14亚芳基(此处,亚烷基为直链或支链,可以取代有卤素,C3〜C12环烷基、C3〜C12亚环烷基、C6〜C14芳基、或C6〜C14亚芳基无取代、或者取代有卤素或C1-C4烷基)、或者(甲基)丙烯酰氧基烷基。 In [0073] formula (Ia), X2 is C1-C12 alkyl, one or more than one 0 atom (an oxygen atom) discontinuous intermittent C2~C12 alkyl, C1~C12 alkoxycarbonyl alkylene , C3~C12 cycloalkyl, C1~C12 alkyl -C3~C12 cycloalkylene, C3~C12 ring burning base -C1~C12 Asia burn the base -C3~C12 cycloalkylene burn group, C6~C14 aryl, C1~C4 burning yl -C6~ C14 arylene, C6~C14 aryl -C1~C4 alkylene -C6~C14 arylene group (here, the alkylene is a straight-chain or branched-chain, may be substituted with halogen , C3~C12 cycloalkyl, C3~C12 cycloalkylene, C6~C14 aryl, or C6~C14 arylene group unsubstituted or substituted with halo or C1-C4 alkyl), or (meth) acrylamide acyloxyalkyl. 式(Ia)中的X2与式(I)中η为1时的A的含义相同。 η same as in formula (Ia) X2 of the formula (I) as Meaning 1 when A is.

[0074] 本说明书中,单独或与其他术语的组合中,"Ci〜C12烷基"为直链或支链的烷基, 可以取代有卤素,也可以被1个或1个以上的〇原子(氧原子)非连续间断,优选为直链烷基。 [0074] the present specification, individually or halogen in combination with other terms in the, "Ci~C12 alkyl" is an alkyl straight or branched, can be substituted, it may be square or more at one or one of (oxygen atom) non-continuously or intermittently, preferably a linear alkyl group. 可以举出烷基的碳原子数的范围为C1〜C12、更优选为C1〜C8、进一步优选为C1〜C6、 特别优选为C1-C4的范围。 Range of carbon atoms include an alkyl group of C1~C12, more preferably C1~C8, more preferably C1~C6, particularly preferably a C1-C4. 作为其具体例,可以举出例如甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正i^一烷基、正十二烷基等直链烷基、异丙基、 异丁基、仲丁基、叔丁基、2-甲基丁基、异辛基、叔辛基、2-乙基己基、叔壬基等支链烷基。 Specific examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-i ^ a alkyl, n-dodecyl and the like straight chain alkyl group, isopropyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, iso-octyl, t-octyl, 2-ethylhexyl , t-nonyl and the like branched chain alkyl group. 作为卤素,可以举出氟原子、氯原子、溴原子和碘原子。 Examples of halogen include fluorine atom, chlorine atom, bromine atom and iodine atom. 作为取代基的卤素优选为氟原子或氯原子、更优选为氟原子。 As the substituent halogen is preferably a fluorine atom or a chlorine atom, more preferably fluorine atom. 取代数为1〜12个、优选为1〜6个、更优选为1〜4个、特别优选为1〜3个。 Unsubstituted number 1~12, and preferably 1~6, and more preferably 1 ~ 4, and particularly preferably of 1 ~ 3 months.

[0075] 本说明书中,单独或与其他术语的组合中,〜C12亚烷基"为直链或支链的亚烷基,可以取代有卤素,也可以被1个或1个以上的NH(亚氨基)或0原子(氧原子)非连续间断(与N原子(氮原子)键合的H原子(氢原子)可以被氨基或C1〜C12的烷基氨基取代),优选为直链的亚烷基。可以举出亚烷基的碳原子数的范围为C1〜C12、更优选为C1〜C8、进一步优选为C1〜C6、特别优选为C1〜C4的范围。作为其具体例,可以举出例如亚甲基、亚乙基、三亚甲基、亚丙基、四亚甲基、1-甲基三亚甲基、2-甲基三亚甲基、3-甲基三亚甲基、五亚甲基、1-甲基四亚甲基、4-甲基四亚甲基、六亚甲基、5-甲基五亚甲基、七亚甲基、八亚甲基、九亚甲基、十亚甲基、i^一亚甲基、十二亚甲基等。作为卤素,可以举出氟原子、氯原子、溴原子和碘原子。作为取代基的卤素优选为氟原子或 [0075] the present specification, individually or halogen in combination with other terms in, ~C12 alkylene "Alkylene is a straight-chain or branched, can be substituted, it may be one or more than one of NH ( imino) or 0 atom (an oxygen atom) discontinuous intermittent (N atom (a nitrogen atom) bonded H atom (hydrogen atoms) may be substituted with an amino or C1~C12 alkyl group), preferably linear alkylene alkyl group may include a range of carbon atoms, alkylene group of C1~C12, more preferably C1~C8, more preferably C1~C6, particularly preferably C1~C4 as specific examples thereof, may be cited an example, methylene, ethylene, trimethylene, propylene, tetramethylene, 1-methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene, pentamethylene , 1-methyl tetramethylene, 4-methyl tetramethylene, hexamethylene, 5-methyl pentamethylene, heptamethylene, octamethylene, nine methylene, ten methylene, i ^ a methylene group, dodecamethylene, etc. Examples of halogen include fluorine atom, chlorine atom, bromine atom and iodine atom as a substituent a halogen is preferably a fluorine atom or 氯原子、更优选为氟原子。 取代数为1〜12个、优选为1〜6个、更优选为1〜4个、特别优选为1〜3个。 A chlorine atom, more preferably fluorine atom substituent number 1~12, and preferably 1~6, and more preferably 1 ~ 4, and particularly preferably of 1 ~ 3 months.

[0076] 本说明书中,对于aC1〜C12烧氧撰基亚烧基"或aC1〜C12亚烧氧撰基亚烧基"的烷氧基或亚烷氧基的碳原子数的范围,可以举出C1〜C12、更优选为C1〜C8、进一步优选为C1〜C6、特别优选为C1〜C4的范围。 Range of carbon atoms, [0076] the present specification, for aC1~C12 burning oxygen essays sulfoxide burn "or aC1~C12 alkylene oxy-fired essays sulfoxide burn group" alkoxy or alkyleneoxy group, can give a C1~C12, more preferably C1~C8, more preferably C1~C6, particularly preferably C1~C4 of. 作为其具体例,可以举出例如,甲氧羰基亚甲基、乙氧羰基亚甲基、正丙氧羰基亚甲基、正丁氧羰基亚甲基、正戊氧羰基亚甲基、正己氧羰基亚甲基、正庚氧羰基亚甲基、正辛氧羰基亚甲基、正壬氧羰基亚甲基、正癸氧羰基亚甲基、正十一烧氧基撰基亚甲基、正十-烧氧基撰基亚甲基等直链基团;异丙氧基撰基亚甲基、异丁氧基羰基亚甲基、仲丁氧基羰基亚甲基、叔丁氧基羰基亚甲基、2-甲基丁氧基羰基亚甲基、异辛氧基撰基亚甲基、叔半氧基撰基亚甲基、2-乙基己氧基撰基亚甲基等支链基团。 Specific examples thereof include e.g., methoxycarbonyl methylene, carbethoxymethylene, n-propoxycarbonyl methylene, n-butoxycarbonyl methylene, n-butoxycarbonyl methylene, n-hexyloxy carbonyl methylene, n-butoxycarbonyl methylene, n-octyl-carbonyl methylene, n-nonyl-carbonyl methylene, n-decyl-carbonyl methylene, n-undecyl burn group essays methylene, n ten - burning oxy essays ylmethylene are straight chain groups; isopropoxy essays methylene, isobutoxycarbonyl methylene, sec-butoxycarbonyl methylene, t-butoxycarbonylimino methyl, 2-methylbutoxy carbonyl methylene, isooctyl group essays methylene, tert-half group essays methylene, 2-ethyl hexyl group essays ylmethylene the like branched-chain group.

[0077]本说明书中,单独或与其他术语的组合中,"C3〜C12环烷基"的碳原子数的范围可以举出C3〜C12、更优选为C3〜C8、进一步优选为C3〜C6、特别优选为C4〜C6的范围。 [0077] this specification, alone or in combination with other terms in, "C3~C12 cycloalkyl" range of carbon atoms may include C3~C12, more preferably C3~C8, more preferably C3~C6 , particularly preferably C4~C6 of. 作为具体例,可以举出环丙基、环丁基、环戊基、环己基、环庚基、环辛基、环壬基、环癸基、环i^一烧基和环十_烧基。 Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, nonyl, cyclodecyl, ring i ^ a burn and cycloalkyl ten _ burn-yl . C3〜C12环烧基优选为环戊基或环己基。 C3~C12 ring burn group is preferably cyclopentyl or cyclohexyl. C3〜C12环烧基无取代、或者可以取代有卤素或C1-C4烷基,作为卤素,可以举出氟原子、氯原子、溴原子、碘原子。 C3~C12 ring burn group unsubstituted or may be substituted with halogen or C1-C4 alkyl group, examples of the halogen include fluorine atom, chlorine atom, bromine atom, iodine atom. 作为取代基的卤素优选为氟原子或氯原子、更优选为氯原子。 As the substituent halogen is preferably a fluorine atom or a chlorine atom, more preferably chlorine atom. 对于作为取代基的C1〜C4烷基, 可以举出甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基。 For a C1~C4 alkyl substituents include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. 作为取代基的C1〜 C4烷基优选为甲基、乙基或正丙基、更优选为甲基或乙基。 As the substituent group C1~ C4 alkyl is preferably methyl, ethyl or n-propyl, more preferably methyl or ethyl. 具有取代基的情况下的取代数为1〜5个、优选为1〜3个、更优选为1〜2个、特别优选为1个。 Substitution number in the case of having a substituent is 1 ~ 5, and preferably 1 ~ 3, more preferably 1 ~ 2, particularly preferably 1.

[0078] 本说明书中,单独或与其他术语的组合中,"C3〜C12亚环烷基"的碳原子数的范围可以举出:为C3〜C12、更优选为C3〜C8、进一步优选为C3〜C6、特别优选为C4〜C6的范围。 [0078] this specification, alone or in combination with other terms in, "C3~C12 cycloalkylene" The range of carbon atoms may include: as C3~C12, more preferably C3~C8, more preferably C3~C6, particularly preferably C4~C6 of. 作为其具体例,可以举出亚环丙基、亚环丁基、亚环戊基、亚环己基、亚环庚基、亚环辛基、亚环壬基、亚环癸基、亚环i^一烷基和亚环十二烷基。 Specific examples thereof include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cycloalkylene nonylene, cyclodecyl group, a cycloalkylene i ^ a alkyl and alkylene cyclododecyl. C3〜C12亚环烷基优选为亚环戊基或亚环己基。 C3~C12 cycloalkylene is preferably cyclopentylene or cyclohexylene. C3〜C12亚环烷基无取代、或者可以取代有卤素或C1〜C4烷基,作为卤素,可以举出氟原子、氯原子、溴原子和碘原子。 C3~C12 cycloalkylene unsubstituted or may be substituted with halo or C1~C4 alkyl group, examples of the halogen include fluorine atom, chlorine atom, bromine atom and iodine atom. 作为取代基的卤素优选为氟原子或氯原子、更优选为氯原子。 As the substituent halogen is preferably a fluorine atom or a chlorine atom, more preferably chlorine atom. 对于作为取代基的C1〜C4烷基,可以举出甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基。 For the group as a substituent C1~C4 alkyl group include methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. 作为取代基的C1〜C4烷基优选为甲基、乙基或正丙基、更优选为甲基或乙基。 As a substituent C1~C4 alkyl group is preferably methyl, ethyl or n-propyl, more preferably methyl or ethyl. 具有取代基的情况下的取代数为1〜4个、优选为1〜3个、更优选为1〜2 个、特别优选为1个。 Substitution number in the case of having a substituent is 1 ~ 4, and preferably 1 ~ 3, more preferably 1 ~ 2, particularly preferably 1.

[0079] 本说明书中,单独或与其他术语的组合中,"C6〜C14芳基"为具有至少1个芳香环的1价基团。 [0079] this specification, alone or in combination with other terms in, "C6~C14 aryl group" is a monovalent group having at least one aromatic ring. 作为其具体例,可以举出苯基、联苯基、萘基、蒽基、菲基等。 Specific examples include phenyl, biphenyl, naphthyl, anthryl, phenanthryl and the like. 优选为苯基、联苯基或萘基、更优选为苯基或萘基。 Preferably phenyl, biphenyl or naphthyl, more preferably phenyl or naphthyl. C6〜C14芳基无取代、或者可以取代有卤素或C1〜C4烷基,作为卤素,可以举出氟原子、氯原子、溴原子和碘原子。 C6~C14 aryl group unsubstituted or may be substituted with halo or C1~C4 alkyl group, examples of the halogen include fluorine atom, chlorine atom, bromine atom and iodine atom. 作为取代基的卤素优选为氟原子或氯原子、更优选为氯原子。 As the substituent halogen is preferably a fluorine atom or a chlorine atom, more preferably chlorine atom. 对于作为取代基的C1〜C4烷基,可以举出甲基、乙基、正丙基、 异丙基、正丁基、异丁基、仲丁基和叔丁基。 For a C1~C4 alkyl substituents include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. 作为取代基的C1〜C4烧基优选为甲基、乙基或正丙基、更优选为甲基或乙基。 As a substituent C1~C4 burning is preferably methyl, ethyl or n-propyl, more preferably methyl or ethyl. 具有取代基的情况下的取代数为1〜5个、优选为1〜3个、 更优选为1〜2个、特别优选为1个。 Substitution number in the case of having a substituent is 1 ~ 5, and preferably 1 ~ 3, more preferably 1 ~ 2, particularly preferably 1.

[0080] 本说明书中,单独或与其他术语的组合中,"c6〜C14亚芳基"为具有至少1个芳香环的2价基团。 [0080] this specification, alone or in combination with other terms in, "c6~C14 arylene" is a divalent group having at least one aromatic ring. 作为其具体例,可以举出亚苯基、亚萘基、亚蒽基、亚菲基等。 Specific examples thereof include phenylene group, naphthylene group, anthrylene group, phenanthrylene and the like. 优选为亚苯基、 亚萘基、更优选为亚苯基、亚萘基。 Preferably a phenylene, naphthylene, more preferably phenylene group, naphthylene group. C6〜C14亚芳基无取代、或者取代有卤素或C1〜C4烷基, 作为卤素,可以举出氟原子、氯原子、溴原子和碘原子。 C6~C14 arylene group unsubstituted or substituted with halo or C1~C4 alkyl group, examples of the halogen include fluorine atom, chlorine atom, bromine atom and iodine atom. 作为取代基的卤素优选为氟原子、氯原子或溴原子、更优选为氟原子或氯原子。 As the substituent halogen is preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a fluorine atom or a chlorine atom. 对于作为取代基的C1〜C4烷基,可以举出甲基、 乙基、正丙基、异丙基、正丁基、异丁基、仲丁基和叔丁基。 For a C1~C4 alkyl substituents include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. 作为取代基的C1〜C4烧基优选为甲基、乙基或正丙基、更优选为甲基或乙基。 As a substituent C1~C4 burning is preferably methyl, ethyl or n-propyl, more preferably methyl or ethyl. 具有取代基的情况下的取代数为1〜4个、优选为1〜3个、更优选为1〜2个、特别优选为1个。 Substitution number in the case of having a substituent is 1 ~ 4, and preferably 1 ~ 3, more preferably 1 ~ 2, particularly preferably 1.

[0081] 对于作为单异氰酸酯化合物的(甲基)丙烯酰氧基烷基异氰酸酯,可以举出下述式(Ib)表不的化合物。 [0081] Compound to as (meth) acryloyloxy alkyl isocyanate monoisocyanate compound include the following formula (Ib) table is not a.

[0082]【化9】 [0082] [Chemical Formula 9]

[0083] H2C=C(R6)-C00-R7-NC0 · · · (lb) [0083] H2C = C (R6) -C00-R7-NC0 · · · (lb)

[0084] 式(lb)中,R6表示氢原子或甲基、R7表示C1〜C6亚烷基。 [0084] formula (lb), R6 is a hydrogen atom or a methyl group, R7 represents C1~C6 alkylene. R7的C1〜C6亚烷基的碳原子数的范围优选为C2〜C6、更优选为C3〜c6。 R7 is C1~C6 alkylene group of carbon number preferably ranges C2~C6, more preferably C3~c6.

[0085] 作为单异氰酸酯化合物,具体地说,可以举出例如,甲基异氰酸酯、乙基异氰酸酯、 正己基异氰酸酯、环己基异氰酸酯、2-乙基己基异氰酸酯、苯基异氰酸酯、苄基异氰酸酯、丙基异氰酸酯、异丙基异氰酸酯、丁基异氰酸酯、庚基异氰酸酯、十二烷基异氰酸酯、十八烷基异氰酸酯、叔丁基异氰酸酯、异氰酸根合乙酸乙酯、异氰酸根合乙酸丁酯、(S)-(-)_2-异氰酸根合丙酸甲酯、异氰酸1-萘酯、异氰酸4-氯苯酯、异氰酸4-氟苯酯、异氰酸苯乙酯、异氰酸对甲苯酯、异氰酸间甲苯酯、异氰酸3, 5-二甲基苯酯等。 [0085] As the monoisocyanate compound specifically includes, for example, 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, tert-butyl isocyanate, isocyanato ethyl isocyanato ester bonded acid, (S ) - (-) _ 2- isocyanato-propionic acid methyl ester, isocyanate 1-naphthyl isocyanate, 4-chlorophenyl isocyanate, 4-fluorophenyl isocyanate, phenyl acrylate, isobutyl cyanate tolyl ester, m-tolyl isocyanate, isocyanate 3, 5-dimethylphenyl and the like.

[0086] 作为(甲基)丙烯酰氧基烷基异氰酸酯,具体地说,可以举出例如,(甲基)丙烯酰氧基甲基异氰酸酯、(甲基)丙烯酰氧基乙基异氰酸酯、(甲基)丙烯酰氧基丙基异氰酸酯等。 [0086] Examples of the (meth) acryloyloxy alkyl isocyanate, in particular, may include, for example, (meth) acryloyloxymethyl isocyanate, (meth) acryloyloxyethyl isocyanate, ( meth) acryloyloxypropyl isocyanate.

[0087](二异氰酸酯化合物) [0087] (diisocyanate compound)

[0088] 作为二异氰酸酯化合物,可以举出下述式(2a)表示的化合物。 [0088] As the diisocyanate compound, the compound represented by the following formula (2a) may be mentioned.

[0089]【化10】 [0089] [Chemical Formula 10]

[0090] O=C=N-X1-N=C=O* · · (2a) [0090] O = C = N-X1-N = C = O * · · (2a)

[0091] 式(2a)中,X1为C1-C12亚烷基、被1个或1个以上的0原子(氧原子)非连续间断的C2〜C12亚烷基、C1〜C12亚烷氧羰基亚烷基、C3〜C12亚环烷基、C1〜C12亚烷基-C3〜 C12亚环烷基、C1〜C12亚烷基-C3〜C12亚环烷基-C1〜C12亚烷基、C3〜C12亚环烷基-C1〜 C12亚烧基_C3〜C12亚环烧基、_C3〜C12环烧_基、C6〜C14亚芳基J1〜C4亚烧基_C6〜 C14亚芳基-C1〜C4亚烷基、或者C6〜C14亚芳基-C1〜C4亚烷基-C6〜C14亚芳基(此处, 亚烷基为直链或支链,可以取代有卤素,C3〜C12亚环烷基或C6〜C14亚芳基无取代、或者取代有卤素或C1〜C4烷基)。 In [0091] of formula (2a), X1 is C1-C12 alkylene group, by one or more than one 0 atom (an oxygen atom) discontinuous intermittent C2~C12 alkylene, C1~C12 alkylene alkoxycarbonyl alkylene, C3~C12 cycloalkylene, C1~C12 alkylene -C3~ C12 cycloalkylene, C1~C12 alkylene -C3~C12 cycloalkylene -C1~C12 alkylene, C3 ~C12 cycloalkylene -C1~ C12 alkylene burn-yl _C3~C12 cycloalkylene burn group, _C3~C12 cycloalkyl burning _ group, C6~C14 arylene J1~C4 alkylene burn-yl _C6~ C14 arylene - C1~C4 alkylene group, or C6~C14 arylene -C1~C4 alkylene -C6~C14 arylene group (here, the alkylene is a straight-chain or branched-chain, may be substituted with halogen, C3~C12 cycloalkylene or C6~C14 arylene group unsubstituted or substituted with halo or C1~C4 alkyl). 式(2a)中的X1与式(I)中η为2时的A的含义相同。 η same as in the formula (2a) X1 in the formula (I) as meaning 2:00 of A in.

[0092]作为二异氰酸酯化合物,具体地说,可以举出例如,二苯基甲烷二异氰酸酯(MDI)、 甲苯二异氰酸酯(TDI)、二甲苯二异氰酸酯(XDI)、氢化二甲苯二异氰酸酯(氢化XDI)、异佛尔酮二异氰酸酯(IPDI)、联甲苯胺二异氰酸酯(Troi)、六亚甲基二异氰酸酯(HDI)、二环己基甲烷二异氰酸酯(HMDI)、2, 4, 4-三甲基六亚甲基二异氰酸酯(TMHDI)、3, 5, 5-三甲基六亚甲基二异氰酸酯(TMHDI)、4, 4' -二异氰酸根合-3, 3' -二甲基联苯、4, 4' -二异氰酸根合-3, 3'-二甲基二苯基甲烷、2, 2-双(4-异氰酸根合苯基)六氟丙烷、2, 4-二异氰酸根合甲苯、1,3-双(2-异氰酸根合-2-丙基)苯、甲苯基-2, 6-二异氰酸酯、1,4-亚苯基二异氰酸酯、1,3-亚苯基二异氰酸酯、1,5-二异氰酸根合萘等。 [0092] As the diisocyanate compound specifically includes, for example, diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), xylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (hydrogenated XDI ), isophorone diisocyanate (IPDI), tolidine diisocyanate (Troi), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (HMDI), 2, 4, 4- trimethyl hexamethylene diisocyanate (TMHDI), 3, 5, 5- trimethyl hexamethylene diisocyanate (TMHDI), 4, 4 '- diisocyanato engagement -3, 3' - dimethyl-biphenyl , 4, 4 '- diisocyanato engagement -3, 3'-dimethyl-diphenyl methane, 2,2-bis (4-isocyanato-phenyl) hexafluoropropane, 2,4-diisobutyl cyanato toluene, 1,3-bis (2-isocyanato-2-propyl) benzene, toluene-2, 6-diisocyanate, 1,4-phenylene diisocyanate, 1,3- phenyl diisocyanate, 1,5-diisocyanato naphthalene.

[0093](三异氰酸酯化合物) [0093] (triisocyanate compound)

[0094] 作为三异氰酸酯化合物,可以举出3末端具有异氰酸酯基的具有异氰脲酸酯结构、缩二脲结构或加成结构的化合物。 [0094] As triisocyanate compounds include 3 having a terminal isocyanate group having isocyanurate structure, biuret structure or an addition compound of the structure. 作为具有异氰脲酸酯结构的三异氰酸酯化合物,可以举出下述式(3a)表示的具有异氰脲酸酯结构的化合物。 As having isocyanurate triisocyanate compound urea ester structure, a compound having the isocyanurate structure represented by the following formula (3a) may be mentioned.

[0095] 【化11】 [0095] [Chemical Formula 11]

[0096] [0096]

Figure CN104428339AD00141

[0097] 式中,R2相同或不同,为直链或支链的C1〜C12亚烷基。 [0097] In the formula, the same or different from R2, is a linear or branched C1~C12 alkylene group.

[0098] 作为具有缩二脲结构的三异氰酸酯化合物,可以举出下述式(3b)表示的化合物。 [0098] As the triisocyanate compound having a biuret structure, a compound represented by the following formula (3b) may be mentioned.

[0099] 【化12】 [0099] [Chemical Formula 12]

[0100] [0100]

Figure CN104428339AD00142

[0101] 式中,R3相同或不同,为直链或支链的C1〜C12亚烷基。 [0101] In the formula, the same or different from R3, a linear or branched C1~C12 alkylene group.

[0102] 作为具有加成结构的三异氰酸酯化合物,可以举出下述式(3c)表示的化合物。 [0102] As the triisocyanate compound having an addition structure, a compound represented by the following formula (3c) may be mentioned.

[0103] 【化13】 [0103] [Chemical Formula 13]

[0104] [0104]

Figure CN104428339AD00143

[0105] 式中,R4相同或不同,为直链或支链的C1〜C12亚烷基,R5为CH。 [0105] In the formula, the same or different from R4, is C1~C12 alkylene group, linear or branched, R5 is CH.

[0106] 作为三异氰酸酯化合物,具体地说,可以举出例如,三(异氰酸根合甲基)异氰脲酸酯、三(异氰酸根合乙酯)异氰脲酸酯、三(异氰酸根合丙基)异氰脲酸酯、三(异氰酸根合丁基)异氰脲酸酯、三(异氰酸根合己基)异氰脲酸酯、N,N'-2_三异氰酸酯甲基丙二酰胺、Ν,Ν' -2-三异氰酸酯己基丙二酰胺等。 [0106] As the triisocyanate compound specifically includes, for example, tris (isocyanato methyl) isocyanurate, tris (isocyanato ethyl) isocyanurate, tris (iso isocyanatopropyl) isocyanurate, tris (isocyanato-butyl) isocyanurate, tris (isocyanato-hexyl) isocyanurate, N, N'-2_ triisocyanates methyl malonamide, Ν, Ν '-2- triisocyanate dihexylmalonate amide.

[0107](四异氰酸酯化合物) [0107] (iv isocyanate compound)

[0108] 作为四异氰酸酯化合物,可以举出下述式(4a)表示的化合物。 [0108] As a four-isocyanate compound, a compound represented by the following formula (4a) may be mentioned.

[0109]【化14】 [0109] [Chemical Formula 14]

[0110] [0110]

Figure CN104428339AD00144

[0111] 式中,X3为由C3〜C12环烷基-C1〜C12亚烷基-C3〜C12环烷基、或者C6〜C14芳基-C1〜C4亚烷基-C6〜C14芳基(亚烷基为直链或支链,可以取代有卤素,C3〜C12环烷基或C6〜C14芳基无取代、或者可以取代有齒素或C1〜C4烧基)衍生的4价基团。 [0111] wherein, X3 by C3~C12 cycloalkyl -C1~C12 alkylene -C3~C12 cycloalkyl, or C6~C14 aryl -C1~C4 alkylene -C6~C14 aryl group ( alkylene is a straight-chain or branched-chain, may be substituted with halogen, C3~C12 cycloalkyl or C6~C14 aryl group unsubstituted or may be substituted with teeth biotin or C1~C4 firing yl) tetravalent group derived.

[0112] 另外,作为四异氰酸酯化合物,可以举出下述式(4b)表示的四异氰酸根合硅烷。 [0112] Further, as the four isocyanate compound include four isocyanate represented by the following formula (4b) sulfato silane.

[0113]【化15】 [0113] [Chemical Formula 15]

[0114] [0114]

Figure CN104428339AD00151

[0115] 作为四异氰酸酯化合物,具体地说,可以举出例如,4, 4' -二苯基甲烷-2, 2',5, 5' -四异氰酸酯、四异氰酸根合硅烷等。 [0115] As a four-isocyanate compound, specifically, includes, for example, 4, 4 '- diphenylmethane -2, 2', 5, 5 '- tetraisocyanate, four isocyanato silane.

[0116]〔多元胺化合物〕 [0116] [a polyamine compound]

[0117] 多元胺化合物为具有至少2个伯氨基的化合物,可以举出例如下述式(5a)表示的多元胺化合物。 [0117] polyamine compound is at least two compounds of primary amino groups, include polyvalent amine compounds represented by the following formula (5a).

[0118] 【化16】 [0118] [Chemical Formula 16]

[0119]NH2-L-NH2 ··· (5a) [0119] NH2-L-NH2 ··· (5a)

[0120] 式中,L为(^〜C12亚烷基、被1个或1个以上的NH(亚氨基)或0原子(氧原子) 非连续间断的C2〜C12亚烷基(与N原子(氮原子)键合的H原子(氢原子)可以被氨基或C1〜C12烷基氨基取代)、C3〜C12亚环烷基、C1〜C12亚烷基-C3〜C12亚环烷基、C1〜 C12亚烷基-C3〜C12亚环烷基-C1〜C12亚烷基、C3〜C12亚环烷基-C1〜C4亚烷基-C3〜 C12亚环烧基、C6〜C14亚芳基、C1〜C4亚烧基-C6〜C14亚芳基、C1〜C4亚烧基-C6〜C14亚芳基-C1〜C4亚烷基、或者C6〜C14亚芳基-C1〜C4亚烷基-C6〜C14亚芳基(此处,亚烷基为直链或支链,可以取代有卤素,C3〜C12亚环烷基或C6〜C14亚芳基无取代、或者可以取代有卤素或C1〜C4烷基)。式(5a)中的L与式(I)、式(Ia)和式(IIa)中的R1的含义相同。 C2~C12 alkylene group [0120] wherein, L is (^ ~C12 alkylene is one or more than one of NH (imino) or 0 atom (an oxygen atom) discontinuous intermittent (with the N atom (a nitrogen atom) bonded H atom (hydrogen atoms) may be substituted with an amino or C1~C12 alkylamino), C3~C12 cycloalkylene, C1~C12 alkylene -C3~C12 cycloalkylene alkyl, C1 ~ C12 alkylene -C3~C12 cycloalkylene -C1~C12 alkylene, C3~C12 cycloalkylene -C1~C4 alkylene -C3~ C12 cycloalkylene burn group, C6~C14 arylene , C1~C4 alkylene burned group -C6~C14 arylene, C1~C4 alkylene burned group -C6~C14 arylene -C1~C4 alkylene group, or C6~C14 arylene -C1~C4 alkylene -C6~C14 arylene group (here, the alkylene is a straight-chain or branched-chain, may be substituted with halogen, C3~C12 cycloalkylene or C6~C14 arylene group unsubstituted or may be substituted with halogen or C1 the same meaning as in formula (Ia) and formula (IIa) R1 in ~C4 alkyl) of formula (5a) L of formula (I).

[0121] 作为多元胺化合物,可以举出具有2个伯氨基的二胺化合物、具有3个伯氨基的三胺化合物等。 [0121] Examples of the polyamine compounds include having two primary amino groups of the diamine compound having three primary amino triamine compound. 作为具有2个伯氨基的二胺化合物,对其没有特别限定,可以举出例如脂肪族二胺、脂环族二胺、芳香族二胺等。 Examples of the diamine compound having two primary amino groups, is not particularly limited, and examples thereof include aliphatic diamines, alicyclic diamines, aromatic diamine. 此外,上述式(5a)表示的化合物之中,L为单键的化合物是肼。 Further, among the compounds represented by the formula (5a), L is a single bond, the compound is hydrazine.

[0122] 作为脂肪族二胺中的具有C1〜C12亚烷基的化合物,具体地说,可以举出例如乙二胺、丙二胺、1,2-二氨基丙烧、1,4- 丁二胺、1,5-戊二胺、1,6-己二胺、1,7-庚二胺、1,8-辛二胺、1,12-十二烧二胺、丙烧-1,2-二胺、1,2-二氨基-2-甲基丙烧等。 [0122] As the aliphatic diamine compounds having a C1~C12 alkylene group, specific examples thereof include e.g., ethylenediamine, propylenediamine, 1,2-diamino propionic burn, 1,4- diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, dodecamethylene burn-diamine, propan-burning -1 2- diamine, 1,2-diamino-2-methylpropane burning and the like.

[0123] 作为脂肪族二胺中的具有被1个或1个以上的0原子(氧原子)非连续间断的直链或支链的C2〜C12的亚烷基的化合物,具体地说,可以举出例如,2, 2' -氧代双(乙胺)、 1,2-双(2-氨基乙氧基)乙烷、1,11-二氨基-3, 6, 9-三氧代i^一烷、双(3-氨基丙基)醚、 1,4-丁二醇双(3-氨基丙基)醚、二甘醇双(3-氨基丙基)醚、乙二醇双(3-氨基丙基)醚等。 [0123] The compound C2~C12 alkylene group having a non-continuous uninterrupted straight or branched chain (an oxygen atom) one or more than one 0 atom aliphatic diamines, in particular, can be Examples thereof include 2, 2 '- oxybis (ethylamine), 1,2-bis (2-aminoethoxy) ethane, 1,11-amino-3, 6, 9-oxo-i ^ a alkyl, bis (3-aminopropyl) ether, 1,4-butanediol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, ethylene glycol bis (3 - aminopropyl) ether and the like.

[0124] 作为脂肪族二胺中的具有被1个或1个以上的NH(亚氨基)非连续间断的直链或支链的C2〜C12的亚烷基(与N原子(氮原子)键合的H原子(氢原子)可以被氨基或C1〜C12的烷基氨基取代)的化合物,具体地说,可以举出例如二亚乙基三胺、三亚乙基四胺、四亚乙基五胺、五亚乙基六胺、三(2-氨基乙基)胺、Ν,Ν' -双(3-氨基丙基)乙二胺、 双(六亚甲基)三胺、3, 3' -二氨基-N-甲基二丙胺、3, 3' -二氨基二丙胺、双(3-氨基丙基)甲胺等。 [0124] Examples of the aliphatic diamines having one or more than one of NH (imino) discontinuous intermittent C2~C12 a straight-chain or branched-chain alkylene group (with the N atom (a nitrogen atom) bond bonded H atom (hydrogen atoms) may be substituted with an amino or C1~C12 alkylamino) compounds, specifically, examples thereof include diethylene triamine, triethylene tetramine, tetraethylene pentamine amine, pentaethylene hexamine, tris (2-aminoethyl) amine, Ν, Ν '- bis (3-aminopropyl) ethylenediamine, bis (hexamethylene) triamine, 3, 3' - diamino -N- methyl-dipropylamine, 3, 3 '- diamino dipropylamine, bis (3-aminopropyl) methylamine.

[0125] 作为脂环族二胺,具体地说,可以举出例如异佛尔酮二胺、1,4_环己二胺、1,3_环己二胺、反式-1,2-环己二胺、1,3_双(氨基甲基)环己烷、4,4'_亚甲基双(环己胺)等。 [0125] Examples of the alicyclic diamines, specifically, includes, for example isophoronediamine, 1,4_ cyclohexanediamine, 1,3_-diaminocyclohexane, trans-1,2 cyclohexanediamine, 1,3_-bis (aminomethyl) cyclohexane, 4,4'_ methylene bis (cyclohexylamine) and the like.

[0126] 作为芳香族二胺,具体地说,可以举出例如对苯二胺、间苯二胺、对苯二甲胺、间苯二甲胺、4, 4' -二氨基二苯基甲烷、1,5-二氨基萘、1,8-二氨基萘、2, 6-二氨基甲苯等。 [0126] Examples of the aromatic diamine, and specifically, examples thereof include p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4, 4 '- diamino diphenyl methane , 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminotoluene and the like.

[0127] 作为具有3个伯氨基的三胺化合物,具体地说,可以举出例如三(4-氨基苯基) 胺、二(3_氨基丙基)胺、下述式表不的二(2-氨基乙基)胺等。 [0127] As triamine compound having three primary amino groups, specifically, examples thereof include tris (4-aminophenyl) amine, bis (3_ aminopropyl) amine, the following formula table is not di ( 2-aminoethyl) amine and the like.

[0128]【化17】 [0128] [Chemical Formula 17]

[0129] [0129]

Figure CN104428339AD00161

[0130] 优选异氰酸酯化合物与肼或与多元胺化合物在有机溶剂中或不加溶剂(无溶剂) 下一边控制温度一边进行反应,对于异氰酸酯化合物1摩尔,肼或多元胺化合物优选为0. 01摩尔〜50摩尔、更优选为0. 1摩尔〜50摩尔、进一步优选为0. 1摩尔〜30摩尔、特别优选为0. 1摩尔〜20摩尔,、温度优选为-KTC〜120°C、更优选为-5°C〜KKTC、进一步优选为(TC〜50°C、特别优选为5〜30°C。 The [0130] Preferably the isocyanate compound with hydrazine or a polyamine compound in an organic solvent or without a solvent (solvent-free) while controlling the temperature of the side reaction, the isocyanate compound of 1 mol of hydrazine or polyamine compound is preferably 0.01 mol ~ 50 moles, more preferably 0.1 mol ~ 50 mol, more preferably 0.1 mol ~ 30 mol, and particularly preferably 0.1 mol ~ 20 mol ,, temperature is preferably -KTC~120 ° C, more preferably It is -5 ° C~KKTC, more preferably (TC~50 ° C, particularly preferably 5~30 ° C.

[0131] 进而,还优选固化剂包含下述化合物,该化合物是将异氰酸酯化合物与肼或与多元胺化合物进行反应而得到的,相对于异氰酸酯化合物所含有的异氰酸酯基1摩尔,肼或多元胺化合物所含有的伯氨基的总数优选为0. 01摩尔〜50摩尔、更优选为0. 1摩尔〜50 摩尔、进一步优选为0. 1摩尔〜30摩尔、特别优选为0. 5摩尔〜20摩尔。 [0131] In addition, further preferably a curing agent comprising the compound, the compound is the isocyanate compound with hydrazine or with a polyamine compound obtained by reacting, with respect to the isocyanate group of isocyanate compound contained in 1 mole of hydrazine or polyamine compound primary amino total contained is preferably 0.01 mol ~ 50 mol, more preferably 0.1 mol ~ 50 mol, more preferably 0.1 mol ~ 30 mol, and particularly preferably 0.5 mol ~ 20 mol.

[0132]〔固化剂〕 [0132] [Curing Agent]

[0133] 本发明涉及的环氧树脂和/或具有至少1个不饱和键的树脂用的固化剂包含下述式⑴表不的化合物。 Epoxy resins of the present invention and or a compound not having at least one resin having an unsaturated bond with a curing agent comprising the following formula ⑴ table [0133] /.

[0134] 本发明的固化剂包含下述式(I)表示的化合物, [0134] the curing agent of the present invention comprises a compound represented by the following formula (I),

[0135]【化18】 [0135] [Chemical Formula 18]

[0136] [0136]

Figure CN104428339AD00162

[0137]〔式中, [0137] [wherein,

[0138] R1为单键,或者为C1〜C12亚烷基、被1个或1个以上的NH(亚氨基)或0氧原子(氧原子)非连续间断的C2〜C12亚烷基(与N原子(氮原子)键合的H原子(氢原子) 可以被氨基或C1〜C12的烷基氨基取代)、C3〜C12亚环烷基、C1〜C12亚烷基-C3〜C12亚环烷基、C1〜C12亚烷基-C3〜C12亚环烷基-C1〜C12亚烷基、C3〜C12亚环烷基-C1〜C12 亚烷基-C3〜C12亚环烷基、C6〜C14亚芳基、C1〜C4亚烷基-C6〜C14亚芳基、C1〜C4亚烷基-C6〜C14亚芳基-C1〜C4亚烷基、或C6〜C14亚芳基-C1〜C4亚烷基-C6〜C14亚芳基(此处,亚烷基为直链或支链,可以取代有卤素,C3〜C12亚环烷基或C6〜C14亚芳基无取代、 或者取代有卤素或C1〜C4烧基), [0138] R1 is a single bond, or a C1~C12 alkylene group is one or more than one of NH (imino) or zero oxygen atom (an oxygen atom) discontinuous intermittent C2~C12 alkylene (with N atom (a nitrogen atom) bonded H atom (hydrogen atoms) may be substituted with an amino or C1~C12 alkylamino), C3~C12 cycloalkylene, C1~C12 alkylene -C3~C12 cycloalkylene group, C1~C12 alkylene -C3~C12 cycloalkylene -C1~C12 alkylene, C3~C12 cycloalkylene -C1~C12 alkylene -C3~C12 alkylene cycloalkyl, C6~C14 arylene, C1~C4 alkylene -C6~C14 arylene, C1~C4 alkylene -C6~C14 arylene -C1~C4 alkylene group, or C6~C14 arylene -C1~C4 alkylene -C6~C14 arylene group (here, the alkylene is a straight-chain or branched-chain, may be substituted with halogen, C3~C12 cycloalkylene or C6~C14 arylene group unsubstituted or substituted with a halo or C1~C4 burn-yl),

[0139]η为1、2、3 或4, [0139] η 2, 3 or 4,

[0140]η为2以上时,R1相互独立,含义与上述相同。 When [0140] η is 2 or more, Rl independently of one another, meaning the same as above.

[0141]η为1时,A为C1〜C12烷基、被1个或1个以上的0原子(氧原子)非连续间断的C2〜C12烷基、C2〜C12烷氧羰基亚烷基、C3〜C12环烷基、C1〜C12烷基-C3〜C12亚环烷基、C3〜C12环烧基-C1〜C12亚烧基-C3〜C12亚环烧基、C6〜C14芳基、C1〜C4烧基-C6〜 C14亚芳基、C6〜C14芳基-C1〜C4亚烷基-C6〜C14亚芳基(此处,亚烷基为直链或支链,可以取代有卤素,C3〜C12环烷基、C3〜C12亚环烷基、C6〜C14芳基或C6〜C14亚芳基无取代、 或者取代有齒素或C1〜C4烧基)、或者(甲基)丙稀醜氧基烧基; [0141] η is 1, A is C1~C12 alkyl, one or more than one 0 atom (an oxygen atom) discontinuous intermittent C2~C12 alkyl, C2~C12 alkoxycarbonyl alkylene, C3~C12 cycloalkyl, C1~C12 alkyl -C3~C12 cycloalkylene, C3~C12 cycloalkyl burning yl -C1~C12 alkylene burn-yl -C3~C12 cycloalkylene burn group, C6~C14 aryl, C1 ~C4 burning yl -C6~ C14 arylene, C6~C14 aryl -C1~C4 alkylene -C6~C14 arylene group (here, the alkylene is a straight-chain or branched-chain, may be substituted with halogen, C3~C12 cycloalkyl, C3~C12 cycloalkylene, C6~C14 aryl, or C6~C14 arylene group unsubstituted or substituted with teeth biotin or C1~C4 burn-yl), or (meth) acrylic ugly group burn-yl;

[0142]η为2时,A为C1〜C12亚烷基、被1个或1个以上的0原子(氧原子)非连续间断的C2〜C12亚烷基、C1〜C12亚烷氧羰基亚烷基、C3〜C12亚环烷基、C1〜C12亚烷基-C3〜C12亚环烷基、C1〜C12亚烷基-C3〜C12亚环烷基-C1〜C12亚烷基、C3〜C12亚环烷基-C1〜 C12亚烧基_C3〜C12亚环烧基、_C3〜C12环烧_基、C6〜C14亚芳基J1〜C4亚烧基_C6〜 C14亚芳基-C1〜C4亚烷基、或者C6〜C14亚芳基-C1〜C4亚烷基-C6〜C14亚芳基(此处, 亚烷基为直链或支链,可以取代有卤素,C3〜C12亚环烷基或C6〜C14亚芳基无取代、或者取代有卤素或C1-C4烷基); [0142] η is 2, A is a C1~C12 alkylene group is one or more than one 0 atom (an oxygen atom) discontinuous intermittent C2~C12 alkylene, C1~C12 alkylene alkoxycarbonylimino alkyl, C3~C12 cycloalkylene, C1~C12 alkylene -C3~C12 alkylene cycloalkyl, C1~C12 alkylene -C3~C12 cycloalkylene -C1~C12 alkylene, C3~ C12 cycloalkylene -C1~ C12 alkylene burn-yl _C3~C12 cycloalkylene burn group, _C3~C12 cycloalkyl burning _ group, C6~C14 arylene J1~C4 alkylene burn-yl _C6~ C14 arylene -C1 ~C4 alkylene group, or C6~C14 arylene -C1~C4 alkylene -C6~C14 arylene group (here, the alkylene is a straight-chain or branched-chain, may be substituted with halogen, C3~C12 alkylene cycloalkyl or C6~C14 unsubstituted arylene, or substituted with halo or C1-C4 alkyl);

[0143]η为3时,A为下述式(1)、下述式⑵或下述式(3), [0143] η is 3, A represented by the following formula (1), the following equation ⑵ or the following formula (3),

[0144]【化19】 [0144] [of 19]

[0145] [0145]

Figure CN104428339AD00171

[0146](式中,R2相同或不同,为直链或支链的C1〜C12亚烷基), [0146] (wherein, the same or different from R2, is a linear or branched C1~C12 alkylene),

[0147]【化20】 [0147] [Chemical Formula 20]

[0148] [0148]

Figure CN104428339AD00172

[0149] (式中,R3相同或不同,为直链或支链的C1〜C12亚烷基), [0149] (wherein, the same or different from R3, a straight-chain or C1~C12 alkylene branched alkyl group),

[0150] 【化21】 [0150] [of 21]

[0151] [0151]

Figure CN104428339AD00181

[0152] (式中,R4相同或不同,为直链或支链的C1-C12亚烷基,R5为CH); [0152] (wherein, R4 are the same or different, is C1-C12 alkylene linear or branched, R5 is CH);

[0153] η为4时,A为下述式(4), [0153] η is 4, A represented by the following formula (4),

[0154] 【化22】 [0154] [Chemical Formula 22]

[0155] [0155]

Figure CN104428339AD00182

[0156] {式中,X3为Si,或者为由C3〜C12环烷基-C1〜C12亚烷基-C3〜C12环烷基、或者C6〜C14芳基-C1〜C4亚烷基-C6〜C14芳基(此处,亚烷基为直链或支链,可以取代有齒素,C3〜C12环烧基或C6〜C14芳基无取代、或者取代有齒素或C1〜C4烧基)衍生的4价残基}〕。 [0156] {in the formula, X3 is Si, or by C3~C12 cycloalkyl -C1~C12 alkylene -C3~C12 cycloalkyl, or C6~C14 aryl -C1~C4 alkylene -C6 ~C14 aryl group (herein, the alkylene group is a straight chain or branched chain, may be substituted with a toothed element, C3~C12 ring burn group or C6~C14 aryl group unsubstituted or substituted with teeth biotin or C1~C4 firing group ) derived from a tetravalent residue}].

[0157] 上述式(I)的化合物优选如下得到:使上述具有至少1个异氰酸酯基(-N=C= 〇)的化合物例如选自上述单异氰酸酯化合物、上述二异氰酸酯化合物、上述三异氰酸酯化合物和上述四异氰酸酯化合物组成的组中的至少一种异氰酸酯化合物与肼或与多元胺化合物发生反应。 [0157] compound of formula (I) is preferably obtained by: so that the at least one isocyanate group (-N = C = square) compounds such as selected from the above monoisocyanate compound, the above-described diisocyanate compound and the triisocyanate compound, and group the four isocyanate compound consisting of at least one isocyanate compound with hydrazine or react with a polyamine compound. 上述式(I)表示的化合物优选是将上述异氰酸酯化合物与上述肼或与多元胺化合物在有机溶剂中或不加溶剂(无溶剂)下通过控制温度进行反应来得到,相对于上述异氰酸酯化合物1摩尔,上述肼或多元胺化合物优选为〇. 01摩尔〜50摩尔、更优选为0. 1摩尔〜50摩尔、进一步优选为0. 1摩尔〜30摩尔、特别优选为0. 1摩尔〜20摩尔,温度优选为-KTC〜120°C、更优选为-5°C〜100°C、进一步优选为(TC〜50°C、特别优选为5 〜30。。。 A compound represented by the above formula (I) is preferably obtained by controlling the temperature of reaction of the isocyanate compound and the above hydrazine or a polyamine compound in an organic solvent or without a solvent (solvent-free) under, with respect to the polyisocyanate compound to 1 mol the hydrazine or polyamine compound is preferably a square. 01 mol ~ 50 mol, more preferably 0.1 mol ~ 50 mol, more preferably 0.1 mol ~ 30 mol, and particularly preferably 0.1 mol ~ 20 mol, temperature is preferably -KTC~120 ° C, more preferably -5 ° C~100 ° C, more preferably (TC~50 ° C, and particularly preferably 5 ~ 30 ...

[0158] 进一步,还优选上述式(I)表示的化合物是将异氰酸酯化合物与肼或与多元胺化合物进行反应时相对于异氰酸酯化合物所含有的异氰酸酯基1摩尔使肼或多元胺化合物所含有的伯氨基的总数优选为〇. 01摩尔〜50摩尔、更优选为0. 1摩尔〜50摩尔、进一步优选为〇. 1摩尔〜30摩尔、特别优选为0. 5摩尔〜20摩尔来进行反应而得到的。 The compound represented by [0158] Further, it is also preferable that the above-mentioned formula (I) is a primary when the isocyanate compound with hydrazine or with a polyamine compound to react with isocyanate groups to 1 mol of hydrazine or polyamine compound isocyanate compound contained in the contained amino total preferably billion. 01 Moore ~ ​​50 moles, more preferably 0.1 mole ~ 50 mol, and more preferably billion. 1 mole ~ 30 mol, particularly preferably 0.5 mole ~ 20 mole be obtained by reacting of.

[0159] 本发明优选为环氧树脂和/或具有至少1个不饱和键的树脂用的固化剂,该固化剂包含上述式(I)表示的化合物之中的由下述式(Ia)表示的化合物。 [0159] The present invention is preferably an epoxy resin and / or having at least one unsaturated bond resin curing agent, the curing agent comprises from among compounds represented by the above formula (I) by the following formula (Ia) represents compound of.

[0160] 本发明的固化剂中,在分子内具有至少1个伯氨基的化合物优选为下述式(Ia), [0160] the curing agent of the present invention, the compound having at least one primary amino group in the molecule is preferably represented by the following formula (Ia),

[0161] 【化23】 [0161] [of 23]

[0162] [0162]

Figure CN104428339AD00191

[0163]〔式中, [0163] [wherein,

[0164]R1相互独立,为单键,或者为C1〜C12亚烷基、被1个或1个以上的NH(亚氨基)或0原子(氧原子)非连续间断的C2〜C12亚烷基(与N原子(氮原子)键合的H原子(氢原子)可以取代有氨基或C1〜C12的烷基氨基)、C3〜C12亚环烷基、C1〜C12亚烷基-C3〜 C12亚环烷基、C1〜C12亚烷基-C3〜C12亚环烷基-C1〜C12亚烷基、C3〜C12亚环烷基-C1〜 C12亚烧基_C3〜C12亚环烧基、C6〜C14亚芳基、(^〜C4亚烧基-C6〜C14亚芳基、C1〜C4亚烷基-C6〜C14亚芳基-C1〜C4亚烷基、或C6〜C14亚芳基-C1〜C4亚烷基-C6〜C14亚芳基(此处,亚烷基为直链或支链,可以取代有卤素,C3〜C12亚环烷基或C6〜C14亚芳基无取代、或者取代有卤素或C1〜C4烧基), [0164] R1 each independently, a single bond, an alkylene or a C1~C12 alkyl, at least one of the one or NH (imino) or 0 atom (an oxygen atom) discontinuous alkylene interrupted C2~C12 (N atom (a nitrogen atom) bonded H atom (hydrogen atoms) may be substituted with amino or C1~C12 alkylamino), C3~C12 cycloalkylene, C1~C12 alkylene -C3~ C12 alkylene cycloalkyl, C1~C12 alkylene -C3~C12 cycloalkylene -C1~C12 alkylene, C3~C12 cycloalkylene -C1~ C12 alkylene burn-yl _C3~C12 cycloalkylene burn group, C6 ~C14 arylene, (^ ~C4 alkylene burn group -C6~C14 arylene, C1~C4 alkylene -C6~C14 arylene -C1~C4 alkylene group, or C6~C14 arylene - C1~C4 alkylene -C6~C14 arylene group (here, the alkylene is a straight-chain or branched-chain, may be substituted with halogen, C3~C12 cycloalkylene or C6~C14 arylene group unsubstituted or substituted with halogen or C1~C4 burn-yl),

[0165] X1为C1〜C12亚烷基、被1个或1个以上的0原子(氧原子)非连续间断的C2〜 C12亚烷基、C1〜C12亚烷氧羰基亚烷基、C3〜C12亚环烷基、C1〜C12亚烷基-C3〜C12亚环烧基、C1〜C12亚烧基_C3〜C12亚环烧基-C1〜C12亚烧基、C3〜C12亚环烧基-C1〜C12亚烧基-C3〜C12亚环烧基、_C3〜C12环烧_基、C6〜C14亚芳基J1〜C4亚烧基_C6〜C14亚芳基-C1〜C4亚烷基、或者C6〜C14亚芳基-C1〜C4亚烷基-C6〜C14亚芳基(此处,亚烷基为直链或支链,可以取代有卤素,C3〜C12亚环烧基或C6〜C14亚芳基无取代、或者取代有齒素或C1〜C4烧基)〕。 [0165] X1 is C1~C12 alkylene group is one or more than one 0 atom (an oxygen atom) discontinuous intermittent C2~ C12 alkylene group, C1~C12 alkylene alkoxycarbonyl, alkylene, C3~ C12 cycloalkylene, C1~C12 alkylene -C3~C12 cycloalkylene burn group, C1~C12 alkylene burning yl _C3~C12 cycloalkylene burn group -C1~C12 alkylene burn group, C3~C12 cycloalkylene burn group -C1~C12 alkylene burning yl -C3~C12 cycloalkylene burn group, _C3~C12 ring burn _ group, C6~C14 arylene J1~C4 alkylene burn group _C6~C14 arylene -C1~C4 alkylene or C6~C14 arylene -C1~C4 alkylene -C6~C14 arylene group (here, the alkylene is a straight-chain or branched-chain, may be substituted with halogen, C3~C12 cycloalkylene burning or C6 ~C14 arylene group unsubstituted or substituted with teeth biotin or C1~C4 burn-yl)].

[0166] 式(Ia)中的X1与式⑴中η为2时的A的含义相同。 η same as in [0166] Formula (Ia) X1 ⑴ Formula 2 for the meanings of A.

[0167] 上述式(Ia)表示的化合物优选是使上述二异氰酸酯化合物与肼或与多元胺化合物反应而得到的。 The compound represented by [0167] the above formula (Ia) is preferably that the above-described diisocyanate compounds with hydrazine or a reaction with a polyamine compound is obtained. 优选二异氰酸酯化合物与肼或与多元胺化合物在有机溶剂中或不加溶剂(无溶剂)下一边控制温度一边进行反应,相对于二异氰酸酯化合物1摩尔,肼或多元胺化合物优选为〇. 01摩尔〜50摩尔、更优选为0. 1摩尔〜50摩尔、进一步优选为0. 1摩尔〜30 摩尔、特别优选为〇. 1摩尔〜20摩尔,温度优选为-KTC〜120°C、更优选为-5°C〜100°C、 进一步优选为〇°C〜50°C、特别优选为5〜30°C。 Preferably a diisocyanate compound with hydrazine or a polyamine compound in an organic solvent or without a solvent (solvent-free) at the side to control the temperature while the reaction, with respect to the diisocyanate compound 1 mole of hydrazine or polyamine compound is preferably a square. 01 mol ~ 50 moles, more preferably 0.1 mol ~ 50 mol, more preferably 0.1 mol ~ 30 mol, particularly preferably square. 1 mol ~ 20 mol, the temperature is preferably -KTC~120 ° C, more preferably -5 ° C~100 ° C, more preferably square ° C~50 ° C, and particularly preferably 5~30 ° C.

[0168] 对于上述二异氰酸酯化合物与例如作为分子内具有3个伯氨基的多元胺化合物的三(2-氨基乙基)胺的反应而得到的化合物,可以举出下述式表示的化合物。 [0168] For the above-described diisocyanate compound with a compound as reaction of the amine tris (2-aminoethyl) having three primary amino groups of the polyamine compound in the molecule obtained, for example, be a compound represented by the following formula exemplified.

[0169]【化24】 [0169] [Chemical Formula 24]

[0170] [0170]

Figure CN104428339AD00192

[0171] 上述式中,X1与式(Ia)中的X1的含义相同。 [0171] In the above formula, the same meaning as X1 in X1 and the formula (Ia).

[0172] 作为上述式(Ia)表示的化合物,可以举出例如, [0172] As the compound represented by the formula (Ia), there may be mentioned, for example,

[0173]1,1' -[亚甲基双(环己烧_1,4_二基)]双[3-(12-氨基十二烧基)脈](A-1)、 [0173] 1,1 '- [methylene bis (cyclohexyl burning _1,4_-diyl)] bis [3- (12-aminododecanoic burn-yl) pulse] (A-1),

[0174] 1,Γ-[亚甲基双(环己烷-1,4-二基)]双[3-(2-氨基乙基)脲](A-2)、 [0174] 1, Γ- [methylene bis (cyclohexane-1,4-diyl)] bis [3- (2-aminoethyl) ureido] (A-2),

[0175] 1,Γ-[亚甲基双(环己烷-1,4_二基)]双[3-(6-氨基己基)脲](A-3)、 [0175] 1, Γ- [methylene bis (cyclohexane -1,4_-diyl)] bis [3- (6-aminohexyl) urea] (A-3),

[0176] 1,1 ' -(己烧-1,6_ 二基)双[3_ (12-氨基十二烧基)脈](A-4)、 [0176] 1,1 '- (cyclohexyl burning -1,6_-diyl) bis [3_ (12-aminododecanoic burn-yl) pulse] (A-4),

[0177] 1,1 ' -(己烧-1,6_ 二基)双[3_ (2_ 氨基乙基)脈](A-5)、 [0177] 1,1 '- (cyclohexyl -1,6_ burn-diyl) bis [3_ (2_ aminoethyl) pulse] (A-5),

[0178] 1,1 ' -(己烧-1,6_ 二基)双[3_ (6_ 氨基己基)脈](A-6)、 [0178] 1,1 '- (cyclohexyl burning -1,6_-diyl) bis [3_ (6_ aminohexyl) pulse] (A-6),

[0179] Ν,Ν'-六亚甲基[羰基双(氮烷二基)-2_氨基乙基]-[羰基双(氮烷二基)-6_氨基己基](A-7)等。 [0179] Ν, Ν'- hexamethylene [carbonyl-bis (azanediyl) -2_ aminoethyl] - [carbonyl-bis (azanediyl) -6_ aminohexyl] (A-7), etc. .

[0180] 作为上述式(Ia)表示的化合物,可以举出例如下述式表示的化合物。 [0180] As the compound represented by the formula (Ia), compounds represented by the following formula may be mentioned.

[0181]【化25】 [0181] [of 25]

Figure CN104428339AD00201

[0183] 本发明优选为环氧树脂和/或具有至少1个不饱和键的树脂用的固化剂,该固化剂包含上述式(I)表示的化合物之中的由下述式(Ib)表示的化合物。 [0183] The present invention is preferably an epoxy resin and / or having at least one unsaturated bond resin curing agent, the curing agent comprises from among compounds represented by the above formula (I) by the following formula (Ib) represented by compound of.

[0184] 本发明的固化剂中,在分子内具有至少1个伯氨基的化合物优选为下述式(Ib)表示的二氨基脲化合物(式中,X1含义与上述相同)。 [0184] the curing agent of the present invention, a compound having a primary amino group of at least one preferably in the molecule (wherein, the X1 meaning as defined above) of two semicarbazide compound represented by the following formula (Ib).

[0185] 【化26】 [0185] [Chemical Formula 26]

[0186] [0186]

Figure CN104428339AD00211

[0187] 式(Ib)中的X1与式(I)中η为2时的A的含义相同。 η same as in [0187] of formula (Ib) X1 in the formula (I) is the meaning of 2:00 of A in.

[0188] 上述式(Ib)表示的化合物优选是使上述二异氰酸酯化合物与肼反应而得到的。 The compound represented by [0188] the above formula (Ib) is preferably so that the reaction of a diisocyanate compound obtained with hydrazine. 优选二异氰酸酯化合物与肼在有机溶剂中或不加溶剂(无溶剂)下一边控制温度一边进行反应来得到,相对于二异氰酸酯化合物1摩尔,肼优选为〇. 01摩尔〜50摩尔、更优选为0. 1 摩尔〜50摩尔、进一步优选为0. 1摩尔〜30摩尔、特别优选为0. 1摩尔〜20摩尔,温度优选为-KTC〜120°C、更优选为-5°C〜KKTC、进一步优选为(TC〜50°C、特别优选为5〜 30。。。 Preferred diisocyanate compounds with hydrazine in an organic solvent or without solvent (solvent-free) at the side of the control temperature while the reaction to obtain, with respect to the diisocyanate compound to 1 mol of hydrazine preferably billion. 01 Moore ~ ​​50 moles, more preferably 0.1 mol ~ 50 mol, more preferably 0.1 mol ~ 30 mol, and particularly preferably 0.1 mol ~ 20 mol, the temperature is preferably -KTC~120 ° C, more preferably -5 ° C~KKTC, more preferably (TC~50 ° C, particularly preferably -5 to 30 ...

[0189] 作为上述式(Ib)表示的二氨基脲化合物,可以举出例如, [0189] Examples of the dicarboxylic semicarbazide compound represented by the formula (Ib), include, for example,

[0190] 4,4'-(亚甲基二-1,4-环己基)双(氨基脲)(BI)、 [0190] 4,4 '- (methylenebis-1,4-cyclohexylene) bis (semicarbazide) (BI),

[0191] 4,4' -六亚甲基双(氨基脲)(B-2)、 [0191] 4,4 '- hexamethylene bis (semicarbazide) (B-2),

[0192] 4, 4' _(2, 2, 4-三甲基六亚甲基)双(氨基脲)(B-3)、 [0192] 4, 4 '_ (2, 2, 4-trimethyl hexamethylene) bis (semicarbazide) (B-3),

[0193] 4,4' -(1,3_环己基双亚甲基)双(氨基脲)(B-4)、 [0193] 4,4 '- (1,3_ cyclohexyl-bis methylene) bis (semicarbazide) (B-4),

[0194] 4, 4' _(1,3-亚苯基双亚甲基)双(氨基脲)(Β-5)、 [0194] 4, 4 '_ (1,3-phenylene-bis-methylene) bis (semicarbazide) (Β-5),

[0195] 4, 4' -异佛尔酮双(氨基脲)(Β-6)等。 [0195] 4, 4 '- isophorone-bis (semicarbazide) (Β-6) and the like.

[0196] 作为上述式(Ib)表示的化合物,可以举出例如下述式表示的化合物。 [0196] As the compound represented by the formula (Ib), compounds represented by the following formula may be mentioned.

[0197]【化27】 [0197] [of 27]

[0198] [0198]

Figure CN104428339AD00221

[0199] 本发明的固化剂优选包含下述式(IIa), [0199] the curing agent is preferably present invention comprises the following formula (IIa),

[0200] 【化28】 [0200] [Chemical Formula 28]

[0201] [0201]

[0202] 〔式中, [0202] [wherein,

Figure CN104428339AD00222

[0203] R1为单键,或者为C1〜C12亚烷基、被1个或1个以上的NH(亚氨基)或0原子(氧原子)非连续间断的C2〜C12亚烷基(与N原子(氮原子)键合的H原子(氢原子) 可以被氨基或C1〜C12的烷基氨基取代)、C3〜C12亚环烷基、C1〜C12亚烷基-C3〜C12亚环烷基、C1〜C12亚烷基-C3〜C12亚环烷基-C1〜C12亚烷基、C3〜C12亚环烷基-C1〜C12 亚烷基-C3〜C12亚环烷基、C6〜C14亚芳基、C1〜C4亚烷基-C6〜C14亚芳基、C1〜C4亚烷基-C6〜C14亚芳基-C1〜C4亚烷基、或C6〜C14亚芳基-C1〜C4亚烷基-C6〜C14亚芳基(此处,亚烷基为直链或支链,可以取代有卤素,C3〜C12亚环烷基或C6〜C14亚芳基无取代、 或者取代有卤素或C1〜C4烧基), [0203] R1 is a single bond, or a C1~C12 alkylene group is one or more than one of NH (imino) or 0 atom (an oxygen atom) discontinuous intermittent C2~C12 alkylene (with N atom (a nitrogen atom) bonded H atom (hydrogen atoms) may be substituted with an amino or C1~C12 alkylamino), C3~C12 cycloalkylene, C1~C12 alkylene -C3~C12 cycloalkylene group , C1~C12 alkylene -C3~C12 cycloalkylene -C1~C12 alkylene, C3~C12 cycloalkylene -C1~C12 alkylene -C3~C12 alkylene cycloalkyl, C6~C14 alkylene an aryl group, C1~C4 alkylene -C6~C14 arylene, C1~C4 alkylene -C6~C14 arylene -C1~C4 alkylene group, or C6~C14 arylene -C1~C4 alkylene alkyl -C6~C14 arylene group (here, the alkylene is a straight-chain or branched-chain, may be substituted with halogen, C3~C12 cycloalkylene or C6~C14 arylene group unsubstituted or substituted with halo or C1~C4 burn-yl),

[0204] X2为C1〜C12烷基、被1个或1个以上的0原子(氧原子)非连续间断的C2〜C12 烷基、C1〜C12烷氧羰基亚烷基、C3〜C12环烷基、C1〜C12烷基-C3〜C12亚环烷基、C3〜C12 环烷基-C1〜C12亚烷基-C3〜C12亚环烷基、C6〜C14芳基、C1〜C4烷基-C6〜C14亚芳基、 C6〜C14芳基-C1〜C4亚烷基-C6〜C14亚芳基(此处,亚烷基为直链或支链,可以取代有卤素,C3〜C12环烷基、C3〜C12亚环烷基、C6〜C14芳基或C6〜C14亚芳基无取代、或者取代有卤素或C1-C4烷基)、或者(甲基)丙烯酰氧基烷基〕。 [0204] X2 is a C1~C12 alkyl, one or more than one 0 atom (an oxygen atom) discontinuous intermittent C2~C12 alkyl, C1~C12 alkoxycarbonyl, alkylene, C3~C12 cycloalkoxy group, C1~C12 alkyl -C3~C12 cycloalkylene, C3~C12 cycloalkyl -C1~C12 alkylene -C3~C12 cycloalkylene, C6~C14 aryl, C1~C4 alkyl - C6~C14 arylene, C6~C14 aryl -C1~C4 alkylene -C6~C14 arylene group (here, the alkylene is a straight-chain or branched-chain, may be substituted with halogen, C3~C12 cycloalkoxy group, C3~C12 cycloalkylene, C6~C14 aryl, or C6~C14 arylene group unsubstituted or substituted with halo or C1-C4 alkyl), or (meth) acryloyloxy alkyl]. 式(IIa)中的X2与式(I)中η为1时的A的含义相同。 η same as in formula (IIa) X2 of the formula (I) as Meaning 1 when A is.

[0205] 上述式(IIa)表示的化合物优选是使上述单异氰酸酯化合物与上述肼或多元胺化合物反应而得到的。 The compound represented by [0205] the above formula (IIa) is preferably so that the monoisocyanate compound which reacts with the hydrazine or polyamine compound is obtained. 优选上述单异氰酸酯化合物与肼或与多元胺化合物在有机溶剂中或不加溶剂(无溶剂)下一边控制温度一边进行反应来得到,相对于上述单异氰酸酯化合物的异氰酸酯基1摩尔,二氨基化合物的氨基优选为〇. 1摩尔〜50摩尔、进一步优选为0. 1摩尔〜30摩尔、特别优选为0. 1摩尔〜20摩尔,温度优选为-KTC〜120°C、更优选为-5°C〜 100°C、进一步优选为(TC〜50°C、特别优选为5〜30°C。 Preferably, the monoisocyanate compound with hydrazine or with a polyamine compound with or without an organic solvent solvent (without solvent) at the side to control the temperature while the reaction to obtain, with respect to the monoisocyanate compound is an isocyanate group 1 mol diamino compound group is preferably a square. 1 mol ~ 50 mol, more preferably 0.1 mol ~ 30 mol, and particularly preferably 0.1 mol ~ 20 mol, the temperature is preferably -KTC~120 ° C, more preferably -5 ° C ~ 100 ° C, more preferably (TC~50 ° C, particularly preferably 5~30 ° C.

[0206] 式(IIa)中R1为单键时,其为氨基脲化合物。 [0206] Formula (IIa) wherein R1 is a single bond, which is a semicarbazide compound. 氨基脲化合物优选为下述式(IIb) 表不的化合物。 Compounds of table is not the following formula (IIb) semicarbazide compound is preferably.

[0207] 【化29】 [0207] [of 29]

[0208] [0208]

Figure CN104428339AD00231

[0209]式中,X2含义与上述相同。 [0209] wherein, X2 meaning as defined above. 式(IIb)中的X2与式(I)中η为1时的A的含义相同。 η same as in the formula (IIb) X2 of the formula (I) as Meaning 1 when A is. [0210]上述式(IIb)表示的化合物优选是使上述单异氰酸酯化合物与肼反应而得到的。 The compound represented by [0210] the above formula (IIb) is preferably so that the monoisocyanate compound is reacted with hydrazine obtained. 优选单异氰酸酯化合物与肼、在有机溶剂中或不加溶剂(无溶剂)下、一边控制温度一边进行反应来得到,相对于单异氰酸酯化合物1摩尔,肼优选为〇. 01摩尔〜50摩尔、更优选为0. 1摩尔〜50摩尔、进一步优选为0. 1摩尔〜30摩尔、特别优选为0. 1摩尔〜20摩尔,温度优选为-KTC〜120°C、更优选为-5°C〜100°C、进一步优选为(TC〜50°C、特别优选为5〜30。。。 Preferably monoisocyanate compound with hydrazine in an organic solvent or without a solvent (solvent-free) under, while controlling the temperature while the reaction to obtain, with respect to the monoisocyanate compound 1 mole of hydrazine is preferably square. 01 mol ~ 50 mol, and more preferably 0.1 mole ~ 50 mol, and more preferably 0.1 mole ~ 30 mol, particularly preferably from 0.1 mol ~ 20 mole, the temperature is preferably -KTC~120 ° C, more preferably -5 ° C~ 100 ° C, more preferably (TC~50 ° C, particularly preferably 5~30 ...

[0211] 作为上述式(IIa)表示的化合物,可以举出例如4_(丙烯酸乙酯)氨基脲(B-7)。 [0211] As the compound represented by the formula (IIa), include, for example 4_ (ethyl acrylate) semicarbazide (B-7).

[0212] 作为上述式(IIb)表示的化合物,可以举出例如下述式表示的化合物。 [0212] As the compound represented by the formula (IIb), compounds represented by the following formula may be mentioned.

[0213]【化30】 [0213] [Chemical Formula 30]

[0214] [0214]

Figure CN104428339AD00241

[0215] 本发明的固化剂还优选为包含下述化合物的固化剂,该化合物是用异氰酸酯化合物进一步对通过上述异氰酸酯化合物与肼或与分子内具有2个以上伯氨基的多元胺化合物的反应所得到的在分子内具有至少1个伯氨基的化合物进行处理而得到的。 [0215] the curing agent is further preferred according to the present invention is a curing agent comprising the compound, the compound with the isocyanate compound is further reacted to polyamine compound ester compound with hydrazine or with two or more primary amino groups by the above-described isocyanate with the molecule being the resulting compound having at least one primary amino group in a molecule obtained by treating.

[0216] 固化剂通过包含用异氰酸酯化合物处理在分子内具有至少1个伯氨基的化合物而得到的化合物,能够提高包含固化剂以及环氧树脂和/或具有至少1个不饱和键的树脂的树脂组合物的液体稳定性,可抑制粘度随着时间经过而上升。 [0216] the curing agent compound-treated compound having at least one primary amino group in a molecule with an isocyanate compound obtained by the inclusion, can be enhanced comprising a curing agent and epoxy resins and / or resin having at least one unsaturated bond resin liquid stability of the composition, can be suppressed viscosity over time rises.

[0217] 在分子内具有至少1个伯氨基的化合物的处理中使用的异氰酸酯化合物只要是具有至少1个异氰酸酯基的化合物就不特别限制。 Compound treatment compound [0217] having at least one primary amino group in the molecule used in the isocyanate compound as long as it has at least one isocyanate group is not particularly limited. 作为异氰酸酯化合物,可优选使用选自上述的异氰酸酯化合物中的至少一种。 As the isocyanate compound, it can be preferably selected from at least one of the above isocyanate compound. 异氰酸酯化合物可单独使用1种,也可组合2种以上使用。 Isocyanate compounds may be used alone or in combination of two or more.

[0218] 处理在分子内具有至少1个伯氨基的化合物的异氰酸酯化合物的用量不特别限制,可根据目的等来适宜选择。 [0218] The amount of treating compound having at least one primary amino group in the molecule of the isocyanate compound is not particularly limited, depending on the purpose or the like is appropriately selected. 以在分子内具有至少1个伯氨基的化合物的氨基数为1摩尔时,异氰酸酯化合物的用量优选为异氰酸酯化合物的异氰酸酯基数达到〇. 01摩尔〜10 摩尔的量、更优选为异氰酸酯化合物的异氰酸酯基数达到0. 02摩尔〜5摩尔的量、进一步优选为异氰酸酯化合物的异氰酸酯基数达到〇. 05摩尔〜2摩尔的量。 When the number of amino compound having at least one primary amino group in the molecule is 1 mol, the amount of the isocyanate compound is preferably isocyanate groups of isocyanate compound into the square. Molar amount of ~ 10 mole 01, and more preferably isocyanate groups of isocyanate compound reaches 0.02 mol ~ 5 molar amount, more preferably isocyanate groups of isocyanate compound into the square amount of 05 mol ~ 2 mol.

[0219] 优选在分子内具有至少1个伯氨基的化合物的基于异氰酸酯化合物的处理在有机溶剂中或不加溶剂(无溶剂)下、一边控制温度一边进行,温度优选为-KTC〜120°C、更优选为_5°C〜100°C、进一步优选为KTC〜90°C、特别优选为20°C〜80°C。 [0219] preferably having at least one compound having a primary amino group in the molecule based on the treatment in an organic solvent, the isocyanate compound or absence of a solvent (solvent-free) under, while controlling the temperature bisamide temperature is preferably -KTC~120 ° C , more preferably at _5 ° C~100 ° C, more preferably KTC~90 ° C, particularly preferably 20 ° C~80 ° C. 处理时间可为例如0. 1〜100小时、优选为0. 5〜50小时。 Treatment time may be, for example, 0.5 1~100 hours, preferably 0. 5~50 hours. 加热混合的时间根据加热混合的温度而异, 温度高则时间缩短,温度低则时间加长,因此,可根据作为固化剂进行使用时的使用目的等来选择最佳的处理时间。 Heating mixing time varies depending on the heating temperature of mixing, the high temperature is shortened, low temperature is longer, thus, may select the optimum treatment time depending on the purpose isochronous be used as a curing agent.

[0220] 本发明的固化剂还优选为包含下述化合物的固化剂,该化合物是用异氰酸酯化合物和环氧树脂进一步对通过上述异氰酸酯化合物与肼或与分子内具有2个以上伯氨基的多元胺化合物的反应所得到的在分子内具有至少1个伯氨基的化合物进行处理而得到的。 [0220] the curing agent of the present invention is also preferably comprises a curing agent of the following compound, the compound is an isocyanate compound and an epoxy resin further polyamines of the above isocyanate compound with hydrazine or with two or more primary amino groups within the molecule reaction of a compound of the obtained compound having at least one primary amino group in a molecule obtained by treating.

[0221] 固化剂通过包含用异氰酸酯化合物和环氧树脂处理在分子内具有至少1个伯氨基的化合物而得到的化合物,能够提高包含固化剂以及环氧树脂和/或具有至少1个不饱和键的树脂的树脂组合物的液体稳定性,可抑制粘度随着时间经过而上升。 [0221] a curing agent comprising a compound with an isocyanate compound and an epoxy compound having at least one primary amino group is treated in a molecule is obtained, it can be improved comprising a curing agent and epoxy resin and / or having at least one unsaturated bond liquid stability of the resin composition of the resin is suppressed viscosity over time rises.

[0222] 在分子内具有至少1个伯氨基的化合物的处理中使用的异氰酸酯化合物只要是具有至少1个异氰酸酯基的化合物就不特别限制。 Compound treatment compound [0222] having at least one primary amino group in the molecule used in the isocyanate compound as long as it has at least one isocyanate group is not particularly limited. 作为异氰酸酯化合物,可优选使用选自上述的异氰酸酯化合物中的至少一种。 The isocyanate compound can be preferably selected from the above-mentioned isocyanate compound is at least one. 异氰酸酯化合物可单独使用1种,也可组合2种以上使用。 Isocyanate compounds may be used alone or in combination of two or more.

[0223] 在分子内具有至少1个伯氨基的化合物的处理中使用的环氧树脂只要是具有至少1个环氧基的化合物就不特别限制,可以从公知的环氧树脂中适当选择来使用。 [0223] treating compound having at least one primary amino group in the molecule, the epoxy resin used as long as it is a compound having at least one epoxy group is not particularly limited, and may be selected from known epoxy resins suitable for use . 作为环氧树脂,可以举出例如,双酚A型环氧树脂、双酚F型环氧树脂、双酚AD型环氧树脂、线型酚醛型环氧树脂、甲酚-线型酚醛型环氧树脂、环状脂肪族环氧树脂、缩水甘油酯系环氧树月旨、缩水甘油胺系环氧树脂、杂环式环氧树脂、氨基甲酸酯改性环氧树脂等。 The epoxy resin may include bisphenol A type epoxy resins, bisphenol F epoxy resin, bisphenol AD ​​type epoxy resins, novolak type epoxy resin, a cresol - novolac ring epoxy resins, cyclic aliphatic epoxy resin, glycidyl ester-based epoxy months purpose, glycidyl amine-based epoxy resin, heterocyclic epoxy resins, urethane-modified epoxy resin. 这些之中,优选使用双酚A型环氧树脂、缩水甘油酯系环氧树脂等。 Among these, bisphenol A type epoxy resin, glycidyl ester-based epoxy resin. 环氧树脂可单独使用1种,也可组合2 种以上使用。 Epoxy resins may be used alone or in combination of two or more.

[0224] 对处理在分子内具有至少1个伯氨基的化合物的异氰酸酯化合物的用量不特别限制,可根据目的等来适宜选择。 [0224] The amount of treating compound having at least one primary amino group in the molecule of the isocyanate compound is not particularly limited, depending on the purpose or the like is appropriately selected. 以在分子内具有至少1个伯氨基的化合物的氨基数为1摩尔时,异氰酸酯化合物的用量优选为异氰酸酯化合物的异氰酸酯基数达到〇. 01摩尔〜10 摩尔的量、更优选为异氰酸酯化合物的异氰酸酯基数达到〇. 02摩尔〜5摩尔的量、进一步优选为异氰酸酯化合物的异氰酸酯基数达到〇. 05摩尔〜2摩尔的量。 When the number of amino compound having at least one primary amino group in the molecule is 1 mol, the amount of the isocyanate compound is preferably isocyanate groups of isocyanate compound into the square. Molar amount of ~ 10 mole 01, and more preferably isocyanate groups of isocyanate compound mol ~ 5 mol reached billion. 02, more preferably isocyanate groups of isocyanate compound into the square. mols ~ 2 moles 05.

[0225] 对处理在分子内具有至少1个伯氨基的化合物的环氧树脂的用量不特别限制,可根据目的等来适宜选择。 [0225] The amount of compound treatment having at least one primary amino group in the molecule of the epoxy resin is not particularly limited, depending on the purpose or the like is appropriately selected. 以在分子内具有至少1个伯氨基的化合物的氨基数为1摩尔时,环氧树脂的用量优选为环氧树脂的环氧基数达到〇. 001摩尔〜10摩尔的量、进一步优选为环氧树脂的环氧基数达到〇. 005摩尔〜1摩尔的量、更优选为环氧树脂的环氧基数达到0. 01 摩尔〜0. 5摩尔的量。 When the number of amino compound having at least one primary amino group in the molecule is 1 mol, the amount of the epoxy resin is preferably epoxy groups of the epoxy resin to achieve the square. Mol ~ 10 mol 001 amount, more preferably an epoxy epoxy groups of the resin reaches square. 005 mol ~ 1 molar amount, more preferably an epoxy resin of epoxy groups to achieve an amount of 0.01 mol ~ 0. 5 mol.

[0226] 优选在分子内具有至少1个伯氨基的化合物的基于异氰酸酯化合物和环氧树脂的处理在有机溶剂中或不加溶剂(无溶剂)下一边控制温度一边进行,温度优选为-KTC〜 120°C、更优选为-5°C〜100°C、进一步优选为KTC〜90°C、特别优选为20°C〜80°C。 [0226] compound having at least one primary amino group preferably having in the molecule the processing isocyanate compound and an epoxy resin-based organic solvent or without a solvent (solvent-free) at the side of the control temperature while performed, the temperature is preferably -KTC~ 120 ° C, more preferably -5 ° C~100 ° C, more preferably KTC~90 ° C, particularly preferably 20 ° C~80 ° C. 处理时间可为例如0. 1〜100小时、优选为0. 5〜50小时。 Treatment time may be, for example, 0.5 1~100 hours, preferably 0. 5~50 hours. 加热混合的时间根据加热混合的温度而异,温度高则时间缩短,温度低则时间加长,因此,可根据作为固化剂进行使用时的使用目的等来选择最佳的处理时间。 Heating mixing time varies depending on the heating temperature of mixing, the high temperature is shortened, low temperature is longer, thus, may select the optimum treatment time depending on the purpose isochronous be used as a curing agent.

[0227] 本发明的固化剂还优选为包含下述化合物的固化剂,该化合物是用异氰酸酯化合物和具有羟基的化合物进一步对通过上述异氰酸酯化合物与肼或分子内具有2个以上伯氨基的多元胺化合物的反应所得到的在分子内具有至少1个伯氨基的化合物进行处理而得到的。 [0227] The present invention curing agent is also preferably include the following compounds curing agent, the compound is an isocyanate compound and having a hydroxyl compounds further by the above-mentioned isocyanate compound with hydrazine or molecules having two or more primary amino groups of the polyamine reaction of a compound of the obtained compound having at least one primary amino group in a molecule obtained by treating.

[0228]固化剂通过包含用异氰酸酯化合物和具有羟基的化合物处理在分子内具有至少1个伯氨基的化合物而得到的化合物,能够提高包含固化剂以及环氧树脂和/或具有至少1 个不饱和键的树脂的树脂组合物的液体稳定性,可抑制粘度随着时间经过而上升。 [0228] Compound a curing agent with an isocyanate compound and a compound having a hydroxyl group comprises treating compound at least one primary amino group in a molecule is obtained, can be improved comprising a curing agent and epoxy resin and / or having at least one unsaturated liquid stability of the resin composition is a resin bond, suppressed the viscosity over time rises.

[0229] 在分子内具有至少1个伯氨基的化合物的处理中使用的异氰酸酯化合物只要是具有至少1个异氰酸酯基的化合物就不特别限制。 Compound treatment compound [0229] having at least one primary amino group in the molecule used in the isocyanate compound as long as it has at least one isocyanate group is not particularly limited. 作为异氰酸酯化合物,可优选使用选自上述的异氰酸酯化合物中的至少一种。 As the isocyanate compound, it can be preferably selected from at least one of the above isocyanate compound. 异氰酸酯化合物可单独使用1种,也可组合2种以上使用。 Isocyanate compounds may be used alone or in combination of two or more.

[0230] 对在分子内具有至少1个伯氨基的化合物的处理中使用的具有羟基的化合物不特别限制,可从公知的化合物中适当选择来使用。 [0230] are not particularly limited processing compound having a hydroxyl compound having at least one primary amino group in the molecule used may be selected from known compounds suitable for use. 作为具有羟基的化合物,具体地说,可以举出醇化合物、酚化合物、羧酸化合物等。 As the compound having a hydroxyl group, specific examples thereof include an alcohol compound, phenol compound, a carboxylic acid compound. 具有羟基的化合物可以为单官能化合物,也可以为多官能化合物。 Compounds having a hydroxyl group may be a monofunctional compound may be a polyfunctional compound.

[0231] 醇化合物之中,作为一元醇化合物,可以举出例如,甲醇、乙醇、1-丙醇、异丙醇、 1- 丁醇、2- 丁醇、异丁醇、叔丁醇、3-甲基-2- 丁醇、叔戊醇、2, 4-二甲基-3-戊醇、3-乙基-3-戊醇、3-甲基-3-戊醇、季戊四醇、3-戊醇、2-丙炔-1-醇、三甲基甲硅烷基甲醇、 烯丙醇、2-溴乙醇、3-乙基-2-甲基-3-戊醇、2-碘乙醇、1-甲氧基-2-丙醇、丙酮氰醇、 (R) - (-) -1-甲氧基-2-丙醇、3-戊炔-1-醇、3- 丁炔-2-醇、3- 丁炔-2-醇、(R) - (+) -3- 丁炔-2-醇、(S) - (-) -3- 丁炔-2-醇、(R) - (+) -3- 丁炔-2-醇、乙烯氰醇、3, 3-二甲基-1- 丁醇、2, 2-二氟乙醇、乙醇酸甲酯、4-庚醇、3-己醇、3-己炔-1-醇、3-甲基-1- 丁醇、 (S)-(-)-2-甲基-1-丁醇、DL-2-甲基-1-丁醇、2-甲基-3-丁炔-2-醇、4-甲基-4-庚醇、2-甲基-2-戊醇、2-戊醇、(S)-(+)-2-戊醇、(R)-(-)-2-戊醇、2, 2, 2-三氟乙醇、 2, 2, 2-三氯乙醇、2, 2, 2-三溴 Among the [0231] alcohol compound, a monohydric alcohol compound include, for example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, t-butanol, 3 - methyl-2-butanol, tert-amyl alcohol, 2, 4-dimethyl-3-pentanol, 3-ethyl-3-pentanol, 3-methyl-3-pentanol, pentaerythritol, 3- pentanol, 2-propyn-1-ol, trimethylsilyl group methanol, allyl alcohol, 2-bromoethanol, 3-ethyl-2-methyl-3-pentanol, 2-iodoethanol, 1 - methoxy-2-propanol, acetone cyanohydrin, (R & lt) - (-) -1- methoxy-2-propanol, 3-pentyn-1-ol, 3-butyn-2-ol , 3-butyn-2-ol, (R) - (+) -3- butyn-2-ol, (S) - (-) -3- butyn-2-ol, (R) - (+ ) -3-butyn-2-ol, ethylene cyanohydrin, 3, 3-dimethyl-1-butanol, 2, 2-fluoro, ethanol, methyl-4-heptanol, 3-hexanol , 3-yn-1-ol, 3-methyl-1-butanol, (S) - (-) - 2- methyl-1-butanol, DL-2- methyl-1-butanol, 2-methyl-3-butyn-2-ol, 4-methyl-4-heptanol, 2-methyl-2-pentanol, 2-pentanol, (S) - (+) - 2- pentyl alcohol, (R) - (-) - 2- pentanol, 2, 2, 2-trifluoroethanol, 2, 2, 2-trichloroethanol, 2, 2, 2-tribromo 醇、3-三甲基甲硅烷基-2-丙炔-1-醇、1-溴-2-丙醇、 1- 丁烯-3-醇、2- 丁炔-1-醇、1-氯-2-丙醇、环庚醇、环丁醇、1-氯-2-甲基-2-丙醇、 1,3-二溴-2-丙醇、1,3-二氯-2-丙醇、2, 6-二甲基-4-庚醇、2, 2-二甲基-3-己醇、2, 5-二甲基-3-己醇、3, 5-二甲基-3-己醇、2-乙基-1-丁醇、1-庚醇、2-庚醇、3-庚醇、1-己醇、 2- 己醇、羟基丙酮、3-甲氧基-1- 丁醇、2-甲基-3- 丁烯-2-醇、4-甲基-2-戊醇、1-癸醇、 1- 壬醇、1-辛醇、1-十二烷醇、3, 7-二甲基-1-辛醇、1-十四烷醇、Ii^一烷醇、1-十六烷醇、1-十八烷醇、1-十五烷醇、2-辛醇、1-二十二烷醇、1-二十烷醇、环己烷甲醇、环十二烷醇、环己烷乙醇、2, 5-二甲基环己醇、2-甲基环己醇、1-环己基-1- 丁醇、2-乙基环己醇、 4-(2-羟基乙基)环己醇、1-环己基-1-戊醇、9-癸烯-1-醇、油烯基醇、4-环己基环己醇、 2- 环己基环己醇、十氢-2-萘酚、1-癸 Alcohol, 3-trimethylsilyl-2-propyn-1-ol, 1-bromo-2-propanol, 1-butene-3-ol, 2-butyn-1-ol, 1-chloro 2-propanol, cyclohexyl alcohol, cyclobutanol, 1-chloro-2-methyl-2-propanol, 1,3-dibromo-2-propanol, 1,3-dichloro-2-propyl alcohol, 2,6-dimethyl-4-heptanol, 2,2-dimethyl-3-hexanol, 2-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, Ii ^ an alcohol, 1-hexadecanol, 1-octadecanol, 1-pentadecanol, 2-octanol , 1-docosanol, 1-eicosanol, cyclohexane methanol, cyclododecanol, cyclohexane, ethanol, 2-dimethyl-cyclohexanol, 2-methylcyclohexanol , 1-cyclohexyl-1-butanol, 2-ethyl-cyclohexanol, 4- (2-hydroxyethyl) cyclohexanol, 1-cyclohexyl-1-pentanol, 9-decen-1-ol , oleyl alcohol, 4-cyclohexyl-cyclohexanol, 2-cyclohexyl-cyclohexanol, decahydro-2-naphthol, 1-decanol -3-醇、1-壬烯-3-醇、3, 5-二甲基-1-金刚烷甲醇、8-二甲氨基-1-辛醇、4-(羟基甲基)环己烷羧酸、反式-4-(羟基甲基)环己烷羧酸、 4_(三氟甲基)环己烷甲醇、2-茨醇、2-(苄氧基)乙醇等。 3-ol, 1-nonene-3-ol, 3, 5-dimethyl-1-adamantane methanol, 8-dimethylamino-1-octanol, 4- (hydroxymethyl) cyclohexanecarboxylic acid acid, trans-4- (hydroxymethyl) cyclohexanecarboxylic acid, 4_ (trifluoromethyl) cyclohexane methanol, 2-Mainz alcohol, 2- (benzyloxy) ethanol and the like.

[0232] 此外,还可以举出2-甲氧基乙醇、二乙二醇单甲醚、十乙二醇单甲醚、十二乙二醇单甲醚、3-甲氧基-1-丙醇、1- 丁氧基-2-丙醇、五乙二醇单甲醚、三乙二醇单甲醚、四乙二醇单甲醚、1,4- 丁二醇单醚等具有醚键的一元醇化合物。 [0232] In addition, also include 2-methoxyethanol, diethylene glycol monomethyl ether, decaethylene glycol monomethyl ether, dodecyl glycol monomethyl ether, 3-methoxy-1-propanesulfonic alcohol, 1-butoxy-2-propanol, pentaethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, 1,4-butanediol monoethers having an ether bond monohydric alcohol compound.

[0233] 作为二醇化合物,可以举出例如,乙二醇、1,3_丙二醇、1,4_ 丁二醇、2, 3-丁二醇、2, 3_二甲基_2, 3_ 丁二醇、2, 2_二甲基_1,3_丙二醇、2_甲基_1,3_丙二醇、 (S,S)-(+)-2, 3- 丁二醇、频哪醇、2, 2-二甲基-1,3-丙二醇、1,7-庚二醇、1,5-戊二醇、(S)-(+)-1,2-丙二醇、(R)-(-)-1,2-丙二醇、1,5_ 戊二醇、(S)-(+)-1,2-丙二醇、 (R) - (-) -1,2-丙二醇、2-丁炔-1,4-二醇、1,6-己二醇、1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,12-十二烷二醇、1,2_癸二醇、1,2_十四烷二醇、1,4_环己烷二甲醇、新戊二醇、 3, 9-双(1,1-二甲基-2-羟基乙基)-2, 4, 8, 10-四氧杂螺环[5. 5]i^一烷、1,3-双(2-羟基乙氧基)苯、1,4-双(2-羟基乙氧基)-2-丁炔、二甘醇、三丙二醇、2, 2-双(4-羟基环己基)丙烧等° [0233] Examples of the diol compound include ethylene glycol, 1,3_ propylene, 1,4_-butanediol, 2,3-butanediol, 2, 3_ dimethyl _2, 3_ D diol, 2, 2_ dimethyl _1,3_ glycol, 2_ methyl _1,3_ propanediol, (S, S) - (+) - 2, 3- butanediol, pinacol, 2, 2-dimethyl-1,3-propanediol, 1,7-hexanediol, 1,5-pentanediol, (S) - (+) - 1,2- propanediol, (R) - (- ) -1,2-propanediol, 1,5_-pentanediol, (S) - (+) - 1,2- propanediol, (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, tetradecane diol 1,2_, 1,4_-cyclohexane dimethanol, neopentyl glycol, 3, 9-bis (1,1-dimethyl-2-hydroxyethyl) -2, 4, 8, 10-tetraoxa-spiro [5. 5] i ^ a, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy yl) -2-butyne, diethylene glycol, triethylene glycol, 2,2-bis (4-hydroxycyclohexyl) prop-burn like °

[0234] 作为三醇化合物,可以举出1,1,1_三(羟基甲基)乙烷、甘油、1,2,8_辛三醇等。 [0234] As triol compounds include 1,1,1_ tris (hydroxymethyl) ethane, glycerol, 1,2,8_ oct-triol.

[0235] 进一步作为4官能以上的多元醇化合物,可以举出二季戊四醇、双甘油、Span20 等。 [0235] As a further 4 or more functional polyol compounds include dipentaerythritol, diglycerol, Span 20 and the like.

[0236] 酚化合物之中,作为单官能酚化合物,可以举出4-甲氧基苯酚、3-氯苯酚、4-氯苯酚、对甲酚、间甲酚、邻甲酚、3, 5-二氯苯酚、邻甲氧基苯酚、4-溴苯酚、2, 6-二氯苯酚、 4_氟苯酚、4-碘苯酚、3-甲氧基苯酚、3, 5-二甲氧基苯酚、4-苯氧基苯酚、3-溴苯酚、2-溴苯酚、2, 4-二氯苯酚、3, 4-二氯苯酚、2, 6-二甲氧基苯酚、2, 6-二甲基苯酚、3, 5-二甲基苯酚、2-氟苯酚、3-氟苯酚、2-碘苯酚、3-碘苯酚、4-甲氧基-1-萘酚、2, 4, 6-三氯苯酚、4-氨基苯酌·、6-溴_2_萘酌·、4-氯-1-萘酌·、2, 3-二氯苯酌·、2, 5-二氯苯酌·、2, 4-二甲基苯酌·、 3, 4-二甲基苯酚、2, 6-二氟苯酚、3, 5-二氟苯酚、2, 6-二溴苯酚、3, 5-二溴苯酚、2, 4, 6-三甲基苯酚、4-氨基苯酚盐酸盐、4-叔丁基苯酚、4-叔丁氧基苯酚、4-羟基苯甲腈、2, 4-二溴苯酚、2, 3-二甲基苯酚、2, 4-二氟苯酚、3, 4-二氟苯酚、3, 4- [0236] Among the phenolic compounds, as monofunctional phenolic compounds 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-phenoxy-phenol, 3-bromophenol, 2-bromophenol, 2,4-dichlorophenol, 3,4-dichlorophenol, 2,6-dimethoxy phenol, 2,6-dimethyl phenol, 3,5-dimethylphenol, 2-fluorophenol, 3-fluorophenol, 2-iodophenol, 3-iodophenol, 4-methoxy-1-naphthol, 2, 4, 6-trichloro phenol, 4-amino-benzene discretion, _2_ 6-bromo-naphthalene discretion, discretion 4-chloro-1-naphthyl, 2, 3-dichlorobenzene discretion, 2, 5-dichlorobenzene discretion *, 2 , 4-dimethylbenzene discretion ·, 3, 4-methylphenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,6-dibromophenol, 3,5-dibromophenol , 2, 4, 6-trimethyl-methylphenol, 4-amino-phenol hydrochloride, 4-tert-butylphenol, 4-tert-butoxy-phenol, 4-hydroxybenzonitrile, 2,4-dibromo-phenol, 2, 3-methylphenol, 2, 4-difluorophenol, 3,4-difluorophenol, 3, 4 甲氧基苯酚、4-乙基苯酚、 4-乙氧基苯酚、4-羟基苯甲醛、4-羟基苯硫醇、4-异丙基苯酚、4-(甲硫基)苯酚、2, 4, 6-三溴苯酚、2, 4, 6-二碘苯酚、2, 3, 6-二氯苯酚、5-氨基-2-萘酚、6-氨基-1-萘酚、3-氨基苯酚、1_溴_2_萘酚、3-溴-2-萘酚、2, 4-二氯-1-萘酚、1,6-二溴-2-萘酚、2, 5-二氟苯酚、 2, 3-二氟苯酚、4-羟基三氟甲苯、3-羟基苯硫醇、五氯苯酚、4-丙基苯酚、2, 3, 4, 6-四氯苯酚、2, 4, 5-二氯苯酚、2-氨基苯酚、5-氨基-1-萘酚、8-氨基-2-萘酚、4-叔戊基苯酚、3-叔丁基苯酚、4-仲丁基苯酚、3-氰基苯酚、3-乙氧基苯酚、3-乙基苯酚、2-乙氧基苯酚、3-羟基苯甲醛、4-苄基苯酚、6-羟基-2-萘酚腈、6-羟基-2-萘酚醛、3-异丙基苯酚、2, 3, 5-三甲基苯酚、2, 3, 6-三甲基苯酚、4-(三氟甲氧基)苯酚、4-氨基-1-萘酚盐酸盐、2-氨基苯酚盐酸盐、2-叔丁基苯酌·、4-丁基苯酌·、4-α-枯基苯 Methoxyphenol, 4-ethylphenol, 4-ethoxy phenol, 4-hydroxybenzaldehyde, 4-hydroxyphenyl mercaptan, 4-isopropyl-phenol, 4- (methylthio) phenol, 2, 4 , 6-tribromophenol, 2, 4, 6-iodophenol, 2, 3, 6-dichlorophenol, 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-difluoro-phenol, 2, 3-fluorophenol, 4-hydroxy-trifluoromethylphenyl, 3-hydroxyphenyl mercaptan, pentachlorophenol, 4-propylphenol, 2, 3, 4, 6-tetrachlorophenol, 2, 4, 5 dichlorophenol, 2-aminophenol, 5-amino-1-naphthol, 8-amino-2-naphthol, 4-t-pentyl phenol, 3-tert-butylphenol, 4-sec-butylphenol, 3- cyanophenol, 3-ethoxy-phenol, 3-ethylphenol, 2-ethoxy-phenol, 3-hydroxybenzaldehyde, 4-benzyl-phenol, 6-hydroxy-2-naphthol-carbonitrile, 6-hydroxy - 2-naphthyl phenol, 3-isopropyl phenol, 2, 3, 5-methylphenol, 2, 3, 6-trimethylphenol, 4- (trifluoromethoxy) phenol, 4-amino - naphthol hydrochloride, 2-aminophenol hydrochloride, 2-tert-butylbenzene discretion ·, 4-butyl benzene discretion ·, 4-α- cumyl phenyl 酌·、2-氰基苯酌·、2, 4-二溴-1-萘酌·、3-(二甲氨基)苯酚、2-乙基苯酚、4' -羟基苯乙酮、4-己基苯酚、2-羟基三氟甲苯、2-羟基苯硫醇、2-异丙基苯酚、2-(甲硫基)苯酚、4-戊基苯酚水杨醛、3-羟基三氟甲苯、2, 3, 5, 6-四氟苯酚、2, 3, 4-三氟苯酚、2-氯苯酚等。 Discretion ·, 2-cyanophenyl discretion ·, 2, 4-dibromo-1-naphthyl discretion ·, 3- (dimethylamino) phenol, 2-ethylphenol, 4 '- hydroxyacetophenone, 4-hexyl phenol, 2-hydroxy-trifluoromethylphenyl, 2-hydroxyphenyl-thiol, 2-isopropyl-phenol, 2- (methylthio) phenol, 4-pentyl-phenol salicylaldehyde, 3-hydroxy-trifluoromethylphenyl, 2, 3, 5, 6-tetrafluoro phenol, 2, 3, 4-trifluoromethyl phenol, 2-chlorophenol and the like.

[0237] 作为具有2个羟基的酚化合物,可以举出4, 4' -二羟基二苯基醚、5-甲氧基间苯二酚、2-甲基间苯二酚、5-甲基间苯二酚一水合物、5-甲基间苯二酚(无水)、氯对苯二酚、 4_氯邻苯二酚、2, 2'-二轻基二苯基醚、1,3-双(4-轻基苯氧基)苯、5-溴间苯二酚、4-氯间苯二酚、3-氯邻苯二酚、4, 6-二氯间苯二酚、2-碘间苯二酚、甲基对苯二酚、4-甲基邻苯二酚、3-甲氧基邻苯二酚、甲氧基对苯二酚、4-溴间苯二酚、1,4-双(3-羟基苯氧基)苯、溴对苯二酚、4-溴邻苯二酚、2, 6-二甲基对苯二酚、2, 5-二甲基间苯二酚、2, 3-二甲基对苯二酚、4-氟邻苯二酚、4-氟间苯二酚、3-甲基邻苯二酚、四氯对苯二酚、4, 4'-二羟基二苯基甲烧、3-溴邻苯二酚、甲酚(异构体混合物)、双(4-轻基苯基)硫醚、2, 6-二溴-1,5-二轻基萘、3-氟邻苯二酚、2, 4, 6-三溴间苯二酚、2, 2-双(4-羟基 [0237] Examples of the phenol compound having two hydroxyl groups include 4, 4 '- dihydroxydiphenyl ether, 5-methoxy-resorcinol, 2-methyl resorcinol, 5-methyl resorcinol monohydrate, 5-methyl resorcinol (anhydrous), chloro-hydroquinone, 4_ chloro catechol, 2, 2'-light diphenyl ether, 1, 3-bis (4-light) benzene, 5-bromo-resorcinol, 4-chlororesorcinol, 3-chloro-catechol, 4, 6-dichloro-resorcinol, 2 - iodo resorcinol, methylhydroquinone, 4-methyl catechol, 3-methoxy catechol, methoxy hydroquinone, 4-bromo-resorcinol, 1 , 4-bis (3-hydroxyphenoxy) benzene, bromo-hydroquinone, 4-bromo-catechol, 2,6-dimethyl hydroquinone, 2, 5-dimethyl terephthaloyl phenol, 2,3-dimethyl hydroquinone, 4-fluoro-catechol, 4-fluoro-resorcinol, 3-methyl catechol, tetrachloro-hydroquinone, 4, 4 ' - dihydroxydiphenyl A burning, 3-bromo-catechol, cresol (isomer mixture), bis (4-light-yl) sulfide, 2,6-dibromo-1,5- light-naphthalene, 3-fluoro-catechol, 2, 4, 6-tribromo resorcinol, 2,2-bis (4-hydroxy 苯基)丙烷、4, 4'-亚乙基双酚、 三甲基对苯二酚、1,2-二羟基萘等2官能酚化合物、4-羟基苯甲醇等单官能酚化合物等。 Phenyl) propane, 4,4'-ethylidene bisphenol, trimethyl bifunctional phenol, hydroquinone, 1,2-dihydroxynaphthalene compounds such as 4-hydroxybenzyl alcohol monofunctional phenolic compounds.

[0238] 作为3官能酚化合物,可以举出1,2, 4-三羟基苯、1,8, 9-三羟基蒽、5-甲基连苯三酚、4, 4',4"-三羟基三苯甲烷等。 [0238] As trifunctional phenol compound include 1,2,4-trihydroxybenzene, 1,8, 9-trihydroxyanthracene, 5-methyl pyrogallol, 4, 4 ', 4 "- tris hydroxy triphenyl methane.

[0239] 作为4官能酚化合物,可以举出1,4, 9, 10-蒽四醇等,作为6官能酚化合物,可以举出六羟基苯、2, 3, 6, 7, 10, 11-六羟基苯并[9, 10]菲水合物等。 [0239] As tetrafunctional phenol compounds include 1,4, 9, 10-anthracene tetracarboxylic alcohol and the like, as a 6-functional phenolic compounds include six-hydroxyphenyl, 2, 3, 6, 7, 10, 11- six hydroxybenzo [9, 10] phenanthrene hydrate.

[0240] 作为羧酸化合物,可以举出甲氧基乙酸、乙醛酸、庚烷酸、癸烷酸、壬烷酸、月桂酸、 十四酸、4-甲基-正辛酸、庚二酸、十七烷酸、16-羟基十六烷酸、15-羟基十五烷酸、棕榈酸、 十五烷酸、硬脂酸、山嵛酸、二十烷酸、二十一烷酸、12-羟基硬脂酸、2-己基癸烷酸等单羧酸、壬二酸、辛二酸、癸二酸、(+)_樟脑酸、十二烷二酸等二羧酸、1,3, 5-戊烷三羧酸等3官能以上的多元羧酸等。 [0240] As the carboxylic acid compounds include methoxy acetic acid, glyoxylic acid, heptane acid, decane acid, azelaic acid, lauric acid, myristic acid, 4-methyl - octanoic acid, pimelic , heptadecanoic acid, 16-hydroxy hexadecanoic acid, 15-hydroxy pentadecanoic acid, palmitic acid, pentadecanoic acid, stearic acid, behenic acid, eicosanoic acid, heneicosanoic acid, 12 - monocarboxylic hydroxy acid, 2-hexyl decanoic acid and the like, azelaic acid, suberic acid, sebacic acid, (+) _ camphoric acid, dodecanedioic acid acid, 1,3, 5- pentane-tricarboxylic acid 3-functional or more polycarboxylic acids and the like.

[0241] 具有羟基的化合物可以单独使用1种,也可以组合使用2种以上。 [0241] compound having a hydroxyl group may be used alone, may be used in combination of two or more thereof. 这些之中,优选使用选自醇化合物(优选二醇化合物)和酚化合物组成的组中的至少一种。 At least one of the group Among these, preferably selected from an alcohol compound (preferably a diol compound) and a phenol compound consisting of.

[0242]对处理在分子内具有至少1个伯氨基的化合物的异氰酸酯化合物的用量不特别限制,可根据目的等来适宜选择。 [0242] The amount of treating compound having at least one primary amino group in the molecule of the isocyanate compound is not particularly limited, depending on the purpose or the like is appropriately selected. 以在分子内具有至少1个伯氨基的化合物的氨基数为1摩尔时,异氰酸酯化合物的用量优选为异氰酸酯化合物的异氰酸酯基数达到〇. 01摩尔〜10 摩尔的量、更优选为异氰酸酯化合物的异氰酸酯基数达到0. 02摩尔〜5摩尔的量、进一步优选为异氰酸酯化合物的异氰酸酯基数达到〇. 05摩尔〜2摩尔的量。 When the number of amino compound having at least one primary amino group in the molecule is 1 mol, the amount of the isocyanate compound is preferably isocyanate groups of isocyanate compound into the square. Molar amount of ~ 10 mole 01, and more preferably isocyanate groups of isocyanate compound reaches 0.02 mol ~ 5 molar amount, more preferably isocyanate groups of isocyanate compound into the square amount of 05 mol ~ 2 mol.

[0243]对处理在分子内具有至少1个伯氨基的化合物的具有羟基的化合物的用量不特别限制,可根据目的等来适宜选择。 [0243] The amount of the compound having a hydroxy group by treating the compound having at least one primary amino group in the molecule is not particularly limited, depending on the purpose or the like is appropriately selected. 以在分子内具有至少1个伯氨基的化合物的氨基数为1摩尔时,具有羟基的化合物的用量优选为羟基数达到〇.OOl摩尔〜10摩尔的量、进一步优选为羟基数达到0. 005摩尔〜1摩尔的量、更优选为羟基数达到0. 01摩尔〜0. 5摩尔的量。 When the number of amino compound having at least one primary amino group in the molecule is 1 mol, with the amount of hydroxyaromatic compounds is preferably up to an amount of mol ~ 10 mol 〇.OOl is the number of hydroxyl groups, more preferably hydroxyl number reached 0.005 mol ~ 1 molar amount, more preferably a hydroxyl number reaches an amount of 0.01 mol ~ 0. 5 mol.

[0244] 优选在分子内具有至少1个伯氨基的化合物的基于异氰酸酯化合物和具有羟基的化合物的处理在有机溶剂中或不加溶剂(无溶剂)下一边控制温度一边进行,温度优选为-HTC〜120°C、更优选为-5°C〜100°C、进一步优选为KTC〜90°C、特别优选为20°C〜 80°C。 [0244] preferably having at least one compound having a primary amino group in the molecule by treating the compound of the isocyanate compound having a hydroxyl group on the side to control the temperature while in an organic solvent or without a solvent (solvent-free), the temperature is preferably -HTC ~120 ° C, more preferably -5 ° C~100 ° C, more preferably KTC~90 ° C, particularly preferably 20 ° C~ 80 ° C. 处理时间可为例如0. 1〜100小时、优选为0. 5〜50小时。 Treatment time may be, for example, 0.5 1~100 hours, preferably 0. 5~50 hours.

[0245][树脂组合物] [0245] [Resin Composition]

[0246] 本发明的树脂组合物包含固化剂(A)、以及环氧树脂和/或分子内具有至少1个不饱和键的树脂(B),所述固化剂(A)包含通过上述异氰酸酯化合物与肼或与分子内具有2个以上伯氨基的多元胺化合物的反应而得到的在分子内具有至少1个伯氨基的化合物。 [0246] The resin composition of the present invention contains a curing agent (A), and epoxy resins, and the / or molecules having at least one unsaturated bond in the resin (B), the curing agent (A) comprises the above-described isocyanate compound at least one compound having a primary amino group in the reaction of the polyamine compound of hydrazine or having two or more primary amino groups within the molecule and is obtained in a molecule. 固化剂(A)优选包含由选自上述式(I)、(la)、(lb)、(IIa)和(IIb)组成的组中的至少一种所表示的化合物,还优选包含对这些化合物用异氰酸酯化合物、用异氰酸酯化合物和环氧树脂、 或者用异氰酸酯化合物和具有羟基的化合物进行处理而成的化合物。 A curing agent (A) preferably comprises selected from the above formulas (I), (la), (lb), (IIa) and (lib) at least one compound represented by the group consisting of, preferably further comprises those compounds an isocyanate compound, an isocyanate compound and an epoxy resin or isocyanate compound and a compound having a hydroxyl group, compound treatment is formed.

[0247]〔环氧树脂〕 [0247] [epoxy]

[0248] 作为环氧树脂,可以使用公知的环氧树脂,可以举出例如双酚A型环氧树脂、双酚F型环氧树脂、双酚AD型环氧树脂、线型酚醛型环氧树脂、甲酚-线型酚醛型环氧树脂、环状脂肪族环氧树脂、缩水甘油酯系树脂、缩水甘油胺系环氧树脂、杂环式环氧树脂、氨基甲酸酯改性环氧树脂等。 [0248] As the epoxy resin, may be used known epoxy resin may include bisphenol A type epoxy resins, bisphenol F epoxy resin, bisphenol AD ​​type epoxy resins, phenol novolac type epoxy resin, a cresol - novolak type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester resins, glycidyl amine epoxy resins, heterocyclic epoxy resins, urethane modified epoxy resin. 这些之中,优选使用双酚A型环氧树脂、甲酚-线型酚醛型环氧树脂等。 Among these, bisphenol A type epoxy resin, a cresol - novolak type epoxy resin and the like. 也可以使用将具有缩水甘油基的树脂用(甲基)丙烯酸进行改性后的环氧(甲基)丙烯酸。 You may be used having a glycidyl group resin is an epoxy (meth) after modification with acrylic acid (meth) acrylic acid. 优选使用使例如日本特开2012-77202号公报中记载的环氧树脂与(甲基)丙烯酸反应而得到的偏酯化环氧树脂。 Preferable to use, for example, an epoxy Japanese Laid-Open Patent Publication No. 2012-77202 described in the partial esterification of the epoxy resin (meth) acrylate obtained by reacting. 具体地说,优选使用相对于环氧树脂的环氧基1当量使(甲基)丙烯酸以优选为10〜90当量%、更优选为20〜80当量%、进一步优选为30〜70当量%、特别优选为40〜60当量%对其反应而得到的偏酯化环氧树脂。 Specifically, preferably used with respect to the epoxy resin equivalent of epoxy group of (meth) acrylic acid is preferably 10 ~ 90 equivalent%, more preferably 20 to 80 equivalent%, more preferably 30~70 equivalent%, particularly preferred for the partial esterification of the epoxy resin 40~60 equivalent% thereof obtained by reacting. 环氧树脂可以单独使用一种,也可以合用两种以上。 Epoxy resins may be used alone or in combination of two or more. 此外,也可以为含有不饱和键的环氧树脂。 Further, also contain an epoxy resin an unsaturated bond.

[0249] 偏酯化环氧树脂可通过下述方法得到:例如,首先,基于常规方法在碱性催化剂的存在下,将双酚A型环氧树脂与丙烯酸或甲基丙烯酸在相对于环氧基2当量的羧酸基为0. 9〜I. 1当量的条件进行反应,向该反应生成物中加入以质量比计约为4倍的甲苯和同量的纯水,在60〜80°C下搅拌1小时后,静置分离为有机层和水层,除去水层;重复该操作3〜5次,最后回收有机层并将残存的甲苯通过真空蒸馏而除去,从而对进行了水溶离子性物质的降低化处理后的偏酯化环氧树脂进行精制。 [0249] Partial esterification of the epoxy resin may be obtained by the following method: For example, first of all, based on a conventional method in the presence of a basic catalyst, a bisphenol A type epoxy resin with acrylic acid or methacrylic acid to the epoxy group 2 equivalents of carboxylic acid groups 0. 9~I. 1 equivalent of the conditions of the reaction, to the reaction product were added pure toluene and the same amount of mass ratio of about 4-fold, at 60~80 ° after stirring at C 1 hour standing separated into an organic layer and an aqueous layer, aqueous layer was removed; this operation was repeated three to five times, and the organic layer was finally recovered and the remaining toluene was removed by vacuum distillation, thereby performs a water-soluble ionic substance reduction of partial esterification of the epoxy resin after the treatment for purification. 作为上述的双酚A型环氧树脂的具体例,可以举出例如Epikote828、834、1001、1004(三菱化学社制造)、EPICL0N850、860、 4055 (DIC社制造)等。 Specific examples of the bisphenol A type epoxy resin includes, for example Epikote828,834,1001,1004 (manufactured by Mitsubishi Chemical), EPICL0N850,860, 4055 (DIC Corp.) and the like. 作为这些原料树脂,优选的是,进行了水溶离子性物质的降低化处理(以下称为高纯度化处理)的树脂、例如EPICLON850S(DIC社制造)等是适合的。 As the raw material resin, preferably it is carried out reducing processing water-soluble ionic substance (hereinafter referred to as high purity process) resins, e.g. EPICLON850S (DIC Corp.) and the like are suitable.

[0250]〔分子内具有至少1个不饱和键的树脂〕 [0250] [having in the molecule at least one unsaturated bond resin]

[0251] 树脂组合物可以包含分子内具有至少1个不饱和键的树脂。 [0251] The resin composition may comprise a molecule having at least one unsaturated bond resin. 作为分子内具有至少1个不饱和键的树脂,可以举出例如,苯乙烯衍生物、乙烯衍生物、马来酰亚胺衍生物、(甲基)丙烯酸衍生物等。 As the resin having at least one unsaturated bond in a molecule includes, for example, styrene derivatives, vinyl derivatives, maleimides derivatives, (meth) acrylic acid derivatives. 其中,优选使用分子内具有至少1个(甲基)丙烯酰基的(甲基) 丙烯酸衍生物。 Wherein the molecule is preferably used at least one (meth) acrylic acid derivatives, (meth) acryloyl group.

[0252]作为(甲基)丙烯酸衍生物,具体地说,可以举出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸叔丁酯等(甲基) 丙烯酸烷基酯;(甲基)丙烯酸苯酯等(甲基)丙烯酸芳基酯;(甲基)丙烯酸苄酯等(甲基)丙烯酸芳烷基酯;(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯、(甲基)丙烯酸丙氧基乙酯、(甲基)丙烯酸丁氧基乙酯等(甲基)丙烯酸烷氧基烷基酯;(甲基)丙烯酸-2-羟基乙酯、(甲基)丙烯酸-3-羟基丙酯、(甲基)丙烯酸-2-羟基丙酯、(甲基) 丙烯酸-4-羟基丁酯等含有羟基的(甲基)丙烯酸酯;(甲基)丙烯酸环己酯之类的脂环式醇的(甲基)丙烯酸酯等。 [0252] As the (meth) acrylic acid derivatives, specifically, include (meth) acrylate, ethyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate butyl (meth) acrylate, t-butyl (meth) acrylate; (meth) acrylate, phenyl (meth) acrylate aryl ester; (meth) acrylate, benzyl (meth) acrylic acid aralkyl esters; (meth) acrylate, ethoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, propoxy ethyl (meth) acrylate, butoxyethyl acrylate, etc. (meth) acrylic acid alkoxyalkyl ester; (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth yl) acrylate, 4-hydroxybutyl acrylate and other hydroxyl group-containing (meth) acrylate; (meth) (meth) acrylate, alicyclic acrylate, cyclohexyl acrylate such cyclic alcohols. 在此,(甲基)丙烯酸是指丙烯酸和甲基丙烯酸这两方。 Here, (meth) acrylic acid means acrylic acid and methacrylic acid both parties.

[0253]在将环氧树脂与分子内具有至少1个不饱和键的树脂合用时,环氧树脂与分子内具有至少1个不饱和键的树脂的混合量可根据固化树脂组合物而成的固化体的目的来适当确定。 [0253] When an epoxy resin having at least one unsaturated bond in the molecule in combination with a resin, epoxy resin molecule having at least a mixing amount of the unsaturated bonds of the resin composition may be obtained by curing the resin according to object member cured appropriately determined. 分子内具有至少1个不饱和键的树脂为分子内具有至少1个(甲基)丙烯酰基的(甲基)丙烯酸衍生物的情况下,优选混配成相对于环氧基1当量使(甲基)丙烯酰基达到0. 1〜9. 0当量,更优选混配成(甲基)丙烯酰基达到0. 3〜4. 0当量。 The case having at least one unsaturated bond in the resin molecule is a molecule having at least one (meth) acryloyl group of (meth) acrylic acid derivative, preferably mixed with respect to equivalent of epoxy group of (A yl) acryloyl reaches 0. 1~9. 0 equivalents, more preferably mixed into the (meth) acryloyl group reached 0. 3 ~ 4. 0 equiv.

[0254]树脂组合物除了上述树脂以外,可以根据需要含有有机硅树脂、脲树脂、酰亚胺树月旨、玻璃等。 [0254] The resin composition in addition to the resin, may contain a silicone resin, a urea resin, an imide tree month purpose, glass, etc. as needed.

[0255]此外,树脂组合物中可以根据需要混配例如抗氧化剂、紫外线吸收剂、光稳定剂、 硅烷偶联剂、涂面改良剂、热阻聚剂、流平剂、表面活性剂、着色剂、保存稳定剂、增塑剂、润滑剂、填料、无机颗粒、抗老化剂、润湿性改良剂、抗静电剂等作为各种添加剂。 [0255] Further, the resin composition may be required compounding such as antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, coating surface improver, thermal polymerization inhibitors, leveling agents, surfactants, coloring agents, storage stabilizers, plasticizers, lubricants, fillers, inorganic particles, anti-aging agents, wettability improvers, and antistatic agents as various additives.

[0256]作为上述固化剂(A)与环氧树脂和/或分子内具有至少1个不饱和键的树脂(B) 的混合量,相对于环氧树脂1当量,固化剂(A)的氨基脲基或伯氨基的总量优选为0. 001〜 10当量、更优选为〇. 01〜8当量、进一步优选为0. 05〜5当量、特别优选为0. 1〜3当量。 [0256] having a mixing amount of at least one unsaturated bond in the resin (B) with the epoxy resin and / or a molecule as the curing agent (A), the epoxy resin to 1 equivalent amino curing agent (A), the total amount of primary amino group or ureido group is preferably 0.5 001~ 10 equivalents, more preferably square. 01~8 equivalents, more preferably 0. 05~5 equivalents, particularly preferably 0.5 ~ 3 equivalents. 相对于环氧树脂的环氧基1当量,固化剂(A)的氨基脲基或伯氨基的总量为0. 1〜3当量时,在液晶显示面板等的密封剂中含有树脂组合物的情况下,可适应于对密封剂所要求的细线化、针对多样被粘接体的粘接性的多样化等,还可显现出能够抑制在切出单元时和安装液晶盒驱动用IC时等的剥落的粘接强度。 Relative to 1 equivalent of the curing agent (A) semicarbazide groups amount of epoxy resin epoxy group or a primary amino group is 0.5 ~ 3 eq, the resin composition comprising the liquid crystal display panel or the like sealant case, can be adapted to the sealing agent is required thinning, for various diversified like adhesive of the adhesive body may exhibit can be suppressed during cut-out unit and mounting the liquid crystal cell driving IC like peeling adhesive strength.

[0257]作为上述固化剂(A)与环氧树脂和/或分子内具有至少1个不饱和键的树脂(B) 的混合量,在单独含有环氧树脂(B)、或者含有环氧树脂和分子内具有至少1个不饱和键的树脂(B)这两方的情况下,相对于环氧树脂的环氧基1当量,固化剂(A)的氨基脲基或伯氨基的总量优选为〇. 0005〜10当量、更优选为0. 005〜8当量、进一步优选为0. 025〜5当量、特别优选为〇. 05〜3当量。 [0257] having a mixing amount of at least one unsaturated bond in the resin (B) with the epoxy resin and / or a molecule as the curing agent (A), in a separate comprising an epoxy resin (B), or contains an epoxy resin amount and the molecule having at least one unsaturated bond in the resin (B) in the case both of with respect to the epoxy equivalent of epoxy group, semicarbazide group or primary curing agent (a) is an amino group is preferably It is a square. 0005~10 equivalents, more preferably 0. 005~8 equivalents, more preferably 0.5 025~5 equivalents, particularly preferably square. 05~3 equivalents.

[0258]此外,在单独含有分子内具有至少1个不饱和键的树脂(B)的情况下,相对于树脂(B)的不饱和键1当量,固化剂㈧的氨基脲基或伯氨基的总量优选为0. 0005〜10当量、 更优选为〇. 005〜8当量、进一步优选为0. 025〜5当量、特别优选为0. 05〜3当量。 [0258] Further, the case having at least one unsaturated bond in the resin (B) in the containing single molecule, relative to the resin (B) is an unsaturated bond 1 equivalent of curing agent (viii) semicarbazide group or a primary amino group preferably 0. 0005~10 total equivalents, more preferably square. 005~8 equivalents, more preferably 0.5 025~5 equivalents, particularly preferably 0.5 equivalents 05~3. 固化剂(A)的相对于树脂(B)的混合量在上述范围内时,在液晶显示面板等的密封剂中含有树脂组合物的情况下,可适应于对密封剂所要求的细线化、针对多样被粘接体的粘接性的多样化,还能够显现出可抑制在切出单元时和安装液晶盒驱动用IC时等的剥落的粘接强度。 Case with the curing agent (A) is within the above range, the resin composition containing the panel of the sealant the mixing amount of the resin (B) in the liquid crystal display, can be adapted to the sealant required thinning for diversification adhesiveness various adherends but also can exhibit adhesion strength of peeling when suppressed during cut-out unit and mounting the liquid crystal cell driving IC.

[0259][液晶密封剂组合物] [0259] [liquid crystal sealant composition]

[0260]本发明涉及含有上述树脂组合物的液晶密封剂组合物。 [0260] The present invention relates to a liquid crystal sealant composition containing the resin composition. 液晶密封剂组合物优选含有树脂组合物、光聚合引发剂(C)和其他根据需要使用的无机填充剂(D),所述树脂组合物含有上述固化剂(A)以及环氧树脂和/或分子内具有至少1个不饱和键的树脂(B)。 The liquid crystal sealant composition preferably contains a resin composition, the photopolymerization initiator (C) and according to other inorganic filler (D) needs to be used, the resin composition containing the curing agent (A) and an epoxy resin and / or molecule having at least one unsaturated bond in the resin (B).

[0261]〔光聚合引发剂(〇〕 [0261] [photopolymerization initiator (square]

[0262] 作为光聚合引发剂,可以举出二苯甲酮、2, 2-二乙氧基苯乙酮、苯偶酰、苯甲酰基异丙醚、安息香双甲醚、1-羟基环己基苯基甲酮、噻吨酮等。 [0262] As the photopolymerization initiator include benzophenone, 2,2-diethoxyacetophenone, benzil, benzoyl isopropyl ether, benzoin double ether, 1-hydroxycyclohexyl phenyl ketone, thioxanthone. 此外,作为光聚合引发剂, 可以使用市售的光自由基聚合引发剂。 Further, as the photopolymerization initiator, commercially available photoradical polymerization initiator. 作为市售的光自由基聚合引发剂,可以举出例如Irgacure907、Irgacure819、Irgacure651、Irgacure369、苯偶姻甲醚、苯偶姻乙醚、苯偶姻异丙醚、LucirinTPO(以上均为BASFJapan社制造)等。 Examples of commercially available photoradical polymerization initiators include Irgacure907, Irgacure819, Irgacure651, Irgacure369, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, LucirinTPO (all of which are manufactured BASFJapan) Wait.

[0263]〔无机填充剂(D)〕 [0263] [Inorganic filler (D)]

[0264] 作为无机填充剂,对其没有特别限定,可以举出例如球状二氧化硅、球状氧化铝、 球状二氧化钛、球状氧化铝、球状碳酸钙等。 [0264] Examples of the inorganic filler is not particularly limited, and examples thereof include spherical silica, spherical alumina, spherical titania, spherical alumina, spherical calcium carbonate. 其中,从分散性优异、提高适于液晶滴注工艺的密封剂的粘接性、固化物的耐湿性的效果上也优异的方面出发,优选球状二氧化硅。 Wherein the dispersibility is excellent to improve the adhesion of the encapsulant is adapted to the liquid crystal dropping process, the effect of the cured product moisture resistance is also excellent in the viewpoint of, preferably spherical silica.

[0265] 作为液晶密封剂组合物的各成分的混合比例,相对于树脂组合物100质量份,(C) 光聚合引发剂为〇. 5〜5质量份、优选为0. 5〜4质量份、更优选为0. 8〜3质量份,(D)无机填充剂为〇〜40质量份、优选为2〜30质量份、更优选为3〜20质量份。 [0265] As the mixing ratio of each component of the liquid crystal sealant composition with respect to 100 parts by mass of the resin composition, (C) a photopolymerization initiator is square. 5~5 parts by mass, preferably 0. 5~4 parts by mass , more preferably 0.5 8~3 parts by mass, (D) an inorganic filler parts 〇~40 mass, preferably 2~30 parts by mass, more preferably in an amount 3~20 mass. 另外,液晶密封剂组合物的总质量中,优选(C)光聚合引发剂为0. 5〜3质量%、(D)无机填充剂为0〜 40质量%。 Further, the total mass of the liquid crystal sealant composition, preferably (C) a photopolymerization initiator 0. 5~3% by mass, (D) the inorganic filler is 0~ 40% by mass.

[0266] 对于液晶密封剂组合物,特别要注意无机填充剂等固体物质的均匀、完全的分散, 优选使用涂料辊等进行充分混炼来制造。 [0266] For the liquid crystal sealant composition, with particular attention to uniform inorganic filler and other solid matter, complete dispersion, preferably using a paint roller or the like sufficiently kneaded to manufacture.

[0267]〔液晶显示面板〕 [0267] [liquid crystal display panel]

[0268] 本发明的液晶密封剂组合物在满足细线化和粘接性的多样化的要求的同时,能够显现出可抑制在切出单元时和安装液晶盒驱动用IC时等的剥落的粘接强度,能够适合用于液晶显示面板的制造中。 [0268] The liquid crystal sealant composition of the present invention meet thinning and diverse requirements of adhesion, and can exhibit suppressed during cut-out unit and install the liquid crystal cell driving IC and the like flaking adhesive strength, can be suitably used for liquid-crystal display panel.

[0269] 即,本发明的液晶显示面板具备:相向的玻璃基板、将相向的玻璃基板粘接的液晶密封剂组合物的固化物、以及由相向的玻璃基板和液晶密封剂组合物的固化物所封装的液晶。 [0269] That is, the liquid crystal of the present invention is a display panel comprising: a glass substrate facing the opposing glass substrate bonded cured product of the liquid crystal sealant composition, and a cured product of opposing glass substrates and a liquid crystal sealant composition the encapsulated liquid crystal.

[0270]〔液晶显示面板的制造方法〕 [0270] [liquid crystal panel manufacturing method of the display]

[0271] 液晶显示面板可通过使用本发明的液晶密封剂组合物在进行光固化后进行热固化来制造。 [0271] The liquid crystal display panel may be thermally cured photocurable manufactured performed by using the present invention, the liquid crystal sealant composition. 图1示出制造液晶显示面板的一实施方式。 Figure 1 shows a manufactured liquid crystal display to an embodiment the panel. 具体地说,如图1(a)的截面图所示,使用玻璃基板1,如图1(b)的截面图所示,在一块玻璃基板1上涂布本发明的液晶密封剂组合物2。 Specifically, FIG. 1 (a) is shown in a sectional view, a glass substrate 1, FIG. 1 (b) is a sectional view, the present invention is coated on a glass substrate 1 of the liquid crystal sealant composition 2 . 接下来,如图1(c)的截面图所示,在一块玻璃基板1上的液晶密封剂组合物2 上相向载置另一块玻璃基板4,在加压下以1,000〜3,OOOmJ的量照射紫外线等光线以使液晶密封剂组合物2固化,从而使一对玻璃基板1、4贴合,进一步在其后在无加压的状态下以100〜120°C的温度加热约1小时,使其充分固化,形成由一对玻璃基板1、4和固化的液晶密封剂2包围的液晶封入用单元5。 Next, FIG. 1 (c) is shown a cross-sectional view of the liquid crystal sealant composition on a glass substrate 1 facing mounting the other glass substrate 24, under pressure to 1,000~3, OOOmJ the irradiation amount of ultraviolet rays to the liquid crystal sealant composition 2 cured, so that a pair of glass substrates 1,4 bonded, further followed by heating from about 1 at a temperature of 100~120 ° C in a non-pressurized state hours to fully cured to form a liquid crystal sealed unit 5 is composed of a pair of glass substrates 1,4, and curing the liquid crystal sealant surrounded 2. 该单元5中,如接下来的图1(d)的俯视图所示,在真空中从液晶注入孔3注入液晶6后,将液晶注入孔3封孔,从而能够制造液晶显示面板7。 The unit 5, as the next in FIG. 1 (d) shown in plan view in vacuo from the liquid crystal injection hole 3 injection liquid after 6, the liquid crystal injection hole 3 plugged, thereby manufacturing a liquid crystal display panel 7. 液晶密封组合物可以点胶涂布于贴有经抛光处理的取向膜的ITO玻璃基板上,其后,将液晶滴注于基板上,通过液晶滴注工艺(0DF工艺)使上下基板贴合,照射紫外线以使其固化(例如,照度和照射时间:l〇〇〇mJ的情况下以100mW/cm2/365nm照射1秒、50mJ的情况下以50mW/cm2/365nm照射1秒),其后例如在120°C的热风烘箱中固化1小时。 The liquid crystal sealing composition may be dispensed coated onto affixed alignment film polished treated ITO glass substrate, and thereafter, the liquid crystals are dropped on the substrate by the liquid crystal dropping process (0DF process) the upper and lower substrates are bonded, irradiated with ultraviolet rays to be cured (e.g., illuminance and radiation time: case l〇〇〇mJ at 100mW / cm2 / 365nm irradiated for 1 second to 50mW / cm2 / 365nm illumination case 50mJ 1 second), followed by e.g. curing in a hot air oven to 120 ° C for 1 hour.

[0272] 实施例 [0272] Example

[0273] 以下通过实施例具体说明本发明,但本发明并非被限定于这些实施例。 [0273] The following detailed description of the present invention through examples, but the present invention is not limited to these embodiments.

[0274]〔固化剂的合成〕 [0274] [curing agent synthesis]

[0275](实施例1) [0275] (Example 1)

[0276] (BI)4, 4'-(亚甲基二-1,4-环己基)双(氨基脲) [0276] (BI) 4, 4 '- (methylenebis-1,4-cyclohexylene) bis (semicarbazide)

[0277]【化31】 [0277] [Chemical Formula 31]

[0278] [0278]

Figure CN104428339AD00311

[0279] 准备在乙醇75g中溶解有二环己基甲烷-4, 4'-二异氰酸酯13. 05g而成的溶解液A、以及在乙醇75g中溶解有肼5g而成的溶解液B。 [0279] prepared by dissolving dicyclohexylmethane in ethanol 75g in-4,4'-diisocyanate, 13. 05g obtained by dissolving solution A, and dissolved in ethanol 75g has dissolved solution of hydrazine 5g formed B. 将溶解液B加入烧瓶中,控制在25°C 进行搅拌,同时以I. 4g/分钟的速度滴加溶解液A。 The dissolved solution B was added to the flask, the control proceeds stirred at 25 ° C, at a rate of I. 4g / min was added dropwise lysate A. 溶解液A的滴加结束后,利用傅利叶变换红外分光光度计测定反应液,确认到来自异氰酸酯基的2250CHT1附近的峰消失后终止反应。 After dissolving solution A is added dropwise, using a Fourier transform infrared spectrophotometer reaction solution was confirmed to peak 2250CHT1 from the vicinity of the isocyanate groups of the reaction was terminated after the disappearance. 按照相对于二环己基甲烷-4, 4'-二异氰酸酯1摩尔、肼为2摩尔(以摩尔比计为1:2) 的方式发生了反应。 According respect dicyclohexylmethane-4,4'-diisocyanate 1 mole, 2 moles of hydrazine (in a molar ratio 1: 2) were reacted manner.

[0280] 反应终止后,使用滤纸(桐山社制造No. 4)利用桐山漏斗(桐山社制造)进行过滤,进行脱液,用蒸馏水50ml来清洗所得到的滤取物,进一步进行过滤,在真空烘箱中以50°C干燥所得到的滤取物。 [0280] After completion of the reaction, using a filter paper (manufactured by Kiriyama No. 4) using a separatory funnel (manufactured by Kiriyama) was filtered for liquid removal, 50ml with distilled water to wash the obtained filtrate was further filtered in vacuo oven at 50 ° C filtered off and drying the resulting extract.

[0281] 干燥后,利用高压粉碎机(商品名:nanojetmizer、AishinNano TechnologiesCO.,LTD制造)进行粉碎,制造平均粒径(中值径)为2. 0μm的均二氨基脲化合物。 [0281] After drying, a high-pressure pulverizer (trade name:. Nanojetmizer, AishinNano TechnologiesCO, LTD, Ltd.) was pulverized, producing an average particle diameter (median diameter) 2. 0μm average diamino urea compound.

[0282] 需要说明的是,平均粒径(中值径)为利用粒度分布计(LA-950V2:堀场制作所制造)进行测定。 [0282] Incidentally, the average particle diameter (median diameter) using a particle size distribution: is measured (LA-950V2 by Horiba Ltd.).

[0283](实施例2) [0283] (Example 2)

[0284] (B-2) 4, 4 '-六亚甲基双(氨基脲) [0284] (B-2) 4, 4 '- hexamethylene bis (semicarbazide)

[0285]【化32】 [0285] [Chemical Formula 32]

[0286] [0286]

Figure CN104428339AD00312

[0287] 准备在乙醇150g中溶解六亚甲基二异氰酸酯16. 8g而成的溶解液A、以及在乙醇150g中溶解有肼IOg而成的溶解液B。 [0287] Preparation was dissolved hexamethylene diisocyanate 16. 8g made in ethanol 150g dissolved solution A, and the dissolving liquid dissolved in ethanol 150g of hydrazine IOg formed B. 将溶解液B控制在25°C进行搅拌,同时以I. 4g/分钟的速度滴加溶解液A。 Dissolving liquid B control was stirred at 25 ° C, at a rate of I. 4g / min was added dropwise lysate A. 溶解液A的滴加结束后,利用傅利叶变换红外分光光度计测定反应液,确认到来自异氰酸酯基的2250CHT1附近的峰消失后终止反应。 After dissolving solution A is added dropwise, using a Fourier transform infrared spectrophotometer reaction solution was confirmed to peak 2250CHT1 from the vicinity of the isocyanate groups of the reaction was terminated after the disappearance. 按照相对于六亚甲基二异氰酸酯1摩尔、肼为2摩尔(以摩尔比计为1:2)的方式发生了反应。 It was reacted ways: according respect hexamethylene diisocyanate, 1 mol of hydrazine 2 moles (2 molar ratio of 1).

[0288] 反应终止后,使用滤纸(桐山社制造No. 4)利用桐山漏斗(桐山社制造)进行过滤,进行脱液,用乙醇50ml来清洗所得到的滤取物,进一步进行过滤,在真空烘箱中以50°C 干燥所得到的滤取物。 [0288] After completion of the reaction, using a filter paper (Kiriyama manufactured No. 4) using a separatory funnel (Kiriyama Co., Ltd.) was filtered for liquid removal, with ethanol 50ml cleaning the obtained filtrate was further filtered in vacuo oven to leach 50 ° C drying the resulting extract. 干燥后,利用高压粉碎机(商品名:nanojetmizer、AishinNano TechnologiesCO.,LTD制造)进行粉碎,制造平均粒径(中值径)为2· 1μm的均二氨基脲化合物。 After drying, a high-pressure pulverizer (trade name:. Nanojetmizer, AishinNano TechnologiesCO, LTD, Ltd.) was pulverized, producing an average particle diameter (median diameter) 2 · 1μm average diamino urea compound.

[0289] (实施例3) [0289] (Example 3)

[0290] (B-7)4-(丙烯酸乙酯)氨基脲 [0290] (B-7) 4- (ethyl acrylate) semicarbazide

[0291] 【化33】 [0291] [Chemical Formula 33]

[0292] [0292]

Figure CN104428339AD00321

[0293] 准备在乙醇150g中溶解有2-异氰酸酯根合丙烯酸乙酯14.Ig而成的溶解液A、 以及在乙醇150g中溶解肼5g而成的溶解液B。 [0293] prepared by dissolving 2-isocyanatoethyl sulfato ethyl acrylate 14.Ig obtained by dissolving solution A, and the lysis buffer hydrazine in ethanol and 150g of 5g formed in ethanol 150g of B. 将溶解液B控制在25°C进行搅拌,同时以I. 4g/分钟的速度滴加溶解液A。 Dissolving liquid B control was stirred at 25 ° C, at a rate of I. 4g / min was added dropwise lysate A. 溶解液A的滴加结束后,利用傅利叶变换红外分光光度计测定反应液,确认到来自异氰酸酯基的2250CHT1附近的峰消失后终止反应。 After dissolving solution A is added dropwise, using a Fourier transform infrared spectrophotometer reaction solution was confirmed to peak 2250CHT1 from the vicinity of the isocyanate groups of the reaction was terminated after the disappearance. 按照相对于2_异氰酸酯根合丙烯酸乙酯1摩尔、肼为1摩尔(以摩尔比计为1:1)的方式发生了反应。 It was reacted way: Following relative 2_ isocyanatomethyl engagement ethyl acrylate 1 mole of hydrazine to 1 mole of (a molar ratio of 1).

[0294] 反应终止后,利用蒸发器在50°C下使乙醇蒸发,利用傅利叶变换红外分光光度计测定精制物,确认到来自乙醇的3300〇114附近的峰消失,制造出液体均二氨基脲化合物。 [0294] After completion of the reaction, an evaporator so that at 50 ° C for evaporation of ethanol, the use of Fourier transform infrared spectrophotometer purified product was confirmed to peak around from ethanol 3300〇114 disappear, producing a liquid are disemicarbazide compound.

[0295] (实施例4) [0295] (Example 4)

[0296] (B-3) 4, 4 ' - (2, 2, 4-三甲基六亚甲基)双(氨基脲) [0296] (B-3) 4, 4 '- (2, 2, 4- trimethyl hexamethylene) bis (semicarbazide)

[0297]【化34】 [0297] [Chemical Formula 34]

[0298] [0298]

Figure CN104428339AD00322

[0299] 准备在乙醇50g中溶解有三甲基六亚甲基二异氰酸酯10. 51g而成的溶解液A、以及在乙醇50g中溶解有肼5.Olg而成的溶解液B。 [0299] Preparation was dissolved in ethanol 50g has trimethyl hexamethylene diisocyanate 10. 51g obtained by dissolving solution A, and dissolved in ethanol and 50g with solvent hydrazine 5.Olg formed B. 将溶解液B控制在25°C进行搅拌,同时以I. 4g/分钟的速度滴加溶解液A。 Dissolving liquid B control was stirred at 25 ° C, at a rate of I. 4g / min was added dropwise lysate A. 溶解液A的滴加结束后,利用傅利叶变换红外分光光度计测定反应液,确认到来自异氰酸酯基的2250cm-1附近的峰消失后终止反应。 After dissolving solution A is added dropwise, using a Fourier transform infrared spectrophotometer reaction solution confirmed that the peak around from an isocyanate group 2250cm-1 disappeared the reaction was terminated. 按照相对于三甲基六亚甲基二异氰酸酯1摩尔、肼为2摩尔(以摩尔比计为1:2)的方式发生了反应。 It was reacted ways: according respect trimethyl hexamethylene diisocyanate, 1 mol of hydrazine 2 moles (2 molar ratio of 1). [0300] 反应终止后,利用蒸发器在50°C下使乙醇蒸发,利用傅利叶变换红外分光光度计测定精制物,确认到来自乙醇的3300〇1^附近的峰消失,制造液体均二氨基脲化合物。 [0300] After completion of the reaction, an evaporator so that at 50 ° C for evaporation of ethanol, the use of Fourier spectrophotometer purified transform infrared confirmed peaks 3300〇1 ^ close from ethanol disappear, producing a liquid are disemicarbazide compound.

[0301] (实施例5) [0301] (Example 5)

[0302] (B-5)4, 4' -(1,3-亚苯基双亚甲基)双(氨基脲) [0302] (B-5) 4, 4 '- (1,3- phenylene-bis-methylene) bis (semicarbazide)

[0303] 【化35】 [0303] [Chemical Formula 35]

[0304] [0304]

Figure CN104428339AD00331

[0305] 准备在异丙醇IOOg中溶解有间二甲苯二异氰酸酯18. 82g而成的溶解液A、以及在异丙醇IOOg中溶解有肼25. 3g而成的溶解液B。 [0305] Preparation was dissolved in isopropanol IOOg there are m-xylylene diisocyanate 18. 82g obtained by dissolving solution A, and was dissolved in isopropanol IOOg the hydrazine lysate 25. 3g formed B. 在三口烧瓶中将溶解液B-边控制在30°C-边进行搅拌,同时以I. 4g/分钟的速度滴加溶解液A。 Dissolving liquid B- side control at 30 ° C- resultant mixture was stirred in a three-necked flask, at a rate of I. 4g / min was added dropwise lysate A. 溶解液A的滴加结束后,利用傅利叶变换红外分光光度计测定反应液,确认到来自异氰酸酯基的2250CHT1附近的峰消失后终止反应。 After dissolving solution A is added dropwise, using a Fourier transform infrared spectrophotometer reaction solution was confirmed to peak 2250CHT1 from the vicinity of the isocyanate groups of the reaction was terminated after the disappearance. 按照相对于间二甲苯二异氰酸酯1摩尔、肼为5摩尔(以摩尔比计为1:5)的方式发生了反应。 It was reacted ways: according respect to m-xylene diisocyanate, 1 mole of hydrazine is 5 mol (5 molar ratio of 1).

[0306] 反应终止后,使用滤纸(桐山社制造No. 4)利用桐山漏斗(桐山社制造)进行过滤,进行脱液,用异丙醇50ml来清洗所得到的滤取物,进一步进行过滤,在真空烘箱中以50°C干燥所得到的滤取物。 [0306] After completion of the reaction, using a filter paper (Kiriyama manufactured No. 4) using a separatory funnel (manufactured by Kiriyama Corporation) was filtered for liquid removal, isopropanol 50ml cleaning the obtained filtrate was further filtered, to filter 50 ° C drying the resulting extract in a vacuum oven.

[0307]干燥后,利用高压粉碎机(商品名:nanojetmizer、AishinNanoTechnologies CO.,LTD制造)进行粉碎,制造平均粒径(中值径)为2· 2μm的均二氨基脲化合物。 [0307] After drying, a high-pressure pulverizer (trade name:. Nanojetmizer, AishinNanoTechnologies CO, LTD, Ltd.) was pulverized, producing an average particle diameter (median diameter) 2 · 2μm average diamino urea compound.

[0308](实施例6) [0308] (Example 6)

[0309] (B-4)4,4, -(1,3_环己基双亚甲基)双(氨基脲) [0309] (B-4) 4,4, - (1,3_ cyclohexyl-bis methylene) bis (semicarbazide)

[0310]【化36】 [0310] [Chemical Formula 36]

[0311] [0311]

Figure CN104428339AD00332

[0312] 准备在异丙醇IOOg中溶解1,3-双(异氰酸根合甲基)环己烷19. 42g而成的溶解液A、以及在异丙醇IOOg中溶解肼25. 3g而成的溶解液B。 [0312] Preparation was dissolved in isopropanol IOOg 1,3-bis (isocyanatomethyl) cyclohexane dissolved solution A 19. 42g formed, and dissolved hydrazine in isopropanol IOOg of 25. 3g and into the dissolving solution B. 在三口烧瓶中将溶解液B- 边控制在30°C-边进行搅拌,同时以I. 4g/分钟的速度滴加溶解液A。 Dissolving liquid B- side control at 30 ° C- resultant mixture was stirred in a three-necked flask, at a rate of I. 4g / min was added dropwise lysate A. 溶解液A的滴加结束后,利用傅利叶变换红外分光光度计测定反应液,确认到来自异氰酸酯基的2250CHT1附近的峰消失后终止反应。 After dissolving solution A is added dropwise, using a Fourier transform infrared spectrophotometer reaction solution was confirmed to peak 2250CHT1 from the vicinity of the isocyanate groups of the reaction was terminated after the disappearance. 按照相对于1,3-双(异氰酸根合甲基)环己烷1摩尔、肼为5摩尔(以摩尔比计为1:5)的方式发生了反应。 It was reacted ways: according respect to 1,3-bis (isocyanatomethyl) cyclohexane 1 mole of hydrazine is 5 mol (5 molar ratio of 1).

[0313] 反应终止后,使用滤纸(桐山社制造No. 4)利用桐山漏斗(桐山社制造)进行过滤,进行脱液,用异丙醇50ml来清洗所得到的滤取物,进一步进行过滤,在真空烘箱中以50°C干燥所得到的滤取物。 [0313] After completion of the reaction, using a filter paper (Kiriyama manufactured No. 4) using a separatory funnel (manufactured by Kiriyama Corporation) was filtered for liquid removal, isopropanol 50ml cleaning the obtained filtrate was further filtered, to filter 50 ° C drying the resulting extract in a vacuum oven.

[0314] (实施例7) [0314] (Example 7)

[0315] (B-6) 4, 4' -异佛尔酮双(氨基脲) [0315] (B-6) 4, 4 '- isophorone-bis (semicarbazide)

[0316] 【化37】 [0316] [Chemical Formula 37]

[0317] [0317]

Figure CN104428339AD00341

[0318] 准备在乙醇IOOg中溶解有异佛尔酮二异氰酸酯22. 22g而成的溶解液A、以及在乙醇IOOg中溶解有肼25. 3g而成的溶解液B。 [0318] Preparation was dissolved in ethanol IOOg have isophorone diisocyanate 22. 22g obtained by dissolving solution A, and hydrazine dissolving liquid 25. 3g obtained by dissolving in ethanol IOOg in B. 在三口烧瓶中将溶解液B-边控制在30°C- 边进行搅拌,同时以I. 4g/分钟的速度滴加溶解液A。 Dissolving liquid B- side control at 30 ° C- resultant mixture was stirred in a three-necked flask, at a rate of I. 4g / min was added dropwise lysate A. 溶解液A的滴加结束后,利用傅利叶变换红外分光光度计测定反应液,确认到来自异氰酸酯基的2250CHT1附近的峰消失后终止反应。 After dissolving solution A is added dropwise, using a Fourier transform infrared spectrophotometer reaction solution was confirmed to peak 2250CHT1 from the vicinity of the isocyanate groups of the reaction was terminated after the disappearance. 按照相对于异佛尔酮二异氰酸酯1摩尔、肼为5摩尔(以摩尔比计为1:5)的方式发生了反应。 It was reacted ways: according respect isophorone diisocyanate 1 mole of hydrazine is 5 mol (5 molar ratio of 1).

[0319] 反应终止后,利用蒸发器在50°C下使乙醇蒸发,利用傅利叶变换红外分光光度计测定精制物,确认到来自乙醇的3300〇11 4附近的峰消失,制造出液体均二氨基脲化合物。 [0319] After completion of the reaction, an evaporator so that at 50 ° C for evaporation of ethanol, the use of Fourier transform infrared spectrophotometer purified product was confirmed to peak around from ethanol 3300〇11 4 disappear, producing a liquid are diamino urea compounds.

[0320] (实施例8) [0320] (Example 8)

[0321] (A-1) 1,1' -[亚甲基双(环己烧_4, 1-二基)]双[3-(12-氨基十二烧基)脈] [0322]【化38】 [0321] (A-1) 1,1 '- [methylene bis (cyclohexyl burning _4, 1-yl)] bis [3- (12-aminododecanoic burn-yl) pulse] [0322] [ of 38]

[0323] [0323]

Figure CN104428339AD00342

[0324] 准备在乙醇79g中溶解有二环己基甲烷-4, 4-二异氰酸酯13. 6gg而成的溶解液A、以及在乙醇IOOg中溶解有1,12-二氨基十二烷(TCI社制造)20. 7g而成的溶解液B。 [0324] prepared by dissolving dicyclohexylmethane in ethanol 79g in-4,4-diisocyanate 13. 6gg obtained by dissolving solution A, and dissolved 1,12-diamino-dodecane (TCI Co. in ethanol IOOg in ) was dissolved was 20. 7g formed B. 在三口烧瓶中将溶解液B-边控制在30°C-边进行搅拌,同时以I. 4g/分钟的速度滴加溶解液A。 Dissolving liquid B- side control at 30 ° C- resultant mixture was stirred in a three-necked flask, at a rate of I. 4g / min was added dropwise lysate A. 滴加结束后,利用傅利叶变换红外分光光度计测定反应液,确认到来自异氰酸酯基的2250CHT1附近的峰消失后终止反应。 After the dropwise addition, the use of Fourier transform infrared spectrophotometer reaction solution confirmed that the peak 2250CHT1 close from isocyanate group disappeared and the reaction was terminated. 按照相对于二环己基甲烷-4, 4-二异氰酸酯1摩尔、 1,12-二氨基十二烷为2摩尔(以摩尔比计为1:2)的方式发生了反应。 According to relative dicyclohexylmethane-4,4-diisocyanate, 1 mol of 1,12-aminododecane 2 mol (molar ratio of 1: 2) the way had reacted.

[0325] 将反应液注入搅拌下的水500g中以促进结晶化,静置1小时后,使用滤纸(桐山社制造No. 4)利用桐山漏斗(桐山社制造)进行过滤,在真空烘箱中以50°C干燥所得到的滤取物。 [0325] The reaction mixture was poured into stirred water 500g to promote crystallization, after standing for 1 hour, using a filter paper (Kiriyama manufactured No. 4) using a separatory funnel (Kiriyama Co., Ltd.) is filtered to in a vacuum oven 50 ° C drying the obtained filtrate was. 干燥后自然冷却至室温,利用高压粉碎机(商品名:nanojetmizer、AishinNano TechnologiesCO.,LTD制造)进行粉碎,制造平均粒径(中值径)为2. 5μm的胺化合物。 After drying naturally cooled to room temperature, high-pressure pulverizer (trade name:. Nanojetmizer, AishinNano TechnologiesCO, LTD, Ltd.) was pulverized, producing an average particle diameter (median diameter) of the amine compound 2. 5μm.

[0326] (实施例9) [0326] (Example 9)

[0327] (Α-3)1,Γ-[亚甲基双(环己烷-4,卜二基)]双[3-(6-氨基己基)脲] [0327] (Α-3) 1, Γ- [methylene bis (cyclohexane -4, Boer Ji)] bis [3- (6-aminohexyl) urea]

[0328]【化39】 [0328] [Chemical Formula 39]

Figure CN104428339AD00351

[0330] 准备在乙醇IOOg中溶解有1,6-二氨基己烷(TCI社制造)12g而成的溶解液A、以及在乙醇79g中溶解有二环己基甲烷-4, 4'-二异氰酸酯13. 6g而成的溶解液B。 [0330] Preparation was dissolved in ethanol IOOg there are 1,6-diaminohexane (TCI Co., Ltd.) was dissolved solution A 12g formed, and dissolved dicyclohexylmethane in ethanol 79g in-4,4'-diisocyanate 13. 6g made of lysis solution B. 在三口烧瓶中将溶解液B-边控制在30°C-边进行搅拌,同时以I. 4g/分钟的速度滴加溶解液A。 Dissolving liquid B- side control at 30 ° C- resultant mixture was stirred in a three-necked flask, at a rate of I. 4g / min was added dropwise lysate A. 滴加结束后,利用傅利叶变换红外分光光度计测定反应液,确认到来自异氰酸酯基的2250CHT1 附近的峰消失后终止反应。 After the dropwise addition, the use of Fourier transform infrared spectrophotometer reaction solution confirmed that the peak 2250CHT1 close from isocyanate group disappeared and the reaction was terminated. 按照相对于二环己基甲烷-4, 4-二异氰酸酯1摩尔、1,6-二氨基己烷为2摩尔(以摩尔比计为1:2)的方式发生了反应。 According respect dicyclohexylmethane-4,4-diisocyanate 1 mole of 1,6-diaminohexane 2 mol (molar ratio of 1: 2) manner had reacted.

[0331] 其后,利用旋转蒸发器在减压下蒸馏除去溶剂。 [0331] Then, using a rotary evaporator, the solvent was removed under reduced pressure distillation. 干燥后自然冷却至室温,利用高压粉碎机(商品名:nanojetmizer、AishinNanoTechnologiesCO.,LTD制造)进行粉碎,制造平均粒径(中值径)为2. 2μm的胺化合物。 Naturally cooled after drying to room temperature, high-pressure pulverizer (trade name:. Nanojetmizer, AishinNanoTechnologiesCO, LTD, Ltd.) was pulverized, producing an average particle diameter (median diameter) of the amine compound 2. 2μm of.

[0332](实施例10) [0332] (Example 10)

[0333] (A-4) 1,1 ' -(己烧_1,6_ 二基)双[3_ (12-氨基十二烧基)脈] [0333] (A-4) 1,1 '- (cyclohexyl burning _1,6_-diyl) bis [3_ (12-aminododecanoic burn-yl) veins]

[0334]【化40】 [0334] [Chemical Formula 40]

[0335] [0335]

Figure CN104428339AD00352

[0336] 准备在乙醇150g中溶解有1,12-二氨基十二烷(TCI社制造)49. 65g而成的溶解液A、以及在乙醇118g中溶解有六亚甲基二异氰酸酯20. 54g而成的溶解液B。 [0336] prepared by dissolving 1,12-diamino-dodecane (TCI Co., Ltd.) was dissolved solution A 49. 65g formed, and dissolved in ethanol 118g has hexamethylene diisocyanate 20. 54g in ethanol 150g of obtained by dissolving solution B. 在三口烧瓶中将溶解液B-边控制在30°C-边进行搅拌,同时以I. 4g/分钟的速度滴加溶解液A。 B- dissolving liquid side control edge at 30 ° C- was stirred in a three-necked flask, at a rate of I. 4g / min was dissolved was added dropwise A. 滴加结束后,利用傅利叶变换红外分光光度计测定反应液,确认到来自异氰酸酯基的2250CHT1 附近的峰消失后终止反应。 After the dropwise addition, the use of Fourier transform infrared spectrophotometer reaction solution confirmed that the peak 2250CHT1 close from isocyanate group disappeared and the reaction was terminated. 按照相对于六亚甲基二异氰酸酯1摩尔、1,12-二氨基十二烷为2摩尔(以摩尔比计为1:2)的方式发生了反应。 It was reacted ways: according with hexamethylene diisocyanate to 1 mol, 1,12-diamino dodecane 2 moles (2 molar ratio of 1).

[0337] 其后利用旋转蒸发器在减压下蒸馏除去溶剂。 [0337] Then using a rotary evaporator, the solvent was distilled off under reduced pressure. 干燥后自然冷却至室温,利用高压粉碎机(商品名:nanojetmizer、AishinNanoTechnologiesCO.,LTD制造)进行粉碎,制造平均粒径(中值径)为2. 1μm的二胺脲化合物。 Naturally cooled after drying to room temperature, high-pressure pulverizer (trade name:. Nanojetmizer, AishinNanoTechnologiesCO, LTD, Ltd.) was pulverized, producing an average particle diameter (median diameter) diamine urea compound 2. 1μm to.

[0338] 反应终止后,使用滤纸(桐山社制造No. 4)利用桐山漏斗(桐山社制造)进行过滤,进行脱液,利用乙醇100ml来清洗所得到的滤取物,进一步进行过滤,在真空烘箱中以50°C干燥所得到的滤取物。 [0338] After completion of the reaction, using a filter paper (Kiriyama manufactured No. 4) using a separatory funnel (Kiriyama Co., Ltd.) was filtered for liquid removal, with ethanol 100ml to wash the obtained filtrate was further filtered in vacuo oven to leach 50 ° C drying the resulting extract.

[0339](实施例11) [0339] (Example 11)

[0340] (A-5) 1,1 ' -(己烧_1,6_ 二基)双[3_ (2_ 氨基乙基)脈] [0340] (A-5) 1,1 '- (cyclohexyl burning _1,6_-diyl) bis [3_ (2_ aminoethyl) pulse]

[0341]【化41】 [0341] [Chemical Formula 41]

[0342] [0342]

Figure CN104428339AD00361

[0343] 准备在乙醇118g中溶解有六亚甲基二异氰酸酯17. 17g而成的溶解液A、以及在乙醇150g中溶解有乙二胺61.36g而成的溶解液B。 [0343] Preparation was dissolved in ethanol 118g has hexamethylene diisocyanate 17. 17g obtained by dissolving solution A, and dissolved in ethanol 150g of ethylenediamine dissolved solution 61.36g obtained by B. 在三口烧瓶中将溶解液B控制在25°C 进行搅拌,同时以I. 4g/分钟的速度滴加溶解液A。 Dissolving liquid B control was stirred at 25 ° C in a three-necked flask, at a rate of I. 4g / min was added dropwise lysate A. 溶解液A的滴加结束后,利用傅利叶变换红外分光光度计测定反应液,确认到来自异氰酸酯基的2250CHT1附近的峰消失后终止反应。 After dissolving solution A is added dropwise, using a Fourier transform infrared spectrophotometer reaction solution was confirmed to peak 2250CHT1 from the vicinity of the isocyanate groups of the reaction was terminated after the disappearance. 按照相对于六亚甲基二异氰酸酯1摩尔、乙二胺为10摩尔(以摩尔比计为1:10)的方式发生了反应。 It was reacted in accordance with hexamethylene diisocyanate, 1 mole of ethylenediamine 10 mol (molar ratio 1:10) manner.

[0344] 反应终止后,使用滤纸(桐山社制造No. 4)利用桐山漏斗(桐山社制造)进行过滤,进行脱液,利用乙醇IOOml来清洗所得到的滤取物,进一步进行过滤,在真空烘箱中以50°C干燥所得到的滤取物。 [0344] After completion of the reaction, using a filter paper (Kiriyama manufactured No. 4) using a separatory funnel (Kiriyama Co., Ltd.) was filtered for liquid removal, with ethanol IOOml to wash the obtained filtrate was further filtered in vacuo oven to leach 50 ° C drying the resulting extract. 干燥后自然冷却至室温,利用高压粉碎机(商品名: nanojetmizer、AishinNanoTechnologiesCO.,LTD制造)进行粉碎,制造平均粒径(中值径)为2·2μπι的胺化合物。 Naturally cooled after drying to room temperature, high-pressure pulverizer (trade name:. Nanojetmizer, AishinNanoTechnologiesCO, LTD, Ltd.) was pulverized, producing an average particle diameter (median diameter) of the amine compound 2 · 2μπι of.

[0345](实施例12) [0345] (Example 12)

[0346] (Α-6) 1,1 ' -(己烧_1,6_ 二基)双[3_ (6_ 氨基己基)脈] [0346] (Α-6) 1,1 '- (cyclohexyl burning _1,6_-diyl) bis [3_ (6_ aminohexyl) veins]

[0347]【化42】 [0347] [Chemical Formula 42]

[0348] [0348]

Figure CN104428339AD00362

[0349] 准备在乙醇150g中溶解有六亚甲基二异氰酸酯17. 17g而成的溶解液Α、以及在乙醇118g中溶解有1,6_二氨基己烷(TCI社制造)94.9g而成的溶解液B。 [0349] Preparation was dissolved in ethanol 150g has hexamethylene diisocyanate dissolved solution Α 17. 17g formed, and dissolved in ethanol 118g has 1,6_-diaminohexane (TCI Corp.) 94.9g made the lysate B. 在三口烧瓶中将溶解液B控制在25°C进行搅拌,同时以I. 4g/分钟的速度滴加溶解液A。 Dissolving liquid B control was stirred at 25 ° C in a three-necked flask, at a rate of I. 4g / min was added dropwise lysate A. 溶解液A的滴加结束后,利用傅利叶变换红外分光光度计测定反应液,确认到来自异氰酸酯基的2250CHT1 附近的峰消失后终止反应。 After dissolving solution A is added dropwise, using a Fourier transform infrared spectrophotometer reaction solution was confirmed to peak 2250CHT1 from the vicinity of the isocyanate groups of the reaction was terminated after the disappearance. 按照相对于六亚甲基二异氰酸酯1摩尔、1,6_二氨基己烷为10 摩尔(以摩尔比计为1:10)的方式发生了反应。 Were reacted in accordance with hexamethylene diisocyanate to 1 mol, 1,6_-diaminohexane is 10 mol (molar ratio 1:10) manner.

[0350] 其后利用旋转蒸发器在减压下蒸馏除去溶剂。 [0350] Then using a rotary evaporator, the solvent was distilled off under reduced pressure. 干燥后自然冷却至室温,利用高压粉碎机(商品名:nanojetmizer、AishinNanoTechnologiesCO.,LTD制造)进行粉碎,制造平均粒径(中值径)为2. 3μm的胺化合物。 Naturally cooled after drying to room temperature, high-pressure pulverizer (trade name:. Nanojetmizer, AishinNanoTechnologiesCO, LTD, Ltd.) was pulverized, producing an average particle diameter (median diameter) of the amine compound 2. 3μm of.

[0351](实施例I3) [0351] (Example I3)

[0352] (A-2) 1,1' -[亚甲基双(环己烧_4, 1-二基)]双[3_(2_氨基乙基)脈] [0352] (A-2) 1,1 '- [methylene bis (cyclohexyl burning _4, 1-yl)] bis [3_ (2_ aminoethyl) pulse]

[0353]【化43】 [0353] [Chemical Formula 43]

[0354] [0354]

Figure CN104428339AD00371

[0355] 准备在乙醇IOOg中溶解有二环己基甲烷4, 4' -二异氰酸酯13. 55g而成的溶解液A、以及在乙醇79g中溶解有乙二胺(TCI社制造)15. 5g而成的溶解液B。 [0355] prepared by dissolving dicyclohexylmethane 4, 4 'in ethanol IOOg in - diisocyanate dissolved solution A 13. 55g formed, and dissolved in ethanol 79g of ethylenediamine (TCI Corp.) 15 5g and into the dissolving liquid B. 在三口烧瓶中将溶解液B控制在25°C进行搅拌,同时以I. 4g/分钟的速度滴加溶解液A。 Dissolving liquid B control was stirred at 25 ° C in a three-necked flask, at a rate of I. 4g / min was added dropwise lysate A. 溶解液A的滴加结束后,利用傅利叶变换红外分光光度计测定反应液,确认到来自异氰酸酯基的2250CHT1 附近的峰消失后终止反应。 After dissolving solution A is added dropwise, using a Fourier transform infrared spectrophotometer reaction solution was confirmed to peak 2250CHT1 from the vicinity of the isocyanate groups of the reaction was terminated after the disappearance. 按照相对于六亚甲基二异氰酸酯1摩尔、1,6-二氨基己烷为5 摩尔(以摩尔比计为1:5)的方式发生了反应。 It was reacted ways: according respect hexamethylene diisocyanate, 1 mol of 1,6-diaminohexane 5 mol (5 molar ratio of 1).

[0356] 反应终止后,使用滤纸(桐山社制造No. 4)利用桐山漏斗(桐山社制造)进行过滤,进行脱液,用乙醇IOOml来清洗所得到的滤取物,进一步进行过滤,在真空烘箱中以50°C干燥所得到的滤取物。 [0356] After completion of the reaction, using a filter paper (Kiriyama manufactured No. 4) using a separatory funnel (Kiriyama Co., Ltd.) was filtered for liquid removal, with ethanol IOOml to wash the obtained filtrate was further filtered in vacuo oven to leach 50 ° C drying the resulting extract. 干燥后自然冷却至室温,利用高压粉碎机(商品名: nanojetmizer、AishinNanoTechnologiesCO.,LTD制造)进行粉碎,制造平均粒径(中值径)为2·2μπι的胺化合物。 Naturally cooled after drying to room temperature, high-pressure pulverizer (trade name:. Nanojetmizer, AishinNanoTechnologiesCO, LTD, Ltd.) was pulverized, producing an average particle diameter (median diameter) of the amine compound 2 · 2μπι of.

[0357](合成例) [0357] (Synthesis Example)

[0358] (Α-5')1,1 ' -(己烧-1,6_ 二基)双[3_ (2_ 氨基乙基)脈] [0358] (Α-5 ') 1,1' - (cyclohexyl burning -1,6_-diyl) bis [3_ (2_ aminoethyl) pulse]

[0359]【化44】 [0359] [Chemical Formula 44]

[0360] [0360]

Figure CN104428339AD00372

[0361] 将乙二胺61.36g(1020mmol)和甲苯150g在三口烧瓶中搅拌,滴加六亚甲基二异氰酸酯17. 17g(102mm〇l)的甲苯118. 5g(150ml)溶液。 [0361] Ethylenediamine 61.36g (1020mmol) and toluene 150g stirred three-neck flask, a solution of hexamethylene diisocyanate 17. 17g (102mm〇l) in toluene 118. 5g (150ml) was added. 反应时间为30分钟,反应液控制在40°C。 The reaction time was 30 minutes, the reaction was controlled at 40 ° C. 滴加结束后,过滤反应液,用甲苯清洗析出物后投入水中。 After completion of the dropwise addition, reaction solution was filtered, poured into water after washing the precipitate with toluene. 搅拌1小时后,进行过滤, 利用蒸发器在减压下对所得到的滤液进行浓缩后,确认到析出物。 After stirring for 1 hour, then filtered, the filtrate obtained was concentrated under reduced pressure using an evaporator, it was confirmed that the precipitates. 对于反应了的六亚甲基二异氰酸酯和乙二胺,相对于六亚甲基二异氰酸酯1摩尔,乙二胺为10摩尔(以摩尔比计为1:10)。 The reaction of hexamethylene diisocyanate and ethylene diamine, with respect to hexamethylene diisocyanate, 1 mole of ethylenediamine 10 mol (molar ratio 1:10). 将所得到的析出物用乙醇(EtOH)清洗,减压干燥,将得到的结晶利用高压粉碎机(商品名:nanojetmizer、AishinNanoTechnologiesCO.,LTD制造)进行粉碎,制造平均粒径(中值径)为2. 1μm的胺化合物。 The resulting precipitate was washed with ethanol (EtOH), dried under reduced pressure, and the resulting crystals were using a high-pressure pulverizer (trade name:. Nanojetmizer, AishinNanoTechnologiesCO, LTD, Ltd.) was pulverized, producing an average particle diameter (median diameter) amine compound 2. 1μm to.

[0362](实施例14) [0362] (Example 14)

[0363] (Α-7)Ν,Ν' -六亚甲基[羰基双(氮烷二基)(2-氨基乙基)]-[羰基双(氮烷二基)(6_氨基己基)] [0363] (Α-7) Ν, Ν '- hexamethylene [carbonyl-bis (azanediyl) (2-aminoethyl)] - [carbonyl-bis (azanediyl) (6_ aminohexyl) ]

[0364]【化45】 [0364] [Chemical Formula 45]

[0365] [0365]

Figure CN104428339AD00381

[0366] 准备在异丙醇240g中溶解有六亚甲基二异氰酸酯(TCI社制造)18. 3g而成的溶解液A、以及在异丙醇72. 6g中溶解有1,6-己二胺33. 48g和乙二胺18. 3g而成的溶解液B。 [0366] Preparation was dissolved in isopropanol 240g has hexamethylene diisocyanate (TCI Co., Ltd.) was dissolved solution A 18. 3g formed, and dissolved in isopropanol 72. 6g has hexamethylene amine 33. 48g and ethylenediamine dissolved solution 18. 3g formed B. 在三口烧瓶中将溶解液B控制在25°C进行搅拌,同时以I. 4g/分钟的速度滴加溶解液A。 Dissolving liquid B control was stirred at 25 ° C in a three-necked flask, at a rate of I. 4g / min was added dropwise lysate A. 溶解液A的滴加结束后,利用傅利叶变换红外分光光度计测定反应液,确认到来自异氰酸酯基的2250CHT1附近的峰消失后终止反应。 After dissolving solution A is added dropwise, using a Fourier transform infrared spectrophotometer reaction solution was confirmed to peak 2250CHT1 from the vicinity of the isocyanate groups of the reaction was terminated after the disappearance. 按照相对于六亚甲基二异氰酸酯1摩尔、乙二胺为5摩尔、1,6-二氨基己烷为5摩尔(以摩尔比计为1:5:5)的方式发生了反应。 Were reacted in the manner as with respect to hexamethylene diisocyanate, 1 mole of ethylenediamine 5 mol, 1,6-diaminohexane 5 mol (5 molar ratio of 1:: 5).

[0367] 反应终止后,使用滤纸(桐山社制造No. 4)利用桐山漏斗(桐山社制造)进行过滤,进行脱液,利用异丙醇IOOml来清洗所得到的滤取物,进一步进行过滤,在真空烘箱中以50°C干燥所得到的滤取物。 [0367] After completion of the reaction, using a filter paper (Kiriyama manufactured No. 4) using a separatory funnel (manufactured by Kiriyama Corporation) was filtered for liquid removal, use of isopropanol IOOml to wash the obtained filtrate was further filtered, to filter 50 ° C drying the resulting extract in a vacuum oven. 干燥后自然冷却至室温,利用高压粉碎机(商品名: nanojetmizer、AishinNanoTechnologiesCO.,LTD制造)进行粉碎,制造平均粒径(中值径)为2·2μπι的胺化合物。 Naturally cooled after drying to room temperature, high-pressure pulverizer (trade name:. Nanojetmizer, AishinNanoTechnologiesCO, LTD, Ltd.) was pulverized, producing an average particle diameter (median diameter) of the amine compound 2 · 2μπι of.

[0368]〔环氧树脂的制造〕 [0368] [epoxy manufacturing]

[0369] 按照日本特开平5-295087号公报所记载的制造方法,制造偏酯化环氧树脂。 [0369] according to the manufacturing method described in Japanese Patent Laid-Open No. 5-295087 Publication described, producing partial epoxies. 具体地说,如下制造偏酯化环氧树脂(部分甲基丙烯酰化环氧树脂)。 Specifically, the following manufacturing partial esterification of the epoxy resin (Part methacryloylated epoxy resin).

[0370] (i)高纯度双酚A型环氧树脂:将EPICL0N-850S〔DIC社制造〕1000质量份、甲基丙烯酸250质量份、甲苯900质量份、三乙胺2质量份、对甲氧基苯酚2质量份混合,在90°C 下加热搅拌8小时,得到部分加成反应产物。 [0370] (i) a high-purity bisphenol A type epoxy resin: The EPICL0N-850S [DIC Corp.] 1000 parts by mass, methacrylic acid, 250 parts by mass parts Toluene 900 mass parts of triethylamine 2 mass of methyl methoxyphenol 2 parts by mass were mixed at 90 ° C for heating and stirring for 8 hours to obtain part of an addition reaction product.

[0371] (ii)上述⑴的生成物中加入甲苯4500质量份,制成稀释溶液,向其中添加纯水4500质量份,在室温搅拌1小时后静置,将水层分离除去。 After the product [0371] (ii) above ⑴ added toluene parts 4500 by mass to prepare a diluted solution, pure water was added to 4,500 parts by mass, stirred at room temperature for 1 hour standing, the aqueous layer was separated and removed. 该清洗操作重复3〜5次,接着重复3〜5次利用同量的1当量NaOH溶液进行的清洗,进一步重复3〜5次仅利用同量的纯水进行的清洗,使用离子电导率测定器(堀场制作所社制造:电导率计)对最终的清洗水测定其离子电导率,确认到其为lOuS/cm以下。 This washing operation was repeated three to five times, and then repeated three to five times using 1 N NaOH solution, the same amount were washed further repeated three to five times using only the same amount of pure water cleaning, using an ion conductivity measuring device (Horiba manufactured: a conductivity meter) was measured ionic conductivity of the final washing water was confirmed as lOuS / cm or less.

[0372] (iii)将过滤上述(ii)的溶液所得的溶液在减压下于70°C进行浓缩,将甲苯完全除去而精制,合成出部分甲基丙烯酰化环氧树脂。 [0372] (iii) The filter obtained in the above (ii) was a solution at 70 ° C and concentrated under reduced pressure, and purified toluene was completely removed synthesized portion methacryloylated epoxy resin.

[0373] 此外,基于上述合成例,使用丙烯酸来代替甲基丙烯酸,通过相同的方法合成了部分丙烯酰化环氧树脂。 [0373] Further, the above Synthesis Example, acrylic acid instead of methacrylic acid, the synthesis of some acrylated epoxy resin by the same method.

[0374]〔液晶密封剂组合物的制造〕 [0374] [Production of liquid crystal sealant composition]

[0375] 将上述部分甲基丙烯酰化环氧树脂100质量份、作为无机填充剂的球状二氧化硅(Admafine社制造,S0-C1) 15质量份、作为有机填料的F-351 (日本Zeon社制造)15质量份、 作为光自由基引发剂的Irgacure907(BASFJapan社制造)3质量份、作为娃烧偶联剂的KBM-403 (信越化学工业社制造)2质量份、以及作为固化剂的实施例1〜5、8〜12、14的固化剂混配,相对于上述部分甲基丙烯酰化环氧树脂的环氧基1当量,该固化剂的混配量为1 当量,使用Three-OneM〇t〇r(IKA社制造,商品名;RW28basic)进行均匀分散,得到液晶密封剂树脂组合物。 [0375] The said portion meth acrylated epoxy resin 100 parts by mass, as an inorganic filler, spherical silica parts (Admafine manufactured, S0-C1) 15 by mass, an organic filler, F-351 (Nippon Zeon Co., Ltd.) 15 parts by mass, as a photo radical initiator Irgacure907 (BASFJapan Co., Ltd.) 3 parts by mass, 2 parts by mass of baby burn coupling agent KBM-403 (Shin-Etsu chemical Co., Ltd.), and as a curing agent curing agent compounded embodiment 1~5,8~12,14 embodiment, with respect to 1 equivalent of the epoxy group said portion meth acrylated epoxy resin, the blend amount of the curing agent is 1 equivalent, using Three- OneM〇t〇r (IKA Co., Ltd., trade name; RW28basic) uniformly dispersed to obtain a liquid crystal sealant resin composition.

[0376] 作为比较例1,使用市售的十二烷二酸酰肼(DDH、大塚化学社制造),作为比较例2,使用市售的1,3-二(3-肼-3-氧代-丙基)-5-(1-甲基乙基)乙内酰脲仏1^(:111^¥0!1、AJINOMOTOFINETECHNO社制造),除此以外与上述相同,制造液晶密封剂组合物。 [0376] As Comparative Example 1, a commercially available dodecanedioic acid hydrazide (DDH, Otsuka Chemical Co., Ltd.), as a 2, commercially available 1,3-bis (3-hydrazino-3-oxo Comparative Example Generation - propyl) -5- (1-methyl ethyl) hydantoin Fo 1 ^ (: 111 ^ ¥ 0! 1, AJINOMOTOFINETECHNO Corp.), except that the same as above, producing a liquid crystal sealant composition .

[0377][粘接强度的测定方法] [0377] [Determination of adhesive strength]

[0378] 图2是对使用实施例1〜5、8〜12、14和比较例1〜2的液晶密封剂组合物测定粘接强度的方法进行说明的图。 [0378] FIG. 2 is the use of a diagram for explaining a method embodiment of the liquid crystal sealant composition 1~5,8~12,14 and Comparative Examples 1 to 2 was measured adhesive strength embodiments. 如图2所示,准备厚度0. 5mm、3.Ocm见方的ITO玻璃8(玻璃表面具有ITO电极膜)和厚度0. 5mm、2. 3cm见方的玻璃9。 As shown in FIG 2, having a thickness 0. 5mm, 8 3.Ocm square ITO glass (glass surface having an ITO electrode film) and a thickness of 0. 5mm, 2. 3cm square glass 9. 在ITO玻璃的中央线上在距两端为9mm的部位按照直径为1. 5〜2. 0mm、且厚度为6. 0〜10. 0μm的方式涂布液晶密封剂组合物2作为粘接面,将3.Ocm见方的ITO玻璃8与2. 3cm见方的玻璃9的1边对齐来将两者贴合,从而制作出试验片10。 In the center line ITO glass away from the ends of 9mm parts according to diameter of 1. 5~2. 0mm, and a thickness of 6. 0~10. 0μm manner applying the liquid crystal sealant composition 2 as an adhesive surface the 3.Ocm square ITO glass 8 and 2. 3cm square glass 1 edge alignment 9 to both bonded to prepare a test piece 10. 对贴合的试验片10照射UV3000mJ(商品名:UB-031-A/ BM-EUEyegraphics社制造)后,在12(TC下加热60分钟,使液晶密封剂组合物2固化。利用Autograph(岛津制作所社制造;AGS)对固化后的试验片10的ITO玻璃8的中央线上的距端部为5mm的点进行冲压,测定粘接强度。结果列于表1。 Test piece bonded 10 irradiated UV3000mJ: after (trade name UB-031-A / BM-EUEyegraphics Co., Ltd.), heated (the TC 12 60 minutes, and the liquid crystal sealant composition 2 cured using Autograph (Shimadzu. Seisakusho manufactured; from the end portion of the center line AGS) of test piece after curing 10 ITO glass 8 is punched point 5mm measured bond strength results are shown in table 1.

[0379][带有取向膜的玻璃粘接强度] [0379] [Glass adhesion strength with the alignment film]

[0380] 准备厚度0. 7mm、3.Ocm见方的经抛光处理的取向膜(SUNEVERSE-7492、日产化学工业社制造)玻璃8 (玻璃表面具有取向膜)、以及厚度0. 7mm、2. 3cm见方的与玻璃8进行了同样处理的取向膜玻璃9。 [0380] Preparation thickness of 0. 7mm, the alignment film buffed 3.Ocm square (SUNEVERSE-7492, Nissan Chemical Industries Co., Ltd.) 8 Glass (glass surface of an alignment film), and a thickness of 0. 7mm, 2. 3cm square glass 8 alignment film glass 9 similarly treated. 如图2所示,在玻璃的中央线上在距两端为9mm的部位按照直径为I. 5mm〜2. 0mm、且厚度为6. 0μm〜10. 0μm的方式涂布液晶密封剂组合物2作为粘接面,将3.Ocm见方的取向膜玻璃8与2. 3cm见方的取向膜玻璃9的1边对齐,将两者贴合,从而制作出试验片10。 As shown, the central line of the glass away from both ends 2 9mm portions according diameter I. 5mm~2. 0mm, and a thickness of 6. 0μm~10. 0μm manner applying the liquid crystal sealant composition 2 as an adhesive surface, the 3.Ocm square alignment film glass 8 and the alignment film glass 2. 3cm square one side aligned. 9, both bonded to prepare a test piece 10. 对贴合的试验片10照射UV3000mJ(商品名:UB-031-A/ BM-EUEyegraphics社制造)后,在12(TC下加热60分钟,使液晶密封剂组合物2固化。利用Autograph(岛津制作所社制造;AGS)对固化后的试验片10的ITO玻璃8的中央线上的距端部为5mm的点进行冲压,测定粘接强度。 Test piece bonded 10 irradiated UV3000mJ: after (trade name UB-031-A / BM-EUEyegraphics Co., Ltd.), heated (the TC 12 60 minutes, and the liquid crystal sealant composition 2 cured using Autograph (Shimadzu. Seisakusho manufactured; AGS) of from the end portion of the center line of the ITO glass test piece cured 10 8 pressing point 5mm measured adhesive strength.

[0381][取向性试验方法] [0381] [Orientation Test Method]

[0382] 使用密封点胶机(dispenser)在贴有经抛光处理的取向膜(寸> $7S'-SE_7492、 日产化学工业社制造)的ITO玻璃基板上(60mmX70mmX0. 7mmt)以截面积为4000μm2点胶涂布使用了实施例11 (固化剂:Α-5)和比较例1 (固化剂:DDH)的液晶密封剂组合物。 On an ITO glass substrate [0382] sealing dispenser (a dispenser) at affixed alignment film buffed (inch> $ 7S'-SE_7492, Nissan Chemical Industries, Ltd.) in (60mmX70mmX0. 7mmt) in cross-sectional area 4000μm2 dispensing the coating liquid in Example 11 using the sealant composition:: (DDH curing agent) (curing agent Α-5) and Comparative Example 1. 其后,在基板上滴注液晶(TN液晶、MLC-11900-080、默克社制造),通过液晶滴注工艺(0DF工艺)使上下基板贴合,照射紫外线(UV照射装置:UVX-01224S1、USHI0INC.社制造,照度和照射时间:50mJ的情况下以50mW/cm2/365nm照射1秒,200mJ的情况下以50mW/cm2/365nm 照射4秒),使其固化,其后在120°C的热风烘箱中进行热固化1小时,制作出用于取向性试验的测试单元。 Thereafter, dropping liquid crystal (TN liquid crystal, MLC-11900-080, Merck Co., Ltd.) on the substrate by the liquid crystal dropping process (0DF process) the upper and lower substrates are bonded, ultraviolet rays (UV irradiation apparatus: UVX-01224S1 ., USHI0INC manufactured, illuminance and exposure time: the case of 50mJ is irradiated 50mW / cm2 / 365nm 1 sec, where 200mJ at 50mW / cm2 / 365nm irradiated for 4 seconds), and cured, followed by 120 ° C for hot air oven heat cured for 1 hour to prepare a test unit used for the alignment of the test. 此外,照度为OmJ的情况下,在贴合后利用遮光罩以对液晶和密封剂照射不到紫外线的状态在120°C的热风烘箱中进行热固化1小时,制作出用于取向性试验的测试单元。 In addition, the illuminance OmJ case, in order to fit the hood after use of the LCD is not irradiated with ultraviolet rays and sealants state in 120 ° C hot air oven heat cured for 1 hour to prepare a test for orientation test unit.

[0383] 对于得到的面板,确认了密封时的液晶的取向状态。 [0383] For the obtained panel was confirmed that the alignment state of liquid crystal at the time of sealing. 确认是利用光学显微镜进行的,将偏振片以正交尼科耳的状态夹持测试单元并以透过的方式进行观察。 It was confirmed using an optical microscope and a polarizing plate in a state of crossed Nicols and clamping manner through the test unit was observed. 观察在照度为200mJ、50mJ时液晶在角部和直线部的取向状态。 Observed illuminance 200mJ, 50mJ when the alignment state of the liquid crystal corner portion and a straight portion. 液晶的取向性的评价基准根据密封时有无取向混乱进行判断。 Have evaluation criteria liquid crystal orientation according to the time of sealing the alignment disorder is determined. 将密封时取向混乱为50μπι以下的情况作为"〇"、将具有其以上的取向混乱的情况作为"X"。 The orientation of the sealing disorder is 50μπι following cases as "square", having above its orientation confusion as "X". 结果列于表2。 The results are shown in Table 2.

[0384]【表1】 [0384] [Table 1]

[0385] [0385]

Figure CN104428339AD00401

[0386]【表2】 [0386] [Table 2]

[0387] [0387]

Figure CN104428339AD00402

[0388] 如表1所示,即使^玻璃与ITO玻^那样的^种材料彼k进行贴合的情况,使用了本发明的固化剂(实施例1〜5、8〜12、14)的液晶密封剂组合物的粘接强度也比使用了比较例1、2的固化剂的情况的大。 [0388] As shown in Table 1, even if the ^ glass and ITO glass ^ as ^ materials He k for the case of bonding, the use of the curing agent of this invention (Example 1~5,8~12,14) of bonding strength of the liquid crystal sealant composition than the case of using a curing agent of Example 1 is comparative large. 此外,实施例11 (固化剂A-5)的液晶密封剂组合物的取向膜的取向性在照度为50mJ、200mJ下密封时的取向混乱均为50μm以下,为良好的状态, 但是使用了比较例1的取向膜的取向性在照度为50mJ、200mJ下密封时的取向混乱均超过50μm。 In addition, the alignment of the alignment film of Example 11 (curing agent A-5) of the liquid crystal sealant composition embodiment of the illumination intensity of 50 mJ, orientation at the lower seal 200mJ confusion are 50μm or less, a good state, but the use of a relatively alignment of the alignment film of Example 1 in the illuminance orientation at the lower seal 50mJ, 200mJ confusion more than 50μm. 由该结果可确认到,本发明的固化剂、使用该固化剂的树脂组合物、液晶密封剂组合物适合于对在液晶显示面板等的粘接中使用的密封剂所要求的细线化和粘接性的多样化, 并且显现出可抑制在切出单元时和安装液晶盒驱动用IC时等的剥落的粘接强度。 From this result, it was confirmed that the curing agents of the present invention, the use of the curing agent resin composition, the liquid crystal sealant composition is suitable for thinning the sealing agent used in bonding the liquid crystal display panel or the like as required, and adhesion diversified, and exhibits a bonding strength of peeling when suppressed during cut-out unit and mounting the liquid crystal cell driving IC.

[0389](实施例15) [0389] (Example 15)

[0390] 准备在乙醇118g中溶解有六亚甲基二异氰酸酯17. 17g而成的溶解液A、以及在乙醇150g中溶解有乙二胺61.36g而成的溶解液B。 [0390] Preparation was dissolved in ethanol 118g has hexamethylene diisocyanate 17. 17g obtained by dissolving solution A, and dissolved in ethanol 150g of ethylenediamine dissolved solution 61.36g obtained by B. 在三口烧瓶中将溶解液B控制在25°C 进行搅拌,同时以I. 4g/分钟的速度滴加溶解液A。 Dissolving liquid B control was stirred at 25 ° C in a three-necked flask, at a rate of I. 4g / min was added dropwise lysate A. 溶解液A的滴加结束后,利用傅利叶变换红外分光光度计测定反应液,确认到来自异氰酸酯基的2250CHT1附近的峰消失后终止反应。 After dissolving solution A is added dropwise, using a Fourier transform infrared spectrophotometer reaction solution was confirmed to peak 2250CHT1 from the vicinity of the isocyanate groups of the reaction was terminated after the disappearance. 按照相对于六亚甲基二异氰酸酯1摩尔,乙二胺为10摩尔(以摩尔比计为1:10)的方式发生了反应。 It was reacted in accordance with hexamethylene diisocyanate, 1 mole of ethylenediamine 10 mol (molar ratio 1:10) manner.

[0391] 反应终止后,使用滤纸(桐山社制造No. 4)利用桐山漏斗(桐山社制造)进行过滤,进行脱液,用乙醇IOOml来清洗所得到的滤取物,进一步进行过滤,在真空烘箱中以50°C干燥所得到的滤取物。 [0391] After completion of the reaction, using a filter paper (Kiriyama manufactured No. 4) using a separatory funnel (Kiriyama Co., Ltd.) was filtered for liquid removal, with ethanol IOOml to wash the obtained filtrate was further filtered in vacuo oven to leach 50 ° C drying the resulting extract. 干燥后自然冷却至室温,利用高压粉碎机(商品名: nanojetmizer、AishinNanoTechnologiesCO.,LTD制造)进行粉碎,制造平均粒径(中值径)为2· 2μm的胺化合物(A-5)。 Naturally cooled after drying to room temperature, high-pressure pulverizer (trade name:. Nanojetmizer, AishinNanoTechnologiesCO, LTD, Ltd.) was pulverized, producing an average particle diameter (median diameter) 2 · 2μm amine compound (A-5).

[0392] 将上述得到的胺化合物(A-5)IOg与六亚甲基二异氰酸酯的I.36g在甲基环己烷80ml中混合,在50°C下进行24小时恒温处理。 [0392] The I.36g amine compound obtained above (A-5) IOg with diisocyanates hexamethylene mixed methylcyclohexane 80ml in 24 hours temperature treatment at 50 ° C.

[0393] 其后,使用滤纸(桐山社制造No. 4)利用桐山漏斗(桐山社制造)对处理液进行过滤,进行脱液。 [0393] Thereafter, using filter paper (Kiriyama manufactured No. 4) using a separatory funnel (Kiriyama Co., Ltd.) of the treatment liquid was filtered for liquid removal. 将所得到的滤取物混合在甲基环己烷IOOml中,进行与上述同样的过滤,重复进行该作业共3次。 The obtained filtrate was mixed methylcyclohexane IOOml, make the same filter described above, repeating this operation three times. 将最终滤取的物质利用真空干燥机(ESPEC社制造)在50°C、ITorr 下干燥12小时,得到含有用异氰酸酯化合物处理胺化合物而成的化合物的固化剂(EI)。 The material was finally collected by filtration using a vacuum dryer (by ESPEC Corp.) and dried at 50 ° C, ITorr 12 hours to obtain a curing agent compound treating the amine with an isocyanate compound obtained by containing (EI).

[0394] 将上述得到的胺化合物(A-5) 10g、六亚甲基二异氰酸酯I. 36g和氢化双酚A型环氧树脂(YX8034、JER社制造)1. 255g混合在甲苯80ml中,在50°C下进行24小时恒温处理。 [0394] The above obtained amine compound (A-5) 10g, hexamethylene diisocyanate I. 36g and hydrogenated bisphenol A epoxy resin (YX8034, JER Corp.) 1. 255g mixed in toluene 80ml, the for 24 hours temperature treatment at 50 ° C.

[0395] 其后,使用滤纸(桐山社制造No. 4)利用桐山漏斗(桐山社制造)对处理液进行过滤,进行脱液。 [0395] Thereafter, using filter paper (Kiriyama manufactured No. 4) using a separatory funnel (Kiriyama Co., Ltd.) of the treatment liquid was filtered for liquid removal. 将所得到的滤取物混合在甲苯IOOml中,进行与上述同样的过滤,重复进行该作业共3次。 The obtained filtrate was mixed in toluene IOOml, make the same filter described above, repeating this operation three times. 将最终滤取的物质利用真空干燥机(ESPEC社制造)在50°C、ITorr下干燥12小时,得到含有用异氰酸酯化合物和环氧树脂处理胺化合物而成的化合物的固化剂(E-2)。 The material was finally collected by filtration using a vacuum dryer (by ESPEC Corp.) and dried at 50 ° C, ITorr 12 hours to obtain a curing agent (E-2) a compound obtained by using an isocyanate compound and an epoxy resin of amine contained .

[0396]〔液晶密封剂组合物的制造〕 [0396] [Production of liquid crystal sealant composition]

[0397] 将上述得到的部分甲基丙烯酰化环氧树脂100质量份、作为无机填充剂的球状二氧化娃(Admafine社制造,S0-C1) 15质量份、作为有机填料的F-351 (日本Zeon社制造)15 质量份、作为光自由基引发剂的Irgacure907(BASFJapan社制造)3质量份、作为硅烷偶联剂的KBM-403 (信越化学工业社制造)2质量份、以及作为固化剂的EI或E-2混配, 相对于上述部分甲基丙烯酰化环氧树脂100质量份,该固化剂的混配量为15质量份,使用Three-OneMotordKA社制造,商品名;RW28basic)进行均匀分散,得到液晶密封剂树脂组合物。 [0397] A portion of the above obtained methyl acrylated epoxy resin 100 parts by mass, as an inorganic filler of spherical parts baby dioxide (manufactured by Admafine, S0-C1) 15 by mass, an organic filler, F-351 ( Japan Zeon Corp.) 15 parts by mass, as a photo-radical initiator Irgacure907 (BASFJapan Corp.) 3 parts by mass, as a silane coupling agent KBM-403 (Shin-Etsu chemical Co., Ltd.) 2 parts by mass, as well as the curing agent the EI or E-2 were blended with respect to 100 parts of the partial methyl acrylated epoxy mass, compounding amount of the curing agent is 15 parts by mass, using the Three-OneMotordKA Ltd., trade name; RW28basic) for uniformly dispersed to obtain a liquid crystal sealant resin composition.

[0398][评价] [0398] [Evaluation]

[0399](稳定性试验) [0399] (Stability test)

[0400] 液体稳定性 [0400] Liquid Stability

[0401] 上述得到的液晶密封剂组合物的初期的粘度是在其刚制备后(2小时以内)测定的。 [0401] Viscosity initial above-obtained liquid crystal sealant composition is after its freshly prepared (less than two hours) assay. 进而测定在25°C、2周后的粘度,以初期的粘度为基准,算出2周后的粘度的变化率/2 周)。 Furthermore measured at 25 ° C, the viscosity after 2 weeks, the viscosity early as a reference, the rate of change in viscosity after 2 weeks was calculated / week).

[0402] 需要说明的是,粘度如下测定。 [0402] Incidentally, the viscosity was measured as follows. 在RE-105U型粘度计(东机产业社制造)中安装3°XR7. 7锥形旋转器,将作为对象的液晶密封剂组合物0. 15ml放入锥性旋转器内,以2. 5rpm测定25°C下的液晶密封剂组合物的粘度。 Installation 3 ° XR7. 7 conical rotators RE-105U type viscometer (Toki Sangyo Co., Ltd.), the a target liquid crystal sealant composition 0. 15ml into the cone of the rotator to 2. 5rpm measuring the viscosity of the liquid crystal sealant composition at 25 ° C. 超出测定范围的情况下,无法测定。 Exceeding the measurement range and could not be measured. 需要说明的是,超出测定范围的基准是1,200,OOOmPa·s。 It should be noted that beyond the measurement range of reference is 1,200, OOOmPa · s.

[0403] 加热液体稳定性 [0403] heating liquid stability

[0404] 对上述得到的液晶密封剂组合物的初期的粘度进行测定,进而对40°C下22小时后的粘度进行测定,以初期的粘度为基准,算出加热22小时后的粘度的变化率/22小时)。 [0404] for viscosity initial above-obtained liquid crystal sealant composition was measured, and further on the viscosity after 22 hours 40 ° C for measurement, the viscosity initial calculated with reference heating rate of change in viscosity after 22 hours / 22 hours).

[0405] 液体稳定性和加热液体稳定性的结果列于表3。 Results [0405] liquid stability and the heating liquid stability are shown in Table 3.

[0406]【表3】 [0406] TABLE 3

[0407] [0407]

Figure CN104428339AD00421

[0408] 由表3的结果可知,对胺化合物加成任意的异氰酸酯而成的异氰酸酯加成胺化合物的液体稳定性、加热液体稳定性的变化率小,特别是加热液体稳定性的变化率明显小。 [0408] From the results of Table 3, the isocyanate of the amine compound addition of any isocyanate obtained by addition of liquid stability of the amine compound, a small change in the rate of heating the liquid stability, in particular the rate of change of the heating liquid stability is significantly small.

[0409](固化性试验) [0409] (Curing test)

[0410] 在以表4中记载的2个条件(仅120°C1小时,以及UV3000mJ/cm2处理后120°C1 小时)下对上述得到的液晶密封剂组合物(树脂组合物)进行固化处理,利用FT-IR测定所得到的固化片,进行固化性的评价。 [0410] In order to two conditions shown in Table 4 described (only 120 ° C1 hours, and UV3000mJ / cm2 120 ° C1 hours after treatment) of the above obtained liquid crystal sealant composition (resin composition) curing treatment under, using the cured sheet FT-IR measurement thus obtained were evaluated curability. 环氧固化率的计算方法使用下式。 Calculating an epoxy curing rate using the following formula. 另外,对于甲基丙烯酰固化率,可通过将下式中的环氧基的峰替换为甲基丙烯酰基的峰来算出。 In addition, a methacryloyloxy curing rate, by the peak replacing the formula of the epoxy group to methacryloyl group peaks calculated.

[0411]【数1】 [0411] [Equation 1]

[0412] [0412]

Figure CN104428339AD00422

[0413]基准峰;1540〜1480CHT1(峰顶1510CHT1附近) [0413] base peak; (near the peak 1510CHT1) 1540~1480CHT1

[0414] 环氧基的峰;925〜895cm1 (峰顶910cm1附近) Peak [0414] epoxy group; 925~895cm1 (peak 910cm1 nearby)

[0415] 甲基丙烯酰基的峰;1650〜1625CHT1(峰顶1635CHT1附近) [0415] methacryloyl peak; (near the peak 1635CHT1) 1650~1625CHT1

[0416]【表4】 [0416] [Table 4]

[0417] [0417]

Figure CN104428339AD00423

[0418] 由表4的结果可知,即使进行异氰酸酯处理,也观察不到显著的固化性的降低。 [0418] From the results of Table 4, even when the isocyanate process, also observed a significant reduction in curability. 艮P,即使进行异氰酸酯处理,固化性也不会降低,能够提高液体稳定性。 Gen P, even if the isocyanate process, curing is not reduced, it is possible to improve the liquid stability.

[0419] 工业实用性 [0419] Industrial Applicability

[0420] 根据本发明,可得到一种固化剂,其满足基于细线化和异种材料的多样化的粘接性的多样化的要求,并且,显现出可充分抑制在切出单元时和安装液晶盒驱动用IC时等的剥落的粘接强度,本发明的固化剂、使用该固化剂的树脂组合物和液晶密封剂组合物适合用作例如液晶显示面板等电子部件的密封剂或封装剂,在产业上有用。 [0420] According to the present invention, obtained one curing agent, which satisfies based on the required adhesion of diverse variety of fine lines and different materials, and exhibits sufficiently suppressed during cut-out unit and the mounting a liquid crystal cell driving bonding strength of peeling when using the IC, the curing agent of the present invention, the use of the curing agent resin composition and the liquid crystal sealant composition suitable for use as, for example, a liquid crystal display sealant electronic parts panel or encapsulant useful in the industry.

[0421] 日本专利申请2012-155976号的公开的全部内容通过参照引入至本说明书中。 [0421] The entire disclosure of Japanese Patent Application No. 2012-155976 by reference herein into the present specification.

[0422] 对于本说明书所记载的全部的文献、专利申请以及技术标准,各个文献、专利申请以及技术标准通过参照被引入是以具体且分别被记载的情况同等程度地通过参照被引入至本说明书中。 [0422] for all the publications, patent applications and technical standards described in the specification of each individual publication, patent applications, and technical standards by reference to be introduced it is specifically and are described in the case where the same extent be incorporated into the present specification by reference in.

[0423][符号说明] [0423] [Description of Symbols]

[0424] 1玻璃基板 [0424] a glass substrate

[0425] 2液晶密封剂组合物 [0425] the second liquid crystal sealant composition

[0426] 3液晶注入孔 [0426] 3 liquid crystal injection hole

[0427] 4玻璃基板 [0427] 4 a glass substrate

[0428] 5液晶封入用单元 [0428] 5 of the liquid crystal sealed unit

[0429] 6 液晶 [0429] 6 of the liquid crystal

[0430] 7液晶显示面板 [0430] 7 liquid crystal display panel

[0431] 8ITO玻璃 [0431] 8ITO glass

[0432] 9 玻璃 [0432] 9 Glass

[0433] 10试验片 [0433] 10 test piece

Claims (14)

  1. 1. 一种固化剂,其为环氧树脂和/或分子内具有至少1个不饱和键的树脂用的固化剂, 该固化剂包含通过异氯酸醋化合物与脱或与分子内具有2个W上伯氨基的多元胺化合物的反应而得到的在分子内具有至少1个伯氨基的化合物。 A curing agent having at least one unsaturated bond resin curing agent to an epoxy resin and / or molecules, the curing agent comprises exclusive-acid vinegar compound removal, or having two intramolecular the reaction polyvalent amine compound on W a primary amino group of the obtained at least one compound having a primary amino group in the molecule.
  2. 2. -种固化剂,其为环氧树脂和/或分子内具有至少1个不饱和键的树脂用的固化剂, 该固化剂包含下述式(I)表示的在分子内具有至少1个伯氨基的化合物, 【化46】 2. - curing agents having at least one unsaturated bond resin curing agent to an epoxy resin and / or molecules, the curing agent comprises represented by the following formula (I) having at least one in the molecule compound having a primary amino group, [Chemical Formula 46]
    Figure CN104428339AC00021
    式(I)中, Ri为单键,或者为Cl〜Ci2亚焼基、被1个或1个W上的NH或0原子非连续间断的C2〜 Ci2亚焼基、〔3〜Ci2亚环焼基、。 In the formula (I), Ri is a single bond, or a Cl~Ci2 alkylene firing group, the non-continuous interrupted one or a NH or 0 atoms on the W C2~ Ci2 alkylene firing group, [3~Ci2 cycloalkylene firing group. 〜Ci2亚焼基-〔3〜Ci2亚环焼基、。 ~Ci2 alkylene firing yl - [3~Ci2 cycloalkylene firing group. 〜Ci2亚焼基-〔3〜 Ci2亚环焼基-Cl〜Ci2亚焼基、Cs〜Ci2亚环焼基-Cl〜Ci2亚焼基-Cs〜Ci2亚环焼基、Ce〜 Cm亚芳基、Cl〜C4亚焼基-Ce〜Cm亚芳基、Cl〜C4亚焼基-Ce〜Cm亚芳基-Cl〜C4亚焼基、或Ce〜Ci4亚芳基-Cl〜C4亚焼基-Ce〜Cm亚芳基,其中所述C2〜Ci2亚焼基中与N原子键合的H原子可W被氨基或Cl〜的焼基氨基取代;此处,亚焼基为直链或支链,可W 取代有团素,〔3〜Ci2亚环焼基或Q〜Cm亚芳基无取代、或者取代有团素或。 ~Ci2 alkylene firing yl - [3~ Ci2 cycloalkylene firing group -Cl~Ci2 alkylene firing group, Cs~Ci2 cycloalkylene firing group -Cl~Ci2 alkylene firing group -Cs~Ci2 cycloalkylene firing group, Ce~ Cm arylene group, Cl~C4 alkylene firing group -Ce~Cm arylene, Cl~C4 alkylene firing group -Ce~Cm arylene -Cl~C4 alkylene firing group, or Ce~Ci4 arylene -Cl~C4 alkylene ware group -Ce~Cm arylene, wherein said C2~Ci2 alkylene firing group with the N-bonded H atoms may be W is a substituted amino group or Cl~ the firing group; where alkylene ware group is a straight-chain or branched chain, may be substituted with W with a group of elements, [3~Ci2 cycloalkylene firing group or Q~Cm arylene group unsubstituted or substituted with a group of biotin or. 〜C4焼基, n 为1、2、3 或4, n为2 W上时,Ri相互独立,含义与上述相同; n为1时,A为Cl〜Ci2焼基、被1个或1个W上的0原子非连续间断的C2〜Ci2焼基、 C2〜Ci2焼氧撰基亚焼基、C3〜Ci2环焼基、Cl〜Ci2焼基-C3〜Ci2亚环焼基、C3〜Ci2环焼基-Cl〜C。 ~C4 firing group, n is 2, 3 or 4, n is the upper 2 W, Ri independently of each other, meaning the same as above; when 1 n is, A is Cl~Ci2 firing group, with one or a 0 atoms on the W non-continuous intermittent C2~Ci2 firing group, C2~Ci2 firing oxygen essays Nokia firing group, C3~Ci2 ring firing group, Cl~Ci2 firing group -C3~Ci2 cycloalkylene firing group, C3~Ci2 cycloalkyl firing group -Cl~C. 亚焼基-C3〜C。 Alkylene firing group -C3~C. 亚环焼基、Ce〜Ci4芳基、Cl〜C4焼基-Ce〜Ci4亚芳基、Ce〜 Cm芳基-Cl〜C4亚焼基-Ce〜Cm亚芳基、或者(甲基)丙帰醜氧基焼基,此处,亚焼基为直链或支链,可W取代有团素,C3〜Ci2环焼基、C3〜Ci2亚环焼基、Ce〜Ci4芳基或Ce〜。 Cycloalkylene firing group, Ce~Ci4 aryl group, Cl~C4 firing group -Ce~Ci4 arylene, Ce~ Cm aryl -Cl~C4 alkylene firing group -Ce~Cm arylene group, or a (meth) acrylic kaesa ugly group ware group, where, alkylene ware group is a straight chain or branched chain, may be substituted with W with a group element, C3~Ci2 ring firing group, C3~Ci2 cycloalkylene firing group, Ce~Ci4 aryl group or Ce~ . 4 亚芳基无取代、或者取代有团素或。 4 arylene group unsubstituted or substituted with a group of biotin or. 〜C4焼基; n为2时,A为Cl〜Ci2亚焼基、被1个或1个W上的0原子非连续间断的C2〜Ci2亚焼基、Cl〜C。 ~C4 firing group; n is 2, A is a Cl~Ci2 alkylene firing group, the 0 atom on one or a W discontinuous interrupted C2~Ci2 alkylene firing group, Cl~C. 亚焼氧撰基亚焼基、C3〜C。 Alkylene firing oxygen essays Nokia firing group, C3~C. 亚环焼基、Cl〜C。 Cycloalkylene firing group, Cl~C. 亚焼基-C3〜C。 Alkylene firing group -C3~C. 亚环焼基、Cl〜 Ci2亚焼基-〔3〜Ci2亚环焼基-。 Cycloalkylene firing group, Cl~ Ci2 alkylene firing yl - [3~Ci2 cycloalkylene firing group -. 〜Ci2亚焼基、〔3〜Ci2亚环焼基-。 ~Ci2 alkylene firing group, [3~Ci2 cycloalkylene firing group -. 〜Ci2亚焼基-〔3〜 Ci2亚环焼基、_〔3〜Ci2环焼_基、Ce〜Ci4亚芳基、Cl〜〔4亚焼基-Ce〜Ci4亚芳基-Cl〜 〔4亚焼基、或者Ce〜亚芳基-Cl〜〔4亚焼基-Ce〜亚芳基,此处,亚焼基为直链或支链,可W取代有团素,C3〜Ci2亚环焼基、Q〜Cm亚芳基无取代、或者取代有团素或Cl〜C4 焼基; n为3时,A为下述式(1)、下述式(2)或下述式(3), 【化47】 ~Ci2 alkylene firing yl - [3~ Ci2 cycloalkylene firing group, _ [3~Ci2 cycloalkyl firing _ group, Ce~Ci4 arylene, Cl~ [4 alkylene firing group -Ce~Ci4 arylene -Cl~ [ 4 alkylene firing group, or Ce~ arylene -Cl~ [4 alkylene firing group -Ce~ arylene group, here, alkylene ware group is a straight chain or branched chain, may be substituted with W with a group of factors, C3~Ci2 alkylene firing cycloalkyl group, Q~Cm unsubstituted arylene, or substituted with groups biotin or Cl~C4 ware group; n is 3, A is the following formula or the following formula (1), the following formula (2) ( 3), [Chemical Formula 47]
    Figure CN104428339AC00022
    Figure CN104428339AC00031
    式(1)中,R2相同或不同,为直链或支链的Cl〜Ci2亚焼基, 【化48】 Formula (1), R2 are the same or different, is Cl~Ci2 alkylene firing of straight-chain or branched, [Chemical Formula 48]
    Figure CN104428339AC00032
    式(2)中,R3相同或不同,为直链或支链的Cl〜Ci2亚焼基, 【化49】 Formula (2), R3 is the same or different, is Cl~Ci2 alkylene firing of straight-chain or branched, [Chemical Formula 49]
    Figure CN104428339AC00033
    式(3)中,R4相同或不同,为直链或支链的Cl〜C。 Of formula (3), R4 is the same or different, is a straight-chain or branched Cl~C. 亚焼基,R5为CH; n为4时,A为下述式(4), 【化50】 Alkylene firing group, R5 is CH; n is 4, A represented by the following formula (4), [Chemical Formula 50]
    Figure CN104428339AC00034
    式(4)中,X3为Si,或者为由C3〜Ci2环焼基-Cl〜Ci2亚焼基-C3〜Ci2环焼基、或Ce〜 Cm芳基-Cl〜C4亚焼基-Q〜Ci4芳基衍生的4价残基,此处,亚焼基为直链或支链,可W 取代有1〜6个团素,Cg〜Ci2环焼基或Cg〜Cm芳基无取代、或者取代有团素或。 (4) In the formula, X3 is Si, or by C3~Ci2 cycloalkyl firing group -Cl~Ci2 alkylene firing group -C3~Ci2 ring firing group, or Ce~ Cm aryl -Cl~C4 alkylene firing group -Q~ Ci4 aryl group derived from a tetravalent residue, where, alkylene ware group is a straight chain or branched chain, may be substituted with W have 1~6 regiments prime, Cg~Ci2 ring firing group or Cg~Cm aryl group unsubstituted or substituted with a group biotin or. 〜C4焼基。 ~C4 firing base.
  3. 3.如权利要求2所述的固化剂,其中,在分子内具有至少1个伯氨基的化合物为下述式(la), 【化51】 Curing agent according to 2 claim, wherein the compound having at least one primary amino group having the following formula (La) in the molecule, [Chemical Formula 51]
    Figure CN104428339AC00035
    式中, In the formula,
    Figure CN104428339AC00036
    Figure CN104428339AC00037
    Figure CN104428339AC00038
    Figure CN104428339AC00039
    Figure CN104428339AC000310
    Ri相互独立,含义与权利要求2中相同, XI为Cl〜Ci2亚焼基、被1个或1个W上的0原子非连续间断的C2〜Ci2亚焼基、Cl〜 Ci2亚焼氧撰基亚焼基、C3〜Ci2亚环焼基、。 Ri independently of each other, 2 the same meaning as claimed in claim, XI is Cl~Ci2 alkylene firing group, the 0 atom on one or a W discontinuous interrupted C2~Ci2 alkylene firing group, Cl~ Ci2 alkylene firing oxygen essays Nokia firing group, C3~Ci2 firing cycloalkylene group. 〜Ci2亚焼基-C3〜Ci2亚环焼基、。 ~Ci2 alkylene firing group -C3~Ci2 cycloalkylene firing group. 〜Ci2亚焼基-〔3〜Ci2亚环焼基-。 ~Ci2 alkylene firing yl - [3~Ci2 cycloalkylene firing group -. 〜Ci2亚焼基、〔3〜Ci2亚环焼基-。 ~Ci2 firing alkylene group, a cycloalkylene [3~Ci2 firing group -. 〜Ci2亚焼基-〔3〜Ci2亚环焼基、二C3〜Ci2环焼二基、Ce〜Ci4亚芳基、Cl〜C4亚焼基-Ce〜Ci4亚芳基-Cl〜C4亚焼基、或Q〜Ci4亚芳基-Cl〜C4亚焼基-Q〜亚芳基,此处,亚焼基为直链或支链,可W 取代有团素,〔3〜Ci2亚环焼基或Q〜Cm亚芳基无取代、或者取代有团素或。 ~Ci2 firing alkylene group - [3~Ci2 firing cycloalkylene group, two C3~Ci2 cyclic firing diyl, Ce~Ci4 arylene, Cl~C4 alkylene group -Ce~Ci4 firing firing alkylene arylene -Cl~C4 group, or Q~Ci4 arylene -Cl~C4 alkylene firing group -Q~ arylene group, here, alkylene ware group is a straight chain or branched chain, may be substituted with W with a group of elements, [3~Ci2 cycloalkylene ware group or Q~Cm arylene group unsubstituted or substituted with a group of biotin or. 〜C4焼基。 ~C4 firing base.
  4. 4. 如权利要求2所述的固化剂,其中,在分子内具有至少1个伯氨基的化合物为下述式(Ila), 【化52】 Said curing agent 2 as claimed in claim, wherein the compound having at least one primary amino group having the following formula (Ila) in the molecule, [Chemical Formula 52]
    Figure CN104428339AC00041
    式中, Ri的含义与权利要求2中相同, X2为Cl〜Ci2焼基、被1个或1个W上的0原子非连续间断的C2〜Ci2焼基、Cl〜 焼氧撰基亚焼基、〔3〜Ci2环焼基、Cl〜Ci2焼基-〔3〜Ci2亚环焼基、〔3〜Ci2环焼基-Cl〜 Ci2亚焼基-〔3〜Ci2亚环焼基、Ce〜Ci4芳基、。 Wherein, Ri of meaning claim same 2, an X2 is a Cl~Ci2 firing group claim is 0 atoms on one or a W discontinuous interrupted C2~Ci2 firing group, Cl~ firing oxygen essays sulfoxide ware group, [3~Ci2 ring firing group, Cl~Ci2 firing yl - [3~Ci2 cycloalkylene firing group, [3~Ci2 ring firing group -Cl~ Ci2 alkylene firing yl - [3~Ci2 cycloalkylene firing group, Ce ~Ci4 aryl group. 〜〔4焼基-Ce〜Ci4亚芳基、Ce〜Ci4芳基-Cl〜〔4亚焼基-Ce〜Ci4亚芳基、或者(甲基)丙帰醜氧基焼基,此处,亚焼基为直链或支链,可W取代有团素,C3〜Ci2环焼基、C3〜Ci2亚环焼基、Ce〜Cm芳基或Ce〜Cm亚芳基无取代、或者取代有团素或Cl〜C4焼基。 ~ [4 ware group -Ce~Ci4 arylene, Ce~Ci4 aryl -Cl~ [4 alkylene firing group -Ce~Ci4 arylene group, or a (meth) acrylic kaesa ugly group ware group, where, firing alkylene group is a straight chain or branched chain, may be substituted with a W group element, C3~Ci2 firing cycloalkyl group, C3~Ci2 firing a cycloalkylene group, an aryl group or Ce~Cm Ce~Cm unsubstituted arylene, or substituted with biotin or group Cl~C4 firing group.
  5. 5. 如权利要求1〜4的任一项所述的固化剂,其中,所述固化剂进一步包含用异氯酸醋化合物处理上述在分子内具有至少1个伯氨基的化合物而得到的化合物。 5. A curing agent according to any one of claims 1 ~ 4 claims, wherein the curing agent further compound obtained by processing the above-described compound having at least one primary amino group in the molecule with a different acid vinegar compound comprising.
  6. 6. 如权利要求1〜4的任一项所述的固化剂,其中,所述固化剂进一步包含用异氯酸醋化合物和环氧树脂处理上述在分子内具有至少1个伯氨基的化合物而得到的化合物。 6. A curing agent according to any one of claims 1 ~ 4 claims, wherein the curing agent further comprising processing the compound having at least one primary amino group in the molecule with a different acid vinegar compound and an epoxy resin compounds obtained.
  7. 7. 如权利要求1〜4的任一项所述的固化剂,其中,所述固化剂进一步包含用异氯酸醋化合物和具有轻基的化合物处理上述在分子内具有至少1个伯氨基的化合物而得到的化合物。 7. A curing agent according to any one of claims 1 ~ 4 claims, wherein the curing agent further compounds with different acid vinegar compound having a light group comprises processing said at least one primary amino group in the molecule compounds obtained.
  8. 8. -种树脂组合物,其包含权利要求1〜7的任一项所述的固化剂(A)、W及环氧树脂和/或具有至少1个不饱和键的树脂炬)。 8. - kind of the resin composition, comprising as claimed in claim curing agent (A) according to any one 1~7 according to, W, and an epoxy resin and / or having at least one unsaturated bond resin torch).
  9. 9. 如权利要求8所述的树脂组合物,其中,环氧树脂为相对于环氧树脂的环氧基1当量使10当量%〜90当量%的(甲基)丙帰酸对其反应而得到的偏醋化环氧树脂。 9. The resin composition according to claim 8, wherein the epoxy resin is an epoxy resin with respect to 1 equivalent of the epoxy group to make 10% ~ 90 equivalent% eq (meth) acrylic acid and its reaction and kaesa the vinylidene esterified epoxy resin.
  10. 10. 如权利要求8或9所述的树脂组合物,其中,相对于环氧树脂的环氧基1当量,固化剂(A)所含有的伯氨基的总量为0. 001当量〜10当量。 10. The resin composition 8 or claim 9, wherein, with respect to equivalent of epoxy resin is epoxy group, the total amount of the primary amino group of the curing agent (A) contained is 0.001 equivalents ~10 equiv. .
  11. 11. 如权利要求8〜10的任一项所述的树脂组合物,其中,相对于环氧树脂的环氧基1 当量与分子内具有至少1个不饱和键的树脂的不饱和键1当量的合计,固化剂(A)所含有的伯氨基的总量为化001当量〜10当量。 The resin composition according to any of 8~10 of claims, wherein, with respect to the epoxy group equivalent of the molecule an epoxy resin having at least one unsaturated bond in the resin an unsaturated bond 1 eq. sum, the total amount of the primary amino group of the curing agent (a) contained is of 001 eq ~ 10 eq.
  12. 12. -种液晶密封剂组合物,其含有权利要求8〜11的任一项所述的树脂组合物。 12. - kind of the liquid crystal sealant composition, comprising as claimed in claim resin composition according 8~11 of one of the.
  13. 13. -种液晶显示面板,其通过使用权利要求12所述的液晶密封剂组合物而得到。 13. - kind of liquid crystal display panel, which is obtained by the use as claimed in claim liquid crystal sealant composition 12.
  14. 14. 一种液晶显示面板的制造方法,其中,在液晶滴注工艺中,使用权利要求12所述的 The method of manufacturing a panel 14. A liquid crystal display, wherein, in the liquid crystal dropping process, a claimed in claim 12, wherein
    Figure CN104428339AC00042
    液晶密封剂组合物,进行光固化后进行热固化。 The liquid crystal sealant composition, the photocured thermally cured.
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