JP6031514B2 - Curing agent and resin composition using the same - Google Patents

Description

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

  In recent years, with the expansion and narrowing of the display portion of a liquid crystal display, the sealing agent has been made thinner. In addition, not only glass but also inorganic materials such as ITO electrodes and SiN films, organic materials such as alignment films, etc. can be applied as adhesion targets for sealing agents. There is a demand for diversification of adhesiveness that enables mutual bonding.

  As a sealing agent for adhering such different materials, for example, a sealing agent for liquid crystal display elements that contains a curable resin such as epoxy (meth) acrylate, a curing agent such as a thermal epoxy curing agent, and does not contain an inorganic filler. It has been proposed (Patent Document 1). Thermal epoxy hardeners used in this sealing agent for liquid crystal display elements include dihydrazide compounds such as sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, and other commercially available products such as Amicure VDH and Amicure UDH (all of which are Ajinomoto Fine Techno Co., Ltd.) Manufactured) and the like.

JP 2010-85712 A

  Combined with the thinning of the sealing agent and the diversification of adhesiveness, the sealing agent has further improved adhesive strength in order to suppress peeling when the cell is cut out and when the IC for driving the liquid crystal cell is mounted. It has been demanded.

  An object of the present invention is to find a latent curing agent that can satisfy the demands of thinning of a sealing agent and diversification of adhesiveness and improve adhesive strength, and has at least one epoxy resin and / or one molecule in the molecule. It is to provide a curing agent for a resin having an unsaturated bond, a resin composition using the same, and a liquid crystal sealant composition.

  As a result of repeated studies to solve the above problems, the present inventors have found that at least one compound having a urea structure in the molecule and having at least one primary amino group is present in the epoxy resin and / or in the molecule. By using a latent curing agent for a resin having one unsaturated bond, it is possible to adapt to thinning of the sealing agent for liquid crystal display panels and the like and diversification of adhesiveness, and to improve the adhesive strength. The present inventors have found that a resin composition and a liquid crystal sealing agent composition can be obtained.

That is, the present invention is as described in [1] to [14].
[1] A compound having at least one primary amino group in the molecule, obtained by reacting an isocyanate compound with hydrazine or a polyvalent amine compound having two or more primary amino groups in the molecule. The curing agent for epoxy resins and / or resins having at least one unsaturated bond in the molecule.

〔式中
Ｒ^１は、単結合であるか、あるいはＣ_１〜Ｃ_１２アルキレン、１つ若しくはそれ以上のＮＨ（イミノ基）若しくはＯ原子（酸素原子）で非連続的に中断されたＣ_２〜Ｃ_１２アルキレン（Ｎ原子（窒素原子）に結合するＨ原子（水素原子）は、アミノ基又はＣ_１〜Ｃ_１２のアルキルアミノ基で置換されていてもよい）、Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_１２アルキレン、Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_６〜Ｃ_１４アリーレン、Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン、Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン、又はＣ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン（ここで、アルキレンは、直鎖又は分岐鎖であり、ハロゲンで置換されていてもよく、Ｃ_３〜Ｃ_１２シクロアルキレン又はＣ_６〜Ｃ_１４アリーレンは、非置換であるか、又はハロゲン若しくはＣ_１〜Ｃ_４アルキルで置換されている）であり、
ｎは、１、２、３又は４であり、
ｎが２以上の場合は、Ｒ^１は、互いに独立して、上記と同義であり、
ｎが１の場合、Ａは、Ｃ_１〜Ｃ_１２アルキル、１つ若しくはそれ以上のＯ原子（酸素原子）で非連続的に中断されたＣ_２〜Ｃ_１２アルキル、Ｃ_２〜Ｃ_１２アルキルオキシカルボニルアルキレン、Ｃ_３〜Ｃ_１２シクロアルキル、Ｃ_１〜Ｃ_１２アルキル−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_３〜Ｃ_１２シクロアルキル−Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_６〜Ｃ_１４アリール、Ｃ_１〜Ｃ_４アルキル−Ｃ_６〜Ｃ_１４アリーレン、Ｃ_６〜Ｃ_１４アリール−Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン（ここで、アルキレンは、直鎖又は分岐鎖であり、ハロゲンで置換されていてもよく、Ｃ_３〜Ｃ_１２シクロアルキル、Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_６〜Ｃ_１４アリール、又はＣ_６〜Ｃ_１４アリーレンは、非置換であるか、又はハロゲン若しくはＣ_１〜Ｃ_４アルキルで置換されている）、又は（メタ）アクリロイルオキシアルキルであり、
ｎが２の場合、Ａは、Ｃ_１〜Ｃ_１２アルキレン、１つ若しくはそれ以上のＯ原子（酸素原子）で非連続的に中断されたＣ_２〜Ｃ_１２アルキレン、Ｃ_１〜Ｃ_１２アルキレンオキシカルボニルアルキレン、Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_１２アルキレン、Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、ジＣ_３〜Ｃ_１２シクロアルカンジイル、Ｃ_６〜Ｃ_１４アリーレン、Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン、又はＣ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン（ここで、アルキレンは、直鎖又は分岐鎖であり、ハロゲンで置換されていてもよく、Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_６〜Ｃ_１４アリーレンは、非置換であるか、又はハロゲン若しくはＣ_１〜Ｃ_４アルキルで置換されている）であり、
ｎが３の場合、Ａは、下記式（１）

（式中、Ｒ^２は、同一又は異なり、直鎖又は分岐鎖のＣ_１〜Ｃ_１２アルキレンである）、下記式（２）

（式中、Ｒ^３は、同一又は異なり、直鎖又は分岐鎖のＣ_１〜Ｃ_１２アルキレンである）又は下記式（３）

（式中、Ｒ^４は、同一又は異なり、直鎖又は分岐鎖のＣ_１〜Ｃ_１２アルキレンであり、Ｒ^５は、ＣＨである）であり、
ｎが４の場合は、Ａは、下記式（４）

｛式中、Ｘ^３は、Ｓｉであるか、又はＣ_３〜Ｃ_１２シクロアルキル−Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキル、若しくはＣ_６〜Ｃ_１４アリール−Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリール（ここで、アルキレンは、直鎖又は分岐鎖であり、１〜６のハロゲンで置換されていてもよく、Ｃ_３〜Ｃ_１２シクロアルキル又はＣ_６〜Ｃ_１４アリールは、非置換であるか、又はハロゲン若しくはＣ_１〜Ｃ_４アルキルで置換されている）から誘導される４価の残基である｝である〕で示される分子内に少なくとも１個の第１級アミノ基を有する化合物を含む、エポキシ樹脂及び／又は分子内に少なくとも１個の不飽和結合を有する樹脂用の硬化剤に関する。[2] Formula (I)

[Wherein R ¹ is either a single bond or a _C 1 _{-C 12} alkylene, one or more NH (imino group) or non-continuously interrupted _C 2 ~ by O atom (an oxygen atom) C ₁₂ alkylene (the H atom (hydrogen atom) bonded to the N atom (nitrogen atom) may be substituted with an amino group or a C _{1 to} C ₁₂ alkylamino group), C _{3 to} C ₁₂ cycloalkylene, C ₁ -C ₁₂ alkylene-C ₃ -C ₁₂ cycloalkylene, C ₁ -C ₁₂ alkylene-C ₃ -C ₁₂ cycloalkylene-C ₁ -C ₁₂ alkylene, C ₃ -C ₁₂ cycloalkylene-C ₁ -C ₁₂ alkylene _-C 3 _{-C 12 cycloalkylene,} C 6 _{-C 14 arylene,} C 1 -C ₄ alkylene _-C 6 _{-C 14 arylene,} C 1 -C ₄ alkylene -C ₆ -C ₁₄ arylene _-C 1 -C ₄ alkylene, or _C 6 _{-C 14} arylene _-C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene (where alkylene is linear or branched, halogen may be _substituted, C 3 _{-C 12} cycloalkylene or _C 6 _{-C 14} arylene is unsubstituted or substituted by halogen or _C 1 -C ₄ alkyl),
n is 1, 2, 3 or 4;
when n is 2 or more, R ¹ is independently the same as defined above;
When n is 1, A is C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkyl, C ₂ -C ₁₂ alkyloxy discontinuously interrupted by one or more O atoms (oxygen atoms) carbonyl _alkylene, C 3 _{-C 12 cycloalkyl,} C 1 _{-C 12} alkyl _-C 3 _{-C 12 cycloalkylene,} C 3 _{-C 12} cycloalkyl _-C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene, C ₆ -C _{14 aryl,} C 1 -C ₄ alkyl _-C 6 _{-C 14 arylene,} C 6 _{-C 14} aryl _-C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene (where alkylene is straight-chain or a branched chain, may be substituted by _halogen, C 3 _{-C 12 cycloalkyl,} C 3 _{-C 12 cycloalkylene,} C 6 _{-C 14} aryl, or ₆ -C ₁₄ arylene is unsubstituted or substituted by halogen or _C 1 -C ₄ alkyl), or (meth) acryloyloxy alkyl,
When n is 2, A is C ₁ -C ₁₂ alkylene, C ₂ -C ₁₂ alkylene, C ₁ -C ₁₂ alkyleneoxy discontinuously interrupted by one or more O atoms (oxygen atoms) carbonyl _alkylene, C 3 _{-C 12 cycloalkylene,} C 1 _{-C 12} alkylene _-C 3 _{-C 12 cycloalkylene,} C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12} alkylene, _{C 3} -C ₁₂ cycloalkylene _-C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene, di _C 3 _{-C 12 cycloalkanediyl,} C 6 _{-C 14 arylene,} C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene _-C 1 -C ₄ alkylene, or _C 6 _{-C 14} arylene _-C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene Here, the alkylene is a straight-chain or branched-chain, may be substituted by _halogen, C 3 _{-C 12 cycloalkylene,} C 6 _{-C 14} arylene, unsubstituted or halogen or _{C 1} ~C is ₄ substituted with alkyl),
When n is 3, A is the following formula (1)

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

(Wherein R ³ are the same or different and are linear or branched C _{1 to} C ₁₂ alkylene) or the following formula (3)

Wherein R ⁴ is the same or different and is a linear or branched C _{1 to} C ₁₂ alkylene and R ⁵ is CH.
When n is 4, A is the following formula (4)

{Wherein X ³ is Si or C ₃ -C ₁₂ cycloalkyl-C ₁ -C ₁₂ alkylene-C ₃ -C ₁₂ cycloalkyl, or C ₆ -C ₁₄ aryl-C ₁ -C _4. Alkylene-C ₆ -C ₁₄ aryl (wherein alkylene is linear or branched and may be substituted with 1-6 halogens, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₁₄ aryl) Is a tetravalent residue that is unsubstituted or substituted with a halogen or C ₁ -C ₄ alkyl)} in the molecule at least one first The present invention relates to a curing agent for an epoxy resin containing a compound having a secondary amino group and / or a resin having at least one unsaturated bond in the molecule.

〔式中、
Ｒ^１は、互いに独立して、上記［２］と同義であり、
Ｘ^１は、Ｃ_１〜Ｃ_１２アルキレン、１つ若しくはそれ以上のＯ原子（酸素原子）で非連続的に中断されたＣ_２〜Ｃ_１２アルキレン、Ｃ_１〜Ｃ_１２アルキレンオキシカルボニルアルキレン、Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_１２アルキレン、Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、ジＣ_３〜Ｃ_１２シクロアルカンジイル、Ｃ_６〜Ｃ_１４アリーレン、Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン、又はＣ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン（ここで、アルキレンは、直鎖又は分岐鎖であり、ハロゲンで置換されていてもよく、Ｃ_３〜Ｃ_１２シクロアルキレン又はＣ_６〜Ｃ_１４アリーレンは、非置換であるか、又はハロゲン若しくはＣ_１〜Ｃ_４アルキルで置換されている）である〕である、上記［２］記載の硬化剤に関する。[3] A compound having at least one primary amino group in the molecule is represented by the following formula (Ia):

[Where,
R ¹ , independently of ^one another, has the same meaning as [2] above,
X ¹ is C ₁ -C ₁₂ alkylene, C ₂ -C ₁₂ alkylene, C ₁ -C ₁₂ alkyleneoxycarbonylalkylene, C ₃ discontinuously interrupted by one or more O atoms (oxygen atoms) -C _{12 cycloalkylene,} C 1 _{-C 12} alkylene _-C 3 _{-C 12 cycloalkylene,} C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12 alkylene,} C 3 _{-C 12} cycloalkylene -C ₁ -C ₁₂ alkylene _-C 3 _{-C 12} cycloalkylene, di _C 3 _{-C 12 cycloalkanediyl,} C 6 _{-C 14 arylene,} C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene _-C 1 ~ C ₄ alkylene, or C ₆ -C ₁₄ arylene-C ₁ -C ₄ alkylene-C ₆ -C ₁₄ arylene (wherein Alkylene is a straight-chain or branched-chain, may be substituted by _halogen, C 3 _{-C 12} cycloalkylene or _C 6 _{-C 14} arylene, unsubstituted or halogen or _C 1 -C ₄ And the curing agent according to the above [2].

〔式中、
Ｒ^１は、上記［２］と同義であり、
Ｘ^２は、Ｃ_１〜Ｃ_１２アルキル、１つ若しくはそれ以上のＯ原子（酸素原子）で非連続的に中断されたＣ_２〜Ｃ_１２アルキル、Ｃ_１〜Ｃ_１２アルキルオキシカルボニルアルキレン、Ｃ_３〜Ｃ_１２シクロアルキル、Ｃ_１〜Ｃ_１２アルキル−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_３〜Ｃ_１２シクロアルキル−Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_６〜Ｃ_１４アリール、Ｃ_１〜Ｃ_４アルキル−Ｃ_６〜Ｃ_１４アリーレン、Ｃ_６〜Ｃ_１４アリール−Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン（ここで、アルキレンは、直鎖又は分岐鎖であり、ハロゲンで置換されていてもよく、Ｃ_３〜Ｃ_１２シクロアルキル、Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_６〜Ｃ_１４アリール又はＣ_６〜Ｃ_１４アリーレンは、非置換であるか、又はハロゲン若しくはＣ_１〜Ｃ_４アルキルで置換されている）、又は（メタ）アクリロイルオキシアルキルである〕である、上記［２］記載の硬化剤に関する。[4] A compound having at least one primary amino group in the molecule is represented by the following formula (IIa):

[Where,
R ¹ has the same meaning as [2] above,
X ² is C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkyl interrupted discontinuously with one or more O atoms (oxygen atoms), C ₁ -C ₁₂ alkyloxycarbonylalkylene, C ₃ -C _{12 cycloalkyl,} C 1 _{-C 12} alkyl _-C 3 _{-C 12 cycloalkylene,} C 3 _{-C 12} cycloalkyl _-C 1 _{-C 12} alkylene _-C 3 _{-C 12 cycloalkylene,} C 6 _{-C 14} aryl C ₁ -C ₄ alkyl-C ₆ -C ₁₄ arylene, C ₆ -C ₁₄ aryl-C ₁ -C ₄ alkylene-C ₆ -C ₁₄ arylene (wherein alkylene is linear or branched, may be substituted with _halogen, C 3 _{-C 12 cycloalkyl,} C 3 _{-C 12 cycloalkylene,} C 6 _{-C 14} aryl or _C 6 _{-C 14} Arylene is unsubstituted or substituted with halogen or C ₁ -C ₄ alkyl), or (meth) acryloyloxyalkyl]. The curing agent according to [2] above.

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

[6] Any one of the above-mentioned [1] to [4], further comprising a compound obtained by treating a compound having at least one primary amino group in the molecule with an isocyanate compound and an epoxy resin. It relates to the curing agent described in 1.

[7] Any of the above [1] to [4], further comprising a compound obtained by treating a compound having at least one primary amino group in the molecule with an isocyanate compound and a compound having a hydroxy group It relates to the hardening | curing agent as described in any one.

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

[9] The above-mentioned [8], wherein the epoxy resin is a partially esterified epoxy resin obtained by reacting 10 to 90 equivalent% of (meth) acrylic acid with respect to 1 equivalent of an epoxy group of the epoxy resin. The present invention relates to a resin composition.

[10] The above [8] or [9], wherein the total amount of primary amino groups contained in the curing agent (A) is 0.001 to 10 equivalents relative to 1 equivalent of epoxy groups of the epoxy resin. The present invention relates to a resin composition.

[11] The primary amino group contained in the curing agent (A) with respect to the sum of one equivalent of epoxy group of the epoxy resin and one equivalent of unsaturated bond of the resin having at least one unsaturated bond in the molecule. It is related with the resin composition as described in any one of said [8]-[10] whose total amount is 0.001-10 equivalent.

[12] The present invention relates to a liquid crystal sealing agent composition containing the resin composition according to any one of [8] to [11] above.

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

[14] The present invention relates to a method for producing a liquid crystal display panel, wherein in the liquid crystal dropping method, photocuring is performed using the liquid crystal sealant composition described in [12] above, followed by thermosetting.

  According to the present invention, the adhesive strength can be applied to the thinning of the sealing agent for liquid crystal display panels and the like and the diversification of adhesiveness, and can suppress peeling when the cell is cut out and when the IC for driving the liquid crystal cell is mounted. Can be expressed.

It is explanatory drawing which shows one Embodiment which manufactures a liquid crystal display panel using a liquid-crystal sealing compound composition. It is explanatory drawing explaining the test method of the adhesive strength of a liquid-crystal sealing compound composition.

In the present specification, a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. The amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition. The description “C _a -C _b ” means that the carbon number is in the range of ab.

[Curing agent]
The present invention has at least one primary amino group in a molecule obtained by reacting an isocyanate compound with hydrazine or a polyvalent amine compound having two or more primary amino groups in the molecule. A curing agent for an epoxy resin and / or a resin having at least one unsaturated bond in the molecule, including a compound. A curing agent containing a compound having a urea structure in addition to at least one primary amino group in the molecule is used as an epoxy resin and / or a resin having at least one unsaturated bond in the molecule (for example, (meth) acrylic). Resin, etc.) is used as a latent curing agent for liquid crystal display panels, etc., and adapts to thinning of the sealing agent and diversification of adhesive properties, and also when cutting out cells and mounting ICs for driving liquid crystal cells. Adhesive strength capable of suppressing peeling can be expressed.

  A compound obtained by reacting an isocyanate compound with hydrazine or a polyvalent amine compound having two or more primary amino groups in the molecule has a urea structure and at least one primary amino group in the molecule. Therefore, it is presumed that the hydrogen bond strength with the adherend is improved and the adhesive strength is higher than that of the hydrazide compound or amine compound used as the curing agent.

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

式（１ａ）において、Ｘ^２は、Ｃ_１〜Ｃ_１２アルキル、１つ若しくはそれ以上のＯ原子（酸素原子）で非連続的に中断されたＣ_２〜Ｃ_１２アルキル、Ｃ_１〜Ｃ_１２アルキルオキシカルボニルアルキレン、Ｃ_３〜Ｃ_１２シクロアルキル、Ｃ_１〜Ｃ_１２アルキル−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_３〜Ｃ_１２シクロアルキル−Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_６〜Ｃ_１４アリール、Ｃ_１〜Ｃ_４アルキル−Ｃ_６〜Ｃ_１４アリーレン、Ｃ_６〜Ｃ_１４アリール−Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン（ここで、アルキレンは、直鎖又は分岐鎖であり、ハロゲンで置換されていてもよく、Ｃ_３〜Ｃ_１２シクロアルキル、Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_６〜Ｃ_１４アリール、又はＣ_６〜Ｃ_１４アリーレンは、非置換であるか、又はハロゲン若しくはＣ_１〜Ｃ_４アルキルで置換されている）、又は（メタ）アクリロイルオキシアルキルである。式（１ａ）におけるＸ^２は、式（Ｉ）において、ｎが１の場合におけるＡと同義である。(Monoisocyanate compound)
Examples of the monoisocyanate compound include compounds represented by the following formula (1a).

In Formula (1a), X ² is C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkyl, C ₁ -C ₁₂ alkyl interrupted discontinuously with one or more O atoms (oxygen atoms). oxycarbonyl _alkylene, C 3 _{-C 12 cycloalkyl,} C 1 _{-C 12} alkyl _-C 3 _{-C 12 cycloalkylene,} C 3 _{-C 12} cycloalkyl _-C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene, C ₆ -C ₁₄ aryl, C ₁ -C ₄ alkyl-C ₆ -C ₁₄ arylene, C ₆ -C ₁₄ aryl-C ₁ -C ₄ alkylene-C ₆ -C ₁₄ arylene (wherein alkylene is linear or a branched chain, may be substituted by _halogen, C 3 _{-C 12 cycloalkyl,} C 3 _{-C 12 cycloalkylene,} C 6 _{-C 14} arylene Or C ₆ -C ₁₄ arylene is unsubstituted or substituted with halogen or C ₁ -C ₄ alkyl), or (meth) acryloyloxyalkyl. X ² in formula (1a) has the same meaning as A in the case where n is 1 in formula (I).

As used herein, alone or in combination with other terms, “C ₁ -C ₁₂ alkyl” is straight or branched chain and may be substituted with one or more halogens. The O atom (oxygen atom) may be discontinuously interrupted, and is preferably linear. Range of the carbon number of the alkyl _is C 1 _{-C 12,} more preferably _C 1 -C _8, more preferably _C 1 -C _6, particularly preferably include a range of _C 1 -C _4. Specific examples thereof include, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n- Examples include straight-chain compounds such as dodecyl and branched-chain compounds such as isopropyl, isobutyl, sec-butyl, t-butyl, 2-methylbutyl, isooctyl, t-octyl, 2-ethylhexyl, and t-nonyl. Examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The halogen as a substituent is preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom. The number of substitution is 1 to 12, preferably 1 to 6, more preferably 1 to 4, particularly preferably 1 to 3.

As used herein, alone or in combination with other terms, “C ₁ -C ₁₂ alkylene” is straight or branched chain and may be substituted with one or more halogens. May be interrupted discontinuously by NH (imino group) or O atom (oxygen atom) (H atom (hydrogen atom) bonded to N atom (nitrogen atom) is an amino group or C _{1 to} C _12. The alkylamino group may be substituted), preferably a straight-chain one. Range of the carbon number of the alkylene _is C 1 _{-C 12,} more preferably _C 1 -C _8, more preferably _C 1 -C _6, particularly preferably include a range of _C 1 -C _4. Specific examples thereof include, for example, methylene, ethylene, trimethylene, propylene, tetramethylene, 1-methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene, pentamethylene, 1-methyltetramethylene, 4-methyltetra Examples include methylene, hexamethylene, 5-methylpentamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene and the like. Examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The halogen as a substituent is preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom. The number of substitution is 1 to 12, preferably 1 to 6, more preferably 1 to 4, particularly preferably 1 to 3.

In the present specification, _"C 1 _{-C 12} alkyloxycarbonyl alkylene" or range of number of carbon atoms in the alkyloxy or alkyleneoxy of _"C 1 _{-C 12} alkyleneoxy carbonyl alkylene" _is a C 1 _{-C 12,} more preferably _C 1 -C _8, more preferably _C 1 -C _6, particularly preferably include a range of _C 1 -C _4. Specific examples thereof include, for example, methoxycarbonylmethylene, ethoxycarbonylmethylene, n-propoxycarbonylmethylene, n-butoxycarbonylmethylene, n-pentyloxycarbonylmethylene, n-hexyloxycarbonylmethylene, n-heptyloxycarbonylmethylene, n -Octyloxycarbonylmethylene, n-nonyloxycarbonylmethylene, n-decyloxycarbonylmethylene, n-undecyloxycarbonylmethylene, n-dodecyloxycarbonylmethylene, and the like, isopropoxycarbonylmethylene, isobutoxycarbonylmethylene , Sec-butoxycarbonylmethylene, t-butoxycarbonylmethylene, 2-methylbutoxycarbonylmethylene, isooctyloxycarbonylmethylene Ren, t-octyloxy carbonyl methylene, those branched chains such as 2-ethylhexyl butyloxycarbonyl methylene and the like.

As used herein, alone or in combination with other terms, the carbon number range of “C ₃ -C ₁₂ cycloalkyl” is C ₃ -C ₁₂ , more preferably C ₃ -C ₈ , preferably _C 3 -C _6, particularly preferred examples include a range of _C 4 -C _6. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl. C ₃ -C ₁₂ cycloalkyl is preferably cyclopentyl or cyclohexyl. C ₃ -C ₁₂ cycloalkyl may be unsubstituted or substituted with halogen or C ₁ -C ₄ alkyl, where halogen includes fluorine, chlorine, bromine and iodine atoms. . The halogen as a substituent is preferably a fluorine atom or a chlorine atom, more preferably a chlorine atom. The _C 1 -C ₄ alkyl as the substituent include methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec- butyl and t- butyl. C ₁ -C ₄ alkyl as the substituent is preferably methyl, ethyl or n- propyl, more preferably methyl or ethyl. In the case of having a substituent, the number of substitution is 1 to 5, preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1.

As used herein, alone or in combination with other terms, the carbon number range of “C ₃ -C ₁₂ cycloalkylene” is C ₃ -C ₁₂ , more preferably C ₃ -C ₈ , preferably _C 3 -C _6, particularly preferred examples include a range of _C 4 -C _6. Specific examples thereof include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene, cyclodecylene, cycloundecylene, and cyclododecylene. C ₃ -C ₁₂ cycloalkylene is preferably cyclopentylene or cyclohexylene. C ₃ -C ₁₂ cycloalkylene can be unsubstituted or substituted with halogen or C ₁ -C ₄ alkyl, which includes fluorine, chlorine, bromine and iodine atoms. . The halogen as a substituent is preferably a fluorine atom or a chlorine atom, more preferably a chlorine atom. The _C 1 -C ₄ alkyl as the substituent include methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec- butyl and t- butyl. C ₁ -C ₄ alkyl as the substituent is preferably methyl, ethyl or n- propyl, more preferably methyl or ethyl. In the case of having a substituent, the number of substitution is 1 to 4, preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1.

As used herein, alone or in combination with other terms, “C ₆ -C ₁₄ aryl” is a monovalent group having at least one aromatic ring. Specific examples thereof include phenyl, biphenyl, naphthyl, anthranyl, phenanthrene and the like. Preferred is phenyl, biphenyl or naphthyl, and more preferred is phenyl or naphthyl. C ₆ -C ₁₄ aryl may be unsubstituted or substituted with halogen or C ₁ -C ₄ alkyl, and halogen includes fluorine atom, chlorine atom, bromine atom and iodine atom. The halogen as a substituent is preferably a fluorine atom or a chlorine atom, more preferably a chlorine atom. The _C 1 -C ₄ alkyl as the substituent include methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec- butyl and t- butyl. C ₁ -C ₄ alkyl as the substituent is preferably methyl, ethyl or n- propyl, more preferably methyl or ethyl. In the case of having a substituent, the number of substitution is 1 to 5, preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1.

As used herein, alone or in combination with other terms, a “C ₆ -C ₁₄ arylene” is a divalent group having at least one aromatic ring. Specific examples thereof include phenylene, naphthylene, anthranylene, phenanthranylene and the like. Preferable are phenylene and naphthylene, and more preferable are phenylene and naphthylene. The C ₆ -C ₁₄ arylene may be unsubstituted or substituted with a halogen or C ₁ -C ₄ alkyl, and the halogen includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The halogen as a substituent is preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a fluorine atom or a chlorine atom. The _C 1 -C ₄ alkyl as the substituent include methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec- butyl and t- butyl. C ₁ -C ₄ alkyl as the substituent is preferably methyl, ethyl or n- propyl, more preferably methyl or ethyl. In the case of having a substituent, the number of substitution is 1 to 4, preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1.

式（１ｂ）において、Ｒ^６は水素原子又はメチル基を示し、Ｒ^７はＣ_１〜Ｃ_６アルキレンを示す。Ｒ^７のＣ_１〜Ｃ_６アルキレンの炭素数の範囲は、好ましくはＣ_２〜Ｃ_６、より好ましくはＣ_３〜Ｃ_６である。Examples of the (meth) acryloyloxyalkyl isocyanate as the monoisocyanate compound include compounds represented by the following formula (1b).

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

  Specific examples of the monoisocyanate compound include methyl isocyanate, ethyl isocyanate, n-hexyl isocyanate, cyclohexyl isocyanate, 2-ethylhexyl isocyanate, phenyl isocyanate, benzyl isocyanate, propyl isocyanate, and isopropyl. Isocyanate, butyl isocyanate, heptyl isocyanate, dodecyl isocyanate, octadecyl isocyanate, t-butyl isocyanate, ethyl isocyanatoacetate, butyl isocyanatoacetate, methyl (S)-(−)-2-isocyanatopropionate, isocyanate 1-naphthyl acid, 4-chlorophenyl isocyanate, 4-fluorophenyl isocyanate, phenethyl isocyanate, p-tolyl isocyanate, m-isocyanate And tolyl and 3,5-dimethylphenyl isocyanate.

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

式（２ａ）において、Ｘ^１は、Ｃ_１〜Ｃ_１２アルキレン、１つ若しくはそれ以上のＯ原子（酸素原子）で非連続的に中断されたＣ_２〜Ｃ_１２アルキレン、Ｃ_１〜Ｃ_１２アルキレンオキシカルボニルアルキレン、Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_１２アルキレン、Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、ジＣ_３〜Ｃ_１２シクロアルカンジイル、Ｃ_６〜Ｃ_１４アリーレン、Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン、又はＣ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン（ここで、アルキレンは、直鎖又は分岐鎖であり、ハロゲンで置換されていてもよく、Ｃ_３〜Ｃ_１２シクロアルキレン又はＣ_６〜Ｃ_１４アリーレンは、非置換であるか、又はハロゲン若しくはＣ_１〜Ｃ_４アルキルで置換されている）である。式（２ａ）におけるＸ^１は、式（Ｉ）において、ｎが２の場合におけるＡと同義である。(Diisocyanate compound)
Examples of the diisocyanate compound include a compound represented by the following formula (2a).

In formula (2a), X ¹ is C ₁ -C ₁₂ alkylene, C ₂ -C ₁₂ alkylene, C ₁ -C ₁₂ alkylene, discontinuously interrupted by one or more O atoms (oxygen atoms) oxycarbonyl _alkylene, C 3 _{-C 12 cycloalkylene,} C 1 _{-C 12} alkylene _-C 3 _{-C 12 cycloalkylene,} C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12} alkylene, C ₃ -C ₁₂ cycloalkylene _-C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene, di _C 3 _{-C 12 cycloalkanediyl,} C 6 _{-C 14 arylene,} C 1 -C ₄ alkylene _-C 6 -C ₁₄ arylene-C ₁ -C ₄ alkylene, or C ₆ -C ₁₄ arylene-C ₁ -C ₄ alkylene-C ₆ -C ₁₄ Arylene (where alkylene is linear or branched chain, may be substituted by halogen, C ₃ -C ₁₂ cycloalkylene or C ₆ -C ₁₄ arylene is unsubstituted or halogen or C ₁ -C a ₄ substituted with alkyl). X ¹ in formula (2a) has the same meaning as A in the case where n is 2 in formula (I).

  Specific examples of the diisocyanate compound include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), xylene diisocyanate (XDI), hydrogenated xylene diisocyanate (hydrogenated XDI), and isophorone. Diisocyanate (IPDI), Tolidine diisocyanate (TPDI), Hexamethylene diisocyanate (HDI), Dicyclohexylmethane diisocyanate (HMDI), 2,4,4-trimethylhexamethylene diisocyanate (TMHDI), 3 , 5,5-trimethylhexamethylene diisocyanate (TMHDI), 4,4'-diisocyanato-3,3'-dimethylbiphenyl, 4,4'-diisocyanato-3,3'-dimethyldiphenylmethane, 2,2-bis (4-isocyanatov Enyl) hexafluoropropane, 2,4-diisocyanatotoluene, 1,3-bis (2-isocyanato-2-propyl) benzene, tolylene-2,6-diisocyanate, 1,4-phenylene diisocyanate, Examples include 1,3-phenylene diisocyanate and 1,5-diisocyanatonaphthalene.

式中、Ｒ^２は、同一又は異なり、直鎖又は分岐鎖のＣ_１〜Ｃ_１２アルキレンである。(Triisocyanate compound)
Examples of the triisocyanate compound include compounds having an isocyanurate structure, a biuret structure, or an adduct structure having an isocyanate group at three terminals. Examples of the triisocyanate compound having an isocyanurate structure include compounds having an isocyanurate structure represented by the following formula (3a).

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

式中、Ｒ^３は、同一又は異なり、直鎖又は分岐鎖のＣ_１〜Ｃ_１２アルキレンである。Examples of the triisocyanate compound having a biuret structure include compounds represented by the following formula (3b).

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

式中、Ｒ^４は、同一又は異なり、直鎖又は分岐鎖のＣ_１〜Ｃ_１２アルキレンであり、Ｒ^５は、ＣＨである。Examples of the triisocyanate compound having an adduct structure include a compound represented by the following formula (3c).

In the formula, R ⁴ is the same or different and is a linear or branched C _{1 to} C ₁₂ alkylene, and R ⁵ is CH.

  Specific examples of the triisocyanate compound include tri (isocyanatomethyl) isocyanurate, tri (isocyanatoethyl) isocyanurate, tri (isocyanatopropyl) isocyanurate, tri (isocyanatobutyl) isocyanurate, tri (Isocyanatohexyl) isocyanurate, N, N′-2-tris-isocyanatomethylmalonic acid amide, N, N′-2-tris-isocyanatohexylmalonic acid amide and the like.

式中、Ｘ^３は、Ｃ_３〜Ｃ_１２シクロアルキル−Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキル、又はＣ_６〜Ｃ_１４アリール−Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリール（アルキレンは、直鎖又は分岐鎖であり、ハロゲンで置換されていてもよく、Ｃ_３〜Ｃ_１２シクロアルキル又はＣ_６〜Ｃ_１４アリールは、非置換であるか、又はハロゲン若しくはＣ_１〜Ｃ_４アルキルで置換されていてもよい）から誘導される４価の基である。(Tetraisocyanate compound)
Examples of the tetraisocyanate compound include compounds represented by the following formula (4a).

In the formula, X ³ is C ₃ -C ₁₂ cycloalkyl-C ₁ -C ₁₂ alkylene-C ₃ -C ₁₂ cycloalkyl, or C ₆ -C ₁₄ aryl-C ₁ -C ₄ alkylene-C ₆ -C _14. Aryl (alkylene is straight or branched chain and may be substituted with halogen, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₁₄ aryl is unsubstituted, halogen or C _1- A tetravalent group derived from (optionally substituted by C ₄ alkyl).

Examples of the tetraisocyanate compound include tetraisocyanatosilane represented by the following formula (4b).

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

式中、Ｌは、Ｃ_１〜Ｃ_１２アルキレン、１つ若しくはそれ以上のＮＨ（イミノ基）若しくはＯ原子（酸素原子）で非連続的に中断されたＣ_２〜Ｃ_１２アルキレン（Ｎ原子（窒素原子）に結合するＨ原子（水素原子）は、アミノ基又はＣ_１〜Ｃ_１２アルキルアミノ基で置換されていてもよい）、Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_１２アルキレン、Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_４アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_６〜Ｃ_１４アリーレン、Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン、Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン、又はＣ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン（ここで、アルキレンは、直鎖又は分岐鎖であり、ハロゲンで置換されていてもよく、Ｃ_３〜Ｃ_１２シクロアルキレン又はＣ_６〜Ｃ_１４アリーレンは、非置換であるか、又はハロゲン若しくはＣ_１〜Ｃ_４アルキルで置換されていてもよい。）である。式（５ａ）におけるＬは、式（Ｉ）、式（Ｉａ）及び式（ＩＩａ）におけるＲ^１と同義である。[Polyvalent amine compound]
The polyvalent amine compound is a compound having at least two primary amino groups, and examples thereof include a polyvalent amine compound represented by the following formula (5a).

Wherein L is C ₁ -C ₁₂ alkylene, C ₂ -C ₁₂ alkylene (N atom (nitrogen) interrupted discontinuously by one or more NH (imino group) or O atom (oxygen atom). H atom bonded to an atom) (hydrogen atoms) may be substituted by an amino group or a _C 1 _{-C 12} alkylamino _group), C 3 _{-C 12 cycloalkylene,} C 1 _{-C 12} alkylene -C ₃ -C _{12 cycloalkylene,} C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12 alkylene,} C 3 _{-C 12} cycloalkylene _-C 1 -C ₄ alkylene _-C 3 _{-C 12} cycloalkylene , _C 6 _{-C 14 arylene,} C 1 -C ₄ alkylene _-C 6 _{-C 14 arylene,} C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene _-C 1 -C Alkylene, or _C 6 _{-C 14} arylene _-C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene (where alkylene is linear or branched chain, may be substituted by _{halogen, C} 3 ~ C ₁₂ cycloalkylene or C ₆ -C ₁₄ arylene is unsubstituted or optionally substituted with halogen or C ₁ -C ₄ alkyl. L in Formula (5a) has the same meaning as R ¹ in Formula (I), Formula (Ia), and Formula (IIa).

  Examples of the polyvalent amine compound include a diamine compound having two primary amino groups, a triamine compound having three primary amino groups, and the like. Although it does not specifically limit as a diamine compound which has two primary amino groups, For example, aliphatic diamine, alicyclic diamine, aromatic diamine etc. are mentioned. Of the compounds represented by the formula (5a), the compound in which L is a single bond is hydrazine.

Specific examples of the aliphatic diamine compound having C _{1 to} C ₁₂ alkylene include, for example, ethylene diamine, propylene diamine, 1,2-diaminopropane, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, and heptamethylene. Examples include diamine, octamethylene diamine, dodecamethylene diamine, propane-1,2-diamine, and 1,2-diamino-2-methylpropane.

Among the aliphatic diamines, as a compound having a linear or branched C _{2 to} C ₁₂ alkylene discontinuously interrupted by one or more O atoms (oxygen atoms), specifically, for example, 2,2′-oxybis (ethylamine), 1,2-bis (2-aminoethoxy) ethane, 1,11-diamino-3,6,9-trioxaundecane, bis (3-aminopropyl) ether, , 4-butanediol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, ethylene glycol bis (3-aminopropyl) ether, and the like.

Of the aliphatic diamines, H atoms bonded to linear or branched C _{2 to} C ₁₂ alkylenes (N atoms (nitrogen atoms)) discontinuously interrupted by one or more NH (imino groups) (hydrogen atom), as a compound having an amino group or a C ₁ may be substituted with an alkylamino group -C _12), specifically, for example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylene Ethylenehexamine, tris (2-aminoethyl) amine, N, N′-bis (3-aminopropyl) ethylenediamine, bis (hexamethylene) triamine, 3,3′-diamino-N-methyldipropylamine, 3,3 Examples include '-diaminodipropylamine and bis (3-aminopropyl) methylamine.

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

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

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

The isocyanate compound and the hydrazine or polyvalent amine compound are preferably 0.01 mol to 50 mol, more preferably 0.1 mol to 50 mol of the hydrazine or polyvalent amine compound with respect to 1 mol of the isocyanate compound. More preferably, it is 0.1 to 30 mol, particularly preferably 0.1 to 20 mol in an organic solvent or neat (no solvent), preferably −10 ° C. to 120 ° C., more preferably − It is preferable to carry out the reaction while controlling at 5 to 100 ° C, more preferably 0 to 50 ° C, particularly preferably 5 to 30 ° C.
Further, the curing agent comprises an isocyanate compound and a hydrazine or polyvalent amine compound with respect to 1 mol of the isocyanate group contained in the isocyanate compound, the primary amino group contained in the hydrazine or polyvalent amine compound. The total number is preferably 0.01 mol to 50 mol, more preferably 0.1 mol to 50 mol, still more preferably 0.1 mol to 30 mol, and particularly preferably 0.5 mol to 20 mol. It is also preferable to contain the compound obtained in this way.

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

〔式中
Ｒ^１は、単結合であるか、あるいはＣ_１〜Ｃ_１２アルキレン、１つ若しくはそれ以上のＮＨ（イミノ基）若しくはＯ酸素原子（酸素原子）で非連続的に中断されたＣ_２〜Ｃ_１２アルキレン（Ｎ原子（窒素原子）に結合するＨ原子（水素原子）は、アミノ基又はＣ_１〜Ｃ_１２のアルキルアミノ基で置換されていてもよい）、Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_１２アルキレン、Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_６〜Ｃ_１４アリーレン、Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン、Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン、又はＣ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン（ここで、アルキレンは、直鎖又は分岐鎖であり、ハロゲンで置換されていてもよく、Ｃ_３〜Ｃ_１２シクロアルキレン又はＣ_６〜Ｃ_１４アリーレンは、非置換であるか、又はハロゲン若しくはＣ_１〜Ｃ_４アルキルで置換されている）であり、
ｎは、１、２、３又は４であり、
ｎが２以上の場合は、Ｒ^１は、互いに独立して、上記と同義である。
ｎが１の場合、Ａは、Ｃ_１〜Ｃ_１２アルキル、１つ若しくはそれ以上のＯ原子（酸素原子）で非連続的に中断されたＣ_２〜Ｃ_１２アルキル、Ｃ_２〜Ｃ_１２アルキルオキシカルボニルアルキレン、Ｃ_３〜Ｃ_１２シクロアルキル、Ｃ_１〜Ｃ_１２アルキル−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_３〜Ｃ_１２シクロアルキル−Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_６〜Ｃ_１４アリール、Ｃ_１〜Ｃ_４アルキル−Ｃ_６〜Ｃ_１４アリーレン、Ｃ_６〜Ｃ_１４アリール−Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン（ここで、アルキレンは、直鎖又は分岐鎖であり、ハロゲンで置換されていてもよく、Ｃ_３〜Ｃ_１２シクロアルキル、Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_６〜Ｃ_１４アリール又はＣ_６〜Ｃ_１４アリーレンは、非置換であるか、又はハロゲン若しくはＣ_１〜Ｃ_４アルキルで置換されている）、又は（メタ）アクリロイルオキシアルキルであり、
ｎが２の場合、Ａは、Ｃ_１〜Ｃ_１２アルキレン、１つ若しくはそれ以上のＯ原子（酸素原子）で非連続的に中断されたＣ_２〜Ｃ_１２アルキレン、Ｃ_１〜Ｃ_１２アルキレンオキシカルボニルアルキレン、Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_１２アルキレン、Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、ジＣ_３〜Ｃ_１２シクロアルカンジイル、Ｃ_６〜Ｃ_１４アリーレン、Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン、又はＣ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン（ここで、アルキレンは、直鎖又は分岐鎖であり、ハロゲンで置換されていてもよく、Ｃ_３〜Ｃ_１２シクロアルキレン又はＣ_６〜Ｃ_１４アリーレンは、非置換であるか、又はハロゲン若しくはＣ_１〜Ｃ_４アルキルで置換されている）であり、
ｎが３の場合、Ａは、下記式（１）

（式中、Ｒ^２は、同一又は異なり、直鎖又は分岐鎖のＣ_１〜Ｃ_１２アルキレンである）、下記式（２）

（式中、Ｒ^３は、同一又は異なり、直鎖又は分岐鎖のＣ_１〜Ｃ_１２アルキレンである）又は下記式（３）

（式中、Ｒ^４は、同一又は異なり、直鎖又は分岐鎖のＣ_１〜Ｃ_１２アルキレンであり、Ｒ^５は、ＣＨである）であり、
ｎが４の場合は、Ａは、下記式（４）

｛式中、Ｘ^３は、Ｓｉであるか、又はＣ_３〜Ｃ_１２シクロアルキル−Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキル、若しくはＣ_６〜Ｃ_１４アリール−Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリール（ここで、アルキレンは、直鎖又は分岐鎖であり、ハロゲンで置換されていてもよく、Ｃ_３〜Ｃ_１２シクロアルキル又はＣ_６〜Ｃ_１４アリールは、非置換であるか、又はハロゲン若しくはＣ_１〜Ｃ_４アルキルで置換されている）から誘導される４価の残基である｝である〕で示される化合物を含む。The curing agent of the present invention has the following formula (I)

[Wherein R ¹ is a single bond, or C ₁ -C ₁₂ alkylene, C ₂ interrupted discontinuously with one or more NH (imino group) or O oxygen atom (oxygen atom). -C ₁₂ alkylene (the H atom (hydrogen atom) bonded to the N atom (nitrogen atom) may be substituted with an amino group or a C ₁ -C ₁₂ alkylamino group), C ₃ -C ₁₂ cycloalkylene C ₁ -C ₁₂ alkylene-C ₃ -C ₁₂ cycloalkylene, C ₁ -C ₁₂ alkylene-C ₃ -C ₁₂ cycloalkylene-C ₁ -C ₁₂ alkylene, C ₃ -C ₁₂ cycloalkylene-C ₁ -C ₁₂ alkylene _-C 3 _{-C 12 cycloalkylene,} C 6 _{-C 14 arylene,} C 1 -C ₄ alkylene _-C 6 _{-C 14 arylene,} C 1 -C ₄ alkylene - ₆ -C ₁₄ arylene _-C 1 -C ₄ alkylene, or _C 6 _{-C 14} arylene _-C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene (where alkylene is linear or branched, halogen And C ₃ -C ₁₂ cycloalkylene or C ₆ -C ₁₄ arylene is unsubstituted or substituted with halogen or C ₁ -C ₄ alkyl).
n is 1, 2, 3 or 4;
When n is 2 or more, R ¹ is independently the same as above.
When n is 1, A is C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkyl, C ₂ -C ₁₂ alkyloxy discontinuously interrupted by one or more O atoms (oxygen atoms) carbonyl _alkylene, C 3 _{-C 12 cycloalkyl,} C 1 _{-C 12} alkyl _-C 3 _{-C 12 cycloalkylene,} C 3 _{-C 12} cycloalkyl _-C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene, C ₆ -C _{14 aryl,} C 1 -C ₄ alkyl _-C 6 _{-C 14 arylene,} C 6 _{-C 14} aryl _-C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene (where alkylene is straight-chain or a branched chain, may be substituted by _halogen, C 3 _{-C 12 cycloalkyl,} C 3 _{-C 12 cycloalkylene,} C 6 _{-C 14} aryl or C _{6 to} C ₁₄ arylene is unsubstituted or substituted with halogen or C _{1 to} C ₄ alkyl), or (meth) acryloyloxyalkyl;
When n is 2, A is C ₁ -C ₁₂ alkylene, C ₂ -C ₁₂ alkylene, C ₁ -C ₁₂ alkyleneoxy discontinuously interrupted by one or more O atoms (oxygen atoms) carbonyl _alkylene, C 3 _{-C 12 cycloalkylene,} C 1 _{-C 12} alkylene _-C 3 _{-C 12 cycloalkylene,} C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12} alkylene, _{C 3} -C ₁₂ cycloalkylene _-C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene, di _C 3 _{-C 12 cycloalkanediyl,} C 6 _{-C 14 arylene,} C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene _-C 1 -C ₄ alkylene, or _C 6 _{-C 14} arylene _-C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene Here, the alkylene is a straight-chain or branched-chain, may be substituted by halogen, C ₃ -C ₁₂ cycloalkylene or C ₆ -C ₁₄ arylene, unsubstituted or halogen or C ₁ ~C is ₄ substituted with alkyl),
When n is 3, A is the following formula (1)

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

(Wherein R ³ are the same or different and are linear or branched C _{1 to} C ₁₂ alkylene) or the following formula (3)

Wherein R ⁴ is the same or different and is a linear or branched C _{1 to} C ₁₂ alkylene and R ⁵ is CH.
When n is 4, A is the following formula (4)

{Wherein X ³ is Si or C ₃ -C ₁₂ cycloalkyl-C ₁ -C ₁₂ alkylene-C ₃ -C ₁₂ cycloalkyl, or C ₆ -C ₁₄ aryl-C ₁ -C _4. Alkylene-C ₆ -C ₁₄ aryl (wherein alkylene is linear or branched and may be substituted with halogen; C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₁₄ aryl is unsubstituted Or a tetravalent residue derived from halogen or substituted with C ₁ -C ₄ alkyl).

The compound of the above formula (I) is a compound having at least one isocyanate group (—N═C═O), for example, the monoisocyanate compound, the diisocyanate compound, the triisocyanate compound, and It is preferably obtained by reacting at least one isocyanate compound selected from the group consisting of the above-mentioned tetraisocyanate compounds with hydrazine or a polyvalent amine compound. The compound represented by the formula (I) preferably contains the isocyanate compound and the hydrazine or polyvalent amine compound, and the hydrazine or polyvalent amine compound with respect to 1 mole of the isocyanate compound. Mol to 50 mol, more preferably 0.1 mol to 50 mol, still more preferably 0.1 mol to 30 mol, particularly preferably 0.1 mol to 20 mol, in an organic solvent or neat (no solvent) ), Preferably −10 ° C. to 120 ° C., more preferably −5 ° C. to 100 ° C., further preferably 0 ° C. to 50 ° C., particularly preferably 5 to 30 ° C. It is preferable.
Furthermore, the compound represented by the above formula (I) contains an isocyanate compound and a hydrazine or polyvalent amine compound in the hydrazine or polyvalent amine compound with respect to 1 mol of the isocyanate group contained in the isocyanate compound. The total number of primary amino groups is preferably 0.01 mol to 50 mol, more preferably 0.1 mol to 50 mol, still more preferably 0.1 mol to 30 mol, particularly preferably 0.5 mol to 20 mol. It is also preferable that it is obtained by reacting so that it becomes a mole.

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

〔式中、
Ｒ^１は、互いに独立して、単結合であるか、あるいはＣ_１〜Ｃ_１２アルキレン、１つ若しくはそれ以上のＮＨ（イミノ基）若しくはＯ原子（酸素原子）で非連続的に中断されたＣ_２〜Ｃ_１２アルキレン（Ｎ原子（窒素原子）に結合するＨ原子（水素原子）は、アミノ基又はＣ_１〜Ｃ_１２のアルキルアミノ基で置換されていてもよい）、Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_１２アルキレン、Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_６〜Ｃ_１４アリーレン、Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン、Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン、又はＣ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン（ここで、アルキレンは、直鎖又は分岐鎖であり、ハロゲンで置換されていてもよく、Ｃ_３〜Ｃ_１２シクロアルキレン又はＣ_６〜Ｃ_１４アリーレンは、非置換であるか、又はハロゲン若しくはＣ_１〜Ｃ_４アルキルで置換されている）であり、
Ｘ^１は、Ｃ_１〜Ｃ_１２アルキレン、１つ若しくはそれ以上のＯ原子（酸素原子）で非連続的に中断されたＣ_２〜Ｃ_１２アルキレン、Ｃ_１〜Ｃ_１２アルキレンオキシカルボニルアルキレン、Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_１２アルキレン、Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、ジＣ_３〜Ｃ_１２シクロアルカンジイル、Ｃ_６〜Ｃ_１４アリーレン、Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン、又はＣ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン（ここで、アルキレンは、直鎖又は分岐鎖であり、ハロゲンで置換されていてもよく、Ｃ_３〜Ｃ_１２シクロアルキレン又はＣ_６〜Ｃ_１４アリーレンは、非置換であるか、又はハロゲン若しくはＣ_１〜Ｃ_４アルキルで置換されている）である〕であることが好ましい。
式（Ｉａ）におけるＸ^１は、式（Ｉ）において、ｎが２の場合におけるＡと同義である。In the curing agent of the present invention, the compound having at least one primary amino group in the molecule is represented by the following formula (Ia):

[Where,
R ¹ , independently of each other, is a single bond or C ₁ -C ₁₂ alkylene, C interrupted discontinuously with one or more NH (imino group) or O atoms (oxygen atoms) _{2 to} C ₁₂ alkylene (the H atom (hydrogen atom) bonded to the N atom (nitrogen atom) may be substituted with an amino group or a C _{1 to} C ₁₂ alkylamino group), C _{3 to} C ₁₂ cyclo Alkylene, C ₁ -C ₁₂ alkylene-C ₃ -C ₁₂ cycloalkylene, C ₁ -C ₁₂ alkylene-C ₃ -C ₁₂ cycloalkylene-C ₁ -C ₁₂ alkylene, C ₃ -C ₁₂ cycloalkylene-C _1- C ₁₂ alkylene-C ₃ -C ₁₂ cycloalkylene, C ₆ -C ₁₄ arylene, C ₁ -C ₄ alkylene-C ₆ -C ₁₄ arylene, C ₁ -C ₄ alkylene -C ₆ -C ₁₄ arylene-C ₁ -C ₄ alkylene, or C ₆ -C ₁₄ arylene-C ₁ -C ₄ alkylene-C ₆ -C ₁₄ arylene (wherein alkylene is linear or branched) Yes, optionally substituted with halogen, C ₃ -C ₁₂ cycloalkylene or C ₆ -C ₁₄ arylene is unsubstituted or substituted with halogen or C ₁ -C ₄ alkyl) ,
X ¹ is C ₁ -C ₁₂ alkylene, C ₂ -C ₁₂ alkylene, C ₁ -C ₁₂ alkyleneoxycarbonylalkylene, C ₃ discontinuously interrupted by one or more O atoms (oxygen atoms) -C _{12 cycloalkylene,} C 1 _{-C 12} alkylene _-C 3 _{-C 12 cycloalkylene,} C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12 alkylene,} C 3 _{-C 12} cycloalkylene -C ₁ -C ₁₂ alkylene _-C 3 _{-C 12} cycloalkylene, di _C 3 _{-C 12 cycloalkanediyl,} C 6 _{-C 14 arylene,} C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene _-C 1 ~ C ₄ alkylene, or C ₆ -C ₁₄ arylene-C ₁ -C ₄ alkylene-C ₆ -C ₁₄ arylene (wherein Alkylene is a straight-chain or branched-chain, may be substituted by _halogen, C 3 _{-C 12} cycloalkylene or _C 6 _{-C 14} arylene, unsubstituted or halogen or _C 1 -C ₄ Preferably substituted with alkyl).
X ¹ in formula (Ia) has the same meaning as A in the case where n is 2 in formula (I).

  The compound represented by the formula (Ia) is preferably obtained by reacting the diisocyanate compound with hydrazine or a polyvalent amine compound. The diisocyanate compound and the hydrazine or polyvalent amine compound are preferably 0.01 mol to 50 mol, more preferably 0.1 mol to 1 mol of the hydrazine or polyvalent amine compound with respect to 1 mol of the diisocyanate compound. 50 mol, more preferably 0.1 mol to 30 mol, particularly preferably 0.1 mol to 20 mol, in an organic solvent or neat (no solvent), preferably −10 ° C. to 120 ° C., more It is preferably obtained by reacting at -5 ° C to 100 ° C, more preferably 0 ° C to 50 ° C, particularly preferably 5 to 30 ° C.

上記式中、Ｘ^１は、式（Ｉａ）におけるＸ^１と同義である。The compound obtained by the reaction of the diisocyanate compound with, for example, tris (2-aminoethyl) amine, which is a polyvalent amine compound having three primary amino groups in the molecule, is represented by the following formula. Compounds.

In the above formulas, ^{X 1} has the same meaning as ^{X 1} in formula (Ia).

As the compound represented by the above formula (Ia), for example,
1,1 ′-[methylenebis (cyclohexane-1,4-diyl)] bis [3- (12-aminododecyl) urea] (A-1),
1,1 ′-[methylenebis (cyclohexane-1,4-diyl)] bis [3- (2-aminoethyl) urea] (A-2),
1,1 ′-[methylenebis (cyclohexane-1,4-diyl)] bis [3- (6-aminohexyl) urea] (A-3),
1,1 ′-(hexane-1,6-diyl) bis [3- (12-aminododecyl) urea] (A-4),
1,1 ′-(hexane-1,6-diyl) bis [3- (2-aminoethyl) urea] (A-5),
1,1 ′-(hexane-1,6-diyl) bis [3- (6-aminohexyl) urea] (A-6),
N, N′-hexamethylene [carbonylbis (azanediyl) -2-aminoethyl]-[carbonylbis (azanediyl) -6-aminohexyl] (A-7)
Etc.

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

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

（式中、Ｘ^１は、上記と同義である。）で示されるジセミカルバジド化合物であることが好ましい。式（Ｉｂ）におけるＸ^１は、式（Ｉ）において、ｎが２の場合におけるＡと同義である。In the curing agent of the present invention, the compound having at least one primary amino group in the molecule is represented by the following formula (Ib):

(Wherein X ¹ has the same meaning as described above), and is preferably a disemicarbazide compound. X ¹ in formula (Ib) has the same meaning as A in the case where n is 2 in formula (I).

  The compound represented by the formula (Ib) is preferably obtained by reacting the diisocyanate compound with hydrazine. The diisocyanate compound and hydrazine are preferably 0.01 mol to 50 mol, more preferably 0.1 mol to 50 mol, and still more preferably 0.1 mol with respect to 1 mol of the diisocyanate compound. In an organic solvent or neat (no solvent), preferably −10 ° C. to 120 ° C., more preferably −5 ° C. to 100 ° C., even more preferably 0.1 mol to 30 mol, particularly preferably 0.1 mol to 20 mol. Is preferably obtained by reaction while controlling at 0 to 50 ° C., particularly preferably 5 to 30 ° C.

As the disemicarbazide compound represented by the above formula (Ib), for example,
4,4 ′-(methylenedi-1,4-cyclohexylene) bis (semicarbazide) (B-1),
4,4′-hexamethylenebis (semicarbazide) (B-2),
4,4 ′-(2,2,4-trimethylhexamethylene) bis (semicarbazide) (B-3),
4,4 ′-(1,3-cyclohexylenebismethylene) bis (semicarbazide) (B-4),
4,4 ′-(1,3-phenylenebismethylene) bis (semicarbazide) (B-5),
4,4′-isophoronebis (semicarbazide) (B-6) and the like.

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

〔式中、
Ｒ^１は、単結合であるか、あるいはＣ_１〜Ｃ_１２アルキレン、１つ若しくはそれ以上のＮＨ（イミノ基）若しくはＯ原子（酸素原子）で非連続的に中断されたＣ_２〜Ｃ_１２アルキレン（Ｎ原子（窒素原子）に結合するＨ原子（水素原子）は、アミノ基又はＣ_１〜Ｃ_１２のアルキルアミノ基で置換されていてもよい）、Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_１２アルキレン、Ｃ_３〜Ｃ_１２シクロアルキレン−Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_６〜Ｃ_１４アリーレン、Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン、Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン、又はＣ_６〜Ｃ_１４アリーレン−Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン（ここで、アルキレンは、直鎖又は分岐鎖であり、ハロゲンで置換されていてもよく、Ｃ_３〜Ｃ_１２シクロアルキレン又はＣ_６〜Ｃ_１４アリーレンは、非置換であるか、又はハロゲン若しくはＣ_１〜Ｃ_４アルキルで置換されている。）であり、
Ｘ^２は、Ｃ_１〜Ｃ_１２アルキル、１つ若しくはそれ以上のＯ原子（酸素原子）で非連続的に中断されたＣ_２〜Ｃ_１２アルキル、Ｃ_１〜Ｃ_１２アルキルオキシカルボニルアルキレン、Ｃ_３〜Ｃ_１２シクロアルキル、Ｃ_１〜Ｃ_１２アルキル−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_３〜Ｃ_１２シクロアルキル−Ｃ_１〜Ｃ_１２アルキレン−Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_６〜Ｃ_１４アリール、Ｃ_１〜Ｃ_４アルキル−Ｃ_６〜Ｃ_１４アリーレン、Ｃ_６〜Ｃ_１４アリール−Ｃ_１〜Ｃ_４アルキレン−Ｃ_６〜Ｃ_１４アリーレン（ここで、アルキレンは、直鎖又は分岐鎖であり、ハロゲンで置換されていてもよく、Ｃ_３〜Ｃ_１２シクロアルキル、Ｃ_３〜Ｃ_１２シクロアルキレン、Ｃ_６〜Ｃ_１４アリール又はＣ_６〜Ｃ_１４アリーレンは、非置換であるか、又はハロゲン若しくはＣ_１〜Ｃ_４アルキルで置換されている。）、又は（メタ）アクリロイルオキシアルキルである。〕で示される化合物を含むことが好ましい。式（ＩＩａ）におけるＸ^２は、式（Ｉ）において、ｎが１の場合におけるＡと同義である。The curing agent of the present invention has the following formula (IIa)

[Where,
R ¹ is a single bond or C ₁ -C ₁₂ alkylene, C ₂ -C ₁₂ alkylene interrupted discontinuously by one or more NH (imino group) or O atoms (oxygen atoms) (The H atom (hydrogen atom) bonded to the N atom (nitrogen atom) may be substituted with an amino group or a C ₁ -C ₁₂ alkylamino group), C ₃ -C ₁₂ cycloalkylene, C _1- C ₁₂ alkylene _-C 3 _{-C 12 cycloalkylene,} C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12 alkylene,} C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12} alkylene -C _{3 to} C ₁₂ cycloalkylene, C _{6 to} C ₁₄ arylene, C _{1 to} C ₄ alkylene-C _{6 to} C ₁₄ arylene, C _{1 to} C ₄ alkylene-C _{6 to} C _{1 4-} arylene-C ₁ -C ₄ alkylene, or C ₆ -C ₁₄ arylene-C ₁ -C ₄ alkylene-C ₆ -C ₁₄ arylene (wherein alkylene is linear or branched and is substituted with halogen) And C ₃ -C ₁₂ cycloalkylene or C ₆ -C ₁₄ arylene is unsubstituted or substituted with halogen or C ₁ -C ₄ alkyl).
X ² is C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkyl interrupted discontinuously with one or more O atoms (oxygen atoms), C ₁ -C ₁₂ alkyloxycarbonylalkylene, C ₃ -C _{12 cycloalkyl,} C 1 _{-C 12} alkyl _-C 3 _{-C 12 cycloalkylene,} C 3 _{-C 12} cycloalkyl _-C 1 _{-C 12} alkylene _-C 3 _{-C 12 cycloalkylene,} C 6 _{-C 14} aryl C ₁ -C ₄ alkyl-C ₆ -C ₁₄ arylene, C ₆ -C ₁₄ aryl-C ₁ -C ₄ alkylene-C ₆ -C ₁₄ arylene (wherein alkylene is linear or branched, may be substituted with _halogen, C 3 _{-C 12 cycloalkyl,} C 3 _{-C 12 cycloalkylene,} C 6 _{-C 14} aryl or _C 6 _{-C 14} Arylene, unsubstituted or halogen or substituted with C ₁ -C ₄ alkyl.), Or (meth) acryloyloxy alkyl. It is preferable that the compound shown by these is included. X ² in formula (IIa) has the same meaning as A in the case where n is 1 in formula (I).

  The compound represented by the formula (IIa) is preferably obtained by reacting the monoisocyanate compound with the hydrazine or polyvalent amine compound. The monoisocyanate compound and the hydrazine or polyvalent amine compound are preferably 0.1 mol to 50 mol, more preferably the amino group of the diamino compound with respect to 1 mol of the isocyanate group of the monoisocyanate compound. In an organic solvent or neat (no solvent) so as to be 0.1 to 30 mol, particularly preferably 0.1 to 20 mol, preferably −10 ° C. to 120 ° C., more preferably −5 ° C. to 100 ° C. It is preferably obtained by reacting at a temperature of 0 ° C., more preferably 0 ° C. to 50 ° C., particularly preferably 5 to 30 ° C.

式中、Ｘ^２は、上記と同義である。式（ＩＩｂ）におけるＸ^２は、式（Ｉ）において、ｎが１の場合におけるＡと同義である。In the formula (IIa), when R ¹ is a single bond, it is a semicarbazide compound. The semicarbazide compound is preferably a compound represented by the following formula (IIb).

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

  The compound represented by the formula (IIb) is preferably obtained by reacting the monoisocyanate compound with hydrazine. The monoisocyanate compound and hydrazine are preferably 0.01 mol to 50 mol, more preferably 0.1 mol to 50 mol, and still more preferably 0.1 mol with respect to 1 mol of the monoisocyanate compound. In an organic solvent or neat (no solvent), preferably −10 ° C. to 120 ° C., more preferably −5 ° C. to 100 ° C., even more preferably 0.1 mol to 30 mol, particularly preferably 0.1 mol to 20 mol. Is preferably obtained by reaction while controlling at 0 to 50 ° C., particularly preferably 5 to 30 ° C.

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

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

The curing agent of the present invention is obtained by reacting the above isocyanate compound with hydrazine or a polyvalent amine compound having two or more primary amino groups in the molecule, and at least one primary in the molecule. It is also preferable that the curing agent contains a compound obtained by further treating a compound having an amino group with an isocyanate compound.
When the curing agent contains a compound obtained by treating a compound having at least one primary amino group in the molecule with an isocyanate compound, the curing agent and the epoxy resin and / or at least one unsaturated bond The liquid stability of a resin composition containing a resin having a viscosity can be improved, and an increase in viscosity over time can be suppressed.

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

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

  Treatment of the compound having at least one primary amino group in the molecule with an isocyanate compound is in an organic solvent or neat (no solvent), preferably -10 ° C to 120 ° C, more preferably -5 ° C to 100 ° C. It is preferable to carry out the reaction at a temperature of 10 ° C., more preferably 10 ° C. to 90 ° C., particularly preferably 20 ° C. to 80 ° C. The treatment time can be 0.1 to 100 hours, for example, and preferably 0.5 to 50 hours. The time for heating and mixing varies depending on the temperature to be heated and mixed, and the time is shortened when the temperature is high, and the time is lengthened when the temperature is low.Therefore, the optimum processing time is selected according to the purpose of use when used as a curing agent. It is possible to select.

The curing agent of the present invention is obtained by reacting the above isocyanate compound with hydrazine or a polyvalent amine compound having two or more primary amino groups in the molecule, and at least one primary in the molecule. It is also preferable that the curing agent contains a compound obtained by further treating a compound having an amino group with an isocyanate compound and an epoxy resin.
The curing agent contains a compound obtained by treating a compound having at least one primary amino group in the molecule with an isocyanate compound and an epoxy resin, whereby the curing agent and the epoxy resin and / or at least one compound is obtained. The liquid stability of a resin composition containing a resin having an unsaturated bond is improved, and an increase in viscosity over time can be suppressed.

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

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

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

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

  Treatment of the compound having at least one primary amino group in the molecule with an isocyanate compound and an epoxy resin is in an organic solvent or neat (no solvent), preferably -10 ° C to 120 ° C, more preferably -5. It is preferable to carry out the reaction while controlling at a temperature of from 100 ° C to 100 ° C, more preferably from 10 ° C to 90 ° C, particularly preferably from 20 ° C to 80 ° C. The treatment time can be 0.1 to 100 hours, for example, and preferably 0.5 to 50 hours. The time for heating and mixing varies depending on the temperature to be heated and mixed, and the time is shortened when the temperature is high, and the time is lengthened when the temperature is low.Therefore, the optimum processing time is selected according to the purpose of use when used as a curing agent. It is possible to select.

The curing agent of the present invention is obtained by reacting the above isocyanate compound with hydrazine or a polyvalent amine compound having two or more primary amino groups in the molecule, and at least one primary in the molecule. It is also preferable that the curing agent contains a compound obtained by treating a compound having an amino group with an isocyanate compound and a compound having a hydroxy group.
When the curing agent contains a compound obtained by treating a compound having at least one primary amino group in the molecule with an isocyanate compound and a compound having a hydroxy group, the curing agent and the epoxy resin and / or at least The liquid stability of a resin composition containing a resin having one unsaturated bond is improved, and an increase in viscosity over time can be suppressed.

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

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

Among the alcohol compounds, examples of the monoalcohol compound include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butyl alcohol, 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, trimethylsilylmethanol, Allyl alcohol, 2-bromoethanol, 3-ethyl-2-methyl-3-pentanol, 2-iodoethanol, 1-methoxy-2-propanol, acetone cyanohydrin, (R)-(-)-1-methoxy 2-propanol, 3-pentyne- -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-difluoroethanol, methyl glycolate, 4-heptanol, 3-hexanol, 3 -Hexyn-1-ol, 3-methyl-1-butanol, (S)-(-)-2-methyl-1-butanol, DL-2-methyl-1-butanol, 2-methyl-3-butyne-2 -Ol, 4-methyl-4-heptanol, 2-methyl-2-pentanol, 2-pentanol, (S)-(+)-2-pentanol, (R)-(-)-2-pentanol 2,2,2-trifluoroethane 2,2,2-trichloroethanol, 2,2,2-tribromoethanol, 3-trimethylsilyl-2-propyn-1-ol, 1-bromo-2-propanol, 1-buten-3-ol, 2-butyn-1-ol, 1-chloro-2-propanol, cycloheptanol, cyclobutanol, 1-chloro-2-methyl-2-propanol, 1,3-dibromo-2-propanol, 1,3-dichloro 2-propanol, 2,6-dimethyl-4-heptanol, 2,2-dimethyl-3-hexanol, 2,5-dimethyl-3-hexanol, 3,5-dimethyl-3-hexanol, 2-ethyl-1 -Butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-hexanol, 2-hexanol, hydroxyacetone, 3 -Methoxy-1-butanol, 2-methyl-3-buten-2-ol, 4-methyl-2-pentanol, 1-decanol, 1-nonanol, 1-octanol, 1-dodecanol, 3,7-dimethyl- 1-octanol, 1-tetradecanol, 1-undecanol, 1-hexadecanol, 1-octadecanol, 1-pentadecanol, 2-octanol, 1-docosanol, 1-eicosanol, cyclohexanemethanol, cyclododecanol , Cyclohexaneethanol, 2,5-dimethylcyclohexanol, 2-methylcyclohexanol, 1-cyclohexyl-1-butanol, 2-ethylcyclohexanol, 4- (2-hydroxyethyl) cyclohexanol, 1-cyclohexyl-1-pen Tanol, 9-decene-1 All, oleyl alcohol, 4-cyclohexylcyclohexanol, 2-cyclohexylcyclohexanol, decahydro-2-naphthol, 1-decen-3-ol, 1-nonen-3-ol, 3,5-dimethyl-1-adamantane methanol, 8-dimethylamino-1-octanol, 4- (hydroxymethyl) cyclohexanecarboxylic acid, trans-4- (hydroxymethyl) cyclohexanecarboxylic acid, 4- (trifluoromethyl) cyclohexanemethanol, borneol, 2- (benzyloxy) ethanol Etc.
Also, 2-methoxyethanol, diethylene glycol monomethyl ether, decaethylene glycol monomethyl ether, dodecaethylene glycol monomethyl ether, 3-methoxy-1-propanol, 1-butoxy-2-propanol, pentaethylene glycol monomethyl ether, triethylene glycol monomethyl ether And monoalcohol compounds having an ether bond such as tetraethylene glycol monomethyl ether and 1,4-butanediol monomethyl ether.

  Examples of the diol compound include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 2,3-dimethyl-2,3-butanediol, and 2,2-dimethyl- 1,3-propanediol, 2-methyl-1,3-propanediol, (S, S)-(+)-2,3-butanediol, pinacol, 2,2-dimethyl-1,3-propanediol, 1,7-heptanediol, 1,5-pentanediol, (S)-(+)-1,2-propanediol, (R)-(−)-1,2-propanediol, 1,5-pentanediol (S)-(+)-1,2-propanediol, (R)-(−)-1,2-propanediol, 2-butyne-1,4-diol, 1,6-hexanediol, 1, 8-octa Diol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,2-decanediol, 1,2-tetradecanediol, 1,4-cyclohexanedimethanol, neopentyl glycol monol 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3-bis (2-hydroxyethoxy) benzene, Examples thereof include 1,4-bis (2-hydroxyethoxy) -2-butyne, diethylene glycol, tripropylene glycol, 2,2-bis (4-hydroxycyclohexyl) propane, and the like.

Examples of the triol compound include 1,1,1-tris (hydroxymethyl) ethane, glycerol, 1,2,8-octanetriol and the like.
Furthermore, examples of the tetrafunctional or higher functional polyol compound include dipentaerythritol, diglycerol, and span 20.

  Among the phenol compounds, monofunctional phenol compounds include 4-methoxyphenol, 3-chlorophenol, 4-chlorophenol, p-cresol, m-cresol, o-cresol, 3,5-dichlorophenol, guaiacol, 4- Bromophenol, 2,6-dichlorophenol, 4-fluorophenol, 4-iodophenol, 3-methoxyphenol, 3,5-dimethoxyphenol, 4-phenoxyphenol, 3-bromophenol, 2-bromophenol, 2,4 -Dichlorophenol, 3,4-dichlorophenol, 2,6-dimethoxyphenol, 2,6-dimethylphenol, 3,5-dimethylphenol, 2-fluorophenol, 3-fluorophenol, 2-iodophenol, 3-iodo Phenol 4-methoxy-1-naphthol, 2,4,6-trichlorophenol, 4-aminophenol, 6-bromo-2-naphthol, 4-chloro-1-naphthol, 2,3-dichlorophenol, 2,5-dichloro Phenol, 2,4-dimethylphenol, 3,4-dimethylphenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,6-dibromophenol, 3,5-dibromophenol, 2,4,6- Trimethylphenol, 4-aminophenol hydrochloride, 4-tert-butylphenol, 4-tert-butoxyphenol, 4-hydroxybenzonitrile, 2,4-dibromophenol, 2,3-dimethylphenol, 2,4-difluorophenol, 3,4-difluorophenol, 3,4-dimethoxyph Nord, 4-ethylphenol, 4-ethoxyphenol, 4-hydroxybenzaldehyde, 4-hydroxybenzenethiol, 4-isopropylphenol, 4- (methylthio) phenol, 2,4,6-tribromophenol, 2,4,6 -Triiodophenol, 2,3,6-trichlorophenol, 5-amino-2-naphthol, 6-amino-1-naphthol, 3-aminophenol, 1-bromo-2-naphthol, 3-bromo-2-naphthol 2,4-dichloro-1-naphthol, 1,6-dibromo-2-naphthol, 2,5-difluorophenol, 2,3-difluorophenol, 4-hydroxybenzotrifluoride, 3-hydroxybenzenethiol, pentachloro Phenol, 4-propylphenol, 2,3,4 , 6-tetrachlorophenol, 2,4,5-trichlorophenol, 2-aminophenol, 5-amino-1-naphthol, 8-amino-2-naphthol, 4-tert-amylphenol, 3-tert-butylphenol, 4-sec-butylphenol, 3-cyanophenol, 3-ethoxyphenol, 3-ethylphenol, 2-ethoxyphenol, 3-hydroxybenzaldehyde, 4-benzylphenol, 6-hydroxy-2-naphthonitrile, 6-hydroxy-2 -Naphthaldehyde, 3-isopropylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 4- (trifluoromethoxy) phenol, 4-amino-1-naphthol hydrochloride, 2-aminophenol Hydrochloride 2-ter -Butylphenol, 4-butylphenol, 4-α-cumylphenol, 2-cyanophenol, 2,4-dibromo-1-naphthol, 3- (dimethylamino) phenol, 2-ethylphenol, 4'-hydroxyacetophenone, 4 -Hexylphenol, 2-hydroxybenzotrifluoride, 2-hydroxybenzenethiol, 2-isopropylphenol, 2- (methylthio) phenol, 4-amylphenol salicylaldehyde, 3-hydroxybenzotrifluoride, 2,3,5,6 -Tetrafluorophenol, 2,3,4-trifluorophenol, 2-chlorophenol and the like can be mentioned.

  Examples of phenolic compounds having two hydroxy groups include 4,4′-dihydroxydiphenyl ether, 5-methoxyresorcinol, 2-methylresorcinol, 5-methylresorcinol monohydrate, 5-methylresorcinol (anhydrous), chlorohydroquinone, 4 -Chlorocatechol, 2,2'-dihydroxydiphenyl ether, 1,3-bis (4-hydroxyphenoxy) benzene, 5-bromoresorcinol, 4-chlororesorcinol, 3-chlorocatechol, 4,6-dichlororesorcinol, 2-iodo Resorcinol, methylhydroquinone, 4-methylcatechol, 3-methoxycatechol, methoxyhydroquinone, 4-bromoresorcinol, 1,4-bis (3-hydroxyphenoxy) benzene, bromohydroquinone, 4 Bromocatechol, 2,6-dimethylhydroquinone, 2,5-dimethylresorcinol, 2,3-dimethylhydroquinone, 4-fluorocatechol, 4-fluororesorcinol, 3-methylcatechol, tetrachlorohydroquinone, 4,4'-dihydroxydiphenylmethane 3-bromocatechol, cresol (isomer mixture), bis (4-hydroxyphenyl) sulfide, 2,6-dibromo-1,5-dihydroxynaphthalene, 3-fluorocatechol, 2,4,6-tribromoresorcinol, Bifunctional phenolic compounds such as 2,2-bis (4-hydroxyphenyl) propane, 4,4′-ethylidenebisphenol, trimethylhydroquinone, 1,2-dihydroxynaphthalene, monofunctional phenols such as 4-hydroxybenzyl alcohol Nord compounds, and the like can be mentioned.

Examples of the trifunctional phenol compound include 1,2,4-trihydroxybenzene, 1,8,9-trihydroxyanthracene, 5-methylpyrogallol, 4,4 ′, 4 ″ -trihydroxytriphenylmethane, and the like. Can do.
Examples of the tetrafunctional phenol compound include leucoquinizarin, and examples of the hexafunctional phenol compound include hexahydroxybenzene, 2,3,6,7,10,11-hexahydroxytriphenylene hydrate, and the like. .

  Examples of carboxylic acid compounds include methoxyacetic acid, glyoxylic acid, heptanoic acid, decanoic acid, nonanoic acid, lauric acid, myristic acid, 4-methyl-n-octanoic acid, pimelic acid, heptadecanoic acid, 16-hydroxyhexadecanoic acid, 15- Monocarboxylic acids such as hydroxypentadecanoic acid, palmitic acid, pentadecanoic acid, stearic acid, behenic acid, arachidic acid, heneicosanoic acid, 12-hydroxystearic acid, 2-hexyldecanoic acid, azelaic acid, suberic acid, sebacic acid, (+) -Dicarboxylic acids such as camphoric acid and dodecanedioic acid, and trifunctional or higher polycarboxylic acids such as 1,3,5-pentanetricarboxylic acid.

  The compound which has a hydroxy group may be used individually by 1 type or in combination of 2 or more types. Among these, it is preferable to use at least one selected from the group consisting of alcohol compounds (preferably diol compounds) and phenol compounds.

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

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

  The treatment of the compound having at least one primary amino group in the molecule with the isocyanate compound and the compound having a hydroxy group is in an organic solvent or neat (no solvent), preferably -10 ° C to 120 ° C, more preferably. Is preferably carried out while controlling at -5 ° C to 100 ° C, more preferably 10 ° C to 90 ° C, particularly preferably 20 ° C to 80 ° C. The treatment time can be 0.1 to 100 hours, for example, and preferably 0.5 to 50 hours.

[Resin composition]
The resin composition of the present invention is obtained by reacting the isocyanate compound with hydrazine or a polyvalent amine compound having two or more primary amino groups in the molecule. A curing agent (A) containing a compound having a secondary amino group and an epoxy resin and / or a resin (B) having at least one unsaturated bond in the molecule are included. The curing agent (A) preferably contains a compound represented by at least one selected from the group consisting of the above formulas (I), (Ia), (Ib), (IIa) and (IIb). It is also preferable to include a compound obtained by treating the compound with an isocyanate compound, an isocyanate compound and an epoxy resin, or an isocyanate compound and a compound having a hydroxy group.

〔Epoxy resin〕
As the epoxy resin, known ones can be used, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, cycloaliphatic. Examples thereof include epoxy resins, glycidyl ester resins, glycidyl amine epoxy resins, heterocyclic epoxy resins, and urethane-modified epoxy resins. Among these, it is preferable to use a bisphenol A type epoxy resin, a cresol novolac type epoxy resin, or the like. Epoxy (meth) acrylic acid obtained by modifying a resin having a glycidyl group with (meth) acrylic acid may be used. For example, it is preferable to use a partially esterified epoxy resin obtained by reacting an epoxy resin described in JP 2012-77202 A and (meth) acrylic acid. Specifically, (meth) acrylic acid is preferably 10 to 90 equivalent%, more preferably 20 to 80 equivalent%, still more preferably 30 to 70 equivalent%, particularly 1 equivalent to the epoxy group of the epoxy resin. It is preferable to use a partially esterified epoxy resin obtained by reacting 40 to 60 equivalent percent (meth) acrylic acid. An epoxy resin may be used individually by 1 type, and may use multiple types together. Moreover, an unsaturated bond containing epoxy resin may be sufficient.

  The partially esterified epoxy resin is, for example, a bisphenol A type epoxy resin and acrylic acid or methacrylic acid, in the presence of a basic catalyst according to a conventional method, with 0.9 to 1 carboxylic acid groups per 2 equivalents of epoxy groups. The reaction product was added with approximately 4 times the mass ratio of toluene and the same amount of pure water, stirred at 60 to 80 ° C. for 1 hour, and allowed to stand for organic reaction. The layer is separated into an aqueous layer and the aqueous layer is removed. This operation is repeated 3 to 5 times, and finally the organic layer is recovered and the remaining toluene is removed by vacuum distillation to obtain a partially esterified epoxy resin that has been subjected to a reduction treatment of water-soluble ionic substances. it can. Specific examples of the above-described bisphenol A type epoxy resin include, for example, Epicoat 828, 834, 1001, 1004 (manufactured by Mitsubishi Chemical Corporation), Epicron 850, 860, 4055 (manufactured by DIC Corporation). As these raw material resins, a resin that has been subjected to a treatment for reducing a water-soluble ionic substance (hereinafter referred to as a purification treatment), such as Epicron 850S (manufactured by DIC), is preferable.

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

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

  When the epoxy resin and a resin having at least one unsaturated bond in the molecule are used in combination, the blending amount of the epoxy resin and the resin having at least one unsaturated bond in the molecule is determined by the resin composition It can be appropriately determined depending on the purpose of the cured product obtained by curing the product. When the resin having at least one unsaturated bond in the molecule is a (meth) acrylic acid derivative having at least one (meth) acryloyl group in the molecule, ) It is preferable to mix | blend so that an acryloyl group may be 0.1-9.0 equivalent, and it is more preferable to mix | blend so that a (meth) acryloyl group may become 0.3-4.0 equivalent.

  The resin composition may contain a silicone resin, a urea resin, an imide resin, glass, or the like as necessary in addition to the resin.

  In addition, the resin composition includes various additives as necessary, for example, antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, coating surface improvers, thermal polymerization inhibitors, leveling agents, interfaces. An activator, a colorant, a storage stabilizer, a plasticizer, a lubricant, a filler, inorganic particles, an anti-aging agent, a wettability improver, an antistatic agent, and the like may be blended.

  The blending amount of the curing agent (A) and the epoxy resin and / or the resin (B) having at least one unsaturated bond in the molecule is that of the curing agent (A) with respect to 1 equivalent of the epoxy resin. The total amount of semicarbazide groups or primary amino groups is preferably 0.001 to 10 equivalents, more preferably 0.01 to 8 equivalents, still more preferably 0.05 to 5 equivalents, and particularly preferably 0.1 to 3 equivalents. Is equivalent. When the total amount of the semicarbazide group or primary amino group of the curing agent (A) is 0.1 to 3 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin, the resin composition is sealed in a liquid crystal display panel or the like When it is contained in the agent, it can be applied to the thinning required for the sealing agent, diversification of the adhesiveness to various adherends, etc., and the mounting of the IC for driving the cell and driving the liquid crystal cell Adhesive strength that can suppress peeling at times and the like can be expressed.

As the blending amount of the curing agent (A) and the epoxy resin and / or the resin (B) having at least one unsaturated bond in the molecule, the epoxy resin (B) is contained alone, or the epoxy resin and the molecule In the case of containing both of the resin (B) having at least one unsaturated bond, the semicarbazide group or the primary amino group of the curing agent (A) is equivalent to 1 equivalent of the epoxy group of the epoxy resin. The total amount is preferably 0.0005 to 10 equivalents, more preferably 0.005 to 8 equivalents, still more preferably 0.025 to 5 equivalents, and particularly preferably 0.05 to 3 equivalents.
Further, when the resin (B) having at least one unsaturated bond in the molecule is contained alone, the semicarbazide group of the curing agent (A) or the second group is added to 1 equivalent of the unsaturated bond of the resin (B). The total amount of primary amino groups is preferably 0.0005 to 10 equivalents, more preferably 0.005 to 8 equivalents, still more preferably 0.025 to 5 equivalents, and particularly preferably 0.05 to 3 equivalents. When the blending amount of the curing agent (A) with respect to the resin (B) is within the above range, the thinning required for the sealing agent when the resin composition is contained in the sealing agent such as a liquid crystal display panel, It is possible to adapt to diversification of adhesiveness to various adherends, and to exhibit adhesive strength that can suppress peeling at the time of cell cutting and mounting of an IC for driving a liquid crystal cell.

[Liquid crystal sealant composition]
This invention is a liquid-crystal sealing compound composition containing the said resin composition. The liquid crystal sealing agent composition includes a resin composition containing the curing agent (A), an epoxy resin and / or a resin (B) having at least one unsaturated bond in the molecule, and a photopolymerization initiator (C ) And, if necessary, an inorganic filler (D).

[Photopolymerization initiator (C)]
Examples of the photopolymerization initiator include benzophenone, 2,2-diethoxyacetophenone, benzyl, benzoyl isopropyl ether, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, and thioxanthone. Moreover, you may use the commercially available radical photopolymerization initiator as a photoinitiator. Commercially available photo radical polymerization initiators include, for example, Irgacure 907, Irgacure 819, Irgacure 651, Irgacure 369, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and lucillin TPO (all of which are manufactured by BASF Japan Ltd.) ) And the like.

[Inorganic filler (D)]
The inorganic filler is not particularly limited, and examples thereof include spherical silica, spherical alumina, spherical titanium oxide, spherical aluminum oxide, and spherical calcium carbonate. Of these, spherical silica is preferred because of its excellent dispersibility and excellent effect of improving the adhesiveness of a sealing agent suitable for the liquid crystal dropping method and the moisture resistance of a cured product.

  As a compounding ratio of each component of the liquid crystal sealant composition, 0.5 to 5 parts by mass, preferably 0.5 to 4 parts by mass of (C) photopolymerization initiator, with respect to 100 parts by mass of the resin composition, More preferably, it is 0.8-3 mass parts, (D) The inorganic filler is 0-40 mass parts, Preferably it is 2-30 mass parts, More preferably, it is 3-20 mass parts. Moreover, it is preferable that (C) photoinitiator is 0.5-3 mass% and (D) inorganic filler is 0-40 mass% in the total mass of a liquid-crystal sealing compound composition.

  The liquid crystal sealant composition is preferably produced by kneading thoroughly using a paint roll or the like, paying particular attention to uniform and complete dispersion of solid materials such as inorganic fillers.

[LCD panel]
The liquid crystal sealant composition of the present invention satisfies the demands for thinning and diversification of adhesiveness, and exhibits adhesive strength that can suppress peeling at the time of cell cutting and mounting of an IC for driving a liquid crystal cell. And can be suitably used for manufacturing a liquid crystal display panel.
That is, the liquid crystal display panel of the present invention is sealed with an opposing glass substrate, a cured product of a liquid crystal sealing agent composition that bonds the opposing glass substrate, and an opposing glass substrate and a cured product of the liquid crystal sealing agent composition. Liquid crystal.

[Manufacturing method of liquid crystal display panel]
A liquid crystal display panel can be manufactured by performing thermosetting after performing photocuring using the liquid crystal sealing agent composition of the present invention. FIG. 1 shows an embodiment for manufacturing a liquid crystal display panel. Specifically, the glass substrate 1 is used as shown in the cross-sectional view of FIG. 1A, and the liquid crystal sealant composition of the present invention is formed on one glass substrate 1 as shown in the cross-sectional view of FIG. Product 2 was applied. Next, as shown in the cross-sectional view of FIG. 1C, the other glass substrate 4 is placed on the liquid crystal sealing agent composition 2 on one glass substrate 1 so as to face each other, and light such as ultraviolet rays is applied under pressure. The liquid crystal sealing agent composition 2 is solidified by irradiation in an amount of 1,000 to 3,000 mJ, and the pair of glass substrates 1 and 4 are bonded together, and then, at a temperature of 100 to 120 ° C. with no pressure applied. By heating for about 1 hour and sufficiently cured, a liquid crystal encapsulation cell 5 surrounded by a pair of glass substrates 1 and 4 and a cured liquid crystal sealant 2 is formed. Next, as shown in the plan view of FIG. 1 (d), after the liquid crystal 6 is injected from the liquid crystal injection hole 3 in a vacuum in the cell 5, the liquid crystal injection hole 3 is sealed, and the liquid crystal display panel 7 is mounted. Can be manufactured. The liquid crystal sealing composition is dispensed on an ITO glass substrate with an alignment film that has been subjected to a rabin treatment, and then a liquid crystal is dropped onto the substrate, and the upper and lower substrates are bonded together by a liquid crystal dropping method (ODF method), and ultraviolet rays (for example, illuminance) and irradiation time: for 1000 ^mJ, when the 100mW / cm 2 / 365nm, 50mJ , 50mW / cm 2 / 365nm in 1 second) and then cured by irradiation with, by 1 hour thermoset Thereafter example 120 ° C. hot air oven Also good.

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

(Synthesis of curing agent)
Example 1
(B-1) 4,4 ′-(Methylenedi-1,4-cyclohexylene) bis (semicarbazide)

A solution A in which 13.05 g of dicyclohexylmethane-4,4′-diisocyanate is dissolved in 75 g of ethanol and a solution B in which 5 g of hydrazine is dissolved in 75 g of ethanol are prepared. Dissolving solution B is put in a flask, and dissolving solution A is dropped at a rate of 1.4 g / min while being controlled and stirred at 25 ° C. After completion of the dropwise addition of the solution A, the reaction solution was measured with a Fourier transform infrared spectrophotometer, and it was confirmed that there was no peak near 2250 cm ⁻¹ derived from the isocyanate group, and the reaction was completed. The reaction was carried out so that hydrazine was 2 mol (1: 2 in molar ratio) with respect to 1 mol of dicyclohexylmethane-4,4′-diisocyanate.
After completion of the reaction, the solution was filtered through a Kiriyama funnel (manufactured by Kiriyama Co., Ltd.) using a filter paper (Kiriyama Co., Ltd. No. 4), and the liquid was removed. The obtained filtered product was dried at 50 ° C. in a vacuum oven.
After drying, the mixture was pulverized with a high-pressure pulverizer (trade name: Nanojet Mizer, manufactured by Aisin Nano Technologies) to produce a carbazide compound having an average particle diameter (median diameter) of 2.0 μm.
In addition, the average particle diameter (median diameter) was measured using a particle size distribution meter (LA-950V2: manufactured by Horiba, Ltd.).

(Example 2)
(B-2) 4,4′-Hexamethylenebis (semicarbazide)

A solution A in which 16.8 g of hexamethylene diisocyanate was dissolved in 150 g of ethanol and a solution B in which 10 g of hydrazine was dissolved in 150 g of ethanol were prepared. The solution A is dropped at a rate of 1.4 g / min while the solution B is controlled and stirred at 25 ° C. After the completion of the dropwise addition of the solution A, the reaction solution was measured with a Fourier transform infrared spectrophotometer, and it was confirmed that there was no peak near 2250 cm ⁻¹ derived from the isocyanate group, and the reaction was completed. The reaction was performed so that hydrazine was 2 mol (molar ratio 1: 2) with respect to 1 mol of hexamethylene diisocyanate.
After completion of the reaction, it was filtered through a Kiriyama funnel (manufactured by Kiriyama Co., Ltd.) using a filter paper (Kiriyama Co., Ltd. No. 4), and the liquid was removed. The obtained filtered product was dried at 50 ° C. in a vacuum oven. After drying, the mixture was pulverized with a high-pressure pulverizer (trade name: NanoJet Mizer, manufactured by Aisin Nano Technologies) to produce a carbazide compound having an average particle diameter (median diameter) of 2.1 μm.

Example 3
(B-7) 4- (Ethyl acrylate) semicarbazide

A solution A in which 14.1 g of 2-isocyanatoethyl acrylate was dissolved in 150 g of ethanol and a solution B in which 5 g of hydrazine was dissolved in 150 g of ethanol were prepared. The solution A was dropped at a rate of 1.4 g / min while the solution B was being stirred at 25 ° C. After the completion of the dropwise addition of the solution A, the reaction solution was measured with a Fourier transform infrared spectrophotometer, and it was confirmed that there was no peak near 2250 cm ⁻¹ derived from the isocyanate group, and the reaction was completed. It was made to react so that it might become 1 mol (molar ratio 1: 1) with respect to 1 mol of 2-isocyanatoethyl acrylate.
After completion of the reaction, ethanol is evaporated at 50 ° C. with an evaporator, and the purified product is measured with a Fourier transform infrared spectrophotometer, and it is confirmed that there is no peak near 3300 cm ⁻¹ derived from ethanol, and a liquid carbazide compound is produced. did.

Example 4
(B-3) 4,4 ′-(2,2,4-trimethylhexamethylene) bis (semicarbazide)

A solution A in which 10.51 g of trimethylhexanemethylene diisocyanate was dissolved in 50 g of ethanol and a solution B in which 5.01 g of hydrazine was dissolved in 50 g of ethanol were prepared. The solution A was dropped at a rate of 1.4 g / min while the solution B was being stirred at 25 ° C. After the completion of the dropwise addition of the solution A, the reaction solution was measured with a Fourier transform infrared spectrophotometer, and it was confirmed that there was no peak near 2250 cm ⁻¹ derived from the isocyanate group, and the reaction was completed. The reaction was carried out so that hydrazine was 2 mol (1: 2 molar ratio) with respect to 1 mol of trimethylhexamethylene diisocyanate.
After completion of the reaction, ethanol is evaporated at 50 ° C. with an evaporator, and the purified product is measured with a Fourier transform infrared spectrophotometer, and it is confirmed that there is no peak near 3300 cm ⁻¹ derived from ethanol, and a liquid carbazide compound is produced. did.

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

A solution A in which 18.82 g of m-xylylene diisocyanate is dissolved in 100 g of isopropanol and a solution B in which 25.3 g of hydrazine are dissolved in 100 g of isopropanol are prepared. The solution A is dropped at a rate of 1.4 g / min while the solution B is being stirred at 30 ° C. in a three-necked flask. After completion of the dropwise addition of the solution A, the reaction solution is measured with a Fourier transform infrared spectrophotometer, and it is confirmed that there is no peak near 2250 cm ⁻¹ derived from the isocyanate group, and the reaction is completed. It was made to react so that hydrazine might be 5 mol (molar ratio 1: 5) with respect to 1 mol of m-xylylene diisocyanate.
After completion of the reaction, the solution was filtered with a Kiriyama funnel (manufactured by Kiriyama Co., Ltd.) using a filter paper (Kiriyama Co., Ltd. No. 4), the liquid was removed, and the resulting filtrate was washed with 50 ml of isopropyl alcohol and further filtered. The obtained filtered product was dried at 50 ° C. in a vacuum oven.
After drying, the mixture was pulverized with a high-pressure pulverizer (trade name: Nanojet Mizer, manufactured by Aisin Nano Technologies) to produce a carbazide compound having an average particle diameter (median diameter) of 2.2 μm.

イソプロパノール１００ｇに１，３−ビス（イソシアナトメチル）シクロヘキサンを１９．４２ｇ溶解した溶解液Ａと、イソプロパノール１００ｇにヒドラジン２５．３ｇを溶解した溶解液Ｂを用意する。三口フラスコで溶解液Ｂを３０℃で制御しながら撹拌しているところに溶解液Ａを１．４ｇ／分のペースで滴下する。溶解液Ａの滴下終了後、反応液をフーリエ変換赤外分光光度計にて測定し、イソシアナート基由来の２２５０ｃｍ^−１付近のピークが無い事を確認し反応終了とする。１，３ビス（イソシアナトメチル）シクロヘキサン１モルに対して、ヒドラジン５モル（モル比で１：５）となるように反応させた。
反応終了後、ろ紙（桐山社製Ｎｏ．４）を使い桐山ロート（桐山社製）にてろ過し、脱液を行い、得られた濾取物をイソプロピルアルコール５０ｍｌで洗浄し、更にろ過を行い、得られた濾取物を真空オーブンにて５０℃で乾燥させた。(Example 6)
(B-4) 4,4 ′-(1,3-cyclohexylenebismethylene) bis (semicarbazide)

A solution A in which 19.42 g of 1,3-bis (isocyanatomethyl) cyclohexane is dissolved in 100 g of isopropanol and a solution B in which 25.3 g of hydrazine are dissolved in 100 g of isopropanol are prepared. The solution A is dropped at a rate of 1.4 g / min while the solution B is being stirred at 30 ° C. in a three-necked flask. After completion of the dropwise addition of the solution A, the reaction solution is measured with a Fourier transform infrared spectrophotometer, and it is confirmed that there is no peak near 2250 cm ⁻¹ derived from the isocyanate group, and the reaction is completed. It was made to react so that it might be set to 5 mol (1: 5 by molar ratio) of hydrazine with respect to 1 mol of 1, 3-bis (isocyanatomethyl) cyclohexane.
After completion of the reaction, the solution was filtered with a Kiriyama funnel (manufactured by Kiriyama Co., Ltd.) using a filter paper (Kiriyama Co., Ltd. No. 4), the liquid was removed, and the resulting filtrate was washed with 50 ml of isopropyl alcohol and further filtered. The obtained filtered product was dried at 50 ° C. in a vacuum oven.

エタノール１００ｇにイソホロンジイソシアナートを２２．２２ｇ溶解した溶解液Ａと、エタノール１００ｇにヒドラジン２５．３ｇを溶解した溶解液Ｂを用意する。三口フラスコで溶解液Ｂを３０℃で制御しながら撹拌しているところに溶解液Ａを１．４ｇ／分のペースで滴下する。溶解液Ａの滴下終了後、反応液をフーリエ変換赤外分光光度計にて測定し、イソシアナート基由来の２２５０ｃｍ^−１付近のピークが無い事を確認し反応終了とする。イソホロンジイソシアナート１モルに対して、ヒドラジン５モル（モル比で１：５）となるように反応させた。
反応終了後、エバポレーターにて５０℃でエタノールをとばし、精製物をフーリエ変換赤外分光光度計にて測定し、エタノール由来の３３００ｃｍ^−１付近のピークが無いことを確認し、液体カルバジド化合物を製造した。(Example 7)
(B-6) 4,4′-isophoronebis (semicarbazide)

A solution A in which 22.22 g of isophorone diisocyanate is dissolved in 100 g of ethanol and a solution B in which 25.3 g of hydrazine are dissolved in 100 g of ethanol are prepared. The solution A is dropped at a rate of 1.4 g / min while the solution B is being stirred at 30 ° C. in a three-necked flask. After completion of the dropwise addition of the solution A, the reaction solution is measured with a Fourier transform infrared spectrophotometer, and it is confirmed that there is no peak near 2250 cm ⁻¹ derived from the isocyanate group, and the reaction is completed. It was made to react so that it might become hydrazine 5 mol (molar ratio 1: 5) with respect to 1 mol of isophorone diisocyanate.
After completion of the reaction, ethanol is evaporated at 50 ° C. with an evaporator, and the purified product is measured with a Fourier transform infrared spectrophotometer, and it is confirmed that there is no peak near 3300 cm ⁻¹ derived from ethanol, and a liquid carbazide compound is produced. did.

(Example 8)
(A-1) 1,1 ′-[methylenebis (cyclohexane-4,1-diyl)] bis [3- (12-aminododecyl) urea]

A solution A in which 13.6 g of dicyclohexylmethane-4,4-diisocyanate was dissolved in 79 g of ethanol and a solution B in which 20.7 g of 1,12-diaminododecane (manufactured by TCI) were dissolved in 100 g of ethanol were prepared. . The solution A was added dropwise at a rate of 1.4 g / min to the place where the solution B was being stirred at 30 ° C. in a three-necked flask. After completion of dropping, the reaction solution was measured with a Fourier transform infrared spectrophotometer, and it was confirmed that there was no peak near 2250 cm ⁻¹ derived from an isocyanate group, and the reaction was completed. The reaction was carried out so that 1 mol of 1,12-diaminododecane was 2 mol (1: 2 in molar ratio) with respect to 1 mol of dicyclohexylmethane-4,4-diisocyanate.
The reaction solution was poured into 500 g of stirring water to promote crystallization and allowed to stand for 1 hour, and then filtered through a Kiriyama funnel (manufactured by Kiriyama Co.) using a filter paper (Kiriyama Co., Ltd. No. 4). The filtered product was dried at 50 ° C. in a vacuum oven. After drying, the mixture was naturally cooled to room temperature, and pulverized with a high-pressure pulverizer (trade name: NanoJet Mizer, manufactured by Aisin Nano Technologies) to produce an amine compound having an average particle diameter (median diameter) of 2.5 μm.

Example 9
(A-3) 1,1 ′-[methylenebis (cyclohexane-4,1-diyl)] bis [3- (6-aminohexyl) urea]

A solution A in which 12 g of 1,6-diaminohexane (manufactured by TCI) was dissolved in 100 g of ethanol and a solution B in which 13.6 g of dicyclohexylmethane-4,4′-diisocyanate was dissolved in 79 g of ethanol were prepared. The solution A was added dropwise at a rate of 1.4 g / min to the place where the solution B was being stirred at 30 ° C. in a three-necked flask. After completion of dropping, the reaction solution was measured with a Fourier transform infrared spectrophotometer, and it was confirmed that there was no peak near 2250 cm ⁻¹ derived from an isocyanate group, and the reaction was completed. The reaction was carried out so that 1 mol of 1,6-diaminohexane was 1 mol per mol of dicyclohexylmethane-4,4-diisocyanate (1: 2 in molar ratio).
Thereafter, the solvent was distilled off under reduced pressure using a rotary evaporator. After drying, the mixture was naturally cooled to room temperature and pulverized with a high-pressure pulverizer (trade name: NanoJet Mizer, manufactured by Aisin Nano Technologies) to produce an amine compound having an average particle diameter (median diameter) of 2.2 μm.

(Example 10)
(A-4) 1,1 ′-(Hexane-1,6-diyl) bis [3- (12-aminododecyl) urea]

A solution A in which 49.65 g of 1,12-diaminododecane (manufactured by TCI) was dissolved in 150 g of ethanol and a solution B in which 20.54 g of hexamethylene diisocyanate was dissolved in 118 g of ethanol were prepared. The solution A was added dropwise at a rate of 1.4 g / min to the place where the solution B was being stirred at 30 ° C. in a three-necked flask. After completion of dropping, the reaction solution was measured with a Fourier transform infrared spectrophotometer, and it was confirmed that there was no peak near 2250 cm ⁻¹ derived from an isocyanate group, and the reaction was completed. It was made to react so that it might become 2 mol of 1,12- diaminododecane (molar ratio 1: 2) with respect to 1 mol of hexamethylene diisocyanate.
Thereafter, the solvent was distilled off under reduced pressure using a rotary evaporator. After drying, the mixture was naturally cooled to room temperature and pulverized with a high-pressure pulverizer (trade name: NanoJet Mizer, manufactured by Aisin Nano Technologies) to produce a diamine urea compound having an average particle diameter (median diameter) of 2.1 μm.
After completion of the reaction, it was filtered through a Kiriyama funnel (manufactured by Kiriyama Co., Ltd.) using a filter paper (Kiriyama Co., Ltd. No. 4), the liquid was removed, and the resulting filtrate was washed with 100 ml of ethanol and further filtered. The obtained filtered product was dried at 50 ° C. in a vacuum oven.

(Example 11)
(A-5) 1,1 ′-(Hexane-1,6-diyl) bis [3- (2-aminoethyl) urea]

A solution A in which 17.17 g of hexamethylene diisocyanate was dissolved in 118 g of ethanol and a solution B in which 61.36 g of ethylenediamine were dissolved in 150 g of ethanol were prepared. The solution A was dropped at a rate of 1.4 g / min while the solution B was being controlled and stirred at 25 ° C. in a three-necked flask. After completion of the dropwise addition of the solution A, the reaction solution was measured with a Fourier transform infrared spectrophotometer, and it was confirmed that there was no peak near 2250 cm ⁻¹ derived from the isocyanate group, and the reaction was completed. It was made to react so that it might be set to 10 mol (1:10 by molar ratio) of ethylenediamine with respect to 1 mol of hexamethylene diisocyanate.
After completion of the reaction, it was filtered through a Kiriyama funnel (manufactured by Kiriyama Co., Ltd.) using a filter paper (Kiriyama Co., Ltd. No. 4), the liquid was removed, and the resulting filtrate was washed with 100 ml of ethanol and further filtered. The obtained filtered product was dried at 50 ° C. in a vacuum oven. After drying, the mixture was naturally cooled to room temperature and pulverized with a high-pressure pulverizer (trade name: NanoJet Mizer, manufactured by Aisin Nano Technologies) to produce an amine compound having an average particle diameter (median diameter) of 2.2 μm.

(Example 12)
(A-6) 1,1 ′-(Hexane-1,6-diyl) bis [3- (6-aminohexyl) urea]

A solution A in which 17.17 g of hexamethylene diisocyanate was dissolved in 150 g of ethanol and a solution B in which 94.9 g of 1,6-diaminohexane (manufactured by TCI) were dissolved in 118 g of ethanol were prepared. The solution A was dropped at a rate of 1.4 g / min while the solution B was being controlled and stirred at 25 ° C. in a three-necked flask. After completion of the dropwise addition of the solution A, the reaction solution was measured with a Fourier transform infrared spectrophotometer, and it was confirmed that there was no peak near 2250 cm ⁻¹ derived from the isocyanate group, and the reaction was completed. The reaction was carried out so that 1,6-diaminohexane was 10 moles (1:10 molar ratio) with respect to 1 mole of hexamethylene diisocyanate.
Thereafter, the solvent was distilled off under reduced pressure using a rotary evaporator. After drying, the mixture was naturally cooled to room temperature and pulverized with a high-pressure pulverizer (trade name: NanoJet Mizer, manufactured by Aisin Nano Technologies) to produce an amine compound having an average particle diameter (median diameter) of 2.3 μm.

(Example 13)
(A-2) 1,1 ′-[methylenebis (cyclohexane-4,1-diyl)] bis [3- (2-aminoethyl) urea]

A solution A in which 13.55 g of dicyclohexylmethane 4,4′-diisocyanate was dissolved in 100 g of ethanol and a solution B in which 15.5 g of ethylenediamine (manufactured by TCI) was dissolved in 79 g of ethanol were prepared. The solution A was dropped at a rate of 1.4 g / min while the solution B was being controlled and stirred at 25 ° C. in a three-necked flask. After completion of the dropwise addition of the solution A, the reaction solution was measured with a Fourier transform infrared spectrophotometer, and it was confirmed that there was no peak near 2250 cm ⁻¹ derived from the isocyanate group, and the reaction was completed. It was made to react so that it might be set to 5 mol (1: 5 by molar ratio) of 1, 6- diaminohexane with respect to 1 mol of hexamethylene diisocyanate.
After completion of the reaction, it was filtered through a Kiriyama funnel (manufactured by Kiriyama Co., Ltd.) using a filter paper (Kiriyama Co., Ltd. No. 4), the liquid was removed, and the resulting filtrate was washed with 100 ml of ethanol and further filtered. The obtained filtered product was dried at 50 ° C. in a vacuum oven. After drying, the mixture was naturally cooled to room temperature and pulverized with a high-pressure pulverizer (trade name: NanoJet Mizer, manufactured by Aisin Nano Technologies) to produce an amine compound having an average particle diameter (median diameter) of 2.2 μm.

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

  Ethylenediamine 61.36 g (1020 mmol) and toluene 150 g were stirred in a three-necked flask, and a solution of hexamethylene diisocyanate 17.17 g (102 mmol) in toluene 118.5 g (150 ml) was added dropwise. The reaction time was controlled at 30 minutes, and the reaction solution was controlled at 40 ° C. After completion of the dropwise addition, the reaction solution was filtered, and the precipitate was washed with toluene and poured into water. After stirring for 1 hour, filtration was performed, and when the obtained filtrate was concentrated under reduced pressure using an evaporator, precipitates were confirmed. The reacted hexamethylene diisocyanate and ethylenediamine were 10 mol of ethylenediamine (1:10 in molar ratio) with respect to 1 mol of hexamethylene diisocyanate. The obtained precipitate was washed with ethanol (EtOH) and dried under reduced pressure. The crystals obtained were pulverized with a high-pressure pulverizer (trade name: NanoJet Mizer, manufactured by Aisin Nano Technologies), and the average particle diameter (median diameter) was obtained. ) A 2.1 μm amine compound was produced.

イソプロパノール２４０ｇにヘキサメチレンジイソシアナート（ＴＣＩ社製）１８．３ｇ溶解した溶解液Ａと、イソプロパノール７２．６ｇに１，６−ヘキサンジアミン３３．４８ｇと、エチレンジアミン１８．３ｇを溶解した溶解液Ｂを用意した。三口フラスコで溶解液Ｂを２５℃で制御し撹拌しているところに溶解液Ａを１．４ｇ／分のペースで滴下した。溶解液Ａの滴下終了後、反応液をフーリエ変換赤外分光光度計にて測定し、イソシアナート基由来の２２５０ｃｍ^−１付近のピークが無い事を確認し反応終了した。ヘキサメチレンジイソシアナート１モルに対して、エチレンジアミン５モル、１，６−ジアミノヘキサン５モル（モル比で１：５：５）となるように反応させた。
反応終了後、ろ紙（桐山社製Ｎｏ．４）を使い桐山ロート（桐山社製）にてろ過し、脱液を行い、得られた濾取物をイソプロパノール１００ｍｌで洗浄し、更にろ過を行い、得られた濾取物を真空オーブンにて５０℃で乾燥させた。乾燥後室温まで自然冷却し、高圧粉砕機（商品名：ナノジェットマイザー、アイシンナノテクノロジーズ社製）で粉砕し、平均粒径（メジアン径）２．２μｍのアミン化合物を製造した。(Example 14)
(A-7) N, N′-hexamethylene [carbonylbis (azanediyl) (2-aminoethyl)]-[carbonylbis (azanediyl) (6-aminohexyl)]

A solution A in which 18.3 g of hexamethylene diisocyanate (manufactured by TCI) was dissolved in 240 g of isopropanol, and a solution B in which 33.48 g of 1,6-hexanediamine and 18.3 g of ethylenediamine were dissolved in 72.6 g of isopropanol were obtained. Prepared. The solution A was dropped at a rate of 1.4 g / min while the solution B was being controlled and stirred at 25 ° C. in a three-necked flask. After completion of the dropwise addition of the solution A, the reaction solution was measured with a Fourier transform infrared spectrophotometer, and it was confirmed that there was no peak near 2250 cm ⁻¹ derived from the isocyanate group, and the reaction was completed. It was made to react with respect to 1 mol of hexamethylene diisocyanate so that it might become 5 mol of ethylenediamine and 5 mol of 1, 6- diaminohexanes (1: 5: 5 by molar ratio).
After completion of the reaction, it was filtered through a Kiriyama funnel (manufactured by Kiriyama Co., Ltd.) using a filter paper (Kiriyama Co., Ltd. No. 4), the liquid was removed, and the resulting filtered product was washed with 100 ml of isopropanol and further filtered. The obtained filtered product was dried at 50 ° C. in a vacuum oven. After drying, the mixture was naturally cooled to room temperature and pulverized with a high-pressure pulverizer (trade name: NanoJet Mizer, manufactured by Aisin Nano Technologies) to produce an amine compound having an average particle diameter (median diameter) of 2.2 μm.

[Manufacture of epoxy resin]
A partially esterified epoxy resin was produced according to the production method described in JP-A-5-295087. Specifically, a partially esterified epoxy resin (partially methacrylated epoxy resin) was produced as follows.
(I) High-purity bisphenol A type epoxy resin: 1000 parts by mass of Epicron-850S (manufactured by DIC), methacrylic acid: 250 parts by mass, toluene: 900 parts by mass, triethylamine: 2 parts by mass, paramethoxyphenol: 2 parts by mass Were mixed and heated and stirred at 90 ° C. for 8 hours to obtain a partial addition reaction product.
(B) To the product of (i) above, 4500 parts by mass of toluene is added to obtain a diluted solution, 4500 parts by mass of pure water is added thereto, and the mixture is stirred for 1 hour at room temperature and left to stand. Separate and remove. This washing operation is repeated 3 to 5 times, then washing with the same amount of 1N NaOH solution is repeated 3 to 5 times, and further washing with only the same amount of pure water is repeated 3 to 5 times. The ion conductivity was measured using a degree measuring device (manufactured by Horiba, Ltd .: conductivity meter), and it was confirmed that it was 10 μS / cm or less.
(C) The solution obtained by filtering the solution of (b) above was concentrated at 70 ° C. under reduced pressure to completely remove and purify toluene to synthesize a partially methacrylated epoxy resin.
Moreover, according to the said synthesis example, it replaced with methacrylic acid and acrylic acid was used, and the partially acrylated epoxy resin was synthesize | combined by the same method.

[Production of liquid crystal sealant composition]
100 parts by mass of the partially methacrylic epoxy resin, 15 parts by mass of spherical silica (manufactured by Admafine, SO-C1) as an inorganic filler, 15 parts by mass of F-351 (manufactured by Zeon Corporation) as an organic filler, photoradical 3 parts by mass of Irgacure 907 (manufactured by BASF Japan) as an initiator, 2 parts by mass of KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, and Examples 1-5, 8-12, and 14 as curing agents A curing agent is blended in an amount of 1 equivalent to 1 equivalent of the epoxy group of the partially methacrylic epoxy resin, and uniformly dispersed with a three-one motor (trade name: RW28basic, manufactured by IKA) to obtain a liquid crystal sealant resin composition. It was.
As Comparative Example 1, commercially available dodecanoic acid hydrazide (DDH, manufactured by Otsuka Chemical Co., Ltd.) was used, and as Comparative Example 2, commercially available 1,3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin (Amicure VDH, Ajinomoto) A liquid crystal sealant composition was produced in the same manner as described above except that Fine Techno Co.) was used.

[Measurement method of adhesive strength]
FIG. 2 is a diagram illustrating a method for measuring adhesive strength using the liquid crystal sealant compositions of Examples 1 to 5, 8 to 12, and 14 and Comparative Examples 1 and 2. As shown in FIG. 2, an ITO glass 8 having a thickness of 0.5 mm and a 3.0 cm square (with an ITO electrode film on the glass surface, a glass 9 having a thickness of 0.5 mm and a 2.3 cm square was prepared. 2. The liquid crystal sealant composition 2 is applied to the glass at the center line of 9 mm from both ends so that the adhesive surface has a diameter of 1.5 to 2.0 mm and a thickness of 6.0 to 10.0 μm. One side of a 0 cm square ITO glass 8 and a 2.3 cm square glass 9 were put together and bonded together to produce a test piece 10. UV 3000 mJ (trade name: UB-031-A) was applied to the bonded test piece 10. / BM-E1, manufactured by Eye Graphics Co., Ltd.) and then heated at 120 ° C. for 60 minutes to cure the liquid crystal sealant composition 2. From the end of the center line of the ITO glass 8 of the cured test piece 10 Auto 5mm point Rough (Shimadzu Corporation; AGS). Press at punching, the adhesive strength was measured results are shown in Table 1.

[Glass bond strength with alignment film]
Thickness 0.7 mm, 3.0 cm square alignment film (Sunever SE-7492, manufactured by Nissan Chemical Industries) glass 8 (having an alignment film on the glass surface), thickness 0.7 mm, 2.3 cm An alignment film glass 9 having the same treatment as the corner glass 8 was prepared. As shown in FIG. 2, a liquid crystal sealing agent composition having a diameter of 1.5 mm to 2.0 mm and a thickness of 6.0 μm to 10.0 μm as an adhesive surface at 9 mm from both ends on the center line of the glass. 2 was applied, one side of the 3.0 cm square alignment film glass 8 and the 2.3 cm square alignment film glass 9 were put together, and both were bonded to prepare a test piece 10. The bonded test piece 10 was irradiated with UV 3000 mJ (trade name: UB-031-A / BM-E1, manufactured by Eye Graphics Co., Ltd.) and then heated at 120 ° C. for 60 minutes to cure the liquid crystal sealant composition 2. . A point of 5 mm from the end of the center line of the ITO glass 8 of the test piece 10 after curing was pushed through an autograph (manufactured by Shimadzu Corporation; AGS), and the adhesive strength was measured.

[Orientation test method]
An alignment film (Sunever SE) obtained by rubbing a liquid crystal sealant composition using Example 11 (curing agent: A-5) and Comparative Example 1 (curing agent: DDH) with a cross-sectional area of 4000 μm ² using a seal dispenser. -7492, manufactured by Nissan Chemical Industries, Ltd.) was dispensed onto an ITO glass substrate (60 mm × 70 mm × 0.7 mmt). Thereafter, liquid crystal (TN liquid crystal, MLC-11900-080, manufactured by Merck & Co., Inc.) is dropped on the substrate, and the upper and lower substrates are bonded together by a liquid crystal dropping method (ODF method), and ultraviolet rays (UV irradiation device: UVX-01224S1, Ushio Electric). company Ltd., illuminance and radiation time: for 50mJ, 50mW ^/ cm 2 ^/ 365nm 1 second, in the case of 200mJ was cured by irradiation with 4 seconds) with 50mW ^/ cm 2 ^/ 365nm, thereafter 120 ° C. hot air oven Thermal curing was performed for 1 hour to prepare a test cell for the orientation test. In the case of illuminance of 0 mJ, with a light-shielding mask after bonding, the liquid crystal and the sealant are not irradiated with ultraviolet rays, and then heat-cured in a hot air oven at 120 ° C. for 1 hour to provide a test cell for the orientation test. Produced.

  About the obtained panel, the alignment state of the liquid crystal at the time of sealing was confirmed. The confirmation was performed with an optical microscope, and the polarizing plate was observed in a transmission state with a test cell sandwiched in a crossed Nicol state. Observe the alignment state of the corners and straight portions of the liquid crystal at illuminance of 200 mJ and 50 mJ. The evaluation criteria for the orientation of the liquid crystal was judged by the presence or absence of alignment disorder during sealing. The case where the alignment disorder was 50 μm or less during sealing was indicated by “◯”, and the case where the alignment disorder was further exceeded was indicated by “X”. The results are shown in Table 2.

  As shown in Table 1, the liquid crystal sealant composition using the curing agent of the present invention (Examples 1 to 5, 8 to 12 and 14) is a case where different materials are bonded together such as glass and ITO glass. Even so, the adhesive strength was greater than when the curing agents of Comparative Examples 1 and 2 were used. In addition, the orientation of the alignment film of the liquid crystal sealant composition of Example 11 (curing agent A-5) was in a good state with an alignment disturbance at the time of sealing of 50 μm or less for both illuminances of 50 mJ and 200 mJ. As for the orientation of the alignment film using Comparative Example 1, the alignment disorder at the time of sealing exceeded 50 μm for both illuminances of 50 mJ and 200 mJ. From this result, the curing agent of the present invention, the resin composition using the same, and the liquid crystal sealing agent composition are adapted to thinning and diversification of adhesiveness required for the sealing agent used for bonding liquid crystal display panels and the like. However, it was confirmed that the adhesive strength capable of suppressing peeling at the time of cutting out the cell and mounting the IC for driving the liquid crystal cell was exhibited.

(Example 15)
A solution A in which 17.17 g of hexamethylene diisocyanate was dissolved in 118 g of ethanol and a solution B in which 61.36 g of ethylenediamine were dissolved in 150 g of ethanol were prepared. The solution A was dropped at a rate of 1.4 g / min while the solution B was being controlled and stirred at 25 ° C. in a three-necked flask. After completion of the dropwise addition of the solution A, the reaction solution was measured with a Fourier transform infrared spectrophotometer, and it was confirmed that there was no peak near 2250 cm ⁻¹ derived from the isocyanate group, and the reaction was completed. It was made to react so that it might be set to 10 mol (1:10 by molar ratio) of ethylenediamine with respect to 1 mol of hexamethylene diisocyanate.
After completion of the reaction, it was filtered through a Kiriyama funnel (manufactured by Kiriyama Co., Ltd.) using a filter paper (Kiriyama Co., Ltd. No. 4), the liquid was removed, and the resulting filtrate was washed with 100 ml of ethanol and further filtered. The obtained filtered product was dried at 50 ° C. in a vacuum oven. After drying, the mixture was naturally cooled to room temperature and pulverized with a high-pressure pulverizer (trade name: NanoJet Mizer, manufactured by Aisin Nano Technologies) to produce an amine compound (A-5) having an average particle diameter (median diameter) of 2.2 μm. .

10 g of the amine compound (A-5) obtained above and 1.36 g of hexamethylene diisocyanate were mixed in 80 ml of methylcyclohexane and subjected to a constant temperature treatment at 50 ° C. for 24 hours.
Thereafter, the treatment liquid was filtered through a Kiriyama funnel (manufactured by Kiriyama Co., Ltd.) using filter paper (Kiriyama Co., Ltd. No. 4), and the liquid was removed. The obtained filtered product was mixed with 100 ml of methylcyclohexane, and the same filtration as described above was repeated three times in total. Curing agent (E-1) containing a compound obtained by drying the final filtered product at 50 ° C. and 1 Torr for 12 hours using a vacuum dryer (manufactured by ESPEC) and treating the amine compound with an isocyanate compound. Got.

10 g of the amine compound (A-5) obtained above, 1.36 g of hexamethylene diisocyanate, and 1.255 g of hydrogenated bisphenol A type epoxy resin (YX8034, manufactured by JER) were mixed in 80 ml of toluene. And constant temperature treatment at 50 ° C. for 24 hours.
Thereafter, the treatment liquid was filtered through a Kiriyama funnel (manufactured by Kiriyama Co., Ltd.) using filter paper (Kiriyama Co., Ltd. No. 4), and the liquid was removed. The obtained filtered product was mixed with 100 ml of toluene, and the same filtration as described above was repeated three times. What was finally collected by filtration was dried at 50 ° C. and 1 Torr for 12 hours in a vacuum dryer (manufactured by ESPEC), and a curing agent (E -2) was obtained.

[Production of liquid crystal sealant composition]
100 parts by mass of the partially methacrylic epoxy resin obtained above, 15 parts by mass of spherical silica (manufactured by Admafine, SO-C1) as an inorganic filler, and F-351 (manufactured by Nippon Zeon) as an organic filler 15 3 parts by mass of Irgacure 907 (manufactured by BASF Japan) as a photoradical initiator, 2 parts by mass of KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent, and E-1 or E- as a curing agent 2 was blended in an amount of 15 parts by mass with respect to 100 parts by mass of the partially methacrylated epoxy resin, and uniformly dispersed with a three-one motor (manufactured by IKA, trade name: RW28basic) to obtain a liquid crystal sealant resin composition.

[Evaluation]
(Stability test)
Liquid stability The initial viscosity of the liquid crystal sealant composition obtained above was measured immediately after preparation (within 2 hours). Further, the viscosity after 2 weeks at 25 ° C. was measured, and the rate of change in viscosity after 2 weeks (% / 2weeks) was calculated based on the initial viscosity.

  The viscosity was measured as follows. A RE-105U viscometer (manufactured by Toki Sangyo Co., Ltd.) is attached with a 3 ° × R7.7 cone rotor, 0.15 ml of the liquid crystal sealant composition to be used is set in the cone rotor, and 25 ° C. at 2.5 rpm. The viscosity of the liquid crystal sealant composition was measured. When the measurement range was over, measurement was impossible. Note that the measurement range over reference is 1,200,000 mPa · s.

Heated liquid stability The initial viscosity of the liquid crystal sealant composition obtained above was measured, the viscosity after 40 hours at 40 ° C. was further measured, and the viscosity after 22 hours warming based on the initial viscosity. Change rate (% / 22 hrs) was calculated.
The results of liquid stability and warmed liquid stability are shown in Table 3.

  As is apparent from the results in Table 3, the isocyanate-added amine compound obtained by adding an arbitrary isocyanate to the amine compound has a small change rate of liquid stability and warming liquid stability, and particularly a change rate of warming liquid stability. It is clear that the small is remarkable.

(Curing test)
The liquid crystal sealant composition (resin composition) obtained above was cured under the two conditions shown in Table 4 below (120 ° C. for 1 hour only, and UV 3000 mJ / cm ² after treatment for 120 hours for 1 hour). The obtained cured pieces were measured by FT-IR and evaluated for curability. The following formula was used for the calculation method of the epoxy curing rate. Moreover, the methacryl cure rate was calculated by replacing the peak of the epoxy group in the following formula with the peak of the methacryl group.

Reference peak: 1540 to 1480 cm ⁻¹ (near peak top 1510 cm ⁻¹ )
Peak of epoxy groups; 925~895cm ^-1 (near peak top 910 cm ^-1)
Methacryl group peak; 1650 to 1625 cm ⁻¹ (near peak top 1635 cm ⁻¹ )

  From the results shown in Table 4, no significant decrease in curability was observed even after isocyanate treatment. That is, even if the isocyanate treatment is performed, the liquid stability can be improved without lowering the curability.

  According to the present invention, the adhesive strength that can sufficiently suppress peeling at the time of cutting out a cell and mounting an IC for driving a liquid crystal cell while satisfying the diversification of adhesiveness by thinning and diversification of different materials. The curing agent of the present invention, the resin composition using the same, and the liquid crystal sealant composition are suitable as a sealant or sealant for electronic parts such as liquid crystal display panels. It can be used and is industrially useful.

The entire disclosure of Japanese Patent Application No. 2012-155976 is incorporated herein by reference.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.

[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Liquid crystal sealing agent composition 3 Liquid crystal injection hole 4 Glass substrate 5 Liquid crystal sealing cell 6 Liquid crystal 7 Liquid crystal display panel 8 ITO glass 9 Glass 10 Test piece

Claims (14)

Including a compound having at least one primary amino group in the molecule, obtained by reacting an isocyanate compound with hydrazine or a polyvalent amine compound having two or more primary amino groups in the molecule; A curing agent for epoxy resins and / or resins having at least one unsaturated bond in the molecule ,
The polyvalent amine compound has the following formula (5a):

[ Wherein L is C ₁ -C ₁₂ alkylene, C ₂ -C ₁₂ alkylene (N atom (N ), interrupted discontinuously by one or more NH (imino group) or O atom (oxygen atom)). H atom bonded to the nitrogen atom) (hydrogen atoms) may be substituted by an amino group or a _C 1 _{-C 12} alkylamino _group), C 3 _{-C 12 cycloalkylene,} C 1 _{-C 12} alkylene -C ₃ -C _{12 cycloalkylene,} C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12 alkylene,} C 3 _{-C 12} cycloalkylene _-C 1 -C ₄ alkylene _-C 3 _{-C 12} cycloalkyl _alkylene, C 6 _{-C 14 arylene,} C 1 -C ₄ alkylene _-C 6 _{-C 14 arylene,} C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene _-C 1 ~ ₄ alkylene, or _C 6 _{-C 14} arylene _-C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene (where alkylene is linear or branched chain, may be substituted by halogen, _{C 3} -C ₁₂ cycloalkylene or C ₆ -C ₁₄ arylene is unsubstituted or optionally substituted by halogen or C ₁ -C ₄ alkyl).
The isocyanate compound is a monoisocyanate compound, a diisocyanate compound, a triisocyanate compound, or a tetraisocyanate compound,
The monoisocyanate compound has the following formula (1a):

[In Formula (1a), X ² is C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkyl discontinuously interrupted by one or more O atoms (oxygen atoms) , C ₁ -C ₁₂ alkyloxycarbonyl _alkylene, C 3 _{-C 12 cycloalkyl,} C 1 _{-C 12} alkyl _-C 3 _{-C 12 cycloalkylene,} C 3 _{-C 12} cycloalkyl _-C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene C ₆ -C ₁₄ aryl, C ₁ -C ₄ alkyl-C ₆ -C ₁₄ arylene, C ₆ -C ₁₄ aryl-C ₁ -C ₄ alkylene-C ₆ -C ₁₄ arylene (wherein alkylene is straight A chain or branched chain, optionally substituted with halogen, C ₃ -C ₁₂ cycloalkyl, C ₃ -C ₁₂ cycloalkylene, C ₆ -C ₁₄ ali Or C ₆ -C ₁₄ arylene is unsubstituted or substituted by halogen or C ₁ -C ₄ alkyl), or (meth) acryloyloxyalkyl] ,
When the curing agent is obtained by reaction of a diisocyanate compound and hydrazine, the diisocyanate compound is represented by the following formula (2a):

In [Formula (2a), ^{X 1} is one or more O atoms (oxygen atom) in interrupted discontinuously a _C 2 _{-C 12 alkylene,} C 1 _{-C 12} alkyleneoxy carbonyl alkylene, _{C 1} -C ₁₂ alkylene _-C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12 alkylene,} C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene, di _C 3 _{-C 12} cycloalkyl _alkanediyl, C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene _-C 1 -C ₄ alkylene, or _C 6 _{-C 14} arylene _-C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene (where alkylene is a straight or branched chain, may be substituted by _halogen, C 3 _{-C 12} cycloalkylene or _C 6 _{-C 14} arylene Rene is unsubstituted or substituted with halogen or C ₁ -C ₄ alkyl)),
When the curing agent is obtained by reaction of a diisocyanate compound and a polyvalent amine compound, the diisocyanate compound is represented by the following formula (2a):

In [Formula (2a), ^{X 1} _is, C 1 _{-C 12} alkylene, one or more O atoms (oxygen atom) in a non-continuously interrupted _C 2 _{-C 12 alkylene,} C 1 _{-C 12} alkyleneoxy carbonyl _alkylene, C 3 _{-C 12 cycloalkylene,} C 1 _{-C 12} alkylene _-C 3 _{-C 12 cycloalkylene,} C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12} alkylene, C ₃ -C ₁₂ cycloalkylene _-C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene, di _C 3 _{-C 12 cycloalkanediyl,} C 6 _{-C 14 arylene,} C 1 -C ₄ alkylene _-C 6 ~ C ₁₄ arylene-C ₁ -C ₄ alkylene, or C ₆ -C ₁₄ arylene-C ₁ -C ₄ alkylene-C ₆ -C ₁₄ Arylene (wherein alkylene is linear or branched and may be substituted with halogen, C ₃ -C ₁₂ cycloalkylene or C ₆ -C ₁₄ arylene is unsubstituted, halogen or Substituted with C ₁ -C ₄ alkyl).
The triisocyanate compound has the following formula (3a):

[Wherein R ² is the same or different and is a linear or branched C _{1 to} C ₁₂ alkylene], a compound having an isocyanurate structure represented by:
The following formula (3b):

[Wherein R ³ is the same or different and is a linear or branched C _{1 to} C ₁₂ alkylene], or a triisocyanate compound having a biuret structure represented by:
The following formula (3c):

[Wherein R ⁴ is the same or different and is a linear or branched C _{1 to} C ₁₂ alkylene, and R ⁵ is CH], a triisocyanate compound having an adduct structure represented by:
The tetraisocyanate compound has the following formula (4a):

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

A tetraisocyanatosilane represented by
Curing agents for epoxy resins and / or resins having at least one unsaturated bond in the molecule . Formula (I)

[Wherein R ¹ is a single bond, or C ₁ -C ₁₂ alkylene, C ₂ -C ₁₂ alkylene interrupted discontinuously with one or more NH or O atoms (bonded to an N atom) H atoms may be substituted by an alkyl amino group of the amino group or a _{C 1 ~C 12), C 3} ~C 12 _{cycloalkylene,} C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene, C ₁ -C ₁₂ alkylene _-C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12 alkylene,} C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12} alkylene _-C 3 _{-C 12 cycloalkylene,} C 6 _{-C 14} arylene , _C 1 -C ₄ alkylene _-C 6 _{-C 14 arylene,} C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene _-C 1 -C ₄ alkylene, and C ₆ -C ₁₄ arylene _-C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene (where alkylene is linear or branched chain, may be substituted by _halogen, C 3 _{-C 12} cycloalkyl Alkylene or C ₆ -C ₁₄ arylene is unsubstituted or substituted by halogen or C ₁ -C ₄ alkyl),
n is 1, 2, 3 or 4;
when n is 2 or more, R ¹ is independently the same as defined above;
When n is 1, A is C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkyl, C ₂ -C ₁₂ alkyloxycarbonylalkylene, C ₂ -C ₁₂ alkyl interrupted discontinuously at one or more O atoms, C ₃ -C _{12 cycloalkyl,} C 1 _{-C 12} alkyl _-C 3 _{-C 12 cycloalkylene,} C 3 _{-C 12} cycloalkyl _-C 1 _{-C 12} alkylene _-C 3 _{-C 12 cycloalkylene,} C 6 _{-C 14} Aryl, C ₁ -C ₄ alkyl-C ₆ -C ₁₄ arylene, C ₆ -C ₁₄ aryl-C ₁ -C ₄ alkylene-C ₆ -C ₁₄ arylene (wherein alkylene is linear or branched) may be substituted by _halogen, C 3 _{-C 12 cycloalkyl,} C 3 _{-C 12 cycloalkylene,} C 6 _{-C 14} aryl, or _C 6 -C ₁ Arylene, unsubstituted or substituted by halogen or C ₁ -C ₄ alkyl), or (meth) acryloyloxy alkyl,
when n is 2, and, when all of ^{R 1} is a single bond, A is one or _C 2 _{-C 12} alkylene in more O atoms is interrupted _{discontinuously,} C 1 _{-C 12} alkyleneoxy carbonyl alkylene, _C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12 alkylene,} C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene, di _C 3 _{-C 12} cycloalkanediyl, _C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene _-C 1 -C ₄ alkylene, or _C 6 _{-C 14} arylene _-C 1 -C ₄ alkylene _-C 6 -C ₁₄ arylene (wherein alkylene is linear or branched, optionally substituted with halogen, C ₃ -C ₁₂ cycloalkylene, C _6- C ₁₄ arylene is unsubstituted or substituted by halogen or or C ₁ -C ₄ alkyl)
when n is 2, and, if at least one of ^{R 1} is other than a single bond, A _is, C 1 _{-C 12} alkylene, one or discontinuously interrupted _C 2 ~ in more O atoms C _{12 alkylene,} C 1 _{-C 12} alkyleneoxy carbonyl _alkylene, C 3 _{-C 12 cycloalkylene,} C 1 _{-C 12} alkylene _-C 3 _{-C 12 cycloalkylene,} C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkyl alkylene _-C 1 _{-C 12 alkylene,} C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene, di _C 3 _{-C 12 cycloalkanediyl,} C 6 _{-C 14} arylene, C ₁ -C ₄ alkylene _-C 6 _{-C 14} arylene _-C 1 -C ₄ alkylene, or _C 6 _{-C 14} arylene _-C 1 -C ₄ alkylene-C ₆ -C ₁₄ arylene (wherein alkylene is linear or branched and may be substituted with halogen, C ₃ -C ₁₂ cycloalkylene, C ₆ -C ₁₄ arylene is non- or substituted, or halogen or or C ₁ is substituted with -C ₄ alkyl),
When n is 3, A is the following formula (1)

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

(Wherein R ³ are the same or different and are linear or branched C _{1 to} C ₁₂ alkylene) or the following formula (3)

Wherein R ⁴ is the same or different and is a linear or branched C _{1 to} C ₁₂ alkylene and R ⁵ is CH.
When n is 4, A is the following formula (4)

{Wherein X ³ is Si or C ₃ -C ₁₂ cycloalkyl-C ₁ -C ₁₂ alkylene-C ₃ -C ₁₂ cycloalkyl, or C ₆ -C ₁₄ aryl-C ₁ -C _4. Alkylene-C ₆ -C ₁₄ aryl (wherein alkylene is linear or branched and may be substituted with 1-6 halogens, C ₃ -C ₁₂ cycloalkyl or C ₆ -C ₁₄ aryl) Is a tetravalent residue that is unsubstituted or substituted with a halogen or C ₁ -C ₄ alkyl)} in the molecule at least one first A curing agent for an epoxy resin and / or a resin having at least one unsaturated bond in the molecule, comprising a compound having a secondary amino group. A compound having at least one primary amino group in the molecule is represented by the following formula (Ia):

[Where,
R ¹ , independently of ^one another, has the same meaning as in claim 2,
When all of R ¹ is a single bond, ^{X 1} is one or more O atoms in the non-continuously interrupted _C 2 _{-C 12 alkylene,} C 1 _{-C 12} alkyleneoxy carbonyl alkylene, _{C 1} -C ₁₂ alkylene _-C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12 alkylene,} C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene, di _C 3 _{-C 12} cycloalkyl alkanediyl, _C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene _-C 1 -C ₄ alkylene, or _C 6 _{-C 14} arylene _-C 1 -C ₄ alkylene _-C 6 _{-C 14} arylene (where alkylene is a straight or branched chain, may be substituted by _halogen, C 3 _{-C 12} cycloalkylene or _C 6 _{-C 14} arylene Is unsubstituted, or Ri halogen or C ₁ -C substituted with ₄ alkyl) der,
If at least one of R ¹ is other than a single bond, ^{X 1} _is, C 1 _{-C 12} alkylene, one or more O atoms in the non-continuously interrupted _C 2 _{-C 12 alkylene, C} 1 ~ C ₁₂ alkyleneoxycarbonylalkylene, C ₃ -C ₁₂ cycloalkylene, C ₁ -C ₁₂ alkylene-C ₃ -C ₁₂ cycloalkylene, C ₁ -C ₁₂ alkylene-C ₃ -C ₁₂ cycloalkylene-C ₁ -C _{12 alkylene,} C 3 _{-C 12} cycloalkylene _-C 1 _{-C 12} alkylene _-C 3 _{-C 12} cycloalkylene, di _C 3 _{-C 12 cycloalkanediyl,} C 6 _{-C 14 arylene,} C 1 -C ₄ alkylene -C ₆ -C ₁₄ arylene _-C 1 -C ₄ alkylene, or _C 6 _{-C 14} arylene _-C 1 -C ₄ alkylene -C -C ₁₄ arylene (where or alkylene is linear or branched chain, may be substituted by _halogen, C 3 _{-C 12} cycloalkylene or _C 6 _{-C 14} arylene is unsubstituted, Or a halogen or a C ₁ -C ₄ alkyl) ]. The compound having at least one primary amino group in the molecule is represented by the following formula (IIa)

[Where,
R ¹ has the same meaning as in claim 2,
X ² is C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkyl, C ₂ -C ₁₂ alkyloxycarbonylalkylene, C ₃ -C ₁₂ cyclo interrupted discontinuously with one or more O atoms. Alkyl, C ₁ -C ₁₂ alkyl-C ₃ -C ₁₂ cycloalkylene, C ₃ -C ₁₂ cycloalkyl-C ₁ -C ₁₂ alkylene-C ₃ -C ₁₂ cycloalkylene, C ₆ -C ₁₄ aryl, C _1- C ₄ alkyl-C ₆ -C ₁₄ arylene, C ₆ -C ₁₄ aryl-C ₁ -C ₄ alkylene-C ₆ -C ₁₄ arylene (wherein alkylene is linear or branched and is substituted with halogen) C ₃ -C ₁₂ cycloalkyl, C ₃ -C ₁₂ cycloalkylene, C ₆ -C ₁₄ aryl or C ₆ -C ₁₄ arylene may be , Unsubstituted or substituted by halogen or C ₁ -C ₄ alkyl), a or (meth) acrylate is acryloyloxy alkyl], curing agent according to claim 2.   The curing agent according to any one of claims 1 to 4, further comprising a compound obtained by treating a compound having at least one primary amino group in the molecule with an isocyanate compound.   The curing agent according to any one of claims 1 to 4, further comprising a compound obtained by treating a compound having at least one primary amino group in the molecule with an isocyanate compound and an epoxy resin.   The curing according to any one of claims 1 to 4, further comprising a compound obtained by treating a compound having at least one primary amino group in the molecule with an isocyanate compound and a compound having a hydroxy group. Agent.   A resin composition comprising the curing agent (A) according to any one of claims 1 to 7, and an epoxy resin and / or a resin (B) having at least one unsaturated bond.   The resin composition of Claim 8 whose epoxy resin is a partially esterified epoxy resin obtained by making 10-90 equivalent% (meth) acrylic acid react with respect to 1 equivalent of epoxy groups of an epoxy resin.   The resin composition of Claim 8 or 9 whose total amount of the primary amino group contained in a hardening | curing agent (A) is 0.001-10 equivalent with respect to 1 equivalent of epoxy groups of an epoxy resin.   The total amount of primary amino groups contained in the curing agent (A) with respect to the total of 1 equivalent of epoxy groups of the epoxy resin and 1 equivalent of unsaturated bonds of the resin having at least one unsaturated bond in the molecule. The resin composition according to claim 8, wherein is 0.001 to 10 equivalents.   The liquid-crystal sealing compound composition containing the resin composition of any one of Claims 8-11.   A liquid crystal display panel obtained using the liquid crystal sealant composition according to claim 12.   A method for producing a liquid crystal display panel, wherein in the liquid crystal dropping method, photocuring is performed using the liquid crystal sealant composition according to claim 12 and then thermosetting is performed.

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