JP2018021102A - Curable composition, adhesive, coating agent, article having coating layer, fiber-reinforced composite material and curable composition kit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition that can achieve both a long pot life and excellent curability in the reaction between a thiol group of a thiol compound and an isocyanate group of an isocyanate compound, and an adhesive, an article having a coating layer, a fiber-reinforced composite material, and a curable composition kit, each of which uses the curable composition.SOLUTION: A curable composition contains a thiol compound (A) having two or more thiol groups in the molecule, an isocyanate compound (B) having two or more isocyanate groups in the molecule, a phosphine compound (C), and a methacrylate compound (D).SELECTED DRAWING: None

Description

  The present invention relates to a curable composition, an adhesive and a coating agent using the same, an article having a coating layer and a fiber-reinforced composite material, and a curable composition kit.

  The thiourethane resin has a thiourethane group formed by a reaction between a thiol group of a thiol compound having two or more thiol groups in the molecule and an isocyanate group of an isocyanate compound having two or more isocyanate groups in the molecule. It is resin which has.

The following points are mentioned as characteristics of the thiourethane resin.
・ Since it has properties similar to urethane resin and is excellent in toughness, impact resistance, wear resistance, etc., it is used in a wide range of applications such as adhesives, coating agents, and matrix of fiber reinforced composite materials.
-Since it is a high refractive index, it is used also for an optical base material (patent document 1).
-Reaction of the thiol group of a thiol compound and the isocyanate group of an isocyanate compound advances rapidly with catalysts, such as a basic compound and a phosphine compound. Therefore, it is not necessary to use a tin-based catalyst that is used in the production of a urethane resin and is concerned about toxicity.

  A thiol compound and an isocyanate compound, which are raw materials for a thiourethane resin, are often used as a two-component curable composition. A thiourethane resin as a cured product is obtained by mixing a composition containing a thiol compound and a composition containing an isocyanate compound in the presence of a catalyst. From the viewpoint of the handleability of the two-component curable composition, it is preferable that the pot life, that is, the time until the curable composition loses its fluidity after mixing all the constituent components has a certain length of time. However, if the amount of the catalyst is reduced in order to increase the pot life, there is a problem that curing failure tends to occur.

As a catalyst for obtaining a thiourethane resin, it has been proposed to use a cocatalyst containing a phosphine compound and a Michael acceptor (Patent Document 2).
This document shows a cocatalyst composition that can provide a pot life of up to 31 minutes.

JP 2007-246690 A Special table 2003-526722 gazette

  However, Patent Document 2 does not describe a cocatalyst composition that can provide a long pot life, for example, a pot life of 40 minutes or more at room temperature, and it has been conventionally possible to achieve both a long pot life and good curability. It was difficult with technology.

  The present invention is a curable composition capable of achieving both a long pot life and good curability in the reaction between the thiol group of the thiol compound and the isocyanate group of the isocyanate compound; excellent in handleability when bonding objects to be bonded; Adhesives with good properties; low viscosity, solvent-free, excellent handling properties, good curability coatings; articles with excellent coating layer toughness, impact resistance, wear resistance, etc .; Fiber-reinforced composite material with excellent matrix impregnation, toughness, impact resistance, wear resistance, etc. in reinforcing fibers; and little change over time during storage, and when mixed, thiol group of thiol compound and isocyanate of isocyanate compound Curable composition kit that can provide a long pot life and good curability in the reaction with the group, and can provide a two-component curable composition excellent in handleability To provide.

ただし、Ｘ^１、Ｘ^２およびＸ^３は、それぞれ炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数１〜８のアルケニル基、炭素数１〜８のアルキニル基、炭素数３〜６のシクロアルキル基、フェニル基、ビフェニル基、ナフチル基、フェノキシ基または複素環基であり、Ｘ^１、Ｘ^２およびＸ^３は、置換基を有していてもよく、置換基は、ハロゲン原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、炭素数１〜８のアルケニル基、炭素数１〜８のアルキニル基、炭素数３〜６のシクロアルキル基、アミノ基、炭素数１〜８のアルキルアミノ基、ニトロ基、フェニル基、ビフェニル基、ナフチル基、フェノキシ基および複素環基からなる群から選ばれる少なくとも１種である。
＜３＞前記ホスフィン化合物（Ｃ）が、トリフェニルホスフィンである、前記＜１＞または＜２＞の硬化性組成物。
＜４＞前記ホスフィン化合物（Ｃ）が、前記チオール化合物（Ａ）に含まれるチオール基に対し、０．０５〜５当量％である、前記＜１＞〜＜３＞のいずれかの硬化性組成物。
＜５＞前記メタクリレート化合物（Ｄ）に含まれるメタクリロイルオキシ基が、前記チオール化合物（Ａ）に含まれるチオール基に対し、０．０５〜５当量％である、前記＜１＞〜＜４＞のいずれかの硬化性組成物。
＜６＞前記チオール化合物（Ａ）に含まれるチオール基に対する前記ホスフィン化合物（Ｃ）の当量％、および、前記チオール化合物（Ａ）に含まれるチオール基に対する前記メタクリレート化合物（Ｄ）に含まれるメタクリロイルオキシ基の当量％、のどちらか一方または両方が、０．３０当量％以下である、前記＜１＞〜＜５＞のいずれかの硬化性組成物。
＜７＞前記＜１＞〜＜６＞のいずれかの硬化性組成物を含む、接着剤。
＜８＞前記＜１＞〜＜６＞のいずれかの硬化性組成物を含む、コーティング剤。
＜９＞前記＜１＞〜＜６＞のいずれかの硬化性組成物の硬化物からなるコーティング層を有する、物品。
＜１０＞前記＜１＞〜＜６＞のいずれかの硬化性組成物の硬化物からなるマトリックスと、強化繊維とを含む、繊維強化複合材料。
＜１１＞分子内に２個以上のチオール基を有するチオール化合物（Ａ）と、ホスフィン化合物（Ｃ）とを含み、下記イソシアネート化合物（Ｂ）と、下記メタクリレート化合物（Ｄ）とを含まない組成物（Ｘ）を収容した第１の容器と；分子内に２個以上のイソシアネート基を有するイソシアネート化合物（Ｂ）と、メタクリレート化合物（Ｄ）とを含み、前記チオール化合物（Ａ）と、前記ホスフィン化合物（Ｃ）とを含まない組成物（Ｙ）を収容した第２の容器とを有する、硬化性組成物キット。 The present invention has the following aspects.
<1> A thiol compound (A) having two or more thiol groups in the molecule, an isocyanate compound (B) having two or more isocyanate groups in the molecule, a phosphine compound (C), and a methacrylate compound (D And the following pot life is 40 minutes or more.
Pot life: The phosphine compound (C) is added to the thiol compound (A) and completely dissolved to obtain the composition (X). A composition (Y) composed of an isocyanate compound (B) and a methacrylate compound (D) is added to the composition (X), and stirred at 25 ° C. for 30 seconds to obtain a mixed solution. Based on the time when the composition (Y) is added to the composition (X) as a reference, the time required to stop flowing even when the mixture is tilted is defined as the pot life.
<2> The curable composition according to <1>, wherein the phosphine compound (C) is a compound represented by the following formula (I).

Provided that X ¹ , X ² and X ³ are each an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an alkynyl group having 1 to 8 carbon atoms, carbon A cycloalkyl group having a number of 3 to 6, a phenyl group, a biphenyl group, a naphthyl group, a phenoxy group or a heterocyclic group, X ¹ , X ² and X ³ may have a substituent, and the substituent is A halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an alkynyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, It is at least one selected from the group consisting of an amino group, an alkylamino group having 1 to 8 carbon atoms, a nitro group, a phenyl group, a biphenyl group, a naphthyl group, a phenoxy group, and a heterocyclic group.
<3> The curable composition according to <1> or <2>, wherein the phosphine compound (C) is triphenylphosphine.
<4> The curable composition according to any one of <1> to <3>, wherein the phosphine compound (C) is 0.05 to 5 equivalent% with respect to the thiol group contained in the thiol compound (A). object.
<5> The methacryloyloxy group contained in the methacrylate compound (D) is 0.05 to 5 equivalent% with respect to the thiol group contained in the thiol compound (A). Any curable composition.
<6> Equivalent% of the phosphine compound (C) with respect to the thiol group contained in the thiol compound (A), and methacryloyloxy contained in the methacrylate compound (D) with respect to the thiol group contained in the thiol compound (A) The curable composition according to any one of <1> to <5>, wherein either one or both of the equivalent% of the group is 0.30 equivalent% or less.
<7> An adhesive comprising the curable composition according to any one of <1> to <6>.
<8> A coating agent comprising the curable composition according to any one of <1> to <6>.
<9> An article having a coating layer made of a cured product of the curable composition according to any one of <1> to <6>.
<10> A fiber-reinforced composite material comprising a matrix made of a cured product of the curable composition according to any one of <1> to <6>, and reinforcing fibers.
<11> A composition containing a thiol compound (A) having two or more thiol groups in the molecule and a phosphine compound (C) and not containing the following isocyanate compound (B) and the following methacrylate compound (D). A first container containing (X); an isocyanate compound (B) having two or more isocyanate groups in the molecule; and a methacrylate compound (D), the thiol compound (A), and the phosphine compound. The curable composition kit which has a 2nd container which accommodated the composition (Y) which does not contain (C).

The curable composition of the present invention can achieve both a long pot life and good curability in the reaction between the thiol group of the thiol compound and the isocyanate group of the isocyanate compound.
The adhesive of this invention is excellent in the handleability at the time of adhere | attaching adhesion | attachment objects, and its sclerosis | hardenability is favorable.
The coating agent of the present invention can be reduced in viscosity and solvent-free, has excellent handleability and good curability.
The article of the present invention is excellent in the toughness, impact resistance, wear resistance and the like of the coating layer.
The fiber-reinforced composite material of the present invention is excellent in matrix impregnation into a reinforcing fiber, toughness, impact resistance, wear resistance, and the like.
The curable composition kit of the present invention has little change over time during storage, and when mixed, can have both a long pot life and good curability in the reaction between the thiol group of the thiol compound and the isocyanate group of the isocyanate compound. A two-component curable composition having excellent properties can be provided.

<Curable composition>
The curable composition of the present invention comprises a thiol compound (A) having two or more thiol groups in the molecule, an isocyanate compound (B) having two or more isocyanate groups in the molecule, and a phosphine compound (C). And a methacrylate compound (D).

(Thiol compound (A))
Examples of the thiol compound (A) include aliphatic polythiol compounds, aromatic polythiol compounds, aromatic polythiol compounds having sulfur atoms in addition to thiol groups (mercapto groups), and aliphatic polythiols having sulfur atoms in addition to thiol groups (mercapto groups). Compounds and the like.

  Aliphatic polythiol compounds include methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexane Dithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2- Dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis (mercaptomethyl) cyclohexane, thiomalic acid bis (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate) 2,3-dimercapto-1-propanol (3 Mercaptopropionate), 2,3-dimercapto-1-propanol (3-mercaptobutyrate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (3-mercaptobutyrate) Rate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene Glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (3-mercaptobutyrate), trimethylolpropane bis (2-mercaptoacetate) Trimethylolpropane bis (3-mercaptopropionate), trimethylolpropane bis (3-mercaptobutyrate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), tetrakis (mercaptomethyl) methane and the like.

  As aromatic polythiol compounds, 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis (mercaptomethyl) benzene, 1,3-bis (mercaptomethyl) ) Benzene, 1,4-bis (mercaptomethyl) benzene, 1,2-bis (mercaptoethyl) benzene, 1,3-bis (mercaptoethyl) benzene, 1,4-bis (mercaptoethyl) benzene, 1,2 , 3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris (mercaptomethyl) benzene, 1,2,4-tris (mercaptomethyl) ) Benzene, 1,3,5-tris (mercaptomethyl) benzene, 1,2,3-tris (mercaptoethyl) , 1,2,4-tris (mercaptoethyl) benzene, 1,3,5-tris (mercaptoethyl) benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di (p- Methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di (p-mercaptophenyl) pentane and the like.

  As aromatic polythiol compounds having sulfur atoms in addition to thiol groups (mercapto groups), 1,2-bis (mercaptoethylthio) benzene, 1,3-bis (mercaptoethylthio) benzene, 1,4-bis (mercapto) Ethylthio) benzene, 1,2,3-tris (mercaptomethylthio) benzene, 1,2,4-tris (mercaptomethylthio) benzene, 1,3,5-tris (mercaptomethylthio) benzene, 1,2,3- Examples include tris (mercaptoethylthio) benzene, 1,2,4-tris (mercaptoethylthio) benzene, 1,3,5-tris (mercaptoethylthio) benzene, and their nuclear alkylated products.

Aliphatic polythiol compounds containing sulfur atoms in addition to thiol groups (mercapto groups) include bis (mercaptomethyl) sulfide, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) sulfide, bis (mercaptoethyl) disulfide, bis ( Mercaptopropyl) sulfide, bis (mercaptomethylthio) methane, bis (2-mercaptoethylthio) methane, bis (3-mercaptopropylthio) methane, 1,2-bis (mercaptomethylthio) ethane, 1,2-bis (2 -Mercaptoethylthio) ethane, 1,2-bis (3-mercaptopropyl) ethane, 1,3-bis (mercaptomethylthio) propane, 1,3-bis (2-mercaptoethylthio) propane, 1,3-bis (3-mercaptopropylthio) propyl Bread, 1,2,3-tris (mercaptomethylthio) propane, 1,2,3-tris (2-mercaptoethylthio) propane, 1,2,3-tris (3-mercaptopropylthio) propane, 1,2 -Bis [(2-mercaptoethyl) thio] -3-mercaptopropane, 4-mercaptomethyl-3,6-dithia-1,8-octanedithiol, 4,8-dimercaptomethyl-1,11-mercapto-3 , 6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-mercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-mercapto-3,6 , 9-trithiaundecane, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis 3-mercaptopropylthiomethyl) methane, bis (2,3-dimercaptopropyl) sulfide, bis (1,3-dimercaptopropyl) sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-dithiane Mercaptomethyl-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, bis (mercaptopropyl) disulfide, etc. And esters of thioglycolic acid, mercaptopropionic acid and mercaptobutanoic acid; hydroxymethyl sulfide bis (2-mercaptoacetate), hydroxymethyl sulfide bis (3-mercaptopropionate), hydroxymethyl sulfide bis (3-mercapto Butyrate), hydroxyethyl sulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxyethyl sulfide bis (3-mercaptobutyrate), hydroxypropyl sulfide bis (2-mercaptoacetate), Hydroxypropyl sulfide bis (3-mercaptopropionate), hydroxypropyl sulfide bis (3-mercaptobutyrate), hydroxymethyl disulfide bis (2-mercaptoacetate), hydroxymethyl disulfide bis (3-mercaptopropionate), hydroxy Methyl disulfide bis (3-mercaptobutyrate), hydroxyethyl disulfide bis (2-mercaptoacetate), hydroxyethyl disulfide Bis (3-mercaptopropionate), hydroxyethyl disulfide bis (3-mercaptobutyrate), hydroxypropyl disulfide bis (2-mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropionate), hydroxypropyl disulfide bis (3-mercaptobutyrate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (3-mercaptobutyrate), 1,4-dithian-2,5-diol bis (2-mercaptoacetate), 1,4-dithian-2,5-diol bis (3-mercaptopropionate), 1,4-dithian-2,5-diol bis 3-mercaptobutyrate), thiodiglycolic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), thiodibutanoic acid bis (2-mercaptoethyl ester), 4,4-thiodibutyric acid Bis (2-mercaptoethyl ester), dithiodiglycolic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester), dithiodibutanoic acid bis (2-mercaptoethyl ester), 4,4- Dithiodibutyric acid bis (2-mercaptoethyl ester), thiodiglycolic acid bis (2,3-dimercaptopropyl ester), thiodipropionic acid bis (2,3-dimercaptopropyl ester), thiodibutanoic acid bis (2, 3-Dimercaptopropyl Este Bis), bis (2,3-dimercaptopropyl ester) dithioglycolate, bis (2,3-dimercaptopropyl ester) dithiodipropionate, bis (2,3-dimercaptopropyl ester) dithiodibutanoate, etc. It is done.
A thiol compound (A) may be used individually by 1 type, and may use 2 or more types together.

(Isocyanate compound (B))
Examples of the isocyanate compound (B) include diisocyanate, modified isocyanate, and triisocyanate.

  Examples of diisocyanates include 1,2-diisocyanatobenzene, 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, ethylphenylene diisocyanate, isopropylphenylene diisocyanate. Narate, dimethylphenylene diisocyanate, diethylphenylene diisocyanate, diisopropylphenylene diisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4'-methylenebis (phenylisocyanate), 4,4'-methylenebis (2-methylphenylisocyanate), bibenzyl-4,4 '-Diisocyanate, bis (isocyanatophenyl) ethylene, isophorone diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hex Methylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 4,4'-methylenebis (2-methylcyclohexyl isocyanate), 3,8-bis (isocyanatomethyl) tricyclodecane, 3 , 9-bis (isocyanatomethyl) tricyclodecane, 4,8-bis (isocyanatomethyl) tricyclodecane, 4,9-bis (isocyanatomethyl) tricyclodecane, and the like.

Examples of the modified isocyanate include diisocyanate biuret type and isocyanurate type.
Examples of the triisocyanate include triisocyanatononane, triphenylmethane triisocyanate, trimethylbenzene triisocyanate, benzene triisocyanate, toluene isocyanate and the like.
Other examples of isocyanate compounds (B) include isocyanate compounds that have been chain extended with one or more polyamines and / or polyols using appropriate materials and techniques known to those skilled in the art.
An isocyanate compound (B) may be used individually by 1 type, and may use 2 or more types together.

(Phosphine compound (C))
The phosphine compound (C) undergoes nucleophilic addition to the methacrylate compound (D), and the resulting strongly basic zwitterionic intermediate serves as a catalyst for the reaction between the thiol group and the isocyanate group.
Examples of the phosphine compound (C) include phosphines and diphosphines.

  Examples of phosphines include trimethylphosphine, triethylphosphine, tripropylphosphine, triisopropylphosphine, tri-n-butylphosphine, tri-t-butylphosphine, tri-n-octylphosphine, tricyclohexylphosphine, tribenzylphosphine, triphenyl. Phosphine, diphenylmethylphosphine, dimethylphenylphosphine, diphenylcyclohexylphosphine, dicyclohexylphenylphosphine, diethylphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri-2,4-ki Silylphosphine, tri-2,5-xylylphosphine, tri-3,5-xylylphosphine, tris (p-methoxyphenyl) phosphine, Lis (pt-butoxyphenyl) phosphine, di-tert-butylphenylphosphine, [4- (N, N-dimethylamino) phenyl] di-tert-butylphosphine, di-tert-butyl (2-butenyl) phosphine , Di-t-butyl (3-methyl-2-butenyl) phosphine, trimesitylphosphine and the like.

Diphosphines include 1,2-bis (dimethylphosphino) ethane, bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,2-bis (diphenylphosphino) propane, , 3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane, 2,3-bis (diphenylphosphino) butane, 1,5-bis (diphenylphosphino) pentane, and the like. .
A phosphine compound (C) may be used individually by 1 type, and may use 2 or more types together.

  The phosphine compound (C) is preferably a compound (I) represented by the following formula (I) from the viewpoint of having nucleophilicity suitable for nucleophilic addition to the methacrylate compound (D).

Provided that X ¹ , X ² and X ³ are each an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an alkynyl group having 1 to 8 carbon atoms, carbon It is a cycloalkyl group, a phenyl group, a biphenyl group, a naphthyl group, a phenoxy group or a heterocyclic group having a number of 3 to 6.
The alkyl group, alkoxy group, alkenyl group and alkynyl group may each be linear or branched.

X ¹ , X ² and X ³ may have a substituent.
As a substituent, a halogen atom, a C1-C8 alkyl group, a C1-C8 alkoxy group, a C1-C8 alkenyl group, a C1-C8 alkynyl group, a C3-C6 Examples thereof include a cycloalkyl group, an amino group, an alkylamino group having 1 to 8 carbon atoms, a nitro group, a phenyl group, a biphenyl group, a naphthyl group, a phenoxy group, and a heterocyclic group.

  As the phosphine compound (C), triphenylphosphine is particularly preferable because the reaction rate of nucleophilic addition to the methacrylate compound (D) is low and a long pot life is obtained.

(Methacrylate compound (D))
Examples of the methacrylate compound (D) include monofunctional methacrylate and polyfunctional methacrylate.

  Monofunctional methacrylates include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, tetrahydro Furfuryl methacrylate, stearyl methacrylate, ethyl carbitol methacrylate, dicyclopentenyloxyethyl methacrylate, isobornyl methacrylate, phenyl carbitol methacrylate, nonylphenoxyethyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, methacryloyloxyethyl succinate, Methacryloyloxyethyl phthalate Cyclohexyl methacrylate, phenyl methacrylate, cyanoethyl methacrylate, tribromophenyl methacrylate, phenoxyethyl methacrylate, tribromophenoxyethyl methacrylate, benzyl methacrylate, p-bromobenzyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, trifluoroethyl methacrylate, 2,2, Examples include 3,3-tetrafluoropropyl methacrylate.

  Polyfunctional methacrylates include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6 -Hexanediol dimethacrylate, hydrogenated dicyclopentadienyl dimethacrylate, ethylene oxide modified bisphenol A dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, tetramethylolmethane tetramethacrylate, pentaerythritol hexamethacrylate, polyfunctional epoxy Methacrylate, polyfunctional urethane Methacrylate, and the like.

(Other ingredients)
The curable composition may contain a monofunctional thiol or a monofunctional isocyanate for the purpose of adjusting the crosslinking density of the cured product.
The curable composition may contain pigments, UV absorbers, adhesion promoters, stabilizers, antioxidants, antifoaming agents, fillers, antisettling agents, plasticizers, viscosity modifiers, solvents, etc., as necessary. An additive may be included.

(Ratio of each component)
The molar ratio (SH / NCO) of all thiol groups to all isocyanate groups present in the curable composition is 0 from the viewpoint of the mechanical properties of the cured product, such as toughness, impact resistance, and abrasion resistance. 5/1 to 3/1 is preferable, and 0.8 / 1 to 2/1 is more preferable.

  0.05-5 equivalent% is preferable with respect to the thiol group contained in a thiol compound (A), and, as for a phosphine compound (C), 0.1-1 equivalent% is more preferable. When the equivalent percentage of the phosphine compound (C) is within the above range, it is possible to achieve both a long pot life and good curability without adversely affecting the material properties.

  0.05-5 equivalent% is preferable with respect to the thiol group contained in a thiol compound (A), and, as for the methacryloyloxy group contained in a methacrylate compound (D), 0.1-1 equivalent% is more preferable. When the equivalent percentage of the methacryloyloxy group contained in the methacrylate compound (D) is within the above range, it is possible to achieve both a long pot life and good curability without adversely affecting the material properties.

  Equivalent% of phosphine compound (C) to thiol group contained in thiol compound (A) and equivalent% of methacryloyloxy group contained in methacrylate compound (D) to thiol group contained in thiol compound (A) Either or both are preferably 0.30 equivalent% or less. If one or both of the phosphine compound (C) and the methacrylate compound (D) are within the above range, a long pot life of 40 minutes or longer at 25 ° C. can be obtained.

(Pot life)
The pot life of the curable composition of the present invention is 40 minutes or longer, preferably 60 minutes or longer. If the pot life of the curable composition of this invention is more than the lower limit of the said range, it is excellent in handleability. The upper limit of the pot life of the curable composition of the present invention is preferably 120 minutes from the viewpoint of minimizing the time required for the curing step.

(Mechanism of action)
In the present invention, a cocatalyst comprising a phosphine compound (C) and a methacrylate compound (D) is used as a catalyst for the reaction between the thiol group of the thiol compound (A) and the isocyanate group of the isocyanate compound (B). The phosphine compound (C) undergoes nucleophilic addition to the methacrylate compound (D), and the resulting strongly basic zwitterionic intermediate serves as a catalyst for the reaction between the thiol group and the isocyanate group. Here, since the methacrylate compound (D) has a lower reactivity with respect to nucleophilic addition than other Michael acceptors such as acrylate compounds, maleic acid, maleimide, vinyl sulfone, etc., the rate of formation of zwitterionic intermediates is low. Slow and long pot life can be obtained.

<Curable composition kit>
Since the thiol compound (A) and the isocyanate compound (B) react even without a catalyst, the curable composition of the present invention usually contains the thiol compound (A) and does not contain the isocyanate compound (B). It is used as a two-component curable composition comprising a composition (X) and a composition (Y) containing an isocyanate compound (B) and not containing a thiol compound (A).

Since the methacrylate compound (D) reacts with the thiol compound (A), it is included in the composition (Y) that does not contain the thiol compound (A).
Since the phosphine compound (C) reacts with the methacrylate compound (D), it is included in the composition (X) not containing the methacrylate compound (D).

  Therefore, as a two-component curable composition, a composition (X) containing a thiol compound (A) and a phosphine compound (C) and not containing an isocyanate compound (B) and a methacrylate compound (D); A composition comprising an isocyanate compound (B) and a methacrylate compound (D) and comprising a thiol compound (A) and a composition (Y) not containing a phosphine compound (C) is preferred.

The two-component curable composition is preferably provided as a curable composition kit having a first container containing the composition (X) and a second container containing the composition (Y). .
According to the curable composition kit, there is little change over time during storage, and when mixed, a long pot life and good curability are obtained in the reaction between the thiol group of the thiol compound (A) and the isocyanate group of the isocyanate compound (B). It is possible to provide a two-component curable composition excellent in handleability.

<Application>
(adhesive)
The curable composition of the present invention can be used as an adhesive. In the adhesive of the present invention, since it contains the curable composition of the present invention that can achieve both a long pot life and good curability, it is excellent in handleability when bonding objects to be bonded and has good curability. It is.

(Coating agent)
The curable composition of the present invention can be used as a coating agent.
Since the coating agent containing the curable composition of the present invention is cured on a substrate to form a coating layer, low molecular weight thiol compounds and isocyanate compounds can be used, and low viscosity and solvent-free are possible. is there. Moreover, in the coating agent of this invention, since the curable composition of this invention which can make a long pot life and favorable sclerosis | hardenability compatible is included, it is excellent in handleability and sclerosis | hardenability is good.

(Article with coating layer)
The article of the present invention has a coating layer formed by applying a coating agent containing the curable composition of the present invention to a substrate and curing it.
In the article of the present invention, since the coating layer is made of a cured product of the curable composition of the present invention, that is, a thiourethane resin, the coating layer is excellent in toughness, impact resistance, wear resistance, and the like.

(Fiber reinforced composite material)
The curable composition of the present invention can be used as a resin for a matrix of a fiber-reinforced composite material.
The fiber-reinforced composite material of the present invention includes a matrix made of a cured product of the curable composition of the present invention and reinforcing fibers. In the fiber-reinforced composite material of the present invention, since the matrix is made of a cured product of the curable composition of the present invention, that is, a thiourethane resin, the matrix is impregnated into the reinforcing fiber, toughness, impact resistance, and abrasion resistance. Excellent in properties.

(Optical substrate)
Since the cured product of the curable composition of the present invention, that is, the thiourethane resin has a high refractive index, it can be used as an optical substrate.
Examples of the optical substrate include a lens, a prism, an optical fiber, and an optical filter.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

(Pot life)
The pot life was measured as follows.
The phosphine compound (C) was added to the thiol compound (A) and heated to room temperature or 80 ° C. to completely dissolve it, thereby obtaining a composition (X). A composition (Y) composed of an isocyanate compound (B) and a methacrylate compound (D) was added to the composition (X) at 25 ° C., and stirred at 25 ° C. for 30 seconds to obtain a uniform mixed solution. Based on the time when the composition (Y) was added to the composition (X) as a reference, the time required to stop flowing even when the mixed solution was tilted was determined visually to make a pot life.

(Evaluation of curability)
The curability was evaluated as follows.
A liquid mixture was prepared in the same manner as the pot life measurement, poured into a plate-shaped mold, and allowed to stand at room temperature (25 ° C.). Six hours after mixing, the cured state was confirmed by touch and evaluated according to the following criteria.
○: There is no tack and the surface is dry.
X: There is tack, the surface is wet, or it is not completely cured.

(Thiol compound (A))
PEMP: Pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by SC Organic Chemicals).
(Isocyanate compound (B))
HMDI: Hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.).
(Phosphine compound (C))
TPP: Triphenylphosphine (Hokuko TPP (registered trademark), manufactured by Hokuko Chemical Co., Ltd.).
(Basic compound: Alternative to phosphine compound (C) and methacrylate compound (D))
DBU: Diazabicycloundecene (Tokyo Chemical Industry Co., Ltd.).
(Methacrylate compound (D))
TEGDMA: tetramethylene glycol dimethacrylate (manufactured by Shin-Nakamura Kogyo Co., Ltd., NK ester 4G).
(Acrylate compound: alternative to methacrylate compound (D))
TEGDA: tetramethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester A-200).
(Vinyl sulfone compound: alternative to methacrylate compound (D))
DVS: divinyl sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.).

Example 1
At the blending amounts shown in Table 1, TPP was added to PEMP and heated to 80 ° C. for complete dissolution. After dissolution, a mixture of HMDI and TEGDMA prepared in the blending amounts shown in Table 1 was added, stirred at 25 ° C. for 30 seconds to form a uniform mixed solution, and the pot life was measured. It was good.

(Examples 2 to 6)
The pot life was measured and the curability was evaluated in the same manner as in Example 1 except that the amounts of TPP and TEGDMA were changed in the amounts shown in Table 1. A long pot life of 40 minutes or more and good curability could be obtained under all conditions.

(Comparative Examples 1-4)
The pot life was measured and the curability was evaluated in the same manner as in Example 1 except that TEGDA (acrylate compound) was used instead of TEGDMA (methacrylate compound (D)) at the blending amounts shown in Table 1. However, only a short pot life of less than 10 minutes could be obtained under all conditions.

(Comparative Examples 5-6)
Measurement of pot life and evaluation of curability were carried out in the same manner as in Example 1 except that DVS (vinyl sulfone compound) was used instead of TEGDMA (methacrylate compound (D)) at the blending amounts shown in Table 1. As a result, only a short pot life of less than 10 minutes could be obtained under all conditions.

(Comparative Examples 7-9)
The pot life was measured and the curability was evaluated in the same manner as in Example 1 except that DBU, which was a base catalyst, was used instead of the TPP / TEGDMA cocatalyst with the blending amounts shown in Table 1. Under the conditions of Comparative Examples 7 and 8, only a short pot life of less than 10 minutes could be obtained, and under the conditions of Comparative Example 9, it was uncured after 3 hours.

  Thus, by using the cocatalyst consisting of the phosphine compound (C) and the methacrylate compound (D), a long pot life and good reaction in the reaction between the thiol group of the thiol compound (A) and the isocyanate group of the isocyanate compound (B). It is possible to obtain a curable composition having both excellent curability.

  The curable composition of the present invention is very useful as an adhesive, a coating agent, a resin for a matrix of a fiber reinforced composite material, a material for an optical substrate, and the like.

Claims (11)

A thiol compound (A) having two or more thiol groups in the molecule;
An isocyanate compound (B) having two or more isocyanate groups in the molecule;
A phosphine compound (C);
A methacrylate compound (D),
The curable composition whose following pot life is 40 minutes or more.
Pot life: The phosphine compound (C) is added to the thiol compound (A) and completely dissolved to obtain the composition (X). A composition (Y) composed of an isocyanate compound (B) and a methacrylate compound (D) is added to the composition (X), and stirred at 25 ° C. for 30 seconds to obtain a mixed solution. Based on the time when the composition (Y) is added to the composition (X) as a reference, the time required to stop flowing even when the mixture is tilted is defined as the pot life. The curable composition according to claim 1, wherein the phosphine compound (C) is a compound represented by the following formula (I).

Provided that X ¹ , X ² and X ³ are each an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an alkynyl group having 1 to 8 carbon atoms, carbon A cycloalkyl group having a number of 3 to 6, a phenyl group, a biphenyl group, a naphthyl group, a phenoxy group or a heterocyclic group, X ¹ , X ² and X ³ may have a substituent, and the substituent is A halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an alkynyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, It is at least one selected from the group consisting of an amino group, an alkylamino group having 1 to 8 carbon atoms, a nitro group, a phenyl group, a biphenyl group, a naphthyl group, a phenoxy group, and a heterocyclic group.   The curable composition according to claim 1 or 2, wherein the phosphine compound (C) is triphenylphosphine.   The curable composition as described in any one of Claims 1-3 whose said phosphine compound (C) is 0.05-5 equivalent% with respect to the thiol group contained in the said thiol compound (A).   The methacryloyloxy group contained in the said methacrylate compound (D) is 0.05-5 equivalent% with respect to the thiol group contained in the said thiol compound (A), It is any one of Claims 1-4. Curable composition.   Equivalent% of the phosphine compound (C) with respect to the thiol group contained in the thiol compound (A), and equivalent of the methacryloyloxy group contained in the methacrylate compound (D) with respect to the thiol group contained in the thiol compound (A) The curable composition as described in any one of Claims 1-5 whose one or both of% is 0.30 equivalent% or less.   The adhesive agent containing the curable composition as described in any one of Claims 1-6.   The coating agent containing the curable composition as described in any one of Claims 1-6.   The article | item which has a coating layer which consists of hardened | cured material of the curable composition as described in any one of Claims 1-6.   The fiber reinforced composite material containing the matrix which consists of a hardened | cured material of the curable composition as described in any one of Claims 1-6, and a reinforced fiber. A composition (X) containing a thiol compound (A) having two or more thiol groups in the molecule and a phosphine compound (C) and not containing the following isocyanate compound (B) and the following methacrylate compound (D). A first container containing
A composition (Y) containing an isocyanate compound (B) having two or more isocyanate groups in the molecule and a methacrylate compound (D), and not containing the thiol compound (A) and the phosphine compound (C). A curable composition kit, comprising: a second container containing