Curing agent, method for producing the same, and curing composition

Abstract

Provided is a curing agent having: a curing catalyst that is either a polyurea porous particle that holds an aluminum chelate, and an aliphatic cyclic polyolefin resin on the surface of the curing catalyst, and a non-water-soluble catalyst powder having a solubility in water of 5% by mass or less.

Description

TECHNICAL FIELD

[0001] The present application relates to a curing agent and a method for producing a curing agent, and a curing composition. BACKGROUND

[0002] Hitherto, an aluminum chelate compound has been mixed with a silanol compound to generate a cationic species, and a curing catalyst capable of curing an epoxy resin at room temperature, but practical use thereof has been difficult because of lack of latency.

[0003] To solve the above problems, the present inventors have conducted intensive studies, and as a result, have proposed microencapsulating the above aluminum chelate compound with a polyurea porous resin obtained by interfacial polymerization of a polyfunctional isocyanate compound, thereby making it possible to perform low-temperature rapid curing of an epoxy resin at a specific temperature, and enabling realization of a curing catalyst for one-liquid storage stability in an epoxy resin (for example, refer to Patent Documents 1 to 3).

[0004] However, in these proposals, the aluminum chelate compound changes in composition upon reaction with water, and thus there is a problem that the activity of the aluminum chelate compound is reduced when hydrolysis occurs upon encapsulation in water using interfacial polymerization of a polyfunctional isocyanate compound.

[0005] To solve the above problems, for example, a method for producing an aluminum chelate-based latent curing agent in which an aluminum chelate compound is added to and filled in an organic solvent in a particulate curing agent produced using an aluminum chelate compound, a silanol compound, and a polyfunctional isocyanate compound, and then surface-treated with an epoxy alkoxysilane coupling agent has been proposed (for example, refer to Patent Document 4). However, the polymerization coating film obtained using the above epoxy alkoxysilane coupling agent is a film obtained by polymerization of a monofunctional epoxy compound, and in particular, one-liquid storage stability at room temperature in a polar solvent system cannot be sufficiently satisfied.

[0006] Further, a latent curing agent composed of a polyurea resin, a porous particle that retains an aluminum chelate compound and an arylsilanol compound, and a film composed of a cured product of a alicyclic epoxy resin on the surface of the above porous particle has been proposed (for example, refer to Patent Document 5). The purpose of this proposal is to have both low-temperature curability and suppression of viscosity increase at the time of storage of a heat-curable epoxy resin composition, but the film composed of a cured product of an alicyclic epoxy resin contains a polar ester group in the structure, and in particular, one-liquid storage stability at room temperature in a polar solvent system cannot be sufficiently satisfied.

[0007] On the other hand, a water-soluble curing agent encapsulated capsule in which a water-soluble curing agent is used as a core, an inner layer of a shell has a water-soluble polymer, and an outer layer of the shell has a hydrophobic polymer has been proposed (for example, refer to Patent Document 6). In Example 12 of this proposal, an aliphatic cyclic polyolefin resin is used as the polymer of the outer layer.

[0008] Prior Art Documents

[0009] Patent Documents

[0010] Patent Document 1: Japanese Patent No. 4381255

[0011] Patent Document 2: Japanese Patent No. 5417982

[0012] Patent Document 3: Japanese Patent No. 5458596

[0013] Patent Document 4: International Publication No. 2017 / 104244

[0014] Patent Document 5: Japanese Patent Application Laid-Open No. 2017-222782

[0015] Patent Document 6: Japanese Patent Application Laid-Open No. 2015-232119 SUMMARY

[0016] PROBLEMS TO BE SOLVED BY THE INVENTION

[0017] However, in the above-described Patent Document 6, the material that can be encapsulated is limited to water-soluble curing agents such as imidazole compounds, amine compounds, and phenol-based compounds, and high-activity curing catalysts that react with water and non-water-soluble curing catalysts cannot be used. In addition, the invention described in Patent Document 6 solidifies the core because the core uses a water-soluble curing agent, and thus adds a polymer, and the shell is formed of an inner layer and an outer layer, which are clearly different from the constitution of the present invention. Further, the invention described in Patent Document 6 is a problem in that the curing reaction proceeds rapidly at the time of curing, and a cured product with few voids is formed, and curing at a lower temperature than before is possible, which is different from the present invention in that the one-liquid storage stability is greatly improved as a problem.

[0018] The present invention is to solve the above-described problems of the prior art, and to achieve the following objects. That is, the object of the present invention is to provide a curing agent in which curing at a lower temperature than before is possible, and the one-liquid storage stability is greatly improved, a method for producing the above-described curing agent, and a curing composition containing the above-described curing agent.

[0019] Method for Solving the Problem

[0020] As a method for solving the above-described problem, the following is provided. That is,

[0021] <1> A curing agent characterized by having a curing catalyst and an aliphatic cyclic polyolefin resin on the surface of the curing catalyst,

[0022] The above curing catalyst is either a polyurea porous particle that retains an aluminum chelate, and a non-water-soluble catalyst powder having a solubility in water of 5% by mass or less.

[0023] <2> The curing agent according to the above <1>, wherein the non-water-soluble catalyst powder contains a curable resin.

[0024] <3> The curing agent according to any one of the above <1> to <2>, wherein the volume average particle diameter is 10 μm or less.

[0025] <4> The curing agent according to any one of the above <1> to <3>, wherein the non-water-soluble catalyst powder is an amine adduct compound.

[0026] <5> The curing agent according to the above <4>, wherein the amine adduct compound is either an imidazole adduct body or an aliphatic amine adduct body.

[0027] <6> The curing agent according to any one of the above <1> to <5>, wherein the glass transition temperature of the aliphatic cyclic polyolefin resin is 140°C or less.

[0028] <7> The curing agent according to any one of the above <1> to <6>, wherein the aliphatic cyclic polyolefin resin is at least either a cyclic olefin copolymer (COC) or a cyclic olefin homopolymer (COP).

[0029] <8> A curing agent characterized in that the carbon atomic amount C1 (atom%) measured by X-ray photoelectron spectroscopy (XPS) method of a first curing agent having an aliphatic cyclic polyolefin resin and the carbon atomic amount C2 (atom%) measured by XPS method of a second curing agent obtained by removing the aliphatic cyclic polyolefin resin from the above first curing agent satisfy the following formula [(C1-C2) / C2] x 100 ≥ 1%.

[0030] <9> A curing agent characterized in that the heat generation start temperature ST1 (°C) and the heat generation peak temperature PT1 in differential scanning calorimetry (DSC) measurement of a first curing composition containing an epoxy resin and a first curing agent having an aliphatic cyclic polyolefin resin and the heat generation start temperature ST2 (°C) and the heat generation peak temperature PT2 (°C) in DSC measurement of a second curing composition containing an epoxy resin and a second curing agent obtained by removing the aliphatic cyclic polyolefin resin from the above first curing agent satisfy the following formulae ST1-ST2 ≥ 4°C, PT1-PT2 ≤ 5°C.

[0031] A method for producing a curing agent, characterized by spray-drying a dispersion liquid in which either of polyurea porous particles that hold an aluminum chelate and a non-water-soluble catalyst powder having a solubility in water of 5% by mass or less are dispersed, in a solution containing an aliphatic cyclic polyolefin resin at a content of 1% by mass or less in an organic solvent.

[0032] An curing composition, characterized by containing the curing agent described in any one of the above <1> to <9> and an epoxy resin.

[0033] A curing composition according to the above <11>, wherein the epoxy resin is at least one selected from the group consisting of an alicyclic epoxy resin, a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, and a solvent-containing epoxy resin in which these are dissolved in a solvent.

[0034] A curing composition according to any one of the above <11> to <12>, further containing a silanol compound.

[0035] Effects of the Invention

[0036] According to the present invention, the above-mentioned problems of the past can be solved, the above-mentioned objects can be achieved, and a curing agent and a method for producing the same, and a curing composition containing the same, which enable curing at a lower temperature than in the past, and greatly improve one-liquid storage stability, can be provided. BRIEF DESCRIPTION OF DRAWINGS

[0037] Figure 1 A graph showing the volume-based particle size distribution of the curing agent of Example 1, Example 2, and Comparative Example 1.

[0038] Figure 2 A graph showing the results of DSC measurement of the curing agent of Example 1, Example 2, and Comparative Example 1.

[0039] Figure 3 A graph showing the relationship between the storage time and the viscosity of the curing agent of Example 1, Example 2, and Comparative Example 1.

[0040] Figure 4 A graph showing the results of DSC measurement of the curing agent of Comparative Example 1 before and after the solvent resistance test.

[0041] Figure 5 A graph showing the results of DSC measurement of the curing agent of Comparative Example 2 before and after the solvent resistance test.

[0042] Figure 6 A graph showing the results of DSC measurement of the curing agent of Example 1 before and after the solvent resistance test.

[0043] Figure 7 A graph showing the results of DSC measurement on the curing agent of Example 2 before and after the solvent resistance test.

[0044] Figure 8 An SEM photograph (5,000x) of the curing agent of Comparative Example 1.

[0045] Figure 9 An SEM photograph (5,000x) of the curing agent of Example 1.

[0046] Figure 10 An SEM photograph (5,000x) of the curing agent of Example 2.

[0047] Figure 11 A graph showing the results of DSC measurement on the curing agent of Example 3 and Comparative Example 1.

[0048] Figure 12 A graph showing the relationship between the storage time and the viscosity of the curing agent of Example 3 and Comparative Example 1.

[0049] Figure 13 A graph showing the volume-based particle size distribution of the curing agent of Example 4 and Comparative Example 4.

[0050] Figure 14 A graph showing the results of DSC measurement on the curing agent of Example 4 and Comparative Example 4.

[0051] Figure 15 A graph showing the results of DSC measurement on the curing agent of Example 5 and Comparative Example 5.

[0052] Figure 16 A graph showing the relationship between the storage time and the viscosity of the curing agent of Example 4 and Comparative Example 4.

[0053] Figure 17 A graph showing the relationship between the storage time and the viscosity of the curing agent of Example 5 and Comparative Example 5.

[0054] Figure 18 A graph showing the results of TG measurement on the COC resin (APL6509T).

[0055] Figure 19 A graph showing the correlation between the COC resin concentration and the TG (mg). DETAILED DESCRIPTION

[0056] (Curing agent)

[0057] The curing agent of the present application has a curing catalyst, which is either a polyurea porous particle that retains an aluminum chelate, and a non-water-soluble catalyst powder having a solubility in water of 5% by mass or less, and an aliphatic cyclic polyolefin resin on the surface of the curing catalyst, and further contains other components as necessary.

[0058] In the present application, an aliphatic cyclic polyolefin resin is present on the surface of the above-described curing catalyst. The presence of the aliphatic cyclic polyolefin resin on the surface of the curing catalyst is not particularly limited, and a coating film of the aliphatic cyclic polyolefin resin is preferably formed, and the aliphatic cyclic polyolefin resin can be held on the surface by any interaction such as adhesion, coagulation, adsorption, van der Waals bond, etc.

[0059] In the case where a coating film of the above-described aliphatic cyclic polyolefin resin is formed on the surface of the above-described curing catalyst, the coating film can be formed by covering the entire surface of the above-described curing catalyst, or the coating film can be formed as a continuous film, and at least a part thereof can include a discontinuous film.

[0060] As a method for analyzing the presence of the aliphatic cyclic polyolefin resin on the surface of the above-described curing catalyst, a method in which the aliphatic cyclic polyolefin resin of the curing catalyst is dissolved using a solvent that selectively dissolves the aliphatic cyclic polyolefin resin, and the aliphatic cyclic polyolefin resin in the solution is analyzed using a thermogravimetric differential thermal analysis device (TG / DTA) or the like can be given. In addition, as the solvent that selectively dissolves the above-described aliphatic cyclic polyolefin resin, cyclohexane, chlorobenzene, or the like can be given.

[0061] In the present application, the carbon atomic amount C1 (atom%) determined by the X-ray photoelectron spectroscopy (XPS) method for the first curing agent having the aliphatic cyclic polyolefin resin and the carbon atomic amount C2 (atom%) determined by the XPS method for the second curing agent in which the aliphatic cyclic polyolefin resin is removed from the above-described first curing agent satisfy the following formula: [(C1-C2) / C2]x100 ≥ 1%.

[0062] It is confirmed that by satisfying the following formula: [(C1-C2) / C2]x100 ≥ 1%, the aliphatic cyclic polyolefin resin is present on the surface of the curing catalyst, and curing at a lower temperature than in the past becomes possible, and such an effect that the one-liquid storage stability is greatly improved is obtained.

[0063] As a method for removing the aliphatic cyclic polyolefin resin from the above-described first curing agent, a method in which the aliphatic cyclic polyolefin resin of the curing catalyst is dissolved using a solvent that selectively dissolves the aliphatic cyclic polyolefin resin (for example, cyclohexane, chlorobenzene, etc.) can be given.

[0064] Further, in the present application, by the fact that the heat generation start temperature ST1 (°C) in differential scanning calorimetry (DSC) measurement of the first curing composition containing the epoxy resin and the first curing agent having the aliphatic cyclic polyolefin resin, the heat generation peak temperature PT1 and the heat generation start temperature ST2 (°C) in DSC measurement of the second curing composition containing the epoxy resin and the second curing agent from which the aliphatic cyclic polyolefin resin is removed from the above first curing agent, the heat generation peak temperature PT2 (°C) satisfy the following formula ST1 - ST2 ≥ 4°C, PT1 - PT2 ≤ 5°C, curing at a lower temperature than in the past becomes possible, and the effect of greatly improving the one-liquid storage stability is obtained.

[0065] As a method of removing the aliphatic cyclic polyolefin resin from the above first curing agent, for example, a method of dissolving the aliphatic cyclic polyolefin resin of the curing catalyst using a solvent that selectively dissolves the aliphatic cyclic polyolefin resin (for example, cyclohexane, chlorobenzene, etc.) can be given.

[0066] < Curing Catalyst >

[0067] The above curing catalyst is any one of a polyurea porous particle that holds an aluminum chelate and a non-water-soluble catalyst powder having a solubility in water of 5% by mass or less.

[0068] < < Polyurea Porous Particle that Holds an Aluminum Chelate > >

[0069] The above porous particle is composed of a polyurea resin,

[0070] The above porous particle holds an aluminum chelate.

[0071] The above porous particle, for example, holds the above aluminum chelate in its fine pores. In other words, the aluminum chelate is taken up in and held by the fine pores present in the matrix of the porous particle composed of a polyurea resin.

[0072] - Polyurea Resin -

[0073] The above polyurea resin is a resin having a urea bond in the resin.

[0074] The above polyurea resin that constitutes the above porous particle is obtained, for example, by polymerizing a polyfunctional isocyanate compound in an emulsion. Details thereof will be described later. The above polyurea resin can have, in the resin, a bond derived from an isocyanate group, a bond other than a urea bond, for example, a urethane bond, etc. In the case of containing a urethane bond, it is sometimes referred to as a polyurea urethane resin.

[0075] - Aluminum Chelate -

[0076] As the above-mentioned aluminum chelate, for example, a complex compound in which three β-ketoenolate anions are coordinated to aluminum, represented by the following general formula (1), can be mentioned. Here, aluminum is not directly bonded to an alkoxy group. This is because if directly bonded, it is easily hydrolyzed, and is not suitable for emulsification treatment.

[0077] [Chem. 1]

[0078]

[0079] In the above-mentioned general formula (1), R 1 , R 2 , and R 3 each independently represent an alkyl group or an alkoxy group.

[0080] As the above-mentioned alkyl group, for example, a methyl group, an ethyl group, and the like can be mentioned.

[0081] As the above-mentioned alkoxy group, for example, a methoxy group, an ethoxy group, an oleyloxy group, and the like can be mentioned.

[0082] As the above-mentioned complex compound represented by the above-mentioned general formula (1), for example, tris(acetylacetonato)aluminum, tris(ethylacetoacetate)aluminum, monoacetylacetonato bis(ethylacetoacetate)aluminum, monoacetylacetonato bis(oleylacetoacetate)aluminum, and the like can be mentioned. They can be used alone as one kind, or two or more kinds can be used in combination.

[0083] The above-mentioned aluminum chelate, if contacted with water, is thermally decomposed, and thus is a compound which is not inherently soluble in water. Therefore, the polyurea porous particle which holds the aluminum chelate is a water-repellent curing catalyst.

[0084] The content of the above-mentioned aluminum chelate in the above-mentioned porous particle is not particularly limited, and can be appropriately selected as desired.

[0085] The average pore diameter of the pores of the above-mentioned porous particle is not particularly limited, and can be appropriately selected as desired, and is preferably 1 nm or more and 300 nm or less, more preferably 5 nm or more and 150 nm or less.

[0086] The volume average particle diameter of the above-mentioned porous particle is not particularly limited, and can be appropriately selected as desired, and is preferably 10 μm or less, more preferably 1 μm or more and 10 μm or less, particularly preferably 1 μm or more and 5 μm or less.

[0087] [Method for producing polyurea porous particle which holds aluminum chelate]

[0088] The above-mentioned method for producing a polyurea porous particle which holds an aluminum chelate includes a porous particle production step, and further includes other steps as necessary.

[0089] - Porous particle production step -

[0090] The porous particle production process includes at least an emulsion production process and a polymerization process, preferably includes a high impregnation process, and further includes other processes as necessary.

[0091] -- Emulsion production process

[0092] The emulsion production process is not particularly limited if it is a process of obtaining an emulsion by emulsifying a liquid obtained by mixing an aluminum chelate compound, a polyfunctional isocyanate compound, and preferably an organic solvent, and can be appropriately selected according to the purpose, for example, can be performed using a homogenizer.

[0093] As the aluminum chelate compound, the aluminum chelate compound described in the above description of the curing agent of the present application can be given.

[0094] The size of the oil droplets in the emulsion is not particularly limited and can be appropriately selected according to the purpose, and is preferably 0.5 μm or more and 100 μm or less.

[0095] -- Polyfunctional isocyanate compound

[0096] The polyfunctional isocyanate compound is a compound having two or more isocyanate groups in one molecule, and preferably a compound having three isocyanate groups. As further preferable examples of such a trifunctional isocyanate compound, a TMP adduct of the following general formula (2) obtained by reacting a diisocyanate compound with 3 moles with trimethylolpropane with 1 mole, an isocyanurate body of the following general formula (3) obtained by self-condensation of a diisocyanate compound with 3 moles, and a biuret body of the following general formula (4) obtained by condensation of a diisocyanate with 1 mole remaining in a diisocyanate urea obtained from 2 moles of a diisocyanate compound with 3 moles.

[0097] [Chem. 2]

[0098]

[0099] In the above general formulas (2) to (4), the substituent R is a moiety in which the isocyanate group of the diisocyanate compound is removed. As specific examples of such a diisocyanate compound, toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, m-xylylene diisocyanate, 1,6-hexane diisocyanate, hexahydro-m-xylylene diisocyanate, isophorone diisocyanate, methylene diphenyl-4,4'-diisocyanate, and the like can be given. They can be used alone as one kind, or two or more kinds can be used in combination.

[0100] The mixing ratio of the aluminum chelate compound to the polyfunctional isocyanate compound is not particularly limited and can be appropriately selected depending on the purpose. If the aluminum chelate compound is too little, the curability of the cationically curable compound to be cured is reduced, and if it is too much, the latency of the obtained curing agent is reduced. In this regard, the aluminum chelate compound is preferably 10 parts by mass or more and 500 parts by mass or less, and more preferably 10 parts by mass or more and 300 parts by mass or less, relative to 100 parts by mass of the polyfunctional isocyanate compound.

[0101] --Organic solvent--

[0102] The organic solvent is not particularly limited and can be appropriately selected depending on the purpose. It is preferably a volatile organic solvent.

[0103] The organic solvent is preferably a good solvent for each of the aluminum chelate compound and the polyfunctional isocyanate compound (the solubility in each is preferably 0.1 g / ml (organic solvent) or more), is substantially insoluble in water (the solubility in water is 0.5 g / ml (organic solvent) or less), and has a boiling point of 100°C or lower at atmospheric pressure. Specific examples of such a volatile organic solvent include alcohols, acetates, ketones, and the like. Among these, ethyl acetate is preferred from the viewpoints of high polarity, low boiling point, and poor water solubility.

[0104] The amount of the organic solvent used is not particularly limited and can be appropriately selected depending on the purpose.

[0105] --Polymerization treatment--

[0106] The polymerization treatment is not particularly limited and can be appropriately selected depending on the purpose, provided that it is a treatment in which the polyfunctional isocyanate compound is polymerized in the emulsion to obtain porous particles.

[0107] The porous particles hold the aluminum chelate compound.

[0108] In the polymerization treatment, part of the isocyanate groups of the polyfunctional isocyanate compound is hydrolyzed to become an amino group, and the amino group reacts with the isocyanate groups of the polyfunctional isocyanate compound to generate a urea bond, thereby obtaining a polyurea resin. Here, the polyfunctional isocyanate compound has a urethane bond, and the obtained polyurea resin also has a urethane bond. In this regard, the generated polyurea resin can also be referred to as a polyurea urethane resin.

[0109] The polymerization time in the polymerization treatment is not particularly limited and can be appropriately selected depending on the purpose. It is preferably 1 hour or more and 30 hours or less, and more preferably 2 hours or more and 10 hours or less.

[0110] As the polymerization temperature in the above polymerization treatment, there is no particular limitation, and it can be appropriately selected depending on the purpose, and is preferably 30°C or higher and 90°C or lower, and more preferably 50°C or higher and 80°C or lower.

[0111] After the polymerization treatment, in order to increase the amount of the aluminum chelate held by the porous particles, a high impregnation treatment of the aluminum chelate can be performed.

[0112] - High Impregnation Treatment -

[0113] As the high impregnation treatment, if it is a treatment in which the aluminum chelate is additionally filled in the above porous particles obtained by the above polymerization treatment, there is no particular limitation, and it can be appropriately selected depending on the purpose, and methods such as a method in which the above porous particles are impregnated in a solution in which the aluminum chelate is dissolved in an organic solvent, and then the above organic solvent is removed from the solution can be cited.

[0114] By performing the above high impregnation treatment, the amount of the aluminum chelate held by the above porous particles is increased. In addition, the above porous particles in which the aluminum chelate is additionally filled can be separated by filtration, washed, and dried as needed, and then pulverized into primary particles using a publicly known pulverizing device.

[0115] The aluminum chelate additionally filled in the above high impregnation treatment can be the same as the above aluminum chelate coordinated with the above liquid as the above emulsion, or can be different. For example, since water is not used in the above high impregnation treatment, the aluminum chelate used in the above high impregnation treatment can be an aluminum chelate in which an alkoxy group is bonded to aluminum. As such an aluminum chelate, for example, diisopropoxyaluminum monooleyl acetoacetate, monoisopropoxyaluminum bis(oyleyl acetoacetate), monoisopropoxyaluminum monooleate monoethyl acetoacetate, diisopropoxyaluminum monolauryl acetoacetate, diisopropoxyaluminum monostearyl acetoacetate, diisopropoxyaluminum monoiso-stearyl acetoacetate, monoisopropoxyaluminum mono-N-lauroyl-β-aluminoxane monolauryl acetoacetate, and the like can be cited. One of them can be used alone, and two or more of them can be used in combination.

[0116] As the organic solvent, there is no particular limitation, and it can be appropriately selected depending on the purpose, and methods such as the above organic solvents exemplified in the above description of the emulsion production treatment, and the like can be cited. The preferable mode is the same.

[0117] As the method of removing the above organic solvent from the above solution, there is no particular limitation, and it can be appropriately selected depending on the purpose, and methods such as a method in which the above solution is heated to a temperature of the boiling point of the above organic solvent or higher, a method in which the above solution is subjected to reduced pressure, and the like can be cited.

[0118] The content of the aluminum chelate in the solution obtained by dissolving the aluminum chelate in the organic solvent is not particularly limited and can be appropriately selected depending on the purpose, and is preferably 10% by mass or more and 80% by mass or less, and more preferably 10% by mass or more and 50% by mass or less.

[0119] <Non-water-soluble catalyst powder>

[0120] The non-water-soluble catalyst powder is hardly soluble in water or insoluble, and has a solubility of 5% by mass or less in water.

[0121] The solubility of the non-water-soluble catalyst powder in water can be confirmed by adding 5 g of the non-water-soluble catalyst powder to 95 g of water at 25°C, stirring with a stirrer for 24 hours, and measuring the weight loss of the non-water-soluble catalyst powder inherent in a high-temperature region of 200°C or higher using a thermogravimetric differential thermal analysis device (TG / DTA) when the liquid obtained by passing through a filter having an average pore diameter of 0.1 μm.

[0122] The non-water-soluble catalyst powder preferably contains a curable resin. As the curable resin, for example, a (meth)acrylic compound and an epoxy compound are preferably contained.

[0123] As the (meth)acrylic compound, for example, a (meth)acrylate compound obtained by reacting a compound having a hydroxyl group with a (meth)acrylic acid, an epoxy (meth)acrylate obtained by reacting a (meth)acrylic acid with an epoxy compound, a urethane (meth)acrylate obtained by reacting a (meth)acrylic acid derivative having a hydroxyl group with an isocyanate compound, and the like can be given. One kind alone can be used, or two or more kinds can be used in combination.

[0124] As the epoxy compound, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a 2,2'-diallyl bisphenol A type epoxy resin, a hydrogenated bisphenol type epoxy resin, an oxirane addition bisphenol A type epoxy resin, a resorcinol type epoxy resin, a diphenyl type epoxy resin, a sulfide type epoxy resin, a diphenyl ether type epoxy resin, a dicyclopentadiene type epoxy resin, a naphthalene type epoxy resin, a phenol novolak type epoxy resin, an o-cresol novolak type epoxy resin, a dicyclopentadiene novolak type epoxy resin, a diphenyl novolak type epoxy resin, a naphthol novolak type epoxy resin, a glycidyl amine type epoxy resin, an alkyl polyhydric alcohol type epoxy resin, a rubber-modified type epoxy resin, a glycidyl ester compound, and the like can be given. One kind alone can be used, or two or more kinds can be used in combination.

[0125] The non-water-soluble catalyst powder is in the form of particles, and the volume average particle diameter thereof is not particularly limited and can be appropriately selected according to the purpose, and is preferably 10 μm or less, more preferably 1 μm or more and 10 μm or less, and particularly preferably 1 μm or more and 5 μm or less.

[0126] The non-water-soluble catalyst powder is preferably an amine adduct compound.

[0127] Examples of the amine adduct compound include adducts of an imidazole compound and an epoxy compound, adducts of an aliphatic amine compound and an epoxy compound, and the like.

[0128] Examples of commercially available amine adduct compounds include Amicure PN-23, Amicure PN-23J, Amicure PN-H, Amicure PN-31, Amicure PN-31J, Amicure PN-40, Amicure PN-40J, Amicure PN-50, Amicure PN-F, Amicure MY-24, Amicure MY-H (all manufactured by Ajinomoto Fine Techno Co., Ltd.), P-0505 (manufactured by Shikoku Chemicals Corporation), P-200 (manufactured by Mitsubishi Chemical Corporation), ADEKA HARDNER EH-5001P, ADEKA HARDNER EH-5057PK, ADEKA HARDNER EH-5030S, ADEKA HARDNER EH-5011S (all manufactured by ADEKA Corporation), Fujicure FXR-1036, Fujicure FXR-1020, Fujicure FXR-1081 (manufactured by T&K TOKA Corporation), and the like. One of them can be used alone, or two or more of them can be used in combination.

[0129] <Aliphatic Cyclic Polyolefin Resin>

[0130] The aliphatic cyclic polyolefin resin refers to a polymer resin having an aliphatic cyclic olefin structure.

[0131] Examples of the aliphatic cyclic polyolefin resin include (1) norbornene-based polymers, (2) polymers of monocyclic cyclic olefins, (3) polymers of cyclic conjugated dienes, (4) vinyl alicyclic hydrocarbon polymers, and hydrogenated products of the above (1) to (4).

[0132] In the present application, the preferred polymer is an addition (co)polymer cyclic polyolefin containing at least one or more repeating units represented by the following general formula (II), and an addition (co)polymer cyclic polyolefin further containing at least one or more repeating units represented by the following general formula (I) as needed. In addition, a ring-opening (co)polymer containing at least one of the repeating units represented by the following general formulae (III) and (IV) can also be suitably used. Among these, at least any one of a cyclic olefin copolymer (cyclic olefin copolymer (COC resin), ethylene-norbornene copolymer) and a cyclic olefin homopolymer (cyclic olefin polymer (COP resin)) is preferred.

[0133] [Chemical Formula 3]

[0134]

[0135] [Chemical Formula 4]

[0136]

[0137] [Chemical Formula 5]

[0138]

[0139] [Chemical Formula 6]

[0140]

[0141] In the above general formulae (I) to (IV), m represents an integer of 0 to 10.

[0142] R 1 ~ R 7 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0143] X 1 ~ X 2 , and Y 1 represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, -(CH2) n COOR 8 , -(CH2) n OCOR 9 , -(CH2) n NCO, -(CH2) n NO2, -(CH2) n CN, -(CH2) n CONR 10 R 11 , -(CH2) n NR 10 R 11 , -(CH2) nOZ, -(CH2) n W, or X 1 and Y 1 or X 2 and Y 1 consisting of (-CO)2O, (-CO)2NR 12 In addition, R 8 , R 9 , R 10 , R 11 , R 12 represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, Z is a hydrocarbon group having 1 to 10 carbon atoms or a hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen, and W is SiR 13 p D 3-p (R 13 is a hydrocarbon group having 1 to 10 carbon atoms, and D is a halogen atom, -OCOR 14 or OR 14 , and p represents an integer of 0 to 3). R 14 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 0 to 10.

[0144] The above norbornene-based polymer hydride is synthesized by adding hydrogen after polyaddition or metathesis ring-opening polymerization of a polycyclic unsaturated compound, as disclosed in Japanese Patent Laid-Open No. 1-240517, Japanese Patent Laid-Open No. 7-196736, Japanese Patent Laid-Open No. 60-26024, Japanese Patent Laid-Open No. 62-19801, Japanese Patent Laid-Open No. 2003-1159767, or Japanese Patent Laid-Open No. 2004-309979, etc.

[0145] In the above norbornene-based polymer, R 5 to R 7 are preferably a hydrogen atom or -CH3, X 2 is preferably a hydrogen atom, Cl, -COOCH3, and other groups are appropriately selected. The above norbornene-based resin is commercially available under a trade name of Arton from JSR Corporation, and under a trade name of Zeonor, Zeonex from Zeon Corporation in Japan.

[0146] The above-described norbornene-based addition (co) polymer is disclosed in Japanese Patent Application Publication No. 10-7732, Japanese Patent Application Publication No. 2002-504184, US Patent No. 2004229157A1, or WO 2004 / 070463A1, or the like. It is obtained by polymerizing norbornene-based polycyclic unsaturated compounds with each other. In addition, norbornene-based polycyclic unsaturated compounds can be polymerized with ethylene, propylene, butylene; conjugated dienes such as butadiene, isoprene; non-conjugated dienes such as ethylene norbornene; linear diene compounds such as acrylonitrile, acrylic acid, methacrylic acid, maleic anhydride, acrylate, methacrylate, maleimide, vinyl acetate, vinyl chloride, or the like, as needed.

[0147] As the above-described norbornene-based addition (co) polymer, it is commercially available under the trade name of Appel from Mitsui Chemicals, Inc. In addition, it is commercially available as a pellet under the trade name of TOPAS from Polyplastics Corporation.

[0148] The glass transition temperature (Tg) of the above-described aliphatic cyclic polyolefin resin is preferably 140°C or lower, more preferably 135°C or lower, and further preferably 120°C or lower. By using the above-described aliphatic cyclic polyolefin resin having a low Tg of 140°C or lower, it is possible to obtain an effect that the temperature responsiveness (hydrogen bond-based destruction) of the polyurea porous particles that hold aluminum chelate is coated with the aliphatic cyclic polyolefin resin without being impaired.

[0149] The amount of the above-described aliphatic cyclic polyolefin resin attached (coating amount) in the above-described curing catalyst is not particularly limited as long as curing at a lower temperature than in the past becomes possible, an effect that the one-liquid storage stability is greatly improved is obtained, and can be appropriately selected as needed.

[0150] (Method for producing curing agent)

[0151] The method for producing the curing agent of the present application is to spray-dry a dispersion liquid in which either of polyurea porous particles that hold aluminum chelate and a non-water-soluble catalyst powder having a solubility in water of 5% by mass or less are dispersed, in a solution containing an aliphatic cyclic polyolefin resin in an organic solvent at a content of 1% by mass or less.

[0152] The content of the aliphatic cyclic polyolefin resin in the organic solvent is 1% by mass or less, preferably 0.5% by mass or less, and more preferably 0.1% by mass or less. The lower limit of the content is preferably 0.01% by mass or more.

[0153] If the content of the aliphatic cyclic polyolefin resin in the organic solvent exceeds 1% by mass, adverse conditions such as stringing, formation of coarse particles, or the like during spray-drying sometimes occur.

[0154] The content of the polyurea porous particles that hold the aluminum chelate or the non-water-soluble catalyst powder having a solubility of 5% by mass or less with respect to water in the above dispersion is preferably 5% by mass or more and 30% by mass or less.

[0155] The above organic solvent is preferably, for example, selected from chloro-based solvents such as dichloromethane and chloroform; solvents of chain hydrocarbons having 3 to 12 carbon atoms, cyclic hydrocarbons having 3 to 12 carbon atoms, aromatic hydrocarbons having 6 to 12 carbon atoms, esters, ketones, and ethers. In addition, the above esters, ketones, and ethers can have a cyclic structure.

[0156] As the chain hydrocarbons having 3 to 12 carbon atoms, for example, hexane, octane, isooctane, decane, and the like can be given.

[0157] As the cyclic hydrocarbons having 3 to 12 carbon atoms, for example, cyclopentane, cyclohexane, or derivatives thereof, and the like can be given.

[0158] As the aromatic hydrocarbons having 6 to 12 carbon atoms, for example, benzene, toluene, xylene, and the like can be given.

[0159] As the esters, for example, ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, amyl acetate, and the like can be given.

[0160] As the ketones, for example, acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, and the like can be given.

[0161] As the ethers, for example, diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole, phenyl ethyl ether, and the like can be given.

[0162] The spray drying is not particularly limited, and a publicly known spray drying device can be used.

[0163] The obtained above curing agent can be washed and coarsely pulverized as needed using an organic solvent, and after drying, pulverized into primary particles using a publicly known pulverizing device.

[0164] The organic solvent used for the above washing is not particularly limited, and can be appropriately selected according to the purpose, and is preferably a non-polar solvent. As the above non-polar solvent, for example, a hydrocarbon-based solvent or the like can be given. As the above hydrocarbon-based solvent, for example, toluene, xylene, cyclohexane, and the like can be given.

[0165] (Curing composition)

[0166] The curing composition of the present application contains the above curing agent of the present application and an epoxy resin, preferably contains a silanol compound, and further contains other components as needed.

[0167] < curing agent >

[0168] The curing agent contained in the above-mentioned curing composition is the above-mentioned curing agent of the present application.

[0169] The content of the above-mentioned curing agent in the above-mentioned curing composition is not particularly limited and can be appropriately selected depending on the purpose, and is preferably 1 part by mass or more and 70 parts by mass or less, more preferably 1 part by mass or more and 50 parts by mass or less, with respect to 100 parts by mass of the above-mentioned epoxy resin. If the content is less than 1 part by mass, the curability sometimes decreases, and if it exceeds 70 parts by mass, the resin properties (for example, flexibility) of the cured product sometimes decrease.

[0170] < epoxy resin >

[0171] The above-mentioned epoxy resin is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include alicyclic epoxy resins, glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, and solvent-containing epoxy resins in which these are dissolved in a solvent.

[0172] The above-mentioned alicyclic epoxy resin is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include vinylcyclopentadiene dioxide, vinylcyclohexene mono- to dioxides, dicyclopentadiene oxide, epoxy-[epoxy-oxaspiro C 8-15 alkyl]-ring C 5-12 alkane (for example, 3,4-epoxy-l-[8,9-epoxy-2,4-dioxaspiro[5.5]undecan-3-yl]-cyclohexane, and the like), 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carbonate, epoxy C 5-12 cycloalkyl C 1-3 alkyl-epoxy C 5-12 cycloalkane carboxylate (for example, 4,5-epoxycyclooctylmethyl-4',5'-epoxycyclooctane carboxylate, and the like), bis(C 1-3 alkyl-epoxy C 5-12 cycloalkyl C 1-3 alkyl)dicarboxylate (for example, bis(2-methyl-3,4-epoxycyclohexylmethyl)hexanedioate, and the like), and the like. One of them can be used alone, or two or more of them can be used in combination.

[0173] In addition, as the alicyclic epoxy resin, from the viewpoint of easy availability as a commercial product, it is preferable to use 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate (manufactured by Daicel Corporation, trade name: celoxide #2021P, epoxy equivalent: 128 to 140).

[0174] In addition, in the above-mentioned examples, C 8-15 , C 5-12 , C 1-3, and each of the descriptions of the number of carbon atoms of 8 to 15, the number of carbon atoms of 5 to 12, and the number of carbon atoms of 1 to 3 indicates that the structure of the compound has a width.

[0175] The following shows a structural formula of an example of the alicyclic epoxy resin.

[0176] [Chem. 7]

[0177]

[0178] As the glycidyl ether type epoxy resin or the glycidyl ester type epoxy resin, for example, it can be in a liquid state or in a solid state, and a substance having an epoxy equivalent of generally 100 to 4,000 or so and having two or more epoxy groups in the molecule is preferable. Examples thereof include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a phthalate type epoxy resin, and the like. One of them can be used alone, and two or more of them can be used in combination. Among these, from the aspect of the properties of the resin, a bisphenol A type epoxy resin can be preferably used. In addition, monomers and oligomers are also included in these epoxy resins.

[0179] <Silanol compound>

[0180] As the silanol compound, for example, an aryl silanol compound and the like can be given.

[0181] The aryl silanol compound is represented by, for example, the following general formula (A).

[0182] [Chem. 8]

[0183] (Ar) m Si(OH) n ... General formula (A)

[0184] However, in the general formula (A), m is 2 or 3, and is preferably 3, and the sum of m and n is 4. Ar is an aryl group which can have a substituent.

[0185] The aryl silanol compound represented by the general formula (A) is a mono-ol or a di-ol.

[0186] Ar in the general formula (A) is an aryl group which can have a substituent.

[0187] As the above-mentioned aryl group, there are, for example, phenyl, naphthyl (e.g., 1-naphthyl, 2-naphthyl, etc.), anthryl (e.g., 1-anthryl, 2-anthryl, 9-anthryl, benzo[a]-9-anthryl, etc.), phenanthryl (e.g., 3-phenanthryl, 9-phenanthryl, etc.), pyrenyl (e.g., 1-pyrenyl, etc.), indenyl, fluorenyl, diphenyl (e.g., 2-diphenyl, 3-diphenyl, 4-diphenyl, etc.), thienyl, furanyl, pyrrolyl, imidazolyl, pyridyl, etc. One of them can be used alone, or two or more of them can be used in combination. Among these, from the viewpoint of ease of obtaining and cost, phenyl is preferred. The m Ar groups can be the same or different, and from the viewpoint of ease of obtaining, it is preferred that the Ar groups be the same.

[0188] These aryl groups can have, for example, 1 to 3 substituents.

[0189] As the above-mentioned substituent, there are, for example, electron-withdrawing group, electron-donating group, etc.

[0190] As the above-mentioned electron-withdrawing group, there are, for example, halogen (e.g., chloro, bromo, etc.), trifluoromethyl, nitro, sulfo, carboxy, alkoxycarbonyl (e.g., methoxycarbonyl, ethoxycarbonyl, etc.), formyl, etc.

[0191] As the above-mentioned electron-donating group, there are, for example, alkyl (e.g., methyl, ethyl, propyl, etc.), alkoxy (e.g., methoxy, ethoxy, etc.), hydroxy, amino, monoalkylamino (e.g., monomethylamino, etc.), dialkylamino (e.g., dimethylamino, etc.), etc.

[0192] As a specific example of the phenyl group having a substituent, there are, for example, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,6-dimethylphenyl, 3,5-dimethylphenyl, 2,4-dimethylphenyl, 2,3-dimethylphenyl, 2,5-dimethylphenyl, 3,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2-ethylphenyl, 4-ethylphenyl, etc.

[0193] Further, by using an electron-withdrawing group as the substituent, it is possible to increase the acidity of the hydroxyl group of the silanol group. By using an electron-donating group as the substituent, it is possible to decrease the acidity of the hydroxyl group of the silanol group. Thus, by the substituent, it is possible to control the curing activity.

[0194] Here, the substituents of the m Ar groups can be different, and from the viewpoint of ease of obtaining, it is preferred that the substituents of the m Ar groups be the same. Further, only a part of the Ar groups can have a substituent, and the other Ar groups can have no substituent.

[0195] Among these, triphenylsilanol, diphenylsilanediol are preferred, and triphenylsilanol is particularly preferred.

[0196] <Other Components>

[0197] As the other component, there is no particular limitation, and it can be appropriately selected depending on the purpose, and examples include an oxetane compound, a silane coupling agent, a filler, a pigment, an antistatic agent, and the like.

[0198] << Oxetane Compound >>

[0199] In the above-mentioned curing composition, by using the above-mentioned oxetane compound in combination with the above-mentioned epoxy resin, it is possible to make the exothermic peak sharp.

[0200] As the above-mentioned oxetane compound, examples include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]diphenyl, 1,4-benzenedicarboxylic acid bis[(3-ethyl-3-oxetanyl)]methyl ester, 3-ethyl-3-(phenoxy-methyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, di[l-ethyl(3-oxetanyl)]methyl ether, 3-ethyl-3-{[3-(triethoxysilyl)propyloxy]methyl}oxetane, oxetanylsilsesquioxane, phenol novolak oxetane, and the like. One of them can be used alone, or two or more of them can be used in combination.

[0201] As the content of the above-mentioned oxetane compound in the above-mentioned curing composition, there is no particular limitation, and it can be appropriately selected depending on the purpose, and it is preferably 10 parts by mass or more and 100 parts by mass or less, and more preferably 20 parts by mass or more and 70 parts by mass or less, with respect to 100 parts by mass of the above-mentioned epoxy resin.

[0202] << Silane Coupling Agent >>

[0203] The above-mentioned silane coupling agent has a function of starting cationic polymerization of the epoxy resin together with an aluminum chelate as described in paragraphs

[0007] to

[0010] of Japanese Patent Application Publication No. 2002-212537. Therefore, by using a small amount of such a silane coupling agent, it is possible to obtain an effect of promoting the curing of the epoxy resin. As such a silane coupling agent, a silane coupling agent having one to three lower alkoxy groups in the molecule can have a reactive group in the molecule, such as a vinyl group, a styryl group, an acryloyloxy group, a methacryloyloxy group, an epoxy group, an amino group, a mercapto group, and the like. In addition, the coupling agent having an amino group or a mercapto group can be used without substantially capturing the generated cationic species, since the curing agent of the present application is a cationic curing agent.

[0204] Examples of silane coupling agents include, for instance, vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-styryltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-epoxypropoxypropyltrimethoxysilane, γ-epoxypropoxypropylmethyldiethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-chloropropyltrimethoxysilane. They can be used individually or in combination of two or more.

[0205] The content of the silane coupling agent in the curing composition is not particularly limited and can be appropriately selected according to the purpose. It is preferably 1 part or more to 300 parts or less, and more preferably 1 part or more to 100 parts or less, relative to 100 parts by mass of the curing agent.

[0206] The curing composition of the present invention enables curing at lower temperatures compared to the past, significantly improves the stability of single-liquid storage, and is highly convenient, thus making it widely applicable to various fields.

[0207] Example

[0208] The following describes embodiments of the present invention, but the present invention is not limited to these embodiments in any way.

[0209] (Example 1)

[0210] <Manufacturing of Curing Agent>

[0211] <<Porous Particle Manufacturing Process>>

[0212] -Modification of the aqueous phase-

[0213] 800 parts by weight of distilled water, 0.05 parts by weight of surfactant (Nurex RT, manufactured by Nippon Oil Co., Ltd.), and 4 parts by weight of polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) as dispersant were placed into a 3-liter interfacial polymerization container equipped with a thermometer and mixed evenly to prepare the aqueous phase.

[0214] -Oil phase preparation-

[0215] Next, 100 parts by mass of a 24% by mass isopropyl alcohol solution of aluminum chelate D (manufactured by Kawaken Fine Chemicals Co., Ltd.) of monoacetylacetone bis(ethylacetoacetate) aluminum, 70 parts by mass of a methylene diphenyl-4,4'-diisocyanate (3 moles) adduct (polyfunctional isocyanate compound, D-109, manufactured by Mitsui Chemicals, Inc.) of trimethylolpropane (1 mole), 30 parts by mass of divinylbenzene (manufactured by Merck) as a radical polymerizable compound, and a radical polymerization initiator (Perroil L, manufactured by Nippon Oil Mills Co., Ltd.) in an amount corresponding to 1% by mass (0.3 parts by mass) of the radical polymerizable compound were dissolved in 100 parts by mass of ethyl acetate to prepare an oil phase.

[0216] -Emulsification-

[0217] The prepared oil phase was added to the prepared water phase, and mixed and emulsified using a homogenizer (10,000 rpm / 5 minutes, T-50, manufactured by IKA Japan Co., Ltd.) to obtain an emulsion.

[0218] -Polymerization-

[0219] The prepared emulsion was subjected to interfacial polymerization and radical polymerization at 80°C for 6 hours. After the reaction was completed, the polymerization reaction solution was allowed to cool to room temperature (25°C), and the resulting polymer particles were separated by filtration and naturally dried at room temperature (25°C) to obtain a block-shaped curing agent. The obtained block-shaped curing agent was pulverized into primary particles using a pulverizing device (A-O jet mill, manufactured by Seishin Enterprise Co., Ltd.) to obtain a particulate curing agent.

[0220] -High impregnation treatment of aluminum chelate-

[0221] The obtained particulate curing agent (10.0 parts by mass) was added to an aluminum chelate solution [a solution in which aluminum chelate D (12.5 parts by mass) and another aluminum chelate (ALCH-TR, 25.0 parts by mass) were dissolved in ethyl acetate (62.5 parts by mass)], and stirring was performed at 200 rpm while the ethyl acetate was allowed to evaporate at 80°C for 9 hours.

[0222] After the stirring was completed, the solution was subjected to filtration treatment and washed with cyclohexane to obtain a block-shaped curing agent. The obtained block-shaped curing agent was vacuum-dried at 30°C for 4 hours, and then pulverized into primary particles using a pulverizing device (A-O jet mill, manufactured by Seishin Enterprise Co., Ltd.) to obtain a particulate curing agent (porous particles) in which the aluminum chelate was subjected to high impregnation treatment (11 parts by mass).

[0223] Preparation of a treatment liquid for spray drying

[0224] APL6509T (COC resin, glass transition temperature: 80°C, manufactured by Mitsui Chemicals, Inc.), which is an aliphatic cyclic polyolefin resin, was dissolved in cyclohexane so as to have a concentration of 0.1 mass%. (Hereinafter, this is sometimes referred to as "APL6509T solution".) Then, a product obtained by ultrasonic dispersion of the particulate curing agent subjected to the high impregnation treatment at a concentration of 10 mass% in the APL6509T solution was set as a treatment liquid for spray drying.

[0225] - Spray treatment -

[0226] Using a spray drying device (Mini Spray Dryer B-290, manufactured by Japan Buchi K.K.), spray drying of the treatment liquid for spray drying was performed, and a coarse particulate curing agent was obtained. The inlet temperature of the curing agent drying chamber was set to 45°C. The obtained coarse particulate curing agent was pulverized into primary particles using a pulverizing device (A-O Jet Mill, manufactured by Seishin Enterprise Co., Ltd.), and thereby a particulate curing agent was obtained. Thus, the curing agent of Example 1 was obtained.

[0227] (Example 2)

[0228] In Example 1, the concentration of APL6509T was changed to 0.01 mass% in the preparation of a treatment liquid for spray drying, and otherwise, the same operation as in Example 1 was performed, and thereby the curing agent of Example 2 was obtained.

[0229] (Comparative Example 1)

[0230] In Example 1, the spray drying using an aliphatic cyclic polyolefin resin was not performed, and otherwise, the same operation as in Example 1 was performed, and thereby the curing agent of Comparative Example 1 was obtained.

[0231] (Comparative Example 2)

[0232] In Example 1, instead of the addition of 100 mass parts of triphenylsilanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and the spray treatment in the preparation of an oil phase, a silane coupling agent surface treatment shown below was performed, and otherwise, the same operation as in Example 1 was performed, and thereby the curing agent of Comparative Example 2 formed of porous particles subjected to surface treatment with a silane coupling agent was obtained.

[0233] - Silane coupling agent surface treatment -

[0234] An epoxy alkoxysilane coupling agent (KBM-303, manufactured by Shin- Etsu Chemical Industry Co., Ltd.) 240 parts by mass was dissolved in cyclohexane 30 parts by mass to prepare a silane coupling agent treatment liquid. The above-mentioned particulate curing agent 30 parts by mass was put into the treatment liquid 300 parts by mass, and the mixture was stirred at 200 rpm for 8 hours at 30°C while the surface treatment of the silane coupling agent was performed. After the completion of the treatment reaction, the treatment was filtered, and washing was performed using cyclohexane, thereby obtaining a block-shaped curing agent. After the block-shaped curing agent obtained was vacuum-dried at 30°C for 4 hours, it was pulverized into primary particles using a pulverizing device (A-O jet mill, manufactured by Seishin Enterprise Co., Ltd.), thereby obtaining a curing agent.

[0235] (Comparative Example 3)

[0236] In the <preparation of an oil phase> in Example 1, instead of the addition of triphenylsilanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 100 parts by mass and the spray treatment, coating treatment with a cured product of a cycloaliphatic epoxy resin shown below was performed, and otherwise, the same operation as in Example 1 was performed, thereby obtaining a curing agent of Comparative Example 3 formed of porous particles whose surfaces were treated with a cured product of a cycloaliphatic epoxy resin.

[0237] The above-mentioned particulate curing agent 25 parts by mass was put into a solution (a solution in which cyclohexane 120 parts by mass and a cycloaliphatic epoxy resin (CEL2021P, manufactured by Daicel Corporation) 180 parts by mass were dissolved) 300 parts by mass, and stirring was performed at 200 rpm for 20 hours at 30°C. During the stirring, the above-mentioned cycloaliphatic epoxy resin was polymerized and cured on the surfaces of the above-mentioned porous particles. As a result, a coating film composed of a cured product of the above-mentioned cycloaliphatic epoxy resin was formed on the surfaces of the above-mentioned porous particles.

[0238] After the completion of the stirring, the treatment was filtered, and washing was performed using cyclohexane, thereby obtaining a block-shaped curing agent. After the block-shaped curing agent obtained was vacuum-dried at 30°C for 4 hours, it was pulverized into primary particles using a pulverizing device (A-O jet mill, manufactured by Seishin Enterprise Co., Ltd.), thereby obtaining a curing agent.

[0239] <particle size distribution>

[0240] The particle size distribution on a volume basis was measured using an MT3300EXII (laser diffraction scattering method, manufactured by microtrack bell Co., Ltd.) with respect to the curing agents of Examples 1 to 2 and Comparative Example 1. The results are shown in Table 1 and Figure 1 .

[0241] [table 1]

[0242]

[0243] From the results of Table 1 and Figure 1 In Examples 1 and 2, the treatment concentration of the COC resin was less than 1 mass%, and therefore no coarse grain was observed.

[0244] <DSC Measurement>

[0245] Next, with respect to the curing agent of Comparative Example 1, Example 1, and Example 2, DSC measurement was performed by operating as follows. The results are shown in Table 2. Further, the DSC charts of Comparative Example 1, Example 1, and Example 2 are shown in Figure 2 .

[0246] Composition for DSC Measurement

[0247] A composition prepared in a manner that EP828 : triphenylsilanol : curing agent = 80 : 8 : 4 in mass ratio was used as a sample for DSC measurement.

[0248] • EP828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation)

[0249] • Triphenylsilanol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0250] • Curing agent: curing agent of Comparative Example 1, Example 1, and Example 2 - DSC measurement conditions

[0251] • Measuring device: DSC6200 (manufactured by Hitachi High-Tech Science Corporation)

[0252] • Evaluation amount: 5 mg

[0253] • Temperature increasing rate: 10°C / min

[0254] [Table 2]

[0255]

[0256] From the results of Table 1 and Figure 2 Table 2, the heat generation start temperature of the COC resin-treated products of Examples 1 and 2 was higher by 10°C or more than that of Comparative Example 1 which was an untreated product. Further, in Examples 1 and 2, a COC resin having a low glass transition temperature Tg was used, and therefore the heat generation peak temperature was higher by less than 3°C than that of Comparative Example 1 which was an untreated product.

[0257] <One-liquid Storage Stability>

[0258] Next, regarding the curing agent of Comparative Example 1, Example 1, and Example 2, one liquid storage stability caused by viscosity change was evaluated by the following operation. The results are shown in Table 3. Further, the viscosity change of Comparative Example 1, Example 1, and Example 2 is shown in Figure 3 .

[0259] Composition for storage stability measurement

[0260] A composition prepared in a manner that the mass ratio of CEL2021P: KBM-403: triphenylsilanol: curing agent = 100: 0.5: 7: 2 was used as a sample for storage stability measurement.

[0261] • CEL2021P (cycloaliphatic epoxy resin, manufactured by Daicel Corporation)

[0262] • KBM-403 (silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0263] • Triphenylsilanol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0264] • Curing agent: curing agent of Comparative Example 1, Example 1, and Example 2 - conditions for storage stability

[0265] • Storage temperature: 25°C

[0266] • Storage period: 48 hours

[0267] • Viscosity measurement: SV-10 (tuning fork vibration type viscometer, manufactured by A&D Company)

[0268] • Viscosity measurement temperature: 20°C

[0269] [Table 3]

[0270]

[0271] From the results of Table 3 and Figure 3 It was confirmed that the curing agent of Example 1 and Example 2, which was treated with a COC resin, showed superior high potential in a cycloaliphatic epoxy resin, which is excellent in cationic polymerizability, compared to the untreated product of Comparative Example 1. Further, it was known that in Examples 1 and 2, the viscosity multiple after 48 hours showed 2 times or less.

[0272] Evaluation of solvent resistance

[0273] Next, regarding the curing agent of Comparative Example 1, Comparative Example 2, Comparative Example 3, Example 1, and Example 2, solvent resistance evaluation was performed by the following operation. The results are shown in Table 4. Further, Figure 4 A graph showing the results of DSC measurement regarding the curing agent of Comparative Example 1. Figure 5A graph showing the results of DSC measurement on the curing agent of Comparative Example 2. Figure 6 A graph showing the results of DSC measurement on the curing agent of Example 1. Figure 7 A graph showing the results of DSC measurement on the curing agent of Example 2.

[0274] Composition for solvent resistance evaluation

[0275] A composition prepared in a manner that the YP solution : YX8000 : triphenylsilanol : curing agent = 50 : 40 : 7 : 3 in terms of mass ratio was used as a test sample for solvent resistance evaluation.

[0276] • YP70 (phenoxy resin, manufactured by Nippon Ferrosi Chemical & Material Co., Ltd.)

[0277] • YP70 solution (a solution in which YP70 was dissolved at 45 mass% in propylene glycol monomethyl ether acetate was used)

[0278] • YX8000 (hydrogenated bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation)

[0279] • Evaluation method: The mixture immediately after mixing (0 hours) and the mixture left to stand at room temperature (25°C) for 4 hours were coated on a PET film using a bar coater at a thickness of 20 μm. Then, the product obtained by drying at 80°C for 5 minutes was evaluated using DSC.

[0280] • Curing agent: curing agents of Comparative Example 1, Comparative Example 2, Comparative Example 3, Example 1, and Example 2 - DSC measurement conditions

[0281] • Measuring device: DSC6200 (manufactured by Hitachi High-Tech Science Corporation)

[0282] • Evaluation amount: 5 mg

[0283] • Temperature increasing rate: 10°C / min

[0284] [Table 4]

[0285]

[0286] From the results of Table 4 and Figures 4 to 7 As compared with Comparative Example 1 (untreated product) and Comparative Example 2 (silane coupling agent surface treatment), Comparative Example 3 (coating treatment with a curing product of an alicyclic epoxy resin), it was confirmed that Examples 1 and 2 had excellent solvent resistance, since no decrease in the total heat generation amount of DSC was observed after leaving to stand at room temperature for 4 hours.

[0287] Surface elemental analysis by XPS

[0288] Next, regarding the curing agent of Comparative Example 1, Example 1, and Example 2, surface elemental analysis was performed using XPS under the following conditions. The results are shown in Table 5.

[0289] -XPS measurement conditions-

[0290] As the measurement device, XPS (PHI 5000 Versa Probe III, manufactured by ulvac-phi, Inc.) was used. As the X-ray source, Al Kα was used, and as the measurement conditions, a current value of 34 mA, an acceleration voltage value of 15 kV, and a scanning speed of 1 eV were used.

[0291] [Table 5]

[0292]

[0293] From the results of Table 5, it was confirmed that the curing agent of Examples 1 and 2 had a tendency of an increase in carbon (C) and a decrease in aluminum (Al) on the surface, compared to the untreated curing agent of Comparative Example 1. Therefore, it was known that the surface of the curing agent had an aliphatic cyclic polyolefin resin (COC resin).

[0294] <SEM (scanning electron microscope) observation>

[0295] Next, regarding the curing agent of Comparative Example 1, Example 1, and Example 2, SEM photographs taken using JSM-6510A (manufactured by JEOL Ltd.) are shown. Figure 8 This is a SEM photograph of the curing agent of Comparative Example 1 at 5,000 times. Figure 9 This is a SEM photograph of the curing agent of Example 1 at 5,000 times, Figure 10 This is a SEM photograph of the curing agent of Example 2 at 5,000 times.

[0296] From the SEM photographs of Figures 8 to 10 Examples 1 and 2 were subjected to coating treatment using a low concentration of COC resin, and thus, compared to the untreated Comparative Example 1, no formation of coarse particles and no heteromorphic change were observed.

[0297] (Example 3)

[0298] In Example 1, in the <Preparation of a treatment liquid for spray drying>, the COC resin (APL6509T) was changed to a COP resin (ZNR1020, glass transition temperature Tg: 102°C, manufactured by Zeon Corporation), and otherwise, the same operations as in Example 1 were performed, and the curing agent of Example 3 was obtained.

[0299] <DSC measurement>

[0300] Next, the DSC measurement was performed on the curing agent of Example 3, in the same manner as in Example 1. The results are shown in Table 6. Further, the DSC charts of Comparative Example 1 and Example 3 are shown in Figure 11 .

[0301] [Table 6]

[0302]

[0303] From the results of Table 6 and Figure 11 It was confirmed that even in the COP treatment, the exothermic onset temperature was greatly increased in temperature. Further, the exothermic peak temperature was increased more than in the COC treatment, but since it was less than 3°C, consistency with Technical Solution 9 was obtained without a problem (PT1-PT2≤5°C).

[0304] <One liquid storage stability>

[0305] Next, the one liquid storage stability resulting from the viscosity change was evaluated on the curing agent of Example 3, in the same manner as in Example 1. The results are shown in Table 7. Further, the viscosity changes of Comparative Example 1 and Example 3 are shown in Figure 12 .

[0306] [Table 7]

[0307]

[0308] (Example 4)

[0309] -Non-water-soluble catalyst powder-

[0310] In Example 1, the particulate curing agent (porous particle) treated with high impregnation of an aluminum chelate was replaced with a non-water-soluble catalyst powder: cure duct P-0505 (imidazole adduct body, manufactured by Shikoku Chemicals Corporation), and otherwise, the same operation as in Example 1 was performed to obtain the curing agent of Example 4, which was treated at a concentration of 0.1 mass% of APL6509T.

[0311] (Example 5)

[0312] -Non-water-soluble catalyst powder-

[0313] In Example 1, the particulate curing agent (porous particle) treated with high impregnation of an aluminum chelate was replaced with a non-water-soluble catalyst powder: Amicure MY-24 (aliphatic amine adduct body, manufactured by Ajinomoto Fine Techno Co., Inc.), and otherwise, the same operation as in Example 1 was performed to obtain the curing agent of Example 5, which was treated at a concentration of 0.1 mass% of APL6509T.

[0314] (Comparative Example 4)

[0315] In Example 4, spray drying using aliphatic cyclic polyolefin resin was not performed. Otherwise, the same procedure as in Example 4 was followed to obtain the curing agent of Comparative Example 4.

[0316] (Comparative Example 5)

[0317] In Example 5, spray drying using aliphatic cyclic polyolefin resin was not performed. Otherwise, the same procedure as in Example 5 was followed to obtain the curing agent of Comparative Example 5.

[0318] <Water Solubility Test>

[0319] When 5g of Cure Duct P-0505 (imidazolium adduct, manufactured by Shikoku Chemical Industry Co., Ltd.) or Amicure MY-24 (aliphatic amine adduct, manufactured by Ajinomoto Fine Techno Co., Ltd.) is added to 95g of water at 25°C and stirred for 24 hours, the liquid obtained after passing through a filter with an average pore size of 0.1μm is measured using a thermogravimetric differential calorimeter (TG / DTA). Typically, in the high-temperature region above 200°C, P-0505 shows 87.2% and MY-24 shows 74.5%, indicating a decrease in weight, but the weight decrease cannot be confirmed.

[0320] Therefore, it was confirmed that Cure Duct P-0505 and Amicure MY-24 are insoluble in water (their solubility relative to water is less than 5% by mass).

[0321] Next, regarding the curing agents of Example 4 and Comparative Example 4 (untreated), the volumetric particle size distribution was measured using MT3300EXII (laser diffraction scattering method, manufactured by Microtrack Bell Co., Ltd.). The results are shown in Table 8 and... Figure 13 .

[0322] [Table 8]

[0323]

[0324] From Table 8 and Figure 13 As a result, in Example 4, since the concentration of COC resin in the treatment solution was kept at a low concentration of less than 1% by mass, no coarse particles were observed to form due to the COC resin coating treatment.

[0325] <DSC Measurement>

[0326] Next, regarding the curing agent of Comparative Example 4, Comparative Example 5, Example 4, and Example 5, DSC measurement was performed by the following operation. The results are shown in Table 9. Further, the DSC chart of Comparative Example 4 and Example 4 is shown in Figure 14 The DSC chart of Comparative Example 5 and Example 5 is shown in Figure 15 .

[0327] Composition for DSC measurement

[0328] A composition prepared in such a manner that EP828 : curing agent = 72 : 8 in mass ratio was used as a sample for DSC measurement.

[0329] • EP828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation)

[0330] • Curing agent: Curing agent of Comparative Example 4, Comparative Example 5, Example 4, and Example 5 - DSC measurement conditions

[0331] • Measuring device: DSC6200 (manufactured by Hitachi High-Tech Science Corporation)

[0332] • Evaluation amount: 5 mg

[0333] • Temperature increasing rate: 10°C / min

[0334] [Table 9]

[0335]

[0336] From the results of Table 9, Figure 14 and Figure 15 Example 4 and 5, as compared with Comparative Examples 4 and 5 which are untreated products, were high-temperature-ized in the heat generation start temperature by the COC resin coating treatment, but the high-temperature-ization amount of the heat generation peak temperature was less than +3°C.

[0337] <One liquid storage stability>

[0338] Next, regarding the curing agent of Comparative Example 4, Example 4, Comparative Example 5, and Example 5, one liquid storage stability was evaluated by the following operation. The results of Comparative Example 4 and Example 4 are shown in Table 10, and the results of Comparative Example 5 and Example 5 are shown in Table 11. Further, the results of Comparative Example 4 and Example 4 are shown in Figure 16 Further, the results of Comparative Example 5 and Example 5 are shown in Figure 17 .

[0339] Composition for storage stability measurement

[0340] A composition prepared in such a manner that EP828 : curing agent = 72 : 8 in mass ratio was used as a sample for DSC measurement.

[0341] • EP828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation)

[0342] • Curing agent: Curing agent of Comparative Example 4, Example 4, and Comparative Example 5, Example 5 - Conditions for storage stability

[0343] • Storage temperature: 30°C

[0344] • Storage period: 72 hours (Comparative Example 4 and Example 4), 168 hours (Comparative Example 5 and Example 5)

[0345] • Viscosity measurement: SV-10 (tuning fork vibration type viscometer, manufactured by A&D Company)

[0346] • Viscosity measurement temperature: 20°C

[0347] [Table 10]

[0348]

[0349] [Table 11]

[0350]

[0351] From the results of Table 10, Table 11, Figure 16 and Figure 17 It was shown that the viscosity multiple after 72 hours of Example 4, which was subjected to COC resin treatment, was less than 1.2 times, regardless of whether or not it was stored at 30°C. Furthermore, in Example 5, the viscosity multiple after 168 hours was shown to be less than 1.1 times.

[0352] <Surface elemental analysis by XPS>

[0353] Next, regarding the curing agent of Comparative Example 4, Comparative Example 5, Example 4, and Example 5, surface elemental analysis was performed by XPS using the following conditions. The results are shown in Table 12.

[0354] -XPS measurement conditions-

[0355] As the measurement device, XPS (PHI 5000 Versa Probe III, manufactured by ulvac-phi, Inc.) was used. As the X-ray source, Al Kα was used, and as the measurement conditions, a current value of 34 mA, an acceleration voltage value of 15 kV, and a scanning speed of 1 eV were used.

[0356] [Table 12]

[0357]

[0358] It was confirmed from the results of Table 12 that the cured catalysts of Examples 4 and 5 had an increased carbon (C) and a decreased nitrogen (N) derived from imidazole or amine on the surface of the cured catalysts, compared with the untreated cured catalysts of Comparative Examples 4 and 5. Thus, it was known that the surface of the cured catalysts of Examples 4 and 5 had an aliphatic cyclic polyolefin resin (COC resin). <Confirmation method of presence of aliphatic cyclic polyolefin resin on the surface of the cured catalyst>

[0359] It was confirmed that the surface of the cured catalyst had an aliphatic cyclic polyolefin resin by the following operation.

[0360] First, regarding the COC resin (APL6509T, glass transition temperature Tg: 80°C, manufactured by Mitsui Chemicals, Inc.), TG was measured using the following conditions. The results are shown in Figure 18 .

[0361] -TG measurement conditions-

[0362] • TG / DTA6200 (manufactured by Hitachi High-Tech Science Corporation)

[0363] • Temperature increasing rate: 10°C / min

[0364] • Measurement weight: 5 mg

[0365] From the results of Table 12, it was confirmed that the cured catalysts of Examples 4 and 5 had an increased carbon (C) and a decreased nitrogen (N) derived from imidazole or amine on the surface of the cured catalysts, compared with the untreated cured catalysts of Comparative Examples 4 and 5. Thus, it was known that the surface of the cured catalysts of Examples 4 and 5 had an aliphatic cyclic polyolefin resin (COC resin). <Confirmation method of presence of aliphatic cyclic polyolefin resin on the surface of the cured catalyst> Figure 18

[0366] Next, a correlation diagram of the measured COC resin concentration and TG (mg) is shown in Figure 19 . The measurement used a product in which the COC resin was dissolved in chlorobenzene. The TG was plotted with the weight reduction value in the range of 400°C to 500°C.

[0367] <COC content of COC-treated cured catalyst particles>

[0368] Based on the above-mentioned Figure 19 correlation diagram, quantitative analysis of the content of the COC resin of Example 1 and Example 2 was performed.

[0369] - Measurement method -

[0370] ​The solidification catalysts treated with the COC resin (Examples 1 and 2) were dispersed in chlorobenzene at a concentration of 25 mass%, and the COC resin was dissolved by stirring at 200 rpm for 7 days at room temperature. After removing the solidification catalyst by treatment with a filter having an average pore diameter of 0.45 μm, the concentration of the COC resin contained in the recovered liquid was measured using TG / DTA, and the COC resin concentration in the measurement liquid was calculated using the above-mentioned COC resin concentration-TG correlation chart. Then, the ratio of the COC resin contained in the solidification catalyst was calculated from the amount of the solidification catalyst treated and the amount of the liquid. The results are shown in Table 13.

[0371] [Table 13]

[0372]

[0373] * The TG in Table 13 (mg) indicates the amount of weight reduction between 400°C and 500°C.

[0374] From the results in Table 13, the COC resin ratio of the solidification catalyst of Example 1 was 0.26 mass%, and the COC resin ratio of the solidification catalyst of Example 2 was 0.06 mass%. Thus, it was confirmed that the COC resin was coated on the surface of the solidification catalyst particles in a thin film state.

[0375] As explained above, the solidification catalyst obtained by coating the surface of either the polyurea porous particles retaining the aluminum chelate or the non-water-soluble catalyst powder having a solubility in water of 5 mass% or less with the aliphatic cyclic polyolefin resin makes it possible to solidify at a lower temperature than before, and it was found that by incorporating the above-mentioned solidification catalyst, an epoxy resin composition having greatly improved one-liquid storage stability was obtained.

Claims

1. A curing agent, wherein, It has a curing catalyst and an aliphatic cyclic polyolefin resin on the surface of the curing catalyst. The curing catalyst is either a polyurea porous particle that retains the aluminum chelate, or a non-water-soluble catalyst powder with a solubility of less than 5% by mass relative to water. The non-water-soluble catalyst powder is an amine adduct compound, which is either an imidazole adduct or an aliphatic amine adduct.

2. The curing agent according to claim 1, wherein, The water-insoluble catalyst powder contains a curable resin.

3. The curing agent according to claim 1 or 2, wherein, The volume average particle size is less than 10 μm.

4. The curing agent according to claim 1 or 2, wherein, The glass transition temperature of the aliphatic cyclic polyolefin resin is below 140°C.

5. The curing agent according to claim 1 or 2, wherein, The aliphatic cyclic polyolefin resin is at least one of cyclic olefin copolymer (COC) and cyclic olefin homopolymer (COP).

6. A method for manufacturing a curing agent, wherein, A dispersion of either polyurea porous particles that retain aluminum chelates or a non-water-soluble catalyst powder with a solubility of 5% or less relative to water, dispersed in an organic solvent solution containing aliphatic cyclic polyolefin resin at a content of less than 1% by mass, is spray-dried.

7. A curing composition, wherein, contain: The curing agent and epoxy resin according to any one of claims 1 to 5.

8. The curing composition according to claim 7, wherein, The epoxy resin is selected from at least one of alicyclic epoxy resins, glycidyl ether epoxy resins, glycidyl ester epoxy resins, and solvent-containing epoxy resins in which they are dissolved in a solvent.

9. The curing composition according to claim 7 or 8, wherein, It further contains silanol compounds.

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