JP2021036027A - Cationic curing agent, method for producing the same, and cationically curable composition - Google Patents

Abstract

To provide a cationic curing agent capable of enhancing the curability without sacrificing the latency, a method for producing the same, and a cationically curable composition based on the cationic curing agent.SOLUTION: A cationic curing agent comprises porous particles, and a compound represented by the general formula (1) in the figure held by the porous particles. In the formula, R1 represents an alkyl group having from 1 to 18 carbon atoms, or a phenyl group; R2 represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, a halogenoalkyl group, an alkoxy group or a phenoxy group.SELECTED DRAWING: None

Description

The present invention relates to a cationic curing agent, a method for producing a cationic curing agent, and a cationic curing composition.

Conventionally, as a cation curing method for an epoxy resin, a method using a catalyst in which an aluminum chelate compound and a silanol compound are used in combination has been known. In this method, the aluminum chelate compound reacts with the silanol compound to produce a cation-curable initiator, thereby exhibiting cation-curability.

As an example of a technique for a latent curing agent using the above curing system, there is a method of retaining an aluminum chelate compound in porous particles. For example, an aluminum compound is contained in porous particles prepared by using a polyfunctional isocyanate compound. A method of physically separating the silanol compound from the silanol compound has been proposed (see, for example, Patent Document 1).
Further, as an example similar to the above-mentioned technique, a method of increasing curability by using a bifunctional isocyanate compound in combination with a polyfunctional isocyanate compound has been proposed (see, for example, Patent Document 2).
Further, a method in which a radically polymerizable compound is used in combination when producing porous particles has been proposed (see, for example, Patent Document 3).
Further, a method of using porous inorganic particles as porous particles has been proposed (see, for example, Patent Document 4).
Further, as a means for further increasing the potential from these methods, for example, a method of treating the surface of porous particles with a specific silane treatment agent has been proposed (see, for example, Patent Document 5).

JP-A-2009-203477 Japanese Unexamined Patent Publication No. 2012-188596 Japanese Unexamined Patent Publication No. 2009-22146 Japanese Unexamined Patent Publication No. 2013-100382 Japanese Unexamined Patent Publication No. 2016-056274

All of the proposed techniques are methods for concealing an aluminum chelate compound, and it is premised that the cation curability is controlled in the state of the porous particles used. Therefore, there is a problem that there is no choice but to have a trade-off relationship between the curability and the control of the potential by devising these porous particles from the principle.

An object of the present invention is to solve the above-mentioned problems in the past and to achieve the following object. That is, an object of the present invention is to provide a cationic curing agent capable of improving curability without impairing the potential, a method for producing the same, and a cationic curing composition using the cationic curing agent.

The means for solving the above-mentioned problems are as follows. That is,
<1> Porous particles and
It is a cationic curing agent characterized by having a compound represented by the following general formula (1) held in the porous particles.
However, in the general formula (1), R ¹ is a branched alkyl group or phenyl group having 1 to 18 carbon atoms, and these may be further substituted with a substituent.
R ² is a hydrogen atom, an alkyl group which may have a branched structure having 1 to 4 carbon atoms, halogenoalkyl group, an alkoxy group, or a phenoxy group, the alkyl group, halogenoalkyl group, an alkoxy group and phenoxy group, more It may be substituted with a substituent. R ¹ and R ² may be the same or different from each other.
<2> Porous particles and
It is a cationic curing agent characterized by having a mixture of a compound represented by the following general formula (1) and a compound represented by the following general formula (2) held in the porous particles.
However, in the general formula (1), R ¹ is a branched alkyl group or phenyl group having 1 to 18 carbon atoms, and these may be further substituted with a substituent.
R ² is a hydrogen atom, an alkyl group which may have a branched structure having 1 to 4 carbon atoms, halogenoalkyl group, an alkoxy group, or a phenoxy group, the alkyl group, halogenoalkyl group, an alkoxy group and phenoxy group, more It may be substituted with a substituent. R ¹ and R ² may be the same or different from each other.
However, in the general formula (2), Z represents a hydrogen atom or an electron-withdrawing group. a is an integer from 0 to 5.
<3> The porous particles are the cationic curing agents according to any one of <1> to <2>, which are either organic porous particles or inorganic porous particles.
<4> The cationic curing agent according to <3>, wherein the organic porous particles are composed of a polyurea resin.
<5> The cationic curing agent according to <4>, wherein the organic porous particles further contain a vinyl resin as a constituent component.
<6> The cationic curing agent according to any one of <1> to <5>, wherein the surface of the porous particles has a reaction product of a silane treatment agent.
<7> The compound represented by the following general formula (1) and the porous particles are allowed to coexist in an organic solvent, and then the solvent is removed to convert the compound represented by the general formula (1) into the porous particles. It is a method for producing a cationic curing agent, which is characterized in that it is retained.
However, in the general formula (1), R ¹ is a branched alkyl group or phenyl group having 1 to 18 carbon atoms, and these may be further substituted with a substituent.
R ² is a hydrogen atom, an alkyl group which may have a branched structure having 1 to 4 carbon atoms, halogenoalkyl group, an alkoxy group, or a phenoxy group, the alkyl group, halogenoalkyl group, an alkoxy group and phenoxy group, more It may be substituted with a substituent. R ¹ and R ² may be the same or different from each other.
<8> The compound represented by the following general formula (1), the compound represented by the following general formula (2), and the porous particles are allowed to coexist in an organic solvent, and then the solvent is removed to obtain the above general formula ( A method for producing a cationic curing agent, which comprises holding a mixture of the compound represented by 1) and the compound represented by the general formula (2) in the porous particles.
However, in the general formula (1), R ¹ is a branched alkyl group or phenyl group having 1 to 18 carbon atoms, and these may be further substituted with a substituent.
R ² is a hydrogen atom, an alkyl group which may have a branched structure having 1 to 4 carbon atoms, halogenoalkyl group, an alkoxy group, or a phenoxy group, the alkyl group, halogenoalkyl group, an alkoxy group and phenoxy group, more It may be substituted with a substituent. R ¹ and R ² may be the same or different from each other.
However, in the general formula (2), Z represents a hydrogen atom or an electron-withdrawing group. a is an integer from 0 to 5.
<9> A cation-curable composition comprising a cation-curing component and the cation-curing agent according to any one of <1> to <6>.
<10> The cationically curable composition according to <9>, which further contains an organic silane compound.
<11> The cationic curable composition according to <10>, wherein the organic silane compound is a compound represented by the following general formula (2).
However, in the general formula (2), Z represents a hydrogen atom or an electron-withdrawing group. a is an integer from 0 to 5.

According to the present invention, a cationic curing agent capable of solving the above-mentioned problems in the past, achieving the above-mentioned object, and improving curability without impairing the potential, a method for producing the same, and the cationic curing agent. A cationically curable composition using the above can be provided.

(Cationic hardener)
In the first form, the cationic curing agent of the present invention has porous particles and a compound represented by the following general formula (1) held in the porous particles, and further, if necessary, other substances. It has the components of.
In the second form, the cationic curing agent of the present invention comprises porous particles, a compound represented by the following general formula (1) and a compound represented by the following general formula (2) held in the porous particles. It has a mixture of and, and if necessary, other components.

In the cationic curing agent, the compound represented by the general formula (1) or a mixture of the compound represented by the general formula (1) and the compound represented by the general formula (2) is porous. It is held by the particles.
The porous particles are, for example, a compound represented by the general formula (1), a compound represented by the general formula (1), and a compound represented by the general formula (2) in the pores thereof. Hold the mixture of.
The cationic curing agent is a so-called latent curing agent.
In the cationic curing agent, the compound represented by the general formula (1) held in the porous particles, or the compound represented by the general formula (1) and the compound represented by the general formula (2). The content of the mixture with and is not particularly limited and may be appropriately selected depending on the intended purpose.

However, in the general formula (1), R ¹ is a branched alkyl group or phenyl group having 1 to 18 carbon atoms, and these may be further substituted with a substituent.
R ² is a hydrogen atom, an alkyl group which may have a branched structure having 1 to 4 carbon atoms, halogenoalkyl group, an alkoxy group, or a phenoxy group, the alkyl group, halogenoalkyl group, an alkoxy group and phenoxy group, more It may be substituted with a substituent. R ¹ and R ² may be the same or different from each other.

^{The alkyl group having 1 to 18 carbon atoms in R 1} in the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose, but an alkyl group having 2 to 10 carbon atoms is preferable. , Alkyl groups having 2 to 8 carbon atoms are more preferable.
The alkyl group having 1 to 18 carbon atoms in R ^{1 may be linear or branched.}
The substituent in the phenyl group which may have the substituent in R ¹ is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an alkyl group having 1 to 18 carbon atoms and a carbon number of carbon atoms. Examples thereof include 1 to 18 alkoxy groups and halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

^{The alkyl group having 1 to 4 carbon atoms in R 2} in the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose, but an alkyl group having 1 to 2 carbon atoms is preferable. ..
The halogenoalkyl group in R ² is not particularly limited and may be appropriately selected depending on the intended purpose. Specific examples thereof include a trifluoromethyl group, a trichloromethyl group and a tribromomethyl group.
The alkoxy group in R ² is not particularly limited and may be appropriately selected depending on the intended purpose, but an alkoxy group having 1 to 10 carbon atoms is preferable, an alkoxy group having 1 to 6 carbon atoms is more preferable, and carbon. Alkoxy groups of numbers 1 to 4 are particularly preferred. Further, the carbon of the alkoxy group may be linear or branched.
The ^{phenoxy group which may have a substituent in R 2} is not particularly limited and may be appropriately selected depending on the intended purpose.
Examples of the substituent of the phenoxy group which may have a substituent in R ² include an alkyl group having 1 to 10 carbon atoms, an alkyl halide group, an alkoxy group having 1 to 10 carbon atoms, a halogen atom and the like. ..

Examples of the compound represented by the general formula (1) include tris [2- (methoxycarbonyl) -phenoxy] aluminum, tris [2- (ethoxycarbonyl) -phenoxy] aluminum, and tris [2- (butoxycarbonyl)). -Phenoxy] aluminum, tris [2- (methoxycarbonyl) -4-methylphenoxy] aluminum, tris [2- (methoxycarbonyl) -5-methylphenoxy] aluminum and the like can be mentioned.

The method for synthesizing the compound represented by the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the compound to be reacted with the aluminum alkoxide may be in a solvent or in a solvent-free manner. Examples thereof include a method of reacting at room temperature (25 ° C.) to about 110 ° C. At that time, the alcohol desorbed from the aluminum alkoxide may be distilled off during the reaction.

However, in the general formula (2), Z represents a hydrogen atom or an electron-withdrawing group. a is an integer from 0 to 5.
Examples of the electron-withdrawing group include a halogen group (for example, a chloro group, a bromo group, etc.), a trifluoromethyl group, a nitro group, a sulfo group, a carboxyl group, and an alkoxycarbonyl group (for example, a methoxycarbonyl group and an ethoxycarbonyl group). Etc.), formyl group and the like.
Examples of the compound represented by the general formula (2) include triphenylsilanol, tris [(4-chloro) phenyl] silanol, tris [(4-trifluoromethyl) phenyl] silanol, and tris [(3,5). -Dichloro) phenyl] silanol, tris (pentafluorophenyl) silanol and the like.

In the present invention, the mixing ratio of the compound represented by the general formula (1) and the compound represented by the general formula (2) can be appropriately selected depending on the effect, and the general formula ( The amount of the compound represented by the general formula (2) is preferably 10 parts by mass or more and 200 parts by mass or less, and 20 parts by mass or more and 100 parts by mass or less is more than 100 parts by mass of the compound represented by 1). preferable.
When the compound represented by the general formula (1) and the compound represented by the general formula (2) are mixed in the organic solvent at the above mixing ratio, the compound represented by the general formula (1) is obtained. The compound of the following general formula (3) may be produced by partially reacting the compound represented by the general formula (2).

In the general formula (3), ^{R 1} and ^{R 2} are the same as ^{R 1} and ^{R 2} of the general formula (1), Z and a are the same as Z and a in the general formula (2) is there. Further, n is an integer of 1 to 3.

The mixture of the compound represented by the general formula (1) and the compound represented by the general formula (2) in the present invention also includes the compound represented by the general formula (3).
The compound represented by the general formula (3) is an unstable compound and decomposes when extracted, but the compound represented by the general formula (1) and the compound represented by the general formula (2). When the compound represented by the general formula (3) is stabilized by being carried on the porous particles in the state of a mixture of the above, the compound can be stably present in the porous particles.
The compound represented by the general formula (1) or a mixture of the compound represented by the general formula (1) and the compound represented by the general formula (2) is inside (in the pores) of the porous particles. It can be confirmed by analyzing silicon (Si) and Al in the pores with SEM / EDX of the cross section of the porous particles.

<Porous particles>
The porous particles are not particularly limited as long as they are particles having many pores, and can be appropriately selected depending on the intended purpose. For example, porous organic resin particles composed of an organic resin and inorganic compounds. Examples include porous inorganic particles composed of.

The average pore diameter of the pores of the porous particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 nm or more and 300 nm or less, and more preferably 5 nm or more and 150 nm or less.

<< Porous organic resin particles >>
The porous organic resin particles are not particularly limited as long as they are porous particles composed of an organic resin, and can be appropriately selected depending on the intended purpose.

The organic resin is not particularly limited and may be appropriately selected depending on the intended purpose, but a polyurea resin is preferable. That is, the porous organic resin particles are preferably composed of at least a polyurea resin.
The porous organic resin particles may further contain a vinyl resin as a constituent component.

<<< Polyurea resin >>>
The polyurea resin is a resin having a urea bond in the resin.
The polyurea resin constituting the porous organic resin particles can be obtained, for example, by polymerizing a polyfunctional isocyanate compound in an emulsion. The polyurea resin may have a bond derived from an isocyanate group in the resin and may have a bond other than the urea bond, for example, a urethane bond.

-Polyfunctional isocyanate compound-
The polyfunctional isocyanate compound is a compound having two or more isocyanate groups, preferably three isocyanate groups in one molecule. Further preferable examples of such a trifunctional isocyanate compound include the TMP adduct compound of the following general formula (4) in which 1 mol of trimethylolpropane is reacted with 3 mol of the diisocyanate compound, and the following general in which 3 mol of the diisocyanate compound is self-condensed. Examples thereof include the isocyanurate compound of the formula (5) and the burette compound of the following general formula (6) in which the remaining 1 mol of diisocyanate is condensed with diisocyanate urea obtained from 2 mol of 3 mol of the diisocyanate compound.

In the general formulas (4) to (6), the substituent R is a portion of the diisocyanate compound excluding the isocyanate group. Specific examples of such diisocyanate compounds include toluene 2,4-diisocyanate, toluene 2,6-diisocyanate, m-xylylene diisocyanate, hexamethylene diisocyanate, hexahydro-m-xylylene diisocyanate, isophorone diisocyanate, and methylene diphenyl-4. , 4'-diisocyanate and the like.

<<< Vinyl resin >>
The vinyl resin is a resin obtained by polymerizing a radically polymerizable vinyl compound.
The vinyl resin improves the mechanical properties of the porous organic resin particles. Thereby, the thermal responsiveness at the time of curing in the cationic curable composition, particularly sharp thermal responsiveness in a low temperature region can be realized.

In the vinyl resin, for example, a radically polymerizable vinyl compound is also contained in an emulsion containing a polyfunctional isocyanate compound, and when the polyfunctional isocyanate compound is polymerized in the emulsion, the radical polymerization is carried out at the same time. It can be obtained by radical polymerization of a sex vinyl compound.

-Radical polymerizable vinyl compound-
The radically polymerizable vinyl compound is a compound having a radically polymerizable carbon-carbon unsaturated bond in the molecule.
The radically polymerizable vinyl compound includes so-called monofunctional radically polymerizable compounds and polyfunctional radically polymerizable compounds.
The radically polymerizable vinyl compound preferably contains a polyfunctional radically polymerizable compound. This is because it becomes easier to realize a sharp thermal responsiveness in a low temperature region by using a polyfunctional radical polymerizable compound. From this point of view, the radically polymerizable vinyl compound preferably contains 30% by mass or more of the polyfunctional radically polymerizable compound, and more preferably 50% by mass or more.

Examples of the monofunctional radically polymerizable compound include a monofunctional vinyl compound (for example, styrene, methylstyrene, etc.), a monofunctional (meth) acrylate compound (for example, butyl acrylate, etc.) and the like.
Examples of the polyfunctional radical polymerizable compound include a polyfunctional vinyl compound (for example, divinylbenzene and divinyl adipate), a polyfunctional (meth) acrylate compound (for example, 1,6-hexanediol diacrylate, and trimethylolpropane). Methylolpropane triacrylate, etc.) and the like.
Among these, a polyfunctional vinyl compound, particularly divinylbenzene, can be preferably used from the viewpoint of potential and thermal responsiveness.

The polyfunctional radical polymerizable compound may be composed of a polyfunctional vinyl compound and a polyfunctional (meth) acrylate compound. When used in combination in this way, effects such as changing the thermal responsiveness and being able to introduce a reactive functional group can be obtained.

The amount of the radically polymerizable vinyl compound to be blended is not particularly limited and may be appropriately selected depending on the intended purpose. However, 1 part by mass or more and 80 parts by mass or less is used with respect to 100 parts by mass of the polyfunctional isocyanate compound. It is preferably 10 parts by mass or more and 60 parts by mass or less, more preferably.

The average particle size of the porous organic resin particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less, and 1 μm or more and 5 μm. The following are particularly preferred.

<< Porous Inorganic Particles >>
The porous inorganic particles are not particularly limited as long as they are porous particles composed of an inorganic compound, and can be appropriately selected depending on the intended purpose.
Examples of the material of the porous inorganic particles include silicon oxide, aluminum silicate, aluminum oxide, zirconium oxide, potassium oxide, calcium oxide, titanium oxide, calcium borate, sodium borosilicate, sodium oxide, and phosphate. Can be mentioned. These may be used alone or in combination of two or more.

Examples of the porous inorganic particles include porous silica particles, porous alumina particles, porous titania particles, porous zirconia particles, and zeolite. These may be used alone or in combination of two or more.

The average particle size of the porous inorganic particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 nm or more and 5,000 μm or less, more preferably 250 nm or more and 1,000 μm or less, and more preferably 500 nm or more. 200 μm or less is particularly preferable.

<< Surface of porous particles >>
The porous particles preferably have a reaction product of a silane coupling agent on the surface in terms of increasing the potential.
The reaction product is obtained by reacting a silane coupling agent.
The reaction product is present on the surface of the porous particles.

The porous particles holding the compound represented by the general formula (1) or a mixture of the compound represented by the general formula (1) and the compound represented by the general formula (2) have a structure thereof. Above, the compound represented by the general formula (1) or a mixture of the compound represented by the general formula (1) and the compound represented by the general formula (2) is present not only on the inside but also on the surface thereof. It seems that it will exist.
Therefore, when an alicyclic epoxy resin having high reactivity is used as the cation-curing component in the cation-curable composition described later, the cation-curable composition using the cation-curing agent greatly thickens with time. To do.
Therefore, the compound represented by the general formula (1) or a mixture of the compound represented by the general formula (1) and the compound represented by the general formula (2) existing on the surface of the porous particles. Is preferably inactivated with a silane coupling agent, as described below.

The silane coupling agent is classified into two types as described below.

The first type is an active compound represented by the general formula (1) retained in the porous particles, or a compound represented by the general formula (1) and a compound represented by the general formula (2). This is a type of silane coupling agent that reduces the activity by coating the surface with a polymer chain having a siloxane structure generated by reacting a mixture with a compound with an alkoxysilyl group in the molecule. Examples of this type of silane coupling agent include alkylalkoxysilane coupling agents having an alkyl group. Specific examples thereof include methyltrimethoxysilane, n-propyltrimethoxysilane, and hexyltrimethoxysilane.

The second type is an active compound represented by the general formula (1) retained in the porous particles, or a compound represented by the general formula (1) and a compound represented by the general formula (2). This is a type of silane coupling agent that reduces the activity by coating the surface with an epoxy polymerized chain produced by reacting a mixture with a compound with an epoxy group in the molecule. Examples of this type of silane coupling agent include epoxy silane coupling agents. Specifically, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyltrimethoxysilane (KBM-403, Shin-Etsu Chemical Co., Ltd.) (Made by company) and so on.

(Manufacturing method of cationic curing agent)
In the first embodiment, the method for producing a cationic curing agent of the present invention comprises coexisting a compound represented by the following general formula (1) and porous particles in an organic solvent, and then removing the solvent to obtain the general formula. The compound represented by (1) is retained in the porous particles.
However, in the general formula (1), R ¹ is a branched alkyl group or phenyl group having 1 to 18 carbon atoms, and these may be further substituted with a substituent.
R ² is a hydrogen atom, an alkyl group which may have a branched structure having 1 to 4 carbon atoms, halogenoalkyl group, an alkoxy group, or a phenoxy group, the alkyl group, halogenoalkyl group, an alkoxy group and phenoxy group, more It may be substituted with a substituent. R ¹ and R ² may be the same or different from each other.

In the second embodiment of the method for producing a cationic curing agent of the present invention, a compound represented by the following general formula (1), a compound represented by the following general formula (2), and porous particles are mixed in an organic solvent. The porous particles are allowed to retain a mixture of the compound represented by the general formula (1) and the compound represented by the general formula (2) by coexistence and then desolving.
However, in the general formula (1), R ¹ is a branched alkyl group or phenyl group having 1 to 18 carbon atoms, and these may be further substituted with a substituent.
R ² is a hydrogen atom, an alkyl group which may have a branched structure having 1 to 4 carbon atoms, halogenoalkyl group, an alkoxy group, or a phenoxy group, the alkyl group, halogenoalkyl group, an alkoxy group and phenoxy group, more It may be substituted with a substituent.
R ¹ and R ² may be the same or different from each other.
However, in the general formula (2), Z represents a hydrogen atom or an electron-withdrawing group. a is an integer from 0 to 5.

As a method for causing the porous particles to retain the compound represented by the general formula (1) or a mixture of the compound represented by the general formula (1) and the compound represented by the general formula (2). In an organic solvent, the compound represented by the general formula (1), or the compound represented by the general formula (1), the compound represented by the general formula (2), and the porous particles are allowed to coexist. A method in which the solvent is subsequently removed is preferable.
Further, as a method for coexisting the compound represented by the general formula (1), the compound represented by the general formula (2) and the porous particles in the organic solvent, the compound represented by the general formula (1) is represented. It is preferable that the compound to be used and the compound represented by the general formula (2) are mixed and dissolved in an organic solvent in advance, and then the porous particles are added. Further, if necessary, the porous particles may be charged and then dispersed by a homogenizer or ultrasonic waves.
Examples of the desolvation method include a method by heating, a method by depressurization, and a combination of both.
The organic solvent to be used is appropriately selected depending on the intended purpose, but preferably has a boiling point of 150 ° C. or lower, and examples thereof include methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, toluene, xylene, acetonitrile and tetrahydrofuran. Be done.
Further, for the purpose of maintaining the fluidity after distilling off the organic solvent when distilling off the organic solvent, an olefin-based, ester-based or silicone-based oil or wax that does not volatilize under the distilling conditions of the organic solvent is added. This is also a preferred embodiment.

As a method for forming the reaction product of the silane coupling agent on the surface of the porous particles, for example, the description in JP-A-2016-056274 can be referred to.

(Conic curable composition)
The cation-curable composition of the present invention contains at least a cation-curing component and a cation-curing agent, preferably an organic silane compound, and further contains other components, if necessary.

<Cationic curing component>
The cation-curing component is not particularly limited as long as it is a cation-curing organic material, and can be appropriately selected depending on the intended purpose. Examples thereof include an epoxy resin, an oxetane compound, and a vinyl ether resin.

<< Epoxy resin >>
The epoxy resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include glycidyl ether type epoxy resin and alicyclic epoxy resin.

The glycidyl ether type epoxy resin may be, for example, liquid or solid, and preferably has an epoxy equivalent of about 100 to 4,000 and has two or more epoxy groups in the molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, ester type epoxy resin and the like can be mentioned. Among these, bisphenol A type epoxy resin can be preferably used from the viewpoint of resin characteristics. In addition, these epoxy resins also include monomers and oligomers.

The alicyclic epoxy resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, vinylcyclopentadiendioxide, vinylcyclohexenemono to dioxide, dicyclopentadieneoxide, epoxy- [epoxy-oxaspiro. C _8-15 alkyl] _{-cyclo C 5-12} alkane (eg, 3,4-epoxy-1- [8,9-epoxy-2,4-dioxaspiro [5.5] undecane-3-yl] -cyclohexane, etc. ), 3,4-Epoxy Cyclohexylmethyl-3', 4'-Epoxy Cyclohexane Carbolate, Epoxy C _5-12 Cycloalkyl C _1-3 Epoxy Epoxy C _5-12 Cycloalcan Carboxylate (eg, 4,5-Epoxy Cyclooctylmethyl-4', 5'-epoxycyclooctanecarboxylate, etc.), bis (C _1-3 alkyl epoxy C _5-12 cycloalkyl C _1-3 alkyl) dicarboxylate (eg, bis (2-methyl-) 3,4-Epoxycyclohexylmethyl) adipate, etc.) and the like.

As the alicyclic epoxy resin, 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate [manufactured by Daicel Co., Ltd., trade name: seroxide # 2021P] is easily available as a commercial product. Epoxy equivalent: 128-140] is preferably used.

In the above example, the descriptions "C _8-15 ", "C _5-12 ", and "C _1-3 " have 8 to 15 carbon atoms, 5 to 12 carbon atoms, and 5 to 12 carbon atoms, respectively. Means that is 1 to 3, indicating that there is a range of structural structures of the compound.

The structural formula of an example of the alicyclic epoxy resin is shown below.

<< Oxetane compound >>
In the cationic curable composition, the exothermic peak can be sharpened by using the oxetane compound in combination with the epoxy resin.

Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, and 4,4'-bis [(3-3-oxythanyl) methoxy] methyl} benzene. Ethyl-3-oxetanyl) methoxymethyl] biphenyl, 1,4-benzenedicarboxylic acid bis [(3-ethyl-3-oxetanyl)] methyl ester, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3 -(2-Ethylhexyloxymethyl) oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, oxetanylsilsesquioki Examples include sun and phenol novolac oxetane.

The content of the cation-curing component in the cation-curable composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 30% by mass or more and 99% by mass or less, and 50% by mass or more and 98% by mass or more. It is more preferably 70% by mass or less, and particularly preferably 70% by mass or more and 97% by mass or less.
The content is the content of the cation-curable composition in the non-volatile content. The same applies to the following.

<Cationic curing agent>
The cation curing agent is the cation curing agent of the present invention.

The content of the cation-curing agent in the cation-curable composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is 1 part by mass or more and 70 parts by mass with respect to 100 parts by mass of the cation-curing component. It is preferably 1 part by mass or less, and more preferably 1 part by mass or more and 50 parts by mass or less. If the content is less than 1 part by mass, the curability may be lowered, and if it exceeds 70 parts by mass, the resin properties (for example, flexibility) of the cured product may be lowered.

<Organic silane compound>
As described in paragraphs [0007] to [0010] of JP-A-2002-212537, the organic silane compound cooperates with the aluminum chelate held in the latent curing agent to form an epoxy resin cation. It has a function of initiating polymerization.
Also in the cation-curable composition, the effect of accelerating the curing of the cation-curing component can be obtained by using the cation-curing agent and the organic silane compound in combination.

Examples of the organic silane compound include aryl silanol compounds and silane coupling agents.

Examples of such an organic silane compound include a silanol compound having high steric hindrance, a silane coupling agent having 1 to 3 lower alkoxy groups in the molecule, and the like. A group having a reactivity with the functional group of the cationic curing component in the molecule of the silane coupling agent, for example, a vinyl group, a styryl group, an acryloyloxy group, a methacryloyloxy group, an epoxy group, an amino group, or a mercapto group. However, a coupling agent having an amino group or a mercapto group can be used when the amino group or the mercapto group does not substantially capture the generated cation species during cation curing. ..

<< Aryl silanol compound >>
The arylsilanol compound is represented by, for example, the following general formula (7).
However, in the general formula (7), m is 2 or 3, preferably 3, but the sum of m and n is 4. Ar is an aryl group that may have a substituent.
The arylsilanol compound represented by the general formula (7) is a monool form or a diol form.

Ar in the general formula (7) is an aryl group which may have a substituent.
Examples of the aryl group include a phenyl group, a naphthyl group (for example, 1-naphthyl group, 2-naphthyl group, etc.), an anthrasenyl group (for example, 1-anthrasenyl group, 2-anthrasenyl group, 9-anthrasenyl group, benz [ a] -9-anthrasenyl group, etc.), phenaryl group (eg, 3-phenylyl group, 9-phenylyl group, etc.), pyrenyl group (eg, 1-pyrenyl group, etc.), azulenyl group, floorenyl group, biphenyl group (eg, eg. 2-biphenyl group, 3-biphenyl group, 4-biphenyl group, etc.), thienyl group, furyl group, pyrrolyl group, imidazolyl group, pyridyl group and the like can be mentioned. Among these, a phenyl group is preferable from the viewpoint of availability and acquisition cost. The m Ars may be the same or different, but are preferably the same from the viewpoint of availability.

These aryl groups can have, for example, 1 to 5 substituents.
Examples of the substituent include an electron-withdrawing group and an electron-donating group.
Examples of the electron-withdrawing group include a halogen group (for example, a chloro group, a bromo group, etc.), a trifluoromethyl group, a nitro group, a sulfo group, a carboxyl group, and an alkoxycarbonyl group (for example, a methoxycarbonyl group and an ethoxycarbonyl group). Etc.), formyl group and the like.
Examples of the electron donating group include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), an alkoxy group (for example, a methoxy group, an ethoxy group, etc.), a hydroxy group, an amino group, and a monoalkylamino group (for example, a monoalkylamino group). For example, a monomethylamino group, etc.), a dialkylamino group (for example, a dimethylamino group, etc.) and the like can be mentioned.

Specific examples of the phenyl group having a substituent include, for example, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2, 4-Dimethylphenyl group, 2,3-dimethylphenyl group, 2,5-dimethylphenyl group, 3,4-dimethylphenyl group, 2,4,6-trimethylphenyl group, 2-ethylphenyl group, 4-ethylphenyl The group and the like can be mentioned.

By using an electron-withdrawing group as the substituent, the acidity of the hydroxyl group of the silanol group can be increased. By using an electron donating group as a substituent, the acidity of the hydroxyl group of the silanol group can be lowered. Therefore, the curability can be controlled by the substituent.
Here, the substituent may be different for each of m Ars, but it is preferable that the substituents are the same for each of m Ars from the viewpoint of availability. Further, only some Ars may have a substituent, and other Ars may not have a substituent.

As the arylsilanol compound, the compound represented by the general formula (2) is preferable in that it further promotes cationic polymerization.
In the present invention, the compound represented by the general formula (2) used to be retained inside the cationic curing agent and the compound represented by the general formula (2) used in the cationic curing composition are the same. It may or may not be different.

<< Silane Coupling Agent >>
The silane coupling agent has 1 to 3 lower alkoxy groups in the molecule and is reactive with the functional group of the thermosetting resin in the molecule, for example, a vinyl group or a styryl group. , Acryloyloxy group, methacryloyloxy group, epoxy group, amino group, mercapto group and the like. The coupling agent having an amino group or a mercapto group is used when the latent curing agent used in the present invention is a cationic curing agent and therefore the amino group or the mercapto group does not substantially capture the generated cation species. be able to.

Examples of the silane coupling agent include vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-styryltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-acryloxypropyl. Trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β- (aminoethyl) -γ -Aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxy Examples thereof include silane and γ-chloropropyltrimethoxysilane.

The content of the organic silane compound in the cation-curable composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is 50 parts by mass or more and 500 parts by mass with respect to 100 parts by mass of the cation-curing agent. It is preferably 100 parts by mass or less, and more preferably 100 parts by mass or more and 300 parts by mass or less.

Hereinafter, examples of the present invention will be described, but the present invention is not limited to these examples.

(Synthesis Example 1)
<Synthesis of compound 1>
Aluminum-sec-butoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.0 g (20.3 mmol) and heptane _{with N 2} introduced in a 200 mL three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube. 70 g was added. 10.79 g (65.0 mmol) of ethyl salicylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto with stirring at room temperature, and then the temperature was raised to 100 ° C. and the reaction was carried out for 2 hours. Immediately after the reaction, crystal precipitation occurred.
After completion of the reaction, filtration under reduced pressure was performed, crystals were collected, washed with heptane, and then dried under reduced pressure at room temperature for 24 hours to obtain compound 1 having pale red crystals represented by the following structural formula. 75 g was obtained.

(Synthesis Example 2)
<Synthesis of compound 2>
In Synthesis Example 1, light red crystalline compound 2 represented by the following structural formula is the same as in Synthesis Example 1 except that ethyl salicylate is 11.71 g of n-propyl salicylate (manufactured by Tokyo Chemical Industry Co., Ltd.). Was obtained in an amount of 8.82 g.

(Synthesis Example 3)
<Synthesis of compound 3>
In Synthesis Example 1, the compound 3 having a light red crystal represented by the following structural formula is the same as in Synthesis Example 1 except that the amount of ethyl salicylate is 12.62 g of n-butyl salicylate (manufactured by Tokyo Chemical Industry Co., Ltd.). Was obtained in an amount of 10.10 g.

(Synthesis Example 4)
<Synthesis of compound 4>
In Synthesis Example 1, a compound having a light red crystal represented by the following structural formula is the same as in Synthesis Example 1, except that ethyl salicylate is 10.79 g of methyl 5-methylsalicylate (manufactured by Tokyo Chemical Industry Co., Ltd.). 8.53 g of 4 was obtained.

(Production Example 1 of Porous Particles)
<Preparation of porous particles A>
800 parts by mass of distilled water, 0.05 parts by mass of a surfactant (Nurex RT, manufactured by Nichiyu Co., Ltd.), and 4 parts by mass of polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) as a dispersant. , Placed in a 3 liter surface polymerization vessel equipped with a thermometer and mixed uniformly. In addition to this mixed solution, 11 parts by mass of a 24 mass% isopropanol solution (aluminum chelate D, manufactured by Kawaken Fine Chemical Co., Ltd.) of aluminum monoacetylacetonate bis (ethylacetacetate) and methylenediphenyl-4,4'-diisocyanate An oil phase solution prepared by dissolving 11 parts by mass of (3 mol) trimethylolpropane (1 mol) adduct (D-109, manufactured by Mitsui Takeda Chemical Co., Ltd.) in 30 parts by mass of ethyl acetate was added to a homogenizer (11). After emulsification and mixing at (000 rpm / 10 minutes), interfacial polymerization was carried out at 60 ° C. overnight.
After completion of the reaction, the polymerization reaction solution was allowed to cool to room temperature, the interfacial polymer particles were filtered off by filtration, and dried under reduced pressure at room temperature for 24 hours to obtain spherical particles having an average particle size of 10.0 μm.
Further, the particles were washed with methyl ethyl ketone and filtered under reduced pressure to obtain a wet cake of porous particles A.

(Production Example 2 of Porous Particles)
<Preparation of porous particles B>
800 parts by mass of distilled water, 0.05 parts by mass of a surfactant (Nurex RT, manufactured by Nichiyu Co., Ltd.), and 4 parts by mass of polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) as a dispersant. , Placed in a 3 liter surface polymerization vessel equipped with a thermometer and mixed uniformly to prepare an aqueous phase.
In addition to this aqueous phase, 100 parts by mass of a 24 mass% isopropanol solution (aluminum chelate D, manufactured by Kawaken Fine Chemical Co., Ltd.) of aluminum monoacetylacetonate bis (ethylacetoacetate) and methylenediphenyl-4 as a polyfunctional isocyanate compound. , 4'-Diisocyanate (3 mol) trimethylolpropane (1 mol) adduct (D-109, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) 70 parts by mass and divinylbenzene (manufactured by Merck Co., Ltd.) 30 as a radically polymerizable compound. An oil phase prepared by dissolving a part by mass of a radical polymerization initiator (Parloyl L, manufactured by Nichiyu Co., Ltd.) in an amount equivalent to 1% by mass (0.3 parts by mass) of a radically polymerizable compound in 100 parts by mass of ethyl acetate. The mixture was charged, emulsified and mixed with a homogenizer (10,000 rpm / 5 minutes, T-50, manufactured by IKA Japan Co., Ltd.), and then surface polymerization and radical polymerization were carried out at 80 ° C. for 6 hours. After completion of the reaction, the polymerization reaction solution was allowed to cool to room temperature, the polymerized particles were filtered off by filtration, and dried under reduced pressure at room temperature for 24 hours to obtain spherical particles having an average particle size of 2.9 μm.
Further, the particles were washed with methyl ethyl ketone and filtered under reduced pressure to obtain a wet cake of porous particles B.

(Production Example 3 of Porous Particles)
<Preparation of porous particles C>
800 parts by mass of distilled water and 0.0 of surfactant (Nurex RT, manufactured by NOF CORPORATION)
5 parts by mass and 4 parts by mass of polyvinyl alcohol (PVA-205, manufactured by Kuraray Co., Ltd.) as a dispersant were placed in a 3 liter interfacial polymerization container equipped with a thermometer and mixed uniformly to prepare an aqueous phase.
In addition to this aqueous phase, 100 parts by mass of a 24 mass% isopropanol solution (aluminum chelate D, manufactured by Kawaken Fine Chemical Co., Ltd.) of aluminum monoacetylacetonate bis (ethylacetoacetate) and methylenediphenyl-4 as a polyfunctional isocyanate compound. , 4'-Diisocyanate (3 mol) trimethylolpropane (1 mol) adduct (D-109, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) 70 parts by mass and 1,6-hexanediol diacrylate 30 as a radically polymerizable compound An oil phase in which 1 part by mass of a radical polymerization initiator (Perloyl L, manufactured by Nichiyu Co., Ltd.) and 1% by mass (0.3 parts by mass) of the radically polymerizable compound are dissolved in 100 parts by mass of ethyl acetate. Was emulsified and mixed with a homogenizer (10,000 rpm / 5 minutes: T-50, manufactured by IKA Japan Co., Ltd.), and then interfacial polymerization and radical polymerization were carried out at 80 ° C. for 6 hours. After completion of the reaction, the polymerization reaction solution was allowed to cool to room temperature, the polymerized particles were filtered off by filtration, and dried under reduced pressure at room temperature for 24 hours to obtain spherical particles having an average particle size of 2.7 μm.
Further, the particles were washed with methyl ethyl ketone and filtered under reduced pressure to obtain a wet cake of porous particles C.

(Production Example 4 of Porous Particles)
<Preparation of porous particles D>
800 parts by mass of water, 0.05 parts by mass of surfactant (product name: Neurox R, manufactured by Nichiyu Co., Ltd.), and 4 parts by mass of polyvinyl alcohol (degree of polymerization of about 500) (manufactured by Wako Pure Chemical Industries, Ltd.) An aqueous phase was prepared by mixing uniformly. On the other hand, 11 parts by mass of aluminum bisethylacetacetate / monoacetylacetone (product name: Aluminum Chelate D, manufactured by Kawaken Fine Chemical Co., Ltd.), an adduct of metaxylylene diisocyanate and trimethylolpropane (product name: Takenate D-). 110N, manufactured by Mitsui Chemicals Co., Ltd.) 8.8 parts by mass, 1,3-bis (isocyanatomethyl) cyclohexane (product name: Takenate 600, manufactured by Mitsui Chemicals Co., Ltd.) 2.2 parts by mass, and 30 parts by mass of ethyl acetate. Was uniformly mixed to prepare an oil phase. While stirring the aqueous phase with a homogenizer (11,000 rpm), the oil phase was added dropwise to the aqueous phase over 5 minutes, further stirred with a homogenizer for 10 minutes (11,000 rpm), and then stirred at 60 ° C. for 12 hours to interface. Polymerization was performed. Then, the particles were cooled to room temperature, the particles were separated by a centrifuge, and then filtered. The obtained particles were dried under reduced pressure for 24 hours to obtain spherical particles having an average particle diameter of 10.4 μm.
Further, the particles were washed with methyl ethyl ketone and filtered under reduced pressure to obtain a wet cake of porous particles D.

(Usage example 1)
Porous silica (manufactured by AGC Si-Tech Co., Ltd., trade name Sunsphere H-32) was prepared as porous particles E.

(Usage example 2)
Triphenylsilanol (manufactured by Kanto Chemical Industry Co., Ltd.) was prepared as the compound represented by the above general formula (2).

(Usage example 3)
Tris [(4-trifluoromethyl) phenyl] silanol (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared as the compound represented by the above general formula (2).

(Example 1-1)
<Preparation of porous particles A-2 in which compound 2 is retained>
An amount corresponding to 7g as a solid content of the wet cake of the porous porous particles A obtained in Production Example 1 of the particles were transferred to three-necked flask 100mL equipped with N ₂ inlet tube, compound 2 7.0 g and toluene 30g was added, after stirring for 15 min at 50 ° C. in an oil bath bath while introducing N ₂ gas, the temperature was raised in an oil bath bath 110 ° C., toluene is distilled off and methyl ethyl ketone with stirring As a result, the liquid was concentrated to retain the compound 2 inside the porous particles A. After completion of the concentration, the mixture was cooled and left at room temperature for 24 hours, 60 g of cyclohexane was added, and the mixture was stirred for 1 hour. Then, after vacuum filtration, washing with 30 g of cyclohexane and vacuum filtration were repeated 4 times. Then, the filtration residue was dried under reduced pressure at 60 ° C. for 4 hours to prepare porous particles A-2 in which compound 2 was retained.

(Example 1-2)
<Preparation of porous particles A-3 in which compound 3 is retained>
Porous particles A-3 in which compound 3 was retained were prepared in the same manner as in Example 1-1 except that compound 2 was replaced with compound 3 in Example 1-1.

(Examples 2-1 to 2-4)
<Preparation of porous particles B-1 to B-4 in which compounds 1 to 4 are retained>
In Example 1-1, the compounds 1 to 4 are inside in the same manner as in Example 1-1, except that the porous particles A are replaced with the porous particles B and the compound 2 is replaced with the compounds 1 to 4. Retained porous particles B-1 to B-4 were prepared.

(Examples 3-1 to 3-4)
<Preparation of Porous Particles C-1 to C-4 in which Compounds 1 to 4 are Retained>
In Example 1-1, the compounds 1 to 4 are inside in the same manner as in Example 1-1, except that the porous particles A are replaced with the porous particles C and the compound 2 is replaced with the compounds 1 to 4. Retained porous particles C-1 to C-4 were prepared.

(Examples 4-1 to 4-4)
<Preparation of porous particles D-1 to D-4 in which compounds 1 to 4 are retained>
In Example 1-1, the compounds 1 to 4 are inside in the same manner as in Example 1-1, except that the porous particles A are replaced with the porous particles D and the compound 2 is replaced with the compounds 1 to 4. Retained porous particles D-1 to D-4 were prepared.

(Example 5-1)
<Preparation of porous particles E-3 in which compound 3 is retained>
First, 7.0 g of porous particles E were placed in a 100 mL three-necked flask and dried under reduced pressure at 100 ° C. for 3 hours. After cooling, the flask was transferred to an oil bath bath, established a _{N 2} inlet tube and a thermometer, _{N 2} gas while the compound 3 7.0 g of toluene 30g addition introduced, after stirring for 15 min at 50 ° C., The temperature of the oil bath was set to 110 ° C., and the solution was concentrated by distilling off toluene while stirring to allow the porous particles E to retain the compound 3. After completion of the concentration, the mixture was cooled and left at room temperature for 24 hours, 60 g of cyclohexane was added, and the mixture was stirred for 1 hour. Then, after vacuum filtration, the mixture was washed with 30 g of cyclohexane, filtered again under reduced pressure, and the filtered residue was dried under reduced pressure at 60 ° C. for 4 hours to prepare porous particles E-3 in which compound 3 was retained.

(Comparative Synthesis Example 1)
<Preparation of Comparative Compound 1>
100 g of aluminum chelate D (24 mass% isopropanol solution (solid content 76 mass%) of aluminum monoacetylacetonate bis (ethylacetacetate)) manufactured by Kawaken Fine Chemicals Co., Ltd. was dried under reduced pressure at 50 ° C. for 24 hours, and then converted to hexane. After washing, dry under reduced pressure at room temperature. 71.4 g of a reddish brown viscous solid of aluminum monoacetylacetonate bis (ethylacetoacetate) was obtained. This compound was designated as Comparative Compound 1.

(Comparative Example 1-1)
<Preparation of Porous Particles A-5 Containing Comparative Compound 1>
An amount corresponding to 7g as a solid content of the wet cake of the porous porous particles A obtained in Production Example 1 of the particles were transferred to three-necked flask 100mL equipped with N ₂ inlet, Comparative Compound 1 7. added 0g and ethyl acetate 30g, after stirring for 15 min at 50 ° C. in an oil bath bath while introducing N ₂ gas, the temperature was raised in an oil bath bath 80 ° C., evaporated ethyl acetate with stirring By doing so, the liquid was concentrated, and the comparative compound 1 was retained inside the porous particles A. After completion of the concentration, the mixture was cooled and left at room temperature for 24 hours, 60 g of cyclohexane was added, and the mixture was stirred for 1 hour. Then, after vacuum filtration, washing with 30 g of cyclohexane and vacuum filtration were repeated 4 times, and then the filtration residue was dried under reduced pressure at 30 ° C. for 24 hours to obtain porous particles A-5 in which Comparative Compound 1 was retained. Made.

(Comparative Examples 1-2 to 1-5)
<Preparation of comparative porous particles B-5 to E-5>
In Comparative Example 1-1, the comparative porous material 1 was retained inside in the same manner as in Comparative Example 1-1, except that the porous particles A were replaced with the porous particles B to D, respectively. Particles B-5 to D-5 were prepared. Further, the comparative porous particles E-5 were prepared in the same manner as in Example 5-1 using Comparative Compound 1.

Table 1 shows the porous particles used and the compounds used in the above examples. In addition, Table 2 shows the porous particles used and the compounds used in Comparative Examples 1-1 to 1-5.

(Examples 6-1 to 6-15 and Comparative Examples 2-1 to 2-5)
<Preparation of cationic curable composition>
100 parts by mass of YL980 (manufactured by Mitsubishi Chemical Co., Ltd., bisphenol A type epoxy resin), 5 parts by mass of triphenylsilanol (manufactured by Kanto Chemical Co., Inc.), and 2 parts by mass of each porous particle prepared in the above Examples and Comparative Examples. Then, a cationically curable composition was prepared.
The porous particles used in each example are shown in Table 3 below, and the porous particles used in each comparative example are shown in Table 4.

(Comparative Examples 2-6 to 2-10)
<Preparation of cationic curable composition>
In Examples 6-1 to 6-15 and Comparative Examples 2-1 to 2-5, a cationically curable composition was prepared by blending 2 parts by mass each of Compounds 1 to 4 and Comparative Compound 1 instead of the porous particles. ..
The compounds used in each comparative example are listed in Table 5.

<Evaluation of cationic curability>
Each 5 mg of the cationic curable composition prepared in Examples 6-1 to 6-15 and Comparative Examples 2-1 to 2-10 was placed in an aluminum container having a diameter of 5 mm for DSC6200, and differential scanning calorimetry was performed. The exothermic peak temperature was evaluated.
As is well known in the art, cation curing is an exothermic reaction, and the exothermic peak temperature by differential scanning calorimetry reflects the curability in cation curing and should be lower.
The conditions for measuring the differential scanning calorimetry are as follows.
[Measurement condition]
-Rising rate: 10 ° C / min (25 ° C to 300 ° C)
・ N ₂ gas: 100 mL / min

<Evaluation of storage stability of cationic curable composition>
The cationic curable compositions prepared in Examples 6-1 to 6-15 and Comparative Examples 2-1 to 2-10 are stored in a closed container at 25 ° C. for 1 day (24 hours) and stored. The reaction rate during storage was estimated by comparing the calorific value in the differential scanning calorimetry before and after. The results are shown in Tables 6 and 7, together with the curability.
The reaction rate was calculated by the following formula.
Reaction rate (%) =
100 x [(calorific value before storage)-(calorific value after storage)] / (calorific value before storage)

From the results of Tables 6 and 7, first, in contrast to Comparative Examples 2-6 to 2-10 in which the compound was added as it was, in the examples, the exothermic peak temperature was increased, but the storage stability was significantly improved. It can be said that the latent state is achieved by encapsulating the porous particles.
Further, comparison with the same porous particles (Examples 6-1 and 6-2 with respect to Comparative Example 2-1, Examples 6-3 to 6-6 with respect to Comparative Example 2-2, and Examples with respect to Comparative Example 2-3. In 6-7 to 6-10, Examples 6-11 to 6-14 with respect to Comparative Example 2-4, and Example 2-5) with respect to Comparative Example 2-5, all of them are porous in which the compound of the present invention is retained. The peak temperature of the particles has been lowered. That is, it was found that the porous particles (cationic curing agent) holding the compound of the present invention had improved curability.

(Example 7-1)
<Preparation of porous particles A-2-1>
1.0 g of n-propyltrimethoxysilane (KBM-3033, manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 9 g of cyclohexane to prepare a surface-inactivating treatment solution, which was prepared in Example 1-1. 1.0 g of porous particles A-2 was added, and the mixture was stirred at 30 ° C. for 20 hours. Then, the mixture was filtered under reduced pressure while being washed with 10 g of cyclohexane, the porous particles were filtered off, and dried under reduced pressure at 40 ° C. for 6 hours to prepare surface-treated porous particles A-2-1.

(Examples 7-2 to 7-15)
<Preparation of other porous particles>
The porous particles shown in Table 8 were surface-treated in the same manner as in Example 7-1, except that the porous particles used in Example 7-1 were replaced as shown in Table 8. ..

(Comparative Examples 3-1 to 3-5)
<Preparation of porous particles for comparison>
The comparative porous particles shown in Table 9 were surface-treated in the same manner as in Example 7-1, except that the porous particles used in Example 7-1 were replaced as shown in Table 9. Made.

(Examples 8-1 to 8-15 and Comparative Examples 4-1 to 4-5)
<Preparation of cationic curable composition>
YL980 (manufactured by Mitsubishi Chemical Co., Ltd., bisphenol A type epoxy resin) 60 parts by mass, celloxide 2021P (manufactured by Daicel Chemical Co., Ltd.) 15 parts by mass, Aron Oxetan OXT-221 (manufactured by Toa Synthetic Co., Ltd.) 25 parts by mass, triphenyl 5 parts by mass of silanol (manufactured by Kanto Chemical Co., Inc.), 2 parts by mass of the porous particles prepared in each of Examples 7-1 to 7-15 and Comparative Examples 3-1 to 3-5 were blended, and Example 8- The cationic curable compositions of Examples 1 to 8-15 and Comparative Examples 4-1 to 4-5 were prepared.
The porous particles used in each example are shown in Table 10 below, and the porous particles used in each comparative example are shown in Table 11.

<Evaluation of cationic curability>
5 mg each of the cationic curable compositions prepared in Examples 8-1 to 8-15 and Comparative Examples 4-1 to 4-5 was placed in an aluminum container having a diameter of 5 mm for DSC6200, and differential scanning calorimetry was performed. , The exothermic peak temperature was evaluated in the same manner as described above.

<Evaluation of storage stability of cationic curable composition>
The cationic curable compositions prepared in Examples 8-1 to 8-15 and Comparative Examples 4-1 to 4-5 are stored in a closed container at 25 ° C. for 1 day (24 hours) and stored. The reaction rate during storage was estimated by comparing the calorific value in the differential scanning calorimetry before and after. The results are shown in Tables 12 and 13 together with the curability.
The reaction rate was calculated by the following formula.
Reaction rate (%) =
100 x [(calorific value before storage)-(calorific value after storage)] / (calorific value before storage)

From the results of Tables 12 and 13, comparisons using the same porous particles (Examples 8-1 and 8-2 with respect to Comparative Example 4-1 and Examples 8-3 to 8-6 with respect to Comparative Example 4-2) were compared. In Examples 8-7 to 8-10 for Example 4-3, Examples 8-11 to 8-14 for Comparative Example 4-4, and Examples 8-5) for Comparative Example 4-5, all of the present invention. The peak temperature has been lowered with the cationic curing agent. That is, it was found that the cationic curing agent of the present invention has improved curability.
Further, the reaction rate when stored at 25 ° C. for 1 day is almost the same as that of the present invention in the comparative example, and it can be said that the cationic curing agent of the present invention has improved curability without impairing the storage stability. That is, it was found that the cationic curing agent of the present invention has improved curability without impairing the potential.

(Example 11-1)
<Preparation of porous particles AA-2 in which a mixture of compound 2 and triphenylsilanol is retained inside>
N ₂ three-necked flask compound 2 5.2 g triphenyl silanol 5.1g of methyl ethyl ketone 30g of 100mL provided with the inlet tube was added, after stirring for 15 min at 50 ° C. in an oil bath bath, of porous particles was charged in an amount equivalent to 7g as a solid content of the wet cake of the obtained porous particles a in preparation example 1, the temperature of the oil bath bath temperature was raised to 80 ° C. while introducing N ₂ gas, while stirring The solution was concentrated by distilling off the methyl ethyl ketone to hold a mixture of compound 2 and triphenylsilanol inside the porous particles A. After completion of the concentration, the mixture was cooled and left at room temperature for 24 hours, 60 g of cyclohexane was added, and the mixture was stirred for 1 hour. Then, after vacuum filtration, washing with 30 g of cyclohexane and vacuum filtration were repeated 4 times, and then the filtration residue was dried under reduced pressure at 60 ° C. for 4 hours to hold a mixture of compound 2 and triphenylsilanol inside. Particles AA-2 were prepared.

(Example 11-2)
<Preparation of porous particles AA-3 in which a mixture of compound 3 and triphenylsilanol is retained inside>
In Example 11-1, compound 3 and triphenylsilanol were prepared in the same manner as in Example 11-1 except that compound 2 was replaced with 5.5 g of compound 3 and the amount of triphenylsilanol was replaced with 5.0 g. Porous particles AA-3 in which the mixture was retained were prepared.

(Examples 12-1 to 12-4)
<Preparation of porous particles BB-1 to BB-4 in which a mixture of compounds 1 to 4 and triphenylsilanol is retained inside>
In Example 11-1, the same as in Example 11-1 except that the porous particles A were replaced with the porous particles B, and the type and the amount of the compound charged were changed as shown in Table 14-1. , Porous particles BB-1 to BB-4 in which a mixture of compounds 1 to 4 and triphenylsilanol was retained inside were prepared.

(Examples 12-5 to 12-8)
<Preparation of porous particles BB-6 to BB-9 in which a mixture of compounds 1 to 4 and tris [(4-trifluoromethyl) phenyl] silanol is retained inside>
In Example 11-1, the same as in Example 11-1 except that the porous particles A were replaced with the porous particles B, and the type and the amount of the compound charged were changed as shown in Table 14-1. , Compounds 1 to 4 and tris [(4-trifluoromethyl) phenyl] silanol were prepared as porous particles BB-6 to BB-9 in which a mixture of silanol was retained.

(Examples 13-1 to 13-4)
<Preparation of porous particles CC-1 to CC-4 in which a mixture of compounds 1 to 4 and triphenylsilanol is retained inside>
In Example 11-1, the compound was prepared in the same manner as in Example 11-1 except that the porous particle A was replaced with the porous particle C, and the type and charge amount of the compound were changed as shown in Table 15. Porous particles CC-1 to CC-4 in which a mixture of 1 to 4 and triphenylsilanol was retained were prepared.

(Examples 14-1 to 14-4)
<Preparation of porous particles DD-1 to DD-4 in which a mixture of compounds 1 to 4 and triphenylsilanol is retained inside>
In Example 11-1, the compound was prepared in the same manner as in Example 11-1 except that the porous particle A was replaced with the porous particle D, and the type and charge amount of the compound were changed as shown in Table 16. Porous particles DD-1 to DD-4 in which a mixture of 1 to 4 and triphenylsilanol was retained were prepared.

(Example 15-1)
<Preparation of porous particles EE-3 in which a mixture of compound 3 and triphenylsilanol is retained inside>
First, 7.0 g of porous particles E were placed in a 100 mL three-necked flask and dried under reduced pressure at 100 ° C. for 3 hours. After cooling, the flask was transferred to an oil bath bath, established a _{N 2} inlet tube and a thermometer, _{N 2} gas is introduced while the compound 3 5.5 g triphenyl silanol 5.0g and 30g of ethyl acetate was added, 50 After stirring at ° C. for 15 minutes, the temperature of the oil bath bath was set to 80 ° C., and the solution was concentrated by distilling ethyl acetate while stirring, and a mixture of compound 3 and triphenylsilanol was added to the porous particles E. It was held. After completion of the concentration, the mixture was cooled and left at room temperature for 24 hours, 60 g of cyclohexane was added, and the mixture was stirred for 1 hour. Then, after filtration under reduced pressure, the mixture was washed with 30 g of cyclohexane, filtered under reduced pressure again, and the filtered residue was dried under reduced pressure at 60 ° C. for 4 hours to retain the mixture of compound 3 and triphenylsilanol in the porous particles EE-. 3 was prepared.

(Comparative manufacturing example)
<Preparation of Comparative Compound 1>
100 g of aluminum chelate D (24 mass% isopropanol solution (solid content 76 mass%) of aluminum monoacetylacetonate bis (ethylacetacetate)) manufactured by Kawaken Fine Chemicals Co., Ltd. was dried under reduced pressure at 50 ° C. for 24 hours, and then converted to hexane. After washing, dry under reduced pressure at room temperature. 71.4 g of a reddish brown viscous solid of aluminum monoacetylacetonate bis (ethylacetoacetate) was obtained. This compound was designated as Comparative Compound 1.

(Comparative Example 11-1)
<Preparation of Porous Particles AA-5 Containing Comparative Compound 1>
An amount corresponding to 7g as a solid content of the wet cake of the porous porous particles A obtained in Production Example 1 of the particles were transferred to three-necked flask 100mL equipped with N ₂ inlet, Comparative Compound 1 7. added 0g and ethyl acetate 30g, after stirring for 15 min at 50 ° C. in an oil bath bath while introducing N ₂ gas, the temperature was raised in an oil bath bath 80 ° C., evaporated ethyl acetate with stirring By doing so, the liquid was concentrated, and the comparative compound 1 was retained inside the porous particles A. After completion of the concentration, the mixture was cooled and left at room temperature for 24 hours, 60 g of cyclohexane was added, and the mixture was stirred for 1 hour. Then, after vacuum filtration, washing with 30 g of cyclohexane and vacuum filtration were repeated 4 times, and then the filtration residue was dried under reduced pressure at 30 ° C. for 24 hours to obtain porous particles AA-5 in which Comparative Compound 1 was retained. Made.

(Comparative Examples 11-2 to 11-4)
<Preparation of comparative porous particles BB-5 to DD-5>
In Comparative Example 11-1, the comparative porous material 1 was retained inside in the same manner as in Comparative Example 11-1 except that the porous particles A were replaced with the porous particles B to D, respectively. Particles BB-5 to DD-5 were prepared.

The porous particles used and the compounds used in the above examples are shown in Tables 17-1 and 17-2. In addition, Table 18 shows the porous particles used and the compounds used in Comparative Examples 11-1 to 11-4.

(Examples 16-1 to 16-19 and Comparative Examples 12-1 to 12-4)
<Preparation of cationic curable composition>
100 parts by mass of YL980 (manufactured by Mitsubishi Chemical Co., Ltd., bisphenol A type epoxy resin), 5 parts by mass of triphenylsilanol (manufactured by Kanto Chemical Co., Inc.), and 2 parts by mass of each porous particle prepared in the above Examples and Comparative Examples. Then, a cationically curable composition was prepared.
The porous particles used in each example are listed in Tables 19-1 and 19-2 below, and the porous particles used in each comparative example are listed in Table 20.

<Evaluation of cationic curability>
Each 5 mg of the cationic curable composition prepared in Examples 16-1 to 16-19 and Comparative Examples 12-1 to 12-4 was placed in an aluminum container having a diameter of 5 mm for DSC6200, and differential scanning calorimetry was performed. The exothermic peak temperature was evaluated.
As is well known in the art, cation curing is an exothermic reaction, and the exothermic peak temperature by differential scanning calorimetry reflects the curability in cation curing and should be lower.
The conditions for measuring the differential scanning calorimetry are as follows.
[Measurement condition]
-Rising rate: 10 ° C / min (25 ° C to 300 ° C)
・ N ₂ gas: 100 mL / min

<Evaluation of storage stability of cationic curable composition>
The cationically curable compositions prepared in Examples 16-1 to 16-19 and Comparative Examples 12-1 to 12-4 are stored in a closed container at 25 ° C. for 1 day (24 hours) and stored. The reaction rate during storage was estimated by comparing the calorific value in the differential scanning calorimetry before and after. The results are shown in Tables 21-1, 21-2 and 22 along with the curability.
The reaction rate was calculated by the following formula.
Reaction rate (%) =
100 x [(calorific value before storage)-(calorific value after storage)] / (calorific value before storage)

From the results of Table 21-1, Table 21-2 and Table 22, comparison with the same porous particles (Examples 16-1 and 16-2 with respect to Comparative Example 12-1 and Example 16-with respect to Comparative Example 12-2). In Examples 3 to 16-6, Examples 16-7 to 16-10 with respect to Comparative Example 12-3, and Examples 16-11 to 16-14) with respect to Comparative Example 12-4, the compounds of the present invention were retained. The peak temperature is lowered with the porous particles. That is, it was found that the porous particles (cation curing agent) of the present invention have improved curability. Further, in the comparison with the particles in which the compound of the general formula (2) was changed (comparison between Examples 16-3 to 16-6 and Examples 16-16 to 16-19), electron extraction was performed on the phenyl group of triphenylsilanol. It can be said that those using tris [(4-trifluoromethyl) phenyl] silanol to which a sex trifluoromethyl group is added have an exothermic peak at a lower temperature and can improve curability.

(Example 17-1)
<Preparation of porous particles AA-2-1>
1.0 g of n-propyltrimethoxysilane (KBM-3033, manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 9 g of cyclohexane to prepare a surface inactivating treatment solution, which was prepared in Example 12-1. 1.0 g of porous particles AA-2 were added, and the mixture was stirred at 30 ° C. for 20 hours. Then, the mixture was filtered under reduced pressure while being washed with 10 g of cyclohexane, the porous particles were filtered off, and dried under reduced pressure at 40 ° C. for 6 hours to prepare surface-treated porous particles AA-2-1.

(Examples 17-2 to 17-19)
<Preparation of other porous particles>
Example 17-, which was surface-treated in the same manner as in Example 14-1 except that the porous particles used in Example 14-1 were replaced as described in Tables 23-1 and 23-2. Porous particles of 2 to Examples 17-19 were prepared.

(Comparative Examples 13-1 to 13-4)
<Preparation of porous particles for comparison>
Comparative Examples 13-1 to 13-4 which were surface-treated in the same manner as in Example 17-1 except that the porous particles used in Example 17-1 were replaced as shown in Table 24. Porous particles for comparison were prepared.

(Examples 18-1 to 18-19 and Comparative Examples 14-1 to 14-4)
<Preparation of cationic curable composition>
YL980 (manufactured by Mitsubishi Chemical Co., Ltd., bisphenol A type epoxy resin) 60 parts by mass, celloxide 2021P (manufactured by Daicel Chemical Co., Ltd.) 15 parts by mass, Aron Oxetan OXT-221 (manufactured by Toa Synthetic Co., Ltd.) 25 parts by mass, triphenyl 5 parts by mass of silanol (manufactured by Kanto Chemical Co., Inc.), 2 parts by mass of the porous particles prepared in each of Examples 17-1 to 17-19 and Comparative Examples 13-1 to 13-4 were blended, and Example 18- The cationic curable compositions of 1-18-19 and Comparative Examples 14-1 to 14-4 were prepared.
The porous particles used in each example are listed in Tables 25-1 and 25-2 below, and the porous particles used in each comparative example are listed in Table 25-3.

(Examples 19-1 to 19-4 and Comparative Example 15-1)
<Preparation of cationic curable composition>
YL980 (manufactured by Mitsubishi Chemical Co., Ltd., bisphenol A type epoxy resin) 60 parts by mass, celloxide 2021P (manufactured by Daicel Chemical Industry Co., Ltd.) 15 parts by mass, Aron Oxetan OXT-221 (manufactured by Toa Synthetic Co., Ltd.) 25 parts by mass, Tris [ (4-Trifluoromethyl) phenyl] 5 parts by mass of silanol (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 2 parts by mass of the porous particles prepared in each of Examples 17-3 to 17-6 and Comparative Example 13-2 are blended. Then, the cationic curable compositions of Examples 19-1 to 19-4 and Comparative Example 15-1 were prepared.
The porous particles used in each example and the porous particles used in the comparative examples are shown in Table 26.

<Evaluation of cationic curability>
5 mg each of the cationic curable compositions prepared in Examples 18-1 to 18-19 and 19-1 to 19-4 and Comparative Examples 14-1 to 14-4 and 15-1 are 5 mm diameter aluminum for DSC6200. It was placed in a container, differential scanning calorimetry was performed, and the exothermic peak temperature was evaluated in the same manner as described above.

<Evaluation of storage stability of cationic curable composition>
The cationic curable compositions prepared in Examples 18-1 to 18-19 and 19-1 to 19-4 and Comparative Examples 14-1 to 14-4 and 15-1 were placed in a closed container at 25 ° C. for 1 day. The reaction rate during storage was estimated by storing (24 hours) and comparing the calorific value in the differential scanning calorimetry before and after storage. The results are shown in Tables 27-1, 27-2 and 27-3 and 28, along with curability.
The reaction rate was calculated by the following formula.
Reaction rate (%) =
100 x [(calorific value before storage)-(calorific value after storage)] / (calorific value before storage)

From the results of Table 27-1, Table 27-2, Table 27-3 and Table 28, comparison with the same porous particles (Examples 18-1 and 18-2 with respect to Comparative Example 14-1 and Comparative Example 14-2) 18-3 to 18-6, 18-7 to 18-10 to Comparative Example 14-3, and 18-11 to 18-14 to Comparative Example 14-4) are all compounds of the present invention. The peak temperature can be lowered by the porous particles that retain the above. That is, it was found that the cationic curing agent of the present invention has improved curability.
Further, in the comparison with the particles in which the compound of the above general formula (2) was changed (comparison between Examples 18-3 to 18-6 and Examples 18-16 to 18-19), the phenyl group of triphenylsilanol was subjected to electron determination. It can be said that those using tris [(4-trifluoromethyl) phenyl] silanol to which an attractive trifluoromethyl group is added have an exothermic peak at a lower temperature and can improve curability.
Further, Comparative Examples 15-1 also in Examples 19-1 to 19-4 in which the compound of the above general formula (2) blended in the cationic curable composition was tris [(4-trifluoromethyl) phenyl] silanol. By comparison with the above, the peak temperature of the porous particles holding the compound of the present invention can be lowered. Further, the peak temperature was lowered also in Examples 18-3 to 18-6 in which triphenylsilanol was blended, and by imparting an electron-attracting group to the phenyl group of triphenylsilanol, an electron-attracting group was added. It can be seen that the curability can be further improved.
Further, the reaction rate when stored at 25 ° C. for 1 day is almost the same as that of the present invention in the comparative example, and it can be said that the porous particles of the present invention have improved curability without impairing the storage stability. That is, it was found that the cationic curing agent of the present invention has improved curability without impairing the potential. It can also be seen that this effect does not change even if the compound of the above general formula (2) in the cationic curing formulation is changed from triphenylsilanol to tris [(4-trifluoromethyl) phenyl] silanol.

The cationic curing agent of the present invention can be suitably used as a latent curing agent for a cationic curing composition.
The cationically curable composition of the present invention can be suitably used as a latently curable cationically curable composition.

Claims (11)

Porous particles and
A cationic curing agent comprising a compound represented by the following general formula (1) held in the porous particles.
However, in the general formula (1), R ¹ is a branched alkyl group or phenyl group having 1 to 18 carbon atoms, and these may be further substituted with a substituent.
R ² is a hydrogen atom, an alkyl group which may have a branched structure having 1 to 4 carbon atoms, halogenoalkyl group, an alkoxy group, or a phenoxy group, the alkyl group, halogenoalkyl group, an alkoxy group and phenoxy group, more It may be substituted with a substituent. R ¹ and R ² may be the same or different from each other. Porous particles and
A cationic curing agent having a mixture of a compound represented by the following general formula (1) and a compound represented by the following general formula (2) held in the porous particles.
However, in the general formula (1), R ¹ is a branched alkyl group or phenyl group having 1 to 18 carbon atoms, and these may be further substituted with a substituent.
R ² is a hydrogen atom, an alkyl group which may have a branched structure having 1 to 4 carbon atoms, halogenoalkyl group, an alkoxy group, or a phenoxy group, the alkyl group, halogenoalkyl group, an alkoxy group and phenoxy group, more It may be substituted with a substituent. R ¹ and R ² may be the same or different from each other.
However, in the general formula (2), Z represents a hydrogen atom or an electron-withdrawing group. a is an integer from 0 to 5. The cationic curing agent according to any one of claims 1 to 2, wherein the porous particles are either organic porous particles or inorganic porous particles. The cationic curing agent according to claim 3, wherein the organic porous particles are composed of a polyurea resin. The cationic curing agent according to claim 4, wherein the organic porous particles further contain a vinyl resin as a constituent component. The cationic curing agent according to any one of claims 1 to 5, wherein the surface of the porous particles has a reaction product of a silane treatment agent. The compound represented by the following general formula (1) and the porous particles are allowed to coexist in an organic solvent, and then the solvent is removed so that the compound represented by the general formula (1) is retained in the porous particles. A method for producing a cationic curing agent.
However, in the general formula (1), R ¹ is a branched alkyl group or phenyl group having 1 to 18 carbon atoms, and these may be further substituted with a substituent.
R ² is a hydrogen atom, an alkyl group which may have a branched structure having 1 to 4 carbon atoms, halogenoalkyl group, an alkoxy group, or a phenoxy group, the alkyl group, halogenoalkyl group, an alkoxy group and phenoxy group, more It may be substituted with a substituent. R ¹ and R ² may be the same or different from each other. The compound represented by the following general formula (1), the compound represented by the following general formula (2), and the porous particles are allowed to coexist in an organic solvent, and then desolvated to obtain the above general formula (1). A method for producing a cationic curing agent, which comprises holding the compound represented by the compound and the compound represented by the general formula (2) in the porous particles.
However, in the general formula (1), R ¹ is a branched alkyl group or phenyl group having 1 to 18 carbon atoms, and these may be further substituted with a substituent.
R ² is a hydrogen atom, an alkyl group which may have a branched structure having 1 to 4 carbon atoms, halogenoalkyl group, an alkoxy group, or a phenoxy group, the alkyl group, halogenoalkyl group, an alkoxy group and phenoxy group, more It may be substituted with a substituent.
R ¹ and R ² may be the same or different from each other.
However, in the general formula (2), Z represents a hydrogen atom or an electron-withdrawing group. a is an integer from 0 to 5. A cationically curable composition comprising a cationically curing component and the cationically curing agent according to any one of claims 1 to 6. The cationically curable composition according to claim 9, further containing an organic silane compound. The cationic curable composition according to claim 10, wherein the organic silane compound is a compound represented by the following general formula (2).
However, in the general formula (2), Z represents a hydrogen atom or an electron-withdrawing group. a is an integer from 0 to 5.