阅读说明：本技术 阳离子固化性组合物 (Cation-curable composition ) 是由 森田恵介 神谷和伸 西尾健 于 2018-07-02 设计创作，主要内容包括：一种阳离子固化性组合物,含有阳离子固化成分、保持铝螯合物的多孔质粒子和下述通式(1)所表示的硅醇化合物。(Ar)<Sub>m</Sub>Si(OH)<Sub>4－m</Sub>···通式(1)；其中,在上述通式(1)中,Ar表示具有吸电子性基团的芳基。m表示2或3。(A cationically curable composition comprising a cationically curable component, porous particles holding an aluminum chelate, and a silanol compound represented by the following general formula (1). (Ar) m Si(OH) 4－m General formula (1); wherein, in the general formula (1), Ar represents an aryl group having an electron-withdrawing group. m represents 2 or 3.)

1. A cationically curable composition characterized in that,

containing a cationic curing component, porous particles holding an aluminum chelate, and a silanol compound represented by the following general formula (1),

(Ar)_mSi(OH)_4－mgeneral formula (1)

Wherein in the general formula (1), Ar represents an aryl group having an electron-withdrawing group, and m represents 2 or 3.

2. The cationically curable composition according to claim 1,

the cationic curing component contains a glycidyl ether type epoxy resin.

3. The cationically curable composition according to claim 2,

the ratio of the glycidyl ether type epoxy resin in the cationic curing component is 60 mass% or more and 100 mass% or less.

4. The cationically curable composition according to claim 2 or 3,

the content of the glycidyl ether type epoxy resin is 500 mass% or more with respect to the content of the porous particles.

5. The cationically curable composition according to any one of claims 2 to 4, wherein,

the content of the glycidyl ether type epoxy resin is 1000 mass% or more and 5000 mass% or less with respect to the content of the porous particles.

6. The cationically curable composition according to any one of claims 1 to 5, wherein,

the content of the silanol compound is 20 mass% or less with respect to the cationic curing component.

7. The cationically curable composition according to any one of claims 1 to 6, wherein,

the content of the porous particles is 20 mass% or less with respect to the cationically curable component.

8. The cationically curable composition according to any one of claims 1 to 7, wherein,

the electron-withdrawing group is any one of a fluoro group, a perfluoroalkyl group, a nitro group, a nitrile group, a sulfo group, a formyl group and an alkoxycarbonyl group.

9. The cationically curable composition according to any one of claims 1 to 8, wherein,

the porous particles are made of polyurea resin.

10. The cationically curable composition according to claim 9,

the porous particles further have a vinyl resin as a constituent component.

11. The cationically curable composition according to any one of claims 1 to 8, wherein,

the porous particles are porous inorganic particles that hold an aluminum chelate.

12. The cationically curable composition according to any one of claims 1 to 11, wherein,

the surface of the porous particle has a reaction product of an alkoxysilane coupling agent.

Technical Field

The present invention relates to a cationically curable composition.

Background

Conventionally, as a means for cationically curing 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, an aluminum chelate compound reacts with a silanol compound to generate a cationic curing initiating species, thereby embodying cationic curing.

One example of a technique for using a latent curing agent of the above curing system is a method for retaining an aluminum chelate compound in porous particles, and for example, the following technique is proposed.

The following methods are proposed: the aluminum compound is held in porous particles produced using a polyfunctional isocyanate, and is physically separated from the silanol compound (see, for example, patent document 1).

In addition, as an example similar to the technique proposed above, a method of improving curability by using a bifunctional isocyanate in combination with a polyfunctional isocyanate has been proposed (for example, see patent document 2).

Further, a method of using a radical polymerizable compound in combination when producing porous particles has been proposed (for example, see patent document 3).

Further, a method of using porous inorganic particles as porous particles has been proposed (for example, see patent document 4).

As a means for further improving the potential by these methods, for example, a method of treating the surface of the porous particles with a specific silane treatment agent has been proposed (for example, see patent document 5).

In curing a cationic curable resin, there is a problem that degassing occurs at the time of curing reaction thereof.

Thus, in order to suppress the occurrence of outgassing, an epoxy resin composition comprising an epoxy compound (A) containing 30 to 55 mass% of a glycidyl-type epoxy compound (a1), 35 to 60 mass% of an alicyclic epoxy compound (a2) and 5 to 30 mass% of a urethane-modified epoxy compound (a3), a curing agent (B) which is an aluminum chelate latent curing agent comprising an aluminum chelate curing agent held in a porous resin obtained by interfacial polymerization of a polyfunctional isocyanate compound, and a curing catalyst (C) which is a specific silanol compound, the amount of the aluminum chelate-based latent curing agent (B) is 0.5 to 5 parts by mass per 100 parts by mass of the epoxy compound (a) (see, for example, patent document 6).

Disclosure of Invention

Technical problem

The technique described in japanese patent No. 5476988 can reduce outgassing, but has a problem that the composition of the epoxy compound in the epoxy resin composition is limited. This is due to: an alicyclic epoxy compound having high cationic polymerizability or a urethane-modified epoxy compound which is less volatile is effective for suppressing degassing, and degassing is being reduced by actively using such an epoxy compound. Therefore, in the technique described in japanese patent No. 5476988, a glycidyl ether type epoxy resin, which is a general-purpose resin, cannot be used much, and as a result, the degree of freedom of the epoxy resin as a cationic curing component is low.

The present invention has been made to solve the above-described problems of the related art and to achieve the following object. That is, the present invention aims to: provided is a cationic curable composition which can reduce degassing and has a high degree of freedom in cationic curing components.

Means for solving the problems

Means for solving the above problems are as follows. Namely:

< 1 > a cationically curable composition characterized in that: containing a cationic curing component, porous particles holding an aluminum chelate, and a silanol compound represented by the following general formula (1),

(Ar)_mSi(OH)_4－mgeneral formula (1)

Wherein in the general formula (1), Ar represents an aryl group having an electron-withdrawing group. m represents 2 or 3.

< 2 > the cationically curable composition according to < 1 >, wherein the cationically curable component contains a glycidyl ether type epoxy resin.

The cationic curable composition of < 3 > or < 2 > wherein the glycidyl ether type epoxy resin is contained in the cationic curable component in an amount of 60 to 100 mass%.

The cationically curable composition according to any one of < 4 > to < 2 > to < 3 >, wherein the content of the glycidyl ether type epoxy resin is 500% by mass or more based on the content of the porous particles.

The cationically curable composition according to any one of < 5 > to < 2 > to < 4 >, wherein the content of the glycidyl ether type epoxy resin is 1000 mass% or more and 5000 mass% or less with respect to the content of the porous particles.

The cationically curable composition according to any one of < 6 > to < 1 > to < 5 >, wherein the content of the silanol compound is 20% by mass or less relative to the cationically curable component.

The cation-curable composition according to any one of < 7 > to < 1 > to < 6 >, wherein the content of the porous particles is 20% by mass or less with respect to the cation-curable component.

The cation curable composition according to any one of < 8 > to < 1 > to < 7 >, wherein the electron-withdrawing group is any one of a fluoro group, a perfluoroalkyl group, a nitro group, a nitrile group, a sulfo group, a formyl group and an alkoxycarbonyl group.

The cation-curable composition according to any one of < 9 > to < 1 > to < 8 >, wherein the porous particles are formed of a polyurea resin.

The cationic curable composition of < 10 > or < 9 > wherein the porous particles further comprise a vinyl resin as a constituent.

The cationically curable composition according to any one of < 11 > to < 1 > to < 8 >, wherein the porous particles are porous inorganic particles holding an aluminum chelate complex.

The cationically curable composition according to any one of < 12 > to < 11 >, wherein the porous particles have a reaction product of an alkoxysilane coupling agent on the surface thereof.

Effects of the invention

The present invention can solve the above-described problems of the prior art, and can achieve the above-described object, and can provide a cationically curable composition which can reduce outgassing and has a high degree of freedom of cationically curable components.

Drawings

Fig. 1 is a schematic diagram for explaining a method of producing a degassing evaluation sample.

FIG. 2 is a photograph showing the results of evaluation of degassing in example 3.

FIG. 3 is a photograph showing the results of evaluation of degassing in comparative example 3.

Detailed Description

(cation-curable composition)

The cationic curable composition of the present invention contains at least a cationic curing component, porous particles, and a silanol compound represented by the following general formula (1), and further contains other components as needed.

(Ar)_mSi(OH)_4－mGeneral formula (1)

Wherein in the general formula (1), Ar represents an aryl group having an electron-withdrawing group. m represents 2 or 3.

< cationic curing component >

The cationic curing component is not particularly limited as long as it is an organic material that can be cationically cured, and can be appropriately selected according to the purpose, and examples thereof include: epoxy resins, oxetane compounds, vinyl ether resins, and the like.

Epoxy resin

The epoxy resin is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include: glycidyl ether type epoxy resins, alicyclic epoxy resins, and the like.

The glycidyl ether type epoxy resin may be, for example, a liquid or solid, and is preferably a glycidyl ether type epoxy resin having an epoxy equivalent of usually about 100 to 4000 and having 2 or more epoxy groups in a molecule. Examples thereof include: 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. Among them, bisphenol a type epoxy resins can be preferably used in view of resin characteristics. In addition, these epoxy resins also contain monomers or oligomers.

The alicyclic epoxy resin is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include: vinylcyclopentadiene dioxide, vinylcyclohexene monoxide or dioxide, dicyclopentadiene oxide, epoxy- [ epoxy-oxaspiro C_8－15Alkyl radical]-Ring C_5－12Alkanes (e.g. 3, 4-epoxy-1- [8, 9-epoxy-2, 4-dioxaspiro [5.5 ]]Undec-3-yl]Cyclohexane, etc.), 3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexanecarboxylate, epoxy C_5－12Cycloalkyl radical C_1－3Alkyl-epoxy radical C_5－12Cycloalkane carboxylates (e.g., 4, 5-epoxycyclooctylmethyl-4 ', 5' -epoxycyclooctane carboxylate), bis (C)_1－3Alkyl epoxy radical C_5－12Cycloalkyl radical C_1－3Alkyl) dicarboxylic acid esters (e.g., bis (2-methyl-3, 4-epoxycyclohexylmethyl) adipate, etc.).

Further, as the alicyclic epoxy resin, it is preferable to use 3, 4-epoxycyclohexylmethyl-3 ', 4' -epoxycyclohexanecarboxylate [ (trade name: CELLOXIDE # 2021P; the epoxy equivalent is 128 to 140 ].

In the above examples, C_8－15、C_5－12、C_1－3The number of carbon atoms is 8 to 15, 5 to 12, and 1 to 3, respectively, and shows the structural breadth of the compound.

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

[ chemical formula 1]

[ oxetane Compound ]

In the above cationic curable composition, the heat generation 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, 4' -bis [ (3-ethyl-3-oxetanyl) methoxymethyl ] biphenyl, bis [ (3-ethyl-3-oxetanyl) ] methyl 1, 4-benzenedicarboxylate, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, bis [ 1-ethyl (3-oxetanyl) ] methyl ether, 3-ethyl-3- { [ 3- (triethoxysilyl) propoxy ] methyl } oxetane, oxetanylsilsesquioxane, novolak oxetane, and the like.

The content of the cationic curing component in the cationic curable composition is not particularly limited, and may be appropriately selected according to the purpose, and is preferably 30% by mass or more and 99% by mass or less, more preferably 50% by mass or more and 98% by mass or less, and particularly preferably 70% by mass or more and 97% by mass or less.

The content is a content in the nonvolatile component of the cationic curable composition. The same applies to the following.

Further, since the cationic curable composition of the present invention has a high degree of freedom of cationic curing components, even when the glycidyl ether type epoxy resin is frequently used as the cationic curing component, degassing can be suppressed.

In this regard, the proportion of the glycidyl ether type epoxy resin in the cationic curing component is preferably 60% by mass or more and 100% by mass or less, and more preferably 70% by mass or more and 100% by mass or less.

The content of the glycidyl ether type epoxy resin is preferably 500 mass% or more, more preferably 500 mass% or more and 10,000 mass% or less, and particularly preferably 1000 mass% or more and 5000 mass% or less with respect to the content of the porous particles.

< porous particle >

The porous particles hold an aluminum chelate.

The porous particles are not particularly limited as long as they have many pores, and may be appropriately selected according to the purpose, and examples thereof include: porous organic resin particles made of an organic resin, porous inorganic particles made of an inorganic compound, and the like.

The porous particles hold the aluminum chelate compound in pores thereof, for example. In other words, the aluminum chelate is taken into and held in the micropores present in the porous particle matrix.

The average pore diameter of the pores of the porous particles is not particularly limited, and may be appropriately selected according to the purpose, and is preferably 1nm to 300nm, more preferably 5nm to 150 nm.

(porous organic resin particle)

The porous organic resin particles are not particularly limited as long as they are porous particles made of an organic resin, and may be appropriately selected according to the purpose.

The organic resin is not particularly limited, and may be appropriately selected according to the purpose, and is preferably a polyurea resin. 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 thereof.

Polyurea resin

The polyurea resin refers to a resin having a urea bond in the resin.

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

(iv) vinyl resin

The vinyl resin is a resin obtained by polymerizing a radical polymerizable vinyl compound.

The vinyl resin improves the mechanical properties of the porous particles. This makes it possible to realize thermal responsiveness of the cationic curing component during curing, particularly sharp thermal responsiveness in a low-temperature region.

The vinyl resin can be obtained, for example, by further containing a radical polymerizable vinyl compound in advance in an emulsion containing a polyfunctional isocyanate compound, and radical polymerizing the radical polymerizable vinyl compound simultaneously with polymerizing the polyfunctional isocyanate compound in the emulsion.

The average particle diameter of the porous organic resin particles is not particularly limited and may be appropriately selected depending on the 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 particularly preferably 1 μm or more and 5 μm or less.

(porous inorganic particle)

The porous inorganic particles are not particularly limited as long as they are porous particles made of an inorganic compound, and may be appropriately selected according to the purpose.

Examples of the material of the porous inorganic particles include: silica, aluminum silicate, alumina, zirconia, potassium oxide, calcium oxide, titanium oxide, calcium borate, sodium borosilicate, sodium oxide, phosphate, and the like. 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, zeolite, and the like. These particles 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 according to the purpose, but is preferably 50nm to 5000 μm, more preferably 250nm to 1000 μm, and particularly preferably 500nm to 200 μm.

Aluminum chelate complex

Examples of the aluminum chelate compound include a complex compound represented by the following general formula (A) in which aluminum is coordinated with 3 β -keto-enolate anions, wherein alkoxy groups are not directly bonded to aluminum, and the reason is that the alkoxy groups are easily hydrolyzed when directly bonded to aluminum, and thus the aluminum chelate compound is not suitable for emulsification treatment in the production of the porous particles.

[ chemical formula 2]

In the above general formula (A), R¹、R²And R³Each independently represents an alkyl group or an alkoxy group.

Examples of the alkyl group include: methyl, ethyl, and the like.

Examples of the alkoxy group include: methoxy, ethoxy, oleoyloxy (oleoyloxy), and the like.

Examples of the complex compound represented by the general formula (a) include: tris (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, monoacetylacetonbis (oleylacetoacetate) aluminum, and the like.

The content of the aluminum chelate compound in the porous particles is not particularly limited, and may be appropriately selected according to the purpose.

Surface of porous particle

The porous particles preferably have a reaction product of an alkoxysilane coupling agent on the surface thereof in order to further improve the potential.

The reaction product is obtained by reacting an alkoxy silane coupling agent.

The reaction product is present on the surface of the porous particles.

The content of the porous particles is not particularly limited and may be appropriately selected according to the purpose, and is preferably 20% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less, and particularly preferably 1% by mass or more and 10% by mass or less with respect to the cationically curable component.

Method for producing porous particles

The method for producing the porous particles holding the aluminum chelate complex is not particularly limited, and may be appropriately selected depending on the purpose.

Examples of the method for producing the porous inorganic particles holding an aluminum chelate compound include the following methods: a porous inorganic particle is immersed in a liquid containing an aluminum chelate compound, and the pores of the porous inorganic particle are filled with the aluminum chelate compound.

Examples of the method for producing the porous organic resin particles holding an aluminum chelate compound include the following production methods.

Method for producing porous organic resin particle

The method for producing the porous organic resin particles includes, for example, at least: the porous particle production step and the passivation step may further include other steps as necessary.

Porous particle preparation step

The porous particle production step includes at least: the emulsion preparation treatment and the polymerization treatment preferably include an additional filling treatment and, if necessary, further include other treatments.

-emulsion preparation treatment- -

The emulsion preparation treatment is not particularly limited as long as it is a treatment in which an aluminum chelate compound, a polyfunctional isocyanate compound and preferably an organic solvent are mixed and the obtained liquid is emulsified to obtain an emulsion, and the treatment can be appropriately selected according to the purpose, and can be carried out using, for example, a homogenizer.

When the resin constituting the porous particles includes not only the polyurea resin but also the vinyl resin, the liquid further includes a radical polymerizable vinyl compound and a radical polymerization initiator.

As the above-mentioned aluminum chelate compound, there may be mentioned: the aluminum chelate compound in the description of the latent curing agent of the present invention is described above.

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

Polyfunctional isocyanate compounds

The polyfunctional isocyanate compound is a compound having 2 or more isocyanate groups, preferably 3 isocyanate groups, per molecule.

Examples of the polyfunctional isocyanate compound include: a difunctional isocyanate compound and a trifunctional isocyanate compound.

As preferred examples of the trifunctional isocyanate compound, there may be mentioned: a TMP adduct of the following general formula (2) obtained by reacting 3 moles of a diisocyanate compound with 1 mole of trimethylolpropane; an isocyanurate body of the following general formula (3) obtained by self-condensing 3 moles of a diisocyanate compound; a biuret product represented by the following general formula (4) obtained by condensing 2 moles of diisocyanate urea obtained from 3 moles of diisocyanate compounds with the remaining 1 mole of diisocyanate.

[ chemical formula 3]

In the above general formulae (2) to (4), the substituent R means a portion of the diisocyanate compound other than 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, methylene diphenyl-4, 4' -diisocyanate, and the like.

Examples of the difunctional isocyanate compound include: toluene diisocyanate, xylylene diisocyanate, naphthalene-1, 5-diisocyanate, tetramethylxylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, trimethylhexamethylene diisocyanate, methylenediphenyl diisocyanate, dichlorobiphenyl diisocyanate, phenylene diisocyanate, tetramethylene diisocyanate, and the like.

The mixing ratio of the aluminum chelate compound and the polyfunctional isocyanate compound is not particularly limited, and may be appropriately selected depending on the purpose, and when the mixing amount of the aluminum chelate compound is too small, the curability of the cationic curing component to be cured is lowered, and when the mixing amount is too large, the latent curing agent to be obtained is lowered. In this regard, the aluminum chelate compound is preferably 10 parts by mass or more and 500 parts by mass or less, more preferably 10 parts by mass or more and 300 parts by mass or less, with respect to 100 parts by mass of the polyfunctional isocyanate compound.

Organic solvents

The organic solvent is not particularly limited, and may be appropriately selected according to the purpose, and is preferably a volatile organic solvent.

The organic solvent is preferably: the aluminum chelate compound, the polyfunctional isocyanate compound, the radical polymerizable vinyl compound and the radical polymerization initiator are each a good solvent (each solubility is preferably 0.1g/ml (organic solvent)) which is substantially insoluble in water (the solubility of water is 0.5g/ml (organic solvent)) and an organic solvent having a boiling point of 100 ℃ or lower under atmospheric pressure. Specific examples of such volatile organic solvents include: alcohols, acetates, ketones, and the like. Among them, ethyl acetate is preferable in terms of high polarity, low boiling point, and poor water solubility.

The amount of the organic solvent used is not particularly limited, and may be appropriately selected depending on the purpose.

Radical polymerizable vinyl compound

The radical polymerizable vinyl compound is a compound having a radical polymerizable carbon-carbon unsaturated bond in the molecule.

The radical polymerizable vinyl compound includes a so-called monofunctional radical polymerizable compound and a polyfunctional radical polymerizable compound.

The radical polymerizable vinyl compound preferably contains a polyfunctional radical polymerizable compound. This is due to: by using a polyfunctional radical polymerizable compound, it becomes easier to achieve sharp thermal responsiveness in a low temperature region. In this sense, the radical polymerizable vinyl compound preferably contains 30% by mass or more, and more preferably contains 50% by mass or more of the polyfunctional radical polymerizable compound.

Examples of the monofunctional radical polymerizable compound include: monofunctional vinyl compounds (e.g., styrene, methylstyrene, etc.), monofunctional (meth) acrylate compounds (e.g., butyl acrylate, etc.), and the like.

Examples of the polyfunctional radical polymerizable compound include: polyfunctional vinyl compounds (e.g., divinylbenzene, divinyl adipate, etc.), polyfunctional (meth) acrylate compounds (e.g., 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, etc.), and the like.

Among these, polyfunctional vinyl compounds, particularly divinylbenzene, can be preferably used from the viewpoint of the potential and thermal responsiveness.

The polyfunctional radical polymerizable compound may be composed of a polyfunctional vinyl compound and a polyfunctional (meth) acrylate compound. By using these compounds in combination, the effect of changing the thermal responsiveness or introducing a reactive functional group can be obtained.

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

Radical polymerization initiator

Examples of the radical polymerization initiator include: peroxide initiators, azo initiators, and the like.

The amount of the radical polymerization initiator to be blended is not particularly limited and may be appropriately selected depending on the purpose, and is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the radical polymerizable vinyl compound.

Polymerization treatment- -

The polymerization treatment is not particularly limited as long as it is a treatment for polymerizing the polyfunctional isocyanate compound in the emulsion to obtain porous particles, and may be appropriately selected according to the purpose.

The porous particles hold the aluminum chelate.

In the polymerization treatment, a part of the isocyanate groups of the polyfunctional isocyanate compound is hydrolyzed to form amino groups, and the amino groups react with the isocyanate groups of the polyfunctional isocyanate compound to form urea bonds, thereby obtaining a polyurea resin. Here, in the case where the above-mentioned polyfunctional isocyanate compound has a urethane bond, the resultant polyurea resin also has a urethane bond, and in this respect, the resultant polyurea resin may also be referred to as a polyurea polyurethane resin.

In the case where the emulsion contains the radical polymerizable vinyl compound and the radical polymerization initiator, the radical polymerizable vinyl compound is subjected to radical polymerization in the presence of the radical polymerization initiator simultaneously with the polymerization of the polyfunctional isocyanate compound in the polymerization treatment.

Therefore, the obtained porous particles contain a polyurea resin and a vinyl resin as the resins constituting them.

The polymerization time in the above polymerization treatment is not particularly limited, and may be appropriately selected according to the purpose, and is preferably 1 hour or more and 30 hours or less, and more preferably 2 hours or more and 10 hours or less.

The polymerization temperature in the polymerization treatment is not particularly limited, and may be appropriately selected according to the purpose, and is preferably 30 ℃ to 90 ℃, and more preferably 50 ℃ to 80 ℃.

-additional filling treatment- -

The additional filling treatment is not particularly limited as long as it is a treatment of additionally filling an aluminum chelate compound into the porous particles obtained by the polymerization treatment, and may be appropriately selected according to the purpose, and examples thereof include: the method for producing the porous particles of the present invention includes the steps of dissolving an aluminum chelate compound in an organic solvent, impregnating the porous particles in the obtained solution, and removing the organic solvent from the solution.

By performing the additional filling treatment, the amount of the aluminum chelate retained by the porous particles is increased. The porous particles additionally filled with the aluminum chelate compound may be filtered, washed, dried, and then pulverized into primary particles using a known pulverizer, if necessary.

The aluminum chelate compound to be additionally charged in the additional charging treatment may be the same as or different from the aluminum chelate compound to be added to the liquid to form the emulsion, and examples of the aluminum chelate compound to be used in the additional charging treatment include aluminum diisopropoxyamonoacetyloleyl acetate, aluminum monoisopropoxybis (oleyl acetoacetate), aluminum monoisopropoxymonoacetyl acetoacetate, aluminum diisopropoxyamonoacetyl acetoacetate, aluminum diisopropoxyacetoacetate lauryl, aluminum diisopropoxyacetoacetate stearyl, aluminum diisopropoxyacetoacetate, aluminum monoisopropoxymono-N-lauroyl- β -aluminum monoacetylate lauryl monoacetyl acetate, and the like.

The organic solvent is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include: the organic solvent exemplified in the description of the emulsion preparation process. The same applies to the preferred embodiments.

The method for removing the organic solvent from the solution is not particularly limited, and may be appropriately selected according to the purpose, and examples thereof include: a method of heating the solution to a boiling point of the organic solvent or higher, a method of reducing the pressure of the solution, and the like.

The content of the aluminum chelate complex in the solution obtained by dissolving the aluminum chelate complex in the organic solvent is not particularly limited and may be appropriately selected according to the purpose, and is preferably 10 mass% or more and 80 mass% or less, and more preferably 10 mass% or more and 50 mass% or less.

Passivation procedure-

The passivation step is not particularly limited as long as it is a step of providing a reaction product of an alkoxysilane coupling agent to the surface of the porous particles, and may be appropriately selected according to the purpose, and is preferably performed by, for example, immersing the porous particles in a solution containing an alkoxysilane coupling agent and an organic solvent, and reacting the alkoxysilane coupling agent.

It is considered that the porous particles have an aluminum chelate not only in the interior but also on the surface of the particles. However, most of the aluminum chelate compound on the surface at the time of interfacial polymerization is deactivated by water present in the polymerization system. Therefore, the porous particles can have latent properties without the passivation step (i.e., without the reaction product of the alkoxysilane coupling agent on the surface).

However, in the case of using an alicyclic epoxy resin having high reactivity as an epoxy resin, a thermosetting epoxy resin composition using a latent curing agent which has not undergone the above-described passivation process is greatly thickened with time. It is thus assumed that: a part of the aluminum chelate complex on the surface of the porous plasmid was not inactivated and maintained its activity.

Therefore, as will be described below, it is preferable to inactivate the aluminum chelate compound present on the surface of the porous plasmid with an alkoxysilane coupling agent.

-alkoxysilane coupling agent- -

As explained below, the above-mentioned alkoxysilane coupling agents are classified into two types.

The first type of silane coupling agent: it reacts with the active aluminum chelate on the surface of the above-mentioned porous plasmid to produce an aluminum chelate-silanol reactant, thereby decreasing the electron density of oxygen adjacent to the aluminum atom (in other words, it decreases the acidity of hydrogen bonded to oxygen, further in other words, it decreases the polarizability between oxygen and hydrogen), resulting in a decrease in activity. As this type of silane coupling agent, there may be mentioned: the alkoxysilane coupling agent in which the electron-donating group is bonded to the silicon atom is preferably an alkylalkoxysilane coupling agent having an alkyl group. Specifically, there may be mentioned: methyltrimethoxysilane, n-propyltrimethoxysilane, hexyltrimethoxysilane, and the like.

The second type of silane coupling agent: the epoxy groups in the molecule react with the active aluminum chelate of the porous particles, and the surface is coated with the resulting epoxy group polymer chains, thereby reducing the activity. As this type of silane coupling agent, an epoxy silane coupling agent can be cited. Specifically, there may be mentioned: 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303, shin-Etsu chemical Co., Ltd.), 3-glycidoxypropyltrimethoxysilane (KBM-403, shin-Etsu chemical Co., Ltd.), and the like.

-organic solvent- -

The organic solvent is not particularly limited and may be appropriately selected according to the purpose, and a nonpolar solvent is preferable. Examples of the nonpolar solvent include hydrocarbon solvents. Examples of the hydrocarbon solvent include: toluene, xylene, cyclohexane, and the like.

The content of the alkoxysilane coupling agent in the solution is not particularly limited and may be appropriately selected according to the purpose, and is preferably 5% by mass or more and 80% by mass or less.

The temperature of the solution in the passivation step is not particularly limited, and may be appropriately selected according to the purpose, and is preferably 10 ℃ to 80 ℃, more preferably 20 ℃ to 60 ℃ in order to prevent aggregation of the porous particles and to prevent the aluminum chelate from flowing out of the porous particles.

The immersion time in the passivation step is not particularly limited, and may be appropriately selected according to the purpose, and is preferably 1 hour or more and 48 hours or less, and more preferably 5 hours or more and 30 hours or less.

In the passivation step, the solution is preferably stirred.

The latent curing agent obtained through the passivation step may be filtered, washed, dried, and then pulverized into primary particles using a known pulverizing apparatus, if necessary.

< silanol Compound >

The silanol compound is represented by the following general formula (1).

(Ar)_mSi(OH)_4－mGeneral formula (1)

Wherein in the general formula (1), Ar represents an aryl group having an electron-withdrawing group. m represents 2 or 3.

The silanol compound represented by the general formula (1) is a monohydric alcohol or a dihydric alcohol.

Here, since the silanol compound represented by the above general formula (1) has an electron-withdrawing group in the aryl group, the polarizability between oxygen and hydrogen adjacent to a silicon atom due to an induction effect is increased, that is, the acidity of the silanol compound is increased. This improves the reactivity of the cationic curable composition, and thus improves the reactivity. As a result, it is considered that the occurrence of the degassing can be suppressed.

Examples of the aryl group include: phenyl, naphthyl (e.g., 1-naphthyl, 2-naphthyl, etc.), anthracenyl (e.g., 1-anthracenyl, 2-anthracenyl, 9-anthracenyl, benzo [ a ] -9-anthracenyl, etc.), phenallyl (e.g., 3-phenallyl, 9-phenallyl, etc.), pyrenyl (e.g., 1-pyrenyl, etc.), azulenyl, fluorenyl, biphenyl (e.g., 2-biphenyl, 3-biphenyl, 4-biphenyl, etc.), thienyl, furyl, pyrrolyl, imidazolyl, pyridyl, etc. Among them, phenyl is preferable from the viewpoint of easiness of obtaining and obtaining cost. The m Ar groups may be the same or different, and are preferably the same from the viewpoint of easiness of acquisition.

Examples of the electron-withdrawing group include: a halogen group (e.g., a fluorine group, a chlorine group, a bromine group, etc.), a perfluoroalkyl group, a nitro group, a nitrile group, a sulfo group, a formyl group, a carboxyl group, an alkoxycarbonyl group (e.g., a methoxycarbonyl group, an ethoxycarbonyl group, etc.), a formyl group, etc. Among them, preferred are a fluoro group, a perfluoroalkyl group, a nitro group, a nitrile group, a sulfo group, a formyl group and an alkoxycarbonyl group.

Examples of the perfluoroalkyl group include: the perfluoroalkyl group having 1 to 6 carbon atoms includes, specifically: trifluoromethyl, pentafluoroethyl, and the like.

In the aryl group, the number of the electron-withdrawing groups may be 1 or more.

In the case where the aryl group is a phenyl group, the electron-withdrawing group is preferably ortho-or para-positioned with respect to the Ar — Si bond in terms of more easily obtaining the inducing effect or the conjugation effect of the electron-withdrawing group. In this respect, the silanol compound is preferably represented by the following general formula (1-1).

[ chemical formula 4]

Wherein, in the above general formula (1-1), R¹、R²And R³Each independently represents an electron-withdrawing group or a hydrogen atom (wherein R¹、R²And R³At least one of them represents an electron-withdrawing group). m represents 2 or 3.

The content of the silanol compound is not particularly limited and may be appropriately selected according to the purpose, and is preferably 20% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less, and particularly preferably 1% by mass or more and 10% by mass or less with respect to the cationic curing component.

The mass ratio of the silanol compound to the porous particles (silanol compound/porous particles) is not particularly limited, and may be appropriately selected according to the purpose, but is preferably 0.1 or more and 10 or less, more preferably 0.2 or more and 5 or less, and particularly preferably 0.5 or more and 2 or less.

< other ingredients >

Examples of the other components include: silane coupling agents, and the like.

Silane coupling agent

The silane coupling agent is a substance having 1 to 3 lower alkoxy groups in the molecule, and may have a group reactive with a functional group of the cationic curing component, for example, a vinyl group, a styryl group, an acryloyloxy group, a methacryloyloxy group, an epoxy group, an amino group, a mercapto group, or the like in the molecule. Since the latent curing agent used in the present invention is a cationic curing agent, a coupling agent having an amino group or a mercapto group can be used without substantially capturing a cationic species occurring in the amino group or the mercapto group.

Examples of the silane coupling agent include vinyltris (β -methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, gamma-styryltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-acryloxypropyltrimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane, N- β - (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-aminopropyltriethoxysilane, N-phenyl-gamma-aminopropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, and gamma-chloropropyltrimethoxysilane.

The content of the silane coupling agent is not particularly limited and may be appropriately selected according to the purpose, and is preferably 1 mass% to 100 mass%, more preferably 2 mass% to 50 mass%, with respect to the porous particles.