JPH11302372A - Thermosetting composition, its curing and cured product obtained by the same curing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new rapidly curable thermosetting composition excellent in mechanical properties, electrical properties, adhesion, heat, moisture and chemical resistances and storage stability, etc., and usable in producing a new cured product useful as a substitute for an epoxy resin in the fields of applications to coating materials, coating agents, adhesives, electrical insulating materials, semiconductor encapsulants, etc., to provide a method for curing the composition and to produce the new cured product obtained by the method. SOLUTION: This thermosetting composition contains 5-95 pts.wt. of an oxetane compound having 1-4 oxetane rings in the molecule, 95-5 pts.wt. of an oxirane compound having >=1 oxirane rings in the molecule and a latent heat cationic polymerizing catalyst in an amount of 0.01-20 pts.wt. based on 100 pts.wt. of the sum total of both the compounds. The new cured product is obtained by heating the composition at 50-200 deg.C temperature for 1 min to 50 h and carrying out the cationic polymerization reaction and has a three- dimensional network structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermosetting composition for producing a novel cured product, comprising an oxetane compound, an oxirane compound and a heat-latent cationic polymerizable catalyst, a method for curing the composition, and a method for curing the composition. It relates to a novel cured product obtained by the method. More specifically, 5-95 parts by weight of an oxetane compound having 1-4 oxetane rings in the molecule, 95-5 parts by weight of a compound having one or more oxirane rings in the molecule, and quaternary ammonium Salt, a phosphonium salt, a sulfonium salt, a diazonium salt and an iodonium salt in an amount of at least one heat-latent cationic polymerizable catalyst selected from the group consisting of oxetane compound and oxirane compound in an amount of 0.01 part by weight based on 100 parts by weight.
A thermosetting composition which can produce a novel cured product by heating; heating the thermosetting composition at a temperature of 50 to 200 ° C. for 1 minute to 50 hours to obtain the oxetane A method for curing the thermosetting composition, the method comprising cationically polymerizing a compound and an oxirane compound;
And a novel cured product produced by the curing method.

[0002] The thermosetting composition of the present invention has a composition of 50 to 200
° C, the composition is rapidly cured by the action of the cationic polymerization catalyst formed from the heat-latent cationic polymerizable catalyst (the oxetane ring in the oxetane compound and the oxirane ring in the oxirane compound). Ring-opening polymerization reaction) to form a novel cured product with an insoluble and infusible three-dimensional network structure, resulting in excellent mechanical properties (such as tensile strength and hardness) and electrical properties (such as electrical insulation). ), Adhesiveness, heat resistance, moisture resistance, chemical resistance, etc. As substitutes for epoxy resin, paints, coatings, adhesives, electrical insulating materials, IC and ultra LSI sealing materials, laminates And other electric / electronic parts, adhesion of reinforced steel sheets, composite materials, etc.

[0003]

2. Description of the Related Art Epoxides, which are three-membered ring ether compounds, ie, oxiranes, and oxetane, which is a four-membered ring ether compound, exhibit high reactivity because the carbon-oxygen bond is polarized. Recently, utilizing the high reactivity of these oxiranes and oxetanes in cationic polymerization,
Some photocationic polymerization of oxirane and / or oxetane in the presence of a cationic photopolymerization initiator has been reported (JP-A-6-16804, JP-A-7-53).
711, JP-A-7-62082 and JP-A-7-62082
-173279, JP-A-8-230348, JP-A-8-239623, JP-A-8-269
392, JP-A-8-277385 and JP-A-9-31186). For example, JP-A-6-16804 discloses the following general formula (VIII)

[0004]

Embedded image

(Wherein R ₇ is a hydrogen atom, a fluorine atom,
R ₈ is a linear or branched alkylene group, a linear or branched poly (alkyleneoxy) group, a di- or tetravalent silicon-containing group, such as a monovalent hydrocarbon group or a monovalent fluorine-substituted hydrocarbon group. Group, a divalent to tetravalent polyvalent group such as a divalent to tetravalent aromatic ring-containing hydrocarbon group, Z is an oxygen atom or a sulfur atom, and m is 2, 3 or 4. 3 shown
A photocurable oxetane composition containing the 3-substituted oxetane monomer, wherein a mixture of the substituted oxetane monomer and a cationic photopolymerization initiator such as a triarylsulfonium salt or a diaryliodonium salt is exposed to ultraviolet light. A method for curing these oxetane monomers, and a cross-linked propyloxy polymer obtained by the curing method, wherein at least one compound is present in a molecule such as a silicone epoxide, a biscyclic aliphatic epoxide, or an epoxide lacking addition strain of a condensed ring. It is disclosed that a mixture of a monomer having an oxirane ring and the cationic photopolymerization initiator is exposed to ultraviolet light.

Further, JP-A-7-53711, JP-A-7-62082, JP-A-7-173279, JP-A-8-230348, and JP-A-8-239.
623, JP-A-8-269392, JP-A-8-277385 and JP-A-9-31186 disclose compounds having two or more oxetane rings in a molecule, and one or more oxetane rings in a molecule. An active energy ray-curable composition comprising a compound having an oxirane ring of the formula (I) and a compound that initiates cationic polymerization by irradiation with active energy rays such as ultraviolet rays, X-rays, and electron beams is disclosed. There is a description that the speed can be equal to or better than the curing speed of the compound having an oxetane ring used.

[0007] However, in the cationic photopolymerization in which an oxetane compound or an oxirane compound is irradiated with an active energy ray in the presence of a cationic photopolymerization initiator as described above, the composition cures rapidly but must be irradiated with an active energy ray. If a hardening reaction does not occur, it is difficult to apply it to large parts that cannot be irradiated with active energy rays or articles that have a structure that cannot be irradiated with active energy rays. There were problems such as becoming. Accordingly, there has been a strong demand for a large-sized component that cannot be irradiated with active energy rays or an article having a structure that cannot be irradiated with active energy rays, that has excellent storage stability and that cures quickly. On the other hand, JP-A-8-2
No. 69391 and JP-A-8-269165 disclose a heat-latent cationic polymerizable catalyst comprising an epoxy group-containing compound and an onium salt such as the quaternary ammonium salt, phosphonium salt, sulfonium salt, diazonium salt or iodonium salt. It is described that a coating film is obtained by heat-curing a composition comprising at least the following, but a thermosetting reaction between the epoxy group-containing compound, that is, the oxirane compound and the heat-latent cationic polymerizable catalyst. Is slow, the solidification time until the desired cured product is obtained is prolonged, and there is still room for improvement in productivity.

Accordingly, the present inventors have developed a quaternary ammonium salt, a phosphonium salt, a sulfonium salt, a diazonium salt and an iodonium salt for the purpose of developing a new reaction of a compound having an oxetane ring and developing it for polymer synthesis. As a result of intensive studies on the thermal cationic polymerization reaction of an oxetane compound having 1 to 4 oxetane rings in the molecule by at least one type of heat-latent cationic polymerizable catalyst selected from the group consisting of salts, the oxetane compound A mixture containing 0.01 to 20 parts by weight of the above-mentioned heat latent cationic polymerizable catalyst per 100 parts by weight is excellent in rapid curability by heat, and the mixture is heated at a temperature of 50 to 200 ° C. for 1 minute to 50 minutes. By heating for a period of time to carry out the ring-opening cationic polymerization of the oxetane compound, a tertiary Reported that the cured product of the insoluble and infusible having a network structure is obtained (see Japanese Patent Application No. Hei 10-72508 specification).

[0009]

However, a thermosetting oxetane composition comprising a mixture of 100 parts by weight of the oxetane compound and 0.01 to 20 parts by weight of the heat-latent cationic polymerization catalyst is heated at 50 to 200 ° C. At a temperature of 1 minute to 50
By heating for a long time, the cured product obtained by thermal cationic polymerization has still to be improved in terms of mechanical properties (tensile strength, hardness, etc.). An object of the present invention is to provide a thermosetting curable composition comprising an oxetane compound, an oxirane compound and a heat-latent cationic polymerizable catalyst, which has excellent storage stability and mechanical properties (tensile strength, hardness, etc.) and can be rapidly cured by heat. An object of the present invention is to provide a composition, a method for curing the composition, and a novel cured product obtained by the method.

[0010]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have investigated the availability of the cured product obtained from the thermal cation polymerization reaction of the oxirane compound to various fields and the thermal cation polymerization of the oxetane compound. As a result of intensive studies on a method for producing a cured product having both rapid curing properties in a polymerization reaction, 5 to 95 parts by weight of an oxetane compound having 1 to 4 oxetane rings in the molecule, and 1 or more in the molecule 95 to 5 parts by weight of an oxirane compound having an oxirane ring, and 100 parts by weight of the oxetane compound and the oxirane compound per 100 parts by weight of the heat-latent cationically polymerizable catalyst which forms a cationically polymerizable catalyst by heating.
50 to 200 ° C.
Is heated at a temperature of 1 minute to 50 hours to carry out a ring-opening cationic polymerization reaction of the oxetane compound and the oxirane compound, whereby a novel insoluble and infusible thermosetting product having an intermolecularly crosslinked three-dimensional network structure is obtained. Was found, and the present invention was completed.

That is, a first invention according to claim 1 is that the compound (A) having 1 to 4 oxetane rings in the molecule is 5 to 95 parts by weight and one compound in the molecule is used. 95 to 5 parts by weight of at least one kind of the compound (B) having an oxirane ring and at least one kind of the heat-latent cationic polymerizable catalyst (C) are the total of the compound (A) and the compound (B). 0.0 to 100 parts by weight
This can be achieved by providing a thermosetting composition comprising 1 to 20 parts by weight. According to a second aspect of the present invention, at least one kind of the compound (A) having 1 to 4 oxetane rings in the molecule has 5 to 95 parts by weight and one or more oxirane rings in the molecule. 95 to 5 parts by weight of at least one kind of the compound (B), and a heat-latent cationically polymerizable catalyst (C)
Is 0.01 to 20 parts by weight based on 100 parts by weight of the total amount of the compound (A) and the compound (B).
A method for producing a cured product, which comprises heating a mixture consisting of parts by weight at a temperature of 50 to 200 ° C. for 1 minute to 50 hours, and a third invention according to claim 3, wherein 1
5 to 95 parts by weight of at least one compound (A) having from 4 to 4 oxetane rings, and 95 to 95 parts by weight of at least one compound (B) having at least one oxirane ring in the molecule.
5 parts by weight and 0.01 to 20 parts by weight of at least one kind of the heat latent cationic polymerizable catalyst (C) based on 100 parts by weight of the total amount of the compound (A) and the compound (B). At a temperature of 50-200 ° C. for 1 minute
It can be achieved by providing each of the cured products obtained by heating for 50 hours.

According to a fourth aspect of the present invention, the heat-latent cationically polymerizable catalyst (C) is a quaternary ammonium salt represented by the following general formula (I): A phosphonium salt represented by the following general formula (III), (IV) or (V); a sulfonium salt represented by the following general formula (VI)
And at least one onium salt selected from the group consisting of a diazonium salt represented by the following formula and an iodonium salt represented by the following general formula (VII): Can be achieved.

According to a fifth aspect of the present invention, the heat latent cationically polymerizable catalyst (C) is a quaternary ammonium salt represented by the following general formula (I): A phosphonium salt represented by the following general formula (III), (IV) or (V); a sulfonium salt represented by the following general formula (VI)
And at least one onium salt selected from the group consisting of a diazonium salt represented by the following general formula (VII) and a iodonium salt represented by the following general formula (VII): Can be achieved. According to a sixth aspect of the present invention, the heat-latent cationically polymerizable catalyst (C) has the following general formula (I)
A quaternary ammonium salt represented by the following general formula (II), a sulfonium salt represented by the following general formula (III), (IV) or (V):
A diazonium salt represented by the formula (I) and the following general formula (VII)
And at least one onium salt selected from the group consisting of iodonium salts represented by the formula (1).

[0014]

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(In the general formula (I), R _{1 to} R ₄ each represent an alkyl group having 1 to 20 carbon atoms;
12 alkenyl groups, aryl groups, alkaryl groups, alkanol groups having 1 to 20 carbon atoms or cycloalkyl groups having 5 to 10 carbon atoms, which may be the same or different from each other, and have a substituent It may or may not have. Two of R _{1 to} R ₄ are bonded to each other,
A heterocyclic ring having N, P, O or S as a hetero atom may be formed. Further, X is BF ₄ , PF ₆ , AsF ₆ ,
SbF ₆ , SbCl ₆ , (C ₆ F ₅ ) ₄ B, SbF
_{5 (OH), HSO 4,} p-CH 3 C 6 H 4 SO 3, H
Represents a monovalent anion selected from the group consisting of CO ₃ , H ₂ PO ₄ , CH ₃ COO and a halogen atom. )

[0016]

Embedded image (In the general formula (II), R _{1 to} R ₄ and X each represent
It is the same as R _{1 to} R ₄ and X in the general formula (I). )

[0017]

Embedded image (In the general formula (III), R _{1 to} R ₃ and X each represent
It is the same as R _{1 to} R ₃ and X in the general formula (I), and two of R _{1 to} R ₃ are bonded to each other to form N,
A heterocyclic ring having P, O or S as a hetero atom may be formed. )

[0018]

Embedded image (In the general formula (IV), R ₁ , R ₂ and X are each
It is the same as R ₁ , R ₂ and X in the general formula (I), and R ₁ and R ₂ may combine with each other to form a heterocyclic ring having N, P, O or S as a hetero atom. . Ar represents an aryl group which may or may not have a substituent. )

[0019]

Embedded image (In the general formula (V), R _{1 to} R ₄ and X each represent
It is the same as R _{1 to} R ₄ and X in the general formula (I). Ar is the same as Ar in the general formula (IV). )

[0020]

Embedded image (In the general formula (VI), Ar and X are the same as Ar in the general formula (IV) and X in the general formula (I), respectively.)

[0021]

Embedded image (In the general formula (VII), X is X in the above general formula (I)
R ₅ and R ₆ may be the same or different from each other, and may be an aryl group which may or may not have a substituent. )

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The thermosetting composition of the present invention is a compound having at least one oxetane compound (A), which is a compound having 1 to 4 oxetane rings in the molecule, and a compound having one or more oxirane rings in the molecule. A mixture of at least one oxirane compound (B) and at least one heat latent thione polymerizable catalyst (C) described below, which can produce the novel cured product of the present invention by a curing method described later. It is.

First, the oxetane compound (A), which is a component of the thermosetting composition of the present invention, will be described. The oxetane compound (A) used in the present invention
Is a compound having 1 to 4 oxetane rings in the molecule, as described above. The compound having one oxetane ring in the molecule is represented by the following general formula (IX)

[0024]

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(Wherein, R ₉ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group,
Examples thereof include a linear or branched alkyl group such as a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, and an isohexyl group. Examples of the compound having one oxetane ring in the molecule include 3-hydroxymethyloxetane in which R ₉ is a hydrogen atom in the formula (IX), and 3-methyl-3-hydroxymethyloxetane in which R ₉ is a methyl group. And the use of 3-ethyl-3-hydroxymethyloxetane wherein R ₉ is an ethyl group is preferred, and among these, the use of 3-methyl-3-hydroxymethyloxetane and 3-ethyl-3-hydroxymethyloxetane is particularly preferred.

On the other hand, a compound having two oxetane rings in the molecule is represented by the following general formula (X)

[0027]

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(In the formula, R ₁₀ is the same group as R ₉ in the general formula (IX), and R ₁₁ is an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a 1,2-
A linear or branched alkylene group having 1 to 12 carbon atoms such as a butylene group, a 1,3-butylene group, a 2,3-butylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a propenylene group, A linear or branched unsaturated hydrocarbon group having 1 to 12 carbon atoms such as a methylpropenylene group or a butenylene group, represented by the following general formula (XI)

[0029]

Embedded image An aromatic hydrocarbon group represented by the following general formula (XII)

[0030]

Embedded image An aromatic hydrocarbon group represented by the following formula

[0031]

Embedded image A carbonyl group represented by the following general formula (XIII)

[0032]

Embedded image An alkylene group containing a carbonyl group represented by the following formula

[0033]

Embedded image A carbonyl group-containing alicyclic hydrocarbon group represented by the following formula

[0034]

Embedded image And a carbonyl group-containing aromatic hydrocarbon group represented by the following general formula (XIV):

[0035]

Embedded image

2 selected from the group consisting of
It is a group having a valence of two. And R ₁₂ represents 1 to 4 carbon atoms such as a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Having a linear or branched alkyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group and ter
Alkoxy groups having 1 to 4 carbon atoms such as t-butoxy group, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, nitro group, cyano group, mercapto group, methoxycarbonyl group, ethoxycarbonyl group , A lower alkylcarboxylate group having 1 to 4 carbon atoms such as a propoxycarbonyl group and a butoxycarbonyl group, a carboxyl group, a carbamoyl group, and a carbon atom group such as a methylcarbamoyl group, an ethylcarbamoyl group, a propylcarbamoyl group and a butylcarbamoyl group. Is a group having a valence of 1 selected from the group consisting of 1 to 4 N-alkylcarbamoyl groups, and R ₁₃ is O, S,
CH ₂ , NH, SO, SO ₂ , C (CF ₃ ) ₂ or C
(CH ₃ ) ₂ . And Y is optionally substituted 1
A linear or branched alkylene group having up to 12 carbon atoms,

[0037]

Embedded image Or

Embedded image An optionally substituted alicyclic hydrocarbon group having a valence of 2, such as a group represented by

[0038]

Embedded image

Alternatively,

Embedded image And k is an integer of 1 to 20), and is a bisoxetane represented by the following formula:

In the present invention, the compound having two oxetane rings in the molecule is preferably a compound in which R ₁₀ is a lower alkyl group, more preferably a methyl group and an ethyl group in the formula (X). R ₁₁ in the general formula (X) may be a linear alkylene group having 1 to 12 carbon atoms or a group represented by the general formula (X
An aromatic hydrocarbon group having a valence of 2 represented by I) is preferable, and a hexamethylene group, and a group in which R ₁₂ is a hydrogen atom in the general formula (XI) is more preferable. Therefore, preferred specific examples of the compound having two oxetane rings in the molecule include the following formulas (1) to (7)
And the like, such as bisoxetane.

[0041]

Embedded image

That is, in the compounds represented by the formulas (1) to (4), in the general formula (X), R ₁₀ is an ethyl group, and R ₁₁ is an ethylene group, a tetramethylene group, or a hexamethylene group, respectively. And octamethylene groups. The compound represented by the formula (5) is a bisoxetane in which, in the general formula (X), R ₁₀ is an ethyl group, R ₁₁ is the general formula (XI), and R ₁₂ is a hydrogen atom. Further, the compound represented by the formula (6) is bisoxetane wherein R ₁₀ is an ethyl group and R ₁₁ is a carbonyl group in the general formula (X). In the compound represented by the formula (7), R ₁₀ is an ethyl group and R ₁₁ is a compound represented by the formula (X) in the formula (X).

[0043]

Embedded image Is a carbonyl group-containing aromatic hydrocarbon group represented by the formula:

The compound having 3 or 4 oxetane rings in the molecule used in the present invention is represented by the following general formula (XV)

[0045]

Embedded image

(In the formula, R ₁₄ is the same group as R ₉ in the general formula (IX), and R ₁₅ is a hydrocarbon group, a substituted hydrocarbon group, and the following general formula (XVI)

[0047]

Embedded image And a group represented by the following general formula (XVII)

[0048]

Embedded image

A polyvalent group having a valence of 3 or 4 selected from the group consisting of
It is. The above general formula (XVI) and the above general formula (XV
In II), each of Z ₁ and Z ₂ is an optionally substituted aliphatic, alicyclic or aromatic hydrocarbon group having a valence of 3 or 4, and p and q both represent 3 or 4 It is. ).

The trivalent or tetravalent hydrocarbon group or the substituted trivalent or tetravalent hydrocarbon group may be a monovalent carbon group such as a polyvalent group represented by the following formulas (8) to (10). To 12 branched alkylene groups.

[0051]

Embedded image

In the above formula (8), R ₁₆ represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group or a tert-butyl group. Is a lower alkyl group having 1 to 4 carbon atoms.

In the general formula (XVI), Z is a trivalent or tetravalent hydrocarbon group which is optionally substituted.
_{As 1}

[0054]

Embedded image

A trivalent aromatic hydrocarbon group represented by the following formula: Further, in the general formula (XVII), Z ₂ which is an optionally substituted tri- or tetravalent hydrocarbon group is represented by the following formula:

[0056]

Embedded image

Or

Embedded image And a trivalent alicyclic or aromatic hydrocarbon group represented by

As the compound having 3 or 4 oxetane rings in the molecule used in the present invention, specifically, in the above general formula (XV), R ₁₄ is a lower alkyl group, and R ₁₅ is It is preferably a branched alkylene group having a valence of 3 and having 1 to 12 carbon atoms represented by the formula (8) or a group represented by the general formula (XVI). Further, in the above general formula (XV), R ₁₄ is an ethyl group and R ₁₅ is the above formula (8) wherein R ₁₆ is an ethyl group, or Z _{1 in the} above general formula (XVI) is The following formula

[0059]

Embedded image And more preferably an aromatic hydrocarbon group represented by and p is 3.

The compound (A) having 1 to 4 oxetane rings in the molecule as described above used in the present invention can be produced as follows. For example, the general formula (IX)
The compound having one oxetane ring in the molecule represented by the following formula (11)
(See J. Am. Chem. Soc., 1957, 79)
It can be synthesized from 1,3-diol.

[0061]

Embedded image

Specifically, in the general formula (IX), R
3-Ethyl-3-hydroxymethyloxetane wherein ₉ is an ethyl group can be obtained from trimethylolpropane and diethyl carbonate by the method of Pattisson described above.

In the general formula (X), R ₁₁ is 1 to 1
A linear or branched alkylene group having 2 carbon atoms, a linear or branched unsaturated hydrocarbon group having 1 to 12 carbon atoms, or a compound represented by formula (XI) or (XII) Bisoxetane compounds containing two ether groups in the molecule, which is an aromatic hydrocarbon group shown,
3-ethyl- synthesized by the method of Pattisson described above.
It can be synthesized from 3-hydroxymethyloxetane and dihalide as shown in the following chemical formula (12).

[0064]

Embedded image

In the above formula (12), R
_11a is a linear or branched alkylene group having 1 to 12 carbon atoms, a linear or branched unsaturated hydrocarbon group having 1 to 12 carbon atoms, or the general formula (X
I) or an aromatic hydrocarbon group represented by the general formula (XII), and X ₁ is a bromine atom, a chlorine atom or an iodine atom. In the general formula (X), R
₁₁ is an alkylene group containing a carbonyl group in which k is an integer of 1 to 6 in the general formula (XIII), or the aforementioned formula

[0066]

Embedded image A bisoxetane compound containing two ester groups in a molecule, which is a carbonyl group-containing aromatic hydrocarbon group, represented by, for example, 3-ethyl-3-hydroxymethyloxetane synthesized by the above-mentioned Pattisson method and diester The compound can be prepared from the compound as shown in the following formula (13) using a transesterification reaction as described in US Pat. No. 3,278,554.

[0067]

Embedded image

In the above formula (13), R ₁₇ is
A linear or branched alkylene group having 1 to 6 carbon atoms, or the following formula:

[0069]

Embedded image

[0070] an aromatic hydrocarbon group shown by, R ₁₈
Is an optionally substituted aliphatic, alicyclic or aromatic hydrocarbon group. Further, in the general formula (XV), a compound in which n is 3 or 4, that is, a compound having 3 or 4 oxetane rings in the molecule can be prepared in the same manner as in the above bisoxetane compound. For example, when R _11a in the formula (12) is a linear or branched alkylene group containing 3 or 4 substitutable groups, a suitable compound represented by the general formula (XV) can be synthesized. .

In the present invention, as the compound (A) having 1 to 4 oxetane rings in the molecule constituting the thermosetting composition, the compound having one oxetane ring in the molecule described above, A bisoxetane compound having two oxetane rings, or one compound selected from compounds having three or four oxetane rings in the molecule may be used alone, or two or more of these may be used in combination. It may be something.

Next, a compound having one or more oxirane rings in the molecule, ie, the oxirane compound (B), which is the second component constituting the thermosetting composition of the present invention, is one or more in the molecule. The following equation

[0073]

Embedded image

A 1,2-epoxide represented by the formula:
Any of monomers, oligomers or polymers can be used. Specific examples of the oxirane compound (B) include:
Conventionally known aliphatic epoxy resins, alicyclic epoxy resins and aromatic epoxy resins are exemplified. Hereinafter, the epoxy resin means a monomer, an oligomer or a polymer.

Preferred examples of the aliphatic epoxy resin include the following general formula (XVIII)

[0076]

Embedded image

(Wherein R ₁₉ and R ₂₀ are each independently a hydrogen atom or a hydrocarbyl containing 1 to 20 carbon atoms). Oxirane compounds having one epoxy group in the molecule represented by the following formula: Can be Typical examples are ethylene oxide, propylene oxide, 1,
2-epoxybutane, cis 2,3-epoxybutane, trans 2,3-epoxybutane, butadiene monooxide, epoxy hexane, epoxy octane, epoxy decane, epoxide decane, epoxy hexadecane, alkylene oxide such as epoxy octadecane, epoxy hexene, Compounds having an epoxy group such as epoxy octene and a double bond unsaturated group, compounds having a glycidyl group such as glycidyl methyl ether, glycidyl isopropyl ether, glycidyl butyl ether, glycidyl acrylate, glycidyl methacrylate, monoglycidyl ether of an aliphatic higher alcohol, etc. A compound containing one epoxy group in the molecule thereof, and a di- or poly-glycol of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof Oxirane compound having two or more epoxy groups in the molecule, such as glycidyl ether. Representative examples of the oxirane compound having two or more epoxy groups in the molecule include diepoxybutane, diepoxyoctane, oligomers having various epoxy groups at both ends, diglycidyl ether of ethylene glycol,
Diglycidyl ether of alkylene glycol such as diglycidyl ether of 1,4-butanediol or diglycidyl ether of 1,6-hexanediol, diglycidyl ether of tetraethylene glycol, di- or triglycidyl of glycerin or an alkylene oxide adduct thereof. Ether, polyglycidyl ether of polyhydric alcohol such as triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol or its alkylene oxide adduct, polyalkylene glycol such as diglycidyl ether of polypropylene glycol or its alkylene oxide adduct or The diglycidyl ether of the alkylene oxide adduct is exemplified. Here, as the alkylene oxide in the alkylene oxide adduct, ethylene oxide, propylene oxide, and the above-mentioned alkylene oxides can be suitably mentioned.

The alicyclic epoxy resin is obtained by epoxidizing a compound having at least one cycloalkene ring such as a cyclohexene or cyclopentene ring with a suitable oxidizing agent such as hydrogen peroxide or peracid. Cyclohexene oxide or cyclopentene oxide-containing compounds are preferred, and specific examples include the following formula:

[0079]

Embedded image

In addition to the alicyclic oxirane compound having one epoxy group in the molecule represented by the above and the like, the alicyclic oxirane compound having two epoxy groups in the molecule is represented by the following formula:

[0081]

Embedded image

3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate represented by the following formula:

[0083]

Embedded image

(Where n ₀ is an integer of ₀ to 100) represented by the following formula:

[0085]

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And the like. Alicyclic oxirane compounds represented by

Preferred as the aromatic epoxy resin are aromatic oxirane compounds having one epoxy group in a molecule such as monoglycidyl ether of phenol, monoglycidyl ether of cresol, epoxypropylbenzene and styrene oxide, and the like. A polyhydric phenol having at least one aromatic nucleus or an aromatic oxirane compound having two or more epoxy groups in a molecule such as a di- or polyglycidyl ether produced by reacting an alkylene oxide adduct thereof with epichlorohydrin; is there. Examples of the aromatic oxirane compound having two or more epoxy groups in the molecule include di- or polyglycidyl ether of bisphenol A or its alkylene oxide adduct, di- or polyglycidyl of hydrogenated bisphenol A or its alkylene oxide adduct Ether and novolak type epoxy resin. Here, as the alkylene oxide in the alkylene oxide adduct, the alkylene oxide described above can be suitably mentioned, as in the case of the aliphatic epoxy resin.

In the present invention, the above-mentioned aliphatic epoxy resin, alicyclic epoxy resin and aromatic epoxy resin may be used as the compound (B) having one or more oxirane rings in the molecule constituting the thermosetting composition. May be used alone, or two or more of these may be used in combination.

In the present invention, the compound (B)
Is from 5 to 95 parts by weight, preferably from 5 to 90 parts by weight, more preferably from 10 to 80 parts by weight, based on 100 parts by weight of the total of the compound (A) and the compound (B). is there. When the compounding amount of the compound (B) exceeds 95 parts by weight, the curing reaction speed described in detail below, that is, the compound (A) and the compound (B) and the heat-latent cationic polymerizable catalyst (C ), The effect of the present invention of increasing the rate of the thermal cationic polymerization reaction with the above and shortening the solidification time until a cured product is obtained is not sufficient. Further, if the compounding amount of the compound (B) is less than 5 parts by weight, further improvement of the rapid curing property in this curing reaction cannot be expected, and also the mechanical properties (tensile strength and hardness , Etc.) are not preferred.
In order to surely prevent the occurrence of these undesired phenomena, it is needless to say that the compounding amount of the compound (B) is preferably within the above-mentioned preferable range, and more preferably within the above-mentioned more preferable range. No.

On the other hand, the heat-latent cationically polymerizable catalyst (C), which is another component of the thermosetting composition of the present invention, is heated to convert the cationically polymerizable catalyst as described above. Ring opening of the oxetane ring formed in the compound (A) having 1 to 4 oxetane rings in the molecule and the oxirane ring in the compound (B) having one or more oxirane rings in the molecule It catalyzes a curing reaction by cationic polymerization. That is, as long as the oxetane compound (A) and the oxirane compound (B) are blended with the oxetane compound (B) and left at room temperature, they are stable for a long period of time. It is a so-called latent curing agent that forms and initiates and accelerates the curing reaction.

Specific examples of the heat-latent cationic polymerizable catalyst (C) include various onium salts as shown below. For example, a quaternary ammonium salt represented by the following general formula (I), a phosphonium salt represented by the following general formula (II), and a sulfonium salt represented by the following general formula (III), (IV) or (V) is there.

[0092]

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(However, in the general formula (I), R _{1 to} R
₄ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, an aryl group, an alkaryl group, an alkanol group having 1 to 20 carbon atoms or a cycloalkyl having 5 to 10 carbon atoms, respectively. An alkyl group, which may be the same or different, and may or may not have a substituent. Two of R _{1 to} R ₄ may be bonded to each other to form a heterocyclic ring having N, P, O or S as a hetero atom. Further, X is BF ₄ , P
F ₆ , AsF ₆ , SbF ₆ , SbCl ₆ , (C ₆ F ₅ )
_{4 B, SbF 5 (OH)} , HSO 4, p-CH 3 C 6 H
Represents a counter ion selected from the group consisting of ₄ SO ₃ , HCO ₃ , H ₂ PO ₄ , CH ₃ COO and a halogen atom, that is, a monovalent anion. )

[0094]

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[0095] (wherein, in the general formula (II), R ₁ ~R ₄ and X are each, R ₁ ~ in the general formula (I)
Same as R ₄ and X. )

[0096]

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[0097] (wherein, in the general formula (III), R ₁ ~R ₃ and X are each, R ₁ ~ in the general formula (I)
It is the same as R ₃ and X, and two of R _{1 to} R ₃ may combine with each other to form a heterocyclic ring having N, P, O or S as a hetero atom. )

[0098]

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[0099] (wherein, in the general formula _{(IV), R 1, R} 2 and X are each, R ₁ in the general formula (I),
It is the same as R ₂ and X, and R ₁ and R ₂ may combine with each other to form a heterocyclic ring having N, P, O or S as a hetero atom. Ar represents an aryl group which may or may not have a substituent. )

[0100]

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[0102] (wherein, in the general formula (V), R ₁ ~R ₄ and X are each, R ₁ ~ in the general formula (I)
Same as R ₄ and X. Ar is the same as Ar in the general formula (IV). )

In the formulas (I) to (V), the alkyl group having 1 to 20 carbon atoms as R ₁ , R ₂ , R ₃ or R ₄ has a substituent. Also,
Examples thereof include a linear or branched alkyl group which may not have, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n -Pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl Group, octadecyl group, nonadecyl group and eicosyl group. As the alkenyl group having 3 to 12 carbon atoms as R ₁ , R ₂ , R ₃ or R ₄ , a linear or branched alkenyl group which may or may not have a substituent. And, for example, an n-propenyl group, n
-Butenyl group, sec-butenyl group, tert-butenyl group, n-pentenyl group, sec-pentenyl group, hexenyl group, n-heptenyl group, sec-heptenyl group,
Examples include an octenyl group, a nonenyl group, a decenyl group and an unenyl group.

The aryl group as R ₁ , R ₂ , R ₃ or R ₄ includes, for example, a substituted or unsubstituted phenyl group, naphthyl group or anthracene group, and a phenyl group is particularly preferred. Examples of the alkaryl group as R ₁ , R ₂ , R ₃ or R ₄ include those composed of the above-mentioned alkyl and aryl groups having 1 to 20 carbon atoms. The alkanol group having 1 to 20 carbon atoms as R ₁ , R ₂ , R ₃ or R ₄ may be a straight-chain or branched alkanol group which may or may not have a substituent. Include, for example, an ethanol group, an n-propanol group, an isopropanol group,
n-butanol group, sec-butanol group, tert-
Butanol group, n-pentanol group, sec-pentanol group, 1-hexanol group, 1-heptanol group, 1
-Octanol group, 1-nonanol group, 1-decanol group, 1-undecanol group, 1-dodecanol group, 1-
Tridecanol group, 1-tetradecanol group, 1-pentadecanol group, 1-hexadecanol group, 1-heptadecanol group, 1-octadecanol group, 1-nonadecanol group, 1-eicosanol group and the like. Can be Further, as the cycloalkyl group having 5 to 10 carbon atoms as R ₁ , R ₂ , R ₃ or R ₄ ,
A cycloalkyl group which may or may not have a substituent and which may have a branch is included, and examples thereof include a cyclopentyl group, a 2-methylcyclopentyl group, a cyclohexyl group and a cycloheptyl group. On the other hand, in the general formulas (IV) and (V), the aryl group which may or may not have a substituent as Ar includes:
Examples include a substituted or unsubstituted phenyl group or a naphthyl group.

In the general formulas (I) to (V), examples of the substituent include a halogen atom such as a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group and an n-butyl group. , Sec-butyl group, te
rt-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-
1 to 1 carbon atoms such as a heptyl group and an n-octyl group
8 alkyl groups, cyclopentyl groups, cyclohexyl groups, cycloheptyl groups and other cycloalkyl groups having 5 to 7 carbon atoms, or methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy. Group, a tert-butoxy group, a pentyloxy group, an isopentyloxy group, a sec-pentyloxy group, a hexyloxy group, an isohexyloxy group, a heptyloxy group, and an octyloxy group. No.

Examples of the quaternary ammonium salt represented by the general formula (I) include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, and tetraethylammonium p
-Toluenesulfonate, N, N-dimethyl-N-benzylanilinium antimony hexafluoride, N, N-dimethyl-N-benzylanilinium boron tetrafluoride, N, N
-Dimethyl-N-benzylpyridinium antimony hexafluoride, N, N-diethyl-N-benzyltrifluoromethanesulfonic acid, N, N-dimethyl-N- (4-methoxybenzyl) pyridinium antimony hexafluoride, N, N
-Diethyl-N- (4-methoxybenzyl) toluidinium antimony hexafluoride; Specific examples of the phosphonium salt represented by the general formula (II) include, for example, ethyltriphenylphosphonium antimony hexafluoride and tetrabutylphosphonium antimony hexafluoride.

Examples of the sulfonium salt represented by formula (III), (IV) or (V) include, for example, triphenylsulfonium boron tetrafluoride, triphenylsulfonium antimony hexafluoride, and triphenylsulfonium hexafluoride. Arsenic arsenide, tri (4-methoxyphenyl) sulfonium arsenide hexafluoride, diphenyl (4-phenylthiophenyl) sulfonium arsenic hexafluoride, Adekaopton SP-150 (manufactured by Asahi Denka Kogyo KK, counter ion: P
F ₆ ), Adeka Opton SP-170 (manufactured by Asahi Denka Kogyo KK, counter ion: SbF ₆ ), Adeka Opton CP-66
(Made by Asahi Denka Kogyo KK, counter ion: SbF ₆ ), Adeka Opton CP-77 (made by Asahi Denka Kogyo KK, counter ion: Sb
F _6), San-Aid SI-60L (Sanshin Chemical Industry Co., Ltd.,
Counter ion: SbF ₆ ), Sun-Aid SI-80L (manufactured by Sanshin Chemical Industries, counter ion: SbF ₆ ), Sun-Aid SI
-100 L (manufactured by Sanshin Chemical Industries, counter ion: Sb
_{F 6), CYRACURE UVI-6974} ( Union Carbide Corporation, counter ion: SbF _6), CYRA
CURE UVI-6990 (manufactured by Union Carbide Co., counter ion: PF ₆ ), UVI-508 (General
Electric), UVI-509 (General Electric), FC-508 (Minnesota Mining and Manufacturing), FC-
509 (manufactured by Minnesota Mining and Manufacturing Co., Ltd.), CD-1010 (manufactured by Sartomer Co., Ltd.), CD-1011 (Sartomer Co., Ltd.) and CI series (manufactured by Nippon Soda Co., Ltd., counter ion: PF _6, SbF ₆₎
And the like.

Further, in the present invention, a diazonium salt represented by the following general formula (VI) or an iodonium salt represented by the following general formula (VII) may be used as the heat-latent cationic polymerizable catalyst (C). it can.

[0108]

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(However, in the general formula (VI), Ar and X
Is the same as Ar in the general formula (IV) and X in the general formula (I), respectively. )

[0110]

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(Wherein, in the general formula (VII), X is the same as X in the general formula (I), and R ₅ and R
₆ is an aryl group which may be the same or different, and may or may not have a substituent. )

In the above formulas (VI) and (VII), specific examples of the aryl group which may or may not have a substituent as Ar and the monovalent anion as X Is as described above. Also, R ₅ and R ₆
Examples of the aryl group which may or may not have a substituent include a substituted or unsubstituted phenyl group, a naphthyl group and an anthracene group, and a phenyl group is particularly preferable. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group and a tert-butyl group. An alkyl group having 1 to 8 carbon atoms such as a group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, an isohexyl group, an n-heptyl group and an n-octyl group, a cyclopentyl group, a cyclohexyl group and a cycloheptyl A cycloalkyl group having 5 to 7 carbon atoms such as a group, or a methoxy group, an ethoxy group, a propoxy group,
Isopropoxy group, butoxy group, isobutoxy group, se
1 carbon atom such as c-butoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, sec-pentyloxy group, hexyloxy group, isohexyloxy group, heptyloxy group and octyloxy group
To 8 alkoxy groups.

Specific examples of the diazonium salt represented by the general formula (VI) include AME manufactured by American Can Inc.
RICURE (counter ion: BF ₄ ) and ULTRASET (counter ion: BF ₄ , PF ₆ ) manufactured by Asahi Denka Kogyo KK can be exemplified. Specific examples of the iodonium salt represented by the general formula (VII) include diphenyliodonium arsenide hexafluoride, di-4-chlorophenyliodonium hexafluoride, di-4-bromophenyliodonium hexafluoride arsenic, phenyl (4 -Methoxyphenyl) iodonium arsenic hexafluoride, UVE series manufactured by General Electric, Minnesota Mining and
FC Series manufactured by Manufacturing, UV-9310C manufactured by Toshiba Silicone (counter ion: SbF ₆ )
And Photoinitiator 2074 from Rhone-Poulenc
(Counter ion: (C ₆ F ₅ ) ₄ B).

In the present invention, the heat-latent cationically polymerizable catalyst (C) comprises a compound (A) having 1 to 4 oxetane rings in the molecule and a compound having one or more oxirane rings in the molecule. 0.01 to 20 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the total amount of compound (B)
Used in an amount of 10 parts by weight. When the amount of the heat latent cationic polymerizable catalyst (C) used is less than 0.01 part by weight per 100 parts by weight of the total amount of the compound (A) and the compound (B), the compound (A) and the compound (B)
In addition, the cationic polymerization reaction by heating the mixture of the catalyst (C) does not sufficiently proceed, and a cured product having a high degree of crosslinking, which is the object of the present invention, cannot be obtained in high yield. Even when the amount of the heat latent cationic polymerizable catalyst (C) used is more than 20 parts by weight per 100 parts by weight of the total amount of the compound (A) and the compound (B), the catalyst (C) The effect of promoting the cationic polymerization reaction by using a large amount thereof is hardly improved, so it is not preferable from the viewpoint of economy, and also the obtained cured product is deteriorated in moisture resistance and chemical resistance, and discoloration occurs. Is not preferred. Needless to say, in order to reliably prevent the occurrence of these undesirable phenomena, the amount of the heat-latent cationically polymerizable catalyst (B) should be within the above-mentioned preferable range.

Therefore, as described above, the thermosetting composition according to one embodiment of the present invention contains one molecule in the molecule.
At least one kind of the compound (A) having at least 4 oxetane rings, at least one kind of the compound (B) having one or more oxirane rings in the molecule, and the heat-latent cationic polymerizable catalyst (C). It is a mixture obtained by blending at least one kind with the above ratio.

Next, a curing method according to another embodiment of the present invention is characterized in that the thermosetting composition is cured by heating and thermally cationic polymerizing the composition. It is as described in. The curing reaction mechanism in the curing method of the present invention is such that the cationic species or Lewis acid generated from the cation-polymerizable catalyst formed from the heat-latent cation-polymerizable catalyst (C) by heating according to the method described below is converted into the compound (A) )) Or the oxirane group in the compound (B), that is, the oxygen atom of the epoxy group in the compound (B) to open them, and then the ring-opening reaction proceeds continuously, thereby at a stretch. It is presumed that it self-polymerizes to form a cured product having a three-dimensional network structure. In the present invention, the above-described curing reaction is usually performed in a solvent-free state, but may be performed in a reaction solvent. When a reaction solvent is used, the thermal cation polymerization reaction of the compound (A) and the compound (B) with the thermal latent cationically polymerizable catalyst (C) is performed at a high temperature as described later. The solvent desirably has a high boiling point, further has an action of dissolving or swelling at least one of the compound (A) and the compound (B), and has a function of dissolving or swelling the compound (A), the compound (B) and the heat. Those having no reactivity with the latent cationic polymerizable catalyst (C) can be used.

Examples of the reaction solvent include amide compounds such as N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC) and hexamethylphosphoric triamide (HMPA), diethylene glycol ethyl ether, and diglyme (diethylene glycol dimethyl ether). ), Triglyme (triethylene glycol dimethyl ether), ether compounds such as anisole and phenetole, o-dichlorobenzene, m
Halogenated aromatic hydrocarbons such as dichlorobenzene and 3,4-dichlorotoluene, nitrobenzene, dimethylsulfoxide (DMSO), sulfolane, tetramethylurea and N-methyl-2-pyrrolidone (NM
P), or a mixture of two or more of these solvents,
Various solvents from non-polar or low-polarity solvents to high-polarity solvents can be suitably used. Among them, DMF, DMAC, HMPA, DMSO and NM
The use of P or the like is preferred.

The amount of the reaction solvent to be used may be at least an amount sufficient to dissolve or swell the compound (A) and / or the compound (B). The amount of the compound (A) and the compound (B) charged, the type and amount of the heat-latent cationically polymerizable catalyst (C), the reaction temperature and the reaction time such as the reaction time, that is, the curing reaction conditions; Furthermore, at the time of the reaction, it differs depending on whether the compound (A) and / or the compound (B) is dissolved in the reaction solvent or swells with the reaction solvent, so that it is difficult to unambiguously define them. Therefore, for example, HMPA, DMSO, DMAC and N
When a polar solvent such as MP is used, the amount of the reaction solvent used is 1 to 10 times (volume / weight ratio) the total amount of the oxetane compound (A) and the compound (B).
Is preferred. When the amount is less than 1 time, the compound (A) and / or the compound (B) is not sufficiently dissolved in the polar reaction solvent, and the reaction proceeds in a heterogeneous system. Cation polymerization reaction is not performed, and the quality of the obtained cured product may vary. On the other hand, even when the above-mentioned polar reaction solvent is used in an amount of 10 times or more, the effect of the reaction solvent that the compound (A) and / or the compound (B) dissolves or swells to allow the cationic polymerization reaction to proceed in a homogeneous system. Has already been achieved, so further effects cannot be expected, and if it is necessary to remove and recover the reaction solvent from the cured product, it is necessary to recover the reaction solvent from the reaction system. It is not profitable because it consumes the above energy.

In the curing method of the present invention, a cationic polymerization reaction of the compound (A) and the compound (B) with the heat-latent cationic polymerizable catalyst (C), that is,
When the curing reaction is performed in a solvent-free state, the compound (A) and / or the compound (B) should be maintained in a molten state during the progress of the curing reaction. On the other hand, when the curing reaction is performed in a reaction solvent in a homogeneous system, the compound (A) and / or the compound (B) is swollen in a state dissolved in the reaction solvent or with the reaction solvent. It is necessary to carry out the curing reaction in a state, and for this purpose, the reaction solvent should be maintained in a liquid state during the progress of the curing reaction. Therefore, the reaction temperature, that is, the heating temperature, when the curing reaction is performed in a solvent-free state, the compound (A) and / or the compound (B)
Should be in a temperature range such that is in a molten state, and at least the lower of the melting point of the compound (A) and the melting point of the compound (B). On the other hand, when the curing reaction is performed in the reaction solvent, at least the compound (A) and / or the compound (B) are dissolved in the reaction solvent or swollen by the reaction solvent. Temperature. Therefore, the heating temperature in the present invention needs to be at least 50 ° C. or more as such a temperature. However, in the above case, the heating temperature is 200 ° C.
If the temperature exceeds the above, an undesirable thermal decomposition reaction of the catalyst (C) and the cured product obtained by the curing method of the present invention will occur at the same time, and the heating temperature in the curing reaction of the present invention is preferably 50 to 200 ° C. Is preferably in the range of 60 to 160 ° C.

In the cationic polymerization reaction of the compound (A) and the compound (B) with the heat-latent cationic polymerizable catalyst (C) in the curing method of the present invention, the reaction pressure is not particularly limited. It can be carried out under any of normal, normal and pressurized conditions. However, if the operation is performed under pressure, the pressure resistance performance of the manufacturing equipment is required, and if the operation is performed under reduced pressure, pressure reduction equipment is required. Is preferred. However, when a cationic polymerization reaction of the compound (A) and the compound (B) with the heat-latent cationic polymerizable catalyst (C) in the reaction solvent, that is, a curing reaction, as described above, During the course of the curing reaction, pressure conditions must be maintained such that the reaction solvent can maintain a liquid state (hence,
(The curing reaction may be performed under pressurized conditions.)
Needless to say. In addition, since the curing rate of the curing reaction increases as the temperature increases, the heating temperature should be as high as possible within the above-described range when the degree of crosslinking of the obtained cured product needs to be increased. However, if the temperature at the time of the curing reaction is too high, the reaction becomes non-uniform, adversely affecting the quality of the obtained cured product such as thermal properties and mechanical properties, or the oxetane compound (A) used. , The oxirane compound (B), the heat-latent cationic polymerizable catalyst (C), and the reaction solvent may be thermally unstable. Therefore, in such a case, it is preferable to reduce the pressure of the reaction system and maintain the reaction temperature low.

Regarding the reaction time in the curing method of the present invention, that is, the heating time, the amount of the compound (A) and the compound (B) charged, the type and the amount of the heat latent cationic polymerizable catalyst (C) used. Whether or not to perform a thermal cationic polymerization reaction in the absence of a solvent, if a reaction solvent is used, it depends on the type and amount of the reaction solvent, and the curing reaction conditions such as heating temperature, but usually 1 minute to
It is 50 hours, preferably 5 minutes to 10 hours, more preferably 10 minutes to 5 hours. When the heating time is shorter than 1 minute, a cationically polymerizable catalyst capable of exhibiting the activity of catalyzing the curing reaction is not sufficiently formed from the heat-latent cationically polymerizable catalyst (C). Since the cationic polymerization reaction of the compound (B) hardly proceeds, the curability of the obtained cured product is reduced. When the heating time is longer than 50 hours,
The obtained cured product may be subjected to a long-term heat history, resulting in deterioration of quality due to thermal degradation, which is not preferable. In order to surely prevent the occurrence of these undesired phenomena, the heating time should be within the above-mentioned preferred range, and more preferably, within the preferred range.

The cationic polymerization reaction of the compound (A) and the compound (B) in the curing method of the present invention is carried out under an inert gas atmosphere in order to prevent the resulting cured product from being deteriorated by undesirable oxidation or the like. It is preferable to be performed. As the inert gas, a rare gas such as an argon gas or a helium gas other than the nitrogen gas can be suitably used.

In the present invention, a method for producing a cured product of the compound (A) and the compound (B) by a cationic polymerization reaction, that is, a curing method is not particularly limited. Good. For example, after dissolving or swelling a predetermined amount of the compound (A) and the compound (B) in a predetermined amount of the reaction solvent as desired,
If necessary, supply to a reaction vessel equipped with a suitable heating device, and further add a predetermined amount of the above-mentioned heat latent cationic polymerizable catalyst (C), and pressurize at a normal pressure or under a predetermined reduced pressure or increased pressure. What is necessary is just to heat to a temperature and react for a predetermined time.

In the curing method of the present invention, as described above, at least one kind of the compound (A), at least one kind of the compound (B), and at least one kind of the heat-latent cationic polymerizable catalyst (C) are used. The thermosetting composition, which is a mixture with a seed, is filled into a reaction vessel having an appropriate shape and releasability, and heated in the absence of a solvent or in the reaction solvent at the reaction temperature described above and for the reaction time described above. Thus, the compound (A), the compound (B) and the catalyst (C)
After the cationic polymerization reaction, i.e., the curing reaction is performed, the reaction mixture obtained by cooling to room temperature by a conventional method such as air cooling or water cooling is taken out of the reaction vessel, and in some cases, subsequently, hot-air drying, vacuum By a known method such as drying and freeze-drying at a temperature of 100 ° C. or less, 2 to 16
It may be dried for a time. Thereby, a novel insoluble and infusible cured product having a three-dimensional network structure, which is another embodiment of the present invention, is obtained as a molded article. Further, after applying the thermosetting composition to a substrate such as metal, rubber, plastic, molded parts, film, paper, wood, glass cloth, concrete and ceramic, and then heating at a predetermined temperature for a predetermined time, A substrate having a cured product as a film can also be obtained. When the curing reaction of the compound (A) and the compound (B) with the thermally latent cationically polymerizable catalyst (C) is performed in the reaction solvent, the reaction mixture obtained after completion of the curing reaction is obtained. To evaporate the reaction solvent, and then cooled to room temperature, optionally followed by drying to obtain the cured product,
After the completion of the curing reaction, the obtained reaction mixture may be cooled to room temperature and used as a flexible cured product containing the reaction solvent.

When the thermosetting composition of the present invention is used,
As long as the effects of the present invention are not impaired, various known additives such as inorganic fillers, reinforcing materials, coloring agents, stabilizers (heat stabilizers, weather resistance improving agents, etc.), extenders, viscosity control Agents, flame retardants, UV absorbers, antioxidants, discoloration inhibitors,
Antibacterial agents, antifungal agents, antioxidants, antistatic agents, plasticizers, lubricants, foaming agents, mold release agents, and the like can be added and mixed. As the colorant, direct dyes, acid dyes, basic dyes, dyes such as metal complex dyes, carbon black, titanium oxide, zinc oxide, iron oxide, inorganic pigments such as mica and coupling azo, condensation azo, Organic pigments such as anthraquinone-based, thioindigo-based, dioxazone-based, and phthalocyanine-based pigments are exemplified. Examples of the stabilizer include hindered phenol-based compounds, hydrazine-based compounds, phosphorus-based compounds, benzophenone-based compounds, benzotriazole-based compounds, and oxalic acid anilide-based compounds. Furthermore, as the inorganic filler, glass fiber, asbestos fiber, carbon fiber, silica fiber, alumina fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, basic magnesium sulfate fiber, boron fiber, Inorganic and metal fibers such as stainless steel fiber, aluminum, titanium, copper, brass and magnesium, metal powder such as copper, iron, nickel, zinc, tin, lead, stainless steel, aluminum, gold and silver, wood powder,
Oxides such as magnesia and calcia, aluminum silicate, diatomaceous earth, quartz powder, talc, clay, hydroxides of various metals, carbonates, sulfates, phosphates, borates, borosilicates, aluminosilicates, Titanates, basic sulfates, basic carbonates and other basic salts, glass materials such as glass hollow spheres, glass flakes, ceramics such as silicon carbide, aluminum nitride, mullite, cordierite,
And waste such as fly ash and microsilica.

[0126]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited by these Examples and Comparative Examples. In the following Examples and Comparative Examples, as raw materials, oxetane compounds having 1 to 4 oxetane rings in the molecule (hereinafter simply referred to as “oxetane compounds”) and compounds having one or more oxirane rings in the molecule (Hereinafter simply referred to as “oxirane compound”) and a predetermined heat latent cationically polymerizable catalyst in a predetermined ratio (hereinafter referred to simply as “raw material mixture A”), an oxetane compound and a predetermined heat latent Oxetane composition (hereinafter, simply referred to as "raw material mixture B") in which a nonionic cation polymerizable catalyst is mixed with a predetermined ratio, and an oxirane compound and a predetermined heat latent cationic polymerizable catalyst are mixed in a predetermined ratio. A thermosetting oxirane composition (hereinafter simply referred to as “raw material mixture C”) and a cured product having a three-dimensional network structure of the product (hereinafter simply referred to as “cured product”) Characteristics of) that were each determined by the following method.

(1) Infrared absorption spectrum (IR) of raw material mixture A Using a 1750 Fourier infrared spectrophotometer manufactured by Perkin-Elmer Co., Ltd., a liquid sample of a small amount of the raw material mixture was converted into KBr.
It was applied on a crystal plate and measured.

(2) Infrared absorption spectrum of cured product (I
R) Using a 1750 Fourier infrared spectrophotometer manufactured by Perkin-Elmer Co., Ltd., a 1 mg sample of a cured product, which had been dried under reduced pressure at 60 ° C. for 10 hours or more to remove water, was subjected to KBr (Merc).
After drying under reduced pressure at 60 ° C. for 10 hours or more to remove water, a pressurized tablet was formed and measured.

(3) Reaction rate of raw material mixtures A, B, and C It was determined by measuring the starting point of the curing reaction of raw material mixtures A, B, and C using a gel time tester manufactured by Toyo Seiki Seisaku-sho, Ltd. That is, about 0.25 g of the raw material mixture A, B or C was added to the sample stage of the gel time tester set at a predetermined temperature, and at the same time, the measurement of the tension applied to the sample of the raw material mixture A, B or C was started. As the viscosity of the sample increases with the progress of the curing reaction, the tension increases. The point at which the tension increases by 1 g from an initial value (in most cases, zero) is defined as a curing reaction starting point.

(4) Solidification Time of Raw Material Mixture A glass container with a lid containing a predetermined amount of the raw material mixture A, B or C is immersed in an oil bath set at a predetermined temperature, shaken lightly, and allowed to stand. And the time until the raw material mixture in the glass container with a lid no longer flows was measured.

(5) Coloring State of Raw Material Mixture and the Final State of Cured Product For each of raw material mixtures A, B and C, the coloring state immediately after solidification was visually observed. The final state of the cured product finally obtained by stopping the heating in the oil bath was visually observed.

The reagents used in the following Examples and Comparative Examples are as follows. (A) Oxetane compound 3-ethyl-3-hydroxymethyloxetane (molecular weight: 116.13, hereinafter abbreviated as “EHO”) and 1,
4-bis [(3-ethyl-3-oxetanylmethoxy)
Methyl] benzene (molecular weight: 334.45, colorless liquid,
(Hereinafter abbreviated as “XDO”) is Ube Industries, Ltd.
And commercial products manufactured by Toa Gosei Co., Ltd. were used.

(B) Oxirane compound (epoxy resin) As a bisphenol A type epoxy resin, a commercial product (trade name: Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.)
Molecular weight: about 380, epoxy equivalent: 190, viscous liquid,
(Hereinafter abbreviated as "EP828"). In addition, as an alicyclic epoxy resin, a commercially available product manufactured by Daicel Chemical Industries, Ltd. (trade name: Celloxide 2021P, epoxy equivalent:
131, viscosity: 231 cp / 25 ° C .;
P ").

(C) Heat Latent Cationic Polymerizable Catalyst As San-Aid SI-100L (hereinafter abbreviated as "SI-100L"), a commercially available product manufactured by Sanshin Chemical Industry Co., Ltd. was used.

EXAMPLE 1 As shown in Table 1, 5.0 g (15 mmol) of XDO and 5.0 g (1
(3 mmol) of EP828, 0.2 g of SI as a heat latent cationic polymerizable catalyst (hereinafter simply referred to as “catalyst”).
After -100 L was added and mixed well, the inside was replaced with nitrogen gas and sealed. Therefore, the raw material charge ratio is
SI-100L / (XDO + EP828) = 2/100
(Weight ratio) and XDO / EP828 = 50/50 (weight ratio). Then, after immersing the glass container with the lid in an oil bath set at 100 ° C. and shaking lightly,
It was left still. The mixed solution in the glass container with the lid was 7 minutes 30 minutes.
After solidifying after 2 seconds and coloring brown, the heating was continued for a total of 5 hours after immersing the glass container with the lid in the oil bath.

During this time, the curing reaction was confirmed by IR spectroscopy.
This was done by tracking changes in the file. That is, the hard
For confirmation of the reaction, SI-100L /
(XDO + EP828) = 2/100 (weight ratio)
5 hours after immersion in the raw material mixture A and the above oil bath
The IR spectrum of the reaction product (cured product) that has passed
Each was measured. Therefore, the IR spectrum of the raw material mixture A is
Figure 1 shows the IR spectrum of the cured product.
Each is shown in FIG. As a result of comparing FIG. 1 and FIG.
980 cm assigned to the oxetane ring of XDO at
^-1Intensity and the oxirane ring of EP828
920cm to be done^-1Both have very strong absorption strength
Is 980 cm in FIG.^-1Based on the oxetane ring of
Absorption intensity and 9 based on the oxirane ring of EP828
20cm ^-1The absorption strength of both is very weak,
Proceeded sufficiently, and a cured product intended for the present invention was obtained.
I understood that. In addition, as a result of measuring the reaction rate,
SI-100L / XDO / EP828 = 2/50/50
Table 3 shows the starting point of the reaction of the raw material mixture A consisting of
As shown in the figure, it was 4 minutes and 30 seconds (4.5 minutes). What
Incidentally, the solidification time of the raw material mixture A, the state of coloring immediately after solidification, etc.
And the final state of the obtained cured product (hereinafter simply referred to as
Reactivity of substance A ". The same applies hereinafter) in Table 4
It was as shown.

Example 2 The amount of the starting materials XDO and EP828 was changed to XDO; 5.0 g.
(15 mmol) and EP828; 5.0 g (13 mmol), XDO; 2.5 g (7.5 mmol) and EP828; 7.5 g (19.7 mmol)
Therefore, XD in the charge ratio of the raw material
O / EP828 ratio (weight ratio) was changed to 50/50 and 2
Except for changing the ratio to 5/75, the same operation as in Example 1 was performed. The solidification time was 10 minutes, and a brown solid was obtained. In addition, the reactivity of the raw material mixture A was as shown in Table 4. As a result of measuring the reaction rate, the starting point of the reaction of the raw material mixture A was 11 minutes as shown in Table 3.

Examples 3 and 4 The amount of the starting materials XDO and EP828 was changed to XDO; 5.0 g.
(15 mmol) and EP828; 5.0 g (13 mmol), and in Example 3, XDO; 7.5 g (2
2.4 mmol) and EP 828; 2.5 g (6.6
Mmol), and in Example 4, XDO; 1.0 g
(3.0 mmol) and EP828; 9.0 g (2
3.7 mmol), and the same operation as in Example 1 was performed. Therefore, the charge ratio of the raw materials was as follows: SI-100L / XDO / EP828 =
2/75/25 (weight ratio), and the case of Example 4 was S
I-100L / XDO / EP828 = 2/10/10 /
(Weight ratio). As a result of measuring the reaction rate, the starting point of the reaction of the raw material mixture A was 59 seconds (0.98 minutes) in Example 3 and 4 in Example 4 as shown in Table 3.
It was 4.8 minutes. The reactivity of the raw material mixture A was as shown in Table 4.

Example 5 In place of 2.5 g (7.5 mmol) of XDO as a raw material, 2.5 g (21.5 mmol) of EHO was used. Therefore, the raw material charge ratio was SI-100L. / EH
Except that O / EP828 = 2/25/75 (weight ratio), the same operation as in Example 2 was performed. The solidification time of the raw material mixture A was 8 minutes and 15 seconds, and a brown solid was obtained. Other reactivities of the raw material mixture A are shown in Table 4.
As shown in FIG.

Examples 6 to 8 The amounts of raw materials EHO and EP828 used were EHO: 2.5 g.
(21.5 mmol) and 7.5 g of EP828 (1
9.7 mmol), and in Example 6, EHO;
5 g (64.6 mmol) and EP828; 2.5 g
(6.6 mmol), EHO in Example 7;
(43.0 mmol) and EP828; 5.0 g (1
3 mmol), and in Example 8, EHO;
(8.6 mmol) and EP 828; 9.0 g (2
3.7 mmol), and the same operation as in Example 5 was performed. Therefore, the charge ratio of the raw materials was as follows: SI-100L / EHO / EP828 =
2/75/25 (weight ratio), the case of Example 7 was SI-1
00L / EHO / EP828 = 2/50/50 (weight ratio), and the case of Example 8 was SI-100L / EHO.
/ EP828 = 2/10/90 (weight ratio). As a result, Table 4 shows the reactivity of the raw material mixture A for each of Examples 6 to 8.

Example 9 In place of 5.0 g (13 mmol) of EP828 as a raw material, 5.01 g of 2021P was used.
Raw material charge ratio is SI-100L / XDO / 2021P
= 2/50/50 (weight ratio), and the same operation as in Example 1 was carried out. The solidification time was 8 minutes and 30 seconds, and a yellow-colored solid was obtained. . As shown in Table 3, the reaction starting point of the raw material mixture A as a result of measuring the reaction rate was 73 seconds (1.21 minutes).

Comparative Example 1 In the same manner as in Example 1, a glass container with a lid having an inner volume of 30 ml was placed
As shown in Table 1, 10.0 g of EP828 (26.3
Mmol) as heat latent cationic polymerizable catalyst.
After adding 2 g of SI-100L and stirring thoroughly, the inside was replaced with nitrogen gas and sealed. Therefore, the charge ratio of the raw materials is SI-100L / EP828 = 2/100.
(Weight ratio). Next, the glass container with the lid was immersed in an oil bath set at 100 ° C., lightly shaken, and then allowed to stand. The mixed solution in the glass container with the lid is 3
After 30 minutes, fluidity disappeared and the solidified material was almost completely obtained. However, even after heating for 1 hour and 30 minutes, the product was still slightly tacky and the solidified state was insufficient. The above SI
Table 4 shows the reactivity of the raw material mixture C composed of -100 L / EP828 = 2/100 (weight ratio). Further, as a result of measuring the reaction rate, the starting point of the reaction of the raw material mixture C was very slow at 100 minutes as shown in Table 3.

Comparative Example 2 10.0 g of XDO (30 mmol) was used in place of 10.0 g of EP828 (26.3 mmol), so that the raw material charge ratio was SI-100L / XDO.
Comparative Example 1 except that the ratio was 2/100 (weight ratio).
When the same operation as that described above was performed, the mixture solidified after heating for 5 minutes and 20 seconds, and was colored light yellow. However, the obtained solidified product cracked immediately after solidification. The SI-
The reactivity of the raw material mixture B composed of 100 L / XDO = 2/100 (weight ratio) was as shown in Table 4. Further, as shown in Table 3, the reaction starting point of the raw material mixture B was 45 seconds (0.75 minutes).

Comparative Example 3 10.0 g of EHO (86 mmol) was used in place of 10.0 g of EP828 (26.3 mmol), so that the raw material charge ratio was SI-100L / EHO.
Comparative Example 1 except that the ratio was 2/100 (weight ratio).
When exactly the same operation as that described above was carried out, the mixture finally solidified after heating for 30 minutes and was colored black-brown. The above SI-10
The reactivity of the raw material mixture B consisting of 0 L / EHO = 2/100 (weight ratio) is as shown in Table 4, and the finally obtained cured product was soft when heated.

Comparative Example 4 10.0 g of 2021P was used instead of 10.0 g of EP828 (26.3 mmol), so that the raw material charge ratio was SI-100L / 2021P = 2/10.
Except that the ratio was 0 (weight ratio), the same operation as in Comparative Example 1 was performed. After heating for 6 minutes, the product was colored yellow-green and solidified. The obtained solidified product was the same as the SI-
The hardness was about the same as the cured product obtained by the curing reaction of the raw material mixture C composed of 100 L / EP828 = 2/100 (weight ratio). Further, as shown in Table 3, the reaction starting point of the raw material mixture C was 12.6 minutes.

Examples 10 and 11 The temperature set for the oil bath, that is, the heating temperature was set to 100 ° C.
As shown in Table 2, in Example 10, 70 ° C.
In Example 11, the same operation as in Example 3 was performed except that the temperature was set to 120 ° C. As a result of measuring the reaction rate, as shown in Table 3, the reaction starting point of the raw material mixture A was 29.1 minutes in Example 10 and 16 seconds (0.27 minutes) in Example 11. Was.

Embodiments 12 and 13 The temperature set for the oil bath, that is, the heating temperature was set to 100 ° C.
, And the same operation as in Example 1 was performed except that the temperature was changed to 70 ° C in Example 12 and to 120 ° C in Example 13. As a result of measuring the reaction rate, the starting point of the reaction of the raw material mixture A was 4 in Example 12 as shown in Table 3.
One minute and 90 seconds (1.5 minutes) in Example 13.

Examples 14 and 15 The temperature set for the oil bath, that is, the heating temperature was set to 100 ° C.
In Example 14, 120 ° C., and Example 15
Then, the same operation as in Example 2 was performed except that the temperature was changed to 160 ° C. As a result of measuring the reaction rate, the raw material mixture A
As shown in Table 3, the reaction starting point of Example 14 was 2.5 minutes in Example 14 and 33 seconds (0.55 in Example 15).
Min).

Examples 16 and 17 The temperature set for the oil bath, that is, the heating temperature was set to 100 ° C.
In Example 16, 120 ° C., and Example 17
Then, the same operation as in Example 4 was performed except that the temperature was changed to 160 ° C. As a result of measuring the reaction rate, the raw material mixture A
As shown in Table 3, the reaction starting point of Example 16 was 15.2 minutes in Example 16 and 2.6 minutes in Example 17.

Example 18 The set temperature of the oil bath, that is, the heating temperature was set to 100 ° C.
Except that the temperature was changed to 120 ° C., the same operation as in Example 9 was performed. As a result of measuring the reaction rate, as shown in Table 3, the reaction starting point of the raw material mixture A was 18 seconds (0.3
Min).

Comparative Examples 5 and 6 The set temperature of the oil bath, that is, the heating temperature was 100 ° C.
The same operation as in Comparative Example 1 was performed except that the temperature was changed to 120 ° C. in Comparative Example 5 and to 160 ° C. in Comparative Example 6. As a result of measuring the reaction rate, as shown in Table 3, the starting point of the reaction of the raw material mixture C was 43.
5 minutes and 7.9 minutes for Comparative Example 6.

Comparative Example 7 The set temperature of the oil bath, that is, the heating temperature was 100 ° C.
The same operation as in Comparative Example 2 was performed except that the temperature was changed to 70 ° C. As a result of measuring the reaction rate, the reaction starting point of the raw material mixture B was 27 minutes as shown in Table 3.

Comparative Example 8 The set temperature of the oil bath, that is, the heating temperature was 100 ° C.
The same operation as in Comparative Example 4 was performed except that the temperature was changed to 120 ° C. As a result of measuring the reaction rate, the starting point of the reaction of the raw material mixture C was 39 seconds (0.6
5 minutes).

[0154]

[Table 1]

[0155]

[Table 2]

[0156]

[Table 3]

[0157]

[Table 4]

Here, according to Table 3, the heating temperature is 100
1 to 4 and Comparative Example 1 with a heating temperature of 120 ° C.
Examples 11, 13, 14 and 16 and Comparative Example 5,
Examples 15 and 17 in which the heating temperature was 160 ° C.
And Comparative Example 6, a thermosetting composition (raw material) of the present invention comprising XDO as an oxetane compound, EP828 of a bisphenol A type epoxy resin as an oxirane compound, and a heat-latent cationic polymerization catalyst. In the mixture A), the curing reaction proceeds extremely rapidly as compared with the thermosetting oxirane composition (raw material mixture C) composed of EP828 and a heat-latent cationic polymerizable catalyst.
It can be seen that the raw material mixture A having a higher compounding ratio of the compound has a higher curing reaction speed. Furthermore, comparing Example 9 and Comparative Example 4 in which the heating temperature is 100 ° C., and Example 18 and Comparative Example 8 in which the heating temperature is 120 ° C.
The thermosetting composition (raw material mixture A) of the present invention comprising XDO which is an oxetane compound, 2021P of an alicyclic epoxy resin which is an oxirane compound, and a heat-latent cation polymerizable catalyst is also 2021P and a heat-latent cation. It can be seen that the curing reaction proceeds very quickly as compared with the thermosetting oxirane composition (raw material mixture C) comprising the polymerizable catalyst.

On the other hand, according to Table 3, the heating temperature was 7
When Examples 10 and 12 at 0 ° C. and Comparative Example 7 were compared with Examples 1 to 4 at a heating temperature of 100 ° C. and Comparative Example 2, XDO which is an oxetane compound was compared.
The heat-curable oxetane composition (raw material mixture B) comprising: a heat-latent cationically polymerizable catalyst comprising XDO, an oxirane compound EP828, and a heat-latent cationically polymerizable catalyst. It can be seen that the rate of the curing reaction is higher than (raw material mixture A). However, as is clear from Table 4, the cured products obtained in Comparative Examples 2 and 3 show cracks, are soft when heated, and are not always satisfactory in mechanical properties. Not something.

[0160]

As described above, according to the present invention, there is provided a novel cured product containing a specific oxetane compound, a specific oxirane compound and a specific heat-latent cationic polymerizable catalyst in a specific ratio. Thermosetting composition, and manufactured by heating the thermosetting composition, excellent mechanical properties, electrical properties, adhesion, heat resistance, moisture resistance and chemical resistance, and, A novel insoluble and infusible cured product having a three-dimensional network structure is obtained. Further, according to the present invention, by heating the thermosetting composition, a conventional thermosetting oxirane composition comprising a bisphenol A type epoxy resin or an alicyclic epoxy resin and the heat latent cationic polymerizable catalyst is used. Cation polymerization reaction of the oxetane compound and the oxirane compound can be performed extremely quickly as compared with the case of the product, and therefore, it is possible to provide a curing method capable of efficiently producing the novel cured product in a high yield. it can. Therefore, the novel cured product of the present invention utilizes the above-mentioned properties to provide paints, coatings, adhesives, electrical insulating materials, IC and VLSI sealing materials, laminates and other electrical and electronic components, and reinforced steel sheets. Bonding, casting compound,
Use as an alternative to epoxy resins such as textile coatings and impregnated tapes can be greatly expected.

[Brief description of the drawings]

FIG. 1 shows a raw material mixture A [SI-1 used in Example 1.
00L / XDO / EP828 = 2/50/50 (weight ratio) thermosetting composition].

FIG. 2 shows a cured product obtained in Example 1 [SI-100L /
XDO / EP828 = 2/50/50 (weight ratio)]
It is the figure which showed the R spectrum.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tsutomu Funakoshi 3-1 Chikko Shinmachi, Sakai City, Osaka Prefecture Ube Industries Co., Ltd. Sakai Plant

Claims (6)

[Claims] 1 to 5 parts by weight of at least one compound (A) having 1 to 4 oxetane rings in the molecule,
Compound (B) having one or more oxirane rings in the molecule
And at least one of the heat-latent cationically polymerizable catalyst (C) is used in an amount of 0.01 to 0.01 parts by weight based on 100 parts by weight of the total amount of the compound (A) and the compound (B). A thermosetting composition comprising up to 20 parts by weight. 2. A compound (A) having 1 to 4 oxetane rings in the molecule, wherein at least one kind of the compound (A) has 5 to 95 parts by weight,
Compound (B) having one or more oxirane rings in the molecule
Is 95 to 5 parts by weight, and at least one kind of the heat-latent cationically polymerizable catalyst (C) is 0.1 part by weight based on 100 parts by weight of the total amount of the compound (A) and the compound (B). Of the mixture consisting of 01 to 20 parts by weight
A method for producing a cured product, comprising heating at a temperature of 200 ° C. for 1 minute to 50 hours. 3. A compound having at least one compound (A) having 1 to 4 oxetane rings in a molecule thereof, in an amount of 5 to 95 parts by weight,
Compound (B) having one or more oxirane rings in the molecule
Is 95 to 5 parts by weight, and at least one kind of the heat-latent cationically polymerizable catalyst (C) is 0.1 part by weight based on 100 parts by weight of the total amount of the compound (A) and the compound (B). Of the mixture consisting of 01 to 20 parts by weight
A cured product obtained by heating at a temperature of 200 ° C. for 1 minute to 50 hours. 4. The heat-latent cationically polymerizable catalyst (C)
Is a quaternary ammonium salt represented by the following general formula (I),
Phosphonium salt represented by the following general formula (II), sulfonium salt represented by the following general formula (III), (IV) or (V), diazonium salt represented by the following general formula (VI), and the following general formula (VII) The thermosetting composition according to claim 1, wherein the thermosetting composition is at least one onium salt selected from the group consisting of iodonium salts represented by the formula: 5. The heat-latent cationically polymerizable catalyst (C)
Is a quaternary ammonium salt represented by the following general formula (I),
Phosphonium salt represented by the following general formula (II), sulfonium salt represented by the following general formula (III), (IV) or (V), diazonium salt represented by the following general formula (VI), and the following general formula (VII) 3. The method for producing a cured product according to claim 2, wherein the at least one onium salt is selected from the group consisting of iodonium salts represented by the formula: 6. The heat-latent cationically polymerizable catalyst (C)
Is a quaternary ammonium salt represented by the following general formula (I),
Phosphonium salt represented by the following general formula (II), sulfonium salt represented by the following general formula (III), (IV) or (V), diazonium salt represented by the following general formula (VI), and the following general formula (VII) 4. The cured product according to claim 3, wherein the cured product is at least one onium salt selected from the group consisting of iodonium salts represented by the formula: Embedded image (In the general formula (I), R _{1 to} R ₄ each represent an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, an aryl group, an alkaryl group,
An alkanol group of 20 or a cycloalkyl group having 5 to 10 carbon atoms, which may be the same or different, and may or may not have a substituent. Also,
Two of R _{1 to} R ₄ may be bonded to each other to form a heterocyclic ring having N, P, O or S as a hetero atom. Further, X is BF ₄ , PF ₆ , AsF ₆ , SbF ₆ , S
bCl ₆ , (C ₆ F ₅ ) ₄ B, SbF ₅ (OH), HS
O ₄ , p-CH ₃ C ₆ H ₄ SO ₃ , HCO ₃ , H ₂ PO
₄ , a monovalent anion selected from the group consisting of CH ₃ COO and a halogen atom. ) (In the general formula (II), R _{1 to} R ₄ and X each represent
It is the same as R _{1 to} R ₄ and X in the general formula (I). ) (In the general formula (III), R _{1 to} R ₃ and X each represent
It is the same as R _{1 to} R ₃ and X in the general formula (I), and two of R _{1 to} R ₃ are bonded to each other to form N,
A heterocyclic ring having P, O or S as a hetero atom may be formed. ) (In the general formula (IV), R ₁ , R ₂ and X are each
It is the same as R ₁ , R ₂ and X in the general formula (I), and R ₁ and R ₂ may combine with each other to form a heterocyclic ring having N, P, O or S as a hetero atom. . Ar represents an aryl group which may or may not have a substituent. ) (In the general formula (V), R _{1 to} R ₄ and X each represent
It is the same as R _{1 to} R ₄ and X in the general formula (I). Ar is the same as Ar in the general formula (IV). ) (In the general formula (VI), Ar and X are the same as Ar in the general formula (IV) and X in the general formula (I), respectively.) (In the general formula (VII), X is X in the above general formula (I)
R ₅ and R ₆ may be the same or different from each other, and may be an aryl group which may or may not have a substituent. )