JP2001310937A - Curable oxetane composition, its curing method and cured product obtained by the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable oxetane composition capable of an excellently fast cationic polymerization with a low viscosity and having an excellent adhesion, and to provide its curing method and a cured product obtained by the same. SOLUTION: The curing oxetane composition consists of an aliphatic or alicyclic compound (A) having one or more hydroxyl groups and two or more oxetanyl group in the molecule and a curing agent (B) as an essential element. The curing material is obtained by either production method of curing material, heating for 0.1 seconds, to 50 hours at 50-200 deg.C after that irradiation of active ray, or irradiation or active ray and heating for 0.1 seconds to 50 hours at 50-200 deg.C of the curing oxetane composition (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a novel cured product for producing a cured product having two or more oxetanyl groups and one hydroxyl group in the molecule.
The present invention relates to a curable oxetane composition comprising at least one aliphatic or alicyclic compound and a curing agent, a method for curing the composition, and a novel cured product obtained by the method.

[0002] The curable oxetane composition of the present invention is heated or irradiated with actinic rays and is subjected to the action of a curing agent to rapidly cure (a ring-opening polymerization reaction of the oxetane ring in the oxetane compound). Causes excellent mechanical properties (tensile strength, hardness, etc.) and electrical properties (electrical insulation, low dielectric constant, etc.) by forming a new cured product with an insoluble and infusible three-dimensional network structure , Adhesiveness, heat resistance,
Shows moisture resistance, chemical resistance, etc. As an alternative to epoxy resin, paints and coatings, varnishing varnishes, inks, paints, adhesives, electrical insulating materials, ICs and ultra-L
SI sealing materials, laminates and other electrical and electronic parts, repair of concrete structures, jointing of old and new concrete, bonding of reinforcing steel plates, civil engineering and building applications such as various linings, molding materials, composite materials, and conductive It is expected to be used in fields such as circuit connection material applications by dispersing particles.

[0003]

2. Description of the Related Art Oxetane, which is a 4-membered cyclic ether compound, exhibits high reactivity due to polarization of the bond between carbon and oxygen, and ring-opening polymerization of oxetane using Lewis acid or the like as a catalyst ( S. Inoue and T. Aid
a, “Ring Opening Polymeriz
ation, "KJ Ivin and T. Sa
egusa, Eds. , Elsevier, London
n, 1984, Vol. 1, pp. 185-298, etc.) and ring-opening polymerization of oxetanylmethyl trimethylsilyl ether using a trialkylaluminum-water reaction product as a catalyst (see JP-A-2-29429).

Recently, some photocationic polymerizations in the presence of a photoacid generator have been reported, utilizing the high reactivity of oxetane in cationic polymerization. For example, JP-A-6-16804, JP-A-7-17958, JP-A-7-173279 and JP-A-8-2
No. 45783 discloses a general formula (3)

[0005]

Embedded image

(Wherein R ⁴ is a hydrogen atom, a fluorine atom,
R ⁵ is a hydrogen atom, or an optionally substituted alkyl group, an optionally substituted aryl group, an alkanoyl group, an aroyl group, a monovalent hydrocarbon group, a monovalent fluorine-substituted hydrocarbon group, or the like. Or a substituted or unsubstituted linear or branched poly (alkyleneoxy) group, a divalent to tetravalent silicon-containing group, or a divalent to tetravalent aromatic ring-containing hydrocarbon group Etc. 1
And m is an integer of from 1 to 4) having 3 to 4 oxetane rings in the molecule represented by
A curable oxetane composition comprising a substituted oxetane monomer and a photoacid generator such as a triarylsulfonium salt or a diaryliodonium salt, comprising irradiating the composition with an active energy ray such as an ultraviolet ray, an X-ray or an electron beam. A method for curing the oxetane monomer and a crosslinked polymer obtained by the curing method are disclosed.
Further, with respect to the thermal cationic polymerization of oxetane using a heat-latent cationic polymerizable catalyst, see JP-A-11-2693.
No. 70 is disclosed.

As an oxetane compound, JP-A-11-1
No. 30766 discloses a compound represented by the general formula (4) and having an oxetanyl group and a hydroxyl group in the molecule. An active energy ray-curable composition using the compound gives a cured product having a high degree of polymerization and excellent adhesion by short-time light irradiation.

Embedded image (Wherein, R ⁶ represents a methyl group or an ethyl group, R ^7, R
⁸ represents a hydrogen atom, a halogen atom, a methyl group, a phenyl group or a trihalogenomethyl group. )

Recently, in the cationic photopolymerization of oxirane compounds in the presence of a photoacid generator, it has been reported that the photocuring reaction proceeds more rapidly when alcohols are added (for example, JV). .Crivello
Et al. Radiat. Curing, 13, 3 (19
86) and JP-A-11-228610). Since the hydroxyl groups of alcohols are involved in the chain transfer reaction,
It is described that such a phenomenon occurs (Chemi
story & Technology of UV & EB
Formulation for Coatings,
Inks & Pigments, Ed. by K. Die
trigger, SITA Technology Lt
d, London, 1991, pp. 352-358).

Since the compound represented by the general formula (4) has an oxetanyl group and a hydroxyl group in the molecule, it is considered that the photocationic polymerization of the oxetane compound proceeded at high speed in the presence of the photoacid generator.

[0010]

However, since the compound represented by the general formula (4) has a rigid aromatic ring in the molecule, there is a problem that the compound has high viscosity and is difficult to handle. Further, in recent years, a solvent-free process has been actively taken up in consideration of the environment, and the compound represented by the general formula (4) cannot satisfy this requirement due to poor compatibility with the base polymer. there were. The present invention provides a curable oxetane composition having a low viscosity, excellent high-speed cationic polymerization ability and excellent adhesion, a method for curing the composition, and a cured product obtained by the method.

[0011]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a curable composition using an aliphatic or alicyclic compound having a hydroxyl group and an oxetanyl group in the molecule has a low viscosity and excellent properties. High cationic polymerization ability. Furthermore, the cured product obtained from the composition was found to exhibit high adhesion and high stability over time, and the present invention was completed.

The invention described in claim 1 comprises an aliphatic or alicyclic compound (A) having at least two oxetanyl groups and at least one hydroxyl group in the molecule, and a curing agent (B) as essential components. The present invention provides a low-viscosity curable oxetane composition having excellent high-speed cationic polymerization ability and excellent adhesion. Claim 2
The invention described in the above, two or more oxetanyl groups in the molecule,
The curable composition according to claim 1, wherein the aliphatic or alicyclic compound (A) having one or more hydroxyl groups is a compound represented by the general formula (1) or the general formula (2). An oxetane composition (C), which provides a curable oxetane composition that can be obtained easily and at low cost in addition to the invention described in claim 1.

[0013]

Embedded image (Where Q represents an oxygen or sulfur atom, R ¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms, or an allyl group; R ² represents a divalent to hexavalent aliphatic or alicyclic organic group corresponding to the value of n, and n represents an integer of 2 to 6.)

Embedded image (Where Q represents an oxygen or sulfur atom, R ¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group or an allyl group having 1 to 6 carbon atoms, and R ³ represents oxetanyl. A divalent aliphatic group capable of forming a ring or an aliphatic organic group which may be substituted by an alicyclic system, and p represents an integer of 0 to 6.)

According to the third aspect of the present invention, there is provided an aliphatic or alicyclic compound (A) having at least two oxetanyl groups and at least one hydroxyl group in the molecule, having 2 to 6 oxetanyl groups in the molecule. And a curable oxetane composition (C) according to claim 1 or 2, which is an aliphatic or alicyclic compound having 1 to 6 hydroxyl groups. The present invention also provides a curable oxetane composition that gives a cured product having a more appropriate crosslinking density.
The invention according to claim 4 is that the oxetanyl group is included in the molecule.
The curable oxetane composition (C) according to any one of claims 1 to 3, wherein the molecular weight of the aliphatic or alicyclic compound (A) having at least one hydroxyl group or at least one hydroxyl group is in the range of 144 to 5,000. The present invention provides a curable oxetane composition which gives a composition and a cured product having high storage stability, in addition to the invention described in claims 1 to 3. The invention according to claim 5 is the curable oxetane composition (C) according to any one of claims 1 to 4, wherein the curing agent (B) is a cationically polymerizable catalyst (B1). In addition to the inventions described in the items 1 to 4, the present invention also provides a curable oxetane composition which cures in a short time and obtains a cured product having a higher crosslinking density. The invention according to claim 6 is the curable oxetane composition (C) according to any one of claims 1 to 4, wherein the cationically polymerizable catalyst (B1) is a latent cationically polymerizable catalyst (B2). And claim 1
Another object of the present invention is to provide a curable oxetane composition having excellent storage stability before cross-linking and high reactivity in addition to the inventions described in the above-mentioned items.

The inventions described in claims 7 to 9 are provided in claims 1 to
In addition to the invention described in 6, the present invention provides a method for producing a cured product having high adhesion and high stability over time. Claim 7
The invention described in (1) provides the curable oxetane composition (C) according to any one of claims 1 to 6 at 50 to 200 ° C.
A method for producing a cured product (D), characterized in that the composition is heated at a temperature of 0.1 seconds to 50 hours, and the invention according to claim 8 is the curable composition according to any one of claims 1 to 6. The method according to claim 9, wherein the oxetane composition (C) is irradiated with an actinic ray.
Irradiating the curable oxetane composition (C) according to any one of claims 1 to 6 with actinic light,
A method for producing a cured product (D), comprising heating at a temperature of 00C for 0.1 second to 50 hours.

The invention according to claims 10 to 12 is the first invention.
In addition to the inventions of (1) to (6), the present invention provides a cured product having high adhesion and high stability over time. The invention according to claim 10 is obtained by heating the curable oxetane composition (C) according to any one of claims 1 to 6 at a temperature of 50 to 200 ° C for 0.1 second to 50 hours. Cured product (D),
The invention described in claim 11 is a cured product (D) obtained by irradiating the curable oxetane composition (C) according to any one of claims 1 to 6 with actinic light, and described in claim 12. The present invention irradiates the curable oxetane composition (C) according to any one of claims 1 to 6 with actinic light,
And a cured product (D) obtained by heating at a temperature of 50 to 200 ° C. for 0.1 second to 50 hours.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (Aliphatic or alicyclic compound having two or more oxetanyl groups and one or more hydroxyl group in the molecule (A)) Aliphatic or alicyclic compound having an oxetanyl group and a hydroxyl group in the molecule used in the present invention The compound (A) is not limited to an aliphatic or alicyclic compound as long as it has an oxetanyl group and a hydroxyl group in the molecule. Among them, an aliphatic or alicyclic compound having 2 to 6 oxetanyl groups and 1 to 6 hydroxyl groups in one molecule is preferable because of excellent curability. Those having one oxetanyl group in one molecule tend to lower the strength of the cured product. When the number of oxetanyl groups in one molecule exceeds 6, the crosslink density of the polymer is too high, so that it is difficult to handle and the intramolecular reaction tends to occur. When the number of hydroxyl groups in one molecule exceeds 6,
There is a tendency that the hydrophilicity of the cured product increases and the hygroscopicity increases. Aliphatic or alicyclic compounds (A) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule of the present invention
The following compounds are preferred examples.

[0018]

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The aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule used in the present invention is represented by the following general formula (1). Are preferred because they are easy to synthesize.

Embedded image

In the general formula (1), Q represents an oxygen or sulfur atom, and is preferably an oxygen atom because of ease of synthesis. In the formula, p represents an integer of 0 to 6, but p = 1 is preferable in terms of availability.

In the general formula (1), R ¹ represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group which is unsubstituted or substituted by an aliphatic or alicyclic organic group. An alkyl group having 1 to 6 carbon atoms such as an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a trifluoromethyl group, a pentafluoroethyl group, Examples thereof include a perfluoroalkyl group having 1 to 6 carbon atoms, such as a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, a 2- (perfluorobutyl) ethyl group, and a perfluorohexyl group. Among them, R ¹
Of these, those having a hydrogen atom, a methyl group, or an ethyl group are preferable because of their high oxetane content.

In the general formula (1), R ² is not particularly limited as long as it is a divalent to hexavalent aliphatic or alicyclic organic group corresponding to an integer n of 2 to 6. Specifically, when n = 2, R ²
Is a divalent aliphatic or alicyclic organic group. Examples of the aliphatic or alicyclic compounds (A) having two or more oxetanyl groups and one or more hydroxyl groups in such a molecule include the following compounds.

[0023]

Embedded image When n = 3, R ² is a trivalent aliphatic or alicyclic organic group. The aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl groups in such a molecule includes the following compounds.

Embedded image

When n = 4, R ² is a tetravalent aliphatic or alicyclic organic group. The aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl groups in such a molecule includes the following compounds.

Embedded image

The aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule used in the present invention is represented by the following general formula (2): Ring compounds are also included.

Embedded image

In the general formula (2), Q represents an oxygen or sulfur atom, and is preferably an oxygen atom because of ease of synthesis. In the formula, p represents an integer of 0 to 6, but p = 1 is preferable in terms of availability.

In the general formula (2), R ¹ represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, an unsubstituted or substituted aliphatic or alicyclic organic group. Butyl group, isobutyl group, se
c-butyl group, tert-butyl group, cyclobutyl group,
An alkyl group having 1 to 6 carbon atoms such as a pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a trifluoromethyl group, a pentafluoroethyl group, a perfluoropropyl group, a perfluoroisopropyl group, a perfluorobutyl group, Examples thereof include a perfluoroalkyl group having 1 to 6 carbon atoms, such as a (perfluorobutyl) ethyl group and a perfluorohexyl group. Among them, those in which R ¹ is a hydrogen atom, a methyl group or an ethyl group are preferable because of their high oxetane content. R ³ has an oxetanyl group, and may be a divalent aliphatic group capable of forming a ring or an aliphatic organic group which may be substituted with an alicyclic group,
There is no particular limitation.

The alicyclic compound having two or more oxetanyl groups and one or more hydroxyl group in the molecule of the general formula (2) has an intramolecular cross-linking structure in advance, and therefore, gives a tough cured product. preferable. Specific examples include the following compounds.

Embedded image Here, W and X represent a combination of a hydroxyl group and an (oxetan-3-yl) methoxy group (I), and Y and Z represent a combination of a hydroxyl group and a (oxetan-3-yl) methoxy group (I).

As the aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl group in the molecule, not only a compound having a single molecular weight but also a compound having a single molecular weight can be used in the present invention. , Oligomer having a molecular weight distribution (A1)
May be used. The composition using such an oligomer (A1) has reduced crystallinity and excellent storage stability. Used in the present invention, two or more oxetanyl groups in the molecule,
The molecular weight of the aliphatic or alicyclic compound (A) or oligomer (A1) having one or more hydroxyl groups is 14
The range of 4 to 10000 is preferable, and the range of 144 to 5000 is more preferable. When the molecular weight is 144 or less, two oxetanyl groups and one hydroxyl group cannot be formed in the molecule, and when it exceeds 10,000, the curing rate tends to decrease. Aliphatic or alicyclic compounds (A) or oligomers (A1) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule used in the present invention
Are used alone or in combination of two or more.

The aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule used in the present invention is used in an amount such that the hydroxyl groups remain after the reaction with the polyhydric alcohol. (3-ethyloxetane-
It can be prepared by reacting 3-yl) methyl tosylate or (3-methyloxetane-3-yl) methyl tosylate or (oxetan-3-yl) methyl tosylate in the presence of a base.

Alternatively, a part of the hydroxyl group of the polyhydric alcohol is protected, and the remaining hydroxyl group and (3-ethyloxetane-3-
It can be produced by reacting yl) methyl tosylate or (3-methyloxetane-3-yl) methyl tosylate or (oxetan-3-yl) methyl tosylate in the presence of a base, followed by deprotection.

Further, in the molecule represented by the general formula (1) or (2) used in the present invention, two or more oxetanyl groups are contained.
As for the aliphatic or alicyclic compound (A) having one or more hydroxyl groups, (3-ethyloxetane-3-yl) methanol or (3-methyloxetane-3-yl) methanol or ( Oxetane-3-
Yl) Methanol can be easily and inexpensively produced by acting on an aliphatic or alicyclic oxirane compound.

(Curing Agent (B)) As the curing agent (B) which is a component of the present invention, an aliphatic or alicyclic compound having at least two oxetanyl groups and at least one hydroxyl group in the molecule ( Any compound can be used as long as it is a compound that undergoes ring-opening polymerization of A) (B ′) or an addition reaction with an oxetane compound (B ″). Two or more oxetanyl groups and one or more hydroxyl groups in the molecule are used. Ring-opening polymerization of aliphatic or alicyclic compound (A) having at least one (B ')
As the cationic polymerizable catalyst, anionic polymerizable catalyst,
Latent cationic polymerization initiators and latent anionic polymerizable catalysts are exemplified. The compound (B ″) that undergoes an addition reaction to an aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl group in the molecule is a difunctional or more carboxylic acid, The above polythiol, difunctional or higher carboxylic anhydride, difunctional or higher phenol, etc. are preferably used, and these can be used alone or in combination of two or more.

When the cationic polymerizable catalyst (B1) is used as the curing agent (B '), the curable oxetane composition (C)
Are cured in a short time, and a cured product having a higher crosslinking density is obtained. As such a cationically polymerizable catalyst (B1),
Proton acids such as sulfuric acid, phosphoric acid, perchloric acid and trifluoromethanesulfonic acid, or Lewis acids such as boron trifluoride, aluminum chloride, titanium tetrachloride and tin tetrachloride are preferably used. These can be used alone or in combination of two or more.

Among the cationically polymerizable catalysts (B1), the so-called latent cationically polymerizable catalysts (B2), which form a cationically polymerizable catalyst by irradiation or heating with actinic rays, have an oxetanyl group in the molecule. Is stable for a long time as long as it is blended with an aliphatic or alicyclic compound (A) having two or more hydroxyl groups and one or more hydroxyl groups and left at room temperature, A cationically polymerizable catalyst can be formed to initiate and accelerate the curing reaction.

The latent cationic polymerizable catalyst (B)
Specifically as 2), a quaternary ammonium salt represented by the following general formula (5), a phosphonium salt represented by the following general formula (6), a quaternary ammonium salt represented by the following general formula (7), (8) or (9) At least one onium salt selected from the group consisting of a sulfonium salt represented by the following, a diazonium salt represented by the following general formula (10), and an iodonium salt represented by the following general formula (11).

Embedded image (In the general formula (5), R ^{9 to} R ¹² 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 ^{9 to} R ¹² may be bonded to each other to form a heterocyclic ring having N, P, O or S as a hetero atom. X is BF ₄ , PF ₆ , AsF ₆ , SbF ₆ , SbC
_{l 6, (C 6 F 5} ) 4 B, SbF 5 (OH), HSO 4, p-
CH ₃ C ₆ H ₄ SO ₃ , HCO ₃ , H ₂ PO ₄ , CH ₃ COO
And a monovalent anion selected from the group consisting of halogen atoms. )

[0037]

Embedded image (In the general formula (6), R ^{9 to} R ¹² and X each represent
It is the same as R ^{9 to} R ¹² and X in the general formula (5). )

Embedded image (In the general formula (7), R ^{9 to} R ¹¹ and X each represent
It is the same as R ^{4 to} R ⁶ and X in the general formula (5), and two of R ^{9 to} R ¹¹ are bonded to each other to form N, P,
A heterocyclic ring having O or S as a hetero atom may be formed. )

[0038]

Embedded image (In the general formula (8), R ⁹ , R ¹⁰ and X each represent
It is the same as R ⁹ , R ¹⁰ and X in the general formula (5), and R ⁹ and R ¹⁰ may combine with each other to form a heterocyclic ring having N, P, O or S as a hetero atom. . Ar ¹ represents a monovalent aryl group which may or may not have a substituent, and Ar ² represents a divalent arylene group which may or may not have a substituent. Express. )

Embedded image (In the general formula (9), R ^{9 to} R ¹² and X each represent
It is the same as R ^{9 to} R ¹² and X in the general formula (5). Further, Ar ¹ is, Ar ¹ in the general formula (8)
Ar ² is the same as A ² in the general formula (8).
is the same as r ^2. )

[0039]

Embedded image (In the general formula (10), Ar ¹ and X are respectively Ar ¹ and the general formula (5) in the general formula (8).
Is the same as X in )

Embedded image (In the general formula (11), X is the same as X in the general formula (5), and Ar ³ and Ar ⁴ may be the same or different from each other, and may have a substituent. It is a monovalent aryl group which may not be present.)

Here, in the general formulas (6) to (9), the alkyl group having 1 to 20 carbon atoms as R ⁹ , R ¹⁰ , R ¹¹ or R ¹² has a substituent. And a linear or branched alkyl group which may or 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 group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl Group, hexadecyl group, octadecyl group, nonadecyl group, eicosyl group and the like. Further, as the alkenyl group having 3 to 12 carbon atoms as R ⁹ , R ¹⁰ , R ¹¹ or R ¹² , 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, octenyl group, nonenyl group, decenyl group, uncenyl group, etc. Is mentioned.

The aryl group as R ⁹ , R ¹⁰ , R ¹¹ or R ¹² includes, for example, a substituted or unsubstituted phenyl group, naphthyl group or anthracene group, and a phenyl group is particularly preferred. As the alkaryl group as R ⁹ , R ¹⁰ , R ¹¹ or R ¹² , the alkaryl group described above includes the alkyl group having 1 to 20 carbon atoms and the aryl group. The alkanol group having 1 to 20 carbon atoms as R ⁹ , R ¹⁰ , R ¹¹ or R ¹² may be a straight-chain or branched alkanol group which may or may not have a substituent. And, 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 ⁹ , R ¹⁰ , R ¹¹ or R ¹² ,
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 (8) and (10), the monovalent aryl group which may or may not have a substituent as Ar ¹ is a substituted or unsubstituted phenyl group or And a naphthyl group. In the general formulas (8) and (9), the divalent arylene group which may or may not have a substituent as Ar ² includes a substituted or unsubstituted phenylene group or naphthylene group. No.

In the general formulas (5) to (10), 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.

In the general formula (11), Ar ³ and Ar ⁴ may be the same or different from each other, and may or may not have a substituent. Examples of the monovalent aryl group 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.

Examples of the quaternary ammonium salt represented by the general formula (5) include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, and tetraethylammonium −
p-toluenesulfonate, N-benzyl-N, N-dimethylanilinium antimony hexafluoride, N-benzyl-N, N-dimethylanilinium boron tetrafluoride, N-
(4-methoxybenzyl) -N, N-dimethylanilinium antimony hexafluoride, N-benzyl-N, N-dimethyltoluidinium antimony hexafluoride, N-benzylpyridinium antimony hexafluoride, N-benzyl-4 −
Cyanopyridinium antimony hexafluoride, 4-cyano-
N- (4-methoxybenzyl) pyridinium antimony hexafluoride and the like can be mentioned.

Specific examples of the phosphonium salt represented by the general formula (6) include, for example, ethyltriphenylphosphonium antimony hexafluoride and tetrabutylphosphonium antimony hexafluoride.

Examples of the sulfonium salt represented by the general formula (7), (8) or (9) include, for example, triphenylsulfonium boron tetrafluoride, triphenylsulfonium antimony hexafluoride, and triphenylsulfonium hexafluoride. Arsenic arsenide, tri (4-methoxyphenyl) sulfonium arsenic 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 Co., Ltd., counter ion: SbF ₆ ), Adeka Opton CP-
66 (manufactured by Asahi Denka Kogyo KK, counter ion: SbF ₆ ),
Adeka Opton CP-77 (manufactured by Asahi Denka Kogyo Co., Ltd., counter ion: SbF ₆ ), San Aid SI-60L (manufactured by San Shin Chemical Co., Ltd., counter ion: SbF ₆ ), Sun Aid SI-80L (San Shin Chemical Industry Co., Ltd.) Made, counter ion: S
bF ₆ ), San-Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd., counter ion: SbF ₆ ), San-Aid SI-1
50 (manufactured by Sanshin Chemical Industry Co., Ltd., 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 (manufactured by Sartomer Co., Ltd.) and CI series (manufactured by Nippon Soda Co., Ltd., counter ion: PF _6, Sb
F ₆ ).

Specific examples of the diazonium salt represented by the general formula (10) include AM manufactured by American Can Inc.
ERICURE (counter ion: BF ₄ ) and ULTRASET (counter ion: BF ₄ , P
F ₆ ).

Specific examples of the iodonium salt represented by the general formula (11) include arsenic diphenyliodonium hexafluoride, arsenic di-4-chlorophenyliodonium hexafluoride, and di (4-bromophenyl) iodonium hexafluoride. Arsenic arsenide, phenyl (4-methoxyphenyl) iodonium arsenide hexafluoride, UVE series manufactured by General Electric, FC series manufactured by Minnesota Mining and Manufacturing, UV-9310C manufactured by Toshiba Silicone (counter ion : SbF ₆ ) and Photoinitiator manufactured by Rhone Poulin
2074 (counter ion: (C ₆ F ₅ ) ₄ B).

The latent cationically polymerizable catalyst (B2) represented by the general formulas (5) to (11) may be used alone or
Used in combination of more than one type.

Aliphatic or alicyclic compounds (A) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule
Specific examples of the curing agent (B ″) that undergoes an addition reaction to the compound include the following compounds. Examples of the bifunctional or more functional carboxylic acid and anhydride include succinic acid, maleic acid, itaconic acid, azelaic acid, sebacic acid, phthalic acid, Tetrahydrophthalic acid, hexahydrophthalic acid, nadic acid, methylnadic acid, dodecenylsuccinic acid, pyromellitic acid, trimellitic acid, cyclopentadienetetracarboxylic acid, square acid, anhydrides thereof, and the like. Examples of the phenolic curing agent include catechol, catechol derivatives, resorcinol, resorcinol derivatives, hydroquinone, hydroquinone derivatives, pyroganol, pyroganol derivatives, tetrahydroxybenzenes, tetrahydroxybenzene derivatives, etc. Bifunctional or higher thiols And is 1,2-ethanedithiol, 1,4-butane dithiol, 1,6-naphthalene dithiol, 1,1-cyclohexane dithiol,
Examples include 1,4-benzenedithiol and 1,4-naphthalenedithiol. These curing agents (B ") are used alone or in combination of two or more.

Aliphatic or alicyclic compounds having two or more oxetanyl groups and one or more hydroxyl groups in the molecule, such as a cationically polymerizable catalyst, an anionic polymerizable catalyst, a latent cationic polymerization initiator, and a latent anionic polymerizable catalyst. The amount of the curing agent (B ′) used for ring-opening polymerization of the compound (A) is based on 100 parts by weight of the aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule. 0.0 for
The amount is preferably 1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight. When the amount of the curing agent (B ′) for ring-opening polymerization of an aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule is less than 0.01 part by weight, the curing is performed. When the amount exceeds 20 parts by weight, the storage stability of the adhesive film before use tends to decrease. Further, difunctional or higher carboxylic acid, difunctional or higher polythiol, difunctional or higher carboxylic acid anhydride,
Oxetanyl groups in the molecule such as phenols
The amount of the curing agent (B ″) that undergoes an addition reaction with the aliphatic or alicyclic compound (A) having at least one hydroxyl group is at least two oxetanyl groups and at least one hydroxyl group in the molecule. 2 to 500 parts by weight, preferably 50 to 30 parts by weight, per 100 parts by weight of the aliphatic or alicyclic compound (A)
0 parts by weight is more preferred. Oxetanyl group in the molecule
If the amount of the curing agent (B ″) that undergoes an addition reaction with the aliphatic or alicyclic compound (A) having one or more hydroxyl groups is less than 2 parts by weight, the curability tends to be insufficient, and 500
If the amount exceeds the weight part, the storage stability of the adhesive film before use tends to decrease.

Aliphatic or alicyclic compounds (A) having at least two oxetanyl groups and at least one hydroxyl group in the molecule
When the reactive monomer (E) described below is used in combination, an aliphatic or alicyclic compound (A) having at least one hydroxyl group
The amount of the curing agent (B ') used for ring-opening polymerization of the compound (A) is 0.1 to 100 parts by weight of the total of the aliphatic or alicyclic compound (A) having one or more hydroxyl groups and the reactive monomer (E).
The amount is preferably from 01 to 20 parts by weight, more preferably from 0.1 to 10 parts by weight. When an aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule and a reactive monomer (E) described later are used in combination, an aliphatic compound having one or more hydroxyl groups is used. The amount of the curing agent (B ″) that undergoes an addition reaction with the aliphatic or alicyclic compound (A) is determined by adding the aliphatic or alicyclic compound (A) having at least one hydroxyl group to the reactive monomer (E). 2 to 500 parts by weight, preferably 50 to 300 parts by weight, per 100 parts by weight.

(Reactive monomer (E)) As a component constituting the curable oxetane composition (C) of the present invention, an aliphatic or oxetanyl group having at least two oxetanyl groups and at least one hydroxyl group in the molecule described above. A reactive monomer (E) other than the alicyclic compound (A) can also be added. Examples of such a reactive monomer (E) include a compound (E1) having an oxetanyl group and a compound (E1) having an oxiranyl group.
2) or a compound having an ethylenically unsaturated group (E
3) and the like, and these can be used alone or in combination of two or more.

The compound (E1) having an oxetanyl group is not particularly limited as long as it has an oxetane ring in the molecule, and any compound can be used. Of these, compounds having 1 to 4 oxetane rings in the molecule are preferred because of excellent physical properties of the cured product.

Examples of the compound having one oxetane ring include a compound represented by the following general formula (12).

[0057]

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In the general formula (12), R ¹³ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, and a fluoroalkyl group having 1 to 6 carbon atoms. , An allyl group, an aryl group, a furyl group or a thienyl group. R ¹⁴ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, a 1-propenyl group, a 2-propenyl group,
An alkenyl group having 2 to 6 carbon atoms such as -methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-butenyl group, 2-butenyl group or 3-butenyl group, phenyl group, benzyl group, fluoro group A group having an aromatic ring such as a benzyl group, a methoxybenzyl group or a phenoxyethyl group,
An alkylcarbonyl group having 2 to 6 carbon atoms such as an ethylcarbonyl group, a propylcarbonyl group or a butylcarbonyl group, an alkoxycarbonyl group having 2 to 6 carbon atoms such as an ethoxycarbonyl group, a propoxycarbonyl group or a butoxycarbonyl group, or ethyl And an N-alkylcarbamoyl group having 2 to 6 carbon atoms such as a carbamoyl group, a propylcarbamoyl group, a butylcarbamoyl group or a pentylcarbamoyl group.

Next, examples of the compound having two oxetane rings include a compound represented by the following general formula (13).

[0060]

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In the general formula (13), R ¹³ is the same group as in the general formula (12). R ¹⁵ is
For example, linear or branched alkylene groups such as ethylene group, propylene group or butylene group, linear or branched poly (alkyleneoxy) groups such as poly (ethyleneoxy) group or poly (propyleneoxy) group, propenylene Or a linear or branched unsaturated hydrocarbon group such as a methylpropenylene group or a butenylene group; an alkylene group containing a carbonyl group or a carbonyl group; an alkylene group containing a carboxyl group; or an alkylene group containing a carbamoyl group.

R ¹⁵ is represented by the following general formulas (14) to (2)
It is also a polyvalent group selected from the groups represented by 5).

[0063]

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In the general formula (14), R ¹⁶ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group. A C1-C4 alkoxy group such as a group, a halogen atom such as a chlorine atom or a bromine atom, a nitro group, a cyano group, a mercapto group, a lower alkylcarboxyl group, a carboxyl group, or a carbamoyl group.

[0065]

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In the general formula (15), R ¹⁷ represents an oxygen atom, a sulfur atom, a methylene group,

Embedded image It is.

[0067]

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In the general formula (16), R ¹⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group. A C1-C4 alkoxy group such as a group, a halogen atom such as a chlorine atom or a bromine atom, a nitro group, a cyano group, a mercapto group, a lower alkylcarboxyl group, a carboxyl group, or a carbamoyl group.

[0069]

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In the general formula (17), R ¹⁹ represents an oxygen atom, a sulfur atom, a methylene group,

Embedded image It is.

[0071]

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In the general formulas (18) and (19), R ²⁰ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group, a methoxy group, an ethoxy group. Group, a C1-C4 alkoxy group such as a propoxy group or a butoxy group, a halogen atom such as a chlorine atom or a bromine atom, a nitro group, a cyano group, a mercapto group, a lower alkylcarboxyl group, a carboxyl group or a carbamoyl group. . Further, R ²⁰ may be substituted with 2 to 4 naphthalene rings.

[0073]

Embedded image However, 1 is 0 to 10, and a mixture of compounds having different numerical values may be used.

Among the compounds having two oxetane rings, preferred examples other than the above-mentioned compounds include compounds represented by the following general formula (26). In the general formula (26), R ¹³ is the same group as in the general formula (12).

[0075]

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Examples of the compound having 3 to 4 oxetane rings include a compound represented by the following general formula (27).

[0077]

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In the general formula (27), R ¹³ is the same group as in the general formula (12), and q is 3 or 4. R ²¹ is, for example, a group having 1 to 1 carbon atoms such as a group represented by the following general formulas (28), (29) and (30).
And a branched poly (alkyleneoxy) group such as a group represented by the following general formula (31).

[0079]

Embedded image (In the general formula (28), R ²² is a lower alkyl group such as a methyl group, an ethyl group or a propyl group.)

[0080]

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[0081]

Embedded image

[0082]

Embedded image (In the general formula (31), r is an integer of 1 to 10.)

Preferred specific examples of the oxetane compound used in the present invention include the following compounds.

[0084]

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Further, in addition to these, a molecular weight of 1,000
A compound having 1 to 4 oxetane rings having a relatively high molecular weight of about 5,000 to about 5,000 is also included. Further, as a polymer containing oxetane, a polymer having an oxetane ring in a side chain (for example, K. Sato, A. Kameyama)
a, and T.A. Nishikubo, Macromo
recules, 25, 1198 (1992))
Etc. can be used similarly. In the present invention, two or more oxetane compounds can be used in combination.

The compound (E2) having an oxiranyl group is not particularly limited as long as it has an oxirane ring in the molecule, and any compound can be used. Examples of the compound having such an oxiranyl group include, for example, ethylene oxide, propylene oxide, cyclohexene oxide, styrene oxide, methyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, ethylene glycol glycidyl phenyl ether, and ethylene glycol benzyl glycidyl. Glycidyl ethers such as ether and diethylene glycol glycidyl tetrahydropyranyl ether; glycidyl esters such as glycidyl methacrylate and glycidyl acetate;

In addition to the above compounds having an oxiranyl group, bisphenol A type epoxy resin, bisphenol F type epoxy resin, halogenated bisphenol A type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, halogenated Condensates of phenol ether epoxy resins such as phenol novolak type epoxy resins, polyols, polyether polyols and the like with epichlorohydrin, diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl Glycol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, etc. Ester epoxy resins such as copolymers of ter-based epoxy resins, glycidyl acrylate, glycidyl methacrylate, etc. and ethylenically unsaturated monomers (methyl methacrylate, ethyl acrylate, acrylonitrile, etc.), aliphatic or alicyclic epoxy resins And other compounds having an oxiranyl group. These are used alone or in combination of two or more. Also,
A part or all of the hydrogen atoms of the compound having oxiranyl may be substituted with a halogen atom such as a fluorine atom.

Compounds having an ethylenically unsaturated group (E
3) has, for example, one double bond in the molecule;
Ester monomers of acrylic acid or methacrylic acid (methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, iso-propyl acrylate, iso-propyl methacrylate, N-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, sec acrylate
-Butyl, sec-butyl methacrylate, t-acrylate
tert-butyl, tert-butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate,
Heptyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, acrylic acid Tetradecyl, tetradecyl methacrylate, hexadecyl acrylate, hexadecyl methacrylate, octadecyl acrylate, octadecyl methacrylate, eicosyl acrylate, eicosyl methacrylate, docosyl acrylate, docosyl methacrylate, cyclopentyl acrylate, cyclopentyl methacrylate, cyclohexyl acrylate, Cyclohexyl methacrylate, cycloheptyl acrylate, cycloheptyl methacrylate, benzyl acrylate, Benzyl acrylic acid, phenyl acrylate, phenyl methacrylate, methoxyethyl acrylate, methacrylic acid methoxyethyl, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate,
Dimethylaminopropyl acrylate, dimethylaminopropyl methacrylate, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, 2-fluoroethyl acrylate, 2-fluoroethyl methacrylate, 2-cyanoethyl acrylate, 2-cyanoethyl methacrylate, Methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxydipropylene glycol acrylate, methoxydipropylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, etc., styrene monomers (styrene, α-methylstyrene) , Pt-butylstyrene, etc.), polyolefin monomers (butadiene, isoprene, chloroprene, etc.), vinyl monomers (salts) Vinyl, vinyl acetate, etc.), nitrile-based monomers (acrylonitrile, methacrylonitrile, etc.), 1- (methacryloyloxy ethoxycarbonyl)
-2- (3'-chloro-2'-hydroxypropoxycarbonyl) benzene and the like.

The compound (E3) having an ethylenically unsaturated group includes ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, and triethylene glycol having two double bonds in the molecule. Diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, hexapropylene glycol diacrylate, hexapropylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol Dimethacrylate,
Butylene glycol diacrylate, butylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate,
1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol diacrylate,
5-pentanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, bisphenol A diacrylate Acrylate, bisphenol A dimethacrylate, 2,2-bis (4-acryloxyethoxyphenyl) propane, 2,
2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloxydiethoxyphenyl) propane, 2,2-bis (4-acryloxypolyethoxyphenyl) propane 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, bisphenol A diglycidyl ether diacrylate, bisphenol A diglycidyl ether dimethacrylate, m-divinylbenzene, p-divinyl Benzene and urethane diacrylate compounds are also included.

Further, as the compound (E3) having an ethylenically unsaturated group, in addition to the above-mentioned compounds, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, ethylene oxide-modified triacrylate Methylolpropane triacrylate, ethylene oxide-modified trimethylolpropane trimethacrylate, trimethylolpropane triglycidyl ether trimethacrylate, trimethylolpropane triglycidyl ether trimethacrylate, trivinylbenzene, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol tetra Acrylate, pentaerythritol Tiger methacrylate, and the like may also be mentioned. These compounds having an ethylenically unsaturated group (E
3) is used alone or in combination of two or more.

Compounds having an ethylenically unsaturated group (E
3) As methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, 2-
Ethylhexyl vinyl ether, n-decyl vinyl ether, n-dodecyl vinyl ether, n-hexadecyl vinyl ether, n-octadecyl vinyl ether, cyclohexyl vinyl ether, divinyl ether, allyl vinyl ether, ethynyl vinyl ether, benzyl vinyl ether, phenyl vinyl ether, p-chlorophenyl vinyl ether, 2-chloro Vinyl ethers such as ethyl vinyl ether, 2-methoxyethyl vinyl ether, diethylene glycol divinyl ether, ethyl (α-methyl vinyl) ether, and butyl (1-propenyl) ether are also included. These compounds (E3) having an ethylenically unsaturated group are used alone or in combination of two or more.

When the reactive monomer (E) is added as a component constituting the curable oxetane composition (C) of the present invention, oxetanyl is present in the molecule during the curing reaction of the curable oxetane composition (C). The hydroxyl group of the aliphatic or alicyclic compound (A) having two or more groups and one or more hydroxyl groups undergoes chain transfer, and the reactivity of the reactive monomer (E) is improved. The amount of the reactive monomer (E) used in producing the curable oxetane composition (C) of the present invention is as follows:
The reactive monomer (E) is used in an amount of 0.1 to 100 parts by weight of the aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule used in the present invention. It is preferable to use 1,000,000 parts by weight, more preferably 1 to 1,000,000 parts by weight, and most preferably 1 to 100,000 parts by weight. When the amount of the reactive monomer used is less than 0.1 part by weight, there is a tendency that a substantial addition effect is not seen,
When the amount is 0000 parts by weight or more, there is a tendency that the effect of chain transfer of the hydroxyl group in the aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl group in the molecule is not recognized.

(Other Components (F)) The curable oxetane composition (C) of the present invention may be used in various forms as long as the effects of the present invention are not impaired. Agents, reinforcements, coloring agents, stabilizers (heat stabilizers,
Weathering improver, etc.), extender, viscosity modifier, flame retardant, ultraviolet absorber, antioxidant, anti-tarnish, antibacterial, antifungal, antioxidant, antistatic, plasticizer, lubricant, foam Agent,
A release agent 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, condensed azo, Organic pigments such as anthraquinone-based, thioindigo-based, dioxazone-based, and phthalocyanine-based pigments are included. Examples of the stabilizer include hindered phenol compounds, hydrazine compounds, phosphorus compounds, benzophenone compounds, benzotriazole compounds, oxalic acid anilide compounds, and the like. Furthermore,
Examples of the inorganic filler include 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, and stainless steel fiber. Inorganic and metal fibers such as aluminum, titanium, copper, brass, magnesium, metal powders such as copper, iron, nickel, zinc, tin, lead, stainless steel, aluminum, gold and silver, wood powder, magnesia, calcia, etc. Oxides, aluminum silicate, diatomaceous earth, quartz powder, talc, clay, hydroxides, carbonates, sulfates, phosphates, borates, borosilicates, aluminosilicates, titanates, bases of various metals Sulfates, basic carbonates and other basic salts, glass materials such as glass hollow spheres and glass flakes, silicon carbide , Aluminum nitride, mullite, ceramic, such as cordierite, and the like waste, such as fly ash and micro silica.

(Solvent (G)) The aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule used in the present invention can be mixed with the curing agent (B). Excellent compatibility. Therefore, there is a feature that it is not necessary to use a solvent when producing the curable oxetane composition (C) of the present invention. However, it is suitable for the properties of each component such as the curing agent (B). Solvents can also be used. As the solvent (G) used when producing the curable oxetane composition (C) of the present invention, a solvent that can mix and disperse each component can be suitably selected. Specific examples of the solvent (G) include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether, toluene, benzene, xylene, acetone, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve, and dioxane. No. The solvent (G) can be used alone or in combination of two or more. The boiling point of the solvent (G) is preferably from 50C to 300C, more preferably from 70C to 250C. When the boiling point of the solvent (G) is less than 50 ° C., the solvent is liable to be scattered at the time of producing a cured product (D) described later,
If the temperature exceeds ℃, the solvent tends to be less likely to be scattered during the production of the cured product (D). The amount of the solvent (G) used in producing the curable oxetane composition (C) of the present invention is such that a uniform curable oxetane composition (C) can be produced,
There is no particular limitation as long as it is within a range that can achieve a predetermined fluidity, but an aliphatic or alicyclic compound having two or more oxetanyl groups and one or more hydroxyl groups in the molecule used in the present invention. It is preferable to use 0.1 to 10000 parts by weight of the solvent (G) per 100 parts by weight of (A).
It is more preferable to use 1 to 10,000 parts by weight,
Most preferably, 5000 parts by weight are used. When the amount of the solvent used is 0.1 parts by weight or less, there is a tendency that a substantial addition effect is not seen, and when the amount is 10000 parts by weight or more,
In producing the cured product (D) of the present invention, not only time is required for distilling off the solvent, but also the strength of the cured product (D) of the present invention tends to decrease.

(Curable Oxetane Composition (C)) The curable oxetane composition (C) of the present invention is, as described above,
At least one kind of the aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule and at least one kind of the curing agent (B); Monomer (E), other components (F),
And a solvent (G) in a ratio as described above, for example, according to a conventional method. here,
When the solvent (G) is used, two oxetanyl groups are present in the molecule.
Aliphatic or alicyclic compound (A) having at least one hydroxyl group and at least one hydroxyl group, a curing agent (B) and a solvent (G), and if necessary, a reactive monomer (E) and other components (F) After mixing, the solvent (G) may be distilled off to obtain the curable oxetane composition (C) of the present invention.

(Method for Producing Cured Product (D)) The method for producing the cured product (D) of the present invention is characterized in that the curable oxetane composition (C) has two or more oxetanyl groups and one hydroxyl group in the molecule. A curing agent (B ′) for ring-opening polymerization of an aliphatic or alicyclic compound (A) having at least one oxetanyl group as a polymerization initiator and an aliphatic system having at least two oxetanyl groups and at least one hydroxyl group in the molecule Alternatively, the alicyclic compound (A) is cured by ring-opening polymerization. Alternatively, a curing agent (B ″) that undergoes an addition reaction with an aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule of the curable oxetane composition (C). Is characterized by being cured by a polyaddition reaction, and the details are as described below.

Aliphatic or alicyclic compounds (A) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule
In the case of a curable oxetane composition (C) containing a cationic polymerizable catalyst (B1) or an anionic polymerizable catalyst as a curing agent (B ′) for ring-opening polymerization of the cured product (D) of the present invention,
The composition (C) can be obtained by leaving the composition (C) at a temperature around room temperature or stirring as needed to obtain a cured product (D). If the reactivity of the curing agent (B ') is good, cool it if necessary.
In the case where the reactivity is poor, a cured product (D) is obtained by heating if necessary. The reaction temperature at that time is -10
0 ° C to 200 ° C is preferred, 0 ° C to 200 ° C
Is more preferable, and 50 to 150 ° C. is most preferable. If the reaction temperature is lower than -100 ° C, the curing reaction does not substantially proceed. When the reaction temperature is 200
When the temperature exceeds ℃, an unwanted side reaction of the cured product tends to proceed. As a curing agent (B ′) for ring-opening polymerization of an aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule, a cationic polymerizable catalyst (B1) or In the production of the cured product (D) of the present invention using the curable oxetane composition (C) containing an anionic polymerizable catalyst, heating or cooling and irradiation with actinic rays may be used in combination. Irradiation with actinic light alone without cooling may be used alone. As the actinic ray, ultraviolet light, visible light, infrared light, and the like are preferably used.

Aliphatic or alicyclic compounds (A) having at least two oxetanyl groups and at least one hydroxyl group in the molecule
In the case of a curable oxetane composition (C) containing a latent cationic polymerizable catalyst (B2) or a latent anionic polymerizable catalyst as a curing agent (B ') for ring-opening polymerization of Cations formed from anionic catalysts / cations / anion species generated from anionic polymerizable catalysts or Lewis acids / Lewis bases are aliphatic or alicyclic systems having at least two oxetanyl groups and at least one hydroxyl group in the molecule. The oxetanyl group in the compound (A) is attacked to open the ring, and then the ring-opening reaction proceeds continuously to self-polymerize at a stretch to form a cured product (D) of the present invention having a three-dimensional network structure. It is estimated that Therefore, the reaction temperature at that time is from 20 ° C. to 20 ° C.
A range of 0 ° C is preferred, a range of 50 ° C to 200 ° C is more preferred, and a range of 60 ° C to 150 ° C is most preferred. When the reaction temperature is 20 ° C. or lower, the curing reaction does not substantially proceed. When the reaction temperature exceeds 200 ° C.,
Undesirable side reactions of the cured product tend to proceed.

As a curing agent (B ') for ring-opening polymerization of an aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule, a latent cationic polymerizable compound is used. In the method for producing the cured product (D) of the present invention using the curable oxetane composition (C) containing the catalyst (B2) or the latent anionic polymerizable catalyst, actinic rays may be irradiated. A cation formed from a latent cation / anionic polymerizable catalyst by irradiation with actinic light / a cation / anion species generated from the anionic polymerizable catalyst or a Lewis acid / Lewis base has two or more oxetanyl groups in the molecule. The oxetanyl group in the aliphatic or alicyclic compound (A) having one or more hydroxyl groups is attacked to open the ring, and then the ring-opening reaction proceeds continuously to self-polymerize at a stretch to form a three-dimensional network. It is estimated that a cured product of the structure is formed. Actinic rays used in the production method of the present invention include ultraviolet light, visible light, and infrared light. Among these actinic rays, ultraviolet rays and visible lights are preferred from the viewpoint of polymerization curing speed, and ultraviolet rays are particularly preferred. The main wavelength of the ultraviolet light is preferably 300 nm or more, and particularly preferably 350 nm or more.
In addition to energy rays, energy rays such as electron beams, X-rays, γ-rays, and microwaves can also be used.
When irradiating with ultraviolet light, various light sources can be used, such as a mercury arc lamp, a xenon arc lamp, a fluorescent lamp, a carbon arc lamp, a tungsten-halogen copying lamp, and curing by irradiation light from surrounding sunlight. Can be done. The irradiation amount of the actinic ray is not particularly limited as long as a sufficient curing reaction proceeds as a result, but is generally about 1 mJ / cm ^{2 to} 500,000 mJ /.
cm ² . Further, irradiation with actinic rays is performed once or twice.
The irradiation can be performed more than once, and the irradiation condition of each actinic ray may be the same or different. The temperature at the time of photopolymerization is not particularly limited, but is preferably within a range up to about 70 ° C., since higher temperatures tend to have better curability. In consideration of working conditions, a range of about 0 ° C. to 50 ° C. is preferable.

Further, as a curing agent (B ') for ring-opening polymerization of an aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule, a latent cationic polymerizable compound is used. In the method for producing the cured product (D) of the present invention using the curable oxetane composition (C) containing the catalyst (B2) or the latent anionic polymerizable catalyst, active light and heating may be used in combination. At this time, irradiation with active light and heating may be performed simultaneously, heating may be performed after irradiation with active light, or active light may be irradiated after heating. When the actinic ray and the heating are used in combination, the irradiation amount of the actinic ray, the heating temperature, and the heating time are not particularly limited, and can be appropriately determined in consideration of progress of a sufficient curing reaction. Further, irradiation with active light and heating can be performed once or twice or more, respectively, and the irradiation condition and heating condition of each active light may be the same or different.

The aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl group in the molecule used in the present invention has excellent compatibility with the curing agent (B). . Therefore, the curable oxetane composition (C) of the present invention may be used as it is in producing the cured product (D) of the present invention using the curing agent (B ′) to be subjected to ring-opening polymerization as a polymerization initiator. However, it may be used after dilution with a solvent. Specific examples of the solvent used when producing the cured product (D) of the present invention include dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethylene glycol dimethyl ether, toluene, benzene, xylene, acetone, methyl ethyl ketone, tetrahydrofuran, Ethyl cellosolve, ethyl cellosolve acetate, butyl cellosolve,
Dioxane and the like. The solvents can be used alone or in combination of two or more. The boiling point of the solvent is 50
C. to 300.degree. C. is preferred, and 70 to 250.degree. C. is more preferred. When the boiling point of the solvent is less than 50 ° C., the solvent tends to be scattered during the production of the cured product (D), and when it exceeds 300 ° C., the solvent tends to be less likely to be scattered during the production of the cured product (D). The amount of the solvent used in the production of the cured product (D) of the present invention using the curing agent (B ') to be subjected to ring-opening polymerization as the polymerization initiator is 100 curable oxetane composition (C).
The solvent (G) is preferably used in an amount of 0.1 to 5,000 parts by weight, more preferably 1 to 5,000 parts by weight, most preferably 1 to 1000 parts by weight based on parts by weight. When the amount of the solvent used is 0.1 parts by weight or less, there is a tendency that no substantial addition effect is observed, and
When the amount is more than the weight part, the viscosity of the composition is greatly reduced and handling becomes difficult. Furthermore, when producing the cured product (D) of the present invention, not only time is required for distilling off the solvent, but also the strength of the cured product (D) of the present invention tends to decrease.

In the production of the cured product (D) of the present invention using the curing agent (B ′) to be subjected to ring-opening polymerization as a polymerization initiator, the reaction pressure is not particularly limited. It can be implemented under any condition of pressure. Of these, it is preferable to produce a cured product under normal pressure because the apparatus can be simplified.

In the production of the cured product (D) of the present invention using the curing agent (B ′) for ring-opening polymerization as a polymerization initiator, the heating time, the time of irradiating with active light, that is, the curing time, Two or more oxetanyl groups and one hydroxyl group
The number of the aliphatic or alicyclic compound (A) and the curing agent (B ') and the amount of the curing agent (B') vary depending on the curing conditions such as the reaction temperature and the intensity of the actinic ray. Time, preferably 0.1 minute to
The time is preferably 10 hours, more preferably 1 minute to 5 hours. If the curing time is shorter than 0.1 second, the polymerization reaction of the oxetane compound (A) does not proceed, and the curability of the resulting cured product tends to decrease. Also, the curing time
If the time exceeds 50 hours, not only the curability is not improved, but also the quality tends to deteriorate due to deterioration.

The production of the cured product (D) of the present invention using the curing agent (B ') for ring-opening polymerization as a polymerization initiator is carried out in an inert gas atmosphere in order to prevent an undesirable reaction due to the influence of oxygen. It is preferable to carry out below. As the inert gas, a rare gas such as an argon gas or a helium gas may be used in addition to the nitrogen gas.

An aliphatic or alicyclic compound (A) having at least two oxetanyl groups and at least one hydroxyl group in the molecule
The cured product (D) of the present invention using the curable oxetane composition (C) containing the curing agent (B ″) that undergoes an addition reaction with the curable oxetane composition (C) is produced by heating the curable oxetane composition (C). The reaction temperature at that time is preferably in the range of 0 ° C. to 200 ° C., more preferably in the range of 30 ° C. to 200 ° C.
0 ° C to 200 ° C is most preferred. When the reaction temperature is 0 ° C. or lower, the curing reaction does not substantially proceed. If the reaction temperature exceeds 200 ° C., unwanted side reactions of the cured product tend to proceed. At the time of the reaction, stirring is not necessary, but stirring may be performed if necessary. Further, a curable oxetane composition (C) containing a curing agent (B ″) that undergoes an addition reaction with an aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule is provided. In the production of the cured product (D) of the present invention, heating or cooling and irradiation with actinic rays may be used in combination, and further, irradiation with actinic rays alone without heating or cooling may be used alone. As the actinic ray, ultraviolet light, visible light, infrared light and the like are preferably used.

The aliphatic or alicyclic compound (A) having at least two oxetanyl groups and at least one hydroxyl group in the molecule used in the present invention has excellent compatibility with the curing agent (B). . Therefore, the curable oxetane composition (C) of the present invention may be used as it is in producing the cured product (D) of the present invention using the curing agent (B ″) for addition polymerization as a polymerization initiator. The solvent may be diluted before use, and the above-mentioned solvents can be suitably used as the solvent.The present invention using the curing agent (B ″) for addition polymerization as a polymerization initiator can be used. The amount of the solvent used when producing the cured product (D) of the present invention is such that the solvent (G) is used in an amount of 0.1 to 5,000 parts by weight based on 100 parts by weight of the curable oxetane composition (C). Preferably, it is more preferable to use 1 to 5000 parts by weight,
It is most preferred to use from 1 to 1000 parts by weight. When the amount of the solvent used is 0.1 parts by weight or less, a substantial addition effect tends not to be seen, and when the amount is 5000 parts by weight or more, the viscosity of the composition is greatly reduced, and handling becomes difficult. Furthermore, when producing the cured product (D) of the present invention, not only time is required for distilling off the solvent, but also the strength of the cured product (D) of the present invention tends to decrease.

In the production of the cured product (D) of the present invention using the curing agent (B ″) for addition polymerization as a polymerization initiator, the reaction pressure is not particularly limited. Although it can be carried out under any of the above conditions, it is preferable to carry out the process under normal pressure because the apparatus can be simplified.

In the production of the cured product (D) of the present invention using the curing agent (B ″) for addition polymerization as a polymerization initiator, the heating time is usually in the range of 5 minutes to 120 hours.
If the curing time is shorter than 5 minutes, the polyaddition reaction of the aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl group in the molecule does not proceed, so that the obtained cured product Curability tends to decrease. When the curing time exceeds 120 hours, not only the curability is not improved, but also the quality tends to deteriorate due to deterioration.

The production of the cured product (D) of the present invention using the curing agent (B ″) for addition polymerization as a polymerization initiator can be carried out in an atmosphere of an inert gas in addition to the atmosphere. As the active gas, a rare gas such as an argon gas or a helium gas may be used in addition to the nitrogen gas.

(Curing Product (D)) According to the method for producing the cured product (D), an insoluble and infusible novel cured product (D) of the present invention having a three-dimensional network structure is obtained. Further, the curable oxetane composition, metal, rubber, plastic, formed parts,
After coating on a substrate such as a film, paper, wood, glass, concrete, or ceramic, and curing according to the production method, a substrate having the cured product as a film can be obtained. When the curing reaction is performed in the solvent, after the curing reaction is completed, the solvent is evaporated from the obtained reaction mixture, and then cooled to room temperature to obtain the cured product, After 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.

The curable oxetane composition of the present invention undergoes a rapid curing reaction (a ring-opening polymerization reaction or a polyaddition reaction of the oxetane ring in the oxetane compound) under the action of a curing agent, resulting in an insoluble and infusible three-dimensional composition. A new cured product having a network structure is formed. Therefore, this new cured product has excellent mechanical properties (tensile strength, hardness, etc.) and electrical properties (electrical insulation,
Low dielectric constant), adhesiveness, heat resistance, moisture resistance, chemical resistance, etc. As an alternative to epoxy resin, paints, coatings, varnishes, inks, paints, adhesives, electrical insulating materials , IC and LSI sealing materials, laminated boards and other electrical and electronic components, optical materials, optical fibers, optical waveguides, single-layer and multilayer wiring board materials, resists,
Dry film resist, repair of concrete structures, connection of old and new concrete, bonding of reinforcing steel plates, civil engineering and construction applications such as various linings, molding materials, composite materials, circuit connection materials by dispersing conductive particles, etc. Can be suitably used in the field of

[0112]

The present invention will be specifically described below with reference to examples.

(Synthesis Example 1) [3,3,18,18-bis (3-oxacyclobutylidene) -7,14-dihydroxy-5,9,12,16
-Synthesis of tetraoxaicosane (II)]

[0114]

Embedded image

The 500 ml reaction vessel was replaced with dry nitrogen,
Sodium hydride (60% oily) 0.9 g (22 mmo
l), 100 ml of N, N-dimethylformamide were added and the suspension was cooled to 0 ° C. There, 2.6 g of 3-ethyl-3- (hydroxymethyl) oxetane (22
(mmol) of N, N-dimethylformamide in 50 ml was slowly added, and the reaction mixture was stirred at 0 ° C. for 30 minutes. Thereafter, a solution of 1.7 g (10 mmol) of ethylene glycol diglycidyl ether in 50 ml of N, N-dimethylformamide was added dropwise, and the reaction solution was stirred for 6 hours under a stream of dry nitrogen while heating to 40 ° C. The reaction solution was poured into water and extracted with chloroform. The extract was dried over anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography to give 3,3,1
8,18-bis (3-oxacyclobutylidene) -7,
2.8 g of 14-dihydroxy-5,9,12,16-tetraoxaicosane (II) was obtained (yield 70%).

(Synthesis Example 2) [Synthesis of 3,3,16,16-bis (3-oxacyclobutylidene) -7,12-dihydroxy-5,14-dioxaoctadecane (III)]

[0117]

Embedded image

The 500 ml reaction vessel was replaced with dry nitrogen,
Sodium hydride (60% oily) 0.9 g (22 mmo
l), 100 ml of N, N-dimethylformamide were added and the suspension was cooled to 0 ° C. There, 2.6 g of 3-ethyl-3- (hydroxymethyl) oxetane (22
(mmol) of N, N-dimethylformamide in 50 ml was slowly added, and the reaction mixture was stirred at 0 ° C. for 30 minutes. Thereafter, a solution of 1.4 g (10 mmol) of 1,2,7,8-diepoxyoctane in 50 ml of N, N-dimethylformamide was added dropwise, and the reaction solution was stirred for 6 hours under a stream of dry nitrogen while heating to 80 ° C. . The reaction solution was poured into water and extracted with chloroform. The extract was dried over anhydrous sodium sulfate and concentrated. The residue was purified by silica gel column chromatography to give 3,3,16,
16-bis (3-oxacyclobutylidene) -7,12
-Dihydroxy-5,14-dioxaoctadecane (II
I) 3.0 g was obtained (80% of yield).

(Example 1) [Preparation of curable oxetane composition] As an aliphatic or alicyclic compound (A) having at least two oxetanyl groups and at least one hydroxyl group in the molecule, 3,3,3 As a curing agent (B), 1.0 g of 18,18-bis (3-oxacyclobutylidene) -7,14-dihydroxy-5,9,12,16-tetraoxaicosane (II) was used as a curing agent (B). Latent Cationic Polymerizable Catalyst San-Aid SI-1
Then, 0.02 g of 00L (IV) was mixed to obtain a curable oxetane composition (a-1).

[0120]

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(Example 2) [Preparation of curable oxetane composition] As an aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl group in the molecule, 3,3,3 16,16-bis (3-oxacyclobutylidene) -7,12-dihydroxy-5,14-dioxaoctadecane (III)
0 g, as a curing agent (B), a latent cationic polymerizable catalyst San-Aid SI-100L (I
V) 0.02 g was mixed and the curable oxetane composition (a
-2) was obtained.

(Example 3) [Preparation of curable oxetane composition] As an aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl group in the molecule, 3,3,3 As a curing agent (B), 1.0 g of 18,18-bis (3-oxacyclobutylidene) -7,14-dihydroxy-5,9,12,16-tetraoxaicosane (II) Latent cation polymerizable catalyst Adeka Opton SP-
The mixture was mixed with 0.02 g of 170 (V) to obtain a curable oxetane composition (a-3).

[0123]

Embedded image

(Example 4) [Preparation of curable oxetane composition] As an aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl group in the molecule, 3,3,3 16,16-bis (3-oxacyclobutylidene) -7,12-dihydroxy-5,14-dioxaoctadecane (III)
0 g, as a curing agent (B), Asahi Denka Kogyo Co., Ltd. latent cationic polymerizable catalyst Adeka Opton SP-170
(V) 0.02 g was mixed to obtain a curable oxetane composition (a-4).

An aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl group in the molecule
Has excellent compatibility with the curing agent (B), and in Examples 1 to 4, a uniform curable oxetane composition (C) could be produced without using the solvent (G).

(Example 5) [Curing reaction of curable oxetane composition] Copper foil (thickness: 35)
μm) on both sides, a copper-clad laminate that is a glass epoxy material (MCL-E-61 manufactured by Hitachi Chemical Co., Ltd.)
Was polished using a polishing machine having a brush equivalent to # 600 (manufactured by Sankei Co., Ltd.), washed with water, and dried in an air stream. The curable oxetane composition (a-1) was applied to the copper-clad laminate so as to have a thickness of about 20 μm.
After heating for an hour, an oxetane cured product (b-1) was obtained.

(Example 6) [Curing reaction of curable oxetane composition] The curable oxetane composition (a-2) was applied to the copper-clad laminate so as to have a thickness of about 20 µm, and then heated at 80 ° C for 2 hours. As a result, an oxetane cured product (b-2) was obtained.

(Example 7) [Curing reaction of curable oxetane composition] The curable oxetane composition (a-3) was applied to the copper-clad laminate to a thickness of about 20 µm, and a high-pressure mercury lamp was provided. Using an ultraviolet irradiation device, ultraviolet light having an illuminance of 1 mW / cm ² at 25 ° C. was irradiated for 2 minutes to obtain a cured oxetane (b-3).

Example 8 Curing Reaction of Curable Oxetane Composition The curable oxetane composition (a-4) was applied to the copper-clad laminate to a thickness of about 20 μm, and a high-pressure mercury lamp was provided. Using an ultraviolet irradiation device, ultraviolet light having an illuminance of 1 mW / cm ² at 25 ° C. was irradiated for 2 minutes to obtain a cured oxetane (b-4).

Comparative Example 1 Preparation of Curable Oxetane Composition As an oxetane compound, 3,3- (3-oxacyclobutylidene) -5-oxaundecane (VI) having no hydroxyl group (Ube Industries, Ltd.) 1.0 g, as a curing agent (B), a latent cationic polymerizable catalyst San-Aid SI manufactured by Sanshin Chemical Industry Co., Ltd.
-100 L (IV) of 0.02 g were mixed to obtain a curable oxetane composition (a′-2).

[0131]

Embedded image

Comparative Example 2 Preparation of Curable Oxetane Composition 3,3- (3-oxacyclobutylidene) -5-oxaundecane (VI)
1.0 g, as a curing agent (B), a latent cationic polymerizable catalyst Adeka Opton SP-170 manufactured by Asahi Denka Kogyo KK
(V) 0.02 g was mixed to obtain a curable oxetane composition (a′-4).

Comparative Example 3 Curing Reaction of Curable Oxetane Composition Curable oxetane composition (a'-2) was applied to the copper-clad laminate to a thickness of about 20 μm.
And heated at 80 ° C. for 2 hours to obtain an oxetane cured product (b′-2).

Comparative Example 4 [Curing Reaction of Curable Oxetane Composition] The curable oxetane composition (a′-4) was added to the copper-clad laminate by about 20 μm.
Then, the mixture was irradiated with ultraviolet rays having an illuminance of 1 mW / cm ² for 2 minutes at 25 ° C. using an ultraviolet irradiation apparatus equipped with a high-pressure mercury lamp to obtain a cured oxetane (b′-4).

[Evaluation of Characteristics of Oxetane Cured Product] (IR spectrum of cured product) Cured products (b-1) to (b-4) and (b'-) prepared in Examples 5 to 8 and Comparative Examples 2 and 3. 2) and the infrared absorption spectrum of (b'-4)
It was measured by the Br tablet method. As a result, it was confirmed that the peak around 950 cm ⁻¹ derived from the oxetane ring disappeared. Therefore, the curable oxetane composition (a-
1) to (a-4) and (a'-2), (a'-4)
It has been found that the curing reaction has sufficiently proceeded.

(Evaluation of Adhesion) The cured coating films on the copper-clad laminates obtained in Examples 5 to 8 and Comparative Examples 2 and 3 were evaluated for adhesion with reference to the cross-cut tape method described in JIS K5400. evaluated. Specifically, 1 mm
An incision was made with a cutter knife so as to have an area of × 1 mm, cellotape (registered trademark) was adhered to the surface of the coating film and peeled off, and the number of oxetane cured products remaining on the copper-clad laminate was measured. Table 1 shows the results.

[0137]

[Table 1]

As can be seen from Table 1, the aliphatic or alicyclic compound (A) having at least two oxetanyl groups and at least one hydroxyl group in the molecule of the present invention and the curing agent (B) are essential components. The cured product (D) using the curable oxetane composition (C) was excellent in adhesion.

(Measurement of Curability) Curable oxetane compositions (a-1) to (a-4), and (a'-2), (a '
-4) was weighed into a sample pan, and the differential scanning calorimeter DSC-7 manufactured by PerkinElmer was used to measure 20K.
At a heating rate of / min from 25 ° C to 200 ° C,
The heat of polymerization was measured. The amount of heat generated at this time is a (J / mo
1) and the total curing heat generation value.

Subsequently, the heat of polymerization was measured under the following three fast curing conditions. [Rapid curing condition 1] Curable oxetane composition (a-1),
(A-2) and (a'-2) were each weighed into a sample pan, and were measured by a differential scanning calorimeter D manufactured by PerkinElmer.
Heated at 100 ° C. for 30 seconds using SC-7. The calorific value at this time is defined as a ′ (J / mol).

[Rapid curing condition 2] The curable oxetane compositions (a-3), (a-4), and (a'-4) were each weighed into a sample pan, and calorimeter with an ultrahigh pressure mercury lamp manufactured by Seiko Instruments Inc. Using a photo DSC
An actinic ray having an illuminance of ² mW / cm ² was irradiated at 25 ° C. for 30 seconds (60 mJ / cm ² ). The calorific value at this time is a '(J
/ Mol)

[Rapid curing condition 3] The curable oxetane compositions (a-1) to (a-4) were each weighed into a sample pan, and a calorimeter (photo DSC) with an ultrahigh pressure mercury lamp manufactured by Seiko Instruments Inc. was first measured. Irradiated with actinic rays having an illuminance of ² mW / cm ² at 25 ° C. for 15 seconds (30
mJ / cm ² ). This sample was subsequently subjected to a differential scanning calorimeter DSC-7 manufactured by PerkinElmer Inc.
Heated at ° C for 15 seconds. The sum of the calorific values at this time is defined as a ′ (J / mol).

Here, the reaction rate at the time of rapid curing is expressed by the following equation (12) under any of the rapid curing conditions. Reaction rate (%) = a '/ a x 100 (12)

The curable oxetane compositions (a-1) to (a)
Tables 2 to 4 show the reaction rates under the respective fast curing conditions of (-4), (a'-2), and (a'-4). In either case of the thermosetting reaction or the photocuring reaction, the curable oxetane composition using an oxetane compound having a hydroxyl group has a higher reaction rate than the curable oxetane composition using an oxetane compound having no hydroxyl group. It was also found that a sufficient reaction rate was exhibited even under curing conditions in which a photocuring reaction and a thermosetting reaction were combined. Therefore, the curable oxetane composition having two or more oxetanyl groups in the molecule of the present invention and an aliphatic or alicyclic compound having one or more hydroxyl groups and a curing agent as an essential component is excellent in rapid curability. You can see that it is.

[0145]

[Table 2] Rapid curing condition 1 ―――――――――――――――――――――――――― Curable composition Curing condition Reaction rate ―――――― ―――――――――――――――――――――― a-1 100 ℃, 30 seconds ○ a-2 100 ℃, 30 seconds ○ a'-2 100 ℃, 30 seconds × ―――――――――――――――――――――――――――― Response rate: ○ 90% or more, × less than 90%

[0146]

[Table 3] Rapid curing condition 2 ―――――――――――――――――――――――――― Curable composition Curing condition Reaction rate ―――――― ―――――――――――――――――――――― a-3 60mJ / cm ² ○ a-4 60mJ / cm ² ○ a'-4 60mJ / cm ² × ――― ――――――――――――――――――――――――― Reaction rate: ○ 70% or more, × less than 70%

[0147]

[Table 4] Rapid curing condition 3 ――――――――――――――――――――――――――――― Curable composition Curing condition Reaction rate ――― ―――――――――――――――――――――――――― a-1 30 mJ / cm ² → 100 ° C, 15 seconds ○ a-2 30 mJ / cm ² → 100 ° C, 15 seconds ○ a-3 30mJ / cm ² → 100 ° C, 15 seconds ○ a-4 30mJ / cm ² → 100 ° C, 15 seconds ○ ―――――――――――――――― ――――――――――――――― Reaction rate: ○ 90% or more, × less than 90%

[0148]

The curable oxetane composition according to claim 1 has a low viscosity, and has excellent high-speed cationic polymerization ability and excellent adhesion. The curable oxetane composition according to claim 2 can be easily and inexpensively obtained in addition to the curable oxetane composition according to claim 1. The curable oxetane composition according to the third aspect is the first or second aspect.
In addition to the curable oxetane composition described above, a cured product having an appropriate crosslinking density can be obtained. Claim 4
The curable oxetane composition described above can provide a composition and a cured product having high storage stability in addition to the curable oxetane composition according to claims 1 to 3. The curable oxetane composition according to the fifth aspect is, in addition to the curable oxetane compositions according to the first to fourth aspects, cured in a short time to obtain a cured product having a higher crosslinking density. Claim 6
The curable oxetane composition according to the present invention has excellent storage stability before crosslinking and high reactivity in addition to the curable oxetane composition according to the first to fifth aspects. According to the method for producing a cured product according to claims 7 to 9, a cured product having high adhesion and high stability over time can be obtained. Claim 10
The cured products described in Nos. 1 to 12 exhibit high adhesion and high stability over time.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Shinno Nishiyama 48 Wadai, Tsukuba-shi, Ibaraki F-term in Hitachi Chemical Co., Ltd. F-term (reference) 4J005 AA07 BB02

Claims (12)

[Claims] 1. A curable oxetane composition comprising an aliphatic or alicyclic compound (A) having at least two oxetanyl groups and at least one hydroxyl group in a molecule, and a curing agent (B) as essential components. C). 2. An aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl group in the molecule represented by the general formula (1) or (2): The curable oxetane composition (C) according to claim 1, wherein Embedded image (Where Q represents an oxygen or sulfur atom, R ¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms, or an allyl group; R ² represents a divalent to hexavalent aliphatic or alicyclic organic group corresponding to the value of n, and n represents an integer of 2 to 6.) (Where Q represents an oxygen or sulfur atom, R ¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group or an allyl group having 1 to 6 carbon atoms, and R ³ represents oxetanyl. A divalent aliphatic group capable of forming a ring or an aliphatic organic group which may be substituted by an alicyclic system, and p represents an integer of 0 to 6.) 3. An aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule has 2 to 6 oxetanyl groups and 1 to 6 hydroxyl groups in the molecule. The curable oxetane composition (C) according to claim 1 or 2, which is an aliphatic or alicyclic compound having the following formula: 4. The molecular weight of the aliphatic or alicyclic compound (A) having two or more oxetanyl groups and one or more hydroxyl groups in the molecule is in the range of 144 to 5,000. The curable oxetane composition (C) according to any one of the above. 5. The curable oxetane composition (C) according to claim 1, wherein the curing agent (B) is a cationically polymerizable catalyst (B1). 6. The curable oxetane composition (C) according to claim 1, wherein the cationically polymerizable catalyst (B1) is a latent cationically polymerizable catalyst (B2). 7. A cured product obtained by heating the curable oxetane composition (C) according to any one of claims 1 to 6 at a temperature of 50 to 200 ° C. for 0.1 second to 50 hours. (D) Manufacturing method. 8. A method for producing a cured product (D), comprising irradiating the curable oxetane composition (C) according to claim 1 with actinic rays. 9. The curable oxetane composition (C) according to claim 1, which is irradiated with an actinic ray and heated at a temperature of 50 to 200 ° C. for 0.1 second to 50 hours. A method for producing a cured product (D). 10. The curable oxetane composition (C) according to claim 1, which is heated at 50 to 200 ° C.
Cured product (D) obtained by heating at a temperature of 0.1 seconds to 50 hours. 11. A cured product (D) obtained by irradiating the curable oxetane composition (C) according to claim 1 with actinic rays. 12. The curable oxetane composition (C) according to claim 1, which is irradiated with actinic rays and heated at a temperature of 50 to 200 ° C. for 0.1 second to 50 hours. Cured product (D).