JP2001115006A - Thermosetting composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polymerizable, curable material (namely thermosetting composition, especially a thermosetting composition for optical field) for providing a polymerized, cured material excellent in transparency, not requiring ultraviolet irradiation. SOLUTION: This thermosetting composition (or thermosetting composition for an optical field) comprises 100 pts.wt. of an oxetane ring-containing compound, 0.1-100 pts.wt. of an acrylic (co)polymer and 0.1-20 pts.wt. of a thermal cationic polymerization initiator. A method for producing the thermosetting composition is provided. This thermoset material is obtained by thermosetting the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermosetting composition (particularly, a thermosetting composition containing a compound having an oxetane ring), a method for producing the same, and a composition obtained by curing the curable composition. Related to cured product. Such thermosetting compositions include metals such as iron, plastics, concrete,
A coating film having excellent hardness, transparency, and the like can be formed on the surface of a substrate such as wood, and is useful in, for example, the optical field, coating application, paint field, and printing field.

[0002]

2. Description of the Related Art As a thermosetting composition, particularly a thermosetting composition containing a compound having an oxetane ring, JP-A-11-43540 discloses a compound having an oxetane ring and two or more carboxyl groups. A thermosetting oxetane composition comprising a compound having the formula:
Japanese Patent No. -60702 discloses a thermosetting oxetane composition comprising a compound having an oxetane ring and a functional acid anhydride or a free acid anhydride. However, in these publications, compounds having an oxetane ring and acrylic (co)
Thermoset compositions comprising the polymer are not described.

On the other hand, Japanese Patent Application Laid-Open No. Hei 8-245783 discloses that a polymerizable compound contains a compound having an oxetane ring and a polyalkyl methacrylate, which has a small shrinkage and is suitable for use for medical and dental purposes. Polymerizable curable materials are disclosed. However, according to this publication, an optical disc, an IC card (optical code), a plastic lens,
There is no description about polymerizable curable materials in the optical field, such as plastic optical fibers and optical fiber coating materials.

[0004] JP-A-10-212343 discloses that
(A) a compound having an epoxy group, (B) a compound having an oxetane ring, (C) a copolymer of a glycidyl group-containing polymerizable unsaturated monomer (such as glycidyl methacrylate) and another polymerizable monomer (such as methyl methacrylate) And (D) a UV-curable can coating composition containing a cationic polymerization initiator that generates cations upon irradiation with ultraviolet light. However, such a composition is not sufficiently satisfactory in terms of transparency and the like of the obtained cured polymer.

Further, it is difficult to apply the above-mentioned ultraviolet curable composition to large parts which cannot be irradiated with ultraviolet rays or articles having a structure which cannot be irradiated with ultraviolet rays, and an expensive ultraviolet irradiation apparatus is required. Also had problems such as. Therefore, a curable composition that can solve the above problem and does not rely on ultraviolet irradiation has been eagerly desired.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a polymer-curable material (ie, a thermosetting composition, particularly a thermosetting composition for the optical field) which gives a polymer-cured product having excellent transparency and does not require ultraviolet irradiation. A composition).

[0007]

The object of the present invention is to provide a compound having an oxetane ring having 100 parts by weight, an acrylic (co) polymer of 0.1 to 100 parts by weight, and a thermal cationic polymerization initiator of 0.1 to 20 parts by weight. A thermosetting composition (or a thermosetting composition for the optical field), a production method thereof, and a thermosetting product obtained by thermosetting the composition.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION [Compound having 1 to 4 oxetane rings in the molecule] As the compound having an oxetane ring used in the present invention, the following compound having 1 to 4 oxetane rings in the molecule: At least one compound selected from the group consisting of:

Among them, the compound having one oxetane ring in the molecule includes a monooxetane compound represented by the formula (2).

[0010]

Embedded image (In the formula, R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)

In the formula (2), R ³ represents a hydrogen atom or a carbon atom such as a methyl group, an ethyl group, an n- (or iso-) propyl group or an n- (or iso-, sec-) butyl group. Examples thereof include an alkyl group of 1 to 6, and among them, a hydrogen atom, a methyl group, and an ethyl group are preferable.
Methyl and ethyl groups are more preferred.

Examples of the monooxetane compound include 3-hydroxymethyloxetane and 3-methyl-3
-Hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, and the like.
3-Methyl-3-hydroxymethyloxetane and 3-ethyl-3-hydroxymethyloxetane are preferred. The monooxetane compound is synthesized by a method of generating a cyclic carbonate from 1,1,1-trimethylolalkane and dialkyl carbonate and then decarboxylating (see J. Am. Chem. Soc., 1957, 79). .

As the compound having two oxetane rings in the molecule, a bisoxetane compound represented by the formula (1) is preferably exemplified. Such compounds include the following. a monoether bisoxetane wherein x = 0, x = 1, and A is an alkylene group (which may contain an unsaturated bond, an aliphatic hydrocarbon ring, or an aromatic ring in the carbon chain); Ether bis oxetanes wherein x is an integer of 2 to 12, wherein A is an ethylene group.

[0014]

Embedded image (Wherein, R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, x represents an integer of 0 to 12. A represents x = 1
Represents an alkylene group (which may form an unsaturated bond, an aliphatic hydrocarbon ring, or an aromatic ring inside the carbon chain), and an integer of x = 2 to 12 represents an ethylene group. )

In the compound represented by the formula (1),
R ¹ and R ² represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and may be the same or different. Among the compounds, those in which R ¹ and R ² are the same as each other are preferable. Among them, those in which R ¹ and R ² are the same as each other and are any of a hydrogen atom, a methyl group, and an ethyl group are preferable. Among them, those in which R ² and R ³ are the same and are either a methyl group or an ethyl group are more preferred.

The monoether bisoxetanes include, for example, bis [(3-ethyl-3-oxetanyl) methyl] ether and bis [(3-methyl-3-oxetanyl) methyl] ether. In addition,
Monoether bisoxetanes include, for example, 3-alkyl-3-hydroxymethyloxetane and 3-alkyl-
It is synthesized by reacting 3-hydroxymethyloxetane with p-toluenesulfonyl chloride.

In the above diether bisoxetanes, the alkylene group (X) may form an unsaturated bond, an aliphatic hydrocarbon ring or an aromatic ring inside the carbon chain. That is, examples of the alkylene group include an alkylene group having 1 to 12 carbon atoms such as an ethylene group, a tetramethylene group, and a hexamethylene group. An aliphatic hydrocarbon ring (e.g., a cyclohexane ring or the like) is formed inside a carbon chain such as an alkylene group having 4 to 6 carbon atoms forming a saturated bond (a carbon-carbon double bond) or a group represented by the formula (4). ) To form an aromatic ring (such as a benzene ring) inside a carbon chain such as an alkylene group having 2 to 6 carbon atoms (excluding ring carbon atoms) or a xylylene group or a group represented by the formula (5). An alkylene group having 2 to 6 carbon atoms (excluding ring carbon atoms) (o
-, M- and p- isomers).

[0018]

Embedded image

Examples of the diether bisoxetanes include 1,2-bis (3-ethyl-3-oxetanylmethoxy) ethane, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6 -Bis (3-ethyl-3-oxetanylmethoxy) hexane, 1,4-bis (3-ethyl-3-oxetanylmethoxy) -2-butene, 1,4- [bis (3-ethyl-3-oxetanyl) Methoxy) methyl] cyclohexane and 1,4- [bis (3-ethyl-3-oxetanylmethoxy) methyl]
Benzene, 4,4 '-[bis (3-ethyl-3-oxetanylmethoxy) methyl] biphenyl, 4,4'-[bis (3-methyl-3-oxetanylmethoxy) methyl]
Biphenyl and the like.

The diether bisoxetanes are synthesized, for example, by reacting the corresponding dibromide (xylylene dibromide, ethylene dibromide, etc.) with 3-alkyl-3-hydroxymethyloxetane.

The polyether bisoxetanes include, for example, diethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis ( 3-ethyl-3-oxetanylmethyl) ether and the like. The polyether bisoxetanes are synthesized, for example, by reacting the corresponding polyethylene glycol (diethylene glycol, triethylene glycol, tetraethylene glycol, etc.) with p-toluenesulfonyl chloride of 3-alkyl-3-hydroxymethyloxetane. You.

As the compound having 3 or 4 oxetane rings in the molecule, a compound represented by the formula (6) is preferably exemplified.

[0023]

Embedded image (In the formula, R ⁴ is the same as R ¹ described above, Z represents a trivalent or tetravalent group, and n is 3 or 4. In addition, Z may have a substituent. Represents a trivalent or tetravalent hydrocarbon group, a trivalent or tetravalent group represented by the formula (7), or a trivalent or tetravalent group represented by the formula (8).

[0024]

Embedded image (In the formula, Y ¹ is a trivalent or tetravalent hydrocarbon group which may have a substituent, and p is 3 or 4.)

[0025]

Embedded image (In the formula, Y ² is a trivalent or tetravalent hydrocarbon group which may have a substituent, and q is 3 or 4.)

In the above Z, the trivalent or tetravalent hydrocarbon group which may have a substituent includes, for example, a group represented by the formula (9)
And trivalent or tetravalent aliphatic hydrocarbon groups having 1 to 12 carbon atoms represented by (11) to (11).

[0027]

Embedded image (In the formula, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

In the above Z, examples of the trivalent or tetravalent group represented by the formula (7) include those in which Y ¹ is a trivalent or tetravalent aromatic hydrocarbon group. Examples of Y ¹ include a trivalent aromatic hydrocarbon group represented by the following formula.

[0029]

Embedded image

In Z, the trivalent or tetravalent group represented by the formula (8) includes, for example, an aliphatic or aromatic hydrocarbon group in which Y ² is trivalent or tetravalent. . Examples of Y ² include a trivalent aliphatic or aromatic hydrocarbon group represented by the following formula.

[0031]

Embedded image

As the compound having 3 or 4 oxetane rings in the molecule, in formula (6), R ⁴ is the above-mentioned alkyl group, and Z is 3 to 4 carbon atoms represented by formula (9).
Those which are a valent aliphatic hydrocarbon group and those wherein R ⁴ is the above-mentioned alkyl group and Z is a trivalent or tetravalent group represented by the formula (7) are preferred. Further, in the formula (6), R ⁴ is an ethyl group, Z is a trivalent aliphatic hydrocarbon group having 1 to 12 carbon atoms represented by the formula (9), and R ⁵ is an ethyl group. And those in which R ⁴ is an ethyl group and Z is a trivalent or tetravalent group represented by the formula (7),
Further, it is more preferable that q = 3.

[0033]

Embedded image

The compound having 3 or 4 oxetane rings in the molecule represented by the above formula (6) is represented by the formula (1) using 3-alkyl-3-hydroxymethyloxetane as a starting material. It is synthesized by the same method as the bisoxetane compound to be used.

[Acrylic (co) polymer] The acrylic (co) polymer used in the present invention, that is, the thermoplastic acrylic (co) polymer, is an acryl (co) polymer obtained by using a (meth) acrylate as an acrylic monomer. A (co) polymer, that is, a (meth) acrylate (co) polymer produced by polymerizing a (meth) acrylate is preferably exemplified. In addition, (co) polymer represents a polymer or a copolymer, and (meth) acrylic acid represents acrylic acid or methacrylic acid.

The (meth) acrylic acid ester is a (meth) acrylic acid having an alkyl group having 1 to 20 (preferably 1 to 16) carbon atoms and having no oxetane ring or epoxy group as a substituent. Examples thereof include alkyl and cycloalkyl (meth) acrylate having 5 to 12 (preferably 5 to 7) carbon atoms and having a cycloalkyl group having no oxetane ring or epoxy group as a substituent. The above-mentioned alkyl group and cycloalkyl group may be further substituted with a halogen atom or the like. Also,
The alkyl group may be one in which a carbon chain constituting the alkyl group, such as a 2-ethoxyethyl group, is formed via at least one ether bond.

Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, a decyl group, a dodecyl group, a perfluorobutyl group and a 2-fluoroalkyl group. (Perfluoroisononyl) ethyl group and the like are specifically exemplified, and as the cycloalkyl group, a cyclohexyl group and the like are specifically exemplified. As the (meth) acrylate, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,
Butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Decyl (meth) acrylate, lauryl (meth) acrylate, perfluorobutyl (meth) acrylate, (meth)
2- (perfluoroisononyl) ethyl acrylate,
Specific examples include cyclohexyl (meth) acrylate. Specific examples of the (meth) acrylate (co) polymer include (co) polymers of these (meth) acrylates.

Among the acrylic (co) polymers, alkyl poly (meth) acrylates such as polymethyl (meth) acrylate and polyethyl (meth) acrylate are preferable. Among them, polymethyl methacrylate and polymethacrylic are preferable. Polyalkyl methacrylates such as ethyl acrylate are more preferred. The acrylic (co) polymer can be used alone or in combination.

In the present invention, the acrylic (co) polymer is
An epoxy group-containing acrylic (co) polymer may be contained in addition to the acrylic (co) polymer. That is, the acrylic (co) polymer may contain an epoxy group-containing acrylic monomer as a constituent unit of the (co) polymer in addition to the acrylic monomer (copolymer of the acrylic monomer and the epoxy group-containing acrylic monomer). And a mixture of the acrylic (co) polymer and the epoxy group-containing acrylic (co) polymer. The epoxy group-containing acrylic monomer or the epoxy group-containing acrylic (co) polymer is contained in an amount of 0 to 90% by weight, more preferably 0 to 90% by weight in the total amount of the acrylic (co) polymer including the epoxy group-containing acrylic monomer or the acrylic (co) polymer. It is preferably contained at a ratio of 80% by weight, and can be used alone or in combination.

The epoxy group-containing acrylic monomer is preferably an epoxy group-containing (meth) acrylic acid ester (ie, a (meth) acrylic acid ester of an epoxy group-containing alcohol), and is preferably an epoxy group-containing acrylic (co) polymer. Suitable examples include epoxy group-containing (meth) acrylate (co) polymers.

As the epoxy group-containing alcohol,
An alkyl group having 1 to 4 carbon atoms (preferably 1 to 2);
An epoxyalkyl alcohol having an alkyl group having an epoxy group as a substituent, or an epoxy having a cycloalkyl group having 5 to 12 (preferably 5 to 7) carbon atoms and having a cycloalkyl group having an epoxy group as a substituent. Cycloalkyl alcohol and the like. In addition,
In this case, the alkyl group or cycloalkyl group may be further substituted with a halogen atom or the like.

As the epoxy group-containing alcohol,
For example, glycidyl alcohol, 3,4-epoxycyclohexylmethanol, etc. are specifically exemplified. And as the epoxy group-containing (meth) acrylate, for example, glycidyl (meth) acrylate, (meth) acrylate
Specific examples include 3,4-epoxycyclohexylmethyl acrylate. Specific examples of the epoxy group-containing (meth) acrylate (co) polymer include (co) polymers of these epoxy group-containing (meth) acrylates.

Among the epoxy group-containing (meth) acrylates, glycidyl (meth) acrylate is preferred, and among them, glycidyl methacrylate is more preferred. And, among the epoxy group-containing (meth) acrylate (co) polymers, poly (glycidyl methacrylate) is preferable, and among them, polyglycidyl methacrylate is more preferable.

The acrylic (co) polymer contains an epoxy group-containing acrylic monomer as a structural unit (ie,
It is a copolymer with an epoxy group-containing acrylic monomer)
In this case, the acrylic (co) polymer is obtained by, for example, copolymerizing (radical polymerization) a (meth) acrylate and an epoxy group-containing (meth) acrylate so as to have the ratio described above by a known method. Also, the acrylic (co) polymer is an epoxy (acrylic) containing epoxy group.
When it is a mixture with a polymer, the acrylic (co) polymer can be obtained, for example, by mixing the (meth) acrylate (co) polymer and the epoxy group-containing (meth) acrylate (co) polymer in the above ratio. Can be.

In the present invention, the acrylic (co) polymer is one that forms a transparent polymer alloy with polyvinyl chloride or polyvinylidene fluoride, or one that contains an acrylic elastomer in the dispersed phase. Is also good.

[Thermal Cationic Polymerization Initiator] As the thermal cationic polymerization initiator used in the present invention, at least one compound selected from compounds capable of initiating oxetane ring opening and cationic polymerization by heat (heating) is used. Compounds. Examples of such a compound include various onium salts as shown below, for example, a quaternary ammonium salt represented by the formula (12), a phosphonium salt represented by the formula (13), and a compound represented by the formulas (14) to (15). And the like.

[0047]

Embedded image (Wherein, R ^{6 to} R ⁹ are an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an alkenyl group having 3 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, 7 ~
It is an aralkyl group of 12 or an alkoxy group having 1 to 20 carbon atoms, which may be the same or different, and may have a substituent. Two of R ^{6 to} R ⁹ may be bonded to each other to form a heterocyclic ring containing N, P, O, or S atoms. X ^- is a counter ion, BF ₄ ^-,
AsF ₆ ⁻ , SbF ₆ ⁻ , SbCl ₆ ⁻ , (C ₆ F ₅ ) ₄ B ⁻ , S
bF ₅ (OH) ⁻ , HSO ₄ ⁻ , p-CH ₃ C ₆ H ₄ SO ₃ ⁻ ,
It is selected from HCO ₃ ⁻ , H ₂ PO ₄ ⁻ , CH ₃ CO ₂ ⁻ , halogen ions (Cl ⁻ , Br ⁻ , I ^{− and the} like). )

[0048]

Embedded image (In the formula, R ^{6 to} R ⁹ and X ⁻ are the same as described above.)

[0049]

Embedded image (Wherein, R ^{6 to} R ⁸ and X ⁻ are each independently the above R ⁶ to R ⁸ )
Same as R ⁹ and X ⁻ . Ar represents an aryl group which may have a substituent. )

[0050]

Embedded image (Wherein, R ^{6 to} R ⁷ , X ⁻ , and Ar each represent the aforementioned R ⁶
And R ⁹ , X ⁻ and Ar. )

[0051]

Embedded image (In the formula, R ^{6 to} R ⁹ , X ⁻ and Ar are the same as described above.)

Examples of the quaternary ammonium salt include tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hydrogen sulfate, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate, N-dimethyl-N-benzylanilinium hexafluoroantimonate, N, N-dimethyl-N-
Benzylanilinium tetrafluoroborate, N, N
-Dimethyl-N-benzylpyridinium hexafluoroantimonate, N, N-diethyl-N-benzyltrifluoromethanesulfonate, N, N-dimethyl-N-
Specific examples include (4-methoxybenzyl) pyridinium hexafluoroantimonate, N, N-diethyl-N- (4-methoxybenzyl) toluidinium hexafluoroantimonate, and the like. Specific examples of the phosphonium salt include ethyltriphenylphosphonium hexafluoroantimonate and tetrabutylphosphonium hexafluoroantimonate.

Examples of the sulfonium salt include, for example, triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsinate, tris (4-methoxyphenyl) sulfonium hexafluoroarsinate, diphenyl (4-phenylthiophenyl) sulfonium hexafluoroarsinate,

Adeka Opton SP-150 (hereinafter, manufactured by Asahi Denka), Adeka Opton SP-170, Adeka Opton CP-66, Adeka Opton CP-77, Sun Aid SI-60L (hereinafter, manufactured by Sanshin Chemical), Sun Aid SI-
80L, Sun-Aid SI-100L, CYRACUR
EUVI-6974 (hereinafter, manufactured by Union Carbide), CYRACURE UVI-6990, and UVI
-508 (hereinafter, General Electric), UV
I-509, FC-508 (hereinafter, manufactured by Minnesota Mining and Manufacturing), FC-
509, CD-1010 (hereinafter, manufactured by Sartomer),
CD-1011 and CI series products (Nippon Soda)
And the like.

Further, in the present invention, a diazonium salt represented by the formula (17) and an iodonium salt represented by the formula (18) can also be used as the thermal cationic polymerization initiator.

[0056]

Embedded image (In the formula, Ar and X are the same as described above.)

[0057]

Embedded image (In the formula, R ^{6 to} R ⁷ and X ⁻ are the same as described above.)

As the diazonium salt, AMERI
CURE (made by American Can), ULTRASET
(Manufactured by Asahi Denka). Examples of the iodonium salt include diphenyliodonium hexafluoroarsinate, bis (4-chlorophenyl) iodonium hexafluoroarsinate, bis (4-bromophenyl) iodonium hexafluoroarsinate, and phenyl (4-methoxyphenyl) iodonium hexafluoroarsinate. Alcinate, UV-9310C (manufactured by Toshiba Silicone), Photoinitiator 2074 (manufactured by Rhone Poulin), UVE series products (manufactured by General Electric), FC series products (manufactured by Minnesota Mining and Manufacturing), etc. .

[Thermosetting Composition] The thermosetting composition of the present invention (or the thermosetting composition for the optical field) contains 1 to 3
It comprises 100 parts by weight of a compound having four oxetane rings, 0.1 to 100 parts by weight of an acrylic (co) polymer, and 0.1 to 20 parts by weight of a thermal cationic polymerization initiator. Among them, compound 1 having 1 to 4 oxetane rings in the molecule
A thermosetting composition (or a thermosetting composition for optical field) comprising 00 parts by weight, 0.1 to 100 parts by weight of an acrylic (co) polymer, and 0.1 to 10 parts by weight of a thermal cationic polymerization initiator. preferable. The compounds having 1 to 4 oxetane rings in the molecule, the acrylic (co) polymer, and the thermal cationic polymerization initiator are preferably those described above.

For example, the composition is prepared by mixing and dissolving an acrylic (co) polymer at a predetermined ratio with respect to 100 parts by weight of a compound having 1 to 4 oxetane rings in the molecule, and then adding a thermal cationic polymerization initiator. Is added at a predetermined ratio and mixed and dissolved. The temperature at this time is a temperature that does not cause thermal cationic polymerization, for example, 50
It is preferable that the temperature is lower than 10 ° C, more preferably 10 to 30 ° C. Usually, the composition is prepared at normal temperature. The pressure and atmosphere during preparation are not particularly limited, and may be normal pressure.

[Thermoset Product] The thermoset product of the present invention can be obtained by heating and thermosetting the thermosetting composition (or thermosetting composition for the optical field). At this time, the heating causes the ring-opening polymerization of the compound having an oxetane ring to proceed and the thermosetting to proceed. The heating (thermal curing reaction) temperature is preferably a temperature at which the composition can maintain a molten state. That is, the heating temperature is preferably 50 ° C. or more, more preferably 50 to 200 ° C., and particularly preferably 60 to 160 ° C.

Although the time of the thermosetting reaction varies depending on the composition of the thermosetting material and the conditions of the thermosetting reaction, it is usually from 1 minute to 50 hours.
Preferably 5 minutes to 10 hours, more preferably 10 minutes to 5 hours
It should be about an hour. The pressure of the thermosetting reaction is not particularly limited as long as the above-mentioned molten state can be maintained, and may be any of normal pressure, pressurization, and pressure reduction. The reaction atmosphere is preferably under drying (particularly under dry air).

The thermosetting reaction can be carried out, for example, by placing the previously prepared composition in a reaction vessel and heating the composition, or by preparing the composition in a reaction vessel and subsequently heating the composition. Can also. Further, the composition, iron, stainless steel, metals such as aluminum,
Rubber, plastic (including molded parts and films),
The method can also be carried out by applying the composition to the surface of a substrate such as paper, wood, glass, cloth, concrete, cement mortar, ceramics (including films, plates, molded parts, and other shaped articles) and then heating. The application of the thermosetting composition to the substrate surface may be performed by a commonly used method such as brush coating, spin coating, spray coating, casting, dipping, roll coating, screen printing, gravure printing, and the like.

When thermosetting is performed in a reaction vessel, the thermosetting product can be obtained by taking out from the obtained reaction mixture and drying at 100 ° C. or lower for 2 to 16 hours. When thermosetting is performed on the substrate surface, the thermosetting product is obtained as a film (coating) formed on the substrate surface.

The thermosetting product of the present invention obtained as described above is excellent in transparency, hardness and the like, and has low odor and irritation. When a thermosetting product is obtained as a film (coating film), the cured product has a thickness of 0.1 to 600 μm, preferably 1 to 500 μm, and a thick film as a protective film (coating material) on the substrate surface. It can be formed. Although the thermosetting material of the present invention has such excellent properties, it is particularly excellent in transparency, so that optical discs, IC cards (optical cords), plastic lenses, plastic optical fibers, and optical fibers, which require transparency, are required. It is suitable for optical fields such as coating materials. That is, the thermosetting composition is useful as a thermosetting composition for the optical field.

[0066]

Next, the present invention will be described specifically with reference to examples and comparative examples. In addition, evaluation of the thermosetting material was performed by the following method.

(1) Thickness of the coating film The thickness (μm) of the coating film formed on the surface of the glass plate is calculated from the total thickness (μm) of the glass plate and the coating film (μm).
m) was subtracted.

(2) Transparency of coating film Judgment was made visually. (○: colorless and transparent, ×: opaque)

(3) Hardness of Paint Film (Pencil Hardness) The hardness of the paint film was evaluated by a pencil hardness test based on JIS K5400.

(4) Adhesiveness of Coating Film The adhesiveness of the coating film was evaluated by a grid tape method based on JIS K 1990.

Reference Example 1 [Synthesis of bis [(3-ethyl-3-oxetanyl) methyl] ether] 2 L internal volume equipped with thermometer, stirrer, rectification tower, cooler, nitrogen gas inlet tube, and dropping funnel (Liter) in a four-necked flask with 3-ethyl-3-hydroxymethyloxetane (hereinafter referred to as EHO) 511.
1 g (4.4 mol) of triethylamine (hereinafter referred to as TEA
222.6 g (2.2 mol), toluene 11
100 g, and the reaction temperature was 10 ° C. in a nitrogen gas atmosphere.
229.1 g (2.0 mol) of methanesulfonyl chloride (hereinafter referred to as MSC) was added dropwise from the dropping funnel while maintaining the following conditions. Thereafter, the reaction was continued at room temperature for another 2 hours to terminate the reaction, and the formed precipitate was removed by filtration.

The washing and the filtrate obtained by washing the precipitate with 100 g of toluene were returned to the reactor together, and 32.2 g of tetra-n-butylammonium bromide (hereinafter referred to as TABA) was added.
After the addition, 60.0 g (1.5 mol) of sodium hydroxide pellets were added at 60 ° C. with stirring for 1 hour.
After completion of the addition, the reaction was continued for 2 hours and further at 70 ° C. for 5 hours. After completion of the reaction, 300 g of pure water was added to separate an organic layer. Next, 307.5 g (1.4 mol: 1.4 mol) of the target bis [(3-ethyl-3-oxetanyl) methyl] ether (hereinafter referred to as DOE) was obtained from the organic layer.
(Yield 71%) was separated by distillation (200 ° C./6 mmH
g). Its purity by gas chromatography analysis (area percentage) is 98.9%, and its vapor pressure is about 140 ° C.
Was 10 mmHg.

Reference Example 2 [Synthesis of 1,2- [bis (3-ethyl-3-oxetanyl) methoxy] ethane] In the same four-necked flask as in Reference Example 1, 220.7 g (1.9 mol) of EHO was added. TEA22
2.6 g (2.2 mol) and 1100 g of toluene were added.
229.1 g (2.0 mol) of MSC as in Reference Example 1.
, Reaction, and separation. The washing solution and the filtrate were returned to the reactor, and 32.2 g of TABA and ethylene glycol 6 were added.
After adding 8.3 g (1.1 mol), sodium hydroxide pellets (1.5 mol) were added in the same manner as in Reference Example 1 to carry out a reaction. After completion of the reaction, the same operation as in Reference Example 1 was performed to obtain the desired 1,2- [bis (3-ethyl-3-oxetanyl) methoxy] ethane (hereinafter referred to as EDOE).
102.8 g (0.63 mol: 63% yield) were separated by distillation (200 ° C./6 mmHg). Its purity by gas chromatography analysis (area percentage) is 98.6.
%, The vapor pressure was about 140 ° C. and 3 mmHg.

Example 1 10 parts by weight of DOE obtained in Reference Example 1 as a compound having 1 to 4 oxetane rings in a molecule (hereinafter referred to as an oxetane compound) was placed in a flask having an inner volume of 30 ml.
And parapet GH as acrylic (co) polymer
(Kuraray Co., Ltd.) was added in an amount of 0.5 part by weight, and the mixture was stirred and mixed and dissolved at 130 to 150 ° C. for 2 hours. After the mixture was cooled to room temperature, SI-60 was used as a hot cationic polymerizable catalyst.
L (manufactured by Sanshin Chemical Co., Ltd.) was added in an amount of 0.2 part by weight, mixed and dissolved to prepare a thermosetting composition.

Next, the thermosetting composition was cast at room temperature on a glass plate (100 mm × 100 mm × 1.7 mm) to which a spacer was attached, and then cast in air.
Heating at 1 ° C. for 1 hour gave a transparent coating having a thickness of 70 μm. The pencil hardness of this coating film was> 2H, and the evaluation by the grid tape method was 100.

Examples 2 to 7 The composition of the thermosetting composition was changed as shown in Table 1 (Examples 2 to 7), and the heating (thermosetting) temperature was changed as shown in Table 1 (Example 5). -7) Except for this, a coating film was obtained in the same manner as in Example 1. The obtained coating film was transparent, had a pencil hardness of> 2H, and had an evaluation of 100 by the grid tape method.

[0077]

[Table 1]

Comparative Examples 1-4 In place of the oxetane compound, 10 parts by weight of an epoxy compound: Cyracure UVR-6110 (manufactured by Union Carbide) was used, and the composition of the thermosetting composition was changed as shown in Table 2. Was obtained in the same manner as in Example 1. Each of the obtained coating films was opaque, having a pencil hardness of> 2H and an evaluation of 0 by the grid tape method.

Comparative Examples 5 to 8 The composition of the thermosetting composition was changed as shown in Table 2 without using an acrylic (co) polymer, and the heating (thermosetting) temperature was changed as shown in Table 2. Was obtained in the same manner as in Example 1. Although the obtained coating films were all transparent, the pencil hardness was <B in Comparative Examples 5 and 6, and the evaluation by the grid tape method was 70 in Comparative Examples 7 and 8.

[0080]

[Table 2]

[0081]

According to the present invention, excellent hardness, transparency, etc.,
It is possible to produce a thermosetting product (a cured product produced by polymerization and curing by heating) having low odor and irritation and capable of forming a thick film. In particular, since the thermosetting material of the present invention is excellent in transparency, optical discs and ICs that require transparency are required.
It is suitable for optical fields such as cards (optical cords), plastic lenses, plastic optical fibers, and optical fiber coating materials, and the thermosetting composition of the present invention is useful as a thermosetting composition for the optical field.

Claims (6)

[Claims] 1. 100 parts by weight of a compound having 1 to 4 oxetane rings in the molecule, 0.1 acrylic (co) polymer
To 100 parts by weight, and a thermal cationic polymerization initiator 0.1 to 2
A thermosetting composition comprising 0 parts by weight. 2. The compound having 1 to 4 oxetane rings in the molecule is a compound represented by the formula (1).
The thermosetting composition according to the above. Embedded image (Wherein, R ¹ and R ² are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, x represents an integer of 0 to 12. A represents x = 1
Represents an alkylene group (which may form an unsaturated bond, an aliphatic hydrocarbon ring, or an aromatic ring inside the carbon chain), and an integer of x = 2 to 12 represents an ethylene group. ) 3. The thermosetting composition according to claim 1, wherein the acrylic (co) polymer is a (meth) acrylate (co) polymer. 4. A compound having 1 to 4 oxetane rings in a molecule, 100 parts by weight, an acrylic (co) polymer 0.1
To 100 parts by weight, and a thermal cationic polymerization initiator 0.1 to 2
A thermosetting composition for optical fields comprising 0 parts by weight. 5. A thermosetting product obtained by thermosetting the thermosetting composition according to claim 1. 6. An acrylic (co) polymer is dissolved in an amount of 0.1 to 100 parts by weight based on 100 parts by weight of a compound having 1 to 4 oxetane rings in a molecule, and then 100 parts by weight of a compound having an oxetane ring is dissolved. A method for producing a thermosetting product, comprising adding 0.1 to 20 parts by weight of a thermal cationic polymerization initiator to a compound having an oxetane ring and subjecting the compound to ring-opening polymerization.