JP2001081182A - Polymerizable resin and polymerizable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin having excellent thermal radical polymerizability and photoradical polymerizability, useful as a coating material, etc., by subjecting a monomer component containing a specific unsaturated monomer to a cationic polymerization. SOLUTION: This polymerizable resin is obtained by subjecting a monomer component containing an unsaturated monomer (A) containing an alicyclic epoxy group and/or oxetane group in the molecule to a cationic polymerization. The monomer component contains a (meth)acryloyl group. The polymerizable resin comprises the component A and (B) another monomer to be subjected to a cationic polymerization, especially an alkyl vinyl ether monomer. This polymerizable resin composition comprises the resin and (C) a radically polymerizable monomer. This polymer comprises the whole or a part of a main chain skeleton of the polymer having a structural unit of the formula (R1 is a (meth)acryloyl group-containing organic group; m is 1-10; X is H or a 1-10C hydrocarbon; n is 2-10).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel polymerizable resin and a polymerizable resin composition containing the same.

[0002]

2. Description of the Related Art Unsaturated polyester resins, urethane acrylate resins and the like have been generally used as radical polymerizable resins used in the fields of paints, adhesives, adhesives, inks and the like.

[0003]

However, these resins are inferior in heat radical polymerizability and photo radical polymerizability, so that when dried in air, curing inhibition by oxygen occurs, and the surface drying property of the coating film is reduced. There is a problem that it is not good. Therefore, an object of the present invention is to provide a novel polymerizable resin excellent in thermal radical polymerizability and photoradical polymerizability, and a resin composition using the same.

[0004]

According to the present invention, a monomer component containing an unsaturated monomer (A) having an alicyclic epoxy group and / or an oxetane group in a molecule is provided. Provided is a polymerizable resin obtained by cationic polymerization.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The novel polymerizable resin of the present invention is obtained by cationically polymerizing a monomer component containing an unsaturated monomer (A) having an alicyclic epoxy group and / or an oxetane group in a molecule. It becomes. The unsaturated group of the unsaturated monomer (A) is not particularly limited as long as it has radical polymerizability, but is preferably a (meth) acryloyl group.

The (meth) acrylate monomer having an alicyclic epoxy group is opened by a cationic polymerization as shown in the following formula, and a part or the whole of the main chain skeleton of the polymer has an alicyclic hydrocarbon group. And a structural unit represented by the following formula (1) having a polyether structure containing: and having an organic group containing at least one or more (meth) acryloyl groups as a substituent of the alicyclic hydrocarbon group. Become.

[0007]

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(Wherein R ¹ is an organic group having a (meth) acryloyl group, m is an integer of 1 to 10. X is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. And n is an integer of 2 to 10.) The (meth) acrylate monomer having an oxetane group is opened by a cationic polymerization as shown in the following formula, and a part or all of the polymer is in the main chain skeleton. Has a poly (1,3-propylene glycol) structure, and at least one or more of the substituents in the 1,3-propylene glycol structure is an organic group containing a (meth) acryloyl group, and the other substituents are It is a structural unit represented by the following formula (2), which is a hydrogen atom and / or a hydrocarbon group having 1 to 10 carbon atoms.

[0009]

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Wherein R ² is an organic group having a (meth) acryloyl group. R ³ is an organic group having a (meth) acryloyl group, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. X is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.) Therefore, the polymerizable resin of the present invention has a monomer unit having an ether bond in the skeleton, and is adjacent to the monomer unit. The methylene group trapping oxygen does not cause curing inhibition due to oxygen, and shows good air curability.

As the (meth) acrylate monomer having an alicyclic epoxy group in the molecule, a compound represented by the following general formula can be mentioned.

[0012]

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[0013]

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[0014]

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[0015]

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[0016]

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[0017]

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(However, in the above chemical formula, R ⁵ is a hydrogen atom or a methyl group, R ⁶ is an alkylene group having 1 to 10 carbon atoms, and w is an integer of 0 to 10). As a specific example,

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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And the like. Examples of the (meth) acrylate monomer having an oxetane group in the molecule include the following compounds.

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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These monomers (A) may be used alone or in combination of two or more. The monomer component contains the above-mentioned monomer (A), and may be composed of only the above-mentioned monomer (A), or may contain other monomers. The other monomer is not particularly limited as long as it is capable of cationic polymerization, and examples thereof include an alkyl vinyl ether monomer, a glycidyl group-containing compound, an aziridine compound, a cyclic sulfide compound, a cyclic ether compound, and a styryl group-containing compound. Among them, the alkyl vinyl ether monomer (B) is preferable. When an alkyl vinyl ether monomer is used, it is possible to freely design a resin suitable for various fields such as paints, adhesives, adhesives, and inks by changing the type of the alkyl vinyl ether monomer used. These other monomers may be used alone or in combination of two or more.

The alkyl vinyl ether monomer (B) is
By cationic polymerization, addition polymerization results in a structural unit represented by the following formula.

[0035]

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(R ⁴ is a hydrocarbon group having 1 to 18 carbon atoms. X is independently a hydrogen atom or 1 to 10 carbon atoms.
Is a hydrocarbon group. Examples of the alkyl vinyl ether monomer (B) include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether,
Stearyl vinyl ether, ethyl propenyl ether, butyl propenyl ether, cyclohexyl propenyl ether, dodecyl propenyl ether, propenyl ether propylene carbonate, and the like,
There is no particular limitation.

The alkyl vinyl ether monomers (B) may be used alone or in combination of two or more. When the monomer component contains a monomer other than the monomer (A), the ratio of the monomer other than the monomer (A) is not particularly limited. %, More preferably 30 to 70% by weight.

In the cationic polymerization of the monomer component, a conventionally known cationic polymerization initiator can be used. Specifically, protonic acids such as perchloric acid, sulfuric acid, phosphoric acid, paratoluenesulfonic acid, trichloroacetic acid, and trifluoroacetic acid; boron trifluoride, aluminum bromide, aluminum chloride, antimony pentachloride, and ferric chloride , Tin tetrachloride, 4
Lewis acids such as titanium chloride, mercury chloride, and zinc chloride; and others such as iodine and triphenylchloromethane. Among them, boron trifluoride and p-toluenesulfonic acid are preferred. These cationic polymerization initiators may be used alone or in combination of two or more. The amount of the cationic polymerization initiator used is, based on the monomer component,
It is preferably 0.05 to 5% by weight, and 0.1 to 2% by weight.
More preferably, it is% by weight.

The polymerizable resin of the present invention is obtained by cationically polymerizing the above monomer component. When only the monomer (A) is used as the monomer component, the monomer (A) ) Is a homopolymer. When a monomer component containing a monomer (A) and another monomer is used, the monomer (A)
And a homopolymer of the monomer (A) and a homopolymer of the monomer other than the monomer (A).

The polymerizable resin of the present invention has a number average molecular weight of 5
00 to 30,000, weight average molecular weight of 700 to 60,
000, and a number average molecular weight of 1,000
0-20,000, weight average molecular weight of 1,000-3
More preferably, it is 0.000. Since the polymerizable resin of the present invention has an unsaturated group having radical polymerizability in a side chain, it exhibits radical polymerizability. Therefore, the polymerizable resin of the present invention can be cured with only the polymerizable resin if desired, but its use is sometimes limited because of its generally high viscosity. Therefore, in this case, it is preferable to use a radical polymerizable resin composition containing the polymerizable resin of the present invention and the radical polymerizable monomer (C). Whether to cure with the polymerizable resin of the present invention alone or to use it in combination with the radically polymerizable monomer (C) as a radically polymerizable resin composition can be selected depending on the intended use or desired. For example, when odor is a problem, a monomer having a low odor may be selected as the radical polymerizable monomer (C), and if there is no problem in workability and curability, the monomer is cured only with the polymerizable resin of the present invention. It is also possible to make it. Examples of applications in which odor is a problem include, for example, coating of civil engineering and building base materials, floor waterproof coating, and coating.

The method for producing such a polymerizable resin composition includes (1) aromatic hydrocarbons such as toluene and xylene;
Esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ethers such as diethyl ether; cationic polymerization of the above monomer components in a normal solvent of a halogenated hydrocarbon such as chloroform. To produce the polymerizable resin of the present invention, devolatilizing the solvent and diluting it with a radical polymerizable monomer (C), or (2) a liquid radical polymerizable monomer (C The cationic polymerization of the above-mentioned monomer components is carried out in the above), whereby the polymerizable resin of the present invention and the radical polymerizable monomer (C)
(I.e., a method of obtaining a mixture with the above (i.e., a polymerizable resin composition)). In particular, the method (2) is preferable because the polymerizable resin composition can be produced in one step.

Examples of the radical polymerizable monomer (C) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and (meth) acrylic acid 2 (Meth) acrylates such as ethylhexyl; dimethyl maleate;
Dibutyl fumarate; diethylene glycol di (meth) acrylate, oligoethylene glycol di (meth) acrylate such as ethylene glycol di (meth) acrylate or oligopropylene glycol di (meth) acrylate; neopentyl glycol di (meth) acrylate, glycerin tri ( At least one monomer selected from meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, styrene, vinyl acetate, diallyl phthalate, etc. Can be used. In particular, it is preferable to use a monomer having a high boiling point such as diethylene glycol di (meth) acrylate for applications in which odor is a problem.

The mixing ratio of the polymerizable resin of the present invention to the radical polymerizable monomer (C) is not particularly limited, but from the viewpoint of good working viscosity and material properties, the weight ratio is (polymerizable resin):
(Radical polymerizable monomer) = 90: 10 to 10:90 is preferable, 70:30 to 30:70 is more preferable, and 6
0:40 to 40:60 is most preferred. In applications where odor is a problem, the polymerizable resin of the present invention and a low-odor, high-boiling radical polymerizable monomer (C) are preferred in consideration of workability, physical properties of the resulting coating film, and other desired performance requirements. ) Can be determined, but the above range is preferably employed.

The polymerizable resin composition of the present invention can be cured in the presence of a thermal radical polymerization initiator represented by various organic peroxides. As the thermal radical polymerization initiator that can be used, various organic peroxides and / or azo-based polymerization initiators can be used. Examples of organic peroxides include benzoyl peroxide, lauroyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, di-te
rt-butyl peroxide, tert-butyl perbenzoate, cyclohexanone peroxide and the like. Examples of the azo polymerization initiator include azobisisobutyronitrile and azobisvaleronitrile.

These thermal radical polymerization initiators may be used alone or in combination of two or more. Further, the addition amount of the thermal radical polymerization initiator is usually 0.3 to 3 parts by weight based on 100 parts by weight of the total amount of the polymerizable resin composition. From the viewpoint of the balance between excellent thermal radical curability and coloring of the cured product, the amount of the thermal radical polymerization initiator is preferably 0.5 to 1.5 parts by weight. The curing temperature when these thermal radical polymerization initiators are used varies depending on the type and amount of polymerization inhibitor, curing accelerator, curing agent or other conditions, but generally ranges from 0 to 140 ° C. Curing takes place in the range.

Further, if necessary, various thermal radical curing accelerators can be used. Examples of the curing accelerator that can be used include a metal salt having a redox effect having a substituent of an aliphatic, aromatic, or alicyclic carboxylic acid, or a metal chelate complex, and particularly, cobalt, manganese,
A compound containing tin, vanadium, and / or copper is preferably used because of a large accelerating effect upon curing. Representative compounds include naphthenates, octenoates, phosphates, and acetylacetonate complexes of the above metals.
It is used in the range of 1 to 0.1 parts by weight. Further, in addition to these curing accelerators, dimethylaniline, acetylacetone, and / or acetoacetic anilide may be used in combination. These may be used alone or in combination of two or more.

In addition to the above-mentioned thermal radical polymerization initiator, it is also possible to use a photo-radical polymerization initiator.
The photo-radical polymerization initiator is not particularly limited as long as it has a capability of generating a radical species by the action of light and initiating a curing reaction of the polymerizable resin composition of the present invention. Specific examples of the photoradical polymerization initiator that can be used include 4-phenoxydichloroacetophenone and 4-t-.
Butyldichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone,
2-hydroxy-2-phenyl-1-phenylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1
Acetophenone-based compounds such as -hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; Benzoin-based compounds such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl 4'-methyldiphenylsulfide, 3,3'-dimethyl-4- Methoxybenzophenone, 4,4′-dimethylaminobenzophenone,
4,4′-diethylaminobenzophenone, 3,3 ′,
4,4'-tetra (t-butylperoxycarbonyl)
Nobenzophenone compounds such as benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-
Thioxanthone compounds such as diethylthioxanthone, 2,4-diisopropylthioxanthone, isopropylthioxanthone, 1-chloro-4-propoxythioxanthone and 2,4-dichlorothioxanthone; α-acyloxime ester, methylphenylglyoxylate, benzyl, 9,10 -Ketone compounds such as phenanthrenequinone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ', 4'-diethylisophthalophenone;2,2'-bis (2-chlorophenyl)-
Imidazole compounds such as 4,4 ', 5,5'-tetraphenyl-1,2'-imidazole; acylphosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; and other carbazole compounds At least one compound selected is given.

These photo-radical polymerization initiators may be used alone or in combination of two or more. Further, the addition amount of the photo-radical polymerization initiator is usually 0.1 to 30 parts by weight based on 100 parts by weight of the total amount of the polymerizable resin composition. In light of the balance between excellent photo-radical curability and coloring of the cured product, the amount of the photo-radical polymerization initiator to be added is preferably 0.5 to 10 parts by weight, and most preferably 1 to 5 parts by weight.

Further, in order to further improve the photocurability of the polymerizable resin composition of the present invention, triethylamine, diethylamine, diethanolamine, ethanolamine, dimethylaminobenzoic acid, dimethylaminobenzoic acid methyl, thioxanthone, -At least one photocuring accelerator selected from isopropylthioxanthone, 2,4-diethylthioxanthone and acetylacetone can be further added.

Further, various polymerization inhibitors can be added to the polymerizable resin composition of the present invention, if necessary. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, hydroquinone monomethyl ether, 2,5-
Di-tert-butylhydroquinone, p-tert-
Butyl catechol, mono-t-butyl hydroquinone,
p-benzoquinone, naphthoquinone, 2,5-di-ter
Examples include quinone / phenol-based inhibitors such as t-butyl-p-cresol, α-naphthol, and nitrophenol, other thioether-based inhibitors, and phosphite-based inhibitors. These compounds are used in an amount of 0.1 to 100 parts by weight of the resin.
0001 to 0.05 part is used, and each is added to the resin alone or in combination of two or more.

Further, the polymerizable resin composition of the present invention contains reinforcing agents such as glass fibers and carbon fibers, fillers such as talc, calcium carbonate, silica and mica, titanium oxide, and the like as long as various physical properties are not significantly reduced. Pigments such as carbon black and phthalocyanine blue, thixotropic agents, foaming agents, antioxidants, ultraviolet absorbers, lubricants, leveling agents, thickeners, thinners, thixotropic agents, antihalation agents, matting agents, It may contain a thermoplastic resin or the like. Further, at least one polymerizable resin selected from other polymerizable resins, for example, an epoxy (meth) acrylate resin, a urethane (meth) acrylate resin, a polyester (meth) acrylate resin, an epoxy resin, an oxetane compound, and an arbitrary ratio May be mixed.

The polymerizable resin composition of the present invention can be used for various FRP molded products, presses, castings, buttons, resins for decorative plates, or insulating varnishes, similarly to commonly used polymerizable resin compositions. Resin, wood, paper, particle board,
Coating materials for various substrates such as metals, plastics, glass, concrete, asphalt, ceramics, coating materials for civil engineering and construction, resins for paints, putties, sealing agents, adhesives, resins for chemical anchors, printing ink binders,
It can be used as a resin for stereolithography, a resin for a solder resist, a resin for a photoresist, a resin for a printing plate, and the like.

[0053]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the following, “parts” and “%” represent “parts by weight” and “% by weight”, respectively, unless otherwise specified.

The gel permeation chromatography measurement conditions and NMR measurement conditions are as follows. <Measurement conditions for gel permeation chromatography> Measuring apparatus: GPC system 8020 series manufactured by Tosoh Corporation Column: TSKgel GMHXL 2 + G2000HXL 2 solvents: Tetrahydrofuran Measurement temperature: 40 ° C Molecular weight calculation: Standard polystyrene equivalent molecular weight Calculated by <NMR Measurement Conditions> Varian Superconducting Fourier Transform Nuclear Magnetic Resonance Spectrometer UNITY-400 Model (Reference Frequency: 400 MHz) ¹ H-NMR Deuterated Chloroform Solvent Tetramethylsilane is used as a reference substance peak [Example 1] Stirrer 60 parts of dehydrated and purified toluene and 4 parts of boron trifluoride ether complex were placed in a four-necked flask equipped with a cooling tube, a dropping funnel, a thermometer, and a dry N ₂ / Air (oxygen content: 7%) introduction tube. Warmed to 50 ° C.
Then, 140 parts of dehydrated and purified oxetane methacrylate (manufactured by Ube Industries) represented by the following chemical formula was added dropwise over 1 hour, and after completion of the addition, the internal temperature was raised to 80 ° C. and maintained at the same temperature for 4 hours. Thereafter, devolatilization was performed at the same temperature under a reduced pressure of 20 Torr for 3 hours to obtain a pale yellow transparent resin.

The obtained resin (70 parts) was diluted with methyl methacrylate (30 parts) at 50 ° C. to obtain a resin composition (1). The obtained resin composition (1) was a pale yellow transparent liquid having a viscosity of 630 cp at 25 ° C., and the resin solid content was 70% as measured by nonvolatile components. The molecular weight of the resin solids measured by gel permeation chromatography was as follows: number average molecular weight (Mn) = 2600, weight average molecular weight (Mw) =
3700. Further, as a result of NMR analysis of the resin solid, it was confirmed that the obtained polymer had a structure in which an oxetane ring was opened. This NMR chart is shown in FIG.

[0056]

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Example 2 A stirring rod, a cooling tube, a dropping funnel,
In a four-necked flask equipped with a thermometer and a dry N ₂ / Air (oxygen content: 7%) introduction tube, 60 parts of dehydrated and purified methyl methacrylate and 4 parts of boron trifluoride etherate were charged, and heated to 50 ° C. did. Then, 140 parts of (epoxycyclohexyl) methyl acrylate (manufactured by Daicel Chemical Industries) represented by the following chemical formula, which was dehydrated and purified, was added dropwise over 1 hour. After holding, the mixture was cooled to obtain a resin composition (2).

The obtained resin composition (2) was a pale yellow transparent liquid having a viscosity of 400 cp at 25 ° C. and a resin solid content of 70% as measured by nonvolatile components. The molecular weight of the resin solids measured by gel permeation chromatography was number average molecular weight (Mn) = 1500 and weight average molecular weight (Mw) = 2800. In addition, N
As a result of MR analysis, it was confirmed that the obtained polymer had a structure in which an epoxy ring was opened. This NMR chart is shown in FIG.

[0059]

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Example 3 A stirring rod, a cooling tube, a dropping funnel,
A four-necked flask equipped with a thermometer and a dry N ₂ / Air (oxygen content: 7%) inlet tube was charged with 60 parts of dehydrated and purified toluene and 4 parts of boron trifluoride etherate, and heated at 50 ° C.
Was heated. Next, the same oxetane methacrylate (manufactured by Ube Industries) 100 used in Example 1 was dehydrated and purified.
And a mixture of 40 parts of isobutyl vinyl ether was added dropwise over 1 hour, and after completion of the addition, the internal temperature was raised to 80 ° C., and maintained at the same temperature for 4 hours. Thereafter, devolatilization was performed at the same temperature under a reduced pressure of 20 Torr for 3 hours to obtain a pale yellow transparent resin.

The obtained resin (70 parts) was diluted with methyl methacrylate (30 parts) at 50 ° C. to obtain a resin composition (3). The obtained resin composition (3) was a pale yellow transparent liquid having a viscosity of 550 cp at 25 ° C., and the resin solid content by non-volatile content measurement was 70%. The molecular weight of the resin solids measured by gel permeation chromatography was as follows: number average molecular weight (Mn) = 2200, weight average molecular weight (Mw) =
3300. In addition, NMR analysis of the resin solid confirmed that the obtained polymer had a structure in which the oxetane ring was opened and a structure in which the double bond of vinyl ether was addition-polymerized. Example 4 A four-necked flask equipped with a stirring rod, a cooling tube, a dropping funnel, a thermometer, and a dry N ₂ / Air (oxygen content: 7%) introduction tube was charged with 60 parts of dehydrated and purified methyl methacrylate and 3 parts of fluorine. 4 parts of a boron halide ether complex were charged and heated to 50 ° C. Then, a mixture of 100 parts of the same oxetane methacrylate (manufactured by Ube Industries) and 40 parts of isobutyl vinyl ether used in Example 1 which had been dehydrated and purified was added dropwise over 1 hour, and after completion of the addition, the internal temperature was raised to 80 ° C. After maintaining at the same temperature for 4 hours, the mixture was cooled to obtain a resin composition (4).

The obtained resin composition (4) was a pale yellow transparent liquid having a viscosity of 480 cp at 25 ° C., and the resin solid content was 70% as measured by nonvolatile components. The molecular weight of the resin solids measured by gel permeation chromatography was such that the number average molecular weight (Mn) = 1900 and the weight average molecular weight (Mw) = 3000. In addition, N
As a result of MR analysis, it was confirmed that the obtained polymer had a structure in which an oxetane ring was opened and a structure in which a double bond of vinyl ether was addition-polymerized. Example 5 A four-necked flask equipped with a stirring rod, a cooling tube, a dropping funnel, a thermometer, and a dry N ₂ / Air (oxygen content: 7%) introduction tube was charged with 60 parts of dehydrated and purified methyl methacrylate and 4 parts of a boron halide ether complex were charged and heated to 50 ° C. Subsequently, a mixture of 100 parts of (epoxycyclohexyl) methyl acrylate (manufactured by Daicel Chemical Industries) and 40 parts of isobutyl vinyl ether used in Example 2 which had been dehydrated and purified was added dropwise over 1 hour. The temperature was raised, and the temperature was maintained for 4 hours, followed by cooling to obtain a resin composition (5).

The obtained resin composition (5) was a light yellow transparent liquid having a viscosity of 450 cp at 25 ° C., and the resin solid content was 70% as measured by nonvolatile components. The molecular weight of the resin solids measured by gel permeation chromatography was such that the number average molecular weight (Mn) = 1900 and the weight average molecular weight (Mw) = 3000. In addition, N
As a result of MR analysis, it was confirmed that the obtained polymer had a structure in which an epoxy ring was opened and a structure in which a double bond of vinyl ether was addition-polymerized. The NMR chart is shown in FIG. Example 6 A four-necked flask equipped with a stirring rod, a cooling tube, a dropping funnel, a thermometer, and a dry N ₂ / Air (oxygen content: 7%) introduction tube was charged with 60 parts of dehydrated and purified methyl methacrylate and 3 parts of fluorine. 4 parts of a boron halide ether complex were charged and heated to 50 ° C. Then, 70 parts of the same oxetane methacrylate (manufactured by Ube Industries) used in Example 1 and 70 parts of (epoxycyclohexyl) methyl acrylate (manufactured by Daicel Chemical) used in Example 2 were dehydrated and purified.
After completion of the dropwise addition, the internal temperature was raised to 80 ° C., and the temperature was maintained at the same temperature for 4 hours, followed by cooling to obtain a resin composition (6).

The obtained resin composition (6) was a pale yellow transparent liquid having a viscosity of 520 cp at 25 ° C. The resin solid content was 70% as measured by nonvolatile components. The molecular weight of the resin solids measured by gel permeation chromatography was number average molecular weight (Mn) = 2100 and weight average molecular weight (Mw) = 3300. In addition, N
As a result of MR analysis, it was confirmed that the obtained polymer had a structure in which an oxetane ring was opened and a structure in which an epoxy ring was opened. Example 7 A four-necked flask equipped with a stirring rod, a cooling tube, a dropping funnel, a thermometer, and a dry N ₂ / Air (oxygen content: 7%) introduction tube was charged with 60 parts of dehydrated and purified diethylene glycol dimethacrylate and 4 parts of a boron halide ether complex were charged and heated to 50 ° C. Next, 140 parts of the same oxetane methacrylate (manufactured by Ube Industries) used in Example 1 that had been dehydrated and purified was added dropwise over 1 hour, and after completion of the addition, the internal temperature was raised to 80 ° C and maintained at the same temperature for 6 hours. After cooling, a resin composition (7) was obtained.

The obtained resin composition (7) was a pale yellow transparent liquid having a viscosity of 70 cp at 25 ° C., and the resin solid content was 70% as measured by nonvolatile components. The molecular weight of the resin solids measured by gel permeation chromatography was number average molecular weight (Mn) = 2900 and weight average molecular weight (Mw) = 4000. In addition, N
As a result of MR analysis, it was confirmed that the obtained polymer had a structure in which an oxetane ring was opened. Example 8 A four-necked flask equipped with a stirring rod, a cooling tube, a dropping funnel, a thermometer, and a dry N ₂ / Air (oxygen content: 7%) introduction tube was charged with 60 parts of dehydrated and purified methoxydiethylene glycol acrylate and 3 parts of fluorinated methoxydiethylene glycol acrylate. 4 parts of a boron halide ether complex were charged and heated to 50 ° C. Next, the same (epoxycyclohexyl) methyl acrylate (manufactured by Daicel Chemical Industries) 140 used in Example 2 was purified by dehydration.
Part over 1 hour, and after the completion of the dropping, the internal temperature is 80 ° C.
And kept at the same temperature for 4 hours, followed by cooling to obtain a resin composition (8).

The obtained resin composition (8) was a pale yellow transparent liquid having a viscosity of 490 cp at 25 ° C. The resin solid content was 70% as measured by nonvolatile components. The molecular weight of the resin solids measured by gel permeation chromatography was number average molecular weight (Mn) = 2000 and weight average molecular weight (Mw) = 4300. In addition, N
As a result of MR analysis, it was confirmed that the obtained polymer had a structure in which an epoxy ring was opened. Comparative Example 1 A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube was charged with 296 parts of phthalic anhydride, 294 parts of maleic anhydride, 152 parts of propylene glycol and 334 parts of diethylene glycol. In addition, after performing a dehydration condensation reaction at 210 ° C. for 6 hours under a nitrogen stream, the mixture was cooled to synthesize 986 parts of unsaturated polyester.

The above unsaturated polyester (140 parts) was dissolved in styrene monomer (60 parts) and the viscosity at 25 ° C. was 37 parts.
An unsaturated polyester resin having 0 cp and an acid value of 18 was obtained.
The obtained resin is designated as PE-1. Comparative Example 2 A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube was charged with 296 parts of phthalic anhydride, 294 parts of maleic anhydride, 152 parts of propylene glycol and 334 parts of diethylene glycol. In addition, after performing a dehydration condensation reaction at 210 ° C. for 6 hours under a nitrogen stream, the mixture was cooled to synthesize 986 parts of unsaturated polyester.

140 parts of the above unsaturated polyester was dissolved in 60 parts of a mixture of styrene monomer / triethylene glycol diacrylate (1/1) to obtain an unsaturated polyester resin having a viscosity of 430 cp and an acid value of 18 at 25 ° C. . The obtained resin is designated as PE-2. Comparative Example 3 A urethane acrylate resin was obtained by using 140 parts of UV-7550B manufactured by Nippon Gohsei as urethane acrylate and 60 parts of triethylene glycol diacrylate as a diluent. The obtained resin was UA-1
And [Examples 9 to 16, Comparative Examples 4 to 6] The resin compositions (1) to (8) obtained in Examples 1 to 8 and P obtained in Comparative Example 1
With respect to each resin composition of E-1, PE-2 obtained in Comparative Example 2, and UA-1 obtained in Comparative Example 3, thermal radical curability and photo radical curability were evaluated by the following methods. Thermal radical curability To each resin composition, 0.5% of cobalt octenoate, 0.2% of dimethylaniline, and 1.0% of a curing agent 328E (manufactured by Kayaku Akzo) are added, and an applicator is placed on a glass substrate. Is applied so as to have a thickness of 0.2 mm,
Cured at room temperature. The time required for the coating film surface to dry to the touch at that time was defined as thermal radical curability, and the obtained cured product was subjected to an acetone rubbing test. The results are shown in Table 1. Photo-radical curability To each resin composition, 2% of a photo-curing agent Irgacure 651 (manufactured by Ciba-Geigy) was added, and 30% was added using a bar coater.
Apply to a thickness of μm, belt conveyor type UV
It was cured with a curing device. The irradiation energy (100 mJ / time) required for touch drying of the coating film surface at that time was defined as photo-radical curability, and the obtained cured product was subjected to an acetone rubbing test. The results are shown in Table 1.

[0069]

[Table 1]

[Examples 17 and 18, Comparative Example 7] Each of the resin compositions (7) and (8) obtained in Examples 7 and 8 and the resin composition of PE-1 obtained in Comparative Example 1 The odor intensity was measured by an odor sensor to evaluate low odor. Sensory evaluation was also performed using the human nose. Table 2 shows the results. The odor intensity measurement method using the odor sensor is as follows. (Measurement method of low odor) Bottom area 625cm ² , Height 30c
m, a semiconductor odor sensor having an intake pipe and an exhaust pipe at the top of a rectangular parallelepiped closed container (Shin-Cosmos Electric X
P329 type).

Next, 10 g of each resin composition was measured in a cylindrical open container having a bottom area of 80 cm ² and a height of 1 cm, and the odor intensity was measured by leaving the resin composition at the bottom of the closed container for 90 minutes. The odor sensitivity (mV) in the table means that the smaller the number is, the less the volatilization of the substance generating the odor is.

[0072]

[Table 2]

[0073]

The novel polymerizable resin of the present invention and the polymerizable resin composition using the same are excellent in thermal radical polymerizability and photoradical polymerizability, so that when cured in air, the curing inhibition by oxygen is inhibited. This does not occur, and a coating film having excellent surface drying properties can be obtained.

[Brief description of the drawings]

FIG. 1 shows the N of the resin (solid content only) obtained in Example 1.
It is an MR chart.

FIG. 2 shows the N of the resin (solid content only) obtained in Example 2.
It is an MR chart.

FIG. 3 shows N of the resin (solid content only) obtained in Example 5.
It is an MR chart.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 133/06 C09D 133/06 4J040 // C09D 11/10 11/10 163/00 163/00 C09J 163 / 00 C09J 163/00 (72) Inventor Hirohiro Katsuyama 5-8 Nishiburi-cho, Suita-shi, Osaka F-term in Nippon Shokubai Co., Ltd. 4J002 CH021 CH031 EA046 EH046 EH076 EH106 EK007 ET007 FD147 GH01 GJ01 4J005 AA05 AA07 4J027 AA08 AB02 AB10 AB17 AC03 AC04 AC06 BA04 BA05 BA07 BA10 BA19 BA20 BA23 BA24 BA26 BA27 CA12 CA14 CA18 CA29 CA36 CB04 CB05 CB10 CC02 CC05 CD02 CD08 CD09 CD10 4J038 CE051 CE052 DF021 DF022 FA041 FA042 FA06 FA06131 FA121 FA121 FA121 FA121 KA06 PA17 PA19 PB03 PB05 PC02 PC03 PC04 PC06 PC08 PC10 4J039 AD20 AD21 AE07 EA03 EA05 4J040 DN061 DN062 EE021 EE022 FA061 FA 062 FA281 FA282 GA02

Claims (7)

[Claims] 1. A polymerizable resin obtained by cationically polymerizing a monomer component containing an unsaturated monomer (A) having an alicyclic epoxy group and / or oxetane group in a molecule. 2. The polymerizable resin according to claim 1, wherein the unsaturated monomer has a (meth) acryloyl group as an unsaturated group. 3. The method according to claim 1, wherein the monomer component is an unsaturated monomer (A).
3. The polymerizable resin according to claim 1, further comprising another monomer capable of cationic polymerization. 4. The polymerizable resin according to claim 3, wherein the other cationically polymerizable monomer is an alkyl vinyl ether monomer (B). 5. A polymerizable resin composition comprising the polymerizable resin according to claim 1 and a radical polymerizable monomer (C). 6. All or a part of the main chain skeleton of the polymer is
A polymer which is a structural unit represented by the following formula (1). Embedded image (Wherein, R ¹ is an organic group having a (meth) acryloyl group, m is an integer of 1 to 10. X is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, n Is 2
Is an integer of 10 to 10. ) 7. All or part of the main chain skeleton of the polymer is
A polymer which is a structural unit represented by the following formula (2). Embedded image (In the formula, R ² is an organic group having a (meth) acryloyl group. R ³ is an organic group having a (meth) acryloyl group, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)