JPH05310811A - Resin composition and cured article obtained therefrom - Google Patents

Abstract

PURPOSE:To obtain a resin composition which cures rapidly to give a cured coating film excellent in gloss, hardness, etc., by mixing a specific polyester-poly(vinyl ether) with a catalyst for cationic photopolymerization to dissolve the catalyst. CONSTITUTION:The title composition contains 100 pts.wt. polyesterpoly(vinyl ether) (A) having 2-6 vinyl ether groups and at least one cyclohexene ring in the molecule and about 0.05-10 pts.wt. cationic photopolymerization catalyst (B). Examples of the component (A) include products of the reaction of an acid halide having a cyclohexene ring (e.g. a chloride or bromide of cyclohexenedicarboxylic acid or cyclohexenetricarboxylic acid) with a hydroxylated vinyl ether (e.g. 2-hydroxyethyl vinyl ether or 3-hydroxypropyl vinyl ether).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a radiation-curable resin composition and a cured product thereof.

[0002]

2. Description of the Related Art Radiation (ultraviolet ray, electron beam, etc.) curable resin composition has been one of the successful ones in the recent tendency toward low pollution, resource saving and energy saving of inks, paints, resists, etc. Ink, paint, resist, etc. This is a reactive resin composition containing substantially no volatile solvent and containing a reactive diluent that is a polymerizable monomer that reacts with the resin during curing to become a part of the cured product. .. Most of the resins and polymerizable monomers that are the main components of these reactive resin compositions are (meth) acrylate compounds, and are classified into, for example, polyester acrylate, epoxy acrylate, polyurethane acrylate, polyether acrylate, alkyd acrylate, and polyol acrylate. can do. These form a characteristic hardened | cured material according to each skeleton.

[0003]

The composition using the acrylates as described above has a strong anaerobic property and has a drawback that the surface curability is poor due to radical consumption by oxygen in the air. Therefore, it is always desired to provide a resin composition having a new characteristic.

[0004]

Therefore, as a result of diligent research, the present inventor has improved the drawbacks of such acrylates,
The present invention has been accomplished by finding a new resin composition having a fast curability and a cured coating film having excellent gloss and hardness. That is, the present invention comprises a resin composition comprising a polyester polyvinyl ether (A) having 2 to 6 vinyl ether groups and at least one cyclohexene nucleus in the molecule and a photocationic polymerization catalyst (B), and Regarding the cured product.

The polyester polyvinyl ether (A) used in the present invention is, for example, an acid halide compound (a) having a cyclohexene nucleus (eg, cyclohexene dicarboxylic acid, cyclohexene tricarboxylic acid, 6-methyl-cyclohexene-1,2,3). -Tricarboxylic acid, hymic acid, endo acid, etc., or halogen substitution products thereof,
For example, het acid, mono and polychlorotetrahydrophthalic acid, mono and polybromotetrahydrophthalic acid or 1,4,5,6,7,7-hexabrom-endo-
5-norbornene-2,3-dicarboxylic acid acid chloride, acid bromide and the like) and a hydroxyl group-containing vinyl ether compound (b) (for example, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutane vinyl ether, 5-hydroxy). (Pentane vinyl ether, 5-hydroxy-3-methyl-pentane-1-vinyl ether, 1,4-cyclohexanedimethylol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, tripropylene glycol monovinyl ether, etc.)
Reaction product, the compound (a), the compound (b) and a polyol compound (c), for example, ethylene glycol, propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, diethylene glycol, tripropylene glycol. , Polyethylene glycol, polytetramethylene glycol, trimethylol propane, cyclohexane dimethylol polyols,
The above-mentioned polyols and polybasic acids or their anhydrides (for example,
Phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, methylhexanehydrophthalic acid, polybutadienedicarboxylic acid, tetrabromophthalic acid, succinic acid,
Maleic acid, fumaric acid, adipic acid, sebacic acid, dodecane diacid, trimethyl adipic acid, 2,4-benzophenone dicarboxylic acid, dodecenyl succinic acid, azelaic acid, tetrahydrophthalic acid, naphthalene polycarboxylic acid, etc., or their acid anhydrides. Reaction products such as polyester polyols, polycaprolactone polyols, polycarbonate polyols, etc., acid halide compounds (d) having no cyclohexene nucleus (eg, phthalic acid, isophthalic acid, terephthalic acid, hexa). Hydrophthalic acid, methylhexahydrophthalic acid, polybutadienedicarboxylic acid, tetrabromophthalic acid, succinic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, dodecanedioic acid, trimethyladipic acid, 2,4-benzophenonedicarboxylic acid Dodecenylsuccinic acid, azelaic acid, tetrahydrophthalic acid, acid chloride or acid bromide of polybasic acids such as naphthalene polycarboxylic acid)
And the compound (b), the polyol acid, and a polybasic acid having a cyclohexene nucleus or an anhydride thereof (for example, cyclohexene dicarboxylic acid, cyclohexene tricarboxylic acid,
Reaction of 6-methyl-cyclohexene-1,2,3-tricarboxylic acid, hymic acid, endo acid, etc. or their anhydrides with polyester polyol reactant (e) or

Polycarboxylic acid ester (f) having a cyclohexene nucleus (eg, tetrahydrophthalic acid dimethyl ester, tetrahydrophthalic acid diethyl ester,
Cyclohexene tricarboxylic acid trimethyl ester, etc.)
And the above-mentioned compound (b).

The reaction product of the compound (a) and the compound (b) can be obtained by reacting the compound (b) with about 2 mol usually to 1 mol of the compound (a). At this time, if a tertiary amine is added to accelerate dehalogenation, the desired product can be obtained in a short time. Examples of the tertiary amines include triethylamine, trimethylamine, tributylamine, pyridine and the like. It is preferable to use 4-dimethylaminopyridine or the like as a catalyst. As the reaction solvent, for example, methylene chloride, diethyl ether, cyclohexane, n-hexane, n-heptane, toluene or the like is used. The reaction temperature is preferably 0 ° C to 50 ° C, particularly preferably 20 to 3
It is 0 ° C. The reaction time is usually 30 minutes to 10 hours.

The reaction product of the compound (a), the compound (b) and the polyol compound (c) is the compound (b) based on 1 equivalent of the acid halide group of the compound (a).
It can be obtained by reacting such that the total amount of the hydroxyl equivalents of the above and the hydroxyl equivalent of the polyol compound (c) is about 1 equivalent. The compound (b) and the polyol compound (c) are preferably used in a ratio of 1 to 5 equivalents of the hydroxyl group of the polyol compound (c) to 1 equivalent of the hydroxyl group of the compound (b). Further, it is preferable to use the tertiary aminos and the catalyst as described above, and further it is preferable to use the reaction solvent described above.
The reaction temperature is preferably 0 ° C to 50 ° C, particularly preferably 2
It is 0 to 30 ° C. The reaction time is usually 30 minutes to 10 hours.

The reaction product of the acid halide compound (d) having no cyclohexene nucleus, the compound (b) and the polyester polyol reaction product (e) is based on 1 equivalent of the acid halide group of the acid halide compound (d). Then, the total amount of the hydroxyl equivalent of the compound (b) and the hydroxyl equivalent of the polyester polyol reaction product (e) is used as about 1 equivalent and the reaction is performed. The compound (b) and the polyester polyol compound (c) are used in a proportion of 1 to 5 hydroxyl groups of the polyester polyol reaction product (e) with respect to 1 equivalent of the hydroxyl group of the compound (b).
It is preferable to use it in an equivalent ratio. Further, it is preferable to use the tertiary amines and catalysts as described above, and it is preferable to use the reaction solvent described above. The reaction temperature is preferably 0 ° C to 50 ° C, particularly preferably 20 to 30
℃. The reaction time is usually 30 minutes to 10 hours.

The reaction product of the polycarboxylic acid ester (f) having a cyclohexene nucleus and the compound (b) is
It can be obtained by reacting with 1 equivalent or more of the hydroxyl group of the compound (b) to 1 equivalent of the ester group of the polycarboxylic acid ester (f) having a cyclohexene nucleus, and an excess amount of the compound after the reaction is obtained. The target substance can be obtained by distilling off (b). In order to accelerate the reaction, it is preferable to use tetraisopropoxide titanium as a transesterification catalyst. Reaction temperature is 150 ~
250 ° C is preferred. The reaction is preferably carried out in N ₂ gas. The reaction time is usually 1 to 20 hours.

The polyester polyvinyl ether (A) used in the present invention can be synthesized in a very wide range of structures and molecular weights by appropriately selecting the kind of raw material at the time of synthesis or the synthesis method. .. However, if the molecular weight is too large, the vinyl ether group concentration as a whole decreases and the curability becomes poor. Therefore, the vinyl ether group equivalent of the vinyl ether oligomer is preferably 10,000 or less, and particularly preferably 5000 or less.

The cationic photopolymerization catalyst (B) used in the present invention is specifically, for example, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, P- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate,
4-chlorophenyldiphenylsulfonium hexafluorophosphate, (2,4-cyclopentadiene-1
-Yl) [(1-methylethyl) benzene] -Fe-hexafluorophosphate and the like. These are easily available from the market. For example,
Asahi Denka Co., Ltd., SP-150, SP-170, Ciba
Examples include Irgacure 261 manufactured by Geigy. The amount of the photo-cationic polymerization catalyst (B) used is preferably 0.05 to 10 parts by weight, and particularly preferably 0.1 to 100 parts by weight of the polyester polyvinyl ether (A).
1 to 5 parts by weight.

In the present invention, it is preferable to use an ethylenically unsaturated compound other than the component (A). As typical examples of the ethylenically unsaturated compound, for example, 1,4-butanediol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, tripropylene glycol divinyl ether,
3-methyl-1,5-pentanediordivinyl ether, 1,4-cyclohexanedimethylol divinyl ether, trimethylolpropane trivinyl ether, polyurethane polyvinyl ether, for example, the hydroxyl group-containing vinyl ether compound (b) and the polyol compound (c). And organic polyisocyanates (eg tolylene diisocyanate, xylylene diisocyanate, 4,
4'-difelmethane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, etc.) vinyl ether compounds other than the component (A), (meth) acrylate compounds (for example, phenoxyethyl (meth) acrylate, isobornyl (meth)). ) Acrylate, tricyclodecane dimethylol diacrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, trimethylol tri (meth) acrylate, polyethylene glycol di (meth) acrylate, phenyl glycidyl ether (meth) acrylate, 1,9 -Nonanediol di (meta)
Acrylate, epoxy (meth) acrylate, for example, (meth) acrylate of bisphenol A epoxy resin, (meth) acrylate of bisphenol F epoxy resin, polyester (meth) acrylate, for example ethylene glycol, propylene glycol, 3-methyl-1 , 5-Pentanediol, trimethylolpropane, and other polyol components and succinic acid, adipic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and other dibasic acids. ) Acrylate etc. can be mentioned. ) And the like.

In the present invention, the ethylenically unsaturated compound other than the component (A) is preferably used in an amount of 0 to 1000 parts by weight, particularly preferably 0 to 500 parts by weight, based on 100 parts by weight of the component (A). It is a department. When (meth) acrylates are used among the ethylenically unsaturated compounds other than these (A) components, (meth) acrylates 10
It is preferable to use 0 to 15 parts by weight of the photopolymerization initiator with respect to 0 part by weight. Examples of such a polymerization initiator include benzoin alkyl ethers such as benzoin ethyl ether, benzoin isobutyl ether and benzoin isopropyl ether, and acetophenone compounds such as 2,2-diethoxyacetophenone and 4'-phenoxy-2,2-dichloroacetophenone. , 2-hydroxy-2-methylpropiophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 4'-dodecyl-2-hydroxy-2-methylpropiophenone and other propiophenone series, Benzyl dimethyl ketal, 1-
Examples thereof include anthraquinone-based photopolymerization initiators such as hydroxycyclohexyl phenyl ketone, 2-ethylanthraquinone, and 2-chloroanthraquinone, and thioxanthone-based photopolymerization initiators.

The resin composition of the present invention may further contain organic solvents such as epoxy resins (for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetrabromobisphenol A type epoxy resin, novolac type). Epoxy resin, etc.), pigments, coloring materials, inorganic fillers, non-reactive resins, and other various additives can be added.

The resin composition of the present invention can be obtained by mixing and dissolving the above-mentioned component (A), component (B) and others. The resin composition of the present invention has good curability in air, and since the coating film after curing has advantages such as gloss and hardness, the resin composition of the present invention includes metal, plastic, paper, It can be applied to various fields such as coating agents, paints, printing inks and molding materials for various materials such as glass, rubber and wood. The cured product of the resin composition of the present invention can be easily obtained by irradiating with an ultraviolet ray or an electron beam by a conventional method.

[0017]

EXAMPLES The present invention will be described in more detail with reference to Synthesis Examples and Examples. Synthesis Example of Polyester Polyvinyl Ether (A) Synthesis Example 1 20.69 g (0.1 mol) of the compound represented by the formula (1)

[0018]

[Chemical 1]

Charge 180 ml of methylene chloride, adjust to 25 ° C., and stir. Then, a mixture of 35.2 g (0.2 mol) of triethylene glycol monovinyl ether, 42.8 ml of triethylamine, 0.36 g of 4-dimethylaminopyridine and 300 ml of methylene chloride is added dropwise thereto. The dropping was completed in about 2 hours, and then the reaction was completed by stirring for 1 hour. The reaction mixture is then treated with 88 g of water and 2 parts of phosphoric acid.
g, 5 g of sodium hydrogen carbonate and 5 g of sodium chloride were washed three times with 800 ml of a mixed solution, the solvent was evaporated under reduced pressure, and the polyester divinyl ether obtained as a residue was a pale yellow liquid with a vinyl ether group equivalent of 279.5. there were.
The structure is as follows:

[0020]

[Chemical 2]

Synthesis Example 2 20.69 g (0.1 mol) of the compound represented by the formula (1)
Charge 180 ml of methylene chloride, adjust to 25 ° C and stir. Then, a mixture of 34 g (0.2 mol) of cyclohexane-1,4-dimethylol monovinyl ether, 42.8 ml of triethylamine, 0.36 g of 4-dimethylaminopyridine and 300 ml of methylene chloride is added dropwise thereto. The dropping was completed in about 2 hours, and then the reaction was completed by stirring for 1 hour. The reaction mixture is then treated with 88 g of water and 2 parts of phosphoric acid.
g, 5 g of sodium hydrogencarbonate and 5 g of sodium chloride were washed three times with 800 ml of a mixed solution, and the solvent was distilled off under reduced pressure to obtain a polyester divinyl ether as a residue, which was a pale yellow liquid and had a vinyl ether group equivalent of 273. It was 5. The structure is as follows:

[0022]

[Chemical 3]

Synthesis Example 3 36.6 g (0.2 mol) of adipic acid chloride and 300 ml of methylene chloride were charged, and the mixture was adjusted to 25 ° C. and stirred. Next, 35.2 g (0.2 mol) of triethylene glycol monovinyl ether, polyester diol (1 mol of tetrahydrophthalic anhydride and ethylene glycol 2)
27.6 g of mole reactant, hydroxyl equivalent 406.6)
(0.1 mol), triethylamine 85.6 ml, 4-
Dimethylaminopyridine 0.72 g and methylene chloride 5
00 ml of the mixture is added dropwise. The dropping was completed in about 2 hours, and then the reaction was completed by stirring for 1 hour. The reaction mixture is then treated with 88 g of water, 2 g of phosphoric acid, 5 parts of sodium hydrogen carbonate.
Polyester divinyl ether obtained by washing 3400 times with 1400 ml of a mixed aqueous solution of g and 5 g of sodium chloride and evaporating off the solvent under reduced pressure was a pale yellow semi-solid, vinyl ether group equivalent 426.

Synthesis Example 4 4-hydroxybutyl vinyl ether 116 g (1 mol), dimethyltetrahydrophthalate 49.5 g
(0.25 mol) and tetraisopropoxide titanium (0.23 g) are mixed with stirring, and the reaction temperature is 170 to 200 ° C.
Then, by-produced methanol is distilled off in about 3 hours while flowing N ₂ gas. After distilling off the methanol, cool it and heat it under reduced pressure.
The polyester divinyl ether obtained by distilling off hydroxybutyl ether and leaving the residue in the kettle was a pale yellow liquid and had a vinyl ether group equivalent of 184. The structural formula is as follows.

[0025]

[Chemical 4]

Synthesis Example 5 20.69 g (0.1 mol) of the compound represented by the formula (1) and 180 ml of methylene chloride were charged, and the mixture was adjusted to 25 ° C. and stirred. Then, a mixture of 17.6 g (0.1 mol) of triethylene glycol monovinyl ether, 4.47 g (0.033 mol) of trimethylolpropane, 42.8 ml of triethylamine, 0.36 g of 4-dimethylaminopyridine and 300 ml of methylene chloride. Is dripped. The dropping was completed in about 2 hours, and then the reaction was completed by stirring for 1 hour. The reaction mixture is then treated with 88 g of water and 2 parts of phosphoric acid.
g, 5 g of sodium hydrogencarbonate and 5 g of sodium chloride were washed three times with 800 ml of a mixed aqueous solution, and the solvent was distilled off under reduced pressure to obtain a polyester polyvinyl ether as a pale yellow semisolid which had a vinyl ether group equivalent of 357. It was

Examples 1 to 7 and Comparative Examples 8 to 11 The components (numbers indicate parts by weight) were mixed in the proportions shown in Table 1 to obtain resin compositions. The resin composition was applied to a paper coated with an oil-based ink with an RI tester so as to have a thickness of 2 μm, and this was applied to a metal halide (80 w / c) of an ultraviolet irradiation device.
m) The coating was passed through one lamp with a distance of 10 cm and cured. In Table 1, Example 7 and Comparative Example 11 were cured with an electron beam by an ordinary method. Curing speed, gloss, adhesion,
The hardness was evaluated as follows. The results are shown in Table 1.

Evaluation method Curing speed: The irradiation dose until the tack on the surface disappears after curing (ultraviolet mJ / cm ² , electron beam Mrad). Mitsuzawa: The gloss after curing was visually evaluated. ○ ・ ・ ・ ・ Excellent gloss △ ・ ・ ・ ・ Gloss slightly deteriorated × ・ ・ ・ ・ No gloss Adhesion: After curing, scotch tape is attached to the surface and peeled off. If only the applied resin is peeled off, it is marked as X, and Δ is in the middle. Hardness: ○ when scratched by scratching the surface after curing with a nail, ○ when scratched easily, and Δ in the middle.

Table 1 Actual Example 1 2 3 4 5 6 7 Polyester divinyl ether obtained in Synthesis Example 1 100 50 100 Polyester divinyl ether 40 obtained in Synthesis Example 2 Polyester divinyl obtained in Synthesis Example 3 Ether 70 Polyester divinyl ether 100 obtained in Synthesis Example 4 Polyester polyvinyl ether 70 SP-170 obtained in Synthesis Example 5 * 1 2 3 2 2 2 2 1 2 Triethylene glycol divinyl ether 30 30 30 20 KAYARAD R -114 * 2 10 KAYARAD PEG400DA * 3 20 KAYARAD TMPTA * 4 Epicoat 828 * 5 30 Irgacure 184 * 6 1.5 Curing speed 10 23 10 10 10 17 0.5 mJ / cm ² mJ / cm ² mJ / cm ² mJ / cm ² mJ / cm ² mJ / cm ² mJ / cm ² Optical power ○ ○ ○ ○ ○ ○ ○ Adhesion ○ ○ ○ ○ ○ ○ ○ Hardness ○ ○ ○ ○ ○ ○ ○ Table 1 (Continued horizontally) Comparison Example 8 9 10 11 Polyester divinyl ether obtained in Synthesis Example 1 Obtained in Synthesis Example 2 Polyester divinyl ether Polyester divinyl ether obtained in Synthesis example 3 Polyester divinyl ether obtained in Synthesis example 4 Polyester polyvinyl ether obtained in Synthesis example 5 SP-170 * 1 Triethylene glycol divinyl ether KAYARAD R-114 * 2 30 30 30 KAYARAD PEG400DA * 3 50 20 50 50 KAYARAD TMPTA * 4 20 50 50 20 Epicoat 828 * 5 Irgacure 184 * 6 5 5 5 Curing speed 28 34 46 3 mJ / cm ² mJ / cm ² mJ / cm ² mJ / cm ² Mitsuzawa ○ ○ ○ ○ Adhesion △ ○ × △ Hardness △ △ △ △

Note * 1 SP-170: Asahi Denka Kogyo Co., Ltd., polyphenylsulfonium hexafluoroantimonate 50% propylene carbonate diluted product,
Photocationic polymerization catalyst * 2 KAYARAD R-114: Nippon Kayaku Co., Ltd.
Made by bisphenol A type epoxy resin acrylate * 3 KAYARAD PEG400DA: Nippon Kayaku Co., Ltd.
Polyethylene glycol diacrylate * 4 KAYARAD TMPTA: Nippon Kayaku Co., Ltd.
Co., Ltd., trimethylolpropane triacrylate * 5 Epicoat 828: Yuka Shell Epoxy Co., Ltd.
Bisphenol A type epoxy resin * 6 Irgacure 184: Ciba Geigy
Photopolymerization initiator

As is clear from Table 1, the resin composition of the present invention has a high curing rate and is excellent in gloss, adhesion, hardness and the like with the cured product.

[0032]

The resin composition of the present invention has excellent curability,
The cured product is excellent in gloss, adhesion and hardness.

Claims (2)

[Claims] 1. A polyester polyvinyl ether (A) having 2 to 6 vinyl ether groups and at least one cyclohexene nucleus in the molecule and a photocationic polymerization catalyst (B).
A resin composition comprising: 2. A cured product of the resin composition according to claim 1.