JPH0616731A - Resin composition and its cured material - Google Patents

Abstract

PURPOSE:To obtain a resin providing a cured material having high curing rate, excellent gloss, adhesiveness hardness, etc. CONSTITUTION:A resin composition comprises (A) a polyester compound containing a vinyl ether group and (meth)acrylate group in the molecule, (B) an optical cationic polymerization catalyst and (C) a photopolymerization initiator as an arbitrary component.

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. There are inks, paints, resists, etc. These are composed of a reactive resin composition containing practically no volatile solvent and containing a reactive diluent which is a polymerizable monomer that reacts with the resin during curing to become a part of the cured product. . Many of the resins and polymerizable monomers that are the main components of these reactive resin compositions are (meth) acrylate compounds, such as polyester acrylate,
It can be classified into epoxy acrylate, polyurethane acrylate, polyether acrylate, alkyd acrylate, polyol acrylate and the like. These form a characteristic hardened | cured material according to each skeleton.

[0003]

The composition using the acrylates as described above has the drawbacks that it is strongly anaerobic and has poor surface curability due to radical consumption by oxygen in the air. From the market, there is always a demand for the provision of new and distinctive resin compositions.

[0004]

Therefore, as a result of diligent research, the present inventor has improved the shortcomings of these 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 is characterized by containing a polyester compound (A) having a vinyl ether group and a (meth) acrylate group in the molecule, a photocationic polymerization catalyst (B), and a photopolymerization initiator (C) as an optional component. The present invention relates to a resin composition and a cured product thereof.

The polyester compound (A) used in the present invention is, for example, an acid halide (a) of a polycarboxylic acid.
(For example, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, hymic acid, entic acid, tetrabromophthalic acid, methylhexahydrophthalic acid, het acid, polybutadienedicarboxylic acid, succinic acid, adipic acid. , Sebacic acid, maleic acid,
Thiodiglycolic acid, benzophenone dicarboxylic acid, trimellitic acid, methylcyclohexene tricarboxylic acid,
Acid chloride or acid bromide of pyromellitic acid) and a hydroxyl group-containing vinyl ether compound (b) (for example, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutane vinyl ether, 5-hydroxypentane vinyl ether, 5-hydroxy-). 3-methyl-pentane-1-vinyl ether,
1,4-cyclohexane dimethylol monovinyl ether, diethylene glycol monovinyl ether, triethylene glycol monovinyl ether, tetraethylene glycol monovinyl ether, tripropylene glycol monovinyl ether, etc.) and a hydroxyl group-containing (meth) acrylate compound (c) (for example, 2-hydroxy). Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ε-caprolactone condensate of 2-hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, phenylglycidyl ether. (Meth) acrylate, etc., or

The acid halide (a), the hydroxyl group-containing vinyl ether compound (b), the hydroxyl group-containing (meth) acrylate compound (c) and the polyol compound (d) (for example, ethylene glycol, propylene glycol, neopentyl glycol, 3 -Polyols such as methyl-1,5-pentanediol, diethylene glycol, tripropylene glycol, polyethylene glycol, polytetramethylene glycol, trimethylolpropane and cyclohexanedimethylol, the above-mentioned polyols and polybasic acids or anhydrides thereof, For example, phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, polybutadienedicarboxylic acid, tetrabromophthalic acid, succinic acid, maleic acid, fumaric acid, adipic acid, Bachin acid, dodecanedioic acid, tetrahydrophthalic acid, azelaic acid, polyester polyols which are reaction products of naphthalene polycarboxylic acid or acid anhydrides thereof, etc., polycaprolactone polyols,
Examples thereof include reaction products with polycarbonate polyols and the like).

The reaction product of the acid halide (a), the hydroxyl group-containing vinyl ether compound (b) and the hydroxyl group-containing (meth) acrylate compound (c) is based on 1 equivalent of the acid halide group of the acid halide (a). Can be obtained by reacting such that the total number of the hydroxyl equivalents of the hydroxyl-containing vinyl ether compound (b) and the hydroxyl-containing (meth) acrylate compound (c) is about 1 equivalent. . The hydroxyl group-containing vinyl ether compound (b) and the hydroxyl group-containing (meth) acrylate compound (c) are used in an amount of 0.5 to 0.5 with respect to 1 equivalent of the hydroxyl group of the compound (b).
It is preferably used in a ratio of 2.0 equivalents. At this time, if a tertiary amine is added in order to promote 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 also preferable to use 4-dimethylaminopyridine or the like as a catalyst. Further, as the reaction solvent, for example, methylene chloride, diethyl ether, cyclohexane, n-hexane, n-heptane, toluene and the like are preferably used. Reaction temperature is 0-50
C is preferable, and 20 to 30 C is particularly preferable. The reaction time is usually 30 minutes to 10 hours.

The acid halide (a) and the compound (b)
And a reaction product of the compound (c) and the polyol compound (d), the compound (b), the compound (c), and the polyol compound (d) with respect to 1 equivalent of the acid halide group of the acid halide (a). It can be obtained by using and reacting so that the total number of hydroxyl equivalents of 1) becomes about 1 equivalent. The proportions of the compound (b), the compound (c) and the polyol compound (d) used are such that the hydroxyl group of the polyol compound (d) is 1 equivalent to the total amount of hydroxyl equivalents of the compound (b) and the compound (c). It is preferably used in a ratio of 1 to 5 equivalents. Further, the compound (b) and the compound (c)
It is preferable to use 0.5 to 2.0 equivalents of the hydroxyl group of the compound (c) with respect to 1 equivalent of the hydroxyl group of the compound (b). Further, it is preferable to use the above-mentioned tertiary amines, catalysts and the like, and further to use the above-mentioned reaction solvent. The reaction temperature is preferably 0 to 50 ° C, particularly preferably 20 to 30 ° C. The reaction time is usually 30 minutes to 10 hours.

The polyester compound (A) used in the present invention can be synthesized in a very wide range of structures and molecular weights by selecting the kind of raw materials used during synthesis and the synthesis method. However, if the molecular weight is too large, the concentration of vinyl ether groups or (meth) acrylate groups may decrease as a whole, resulting in poor curability or curing. Therefore, the molecular weight is preferably 10,000 or less, and particularly preferably 5000 or less. Is.

The photocationic polymerization 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. product, SP-150, SP-170, Ciba Geigy company make, Irgacure 261 etc. can be mentioned. The amount of the photocationic polymerization catalyst (B) used is preferably 0.05 to 20 parts by weight, and particularly preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the polyester compound (A).

Examples of the photopolymerization initiator (c) include benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether and other benzoin alkyl ethers, 2,2-diethoxyacetophenone, 4'-phenoxy-2,2-dichloroacetophenone. Such as acetophenone-based, 2-hydroxy-2-methylpropiophenone, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, 4'-dodecyl-
Examples thereof include propiophenone-based compounds such as 2-hydroxy-2-methylpropiophenone, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone and anthraquinone-based compounds such as 2-ethylanthraquinone and 2-chloroanthraquinone, and the like. The photopolymerization initiator (c) is preferably 0 to 60 parts by weight, particularly preferably 0 to 20 parts by weight, based on 100 parts by weight of the polyester compound (A).

In the present invention, if necessary, an ethylenically unsaturated compound other than the component (A) can be used. Examples of ethylenically unsaturated compounds that can be used include, for example, 1,4-butanediol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, tripropylene glycol divinyl ether, 3-methyl-1,5- Vinyl ether compounds such as pentanediol divinyl ether, 1,4-cyclohexane dimethyl roll divinyl ether, trimethyl roll propane trivinyl ether, polyester polyvinyl ether, polyurethane polyvinyl ether, and (meth) acrylate compounds [eg, 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, carbitol (meth) acrylate, tricyclodecanedimethylol di (meth) acrylate, hydroxypivalic acid Neopentyl glycol di (meth) acrylate, di- (meth) acrylate of ε-caprolactone reaction product of neopentyl glycol hydroxypivalate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HX-220,
HX-620, etc.), polyethylene glycol di (meth)
Acrylate, 1,9-nonanediol di (meth) acrylate, phenylglycidyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin polypropoxytri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylol Propane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane polyethoxytri (meth)
Acrylate, Bisphenol A Polyethsidi (meth)
Examples thereof include acrylate, dipentaerythritol penta- and hexa (meth) acrylate, epoxy (meth) acrylate, polyurethane (meth) acrylate, polyester poly (meth) acrylate, and polycarbonate poly (meth) acrylate. ] Etc. are mentioned.

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 50 to 500 parts by weight, based on 100 parts by weight of the component (A). Is. In the resin composition of the present invention, further organic solvent, epoxy resin, if necessary,
A pigment, a coloring material, an inorganic filler, a non-reactive resin, other various additives and the like can be added.

The resin composition of the present invention can be obtained by mixing and dissolving the above-mentioned components (A), (B) and (C), and others. According to the resin composition of the present invention, the curability in air is good, and the coating film after curing has advantages such as excellent gloss and hardness. Therefore, the resin composition of the present invention comprises metal, plastic, Coating agents, paints for various materials such as paper, glass, rubber, wood, etc.
It can be applied to various fields such as printing ink and molding materials. The cured product of the resin composition of the present invention can be easily obtained by irradiating with an ultraviolet ray and an electron beam.

[0015]

EXAMPLES Next, the present invention will be described more specifically by way of synthesis examples and examples. Synthesis Example of Polyester Compound (A) Synthesis Example 1 20.3 g (0.1 mol) of isophthalic acid dichloride,
Charge 180 ml of methylene chloride, adjust to 25 ° C and stir. Next, 17.6 g (0.1 mol) of triethylene glycol monovinyl ether, 11.6 g (0.1 mol) of 2-hydroxyethyl acrylate, 42.8 ml of triethylamine, 0.36 g of 4-dimethylaminopyridine, and metoquinone were added thereto. A mixture of 0.01 g and 300 ml of methylene chloride is added dropwise. Next, the reaction mixture was washed three times with 800 ml of a mixed aqueous solution of 88 g of water, 2 g of phosphoric acid, 5 g of sodium hydrogen carbonate, and 5 g of sodium chloride, and the solvent was evaporated under reduced pressure to obtain a polyester compound (A-1) obtained as a bottom residue. Was a pale yellow liquid. The structure was as follows:

[0016]

[Chemical 1]

Synthesis Example 2 Hexahydrophthalic acid dichloride 20.9 g (0.1
Mol), 180 ml of methylene chloride are charged, the temperature is adjusted to 25 ° C. and the mixture is stirred, then 17.6 g (0.1 mol) of triethylene glycol monovinyl ether, 13.0 g (0.1 mol) of 2-hydroxypropyl acrylate,
A mixture of 42.8 ml of triethylamine, 0.36 g of 4-dimethylaminopyridine, 0.01 g of metoquinone and 300 ml of methylene chloride is added dropwise. Next, the reaction mixture was washed 3 times with 88 g of water, 2 g of phosphoric acid, 800 g of a mixed aqueous solution of 5 g of sodium hydrogen carbonate and 5 g of sodium chloride, and the solvent was evaporated off under reduced pressure to obtain a polyester compound (A-2 ) Was a pale yellow liquid. The structure was as follows:

[0018]

[Chemical 2]

Synthesis Example 3 20.3 g (0.1 mol) of terephthalic acid dichloride was charged with 180 ml of methylene chloride, and the mixture was adjusted to 25 ° C. and stirred. Next, 17 g (0.1 mol) of cyclohexane-1,4-dimethylol monovinyl ether, 33.4 g (0.1 mol) of a reaction product of ε-caprolactone of 2-hydroxyethyl acrylate (molecular weight 334), and triethylamine 42. A mixture of 8 ml, 4-dimethylaminopyridine 0.36 g, metoquinone 0.01 g and methylene chloride 300 ml is added dropwise. Then, the reaction mixture was washed 3 times with 800 ml of a mixed aqueous solution of 88 g of water, 2 g of phosphoric acid, 5 g of sodium hydrogen carbonate and 5 g of sodium chloride, and the solvent was evaporated under reduced pressure to obtain a polyester compound (A-3) obtained as a bottom residue. Was a pale yellow liquid. The structure was as follows:

[0020]

[Chemical 3]

Synthesis Example 4 36.6 g (0.2 mol) of adipic dichloride and 300 ml of methylene chloride were charged and the temperature was adjusted to 25 ° C., followed by stirring. Next, triethylene glycol, 17.6 g (0.1 mol) of monovinyl ether, 11.6 g (0.1 mol) of 2-hydroxyethyl acrylate, polyester diol (a reaction product of 1 mol of tetrahydrophthalic anhydride and 2 mol of ethylene glycol, Hydroxyl equivalent 406.6) 2
7.6 g (0.1 mol), triethylamine 85.6 m
A mixture of 1, 4-dimethylaminopyridine 0.72 g, methoquinone 0.01 g and methylene chloride 500 ml is added dropwise. The dropping was completed in about 2 hours, and then the reaction was completed by stirring for 1 hour. Then, the reaction mixture was washed 3 times with 1400 ml of a mixed aqueous solution of 88 g of water, 2 g of phosphoric acid, 5 g of sodium hydrogen carbonate and 5 g of sodium chloride, and the solvent was evaporated under reduced pressure to obtain a polyester compound (A-4) obtained as a bottom residue.
Was a pale yellow semi-solid.

Synthesis Example 5 18.3 g (0.1 mol) of adipic dichloride and 180 ml of methylene chloride were charged, and the mixture was adjusted to 25 ° C. and stirred. Next, 5.8 g (0.05 mol) of 4-hydroxybutyl vinyl ether, 5.8 g (0.1 mol) of 2-hydroxyethyl acrylate, 4.47 g (0.033 mol) of trimethylolpropane, and triethylamine 42. 8 ml, 4-dimethylaminopyridine 0.36
g, 0.01 g of metoquinone and 300 ml of methylene chloride
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 water 8
8 g, phosphoric acid 2 g, sodium hydrogencarbonate 5 g and salt 5
The polyester compound (A-5) obtained as a residue after evaporation was distilled off under reduced pressure to remove the solvent 3 times with 800 ml of a mixed aqueous solution of g.

Examples 1 to 7 and Comparative Examples 1 to 4 The respective components (numerals indicate all 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 to a thickness of 2 μm, and this was applied to a metal halide (80w / cm) of an ultraviolet irradiator.
The coated material was passed under a lamp and one lamp at a distance of 10 cm.
In Table 1, Example 7 and Comparative Example 4 were cured with an electron beam by a conventional method. The following items were evaluated for curing speed, gloss, adhesion and hardness. The results are shown in Table 1.

Evaluation method Curing speed: It is expressed by the irradiation amount (ultraviolet mJ / cm ² , electron beam Mrad) until the tack on the surface disappears after curing. Gloss: 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. When only the applied resin was peeled off, it was evaluated as ×, and Δ is in the middle. Hardness: ◯ when scratched by scratching the surface after curing, × when scratched easily, and Δ in the middle.

Table 1-1 Example 1 2 3 4 5 6 7 Polyester compound (A-1) 70 50 100 Polyester compound (A-2) 40 Polyester compound (A-3) 70 Polyester compound (A-4) 50 Polyester compound (A-5) 50 SP-170 * 1 2 2 2 2 2 2 1 2 KAYARAD R-114 * 2 10 KAYARAD PEG400DA * 3 30 10 20 KAYARAD TMPTA * 4 20 Triethylene glycol divinyl ether 30 30 30 20 50 20 Irgacure 184 * 5 3 1.5 3 5 3 3 Curing speed (mJ / cm ² ) 20 25 20 25 10 25 0.5 Mrad Gloss ○ ○ ○ ○ ○ ○ ○ Adhesion ○ ○ ○ ○ ○ ○ ○ Hardness ○ ○ ○ ○ ○ ○ ○ Table 1-2 Comparative example 1 2 3 4 Polyester compound (A-1) Polyester compound (A-2) Polyester compound (A-3) Polyester compound (A-4) Polyester compound (A-5) SP- 170 * 1 KAYARAD R-114 * 2 30 30 3 0 KAYARAD PEG400DA * 3 50 20 50 50 KAYARAD TMPTA * 4 20 50 50 20 Triethylene glycol divinyl ether Irgacure 185 * 5 5 5 5 cure speed ^{(mJ / cm 2) 28 34} 46 3 Mrad gloss ○ ○ ○ ○ adhesiveness △ ○ × △ 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., acrylate of bisphenol A type epoxy resin * 3 KAYARAD PEG400DA: Nippon Kayaku Co., Ltd., polyethylene glycol diacrylate * 4 KAYARAD TMPTA: Nippon Kayaku Yakuhin Co., Ltd., trimethylolpropane triacrylate * 5 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 the cured product is excellent in gloss, adhesion and hardness.

[0028]

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

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C09D 167/07 PEN 8933-4J

Claims (2)

[Claims] 1. A resin composition comprising a polyester compound (A) having a vinyl ether group and a (meth) acrylate group in the molecule, a photocationic polymerization catalyst (B) and a polymerization initiator (C) as an optional component. object. 2. A cured product of the resin composition according to claim 1.