JPH1087771A - Resim composition, printing ink composition and its cured material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition that contains a (meth)acrylic ester of a specific polyester polyol and a photopolymerization initiator, and can provide an ultraviolet-curing ink composition which has excellent moisture-, grease- and water-proofness, and high washability. SOLUTION: This resin composition contains (A) a (meth)acrylic ester of a polyester polyol (A1 ) which is a reaction product of trimethylol octane (A1 ') with a polybasic acid (anhydride) (A1 "), and (B) a photopolymerization initiator, such as 2,4-diethyl thioxanthone or benzophenone. The component A is obtained, for example, by a dehydration reaction of 1 equivalent of OH A1 ' with 0.01-0.7 equivalent of carboxyl group of A1 " in an organic solvent serving as a dehydrating azeotropic agent at temperature of 90-200 deg.C to produce A1 , and then making 1 equivalent of OH A1 react with 0.9-3 equivalents of (meth)acrylic acid in the presence of a dehydrating azeotropic agent, an esterification catalyst and a polymerization inhibitor.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition and, more particularly, to an ultraviolet-curable printing ink composition which can be suitably used in a lithographic printing method.

[0002]

2. Description of the Related Art In recent years, ultraviolet curable printing inks have been actively developed for the purpose of preventing pollution by eliminating the solvent of printing inks, improving productivity by rapid curing, or improving physical properties of cured films. Various ultraviolet curable printing inks have been proposed so far.

[0003]

The conventional flat inks are:
Although there are many things that can be satisfied with the ultraviolet curability, they are easily emulsified by dampening water (stain) and are liable to cause soiling. Also, when the printing machine is washed due to poor solubility in petroleum solvents, It has the disadvantage of requiring a special cleaning solution.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to improve the above-mentioned problems, and as a result, have been found that ultraviolet light having excellent emulsification resistance to fountain solution (emulsion resistance to fountain solution) and detergency is excellent. A resin composition useful as a curable printing ink composition was found, and the present invention was completed. That is, the present invention
(1) It contains a (meth) acrylate (A) of a polyester polyol (b), which is a reaction product of trimethyloloctane and a polybasic acid or its anhydride (a), and a photopolymerization initiator (B). (2) a resin composition comprising:
(1) The resin composition according to (1), further comprising an unsaturated group-containing compound (C) other than the component (A), (3)
Cured product of the resin composition according to (1) or (2), (4)
Polyester polyol (b) which is a reaction product of trimethyloloctane and polybasic acid or its anhydride (a)
A printing ink composition comprising (A) a (meth) acrylic acid ester (A), a photopolymerization initiator (B) and a pigment; (5) further containing an unsaturated group other than the (A) component of (4). The printing ink composition of (4), characterized by containing the compound (C), (6) a cured product of the printing ink composition according to (4) or (5), (7) on a substrate, (6) And (8) and (7), wherein the printed ink composition is printed and cured.

[0005] In the present invention, trimethylol octane,
A (meth) acrylic acid ester (A) of a polyester polyol (b) which is a reaction product with a polybasic acid or its acid anhydride (a) is used. Trimethyloloctane is a compound in which three methylol groups are bonded to the terminal methyl group of n-octane, and is sold, for example, by Mitsubishi Chemical Corporation. Examples of the polybasic acid or the acid anhydride (a) include succinic acid, maleic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 4-methyl-tetrahydrophthalic acid, Benzene-1,2,4,5-tetracarboxylic acid, trimellitic acid and the like and anhydrides of these acids are mentioned.

As a method for producing the (meth) acrylic acid ester (A), for example, a polyester polyol (b) is obtained by reacting trimethyloloctane with a polybasic acid or its anhydride (a). The (meth) acrylic ester (A) is obtained by reacting the polyester polyol (b) with (meth) acrylic acid. Specifically, the carboxyl group of the polybasic acid or the acid anhydride (a) is 0.01 to 1 equivalent of the hydroxyl group of trimethyloloctane.
Preferably, the reaction is carried out in an amount of from 0.7 to 0.7 equivalent, particularly preferably from 0.1 to 0.5 equivalent. As a reaction solvent, an organic solvent also serving as a dehydrating azeotropic agent (for example, toluene, benzene, cyclohexane, n-hexane, n-heptane, etc.) or a solvent-free reaction temperature of 90 can be used.
The polyester polyol (b) is obtained by performing a dehydration reaction at -200 ° C. Next, the polyester polyol (b), (meth) acrylic acid, the dehydrating azeotropic agent, the esterification catalyst (for example, p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, etc.) and the polymerization inhibitor (for example, methylhydroquinone, Hydroquinone, methoquinone, etc.) and react. The end point of the reaction may be determined by the amount of by-produced water. After completion of the reaction, the reaction solution is washed with water,
After separating the aqueous layer, the solvent is distilled off under reduced pressure to obtain the desired (meth) acrylate (A). It is preferable to use 0.9 to 3 equivalents of (meth) acrylic acid with respect to 1 equivalent of the hydroxyl group of the polyester polyol (b), particularly preferably 1.0 to 1.5 equivalents.

In the present invention, a photopolymerization initiator (B) is used. Specific examples of the photopolymerization initiator (B) include, for example, 2
-Hydroxy-2-methyl-1-phenylpropane-1
-One, 1-hydroxycyclohexylphenyl ketone, methylphenylglyoxylate, benzyldimethylketal, Michler's ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-chlorothioxanthone, , 4-diethylthioxanthone, 2-isopropylthioxanthone,
Benzoin ethyl ether, benzoin isopropyl ether, o-benzoyl benzoic acid methyl ester, p-
Dimethylaminoacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2-ethylanthraquinone, 2-chloroanthraquinone, p-dimethyl Examples include aminobenzoic acid isoamyl ester, p-dimethylaminobenzoaldehyde, benzophenone, p-dimethylaminobenzophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morphonopropan-1-one, and the like.

The photopolymerization initiator (B) can be used alone or as a mixture of two or more. Preferred photopolymerization initiators (B) include 2,4-diethylthioxanthone, 2-isopropylthioxanthone, benzyldimethylketal, 1-hydroxycyclohexylphenylketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6 -Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid isoamyl ester,
Benzophenone, 2-methyl-1- [4- (methylthio) phenyl] -2-morphono-propan-1-one and the like.

The resin composition of the present invention may use an unsaturated group-containing compound (C) other than the component (A). As the unsaturated group-containing compound (C), an acrylate-based reactive compound is preferable, and examples thereof include an acrylate oligomer and an acrylate monomer. Specific examples of the acrylate oligomer that can be used include (meth) acrylate of epoxy resin, rosin-modified urethane (meth) acrylate, polyester (meth) acrylate, and (meth) acrylate of aliphatic modified Alkit resin. Examples of the epoxy resin in the (meth) acrylate of the epoxy resin include bisphenol A type epoxy resin, phenol novolak type epoxy resin, epoxidized aliphatic or alicyclic olefin, epoxidized polybutadiene, and epoxidized rosin. ,

As the acrylate monomer, for example, 2
-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, 2-ethylhexylpolyethoxy (meth) acrylate, benzyl (meth)
Acrylate, phenyloxyethyl (meth) acrylate, phenyloxyethyloxyethyl (meth) acrylate, tricyclodecane mono (meth) acrylate, isobornyl (meth) acrylate, acryloylmorpholine, N-vinylcaprolactam, 2-hydroxy-3-phenyl Oxypropyl (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tripropoxy tri (meth) acrylate, trimethyloloctane tri (meth) acrylate, glycerin tripropoxy Tri (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, bisphenol A
Examples thereof include polyethoxydi (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta and hexa (meth) acrylate, and ditrimethylolpropanetetra (meth) acrylate.

The resin composition of the present invention may further contain, if necessary, a non-reactive resin, a colorant, a polymerization inhibitor, a solubilizer, a filler, an antioxidant, a light stabilizer, an ultraviolet absorber, an organic solvent,
An antifoaming agent, a leveling agent, a coupling agent and other auxiliaries can be used in combination.

Examples of the non-reactive resin include diallyl phthalate resin, petroleum resin, cyclic ketone resin, aromatic hydrocarbon / formaldehyde resin, natural resin modified phenol resin, acrylic resin and the like. As the diallyl phthalate resin, for example, Daiso Dap A manufactured by Osaka Soda Co., Ltd., and as the petroleum resin, for example, Escolets manufactured by Tonen Petrochemical Co., Ltd .; Nippon Zeon Co., Ltd., Quinton, Nippon Petrochemical Co., Ltd., Neopolymer, Toho Oil Co., Ltd., High Resin, Arakawa Chemical Co., Ltd., Alcon, Toyo Soda Co., Ltd. As the ketone resin, for example, Hitachi Chemical Co., Ltd.
Hi-Lack 80, Hi-Lak 110H, Hi-Lack 111, Hi-Lak 222, Halon 80, Ha-Lon 110, etc. manufactured by Honshu Chemical Co., Ltd. are used as aromatic hydrocarbon / formaldehyde resins, for example, Mitsubishi Gas Chemical Co., Ltd. And National Xylene manufactured by Matsushita Electric Works, Ltd., respectively. The softening point of these non-reactive resins is preferably 70 to 160 ° C.

In the resin composition of the present invention, the (meth) acrylate (A) is preferably used in an amount of 5 to 95 parts by weight, more preferably 10 to 90 parts by weight, and the photopolymerization initiator (B) is preferably used in an amount of 0 to 10 parts by weight. 0.5 to 40 parts by weight, more preferably 1 to 3
0 parts by weight of the unsaturated group-containing compound (C) in a desired amount, preferably 0 to 90 parts by weight, more preferably 5 to 85 parts by weight, and if necessary, a non-reactive resin, a polymerization inhibitor,
Kneading machine such as a roll mill, adding a coloring agent, a solvating agent, a filler, an antioxidant, a light stabilizer, an ultraviolet absorber, an organic solvent, an antifoaming agent, a leveling agent, a coupling agent and other auxiliaries. It can be prepared by dissolving, mixing and dispersing in a medium.

The cured product of the resin composition of the present invention can be obtained by generally irradiating the resin composition, preferably a thin film thereof, with energy rays such as ultraviolet rays and electron beams by a conventional method. Examples of the light source such as ultraviolet rays include a low-pressure or high-pressure mercury lamp, a metal halide lamp, a xenon lamp, and the like. Generally, the thickness of the thin film of the resin composition is preferably about 1 to 100 μm. The thin film can be obtained by applying it to the surface of a molded product of various materials such as paper, plastic, wood, and glass.

The ultraviolet-curable printing ink composition of the present invention is obtained by adding a pigment to the above-mentioned resin composition of the present invention. As the pigment, any of an organic pigment and an inorganic pigment can be used. As organic pigments, for example, lithol red, lake red, permanent green, permanent rhodamine, phthalocyanine blue, etc., and as inorganic pigments, for example, alumina, barium sulfate, graphite, navy blue, titanium white, carbon black, etc. Is raised. The content thereof is preferably about 10 to 30% by weight, more preferably about 13 to 25% by weight in the ultraviolet-curable printing ink composition of the present invention.

The ultraviolet-curable printing ink composition of the present invention contains the (meth) acrylate (A) in an amount of preferably 5 to 95 parts by weight, more preferably 10 to 90 parts by weight.
Preferably 0.5 to 40 parts by weight of the photopolymerization initiator (B),
More preferably, 1 to 30 parts by weight, a desired amount of the unsaturated group-containing compound (C), preferably 0 to 90 parts by weight, more preferably 5 to 85 parts by weight, and the pigment is cured by the ultraviolet ray of the present invention. 10 to 10 in the printing ink composition
30% by weight, more preferably 13 to 25% by weight, and further, if necessary, a non-reactive resin, a polymerization inhibitor, a solubilizer, a filler, an antioxidant, a light stabilizer, and an ultraviolet absorber. , An organic solvent, an antifoaming agent, a leveling agent, a coupling agent and other auxiliaries are added, and the mixture is heated, dissolved, mixed and dispersed in a kneader such as a roll mill.

The printed material of the present invention can be obtained by printing and curing the ink composition of the present invention on a substrate so as to have a thickness of about 1 to 50 μm. Examples of the substrate include paper, plastic sheet, metal foil and the like.
As a printing method, for example, lithographic printing (offset printing)
Method, letterpress printing method, screen printing method, sheet-fed printing method, etc., and offset printing method is preferable. Curing by ultraviolet irradiation of the ink composition of the present invention printed on a substrate can be performed by a conventional method. For example, ultraviolet irradiation may be performed using a low-pressure or high-pressure mercury lamp, a metal halide lamp, a xenon lamp, or the like.

An article comprising the printed body of the present invention can be obtained by molding the above printed body. Examples of the article include paper drink containers such as milk packs, sake packs, and juice packs, and exterior boxes such as various cosmetic boxes.

[0019]

Next, the present invention will be described more specifically with reference to examples and comparative examples. Parts in the examples represent parts by weight. (Synthesis example of (meth) acrylate (A)) Synthesis example 1 408 parts of trimethyloloctane, phthalic anhydride 11
8.4 parts and 500 parts of toluene were charged and heated to about 11 parts.
A dehydration reaction is performed at 0 to 125 ° C., and the amount of by-produced water is 1
The reaction was carried out to 4.4 parts, then cooled to 40 ° C. or lower, 380 parts of acrylic acid, 35 parts of p-toluenesulfonic acid and 5 parts of hydroquinone were charged, and heated to about 1 part.
A dehydration reaction was carried out at a temperature of from 0.5 to 120 ° C., and the reaction was carried out until the amount of by-produced water became 93.6 parts. After the reaction was completed, the reaction mixture was cooled, and 2,000 parts of toluene was charged into the reaction mixture.
A 300% aqueous NaOH solution was charged, neutralized, decolorized, allowed to stand, and the aqueous layer was separated. Then, 500 parts of a 15% NaCl aqueous solution was charged, washed, separated into aqueous layers, and then toluene was distilled off. (Meth) acrylic acid ester (A
-1) was obtained. The viscosity of the product is 85 (25 ° C, poise)
Met.

Synthesis Example 2 408 parts of trimethyloloctane were charged, 122 parts of tetrahydrophthalic acid and 500 parts of toluene were charged, and the reaction was carried out in the same manner as in Synthesis Example 1.
Parts, 35 parts of p-toluenesulfonic acid and 5 parts of hydroquinone, and reacted in the same manner as in Synthesis Example 1 (meta).
An acrylate (A-2) was obtained. The viscosity of the product was 70 (25 ° C., poise).

Synthesis Example 3 408 parts of trimethyloloctane, 100 succinic anhydride
And 500 parts of toluene, and the reaction was carried out in the same manner as in Synthesis Example 1. Then, 346 parts of acrylic acid, 30 parts of p-toluenesulfonic acid and 5 parts of hydroquinone were charged, and the reaction was carried out in the same manner as in Synthesis Example 1 (meta). Acrylic ester (A-3) was obtained. The viscosity of the product is 100 (25
° C, Hois).

Examples 1 to 3 and Comparative Example 1 According to the composition shown in Table 1, each component was mixed and dispersed, and the mixture was kneaded with a three-roll mill to prepare an ultraviolet-curable printing ink. Using each of the prepared and prepared printing inks, a test was conducted for emulsification resistance, curability, and washability with washing oil.

(Test Method) Emulsion resistance: A dampening solution was applied to the ink on the kneading roller of an RI-2 type printing tester manufactured by Mei Seisakusho to observe the emulsified state. Bad: emulsified. Slightly poor ... Slightly emulsified. Good: No emulsification at all. Curability: After applying the ink on paper with a RI-2 type printing tester so that the ink film thickness becomes 3 μm, a high-pressure mercury lamp (80 w / cm /
(Light) under the light of 8 cm, and the irradiation amount (mJ / cm ² ) required for dryness to the touch was measured. Washing oil washability: Kerosene and ink were mixed at a weight ratio of 5: 1, the degree of compatibility was observed, and the washability was determined. Poor: Separated without melting. Slightly defective ... Partially separated without complete dissolution. Good: Uniformly dissolved and dispersed.

[0024]

Table 1 Example 1 Comparative Example 1 2 3 1 Acrylic ester (A-1) obtained in Synthetic Example 1 52 Acrylic ester (A-2) obtained in Synthetic Example 2 55 Obtained in Synthetic Example 3 Acrylic acid ester (A-3) 40 KAYARAD R-114 * 1 40 Ditrimethylolpropane tetraacrylate 13 12 Neopentylglycol hydroxypivalate diacrylate 8 8 Trimethylolpropane triacrylate 26 Benzophenone 7 77 7 7 p-Dimethylaminobenzoic acid Isoamyl ester 7 7 7 7 "Bright Red" (pigment, manufactured by Toyo Ink Mfg. Co., Ltd.) 18 18 18 18 Methylhydroquinone 0.1 0.1 0.1 0.1 "Nicanol HP-100" * 2 3 3 --- --- ------ −−−−−−−−−−−−−−−−−−−−−−−−−− Emulsification resistance Good Good Good Poor Ink curability (mJ / cm ² ) 21 18 21 23 Washing oil washability good good good poor

Note) * 1 KAYARAD R-114:
Nippon Kayaku Co., Ltd., Shell Chemical Co., Ltd. Epicoat 82
8 acrylic ester * 2 "Nicanol HP-100": Xylene resin manufactured by Mitsubishi Gas Chemical Company, Ltd.

From the evaluation results shown in Table 1, it is clear that the resin composition of the present invention is particularly excellent in wet resistance to water emulsification and detergency.

[0027]

The resin composition and the ultraviolet-curable printing ink composition of the present invention are particularly excellent in humid resistance to water emulsification and detergency, and are particularly suitable for lithographic printing ink. The resin composition of the present invention is excellent in wettability to a pigment and adhesion to a substrate. Also, by using an unsaturated group-containing compound (C) other than the component (A) in combination, the viscosity of the composition can be adjusted, and the hardness, flexibility, and other characteristics of the cured film can be adjusted. Can be. The composition of the present invention is useful as a printing ink composition for lithographic printing (offset printing), letterpress printing, screen printing, sheet-fed printing, etc., but also includes overprint varnishes, paints, optical materials, adhesives, It is useful in a wide range of fields such as casting, insulating paint, and waterproof paint.

Claims (8)

[Claims] 1. A method for preparing a poly (meth) acrylate (A) of a polyester polyol (b), which is a reaction product of trimethyloloctane and a polybasic acid or its anhydride (a), and a photopolymerization initiator (B). A resin composition comprising: 2. The resin composition according to claim 1, further comprising an unsaturated group-containing compound (C) other than the component (A). 3. A cured product of the resin composition according to claim 1. 4. A (meth) acrylic acid ester (A) of a polyester polyol (b) which is a reaction product of trimethyloloctane and a polybasic acid or an acid anhydride (a) thereof, a photopolymerization initiator (B) and A printing ink composition comprising a pigment. 5. The printing ink composition according to claim 4, comprising an unsaturated group-containing compound (C) other than the component (A) according to claim 1. 6. A cured product of the printing ink composition according to claim 4 or 5. 7. A printed body obtained by printing and curing the printing ink composition according to claim 6 on a substrate. 8. An article comprising the printed body according to claim 7.