JPH02284908A - Resin composition and ink composition - Google Patents

Abstract

PURPOSE:To obtain the a resin composition which is suitable for planography ink, because of its excellent ultraviolet curing properties and adhesion by using an acrylic acid ester of a reaction product from bisphenol-A or the like and ethylene oxide and other ethylenically unsaturated compounds. CONSTITUTION:The subject composition is composed of acrylic acid ester of a reaction product from bisphenol-A or bisphenol-F and ethylene oxide, thus containing more than 70% of the compound of formula I (R is -CH2-, formula II), and of an ethylenically unsaturated compound other than the above-stated compounds, preferably dipentaerythritol pentaacrylate, optionally a photopolymerization initiator such as 2,4-diethylthioxanthone or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a resin composition and an ultraviolet curable printing ink composition.

(Prior Art) In recent years, development of ultraviolet curable printing inks has been actively carried out for the purpose of preventing pollution by making printing inks solvent-free, improving productivity by rapid curing, or improving the physical properties of cured films.

(Problem to be solved by the invention) Many acrylic esters are used as conventional ultraviolet curable printing inks, but among them, bisphenol is used because of its curability, suitability for lithographic printing, and low toxicity. An acrylic ester of a compound obtained by addition-reacting an average of about 4 moles of ethylene oxide to 1 mole of A is often used. However, printing inks using acrylic esters of compounds obtained by addition-reacting 1 mole of bisphenol A with an average of about 4 moles of ethylene oxide have the drawback of poor adhesion to various substrates.

(Means for Solving the Problems) In order to improve the above-mentioned problems, the present inventors, as a result of intensive research, have developed an acrylic ester of a compound obtained by adding two moles of ethylene oxide to 1 mole of bisphenol A or bisphenol F. Found a resin composition that is particularly useful as a printing ink composition with excellent curability, lithographic printability, adhesion, etc. by using an acrylic acid ester of a reaction product of bisphenol A or bisphenol F and ethylene oxide as a component. , we have completed the present invention.

That is, the present invention provides: 1) an acrylic ester of a reaction product of bisphenol A or bisphenol P and ethylene oxide containing 70% or more of a compound represented by the general formula CI) and an ethylenically unsaturated substance other than the prison component; Resin composition characterized by containing a group-containing compound (B) and a photopolymerization initiator (q) as an optional component and 2)
The present invention relates to an ink composition characterized by containing the above acrylic ester, an ethylenically unsaturated group-containing compound 03) other than component (A), and a photopolymerization initiator 1c) as an optional component.

to the acrylic ester used in the present invention) is expressed by the general formula [
A reaction product of bisphenol A or bisphenol F containing 70% or more of the compound represented by [I] and ethylene oxide and acrylic acid with sulfuric acid or p-) An esterification catalyst such as toluene and sulfonic acid, and a polymerization inhibitor such as hydroquinone. It can be obtained by reacting in the presence of an agent, preferably at a temperature of 70 to 140°C. The ratio of the reaction product of bisphenol A or bisphenol F and ethylene oxide to acrylic acid is 1:1 to 4 (molar ratio).
The ratio is preferably 1:2 to 3 (molar ratio). A reaction product of bisphenol A or bisphenol F containing 70% or more of the compound represented by general formula [I] and ethylene oxide can also be easily obtained manually from the market. For example, the bisphenol A type is BPF'-20 manufactured by Sanyo Chemical ■, and the bisphenol F type is BFE-20 manufactured by Sanyo Chemical ■.

In the present invention, an ethylenically unsaturated group-containing compound (B) other than the prison component is used. Specific examples of the component (B) include:
Tripropylene glycol diacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tripropoxy triacrylate, neopentyl hydroxypivalate glycol diacrylate, pentaerythritol tetrapropoxytetraacrylate, tricyclodecane dimethylol diacrylate, Pentaerythritol penta and hexaacrylate, ditrimethylolpropane tetraacrylate, - urethane-modified polyacrylate or epoxy acrylate having an acryloyl group in the molecule, polyester acrylate consisting of polyhydric alcohol and polybasic acid, bisphenol A type, novolak type or resin Epoxy acrylate, which is an acrylate of a cyclic epoxy resin; polyurethane acrylate, which is a reaction product of an isocyanate compound and a hydrocarbon such as 2-hydroxyethyl acrylate;
Alkyd acrylates and the like can be used alone or in combination.

Preferred (B) components include dipentaerythritol penta and hexaacrylate, ditrimethylolpropane tetraacrylate, trimethylolpropane triproxy triacrylate, neopentyl hydroxypivalate glycol diacrylate, tricyclodecane dimethylol diacrylate, and epoxy Examples include acrylate, polyester acrylate, and the like. Next, in the present invention, a photopolymerization initiator (q is, for example, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, benzine ethyl ether, penzoiniso Globyl ether, diethylthioxanthone, isopropylthioxanthone, 2-hydroquino-2-methylglopiophenone, benzyl dimethyl ketal, 1-
Hydroxycyclohexyl phenyl ketone, benzophenone, 0-benzoylbenzoic acid methyl ester, p-dimethylaminoacetophenone, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzaldehyde, p-dimethyl Examples include aminobenzophenone.

Such photopolymerization initiators can be used alone or in combination of two or more. Preferred photoinitiators (q include, for example, 2,4-diethylthioxanthone, isopropylthioxanthone, 2-hydroxy-2-methylpropiophenone, benzyl dimethyl ketal, 1-
Examples thereof include hydroxycyclohexyl phenyl ketone, benzophenone, -9 methylaminobenzoic acid ethyl ester, and the like.

The resin composition and ink composition of the present invention preferably contain 5 to 70 parts by weight, more preferably 10 to 50 parts by weight of the acrylic acid ester hole) and preferably 10 to 50 parts by weight of the ethylenically unsaturated group-containing compound (13). , 30 to 95 parts by weight, more preferably 50 to 90 parts by weight, and a photopolymerization initiator (Q,
Preferably, it is formed by mixing at a ratio of 0 to 30 parts by weight, more preferably 2 to 25 parts by weight.

The resin composition and ink composition of the present invention may optionally include resins, such as diallyl phthalate resin (Osaka Soda, Daiso Tsubu A), petroleum resin (for example, Tonen Petrochemical (Kiki, Escolenotsu, Mitsui Petrochemical). Made by ■, Hylac, Vetrozin, Tac Ace, Nippon Zeon ■, Quinton, Nippon Petrochemical ■, Neopolymer Toho Oil ■, HiResin, Department chemicals (Kikusei, Alcon, Toyo Noda, Vetcol, etc.), Cyclic resins (e.g.
Made by Hitachi Chemical ■, Hilac 80.110■-1,111
, 222, manufactured by Honshu Kagaku ■, Ron 80, 110, etc.),
Examples of the resin include aromatic hydrocarbon/formaldehyde resins (for example, Mitsubishi Gas Chemical ■, Nikanol, Osaka Denko ■, National Xylene, etc.), natural resin-modified phenolic resins, acrylic resins, and the like. Also, solvents such as methyl ethyl ketone, butyl acetate, toluene, butanol,
Examples include solvent naphtha. Furthermore, additives, such as thermal polymerization inhibitors (for example, hydroquinone, p-benzoquinone, phenothiazine, t-butylcatechol, etc.) to prevent gelation due to dark reactions during manufacturing or storage, and organic pigments. , inorganic pigments, etc. can be used.

The resin composition of the present invention is useful not only as an ink composition, but also as a gloss coating agent, a protective coating agent, etc. for paper.

The ink composition of the present invention can be used for planographic printing (offset printing)
It is printed on paper, plastic, metal, wood, etc. by means such as letterpress printing, screen printing, sheet-fed printing, etc., and then cured by irradiation with electron beams or ultraviolet rays by a conventional method.

(Example) Next, the present invention will be specifically explained using Examples and Comparative Examples.

Parts in the examples represent parts by weight.

[Example of synthesis of acrylic acid ester hole]

Synthesis Example 1 Reaction product of bisphenol A and ethylene oxide [manufactured by Sanyo Kasei ■, BPE-20, 82.5% adduct of 2 moles of ethylene oxide and 15.8% of adduct of 3 moles of ethylene oxide to 81 moles of bisphenol , ethylene oxide 4 mole adduct 1.8%, the above data shows gas chromatography area ratio 9280 parts, acrylic acid 216 parts, sulfuric acid 7 parts,
1 part of hydroquinone, 240 parts of benzene, and 60 parts of cyclohexane were charged, and the resulting water was heated from 1 to 1. The water produced was distilled together with a solvent, condensed, and cooled when 35 parts of water was produced in a separator. The reaction temperature was 84-90°C. The reaction mixture is dissolved in 800 parts of benzene and 200 parts of cyclohexane, neutralized with 20% NaOH aqueous solution, and then washed three times with 100 parts of 20% NaCl aqueous solution. The solvent was distilled off under reduced pressure to obtain 360 parts of liquid. The viscosity (25°C) is 4900 CPS.

Synthesis Example 2 Reaction product of bisphenol F and ethylene oxide (Sanyo Kasei 13FE-20, 74% adduct of 2 moles of ethylene oxide, 14% of adduct of 3 moles of ethylene oxide, 4% of adduct of ethylene oxide to bisphenol Fi-E-l) Molar adduct 1.6% The above data is gas chromatography area ratio)
252 parts of acrylic acid, 216 parts of acrylic acid, 7 parts of sulfuric acid, 1 part of nohydroquinone, 240 parts of benzene, and 60 parts of cyclohexane were charged and heated, and the produced water was distilled together with the solvent and condensed to produce 35 parts of water in a separator. At that point, it was cooled. The reaction temperature was 84-90°C. The reaction mixture was dissolved in 800 parts of benzene and 200 parts of cyclohexane, and 20% N
After neutralization with aOH aqueous solution, 20% Na CL aqueous solution 1
Wash 3 times with 00 parts. The solvent was distilled off under reduced pressure to obtain liquid 331.
I got the department. The viscosity (25°C) is 940 CPS.

Comparative Synthesis Example 3 Reaction product of bisphenol A and ethylene oxide (Sanyo Kasei ■, BPE-40, 2 mole adduct of ethylene oxide 10.0%, 29.8% adduct of 3 mole ethylene oxide per 1 mole of bisphenol A) , 4 mole ethylene oxide adduct 33%, 5 mole ethylene oxide adduct 18.5%, 6 mole ethylene oxide adduct 7
．． 5%, 7 mol ethylene oxide adduct 0.4%, the above data is gas chromatography area ratio) 368 parts, acrylic acid 216 parts, p) luenesulfonic acid 10 parts, hydroquinone 1 part, benzene 320 parts, cyclohexane 80 parts
The resulting water was distilled together with the solvent, condensed, and cooled when 36 parts of water had been produced in the separator. The reaction temperature was 84-90°C. The reaction mixture was dissolved in 800 parts of benzene and 200 parts of cyclohexane, and 20% N
After neutralizing with a 01-I aqueous solution, the sample is washed three times with 200 parts of 20% NaCj aqueous solution. Distill the solvent under reduced pressure to obtain liquid 4.
Got 30 copies. Viscosity (25°C) is 900 CPS.

Example 1゜40 parts of acrylic ester (A) obtained in Synthesis Example 1, 10 parts of ditrimethylolpropane tetraacrylate, 1 part of "Neopolymer 120J (manufactured by Nippon Petrochemical ■, petroleum resin)"
8 parts, 0.1 part of methylhydroquinone at 120℃
After stirring and dissolving for 0 minutes, and then cooling, rBright R
edJ (manufactured by Toyo Ink ■) 18 parts, benzophenone 7
Part, p-dimethylamitubenzoic acid isoamyl ester 7
The mixture was mixed and kneaded using a three-roll mill to obtain an ink composition.

This ink composition was spread on milk carton paper using an RI-2 printing tester manufactured by Mei Seisakusho ■, passed through a metal halide lamp (80 W/cm, 1 light) at a distance of 8 cm, cured with ultraviolet light, and then coated with cellophane tape. A peel test was performed, but there was no part that peeled off.

Example 2゜208 parts of neopentyl glycol, 166 parts of terephthalic acid
parts, 40 parts of toluene, 09 parts of p-toluenesulfonic acid,
18 parts by adding 09 parts of hypophosphorous acid and blowing in nitrogen gas.
Heat to 0°C and react for 6 hours. The reaction takes place at an acid value of 10
Continue until below.

Next, 142 parts of acrylic acid, 54 parts of cyclohexane, and 0.1 part of hydroquinone were added, and the reaction was continued at 100°C.
After continuing until the acid value becomes 25 or less, toluene and cyclohexane are removed under reduced pressure. Next, 100 parts of the acrylic ester (A) obtained in Synthesis Example 2 was added to obtain polyester acrylate.

47 parts of polyester acrylate obtained above, 21.5 parts of acrylic ester (A) obtained in Synthesis Example 2, 01 part of methylhydroquinone, "13right 1lcd"
18 parts of J, 7 parts of benzophenone, and 7 parts of p-dimethylaminobenzoic acid isoamyl ester were mixed and kneaded in a three-roll mill to obtain an in.~=1', n substitute. This ink composition was spread on milk back paper in the same manner as in Example 1, cured with ultraviolet rays, and subjected to a cellophane tape peeling test, but there was no part that separated by 7.11.

Example 3゜40 parts of acrylic ester (A) obtained in Synthesis Example 1, KA
YARAD DPI-IA (manufactured by Nippon Kayaku ■, dipentaerythritol penta and hexaacrylate mixture)
10 parts, Paraloid B-60 (manufactured by Rohm & Haas, acrylic polymer), 15 parts, Tomer 3016 (san no pco, epoxy acrylate), 35 parts, Irgacure 184 (manufactured by Ciba Geigy, photopolymerization initiator) )5
1 part and 40 parts of methyl ethyl ketone were mixed and dissolved to obtain a resin composition. This resin composition was applied with a wire bar onto paper printed with oil-based ink, and after drying the solvent (methyl ethyl ketone), it was cured with ultraviolet rays, and a cellophane tape peeling test was performed, but there was no part that peeled off.

Comparative Example 1 An ink composition was obtained in the same manner as in Example 1 except that Synthesis Example 1 was replaced with Comparative Synthesis Example 3. This ink composition was spread on milk carton paper in the same manner as in Example, cured with ultraviolet rays, and subjected to a cellophane tape peeling test. As a result, it was almost completely peeled off.

Comparative Example 2 A resin composition was obtained in the same manner as in Example 3, except that Synthesis Example 1 was replaced with Comparative Synthesis Example 3. This resin composition was applied with a wire bar onto paper printed with oil-based ink in the same manner as in Example 3, and after drying the solvent, it was cured with ultraviolet rays, and a cellophane tape peeling test was performed. completely peeled off.

(Effects of the Invention) The resin composition and ink composition of the present invention have good curability with ultraviolet rays, excellent adhesion, and are suitable for lithographic printing inks.

Claims (1)

[Claims] 1. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] (However, in the formula [I], R is -CH_2- or ▲ Numerical formulas, chemical formulas, tables, etc. Acrylic acid ester (A) of the reaction product of bisphenol A or bisphenol F and ethylene oxide containing 70% or more of the compound represented by A resin composition comprising a compound (B) and a photopolymerization initiator (C) as an optional component. 2. An ink containing the acrylic ester (A) described in item 1, an ethylenically unsaturated group-containing compound (B) other than the component (A), and a photopolymerization initiator (C) as an optional component. Composition.