JPH04283212A - Resin composition and printing ink composition - Google Patents

Abstract

PURPOSE:To provide a printing ink composition excellent in resistance to emulsification in dampening water. CONSTITUTION:A printing ink composition containing an acrylic ester (A) which is a reaction product of dipentaerythritol having a content of dipentaerythritol pentaacrylate of 20% or below with acrylic acid and an ethylenically unsaturated compound (B) other than component A and excelling in resistance to emulsification in dampening water.

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 an ultraviolet curable printing ink composition which can be suitably used in lithographic printing in particular.

0002

BACKGROUND OF THE INVENTION In recent years, the development of ultraviolet curable printing inks has been actively promoted for the purpose of preventing pollution by making printing inks solvent-free, improving productivity by rapid curing, and improving the physical properties of cured films. Various types of ultraviolet curable printing inks have been proposed so far.

0003

Many conventional ultraviolet curable printing inks contain a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (a reaction product of dipentaerythritol and acrylic acid) as a diluent. The ratio of dipentaerythritol pentaacrylate to dipentaerythritol hexaacrylate is approximately 40%-60%:60%-40%). Most of these printing inks are satisfactory in terms of UV curing speed, but because they contain a high content of dipentaerythritol pentaacrylate, they are difficult to emulsify with dampening water due to the influence of the OH groups contained in dipentaerythritol pentaacrylate. Because it is easy to clean, it tends to cause staining, which is a problem.

0004

[Means for Solving the Problems] As a result of intensive research in order to improve the above-mentioned problems, the present inventors have discovered a resin composition that is particularly useful as an ultraviolet curable printing ink composition with excellent moisture resistance and water emulsification properties. This discovery led to the completion of the present invention. That is, the present invention

1. Acrylic acid ester, which is a reaction product of dipentaerythritol and acrylic acid, with a content of dipentaerythritol pentaacrylate of 20% or less (
A resin composition characterized by containing A) and an ethylenically unsaturated group-containing compound (B) other than the component (A); 2. Dipentaerythritol pentaacrylate content is 20%
3. A printing ink composition characterized by containing an acrylic ester (B) which is a reaction product of dipentaerythritol and acrylic acid as follows; 3. 4. A cured product of the resin composition according to item 1. 2. A cured product of the printing ink composition according to item 2.

[0006] The ecrylic ester (A), which is a reaction product of dipentaerythritol and acrylic acid and has a content of dipentaerythritol pentaacrylate of 20% or less, used in the present invention is produced as follows. That is, for 1 chemical equivalent of hydroxyl group of dipentaerythritol, 1.1 to 5.0 chemical equivalents of acrylic acid, preferably 1 chemical equivalent of acrylic acid, is used.
．． It is produced by reacting 5 to 2.5 chemical equivalents. In order to accelerate the reaction during production, it is preferable to use an esterification catalyst (eg, p-toluenesulfonic acid, sulfuric acid, methanesulfonic acid, etc.). The amount of the esterification catalyst used is usually 0.1 to 1 based on the acrylic acid used.
It is 5 mol%, preferably 1 to 6 mol%. Further, in order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor such as hydroquinone or phenothiazine. The reaction temperature is 7
0 to 150°C is preferable, particularly preferably 80 to 130°C.
It is ℃. As a solvent for the reaction, benzene, toluene,
Preferably, non-reactive solvents such as cyclohexane and n-hexane are used.

In the present invention, an ethylenically unsaturated group-containing compound (B) other than component (A) is used. Specific examples of component (B) preferably include compounds having a (meth)acryloyl group, such as neopentyl hydroxypivalic acid glycol di(meth)acrylate, tricyclodecane dimethylol di(meth)acrylate, polyethylene Glycol di(meth)acrylate

000
8]

Trimethylolpropane tripropoxytri(meth)acrylate, trimethylolpropanetriethoxytri(meth)acrylate, pentaerythritol tetrapropoxytetra(meth)acrylate, polyethoxydi(meth)acrylate of bisphenol A, polyethoxydi(meth)acrylate of bisphenol F ) acrylate, ditrimethylolpropane tetra(meth)acrylate, ditrimethylolpropane polypropoxytetra(meth)acrylate, urethane-modified (meth)acrylate or epoxy(meth)acrylate having an acryloyl group in one molecule, polyhydric alcohol and (meth)acrylate of polyester consisting of basic acid, epoxy (meth)acrylate of epoxy resin which is (meth)acrylate of bisphenol type, novolac type or alicyclic type epoxy resin, 2-hydroxyethyl (meth)acrylate, penta Erythritoltri (meth)
Polyurethane (meth)acrylates, alkyd (meth)acrylates, etc., which are reaction products of hydroxyl groups such as acrylates and isocyanate compounds, can be used alone or in combination. Particularly preferred component (B) is ditrimethylolpropane tetraacrylate, trimethylolpropane tripropoxy triacrylate, neopentyl glycol diacrylate hydroxypivalate, tricyclodecane dimethylol diacrylate compound of formula (1), bisphenol A Examples include polyethoxy diacrylate, epoxy acrylate, and polyester acrylate.

When photocuring the resin composition of the present invention, it is preferable to use a photopolymerization initiator (C) that absorbs light energy and generates radicals. Examples of the photopolymerization initiator (C) include 2,4-diethylthioxanthone, benzophenone, isopropylthioxanthone, 2-hydroxy-2-methylpropiophenone, benzyldimethylketanol, 1-hydroxycyclohexyl phenylketone, Irgacure- 907 (manufactured by Ciba Geigy, photopolymerization initiator), 0-benzoylbenzoic acid methyl ester, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminoacetophenone,
Examples include p-dimethylaminobenzaldehyde. Such photopolymerization initiators can be used alone or in combination of two or more. Preferred photoinitiators (C) include benzophenone, 2,4-diethylthioxanthone, 2-hydroxy-2-methylpropiophenone, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, Irgacure-907, p-dimethylamino Examples include benzoic acid ethyl ester. When the resin composition of the present invention is cured by electron beam irradiation, there is no need to add a photopolymerization initiator (C).

The resin composition and printing ink composition of the present invention contain 10 to 10 parts by weight of the ethylenically unsaturated group-containing compound (B) per 100 parts by weight of the acrylic ester (A).
Preferably, 900 parts by weight are used, particularly preferably 50 to 500 parts by weight. The amount of photopolymerization initiator (C) used is preferably 0 to 30 parts by weight, based on 100 parts by weight of the total amount of component (A) + component (B), and is formed by mixing at a ratio of 2 to 25 parts by weight. It is more preferable.

The resin composition and printing ink composition of the present invention may optionally contain resins such as diallylphthaler resin (Daiso Dapp A manufactured by Osaka Soda Co., Ltd.), petroleum resins (such as Tonen Petrochemical Co., Ltd.) Co., Ltd., Escolettes,
Manufactured by Mitsui Petrochemical Co., Ltd., Hilets, Petrogy, Tac Ace, Nippon Zeon Co., Ltd., Quinton, Nippon Petrochemical Co., Ltd., Neopolymer, Toho Oil Co., Ltd., Hi-Resin, Arakawa Chemical Co., Ltd., Alcon, Toyo Soda, Petcol, etc.), cyclic ketone resins (e.g., Hitachi Chemical Co., Ltd., Hilac 80, 110H, 111, 222, Honshu Chemical Co., Ltd., Halon 80, 110, etc.), aromatic carbonization Hydrogen formaldehyde resin (e.g., Mitsubishi Gas Chemical Co., Ltd., Nicanol, Matsushita Electric Works, Ltd., National Xylene, etc.), natural resin-modified phenolic resin, acrylic resin,
Still polymers and the like can be used. Also, solvents such as methyl ethyl ketone, butyl acetate, toluene n-butanol, butyl cellosolve acetate, carbitol acetate, solvent naphtha, etc. can be used. Additionally, additives may be added, e.g. during manufacturing or
Thermal polymerization inhibitor to prevent gelation due to dark reaction during storage (
For example, hydroquinone, p-benzoquinone, phenothiazine, t-butylcatechol, etc.), organic pigments, inorganic pigments, silane coupling agents, leveling agents, slip agents, antioxidants, light stabilizers, antistatic agents, etc. can be used. The resin composition of the present invention can be obtained by uniformly mixing each component.

The resin composition of the present invention is particularly useful as a printing ink composition, but is also useful as a gloss coating agent for paper, a solder resist, a photo-developable solder resist, a hard coat agent, a protective coating agent, etc. It is. The cured product of the resin composition of the present invention can be obtained by curing the resin composition by irradiating it with electron beams or ultraviolet rays in a conventional manner. In particular, the printing ink composition is printed on paper, plastic, metal, glass, ceramic, wood, stone, etc. by means such as lithographic printing (offset printing), letterpress printing, screen printing, sheet-fed printing, etc., and then It is cured by irradiation with electron beams or ultraviolet rays.

[0014]

[Examples] Next, the present invention will be specifically explained with reference to Examples and Comparative Examples. Parts in the examples represent parts by weight. Synthesis example of acrylic acid ester (A) Synthesis example 1 254 parts of dipentaerythritol, 735 parts of acrylic acid, 24 parts of sulfuric acid, 7 parts of hydroquinone, 600 parts of benzene, and 150 parts of cyclohexane were charged and heated, and the produced water was mixed with the solvent. It was distilled, condensed and cooled when 108 parts of water was produced in the separator. The reaction temperature was 85-95°C. The reaction mixture is dissolved in 1200 parts of benzene and 300 parts of cyclohexane, neutralized with 20% aqueous sodium hydroxide solution, washed three times with 500 parts of 20% aqueous sodium chloride solution, and 0.29 part of methoquinone is added. The solvent was distilled off under reduced pressure to obtain 520 parts of liquid. The viscosity (25°C) was 80 poise. Dipentaerythritol pentaacrylate in the product was 10%. (Based on liquid chromatography analysis.)

Example 1 208 parts of neopentyglycol, 166 parts of terephthalic acid, 40 parts of toluene, 0.9 parts of p-toluenesulfonic acid,
18 while adding 0.9 part of phosphorous 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 are added, and the reaction is continued at 100°C until the acid value becomes 25 or less, and then toluene and cyclohexane are removed under reduced pressure. Next, hydroxypivalic acid neopentyl glycol diacrysate (manufactured by Nippon Kayaku Co., Ltd., KATARA)
DMANDA) was added to obtain polyester acrylate. 35 parts of polyester acrylate (B) obtained above, acrylic ester (A) obtained in Synthesis Example 1
) 35 parts, 0.1 part of methylhydroquinone
t Red" (manufactured by Toyo Ink Co., Ltd.), 7 parts of benzophenone, and 7 parts of p-dimethylamino)benzoic acid ethyl ester were mixed and kneaded in a three-roll mill to obtain a printing ink composition. .

Example 2 30 parts of acrylic ester (A) obtained in Synthesis Example 1, 25 parts of ditrimethylolpropane tetraacrylate (B), 13 parts of "Neopolymer 120" (manufactured by Nippon Petrochemical Co., Ltd., petroleum resin) 1 part of "Bright Red" by heating and dissolving 0.1 part of methylhydroquinone, and then cooling.
8 parts of benzophenone, 7 parts of benzophenone, and 7 parts of p-dimethylaminobenzoic acid ethyl ester were mixed and milled using a three-roll mill to obtain a printing ink composition.

Example 3 The same procedure as in Example 1 was carried out except for benzophenone and p-dimethylaminobenzoic acid ethyl ester in Example 1.
A printing ink composition was obtained.

Comparative Example 1 The acrylic ester (A) in Example 1 was replaced with KAYARAD.
A printing ink composition was prepared in the same manner as in Example 1, except that 35 parts of DPHA (manufactured by Nippon Kayaku Co., Ltd., polyacrylate containing 44% dipentaerythritol hexaacrylate and 30% dipentaerythritol pentaacrylate) was used. I got it. Evaluation tests were conducted on the following items using the inks in each of the above examples, and the results are shown in Table 1.

(1) Emulsification Resistance Dampening water was poured onto the ink on the mixing roll of a RI-2 printing tester manufactured by Mei Seisakusho, and the emulsification ability was observed. Poor evaluation ───── Emulsified, slightly poor ───── Slightly emulsified, good ─
─── Not emulsified at all (2) Curing After spreading the ink on paper using an RI-2 printing tester so that the ink film thickness was 3 μm, for Examples 1 and 2 and Comparative Example 1,
The amount of irradiation required to be dry to the touch (mJ/cm 2 ) when passed through a point 8 cm below a high-pressure mercury lamp (80 W/cm, 1 lamp)
was measured. For Example 3, an electron beam was irradiated with an electron beam irradiator (manufactured by ESI, voltage 175 V), and the irradiation amount (megarad) required for dryness to the touch was measured. (3) Washing oil detergency Kerosene and ink were mixed at a weight ratio of 5:1, and their compatibility was taken as a measure of detergency. Poor evaluation --- Slightly poor, with no dissolution and separation --- Good, with a portion not completely dissolved and separation --- Uniformly dissolved and dispersed.

[0020]
Table 1
Example
Comparison example
1 2
3 1
Good emulsification resistance
Good Good
Defective Ink hardenability 20mJ/c
m2 25mJ/cm2 1 mechanism rat
23mJ/cm 2 Washing oil detergency
Good Good
Good Slightly poor

[0021]

EFFECTS OF THE INVENTION The resin composition and printing ink composition of the present invention are particularly excellent in moisture resistance, water emulsifying properties, washability, and curing properties, and are particularly suitable for use as lithographic printing inks. The resin composition and printing ink composition of the present invention have excellent wettability to pigments, excellent adhesion to substrates, and low toxicity.

Claims (4)

[Claims] Claim 1: An acrylic ester (A) which is a reaction product of dipentaerythritol and acrylic acid and has a dipentaerythritol pentaacrylate content of 20% or less.
and an ethylenically unsaturated group-containing compound other than component (A) (B
) A resin composition comprising: 2. Acrylic acid ester (which is a reaction product of dipentaerythritol and acrylic acid) containing 20% or less of dipentaerythritol pentaacrylate (
A printing ink composition comprising A) and an ethylenically unsaturated group-containing compound (B) other than component (A). 3. A cured product of the resin composition according to claim 1. 4. A cured product of the printing ink composition according to claim 2.