JPS58191773A - Ink composition curable with active energy ray - Google Patents

Abstract

PURPOSE:The titled composition, prepared by incorporating an epoxy compound with a low-molecular weight unsaturated compound obtained by adding an alkylene oxide to phenol, etc., and esterifying the resultant addition product with (meth)acrylic acid and a photosensitizer, and curable in a short time. CONSTITUTION:A composition obtained by incorporating (A) an epoxy compound having preferably 200-4,000 molecular weight, e.g. bisphenol type epoxy compound, with (B) a low-molecular weight unsaturated compound obtained by adding an alkylene oxide to at least one of (un)substituted phenol, bisphenol and aliphatic polyhydric alcohol, and further esterifying the resultant addition product with (meth)acrylic acid, and (C) if necessary a radical polymerization initiator, e.g. benzoin, preferably at (10-80):(20-90):(0-15) weight ratio of the components (A), (B) and (C). EFFECT:Improved adhesion and bending property and, suitable for offset printing.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an active energy ray-curable ink composition, and more specifically, it is cured in an extremely short time by irradiation with ultraviolet rays or electron beams, and has excellent adhesion to substrates and foldability. The present invention relates to an active energy ray-curable ink composition that has excellent processability such as compatibility and is excellent for letterpress printing, intaglio printing, and off-cent printing that does not use water.

In recent years, research on coating compositions curable with active energy rays has been actively conducted, and among them, printing inks,
Clear varnish, paint, adhesive.

Practical use is progressing in fields such as photoresists.

These are composed of a radically polymerizable prepolymer and monomer, and a radical polymerization initiator if necessary.The prepolymers include alkyd acrylate, polyester acrylate, epoxy acrylate,
Urethane-modified acrylates have been used, and as monomers, acrylates of aliphatic alcohols, 1-alkylene oxide nonadditive acrylates of phenolic hydroxyl groups, acrylates of glycidyl compounds, etc. have been used.

Alkyd acrylates are plasticized by resin acids, soften the curing test, and have poor solvent resistance. Although epoxy acrylate has excellent curability, it has the disadvantage of poor adhesiveness. In addition, acrylate using a polyisocyanate medium of fatty acid-modified alkyd has poor workability because it becomes uniformly viscous due to the urethane bonds in one molecule. Increase.

It has the disadvantage of poor hardenability.

In this way, when these active energy ray-curable ink compositions are used as coating compositions.

Depending on the type of target metal material and various types of organic coating coated plastic films, etc., adhesion may be insufficient, and there may be problems with processing resistance such as bendability and punching properties, so it is not necessarily suitable for practical use. There were few.

As a result of intensive research to improve these drawbacks, the present invention has excellent curability and excellent processing resistance such as adhesion to substrates and bendability. This led to the invention of an active energy cotton-curable ink composition.

That is, the present invention.

(a) an epoxy compound having one or more epoxy groups per molecule; (b) an alkylene oxide added to at least one compound selected from phenol, bisphenol, and aliphatic polyhydric alcohol, which may have a substituent; This is an active energy ray-curable ink composition comprising a low molecular weight unsaturated compound (C) obtained by esterifying acrylic acid or methacrylic acid, and optionally a radical polymerization initiator.

In the present invention, the epoxy compound may have one or more epoxy groups in one molecule, preferably 1.5 or more, and includes glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, Linear aliphatic epoxides, alicyclic epoxy resins, etc. can be suitably used. Examples of the glycidyl ether type epoxy resin include bisphenol A diglycidyl ether, bisphenol A di-β methyl glycidyl ether, and bisphenol A diglycidyl ether.

Water-added bisphenol A glycidyl ether, bisphenol A alkylene oxide adduct diglycidyl ether, novolac glycidyl ether, polyalkylene glycol diglycidyl ether, epoxy urethane resin, etc. Glycidyl ester type epoxy resin includes diglycidyl phthalate ester , dimer acid diglycidyl ester, etc.; glycidylamine type epoxy resins include triglycidyl isocyanurate; linear aliphatic epoxy resins include epoxidized polybutadiene, epoxidized soybean oil, etc.; Examples of the epoxy resin include bis(3゜4-epoxy-6-methylcyclohexylmethyl)adipate, 3.4-epoxy-6-methylcyclohexylmethyl, and 3.4-epoxy-6-methylcyclohexanecarboxylate. can.

Although the above-mentioned epoxy compounds can be used, it is particularly preferable to use a bisphenol epoxy compound in order to improve processability.

Therefore, the ratio of both can be changed depending on the quality required.

If the epoxy compound (a) has a molecular weight lower than 200, the amount of the monomer (b) used will be reduced and the strength of the cured film will be weakened. In addition, the molecular weight is 4000
If more than 20% is used, the amount of monomer (b) used increases, which increases the crosslinking density and causes deterioration in adhesiveness and processability, which is not preferable.

The low molecular weight unsaturated compound (b) is phenol.

A small number of compounds selected from alkylphenols, resorcinols, bisphenols, trimethylolpropane, pentaerythritol, dipentaerythritol, glycerin, and compounds with substituents introduced into these compounds (both include alkylene oxides such as ethylene oxide and propylene oxide F) It is a (meth)acrylic acid ester monomer obtained by adding an oxide and further esterifying acrylic acid or methacrylic acid.

The amount of alkylene oxide added to phenol, bisphenol, or aliphatic polyhydric alcohol is usually 1 to 8 equivalents, preferably 1 to 4 equivalents per 1 equivalent of hydroxyl group. Moreover, the amount of reaction of acrylic acid or methacrylic acid is a ratio of carboxyl group/hydroxyl group generated by addition of alkylene oxide from -1.1 to 0.9.

In the present invention, when the active energy ray is ultraviolet rays, it is necessary to add a photosensitizer (radical polymerization initiator), including benzoin, benzoin ethyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-chlorobenzoin , benzoin-based 3M sensitizers such as α-allylbenzoin, benzophenone, p-methylbenzophenone, p-chlorobenzophenone, 0-
Aryl kets such as methyl benzoyl benzoate and acetophenone! - Thread sensitizer, 4.4-bisdiethylaminobenzophenone, isoamyl p-dimethylaminobenzoate,
Examples include dialkylaminoarylketone sensitizers such as p-trimethylaminoacetophenone, and polycyclic carbonyl sensitizers such as thioxanthone, xanthone and their halogen-substituted products, and these may be used alone or in appropriate combinations. These photosensitizers are present in the composition.
Although it can be used in a range of 30% by weight, it is preferably in a range of 0 to 15% by weight.

In the present invention, the blending ratio of (a) and (b) is not particularly limited, but preferably (a) 1O~80
(b) 20 to 90% by weight. When producing a diluted varnish with this blending ratio, it is preferable to add a thermal polymerization inhibitor such as hydroquinone or methoxyhydroquinone at 120° C. or lower in order to prevent gelation.

To prepare an active energy ray-curable ink composition, a pigment is usually dispersed in the diluted varnish.

The method is not particularly limited, and can be carried out by conventional dispersion methods such as a three-roll mill or a ball mill. Also, organic 1. In addition to the inorganic 9 extender pigment, plasticizers, surfactants, etc. can be added as necessary. Of course, an ink composition that does not use a pigment may also be used. Furthermore, it is also possible to use other monomers and prepolymers in combination within a range that does not impede the effects of the present invention.

The present invention will be explained below using specific examples. All parts in the examples indicate parts by weight.

Production Example 1 500 parts of Epicoat 1001 (Shell Chemical Co., Ltd. bisphenol A type epoxy resin 1 molecular weight 900),
500 parts of resorcinol ethylene oxide adduct diacrylate obtained as described below and 1 part of hydroquinone are placed in a four-bottle flask equipped with a stirrer, and while blowing air, they are dissolved at 90 to 100°C and pumped out. Let's call it varnish A.

Synthesis of resorcinol/ethylene oxide adduct diacrylate> 347 parts of resorcinol and 17 parts of sodium hydroxide were charged into a small autoclave equipped with a thermometer, a nitrogen introduction device/alkylene oxide introduction device, and a stirring device.
The system was replaced with nitrogen gas while accompanied by Wi, and the temperature was first heated and raised.
At 130 to 160°C, 353 parts of ethylene oxide is gradually introduced at a rate of 5 kg/(<d) and reacted. After the introduction is complete, stirring is continued until the gauge pressure becomes 0.1 kg/C or less to complete one reaction. It took about 30 minutes to obtain a pale yellow viscous liquid of resorcinol/ethylene oxide adduct (average addition amount n-1,3).63 parts of the obtained adduct, 1 part acrylic acid While blowing air into the 4-hole flask.

React for 9 hours at 90-100°C in a benzene stream.

Debenzene at 110° to 120°C when acid value is 4.0
I went there for 2 hours. The obtained product was a pale yellow liquid with a viscosity of 3 voids/25°C.

Production Example 2 Epicoat 1004 (CHE) Kagaku Co., Ltd. I! Bisphenol A type epoxy resin molecule II 600) 40
A resin varnish was prepared in the same manner as in Production Example 1 using 0 part of A-BPE, 4600 parts of A-BPE (bisphenol A-ethylene oxide adduct diacrylate manufactured by Shin-Nakamura Kagaku (1)), and 1 part of methoxyhydroquinone.

Production example 3 YDCN-220M (manufactured by Kyoto Chemical Co., Ltd. 〇-cresol type novolac epoxy resin, epoxy equivalent: 23
0. Resin varnish C was prepared in the same manner as in Production Example 1 using 450 parts of softening point 75°C), 4550 parts of A-BPE, and 1 part of hydroquinone.

Production Example 4 DEN'438 (Dow Chemical Co., Ltd. pseudocarboxylic acid type novolazo epoxy resin, epoxy equivalent 17B) 500
Part, A-BPE-4400 Part 5 DPHA (Dipentaerythritol hexaacrylate manufactured by Japan Tohoku Co., Ltd.) 10
Resin varnish D was produced in the same manner as in the production example using 0 parts of Hydrokino and 71 parts of Hydrokino.

2 Production Example 5 Epicoat 828 (Shell Chemical 11 Bisulfonic Nol Type Epoxy Resin 2 Molecular Weight 380) 717 parts.

Place 4 pieces in a flask and heat to 90℃ while blowing air.
The mixture is reacted at ~120° C. for 15 to 20 hours, the acid value is reduced to 1 or less, and the mixture is pumped out to obtain resin varnish E.

Production Example 6 20 parts of linseed oil fatty acid and 47 parts of trimethylolpropane were heated to an acid value of 5 at 240°C under a stream of N1 gas in a fourth flask.
The mixture was allowed to react to the following level, and 33 parts of phthalic anhydride #& was added thereto and allowed to react at the same temperature for 3 hours to obtain an alkyd with an excess of hydroxyl groups and an acid value of 5.08 and a valence of 310.

Next, 71.5 parts of this alkyd and 14 parts of cyclohexane were placed in a flask, and air was blown into the flask.

The reaction was carried out at 90-110°C for 12 hours, and when the acid value reached 10, membrane cyclohexane reaction was carried out at 110-120°C for 2 hours. The resulting resin had an acid value of 8.2. Viscosity 2000 poise/2
The temperature was 5°C. This was designated as resin varnish F.

Examples and comparative examples Each of the ink compositions shown in Table 1 was applied to a tin plate.

Each coated TFS plate, aluminum plate, and tin plate coated with alkyd resin, vinyl resin, or acrylic resin paint was printed with a coating amount of 30 cm/100 cd using an R1 tester, and then printed using a curtain beam type electron beam irradiation device. Perform 10 Mrad irradiation.

A cured film was prepared. The results are shown in Table 2.

Furthermore, the lamps shown in Table 1) t/-1, 3, 5, 7°9.
11 was printed on a tin plate coated with a vinyl primer using an R1 tester at a coating amount of 30 cm/100 cIa, and immediately after that, 62 with an intensity of 67 W/cm was placed 10 cm under a high-pressure mercury lamp on a conveyor. , irradiated and dried.

The results obtained are shown in Table 3.

J:), (b' Example 9 Using the ink of Example 5, on a nylon plate manufactured by West Germany BASP, with Heidel KORD, SK Co. manufactured by Chongyang Kokusaku Pulp) As a result of printing 10,000 sheets, there were no solid plating or tint spots. Printed matter with good reproducibility was obtained.

Claims (1)

[Claims] 1. (a) an epoxy compound having one or more epoxy groups per molecule; (b) at least one member selected from phenol, bisphenol, and aliphatic polyhydric alcohol, which may have a substituent; A low molecular weight unsaturated compound (C) obtained by adding alkylene oxide to and further esterifying alrylic acid or methacrylic acid, which is curable with active energy rays and optionally containing a radical polymerization initiator. Ink composition. The active energy ray-curable ink composition according to claim 11, wherein the 2° epoxy compound has a molecular weight of 200 to 4,000. 3. The active energy ray-curable ink composition according to claim 1 or 2, wherein the epoxy compound is at least one selected from bisphenol type epoxy compounds and novolak type epoxy compounds.