JPH06157691A - Radiation-curing resin composition and cured product therefrom - Google Patents

Abstract

PURPOSE:To obtain the subject composition which is water-developable and can give a cured part excellent in water, solvent and chemical resistances by mixing a reactional product of a specified polyesterpolycarboxylic acid with a specified compound with a reactive diluent and/or water. CONSTITUTION:This resin composition comprises a reactional product of a polyesterpolycarboxylic acid having a quat. ammonium salt group the counter ion of which is R1OSO2O<-> or R2COO<-> (wherein R1 and R2 are each alkyl) (e.g. a compound obtained by reacting a diol of formula I with succinic acid) in the molecule with a compound having one epoxy group and a (meth)acryloyl group in the molecule, a reactive diluent (e.g. carbitol acrylate) and/or water and optionally a photopolymerization initiator (e.g. Darocur 2959, a product of Ciba-Geigy).

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. More specifically, it relates to a radiation curable resin composition containing a (meth) acrylate having a specific quaternary ammonium salt group in its molecule as one component, and a cured product thereof.

[0002]

2. Description of the Related Art A radiation curable resin composition curable with ultraviolet rays or electron beams may be used in a solventless form for coating agents and other applications. However, organic solvents are often used in combination in order to improve various properties, and there is a strong demand for water-based resins of this type. Nevertheless, a satisfactory water-soluble radiation-curable resin composition has not been obtained yet. Further, as a photosensitive resin composition such as a printing plate material, a printing ink and a photoresist, there are various types such as an alcohol-soluble type, an alkali-soluble type and an organic solvent-soluble type.
From the standpoints of development processing step, waste liquid processing step, and safety in various operations, the water-soluble type is drawing more attention. Currently, such a water-soluble photosensitive resin composition is mainly of a form in which a diazo compound or the like as a filler is used in combination with a water-soluble emulsion such as partially saponified polyvinyl acetate or polyvinyl acetate. It is used as a plate-making material. Further, JP-A-55-23163 discloses that a water-soluble polymer compound itself has photo-crosslinking property, and a stilbazolium group is introduced into a partially saponified polyvinyl acetate polymer. Resins and photosensitive resin compositions are disclosed.

However, each of the above-mentioned various photosensitive resins or photosensitive resin compositions has a fatal defect or defect, so that there are too many problems for practical use. That is, first, the base polymer itself forming an aqueous emulsion has poor solvent resistance. Therefore, if the amount of partially saponified polyvinyl acetate used is increased in order to improve such solvent resistance in such a photosensitive resin composition, then the water resistance will decrease. Moreover, since the use of a surfactant or the like is indispensable for emulsification of a polymer emulsion, it is more difficult to obtain a product having excellent water resistance and solvent resistance. In addition, in the case of an emulsion composed of polyvinyl acetate and a diazo compound, water (moisture) in the air is absorbed, the diazo group is hydrolyzed, and the photosensitivity is lost. As a result, it becomes an insoluble compound, and as a result, it can be stored for only a few weeks in the mixed state with polyvinyl acetate even at room temperature, and therefore, it has great practicality in terms of storage stability. Will be lacking. On the other hand, a polymer in which a water-soluble polymer compound itself is provided with photo-crosslinking properties is excellent in terms of sensitivity and storage stability, but is practical in terms of water resistance, solvent resistance, etc. The big problem above remains.

[0004]

SUMMARY OF THE INVENTION A resin composition which eliminates various drawbacks in the prior art as described above, that is,
It can be developed with water, and even after the film is dried, the uncured part can be easily redissolved in water and easily removed, and the cured part has excellent water resistance, solvent resistance, chemical resistance, etc. A curable resin composition is provided.

[0005]

Therefore, the present inventors have
As a result of intensive studies, by using a specific compound having a quaternary ammonium salt group and a (meth) acryloyl group in the molecule, compatibility is excellent, storage stability is excellent, and the cured product is water resistant, The present invention has been completed by finding a resin composition which is excellent in solvent resistance and chemical resistance and which can be developed with water.

That is, according to the present invention, a quaternary ammonium salt group (where the counter ion is R ₁ OSO ₂ O ⁻ or R ₂ COO ⁻⁾ in the molecule and R ₁ and R ₂ are C _1-5 alkyl groups. A), a reaction product (A) of a polyester polycarboxylic acid (a) having (a) with a compound (b) having one epoxy group and a (meth) acryloyl group in the molecule, a reactive diluent and / or water ( B) and a radiation-curable resin composition containing a photopolymerization initiator (C) as an optional component and a cured product thereof.

In the present invention, a reaction product of the above-mentioned polyester polycarboxylic acid (a) having a quaternary ammonium salt group in the molecule and a compound (b) having one epoxy group and a (meth) acryloyl group in the molecule ( Use A). Specific examples of the polyester polycarboxylic acid (a) which is a raw material of the reaction product (A) include, for example,

[0008]

[Chemical 1]

[0009]

[Chemical 2]

[0010]

[Chemical 3]

[0011]

[Chemical 4]

[0012]

[Chemical 5]

A diol compound (a-1) such as a polybasic acid or an anhydride thereof (a-2) (for example, adipic acid, isophthalic acid, terephthalic acid, azelaic acid, fumaric acid, maleic acid, maleic anhydride, Phthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.) and, if necessary, a polyhydric alcohol (a-3) other than the diol compound (a-1) (for example,
3-methyl 1,5-pentanediol, ethylene glycol, propylene glycol, 1,3-butylene glycol, diethylene glycol, tetraethylene glycol, glycerin, etc.) can be used as a polyester polycarboxylic acid.

The acid component and the alcohol component are reacted in an equivalent ratio such that the acid component is in excess, to obtain a polyester polycarboxylic acid (a) having a carboxyl group at the molecular end. Acid value of polyester polycarboxylic acid (a) (mgKOH /
Suitable as g) is in the range of 30 to 400. The content of the quaternary ammonium salt group in the polyester polycarboxylic acid (a) is preferably 1.0 to 5.0 mmol / g (g).

Next, specific examples of the compound (b) having one epoxy group and (meth) acryloyl group in the molecule include, for example, glycidyl (meth) acrylate,

[0016]

[Chemical 6]

[0017]

[Chemical 7]

[0018]

[Chemical 8]

[0019]

[Chemical 9]

And the like. The reaction product (A) is reacted with the epoxy group of the compound (b), preferably 0.4 to 1.0 equivalent per equivalent of the carboxyl group of the polyester polycarboxylic acid (a). Obtainable. A catalyst (eg, triethylamine, benzyldimethylamine, tetramethylammonium chloride, triphenylstibine, triphenylphosphine, etc.) is preferably used to accelerate the reaction, and the amount of the catalyst used is based on the reaction raw material mixture. It is preferably used in the range of 0.1 to 10 weight.
In order to prevent the polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, hydroquinone, methylhydroquinone, p-methoxyphenol, phenothiazine, etc.), and the amount thereof is 0.01 to the reaction raw material mixture.
It is preferably used in the range of 1% by weight. The reaction temperature is usually 60 to 150 ° C. The reaction time is usually 5-6.
It's 0 hours. The content of the quaternary ammonium salt group in the obtained reaction product (A) is preferably 0.5 to 3.0 mmol / g, particularly preferably 0.8 to 2.0 mmol / g.
Is.

In the present invention, a reactive diluent and / or water (B) is used. Specific examples of the reactive diluent are widely used from monofunctional ones to polyfunctional ones, and among them, particularly preferable ones are 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl ( (Meth) acrylate, N-vinylpyrrolidone, acryloylmorpholine, carbitol (meth) acrylate, polyethylene glycol di (meth) acrylate,
Examples thereof include water-soluble ones such as glycerin di (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol tri (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate di (meth) acrylate.

Next, specific examples of the photopolymerization initiator (C) used as an optional component include 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propylketone) and (4-benzoylbenzyl). ) Trimethylammonium chloride, (2-acryloxyethyl) (4-benzoylbenzyl) dimethylammonium bromide,
2- (3-Dimethylamino-2-hydroxypropoxy) -3,4-dimethyl-9H-thioxanthene-9-
Water-soluble ones such as on-methyl chloride are preferred.

The radiation curable resin composition of the present invention can be obtained by a method of mixing, dissolving, dispersing and kneading the components (A) to (C).

The proportion of each component used in the present invention is preferably 29 to 95% by weight, and particularly preferably 39 to 95% by weight of the component (A).
80% by weight, component (B) is preferably 5 to 70% by weight, particularly preferably 20 to 60% by weight, (C)
The component is preferably 0 to 15% by weight, particularly preferably 0 to
It is 10% by weight.

The radiation curable resin composition of the present invention may further contain, if necessary, water solubility, storage stability, water resistance, solvent resistance, chemical resistance, etc. within the range not departing from the object of the present invention. It does not prevent addition of known and commonly used organic solvents, inorganic fillers, additives, water-soluble resins of other types (eg, polyvinylpyrrolidone, etc.) within a range in which the above can be maintained. Further, known and commonly used photopolymerization accelerators can be used in combination, and particularly representative photopolymerization accelerators include amines, ureas and other nitrogen-containing compounds, and the use of water-soluble ones. Is desirable.

Radiation in the present invention means electron beam, α-ray,
It is a collective term for ionizing radiation and light such as β rays, γ rays, X rays, neutron rays, and ultraviolet rays. The cured product of the radiation curable resin composition of the present invention can usually be obtained by curing it by radiating the above-mentioned radiation. The resin composition of the present invention can be used, for example, in paints, adhesives, printing inks, plate-making materials, coatings, photoresists and the like.

[0027]

EXAMPLES Next, the present invention will be described in more detail by way of examples. In the following, all parts are by weight unless otherwise specified.

Synthesis Example of Reactant (A) Synthesis Example 1 597 parts of the diol compound represented by the above formula (3) and 200 parts of succinic anhydride were charged, and the reaction solution was heated to 95 ° C. and reacted for about 24 hours, A polyester dicarboxylic acid having an acid value of 141 (mg / KOH / g) and a quaternary ammonium salt content of 1.25 mmol / g was obtained. Then, this reaction liquid was cooled to 60 ° C., 390 parts of the compound represented by the above formula (7) and 3.5 parts of triphenylphosphine were charged, heated to 95 ° C., and reacted for about 24 hours to obtain a reaction product. (A-1) was obtained.
The reaction product (A-1) contained 1.01 m of quaternary ammonium salt group.
has mol / g.

Synthesis Example 2 574 parts of the diol compound represented by the above formula (5) and 100 parts of succinic anhydride were charged, the reaction solution was gradually heated to 200 to 220 ° C. in a nitrogen stream, and 18 parts of distilled water was added. Was removed, then cooled to 60 ° C., 308 parts of hexahydrophthalic anhydride was added, and gradually heated to 90 ° C. in a nitrogen stream, the acid value was 159.4 mg KOH / g, and the content of the quaternary ammonium salt group was 2 0.84 mol / g of polyester dicarboxylic acid was obtained. Next, this reaction solution was cooled to 60 ° C., charged with 390 parts of the compound represented by the above formula (7) and 3.9 parts of triphenylphosphine, and heated to 95 ° C. to about 24
The reaction was carried out for a time to obtain a reaction product (A-2). Reaction product (A-
2) has a quaternary ammonium base of 1.82 mmol / g.

Synthesis Example 3 369 parts of the diol compound represented by the above formula (4) and 196 parts of maleic anhydride were charged, and the reaction solution was heated to 95 ° C. and reacted for about 24 hours to give an acid value of 198.6 mg KOH / g. Thus, a polyester dicarboxylic acid having a quaternary ammonium salt content of 1.77 mmol / g was obtained. Next, this reaction solution is heated to 60 ° C.
To 390 parts of the compound represented by the formula (7),
3.4 parts of triphenylphosphine was charged, heated to 95 ° C., and reacted for about 24 hours to obtain a reaction product (A-3). The reaction product (A-3) was prepared by adding 1.
It has 04 mol / g.

Examples 1 to 5 The respective components (numerical values indicate parts by weight) were mixed in the proportions shown in Table 1 to obtain radiation curable resin compositions, which were made into paints. Next, each of the obtained paints was applied onto a mild steel plate to give a thickness of 50 μm.
It was applied so as to have a film thickness of, and dried at 40 ° C. for 10 minutes. Each of the coating films after coating and drying could be redissolved in water. After that, 500mJ / cm for each coating film with a mercury lamp.
Ultraviolet rays were irradiated to obtain a cured coating film. The results of the performance evaluation of each cured coating film are as shown in Table 1.

[0032]

[Table 1] Table 1 Example * 7 1 2 3 4 5 Urethane acrylate (A-1) 60 35 Urethane acrylate (A-2) 60 30 Urethane acrylate (A-3) 65 30 30 Carbitol acrylate 20 10 20 10 20 Polyethylene glycol diacrylate 20 10 20 10 Glycerin monoacrylate 20 2-Hydroxyethyl acrylate 10 Water 20 25 20 25 Darocur 2959 * 1 5 5 5 5 Redissolvability of uncured coating * 2 ○ ○ ○ ○ ○ Cured coating Membrane Water resistance * 3 ◎ ◎ ◎ ◎ ◎ ◎ Solvent resistance * 4 ◎ ◎ ◎ ◎ ◎ ◎ Alkali resistance * 5 ◎ ◎ ◎ ◎ ◎ ◎ Corrosion test * 6 ○ ○ ○ ○ ○

Note * 1 Darocur 2959: Ciba-Geigy photopolymerization initiator, 4- (2-hydroxyethoxy) phenyl (2-hydroxy-2-propyl) ketone * 2 Evaluation criteria ○ ・ ・ ・ ・ Complete dissolution △・ ・ ・ ・ Insoluble portion remains × ・ ・ ・ ・ ・ ・ Not redissolved * 3, 4, 5: Water, acetone or 1 in gauze respectively
% Evaluation criteria according to the degree of decrease in film thickness after rubbing 20 times with sodium hydroxide ◎ ・ ・ ・ ・ No change ○ ・ ・ ・ ・ 1-5 μm △ ・ ・ ・ ・ 5-10 μm × ... 10 μm or more * 6 Corrosion test: A test piece of SUS304 was dipped in the composition of each example and left at 60 ° C. for 1 week, and the appearance of the test piece was observed. ○ ・ ・ ・ ・ No abnormalities in appearance △ ・ ・ ・ ・ Very slight corrosion × ・ ・ ・ ・ Corrosion on the entire surface * 7 The coating film of Example 3 was irradiated with an electron beam of 5 megarads. A cured coating film was obtained.

As is clear from the evaluation results in Table 1, the resin composition of the present invention can be diluted with water.
It has no effect on the environment or working process and can be redissolved in water up to the uncured portion after the curing treatment. In addition, it is water developable and its cured part (coating film)
However, it has excellent water resistance, solvent resistance, and alkali resistance.

[0035]

The radiation-curable resin composition of the present invention can be diluted with water, and the uncured portion after the curing treatment can be redissolved in water, and the cured portion (coating film) is Excellent in water resistance, solvent resistance, chemical resistance, etc., coating agent,
It is extremely useful in a wide range of applications such as photoresists, printing inks, and plate making materials.

Claims (2)

[Claims] 1. A quaternary ammonium salt group in the molecule (provided that the counterion is R ₁ OSO ₂ O ⁻ or R ₂ COO ⁻ ,
R ₁ and R ₂ are C _1-5 alkyl groups. ) A polyester polycarboxylic acid (a) having a) and a compound (b) having one epoxy group and a (meth) acryloyl group in the molecule (A), a reactive diluent and / or water (B) And a radiation-curable resin composition comprising a photopolymerization initiator (C) as an optional component. 2. A cured product of the radiation curable resin composition according to claim 1.