JPH06157693A - Radiation-curing resin composition and cured product therefrom - Google Patents

Abstract

PURPOSE:To obtain the subject composition which can be diluted with water and can give a cured part (coating film) excellent in water, solvent and chemical resistances, etc., and from which the uncured part can be removed by redissolution in water. CONSTITUTION:This resin composition comprises a urethane (meth)acrylate which is a reactional product of a polyol compound (a) having a carboxybetaine- type quat. ammonium salt group in the molecule, a polyol compound (b) other than component (a), an organic polyisocyanate (c) and a hydroxylated (meth) acrylate (d), a reactive diluent and/or water, and optionally a photopolymerization initiator.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a radiation curable resin composition. More specifically, it relates to a radiation curable resin composition containing a specific (meth) acrylate having a carboxybetaine type quaternary ammonium salt group in its molecule as one component.

[0002]

Radiation curable resin compositions which can be cured by ultraviolet rays or electron beams are sometimes used in a solventless form for coating agents and other purposes, but organic solvents are used to improve various performances. In many cases, they are used in combination, and there is a strong demand for water-based resins of this type. Nevertheless, the fact is that a satisfactory water-soluble radiation-curable resin composition has not yet been obtained. Further, as a photosensitive resin composition such as a printing plate material, a printing ink, and a photoresist, an alcohol-soluble type,
There are various types such as alkali-soluble type and organic solvent-soluble type, but from the viewpoint of safety in development process, waste liquid treatment process and various work, the water-soluble type is more focused. Is becoming popular. Currently, such a water-soluble photosensitive resin composition is mainly in the form of using a diazo compound or the like as a filler together with a water-soluble emulsion of partially saponified polyvinyl acetate or polyvinyl acetate. , Are used as plate making materials. In addition, JP-A-55-2
3163 discloses a photosensitive resin in which a stilbazolium group is introduced into a partially saponified polyvinyl acetate polymer as a water-soluble polymer compound itself having photocrosslinking property, and a photosensitive resin. Compositions are disclosed.

However, since the above-mentioned various photosensitive resins or photosensitive resin compositions have fatal defects or defects, they are practically used.
There are too many problems. 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 the polymer emulsion, it becomes more difficult to obtain a product having excellent water resistance and solvent resistance. There is a drawback that. In addition, in the case of an emulsion composed of polyvinyl acetate and a diazo compound, the 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 a mixed state with polyvinyl acetate even at room temperature, and therefore, it can be practically used in storage stability. It lacks sex. On the other hand, a polymer in which a water-soluble polymer compound itself has photo-crosslinking properties is excellent in terms of sensitivity and storage stability, but it is practical in terms of water resistance and dissolution resistance. 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 portion is easily redissolved in water and easily removed. Further, it provides a radiation curable resin composition having a cured portion excellent in water resistance, solvent resistance, chemical resistance and the like.

[0005]

Therefore, as a result of intensive investigations, the present inventors have found that they are compatible with each other and have excellent storage stability, and that their cured products have water resistance, solvent resistance, chemical resistance, etc. The present invention has been completed by finding a resin composition which is excellent in development and can be developed with water. That is, the present invention relates to a polyol compound (a) having a carboxybetaine type quaternary ammonium salt group in the molecule, a polyol compound (b) other than the component (a), an organic polyisocyanate (c), and a hydroxyl group-containing (meth) acrylate ( Radiation-curable, containing urethane (meth) acrylate (A) which is a reaction product with d), a reactive diluent and / or water (B) and a photopolymerization initiator (C) as an optional component. The present invention relates to a resin composition and a cured product thereof.

In the present invention, the polyol compound (a) having a carboxybetaine type quaternary ammonium salt group in the molecule, the polyol compound (b) other than the component (a), the organic polyisocyanate (c), and the hydroxyl group-containing (meth) acrylate. Urethane (meth) acrylate (A) which is a reaction product with (d) is used. Polyol compound (a) having a carboxybetaine type quaternary ammonium salt group in the molecule which is a raw material of urethane (meth) acrylate (A)
For example,

[0007]

[Chemical 1]

[0008]

[Chemical 2]

[0009]

[Chemical 3]

[0010]

[Chemical 4]

[0011]

[Chemical 5]

A diol compound (a-1) such as the above, the diol compound (a-1) and a polybasic acid or an anhydride thereof (eg adipic acid, isophthalic acid, azelaic acid,
A polyester diol compound (a-2) which is a reaction product with fumaric acid, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, etc., and the above diol compound (a-
Examples thereof include a polycaprolactone diol compound (a-3), which is a reaction product of 1) with ε-caprolactone. Specific examples of the polyol compound (b) other than the component (a) include ethylene glycol, propylene glycol, 1,6 hexanediol, and 3-methyl-.
1,5-pentanediol, trimethylolpropane,
Polyethylene glycol, polypropylene glycol,
Examples thereof include polytetramethylene glycol, polycarbonate diol, polyester polyol, and polycaprolactone polyol. The ratio of the components (a) and (b) used is (a) component: (b) component = 4.
0 to 95: 5 to 60 (% by weight) is preferable.

Specific examples of the organic polyisocyanate (c) include 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, dicyclohexylmethane-diisocyanate,
Examples thereof include isophorone diisocyanate and hexamethylene diisocyanate. Specific examples of the hydroxyl group-containing (meth) acrylate (d) include 2-hydroxyethyl (meth) acrylate and 2-
Hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerin di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di ( Examples thereof include (meth) acrylate and N-methylol (meth) acrylamide.

The above polyol compound (a) and the above (a)
The reaction of the polyol compound (b) other than the component and the organic polyisocyanate (c) is performed by reacting the polyol compound (a) with the polyol compound (b) other than the component (a).
The isocyanate group of the organic polyisocyanate (c) is preferably 1.1 to 2.0 equivalents relative to 1 equivalent of the hydroxyl group of the mixture.

The reaction temperature is preferably 60 to 100 ° C, particularly preferably 75 to 85 ° C. Reaction time is 5 to 20
Time is preferred. Then, the polyol compound (a)
And an isocyanate group of a reaction product of the polyol compound (b) other than the component (a) and the organic polyisocyanate (c), 1 equivalent of the hydroxyl group of the hydroxyl group-containing (meth) acrylate (d), 0.95 A urethane (meth) acrylate (A) can be obtained by reacting ~ 1.2 equivalents. At this time, in order to prevent polymerization, it is preferable to use a polymerization inhibitor such as methylhydroquinone, p-methoxyphenol, or hydroquinone. The amount of the polymerization inhibitor used is 0.01 to 0.
5% by weight is preferred. The reaction temperature is preferably 60 to 100 ° C, particularly preferably 75 to 85 ° C. The reaction time is preferably 5 to 20 hours. The content of the quaternary ammonium halide in the obtained urethane (meth) acrylate (A) is preferably 0.5 to 3.0 mmol (mmol) / gram (g), particularly preferably 0.8 to It is 2.0 mmol (m mol) / gram (g).

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. 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, glycerin di (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol tri (meth) acrylate, Water-soluble substances such as tris (2-hydroxyethyl) isocyanurate di (meth) acrylate can be mentioned.

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) trimethyl. Ammonium chloride (2-acryloxyethyl) (4-benzoylbenzyl) dimethylammonium bromide, 2-
(3-dimethylamino-2-hydroxypropoxy)
3,4-Dimethyl-9H-thioxanthen-9-one-
Water-soluble substances such as 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 of the component (A), particularly preferably 39.
To 80% by weight, the component (B) is preferably 5 to 70% by weight, particularly preferably 20 to 60% by weight,
The component (C) is preferably 0 to 15% by weight, particularly preferably 0 to 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 (for example, polyvinylpyrrolidone, etc.) within a range in which the above can be maintained. Further, known and commonly used photopolymerization accelerators can also be used in combination, and particularly representative photopolymerization accelerators include amines, ureas and other nitrogen-containing compounds, which are water-soluble. Use 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 be usually obtained by curing it by irradiating 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.

[0022]

EXAMPLES Next, examples of the present invention will be further described. In the following, all parts are by weight unless otherwise specified. Synthesis Example of Urethane (Meth) Acrylate (A) Synthesis Example 1 177 parts of the compound represented by the formula (5) and polyethylene glycol (molecular weight 1000, OH value (mgKOH / g) 11
2) Charge 323 parts and isophorone diisocyanate 441 parts and react at 80 ° C. for about 10 hours, then charge 2-hydroxyethyl acrylate 161 parts and p-methoxyphenol 0.5 part and react at 80 ° C. for about 15 hours,
Urethane acrylate (A-1) was obtained. This is a carboxybetaine-type quaternary ammonium base in the molecule 0.9
It has millimoles (mmol) / gram (g).

Synthesis Example 2 367 parts of polyester diol, which is a reaction product of 2 mol of the compound represented by the formula (2) and 1 mol of adipic acid, polytetramethylene glycol (molecular weight 850, OH value (mg
KOH / g) 132) 383 parts, tolylene diisocyanate 3
Charged 78.6 parts, reacted at 80 ° C. for about 10 hours, and then 176.7 parts 2-hydroxyethyl acrylate, p
-Prepare 0.6 parts of methoxyphenol, about 1 at 80 ℃
The reaction was carried out for 5 hours to obtain urethane acrylate (A-2). It has 1.5 mmol (mmol) / gram (g) carboxybetaine-type quaternary ammonium base in the molecule.

Synthesis Example 3 353 parts of the compound represented by the above formula (1) and polytetramethylene glycol (molecular weight 1000, OH value 112) 1
Charge 47 parts and 382.3 parts of isophorone diisocyanate and react at 80 ° C. for about 10 hours, then charge 139.7 parts of 2-hydroxyethyl acrylate and 0.5 part of p-methoxyphenol and react at 80 ° C. for about 15 hours. And urethane acrylate (A-3) was obtained. It has 0.98 mmol (mmol) / gram (g) of carboxybetaine-type quaternary ammonium base in the molecule.

Examples 1 to 5 The components (numerical values indicate parts by weight) were mixed in the proportions shown in Table 1 to obtain a radiation curable resin composition, which was made into a paint. 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 ^{2 was} applied to 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.

[0026]

[Table 1] Table 1 Examples * 7 1 2 3 4 5 6 Urethane acrylate obtained in Synthesis Example 1 (A-1) 70 35 60 Urethane acrylate obtained in Synthesis Example 2 (A-2) 60 40 Synthesis Example Urethane acrylate obtained in 3 (A-3) 50 30 30 2-hydroxyethyl acrylate 10 Polyethylene glycol diacrylate 10 30 20 20 Glycerin monoacrylate 10 20 Water 30 30 40 20 30 Darocure 2959 * 1 5 5-5 5 5 5 Not Resolubility of cured coating * 2 ○ ○ ○ ○ ○ ○ Cured coating Water resistance * 3 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Solubility resistance * 4 ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ Alkali resistance * 5 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Composition Metal corrosiveness of objects * 6 ○ ○ ○ ○ ○ ○

Note * 1 Darocur 2959: manufactured by Ciba-Geigy, a photopolymerization initiator, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone * 2 Evaluation Criteria ○ ... Complete Dissolved △ ・ ・ ・ ・ Insoluble portion remains × ・ ・ ・ ・ No re-dissolution * 3,4,5: Gauze was impregnated with water, acetone or 1% sodium hydroxide, and rubbed 20 times. Evaluation criteria according to the degree of decrease of the film thickness ◎ ・ ・ ・ ・ No change ○ ・ ・ ・ ・ 1 to 5 μm △ ・ ・ ・ ・ 5 to 10 μm × ・ ・ ・ ・ 10 μm or more * 6 SUS304 in each example Soak in the composition of 60
After standing at 7 ° C for 7 days, the degree of corrosion of SUS304 was observed. Evaluation criteria ○ ・ ・ ・ ・ No abnormality at all △ ・ ・ ・ ・ Slight corrosion was observed × ・ ・ ・ ・ Corrosion was observed on the entire surface. * 7 The coating film of Example 3 was irradiated with an electron beam of 5 mega rat and cured. Got

As is clear from Table 1, the resin composition of the present invention can be diluted with water and therefore has no effect on the environment or working process, and the uncured portion after the curing treatment can be redissolved in water. Therefore, it is water-developable, and its cured portion (coating film) is excellent in water resistance, solvent resistance, alkali resistance and the like.

[0029]

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

Claims (2)

[Claims] 1. A polyol compound (a) having a carboxybetaine type quaternary ammonium salt group in the molecule, a polyol compound (b) other than the component (a), an organic polyisocyanate (c), and a hydroxyl group-containing (meth) acrylate (d). ) Urethane (meth) acrylate (A), which is a reaction product with
A radiation curable resin composition comprising a reactive diluent and / or water (B) and a photopolymerization initiator (C) as an optional component. 2. The radiation curable resin composition according to claim 1.