JPH06184267A - Optically curable resin composition having excellent adhesivity - Google Patents

Abstract

PURPOSE:To obtain the subject composition useful as a coating compound, etc., having excellent adhesiveness, comprising a polyurethane (meth)acrylate prepared by reacting a specific polyhydroxy compound with a specific unsaturated monohydroxy compound and a specific polyisocyanate compound. CONSTITUTION:This resin composition comprises a polyurethane (meth)acrylate prepared by reacting (A) a polyhydroxy compound such as chlorinated polyhydroxy compound with (B) a polyisocyanate compound such as tetramethylene diisocyanate and (C) an unsaturated monohydroxy compound containing one hydroxyl group and one or more (meth)acryloyl groups in the molecule such as 2-hydroxyethyl (meth)acrylate and has >=5.0wt.% (calculated as solid content) of the component A in the polyurethane (meth)acrylate.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention has excellent adhesiveness,
The present invention relates to a photocurable resin composition suitable for applications such as adhesives and ink binders.

[0002]

2. Description of the Related Art Photocurable resins are widely used in paints, adhesives, printing inks, hard coats, OP varnishes and the like. These coated objects (bases) include metals, woods, paper plastics, etc., and as basic performance, adhesion to the coated object is required. Not only hard coats but also printing inks are often printed on plastics in the field of screen printing, and recently printing on plastic bottles has become the mainstream, and these materials are polyolefins such as polyethylene and polypropylene, and polyethylene terephthalate. is there.

[0003]

However, various conventional resins have insufficient adhesion to polyolefin and polyethylene terephthalate, and there have been many demands for resins having good adhesion. As a method for improving such a defect, for example, Japanese Patent Laid-Open No. 63-150304 has been proposed, but adhesion to polyolefin and polyethylene terephthalate is insufficient, and a practically satisfactory one is not found. Absent. In view of the above-mentioned drawbacks in the conventional technique, the present inventor provides a photocurable resin composition having excellent adhesion to all plastics in order to meet the strong demands of the industry.

[0004]

Means for Solving the Problems The present inventors have completed the present invention as a result of intensive studies for solving the above problems. That is, the present invention relates to a polyhydroxy compound (A), a polyisocyanate compound (B), and an unsaturated monohydroxy compound (C) having one hydroxy group and one or more (meth) acryloyl group in the molecule. In a polyurethane (meth) acrylate reacted with another person, the polyhydroxy compound is a chlorinated polyhydroxy compound, and is contained in the polyurethane (meth) acrylate in an amount of 5.0% by weight (solid content conversion). The present invention relates to a photocurable resin composition having excellent adhesion.
As used in the present invention, the expression (meth) acrylate means acrylate and / or methacrylate. The same applies to other expressions such as (meth) acryloyl and (meth) acrylic acid.

The chlorinated polyhydroxy compound used in the present invention is obtained by a dehydration condensation reaction between a chlorinated dicarboxylic acid or acid anhydride and a diol. As the chlorinated dicarboxylic acid or acid anhydride, any one having at least one chlorine in the molecule can be used. For example, chlorendic acid (1,4,5,6,7,7-Hexachloro
-endo-5-norbornene-2,3-dicarboxylic acid), chlorendic anhydride, tetrachlorophthalic acid, tetrachlorophthalic anhydride, tetrachlorosuccinic acid, dichlorofumaric acid, dichloroitaconic acid, octachloroadipic acid, dichloromalein Acid etc. are mentioned. These may be used alone or in combination of two or more. Examples of the diol include butanediol, hexanediol, ethylene glycol,
Examples include neopentyl glycol, bisphenol A, cyclohexanedimethanol, trimethylolpropane, glycerin, pentaerythritol, and furandmethanol. These may be used alone or in combination of two or more. Further, in the dehydration condensation reaction of the chlorinated dicarboxylic acid or acid anhydride and the diol, it is possible to use a dicarboxylic acid or acid anhydride containing no chlorine in the molecule together. It is also possible to use these chlorinated polyhydroxy compounds in combination with known polyhydroxy compounds which are usually used in urethanization reaction. These chlorinated dicarboxylic acids, acid anhydrides and diols can be appropriately selected according to the purpose and application, and the required physical properties such as hardness and softness can be easily designed.

Examples of the polyisocyanate compound used in the present invention include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and 2,8-diisocyanate methylcapsule. aliphatic diisocyanates such as Puroeto, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, dicyclohexylmethane-4,4 ^'- diisocyanate, alicyclic diisocyanates such as methylcyclohexyl-2,4-diisocyanate, Tolylene diisocyanate, diphenylmethane diisocyanate, 1,
Aromatic diisocyanates such as 5-naphthylene diisocyanate, diphenylmethylmethane diisocyanate, and tetraalkyldiphenylmethane diisocyanate, etc. may be mentioned. These may be used alone or in combination of two or more. Examples of the unsaturated monohydroxy compound having one hydroxy group and one or more (meth) acryloyl group in the molecule used in the present invention include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth). Hydroxyalkyl (meth) acrylates such as acrylates, N-hydroxyalkyl (meth) acrylamides such as N-hydroxymethyl (meth) acrylamide, ethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) ) Polyalkylene glycol mono (meth) acrylates such as acrylates can be mentioned. These may be used alone or in combination of two or more.

The method for producing the polyurethane (meth) acrylate obtained by the present invention is as follows. The polyhydroxy compound (A) is reacted with the polyisocyanate compound (B) to obtain a prepolymer having a terminal NCO group, and then the molecule is further added to the molecule. A polyurethane (meth) acrylate is obtained by reacting an unsaturated monohydroxy compound (C) having one hydroxy group and one or more (meth) acryloyl groups.
There is also a method of separately reacting (A), (B) and (C) at the same time, or reacting (B) and (C) and then reacting with (A). The polyurethane (meth) acrylate obtained by the present invention is, for example, 2-ethylhexyl (meth) as a monofunctional unsaturated compound in which various monofunctional unsaturated compounds or polyfunctional unsaturated compounds can be used as necessary. Acrylate, dodecyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate Examples thereof include acryloylmorpholine and N-vinyl-2-pyrrolidone. Examples of polyfunctional unsaturated compounds include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and bisphenol A. ． Examples thereof include ethylene oxide adduct di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trisacryloyloxyethyl isocyanurate, and dipentaerythritol hexa (meth) acrylate. These monofunctional unsaturated compounds and polyfunctional unsaturated compounds may be used alone or in combination of two or more kinds.

The photocurable resin composition of the present invention may optionally contain various additives such as a photopolymerization initiator, a sensitization aid, a surfactant, a defoaming agent, an acid value inhibitor, and a thickener. Be compounded. The photopolymerization initiator is not particularly limited, but for example, benzoyl, benzoin methyl ether, benzyl, benzophenone, 2-hydroxy-2-methylpropiophenone, 2,2-diethoxyacetophenone, benzyldimethylketal, anthraquinone. , Diphenyl sulfide, 2-chlorothioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. These may be used alone or in combination of two or more kinds, and amines such as Michler's ketone, triethylamine and alkylmorpholine may be used in combination with these photopolymerization initiators. The use ratio of these photopolymerization initiators is usually
From 1% by weight to the resin solid content of the resin composition of the present invention
It is 10% by weight, preferably 2% to 6% by weight. The photocurable resin composition of the present invention is used for paints, printing inks, hard coating agents, overprint varnishes and the like, making the most of its excellent adhesiveness.

[0009]

EXAMPLES In order to more specifically describe the present invention, examples and comparative examples will be described below, but the present invention is not limited to these examples. Synthesis Example 1 (Synthesis of chlorinated polyol) 2000 m equipped with thermometer, stirrer, packed tower, cooling pipe, nitrogen (air) inlet pipe
In a 4-necked 4-liter flask, add 6 parts of tetrachlorophthalic anhydride.
82.6 g and 360.3 g of 1,6 hexanediol were charged, the temperature was raised to 190 ° C. while introducing nitrogen, and the esterification reaction was carried out for 10 hours. The dehydration amount was 43.5 g and the acid value was 0.4. The molecular weight of the chlorinated polyol thus obtained was 1485 (calculated from OH number).
Met. Synthesis Example 2 (Synthesis of non-chlorinated polyol) Thermometer, stirrer,
2000 equipped with a packed tower, cooling pipe, and nitrogen (air) inlet pipe
Add tetraphthalic anhydride to 54 ml four-necked flask.
9.8 g and 517.0 g of 1,6 hexanediol were charged, the temperature was raised to 190 ° C. while introducing nitrogen, and the esterification reaction was carried out for 10 hours. The dehydration amount was 67.2 g and the acid value was 0.4. The molecular weight of the thus obtained polyol was 1488 (converted from OH value).

Synthetic Example 3 742.5 g of the chlorinated polyol obtained in Synthetic Example 1 and 241.8 g of ethyl acetate were placed in a 2000 ml four-necked flask equipped with a thermometer, a stirrer and a cooling tube, and the mixture was placed under a nitrogen stream at 70 The temperature was raised to ° C. Next, 166.5 g of isophorone diisocyanate was added, and when the NOC groups were made to react at 70 ° C. and became 1/3 of the initial amount, 58.0 g of 2-hydroxyethyl acrylate and 0.1 g of hydroquinone were added to this reaction solution, While bubbling air into the reaction solution, the reaction was further performed at 70 ° C. for 6 hours to obtain polyurethane acrylate (A-1). Synthesis Example 4 371.3 g of the chlorinated polyol obtained in Synthesis Example 1, 250 g of polytetramethylene ether glycol having a molecular weight of 1000, and 211.5 g of ethyl acetate were mixed with a thermometer, a stirrer,
A 2000 ml four-necked flask equipped with a cooling tube was charged and heated to 70 ° C. under a nitrogen stream. Next, 166.5 g of isophorone diisocyanate was added, and when the NOC groups were made to react at 70 ° C. and became 1/3 of the initial amount, 58.0 g of 2-hydroxyethyl acrylate and 0.1 g of hydroquinone were added to this reaction solution, While bubbling air through the reaction solution, the reaction was further performed at 70 ° C. for 6 hours to obtain polyurethane acrylate (A-2).

Synthetic Example 5 744 g of the non-chlorinated polyol obtained in Synthetic Example 2 and 242.1 g of ethyl acetate were placed in a 2000 ml four-necked flask equipped with a thermometer, a stirrer and a cooling tube, and heated to 70 ° C. under a nitrogen stream. The temperature was raised. Next, 166.5 g of isophorone diisocyanate was added and reacted at 70 ° C., and when the NOC groups became 1/3 of the initial amount, 58.0 g of 2-hydroxyethyl acrylate was added to this reaction solution.
1 g was added, and air was bubbled through the reaction solution to 70
Further, the mixture was reacted at 6 ° C. for 6 hours to obtain a polyurethane acrylate (A-3). Synthesis Example 6 36.3 g of the chlorinated polyol obtained in Synthesis Example 1 and the non-chlorinated polyol 707. 5
g and 242.1 g of ethyl acetate were charged into a 2000 ml four-necked flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was raised to 70 ° C. under a nitrogen stream. Next, 166.5 g of isophorone diisocyanate was added and reacted at 70 ° C.
When the C group became 1/3 of the initial amount, 2-
Hydroxyethyl acrylate (58.0 g) and hydroquinone (0.1 g) were added, and the mixture was further reacted at 70 ° C. for 6 hours while bubbling air into the reaction solution to obtain a polyurethane acrylate (A-4).

Examples 1 to 5 and Comparative Examples 1 to 4 Based on the formulation contents (parts by weight) shown in Table 1, the predetermined photocurable resin obtained in the synthesis example and the predetermined monofunctional unsaturated compound, or A polyfunctional unsaturated compound and a predetermined photopolymerization initiator were added, and they were sufficiently mixed and stirred to obtain respective photocurable resin compositions. (Evaluation Method of Photocurable Resin) The photocurable resin compositions obtained in Examples and Comparative Examples were evaluated as follows, and the results are shown in Table 2.

[0013]

[Table 1]

[0014]

[Table 2]

1) Adhesion property Each plastic test piece was coated with a bar coater so that the coating film thickness after curing was 5 to 6 μm, and the solvent in the coating film was volatilized at 80 ° C./5 minutes. After that, using an irradiation device in which a high-pressure mercury lamp 80 w / cm was set perpendicularly to the sample passage direction, curing was carried out at a conveyor speed of 8 m / min at a position 15 cm below the light source. After the cellophane tape was attached to the test piece, it was peeled off at once and the peeled state of the coating film at that time was displayed.

[0016]

EFFECTS OF THE INVENTION It is clear from Table 2 that the photocurable resin composition of the present invention has excellent adhesion to plastic materials.

Claims (1)

[Claims] 1. A trihydroxy compound (A), a polyisocyanate compound (B), and an unsaturated monohydroxy compound (C) having one hydroxy group and one or more (meth) acryloyl group in the molecule. In a polyurethane (meth) acrylate reacted with a human, the polyhydroxy compound is a chlorinated polyhydroxy compound, and 5.0% in the polyurethane (meth) acrylate.
A photocurable resin composition having excellent adhesion, which is characterized by containing at least wt% (as calculated as solid content).