JPS61266406A - Ultraviolet-curing resin composition - Google Patents

Abstract

PURPOSE:To improve adhesion of film to metal, by using a specified compound as a reactive diluent in a composition which consists mainly of a base resin, a reactive diluent and a photopolymerization initiator and forms a film by irradiation with ultraviolet rays. CONSTITUTION:The purpose ultraviolet-curing resin composition is obtained by using a base resin (A) (e.g., polyester polyvinyl compound), a reactive diluent partially or entirely consisting of a compound (B) of formula I and a photopolymerization initiator (C) (e.g., benzophenone). By applying this composition to a substrate and irradiating it with ultraviolet rays, a film having excellent adhesion to the substrate can be formed. The compound of formula I can be advantageously produced by reacting cyclohexanone with glycerin and transesterifying the obtained reaction product of formula II with methyl acrylate.

Description

Detailed Description of the Invention A3 Industrial Field of Application The present invention relates to a resin composition that is cured by ultraviolet rays, and more specifically to a resin composition that has good adhesion to various substrates, particularly paper and polyethylene terephthalate resin substrates. This invention relates to an excellent ultraviolet curable resin composition.

B. Prior Art In recent years, so-called active energy ray-curable resin compositions, which are cured by irradiation with active energy rays such as ultraviolet rays, have been widely used in various plastics, metals, It is being used industrially for painting paper, printing, etc.

C9 Problems to be Solved by the Invention Ultraviolet curable resin compositions used for such purposes generally include (a) a base resin, (b) a reactive diluent, and (c)
It is formed mainly from a photopolymerization initiator. The base resin (a) is also called a prepolymer or oligomer, and is a compound having at least one ethylenically unsaturated group in the molecule. This material is often an extremely viscous liquid at room temperature, and has the property of slow curing speed if left as is. These properties cause significant difficulties in terms of workability when coating and curing the substrate, so in order to improve this point (
B) A polymerizable monomer called a reactive diluent is used in combination. This material is required to have two properties: a diluent, that is, a viscosity-reducing effect by incorporating it, and curing acceleration. Generally, polyfunctional acrylates such as trimethylolpropane triacrylate, diethyl glycol diacrylate, neopentyl glycol diacrylate, and 1,6-hequinanediol diacrylate are used to meet the latter performance requirements. However, when such a polyfunctional reactive diluent is used, it is known that residual stress is generated in the film due to intense curing, and the cured film is brittle, resulting in a decrease in adhesion. .

Means for Solving Problem D8 Based on this background, the present inventors solved the above-mentioned defects in acrylic resin systems that are cured by irradiating ultraviolet rays without reducing the curing speed, and We conducted extensive research with the aim of developing an ultraviolet curable resin composition that has excellent adhesion to.

As a result, a compound represented by the following chemical formula (I), namely (cyclohexane spiro-2'-(1', 3'
The present inventors have discovered that the above object can be achieved by using -dioquinrane)-4'-yl) methyl acrylate in place of or in combination with conventional reactive diluents, and have completed the present invention.

The compound represented by the above chemical formula (I) (hereinafter simply referred to as compound <I) is a new compound that has not been described in any literature, and the present inventors have previously discovered that it is a material and reactivity of a curable film composition. It was found to be useful as a diluent.

The present invention was made based on this knowledge, and provides an ultraviolet curable resin composition containing compound (I) as an active ingredient.

50 Effects The compound (I) blended in the present invention is an intermediate obtained by reacting cyclohexanone with glycerin (2-methyl-2-(cyclohexane spiro-2'-(1'),
3'-dioxolane)-4'-yl)methanol (
II> can be advantageously prepared by transesterification with methyl acrylate.

In the present invention, the base resin only needs to have a polymerizable ethylenically unsaturated group; for example, as a typical example (
a) A polyester-based polyvinyl compound obtained by condensation oligomerization of a polyhydric alcohol, a polycarboxylic acid, and an ethylenically unsaturated monocarboxylic acid, (
b) Epoxy-based polyvalent e-nyl compound obtained by adding an ethylenically unsaturated carboxylic acid to a polyvalent epoxy compound, (C) Polyurethane-based polyvalent compound obtained by addition-reacting a polyvalent isocyanate and a hydroxyl group-containing ethylenically unsaturated monomer. Examples include vinyl compounds.

It is also possible to use these compounds alone or in combination of two or more.

In the present invention, the photopolymerization initiator is benzophenone,
It is possible to use any known initiator that generates radicals upon irradiation with ultraviolet light, such as acetophenone, benzyl, O-benzoic acid, and methyl O-benzoylbenzoate.

F7 Example Next, the content of the present invention will be explained in more detail with reference to Examples and Comparative Examples. Note that the present invention is not limited to this example. "Parts" in Examples and Comparative Examples are parts by weight.

For reference, an example of the production of compound (T) is as follows.

[Manufacturing example]

In a three-bottle flask equipped with a stirrer, thermometer, and condenser, 147 ff (1,5 mol) of cyclohexanone, 92 g (1 mol) glycerin, and 1 ml of pl-luenesulfonic acid were added.
g and 200 d of benzene were added, and the mixture was heated and stirred. The produced water was distilled and condensed together with benzene, and only the water was removed from the system using a separator, and the benzene was returned to the reactor. water is 18
3. It was cooled when it was produced. After removing methyl ethyl ketone and benzene from the reaction mixture using an evaporator, the intermediate cyclohexane spiro-2'-
(1',3'-dioxolane)-4'-yl)methanol was obtained with a yield of 88%.

172 g of the above intermediate (1
mol), 258 g (3 mol) of methyl acrylate, 3.0 g of phenothiazine and 10 mol of titanium vin-butyl.
g and heated while stirring until it boiled. An azeotropic mixture of methanol and methyl acrylate produced in n1 was removed by distillation. The transesterification reaction was completed in 5 hours, and the resulting reaction mixture was directly distilled under reduced pressure to obtain the target compound (I
) was obtained with a yield of 83%.

・Viscosity (at25℃): 26cps・Boiling point 11
5-b ・Infrared absorption spectrum (liquid film, α-1) 2980.29
40 <c-H>1730 (C=O ester) 1630 (C=C ester) 1190 (C-01,3-dioxolane) [Example 1] Ultraviolet curable resin composition ■ is made with the following formulation! I made it.

・Oligoester acrylate CM-6200, Toagosei Chemical Industry Co., Ltd. (l grade) 45 parts ・Compound (I > 25
parts / trimethylolpropane triacrylate 17 parts / diethylaminoethyl methacrylate 7 parts / 0
-Methyl benzoylbenzoate 6 parts 100
Part composition ■ was added to a polyethylene terephthalate plate (thickness 10
mm) to a coating thickness of 20μ using a bar coater, and using a high-pressure mercury lamp (120W/Cm) to a height of 10cm.
It was cured by irradiating ultraviolet rays from the position m for about 3 seconds. The properties of this coating film are shown in Table 1.

(Example 2) An ultraviolet curable resin composition (2) was prepared using the following formulation.

- Oligoester acrylate CM-6420X, manufactured by Toagosei Kagaku Kogyo ■] 50 parts - Compound (I) 20 parts - Trimethylolpropane triacrylate - 1-10 parts - Triethylene glycol diacrylate 10 parts - Diethylaminoethyl methacrylate 6 0-Methyl benzoylbenzoate 4 parts 100 parts Composition (2) was applied to base paper for a cosmetic box so that the cured film was 5μ, and using the same high-pressure mercury lamp as used in Example 1,
It was cured by irradiating ultraviolet light for about 2 seconds. The properties of this coating film are shown in Table 1.

[Comparative Example 1] The composition of Example 1 was carried out in the same manner as in Example 1 except that compound (I) was replaced with trimethylolpropane triacrylate, and the properties of the resulting coating film are shown in Table 1.
It was shown to.

[Comparative Example 2] The composition of Example 2 was carried out in the same manner as in Example 2, except that compound (I) was replaced with trimethylolpropane triacrylate, and the properties of the resulting coating film are shown in Table 1. Indicated.

Effects of the G1 Invention From the results in Table 1, it was observed that the adhesion was significantly improved by blending compound (1) without impairing the curability, and the effectiveness of the present invention is clear.

It was displayed in

Curability: Tested with and without finger tack.

◎: Not at all △: Slightly tacky ×: Contents of surface uncured correction (procedural amendments imported) August 16, 1985 1. Indication of the incident 1985 Patent Application No. 108798 2. Invention Name: Ultraviolet Curing Resin Composition 3, Relationship with the Amendment Case Patent Applicant Address: 1-4-5 Marunouchi, Chiyoda-ku, Tokyo
Name (234) Sanyo Kokusaku Pulp Co., Ltd. 4, Agent address: 16 Kanda Kita Jorimono-cho, Chiyoda-ku, Tokyo
101 Ei Building 3rd floor 5, subject of amendment 1, deleted from the last line of page 4 to line 7 of page 5 of the specification.

2. On page 5, line 9 of the specification, the statement ``The said compound (I>is)'' has been corrected to ``J, although the said compound (I) can be produced, for example, by the method described in JP-A-60-72833.

3, same page line 133 [Methyl acrylate] [Methyl acrylate and titanium @ n-butyl] Corrected.

4, same page line 144 It says "advantageously" "More advantageous" I corrected.

5. Line 8 from the bottom of page 11 of the specification It says "board port" Corrected to "board port".

Claims (1)

[Claims] (1) In an ultraviolet curable resin composition whose main components are a base resin, a reactive diluent, and a photopolymerization initiator, and which is used to form a film by irradiating ultraviolet rays, part or all of the reactive diluent is (cyclohexane spiro-2'-(1',3'-
Dioxolane)-4'-yl) methyl acrylate▲Mathematical formula, chemical formula, table, etc.▼・・・・・・(I) An ultraviolet curable resin composition characterized by being blended with (I).