JPS61185542A - Photo-sensitive composition - Google Patents

Abstract

PURPOSE:To provide a photo-sensitive composition composed of a butadiene (co)polymer, an unsaturated carboxylic acid ester having hydroxyl group in the molecule, and a specific photo-sensitizer, and having improved hardening time, adhesivity to the adherend and odor, etc. CONSTITUTION:The objective composition is produced by compounding (A) a butadiene polymer (e.g. 1,4-polybutadiene) and/or a copolymer of butadiene and other polymerizable monomer (e.g. butadiene-acrylonitrile copolymer) having a molecular weight of 1,000-200,000, (B) an unsaturated carboxylic acid ester having hydroxyl group in the molecule (e.g. 2-hydroxyethyl methacrylate) and (C) a photo-sensitizer of formula (R is 1-3C alkyl; R' is phenyl which may be substituted with 1-3C alkyl, Cl or amino) (e.g. 2,2-dimethoxyacetophenone). The amounts of the components A, B and C are preferably 5-50pts.(wt.), 1-30pts. and 0.01-5pts., respectively, and the weight ratio of A:B is preferably 99:1-55:45.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a photosensitive composition, which is suitable for application fields such as inks, coating agents, resists, paints, and adhesives.

(Prior art) In recent years, photosensitive materials have been supported by the use of chemical reactions caused by energy rays, and have been used in photosensitive materials for copying, materials for displays, inks, paints, hole and turn formation in ten fields, etc.
It is widely used for bonding transparent materials. In particular, it is attracting attention as a pattern forming material in printed wiring boards for consumer devices, liquid crystal sealing, optical component adhesion, and IC fields. For this reason, many types of photosensitive compositions have been discovered, and many types of photosensitive compositions having unique performances depending on their uses have been proposed.

Energy rays such as ultraviolet rays, visible light, infrared light, electron beams, and X-rays are generally used to cure photosensitive compositions, and the most commonly used is ultraviolet rays.

The wavelength of ultraviolet light used is 200 to 400 nm, and the light source used is a high-pressure mercury lamp, a xenon lamp, a chemical ride lamp, a metal halide lamp, or the like.

The composition of a photosensitive composition generally consists of a polymerizable vinyl monomer and a photosensitizer, and when this photosensitizer absorbs light energy, polymerization starts and a curing reaction progresses. Depending on the type of vinyl monomer and the type of photosensitizer, the odor, toxicity, and
It adversely affects the viscosity and curing time, and also affects the properties of the cured product, such as adhesion to adherends, transparency, and durability under the usage environment. For example, the special public official court in 1977-
No. 49033 discloses a 1.2-, f-liptadiene oligomer, but the composition shown therein is
Although the curing time is fast, the vinyl monomer type shown in the examples has problems with odor and adhesion to adherends. In addition, Japanese Patent Publication No. 52-8856 discloses a liquid polymer substance having a butadiene bond in its molecule, and a methacrylic acid di-C-0-ster monomer or acrylic acid monomer having 11 groups in its molecule that is easily activated by light energy. A photosensitive adhesive containing an ester monomer as a main component is described, but the photosensitive adhesive shown therein has good adhesion to the adherend, but when cured, the vinyl of the resin having an unsaturated group A photocurable coating composition containing tetramethylthiuram monosulfide as a photosensitizer in a monomer solution is described, but in the composition shown therein, the photosensitizer contains a large amount of sulfur. Therefore, its use is restricted in applications where metal corrosion is averse, such as electronic parts.

(Problems to be Solved by the Invention) An object of the present invention is to provide a photosensitive composition that cures in an extremely short period of time, improves adhesion strength to adherends, and solves all of the problems of the above-mentioned known techniques. It is something.

(Means for solving the problem) The present invention provides (1) a butadiene polymer and/or a copolymer with a butanoe/toike polymerizable monomer, (2) an unsaturated carbon having a hydroxyl group in the molecule. Acid ester and (3
) Photosensitizer R represented by the following general formula (where R is an alkyl group having 1 to 3 carbon atoms, and R' is a phenyl group, an alkyl group having 1 to 3 carbon atoms, chlorine or an amine group) This is a photosensitive composition consisting of a phenyl group. Here, as the butadiene polymer and/or the copolymer of butadiene and other polymerizable monomers, specifically, 1,4-polybutadiene and 1,2-polybutadiene are representative examples of the butadiene polymer. , and as modified products of these polymers,
The terminal group may be an OH group, a C0OH group, or a vinyl-terminated product. Typical copolymers of butadiene and other polymerizable monomers include butadiene-7+lonitrile copolymers and butadiene-acrylonitrile-styrene copolymers, and modified products of these polymers include Examples include, but are not limited to, terminal groups such as OH groups, COOH groups, and vinyl-terminated products. In addition, these polymers have a molecular weight of 1.
000 to 200,000 is suitable.

Next, unsaturated carboxylic acid esters having a hydroxyl group in the molecule include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, ethylene glycol mono(meth)acrylate, and noethylene glycol mono(meth)acrylate. ) acrylate, glycerin mono(meth)acrylate, trimethylolgulogunmono(meth)acrylate, trimethylolglopandi(
Examples include, but are not limited to, meth)acrylate and bisphenol A mono(meth)acrylate.

R is an alkyl group having a prime number of 1 to 3, and R' is a phenyl group, an alkyl group having 1 to 3 carbon atoms, a phenyl group directly substituted with chlorine or an amine group), 2,2-dimethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-noethoxyacetophenone, 2,2-nobropoxyacetophenone, 2,2-dimethoxy-2-chlor Examples include phenylacetophenone, 2,2-dimethoxy-2-aminophenylacetophenone, and the like.

The composition ratio of these requirements varies depending on the application, but preferably 5 to 50 parts by weight for (1), 1 to 30 parts by weight for (2), and 0.01 to 5 parts by weight for (3), especially ( 1)
The blending ratio (weight ratio) of and (2) is 99:1 to 55:45
is particularly preferred from the viewpoint of compatibility.

In addition to these, other compatible organic compounds may also be added. Examples include vinyl monomers that do not contain hydroxyl groups, plasticizers, surfactants, silane coupling agents, and the like. In particular, it has been found that the addition of silane coupling agents (1) and (2) in the presence of the present composition improves the adhesion of the adherend, and above all, improves the long-term moisture and water resistance.

In addition to this, it is also effective to add an inorganic filler that is highly transparent to ultraviolet rays, if necessary.

As described above, the present invention can provide a photosensitive composition having unprecedented performance by combining specific chemical compounds, thereby achieving the object.

(Example) Examples of the present invention will be described below.

Example 1゜Vinyl-terminated polybutadiene oligomer [average molecular weight 2
000 (TE-2000 Nippon Sodasha)] 200g and 2-
Hydroxyethyl methacrylate 100. ! 9 and 0.25 g of hydroquinone were placed in a 500 rrLl Mitsuro flask and stirred for 2 hours in a nitrogen stream while heating the flask to 80°C. Thereafter, 3 g of vinyl-tris(2-methoxy) 7ran (A-172 Nippon Unicar Co., Ltd.) and 73 g of 2゜2-dimethoxy-2-phenylacetophenone were added, the temperature was returned to room temperature, and the mixture was stirred for 1 hour in a cool, dark place. ) was prepared.

Example 2 Sample (2) was prepared in the same manner as in Example 1 except that a terminal hydroxyl group-type polybutadiene oligomer [molecular weight 2000 (G-2000 Nippon Soda Co., Ltd.)] was used instead of the vinyl-terminated polybutadiene oligomer 0 in Example 1. was prepared.

Example 3 Sample (3) was prepared in the same manner as Example 1 except that 2-hydroxypropyl methacrylate was used instead of 2-hydroxyethyl methacrylate and vinyl-tris-(2-methoxy)silane was not added. Manufactured.

Example 4 Terminal allyl type polybutadiene oligomer [average molecular weight 3
000 (B-3000 Nippon Petrochemicals)] 2200g
Put 50 g of 2-hydroxyethyl methacrylate, 50 g of ethylene glycol dimethacrylate, and 0.2 g of hydroquinone monomethyl ether into a Mitsuro flask and mix at 80 g.
The mixture was stirred for 2 hours in a nitrogen stream while warming to ℃. After cooling, 3 g of gamma methacryoxypropyltrimethoxysilane (A-174 Nippon Unicar Co., Ltd. > 39.2,2-dimethoxy-2-phenylacetophenone) was added in a cool, dark place and stirred for 1 hour to prepare sample (4).

Example 5゜Vinyl-terminated polybutadiene oligomer [average molecular weight 2
000 (TB-2000 Nippon Sodasha)] 100.9,
2-Hydroxyethyl methacrylate 100. li',
Hydroquinone monomethyl ether 0.2g, vinyl-
Sample (5) was prepared in the same manner as in Example 1 with a composition of 2 g of tris-(2-methoxy)silane and 2 g of 2,2-zomethoxy-2-phenylacetophenone.

Comparative example 1゜1.2-polybutadiene oligomer [average molecular weight 400
0 (B-4000 Nippon Oil)] 7゜l, 2-hydroxy methacrylate 30g, hexachlorocyclopentanoene 1g, and hydroquinone 0.003g were stirred in vacuum for 30 minutes at 20℃ in a light-shielded flask, and the sample (ratio 1 )
was prepared.

Comparative Example 2゜1.2-polybutadiene oligomer [average molecular weight 300
0 (B-3000 Nippon Soda)] 5゜y and diallyl maleate 8,9. A sample (ratio 2) was prepared by stirring 4.0 g of N-vinylpyrrolidone, 0.02 g of hydroquinone monomethyl ether, and benzoin ethyl ether α,6y in a light-shielded flask at 20'C in a nitrogen stream for 30 minutes.

Comparative Example 3 A sample (ratio 3) was prepared with the composition of Example 1 except that the vinyl-terminated polybutadiene oligomer was not used.

Comparative Example 4 A sample (ratio 4) was prepared with the composition of Example 4 except that 2-hydroxyethyl methacrylate was not used.

Tables 1 and 2 show the results of various physical property measurements for the samples of the above Examples and Comparative Examples.

Claims (3)

[Claims] (1) Butadiene polymer and/or copolymer of butadiene and other polymerizable monomers, (2) Unsaturated carboxylic acid ester having a hydroxyl group in the molecule and (3) Photosensitizer represented by the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Here, R is an alkyl group having 1 to 3 carbon atoms, and R' is a phenyl group or a carbon number 1 to 3. 3) which is a phenyl group substituted with an alkyl group, chlorine or amino group.