JPS5986042A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a rapidly curing photosensitive resin composition giving a film with superior bonding strength and shock resistance by mixing vinyl ester resin with an acrylic monomer, acrylic modified 1,4-polybutadiene, and a photopolymn. initiator. CONSTITUTION:The desired photosensitive resin composition is obtd. by mixing vinyl ester resin (A) with an acrylic monomer (B) such as 1,6-hexanediol diacrylate, terminal acrylic modified 1,4-polybutadiene (C) represented by one of the formulae (where R is H or CH3), and a photopolymn. initiator (D) such as benzoin ethyl ether. The amount of the component C is 10-70wt% of the amount of the composition. The component C is prepd. by successively reacting 1,4- polybutadiene having hydroxyl groups at terminals with toluene diisocyanate and an acrylic monomer having a hydroxyl group such as hydroxyethyl (meth)acrylate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] This invention relates to photosensitive resin compositions, particularly vinyl ester resin compositions.

[Background technology]

It is generally known that when a compound having an unsaturated double bond is exposed to ultraviolet rays in the presence of a photopolymerization initiator, crosslinking polymerization is promoted and the compound is cured. This vinyl ester with unsaturated double bonds has good workability in that it can form a coating film even without a solvent.
It has a practical value not found in solvent-type resin compositions in terms of resource saving and the like, and has the advantage of curing in a short time, so it is useful as coating agents and adhesives.

But-! d! l + These cured products are hard and brittle;
The disadvantage is that it has inferior adhesive strength and impact resistance compared to epoxy resin. Although this improvement in adhesion and impact resistance is achieved by adding plastic substances, gonographs, and elastic substances, the deterioration of the fast curing performance, which is an original feature of vinyl ester resin, is sacrificed, and both performances are not satisfied. Can not.

[Purpose of the invention]

This invention was made in view of the above facts, and has excellent adhesive strength and impact resistance, which are evaluated as coating film performance.
Another object of the present invention is to provide a photosensitive resin composition that has excellent fast curing properties, which are evaluated as performance during the process of forming a coating film.

[Disclosure of the invention]

This invention contains a vinyl ester resin, an acrylic monomer, an acrylic-modified 1.4 polybutadiene, and a photopolymerization initiator, and the acrylic-modified polybutadiene contains 10 to 7 polybutadiene.
The present invention provides a photosensitive resin composition characterized in that it contains 0 weight percent.

This invention will be explained in detail below. First of all, vinyl ester resins are limitedly employed as the polymeric substances contained as constituents of the photosensitive resin composition according to the present invention.

As the vinyl ester resin, a vinyl ester oligomer obtained by reacting an epoxy resin containing two or more epoxy threads with an unsaturated carboxylic acid is employed. This vinyl ester resin has the property of being excited by a photopolymerization initiator and starting polymerization when irradiated with ultraviolet rays, and its properties are solid or viscous liquid at a constant temperature.

The acrylic monomer acts as a diluent that has the ability to dissolve vinyl ester oligomers, and when irradiated with ultraviolet light, it reacts with the vinyl ester oligomers to form part of the polymer produced. It is a sex diluent.

The blending amount of this acrylic monomer is preferably 50% by weight or more based on the vinyl ester resin. Specific examples of acrylic monomers include methyl methacrylate, butyl methacrylate-1, and hydroxyethyl methacrylate-1.
, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate], pentaerythritol tri(meth)acrylate, etc. are used.

Next, to explain the photopolymerization initiators, benzoin, benzoin methyl ether, benzoin ethyl ether,
Benzoin isopropyl ether.

Benzyl, benzophenone, acetophenone, anthraquinone, 2-ethyl anthraquinone, benzyl methyl ketal, etc. are used, and the blending amount relative to the entire composition is 1;
J, 0.5-5% is appropriate.

Further explaining the acrylic-modified 1.4 polybutadiene, for example, a polymer represented by the following formula is employed.

R (Here, k is H or CH3) This terminal acrylic-modified 1.4 polybutadiene is produced by reacting toluene diisocyanate with 1,4 polybutadiene having a hydroxyl group at the terminal, and then converting it to hydroxyethyl (meth).
It is obtained by reacting acrylic monomers having hydroxyl groups such as acrylate and hydroxypropyl (meth)acrylate.

As the ratio of 1.4 bonds increases, the comb elasticity of the formed coating film increases, and the MJgA resistance is more effective than 1.1.
When the proportion of 4-bonds decreases, the rubber elasticity of the formed coating film decreases and there is no effect on impact resistance. This acrylic modified 1.4 polybutadiene has a concentration of 10 to 70% based on the entire composition.
% by weight. That is, if it is less than 10% by weight, no improvement in impact resistance is observed, and 70 m, r', ll,'
This is because if it exceeds 6, the performance of the coating film formed and the adhesion strength will not be the same, and the curing speed will tend to be slow.

Note that photosensitive resin compositions containing these components do not exclude those that contain a compensating agent, an R material, and a filler, and may be used by adding them as necessary. .

Examples that specifically demonstrate the effects of this invention will be given below.

1ξ Shiiretsu ~ Comparative Example A photosensitivity composition was prepared and R and C tests were conducted on each performance. In addition, ultraviolet irradiation is 80
It was carried out using high-pressure mercury phantom of ゞV/.

m In addition, each performance evaluation was performed as follows.

The photosensitive resin compositions according to Examples and Comparative Examples were coated on a photocurable near-aluminum plate using a bar coater to a thickness of approximately 20 μnt, and then irradiated with irradiation 1 until the surface of the coating film reached a non-adhesive state. The stones were measured and evaluated.

Grid test: After coating the photosensitive resin compositions according to Examples and Comparative Examples on an aluminum plate with a bar coater to a thickness of about 20 μm, 1010
Cured by irradiating 0 O/d ultraviolet rays to JISK5400
-79, a cross-cut test was conducted.

After applying adhesive on the adhesive crab glass epoxy substrate using a bar coater to a thickness of about 60 μm, a cylindrical chip of an electronic component was placed on it, and the chip was adhered by irradiating it with 2000"'4.H ultraviolet rays. The shear adhesive strength of the chip was measured using a push-pull gauge.

Impact resistance: A sample similar to that used in the measurement of adhesive strength was prepared and dropped from a height of 1 m onto the floor of concrete 1, and the number of chips that remained without being detached was determined and the n1 value was determined by the retention rate.

〔Effect of the invention〕

As listed in the above Examples and Comparative Examples, acrylic modified 1
．． Photo-cured bone with 6.1 ratio of 4-polybutadiene, contact?
It is clear that 'E is influenced by 'tt' and 'tt' by ``1'' and ξt resistance rl'+''.

Special e1)) Su1ninmatsu-1” ?i-+, 2E Co., Ltd. Attorney = 1 Toshimaru Takemoto (and 2 others) Te UC Ne Ichi Seiko 21. Display of the case 11?+f1 .+ 1957 Special Fraud Application No. 1.97281
No. 2, Name of the invention Photosensitive resin composition 3, Relationship with the person making the amendment Case 1 Patent applicant address OML Kadoma City Oaza Mon nxo 4s Name (583) Matsushita Electric Works Co., Ltd. Representative Iku Kobayashi 4. Agent address: Dai+1#FT Kadoma City, Kadoma 104
Contents of amendment at address 8 (1) Specification-4 in the i'r^゛111 description column of the invention
In lines 11 and 12 of page 1, correct ``1-'' by ``1'' by δ1.

(2) In the nY'f'lll explanation column of the invention, the "cylindrical child knob" on page 7, lines 8 to 9 of the specification is corrected to 1 cylindrical chip resistor J.

that's all 250-

Claims (1)

[Claims] (1) Vinyl ester resin, acrylic monomer. Contains acrylic-modified 1.4 polybutadiene and a photopolymerization initiator, and the acrylic-modified polybutadiene is 10 to 10%.
7 (triple box:%).