JPS584953B2 - photosensitive adhesive - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel one-component photosensitive adhesive that is rapidly cured by sunlight, artificial light, radiation, or the like.

One-component photosensitive adhesives do not have the disadvantages inherent to two-component adhesives, such as measuring, mixing, non-uniformity of the system, bubbles, pot life, etc., as well as being non-solvent based and Recently, it has been increasingly used because it has many advantages such as sufficient time for positioning and extremely short curing time.

Generally, the main component is a known one-pack acrylic ester monomer, methacrylic ester monomer, or a derivative of these monomers, to which a photosensitizer or the like is added.

Many of these photosensitive adhesives are found to have excellent static adhesion, but the adhesive itself is extremely hard after curing, and when subjected to repeated stress or impact on the adhesive interface, Resistance is not always sufficient.

Furthermore, when adhering industrial transparent materials such as glass, water resistance and moisture resistance are usually required due to the intended use, but conventional photosensitive adhesives cannot necessarily be said to be satisfactory.

An object of the present invention is to provide a photosensitive adhesive having high adhesive strength and excellent water resistance, heat resistance, and weather resistance.

(A) A molecule obtained by adding an acrylic compound containing a carboxyl group or a hydroxyl group to a polymeric substance having an unsaturated double bond in the molecule in the presence of an alkyl hypohalide or an N-haloamide compound. The following (1) to (I
) formula (in the formula, R represents a hydrogen atom or a methyl group, n represents an integer of 2 to 5, m represents an integer of 1 to 4, and l represents an integer of 1 to 30)
The present invention relates to a photosensitive adhesive mainly consisting of a mixture consisting of 100 parts by weight of a polymeric substance having an acryloxy group or methacryloxy group represented by (B) at least 50 parts by weight of cyclohexyl methacrylate.

Specifically, the acryloxy group or methacryloxy group contained in the polymer substance (A), which is one of the main components of the photosensitive adhesive of the present invention, is expressed by the following formulas (1) to (2) (formula R is a hydrogen atom or a methyl group, n is an integer from 2 to 5, m is an integer from 1 to 4, and l is an integer from 1 to 30)
It is indicated by.

The polymeric substances having the above-mentioned functional groups are
As described in Publication No. 98, an active hydrogen atom is added to a polymer compound having an olefinic double bond at the end with acrylic acid, methacrylic acid, or an ester thereof in the presence of an alkyl hypohalide or an N-haloamide compound. It can be obtained by adding a compound having

The above-mentioned polymeric compound having an olefinic double bond can be selected from a wide range of options, including natural rubber, cis-1,4-polyisoprene, cis-1,4-polybutadiene, polychloroprene, butadiene-styrene copolymer, and butadiene. −
Acrylonitrile copolymer, inbutylene-isoprene copolymer, acrylic acid-bucudiene copolymer, methacrylic acid methylpucdiene copolymer, ethylene-propylene-cyclopencdiene copolymer, ethylene-propylene-5-ethylidene- Materials with rubber elasticity such as 2-norbornene copolymer, ethylene-propylene-1,4-hexadiene copolymer, and ethylene-propylene-1,4-hexadiene copolymer have high impact resistance and absorption properties. Therefore, it is suitably used.

Of course, for applications that do not strictly require shock absorption properties, polymer compounds other than those mentioned above, such as trans-1,4-polyisoprene, trans-1,4-polybutadiene, 1,
2-polybutadiene and the like can also be used.

Acryloxy groups or methacryloxy groups in polymeric substances can be contained in any proportion, but if the content is too low (
The affinity with component B) cyclohexyl methacrylate deteriorates, and the transparency also decreases.

Therefore, it is preferable that the functional group is present at least one functional group per 50,000 molecular weight of the polymer material, more preferably at least one functional group per 20,000 molecular weight.

Another main component (B) of the photosensitive adhesive of the present invention is cyclohexyl methacrylate.

Addition of component (B) improves adhesive strength.

When the adhesive of the present invention is used for bonding glass, (A
Sufficient adhesive strength can be obtained by adding 50 parts by weight or more of component (B) to 100 parts by weight of component ().

The photosensitive adhesive of the present invention includes (B) as a monomer component.
In addition to cyclohexyl methacrylate, an acryloxy group- or methacryloxy group-containing compound selected from acrylic acid, methacrylic acid, and derivatives thereof can be added.

Esters and amides are the most common derivatives of acrylic or methacrylic acid.

Examples of alcohol residues in esters include alkyl groups such as methyl group, ethyl group, dodecyl group, stearyl group, and lauryl group, as well as cyclohexyl group, tetrahyrofurfuryl group, aminoethyl group, 2-hydroxyethyl group, Examples include 3-hydroxyethyl group and 3-chloro-2-hydroxypropyl group.

Also, esters with ethylene glycol, triethylene glycol, and polyethylene glycol can be used similarly.

A typical example of the amide is diacetone acrylamide.

When using the above-mentioned monomer components, it is preferable that component (I) is contained in an amount of at least 5% by weight in the total amount of the polymeric substance (A), cyclohexyl meccrylate (B), and the monomer components.

The lower the content of component (A) is, the less improvement in impact resistance and water resistance can be expected when component (B) and monomer are added.

In the present invention, a silane coupling agent may be added in an amount of 10% by weight or less in order to further improve adhesive strength.

Examples of the silane coupling agent include γ-chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris(β-methoxyethoxy)silane, and γ-methacryloxypropyltrimethoxysilane.

β-(3,4-Ethoxycyclohexyl)ethyl-trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, λγ-aminopropyltriethoxysilane, N-β- (Aminoethyl)-γ-aminopropyltrimethoxysilane and the like.

Furthermore, to adjust the curing speed, benzoin, benzophenone, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, dibenzyl, 5-nitroacenaphthene, hexachlorocyclopentadiene, varanitrodiphenyl, varanitroaniline, 2,4.6 -trinitroaniline, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,
A photosensitizer such as 9-benzathrone may be added in an amount of 10% by weight or more and a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, P-benzoquinone, methylhydroquinone or the like may be added in an amount of 5% by weight or less to increase needle storage stability. .

In addition to these, discoloration inhibitors, stabilizers, and the like can be optionally added.

Using this adhesive, the adhesion strength between glass and various metal plates was tested.

An adherend with a size of 25 x 40 x 5 mm is wiped with tissue paper in the case of glass, and surface treated with a sandpaper buff in the case of metal, and the adhesive area is 1. ocm2, fixed with adhesive clips with adhesive thickness of 0.05 mm, and a 400W mercury lamp at a distance of 15c.
It was cured by irradiating ultraviolet rays at m for 5 minutes.

The adhesive strength was evaluated by measuring compressive shear force using a tensile tester at a speed of 50 mm/min.

The results are shown in Table 1. Example 2 The durability of a glass-glass adhesive test piece prepared in the same manner as in Example 1 was measured.

For comparison, a test piece was prepared and tested under the same conditions using a commercially available photosensitive adhesive.

Durability conditions Hot water resistance: immersed in 50℃ hot water for up to 4 weeks Heat resistance: left in oven at 100℃ for 6 weeks Weather resistance: Irradiated with a 100W mercury lamp at a distance of 15cm for 6 weeks The results are shown in Table 2.

An adhesive having the above composition was prepared and evaluated in the same manner as in Example 1, and the initial adhesive strength between glass and glass was 165 ky/cm2, and the adhesive strength after being immersed in hot water at 50°C for one week. was 195 kg/cm2, and glass was broken in all cases.

Prepare the adhesive by kneading each of the above ingredients in a roll mill,
An adhesion test was conducted in the same manner as in Example 1.

The results are shown in Table 3. Example 5 Adhesives having the compositions shown in Table 4 were treated in the same manner as in Example 1, and the glass-to-glass adhesive strength was measured.

Claims (1)

[Scope of Claims] 1 (A) An acrylic compound containing a carboxyl group or a hydroxyl group is added to a polymeric substance having an unsaturated double bond in the molecule in the presence of an alkylhypolite or an N-haloamide compound. The following (1) to (
■) Formula (in the formula, R is a hydrogen atom or a methyl group, n is an integer from 2 to 5, m is an integer from 1 to 4, and l is an integer from 1 to 30)
100 parts by weight of a polymeric substance having an acryloxy group or methacryloxy group represented by: (2) at least 50 parts by weight of cyclohexyl meccrylate;