JPS58168515A - Bonding method - Google Patents

Abstract

PURPOSE:To strongly attach goods to a film at room temperature, by a method wherein polymerization initiator is added to one side of macromolecular film and the liquid material such as monomer, etc. causeded to adhere to by dissolving its surface layer, polymerization promotor being added to another side, thus the film being compressingly attached to the goods, and they are polymerized. CONSTITUTION:When goods are attached to a macromolecular film or a sheet, by the use of a liquid material composed of vinyl monomer [for example : methyl (meta) acrylate, etc.] caused to adhere to by dissolving and swelling the surface layer part of this film, and/or oligomer as main components, polymerization initiator (fo example : ketone peroxide, etc.) is contained in either one of this film or the liquid material, and polymerization promotor (for example : dimethylaniline, etc.) is contained in another side of them. This liquid material is put between the goods and the film, and the liquid material is polymerized by compressingly making them adhere to. Thus, the goods is caused to adhere to the film.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for firmly adhering a single polymer film (or sheet) or one surface of the film supported by a facing material to an article surface at room temperature. It is.

In general, so-called adhesives such as reaction-curing adhesives that are liquid at room temperature, water, solvent or heat-activated adhesives, and solvent volatilization adhesives are known for adhering different types of persimmons or applications of the same persimmon to each other; In addition to insufficient initial adhesive strength, the adhesive workability is complicated, and various problems have been raised in terms of pollution and safety.

That is, the reaction curing type requires a heating device, and the improved room temperature curing type has the problem of a so-called pot life. The water or solvent activated type and the solvent volatilization type have short tack times, while the solvent type has environmental pollution and health problems due to the solvent volatilized into the air, and there are problems from a safety perspective. The problem with molds is that they absorb moisture even after solidification, reducing adhesive strength. Furthermore, the heat-activated type has the disadvantage that it can only be used in cases where the application body has heat resistance, and that the adhesive strength deteriorates rapidly even after solidification when exposed to high temperatures.

On the other hand, pressure-sensitive adhesives, which are essentially different from these adhesives, are widely used, and which achieve a certain purpose of adhesion to the target surface of the object to be applied or to each other by simple pressure bonding means. The characteristic of this adhesive is that it has superior initial adhesion and holding power compared to the above-mentioned adhesives, but after adhesion, it does not tend to increase cohesive force like the above-mentioned adhesives. This is a drawback.

The present invention has adhesiveness sufficient to hold the article at the initial stage of adhesion, and also exhibits wettability to the surface of the article with a rough surface, and after adhesion, a large adhesive layer is formed.
The present invention provides a new bonding method that allows strong bonding with a hammer and does not volatilize harmful substances during bonding work.

To explain the details of the present invention in detail, when adhering an article and a polymer film (or sheet), a vinyl monomer and/or oligomer that dissolves or swells the surface layer of the film to make it sticky is used. A liquid substance is used as a main component, and each of the film and the liquid substance contains a polymerization initiator on one side and a polymerization accelerator on the other side, and the liquid substance is present between the article and the film. The present invention provides an adhesion method characterized in that the article and the film are adhered by pressure-bonding the article and polymerizing the liquid material.

One embodiment of the present invention is a self-supporting polymer film and a liquid material mainly composed of vinyl monomers and/or oligomers that dissolves or swells the surface layer of the film to make it sticky. At the same time, a polymerization initiator is placed on one side of the film or the liquid material, and a polymerization accelerator is placed on the other side, and each of these is placed between the article to be attached and the first film. 1111 on one or both surfaces
Applying and bonding the liquid material, polymerizing the liquid material,
The method is to adhere the film and the article.

According to this method, the surface layer portion of the polymer film is dissolved or swollen with a liquid substance and becomes sticky, and the interface portion with the article is polymerized by the action of a polymerization initiator and a polymerization accelerator. In this process, a microscopically non-uniform sea-island structure is formed consisting of a part of the polymer film and a liquid metal material (or cured product), which shows strong adhesion to the surface of the product. It is something. Therefore, it is understood that the method of the present invention is useful when the polymer film is attached to the surface of an article for various purposes such as purulent retention, anticorrosion, decoration, or display.

However, as another aspect of the present invention, when one surface of the polymer film is supported by a facing material, the film may be adhered to the target article surface via the embossed surface of the film. , will be understood to be encompassed by the present invention. Therefore, the molecular film when supported by the facing material functions as part of the adhesive material for adhering the material to the surface of the article.

Examples of the facing material include paper, nonwoven fabric, woven fabric, rubber and/or plastic films, sheets, tapes, processed products thereof such as foamed films (or sheets), metal foils, and the like.

Vinyl monomers and/or oligomers used in the practice of the present invention may be monofunctional or polyfunctional as long as they are polymerized by active radicals generated by decomposition of a polymerization initiator. It is possible to do so, and all specific examples thereof are as follows.

- Functional vinyl monomers: for example methyl (meth)acrylate, ethyl (meth)acrylate, rubutyl (meth)acrylate, isobutyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, ) acrylate, alkyl or cycloalkyl acrylate or methacrylate such as lauryl (meth)acrylate, vinyl acetate, vinyl propionate, (meth)acrylonitrile, styrene, vinyltoluene, (meth)acrylic acid, 2
- Multifunctional vinyl monomers, such as hydroxy esters of (meth)acrylic acid, such as hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, diethylaminoethyl (meth)acrylate: e.g. Ethylene glycol or propylene glycol diester of (meth)acrylic acid such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolbropantoso(meth)acrylate, tetra -Functional oligomers such as methylolpropane tetra(meth)acrate: e.g. polyester resins and (
Polyfunctional oligomers such as polyester heptano(meth)acrylate obtained by reaction with meth)acrylic acid: e.g. polyethylene glycol di(meth)acrylate, epoxy( meth)acrylates, polytosocyanate compounds and hydroxyacrylic(meth)
Urethane (meth)acrylate obtained by reaction with acrylate, polyester di(meth)acrylate or polyether di(meth)acrylate obtained by reaction of polyester resin and (meth)acrylic acid, etc. These vinyl monomers and/or The liquid material mainly composed of oligomers is composed of one or more types of vinyl monomers and/or oligomers, but its viscosity is 0.01 to 100 voise, which is low in practical use, considering the workability of coating. Generally speaking, it is preferable to adjust the number to 50 voids or less.
00g/4n2, preferably in the range of 10 to 5009/4n2.

It is activated by being bathed or swollen with a liquid substance whose main component is polymer, and after polymerization, a part of the polymer consisting of a polymer film and a polymer (or cured product) of the liquid substance are deposited on the interface with the article. Rubbers such as natural rubber, isoprene rubber, chloroprene rubber, nitrile rubber, phthalene-styrene copolymer rubber, acrylic rubber, and/or polyester resins, chlorosulfonated polyethylene, etc. A film (or sheet) with a thickness of 5 to 5000 μm made of synthetic resins such as resin, polybutyral resin, polyacrylic resin, polyether fruit resin, polyamide resin, polyurethane resin, and the above-mentioned rubbers and/or synthetic resins. Examples of processed products include foamed films, synthetic papers, nonwoven fabrics, and woven fabrics, but those selected from the group of polyester resins, chlorosulfonated polyethylene resins, and polyacrylic resins are particularly preferred. The above-mentioned facing material may be bonded to one of these polymer films (or sheets).

The polymerization initiator mixed in one of the liquid proboscis and the valley of the molecular film is one that decomposes by the redox reaction of the polymerization accelerator to generate active radicals and polymerize the liquid material. For example, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester, peroxy carbonate, benzoyl peroxide, cumene hydroperoxide, methyl ethyl kent peroxide. Organic peroxide = azo compounds such as 22-azobisisobutyronitrile, 2,2-azobis-(thimethoxy-2,4-dimethylvaleronitrile), and 1,1-azobis(cyclohexane-1-carbonitrile) Examples include. The polymerization initiator is blended into either the liquid material or the polymer film in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight.

However, in order to improve the storage stability of the system containing a polymerization initiator, hydroquinone, hydroquinone 7-methyl ether, methylhydroquinone, p-benzoquinone, catechol, phenoazine picrate, A-
A polymerization inhibitor such as butylcatechol, 2-butyl-4-hydroxyanisole, and 2,6-di-tert-butyl-p-cresol can be blended in an amount of 1/10 or less of the polymerization initiator.

Either the liquid material or the polymer film, which does not contain a polymerization initiator, contains a polymerization accelerator that decomposes the polymerization initiator by redox reaction and facilitates generation of active radicals, such as dimethylaniline, dimethyl-P-)
Luidine, diethyl-P-toluidine, diisopropanol-P-)luidine, cobalt naphthenate, copper naphthenate, zinc naphthenate, thiourea, acetylthiourea,
Sodium ascorbate, a condensate of n-butyraldehyde and aniline, etc. are blended in a range of 0.1 to 10% by weight. If it is less than 0.1% by weight, there is no effect of addition;
If the amount is 0% or more, the adhesive strength decreases, which is not preferable.

Therefore, the method of the present invention can be applied to structures such as steel structures, architectural structures, metal sheets, plastic sheets, rubber sheets, etc., for purposes such as protection, anti-corrosion, waterproofing, sealing or display. When adhering to an article surface such as a sheet, a sheet-like article such as a glass plate, or similar articles thereof, the liquid material and the polymerization initiator are combined, and either or both of the polymer film and/or the article surface is bonded. The product is characterized in that the liquid material is applied to the surface of the polymer film, and the surface of the polymer film is made to adhere by dissolving or swelling the liquid material, thereby uniformly contacting the surface of the article, and causing the liquid material to polymerize. It is.

Furthermore, even when one surface of the polymer film (or sheet) is supported by the above-mentioned facing material, the polymer film is also characterized in that it is firmly adhered to the surface of the article.

Therefore, according to the method of the present invention, the synergistic effect of the liquid material and the polymer film dissolved or swollen in the liquid material increases the wettability to the article, increases the final adhesive area, and furthermore, the adhesive interface Because the polymer formed by polymerizing liquid materials and a portion of the polymer formed from polymer film form microscopically non-uniform sea-island formations, strong adhesion *& can be obtained, and after adhesion, high temperatures can be achieved. It has the characteristic that adhesive strength does not decrease even when exposed to humidity.

Examples of the present invention will be shown below. The text middle part means the weight part. In addition, when measuring the shear adhesive strength in Examples, if the strength of the sample body was weaker than the adhesive strength, the sample body was reinforced with a reinforcement material and the adhesive strength of the adhesive interface was measured.

Example 1 A product consisting of 100 parts of polybutyral resin and 3 parts of dimethyl-p-toluidine was made into a 50% base with a mixed solvent of ethyl alcohol:toluene 2:8 (weight ratio),
This was applied onto a release liner so that the thickness after drying would be 100 μm, and dried at 60”C for 10 minutes to obtain a polybutyral resin film.

On the other hand, a liquid material consisting of 50 parts of methyl acrylate, 50 parts of ethyl methacrylate, and 2 parts of benzoyl peroxide is used.

A sample is made by cutting the film into 1lllld 20 pieces and 100 pieces in length, and a 20v
Apply the liquid in an amount of 10 to 2 up to point n,
This was glued to one end of a Bakelite plate with a thickness of 3 mm, a width of 20 mm, and a length of 1 oomm, and left at 20° C. for 24 hours to prepare a sample body.

This sample was tested using a universal tensile tester (tensile speed 5s/min).
The shear adhesive strength was measured at 25.7 kQ/a.
The value of was obtained.

Example 80 parts of ethyl methacrylate and 2 parts of butyl acrylate
A copolymer consisting of 0 parts was dissolved in methyl ethyl ketone to make a 30% solution, 2 parts (solid content ratio) of zinc naphthenate was added thereto, and a thickness of 500% after drying was prepared on the release liner.
A polyacrylic film was obtained by coating and drying to a thickness of μm.

On the other hand, methyl methacrylate-1 = 70 ff1s, 15 parts of bisphenol F-type epoxy dimethacrylate,
A liquid product consisting of 15 parts of 2-hydroxyethyl acrylate, 1.5 parts of methyl ethyl (l-) amber oxide and 7 parts of hydroquinone methyl ether is used.

Hereinafter, in the same manner as in Example 1, the sample body (however, the amount of liquid applied was 10
≠2, 36 hours under polymerization conditions for 2 cycles) was prepared, and the shear adhesive strength was measured, and a value of 21.2 kg/cm2 was obtained.

Example 3 A polyimide film with a thickness of 80 μm was used as a surface material, and a copolymer of 50 parts of methyl methacrylate and 50 parts of ethyl acrylate was dissolved in toluene to make a 60% solution, and 6 parts (solid A polyacrylic resin layer was formed by blending a condensate of rubyraldehyde and aniline (common ratio) and coating and drying to a thickness of 10 μm after drying.

On the other hand, 100 parts of polyester polymethacrylate having a viscosity of 1.2 voids at 25"C (a reaction product consisting of 152 parts of tetrahydro-7-talic anhydride, 212 parts of diethylene glycol, 172 parts of methacrylic rj!!) and 4 parts of benzoyl peroxide. Prepare a liquid product consisting of

Hereinafter, the sample body was prepared in the same manner as in Example 1 (however, the amount of liquid applied was the above resin 1-, the production cloth lid was 1W 2, and the polymerization conditions were 25'C).
8 hours) and measured the shear adhesive strength.
A value of 19.4 kq/cyx was obtained.

Example 4 A biaxially stretched insoluble polyester film with a thickness of 50 μm was used as a facing material, and a mixture of 100 parts of soluble saturated polyester resin and 1.5 parts of cobalt heptenoate was applied to the surface of the film in a mixture of methyl ethyl naton and toluene. The thickness after drying is 20μ when dissolved in a solvent to make a 30% solution.
m and dried at 150''C for 5 minutes to form the entire soluble saturated Boriel resin layer.

On the other hand, 60 parts of butyl methacrylate, 65 parts of styrene,
Bisphenol F type epoxy acrylate (viscosity 50
A liquid consisting of 00 Pois at, 2r 5 B and 1.5 parts of cumene hydroperoxide is prepared.

Hereinafter, the same procedure as in Example 6 was carried out on the sample (however, the amount of liquid applied was 1
09/m for 24 hours under polymerization conditions 20-C), and the shear adhesive strength was measured, and a value of 12.50 parts/pieces 2 was obtained.

Example 5 A 75 μm thick fluororesin film whose surface was treated with sodium was used as a mounting material, and the treated surface of this film was
A 15% solution of a copolymer consisting of 50 parts of styrene and 50 parts of ethyl acrylate dissolved in toluene is mixed with 2 parts (solid fraction) of dimethylaniline, and the thickness after drying is 15 μm. Apply 160°
C for 10 minutes to form a polyacrylic resin layer.

On the other hand, a liquid material consisting of 95 parts of methyl methacrylate, 5 parts of diethylene glycol dimethacrylate, and 2 parts of benzoyl peroxide is prepared.

Hereinafter, the same procedure as in Example 6 was carried out on the sample body (however, the article to be adhered to was a stainless steel plate, the amount of liquid applied was 13ρ, the polymerization condition was 2σC, and 24
When the shear adhesive strength was measured, it was found that 18
．． A value of 2kQ/C1l'' was obtained.

As is clear from the above examples, according to the method of the present invention, the fact that the polymer film surface firmly adheres to the article surface is remarkable.

Applicant: Nitto Electric Industrial Company Representative: 3rd Department

Claims (1)

[Scope of Claims] 1) When adhering an article and a polymer film (or sheet), a material mainly composed of vinyl monomers and/or oligomers that dissolves or swells the surface layer of the film to make it sticky. Using a liquid material, either the film or the liquid material contains a polymerization initiator, and the other contains a polymerization accelerator,
An adhesion method characterized in that the liquid substance is placed between the article and the film to form a stop layer, the liquid substance is polymerized, and the article and the film are adhered. 2) Claim 1, in which one surface of the polymer film (or sheet) is supported by a facing material.
Adhesion method described in section.