JPS58168513A - Bonding method - Google Patents

Abstract

PURPOSE:To attach multiple pieces of hetero-geneneous goods with high adhesion strength at room temperature, by a method wherein self-supporting macromolecular film and its surface layer is compressingly polymerized by adding polymerization initiator to one side and polymerization promotor to another side using liquid material such as soluble monomer, etc. CONSTITUTION:When 2 or not less than 2 pieces of goods are attached to, by the use of the liquid material composed of vinyl monomer adhered by dissolving or swelling the macromolecular film having self-supporting performance and at least the surface layer part of 2 films, and/or of oligomer as main components, polymerization initiator is contained in either one of the film or the liquid material, and polymerization promotor is contained in another material. They are contactly bonded under a condition wherein this liquid material and the flm exist between the inner surfaces of opposing goods and 2 or not less than 2 pieces of goods are bonded by polimerizing the liquid material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides two or more materials made of the same or different materials.
The present invention relates to a method for gluing articles of 1) at room temperature.

Many methods are known for bonding two or more articles together. Typical examples include a method using an adhesive tape with pressure-sensitive adhesive properties on both sides, a method using an organic solvent-based adhesive, a method using an adhesive activated by water, a solvent, or heat, and a method using a heating method. A method using an adhesive that hardens due to moisture absorption, a method using an adhesive that hardens due to moisture absorption, etc. are known.

However, methods using adhesive tapes have the disadvantage that when various types of stress are continuously applied to the adhesive layer, flow occurs inside the adhesive layer and the adhesive tape peels off from the surface of the article. The method used has safety issues such as environmental pollution due to solvent volatilization, fire, and health problems. When using adhesives that are activated by water, it is necessary to completely volatilize the water in order to obtain sufficient adhesive strength, and even after assimilation, water is absorbed and the bond strength decreases significantly. However, adhesives activated by solvents have the same problems as those using organic solvent-based adhesives. When using an adhesive that is activated by heating or an adhesive that hardens by heating, a large amount of heat capacity is required, and in the case of a type that is activated once, the adhesive strength decreases when exposed to high temperatures after assimilation. There is a problem of a significant decrease.

Adhesives of the type that harden due to moisture absorption do not pose much of a problem during the adhesion process and after adhesion, but they have the disadvantage that storage of the adhesive is complicated and expensive.

The present invention does not require the use of heating means that require a large amount of heat capacity, such as a heat curing type, and exhibits sufficient wettability even on the surface of an article with a rough surface, so that the articles can be firmly bonded to each other after polymerization. This invention provides a new bonding method that does not cause volatilization of substances that may occur during bonding operations.The details of the present invention will be explained in detail. In this process, a self-supporting polymer film and a liquid material mainly composed of a vinyl monomer and/or oligomer that dissolves or swells at least the surface layer of the film to make it sticky are used. A polymerization initiator is contained in one of the valleys of the object, and a polymerization accelerator is contained in the other, and the liquid material is polymerized by pressing the object with the liquid material and the film present between the opposing inner surfaces of the product. , provides a bonding method characterized by bonding two or more articles.

One embodiment of the present invention is a self-supporting polymer film, and a vinyl monomer and r/d/co-vinyl compound that dissolves or swells at least the surface layer of the film to make it sticky.
Or, two or more articles for the purpose of adhesion, using a liquid material mainly composed of oligomers, and containing a polymerization initiator in either the film or the liquid material, and a polymerization accelerator in the other. In between, a liquid substance, a film, and a liquid substance are present in this order and are pressed together to polymerize the liquid substance,
The above-mentioned articles are bonded to each other. According to such a method, at least the surface layer portion of the polymer film is dissolved or swollen with the liquid material and has adhesive properties, and the liquid material is polymerized by the action of the polymerization initiator and the polymerization accelerator.
At the interface with the article, there is a microscopically non-uniform sea island consisting of a part of the polymer made of a polymer film and a vulcanized rubber-like or resin-like polymer made of a polymer (or cured product) of a liquid substance. The structure is formed and exhibits a strong adhesion to the surface of the article, allowing two or more articles to be firmly adhered to each other.

Therefore, the polymer film and the liquid substance to be present between the articles may be applied by applying the liquid substance to both sides of the film and being interposed between the articles, or by applying the liquid substance to the inner surface of the article in advance and interposing the film between the two articles. It will be understood that they may be superimposed. In addition, if the polymer film is made of a material or has a thickness that is almost completely dissolved or swollen in relation to the liquid substance and permeates through the back surface 4, the liquid substance is not present on both sides of the film. Even if it is present only on one side, the film will substantially support the liquid, so
It will be understood that the adhesive strength targeted by the present invention can be obtained. Articles that can be bonded by the bonding method of the present invention are not particularly limited, and include, for example, Examples include plastics, rubbers, metals, stones, glasses, and processed products made from these materials.

Essential materials used in carrying out the invention
, 4. A molecular film (or sheet), a liquid material mainly composed of a vinyl sulfur compound and/or oligomer, which is made into an adhesive by dissolving or swelling at least the surface layer of the film;
There are four types of materials: a polymerization accelerator and a polymerization initiator. Naturally, each of these materials is selected depending on the article to be bonded, and the combination of the four materials is the most prominent. A combination that produces an effect is selected.

Beer 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. Specific examples thereof are as follows.

Monofunctional vinyl monomer: for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate,
Alkyl or cycloalkyl acrylates or methacrylates such as cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, vinyl acetate, vinyl propionate, (meth)acrylonitrile, styrene, vinyl Toluene, (meth)acrylic acid,
(meth) such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate
Hydroxyester of acrylic acid, glycidyl (meth)
Polyfunctional vinyl monomers such as acrylate and diethylaminoethyl (meth)acrylate; for example, ethylene glycol di(meth)acrylate, diethylene glycol
- ethylene glycol or propylene glycol diester of (meth)acrylic acid such as di(meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpronotri(meth)acrylate, tetramethylolpropane tetra(meth)acrylate, etc. - Functional oligomers: e.g. polyester heptano(meth)-acrylate obtained by reaction of polyester resin and (meth)acrylic acid, polyfunctional oligomers: e.g. polyethylene glycol di(meth)
Acrylate, epoxy (meth)acrylate obtained by reaction of epoxy resin and (meth)acrylic acid,
Urethane obtained by the reaction of polyisocyanate-1 compound and hydroxyacrylic (meth)acrylate (
meth)acrylate, polyether di(meth)acrylate or polyester di(meth)acrylate obtained by reaction of polyester resin and (meth)acrylic acid.

These liquid materials mainly composed of vinyl monomers and/or oligomers are composed of a complement or 2.1* or more of the vinyl monomers and/or oligomers, but the viscosity depends on the coating workability. Considering 0. (11 to 100 voids, preferably within the range of 50 voids or less for practical purposes), and the liquid material is applied to the interface between the polymer film and the article in a range of 0.1 to 100 voids*preferably 1. = 3014
The coating can be applied within the z range.

After being activated by being dissolved or swollen in a liquid material containing polymer as a main component, a part of the polymer consisting of a polymer film and a polymer (or cured product) of the liquid material are placed at the interface with the article after polymerization.
2. Rubbers such as natural rubber, isoprene rubber, chloroprene rubber, nitrile rubber, phthalene-styrene copolymer rubber, acrylic rubber, etc. and/or polyester resins constitute a microscopically non-uniform sea-island structure. , a film (or sheet) with a thickness of 5 to 200 μm made of synthetic resins such as chlorosulfonated polyethylene resin, polybutyral resin, polyacrylic resin, polyether resin, polyamide resin, polyurethane resin, and the above-mentioned rubbers. and/or processed products made of synthetic resins, such as foamed films, synthetic papers, non-woven fabrics, woven fabrics, etc., especially those selected from the group of polyester resins, chlorosulfate polyethylene resins, and polyacrylic resins. It is preferable that p) is 0. The polymerization initiator blended into either the liquid material or the cylindrical molecular film is decomposed by the Redo or Nox reaction of the polymerization accelerator to generate active radicals, and It polymerizes substances, such as Kenton peroxide, peroxyketal, hydroperoxide, sialgyl peroxide, diacyl peroxide, peroxy7 ester, peroxycarbonate, benzoyl peroxide, cumenohydrobar. oxide, organic peroxide such as methyl ethyl ketone peroxide,
2+ 2'-azobisisobutyronitrile, 2127
-azobis-(4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1
Examples include azo compounds such as -carbonitrile). The polymerization initiator is added to either the liquid material or the polymer film in an amount of 0.001 to 10% by weight, preferably 0.1 to 10% by weight.
It is blended within a range of 5% by weight.

However, in order to improve the storage stability of the system containing a polymerization initiator, hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, p-benzoquinone, catechol/l/, phenoazine hyfurinate, A-butylcatechol, Polymerization inhibitors such as 2-butyl-4-hydroxyanisole and 2,6-di-tert-butyl-P-cresol can be blended in an amount that is less than % 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-toluidine, diethyl-p-toluidine, diisopropanol-p-toluidine, cobalt naphthenate, copper naphthenate, copper lead naphthenate, boron 1, acetylthiourea, sodium ascorbate, n-butyraldehyde A condensate of aniline and aniline is blended in a weight range of 01-10. If it is less than 0.1% by weight, the addition has no effect, and if it is more than 10% by weight, the adhesive strength decreases, which is not preferable.

Therefore, the bonding method of the present invention combines the polymer film, the liquid material, and a polymerization initiator and a polymerization accelerator that are respectively blended into each of these to bond two or more articles together. , on one or both sides of the polymer film,
By applying the liquid substance or applying it to the surface of the article for the purpose of adhesion, the liquid substance is present, and the entire film is dissolved, or the surface layer portion of the film is dissolved or swollen to become sticky. It is characterized in that the adhesive is brought into even and reliable contact with the surface and the liquid material is polymerized and adhered.

Therefore, according to the method of the present invention, the liquid material and the polymer film dissolved or swollen by the liquid material increase the wettability to the surface of the article, and the final adhesion area becomes large, so that the polymerization of the liquid material increases. At the same time, a large adhesive strength can be obtained, and furthermore, a heating device or the like is not required.

Examples of the present invention will be shown below. The text middle part means the weight part. Note that 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 reinforcing material and the adhesive strength of the adhesive interface was measured.

Example 1 1 part of a condensate such as n-butyraldehyde and aniline was added to 100 parts of the resin to a 50 wt% base polybutyral resin bath solution dissolved in a 1:4 mixed solvent of ethyl alcohol:toluene. It was coated on the mold release liner so that the thickness after drying was 20μ2n, and it was heated at 50℃ for 2 hours.
Dry for 0 minutes to obtain a polybutyral resin film.

On the other hand, a liquid material consisting of 50 parts of styrene, 30 parts of 2-ethylhexyl acrylate, 20 parts of 2-hydroxyethyl acrylate, and 1 part of benzoyl peroxide is prepared.

Next, the previous day's film (-!llumburu shape 20ml ×
The liquid material was applied to both sides of the 20m FI +) so as to form five rings, and one surface was coated with a 75 μm thick fluororesin film (1@20 mrn) whose surface had been treated with sodium.
, length 100mm) and a thickness of 3tn on the other surface.
Bakelite board (width 20mm, length 100mm)
) was pasted on different levels and left at 20°C for 24 hours to create a sample.
n) (The shear adhesive strength was measured at 24.4'
A value of F5y/6n/ was obtained.

Examples 2 to 5 Adhered articles were adhered to each other using the liquid material and polymer film shown in Table 1.

Table 1 As is clear from the above examples, it is clear that the adhesive method t of the present invention can firmly adhere similar or different types of articles Patent applicant Sanbe Hijikata, representative of Nitto Electric Industry Co., Ltd.

Claims (1)

[Claims] When bonding two or more articles, the main components are a self-supporting polymer film and a vinyl monomer and/or oligomer that dissolves or swells at least the surface layer of the film to make it sticky. Using a liquid material, one of the film or the liquid material contains a polymerization initiator and the other contains a polymerization accelerator, and the liquid material and the film are present between the opposing inner surfaces of the article. An adhesion method characterized by adhering two or more articles by pressure bonding and polymerizing the liquid material.