JPS58168514A - Bonding method - Google Patents

Abstract

PURPOSE:To attach goods to a film by high strength without volatilizing noxious materials, by a method wherein polymerization initiator is added to one side of the liquid material such as monomer, etc. caused to adhere to by dissolving macromolecular film and its surface layer, the goods being compressingly attached to the film and they are heated. CONSTITUTION:When goods are attached to a macromolecular film or sheet, by the use of the liquid material composed of vinyl monomer [for example : methyl (meta) acrylate, etc.] caused to adhere to by dissolving or swelling the surface layer part of this film, and/or of oligomer as main components, polymerization initiator (for example : ketone peroxide, etc.) is contained in either one of this film or liquid material, and the liquid material is put between the goods and the film, they being heated. Thus, the goods is caused to adhere to the film by polimerizing this liquid material.

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.

In general, so-called adhesives such as anti-medical adhesives that are liquid at room temperature, water, solvent or heat-activated adhesives, and solvent volatilization adhesives are known for adhering different or similar types of applications, but these adhesives have the same properties in common. 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 short pot stripes.1, the water or solvent activation type and the solvent volatilization type
The tack time is short, and solvent-based products have problems from a public and safety perspective, such as environmental pollution and health hazards due to the solvent volatilized into the air, and water-activated products absorb moisture even after solidification. There is a problem that adhesive strength decreases. Furthermore, in addition to the limitation that the heat-activated type can only be used on heat-resistant materials, it also has the disadvantage that the adhesive strength significantly decreases when exposed to high temperatures even after solidification1.On the other hand, these Pressure-sensitive adhesives are widely used, which are essentially different from other adhesives, 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. A feature of this adhesive is that it has superior initial adhesion and holding power compared to the adhesives mentioned above, but one of the characteristics of this adhesive is that it does not tend to increase cohesive force after adhesion like the adhesives mentioned above. Although this may be a drawback, the present invention has sufficient adhesion to hold the object at the initial stage of adhesion, and also exhibits wettability to the surface of the object, which has a rough surface. To provide a new adhesion method that provides strong adhesion and does not volatilize harmful substances during skin contact work.

To explain the details of the present invention in detail, it is used to bond an article and a polymer film (or sheet), and a vinyl monomer and/or oligomer that melts or swells the surface layer of the film to make it stick. Using a liquid material as a main component, either the film or the liquid material contains a polymerization initiator, the liquid material is present between the article and the film, and heating is performed to form the liquid material. The present invention provides an adhesion method characterized by polymerizing an object and adhering the object and a film.

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, either the film or the liquid material contains a polymerization initiator, and the liquid material is applied to the surface of one or both of the valleys between the film and the article to be bonded. Apply and paste,
Thereafter, the liquid material is polymerized by heating, and the film and the article are bonded together.

According to this method, the surface layer portion of the polymer film is dissolved or swollen with a liquid material and becomes sticky, and the liquid material is polymerized by heating, so that the interface portion with the article is made of the polymer film. Since a microscopically non-uniform seabird structure consisting of a polymer part and a liquid polymer (or cured product) is formed, it exhibits strong adhesion to the surface of the article. It is understood that the method is useful when the polymer film is attached for various purposes such as protection, anticorrosion, decoration, or display of the surface of an article.

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 surface of the article through the exposed portion of the film. , will be understood to be encompassed by the present invention. The polymeric film, when supported by a facing material, therefore functions as part of the adhesive material for bonding the packaging material to the article surface.

Examples of the facing material include paper, nonwoven fabric, woven fabric, rubber and/or glass film, sheet, tape, processed products thereof such as foamed film (or sheet), metal foil, and the like.

The vinyl monomer and/or oligomer used in carrying out the present invention is one that dissolves or swells the surface layer of the polymer film to be adhered to make it sticky, and is used for decomposition of the polymerization initiator as described below. As long as it is polymerized by active radicals generated in , it can be used regardless of whether it has -functionality or polyfunctionality, and specific examples thereof are as follows.

Ichinomiya functional vinyl monomers: e.g. methyl (meth)acrylate, ethyl(meth)acrylate, n-butyl/l
/ Alkyl such as (meth)acrylate, isobutyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexy)V (meth)acrylate, dec)V (meth)acrylate, furi/L/(meth)acrylate or cycloalkyl acrylate or methacrylate, vinyl acetate, vinyl gropionate, (meth)acrylonitrile, styrene, vinyltoluene, (
Hydroxyesters of (meth)acrylic acid, glycidi)V (meth)acrylate, diethylami)eth)V (meth)acrylic acid, 2-hydroxyethyl(meth)acrylate or 2-hydroxypropyl(meth)acrylate Polyfunctional vinyl monomers such as meth)acrylate; ethylene glycol or propylene of (meth)acrylic acid such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate; -functional oligomers such as glycol diester, trimethylolpropane tri(meth)acrylate, and tetramethylolpropane tri(meth)acrylate; ) Polyfunctional oligomers such as acrylates: for example, polyethylene glycol di(meth)acrylate, epoxy(meth)acrylate obtained by reaction of epoxy resin and (meth)acrylic acid, polyisocyanate compound and hydroxyacrylic/L/(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 A liquid material mainly composed of oligomers is composed of one or more of the above-mentioned vinyl monomers and/or oligomers, and its viscosity is 0.01 to 100 voids, which is practically The liquid substance is preferably adjusted to a range of 50 poise or less, and the liquid substance is applied to the interface between the polymer film and the article in a range of 1 to 5 poise based on the thickness of the polymer film of 100 μm.
00 f/m'', preferably in the range of 10 to 3009 f/m''.

The product is activated by being dissolved or swollen in a liquid material containing polymer as a main component, and after polymerization, it is microscopically invisible at the interface with the article by a part of the polymer consisting of a polymer film and a polymer or cured product of the liquid material. Consists of a uniform seabird structure, such as rubbers such as natural rubber, isoprene rubber, chloroprene rubber, nitrile rubber, phthadiene-styrene copolymer rubber, acrylic rubber, and/or polyester resin, chlorosulfonated polyethylene resin, polyester resin, etc. Thickness 5 made of synthetic resins such as butyral resin, polyacrylic resin, polyether resin, polyamide resin, polyurethane resin, etc.
Examples include films (or sheets) of ~5000 μm, and processed products made of the above-mentioned rubbers and/or synthetic resins, such as foam films, synthetic papers, nonwoven fabrics, textiles, etc.
Particularly preferred are those selected from the group of polyester resins, chlorosulfonated polyethylene resins, and polyacrylic resins. The above-mentioned mounting material may be bonded to one side of these polymer films (or sheets).

The polymerization initiator blended into either the liquid material or the polymer film is one that decomposes upon heating to generate active radicals and polymerizes the liquid material, such as polymer oxide. , peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxine esters, peroxycarbonates, benzoyl peroxide, cumene hydroxyveroxide, methyl ethyl ketone peroxide, and other organic peracids; 2. 2'-azobisisobutyronitrile, 212'-azobis=(4-methoxy-
Examples include azo compounds such as 2,4-dimethylvaleronitrile) and 1,1'-azobis(cyclohexane-1-carbonitri/I/). The polymerization initiator is used in either the liquid material or the polymer film, K of 0.01 to
It is blended in an amount of 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 monomethyl ether, methylhydroquinone, p-benzoquinone, catechol, phenoazine picrate, A-
A polymerization inhibitor such as butylcatechol, 2-butyl-4-hydroquinanisole, and 2,6-di-turnybutyl-p-cresol can be blended in an amount of 1/10 or less of the polymerization initiator. . In order to accelerate polymerization by heating, a polymerization promoter such as dimethylaniline or a condensate of n-butyraldehyde and aniline may be added.

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, corrosion prevention, waterproofing, decoration, or display. When adhering to the surface of a sheet-like article such as a glass plate or similar article, the liquid material and the polymerization initiator are combined, and either one of the polymer film and/or the surface of the article or the like is bonded. By applying the liquid substance to both surfaces and melting or swelling the liquid substance on the polymer film surface to make it sticky,
Weld it uniformly on the surface of the article, and then heat it at 30 to 150℃ for 5 minutes.
The method is characterized in that the liquid material is polymerized by heating for a period of seconds to 48 hours.

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, 1. Due to the synergistic effect of the liquid material and the polymer film dissolved or swollen in the liquid material,
), the wettability to the article is increased, the final adhesive area is increased, and the adhesive interface is microscopically non-uniform between a polymer made by polymerizing a liquid and a part of the polymer made of a polymer film. Because it has a seabird structure, it has a strong adhesive strength, and after bonding, the adhesive strength does not decrease even when exposed to high temperature and high 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 reinforcing material and the adhesive strength of the adhesive interface was measured.

Example 1 Methyl methacrylate 50 parts, ethyl acrylate 40 parts and 2-hydroxyethyl methacrylate 10 parts
1596 in a methyl ethyl ketone solution to make a copolymer, and place this on a release liner with a dry thickness of 1.
A polyacrylic polymer sheet is obtained by coating and drying to a thickness of 00 μm.

This sheet (sample shape lpli 20 mm, length 10
80 parts of ethyl methacrylate, 20 parts of methacrylic acid and [
- Apply 10 g of a liquid consisting of 1.5 parts of butyl peroxypivalate to a 1.6 mm thick steel plate (a cold-open rolled steel plate whose back surface was sandblasted and degreased with trichlorethylene, width 20 mm). Attach the ends of the length 100 mm in different steps and heat at 130°C for 20 minutes.
A sample body was prepared.

This sample was tested using a universal tensile tester (tensile speed 5 mm/min).
) The shear adhesive strength was measured at 19.3Kjl.
'/d value was obtained.

Example 2 Up to 20 mm from the edge of one side of a sample made of a 200 μm thick soluble saturated polyester sheet,
80 parts of methyl methacrylate, 15 parts of 2-hydroxyethyl methacrylate, 5 parts of polyethylene glycol dimethacrylate, 2,2'-Azohis-(4-methoxy-2,4-dimethylvalero=)! J/L/) and 0.03 parts of hydroquinone monomethyl ether was applied to a thickness of 3 mm.
A sample was prepared by attaching it to the edge of an ABS resin plate with a width of 20 mm and a length of 100 mm and heating it at 80°C for 30 minutes.The shear adhesive strength was measured and the value of soba was 15.1. Obtained.

Example 3 A vulcanized butyl rubber sheet (thickness: 3 mm) was used as the facing material. A 30% solution of dissolved natural rubber in methyl ethyl ketone was applied to one side of the sheet so that the thickness after drying was 30 μm, and the sheet was heated at 130°C. Dry for one part.

On the other hand, a liquid material consisting of 50 parts of nutylene, 50 parts of butyl acrylate, 2 parts of trimethylolpropane triacrylate, and 2 parts of t-butylperoxypivalate is prepared.

Next, the vulcanized butyl rubber sheet was cut to a width of 20 m.
A sample with a length of 100 mm was prepared, and the liquid material was applied at an amount of 40 P/m'' in front of the natural rubber layer up to 20 mm from the end of the sample, and the sample was coated through this coated surface. A sample was prepared by bonding it to the same steel plate as in Example 1 and heating it at 90°C for 10 minutes, and the shear adhesive strength was measured, and a value of 3.6 Kl/2"m" was obtained. It was done.

Example 4 An aluminum sheet with a thickness of 100 μm was used as a covering material,
On one side of this is a chlorosulfonated polyethylene layer (thickness 20
μm) was formed by a casting method.

On the other hand, a liquid material containing 50 parts of methyl methacrylate, 50 parts of glycidyl methacrylate, 1.5 parts of cumyl peroxyneodecanoate, and 0.01 part of hydroquinone is prepared. .

Hereinafter, in the same manner as in Example 3, the sample body (however, the liquid material was applied)
309/rn", heated at 80°C for 20 minutes. The shear adhesive strength was measured and was 28.3 VJI.
/cnf values were obtained.

Example 5 A biaxially stretched insoluble polyester film with a thickness of 25 μm was used as a covering material, and a solution made of a 30% paste of a mixed solvent of methyl ethyl ketone nyrelenine of a soluble saturated polyester resin was applied to this so that the thickness after drying would be 15 μm. It was applied and dried at 150°C for 5 minutes.

Polymethacrylate (tetrahydrophthalic anhydride 152
100 parts of a reaction product consisting of 212 parts of diethylene glyco/L/172 parts of methacrylic acid and 1 part of 2,2-azobisisobutyronitrile are prepared.

Next, as in Example 3, the sample body (however, the amount of liquid applied was 10
Example 6 A flexible polyvinyl chloride film with a thickness of 120 μm was prepared and the shear adhesive strength was measured. As a surface material, 3 parts (in terms of solid content) of 2.2-azobis-(4-methquine- 24-dimethylvaleronitrile) was applied to a thickness of 107 parts after drying and dried at 60'C for 15 minutes.Meanwhile, 90 parts of methyl methacrylate and 2-hydroxy Prepare a liquid substance consisting of 10 parts of ethyl acrylate.1 Next, as in Example 3, prepare a sample (however, the amount of liquid applied is 5f).
/m'', 8 (heated at 1 for 30 minutes) and measured the shear adhesive strength, and a value of 16.6 Kf/cm' was obtained.As is clear from the above examples, the method of the present invention 1, it is clear that the polymer film (or sheet) adheres strongly to the surface of the article.

Patent applicant: Nitto Electric Industry Co., Ltd. Representative Hijikata Sanbe

Claims (1)

[Claims] 1) When adhering an article to a polymer film (or sheet), the main component is a vinyl monomer and/or oligomer that dissolves or swells the surface layer of the film to make it sticky. using a liquid material containing a polymerization initiator in either the film or the liquid material, allowing the liquid material to exist between the article and the film, and heating the liquid material to polymerize the liquid material; An adhesion method characterized by adhering the article and a film. 2) One surface of the polymer film (or sheet) is supported by a facing material. Claim 1
Adhesion method described in section.