JPH0675610B2 - Method of adhering ski surface material or ski-sliding surface material - Google Patents

Description

The present invention relates to a method of bonding a ski upper surface reinforcing material and a ski surface material or a ski lower surface reinforcing material and a ski sliding surface material.

Generally, a so-called adhesive such as a reaction hardening type or a heat activating type that is liquid at room temperature is used to bond the ski upper surface reinforcing material and the ski surface material or the ski lower surface reinforcing material and the ski sliding surface material. Various problems have been raised due to the complexity of workability.

That is, the reaction curing type requires a heating device,
Even the improved room temperature curing type has a problem in that the initial adhesive strength is insufficient because it is liquid, and pressure clamping is required until curing proceeds to some extent. Further, the heat-activatable type has a limitation that the applied body can be used only for those having heat resistance, and that the adhesive strength is remarkably lowered when exposed to a high temperature even after solidification.

This invention has, at the beginning of sticking, the above-mentioned reinforcing material or surface which has adhesiveness enough to maintain the adhesion between the ski upper surface reinforcing material and the ski surface material or the ski lower surface reinforcing material and the ski gliding surface material. It exhibits wettability to the other surface of the material (or sliding surface material), and because it cures at room temperature, it adheres firmly with a large adhesion area after adhesion and is harmful during adhesion work. It is intended to provide a novel bonding method without volatilization of various substances.

The details of the present invention will be explained in detail. Before adhering a ski upper surface reinforcing material and a ski surface material or a ski lower surface reinforcing material and a ski sliding surface material, a polymer film (or sheet) is previously attached to the reinforcing material or surface. A film (or sliding surface material), and a liquid material containing a vinyl monomer and / or an oligomer as a main component, which dissolves or swells the surface layer portion of the polymer film to make it tacky, and the film or liquid material is used. Each of one of the above contains a polymerization initiator and the other contains a polymerization accelerator, and the above liquid is formed between the reinforcing material or the surface material (or the sliding surface material) on which the polymer film is formed and the other. A ski surface material or a ski sliding surface material, wherein the reinforcing material and the surface material (or the sliding surface material) are adhered to each other by causing a substance to be present and press-bonding to polymerize the liquid material. It is intended to provide.

Hereinafter, the method of the present invention will be described in detail by taking as an example the adhesion between the ski upper surface reinforcing material and the ski surface material. The constitution and effects of the present invention described below are the ski lower surface reinforcing material and the ski sliding surface material. The same is true for adhesion with.

One embodiment embodying the present invention is mainly composed of a polymer film previously formed on a ski upper surface reinforcing material or a surface material and a vinyl monomer and / or oligomer for dissolving or swelling a surface layer portion of the film to make it tacky. While using a liquid material as a component, a polymerization initiator is contained in one of the film or the liquid material and a polymerization accelerator in the other, and either the reinforcing material or the surface material for adhesion is used. One or both of the polymer film formed on the other surface and the polymer film, or both surfaces are coated by applying the liquid material, the liquid material is polymerized, the reinforcing material and the surface material. It is to adhere.

According to such a method, the surface layer portion of the polymer film formed on either one of the reinforcing material or the surface material has a tackiness due to being dissolved or swollen by a liquid material, and has a polymerization initiator and a polymerization accelerator. By polymerizing the liquid substance by the action, the polymer part (polymerized product) of the polymer film and the liquid substance (or cured product) is formed at the interface part with the other material.
Since a microscopically non-uniform sea-island structure composed of is formed, it exhibits strong adhesion to the other surface of the adherend. Therefore, it is understood that the method of the present invention is useful for firmly adhering the ski upper surface reinforcement and the ski surface at room temperature.

In order to further strengthen the adhesion between the ski upper surface reinforcing material and the ski surface material, the surface of the reinforcing material and / or surface material is subjected to sanding treatment, chromic acid mixed liquid treatment, sputter treatment, corona treatment, hot air treatment, flame treatment, caging. Known surface treatment methods such as treatment and ultraviolet treatment may be applied,
Alternatively, a silicone resin, a silane coupling agent, an epoxy resin, organic titanium, polyethyleneimine, polyisocyanate, or the like may be applied as a primer, and a primer may be applied after the above surface treatment method.

Further, the liquid material dissolves or swells the polymer film and penetrates to the interface portion of the reinforcing material or the surface material which has been formed in advance, so that the adhesiveness is improved and the adhesive is firmly adhered by the subsequent curing.

The ski upper surface reinforcing material used in the practice of the present invention may be one that has a strong repulsion property when stepping on the ski, that is, one that increases internal energy, and generally fiber reinforced plastic (hereinafter referred to as FRP) is used. To be done.

Further, the ski surface material may be a thermoplastic resin having excellent impact resistance, cold resistance, toughness and good workability, such as an acrylonitrile-butadiene-styrene copolymer resin (hereinafter, ABS).
Resin) and ionomer resins are often used.

The vinyl monomer and / or oligomer used in the practice of the present invention may be monofunctional or polyfunctional without distinction as long as it is polymerized by active radicals generated by decomposition of the polymerization initiator. The following is a specific example of what can be done.

Monofunctional vinyl monomer: for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate,
Alkyl or cycloalkyl acrylate or methacrylate 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
Acrylic acid hydroxy ester, glycidyl (meth)
Acrylate, diethylaminoethyl (meth) acrylate, etc.

Polyfunctional vinyl monomer: For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth)
Ethylene glycol or propylene glycol diester of (meth) acrylic acid such as acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate and the like.

Monofunctional oligomers: for example, polyester mono (meth) acrylates obtained by reacting a polyester resin with (meth) acrylic acid.

Polyfunctional oligomers: for example, polyethylene glycol di (meth) acrylate, epoxy (meth) acrylate obtained by reaction of epoxy resin with (meth) acrylic acid, and reaction of polyisocyanate compound with hydroxyacryl (meth) acrylate. The urethane (meth) acrylate obtained by the reaction, polyester di (meth) acrylate obtained by the reaction between the polyester resin and (meth) acrylic acid, and the like.

The liquid material containing these vinyl monomers and / or oligomers as a main component is one or two or more of the vinyl monomers and / or oligomers described above and, if necessary, these and additive components such as a film-forming polymer. In consideration of coating workability, its viscosity is preferably 0.01 to 100 poise, and practically it is preferable to adjust it to a range of 50 poise or less. the interface between one polymer film and other formed on one each record or the 1 to 500 g / m ^2, based on the thickness 100μm polymeric film, preferably applied in the range of 10 to 300 g / m ² It

Further, the polymer film (or sheet) formed on either one of the ski upper surface reinforcement material and the ski surface material is dissolved in a liquid material containing at least the surface layer portion as the main component of the vinyl monomer and / or oligomer. Or, after being polymerized by being swollen and activated, at the interface with either one of the reinforcing material or the surface body which is an adherend, a polymer portion composed of a polymer film and a polymer (or cured product) of a liquid substance To form a microscopically non-uniform sea-island structure. For example, rubbers such as natural rubber, isoprene rubber, chloroprene rubber, nitrile rubber, butadiene-styrene copolymer rubber, acrylic rubber and / or polyester resin. , Chlorosulphonated polyethylene resin, polybutyral resin, polyacrylic resin, polyether resin, polyamide resin, polyurethane Examples of the film (or sheet) having a thickness of 5 to 500 μm made of synthetic resins such as tongue resin, and processed products made of the rubbers and / or synthetic resins such as foam film, non-woven fabric, and woven fabric, In particular, those selected from the group of polyester resins and polyacrylic resins are preferable.

The polymerization initiator to be blended with either the liquid material or the polymer film is a compound that is decomposed by the redox reaction of the polymerization accelerator to generate active radicals to polymerize the liquid material.

For example, ketone peroxide such as methyl ethyl ketone peroxide, hydroperoxide such as cumene hydroperoxide, diacyl peroxide such as benzoyl peroxide, peroxyketal, dialkyl peroxide, peroxy ester,
Examples thereof include organic peroxides such as peroxycarbonate.

The polymerization initiator is added to either one of the liquid material or the polymer film and the vinyl monomer and / or oligomer.
The amount is 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight.

However, for the purpose of improving the preservability of the system containing a polymerization initiator, hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, p-benzoquinone, catechol, phenoazine picrate, and 4-
A polymerization inhibitor such as butyl catechol, 2-butyl-4-hydroxyanisole, and 2,6-ditersialybutyl-p-cresol can be added in an amount of 1/10 or less of the polymerization initiator.

Each of the other one of the liquid material and the polymer film in which the polymerization initiator is not blended is a polymerization accelerator that decomposes the polymerization initiator by a redox reaction to facilitate generation of an active radical, for example, dimethylaniline, Dimethyl-p-
Triidin, diisopropanol-p-toluidine, cobalt naphthenate, copper naphthenate, zinc naphthenate, thiourea, acetylthiourea, sodium ascorbate, a condensate of n-butyraldehyde and aniline, vanadium pentoxide and the like are vinyl monochlorides. It is compounded in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the monomer and / or oligomer. If it is less than 0.1 part by weight, the effect of addition is not obtained, and if it exceeds 10 parts by weight, the adhesive strength is lowered, which is not preferable.

In the method of the present invention, when the ski upper surface reinforcing material and the ski surface material are adhered, the polymer film, the liquid material, and the polymerization initiator and the polymerization accelerator which are respectively mixed with each of them are combined. , A polymer film formed on one or both of a ski upper surface reinforcement material and a ski surface material and / or the liquid material is applied to one or both of the other surface and the polymer film surface. It is characterized in that the liquid material is dissolved or swelled to be tackified so that it is uniformly brought into contact with the other surface to polymerize the liquid material.

Therefore, the present invention has the following effects.

(1) Since the polymer film is formed in advance on the ski upper surface reinforcing material or the ski surface material with a uniform thickness, an adhesive layer having a uniform thickness can be easily formed and the surface smoothness is good.

(2) By the synergistic action of the liquid material and the polymer film dissolved or swollen with the liquid material, the wettability to the adherend becomes large and the final adhesion area can be increased.

(3) At the adhesive interface, a polymer obtained by polymerizing a liquid material and a polymer portion made of a polymer film form a microscopically nonuniform sea-island structure, so that a strong adhesive strength can be obtained.

(4) The liquid material dissolves or swells the polymer film,
Since it penetrates to the interface portion of the reinforcing material or surface material that has been formed in advance, the adhesion is improved, and the adhesive is firmly adhered by subsequent curing.

(5) The physical properties of the adhesive layer can be controlled by selecting the type of polymer film, vinyl monomer and / or oligomer, and initiator system.

Examples of the present invention will be shown below. "Parts" and "%" mean "parts by weight" and "% by weight", respectively.

Example 1 A mixture of 100 parts of polybutyral resin and 3 parts of benzoyl peroxide was used as ethyl alcohol: toluene =
Make a 50% base with a mixed solvent of 2: 8 (weight ratio), apply this on a release liner so that the thickness after drying will be 40 μm, and dry for 20 minutes at 50 ° C. to obtain a polybutyral resin film. Obtained.

On the other hand, a liquid material comprising 90 parts of methyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate and 3 parts of dimethyl-p-toluidine is prepared.

The film is heat-transferred at a temperature of 100 ° C onto the treated surface of an ABS sheet having a thickness of 0.7 mm and subjected to corona treatment, and a width of 20 mm and a length of 1
A sample is made by cutting it into 50 mm, and the liquid substance is applied on the film of this sample with a coating amount of 60 g / m ² and a width of 20 mm and a length.
Apply to 100mm part, thickness 0.5mm, width 20mm, length
Laminated on a 150 mm FRP with the above coated surface inside, 20 ℃
A sample body was prepared by leaving it inside for 24 hours.

When the 90 ° peel strength was measured at a tensile speed of 10 mm / min using a universal tensile tester, the liquid-coated portion of this sample body was 4.2 kg.
It was a material destruction of FRP that can obtain a value of / 20 mm width.

Further, the specimen obtained in the same manner was left at −20 ° C. for 5 hours, and was hit hard at the edge of the ski to evaluate the cold impact resistance. It showed cold shock resistance.

Example 2 Soluble saturated polyester resin 10 on a 0.6 mm thick ABS sheet
A mixture of 0 part, 1.5 parts cobalt naphthenate and 1 part dimethylaniline was dissolved in a mixed solvent of methyl ethyl ketone: toluene to make a 30% solution, and the thickness after drying was 60μ.
m so that it was coated and dried at 70 ° C. for 3 minutes to form a soluble saturated polyester resin layer.

On the other hand, 50 parts of ethyl acrylate, butyl methacrylate
A liquid substance consisting of 50 parts and 2 parts of methyl ethyl ketone peroxide is prepared.

Width 20mm width 20mm, a sample is made by cutting the ABS sheet having a soluble saturated polyester resin layer formed into a length of 150mm, and the liquid material is applied on the resin layer of this sample at a coating amount of 100g / m ² and a width of 20mm and a length of 100mm. Was applied to the above-mentioned portion, and using this, a sample body was prepared in the same manner as in Example 1. When the 90-degree peel strength was measured, a value of 5 kg / 20 mm width was obtained, which resulted in material destruction of FRP. When the cold shock resistance was examined by the same method as in Example 1, good cold shock resistance was shown.

Example 3 50 parts butyl acrylate and 50 parts ethyl acrylate
100 parts of a polymer obtained by grafting 50 parts of methyl methacrylate to a copolymer composed of 3 parts of 2-hydroxyethyl acrylate and dissolved in methyl ethyl ketone to give a 30% solution, and 3 mol of isophorone diisocyanate and 1 mol of triethyl 3 parts (solid content ratio) of what reacted with methylolpropane and 5 parts (solid content ratio) of cumene hydroperoxide were added and dried on a release liner so that the thickness after drying would be 50 μm. Thus, a polyacrylic film was obtained.

On the other hand, a liquid material comprising 85 parts of methyl methacrylate, 10 parts of acrylic acid, 5 parts of ethylene glycol dimethacrylate, 3 parts of nitric acid and 0.3% of vanadium pentoxide dissolved in dioctyl phthalate, and 0.05 part of hydroquinone is prepared.

The same procedure as in Example 1 below (however, the coating amount of the liquid material is 50
g / 2m ² ) was prepared and 90 degree peel strength was measured.
The value of kg / 20mm width was obtained, and it became the anchorage destruction with the ABS sheet. When the cold shock resistance was examined in the same manner as in Example 1, it showed good cold shock resistance.

Example 4 A 0.7% -thick ionomer sheet subjected to corona treatment was dissolved in toluene with a mixture of 100 parts of chlorosulfonated polyethylene resin and 1.5 parts of benzoyl peroxide, and a 35% solution was dried. After that, it was applied so as to have a thickness of 35 μm and dried at 50 ° C. for 15 minutes to form a chlorosulfonated polyethylene resin layer.

On the other hand, 70 parts of methyl methacrylate, 30 parts of butyl methacrylate, 5 parts of bisphenol F-type epoxy acrylate and 1.5 parts of a condensate of n-butyraldehyde and aniline.
Part, 2.6-ditersiabutyl-p-cresol.
Prepare a liquid material consisting of 03 parts.

A sample body (however, the coating amount of the liquid substance was 50 g / m ² ) was prepared in the same manner as in Example 2 using the ionomer sheet having the chlorosulfonated polyethylene resin layer formed thereon. When the 90-degree peel strength was measured, a value of 3.6 kg / 20 mm width was obtained, which resulted in material destruction of FRP.

When the cold shock resistance was examined in the same manner as in Example 1, it showed good cold shock resistance.

As is clear from the above examples, according to the method of the present invention, the ski upper surface reinforcing material and the ski surface material are firmly bonded to each other and exhibit excellent cold shock resistance.

The above examples relate to the adhesion of the ski upper surface reinforcing material and the ski surface material, but when the above method is separately applied to the adhesion of the ski lower surface reinforcing material and the ski sliding surface material, the same effect as described above is obtained. Was obtained. As the ski lower surface reinforcing material, one having characteristics of repulsion, impact resistance, and toughness is used, and generally FRP is used. As the ski running surface material, one having characteristics of low friction, cold resistance and toughness is used, and generally polyethylene or the like is used.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroyuki Go, 1-2-1 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto Denki Kogyo Co., Ltd. (72) Inventor Akira Kaneko 10-1 Nakazawa-machi, Hamamatsu-shi, Shizuoka Japan Musical Instruments Manufacturing Co., Ltd. (72) Inventor Masashi Takazawa 10-1 Nakazawa-machi, Hamamatsu-shi, Shizuoka Prefecture Japan Musical Instruments Manufacturing Co., Ltd. (72) Inventor Hirohisa Nagashima 10-1 Nakazawa-machi, Hamamatsu-shi, Shizuoka Prefecture Nippon Musical Instruments (56) References JP-A-47-9916 (JP, A) JP-A-59-12984 (JP, A) JP-A-57-18569 (JP, A) JP-A-54-111534 (JP , A) Actual Development Sho 50-12058 (JP, U) Japanese Patent Sho 51-40492 (JP, B1)

Claims (3)

[Claims] 1. A polymer film (or sheet) is previously attached to a reinforcing film or a surface material (or a sliding surface material) before bonding a ski upper surface reinforcing material and a ski surface material or a ski lower surface reinforcing material and a ski sliding surface material. ), And a liquid material containing vinyl monomers and / or oligomers as a main component, which dissolves or swells the surface layer portion of the polymer film to make it tacky, and A polymerization initiator is added to the other side of the polymerization initiator, and the liquid material is present between the reinforcing material or surface material (or the sliding surface material) on which the polymer film is formed and the other, and pressure-bonded. An adhesive method, characterized in that the liquid material is polymerized to bond the reinforcing material to the surface material (or the sliding surface material). 2. The bonding method according to claim 1, wherein the ski upper surface reinforcing material is a fiber reinforced plastic. 3. The bonding method according to claim 1 or 2, wherein the ski surface material is an acrylonitrile-butadiene-styrene copolymer resin or an iomonomer resin.