JPH09193318A - Laminate and window frame for vehicle therewith - Google Patents

Abstract

PROBLEM TO BE SOLVED: To materialize a laminate in which primer treatment is unnecessary and adhesion properties to a urethane resin are good by laminating a urethane resin layer on a resin layer consisting of both a vinyl chloride-based resin containing a functional group of a specific part weight and a plsticizer and producing the laminate. SOLUTION: A laminate is produced by laminating a urethane resin layer on a resin layer which is obtained by forming a vinyl chloride-based resin composition consisting of 100 pts.wt. vinyl chloride-based containing a hydroxyl group and/or a carboxylic group and 20-150 pts.wt. plasticizer. Accordingly, even when primer treatment is not performed, the adhesion properties of the vinyl chloride-based resin layer and a urethane resin layer are excellent. The laminate is effectively used as a window frame for a vehicle.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated body in which a urethane resin layer is laminated on a resin layer made of a vinyl chloride resin composition, and a vehicle window frame made of the laminated body.

[0002]

2. Description of the Related Art When a window glass is attached to a window opening of a vehicle such as an automobile, a frame body (hereinafter referred to as "window frame") is interposed between the glass plate and the window opening. This window frame is
A vinyl chloride resin is mainly used because it is made of a synthetic resin and is excellent in various properties such as weather resistance and mechanical strength. On the other hand, when a window glass body having a window frame at the peripheral edge of the glass plate is attached to the window opening of the vehicle body, the glass plate surface of the window glass body to which a primer is applied is usually an adhesive layer made of urethane resin It is attached by adhering to the window opening flange of the vehicle through. In this case, in order to ensure the weather resistance of the adhesive, the hiding layer is laminated on the part of the glass plate surface where the adhesive is applied, but as a result, the area of the transparent part of the glass plate surface is reduced. I will end up. Therefore,
It has been proposed to attach a window glass to a vehicle by attaching a glass plate to a window frame in advance and attaching the window frame and the window opening flange via an adhesive layer. In this way, the concealing layer on the glass plate surface can be omitted,
The opening area of the window can be secured.

[0003]

Generally, the adhesive force between the vinyl chloride resin and the urethane resin, which is used for the window frame, is not so large that a desired primer treatment is required in order to develop a large adhesive force between them. Is required. Therefore,
Also in the above-mentioned mounting method, since the adhesive strength between the window frame and the adhesive layer is weak, it is necessary to subject the surface of the window frame to a primer treatment in advance. Moreover, even with this primer treatment, the adhesive strength between the window frame made of vinyl chloride resin and the adhesive layer made of urethane resin is not sufficient, and the window frame cannot be firmly adhered to the window opening flange. It was
The present invention provides a laminated body and a vehicle window frame in which a urethane resin layer is laminated on a resin layer made of a vinyl chloride resin composition having good adhesion to a urethane resin without a primer treatment. With the goal.

[0004]

That is, the gist of the present invention is as follows.
Urethane in a resin layer formed by molding a vinyl chloride resin composition comprising 100 parts by weight of a vinyl chloride resin containing a hydroxyl group and / or a carboxyl group (vinyl chloride resin containing a functional group) and 20 to 150 parts by weight of a plasticizer. The present invention resides in a laminate comprising a resin layer laminated, and another feature of the present invention is that the functional group-containing vinyl chloride resin is a polymer of the following (1) and (2): And / or the above laminate comprising a polymer of (1), (2) and (3) (1) vinyl chloride monomer (2) containing a hydroxyl group and / or a carboxyl group,
Monomers copolymerizable with vinyl chloride monomers (hydroxyl groups and /
Or a monomer containing a carboxyl group) (3) a monomer copolymerizable with a vinyl chloride monomer other than (2), a hydroxyl group of the vinyl chloride resin containing the functional group and /
Alternatively, the content of the monomer containing a carboxyl group is 0.
01-15 mol% of the above-mentioned laminate, the above-mentioned laminate in which the content of the monomer containing a hydroxyl group and / or a carboxyl group of the vinyl chloride resin containing a functional group is 0.1-5 mol%, and the above-mentioned laminate. It exists in a vehicle window frame made of a laminated body of.

[0005]

The present invention will be described in more detail below. The vinyl chloride-based resin containing a hydroxyl group and / or a carboxyl group used in the present invention (hereinafter referred to as “functional group-containing vinyl chloride-based resin”) may be composed of only a functional group-containing vinyl chloride-based resin, Alternatively, a mixture of this and a vinyl chloride resin containing no hydroxyl group or carboxyl group may be used. As the functional group-containing vinyl chloride resin, for example, a monomer containing a hydroxyl group and / or a carboxyl group and copolymerizable with a vinyl chloride monomer (hereinafter,
"A monomer containing a hydroxyl group and / or a carboxyl group") and a vinyl chloride monomer or a monomer which does not contain a hydroxyl group or a carboxyl group and is copolymerizable with a vinyl chloride monomer The obtained polymer may be mentioned. It may also be a mixture of these polymers.

Examples of the monomer containing a hydroxyl group and / or a carboxyl group include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxyethyl methacrylate.
Hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, ethyl-2-hydroxyethyl fumarate, hydroxybutyl vinyl ether, methacrylic acid, acrylic acid, monobutyl maleate, undecylene. Acid etc. are mentioned.

As a monomer which does not contain a hydroxyl group or a carboxyl group and which can be copolymerized with a vinyl chloride monomer,
For example, vinyl acetate, vinyl propionate, vinyl esters such as vinyl laurate, acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, dibutyl maleate,
Maleic acid esters such as diethyl maleate, fumaric acid esters such as dibutyl fumarate and diethyl fumarate, vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether, vinyl cyanides such as acrylonitrile and methacrylonitrile. Α-olefins such as ethylene and propylene, vinylidene chloride, vinylidene halides other than vinyl chloride such as vinyl bromide or vinyl halides, diallyl phthalate, and polyfunctional monomers such as ethylene glycol dimethacrylate. However, of course, the monomer is not limited to the above.

In addition to the above, the functional group-containing vinyl chloride resin is obtained by chemically treating a vinyl chloride polymer having a functional group capable of forming a hydroxyl group or a carboxyl group in the molecule by a chemical treatment. There are some. As such, for example, a method of hydrolyzing a vinyl chloride-vinyl ester copolymer, a method of hydrolyzing a vinyl chloride-acrylic acid ester copolymer, a vinyl chloride monomer and a vinyl monomer having an epoxy group Examples thereof include those obtained by treating the copolymer with an acid to open the epoxy group and hydrolyzing the vinyl chloride-N-alkoxymethylacrylamide copolymer. Alternatively, a vinyl chloride-N-alkoxymethylacrylamide copolymer or a vinyl chloride-epoxy compound copolymer which is used as it is without being chemically treated to produce a hydroxyl group during kneading is also used. To be

Next, as the vinyl chloride resin containing no hydroxyl group or carboxyl group, a vinyl chloride monomer alone or a vinyl chloride monomer and a monomer containing no hydroxyl group or carboxyl group copolymerizable therewith can be used. All the compounds obtained by polymerizing the mixture of the above-mentioned by a usual method such as a suspension polymerization method, a bulk polymerization method, a fine suspension polymerization method or an emulsion polymerization method and a mixture thereof can be used. The amount of monomers other than the vinyl chloride monomer is 30% by weight or less, preferably 20% by weight or less in the constituent components of the vinyl chloride resin containing a functional group.

The content of the hydroxyl group- and / or carboxyl group-containing monomer in the functional group-containing vinyl chloride resin is preferably 0.01 to 15 mol%, more preferably 0.05 to 5 mol%.
mol% is more preferable, and 0.1 to 5 mol% is particularly preferable. When the content of the monomer is less than 0.01 mol%, a resin layer composed of a vinyl chloride resin composition (hereinafter,
The adhesiveness between the "vinyl chloride resin layer") and the urethane resin layer is poor, and if it exceeds 15 mol%, it is not preferable because the vinyl chloride resin composition is poorly dispersed during processing and sticks to a molding machine or the like.

When a monomer having a plurality of hydroxyl groups and / or carboxyl groups in one molecule, such as glycerin monomethacrylate, is used, the functional group-containing vinyl chloride resin referred to in the present invention is used. The content of the monomer is considered as a value obtained by multiplying the actual content by the number of hydroxyl groups and / or carboxyl groups in the molecule of the monomer. The average degree of polymerization of the functional group-containing vinyl chloride resin is preferably 400 to 8,000, more preferably 500 to 4,000 from the viewpoint of processability and moldability.

The plasticizer used in the present invention may be any plasticizer commonly used in vinyl chloride resins, for example, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diisodecyl phthalate,
Phthalate ester plasticizers such as dibutyl phthalate and dihexyl phthalate; Linear dibasic acid ester plasticizers such as dioctyl adipate and dioctyl sebacate; Trimellitic acid ester plasticizers; Polyester polymer plasticizers; Large epoxidation Epoxy plasticizers such as soybean oil, epoxidized linseed oil and liquid epoxy resin; phosphoric ester plasticizers such as triphenyl phosphate, trixylyl phosphate, tricresyl phosphate and the like, and one or more of them may be used. It may be mixed and used. The compounding amount of the plasticizer is 20 to 150 parts by weight based on 100 parts by weight of the functional group-containing vinyl chloride resin. If the amount of the plasticizer is less than 20 parts by weight, the moldability will be poor, and if it is more than 150 parts by weight, bleeding may occur on the surface of the molded product.

Further, the vinyl chloride resin composition used in the present invention may contain a stabilizer, a filler, a lubricant, an antioxidant, an ultraviolet ray, if necessary, within a range that does not impair the physical properties of the vinyl chloride resin composition. Absorbent, flame retardant, colorant, antistatic agent,
You may mix | blend a modifier, such as a polymethylmethacrylate type processing aid and an acrylic rubber, an acrylonitrile-butadiene copolymer, a partially crosslinked acrylonitrile-butadiene copolymer.

As the stabilizer, synthetic hydrotalcite, calcium stearate, barium stearate,
Dibasic lead stearate, basic lead sulfite, dibasic lead phosphite, dibutyltin dilaurate, dibutyltin malate, dibutyltin mercaptide, dioctyltin malate stabilizer, dioctyltin laurate stabilizer, dioctyltin spume Stabilizers such as lucaptide-based stabilizers and / or their complexes are used. The amount of the stabilizer used is usually 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of the functional group-containing vinyl chloride resin. As the filler, calcium carbonate, clay, talc, fine silica powder, aluminum hydroxide and the like are used. The amount of the filler used is preferably in the range of 5 to 100 parts by weight per 100 parts by weight of the functional group-containing vinyl chloride resin.

As the lubricant, higher fatty acids or metal salts thereof, various paraffins, higher alcohols, natural waxes, polyethylene wax, fatty acid esters, fatty acid amides and the like are used. The amount of the lubricant used is preferably in the range of 0.1 to 10 parts by weight per 100 parts by weight of the functional group-containing vinyl chloride resin. As the antioxidant, phenol derivatives such as di-t-butyl-p-cresol, benzimidazole, amines such as N-phenyl-N′-cyclohexylparaphenylenediamine and phenylalphanaphthylamine, and derivatives thereof are used. The amount of the antioxidant used is preferably in the range of 0.1 to 10 parts by weight per 100 parts by weight of the functional group-containing vinyl chloride resin.

As the ultraviolet absorber, hydroquinone type, salicylic acid type, benzophenone type and benzotriazole type ultraviolet absorbers are used. The amount of the ultraviolet absorber used is preferably in the range of 0.1 to 10 parts by weight per 100 parts by weight of the functional group-containing vinyl chloride resin. Examples of flame retardants include phosphoric acid esters such as tributyl phosphate and diphenyloctyl phosphate; halogen-containing phosphoric acid esters such as tri-2,3-dibromopropyl-phosphate and tri-bromochloropropyl-phosphate; chlorinated diphenyl and tetra Halides such as bromobenzene; antimony-based flame retardants such as antimony trioxide and triphenylstibine are used. The amount of the flame retardant used is preferably in the range of 0.1 to 20 parts by weight per 100 parts by weight of the functional group-containing vinyl chloride resin.

Examples of colorants include titanium oxide, zinc white, lead white, calcium carbonate, gypsum, precipitated silica, carbon black, red iron oxide, molybdenum red, cadmium yellow, yellow lead, titanium yellow, chromium oxide green and ultramarine blue. Inorganic pigments: Organic pigments such as permanent red 4R, Hansa Yellow 10G, benzidine yellow GR, permanent carmine FB, phthalocyanine blue B and phthalocyanine green are used. The amount of the colorant used is preferably in the range of 3 to 150 parts by weight per 100 parts by weight of the functional group-containing vinyl chloride resin. As the antistatic agent, polyoxyethylene alkylamine, polyoxyethylene alkylamide, polyoxyethylene alkyl ether, glycerin fatty acid ester, sorbitan fatty acid ester, alkyl sulfonate, alkyl benzene sulfonate,
Quaternary ammonium chloride and quaternary ammonium sulfate are used. The amount of antistatic agent used is
0.1 per 100 parts by weight of functional group-containing vinyl chloride resin
A range of from 10 to 10 parts by weight is preferred.

The apparatus used for mixing the functional group-containing vinyl chloride resin, the plasticizer and the above-mentioned compounding ingredients may be any apparatus as long as they can be mixed substantially uniformly, for example, a Henschel mixer, ribbon blender, planetary. A mixer or the like can be used. To knead the obtained mixture, for example, an extruder, roll, Banbury mixer, kneader, or other device capable of kneading under heating while being heated may be used.

Next, the isocyanate and polyol used in the urethane resin layer of the laminate and the vehicle window frame of the present invention are not particularly limited, and those generally used may be used. As the isocyanate,
For example, methylene diphenyl isocyanate (MDI),
Tolylene diisocyanate (TDI), 1,5-naphthalene diisocyanate (NDI), tolidine diisocyanate (TODI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI)
And the like. Examples of the polyol include polyether polyol or modified polypropylene polypropylene glycol or polytetramethylene glycol, and polyester polyol or modified polyester polyol such as condensed polyester polyol or lactone polyester polyol.

The laminate of the present invention is obtained, for example, by coating a vinyl chloride resin layer with a composition comprising isocyanate and polyol to form a urethane resin layer. In addition, the vehicle window frame of the present invention, for example, a vinyl chloride resin composition is directly extruded to the glass peripheral portion, and molded into any shape, or, by combining a molding die and glass, a space in the peripheral portion of the glass. Is obtained, and then a vinyl chloride resin composition is injected and filled into this space to be solidified, and then a composition comprising an isocyanate and a polyol is applied to form a urethane resin layer.

[0021]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The evaluation of the adhesiveness between the vinyl chloride resin layer and the urethane resin layer was performed by the following method.

<Evaluation of Adhesiveness> After forming a sheet having a thickness of 1 mm from a vinyl chloride resin sheet by a compression molding machine,
A test piece was prepared by cutting it out to a length of 150 mm and a width of 20 mm.

A metal plate primer (Hamatite G (GC20) manufactured by Yokohama Rubber Co., Ltd.) is 150 m long on a stainless steel plate.
m, width 30 mm, and dried under conditions of 23 ° C. for 30 minutes, and then a metal primer (Hamatite G (MS90) manufactured by Yokohama Rubber Co., Ltd.) was similarly applied,
It was dried in an oven at 40 ° C. for 1 hour. Urethane sealant (WS-70 manufactured by Yokohama Rubber Co., Ltd.) on the metal primer is 150 mm long, 20 mm wide, and 1 m thick.
After coating with m, the test piece was placed thereon so as to be orthogonal to the urethane sealant coating film (at this time, the adhesive area between the test piece and the urethane sealant coating film was 20 × 20 (m
m ² ). ), And in Comparative Example 2,
A vinyl chloride resin primer (Hamatite VC250, manufactured by Yokohama Rubber Co., Ltd.) was applied to the test piece, the coated surface was overlaid on the urethane sealant coating film, and a load of 1 kgf was applied to the test piece, which was left at 23 ° C. for 1 week. Next, a peeling test was performed by an autograph (peeling at a 180 ° C. angle in the longitudinal direction of the test piece) to measure the adhesive strength. The results are shown in Table 1.

(Peeling Test Conditions) (1) Load Cell; for 50 kg (2) Test Speed (Peeling Speed); 200 mm / min (3) Chart Speed; 200 mm / min (4) Peeling Distance; 2 cm (5) Unit; kg / 2 cm The adhesion (peel) strength is a peak value in a peel distance of 2 cm.

Examples 1 to 5 and Comparative Examples 1 to 2 PVC-1 (Central PVC SG70 manufactured by Mitsubishi Chemical Corporation)
0, average degree of polymerization 700) and PVC-2 (Vinica (registered trademark) paste P100 manufactured by Mitsubishi Chemical Corporation), average degree of polymerization 1350, 3-hydroxypropyl acrylate 3
(Wt% copolymer) was weighed out in an amount shown in Table 1, and 53 parts by weight of a plasticizer (Dinp manufactured by Mitsubishi Chemical Corporation), 40 parts by weight of calcium carbonate, 3 parts by weight of epoxidized soybean oil, and Fight-based chelator (Mark 15 manufactured by Asahi Denka Co., Ltd.)
05A) 1 part by weight, 0.3 part by weight of zinc stearate, and 2 parts by weight of synthetic hydrotalcite were mixed, and the surface temperature of the roll was set to 150 on a 9-inch mill roll.
The mixture was kneaded at 5 ° C. for 5 minutes to obtain a vinyl chloride resin sheet having a thickness of about 1 mm.

[0026]

[Table 1]

INDUSTRIAL APPLICABILITY The laminate and the vehicle window frame of the present invention are excellent in the adhesiveness between the vinyl chloride resin layer and the urethane resin layer and are extremely useful.

Front page continuation (72) Inventor Yoshihisa Iwata 2 Oike, Iwazuka-cho, Nakamura-ku, Aichi Prefecture Nagoya, Mitsubishi Chemical MKB Co., Ltd. (72) Inventor Kanji Kato 2 Oike, Iwatsuka-cho, Nakamura-ku, Aichi Prefecture Mitsubishi Chemical MKV Co., Ltd., Nagoya Works (72) Inventor Nobuyuki Tamai, Asahi Glass Co., Ltd. Aichi Factory, No. 1 Asahi, Taketoyo-cho, Chita-gun, Aichi

Claims (5)

[Claims] 1. 100 parts by weight of a vinyl chloride resin containing a hydroxyl group and / or a carboxyl group (hereinafter referred to as "functional group-containing vinyl chloride resin") and 20 to 15 plasticizers.
A laminate comprising a urethane resin layer laminated on a resin layer formed by molding a vinyl chloride resin composition comprising 0 parts by weight. 2. A functional group-containing vinyl chloride resin is a polymer of the following (1) and (2) and / or (1) and (2):
The laminate according to claim 1, which comprises a polymer of (3) and (3). (1) vinyl chloride monomer (2) containing a hydroxyl group and / or a carboxyl group,
Monomer copolymerizable with vinyl chloride monomer (hereinafter referred to as "monomer having hydroxyl group and / or carboxyl group") (3) Other than (2) copolymerizable with vinyl chloride monomer Monomer of 3. The laminate according to claim 2, wherein the content of the hydroxyl group- and / or carboxyl group-containing monomer in the functional group-containing vinyl chloride resin is 0.01 to 15 mol%. 4. The laminate according to claim 2, wherein the content of the hydroxyl group- and / or carboxyl group-containing monomer of the functional group-containing vinyl chloride resin is 0.1 to 5 mol%. 5. A vehicle window frame made of the laminated body according to any one of claims 1 to 4.