JPH11129411A - Vinyl chloride resin-coated layer for interior material of vehicle, and laminate using the resin-coated layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride resin-coated layer for the interior material of a vehicle which suppresses the generation of a hydrogen chloride gas and at the same time, shows high mechanical strength, a remarkable adhesion with a foamed urethane and outstanding heat stability and weatherability as well as a laminate using this vinyl chloride resin-coated layer. SOLUTION: This vinyl chloride resin-coated layer for the interior material of a vehicle is formed of a vinyl chloride resin composition comprising 50-100 pts.wt. of plasticizer, 50-100 pts.wt. of calcium carbonate with an average particle diameter of 0.1 μm or lass and 0.5-10 pts.wt. of an organic ester compound with a hydroxy group blended with 100 pts.wt. of vinyl chloride resin with an average degree of polymerization of 2000-4000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is used as a vehicle interior material for automobiles and the like, suppresses generation of hydrogen chloride gas during combustion, and is excellent in mechanical strength, adhesiveness, heat stability and weather resistance. TECHNICAL FIELD The present invention relates to a vinyl chloride resin coating layer for a vehicle interior molded from a resin composition, and a laminate comprising the same and a urethane foam layer.

[0002]

2. Description of the Related Art Conventionally, headrests, armrests, crash pads, glove boxes, console boxes, door trims, etc., which are interior materials of vehicles such as automobiles, are provided with a layer of urethane foam to provide flexibility and cushioning. A laminate with a layer molded from the above-mentioned vinyl chloride resin composition is frequently used. Layers formed with this vinyl chloride resin composition are harmful to the human body during incineration and have the problem of generating hydrogen chloride gas that corrodes metals and the like, and the use of polyvinyl chloride can be considered. Have been. However, about 60% of the weight of polyvinyl chloride is chlorine, and the consumption of petroleum, which is a limited resource, is small.
Since it is a resource-saving plastic, a vinyl chloride resin that generates less hydrogen chloride gas has been demanded.

[0003]

In order to suppress the generation of hydrogen chloride gas, a method of adding a large amount of an inorganic filler such as calcium carbonate to a vinyl chloride resin has been used. Since the strength, elongation, and mechanical strength such as tear strength are reduced, the coating layer having the urethane foam layer may not only be cut or torn, but also reduce the adhesiveness with the urethane foam. And heat stability and weather resistance. For this reason, inorganic compounds such as lithium hydroxide having a high hydrogen chloride gas trapping effect with a small amount of addition have been proposed, but in addition to the problem of cost, the problem of initial coloring and deterioration due to strong alkali, or as a product. In terms of durability, it could not be used as a vehicle interior material. Therefore, the present invention solves the above-mentioned problems, and suppresses the generation of hydrogen chloride gas, and has excellent mechanical strength, adhesion to urethane foam, heat stability and weather resistance. It is an object to provide a vinyl-based resin coating layer and a laminate using the same.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems, and as a result, the decrease in mechanical strength is caused by an average degree of polymerization of the vinyl chloride resin of 2,000 to 4,000.
Can maintain the strength as a laminate comprising a vinyl chloride resin layer and a foamed urethane layer, and by using an organic ester compound having a hydroxy group, a vinyl chloride resin coating layer can be obtained. And the adhesive strength between the layers of urethane foam
It has been found that this organic ester compound can suppress the generation of hydrogen chloride gas during combustion than adding calcium carbonate having an average particle diameter of 0.1 μm or less alone, and also has the effect of increasing thermal stability and weather resistance, The present invention has been completed.

That is, according to the present invention, the average degree of polymerization is 200
For 100 parts by weight of vinyl chloride resin of 0 to 4000,
A vinyl chloride resin composition comprising 50 to 100 parts by weight of a plasticizer, 50 to 100 parts by weight of calcium carbonate having an average particle diameter of 0.1 μm or less, and 0.5 to 10 parts by weight of an organic ester compound having a hydroxy group. Is characterized by a vinyl chloride-based resin coating layer for vehicle interiors formed by molding. Further, it is preferable that the laminate is a vehicle interior laminate in which a urethane foam layer is laminated on the vinyl chloride resin coating layer.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, as the vinyl chloride resin constituting the vinyl chloride resin composition as a molding material of the vinyl chloride resin coating layer of the present invention, a vinyl chloride homopolymer, 50% by weight
Examples of the above vinyl chloride monomer, a copolymer of a vinyl monomer copolymerizable therewith, or a graft copolymer obtained by graft-polymerizing vinyl chloride to a polymer other than these, Among them, a vinyl chloride homopolymer is preferred.
These exemplified vinyl chloride resins have an average degree of polymerization of 2000 to 4 from the viewpoint of balance between moldability and mechanical properties.
When the average degree of polymerization is less than 2,000, the strength as a vinyl chloride resin coating layer cannot be maintained, and when it exceeds 4,000, molding becomes difficult. Not preferred.

The vinyl monomers copolymerizable with the vinyl chloride monomer include, for example, α-olefins such as ethylene, propylene, and butylene; vinyl acetate, vinyl caproate, vinyl laurate, and stearin. Vinyl esters such as vinyl acid; alkyl vinyl ethers such as butyl vinyl ether, octyl vinyl ether, dodecyl vinyl ether, and phenyl vinyl ether; acrylic acid such as ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate; Esters of methacrylic acid; aromatic vinyls such as styrene and α-methylstyrene; halogenated olefins such as vinylidene chloride, vinyl fluoride, vinyl bromide and propylene chloride;
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; and acrylic derivatives such as acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, itaconic anhydride and the like. These may be used alone or in combination of two or more. Used in combination.

Examples of the polymer which can be graft-polymerized with a vinyl chloride monomer include ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-ethyl acrylate copolymer, ethylene Ethyl acrylate / carbon monoxide copolymer, ethylene / methyl methacrylate copolymer, ethylene / propylene copolymer, acrylonitrile / butadiene copolymer, polyurethane, chlorinated polyethylene, chlorinated polypropylene, methyl methacrylate / butadiene / styrene copolymer Coalescing,
Examples include acrylonitrile / butadiene / α-methylstyrene copolymer, polybutyl acrylate, butyl rubber, polystyrene, styrene / butadiene copolymer, and acrylic rubber, and these are used alone or in combination of two or more. These may be used in combination with a monomer having at least one unsaturated group copolymerizable with the vinyl chloride monomer.

The plasticizer constituting the vinyl chloride resin composition used in the present invention may be any plasticizer that is compatible with the vinyl chloride resin exemplified above. Examples of the plasticizer include dimethyl phthalate, Diethyl phthalate, dibutyl phthalate, di-n-octyl phthalate, diisodecyl phthalate, butylbenzyl phthalate, or 11 to 1 carbon atoms
Phthalates such as phthalates of higher alcohols of about 3; dibutyl adipate, di-n-adipate
-Hexyl, aliphatic dibasic acid esters with dibutyl sebacate; Tributyl phosphate, tri-2-n-ethylhexyl phosphate, tricresyl phosphate, triphenyl phosphate, and other phosphate esters; trimellitic acid-tri- Trimellitic esters such as 2-ethylhexyl and tributyl trimellitate; glycol esters such as pentaerythritol ester and diethylene glycol benzoate; epoxidized esters such as epoxidized soybean oil and epoxidized linseed oil; acetyl tributyl citrate and acetyl trioctyl Citrates such as citrate and tri-n-butyl citrate; tetra-n-octyl pyromellitate, polypropylene adipate, and other polyester plasticizers; these may be used alone or in combination of two or more. It is used in the back. Above all, phthalic acid esters are preferably employed in consideration of mechanical strength, weather resistance and the like. These plasticizers are added in the range of 50 to 100 parts by weight based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 50 parts by weight, the flexibility as a coating layer cannot be obtained, and molding becomes difficult. Is also not preferred because the adhesiveness of the rubber becomes poor.

The calcium carbonate constituting the vinyl chloride resin composition used in the present invention has an average particle size of 0.1.
Those having an average particle diameter of more than 0.1 μm are not preferred because the specific surface area is small and the effect of trapping hydrogen chloride gas is small. This average particle diameter is 0.1 μm
The following calcium carbonate is the above-mentioned vinyl chloride resin 100
It is added in the range of 50 to 100 parts by weight based on parts by weight. If it is less than 50 parts by weight, the effect of capturing hydrogen chloride gas is not sufficient, and if it exceeds 100 parts by weight, mechanical strength and
It is not preferable because it is impossible to cover a decrease in adhesion to the urethane foam layer. In addition, it is more preferable to use the calcium carbonate surface-treated with a fatty acid or the like from the viewpoint of dispersibility.

The organic ester compound having a hydroxy group constituting the vinyl chloride resin composition used in the present invention is not particularly limited as long as it is a commonly used organic ester compound, but preferably contains an alcoholic hydroxyl group. A bifunctional hydroxy polyester is employed. Further, the organic ester compound, for example, adipic acid, sebacic acid, pimelic acid, suberic acid, carboxylic acid such as azelaic acid and ethylene glycol, propylene glycol,
1,4-butanediol, 1,3-butanediol,
1, -pentanediol, 1,6-hexanediol,
Manufactured from polyhydric alcohols such as diethylene glycol, 2,2-dimethylpropylene glycol, pentaerythritol, sorbitol, and glycerin, and diluted with benzyl butyl phthalate to adjust the viscosity in view of compatibility with vinyl chloride resins and workability. Solutions are mainly used. This organic ester compound is added to supplement the adhesion between the vinyl chloride resin coating layer and the urethane foam layer,
In the present invention, this also has an excellent effect of suppressing generation of hydrogen chloride gas, preventing discoloration during molding, and improving weather resistance. The organic ester compound having a hydroxy group is added in an amount of 0.5 to 10 parts by weight, preferably 1 to 8 parts by weight, based on 100 parts by weight of the vinyl chloride resin. This is 0.
If the amount is less than 5 parts by weight, not only the adhesion to the urethane foam layer is poor, but also the effect of suppressing hydrogen chloride gas and the effect of preventing discoloration are not obtained. Economy.

The vinyl chloride resin composition used in the present invention may contain, if necessary, stabilizers, lubricants, modifiers, fillers, coloring agents, etc., which are generally used for vinyl chloride resins.
It can be added and compounded within a range that does not impair the purpose of the present invention. As the stabilizer, for example, lead-based stabilizers such as tribasic lead sulfate, dibasic lead phosphite, basic lead sulfite, dibasic lead phthalate, lead white, lead laurate or stearate; butyl Tin malate, octyltin malate, di-
n-alkyltin mercaptide, di-n-alkyltin dilaurate, dibutyltin dimaleate, dibutyltin lauryl mercaptide, di-octyltin S, S'-bis- (isooctyl-mercaptoacetate), dibutyltin bis-
Isooctylthioglycolate, di- (n-octyl)
Tin-based stabilizers such as tin malate polymer and dibutyltin mercaptopropionate; organic metal salt-based stabilizers such as calcium, cadmium, barium or zinc laurate or stearate; and metal soap-based stabilizers; antimony mercaptocarboxylic acid Antimony stabilizers such as salts or ester salts; phosphate stabilizers; epoxidized oil stabilizers such as epoxidized soybean oil and epoxidized linseed oil, BH
UV absorbers such as hindered phenols such as bisphenol dimerized with T, sulfur and methylene groups, salicylic acid esters, benzophenone, benzotriazole, etc., and these may be used alone or in combination of two or more. You.

As the lubricant, for example, low molecular wax,
Aliphatic hydrocarbon lubricants such as polyethylene wax, paraffin wax and liquid paraffin; higher aliphatic alcohol lubricants such as stearyl alcohol; aliphatic amide lubricants such as stearamide, palmitic amide and methylenebisstearamide; Fatty acid ester-based lubricants such as glycerin stearate, ethyl diaminostearate, and butyl stearate; or metal soaps, silicone oils, etc., each of which may be used alone or in combination.
Used in combination of more than one species.

As the modifier, for example, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, chlorinated polyethylene, methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer Impact modifiers such as coalesce, acrylic rubber; gelling accelerators such as polymethyl methacrylate; acrylonitrile / butadiene / α-methylstyrene copolymer, methyl methacrylate / acrylate copolymer, and other copolymers using maleimide Flame retardants such as antimony trioxide, aluminum hydroxide, sodium antimonate, phosphate esters and phosphate compounds, chlorinated paraffins, chlorinated olefins, hexabromobenzene; partially crosslinked NBR; Elasticity of acrylic rubber, polyurethane, etc. ; More foaming agents, antistatic agents,
Arbitrarily selected from surfactants, conductivity-imparting agents, etc., and
These are used alone or in combination of two or more.

As the filler, for example, carbonates such as magnesium carbonate and dawsonite; oxides such as silica, diatomaceous earth and titanium oxide; hydroxides such as aluminum hydroxide and magnesium hydroxide; calcium sulfate Silicates such as talc, clay, mica and calcium silicate; carbons such as carbon black and graphite; hollow or solid glass beads;
Inorganic fiber type such as glass short fiber, metal fiber, carbon short fiber, carbon fiber; metal powder type such as iron powder and copper powder; heat-resistant resin such as polyimide and silicone; Used in combination of more than one species.

As the coloring agent, any one can be selected from those commonly used for coloring plastics. Examples of such a coloring agent include metal powders such as aluminum powder and bronze powder, carbon salts such as carbon black, titanium oxide, zinc oxide, oxides such as porcelain, sulfates such as precipitated barium sulfate, and the like. Carbonates such as calcium carbonate and basic magnesium carbonate,
Silicates such as clay and ultramarine, chromates such as graphite,
Inorganic pigments such as aluminates such as cobalt blue and ferrocyan compounds such as dark blue; azo pigments such as toluidine red, permanent carmine FB, disazo yellow AAA and lake red C, phthalocyanine blue, indanthrone blue, quinacridone red and the like; Dyeing lakes such as polycyclic pigments, Victoria Pure Blue BO Lake, Alkaline Blue Toner, organic pigments such as azine pigments, fluorescent pigments and the like, basic dyes, acid dyes, oil-soluble dyes,
Dyes such as disperse dyes are used, and these are used alone or in combination of two or more.

The vinyl chloride resin composition comprising the above components is mixed by a mixer such as a super mixer, a Henschel mixer, a ribbon blender or the like, and then mixed with a Banbury mixer, a mixing roll, a single screw or twin screw extruder. The mixture is kneaded and granulated. This is kneaded with a single-screw or twin-screw extruder or the like under a commonly used method and conditions, and is sandwiched by a mold and molded by blowing air to form a vinyl chloride resin coating layer suitable as a vehicle interior. Can be produced.

Next, the invention according to claim 2 is a laminate of the vinyl chloride resin coating layer and the urethane foam layer, wherein the urethane foam layer usually comprises a polyol and a polyisocyanate as a foaming agent. And in the presence of a catalyst. As the polyol, polyester, polyether, polyetherester and the like are generally used. As the polyether, for example, polyethylene polyol having a functionality of 2 to 3 and an average molecular weight of 2000 to 3000,
Examples of the polyester include polypropylene polyol and polytetramethylene polyol. Examples of the polyester include a linear polyester obtained by condensation of adipic acid and a bifunctional compound such as ethylene glycol. As the polyisocyanate, 4,4′-diphenylmethane-diisocyanate (MDI), 2,4-tolylene-diisocyanate (2,4-TDI), 2,6-
Tolylene diisocyanate (2,6-TDI), ethylene diisocyanate, hexamethylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate Isocyanate, m-xylylene diisocyanate, p-
Xylylene diisocyanate and the like.

The foaming agent used in the reaction between the polyol and the polyisocyanate includes, for example,
Water, methylene chloride, trichlorofluoromethane and the like. Further, as a catalyst, a tertiary amine such as pentamethyldiethyltriamine, trimethylaminoethylethanolamine, tetramethylamino-bis-propylamine, 2,6-diaza -2,6-dimethyl-10
-Hydroxydecane, N-dimethylaminopropylamine, triethylenediamine, N, N-dimethylaminoethoxyethanol, N, N-diethylaminoethoxyethanol, tetramethyl-2-hydroxypropyldiethyltriamine, dimethylaminoethanol, hydroxypropylpiperazine, bis -Dimethylaminoethylpiperazine, N, 2-hydroxypropylmorpholine and the like.

In order to produce the laminate of the present invention, first, a coating layer formed of the above-mentioned vinyl chloride resin composition is laid in a mold, and a polyol and a polyisocyanate, which are components of the urethane foam, are placed therein. By adding a foaming agent, a catalyst and the like, a laminate of a vinyl chloride resin coating layer and a urethane foam layer can be produced.

[0021]

EXAMPLES Hereinafter, specific embodiments of the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to these descriptions. The components of the formulations shown in Tables 1 and 2 were put into a 20-liter Henschel mixer and mixed, and the mixture was mixed with a 50 mm 2 screw using a full flight screw having an L / D of 22 and a compression ratio of 3.0. Granulation was performed using a screw extruder to obtain a sample (pellet). These samples were evaluated as follows, and the results are shown in Tables 1 and 2.

Manufacture of headrests-Vinyl chloride resin coating layer Samples (pellets) are 150-160 using a single screw extruder.
The material extruded into a cylindrical shape is heated and kneaded under the condition of ° C., and is sandwiched between two molds, and air is blown into the mold so that the material is brought into close contact with the inner wall of the mold. A molded product was obtained.・ Production of laminated body The coating layer obtained above is spread in a mold, and a polyol mixed solution [polyether polyol, catalyst (triethylenediamine), foaming agent (water), foam stabilizer (silicone)] and isocyanate mixed solution [ Diphenylmethane diisocyanate,
Tolylene diisocyanate, prepolymer] from the inlet of the coating layer, and cured in a heating furnace at 40 to 50 ° C. for 6 minutes to form a urethane foam layer, and a headrest comprising a vinyl chloride resin coating layer and a urethane foam layer I got

(Specification of components) Vinyl chloride resin (referred to as PVC in the table): TK-1
300 (trade name, average degree of polymerization 130, manufactured by Shin-Etsu Chemical Co., Ltd.)
0 vinyl chloride homopolymer). -Vinyl chloride resin (referred to as PVC in the table): TK-2
500PE (Shin-Etsu Chemical Co., Ltd., trade name, average degree of polymerization 3
000 vinyl chloride homopolymer).・ Plasticizer: DINP (Shin Nippon Rika Co., Ltd., trade name) ・ Plasticizer: Epoxidized soybean oil ・ O-130P (Asahi Denka Kogyo Co., Ltd., trade name) ・ Calcium carbonate A: Calfine 200M (Maruo Calcium Co., Ltd.) , Trade name, average particle size 0.05 μm). -Calcium carbonate B: Whiten SB (trade name, average particle size 1.85 µm, manufactured by Bihoku Powder Chemical Industry Co., Ltd.).・ Organic ester compound having hydroxy group: Bond
ing Agent TN / S50 (manufactured by Bayer Japan, trade name, benzyl butyl phthalate 50%) Ba-Zn based stabilizer AC-255 (manufactured by Asahi Denka Kogyo Co., Ltd.) Pigment [titanium oxide DAP-4050 ( Made by Dainichi Seika,
Product name)]

(Specification of Test Method) Measurement of Hydrogen Chloride Gas Emission A sample (pellet) was used in accordance with JIS K7217. That is, about 0.1 g of a sample is weighed in a sample dish, heated and burned to collect combustion gas,
Tables 1 and 2 show the hydrogen chloride gas generation amount and the hydrogen chloride gas trapping rate. In addition, the hydrogen chloride gas capture rate was calculated using the following equation.

Measurement of mechanical strength: Tensile test The skin of the headrest formed above was peeled off, and JIS
It was punched out with a K6301 dumbbell No. 1, and a 40 mm mark was drawn to obtain a test piece. This was pulled at a speed of 200 mm / min by a Shopper type tensile tester, the maximum load required for the test piece to break and the distance between the marked lines at the time of break were measured, and the tensile strength and elongation were calculated. Are shown in Tables 1 and 2. In addition, as a value which does not cause any problem to be used as the coating layer from the conventional results, the tensile strength is 8.0 MPa.
As described above, the elongation of 250% or more is set as the target value.

Tearing test The skin of the headrest formed above was peeled off and subjected to JIS.
A B-type test piece of K6301 was punched out, pulled at a speed of 200 mm / min by a shopper type tensile tester, the maximum load required to tear the test piece was measured, and the tear strength was determined. The results were shown in Tables 1 and 2. It was shown to. In addition, as a value that does not have a problem to use as a coating layer from the past results,
The target value was set to a tear strength of 25.0 kg / cm or more.

Adhesive strength: A test piece having a width of 25 mm, a length of 150 mm, and a thickness of 10 mm is sampled from the headrest formed as described above, and is peeled off in advance by 50 mm from the lengthwise side of the test piece, and 10 mm is gripped by a tensile tester. Attach to the tool, 10
An average value was calculated from the maximum load when the film was pulled at a speed of 0 mm / min and peeled off by 50 mm, and the obtained value was defined as the adhesive force.
In addition, as a value which does not have any problem from the conventional results, an adhesive force of 0.3 kgf / 25 mm or more was set as a target value.

Heat resistance test: Peel off the skin of the headrest formed above, take a test piece 70 mm wide and 200 mm long, and make the same size slab urethane foam on the back side with the vinyl film side, thickness 10 ± 80 with 1mm
After being kept for 400 hours in a gear aging tester controlled at +/- 2 ° C, the degree of discoloration and deterioration was represented by the following evaluation criteria.

Weathering test: The skin of the headrest molded above was peeled off, a test piece having a width of 70 mm and a length of 200 mm was taken, a slab urethane foam having the vinyl film side as the front side and the same size on the back side, and a thickness of 10 ± After attaching 1 mm to a high-temperature type fed-ometer and irradiating for 400 hours, the degree of discoloration and deterioration was represented by the following evaluation criteria. (Evaluation criteria) 5: Discoloration and deterioration are not recognized at all. 4: Discoloration and deterioration are slightly observed but not conspicuous. 3: Discoloration and deterioration are clearly observed but not conspicuous. 2: Discoloration and deterioration are slightly remarkable. 1: Discoloration and deterioration are considerably remarkable.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

According to the present invention, it is possible to capture about 80% of the theoretical amount of hydrogen chloride gas, suppress the generation of hydrogen chloride gas, mechanical strength, adhesiveness to urethane foam, heat It is possible to provide a vinyl chloride-based resin coating layer having excellent stability and weather resistance and having a sufficient function as a vehicle interior material for automobiles and the like, and a laminate using the same.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hidekazu Oike 10-2 Koroku-cho, Moriyama-ku, Nagoya-shi, Aichi Pref. No. 10-2, Towa Kasei Head Office

Claims (2)

[Claims] 1. A plasticizer of 50 to 100 parts by weight per 100 parts by weight of a vinyl chloride resin having an average degree of polymerization of 2,000 to 4,000.
5 parts by weight of calcium carbonate 5 having an average particle size of 0.1 μm or less
A vinyl chloride resin coating for a vehicle interior, which is formed by molding a vinyl chloride resin composition containing 0 to 100 parts by weight and 0.5 to 10 parts by weight of an organic ester compound having a hydroxy group. layer. 2. A vehicle interior laminate comprising the vinyl chloride resin coating layer according to claim 1 and a urethane foam layer laminated thereon.