JP2004195863A - Polyvinyl chloride resin-coated layer for vehicle interior trim and laminate using this layer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate which shows remarkable staining properties and is composed of a coated layer molded of a polyvinyl chloride resin composition having favorable adhesion with urethane which reduces a foreign sound generated by friction with another component due to a vibration during the traveling of a vehicle and a foamed urethane layer. <P>SOLUTION: The laminate is composed of the polyvinyl chloride resin-coated layer for a vehicle interior trim which is molded of the polyvinyl chloride resin composition obtained by blending 30 to 150 pts.wt. of a plasticizer and 5 to 100 pts.wt. of an acryl-modified polyorganosiloxane obtained by emulsion graft copolymerization to 100 pts.wt. of the polyvinyl chloride resin with a degree of partial crosslinking of 10 to 50 wt%. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００３０】
【表２】

【００３１】
(成分の明細)
・ 塩化ビニル系樹脂(同前) : GR-1300T (信越化学工業社製、商品名、ゲル分17%)
・ 塩化ビニル系樹脂(同前) : GR-2500S (信越化学工業社製、商品名、ゲル分20%)
・ 塩化ビニル系樹脂(表中、PVCとする) : TK-1700E (信越化学工業社製、商品名、平均重合度1700、ゲル分0%)
・ 可塑剤 : DINP(新日本理化社製、商品名)
・ 可塑剤 : エポキシ化大豆油 O-130P(旭電化工業社製、商品名)
・ 炭酸カルシウム : ホワイトンSB (備北粉化工業社製、商品名)
・ Ba-Zn系安定剤 : AC-255(旭電化工業社製、商品名)
・ 安定助剤 : Bonding Agent TN/S 50 (バイエルジャパン社製、商品名、ベンジルブチルフタレート50%)
・ アクリル変性ポリオルガノシロキサン : シャリーヌR (日信化学工業社製、商品名、イ : ロ=7 : 3)
・ BLACK顔料 : DAP-4710(大日精化社製、商品名)
・ シリコーンオイル : KF-96 (信越化学工業社製、商品名)
【００３２】
【発明の効果】
自動車等の車両内装材料として用いられる塩化ビニル系樹脂被覆層と発泡ウレタンの層からなる積層体において、汚染性に優れ、車両走行時の振動により他部品と摩擦することによって生じる異音を低減し、かつ被覆層と発泡ウレタン層の接着も問題ない。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a laminate composed of a vinyl chloride resin coating layer and a urethane foam layer used as a vehicle interior material for automobiles and the like, which has excellent contamination properties and is caused by friction with other parts due to vibrations during running of the vehicle. The present invention relates to a laminate comprising a coating layer molded from a vinyl chloride resin composition having good adhesion to urethane for reducing sound and a layer of urethane foam.
[0002]
[Prior art]
Headrests, armrests, crash pads, glove boxes, console boxes, door trims, etc., which are interior materials for automobiles and the like, are molded with a vinyl chloride resin composition having a urethane foam layer inside to give flexibility. Coating layers are frequently used. However, since the coating layer formed of this vinyl chloride resin composition is formed using a soft vinyl chloride resin containing a plasticizer as a raw material, the surface is sticky and impairs the appearance due to dust and dirt adherence and human hand stains. There was something. In addition, a problem has been pointed out that friction due to a high coefficient of friction causes friction with other components due to vibrations during running of the vehicle, thereby generating abnormal sounds such as rubbing noise and squeaking noise.
[0003]
In general, the polyvinyl chloride layer of the laminate is formed by blow molding or injection molding, and a method of subjecting a mold to a graining process to suppress surface stickiness has been conventionally performed. However, although the texture is improved by the graining, it is not possible to suppress the adhesion of dust and dirt and human dirt, and there is no effect in reducing abnormal noise. In order to reduce surface stickiness and abnormal noise, a method of adding a lubricating agent such as paraffin wax and fatty acid amide and a silicone oil in advance has been proposed, but a polyvinyl chloride resin molded by this method has been proposed. The product bleeds out to the surface with the passage of time, dust and dirt tend to adhere and become contaminated, and the adhesiveness to the urethane foam layer is deteriorated, which is not preferable (for example, see Reference Document 1).
[0004]
[Reference 1] JP-A-57-30754 (pages 1-2)
[0005]
[Problems to be solved by the invention]
Accordingly, the present inventors have conducted intensive studies to solve the above-described problems, and as a result, have excellent contamination properties, and have an adhesive property with urethane that reduces abnormal noise caused by friction with other parts due to vibration during vehicle running. An object of the present invention is to provide a laminate comprising a layer formed of a good vinyl chloride resin composition and a layer of urethane foam.
[0006]
[Means for solving the problem]
The polyvinyl chloride coating layer of the present invention has a degree of partial cross-linking of 10 to 50% by weight with respect to 100 parts by weight of a vinyl chloride-based resin, and a plasticizer of 30 to 150 parts by weight. Molded from a vinyl chloride resin composition containing 5 to 100 parts by weight of an acrylic-modified polyorganosiloxane obtained by the above method.
[0007]
Another aspect of the present invention relates to a laminate including the coating layer and a urethane foam layer.
[0008]
The vinyl chloride resin having a degree of partial cross-linking of 10 to 50% by weight used as the vinyl chloride resin composition as the molding material of the coating layer of the present invention is a vinyl chloride monomer or a vinyl chloride monomer and Is obtained by adding a polyfunctional monomer in an amount corresponding to a desired degree of cross-linking to the polymerization system at the time of suspension polymerization of a mixture with the above monomer.
[0009]
Here, as the polyfunctional monomer, a monomer containing two or more ethylenic double bonds in the molecule, for example, diallyl esters of phthalic acid such as diallyl phthalate, diallyl maleate, diallyl fumarate, diallyl itaconate and the like Ethylene unsaturated dibasic acid diallyl esters, diallyl ether, triallyl cyanurate, ethylene glycol divinyl ether, n-butanediol divinyl ether and other divinyl ethers, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol Di (meth) acrylates of polyhydric alcohols such as dimethacrylate.
[0010]
The polyfunctional monomer is desirably added in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of a vinyl chloride monomer or a mixture of a vinyl chloride monomer and another monomer.
[0011]
Other monomers include vinyl acetates such as vinyl acetate and vinyl propionate, (meth) acrylates such as methyl methacrylate, ethyl methacrylate, methyl acrylate, and ethyl acrylate, ethylene and propylene. And olefinic acids, maleic anhydride, acrylonitrile, styrene and the like, and these are used alone or in combination of two or more.
[0012]
It is preferable that the partially crosslinked polyvinyl chloride resin has a gel content insoluble in tetrohydrofuran (THF) of 10 to 50% by weight, preferably 15 to 40% by weight. If the gel content is less than 5% by weight, the matting effect is insufficient, and if it exceeds 90% by weight, the mechanical strength is reduced and the moldability is remarkably deteriorated.
It is also possible to blend with a non-crosslinked vinyl chloride resin, but in this case, there is no problem if the gel content insoluble in tetrohydrofuran (THF) in the entire vinyl chloride resin is 10 to 50% by weight.
[0013]
These exemplified partially cross-linked vinyl chloride resins, the average degree of polymerization in the range of 300 to 4000 is used in terms of balance between mechanical strength and fluidity, but the average degree of polymerization is less than 300. In the case of, the mechanical strength is weak, and the plasticizer has poor holding power, so the plasticizer may migrate toward the skin layer.Conversely, if it exceeds 4000, the workability will be extremely deteriorated. Not preferred.
[0014]
The plasticizer used in the polyvinyl chloride resin composition as the coating layer of the present invention may be any plasticizer that is compatible with the vinyl chloride resin, and examples thereof include dimethyl phthalate, diethyl phthalate, Phthalates such as dibutyl phthalate, di-n-octyl phthalate (hereinafter referred to as DOP), diisodecyl phthalate and butylbenzyl phthalate; dibutyl adipate, di-n-hexyl adipate, dibutyl sebacate and the like Aliphatic dibasic acid esters; Tributyl phosphate, tri-2-n-ethylhexyl phosphate, tricresyl phosphate, triphenyl phosphate, etc .; phosphate esters; trimellitate-tri-2-ethylhexyl, trimellitate Trimellitic esters such as tributyl acid; glycol esters such as pentaerythritol ester and diethylene glycol benzoate Epoxidized esters such as epoxidized soybean oil and epoxidized linseed oil; citrates such as acetyl tributyl citrate, acetyl trioctyl citrate and tri-n-butyl citrate; tetra-n-octyl pyromelli Tate, polypropylene adipate, and other polyester-based plasticizers are used, and these are used alone or in combination of two or more.
These plasticizers are added in an amount of 30 to 150 parts by weight, preferably 50 to 100 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 30 parts by weight, the flexibility of the coating layer cannot be obtained, and if it exceeds 150 parts by weight, not only the strength is reduced and the coating layer may be torn, but also stainability and slidability are impaired.
[0015]
In the vinyl chloride-based resin coating layer of the present invention, the acrylic-modified polyorganosiloxane used as the third component is, as described earlier, one obtained by emulsion graft copolymerization of the above (a) and (b) in a ratio.
The acryl-modified polyorganosiloxane is used in an amount of 5 to 100 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 5 parts by weight, the stain resistance and the noise prevention effect are insufficient.If the amount exceeds 100 parts by weight, the contamination resistance and the noise prevention effect are not improved in proportion to the amount added, so that it is uneconomical. is there.
[0016]
In the general formula, R ¹ , R ² and R ³ each represent an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, or an aryl group such as a phenyl group, a tolyl group, a xylyl group, or a naphthyl group. A hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms in which at least one of hydrogen atoms bonded to carbon atoms of these hydrocarbon groups is substituted with a halogen atom, Each may be the same or different from each other.
Y is an organic group having a radical reactive group such as a vinyl group, an allyl group, a γ-allyloxypropyl group, a γ-methacryloxypropyl group, a γ-mercaptopipropyl group, or an SH group, or both.
Z ¹ and Z ² are a hydrogen atom, a methyl group, an ethyl group, a propyl group, a lower alkyl group such as a butyl group or a triorganosilyl group, and R ⁴ and R ⁵ in the triorganosilyl group are the same or different, respectively. R6 is a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, R6 is a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, or a radical reactive group or an organic group having an SH group or both. is there. Examples of the organic group having a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group, or a radical reactive group or an SH group or both in the triorganosilyl group include those described above. . Z ¹ and Z ² may be the same or different.
m is a positive integer of 10,000 or less, preferably an integer in the range of 500 to 8,000, and n is an integer of 1 or more, preferably an integer in the range of 1 to 500.
[0017]
As the (meth) acrylate used in the present invention, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, pentyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, stearyl acrylate And the like; alkoxyalkyl acrylates such as methoxyethyl acrylate and butoxyethyl acrylate; cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, and the like, which are used alone or in combination of two or more.
Examples of the copolymerizable monomer used together if desired include, for example, 2-hydroxyethyl (meth) acrylate, and a hydroxyl group-containing unsaturated monomer such as 2-hydroxypropyl (meth) acrylate. These are used alone or in combination of two or more.
[0018]
The vinyl chloride resin composition used in the coating layer of the present invention may, if necessary, include 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 object of the 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 maleate, octyltin malate, di-n-alkyltin mercaptide, di-n-alkyltin dilaurate, dibutyltin dimaleate, dibutyltin lauryl mercaptide, di-octyltin S, S'-bis- (isooctyl-mercaptoacetate) , Tin-based stabilizers such as dibutyltin bis-isooctylthioglycolate, di- (n-octyl) tin malate polymer, dibutyltin mercaptopropionate; calcium, cadmium, barium or zinc laurate or stearate, etc. Organic metal salt stabilizers and metal soap stabilizers; antimony salts such as antimony mercaptocarboxylate or ester salts Epoxidized oil stabilizers such as epoxidized soybean oil and epoxidized linseed oil, hindered phenols such as bisphenol dimerized with BHT, sulfur and methylene groups, salicylic acid esters, Examples include ultraviolet absorbers such as benzophenone and benzotriazole, which are used alone or in combination of two or more.
[0019]
As the lubricant, for example, aliphatic hydrocarbon-based lubricants such as low molecular wax, polyethylene wax, paraffin wax, liquid paraffin; higher aliphatic alcohol-based lubricants such as stearyl alcohol; stearamide, palmitic amide, methylene bisstearol Aliphatic amide-based lubricants such as amides; fatty acid ester-based lubricants such as glyceryl monostearate, ethyl diaminostearate, and butyl stearate; or metal soaps, silicone oils, and the like. These may be used alone or in combination of two or more. Used in combination.
[0020]
As the modifier, for example, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, chlorinated polyethylene, methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, acrylic Impact modifiers such as 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 ammonium trioxide, aluminum hydroxide, sodium antimonate, phosphate esters and phosphate compounds, chlorinated paraffins, chlorinated olefins, hexabromobenzene; partially crosslinked NBR, acrylic rubber, Elasticity-imparting agents such as polyurethane; and foaming , Antistatic agents, surfactants, optionally selected from among such conductive agent is used singly or two or more in combination.
[0021]
Examples of the filler include carbonates such as heavy calcium carbonate, light calcium carbonate, precipitated calcium carbonate, magnesium carbonate, and dawsonite; oxides such as silica, diatomaceous earth, and titanium oxide; aluminum hydroxide, water Hydroxide type such as magnesium oxide; (sulfite) type such as calcium sulfate and barium sulfate; silicate type such as talc, clay, mica and calcium silicate; carbon type such as carbon black and graphite; hollow or Inorganic glass such as solid glass beads, glass short fibers, metal fibers, carbon short fibers, and carbon fibers; metal powders such as iron powder and copper powder; heat-resistant resins such as polyimide and silicone; and the like. Used alone or in combination of two or more.
[0022]
As the colorant, any one can be selected from those conventionally used for coloring plastics. Examples of such coloring agents include, for example, aluminum powder, metal powders such as bronze powder, carbon salts such as carbon black, titanium oxide, zinc oxide, oxides such as red iron oxide, sulfates such as precipitated barium sulfate, Inorganic pigments such as carbonates such as calcium carbonate and basic magnesium carbonate, silicates such as clay and ultramarine blue, chromates such as graphite, aluminates such as cobalt blue, and ferrocyan compounds such as dark blue; toluidine Azo pigments such as red, permanent carmine FB, disazo yellow AAA, and lake red C; polycyclic pigments such as phthalocyanine blue, indanthrone blue, and quinacridone red; dyed lakes such as Victoria Pure Blue BO lake and alkaline blue toner And organic pigments such as azine pigments and fluorescent pigments Sexual dyes, acid dyes, solvent dye, include dyes such as disperse dyes, which are used singly or two or more in combination.
[0023]
The urethane foam layer of the present invention is usually obtained by reacting a polyol and a polyisocyanate in the presence of a foaming agent and a catalyst.
[0024]
As the polyol, polyester, polyether, polyetherester and the like are generally used.
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, m-xylylene diisocyanate, p-xylylene diisocyanate And the like.
[0025]
A coating layer molded from the vinyl chloride resin composition is laid in a mold, and a polyol and a polyisocyanate, which are components of the urethane foam, are charged with a foaming agent or the like therein. A laminate is manufactured.
[Preferred embodiment]
The vinyl chloride resin molding material of the present invention comprising the above components is mixed with a mixer such as a super mixer and a ribbon blender like the conventional vinyl chloride resin composition, and then mixed with a Banbury mixer, a mixing roll, a single screw or It can be kneaded and granulated by a twin screw extruder or the like.
[0026]
【Example】
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.
Each component (parts by weight) of the formulations shown in Tables 1 and 2 was charged into a 20-liter Henschel mixer and mixed, and the mixture was L / D = 22, using a full flight screw having a compression ratio of 3.0. A sample (pellet) was obtained by granulation with a 50 mm single screw extruder. This was tested by the following method, and the results are shown in Tables 1 and 2. The details of each component used are shown below.
[0027]
Manufacture of headrest ・ The vinyl chloride resin coating layer sample (pellet) is heated and kneaded with a single screw extruder at 150 to 160 ° C, and the material extruded into a cylindrical shape is sandwiched between two molds. Air was blown into the mold to bring it into close contact with the inner wall of the mold, and at the same time, the mold was cooled to obtain a hollow molded article to be a vinyl chloride resin coating layer.
Production of laminate The coating layer obtained above is spread in a mold, and a polyol mixture [polyether polyol, catalyst (triethylenediamine), foaming agent (water), foam stabilizer (silicone)] and isocyanate mixture [ Diphenylmethane diisocyanate, tolylene diisocyanate, prepolymer] from the inlet of the coating layer, and cure in a heating furnace at 40 to 50 ° C. for 6 minutes to form a urethane foam layer, a vinyl chloride resin coating layer and a urethane foam A layered headrest was obtained.
[0028]
(Test method)
(1) Long-term contamination After the headrest manufactured as described above was left in a room at 23 ° C for one year, the appearance of the product was determined according to the following evaluation criteria, and is also shown in Table-2. It should be noted that no movement or contact should be made during leaving.
:: Almost no dirt is noticeable.
×: Dust and dirt are conspicuous.
(2) Instantaneous contamination Take a 10 cm square sample from the headrest epidermis produced above, weigh 1 g of tobacco ash, and spread it thinly. The sample was set upright, the tobacco ash on the sample was dropped, and the degree of contamination on the product surface was determined according to the following evaluation criteria.
:: No stain is seen at all.
:: Almost no dirt is noticeable.
×: Dirt is noticeable.
(3) Sliding property:
Using Haydon 14-D-ANL (trade name, manufactured by Shinto Kagaku Co., Ltd.) as a friction tester, measure the static / dynamic friction coefficient of the headrest skin under the conditions of a 10φ SUS steel ball, a load of 50 g, and a pulling speed of 100 mm / min, and slide. The evaluation of the properties is shown in Tables 1 and 2.
(4) Adhesive strength:
A test piece having a width of 25 mm, a length of 150 mm, and a thickness of 10 mm was sampled from the headrest molded above, peeled off in advance by 50 mm from the side in the longitudinal direction of the test piece, and 10 mm was attached to a gripper of a tensile tester, and 100 mm / min. The average value was calculated from the maximum load when the film was peeled off at a speed of 50 mm and peeled off by 50 mm, and the average value was shown in Tables 1 and 2 as the adhesive force.
(5) Matting:
The surface of the headrest prepared above was measured with a gloss meter, and the results are shown in Tables 1 and 2.
[0029]
[Table 1]

[0030]
[Table 2]

[0031]
(Details of ingredients)
・ Vinyl chloride resin (before): GR-1300T (Shin-Etsu Chemical Co., Ltd., trade name, gel content 17%)
・ Vinyl chloride resin (before): GR-2500S (Shin-Etsu Chemical Co., Ltd., trade name, gel content 20%)
・ Vinyl chloride resin (PVC in the table): TK-1700E (Shin-Etsu Chemical Co., Ltd., trade name, average polymerization degree 1700, gel content 0%)
・ Plasticizer: DINP (Shin Nippon Rika Co., Ltd., trade name)
・ Plasticizer: Epoxidized soybean oil O-130P (Asahi Denka Kogyo Co., Ltd., trade name)
・ Calcium carbonate: Whiteton SB (Bihoku Powder Chemical Industry Co., Ltd., trade name)
・ Ba-Zn stabilizer: AC-255 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd.)
・ Stabilizer: Bonding Agent TN / S 50 (manufactured by Bayer Japan, trade name, benzyl butyl phthalate 50%)
・ Acrylic-modified polyorganosiloxane: Charine R (manufactured by Nissin Chemical Industry Co., Ltd., trade name, a: b = 7: 3)
・ BLACK pigment: DAP-4710 (trade name, manufactured by Dainichi Seika)
・ Silicone oil: KF-96 (Shin-Etsu Chemical Co., Ltd., trade name)
[0032]
【The invention's effect】
A laminate consisting of a vinyl chloride resin coating layer and a urethane foam layer used as a vehicle interior material for automobiles, etc., has excellent contamination properties and reduces abnormal noise caused by friction with other parts due to vibration during vehicle running. Also, there is no problem in adhesion between the coating layer and the urethane foam layer.

Claims (2)

The degree of partial cross-linking is 10 to 50% by weight, and 100 to 100 parts by weight of a vinyl chloride resin, and 30 to 150 parts by weight of a plasticizer, the following (a) and (b) are acrylic-modified polyorganosiloxanes 5 to 10 obtained by emulsion graft copolymerization. A vinyl chloride resin coating layer for vehicle interiors, which is formed from a vinyl chloride resin composition containing 100 parts by weight.
B. General formula

Wherein R ¹ , R ² and R ³ in the formula are the same or different, each having 1 to 20 carbon atoms or a halogenated hydrocarbon group, and Y is a radical reactive group or an SH group. Or an organic group having both of them, Z ¹ and Z ² are the same or different hydrogen atoms, lower alkyl groups or

Groups (R ⁴ and R 5 are the same or different, each having 1 to 20 carbon atoms or a halogenated hydrocarbon group; R ⁶ is a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group, or a radical reaction M is a positive integer of 10,000 or less, and n is an integer of 1 or more.
B. General formula

Or a mixture of 70% by weight or more of the (meth) acrylate and 30% by weight or less of a copolymerizable monomer.
Here, R ⁷ in the formula is a hydrogen atom or a methyl group, and R ⁸ is an alkyl group, an alkoxy-substituted alkyl group, a cycloalkyl group or an aryl group. 2. A laminate obtained by laminating a urethane foam layer on the coating layer according to claim 1.