JPH08295863A - Adhesive composition, adhesive molded form therefrom and its production, composite molded form and multilayer molded form each having adhesive layer from the composition and their production - Google Patents

Abstract

PURPOSE: To obtain an adhesive composition comprising a vinyl chloride-based resin and a polyolefin having specific viscosity characteristics, and providing an adhesive layer capable of firmly and integrally bonding a vinyl chloride-based resin layer and a polyolefin layer to each other. CONSTITUTION: This adhesive composition comprises (A) 100 pts.wt. of a vinyl chloride-based resin and (B) 10-350 pts.wt. of a polyolefin with a complex dynamic viscosity η* of <=1.2×10<5> poise (pref. olefin-based thermoplastic elastomer), and pref. furthermore, (C) <=20 (pref. 0.1-20, more pref. 2-10) pts.wt. of a foaming agent. This composition can be easily made into an adhesive molded form, for example, by powder molding thereof. And a composite molded form where the above molded form lies integrally laminated with a vinyl chloride-based resin molded form (e.g. a powder-molded sheet obtained by powder molding of vinyl chloride-based resin powder) can also be obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an adhesive composition, an adhesive molded article obtained by molding the same, a method for producing the same, a composite molded article having an adhesive layer formed by molding the adhesive composition, and a multilayer. TECHNICAL FIELD The present invention relates to a molded body and a method for manufacturing them.

[0002]

2. Description of the Related Art Conventionally, a molded product having a complicated pattern such as a skin grain or a stitch on its surface has been used as an interior material for automobiles, and the molded product is, for example, a vinyl chloride resin layer and a polyolefin layer. Is known (Japanese Patent Laid-Open No. 63-151206). However, since the vinyl chloride resin layer and the polyolefin layer are inferior in adhesiveness to each other, there is a problem that the multilayer molded body is easily peeled off from each other.

As a solution to such a problem, an adhesive composition comprising a vinyl chloride resin and a polyolefin has been proposed, and a vinyl chloride resin layer and a vinyl chloride resin layer are formed through an adhesive layer formed by molding the adhesive composition. A multilayer molded body in which a polyolefin layer is integrally laminated is known (Japanese Patent Laid-Open No. 2-198811 and Japanese Patent Laid-Open No. 2-1988).
No. 12). However, such an adhesive composition does not always provide an adhesive layer capable of firmly adhering the vinyl chloride resin layer and the olefin layer, and is not industrially sufficiently satisfactory.

[0004]

SUMMARY OF THE INVENTION Accordingly, the present inventors
As a result of intensive studies to develop an adhesive composition capable of providing an adhesive layer having excellent adhesiveness between a vinyl chloride resin layer and a polyolefin layer, an adhesive composition comprising a vinyl chloride resin and a polyolefin having specific viscosity characteristics It was found that the product can provide an adhesive layer capable of firmly bonding and integrating a vinyl chloride resin layer and a polyolefin layer, and thus the present invention has been completed.

[0005]

That is, according to the present invention, 10 to ³ polyolefins having a complex dynamic viscosity η ^* of 1.2 × 10 ⁵ poise or less per 100 parts by weight of a vinyl chloride resin are used.
An adhesive composition comprising 50 parts by weight is provided.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The vinyl chloride resin which is one component constituting the adhesive composition of the present invention includes, for example, vinyl chloride homopolymer, vinyl chloride and other monomers copolymerizable therewith. Copolymers, for example vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-chloride Vinylidene copolymer, Ena vinyl-butadiene copolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer , Vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, Vinyl - styrene - acrylonitrile terpolymer, ethylene - but graft copolymer of vinyl chloride to vinyl acetate copolymer and mixtures thereof, and the like, but is not limited thereto.

Examples of the polyolefin that is another component of the adhesive composition of the present invention include polyolefin resin, polyolefin rubber, olefin thermoplastic elastomer, and mixtures thereof.

The polyolefin resin is a crystalline polymer or copolymer formed by polymerizing or copolymerizing one or more olefins, and examples thereof include polyethylene, polypropylene and ethylene-propylene copolymers.
Examples of the ethylene-butene copolymer, propylene-1-butene copolymer, propylene-2-butene copolymer and the like, among them, in that it can give an adhesive layer excellent in flexibility,
Ethylene-propylene copolymer, propylene-1-butene copolymer and the like are preferably used.

Polyolefin rubber is a polymer or copolymer of non-crystalline olefins, such as ethylene.
Examples include α-olefin copolymer rubber. Α- in the ethylene / α-olefin-based copolymer rubber
Examples of the olefin include propylene and 1-butene, and examples of the non-conjugated diene include dicyclopentadiene, ethylidene norbornene, 1,4-hexadiene, cyclooctadiene and methylene norbornene. Specific examples of such ethylene / α-olefin copolymer rubbers include ethylene-propylene copolymer rubber, ethylene-propylene-ethylidene norbornene copolymer rubber (hereinafter referred to as EPDM), and mixtures thereof. However, EPDM is preferably used because it can provide an adhesive layer having excellent heat resistance.

Examples of the olefinic thermoplastic elastomer include a composition composed of a polyolefin resin and a polyolefin rubber, a partially crosslinked composition composed of a polyolefin resin and a polyolefin rubber, and the like. It can be easily produced by kneading the polyolefin-based resin and the polyolefin-based rubber, or by further dynamically crosslinking after kneading.

In the dynamic cross-linking for obtaining the partially cross-linking type composition, the composition comprising the polyolefin resin and the polyolefin rubber obtained by kneading in advance and the cross-linking agent may be kneaded under heating, As such a crosslinking agent, an organic peroxide is usually used. Examples of such organic peroxides include dialkyl peroxides such as 2,5-dimethyl-2,2-di (t-butylperoxyno) hexane and dicumulperoxide, and the amount thereof is the kneading amount mentioned above. The amount is usually 1 part by weight or less, preferably 0.8 parts by weight or less, based on 100 parts by weight of the total amount of the polyolefin resin and the polyolefin rubber used in.

When an organic peroxide is used as a cross-linking agent, when the dynamic cross-linking is carried out in the presence of a cross-linking aid such as a bismaleimide compound, the cross-linking progresses appropriately and the adhesive layer has excellent heat resistance. Can be obtained. In this case, the amount of the organic peroxide used is usually 1 part by weight or less, preferably 0.8 parts by weight or less, more preferably 0.6 parts by weight, based on 100 parts by weight of the total amount of the polyolefin resin and the polyolefin rubber. The amount of the crosslinking aid used is usually 1.5 per 100 parts by weight of the total amount of the polyolefin resin and the polyolefin rubber.
It is less than or equal to part by weight, preferably less than or equal to 0.8 part by weight. In addition,
The cross-linking aid is preferably added prior to dynamic cross-linking, and is usually added in the previous kneading.

At the time of dynamic crosslinking, the composition comprising the polyolefin resin and the polyolefin rubber and the crosslinking agent are kneaded by an ordinary method, for example, a method using a uniaxial kneader, a biaxial kneader or the like.

By such dynamic crosslinking, the polyolefin rubber is usually preferentially crosslinked among the compositions composed of the polyolefin resin and the polyolefin rubber to obtain the desired partially crosslinked composition. In the partially crosslinked composition, an uncrosslinked polyolefin-based rubber may be present, or a crosslinked product of a polyolefin-based resin and a polyolefin-based rubber may be present, and in some cases, a polyolefin-based resin A crosslinked product may be present.

Further, such a partially crosslinked composition may be used by additionally blending a polyolefin rubber therein. The polyolefin rubber additionally blended here may be the same as the above-mentioned polyolefin rubber, but normally, α-olefin is propylene, 1
-Ethylene / α-olefin copolymer rubber such as butene is used, and among them, the ethylene unit content is 40-
90% by weight, preferably 70-80% by weight of ethylene-
Propylene copolymer rubber is preferably used. The amount of polyolefin rubber additionally compounded in this way is
It is usually 50 parts by weight or less based on 100 parts by weight of the total amount of the polyolefin resin and the polyolefin rubber used in the above kneading.

The composition comprising the polyolefin resin and the polyolefin rubber or the partially crosslinked composition comprising the polyolefin resin and the polyolefin rubber thus obtained can be used in the same various kinds as when blended in a usual thermoplastic elastomer. You may contain compounding agents and rubbers. As a compounding agent, for example, a mineral oil-based softening agent such as a paraffin-based process oil, a phenol-based, a sulfite-based, a phenylalkane-based, a phosphite-based, an amine-based, an amide-based heat stabilizer, an antiaging agent, and a weather resistance stabilizer. Agents, antistatic agents, metal soaps, lubricants such as waxes, and internally added release agents such as methylpolysiloxane compounds. Examples of rubbers include styrene / butadiene rubber, hydrogenated styrene / butadiene rubber, nitrile rubber, Natural rubber etc. are mentioned. These compounding agents and rubbers
It may be contained in advance in the raw material polyolefin-based resin or polyolefin-based rubber, or may be appropriately blended during the above-mentioned kneading or dynamic cross-linking, or thereafter by a usual method such as kneading.

Among them, a mineral oil-based softening agent is preferably used because it can give an adhesive layer having excellent flexibility when it is contained in a thermoplastic elastomer. By using a polyolefin rubber, the above kneading and dynamic crosslinking can be performed more easily. The amount of the mineral oil-based softening agent used in the oil-extended polyolefin-based rubber is usually 120 parts by weight or less, preferably 30 to 120 parts by weight, based on 100 parts by weight of the polyolefin-based rubber.

The polyolefin used in the adhesive composition of the present invention is the above-mentioned polyolefin resin, polyolefin rubber, olefin thermoplastic elastomer, etc., and its complex dynamic viscosity η ^* is 1.2 ×. 10 ⁵
It is necessary that the poise or less, for that, when the polyolefin used is a polyolefin-based resin or a polyolefin-based rubber, it is necessary to appropriately select and use the type and molecular weight distribution, and the polyolefin used In the case of the above composition or partially crosslinked composition, it is necessary to appropriately select the type of each component constituting the composition and the weight ratio thereof, the degree of crosslinking, the type of various compounding agents and the amount used thereof. . In the latter case, the shear rate in kneading or dynamic crosslinking has a great influence on the complex dynamic viscosity η ^* , and it is preferable to carry out kneading or dynamic crosslinking at a shear rate of 1 × 10 ³ sec ⁻¹ or more.

Here, the complex dynamic viscosity η ^* means a temperature of 250
From the storage viscoelastic modulus G'and the loss viscoelasticity G '' measured under the conditions of ℃ and frequency ω of 1 radian / second, the formula (1) η ^* = [(G ') ² + (G'') ² ] ^1/2 / ω (1), preferably 1 × 10 ²
~ 1.2 × 10 ⁵ poise, more preferably 1 × 10 ²
The range is from 1 × 10 ⁵ poise. When the complex dynamic viscosity η ^* exceeds 1.2 × 10 ⁵ poise, an adhesive layer having poor adhesion between the vinyl chloride resin layer and the polyolefin layer can be obtained.

The polyolefin used in the adhesive composition of the present invention is as described above. Among them, the adhesive molded body obtained by the powder molding described below can be easily released from the mold. Therefore, an olefin-based thermoplastic elastomer is preferably used.

The adhesive composition of the present invention comprises the vinyl chloride resin and the polyolefin as described above. The polyolefin in the adhesive composition is 10 to 350 parts by weight per 100 parts by weight of the vinyl chloride resin. , Preferably 20 to 200 parts by weight, more preferably 30 to 150 parts by weight. When the content of the polyolefin is less than 10 parts by weight, an adhesive layer having poor adhesion to the polyolefin layer is obtained, and when it exceeds 350 parts by weight, the adhesiveness to the vinyl chloride resin layer becomes poor.

The adhesive composition of the present invention comprises such a vinyl chloride resin and a polyolefin, but such an adhesive composition may further contain a foaming agent. Usually, a pyrolytic foaming agent is used. Examples of such a thermal decomposition type foaming agent include azo compounds such as azodicarbonamide, 2,2′-azobisisobutyronitrile and diazoaminobenzene, benzenesulfonylhydrazine, benzene-1,3-sulfonylhydrazide, diphenylsulfone- 3,3'-disulfonyl hydrazide, diphenyl oxide-4,4'-
Sulfonyl hydrazide compounds such as disulfonyl hydrazide, 4,4′-oxybis (benzenesulfonyl hydrazide), p-toluenesulfonyl hydrazide, N,
N'-dinitrosopentamethylene methylene teramine, N, N'-
Nitroso compounds such as dinitroso-N, N'-dimethylterephthalamide, terephthalazide, azide compounds such as p-tertiarybutylbenzazide, sodium bicarbonate,
Examples thereof include carbonates such as ammonium bicarbonate and ammonium carbonate, and among them, azo compounds such as azodicarbonamide are preferably used. The content of these foaming agents is usually 20 parts by weight or less, preferably 0.1 to 20 parts by weight, and more preferably 2 to 10 parts by weight per 100 parts by weight of the vinyl chloride resin.

Such an adhesive composition of the present invention further comprises a plasticizer, stabilizer, crosslinking agent, quaternary ammonium salt, polyvalent epoxy compound, epoxy resin curing agent, antistatic agent, metal soap, lubricant, pigment. , A foaming aid, a foaming inhibitor, a liquid coating agent, a release agent, and the like may be contained.

As the plasticizer, for example, diisodecyl phthalate, diisoundecyl phthalate and the like, dialkyl phthalates having an alkyl group having 9 to 11 carbon atoms, trioctyl trimellitate, tri-2-ethylhexyl trimellitate, tridecyl trimerate. Examples thereof include trialkyl trimellitates having an alkyl group having 7 to 11 carbon atoms such as mellitate, and the content thereof is vinyl chloride resin 100.
It is usually in the range of 40 to 120 parts by weight per part by weight.

Examples of the stabilizer include zinc, barium,
Compounds of metals such as sodium, potassium, calcium, lithium and tin, for example, carboxylic acid salts are mentioned, and among them, composite stabilizers thereof are preferably used. Also,
In addition to these stabilizers, hydrotalcite compounds, lithium-aluminum composite hydroxide salts, zinc oxide, barium oxide, calcium oxide, barium phosphate and the like may be used in combination. Further, a phenol-based, thioether-based, phosphorus-based antioxidant, a diketo compound-based, a salicylic acid-based, a benzophenone-based, a benzotriazole-based light stabilizer, an epoxy-based compound, or the like may be used in combination. The content of these stabilizers is usually in the range of 3 to 15 parts by weight per 100 parts by weight of the vinyl chloride resin.

As the crosslinking agent, for example, a homopolymer of a monomer having at least one active hydrogen, a copolymer of the monomer and another monomer copolymerizable therewith, a crosslinkable isocyanate compound, etc. Is mentioned.

As the monomer having at least one active hydrogen, for example, a monomer having a hydroxyl group such as hydroxyallylic acid and a monomer having an epoxy group such as glycidyl acrylic acid are copolymerized with these. Examples of other monomers to be obtained include vinyl chloride and alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate, and examples of copolymers thereof include vinyl chloride-hydroxyacrylic acid copolymer. Polymer, vinyl chloride-glycidyl acrylic acid copolymer, methyl acrylate-
Hydroxyacrylic acid copolymer, butyl acrylate-glycidyl acrylic acid copolymer and the like can be mentioned, and the content thereof is usually 40 parts by weight or less, preferably 0.5 to 40 parts by weight, per 100 parts by weight of the vinyl chloride resin. , And more preferably 1 to 20 parts by weight.

Examples of the crosslinkable isocyanate compound include compounds having an isocyanate group in the molecule such as diphenylmethane diisocyanate and toluylene diisocyanate, and compounds having a blocked isocyanate group in which the isocyanate group of the compound is blocked with phenol, cresol or the like. The content thereof is usually 10 parts by weight or less, preferably 0.1 to 10 parts by weight, and more preferably 0.5 per 100 parts by weight of the vinyl chloride resin.
Is in the range of 5 parts by weight.

The quaternary ammonium salt is represented by the general formula (2) (R) ₄ NX (2) (wherein R represents an alkyl group or an aralkyl group, X represents a halogen atom or an acid group, provided that R is R. They may be the same or different, and two Rs may combine with each other to form a heterocycle with N.)
In the quaternary ammonium salt, the alkyl group represented by R is, for example, a methyl group, an octyl group, or the like, and the aralkyl group is, for example, a benzyl group or the like, and two Rs are bonded to each other. Examples of the heterocycle in the case of forming a heterocycle with N include a pyridine ring. The halogen atom represented by X includes chlorine atom, bromine atom and the like, and the acid group includes sulfonic acid group, nitric acid group and the like. Examples of such a quaternary ammonium salt include trioctyl monomethyl ammonium chloride, N
-Methylpyridinium ammonium chloride and the like are contained, and the content thereof is usually 5 parts by weight or less, preferably 0.02 to 5 parts by weight or less per 100 parts by weight of the vinyl chloride resin.

The polyvalent epoxy compound is a compound having two or more epoxy groups in one molecule, and examples thereof include epoxidized soybean oil, epoxidized linseed oil and epoxy resin, the content of which is vinyl chloride. It is usually 30 parts by weight or less, preferably 1 to 30 parts by weight per 100 parts by weight of the resin.

Examples of the epoxy resin curing agent include the same compounds as commonly used as ordinary epoxy resin curing agents. Examples of such compounds include amine compounds, diamine compounds, polyamine compounds, polyamide compounds, amino acids, 2 Examples thereof include polybasic acids having the above carboxyl groups and acid anhydrides thereof. Among them, amino acids such as ε-aminocaproic acid, polybasic acids such as adipic acid, succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride,
An acid anhydride such as methylhexahydrophthalic anhydride and a condensate of polybasic acid corresponding to these acid anhydride and glycol are preferably used. Such epoxy resin curing agents are used alone or in admixture of two or more, and the content thereof is usually 10 parts by weight or less, preferably 0.2 to 1 per 100 parts by weight of the vinyl chloride resin.
It is in the range of 0 parts by weight.

Such an adhesive composition of the present invention may be a powder or a melt-kneaded product, and any of these may be a conventional method such as an open roll, a blender, a Banbury type mixer, It can be easily produced by a method using a kneader, a high-speed rotary mixer, or the like.

As a concrete manufacturing method, for example, the powder of the adhesive composition used in the powder molding described later uses a granular vinyl chloride resin and a fine vinyl chloride resin as the vinyl chloride resin, and It can be easily produced by using a polyolefin powder.

As the granular vinyl chloride resin, the same vinyl chloride resin as described above can be mentioned, and the particle size thereof is usually in the range of 100 to 150 μm, and usually, such as suspension polymerization method and bulk polymerization method. Manufactured by the method. The fine-grained vinyl chloride-based resin is for coating the granular vinyl chloride-based resin to prevent mutual adhesion of the powders of the composition, and examples thereof include the same vinyl chloride-based resin as described above. The diameter is usually in the range of 0.1 to 10 μm,
Usually, it is produced by an emulsion polymerization method, a micro polymerization method, or the like, and the amount used is a granular vinyl chloride resin 100.
It is usually in the range of 5 to 20 parts by weight with respect to parts by weight. As the polyolefin powder, the above-mentioned polyolefin-based resin or olefin-based thermoplastic elastomer powder is preferably used because the powder of the adhesive composition that can be easily powder-molded is easily obtained, and the particle size thereof is usually 0. .1-250
It is in the range of 0 μm, preferably 1 to 1800 μm.

When the powder of the adhesive composition is produced, for example, a fine grain vinyl chloride resin is blended with a granular vinyl chloride resin using a blending machine, and then a polyolefin powder is blended. The temperature when blending the fine-grained vinyl chloride resin is usually in the range of 40 to 80 ° C, and the temperature when blending the polyolefin powder is usually in the range of 20 to 60 ° C. At the time of blending, for example, a blender such as a blender or a high-speed rotary mixer is used, and among them, a blender capable of applying a shearing force such as a high-speed rotary mixer is preferable in that it can prevent mutual adhesion of the powders. Is carried out while removing heat from the jacket in order to prevent heat fusion of the powder due to heat generated by shearing.

When the powder of the adhesive composition of the present invention thus obtained contains the above-mentioned additive, such an additive is usually dry-blended in advance with a granular vinyl chloride resin. When used, it is preferably blended after dry blending, with or after cooling, prior to blending the finely divided vinyl chloride resin.

For dry blending, the same compounding machine as described above is usually used, and the temperature is usually 60 to 1
It is in the range of 30 ° C. When a cross-linking agent is used, it is usually added in the temperature range of 50 to 130 ° C.

Thus, the adhesive composition of the present invention is obtained. Such an adhesive composition can be easily molded and can be introduced into an adhesive molded article. Examples of the molding method of the adhesive composition include a powder molding method, an inflation method, an extrusion molding method, and the like. The molding temperature when the adhesive composition does not contain a foaming agent is usually 160 to 300 ° C., preferably It is in the range of 180 to 280 ° C., and usually 180 to 280 ° C., preferably 180 to 26 when a foaming agent is contained.
It is in the range of 0 ° C. The thickness of the adhesive molding thus obtained is not particularly limited, and is usually 0.3 to 2 mm, preferably 0.5 to 1 mm when the adhesive composition used does not contain a foaming agent. When it contains a foaming agent, it is usually 0.5 to 5 mm, preferably 1 to 3 mm.

For example, when molding by a powder molding method,
The powder of the adhesive composition may be used for powder molding. In powder molding, it may be operated as usual,
Specifically, for example, the powder of the adhesive composition is supplied onto the molding surface of a powder molding mold heated to a temperature sufficiently higher than the melting temperature of the powder, and the powders are mutually separated on the molding surface of the mold. The sheet-like material may be obtained by heat fusion, and when the adhesive composition used contains a foaming agent, the sheet-like material obtained by further heating may be foamed.

Here, the heating method of the mold is not particularly limited, and for example, a gas heating furnace method, an electric heating furnace method,
The heating medium oil circulation method, the heating medium oil or the immersion method in the heat fluidized sand, the high frequency induction heating method and the like can be mentioned. The heating temperature of the mold is the same as described above, and the molding time is not particularly limited. Instead, it is appropriately selected depending on the thickness and size of the intended adhesive molded body. Further, when the powder of the adhesive composition containing the foaming agent is used, the obtained sheet-like material is foamed by further heating, but the sheet-like material is not released from the mold during the foaming. It may be heated together with the mold, or may be heated after being released from the mold. The heating temperature at this time is the same as the above-mentioned molding temperature, and the heating and foaming time is not particularly limited, and is appropriately selected depending on the thickness of the target adhesive molded body and the expansion ratio.

The powder molding method is not particularly limited, and a usual method such as a fluidized-bed method, a powder firing method,
The electrostatic coating method, the powder spraying method, the powder rotational molding method, the powder slush molding method (see, for example, JP-A-58-132057, etc.) and the like can be mentioned. Among them, the powder slush molding method is preferably used.

For example, the powder slush molding method will be described in detail. A mold for powder molding is heated to a temperature sufficiently higher than the melting temperature of the adhesive composition, and the heated state is maintained. The opening and the opening of the container containing the powder of the adhesive composition are brought into intimate contact with each other to integrate them, and then the surface of the mold is molded by rotating or rotating it by 180 ° and swinging. The powder is attached to and melted in a sheet to form a sheet, and then the excess powder that has not adhered or melted may be collected in a container. When the adhesive composition used contains a foaming agent, it is obtained. The sheet-like material may be further heated to foam. Even when the adhesive composition does not contain a foaming agent, the thickness of the obtained adhesive molded article can be made more uniform by further heating the obtained sheet-like material, which is preferable.

Since the adhesive molded article thus obtained has excellent adhesiveness with vinyl chloride resin and polyolefin,
It can be used for forming an adhesive layer in the method described below as a method for producing a multilayer molded body including a vinyl chloride resin layer, an adhesive layer and a polyolefin layer.

The vinyl chloride resin layer is a layer made of the same vinyl chloride resin as described above or a mixture with another thermoplastic resin or a thermoplastic elastomer containing the vinyl chloride resin as a main component and containing almost no bubbles inside. Is. The vinyl chloride resin used in the vinyl chloride resin layer may be the same as or different from that used in the adhesive composition.

The vinyl chloride resin layer is formed from a vinyl chloride resin molded body, for example, in the production of a multilayer molded body described later. Here, the vinyl chloride resin molded article may be the same film or sheet as that which is usually used, but in terms of easily forming a complicated pattern on the surface thereof, the vinyl chloride resin molded article is A powder molded sheet obtained by powder molding a powder is preferably used.

As the vinyl chloride-based resin powder, for example, the same vinyl chloride-based resin as described above as the vinyl chloride-based resin and fine vinyl chloride-based resin are used, and the granular vinyl chloride-based resin is used in the same manner as described above. It can be easily produced by blending a fine-grained vinyl chloride resin with the resin. Such vinyl chloride-based resin may contain the same additives as described above, and such additives are usually preliminarily blended into the granular vinyl chloride-based resin by dry blending as described above.

In powder molding, for example, the above-mentioned vinyl chloride resin powder is heated to a temperature sufficiently higher than the melting temperature of the powder, and the molding surface may have a complicated pattern. The powder may be supplied onto the molding surface of the mold, and the powders may be heat-sealed to each other on the molding surface of the mold to obtain a sheet-like material, which is then cooled and then demolded.

Such a vinyl chloride resin molded article may be used alone in the production of a multilayer molded article described later, but the vinyl chloride resin layer and the adhesive layer in the obtained multilayer molded article are more firmly adhered to each other. From the viewpoint of obtaining, it is preferably used as a composite molded body that is integrally laminated in advance.

The method for producing such a composite molded article is not particularly limited, and it can be easily produced, for example, by superposing the adhesive molded article and the vinyl chloride resin molded article, heating and pressing. . The heating temperature is usually 15
The range of 0 to 280 ° C., preferably 180 to 250 ° C., the pressurizing pressure is usually 1 to 50 kg / cm ² , preferably 10 to
It is in the range of 30 kg / cm ² .

In the case where the composite molded body is formed by integrally laminating the vinyl chloride resin molded body manufactured by the powder molding method and the adhesive molded body manufactured by the powder molding method, the composite molded body may be, for example, bonded. It may be produced by a powder multi-layer molding method using a powder of a resin composition and a powder of a vinyl chloride resin composition.

Specifically, for example, a powder of vinyl chloride resin is supplied to the molding surface of a mold, which may have a complicated pattern, heated to a temperature sufficiently higher than the melting temperature of the powder, and the powder After heat-sealing each other to obtain a sheet-like material, the excess powder that has not been fused is removed, and then the powder of the adhesive composition is supplied onto the sheet-like material so that the powders are mutually joined. After heat-sealing to obtain a sheet-like product, the excess powder that has not been fused is removed to obtain a sheet-like product comprising two layers of a vinyl chloride resin layer and an adhesive composition layer. If the adhesive composition used contains a foaming agent, the obtained two-layer sheet material may be further heated to foam. Here, the heating temperature of the mold, the heating time, and the method of heating the mold when obtaining the two-layer sheet-like product are the same as those described above, and heating when the obtained two-layer sheet-like product is heated to foam. The foaming temperature, heating time and heating method are the same as described above.

More specifically, for example, a method for producing a composite molded body by the double slush molding method will be described. The mold for powder molding is heated to a temperature sufficiently higher than the melting temperature of the vinyl chloride resin, and the heating state is changed. While maintaining this, the opening of the mold and the opening of the container containing the powder of vinyl chloride resin are brought into close contact with each other to integrate them, and then they are rotated or rotated by 180 ° and then rocked. By adhering and melting the powder on the molding surface of the mold to form a sheet, the excess powder that did not adhere and melt is collected in a container and vinyl chloride-based on the molding surface of the mold. A resin layer is obtained, and then a mold for powder molding with the vinyl chloride resin layer held, and a container containing the powder of the adhesive composition are integrated in the same manner as above, and the same operation is performed as above. Adhesive composition powder The deposited over the vinyl chloride resin layer,
Melt to form a layer composed of the adhesive composition, and obtain a sheet-like material composed of two layers, a vinyl chloride resin layer and a layer composed of the adhesive composition, on the molding surface of the mold, and then adhere,
Excess powder that has not been melted may be collected in a container and the container may be removed. When the adhesive composition used contains a foaming agent, the obtained two-layer sheet-like product is further heated to foam. Good. Even when the adhesive composition does not contain a foaming agent, the thickness of the obtained adhesive layer can be made more uniform by further heating the obtained sheet-like material, which is preferable.

Examples of the polyolefin in the polyolefin layer, which is another layer constituting the multilayer molded article, include the same polyolefins as those in the adhesive composition of the present invention described above. Polyolefin resins such as copolymers with α-olefins such as propylene-ethylene copolymers and propylene-1-butene copolymers are preferably used. The melt flow rate (J
Temperature 190 ° C, load 2.1 according to IS K6730
It is a value measured at 6 kg and is hereinafter referred to as MFR. ) Is usually 0.1 to 300 g / 10 minutes, preferably 1 to 200
It is in the range of g / 10 minutes, and the polyolefin may contain various fillers such as inorganic fillers, various fillers such as glass fibers, pigments, lubricants, antistatic agents and stabilizers.

A multilayer molded article composed of such a vinyl chloride resin layer, an adhesive layer and a polyolefin layer has, for example, a vinyl chloride resin molded article on one surface side of the adhesive molded article.
Arrange the polyolefin melt on the other side,
It can be easily manufactured by a method of applying pressure and then cooling. Here, the polyolefin melt is a polyolefin in a state of being heated above its melting temperature,
The vinyl chloride resin molded body and the adhesive molded body are bonded by heat conduction and pressure from the polyolefin melt, but in that the vinyl chloride resin layer and the adhesive layer can be more firmly bonded, It is preferable to use these as the above-mentioned composite molded body that is integrally laminated in advance.

As a method for producing such a multilayer molded article, specifically, for example, a vinyl chloride resin molded article and an adhesive molded article are supplied between a pair of open male and female dies, and then the adhesive molded article and this are molded. After the polyolefin melt is supplied between one of the molds facing the mold, both molds may be clamped and cooled. Further, the above method may be a method of clamping both molds while supplying the polyolefin melt. The opening / closing direction of the mold is not particularly limited here, and may be the vertical direction or the horizontal direction depending on the mold clamping device.

The vinyl chloride resin molded product or the composite molded product to be used may be in the form of a film or a sheet, or may be preliminarily shaped and used according to the desired shape of the multilayer molded product. In the former case, the vinyl chloride resin molded product or the composite molded product may be directly supplied between the two molds, but in the latter case, it is preferable to hold it in one mold. When the resin molding or the composite molding is manufactured by the powder molding method or the powder multi-layer molding method, a mold for powder molding is formed on the molding surface of the vinyl chloride resin molding obtained by the powder molding method. It may be used as one of the molds in the production of the above-mentioned multilayer molded body while holding the body or the composite molded body. According to this method, since the vinyl chloride resin molded body or the composite molded body having a complicated pattern transferred to the surface thereof is supplied between the molds without being released from the mold, the pattern is hardly broken, The desired multilayer molded article can be manufactured.

The polyolefin melt can be supplied after closing both the molds, but since the vinyl chloride resin molded product is hardly displaced and the pattern is hardly broken, the male and female molds are clamped. It is preferable to feed before starting or simultaneously with mold clamping. The method for supplying the polyolefin melt is not particularly limited, and may be supplied, for example, from a melt passage provided in one of the molds facing the adhesive molding, or between the two molds opened. A method may be used in which a supply nose of the polyolefin melt is inserted to supply the polyolefin melt, and then the supply nose is retracted from the system.

As a pair of male and female molds, for example, one in which the outer peripheral surface of one mold and the inner peripheral surface of the other mold are slidable may be used. In this case, sliding of both molds is possible. By making the surface clearance approximately equal to the thickness of the vinyl chloride resin molded body, a multilayer molded body having an extra vinyl chloride resin layer at its end can be obtained. By folding the layer back to the back surface of the multilayer molded body, it is possible to obtain a multilayer molded body whose end is covered with the vinyl chloride resin layer.

Since the vinyl chloride resin layer and the polyolefin layer are firmly bonded and integrated through the adhesive layer, the multilayer molded article thus obtained can be used in various fields. For example, automotive parts include instrument panels, console boxes, armrests, headrests, door trims, rear panels, pillar trims, sun visors, luggage compartment trims, trunk lid trims, airbag storage boxes, seat buckles, headliners, glove boxes, steering wheels. Interior materials such as covers and ceiling materials, kicking plates,
It can be used for change lever boots, spoilers, side moldings, license plate housings, mirror housings, air dam skirts, mudguards, etc.
In the field of home appliances and office automation, it can be used as an exterior member for televisions, videos, washing machines, dryers, vacuum cleaners, coolers, air conditioners and the like. In the field of sports goods, for example, it is suitable for interior materials for boats, marine sports parts, etc., and in the field of construction and housing, for example, furniture,
It is suitable for desks, chairs, gates, doors, fences, wall decoration materials, ceiling decoration materials, indoor floor materials such as kitchens, toilets, and washrooms, and can also be used for industrial products and miscellaneous goods.

[0060]

The adhesive composition of the present invention can provide an adhesive layer capable of firmly bonding and integrating the vinyl chloride resin layer and the polyolefin layer.

[0061]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

[0062] Evaluation Method (1) complex dynamic viscosity η ^* complex dynamic viscosity η ^* is of the polyolefin used, dynamic analyzer RDS-770 manufactured by Rheometrics
The storage viscoelastic modulus G ′ and the loss viscoelastic modulus G ″ were measured by using a 0 type, a parallel mode, an applied strain of 5%, a sample temperature of 250 ° C., and an oscillation frequency ω of 1 radian / sec. ) Was calculated. (2) Average particle size of polyolefin and adhesive composition The particle size distribution was determined using a Tyler standard sieve, and the size corresponding to a cumulative percentage of 50% in the weight distribution curve was taken as the average particle size. (3) Evaluation method of multilayer molded body The obtained multilayer molded body was cut into a strip shape with a width of 20 mm,
Peeling temperature 20 ° C, peeling speed 200 mm / min, peeling angle 1
A peel test was performed at 80 °.

Reference Example 1 (Production of Vinyl Chloride Resin Powder) Granular vinyl chloride resin (Sumitomo Chemical Co., Sumit S
x-8G) 90 parts by weight were added, and the mixture was heated with stirring at a constant rotation speed, and when the temperature reached 80 ° C., 60 parts by weight of the trimellitic acid ester plasticizer, barium-zinc stabilizer 3
Parts by weight and 1 part by weight of pigment were added, and the mixture was further heated under stirring to carry out dry blending. Then, when the temperature reached 120 ° C., cooling was started, and when the temperature reached 50 ° C., fine-grained vinyl chloride resin (Sumitomo Px-Q manufactured by Sumitomo Chemical Co., Ltd.).
LT) (10 parts by weight) was added, and the mixture was stirred and uniformly dispersed to obtain a vinyl chloride resin powder. The average particle size was 150 μm.

Reference Example 2 (Production of powder of olefinic thermoplastic elastomer) E
PDM (Propylene unit content 28% by weight, iodine value 1
2) 25 parts by weight and mineral oil-based softener (made by Idemitsu Kosan Co., Ltd.,
Diana Process PW-380) 50 parts by weight of oil-extended EPDM consisting of 25 parts by weight, propylene-ethylene random copolymer resin (ethylene unit content 5% by weight, MFR =
90 g / 10 minutes) and 0.4 parts by weight of a cross-linking auxiliary (Sumitomo Chemical Co., Ltd., Sumifine BM, bismaleimide compound) were kneaded for 10 minutes using a Banbury type mixer,
Pellets were obtained using an extruder.

100 parts by weight of the pellets obtained above and an organic peroxide (manufactured by Sanken Kako Co., San Perox APO,
2,5-Dimethyl-2,5-di (t-butylperoxy) hexane) (0.1 part by weight)
Dynamic cross-linking was performed at 0 ° C. to obtain pellets of olefinic thermoplastic elastomer. By cooling the pellets to -100 ° C with liquid nitrogen and freeze-grinding,
Powder of olefin-based thermoplastic elastomer (complex dynamic viscosity η ^* = 5.2 × 10 ³ poise, average particle diameter 190μ
m) was obtained.

Example 1 (Production of Adhesive Composition Powder) 100 parts by weight of the vinyl chloride resin powder obtained in Reference Example 1 and 48 parts by weight of the olefinic thermoplastic elastomer powder obtained in Reference Example 2 were rapidly fed. By stirring at 25 ° C. using a rotary mixer,
A powder of the adhesive composition was obtained.

(Production of Composite Molded Product) The vinyl chloride resin powder obtained in Reference Example 1 was sprinkled on a nickel mold (15 × 15 cm) for powder molding which had been heated to 240 ° C. in advance, and after 5 seconds, an extra powder was obtained. Then, the powder of the adhesive composition obtained above is sprinkled immediately, the excess powder is shaken off after 20 seconds, then put in an oven at 280 ° C. for 90 seconds, cooled and demolded. A composite molded body in which the vinyl resin layer and the adhesive layer were integrally laminated was obtained. The thickness of the vinyl chloride resin layer of the obtained composite molded article was 0.8 mm, and the thickness of the adhesive layer was 0.6 mm.

(Production of Multilayer Molded Product) Polypropylene Resin Sheet (Block Polypropylene, MFR = 40 g / 1
0 minutes, talc content 15% by weight) on an aluminum plate,
By heating in an oven at 220 ° C. for 5 minutes, a sheet-shaped polypropylene resin melt was obtained. After placing the composite molded body obtained above on an aluminum plate with the vinyl chloride resin layer facing downward, the polypropylene resin melt obtained above was maintained in a heated state and held on an aluminum plate. As it was, it was inverted together with the aluminum plate, placed on the composite molded body, then pressurized at a pressure of 25 g / cm ² , depressurized, and cooled to obtain a multilayer molded body. Table 1 shows the evaluation results.

Example 2 Instead of the powder of the olefinic thermoplastic elastomer obtained in Reference Example 2, a powder of polyethylene (G40 manufactured by Sumitomo Seika Co., Ltd.)
1, complex dynamic viscosity η ^* = 9.3 × 10 ³ poise, average particle diameter 230 μm)
An adhesive composition was obtained in the same manner as in Example 1, a composite molded article was obtained in the same manner as in Example 1, and a multilayer molded article was obtained in the same manner as in Example 1. Table 1 shows the evaluation results.

Example 3 Instead of the olefinic thermoplastic elastomer powder obtained in Reference Example 2, polypropylene powder (D5 manufactured by Sumitomo Chemical Co., Ltd.) was used.
01, complex dynamic viscosity η ^* = 1.0 × 10 ⁵ poise, average particle size 240 μm) 48 parts by weight were used to obtain an adhesive composition in the same manner as in Example 1, except that Example 1 was used. A composite molded body was obtained in the same manner as described above, and a multilayer molded body was obtained in the same manner as in Example 1. Table 1 shows the evaluation results.

Comparative Example 1 A composite molded article was prepared in the same manner as in Example 1 except that the vinyl chloride resin powder obtained in Reference Example 1 was used in place of the adhesive composition powder obtained in Example 1. Then, the same operation as in Example 1 was carried out to obtain a multilayer molded body. Table 1 shows the evaluation results.

Comparative Example 2 Powder of olefinic thermoplastic elastomer obtained in Reference Example 2
Powder of olefinic thermoplastic elastomer instead of powder
(Sumitomo Chemical Co., Ltd., TPE820, complex dynamic viscosity η ^*=
1.3 x 10^FivePoise, average particle size 240μm) 48 layers
Adhesion was performed in the same manner as in Example 1 except that the amount part was used.
A composition was obtained and the same procedure as in Example 1 was conducted to give a composite molded article.
Then, the same operation as in Example 1 was carried out to obtain a multilayer molded body. Evaluation
Table 1 shows the results.

Comparative Example 3 Instead of the olefinic thermoplastic elastomer powder obtained in Reference Example 2, an olefinic thermoplastic elastomer powder (manufactured by Sumitomo Chemical Co., Ltd., TPE3681, complex dynamic viscosity η ^* =)
An adhesive composition was obtained in the same manner as in Example 1 except that 48 parts by weight of 2.6 × 10 ⁵ poise and average particle diameter of 230 μm) were used, and a composite molded body was obtained in the same manner as in Example 1. Then, the same operation as in Example 1 was carried out to obtain a multilayer molded body. Table 1 shows the evaluation results.

Comparative Example 4 Instead of the powder of the olefinic thermoplastic elastomer obtained in Reference Example 2, polyethylene powder (Showa Denko 555) was used.
1Z, complex dynamic viscosity η ^* = 2.3 × 10 ⁵ poise, average particle diameter 130 μm) 48 parts by weight except that the same procedure as in Example 1 was carried out to obtain an adhesive composition. A composite molded body was obtained in the same manner as described above, and a multilayer molded body was obtained in the same manner as in Example 1. Table 1 shows the evaluation results.

[0075]

[Table 1] Examples of polyolefin Complex dynamic viscosity η ^* Peel strength (poise) (g / 20 mm width) Example 1 5.2 × 10 ³ 650 Example 2 9.3 × 10 ³ 600 Example 3 1.0 × 10 ⁵ 750 Comparative Example 1-70 Comparative Example 2 1.3 × 10 ⁵ 200 Comparative Example 3 2.6 × 10 ⁵ 120 Comparative Example 4 2.3 × 10 ⁵ 120

Reference Example 3 Instead of the pigment, azodicarbonamide (A, manufactured by Otsuka Chemical Co., Ltd.
A vinyl chloride resin powder was obtained in the same manner as in Reference Example 1 except that 3 parts by weight of Z-S) and 1 part by weight of a foaming aid (zinc white) were used.

Example 4 (Production of Adhesive Composition Powder) 100 parts by weight of the vinyl chloride resin powder obtained in Reference Example 3 and 48 parts by weight of the olefinic thermoplastic elastomer powder obtained in Reference Example 2 were rapidly added. By stirring at 25 ° C. using a rotary mixer,
A powder of the adhesive composition was obtained.

(Production of Composite Molded Product and Multilayer Molded Product) Next, the same procedure as in Example 1 was carried out to obtain a composite molded product. The thickness of the vinyl chloride resin layer of the obtained composite molded body is 0.8 m.
m, the adhesive layer is foamed, and its thickness is 2.5 m.
It was m. Then, the same operation as in Example 1 was carried out to obtain a multilayer molded body. Table 2 shows the evaluation results.

Example 5 Instead of the powder of the olefinic thermoplastic elastomer obtained in Reference Example 2, a powder of the olefinic thermoplastic elastomer (complex dynamic viscosity η ^* = 1.4 × 10 ³ poise, average particle diameter 130 μm) A composite molded body was obtained in the same manner as in Example 4 except that 48 parts by weight was used, and a multilayer molded body was obtained in the same manner as in Example 4. Table 2 shows the evaluation results.

Example 6 Instead of the powder of the olefinic thermoplastic elastomer obtained in Reference Example 2, a powder of polyethylene (G40 manufactured by Sumitomo Seika Co., Ltd.)
1. Complex dynamic viscosity η ^* = 9.3 × 10 ³ poise, average particle size 230 μm) 48 parts by weight except that the same procedure as in Example 4 was carried out to obtain a composite molded body, and in the same manner as in Example 4. By operation, a multilayer molded body was obtained. Table 2 shows the evaluation results.

Example 7 Instead of the powder of the olefinic thermoplastic elastomer obtained in Reference Example 2, polypropylene powder (B2 manufactured by Sumitomo Seika Chemicals Co., Ltd.)
00, complex dynamic viscosity η ^* = 9.8 × 10 ⁴ poise, average particle size 220 μm) except that 48 parts by weight of Example 4 was used.
A composite molded body was obtained in the same manner as in 1. and a multilayer molded body was obtained in the same manner as in Example 4. Table 2 shows the evaluation results.

Comparative Example 5 A composite molded article was prepared in the same manner as in Example 4 except that the vinyl chloride resin powder obtained in Reference Example 3 was used in place of the adhesive composition powder obtained in Example 4. Then, the same operation as in Example 4 was carried out to obtain a multilayer molded article. Table 2 shows the evaluation results.

Comparative Example 6 Instead of the olefinic thermoplastic elastomer powder obtained in Reference Example 2, an olefinic thermoplastic elastomer powder (manufactured by Sumitomo Chemical Co., Ltd., TPE3681, complex dynamic viscosity η ^* =)
A composite molded body was obtained in the same manner as in Example 4 except that 48 parts by weight of 2.6 × 10 ⁵ poise and an average particle diameter of 230 μm) were used, and a multilayer molded body was obtained in the same manner as in Example 4. .
Table 2 shows the evaluation results.

Comparative Example 7 Polyethylene powder (555, manufactured by Showa Denko KK) was used in place of the powder of the olefinic thermoplastic elastomer obtained in Reference Example 2.
Example 4 except that 48 parts by weight of 1 Z, complex dynamic viscosity η ^* = 2.3 × 10 ⁵ poise, average particle diameter 130 μm) were used.
A composite molded body was obtained in the same manner as in 1. and a multilayer molded body was obtained in the same manner as in Example 4. Table 2 shows the evaluation results.

Comparative Example 8 Polyethylene powder (3001Y, manufactured by Union Polymer Co., complex dynamic viscosity η ^* = 3.0 × 10 ⁵ poise, average particle size) was used in place of the olefinic thermoplastic elastomer powder obtained in Reference Example 2. A composite molded body was obtained in the same manner as in Example 4 except that 48 parts by weight (diameter 120 μm) was used.
The same procedure was followed to obtain a multilayer molded body. Table 2 shows the evaluation results.

[0086]

[Table 2] Examples of polyolefin Complex dynamic viscosity η ^* Peel strength (poise) (g / 20 mm width) Example 4 6.4 x 10 ³ 1420 Example 5 1.4 x 10 ³ 3200 Example 6 9.3 × 10 ³ 600 Example 7 9.8 × 10 ⁴ 1200 Comparative Example 5-90 Comparative Example 6 2.6 × 10 ⁵ 320 Comparative Example 7 2.3 × 10 ⁵ 180 Comparative Example 8 3.0 × 10 ⁵ 150

Examples 8-11, Comparative Examples 9-10 Powders of olefinic thermoplastic elastomer (complex dynamic viscosity
Degree η^*= 1.4 × 10 ³Poise, average particle size 180μ
Except that the amount used in m) is as shown in Table 3 below.
The same operation as in Example 5 was carried out to obtain a composite molded body, which was the same as in Example 4.
The same procedure was followed to obtain a multilayer molded product. The evaluation results are shown in Table 3.
You

[0088]

Table 3 Examples of Polyolefin Usage Amount Peeling strength (parts by weight) (g / 20 mm width) Comparative Example 9 8 300 Example 8 16 520 Example 9 80 2000 2000 Example 10 160 700 Example 11 320 500 Comparative Example 10 480 180

Example 12 Polyethylene powder (B20 manufactured by Sumitomo Seika Chemicals Co., Ltd.) was used in place of the powder of the olefinic thermoplastic elastomer obtained in Reference Example 2.
0, complex dynamic viscosity η ^* = 9.8 × 10 ⁴ poise, average particle size 400 μm) except that 48 parts by weight were used, a composite molded body was obtained in the same manner as in Example 4 and in the same manner as in Example 4. By operation, a multilayer molded body was obtained. Table 4 shows the evaluation results.

Example 13 Polyethylene powder (B20 manufactured by Sumitomo Seika Chemicals Co., Ltd.) was used in place of the powder of the olefinic thermoplastic elastomer obtained in Reference Example 2.
0, complex dynamic viscosity η ^* = 9.8 × 10 ⁴ poise, average particle size 1500 μm) Example 4 except that 48 parts by weight were used.
A composite molded body was obtained in the same manner as in 1. and a multilayer molded body was obtained in the same manner as in Example 4. Table 4 shows the evaluation results.

[0091]

[Table 4] Examples of polyolefin powder Average particle size Peel strength (μm) (g / 20 mm width) Example 12 400 1200 Example 13 1500 750

Example 14 As shown in FIG. 1, a vinyl chloride resin powder (3) obtained in the same manner as in Reference Example 1 was placed in a container (1) and heated at 240 ° C.
A powder-molding-like mold (2) having a leather grain pattern on the heated molding surface is placed with its opening aligned with the opening of the container (1), and is attached around both openings. The frames were brought into close contact with each other and fixed to each other to be integrated.
Immediately, the integrated container and the mold were rotated once by a uniaxial rotating device (not shown) for 5 seconds so that the powder composition (3) was placed on the molding surface of the powder molding mold (2). After supplying, adhering and melting, and stopping the rotation, the extra powder that was not adhered and melted was collected in the container (1). Then
Immediately, a container containing the powder of the adhesive composition obtained in the same manner as in Example 4 was attached, the container and the mold were integrated, and this was rotated twice for 15 seconds by a uniaxial rotating device to perform adhesion. The powder of the sexual composition was adhered and melted, and then the excess powder which was not adhered and melted was collected in a container.

Next, the mold is removed from the container, the mold is heated at 240 ° C. for 2 minutes and then cooled to obtain a composite molded article (4) comprising a vinyl chloride resin layer (5) and an adhesive layer (6). Was obtained (Fig. 2). Next, as shown in FIG. 3, the powder molding die while holding the composite molded body (4) was integrated with the mold base (7) to form a female die (9). Then, while clamping the female mold (9) and the male mold (8),
Polypropylene resin heated to 190 ° C through the melt passage (10) (Sumitomo Noblen AX5 manufactured by Sumitomo Chemical Co., Ltd.)
68, MFR = 65 g / 10 min) was supplied, and then both dies (8, 9) were clamped at a molding surface pressure of 50 kg / cm ² (FIG. 4).

After cooling, both molds are opened and released to obtain a multilayer molded product (13) comprising a vinyl chloride resin layer (5), an adhesive layer (6) and a polypropylene resin layer (12). It was FIG. 5 shows a cross-sectional view of the obtained multilayer molded body. The obtained multilayer molded article had a vinyl chloride resin layer thickness of 0.8 mm, an adhesive layer thickness of 2.1 mm, and a polypropylene resin layer thickness of 2.3 mm, and a skin grain pattern was transferred to its surface. It was a multi-layer molded product having a good appearance. In addition, this multi-layer molded article had a large adhesiveness between the vinyl chloride resin layer and the polypropylene resin layer, and the peel strength was 2600 g / 20 mm width.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a container containing a vinyl chloride resin powder and a powder molding die.

FIG. 2 is a cross-sectional view of a powder molding die holding a composite molded body.

FIG. 3 is a cross-sectional view showing a state in which a polypropylene resin melt is being supplied after a powder molding die holding a composite molded body is integrated with a mold base.

FIG. 4 is a cross-sectional view showing a state where the male and female dies are clamped together.

FIG. 5 is a cross-sectional view of a multilayer molded body including a vinyl chloride resin layer, an adhesive layer, and a polyolefin layer.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Container 2 ... Powder molding die 3 ... Vinyl chloride resin powder 4 ... Composite molded body 5 ... Vinyl chloride resin layer 6 ... Adhesive layer 7 ... Mold base 8 ... Female mold 9 ... Male mold 10 ... Melt passage 11 ... Polypropylene resin melt 12 ... Polypropylene resin layer 13 ... Multi-layer molded body

[Procedure amendment]

[Submission date] March 5, 1996

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0089

[Correction method] Change

[Correction content]

[0089] Example 12 Reference Example polypropylene powder in place of the powder of the olefin-based thermoplastic elastomer obtained in 2 (manufactured by Sumitomo Seika Chemicals Co., Ltd., B2
00, complex dynamic viscosity η ^* = 9.8 × 10 ⁴ poise, average particle diameter 400 μm) Example 4 except that 48 parts by weight are used.
A composite molded body was obtained in the same manner as in 1. and a multilayer molded body was obtained in the same manner as in Example 4. Table 4 shows the evaluation results.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0090

[Correction method] Change

[Correction content]

[0090] Example 13 Reference Example 2 in place of the powder of the olefin-based thermoplastic elastomer obtained poly propylene powder (manufactured by Sumitomo Seika Chemicals Co., Ltd., B2
00, complex dynamic viscosity η ^* = 9.8 × 10 ⁴ poise, average particle size 1500 μm) except that 48 parts by weight are used, a composite molded body is obtained in the same manner as in Example 4, and in the same manner as in Example 4. By operation, a multilayer molded body was obtained. Table 4 shows the evaluation results.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B32B 27/30 101 B32B 27/30 101 27/32 27/32 C C08L 23/00 LCJ C08L 23 / 00 LCJ 27/06 LEP 27/06 LEP C09J 123/00 JBX C09J 123/00 JBX // B29K 23:00 B29L 9:00 (72) Inventor Toshiro Igarashi 2-10-1 Tsukahara, Takatsuki, Osaka Sumitomo Chemical Gaku Kogyo Co., Ltd. (72) Inventor Satoshi Funakoshi 2-10-1 Tsukahara, Takatsuki City, Osaka Sumitomo Chemical Gaku Kogyo Co., Ltd.

Claims (13)

[Claims] 1. An adhesive composition comprising 10 to 350 parts by weight of a polyolefin having a complex dynamic viscosity η ^* of 1.2 × 10 ⁵ poise or less per 100 parts by weight of a vinyl chloride resin. 2. A composition comprising 10 to 350 parts by weight of a polyolefin having a complex dynamic viscosity η ^* of 1.2 × 10 ⁵ poise or less and 20 parts by weight or less of a foaming agent per 100 parts by weight of a vinyl chloride resin. A characteristic adhesive composition. 3. The adhesive composition according to claim 1, wherein the polyolefin is an olefinic thermoplastic elastomer. 4. An adhesive molded article obtained by molding the adhesive composition according to claim 1 or 2. 5. An adhesive molded article obtained by powder-molding the powder of the adhesive composition according to claim 1 or 2. 6. A composite molded body comprising a vinyl chloride resin molded body integrally laminated on the adhesive molded body according to claim 4. 7. A composite molded article, characterized in that the adhesive molded article according to claim 5 is integrally laminated with a powder molded sheet obtained by powder molding a powder of vinyl chloride resin. 8. A vinyl chloride resin powder is supplied onto the molding surface of a mold heated to a melting temperature of the powder or higher, and the powders are heat-sealed to each other, and then the excess is not fused. 2. A vinyl chloride resin layer is obtained by removing the powder of claim 1, and then the vinyl chloride resin layer is obtained.
The powder of the adhesive composition according to claim 1 is supplied, and the powder is heat-fused to each other on the vinyl chloride resin layer to obtain a layer of the adhesive composition. A method for producing the composite molded article according to item 1. 9. A vinyl chloride resin powder is supplied onto a molding surface of a mold heated to a melting temperature of the powder or higher, and the powders are heat-fused to each other, and then the non-fused excess is added. The vinyl chloride resin layer is obtained by removing the powder of claim 1, and then the vinyl chloride resin layer is obtained.
The powder of the adhesive composition described in 1. is supplied, and the powder is heat-fused to each other on the vinyl chloride resin layer to obtain a layer made of the adhesive composition, followed by heating and foaming. The method for producing a composite molded body according to claim 7, wherein. 10. A multilayer molded article comprising a vinyl chloride resin layer, an adhesive layer and a polyolefin layer, wherein the adhesive layer is an adhesive layer formed by molding the adhesive composition according to claim 1 or 2. A multi-layer molded article characterized by being present. 11. A vinyl chloride resin molded body is arranged on one surface side of the adhesive molded body according to claim 4, and a polyolefin melt is arranged on the other surface side thereof, followed by pressurizing and cooling. The method for producing a multilayer molded article according to claim 10, which is characterized in that. 12. A vinyl chloride resin molded product and the adhesive molded product according to claim 4 are supplied between a pair of open male and female dies, and then the adhesive molded product and one of the opposing ones are provided. The method for producing a multilayer molded product according to claim 10, wherein both molds are clamped and cooled after or after supplying the polyolefin melt with the mold. 13. The method for producing a multilayer molded product according to claim 11 or 12, wherein the vinyl chloride resin molded product and the adhesive molded product are the composite molded product according to claim 5. .