JP2016002680A - Foaming polyvinyl chloride laminate member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate member that has a foam layer directly placed on a polyvinyl chloride resin sheet.SOLUTION: A foaming polyvinyl chloride laminate member comprises a polyvinyl chloride resin sheet layer, and a foaming polyvinyl chloride layer directly placed on at least one side of the polyvinyl chloride resin sheet. Polyvinyl chloride constituting the foaming polyvinyl chloride layer has a K value of 55-90.

Description

  The present invention relates to a foamed polyvinyl chloride laminated member, and more particularly to a laminated member in which a foamed polyvinyl chloride layer is directly laminated on a polyvinyl chloride resin sheet.

  Foamed members having a foamed resin layer on at least one surface of a polyvinyl chloride sheet or a polyolefin-based sheet are widely used for automobile interior materials, building materials, and the like. As shown in FIG. 2A, the foamed member is usually configured by laminating a foamed resin layer 21 on a base material 22 with an adhesive layer 23 interposed therebetween. For example, a laminated member for an automobile interior ceiling in which polyurethane foam is laminated on a mica-containing polypropylene sheet via a hot-melt adhesive layer is known (Patent Document 1). As shown in FIG. 2 (b), the foamed member is produced by forming the foamed layer in a process different from the molding of the sheet layer, and laminating the foamed layer after applying the adhesive layer to the sheet layer. Not only is the process cumbersome, but the manufacturing cost is high.

  On the other hand, what laminated | stacked the foaming layer without interposing an adhesive bond layer is also proposed. For example, a vibration-damping and sound-proofing sheet for vehicles (Patent Document 2) in which a vibration-damping layer forming agent made of a rubber-based adhesive compound and a sound-proofing layer-forming material made of a foamed rubber compound are bonded and laminated. There is a foam composite (Patent Document 3) including a foam layer that adheres to an adherend.

JP 2006-82456 A JP 61-104836 A JP 2002-30262 A

  However, although the foamed rubber composition in Patent Document 2 adheres to the rubber-based adhesive compound, it is difficult to adhere to the polyvinyl chloride resin. Moreover, although the ethylene-vinyl acetate copolymer resin in Patent Document 3 is excellent in adhesiveness, it has problems in terms of physical properties such as chemical resistance and heat resistance.

  Therefore, an object of the present invention is to provide a laminated member in which a foam layer is laminated directly on a polyvinyl chloride resin sheet, that is, without an adhesive layer.

A first embodiment of the present invention includes a polyvinyl chloride resin sheet layer, and a foamed polyvinyl chloride layer directly laminated on at least one surface of the polyvinyl chloride resin sheet. It is a foamed polyvinyl chloride laminated member whose K value of the polyvinyl chloride to comprise is 55-90.
It is preferable that K value of the polyvinyl chloride which comprises the said foaming polyvinyl chloride layer is 60-80.
The second embodiment of the present invention is a foamed polyvinyl chloride laminated member further comprising an adhesive layer laminated on the foamed polyvinyl chloride layer.
Moreover, this invention relates to the assembled wire for motor vehicles containing the foamed polyvinyl chloride laminated member in any one of the said.
Furthermore, this invention is a method of making the foamed polyvinyl chloride laminated member including the following processes.
(1) a step of directly applying a foamable polyvinyl chloride composition on one surface of a polyvinyl chloride resin sheet to obtain a laminate; and (2) heating the laminate obtained in step (1). Forming a foamed polyvinyl chloride layer from the foamable polyvinyl chloride composition,
The foamable polyvinyl chloride composition is a polyvinyl chloride having a K value of 55 to 90, a plasticizer of 50 to 150 parts by mass, and a filler of 10 to 30 parts by mass with respect to 100 parts by mass of the polyvinyl chloride. 1 to 10 parts by weight of stabilizer and 10 to 20 parts by weight of blowing agent.

  The foamed polyvinyl chloride laminated member of the present invention does not need to form an adhesive layer, and can be produced by a simple process and at a low cost.

Fig.1 (a) is sectional drawing which shows one embodiment of the foamed polyvinyl chloride laminated member of this invention, FIG.1 (b) is process drawing which shows the manufacturing method. FIG. 2A is a cross-sectional view of an example of a conventional foamed resin laminated member, and FIG. 2B is a process diagram illustrating the manufacturing method thereof. It is sectional drawing which shows the 2nd embodiment of the foamed polyvinyl chloride laminated member of this invention.

  The foamed polyvinyl chloride laminated member of the present invention is directly laminated on at least one surface of a polyvinyl chloride resin sheet layer 2 (hereinafter sometimes referred to as “sheet layer 2”) as shown in FIG. A foamed polyvinyl chloride layer 1 (hereinafter sometimes referred to as “foam layer 1”) is provided. In the present invention, “direct lamination” means that lamination is performed without using an adhesive layer.

  The polyvinyl chloride has a K value of 55 to 90, preferably 60 to 80. The K value can be determined according to Japanese Industrial Standard (JIS) K 7367 and is a measure of the average degree of polymerization. Polyvinyl chloride having a K value within the above range can achieve both adhesiveness to the sheet layer 2 and foamability. Polyvinyl chloride less than the lower limit value has a low expansion ratio and may not have sufficient adhesion to the sheet layer 2. On the other hand, polyvinyl chloride having a K value less than the upper limit also has a low expansion ratio.

  The polyvinyl chloride constituting the foam layer 1 may be polyvinyl chloride obtained by any of bulk polymerization, suspension polymerization, and emulsion polymerization. Polyvinyl chloride obtained by suspension polymerization or emulsion polymerization is preferably used in that it can be paste-formed and heat-foamed.

  The expansion ratio of the foam layer 1 is preferably 1.2 or more, and more preferably 2 or more. It is preferable that it is 5-15 for the protective material use of the assembled wire for motor vehicles mentioned later.

  The resin constituting the sheet layer 2 is not limited to a polyvinyl chloride homopolymer, but is a copolymer mainly composed of vinyl chloride, such as vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-ethylene copolymer. Resin, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer , Vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, or vinyl chloride-acrylonitrile copolymer can be used. Moreover, it may be either hard or soft depending on the use, and may contain commonly used additives such as plasticizers, antioxidants, fillers and the like.

  FIG. 3 is a cross-sectional view showing a second embodiment of the expanded polyvinyl chloride laminated member of the present invention, and elements corresponding to the first embodiment are referred to by corresponding numerals. In the figure, an adhesive layer 34 is laminated on a foamed polyvinyl chloride layer 31, that is, on the surface opposite to the sheet layer 32. Furthermore, a peelable sheet made of paper or the like that is peeled off during use may be provided on the pressure-sensitive adhesive layer 34.

    There is no restriction | limiting in particular as an adhesive which comprises this adhesive layer 34, Usually used adhesives, such as an acrylic type, a urethane type, a silicone type, a polyester type, and a rubber type, are included. Preferably, an acrylic adhesive or a rubber adhesive is used.

  The foamed polyvinyl chloride laminated member of the present invention is useful for building materials, automobile interior materials, sound insulation materials, and the like, and is particularly suitable as a protective material for automobile assembled wires. In the case of a typical automotive assembled wire use, the sheet layer is made of a polyvinyl chloride resin having a thickness of 0.1 to 0.5 mm, the foam layer is 1 to 5 mm in thickness, and the adhesive layer is a rubber having a thickness of 10 to 40 μm. It consists of an adhesive.

Next, the manufacturing method of the foamed polyvinyl chloride laminated member of this invention is demonstrated.
The foamed polyvinyl chloride laminated member of the first embodiment can be produced by the method shown in FIG. First, a polyvinyl chloride resin sheet is formed. The molding can be performed according to a conventional method such as extrusion molding or calendar molding.

  Next, a foamable polyvinyl chloride composition for forming a foamed polyvinyl chloride layer is directly applied on at least one surface of the polyvinyl chloride resin sheet to obtain a laminate. As the application method, a roll coater method, a die coating method, a wire bar coating method, a knife coating method, or the like can be used.

  Next, the obtained laminate is heated to foam the foamable polyvinyl chloride composition to form a foamed polyvinyl chloride layer. The heating condition varies depending on the foaming agent contained in the foamable polyvinyl chloride composition, but is typically about 1 to 3 minutes at a temperature of 150 to 230 ° C.

  According to the second embodiment, when the pressure-sensitive adhesive layer is provided, the pressure-sensitive adhesive layer is applied after the foam layer is formed. The application method is not limited, and a roll coater method, a die coating method, a wire bar coating method, a knife coating method, or the like can be used. After the application, the adhesive is subjected to a curing treatment or the like as necessary. A protective peelable sheet may be stuck on the obtained pressure-sensitive adhesive layer. Alternatively, the pressure-sensitive adhesive layer may be transferred by separately applying a pressure-sensitive adhesive on the peelable sheet and then sticking it on the foamed layer.

  As the peelable sheet, for example, paper such as glassine paper, coated paper, laminated paper, or a plastic film coated with a release agent such as a silicone resin can be used.

  The foamable polyvinyl chloride composition (hereinafter sometimes referred to as “vinyl chloride composition”) is added to the above-mentioned polyvinyl chloride having a K value of 55 to 90, in addition to 100 parts by mass of the polyvinyl chloride. 50 to 150 parts by weight of plasticizer, 10 to 30 parts by weight of filler, 1 to 10 parts by weight of stabilizer, and 10 to 20 parts by weight of foaming agent. The vinyl chloride composition may be a liquid or a paste having a viscosity suitable for application on the sheet layer, and is preferably a paste.

  Examples of the plasticizer include di-n-butyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate, diisooctyl phthalate, diisononyl phthalate, octyldecyl phthalate, diisodecyl phthalate, and phthalic acid. Phthalic acid plasticizers such as butylbenzyl and di-2-ethylhexyl isophthalate; di-2-ethylhexyl adipate, diisodecyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate, etc. Fatty acid ester plasticizers; phosphate ester plasticizers such as tributyl phosphate, tri-2-ethylhexyl phosphate, tricresyl phosphate, trixyl phosphate; chlorinated plasticizers such as chlorinated paraffin and chlorinated fatty acid ester; From epoxy plasticizer and polyester plasticizer It can be used at least one barrel. Preferably diisononyl phthalate is used.

  The compounding amount of the plasticizer is 50 to 150 parts by mass, preferably 60 to 120 parts by mass with respect to 100 parts by mass of polyvinyl chloride.

  As the filler, inorganic fillers such as calcium carbonate, talc, kaolin clay, synthetic silicic acid, quartz powder, calcium sulfate, calcium sulfite, calcium hydroxide, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium oxide, asbestos , Silica, glass fiber, mineral fiber; organic fillers such as wood powder, coconut shell powder, pulp powder, crosslinked polyester particles, polystyrene particles, carbon fibers, and natural fibers can be used. Preferably, calcium carbonate is used.

  The blending amount of the filler is 10 to 30 parts by mass, preferably 15 to 25 parts by mass with respect to 100 parts by mass of polyvinyl chloride.

  Examples of the stabilizer include carboxylic acid metal salts such as calcium stearate and barium stearate; organotin stabilizers such as dibutyltin laurate and dioctyltin maleate; lead stabilizers such as lead sulfate and lead phosphite; alkyl At least one selected from non-metallic stabilizers such as aryl phosphite, dibenzoylmethane, pentaerythritol and the like can be used. Preferably, calcium / zinc based carboxylates are used.

  The blending amount of the stabilizer is 1 to 10 parts by mass, preferably 2 to 5 parts by mass with respect to 100 parts by mass of polyvinyl chloride.

  As the foaming agent, a pyrolytic foaming agent is preferably used. Examples of the pyrolytic organic foaming agent include inorganic foaming agents such as sodium bicarbonate, ammonium bicarbonate, ammonium carbonate, sodium borohydride, calcium azide; organic foaming agents such as azodicarbonamide, azobisisobutyronitrile. , Barium azodicarboxylate, N, N′-dinitropentamethylenetetramine, p, p′-oxybis (benzenesulfonyl hydrazide, p-toluenesulfonyl hydrazide, p-toluenesulfonyl semicarbazide can be used. Preferably, azodicarbonamide is used.

  The blending amount of the foaming agent is 10 to 20 parts by mass, preferably 14 to 18 parts by mass with respect to 100 parts by mass of polyvinyl chloride.

  The vinyl chloride composition may further contain a foaming aid. Examples of the foaming aid include metal oxides such as zinc oxide, lead oxide, cadmium oxide, magnesium oxide, calcium stearate, barium stearate, and zinc acetate; urea foaming aid, salicylic acid foaming aid, benzoic acid At least one selected from a foaming aid, glycerin, and diethylene glycol can be used. Preferably, zinc oxide is used.

  The blending amount of the foaming aid is 2 to 20 parts by mass, preferably 3 to 18 parts by mass with respect to 100 parts by mass of polyvinyl chloride.

  In addition to the above components, the vinyl chloride composition may contain a solvent, a flame retardant, an antioxidant, a weathering agent, a lubricant, a crosslinking agent, a dispersion accelerator, and the like in amounts that do not impair the object of the present invention. .

  The vinyl chloride composition can be produced by mixing the above-mentioned components and, if desired, various additives according to a conventional method. As a mixing means, a Henschel mixer, a kneader, a Banbury mixer, a roll mill, or the like can be used.

  Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

[Examples 1 to 9, Comparative Examples 1 and 2]
A vinyl chloride composition was obtained by mixing the components (parts by mass) shown in Table 1 with a dissolver mixer. Details of each component in Table 1 are as follows.
Polyvinyl chloride: PSL-675 (trade name), manufactured by Kaneka Corporation, K value 60
Polyvinyl chloride: PCH-175 (trade name), manufactured by Kaneka Corporation, K value 76
Polyvinyl chloride: PCH-843 (trade name), manufactured by Kaneka Corporation, K value 80
Polyvinyl chloride (for comparison): TH-500 (trade name), manufactured by Taiyo PVC Co., Ltd., K value 52
Polyvinyl resin (for comparison): TH-3800 (trade name), manufactured by Taiyo PVC Co., Ltd., K value 93
Plasticizer: Diisononyl phthalate
Filler: Calcium carbonate Stabilizer: Adeka Stub (trade name)
Foaming agent: Azodicarbonamide Foaming aid 1: Zinc oxide Foaming aid 2: Urea

  Each vinyl chloride composition is applied to a thickness of about 0.3 mm on one surface of a polyvinyl chloride sheet (manufactured by Yazaki Parts Co., Ltd.) having a thickness of 0.2 mm using an applicator to obtain a laminate. It was. Each laminate was placed in an oven at the temperature shown in Table 1 for 1.5 minutes to foam each vinyl chloride composition. From the ratio of the thickness before and after foaming, the foaming ratio shown in Table 1 was obtained. Also, by evaluating whether the foamed layer and the sheet layer can be peeled by hand, the adhesiveness of the foamed layer to the polyvinyl chloride sheet layer was evaluated. X.

  As shown in Table 1, all the examples using polyvinyl chloride having a predetermined K value were able to obtain a foamed layer exhibiting good adhesion to the sheet layer and good foaming ratio. On the other hand, in the comparative example using polyvinyl chloride lacking this requirement, it was in an unfoamed state as a whole, the expansion ratio could not be measured, and the adhesion to the polyvinyl chloride sheet was poor.

  The foamed polyvinyl chloride laminated member of the present invention can be produced by a simple process. The foamed member is useful as a protective material for automobile assembled wires.

1, 31 Foamed polyvinyl chloride layer 2, 32 Polyvinyl chloride resin sheet 34 Adhesive layer

Claims (5)

  A polyvinyl chloride resin sheet layer, and a foamed polyvinyl chloride layer directly laminated on at least one surface of the polyvinyl chloride resin sheet, and the polyvinyl chloride constituting the foamed polyvinyl chloride layer has a K value of 55 A foamed polyvinyl chloride laminate member of ~ 90.   The foamed polyvinyl chloride laminate member according to claim 1, wherein the polyvinyl chloride constituting the foamed polyvinyl chloride layer has a K value of 60 to 80.   The foamed polyvinyl chloride laminated member according to claim 1, further comprising an adhesive layer laminated on the foamed polyvinyl chloride layer.   The assembled wire for motor vehicles containing the foamed polyvinyl chloride laminated member of any one of Claims 1-3. (1) a step of directly applying a foamable polyvinyl chloride composition on one surface of a polyvinyl chloride resin sheet to obtain a laminate; and (2) heating the laminate obtained in step (1). Forming a foamed polyvinyl chloride layer from the foamable polyvinyl chloride composition,
The foamable polyvinyl chloride composition is a polyvinyl chloride having a K value of 55 to 90, a plasticizer of 50 to 150 parts by mass, and a filler of 10 to 30 parts by mass with respect to 100 parts by mass of the polyvinyl chloride. A method of making a foamed polyvinyl chloride laminate comprising 1 to 10 parts by weight stabilizer and 10 to 20 parts by weight foaming agent.

Images