WO2016139959A1 - 粉体成形用塩化ビニル樹脂組成物、塩化ビニル樹脂成形体及び積層体 - Google Patents
粉体成形用塩化ビニル樹脂組成物、塩化ビニル樹脂成形体及び積層体 Download PDFInfo
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- WO2016139959A1 WO2016139959A1 PCT/JP2016/001210 JP2016001210W WO2016139959A1 WO 2016139959 A1 WO2016139959 A1 WO 2016139959A1 JP 2016001210 W JP2016001210 W JP 2016001210W WO 2016139959 A1 WO2016139959 A1 WO 2016139959A1
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- chloride resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/18—Slush casting, i.e. pouring moulding material into a hollow mould with excess material being poured off
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/02—Low molecular weight, e.g. <100,000 Da.
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Definitions
- the present invention provides a vinyl chloride resin composition for powder molding that gives a molded article with low fluffing properties, a vinyl chloride resin molded article obtained by powder molding the vinyl chloride resin composition for powder molding, and the vinyl chloride.
- the present invention relates to a laminate having a resin molded body and a foamed polyurethane molded body.
- An automobile instrument panel has a structure in which a polyurethane foam layer is provided between a skin made of a soft resin and a base material.
- a resin composition comprising a vinyl chloride resin, which is a kind of soft resin, and silicone oil has been studied (for example, see Patent Document 1). And since the resin composition described in Patent Document 1 has a smooth feel, the vinyl chloride resin molded body formed by molding the resin composition is useful for the skin of an automobile instrument panel. is there. On the other hand, the vinyl chloride resin molded article has a problem that the plasticizer contained in the material is transferred to the surface due to the influence of heat, light, etc., and the soft feeling is lost.
- thermoplastic polyurethane instead of vinyl chloride resin
- a polyurethane resin composition for powder molding containing powdered thermoplastic polyurethane and a hydroxyl group-modified and / or (meth) acryloxy-modified silicone oil has been studied (for example, see Patent Document 2).
- the problem to be solved by the present invention is to provide a vinyl chloride resin composition for powder molding that gives a molded article having low fluffing properties.
- the inventor of the present invention as a result of intensive studies to solve the above-mentioned problems, found that a vinyl chloride resin composition for powder molding comprising a specific amount of silicone oil having a specific viscosity blended in a vinyl chloride resin is the above-mentioned problem. Has been found to solve the problem, and the present invention has been completed.
- the vinyl chloride resin composition for powder molding of the present invention comprises (a) a vinyl chloride resin, and (b) a silicone oil having a viscosity of 10 cs or more and 200 ⁇ 10 4 cs or less, and (b) the viscosity is 10 cs or more. Content of the silicone oil which is 200 * 10 ⁇ 4 > cs or less is 0.1 to 10 mass parts per 100 mass parts of said (a) vinyl chloride resin.
- “viscosity” can be measured using an Ubbelohde viscometer according to ASTM D 445-46T.
- the (a) vinyl chloride resin is preferably (a1) vinyl chloride resin particles having an average degree of polymerization of 800 or more and 5000 or less, and (a2 ) Composed of vinyl chloride resin fine particles having an average degree of polymerization of 500 or more and 5000 or less, and (a1) the content of vinyl chloride resin particles having an average degree of polymerization of 800 or more and 5000 or less is 70% by mass or more and 100% by mass or less.
- the content ratio of the (a2) vinyl chloride resin fine particles having an average degree of polymerization of 500 or more and 5000 or less is 0% by mass or more and 30% by mass or less.
- “resin particles” refers to particles having a particle size of 30 ⁇ m or more, and “resin particles” refers to particles having a particle size of less than 30 ⁇ m.
- the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles and the vinyl chloride resin fine particles conforms to JIS K 6720-2. Measured.
- the vinyl chloride resin composition for powder molding of the present invention further contains a plasticizer, and the content of the plasticizer is 90 parts by mass or more per 100 parts by mass of the (a) vinyl chloride resin. preferable.
- the vinyl chloride resin composition for powder molding of the present invention is preferably used for powder slush molding.
- the present invention is a vinyl chloride resin molded body obtained by powder molding any one of the above-mentioned vinyl chloride resin compositions for powder molding.
- the vinyl chloride resin molded article of the present invention is preferably formed by powder slush molding of the above-mentioned vinyl chloride resin composition for powder molding.
- the vinyl chloride resin molded article of the present invention is preferably for an automotive instrument panel skin.
- this invention is a laminated body which has a foaming polyurethane molding and one of the vinyl chloride resin moldings mentioned above.
- the laminate of the present invention is preferably for an automobile instrument panel.
- the vinyl chloride resin molded product of the present invention obtained by powder molding the vinyl chloride resin composition for powder molding of the present invention has low fuzziness.
- the vinyl chloride resin composition for powder molding of the present invention contains (a) a vinyl chloride resin and (b) a silicone oil having a viscosity of 10 cs or more and 200 ⁇ 10 4 cs or less, optionally further containing an additive. contains.
- the content of (a) silicone oil having a viscosity of 10 cs or more and 200 ⁇ 10 4 cs or less per 100 parts by mass of vinyl chloride resin is 0. .1 to 10 parts by mass.
- the vinyl chloride resin is a polymer containing units derived from vinyl chloride as a monomer, and is not particularly limited.
- (a1) vinyl chloride resin particles having a predetermined degree of polymerization and (A2) Vinyl chloride resin fine particles having a predetermined degree of polymerization are included.
- the (a) vinyl chloride resin more preferably comprises (a1) vinyl chloride resin particles and (a2) vinyl chloride resin fine particles having a predetermined content ratio.
- “(a1) vinyl chloride resin particles having an average degree of polymerization of 800 or more and 5000 or less” means “(a1) vinyl chloride resin particles having a predetermined degree of polymerization” or “(a1) vinyl chloride resin.
- (a2) vinyl chloride resin fine particles having an average degree of polymerization of 500 to 5000 is the same as “(a2) vinyl chloride resin fine particles having a predetermined degree of polymerization” and “(a2) vinyl chloride resin fine particles”.
- the mass of (a) vinyl chloride resin is the mass of (a1) vinyl chloride resin particles.
- (a2) refers to the total mass of the vinyl chloride resin fine particles.
- the vinyl chloride resin that can constitute the (a1) vinyl chloride resin particles and the (a2) vinyl chloride resin fine particles in addition to the vinyl chloride homopolymer, the vinyl chloride unit is preferably 50% by mass or more, more preferably. Is a copolymer containing 70% by mass or more.
- monomers (comonomers) copolymerizable with vinyl chloride in vinyl chloride copolymers include olefins such as ethylene and propylene; allyl chloride, vinylidene chloride, vinyl fluoride, trifluoride chloride Halogenated olefins such as ethylene; carboxylic acid vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as isobutyl vinyl ether and cetyl vinyl ether; allyl such as allyl-3-chloro-2-oxypropyl ether and allyl glycidyl ether Ethers; unsaturated carboxylic acids such as acrylic acid, maleic acid, itaconic acid, 2-hydroxyethyl acrylate, methyl methacrylate, monomethyl maleate, diethyl maleate, maleic anhydride, esters thereof, and acid anhydrides thereof Acrylonitrile, Unsaturated nitriles such as tacrylonitrile; acrylamide
- the monomers exemplified above are only a part of the comonomer, and examples of the comonomer include “polyvinyl chloride” edited by the Kinki Chemical Association Vinyl Division, Nikkan Kogyo Shimbun (1988), No. 75- Various monomers exemplified on page 104 can be used. One or more of these monomers can be used.
- the vinyl chloride resin constituting the above (a1) vinyl chloride resin particles may be a resin such as ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl acrylate copolymer, chlorinated polyethylene, It also includes (1) vinyl chloride or (2) a resin obtained by graft polymerization of vinyl chloride and the comonomer.
- (meth) acryl means acryl and / or methacryl.
- the vinyl chloride resin can be produced by any conventionally known production method such as a suspension polymerization method, an emulsion polymerization method, a solution polymerization method or a bulk polymerization method.
- the (a) vinyl chloride resin preferably contains (a1) vinyl chloride resin particles having a predetermined degree of polymerization.
- (a1) vinyl chloride resin particles normally function as a matrix resin.
- a vinyl chloride resin produced by a suspension polymerization method is particularly preferable.
- the average degree of polymerization of the (a1) vinyl chloride resin particles is preferably 800 or more, more preferably 1200 or more, further preferably 1600 or more, particularly preferably 1900 or more, preferably It is 5000 or less, More preferably, it is 3000 or less.
- the average degree of polymerization of the above (a1) vinyl chloride resin particles is within the above range, good heat aging resistance is imparted to a vinyl chloride resin molded product obtained by powder molding a vinyl chloride resin composition for powder molding. In addition, lower fluffing properties can be imparted.
- (a1) vinyl chloride resin particle only 1 type may be used and you may use together 2 or more types (a1) vinyl chloride resin particle from which average polymerization degree differs.
- the average particle diameter of the (a1) vinyl chloride resin particles is usually 30 ⁇ m or more, preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more, preferably 500 ⁇ m or less, more preferably 250 ⁇ m or less. More preferably, it is 200 ⁇ m or less.
- the average particle diameter of the (a1) vinyl chloride resin particles is within the above range, the powder flowability of the powder moldable vinyl chloride resin composition is improved, and the powder moldable vinyl chloride resin composition is The smoothness of the vinyl chloride resin molded product formed by powder molding is improved. In addition, low fluffing properties can be imparted by the vinyl chloride resin molded article.
- the “particle diameter” and “average particle diameter” of the vinyl chloride resin particles can be measured by a laser diffraction method in accordance with JIS Z8825.
- the content ratio of (a1) vinyl chloride resin particles in 100% by mass of (a) vinyl chloride resin is preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 75% by mass. Yes, it can be 100% by mass, preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.
- the content ratio of the (a1) vinyl chloride resin particles is not less than the above lower limit, good heat aging resistance can be imparted by the vinyl chloride resin molded body produced using the vinyl chloride resin composition for powder molding.
- the content rate of (a1) vinyl chloride resin particle is below the said upper limit, the powder fluidity
- the (a) vinyl chloride resin may contain (a2) vinyl chloride resin fine particles having a predetermined degree of polymerization as required.
- (a2) vinyl chloride resin fine particles function as a dusting agent (powder fluidity improver) that improves the powder fluidity of the vinyl chloride resin composition.
- a vinyl chloride resin produced by an emulsion polymerization method is particularly preferable.
- the average degree of polymerization of the vinyl chloride resin constituting the (a2) vinyl chloride resin fine particles is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, preferably 5000 or less, More preferably, it is 3000 or less, More preferably, it is 2500 or less. More preferably, it is 2300 or less.
- the average polymerization degree of the vinyl chloride resin constituting the (a2) vinyl chloride resin fine particles is within the above range, the powder flowability of the vinyl chloride resin composition for powder molding is good, and the vinyl chloride resin Good heat aging resistance can be imparted to the molded body.
- the (a2) vinyl chloride resin fine particles only one kind may be used, or two or more kinds of (a2) vinyl chloride resin fine particles having different average polymerization degrees may be used. From the viewpoint of further improving the powder fluidity of the resin composition, it is preferable to use two different types of (a2) vinyl chloride resin fine particles in combination.
- the average particle size of the above (a2) vinyl chloride resin fine particles is usually less than 30 ⁇ m, preferably 10 ⁇ m or less, and preferably 0.1 ⁇ m or more. When the average particle diameter of the (a2) vinyl chloride resin fine particles is within the above range, the powder flowability of the powder moldable vinyl chloride resin composition is improved.
- the “particle diameter” and “average particle diameter” of the vinyl chloride resin fine particles can be measured by a laser diffraction method in accordance with JIS Z8825.
- the content ratio of the (a2) vinyl chloride resin fine particles in 100% by mass of the (a) vinyl chloride resin is 0% by mass or more, preferably 1% by mass or more, more preferably 5% by mass or more, More preferably, it is 8 mass% or more, Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less.
- the content ratio of the above (a2) vinyl chloride resin fine particles is within the above range, the powder flowability of the vinyl chloride resin composition for powder molding is good, and the vinyl chloride resin molded article has good heat aging resistance. Sex can be imparted.
- the vinyl chloride resin composition for powder molding of the present invention comprises (b) a silicone oil having a viscosity of 10 cs or more and 200 ⁇ 10 4 cs or less (in this specification, simply “(b) silicone oil” or “(b) It may be referred to as “silicone oil having a predetermined viscosity”).
- the silicone oil may be a polar group-unmodified silicone oil or a polar group-modified silicone oil.
- the polar group-unmodified silicone oil is a polymer having a polysiloxane structure.
- polar group-unmodified silicone oil examples include polydimethylsiloxane, polydiethylsiloxane, poly (methylethyl) siloxane, and mixtures thereof.
- examples of the polar group-modified silicone oil include silicone oils in which polar groups such as carboxyl group, hydroxyl group, mercapto group, amino group, epoxy group, and (meth) acryloyloxy group are introduced into a polymer having a polysiloxane structure. It is done. The site into which the polar group is introduced is the terminal and / or side chain of a polymer having a polysiloxane structure.
- (b) silicone oil a polar group-unmodified silicone oil is preferable, and polydimethylsiloxane is more preferable.
- (meth) acryloyloxy group means an acryloyloxy group and / or a methacryloyloxy group.
- the viscosity of (b) silicone oil needs to be 10 cs or more and 200 ⁇ 10 4 cs or less. Further, the viscosity of (b) silicone oil is preferably 50 cs or more, more preferably 1000 cs or more, further preferably 5000 cs or more, and preferably 150 ⁇ 10 4 cs or less, It is more preferable that it is 10 4 cs or less.
- the viscosity of the silicone oil is within the above range, the releasability of the vinyl chloride resin molded article obtained by powder molding the vinyl chloride resin composition for powder molding is improved, and the vinyl chloride resin molded article Can reduce the fluffiness.
- the content of (b) silicone oil with respect to 100 parts by mass of (a) vinyl chloride resin needs to be 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.2 parts by mass or more, 0.4 parts by mass or more is more preferable, 1 part by mass or more is more preferable, 2 parts by mass or more is particularly preferable, 8 parts by mass or less is preferable, 6 parts by mass or less is further preferable, and 5 parts by mass or less is more preferable. Part by mass or less is particularly preferable.
- (B) When the content of the silicone oil is within the above range, the release property of a vinyl chloride resin molded product obtained by powder molding a vinyl chloride resin composition for powder molding is improved, and the vinyl chloride resin molding is performed. Reduces the fluffiness of the body.
- the content of (b) silicone oil is preferably 0.20 parts by mass or more with respect to 100 parts by mass of the plasticizer when the vinyl chloride resin composition for powder molding further contains a plasticizer described later. 30 parts by mass or more is more preferable, 0.50 parts by mass or more is more preferable, 3.0 parts by mass or less is preferable, 2.5 parts by mass or less is more preferable, and 2.0 parts by mass or less is still more preferable.
- the content of silicone oil is not less than the above lower limit, the releasability of a vinyl chloride resin molded product obtained by powder molding a vinyl chloride resin composition for powder molding is further improved, and the vinyl chloride resin The fluffing property of the molded product can be further reduced. Further, if the content of (b) silicone oil is not more than the above upper limit, (b) better release properties while suppressing stickiness of the vinyl chloride resin molded article without excessively containing silicone oil And fluffiness can be realized.
- the additive that the vinyl chloride resin composition for powder molding may further contain in addition to (a) vinyl chloride resin and (b) silicone oil having a viscosity of 10 cs to 200 ⁇ 10 4 cs is particularly limited. Without further including, for example, a plasticizer, perchloric acid-treated hydrotalcite, zeolite, ⁇ -diketone, fatty acid metal salt, (a2) a dusting agent other than vinyl chloride resin fine particles, and other additives. Can do.
- the vinyl chloride resin composition for powder molding of the present invention preferably further contains a plasticizer.
- a plasticizer include the following primary plasticizer and secondary plasticizer.
- Trimellitic acid esters such as esters having more than one species; Pyromellitic acid tetra-n-hexyl, pyromellitic acid tetra-n-heptyl, pyromellitic acid tetra-n-octyl, pyromellitic acid tetra- (2-ethylhexyl), pyromellitic acid tetra-n-nonyl, pyromellitic acid Tetra-n-decyl, pyromellitic acid tetraisodecyl, pyromellitic acid tetra-n-undecyl, pyromellitic acid tetra-n-dodecyl, pyromellitic acid tetra-n-alkyl ester (an alkyl group having a different carbon number [however, A carbon number of 6 to 12.] An ester having two or more in the molecule thereof) or a pyromelli
- a glycol derivative of Glycerol derivatives such as glycerol monoacetate, glycerol triacetate, glycerol tributyrate; Epoxy derivatives such as epoxyhexahydrophthalate diisodecyl, epoxy triglyceride, epoxidized octyl oleate, epoxidized decyl oleate; Polyester plasticizers such as adipic acid polyester, sebacic acid polyester, phthalic acid polyester; Etc.
- the primary plasticizer mentioned above may use 1 type (s) or 2 or more types. Among these, trimellitic acid tri-n-alkyl ester (an ester having two or more kinds of alkyl groups having different carbon numbers [wherein the carbon number is 6 to 12] in the molecule) is preferable as the primary plasticizer.
- secondary plasticizers include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; chlorinated paraffins; fatty acid esters of glycols such as triethylene glycol dicaprylate; phenyl oleate; methyl dihydroabietic acid And the like.
- the secondary plasticizer mentioned above may use together 1 type (s) or 2 or more types with a primary plasticizer.
- a secondary plasticizer an epoxidized vegetable oil is preferable and an epoxidized soybean oil is more preferable.
- the primary plasticizer more than equal mass with it is preferably used together.
- the content of the plasticizer with respect to 100 parts by mass of the vinyl chloride resin (a) is preferably 30 parts by mass or more, more preferably 60 parts by mass or more, still more preferably 90 parts by mass or more, and preferably 190 parts by mass or less.
- the amount is more preferably equal to or less than part by mass, and still more preferably equal to or less than 160 parts by mass.
- the fluffing property may be increased.
- the vinyl chloride resin composition for powder molding contains the predetermined silicone oil, even when the amount of the plasticizer is increased as compared with the conventional case, the fluff is reduced. Adhesiveness can be sufficiently reduced.
- the vinyl chloride resin composition for powder molding of the present invention may contain perchloric acid-treated hydrotalcite.
- Perchloric acid-treated hydrotalcite for example, by adding hydrotalcite to a dilute aqueous solution of perchloric acid, stirring, and then filtering, dehydrating or drying as necessary, thereby allowing carbonate anions in hydrotalcite It can be easily produced by substituting at least a part of (CO 3 2 ⁇ ) with a perchlorate anion (ClO 4 ⁇ ) (2 mol of perchlorate anion is substituted for 1 mol of carbonate anion).
- the molar ratio of the hydrotalcite to the perchloric acid can be arbitrarily set, it is generally 0.1 mol or more and 2 mol or less of perchloric acid with respect to 1 mol of hydrotalcite.
- the substitution rate of the carbonate anion to the perchlorate anion in the untreated (unsubstituted) hydrotalcite is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 85 mol% or more. Further, the substitution rate of the carbonate anion to the perchlorate anion in the untreated (unsubstituted) hydrotalcite is preferably 95 mol% or less.
- the vinyl resin molded product can be imparted with good flexibility at low temperatures, and the fluffiness of the vinyl chloride resin molded product can be further reduced.
- Hydrotalcite is a non - stoichiometric compound represented by the general formula [Mg 1-x Al x (OH) 2 ] x + [(CO 3 ) x / 2 ⁇ mH 2 O] x- and is a positively charged base layer It is an inorganic substance having a layered crystal structure consisting of [Mg 1-x Al x (OH) 2 ] x + and a negatively charged intermediate layer [(CO 3 ) x / 2 ⁇ mH 2 O] x- .
- x is a number in the range of greater than 0 and less than or equal to 0.33.
- Natural hydrotalcite is Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O.
- Mg 4.5 Al 2 (OH) 13 CO 3 .3.5H 2 O is commercially available as the synthesized hydrotalcite.
- a method for synthesizing synthetic hydrotalcite is described in, for example, Japanese Patent Publication No. 61-174270.
- the content of perchloric acid-treated hydrotalcite with respect to 100 parts by mass of the (a) vinyl chloride resin is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and further preferably 1.5 parts by mass or more. It is preferably no greater than 6 parts by mass, more preferably no greater than 6 parts by mass, and even more preferably no greater than 5.5 parts by mass.
- the content of the perchloric acid-treated hydrotalcite is within the above range, good flexibility at low temperatures is imparted to a vinyl chloride resin molded product obtained by powder molding a vinyl chloride resin composition for powder molding. This is because the fluffiness of the vinyl chloride resin molded product can be further reduced.
- the vinyl chloride resin composition for powder molding of the present invention can contain zeolite as a stabilizer.
- Zeolite is represented by the general formula: M x / n ⁇ [(AlO 2 ) x ⁇ (SiO 2 ) y ] ⁇ zH 2 O (in the above general formula, M is a metal ion of valence n, x + y is four sides per unit cell) Body number, z is the number of moles of water), and the type of M in the general formula is a monovalent or divalent metal such as Na, Li, Ca, Mg, Zn, and the like. These mixed types are mentioned.
- Zeolite content is not limited to a specific range.
- the content of zeolite is preferably 0.1 parts by mass or more and preferably 5 parts by mass or less with respect to (a) 100 parts by mass of the vinyl chloride resin.
- a vinyl chloride resin molded product obtained by powder molding a vinyl chloride resin composition for powder molding can be given good low-temperature flexibility and vinyl chloride resin molding. The fluffiness of the body can be lowered.
- ⁇ -diketone can be used in order to more effectively suppress fluctuations in the initial color tone of a vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition for powder molding of the present invention.
- ⁇ -diketone are dibenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, and the like. These ⁇ -diketones may be used alone or in combination of two or more.
- the content of ⁇ -diketone is not limited to a specific range.
- the content of ⁇ -diketone is preferably 0.1 parts by mass or more and preferably 5 parts by mass or less with respect to 100 parts by mass of (a) vinyl chloride resin.
- the vinyl chloride resin composition for powder molding of the present invention may contain a fatty acid metal salt.
- Preferred fatty acid metal salts are monovalent fatty acid metal salts, more preferred fatty acid metal salts are monovalent fatty acid metal salts having 12 to 24 carbon atoms, and more preferred fatty acid metal salts having 15 to 21 carbon atoms. It is a monovalent fatty acid metal salt.
- Specific examples of the fatty acid metal salt include lithium stearate, magnesium stearate, aluminum stearate, calcium stearate, strontium stearate, barium stearate, zinc stearate, calcium laurate, barium laurate, zinc laurate, 2-ethylhexane.
- the metal constituting the fatty acid metal salt is preferably a metal capable of generating a polyvalent cation, more preferably a metal capable of generating a divalent cation, and a divalent cation of the third to sixth periods of the periodic table. Is more preferable, and a metal capable of generating a divalent cation in the fourth period of the periodic table is particularly preferable.
- the most preferred fatty acid metal salt is zinc stearate.
- the content of the fatty acid metal salt with respect to 100 parts by mass of the (a) vinyl chloride resin is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, preferably 5 parts by mass or less, more preferably 1 part by mass or less. 0.5 parts by mass or less is more preferable.
- a vinyl chloride resin molded article obtained by powder molding a vinyl chloride resin composition for powder molding can be imparted with good flexibility at low temperatures and a vinyl chloride resin.
- the fluffing property of the molded body can be further reduced, and further, the discoloration after the heat resistance test can be reduced.
- the vinyl chloride resin composition for powder molding of the present invention may further contain (a2) a dusting agent other than the vinyl chloride resin fine particles (hereinafter sometimes referred to as “other dusting agent”).
- other dusting agents include inorganic fine particles such as calcium carbonate, talc, and aluminum oxide; polyacrylonitrile resin fine particles, poly (meth) acrylate resin fine particles, polystyrene resin fine particles, polyethylene resin fine particles, polypropylene resin fine particles, polyester resin Organic fine particles such as fine particles and polyamide resin fine particles; Among these, inorganic fine particles having an average particle size of 10 nm to 100 nm are preferable.
- the content of other dusting agents is not limited to a specific range.
- the content of other dusting agents is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and can be 0 parts by mass with respect to 100 parts by mass of (a) the vinyl chloride resin. .
- the vinyl chloride resin composition for powder molding of the present invention comprises a colorant, an impact modifier, a perchloric acid compound other than perchloric acid-treated hydrotalcite (sodium perchlorate, potassium perchlorate, etc.), oxidation It may further contain other additives such as an inhibitor, an antifungal agent, a flame retardant, an antistatic agent, a filler, a light stabilizer, and a foaming agent.
- the colorant are quinacridone pigments, perylene pigments, polyazo condensation pigments, isoindolinone pigments, copper phthalocyanine pigments, titanium white, and carbon black.
- the quinacridone pigment is obtained by treating p-phenylene dianthranilic acid with concentrated sulfuric acid and exhibits a yellowish red to reddish purple hue.
- Specific examples of the quinacridone pigment are quinacridone red, quinacridone magenta, and quinacridone violet.
- the perylene pigment is obtained by a condensation reaction of perylene-3,4,9,10-tetracarboxylic anhydride and an aromatic primary amine, and exhibits a hue from red to magenta and brown.
- the perylene pigment are perylene red, perylene orange, perylene maroon, perylene vermilion, and perylene bordeaux.
- the polyazo condensation pigment is obtained by condensing an azo dye in a solvent to obtain a high molecular weight, and exhibits a hue of a yellow or red pigment.
- Specific examples of the polyazo condensation pigment are polyazo red, polyazo yellow, chromophthal orange, chromophthal red, and chromophthal scarlet.
- the isoindolinone pigment is obtained by a condensation reaction of 4,5,6,7-tetrachloroisoindolinone and an aromatic primary diamine, and exhibits a hue of greenish yellow to red and brown.
- the isoindolinone pigment is isoindolinone yellow.
- the copper phthalocyanine pigment is a pigment in which copper is coordinated to phthalocyanines, and exhibits a hue of yellowish green to vivid blue.
- Specific examples of the copper phthalocyanine pigment are phthalocyanine green and phthalocyanine blue.
- Titanium white is a white pigment made of titanium dioxide and has a large hiding power, and there are anatase type and rutile type.
- Carbon black is a black pigment containing carbon as a main component and containing oxygen, hydrogen, and nitrogen. Specific examples of carbon black are thermal black, acetylene black, channel black, furnace black, lamp black, and bone black.
- the impact resistance improver include acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, chlorinated polyethylene, ethylene-vinyl acetate copolymer, chlorosulfonated polyethylene and the like.
- the vinyl chloride resin composition for powder molding of the present invention one or more impact resistance improvers can be used.
- the impact resistance improver is dispersed as a heterogeneous phase of fine elastic particles in the vinyl chloride resin composition for powder molding.
- the chain and polar group graft-polymerized on the elastic particles are compatible with (a) the vinyl chloride resin, and the impact resistance of the vinyl chloride resin composition is improved.
- antioxidants include phenolic antioxidants, sulfur antioxidants, phosphorus antioxidants, and the like.
- fungicide examples include aliphatic ester fungicides, hydrocarbon fungicides, organic nitrogen fungicides, organic nitrogen sulfur fungicides, and the like.
- flame retardants are halogen flame retardants such as chlorinated paraffin; phosphorus flame retardants such as phosphate esters; inorganic hydroxides such as magnesium hydroxide and aluminum hydroxide;
- antistatic agent examples include anionic antistatic agents such as fatty acid salts, higher alcohol sulfates and sulfonates; cationic antistatic agents such as aliphatic amine salts and quaternary ammonium salts; polyoxyethylene alkyl Nonionic antistatic agents such as ethers and polyoxyethylene alkylphenol ethers;
- filler examples include silica, talc, mica, calcium carbonate, clay and the like.
- light stabilizers include benzotriazole-based, benzophenone-based, nickel chelate-based ultraviolet absorbers, hindered amine-based light stabilizers, and the like.
- blowing agent examples include azo compounds such as azodicarbonamide and azobisisobutyronitrile, nitroso compounds such as N, N′-dinitrosopentamethylenetetramine, p-toluenesulfonyl hydrazide, p, p-oxybis (benzene)
- Organic foaming agents such as sulfonyl hydrazide compounds such as sulfonyl hydrazide; volatile hydrocarbon compounds such as chlorofluorocarbon gas, carbon dioxide gas, water and pentane; gas-based foaming agents such as microcapsules enclosing these.
- the mixing method of (a) vinyl chloride resin, (b) silicone oil, and the additive added as needed is not limited.
- components other than the dusting agent including (a2) vinyl chloride resin fine particles and other dusting agent added as necessary
- the Henschel mixer is preferably used for dry blending.
- the temperature during dry blending is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, preferably 100 ° C. or lower, and more preferably 80 ° C. or lower.
- the vinyl chloride resin molded article of the present invention is obtained by powder molding, preferably powder slush molding, of the vinyl chloride resin composition for powder molding of the present invention.
- the vinyl chloride resin molded article of the present invention is suitably used as an automobile interior material, for example, a skin of an automobile instrument panel, a door trim or the like.
- the mold temperature at the time of powder slush molding is preferably 200 ° C. or higher, more preferably 220 ° C. or higher, preferably 300 ° C. or lower, more preferably 280 ° C. or lower.
- the vinyl chloride resin molded body of the present invention is obtained by, for example, sprinkling a powder molding vinyl chloride resin composition on a mold in the above temperature range and leaving it for 5 seconds to 30 seconds, and then surplus vinyl chloride resin. The composition is shaken off, and is further allowed to stand for 30 seconds to 3 minutes at an arbitrary temperature. Thereafter, the mold is cooled to 10 ° C. or more and 60 ° C. or less, and the obtained vinyl chloride resin molded article is removed from the mold to be suitably obtained.
- the laminate of the present invention can be obtained by laminating the above-described vinyl chloride resin molded article and foamed polyurethane molded article.
- the lamination method is as follows: (1) A vinyl chloride resin molded body and a foamed polyurethane molded body are separately manufactured, and then bonded together by using thermal fusion, thermal bonding, or a known adhesive; (2) Chlorination Polymerization is performed by reacting isocyanates, which are raw materials of the foamed polyurethane molded body, and polyols on the vinyl resin molded body, and polyurethane is foamed by a known method, and the polyurethane foam is formed on the vinyl chloride resin molded body.
- the laminated body of this invention is used suitably as a vehicle interior material, for example, a vehicle instrument panel, a door trim, etc.
- ⁇ Average polymerization degree of vinyl chloride resin> According to JIS K6720-2, the average degree of polymerization of (a1) vinyl chloride resin particles and (a2) vinyl chloride resin particles constituting the vinyl chloride resin fine particles is (a1) vinyl chloride resin particles and (a2) vinyl chloride resin. Each fine particle was calculated by dissolving in cyclohexanone and measuring the viscosity.
- the average particle diameter (volume average particle diameter) of the (a1) vinyl chloride resin particles and (a2) vinyl chloride resin fine particles is obtained by dispersing the vinyl chloride resin particles and the vinyl chloride resin fine particles in a water tank, respectively. It was calculated by measuring and analyzing the light diffraction / scattering intensity distribution and measuring the particle size and volume-based particle size distribution.
- ⁇ Apparatus Laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, model number “SALD-2300”) ⁇ Measuring method: Laser diffraction and scattering ⁇ Measuring range: 0.017 ⁇ m to 2500 ⁇ m
- Light source Semiconductor laser (wavelength 680 nm, output 3 mW)
- ⁇ Fuzzy property test> The obtained laminate made of polyurethane foam was used as a sample, the sample was cut into a test piece having a size of 170 mm ⁇ 300 mm, and the test piece was subjected to a Gakushin-type wear tester (manufactured by Daiei Kagaku Seiki Seisakusho, The sample was placed on the sample stage of the product name “RT-200” so that the vinyl chloride resin molded article side was up. And the load of 500g was attached to the said abrasion tester, and the total load applied to a test piece was set to 500g.
- the paper towel is attached to the surface of the test piece on the side of the vinyl chloride resin molding.
- the test piece surface and the paper towel were worn by reciprocating 10 times while in contact.
- 20 spots having different adhesion degrees on the test piece (vinyl chloride resin molded article side) were selected according to the degree of adhesion of the fiber residue generated from the paper towel cloth on the surface of the test piece after being worn.
- ⁇ Manufacture of vinyl chloride resin molding> The obtained vinyl chloride resin composition for powder molding is sprinkled on a mold with a texture heated to a temperature of 250 ° C., and an arbitrary time of about 8 seconds to 20 seconds so that the thickness of the vinyl chloride resin molded sheet becomes 1 mm. After leaving it to melt, the excess vinyl chloride resin composition was shaken off. Thereafter, the embossed mold sprinkled with the vinyl chloride resin composition was allowed to stand in an oven set at a temperature of 200 ° C., and after 60 seconds had elapsed from standing, the embossed mold was cooled with cooling water.
- a polyol mixture consisting of parts was prepared. Then, the prepared polyol mixture and polymethylene polyphenylene polyisocyanate (polymeric MDI) were mixed at a ratio of an index of 98 to prepare a mixed solution.
- the prepared liquid mixture was each poured on 2 sheets of vinyl chloride resin molding sheets spread
- ZEST 2500Z manufactured by Shin-Daiichi PVC Co., Ltd. ((a1) vinyl chloride resin particles obtained by suspension polymerization, average polymerization degree 2500, average particle diameter 130 ⁇ m) 2) Made by Kao Corporation, Trimex N-08 3) Adeka Sizer O-130S manufactured by ADEKA Corporation 4) Alkamizer 5 manufactured by Kyowa Chemical Industry Co., Ltd. 5) MIZUKALIZER DS, manufactured by Mizusawa Chemical Co., Ltd. 6) Karenz DK-1, manufactured by Showa Denko K.K.
- the vinyl chloride resin composition for powder molding according to the present invention is suitably molded on the skin of automobile interior materials such as automobile instrument panels and door trims.
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Abstract
Description
そこで、本発明が解決しようとする課題は、毛羽付き性が低い成形体を与える粉体成形用塩化ビニル樹脂組成物の提供である。
なお、本発明において、「粘度」は、ASTM D 445-46Tに従い、ウッベローデ粘度計を用いて測定することができる。
なお、本発明において、「樹脂粒子」とは、粒子径が30μm以上の粒子を指し、「樹脂微粒子」とは、粒子径が30μm未満の粒子を指す。
また、塩化ビニル樹脂粒子及び塩化ビニル樹脂微粒子(以下、「塩化ビニル樹脂(微)粒子」と称することがある。)を構成する塩化ビニル樹脂の平均重合度は、JIS K 6720-2に準拠して測定される。
本発明の粉体成形用塩化ビニル樹脂組成物は、(a)塩化ビニル樹脂と、(b)粘度が10cs以上200×104cs以下であるシリコーンオイルとを含有し、任意に添加剤を更に含有する。そして、本発明の粉体成形用塩化ビニル樹脂組成物は、(a)塩化ビニル樹脂100質量部当たりの(b)粘度が10cs以上200×104cs以下であるシリコーンオイルの含有量が、0.1質量部以上10質量部以下である。
(a)塩化ビニル樹脂は、単量体としての塩化ビニルに由来する単位を含む重合体であり、特に制限されることなく、好ましくは、(a1)所定の重合度を有する塩化ビニル樹脂粒子及び/又は(a2)所定の重合度を有する塩化ビニル樹脂微粒子を含む。また、(a)塩化ビニル樹脂は、より好ましくは、所定の含有割合の(a1)塩化ビニル樹脂粒子及び(a2)塩化ビニル樹脂微粒子からなる。
なお、本発明において、「(a1)平均重合度が800以上5000以下である塩化ビニル樹脂粒子」は、「(a1)所定の重合度を有する塩化ビニル樹脂粒子」、「(a1)塩化ビニル樹脂粒子」と同様の意味を有する。また、「(a2)平均重合度が500以上5000以下である塩化ビニル樹脂微粒子」は、「(a2)所定の重合度を有する塩化ビニル樹脂微粒子」、「(a2)塩化ビニル樹脂微粒子」と同様の意味を有する。
また、例えば、(a)塩化ビニル樹脂が(a1)塩化ビニル樹脂粒子及び(a2)塩化ビニル樹脂微粒子からなる場合は、(a)塩化ビニル樹脂の質量は、(a1)塩化ビニル樹脂粒子の質量及び(a2)塩化ビニル樹脂微粒子の質量を合わせた質量を指す。
塩化ビニル共重合体における、塩化ビニルと共重合可能な単量体(共単量体)の具体例は、エチレン、プロピレンなどのオレフィン類;塩化アリル、塩化ビニリデン、フッ化ビニル、三フッ化塩化エチレンなどのハロゲン化オレフィン類;酢酸ビニル、プロピオン酸ビニルなどのカルボン酸ビニルエステル類;イソブチルビニルエーテル、セチルビニルエーテルなどのビニルエーテル類;アリル-3-クロロ-2-オキシプロピルエーテル、アリルグリシジルエーテルなどのアリルエーテル類;アクリル酸、マレイン酸、イタコン酸、アクリル酸-2-ヒドロキシエチル、メタクリル酸メチル、マレイン酸モノメチル、マレイン酸ジエチル、無水マレイン酸などの不飽和カルボン酸、そのエステルまたはその酸無水物類;アクリロニトリル、メタクリロニトリルなどの不飽和ニトリル類;アクリルアミド、N-メチロールアクリルアミド、アクリルアミド-2-メチルプロパンスルホン酸、(メタ)アクリルアミドプロピルトリメチルアンモニウムクロライドなどのアクリルアミド類;アリルアミン安息香酸塩、ジアリルジメチルアンモニウムクロライドなどのアリルアミンおよびその誘導体類;などである。以上に例示される単量体は、共単量体の一部に過ぎず、共単量体としては、近畿化学協会ビニル部会編「ポリ塩化ビニル」日刊工業新聞社(1988年)第75~104頁に例示されている各種単量体が使用され得る。これらの単量体の1種又は2種以上が使用され得る。上記(a1)塩化ビニル樹脂粒子を構成する塩化ビニル樹脂は、エチレン-酢酸ビニル共重合体、エチレン-メタクリル酸メチル共重合体、エチレン-アクリル酸エチル共重合体、塩素化ポリエチレンなどの樹脂に、(1)塩化ビニルまたは(2)塩化ビニルと前記共単量体とがグラフト重合された樹脂も含む。
ここで、本明細書において、「(メタ)アクリル」とは、アクリル及び/又はメタクリルを意味する。
(a)塩化ビニル樹脂は、(a1)所定の重合度を有する塩化ビニル樹脂粒子を含有することが好ましい。
なお、粉体成形用塩化ビニル樹脂組成物において、(a1)塩化ビニル樹脂粒子は、通常、マトリックス樹脂として機能する。
また、(a1)塩化ビニル樹脂粒子を構成する塩化ビニル樹脂としては、特に、懸濁重合法により製造された塩化ビニル樹脂が好ましい。
なお、(a1)塩化ビニル樹脂粒子としては、1種のみを用いても良く、平均重合度が異なる2種以上の(a1)塩化ビニル樹脂粒子を併用しても良い。
なお、(a1)塩化ビニル樹脂粒子の「粒子径」及び「平均粒子径」とは、JIS Z8825に準拠し、レーザー回折法によって測定することができる。
上記(a)塩化ビニル樹脂は、必要に応じて所定の重合度を有する(a2)塩化ビニル樹脂微粒子を含有し得る。
なお、粉体成形用塩化ビニル樹脂組成物において、(a2)塩化ビニル樹脂微粒子は、塩化ビニル樹脂組成物の粉体流動性を向上させるダスティング剤(粉体流動性改良剤)として機能する。
また、(a2)塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂としては、特に、乳化重合法により製造された塩化ビニル樹脂が好ましい。
なお、(a2)塩化ビニル樹脂微粒子としては、1種のみを用いても良く、平均重合度が異なる2種以上の(a2)塩化ビニル樹脂微粒子を用いても良いが、粉体成形用塩化ビニル樹脂組成物の粉体流動性を更に高める観点からは、異なる2種の(a2)塩化ビニル樹脂微粒子を併用することが好ましい。
なお、(a2)塩化ビニル樹脂微粒子の「粒子径」及び「平均粒子径」は、JIS Z8825に準拠し、レーザー回折法によって測定することができる。
本発明の粉体成形用塩化ビニル樹脂組成物は、(b)粘度が10cs以上200×104cs以下であるシリコーンオイル(本明細書において、単に「(b)シリコーンオイル」又は「(b)所定粘度を有するシリコーンオイル」と称する場合がある。)を含有する。(b)シリコーンオイルは、極性基未変性のシリコーンオイルでも、極性基変性シリコーンオイルでもよい。極性基未変性のシリコーンオイルは、ポリシロキサン構造を有する高分子である。極性基未変性のシリコーンオイルの具体例としては、例えば、ポリジメチルシロキサン、ポリジエチルシロキサン、ポリ(メチルエチル)シロキサン、及びこれらの混合物が挙げられる。また、極性基変性シリコーンオイルとしては、カルボキシル基、水酸基、メルカプト基、アミノ基、エポキシ基、(メタ)アクリロイロキシ基等の極性基がポリシロキサン構造を有する高分子に導入されているシリコーンオイルが挙げられる。上記極性基が導入される部位は、ポリシロキサン構造を有する高分子の末端及び/又は側鎖である。中でも、(b)シリコーンオイルとしては、極性基未変性のシリコーンオイルが好ましく、ポリジメチルシロキサンがより好ましい。
なお、本明細書において、「(メタ)アクリロイロキシ基」とは、アクリロイロキシ基及び/又はメタクリロイロキシ基を意味するものとする。
粉体成形用塩化ビニル樹脂組成物が、(a)塩化ビニル樹脂、及び(b)粘度が10cs以上200×104cs以下であるシリコーンオイルに加えて更に含み得る添加剤としては、特に制限されることなく、例えば、可塑剤、過塩素酸処理ハイドロタルサイト、ゼオライト、β-ジケトン、脂肪酸金属塩、(a2)塩化ビニル樹脂微粒子以外のダスティング剤、及び、その他の添加剤を更に含むことができる。
本発明の粉体成形用塩化ビニル樹脂組成物は、好ましくは更に可塑剤を含有する。可塑剤の具体例としては、例えば、以下の一次可塑剤及び二次可塑剤などが挙げられる。
トリメリット酸トリ-n-ヘキシル、トリメリット酸トリ-n-ヘプチル、トリメリット酸トリ-n-オクチル、トリメリット酸トリ-(2-エチルヘキシル)、トリメリット酸トリ-n-ノニル、トリメリット酸トリ-n-デシル、トリメリット酸トリイソデシル、トリメリット酸トリ-n-ウンデシル、トリメリット酸トリ-n-ドデシル、トリメリット酸トリ-n-アルキルエステル(炭素数が異なるアルキル基〔但し、炭素数は6~12である。〕を分子内に2種以上有するエステル)、トリメリット酸トリアルキルエステル(炭素数が異なるアルキル基〔但し、炭素数は8~10である。〕を分子内に2種以上有するエステル)等のトリメリット酸エステル;
ピロメリット酸テトラ-n-ヘキシル、ピロメリット酸テトラ-n-ヘプチル、ピロメリット酸テトラ-n-オクチル、ピロメリット酸テトラ-(2-エチルヘキシル)、ピロメリット酸テトラ-n-ノニル、ピロメリット酸テトラ-n-デシル、ピロメリット酸テトライソデシル、ピロメリット酸テトラ-n-ウンデシル、ピロメリット酸テトラ-n-ドデシル、ピロメリット酸テトラ-n-アルキルエステル(炭素数が異なるアルキル基〔但し、炭素数は6~12である。〕を分子内に2種以上有するエステル)等のピロメリット酸エステル;
ジメチルフタレート、ジエチルフタレート、ジブチルフタレート、ジ-(2-エチルヘキシル)フタレート、ジ-n-オクチルフタレート、ジイソブチルフタレート、ジヘプチルフタレート、ジフェニルフタレート、ジイソデシルフタレート、ジトリデシルフタレート、ジウンデシルフタレート、ジベンジルフタレート、ブチルベンジルフタレート、ジノニルフタレート、ジシクロヘキシルフタレート等のフタル酸誘導体;
ジメチルイソフタレート、ジ-(2-エチルヘキシル)イソフタレート、ジイソオクチルイソフタレート等のイソフタル酸誘導体;
ジ-(2-エチルヘキシル)テトラヒドロフタレート、ジ-n-オクチルテトラヒドロフタレート、ジイソデシルテトラヒドロフタレート等のテトラヒドロフタル酸誘導体;
ジ-n-ブチルアジペート、ジ(2-エチルヘキシル)アジペート、ジイソデシルアジペート、ジイソノニルアジペート等のアジピン酸誘導体;
ジ-(2-エチルヘキシル)アゼレート、ジイソオクチルアゼレート、ジ-n-ヘキシルアゼレート等のアゼライン酸誘導体;
ジ-n-ブチルセバケート、ジ-(2-エチルヘキシル)セバケート、ジイソデシルセバケート、ジ-(2-ブチルオクチル)セバケート等のセバシン酸誘導体;
ジ-n-ブチルマレエート、ジメチルマレエート、ジエチルマレエート、ジ-(2-エチルヘキシル)マレエート等のマレイン酸誘導体;
ジ-n-ブチルフマレート、ジ-(2-エチルヘキシル)フマレート等のフマル酸誘導体;
トリエチルシトレート、トリ-n-ブチルシトレート、アセチルトリエチルシトレート、アセチルトリ-(2-エチルヘキシル)シトレート等のクエン酸誘導体;
モノメチルイタコネート、モノブチルイタコネート、ジメチルイタコネート、ジエチルイタコネート、ジブチルイタコネート、ジ-(2-エチルヘキシル)イタコネート等のイタコン酸誘導体;
ブチルオレエート、グリセリルモノオレエート、ジエチレングリコールモノオレエート等のオレイン酸誘導体;
メチルアセチルリシノレート、ブチルアセチルリシノレート、グリセリルモノリシノレート、ジエチレングリコールモノリシノレート等のリシノール酸誘導体;
n-ブチルステアレート、ジエチレングリコールジステアレート等のステアリン酸誘導体;
ジエチレングリコールモノラウレート、ジエチレングリコールジペラルゴネート、ペンタエリスリトール脂肪酸エステル等のその他の脂肪酸誘導体;
トリエチルホスフェート、トリブチルホスフェート、トリ-(2-エチルヘキシル)ホスフェート、トリブトキシエチルホスフェート、トリフェニルホスフェート、クレジルジフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、トリス(クロロエチル)ホスフェート等のリン酸誘導体;
ジエチレングリコールジベンゾエート、ジプロピレングリコールジベンゾエート、トリエチレングリコールジベンゾエート、トリエチレングリコールジ-(2-エチルブチレート)、トリエチレングリコールジ-(2-エチルヘキソエート)、ジブチルメチレンビスチオグリコレート等のグリコール誘導体;
グリセロールモノアセテート、グリセロールトリアセテート、グリセロールトリブチレート等のグリセリン誘導体;
エポキシヘキサヒドロフタル酸ジイソデシル、エポキシトリグリセライド、エポキシ化オレイン酸オクチル、エポキシ化オレイン酸デシル等のエポキシ誘導体;
アジピン酸系ポリエステル、セバシン酸系ポリエステル、フタル酸系ポリエステル等のポリエステル系可塑剤;
等が挙げられる。上述した一次可塑剤は、1種又は2種以上を使用してもよい。中でも、一次可塑剤としては、トリメリット酸トリ-n-アルキルエステル(炭素数が異なるアルキル基〔但し、炭素数は6~12である。〕を分子内に2種以上有するエステル)が好ましい。
本発明の粉体成形用塩化ビニル樹脂組成物は、過塩素酸処理ハイドロタルサイトを含有していてもよい。過塩素酸処理ハイドロタルサイトは、例えば、ハイドロタルサイトを過塩素酸の希薄水溶液中に加えて撹拌し、その後必要に応じて、ろ過、脱水または乾燥することによって、ハイドロタルサイト中の炭酸アニオン(CO3 2-)の少なくとも一部を過塩素酸アニオン(ClO4 -)で置換(炭酸アニオン1モルにつき過塩素酸アニオン2モルが置換)して、容易に製造することができる。上記ハイドロタルサイトと上記過塩素酸とのモル比は任意に設定できるが、一般には、ハイドロタルサイト1モルに対し、過塩素酸0.1モル以上2モル以下とする。
本発明の粉体成形用塩化ビニル樹脂組成物は、ゼオライトを安定剤として含有し得る。ゼオライトは、一般式:Mx/n・[(AlO2)x・(SiO2)y]・zH2O(上記一般式中、Mは原子価nの金属イオン、x+yは単位格子当たりの四面体数、zは水のモル数である)で表されるものであって、当該一般式中のMの種類としてはNa、Li、Ca、Mg、Znなどの一価又は二価の金属及びこれらの混合型が挙げられる。
β-ジケトンは、本発明の粉体成形用塩化ビニル樹脂組成物を粉体成形して得られる塩化ビニル樹脂成形体の初期色調の変動をより効果的に抑えるために用いられ得る。β-ジケトンの具体例は、ジベンゾイルメタン、ステアロイルベンゾイルメタン、パルミトイルベンゾイルメタン等である。これらのβ-ジケトンは1種を用いてもよいし、2種以上を組み合わせて用いてもよい。
なお、β-ジケトンの含有量は特定の範囲に限定されない。β-ジケトンの含有量は、(a)塩化ビニル樹脂100質量部に対して0.1質量部以上が好ましく、5質量部以下が好ましい。
本発明の粉体成形用塩化ビニル樹脂組成物は、脂肪酸金属塩を含有していてもよい。好ましい脂肪酸金属塩は、一価脂肪酸金属塩であり、より好ましい脂肪酸金属塩は、炭素数12以上24以下の一価脂肪酸金属塩であり、更に好ましい脂肪酸金属塩は、炭素数15以上21以下の一価脂肪酸金属塩である。脂肪酸金属塩の具体例は、ステアリン酸リチウム、ステアリン酸マグネシウム、ステアリン酸アルミニウム、ステアリン酸カルシウム、ステアリン酸ストロンチウム、ステアリン酸バリウム、ステアリン酸亜鉛、ラウリン酸カルシウム、ラウリン酸バリウム、ラウリン酸亜鉛、2-エチルヘキサン酸バリウム、2-エチルヘキサン酸亜鉛、リシノール酸バリウム、リシノール酸亜鉛等である。脂肪酸金属塩を構成する金属としては、多価陽イオンを生成しうる金属が好ましく、2価陽イオンを生成しうる金属がより好ましく、周期表第3周期~第6周期の、2価陽イオンを生成しうる金属が更に好ましく、周期表第4周期の、2価陽イオンを生成しうる金属が特に好ましい。最も好ましい脂肪酸金属塩はステアリン酸亜鉛である。
本発明の粉体成形用塩化ビニル樹脂組成物は、(a2)塩化ビニル樹脂微粒子以外のダスティング剤(以下、「その他のダスティング剤」ということがある。)を更に含有し得る。その他のダスティング剤の具体例としては、炭酸カルシウム、タルク、酸化アルミニウムなどの無機微粒子;ポリアクリロニトリル樹脂微粒子、ポリ(メタ)アクリレート樹脂微粒子、ポリスチレン樹脂微粒子、ポリエチレン樹脂微粒子、ポリプロピレン樹脂微粒子、ポリエステル樹脂微粒子、ポリアミド樹脂微粒子などの有機微粒子;等が挙げられる。中でも、平均粒子径が10nm以上100nm以下の無機微粒子が好ましい。
本発明の粉体成形用塩化ビニル樹脂組成物は、着色剤、耐衝撃性改良剤、過塩素酸処理ハイドロタルサイト以外の過塩素酸化合物(過塩素酸ナトリウム、過塩素酸カリウム等)、酸化防止剤、防カビ剤、難燃剤、帯電防止剤、充填剤、光安定剤、発泡剤等の、その他の添加剤を更に含有し得る。
ペリレン系顔料は、ペリレン-3,4,9,10-テトラカルボン酸無水物と芳香族第一級アミンとの縮合反応により得られ、赤から赤紫、茶色の色相を示す。ペリレン系顔料の具体例は、ペリレンレッド、ペリレンオレンジ、ペリレンマルーン、ペリレンバーミリオン、ペリレンボルドーである。
ポリアゾ縮合顔料は、アゾ色素が溶剤中で縮合されて高分子量化されて得られ、黄、赤系顔料の色相を示す。ポリアゾ縮合顔料の具体例は、ポリアゾレッド、ポリアゾイエロー、クロモフタルオレンジ、クロモフタルレッド、クロモフタルスカーレットである。
イソインドリノン系顔料は、4,5,6,7-テトラクロロイソインドリノンと芳香族第一級ジアミンの縮合反応により得られ、緑みの黄色から、赤、褐色の色相を示す。イソインドリノン系顔料の具体例は、イソインドリノンイエローである。銅フタロシアニン系顔料は、フタロシアニン類に銅を配位した顔料で、黄みの緑から鮮やかな青の色相を示す。
銅フタロシアニン系顔料の具体例は、フタロシアニングリーン、フタロシアニンブルーである。
チタンホワイトは、二酸化チタンからなる白色顔料で、隠蔽力が大きく、アナタース型とルチル型がある。カーボンブラックは、炭素を主成分とし、酸素、水素、窒素を含む黒色顔料である。
カーボンブラックの具体例は、サーマルブラック、アセチレンブラック、チャンネルブラック、ファーネスブラック、ランプブラック、ボーンブラックである。
ここで、(a)塩化ビニル樹脂、(b)シリコーンオイル及び必要に応じて添加される添加剤の混合方法は限定されない。好ましい混合方法は、ダスティング剤((a2)塩化ビニル樹脂微粒子と、必要に応じて添加されるその他のダスティング剤とを含む)を除く成分を一旦ドライブレンドにより混合し、その後、ダスティング剤を添加、混混合する方法である。ドライブレンドには、ヘンシェルミキサーの使用が好ましい。また、ドライブレンド時の温度は、50℃以上が好ましく、70℃以上がより好ましく、100℃以下が好ましく、80℃以下がより好ましい。
本発明の塩化ビニル樹脂成形体は、本発明の粉体成形用塩化ビニル樹脂組成物を粉体成形、好ましくはパウダースラッシュ成形して得られる。そして、本発明の塩化ビニル樹脂成形体は、自動車内装材、例えば、自動車インスツルメントパネル、ドアトリム等の表皮として好適に用いられる。
ここで、パウダースラッシュ成形時の金型温度は、好ましくは200℃以上、より好ましくは220℃以上であり、好ましくは300℃以下、より好ましくは280℃以下である。
また、本発明の塩化ビニル樹脂成形体は、例えば、上記温度範囲の金型に粉体成形用塩化ビニル樹脂組成物を振りかけて5秒以上30秒以下の間放置した後、余剰の塩化ビニル樹脂組成物を振り落とし、さらに、任意の温度下、30秒以上3分以下の間放置する。その後、金型を10℃以上60℃以下に冷却し、得られた塩化ビニル樹脂成形体を金型から脱型することにより、好適に得られる。
本発明の積層体は、上述した塩化ビニル樹脂成形体と発泡ポリウレタン成形体を積層して得ることができる。積層方法は、(1)塩化ビニル樹脂成形体と、発泡ポリウレタン成形体とを別途製造した後に、熱融着、熱接着、又は公知の接着剤などを用いることにより貼り合わせる方法;(2)塩化ビニル樹脂成形体上で、発泡ポリウレタン成形体の原料となるイソシアネート類とポリオール類などとを反応させて重合を行うと共に、公知の方法によりポリウレタンの発泡を行い、塩化ビニル樹脂成形体上に発泡ポリウレタン成形体を直接形成する方法;などが挙げられる。後者の方法(2)の方が、工程が簡素であり、かつ、種々の形状の積層体を得る場合においても、塩化ビニル樹脂成形体と発泡ポリウレタン成形体との接着を確実に行うことができるのでより好適である。
シリコーンオイルの粘度は、ASTM D 445-46Tに従い、ウッベローデ粘度計を用いて、温度25℃における動粘度ηCS/25(単位:mm2/s=cs)として測定した。
(a1)塩化ビニル樹脂粒子及び(a2)塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂の平均重合度は、JIS K6720-2に準拠して、(a1)塩化ビニル樹脂粒子及び(a2)塩化ビニル樹脂微粒子のそれぞれを、シクロヘキサノンに溶解させて粘度を測定することにより、算出した。
(a1)塩化ビニル樹脂粒子及び(a2)塩化ビニル樹脂微粒子の平均粒子径(体積平均粒子径)は、塩化ビニル樹脂粒子及び塩化ビニル樹脂微粒子を、それぞれ水槽内に分散させ、以下に示す装置を用いて、光の回折・散乱強度分布を測定・解析し、粒子径及び体積基準の粒子径分布を測定することにより、算出した。
・装置:レーザー回折式粒度分布測定機(島津製作所製、型番「SALD-2300」)
・測定方式:レーザー回折及び散乱
・測定範囲:0.017μm~2500μm
・光源:半導体レーザー(波長680nm、出力3mW)
得られた発泡ポリウレタン成形体が裏打ちされた積層体を試料とし、当該試料を170mm×300mmの寸法の試験片に切り出し、当該試験片を、学振型摩耗試験機(大栄科学精器製作所製、製品名「RT-200」)の試料台の上に、塩化ビニル樹脂成形体側が上になるように置いた。そして、当該摩耗試験機に500gの荷重を取り付けて試験片に掛かる合計荷重を500gとした。次に、摩耗試験機の先端にペーパータオル(日本製紙クレシア(株)製、製品名「COMFORT」)1枚を取り付けた後、取り付けたペーパータオルを、ペーパータオルが試験片の塩化ビニル樹脂成形体側の表面と接触する状態で10往復させることにより、試験片表面とペーパータオルとを摩耗させた。続けて、摩耗させた後の試験片表面についた、ペーパータオル地から生じた繊維カスの付着度合いに応じて、試験片(塩化ビニル樹脂成形体側)上で異なる付着度合いを有する20箇所を選定した。そして、当該20箇所における摩耗試験前後での試験片表面の明度の差(ΔL値)を色差計(コニカミノルタセンシング社製、製品名「CR-400」)を用いて測定した。ΔL値が小さいほど、塩化ビニル樹脂成形体の毛羽付き性が優れていることを示す。
得られた塩化ビニル樹脂成形体としての塩化ビニル樹脂成形シートを試料とし、当該試料をJIS K 6251に記載の1号ダンベルで打ち抜いた。そして、JIS K 7113に準拠して、引張速度200mm/分、-35℃の低温下における、引張応力(MPa)及び引張伸び(%)を測定した。-35℃での引張伸びが大きいほど、塩化ビニル樹脂成形体が、低温での柔軟性に優れていることを示す。
得られた発泡ポリウレタン成形体が裏打ちされた積層体を試料とし、当該試料をオーブンに入れ、温度130℃の環境下で100時間、当該試料を加熱した。その後、発泡ポリウレタン層を当該試料から剥離し、上記低温引張試験(初期)と同様の条件で、-35℃の低温下における、引張応力(MPa)及び引張伸び(%)を測定した。-35℃での引張伸びが大きいほど、塩化ビニル樹脂成形体が、耐熱性(加熱後の低温での柔軟性)に優れていることを示す。
<塩化ビニル樹脂組成物の調製>
表1に示す配合成分のうち、可塑剤としてのトリメリット酸エステル可塑剤及びエポキシ化大豆油と、ダスティング剤A、Bとしての2種類の塩化ビニル樹脂微粒子とを除く成分をヘンシェルミキサーに入れて混合した。そして、混合物の温度が80℃に上昇した時点で上記可塑剤を全て添加して混合物を得、当該混合物を更に昇温することにより、ドライアップ(可塑剤が塩化ビニル樹脂粒子に吸収されて、上記混合物がさらさらになった状態をいう。)させた。その後、ドライアップさせた混合物が温度70℃以下に冷却された時点で、ダスティング剤A、Bとしての2種類の塩化ビニル樹脂微粒子を添加し、粉体成形用塩化ビニル樹脂組成物を調製した。
<塩化ビニル樹脂成形体の製造>
得られた粉体成形用塩化ビニル樹脂組成物を、温度250℃に加熱したシボ付き金型に振りかけ、塩化ビニル樹脂成形シートの厚みが1mmになるよう、8秒~20秒程度の任意の時間放置して溶融させた後、余剰の塩化ビニル樹脂組成物を振り落とした。その後、塩化ビニル樹脂組成物を振りかけたシボ付き金型を、温度200℃に設定したオーブンに静置させ、静置から60秒経過した時点で、シボ付き金型を冷却水で冷却した。金型温度が40℃まで冷却された時点で、塩化ビニル樹脂成形体として、150mm×200mm×1mmの塩化ビニル樹脂成形シートを金型から脱型した。
そして、得られた塩化ビニル樹脂成形シートについて、上述の方法に従って、低温引張試験(初期)を実施した。結果を表1に示す。
得られた塩化ビニル樹脂成形シート2枚を、200mm×300mm×10mmの金型中に、シボ付き面を下にして重ならないように敷いた。
別途、プロピレングリコールのプロピレンオキサイド・エチレンオキサイド(PO・EO)ブロック付加物(水酸基価28、末端EO単位の含有量=10%、内部EO単位の含有量4%)50質量部、グリセリンのPO・EOブロック付加物(水酸基価21、末端EO単位の含有量=14%)50質量部、水2.5質量部、トリエチレンジアミンのエチレングリコ-ル溶液(東ソー(株)製、商品名「TEDA-L33」)0.2質量部、トリエタノールアミン1.2質量部、トリエチルアミン0.5質量部、及び整泡剤(信越化学工業(株)製、商品名「F-122」)0.5質量部からなるポリオール混合物を用意した。そして、用意したポリオール混合物と、ポリメチレンポリフェニレンポリイソシアネート(ポリメリックMDI)とを、インデックスが98になる比率で混合して混合液を調製した。そして、調製した混合液を、上述の通り金型中に敷かれた塩化ビニル樹脂成形シート2枚の上にそれぞれ注いだ。その後、金型に348mm×255mm×10mmのアルミニウム板で金型に蓋をすることで金型を密閉した。金型を密閉してから5分後、1mm厚の塩化ビニル樹脂成形シートからなる表皮に、9mm厚、密度0.18g/cm3の発泡ポリウレタン成形体が裏打ちされた積層体を金型から取り出した。
そして、得られた積層体について、上述の方法に従って、毛羽付き性試験及び低温引張試験(加熱後)を実施した。結果を表1に示す。
2)花王(株)製、トリメックスN-08
3)(株)ADEKA製、アデカサイザーO-130S
4)協和化学工業(株)製、アルカマイザー5
5)水澤化学工業(株)製、MIZUKALIZER DS
6)昭和電工(株)製、カレンズ DK-1
7)堺化学工業(株)、SAKAI SZ2000
8)(株)ADEKA製、LA-72
9)(株)ADEKA製、アデカスタブ 522A
10)(株)ADEKA製、アデカスタブ LS-12
11)信越シリコーン(株)製、KF-9701
12)信越シリコーン(株)製、KF-96H-1万cs
13)信越シリコーン(株)製、KF-96H-10万cs
14)信越シリコーン(株)製、KF-96H-30万cs
15)信越シリコーン(株)製、KF-96H-100万cs
16)新第一塩ビ(株)製、ZEST PQLTX(乳化重合で得られた(a2)塩化ビニル樹脂微粒子、平均重合度800、平均粒子径2μm)
17)東ソー(株)製、リューロンペースト761(乳化重合で得られた(a2)塩化ビニル樹脂微粒子、平均重合度2100、平均粒子径2μm)
18)大日精化工業(株)製、DA PX-1720 ブラック(A)
Claims (9)
- (a)塩化ビニル樹脂、及び(b)粘度が10cs以上200×104cs以下であるシリコーンオイルを含み、前記(b)粘度が10cs以上200×104cs以下であるシリコーンオイルの含有量が、前記(a)塩化ビニル樹脂100質量部当たり、0.1質量部以上10質量部以下である、粉体成形用塩化ビニル樹脂組成物。
- 前記(a)塩化ビニル樹脂が、(a1)平均重合度が800以上5000以下である塩化ビニル樹脂粒子、及び(a2)平均重合度が500以上5000以下である塩化ビニル樹脂微粒子からなり、
前記(a1)平均重合度が800以上5000以下である塩化ビニル樹脂粒子の含有割合が70質量%以上100質量%以下であり、
前記(a2)平均重合度が500以上5000以下である塩化ビニル樹脂微粒子の含有割合が0質量%以上30質量%以下である、請求項1に記載の粉体成形用塩化ビニル樹脂組成物。 - 更に可塑剤を含み、前記可塑剤の含有量が、前記(a)塩化ビニル樹脂100質量部当たり、90質量部以上である、請求項1又は2に記載の粉体成形用塩化ビニル樹脂組成物。
- パウダースラッシュ成形に用いられる、請求項1~3のいずれか1項に記載の粉体成形用塩化ビニル樹脂組成物。
- 請求項1~4のいずれか1項に記載の粉体成形用塩化ビニル樹脂組成物を粉体成形してなる、塩化ビニル樹脂成形体。
- 請求項1~4のいずれか1項に記載の粉体成形用塩化ビニル樹脂組成物をパウダースラッシュ成形してなる、塩化ビニル樹脂成形体。
- 自動車インスツルメントパネル表皮用である、請求項5又は6に記載の塩化ビニル樹脂成形体。
- 発泡ポリウレタン成形体と、請求項5~7のいずれか1項に記載の塩化ビニル樹脂成形体とを有する、積層体。
- 自動車インスツルメントパネル用である、請求項8に記載の積層体。
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