WO2020196396A1 - 塩化ビニル樹脂組成物、塩化ビニル樹脂成形体および積層体 - Google Patents
塩化ビニル樹脂組成物、塩化ビニル樹脂成形体および積層体 Download PDFInfo
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- WO2020196396A1 WO2020196396A1 PCT/JP2020/012693 JP2020012693W WO2020196396A1 WO 2020196396 A1 WO2020196396 A1 WO 2020196396A1 JP 2020012693 W JP2020012693 W JP 2020012693W WO 2020196396 A1 WO2020196396 A1 WO 2020196396A1
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- Prior art keywords
- vinyl chloride
- chloride resin
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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
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C39/12—Making multilayered or multicoloured articles
- B29C39/123—Making multilayered articles
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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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- 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
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C39/10—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles incorporating preformed parts or layers, e.g. casting around inserts or for coating articles
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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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- 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
- B32B5/20—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 foamed in situ
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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
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
- B29K2027/06—PVC, i.e. polyvinylchloride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
- B29L2031/3005—Body finishings
- B29L2031/3008—Instrument panels
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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
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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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
- B32B2266/00—Composition of foam
- B32B2266/02—Organic
- B32B2266/0214—Materials belonging to B32B27/00
- B32B2266/0278—Polyurethane
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- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
- B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
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- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
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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
- B32B2605/00—Vehicles
- B32B2605/003—Interior finishings
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
Definitions
- the present invention relates to a vinyl chloride resin composition, a vinyl chloride resin molded product and a laminate.
- Vinyl chloride resin is generally used for various purposes because it has excellent properties such as cold resistance, heat resistance, and oil resistance.
- a foam material such as polyurethane foam is lined on a skin made of a vinyl chloride resin molded product or a skin made of a vinyl chloride resin molded product.
- Automotive interior materials such as laminated bodies made of plastic are used.
- the vinyl chloride resin molded body constituting the skin of the automobile interior parts such as an automobile instrument panel is made by powdering a vinyl chloride resin composition containing, for example, a vinyl chloride resin, a plasticizer, and an additive such as a pigment. It is manufactured by molding using a known molding method such as slush molding (see, for example, Patent Document 1).
- a vinyl chloride resin composition containing vinyl chloride resin particles, a trimellitic acid ester-based plasticizer, and an additive such as a pigment composed of a mixture of phthalocyanine blue, titanium oxide and carbon.
- a skin made of a vinyl chloride resin molded product is manufactured by powder molding the product.
- the vinyl chloride resin molded product used as the skin or the like of an automobile interior part is required to have excellent flexibility when evaluated at a low temperature (hereinafter, may be referred to as "low temperature flexibility").
- low temperature flexibility When the vinyl chloride resin molded product is heated, its low temperature flexibility is reduced due to heat aging or the like. Therefore, the vinyl chloride resin molded product is further required to have a small decrease in low temperature flexibility due to heating, that is, to maintain good low temperature flexibility before and after heating.
- the vinyl chloride resin composition is required to be able to suppress contamination of the mold after demolding the vinyl chloride resin molded product obtained by molding, that is, to be excellent in mold contamination resistance.
- the vinyl chloride resin composition of the above-mentioned prior art has room for improvement in mold stain resistance.
- an object of the present invention is to provide a vinyl chloride resin composition capable of forming a vinyl chloride resin molded product capable of maintaining good low temperature flexibility before and after heating and having excellent mold contamination resistance. And. Another object of the present invention is to provide a vinyl chloride resin molded product capable of maintaining good low temperature flexibility before and after heating. Furthermore, an object of the present invention is to provide a laminate provided with the vinyl chloride resin molded product.
- the present inventor has conducted diligent studies for the purpose of solving the above problems. Then, the present inventor uses a polyester containing a trimellitic acid ester and a predetermined structural unit as a plasticizer, sets the total content of the trimellitic acid ester and the polyester to a predetermined value or more, and contains the total content. If the vinyl chloride resin composition is obtained so that the ratio of the polyester content to the amount exceeds a predetermined value, it is possible to form a vinyl chloride resin molded body capable of maintaining good low-temperature flexibility before and after heating. At the same time, they have found that they are also excellent in mold contamination resistance, and have completed the present invention.
- the present invention aims to advantageously solve the above problems, and the vinyl chloride resin composition of the present invention contains (a) a vinyl chloride resin and (x) a plasticizer.
- the (x) plasticizer contains (b) trimellitic acid ester, (c) structural units derived from adipic acid, and structural units derived from 3-methyl-1,5-pentanediol.
- the total content of the (b) trimellitic acid ester and the (c) polyester is 65 parts by mass or more per 100 parts by mass of the (a) vinyl chloride resin, and the above (b).
- the ratio of the content of the (c) polyester to the total content of the trimellitic acid ester and the (c) polyester is more than 50% by mass.
- the vinyl chloride resin, the trimellitic acid ester as a plasticizer, and the polyester containing a predetermined structural unit are contained, and the total content of the trimellitic acid ester and the polyester is at least a predetermined value and If the ratio of the polyester content to the total content exceeds a predetermined value, a vinyl chloride resin molded body capable of maintaining good low-temperature flexibility before and after heating can be formed. , Excellent mold contamination resistance can be exhibited.
- the total content of the (b) trimellitic acid ester and the (c) polyester is 90 parts by mass or more per 100 parts by mass of the (a) vinyl chloride resin. It is preferable to have. As described above, when the total content of (b) trimellitic acid ester and (c) polyester is at least the above-mentioned predetermined value, the meltability of the vinyl chloride resin composition can be enhanced.
- the vinyl chloride resin (a) has a volume average particle diameter of 30 ⁇ m or more and 500 ⁇ m or less, and a vinyl chloride resin having a volume average particle diameter of less than 30 ⁇ m. It is preferable to contain fine particles. As described above, if the vinyl chloride resin (a) contains vinyl chloride resin particles having a volume average particle diameter within a predetermined range and vinyl chloride resin fine particles having a volume average particle diameter of less than a predetermined value, vinyl chloride The meltability of the resin composition can be increased.
- the "volume average particle diameter" of the vinyl chloride resin particles and the vinyl chloride resin fine particles can be measured by a laser diffraction method in accordance with JIS Z8825.
- the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is preferably 5000 or less.
- the meltability of the vinyl chloride resin composition can be further enhanced.
- the "average degree of polymerization" of the vinyl chloride resin can be measured according to JIS K6720-2.
- the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles is preferably 2600 or less.
- the meltability of the vinyl chloride resin composition can be further enhanced.
- the (x) plasticizer contains the (b) trimellitic acid ester in an amount of 7% by mass or more and less than 49.5% by mass, and the polyester (c) in an amount of 37.5. It contains more than 75% by mass and 75% by mass or less, (d) 1% by mass or more and 20% by mass or less of dodecane diester, and (e) 0% by mass of plasticizers other than the above (b), (c) and (d). It is preferable that the content is 5% by mass or less.
- the plasticizers (x) are (b) trimellitic acid ester, (c) polyester, (d) dodecanedioic acid diester, and (e) plasticizers other than the above (b) to (d). If it is included in a ratio, it is possible to increase the tensile elongation (hereinafter, may be referred to as "low temperature tensile elongation") when the vinyl chloride resin molded product to be formed is evaluated at a low temperature after being heated.
- low temperature tensile elongation tensile elongation
- the vinyl chloride resin composition of the present invention contains 66 parts by mass of the (b) trimellitic acid ester, the (c) polyester, and the (d) dodecanedioic acid diester per 100 parts by mass of the vinyl chloride resin. It is preferable to contain more than 200 parts by mass. If the vinyl chloride resin composition contains (b) trimellitic acid ester, (c) polyester, and (d) dodecanedioic acid diester in the above-mentioned predetermined amounts in total, the low temperature after heating of the vinyl chloride resin molded product formed. The tensile elongation can be further increased.
- the mass ratio (c / d) of the (c) polyester and the (d) dodecanedioic acid diester is preferably 3/2 or more and 10/1 or less.
- the mass ratio (c / d) of (c) polyester and (d) dodecanedioic acid diester is within the above-mentioned predetermined range, the low-temperature tensile elongation after heating of the vinyl chloride resin molded product can be further enhanced.
- the vinyl chloride resin composition of the present invention is preferably used for powder molding.
- a vinyl chloride resin molded product that can be satisfactorily used as an automobile interior material such as a skin for an automobile instrument panel can be easily obtained.
- the vinyl chloride resin composition of the present invention is preferably used for powder slush molding.
- a vinyl chloride resin molded product that can be satisfactorily used as an automobile interior material such as a skin for an automobile instrument panel can be more easily obtained.
- the vinyl chloride resin molded product of the present invention is preferably for the skin of an automobile instrument panel.
- the manufactured automobile instrument panel has a skin that can maintain good low temperature flexibility before and after heating.
- the present invention is intended to advantageously solve the above problems, and the laminate of the present invention is characterized by having either a foamed polyurethane molded product or the above-mentioned vinyl chloride resin molded product.
- the polyurethane foam molded body and the laminate having the vinyl chloride resin molded body described above include a vinyl chloride resin molded body portion capable of maintaining good low temperature flexibility before and after heating.
- the laminate of the present invention is for an automobile instrument panel.
- the skin of the manufactured automobile instrument panel can maintain good low temperature flexibility before and after heating.
- a vinyl chloride resin molded product capable of forming a vinyl chloride resin molded product capable of maintaining good low temperature flexibility before and after heating, and also providing a vinyl chloride resin composition having excellent mold contamination resistance. .. Further, according to the present invention, it is possible to provide a vinyl chloride resin molded product capable of maintaining good low temperature flexibility before and after heating. Further, according to the present invention, it is possible to provide a laminated body including the vinyl chloride resin molded body.
- the vinyl chloride resin composition of the present invention can be used, for example, when forming the vinyl chloride resin molded product of the present invention. Then, the vinyl chloride resin molded product formed by using the vinyl chloride resin composition of the present invention is suitably used as an automobile interior material such as a skin provided in an automobile interior part such as an automobile instrument panel and a door trim. Can be done. Further, the vinyl chloride resin molded product of the present invention can be used, for example, when forming the laminated body of the present invention. Then, the laminate formed by using the vinyl chloride resin molded product of the present invention can be suitably used as an automobile interior material used when manufacturing automobile interior parts such as an automobile instrument panel and a door trim.
- the vinyl chloride resin composition of the present invention contains (a) a vinyl chloride resin and (x) a plasticizer.
- the vinyl chloride resin composition of the present invention contains (x) a plasticizer, (b) a trimellitic acid ester, (c) a polyester containing a predetermined structural unit, and (b) a trimellitic acid ester.
- the total content of polyester containing a predetermined structural unit is 65 parts by mass or more per 100 parts by mass of (a) vinyl chloride resin, (b) trimellitic acid ester and (c) predetermined structure.
- the vinyl chloride resin composition of the present invention may optionally further contain components other than the above-mentioned (a) vinyl chloride resin and (x) plasticizer. Further, the vinyl chloride resin composition of the present invention further comprises (x) a plasticizer other than the above-mentioned (b) trimellitic acid ester and (c) polyester containing a predetermined structural unit. It may be included.
- the vinyl chloride resin composition of the present invention is capable of forming a vinyl chloride resin molded product capable of maintaining good low-temperature flexibility before and after heating, and is excellent in mold contamination resistance. Therefore, if the vinyl chloride resin composition of the present invention is used, chloride suitable as an automobile interior material, for example, an automobile instrument panel skin and a door trim skin that can maintain good low-temperature flexibility before and after heating. A vinyl resin molded product can be obtained.
- the vinyl chloride resin composition of the present invention is a powder. It is preferably used for molding, and more preferably used for powder slush molding.
- the vinyl chloride resin (a) a particulate vinyl chloride resin is usually used.
- the vinyl chloride resin (a) may contain, for example, one or more types of vinyl chloride resin particles, and optionally further contains one or more types of vinyl chloride resin fine particles. Can be done.
- (a) vinyl chloride resin preferably contains at least vinyl chloride resin particles, and more preferably contains vinyl chloride resin particles and vinyl chloride resin fine particles.
- the vinyl chloride resin (a) can be produced by any conventionally known production method such as a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, and a bulk polymerization method.
- the “resin particles” refer to particles having a particle diameter of 30 ⁇ m or more
- the “resin fine particles” refer to particles having a particle diameter of less than 30 ⁇ m.
- (a) vinyl chloride resin in addition to the copolymer composed of the vinyl chloride monomer unit, vinyl chloride containing the vinyl chloride monomer unit in an amount of preferably 50% by mass or more, more preferably 70% by mass or more.
- a system copolymer can be mentioned.
- a monomer (comonomer) copolymerizable with a vinyl chloride monomer that can constitute a vinyl chloride-based copolymer for example, International Publication No. 2016/098344 is described. You can use things. In addition, one of these components may be used alone, or two or more of these components may be used in combination at any ratio.
- Vinyl chloride resin particles In the vinyl chloride resin composition, the vinyl chloride resin particles usually function as a matrix resin (base material). The vinyl chloride resin particles are preferably produced by a suspension polymerization method.
- the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is preferably 800 or more, more preferably 1000 or more, further preferably 1300 or more, and more preferably 5000 or less. It is preferably 3000 or less, more preferably 2800 or less, particularly preferably 2300 or less, and even more preferably 1900 or less.
- tension is obtained while sufficiently ensuring the physical strength of the vinyl chloride resin molded product formed by using the vinyl chloride resin composition. This is because the characteristics, especially the tensile elongation, can be improved.
- a vinyl chloride resin molded product having good tensile elongation can be used, for example, as a skin of an automobile instrument panel having excellent ductility, which breaks as designed without scattering debris when the airbag expands and expands. It can be suitably used as an automobile interior material. Further, when the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is not more than the above upper limit, the meltability of the vinyl chloride resin composition can be improved.
- the volume average particle diameter of the 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, and more preferably 200 ⁇ m or less. This is because when the volume average particle diameter of the vinyl chloride resin particles is at least the above lower limit, the powder fluidity of the vinyl chloride resin composition is further improved. Further, when the volume average particle diameter of the vinyl chloride resin particles is equal to or less than the above upper limit, the meltability of the vinyl chloride resin composition is improved and the surface smoothness of the vinyl chloride resin molded product formed by using the composition is improved. Because it can be improved.
- the content ratio of the vinyl chloride resin particles in the (a) vinyl chloride resin is preferably 70% by mass or more, more preferably 80% by mass or more, and can be 100% by mass, 95. It is preferably 1% by mass or less, and more preferably 90% by mass or less.
- the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles is preferably 500 or more, more preferably 700 or more, preferably 2600 or less, and more preferably 2400 or less.
- the powder fluidity of the vinyl chloride resin composition becomes better and the composition is used. This is because the tensile elongation of the obtained molded product becomes better.
- the meltability of the vinyl chloride resin composition is improved, and the vinyl chloride resin molded product formed by using the composition is improved. This is because the surface smoothness is improved.
- the volume average particle size of the vinyl chloride resin fine particles is usually less than 30 ⁇ m, preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, preferably 0.1 ⁇ m or more, and 1 ⁇ m or more. Is more preferable.
- the volume average particle diameter of the vinyl chloride resin fine particles is not less than the above lower limit, the powder fluidity of the vinyl chloride resin composition can be further improved without, for example, excessively reducing the size as a dusting agent. Because. Further, when the volume average particle diameter of the vinyl chloride resin fine particles is not more than the above upper limit, the meltability of the vinyl chloride resin composition is increased, and the surface smoothness of the formed vinyl chloride resin molded product can be further improved. Is.
- the content ratio of the vinyl chloride resin fine particles in the (a) vinyl chloride resin may be 0% by mass, but is preferably 5% by mass or more, more preferably 10% by mass or more. It is preferably 30% by mass or less, and more preferably 20% by mass or less. This is because if the content ratio of the vinyl chloride resin fine particles in the vinyl chloride resin is not less than the above lower limit, the powder fluidity of the vinyl chloride resin composition is further improved. Further, (a) When the content ratio of the vinyl chloride resin fine particles in the vinyl chloride resin is not more than the above upper limit, the physical strength of the vinyl chloride resin molded product formed by using the vinyl chloride resin composition can be further increased. Because.
- the plasticizer contains (b) a trimellitic acid ester and (c) a polyester containing a predetermined structural unit. Further, the (x) plasticizer may further contain (d) a dodecanedioic acid diester. Further, the (x) plasticizer further contains (e) other plasticizers other than (b) trimellitic acid ester, (c) polyester containing a predetermined structural unit, and (d) dodecanedioic acid diester. You may be.
- the content of (x) plasticizer in the vinyl chloride resin composition ((b) trimellitic acid ester, (c) polyester containing a predetermined structural unit, (d) dodecane diic acid diester, and (e). )
- the total content of other plasticizers is preferably 70 parts by mass or more, more preferably 85 parts by mass or more, and further preferably 95 parts by mass with respect to 100 parts by mass of the above (a) vinyl chloride resin. It is 5 parts by mass or more, preferably 200 parts by mass or less, more preferably 160 parts by mass or less, and further preferably 140 parts by mass or less.
- the vinyl chloride resin molded product formed by using the vinyl chloride resin composition can further maintain low temperature flexibility before and after heating. Further, when the content of the (x) plasticizer is at least the above lower limit, the low temperature flexibility of the vinyl chloride resin molded product formed by using the vinyl chloride resin composition can be enhanced. Further, when the content of the (x) plasticizer is at least the above lower limit, the meltability of the vinyl chloride resin composition can be enhanced. On the other hand, when the content of the (x) plasticizer is not more than the above upper limit, it is possible to suppress stickiness on the surface of the vinyl chloride resin molded product formed by using the vinyl chloride resin composition.
- trimellitic acid ester is preferably an ester compound of trimellitic acid and a monohydric alcohol.
- the monohydric alcohol are not particularly limited, and include 1-hexanol, 1-heptanol, 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol and the like.
- Fatty alcohols can be mentioned.
- the monohydric alcohol an aliphatic alcohol having 6 to 18 carbon atoms is preferable, and a linear aliphatic alcohol having 6 to 18 carbon atoms is more preferable.
- trimellitic acid ester examples include trimellitic acid tri-n-hexyl, trimellitic acid tri-n-heptyl, trimellitic acid tri-n-octyl, trimellitic acid tri- (2-ethylhexyl).
- Trimellitic acid tri-n-nonyl Trimellitic acid tri-n-decyl, trimellitic acid triisodecyl, trimellitic acid tri-n-undecyl, trimellitic acid tri-n-dodecyl, trimellitic acid trialkyl ester ( Alkyl groups with different carbon numbers [however, esters having two or more types of carbon numbers in the molecule], trimellitic acid tri-n-alkyl esters (alkyl groups with different carbon numbers [however, carbons] The number is 6 to 18. Esters having two or more kinds in the molecule), and mixtures thereof and the like.
- trimellitic acid ester More preferred (b) specific examples of the trimellitic acid ester are trimellitic acid tri-n-octyl, trimellitic acid tri- (2-ethylhexyl), trimellitic acid tri-n-nonyl, trimellitic acid tri-n-. These include decyl, trimellitic acid tri-n-alkyl esters (esters having two or more alkyl groups having different carbon atoms [however, the number of carbon atoms is 6 to 18] in the molecule), and mixtures thereof.
- the content of (b) trimellitic acid ester in the vinyl chloride resin composition is preferably 5 parts by mass or more, and more preferably 10 parts by mass with respect to 100 parts by mass of the (a) vinyl chloride resin. It is more preferably 15 parts by mass or more, preferably 70 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less.
- the content of (b) trimellitic acid ester in the vinyl chloride resin composition is at least the above lower limit, the meltability of the vinyl chloride resin composition can be enhanced. Further, when the content of (b) trimellitic acid ester in the vinyl chloride resin composition is at least the above lower limit, the mold contamination resistance of the vinyl chloride resin composition can be further enhanced.
- the vinyl chloride resin molded product formed by using the vinyl chloride resin composition has low temperature flexibility before and after heating. It can be maintained even better. Further, when the content of (b) trimellitic acid ester in the vinyl chloride resin composition is not more than the above upper limit, the low temperature flexibility of the vinyl chloride resin molded product formed by using the vinyl chloride resin composition can be enhanced. it can.
- polyester containing a predetermined structural unit contains a structural unit derived from adipic acid and a structural unit derived from 3-methyl-1,5-pentanediol.
- polyester containing a predetermined structural unit may have a structural unit other than the structural unit derived from adipic acid and the structural unit derived from 3-methyl-1,5-pentanediol, but adipine.
- the total of the acid-derived structural units and the 3-methyl-1,5-pentanediol-derived structural units is preferably 50% by mass or more, and more preferably 80% by mass or more of the total structural units.
- the polyester containing a predetermined structural unit preferably has only a structural unit derived from adipic acid and a structural unit derived from 3-methyl-1,5-pentanediol as repeating units.
- the polyester containing the predetermined structural unit (c) is not particularly limited, and can be obtained by condensation polymerization of adipic acid and 3-methyl-1,5-pentanediol.
- the condensation polymerization described above can be carried out in the presence of a catalyst.
- the condensation polymerization described above can be carried out using an alcohol and / or a monobasic acid as the terminal stop component.
- the condensation polymerization of adipic acid and 3-methyl-1,5-pentanediol and the termination reaction of the obtained condensed polymer and the terminal stop component may be carried out collectively or separately. May be done in.
- the product obtained through the condensation polymerization and the termination reaction may be subjected to post-treatment such as distillation. Then, known conditions can be adopted as the reaction conditions for condensation polymerization such as the amounts of the above-mentioned monomer, catalyst, and terminal stop component used.
- the polyester containing the predetermined structural unit (c) a commercially available product may be used.
- the catalyst used in the condensation polymerization reaction is not particularly limited, and examples thereof include dibutyltin oxide and tetraalkyl titanate.
- alcohols that can be used as terminal arrest components include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, isohexanol, heptanol, isoheptanol, octanol, isooctanol, and 2-ethyl.
- examples of the monobasic acid that can be used as the terminal stop component include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid, caproic acid, heptanic acid, capric acid, 2-ethylhexic acid, and pelargonic acid. Included are capric acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, benzoic acid and mixtures thereof. Of these, 2-ethylhexanol is preferable as the terminal arrest component.
- the polyester containing the predetermined structural unit (c) preferably has a number average molecular weight of 1000 or more, more preferably 2000 or more, preferably 10000 or less, and preferably 7000 or less. Is more preferable.
- the "number average molecular weight" can be measured by the VPO (vapor pressure osmotic pressure) method.
- the polyester containing the predetermined structural unit (c) preferably has an acid value of 1 or less.
- the polyester containing the predetermined structural unit (c) preferably has a hydroxyl value of 30 or less.
- the above-mentioned (c) predetermined polyester preferably has a viscosity of 500 mPa ⁇ s or more, more preferably 1000 mPa ⁇ s or more, preferably 8000 mPa ⁇ s or less, and 5000 mPa ⁇ s or less. Is more preferable.
- the "viscosity" conforms to JIS Z8803 and can be measured at a temperature of 23 ° C.
- the content of the polyester containing the predetermined structural unit (c) in the vinyl chloride resin composition is preferably 30 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin (a). It is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, preferably 150 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 90 parts by mass or less, and particularly preferably. Is 80 parts by mass or less.
- the content of (c) polyester containing a predetermined structural unit in the vinyl chloride resin composition is equal to or higher than the above lower limit, the vinyl chloride resin molded product formed by using the vinyl chloride resin composition is low-temperature flexible before and after heating. The sex can be maintained even better.
- the content of (c) polyester containing a predetermined structural unit in the vinyl chloride resin composition is equal to or higher than the above lower limit, the low temperature flexibility of the vinyl chloride resin molded product formed by using the vinyl chloride resin composition. Can be enhanced.
- the content of (c) polyester containing a predetermined structural unit in the vinyl chloride resin composition is not more than the above upper limit, the meltability of the vinyl chloride resin composition can be enhanced.
- the content of (c) polyester containing a predetermined structural unit in the vinyl chloride resin composition is not more than the above upper limit, the mold contamination resistance of the vinyl chloride resin composition can be further enhanced.
- the total content of (b) trimellitic acid ester and (c) polyester containing the predetermined structural unit in the vinyl chloride resin composition is 65 parts by mass with respect to 100 parts by mass of (a) vinyl chloride resin. It is necessary that it is 80 parts by mass or more, more preferably 90 parts by mass or more, preferably 200 parts by mass or less, and more preferably 160 parts by mass or less. , 140 parts by mass or less is more preferable.
- the total content of (b) trimellitic acid ester and polyester containing the above-mentioned (c) predetermined structural unit is not more than the above lower limit, the vinyl chloride resin molded product formed by using the vinyl chloride resin composition is heated.
- the vinyl chloride resin molded product formed by using the vinyl chloride resin composition It is possible to prevent the surface from becoming sticky.
- the content of the polyester containing the predetermined structural unit (c) in the total content of the (b) trimellitic acid ester and the polyester containing the predetermined structural unit in the vinyl chloride resin composition needs to be more than 50% by mass, preferably more than 52% by mass, more preferably more than 55% by mass, and further preferably more than 70% by mass.
- the ratio of the content of (b) trimellitic acid ester and the polyester containing the predetermined structural unit to the total content of the polyester containing the predetermined structural unit (c) exceeds 50% by mass.
- the vinyl chloride resin molded body formed by using the vinyl chloride resin composition can maintain good low temperature flexibility before and after heating.
- the ratio of the content of the polyester containing the predetermined structural unit to the total content of the trimellitic acid ester and the polyester containing the predetermined structural unit exceeds the above lower limit. If this is the case, the low temperature flexibility of the vinyl chloride resin molded product formed by using the vinyl chloride resin composition can be enhanced.
- the ratio of the above needs to be less than 100% by mass, preferably less than 98% by mass, more preferably less than 95% by mass, and even more preferably less than 92% by mass.
- the ratio of the content of (b) trimellitic acid ester and the polyester containing the predetermined structural unit to the total content of the polyester containing the predetermined structural unit is less than 100% by mass. If there is, the mold contamination resistance of the vinyl chloride resin composition can be sufficiently enhanced. Further, the ratio of the content of the polyester containing the predetermined structural unit to the total content of the trimellitic acid ester and the polyester containing the predetermined structural unit is less than the above upper limit. If there is, the meltability of the vinyl chloride resin composition can be enhanced.
- the dodecanedioic acid diester that can be contained in the plasticizer (d) consists of a diester obtained by esterifying dodecanedioic acid or an alkylated product thereof with an alcohol.
- the alcohol esterified with dodecanedioic acid may be an aliphatic alcohol, an alicyclic alcohol, or an aromatic alcohol.
- Preferred alcohols are aliphatic alcohols.
- the alcohol may be one kind or a combination of two or more kinds of alcohols.
- the carbon number of the alcohol is preferably 6 or more and 12 or less, and more preferably 8 or more and 10 or less.
- dodecane diacid diesters include dimethyl dodecane diate, diethyl dodecane diate, dipropyl dodecane diate, diisopropyl dodecane diate, dibutyl dodecane diate, diisobutyl dodecane diate, dipentyl dodecane diate, dodecane diacid Diisopentyl, dihexyl dodecane diate, diisohexyl dodecane diate, diheptyl dodecane diate, diisoheptyl dodecane diate, di-n-octyl dodecane diate, diisooctyl dodecane diate, bis dodecane diate (2-ethylhexyl), n dodecane diate -Octyl (2-ethylhexyl), di-n-nonyl dodecane, diisononyl
- the preferred (b) dodecane diester is a dodecane diester composed of dodecane diic acid and an aliphatic alcohol having 6 to 12 carbon atoms
- the more preferable (b) dodecane diacid diester is dodecane diacid and carbon atoms.
- the preferred (b) dodecane diester is bis dodecane diate (2-ethylhexyl).
- the dodecane diester may be used alone or in combination of two or more.
- the content ratio of (b) trimellitic acid ester in (x) plasticizer is preferably 7% by mass or more, more preferably 25% by mass or more, and 49.5% by mass. It is preferably less than.
- the content ratio of (b) trimellitic acid ester in (x) plasticizer is within the above-mentioned predetermined range, the low-temperature flexibility of the vinyl chloride resin molded product to be formed and the low-temperature tensile elongation after heating can be further enhanced. it can.
- the content ratio of the polyester containing the predetermined structural unit (c) in the (x) plasticizer is preferably more than 37.5% by mass, more preferably more than 49% by mass, 75. It is preferably 5% by mass or less, more preferably 55% by mass or less, further preferably 54% by mass or less, and further preferably 53% by mass or less.
- the content ratio of (x) polyester containing a predetermined structural unit in the plasticizer is within the above range, the flexibility of the vinyl chloride resin molded product formed at low temperature and the low temperature tensile elongation after heating Can be further enhanced.
- the content ratio of the (d) dodecanedioic acid diester in the (x) plasticizer is preferably 1% by mass or more, more preferably 5% by mass or more, and 6% by mass or more. Is more preferably 7% by mass or more, more preferably 20% by mass or less, further preferably 19% by mass or less, still more preferably 18% by mass or less.
- (X) When the content ratio of (d) dodecanedioic acid diester in the plasticizer is within the above range, the flexibility of the formed vinyl chloride resin molded product at low temperature and the low temperature tensile elongation after heating are further enhanced. Can be done.
- the total content of (b) trimellitic acid ester, (c) polyester containing a predetermined structural unit, and (d) dodecane diic acid diester in the vinyl chloride resin composition is (a) chloride.
- the vinyl resin With respect to 100 parts by mass of the vinyl resin, it is preferably 30 parts by mass or more, more preferably 60 parts by mass or more, further preferably 66 parts by mass or more, still more preferably 80 parts by mass or more, and preferably. It is 200 parts by mass or less, more preferably 160 parts by mass or less, and further preferably 140 parts by mass or less.
- the mass ratio (c / d) of (c) polyester and (d) dodecanedioic acid diester in the vinyl chloride resin composition is preferably 3/2 or more, more preferably 7/4 or more, and further. It is preferably 2/1 or more, preferably 10/1 or less, more preferably 6/1 or less, and further preferably 3/1 or less.
- the mass ratio (c / d) of (c) polyester and (d) dodecanedioic acid diester is within the above-mentioned predetermined range, the low-temperature tensile elongation after heating of the vinyl chloride resin molded product to be formed is further enhanced. Can be done.
- the (x) plasticizer contained in the vinyl chloride resin composition is optionally other than (b) trimellitic acid ester described above, (c) polyester containing a predetermined structural unit, and (d) dodecanedioic acid diester. It may contain a plasticizer ((e) other plasticizer).
- plasticizers include the above-mentioned (b) trimellitic acid ester and (c) polyester containing a predetermined structural unit among the plasticizers described in International Publication No. 2016/098344. And (d) plasticizers other than dodecanedioic acid diesters and the like. Above all, it is preferable to use epoxidized soybean oil from the viewpoint of suppressing a decrease in low-temperature flexibility before and after heating of the vinyl chloride resin molded product to be formed.
- the content of the above-mentioned (e) and other plasticizers in the vinyl chloride resin composition can be 0 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the above-mentioned (a) vinyl chloride resin.
- the vinyl chloride resin composition of the present invention may further contain various additives in addition to the above-mentioned components.
- the additive is not particularly limited, and is a lubricant; a stabilizer such as perchloric acid-treated hydrotalcite, zeolite, ⁇ -diketone, fatty acid metal salt; a mold release agent; other compounds other than the above-mentioned vinyl chloride resin fine particles.
- Stinging agent is a lubricant; a stabilizer such as perchloric acid-treated hydrotalcite, zeolite, ⁇ -diketone, fatty acid metal salt; a mold release agent; other compounds other than the above-mentioned vinyl chloride resin fine particles.
- Stinging agent Impact resistance improving agent
- Perchloric acid compounds other than perchloric acid-treated hydrotalcite sodium perchlorate, potassium perchlorate, etc.
- Antioxidant Antifungal agent
- Flame retardant Antistatic agent
- Fillers light stabilizers; foaming agents; pigments
- the vinyl chloride resin composition of the present invention preferably contains a silicone oil. If the vinyl chloride resin composition is contained, the mold contamination resistance of the vinyl chloride resin composition can be further enhanced.
- the silicone oil that can be contained in the vinyl chloride resin composition include the silicone oil described in JP-A-2018-35304.
- the content of the silicone oil in the vinyl chloride resin composition is preferably 0.1 part by mass or more, and 0.2 part by mass or more, based on 100 parts by mass of the vinyl chloride resin (a). It is more preferably 1 part by mass or less, and more preferably 0.8 part by mass or less. When the content of the silicone oil in the vinyl chloride resin composition is within the above-mentioned predetermined range, the mold contamination resistance of the vinyl chloride resin composition can be further enhanced.
- the vinyl chloride resin composition of the present invention can be prepared by mixing the above-mentioned components.
- the method of mixing with the agent is not particularly limited, and for example, a method of mixing components excluding the dusting agent (including vinyl chloride resin fine particles) by a dry blend, and then adding and mixing the dusting agent is used. Can be mentioned.
- the temperature at the time of dry blending is not particularly limited, and is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and preferably 200 ° C. or lower.
- the obtained vinyl chloride resin composition can be suitably used for powder molding, and can be suitably used for powder slush molding.
- the vinyl chloride resin molded product of the present invention is characterized by being obtained by molding the above-mentioned vinyl chloride resin composition by an arbitrary method. Since the vinyl chloride resin molded product of the present invention is formed by using the above-mentioned vinyl chloride resin composition, usually, at least (a) vinyl chloride resin and (x) (b) as a plasticizer are used. When the total content of (b) trimellitic acid ester and (c) polyester containing a predetermined structural unit is equal to or higher than the above-mentioned predetermined value, including trimellitic acid ester and (c) polyester containing a predetermined structural unit.
- the vinyl chloride resin molded product of the present invention can maintain good low-temperature flexibility before and after heating. Therefore, the vinyl chloride resin molded product of the present invention does not scatter debris even when it is placed at a high temperature and then at a lower temperature, for example, when the airbag expands and expands. It can be suitably used as an automobile interior material such as the skin of an automobile instrument panel having excellent ductility that breaks as designed.
- the mold temperature during powder slash molding is not particularly limited, and is preferably 200 ° C. or higher, preferably 220 ° C. or higher. More preferably, it is preferably 300 ° C. or lower, and more preferably 280 ° C. or lower.
- the following method can be used without particular limitation. That is, the vinyl chloride resin composition of the present invention is sprinkled on a mold in the above temperature range, left for 5 seconds or more and 30 seconds or less, then the excess vinyl chloride resin composition is shaken off, and further, under an arbitrary temperature. , Leave it for 30 seconds or more and 3 minutes or less. Then, the mold is cooled to 10 ° C. or higher and 60 ° C. or lower, and the obtained vinyl chloride resin molded product of the present invention is removed from the mold. Then, a sheet-shaped molded body in the shape of a mold is obtained. Since the vinyl chloride resin composition of the present invention described above is used in the above method, it is possible to suppress contamination of the mold after the obtained vinyl chloride resin molded product is demolded.
- the laminated body of the present invention includes a foamed polyurethane molded body and the vinyl chloride resin molded body described above.
- the vinyl chloride resin molded product usually constitutes one surface of the laminated body.
- the laminate of the present invention has, for example, a vinyl chloride resin molded product formed by using the vinyl chloride resin composition of the present invention and capable of maintaining good low-temperature flexibility before and after heating. It is suitably used as an interior part, particularly as an automobile interior material for forming an automobile instrument panel.
- the method of laminating the foamed polyurethane molded product and the vinyl chloride resin molded product is not particularly limited, and for example, the following method can be used. That is, (1) a method in which a foamed polyurethane molded body and a vinyl chloride resin molded body are separately prepared and then bonded by heat fusion, heat bonding, or using a known adhesive or the like; (2) vinyl chloride. Polyurethane foamed on a resin molded body Polyurethane foamed on a vinyl chloride resin molded body by reacting isocyanates, which are the raw materials of the molded body, with polyols to polymerize, and foaming polyurethane by a known method.
- the latter method (2) is preferable because the process is simple and the vinyl chloride resin molded body and the foamed polyurethane molded body can be easily firmly adhered even when a laminated body having various shapes is obtained. Is.
- the surface of the demolded vinyl chloride resin molded sheet was visually observed, and the temperature of the melted portion was defined as the melting temperature.
- the melted portion was determined to be a portion of the molded vinyl chloride resin molded sheet having a smooth surface without leaving a particle shape. The lower the melting temperature, the better the meltability of the vinyl chloride resin composition.
- the weight was removed, the mixture was taken out of the oven and returned to room temperature, the aluminum plate was removed, and then the vinyl chloride resin molded sheet was peeled off from the polyurethane plate.
- the peak top temperature of the loss elastic modulus was measured under the same operations and conditions as in the case before heating. The lower the peak top temperature, the better the low temperature flexibility of the vinyl chloride resin molded sheet after heating (heat aging test).
- the sample was placed in an oven and heated in an environment at a temperature of 120 ° C. for 500 hours.
- the foamed polyurethane molded body was peeled off from the heated laminate to prepare only a vinyl chloride resin molded sheet.
- the tensile elongation at break (%) of the vinyl chloride resin molded sheet after heating for 500 hours was measured. The larger the value of tensile elongation at break, the more excellent the vinyl chloride resin molded sheet is in low temperature tensile elongation after heating (heat aging test).
- polyesters used in Examples and Comparative Examples were prepared as follows.
- ⁇ Polyester A> Adipic acid as a polyvalent carboxylic acid, 3-methyl-1,5-pentanediol as a polyhydric alcohol, and 2-ethylhexanol as a stopper (terminal stop component) are charged in a reaction vessel, and tetraisopropyl titanate is used as a catalyst.
- a solvent was appropriately added, and the temperature was raised while stirring.
- the by-product water was removed under normal pressure and reduced pressure, and finally the temperature was raised to 220 to 230 ° C. to complete the dehydration condensation reaction.
- Example 1 ⁇ Preparation of vinyl chloride resin composition> Among the ingredients shown in Table 1, the ingredients excluding the plasticizer (trimellitic acid ester, polyester A, and epoxidized soybean oil) and the vinyl chloride resin fine particles as the dusting agent were put into a Henschel mixer and mixed. Then, when the temperature of the mixture rises to 80 ° C., all the above plasticizers are added, and dry-up (a state in which the plasticizer is absorbed by vinyl chloride resin particles which are vinyl chloride resins and the mixture becomes smoother). To say.) Then, when the dried-up mixture was cooled to a temperature of 70 ° C.
- the plasticizer trimellitic acid ester, polyester A, and epoxidized soybean oil
- vinyl chloride resin fine particles as a dusting agent were added to prepare a vinyl chloride resin composition.
- the obtained vinyl chloride resin composition was used to evaluate the melting temperature and mold stain resistance. The results are shown in Table 1.
- ⁇ Formation of vinyl chloride resin molded product> A vinyl chloride resin molded sheet having dimensions of 145 mm ⁇ 175 mm ⁇ 1 mm was produced as follows. Specifically, the vinyl chloride resin composition obtained above is sprinkled on a textured mold heated to a temperature of 250 ° C., left to melt for an arbitrary time, and then the surplus vinyl chloride resin composition is sprinkled. Dropped.
- the textured mold sprinkled with the vinyl chloride resin composition was allowed to stand in an oven set at a temperature of 200 ° C., and 60 seconds after the standing, the textured mold was cooled with cooling water. ..
- the vinyl chloride resin molded sheet as the vinyl chloride resin molded body was removed from the mold.
- the obtained vinyl chloride resin molded sheet (dimensions: 145 mm ⁇ 175 mm ⁇ 1 mm) was evaluated for low temperature flexibility before (initial) heating and after heating (heat aging test) according to the above method. The results are shown in Table 1.
- Examples 2 to 7, Comparative Examples 1 to 5 A vinyl chloride resin composition and a vinyl chloride resin molded product were prepared in the same manner as in Example 1 except that the amounts of the trimellitic acid ester and polyester A used were changed as shown in Table 1. Then, measurement and evaluation were performed in the same manner as in Example 1. The results are shown in Table 1. Since the vinyl chloride resin composition obtained in Comparative Example 5 did not exhibit sufficient meltability, the melting temperature could not be measured. Further, an attempt was made to form a vinyl chloride resin molded product using the vinyl chloride resin composition obtained in Comparative Example 5, but only a brittle molded product having many unmelted portions and easily torn was obtained, and powder was appropriately obtained. Since it could not be molded, it was not possible to evaluate the mold contamination resistance and low temperature flexibility.
- Example 8 ⁇ Preparation of vinyl chloride resin composition> Among the ingredients shown in Table 2, the ingredients excluding the plasticizer (trimellitic acid ester, polyester A, and epoxidized soybean oil) and the vinyl chloride resin fine particles as the dusting agent were put into a Henschel mixer and mixed. Then, when the temperature of the mixture rises to 80 ° C., all the above plasticizers are added, and dry-up (a state in which the plasticizer is absorbed by vinyl chloride resin particles which are vinyl chloride resins and the mixture becomes smoother). To say.) Then, when the dried-up mixture was cooled to a temperature of 70 ° C.
- the plasticizer trimellitic acid ester, polyester A, and epoxidized soybean oil
- vinyl chloride resin fine particles as a dusting agent were added to prepare a vinyl chloride resin composition.
- a vinyl chloride resin molded sheet having dimensions of 145 mm ⁇ 175 mm ⁇ 1 mm and a vinyl chloride resin molded sheet having dimensions of 200 mm ⁇ 300 mm ⁇ 1 mm were prepared as follows. Specifically, the vinyl chloride resin composition obtained above is sprinkled on a textured mold heated to a temperature of 250 ° C., left to melt for an arbitrary time, and then the surplus vinyl chloride resin composition is sprinkled. Dropped.
- the textured mold sprinkled with the vinyl chloride resin composition was allowed to stand in an oven set at a temperature of 200 ° C., and 60 seconds after the standing, the textured mold was cooled with cooling water. ..
- the vinyl chloride resin molded sheet as the vinyl chloride resin molded body was removed from the mold.
- the obtained vinyl chloride resin molded sheet (dimensions: 145 mm ⁇ 175 mm ⁇ 1 mm) was measured and evaluated for low temperature flexibility before heating (initial) according to the above method.
- the obtained vinyl chloride resin molded sheet (dimensions: 200 mm ⁇ 300 mm ⁇ 1 mm) was measured and evaluated at low temperature tensile elongation before heating (initial) according to the above method. The results are shown in Table 2.
- a mixed solution was prepared by mixing the obtained polyol mixture and polymethylene polyphenylene polyisocyanate (polymeric MDI) at a ratio of 98. Then, the prepared mixed solution was poured onto a vinyl chloride resin molded sheet laid in the mold as described above. Then, the mold was covered with an aluminum plate having a size of 348 mm ⁇ 255 mm ⁇ 10 mm, and the mold was sealed. By leaving the mold sealed for 5 minutes, the vinyl chloride resin molded sheet (thickness: 1 mm) as the skin is lined with a polyurethane foam molded body (thickness: 9 mm, density: 0.2 g / cm 3 ). The laminated body was formed. Then, the formed laminate was taken out from the mold, and the low-temperature tensile elongation after heating (heat aging test) of the vinyl chloride resin sheet in the laminate was measured and evaluated according to the above method. The results are shown in Table 2.
- Example 9 The vinyl chloride resin composition, the vinyl chloride resin molded product, and the laminate were prepared in the same manner as in Example 8 except that the compounding amount of bis (2-ethylhexyl) dodecanedioate shown in Table 2 was further used as a plasticizer. Made. Then, measurement and evaluation were performed in the same manner as in Example 8. The results are shown in Table 2.
- the vinyl chloride resin composition of Comparative Example 1 in which (b) the trimellitic acid ester was not used as the plasticizer and only the above (c) polyester was used can maintain good low temperature flexibility before and after heating. It can be seen that a vinyl chloride resin molded product can be formed, but the mold contamination resistance is inferior. Further, (b) a trimellitic acid ester and (c) a polyester containing a predetermined structural unit were used, and the total content of (b) the trimellitic acid ester and the above (c) polyester was set to a predetermined value or more.
- the vinyl chloride resin compositions of Comparative Examples 2 to 4 in which the ratio of the polyester content (c) to the total content is not more than a predetermined value have good mold contamination resistance, but are low in temperature before and after heating. It can be seen that a vinyl chloride resin molded body capable of maintaining good flexibility cannot be formed. Further, the vinyl chloride resin composition of Comparative Example 5 in which the total content of (b) trimellitic acid ester and (c) polyester is less than a predetermined value does not have sufficient meltability and is appropriately a vinyl chloride resin. It can be seen that the molded body cannot be formed.
- the vinyl chloride resin molded product formed by using the vinyl chloride resin compositions of Examples 9 to 10 using the plasticizer containing the agents in a predetermined ratio includes (d) a plasticizer containing no dodecane diester. It can be seen that the vinyl chloride resin molded body formed by using the vinyl chloride resin composition of Example 8 used is excellent in low-temperature tensile elongation after heating.
- a vinyl chloride resin molded product capable of forming a vinyl chloride resin molded product capable of maintaining good low temperature flexibility before and after heating, and also providing a vinyl chloride resin composition having excellent mold contamination resistance. .. Further, according to the present invention, it is possible to provide a vinyl chloride resin molded product capable of maintaining good low temperature flexibility before and after heating. Further, according to the present invention, it is possible to provide a laminated body including the vinyl chloride resin molded body.
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Abstract
Description
具体的には、例えば、自動車インスツルメントパネルおよびドアトリム等の自動車内装部品の形成には、塩化ビニル樹脂成形体からなる表皮や塩化ビニル樹脂成形体からなる表皮に発泡ポリウレタン等の発泡体を裏打ちしてなる積層体などの自動車内装材が用いられている。
しかしながら、上記従来技術の塩化ビニル樹脂組成物を成形して得られる塩化ビニル樹脂成形体は、加熱前後で低温柔軟性を良好に維持する点に改善の余地があった。
しかしながら、上記従来技術の塩化ビニル樹脂組成物は、耐金型汚染性に改善の余地があった。
また、本発明は、加熱前後で低温柔軟性を良好に維持し得る塩化ビニル樹脂成形体を提供することを目的とする。
さらに、本発明は、当該塩化ビニル樹脂成形体を備える積層体を提供することを目的とする。
なお、本発明において、塩化ビニル樹脂粒子および塩化ビニル樹脂微粒子の「体積平均粒子径」は、JIS Z8825に準拠し、レーザー回折法により測定することができる。
なお、本発明において、塩化ビニル樹脂の「平均重合度」は、JIS K6720-2に準拠して測定することができる。
また、本発明によれば、加熱前後で低温柔軟性を良好に維持し得る塩化ビニル樹脂成形体を提供することができる。
さらに、本発明によれば、当該塩化ビニル樹脂成形体を備える積層体を提供することができる。
本発明の塩化ビニル樹脂組成物は、例えば、本発明の塩化ビニル樹脂成形体を形成する際に用いることができる。そして、本発明の塩化ビニル樹脂組成物を用いて形成した塩化ビニル樹脂成形体は、例えば、自動車インスツルメントパネルおよびドアトリム等の自動車内装部品が備える表皮などの、自動車内装材として好適に用いることができる。
また、本発明の塩化ビニル樹脂成形体は、例えば、本発明の積層体を形成する際に用いることができる。そして、本発明の塩化ビニル樹脂成形体を用いて形成した積層体は、例えば、自動車インスツルメントパネルおよびドアトリム等の自動車内装部品を製造する際に用いる自動車内装材として好適に用いることができる。
本発明の塩化ビニル樹脂組成物は、(a)塩化ビニル樹脂と、(x)可塑剤とを含んでいる。そして、本発明の塩化ビニル樹脂組成物は、(x)可塑剤として、(b)トリメリット酸エステルと、(c)所定の構造単位を含有するポリエステルとを含み、(b)トリメリット酸エステルおよび(c)所定の構造単位を含有するポリエステルの合計含有量が、(a)塩化ビニル樹脂100質量部当たり、65質量部以上であり、(b)トリメリット酸エステルおよび(c)所定の構造単位を含有するポリエステルの合計含有量に占める(c)所定の構造単位を含有するポリエステルの含有量の割合が50質量%を超えることを特徴とする。
なお、本発明の塩化ビニル樹脂組成物は、任意に、上記(a)塩化ビニル樹脂、および(x)可塑剤以外のその他の成分を更に含んでいてもよい。
また、本発明の塩化ビニル樹脂組成物は、(x)可塑剤として、任意に、上記(b)トリメリット酸エステルおよび(c)所定の構造単位を含有するポリエステル以外のその他の可塑剤を更に含んでいてもよい。
したがって、本発明の塩化ビニル樹脂組成物を使用すれば、例えば、加熱前後で低温柔軟性を良好に維持し得る自動車インスツルメントパネル用表皮およびドアトリム用表皮などの、自動車内装材として好適な塩化ビニル樹脂成形体を得ることができる。
なお、例えば、本発明の塩化ビニル樹脂組成物を用いて、自動車内装材として良好に使用し得る塩化ビニル樹脂成形体を容易に得る観点からは、本発明の塩化ビニル樹脂組成物は、粉体成形に用いられることが好ましく、パウダースラッシュ成形に用いられることがより好ましい。
(a)塩化ビニル樹脂としては、通常、粒子状の塩化ビニル樹脂を用いる。そして、(a)塩化ビニル樹脂としては、例えば、1種類または2種類以上の塩化ビニル樹脂粒子を含有することができ、任意に、1種類または2種類以上の塩化ビニル樹脂微粒子を更に含有することができる。中でも、(a)塩化ビニル樹脂は、少なくとも塩化ビニル樹脂粒子を含有することが好ましく、塩化ビニル樹脂粒子および塩化ビニル樹脂微粒子を含有することがより好ましい。
そして、(a)塩化ビニル樹脂は、懸濁重合法、乳化重合法、溶液重合法、塊状重合法など、従来から知られているいずれの製造法によっても製造し得る。
なお、本明細書において、「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。
塩化ビニル樹脂組成物において、塩化ビニル樹脂粒子は、通常、マトリックス樹脂(基材)として機能する。なお、塩化ビニル樹脂粒子は、懸濁重合法により製造することが好ましい。
そして、塩化ビニル樹脂粒子を構成する塩化ビニル樹脂の平均重合度は、800以上であることが好ましく、1000以上であることがより好ましく、1300以上であることが更に好ましく、5000以下であることが好ましく、3000以下であることがより好ましく、2800以下であることが更に好ましく、2300以下であることが特に好ましく、1900以下であることがより一層好ましい。塩化ビニル樹脂粒子を構成する塩化ビニル樹脂の平均重合度が上記下限以上であれば、塩化ビニル樹脂組成物を用いて形成した塩化ビニル樹脂成形体の物理的強度を十分確保しつつ、例えば、引張特性、特には引張伸びをより良好にできるからである。そして、引張伸びが良好な塩化ビニル樹脂成形体は、例えば、エアバッグが膨張、展開した際に、破片が飛散することなく設計通りに割れる、延性に優れた自動車インスツルメントパネルの表皮などの自動車内装材として好適に用いることができる。また、塩化ビニル樹脂粒子を構成する塩化ビニル樹脂の平均重合度が上記上限以下であれば、塩化ビニル樹脂組成物の溶融性を向上させることができるからである。
また、塩化ビニル樹脂粒子の体積平均粒子径は、通常30μm以上であり、50μm以上が好ましく、100μm以上がより好ましく、500μm以下が好ましく、200μm以下がより好ましい。塩化ビニル樹脂粒子の体積平均粒子径が上記下限以上であれば、塩化ビニル樹脂組成物の粉体流動性がより向上するからである。また、塩化ビニル樹脂粒子の体積平均粒子径が上記上限以下であれば、塩化ビニル樹脂組成物の溶融性が向上すると共に、当該組成物を用いて形成した塩化ビニル樹脂成形体の表面平滑性を向上できるからである。
そして、(a)塩化ビニル樹脂中の塩化ビニル樹脂粒子の含有割合は、70質量%以上であることが好ましく、80質量%以上であることがより好ましく、100質量%とすることができ、95質量%以下であることが好ましく、90質量%以下であることがより好ましい。(a)塩化ビニル樹脂中の塩化ビニル樹脂粒子の含有割合が上記下限以上であれば、塩化ビニル樹脂組成物を用いて形成した塩化ビニル樹脂成形体の物理的強度を十分確保しつつ引張伸びを良好にできるからである。また、(a)塩化ビニル樹脂中の塩化ビニル樹脂粒子の含有割合が上記上限以下であれば、塩化ビニル樹脂組成物の粉体流動性が向上するからである。
塩化ビニル樹脂組成物において、塩化ビニル樹脂微粒子は、通常、ダスティング剤(粉体流動性改良剤)として機能する。なお、塩化ビニル樹脂微粒子は、乳化重合法により製造することが好ましい。
そして、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、500以上が好ましく、700以上がより好ましく、2600以下が好ましく、2400以下がより好ましい。ダスティング剤としての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が上記下限以上であれば、塩化ビニル樹脂組成物の粉体流動性がより良好になると共に、当該組成物を用いて得られる成形体の引張伸びがより良好になるからである。また、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が上記上限以下であれば、塩化ビニル樹脂組成物の溶融性が向上し、当該組成物を用いて形成した塩化ビニル樹脂成形体の表面平滑性が向上するからである。
また、塩化ビニル樹脂微粒子の体積平均粒子径は、通常30μm未満であり、10μm以下であることが好ましく、5μm以下であることがより好ましく、0.1μm以上であることが好ましく、1μm以上であることがより好ましい。塩化ビニル樹脂微粒子の体積平均粒子径が上記下限以上であれば、例えばダスティング剤としてのサイズを過度に小さくすることなく、塩化ビニル樹脂組成物の粉体流動性を更に良好にすることができるからである。また、塩化ビニル樹脂微粒子の体積平均粒子径が上記上限以下であれば、塩化ビニル樹脂組成物の溶融性が高まり、形成される塩化ビニル樹脂成形体の表面平滑性を更に向上させることができるからである。
そして、(a)塩化ビニル樹脂中の塩化ビニル樹脂微粒子の含有割合は、0質量%であってもよいが、5質量%以上であることが好ましく、10質量%以上であることがより好ましく、30質量%以下であることが好ましく、20質量%以下であることがより好ましい。(a)塩化ビニル樹脂中の塩化ビニル樹脂微粒子の含有割合が上記下限以上であれば、塩化ビニル樹脂組成物の粉体流動性が更に向上するからである。また、(a)塩化ビニル樹脂中の塩化ビニル樹脂微粒子の含有割合が上記上限以下であれば、塩化ビニル樹脂組成物を用いて形成した塩化ビニル樹脂成形体の物理的強度をより高めることができるからである。
(x)可塑剤は、(b)トリメリット酸エステルと、(c)所定の構造単位を含有するポリエステルと、を含んでいる。また、(x)可塑剤は、(d)ドデカン二酸ジエステルを更に含んでいてもよい。また、(x)可塑剤は、(b)トリメリット酸エステル、(c)所定の構造単位を含有するポリエステル、および(d)ドデカン二酸ジエステル以外の、(e)その他の可塑剤を更に含んでいてもよい。
(b)トリメリット酸エステルは、好ましくは、トリメリット酸と一価アルコールとのエステル化合物である。
上記(b)トリメリット酸エステルは、単一の化合物からなるものであってもよいし、異なる化合物の混合物であってもよい。
より好ましい(b)トリメリット酸エステルの具体例は、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-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6~18である。〕を分子内に2種以上有するエステル)、及びこれらの混合物等である。
(c)所定の構造単位を含有するポリエステルは、アジピン酸由来の構造単位と、3-メチル-1,5-ペンタンジオール由来の構造単位とを含有する。
なお、(c)所定の構造単位を含有するポリエステルは、アジピン酸由来の構造単位および3-メチル-1,5-ペンタンジオール由来の構造単位以外の構造単位を有していてもよいが、アジピン酸由来の構造単位および3-メチル-1,5-ペンタンジオール由来の構造単位の合計が、全構造単位の50質量%以上であることが好ましく、80質量%以上であることがより好ましい。また、(c)所定の構造単位を含有するポリエステルは、繰り返し単位としてアジピン酸由来の構造単位および3-メチル-1,5-ペンタンジオール由来の構造単位のみを有することが好ましい。
なお、上記(c)所定の構造単位を含有するポリエステルとしては、市販品を用いてもよい。
更に、末端停止成分として使用し得る一塩基酸としては、例えば、酢酸、プロピオン酸、酪酸、イソ酪酸、吉草酸、ピバル酸、カプロン酸、ヘプタン酸、カプリル酸、2-エチルヘキシル酸、ペラルゴン酸、カプリン酸、ウンデカン酸、ラウリン酸、トリデカン酸、ミリスチン酸、ペンタデカン酸、パルミチン酸、ヘプタデカン酸、ステアリン酸、安息香酸およびそれらの混合物が挙げられる。
中でも、末端停止成分としては、2-エチルヘキサノールが好ましい。
なお、「数平均分子量」は、VPO(蒸気圧浸透圧)法にて測定することができる。
また、上記(c)所定の構造単位を含有するポリエステルは、酸価が1以下であることが好ましい。
更に、上記(c)所定の構造単位を含有するポリエステルは、水酸基価が30以下であることが好ましい。
なお、「粘度」は、JIS Z8803に準拠し、温度23℃で測定することができる。
塩化ビニル樹脂組成物中における(b)トリメリット酸エステルおよび上記(c)所定の構造単位を含有するポリエステルの合計含有量は、上記(a)塩化ビニル樹脂100質量部に対して、65質量部以上であることが必要であり、80質量部以上であることが好ましく、90質量部以上であることがより好ましく、200質量部以下であることが好ましく、160質量部以下であることがより好ましく、140質量部以下であることが更に好ましい。(b)トリメリット酸エステルおよび上記(c)所定の構造単位を含有するポリエステルの合計含有量が上記下限以上であると、塩化ビニル樹脂組成物を用いて形成した塩化ビニル樹脂成形体は、加熱前後で低温柔軟性を良好に維持することができる。また、(b)トリメリット酸エステルおよび上記(c)所定の構造単位を含有するポリエステルの合計含有量が上記下限以上であれば、塩化ビニル樹脂組成物を用いて形成した塩化ビニル樹脂成形体の低温柔軟性を更に高めることができる。さらに、(b)トリメリット酸エステルおよび上記(c)所定の構造単位を含有するポリエステルの合計含有量が、上記(a)塩化ビニル樹脂100質量部に対して90質量部以上であれば、塩化ビニル樹脂組成物は優れた溶融性を発揮することができる。一方、(b)トリメリット酸エステルおよび上記(c)所定の構造単位を含有するポリエステルの合計含有量が上記上限以下であれば、塩化ビニル樹脂組成物を用いて形成した塩化ビニル樹脂成形体の表面がべた付くことを抑制することができる。
なお、塩化ビニル樹脂組成物中における(b)トリメリット酸エステルおよび上記(c)所定の構造単位を含有するポリエステルの合計含有量に占める上記(c)所定の構造単位を含有するポリエステルの含有量の割合は、100質量%未満であることが必要であり、98質量%未満であることが好ましく、95質量%未満であることがより好ましく、92質量%未満であることが更に好ましい。(b)トリメリット酸エステルおよび上記(c)所定の構造単位を含有するポリエステルの合計含有量に占める上記(c)所定の構造単位を含有するポリエステルの含有量の割合が上記100質量%未満であると、塩化ビニル樹脂組成物の耐金型汚染性を十分に高めることができる。また、(b)トリメリット酸エステルおよび上記(c)所定の構造単位を含有するポリエステルの合計含有量に占める上記(c)所定の構造単位を含有するポリエステルの含有量の割合が上記上限未満であれば、塩化ビニル樹脂組成物の溶融性を高めることができる。
(x)可塑剤は、上述した(b)トリメリット酸エステルおよび(c)所定の構造単位を含有するポリエステルに加えて、(d)ドデカン二酸ジエステルを更に含んでいてもよい。(x)可塑剤が上述した(b)トリメリット酸エステルおよび(c)所定の構造単位を含有するポリエステルに加えて、(d)ドデカン二酸ジエステルを更に含むことにより、形成される塩化ビニル樹脂成形体の加熱後の低温引張伸びを高めることができる。
しかしながら、可塑剤として、上述した(b)トリメリット酸エステルおよび(c)所定の構造単位を含有するポリエステルに加えて、(d)ドデカン二酸ジエステルを更に使用して得られる塩化ビニル樹脂組成物であれば、理由は明らかではないが、加熱後の低温引張伸びに優れた塩化ビニル樹脂成形体を形成可能であることがわかった。
(x)可塑剤が、(b)トリメリット酸エステルおよび(c)所定の構造単位を含有するポリエステルに加えて、(d)ドデカン二酸ジエステルを更に含んでいる場合、(x)可塑剤中における(b)トリメリット酸エステル、(c)所定の構造単位を含有するポリエステル、(d)ドデカン二酸ジエステル、および(e)その他の可塑剤の各可塑剤の含有割合が所定範囲内であることが好ましい。(x)可塑剤が、(b)トリメリット酸エステル、(c)所定の構造単位を含有するポリエステル、(d)ドデカン二酸ジエステル、および(e)その他の可塑剤をそれぞれ所定の含有割合で含んでいれば、形成される塩化ビニル樹脂成形体の低温柔軟性および加熱後の低温引張伸びを更に高めることができる。
さらに、塩化ビニル樹脂組成物中における(b)トリメリット酸エステル、上記(c)所定の構造単位を含有するポリエステル、および(d)ドデカン二酸ジエステルの含有量の合計は、上記(a)塩化ビニル樹脂100質量部に対して、好ましくは30質量部以上であり、より好ましくは60質量部以上であり、更に好ましくは66質量部以上であり、一層好ましくは80質量部以上であり、好ましくは200質量部以下であり、より好ましくは160質量部以下であり、更に好ましくは140質量部以下である。塩化ビニル樹脂組成物中における(b)トリメリット酸エステル、上記(c)所定の構造単位を含有するポリエステル、および(d)ドデカン二酸ジエステルの含有量の合計が上記範囲内であれば、形成される塩化ビニル樹脂成形体の低温柔軟性および加熱後の低温引張伸びを更に高めることができる。
塩化ビニル樹脂組成物中における(c)ポリエステルと(d)ドデカン二酸ジエステルとの質量比(c/d)は、好ましくは3/2以上であり、より好ましくは7/4以上であり、更に好ましくは2/1以上であり、好ましくは10/1以下であり、より好ましくは6/1以下であり、更に好ましくは3/1以下である。(c)ポリエステルと(d)ドデカン二酸ジエステルとの質量比(c/d)が上記所定の範囲内であれば、形成される塩化ビニル樹脂成形体の加熱後の低温引張伸びを更に高めることができる。
塩化ビニル樹脂組成物に含まれる(x)可塑剤は、任意で、上述した(b)トリメリット酸エステル、(c)所定の構造単位を含有するポリエステル、および(d)ドデカン二酸ジエステル以外の可塑剤((e)その他の可塑剤)を含んでいてもよい。
本発明の塩化ビニル樹脂組成物は、上述した成分以外に、各種添加剤を更に含有してもよい。添加剤としては、特に限定されることなく、滑剤;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、脂肪酸金属塩などの安定剤;離型剤;上記塩化ビニル樹脂微粒子以外のその他のダスティング剤;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;顔料;などが挙げられる。
なお、塩化ビニル樹脂組成物が含み得るシリコーンオイルとしては、例えば、特開2018-35304号公報に記載のシリコーンオイルなどが挙げられる。
そして、塩化ビニル樹脂組成物中におけるシリコーンオイルの含有量は、上記(a)塩化ビニル樹脂100質量部に対して、0.1質量部以上であることが好ましく、0.2質量部以上であることがより好ましく、1質量部以下であることが好ましく、0.8質量部以下であることがより好ましい。塩化ビニル樹脂組成物中におけるシリコーンオイルの含有量が上記所定範囲内であれば、塩化ビニル樹脂組成物の耐金型汚染性を一層高めることができる。
本発明の塩化ビニル樹脂組成物は、上述した成分を混合して調製することができる。
ここで、(a)塩化ビニル樹脂と、(b)トリメリット酸エステルおよび(c)所定の構造単位を含有するポリエステルを少なくとも含む(x)可塑剤と、必要に応じて更に配合される各種添加剤との混合方法としては、特に限定されることなく、例えば、ダスティング剤(塩化ビニル樹脂微粒子を含む)を除く成分を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、混合する方法が挙げられる。ここで、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、特に制限されることなく、50℃以上が好ましく、70℃以上がより好ましく、200℃以下が好ましい。
そして、得られた塩化ビニル樹脂組成物は、粉体成形に好適に用いることができ、パウダースラッシュ成形により好適に用いることができる。
本発明の塩化ビニル樹脂成形体は、上述した塩化ビニル樹脂組成物を、任意の方法で成形することにより得られることを特徴とする。そして、本発明の塩化ビニル樹脂成形体は、上述した塩化ビニル樹脂組成物を用いて形成されているため、通常、少なくとも、(a)塩化ビニル樹脂と、(x)可塑剤としての(b)トリメリット酸エステルおよび(c)所定の構造単位を含有するポリエステルとを含み、(b)トリメリット酸エステルおよび(c)所定の構造単位を含有するポリエステルの合計含有量が上述した所定値以上であり、当該合計含有量に占める(c)所定の構造単位を含有するポリエステルの含有量の割合が50質量%を超えている。そして、本発明の塩化ビニル樹脂成形体は、加熱前後で低温柔軟性を良好に維持することができる。
したがって、本発明の塩化ビニル樹脂成形体は、高温下に置かれた後に更に低温下に置かれた状態であっても、例えば、エアバッグが膨張、展開した際に、破片が飛散することなく設計通りに割れる、延性に優れた自動車インスツルメントパネルの表皮などの自動車内装材として好適に用いることができる。
ここで、パウダースラッシュ成形により塩化ビニル樹脂成形体を形成する場合、パウダースラッシュ成形時の金型温度は、特に制限されることなく、200℃以上とすることが好ましく、220℃以上とすることがより好ましく、300℃以下とすることが好ましく、280℃以下とすることがより好ましい。
なお、上記方法では、上述した本発明の塩化ビニル樹脂組成物を用いているため、得られた塩化ビニル樹脂成形体を脱型した後の金型の汚染を抑制することができる。
本発明の積層体は、発泡ポリウレタン成形体と、上述した塩化ビニル樹脂成形体とを有する。なお、塩化ビニル樹脂成形体は、通常、積層体の一方の表面を構成する。
そして、本発明の積層体は、例えば、本発明の塩化ビニル樹脂組成物を用いて形成され、加熱前後で低温柔軟性を良好に維持し得る塩化ビニル樹脂成形体を有しているため、自動車内装部品、特に、自動車インスツルメントパネルを形成する自動車内装材として好適に用いられる。
そして、塩化ビニル樹脂組成物の溶融温度および耐金型汚染性、並びに、塩化ビニル樹脂成形体の加熱前(初期)および加熱(熱老化試験)後の低温柔軟性および低温引張伸びは、下記の方法で測定および評価した。
実施例および比較例で得られた塩化ビニル樹脂組成物の溶融温度は、加熱した金型を用いて測定した。具体的には、金型を170℃から270℃までの範囲で等間隔に段階的に加熱した熱板上に置き、段階的に加熱した金型を得た。そして、塩化ビニル樹脂組成物を、当該段階的に加熱した金型に厚みが1mmとなるように振りかけ、30秒間放置することにより溶融させた。次に、余剰の塩化ビニル樹脂組成物を振り落とし、金型を水で冷却することにより、塩化ビニル樹脂がベルト状に成形された塩化ビニル樹脂成形シートを金型から脱型した。脱型した塩化ビニル樹脂成形シート表面を目視で観察し、溶融した箇所の温度を溶融温度とした。なお、当該溶融した箇所は、成形された塩化ビニル樹脂成形シートにおいて、粒子形状を残すことなく平滑な表面を有する箇所として判断した。溶融温度が低いほど、塩化ビニル樹脂組成物が溶融性に優れることを示す。
金型をサンドブラストにより洗浄した後、温度250℃に加熱したシボ付き金型に対して、実施例および比較例で得られた塩化ビニル樹脂組成物を振りかけ、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、当該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内に静置し、静置から60秒経過した時点で当該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の、145mm×175mm×1mmの塩化ビニル樹脂成形シートをシボ付き金型から脱型した。上述した加熱、成形、および冷却の操作を5回繰り返した後、マイクロスコープでシボ付き金型の表面の10cm×10cmの領域を観察した。当該領域内において、円相当径が100μm以上である粒子の数を計測して、下記の基準に従って、塩化ビニル樹脂組成物の耐金型汚染性を評価した。なお、円相当径が100μm以上である粒子の数が少ないほど、塩化ビニル樹脂組成物は耐金型汚染性に優れることを示す。
A:500個未満
B:500個以上1000個未満
C:1000個以上
<<加熱前(初期)>>
実施例および比較例で得られた塩化ビニル樹脂成形シート(寸法:145mm×175mm×1mm)を10mm×40mmの寸法で打ち抜き、JIS K7244-4に準拠して、周波数10Hz、測定温度範囲-90℃~+100℃、昇温速度2℃/分で損失弾性率のピークトップ温度を測定した。塩化ビニル樹脂成形シートは、当該ピークトップ温度が低いほど、加熱前(初期)の低温柔軟性に優れている。
<<加熱(熱老化試験)後>>
実施例および比較例で得られた塩化ビニル樹脂成型シート(寸法:145mm×175mm×1mm)を、DURO-A硬度が90°のポリウレタン製の板(寸法:230mm×320mm×3mm)の上に乗せ、250mm×340mm×2mmのアルミ板で上下を挟んだ。その上に2kgの重りを載せた状態にし、オーブンに入れて、120℃にて1週間加熱を行った。その後、重りを取り除き、オーブンから取り出して室温に戻した後、アルミ板を除いてからポリウレタン製の板から塩化ビニル樹脂成形シートを剥がした。得られた加熱(熱老化試験)後の塩化ビニル樹脂成形シートを用いて、上記加熱前の場合と同じ操作および条件で、損失弾性率のピークトップ温度を測定した。当該ピークトップ温度が低いほど、塩化ビニル樹脂成形シートは加熱(熱老化試験)後の低温柔軟性に優れている。
<<加熱前後での低温柔軟性の維持>>
塩化ビニル樹脂成形シートの加熱前の損失弾性率のピークトップ温度と、加熱後の損失弾性率のピークトップ温度との差を求めることにより、加熱前後での低温柔軟性の維持の程度を評価した。なお、加熱前の損失弾性率のピークトップ温度と、加熱後の損失弾性率のピークトップ温度との差が小さいほど、塩化ビニル樹脂成形シートは加熱前後で低温柔軟性を良好に維持できていることを示す。
<<加熱前(初期)>>
得られた塩化ビニル樹脂成形シートを、JIS K6251に記載の1号ダンベルで打ち抜き、JIS K7113に準拠して、引張速度200mm/分で、-10℃の低温下における引張破断伸び(%)を測定した。引張破断伸びの値が大きいほど、塩化ビニル樹脂成形シートは加熱前(初期)の低温引張伸びに優れている。
<<加熱(熱老化試験)後>>
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た。当該試料をオーブンに入れ、温度120℃の環境下で500時間加熱を行った。次に、加熱後の積層体から発泡ポリウレタン成形体を剥離して、塩化ビニル樹脂成形シートのみを準備した。そして、上記初期の場合と同様の条件にて、500時間加熱後の塩化ビニル樹脂成形シートの引張破断伸び(%)を測定した。引張破断伸びの値が大きいほど、塩化ビニル樹脂成形シートは加熱(熱老化試験)後の低温引張伸びに優れている。
実施例および比較例で使用したポリエステルは、以下のようにして調製した。
<ポリエステルA>
多価カルボン酸としてのアジピン酸、多価アルコールとしての3-メチル-1,5-ペンタンジオール、及びストッパー(末端停止成分)としての2-エチルヘキサノールを反応容器に仕込み、触媒としてテトライソプロピルチタネートを加え、適宜溶剤を添加し、攪拌しながら昇温した。副生する水は常圧および減圧で除去し、最終的に220~230℃まで温度を上げて脱水縮合反応を完結させた。得られた生成物について、圧力4~80Pa、外套温度250℃の条件下で薄膜蒸留を行なうことで、末端が2-エチルヘキソキシ基からなるポリエステルA(粘度:3600mPa・s、数平均分子量:5300、酸価:0.32、水酸基価:12.7)を得た。
<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(トリメリット酸エステル、ポリエステルA、およびエポキシ化大豆油)と、ダスティング剤である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、ドライアップ(可塑剤が、塩化ビニル樹脂である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である塩化ビニル樹脂微粒子を添加し、塩化ビニル樹脂組成物を調製した。
得られた塩化ビニル樹脂組成物を用いて、溶融温度および耐金型汚染性を評価した。結果を表1に示す。
<塩化ビニル樹脂成形体の形成>
以下のようにして、寸法が145mm×175mm×1mmの塩化ビニル樹脂成形シートを作製した。
具体的には、上述で得られた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、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、当該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内に静置し、静置から60秒経過した時点で当該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(寸法:145mm×175mm×1mm)について、上述の方法に従って、加熱前(初期)および加熱(熱老化試験)後の低温柔軟性を評価した。結果を表1に示す。
トリメリット酸エステル、およびポリエステルAの使用量を表1に示すように変更した以外は実施例1と同様にして、塩化ビニル樹脂組成物、および塩化ビニル樹脂成形体を作製した。そして、実施例1と同様にして測定および評価を行った。結果を表1に示す。
なお、比較例5で得られた塩化ビニル樹脂組成物は、十分な溶融性を発揮しなかったため、溶融温度を測定することができなかった。また、比較例5で得られた塩化ビニル樹脂組成物を用いて塩化ビニル樹脂成形体の形成を試みたが、未溶融部分が多く、引裂けやすい脆い成形品しか得られず、適切に粉体成形をすることができなかったため、耐金型汚染性および低温柔軟性の評価を行うことができなかった。
<塩化ビニル樹脂組成物の調製>
表2に示す配合成分のうち、可塑剤(トリメリット酸エステル、ポリエステルA、およびエポキシ化大豆油)と、ダスティング剤である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、ドライアップ(可塑剤が、塩化ビニル樹脂である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である塩化ビニル樹脂微粒子を添加し、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形成>
以下のようにして、寸法が145mm×175mm×1mmの塩化ビニル樹脂成形シートおよび寸法が200mm×300mm×1mmの塩化ビニル樹脂成形シートをそれぞれ調製した。
具体的には、上述で得られた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、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、当該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内に静置し、静置から60秒経過した時点で当該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(寸法:145mm×175mm×1mm)について、上述の方法に従って、加熱前(初期)の低温柔軟性を測定、評価した。また、得られた塩化ビニル樹脂成形シート(寸法:200mm×300mm×1mm)について、上述の方法に従って、加熱前(初期)の低温引張伸びを測定、評価した。結果を表2に示す。
<積層体の形成>
得られた塩化ビニル樹脂成形シート(寸法:200mm×300mm×1mm)を、200mm×300mm×10mmの金型の中に、シボ付き面を下にして敷いた。
別途、プロピレングリコールのPO(プロピレンオキサイド)・EO(エチレンオキサイド)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%)を50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%)を50部、水を2.5部、トリエチレンジアミンのエチレングリコール溶液(東ソー社製、商品名「TEDA-L33」)を0.2部、トリエタノールアミンを1.2部、トリエチルアミンを0.5部、および整泡剤(信越化学工業製、商品名「F-122」)を0.5部混合して、ポリオール混合物を得た。また、得られ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た混合液を調製した。そして、調製した混合液を、上述の通り金型内に敷かれた塩化ビニル樹脂成形シートの上に注いだ。その後、348mm×255mm×10mmのアルミニウム板で上記金型に蓋をして、金型を密閉した。金型を密閉してから5分間放置することにより、表皮としての塩化ビニル樹脂成形シート(厚さ:1mm)に、発泡ポリウレタン成形体(厚み:9mm、密度:0.2g/cm3)が裏打ちされた積層体が、形成された。
そして、形成された積層体を金型から取り出し、積層体における塩化ビニル樹脂シートについて、上述の方法に従って、加熱(熱老化試験)後の低温引張伸びを測定、評価した。結果を表2に示す。
表2に示す配合量のドデカン二酸ビス(2-エチルヘキシル)を可塑剤として更に使用した以外は、実施例8と同様にして、塩化ビニル樹脂組成物、塩化ビニル樹脂成形体、および積層体を作製した。そして、実施例8と同様にして測定および評価を行った。結果を表2に示す。
2)新第一塩ビ社製、製品名「ZEST PQLTX」(乳化重合法で調製、平均重合度:800、体積平均粒子径:1.8μm)
3)東ソー社製、製品名「リューロンペースト761」(乳化重合法で調製、平均重合度:2100、体積平均粒子径:1.7μm)
4)花王社製、製品名「トリメックスN-08」
5)ADEKA社製、製品名「アデカサイザー O-130S」
6)協和化学工業社製、製品名「アルカマイザー(登録商標)5」
7)水澤化学工業社製、製品名「MIZUKALIZER DS」
8)昭和電工社製、製品名「カレンズDK-1」
9)ADEKA社製、製品名「アデカスタブ SC-131」
10)ADEKA社製、製品名「LA-72」
11)堺化学工業社、製品名「SAKAI SZ2000」
12)ADEKA社製、製品名「アデカスタブ LS-12」
13)信越シリコーン社製、製品名「KF-96H-30万cs」(未変性シリコーンオイル(ポリジメチルシロキサン)、粘度:30×104cs)
14)大日精化社製、製品名「DA PX 1720(A)ブラック」
15)新第一塩ビ社製、製品名「ZEST(登録商標)1300S」(懸濁重合法で調製、平均重合度:1300、体積平均粒子径:132μm)
16)和光純薬工業社製
一方、可塑剤として、(b)トリメリット酸エステルを使用せず、上記(c)ポリエステルのみを使用した比較例1の塩化ビニル樹脂組成物は、加熱前後で低温柔軟性を良好に維持し得る塩化ビニル樹脂成形体を形成可能であるが、耐金型汚染性に劣ることが分かる。
また、(b)トリメリット酸エステルおよび(c)所定の構造単位を含有するポリエステルを使用し、(b)トリメリット酸エステルおよび上記(c)ポリエステルの合計含有量を所定値以上としたが、当該合計含有量に占める上記(c)ポリエステルの含有量の割合が所定値以下である比較例2~4の塩化ビニル樹脂組成物は、耐金型汚染性は良好であるが、加熱前後で低温柔軟性を良好に維持し得る塩化ビニル樹脂成形体を形成できないことが分かる。
さらに、(b)トリメリット酸エステルおよび上記(c)ポリエステルの合計含有量が所定値未満である比較例5の塩化ビニル樹脂組成物は、十分な溶融性を有さず、適切に塩化ビニル樹脂成形体を形成することができないことが分かる。
また、本発明によれば、加熱前後で低温柔軟性を良好に維持し得る塩化ビニル樹脂成形体を提供することができる。
さらに、本発明によれば、当該塩化ビニル樹脂成形体を備える積層体を提供することができる。
Claims (14)
- (a)塩化ビニル樹脂と、(x)可塑剤とを含む塩化ビニル樹脂組成物であって、
前記(x)可塑剤が、
(b)トリメリット酸エステルと、
(c)アジピン酸由来の構造単位および3-メチル-1,5-ペンタンジオール由来の構造単位を含有するポリエステルと、を含み、
前記(b)トリメリット酸エステルおよび前記(c)ポリエステルの合計含有量が、前記(a)塩化ビニル樹脂100質量部当たり、65質量部以上であり、
前記(b)トリメリット酸エステルおよび前記(c)ポリエステルの合計含有量に占める前記(c)ポリエステルの含有量の割合が50質量%超である、塩化ビニル樹脂組成物。 - 前記(b)トリメリット酸エステルおよび前記(c)ポリエステルの合計含有量が、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に記載の塩化ビニル樹脂組成物。
- 前記(a)塩化ビニル樹脂が、体積平均粒子径が30μm以上500μm以下である塩化ビニル樹脂粒子と、体積平均粒子径が30μm未満である塩化ビニル樹脂微粒子とを含有する、請求項1または2に記載の塩化ビニル樹脂組成物。
- 前記塩化ビニル樹脂粒子を構成する塩化ビニル樹脂の平均重合度が5000以下である、請求項3に記載の塩化ビニル樹脂組成物。
- 前記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が2600以下である、請求項3または4に記載の塩化ビニル樹脂組成物。
- 前記(x)可塑剤が、
前記(b)トリメリット酸エステルを7質量%以上49.5質量%未満含み、
前記(c)ポリエステルを37.5質量%超75質量%以下含み、
(d)ドデカン二酸ジエステルを1質量%以上20質量%以下含み、
(e)前記(b)、(c)および(d)以外の可塑剤を0質量%以上5質量%以下含む、請求項1~5の何れかに記載の塩化ビニル樹脂組成物。 - 前記塩化ビニル樹脂100質量部当たり、前記(b)トリメリット酸エステル、前記(c)ポリエステル、および前記(d)ドデカン二酸ジエステルを合計で66質量部以上200質量部以下含む、請求項6に記載の塩化ビニル樹脂組成物。
- 前記(c)ポリエステルと前記(d)ドデカン二酸ジエステルとの質量比(c/d)が3/2以上10/1以下である、請求項6または7に記載の塩化ビニル樹脂組成物。
- 粉体成形に用いられる、請求項1~8の何れかに記載の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1~9の何れかに記載の塩化ビニル樹脂組成物。
- 請求項1~10の何れかに記載の塩化ビニル樹脂組成物を成形してなる、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11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11または12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13に記載の積層体。
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| EP20776641.1A EP3950254B1 (en) | 2019-03-26 | 2020-03-23 | Vinyl chloride resin composition, vinyl chloride resin molded article, and laminate |
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| WO2022004320A1 (ja) * | 2020-07-02 | 2022-01-06 | Dic株式会社 | 塩化ビニル樹脂用可塑剤、塩化ビニル樹脂組成物及びその成形品 |
| WO2023127608A1 (ja) * | 2021-12-27 | 2023-07-06 | 日本ゼオン株式会社 | 塩化ビニル樹脂組成物、塩化ビニル樹脂成形体および積層体 |
| EP4269060A4 (en) * | 2020-12-24 | 2024-11-13 | Zeon Corporation | Vinyl chloride resin composition, vinyl chloride resin molded body, and multilayer body |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022004320A1 (ja) * | 2020-07-02 | 2022-01-06 | Dic株式会社 | 塩化ビニル樹脂用可塑剤、塩化ビニル樹脂組成物及びその成形品 |
| JPWO2022004320A1 (ja) * | 2020-07-02 | 2022-01-06 | ||
| JP7235172B2 (ja) | 2020-07-02 | 2023-03-08 | Dic株式会社 | 塩化ビニル樹脂用可塑剤、塩化ビニル樹脂組成物及びその成形品 |
| EP4177310B1 (en) | 2020-07-02 | 2025-10-29 | DIC Corporation | Vinyl chloride resin plasticizer, vinyl chloride resin composition, and molded article thereof |
| EP4269060A4 (en) * | 2020-12-24 | 2024-11-13 | Zeon Corporation | Vinyl chloride resin composition, vinyl chloride resin molded body, and multilayer body |
| WO2023127608A1 (ja) * | 2021-12-27 | 2023-07-06 | 日本ゼオン株式会社 | 塩化ビニル樹脂組成物、塩化ビニル樹脂成形体および積層体 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112969561A (zh) | 2021-06-15 |
| EP3950254A4 (en) | 2022-12-21 |
| US20220153982A1 (en) | 2022-05-19 |
| JP7476884B2 (ja) | 2024-05-01 |
| US12351709B2 (en) | 2025-07-08 |
| EP3950254A1 (en) | 2022-02-09 |
| EP3950254B1 (en) | 2025-06-18 |
| CN112969561B (zh) | 2023-04-14 |
| JPWO2020196396A1 (ja) | 2020-10-01 |
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