Classifications

• • 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
• • 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
• • 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
• • 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
• • 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
• • 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
• • 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
• • 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
• • 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
  • B32B2250/24—All layers being polymeric
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/66—Polyesters containing oxygen in the form of ether groups
  • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/672—Dicarboxylic acids and dihydroxy compounds
• • 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
• • 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
  • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
• • 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
  • C08L2205/06—Polymer mixtures characterised by other features having improved processability or containing aids for moulding methods

Definitions

• the present invention relates to a vinyl chloride resin composition, a vinyl chloride resin molded body, and a laminate.
• Polyvinyl chloride resins are generally used in a variety of applications due to their excellent properties such as cold resistance, heat resistance, and oil resistance.
• automobile interior parts such as automobile instrument panels and door trims are formed using automobile interior materials such as a skin made of a polyvinyl chloride resin molded product and a laminate in which a skin made of a polyvinyl chloride resin molded product is backed with a foam such as polyurethane foam.
• the polyvinyl chloride resin molded body that constitutes the skin of automobile interior parts such as automobile instrument panels is manufactured, for example, by molding a polyvinyl chloride resin composition containing polyvinyl chloride resin, a plasticizer, and additives using a powder molding method such as powder slush molding (see, for example, Patent Document 1).
• a vinyl chloride resin molded body is produced by powder slush molding a vinyl chloride resin composition containing vinyl chloride resin particles, a plasticizer such as a polyester plasticizer, and additives such as a hydrotalcite-based stabilizer, a zeolite-based stabilizer, and ⁇ -diketones.
• the present inventors have conducted extensive research with the aim of solving the above problems.
• the inventors have discovered that by using a vinyl chloride resin composition containing a polyester plasticizer whose number average molecular weight is less than a predetermined value and a polyester resin whose number average molecular weight is equal to or greater than a predetermined value, it is possible to form a vinyl chloride resin molded article having excellent low-temperature tensile elongation, and have completed the present invention.
• an object of the present invention is to advantageously solve the above-mentioned problems, and the present invention provides: [1] a vinyl chloride resin composition comprising a vinyl chloride resin, a polyester plasticizer having a number average molecular weight of less than 8,000, and a polyester resin having a number average molecular weight of 8,000 or more.
• a vinyl chloride resin composition containing a vinyl chloride resin, a polyester plasticizer having a number average molecular weight less than the above-mentioned specified value, and a polyester resin having a number average molecular weight equal to or greater than the above-mentioned specified value can be used to form a vinyl chloride resin molded product having excellent low-temperature tensile elongation.
• the "number average molecular weight" of the polyester plasticizer and the polyester resin can be measured by the method described in the examples of this specification.
• the content of the polyester resin is preferably 0.1 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the vinyl chloride resin.
• the content of the polyester resin is within the above-mentioned range, the low-temperature tensile elongation of the vinyl chloride resin molded article formed can be further improved and the stickiness of the surface of the vinyl chloride resin molded article can be suppressed.
• the content of the polyester resin is within the above-mentioned range, the powder flowability of the vinyl chloride resin composition can be improved.
• the polyester resin contains a structural unit derived from a dicarboxylic acid and an alkylene oxide structural unit.
• the dicarboxylic acid preferably contains an aromatic dicarboxylic acid. If an aromatic dicarboxylic acid is used as the dicarboxylic acid forming the structural unit derived from the dicarboxylic acid in the polyester resin, the low-temperature tensile elongation of the resulting vinyl chloride resin molded article can be further improved.
• the aromatic dicarboxylic acid preferably contains at least one of terephthalic acid and isophthalic acid. If at least one of terephthalic acid and isophthalic acid is used as the aromatic dicarboxylic acid, the low-temperature tensile elongation of the resulting vinyl chloride resin molded article can be further improved.
• the alkylene oxide structural unit preferably contains at least one selected from the group consisting of an ethylene oxide structural unit, a tetramethylene oxide structural unit, and a 2,2-dimethylpropylene oxide structural unit. If the polyester resin contains the above-mentioned specific alkylene oxide structural unit, the low-temperature tensile elongation of the resulting vinyl chloride resin molded article can be further improved.
• the polyester resin preferably has a polyalkylene oxide region in which the alkylene oxide structural units are continuously arranged. If the polyester resin has a polyalkylene oxide region, the low-temperature tensile elongation of the resulting vinyl chloride resin molded article can be further improved.
• the proportion of the alkylene oxide structural units contained in the polyalkylene oxide region is 5 mol % or more and 80 mol % or less.
• the proportion of alkylene oxide structural units contained in the polyalkylene oxide region is within the above-mentioned specified range, the low-temperature tensile elongation of the resulting vinyl chloride resin molded article can be further improved and stickiness of the surface of the vinyl chloride resin molded article can be suppressed.
• the proportion of each structural unit when all structural units in the polyester resin are taken as 100 mol % i.e., the composition of the polyester resin
• the proportion of each structural unit when all structural units in the polyester resin are taken as 100 mol % can be measured by the method described in the examples of this specification.
• the content of the polyester plasticizer is preferably 30 parts by mass or more and 200 parts by mass or less per 100 parts by mass of the vinyl chloride resin.
• the content of the polyester plasticizer is within the above-mentioned range, the low-temperature tensile elongation of the vinyl chloride resin molded article to be formed can be further improved.
• the powder fluidity of the vinyl chloride resin composition can be sufficiently high, and the heat shrinkage resistance of the vinyl chloride resin molded article to be formed can be improved.
• the vinyl chloride resin composition according to any one of [1] to [9] above is preferably used for powder molding.
• the vinyl chloride resin composition for powder molding it is possible to easily obtain a vinyl chloride resin molded article which can be used favorably as an automobile interior material, such as the skin for an automobile instrument panel.
• Any of the vinyl chloride resin compositions according to [1] to [10] above is preferably used for powder slush molding.
• the vinyl chloride resin composition for powder slush molding it is possible to more easily obtain a vinyl chloride resin molded article which can be suitably used as an automobile interior material, such as the skin for an automobile instrument panel.
• Another object of the present invention is to advantageously solve the above-mentioned problems, and the present invention relates to [12] a vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition according to any one of the above [1] to [11].
• the vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition described above has excellent low-temperature tensile elongation and can be suitably used as an automobile interior material.
• the vinyl chloride resin molded article according to [12] above is preferably used for an automobile instrument panel skin.
• the vinyl chloride resin molded article of the present invention is used for the surface of an automobile instrument panel, it is possible to produce an automobile instrument panel having a surface excellent in low-temperature tensile elongation.
• the present invention has an object to advantageously solve the above-mentioned problems, and is directed to a laminate having a polyurethane foam molding [14] and the vinyl chloride resin molding [12] or [13] above.
• a laminate having a polyurethane foam molded product and the above-mentioned vinyl chloride resin molded product has a vinyl chloride resin molded product portion that is excellent in low-temperature tensile elongation.
• the laminate according to [14] above is preferably used for an automobile instrument panel. In this way, by using the laminate of the present invention in an automobile instrument panel, it is possible to improve the low-temperature tensile elongation of the skin of the manufactured automobile instrument panel.
• a vinyl chloride resin composition capable of forming a vinyl chloride resin molded article having excellent low-temperature tensile elongation. Furthermore, according to the present invention, it is possible to provide a vinyl chloride resin molded article having excellent low-temperature tensile elongation. Furthermore, according to the present invention, it is possible to provide a laminate comprising the vinyl chloride resin molded article.
• the vinyl chloride resin composition of the present invention can be used, for example, when forming the vinyl chloride resin molded article of the present invention.
• the vinyl chloride resin molded article formed using the vinyl chloride resin composition of the present invention can be suitably used, for example, as an automobile interior material, such as the skin of an automobile interior part, such as an automobile instrument panel or door trim.
• the vinyl chloride resin molded article of the present invention can be used, for example, when forming the laminate of the present invention.
• the laminate formed using the vinyl chloride resin molded article of the present invention can be suitably used, for example, as an automobile interior material used when producing automobile interior parts such as automobile instrument panels and door trims.
• the vinyl chloride resin composition of the present invention is characterized by comprising: (a) a vinyl chloride resin; (b) a polyester plasticizer having a number average molecular weight of less than a predetermined value (hereinafter may be abbreviated as “(b) polyester plasticizer”); and (c) a polyester resin having a number average molecular weight of a predetermined value or more (hereinafter may be abbreviated as “(c) polyester resin”).
• the vinyl chloride resin composition of the present invention may optionally further contain a plasticizer other than the above-mentioned (b) polyester plasticizer (hereinafter, sometimes referred to as “(d) other plasticizer”).
• the vinyl chloride resin composition of the present invention may optionally further contain additives other than the above-mentioned (a) vinyl chloride resin, (b) polyester plasticizer, (c) polyester resin, and (d) other plasticizers.
• the vinyl chloride resin composition of the present invention can be used to form vinyl chloride resin molded articles that have excellent low-temperature tensile elongation.
• vinyl chloride resin composition of the present invention it is possible to obtain vinyl chloride resin molded articles that are suitable for use as automotive interior materials, such as skins for automotive instrument panels and door trims, that have excellent fogging resistance.
• the vinyl chloride resin composition of the present invention is preferably used for powder molding, and more preferably for powder slush molding.
• vinyl chloride resin (a) a particulate vinyl chloride resin is usually used.
• the vinyl chloride resin (a) for example, one or more kinds of vinyl chloride resin particles can be contained, and optionally, one or more kinds of vinyl chloride resin microparticles can be further contained.
• the vinyl chloride resin (a) preferably contains at least vinyl chloride resin particles, and more preferably contains vinyl chloride resin particles and vinyl chloride resin microparticles.
• the (a) vinyl chloride resin can be produced by any of the conventionally known production methods, such as suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization.
• the term "resin particles” refers to particles having a particle diameter of 30 ⁇ m or more
• the term “resin fine particles” refers to particles having a particle diameter of less than 30 ⁇ m.
• the vinyl chloride resin (a) may be a homopolymer consisting of vinyl chloride monomer units, or a vinyl chloride copolymer containing preferably 50% by mass or more, more preferably 70% by mass or more, of vinyl chloride monomer units.
• monomers (comonomers) that can be copolymerized with vinyl chloride monomers and that can constitute vinyl chloride copolymers include those described in International Publication No. 2016/098344. These components may be used alone or in combination of two or more types in any ratio.
• the vinyl chloride resin particles usually function as a matrix resin (substrate).
• 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, more preferably 5000 or less, more preferably 3000 or less, and even more preferably 2800 or less. If the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is the above lower limit or more, the physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition can be sufficiently high, while, for example, the tensile properties, particularly the tensile elongation, can be improved.
• a vinyl chloride resin molded body having good tensile elongation can be suitably used as an automobile interior material such as the skin of an automobile instrument panel having excellent ductility, which breaks as designed without scattering fragments when an airbag is inflated and deployed.
• the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is the above upper limit or less, the meltability of the vinyl chloride resin composition can be improved.
• the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles may be 1,400 or more, 1,500 or more, or 1,600 or more, or may be 1,600 or less, 1,500 or less, or 1,400 or less.
• the "average degree of polymerization" can be measured in accordance with JIS K6720-2.
• the average particle size of the vinyl chloride resin particles is usually 30 ⁇ m or more, preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more, and preferably 500 ⁇ m or less, more preferably 200 ⁇ m or less. If the average particle size of the vinyl chloride resin particles is the above lower limit or more, the powder flowability of the vinyl chloride resin composition can be improved. On the other hand, if the average particle size of the vinyl chloride resin particles is the above upper limit or less, the meltability of the vinyl chloride resin composition can be improved, and the surface smoothness of the vinyl chloride resin molded body formed using the vinyl chloride resin composition can be increased.
• the "average particle size" can be measured as a volume average particle size by a laser diffraction method in accordance with JIS Z8825.
• the content 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, and is preferably 95% by mass or less, and more preferably 90% by mass or less. If the content of the vinyl chloride resin particles in the (a) vinyl chloride resin is equal to or more than the above lower limit, the tensile elongation can be improved while ensuring a sufficiently high physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition. On the other hand, if the content of the vinyl chloride resin particles in the (a) vinyl chloride resin is equal to or less than the above upper limit, the powder flowability of the vinyl chloride resin composition can be improved.
• the vinyl chloride resin fine particles usually function as a dusting agent (powder flow improver).
• the vinyl chloride resin fine particles are preferably produced by an emulsion polymerization method.
• the average polymerization degree of the vinyl chloride resin constituting the vinyl chloride resin microparticles is preferably 500 or more, more preferably 700 or more, and more preferably 2600 or less, and more preferably 2400 or less. If the average polymerization degree of the vinyl chloride resin constituting the vinyl chloride resin microparticles as a dusting agent is above the above lower limit, the powder fluidity of the vinyl chloride resin composition can be improved and the tensile elongation of the vinyl chloride resin molded body formed using the vinyl chloride resin composition can be improved.
• the melting property of the vinyl chloride resin composition can be improved, and the surface smoothness of the vinyl chloride resin molded body formed using the vinyl chloride resin composition can be increased.
• the 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 more preferably 1 ⁇ m or more. If the average particle size of the vinyl chloride resin fine particles is equal to or greater than the above lower limit, the powder flowability of the vinyl chloride resin composition can be improved without excessively reducing the size of the particles as a dusting agent. On the other hand, if the average particle size of the vinyl chloride resin fine particles is equal to or less than the above upper limit, the melting property of the vinyl chloride resin composition can be improved, and the surface smoothness of the vinyl chloride resin molded article formed can be improved.
• the content 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, and preferably 30% by mass or less, and more preferably 20% by mass or less. If the content of the vinyl chloride resin fine particles in the (a) vinyl chloride resin is equal to or greater than the lower limit, the powder flowability of the vinyl chloride resin composition can be improved. On the other hand, if the content of the vinyl chloride resin fine particles in the (a) vinyl chloride resin is equal to or less than the upper limit, the physical strength of the vinyl chloride resin molded article formed using the vinyl chloride resin composition can be increased.
• the (b) polyester plasticizer is a component that can impart flexibility to a vinyl chloride resin molded article formed using the vinyl chloride resin composition, thereby improving the tensile properties (particularly low-temperature tensile elongation) of the vinyl chloride resin molded article.
• the (b) polyester plasticizer as a plasticizer, when a laminate is produced by backing a polyurethane foam molded article on a vinyl chloride resin molded article formed using the vinyl chloride resin composition, the (b) polyester plasticizer is unlikely to migrate from the vinyl chloride resin molded article to the polyurethane foam molded article even at high temperatures, and therefore the heat shrinkage resistance of the vinyl chloride resin molded article can be improved.
• the (b) polyester plasticizer is not particularly limited, and examples of polyesters that can be used include polyesters containing structural units derived from adipic acid (adipic acid-based polyesters), polyesters containing structural units derived from sebacic acid (sebacic acid-based polyesters), and polyesters containing structural units derived from phthalic acid (phthalic acid-based polyesters). These polyesters may be used alone or in combination of two or more in any ratio. Among these, from the viewpoint of further enhancing the heat shrinkage resistance of the vinyl chloride resin molded article, it is preferable to use an adipic acid-based polyester (a polyester containing a structural unit derived from adipic acid) as the (b) polyester plasticizer.
• adipic acid-based polyester a polyester containing a structural unit derived from adipic acid
• the number average molecular weight (Mn) of the (b) polyester plasticizer must be less than 8,000, and is preferably 7,000 or less, more preferably 6,000 or less, even more preferably 5,000 or less, and even more preferably 4,000 or less. If the number average molecular weight (Mn) of the (b) polyester plasticizer is less than 8,000, the low-temperature tensile elongation of the vinyl chloride resin molded article formed can be sufficiently improved. If the number average molecular weight of the (b) polyester plasticizer is equal to or less than the upper limit, the low-temperature tensile elongation of the vinyl chloride resin molded article formed can be further improved.
• the lower limit of the number average molecular weight (Mn) of the polyester plasticizer (b) is not particularly limited, but is preferably, for example, 500 or more, more preferably 1,000 or more, and even more preferably 2,000 or more.
• the viscosity of the (b) polyester plasticizer is preferably 500 mPa ⁇ s or more, more preferably 1000 mPa ⁇ s or more, and is preferably 8000 mPa ⁇ s or less, more preferably 5000 mPa ⁇ s or less, and even more preferably 4,000 mPa ⁇ s or less.
• the "viscosity" can be measured at a temperature of 23°C in accordance with JIS Z8803.
• the content of the (b) polyester plasticizer in the vinyl chloride resin composition is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 70 parts by mass or more, even more preferably 80 parts by mass or more, even more preferably 85 parts by mass or more, and preferably 200 parts by mass or less, more preferably 180 parts by mass or less, even more preferably 150 parts by mass or less, even more preferably 130 parts by mass or less, and even more preferably 110 parts by mass or less, relative to 100 parts by mass of the (a) vinyl chloride resin.
• the content of the (b) polyester plasticizer in the vinyl chloride resin composition is the above lower limit or more, the low-temperature tensile elongation and heat shrinkage resistance of the vinyl chloride resin molded article formed can be further improved.
• the content of the (b) polyester plasticizer in the vinyl chloride resin composition is the above upper limit or less, the powder flowability of the vinyl chloride resin composition can be sufficiently high.
• the content of the (b) polyester plasticizer in the vinyl chloride resin composition may be 90 parts by mass or more, 95 parts by mass or more, or 100 parts by mass or more, or may be 100 parts by mass or less, 95 parts by mass or less, or 90 parts by mass or less, relative to 100 parts by mass of the (a) vinyl chloride resin.
• the (c) polyester resin is a component that can improve the low-temperature tensile elongation (particularly the low-temperature tensile elongation after heating) of a vinyl chloride resin molded article formed using the vinyl chloride resin composition.
• the number average molecular weight (Mn) of the (c) polyester resin must be 8,000 or more, is preferably 10,000 or more, is more preferably 15,000 or more, is even more preferably 20,000 or more, is even more preferably 25,000 or more, is even more preferably 30,000 or more, and is particularly preferably 33,000 or more, and is preferably 100,000 or less, is more preferably 80,000 or less, is even more preferably 60,000 or less, is even more preferably 50,000 or less, and is even more preferably 43,000 or less.
• the number average molecular weight (Mn) of the (c) polyester resin is 8,000 or more, the low-temperature tensile elongation of the vinyl chloride resin molded article formed can be sufficiently improved.
• the number average molecular weight (Mn) of the (c) polyester plasticizer is equal to or more than the lower limit, the powder fluidity of the vinyl chloride resin composition can be improved, and the low-temperature tensile elongation of the vinyl chloride resin molded article formed can be further improved, and the stickiness of the surface of the vinyl chloride resin molded article can be suppressed.
• the number average molecular weight (Mn) of the (c) polyester resin when the number average molecular weight (Mn) of the (c) polyester resin is equal to or less than the upper limit, the low-temperature tensile elongation of the vinyl chloride resin molded article formed can be further improved, and the stickiness of the surface of the vinyl chloride resin molded article can be suppressed.
• the number average molecular weight (Mn) of the (c) polyester resin may be 35,000 or more, or 38,000 or more, or may be 38,000 or less, or 35,000 or less, or 33,000 or less, or 30,000 or less.
• the weight average molecular weight (Mw) of the (c) polyester resin is preferably 9,000 or more, preferably 12,000 or more, more preferably 18,000 or more, even more preferably 20,000 or more, even more preferably 40,000 or more, even more preferably 50,000 or more, and particularly preferably 60,000 or more, and is preferably 150,000 or less, more preferably 120,000 or less, even more preferably 100,000 or less, even more preferably 90,000 or less, and even more preferably 80,000 or less.
• the powder fluidity of the vinyl chloride resin composition can be improved, and the low-temperature tensile elongation of the vinyl chloride resin molded article formed can be further improved, and the stickiness of the surface of the vinyl chloride resin molded article can be suppressed.
• the weight average molecular weight (Mw) of the (c) polyester resin is equal to or lower than the upper limit, the low-temperature tensile elongation of the vinyl chloride resin molded article formed can be further improved, and the stickiness of the surface of the vinyl chloride resin molded article can be suppressed.
• the weight average molecular weight (Mw) of the (c) polyester resin may be 63,000 or more, or 65,000 or more, or may be 65,000 or less, or 63,000 or less, or 60,000 or less, or 50,000 or less.
• the "weight average molecular weight" of the polyester resin (c) can be measured by the method described in the examples of this specification.
• the polyester resin (c) is not particularly limited, but preferably contains a structural unit derived from a dicarboxylic acid and an alkylene oxide structural unit.
• the polyester resin (c) can be obtained, for example, by subjecting a dicarboxylic acid and a glycol to an esterification reaction and polycondensation.
• the structural unit derived from a dicarboxylic acid in the polyester resin is a repeating unit having a structure formed by a dicarboxylic acid.
• Examples of dicarboxylic acids that can form structural units (repeating units) derived from dicarboxylic acids in the polyester resin include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid; and aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and 1,4-cyclohexanedicarboxylic acid.
• the vinyl chloride resin molded article to be formed may be used alone or in combination of two or more kinds in any ratio.
• it is preferable to use at least an aromatic dicarboxylic acid as the dicarboxylic acid it is more preferable to use at least one of terephthalic acid and isophthalic acid, it is even more preferable to use at least isophthalic acid, and it is even more preferable to use a combination of terephthalic acid and isophthalic acid.
• the alkylene oxide structural unit has the formula (I): [wherein p is an integer of 1 or more.] It is a repeating unit composed only of an alkylene oxide structure represented by the following formula: From the viewpoint of further improving the low-temperature tensile elongation of the vinyl chloride resin molded article to be formed, p in the above formula (I) is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more, and is preferably 10 or less, more preferably 8 or less, even more preferably 6 or less, still more preferably 5 or less, and particularly preferably 4.
• the alkylene oxide structural unit contained in the polyester resin (c) is preferably an ethylene oxide structural unit, a tetramethylene oxide structural unit, or a 2,2-dimethylpropylene oxide structural unit, more preferably a tetramethylene oxide structural unit or a 2,2-dimethylpropylene oxide structural unit, and even more preferably a tetramethylene oxide structural unit.
• the alkylene oxide structural unit in the (c) polyester resin is formed, for example, from a glycol used in producing the (c) polyester resin.
• glycols capable of forming an alkylene oxide structural unit in the polyester resin include those represented by the formula (II): [wherein p is the same as above.] and an alkylene glycol represented by formula (III): [wherein n is an integer of 2 or more, and p is the same as above.] and the like can be used. These glycols may be used alone or in combination of two or more at any ratio.
• alkylene glycol for example, linear alkylene glycols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc.; branched alkylene glycols such as 2-methylpropanediol, 2,3-dimethylbutanediol, butylethylpropanediol, neopentyl glycol, etc. can be used. These alkylene glycols may be used alone or in combination of two or more in any ratio.
• ethylene glycol, 1,4-butanediol, and neopentyl glycol as the alkylene glycol, and it is more preferable to use 1,4-butanediol.
• polyoxyalkylene glycol diethylene glycol, polyethylene glycol, polyoxytetramethylene glycol (sometimes referred to as "polytetramethylene ether glycol"), polyoxypropylene glycol, a copolymer of tetramethylene oxide (tetrahydrofuran) and neopentylene oxide, a copolymer of tetramethylene oxide (tetrahydrofuran) and propylene oxide, etc., can be used.
• polyoxyalkylene glycols may be used alone or in combination of two or more in any ratio.
• diethylene glycol or polyoxytetramethylene glycol as the polyoxyalkylene glycol, and it is more preferable to use polyoxytetramethylene glycol.
• the glycol is not particularly limited, but typically at least an alkylene glycol is used. From the viewpoint of further improving the low-temperature tensile elongation of the resulting polyvinyl chloride resin molded body, it is preferable to use an alkylene glycol in combination with a polyoxyalkylene glycol.
• the resulting (c) polyester resin has at least a polyester region in which structural units derived from the dicarboxylic acid and alkylene oxide structural units derived from the alkylene glycol are arranged alternately.
• polyoxyalkylene glycol is further used as the glycol during production of the (c) polyester resin
• the obtained (c) polyester resin further has a polyalkylene oxide region in which alkylene oxide structural units derived from the polyoxyalkylene glycol are continuously arranged.
• the (c) polyester resin may have only a polyester region, but from the viewpoint of further improving the low-temperature tensile elongation of the resulting vinyl chloride resin molded article, it is preferable that the polyester resin further has a polyalkylene oxide region in addition to the polyester region.
• the proportion of the alkylene oxide structural unit derived from alkylene glycol in the (c) polyester resin can be, for example, 50 mol% or less, preferably 40 mol% or less, more preferably 35 mol% or less, even more preferably 30 mol% or less, even more preferably 25 mol% or less, preferably 10 mol% or more, and more preferably 15 mol% or more, when the total structural units (total repeating units) in the (c) polyester resin are taken as 100 mol%.
• the proportion of the alkylene oxide structural unit derived from alkylene glycol in the (c) polyester resin i.e., contained in the polyester region
• the low-temperature tensile elongation of the vinyl chloride resin molded article formed can be further improved and the stickiness of the surface of the vinyl chloride resin molded article can be suppressed.
• the proportion of the alkylene oxide structural unit derived from alkylene glycol in the (c) polyester resin i.e., contained in the polyester region
• the low-temperature tensile elongation of the vinyl chloride resin molded article formed can be further improved.
• the proportion of the alkylene oxide structural unit derived from polyoxyalkylene glycol in the (c) polyester resin can be 0 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, even more preferably 40 mol% or more, even more preferably 50 mol% or more, preferably 80 mol% or less, and more preferably 70 mol% or less, when the total structural units (total repeating units) in the (c) polyester resin are taken as 100 mol%.
• the proportion of the alkylene oxide structural unit derived from polyoxyalkylene glycol in the (c) polyester resin i.e., contained in the polyalkylene oxide region
• the low-temperature tensile elongation of the vinyl chloride resin molded article formed can be further improved and the stickiness of the surface of the vinyl chloride resin molded article can be suppressed.
• the proportion of alkylene oxide structural units derived from polyoxyalkylene glycol in the (c) polyester resin i.e., contained in the polyalkylene oxide region
• the proportion of alkylene oxide structural units derived from polyoxyalkylene glycol in the (c) polyester resin i.e., contained in the polyalkylene oxide region
• the low-temperature tensile elongation of the resulting vinyl chloride resin molded article can be further improved.
• the ratio of the structural unit derived from dicarboxylic acid in the (c) polyester resin can be, for example, 50 mol% or less, preferably 40 mol% or less, more preferably 35 mol% or less, even more preferably 30 mol% or less, even more preferably 25 mol% or less, preferably 10 mol% or more, and more preferably 15 mol% or more, when the total structural units (total repeating units) in the (c) polyester resin are taken as 100 mol%.
• the ratio of the structural unit derived from dicarboxylic acid in the (c) polyester resin is below the above upper limit, the low-temperature tensile elongation of the vinyl chloride resin molded article formed can be further improved and the stickiness of the surface of the vinyl chloride resin molded article can be suppressed.
• the ratio of the structural unit derived from dicarboxylic acid in the (c) polyester resin is above the above lower limit, the low-temperature tensile elongation of the vinyl chloride resin molded article formed can be further improved.
• the (c) polyester resin may be a crystalline polyester, an amorphous polyester, or a mixture of a crystalline polyester and an amorphous polyester. From the viewpoints of further improving the low-temperature tensile elongation of the vinyl chloride resin molded article to be formed and suppressing stickiness of the surface of the vinyl chloride resin molded article, it is preferable that the (c) polyester resin is a crystalline polyester. When the (c) polyester resin is a crystalline polyester, the (c) polyester resin has a melting point.
• the melting point of the (c) polyester resin is preferably 85°C or higher, more preferably 95°C or higher, even more preferably 100°C or higher, even more preferably 110°C or higher, even more preferably 120°C or higher, and is preferably 180°C or lower, more preferably 150°C or lower, and even more preferably 135°C or lower. (c) If the melting point of the polyester resin is within the above-mentioned range, the low-temperature tensile elongation of the vinyl chloride resin molded article to be formed can be further improved, and the stickiness of the surface of the vinyl chloride resin molded article can be further suppressed.
• the (c) polyester resin can be obtained by carrying out an esterification reaction of the above-mentioned dicarboxylic acid and glycol at 150° C. to 250° C., followed by polycondensation at 230° C. to 300° C. while reducing the pressure.
• the (c) polyester resin can be obtained by carrying out an ester exchange reaction at 150° C. to 250° C. using a derivative of the above-mentioned dicarboxylic acid, such as a dimethyl ester, and glycol, followed by polycondensation at 230° C. to 300° C. while reducing the pressure.
• the content of the (c) polyester resin in the vinyl chloride resin composition is, relative to 100 parts by mass of the (a) vinyl chloride resin, preferably 0.1 part by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, even more preferably 4 parts by mass or more, even more preferably 5 parts by mass or more, particularly preferably 7 parts by mass or more, and is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, even more preferably 12 parts by mass or less, and even more preferably 10 parts by mass or less.
• the content of the (c) polyester resin in the vinyl chloride resin composition is equal to or greater than the above lower limit, the low-temperature tensile elongation of the vinyl chloride resin molded article formed can be further improved. If the content of the (c) polyester resin in the vinyl chloride resin composition is equal to or greater than the above lower limit, the powder flowability of the vinyl chloride resin composition can be improved and the stickiness of the surface of the vinyl chloride resin molded article formed can be suppressed.
• the powder flowability of the vinyl chloride resin composition can be sufficiently high and the low-temperature tensile elongation of the vinyl chloride resin molded article formed can be further improved.
• the content of the (c) polyester resin in the vinyl chloride resin composition is, relative to 100 parts by mass of the (b) polyester plasticizer, preferably 0.1 part by mass or more, more preferably 1 part by mass or more, even more preferably 2 parts by mass or more, even more preferably 3 parts by mass or more, even more preferably 4 parts by mass or more, even more preferably 5 parts by mass or more, particularly preferably 7 parts by mass or more, and is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, even more preferably 12 parts by mass or less, and even more preferably 10 parts by mass or less.
• the content of the (c) polyester resin in the vinyl chloride resin composition is equal to or greater than the above lower limit, the low-temperature tensile elongation of the vinyl chloride resin molded article formed can be further improved. If the content of the (c) polyester resin in the vinyl chloride resin composition is equal to or greater than the above lower limit, the powder flowability of the vinyl chloride resin composition can be improved and the stickiness of the surface of the vinyl chloride resin molded article formed can be suppressed.
• the powder flowability of the vinyl chloride resin composition can be sufficiently high and the low-temperature tensile elongation of the vinyl chloride resin molded article formed can be further improved.
• the vinyl chloride resin composition of the present invention may optionally further contain (d) another plasticizer other than the above-mentioned (b) polyester plasticizer.
• plasticizers include those plasticizers described in WO 2016/098344 other than the above-mentioned (b) polyester plasticizer.
• plasticizers described in WO 2016/098344 other than the above-mentioned (b) polyester plasticizer.
• epoxidized vegetable oil from the viewpoint of further improving the low-temperature tensile elongation of the polyvinyl chloride resin molded body to be formed, it is preferable to use epoxidized vegetable oil, and it is more preferable to use epoxidized soybean oil.
• the content of the (d) other plasticizer in the vinyl chloride resin composition is not particularly limited, but can be 0 parts by mass or more and 15 parts by mass or less per 100 parts by mass of the (a) vinyl chloride resin.
• an epoxidized vegetable oil such as epoxidized soybean oil
• the content of the epoxidized vegetable oil as the (d) other plasticizer is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and even more preferably 4 parts by mass or more, and is preferably 10 parts by mass or less, and more preferably 7 parts by mass or less, per 100 parts by mass of the above-mentioned (a) vinyl chloride resin.
• the content of the (d) other plasticizer in the vinyl chloride resin composition is not particularly limited, but can be 0 parts by mass or more and 15 parts by mass or less per 100 parts by mass of the (b) polyester plasticizer.
• an epoxidized vegetable oil such as epoxidized soybean oil is used as the (d) other plasticizer, from the viewpoint of further improving the low-temperature tensile elongation of the vinyl chloride resin molded body formed
• the content of the epoxidized vegetable oil as the (d) other plasticizer is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and even more preferably 4 parts by mass or more, and is preferably 10 parts by mass or less, and more preferably 7 parts by mass or less, per 100 parts by mass of the above-mentioned (b) polyester plasticizer.
• the vinyl chloride resin composition of the present invention may further contain various additives in addition to the above-mentioned components.
• the additives are not particularly limited, and examples thereof include lubricants, stabilizers such as perchloric acid-treated hydrotalcite, zeolite, ⁇ -diketone, and fatty acid metal salts, release agents, dusting agents other than the above-mentioned vinyl chloride resin fine particles, impact resistance improvers, perchloric acid compounds other than perchloric acid-treated hydrotalcite (sodium perchlorate, potassium perchlorate, etc.), antioxidants, antifungal agents, flame retardants, antistatic agents, fillers, light stabilizers, foaming agents, and pigments.
• the additives that may be contained in the vinyl chloride resin composition of the present invention include, for example, those described in WO 2016/098344, and the preferred content thereof may be the same as that described in WO 2016/098344.
• the vinyl chloride resin composition of the present invention may further contain an amide compound and silicone oil as additives.
• the amide compound is a component that can improve the demoldability of the vinyl chloride resin molded article that is formed.
• the amide compound is a compound having an amide group, and is, for example, represented by the following formula (1): R1 ( NR2COR3 ) n (1)
• R1 is an n-valent hydrocarbon group
• R2 is a monovalent hydrocarbon group or hydrogen
• R3 is a monovalent hydrocarbon group
• the n R2s may be the same or different
• the n R3s may be the same or different.
• the amide compound has a structure in which n hydrogen atoms of a hydrocarbon are substituted with amide groups represented by -NR2COR3 .
• n in the above formula (1) is, for example, an integer between 2 and 6 inclusive, and may be an integer between 2 and 3 inclusive, or may be 2.
• R 1 in the above formula (1) is an n-valent hydrocarbon group, which may be an n-valent aliphatic hydrocarbon group or an n-valent aromatic hydrocarbon group. Furthermore, the number of carbon atoms contained in R 1 may be, for example, 1 or more, 2 or more, 8 or less, or 6 or less.
• R1 examples include a methylene group, a methylmethylene group, an ethylene group (dimethylene group), a dimethylmethylene group, an isopropylene group, a trimethylene group, an isobutylene group, a tetramethylene group, and a hexamethylene group.
• R2 in the above formula (1) is a monovalent hydrocarbon group or hydrogen, and n R2s may be the same or different from each other.
• the monovalent hydrocarbon group of R2 may be a monovalent aliphatic hydrocarbon group or a monovalent aromatic hydrocarbon group.
• the monovalent aliphatic hydrocarbon group is, for example, a monovalent chain aliphatic hydrocarbon group.
• the monovalent aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.
• the hydrocarbon group of R2 has, for example, 1 or more and 2 or less carbon atoms. Examples of R2 include hydrogen, a methyl group, and an ethyl group.
• n R2 may be hydrogen, or all of n R2 may be hydrogen.
• R3 in the above formula (1) is a monovalent hydrocarbon group, and n R3 may be the same or different from each other.
• a saturated hydrocarbon group of R3 and an unsaturated hydrocarbon group of R3 may be mixed in one molecule, or only an unsaturated hydrocarbon group of R3 may be present, or only a saturated hydrocarbon group of R3 may be present.
• the saturated hydrocarbon group of R3 is, for example, a monovalent chain saturated aliphatic hydrocarbon group.
• the number of carbon atoms in the saturated hydrocarbon group of R3 may be 11 or more, 13 or more, 15 or more, 23 or less, 21 or less, 19 or less, or 17.
• saturated hydrocarbon groups for R3 include CH3 ( CH2 ) 10- , CH3 ( CH2 ) 12- , CH3 ( CH2 ) 14- , CH3 ( CH2 ) 16- , CH3( CH2 ) 18- , CH3 ( CH2 ) 20- , CH3 ( CH2 ) 22- , and the like.
• the unsaturated hydrocarbon group of R3 is, for example, a monovalent chain unsaturated aliphatic hydrocarbon group.
• the number of carbon atoms in the unsaturated hydrocarbon group of R3 may be 11 or more, 13 or more, 15 or more, 23 or less, 21 or less, 19 or less, or 17.
• Examples of the unsaturated hydrocarbon group for R 3 include monounsaturated hydrocarbon groups such as CH 3 (CH 2 ) 7 CH ⁇ CH(CH 2 ) 7 - and CH 3 (CH 2 ) 7 CH ⁇ CH(CH 2 ) 11 -; diunsaturated hydrocarbon groups such as CH 3 (CH 2 ) 4 (CH ⁇ CHCH 2 ) 2 (CH 2 ) 6 -; triunsaturated hydrocarbon groups such as CH 3 CH 2 (CH ⁇ CHCH 2 ) 3 (CH 2 ) 6 -; tetraunsaturated hydrocarbon groups; pentaunsaturated hydrocarbon groups; hexaunsaturated hydrocarbon groups; and other unsaturated hydrocarbon groups having a carbon-carbon double bond, as well as unsaturated hydrocarbon groups having a carbon-carbon triple bond.
• monounsaturated hydrocarbon groups such as CH 3 (CH 2 ) 7 CH ⁇ CH(CH 2 ) 7 - and CH 3 (CH 2 ) 7 CH ⁇ CH(CH 2 ) 11 -
• amide compounds include ethylene bis oleamide (particularly dimethylene bis oleamide), ethylene bis erucamide, hexamethylene bis oleamide, ethylene bis laurate, ethylene bis stearamide (particularly dimethylene bis stearamide), ethylene bis palmitate, and hexamethylene bis stearamide.
• the content of the amide compound in the vinyl chloride resin composition may be 0 parts by mass, 0.1 parts by mass or more, 0.25 parts by mass or more, 1.5 parts by mass or less, 1.25 parts by mass or less, or 1 part by mass or less, relative to 100 parts by mass of the vinyl chloride resin (a) described above.
• the content of the amide compound in the vinyl chloride resin composition may be 0 parts by mass, 0.1 parts by mass or more, 0.25 parts by mass or more, 1.5 parts by mass or less, 1.25 parts by mass or less, or 1 part by mass or less, relative to 100 parts by mass of the (b) polyester plasticizer.
• the vinyl chloride resin composition of the present invention does not have to contain an amide compound.
• the silicone oil is a component that can improve the powder flowability of the vinyl chloride resin composition and can suppress the stickiness of the surface of the vinyl chloride resin molded article to be formed.
• As the silicone oil either an unmodified silicone oil or a modified silicone may be used.
• the content of the silicone oil in the vinyl chloride resin composition may be 0 parts by mass, 0.1 parts by mass or more, 0.25 parts by mass or more, 1.5 parts by mass or less, 1.25 parts by mass or less, or 1 part by mass or less, relative to 100 parts by mass of the vinyl chloride resin (a) described above.
• the content of the silicone oil in the vinyl chloride resin composition may be 0 parts by mass, 0.1 parts by mass or more, 0.25 parts by mass or more, 1.5 parts by mass or less, 1.25 parts by mass or less, or 1 part by mass or less, relative to 100 parts by mass of the polyester plasticizer (b).
• the vinyl chloride resin composition of the present invention does not have to contain silicone oil.
• the vinyl chloride resin composition of the present invention can be prepared by mixing the above-mentioned components.
• the method of mixing the (a) vinyl chloride resin, (b) polyester plasticizer, (c) polyester resin, and (d) other plasticizers and various additives further blended as necessary is not particularly limited, and for example, a method of mixing the components other than the dusting agent (including vinyl chloride resin fine particles) by dry blending, and then adding and mixing the dusting agent can be mentioned.
• a Henschel mixer for dry blending.
• the temperature during 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 vinyl chloride resin composition thus obtained can be suitably used for powder molding, and more suitably used for powder slush molding.
• the vinyl chloride resin molded article of the present invention is characterized in that it is obtained by molding the above-mentioned vinyl chloride resin composition by any method. Since the vinyl chloride resin molded article of the present invention is formed using the above-mentioned vinyl chloride resin composition, it usually contains at least (a) vinyl chloride resin, (b) polyester plasticizer, and (c) polyester resin.
• the vinyl chloride resin molded article of the present invention is excellent in low-temperature tensile elongation. Therefore, the vinyl chloride resin molded article of the present invention can be suitably used as an automobile interior material such as the surface of an automobile instrument panel.
• the mold temperature during powder slush molding is not particularly limited, but is preferably 200° C. or higher, more preferably 220° C. or higher, and is preferably 300° C. or lower, and more preferably 280° C. or lower.
• the following method can be used, for example, without any particular limitations. That is, the vinyl chloride resin composition of the present invention is sprinkled onto a mold having a temperature in the above range, and left for 5 to 30 seconds, after which the excess vinyl chloride resin composition is shaken off, and the product is further left for 30 seconds to 3 minutes at any temperature. The mold is then cooled to 10°C to 60°C, and the obtained vinyl chloride resin molded article of the present invention is demolded from the mold. Then, a sheet-like molded article having the shape of the mold is obtained.
• the laminate of the present invention comprises a polyurethane foam molded article and the above-mentioned vinyl chloride resin molded article.
• the vinyl chloride resin molded article usually constitutes one surface of the laminate.
• the laminate of the present invention is formed, for example, using the vinyl chloride resin composition of the present invention and has a vinyl chloride resin molded article excellent in low-temperature tensile elongation, and is therefore suitably used as an automobile interior part, in particular an automobile interior material for forming an automobile instrument panel.
• the lamination method of the foamed polyurethane molded body and the polyvinyl chloride resin molded body is not particularly limited, and the following methods can be used, for example. That is, (1) a method in which a foamed polyurethane molded body and a polyvinyl chloride resin molded body are prepared separately, and then bonded together by heat fusion, heat adhesion, or using a known adhesive; (2) a method in which isocyanates and polyols, which are the raw materials for the foamed polyurethane molded body, are reacted on the polyvinyl chloride resin molded body to polymerize, and polyurethane is foamed by a known method to directly form a foamed polyurethane molded body on the polyvinyl chloride resin molded body; etc.
• the latter method (2) is preferred because of its simple process and the ease of firmly bonding the polyvinyl chloride resin molded body and the foamed polyurethane molded body even when laminates
• ⁇ Number average molecular weight and weight average molecular weight> The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polyester plasticizer and polyester resin were determined as polystyrene equivalent values by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.
• the melting point of the polyester resin was measured using a differential scanning calorimeter "DSC7000X” manufactured by Hitachi High-Tech Science Corporation by placing 5.0 mg of the polyester resin as a measurement sample in an aluminum pan, sealing it by pressing the lid, heating it from 20°C to 250°C at 10°C/min, holding it for 5 minutes to completely melt the sample, then lowering the temperature to 0°C at 20°C/min, holding it for 5 minutes, and then heating it again to 250°C at 20°C/min.
• the endothermic peak in the obtained thermogram curve was taken as the melting point of the polyester resin.
• composition of the polyester resin i.e., the ratio of each structural unit when all structural units in the polyester resin are 100 mol %) was calculated from the proton integral ratio obtained by 1H -NMR (nuclear magnetic resonance) method.
• 1H -NMR nuclear magnetic resonance
• the surface stickiness of the polyvinyl chloride resin molded sheets obtained in the Examples and Comparative Examples was evaluated by measuring the dynamic friction coefficient as follows. Specifically, the kinetic friction coefficient of the surface of the polyvinyl chloride resin molded sheet before the formation of the laminate was measured by contacting the tactile contactor with a texture tester (manufactured by Trinity Labs, product name "TL201Ts") under the following conditions: load: 50 g, speed: 10 mm/sec, test range: 50 mm, measurement range: 30 mm excluding 10 mm before and after the test range, in a measurement environment of 23°C and 50% relative humidity. The smaller the kinetic friction coefficient, the more the stickiness of the surface of the polyvinyl chloride resin molded body is suppressed.
• polyester resins A to F used in the examples were produced according to the following Production Examples 1 to 6.
• Polyester resins B to F were produced and various measurements were carried out in the same manner as in Production Example 1, except that at least one of the type and amount of the dicarboxylic acid and glycol used was changed so that the composition of the resulting polyester resin would be as shown in Table 1. The results are shown in Table 1.
• Example 1 Preparation of vinyl chloride resin composition> Of the ingredients shown in Tables 2 and 3, the ingredients except for the plasticizer (polyester plasticizer and epoxidized soybean oil) and the vinyl chloride resin fine particles as a dusting agent were put into a Henschel mixer and mixed. Then, when the temperature of the mixture rose to 80°C, all of the plasticizer was added and the mixture was allowed to dry up (referring to the state in which the plasticizer is absorbed into the vinyl chloride resin particles as the vinyl chloride resin and the mixture becomes smooth). Thereafter, when the dried-up mixture was cooled to a temperature of 70°C or less, the vinyl chloride resin fine particles as a dusting agent were added to prepare a vinyl chloride resin composition.
• the plasticizer polyester plasticizer and epoxidized soybean oil
• the vinyl chloride resin fine particles as a dusting agent were put into a Henschel mixer and mixed. Then, when the temperature of the mixture rose to 80°C, all of the plasticizer was added and the mixture was allowed to dry
• the resulting vinyl chloride resin composition was evaluated for powder flowability, and the results are shown in Table 2.
• ⁇ Formation of vinyl chloride resin molded article> The obtained vinyl chloride resin composition was sprinkled on a textured mold heated to a temperature of 250° C., and allowed to stand for an arbitrary time to melt, after which the excess vinyl chloride resin composition was shaken off.
• the textured mold on which the vinyl chloride resin composition was sprinkled was then placed in an oven set at a temperature of 200° C., and 60 seconds after being placed in the oven, the textured mold was cooled with cooling water.
• a vinyl chloride resin molded sheet of 145 mm ⁇ 175 mm ⁇ 1 mm was removed from the mold as a vinyl chloride resin molded product.
• the vinyl chloride resin composition thus obtained was evaluated for surface stickiness and low-temperature tensile elongation (initial value), and the results are shown in Table 2.
• ⁇ Formation of Laminate> The obtained vinyl chloride resin molded sheet was cut into a size of 100 mm x 100 mm, and two of the cut vinyl chloride resin molded sheets were placed in a 200 mm x 300 mm x 10 mm mold so as not to overlap, with the textured side facing down.
• PO-EO
• the prepared mixture was then poured onto two vinyl chloride resin molded sheets laid in the mold as described above.
• the mold was then sealed by covering it with an aluminum plate measuring 348 mm x 255 mm x 10 mm.
• Five minutes after sealing a laminate consisting of a 1 mm thick vinyl chloride resin molded sheet backed by a polyurethane foam molded body was removed from the mold, and the vinyl chloride resin molded sheet in the laminate was evaluated for low-temperature tensile elongation (after heating). The results are shown in Table 2.
• Examples 2 to 12 Vinyl chloride resin compositions, vinyl chloride resin molded articles and laminates were prepared and various evaluations were carried out in the same manner as in Example 1, except that the blending compositions were changed as shown in Tables 2 and 3. The results are shown in Tables 2 and 3.
• a vinyl chloride resin composition capable of forming a vinyl chloride resin molded article having excellent low-temperature tensile elongation. Furthermore, according to the present invention, it is possible to provide a vinyl chloride resin molded article having excellent low-temperature tensile elongation. Furthermore, according to the present invention, it is possible to provide a laminate comprising the vinyl chloride resin molded article.

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• 2023
  • 2023-09-22 JP JP2024549340A patent/JPWO2024070984A1/ja active Pending
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