WO2024070985A1 - 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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- WO2024070985A1 WO2024070985A1 PCT/JP2023/034595 JP2023034595W WO2024070985A1 WO 2024070985 A1 WO2024070985 A1 WO 2024070985A1 JP 2023034595 W JP2023034595 W JP 2023034595W WO 2024070985 A1 WO2024070985 A1 WO 2024070985A1
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- chloride resin
- vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
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 powder molding a polyvinyl chloride resin composition that contains polyvinyl chloride resin, a plasticizer, and additives such as stabilizers and pigments using a known molding method such as powder slush molding (see, for example, Patent Document 1).
- a skin made of a vinyl chloride resin molded body is produced by powder slush molding a vinyl chloride resin composition containing vinyl chloride resin, a plasticizer such as a trimellitic ester and a specific polyester, and additives such as a stabilizer and a pigment.
- a further object of the present invention is to provide a laminate comprising the vinyl chloride resin molded article.
- 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 vinyl chloride resin, a predetermined amount or more of a plasticizer, and a hindered amine light stabilizer whose molecular weight is within a predetermined range, it is possible to suppress changes in gloss of a vinyl chloride resin molded body formed using the vinyl chloride resin composition, 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 a vinyl chloride resin composition
- a vinyl chloride resin composition comprising: [1] a vinyl chloride resin, a plasticizer, and a hindered amine-based light stabilizer having a molecular weight of 550 or more and 1,500 or less, wherein the content of the plasticizer is 75 parts by mass or more per 100 parts by mass of the vinyl chloride resin.
- a vinyl chloride resin composition containing a vinyl chloride resin, a predetermined amount or more of a plasticizer, and a hindered amine-based light stabilizer having a molecular weight within a predetermined range can form a vinyl chloride resin molded article in which gloss change is suppressed.
- the content of the hindered amine light stabilizer is preferably 0.01 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the vinyl chloride resin. If the content of the hindered amine light stabilizer is within the above-mentioned range, the change in gloss of the vinyl chloride resin molded article formed can be further suppressed, and the change in color tone of the vinyl chloride resin molded article due to irradiation of light, etc. (hereinafter, may be abbreviated as "color tone change”) and stickiness of the surface can be suppressed.
- the tensile elongation (particularly tensile elongation at low temperatures) of the vinyl chloride resin molded article formed can be improved.
- the hindered amine light stabilizer is represented by the following formula (I): [In formula (I), R 1 is a hydrogen atom or an alkyl group, and "*" indicates a bond.] It is preferable that the aryl group has a monovalent organic group represented by the following formula: When the hindered amine light stabilizer has an organic group represented by the above formula (I), the change in gloss of the resulting vinyl chloride resin molded article can be further suppressed.
- R 1 is a methyl group.
- R 1 in the above formula (I) is a methyl group, the change in gloss of the vinyl chloride resin molded article to be formed can be further suppressed.
- the hindered amine light stabilizer is represented by the following formula (II): [In formula (II), R2 and R3 each independently represent a hydrogen atom or an alkyl group, and "*" represents a bond.] It is preferable that the aryl group has a monovalent organic group represented by the following formula: When the hindered amine light stabilizer has an organic group represented by the above formula (II), the change in gloss of the resulting vinyl chloride resin molded article can be further suppressed.
- both of R 2 and R 3 are a tert-butyl group.
- R 2 and R 3 in the above formula (II) are both tert-butyl groups, the change in gloss of the resulting vinyl chloride resin molded article can be further suppressed.
- the hindered amine light stabilizer is represented by the following formula (III): It is preferable that the compound contains a compound represented by the following formula: By using the compound represented by the above formula (III) as the hindered amine light stabilizer, the change in gloss of the resulting vinyl chloride resin molded article can be further suppressed.
- the plasticizer preferably contains at least one of a trimellitic acid ester and a polyester.
- the vinyl chloride resin compositions of the above [1] to [8] preferably further contain a crosslinked vinyl chloride resin.
- the use of a crosslinked vinyl chloride resin can improve the powder flowability of the vinyl chloride resin composition and suppress the stickiness of the surface of the vinyl chloride resin molded article to be formed, and can further suppress the change in gloss of the vinyl chloride resin molded article to be formed.
- the vinyl chloride resin compositions of the above [1] to [9] are 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.
- the vinyl chloride resin compositions of the above [1] to [10] are 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 above-mentioned vinyl chloride resin composition of the present invention is inhibited from changing in gloss and has excellent appearance stability.
- the vinyl chloride resin molded article according to [12] above is preferably used for an automobile instrument panel skin.
- INDUSTRIAL APPLICABILITY The vinyl chloride resin molded article of the present invention is suitable for use as the surface of an automobile instrument panel, which is suppressed in change in gloss and has excellent appearance stability.
- 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 of the present invention has a vinyl chloride resin molded product portion in which gloss change is suppressed and which has excellent appearance stability.
- 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 suppress changes in gloss of the surface of the manufactured automobile instrument panel and improve the stability of its appearance.
- a vinyl chloride resin composition capable of forming a vinyl chloride resin molded article in which change in gloss is suppressed. Furthermore, according to the present invention, it is possible to provide a vinyl chloride resin molded article in which changes in gloss are suppressed. 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 plasticizer, and (c) a hindered amine light stabilizer having a molecular weight within a predetermined range (hereinafter, may be abbreviated as “(c) hindered amine light stabilizer”).
- the vinyl chloride resin composition of the present invention may further contain (d) a crosslinked vinyl chloride resin.
- the vinyl chloride resin composition of the present invention may optionally contain further additives other than the above-mentioned (a) vinyl chloride resin, (b) plasticizer, (c) hindered amine light stabilizer, and (d) cross-linked vinyl chloride resin.
- the vinyl chloride resin composition of the present invention it is possible to form a vinyl chloride resin molded article in which change in gloss is suppressed. Therefore, by using the vinyl chloride resin composition of the present invention, it is possible to obtain vinyl chloride resin molded articles suitable for use as automobile interior materials, such as skins for automobile instrument panels and door trim skins. From the viewpoint of easily obtaining a vinyl chloride resin molded article that can be favorably used as an automobile interior material, for example, using the vinyl chloride resin composition of the present invention, the vinyl chloride resin composition of the present invention is preferably used for powder molding, and more preferably used 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 made 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. WO 2016/098344. These components may be used alone or in combination of two or more in any ratio.
- the (a) vinyl chloride resin is defined as a non-crosslinked vinyl chloride resin, i.e., the (a) vinyl chloride resin does not include the (d) crosslinked vinyl chloride resin described below.
- 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 ensured, while, for example, the tensile properties, particularly the tensile elongation, can be made good.
- the 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" 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 article formed can be improved.
- 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 80% by mass or more, more preferably 90% by mass or more, and can be 100% by mass, and is preferably 99% 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 lower limit, the tensile elongation of the vinyl chloride resin molded article formed can be improved while ensuring sufficient physical strength. 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 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 preferably 2600 or less, 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 equal to or higher than the lower limit, the powder flowability of the vinyl chloride resin composition can be improved and the tensile elongation of the vinyl chloride resin molded article formed can be improved.
- the meltability of the vinyl chloride resin composition can be increased and the surface smoothness of the vinyl chloride resin molded article formed can be improved.
- 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 meltability 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 1% by mass or more, preferably 20% by mass or less, and more preferably 10% by mass or less. If the content of the vinyl chloride resin fine particles in the (a) vinyl chloride resin is equal to or more 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 can be increased.
- the (b) plasticizer is not particularly limited, but preferably contains at least one of (b1) trimellitic acid ester and (b2) polyester. If at least one of (b1) trimellitic acid ester and (b2) polyester is used as the (b) plasticizer used in the vinyl chloride resin composition of the present invention, a vinyl chloride resin molded body excellent in tensile properties (tensile elongation and tensile stress) can be formed.
- polyester is used as the (b) plasticizer
- the plasticizer contained in the vinyl chloride resin molded body can be migrated to the foamed polyurethane molded body at high temperatures, and the thermal shrinkage of the vinyl chloride resin molded body caused by this can be suppressed. That is, if (b2) polyester is used as the (b) plasticizer, the heat shrinkage resistance of the vinyl chloride resin molded body formed can be improved.
- the (b) plasticizer may contain both the (b1) trimellitic acid ester and the (b2) polyester, or may contain one of the (b1) trimellitic acid ester and the (b2) polyester without containing the other.
- the (b) plasticizer may contain a plasticizer other than the (b1) trimellitic acid ester and the (b2) polyester (hereinafter, sometimes referred to as "(b3) other plasticizers").
- the content of the (b) plasticizer in the vinyl chloride resin composition i.e., the total content of the (b1) trimellitic ester, (b2) polyester, and (b3) other plasticizer
- the content of the (b) plasticizer in the vinyl chloride resin composition must be 75 parts by mass or more, preferably 80 parts by mass or more, more preferably 85 parts by mass or more, even more preferably 90 parts by mass or more, even more preferably 100 parts by mass or more, even more preferably 110 parts by mass or more, preferably 200 parts by mass or less, more preferably 180 parts by mass or less, even more preferably 160 parts by mass or less, even more preferably 140 parts by mass or less, and even more preferably 125 parts by mass or less.
- the content of the (b) plasticizer in the vinyl chloride resin composition is equal to or more than the above lower limit, the vinyl chloride resin composition can be well molded (particularly powder molded), and sufficient flexibility can be imparted to the vinyl chloride resin molded body formed.
- the content of the (b) plasticizer in the vinyl chloride resin composition is equal to or less than the above upper limit, the change in gloss of the vinyl chloride resin molded body formed can be further suppressed, and the change in color tone and stickiness of the surface of the vinyl chloride resin molded body can be suppressed.
- the content of the (b) plasticizer in the vinyl chloride resin composition can be appropriately adjusted within a range in which the desired effects of the present invention can be obtained, and can be, for example, 35% by mass or more and 65% by mass or less.
- the "content of the plasticizer" in the vinyl chloride resin composition can be measured by using the vinyl chloride resin composition or a vinyl chloride resin molded product formed using the vinyl chloride resin composition as a measurement sample, and applying a Soxhlet extraction method.
- the (b1) trimellitic acid ester contained in the (b) plasticizer is preferably an ester compound of trimellitic acid and a monohydric alcohol.
- the monohydric alcohol include, but are not limited to, aliphatic alcohols such as 1-hexanol, 1-heptanol, 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, and 1-dodecanol.
- aliphatic alcohols having 6 to 18 carbon atoms are preferred as the monohydric alcohol, and linear aliphatic alcohols having 6 to 18 carbon atoms are more preferred.
- the trimellitic acid ester (b1) is preferably a triester product in which substantially all of the carboxy groups of trimellitic acid are esterified with the above-mentioned monohydric alcohol.
- the alcohol residue portions in the triester product may be derived from the same alcohol or from different alcohols.
- the trimellitic acid ester (b1) may be composed of a single compound or may be a mixture of different compounds.
- trimellitic acid esters include tri-n-hexyl trimellitate, tri-n-heptyl trimellitate, tri-n-octyl trimellitate, tri-(2-ethylhexyl) trimellitate, tri-n-nonyl trimellitate, tri-n-decyl trimellitate, triisodecyl trimellitate, tri-n-undecyl trimellitate, tri-n-dodecyl trimellitate, trialkyl trimellitate (esters having two or more alkyl groups with different carbon numbers [however, the number of carbon atoms is 6 to 18] in the molecule), tri-n-alkyl trimellitate (esters having two or more alkyl groups with different carbon numbers [however, the number of carbon atoms is 6 to 18] in the molecule), and mixtures thereof.
- trimellitic acid ester More preferred specific examples of the (b1) trimellitic acid ester include tri-n-octyl trimellitate, tri-(2-ethylhexyl) trimellitate, tri-n-nonyl trimellitate, tri-n-decyl trimellitate, tri-n-alkyl trimellitate (esters having two or more alkyl groups with different carbon numbers [however, the number of carbon atoms is 6 to 18] in the molecule), and mixtures thereof.
- the content of (b1) trimellitic acid ester in (b) plasticizer is preferably 90% by mass or more, more preferably 92% by mass or more, even more preferably 93% by mass or more, and can be 100% by mass or less, preferably 99% by mass or less, and more preferably 98% by mass or less. If the content of (b1) trimellitic acid ester in (b) plasticizer is within the above specified range, the powder fluidity of the vinyl chloride resin composition can be improved, and the tensile elongation of the vinyl chloride resin molded article formed can be improved.
- the content of the trimellitic acid ester (b1) in the vinyl chloride resin composition is preferably 70 parts by mass or more, more preferably 75 parts by mass or more, even more preferably 80 parts by mass or more, even more preferably 85 parts by mass or more, even more preferably 95 parts by mass or more, even more preferably 105 parts by mass or more, preferably 195 parts by mass or less, more preferably 175 parts by mass or less, even more preferably 155 parts by mass or less, even more preferably 135 parts by mass or less, and even more preferably 120 parts by mass or less, relative to 100 parts by mass of the vinyl chloride resin (a).
- the content of the trimellitic acid ester (b1) in the vinyl chloride resin composition is equal to or more than the lower limit, the powder flowability of the vinyl chloride resin composition can be improved and the tensile elongation of the vinyl chloride resin molded body formed can be improved.
- the content of the trimellitic acid ester (b1) in the vinyl chloride resin composition is equal to or less than the upper limit, the gloss change of the vinyl chloride resin molded body formed can be further suppressed, and the color change and surface stickiness of the vinyl chloride resin molded body can be suppressed.
- the (b2) polyester contained in the (b) 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 improving 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 polyester (b2).
- the viscosity of the (b2) polyester 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 (b2) polyester in (b) plasticizer is preferably 90% by mass or more, more preferably 92% by mass or more, even more preferably 93% by mass or more, and can be 100% by mass or less, preferably 99% by mass or less, and more preferably 98% by mass or less. If the content of (b2) polyester in (b) plasticizer is within the above-mentioned specified range, the powder fluidity of the vinyl chloride resin composition can be improved, and the tensile elongation of the vinyl chloride resin molded article formed can be improved.
- the content of the (b2) polyester in the vinyl chloride resin composition is preferably 70 parts by mass or more, more preferably 75 parts by mass or more, even more preferably 80 parts by mass or more, even more preferably 85 parts by mass or more, even more preferably 95 parts by mass or more, even more preferably 105 parts by mass or more, preferably 195 parts by mass or less, more preferably 175 parts by mass or less, even more preferably 155 parts by mass or less, even more preferably 135 parts by mass or less, and even more preferably 120 parts by mass or less, relative to 100 parts by mass of the (a) vinyl chloride resin.
- the content of the (b2) polyester in the vinyl chloride resin composition is equal to or more than the lower limit, the powder flowability of the vinyl chloride resin composition can be improved and the tensile elongation of the vinyl chloride resin molded body formed can be improved.
- the content of the (b2) polyester in the vinyl chloride resin composition is equal to or less than the upper limit, the gloss change of the vinyl chloride resin molded body formed can be further suppressed, and the color change and surface stickiness of the vinyl chloride resin molded body can be suppressed.
- the (b) plasticizer contained in the vinyl chloride resin composition may optionally contain a plasticizer other than the above-mentioned (b1) trimellitic acid ester and (b2) polyester (sometimes referred to as "(b3) other plasticizer").
- (b3) other plasticizers include primary plasticizers other than the above-mentioned (b1) trimellitic acid esters and (b2) polyesters, as well as secondary plasticizers, among the plasticizers described in WO 2016/098344.
- the so-called primary plasticizers are: Pyromellitic acid ester plasticizers such as tetra-n-hexyl pyromellitic acid, tetra-n-heptyl pyromellitic acid, tetra-n-octyl pyromellitic acid, tetra-(2-ethylhexyl) pyromellitic acid, tetra-n-nonyl pyromellitic acid, tetra-n-decyl pyromellitic acid, tetraisodecyl pyromellitic acid, tetra-n-undecyl pyromellitic acid, tetra-n-dodecyl pyromellitic acid, and tetra-n-alkyl pyromellitic acid esters (esters having two or more alkyl groups with different carbon numbers [wherein the number of carbon atoms is 6 to 12] in
- secondary plasticizers include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; chlorinated paraffin, glycol fatty acid esters such as triethylene glycol dicaprylate, butyl epoxy stearate, phenyl oleate, and methyl dihydroabietic acid.
- epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil
- chlorinated paraffin such as triethylene glycol dicaprylate, butyl epoxy stearate, phenyl oleate, and methyl dihydroabietic acid.
- glycol fatty acid esters such as triethylene glycol dicaprylate, butyl epoxy stearate, phenyl oleate, and methyl dihydroabietic acid.
- the content ratio of the above (b3) other plasticizer in the (b) plasticizer is not particularly limited, but can be, for example, 0% by mass or more, 1% by mass or more, 3% by mass or more, 10% by mass or less, 8% by mass or less, or 7% by mass or less.
- the content of the (b3) 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 (b3) 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 (a) vinyl chloride resin.
- the hindered amine light stabilizer is a component that can suppress a change in gloss of a vinyl chloride resin molded article formed using the vinyl chloride resin composition.
- the molecular weight of the (c) hindered amine light stabilizer must be 550 or more, preferably 575 or more, more preferably 600 or more, even more preferably 625 or more, still more preferably 650 or more, and even more preferably 675 or more; it must be 1500 or less, preferably 1200 or less, more preferably 1000 or less, even more preferably 900 or less, still more preferably 800 or less, and even more preferably 700 or less. If the molecular weight of the (c) hindered amine light stabilizer is equal to or greater than the lower limit, the change in gloss of the vinyl chloride resin molded body formed can be sufficiently suppressed.
- the molecular weight of the (c) hindered amine light stabilizer is equal to or greater than the lower limit, the stickiness of the surface of the vinyl chloride resin molded body formed can be suppressed, and the tensile elongation (particularly at low temperatures) of the vinyl chloride resin molded body can be improved.
- the molecular weight of the (c) hindered amine light stabilizer is equal to or less than the upper limit, the change in gloss of the vinyl chloride resin molded body formed can be sufficiently suppressed.
- the molecular weight of the (c) hindered amine light stabilizer is equal to or less than the upper limit, the tensile elongation (particularly at low temperatures) of the vinyl chloride resin molded body formed can be sufficiently high.
- the vinyl chloride resin composition of the present invention may further contain a hindered amine light stabilizer having a molecular weight outside the above-mentioned range (e.g., a molecular weight less than 550 or more than 1500) in addition to the (c) hindered amine light stabilizer having a molecular weight within the above-mentioned range.
- a hindered amine light stabilizer having a molecular weight outside the above-mentioned range e.g., a molecular weight less than 550 or more than 1500
- the vinyl chloride resin composition of the present invention does not contain a hindered amine light stabilizer having a molecular weight outside the above-mentioned range.
- the hindered amine light stabilizer is represented by the following formula (I): [In formula (I), R 1 is a hydrogen atom or an alkyl group, and "*" indicates a bond.]
- R 1 is a hydrogen atom or an alkyl group
- "*" indicates a bond.
- R 1 in the above formula (I) is preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, even more preferably an alkyl group having 1 to 5 carbon atoms, still more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group. That is, it is particularly preferable that the (c) hindered amine light stabilizer is an N-methyl hindered amine light stabilizer.
- the number of monovalent organic groups represented by the above formula (I) is preferably 1 or more, more preferably 2 or more, preferably 4 or less, more preferably 3 or less, and particularly preferably 2 per molecule of the hindered amine light stabilizer (c).
- the hindered amine light stabilizer (c) is a compound represented by the following formula (II): [In formula (II), R2 and R3 each independently represent a hydrogen atom or an alkyl group, and "*" represents a bond.]
- R2 and R3 each independently represent a hydrogen atom or an alkyl group, and "*" represents a bond.
- R2 and R3 in the above formula (II) is an alkyl group, and it is more preferable that both of R2 and R3 are alkyl groups.
- the number of carbon atoms in the alkyl group that can constitute R2 and R3 in the above formula (II) is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, still 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.
- R 2 and R 3 in the above formula (II) are both tert-butyl groups (also referred to as "1,1-dimethylethyl groups").
- the number of monovalent organic groups represented by the above formula (II) is preferably 1 or more, more preferably 3 or less, more preferably 2 or less, and particularly preferably 1, per molecule of the (c) hindered amine light stabilizer.
- the (c) hindered amine-based light stabilizer is preferably a compound represented by the following formula (III): It is particularly preferable to use a compound represented by the formula:
- hindered amine light stabilizer As the hindered amine light stabilizer, commercially available products can be used, for example, "Tinuvin 144" manufactured by BASF Japan Ltd. (compound name: butyl (3,5-di-tert-butyl-4-hydroxybenzyl) malonate bis (1,2,2,6,6-pentamethyl-4-piperidyl)).
- the hindered amine light stabilizer (c) is not particularly limited as long as it is a hindered amine light stabilizer whose molecular weight is within the above-mentioned specified range, and one type may be used alone, or two or more types may be used in combination in any ratio.
- the content of the (c) hindered amine light stabilizer in the vinyl chloride resin composition is not particularly limited, but is preferably 0.01 part by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 part by mass or more, still more preferably 0.15 parts by mass or more, even more preferably 0.2 parts by mass or more, and particularly preferably 0.25 parts by mass or more, preferably 20 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, still more preferably 1.5 parts by mass or less, even more preferably 1 part by mass or less, still more preferably 0.8 parts by mass or less, and particularly preferably 0.5 parts by mass or less, relative to 100 parts by mass of the (a) vinyl chloride resin.
- the content of the (c) hindered amine light stabilizer in the vinyl chloride resin composition is equal to or greater than the above lower limit, the change in gloss of the vinyl chloride resin molded body formed can be further suppressed.
- the content of the (c) hindered amine light stabilizer in the vinyl chloride resin composition is equal to or greater than the above lower limit, the change in color tone of the vinyl chloride resin molded body formed can be suppressed, and the tensile elongation (particularly at low temperatures) of the vinyl chloride resin molded body can be improved.
- the content of the (c) hindered amine light stabilizer in the vinyl chloride resin composition is equal to or less than the above upper limit, the change in gloss of the vinyl chloride resin molded body formed can be further suppressed.
- the content of the (c) hindered amine light stabilizer in the vinyl chloride resin composition is equal to or less than the above upper limit, the stickiness of the surface of the vinyl chloride resin molded body formed can be suppressed, and the tensile elongation (particularly at low temperatures) of the vinyl chloride resin molded body can be sufficiently high.
- the content of the (c) hindered amine light stabilizer in the vinyl chloride resin composition is not particularly limited, but is preferably 0.01 part by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 part by mass or more, still more preferably 0.15 parts by mass or more, even more preferably 0.2 parts by mass or more, and particularly preferably 0.22 parts by mass or more, preferably 20 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, still more preferably 1.5 parts by mass or less, even more preferably 1 part by mass or less, still more preferably 0.8 parts by mass or less, and particularly preferably 0.45 parts by mass or less, relative to 100 parts by mass of the (b) plasticizer.
- the content of the (c) hindered amine light stabilizer in the vinyl chloride resin composition is equal to or greater than the above lower limit, the change in gloss of the vinyl chloride resin molded body formed can be further suppressed.
- the content of the (c) hindered amine light stabilizer in the vinyl chloride resin composition is equal to or greater than the above lower limit, the change in color tone of the vinyl chloride resin molded body formed can be suppressed, and the tensile elongation (particularly at low temperatures) of the vinyl chloride resin molded body can be improved.
- the content of the (c) hindered amine light stabilizer in the vinyl chloride resin composition is equal to or less than the above upper limit, the change in gloss of the vinyl chloride resin molded body formed can be further suppressed.
- the content of the (c) hindered amine light stabilizer in the vinyl chloride resin composition is equal to or less than the above upper limit, the stickiness of the surface of the vinyl chloride resin molded body formed can be suppressed, and the tensile elongation (particularly at low temperatures) of the vinyl chloride resin molded body can be sufficiently high.
- the vinyl chloride resin composition of the present invention preferably further contains (d) cross-linked vinyl chloride resin in addition to the above-mentioned (a) vinyl chloride resin, (b) plasticizer, and (c) hindered amine light stabilizer.
- (d) cross-linked vinyl chloride resin can function as a dusting agent (powder flow improver). If the vinyl chloride resin composition further contains (d) cross-linked vinyl chloride resin, the powder flowability of the vinyl chloride resin composition can be improved. In addition, if the vinyl chloride resin composition further contains (d) cross-linked vinyl chloride resin, the stickiness of the surface of the vinyl chloride resin molded body formed can be further suppressed.
- the vinyl chloride resin composition of the present invention by using the above-mentioned (c) hindered amine light stabilizer and (d) crosslinked vinyl chloride resin in combination, the change in gloss of the vinyl chloride resin molded article to be formed can be further suppressed.
- Crosslinked vinyl chloride resin is a resin obtained by crosslinking vinyl chloride resin.
- Crosslinked vinyl chloride resin (d) can be prepared by crosslinking uncrosslinked vinyl chloride resin.
- uncrosslinked vinyl chloride resin that can be used as a material for preparing crosslinked vinyl chloride resin (d) include homopolymers and vinyl chloride copolymers composed of vinyl chloride monomer units, which are mentioned above as specific examples of vinyl chloride resin (a).
- the method for crosslinking vinyl chloride resin is not particularly limited, and may be, for example, a method of chemically crosslinking using a known crosslinking agent, or a method of crosslinking by irradiation with radiation such as an electron beam.
- the (d) cross-linked vinyl chloride resin a particulate cross-linked vinyl chloride resin is usually used.
- the (d) cross-linked vinyl chloride resin preferably contains cross-linked vinyl chloride resin fine particles, and more preferably consists of only cross-linked vinyl chloride resin fine particles.
- the (d) cross-linked vinyl chloride resin can contain one or more types of cross-linked vinyl chloride resin fine particles.
- the average particle diameter of the cross-linked vinyl chloride resin microparticles 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 diameter of the cross-linked vinyl chloride resin microparticles is equal to or greater than the above lower limit, the powder fluidity (particularly high-temperature powder fluidity) of the vinyl chloride resin composition can be further improved, for example, without excessively reducing the size as a dusting agent.
- the meltability of the vinyl chloride resin composition can be increased, and the surface smoothness of the vinyl chloride resin molded body formed can be improved.
- the content of the (d) cross-linked vinyl chloride resin in the vinyl chloride resin composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, even more preferably 4 parts by mass or more, even more preferably 6 parts by mass or more, even more preferably 7 parts by mass or more, preferably 30 parts by mass or less, more preferably 25 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, relative to 100 parts by mass of the (a) vinyl chloride resin.
- the content of the (d) cross-linked vinyl chloride resin in the vinyl chloride resin composition is equal to or more than the above lower limit, the gloss change of the vinyl chloride resin molded body formed can be further suppressed.
- the content of the (d) cross-linked vinyl chloride resin in the vinyl chloride resin composition is equal to or more than the above lower limit, the powder flowability of the vinyl chloride resin composition can be further improved and the stickiness of the surface of the vinyl chloride resin molded body formed can be further suppressed.
- the content of the (d) cross-linked vinyl chloride resin in the vinyl chloride resin composition is equal to or less than the above upper limit, the tensile elongation of the vinyl chloride resin molded body formed can be sufficiently high.
- the mass ratio of (d) cross-linked vinyl chloride resin to the vinyl chloride resin fine particles (cross-linked vinyl chloride resin/vinyl chloride resin fine particles) in the vinyl chloride resin composition is preferably 1/2 or more, more preferably 2/3 or more, even more preferably 1/1 or more, preferably 20/1 or less, more preferably 15/1 or less, and even more preferably 10/1 or less. If the mass ratio of (d) cross-linked vinyl chloride resin to vinyl chloride resin fine particles (cross-linked vinyl chloride resin/vinyl chloride resin fine particles) in the vinyl chloride resin composition is equal to or greater than the lower limit, the powder flowability of the vinyl chloride resin composition can be further improved and the stickiness of the surface of the vinyl chloride resin molded body formed can be further suppressed.
- the mass ratio of (d) cross-linked vinyl chloride resin to vinyl chloride resin fine particles (cross-linked vinyl chloride resin/vinyl chloride resin fine particles) in the vinyl chloride resin composition is equal to or less than the upper limit, the tensile elongation of the vinyl chloride resin molded body formed can be sufficiently high.
- the content of the (d) cross-linked vinyl chloride resin in the vinyl chloride resin composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, even more preferably 4 parts by mass or more, even more preferably 5 parts by mass or more, even more preferably 6 parts by mass or more, preferably 30 parts by mass or less, more preferably 25 parts by mass or less, even more preferably 18 parts by mass or less, even more preferably 13 parts by mass or less, and even more preferably 10 parts by mass or less, relative to 100 parts by mass of the (b) plasticizer.
- the content of the (d) cross-linked vinyl chloride resin in the vinyl chloride resin composition is equal to or more than the above lower limit, the gloss change of the vinyl chloride resin molded body formed can be further suppressed.
- the content of the (d) cross-linked vinyl chloride resin in the vinyl chloride resin composition is equal to or more than the above lower limit, the powder flowability of the vinyl chloride resin composition can be further improved and the stickiness of the surface of the vinyl chloride resin molded body formed can be further suppressed.
- the content of the (d) cross-linked vinyl chloride resin in the vinyl chloride resin composition is equal to or less than the above upper limit, the tensile elongation of the vinyl chloride resin molded body formed can be sufficiently high.
- 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 for powder molding of the present invention may further contain an amide compound as an additive other than those described above.
- an amide compound in the vinyl chloride resin composition By further containing an amide compound in the vinyl chloride resin composition, the demoldability of the vinyl chloride resin molded article formed can be improved.
- the amide compound is a compound having an amide group, and is, for example, represented by the following formula (1): R4 ( NR5COR6 ) n (1)
- R4 is an n-valent hydrocarbon group
- R5 is a monovalent hydrocarbon group or hydrogen
- R6 is a monovalent hydrocarbon group
- the n R5s may be the same or different
- the n R6s 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 -NR5COR6 .
- 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.
- R4 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 in R 4 may be, for example, 1 or more, 2 or more, 8 or less, or 6 or less.
- R4 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.
- R5 in the above formula (1) is a monovalent hydrocarbon group or hydrogen, and n R5s may be the same or different from each other.
- the monovalent hydrocarbon group of R5 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 R 5 has, for example, 1 or more and 2 or less carbon atoms. Examples of R5 include hydrogen, a methyl group, and an ethyl group.
- n R5 may be hydrogen, or all of n R5 may be hydrogen.
- R6 in the above formula (1) is a monovalent hydrocarbon group, and n R6 may be the same or different from each other.
- a saturated hydrocarbon group of R6 and an unsaturated hydrocarbon group of R6 may be mixed in one molecule, or only an unsaturated hydrocarbon group of R6 may be present, or only a saturated hydrocarbon group of R6 may be present.
- the saturated hydrocarbon group of R6 is, for example, a monovalent chain saturated aliphatic hydrocarbon group.
- the number of carbon atoms in the saturated hydrocarbon group of R6 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 R6 is, for example, a monovalent chain unsaturated aliphatic hydrocarbon group.
- the number of carbon atoms in the unsaturated hydrocarbon group of R6 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 6 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) plasticizer.
- the vinyl chloride resin composition of the present invention does not have to contain an amide compound.
- the proportion of tetrahydrofuran insoluble matter in the vinyl chloride resin composition is preferably 8.5% by mass or more, more preferably 9% by mass or more, even more preferably 9.5% by mass or more, and even more preferably 9.7% by mass or more, and is preferably 20% by mass or less, more preferably 18% by mass or less, even more preferably 16% by mass or less, and even more preferably 15% by mass or less. If the proportion of the tetrahydrofuran insoluble matter in the vinyl chloride resin composition is equal to or greater than the lower limit, the powder flowability of the vinyl chloride resin composition can be improved.
- the proportion of the tetrahydrofuran insoluble matter in the vinyl chloride resin composition is equal to or greater than the lower limit, the stickiness of the surface of the vinyl chloride resin molded article formed can be suppressed.
- the proportion of the tetrahydrofuran insoluble matter in the vinyl chloride resin composition is equal to or less than the upper limit, the tensile elongation of the vinyl chloride resin molded article formed can be sufficiently high.
- the proportion of the tetrahydrofuran insoluble matter in the vinyl chloride resin composition can be adjusted by changing the amount of each component (e.g., (a) vinyl chloride resin, (b) plasticizer, (c) hindered amine light stabilizer, and (d) cross-linked vinyl chloride resin) used when preparing the vinyl chloride resin composition.
- the "proportion of tetrahydrofuran insoluble matter" of a vinyl chloride resin composition can be measured using the vinyl chloride resin composition or a vinyl chloride resin molded article formed using the vinyl chloride resin composition as a measurement sample, according to the method described in the Examples of the present specification.
- the ratio of the proportion of tetrahydrofuran insoluble matter in the vinyl chloride resin composition to the content of the plasticizer is preferably 0.17 or more, more preferably 0.175 or more, even more preferably 0.185 or more, still more preferably 0.19 or more, even more preferably 0.195 or more, and is preferably 0.50 or less, more preferably 0.45 or less, even more preferably 0.40 or less, still more preferably 0.35 or less, and even more preferably 0.32 or less.
- the powder flowability of the vinyl chloride resin composition can be improved. If the ratio of the tetrahydrofuran insoluble content of the vinyl chloride resin composition to the content of the plasticizer (tetrahydrofuran insoluble content/plasticizer content) is equal to or greater than the lower limit, the stickiness of the surface of the vinyl chloride resin molded body formed can be suppressed.
- the ratio of the tetrahydrofuran insoluble content of the vinyl chloride resin composition to the content of the plasticizer is equal to or less than the upper limit, the tensile elongation of the vinyl chloride resin molded body formed can be sufficiently high.
- 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) plasticizer, (c) hindered amine light stabilizer, (d) cross-linked vinyl chloride resin further blended as necessary, and various additives is not particularly limited, and for example, a method of mixing components other than the dusting agent (including vinyl chloride resin fine particles and the optional (d) cross-linked vinyl chloride resin) by dry blending, and then adding and mixing the dusting agent can be mentioned.
- 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 obtained vinyl chloride resin composition can be suitably used for powder molding, and can be 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 vinyl chloride resin composition described above by any method. Since the vinyl chloride resin molded article of the present invention is formed using the vinyl chloride resin composition described above, it usually contains at least (a) vinyl chloride resin, (b) plasticizer, and (c) hindered amine light stabilizer, and optionally further contains (d) crosslinked vinyl chloride resin and various additives. And, since the vinyl chloride resin molded article of the present invention is formed using the vinyl chloride resin composition described above, gloss change is suppressed and it has excellent appearance stability. Therefore, a laminate formed by backing a polyurethane foam molding with the vinyl chloride resin molding 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 suitable for use as an automobile interior part, particularly as an automobile interior material 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
- the present invention will be specifically described below based on examples, but the present invention is not limited to these examples.
- “%” and “parts” expressing amounts are based on mass unless otherwise specified.
- the "content of plasticizer” in a vinyl chloride resin composition usually corresponds to the ratio of the amount of plasticizer used to the total amount of components used in preparing the vinyl chloride resin composition.
- the powder flowability and the proportion of tetrahydrofuran insoluble matter of the vinyl chloride resin composition, as well as the tensile elongation, surface stickiness, color change and gloss change of the vinyl chloride resin molded sheet were measured and evaluated by the following methods.
- ⁇ Ratio of tetrahydrofuran insoluble matter About 0.3 g of a vinyl chloride resin molded body (vinyl chloride resin molded sheet) as a measurement sample was cut out, finely chopped, and placed in a 100 mL glass bottle, and the mass of the sample was determined by precisely weighing. 90 mL of tetrahydrofuran (THF) was added to the measured sample after weighing, and the measured sample was dissolved by leaving it to stand for 24 hours.
- THF tetrahydrofuran
- One piece of glass fiber filter paper "GF-75 ⁇ 110 mm" manufactured by Advantec Co., Ltd. was taken out and precisely weighed to determine the mass of the filter paper before the test.
- the stickiness of the surface of the polyvinyl chloride resin molded article 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.
- the smaller the ⁇ E value the more suppressed the color tone change of the vinyl chloride resin molded article is, meaning that the color tone stability is excellent.
- the gloss value was measured by measuring the 60° reflectance with a gloss meter (GM-268A Gloss Meter manufactured by Konica Minolta Japan Co., Ltd.) and determining ⁇ gloss, which is the difference (amount of change) between the gloss value before irradiation and the gloss value after irradiation.
- ⁇ gloss is the difference (amount of change) between the gloss value before irradiation and the gloss value after irradiation.
- the smaller the ⁇ gloss value the more suppressed the change in gloss of the vinyl chloride resin molded article is, meaning that the appearance stability is excellent.
- Example 1 Preparation of vinyl chloride resin composition> Of the ingredients shown in Table 1, the ingredients except for the plasticizer (adipic acid-based polyester and epoxidized soybean oil) and the dusting agent (vinyl chloride resin fine particles) were mixed in a Henschel mixer. 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, which are vinyl chloride resin, and the mixture becomes smooth). After that, when the dried-up mixture was cooled to a temperature of 70°C or less, the dusting agent (vinyl chloride resin fine particles) was added to prepare a vinyl chloride resin composition.
- the plasticizer adipic acid-based polyester and epoxidized soybean oil
- the dusting agent vinyl chloride resin fine particles
- the resulting vinyl chloride resin composition was evaluated for powder flowability, and the results are shown in Table 1.
- ⁇ 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.
- PO-EO prop
- 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 tensile elongation (after heating) of the vinyl chloride resin molded sheet in the laminate was evaluated. The results are shown in Table 1.
- Examples 2 to 5 Comparative Examples 1 to 6
- a vinyl chloride resin composition, a vinyl chloride resin molded article, and a laminate 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 1 to 3.
- the results are shown in Tables 1 to 3.
- the crosslinked vinyl chloride resin fine particles as a dusting agent were added simultaneously with the vinyl chloride resin fine particles as a dusting agent.
- Tables 1 to 3 show that the use of the vinyl chloride resin compositions of Examples 1 to 5, which contain vinyl chloride resin, a specified amount or more of plasticizer, and a hindered amine light stabilizer whose molecular weight is within a specified range, suppresses changes in gloss of the vinyl chloride resin molded body formed, compared to the use of the vinyl chloride resin compositions of Comparative Examples 1 to 6, which do not contain a hindered amine light stabilizer whose molecular weight is within the specified range.
- a vinyl chloride resin composition capable of forming a vinyl chloride resin molded article in which change in gloss is suppressed. Furthermore, according to the present invention, it is possible to provide a vinyl chloride resin molded article in which changes in gloss are suppressed. Furthermore, according to the present invention, it is possible to provide a laminate comprising the vinyl chloride resin molded article.
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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は、当該塩化ビニル樹脂組成物を用いて形成された塩化ビニル樹脂成形体の光沢変化を抑制する点において、改善の余地があった。
また、本発明は、光沢変化が抑制された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。
このように、塩化ビニル樹脂と、所定量以上の可塑剤と、分子量が所定の範囲内であるヒンダードアミン系光安定剤とを含む塩化ビニル樹脂組成物によれば、光沢変化が抑制された塩化ビニル樹脂成形体を形成可能である。
ヒンダードアミン系光安定剤の含有量が上記所定の範囲であれば、形成される塩化ビニル樹脂成形体の光沢変化を更に抑制し得ると共に、当該塩化ビニル樹脂成形体の光の照射等による色調の変化(以下、「色調変化」と略記することがある。)および表面のべた付きを抑制することができる。また、ヒンダードアミン系光安定剤の含有量が上記所定の範囲であれば、形成される塩化ビニル樹脂成形体の引張伸び(特に低温下での引張伸び)を向上させることができる。
で表される1価の有機基を有することが好ましい。
ヒンダードアミン系光安定剤が上記式(I)で表される有機基を有していれば、形成される塩化ビニル樹脂成形体の光沢変化を更に抑制することができる。
上記式(I)中のR1がメチル基であれば、形成される塩化ビニル樹脂成形体の光沢変化を一層抑制することができる。
で表される1価の有機基を有することが好ましい。
ヒンダードアミン系光安定剤が上記式(II)で表される有機基を有していれば、形成される塩化ビニル樹脂成形体の光沢変化を更に抑制することができる。
上記式(II)中のR2およびR3がいずれもtert-ブチル基であれば、形成される塩化ビニル樹脂成形体の光沢変化を一層抑制することができる。
ヒンダードアミン系光安定剤として上記式(III)で表される化合物を用いれば、形成される塩化ビニル樹脂成形体の光沢変化を更に抑制することができる。
可塑剤としてトリメリット酸エステルおよびポリエステルの少なくとも一方を用いれば、形成される塩化ビニル樹脂成形体の引張特性(引張伸びおよび引張応力)を向上させることができる。
架橋塩化ビニル樹脂を更に用いれば、塩化ビニル樹脂組成物の粉体流動性を向上させると共に、形成される塩化ビニル樹脂成形体の表面のべた付きを抑制することができる。また、架橋塩化ビニル樹脂を更に用いれば、形成される塩化ビニル樹脂成形体の光沢変化を更に抑制することができる。
塩化ビニル樹脂組成物を粉体成形に用いれば、例えば、自動車インスツルメントパネル用表皮などの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が容易に得られる。
塩化ビニル樹脂組成物をパウダースラッシュ成形に用いれば、例えば、自動車インスツルメントパネル用表皮などの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がより容易に得られる。
このように、上述した本発明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は、光沢変化が抑制されていて、外観安定性に優れている。
本発明の塩化ビニル樹脂成形体は、光沢変化が抑制され、外観安定性に優れた自動車インスツルメントパネルの表皮として好適に用いることができる。
発泡ポリウレタン成形体および上述した本発明の塩化ビニル樹脂成形体を有する積層体は、光沢変化が抑制され、外観安定性に優れた塩化ビニル樹脂成形体部分を備えている。
このように、本発明の積層体を自動車インスツルメントパネルに用いれば、製造される自動車インスツルメンツパネルの表皮の光沢変化を抑制し、外観安定性を向上させることができる。
また、本発明によれば、光沢変化が抑制された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、(b)可塑剤と、(c)分子量が所定の範囲内であるヒンダードアミン系光安定剤(以下、「(c)ヒンダードアミン系光安定剤」と略記する場合がある。)と、を含むことを特徴とする。
また、本発明の塩化ビニル樹脂組成物は、(d)架橋塩化ビニル樹脂を更に含んでいてもよい。
さらに、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、(b)可塑剤、(c)ヒンダードアミン系光安定剤、および(d)架橋塩化ビニル樹脂以外の添加剤を更に含んでいてもよい。
そして、本発明の塩化ビニル樹脂組成物によれば、光沢変化が抑制された塩化ビニル樹脂成形体を形成することができる。
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、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。
なお、本発明において、(a)塩化ビニル樹脂は、架橋されていない塩化ビニル樹脂であるものとする。即ち、(a)塩化ビニル樹脂には、後述する(d)架橋塩化ビニル樹脂は含まれないものとする。
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、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に確保しつつ、例えば、引張特性、特には引張伸びを良好にすることできる。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。一方、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。
なお、本発明において「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、塩化ビニル樹脂粒子の平均粒子径は、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を向上させることができる。一方、塩化ビニル樹脂粒子の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を向上させると共に、形成される塩化ビニル樹脂成形体の表面平滑性を向上させることができる。
なお、本発明において、「平均粒子径」は、JIS Z8825に準拠し、レーザー回折法により体積平均粒子径として測定することができる。
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、80質量%以上であることが好ましく、90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、99質量%以下であることが好ましい。(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、形成される塩化ビニル樹脂成形体の物理的強度を十分確保しつつ、当該塩化ビニル樹脂成形体の引張伸びを向上させることができる。一方、(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を向上させることができる。
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を向上させると共に、形成される塩化ビニル樹脂成形体の引張伸びを向上させることができる。一方、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を高めて、形成される塩化ビニル樹脂成形体の表面平滑性を向上させることができる。
また、塩化ビニル樹脂微粒子の平均粒子径は、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向上させることができる。一方、塩化ビニル樹脂微粒子の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を高めて、形成される塩化ビニル樹脂成形体の表面平滑性を向上させることができる。
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、1質量%以上であることが好ましく、20質量%以下であることが好ましく、10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を向上させることができる。一方、(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、形成される塩化ビニル樹脂成形体の物理的強度を高めることができる。
(b)可塑剤は、特に限定されないが、(b1)トリメリット酸エステル、および(b2)ポリエステルの少なくとも一方を含有することが好ましい。本発明の塩化ビニル樹脂組成物に使用する(b)可塑剤として、(b1)トリメリット酸エステル、および(b2)ポリエステルの少なくとも一方を用いれば、引張特性(引張伸びおよび引張応力)に優れる塩化ビニル樹脂成形体を形成可能である。また、(b)可塑剤として(b2)ポリエステルを用いれば、形成される塩化ビニル樹脂成形体に発泡ポリウレタン成形体を裏打ちしてなる積層体を作製した場合に、高温下において塩化ビニル樹脂成形体に含まれる可塑剤が発泡ポリウレタン成形体に移行して生じる塩化ビニル樹脂成形体の熱収縮を抑制することができる。即ち、(b)可塑剤として(b2)ポリエステルを用いれば、形成される塩化ビニル樹脂成形体の耐熱収縮性を向上させることができる。
(b)可塑剤は、(b1)トリメリット酸エステルおよび(b2)ポリエステルの双方を含有していてもよいし、(b1)トリメリット酸エステルおよび(b2)ポリエステルのうち一方を含有し、他方を含有しなくてもよい。
なお、(b)可塑剤は、(b1)トリメリット酸エステル、および(b2)ポリエステル以外の可塑剤(以下、「(b3)その他の可塑剤」と称することがある。)を含んでいてもよいものとする。
なお、本発明において、塩化ビニル樹脂組成物中の「可塑剤の含有割合」は、塩化ビニル樹脂組成物または当該塩化ビニル樹脂組成物を用いて形成された塩化ビニル樹脂成形体を測定試料とし、ソックスレー抽出法を用いて測定することができる。
(b)可塑剤中に含まれる(b1)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(b1)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(b1)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。
(b)可塑剤に含まれる(b2)ポリエステルとしては、特に限定されることはなく、例えば、アジピン酸由来の構造単位を含有するポリエステル(アジピン酸系ポリエステル)、セバシン酸由来の構造単位を含有するポリエステル(セバシン酸系ポリエステル)、およびフタル酸由来の構造単位を含有するポリエステル(フタル酸系ポリエステル)などのポリエステルを用いることができる。なお、これらのポリエステルは、1種を単独で用いてもよいし、2種以上を任意の比率で混合して用いてもよい。
中でも、塩化ビニル樹脂成形体の耐熱収縮性を更に高める観点から、(b2)ポリエステルとしては、アジピン酸系ポリエステル(アジピン酸由来の構造単位を含有するポリエステル)を用いることが好ましい。
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に含まれる(b)可塑剤は、任意で、上述した(b1)トリメリット酸エステル、および(b2)ポリエステル以外の可塑剤(「(b3)その他の可塑剤」と称することがある。)を含んでいてもよい。
ピロメリット酸テトラ-n-ヘキシル、ピロメリット酸テトラ-n-ヘプチル、ピロメリット酸テトラ-n-オクチル、ピロメリット酸テトラ-(2-エチルヘキシル)、ピロメリット酸テトラ-n-ノニル、ピロメリット酸テトラ-n-デシル、ピロメリット酸テトライソデシル、ピロメリット酸テトラ-n-ウンデシル、ピロメリット酸テトラ-n-ドデシル、ピロメリット酸テトラ-n-アルキルエステル(炭素数が異なるアルキル基〔但し、炭素数は6~12である。〕を分子内に2種以上有するエステル)等のピロメリット酸エステル可塑剤;
ジメチルフタレート、ジエチルフタレート、ジブチルフタレート、ジ-(2-エチルヘキシル)フタレート、ジ-n-オクチルフタレート、ジイソブチルフタレート、ジヘプチルフタレート、ジフェニルフタレート、ジイソデシルフタレート、ジトリデシルフタレート、ジウンデシルフタレート、ジベンジルフタレート、ブチルベンジルフタレート、ジノニルフタレート、ジシクロヘキシルフタレート等のフタル酸誘導体;
ジメチルイソフタレート、ジ-(2-エチルヘキシル)イソフタレート、ジイソオクチルイソフタレート等のイソフタル酸誘導体;
ジ-(2-エチルヘキシル)テトラヒドロフタレート、ジ-n-オクチルテトラヒドロフタレート、ジイソデシルテトラヒドロフタレート等のテトラヒドロフタル酸誘導体;
ジ-n-ブチルアジペート、ジ(2-エチルヘキシル)アジペート、ジイソデシルアジペート、ジイソノニルアジペート等のアジピン酸誘導体;
ジ-(2-エチルヘキシル)アゼレート、ジイソオクチルアゼレート、ジ-n-ヘキシルアゼレート等のアゼライン酸誘導体;
ジ-n-ブチルセバケート、ジ-(2-エチルヘキシル)セバケート、ジイソデシルセバケート、ジ-(2-ブチルオクチル)セバケート等のセバシン酸誘導体;
ジ-n-ブチルマレエート、ジメチルマレエート、ジエチルマレエート、ジ-(2-エチルヘキシル)マレエート等のマレイン酸誘導体;
ジ-n-ブチルフマレート、ジ-(2-エチルヘキシル)フマレート等のフマル酸誘導体;
トリエチルシトレート、トリ-n-ブチルシトレート、アセチルトリエチルシトレート、アセチルトリ-(2-エチルヘキシル)シトレート等のクエン酸誘導体;
モノメチルイタコネート、モノブチルイタコネート、ジメチルイタコネート、ジエチルイタコネート、ジブチルイタコネート、ジ-(2-エチルヘキシル)イタコネート等のイタコン酸誘導体;
ブチルオレエート、グリセリルモノオレエート、ジエチレングリコールモノオレエート等のオレイン酸誘導体;
メチルアセチルリシノレート、ブチルアセチルリシノレート、グリセリルモノリシノレート、ジエチレングリコールモノリシノレート等のリシノール酸誘導体;
n-ブチルステアレート、ジエチレングリコールジステアレート等のステアリン酸誘導体;
ジエチレングリコールモノラウレート、ジエチレングリコールジペラルゴネート、ペンタエリスリトール脂肪酸エステル等のその他の脂肪酸誘導体;
トリエチルホスフェート、トリブチルホスフェート、トリ-(2-エチルヘキシル)ホスフェート、トリブトキシエチルホスフェート、トリフェニルホスフェート、クレジルジフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、トリス(クロロエチル)ホスフェート等のリン酸誘導体;
ジエチレングリコールジベンゾエート、ジプロピレングリコールジベンゾエート、トリエチレングリコールジベンゾエート、トリエチレングリコールジ-(2-エチルブチレート)、トリエチレングリコールジ-(2-エチルヘキソエート)、ジブチルメチレンビスチオグリコレート等のグリコール誘導体;
グリセロールモノアセテート、グリセロールトリアセテート、グリセロールトリブチレート等のグリセリン誘導体;
エポキシヘキサヒドロフタル酸ジイソデシル、エポキシトリグリセライド、エポキシ化オレイン酸オクチル、エポキシ化オレイン酸デシル等のエポキシ誘導体;
等が挙げられる。
また、いわゆる二次可塑剤としては、エポキシ化大豆油、エポキシ化亜麻仁油等のエポキシ化植物油;塩素化パラフィン、トリエチレングリコールジカプリレート等のグリコールの脂肪酸エステル、ブチルエポキシステアレート、フェニルオレエート、ジヒドロアビエチン酸メチル等が挙げられる。
中でも、形成される塩化ビニル樹脂成形体の引張特性(引張伸びおよび引張応力)を更に高める観点から、エポキシ化植物油を用いることが好ましく、エポキシ化大豆油を用いることがより好ましい。
そして、(b3)その他の可塑剤としてエポキシ化大豆油などのエポキシ化植物油を用いる場合、形成される塩化ビニル樹脂成形体の引張特性(引張伸びおよび引張応力)を一層向上させる観点から、(b3)その他の可塑剤としてのエポキシ化植物油の含有量は、上記(a)塩化ビニル樹脂100質量部に対して、2質量部以上であることが好ましく、3質量部以上であることがより好ましく、4質量部以上であることが更に好ましく、10質量部以下であることが好ましく、7質量部以下であることがより好ましい。
(c)ヒンダードアミン系光安定剤は、塩化ビニル樹脂組成物を用いて形成される塩化ビニル樹脂成形体の光沢変化を抑制し得る成分である。
ここで、(c)ヒンダードアミン系光安定剤の分子量は、550以上であることが必要であり、575以上であることが好ましく、600以上であることがより好ましく、625以上であることが更に好ましく、650以上であることが一層好ましく、675以上であることがより一層好ましく、1500以下であることが必要であり、1200以下であることが好ましく、1000以下であることがより好ましく、900以下であることが更に好ましく、800以下であることが一層好ましく、700以下であることがより一層好ましい。
(c)ヒンダードアミン系光安定剤の分子量が上記下限以上であれば、形成される塩化ビニル樹脂成形体の光沢変化を十分に抑制することができる。また、(c)ヒンダードアミン系光安定剤の分子量が上記下限以上であれば、形成される塩化ビニル樹脂成形体の表面のべた付きを抑制し得ると共に、当該塩化ビニル樹脂成形体の引張伸び(特に低温下での引張伸び)を向上させることができる。一方、(c)ヒンダードアミン系光安定剤の分子量が上記上限以下であれば、形成される塩化ビニル樹脂成形体の光沢変化を十分に抑制することができる。また、(c)ヒンダードアミン系光安定剤の分子量が上記上限以下であれば、形成される塩化ビニル樹脂成形体の引張伸び(特に低温下での引張伸び)を十分に高く確保することができる。
(c)ヒンダードアミン系光安定剤は、下記式(I):
で表される1価の有機基を有することが好ましい。(c)ヒンダードアミン系光安定剤が上記(I)で表される1価の有機基を有していれば、形成される塩化ビニル樹脂成形体の光沢変化を更に抑制することができる。
で表される1価の有機基を有することが好ましい。(c)ヒンダードアミン系光安定剤が上記(II)で表される1価の有機基を有していれば、形成される塩化ビニル樹脂成形体の光沢変化を更に抑制することができる。
上記式(II)中のR2およびR3を構成し得るアルキル基の炭素数は、1以上であることが好ましく、2以上であることがより好ましく、3以上であることが更に好ましく、4以上であることが一層好ましく、10以下であることが好ましく、8以下であることがより好ましく、6以下であることが更に好ましく、5以下であることが一層好ましく、4であることが特に好ましい。R2およびR3を構成し得るアルキル基の炭素数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光沢変化をより一層抑制することができる。
そして、形成される塩化ビニル樹脂成形体の光沢変化を更に一層抑制する観点から、上記式(II)中のR2およびR3はいずれもtert-ブチル基(「1,1-ジメチルエチル基」とも称する。)であることが特に好ましい。
塩化ビニル樹脂組成物中における(c)ヒンダードアミン系光安定剤の含有量は、特に限定されないが、上記(a)塩化ビニル樹脂100質量部に対して、0.01質量部以上であることが好ましく、0.05質量部以上であることがより好ましく、0.1質量部以上であることが更に好ましく、0.15質量部以上であることが一層好ましく、0.2質量部以上であることがより一層好ましく、0.25質量部以上であることが特に好ましく、20質量部以下であることが好ましく、5質量部以下であることがより好ましく、3質量部以下であることが更に好ましく、1.5質量部以下であることが一層好ましく、1質量部以下であることがより一層好ましく、0.8質量部以下であることが更に一層好ましく、0.5質量部以下であることが特に好ましい。
塩化ビニル樹脂組成物中における(c)ヒンダードアミン系光安定剤の含有量が上記下限以上であれば、形成される塩化ビニル樹脂成形体の光沢変化を更に抑制することができる。また、塩化ビニル樹脂組成物中における(c)ヒンダードアミン系光安定剤の含有量が上記下限以上であれば、形成される塩化ビニル樹脂成形体の色調変化を抑制し得ると共に、当該塩化ビニル樹脂成形体の引張伸び(特に低温下での引張伸び)を向上させることができる。一方、塩化ビニル樹脂組成物中における(c)ヒンダードアミン系光安定剤の含有量が上記上限以下であれば、形成される塩化ビニル樹脂成形体の光沢変化を更に抑制することができる。また、塩化ビニル樹脂組成物中における(c)ヒンダードアミン系光安定剤の含有量が上記上限以下であれば、形成される塩化ビニル樹脂成形体の表面のべた付きを抑制し得ると共に、当該塩化ビニル樹脂成形体の引張伸び(特に低温下での引張伸び)を十分に高く確保することができる。
塩化ビニル樹脂組成物中における(c)ヒンダードアミン系光安定剤の含有量が上記下限以上であれば、形成される塩化ビニル樹脂成形体の光沢変化を更に抑制することができる。また、塩化ビニル樹脂組成物中における(c)ヒンダードアミン系光安定剤の含有量が上記下限以上であれば、形成される塩化ビニル樹脂成形体の色調変化を抑制し得ると共に、当該塩化ビニル樹脂成形体の引張伸び(特に低温下での引張伸び)を向上させることができる。一方、塩化ビニル樹脂組成物中における(c)ヒンダードアミン系光安定剤の含有量が上記上限以下であれば、形成される塩化ビニル樹脂成形体の光沢変化を更に抑制することができる。また、塩化ビニル樹脂組成物中における(c)ヒンダードアミン系光安定剤の含有量が上記上限以下であれば、形成される塩化ビニル樹脂成形体の表面のべた付きを抑制し得ると共に、当該塩化ビニル樹脂成形体の引張伸び(特に低温下での引張伸び)を十分に高く確保することができる。
本発明の塩化ビニル樹脂組成物は、上述した(a)塩化ビニル樹脂、(b)可塑剤、および(c)ヒンダードアミン系光安定剤に加えて、(d)架橋塩化ビニル樹脂を更に含むことが好ましい。塩化ビニル樹脂組成物において、(d)架橋塩化ビニル樹脂は、ダスティング剤(粉体流動性改良剤)として機能し得る。そして、塩化ビニル樹脂組成物が(d)架橋塩化ビニル樹脂を更に含めば、塩化ビニル樹脂組成物の粉体流動性を向上させることができる。また、塩化ビニル樹脂組成物が(d)架橋塩化ビニル樹脂を更に含めば、形成される塩化ビニル樹脂成形体の表面のべた付きを更に抑制することができる。
さらに、本発明の塩化ビニル樹脂組成物においては、上記(c)ヒンダードアミン系光安定剤と、(d)架橋塩化ビニル樹脂とを併用することにより、形成される塩化ビニル樹脂成形体の光沢変化を更に抑制することができる。
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。
また、本発明の粉体成形用塩化ビニル樹脂組成物は、上記以外の添加剤として、アミド化合物を含んでいてもよい。塩化ビニル樹脂組成物がアミド化合物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脱型性を向上させることができる。
アミド化合物は、アミド基を有する化合物であり、例えば、下記式(1):
R4(NR5COR6)n (1)
〔式(1)中、nは2以上6以下の整数であり、R4はn価の炭化水素基であり、R5は1価の炭化水素基または水素であり、R6は1価の炭化水素基であり、n個のR5は互いに同一でも異なっていてもよく、n個のR6は互いに同一でも異なっていてもよい〕で示される。即ち、上記アミド化合物は、例えば、炭化水素のn個の水素が-NR5COR6で示されるアミド基で置換された構造を有している。
また、R4が有する炭素数は、例えば、1以上であってもよいし、2以上であってもよいし、8以下であってもよいし、6以下であってもよい。
また、R5の炭化水素基が有する炭素数は、例えば、1以上2以下である。
R5としては、例えば、水素、メチル基、エチル基が挙げられる。
また、R6の飽和炭化水素基が有する炭素数は、それぞれ11以上であってもよいし、13以上であってもよいし、15以上であってもよいし、23以下であってもよいし、21以下であってもよいし、19以下であってもよいし、17であってもよい。
R3の飽和炭化水素基としては、例えば、CH3(CH2)10-、CH3(CH2)12-、CH3(CH2)14-、CH3(CH2)16-、CH3(CH2)18-、CH3(CH2)20-、CH3(CH2)22-、等が挙げられる。
また、R6の不飽和炭化水素基が有する炭素数は、それぞれ11以上であってもよいし、13以上であってもよいし、15以上であってもよいし、23以下であってもよいし、21以下であってもよいし、19以下であってもよいし、17であってもよい。
塩化ビニル樹脂組成物のテトラヒドロフラン不溶分の割合は、8.5質量%以上であることが好ましく、9質量%以上であることがより好ましく、9.5質量%以上であることが更に好ましく、9.7質量%以上であることが一層好ましく、20質量%以下であることが好ましく、18質量以下であることがより好ましく、16質量%以下であることが更に好ましく、15質量%以下であることが一層好ましい。
塩化ビニル樹脂組成物のテトラヒドロフラン不溶分の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を向上させることができる。また、塩化ビニル樹脂組成物のテトラヒドロフラン不溶分の割合が上記下限以上であれば、形成される塩化ビニル樹脂成形体の表面のべた付きを抑制することができる。一方、塩化ビニル樹脂組成物のテトラヒドロフラン不溶分の割合が上記上限以下であれば、形成される塩化ビニル樹脂成形体の引張伸びを十分に高く確保することができる。
なお、塩化ビニル樹脂組成物のテトラヒドロフラン不溶分の割合は、塩化ビニル樹脂組成物を調製する際に使用する各成分(例えば、(a)塩化ビニル樹脂、(b)可塑剤、(c)ヒンダードアミン系光安定剤、および(d)架橋塩化ビニル樹脂など)の使用量を変更することにより調整することができる。
本発明において、塩化ビニル樹脂組成物の「テトラヒドロフラン不溶分の割合」は、塩化ビニル樹脂組成物または当該塩化ビニル樹脂組成物を用いて形成された塩化ビニル樹脂成形体を測定試料として用い、本明細書の実施例に記載の方法に従って測定することができる。
塩化ビニル樹脂組成物のテトラヒドロフラン不溶分の割合と、可塑剤の含有割合との比(テトラヒドロフラン不溶分の割合/可塑剤の含有割合)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を向上させることができる。また、塩化ビニル樹脂組成物のテトラヒドロフラン不溶分の割合と、可塑剤の含有割合との比(テトラヒドロフラン不溶分の割合/可塑剤の含有割合)が上記下限以上であれば、形成される塩化ビニル樹脂成形体の表面のべた付きを抑制することができる。一方、塩化ビニル樹脂組成物のテトラヒドロフラン不溶分の割合と、可塑剤の含有割合との比(テトラヒドロフラン不溶分の割合/可塑剤の含有割合)が上記上限以下であれば、形成される塩化ビニル樹脂成形体の引張伸びを十分に高く確保することができる。
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、上記(a)塩化ビニル樹脂と、(b)可塑剤と、(c)ヒンダードアミン系光安定剤と、必要に応じて更に配合される(d)架橋塩化ビニル樹脂および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および任意成分の(d)架橋塩化ビニル樹脂を含む)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更に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。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、(b)可塑剤と、(c)ヒンダードアミン系光安定剤とを含み、任意で、(d)架橋塩化ビニル樹脂および各種添加剤を更に含んでいる。そして、本発明の塩化ビニル樹脂成形体は、上述した本発明の塩化ビニル樹脂組成物を用いて形成されているため、光沢変化が抑制されていて、外観安定性に優れている。
したがって、本発明の塩化ビニル樹脂成形体に発泡ポリウレタン成形体を裏打ちして形成された積層体は、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。
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、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。
なお、塩化ビニル樹脂組成物中の「可塑剤の含有割合」は、別に断らない限り、通常は、塩化ビニル樹脂組成物の調製に使用した成分の総量に対する可塑剤の使用量の割合と一致する。
そして、塩化ビニル樹脂組成物の粉体流動性およびテトラヒドロフラン不溶分の割合、並びに、塩化ビニル樹脂成形シートの引張伸び、表面のべた付き性、色調変化および光沢変化は、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を用いて、JIS-K-6720に記載のかさ比重測定装置を使用し、100mLの容器に入った重量よりかさ密度を測定した。その際に得られた100mLの容器に入った塩化ビニル樹脂組成物の粉体をかさ比重測定装置に戻し、直ちにダンパーを開けてからすべての粉体が流動するまでの時間を測定し、落下秒数を得た。なお、1分間待っても流れ切らない場合は「流動せず」とした。上記操作はいずれも常温(23℃)下にて行った。なお、落下秒数が小さいほど、塩化ビニル樹脂組成物は常温状態の粉体流動性に優れていることを示す。
測定試料としての塩化ビニル樹脂成形体(塩化ビニル樹脂成形シート)を0.3g程度切り取って、細かく刻んで100mLのガラス瓶に入れて、精密に計量して試料の質量を求めた。計量後の測定試料に対してテトラヒドロフラン(THF)を90mL添加し、24時間静置して測定試料を溶解させた。アドバンテック社製ガラス繊維濾紙「GF-75 φ110mm」を1枚取り出し、精密に計量し、試験前の濾紙の質量を求めた。当該濾紙を使用して、測定試料を溶解したTHF溶液の減圧濾過を行い、濾過後の濾紙を40℃のオーブンで3時間乾燥した。乾燥後のろ紙の質量を精密に計量して試験後の濾紙の質量を求めた。そして、下記の式により、塩化ビニル樹脂組成物のTHF不溶分の割合を求めた。
THF不溶分の割合={(試験後の濾紙の質量-試験前の濾紙の質量)/試料の質量}×100(%)
[初期(未加熱状態)]
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。なお、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引張伸びに優れていることを示す。
[加熱(熱老化試験)後]
実施例および比較例で得られた、塩化ビニル樹脂成形シートに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400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(未加熱状態)の場合と同様にして、120℃400時間加熱後の塩化ビニル樹脂成形シートの低温(-10℃)下における引張破断伸び(%)を測定した。
塩化ビニル樹脂成形体の表面のべた付き性は、以下の通り、動摩擦係数を測定することにより評価した。
具体的には、風合いテスター(トリニティラボ社製、製品名「TL201Ts」)を用いて、温度23℃、相対湿度50%の測定環境下において、荷重:50g、速度:10mm/秒、試験範囲:50mm、計測範囲:試験範囲の前後10mmを除いた30mm、の条件にて、触覚接触子を、積層体を形成する前の塩化ビニル樹脂成形シートに接触させることにより、当該シート表面の動摩擦係数を測定した。動摩擦係数の値が小さいほど、塩化ビニル樹脂成形体の表面のべた付きが抑制されていることを示す。
発泡ポリウレタン成形体が裏打ちされた積層体を7cm×14cmの寸法に切り出して
試験片とした。
スーパーキセノンウェザーメーター(スガ試験機製「SX75」)を使用して、ブラックパネル温度83℃、照射強度150w/m2の条件で150MJ照射し、照射前後のΔE値とグロス値の変化量(Δグロス)とを求めた。
ΔEは、色差計(コニカミノルタジャパン社製「分光測色計CM-700D」)を用いてCIE表色系(L*,a*,b*)で計測し、照射前後での明度(L*)の差ΔL*、色度(a*,b*)の差Δa*およびΔb*から、式:ΔE=〔(ΔL*)2+(Δa*)2+(Δb*)2〕1/2によりΔEを算出した。ΔEの値が小さいほど、塩化ビニル樹脂成形体の色調変化が抑制されていて、色調安定性に優れることを意味する。
グロス値は、60°反射率をグロスメータ(コニカミノルタジャパン社製「グロスメータGM-268A」)で測定し、照射前のグロス値と照射後のグロス値との差(変化量)であるΔグロスを求めた。Δグロスの値が小さいほど、塩化ビニル樹脂成形体の光沢変化が抑制されていて、外観安定性に優れることを意味する。
<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(アジピン酸系ポリエステル、およびエポキシ化大豆油)と、ダスティング剤(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(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、粉体流動性を評価した。結果を表1に示す。
<塩化ビニル樹脂成形体の形成>
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、145mm×175mm×1mmの塩化ビニル樹脂成形シートを金型から脱型した。
得られた塩化ビニル樹脂成形体を用いて、テトラヒドロフラン不溶分の割合、引張伸び(初期)、表面のべた付き性、色調変化および光沢変化を評価した。結果を表1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を100mm×100mmに切り取り、切り取られた塩化ビニル樹脂成形シート2枚を、200mm×300mm×10mmの金型中に重ならないように敷き、シボ付き面を下にして置いた。
別途、プロピレングリコールのプロピレンオキサイド・エチレンオキサイド(PO・EO)ブロック付加物(水酸基価28、末端EO単位の含有量=10%、内部EO単位の含有量4%)50質量部、グリセリンのPO・EOブロック付加物(水酸基価21、末端EO単位の含有量=14%)50質量部、水2.5質量部、トリエチレンジアミンのエチレングリコ-ル溶液(東ソー(株)製、商品名:「TEDA-L33」)0.2質量部、トリエタノールアミン1.2質量部、トリエチルアミン0.5質量部及び整泡剤(信越化学工業(株)製、商品名:「F-122」)0.5質量部からなるポリオール混合物と、ポリメチレンポリフェニレンポリイソシアネート(ポリメリックMDI)とを、インデックスが98になる比率で混合して混合液を調製した。そして、調製した混合液を、上述の通り金型中に敷かれた塩化ビニル樹脂成形シート2枚の上にそれぞれ注いだ。その後、348mm×255mm×10mmのアルミ板で金型に蓋をすることで金型を密閉した。密閉してから5分後、1mm厚の塩化ビニル樹脂成形シートに発泡ポリウレタン成形体が裏打ちされてなる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成形シートについて、引張伸び(加熱後)を評価した。結果を表1に示す。
配合組成を表1~3に示す通りに変更したこと以外は、実施例1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、各種の評価を行った。結果を表1~3に示す。なお、塩化ビニル樹脂組成物の調製の際、ダスティング剤である架橋塩化ビニル樹脂微粒子は、同じくダスティング剤である塩化ビニル樹脂微粒子と同時に添加した。
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、平均粒子径:1.8μm)
3)花王社製、製品名「トリメックスN-08」(トリメリット酸トリ-n-アルキル(n-アルキル基としてn-オクチル基およびn-デシル基が混在))
4)ADEKA社製、製品名「アデカサイザー HPN-3130」(アジピン酸系ポリエステル、粘度:4,000mPa・s)
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)堺化学工業社、製品名「SAKAI SZ2000」
10)ADEKA社製、製品名「アデカスタブ LS-12」
11)日本化成社製、製品名「スリパックス(登録商標)O」
12)BASFジャパン社製、製品名「Tinuvin 765」(下記式(IV)で表されるヒンダードアミン系光安定剤、化合物名:セバシン酸ビス(1,2,2,6,6-ペンタメチル-4-ピペリジル)、分子量:509)
16)大日精化社製、製品名「DA P 4720 ブラック」
また、本発明によれば、光沢変化が抑制された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 (15)
- 塩化ビニル樹脂と、可塑剤と、分子量が550以上1500以下であるヒンダードアミン系光安定剤とを含み、
前記可塑剤の含有量が、前記塩化ビニル樹脂100質量部に対して、75質量部以上である、塩化ビニル樹脂組成物。 - 前記ヒンダードアミン系光安定剤の含有量が、前記塩化ビニル樹脂100質量部に対して、0.01質量部以上20質量部以下である、請求項1に記載の塩化ビニル樹脂組成物。
- 前記R1がメチル基である、請求項3に記載の塩化ビニル樹脂組成物。
- 前記R2および前記R3がいずれもtert-ブチル基である、請求項5に記載の塩化ビニル樹脂組成物。
- 前記可塑剤が、トリメリット酸エステルおよびポリエステルの少なくとも一方を含有する、請求項1に記載の塩化ビニル樹脂組成物。
- 架橋塩化ビニル樹脂を更に含む、請求項1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に記載の塩化ビニル樹脂組成物。
- 請求項1~11のいず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12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14に記載の積層体。
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| JP2024549341A JPWO2024070985A1 (ja) | 2022-09-29 | 2023-09-22 | |
| CN202380051396.XA CN119403876A (zh) | 2022-09-29 | 2023-09-22 | 氯乙烯树脂组合物、氯乙烯树脂成型体以及层叠体 |
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| WO2016143343A1 (ja) * | 2015-03-10 | 2016-09-15 | 日本ゼオン株式会社 | 粉体成形用塩化ビニル樹脂組成物、塩化ビニル樹脂成形体及び積層体 |
| WO2021166722A1 (ja) * | 2020-02-17 | 2021-08-26 | 日本ゼオン株式会社 | 粉体成形用塩化ビニル樹脂組成物、塩化ビニル樹脂成形体および積層体 |
| JP2021134335A (ja) * | 2020-02-28 | 2021-09-13 | 日本ゼオン株式会社 | 粉体成形用塩化ビニル樹脂組成物、粉体成形用塩化ビニル樹脂成形体および積層体 |
| JP2022086823A (ja) * | 2020-11-30 | 2022-06-09 | 日本ゼオン株式会社 | 粉体成形用塩化ビニル樹脂組成物、塩化ビニル樹脂成形体および積層体 |
-
2023
- 2023-09-22 EP EP23872210.2A patent/EP4596621A1/en active Pending
- 2023-09-22 WO PCT/JP2023/034595 patent/WO2024070985A1/ja not_active Ceased
- 2023-09-22 CN CN202380051396.XA patent/CN119403876A/zh active Pending
- 2023-09-22 JP JP2024549341A patent/JPWO2024070985A1/ja active Pending
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2025
- 2025-03-24 MX MX2025003466A patent/MX2025003466A/es unknown
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| JPH0372550A (ja) * | 1989-05-23 | 1991-03-27 | Sumitomo Chem Co Ltd | 塩化ビニル樹脂組成物 |
| JPH05140396A (ja) * | 1991-11-22 | 1993-06-08 | Asahi Denka Kogyo Kk | 可塑剤組成物 |
| JP2003181959A (ja) * | 2001-12-13 | 2003-07-03 | Hiraoka & Co Ltd | 遮水シート用被覆保護材及びその施工方法 |
| JP2015189969A (ja) * | 2014-03-31 | 2015-11-02 | アサヒゴム株式会社 | シーリング材組成物 |
| WO2016098344A1 (ja) | 2014-12-17 | 2016-06-23 | 日本ゼオン株式会社 | 塩化ビニル樹脂組成物及びその製造方法、塩化ビニル樹脂成形体及びその製造方法、並びに、積層体 |
| WO2016143343A1 (ja) * | 2015-03-10 | 2016-09-15 | 日本ゼオン株式会社 | 粉体成形用塩化ビニル樹脂組成物、塩化ビニル樹脂成形体及び積層体 |
| WO2021166722A1 (ja) * | 2020-02-17 | 2021-08-26 | 日本ゼオン株式会社 | 粉体成形用塩化ビニル樹脂組成物、塩化ビニル樹脂成形体および積層体 |
| JP2021134335A (ja) * | 2020-02-28 | 2021-09-13 | 日本ゼオン株式会社 | 粉体成形用塩化ビニル樹脂組成物、粉体成形用塩化ビニル樹脂成形体および積層体 |
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| EP4596621A1 (en) | 2025-08-06 |
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