Vinyl chloride resin composition, vinyl chloride resin molded article, and laminate

Abstract

Provided is a vinyl chloride resin composition capable of forming a vinyl chloride resin molded article having excellent low-temperature tensile elongation. This vinyl chloride resin composition contains a vinyl chloride resin, a polyester plasticizer having a number average molecular weight of less than 8000, and a polyester resin having a number average molecular weight of 8000 or more. In addition, the vinyl chloride resin composition is preferably used for powder molding.

Description

Technical Field

[0001] The present invention relates to a vinyl chloride resin composition, a vinyl chloride resin molded body and a laminate. Background Art

[0002] Generally, vinyl chloride resin is used in various applications because of its excellent properties such as cold resistance, heat resistance, and oil resistance.

[0003] Specifically, for example, in the formation of automobile interior parts such as automobile instrument panels and door interiors, automobile interior materials such as skins formed of vinyl chloride resin molded bodies and laminates formed by lining the skins formed of vinyl chloride resin molded bodies with foamed bodies such as foamed polyurethane are used.

[0004] Furthermore, a vinyl chloride resin molded body constituting the surface of an automobile interior component such as an automobile instrument panel can be produced by molding a vinyl chloride resin composition containing a vinyl chloride resin, a plasticizer and an additive using a powder molding method such as powder slush molding (for example, see Patent Document 1).

[0005] Specifically, for example, in 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 stabilizer, a zeolite stabilizer, and β-diketones.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: Japanese Patent Application Publication No. 2012-197394. Summary of the invention

[0009] Problem that the invention aims to solve

[0010] However, there is room for improvement in the tensile elongation at low temperatures (hereinafter sometimes referred to as "low-temperature tensile elongation") of vinyl chloride resin molded articles formed using the above-mentioned conventional vinyl chloride resin compositions containing polyester plasticizers.

[0011] Therefore, an object of the present invention is to provide a vinyl chloride resin composition capable of forming a vinyl chloride resin molded body having excellent low-temperature tensile elongation.

[0012] Another object of the present invention is to provide a vinyl chloride resin molded article having excellent low-temperature tensile elongation.

[0013] Furthermore, an object of the present invention is to provide a laminate having the vinyl chloride resin molded article.

[0014] Solutions for solving problems

[0015] The present inventors have conducted intensive research with the purpose of solving the above problems. Then, the present inventors found that if a vinyl chloride resin composition containing a polyester plasticizer having a number average molecular weight less than a specified value and a polyester resin having a number average molecular weight greater than a specified value is used, a vinyl chloride resin molded body having excellent low-temperature tensile elongation can be formed, thereby completing the present invention.

[0016] That is, the object of the present invention is to advantageously solve the above-mentioned problems. The present invention is [1] a vinyl chloride resin composition comprising a vinyl chloride resin, a polyester plasticizer having a number average molecular weight of less than 8000, and a polyester resin having a number average molecular weight of 8000 or more.

[0017] Thus, according to the vinyl chloride resin composition comprising a vinyl chloride resin, a polyester plasticizer having a number average molecular weight less than the above specified value, and a polyester resin having a number average molecular weight greater than the above specified value, a vinyl chloride resin molded body having excellent low-temperature tensile elongation can be formed.

[0018] In the present invention, the "number average molecular weight" of the polyester plasticizer and the polyester resin can be measured using the method described in the Examples of the present specification.

[0019] [2] In the vinyl chloride resin composition of [1] above, the content of the polyester resin is preferably 0.1 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the vinyl chloride resin.

[0020] If the content of the polyester resin is within the above-specified range, the low-temperature tensile elongation of the formed vinyl chloride resin molded body can be further improved while suppressing the stickiness of the surface of the vinyl chloride resin molded body. In addition, if the content of the polyester resin is within the above-specified range, the powder fluidity of the vinyl chloride resin composition can be improved.

[0021] [3] In the vinyl chloride resin composition of [1] or [2] above, the polyester resin preferably contains a structural unit derived from a dicarboxylic acid and an alkylene oxide structural unit.

[0022] [4] In the vinyl chloride resin composition of [3] above, it is preferred that the dicarboxylic acid contains an aromatic dicarboxylic acid.

[0023] When 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 formed vinyl chloride resin molded article can be further increased.

[0024] [5] In the vinyl chloride resin composition of [4] above, the aromatic dicarboxylic acid preferably contains at least one of terephthalic acid and isophthalic acid.

[0025] When 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 increased.

[0026] [6] In the vinyl chloride resin composition according to any one of [3] to [5], 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.

[0027] When the polyester resin contains the above-specified alkylene oxide structural unit, the low-temperature tensile elongation of the resulting vinyl chloride resin molded article can be further improved.

[0028] [7] In the vinyl chloride resin composition according to any one of [3] to [6], the polyester resin preferably has a polyalkylene oxide region in which the alkylene oxide structural units are continuously arranged.

[0029] When the polyester resin has a polyalkylene oxide region, the low-temperature tensile elongation of the resulting vinyl chloride resin molded article can be further increased.

[0030] [8] In the vinyl chloride resin composition of the above-mentioned [7], preferably, when all the structural units in the above-mentioned polyester resin are 100 mol %, the proportion of the above-mentioned alkylene oxide structural units contained in the above-mentioned polyalkylene oxide region is 5 mol % or more and 80 mol % or less.

[0031] When the ratio of the alkylene oxide structural unit contained in the polyalkylene oxide region is within the above-specified range, the low-temperature tensile elongation of the formed vinyl chloride resin molded article can be further improved while suppressing the stickiness of the surface of the vinyl chloride resin molded article.

[0032] In the present invention, the ratio of each structural unit when all structural units in the polyester resin are taken as 100 mol % (ie, the composition of the polyester resin) can be measured by the method described in Examples of the present specification.

[0033] [9] In the vinyl chloride resin composition according to any one of [1] to [8], 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.

[0034] If the content of the polyester plasticizer is within the above-specified range, the low-temperature tensile elongation of the formed vinyl chloride resin molded body can be further improved. In addition, if the content of the polyester plasticizer is within the above-specified range, the heat shrinkage resistance of the formed vinyl chloride resin molded body can be improved while ensuring that the powder fluidity of the vinyl chloride resin composition is sufficiently high.

[0035]

[10] The vinyl chloride resin composition according to any one of [1] to [9] is preferably used for powder molding.

[0036] When the vinyl chloride resin composition is used for powder molding, a vinyl chloride resin molded body which can be suitably used as, for example, an automobile interior material such as an automobile instrument panel skin can be easily obtained.

[0037]

[11] The vinyl chloride resin composition according to any one of [1] to

[10] is preferably used for powder slush molding.

[0038] When the vinyl chloride resin composition is used for powder slush molding, a vinyl chloride resin molded body which can be preferably used as an automobile interior material such as a surface skin for automobile instrument panels can be more easily obtained.

[0039] In addition, the object of the present invention is to advantageously solve the above-mentioned problems. The present invention is

[12] a vinyl chloride resin molded product obtained by molding the vinyl chloride resin composition of any one of the above [1] to

[11] .

[0040] As described above, a vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition has excellent low-temperature tensile elongation and can therefore be suitably used as an automobile interior material.

[0041]

[13] The above-mentioned

[12] vinyl chloride resin molded article is preferably used for the surface skin of automobile instrument panels.

[0042] When the vinyl chloride resin molded article of the present invention is used for the surface skin of an automobile instrument panel, an automobile instrument panel having a surface skin excellent in low-temperature tensile elongation can be produced.

[0043] Then, the object of the present invention is to advantageously solve the above-mentioned problems. The present invention is

[14] a laminate comprising a foamed polyurethane molded product and the vinyl chloride resin molded product of

[12] or

[13] above.

[0044] The laminate comprising the foamed polyurethane molded article and the above-mentioned vinyl chloride resin molded article has a vinyl chloride resin molded article portion having excellent low-temperature tensile elongation.

[0045]

[15] The laminate of the above-mentioned

[14] is preferably used for an automobile instrument panel.

[0046] As described above, when the laminate of the present invention is used for an automobile instrument panel, the low-temperature tensile elongation of the surface skin of the manufactured automobile instrument panel can be improved.

[0047] Effects of the Invention

[0048] According to the present invention, there can be provided a vinyl chloride resin composition capable of forming a vinyl chloride resin molded body having excellent low-temperature tensile elongation.

[0049] Furthermore, according to the present invention, a vinyl chloride resin molded product having excellent low-temperature tensile elongation can be provided.

[0050] Furthermore, according to the present invention, a laminated body having the vinyl chloride resin molded body can be provided. DETAILED DESCRIPTION

[0051] Hereinafter, embodiments of the present invention will be described in detail.

[0052] The vinyl chloride resin composition of the present invention can be used, for example, to form the vinyl chloride resin molded body of the present invention. Furthermore, the vinyl chloride resin molded body formed using the vinyl chloride resin composition of the present invention can be suitably used as an automobile interior material such as the surface skin of automobile interior parts such as automobile instrument panels and door interiors.

[0053] The vinyl chloride resin molded article of the present invention can be used, for example, to form a laminate of the present invention. Furthermore, the laminate formed using the vinyl chloride resin molded article of the present invention can be suitably used as an automobile interior material used in the manufacture of automobile interior parts such as automobile instrument panels and door interiors.

[0054] (Vinyl chloride resin composition)

[0055] 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 less than a specified value (hereinafter, sometimes simply referred to as "(b) polyester plasticizer"), and (c) a polyester resin having a number average molecular weight greater than a specified value (hereinafter, sometimes simply referred to as "(c) polyester resin").

[0056] Furthermore, the vinyl chloride resin composition of the present invention may further optionally contain a plasticizer other than the above-mentioned (b) polyester plasticizer (hereinafter, sometimes referred to as "(d) other plasticizer").

[0057] Furthermore, the vinyl chloride resin composition of the present invention may further optionally contain additives other than the above-mentioned (a) vinyl chloride resin, (b) polyester plasticizer, (c) polyester resin and (d) other plasticizer.

[0058] Furthermore, the vinyl chloride resin composition of the present invention can form a vinyl chloride resin molded article having excellent low-temperature tensile elongation.

[0059] Therefore, by using the vinyl chloride resin composition of the present invention, it is possible to obtain a vinyl chloride resin molded product which is excellent in anti-fogging property and is suitable as an automobile interior material, such as an automobile instrument panel skin and a door trim skin.

[0060] Furthermore, for example, from the viewpoint that a vinyl chloride resin molded body which can be favorably used as an automobile interior material can be easily obtained 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 for powder slush molding.

[0061] <(a) Vinyl chloride resin>

[0062] As the (a) vinyl chloride resin, a granular vinyl chloride resin is generally used. Moreover, as the (a) vinyl chloride resin, for example, one or two or more vinyl chloride resin particles can be contained, and one or two or more vinyl chloride resin microparticles can be contained arbitrarily. Among them, the (a) vinyl chloride resin preferably contains at least vinyl chloride resin particles, and more preferably contains vinyl chloride resin particles and vinyl chloride resin microparticles.

[0063] The (a) vinyl chloride resin can be produced by any conventionally known production method such as suspension polymerization, emulsion polymerization, solution polymerization, or bulk polymerization.

[0064] In the present specification, "resin particles" refer to particles having a particle size of 30 μm or more, and "resin fine particles" refer to particles having a particle size of less than 30 μm.

[0065] In addition, examples of the (a) vinyl chloride resin include, in addition to a homopolymer composed of a vinyl chloride monomer unit, a vinyl chloride resin preferably containing 50% by mass or more, more preferably 70% by mass or more of a vinyl chloride monomer unit.

[0066] Vinyl chloride copolymer. As specific examples of monomers (comonomers) that can constitute vinyl chloride copolymers and can be copolymerized with vinyl chloride monomers, for example, monomers described in International Publication No. 2016 / 098344 can be used. In addition, these components can be used alone or in combination of two or more in any ratio.

[0067] <<Vinyl chloride resin granules>>

[0068] In a vinyl chloride resin composition, vinyl chloride resin particles generally function as a base resin (substrate). In addition, the vinyl chloride resin particles are preferably produced by a suspension polymerization method.

[0069] [Average degree of polymerization]

[0070] Moreover, 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, preferably 5000 or less, more preferably 3000 or less, and further preferably 2800 or less. If the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is above the above lower limit, it is possible to improve, for example, tensile properties, particularly tensile elongation, while ensuring that the physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition is sufficiently high. Moreover, the vinyl chloride resin molded body with good tensile elongation can be suitably used as, for example, an automobile interior material such as the surface of an automobile instrument panel that has excellent ductility and does not scatter fragments but cracks as designed when the airbag is inflated and deployed. On the other hand, if the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is below the above upper limit, the solubility of the vinyl chloride resin composition can be improved.

[0071] The average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles may be 1400 or more, 1500 or more, or 1600 or more, or may be 1600 or less, 1500 or less, or 1400 or less.

[0072] In the present invention, the "average degree of polymerization" can be measured in accordance with JIS K6720-2.

[0073] [Average particle size]

[0074] In addition, the average particle size of the vinyl chloride resin particles is usually 30 μm or more, preferably 50 μm or more, more preferably 100 μm or more, preferably 500 μm or less, more preferably 200 μm or less. If the average particle size of the vinyl chloride resin particles is above the above lower limit, the powder fluidity 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 below the above upper limit, the solubility 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 improved.

[0075] In the present invention, the "average particle size" can be measured as a volume average particle size by a laser diffraction method in accordance with JIS Z8825.

[0076] [Content ratio]

[0077] Moreover, 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, can be set to 100% by mass, preferably 95% by mass or less, more preferably 90% by mass or less. If the content of the vinyl chloride resin particles in the (a) vinyl chloride resin is above the above lower limit, the tensile elongation can be improved while ensuring that the physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition is sufficiently high. On the other hand, if the content of the vinyl chloride resin particles in the (a) vinyl chloride resin is below the above upper limit, the powder fluidity of the vinyl chloride resin composition can be improved.

[0078] <<Vinyl chloride resin particles>>

[0079] In a vinyl chloride resin composition, vinyl chloride resin fine particles generally function as a release agent (powder flowability improver). In addition, the vinyl chloride resin fine particles are preferably produced by an emulsion polymerization method.

[0080] [Average degree of polymerization]

[0081] Furthermore, the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin microparticles is preferably 500 or more, more preferably 700 or more, preferably 2600 or less, more preferably 2400 or less. If the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin microparticles as the release agent is above the above 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 using the vinyl chloride resin composition can be improved. On the other hand, if the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is below the above upper limit, the solubility 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 improved.

[0082] [Average particle size]

[0083] In addition, the average particle size of the vinyl chloride resin microparticles is usually less than 30 μm, preferably less than 10 μm, more preferably less than 5 μm, preferably more than 0.1 μm, more preferably more than 1 μm. If the average particle size of the vinyl chloride resin microparticles is above the above lower limit, the powder fluidity of the vinyl chloride resin composition can be improved without excessively reducing the size, for example, as a release agent. On the other hand, if the average particle size of the vinyl chloride resin microparticles is below the above upper limit, the solubility of the vinyl chloride resin composition can be improved, and the surface smoothness of the formed vinyl chloride resin molded body can be improved.

[0084] [Content ratio]

[0085] Furthermore, the content of the vinyl chloride resin microparticles in the (a) vinyl chloride resin may be 0% by mass, preferably 5% by mass or more, more preferably 10% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less. If the content of the vinyl chloride resin microparticles in the (a) vinyl chloride resin is above the above lower limit, the powder fluidity of the vinyl chloride resin composition can be improved. On the other hand, if the content of the vinyl chloride resin microparticles in the (a) vinyl chloride resin is below the above upper limit, the physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition can be improved.

[0086] <(b) Polyester plasticizer>

[0087] The (b) polyester plasticizer is a component that can impart flexibility to a vinyl chloride resin molded body formed using a vinyl chloride resin composition and improve the tensile properties (particularly low-temperature tensile elongation) of the vinyl chloride resin molded body. In addition, when a laminated body is prepared in which a foamed polyurethane molded body is lined on a vinyl chloride resin molded body formed using a vinyl chloride resin composition, the (b) polyester plasticizer is unlikely to transfer from the vinyl chloride resin molded body to the foamed polyurethane molded body even at high temperatures, thereby improving the heat shrinkage resistance of the vinyl chloride resin molded body.

[0088] The polyester plasticizer (b) is not particularly limited, and for example, 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) can be used. In addition, these polyesters can be used alone or in combination of two or more at any ratio.

[0089] From the viewpoint of further improving the heat shrinkage resistance of the vinyl chloride resin molded article, it is particularly preferable to use adipic acid-based polyester (polyester containing a structural unit derived from adipic acid) as the (b) polyester plasticizer.

[0090] <<Number average molecular weight (Mn)>>

[0091] (b) The number average molecular weight (Mn) of the polyester plasticizer needs to be less than 8,000, preferably 7,000 or less, more preferably 6,000 or less, further preferably 5,000 or less, and further preferably 4,000 or less.

[0092] If the number average molecular weight (Mn) of the (b) polyester plasticizer is less than 8000, the low temperature tensile elongation of the formed vinyl chloride resin molded body can be sufficiently improved. In addition, if the number average molecular weight of the (b) polyester plasticizer is below the above upper limit, the low temperature tensile elongation of the formed vinyl chloride resin molded body can be further improved.

[0093] The lower limit of the number average molecular weight (Mn) of the (b) polyester plasticizer is not particularly limited, but is, for example, preferably 500 or more, more preferably 1000 or more, and even more preferably 2000 or more.

[0094] <<Viscosity>>

[0095] (b) The viscosity of the 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 further preferably 4000 mPa·s or less.

[0096] In addition, "viscosity" can be measured at a temperature of 23°C in accordance with JIS Z8803.

[0097] <<Content>>

[0098] 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, further preferably 70 parts by mass or more, further preferably 80 parts by mass or more, and further preferably 85 parts by mass or more, and is preferably 200 parts by mass or less, more preferably 180 parts by mass or less, further preferably 150 parts by mass or less, further preferably 130 parts by mass or less, and further preferably 110 parts by mass or less. If the content of the (b) polyester plasticizer in the vinyl chloride resin composition is above the above lower limit, the low-temperature tensile elongation and heat shrinkage resistance of the formed vinyl chloride resin molded article can be further improved. On the other hand, if the content of the (b) polyester plasticizer in the vinyl chloride resin composition is below the above upper limit, the powder fluidity of the vinyl chloride resin composition can be ensured to be sufficiently high.

[0099] 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, relative to 100 parts by mass of the above-mentioned (a) vinyl chloride resin. Furthermore, the content may be less than 100 parts by mass, less than 95 parts by mass, or less than 90 parts by mass.

[0100] <(c) Polyester resin>

[0101] (c) The 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.

[0102] <<Number average molecular weight (Mn)>>

[0103] Here, the number average molecular weight (Mn) of the (c) polyester resin needs to be 8,000 or more, preferably 10,000 or more, more preferably 15,000 or more, further preferably 20,000 or more, further preferably 25,000 or more, further preferably 30,000 or more, particularly preferably 33,000 or more, preferably 100,000 or less, more preferably 80,000 or less, further preferably 60,000 or less, further preferably 50,000 or less, further preferably 43,000 or less.

[0104] If the number average molecular weight (Mn) of the (c) polyester resin is 8,000 or more, the low-temperature tensile elongation of the formed vinyl chloride resin molded body can be sufficiently improved. In addition, if the number average molecular weight (Mn) of the (c) polyester resin is above the above lower limit, the powder fluidity of the vinyl chloride resin composition can be improved, and the low-temperature tensile elongation of the formed vinyl chloride resin molded body can be further improved, and the stickiness of the surface of the vinyl chloride resin molded body can be suppressed. On the other hand, if the number average molecular weight (Mn) of the (c) polyester resin is below the above upper limit, the low-temperature tensile elongation of the formed vinyl chloride resin molded body can be further improved, and the stickiness of the surface of the vinyl chloride resin molded body can be suppressed.

[0105] The number average molecular weight (Mn) of the (c) polyester resin may be 35,000 or more, or 38,000 or more, or 38,000 or less, 35,000 or less, 33,000 or less, or 30,000 or less.

[0106] <<Weight average molecular weight (Mw)>>

[0107] (c) The weight average molecular weight (Mw) of the polyester resin is preferably 9,000 or more, preferably 12,000 or more, more preferably 18,000 or more, further preferably 20,000 or more, further preferably 40,000 or more, further preferably 50,000 or more, particularly preferably 60,000 or more, preferably 150,000 or less, more preferably 120,000 or less, further preferably 100,000 or less, further preferably 90,000 or less, further preferably 80,000 or less.

[0108] When the weight average molecular weight (Mw) of the (c) polyester resin is not less than the above lower limit, the powder flowability of the vinyl chloride resin composition can be improved, and the low-temperature tensile elongation of the formed vinyl chloride resin molded body can be further improved, and the stickiness of the surface of the vinyl chloride resin molded body can be suppressed. On the other hand, when the weight average molecular weight (Mw) of the (c) polyester resin is not more than the above upper limit, the low-temperature tensile elongation of the formed vinyl chloride resin molded body can be further improved, and the stickiness of the surface of the vinyl chloride resin molded body can be suppressed.

[0109] The weight average molecular weight (Mw) of the (c) polyester resin may be 63,000 or more, or 65,000 or more, or 65,000 or less, 63,000 or less, 60,000 or less, or 50,000 or less.

[0110] In the present invention, "(c) the weight average molecular weight of the polyester resin" can be measured using the method described in Examples of the present specification.

[0111] <<Composition>>

[0112] The (c) polyester resin is not particularly limited, but preferably contains a structural unit derived from a dicarboxylic acid and an alkylene oxide structural unit.

[0113] The (c) polyester resin can be obtained by, for example, subjecting a dicarboxylic acid and a diol to an esterification reaction and polycondensation.

[0114] [Structural unit derived from dicarboxylic acid]

[0115] (c) The structural unit derived from dicarboxylic acid in the polyester resin is a repeating unit composed of a structure formed by dicarboxylic acid.

[0116] Examples of the dicarboxylic acid that can form the dicarboxylic acid-derived structural unit (repeating unit) in the (c) polyester resin include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid; and aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and 1,4-cyclohexane dicarboxylic acid.

[0117] These may be used alone or in combination of two or more at any ratio.

[0118] Moreover, from the viewpoint of further improving the low-temperature tensile elongation of the formed vinyl chloride resin molded body, it is preferred to use at least an aromatic dicarboxylic acid as the dicarboxylic acid, it is more preferred to use at least one of terephthalic acid and isophthalic acid, it is further preferred to use at least isophthalic acid, and it is further preferred to use terephthalic acid and isophthalic acid in combination.

[0119] [Alkylene oxide structural unit]

[0120] The alkylene oxide structural unit is a repeating unit consisting only of an alkylene oxide structure represented by the formula (I).

[0121] [Chemical formula 1]

[0122]

[0123] [wherein p is an integer greater than or equal to 1].

[0124] Here, from the viewpoint of further improving the low-temperature tensile elongation of the formed vinyl chloride resin molded body, p in the above formula (I) is preferably 2 or more, more preferably 3 or more, further preferably 4 or more, preferably 10 or less, more preferably 8 or less, further preferably 6 or less, further preferably 5 or less, and particularly preferably 4.

[0125] Moreover, from the viewpoint of further improving the low-temperature tensile elongation of the formed vinyl chloride resin molded product, the alkylene oxide structural unit contained in the (c) polyester resin is preferably an ethylene oxide structural unit, a tetramethylene oxide and a 2,2-dimethylpropylene oxide structural unit, more preferably a tetramethylene oxide and a 2,2-dimethylpropylene oxide structural unit, and still more preferably a tetramethylene oxide.

[0126] The alkylene oxide structural unit in the (c) polyester resin can be formed by, for example, the diol used when producing the (c) polyester resin.

[0127] Examples of the diol that can form the alkylene oxide structural unit in the polyester resin (c) include alkylene glycols represented by formula (II) and polyoxyalkylene glycols (sometimes referred to as "polyalkylene glycols", "polyalkylene ether glycols", "polyalkylene oxides", etc.) represented by formula (III).

[0128] [Chemical formula 2]

[0129]

[0130] [where p is the same as above];

[0131] [Chemical formula 3]

[0132]

[0133] [wherein n is an integer greater than 2, and p is the same as above].

[0134] These diols may be used alone or in combination of two or more at any ratio.

[0135] As the alkylene glycol, for example, linear alkylene glycols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol; and branched alkylene glycols such as 2-methylpropylene glycol, 2,3-dimethylbutylene glycol, butylethylpropylene glycol, and neopentyl glycol can be used. These alkylene glycols can be used alone or in combination of two or more at any ratio. Among them, from the viewpoint of further improving the low-temperature tensile elongation of the formed vinyl chloride resin molded body, ethylene glycol, 1,4-butanediol, and neopentyl glycol are preferably used as the alkylene glycol, and 1,4-butanediol is more preferably used.

[0136] As the polyoxyalkylene glycol, diethylene glycol, polyethylene glycol, polyoxytetramethylene glycol (sometimes referred to as "polytetramethylene ether glycol", etc.), polyoxypropylene glycol, copolymers of tetramethylene oxide (tetrahydrofuran) and neopentylene oxide (neopentylene oxide), copolymers of tetramethylene oxide (tetrahydrofuran) and propylene oxide, etc. can be used. These polyoxyalkylene glycols can be used alone or in combination of two or more in any ratio. Among them, from the viewpoint of further improving the low-temperature tensile elongation of the formed vinyl chloride resin molded body, diethylene glycol and polyoxytetramethylene glycol are preferably used as the polyoxyalkylene glycol, and polyoxytetramethylene glycol is more preferably used.

[0137] The diol is not particularly limited, but usually at least an alkylene glycol is used. From the viewpoint of further improving the low-temperature tensile elongation of the formed vinyl chloride resin molded article, it is preferred to use an alkylene glycol and a polyoxyalkylene glycol in combination.

[0138] When at least dicarboxylic acid and alkylene glycol as diol are used in producing the (c) polyester resin, the obtained (c) polyester resin has at least a polyester region in which structural units derived from dicarboxylic acid and alkylene oxide structural units derived from alkylene glycol are alternately arranged.

[0139] When polyoxyalkylene glycol is further used as diol in producing 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.

[0140] The (c) polyester resin may have only a polyester region, but preferably has a polyalkylene oxide region in addition to the polyester region from the viewpoint of further improving the low-temperature tensile elongation of the resulting vinyl chloride resin molded article.

[0141] [Ratio of alkylene oxide structural unit derived from alkylene glycol]

[0142] When all structural units (all repeating units) in the (c) polyester resin are 100 mol%, the ratio of the alkylene oxide structural unit derived from the alkylene glycol (i.e., contained in the polyester region) in the (c) polyester resin can be, for example, 50 mol% or less, preferably 40 mol% or less, more preferably 35 mol% or less, further preferably 30 mol% or less, further preferably 25 mol% or less, preferably 10 mol% or more, and more preferably 15 mol% or more. If the ratio of the alkylene oxide structural unit derived from the alkylene glycol (i.e., contained in the polyester region) in the (c) polyester resin is below the upper limit, the low-temperature tensile elongation of the formed vinyl chloride resin molded body can be further improved while suppressing the stickiness of the surface of the vinyl chloride resin molded body. On the other hand, if the ratio of the alkylene oxide structural unit derived from the alkylene glycol (i.e., contained in the polyester region) in the (c) polyester resin is above the lower limit, the low-temperature tensile elongation of the formed vinyl chloride resin molded body can be further improved.

[0143] [Ratio of alkylene oxide structural unit derived from polyoxyalkylene glycol]

[0144] When all structural units (all repeating units) in the (c) polyester resin are 100 mol%, the ratio of the alkylene oxide structural unit derived from the polyoxyalkylene glycol (i.e., included in the polyalkylene oxide region) in the (c) polyester resin can be 0 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, further preferably 40 mol% or more, further preferably 50 mol% or more, preferably 80 mol% or less, and more preferably 70 mol% or less. If the ratio of the alkylene oxide structural unit derived from the polyoxyalkylene glycol (i.e., included in the polyalkylene oxide region) in the (c) polyester resin is above the above lower limit, the low-temperature tensile elongation of the formed vinyl chloride resin molded article can be further improved while suppressing the stickiness of the surface of the vinyl chloride resin molded article. On the other hand, if the ratio of the alkylene oxide structural unit derived from the polyoxyalkylene glycol (i.e., included in the polyalkylene oxide region) in the (c) polyester resin is below the above upper limit, the low-temperature tensile elongation of the formed vinyl chloride resin molded article can be further improved.

[0145] [Ratio of structural units derived from dicarboxylic acid]

[0146] In addition, when all structural units (all repeating units) in the (c) polyester resin are 100 mol%, the proportion of structural units 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, further preferably 30 mol% or less, further preferably 25 mol% or less, preferably 10 mol% or more, and more preferably 15 mol% or more. If the proportion of structural units derived from dicarboxylic acid in the (c) polyester resin is below the upper limit, the low-temperature tensile elongation of the formed vinyl chloride resin molded body can be further improved while suppressing the stickiness of the surface of the vinyl chloride resin molded body. On the other hand, if the proportion of structural units derived from dicarboxylic acid in the (c) polyester resin is above the lower limit, the low-temperature tensile elongation of the formed vinyl chloride resin molded body can be further improved.

[0147] <<Crystallinity>>

[0148] The (c) polyester resin may be a crystalline polyester, an amorphous polyester, or a mixture of a crystalline polyester and an amorphous polyester.

[0149] Furthermore, from the viewpoint of being able to further improve the low-temperature tensile elongation of the formed vinyl chloride resin molded body and suppress the stickiness of the surface of the vinyl chloride resin molded body, the (c) polyester resin is preferably a crystalline polyester. When the (c) polyester resin is a crystalline polyester, the (c) polyester resin has a melting point.

[0150] <<Melting Point>>

[0151] (c) The melting point of the polyester resin is preferably 85°C or higher, more preferably 95°C or higher, further preferably 100°C or higher, further preferably 110°C or higher, further preferably 120°C or higher, and preferably 180°C or lower, more preferably 150°C or lower, further preferably 135°C or lower.

[0152] When the melting point of the (c) polyester resin is within the above-specified range, the low-temperature tensile elongation of the formed vinyl chloride resin molded article can be further increased, and the tackiness of the surface of the vinyl chloride resin molded article can be further suppressed.

[0153] <<Manufacturing method>>

[0154] As a method for producing the (c) polyester resin, a known method (for example, the method described in Japanese Patent Application Laid-Open No. 10-182954) can be adopted. For example, the polyester resin (c) can be obtained by subjecting the above-mentioned dicarboxylic acid and diol to an esterification reaction at 150° C. to 250° C., followed by polycondensation at 230° C. to 300° C. under reduced pressure. Alternatively, the polyester resin (c) can be obtained by subjecting a derivative such as a dimethyl ester of the above-mentioned dicarboxylic acid and diol to an ester exchange reaction at 150° C. to 250° C., followed by polycondensation at 230° C. to 300° C. under reduced pressure.

[0155] <<Content>>

[0156] The content of the (c) polyester resin in the vinyl chloride resin composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, further preferably 2 parts by mass or more, further preferably 3 parts by mass or more, further preferably 4 parts by mass or more, further 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, further preferably 20 parts by mass or less, further preferably 15 parts by mass or less, further preferably 12 parts by mass or less, and further preferably 10 parts by mass or less.

[0157] If the content of the (c) polyester resin in the vinyl chloride resin composition is above the above lower limit, the low-temperature tensile elongation of the formed vinyl chloride resin molded body can be further improved. In addition, if the content of the (c) polyester resin in the vinyl chloride resin composition is above the above lower limit, the powder fluidity of the vinyl chloride resin composition can be improved while suppressing the stickiness of the surface of the formed vinyl chloride resin molded body. On the other hand, if the content of the (c) polyester resin in the vinyl chloride resin composition is below the above upper limit, the low-temperature tensile elongation of the formed vinyl chloride resin molded body can be further improved while ensuring a sufficiently high powder fluidity of the vinyl chloride resin composition.

[0158] The content of the (c) polyester resin in the vinyl chloride resin composition is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, further preferably 2 parts by mass or more, further preferably 3 parts by mass or more, further preferably 4 parts by mass or more, further 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, further preferably 20 parts by mass or less, further preferably 15 parts by mass or less, further preferably 12 parts by mass or less, and further preferably 10 parts by mass or less.

[0159] If the content of the (c) polyester resin in the vinyl chloride resin composition is above the above lower limit, the low-temperature tensile elongation of the formed vinyl chloride resin molded body can be further improved. In addition, if the content of the (c) polyester resin in the vinyl chloride resin composition is above the above lower limit, the powder fluidity of the vinyl chloride resin composition can be improved while suppressing the stickiness of the surface of the formed vinyl chloride resin molded body. On the other hand, if the content of the (c) polyester resin in the vinyl chloride resin composition is below the above upper limit, the low-temperature tensile elongation of the formed vinyl chloride resin molded body can be further improved while ensuring that the powder fluidity of the vinyl chloride resin composition is sufficiently high.

[0160] <(d) Other plasticizers>

[0161] The vinyl chloride resin composition of the present invention may optionally further contain other plasticizers in addition to the above-mentioned (b) polyester plasticizer.

[0162] Specific examples of (d) other plasticizers include plasticizers described in International Publication No. 2016 / 098344 except for the above-mentioned (b) polyester plasticizers. Among them, from the viewpoint of further improving the low-temperature tensile elongation of the formed vinyl chloride resin molded body, epoxidized vegetable oil is preferably used, and epoxidized soybean oil is more preferably used.

[0163] 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 relative to 100 parts by mass of the (a) vinyl chloride resin.

[0164] Moreover, when an epoxidized vegetable oil such as epoxidized soybean oil is used as (d) other plasticizer, from the viewpoint of further improving the low-temperature tensile elongation of the formed vinyl chloride resin molded product, the content of the epoxidized vegetable oil as (d) other plasticizer is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, further 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, relative to 100 parts by mass of the above-mentioned (a) vinyl chloride resin.

[0165] 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 relative to 100 parts by mass of the (b) polyester plasticizer.

[0166] Moreover, when an epoxidized vegetable oil such as epoxidized soybean oil is used as (d) other plasticizer, from the viewpoint of further improving the low-temperature tensile elongation of the formed vinyl chloride resin molded product, the content of the epoxidized vegetable oil as (d) other plasticizer is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, further preferably 4 parts by mass or more, and preferably 10 parts by mass or less, more preferably 7 parts by mass or less, relative to 100 parts by mass of the above-mentioned (b) polyester plasticizer.

[0167] <Additives>

[0168] 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, β-diketone, fatty acid metal salts, etc.; release agents; other release agents other than the above-mentioned vinyl chloride resin particles; impact resistance improvers; perchloric acid compounds (sodium perchlorate, potassium perchlorate, etc.) other than perchloric acid-treated hydrotalcite; antioxidants; mildew inhibitors; flame retardants; antistatic agents; fillers; light stabilizers; foaming agents; pigments, etc.

[0169] Furthermore, as the additives that can be contained in the vinyl chloride resin composition of the present invention, for example, additives described in International Publication No. 2016 / 098344 can be used, and the preferred content thereof can also be the same as that described in International Publication No. 2016 / 098344.

[0170] In addition, the vinyl chloride resin composition of the present invention may further contain an amide compound and silicone oil as additives.

[0171] <<Amide Compound>>

[0172] The amide compound is a component that can improve the releasability of the formed vinyl chloride resin molded article.

[0173] The amide compound is a compound having an amide group, and is represented by the following formula (1), for example:

[0174]

[0175] [In formula (1), n ​​is an integer of 2 to 6, R 1 is an n-valent hydrocarbon group, R 2 is a monovalent hydrocarbon group or hydrogen, R 3 is a monovalent hydrocarbon group, n R 2 They can be the same or different. 3 may be the same or different from each other]. That is, the above-mentioned amide compound has, for example, n hydrogen atoms of a hydrocarbon replaced by -NR 2 COR 3 The structure represented by the amide group substitution.

[0176] Here, n in the above formula (1) is, for example, an integer of 2 to 6, and n may be an integer of 2 to 3, or 2.

[0177] In addition, R in the above formula (1) 1 It is an n-valent hydrocarbon group, and may be an n-valent aliphatic hydrocarbon group or an n-valent aromatic hydrocarbon group.

[0178] In addition, R 1 The number of carbon atoms may be, for example, 1 or more, or 2 or more, or 8 or less, or 6 or less.

[0179] As R 1 , for example, a methylene group, a methylmethylene group, an ethylene (dimethylene group), a dimethylmethylene group, an isopropylene group, a trimethylene group, an isobutenyl group, a tetramethylene group, a hexamethylene group, etc. can be mentioned.

[0180] In addition, R in the above formula (1) 2 is a monovalent hydrocarbon group or hydrogen, n R 2 They may be the same or different from each other. 2 The monovalent hydrocarbon group 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. In addition, the monovalent aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.

[0181] In addition, R 2 The hydrocarbon group has, for example, 1 or more and 2 or less carbon atoms.

[0182] As R 2 , for example, hydrogen, methyl and ethyl can be mentioned.

[0183] As R 2 , you can have n R 2 At least one of them is hydrogen, and n R 2 All hydrogen.

[0184] In addition, R in the above formula (1) 3 is a monovalent hydrocarbon group, n R 3 They may be the same or different. That is, in the amide compound (e), R 3 The saturated hydrocarbon group and R 3 The unsaturated hydrocarbon group may only have R 3 The unsaturated hydrocarbon group may only have R 3 of saturated hydrocarbon groups.

[0185] Here, R 3The saturated hydrocarbon group is, for example, a monovalent chain saturated aliphatic hydrocarbon group.

[0186] In addition, R 3 The number of carbon atoms in the saturated hydrocarbon group may be 11 or more, 13 or more, or 15 or more, or 23 or less, 21 or less, or 19 or less, or 17.

[0187] As R 3 The saturated hydrocarbon group includes, for example, CH 3 (CH 2 ) 10 -、CH 3 (CH 2 ) 12 -、CH 3 (CH 2 ) 14 -、CH 3 (CH 2 ) 16 -、CH 3 (CH 2 ) 18 -、CH 3 (CH 2 ) 20 -、CH 3 (CH 2 ) 22 -wait.

[0188] Here, R 3 The unsaturated hydrocarbon group is, for example, a monovalent chain unsaturated aliphatic hydrocarbon group.

[0189] In addition, R 3 The number of carbon atoms of the unsaturated hydrocarbon group may be 11 or more, 13 or more, or 15 or more, or 23 or less, 21 or less, or 19 or less, or 17.

[0190] As R 3 The unsaturated hydrocarbon group includes, for example, CH 3 (CH 2 ) 7 CH=CH(CH 2 ) 7 -、CH 3 (CH 2 ) 7 CH=CH(CH 2 ) 11 - etc. monounsaturated hydrocarbon groups; CH 3 (CH 2 ) 4 (CH=CHCH 2 )2 (CH 2 ) 6 - etc. diunsaturated hydrocarbon groups; CH 3 CH 2 (CH=CHCH 2 ) 3 (CH 2 ) 6 -, triunsaturated hydrocarbon groups; tetraunsaturated hydrocarbon groups; pentaunsaturated hydrocarbon groups; hexaunsaturated hydrocarbon groups, etc., unsaturated hydrocarbon groups having a carbon-carbon double bond, and unsaturated hydrocarbon groups having a carbon-carbon triple bond, etc.

[0191] Specific examples of the amide compound include ethylenebisoleamide (particularly dimethylenebisoleamide), ethylenebiserucamide, hexamethylenebisoleamide, ethylenebislauramide, ethylenebisstearamide (particularly dimethylenebisstearamide), ethylenebispalmitamide, and hexamethylenebisstearamide.

[0192] The content of the amide compound in the vinyl chloride resin composition may be 0 part by mass, 0.1 part by mass or more, or 0.25 part by mass or more, or 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 above-mentioned (a) vinyl chloride resin.

[0193] 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 above-mentioned (b) polyester plasticizer.

[0194] Furthermore, of course, the vinyl chloride resin composition of the present invention may not contain an amide compound.

[0195] <<Silicone Oil>>

[0196] The silicone oil is a component that can improve the powder fluidity of the vinyl chloride resin composition and suppress the stickiness of the surface of the formed vinyl chloride resin molded article. As the silicone oil, either unmodified silicone oil or modified silicone oil can be used.

[0197] The content of the silicone oil in the vinyl chloride resin composition may be 0 part by mass, 0.1 part by mass or more, or 0.25 part by mass or more, or 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 above-mentioned (a) vinyl chloride resin.

[0198] The content of 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 above-mentioned (b) polyester plasticizer.

[0199] Furthermore, of course, the vinyl chloride resin composition of the present invention may not contain silicone oil.

[0200] <Method for preparing vinyl chloride resin composition>

[0201] The vinyl chloride resin composition of the present invention can be prepared by mixing the above components.

[0202] Here, the mixing method of the above-mentioned (a) vinyl chloride resin, (b) polyester plasticizer, (c) polyester resin, and (d) other plasticizers and various additives further mixed as needed is not particularly limited, and for example, the following method can be mentioned: the components other than the release agent (including vinyl chloride resin particles) are mixed by dry mixing, and then the release agent is added and mixed. Here, a Henschel mixer is preferably used for dry mixing. In addition, the temperature during dry mixing is not particularly limited, but is preferably 50°C or more, more preferably 70°C or more, and preferably 200°C or less.

[0203] <Application of vinyl chloride resin composition>

[0204] Furthermore, the obtained vinyl chloride resin composition can be preferably used for powder molding, and more preferably for powder slush molding.

[0205] (Vinyl chloride resin molded article)

[0206] 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. Moreover, 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 the above-mentioned (a) vinyl chloride resin, (b) polyester plasticizer and (c) polyester resin. Moreover, the vinyl chloride resin molded article of the present invention is excellent in low-temperature tensile elongation.

[0207] Therefore, the vinyl chloride resin molded article of the present invention can be suitably used as an automobile interior material such as the surface skin of an automobile instrument panel.

[0208] <Method for Forming Vinyl Chloride Resin Molded Article>

[0209] Here, when a vinyl chloride resin molded body is formed by powder slush molding, the metal mold temperature during powder slush molding is not particularly limited, but is preferably set to above 200°C, more preferably above 220°C, preferably below 300°C, more preferably below 280°C.

[0210] Furthermore, when manufacturing a vinyl chloride resin molded body, there is no particular limitation, and for example, the following method can be used. That is, the vinyl chloride resin composition of the present invention is sprinkled in a metal mold in the above-mentioned temperature range, and after being left for a period of time of more than 5 seconds and less than 30 seconds, the remaining vinyl chloride resin composition is shaken off, and further left at an arbitrary temperature for a period of time of more than 30 seconds and less than 3 minutes. Then, the metal mold is cooled to a temperature of more than 10°C and less than 60°C, and the obtained vinyl chloride resin molded body of the present invention is demolded from the metal mold. Then, a sheet-like molded body having a shape similar to that of the metal mold is obtained.

[0211] (Laminate)

[0212] The laminate of the present invention comprises a foamed polyurethane molded body and the above-mentioned vinyl chloride resin molded body. In addition, the vinyl chloride resin molded body usually constitutes one surface of the laminate.

[0213] Furthermore, the laminate of the present invention is suitable for use as an automobile interior component, particularly an automobile interior material for forming an automobile instrument panel, because it has a vinyl chloride resin molded body having excellent low-temperature tensile elongation, for example, formed using the vinyl chloride resin composition of the present invention.

[0214] Here, the lamination method of the foamed polyurethane molded body and the vinyl chloride resin molded body is not particularly limited, and for example, the following methods can be used. That is, the following methods can be mentioned: (1) a method of preparing a foamed polyurethane molded body and a vinyl chloride resin molded body separately, and then laminating them using heat fusion, thermal bonding or a known adhesive or the like; (2) a method of directly forming a foamed polyurethane molded body on the vinyl chloride resin molded body by reacting isocyanates and polyols, etc., which are raw materials for the foamed polyurethane molded body, on the vinyl chloride resin molded body to polymerize, and foaming polyurethane by a known method. Among them, the latter method (2) is preferred from the viewpoint of simple process and the viewpoint that the vinyl chloride resin molded body and the foamed polyurethane molded body can be firmly bonded even when a laminated body of various shapes is obtained.

[0215] Example

[0216] Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to these Examples. In addition, in the following description, "%" and "part" indicating an amount are based on mass unless otherwise specified.

[0217] Furthermore, the number average molecular weight and weight average molecular weight of the polyester plasticizer and the polyester resin, the melting point and composition of the polyester resin, the powder fluidity of the vinyl chloride resin composition, and the low-temperature tensile elongation and surface tackiness of the vinyl chloride resin molded body (vinyl chloride resin molded sheet) were measured and evaluated by the following methods.

[0218] <Number Average Molecular Weight and Weight Average Molecular Weight>

[0219] The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polyester plasticizer and the polyester resin were respectively determined as values ​​converted to styrene by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.

[0220] <Melting Point of Polyester Resin>

[0221] The melting point of the polyester resin was measured by the following method: 5.0 mg of the polyester resin as a measurement sample was placed in an aluminum pan using a differential scanning calorimeter "DSC7000X" manufactured by Hitachi High-Technologies Corporation, and the pan was sealed with a lid, and the temperature was raised from 20°C to 250°C at 10°C / min, and the sample was kept for 5 minutes to completely melt, and then the temperature was lowered to 0°C at 20°C / min, and the sample was kept for 5 minutes, and then the temperature was raised to 250°C at 20°C / min again. The endothermic peak in the obtained differential thermal analysis curve was taken as the melting point of the polyester resin.

[0222] <Composition of polyester resin>

[0223] The composition of the polyester resin (i.e., the ratio of each structural unit when all structural units in the polyester resin are 100 mol%) is determined by 1 The proton integral ratio obtained by H-NMR (nuclear magnetic resonance) method is calculated. 1 In the H-NMR method, a measurement sample prepared by dissolving a polyester resin in deuterated chloroform as a solvent is used.

[0224] <Powder fluidity>

[0225] The bulk density of the vinyl chloride resin composition obtained in the examples and comparative examples was measured using a bulk density measuring apparatus described in JIS-K-6720 based on the weight in a 100 mL container. The powder of the vinyl chloride resin composition in the 100 mL container obtained at this time was returned to the bulk density measuring apparatus, and the time from the immediate opening of the baffle to the flow of all the powder was measured to obtain the falling seconds. In addition, if it does not flow completely after waiting for 1 minute, it is recorded as "not flowing". The above operations were all performed at room temperature (23°C). In addition, the smaller the falling seconds, the better the powder fluidity of the vinyl chloride resin composition at room temperature.

[0226] <Surface stickiness>

[0227] The tackiness of the surface of the vinyl chloride resin molded sheets obtained in Examples and Comparative Examples was evaluated by measuring the dynamic friction coefficient as shown below.

[0228] Specifically, a touch tester (manufactured by Trinity Lab Co., Ltd., product name "TL201Ts") was used to measure the dynamic friction coefficient of the surface of the vinyl chloride resin molded body before forming the laminated body under the conditions of load: 50 g, speed: 10 mm / sec, test range: 50 mm, and measurement range: 30 mm excluding 10 mm before and after the test range, under the conditions of a temperature of 23°C and a relative humidity of 50%. The smaller the value of the dynamic friction coefficient, the more the stickiness of the surface of the vinyl chloride resin molded body is suppressed.

[0229] <Tensile elongation at low temperature>

[0230] [Initial stage (unheated state)]

[0231] The vinyl chloride resin molded sheets obtained in the examples and comparative examples were punched out with a dumbbell cutter No. 1 described in JIS K6251, and the tensile elongation at break (%) at a low temperature of -10°C was measured at a tensile speed of 200 mm / min in accordance with JIS K7113. In addition, the larger the value of the tensile elongation at break at low temperature, the more excellent the low-temperature tensile elongation of the vinyl chloride resin molded sheet is.

[0232] [After heating (heat aging test)]

[0233] The laminated body obtained in the examples and comparative examples, in which the polyurethane foam is added to the vinyl chloride resin molded sheet, is used as a sample. The sample is placed in an oven and heated for 400 hours at a temperature of 120°C. Next, the polyurethane foam is peeled off from the heated laminated body, and only the vinyl chloride resin molded sheet is prepared. Then, the tensile elongation at break (%) of the vinyl chloride resin molded sheet at a low temperature of -10°C after heating at 120°C for 400 hours is measured in the same manner as in the above-mentioned initial stage (unheated state).

[0234] (Manufacturing Example)

[0235] The polyester resins A to F used in the examples were produced according to the following Production Examples 1 to 6.

[0236] <Production Example 1>

[0237] The polyester resin A was produced by subjecting terephthalic acid and isophthalic acid as dicarboxylic acids and 1,4-butanediol and polyoxytetramethylene glycol as diols to an esterification reaction at 150 to 250° C. according to a conventional method and then polycondensing at 230 to 300° C. under reduced pressure.

[0238] The number average molecular weight, weight average molecular weight, melting point and composition of the obtained polyester resin A were measured.

[0239] <Production Examples 2 to 6>

[0240] Polyester resins B to F were produced in the same manner as in Production Example 1 except that at least one of the type and amount of the dicarboxylic acid and diol used was changed so that the composition of the obtained polyester resin would be as shown in Table 1, and various measurements were performed.

[0241] (Example 1)

[0242] <Preparation of Vinyl Chloride Resin Composition>

[0243] Among the ingredients shown in Tables 2 and 3, the ingredients except the plasticizer (polyester plasticizer and epoxidized soybean oil) and the vinyl chloride resin particles as a release agent were put into a Henschel mixer for mixing. Then, when the temperature of the mixture rose to 80°C, all the above plasticizers were added to dry it (meaning that the plasticizer was absorbed by the vinyl chloride resin particles as the vinyl chloride resin, and the above mixture became dry). Then, when the dried mixture was cooled to below 70°C, the vinyl chloride resin particles as a release agent were added to prepare a vinyl chloride resin composition.

[0244] The obtained vinyl chloride resin composition was used to evaluate powder flowability. The results are shown in Table 2.

[0245] <Formation of Vinyl Chloride Resin Molded Article>

[0246] The obtained vinyl chloride resin composition was sprinkled on a textured metal mold heated to 250°C, left for an arbitrary time to melt, and then the remaining vinyl chloride resin composition was shaken off. Then, the textured metal mold sprinkled with the vinyl chloride resin composition was left to stand in an oven set at 200°C, and the textured metal mold was cooled with cooling water after 60 seconds from the standing. When the metal mold temperature was cooled to 40°C, a 145 mm×175 mm×1 mm vinyl chloride resin molded body was demolded from the metal mold.

[0247] The surface tack and low-temperature tensile elongation (initial period) of the obtained vinyl chloride resin molded article were evaluated.

[0248] <Formation of Laminated Body>

[0249] The obtained vinyl chloride resin molded sheet was cut into 100 mm×100 mm, and two cut vinyl chloride resin molded sheets were laid in a metal mold of 200 mm×300 mm×10 mm without overlapping, with the textured surface facing downward.

[0250] Separately, a polyol mixture consisting of 50 parts by mass of a propylene oxide-ethylene oxide (PO-EO) block adduct of propylene glycol (hydroxyl value 28, content of terminal EO unit = 10%, content of internal EO unit 4%), 50 parts by mass of a PO-EO block adduct of glycerol (hydroxyl value 21, content of terminal EO unit = 14%), 2.5 parts by mass of water, 0.2 parts by mass of an ethylene glycol solution of triethylenediamine (manufactured by Tosoh Corporation, trade name: "TEDA-L33"), 1.2 parts by mass of triethanolamine, 0.5 parts by mass of triethylamine, and 0.5 parts by mass of a foam stabilizer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: "F-122") and polymethylene polyphenylene polyisocyanate (polymeric MDI) were mixed at a ratio to give an index of 98 to prepare a mixed solution. Then, the prepared mixed solutions were respectively injected onto the two polyethylene resin molding sheets placed in the metal mold as described above. Then, the metal mold was covered with an aluminum plate of 348 mm × 255 mm × 10 mm, thereby sealing the metal mold. After sealing for 5 minutes, the laminated body formed by lining the foamed polyurethane molded body on the 1 mm thick vinyl chloride resin molded sheet was taken out from the mold, and the low-temperature tensile elongation (after heating) of the vinyl chloride resin molded sheet in the laminated body was evaluated. The results are shown in Table 2.

[0251] (Examples 2 to 12, Comparative Examples 1 to 3)

[0252] A vinyl chloride resin molded body and a laminate were produced in the same manner as in Example 1 except that the compounding composition was changed as shown in Tables 2 to 3, and various evaluations were performed. The results are shown in Tables 2 to 3.

[0253] [Table 1]

[0254]

[0255] [Table 2]

[0256]

[0257] [Table 3]

[0258]

[0259] 1) Shin-Daiichi Vinyl Chloride Co., Ltd., product name "ZEST (registered trademark) 1700ZI" (prepared by suspension polymerization, average degree of polymerization: 1700, average particle size 145 μm)

[0260] 2) Shin-Daiichi Vinyl Chloride Co., Ltd., product name "ZEST (registered trademark) 1300SI" (prepared by suspension polymerization, average degree of polymerization: 1300, average particle size 118 μm)

[0261] 3) Shin-Daiichi Vinyl Chloride Co., Ltd., product name "ZEST PQLTX" (prepared by emulsion polymerization, average degree of polymerization: 800, average particle size 1.8 μm)

[0262] 4) ADK CIZER HPN-3130 manufactured by ADK Co., Ltd. (adipic acid-based polyester, number average molecular weight (Mn): 3626, viscosity: 4000 mPa·s)

[0263] 5) ADK CIZER O-130S manufactured by ADK Co., Ltd.

[0264] 6) Kyowa Chemical Industry Co., Ltd., product name "ALCAMAIZER (registered trademark) 5"

[0265] 7) Made by Mizusawa Chemical Industry Co., Ltd., product name: "MIZUKALIZER DS"

[0266] 8) Made by Showa Denko K.K., product name "Karenz DK-1"

[0267] 9) Made by Sakai Chemical Industry Co., Ltd., product name "SAKAI SZ2000"

[0268] 10) ADK Co., Ltd., product name: ADK STAB LS-12

[0269] 11) Made by Nippon Chemical Industry Co., Ltd., product name: "SLIPACKS (registered trademark) O"

[0270] 12) Shin-Etsu Silicone Co., Ltd., product name "KF-96H-300,000 cs" (unmodified silicone oil (polydimethylsiloxane), viscosity: 30×10 4 cs)

[0271] 13) Made by Dainichi Seika Co., Ltd., product name: "DA P 4720 BLACK"

[0272] As can be seen from Tables 1 to 3, by using the vinyl chloride resin compositions of Examples 1 to 12 comprising a vinyl chloride resin, a polyester plasticizer having a number average molecular weight less than a specified value, and a polyester resin having a number average molecular weight greater than a specified value, a vinyl chloride resin molded body having excellent low-temperature tensile elongation can be formed.

[0273] On the other hand, it is found that the vinyl chloride resin molded articles formed using the vinyl chloride resin compositions of Comparative Examples 1 to 3 containing a polyester plasticizer having a number average molecular weight less than a predetermined value but not containing a polyester resin having a number average molecular weight greater than a predetermined value have poor low-temperature tensile elongation.

[0274] Industrial Applicability

[0275] According to the present invention, there can be provided a vinyl chloride resin composition capable of forming a vinyl chloride resin molded body having excellent low-temperature tensile elongation.

[0276] Furthermore, according to the present invention, a vinyl chloride resin molded product having excellent low-temperature tensile elongation can be provided.

[0277] Furthermore, according to the present invention, a laminated body having the vinyl chloride resin molded body can be provided.

Claims

1. A vinyl chloride resin composition comprising a vinyl chloride resin, a polyester plasticizer having a number average molecular weight of less than 8000, and a polyester resin having a number average molecular weight of 8000 or more.

2. The vinyl chloride resin composition according to claim 1, wherein The content of the polyester resin is 0.1 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the vinyl chloride resin.

3. The vinyl chloride resin composition according to claim 1, wherein The polyester resin contains a structural unit derived from a dicarboxylic acid and an alkylene oxide structural unit.

4. The vinyl chloride resin composition according to claim 3, wherein The dicarboxylic acid contains an aromatic dicarboxylic acid.

5. The vinyl chloride resin composition according to claim 4, wherein The aromatic dicarboxylic acid contains at least one of terephthalic acid and isophthalic acid.

6. The vinyl chloride resin composition according to claim 3, wherein The alkylene oxide structural unit 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.

7. The vinyl chloride resin composition according to claim 3, wherein The polyester resin has a polyalkylene oxide region in which the alkylene oxide structural units are continuously arranged.

8. The vinyl chloride resin composition according to claim 7, wherein When all the structural units in the polyester resin are 100 mol %, the ratio of the alkylene oxide structural unit contained in the polyalkylene oxide region is 5 mol % or more and 80 mol % or less.

9. The vinyl chloride resin composition according to claim 1, wherein The content of the polyester plasticizer is 30 parts by mass or more and 200 parts by mass or less relative to 100 parts by mass of the vinyl chloride resin.

10. The vinyl chloride resin composition according to claim 1, wherein The vinyl chloride resin composition is used for powder molding.

11. The vinyl chloride resin composition according to claim 1, wherein The vinyl chloride resin composition is used for powder slush molding. 12 . A vinyl chloride resin molded article obtained by molding the vinyl chloride resin composition according to claim 1 .

13. The vinyl chloride resin molded article according to claim 12, wherein The vinyl chloride resin molded body is used for the surface skin of automobile instrument panels. 14 . A laminate comprising a foamed polyurethane molded product and the vinyl chloride resin molded product according to claim 12 .

15. The laminate according to claim 14, wherein The laminate is used for automobile instrument panels.

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