Vinyl chloride resin composition for powder molding, vinyl chloride resin molded body, and laminate

Abstract

An object of the present invention is to provide a vinyl chloride resin composition for powder molding that can form a vinyl chloride resin molded body having excellent alcohol resistance and low-temperature flexibility. The vinyl chloride resin composition for powder molding of the present invention comprises: (a) a vinyl chloride resin; and (b) a 3-methyl-1,5-pentanediol sebacic acid polyester containing structural units derived from sebacic acid and structural units derived from 3-methyl-1,5-pentanediol. The vinyl chloride resin composition for powder molding of the present invention is preferably used for powder slush molding.

Description

Technical Field

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

[0002] Vinyl chloride resin generally has excellent properties such as cold resistance, heat resistance, and oil resistance, and is therefore used in a variety of applications.

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

[0004] Moreover, the vinyl chloride resin molded body constituting the surface of automobile interior parts such as automobile instrument panels can be produced by powder molding a vinyl chloride resin composition containing vinyl chloride resin, plasticizers, and additives such as pigments using a known molding method such as powder slush molding (for example, refer to Patent Documents 1 and 2).

[0005] Specifically, for example, in Patent Document 1, a laminate having a vinyl chloride resin molded body formed by powder molding a vinyl chloride resin composition for powder molding is produced, wherein the vinyl chloride resin composition for powder molding contains a vinyl chloride resin, trimellitic acid ester, and a polyester containing a structural unit derived from adipic acid and a structural unit derived from 3-methyl-1,5-pentanediol.

[0006] Furthermore, for example, in Patent Document 2, a skin formed of a vinyl chloride resin molded body is produced by powder slush molding a vinyl chloride resin composition containing vinyl chloride resin particles, a trimellitate plasticizer, and additives such as a pigment formed from a mixture of phthalocyanine blue, titanium oxide, and carbon.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: International Publication No. 2020 / 090556;

[0010] Patent Document 2: Japanese Patent Application Laid-Open No. 8-291243. Summary of the Invention

[0011] Problems to be solved by the invention

[0012] Here, the surface of automobile interior parts is sometimes wiped with alcohol to maintain a good hygienic condition. Therefore, vinyl chloride resin molded articles used as the surface of automobile interior parts are required to have excellent alcohol resistance.

[0013] However, the alcohol resistance of vinyl chloride resin molded articles obtained by slush molding the above-mentioned conventional vinyl chloride resin composition powder still needs to be improved.

[0014] Furthermore, a vinyl chloride resin molded article obtained by slush molding a vinyl chloride resin composition powder is required to have excellent low-temperature flexibility.

[0015] Therefore, an object of the present invention is to provide a vinyl chloride resin composition for powder molding that can form a vinyl chloride resin molded body having excellent alcohol resistance and low-temperature flexibility.

[0016] Another object of the present invention is to provide a vinyl chloride resin molded article and a laminate having excellent alcohol resistance and low-temperature flexibility.

[0017] Solutions for solving problems

[0018] The present inventors conducted intensive research with the goal of solving the above-mentioned problems. Furthermore, the present inventors discovered that powder molding of a vinyl chloride resin composition for powder molding using sebacic acid polyester as a plasticizer can produce a vinyl chloride resin molded article having excellent alcohol resistance and low-temperature flexibility, thereby completing the present invention.

[0019] Specifically, the present invention aims to advantageously solve the above-mentioned problems. The vinyl chloride resin composition for powder molding of the present invention is characterized by comprising: (a) a vinyl chloride resin; and (b) a sebacic acid polyester obtained by thin-film distillation, comprising structural units derived from sebacic acid and 3-methyl-1,5-pentanediol and having a terminal structure derived from 2-ethylhexanol. Thus, when the vinyl chloride resin composition for powder molding contains the sebacic acid polyester, the alcohol resistance and low-temperature flexibility of a vinyl chloride resin molded article obtained by powder molding the vinyl chloride resin composition for powder molding can be improved.

[0020] Furthermore, the vinyl chloride resin composition for powder molding of the present invention preferably contains 5 parts by mass or more and 200 parts by mass or less of (b) sebacic acid polyester relative to 100 parts by mass of (a) vinyl chloride resin. When the content of sebacic acid polyester is within the above range, the alcohol resistance and low-temperature flexibility of a vinyl chloride resin molded article obtained by powder molding the vinyl chloride resin composition for powder molding can be further improved.

[0021] Furthermore, the vinyl chloride resin composition for powder molding of the present invention may further contain (c) an additional ester other than sebacic acid polyester. If the vinyl chloride resin composition for powder molding further contains the additional ester, the powder flowability of the vinyl chloride resin composition for powder molding can be further improved.

[0022] Furthermore, the vinyl chloride resin composition for powder molding of the present invention preferably contains 5 parts by mass or more and 99 parts by mass or less of (b) sebacic acid polyester relative to 100 parts by mass of the total plasticizer. When the content of the sebacic acid polyester is within the above range, the alcohol resistance and low-temperature flexibility of a vinyl chloride resin molded article obtained by powder molding the vinyl chloride resin composition for powder molding can be further improved.

[0023] Furthermore, the present invention aims to advantageously solve the above-mentioned problems. The vinyl chloride resin molded article of the present invention is characterized in that it is formed by powder molding (e.g., powder slush molding) any of the above-mentioned vinyl chloride resin compositions for powder molding. The vinyl chloride resin molded article formed by powder molding the above-mentioned vinyl chloride resin composition for powder molding exhibits excellent alcohol resistance and low-temperature flexibility.

[0024] Furthermore, the vinyl chloride resin molded article of the present invention is preferably used as a surface skin for automotive interior parts. This is because the vinyl chloride resin molded article is less susceptible to alcohol-induced degradation, allowing the production of automotive interior parts such as instrument panels that have high low-temperature flexibility.

[0025] Furthermore, the present invention aims to advantageously solve the above-mentioned problems. The laminate of the present invention is characterized by comprising a polyurethane foam molded article and any of the above-mentioned vinyl chloride resin molded articles. The laminate comprising the polyurethane foam molded article and the above-mentioned vinyl chloride resin molded article is less susceptible to degradation by alcohol and can be preferably used as an automotive interior material for the manufacture of automotive interior parts such as automotive instrument panels that have high low-temperature flexibility.

[0026] Effects of the Invention

[0027] According to the vinyl chloride resin composition for powder molding of the present invention, a vinyl chloride resin molded article having excellent alcohol resistance and low-temperature flexibility can be formed.

[0028] Furthermore, according to the present invention, a vinyl chloride resin molded article and a laminate having excellent alcohol resistance and low-temperature flexibility can be provided. DETAILED DESCRIPTION

[0029] Hereinafter, embodiments of the present invention will be described in detail.

[0030] The vinyl chloride resin composition for powder molding of the present invention can be used, for example, when powder molding the vinyl chloride resin molded article of the present invention. Furthermore, the vinyl chloride resin molded article powder molded using the vinyl chloride resin composition for powder molding of the present invention can be preferably used as an automotive interior material, such as the surface covering of automotive interior parts such as automotive instrument panels and door trims.

[0031] The vinyl chloride resin molded article of the present invention can be used, for example, to form the laminate of the present invention. Furthermore, the laminate formed using the vinyl chloride resin molded article of the present invention can be preferably used as an automotive interior material for use in the manufacture of automotive interior parts such as automotive instrument panels and door trims.

[0032] (Vinyl chloride resin composition for powder molding)

[0033] The vinyl chloride resin composition for powder molding of the present invention comprises: (a) a vinyl chloride resin containing vinyl chloride resin particles; and (b) a sebacic acid polyester obtained by thin film distillation, comprising structural units derived from sebacic acid and structural units derived from 3-methyl-1,5-pentanediol and having a terminal structure derived from 2-ethylhexanol. Furthermore, the vinyl chloride resin composition for powder molding of the present invention may further comprise (c) an additional ester other than the sebacic acid polyester. Furthermore, the vinyl chloride resin composition for powder molding of the present invention may optionally comprise other additives. Furthermore, since the vinyl chloride resin composition for powder molding of the present invention comprises at least (a) the vinyl chloride resin and (b) the sebacic acid polyester, the composition can be used to powder mold vinyl chloride resin molded articles having excellent alcohol resistance and low-temperature flexibility. Therefore, the vinyl chloride resin composition for powder molding of the present invention can produce vinyl chloride resin molded articles that are suitable for automotive interior materials, such as automotive instrument panel skins and door trim skins, that have excellent alcohol resistance and low-temperature flexibility.

[0034] Furthermore, for example, the vinyl chloride resin composition for powder molding of the present invention is preferably used for powder slush molding because a vinyl chloride resin molded body that can be suitably used as an automobile interior material can be easily obtained using the vinyl chloride resin composition for powder molding of the present invention.

[0035] <(a) Vinyl chloride resin>

[0036] As the vinyl chloride resin (a), a granular vinyl chloride resin is generally used. The vinyl chloride resin (a) contains one or two or more vinyl chloride resin particles, and may optionally contain one or two or more vinyl chloride resin fine particles.

[0037] 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.

[0038] In this specification, “resin particles” refer to particles having a particle size of 30 μm or larger, and “resin fine particles” refer to particles having a particle size of less than 30 μm.

[0039] In addition, as the vinyl chloride resin (a), in addition to homopolymers formed from vinyl chloride monomer units, vinyl chloride copolymers preferably containing 50% by mass or more, more preferably 70% by mass or more of vinyl chloride monomer units can be mentioned. Specific examples of monomers (comonomers) that can constitute vinyl chloride copolymers and can be copolymerized with vinyl chloride monomers include, for example, monomers described in International Publication No. 2016 / 098344. These components may be used alone or in combination of two or more at any ratio.

[0040] <<Vinyl Chloride Resin Granules>>

[0041] In the vinyl chloride resin composition for powder molding, the vinyl chloride resin particles generally function as a matrix resin (base material). The vinyl chloride resin particles are preferably produced by suspension polymerization.

[0042] [Average degree of polymerization]

[0043] Furthermore, the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin pellets is preferably 800 or higher, more preferably 1000 or higher, preferably 5000 or lower, more preferably 3000 or lower, and even more preferably 2800 or lower. This is because, if the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin pellets is at least the lower limit, the physical strength of the vinyl chloride resin molded article formed using the vinyl chloride resin composition for powder molding can be sufficiently ensured, and tensile properties, particularly tensile elongation, can be improved. Furthermore, vinyl chloride resin molded articles with excellent tensile elongation can be preferably used as automotive interior materials, such as the surface of automobile instrument panels, which exhibit excellent ductility and break as designed during airbag inflation and deployment without scattering fragments. Furthermore, if the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin pellets is at most the upper limit, the meltability of the vinyl chloride resin composition for powder molding can be improved.

[0044] In the present invention, the "average degree of polymerization" can be measured in accordance with JIS K6720-2.

[0045] [Average particle size]

[0046] The average particle size of the vinyl chloride resin particles is generally 30 μm or greater, preferably 50 μm or greater, more preferably 100 μm or greater, and preferably 500 μm or less, more preferably 200 μm or less. This is because, when the average particle size of the vinyl chloride resin particles is at least the lower limit, the powder flowability of the vinyl chloride resin composition for powder molding is further improved. Furthermore, when the average particle size of the vinyl chloride resin particles is at most the upper limit, the meltability of the vinyl chloride resin composition for powder molding is further improved, and the surface smoothness of a vinyl chloride resin molded article formed using the composition can be improved.

[0047] 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.

[0048] [Content ratio]

[0049] Furthermore, the content of the vinyl chloride resin particles in the vinyl chloride resin (a) is preferably 70% by mass or greater, more preferably 80% by mass or greater, and can be 100% by mass, preferably 95% by mass or less, and more preferably 90% by mass or less. This is because, if the content of the vinyl chloride resin particles in the vinyl chloride resin (a) is at least the above lower limit, the physical strength of the vinyl chloride resin molded article formed using the vinyl chloride resin composition for powder molding can be sufficiently ensured, and the tensile elongation can be improved. Furthermore, if the content of the vinyl chloride resin particles in the vinyl chloride resin (a) is at most the above upper limit, the powder flowability of the vinyl chloride resin composition for powder molding is improved.

[0050] <<Vinyl Chloride Resin Microparticles>>

[0051] In a vinyl chloride resin composition for powder molding, vinyl chloride resin microparticles generally function as a dusting agent (powder flowability improver). Furthermore, the vinyl chloride resin microparticles are preferably produced by emulsion polymerization.

[0052] [Average degree of polymerization]

[0053] Furthermore, the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin microparticles is preferably 500 or higher, more preferably 700 or higher, and preferably 2000 or lower, more preferably 1800 or lower. This is because, if the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin microparticles serving as a release agent is at least the above lower limit, the powder flowability of the vinyl chloride resin composition for powder molding is improved, and the tensile elongation of molded articles obtained using the composition is improved. Furthermore, if the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin microparticles is at most the above upper limit, the meltability of the vinyl chloride resin composition for powder molding is improved, and the surface smoothness of vinyl chloride resin molded articles formed using the composition is improved.

[0054] [Average particle size]

[0055] The average particle size of the vinyl chloride resin microparticles is generally less than 30 μm, preferably 10 μm or less, more preferably 5 μm or less, and preferably 0.1 μm or more, more preferably 1 μm or more. This is because, when the average particle size of the vinyl chloride resin microparticles is at least this lower limit, the particle size, for example, used as a release agent, is prevented from being too small, thereby improving the powder flowability of the vinyl chloride resin composition for powder molding. Furthermore, when the average particle size of the vinyl chloride resin microparticles is at most this upper limit, the meltability of the vinyl chloride resin composition for powder molding is further improved, thereby further improving the surface smoothness of the resulting vinyl chloride resin molded article.

[0056] [Content ratio]

[0057] Furthermore, the content of the vinyl chloride resin microparticles in the vinyl chloride resin (a) may be 0% by mass, but is preferably 5% by mass or greater, more preferably 10% by mass or greater, preferably 30% by mass or less, and more preferably 20% by mass or less. This is because, if the content of the vinyl chloride resin microparticles in the vinyl chloride resin (a) is at least the above lower limit, the powder flowability of the vinyl chloride resin composition for powder molding is further improved. Furthermore, if the content of the vinyl chloride resin microparticles in the vinyl chloride resin (a) is at most the above upper limit, the physical strength of a vinyl chloride resin molded article formed using the vinyl chloride resin composition for powder molding can be further improved.

[0058] <(b) Sebacic Acid Polyester>

[0059] The (b) sebacic acid polyester contained in the vinyl chloride resin composition for powder molding generally functions as a plasticizer. (b) Sebacic acid polyester refers to a polyester obtained by thin-film distillation containing structural units derived from sebacic acid and structural units derived from 3-methyl-1,5-pentanediol, and having terminal structures derived from 2-ethylhexanol. In (b) sebacic acid polyester, structural units derived from sebacic acid and structural units derived from 3-methyl-1,5-pentanediol are generally linked alternately.

[0060] Furthermore, the (b) sebacic acid polyester may contain structural units other than structural units derived from sebacic acid and structural units derived from 3-methyl-1,5-pentanediol. The total amount of structural units derived from sebacic acid and structural units derived from 3-methyl-1,5-pentanediol is preferably 50% by mass or more of all structural units, and more preferably 80% by mass or more. Furthermore, the (b) sebacic acid polyester preferably contains only structural units derived from sebacic acid and structural units derived from 3-methyl-1,5-pentanediol as repeating units. Furthermore, since the composition of the present invention contains the (b) sebacic acid polyester, a vinyl chloride resin molded article obtained using the composition exhibits excellent alcohol resistance and low-temperature flexibility.

[0061] Here, the above-mentioned (b) sebacic acid polyester is not particularly limited and can be obtained by polycondensing sebacic acid with 3-methyl-1,5-pentanediol. In addition, the above-mentioned polycondensation can be carried out in the presence of a catalyst. In addition, the above-mentioned polycondensation can be carried out using 2-ethylhexanol as the terminal termination component. In addition, the product obtained by the polycondensation can be subjected to post-treatment of thin film distillation, and other post-treatments can also be carried out. The above-mentioned (b) sebacic acid polyester is obtained by thin film distillation, thereby improving the atomization property. Moreover, the reaction conditions for the polycondensation such as the amount of the above-mentioned monomers, catalysts and terminal termination components, the pressure and temperature of the thin film distillation, etc., can adopt known conditions.

[0062] Furthermore, as the (b) sebacic acid polyester, a commercially available product may also be used.

[0063] The catalyst used in the polycondensation reaction is not particularly limited, and examples thereof include dibutyltin oxide and tetraalkyl titanate.

[0064] The number average molecular weight of the (b) sebacic acid polyester is preferably 1,000 or more, more preferably 2,000 or more, and is preferably 10,000 or less, more preferably 7,000 or less.

[0065] In addition, the "number average molecular weight" can be measured by a VPO (vapor pressure osmotic pressure) method.

[0066] Furthermore, the acid value of the (b) sebacic acid polyester is preferably 1 or less.

[0067] Furthermore, the hydroxyl value of the sebacic acid polyester (b) is preferably 30 or less.

[0068] Furthermore, the viscosity of the sebacic acid polyester (b) is preferably 500 mPa·s or more, more preferably 1000 mPa·s or more, and is preferably 10000 mPa·s or less, more preferably 8000 mPa·s or less.

[0069] In addition, "viscosity" can be measured at a temperature of 23°C in accordance with JIS Z8803.

[0070] The content of the sebacic acid polyester (b) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 20 parts by mass or more, and preferably 200 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably 80 parts by mass or less, relative to 100 parts by mass of the vinyl chloride resin (a). When the content of the sebacic acid polyester (b) is at least the lower limit, the alcohol resistance and low-temperature flexibility of the vinyl chloride resin molded article are improved. Furthermore, when the content of the sebacic acid polyester (b) is at most the upper limit, for example, by adding additional ingredients such as the additional ester (c) to the composition, the physical properties of the vinyl chloride resin composition for powder molding, such as powder flowability, can be improved.

[0071] <(c) Additional Ester>

[0072] The additional ester (c) contained in the vinyl chloride resin composition for powder molding generally functions as a plasticizer. Considering that the aforementioned sebacic acid polyester (b) can improve the alcohol resistance and low-temperature flexibility of the vinyl chloride resin molded article, but can reduce the powder flowability of the vinyl chloride resin composition for powder molding, it is preferable to use the additional ester (c) in combination to improve the powder flowability. The additional ester (c) is not particularly limited as long as it is an ester other than sebacic acid polyester. Examples include ester compounds of aromatic carboxylic acids and monohydric alcohols, and polyesters containing structural units derived from dicarboxylic acids other than sebacic acid and structural units derived from diols (hereinafter referred to as "additional polyesters").

[0073] Examples of the ester compound of an aromatic carboxylic acid and a monohydric alcohol include trimellitic acid ester and pyromellitic acid ester. The trimellitic acid ester and pyromellitic acid ester are preferably ester compounds of trimellitic acid or pyromellitic acid and a monohydric alcohol.

[0074] Specific examples of the monohydric alcohol include, but are not particularly limited to, aliphatic alcohols such as 1-hexanol, 1-heptanol, 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, and 1-dodecanol. Among these, the monohydric alcohol is preferably an aliphatic alcohol having 6 to 18 carbon atoms, and more preferably a linear aliphatic alcohol having 6 to 18 carbon atoms.

[0075] Among them, the trimellitic acid ester or pyromellitic acid ester is preferably a trimellitic acid triester or a pyromellitic acid tetraester in which substantially all the carboxyl groups of trimellitic acid or pyromellitic acid are esterified with the above-mentioned monohydric alcohol. The alcohol residues in the trimellitic acid triester or the pyromellitic acid tetraester may be derived from the same alcohol or from different alcohols.

[0076] The trimellitic acid ester or the pyromellitic acid ester may be formed from a single compound or may be a mixture of different compounds.

[0077] Examples of trimellitic acid esters or pyromellitic acid esters include trimethyl trimellitic acid, triethyl trimellitic acid, tri-n-propyl trimellitic acid, tri-n-butyl trimellitic acid, tri-n-pentyl trimellitic acid, tri-n-hexyl trimellitic acid, tri-n-heptyl trimellitic acid, tri-n-octyl trimellitic acid, tri-n-nonyl trimellitic acid, tri-n-decyl trimellitic acid, tri-n-undecyl trimellitic acid, tri-n-dodecyl trimellitic acid, tri-n-tridecyl trimellitic acid, tri-n-decyl trimellitic acid, and tri-n-decyl trimellitic acid. Linear-chain trimellitic acid esters in which the alkyl group constituting the ester is linear, such as tetraalkyl esters, tri-n-pentadecyl trimellitate, tri-n-hexadecyl trimellitate, tri-n-heptadecyl trimellitate, tri-n-octadecyl trimellitate, and tri-n-alkyl trimellitate (the number of carbon atoms in the alkyl group of the tri-n-alkyl trimellitate may differ within one molecule) [these trimellitic acid esters may be formed from a single compound or a mixture];

[0078] Branched-chain trimellitic acid esters having a branched alkyl group constituting the ester, such as triisopropyl trimellitate, triisobutyl trimellitate, triisoamyl trimellitate, triisohexyl trimellitate, triisoheptyl trimellitate, triisooctyl trimellitate, tri-(2-ethylhexyl) trimellitate, triisononyl trimellitate, triisodecyl trimellitate, triisoundecyl trimellitate, triisododecyl trimellitate, triisotridecyl trimellitate, triisotetradecyl trimellitate, triisopentadecyl trimellitate, triisohexadecyl trimellitate, triisoheptadecyl trimellitate, triisooctadecyl trimellitate, and trialkyl trimellitate (the number of carbon atoms in the alkyl group of the trialkyl trimellitate may differ within one molecule) [these trimellitic acid esters may be formed from a single compound or a mixture];

[0079] Linear-chain pyromellitic acid esters such as tetramethyl pyromellitic acid, tetraethyl pyromellitic acid, tetra-n-propyl pyromellitic acid, tetra-n-butyl pyromellitic acid, tetra-n-pentyl pyromellitic acid, tetra-n-hexyl pyromellitic acid, tetra-n-heptyl pyromellitic acid, tetra-n-octyl pyromellitic acid, tetra-n-nonyl pyromellitic acid, tetra-n-decyl pyromellitic acid, tetra-n-undecyl pyromellitic acid, tetra-n-dodecyl pyromellitic acid, tetra-n-tridecyl pyromellitic acid, tetra-n-tetradecyl pyromellitic acid, tetra-n-pentadecyl pyromellitic acid, tetra-n-hexadecyl pyromellitic acid, tetra-n-heptadecyl pyromellitic acid, tetra-n-octadecyl pyromellitic acid, and tetra-n-alkyl pyromellitic acid (herein, the number of carbon atoms of the alkyl group in the tetra-n-alkyl pyromellitic acid may differ in one molecule), wherein the alkyl group constituting the ester is linear [these pyromellitic acid esters may be formed from a single compound or a mixture];

[0080] Branched-chain pyromellitic acid esters in which the alkyl group constituting the ester is branched, such as tetraisopropyl pyromellitic acid, tetraisobutyl pyromellitic acid, tetraisopentyl pyromellitic acid, tetraisohexyl pyromellitic acid, tetraisoheptyl pyromellitic acid, tetraisooctyl pyromellitic acid, tetra-(2-ethylhexyl) pyromellitic acid, tetraisononyl pyromellitic acid, tetraisodecyl pyromellitic acid, tetraisoundecyl pyromellitic acid, tetraisododecyl pyromellitic acid, tetraisotridecyl pyromellitic acid, tetraisotetradecyl pyromellitic acid, tetraisoheptadecyl pyromellitic acid, tetraisooctadecyl pyromellitic acid, and tetraalkyl pyromellitic acid esters (herein, the number of carbon atoms of the alkyl group in the tetraalkyl pyromellitic acid ester may differ within one molecule) [in addition, these pyromellitic acid esters may be formed from a single compound or a mixture].

[0081] Examples of the additional polyester include polyesters containing a structural unit derived from a dicarboxylic acid such as adipic acid and phthalic acid and a structural unit derived from the above-mentioned diol.

[0082] When the powder molding vinyl chloride resin composition contains the additional ester (c), the content of the additional ester (c) relative to 100 parts by mass of the vinyl chloride resin (a) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and most preferably 10 parts by mass or more, and preferably 200 parts by mass or less, more preferably 150 parts by mass or less, further preferably 130 parts by mass or less, and most preferably 120 parts by mass or less. When the content of the additional ester (c) is above the lower limit, the powder flowability of the powder molding vinyl chloride resin composition, the atomization properties of the vinyl chloride resin molded article, and the low-temperature flexibility are improved. In addition, the additional ester (c) is well absorbed by the vinyl chloride resin (a), and the powder moldability of the powder molding vinyl chloride resin composition is improved. Furthermore, when the content of the additional ester (c) is below the upper limit, the heat shrinkage resistance of the vinyl chloride resin molded article is improved.

[0083] Furthermore, the combined content of the (b) sebacic acid polyester and the (c) additional ester relative to 100 parts by mass of the vinyl chloride resin particles is preferably 30 parts by mass or greater, more preferably 50 parts by mass or greater, and even more preferably 80 parts by mass or greater, and preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and even more preferably 130 parts by mass or less. If the combined content of the (b) sebacic acid polyester and the (c) additional ester is at or above the lower limit, the powder flowability of the vinyl chloride resin composition for powder molding and the low-temperature flexibility of the vinyl chloride resin molded article can be improved. Furthermore, if the combined content of the (b) sebacic acid polyester and the (c) additional ester is at or below the upper limit, the fogging resistance and heat shrinkage resistance can be sufficiently improved.

[0084] Moreover, the content of (b) sebacic acid polyester relative to 100 parts by mass of the total plasticizer is preferably 5 parts by mass or more, more preferably 9 parts by mass or more, further preferably 18 parts by mass or more, particularly preferably 40 parts by mass or more, preferably 99 parts by mass or less, more preferably 90 parts by mass or less, and particularly preferably 80 parts by mass or less. In addition, when the vinyl chloride resin composition for powder molding contains the above-mentioned (c) additional ester, the content of (b) sebacic acid polyester relative to 100 parts by mass of the total plasticizer is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, further preferably 60 parts by mass or less, and particularly preferably 50 parts by mass or less. If the content of (b) sebacic acid polyester relative to the total plasticizer content is above the above lower limit, the alcohol resistance and low-temperature flexibility of the vinyl chloride resin molded article can be sufficiently improved. If the content of (b) sebacic acid polyester relative to the total plasticizer content is below the above upper limit, the powder flowability of the vinyl chloride resin composition for powder molding can be sufficiently improved.

[0085] <Additives>

[0086] The vinyl chloride resin composition for powder molding of the present invention may contain various additives in addition to the above-mentioned components. Examples of such additives include, but are not particularly limited to, components other than the above-mentioned sebacic acid polyester (b) and the additional ester (c) that can function as plasticizers (e.g., epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; chlorinated paraffin, butyl epoxystearate, phenyl oleate, and methyl dihydroabietate); lubricants; stabilizers such as perchloric acid-treated hydrotalcite, zeolite, β-diketone, and fatty acid metal salts; release agents; release agents other than the above-mentioned vinyl chloride resin microparticles; impact modifiers; perchloric acid compounds other than perchloric acid-treated hydrotalcite (e.g., sodium perchlorate and potassium perchlorate); antioxidants; mildew inhibitors; flame retardants; antistatic agents; fillers; light stabilizers; foaming agents; and pigments.

[0087] Furthermore, as the additives that may be contained in the vinyl chloride resin composition for powder molding 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.

[0088] <Shape and Physical Properties of Vinyl Chloride Resin Composition for Powder Molding>

[0089] From the perspective of suitability for powder molding (e.g., powder slush molding), the vinyl chloride resin composition for powder molding of the present invention is preferably in a granular form, more preferably in a dry state with low moisture and viscosity. This state is indicated by the vinyl chloride resin composition for powder molding having physical property values ​​within a predetermined range indicating powder properties. Examples of such physical property values ​​include falling seconds and bulk density.

[0090] <Method for preparing vinyl chloride resin composition for powder molding>

[0091] The vinyl chloride resin composition for powder molding of the present invention can be prepared by mixing the above-mentioned components.

[0092] The mixing method for the (a) vinyl chloride resin, (b) sebacic acid polyester, (c) additional esters (if further added as needed), and various additives (if further added as needed) is not particularly limited, but a mixing method in which the vinyl chloride resin composition for powder molding is formed into a granular composition is preferred. Examples of such mixing methods include dry blending the components other than the release agent (including the vinyl chloride resin microparticles contained in the (a) vinyl chloride resin), allowing the mixture to dry thoroughly (the vinyl chloride resin particles contained in the (a) vinyl chloride resin absorb the plasticizer, leaving the mixture in a dry state), and then adding and mixing the release agent. Dry blending can be performed using, for example, a powder mixer (e.g., a high-performance fluid mixer such as a Henschel mixer). The temperature during dry blending is not particularly limited, but is preferably 50°C or higher, more preferably 70°C or higher, from the perspective of promoting absorption of the other components by the vinyl chloride resin particles. From the perspective of suppressing deterioration or decomposition of the components of the mixture, it is preferably 200°C or lower.

[0093] <Application of vinyl chloride resin composition for powder molding>

[0094] Furthermore, the obtained vinyl chloride resin composition for powder molding can be used for powder molding, and can be preferably used for powder slush molding.

[0095] (Vinyl chloride resin molded article)

[0096] The vinyl chloride resin molded article of the present invention is characterized in that it can be obtained by powder molding the aforementioned vinyl chloride resin composition for powder molding using any powder molding method (e.g., powder slush molding). Furthermore, since the vinyl chloride resin molded article of the present invention is formed using the aforementioned vinyl chloride resin composition for powder molding, it generally contains at least (a) vinyl chloride resin and (b) sebacic acid polyester and exhibits excellent alcohol resistance and low-temperature flexibility.

[0097] Therefore, the vinyl chloride resin molded article of the present invention is preferably used for producing surface skins of automobile interior parts such as automobile instrument panels and door trims that are excellent in alcohol resistance and low-temperature flexibility.

[0098] <Method for Forming Vinyl Chloride Resin Molded Article>

[0099] Here, when the vinyl chloride resin molded body is formed by powder slush molding, 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 preferably 300°C or lower, more preferably 280°C or lower.

[0100] The production of vinyl chloride resin molded articles is not particularly limited, but the following method can be used, for example. Specifically, the vinyl chloride resin composition for powder molding of the present invention is sprinkled into a mold within the above-described temperature range, left for a period of 5 to 30 seconds, and then the remaining vinyl chloride resin composition for powder molding is shaken off. The mold is then left to stand at any temperature for a period of 30 to 3 minutes. The mold is then cooled to a temperature of 10°C to 60°C, and the resulting vinyl chloride resin molded article of the present invention is released from the mold. This results in a sheet-like molded article resembling the shape of the mold.

[0101] (Laminated body)

[0102] The laminate of the present invention comprises a foamed polyurethane molded article and the above-mentioned vinyl chloride resin molded article. The vinyl chloride resin molded article usually constitutes one surface of the laminate.

[0103] Furthermore, the laminate of the present invention, for example, comprises a vinyl chloride resin molded article formed using the vinyl chloride resin composition for powder molding of the present invention, and thus exhibits excellent alcohol resistance and low-temperature flexibility. Therefore, the laminate of the present invention is preferably used as an automotive interior material for forming automotive interior parts such as instrument panels and door trims.

[0104] The method for laminating the polyurethane foam molded article and the vinyl chloride resin molded article is not particularly limited, and the following methods can be used, for example. Specifically, the following methods can be used: (1) a method in which the polyurethane foam molded article and the vinyl chloride resin molded article are prepared separately and then bonded together using heat fusion, thermal bonding, or a known adhesive; (2) a method in which isocyanates and polyols, which are raw materials for the polyurethane foam molded article, are reacted and polymerized on the vinyl chloride resin molded article, and polyurethane is foamed by a known method, thereby forming the polyurethane foam molded article directly on the vinyl chloride resin molded article. Of these, the latter method (2) is preferred from the perspectives of simplifying the process and facilitating the strong bonding of the vinyl chloride resin molded article and the polyurethane foam molded article when obtaining laminated articles of various shapes.

[0105] Example

[0106] Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited to these Examples. In the following description, "%" and "parts" showing amounts are based on mass unless otherwise specified.

[0107] Then, the powder properties (falling seconds, bulk density) of the vinyl chloride resin composition for powder molding, the low-temperature tensile elongation of the vinyl chloride resin molded body (initial, after heating (heat aging test) and after alcohol immersion), and the peak top temperature of the loss modulus (initial, after heating (heat aging test) and after alcohol immersion) were measured and evaluated by the following methods.

[0108] <Measurement Method of Powder Properties (Falling Seconds, Bulk Density)>

[0109] The vinyl chloride resin composition obtained in each example and comparative example was poured into a 100cc stainless steel cylinder of a previously measured weight from the funnel of a powder testing machine ("TESTERTYPE 6721" manufactured by Nippon Oil Tester Co., Ltd.) until the vinyl chloride resin composition overflowed. The filling was then smoothed with a smooth rod. The weight of the filled cylinder was measured, and the weight of the powder added was subtracted from the weight of the cylinder to obtain the weight. The result was divided by 100 to calculate the bulk density (g / cm 3 ). The vinyl chloride resin composition filled in the cylinder is then added back to the hopper. Once fully loaded, the lower pressing plate is pulled out, causing the composition to drop onto a flat plate. The time it takes for the entire composition to fall is measured as the falling seconds. The shorter the falling seconds, the better the powder flowability of the vinyl chloride resin composition.

[0110] <Low-temperature tensile elongation>

[0111] [initial]

[0112] The resulting vinyl chloride resin molded sheet was punched out using a No. 1 dumbbell cutter 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. The greater the tensile elongation at break, the better the low-temperature tensile elongation of the initial (unheated) vinyl chloride resin molded article.

[0113] [After heating (heat aging test)]

[0114] A laminated body lined with a foamed polyurethane molded body is used as a sample. The sample is placed in an oven and heated at a temperature of 120°C for 500 hours. Next, the foamed polyurethane molded body is peeled off from the heated laminated body, and only a vinyl chloride resin molded sheet is prepared. Then, under the same conditions as the initial case mentioned above, the tensile elongation at break (%) of the vinyl chloride resin molded sheet after heating for 500 hours is measured. The larger the value of the tensile elongation at break, the better the tensile elongation of the vinyl chloride resin molded body after heating (heat aging test), and the better the aging resistance.

[0115] <Alcohol resistance test (low-temperature tensile elongation after alcohol immersion)>

[0116] The obtained vinyl chloride resin molded sheet was adjusted to 130 mm × 120 mm. The vinyl chloride resin molded sheet was placed in a 140 mm × 180 mm × 30 mm container to which 300 mL of ethanol was added, and a lid was placed on the container. The vinyl chloride resin molded sheet was taken out after being immersed at room temperature for 3 days. The sample was prepared by air-drying the vinyl chloride resin molded sheet at room temperature for one day. After that, the vinyl chloride resin molded sheet was punched out with a No. 1 dumbbell cutter and a tensile test was performed at -10°C. The larger the value of the tensile elongation at break, the better the tensile elongation of the vinyl chloride resin molded body after alcohol immersion at low temperature, and the better the alcohol resistance.

[0117] <Measurement of Loss Modulus Peak Top Temperature and Evaluation of Its Fluctuation>

[0118] [initial]

[0119] The flexibility of a vinyl chloride resin molded body is evaluated by measuring the peak temperature of the loss modulus (E") based on a dynamic viscoelasticity test (DMA) as an indicator. Specifically, the obtained vinyl chloride resin molded sheet is punched out into a size of 10 mm wide by 40 mm long, thereby serving as a test specimen. Then, in accordance with JIS K7244-4, the peak temperature (°C) of the loss modulus (E") of the test specimen is measured at a frequency of 10 Hz, a heating rate of 2°C / min, and a measurement temperature range of -90°C to +100°C. The lower the peak temperature of the vinyl chloride resin molded sheet, the better the low-temperature flexibility.

[0120] [After heating (heat aging test)]

[0121] The measurement sample prepared in the same manner as in the initial situation described above is placed in an oven and heated at a temperature of 120°C for 500 hours. Next, the foamed polyurethane molding is peeled off from the heated laminate, and only the vinyl chloride resin molding sheet is prepared. Then, under the same conditions as in the initial situation described above, the peak top temperature (°C) of the loss modulus (E") of the measurement sample of the vinyl chloride resin molding sheet after heating for 500 hours is measured, and the degree of variation in the peak top temperature (°C) of the loss modulus (E") of the measurement sample compared to that of the initial state is calculated. The smaller the degree of variation, the better the aging resistance of the vinyl chloride resin molding sheet.

[0122] [After alcohol immersion]

[0123] Place the measurement sample prepared in the same manner as the initial situation described above into a 140mm×180mm×30mm container to which 300mL of ethanol has been added, and cover the container with a lid. Take out the vinyl chloride resin molded sheet after immersing it at room temperature for 3 days. Prepare the sample by air-drying the vinyl chloride resin molded sheet at room temperature for one day. Thereafter, measure the peak temperature (°C) of the loss modulus (E”) of the measurement sample, and calculate the degree of variation in the peak temperature (°C) of the loss modulus (E”) of the measurement sample compared to the initial state. The smaller the degree of variation, the better the alcohol resistance of the vinyl chloride resin molded sheet.

[0124] (Production Example of Polyester Plasticizer)

[0125] The polyester plasticizers (polyesters of dicarboxylic acid and diol) used in Examples and Comparative Examples were prepared as follows.

[0126] Adipic acid or sebacic acid as a dicarboxylic acid, 3-methyl-1,5-pentanediol as a diol, and 2-ethylhexanol as a terminator (terminator) were placed in a reaction vessel. Tetraisopropyl titanate was added as a catalyst, and a suitable solvent was added. The temperature was raised while stirring. Byproduct water was removed under normal and reduced pressure to complete the dehydration condensation reaction. The resulting product was subjected to thin-film distillation to obtain polyester plasticizers A and B with 2-ethylhexyloxy groups at the end. The results are shown in Table 1.

[0127] [Table 1]

[0128]

[0129] (Example 1)

[0130] <Preparation of vinyl chloride resin composition for powder molding>

[0131] The ingredients listed in Table 2, excluding the plasticizers (trimellitate, polyester plasticizer B, and epoxidized soybean oil (ESBO)) and vinyl chloride resin microparticles as a release agent, were mixed in a Henschel mixer. All of the plasticizers were added when the mixture reached 80°C, and the mixture was allowed to dry completely (this refers to the plasticizer being absorbed by the vinyl chloride resin particles, resulting in a dry mixture). After the dried mixture was cooled to below 70°C, vinyl chloride resin microparticles were added as a release agent to prepare a vinyl chloride resin composition.

[0132] <Preparation of Resin Molded Sheet for Evaluation>

[0133] The resulting vinyl chloride resin composition was poured into a textured mold heated to 250°C and allowed to melt for an arbitrary period of time, after which the excess vinyl chloride resin composition was shaken off. The textured mold containing the vinyl chloride resin composition was then placed in an oven set at 200°C and allowed to stand. After 60 seconds had passed since the start of the standstill, the textured mold was cooled with cooling water. When the mold temperature cooled to 40°C, a 145 mm x 175 mm x 1 mm vinyl chloride resin molded sheet was released from the mold.

[0134] <Skin / Polyurethane (PU) Laminate>

[0135] One of the obtained vinyl chloride resin molded sheets was placed in a mold of 200 mm×300 mm×10 mm with the etched surface facing downward.

[0136] Separately, 50 parts of a PO (propylene oxide)·EO (ethylene oxide) block adduct of propylene glycol (hydroxyl number 28, terminal EO unit content = 10%, internal EO unit content = 4%), 50 parts of a PO·EO block adduct of glycerol (hydroxyl number 21, terminal EO unit content = 14%), 2.5 parts of water, 0.2 parts of an ethylene glycol solution of triethylenediamine (manufactured by Tosoh Corporation, trade name "TEDA-L33"), 1.2 parts of triethanolamine, 0.5 parts of triethylamine, and 0.5 parts of a foam stabilizer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "F-122") were mixed to obtain a polyol mixture. Furthermore, the obtained polyol mixture and polymethylene polyphenylene polyisocyanate (polymeric MDI) were mixed at a ratio to give an index of 98 to prepare a mixed solution. This mixed solution was then poured onto a vinyl chloride resin molded sheet placed in a mold.

[0137] After that, the mold was covered with a 348 mm × 255 mm × 10 mm aluminum plate from above to seal the mold. After the mold was sealed, it was left for 5 minutes to form a foamed polyurethane molded body (thickness: 9 mm, density: 0.2 g / cm 3 ) is lined with a laminate of a vinyl chloride resin molded sheet (thickness: 1 mm) as the surface.

[0138] (Example 2)

[0139] A vinyl chloride resin composition for powder molding, a vinyl chloride resin molded sheet, and a laminate were prepared in the same manner as in Example 1, except that the amounts of polyester plasticizer B and trimellitate used were changed as shown in Table 2 (trimellitate was not contained). Measurements and evaluations were then performed in the same manner as in Example 1. The results are shown in Table 2.

[0140] (Comparative Example 1)

[0141] A vinyl chloride resin composition for powder molding, a vinyl chloride resin molded sheet, and a laminate were prepared in the same manner as in Example 1, except that the amounts of polyester plasticizer B and trimellitate used were changed as shown in Table 2 (polyester plasticizer B was not included). Measurements and evaluations were then performed in the same manner as in Example 1. The results are shown in Table 2.

[0142] (Comparative Examples 2 and 3)

[0143] In Comparative Examples 2 and 3, as shown in Table 2, polyester plasticizer A was used instead of polyester plasticizer B. Powder molding vinyl chloride resin compositions, vinyl chloride resin molded sheets, and laminates were prepared in the same manner as in Examples 1 and 2, respectively. Measurements and evaluations were then performed in the same manner as in Example 1. The results are shown in Table 2.

[0144] [Table 2]

[0145]

[0146] The contents of the ingredients expressed by product names in the table are as follows.

[0147] <Vinyl chloride resin pellets>

[0148] ZEST (registered trademark) 1700ZI (Manufacturer: Shin-Daiichi Polyvinyl Chloride Co., Ltd.): Vinyl chloride resin (suspension polymerization, average particle size: 129 μm, degree of polymerization: 1700)

[0149] ZEST (registered trademark) 1300SI (Manufacturer: Shin-Daiichi Polyvinyl Chloride Co., Ltd.): Vinyl chloride resin (suspension polymerization, average particle size: 132 μm, degree of polymerization: 1300)

[0150] <Vinyl chloride resin particles (release agent)>

[0151] ZEST PQLTX (Manufacturer: Shin-Daiichi Polyvinyl Chloride Co., Ltd.): Vinyl chloride resin (emulsion polymerization, average particle size: 1.8 μm, degree of polymerization: 800)

[0152] <Plasticizer>

[0153] Trimex N-08 (Manufacturer: Kao Corporation): Trimellitate plasticizer (n-C8, C10 trimellitate)

[0154] ADK Cizer O-130S (Manufacturer: ADK Co., Ltd.): Epoxidized soybean oil (ESBO)

[0155] <Stabilizer>

[0156] Alkamizer (registered trademark) 5 (manufacturer: Kyowa Chemical Industry Co., Ltd.): Perchloric acid partially introduced hydrotalcite (90% ClO4HDT)

[0157] MIZUKALIZER DS (Manufacturer: Mizusawa Chemical Industry Co., Ltd.): Na-zeolite

[0158] Karenz DK-1 (Manufacturer: Showa Denko K.K.): β-diketone

[0159] Adekastub LA-72 (manufacturer: Adeka Co., Ltd.): hindered amine light stabilizer (HALS).

[0160] SAKAI SZ2000 (manufacturer: Sakai Chemical Industry Co., Ltd.): Zinc stearate

[0161] <Release Agent>

[0162] Adekastub LS-12 (Manufacturer: Adeka Co., Ltd.): 12-hydroxystearic acid

[0163] <Pigment>

[0164] DA PX 1720(A) Black (Manufacturer: Dainichi Seika Industries, Ltd.): Colorant

[0165] Table 2 shows that the vinyl chloride resin molded articles using polyester plasticizer B (sebacic acid polyester) as a plasticizer (Examples 1 and 2) exhibit higher tensile elongation after 3 days of alcohol immersion and 500 hours of heating, compared to the vinyl chloride resin molded articles containing no polyester plasticizer B (Comparative Example 1) and the vinyl chloride resin molded articles using polyester plasticizer A (adipate polyester) as a plasticizer (Comparative Examples 2 and 3). This demonstrates that the vinyl chloride resin molded articles using sebacic acid polyester as a plasticizer exhibit superior alcohol resistance compared to the vinyl chloride resin molded articles using adipic acid polyester as a plasticizer.

[0166] Furthermore, it was shown that, since low peak top temperatures of the loss modulus (E") were obtained in Examples 1 and 2, the vinyl chloride resin molded article using sebacic acid polyester as a plasticizer had excellent low-temperature flexibility.

[0167] Furthermore, in Examples 1 and 2, the fluctuations in the peak top temperatures of the loss modulus (E") after 3 days of alcohol immersion and after 500 hours of heating were small, indicating that the vinyl chloride resin molded article using sebacic acid polyester as a plasticizer has excellent low-temperature flexibility.

[0168] (Example 3)

[0169] A vinyl chloride resin composition for powder molding, a vinyl chloride resin molded sheet, and a laminate were prepared in the same manner as in Example 1, except that the amounts of polyester plasticizer B and trimellitate used, as well as the type of vinyl chloride resin particles, were changed as shown in Table 3. Measurements and evaluations were then performed in the same manner as in Example 1. The results are shown in Table 3.

[0170] (Comparative Example 4)

[0171] As shown in Table 3, a vinyl chloride resin composition for powder molding, a vinyl chloride resin molded sheet, and a laminate were prepared in the same manner as in Example 3, except that polyester plasticizer A was used instead of polyester plasticizer B. Measurements and evaluations were then performed in the same manner as in Example 1. The results are shown in Table 3.

[0172] [Table 3]

[0173]

[0174] Table 3 shows that, although the total amount of plasticizers and the type of vinyl chloride resin particles differ from those in Table 2, the vinyl chloride resin molded article using polyester plasticizer B (sebacic acid polyester) as the plasticizer (Example 3) exhibits higher tensile elongation after 3 days of alcohol immersion and 500 hours of heating than the vinyl chloride resin molded article using polyester plasticizer A (adipate polyester) as the plasticizer (Comparative Example 4). This demonstrates that, regardless of the total amount of plasticizers or the type of vinyl chloride resin particles, the vinyl chloride resin molded article using sebacic acid polyester as the plasticizer exhibits superior alcohol resistance compared to the vinyl chloride resin molded article using adipic acid polyester as the plasticizer.

[0175] Furthermore, in Example 3, a low peak top temperature of the loss modulus (E") was obtained, indicating that the vinyl chloride resin molded article using sebacic acid polyester as a plasticizer has excellent low-temperature flexibility, regardless of the total amount of the plasticizer or the type of vinyl chloride resin particles. Furthermore, in Example 3, the fluctuation in the peak top temperature of the loss modulus (E") after immersion in alcohol for 3 days and after heating for 500 hours was small, indicating that the vinyl chloride resin molded article using sebacic acid polyester as a plasticizer has excellent low-temperature flexibility, regardless of the total amount of the plasticizer or the type of vinyl chloride resin particles.

[0176] (Examples 4 and 5)

[0177] A vinyl chloride resin composition for powder molding, a vinyl chloride resin molded sheet, and a laminate were prepared in the same manner as in Example 1, except that the amounts of polyester plasticizer B and trimellitate used were changed as shown in Table 4. Measurements and evaluations were then performed in the same manner as in Example 1. The results are shown in Table 4 along with those of Examples 1 and 2 and Comparative Example 1.

[0178] [Table 4]

[0179]

[0180] The comparison of embodiment 1,2,4,5 and comparative example 1 in table 4 shows that the containing ratio of sebacic acid polyester is higher, and the low-temperature tensile elongation after alcohol dipping for 3 days and heating for 500 hours is more suppressed relative to the reduction degree of the low-temperature tensile elongation of initial state.Thus show that the containing ratio of sebacic acid polyester is higher, and the low-temperature tensile elongation after alcohol dipping for 3 days and heating for 500 hours is maintained more well, and alcohol resistance and low-temperature flexibility improve more.Show in addition that along with the containing ratio of trimellitic acid ester plasticizer uprises, the falling seconds of composition (powder) increases, and therefore by improving the containing ratio of the ester component except sebacic acid polyester, the powder flowability of composition improves.

[0181] Industrial applicability

[0182] According to the vinyl chloride resin composition for powder molding of the present invention, a vinyl chloride resin molded article having excellent alcohol resistance and low-temperature flexibility can be formed.

[0183] Furthermore, according to the present invention, a vinyl chloride resin molded article and a laminate having excellent alcohol resistance and low-temperature flexibility can be provided.

Claims

1. A vinyl chloride resin composition for powder molding, comprising: (a) vinyl chloride resin; and (b) a sebacic acid polyester obtained by thin film distillation, the sebacic acid polyester consisting of a structural unit derived from sebacic acid, a structural unit derived from 3-methyl-1,5-pentanediol, and a terminal structure derived from 2-ethylhexanol, The (a) vinyl chloride resin contains vinyl chloride resin particles having a particle size of 30 μm or more and vinyl chloride resin fine particles having a particle size of less than 30 μm.

2. The vinyl chloride resin composition for powder molding according to claim 1, wherein The vinyl chloride resin composition for powder molding contains 5 parts by mass or more and 200 parts by mass or less of (b) sebacic acid polyester relative to 100 parts by mass of (a) vinyl chloride resin.

3. The vinyl chloride resin composition for powder molding according to claim 1, wherein The vinyl chloride resin composition for powder molding further contains (c) an additional ester other than the sebacic acid polyester.

4. The vinyl chloride resin composition for powder molding according to claim 1, wherein The vinyl chloride resin composition for powder molding contains 5 parts by mass or more and 99 parts by mass or less of (b) sebacic acid polyester based on 100 parts by mass of all plasticizers. 5 . A vinyl chloride resin molded article produced by powder slush molding the vinyl chloride resin composition for powder molding according to claim 1 . The vinyl chloride resin molded article according to claim 5, wherein The vinyl chloride resin molded article is used for automobile instrument panels.

7. A laminated body obtained by laminating the vinyl chloride resin molded body according to claim 5 and polyurethane foam.

8. The laminate according to claim 7, wherein The laminate is used for automobile instrument panels.

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