Vinyl chloride resin composition, vinyl chloride resin molded article, laminate, and automobile instrument panel

Abstract

Provided is a vinyl chloride resin composition capable of forming a vinyl chloride resin molded article having excellent adhesion to a polyolefin substrate. The present invention is a vinyl chloride resin composition comprising a vinyl chloride resin, a plasticizer, and a chlorinated polyolefin.

Description

Technical Field

[0001] The present invention relates to a vinyl chloride resin composition, a vinyl chloride resin molded article, a laminate, and an automotive instrument panel. Background Art

[0002] Vinyl chloride resins are usually used for various applications because of their excellent properties such as cold resistance, heat resistance, and oil resistance. Specifically, for example, a skin formed of a vinyl chloride resin molded article is used in the formation of automotive interior parts such as automotive instrument panels and door trims.

[0003] Moreover, a vinyl chloride resin molded article constituting the skin of an automotive interior part such as an automotive instrument panel is manufactured by a molding method such as powder slush molding to form a vinyl chloride resin composition containing a vinyl chloride resin, a plasticizer, and an additive.

[0004] On the other hand, as a base material for the skin, a polyolefin base material is known. Since the vinyl chloride resin molded article and the polyolefin base material lack adhesiveness, the polyolefin base material is usually treated with a primer and then the vinyl chloride resin molded article is adhered (for example, Patent Document 1).

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Japanese Patent Application Laid-Open No. 61-115839. Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] It would be convenient if there were a vinyl chloride resin molded article that has good adhesiveness to a polyolefin base material even without primer treatment, and there is a need for a vinyl chloride resin composition capable of forming such a vinyl chloride resin molded article.

[0010] Therefore, an object of the present invention is to provide a vinyl chloride resin composition capable of forming a vinyl chloride resin molded article having good adhesiveness to a polyolefin base material.

[0011] In addition, an object of the present invention is to provide a vinyl chloride resin molded article having good adhesiveness to a polyolefin base material.

[0012] Furthermore, an object of the present invention is to provide a laminate having the vinyl chloride resin molded article and an automotive instrument panel including the laminate.

[0013] Means for Solving the Problems

[0014] The inventor of the present invention has conducted in-depth research to solve the above problems. Then, the inventor found that if chlorinated polyolefin is added to a vinyl chloride resin composition, the adhesiveness of a vinyl chloride resin molded article formed using the vinyl chloride resin composition to a polyolefin substrate can be improved, thereby completing the present invention.

[0015] That is, the object of the present invention is to advantageously solve the above problems, and its main configuration is as described below.

[0016] [1] A vinyl chloride resin composition comprising a vinyl chloride resin, a plasticizer, and a chlorinated polyolefin.

[0017] [2] The vinyl chloride resin composition according to [1], wherein the chlorinated polyolefin is 0.1 part by mass or more and 50 parts by mass or less relative to 100 parts by mass of the vinyl chloride resin.

[0018] [3] The vinyl chloride resin composition according to [1] or [2], wherein the percentage content of chlorine in the chlorinated polyolefin is 10% by mass or more and 45% by mass or less.

[0019] [4] The vinyl chloride resin composition according to any one of [1] to [3], wherein the weight average molecular weight of the chlorinated polyolefin is 10,000 or more and 260,000 or less.

[0020] [5] The vinyl chloride resin composition according to any one of [1] to [4], wherein the plasticizer is 30 parts by mass or more and 140 parts by mass or less relative to 100 parts by mass of the vinyl chloride resin.

[0021] [6] The vinyl chloride resin composition according to any one of [1] to [5], wherein the vinyl chloride resin composition is used for powder molding.

[0022] [7] The vinyl chloride resin composition according to [6], wherein the vinyl chloride resin composition is used for powder slush molding.

[0023] [8] A vinyl chloride resin molded article formed by molding the vinyl chloride resin composition according to any one of [1] to [7].

[0024] [9] The vinyl chloride resin molded article according to [8], wherein the vinyl chloride resin molded article is used for an automotive instrument panel.

[0025]

[10] A laminate having the vinyl chloride resin molded article according to [8] or [9] and a polyolefin substrate.

[0026]

[11] An automotive instrument panel comprising the laminate according to

[10] .

[0027] Advantages of the Invention

[0028] According to the present invention, a vinyl chloride resin composition capable of forming a vinyl chloride resin molded body having excellent adhesiveness to a polyolefin substrate can be provided.

[0029] In addition, according to the present invention, a vinyl chloride resin molded body having excellent adhesiveness to a polyolefin substrate can be provided.

[0030] Furthermore, according to the present invention, a laminate having the vinyl chloride resin molded body and an automotive instrument panel including the laminate can be provided.

[0031] According to the present invention, excellent adhesiveness of the vinyl chloride resin molded body to the polyolefin substrate can be obtained even without primer treatment, and thus the industrial usefulness is high. Detailed Description of Embodiments

[0032] Hereinafter, embodiments of the present invention will be described in detail.

[0033] The vinyl chloride resin composition of the present invention can be used when forming the vinyl chloride resin molded body of the present invention.

[0034] The vinyl chloride resin molded body formed using the vinyl chloride resin composition of the present invention can preferably be used as automotive interior materials such as the skin of automotive interior parts such as automotive instrument panels and door trims.

[0035] In addition, the vinyl chloride resin molded body of the present invention can be used when forming the laminate of the present invention. Moreover, the laminate formed using the vinyl chloride resin molded body of the present invention can preferably be used as automotive interior materials used, for example, when manufacturing automotive interior parts such as automotive instrument panels and door trims. The present invention also relates to such an automotive instrument panel.

[0036] (Vinyl Chloride Resin Composition)

[0037] The vinyl chloride resin composition of the present invention is characterized by containing (a) a vinyl chloride resin, (b) a plasticizer, and (c) a chlorinated polyolefin.

[0038] In addition, the vinyl chloride resin composition of the present invention may optionally contain additives in addition to the above-mentioned (a) vinyl chloride resin, (b) plasticizer, and (c) chlorinated polyolefin.

[0039] From the viewpoint of easily obtaining a vinyl chloride resin molded body that can be preferably used as an automotive interior material by using the vinyl chloride resin composition of the present invention, the vinyl chloride resin composition of the present invention is preferably used for powder molding, and more preferably used for powder slush molding.

[0040] The vinyl chloride resin composition of the present invention can be in a granular form. From the viewpoint of ensuring fluidity, the average particle size of the granular composition is preferably 100 μm or more, and from the viewpoint of the uniformity of the surface of the obtained molded body, it is preferably 500 μm or less.

[0041] In addition, in the present invention, the "average particle size" can be measured as the volume average particle size (D50 (median particle size)) by the laser diffraction method in accordance with JIS Z8825.

[0042] <(a) Vinyl chloride resin>

[0043] As the (a) vinyl chloride resin, a granular vinyl chloride resin is usually used. As the (a) vinyl chloride resin, for example, one or more vinyl chloride resin particles can be contained, and one or more vinyl chloride resin fine particles can also be optionally contained. The (a) vinyl chloride resin particularly preferably contains at least vinyl chloride resin particles, and more preferably contains vinyl chloride resin particles and vinyl chloride resin fine particles.

[0044] (a) The vinyl chloride resin can also be produced by any of the known production methods such as suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization.

[0045] In addition, in this 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 less than 30 μm.

[0046] As the (a) vinyl chloride resin, in addition to homopolymers composed of 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 also be cited. Specific examples of monomers (comonomers) that can copolymerize with vinyl chloride monomers and can form vinyl chloride copolymers can use, for example, the monomers described in International Publication No. 2016 / 098344. These components can be used alone or in combination of two or more in any ratio.

[0047] <<Vinyl chloride resin particles>>

[0048] In the vinyl chloride resin composition, the vinyl chloride resin particles usually function as a matrix resin (base material). In addition, the vinyl chloride resin particles are preferably produced by suspension polymerization.

[0049] [Average degree of polymerization]

[0050] 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, and further preferably 5000 or less, more preferably 3000 or less, and still more preferably 2800 or less. If the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is at least the above lower limit, the physical strength of the vinyl chloride resin molded body formed using the vinyl chloride resin composition can be sufficiently ensured, and the tensile properties, particularly the tensile elongation, can be improved. Moreover, a vinyl chloride resin molded body having good tensile elongation can be preferably used as, for example, an automotive interior material such as the skin of an instrument panel of a vehicle having excellent ductility in which fragments do not fly but break as designed when the airbag expands and deploys. In addition, if the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is at most the above upper limit, the meltability of the vinyl chloride resin composition can be improved.

[0051] In addition, in the present invention, the "average degree of polymerization" can be measured in accordance with JIS K6720-2.

[0052] [Average particle size]

[0053] 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, and further preferably 500 μm or less, more preferably 200 μm or less. If the average particle size of the vinyl chloride resin particles is at least 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 at most the above upper limit, the meltability of the vinyl chloride resin composition can be improved, and the surface smoothness of the formed vinyl chloride resin molded body can be improved.

[0054] [Content ratio]

[0055] (a) The content ratio of the vinyl chloride resin particles in the vinyl chloride resin is preferably 70% by mass or more, more preferably 80% by mass or more, and can be 100% by mass, and further preferably 95% by mass or less, more preferably 90% by mass or less. If the content ratio of the vinyl chloride resin particles in (a) the vinyl chloride resin is at least the above lower limit, the physical strength of the formed vinyl chloride resin molded body can be sufficiently ensured, and the tensile elongation of the vinyl chloride resin molded body can be improved. On the other hand, if the content ratio of the vinyl chloride resin particles in (a) the vinyl chloride resin is at most the above upper limit, the powder fluidity of the vinyl chloride resin composition can be improved.

[0056] [[Vinyl chloride resin fine particles]]

[0057] In the vinyl chloride resin composition, the vinyl chloride resin fine particles usually function as a release agent (powder fluidity improver). In addition, the vinyl chloride resin fine particles are preferably produced by an emulsion polymerization method.

[0058] [Average degree of polymerization]

[0059] The average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles is preferably 500 or more, more preferably 700 or more, and further 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 particles as an anti-blocking agent is above the above lower limit, the powder fluidity of the vinyl chloride resin composition can be improved, and the tensile elongation of the formed vinyl chloride resin molded article 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 meltability of the vinyl chloride resin composition can be improved, and the surface smoothness of the formed vinyl chloride resin molded article can be improved.

[0060] In addition, the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin particles can be 2000 or less, 1500 or less, 1000 or less, or 800 or less.

[0061] [Average particle size]

[0062] The average particle size of the vinyl chloride resin particles is usually less than 30 μm, preferably 10 μm or less, more preferably 5 μm or less, and further preferably 0.1 μm or more, more preferably 1 μm or more. If the average particle size of the vinyl chloride resin particles is above the above lower limit, for example, the powder fluidity of the vinyl chloride resin composition can be improved without excessively reducing the size as an anti-blocking agent. On the other hand, if the average particle size of the vinyl chloride resin particles is below the above upper limit, the meltability of the vinyl chloride resin composition can be improved, and the surface smoothness of the formed vinyl chloride resin molded article can be improved.

[0063] [Content ratio]

[0064] (a) The content ratio of the vinyl chloride resin particles in the vinyl chloride resin can be 0% by mass, preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 30% by mass or less, more preferably 20% by mass or less. If the content ratio of the vinyl chloride resin particles in (a) the 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 ratio of the vinyl chloride resin particles in (a) the vinyl chloride resin is below the above upper limit, the physical strength of the formed vinyl chloride resin molded article can be improved.

[0065] <(b) Plasticizer>

[0066] (b) A plasticizer is a component that can impart flexibility to a vinyl chloride resin molded article formed from a vinyl chloride resin composition and improve the tensile properties (especially the tensile elongation). In addition, the vinyl chloride resin composition (b) contains a plasticizer, whereby the molding (especially powder molding) of the vinyl chloride resin composition can be easily performed.

[0067] In the vinyl chloride resin composition, the content of the (b) plasticizer is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, further preferably 70 parts by mass or more, still further preferably 80 parts by mass or more, even still further preferably 90 parts by mass or more, particularly preferably 100 parts by mass or more, based on 100 parts by mass of the above-mentioned (a) vinyl chloride resin. In addition, it is preferably 200 parts by mass or less, more preferably 180 parts by mass or less, further preferably 160 parts by mass or less, still further preferably 140 parts by mass or less, even still further preferably 120 parts by mass or less.

[0068] If the content of the (b) plasticizer in the vinyl chloride resin composition is at or above the above lower limit, the tensile properties (especially the tensile elongation) of the formed vinyl chloride resin molded article can be further improved. On the other hand, if the content of the (b) plasticizer in the vinyl chloride resin composition is at or below the above upper limit, the adhesiveness of the formed vinyl chloride resin molded article to the foamed polyurethane molded article can be ensured sufficiently high.

[0069] Examples of plasticizers that can be used as the (b) plasticizer include the following main plasticizers and auxiliary plasticizers, etc.

[0070] Examples of the so-called main plasticizers include:

[0071] Tri-n-hexyl trimellitate, tri-n-heptyl trimellitate, tri-n-octyl trimellitate, tris(2-ethylhexyl) trimellitate, tri-n-nonyl trimellitate, tri-n-decyl trimellitate, triisodecyl trimellitate, tri-n-undecyl trimellitate, tri-n-dodecyl trimellitate, tri-n-alkyl trimellitates (esters having two or more alkyl groups with different carbon atom numbers [where the carbon atom numbers are 6 to 12] in the molecule), tri-alkyl trimellitates (esters having two or more alkyl groups with different carbon atom numbers [where the carbon atom numbers are 8 to 10] in the molecule), etc. trimellitates;

[0072] Tetra-n-hexyl pyromellitate, tetra-n-heptyl pyromellitate, tetra-n-octyl pyromellitate, tetra(2-ethylhexyl) pyromellitate, tetra-n-nonyl pyromellitate, tetra-n-decyl pyromellitate, tetraisodecyl pyromellitate, tetra-n-undecyl pyromellitate, tetra-n-dodecyl pyromellitate, tetra-n-alkyl pyromellitates (esters having two or more alkyl groups with different carbon atom numbers [where the carbon atom numbers are 6 to 12] in the molecule), etc. pyromellitates;

[0073] Dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis(2-ethylhexyl) phthalate, di-n-octyl phthalate, diisobutyl phthalate, diheptyl phthalate, diphenyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, dinonyl phthalate, dicyclohexyl phthalate and other phthalic acid derivatives;

[0074] Dimethyl isophthalate, bis(2-ethylhexyl) isophthalate, diisooctyl isophthalate and other isophthalic acid derivatives;

[0075] Bis(2-ethylhexyl) tetrahydrophthalate, di-n-octyl tetrahydrophthalate, diisodecyl tetrahydrophthalate and other tetrahydrophthalic acid derivatives;

[0076] Di-n-butyl adipate, bis(2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate and other adipic acid derivatives;

[0077] Bis(2-ethylhexyl) azelate, diisooctyl azelate, di-n-hexyl azelate and other azelaic acid derivatives;

[0078] Di-n-butyl sebacate, bis(2-ethylhexyl) sebacate, diisodecyl sebacate, bis(2-butyl octyl) sebacate and other sebacic acid derivatives;

[0079] Di-n-butyl maleate, dimethyl maleate, diethyl maleate, bis(2-ethylhexyl) maleate and other maleic acid derivatives;

[0080] Di-n-butyl fumarate, bis(2-ethylhexyl) fumarate and other fumaric acid derivatives;

[0081] Triethyl citrate, tri-n-butyl citrate, acetyltriethyl citrate, acetyltri(2-ethylhexyl) citrate and other citric acid derivatives;

[0082] Monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, di-n-butyl itaconate, bis(2-ethylhexyl) itaconate and other itaconic acid derivatives;

[0083] Butyl oleate, glycerol monooleate, diethylene glycol monooleate and other oleic acid derivatives;

[0084] Methyl acetyl ricinoleate, butyl acetyl ricinoleate, glycerol monoricinoleate, diethylene glycol monoricinoleate and other ricinoleic acid derivatives;

[0085] Stearic acid butyl ester, stearic acid derivatives such as diethylene glycol distearate;

[0086] Other fatty acid derivatives such as diethylene glycol monolaurate, diethylene glycol dinonanoate, pentaerythritol fatty acid ester;

[0087] Phosphoric acid derivatives such as triethyl phosphate, tributyl phosphate, tris(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tolyldiphenyl phosphate, tricresyl phosphate, tris(dimethylphenyl) phosphate, tris(chloroethyl) phosphate;

[0088] Glycol derivatives such as diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol bis(2-ethylbutyrate), triethylene glycol bis(2-ethylhexanoate), dibutyl methylene dithioglycolate;

[0089] Glycerol derivatives such as glycerol monoacetate, glycerol triacetate, glycerol tributyrate;

[0090] Epoxy derivatives such as diisodecyl epoxyhexahydrophthalate, epoxidized triglyceride, octyl epoxidized oleate, decyl epoxidized oleate;

[0091] Polyester plasticizers such as polyesters containing structural units derived from adipic acid (adipic acid-based polyesters), polyesters containing structural units derived from sebacic acid (sebacic acid-based polyesters), polyesters containing structural units derived from phthalic acid (phthalic acid-based polyesters), etc.

[0092] As so-called auxiliary plasticizers, there can be mentioned: epoxidized vegetable oils such as epoxidized soybean oil, epoxidized linseed oil; fatty acid esters of glycols such as chlorinated paraffin, triethylene glycol dioctoate; butyl epoxidized stearate, phenyl oleate, methyl dihydroabietate, etc.

[0093] These plasticizers can be used alone or two or more of them can be used in any ratio.

[0094] As the (b) plasticizer, it is particularly preferred to use at least one of trimellitate and polyester, and more preferably at least use trimellitate (hereinafter, sometimes referred to as “(b1) trimellitate”). If (b1) trimellitate is used as the (b) plasticizer, the tensile elongation of the formed vinyl chloride resin molded article can be further improved.

[0095] As the (b) plasticizer, in addition to (b1) trimellitate, plasticizers other than (b1) trimellitate (hereinafter, sometimes referred to as “(b2) other plasticizers”) can be further used.

[0096] <<(b1) trimellitate>>

[0097] (b) The content ratio of (b1) trimellitate ester in the plasticizer is preferably 90% by mass or more, more preferably 92% by mass or more, further preferably 93% by mass or more. In addition, it can be 100% by mass or less, preferably 99% by mass or less, more preferably 98% by mass or less.

[0098] If the content ratio of (b1) trimellitate ester in the (b) plasticizer is above the above lower limit, the tensile elongation of the formed vinyl chloride resin molded body can be further improved. On the other hand, if the content ratio of (b1) trimellitate ester in the (b) plasticizer is below the above upper limit, the adhesiveness of the formed vinyl chloride resin molded body to the foamed polyurethane molded body can be ensured sufficiently high.

[0099] The content of (b1) trimellitate ester in the vinyl chloride resin composition is preferably 25 parts by mass or more, more preferably 45 parts by mass or more, further preferably 65 parts by mass or more, still further preferably 75 parts by mass or more, even still further preferably 85 parts by mass or more, particularly preferably 95 parts by mass or more, with respect to 100 parts by mass of the above (a) vinyl chloride resin. In addition, it is preferably 195 parts by mass or less, more preferably 175 parts by mass or less, further preferably 155 parts by mass or less, still further preferably 135 parts by mass or less, even still further preferably 115 parts by mass or less.

[0100] If the content of (b1) trimellitate ester in the vinyl chloride resin composition is above the above lower limit, the tensile elongation of the formed vinyl chloride resin molded body can be further improved. On the other hand, if the content of (b1) trimellitate ester in the vinyl chloride resin composition is below the above upper limit, the adhesiveness of the formed vinyl chloride resin molded body to the foamed polyurethane molded body can be ensured sufficiently high.

[0101] <<(b2) Other plasticizers>>

[0102] As the (b2) other plasticizer, from the viewpoint of further improving the tensile properties (tensile elongation and tensile stress) of the formed vinyl chloride resin molded body, epoxidized vegetable oil is preferably used, and epoxidized soybean oil is more preferably used.

[0103] The content ratio of the above (b2) other plasticizer in the (b) plasticizer is not particularly limited, and can be, for example, 0% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more. In addition, it can be 10% by mass or less, preferably 8% by mass or less, more preferably 7% by mass or less.

[0104] The content of the (b2) other plasticizer in the vinyl chloride resin composition is not particularly limited, and can be 0 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the above (a) vinyl chloride resin.

[0105] Moreover, in the case of using an epoxidized vegetable oil such as epoxidized soybean oil as the (b2) other plasticizer, from the viewpoint of further improving the tensile properties (tensile elongation and tensile stress) of the formed vinyl chloride resin molded article, the content of the epoxidized vegetable oil as the (b2) other plasticizer is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, still more preferably 4 parts by mass or more, and in addition, 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 (a) vinyl chloride resin.

[0106] <(c) Chlorinated polyolefin>

[0107] (c) Chlorinated polyolefin is a component that can improve the adhesiveness of a vinyl chloride resin molded article formed using a vinyl chloride resin composition to a polyolefin substrate.

[0108] Here, chlorinated polyolefin refers to a substance obtained by chlorinating a polyolefin. Here, olefins include olefin polymers and their modified products.

[0109] Olefin polymers include homopolymers of α-olefins, copolymers of two or more α-olefins, and copolymers of α-olefins and other non-polar monomers. The copolymer can be a random copolymer or a block copolymer. The percentage content of each monomer unit of the copolymer can be calculated based on the usage amount of each monomer used to manufacture the olefin polymer and the analysis results of the copolymer (for example, NMR analysis results).

[0110] Examples of the α-olefin include α-olefins having 2 to 12 carbon atoms, such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 3-methyl-1-butene, 1-hexene, and 1-octene. As the α-olefin, ethylene and propylene are preferred.

[0111] Examples of other non-polar monomers include styrene-based monomers such as styrene, conjugated dienes such as butadiene, and cyclic olefins such as norbornene. These non-polar monomers can be included as long as the effects of the present invention are not impaired. For example, in the copolymer, 30% by mass or less can be monomer units derived from other non-polar monomer units.

[0112] As the olefin polymer, a homopolymer of propylene, a copolymer of propylene and other α-olefins (for example, ethylene-propylene copolymer, ethylene-propylene-1-butene copolymer), etc. are preferred.

[0113] Examples of the modified product of the olefin polymer include an acid-modified product of the olefin polymer, and examples thereof include modified products of unsaturated carboxylic acids or their derivatives. The modified product can be a graft-modified product or can be introduced as a monomer unit into the copolymer.

[0114] Examples of the unsaturated carboxylic acid include (meth)acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic acid, etc. Maleic acid is particularly preferred. One or more than two kinds of unsaturated carboxylic acids can be used.

[0115] Examples of the derivative of the unsaturated carboxylic acid include acid anhydride, acyl halide, amide, imide, ester, and salt of the unsaturated carboxylic acid. Examples of the derivative of the unsaturated carboxylic acid include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic anhydride, maleoyl chloride, acrylamide, methacrylamide, maleimide, dimethyl maleate, monomethyl maleate, diethyl maleate, monoethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconate, dimethyl tetrahydrophthalate, dimethyl bicyclo[2.2.1]hept-2-ene-5,6-dicarboxylate, (meth)acrylic acid alkyl ester, (meth)acrylic acid 2-hydroxyethyl ester, (meth)acrylic acid 2-hydroxypropyl ester, (meth)acrylic acid glycidyl ester, ammonium salt of the unsaturated carboxylic acid, amine salt of the unsaturated carboxylic acid, etc. Among these, acid anhydride of the unsaturated carboxylic acid is preferred, and maleic anhydride is more preferred. One or more than two kinds of derivatives of the unsaturated carboxylic acid can be used.

[0116] As the modified product of the olefin polymer, preferably an acid-modified product of an olefin polymer selected from homopolymers of propylene, copolymers of propylene and other α-olefins (for example, ethylene-propylene copolymer, ethylene-propylene-1-butene copolymer), etc., and more preferably a maleic acid-modified product, a maleic anhydride-modified product, etc.

[0117] The structural unit derived from the unsaturated carboxylic acid or its derivative in the modified product of the olefin polymer with the unsaturated carboxylic acid or its derivative is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. The above total ratio is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 4% by mass or less.

[0118] (c) The chlorinated polyolefin is a substance obtained by chlorinating the olefin polymer and its modified product. The percentage content of chlorine is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and in addition, preferably 45% by mass or less, more preferably 40% by mass or less. The percentage content of chlorine can be measured based on JIS K 7229:1995.

[0119] From the viewpoint of the adhesiveness to the polyolefin substrate, the weight-average molecular weight (Mw) of the chlorinated polyolefin is preferably 10,000 or more, and more preferably 20,000 or more. In addition, from the viewpoint of melting it during molding, the number-average molecular weight (Mw) is preferably 260,000 or less, and more preferably 240,000 or less.

[0120] Mw refers to the value measured by gel permeation chromatography using polystyrene as a reference substance and is the value measured by the method in accordance with JIS K 7252-1:2016.

[0121] Examples of the chlorinated polyolefin include commercially available products manufactured by Nippon Paper Industries Co., Ltd. (Superchlon 814HS, Superchlon 390S, etc.) and commercially available products manufactured by Toyobo Co., Ltd. (trade names: Hardlen 13-LLP, Hardlen 15-LLP).

[0122] From the viewpoint of adhesion to the polyolefin substrate, the content of the (c) chlorinated polyolefin in the vinyl chloride resin composition is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and further preferably 1.0 part by mass or more, relative to 100 parts by mass of the above-mentioned (a) vinyl chloride resin. In addition, from the viewpoint of the tensile elongation of the resin composition, the content of the (c) chlorinated polyolefin in the vinyl chloride resin composition is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, further preferably 20 parts by mass or less, still further preferably 10 parts by mass or less, and even further preferably 8 parts by mass or less, relative to 100 parts by mass of the above-mentioned (a) vinyl chloride resin.

[0123] <Additive>

[0124] The vinyl chloride resin composition of the present invention may further contain various additives in addition to the above components. The additives are not particularly limited, and examples thereof include: lubricants; stabilizers such as perchloric acid-treated hydrotalcite, zeolite, β-diketone, and fatty acid metal salts; release agents; other release agents other than the above-mentioned vinyl chloride resin particles; impact modifiers; perchloric acid compounds other than perchloric acid-treated hydrotalcite (sodium perchlorate, potassium perchlorate, etc.); antioxidants; fungicides; flame retardants; antistatic agents; fillers; light stabilizers; foaming agents; pigments, etc.

[0125] As the above additives that the vinyl chloride resin composition of the present invention can contain, for example, the additives described in International Publication No. 2016 / 098344 can be used, and their preferred contents can also be the same as those described in International Publication No. 2016 / 098344.

[0126] By containing a foaming agent in the vinyl chloride resin composition of the present invention, a foamed vinyl chloride resin molded article can be obtained.

[0127] <Preparation method of vinyl chloride resin composition>

[0128] The vinyl chloride resin composition of the present invention can be prepared by mixing the above components.

[0129] Herein, the method of mixing the above (a) vinyl chloride resin, (b) plasticizer, (c) chlorinated polyolefin, and various additives further compounded as required is not particularly limited. For example, a method of dry-mixing the components other than the release agent (including vinyl chloride resin particles) and then adding the release agent for mixing can be cited. Herein, a Henschel mixer is preferably used for dry-mixing. In addition, the temperature during dry-mixing is not particularly limited, preferably 50°C or higher, more preferably 70°C or higher, and preferably 200°C or lower.

[0130] <Use of vinyl chloride resin composition>

[0131] The vinyl chloride resin composition of the present invention can be used for the manufacture of molded articles. It is advantageous to carry out the molding under temperature conditions of 150°C or higher. If the temperature conditions during the molding of the vinyl chloride resin composition are 150°C or higher, the meltability of the vinyl chloride resin composition can be sufficiently improved, and the surface smoothness of the formed vinyl chloride resin molded article can be sufficiently improved.

[0132] The temperature conditions during the molding of the vinyl chloride resin composition of the present invention are preferably 180°C or higher, more preferably 200°C or higher, further preferably 220°C or higher, and preferably 300°C or lower, more preferably 280°C or lower. If the temperature conditions during the molding of the vinyl chloride resin composition are above the above lower limit, the surface smoothness of the formed vinyl chloride resin molded article can be further improved, and the generation of pinholes on the design surface can be suppressed. On the other hand, if the temperature conditions during the molding of the vinyl chloride resin composition are below the above upper limit, the yellowing during molding of the formed vinyl chloride resin molded article and the poor release from the mold can be suppressed.

[0133] The vinyl chloride resin composition of the present invention can be preferably used for powder molding, and more preferably for powder slush molding.

[0134] (Vinyl chloride resin molded article)

[0135] The vinyl chloride resin molded article of the present invention is characterized in that it is obtained by molding the above vinyl chloride resin composition by any method. Moreover, since the vinyl chloride resin molded article of the present invention is formed using the above vinyl chloride resin composition, it usually contains at least (a) vinyl chloride resin, (b) plasticizer, and (c) chlorinated polyolefin. Moreover, the vinyl chloride resin molded article of the present invention has excellent adhesion to a polyolefin substrate.

[0136] Therefore, the vinyl chloride resin molded article of the present invention can be preferably used as an automotive interior material such as the skin of an automotive instrument panel.

[0137] <Manufacturing method of vinyl chloride resin molded article>

[0138] The vinyl chloride resin molded article of the present invention can be manufactured by molding the above-mentioned vinyl chloride resin composition of the present invention. The temperature conditions during molding of the vinyl chloride resin composition can be within the range described in the item of "Use of the vinyl chloride resin composition".

[0139] For example, in the case of forming a vinyl chloride resin molded article by powder slush molding, the mold temperature during powder slush molding can be 150°C or higher, preferably 200°C or higher, more preferably 220°C or higher, and in addition, preferably 300°C or lower, more preferably 280°C or lower.

[0140] When manufacturing the vinyl chloride resin molded article, there is no particular limitation. For example, the following method can be used. That is, the vinyl chloride resin composition of the present invention is sprinkled in the mold within the above temperature range, and after leaving it for 5 seconds or more and 30 seconds or less, the remaining vinyl chloride resin composition is shaken off, and further left at any temperature for 30 seconds or more and 3 minutes or less. Then, the mold is cooled to 10°C or higher and 60°C or lower, and the obtained vinyl chloride resin molded article of the present invention is released from the mold. Then, a sheet-like molded article shaped like the mold is obtained.

[0141] (Laminate)

[0142] The vinyl chloride resin molded article of the present invention has excellent adhesiveness to a polyolefin substrate even without a primer, and the present invention also relates to a laminate having a vinyl chloride resin molded article and a polyolefin substrate.

[0143] Examples of the polyolefin in the polyolefin substrate include propylene-based resins such as homopolypropylene, propylene-ethylene block copolymer, propylene-butene random copolymer, ethylene-propylene-butene terpolymer, polyethylene, olefin-based thermoplastic elastomers, and mixtures thereof. The MFR thereof is preferably in the range of 0.1 to 300 g / 10 minutes, particularly preferably in the range of 1 to 200 g / 10 minutes. These polyolefins can contain various fillers such as inorganic fillers and glass fibers, pigments, lubricants, antistatic agents, stabilizers, and other additives. The vinyl chloride resin molded article usually constitutes one surface of the laminate.

[0144] Here, the method of laminating the vinyl chloride resin molded article and the polyolefin substrate is not particularly limited, and examples thereof include a method of laminating by using hot melt bonding, thermal bonding, etc. after separately preparing the vinyl chloride resin molded article and the polyolefin substrate. When manufacturing the laminate, an adhesive can be used, or the polyolefin substrate can be pre-treated with a primer. However, the vinyl chloride resin molded article of the present invention has excellent adhesiveness to the polyolefin substrate, and the laminate can be easily manufactured without the need for an adhesive or pre-treatment of the polyolefin substrate with a primer.

[0145] The laminate of the present invention is preferably used as an automotive interior material for forming automotive interior components, particularly for forming an automotive instrument panel. The present invention also relates to an automotive instrument panel including the laminate of the present invention.

[0146] The vinyl chloride resin molded body of the present invention can be a foamed vinyl chloride resin molded body. The foamed vinyl chloride resin molded body of the present invention and the non-foamed vinyl chloride resin molded body of the present invention can also be laminated and used for automotive interior components.

[0147] The vinyl chloride resin molded body of the present invention can also be laminated with a foamed polyurethane molded body and used for automotive interior components. The lamination method with the foamed polyurethane molded body is not particularly limited, and examples thereof include: after separately preparing a vinyl chloride resin molded body and a foamed polyurethane molded body, a method of bonding them by using hot melt bonding, thermal bonding, an adhesive, etc.; a method of reacting isocyanates and polyols, etc., which are raw materials of the foamed polyurethane molded body, on the vinyl chloride resin molded body, polymerizing them, and simultaneously foaming the polyurethane, thereby forming a foamed polyurethane molded body on the vinyl chloride resin molded body.

[0148] Examples

[0149] Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "%" and "parts" representing amounts are based on mass.

[0150] <Preparation of vinyl chloride resin composition>

[0151] The vinyl chloride resin compositions of the examples and comparative examples were prepared as follows.

[0152] Among the compounding components shown in Table 1, the components other than the plasticizers (trimellitate and epoxidized soybean oil) and the vinyl chloride resin fine particles as a release agent were put into a Henschel mixer and mixed. Then, all the above plasticizers were added at the moment when the temperature of the mixture rose to 80°C, and it was allowed to dry (which means that the plasticizers were absorbed by the vinyl chloride resin particles as the vinyl chloride resin, and the above mixture became a dry state). After that, the vinyl chloride resin fine particles as a release agent were added at the moment when the dried mixture was cooled to a temperature of 70°C or lower, and a granular vinyl chloride resin composition was prepared.

[0153] <Production of vinyl chloride resin molded sheet>

[0154] The vinyl chloride resin molded sheet was produced from the vinyl chloride resin composition as follows.

[0155] The granular vinyl chloride resin composition obtained as described above is sprinkled into a grained metal mold heated to a temperature of 250°C, allowed to melt for an arbitrary period of time, and the remaining vinyl chloride resin composition is shaken off. Thereafter, the grained metal mold with the vinyl chloride resin composition sprinkled thereon is left standing in an oven set at a temperature of 200°C. At the moment 60 seconds have elapsed since leaving standing, the grained metal mold is cooled with cooling water. At the moment the temperature of the metal mold has cooled to 40°C, a 145 mm × 175 mm × 1 mm vinyl chloride resin molded sheet, which is a vinyl chloride resin molded article, is released from the mold.

[0156] <Adhesion to polyolefin-based substrates>

[0157] The adhesion of the vinyl chloride resin molded sheet, which is a vinyl chloride resin molded article, to a polyolefin-based substrate is evaluated as follows.

[0158] The obtained vinyl chloride resin molded sheet is cut into 50 mm × 50 mm, overlapped with a 50 mm × 50 mm × 3 mm polypropylene (PP) plate, placed in a press heated to 200°C, and clamped and held at 0.5 kN for 5 minutes. After 5 minutes, the pressure is increased to 1.6 kN and held for 10 seconds, and after releasing the pressure and taking out the sample, it is air-cooled at room temperature (23°C).

[0159] After air-cooling to room temperature, the sample is cut into 20 mm × 50 mm to make a strip. The end of the strip is peeled 10 mm in the length direction, clamped with a jig, and peeled at 90° at a speed of 50 mm / minute, and the maximum test force (N) at this time is recorded as the peel force. The measurement is carried out at room temperature. The results are shown in Table 1.

[0160] The greater the peel force, the more excellent the adhesion of the vinyl chloride resin molded sheet (vinyl chloride resin molded article) to the polypropylene substrate.

[0161] [Table 1]

[0162]

[0163] 1) Manufactured by Shin-Etsu Vinyl Co., Ltd., product name "ZEST 1700ZI" (prepared by suspension polymerization method, average degree of polymerization: 1700, average particle size: 130 μm)

[0164] 2) Manufactured by Shin-Etsu Vinyl Co., Ltd., product name "ZEST PQLTX" (prepared by emulsion polymerization method, average degree of polymerization: 800, average particle size: 1.8 μm)

[0165] 3) Manufactured by Mitsubishi Gas Chemical Co., Ltd., product name "TOTM" (tri-2-ethylhexyl trimellitate)

[0166] 4) Manufactured by ADEKA Corporation, product name "ADK CIZER O-130S"

[0167] 5) Manufactured by Kyowa Chemical Industry Co., Ltd., product name "ALCAMAIZER (registered trademark) 5"

[0168] 6) Manufactured by Mizusawa Chemical Industry Co., Ltd., product name "MIZUKALIZER DS"

[0169] 7) Manufactured by Showa Denko K.K., product name "Karenz DK-1"

[0170] 8) Manufactured by Sakai Chemical Industry Co., Ltd., product name "SAKAI SZ2000"

[0171] 9) Manufactured by ADEKA Corporation, product name "ADK STAB LS-12"

[0172] 10) Product of Mitsubishi Chemical Corporation, product name "Metablen L-1000"

[0173] 11) Manufactured by Nippon Paper Industries Co., Ltd., product name "Superchlon 803MWS" (chlorinated polyolefin. Chlorine content is 29.5% by mass)

[0174] 12) Manufactured by Nippon Paper Industries Co., Ltd., product name "Superchlon 390S" (chlorinated polyolefin. Chlorine content is 36% by mass)

[0175] 13) Manufactured by Nippon Paper Industries Co., Ltd., product name "Superchlon 3221S" (acid-modified chlorinated polyolefin. Chlorine content is 21% by mass)

[0176] 14) Manufactured by Nippon Paper Industries Co., Ltd., product name "Superchlon 3228S" (acid-modified chlorinated polyolefin. Chlorine content is 28% by mass)

[0177] 15) Manufactured by Dainichi Seika Kogyo Co., Ltd., product name "DA P 4720BLACK"

[0178] The weight-average molecular weight (Mw) of the chlorinated polyolefin in the following measurement table was measured.

[0179] It refers to the value measured by gel permeation chromatography using polystyrene as the reference substance, that is, the value measured by the method in accordance with JIS K7252-1:2016.

[0180] [GPC measurement conditions]

[0181] Measurement device: GPC device "1260Infinity II HPLC" manufactured by Agilent Technologies, Inc.

[0182] Chromatographic column:

[0183] “PLgel 20μm MiniMIX - A Guard 50x4.6mm” manufactured by Agilent Technologies, Inc. +

[0184] “PLgel 20μm MiniMIX - A 250x4.6mm” manufactured by Agilent Technologies, Inc. +

[0185] “PLgel 20μm MiniMIX - A 250x4.6mm” manufactured by Agilent Technologies, Inc. +

[0186] “PLgel 20μm MiniMIX - A 250x4.6mm” manufactured by Agilent Technologies, Inc.

[0187] Detector: RI (Differential Refractometer)

[0188] Data processing: “OpenL ABC DS2” manufactured by Agilent Technologies, Inc.

[0189] Column temperature: 40°C

[0190] Eluent: Tetrahydrofuran

[0191] Flow rate: 0.3 mL / min

[0192] Test sample: Dissolve 5 mg of the sample in 5 ml of tetrahydrofuran, filter the resulting solution through a microfilter, and use the filtered filtrate as the test sample.

[0193] Sample injection volume: 50 μl

[0194] Standard sample: According to the measurement manual of the above “OpenL ABC DS2”, use the following monodisperse polystyrene with known molecular weight.

[0195] (Monodisperse polystyrene)

[0196] “A - 2500” manufactured by Tosoh Corporation

[0197] “A - 5000” manufactured by Tosoh Corporation

[0198] “F - 1” manufactured by Tosoh Corporation

[0199] “F - 2” manufactured by Tosoh Corporation

[0200] “F - 4” manufactured by Tosoh Corporation

[0201] “F - 10” manufactured by Tosoh Corporation

[0202] “F - 20” manufactured by Tosoh Corporation

[0203] “F-40” manufactured by Tosoh Corporation

[0204] “F-80” manufactured by Tosoh Corporation

[0205] “F-128” manufactured by Tosoh Corporation

[0206] As can be seen from Table 1, by using the vinyl chloride resin compositions of Examples 1 to 7 containing vinyl chloride resin, plasticizer, and chlorinated polyolefin, a vinyl chloride resin molded article having excellent adhesiveness to a polyolefin substrate can be formed.

[0207] On the other hand, it can be seen that the vinyl chloride resin molded article formed from the vinyl chloride resin composition of Comparative Example 1 that does not contain chlorinated polyolefin has poor adhesiveness to the polyolefin substrate.

[0208] Industrial applicability

[0209] According to the present invention, a vinyl chloride resin composition capable of forming a vinyl chloride resin molded article having excellent adhesiveness to a polyolefin substrate can be provided.

[0210] In addition, according to the present invention, a vinyl chloride resin molded article having excellent adhesiveness to a polyolefin substrate can be provided.

[0211] Furthermore, according to the present invention, a laminate having the vinyl chloride resin molded article and an automotive instrument panel including the laminate can be provided.

[0212] According to the present invention, excellent adhesiveness of the vinyl chloride resin molded article to the polyolefin substrate can be obtained even without primer treatment, and it has high industrial utility.

Claims

1. A vinyl chloride resin composition comprising a vinyl chloride resin, a plasticizer, and a chlorinated polyolefin.

2. The vinyl chloride resin composition according to claim 1, wherein, The chlorinated polyolefin is 0.1 part 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 percentage content of chlorine in the chlorinated polyolefin is 10% by mass or more and 45% by mass or less.

4. The vinyl chloride resin composition according to claim 1, wherein, The weight-average molecular weight of the chlorinated polyolefin is 10,000 or more and 260,000 or less.

5. The vinyl chloride resin composition according to claim 1, wherein The plasticizer is 30 parts by mass or more and 140 parts by mass or less relative to 100 parts by mass of the vinyl chloride resin.

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

7. The vinyl chloride resin composition according to claim 6, wherein, The vinyl chloride resin composition is used for powder slush molding.

8. A vinyl chloride resin molded article formed by molding the vinyl chloride resin composition according to any one of claims 1 to 7.

9. The vinyl chloride resin molded article according to claim 8, wherein, The vinyl chloride resin molded article is used for an automotive instrument panel.

10. A laminate having the vinyl chloride resin molded article according to claim 8 and a polyolefin substrate.

11. An automotive instrument panel comprising the laminate according to claim 10.

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