Thermoplastic elastomer composition and molded article

Abstract

The purpose of the present invention is to provide a thermoplastic elastomer composition having excellent low-temperature bendability. The present invention includes a thermoplastic elastomer composition containing a vinyl chloride polymer (A), a chlorinated polyolefin (B) having a melt flow rate of 1.5 g / 10 minutes or less and a brittle temperature of-60 DEG C or less as measured at 180 DEG C under a load of 21.6 kg, and a plasticizer (C).

Description

Technical Field

[0001] The present invention relates to a thermoplastic elastomer composition and a molded article, and more particularly, to a thermoplastic elastomer composition containing vinyl chloride and chlorinated polyolefin, and a molded article containing the thermoplastic elastomer composition. Background Art

[0002] Vinyl chloride resin is used as a general-purpose resin due to its advantages in chemical and mechanical stability, processing, and moldability. As uses of vinyl chloride resin, it has been widely used for pipes such as water supply pipes, wire coating, corrugated sheets, rain gutters, fiber-reinforced soft sheets, agricultural films, gaskets, and the like.

[0003] However, vinyl chloride resin has the following problems: when used in cold regions, in the case of a normal formulation, the low-temperature properties are poor, and when formed into a molded article, it is easily damaged by external impact. In order to obtain a vinyl chloride resin with improved cold resistance, measures such as increasing the amount of plasticizer and using a plasticizer with excellent low-temperature properties have been taken. However, when the amount of plasticizer is increased, the mechanical properties are reduced. In addition, when a plasticizer with excellent low-temperature properties is used, the price is high and the molecular weight is low. Therefore, there are problems such as a reduction in heat resistance and an increase in cost.

[0004] In this regard, for example, Patent Document 1 discloses a thermoplastic elastomer composition containing 100 parts by weight of crystalline chlorinated polyethylene having a DOP oil absorption of 25 or more and 10 to 75 parts by weight of a plasticizer as main components. The chlorinated degree of the crystalline chlorinated polyethylene is 20 to 45% and the heat of crystal melting by DSC method is 5 to 35 cal / g. The crystalline chlorinated polyethylene uses di-2-ethylhexyl phthalate (DOP) as the oil component. Here, in Patent Document 1, a thermoplastic elastomer composition containing a vinyl chloride-based resin in addition to chlorinated polyethylene and a plasticizer is also disclosed, and it is also described that by blending a vinyl chloride-based resin in chlorinated polyethylene, the moldability is improved synergistically with the action of the plasticizer, and further, effects such as improving low-temperature properties and preventing the bleeding phenomenon of the plasticizer are achieved. It should be noted that in Patent Document 1, it is not described that the amount of the vinyl chloride-based resin in the thermoplastic elastomer composition is more than that of the crystalline chlorinated polyethylene.

[0005] In addition, as a known technique, a method of increasing oil to improve cold resistance and a method of using a cold-resistant plasticizer are known. In this regard, for example, Patent Document 2 discloses an attempt to obtain a molded article having sufficient high cold resistance while having a certain hardness and transparency by further containing 1,3,2,4-di(p-methylbenzylidene)sorbitol in a halogen-based soft resin composition containing a halogen-based resin and a plasticizer.

[0006] Prior Art Documents

[0007] Patent Document

[0008] Patent Document 1: Japanese Unexamined Patent Application Publication No. 5-247290

[0009] Patent Document 2: Japanese Unexamined Patent Application Publication No. 8-253643 Summary of the Invention

[0010] Problems to be Solved by the Invention

[0011] In the past, various attempts have been made to improve the cold resistance of vinyl chloride resins, etc. However, in the prior arts such as the invention described in Patent Document 1 above, sufficient cold resistance still cannot be obtained. In addition, even in a composition containing chlorinated polyethylene, vinyl chloride, and a plasticizer, in a composition having chlorinated polyethylene as the main component as in the composition described in Patent Document 1, there is a tendency for the heat distortion temperature to be lower compared to a composition having vinyl chloride as the main component. In addition, when the content of the plasticizer in a composition having chlorinated polyethylene as the main component is increased, there is a tendency for the plasticizer to exude easily. Especially when the content of the cold-resistant plasticizer is increased, since the molecular weight of the cold-resistant plasticizer is low, the heat aging resistance sometimes deteriorates.

[0012] The present invention has been made in view of the above problems, and an object thereof is to provide a thermoplastic elastomer composition having excellent low-temperature bendability.

[0013] Means for Solving the Problems

[0014] The inventors of the present application repeatedly conducted in-depth studies to solve the above problems, and as a result, found that a thermoplastic elastomer composition using a composition containing a specific chlorinated polyolefin has excellent low-temperature bendability.

[0015] That is, the present invention includes the following thermoplastic elastomer composition and a molded article containing the thermoplastic elastomer composition.

[0016] [1] A thermoplastic elastomer composition comprising a vinyl chloride polymer (A), a chlorinated polyolefin (B), and a plasticizer (C), wherein the melt flow rate of the chlorinated polyolefin (B) measured at 180°C under a load of 21.6 kg is 1.5 g / 10 minutes or less and the embrittlement temperature is -60°C or less.

[0017] [2] The thermoplastic elastomer composition according to [1], wherein the chlorinated polyolefin (B) is chlorinated polyethylene.

[0018] [3] The thermoplastic elastomer composition according to [1] or [2], wherein the chlorine content of the chlorinated polyolefin (B) is 5 to 50% by mass.

[0019] [4] The thermoplastic elastomer composition according to any one of [1] to [3], wherein the average degree of polymerization of the vinyl chloride polymer (A) is 300 to 10,000.

[0020] [5] The thermoplastic elastomer composition according to any one of [1] to [4], wherein the plasticizer (C) is a phthalate plasticizer.

[0021] [6] The thermoplastic elastomer composition according to any one of [1] to [5], wherein the chlorinated polyolefin (B) is 1.0 to 80.0 parts by mass with respect to 100 parts by mass of the vinyl chloride polymer (A).

[0022] [7] The thermoplastic elastomer composition according to any one of [1] to [6], wherein the plasticizer (C) is 1.0 to 110.0 parts by mass with respect to 100 parts by mass of the vinyl chloride polymer (A).

[0023] [8] The thermoplastic elastomer composition according to any one of [1] to [7], wherein the melt flow rate of the chlorinated polyolefin (B) measured at 180 °C under a load of 21.6 kg is 0.01 g / 10 minutes or more.

[0024] [9] The thermoplastic elastomer composition according to any one of [1] to [8], wherein the embrittlement temperature of the chlorinated polyolefin (B) is -150 °C or higher.

[0025]

[10] A molded article comprising the thermoplastic elastomer composition according to any one of [1] to [9].

[0026]

[11] A cable coating material, sheet or film comprising the thermoplastic elastomer composition according to any one of [1] to [9].

[0027]

[12] A tube, gasket or sealing ring comprising the thermoplastic elastomer composition according to any one of [1] to [9].

[0028] Advantages of the Invention

[0029] According to the present invention, a thermoplastic elastomer composition excellent in low-temperature bendability can be provided.

[0030] In addition, when the thermoplastic elastomer composition of the present invention is used, good cold resistance can be obtained, and a molded article with stable performance can be obtained. Detailed Description

[0031] Hereinafter, embodiments of the present invention will be described in detail. It should be noted that the embodiments described below show an example of a representative embodiment of the present invention, and do not thereby interpret the scope of the present invention narrowly. In addition, unless otherwise specified, the description of "A to B" for a numerical range means A or more and B or less. For example, the description of "1 to 5%" means 1% or more and 5% or less.

[0032] [Thermoplastic elastomer composition]

[0033] One embodiment of the present invention is a thermoplastic elastomer composition comprising a vinyl chloride polymer (A), a chlorinated polyolefin (B), and a plasticizer (C).

[0034] The above-mentioned chlorinated polyolefin (B) has a melt flow rate of 1.5 g / 10 minutes or less and a brittle temperature of -60°C or less measured at 180°C and a load of 21.6 kg.

[0035] [Vinyl chloride polymer (A)]

[0036] The vinyl chloride polymer (A) is a homopolymer or copolymer of vinyl chloride. Examples thereof include vinyl chloride homopolymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-ethylene copolymers, vinyl chloride-ethylene-vinyl acetate copolymers, and vinyl chloride-based graft copolymers formed by graft-polymerizing vinyl chloride onto an ethylene-propylene copolymer.

[0037] From the aspect of obtaining sufficiently high mechanical strength when forming the thermoplastic elastomer composition, the value of the average degree of polymerization of the vinyl chloride polymer (A) measured in accordance with JIS K6721-1977 is preferably 300 or more, more preferably 1000 or more, and still more preferably 1200 or more. On the other hand, from the aspect of ease of processing when forming the thermoplastic elastomer composition, the average degree of polymerization of the vinyl chloride polymer (A) is preferably 10000 or less, more preferably 3000 or less, and still more preferably 1400 or less. In a suitable and illustrative mode of the present invention, the average degree of polymerization of the vinyl chloride polymer (A) is 300 to 10000, more preferably 500 to 5000, and still more preferably 1000 to 3000.

[0038] [Chlorinated polyolefin (B)]

[0039] The chlorinated polyolefin (B) used in the present invention is formed by chlorinating a polyolefin. As the chlorinated polyolefin (B), a high molecular weight chlorinated polyolefin is preferred.

[0040] Here, as the physical property related to the molecular weight of the chlorinated polyolefin (B), the melt flow rate can be cited. The melt flow rate of the chlorinated polyolefin (B) used in the present invention is 1.5 g / 10 minutes or less. This melt flow rate is preferably 1.0 g / 10 minutes or less, and more preferably 0.5 g / 10 minutes or less. If the melt flow rate of the chlorinated polyolefin is 1.5 g / 10 minutes or less, the cold resistance (impact embrittlement) is good, and thus it is preferred. On the other hand, the melt flow rate of the chlorinated polyolefin (B) is preferably 0.01 g / 10 minutes or more, and more preferably 0.1 g / 10 minutes or more. The melt flow rate is a value measured under the conditions of a temperature of 180 °C and a load of 21.6 kg in accordance with JIS K7210-1999.

[0041] As another physical property related to the molecular weight of the chlorinated polyolefin (B), the embrittlement temperature can be cited. The embrittlement temperature of the chlorinated polyolefin (B) used in the present invention is -60 °C or less, preferably -65 °C or less, and more preferably -70 °C or less. The embrittlement temperature of the chlorinated polyolefin (B) used in the present invention is preferably -150 °C or more, and more preferably -100 °C or more.

[0042] In addition, the molecular weight of the chlorinated polyolefin (B) can also be evaluated using the viscosity-average molecular weight. Here, in one embodiment of the present invention, the viscosity-average molecular weight of the chlorinated polyolefin (B) used in the present invention is preferably 300,000 or more. This viscosity-average molecular weight is more preferably 320,000 or more, and further preferably 340,000 or more. If the viscosity-average molecular weight of the chlorinated polyolefin (B) is 300,000 or more, a molded product having homogeneous cells can be obtained from the thermoplastic elastomer composition, and thus it is preferred. On the other hand, the viscosity-average molecular weight of the chlorinated polyolefin (B) is preferably 6,000,000 or less, more preferably 2,000,000 or less, and further preferably 500,000 or less. The viscosity-average molecular weight can be measured in accordance with ASTM D4020.

[0043] The type of the polyolefin (hereinafter referred to as "polyolefin (B0)") as the raw material of the chlorinated polyolefin (B) is not particularly limited, and examples thereof include homopolymers of ethylene; homopolymers of α-olefins such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 4-methyl-1-pentene; copolymers of ethylene and α-olefins; copolymers of two or more α-olefins, etc. As the copolymer, it can be any copolymer of a random copolymer or a block copolymer. These polyolefins (B0) can be used alone or in combination of two or more. Among them, homopolymers of ethylene and copolymers of ethylene and propylene, that is, polyethylene and ethylene-propylene copolymers are preferred, and polyethylene is more preferred.

[0044] In addition, when the chlorinated polyolefin (B) has a high molecular weight, the above-mentioned polyolefin (B0) usually has a high molecular weight. In one embodiment of the present invention, the viscosity-average molecular weight of the above-mentioned polyolefin (B0) is preferably 150,000 or more, more preferably 170,000 or more, and further preferably 220,000 or more. If the viscosity-average molecular weight of the polyolefin (B0) is above the above lower limit value, especially 150,000 or more, a molded article having homogeneous cells can be obtained from the thermoplastic elastomer composition, which is thus preferred. On the other hand, the viscosity-average molecular weight of the above-mentioned polyolefin (B0) is preferably 6,000,000 or less, more preferably 2,000,000 or less, and further preferably 500,000 or less. The above viscosity-average molecular weight is measured by the method described in the examples. It should be noted that a polyolefin having a viscosity-average molecular weight of 300,000 or more is sometimes referred to as a high molecular weight polyolefin.

[0045] The above-mentioned polyolefin (B0) can be used alone or in combination of two or more.

[0046] The chlorinated polyolefin (B) used in the present invention can be obtained by chlorinating the above-mentioned polyolefin (B0). Here, the method for chlorinating the above-mentioned polyolefin (B0) is not particularly limited, and known methods can be adopted. As known methods, an aqueous suspension method and a gas phase method can be mentioned. Among them, the aqueous suspension method is preferred. Specifically, the manufacturing method using the aqueous suspension method can utilize the methods described in Japanese Patent Laid-Open No. 54-124096, Japanese Patent Laid-Open No. 4-106109, etc. Taking the case of manufacturing chlorinated polyethylene from polyethylene as an example, as an example of the manufacturing method of chlorinated polyethylene using the aqueous suspension method, the following method can be mentioned: Chlorine is introduced into a suspension obtained by mixing polyethylene powder and a surfactant in water and suspending the polyethylene powder in water, or a solution obtained by dissolving polyethylene in a solvent, and chlorination is carried out by heating or ultraviolet irradiation.

[0047] The above-mentioned chlorinated polyolefin (B) is preferably chlorinated polyethylene and chlorinated ethylene-propylene copolymer, more preferably chlorinated polyethylene, and further preferably chlorinated polyethylene obtained by the aqueous suspension method.

[0048] The chlorinated polyolefin (B) used in the present invention can be used alone or in combination of two or more.

[0049] In addition, the chlorine content of the chlorinated polyolefin (B) is preferably 5 to 50% by mass, more preferably 20 to 50% by mass, still more preferably 25 to 45% by mass, and particularly preferably 30 to 40% by mass. When the chlorine content of the chlorinated polyolefin (B) is at least the above lower limit value, especially at least 5% by mass, a rubber elastomer can be obtained in such a manner that no crystals of the raw material polyethylene remain, and the cold resistance can be improved, which is thus preferred. When the chlorine content of the chlorinated polyolefin (B) is at most the above upper limit value, especially at most 50% by mass, the cohesive force of chlorine is small, the hardness does not increase, an elastomer can be obtained, and the cold resistance can be improved, which is thus preferred.

[0050] Furthermore, the heat of crystal melting of the chlorinated polyolefin (B) used in the present invention, obtained by the DSC method, is preferably 3 to 90 J / g, more preferably 5 to 60 J / g, still more preferably 10 to 30 J / g. If the heat of crystal melting is at least 3 J / g, crystals are present, and thus adhesiveness can be obtained in the molded article, which is thus preferred. If the heat of crystal melting is at most 90 J / g, good flexibility can be obtained, which is thus preferred.

[0051] The above DSC method is a method for quantifying the heat change that occurs when a sample is heated and cooled at a constant rate in terms of thermal energy, and is also known as the Differential Scanning Calorimetry method. The heat of crystal melting can be determined based on the value obtained by calculating the heat of crystal melting from the area of the crystallization peak by the DSC method. The actual measurement can be carried out as follows: The precisely weighed chlorinated polyolefin is placed in a DSC measuring device and heated at a heating rate of 10 °C / minute in the temperature range of 30 to 170 °C.

[0052] The chlorinated polyolefin (B) used in the present invention can be amorphous or crystalline. The amorphousness in the present invention means that the heat of crystal melting is 2.0 J / g or less, and the heat of crystal melting is measured by heating the measurement sample from room temperature at a heating rate of 10 °C per minute using a differential scanning calorimeter.

[0053] With respect to 100 parts by mass of the vinyl chloride polymer (A), the amount of the chlorinated polyolefin (B) used in the present invention is preferably 1.0 part by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more. If the amount of the chlorinated polyolefin (B) used is above the above lower limit, the properties of the chlorinated polyolefin as a rubber elastomer can be fully exhibited, and the cold resistance when producing the thermoplastic elastomer composition can be improved, so it is preferred. With respect to 100 parts by mass of the vinyl chloride polymer (A), the amount of the chlorinated polyolefin (B) used is preferably 100.0 parts by mass or less, more preferably 80 parts by mass or less, and still more preferably 40 parts by mass or less. If the amount of the chlorinated polyolefin (B) used is below the above upper limit, when producing the thermoplastic elastomer composition, the change in hardness compared with the corresponding composition without adding the chlorinated polyolefin (B) is small, so it is preferred.

[0054] <Plasticizer (C)>

[0055] As the plasticizer (C), plasticizers commonly used for polyvinyl chloride can be used. As examples of the plasticizer (C) that can be used in the present invention, specifically, the following can be cited:

[0056] Phthalic acid diesters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di-2-ethylhexyl phthalate (commonly referred to as dioctyl phthalate, DOP), diisononyl phthalate (hereinafter also referred to as "DINP"), octyl decyl phthalate, diisodecyl phthalate, ditridecyl phthalate, butyl benzyl phthalate, dicyclohexyl phthalate, etc., and tetrahydrophthalic acid diesters such as di-n-octyl tetrahydrophthalate, di-2-ethylhexyl tetrahydrophthalate, diisodecyl tetrahydrophthalate, etc.;

[0057] Aliphatic monocarboxylic acid ester plasticizers such as butyl oleate and glycerol monooleate;

[0058] Aliphatic dicarboxylic acid ester plasticizers such as dibutyl adipate, di-n-hexyl adipate, di-2-ethylhexyl adipate, diisononyl adipate, diisodecyl adipate, di-n-alkyl adipate, bis(butoxyethoxyethyl) adipate, di-2-ethylhexyl azelate, di-n-hexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate, etc.;

[0059] Trimellitic acid trialkyl esters such as trioctyl trimellitate (hereinafter also referred to as "TOTM"), tris(2-ethylhexyl) trimellitate, trioctyl trimellitate, etc., and trimellitic acid ester plasticizers;

[0060] Polyester plasticizers formed from polymers of dibasic acids such as adipic acid, azelaic acid, sebacic acid, phthalic acid, etc. and diols, glycerols, and monobasic acids, etc., such as adipic acid - propylene glycol series, adipic acid - 1,3 - butanediol series, etc.;

[0061] Phosphate plasticizers such as triethyl phosphate, tributyl phosphate, tris(2 - ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trichloroethyl phosphate, tris(dichloropropyl) phosphate, tributoxyethyl phosphate, tris(2 - chloro - 1 - methylethyl) phosphate, octyldiphenyl phosphate, tris(isopropylphenyl) phosphate, tolyldiphenyl phosphate, etc.; and,

[0062] Chlorinated paraffin plasticizers, etc.

[0063] Among them, phthalate plasticizers are preferred, and diisononyl phthalate is more preferred.

[0064] These plasticizers (C) can be used alone or in combination of two or more. Relative to 100 parts by mass of the above - mentioned vinyl chloride polymer (A), the addition amount can be 1.0 to 110.0 parts by mass, preferably 20.0 to 90.0 parts by mass, and more preferably 30.0 to 50.0 parts by mass. If the addition amount is within this range, appropriate plasticization can be achieved, so it is preferred. Here, when the addition amount of plasticizer (C) is excessively increased, sufficient high hardness and tensile strength may not be obtained when forming a molded article. Therefore, in order to obtain sufficient high hardness, etc. when the thermoplastic elastomer composition of the present invention is used for applications such as sheets and wirings, it is preferred to make the amount of plasticizer (C) relatively small to some extent (for example, 1.0 to 20.0 parts by mass relative to 100 parts by mass of the above - mentioned vinyl chloride polymer (A)).

[0065] Relative to 100 parts by mass of the above - mentioned chlorinated polyolefin (B), the addition amount of plasticizer (C) can preferably be 1.0 to 400.0 parts by mass, particularly more preferably 20.0 to 300.0 parts by mass, and further preferably 30.0 to 250.0 parts by mass. If the addition amount of plasticizer (C) is within this range, appropriate plasticization can be achieved, so it is preferred.

[0066] <Other components>

[0067] As described above, the thermoplastic elastomer composition of the present invention contains the above-mentioned vinyl chloride polymer (A), the above-mentioned chlorinated polyolefin (B), and the above-mentioned plasticizer (C). Here, in one embodiment of the present invention, the thermoplastic elastomer composition of the present invention is composed of the above-mentioned vinyl chloride polymer (A), the above-mentioned chlorinated polyolefin (B), and the above-mentioned plasticizer (C). However, the thermoplastic elastomer composition of the present invention is not limited to such an embodiment, and in addition to these components, other components that do not belong to any of the above-mentioned vinyl chloride polymer (A), the above-mentioned chlorinated polyolefin (B), and the above-mentioned plasticizer (C) (hereinafter also referred to as "other components") may be further contained.

[0068] As the "other components" that can be contained in the thermoplastic elastomer composition of the present invention, various compounding agents commonly used in the art can be cited, such as fillers, stabilizers, lubricants, pigments, flame retardants, ultraviolet absorbers, light stabilizers, foaming agents, and the like.

[0069] The filler that can be contained in the thermoplastic elastomer composition of the present invention is not particularly limited. As specific examples thereof, fillers that can be compounded with distinct colors such as calcium carbonate, talc, mica, clay, silica, aluminum hydroxide, magnesium hydroxide, and carbon black can be cited. In addition, these fillers may also be fillers that have been surface-treated for the purpose of antistatic properties or the like.

[0070] With respect to a total of 100 parts by mass of the above-mentioned vinyl chloride polymer (A) and the above-mentioned chlorinated polyolefin (B), the addition amount of the above-mentioned filler is preferably 1 to 500 parts by mass, more preferably 10 to 100 parts by mass.

[0071] As examples of the above-mentioned stabilizer, metal soaps, organotin compounds, inorganic acid salts, composite stabilizers, and hydrotalcite can be cited. With respect to a total of 100 parts by mass of the above-mentioned vinyl chloride polymer (A) and the above-mentioned chlorinated polyolefin (B), the addition amount of the above-mentioned stabilizer is preferably 0.5 to 5.0 parts by mass, more preferably 1.0 to 3.0 parts by mass.

[0072] As examples of the above-mentioned lubricant, fatty acid metal soaps, ester compounds, hydrocarbon compounds, fatty acid compounds, and higher alcohols can be cited. As examples of the above-mentioned pigment, carbon black, titanium oxide, and organic pigments can be cited. As examples of the above-mentioned flame retardant, antimony trioxide, halogen-based flame retardants, phosphorus-based flame retardants, and composite flame retardants can be cited.

[0073] As an example of the above light stabilizer, a hindered amine-based light stabilizer can be used. Among them, as an example of a low molecular weight type light stabilizer, bis((2,2,6,6-tetramethyl-1(octyloxy)-4-piperidinyl)-4-yl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, a mixture of bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidinyl sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, tetra(2,2,6,6-tetramethyl-4-piperidinyl) 1,2,3,4-butane tetracarboxylate, tetra(1,2,2,6,6-pentamethyl-4-piperidinyl) 1,2,3,4-butane tetracarboxylate, a mixture of 2,2,6,6-tetramethyl-4-piperidinyl 1,2,3,4-butane tetracarboxylate and tridecyl 1,2,3,4-butane tetracarboxylate, a mixture of 1,2,2,6,6-pentamethyl-4-piperidinyl 1,2,3,4-butane tetracarboxylate and tridecyl 1,2,3,4-butane tetracarboxylate, etc. can be cited.

[0074] As examples of the foaming agent, azo compounds, nitroso compounds, and sulfonyl hydrazides can be cited.

[0075] [Method for manufacturing a thermoplastic elastomer composition]

[0076] The thermoplastic elastomer composition of the present invention can be obtained by kneading the above vinyl chloride polymer (A), the above chlorinated polyolefin (B), the above plasticizer (C), and optionally the above "other components" using a method commonly used in the industry (such as a roll mill, Banbury mixer, kneader, extruder, etc.).

[0077] The above thermoplastic elastomer composition is suitable for use in a molded article containing the same.

[0078] [Molded article]

[0079] One embodiment of the present invention is a molded article containing the above thermoplastic elastomer composition. As a suitable usage mode of the molded article, it is a cable coating material, a sheet, or a film.

[0080] In addition, as other suitable usage modes of the molded article, they are a pipe, a gasket, or an O-ring.

[0081] Here, in one aspect of the present invention, the above-mentioned molded body only contains the above-mentioned thermoplastic elastomer composition. However, the above-mentioned molded body is not limited to the molded body that only contains the above-mentioned thermoplastic elastomer composition, and it may further contain materials other than the above-mentioned thermoplastic elastomer composition in addition to the above-mentioned thermoplastic elastomer composition. For example, it may contain one or more members made of the above-mentioned thermoplastic elastomer composition and one or more members made of materials other than the above-mentioned thermoplastic elastomer composition. In addition, it may also contain a member having a mixed structure of the above-mentioned thermoplastic elastomer composition and a material other than the above-mentioned thermoplastic elastomer composition. Here, examples of the material other than the above-mentioned thermoplastic elastomer composition include metals, various resins, etc.

[0082] These molded bodies can be appropriately obtained from the above-mentioned thermoplastic elastomer composition by various molding methods known in the past.

[0083] Examples

[0084] Hereinafter, the present invention will be described by way of examples and comparative examples, but the present invention is not limited by any of the following examples.

[0085] [Methods for Measuring Various Physical Properties]

[0086] <Chlorine Content>

[0087] The chlorine content was measured by the following method. In a glass tube, the sample was heated and burned using the flame of a gas burner to carry out dehydrochlorination decomposition, and the generated hydrochloric acid gas was absorbed by distilled water and quantitatively determined by neutralization titration using a 0.1 mol / 1 sodium hydroxide equivalent solution.

[0088] <Melt Flow Rate>

[0089] The melt flow rate (hereinafter referred to as "MFR") was measured in accordance with JIS K7210-1999.

[0090] Here, the measurement conditions for the melt flow rate were set to a temperature of 180 °C and a load of 21.6 kg.

[0091] <De Mattia Flexing Test>

[0092] It was carried out by the method specified in JIS K6260:2017.

[0093] <Brittleness Temperature>

[0094] The brittleness temperature was measured by the method specified in Method B of JIS K6261-2:2017.

[0095] [Example 1]

[0096] Under solvent-free conditions, 100 parts by mass of a vinyl chloride resin (manufactured by Shin-Etsu Chemical Co., Ltd., TK-1300) as a vinyl chloride polymer (A), 70 parts by mass of diisononyl phthalate (manufactured by Shin Nippon Rika Co., Ltd., Sanso Sizer DINP (hereinafter sometimes referred to as "DINP")) as a plasticizer (C), 3 parts by mass of barium stearate as a stabilizer, and 10 parts by mass of calcium carbonate as a filler were mixed using a Henschel mixer, and the resulting mixture was discharged from the Henschel mixer at 100 to 110°C.

[0097] Then, 50 parts by mass of chlorinated polyethylene (manufactured by Showa Denko K.K., Elaslen (registered trademark) 301MB) as a chlorinated polyolefin (B) was added to the mixture, and manual blending was carried out at room temperature (10 to 50°C). Then, it was kneaded for 3 minutes using a roll mill at 170°C, and sheet output was performed.

[0098] Then, in a compression molding machine, after preheating at 170°C for 3 minutes, pressure was applied and cooled for 3 minutes, and pressure was applied for 3 minutes to form a smooth sheet with a thickness of 2 mm.

[0099] [Examples 2 to 7 and Comparative Examples 1 to 6]

[0100] In Examples 2 to 7 and Comparative Examples 1 to 6, the compounding amounts of the vinyl chloride resin, chlorinated polyethylene, plasticizer, and stabilizer were changed to the amounts described in Tables 1-1 and 1-2 below, and otherwise, the same procedure as in Example 1 was carried out. Here, various Elaslen (registered trademark) described in Tables 1-1, 1-2, and 2 below are chlorinated polyethylene manufactured by Showa Denko K.K.

[0101] [Table 1-1]

[0102]

[0103] [Table 1-2]

[0104]

[0105] The physical properties of the chlorinated polyethylene used in each example and each comparative example are shown in Table 2 below. Here, the "chlorine content", "MFR", and "brittleness temperature" described in Table 2 below are the values measured by the methods described in the "Measurement methods of various physical properties" for "chlorine content", "melt flow rate", and "brittleness temperature", respectively.

[0106] [Table 2]

[0107]

[0108] The evaluation results of the sheets obtained for each example and each comparative example are shown in Table 1-1 and Table 1-2 above. Here, the values shown in the item of "low-temperature bendability" in Table 1-1 and Table 1-2 above are the values measured by the method described in the "Demicia bend test" described in the "measurement methods of various physical properties" above.

Claims

1. A thermoplastic elastomer composition comprising a vinyl chloride polymer (A), a chlorinated polyolefin (B), and a plasticizer (C), wherein the chlorinated polyolefin (B) has a melt flow rate of 1.5 g / 10 min or less and a embrittlement temperature of -60°C or less as measured at 180°C under a load of 21.6 kg.

2. The thermoplastic elastomer composition according to claim 1, wherein the chlorinated polyolefin (B) is chlorinated polyethylene.

3. The thermoplastic elastomer composition according to claim 1 or 2, wherein the chlorinated polyolefin (B) has a chlorine content of 5 to 50% by mass.

4. The thermoplastic elastomer composition according to claim 1 or 2, wherein the vinyl chloride polymer (A) has an average degree of polymerization of 300 to 10,000.

5. The thermoplastic elastomer composition according to claim 1 or 2, wherein the plasticizer (C) is a phthalate plasticizer.

6. The thermoplastic elastomer composition according to claim 1 or 2, wherein the chlorinated polyolefin (B) is 1.0 to 80.0 parts by mass relative to 100 parts by mass of the vinyl chloride polymer (A).

7. The thermoplastic elastomer composition according to claim 1 or 2, wherein the plasticizer (C) is 1.0 to 110.0 parts by mass relative to 100 parts by mass of the vinyl chloride polymer (A).

8. The thermoplastic elastomer composition according to claim 1 or 2, wherein the chlorinated polyolefin (B) has a melt flow rate of 0.01 g / 10 min or more as measured at 180°C under a load of 21.6 kg.

9. The thermoplastic elastomer composition according to claim 1 or 2, wherein the chlorinated polyolefin (B) has an embrittlement temperature of -150°C or more.

10. A molded article comprising the thermoplastic elastomer composition according to claim 1 or 2.

11. A cable coating material, sheet or film comprising the thermoplastic elastomer composition according to claim 1 or 2.

12. A tube, gasket or sealing ring comprising the thermoplastic elastomer composition according to claim 1 or 2.

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