Composition for thermoplastic material

Abstract

To provide a thermoplastic material which maintains ordinary physical properties, and has low hardness and excellent tensile permanent distortion property.SOLUTION: There are provided a composition for a thermoplastic material which contains an acrylic copolymer (A) containing 45 to 89.5 mass% of a constitutional unit (a) derived from alkyl acrylate and / or a constitutional unit derived from alkoxyalkyl acrylate, 10 to 50 mass% of a constitutional unit (b) derived from alkyl methacrylate having an alkyl group having 3 to 16 carbon atoms, 0.5 to 5.5 mass% of a constitutional unit (c) derived from a crosslinkable monomer, a thermoplastic polyester resin (B), and a thermoplastic polyester elastomer (C) which has flexural elastic modulus of 30 MPa or more and has a polyester unit as a soft segment; and a thermoplastic material which is obtained from the composition for the thermoplastic material.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a composition for a thermoplastic material, a thermoplastic material, and a method for producing the same, which maintain normal physical properties and have low hardness and excellent tensile permanent strain properties for a thermoplastic material.

Background Art

[0002] Generally, acrylic rubber is excellent in heat resistance, oil resistance, etc., and is widely used in automotive parts, sealing materials, packings, tubes, etc. Conventionally, from the viewpoint of heat resistance, acrylic rubber has been used as a cross-linked product through a vulcanization process.

[0003] In recent years, thermoplastic elastomers, which are soft materials having rubber elasticity, have been frequently used as materials to replace vulcanized rubber in fields such as automotive parts and home appliance parts. In particular, in fields where vulcanized rubber has been conventionally used, it is necessary that mechanical properties such as low hardness and excellent permanent strain properties are stable.

[0004] As a thermoplastic elastomer having excellent sealing properties, there is an acrylic rubber containing at least one selected from an alkyl acrylate monomer or an alkoxyalkyl acrylate monomer and a monomer having an epoxy group, which is a cross-linkable group, in a side chain, a thermoplastic polyester, and a cross-linking agent. Thereby, a thermoplastic elastomer excellent in mechanical strength and permanent strain properties has been proposed (see Patent Document 1). Patent Document 2 proposes a thermoplastic elastomer composition containing (a) a carboxyl group-containing acrylic rubber, (b) a polyester-based polymer, and (c) an epoxy group-containing polymer. However, in any of the prior documents, although they are excellent in mechanical strength and permanent strain properties, there is a problem that a composition having low hardness cannot be obtained, or when the acrylic rubber composition is increased to obtain it, the processability is poor.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] The problem of the present invention is to provide a composition for a thermoplastic material and a thermoplastic material obtained from the composition for a thermoplastic material, which maintain normal physical properties and have a thermoplastic material having low hardness and excellent tensile permanent strain properties.

Means for Solving the Problems

[0007] The present inventors have found that a constituent unit derived from an alkyl acrylate and / or a constituent unit derived from an alkoxyalkyl acrylate (a) 45 to 89.5% by mass, a constituent unit derived from an alkyl methacrylate having an alkyl group having 3 to 16 carbon atoms (b) 10 to 50% by mass, a constituent unit derived from a crosslinkable monomer (c) 0.5 to 5.5% by mass, an acrylic copolymer (A), a thermoplastic polyester resin (B), and a thermoplastic polyester elastomer (C) having a flexural modulus of 30 MPa or more and having a polyester unit as a soft segment, and a thermoplastic material obtained from the composition for a thermoplastic material solve the above problems, and have completed the present invention.

[0008] That is, the present invention relates to the following. Constituent unit derived from an alkyl acrylate and / or a constituent unit derived from an alkoxyalkyl acrylate (a) 45 to 89.5% by mass, constituent unit derived from an alkyl methacrylate having an alkyl group with 3 to 16 carbon atoms (b) 10 to 50% by mass, constituent unit derived from a crosslinkable monomer (c) 0.5 to 5.5% by mass, an acrylic copolymer (A), a thermoplastic polyester resin (B), and a thermoplastic polyester elastomer (C) having a flexural modulus of 30 MPa or more and having a polyester unit as a soft segment, a composition for a thermoplastic material. The composition for a thermoplastic material according to Item 1, which contains 5 to 95 parts by mass in total of the thermoplastic polyester resin (B) and the thermoplastic polyester elastomer (C) with respect to 100 parts by mass of the acrylic copolymer. The composition for a thermoplastic material according to Item 1, further containing a crosslinking agent (D) for crosslinking the acrylic copolymer. A thermoplastic material obtained from the composition for a thermoplastic material according to any one of Items 1 to 3. The thermoplastic material according to Claim 4, which is a thermoplastic elastomer. A method for producing a thermoplastic material, in which the acrylic copolymer is crosslinked while kneading the composition for a thermoplastic material according to any one of Items 1 to 3 in a kneader.

Advantages of the Invention

[0009] The thermoplastic material of the present invention maintains its normal physical properties and has low hardness and excellent tensile permanent strain properties, so it is useful as automotive parts, sealing materials, packings, tubes, etc.

Modes for Carrying Out the Invention

[0010] The present invention will be described in detail below.

[0011] The composition for a thermoplastic material of the present invention contains 45 to 89.5% by mass of a structural unit derived from an alkyl acrylate and / or a structural unit derived from an alkoxyalkyl acrylate (a), 10 to 50% by mass of a structural unit derived from an alkyl methacrylate having an alkyl group with 3 to 16 carbon atoms (b), 0.5 to 5.5% by mass of a structural unit derived from a crosslinkable monomer (c), an acrylic copolymer (A), a thermoplastic polyester resin (B), and a thermoplastic polyester elastomer (C) having a flexural modulus of 30 MPa or more and having a polyester unit as a soft segment. The thermoplastic material obtained from the composition for a thermoplastic material of the present invention maintains normal physical properties and has low hardness and excellent tensile permanent set.

[0012] In the present invention, the reason for obtaining the above effects is not clear, but it is presumed as follows. The acrylic copolymer (A) containing a specific structural unit, the thermoplastic polyester resin (B), and the thermoplastic polyester elastomer (C) having a flexural modulus of 30 MPa or more and having a polyester unit as a soft segment have high compatibility, and a composition for a thermoplastic material in which the acrylic copolymer (A) is well dispersed in the thermoplastic polyester resin (B) and the thermoplastic polyester elastomer (C) having a flexural modulus of 30 MPa or more and having a polyester unit as a soft segment is obtained. Then, the thermoplastic material obtained by crosslinking the composition for a thermoplastic material has the crosslinked acrylic copolymer (A) well dispersed in the thermoplastic polyester resin (B) and the thermoplastic polyester elastomer (C) having a flexural modulus of 30 MPa or more and having a polyester unit as a soft segment, maintains normal physical properties, and has low hardness and excellent tensile permanent set properties.

[0013] In this specification, the composition for a thermoplastic material means a composition before processing for a thermoplastic material containing an acrylic copolymer (A), a thermoplastic polyester resin (B), and a thermoplastic polyester elastomer (C) having a flexural modulus of 30 MPa or more and having a polyester unit as a soft segment. The processing is preferably crosslinking (that is, the composition for a thermoplastic material is a composition before crosslinking for a thermoplastic material containing an acrylic copolymer (A), a thermoplastic polyester resin (B), and a thermoplastic polyester elastomer (C) having a flexural modulus of 30 MPa or more and having a polyester unit as a soft segment), and the thermoplastic material is preferably a composition after crosslinking. Here, the method of crosslinking is not particularly limited. However, especially when dynamic crosslinking is performed, the crosslinked acrylic copolymer (A) is dispersed in the thermoplastic polyester resin (B) and the thermoplastic polyester elastomer (C) having a flexural modulus of 30 MPa or more and having a polyester unit as a soft segment, resulting in a state different from that of a normal crosslinked product. Therefore, it can also be described as a thermoplastic material composition that means a composition after crosslinking without describing it as a crosslinked product. Further, the composition for a thermoplastic material can be described as a composition for a thermoplastic elastomer, and the thermoplastic material can be described as a thermoplastic elastomer. In this specification, the polymer means a polymer, and examples include an acrylic copolymer, a thermoplastic polyester resin, and a thermoplastic polyester elastomer.

[0014] Next, the acrylic copolymer (acrylic rubber) (A) in the present invention will be described. The acrylic copolymer (A) of the present invention contains 45 to 89.5% by mass of a structural unit derived from an alkyl acrylate and / or a structural unit derived from an alkoxyalkyl acrylate (a), 10 to 50% by mass of a structural unit derived from an alkyl methacrylate having an alkyl group having 3 to 16 carbon atoms (b), and 0.5 to 5.5% by mass of a structural unit derived from a crosslinkable monomer (c). The acrylic copolymer (A) may be used alone or in combination of two or more. Note that the ratio of each of these constituent units is preferably the ratio when the total amount of the acrylic copolymer (A) is 100% by mass. The acrylic copolymer (A) may contain constituent units other than the constituent unit (a), the constituent unit (b), and the constituent unit (c), and may further contain a constituent unit (d) derived from a polyfunctional (meth)acrylate monomer. However, in 100% by mass of the acrylic copolymer (A), the total content of the constituent unit (a), the constituent unit (b), the constituent unit (c), and the constituent unit (d) is, for example, 55.5% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, particularly preferably 90% by mass or more, may be 95% by mass or more, may be 98% by mass or more, or may be 100% by mass.

[0015] The alkyl acrylate preferably has an alkyl group with 1 to 8 carbon atoms, more preferably 2 to 4 carbon atoms. The alkoxyalkyl acrylate preferably has an alkoxyalkyl group with 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms. The alkyl acrylate and the alkoxyalkyl acrylate may be used alone or in combination of two or more.

[0016] Specific examples of the constituent unit derived from the alkyl acrylate include constituent units derived from acrylic esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, etc., and are preferably constituent units derived from ethyl acrylate and n-butyl acrylate. Specific examples of the structural unit derived from an alkoxyalkyl acrylate include structural units derived from acrylate esters such as methoxymethyl acrylate, methoxyethyl acrylate, ethoxymethyl acrylate, 2-ethoxyethyl acrylate, 2-propoxyethyl acrylate, 2-butoxyethyl acrylate, 2-methoxypropyl acrylate, 2-ethoxypropyl acrylate, 3-methoxypropyl acrylate, 3-ethoxypropyl acrylate, 4-methoxybutyl acrylate, and 4-ethoxybutyl acrylate. It is preferably a structural unit derived from methoxyethyl acrylate.

[0017] In the acrylic copolymer (A) of the present invention, the content of the structural unit derived from an alkyl acrylate and / or the structural unit (a) derived from an alkoxyalkyl acrylate is 45 to 89.5% by mass, preferably 50 to 89.5% by mass, and more preferably 60 to 89.5% by mass in 100% by mass of the acrylic copolymer (A). When the structural unit (a) is within the above range, the effects of the present invention tend to be more favorably exhibited, and it is preferable in terms of cold resistance and oil resistance. When containing two or more types of structural units (a), the content of the structural unit (a) means the total content. The same applies to other descriptions.

[0018] In the acrylic copolymer (A) of the present invention, in the structural unit derived from an alkyl acrylate and / or the structural unit (a) derived from an alkoxyalkyl acrylate, it is preferable to contain the structural unit derived from an alkyl acrylate, and it is more preferable to contain both the structural unit (a1) derived from an acrylate having an alkyl group with 1 to 3 carbon atoms and the structural unit (a2) derived from an acrylate having an alkyl group with 4 to 8 carbon atoms. The mass ratio of the structural unit (a1) to the structural unit (a2) is preferably 10 to 90:90 to 10 (i.e., (a1):(a2) = 10:90 to 90:10), more preferably 20:80 to 80:20. Even more preferably, it is 30:70 to 70:30, and most preferably 40:60 to 60:40.

[0019] In the acrylic copolymer (A) of the present invention, in 100% by mass of the structural unit derived from an alkyl acrylate and / or the structural unit (a) derived from an alkoxyalkyl acrylate, the content of the structural unit derived from an alkyl acrylate is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, most preferably 90% by mass or more, and even most preferably 95% by mass or more, and it may be 100% by mass.

[0020] The alkyl methacrylate having an alkyl group with 3 to 16 carbon atoms (preferably 4 to 16 carbon atoms) means that the number of carbon atoms in the alkyl group of the alkyl methacrylate is 3 to 16 (preferably 4 to 16). Examples of the structural unit (b) derived from the alkyl methacrylate include structural units derived from alkyl methacrylates such as n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, n-decyl methacrylate, isodecyl methacrylate, n-dodecyl methacrylate, n-lauryl methacrylate, and n-octadecyl methacrylate. Among them, the structural unit derived from an alkyl methacrylate selected from n-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, and n-lauryl methacrylate is preferable. More preferably, the structural unit (b) is derived from an alkyl methacrylate having 4 or more and 9 or less carbon atoms in the alkyl group (more preferably 8 or less, even more preferably 7 or less, and particularly preferably 6 or less). For example, the structural unit derived from n-butyl methacrylate, n-hexyl methacrylate, or 2-ethylhexyl methacrylate is more preferable. These may be structural units derived from a single alkyl methacrylate or two or more alkyl methacrylates.

[0021] In the acrylic copolymer (A) of the present invention, the content of the structural unit (b) derived from an alkyl methacrylate having an alkyl group with 3 to 16 carbon atoms is 10 to 50% by mass, preferably 10 to 40% by mass, and more preferably 10.5 to 30% by mass in 100% by mass of the acrylic copolymer (A). Also, 10 to 48% by mass, 10 to 38% by mass, etc. are also preferred embodiments. When the structural unit (b) is within the above range, the effects of the present invention tend to be more favorably exhibited, and it is preferable in terms of heat resistance, oil resistance, and cold resistance.

[0022] The constituent unit (c) derived from the crosslinkable monomer is not particularly limited as long as it is a constituent unit derived from a crosslinkable monomer having a crosslinking group capable of reacting with a crosslinking agent. Examples thereof include constituent units derived from crosslinkable monomers having any of a carboxy group, an epoxy group, and a halogen group. However, a constituent unit derived from a crosslinkable monomer having a halogen group or a carboxy group is preferable. The crosslinkable monomer having a crosslinking group capable of reacting with a crosslinking agent may be used alone or in combination of two or more.

[0023] Examples of the constituent unit derived from a crosslinkable monomer having an epoxy group as a crosslinking group include constituent units derived from epoxy group-containing (meth)acrylic acid esters such as glycidyl (meth)acrylate, constituent units derived from epoxy group-containing styrenes such as p-vinylbenzyl glycidyl ether, allyl glycidyl ether and vinyl glycidyl ether, 3,4-epoxy-1-pentene, 3,4-epoxy-1-butene, 4,5-epoxy-2-pentene, 4-vinylcyclohexyl glycidyl ether, cyclohexenylmethyl glycidyl ether, 3,4-epoxy-1-vinylcyclohexene, and constituent units derived from epoxy group-containing ethers such as allylphenyl glycidyl ether. These can be used alone or in combination of two or more.

[0024] Examples of the constituent unit derived from a crosslinkable monomer having a halogen group as a crosslinking group include constituent units derived from 2-chloroethyl vinyl ether, 2-chloroethyl acrylate, vinylbenzyl chloride, vinyl monochloroacetate, allyl chloroacetate, and the like. These can be used alone or in combination of two or more. As the constituent unit derived from a crosslinkable monomer having a halogen group, 2-chloroethyl vinyl ether and vinyl monochloroacetate are preferable, and vinyl monochloroacetate is more preferable.

[0025] Examples of the structural unit derived from a crosslinkable monomer having a carboxy group include structural units derived from ethylenically unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, 2-pentenoic acid, and cinnamic acid; structural units derived from ethylenically unsaturated dicarboxylic acids such as fumaric acid, maleic acid, and itaconic acid; structural units derived from monoalkyl esters of ethylenically unsaturated dicarboxylic acids such as monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, monobutyl fumarate, monohexyl fumarate, monooctyl fumarate, monomethyl maleate, monoethyl maleate, monopropyl maleate, monobutyl maleate, monopentyl maleate, monodecyl maleate, monomethyl itaconate, monoethyl itaconate, monopropyl itaconate, and monobutyl itaconate. These can be used alone or in combination of two or more. As the structural unit derived from a crosslinkable monomer having a carboxy group, a monoester of an ethylenically unsaturated dicarboxylic acid is preferable, a monoalkyl ester of fumaric acid is more preferable, and a monoalkyl ester of fumaric acid having an alkyl group with 1 to 4 carbon atoms is most preferable.

[0026] The content of the structural unit (c) derived from the crosslinkable monomer in the acrylic copolymer (A) of the present invention is 0.5 to 5.5% by mass, preferably 0.6 to 5% by mass, and more preferably 0.7 to 3% by mass in 100% by mass of the acrylic copolymer (A). When the structural unit (c) derived from the crosslinkable monomer (preferably the structural unit derived from a crosslinkable monomer having a halogen group or a carboxy group) is within the above range, the effects of the present invention tend to be more favorably exhibited, and it is preferable in terms of physical properties such as strength. When the acrylic copolymer (A) contains the structural unit (d) derived from a polyfunctional (meth)acrylate monomer, it may be 0.45 to 5.5% by mass, may be 0.55 to 5% by mass, or may be 0.65 to 3% by mass.

[0027] In the acrylic copolymer (A) of the present invention, it may contain a structural unit (d) derived from a polyfunctional (meth)acrylate monomer. The polyfunctional (meth)acrylate monomer refers to a monomer having a plurality of (meth)acryloyl groups. Examples of the polyfunctional (meth)acrylate monomer include difunctional (meth)acrylates such as ethylene glycol di(meth)acrylate and 1,6-hexanediol di(meth)acrylate, trimethylolpropane (meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate; trifunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, and dipentaerythritol tetra(meth)acrylate; pentafunctional (meth)acrylates such as dipentaerythritol penta(meth)acrylate and ditrimethylolpropane penta(meth)acrylate; and hexafunctional (meth)acrylates such as dipentaerythritol hexa(meth)acrylate and ditrimethylolpropane hexa(meth)acrylate.

[0028] The content of the structural unit (d) derived from the polyfunctional (meth)acrylate monomer in the acrylic copolymer (A) of the present invention is 0.001 to 1% by mass, preferably 0.005 to 3% by mass, and more preferably 0.01 to 1% by mass in 100% by mass of the acrylic copolymer (A).

[0029] Furthermore, the acrylic copolymer (A) of the present invention may contain, in addition to the above-mentioned structural units (a) to (d), structural units derived from other monomers copolymerizable therewith. Examples of the other structural units include structural units derived from ethylenically unsaturated nitriles, structural units derived from (meth)acrylamide-based monomers, structural units derived from aromatic vinyl-based monomers, structural units derived from conjugated diene-based monomers, structural units derived from non-conjugated dienes, and structural units derived from other olefins. These can be used alone or in combination of two or more.

[0030] Examples of the structural units derived from ethylenically unsaturated nitriles include structural units derived from compounds such as acrylonitrile, methacrylonitrile, α-methoxyacrylonitrile, and vinylidene cyanide.

[0031] Examples of the structural units derived from (meth)acrylamide-based monomers include structural units derived from compounds such as acrylamide, methacrylamide, diacetone acrylamide, diacetone methacrylamide, N-butoxymethyl acrylamide, N-butoxymethyl methacrylamide, N-butoxyethyl acrylamide, N-butoxyethyl methacrylamide, N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide, N-propioxymethyl acrylamide, N-propioxymethyl methacrylamide, N-methyl acrylamide, N-methyl methacrylamide, N,N-dimethyl acrylamide, N,N-dimethyl methacrylamide, N,N-diethyl acrylamide, N,N-diethyl methacrylamide, N-methylol acrylamide, N-methylol methacrylamide, ethacrylamide, crotonamide, cinnamic acid amide, maleic diamide, itaconic diamide, methyl maleic amide, methyl itaconic amide, maleimide, and itaconimide.

[0032] Examples of the structural unit derived from an aromatic vinyl monomer include structural units derived from compounds such as styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, α-fluorostyrene, p-trifluoromethylstyrene, p-methoxystyrene, p-aminostyrene, p-dimethylaminostyrene, p-acetoxystyrene, styrenesulfonic acid or its salt, α-vinylnaphthalene, 1-vinylnaphthalene-4-sulfonic acid or its salt, 2-vinylfluorene, 2-vinylpyridine, 4-vinylpyridine, divinylbenzene, diisopropenylbenzene, vinylbenzyl chloride, etc.

[0033] Examples of the structural unit derived from a conjugated diene monomer include structural units derived from compounds such as 1,3-butadiene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,2-dichloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-neopentyl-1,3-butadiene, 2-bromo-1,3-butadiene, 2-cyano-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, chloroprene, piperylene, etc.

[0034] Examples of the structural unit derived from non-conjugated dienes include structural units derived from compounds of non-conjugated dienes such as 1,4-pentadiene, 1,4-hexadiene, ethylidene norbornene, norbornadiene, dicyclopentadiene, etc.

[0035] Examples of the structural units derived from other olefin monomers include esters such as dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, dicyclopentadienyl ethyl acrylate, and dicyclopentadienyl ethyl methacrylate, and structural units derived from compounds such as ethylene, propylene, vinyl chloride, vinylidene chloride, 1,2-dichloroethylene, vinyl acetate, vinyl fluoride, vinylidene fluoride, 1,2-difluoroethylene, vinyl bromide, vinylidene bromide, 1,2-dibromoethylene, ethyl vinyl ether, and butyl vinyl ether.

[0036] In the acrylic copolymer of the present invention, when containing the structural units derived from these copolymerizable other monomers, the content in all the structural units is preferably 0 to 45% by mass, more preferably 0 to 20% by mass, still more preferably 0 to 10% by mass, and particularly preferably 0 to 5% by mass.

[0037] In the acrylic copolymer (A) of the present invention, the content of its structural units can be determined by the nuclear magnetic resonance spectrum of the obtained polymer.

[0038] <Method for producing acrylic copolymer (A)> The acrylic copolymer used in the present invention can be obtained by polymerizing various monomers respectively. The monomers used may all be commercially available products, and there are no particular restrictions.

[0039] As the form of the polymerization reaction, any of emulsion polymerization method, suspension polymerization method, bulk polymerization method, and solution polymerization method can be used. However, from the viewpoint of ease of controlling the polymerization reaction, etc., it is preferably by the emulsion polymerization method under normal pressure which is generally used as a conventional method for producing acrylic copolymers.

[0040] In the case of polymerization by emulsion polymerization, a usual method may be used, and conventionally known ones such as polymerization initiators, emulsifiers, chain transfer agents, and polymerization terminators can be used.

[0041] The emulsifier used in the present invention is not particularly limited, and nonionic emulsifiers, anionic emulsifiers, etc. generally used in the emulsion polymerization method can be used. Examples of nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alcohol ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene polycyclic phenyl ethers, polyoxyalkylene alkyl ethers, sorbitan fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Examples of anionic emulsifiers include alkylbenzene sulfonates, alkyl sulfate esters, polyoxyethylene alkyl ether sulfate esters, polyoxyalkylene alkyl ether phosphate esters or their salts, fatty acid salts, etc. One or more of these may be used. As the anionic emulsifier, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, triethanolamine dodecyl sulfate, or polyoxyethylene alkyl ether phosphate salt may be used.

[0042] The amount of the emulsifier used in the present invention may be an amount generally used in the emulsion polymerization method. Specifically, it is in the range of 0.01 to 10% by mass, preferably 0.03 to 7% by mass, more preferably 0.05 to 5% by mass, based on the amount of the monomers charged. When a reactive surfactant is used as the monomer component, the addition of an emulsifier is not necessarily required.

[0043] The polymerization initiator used in the present invention is not particularly limited, and polymerization initiators generally used in the emulsion polymerization method can be used. Specific examples thereof include inorganic peroxide-based polymerization initiators typified by persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, 2,2-bis(4,4-di-(t-butylperoxy)cyclohexyl)propane, 1-di-(t-hexylperoxy)cyclohexane, 1,1-di-(t-butylperoxy)cyclohexane, n-butyl 4,4-di-(t-butylperoxy)valerate, 2,2-di(t-butylperoxy)butane, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-butyl cumyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, di(2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, diisobutyryl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, disuccinic peroxide, dibenzoyl peroxide, di(3-methylbenzoyl) peroxide, benzoyl(3-methylbenzoyl) peroxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(4-t-butylcyclohexyl) peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, di-sec-butyl peroxydicarbonate, cumyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxypivalate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxylaurate, t-butyl peroxy-3,5,Organic peroxide-based polymerization initiators (including hydroperoxide-based polymerization initiators) such as 5-trimethylhexanate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxyacetate, t-hexyl peroxybenzoate, t-butyl peroxybenzoate, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, etc., azo-based initiators such as azobisisobutyronitrile, 4-4'-azobis(4-cyanovaleric acid), 2-2'-azobis[2-(2-imidazolin-2-yl)propane], 2-2'-azobis(propane-2-carboxamidine), 2-2'-azobis[N-(2-carboxyethyl)-2-methylpropanamide], 2-2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}, 2-2'-azobis(1-imino-1-pyrrolidino-2-methylpropane) and 2-2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propanamide}, etc. These polymerization initiators may be used alone or in combination of two or more kinds.,

[0044] The amount of the polymerization initiator used in the present invention may be an amount generally used in the emulsion polymerization method. Specifically, it is in the range of 0.001 to 5% by mass, preferably 0.003 to 4% by mass, more preferably 0.005 to 3% by mass, based on the amount of the monomer charged.,

[0045] In addition, organic peroxides and inorganic peroxides as polymerization initiators can be used as redox polymerization initiators by combining them with a reducing agent. The reducing agent used in combination is not particularly limited, but examples include compounds containing metal ions in a reduced state such as ferrous sulfate and cuprous naphthenate, methane compounds such as sodium methanesulfonate, amine compounds such as dimethylaniline, ascorbic acid and its salts, and inorganic salts having reducing properties such as alkali metal salts of sulfurous acid and thiosulfuric acid. These reducing agents can be used alone or in combination of two or more. The amount of the reducing agent used is preferably 0.0003 to 10.0 parts by mass with respect to 100 parts by mass of the charged monomer.

[0046] The chain transfer agent can be used as needed. Specific examples of the chain transfer agent include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and n-stearyl mercaptan; xanthogen compounds such as 2,4-diphenyl-4-methyl-1-pentene, 2,4-diphenyl-4-methyl-2-pentene, dimethylxanthogen disulfide, and diisopropylxanthogen disulfide; thiuram compounds such as terpinolene, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and tetramethylthiuram monosulfide; phenolic compounds such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol; allyl compounds such as allyl alcohol; halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, and carbon tetrabromide; vinyl ethers such as α-benzyloxystyrene, α-benzyloxyacrylonitrile, and α-benzyloxyacrylamide; triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, and 2-ethylhexyl thioglycolate. One or more of these can be used. The amount of these chain transfer agents is not particularly limited, but it is usually used in an amount of 0 to 5 parts by mass with respect to 100 parts by mass of the charged monomer amount.

[0047] Examples of the polymerization terminator include hydroxylamine, hydroxylamine sulfate, diethylhydroxylamine, hydroxylamine sulfonic acid and its alkali metal salts, sodium dimethyldithiocarbamate, and quinone compounds such as hydroquinone. The amount of the polymerization terminator used is not particularly limited, but is usually 0 to 2 parts by mass with respect to 100 parts by mass of the total monomers.

[0048] Furthermore, the polymer obtained by the above method can adjust the pH by using a base as a pH adjuster as needed. Specific examples of the base include sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, inorganic ammonium compounds, organic amine compounds, and the like. The pH range is pH 1 to 11, preferably pH 1.5 to 10.5, more preferably pH 2 to 10.

[0049] In addition, polymerization auxiliary materials such as a particle size adjuster, a chelating agent, and an oxygen scavenger can be used as needed.

[0050] The emulsion polymerization may be carried out in any of a batch system, a semi-batch system, and a continuous system. The polymerization time and the polymerization temperature are not particularly limited and can be appropriately selected from the type of the polymerization initiator used and the like. Generally, the polymerization temperature is 10 to 100 ° C and the polymerization time is 0.5 to 100 hours.

[0051] There is no particular limitation on the method for recovering the polymer obtained by the above method, and a generally used method can be adopted. As an example of the method, a method of continuously or batchwise supplying the polymerization solution to an aqueous solution containing a coagulant can be mentioned, and a coagulated slurry can be obtained by this operation. At this time, the temperature of the aqueous solution containing the coagulant is affected by factors such as the type and amount of the monomer, and the shear force due to stirring and the like, so it cannot be uniformly specified, but generally it is 50 ° C or higher, preferably in the range of 60 ° C to 100 ° C. There are no particular restrictions on the coagulant that can be used for this purpose, and it is preferably an inorganic metal salt. Specific examples thereof include sodium sulfate, magnesium sulfate, aluminum sulfate, sodium chloride, calcium chloride, and the like.

[0052] The coagulated slurry obtained by the above method is preferably washed with water to remove the coagulant. If no water washing is performed at all or the washing is insufficient, there is a risk that ionic residues derived from the coagulant will precipitate in the forming process.

[0053] An acrylic copolymer can be obtained by removing moisture from the coagulated slurry after washing with water and drying it. The drying method is not particularly limited, but generally, it is dried using a flash dryer, a fluidized dryer, or the like. Further, a dehydration step using a centrifuge or the like may be performed before the drying step.

[0054] An acrylic copolymer (A) can be obtained which contains a structural unit derived from an alkyl acrylate and / or a structural unit derived from an alkoxyalkyl acrylate (a) 45 to 89.5% by mass, a structural unit derived from an alkyl methacrylate having an alkyl group having 3 to 16 carbon atoms (b) 10 to 50% by mass, and a structural unit derived from a crosslinkable monomer (c) 0.5 to 5.5% by mass.

[0055] The composition for a thermoplastic material of the present invention may contain, as an acrylic copolymer, an acrylic copolymer other than the acrylic copolymer (A) together with the acrylic copolymer (A). However, in 100% by mass of the acrylic copolymer, the content of the acrylic copolymer (A) is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, particularly preferably 80% by mass or more, most preferably 90% by mass or more, and even most preferably 95% by mass or more, and may be 100% by mass.

[0056] The thermoplastic polyester resin (B) in the present invention refers to a resin having an ester bond in the main chain that can be a known one, and examples include polymers of dicarboxylic acids or their ester-forming derivatives and glycols, polymers of monomers having a carboxyl group and a hydroxyl group in the molecule, etc., and known ones can be used. For example, aromatic polyester resins such as polybutylene terephthalate resin, polyethylene terephthalate resin, polypropylene terephthalate resin, polybutylene naphthalate resin, polypropylene naphthalate resin, and polylactic acid resin can be mentioned. It is preferably an aromatic polyester resin, more preferably polybutylene terephthalate resin or polyethylene terephthalate resin, and particularly preferably polybutylene terephthalate resin.

[0057] The melting point of the thermoplastic polyester resin (B) is preferably 60 to 400 °C, more preferably 80 to 350 °C, and still more preferably 100 to 300 °C. When within the above range, the effects tend to be more preferably obtained. In this specification, the melting point of the thermoplastic polyester resin (B) is measured by DSC (differential scanning calorimetry) in accordance with JIS K6240.

[0058] The glass transition temperature of the thermoplastic polyester resin (B) is preferably -100 to 300 °C, more preferably -80 to 250 °C, and still more preferably -60 to 200 °C. When within the above range, the effects tend to be more preferably obtained. In this specification, the glass transition temperature of the thermoplastic polyester resin (B) is measured by DSC (differential scanning calorimetry) in accordance with JIS K6240.

[0059] In the composition for a thermoplastic material of the present invention, the content of the thermoplastic polyester resin (B) is preferably 5 to 90 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 20 to 40 parts by mass with respect to 100 parts by mass of the acrylic copolymer. When containing two or more kinds of thermoplastic polyester resins, the content of the thermoplastic polyester resin (B) means the total content. The same applies to other descriptions.

[0060] The thermoplastic polyester elastomer (C) having a flexural modulus of 30 MPa or more and having a polyester unit as a soft segment is preferably a block copolymer composed of a hard segment and a soft segment. As the hard segment of the thermoplastic polyester elastomer (C) having a flexural modulus of 30 MPa or more and having a polyester unit as a soft segment, dicarboxylic acids such as terephthalic acid, dimethyl terephthalate, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, and diols having a molecular weight of 200 or less, 1,4-butanediol, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol and other aliphatic diols, alicyclic diols such as 1,4-cyclohexanedimethanol, and aromatic diols such as xylylene glycol may be used. Among them, aromatic polyesters formed from aromatic dicarboxylic acids and aliphatic diols are preferred, and polybutylene terephthalate, polybutylene naphthalate and the like are more preferred.

[0061] As the soft segment of the thermoplastic polyester elastomer (C) having a flexural modulus of 30 MPa or more and having a polyester unit as a soft segment, an aliphatic polyester is preferably used. Examples of the aliphatic polyester include poly(ε-caprolactone), polyenanthrolactone, polycaprolactone, polybutylene adipate and the like.

[0062] In the thermoplastic polyester elastomer (C) having a bending elastic modulus of 30 MPa or more and having a polyester unit as a soft segment, the (mass) ratio of the hard segment to the soft segment is preferably such that hard segment:soft segment is 10:90 to 90:10, more preferably 20:80 to 80:20, and may be 30:70 to 70:30.

[0063] The bending elastic modulus of the thermoplastic polyester elastomer (C) having a polyester unit as a soft segment of the present invention is 30 MPa or more. The lower limit of the bending elastic modulus of the thermoplastic polyester elastomer (C) having a polyester unit as a soft segment is more preferably 50 MPa or more, and particularly preferably 100 MPa or more. The upper limit is preferably 1000 MPa or less, more preferably 600 MPa or less, and particularly preferably 300 MPa or less. As a method for measuring the bending elastic modulus, it is measured by a universal testing machine in accordance with JIS K7171.

[0064] In the composition for a thermoplastic material of the present invention, the content of the thermoplastic polyester elastomer (C) having a bending elastic modulus of 30 MPa or more is preferably 3 to 90 parts by mass, more preferably 4 to 50 parts by mass, and still more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the acrylic copolymer.

[0065] In the composition for a thermoplastic material of the present invention, the total amount of the thermoplastic polyester resin (B) and the thermoplastic polyester elastomer (C) having a bending elastic modulus of 30 MPa or more and having a polyester unit as a soft segment is preferably 5 to 95 parts by mass, more preferably 15 to 70 parts by mass, and still more preferably 25 to 50 parts by mass with respect to 100 parts by mass of the acrylic copolymer.

[0066] The composition for a thermoplastic material of the present invention preferably contains a crosslinking agent (D) for crosslinking an acrylic copolymer. Examples of the crosslinking agent (D) for crosslinking an acrylic copolymer include quinoxaline-based crosslinking agents, thiourea-based crosslinking agents, triazine-based crosslinking agents, polyvalent amine compounds, polyvalent epoxy compounds, polyvalent isocyanate compounds, aziridine compounds, sulfur compounds, basic metal oxides, and organometallic halides, which are conventionally known crosslinking agents commonly used for crosslinking rubber. Among these, triazine-based crosslinking agents or polyvalent amine compounds are preferably used.

[0067] Examples of the quinoxaline-based crosslinking agent include 2,3-dimercaptoquinoxaline, quinoxaline-2,3-dithiocarbonate, 6-methylquinoxaline-2,3-dithiocarbonate, 5,8-dimethylquinoxaline-2,3-dithicarbonate, and the like.

[0068] Examples of the thiourea-based crosslinking agent include 2-mercaptoimidazoline (ethylene thiourea), 1,3-diethylthiourea, 1,3-dibutylthiourea, trimethylthiourea, and the like.

[0069] Examples of the triazine crosslinking agent include 1,3,5-triazine trithiol (2,4,6-trimercapto-s-triazine), 6-anilino-1,3,5-triazine-2,4-dithiol, 6-methylamino-1,3,5-triazine-2,4-dithiol, 6-dimethylamino-1,3,5-triazine-2,4-dithiol, 6-ethylamino-1,3,5-triazine-2,4-dithiol, 6-diethylamino-1,3,5-triazine-2,4-dithiol, 6-propylamino-1,3,5-triazine-2,4-dithiol, 6-dipropylamino-1,3,5-triazine-2,4-dithiol, 6-butylamino-1,3,5-triazine-2,4-dithiol, 6-dibutylamino-1,3,5-triazine-2,4-dithiol, 6-hexylamino-1,3,5-triazine-2,4-dithiol, 6-octylamino-1,3,5-triazine-2,4-dithiol, 6-decylamino-1,3,5-triazine-2,4-dithiol, and the like.

[0070] Practically preferred crosslinking agents include 2-mercaptoimidazoline (ethylene thiourea), 6-methylquinoxaline-2,3-dithiocarbonate, and 1,3,5-triazine trithiol (2,4,6-trimercapto-s-triazine). Particularly preferred vulcanizing agents include 1,3,5-triazine trithiol (2,4,6-trimercapto-s-triazine).

[0071] Examples of polyvalent amine compounds include aliphatic polyvalent amine compounds such as hexamethylenediamine, hexamethylenediamine carbamate, and N,N'-dicinamylidene-1,6-hexanediamine; and aromatic polyvalent amine compounds such as 4,4'-methylenedianiline, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-(m-phenylenediisopropylidene)dianiline, 4,4'-(p-phenylenediisopropylidene)dianiline, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 4,4'-diaminobenzanilide, 4,4'-bis(4-aminophenoxy)biphenyl, m-xylylenediamine, p-xylylenediamine, 1,3,5-benzenetriamine, 1,3,5-benzenetriaminomethyl, and isophthalic acid dihydrazide.

[0072] Examples of polyvalent epoxy compounds include glycidyl ether type epoxy compounds such as phenol novolak type epoxy compounds, cresol novolak type epoxy compounds, cresol type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, brominated bisphenol A type epoxy compounds, brominated bisphenol F type epoxy compounds, and hydrogenated bisphenol A type epoxy compounds; and other polyvalent epoxy compounds such as alicyclic epoxy compounds, glycidyl ester type epoxy compounds, glycidyl amine type epoxy compounds, and isocyanurate type epoxy compounds.

[0073] Examples of polyvalent isocyanate compounds include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 1,3,6-hexamethylene triisocyanate, 1,6,11-undecane triisocyanate, and bicycloheptane triisocyanate.

[0074] Examples of the aziridine compounds include tris-2,4,6-(1-aziridinyl)-1,3,5-triazine, tris[1-(2-methyl)aziridinyl]phosphine oxide, hexa[1-(2-methyl)aziridinyl]triphosphatotriazine, and the like.

[0075] Examples of the sulfur compounds include sulfur, 4,4'-dithiomorpholine, tetramethylthiuram disulfide, tetraethylthiuram disulfide, and the like.

[0076] Examples of the basic metal oxides include zinc oxide, lead oxide, calcium oxide, magnesium oxide, and the like.

[0077] Examples of the organometallic halides include dicyclopentadienyl metal dihalides, and examples of the metal include titanium, zirconium, and the like.

[0078] These crosslinking agents (D) may be used alone or in combination of two or more. The content of the crosslinking agent (D) is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the acrylic copolymer.

[0079] In addition to the crosslinking agent, the composition for the thermoplastic material of the present invention may contain a metal compound and / or an inorganic microporous crystal as an acid acceptor.

[0080] Examples of the metal compounds serving as acid acceptors include oxides, hydroxides, carbonates, carboxylates, silicates, borates, phosphites of Group II metals in the periodic table, oxides, basic carbonates, basic carboxylates, basic phosphites, basic sulfites, tribasic sulfates of Group IVA metals in the periodic table, and the like.

[0081] Specific examples of the metal compound serving as the acid acceptor include magnesia, magnesium hydroxide, barium hydroxide, magnesium carbonate, barium carbonate, sodium carbonate, quicklime, slaked lime, calcium carbonate, calcium silicate, calcium stearate, zinc stearate, calcium phthalate, calcium phosphite, zinc white, tin oxide, litharge, red lead, white lead, dibasic lead phthalate, dibasic lead carbonate, basic lead silicate, tin stearate, basic lead phosphite, basic tin phosphite, basic lead sulfite, tribasic lead sulfate, and the like.

[0082] The inorganic microporous crystal means a crystalline porous body and can be clearly distinguished from an amorphous porous body such as silica gel, alumina, etc. Examples of such inorganic microporous crystals include zeolites, aluminophosphate type molecular sieves, layered silicates, synthetic hydrotalcites, alkali metal titanates, and the like. Preferred acid acceptors include synthetic hydrotalcite, and more preferred acid acceptors include synthetic hydrotalcite with a weight loss on heating at 300 °C for 1 hour of 4.5% by mass or less, such as calcined hydrotalcite.

[0083] The content of the acid acceptor is preferably 1 to 20 parts by mass, more preferably 2 to 10 parts by mass, based on 100 parts by mass of the acrylic copolymer.

[0084] In addition, the composition of the present invention can contain a compatibilizer (E) for finely dispersing components (A), (B), and (C) or reinforcing the interface. Examples of the compatibilizer (E) include functional group-containing olefin polymers, functional group-modified olefin polymers, functional group-containing olefin graft copolymers, functional group-containing styrene copolymers, functional group-modified styrene polymers, functional group-containing macromonomer copolymers, and the like. Examples of the functional group-containing olefin copolymer include ethylene·GMA copolymer, ethylene·GMA·VA copolymer, ethylene·GMA·MA copolymer, ethylene·GMA·MAH copolymer. Examples of the functional group-modified polyolefin include maleic anhydride (MAH)-modified polyethylene, maleic anhydride-modified polypropylene, etc. Examples of the functional group-containing styrene polymer include styrene·oxazoline copolymer, styrene·MAH copolymer, etc. Examples of the functional group-containing macromonomer copolymer include epoxy group-containing acrylic monomer·PMMA macromonomer copolymer, etc. In particular, an epoxy group-containing copolymer is preferred.

[0085] The content of the compatibilizer (E) is preferably 0 to 15 parts by mass, more preferably 2 to 10 parts by mass, based on 100 parts by mass of the acrylic copolymer.

[0086] In addition, the composition for the thermoplastic material of the present invention can optionally contain other additives commonly used in the art, such as lubricants, anti-aging agents, light stabilizers, fillers, reinforcing agents, plasticizers, processing aids, pigments, colorants, crosslinking accelerators, crosslinking aids, crosslinking retardants, antistatic agents, foaming agents, etc. These can be used alone or in combination of two or more.

[0087] The crosslinking accelerator is not particularly limited, and specifically includes aliphatic tertiary amines, dithiocarbamate salts, diazabicycloalkene compounds, and the like.

[0088] As the aliphatic tertiary amine, although not particularly limited, specific examples include trimethylamine, triethylamine, tripropylamine, triallylamine, triisopropylamine, tri-n-butylamine, tri-t-butylamine, tri-sec-butylamine, trihexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, triundecylamine, tridodecylamine, and the like.

[0089] As the dithiocarbamate, although not particularly limited, specific examples include zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dipentyldithiocarbamate, zinc dihexyldithiocarbamate, zinc N-pentamethylenedithiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc dibenzyldithiocarbamate, copper dipropyldithiocarbamate, copper diisopropyldithiocarbamate, copper dibutyldithiocarbamate, sodium diethyldithiocarbamate, sodium diisopropyldithiocarbamate, sodium dibutyldithiocarbamate, ferric dimethyldithiocarbamate, ferric diethyldithiocarbamate, and the like.

[0090] As the diazabicycloalkene compound, although not particularly limited, specific examples include 1,8-diazabicyclo(5.4.0)undecene-7, 1,5-diazabicyclo(4.3.0)nonene-5, 1,4-diazabicyclo(2.2.2)octane, and their p-toluenesulfonate salts, phenol salts, phenol resin salts, orthophthalate salts, formate salts, octylate salts, naphthoate salts, and the like.

[0091] As the guanidine compound, although not particularly limited, specific examples include 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, 1-o-tolylbiguanide, di-o-tolylguanidine salt of dicatecholborate, 1,3-di-o-cumenylguanidine, 1,3-di-o-biphenylguanidine, 1,3-di-o-cumenyl-2-propionylguanidine, and the like.

[0092] As the crosslinking accelerator, it may be used alone or in combination of two or more. The content of the crosslinking accelerator is preferably 0.1 to 10 parts by mass, more preferably 0.15 to 8 parts by mass, and still more preferably 0.2 to 7 parts by mass with respect to 100 parts by mass of the acrylic copolymer.

[0093] As the filler, known fillers can be used. Specifically, calcium carbonate, talc, silica, clay, carbon fiber, glass fiber, carbon black, titanium oxide, magnesium oxide, hydrotalcite, magnesium hydroxide, antimony oxide, zinc oxide, carbon black, etc. can be mentioned, and silica and carbon black are preferable.

[0094] The content of the filler may be 1 to 20 parts by mass, preferably 1.5 to 10 parts by mass with respect to 100 parts by mass of the acrylic copolymer.

[0095] Examples of the processing aid include lubricating oil, process oil, coal tar, castor oil, stearic acid, calcium stearate, ester wax, etc.

[0096] The content of the processing aid may be 0 to 10 parts by mass, may be 0.3 to 10 parts by mass, or may be 0.5 to 7 parts by mass with respect to 100 parts by mass of the acrylic copolymer.

[0097] Examples of the anti-aging agent include amines, phosphates, quinolines, cresols, phenols, metal salts of dithiocarbamate, etc. Diphenylamine derivatives such as 4,4'-bis(α,α-dimethylbenzyl)diphenylamine and amines such as phenylenediamine derivatives are preferable.

[0098] The content of the anti-aging agent may be 0.3 to 10 parts by mass, preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the acrylic copolymer.

[0099] The plasticizer is not particularly limited as long as it exhibits the effects of the present invention. Examples thereof include polyester plasticizers, polyether ester plasticizers, polyvalent carboxylic acid ester plasticizers, glycerin plasticizers, sulfonamide plasticizers, and phosphate ester plasticizers.

[0100] The SP value of the plasticizer is preferably 8.5 to 11, more preferably 9.5 to 10.

[0101] The molecular weight of the plasticizer is preferably 200 to 5000, more preferably 300 to 3000.

[0102] Examples of the polyester plasticizer include polyesters obtained by reacting acid components such as adipic acid, sebacic acid, terephthalic acid, and isophthalic acid with diols such as propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and ethylene glycol. The polyether ester plasticizer is preferably an acid ester of a polyalkylene glycol. Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, and polybutylene glycol. Examples of the acid include butanoic acid, isobutanoic acid, 2-ethylbutyric acid, and 2-ethylhexanoic acid. Examples of the polyvalent carboxylic acid ester plasticizer include aliphatic dicarboxylic acid esters, aromatic dicarboxylic acid esters, and trimellitic acid esters. Examples of the aliphatic dicarboxylic acid ester include adipic acid esters, azelaic acid esters, and sebacic acid esters. Examples of the aromatic dicarboxylic acid ester include phthalic acid esters. Examples of trimellitic acid esters include trimethyl trimellitate, triethyl trimellitate, tripropyl trimellitate, tributyl trimellitate, triamyl trimellitate, trihexyl trimellitate, triheptyl trimellitate, tri-n-octyl trimellitate, tri-2-ethylhexyl trimellitate, trinonyl trimellitate, triisononyl trimellitate, and the like. The polyvalent carboxylic acid ester plasticizer preferably contains an ether bond. However, a polyvalent carboxylic acid ester plasticizer that does not contain a polyalkylene oxide structure is preferred from the viewpoints of flexibility and heat resistance. Examples of glycerin plasticizers include glycerin monoacetomonolaurate, glycerin diacetomonolaurate, and glycerin monoacetomonostearate. Examples of sulfonamide plasticizers include N-butylbenzenesulfonamide and p-toluenesulfonamide. Examples of phosphate ester plasticizers include tributyl phosphate, tri-2-ethylhexyl phosphate, trioctyl phosphate, and triphenyl phosphate.

[0103] The content of the plasticizer may be 0 to 100 parts by mass, preferably 5 to 50 parts by mass, and may be 5 to 30 parts by mass with respect to 100 parts by mass of the acrylic copolymer.

[0104] When using plasticizers in combination, the proportion of plasticizers with an SP value of 9.5 to 10 is preferably 5 to 95% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 70% by mass. The proportion of plasticizers with an SP value different from 9.5 to 10 (SP value is 8.5 or more and less than 9.5, SP value is more than 10 and 11 or less) is preferably 5 to 95% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 70% by mass.

[0105] The thermoplastic material composition of the present invention is obtained from the composition for thermoplastic materials of the present invention. Specifically, the thermoplastic material composition of the present invention is obtained by crosslinking the composition for thermoplastic materials of the present invention. The crosslinking method is not particularly limited, but dynamic crosslinking is preferred. That is, the thermoplastic material composition of the present invention is preferably a dynamically crosslinked thermoplastic material composition obtained by dynamically crosslinking the composition for thermoplastic materials of the present invention. In this specification, dynamic crosslinking means proceeding with crosslinking while kneading.

[0106] As a method for producing a (dynamically crosslinked type) thermoplastic material composition characterized by selectively crosslinking an acrylic copolymer while kneading the composition for thermoplastic materials of the present invention in a kneader, any method may be used as long as the crosslinked acrylic copolymer is substantially homogeneously dispersed in a thermoplastic polyester resin and a thermoplastic polyester elastomer having a flexural modulus of 30 MPa or more. First, the acrylic copolymer, the thermoplastic polyester resin, and the thermoplastic polyester elastomer having a flexural modulus of 30 MPa or more are sufficiently blended (pre-kneaded) in a kneader in advance, and then a crosslinking agent capable of crosslinking the acrylic copolymer is added, and a method of selectively crosslinking the acrylic copolymer while kneading (dynamic vulcanization) is most suitable in the above respects.

[0107] As the kneader, a device capable of kneading under a shearing force while heating, such as a kneader, a Banbury mixer, a twin-screw kneading extruder, etc., is appropriately selected. Also, the temperature and time for crosslinking the acrylic copolymer while kneading are appropriately set according to the crosslinking agent of the acrylic copolymer used or the added thermoplastic resin and thermoplastic elastomer. In the present invention, it is desirable that the temperature is in the range of 160 to 350 °C and the time is in the range of 2 to 30 minutes.

[0108] Before adding the crosslinking agent, when preliminarily and sufficiently blending (pre-kneading) an acrylic copolymer, a thermoplastic polyester resin, and a thermoplastic polyester elastomer having a flexural modulus of 30 MPa or more and having a polyester unit as a soft segment in a kneader, in order to further improve the dispersibility of these compounds and more suitably obtain the effects of the present invention, it is preferable to knead these compounds in the kneader for a longer time. The pre-kneading time is preferably 1 minute or more, more preferably 2 minutes or more, still more preferably 3 minutes or more, and the upper limit is not particularly limited, but for example, it is 15 minutes or less. The kneading temperature is preferably as follows. Also, the rotation speed of the kneader during pre-kneading is preferably 80 to 120 rpm, more preferably 90 to 110 rpm.

[0109] Specific embodiments for carrying out the present invention will be described below with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not deviated from.

[0110] The production of the acrylic copolymer will be described. (Production of Acrylic Copolymer A) Into a polymerization reactor equipped with a thermometer, a stirring device, a nitrogen inlet tube, and a decompression device, 100 parts by mass of water, 0.4 part by mass of a polyoxyalkylene alkyl ether phosphate ester, and 1.5 parts by mass of a polyoxyethylene alkyl ether phosphate salt were added. As monomers, 29.3 parts by mass of ethyl acrylate, 39.1 parts by mass of n-butyl acrylate, 29.3 parts by mass of n-butyl methacrylate, 2.2 parts by mass of vinyl monochloroacetate, and 0.02 part by mass of 1,6-hexanediol diacrylate were charged. After repeating degassing under reduced pressure and nitrogen substitution to sufficiently remove oxygen, 0.01 part by mass of sodium ascorbate, 0.005 part by mass of ferrous sulfate, and 0.01 part by mass of t-butyl hydroperoxide (purity 69%) were added to initiate an emulsion polymerization reaction at normal pressure and room temperature. Further, 0.025 part by mass of sodium ascorbate was added, and the reaction was continued until the polymerization conversion rate reached 95%, and then the polymerization was stopped. The obtained emulsion polymerization liquid was coagulated with an aqueous calcium chloride solution, washed with water, and dried to obtain an acrylic copolymer A. The composition ratios shown from the charged composition are shown in Table 1.

[0111]

Table 1

[0112] A method for producing a (dynamically crosslinked) thermoplastic material composition (thermoplastic elastomer composition) will be described.

[0113] The melting point in the thermoplastic resin or thermoplastic elastomer in Examples and Comparative Examples was measured with a DSC8000 manufactured by PerkinElmer in accordance with JIS K6240.

[0114] 「Example 1」 Using a 60 cc kneader heated to 230°C, as shown in Table 2, 100 parts by mass of acrylic copolymer A, 38.5 parts by mass of polybutylene terephthalate (PBT) (manufactured by Mitsubishi Chemical Corporation, Novaduran 5020, melting point 224°C) as a thermoplastic resin, 8 parts by mass of thermoplastic polyester elastomer (TPC) (manufactured by Toyobo Co., Ltd., Pelprene S-1002, melting point 204°C, flexural modulus 125 MPa, hard segment is aromatic polyester - soft segment is aliphatic polyester) as a thermoplastic elastomer, 3.1 parts by mass of Greg G8205 (manufactured by NI Chemtec Co., Ltd., ester wax), 1.9 parts by mass of stearic acid (manufactured by NOF Corporation, Sakura stearic acid), 1.9 parts by mass of Nocrack CD (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., 4,4'-bis(α,α-dimethylbenzyl)diphenylamine), 8 parts by mass of RS-735 (manufactured by ADEKA Corporation, SP value 9.2) were added. After kneading at 100 rpm for 3 minutes, 0.92 parts by mass of Actar TSH (manufactured by Kawaguchi Chemical Industry Co., Ltd., 2,4,6-trimercapto-s-triazine), 1.38 parts by mass of Noxeller BZ (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., zinc dibutyldithiocarbamate), 8 parts by mass of N-butylbenzenesulfonamide (manufactured by Toray Fine Chemical Co., Ltd., BBSA, SP value 10.5) were added and dynamic crosslinking was carried out at 100 rpm for 3 minutes, then taken out, preheated at a press set at 245°C for 3 minutes, heated for 3 minutes, and then cooled to mold a 2 mm thick sheet, and punched out with a punching die to obtain a No. 3 dumbbell shown in JIS K-6251.

[0115] "Comparative Examples 1 to 3" In Comparative Examples 1 to 3, as shown in Table 2, dumbbell No. 3 was obtained in the same manner as in Example 1, except that only the thermoplastic polyester elastomer was changed from Example 1. The thermoplastic polyester elastomers used at this time were Pelprene P-40B (manufactured by Toyobo Co., Ltd., melting point 180°C, flexural modulus 23 MPa, hard segment being aromatic polyester - soft segment being aliphatic polyether), Pelprene P-90B (manufactured by Toyobo Co., Ltd., melting point 203°C, flexural modulus 162 MPa, hard segment being aromatic polyester - soft segment being aliphatic polyether), and Pelprene P-90BD (manufactured by Toyobo Co., Ltd., melting point 203°C, flexural modulus 162 MPa, hard segment being aromatic polyester - soft segment being aliphatic polyether).

[0116] "Comparative Example 4" In Comparative Example 4, as shown in Table 2, dumbbell No. 3 was obtained in the same manner as in Example 1, except that 46.2 parts by mass of polybutylene terephthalate was used instead of adding 8 parts by mass of the thermoplastic polyester elastomer from Example 1.

[0117] "Example 2" As shown in Table 3, the addition amounts were changed from those in Example 1 to 37 parts by mass of polybutylene terephthalate, 3.2 parts by mass of Greg G8205, 0.94 parts by mass of Actar TSH, and 1.42 parts by mass of Noxeller BZ, and dumbbell No. 3 was obtained in the same manner as in Example 1, except that 5 parts by mass of Reseda GP-301 (a methyl methacrylate copolymer containing an epoxy group, manufactured by Toagosei Co., Ltd.) was added.

[0118] "Comparative Examples 5 to 6" In Comparative Examples 5 to 6, as shown in Table 3, dumbbell No. 3 was obtained in the same manner as in Example 1, except that only the thermoplastic polyester elastomer was changed from Example 2. The thermoplastic polyester elastomers used at this time were Pelprene P-40B and Pelprene P-90B.

[0119] "Comparative Example 7" In Comparative Example 7, as shown in Table 3, starting from Comparative Example 4, the addition amounts were changed to 44.9 parts by mass of polybutylene terephthalate, 3.2 parts by mass of Greg G8205, 0.94 parts by mass of Actar TSH, and 1.42 parts by mass of Noxeller BZ, and a dumbbell No. 3 was obtained in the same manner as in Example 1 except that 5 parts by mass of Reseda GP-301 was added.

[0120] "Example 3" As shown in Table 4, a dumbbell No. 3 was obtained in the same manner as in Example 1 except that the plasticizer was changed from RS-735 to RS-1000 (manufactured by ADEKA Corporation, SP value 9.7).

[0121] "Example 4" As shown in Table 4, a dumbbell No. 3 was obtained in the same manner as in Example 1 except that the addition amounts were changed to 29.1 parts by mass of polybutylene terephthalate and 16 parts by mass of thermoplastic polyester elastomer from Example 3.

[0122] "Comparative Examples 8 - 10" In Comparative Examples 8 - 10, as shown in Table 4, dumbbell No. 3 was obtained in the same manner as in Example 1 except that only the polyester elastomer was changed from Example 3. The thermoplastic polyester elastomers used at this time were Pelprene P-40B, Pelprene P-90B, and Pelprene P-90BD.

[0123] Performance Test For each test piece obtained in Examples 1 - 4 and Comparative Examples 1 - 10, a tensile test (tensile speed: 200 mm / min) was performed using AGS-5KNY manufactured by Shimadzu Corporation according to the method described in JIS K-6251, and the tensile strength and elongation at break were measured. Hardness measurement was carried out using an Asker rubber hardness tester type A manufactured by Polymer Instrument Co., Ltd. according to the method described in JIS K-6253. The constant elongation tensile permanent set was tested according to JIS K6273 under the conditions of 23°C × 24 hours and 30% elongation using an I-shaped sample. The results are shown in Tables 5 - 7.

[0124]

Table 2

[0125]

Table 3

[0126]

Table 4

[0127]

Table 5

[0128] When comparing Example 1 with Comparative Examples 1 to 3, in the thermoplastic material composition, those with different constitutions and flexural modulus of the thermoplastic polyester elastomer were replaced in equal amounts. However, in the thermoplastic material of Example 1 obtained, while maintaining the normal physical properties, it has a lower hardness and excellent constant elongation tensile permanent set. Also, as shown in Comparative Example 1, the constant elongation tensile permanent set when using a thermoplastic polyester elastomer with a flexural modulus of 30 MPa or less became unmeasurable because the test piece broke during the measurement. When comparing Example 1 with Comparative Example 4, Comparative Example 4 is a thermoplastic material composition composed of an acrylic copolymer and polybutylene terephthalate that does not contain a thermoplastic polyester elastomer. However, by adding a thermoplastic polyester elastomer, the normal physical properties are maintained, and the hardness is low and the constant elongation tensile permanent set is improved.

[0129]

Table 6

[0130] When comparing Example 2 with Comparative Examples 5 to 7, in the thermoplastic material composition, it is a replacement of an equal amount of those with different configurations and flexural modulus of the thermoplastic polyester elastomer in the formulation where RS-735 and GP-301 were added to Example 1. However, in the obtained thermoplastic material of Example 2, the constant elongation tensile permanent set is excellent. Also, as shown in Comparative Example 5, when using a thermoplastic polyester elastomer with a flexural modulus of 30 MPa or less, the constant elongation tensile permanent set could not be measured because the test piece broke during the measurement. When comparing Example 2 with Comparative Example 7, Comparative Example 7 is a thermoplastic material composed of an acrylic copolymer not containing a thermoplastic polyester elastomer and thermoplastic polybutylene terephthalate. However, by adding a thermoplastic polyester elastomer, it maintains its normal physical properties and has low hardness and excellent tensile permanent set properties.

[0131]

Table 7

[0132] When comparing Example 3 with Comparative Examples 8 to 10, in the thermoplastic material composition, it is a replacement of an equal amount of those with different configurations and flexural modulus of the thermoplastic polyester elastomer in the formulation where RS-1000 and GP-301 were added to Example 1. However, in the obtained thermoplastic material of Example 3, it maintains its normal physical properties and has low hardness and excellent tensile permanent set properties. As shown in Example 4, even when changing the ratio of the thermoplastic polybutylene terephthalate and the thermoplastic polyester elastomer added from Example 3, it is possible to obtain a thermoplastic material that maintains its normal physical properties and has low hardness and excellent tensile permanent set properties.

[0133] From the comparison between Example 1 and Comparative Examples 1 to 4, Example 2 and Comparative Examples 5 to 7, and Example 3 and Comparative Examples 8 to 10, by adding a thermoplastic polyester elastomer with a flexural modulus of 30 MPa or less and an aliphatic polyester as the soft segment, it is possible to obtain a thermoplastic material that maintains normal physical properties and has low hardness and excellent tensile permanent set properties. Also, by using a plasticizer with an SP value of 9.5 to 10 at that time, the permanent set properties can be further improved.

Industrial Applicability

[0134] The thermoplastic material obtained by using the thermoplastic material composition of the present invention is useful as automotive parts, sealing materials, packings, tubes, etc. because it maintains normal physical properties and has low hardness and excellent tensile permanent set properties.

Claims

1. A composition for a thermoplastic material containing: a structural unit derived from an alkyl acrylate and / or a structural unit derived from an alkoxyalkyl acrylate (a) 45 to 89.5% by mass, a structural unit derived from an alkyl methacrylate having an alkyl group with 3 to 16 carbon atoms (b) 10 to 50% by mass, and a structural unit derived from a crosslinkable monomer (c) 0.5 to 5.5% by mass, an acrylic copolymer (A), a thermoplastic polyester resin (B), and a thermoplastic polyester elastomer (C) having a flexural modulus of 30 MPa or more and having a polyester unit as a soft segment.

2. The composition for a thermoplastic material according to Claim 1, containing 5 to 95 parts by mass in total of the thermoplastic polyester resin (B) and the thermoplastic polyester elastomer (C) with respect to 100 parts by mass of the acrylic copolymer.

3. The composition for a thermoplastic material according to Claim 1, further containing a crosslinking agent (D) for crosslinking the acrylic copolymer.

4. A thermoplastic material obtained from the composition for a thermoplastic material according to any one of Claims 1 to 3.

5. The thermoplastic material according to Claim 4, which is a thermoplastic elastomer.

6. A method for producing a thermoplastic material, in which the acrylic copolymer is crosslinked while kneading the composition for a thermoplastic material according to any one of Claims 1 to 3 in a kneader.

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