Thermoplastic resin composition, molding material and molded article

Abstract

The present invention provides a thermoplastic resin composition which contains: a compound (F) that is at least one compound selected from the group consisting of a macromonomer (A) represented by formula (1) and a copolymer (C) that contains a structural unit derived from the macromonomer (A); and a compound (G) that is represented by formula (2). (In formula (1), each of R0 to Rn independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group; each of X1 to Xn independently represents a hydrogen atom or a methyl group; Z represents an end group; and n represents a natural number of 1 to 10,000.) (In formula (2), each of R0 to R4 independently represents an alkyl group having 1 to 5 carbon atoms; and R5 represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom.)

Description

[Technical Field]

[0001] The present invention relates to a thermoplastic resin composition that exhibits excellent resistance to thermal decomposition during molding, a molding material containing the same, and a molded article obtained by molding the same. This application claims priority based on Japanese Patent Application No. 2022-021457, filed on February 15, 2022, the contents of which are incorporated herein by reference. [Background technology]

[0002] Many monomers containing reactive unsaturated bonds can be reacted under appropriate conditions with a catalyst that induces chain transfer to produce polymers. Typical examples of such unsaturated monomers include vinyl compounds such as styrene, alkylstyrene, and alkoxystyrene. A wide variety of polymers with different physical properties can be synthesized by using these vinyl compounds alone or by copolymerization. For industrial applications, homopolymers made from a single monomer cannot meet the diverse material requirements, so a method of blending different polymers is used. However, simply blending different polymers often results in incompatibility between the polymers, resulting in a phase-separated structure with relatively large domains (called macrophase separation). Therefore, it is often difficult to fully utilize the properties of each polymer in a blend of different polymers.

[0003] One known method for solving the above problems is to use block copolymers, in which two or more polymer segments are chemically bonded. As mentioned above, mixtures of different polymers undergo phase separation due to the low compatibility between the polymers. However, in block polymers, the polymer segments are chemically linked to each other, resulting in a phase-separated structure on the nanometer scale (known as microphase separation). This allows the properties of each polymer segment to be fully expressed. Among block copolymers, (meth)acrylic block copolymers are being used in a variety of applications requiring transparency and weather resistance.

[0004] Atom transfer radical polymerization (ATRP) is a well-known method for producing such (meth)acrylic block copolymers. However, the use of metal catalysts in ATRP complicates the polymer production process, resulting in increased costs and reduced productivity. Other methods that do not require metal catalysts, such as reversible addition-fragmentation chain transfer (RAFT) polymerization, have been proposed. However, these methods have presented problems, such as residual sulfur atoms reducing weather resistance and discoloring molded articles of the resulting polymer.

[0005] A known method for solving these problems is to prepare an acrylic macromonomer copolymer, which is an acrylic block-graft copolymer, by first preparing an acrylic macromonomer using a very small amount of a cobalt complex with an extremely high chain transfer constant and then copolymerizing that acrylic macromonomer with another acrylic monomer (see, for example, Patent Document 1). Here, a macromonomer is a polymer having functional groups capable of undergoing a polymerization reaction, and is also called a macromer.

[0006] The acrylic macromonomer used in the method of Patent Document 1 has low thermal decomposition resistance (a property of being stable to heat and not easily decomposed) because depolymerization occurs at a relatively low temperature, making it unsuitable for thermoforming. Therefore, the thermal decomposition resistance is reduced due to the influence of unreacted macromonomer contained in the macromonomer copolymer, and improving thermal decomposition resistance has been an issue. Therefore, Patent Document 2 investigates a method for improving the thermal decomposition resistance of a macromonomer copolymer by using a non-metallic chain transfer agent when copolymerizing the acrylic macromonomer with a comonomer (Patent Document 2). Patent Document 3 also investigates a method for improving thermal decomposition resistance by reducing the amount of unreacted macromonomer contained in the macromonomer copolymer (see Patent Document 3). [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Special Publication No. 2000-514845 [Patent Document 2] WO2015 / 056668 [Patent Document 3] WO2017 / 199562 Summary of the Invention [Problem to be solved by the invention]

[0008] Although Patent Documents 2 and 3 can reduce the amount of unreacted macromonomer, it is difficult to obtain a macromonomer copolymer that does not contain unreacted macromonomer, and improving the thermal decomposition resistance of resin compositions containing acrylic macromonomers remains an issue. The present invention provides a thermoplastic resin composition having good resistance to thermal decomposition, a molding material, and a molded article obtained by molding the resin composition. [Means for solving the problem]

[0009] The present invention has the following aspects. [1] A thermoplastic resin composition comprising: compound (F) which is at least one compound selected from the group consisting of macromonomer (A) represented by formula (1) below and copolymer (C) containing a structural unit derived from macromonomer (A) represented by formula (1) below; and compound (G) represented by formula (2) below:

[0010] [ka]

[0011] (In formula (1), R 0 ~R n are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. 1 ~X n are each independently a hydrogen atom or a methyl group. Z is a terminal group. n is a natural number from 1 to 10,000.

[0012] [ka]

[0013] (In formula (2), R 1 ~R 4 each independently represents an alkyl group having 1 to 5 carbon atoms; R 5 represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom. [2] The copolymer (C) is contained, The thermoplastic resin composition according to [1], wherein the copolymer (C) has a chemical structure (E) represented by the following formula (3):

[0014] [ka]

[0015] (In formula (3), R 0 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. [3] The compound (F) has a chemical structure (E) represented by the following formula (3): The thermoplastic resin composition according to [1] or [2], wherein X is 0.01 or more and 100 or less when the molar ratio of the chemical structure (E) to the compound (G) is expressed as the chemical structure (E):compound (G)=1:X.

[0016] [ka]

[0017] (In formula (3), R 0 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. [4] The compound (F) has a chemical structure (E) represented by the following formula (3): The thermoplastic resin composition according to [1] or [2], wherein X is 0.05 or more and 30 or less when the molar ratio of the chemical structure (E) to the compound (G) is expressed as the chemical structure (E):compound (G)=1:X.

[0018] [ka]

[0019] (In formula (3), R 0 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. [5] The compound (F) has a chemical structure (E) represented by the following formula (3): The thermoplastic resin composition according to [1] or [2], wherein X is 0.2 or more and 10 or less when the molar ratio of the chemical structure (E) to the compound (G) is expressed as the chemical structure (E):the compound (G)=1:X.

[0020] [ka]

[0021] (In formula (3), R 0 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. [6] The thermoplastic resin composition according to any one of [1] to [5], further comprising a polymer (M) different from the compound (F). [7] The thermoplastic resin composition according to [6], wherein the polymer (M) is at least one selected from the group consisting of polymethyl methacrylate, polycarbonate, polyvinyl chloride, polyolefin, polyurethane, and polyester. [8] The thermoplastic resin composition according to [6] or [7], wherein the content of the polymer (M) is 10 to 95 mass % of the total amount of the thermoplastic resin composition. [9] A thermoplastic resin composition for injection molding or extrusion molding, which is the thermoplastic resin composition according to any one of [1] to [8].

[10] Use of the thermoplastic resin composition according to any one of [1] to [9] in injection molding or extrusion molding.

[11] A molding material comprising the thermoplastic resin composition according to any one of [1] to [9].

[12] A molded body obtained by molding the molding material according to

[11] .

[13] A vehicle component obtained by molding the molding material according to

[11] .

[14] An electric / electronic component obtained by molding the molding material according to

[11] .

[15] An optical member obtained by molding the molding material according to

[11] .

[16] A medical component obtained by molding the molding material according to

[11] .

[17] A food package obtained by molding the molding material according to

[11] .

[18] A method for producing a molded body, comprising molding the molding material according to

[11] to obtain a molded body.

[19] The method for producing a molded article according to

[18] , wherein the molding is injection molding or extrusion molding.

[20] The thermoplastic resin composition according to any one of [1] to [8], wherein the content of the compound (F) is preferably 80 to 99.99 mass%, more preferably 90 to 99.99 mass%, and even more preferably 95 to 99.99 mass%, of the total amount of the thermoplastic resin composition.

[21] The compound (F) contains the macromonomer (A), The content of the macromonomer (A) is preferably 80 to 99.99 mass%, more preferably 90 to 99.99 mass%, and even more preferably 95 to 99.99 mass%, of the total amount of the thermoplastic resin composition. The thermoplastic resin composition according to any one of [1] to [8] and

[20] .

[22] The compound (F) contains the copolymer (C), The content of the copolymer (C) is preferably 80 to 99.99 mass%, more preferably 90 to 99.99 mass%, and even more preferably 95 to 99.99 mass%, of the total amount of the thermoplastic resin composition. The thermoplastic resin composition according to any one of [1] to [8],

[20] , and

[21] .

[23] The thermoplastic resin composition according to any one of [1] to [8] and

[20] to

[22] , wherein the content of the compound (G) is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 3.0 mass%, and even more preferably 0.08 to 1.5 mass%, of the total amount of the thermoplastic resin composition.

[24] further comprising an additive (D), The thermoplastic resin composition according to any one of [1] to [8] and

[20] to

[23] , wherein the additive (D) is at least one selected from the group consisting of various stabilizers such as antioxidants, ultraviolet absorbers, and heat stabilizers; colorants such as inorganic pigments, organic pigments, and dyes; conductivity imparting agents such as carbon black and ferrite; inorganic fillers; lubricants; mold release agents; plasticizers; organic peroxides; neutralizing agents; crosslinking agents; and reinforcing agents.

[25] The thermoplastic resin composition according to

[24] , wherein the content of the additive is preferably 0 to 20 mass%, more preferably 0 to 10 mass%, and even more preferably 0 to 3.0 mass%, of the total amount of the thermoplastic resin composition.

[26] The compound (F) contains the macromonomer (A), the macromonomer (A) contains a structural unit derived from methacrylate, The thermoplastic resin composition according to any one of [1] to [8] and

[20] to

[25] , wherein the methacrylate is preferably methyl methacrylate, n-butyl methacrylate, lauryl methacrylate, dodecyl methacrylate, stearyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, benzyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, or 4-hydroxybutyl methacrylate, more preferably methyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, or 4-hydroxybutyl methacrylate, and still more preferably methyl methacrylate or phenyl methacrylate.

[27] The thermoplastic resin composition according to

[26] , wherein the content of the methacrylate-derived structural unit is preferably 50 to 100 mass%, more preferably 60 to 100 mass%, and even more preferably 70 to 100 mass%, of the total amount of the macromonomer (A).

[28] The compound (F) contains the macromonomer (A), the macromonomer (A) contains a structural unit derived from methyl methacrylate, The thermoplastic resin composition according to any one of [1] to [8] and

[20] to

[27] , wherein the content of the structural unit derived from methyl methacrylate is preferably 50 to 100 mass%, more preferably 60 to 100 mass%, and even more preferably 70 to 100 mass%, of the total amount of the macromonomer (A).

[29] The compound (F) contains the macromonomer (A), the macromonomer (A) contains a structural unit derived from a methacrylate other than methyl methacrylate, The thermoplastic resin composition according to any one of [1] to [8] and

[20] to

[28] , wherein the content of the methacrylate other than methyl methacrylate is preferably 0 to 30 mass%, more preferably 0 to 20 mass%, and even more preferably 0 to 15 mass% of the total amount of the macromonomer (A).

[30] The compound (F) contains the macromonomer (A), the macromonomer (A) contains an acrylate-derived structural unit, The thermoplastic resin composition according to any one of [1] to [8] and

[20] to

[29] , wherein the acrylate is preferably methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, or t-butyl acrylate, and more preferably methyl acrylate.

[31] The thermoplastic resin composition according to

[30] , wherein the content of the acrylate-derived structural unit is preferably 0 to 20 mass%, more preferably 0 to 10 mass%, and even more preferably 0 to 8 mass%, of the total amount of the macromonomer (A).

[32] The compound (F) contains the macromonomer (A), The number average molecular weight (Mn) of the macromonomer (A) is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 25,000. The thermoplastic resin composition according to any one of [1] to [8] and

[20] to

[31] .

[33] The compound (F) contains the macromonomer (A), The thermoplastic resin composition according to any one of [1] to [8] and

[20] to

[33] , wherein the mass average molecular weight (Mw) of the macromonomer (A) is preferably 3,000 to 80,000, more preferably 5,000 to 50,000, and even more preferably 7,000 to 40,000.

[34] The compound (F) contains the macromonomer (A), The macromonomer (A) has a chemical structure (E) represented by the following formula (3): When the molar ratio of the chemical structure (E) to the compound (G) is expressed as the chemical structure (E):the compound (G)=1:X, X is preferably 0.01 or more and 100 or less, more preferably 0.03 or more and 10 or less, even more preferably 0.05 or more and 1 or less, particularly preferably 0.05 or more and 0.50 or less, and most preferably 0.2 or more and 0.45 or less. The thermoplastic resin composition according to any one of [1] to [8] and

[20] to

[33] .

[0022] [ka]

[0023] (In formula (3), R 0 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.

[35] The compound (F) contains the copolymer (C), the copolymer (C) contains a structural unit derived from the macromonomer (A), The content of the structural unit derived from the macromonomer (A) is preferably 10 to 100 mass%, more preferably 20 to 80 mass%, and even more preferably 30 to 60 mass%, of the total amount of the copolymer (C). The thermoplastic resin composition according to any one of [1] to [8] and

[20] to

[34] .

[36] The compound (F) contains the copolymer (C), the copolymer (C) contains a structural unit derived from a comonomer (B) other than the macromonomer (A), The comonomer (B) is preferably a (meth)acrylate or an aromatic vinyl, more preferably an acrylate or an aromatic vinyl, and further preferably n-butyl acrylate, 2-methoxyethyl acrylate, or styrene. The thermoplastic resin composition according to any one of [1] to [8] and

[20] to

[35] .

[37] The thermoplastic resin composition according to

[36] , wherein the content of the structural unit derived from the comonomer (B) is preferably 0 to 90 mass%, more preferably 20 to 80 mass%, and even more preferably 40 to 70 mass%, of the total amount of the copolymer (C).

[38] The macromonomer (A) contains a structural unit derived from methacrylate, The thermoplastic resin composition according to any one of

[35] to

[37] , wherein the methacrylate is preferably methyl methacrylate, n-butyl methacrylate, lauryl methacrylate, dodecyl methacrylate, stearyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, benzyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, or 4-hydroxybutyl methacrylate, more preferably methyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, or 4-hydroxybutyl methacrylate, and even more preferably methyl methacrylate or phenyl methacrylate.

[39] The thermoplastic resin composition according to

[38] , wherein the content of the methacrylate-derived structural unit is preferably 50 to 100 mass%, more preferably 60 to 100 mass%, and even more preferably 70 to 100 mass%, of the total amount of the macromonomer (A).

[40] The macromonomer (A) contains a structural unit derived from methyl methacrylate, The thermoplastic resin composition according to any one of

[35] to

[39] , wherein the content of the structural unit derived from methyl methacrylate is preferably 50 to 100 mass%, more preferably 60 to 100 mass%, and even more preferably 70 to 100 mass% of the total amount of the macromonomer (A).

[41] The macromonomer (A) contains a structural unit derived from a methacrylate other than methyl methacrylate, The thermoplastic resin composition according to any one of

[35] to

[40] , wherein the content of the methacrylate other than methyl methacrylate is preferably 0 to 30 mass%, more preferably 0 to 20 mass%, and even more preferably 0 to 15 mass%, of the total amount of the macromonomer (A).

[42] The macromonomer (A) contains an acrylate-derived structural unit, The thermoplastic resin composition according to any one of

[35] to

[41] , wherein the acrylate is preferably methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, or t-butyl acrylate, and more preferably methyl acrylate.

[43] The thermoplastic resin composition according to

[42] , wherein the content of the acrylate-derived structural unit is preferably 0 to 20 mass%, more preferably 0 to 10 mass%, and even more preferably 0 to 8 mass%, of the total amount of the macromonomer (A).

[44] The thermoplastic resin composition according to any one of

[35] to

[43] , wherein the number average molecular weight (Mn) of the macromonomer (A) is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 25,000.

[45] The thermoplastic resin composition according to any one of

[35] to

[44] , wherein the mass average molecular weight (Mw) of the macromonomer (A) is preferably 3,000 to 80,000, more preferably 5,000 to 50,000, and even more preferably 7,000 to 40,000.

[46] The thermoplastic resin composition according to any one of

[35] to

[45] , wherein the mass average molecular weight (Mw) of the copolymer (C) is preferably 100,000 to 3,000,000, more preferably 200,000 to 2,500,000, and even more preferably 250,000 to 2,000,000.

[47] The copolymer (C) has a chemical structure (E) represented by the following formula (3): The thermoplastic resin composition according to any one of

[35] to

[46] , wherein when the molar ratio of the chemical structure (E) to the compound (G) is expressed as the chemical structure (E):the compound (G)=1:X, X is preferably 0.01 or more and 100 or less, more preferably 0.05 or more and 30 or less, and even more preferably 0.2 or more and 10 or less.

[0024] [ka]

[0025] (In formula (3), R 0 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.

[48] ​​The thermoplastic resin composition according to any one of

[35] to

[47] , wherein the molar concentration of the terminal double bond of the copolymer (C), as defined by the method described in the Examples, is preferably 0.0010 to 0.0100 mmol / g, more preferably 0.0015 to 0.0080 mmol / g, and even more preferably 0.0020 to 0.0075 mmol / g.

[49] The compound (G) may be a compound represented by the formula (2), 1 ~R 4 are each independently a branched alkyl group having 3 to 5 carbon atoms, and R 5is preferably a linear alkyl group having 1 to 3 carbon atoms or a hydrogen atom, and examples thereof include 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd.; trade name Sumilizer GM), 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd.; trade name Sumilizer GS), 2-t-butyl-6-(3'-t-butyl-2'-hydroxy-5'-methyl-methylbenzyl)-4-methylphenyl acrylate, and 2,5-di-t-butyl-6

[48] ​​The thermoplastic resin composition according to any one of [1] to

[48] , wherein 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-phenyl acrylate is more preferred, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate and 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate are even more preferred, and 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate is particularly preferred.

[50] The thermoplastic resin composition according to any one of [1] to

[49] , wherein the terminal group is a group derived from a hydrogen atom and a radical polymerization initiator, and the radical polymerization initiator is preferably benzoyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), or 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile).

[51] A molding material comprising the thermoplastic resin composition according to any one of [1] to

[50] .

[52] A molded body obtained by molding the molding material according to

[51] .

[53] A vehicle component obtained by molding the molding material according to

[51] .

[54] An electric / electronic component obtained by molding the molding material according to

[51] .

[55] An optical member obtained by molding the molding material according to

[51] .

[56] A medical device obtained by molding the molding material according to

[51] .

[57] A food package obtained by molding the molding material according to

[51] .

[58] A method for producing a molded article, comprising molding the molding material according to

[51] to obtain a molded article.

[59] The method for producing a molded article according to

[52] , wherein the molding is injection molding or extrusion molding. [Effects of the Invention]

[0026] According to the present invention, a thermoplastic resin composition having good resistance to thermal decomposition, a molding material, and a molded article obtained by molding the molding material are obtained. [Brief explanation of the drawings]

[0027] [Figure 1] 1 is a schematic cross-sectional view showing an example of a lamp using a lamp cover as a vehicle component formed from the thermoplastic resin composition of the present invention. [Figure 2] 1 is a schematic cross-sectional view showing an example of a touch panel as an electrical / electronic member formed from the thermoplastic resin composition of the present invention. [Figure 3] 1 is a schematic cross-sectional view showing an example of a light guide plate for image display as an optical member formed from the thermoplastic resin composition of the present invention. [Figure 4] 1 is a schematic cross-sectional view showing an example of a tube as a medical member formed from the thermoplastic resin composition of the present invention. [Figure 5] 1 is a plan view showing an example of a double-bag package as food packaging formed from the thermoplastic resin composition of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0028] Below, we will explain in detail the form for implementing the present invention (hereinafter referred to as the ``present embodiment''), but the present invention is not limited to the following description and can be implemented in various modified forms within the scope of its gist. In the following, the monomer component before polymerization will be referred to as "monomer" and sometimes abbreviated as "monomer." Furthermore, a constituent unit (structural unit) derived from a monomer that constitutes a polymer will also be referred to as "monomer unit." Furthermore, (meth)acrylate refers to methacrylate or acrylate.

[0029] The thermoplastic resin composition according to the present invention contains a macromonomer (A) represented by the following formula (1) and / or a copolymer (C) containing a structural unit derived from formula (1) (hereinafter referred to as "compound (F)") and a compound (G). The thermoplastic resin composition is a composition containing at least one thermoplastic resin. That is, the thermoplastic resin composition according to the present embodiment contains at least compound (F) and compound (G), and may optionally contain a thermoplastic resin (X) different from compound (F). When the thermoplastic resin composition does not contain thermoplastic resin (X), compound (F) is a thermoplastic resin. When the thermoplastic resin composition contains thermoplastic resin (X), compound (F) may or may not exhibit thermoplasticity. The thermoplastic resin composition may contain a copolymer of macromonomer (A) and comonomer (B) as copolymer (C) containing a structural unit derived from formula (1). The thermoplastic resin composition can be used as a molding material to produce a molded article.

[0030] [Compound (F)] The thermoplastic resin composition of the present invention contains a compound (F) which is a macromonomer (A) represented by the following formula (1) and / or a copolymer (C) containing a structural unit derived from formula (1).

[0031] [ka]

[0032] (In formula (1), R 0 ~R n are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. 1 ~Xn are each independently a hydrogen atom or a methyl group. Z is a terminal group. n is a natural number from 1 to 10,000.

[0033] [Macromonomer (A)] The macromonomer (A) has a group having a radically polymerizable unsaturated double bond at one end of a poly(meth)acrylate segment. The macromonomer (A) is a compound represented by the following formula (1):

[0034] [ka]

[0035] (In formula (1), R 0 ~R n are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. 1 ~X n are each independently a hydrogen atom or a methyl group. Z is a terminal group. n is a natural number from 1 to 10,000.

[0036] [R 0 ~R n ] In formula (1), R 0 ~R n are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. The alkyl group, cycloalkyl group, aryl group, or heterocyclic group may have a substituent.

[0037] R 0 ~R nExamples of the alkyl group include branched or linear alkyl groups having 1 to 20 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl. Among these, in terms of availability, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, and octyl are preferred, with methyl, ethyl, n-propyl, i-propyl, n-butyl, and t-butyl being more preferred, and methyl being particularly preferred.

[0038] R 0 ~R n Examples of the cycloalkyl group include cycloalkyl groups having 3 to 20 carbon atoms. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a t-butylcyclohexyl group, an isobornyl group, an adamantyl group, etc. In view of availability, a cyclopropyl group, a cyclobutyl group, and an adamantyl group are preferred.

[0039] R 0 ~R n The aryl group may be, for example, an aryl group having a carbon number of 6 to 18. Specific examples include a phenyl group, a benzyl group, and a naphthyl group.

[0040] R 0 ~R n Examples of the heterocyclic group include heterocyclic groups having 5 to 18 carbon atoms. Specific examples include a γ-lactone group, an ε-caprolactone group, a morpholine group, etc. Examples of heteroatoms contained in the heterocycle include an oxygen atom, a nitrogen atom, a sulfur atom, etc.

[0041] R 0 ~Rn Examples of the substituents that can be introduced into each independently include a group or atom selected from the group consisting of an alkyl group, an aryl group, a carboxy group, an alkoxycarbonyl group (-COOR'), a carbamoyl group (-CONR'R''), a cyano group, a hydroxy group, an amino group, an amide group (-NR'R''), a halogen atom, an allyl group, an epoxy group, an alkoxy group (-OR'), and a group exhibiting hydrophilicity or ionicity. Examples of R' and R'' each independently include the same groups as R (excluding heterocyclic groups).

[0042] R 0 ~R n Examples of the alkoxycarbonyl group as a substituent of include a methoxycarbonyl group. R 0 ~R n Examples of the carbamoyl group as a substituent of include an N-methylcarbamoyl group and an N,N-dimethylcarbamoyl group. R 0 ~R n The amide group as the substituent of the formula (I) may be, for example, a dimethylamide group. R 0 ~R n Examples of the halogen atom as a substituent of include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 0 ~R n Examples of the alkoxy group as the substituent include an alkoxy group having 1 to 12 carbon atoms. A specific example is a methoxy group. R 0 ~R n Examples of the hydrophilic or ionic group as a substituent include an alkali salt of a carboxy group or an alkali salt of a sulfoxyl group, a poly(alkylene oxide) group such as a polyethylene oxide group or a polypropylene oxide group, and a cationic substituent such as a quaternary ammonium base.

[0043] R 0 ~R nis preferably at least one selected from an alkyl group, a cycloalkyl group, an aryl group, and a hydroxy group. The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, or an i-propyl group, and from the viewpoint of availability, a methyl group is more preferred.

[0044] [X 1 ~X n ] In formula (1), X 1 ~X n are each a hydrogen atom or a methyl group, and a methyl group is preferred. Furthermore, from the viewpoint of ease of synthesis of the macromonomer (A), X1 to X n It is preferable that at least half of the groups are methyl groups.

[0045] [Z] In formula (1), Z is a terminal group of the macromonomer (A). Examples of the terminal group of the macromonomer (A) include a hydrogen atom and a group derived from a radical polymerization initiator, similar to the terminal groups of polymers obtained by known radical polymerization.

[0046] [Chemical structure (E) represented by formula (3)] The left side portion of the macromonomer (A) or copolymer (C), i.e., the compound containing a structural unit of formula (1) or formula (1), may contain a chemical structure (E) represented by the following formula (3):

[0047] [ka]

[0048] (In formula (3), R 0 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.

[0049] [R 0 ] In equation (3), R 0is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. The alkyl group, cycloalkyl group, aryl group, or heterocyclic group may have a substituent.

[0050] R 0 Examples of the alkyl group include branched or linear alkyl groups having 1 to 20 carbon atoms. Specific examples include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl. Among these, in terms of availability, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, and octyl are preferred, with methyl, ethyl, n-propyl, i-propyl, n-butyl, and t-butyl being more preferred, and methyl being particularly preferred.

[0051] R 0 Examples of the cycloalkyl group include cycloalkyl groups having 3 to 20 carbon atoms. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a t-butylcyclohexyl group, an isobornyl group, an adamantyl group, etc. In view of availability, a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and an adamantyl group are preferred.

[0052] R 0 The aryl group may be, for example, an aryl group having a carbon number of 6 to 18. Specific examples include a phenyl group, a benzyl group, and a naphthyl group.

[0053] R 0Examples of the heterocyclic group include heterocyclic groups having 5 to 18 carbon atoms. Specific examples include a γ-lactone group, an ε-caprolactone group, a morpholine group, etc. Examples of heteroatoms contained in the heterocycle include an oxygen atom, a nitrogen atom, a sulfur atom, etc.

[0054] R 0 Examples of the substituents that can be introduced into each independently include a group or atom selected from the group consisting of an alkyl group, an aryl group, a carboxy group, an alkoxycarbonyl group (-COOR'), a carbamoyl group (-CONR'R''), a cyano group, a hydroxy group, an amino group, an amide group (-NR'R''), a halogen atom, an allyl group, an epoxy group, an alkoxy group (-OR'), and a group exhibiting hydrophilicity or ionicity. Examples of R' and R'' each independently include the same groups as R (excluding heterocyclic groups).

[0055] R 0 Examples of the alkoxycarbonyl group as a substituent of include a methoxycarbonyl group. R 0 Examples of the carbamoyl group as a substituent of include an N-methylcarbamoyl group and an N,N-dimethylcarbamoyl group. R 0 An example of the amide group as a substituent of R is a dimethylamide group. 0 , R 1 Examples of the halogen atom as a substituent of include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. R 0 Examples of the alkoxy group as the substituent include an alkoxy group having 1 to 12 carbon atoms. A specific example is a methoxy group. R 0 Examples of the hydrophilic or ionic group as a substituent include an alkali salt of a carboxy group or an alkali salt of a sulfoxyl group, a poly(alkylene oxide) group such as a polyethylene oxide group or a polypropylene oxide group, and a cationic substituent such as a quaternary ammonium base.

[0056] R 0 is preferably at least one selected from an alkyl group, a cycloalkyl group, an aryl group, and a hydroxy group. The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, or an i-propyl group, and from the viewpoint of availability, a methyl group is more preferred.

[0057] [Raw material monomer for macromonomer (A)] Examples of raw material monomers for obtaining the macromonomer (A) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl ( (Meth)acrylates such as benzyl (meth)acrylate, isobornyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and phenoxyethyl (meth)acrylate; hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and glycerol (meth)acrylate; (meth)acrylic Acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxypropyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic Carboxy group-containing vinyl monomers such as maleic anhydride, itaconic acid, monomethyl maleate, and monomethyl itaconate; acid anhydride group-containing vinyl monomers such as maleic anhydride and itaconic anhydride; epoxy group-containing vinyl monomers such as glycidyl (meth)acrylate, glycidyl α-ethyl acrylate, and 3,4-epoxybutyl (meth)acrylate; amino group-containing (meth)acrylate vinyl monomers such as dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate;Examples of the vinyl monomer include vinyl monomers containing an amide group, such as (meth)acrylamide, Nt-butyl(meth)acrylamide, N-methylol(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, diacetone acrylamide, maleic acid amide, and maleimide; vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, (meth)acrylonitrile, vinyl chloride, vinyl acetate, and vinyl propionate; and polyfunctional vinyl monomers such as divinylbenzene, ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, allyl (meth)acrylate, and N,N'-methylenebis(meth)acrylamide. One or more of these can be appropriately selected and used. Among these, methacrylate is preferred in terms of easy availability of the monomer. As the methacrylate, methyl methacrylate, n-butyl methacrylate, lauryl methacrylate, dodecyl methacrylate, stearyl methacrylate, 2-ethylhexyl methacrylate, phenyl methacrylate, benzyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, and 4-hydroxybutyl methacrylate are preferred, methyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, and 4-hydroxybutyl methacrylate are more preferred, and methyl methacrylate and phenyl methacrylate are even more preferred.

[0058] Furthermore, it is preferable to use methyl methacrylate in terms of the ease of obtaining the macromonomer (A), etc. The proportion of methyl methacrylate in the total 100% by mass of the monomer composition for obtaining the macromonomer (A) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0059] Furthermore, as the raw material monomer for obtaining the macromonomer (A), a monomer composition containing the above-mentioned methacrylate or acrylate is preferred from the viewpoint of the thermal decomposition resistance of the macromonomer (A) and the macromonomer copolymer using the macromonomer (A) as a raw material. Examples of acrylates include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, and t-butyl acrylate. Among these, methyl acrylate is preferred in terms of availability.

[0060] The methacrylate content in the monomer composition for obtaining macromonomer (A) is preferably 80% by mass or more, more preferably 82% by mass or more, and even more preferably 84% by mass or more, from the viewpoint of the heat resistance of macromonomer (A), macromonomer copolymers using macromonomer (A) as a raw material, resin compositions containing the same, and molded articles therefrom. Furthermore, the methacrylate content in the monomer composition for obtaining macromonomer (A) is preferably 100% by mass or less, more preferably 99% by mass or less, and even more preferably 98% by mass or less, from the viewpoint of the thermal decomposition resistance of macromonomer (A), macromonomer copolymers using macromonomer (A) as a raw material, resin compositions containing the same, and molded articles therefrom. The acrylate content in the monomer composition for obtaining macromonomer (A) is preferably 0% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more. An acrylate content of 1% by mass or more improves the thermal decomposition resistance of macromonomer (A), macromonomer copolymers using macromonomer (A) as a raw material, resin compositions containing the same, and molded articles therefrom. The content of the acrylate in the monomer composition for obtaining the macromonomer (A) is preferably 20% by mass or less, more preferably 18% by mass or less, and even more preferably 16% by mass or less. If the content of the acrylate in the monomer composition for obtaining the macromonomer (A) is 20% by mass or less, the heat resistance of the resin composition containing it and the molded article therefrom will be good. In this specification, the content of the structural unit contained in the polymer can be calculated from the amount of monomer charged during polymerization.

[0061] [Method for producing macromonomer (A)] The macromonomer (A) can be produced by known methods, such as a method using a cobalt chain transfer agent (U.S. Pat. No. 4,680,352), a method using an α-substituted unsaturated compound such as α-bromomethylstyrene as a chain transfer agent (WO 88 / 04304), and a thermal decomposition method (JP-A-11-240854). Among these, the method for producing the macromonomer (A) is preferably a method using a cobalt chain transfer agent, since it requires fewer production steps and uses a catalyst with a high chain transfer constant.

[0062] Methods for producing macromonomer (A) using a cobalt chain transfer agent include, for example, bulk polymerization, solution polymerization, and aqueous dispersion polymerization methods such as suspension polymerization and emulsion polymerization. Among these, aqueous dispersion polymerization is preferred from the viewpoint of simplifying the recovery process of macromonomer (A). It is also possible to obtain a macromonomer copolymer by polymerization reaction by adding comonomer (B) and a thermal polymerization initiator directly to macromonomer (A) without recovering it.

[0063] The cobalt chain transfer agent used in the present invention may be a cobalt chain transfer agent represented by formula (4), and examples of the cobalt chain transfer agent that can be used include those described in Japanese Patent No. 3587530, JP-A-6-23209, JP-A-7-35411, U.S. Pat. Nos. 45269945, 4694054, 4834326, 4886861, 5324879, WO 95 / 17435, and JP-A-9-510499.

[0064] [ka]

[0065] [In the formula, R1 to R4 each independently represent an alkyl group, a cycloalkyl group, or an aryl group; and X each independently represent an F atom, a Cl atom, a Br atom, an OH group, an alkoxy group, an aryloxy group, an alkyl group, or an aryl group.]

[0066] Specific examples of cobalt chain transfer agents include bis(borondifluorodimethyldioximinocyclohexane)cobalt(II), bis(borondifluorodimethylglyoximate)cobalt(II), bis(borondifluorodiphenylglyoximate)cobalt(II), cobalt(II) complexes of vicinaliminohydroxyimino compounds, cobalt(II) complexes of tetraazatetraalkylcyclotetradecatetraenes, N,N'-bis(salicylidene)ethylenediaminocobalt(II) complexes, cobalt(II) complexes of dialkyldiazadioxodialkyldodecadienes, and cobalt(II) porphyrin complexes. Among these, bis(borondifluorodiphenylglyoximate)cobalt(II) (R1 to R4: phenyl groups, X: F atom) is preferred because it is stable in aqueous media and has a high chain transfer effect. One or more of these can be appropriately selected and used.

[0067] The amount of the cobalt chain transfer agent used is preferably 20 ppm or more and 350 ppm or less based on 100 parts by mass of the monomer for obtaining the macromonomer (A). When the amount of the cobalt chain transfer agent used is 20 ppm or more, the desired molecular weight reducing effect is easily achieved, and when it is 350 ppm or less, coloration of the obtained macromonomer (A) is easily prevented.

[0068] Examples of solvents used when obtaining the macromonomer (A) by solution polymerization include hydrocarbons such as toluene, ethers such as diethyl ether and tetrahydrofuran, halogenated hydrocarbons such as dichloromethane and chloroform, ketones such as acetone, alcohols such as methanol, nitriles such as acetonitrile, vinyl esters such as ethyl acetate, carbonates such as ethylene carbonate, and supercritical carbon dioxide. These can be used alone or in combination of two or more.

[0069] [Comonomer (B)] The comonomer (B) can be used when producing the copolymer (C) described below. The comonomer (B) is not particularly limited as long as it is copolymerizable with the macromonomer (A), and various polymerizable monomers can be used as needed. As the comonomer (B), a monomer having a double bond and radical polymerizability can be used alone or in combination of two or more kinds. Furthermore, when the comonomer (B) contains multiple monomer types, it is also possible to use a monomer that has poor copolymerizability with the macromonomer (A) as part of the comonomer (B). Specific examples include the same monomers as those used to obtain the macromonomer (A). The comonomer (B) is preferably a (meth)acrylate or an aromatic vinyl because of its good copolymerizability with the macromonomer (A). Examples of the (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, methoxypropyl (meth)acrylate, methoxybutyl (meth)acrylate, ethoxymethyl (meth)acrylate, ethoxyethyl (meth)acrylate, ethoxypropyl (meth)acrylate, ethoxy ... Examples of suitable vinyl acrylates include propoxymethyl (meth)acrylate, propoxyethyl (meth)acrylate, propoxypropyl (meth)acrylate, ethoxybutyl (meth)acrylate, propoxymethyl (meth)acrylate, propoxyethyl (meth)acrylate, propoxypropyl (meth)acrylate, propoxybutyl (meth)acrylate, butoxymethyl (meth)acrylate, butoxyethyl (meth)acrylate, butoxypropyl (meth)acrylate, butoxybutyl (meth)acrylate, "Blemmer PME-100" (a methoxypolyethylene glycol methacrylate (having two ethylene glycol chains), product name, manufactured by NOF Corporation), and "Blemmer PME-200" (a methoxypolyethylene glycol methacrylate (having four ethylene glycol chains), product name, manufactured by NOF Corporation). Examples of aromatic vinyl acrylates include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, and pt-butylstyrene, vinylethylbenzene, vinyltoluene, vinylxylene, vinylnaphthalene, diphenylethylene, and divinylbenzene. The comonomer (B) can be used alone or in combination of two or more kinds.

[0070] Among the above monomers, it is preferable to select acrylates because of their good copolymerizability with the macromonomer (A).Preferred examples of acrylates include 2-ethylhexyl acrylate, 4-hydroxybutyl acrylate, n-butyl acrylate, n-propyl acrylate, ethyl acrylate, 2-hydroxyethyl acrylate, methoxymethyl acrylate, methoxyethyl acrylate, methoxypropyl acrylate, methoxybutyl acrylate, methoxypolyethylene glycol acrylate, methoxymethyl methacrylate, methoxyethyl methacrylate, methoxypropyl methacrylate, methoxybutyl methacrylate, methoxypolyethylene glycol methacrylate, and methyl acrylate.

[0071] Furthermore, when functions such as flexibility, toughness, and improved impact resistance are to be imparted to a polymer of comonomer (B), a comonomer having a low glass transition temperature (Tg) of the homopolymer can be selected. The glass transition temperatures (Tg) of homopolymers are described in, for example, Polymer Handbook [Polymer Handbook, J. Brandrup, Interscience, 1989]. Examples of comonomers (B) having a low glass transition temperature of the homopolymer include 2-ethylhexyl acrylate, n-butyl acrylate, n-propyl acrylate, lauryl acrylate, methoxymethyl acrylate, methoxyethyl acrylate, methoxypropyl acrylate, methoxybutyl acrylate, methoxypolyethylene glycol acrylate, methoxymethyl methacrylate, methoxyethyl methacrylate, methoxypropyl methacrylate, methoxybutyl methacrylate, methoxypolyethylene glycol methacrylate, and methyl acrylate.

[0072] Furthermore, when the function of inhibiting protein adhesion is to be imparted to a polymer of comonomer (B), preferred comonomers (B) are methoxymethyl acrylate, methoxyethyl acrylate, methoxypropyl acrylate, methoxybutyl acrylate, methoxypolyethylene glycol acrylate, methoxymethyl methacrylate, methoxyethyl methacrylate, methoxypropyl methacrylate, methoxybutyl methacrylate, and methoxypolyethylene glycol methacrylate, more preferred are methoxyethyl acrylate, methoxypropyl acrylate, methoxypolyethylene glycol acrylate, and methoxypolyethylene glycol methacrylate, and even more preferred are methoxyethyl acrylate and methoxyethyl methacrylate.

[0073] Furthermore, as the comonomer (B), an aromatic vinyl can be used as a high refractive index component in order to match the refractive index of a homopolymer of the comonomer (B) with that of the polymer (M) described below or the macromonomer (A).

[0074] Examples of aromatic vinyls include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, pt-butylstyrene, vinylethylbenzene, vinyltoluene, vinylxylene, vinylnaphthalene, diphenylethylene, and divinylbenzene. Among these, styrene is preferred from the viewpoints of practical properties and productivity. These can be used alone or in combination of two or more.

[0075] When the aforementioned acrylate and aromatic vinyl are used as comonomer (B), the proportion of aromatic vinyl in 100% by mass of the total of comonomer (B) is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and particularly preferably 26% by mass or more. When the aromatic vinyl is 10% by mass or more, the transparency of the thermoplastic resin composition and molding materials and molded articles made therefrom is good. When the aforementioned acrylate and aromatic vinyl are used as comonomer (B), the proportion of aromatic vinyl in 100% by mass of the total of comonomer (B) is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less. When the aromatic vinyl is 50% by mass or less, the weather resistance is good.

[0076] [Copolymer (C)] The compound (F) contained in the thermoplastic resin composition of the present invention may be a copolymer (C). The copolymer (C) is a macromonomer copolymer obtained by copolymerizing a macromonomer (A) and a comonomer (B). The copolymerization reaction mechanism between the macromonomer (A) and the comonomer (B) is described in detail in a report by Yamada et al. (Prog. Polym. Sci. 31 (2006) pp. 835-877). When radical polymerization is performed in the presence of the macromonomer (A) and the comonomer (B), if the chemical structure (E) is present at the end of the macromonomer (A), it may migrate to the end of a newly generated polymer chain due to addition-fragmentation chain transfer. Therefore, part or all of the copolymer (C) has the chemical structure (E).

[0077] [Method for producing copolymer (C)] The copolymer (C) is obtained by copolymerizing the macromonomer (A) and the comonomer (B). When the copolymerization reaction to obtain the copolymer (C) is carried out, a radical polymerization initiator and, if necessary, a chain transfer agent are used.

[0078] The method for producing the copolymer (C) is not particularly limited, and various methods can be used, such as solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization, etc. Aqueous polymerization such as suspension polymerization or emulsion polymerization is preferred because it is easy to control the heat generated by polymerization and has excellent productivity, and suspension polymerization is more preferred because the polymerization and recovery operations are simpler.

[0079] Examples of the method for producing the copolymer (C) by suspension polymerization include the following methods [I] and [II]. [I] Macromonomer (A) is dissolved in comonomer (B) and a radical polymerization initiator is added. This macromonomer (A) solution is dispersed in an aqueous solution containing a dispersant to obtain a syrup dispersion. The obtained syrup dispersion is then subjected to suspension polymerization. [II] A comonomer (B) is added to an aqueous suspension obtained by synthesizing a macromonomer (A) by suspension polymerization to obtain a syrup suspension, which is a dispersion of the comonomer (B) in which the macromonomer (A) is dissolved. The obtained syrup suspension is then subjected to suspension polymerization.

[0080] The copolymer (C) obtained by the production method [I] tends to have excellent optical properties. In addition, the production method [II] can shorten the production process by eliminating the step of recovering the macromonomer (A).

[0081] In either method [I] or [II], it is preferable to heat the macromonomer (A) when dissolving it in the comonomer (B). The heating temperature is preferably 30 to 90°C. A heating temperature of 30°C or higher can improve the solubility of the macromonomer (A). A heating temperature of 35°C or higher is more preferable. Furthermore, a heating temperature of 90°C or lower can suppress the volatilization of the comonomer (B). A heating temperature of 75°C or lower is more preferable.

[0082] In the production method [I], the timing of adding the radical polymerization initiator to the comonomer (B) in which the macromonomer (A) has been dissolved is preferably after the macromonomer (A) has been dissolved in the comonomer (B). The temperature at which the radical polymerization initiator is added to the macromonomer (A) and / or comonomer (B) is preferably lower than the SADT (the lowest temperature at which self-accelerating decomposition occurs) and is preferably 20°C or more lower than the 10-hour half-life temperature of the radical polymerization initiator. The temperature at which the polymerization reaction is carried out is preferably equal to or higher than the 10-hour half-life temperature of the radical polymerization initiator and is preferably 5 to 20°C higher than the 10-hour half-life temperature.

[0083] Examples of the radical polymerization initiator include organic peroxides and azo compounds. Specific examples of organic peroxides include 2,4-dichlorobenzoyl peroxide, t-butyl peroxypivalate, o-methylbenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, t-butylperoxy-2-ethylhexanoate, cyclohexanone peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, lauroyl peroxide, diisopropylbenzene hydroperoxide, t-butyl hydroperoxide, and di-t-butyl peroxide. Specific examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile). In view of availability, benzoyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile) and 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) are preferred. The radical polymerization initiators can be used alone or in combination of two or more kinds.

[0084] The amount of radical polymerization initiator added is preferably 0.0001 to 10 parts by mass per 100 parts by mass of the total amount of macromonomer (A) and comonomer (B) in terms of controlling heat generated by polymerization.

[0085] The chain transfer agent is added as needed to adjust the molecular weight of the copolymer (C) and the polymerization reaction rate. The chain transfer agent also has the effect of preventing the terminal double bond group of the macromonomer (A) from remaining unreacted. Examples of the chain transfer agent include sulfur-containing chain transfer agents such as t-dodecyl mercaptan and n-octyl mercaptan, α-methylstyrene dimer, carbon tetrachloride, and terpenoids. However, sulfur-containing chain transfer agents are preferred from the viewpoints of availability and high chain transfer ability.

[0086] When a chain transfer agent is used, its content is preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, and even more preferably 0.05 parts by mass or more, per 100 parts by mass of the monomer mixture. When the content of the chain transfer agent is 0.01 parts by mass or more, the effect of adding it is sufficiently obtained. When the content of the chain transfer agent is 0.5 parts by mass or less, more preferably 0.3 parts by mass or less, and even more preferably 0.2 parts by mass or less, per 100 parts by mass of the monomer mixture. When the content of the chain transfer agent is 0.5 parts by mass or less, the mechanical strength of the resulting copolymer (C) is excellent.

[0087] [Compound (G)] The thermoplastic resin composition of the present invention contains compound (G). Compound (G) is represented by the following formula (2). Compound (G) has a phenolic hydroxyl group and a CH═CH- group as functional groups. This compound (G) is presumed to exhibit an effect of preventing thermal degradation of the thermoplastic resin composition by effectively capturing radicals generated by depolymerization of macromonomer (A) contained in the thermoplastic resin composition with the CH═CH- group and stabilizing the radicals by rapidly transferring hydrogen atoms from the phenolic hydroxyl group via intramolecular hydrogen bonding. Therefore, thermoplastic resin compositions containing compound (G) have excellent thermal decomposition resistance during molding and processing.

[0088] [ka]

[0089] R in equation (2) 1 ~R 4 each independently represents an alkyl group having 1 to 5 carbon atoms, and R 5 represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom. Specific examples of compound (G) include 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd.; trade name Sumilizer GM), 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate (manufactured by Sumitomo Chemical Co., Ltd.; trade name Sumilizer GS), 2-t-butyl-6-(3'-t-butyl-2'-hydroxy-5'-methyl-methylbenzyl)-4-methylphenyl acrylate, and 2,5-di-t-butyl-6-(3'-5'-di-t-butyl-2'-hydroxymethylbenzyl)-phenyl acrylate. Among these, 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate or 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate is preferred, and 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate is more preferred.

[0090] The amount of compound (G) added to the thermoplastic resin composition is adjusted as appropriate depending on the amount of chemical structure (E) contained in the thermoplastic resin composition and the molding conditions of the thermoplastic resin composition. Even a very small amount of compound (G) can improve the thermal decomposition resistance of the thermoplastic resin composition during molding. However, to sufficiently improve thermal decomposition resistance, the amount of compound (G) is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more, based on 100% by mass of the total thermoplastic resin composition. Furthermore, to prevent a decrease in the mechanical strength of the thermoplastic resin composition and contamination of molds and the like due to bleed-out, the amount of compound (G) is preferably 6% by mass or less, more preferably 3% by mass or less, based on 100% by mass of the total thermoplastic resin composition.

[0091] Furthermore, the amount of compound (G) added to the thermoplastic resin composition is preferably adjusted in consideration of the content of chemical structure (E). When the molar ratio of chemical structure (E) to compound (G) contained in the thermoplastic resin composition is expressed as chemical structure (E):compound (G)=1:X, the value of X is preferably 0.01 or more and 100 or less. Furthermore, the value of X is preferably 0.01 or more, more preferably 0.05 or more, and even more preferably 0.2 or more. Furthermore, the value of X is preferably 100 or less, preferably 30 or less, and even more preferably 10 or less. When the value of X is 0.01 or more, the effect of improving the thermal decomposition resistance of the thermoplastic resin composition is exhibited. When the value of X is 100 or less, deterioration in the physical properties of a molded article made of the thermoplastic resin composition is suppressed, and costs can be reduced.

[0092] [Content of Chemical Structure (E) in Thermoplastic Resin Composition] The content of the chemical structure (E) contained in the thermoplastic resin composition is 1 This can be confirmed by H-NMR measurement. Specifically, the integral value of the proton peak at the trans position of the terminal double bond of the chemical structure (E) is confirmed, and the molar concentration of the chemical structure (E) contained in the thermoplastic resin composition can be calculated. For example, in the formula (3) of the chemical structure (E), 0When R is a methyl group and the monomer unit adjacent to chemical structure (E) is a methacrylate unit, the proton peak at the trans position of the terminal double bond group derived from chemical structure (E) is observed at 5.48 ppm, and R 0 is a methyl group and the monomer unit adjacent to chemical structure (E) is an acrylate unit, the trans proton peak is known to be observed at 5.54 ppm (Reference: J. Polym. Sci: Part A: Polym. Chem., Vol. 41, pp. 645-654 (2003)). For example, the number average molecular weight of macromonomer (A) having chemical structure (E) is 3,000 [g / mol] as determined by GPC (gel permeation chromatography). 1 Consider the case where the introduction rate of the terminal double bond confirmed by H-NMR measurement is 99% or more. In this case, the molar concentration (millimolar concentration) of the terminal double bond of the macromonomer (A) is 1 ÷ 3,000 × 1,000 = 0.333 [mmol / g] In this way, the molar concentration of the chemical structure (E) contained in the thermoplastic resin composition can be calculated. When calculating the content of the chemical structure (E) in the copolymer (C) or a mixture of the copolymer (C) and the polymer (M), 1 By adding a standard substance during H-NMR measurement and comparing it, the molar concentration of chemical structure (E) can be calculated.

[0093] Polymer The thermoplastic resin composition of the present invention may optionally contain a polymer (M) different from the macromonomer (A) represented by formula (1) and / or the copolymer (C) containing a structural unit derived from formula (1). The polymer (M) preferably does not have the chemical structure (E). For example, it is preferable that the thermoplastic resin composition contains the polymer (M) as one of its main components in combination with the macromonomer (A) and / or the copolymer (C). As described above, when the compound (F) contained in the thermoplastic resin composition is a compound that does not exhibit thermoplasticity, the thermoplastic resin (X) must be contained, and therefore the polymer (M) must be the thermoplastic resin (X). Even when the compound (F) is a polymer that is a thermoplastic resin, the polymer (M) is preferably a thermoplastic resin. In this case, any general-purpose thermoplastic resin can be used as the polymer (M) without any particular limitations. Examples of polymer (M) include polymethyl methacrylate, polycarbonate, rigid polyvinyl chloride, flexible polyvinyl chloride, polyolefin, polyurethane, polyester, polystyrene, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), and methyl methacrylate-styrene copolymer (MS resin). Among these, at least one selected from the group consisting of polymethyl methacrylate, polycarbonate, polyvinyl chloride, polyolefin, polyurethane, and polyester is preferred, with polymethyl methacrylate and polycarbonate being more preferred, and polymethyl methacrylate being most preferred. These polymers (M) may be used alone or in combination.

[0094] Further, some polymers (M) will be specifically explained. Polymethyl methacrylate is a polymer containing 80% by mass or more of methyl methacrylate units, and is also called methacrylic resin. Examples of polymethyl methacrylate include ACRYPET, a product name manufactured by Mitsubishi Chemical Corporation. Representative types of ACRYPET include VH, MD, MF, VH5, TF8, TF9, VH6, VHM, VHS, SV, VH4, TN100, and the like.

[0095] Polycarbonates include aromatic polycarbonates and aliphatic polycarbonates. Examples of aromatic polycarbonates include polycarbonates having a bisphenol-A skeleton. Examples of aliphatic polycarbonates include polycarbonates containing an isosorbide skeleton, such as Durabio (trade name, manufactured by Mitsubishi Chemical Corporation). Representative Durabio varieties include D7340R, D6350R, D5360R, and D5380R.

[0096] Polyvinyl chloride (PVC) includes rigid PVC and flexible PVC, and is a resin composition containing a reinforcing agent, a plasticizer, a stabilizer, and the like. Examples of PVC include products manufactured by Shin-Etsu Chemical Co., Ltd. under the series name Straight Polymer. Representative varieties of Shin-Etsu PVC Straight Polymer include, for example, TK-500, TK-600, TK-700, TK-800, TK-1000, TK-1300, and TK-1400. Examples of additives such as reinforcing agents and processing aids include products manufactured by Mitsubishi Chemical Corporation under the trade name Metablen. Representative varieties of Metablen suitable for PVC include, for example, P-type, L-1000, S-2001, W-300A, W-450A, W-377, C-223A, C-215A, C-201A, C-140A, F-410, and H-602. Examples of plasticizers include DOP, DINP, and TOTM from J-Plus Corporation, and DINCH from BASF. Examples of stabilizers include complex metal soap stabilizers such as Ba-Zn, Ca-Zn, Ba-Ca-Sn, Ca-Mg-Sn, Ca-Zn-Sn, Pb-Sn, and Pb-Ba-Ca. Examples of antioxidants include epoxy compounds such as epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil.

[0097] When the thermoplastic resin composition contains polymer (M), the polymer (M) preferably accounts for 10 to 95 mass%, more preferably 20 to 90 mass%, and even more preferably 30 to 80 mass%, of the total 100 mass% of the thermoplastic resin composition. By ensuring that the proportion of polymer (M) falls within the above range, the characteristics of polymer (M) can be imparted to the thermoplastic resin composition.

[0098] [Additive (D)] The thermoplastic resin composition of the present invention may contain an additive (D) as needed. Various additives other than the compound (G) may be selected as the additive (D). Examples of the additive (D) include various stabilizers such as antioxidants, ultraviolet absorbers, and heat stabilizers; colorants such as inorganic pigments, organic pigments, and dyes; conductivity-imparting agents such as carbon black and ferrite; inorganic fillers; lubricants; mold release agents; plasticizers; organic peroxides; neutralizers; crosslinking agents; and reinforcing agents. When additive (D) is added, the proportion of additive (D) is preferably 20% by mass or less, more preferably 10% by mass or less, relative to 100% by mass of the resin composition. By setting the proportion of additive (D) to 20% by mass or less, the inherent properties of the thermoplastic resin composition are maintained. The total content (mass %) of the compound (F), the compound (G), and the additive (D) relative to the total amount of the thermoplastic resin composition does not exceed 100 mass %.

[0099] [Method of producing thermoplastic resin composition] The method for producing the thermoplastic resin composition of the present invention is not particularly limited, and commonly used resin mixing methods and melt-kneading methods can be applied. The thermoplastic resin composition is produced by mixing and / or kneading the compound (F) and the compound (G) as essential components with the polymer (M) or the like added as needed. Examples of resin mixing and / or melt-kneading methods include a Henschel mixer, a Banbury mixer, a V-type mixer, a ribbon blender, a roll mill, a single-screw extruder, and a twin-screw extruder. These production methods can be combined as appropriate.

[0100] [Molding materials and molded articles using thermoplastic resin compositions] The thermoplastic resin composition of the present invention has good resistance to thermal decomposition during molding and is therefore suitable for use as a molding material for various purposes. Molding materials are obtained by heating the thermoplastic resin composition to give it fluidity that allows molding, imparting it with a desired shape, and then cooling and hardening it to produce a molded article.

[0101] The method for obtaining a molded article using the molding material of the present invention is not particularly limited, and commonly used molding methods can be applied. Examples of molding methods include injection molding (including insert molding, two-color molding, sandwich molding, and gas injection molding), extrusion molding, inflation molding, T-die film molding, lamination molding, blow molding, hollow molding, compression molding, and calendar molding, which can be used to process the material into various molded articles. Among these, injection molding and extrusion molding are preferred, with injection molding being particularly preferred, given the need for heat resistance. The shape of the molded article is not particularly limited, and examples include sheets, films, plates, particles, lumps, fibers, rods, porous bodies, and foams. The molded film can also be uniaxially or biaxially stretched. Examples of stretching methods include rolls, tentering, and tubular methods. Furthermore, surface treatments commonly used in industry, such as corona discharge treatment, flame treatment, plasma treatment, and ozone treatment, can also be applied.

[0102] The thermoplastic resin composition of the present invention has good thermal decomposition resistance during molding and processing, and therefore contains few low-molecular-weight components, such as monomers and oligomers, resulting from polymer decomposition. Therefore, molding materials containing the resin composition of the present invention and molded articles produced therefrom contain few low-molecular-weight components. Due to these characteristics, the molding material and / or molded article of the present invention are prevented from suffering from poor appearance, reduced mechanical properties, and reduced optical performance due to gas generation during molding and processing. Furthermore, leachable materials can be reduced in leachable material tests required for food packaging, medical packaging, food manufacturing equipment, pharmaceutical manufacturing equipment, medical instruments, and peripheral devices and components. Furthermore, the molding material and / or molded article exhibit reduced odor during storage, molding, and use.

[0103] [use] The uses of the molded article containing the resin composition of the present invention are not particularly limited, but examples thereof include the following uses. In the field of electrical and electronic components, these include covering materials for electric wires, cords, and wire harnesses, insulating sheets, displays and touch panels for office automation equipment, membrane switches, photo covers, relay parts, coil bobbins, IC sockets, fuse cases, camera pressure plates, FDD collets, and floppy hubs. In the field of optical components, these include optical disc substrates, optical disc pickup lenses, optical lenses, LCD substrates, PDP substrates, television screens for projection televisions, phase difference films, fog lamp lenses, illuminated switch lenses, sensor switch lenses, Fresnel lenses, protective glasses, projection lenses, camera lenses, sunglasses, light guide plates, camera strobe reflectors, and LED reflectors. In the field of automotive components, these include headlamp lenses, turn signal lamp lenses, tail lamp lenses, plastic window glass, meter covers, outer panels, door handles, rear panels, wheel caps, visors, roof rails, sunroofs, instrument panels, panels, control cable covering materials, airbag covers, mudguards, bumpers, boots, air hoses, and lamp packing. bolts, gaskets, various moldings such as window moldings, sight shields, weather strips, glass run channels, grommets, vibration control and sound insulation materials, joint materials in the building materials field, handrails, windows, table edge materials, sashes, bathtubs, window frames, signs, lighting covers, water tanks, staircase wainscoting, carports, highway sound insulation walls, multi-wall sheets, steel wire coating materials, lighting globes, switch breakers, protective covers for machine tools, industrial deep-drawn vacuum formed containers, pump housings, home appliances, various packings in the low-voltage field, grips, belts, Rubber feet, rollers, protectors, suction cups, gaskets for refrigerators, switches, connector covers, game machine covers, pachinko machines, OA housings, notebook PC housings, HDD head trays, instrument windows, transparent housings, OA gear rollers, switch case sliders, gas cock knobs, watch frames, watch wheel train center pieces, amber caps, various rolls for OA equipment, tubular molded products such as hoses and tubes, irregular extrusion products, leather-like products, interlocking tools, toys such as soft-touch dolls, pen grips, straps, suction cups,Examples of applications include general goods such as watches, umbrella ribs, cosmetic cases, and toothbrush handles; containers such as housewares and Tupperware; cable ties; various bottles such as blow-molded infusion bottles, food bottles, water bottles, and bottles for personal care such as cosmetics; catheters, syringes, syringe gaskets, drip tubes, tubes, ports, caps, rubber stoppers, dialyzers, blood connectors, dentures, and disposable containers in medical components; and applications involving foam molding are also possible.

[0104] The applications of the molded article containing the thermoplastic resin composition of the present invention in the field of films and sheets are not particularly limited, but examples thereof include the following applications. Namely, stretch film for packaging, wrap film for commercial or household use, pallet stretch film, stretch label, shrink film, shrink label, sealant film, retort film, retort sealant film, aroma-retaining heat seal film, A-PET sealant, frozen food containers and lids, cap seals, heat welding film, heat adhesive film, heat sealing film, bag-in-box sealant film, retort pouches, stand-up pouches, spout pouches, laminated tubes, heavy-duty bags, textile packaging film and other food and miscellaneous goods packaging fields, greenhouse films, mulch films and other agricultural films, infusion bags, multi-chamber containers for high-calorie infusions, peritoneal dialysis (CAPD), antibiotic kit bags and other such products, peritoneal dialysis drainage bags, blood bags, urine bags, surgical bags, ice pillows, ampoule cases, PTP packaging and other medical films and sheets, civil engineering waterproof sheets, waterproof materials, mats, joint materials, flooring materials, roofing applications include construction materials such as filming, decorative films, surface films, and wallpaper; vehicle components such as leather, ceiling materials, trunk linings, interior surface materials, vibration-damping sheets, and sound-insulating sheets; low-voltage applications such as display covers, battery cases, mouse pads, mobile phone cases, IC card holders, floppy disk cases, and CD-ROM cases; toiletries and sanitary products such as toothbrush cases, puff cases, cosmetic cases, medicine cases for eye drops, tissue cases, and face masks; office supplies such as stationery films and sheets, clear files, pen cases, notebook covers, desk mats, keyboard covers, book covers, and binders; furniture leather, toys such as beach balls, rain gear such as umbrellas and raincoats, tablecloths, blister packages, bathtub covers, towel cases, fancy cases, tag cases, pouches, amulet bags, insurance card covers, bankbook cases, passport cases, and knife cases; and general household and miscellaneous goods applications such as retroreflective sheets and synthetic paper.In addition, examples of adhesive compositions or films and sheets to which adhesive properties have been imparted by applying an adhesive to a substrate include carrier tape, adhesive tape, marking film, dicing film for semiconductors or glass, surface protection film, steel plate and plywood protection film, automobile protection film, adhesive tape for packaging and binding, adhesive tape for office and household use, adhesive tape for joining, adhesive tape for paint masking, adhesive tape for surface protection, adhesive tape for sealing, adhesive tape for corrosion prevention and waterproofing, adhesive tape for electrical insulation, adhesive tape for electronic devices, adhesive film for clothing, adhesive tape for medical and sanitary materials such as adhesive tape base film, adhesive tape for identification and decoration, tape for display, packaging tape, surgical tape, adhesive tape for labels, etc.

[0105] FIG. 1 is a schematic cross-sectional view showing an example of a lamp using a lamp cover as a vehicle component formed from the thermoplastic resin composition of the present invention. FIG. 1 shows an example of a headlamp cover using an LED light source as the light source, and the lamp cover 1 protects the vehicle headlight and diffuses and emits light from the LED light source at high brightness. The lamp cover 1 in FIG. 1 has a structure in which the lamp cover 1 is disposed in front of a projection lens 3 disposed in front of an LED light source 4 fixed on a support substrate 5 so as to protect the projection lens 3, and the lamp cover 1 and a housing 2 form a lamp chamber. The lamp cover 1 is formed from the thermoplastic resin composition of the present invention. The housing 2 and support substrate 5 may each be formed from the thermoplastic resin composition of the present invention or from another thermoplastic resin composition.

[0106] FIG. 2 is a schematic cross-sectional view showing an example of a touch panel as an electrical / electronic component formed from the thermoplastic resin composition of the present invention. The microrelief structure 10 as a touch panel in FIG. 2 comprises a substrate 12; a cured resin layer 20 having a microrelief structure 18 formed on the surface of the substrate 12, the microrelief structure 18 comprising a plurality of convex portions 14 and concave portions 16 formed between the convex portions 14; and a dam portion 22 formed on the microrelief structure 18 of the cured resin layer 20 and extending along the surface of the cured resin layer 20 so as to divide the surface of the cured resin layer 20 into Region I and Region II. The substrate 12 is formed from the thermoplastic resin composition of the present invention. The cured resin layer 20 may be formed from the thermoplastic resin composition of the present invention or another thermoplastic resin composition.

[0107] Fig. 3 is a schematic cross-sectional view showing an example of a light guide plate for image display as an optical member formed from the thermoplastic resin composition of the present invention. In the light guide plate for image display 1004 of Fig. 3, a first resin substrate 1001, a hologram layer 1002, and a second resin substrate 1003 are arranged in this order in the thickness direction. At least one of the first resin substrate 1001 and the second resin substrate 1003 is formed from the thermoplastic resin composition of the present invention. The other may be formed from the thermoplastic resin composition of the present invention or from another thermoplastic resin composition.

[0108] Fig. 4 is a schematic cross-sectional view showing an example of a tube as a medical device formed from the thermoplastic resin composition of the present invention. Tube 40 in Fig. 4 has a resin layer 41 formed from the thermoplastic resin composition of the present invention, and the inside of tube 40 is hollow.

[0109] Figure 5 is a plan view showing an example of a double-bag package as a food package formed from the thermoplastic resin composition of the present invention. The double-bag package 40c shown in Figure 5 may be produced by the following process. The single leaf 30a is a creased single leaf 40a with creases 41 to 44 formed at the positions of the dot-dash lines shown in Figure 5(A). The creased single leaf 40a has both left and right ends folded toward the center along creases 41 and 42. The bottom end is also folded upward along crease 43. These folds result in heat-sealing of overlapping portions 45 between the left and right sides of the single leaf 40a and overlapping portion 46 where the bottom end is folded back, producing an intermediate product 40b. The intermediate product 40b shown in Fig. 5(B) becomes a container having an opening 47 at the top. An item to be contained, such as food, is placed inside the intermediate product 40b through the opening 47, the opening 47 is folded downward along the crease 44, and the overlapping portion 48 created by the folding is heat-sealed to produce a double-bag package 40c containing the item. The single sheet 30a is formed from the thermoplastic resin composition of the present invention.

[0110] The 5% weight loss temperature (°C) of the thermoplastic resin composition containing the macromonomer (A) as the compound (F), as defined by the measurement method described in the Examples, is preferably 250 to 400°C, more preferably 260 to 350°C, and still more preferably 270 to 330°C. The improvement in 5% weight loss temperature (°C) of the thermoplastic resin composition containing the macromonomer (A) as the compound (F), as calculated and defined by the measurement method described in the Examples, is preferably 30°C or higher, more preferably 30 to 80°C, and even more preferably 35 to 70°C. The 5% weight loss temperature (°C) of the thermoplastic resin composition containing copolymer (C) as compound (F), as defined by the measurement method described in the Examples, is preferably 250 to 500°C, more preferably 260 to 400°C, and more preferably 270 to 350°C. The improvement range (°C) of the 5% weight loss temperature of the thermoplastic resin composition containing the copolymer (C) as the compound (F), which is calculated and defined by the measurement method described in the Examples, is preferably 1 to 150°C, more preferably 3 to 100°C, and even more preferably 5 to 90°C. [Example]

[0111] EXAMPLES The present invention will be explained in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the examples, "parts" means "parts by mass" or "parts by weight".

[0112] <Evaluation method> The evaluations in the examples and comparative examples were carried out by the following methods.

[0113] (Mass average molecular weight (Mw) and number average molecular weight (Mn) of macromonomer (A)) The mass average molecular weight (Mw) and number average molecular weight (Mn) of the macromonomer (A) obtained in the examples and comparative examples were measured by gel permeation chromatography (GPC). 10 mg of the copolymer obtained was dissolved in 10 ml of tetrahydrofuran, and the solution was filtered through a 0.45 μm filter to prepare a sample for GPC measurement. A polymer measurement guard column (manufactured by Tosoh Corporation, product name: TSK-GUARD COLUMN SUPER HH) and two polymer measurement columns (manufactured by Tosoh Corporation, product name: TSK-GEL SUPER HM-H) were connected in series to a gel permeation chromatography measurement device (manufactured by Tosoh Corporation, model name: HLC-8320). A differential refractometer (RI) was used as the detector. Measurements were performed under the following conditions: separation column temperature: 40°C, mobile phase: tetrahydrofuran, mobile phase flow rate: 0.6 mL / min, and sample injection volume: 10 μL. A calibration curve was created using several types of polymethyl methacrylate with known molecular weights (Polymer Laboratories, peak molecular weight (Mp) 1,560 to 19,500,000) as standard polymers, and Mw and Mn were determined.

[0114] (Mass average molecular weight (Mw) and number average molecular weight (Mn) of copolymer (C)) The mass average molecular weight (Mw) and number average molecular weight (Mn) of the copolymer (C) obtained in the examples and comparative examples were measured using gel permeation chromatography (GPC). 10 mg of the copolymer was dissolved in 10 ml of tetrahydrofuran, and the solution was filtered through a 0.45 μm filter to prepare a sample for GPC measurement. For GPC measurement of the copolymer, a high-performance liquid chromatography analyzer (Tosoh Corporation, model name: HLC-8320) was used, connected in series with a polymer measurement guard column (Tosoh Corporation, product name: TSK-GUARD COLUMN SUPER HH) and one ultra-polymer measurement column (Tosoh Corporation, product name: TSK-GEL GMHHR-H). A differential refractometer (RI) was used as the detector. Measurements were performed under the following conditions: separation column temperature: 40°C, mobile phase: tetrahydrofuran, mobile phase flow rate: 0.6 mL / min, and sample injection volume: 10 μL. Using several types of polymethyl methacrylate with known molecular weights (Polymer Laboratories, peak molecular weights (Mp) 1,560 to 19,500,000) as standard polymers, a calibration curve was created, and the mass-average molecular weight (Mw) and number-average molecular weight (Mn), which are relative molecular weights converted to polymethyl methacrylate, were determined.

[0115] (Molar concentration of chemical structure (E)) The molar concentration of chemical structure (E) is: 1 The introduction rate of the terminal double bond group of the macromonomer (A) was determined by comparing the concentration of the chemical structure (E) with the number average molecular weight (Mn) determined by GPC. 1 H-NMR measurements were carried out using a nuclear magnetic resonance spectrometer under the following conditions: Equipment: JNM-ECZ400 (manufactured by JEOL Ltd.) Deuterated solvent: deuterated chloroform (Sigma-Aldrich) Sample preparation: 1.0 g of deuterated chloroform was added to 0.010 g of macromonomer (A) or macromonomer copolymer. Measurement conditions: 2048 counts, measurement temperature 23°C

[0116] (Thermal decomposition resistance evaluation) Thermal decomposition resistance was evaluated by tracking the weight loss of the sample using a thermogravimetric / differential thermal analyzer. The 5% weight loss temperature is the temperature at which the weight loss reaches 5%, assuming the weight at the start of the measurement to be 100%. The improvement in the 5% weight loss temperature was calculated by subtracting the 5% weight loss temperature when compound (G) was not added from the 5% weight loss temperature when compound (G) was added. The measurement conditions are shown below. Equipment: Hitachi High-Tech Science STA7300 Measurement conditions: Nitrogen flow 200 mL / min, 110°C to 550°C, temperature rise rate 10°C / min

[0117] [Raw materials used] The abbreviations and manufacturers of the compounds used in the following Production Examples, Examples, and Comparative Examples are as follows: MMA: Methyl methacrylate [Mitsubishi Chemical Corporation] MA: Methyl acrylate [Mitsubishi Chemical Corporation] PHMA: Phenyl methacrylate [Mitsubishi Chemical Corporation] BA: n-butyl acrylate [Mitsubishi Chemical Corporation] St: Styrene [Fujifilm Wako Pure Chemical Industries, Ltd.] MEA: 2-Methoxyethyl acrylate [Osaka Organic Chemical Industry Co., Ltd., product name 2-MTA] Perocta O [NOF Corporation] AMBN: 2,2'-azobis(2-methylbutyronitrile) [Fujifilm Wako Pure Chemical Industries, Ltd., product name V59] V-601: Dimethyl 2,2'-azobis(2-methylpropionate) [Fujifilm Wako Pure Chemical Industries, Ltd., product name] nOM: n-octyl mercaptan (Kanto Chemical Co., Ltd.) Sumilizer GS: 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate (product name, manufactured by Sumitomo Chemical Co., Ltd.) ADEKA STAB AO-60: Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (ADEKA Corporation; product name) ADEKA STAB 2112: Tris(2,4-di-t-butylphenyl) phosphite (manufactured by ADEKA Corporation; product name) Tinuvin 770DF: bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (product name, manufactured by BASF) Sumilizer TP-D: Pentaerythritol tetra(3-dodecylthiopropionate) (Sumitomo Chemical Co., Ltd.; product name)

[0118] [Example of production of macromonomer (A) and evaluation of thermal decomposition resistance] [Production Example 1: Synthesis of Dispersant (1)] A reactor equipped with a stirrer, a condenser, and a thermometer was charged with 61.6 parts of a 17% by mass aqueous solution of potassium hydroxide, 19.1 parts of methyl methacrylate, and 19.3 parts of deionized water. The liquid in the reactor was then stirred at room temperature, and after confirming the exothermic peak, the mixture was stirred for 4 hours. The reaction liquid in the reactor was then cooled to room temperature to obtain an aqueous solution of potassium methacrylate.

[0119] Next, 900 parts of deionized water, 70 parts of a 42% by weight aqueous solution of sodium 2-sulfoethyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester SEM-Na), 16 parts of the above potassium methacrylate aqueous solution, and 7 parts of methyl methacrylate were added to a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, and the mixture was stirred. While the atmosphere inside the polymerization apparatus was replaced with nitrogen, the temperature of the liquid in the reaction apparatus was raised to 50°C. 0.053 parts of V-50 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name: 2,2'-azobis(2-methylpropionamidine) dihydrochloride) was added as a polymerization initiator to the polymerization apparatus, and the temperature of the liquid in the reaction apparatus was raised to 60°C. After adding the polymerization initiator, 1.4 parts of methyl methacrylate was added in five increments (total amount of methyl methacrylate: 7 parts) every 15 minutes. Thereafter, the liquid in the polymerization apparatus was kept at 60° C. for 6 hours while being stirred, and then cooled to room temperature to obtain a dispersant (1) in the form of a transparent aqueous solution with a solid content of 8% by mass.

[0120] [Production Example 2: Synthesis of Chain Transfer Agent (1)] In a synthesis apparatus equipped with a stirrer, 2.00 g (8.03 mmol) of cobalt (II) acetate tetrahydrate (Fujifilm Wako Co., Ltd., Wako special grade), 3.86 g (16.1 mmol) of diphenylglyoxime (Tokyo Chemical Industry Co., Ltd., EP grade), and 100 ml of diethyl ether that had been deoxygenated in advance by nitrogen bubbling were placed under a nitrogen atmosphere, and the mixture was stirred at room temperature for 2 hours.

[0121] Next, 20 ml of boron trifluoride diethyl ether complex (manufactured by Tokyo Chemical Industry Co., Ltd., EP grade) was added, and the mixture was stirred for another 6 hours. The obtained mixture was filtered, and the solid was washed with diethyl ether and dried at 100 MPa or less at 20°C for 12 hours to obtain 5.02 g (7.93 mmol, yield 99% by mass) of chain transfer agent (1) as a brown solid.

[0122] [Production Example 3: Synthesis of Macromonomer (A-1)] A polymerization apparatus equipped with a stirrer, a condenser, and a thermometer was charged with 145 parts of deionized water, 0.13 parts of sodium sulfate (NaSO), and 0.26 parts of dispersant (1) (solid content 10% by mass) produced in Production Example 1, and the mixture was stirred to form a uniform aqueous solution. Next, 100 parts of MMA, 0.0045 parts (45 ppm) of chain transfer agent (1) produced in Production Example 2, and 0.5 parts of Perocta O (1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, product name, manufactured by NOF Corporation) as a polymerization initiator were added to form an aqueous dispersion.

[0123] The inside of the polymerization reactor was then thoroughly purged with nitrogen, and the aqueous dispersion was heated to 80°C and maintained there for 4 hours, and then heated to 92°C and maintained there for 2 hours. The reaction solution was then cooled to 40°C to obtain an aqueous suspension of a macromonomer. This aqueous suspension was filtered through a filter cloth, and the filtrate was washed with deionized water and dried at 40°C for 16 hours to obtain macromonomer (A-1). The macromonomer (A-1) had an Mn of 3,200 and an Mw of 7,800, and the terminal double bond introduction rate exceeded 99%.

[0124] [Production Examples 4 to 6: Synthesis of Macromonomers (A-2) to (A-4)] Macromonomers (A-1) to (A-4) were synthesized in the same manner as in Production Example 3, except that the charging conditions were changed to those shown in Table 1. The results are summarized in Table 1.

[0125] [Table 1]

[0126] Example 1: Evaluation of thermal decomposition resistance 99 parts by mass of the macromonomer (A-1) synthesized in Production Example 1 and 1.0 part by mass of Sumilizer GS (product name, manufactured by Sumitomo Chemical Co., Ltd.), which corresponds to compound (G), were dissolved and mixed in tetrahydrofuran (THF), and then the mixture was vacuum dried at room temperature to remove the THF, yielding a sample of a thermoplastic resin composition. The obtained sample was evaluated for thermal decomposition resistance. The evaluation results are summarized in Table 2.

[0127] [Examples 2 to 4, Comparative Examples 1 to 5] Thermoplastic resin composition samples were obtained in the same manner as in Example 1, except that the charging conditions were changed to those shown in Table 2. Using each of the obtained samples, thermal decomposition resistance was evaluated in the same manner as in Example 1. The evaluation results are summarized in Table 2.

[0128] [Table 2]

[0129] In Example 1, the addition of compound (G) to macromonomer (A-1) improved the 5% weight loss temperature by 54°C compared to Comparative Example 1, where no compound was added. Similarly, when compound (G) was added to macromonomers (A-2) to (A-4) in Examples 2 to 4, the 5% weight loss temperature also significantly improved. On the other hand, when compound (G) was not used, the following conditions were not observed: A common phenolic antioxidant, ADEKA STAB AO-60, was used in Comparative Example 2; a common phosphorus-based antioxidant, ADEKA STAB 2112, was used in Comparative Example 3; a common hindered amine light stabilizer (HALS), Tinuvin 770DF, was used in Comparative Example 4; and a common sulfur-based antioxidant, Sumilizer TP-D, was used in Comparative Example 5. Therefore, it was found that the addition of compound (G) specifically improved the thermal decomposition resistance of macromonomer (A). In other words, it is believed that the addition of compound (G) can stop the depolymerization of macromonomer (A).

[0130] [Example of production of copolymer (C) and evaluation of thermal decomposition resistance] [Production Example 7: Synthesis of Copolymer (C-1)] In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 50 parts of the macromonomer (A-2) obtained in Production Example 4, 150 parts of deionized water, 0.26 parts of dispersant (1), and 0.3 parts of sodium sulfate were added and stirred to obtain an aqueous suspension. Next, the temperature inside the polymerization apparatus was raised to 70°C, and 41.5 parts of BA and 8.5 parts of St were slowly added. The mixture was then maintained at 70°C for 1 hour with stirring to dissolve the macromonomer (A-2) in the BA and St, obtaining a dispersion. The polymerization apparatus was then cooled to 40°C, and 0.5 parts of the radical polymerization initiator AMBN was added and stirred for 30 minutes to dissolve the mixture. The atmosphere inside the polymerization apparatus was then thoroughly purged with nitrogen, and the aqueous dispersion was heated to 82°C and maintained for 4 hours, then heated to 90°C and maintained for 1 hour. After cooling to below 40°C, the mixture was filtered through a filter cloth, and the filtrate was washed with deionized water. The filtered product was then dried in a hot air circulation dryer at 40° C. for 12 hours to obtain copolymer (C-1) in the form of beads. Table 3 shows the charged composition and the polymerization results of the copolymer.

[0131] [Production Example 8: Synthesis of Copolymer (C-2)] A reactor equipped with a stirrer, condenser, and thermometer was charged with 145 parts of deionized water, 0.36 parts of sodium sulfate, 1.25 parts of dispersant (1) prepared in Preparation Example 1, 40 parts of macromonomer (A-3) prepared in Preparation Example 5, 60 parts of MEA, and 0.2 parts of nOM. The mixture was heated to 55°C with stirring to obtain a syrup-dispersed composition. After cooling the composition to below 40°C, 0.12 parts of V-601 was dissolved in the composition to obtain a syrup-dispersed polymerizable composition. The syrup dispersion was then heated to 75°C and maintained for 2 hours. The temperature was then raised to 85°C and maintained for 90 minutes. The suspension was cooled to below 40°C, filtered, and the filtrate was washed with deionized water and dried at 70°C for 12 hours to obtain copolymer (C-2). The polymerization results are shown in Table 3.

[0132] [Production Example 9: Synthesis of Copolymer (C-3)] An aqueous dispersion medium for suspension polymerization was prepared by mixing 145 parts of deionized water, 0.13 parts of sodium sulfate, and 0.26 parts of dispersant (1) prepared in Production Example 1. A separable flask equipped with a condenser was charged with 40 parts of the macromonomer (A-4) prepared in Production Example 6, 42.6 parts of BA, and 17.4 parts of St, totaling 100 parts, and the mixture was heated to 60°C with stirring to obtain a raw syrup. After cooling the raw syrup to below 40°C, 0.5 parts of AMBN was dissolved in the raw syrup to obtain a syrup. Next, the aqueous dispersion medium for suspension polymerization was added to the syrup, and the atmosphere in the separable flask was replaced with nitrogen by nitrogen bubbling, while the stirring speed was increased to obtain a syrup dispersion. The syrup dispersion was heated to 82°C and maintained for 5 hours. The syrup dispersion was then heated to 90°C and maintained for 30 minutes to complete the polymerization, obtaining a suspension. After the suspension was cooled to below 40°C, the suspension was filtered through a filter cloth, the filtered product was washed with deionized water, and dried at 40°C for 16 hours to obtain copolymer (C-3). The polymerization results are shown in Table 3.

[0133] [Table 3]

[0134] [Example 5] 99.9 parts by mass of the copolymer (C-1) obtained in Production Example 7 and 0.1 parts by mass of Sumilizer GS (product name, manufactured by Sumitomo Chemical Co., Ltd.) were dissolved and mixed in tetrahydrofuran (THF), and then the mixture was vacuum dried at room temperature to remove the THF, thereby obtaining a sample of a thermoplastic resin composition. The obtained sample was evaluated for thermal decomposition resistance. The evaluation results are summarized in Table 4.

[0135] [Examples 6 to 12, Comparative Examples 6 to 8] Thermoplastic resin composition samples were obtained in the same manner as in Example 5, except that the charging conditions were changed to those shown in Table 4. Using each of the obtained samples, thermal decomposition resistance was evaluated in the same manner as in Example 5. The evaluation results are summarized in Tables 4 and 5.

[0136] [Reference example 1] In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate (Na2SO4), and 0.26 parts of dispersant (1) (solid content 10% by mass) produced in Production Example 1 were placed and stirred to form a uniform aqueous solution. Next, 95 parts of MMA, 5 parts of MA, 0.6 parts of 1-octanethiol as a chain transfer agent, and 0.1 part of AMBN as a polymerization initiator were added to form an aqueous dispersion.

[0137] Next, the inside of the polymerization reactor was thoroughly purged with nitrogen, and the aqueous dispersion was heated to 78°C and held there for 3 hours, then heated to 92°C and held there for 2 hours. The reaction solution was then cooled to 40°C to obtain an aqueous suspension of the polymer. This aqueous suspension was filtered through a filter cloth, and the filtrate was washed with deionized water and dried at 40°C for 16 hours to obtain a copolymer (C-4) that did not contain macromonomer (A). The Mn of the copolymer (C-4) was 29,000 and the Mw was 47,500, and no terminal double bonds were observed. The copolymer (C-4) was dissolved and mixed in tetrahydrofuran (THF), and then vacuum-dried at room temperature to remove the THF, yielding a sample of a thermoplastic resin composition. The thermal decomposition resistance of the obtained sample was evaluated in the same manner as in Example 5. The evaluation results are summarized in Table 5.

[0138] [Reference example 2] In a polymerization apparatus equipped with a stirrer, a condenser, and a thermometer, 145 parts of deionized water, 0.1 part of sodium sulfate (NaSO), and 0.26 parts of dispersant (1) (solid content 10% by mass) produced in Production Example 1 were placed and stirred to form a uniform aqueous solution. Next, 100 parts of MMA, 0.6 parts of 1-octanethiol as a chain transfer agent, and 0.1 part of AMBN as a polymerization initiator were added to form an aqueous dispersion.

[0139] Next, the inside of the polymerization reactor was thoroughly purged with nitrogen, and the aqueous dispersion was heated to 78°C and held there for 3 hours, then heated to 92°C and held there for 2 hours. The reaction solution was then cooled to 40°C to obtain an aqueous suspension of the polymer. This aqueous suspension was filtered through a filter cloth, and the filtrate was washed with deionized water and dried at 40°C for 16 hours to obtain a copolymer (C-5) that did not contain macromonomer (A). The Mn of the copolymer (C-5) was 28,500 and the Mw was 46,400, and no terminal double bonds were observed. The copolymer (C-5) was dissolved and mixed in tetrahydrofuran (THF), and then vacuum-dried at room temperature to remove the THF, yielding a sample of a thermoplastic resin composition. The thermal decomposition resistance of the obtained sample was evaluated in the same manner as in Example 5. The evaluation results are summarized in Table 5.

[0140] [Table 4]

[0141] [Table 5]

[0142] Examples 5 to 7 and Comparative Example 6 show that adding compound (G) to copolymer (C-1) improved thermal decomposition resistance. Examples 8 to 9 and Comparative Example 7 show that adding compound (G) to copolymer (C-2) improved thermal decomposition resistance. Examples 10 to 12 and Comparative Example 8 show that adding compound (G) to copolymer (C-3) improved thermal decomposition resistance. Reference Examples 1 and 2 show that copolymers or polymers that do not contain macromonomer (A) represented by formula (1) and / or copolymer (C) containing a structural unit derived from formula (1) exhibit good thermal decomposition resistance and do not present the problems that the present invention aims to solve. However, these copolymers or polymers cannot solve the problems that conventional (meth)acrylic block copolymers and homopolymers have.

[0143] [Evaluation of thermal decomposition resistance of thermoplastic resin compositions] Polymethyl methacrylate, polycarbonate, polyvinyl chloride, polyolefin, polyurethane, or polyester was added to the thermoplastic resin composition obtained in each example, and the thermal decomposition resistance was evaluated in the same manner as in Example 5. Even when the polymer (M) is contained, the effects of the thermoplastic resin composition obtained in each example are not impaired, and good thermal decomposition resistance can be obtained. In particular, when the content of the polymer (M) is 10 to 95 mass% of the total amount of the thermoplastic resin composition, good thermal decomposition resistance can be obtained, similar to the thermoplastic resin compositions obtained in each example. [Industrial Applicability]

[0144] According to the present invention, a thermoplastic resin composition having good resistance to thermal decomposition, a molding material, and a molded article obtained by molding the molding material are obtained. [Explanation of symbols]

[0145] 1 Lamp cover 2. Housing 3 Projection Lens 4 LED light source 5 Support substrate 10 Finely textured structure 12 Base material 14 Convex part 16 Recess 18 Fine uneven structure 20 Cured resin layer 22 Weir I Area I II Area II 1001 First resin base material 1002 Hologram Layer 1003 Second resin base material 1004 Light guide plate for image display 40 tubes 41 Resin layer 40a Single leaf (with fold) 40b intermediate product 40c double bag packaging bag 41, 42, 43, 44 folds 45, 46, 48 Overlapping parts 47 Aperture

Claims

1. A thermoplastic resin composition comprising: compound (F), which is at least one compound selected from the group consisting of macromonomer (A) represented by formula (1) below and copolymer (C) containing a structural unit derived from macromonomer (A) represented by formula (1) below; and compound (G), which is represented by formula (2) below: 【Chemistry 1】 (In formula (1), R ０ ~R ｎ are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group. １ ~X ｎ are each independently a hydrogen atom or a methyl group. Z is a terminal group. n is a natural number from 1 to 10,000. 【Chemistry 2】 (In formula (2), R １ ~R ４ each independently represents an alkyl group having 1 to 5 carbon atoms; R ５ represents an alkyl group having 1 to 5 carbon atoms or a hydrogen atom.

2. The copolymer (C) is contained, The thermoplastic resin composition according to claim 1, wherein the copolymer (C) has a chemical structure (E) represented by the following formula (3): 【Transformation 3】 (In formula (3), R ０ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.

3. The compound (F) has a chemical structure (E) represented by the following formula (3):

2. The thermoplastic resin composition according to claim 1, wherein, when the molar ratio of the chemical structure (E) to the compound (G) is expressed as the chemical structure (E):the compound (G)=1:X, X is 0.01 or more and 100 or less. 【Chemistry 4】 (In formula (3), R ０ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.

4. The compound (F) has a chemical structure (E) represented by the following formula (3):

2. The thermoplastic resin composition according to claim 1, wherein, when the molar ratio of the chemical structure (E) to the compound (G) is expressed as the chemical structure (E):the compound (G)=1:X, X is 0.05 or more and 30 or less. 【Transformation 5】 (In formula (3), R ０ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.

5. The compound (F) has a chemical structure (E) represented by the following formula (3):

2. The thermoplastic resin composition according to claim 1, wherein, when the molar ratio of the chemical structure (E) to the compound (G) is expressed as the chemical structure (E):the compound (G)=1:X, X is 0.2 or more and 10 or less. 【Transformation 6】 (In formula (3), R ０ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.

6. The thermoplastic resin composition according to claim 1 , further comprising a polymer (M) different from the compound (F).

7. The thermoplastic resin composition according to claim 6, wherein the polymer (M) is at least one selected from the group consisting of polymethyl methacrylate, polycarbonate, polyvinyl chloride, polyolefin, polyurethane, and polyester.

8. The thermoplastic resin composition according to claim 6, wherein the content of the polymer (M) is 10 to 95 mass% of the total amount of the thermoplastic resin composition.

9. A thermoplastic resin composition for injection molding or extrusion molding, comprising the thermoplastic resin composition according to claim 8.

10. Use of the thermoplastic resin composition according to any one of claims 1 to 9 in injection molding or extrusion molding.

11. A molding material comprising the thermoplastic resin composition according to any one of claims 1 to 9.

12. A molded article obtained by molding the molding material according to claim 11.

13. A vehicle component obtained by molding the molding material according to claim 11.

14. An electric / electronic component obtained by molding the molding material according to claim 11.

15. An optical member obtained by molding the molding material according to claim 11.

16. A medical device obtained by molding the molding material according to claim 11.

17. A food package formed from the molding material according to claim 11.

18. A method for producing a molded article, comprising molding the molding material according to claim 11 to obtain a molded article.

19. The method for producing a molded article according to claim 18, wherein the molding is injection molding or extrusion molding.

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