JP2019059906A - (Meth) acrylic acid ester type copolymer, thermoplastic resin composition and molded article thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having excellent fluidity, color development property, heat resistance and scratch resistance, and a molded product thereof. A vinyl-based monomer mixture (m1) containing a (meth) acrylic acid ester monomer, an N-substituted maleimide monomer, and an aromatic vinyl monomer, the vinyl-based monomer mixture. The content of the N-substituted maleimide monomer in the total 100% by mass of (m1) is less than 9% by mass, and the content of the aromatic vinyl monomer is 7 to 39% by mass of the vinyl-based monomer mixture (m1). ) Is polymerized (meth) acrylic acid ester-based copolymer (A). The (meth) acrylic acid ester-based copolymer (A) and the graft copolymer (C) obtained by polymerizing the vinyl-based monomer mixture (m2) in the presence of the rubber-like polymer (B). A thermoplastic resin composition containing. [Selection diagram] None

Description

The present invention can provide a thermoplastic resin composition which is excellent in fluidity, and excellent in color development, heat resistance and scratch resistance (meth) acrylate copolymer (A), and this (meth) The present invention relates to a thermoplastic resin composition containing an acrylic ester copolymer (A) and a molded article thereof.
In the present specification, "(meth) acrylic acid" refers to one or both of "acrylic acid" and "methacrylic acid".

  (Meth) acrylic ester resins represented by polymethyl methacrylate (PMMA) have excellent color forming properties, surface hardness, weather resistance and high mechanical properties, so they can be used as building materials and automotive fields as highly colored materials. Are widely used. However, the (meth) acrylic acid ester resin has low heat resistance, and improvement of heat resistance has been required to expand its application field.

As a method of improving the heat resistance of (meth) acrylic acid ester resin, a method of copolymerizing N-substituted maleimide is known, and in order to provide higher heat resistance, the N-substituted maleimide monomer ratio is You should raise it high. However, when the ratio of N-substituted maleimide monomer is increased, a large amount of maleimide monomer tends to remain in the polymer, and there is a problem that the maleimide compound is volatilized when processing the obtained resin. Moreover, although it is common to add alkyl mercaptans as a chain transfer agent at the time of manufacture for molecular weight adjustment of (meth) acrylic acid ester resin, and thermal stability improvement, it is Michael addition to maleimide of alkyl mercaptans. Also has the problem that the product tends to be colored. Furthermore, in an aqueous system, hydrolysis of the N-substituted maleimide generates an amine compound, which is likely to cause coloration originating from this. In particular, it is known that the use of N-aryl maleimide which generates arylamine by decomposition has a large influence on coloring.

  From these facts, the heat-resistant (meth) acrylic acid ester resin using N-substituted maleimide is limited in its use for a highly colored material.

  In addition, there is also a problem that the flowability is significantly reduced by copolymerizing the N-substituted maleimide. From this, the heat-resistant (meth) acrylic acid ester resin using N-substituted maleimide is also limited in the size of the molded article.

Conventionally, it has been proposed to use N-cycloalkyl maleimide such as cyclohexyl maleimide as a method for improving the color developability of a heat-resistant (meth) acrylic ester resin using N-substituted maleimide 304013). However, N-cycloalkyl maleimide is less effective in improving heat resistance than N-aryl maleimide. Further, it has been proposed to improve the heat coloring and reduce the amount of residual maleimide by performing polymerization using two types of polymerization initiators having different half-life temperatures of 10 hours (Japanese Patent Application Laid-Open No. 63-304013). Japanese Patent Laid-Open Publication No. 3-188111) is still insufficient.
In addition, in the automotive field, in addition to color development, impact resistance, heat resistance, and demand for larger size and higher appearance of molded products, improvement of fluidity is required, but improvement of fluidity has not been made yet. It is sufficient (Japanese Patent Publication No. 7-72243).

Japanese Patent Application Laid-Open No. 63-304013 JP-A-3-188111 Japanese Examined Patent Publication 7-72243

  Therefore, the object of the present invention is a thermoplastic resin composition which itself is excellent in fluidity, color development, heat resistance and scratch resistance in a well-balanced manner, excellent in fluidity and color development, and excellent in heat resistance and scratch resistance. To provide a (meth) acrylic acid ester copolymer (A) which can be provided, a thermoplastic resin composition containing the (meth) acrylic acid ester copolymer (A), and a molded article thereof is there.

  As a result of intensive studies to solve the above problems, the present inventors found that a (meth) acrylic acid ester monomer, a specific amount of an N-substituted maleimide monomer, and a specific amount of an aromatic vinyl monomer (Meth) acrylic acid ester type copolymer (A) which is obtained by polymerizing is itself excellent in fluidity, in color balance, heat resistance and scratch resistance in a well-balanced manner, excellent in flowability, color developability, heat resistance, The inventors have found that a thermoplastic resin composition excellent in scratch resistance can be provided and completed the present invention.

  That is, the present invention provides the following.

[1] A vinyl monomer mixture (m1) containing a (meth) acrylic acid ester monomer, an N-substituted maleimide monomer and an aromatic vinyl monomer, wherein the vinyl monomer mixture ((1) Vinyl-based monomer mixture in which the content of the N-substituted maleimide monomer in the total 100% by mass of m1) is less than 9% by mass and the content of the aromatic vinyl monomer is 7 to 39% by mass ((1) (Meth) acrylate copolymer (A) formed by polymerizing m1).

[2] The (meth) described in [1], wherein the content of the (meth) acrylic acid ester monomer in the total 100% by mass of the vinyl-based monomer mixture (m1) is 52 to 92% by mass Acrylic acid ester copolymer (A).

[3] A thermoplastic resin composition comprising the (meth) acrylate copolymer (A) according to [1] or [2].

[4] A graft copolymer obtained by polymerizing a vinyl-based monomer mixture (m2) in the presence of the (meth) acrylic acid ester-based copolymer (A) and the rubbery polymer (B) C), and the thermoplastic resin composition as described in [3].

[5] The graft copolymer (C) is obtained by polymerizing 20 to 80% by mass of a vinyl monomer mixture (m2) in the presence of 20 to 80% by mass of the rubbery polymer (B) ( However, the total of 100% by mass of the rubbery polymer (B) and the vinyl monomer mixture (m2)), the rubbery polymer (B) is a diene rubbery polymer, an acrylic rubbery weight It is 1 type, or 2 or more types chosen from a combination, an olefin type rubbery polymer, and a silicone type rubbery polymer, This vinyl type monomer mixture (m2) is a vinyl type monomer mixture (m2) The heat according to [4], which contains 65 to 82% by mass of an aromatic vinyl monomer, 18 to 35% by mass of a vinyl cyanide monomer in 100% by mass in total, and the graft ratio is 10 to 150%. Plastic resin composition.

[6] A composite of a polyorganosiloxane (b-1) having a volume average particle diameter of 50 nm or more and less than 240 nm and an alkyl (meth) acrylate polymer (b-2) as the graft copolymer (C) A graft polymer (C1) obtained by polymerizing a vinyl monomer mixture (m2) containing an aromatic vinyl monomer and a vinyl cyanide monomer in the presence of a rubbery polymer (B1) The thermoplastic resin composition as described in [4].

[7] The polyorganosiloxane (b-1) in a total of 100% by mass of the polyorganosiloxane (b-1) and the alkyl (meth) acrylate polymer (b-2) in the composite rubbery polymer (B1) The thermoplastic resin composition as described in [6] whose ratio is 1 mass% or more and less than 25 mass%.

[8] The graft polymer (C1) is prepared by polymerizing 20 to 90% by mass of the vinyl monomer mixture (m2) in the presence of 10 to 80% by mass of the composite rubbery polymer (B1) (However, the total of the composite rubbery polymer (B1) and the vinyl monomer mixture (m2) is 100% by mass), and the vinyl monomer mixture (m2) is a vinyl monomer mixture ( or 65% to 82% by mass of an aromatic vinyl monomer, 18 to 35% by mass of a vinyl cyanide monomer in 100% by mass of the total m2), and the graft ratio is 35 to 60%, [6] or The thermoplastic resin composition as described in [7].

[9] A total of 100% by mass of the (meth) acrylate copolymer (A) and the graft copolymer (C) contains 50 of the (meth) acrylate copolymer (A). The thermoplastic resin composition according to any one of [4] to [8], containing 90% by mass.

[10] The (meth) acrylic acid ester copolymer (A) according to [1] or [2] or the thermoplastic resin composition according to any of [3] to [9] Molded articles.

  ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin composition which was excellent in fluidity | liquidity and was excellent in coloring property, heat resistance, and scratch resistance, and its molded article can be provided.

Embodiments of the present invention will be described in detail below.
The following definitions of terms apply throughout the specification and claims.
"(Meth) acrylic acid" refers to one or both of "acrylic acid" and "methacrylic acid".
"Molded article" means what is obtained by molding a thermoplastic resin composition.
"Lightness (L *)" means the lightness value (L *) among the color values in the L * a * b * color system adopted in JIS Z 8729.
The "SCE method" means a method of measuring a color by removing a specularly reflected light by an optical trap using a spectrocolorimeter conforming to JIS Z 8722.

[(Meth) Acrylate Copolymer (A)]
The (meth) acrylic acid ester copolymer (A) of the present invention contains a (meth) acrylic acid ester monomer, a specific amount of an N-substituted maleimide monomer, and a specific amount of an aromatic vinyl monomer It is obtained by polymerizing a vinyl-based monomer mixture (m1), and as such, it has excellent fluidity, color developability, heat resistance and scratch resistance in a well-balanced manner.

<(Meth) acrylic acid ester monomer>
Examples of (meth) acrylic acid ester monomers used in the present invention include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) methacrylate, for example. Among these, butyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclodecyl (meth) acrylate, phenyl (meth) acrylate, 2,4,6-tribromophenyl (meth) acrylate and the like can be mentioned. Methyl methacrylate is most preferred. These (meth) acrylic acid ester monomers can be used in combination of two or more, as required. When using together, it is preferable to contain 25 mass% or more of methyl methacrylate with respect to the whole quantity of a (meth) acrylic acid ester monomer, and it is more preferable to contain 50 mass% or more.

  The content of the (meth) acrylic acid ester monomer in the vinyl-based monomer mixture (m1) is the obtained (meth) acrylic acid ester copolymer (A), a thermoplastic resin composition, and a molded article thereof 52 to 92% by mass is preferable, and more preferably 60 to 85% by mass in the total 100% by mass of the vinyl monomer mixture (m1), because the color developability, scratch resistance, flowability and the like of the above are excellent. More preferably, it is 65-80 mass%. The color developability and scratch resistance of the (meth) acrylic acid ester copolymer (A), the thermoplastic resin composition and the molded article obtained as the content of the (meth) acrylic acid ester monomer is within the above range Stickiness, fluidity, and impact resistance become excellent.

<N-substituted maleimide monomer>
The N-substituted maleimide monomer used in the present invention is not limited to these, for example, N-substituted aryl maleimides such as N-phenyl maleimide, N-o-chlorophenyl maleimide, etc., N-methyl N-substituted alkyl maleimides such as maleimide, N-ethyl maleimide, N-propyl maleimide, N-butyl maleimide, N-t-butyl maleimide, N-substituted cycloalkyl maleimides such as N-cyclohexyl maleimide, and the like. Among these, N-phenyl maleimide having a high heat resistance improvement effect is preferable. Two or more types of these N-substituted maleimide monomers can be used in combination as necessary, but when used in combination, N-phenylmaleimide is used in 25 parts of the total amount of N-substituted maleimide monomers. It is preferable to contain mass% or more, and it is more preferable to contain 50 mass% or more.

  The content of the N-substituted maleimide monomer in the vinyl-based monomer mixture (m1) is the heat resistance of the resulting (meth) acrylate copolymer (A), the thermoplastic resin composition, and the molded article thereof And less than 9% by mass, preferably 2% by mass to less than 9% by mass, and more preferably 3% by mass, based on 100% by mass of the vinyl monomer mixture (m1). It is more than 9% by mass. (Meth) acrylic acid ester copolymer (A) obtained when the content of N-substituted maleimide is 9% by mass or more, the thermoplastic resin composition and the colorability and fluidity of a molded article thereof, surface impact resistance It is inferior in sex. Heat resistance, color developability, flowability, (meth) acrylic acid ester copolymer (A), thermoplastic resin composition and molded articles obtained when the content of N-substituted maleimide is within the above range The surface impact resistance is excellent.

<Aromatic vinyl monomer>
Examples of the aromatic vinyl monomer used in the present invention include, but are not limited to, styrene, α-methylstyrene, vinyl toluene, etc., among which styrene and α-methylstyrene are preferable. preferable. About these aromatic vinyl monomers, 2 or more types can also be used together as needed. When using together, it is preferable to contain 25 mass% or more of styrene and / or alpha-methylstyrene with respect to the whole quantity of an aromatic vinyl monomer, and it is more preferable to contain 50 mass% or more.

  The content of the aromatic vinyl monomer in the vinyl-based monomer mixture (m1) is determined by the colorability of the resulting (meth) acrylate copolymer (A), the thermoplastic resin composition and the molded article thereof And 7 to 39% by mass, preferably 8 to 30% by mass, and more preferably 9 to 25% by mass in the total 100% by mass of the vinyl-based monomer mixture (m1). When the content of the aromatic vinyl monomer is less than 7% by mass, the fluidity of the (meth) acrylic acid ester copolymer (A) to be obtained, the thermoplastic resin composition, and the molded article thereof becomes inferior. If the amount is more than 39% by mass, coloring properties and impact resistance become poor.

<Other vinyl monomers>
The vinyl-based monomer mixture (m1) used in the present invention can be copolymerized with (meth) acrylic acid ester monomers, N-substituted maleimide monomers, and aromatic vinyl monomers, in addition to these monomers. The following vinyl-based monomers may be contained as required. As other vinyl monomers that can be copolymerized, for example, conjugated dienes such as butadiene and isoprene, vinyl cyanides such as acrylonitrile, unsaturated carboxylic acids such as acrylic acid, maleic acid and maleic anhydride, etc. It can be mentioned. One of these may be used alone, or two or more may be used in combination.

  These other vinyl-based monomers may be added according to the required characteristics of the (meth) acrylic acid ester-based copolymer (A), but the (meth) acrylic acid ester-based copolymer (A) From the viewpoint of easily maintaining basic properties such as heat resistance, color development, surface hardness, weatherability and high mechanical properties, other vinyl monomers in 100% by mass of the vinyl monomer mixture (m1) The content is preferably at most 20% by mass, particularly preferably at most 10% by mass.

<The manufacturing method of (meth) acrylic acid ester type copolymer (A)>
The (meth) acrylic acid ester-based copolymer (A) is obtained by polymerizing a vinyl-based monomer mixture (m1). The polymerization method of the vinyl-based monomer mixture (m1) is not particularly limited, and examples of the polymerization method include known polymerization methods (emulsion polymerization, suspension polymerization, solution polymerization, and the like).

  As a method for producing the (meth) acrylic acid ester copolymer (A) by the emulsion polymerization method, for example, a vinyl monomer mixture (m1), an emulsifier, a polymerization initiator and a chain transfer agent in a reactor. There is a method of charging, heating and polymerizing, and recovering the (meth) acrylic acid ester copolymer (A) from the aqueous dispersion containing the (meth) acrylic acid ester copolymer (A) by the precipitation method. .

  Examples of the emulsifier include conventional emulsifiers for emulsion polymerization (potassium rosin acid, sodium alkylbenzene sulfonate and the like).

  Examples of the polymerization initiator include organic and inorganic peroxide initiators.

  As a chain transfer agent, mercaptans, the (alpha)-methylstyrene dimer, terpenes etc. are mentioned.

  As a method for producing a (meth) acrylic acid ester copolymer (A) by suspension polymerization, for example, a vinyl monomer mixture (m1) and a suspending agent, a suspending agent, polymerization in a reactor The initiator and chain transfer agent may be charged, heated for polymerization, and the slurry may be dewatered and dried to recover the (meth) acrylic acid ester copolymer (A).

  As the suspending agent, for example, anionic water-soluble polymers, nonionic water-soluble polymers, water-insoluble inorganic salts and the like can be mentioned.

  As the anionic water-soluble polymer, for example, polyacrylic acid, sodium polyacrylate, potassium polyacrylate, polymethacrylic acid, sodium polymethacrylate, potassium polymethacrylate, sodium methacrylate-methacrylic acid alkyl ester copolymer Etc. One or two or more of them may be mentioned. Among them, sodium polyacrylate and sodium polymethacrylate are preferable.

  Examples of nonionic water-soluble polymers include polyvinyl alcohol, methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyvinyl pyrrolidone, hydroxypropyl methyl cellulose, polyalkylene oxides such as polyethylene oxide, and polyoxyethylene-polyoxypropylene block copolymers And one or more water-soluble polymers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol fatty acid ester, and polyoxyethylene lauryl amine. Preferably, it is polyvinyl alcohol, a polyoxyethylene-polyoxypropylene copolymer, more preferably a polyoxyethylene-polyoxypropylene block copolymer.

  As the hardly water-soluble inorganic salt, for example, one or two or more kinds of barium sulfate, calcium phosphate tribasic, magnesium carbonate and the like can be mentioned. Preferably it is tribasic calcium phosphate.

  The suspending agent is preferably used in an amount of 0.1 to 3 parts by mass with respect to 100 parts by mass of the vinyl monomer mixture (m1).

  As the suspension aid, carboxylates (eg sodium sarcosinate, fatty acid potassium, fatty acid sodium, alkenyl succinate potassium, alkenyl succinate dipotassium, rosin acid soap etc.), alkyl sulfate ester salt, alkyl benzene sulfonate sodium, alkyl One or two or more kinds of dibasic acids having an alkyl group and / or alkenyl group such as sodium sulfosuccinate, sodium polyoxyethylene nonylphenyl ether sulfate and the like, or salts thereof can be mentioned.

  As the suspension aid, potassium alkenyl succinate may be used from the viewpoint of the stability at the time of production, the (meth) acrylate copolymer (A) to be obtained and the color developability of the thermoplastic resin composition, etc. preferable.

  The suspending aid is preferably used in an amount of 0.0001 to 1 part by mass with respect to 100 parts by mass of the vinyl monomer mixture (m1).

The polymerization initiator includes organic peroxides.
The polymerization initiator is preferably used in an amount of 0.15 to 0.7 parts by mass with respect to 100 parts by mass of the vinyl monomer mixture (m1).

As a chain transfer agent, mercaptans, the (alpha)-methylstyrene dimer, terpenes etc. are mentioned.
The chain transfer agent is preferably used in an amount of 0.3 to 1.2 parts by mass with respect to 100 parts by mass of the vinyl monomer mixture (m1).

<Method for Producing Preferred (Meth) Acrylate Copolymer (A)>
In the present invention, it is particularly preferable to produce the (meth) acrylic acid ester copolymer (A) by the suspension polymerization method, and at that time, the 10 hour half-life temperature is 40 to 60 ° C. as a polymerization initiator. A combination of a radical polymerization initiator (D-1) and a radical polymerization initiator (D-2) having a 10-hour half-life temperature of 70 to 90 ° C., as a chain transfer agent, alkyl mercaptan and α-methylstyrene The dimer is used in combination, the polymerization reaction is started at 40 to 60 ° C, the temperature is raised continuously or stepwise from 100 to 140 ° C at the temperature rising rate of 1 to 20 ° C / hr, and 5 to 12 hours from the start of the reaction It is preferable to complete the polymerization reaction in producing the (meth) acrylic acid ester copolymer (A) more excellent in color developability and heat resistance.
That is, by starting the polymerization reaction at a relatively low temperature of 40 to 60 ° C., the N-substituted maleimide monomer is easily incorporated into the polymer, while the polymerization completion temperature is increased to a certain extent to 100 to 140 ° C. Can reduce the amount of residual N-substituted maleimide monomer. In addition, since the rapid progress of the reaction causes coloration, the polymerization rate is suppressed by setting the addition of α-methylstyrene dimer and the temperature rising rate to a specific range, and the addition of an alkyl mercaptan further suppresses the polymerization. By suppressing the high viscosity effect, it is possible to suppress the coloration of the (meth) acrylate copolymer (A) due to the rapid reaction. Moreover, in order to suppress hydrolysis of the N-substituted maleimide monomer in water in suspension polymerization, the polymerization reaction is completed in such a time that rapid reaction does not proceed, that is, 5 to 12 hours. By adopting such conditions, it is possible to produce a (meth) acrylic acid ester copolymer (A) excellent in color developability and heat resistance.

  The specific polymerization method in the method for producing this suitable (meth) acrylic acid ester copolymer (A) is not particularly limited. For example, as a water solvent, vinyl monomer mixture (m1), as a polymerization initiator Add a radical polymerization initiator (D-1) and a radical polymerization initiator (D-2), a chain transfer agent alkyl mercaptan and an α-methylstyrene dimer, and optionally, a suspension dispersant and a dispersion aid (Hereafter, a monomer mixture to which a polymerization initiator, a chain transfer agent, an aqueous solvent, and other components are added may be referred to as a “reaction material mixture”.) By heating with stirring (meth) An acrylic ester copolymer (A) can be produced. The addition method of each component at that time may be any of batch, continuous, and sequential addition.

  The radical polymerization initiator (D-1) having a 10-hour half-life temperature of 40 to 60 ° C. is not particularly limited, and, for example, 1,1,3,3-tetramethylbutyl peroxy neodecanate, t And peroxides such as hexyl peroxy neodecanoate, t-butyl peroxy neoheptanoate, t-hexyl peroxy pivalate, and t-butyl peroxy pivalate. These may use only 1 type and may use 2 or more types together.

  The addition amount of the radical polymerization initiator (D-1) having a 10-hour half-life temperature of 40 to 60 ° C. is 0.1 to 0.5 parts by mass with respect to 100 parts by mass of the vinyl-based monomer mixture (m1) It is preferable to use it, more preferably 0.1 to 0.3 parts by mass. (Meth) acrylic acid ester obtained because the reaction at a low temperature hardly progresses when the addition amount of the radical polymerization initiator (D-1) having a half-life temperature of 10 hours is 40 to 60 ° C. is less than the above lower limit The color developability of the copolymer (A) is inferior, and when the above upper limit is exceeded, a rapid reaction tends to occur, and the color developability of the (meth) acrylic acid ester copolymer (A) obtained is also inferior. There is.

  The radical polymerization initiator (D-2) having a 10-hour half-life temperature of 70 to 90 ° C. is not particularly limited, and, for example, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy -2-ethylhexanoate, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1 Peroxides such as 1-di (t-hexylperoxy) cyclohexane, 1,1-di (t-butylperoxy) cyclohexane and the like can be mentioned. These may use only 1 type and may use 2 or more types together.

  The addition amount of the radical polymerization initiator (D-2) having a 10-hour half-life temperature of 70 to 90 ° C. is preferably 0.01 to 0.3 parts by mass with respect to 100 parts by mass of the monomer mixture And more preferably 0.03 to 0.25 parts by mass. The residual amount in the (meth) acrylic acid ester copolymer (A) obtained when the addition amount of the radical polymerization initiator (D-2) having a half-life temperature of 10 hours is 70 to 90 ° C. is less than the above lower limit As the N-substituted maleimide monomer increases and the color developability becomes poor, when the above upper limit is exceeded, coloration occurs due to a side reaction at a high temperature by the residual radical polymerization initiator, and (meth) acrylic acid ester type co-obtained also The color developability of the polymer (A) tends to be poor.

In addition, a radical polymerization initiator (D-1) and a radical polymerization initiator (D-2) are mass ratio of 1: 0.01-1 with respect to 100 mass parts of vinyl-type monomer mixtures (m1). It is preferable to add 0.15-0.7 mass parts in total. Moreover, it is preferable that the 10-hour half-life temperature of a radical polymerization initiator (D-1) and a radical polymerization initiator (D-2) has a difference of 20 degreeC or more.
Also, as a radical polymerization initiator, a radical polymerization initiator having a 10-hour half-life temperature outside the range of 40 to 60 ° C. or 70 to 90 ° C., for example, a radical polymerization initiator having a 10-hour half-life temperature of less than 40 ° C. It is preferable not to use a radical polymerization initiator having a time half-life temperature of more than 60 ° C. and less than 70 ° C. or a radical polymerization initiator having a 10-hour half-life temperature of more than 90 ° C.

  The chain transfer agent alkyl mercaptan includes, but is not limited to, for example, n-butyl mercaptan, sec-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-stearyl Among them, mercaptan and the like can be mentioned, and among them, n-octyl mercaptan and t-dodecyl captan are particularly preferably used. These may use only 1 type and may use 2 or more types together.

  The addition amount of the alkyl mercaptan is preferably 0.05 to 1.0 parts by mass, particularly 0.2 to 0.7 parts by mass with respect to 100 parts by mass of the vinyl monomer mixture (m1). If the addition amount of the alkyl mercaptan is less than the above lower limit, high viscosity effect tends to occur and rapid reaction occurs, and the color developability of the obtained (meth) acrylate copolymer (A) tends to decrease. In addition, when the addition amount of the alkyl mercaptan exceeds the above range, a Michael adduct formed by the alkyl mercaptan and the N-substituted maleimide monomer is generated, and as a result, the N-substituted maleimide monomer remains, which is also obtained The color developability of the (meth) acrylate copolymer (A) tends to be reduced.

  The α-methylstyrene dimer is a component that effectively suppresses the yellowness and heat coloration of the (meth) acrylate copolymer (A) obtained by reducing the reaction rate. The addition amount of α-methylstyrene dimer is preferably 0.05 to 1.0 parts by mass, particularly 0.1 to 0.4 parts by mass with respect to 100 parts by mass of the vinyl monomer mixture (m1). . If the addition amount of the α-methylstyrene dimer is less than the above lower limit, a rapid reaction occurs, and the color developability of the obtained (meth) acrylic acid ester copolymer (A) decreases, and if it exceeds the above upper limit The reaction at a relatively low temperature hardly progresses, and as a result, the color developability of the (meth) acrylic acid ester copolymer (A) also tends to decrease.

  In addition, it is preferable to add 0.3 to 1.2 mass parts in total with respect to 100 mass parts of monomer mixtures by a mass ratio of 1: 0.1-1 of an alkyl mercaptan and an alpha-methylstyrene dimer. .

  In the preferred method for producing the (meth) acrylate copolymer (A) of the present invention, a polymerization reaction is initiated at a temperature of 40 to 60 ° C. with respect to the above-mentioned reaction raw material mixture to continuously or stepwisely. The temperature is raised to 100 to 140 ° C. so that the temperature rising rate per hour is 1 to 20 ° C., and the polymerization reaction is completed in 5 to 12 hours.

  When the polymerization start temperature is less than 40 ° C., temperature control becomes difficult when the temperature is high in summer or the like, and when it exceeds 60 ° C., the (meth) acrylate copolymer (A) obtained tends to be easily colored It is inferior to sex. Therefore, the polymerization initiation temperature is preferably 40 to 60 ° C.

  If the heating rate during the reaction is less than 1 ° C./hr, it may not be possible to reach the temperature for completing the reaction described below, or it is necessary to increase the heating rate during the reaction, and if it exceeds 20 ° C./hr The (meth) acrylic acid ester copolymer (A) to be obtained may be easily colored and may be inferior in color developability. Therefore, the temperature rising rate is preferably 1 to 20 ° C./hr, more preferably 3 to 12 ° C./hr. The temperature rising rate may be constant or may change during the polymerization reaction, but the temperature rising rate per hour is preferably 1 to 20 ° C. in any period during the polymerization reaction. Preferably it is 3 to 12 ° C.

When the temperature for completing the reaction is less than 100 ° C., the residual N-substituted maleimide monomer increases in the obtained (meth) acrylic acid ester copolymer (A), and if it exceeds 140 ° C., high temperature Side reactions tend to occur, and the resulting (meth) acrylate copolymer (A) tends to be easily colored and to be inferior in color developability. Therefore, the temperature for completing the reaction is preferably 100 to 140 ° C., more preferably 100 to 125 ° C.
Here, the temperature at which the reaction is completed usually corresponds to the maximum temperature of the polymerization reaction.
However, the reaction temperature is raised from the start of the reaction, and the reaction is not limited to completion at the highest temperature, and after reaching the highest temperature, the reaction may be terminated at a temperature lowered from the highest temperature. In any case, the maximum temperature of the polymerization reaction is preferably in the range of 100 to 140 ° C., particularly 100 to 125 ° C.

  If the polymerization reaction time is less than 5 hours, the amount of remaining N-substituted maleimide monomer increases or a rapid reaction easily occurs, and the color developability of the obtained (meth) acrylate copolymer (A) is inferior It tends to be things. When the polymerization reaction time exceeds 12 hours, the time in the high temperature water solvent becomes long, coloring by hydrolysis tends to occur, and the color forming property of the obtained (meth) acrylate copolymer (A) is inferior It tends to be things. Therefore, the polymerization reaction time is preferably 5 to 12 hours, particularly 7 to 10 hours.

  Here, the polymerization reaction time refers to the time from the start of the polymerization reaction at a temperature of 40 to 60 ° C., the termination of the polymerization reaction, and the use of the reaction product for cooling.

<Physical Properties of (Meth) Acrylate Ester Copolymer (A)>
The content of the N-substituted maleimide monomer in the total 100% by mass of the vinyl monomer mixture (m1) is less than 9% by mass, and the content of the aromatic vinyl monomer is 7 to 39% by mass, The (meth) acrylic acid ester copolymer of the present invention formed by polymerizing the above-mentioned vinyl monomer mixture (m1) having a content of the meta) acrylic acid ester monomer of preferably 52 to 92% by mass (A) is usually 9% by mass of N-substituted maleimide monomer units in 100% by mass in total of all monomer units constituting the (meth) acrylate copolymer (A) The content of the aromatic vinyl monomer unit is 7 to 39% by mass, preferably 8 to 30% by mass, preferably at 2% to 9% by mass, more preferably 3% to 9% by mass. More preferably 9 to 25% by mass (meth) acrylic acid S Le content of monomer units is preferably 52 to 92 wt%, more preferably 60 to 85 wt%, more preferably becomes 65 to 80 mass%.
Here, “unit” means a structural part derived from a compound (monomer) before polymerization, contained in the copolymer, and, for example, “(meth) acrylic acid ester monomer unit” "A structural part derived from a (meth) acrylic acid ester monomer and contained in a (meth) acrylic acid ester copolymer (A)" is meant. In general, the content of the monomer unit of each polymer corresponds to the amount of the monomer used for producing the polymer.

  The mass average molecular weight of the (meth) acrylate copolymer (A) of the present invention is not particularly limited, but is preferably in the range of 10,000 to 300,000, and particularly preferably 50,000 to 200,000. It is preferable to be in the range of If the mass average molecular weight of the (meth) acrylate copolymer (A) is within the above range, the fluidity of the obtained (meth) acrylate copolymer (A) or thermoplastic resin composition, It will be excellent in scratch resistance and impact resistance.

  The mass average molecular weight of the (meth) acrylate copolymer (A) was determined by gel permeation chromatography (GPC), dissolved in tetrahydrofuran (THF) and measured in terms of standard polystyrene (PS) It is a thing.

The (meth) acrylate copolymer (A) of the present invention preferably has a glass transition temperature (Tg) of 110 to 130 ° C., particularly preferably 115 to 125 ° C., from the viewpoint of heat resistance.
In addition, the glass transition temperature (Tg) of a (meth) acrylic acid ester type copolymer (A) is measured by the method described in the term of the below-mentioned Example.

  From the viewpoint of scratch resistance, the (meth) acrylic acid ester copolymer (A) of the present invention has a surface hardness (pencil hardness) of H or more, which is measured by the method described in the section of Examples described later. In particular, 2H or more is preferable.

[Graft copolymer (C)]
The thermoplastic resin composition of the present invention polymerizes the vinyl monomer mixture (m2) in the presence of the (meth) acrylic acid ester copolymer (A) of the present invention and the rubbery polymer (B) And the graft copolymer (C) obtained by The graft copolymer (C) may be a graft polymer (C1) described later.

<Rubber-like polymer (B)>
There is no restriction | limiting in particular as a rubber-like polymer (B), A diene rubber-like polymer, an acrylic rubber-like polymer, an olefin rubber-like polymer, a silicone rubber-like polymer etc. are mentioned, These are independent. Or in combination of two or more.

  The diene rubber-like polymer is, for example, a diene rubber polymer containing, as a component, a diene component such as butadiene and isoprene and, if necessary, a monomer component copolymerizable therewith, Polybutadiene, polyisoprene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, butadiene-isoprene-styrene copolymer, polychloroprene and the like can be mentioned. One of these may be used alone, or two or more of these may be used in combination.

  The method for producing the diene rubber-like polymer is not particularly limited, but a known emulsion polymerization method is preferable. At that time, known emulsifiers, polymerization initiators, chain transfer agents and the like can also be used. Further, in controlling the particle diameter, a diene rubber-like polymer having a small particle diameter may be prepared in advance, and then the particle diameter may be increased by a known enlargement treatment.

  The acrylic rubber-like polymer is a copolymer having a unit derived from a (meth) acrylic acid ester monomer and a unit derived from a crosslinking agent and / or a unit derived from a graft crossing agent. Is preferred. (Meth) acrylic acid ester monomers such as (meth) acrylic acid alkyl esters having 1 to 12 carbon atoms in the alkyl group, acrylic acid esters having an aromatic hydrocarbon group (phenyl group, benzyl group, etc.), etc. N-butyl acrylate, 2-ethylhexyl acrylate, and ethyl acrylate are preferred from the viewpoint of the impact resistance of the resulting molded article. As the (meth) acrylic acid ester, one type may be used alone, or two or more types may be used in combination.

  Examples of the crosslinking agent include dimethacrylate compounds such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate. Examples of the grafting agent include allyl compounds such as allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like.

  The method for producing the acrylic rubber polymer is not particularly limited. For example, a method of obtaining an aqueous dispersion of an acrylic rubber polymer by emulsion polymerization of a monomer mixture containing (meth) acrylic acid ester monomer and either or both of a crosslinking agent and a grafting agent; Method of heteroflocculating or co-expanding the aqueous dispersion of the acrylic rubber polymer and the aqueous dispersion of the other rubber component; any of the aqueous dispersion of the acrylic rubbery polymer and the other aqueous dispersion of the rubber component The method of polymerizing and compounding the monomer mixture which comprises the other in the presence of one side etc. is mentioned.

The volume average particle diameter of the rubbery polymer (B) is preferably 0.01 to 1.00 μm, and more preferably 0.05 to 0.60 μm. It is excellent in impact resistance that the volume average particle diameter of a rubber-like polymer (B) is more than the said lower limit, and excellent in coloring property as it is below the said upper limit, so it is preferable. In order to obtain the rubbery polymer (B) having such a volume average particle diameter, the volume of the rubbery polymer (B) is adjusted by adjusting the amount of the emulsifier added at the time of production of the rubbery polymer (B). The average particle size may be adjusted.
In addition, the volume average particle diameter of a rubber-like polymer (B) is measured by the method described in the term of the below-mentioned Example.

<Vinyl-based monomer mixture (m2)>
The vinyl monomer mixture (m2) is at least one vinyl monomer selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers, and other vinyl monomers. It contains the body.

  Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, p-t-butylstyrene, ethylstyrene etc. Styrene and α-methylstyrene are preferred from the viewpoint of flowability of the resin composition, color development of molded articles, and impact resistance. An aromatic vinyl monomer may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the aromatic vinyl monomer is preferably 65 to 82% by mass, more preferably 73 to 80% by mass, and still more preferably 75 to 80% by mass in 100% by mass of the vinyl-based monomer mixture (m2). If the content of the aromatic vinyl monomer is within the above range, the colorability and impact resistance of the resulting molded article will be further improved.

  Examples of vinyl cyanide monomers include acrylonitrile and methacrylonitrile. The vinyl cyanide monomer may be used alone or in combination of two or more.

  The content of the vinyl cyanide monomer is preferably 18 to 35% by mass, more preferably 20 to 27% by mass, and still more preferably 20 to 25% by mass in 100% by mass of the vinyl-based monomer mixture (m2). If the content of the vinyl cyanide monomer is in the above range, the colorability and impact resistance of the resulting molded article will be further improved.

  As other vinyl monomers, for example, methacrylic acid ester (methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, methacrylic acid t-Butyl, amyl methacrylate, isoamyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, pentyl methacrylate, phenyl methacrylate, etc., maleimide compounds (N -Methyl maleimide, N-ethyl maleimide, N-n-propyl maleimide, N-i-propyl maleimide, N-n-butyl maleimide, N-i-butyl maleimide, N-tert-butyl maleimide, N-cycloalkyl malee (N-cyclohexyl maleimide etc.), N-aryl maleimide (N-phenyl maleimide, N-alkyl substituted phenyl maleimide, N-chlorophenyl maleimide etc.), N-aralkyl maleimide etc., acrylic ester (methyl acrylate, acrylic acid) Ethyl, propyl acrylate, butyl acrylate and the like can be mentioned. The other vinyl monomers may be used alone or in combination of two or more.

  The content of the other vinyl monomer is preferably 0 to 50% by mass, more preferably 0 to 30% by mass, and still more preferably 0 to 10% by mass in 100% by mass of the vinyl-based monomer mixture (m2). . By using other vinyl monomers, various functions can be improved according to the purpose, but when the content is too large, aromatic vinyl monomers and vinyl cyanide monomers There is a possibility that the effect by using may be impaired.

<Method of producing graft copolymer (C)>
The graft copolymer (C) is obtained by polymerizing the vinyl monomer mixture (m2) in the presence of the rubbery polymer (B).

  The graft copolymer (C) is, in the presence of 20 to 80% by mass of the rubbery polymer (B), 20 to 80% by mass of the vinyl monomer mixture (m2) (but the rubbery polymer (B) And the vinyl monomer mixture (m2) are preferably obtained by polymerizing 100% by mass), and the vinyl monomer amount is preferably in the presence of 25 to 75% by mass of the rubbery polymer (B). The mixture obtained by polymerizing 25 to 75% by mass of body mixture (m2) is more preferable, and vinyl monomer mixture (m2) 30 to 30 in the presence of 30 to 70% by mass of rubbery polymer (B) Those obtained by polymerizing 70% by mass are more preferable. If the proportion of the rubbery polymer (B) is within the above range, the productivity of the graft copolymer (C) is good and the colorability and impact resistance of the resulting molded article are further improved Become.

  Examples of the polymerization method of the graft copolymer (C) include known polymerization methods (emulsion polymerization method, solution polymerization method, suspension polymerization method, bulk polymerization method).

  For example, when manufactured by emulsion polymerization, a vinyl monomer mixture (m2) is added to an aqueous dispersion of a rubbery polymer (B), and the vinyl monomer mixture (m2) is radicalized in the presence of an emulsifier. It is manufactured by polymerizing. Various known chain transfer agents may be added to control the grafting rate and the molecular weight of the grafting component.

  Examples of the radical polymerization initiator include peroxides, azo initiators, redox initiators in which an oxidant and a reducing agent are combined, and the like, and from the viewpoint of facilitating control of the graft polymerization reaction, redox initiators. A sulfoxylate initiator in which ferrous sulfate-ethylenediaminetetraacetic acid disodium salt-long gallite-hydroperoxide is combined is particularly preferable.

  Preferred specific examples of the emulsifier include sodium or potassium salts of fatty acids (oleic acid, stearic acid, myristic acid, stearic acid, palmitic acid etc.), sodium lauryl sulfate, sodium N-lauroyl sarcosinate, dipotassium alkenyl succinate (octade Examples include dipotassium succinate, dipotassium heptadecenyl succinate, dipotassium hexadecenyl succinate, etc., sodium alkyl diphenyl ether disulfonate, and the like. An emulsifier may be used individually by 1 type, and may be used in combination of 2 or more type.

  In addition, as an emulsifier, you may use the emulsifier used in the case of manufacture of a rubber-like polymer (B) as it is. That is, the emulsifier contained in the aqueous dispersion of the rubbery polymer (B) may be used as it is, and no emulsifier may be added at the time of graft polymerization, or an emulsifier may be added at the time of graft polymerization as necessary. It is also good.

  As a method of recovering a graft copolymer (C) from an aqueous dispersion of a graft copolymer (C), the aqueous dispersion is put into hot water in which a coagulant is dissolved, and coagulated in a slurry state Method to recover by spraying (wet method); method to recover graft copolymer (C) semi-directly by spraying aqueous dispersion of graft copolymer (C) in heating atmosphere (spray drying Law) etc.

  Examples of the coagulant include inorganic acids (such as sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid), metal salts (such as calcium chloride, calcium acetate and aluminum sulfate). The coagulant is selected according to the emulsifier used in the polymerization. That is, when only sodium or potassium salts of fatty acids or sodium or potassium salts of carboxylic acids such as sodium or potassium salts of rosin acids are used as an emulsifier, any coagulant may be used. In the case where an emulsifier exhibiting stable emulsifying power even in an acidic region such as sodium dodecylbenzene sulfonate is contained as an emulsifier, it is necessary to use a metal salt.

  As a method of obtaining the graft copolymer (C) in the dry state from the graft copolymer (C) in the slurry state, after the emulsifier residue remaining in the slurry is eluted in water by washing, (i) the slurry A method of dewatering with a centrifugal dehydrator or press dehydrator and further drying with a flash dryer etc., (ii) A method of simultaneously carrying out dewatering and drying with a squeeze dehydrator, an extruder etc, etc. may be mentioned. After drying, the graft copolymer (C) is obtained in the form of powder or particles. Alternatively, the graft copolymer (C) discharged from the press dehydrator or extruder may be directly sent to an extruder or molding machine for producing a thermoplastic resin composition.

  The graft ratio of the graft copolymer (C) is preferably 10 to 150%, particularly 15 to 120%. It is excellent in impact resistance that the graft ratio of a graft copolymer (C) is more than the said lower limit, and excellent in fluidity | liquidity as it is below the said upper limit, so it is preferable.

  In addition, the graft ratio of a graft copolymer (C) is measured by the method described in the term of the below-mentioned Example.

[Graft polymer (C1)]
The thermoplastic resin composition of the present invention comprises, as a graft copolymer (C), a polyorganosiloxane (b-1) having a volume average particle diameter of 50 nm or more and less than 240 nm, and an alkyl (meth) acrylate polymer (b Graft obtained by polymerizing a vinyl-based monomer mixture (m2) containing an aromatic vinyl monomer and a vinyl cyanide monomer in the presence of the composite rubbery polymer (B1) of (2) It may contain the polymer (C1).

Among the graft copolymers (C) obtained by polymerizing the vinyl monomer mixture (m2) in the presence of the rubbery polymer (B), polyorganosiloxanes having a volume average particle diameter of 50 nm or more and less than 240 nm Vinyl-based monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in a composite rubbery polymer (B1) of (b-1) and an alkyl (meth) acrylate polymer (b-2) Using a graft copolymer (C1) obtained by polymerizing m2), melt kneading it with the (meth) acrylic acid ester copolymer (A) of the present invention to obtain a thermoplastic resin composition Thus, a thermoplastic resin composition excellent in fluidity, color developability, heat resistance and scratch resistance can be obtained, so that it can be suitably used as a molding material for vehicle interior and exterior parts, office equipment, home appliances, building materials, etc. .
The graft polymer (C1) will be described below.

<Polyorganosiloxane (b-1)>
The polyorganosiloxane (b-1) constituting the composite rubbery polymer (B1) is not particularly limited, but a polyorganosiloxane having a vinyl polymerizable functional group (vinyl polymerizable functional group-containing polyorganosiloxane) is preferable And more preferably a polyorganosiloxane having a vinyl polymerizable functional group-containing siloxane unit and a dimethylsiloxane unit. In this case, the proportion of the vinyl polymerizable functional group-containing siloxane unit in the polyorganosiloxane (b-1) is preferably 0.3 to 3 mol%. When the ratio of the vinyl polymerizable functional group-containing siloxane unit is within the above range, molding obtained by sufficiently complexing the polyorganosiloxane (b-1) and the alkyl (meth) acrylate polymer (b-2) It becomes difficult for the polyorganosiloxane (b-1) to bleed out on the surface of the product. As a result, the color developability, in particular, the color developability of the resulting molded article at the time of black coloring becomes better, and the impact resistance of the molded article is further improved.

  As the polyorganosiloxane (b-1), since the color developability of the molded product at the time of black coloring is further improved, the silicon atom having three or more siloxane bonds is 0 to the total silicon atoms in the polyorganosiloxane. What is 1 mol% is preferable. As a preferable aspect of a polyorganosiloxane (b-1), 0.3-3 mol% of vinyl polymerizable functional group containing siloxane units and 99.7-97 mol% of dimethylsiloxane units (however, vinyl polymerizable functional group containing) A polyorganosiloxane comprising a total of siloxane units and dimethylsiloxane units of 100 mol%), and a silicon atom having three or more siloxane bonds being 1 mol% or less based on the total silicon atoms in the polyorganosiloxane Can be mentioned.

  The average particle size of the polyorganosiloxane (b-1) is not particularly limited, but is preferably 400 nm or less, more preferably 150 nm or less, because the color developability of the molded article is further improved. On the other hand, the lower limit value of the average particle diameter of the polyorganosiloxane (b-1) is preferably 20 nm or more. Here, the average particle diameter of the polyorganosiloxane (b-1) is a value calculated from the particle diameter distribution obtained by measuring the particle diameter distribution on a mass basis using a particle size distribution measurement device (volume average particle diameter ).

  The polyorganosiloxane (b-1) is obtained, for example, by polymerizing a siloxane mixture containing dimethylsiloxane and a vinyl polymerizable functional group-containing siloxane. The polymerization method is not particularly limited, but emulsion polymerization is preferred.

  The dimethylsiloxane is preferably a three- or more-membered dimethylsiloxane cyclic group, more preferably a three- to seven-membered dimethylsiloxane cyclic group. Specifically, hexamethyl cyclotrisiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, dodecamethyl cyclohexasiloxane and the like can be mentioned. One of these dimethylsiloxanes may be used alone, or two or more thereof may be used in combination.

  The vinyl polymerizable functional group-containing siloxane is not particularly limited as long as it contains a vinyl polymerizable functional group and can be bonded to dimethylsiloxane via a siloxane bond, but in view of reactivity with dimethylsiloxane And various alkoxysilane compounds containing a vinyl polymerizable functional group are preferable. Specifically, β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, Methacryloyloxy siloxanes such as γ-methacryloyloxypropyl diethoxymethylsilane, δ-methacryloyloxybutyl diethoxymethylsilane; vinyl siloxanes such as tetramethyl tetravinyl cyclotetrasiloxane; p-vinylphenyldimethoxymethylsilane, γ-mercaptopropyldimethoxyme Mercaptosiloxanes, such as methylsilane and (gamma)-mercapto propyl trimethoxysilane, etc. are mentioned. These vinyl polymerizable functional group-containing siloxanes may be used alone or in combination of two or more.

  The polymerization of the siloxane mixture is usually carried out using an emulsifier, water and an acid catalyst. As an emulsifier, an anionic emulsifier is preferable. Specifically, sodium alkylbenzene sulfonate, sodium lauryl sulfonate, sodium polyoxyethylene nonylphenyl ether sulfate and the like can be mentioned. Among these, sulfonic acid emulsifiers such as sodium alkylbenzene sulfonate and sodium lauryl sulfonate are preferable. One of these emulsifying agents may be used alone, or two or more thereof may be used in combination. The amount of the emulsifier used is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the siloxane mixture. When the amount of the emulsifier used is 0.05 parts by mass or more, the dispersed state is easily stabilized, and the emulsified state of fine particle diameter is easily maintained. On the other hand, when the amount of the emulsifier used is 5 parts by mass or less, the coloring of the molded article caused by the emulsifier can be suppressed.

  Examples of the acid catalyst include organic acid catalysts such as sulfonic acids (eg, aliphatic sulfonic acid, aliphatic substituted benzene sulfonic acid, aliphatic substituted naphthalene sulfonic acid, etc.); and inorganic acids such as mineral acids (eg, sulfuric acid, hydrochloric acid, nitric acid, etc.) A catalyst etc. are mentioned. These acid catalysts may be used alone or in combination of two or more. Among these, aliphatic substituted benzenesulfonic acid is preferable and n-dodecylbenzenesulfonic acid is particularly preferable in that it is also excellent in the stabilizing action of a latex of siloxane latex (Ba) described later. In addition, when n-dodecylbenzenesulfonic acid and a mineral acid such as sulfuric acid are used in combination, the color of the emulsifier used in the production of the polyorganosiloxane (b-1) can be minimized to a small extent the color of the molded article obtained. it can. Although the addition amount of the acid catalyst may be determined appropriately, it is usually about 0.1 to 20 parts by mass with respect to 100 parts by mass of the siloxane mixture.

  The mixing of the acid catalyst may be performed at the timing of mixing the siloxane mixture, the emulsifying agent and water, or the emulsifying agent and water are added to the siloxane mixture and emulsified to obtain a latex (siloxane latex (Ba)). It may be after micronization. It is preferable to mix the siloxane latex (Ba) and the acid catalyst after micronizing the siloxane latex (Ba), since the particle diameter of the resulting polyorganosiloxane (b-1) can be easily controlled. In particular, it is preferable to drop the micronized siloxane latex (Ba) into the aqueous acid catalyst solution at a constant rate. In addition, when mixing an acid catalyst with the timing which mixes a siloxane mixture, an emulsifier, and water, it is preferable to micronize after mixing these.

  The siloxane latex (Ba) can be micronized by using, for example, a homomixer which micronizes by shear force by high speed rotation, or a homogenizer which micronizes by jet output of a high pressure generator. As a method of mixing a siloxane mixture, an emulsifier, water and an acid catalyst, and as a method of mixing micronized siloxane latex (Ba) and an acid catalyst, for example, mixing by high speed stirring, mixing by a high pressure emulsifying apparatus such as a homogenizer, etc. Can be mentioned. Among them, the method using a homogenizer is preferable because the distribution of the particle diameter of the polyorganosiloxane (b-1) can be reduced.

  50 degreeC or more is preferable and, as for superposition | polymerization temperature, 80-90 degreeC is more preferable. When the micronized siloxane latex (Ba) is dropped into the aqueous acid catalyst solution, the temperature of the aqueous acid catalyst solution is preferably 50 ° C. or higher, and more preferably 80 to 90 ° C.

  The polymerization time is preferably 2 hours or more, more preferably 5 hours or more, in the case of mixing the acid catalyst at the timing of mixing the siloxane mixture, the emulsifier and the water. On the other hand, in the case where the micronized siloxane latex (Ba) and the acid catalyst are mixed, it is preferable to hold the micronized siloxane latex (Ba) in an aqueous acid catalyst solution for about one hour.

  The termination of the polymerization is to neutralize the reaction solution with an alkaline substance such as sodium hydroxide, potassium hydroxide, sodium carbonate or the like so that the pH of the reaction solution at 25 ° C. becomes about 6 to 8 after cooling the reaction solution. Can be done by

  The average particle size of the polyorganosiloxane (b-1) can be controlled by adjusting the composition of the siloxane mixture, the amount of the acid catalyst used (content of the acid catalyst in the aqueous acid catalyst solution), the polymerization temperature, and the like. For example, the average particle size tends to increase as the amount of the acid catalyst used decreases, and the average particle size tends to decrease as the polymerization temperature increases.

<Alkyl (Meth) Acrylate Polymer (b-2)>
The (meth) acrylate polymer (b-2) constituting the composite rubbery polymer (B1) is obtained by polymerizing a monomer component containing one or more kinds of alkyl (meth) acrylate monomers is there. The monomer component may contain a monomer (other monomer) other than the alkyl (meth) acrylate monomer.

  As the alkyl (meth) acrylate monomer, for example, acrylic acid alkyl ester such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate; hexyl methacrylate, methacrylic acid Examples thereof include methacrylic acid alkyl esters such as 2-ethylhexyl and n-lauryl methacrylate. These alkyl (meth) acrylate monomers may be used alone or in combination of two or more. Among them, n-butyl acrylate is preferable in that the impact resistance of the resulting molded article is further improved. 80-100 mass% is preferable, and, as for the ratio of the alkyl (meth) acrylate monomer in 100 mass% of monomer components, 90-100 mass% is more preferable.

  Other monomers are not particularly limited as long as they can be copolymerized with alkyl (meth) acrylate monomers, but aromatic vinyl monomers (eg, styrene, α-methylstyrene, p-methylstyrene etc.) And vinyl cyanide monomers (eg, acrylonitrile, methacrylonitrile, etc.). One of these other monomers may be used alone, or two or more thereof may be used in combination.

  The method for producing the alkyl (meth) acrylate polymer (b-2) is not particularly limited, and can be carried out according to known methods.

<Compound rubbery polymer (B1)>
The composite rubbery polymer (B1) is a composite rubber in which the polyorganosiloxane (b-1) and the alkyl (meth) acrylate polymer (b-2) are composited.

  The volume average particle diameter of the composite rubbery polymer (B1) is 50 nm or more and less than 240 nm, preferably 90 or more and less than 160 nm. The impact resistance of the molded article obtained decreases that the volume average particle size of the composite rubbery polymer (B1) is less than 50 nm, and the color development of the molded article tends to decrease when the volume average particle size is 240 nm or more. There is. Here, the volume average particle diameter of the composite rubber-like polymer (B1) is a value calculated from the particle diameter distribution obtained by measuring the volume-based particle diameter distribution using a particle size distribution measuring device.

The proportion of particles having a particle diameter of 300 to 500 nm in the total particles in the composite rubbery polymer (B1) is preferably 0 to 25% by volume. That is, the composite rubbery polymer (B1) preferably has a particle size distribution in which particles having a particle diameter of 300 to 500 nm occupy a ratio of 0 to 25% by volume in all particles. When the proportion of particles having a particle diameter of 300 to 500 nm exceeds the above upper limit, the color developability of the resulting molded article, particularly the jet blackness at the time of black coloring tends to decrease. The proportion of particles having a particle diameter of 300 to 500 nm is preferably 0 to 25% by volume, since the impact resistance and color developability of the resulting molded article, and in particular the balance of jet blackness at the time of black coloring, will be better. .
Further, the proportion of particles having a particle diameter of more than 500 nm in the total particles in the composite rubbery polymer (B1) is preferably less than 1% by volume, and more preferably less than 0.1% by volume.

<Method of producing composite rubbery polymer (B1)>
The method for producing the composite rubbery polymer (B1) is not particularly limited, but heteroaggregation or co-aggregation of a plurality of latexes each containing the polyorganosiloxane (b-1) and the alkyl (meth) acrylate polymer (b-2) Method for enlarging: a monomer component for forming the other polymer in the presence of a latex containing either one of the polyorganosiloxane (b-1) and the alkyl (meth) acrylate polymer (b-2) The method of making it superpose | polymerize and making it compound etc. is mentioned. In particular, since the volume average particle diameter of the composite rubbery polymer (B1) can be easily adjusted to be within the above-mentioned range, the alkyl (meth) acrylate in the presence of the latex-like polyorganosiloxane (b-1) After radically polymerizing a monomer component containing one or more monomers to obtain a copolymer latex (radical polymerization step), the copolymer latex and the acid group-containing copolymer latex are mixed. And a method of enlarging the copolymer latex (the enlargement step) is preferable. Furthermore, it is preferable to add a condensation acid salt to the copolymer latex before mixing the copolymer latex and the acid group-containing copolymer latex.
Each step will be described below.

  The radical polymerization step is a step of radically polymerizing a monomer component containing one or more alkyl (meth) acrylate monomers in the presence of the latex-like polyorganosiloxane (b-1). The monomer component containing one or more kinds of alkyl (meth) acrylate monomers may be added collectively to the latex-like polyorganosiloxane (b-1), or added continuously or intermittently. You may

  When radically polymerizing a monomer component containing one or more kinds of alkyl (meth) acrylate monomers, a graft crossing agent or a crosslinking agent may be used as needed. As a graft crossing agent and a crosslinking agent, for example, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, divinyl benzene, ethylene glycol diester of dimethacrylic acid, propylene glycol diester of dimethacrylic acid, 1,3-butylene glycol diester of dimethacrylic acid And dimethacrylic acid 1,4-butylene glycol diester and the like. One of these may be used alone, or two or more may be used in combination.

For radical polymerization, a radical polymerization agent and an emulsifier are usually used.
Examples of the radical polymerization initiator include peroxides, azo initiators, and redox initiators in which an oxidizing agent and a reducing agent are combined. Among these, redox initiators are preferable, and particularly, sulfoxylate initiators obtained by combining ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, sodium formaldehyde sulfoxylate and hydroperoxide are preferable.

  The emulsifier is not particularly limited, but various carboxylic acids such as sodium sarcosinate, fatty acid potassium, fatty acid sodium, dipotassium alkenyl succinate, rosin acid soap and the like because the stability of the latex during radical polymerization is excellent and the polymerization rate can be increased. Salt is preferred. Among these, dipotassium alkenyl succinate is preferable because it can suppress gas generation when the resulting graft copolymer (C1) and a thermoplastic resin composition containing the same are molded at high temperature. Specific examples of alkenyl potassium succinate include dipotassium octadecenyl succinate, dipotassium heptadecenyl succinate, dipotassium hexadecenyl succinate and the like. An emulsifier may be used individually by 1 type, and may be used in combination of 2 or more type.

  The enlargement step is a step of enlarging the copolymer latex by mixing the copolymer latex obtained in the radical polymerization step with the acid group-containing copolymer latex. The acid group-containing copolymer latex used for enlargement includes, in water, an acid group-containing monomer, an alkyl (meth) acrylate monomer, and, if necessary, other monomers copolymerizable therewith. It is a latex of an acid group containing copolymer obtained by polymerizing the monomer component to contain.

  As the acid group-containing monomer, an unsaturated compound having a carboxy group is preferable. Examples of the compound include (meth) acrylic acid, itaconic acid, crotonic acid and the like, and (meth) acrylic acid is particularly preferable. As the acid group-containing monomer, one type may be used alone, or two or more types may be used in combination.

  Examples of the alkyl (meth) acrylate monomer include esters of (meth) acrylic acid and alcohols having a linear or branched alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, Methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylate n -Butyl, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate and the like can be mentioned. The alkyl (meth) acrylate monomers may be used alone or in combination of two or more.

  The other monomer is a monomer copolymerizable with the acid group-containing monomer and the alkyl (meth) acrylate monomer, and other than the acid group-containing monomer and the alkyl (meth) acrylate monomer Is a monomer of Other monomers include aromatic vinyl monomers (eg, styrene, α-methylstyrene, p-methylstyrene, etc.), vinyl cyanide monomers (eg, acrylonitrile, methacrylonitrile, etc.), two The compounds having the above polymerizable functional group (for example, allyl methacrylate, polyethylene glycol dimethacrylate methacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate etc., and the like can be mentioned. The other monomers may be used alone or in combination of two or more.

  As the amount used of these monomers, an amount of 5 to 40% by mass of the acid group-containing monomer unit as a proportion of the solid content of 100% by mass of the acid group-containing copolymer latex, alkyl (meth) acrylate Preferably, an amount of 60 to 95% by mass of monomer units, an amount of 0 to 48% by mass of other monomer units, an amount of 8 to 30% by mass of acid group-containing monomer units, alkyl More preferably, the amount of the (meth) acrylate monomer unit is 70 to 92% by mass, and the amount of the other monomer units is 0 to 30% by mass. When the ratio of the acid group-containing monomer unit is 5% by mass or more and the ratio of the alkyl (meth) acrylate monomer unit is 95% by mass or less, sufficient enlargement capacity can be obtained. In addition, when the ratio of the acid group-containing monomer unit is 40% by mass or less and the ratio of the alkyl (meth) acrylate monomer unit is 60% by mass or more, a large amount of acid group-containing copolymer latex is produced. It is possible to suppress the formation of agglomerates. In addition, when the amount of the other monomer units is 48% by mass or less, the obtained acid group-containing copolymer latex can have a sufficient enlargement capacity.

  The acid group-containing copolymer latex can be produced by a general emulsion polymerization method. Emulsifiers used in emulsion polymerization include carboxylic acid emulsifiers such as oleic acid, palmitic acid, stearic acid, alkali metal salts of rosin acid, alkali metal salts of alkenyl succinic acid; alkyl sulfates, sodium alkylbenzene sulfonates, Examples of known emulsifiers include anionic emulsifiers such as sodium alkylsulfosuccinate and sodium polyoxyethylene nonylphenyl ether sulfate ester. One of these emulsifying agents may be used alone, or two or more thereof may be used in combination.

  The emulsifier may be added all at once at the beginning of polymerization, or may be added continuously or intermittently. Depending on the amount of emulsifier and the method of using it, the particle size of the acid group-containing copolymer latex and, in turn, the particle size of the composite rubber-like polymer (B1) latex having an increased particle size may be affected. It is preferred to select the amount and method of use.

  As a polymerization initiator used for emulsion polymerization, a thermal decomposition type initiator, a redox type initiator, etc. can be used. Examples of the thermal decomposition initiator include potassium persulfate, sodium persulfate, ammonium persulfate and the like, and as the redox initiator, an organic peroxide represented by cumene hydroperoxide-sodium formaldehyde sulfoxylate-iron A combination of salts etc. is exemplified. One of these polymerization initiators may be used alone, or two or more thereof may be used in combination.

  In emulsion polymerization, a chain transfer agent such as mercaptans (eg t-dodecyl mercaptan, n-octyl mercaptan etc.), terpinolene, α-methylstyrene dimer etc. is used to adjust molecular weight, or pH is adjusted. Therefore, an electrolyte can be added as an alkali, an acid, or a viscosity reducing agent.

  The addition amount (solid content equivalent amount) of the acid group-containing copolymer latex in the enlargement step is adjusted so that the volume average particle diameter and particle diameter distribution of the composite rubbery polymer (B1) fall within the above-mentioned range. Although it may be sufficient, in general, 0.1 to 5 parts by mass is preferable, and 0.3 to 3 parts by mass is more preferable with respect to 100 parts by mass of the solid content of the copolymer latex obtained in the radical polymerization step. When the addition amount of the acid group-containing copolymer latex is 0.1 parts by mass or more, the enlargement proceeds sufficiently. In addition, generation of a large amount of agglomerates can be suppressed. On the other hand, if the addition amount of the acid group-containing copolymer latex is 5 parts by mass or less, the pH of the enlarged latex can be suppressed from decreasing, and the latex is less likely to be unstable. The acid group-containing copolymer latex may be added collectively to the copolymer latex, or may be added continuously or intermittently by dropwise addition.

  Further, it is more preferable to add a condensed acid salt to the copolymer latex prior to the enlargement step. If a condensation salt is added to the copolymer latex before the addition of the acid group-containing copolymer latex, the addition of the acid group-containing copolymer latex can be reduced by facilitating the progress of enlargement. This becomes possible, and it becomes easy to adjust the volume average particle diameter and particle diameter distribution of the composite rubbery polymer (B1) to be obtained within the above-mentioned range.

  As the condensed acid salt, for example, salts of condensed acids such as phosphoric acid and silicic acid and alkali metals and / or alkaline earth metals are used. Among these, pyrophosphate which is a condensed acid of phosphoric acid and a salt of an alkali metal are preferable, and sodium pyrophosphate or potassium pyrophosphate is particularly preferable.

  The addition amount of the condensed acid salt may be adjusted so that the volume average particle size and particle size distribution of the composite rubbery polymer (B1) fall within the above-mentioned range, but it is usually obtained in the radical polymerization step. The amount is preferably 0.1 to 5 parts by mass, and more preferably 0.3 to 3 parts by mass with respect to 100 parts by mass of the solid content of the copolymer latex. If the addition amount of the condensed acid salt is 0.1 parts by mass or more, the enlargement proceeds sufficiently, and if 5 parts by mass or less, the enlargement proceeds sufficiently, or the rubber latex is easily stabilized, and a large amount of coagulation It is possible to suppress the generation of lumps. The condensed acid salt is preferably added to the copolymer latex all at once.

  The pH at 25 ° C. of the mixture of the copolymer latex and the condensed acid salt is preferably 7 or more. When the pH is 7 or more, the hypertrophy can be sufficiently progressed. Common alkaline compounds such as sodium hydroxide and potassium hydroxide can be used to adjust the pH to 7 or more.

  It is preferable to control the stirring at the time of enlargement appropriately. If the stirring is insufficient, the unexpanded rubbery polymer may remain due to the progress of the enlargement locally. On the other hand, excessive stirring may make the enlarged latex unstable and generate a large amount of agglomerates. Although the temperature in particular at the time of performing enlargement is not restrict | limited, 20-90 degreeC is preferable and 30-80 degreeC is more preferable. If the temperature is outside this range, the enlargement may not proceed sufficiently.

  The composite rubbery polymer (B1) is enlarged using the acid group-containing copolymer latex as described above, and then the monomer component containing one or more kinds of alkyl (meth) acrylate monomers is further added. It may be produced by addition and polymerization.

  The ratio of the polyorganosiloxane (b-1) to the alkyl (meth) acrylate polymer (b-2) in the composite rubbery polymer (B1) is the same as that of the polyorganosiloxane (b-1) and the alkyl (meth) acrylate It is preferable that the ratio of polyorganosiloxane (b-1) is 1 mass% or more and less than 25 mass%, when the sum total with a system polymer (b-2) is 100 mass%. When the proportion of polyorganosiloxane (b-1) is less than 1% by mass, the resulting molded article is inferior in scratch resistance and impact resistance, and the proportion of polyorganosiloxane (b-1) is 25% by mass or more. If there is, it tends to be inferior in color developability.

<Vinyl-based monomer mixture (m2)>
The vinyl-based monomer mixture (m2) used for producing the graft polymer (C1) is the same as the vinyl-based monomer mixture (m2) used for producing the above-mentioned graft copolymer (C), and is preferably a single monomer. The same applies to the mass composition.

<Method of producing graft copolymer (C1)>
The graft copolymer (C1) is obtained by polymerizing the vinyl monomer mixture (m2) in the presence of the composite rubbery polymer (B1).

  The method for polymerizing the vinyl-based monomer mixture (m1) in the presence of the composite rubbery polymer (B1) is not particularly limited, but the emulsion polymerization is possible because the reaction can be controlled to proceed stably. Is preferred. Specifically, a method in which a vinyl-based monomer mixture (m2) is collectively charged to the composite rubber-like polymer (B1) and then polymerized; a vinyl-based monomer mixture (composite rubber-like polymer (B1) A method of charging a part of m2) first and dropping the rest into the polymerization system while optionally polymerizing; optionally polymerizing while dropping the whole amount of the vinyl monomer mixture (m2) to the composite rubbery polymer (B1) These may be divided into one or two or more stages. Moreover, it is also possible to carry out by changing the kind and composition ratio of the vinyl-based monomer mixture (m2) in each stage.

  The mass ratio of the composite rubbery polymer (B1) and the vinyl monomer mixture (m2) is not particularly limited, but the balance between impact resistance and color developability of the resulting molded article is better. Preferably, the composite rubbery polymer (B1) is 10 to 80% by mass, and the vinyl monomer mixture (m2) is 20 to 90% by mass, and the composite rubbery polymer (B1) is 30 to 70%. %, And it is particularly preferable to set the vinyl monomer mixture (m2) to 30 to 70% by mass (however, the total of the composite rubbery polymer (B1) and the vinyl monomer mixture (m2) is 100% by mass) And). When graft polymerization is carried out at this mass ratio, the flowability of the resulting thermoplastic resin composition, and the impact resistance and color developability of the molded article become more excellent.

  In the graft polymerization, a radical polymerization initiator and an emulsifier are usually used. As these radical polymerization initiators and emulsifiers, the radical polymerization initiators and emulsifiers exemplified above in the description of the method for producing the composite rubbery polymer (B1) may be mentioned. In addition, when radical polymerization is performed, various known chain transfer agents may be added to control the molecular weight and grafting ratio of the resulting graft copolymer (C1).

  The graft copolymer (C1) is usually obtained in the form of a latex. As a method of recovering the graft copolymer (C1) from the latex of the graft copolymer (C1), for example, the latex of the graft copolymer (C1) is introduced into hot water in which the coagulant is dissolved. A wet method of coagulating in a slurry state; and a spray drying method of semi-directly recovering the graft copolymer (C1) by spraying a latex of the graft copolymer (C1) in a heating atmosphere.

  Examples of the coagulant used in the wet method include inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and nitric acid; metal salts such as calcium chloride, calcium acetate and aluminum sulfate, etc., and are selected according to the emulsifier used in polymerization. . For example, when only carboxylic acid soaps such as fatty acid soaps and rosin acid soaps are used as emulsifiers, one or more of the coagulants described above can be used. When an emulsifying agent which exhibits stable emulsifying power even in an acidic region such as sodium alkylbenzene sulfonate is used as the emulsifying agent, a metal salt is suitable as the coagulant.

  By using a wet process, a slurry-like graft copolymer (C1) is obtained. As a method of obtaining the graft copolymer (C1) in a dry state from the slurry-like graft copolymer (C1), the remaining emulsifier residue is first eluted in water and washed, and then the slurry is centrifuged or pressed. A method of dewatering with a dehydrator or the like and then drying with an air flow drier or the like; By such a method, a powder or particulate dry graft copolymer (C1) is obtained.

  The graft ratio of the graft polymer (C1) is preferably 35 to 60%, particularly 40 to 50%. It is excellent in impact resistance that the grafting rate of a graft polymer (C1) is more than the said lower limit, and excellent in fluidity | liquidity as it is below the said upper limit, so it is preferable.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present invention contains the (meth) acrylic acid ester copolymer (A) of the present invention, and the (meth) acrylic acid ester copolymer (A) of the present invention as a resin component The (meth) acrylic acid ester copolymer (A) of the present invention and the above graft copolymer (C) (as mentioned above, the graft copolymer (C) may be It may be a graft polymer (C1). Alternatively, it may contain the (meth) acrylic acid ester copolymer (A) of the present invention and other thermoplastic resins described later.

<Content of (meth) acrylate copolymer (A)>
When the thermoplastic resin composition of the present invention contains a (meth) acrylic acid ester copolymer (A) and the above graft copolymer (C), the (meth) acrylic acid ester copolymer (A) The content is 50 to 90% by mass, in particular 50 to 80% by mass, particularly when the total of the (meth) acrylate copolymer (A) and the graft copolymer (C) is 100% by mass. It is preferable that it is 60-70 mass%.
When the content of the (meth) acrylate copolymer (A) is within the above range, the fluidity, color developability, heat resistance, scratch resistance, impact resistance of the thermoplastic resin composition and the molded article thereof The surface impact resistance is excellent.

<Other thermoplastic resin>
The thermoplastic resin composition of the present invention may optionally contain other thermoplastic resins other than the (meth) acrylic acid ester copolymer (A) and the graft copolymer (C). The other thermoplastic resin is not particularly limited, and examples thereof include polymethyl methacrylate (PMMA resin), methyl methacrylate-N-cyclohexyl maleimide-N-phenyl maleimide-styrene copolymer, polycarbonate resin, polybutylene terephthalate (PBT) Resin), polyethylene terephthalate (PET resin), polyvinyl chloride, polystyrene, polyacetal resin, modified polyphenylene ether (modified PPE resin), ethylene-vinyl acetate copolymer, polyarylate, liquid crystal polyester resin, polyethylene resin, polypropylene resin, fluorine Resin and polyamide resin (nylon) etc. are mentioned. One of these may be used alone, or two or more of these may be used in combination.

  When the thermoplastic resin composition of the present invention contains these other thermoplastic resins, it comprises the (meth) acrylic acid ester copolymer (A) of the present invention and the graft copolymer (C) described above. The content of the other thermoplastic resin in 100% by mass of the total thermoplastic resin component in the thermoplastic resin composition is from the viewpoint of more effectively obtaining the effects of fluidity, color development, heat resistance and scratch resistance by the The content is preferably 80% by mass or less, particularly 50% by mass or less.

<Additives>
In the thermoplastic resin composition of the present invention, other additives commonly used at the time of production (at the time of mixing) of the thermoplastic resin composition and at the time of molding as long as the physical properties of the thermoplastic resin composition and its molded articles are not impaired. For example, lubricants, pigments, dyes, fillers (carbon black, silica, titanium oxide, etc.), heat-resistant agents (thermal stabilizers), antioxidative deterioration agents, weathering agents (ultraviolet light absorbers, light stabilizers), release agents , Plasticizer, antistatic agent, flame retardant, flame retardant auxiliary, curing agent, curing accelerator, conductivity imparting agent, stress relaxation agent, crystallization accelerator, hydrolysis inhibitor, lubricant, impact modifier, slide Dynamic modifier, compatibilizer, nucleating agent, toughening agent, flow control agent, sensitizer, thickener, anti-settling agent, anti-drip agent, anti-foaming agent, coupling agent, light diffusing fine particles, rust prevention An agent, an antibacterial agent, an antifungal agent, an antifouling agent, a conductive polymer and the like can be blended.

<Method of producing thermoplastic resin composition>
The thermoplastic resin composition of the present invention can be produced by a known method using a known device. For example, there is a melt mixing method as a general method, and as an apparatus used in this method, an extruder, a Banbury mixer, a roller, a kneader, etc. may be mentioned. Either a batch system or a continuous system may be adopted for mixing. Moreover, there is no restriction | limiting in particular also in the order of mixing of each component, etc., and all the components should just be mixed uniformly.

[Molding]
The molded article of the present invention is formed by molding the thermoplastic resin composition of the present invention. Examples of the molding method include an injection molding method, an injection compression molding machine method, an extrusion method, a blow molding method, a vacuum molding method, a pressure forming method, a calendar molding method, and an inflation molding method. Among them, injection molding method and injection compression molding method are preferable because they are excellent in mass productivity and can obtain molded products with high dimensional accuracy.

[Use]
The thermoplastic resin composition of the present invention and the molded article thereof containing the (meth) acrylate copolymer (A) of the present invention are excellent in fluidity, and also excellent in color development, heat resistance and scratch resistance. It is suitably used in a wide range of fields such as interior and exterior parts of vehicles, office equipment, home appliances and building materials.

Hereinafter, the present invention will be described with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.
In the following, “%” means “mass%” and “parts” means “mass parts”.

[Measurement and evaluation method]
Various measurement and evaluation methods in the following examples and comparative examples are as follows.

<Method of measuring volume average particle diameter of rubbery polymer (B) or composite rubbery polymer (B1)>
The rubbery polymer (B) or the composite rubbery polymer (B1) dispersed in an aqueous dispersion using ion transport water as a measurement solvent using Microtrac (“Nanotrac 150” manufactured by Nikkiso Co., Ltd.) The volume average particle size was measured.

<Method of measuring graft ratio of graft copolymer (C) or graft polymer (C1)>
Add 1 g of the graft copolymer (C) or graft polymer (C1) to 80 mL of acetone, heat to reflux at 65 to 70 ° C. for 3 hours, and centrifuge the obtained suspension acetone solution (Hitachi Koki The mixture was centrifuged at 14,000 rpm for 30 minutes using "CR21E" manufactured by Co., Ltd. to separate the precipitated component (acetone-insoluble component) and the acetone solution (acetone-soluble component). And the precipitation component (acetone insoluble component) was dried, the mass (Y (g)) was measured, and the graft ratio was computed by following formula (1). In addition, Y in Formula (1) is a mass (g) of the acetone insoluble component of a graft copolymer (C) or a graft polymer (C1), X is a graft copolymer (C) used when calculating | requiring Y Or the total mass (g) and rubber fraction of the graft polymer (C1) are the rubbery polymer (B) or composite rubbery polymer used for the production of the graft copolymer (C) or the graft polymer (C1) It is solid content concentration in the aqueous dispersion of (B1).
Graft ratio (mass%) = {(Y-X × rubber fraction) / X × rubber fraction} × 100 (1)

<Molecular weight measurement of (meth) acrylic acid ester type copolymer (A)>
The mass average molecular weight of the (meth) acrylate copolymer (A) was determined by gel permeation chromatography (GPC), dissolved in tetrahydrofuran (THF) and measured in terms of standard polystyrene (PS) It is a thing.

<Glass transition temperature (Tg) of (meth) acrylate copolymer (A)>
The glass transition temperature (Tg) of the (meth) acrylate copolymer (A) was determined by differential scanning calorimetry (DSC). Specifically, after raising the temperature of the (meth) acrylate copolymer (A) from 35 ° C. to 250 ° C. at 10 ° C./min in a nitrogen atmosphere, it is cooled to 35 ° C., and then to 250 ° C. The glass transition temperature observed when the temperature was raised was determined. The higher the glass transition temperature, the better the heat resistance.
From the viewpoint of heat resistance, the glass transition temperature (Tg) of the (meth) acrylic acid ester copolymer (A) is preferably 110 ° C. to 130 ° C., particularly at 115 ° C. to 125 ° C., as described above. Is preferred.

<Composition analysis of (meth) acrylic acid ester copolymer (A)>
The compositional analysis of the (meth) acrylic acid ester copolymer (A) is carried out based on the elemental analysis results (N amount, O amount) using an element analysis apparatus MT-6 manufactured by Yanaco, the amount of N-phenylmaleimide, The amount of methyl methacrylate was determined, and the remainder was calculated as the amount of styrene.

[material]
The raw materials used in the following Examples and Comparative Examples are as follows.

<Monomer raw material>
Methyl methacrylate: manufactured by Mitsubishi Rayon Co., Ltd., Acryester (registered trademark) M
N-phenyl maleimide: Nippon Shokubai Co., Ltd.
Styrene: NS Styrene Monomer Co., Ltd.

<Radical polymerization initiator>
t-Butyl peroxypivalate: manufactured by NOF Corporation, Perbutyl PV (10-hour half-life temperature: 54.6 ° C)
t-Butylperoxy-2-ethylhexanoate: manufactured by NOF Corporation, Perbutyl O (10-hour half-life temperature: 72.1 ° C)
1,1-di (t-hexylperoxy) cyclohexane: manufactured by NOF Corporation, perhexa HC (10-hour half-life temperature: 87.1 ° C.)

<Chain transfer agent>
t-dodecyl mercaptan: manufactured by Arkema Co., Ltd. α-methylstyrene dimer: manufactured by Mitsui Chemicals, Inc.

<Suspension dispersant / dispersion aid>
Tertiary calcium phosphate: manufactured by Ube Materials Co., Ltd. Potassium alkenyl succinate: manufactured by Kao Corporation, Latem DSK

[Production of (Meth) Acrylic Ester Copolymer (A)]
<Production of (Meth) Acrylate Ester Copolymer (A-1)>
In 100 parts by mass of a vinyl monomer mixture of 76 parts by mass of methyl methacrylate, 8 parts by mass of N-phenylmaleimide and 16 parts by mass of styrene, 0.1 parts by mass of perbutyl PV, 0.05 parts by mass of perbutyl O, 0.05 parts by mass of perhexa HC Parts, 0.6 parts by mass of t-dodecyl mercaptan and 0.2 parts by mass of α-methylstyrene dimer are mixed beforehand, and 0.5 parts by mass of calcium phosphate tribasic in 200 parts by mass of pure water and 0.003 parts by mass of potassium alkenyl succinate Part was added and charged in a 20-liter pressure-resistant reaction vessel equipped with a stirrer, and polymerization was started from 40.degree. The temperature rise rate in the polymerization reaction is 5 to 10 ° C./hr for 9 hours, and after completion of the polymerization at 120 ° C., it is cooled, washed, filtered and dried to be bead polymer (meth) acrylic. An acid ester copolymer (A-1) was obtained. The properties of the obtained (meth) acrylate copolymer (A-1) are shown in Table 1.

<Production of (Meth) Acrylate Ester Copolymer (A-2) to (A-11)>
(Meth) acrylic acid ester-based copolymers (A-2) to (A-11) in the same manner as the (meth) acrylic acid ester-based copolymer (A-1) except that the components are blended as shown in Table 1 Manufactured. The properties of the obtained (meth) acrylic acid ester-based copolymers (A-2) to (A-11) are shown in Table 1.
Hereinafter, the (meth) acrylic acid ester-based copolymers (A-1) to (A-11) will be referred to as “copolymers (A-1) to (A-11)”, respectively.

[Production of rubbery polymer (B)]
<Production of Rubbery Polymer (B-1)>
0.27 parts of dipotassium alkenyl succinate, 175 parts of ion exchanged water, 50 parts of n-butyl acrylate, 0.16 parts of allyl methacrylate, 0.08 parts of 1,3-butylene glycol dimethacrylate, and t-butyl hydroperoxide 0.1 part of the mixture was charged to the reactor. The reactor was purged with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60.degree. When the internal temperature reaches 50 ° C., add an aqueous solution consisting of 0.00015 parts of ferrous sulfate, 0.00045 parts of ethylenediaminetetraacetic acid disodium salt, 0.24 parts of Rongalite, and 5 parts of ion-exchanged water The polymerization was initiated and the internal temperature was raised to 75 ° C. Further, this state was maintained for 1 hour to obtain a rubbery polymer (B-1) having a volume average particle diameter of 0.20 μm.

<Production of Rubbery Polymer (B-2)>
150 parts of deionized water, 100 parts of butadiene monomer, 3.0 parts of hardened fatty acid potassium soap, 0.3 parts of organic sodium sulfonate, 0.2 parts of tert-dodecyl mercaptan, 0 parts of potassium persulfate in a pressure vessel equipped with a stirrer Charge .3 parts and 0.14 parts of potassium hydroxide, raise temperature to 60 ° C while stirring under nitrogen atmosphere, start polymerization, dissolve 0.1 parts of potassium persulfate when the conversion is 65% 5 parts of the deionized water was added to the above pressure container to raise the polymerization temperature to 70.degree. C., complete the polymerization with a polymerization conversion ratio of 95% with a reaction time of 13 hours, and a volume average particle diameter of 80 nm and a solid content of 52.0% I got a latex. To this latex was added 1.0 part of a 20% aqueous acetic acid solution as acetic acid, and enlargement was carried out to obtain a rubbery polymer (B-2) having a volume average particle diameter of 0.20 μm.

[Production of Graft Copolymer (C)]
<Production of Graft Copolymer (C-1)>
While maintaining the internal temperature of the reactor at 75 ° C., 0.15 part of Rongalite, 0.65 part of dipotassium alkenyl succinate and 50 parts of a rubbery polymer (B-1) (as solid content), and ions An aqueous solution consisting of 10 parts of exchanged water was added, and then a mixed solution consisting of 6.3 parts of acrylonitrile, 18.7 parts of styrene, and 0.11 part of t-butyl hydroperoxide was dropped over 1 hour, and graft polymerization was performed. . Five minutes after completion of the dropwise addition, an aqueous solution consisting of 0.001 part of ferrous sulfate, 0.003 parts of ethylenediaminetetraacetic acid disodium salt, 0.15 parts of Rongalite, and 5 parts of ion-exchanged water is added, followed by acrylonitrile 6 A mixed solution consisting of 3 parts, 18.7 parts of styrene, 0.19 parts of t-butyl hydroperoxide, and 0.014 parts of n-octylmercaptan was dropped and grafted for 1 hour. After completion of the dropwise addition, the internal temperature is maintained at 75 ° C. for 10 minutes, followed by cooling, and when the internal temperature reaches 60 ° C., 0.2 parts of an antioxidant (Antage W500 manufactured by Yoshitomi Pharmaceutical Co., Ltd.) and alkenylsuccinics An aqueous solution of 0.2 parts of dipotassium acid dissolved in 5 parts of ion-exchanged water was added. Then, the aqueous dispersion of the reaction product was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain a graft copolymer (C-1). The graft ratio of the graft copolymer (C-1) was 40%.

<Production of Graft Copolymer (C-2)>
The rubbery polymer (B-2) (50 parts as solid content) is placed in a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer, and 0.3 part of potassium disproportionated rosin acid (Solid content), 0.01 part of ferrous sulfate heptahydrate, 0.2 parts of sodium pyrophosphate, and 0.5 parts of crystalline glucose were charged, and the contents in the reactor were heated to 60 ° C. while stirring. The A mixture of 39 parts of styrene, 11 parts of acrylonitrile, 0.4 parts of tertiary dodecyl mercaptan and 0.35 parts of cumene hydroperoxide is continuously added dropwise over 2 hours to supply graft polymerization. I did. Meanwhile, the jacket temperature was controlled so as to keep the temperature in the reactor at 60 ° C. After completion of the dropwise addition, the temperature was raised to 70 ° C., and the temperature was further maintained for 1 hour to complete the graft polymerization reaction. After cooling, an antioxidant (dilauryl thiodipropionate) was added to obtain a latex of the graft copolymer (C-2). The obtained latex of the graft copolymer (C-2) is poured into one volume of a 2.5% aqueous solution of sulfuric acid (80 ° C.) with stirring, and then solidified by maintaining it at 90 ° C. for 5 minutes. Thus, a slurry of graft copolymer (C-2) was obtained. The slurry was repeatedly washed with water and dehydrated twice, and then allowed to stand overnight at 70 ° C. and dried to obtain a graft copolymer (C-2) of a milky white powder. The graft ratio of the graft copolymer (C-2) was 41%.

[Production of Composite Rubbery Polymer (B1)]
<Production of Polyorganosiloxane (b-1-1)>
96 parts of octamethyltetracyclosiloxane, 2 parts of γ-methacryloxypropyldimethoxymethylsilane and 2 parts of ethyl orthosilicate were mixed to obtain 100 parts of a siloxane-based mixture. To this was added 300 parts of ion-exchanged water in which 10 parts of sodium dodecylbenzene sulfonate was dissolved, and the mixture was stirred at 10,000 rpm for 2 minutes with a homomixer, then passed once through a homogenizer at a pressure of 30 MPa for stable premixed organosiloxanes. I got a latex.
Separately, 2 parts of dodecylbenzenesulfonic acid and 98 parts of ion-exchanged water were injected into a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirrer to prepare a 2% aqueous solution of dodecylbenzenesulfonic acid. . While this aqueous solution was heated to 85 ° C., a premixed organosiloxane latex was added dropwise over 4 hours, and after completion of the dropwise addition, the temperature was maintained for 1 hour and cooled. The reaction solution was allowed to stand at room temperature for 48 hours, and then neutralized with an aqueous solution of sodium hydroxide to obtain a latex of polyorganosiloxane (b-1-1). A part of the polyorganosiloxane (b-1-1) latex was dried at 170 ° C. for 30 minutes to obtain a solid content concentration, which was 17.3%. Moreover, the volume average particle diameter of polyorganosiloxane (b-1-1) dispersed in the latex was 30 nm.

  In a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirring device, 8.0 parts of the latex of polyorganosiloxane (b-1-1) in terms of solid content, polyoxyethylene alkyl phenyl ether sulfate 0.8 parts of sodium was charged, and 190 parts of ion exchange water was added and mixed. Thereafter, 42.0 parts of n-butyl acrylate, 0.14 parts of allyl methacrylate, and 0.075 parts of 1,3-butylene glycol dimethacrylate as monomers constituting the methacrylate polymer (b-2-1) And a mixture of 0.088 parts of t-butyl hydroperoxide was added. The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60.degree. When the temperature inside the reactor reached 60 ° C., 0.0001 part of ferrous sulfate, 0.0003 part of ethylenediaminetetraacetic acid disodium salt and 0.24 part of Rongalite were dissolved in 10 parts of ion-exchanged water An aqueous solution was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. due to the polymerization of the (meth) acrylic acid ester component. This state was maintained for 1 hour, and polymerization was continued until no polymerization exotherm was confirmed, to obtain a latex of the composite rubbery polymer (B1-1). The volume average particle diameter of the composite rubbery polymer (B1-1) dispersed in the latex was 91 nm, and the particle ratio of 300 to 500 nm was 0% by volume.

[Production of Graft Polymer (C1)]
<Manufacture of graft polymer (C1-1)>
Subsequently to the production of the composite rubbery polymer (B1-1), after the liquid temperature inside the reactor was lowered to 60 ° C., an aqueous solution in which 0.4 part of Rongalite was dissolved in 10 parts of ion exchanged water was added. Then, a mixture of 7.5 parts of acrylonitrile, 22.5 parts of styrene and 0.1 parts of t-butyl hydroperoxide was dropped and polymerized over about 1 hour. After holding for 1 hour after completion of the dropwise addition, an aqueous solution in which 0.0002 parts of ferrous sulfate, 0.0006 parts of ethylenediaminetetraacetic acid disodium salt and 0.25 parts of Rongalite were dissolved in 10 parts of ion-exchanged water was added. Then, a mixture of 5.0 parts of acrylonitrile, 15.0 parts of styrene and 0.1 parts of t-butyl hydroperoxide was dropped and polymerized over about 40 minutes. It hold | maintained for 1 hour after completion | finish of dripping, it cooled, and obtained the latex of a graft copolymer (C1-1). Subsequently, 150 parts of an aqueous solution in which calcium acetate was dissolved at a ratio of 5% was heated to 60 ° C. and stirred. In the calcium acetate aqueous solution, 100 parts of the latex of the graft copolymer (C1-1) was gradually dropped and solidified. The obtained coagulated material was separated, washed, and dried to obtain a dry powder of graft copolymer (B-1). The graft ratio of the graft copolymer (C1-1) was 40%.

<Production of Graft Copolymer (C1-2) to (C1-6)>
As shown in Table 2, except for changing the mass ratio of polyorganosiloxane (b-1-1) and n-butyl acrylate and the addition amount (parts) of sodium polyoxyethylene alkylphenyl ether sulfate, the graft co-weight was The graft copolymers (C1-2) to (C1-6) were obtained in the same manner as in the united (C1-1).
The volume average particle diameter of the composite rubbery polymer (B1) dispersed in the latex, the particle ratio of 300 to 500 nm, and the graft ratio of the graft copolymers (C1-2) to (C1-6) are shown in Table 2. .

<Production of Graft Copolymer (C1-7)>
(Production of acid group-containing copolymer latex)
200 parts of ion exchanged water, 2 parts of potassium oleate, 4 parts of sodium dioctyl sulfosuccinate, 0.003 of ferrous sulfate in a reactor equipped with a reagent injection container, a cooling pipe, a jacket heater and a stirring device Parts, 0.009 parts of ethylenediaminetetraacetic acid disodium salt and 0.3 parts of sodium formaldehyde sulfoxylate were charged under a nitrogen stream, and the temperature was raised to 60.degree. From 60 ° C., a mixture consisting of 85 parts of n-butyl acrylate, 15 parts of methacrylic acid and 0.5 parts of cumene hydroperoxide was continuously added dropwise over 120 minutes. After completion of the dropwise addition, aging is carried out while maintaining the temperature at 60 ° C. for 2 hours to obtain an acid group containing 33% of solid content, 96% of polymerization conversion, 120 nm of volume average particle diameter of acid group-containing copolymer. Copolymer latex (X) was obtained.

(Radical polymerization)
In a reactor equipped with a reagent injection vessel, a cooling pipe, a jacket heater and a stirrer, 4.0 parts of the latex of polyorganosiloxane (b-1-1) in terms of solid content, 0. 48 parts and 190 parts of ion exchange water were charged and mixed. Next, as monomers constituting the alkyl (meth) acrylate polymer (b-2-2), 45.0 parts of n-butyl acrylate, 0.4 parts of allyl methacrylate, 1,3-butylene glycol dimethacrylate 0 A mixture of .09 parts, 0.12 parts of t-butyl hydroperoxide was added. The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the internal temperature was raised to 60.degree. When the internal temperature reaches 60 ° C., 0.000075 parts of ferrous sulfate heptahydrate, 0.00023 parts of ethylenediaminetetraacetic acid disodium salt, 0.2 parts of sodium formaldehyde sulfoxylate, and 10 parts of ion-exchanged water The aqueous solution was added to initiate radical polymerization. After the heat of polymerization is confirmed, the jacket temperature is set to 75 ° C., the polymerization is continued until the heat of polymerization is not confirmed, and this state is maintained for another hour, and a composite rubber in which polyorganosiloxane and polybutyl acrylate rubber are complexed. (Radical polymerization step).
The volume average particle diameter of the obtained composite rubber was 100 nm.

(Bloated)
After the liquid temperature inside the above reactor dropped to 70 ° C., 0.20 parts of a 5% aqueous sodium pyrophosphate solution as a solid content was added. After controlling at an internal temperature of 70 ° C., 0.30 parts of acid group-containing copolymer latex (X) as solid content is added, stirring is performed for 30 minutes, and enlargement is carried out to obtain a composite rubbery polymer (B1-2). A latex was obtained (bloating step).
The volume average particle diameter of the obtained latex-like composite rubbery polymer (B1-2) was 165 nm. In addition, the proportion of particles having a particle diameter of 300 to 500 nm in the total particles of the composite rubbery polymer (B1-2) was 10% by volume.

(Production of graft copolymer (C1-7))
It consists of 0.001 part of ferrous sulfate heptahydrate, 0.003 parts of ethylenediaminetetraacetic acid disodium salt, 0.3 parts of Rongalite, and 10 parts of ion exchange water in the latex of the composite rubbery polymer (B1-2). The aqueous solution was added. Then, a mixed solution consisting of 10 parts of acrylonitrile, 30 parts of styrene and 0.18 parts of t-butyl hydroperoxide was dropped over 80 minutes to polymerize. After completion of dropping, the mixture is maintained at a temperature of 75 ° C. for 30 minutes, and then a mixture of 2.5 parts of acrylonitrile, 7.5 parts of styrene, 0.05 parts of t-butyl hydroperoxide and 0.02 parts of n-octylmercaptan Was added dropwise over 20 minutes to polymerize. After completion of the dropwise addition, the temperature of 75 ° C. is maintained for 30 minutes, 0.05 part of cumene hydroperoxide is added, and the temperature of 75 ° C. is maintained for 30 minutes, and then cooled to give a composite rubbery polymer ( A latex of a graft copolymer (C1-7) obtained by polymerizing acrylonitrile and styrene in the presence of B1-2) was obtained. Next, 150 parts of a 1% aqueous solution of calcium acetate was heated to 60 ° C., and 100 parts of the latex of the graft copolymer (C1-7) was gradually dropped into this to coagulate. Then, the precipitate was separated, dehydrated and washed, and then dried to obtain a graft copolymer (C1-7).

<Production of Graft Copolymer (C1-8) to (C1-12)>
The amount of polyorganosiloxane (b-1-1), dipotassium alkenyl succinate, and n-butyl acrylate, the amount of sodium pyrophosphate used in the thickening step, and the acid group-containing copolymer latex (X) The graft copolymers (C1-8) to (C1-12) were obtained in the same manner as the graft copolymer (C1-7) except that the amounts were changed as shown in Table 1.

  The volume average particle diameter of the composite rubbery polymer (B1) constituting the graft copolymers (C1-7) to (C1-12) obtained in each of the above examples, and the particle diameter occupied in all particles are 300 to 300 The proportion of particles having a diameter of 500 nm and the grafting ratio of the graft copolymers (C1-7) to (C1-12) are shown in Table 2.

[Examples 1 to 6, Comparative Examples 1 to 5]
100 parts by weight of the (meth) acrylate copolymer (A) shown in Table 3 and Table 4 is mixed with 0.8 parts of carbon black, and a 30 mm diameter vacuum-vented twin screw extruder ("PCM 30" manufactured by Ikegai Co., Ltd.) ) And melt-kneaded at 240 ° C. to obtain pellets of (meth) acrylic acid ester copolymer (A). The melt volume rate of the obtained (meth) acrylate copolymer (A) pellet was evaluated by the following method. Moreover, the color development property, heat resistance, and scratch resistance were evaluated by the following method about the molded article which injection-molded the pellet of the obtained (meth) acrylic acid ester type copolymer (A).
The evaluation results are shown in Tables 3 and 4.

[Examples 7 to 13, Comparative Examples 6 to 11]
Each component is mixed according to the composition shown in Table 5 and Table 6 (parts by mass), and 0.8 parts of carbon black is further mixed therein, and a 30 mm diameter vacuum-vented twin-screw extruder ("PCM 30" manufactured by Ikegai Co., Ltd.) The mixture was melt-kneaded at 240 ° C. to obtain pellets of a thermoplastic resin composition. The melt volume rate and the spiral flow length of the pellets of the obtained thermoplastic resin composition were evaluated by the following methods. Moreover, the color development property, heat resistance, scratch resistance, impact resistance, and surface impact resistance were evaluated by the following methods about the molded article which injection-molded the pellet of the obtained thermoplastic resin composition.
The evaluation results are shown in Tables 5 and 6.

[Each evaluation method]
(Measurement of melt volume rate (MVR))
It measured on the conditions of 220 degreeC or 230 degreeC according to ISO1133 specification about the pellet of a (meth) acrylic-ester type copolymer (A) or a thermoplastic resin composition. MVR is a measure of liquidity.

(Measurement of spiral flow length)
A pellet of the thermoplastic resin composition is a spiral mold having a cross section of 3.1 mm × 12.7 mm at a cylinder temperature of 280 ° C. and a mold temperature of 60 ° C. by an injection molding machine (“J85AD-110H” manufactured by Japan Steel Works, Ltd.) The length of the thermoplastic resin composition flowing in the mold was measured, and the longer the flowing length, the better the fluidity.

<Injection molding 1>
A pellet of (meth) acrylate copolymer (A) or a thermoplastic resin composition was subjected to an injection molding machine (“IS55FP-1.5A” manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 200 to 270 ° C., a mold temperature of 60 A molded article having a length of 80 mm, a width of 10 mm and a thickness of 4 mm was molded under the condition of ° C., and used as a molded article for Charpy impact test and a molded article for measurement of deflection temperature under load (molded article (Ma1)).

<Injection molding 2>
A pellet of (meth) acrylate copolymer (A) or a thermoplastic resin composition is injected at a cylinder temperature of 200 to 270 ° C. by an injection molding machine (“J-75 EII-P” manufactured by Japan Steel Works, Ltd.), mold A molded product of 100 mm long, 100 mm wide and 3 mm thick is molded at a temperature of 60 ° C., and a molded product for evaluating color development, a molded product for scratch resistance evaluation, a molded product for falling ball impact strength measurement (molded product (Ma2 ) Was used.

<Evaluation of heat resistance>
The deflection temperature under load (HDT) (° C.) of the molded product (Ma1) was measured by the flat width method at 1.83 MPa and 4 mm in accordance with the ISO test method 75 standard.

<Evaluation of chromogenicity>
The lightness L ^* of the molded product (Ma2) was measured by the SCE method using a spectrocolorimeter ("CM-500d" manufactured by Konica Minolta Optips). The measured L ^* is taken as "L ^* (ma)". The lower the L ^* , the blacker the color developability is.

<Evaluation of impact resistance: Charpy impact test>
The molded article (Ma1) was subjected to a Charpy impact test (notched) at 23 ° C. in accordance with the ISO 179 standard to measure the Charpy impact strength.

<Scratch resistance>
The pencil hardness of the molded product (Ma2) was measured at a load of 750 g in accordance with JIS K5600. The higher the pencil hardness, the better the scratch resistance.
The (meth) acrylic acid ester copolymer (A) and the thermoplastic resin composition of the present invention preferably have a pencil hardness of H or more, particularly 2H or more.

<Evaluation of surface impact resistance: Drop ball impact strength measurement>
The falling ball impact strength was measured for the molded article (Ma2) temperature-controlled to -30 ° C. A steel ball with a weight of 500 g was dropped from the height of 10 cm onto the surface of the molded article (Ma2), and if not broken, the drop height was increased every 10 cm to confirm the presence or absence of cracking or cracking. Of the three samples, the falling height at which two or more cracks and cracks did not occur was taken as the falling ball impact height. The higher the falling ball impact height, the better the surface impact resistance.

  As shown in Examples 1 to 13, the (meth) acrylic acid ester copolymer (A) of the present invention and the thermoplastic resin of the present invention containing the (meth) acrylic acid ester copolymer (A) The composition is excellent in fluidity, and the molded article obtained by using the (meth) acrylic acid ester copolymer (A) of the present invention and the thermoplastic resin composition of the present invention is excellent in color development, heat resistance and scratch resistance. It was excellent in stickiness. Moreover, the molded article formed by shape | molding the thermoplastic resin composition of this invention is excellent in impact resistance, especially surface impact resistance.

  On the other hand, Comparative Example 1, Comparative Example 4, Comparative Example 6, and Comparative Example 9 have high fluidity because the content of the N-substituted maleimide monomer of the (meth) acrylic acid ester copolymer (A) is high. The color developability was extremely poor. In addition, as in Comparative Example 6 and Comparative Example 9, when the graft copolymer (C) was contained, the surface impact resistance was significantly inferior, and in Comparative Example 9, the impact resistance was also poor. Since the content rate of the aromatic vinyl monomer of the (meth) acrylic acid ester type copolymer (A) was low, Comparative Example 2 and Comparative Example 7 were significantly inferior in fluidity. Further, as in Comparative Example 7, when the graft copolymer (C) was contained, the color developability and scratch resistance were inferior. In Comparative Example 3 and Comparative Example 8, the content of the aromatic vinyl monomer in the (meth) acrylic acid ester copolymer (A) was high, so the scratch resistance was significantly inferior. Further, as in Comparative Example 8, when the graft copolymer (C) was contained, the surface impact resistance was inferior. In Comparative Example 5 and Comparative Example 10, since the (meth) acrylic acid ester copolymer (A) does not contain the N-substituted maleimide monomer and the content of the aromatic vinyl monomer is low, heat resistance and The liquidity was extremely poor. The comparative example 11 blends the copolymer (A-10) with a high content rate of the N-substituted maleimide monomer, and the copolymer (A-11) which does not contain the N-substituted maleimide monomer. The total amount of N-substituted maleimide in the thermoplastic resin composition is adjusted, but the content of the N-substituted maleimide monomer in the (meth) acrylic acid ester copolymer (A) In addition to the above, the flowability is extremely poor, and the impact resistance and the color development are also poor.

[Examples 14 to 30, Reference Examples 1 and 2, Comparative Examples 12 to 17]
Each component is mixed by the composition shown in Tables 7 to 9 (parts by mass), and 0.8 parts of carbon black is further mixed therein, and a 30 mm diameter vacuum-vented twin-screw extruder (manufactured by Ikegai, "PCM 30") The mixture was melt-kneaded at 200 to 260 ° C. under a vacuum of 93.325 kPa, and pelletized using a pelletizer (“SH-type pelletizer” manufactured by Soken Co., Ltd.) to obtain pellets of a thermoplastic resin composition.
The melt volume rate of the pellets of the obtained thermoplastic resin composition was measured by the method described above.
Moreover, impact resistance, color development property, heat resistance, and scratch resistance were evaluated by the above-mentioned method about the molded article which injection-molded the pellet of the obtained thermoplastic resin composition.
The evaluation results are shown in Tables 7-9.

  As shown in Examples 14 to 30, according to each of the examples using the thermoplastic resin composition of the present invention, a molded article having excellent fluidity, impact resistance, color development, heat resistance and scratch resistance is provided. The goods were obtained.

On the other hand, the thermoplastic resin compositions obtained in Comparative Examples 12 to 17 were insufficient in any of flowability, impact resistance, color development, heat resistance and scratch resistance.
The reference examples 1 and 2 use the (meth) acrylic ester copolymer (A) of the present invention, but in the reference example 1, the (meth) acrylic ester copolymer (A) The impact resistance is insufficient because the volume average particle diameter of the graft copolymer (C1-4) blended in the above is too small. Moreover, in the reference example 2, since the volume average particle diameter of a graft copolymer (C1-11) is too large, coloring property is inferior.

  The thermoplastic resin composition of the present invention is useful as an interior / exterior part of a vehicle, office equipment, home appliances, building materials and the like.

Claims (10)

  A vinyl monomer mixture (m1) containing (meth) acrylic acid ester monomer, N-substituted maleimide monomer and aromatic vinyl monomer, wherein the vinyl monomer mixture (m1) A vinyl-based monomer mixture (m1) in which the content of the N-substituted maleimide monomer in the total 100% by mass is less than 9% by mass and the content of the aromatic vinyl monomer is 7 to 39% by mass (Meth) acrylic acid ester type copolymer (A) formed by polymerization.   The (meth) acrylic acid ester according to claim 1, wherein the content of the (meth) acrylic acid ester monomer in the total 100% by mass of the vinyl-based monomer mixture (m1) is 52 to 92% by mass. Copolymer (A).   The thermoplastic resin composition containing the (meth) acrylic-ester type copolymer (A) of Claim 1 or 2.   A graft copolymer (C) obtained by polymerizing a vinyl-based monomer mixture (m2) in the presence of the (meth) acrylic acid ester-based copolymer (A) and the rubbery polymer (B) The thermoplastic resin composition according to claim 3, comprising The graft copolymer (C) is
In the presence of 20 to 80% by mass of the rubbery polymer (B), 20 to 80% by mass of the vinyl monomer mixture (m2) is polymerized (however, the rubbery polymer (B) and the vinyl monomer 100 mass% in total with the mixture of monomers (m2),
The rubbery polymer (B) is one or more selected from a diene rubbery polymer, an acrylic rubbery polymer, an olefin rubbery polymer, and a silicone rubbery polymer,
The vinyl monomer mixture (m2) contains 65 to 82% by mass of an aromatic vinyl monomer and 18 to 18 vinyl cyanide monomers in a total of 100% by mass of the vinyl monomer mixture (m2). 35% by mass,
The thermoplastic resin composition according to claim 4, wherein the graft ratio is 10 to 150%.   Composite rubber-like weight of polyorganosiloxane (b-1) having a volume average particle diameter of 50 nm or more and less than 240 nm and alkyl (meth) acrylate polymer (b-2) as the graft copolymer (C) The graft polymer (C1) is obtained by polymerizing a vinyl monomer mixture (m2) containing an aromatic vinyl monomer and a vinyl cyanide monomer in the presence of the united body (B1). The thermoplastic resin composition according to Item 4.   In the composite rubbery polymer (B1), the ratio of the polyorganosiloxane (b-1) in the total 100 mass% of the polyorganosiloxane (b-1) and the alkyl (meth) acrylate polymer (b-2) is 1 The thermoplastic resin composition according to claim 6, which is not less than 25% by mass. The graft polymer (C1) is obtained by polymerizing 20 to 90% by mass of the vinyl monomer mixture (m2) in the presence of 10 to 80% by mass of the composite rubbery polymer (B1) (however, And the total of the composite rubbery polymer (B1) and the vinyl monomer mixture (m2) is 100% by mass),
The vinyl monomer mixture (m2) contains 65 to 82% by mass of an aromatic vinyl monomer and 18 to 18 vinyl cyanide monomers in a total of 100% by mass of the vinyl monomer mixture (m2). 35% by mass,
The thermoplastic resin composition according to claim 6 or 7, wherein the graft ratio is 35 to 60%.   50 to 90 mass of (meth) acrylic acid ester copolymer (A) in a total of 100% by mass of the (meth) acrylic acid ester copolymer (A) and the graft copolymer (C) The thermoplastic resin composition according to any one of claims 4 to 8, wherein the composition comprises   A molded article formed by molding the (meth) acrylic acid ester copolymer (A) according to claim 1 or 2, or the thermoplastic resin composition according to any one of claims 3 to 9.