JP2010001344A - Thermoplastic resin composition, method for producing it, and molded product of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having excellent transparency, heat resistance, shock resistance, and toughness, and in particular, exhibiting excellent transparency by removing a specific rubber constituent or coarse particles of 10 μm or more in application. <P>SOLUTION: In the thermoplastic resin composition prepared by compounding a thermoplastic resin A and a gum-containing polymer B, the coarse particles, which consist of the gum-containing polymer B and larger than 10 μm, are 100 pieces/g or less. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is excellent in transparency and excellent in heat resistance, impact resistance, and toughness, and in particular, a thermoplastic resin composition having excellent transparency by blending a specific rubber component or removing coarse particles of 10 μm or more. It is about.

  Amorphous resins such as polymethyl methacrylate (hereinafter referred to as PMMA) and polycarbonate (hereinafter referred to as PC) make use of their transparency and dimensional stability to make various parts such as optical materials, household electrical appliances, office automation equipment and automobiles. Used in a wide range of fields.

  In recent years, these resins have been widely used for higher performance optical materials such as optical lenses, prisms, mirrors, optical disks, optical fibers, liquid crystal display sheets or films, light guide plates, etc. The optical properties, molding processability and heat resistance required for these are also higher.

  At present, these transparent resins are also used as lamp members for automobiles such as tail lamps and head lamps. In recent years, in order to increase the interior space and improve gasoline fuel efficiency, the distance between various lenses such as tail lamp lenses, inner lenses, headlamps, shield beams, and light sources can be reduced, or the thickness of parts can be reduced. There is a tendency, and excellent moldability is required. Further, since the vehicle is used under severe conditions, it is required to have a small shape change under high temperature and high humidity, and excellent scratch resistance, weather resistance and oil resistance.

  However, although the PMMA resin has excellent transparency and weather resistance, there is a problem that heat resistance and impact resistance are not sufficient. PC resin, on the other hand, is excellent in heat resistance and impact resistance, but has a large birefringence, which is an optical distortion, causes optical anisotropy in the molded product, and has moldability, scratch resistance and solvent resistance. There was a problem that it was extremely inferior. Therefore, for the purpose of improving the heat resistance of PMMA, a resin in which a maleimide monomer or a maleic anhydride monomer is introduced as a heat resistance imparting component has been developed. However, the maleimide monomer is expensive and has low reactivity, and maleic anhydride has a problem of poor thermal stability.

As a method for solving these problems, it contains glutaric anhydride-containing units obtained by heating a copolymer containing unsaturated carboxylic acid monomer units using an extruder to cause a cyclization reaction. Copolymers are disclosed (see Patent Documents 1 and 2). Further, as a method for improving mechanical properties such as impact resistance, a method of adding a rubber-containing polymer to a copolymer containing a glutaric anhydride-containing unit has been disclosed (Patent Documents 3 and 4). 5, 6, 7). However, in the methods disclosed in these patent documents, although mechanical properties such as impact resistance are improved, the coloration and transparency of the resin composition are insufficient. A resin composition with less coloring that has mechanical properties such as good impact resistance while having higher optical properties required in recent years, that is, transparency and optical isotropy, has not been known.
JP-A-49-85184 (page 1-2, Examples) JP-A-1-103612 (page 1-2, Examples) JP-A-60-67557 (Page 1-2, Examples) JP-A-60-120734 (page 1-2, Examples) JP-A-4-277546 (Page 1-2, Examples) Japanese Patent Laid-Open No. 5-186659 (page 1-2, Examples) JP 2004-292812 A (Page 1-2, Examples)

  An object of the present invention is to provide a thermoplastic resin composition that is excellent in transparency and excellent in heat resistance, impact resistance, and toughness, and that is particularly excellent in transparency by blending a specific rubber component.

That is, the present invention
[1] A thermoplastic resin composition comprising a thermoplastic resin (A) and a rubber-containing polymer (B), wherein the composition comprises a rubber-containing polymer (B) of 10 μm or more. A thermoplastic resin composition, wherein the number of coarse particles is 100 particles / g or less.
[2] The thermoplastic resin composition according to [1], wherein the coarse particles of 10 μm or more are agglomerated particles and / or single particles of fine particles of the rubber-containing polymer (B).
[3] The thermoplastic resin composition according to [1], wherein the rubber-containing polymer (B) is a multilayer structure polymer having at least one rubber layer therein.
[4] The thermoplastic resin according to [3], wherein the polymer constituting the outermost layer of the multilayer structure polymer is a polymer containing (i) a glutaric anhydride structural unit represented by the following general formula (1): Resin composition.

(In the above formula, R ¹ and R ² are the same or different and represent any one selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms.)
[5] The heat according to [3] or [4], wherein the polymer constituting the rubbery layer of the multilayer structure polymer is a polymer containing an alkyl acrylate unit and a substituted or unsubstituted styrene unit. Plastic resin composition.
[6] The thermoplastic resin (A) is represented by the following general formula (1): (i) glutaric anhydride structural unit 10 to 50% by weight, (ii) unsaturated carboxylic acid alkyl ester unit 50 to 90% by weight (Iii) The thermoplastic resin composition according to any one of [1] to [5], which is a thermoplastic resin having 10% by weight or less of an unsaturated carboxylic acid unit.

(In the above formula, R ¹ and R ² are the same or different and represent any one selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms.)
[7] The thermoplastic resin (A) is a copolymer having (iv) 10% by weight or less of other vinyl monomer units in addition to the above units (i), (ii) and (iii). The thermoplastic resin composition according to [6].
[8] A thermoplastic resin (A) produced by heat-treating a copolymer (a) containing (ii) an unsaturated carboxylic acid alkyl ester unit and (iii) an unsaturated carboxylic acid unit in a heat treatment apparatus. The thermoplastic resin composition according to any one of [1] to [7], which is a product.
[9] The rubber-containing polymer (B) latex obtained in the polymerization step of the rubber-containing polymer (B) is obtained by measuring the volume average particle diameter measured by a laser diffraction method of the rubber-containing polymer (B) latex. 9) The thermoplastic resin (A) and the rubber-containing polymer (1) according to any one of claims 1 to 8, which are melt-kneaded with the thermoplastic resin (A) after being filtered through a filter having an absolute filtration accuracy of 5 to 10 μm. A method for producing a thermoplastic resin composition comprising B).
[10] A molded article comprising the thermoplastic resin composition according to any one of [1] to [8].
[11] The molded product according to [10], wherein the molded product is a film or a sheet.

  The present invention is excellent in transparency, heat resistance, impact resistance, and toughness. In particular, it is excellent in transparency of thick molded products containing specific rubber components. It is extremely useful for applications such as recording or optical communication-related parts, information equipment-related parts, transportation equipment-related parts such as automobiles, medical equipment-related parts, and building material-related parts.

  Hereafter, the manufacturing method of the thermoplastic resin composition of this invention is demonstrated concretely.

  The thermoplastic resin (A) of the present invention is not particularly limited and any one can be used. For example, polyolefin resin such as polyacetal resin, polyester resin, polyamide resin, polyethylene resin and polypropylene resin, polystyrene resin, acrylic resin, polyurethane resin, chlorinated polyethylene resin, chlorinated polypropylene resin, aromatic and aliphatic polyketone resin, Fluorine resin, polyphenylene sulfide resin, polyether ether ketone resin, polyimide resin, AS resin, ABS resin, AES resin, ACS resin, polyvinyl chloride resin, polyvinylidene chloride resin, vinyl ester resin, polyurethane resin, MS resin, Polycarbonate resin, polyarylate resin, polysulfone resin, polyethersulfone resin, phenoxy resin, polyphenylene oxide resin, poly-4-methylpentene-1, polyester Teruimido resins, cellulose acetate resins, polyvinyl alcohol resins, and the like. Of these, acrylic resins are preferred because they are excellent in mechanical properties and transparency. Examples of the acrylic resin include an acrylic resin mainly composed of an unsaturated carboxylic acid alkyl ester unit represented by the structure represented by the following general formula (2).

(However, R ³ represents any one selected from hydrogen and an alkyl group having 1 to 5 carbon atoms, and R ⁴ is an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms substituted with a hydroxyl group or halogen and carbon. Any one selected from alicyclic hydrocarbon groups of 3 to 6)

  The content of the unsaturated carboxylic acid alkyl ester unit, which is the main constituent unit of the acrylic resin, is preferably 50 to 90% by weight, more preferably 60 to 100% in 100% by weight of the thermoplastic resin (A). 85% by weight.

  The acrylic resin that can be used as the thermoplastic resin (A) of the present invention may further contain (i) a glutaric anhydride structural unit represented by the following general formula (1).

(In the above formula, R ¹ and R ² are the same or different and represent any one selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms.)

  Among them, an acrylic resin having (i) a glutaric anhydride-containing unit represented by the general formula (1) and (ii) an unsaturated carboxylic acid alkyl ester unit is preferable. The content of the (i) glutaric anhydride structural unit represented by the general formula (1) in the acrylic resin is preferably 10 to 50% by weight, more preferably 100% by weight in the thermoplastic resin (A). Is from 15 to 40% by weight. (I) It is preferable to contain 10 to 50% by weight of a glutaric anhydride structural unit because heat resistance, birefringence characteristics (optical isotropy) and solvent resistance are improved.

  The acrylic resin that can be used as the thermoplastic resin (A) of the present invention may further contain (iii) an unsaturated carboxylic acid unit represented by the following general formula (3).

(However, R ⁵ represents any one selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms)

  The content of the unsaturated carboxylic acid unit represented by the general formula (3) in the acrylic resin is 10% by weight or less, that is, 0 to 10% by weight in 100% by weight of the thermoplastic resin (A). Preferably, it is 0 to 5% by weight, most preferably 0 to 1% by weight. (iii) Setting the unsaturated carboxylic acid unit to 10% by weight or less is preferable in terms of colorless transparency and retention stability.

  The content of (iv) other vinyl monomer units contained in 100% by weight of the thermoplastic resin (A) of the present invention is preferably 10% by weight or less, that is, in the range of 0 to 10% by weight. . The (iv) other vinyl monomer units referred to here are copolymerizable vinyl monomer units not belonging to any of the above (i) to (iii). Further, (iv) as the other vinyl monomer unit, a vinyl monomer unit containing no aromatic ring is preferable. In the case of an aromatic vinyl monomer unit such as styrene, if the content is high, the colorless transparency, optical isotropy, and solvent resistance tend to decrease, so the content is 5% by weight or less, that is, 0 to 0%. The range is preferably 5% by weight, more preferably 0 to 3% by weight.

In general, an infrared spectrophotometer or a proton nuclear magnetic resonance ( ¹ H-NMR) measuring instrument is used for quantification of each component unit in the acrylic resin. In infrared spectroscopy (i) glutaric anhydride structural units are characteristic absorption of 1800 cm ^-1 and 1760 cm ^-1, (iii) unsaturated carboxylic acid unit and (ii) an unsaturated carboxylic acid alkyl ester unit Can be distinguished from In the ¹ H-NMR method, the copolymer composition can be determined from the integral ratio of the spectrum. For example, in the case of a copolymer consisting of a glutaric anhydride unit, a methacrylic acid unit, and a methyl methacrylate unit, the spectral assignment measured in dimethyl sulfoxide heavy solvent is 0.5 to 1.5 ppm. Acid, methyl methacrylate and glutaric anhydride α-methyl group hydrogen, 1.6-2.1 ppm peak is methylene group hydrogen of polymer main chain, 3.5 ppm peak is methyl methacrylate carboxylate Hydrogen of (—COOCH ₃ ), the peak at 12.4 ppm is hydrogen of carboxylic acid of methacrylic acid.

  In addition to the above, (iv) in the case of a copolymer containing styrene as a copolymerization component of other vinyl monomer units, hydrogen of an aromatic ring of styrene is seen at 6.5 to 7.5 ppm. Similarly, the copolymer composition can be determined from the spectral ratio.

  The acrylic resin preferably has a weight average molecular weight of 30,000 to 180,000, more preferably 50,000 to 160,000, particularly preferably 70,000 to 140,000. When the weight average molecular weight is within this range, coloring during heat deaeration in the subsequent step can be reduced, a polymer having a small yellowness can be obtained, and the mechanical strength of the molded product can also be increased. . In addition, the weight average molecular weight as used in the field of this invention shows the weight average molecular weight in the absolute molecular weight measured by multi-angle light scattering gel permeation chromatography (GPC-MALLS).

  The acrylic resin used in the present invention preferably has a glass transition temperature (Tg) of 120 ° C. or more in terms of heat resistance. The glass transition temperature is more preferably 125 ° C. or higher, and particularly preferably 130 ° C. or higher. Moreover, as an upper limit, it is about 170 degreeC normally. In addition, the glass transition temperature here is a glass transition temperature (Tg) measured at a heating rate of 20 ° C./min using a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer).

  The acrylic resin used in the present invention has a yellowness index value of 5 or less, and coloring is extremely suppressed. In a more preferred embodiment, it is preferably 4 or less, and in a most preferred embodiment, it is preferably 3 or less. . Accordingly, the yellowness of the thermoplastic resin composition of the present invention obtained by blending the thermoplastic resin (A) can also be 5 or less, more preferably 4 or less, and most preferably 3 or less, which is extremely excellent. It is preferable because a molded article or film having colorlessness can be obtained. Further, when the yellowness value of the thermoplastic resin (A) is large, a part of the thermoplastic resin (A) may be thermally decomposed, and the heat of the present invention containing the thermoplastic resin (A) The mechanical properties of the plastic resin composition tend to decrease. Also in this respect, the yellowness of the thermoplastic resin (A) is preferably in the above range. Here, the yellowness index means that the thermoplastic resin (A) or the thermoplastic resin composition of the present invention is injection molded, and the resulting 1 mm-thick molded product is SM color according to JIS-K7103. It is the value measured using the computer (made by Suga Test Instruments Co., Ltd.).

  The acrylic resin containing the (i) glutaric anhydride structural unit represented by the general formula (1) used in the present invention can be produced by the following method.

  In advance, an unsaturated carboxylic acid monomer and an unsaturated carboxylic acid alkyl ester monomer are copolymerized to obtain a copolymer (a). In that case, when the above (iv) other vinyl monomer unit is included, the vinyl monomer giving the unit may be copolymerized. The obtained copolymer (a) is heated in the presence or absence of a suitable catalyst, and an intramolecular cyclization reaction is carried out by dealcoholization and / or dehydration. (I) A thermoplastic resin (A) containing a glutaric anhydride structural unit can be produced. Thus, by heating the copolymer (a), a dehydration reaction between the carboxyl groups of two adjacent (iii) unsaturated carboxylic acid units, or an adjacent (iii) unsaturated carboxylic acid unit ( ii) One unit of (i) glutaric anhydride structural unit represented by the general formula (1) is generated by dealcoholization reaction between unsaturated carboxylic acid alkyl ester units.

  As the unsaturated carboxylic acid monomer used for obtaining the copolymer (a) used in the present invention, any unsaturated carboxylic acid monomer that can be copolymerized with other vinyl compounds can be used. It is. Preferable unsaturated carboxylic acid monomer includes a compound represented by the following general formula (4), a hydrolyzate of maleic acid and maleic anhydride, and the like.

(However, R ⁶ represents any one selected from hydrogen and an alkyl group having 1 to 5 carbon atoms)

  In particular, acrylic acid or methacrylic acid is preferable from the viewpoint of excellent thermal stability, and methacrylic acid is more preferable. These can be used alone or in combination of two or more thereof. The unsaturated carboxylic acid monomer represented by the general formula (4) gives a (iii) unsaturated carboxylic acid unit having a structure represented by the general formula (3) when copolymerized.

  Moreover, what is represented by following General formula (5) can be mentioned as a preferable example of an unsaturated carboxylic-acid alkylester monomer.

(However, R ⁷ represents any one selected from hydrogen and an alkyl group having 1 to 5 carbon atoms, and R ⁸ is an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms substituted with a hydroxyl group or halogen and carbon. Any one selected from alicyclic hydrocarbon groups of 3 to 6)

  Of these, acrylic esters and / or methacrylic esters are particularly preferred. The unsaturated carboxylic acid alkyl ester monomer represented by the general formula (5) gives a (ii) unsaturated carboxylic acid alkyl ester unit having the structure represented by the general formula (2) when copolymerized. . Specific preferred examples of the unsaturated carboxylic acid alkyl ester monomer include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, n-butyl acrylate, N-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, chloromethyl acrylate, chloromethyl methacrylate, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2,3,4,5, acrylic acid 6-Penta Examples include droxyhexyl, 2,3,4,5,6-pentahydroxyhexyl methacrylate, 2,3,4,5-tetrahydroxypentyl acrylate, and 2,3,4,5-tetrahydroxypentyl methacrylate. Among them, methyl methacrylate is most preferably used. These can be used alone or in combination of two or more thereof.

  Moreover, in manufacture of the copolymer (a) used by this invention, you may use another vinyl monomer in the range which does not impair the effect of this invention. When this other vinyl monomer is copolymerized, the above (iv) other vinyl monomer units are obtained. Preferred specific examples of other vinyl monomers include aromatics such as styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, and pt-butylstyrene. Vinyl monomers, vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, ethacrylonitrile, allyl glycidyl ether, styrene-p-glycidyl ether, p-glycidyl styrene, maleic anhydride, itaconic anhydride, N-methyl Maleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, aminoethyl acrylate, propylene acrylate Aminoethyl, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p- Examples include aminostyrene, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline, and 2-styryl-oxazoline. From the viewpoint of transparency, optical isotropy and solvent resistance, a monomer containing no aromatic ring can be used more preferably. These may be used alone or in combination of two or more.

  In the present invention, a preferred ratio of these monomer mixtures used in the production of the copolymer (a) is 5 to 50% by weight of the unsaturated carboxylic acid monomer based on 100% by weight of the whole monomer mixture. %, More preferably 10 to 45% by weight, and the unsaturated carboxylic acid alkyl ester monomer is 50 to 95% by weight, more preferably 55 to 90% by weight. When other vinyl monomers copolymerizable with these are used, the preferred ratio is 0 to 10% by weight. When the other vinyl monomer is an aromatic vinyl monomer, the preferable ratio is 0 to 5% by weight, and the more preferable ratio is 0 to 3% by weight.

  When the content of the unsaturated carboxylic acid monomer is less than 5% by weight, when the thermoplastic resin (A) is produced by heating the copolymer (a), it is represented by the general formula (1). (I) The amount of glutaric anhydride structural units produced is reduced, and the heat resistance improvement effect of the thermoplastic resin (A) tends to be reduced. On the other hand, when the content of the unsaturated carboxylic acid monomer exceeds 50% by weight, (iii) the unsaturated carboxylic acid is produced when the thermoplastic resin (A) is produced by heating the copolymer (a). There is a tendency for a large amount of acid units to remain, and there is a tendency for the colorless transparency and residence stability of the thermoplastic resin (A) to decrease.

  The production method of the copolymer (a) used in the present invention is basically the same as known polymerization methods such as bulk polymerization by radical polymerization, solution polymerization, suspension polymerization, emulsion polymerization, precipitation polymerization, and bulk suspension polymerization. A polymerization method by a combination of known polymerization methods can also be used. Solution polymerization, bulk polymerization, suspension polymerization, and precipitation polymerization are preferred polymerization methods in terms of fewer impurities. Although there is no restriction | limiting in particular about the polymerization temperature of a copolymer (a), It is preferable to superpose | polymerize especially in the range of 60-160 degreeC. By controlling the polymerization temperature within the above range, the acceleration phenomenon of the polymerization rate due to the gel effect can be suppressed, and the formation of a dimer generated at the time of high temperature polymerization can be suppressed. Therefore, the thermoplastic resin (A) having excellent thermal stability is efficiently used. Can be manufactured well.

  The polymerization time of the copolymer (a) is determined by the target polymerization rate, polymerization temperature, initiator type and amount used, but the range is preferably 1 to 7 hours, more preferably 2 to 6 hours. is there. By setting it in this range, the polymerization control is stabilized and a high-quality thermoplastic resin (A) can be produced. When the polymerization time is shorter than 1 hour, it is necessary to increase the amount of the initiator used, and it tends to be difficult to control the polymerization, and it is preferably 2 hours or longer. Since productivity will fall when it exceeds 7 hours, More preferably, it is 6 hours or less.

  As described above, the thermoplastic resin (A) of the present invention preferably has a weight average molecular weight of 30,000 to 180,000. The thermoplastic resin (A) having such a molecular weight is achieved by pre-controlling the copolymer (a) to a weight average molecular weight of 30,000 to 180,000 during the production of the copolymer (a). can do.

  As for the molecular weight control method of the copolymer (a), for example, the addition amount of radical polymerization initiators such as azo compounds and peroxides, or alkyl mercaptans, carbon tetrachloride, carbon tetrabromide, dimethylacetamide, dimethylformamide, It can be controlled by the addition amount of a chain transfer agent such as triethylamine. In particular, a method of controlling the amount of alkyl mercaptan added as a chain transfer agent can be preferably used from the viewpoint of stability of polymerization, ease of handling, and the like. Examples of the alkyl mercaptan include n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan, 2-ethylhexyl 3-mercaptopropionate and the like, t-dodecyl mercaptan, n-dodecyl mercaptan and 2-ethylhexyl 3-mercaptopropionate are preferably used. The addition amount of the alkyl mercaptan is preferably 0.2 to 5.0 parts by weight, more preferably 0.3 to 4.0 parts with respect to 100 parts by weight of the total amount of the monomer mixture in order to control the molecular weight to a preferable level. Part by weight, particularly preferably 0.4 to 3.0 parts by weight.

  The method for producing a thermoplastic resin (A) containing a glutaric anhydride structural unit by heating the copolymer (a) in the present invention, performing an intramolecular cyclization reaction by dehydration and / or dealcoholization, Although there is no limitation, a method of passing the copolymer (a) through a heated extruder having a vent or a method of heating and devolatilizing under an inert gas atmosphere or vacuum is preferable. When an intramolecular cyclization reaction is carried out by heating in the presence of oxygen, the yellowness tends to deteriorate, so it is preferable to sufficiently replace the system with an inert gas such as nitrogen. Particularly preferable apparatuses include, for example, a single-screw extruder equipped with a “unimelt” type screw, a twin-screw extruder, a twin-screw / single-screw combined continuous kneading extruder, a three-screw extruder, a continuous or batch kneader type. In particular, a twin screw extruder or a twin / single screw combined continuous kneading and extruding apparatus can be preferably used. As the biaxial / uniaxial composite continuous kneading and extruding apparatus, for example, an apparatus described in JP-A No. 2004-307834 (page 1-2, Examples) can be used. Further, it is more preferable that these apparatuses have a structure capable of introducing an inert gas such as nitrogen. For example, as a method of introducing an inert gas such as nitrogen into a twin-screw extruder or a twin-screw / single-screw composite continuous kneading extrusion apparatus, the upper and / or lower portions of the hopper are about 10 to 100 liters / minute. The method of connecting the piping of an active gas stream is mentioned.

  In addition, the temperature for heat devolatilization by the above method is not particularly limited as long as the intramolecular cyclization reaction is caused by dehydration and / or dealcoholization. It is in the range of 310 ° C.

  In addition, the time for heating and devolatilization in this case can be appropriately set according to the desired copolymer composition, but is usually preferably 1 minute to 60 minutes, more preferably 2 minutes to 30 minutes, and particularly preferably 3 The range is ~ 20 minutes. In order to secure a heating time for a sufficient intramolecular cyclization reaction to proceed using an extruder, L / D is 40 or more and 110 or less, where L is the length of the extruder screw and D is the diameter. It is preferable. When an extruder with a short L / D is used, a large amount of unreacted unsaturated carboxylic acid units remain, so that the reaction proceeds again during the heat molding process, and there is a tendency for silver and bubbles to be seen in the molded product and molding retention. Sometimes color tends to deteriorate. When the L / D of the extruder is larger than 110, it is not preferable because practical advantages are reduced due to mechanical strength and structural problems of the extruder.

  Furthermore, in the present invention, at least one selected from acids, alkalis and salt compounds is added as a catalyst for promoting the cyclization reaction to glutaric anhydride when the copolymer (a) is heated by the above method or the like. can do. The addition amount is preferably about 0.01 to 1 part by weight per 100 parts by weight of the copolymer (a). Examples of the acid catalyst include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, phosphoric acid, phosphorous acid, phenylphosphonic acid, and methyl phosphate. Examples of the basic catalyst include metal hydroxides, amines, imines, alkali metal derivatives, alkoxides, ammonium hydroxide and the like. Furthermore, examples of the salt-based catalyst include acetic acid metal salts, stearic acid metal salts, metal carbonate salts, and ammonium salts including various alkyl ammonium salts. However, it is preferable to add the catalyst in such a range that the color of the catalyst does not adversely affect the coloring of the thermoplastic resin and the transparency is not lowered. Among them, the compound containing an alkali metal can be preferably used because it exhibits an excellent reaction promoting effect with a relatively small addition amount. Specifically, hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, alkoxide compounds such as sodium methoxide, sodium ethoxide, sodium phenoxide, potassium methoxide, potassium ethoxide, and potassium phenoxide, lithium acetate And organic carboxylates such as sodium acetate, potassium acetate and sodium stearate. In particular, sodium hydroxide, sodium methoxide, lithium acetate, and sodium acetate can be preferably used.

  Next, the rubber-containing polymer (B) of the present invention will be described.

  The rubber-containing polymer (B) used in the present invention is composed of a layer containing one or more rubbery polymers and one or more layers composed of different polymers, and 1 inside. A multilayer structure polymer called a core-shell type having a structure containing a rubber polymer of more than one layer, or a monomer mixture composed of a vinyl monomer in the presence of a rubber polymer is copolymerized. Graft copolymers and the like can be preferably used, but multi-layered polymers are particularly preferred because they are excellent in transparency and little coloring.

The number of layers constituting the multilayer polymer used in the present invention may be two or more, and may be three or more or four or more, but one or more rubber layers (core) In the multilayer polymer of the present invention, the type of the rubber layer is not particularly limited and is composed of a polymer component having rubber elasticity. Anything is acceptable. For example, acrylic monomers, silicone monomers, styrene monomers, nitrile monomers, conjugated diene monomers, monomers that form urethane bonds, ethylene monomers, propylene monomers Examples thereof include rubbers formed by polymerizing monomers and isobutene monomers.

  Preferred rubbers include, for example, acrylic units such as ethyl acrylate units and butyl acrylate units, silicone units such as dimethylsiloxane units and phenylmethylsiloxane units, styrene units such as styrene units and α-methylstyrene units, It is a rubber composed of nitrile units such as acrylonitrile units and methacrylonitrile units, and conjugated diene units such as butadiene units and isoprene units.

  A rubber composed of a combination of two or more of these components is also preferred. For example, (1) rubber composed of acrylic units such as ethyl acrylate units and butyl acrylate units and silicone units such as dimethylsiloxane units and phenylmethylsiloxane units, and (2) ethyl acrylate units and butyl acrylate. Rubber composed of acrylic units such as units and styrene units such as styrene units and α-methylstyrene units, (3) acrylic units such as ethyl acrylate units and butyl acrylate units, butanediene units, and isoprene units And (4) acrylic units such as ethyl acrylate units and butyl acrylate units, silicone units such as dimethylsiloxane units and phenylmethylsiloxane units, styrene units and α- Methyl styrene unit The rubber | gum comprised from which styrenic unit is mentioned. Among these, a rubber which is an acrylate containing an acrylic acid alkyl ester unit and a substituted or unsubstituted styrene unit is most preferable from the viewpoint of transparency and mechanical properties. In addition to these components, rubber obtained by crosslinking a copolymer composed of crosslinkable components such as divinylbenzene units, allyl acrylate units, allyl methacrylate units, butylene glycol diacrylate units and butylene glycol dimethacrylate units is also available. preferable.

  In the multilayer structure polymer of the present invention, the type of layer other than the rubber layer is not particularly limited as long as it is composed of a polymer component having thermoplasticity, but the glass transition temperature is higher than that of the rubber layer. A high polymer component is preferred. Polymers having thermoplastic properties include unsaturated carboxylic acid alkyl ester units, unsaturated carboxylic acid units, unsaturated glycidyl group-containing units, unsaturated dicarboxylic anhydride units, aliphatic vinyl units, aromatic vinyl units, cyanide. Examples thereof include polymers containing one or more units selected from vinyl units, maleimide units, unsaturated dicarboxylic acid units, and other vinyl units. Among them, a polymer containing an unsaturated carboxylic acid alkyl ester unit is preferable, and in addition, one or more units selected from an unsaturated glycidyl group-containing unit, an unsaturated carboxylic acid unit and an unsaturated dicarboxylic anhydride unit are contained. More preferred is a polymer.

  Although it does not specifically limit as a monomer used as the raw material of the said unsaturated carboxylic acid alkylester unit, Acrylic acid alkylester or methacrylic acid alkylester is used preferably. Specifically, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate , T-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, stearyl acrylate, stearyl methacrylate, octadecyl acrylate , Octadecyl methacrylate, phenyl acrylate, phenyl methacrylate, benzyl acrylate, benzyl methacrylate, chloromethyl acrylate, chloromethyl methacrylate, 2-chloroethyl acrylate, methacrylic acid -Chloroethyl, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2,3,4,5,6-pentahydroxyhexyl acrylate, methacrylic acid 2 , 3,4,5,6-pentahydroxyhexyl, 2,3,4,5-tetrahydroxypentyl acrylate, 2,3,4,5-tetrahydroxypentyl methacrylate, aminoethyl acrylate, propylamino acrylate Examples include ethyl, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, and cyclohexylaminoethyl methacrylate. From the viewpoint that the effect of improving impact resistance is great, methyl acrylate or methyl methacrylate is preferably used. These units can be used alone or in combination of two or more.

  The unsaturated carboxylic acid monomer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, maleic acid, and further a hydrolyzate of maleic anhydride. In particular, acrylic acid and methacrylic acid are preferable from the viewpoint of excellent thermal stability, and methacrylic acid is more preferable. These can be used alone or in combination.

  The monomer used as a raw material for the unsaturated glycidyl group-containing unit is not particularly limited, but is glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, diglycidyl itaconate, allyl glycidyl ether, styrene-4-glycidyl. Examples include ether and 4-glycidylstyrene, and glycidyl acrylate or glycidyl methacrylate is preferably used from the viewpoint that the effect of improving impact resistance is large. These units can be used alone or in combination of two or more.

  Examples of the monomer used as the raw material for the unsaturated dicarboxylic acid anhydride unit include maleic anhydride, itaconic anhydride, glutaconic anhydride, citraconic anhydride, and aconitic anhydride, which have the effect of improving impact resistance. From the viewpoint of being large, maleic anhydride is preferably used. These units can be used alone or in combination of two or more.

  Moreover, ethylene, propylene, butadiene, etc. can be used as a monomer used as the raw material of the said aliphatic vinyl unit. Examples of the monomer used as a raw material for the aromatic vinyl unit include styrene, α-methylstyrene, 1-vinylnaphthalene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, and 2-ethyl. -4-Benzylstyrene, 4- (phenylbutyl) styrene, halogenated styrene and the like can be used. Acrylonitrile, methacrylonitrile, ethacrylonitrile, etc. can be used as a monomer as a raw material for the vinyl cyanide unit. Examples of the monomer used as a raw material for the maleimide unit include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (p- Bromophenyl) maleimide and N- (chlorophenyl) maleimide can be used. As a monomer used as the raw material of the unsaturated dicarboxylic acid unit, maleic acid, maleic acid monoethyl ester, itaconic acid, phthalic acid, and the like can be used. Examples of other monomers used as a raw material for vinyl units include acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, N-vinyldiethylamine, N-acetylvinylamine, allylamine, and methallylamine. N-methylallylamine, p-aminostyrene, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline, 2-styryl-oxazoline, and the like can be used. These monomers can be used alone or in combination of two or more.

  As the multilayer structure polymer used as the rubber-containing polymer (B) used in the present invention, the type of the outermost layer (shell layer) is, as described above, an unsaturated carboxylic acid alkyl ester unit, an unsaturated carboxylic acid unit, One or more types of units such as unsaturated glycidyl group-containing units, aliphatic vinyl units, aromatic vinyl units, vinyl cyanide units, maleimide units, unsaturated dicarboxylic acid units, unsaturated dicarboxylic anhydride units, and other vinyl units And at least one selected from polymers containing. Among these, at least one selected from polymers containing unsaturated carboxylic acid alkyl ester units, unsaturated carboxylic acid units, unsaturated glycidyl group-containing units, unsaturated dicarboxylic acid anhydride units, and the like is preferable.

  In the present invention, as the rubbery polymer (B) to be subjected to melt kneading with the thermoplastic resin (A), a multilayer containing an unsaturated carboxylic acid alkyl ester unit and a polymer containing an unsaturated carboxylic acid unit as the outermost layer. Most preferably, a structural polymer is used. When the outermost layer is a polymer containing an unsaturated carboxylic acid alkyl ester unit and an unsaturated carboxylic acid unit, by heating, as in the production of the thermoplastic copolymer (A) of the present invention described above, The intramolecular cyclization reaction proceeds to produce a glutaric anhydride structural unit represented by the general formula (1). Therefore, by mixing the multilayer structure polymer having a polymer containing an unsaturated carboxylic acid alkyl ester unit and an unsaturated carboxylic acid unit in the outermost layer with the thermoplastic copolymer (A), by heating during melt kneading, A multilayer structure polymer containing the glutaric anhydride structural unit represented by the general formula (1) in the outermost layer is obtained. As a result, the multilayer copolymer containing the (i) glutaric anhydride structural unit represented by the general formula (1) in the thermoplastic copolymer (A) serving as the continuous phase (matrix phase) is good. It is considered that a very high degree of transparency can be expressed with improvement in mechanical properties such as impact resistance of the thermoplastic resin composition of the present invention.

  As a monomer used as the raw material of the unsaturated carboxylic acid alkyl ester unit here, an acrylic acid alkyl ester or a methacrylic acid alkyl ester is preferable, and methyl acrylate or methyl methacrylate is more preferably used. Moreover, as a monomer used as the raw material of an unsaturated carboxylic acid unit, acrylic acid or methacrylic acid is preferable, and methacrylic acid is more preferably used.

  As a preferable example of the multilayer structure polymer to be included in the thermoplastic resin composition of the present invention, the core layer is a butyl acrylate / styrene copolymer, and the outermost layer is represented by methyl methacrylate / general formula (1). (I) a copolymer comprising a glutaric anhydride structural unit, a core layer is represented by butyl acrylate / styrene copolymer, and an outermost layer is represented by methyl methacrylate / formula (1). (I) Glutaric anhydride structural unit / methacrylic acid copolymer, core layer is dimethylsiloxane / butyl acrylate copolymer and outermost layer is methyl methacrylate polymer, core layer is butanediene / styrene Copolymers whose outermost layer is a methyl methacrylate polymer, and those whose core layer is a butyl acrylate polymer and whose outermost layer is a methyl methacrylate polymer And the like. Here, “/” indicates copolymerization. Furthermore, a preferable example is one in which either one or both of the rubber layer and the outermost layer is a polymer containing a glycidyl methacrylate unit. Among them, the core layer is a butyl acrylate / styrene polymer, the outermost layer is a copolymer of methyl methacrylate / glutaric anhydride structural unit represented by the general formula (1), and the core layer is an acrylic. A butyl acid / styrene copolymer whose outermost layer is methyl methacrylate / glutaric anhydride structural unit represented by the general formula (1) / methacrylic acid polymer is a continuous phase (matrix phase). It becomes possible to approximate the refractive index with the thermoplastic copolymer (A) and to obtain a good dispersion state in the resin composition, and the transparency that can satisfy the demand for more advanced in recent years is expressed. Therefore, it can be preferably used.

  In the multilayer structure polymer of the present invention, the weight ratio of the core to the shell is preferably 40% by weight to 90% by weight and more preferably 50% by weight to 80% by weight with respect to the whole multilayer structure polymer. More preferably, it is less than or equal to weight percent.

  About the average particle diameter of the multilayer structure polymer of this invention, it is preferable that it is 0.01-1.00 micrometer. The average particle size is more preferably 0.02 to 0.80 μm, further preferably 0.05 to 0.50 μm, and most preferably 0.05 to 0.5 μm.

  The average particle diameter of the multilayer structure polymer is a volume average particle diameter measured by a laser diffraction method, which is a particle size distribution measurement method using a light diffraction phenomenon and a Mie scattering phenomenon. It is a preferred method to measure multi-layer polymer products dissolved in a solvent.

  As another method, it is possible to calculate from a Guinier plot or a transmission electron micrograph by small-angle light scattering measurement.

  As the multilayer structure polymer of the present invention, a commercially available product that satisfies the above-described conditions may be used, or it may be prepared by a known method. As a commercial product of a multilayer structure polymer, for example, “Metablene (registered trademark)” manufactured by Mitsubishi Rayon Co., Ltd., “Kaneace (registered trademark)” manufactured by Kaneka Chemical Industry Co., Ltd., “Paralloid (registered trademark)” manufactured by Kureha Chemical Industry Co., Ltd. , “Acryloid (registered trademark)” manufactured by Rohm and Haas, “Staffyroid (registered trademark)” manufactured by Gantz Kasei Kogyo Co., Ltd., and “Parapet (registered trademark) SA” manufactured by Kuraray Co., Ltd. More than seeds can be used.

  When the refractive indexes of the thermoplastic resin (A) and the rubber-containing polymer (B) are approximate, it is preferable because a thermoplastic resin composition excellent in transparency can be obtained. Specifically, the difference in refractive index between the two is preferably 0.05 or less, more preferably 0.03 or less, and particularly preferably 0.01 or less. In order to satisfy such a refractive index condition, a method for adjusting the composition of each monomer unit of the thermoplastic resin (A) and / or a rubber polymer used for the rubber-containing polymer (B) or Examples thereof include a method for preparing a monomer composition. In addition, the refractive index difference said here is the value measured by the method shown below. In the solvent in which the thermoplastic resin (A) is soluble, the thermoplastic resin composition of the present invention is sufficiently dissolved under appropriate conditions to obtain a cloudy solution, which is subjected to an operation such as centrifugation, whereby a solvent soluble part and an insoluble part. To separate. The soluble part (part containing the thermoplastic resin (A)) and the insoluble part (part containing the rubber-containing polymer (B)) were purified and then measured for the refractive index (23 ° C., measurement wavelength: 550 nm). Is defined as a difference in refractive index. The copolymer composition of the thermoplastic resin (A) and the rubber-containing polymer (B) in the resin composition is such that each component is individually separated after the separation operation of the soluble component and the insoluble component by the solvent. analyse.

  There is no restriction | limiting in particular as a manufacturing method of the rubber-containing polymer (B) in this invention, It can obtain by well-known polymerization methods, such as block polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Of these, emulsion polymerization, which allows easy particle size control, is preferably used. Emulsion polymerization can be performed according to a known method, and the multilayer structure polymer of the present invention can be obtained by sequentially polymerizing each layer. For example, as a method for producing a multilayer structure polymer having a two-layer structure, an emulsion polymerization reaction is first performed to form a rubber component as an inner layer, and the obtained latex is used, and an unsaturated carboxylic acid alkyl ester as an outermost layer. By forming the thermoplastic resin component layer by emulsion polymerization of units and the like, a multilayer structure polymer having the thermoplastic resin layer as the outermost layer and at least one rubber component layer as the inner layer can be produced.

  The temperature of emulsion polymerization is not necessarily limited, but a general range is 0 ° C to 100 ° C. Examples of the emulsifier used herein include aliphatic alkali metal salts such as sodium oleate, sodium laurate, and sodium stearate; sulfate esters of aliphatic alcohols such as sodium lauryl sulfate; and rosinates such as potassium rosinate. An alkylallylsulfonic acid such as dodecylbenzenesulfonic acid, and the like, and these are used in a combination of one or two or more. As a polymerization initiator used in emulsion polymerization, a radical polymerization initiator is generally used. As specific examples of the radical polymerization initiator, peroxides such as persulfate, azobisisobutyronitrile, and benzoyl peroxide can be used alone. In addition, as a radical polymerization initiator, a redox initiator using a combination of organic hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide and a reducing agent such as a transition metal salt is used. can do. Moreover, a chain transfer agent can be used as needed. Specific examples include mercaptans such as n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, mercaptoethanol; terpenes comprising terpinolene, dipentene, t-terpinene and a small amount of other cyclic terpenes. Mixtures: Halogenated hydrocarbons such as chloroform and carbon tetrachloride, and the like. Among them, alkyl mercaptans such as n-octyl mercaptan are preferable.

  The rubber-containing polymer (B) latex is obtained by performing the above emulsion polymerization. However, since the latex is in a state where the rubber-containing polymer (B) single particles are stably dispersed (emulsified) in the aqueous medium, it is necessary to take out only the rubber-containing polymer (B). The method for taking out the rubber-containing polymer (B) from the latex is not particularly limited as long as it is a known method, but freeze drying method, spray drying method (spray drying method), acid precipitation method, salting out method, etc. There are various methods. For example, in the case of acid precipitation and salting out, an aqueous solution of inorganic acid such as sulfuric acid and hydrochloric acid, inorganic salt such as calcium chloride and magnesium sulfate, organic salt such as calcium formate and calcium acetate is added as a coagulant. The rubber-containing polymer (B) agglomerated particles can be obtained by coagulating the rubber-containing polymer (B) of the rubber-containing polymer (B) latex and dehydrating and drying the coagulated slurry. The rubber-containing polymer (B) aggregated particles obtained here may form aggregated particles (secondary particles) in which a large number of primary particles obtained by polymerization are aggregated, and more than that. Higher order structures are also possible. However, in the case of such an agglomerated structure, it is preferable that the primary particles are not firmly bonded to each other due to dispersibility and are loosely aggregated.

  In addition, in emulsion polymerization, insufficient emulsification and excessive emulsification may occur due to insufficient local stirring and excessive stirring, and coarse particles of 10 μm or more having the same composition as the rubber-containing polymer (B) may be produced. Coarse particles are spherical and / or amorphous single particles, or agglomerated particles of fine particles attached (scaled) to the wall surface of the polymerization tank or a stirrer, and have almost the same composition as the rubber-containing polymer (B).

  The fine particle agglomerated particles here are those that are difficult to disintegrate into single particles when melt-kneaded with the thermoplastic resin (A), or organic solvents (methanol, tetrahydrofuran, etc.) in which the rubber-containing polymer (B) can be dispersed. What is difficult to dissolve. Since these coarse particles are mixed in the polymerized latex, the quality of the rubber-containing polymer (B) product is greatly impaired, and the transparency of the thick molded product is greatly deteriorated.

  The number of coarse particles produced during the production of the rubber-containing polymer (B) is slightly different depending on the polymerization formulation, polymerization batch and polymerization scale, but is 0.01% or less by weight and assumed to be spherical particles having a diameter of 10 μm. In this case, a huge number of 100,000 to 2 million pieces / g is generated in terms of the number.

  Therefore, the transparency of the thick molded product can be greatly improved by using the method of the present invention and setting the number of coarse particles of 10 μm or more comprising the rubber-containing polymer (B) to 100 particles / g or less. The number of coarse particles composed of a rubber-containing polymer (B) of 10 μm or more is preferably 100 / g or less, more preferably 50 / g or less, and most preferably 10 / g or less.

  In the method of counting the number of coarse particles of 10 μm or more composed of the rubber-containing polymer (B) in the thermoplastic resin composition of the present invention, it is important to measure by dispersing the rubber-containing polymer (B). . For example, an organic solvent (methyl ethyl ketone, tetrahydrofuran, etc.) in which the thermoplastic resin (A) is dissolved in the thermoplastic resin composition of the present invention and the rubber-containing polymer (B) can be dispersed is used, and the thermoplasticity is allowed to stand at room temperature. 1 g of the resin composition is dissolved to obtain a cloudy dispersion solution. The white turbid dispersion was poured into a suction filtration apparatus equipped with a 5 μm mesh screen (manufactured electric test sieve made by Manabe Industries Co., Ltd.), and the remaining coarse particles (filtered material) on the 5 μm mesh screen were observed with a microscope. (50 times), and a method for obtaining by counting only the number of coarse particles (filtered material) of 10 μm or more, an organic solvent (methanol, tetrahydrofuran, etc.) in which the rubber-containing polymer (B) used in the present invention can be dispersed. ), 1 g of the rubber-containing polymer (B) was dissolved at room temperature to obtain a white turbid dispersion solution, and the white turbid dispersion solution was fitted with a 5 μm screen (manufactured electric test sieve made by Manabe Industries). Pour while sucking into the suction filtration device, and the remaining coarse particles (filtered material) on the 5 μm mesh screen are observed with a microscope (50 times) and coarse particles of 10 μm or more. The number of coarse particles) is counted, and the number of coarse particles is converted by the content of the rubber-containing polymer (B) in the thermoplastic resin composition, the rubber-containing polymer (B) used in the present invention. Using the latex produced after the emulsion polymerization of the rubber-containing polymer (B), weighed the latex corresponding to 1 g of solid content, and attached it to a suction filtration device equipped with a 5 μm mesh screen (manufactured electric test sieve made by Manabe Industries). The mixture was poured while sucking, and the remaining coarse particles (filtered product) on the 5 μm mesh screen were observed with a microscope (50 times), and the number of coarse particles (filtered product) of 10 μm or more was counted, and the thermoplastic resin composition Examples thereof include a method of converting the number of coarse particles depending on the content of the rubber-containing polymer (B) therein. The criterion for determining coarse particles of 10 μm or more at this time is a size in which the major axis of the coarse particles is compared with a micrometer for microscope, and even if the minor axis is 10 μm or less, the major particle is counted as coarse particles if the major axis is 10 μm. Moreover, as a method for specifying the composition of coarse particles, it can be identified by measuring the infrared spectrum of the filtered material using a micro-infrared spectrophotometer.

  There is no limitation on the method for reducing coarse particles of 10 μm or more comprising the rubbery polymer (B), but the rubbery polymer (B) latex obtained in the emulsion polymerization process of the rubbery polymer (B) is used. A method of filtering, removing and reducing, after obtaining a rubbery polymer (B) product, dissolving in a dispersible organic solvent (methanol, THF, etc.), filtering the solution, removing and reducing, After making a thermoplastic resin composition, it is dissolved in a dispersible organic solvent (MEK, NMP, etc.), and the solution is filtered, removed and reduced. After making a thermoplastic resin composition, it is filtered in a molten state. A method of removing, reducing, etc. is a preferable production method. Among them, a method of filtering the rubber-containing polymer (B) latex obtained in the emulsion polymerization process of the rubber-containing polymer (B) to remove and reduce coarse particles is a particularly preferable method. Moreover, you may manufacture combining the method of 2 types of removal and reduction.

  As a production method for removing and reducing coarse particles of 10 μm or more consisting of a specific rubbery polymer (B), latex obtained in the emulsion polymerization process of the rubbery polymer (B) has a specific filtration accuracy ( A method of filtration using a filter having a μm) can be preferably used. The filtration accuracy referred to in the present invention refers to absolute filtration accuracy, tested by a method according to JIS-B8356, and has a minimum size (aperture) capable of capturing 99.9% or more of coarse particles having a filtration accuracy size (aperture). Say. The preferred absolute filtration accuracy of Forter can be determined from the volume average particle size (hereinafter referred to as “primary particle average particle size”) measured by the laser diffraction method of the rubber-containing polymer (B) latex. Preferably, “primary particle average particle size × 5” to 10 μm, more preferable absolute filtration accuracy (μm) is “primary particle average particle size × 6” to 8 μm, and particularly preferable absolute filtration accuracy is “primary particle average particle size”. Particle size × 7 ”to 6 μm.

  When the absolute filtration accuracy (μm) of the filter is smaller than the “average particle size of primary particles × 5”, even the primary particles of the rubber-containing polymer (B) that must be obtained as a product are captured and produced by the filter. Since the amount tends to deteriorate significantly, it is not preferable. On the other hand, if it exceeds 10 μm, coarse particles of 10 μm or more composed of the rubber-containing polymer (B) that need to be removed pass through, and the turbidity of the thick molded product tends to deteriorate and the transparency tends to decrease.

  The filtration referred to in the present invention is carried out using a filter having an absolute filtration accuracy with an opening in the range of “primary particle average particle size × 5” to 10 μm. Even if a filter with a general-purpose nominal filtration accuracy (minimum size capable of capturing coarse particles of 95.0% or more) or a filter combined with a wire mesh can be used, a certain degree of coarse particle removal effect can be obtained, but coarse particles of 10 μm or larger Is less than 100 / g. In order to use a general-purpose nominal filtration accuracy filter or a wire mesh to reduce coarse particles of 10 μm or more to 100 particles / g or less, a filter having an opening substantially equal to the particle size of the rubber-containing polymer (B) product is used. This is not preferable because not only a large amount of primary particles of the rubber-containing polymer (B) are trapped by the filter but also filtration at a high pressure is required, resulting in a marked deterioration in production.

  Various filter shapes such as a bag type filter, a candle type cylindrical filter, a pleated type cylindrical filter, a tube type filter, a disc type filter, and a leaf disc type filter can be used. Filter materials are also cotton, polyolefin (polyethylene, polypropylene, etc.), polyester, nylon, polyphenylene sulfide, Teflon (registered trademark), aramid, glass, stainless steel, foam, fiber, powder, heat-welded fiber, heat-welded powder Various forms such as a body can be used. These may be selected according to the type of organic solvent used during filtration, the filtration temperature, the resin viscosity, and the like.

Furthermore, as a method of removing and reducing by combining two kinds of filtration methods, the rubber-containing polymer (B) latex obtained in the production process of the rubber-containing polymer (B) is filtered to remove coarse particles. A method of reducing and reducing a thermoplastic resin composition and then filtering it in a molten state is a particularly preferable method.
Specifically, the rubber-containing polymer (B) and the thermoplastic resin (A) obtained by the production method in which the latex is filtered are melt-kneaded to obtain a thermoplastic resin composition. A method of performing filtration with a filter in a molten state, and a method of performing filtration with a filter in a molten state in other processing steps (sheet formation, film formation, etc.) after obtaining a thermoplastic resin composition pellet are preferred.

  The thermoplastic resin composition obtained by blending the thermoplastic resin (A) of the present invention and the rubber-containing polymer (B) has a total of (A) and (B) as 100% by weight, and the thermoplastic resin (A ) Is preferably 10 to 99% by weight, and the rubber-containing polymer (B) is preferably 1 to 90% by weight. More preferably, the thermoplastic resin (A) is 30 to 95% by weight, and the rubbery polymer (B) is 5 to 30% by weight. By setting it as such a composition, the thermoplastic resin composition excellent in transparency, heat resistance, large impact property, and toughness can be obtained.

  Although there is no restriction | limiting in particular in the method of manufacturing the thermoplastic resin composition formed by mix | blending the thermoplastic resin (A) and rubber-containing polymer (B) of this invention, For example, a thermoplastic polymer (A) and rubber | gum A method of producing a thermoplastic resin composition by heating and melting and mixing the polymer-containing polymer (B) under an appropriate shear field can be preferably used. There is no restriction | limiting in particular as a method of carrying out heating melt mixing under a moderate shear field, Melt kneading apparatuses, such as a well-known extruder used for resin processing, a continuous kneader, can be used. For example, a single screw extruder and kneader with one screw, a twin screw extruder and kneader with two screws, a multi-screw extruder and kneader with three or more screws, and an extruder and kneader with one screw Tandem extruder with two machines, extruders and kneaders, multi-stage extruder with three or more extruders and kneaders, extruders and kneaders with side feeders that can only supply raw materials without melting and kneading, etc. It is not limited. In addition, in the screw element design, there is no particular limitation on the combination of a melting or non-melting conveyance zone having a full flight screw, a sealing zone having a seal ring, etc., a mixing zone having unimelt, kneading and the like.

  As the melt-kneading apparatus of the present invention, for example, a continuous melt-kneading apparatus having two or more sealing zones and / or mixing zones and two or more raw material supply ports is preferable, and two sealing zones and / or mixing zones are preferable. More preferably, a continuous melt kneader having a biaxial screw part having two or more raw material supply ports, two shafts having two or more seal zones and / or mixing zones, and two or more raw material supply ports. An extruder is most preferred.

  When using such a twin screw extruder, a part of the thermoplastic resin (A) and the rubber-containing polymer (B) are supplied from the main raw material supply port farthest from the discharge port, It is preferable that the remaining thermoplastic resin (A) is supplied from a raw material supply port located in the middle of the discharge port and melt kneaded. At this time, the raw material supply port for supplying the thermoplastic resin (A2) is an intermediate between the main raw material supply port and the discharge port, specifically, a seal zone and / or a mixing zone closest to the main raw material supply port in the screw element design. It suffices if it is in the middle of the seal zone and / or the mixing zone closest to the discharge port, but if the distance from the main raw material supply port to the discharge port is 1, it should be in the position of 1/5 to 5/5 Is preferred.

  The thermoplastic resin composition produced by the production method of the present invention is excellent in mechanical properties and molding processability, and can be melt-molded, so that extrusion molding, injection molding, press molding, etc. are possible. Films, sheets, tubes, rods, and other molded articles having any desired shape and size can be used. For example, a well-known method can be used for the manufacturing method of the film which consists of a thermoplastic resin composition manufactured with the manufacturing method of this invention. That is, production methods such as an inflation method, a T-die method, a calendar method, a cutting method, a casting method, an emulsion method, and a hot press method can be used. Preferably, an inflation method, a T-die method, a cast method or a hot press method can be used. In the case of a production method using an inflation method or a T-die method, an extruder type melt extrusion apparatus equipped with a single screw or twin screw can be used. The melt extrusion temperature for producing the film of the present invention is preferably 150 to 350 ° C, more preferably 200 to 300 ° C. Moreover, when melt-kneading using a melt-extrusion apparatus, it is preferable to perform the melt-kneading under reduced pressure or the melt-kneading under nitrogen stream from a viewpoint of coloring suppression. When the film of the present invention is produced by the casting method, solvents such as tetrahydrofuran, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone can be used. Preferred solvents are acetone, methyl ethyl ketone, N-methylpyrrolidone and the like. The film is prepared by dissolving the thermoplastic resin composition of the present invention in one or more of the above solvents, and using the solution with a bar coater, a T die, a T die with a bar, a die coat, etc. It can be produced by casting on a flat plate or curved plate (roll) such as a film, steel belt, or metal foil and using a dry method in which the solvent is removed by evaporation, or a wet method in which the solution is solidified with a coagulating liquid. The molded product or film thus obtained can be used in various applications such as electrical and electronic parts, automobile parts, mechanical mechanism parts, OA equipment, home appliances and other housings and their parts, general miscellaneous goods, taking advantage of its excellent heat resistance. Can be used.

  The molded article or film of the thermoplastic resin composition produced by the production method of the present invention is particularly excellent in transparency and heat resistance, so that it is used for imaging equipment such as cameras, VTRs, projection TVs, etc. as video equipment-related parts. Various optical disc (VD, CD, DVD, MD, LD, etc.) substrates, various disc substrate protective films, optical disc player pickup lens, optical fiber, optical, etc. as optical recording or optical communication related parts such as lenses, viewfinders, filters, prisms, Fresnel lenses, etc. Information equipment-related parts such as switches and optical connectors such as liquid crystal displays, flat panel displays, plasma display light guide plates, Fresnel lenses, polarizing plates, polarizing plate protective films, retardation films, light diffusion films, viewing angle widening films, reflections Film, antireflection film , Anti-glare film, brightness enhancement film, prism sheet, pickup lens, conductive film for touch panel, cover, etc., transportation equipment related parts such as automobiles, tail lamp lens, head lamp lens, inner lens, amber cap, reflector, extension, Side mirrors, rearview mirrors, side visors, instrument needles, instrument covers, glazing typified by window glass, etc. as medical equipment related parts such as spectacle lenses, spectacle frames, contact lenses, endoscopes, optical cells for analysis, etc. As parts, it is extremely useful for applications such as daylighting windows, road translucent plates, lighting covers, signboards, translucent sound insulation walls, bathtub materials, and the like.

  Hereinafter, the configuration and effects of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Reference Example 1: Production of thermoplastic resin (A-1) 20 parts by weight of methyl methacrylate, 80 parts by weight of acrylamide, 0.3 part by weight of potassium persulfate and 1500 parts by weight of ion-exchanged water were charged into the reactor. The inside was maintained at 70 ° C. while being replaced with nitrogen gas. The reaction was continued until the monomer was completely converted into a polymer to obtain an aqueous solution of methyl methacrylate / acrylamide copolymer. The resulting aqueous solution was used as a suspending agent.

  A solution prepared by dissolving 0.05 parts by weight of the above-mentioned methyl methacrylate / acrylamide copolymer suspension in 165 parts by weight of ion-exchanged water in a stainless steel autoclave having a volume of 5 liters and equipped with a baffle and a foudra-type stirring blade. The mixture was supplied and stirred at 400 rpm, and the inside of the system was replaced with nitrogen gas. Next, the following mixed substances were added while stirring the reaction system, and the temperature was raised to 70 ° C. The time when the internal temperature reached 70 ° C. was set as the start of polymerization, and kept for 180 minutes to complete the polymerization. Thereafter, the reaction system was cooled, the polymer was separated, washed and dried according to the usual method to obtain a bead-shaped copolymer (a-1).

The copolymer (a-1) had a weight average molecular weight of 60,000 and a polymerization rate of 98%.
Methacrylic acid 28 parts by weight Methyl methacrylate 72 parts by weight n-dodecyl mercaptan 0.8 parts by weight Lauroyl peroxide 0.4 parts by weight.

  Next, the obtained (a-1) is an HTM 38 mm (biaxial part L / D = 34, uniaxial part) which is a non-meshing different direction rotating biaxial / single-axial composite continuous kneading extrusion apparatus equipped with a flow control valve L / D = 14, manufactured by CTE), 0.2 parts of lithium acetate was added, and the intramolecular cyclization reaction was performed at a raw material supply rate of 10 kg / h, a screw rotation speed: 75 rpm, and a cylinder temperature of 285 to 305 ° C. It carried out and obtained the pellet-shaped thermoplastic resin (A-1). The reaction was carried out while purging nitrogen from the hopper at a rate of 10 L / min.

The results obtained thermoplastic resin (A-1) was analyzed with an infrared spectrophotometer, either 1800 cm ^-1 and absorption peaks were observed at 1760 cm ^-1, the thermoplastic resin (A-1) in It was confirmed that glutaric anhydride units were formed. Subsequently, each copolymer component composition and various characteristic evaluation results determined by ¹ H-NMR are shown in Table 1.

Reference Example 2: Production of thermoplastic resin (A-2) 20 parts by weight of methyl methacrylate, 80 parts by weight of acrylamide, 0.3 part by weight of potassium persulfate and 1500 parts by weight of ion-exchanged water were charged into the reactor. The inside was maintained at 70 ° C. while being replaced with nitrogen gas. The reaction was continued until the monomer was completely converted into a polymer to obtain an aqueous solution of methyl methacrylate / acrylamide copolymer. The resulting aqueous solution was used as a suspending agent.

A solution prepared by dissolving 0.05 parts by weight of the above-mentioned methyl methacrylate / acrylamide copolymer suspension in 165 parts by weight of ion-exchanged water in a stainless steel autoclave having a volume of 5 liters and equipped with a baffle and a foudra-type stirring blade. The mixture was supplied and stirred at 400 rpm, and the inside of the system was replaced with nitrogen gas. Next, the following mixed substances were added while stirring the reaction system, and the temperature was raised to 70 ° C. The time when the internal temperature reached 70 ° C. was set as the start of polymerization, and kept for 180 minutes to complete the polymerization. Thereafter, the reaction system was cooled, the polymer was separated, washed and dried according to the usual method to obtain a bead-shaped copolymer (a-2). The weight average molecular weight of this copolymer (a-2) was 130,000, and the polymerization rate was 98%.
Methacrylic acid 28 parts by weight Methyl methacrylate 72 parts by weight n-dodecyl mercaptan 0.4 part by weight Lauroyl peroxide 0.4 part by weight.

  Next, a pellet-shaped thermoplastic resin (A-2) was obtained from the obtained bead copolymer (a-2) by using the same method as in the preparation of (A-1). Table 1 shows each copolymer component composition and various characteristics evaluation results determined by 1H-NMR.

Reference Example 3: Production of rubber-containing polymer (B-1) 120 parts by weight of deionized water, 0.5 parts by weight of potassium carbonate, 0.5% dioctyl sulfosuccinate in a glass container (capacity 5 liters) with a cooler Part by weight and 0.005 part by weight potassium persulfate were charged, and after stirring in a nitrogen atmosphere, 51 parts by weight of butyl acrylate, 19 parts by weight of styrene and 1 part by weight of allyl methacrylate (crosslinking agent) were charged. These mixtures were reacted at 70 ° C. for 30 minutes to obtain a core layer polymer. Next, a mixture of 21 parts by weight of methyl methacrylate, 9 parts by weight of methacrylic acid and 0.005 part by weight of potassium persulfate was continuously added over 90 minutes, and the mixture was further maintained for 90 minutes to polymerize the shell layer. As a result of measuring the volume average particle size of this polymer latex with a laser diffraction / scattering particle size distribution analyzer LS230 (manufactured by Beckman Coulter), it was 165 nm.

  This polymer latex is coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered (solid-liquid separation with buchner funnel / filter paper) and dried to give a rubber-containing polymer (B-1) having a two-layer structure. Obtained. Various properties of the obtained rubber-containing polymer (B-1) are shown in Table 2.

Reference Example 4: Production of rubber-containing polymer (B-2) A polymer latex was produced in the same manner as in Reference Example 3. It was 165 nm as a result of measuring the volume average particle diameter of the two-layer structure rubber-containing polymer for the polymer latex using a laser diffraction scattering particle size distribution analyzer LS230 (manufactured by Beckman Coulter). The polymer latex was filtered using a cartridge filter (MWX030 manufactured by Yamasin Filter Co., Ltd.) having an absolute filtration accuracy of 3 μm. The obtained filtration polymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered (solid-liquid separation with buchner funnel / filter paper), dried, and a two-layer rubbery polymer (B- 2) was obtained. Various properties of the obtained rubber-containing polymer (B-2) are shown in Table 2.

Reference Example 5: Production of rubber-containing polymer (B-3) A polymer latex was produced in the same manner as in Reference Example 3. It was 160 nm as a result of measuring the volume average particle diameter of the two-layer structure rubber-containing polymer for the polymer latex using a laser diffraction scattering particle size distribution analyzer LS230 (manufactured by Beckman Coulter). The polymer latex was filtered using a cartridge filter (MWX010, manufactured by Yamachine Filter) having an absolute filtration accuracy of 1 μm. The obtained filtration polymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered (solid-liquid separation with buchner funnel / filter paper), dried, and a two-layer rubbery polymer (B- 3) was obtained. Various properties of the obtained rubber-containing polymer (B-3) are shown in Table 2.

Reference Example 6: Production of rubber-containing polymer (B-4) A polymer latex was produced in the same manner as in Reference Example 3. It was 160 nm as a result of measuring the volume average particle diameter of the two-layer structure rubber-containing polymer for the polymer latex using a laser diffraction scattering particle size distribution analyzer LS230 (manufactured by Beckman Coulter). The polymer latex was filtered using a cartridge filter having an absolute filtration accuracy of 13 μm (MWE500, manufactured by Yamachine Filter). The obtained filtration polymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered (solid-liquid separation with buchner funnel / filter paper), dried, and a two-layer rubbery polymer (B- 4) was obtained. Various properties of the obtained rubber-containing polymer (B-4) are shown in Table 2.

Reference Example 7: Production of Rubber-Containing Polymer (B-5) 20 parts by weight of “Metablen (registered trademark)” W377 manufactured by Mitsubishi Rayon Co., Ltd., which is a commercial product of a multilayer structure polymer, and 80 parts by weight of tetrahydrofuran were stirred at room temperature. While dissolving. The obtained multilayer polymer solution was measured to measure the volume average particle size of the two-layered rubber-containing polymer with a laser diffraction / scattering particle size distribution analyzer LS230 (manufactured by Beckman Coulter), and was 300 nm. The multilayer polymer solution was filtered using a cartridge filter (MWX030, manufactured by Yamachine Filter) having an absolute filtration accuracy of 3 μm. The obtained filtered solution was dried to obtain a rubber-containing polymer (B-5) having a two-layer structure. Various properties of the obtained rubber-containing polymer (B-5) are shown in Table 2.

Reference Example 8: Production of Rubber-Containing Polymer (B-6) 20 parts by weight of “Metablen (registered trademark)” W377 manufactured by Mitsubishi Rayon Co., Ltd., which is a commercial product of a multilayer structure polymer, and 80 parts by weight of tetrahydrofuran were stirred at room temperature. While dissolving. The obtained multilayer polymer solution was measured to measure the volume average particle size of the two-layered rubber-containing polymer with a laser diffraction / scattering particle size distribution analyzer LS230 (manufactured by Beckman Coulter), and was 300 nm. The multilayer polymer solution was filtered using a cartridge filter (MWX010, manufactured by Yamachine Filter) having an absolute filtration accuracy of 3 μm. The obtained filtered solution was dried to obtain a rubber-containing polymer (B-6) having a two-layer structure. Various properties of the obtained rubber-containing polymer (B-6) are shown in Table 2.

[Examples 1-9, Comparative Examples 1-5]
Using a twin screw extruder TEX30 (L / D = 44.5, manufactured by Nippon Steel Co., Ltd.) with a thermoplastic resin (A) and a rubber-containing polymer (B) in the proportions shown in Table 2, a set temperature of 280 ° C., screw The mixture was melt-kneaded at a rotation speed of 150 rpm to obtain a pellet-shaped thermoplastic resin composition. For Examples 1 to 4 and Comparative Examples 1 to 4 containing rubber-containing polymers (B-1, B-2, B-3, B-4), the thermoplastic resin composition was dispersed in tetrahydrofuran, After isolating the rubbery polymer by centrifuging and analyzing using an infrared spectrophotometer, absorption peaks were confirmed at 1800 cm-1 and 1760 cm-1, and both were found in the rubbery polymer. It was confirmed that a glutaric anhydride unit was formed.

After drying the obtained pellet-shaped thermoplastic resin composition with a hot air dryer set at 80 ° C. for 10 hours, a screw in-line injection molding machine (SG-75H MIV manufactured by Sumitomo Heavy Industries, Ltd.) with a clamping pressure of 75 t is used. Various test pieces were injection molded under the following conditions.
Molding temperature: Glass transition temperature (° C) of thermoplastic resin (A) + 150 ° C
Mold temperature: 80 ℃
Molding cycle: injection time 15 seconds / cooling time 30 seconds (80 mm × 80 mm × 5 mm thickness test piece)
: Injection time 15 seconds / cooling time 20 seconds (127 mm × 12.7 mm × 3.2 mm thickness test piece)
: Injection time 15 seconds / cooling time 20 seconds (64 mm × 12.7 mm × 3.2 mm thickness test piece)
Molding pressure: Pressure at which the resin is completely filled in the mold (molding lower limit pressure) +1 MPa.

  The measuring methods of various physical properties used in the examples are described below.

(1) Transparency (total light transmittance, haze)
The thermoplastic resin composition pellets of the present invention were injection molded at a glass transition temperature of the thermoplastic resin (A) + 150 ° C. to obtain a molded product having a thickness of 80 mm × 80 mm × 5 mm. Using a direct reading haze meter manufactured by Toyo Seiki Co., Ltd., the total light transmittance (%) and haze (cloudiness) (%) at 23 ° C. of the obtained molded product were measured to evaluate transparency.

(2) Yellowness (b value)
The thermoplastic resin composition pellets of the present invention were dissolved in methyl ethyl ketone at a concentration of 25% by weight to prepare a polymer solution, which was cast to a thickness of about 500 μm to form a film. This was air-dried at room temperature to obtain a thermoplastic resin composition film having a thickness of about 50 μm. The ΔYI value of the obtained film was measured according to JIS-K7103 using an SM color computer (manufactured by Suga Test Instruments Co., Ltd.).

(3) Thermal deformation temperature The thermoplastic resin composition pellets of the present invention were injection molded at the glass transition temperature of the thermoplastic resin (A) + 150 ° C. to obtain a test piece of 127 mm × 12.7 mm × 3.2 mm thickness. It was. Using the obtained plate-like test piece, the heat distortion temperature was measured according to ASTM D648 (load: 0.46 MPa), and the heat resistance was evaluated.

(4) Impact resistance (Izod impact value)
The thermoplastic resin composition pellets of the present invention were injection molded at a glass transition temperature of the thermoplastic resin (A) + 150 ° C. to obtain a notched test piece having a thickness of 64 mm × 12.7 mm × 3.2 mm. Using the obtained test piece, Izod impact strength was measured at 23 ° C. according to ASTM D-256, and the impact characteristics were evaluated.

(5) Number of coarse particles in the composition (number / g)
The thermoplastic resin composition pellet of the present invention is dissolved in 1 g of the thermoplastic resin composition pellet at room temperature by using methyl ethyl ketone to obtain a cloudy solution. The cloudy solution was poured while sucking into a suction filtration apparatus equipped with a 5 μm mesh screen (manufactured electric test sieve manufactured by Manabe Industries Co., Ltd.), and the remaining coarse particles (filtered material) on the 5 μm mesh screen were observed with a microscope ( 50 times) and only the coarse particles (filtered material) of 10 μm or more were evaluated by counting the number. (The criterion for determining coarse particles of 10 μm or more is a size in which the major axis of the coarse particles is compared with a micrometer for microscope, and even if the minor axis is 10 μm or less, the major axis is counted as coarse particles if the major axis is 10 μm)

  From the results of Examples 1 to 4, 100 coarse particles of 10 μm or more composed of the rubbery polymer (B) using a method of removing and reducing coarse particles in the production process of the rubbery polymer (B). It can be seen that by using the thermoplastic resin composition of the present invention which is not more than / g, it is an excellent transparent material having good transparency and haze (cloudiness). On the other hand, the rubber-containing polymer (B) that was not removed and reduced as shown in Comparative Examples 1 and 2 and the rubber that was removed and reduced using a filter outside the absolute filtration accuracy range shown in Comparative Examples 3 and 4 When a thermoplastic resin composition having 1000 particles / g or more of coarse particles having a particle size of 10 μm or more composed of the polymer-containing polymer (B) is used, it can be seen that the transparency and haze (cloudiness) are greatly reduced.

  From the results of Examples 5 to 6, the rubbery polymer (B) having a rubbery polymer (B) of 10 μm or more composed of the rubbery polymer (B) using a method of removing and reducing coarse particles after dissolving using a commercial product. It can be seen that the use of the thermoplastic resin composition of the present invention having coarse particles of 100 particles / g or less is an excellent transparent material having good transparency and haze (cloudiness). However, the product yield tends to drop to about 66%. Further, from the results of Examples 7 to 8, 10 μm comprising the rubbery polymer (B) using a method of removing and reducing coarse particles after dissolving a commercially available rubbery polymer (B) using a commercial product. It can be seen that by using the thermoplastic resin composition of the present invention having the above coarse particles of 100 particles / g or less, the transparent material is excellent in transparency and haze (cloudiness). However, the product yield tends to drop significantly to about 26%. On the other hand, the coarse particles of 10 μm or more composed of the rubber-containing polymer (B) using a commercially available product as the rubber-containing polymer (B) which was not removed and reduced as shown in Comparative Example 5 were 1000 particles / g or more. When a thermoplastic resin composition is used, it turns out that it is a transparent material which transparency and haze (haze) fell greatly.

  From the result of Example 9, the rubbery polymer (B) using a method of removing and reducing coarse particles after dissolving PMMA as a base polymer and using a commercial product as the rubbery polymer (B). By using the thermoplastic resin composition of the present invention having 100 / g or less coarse particles having a size of 10 μm or more, it can be seen that the transparent material is excellent in transparency and haze (cloudiness). On the other hand, coarse particles of 10 μm or more composed of a rubbery polymer (B) using a commercial product as the rubbery polymer (B) that was not removed or reduced using PMMA as the base polymer shown in Comparative Example 6 When a thermoplastic resin composition having a density of 1000 / g or more is used, it is understood that the transparency and haze (cloudiness) are greatly reduced.

Claims (11)

A thermoplastic resin composition obtained by blending a thermoplastic resin (A) and a rubber-containing polymer (B), and 100 coarse particles of 10 μm or more made of the rubber-containing polymer (B) in the composition. / G or less, a thermoplastic resin composition. 2. The thermoplastic resin composition according to claim 1, wherein the coarse particles of 10 μm or more are aggregated particles and / or single particles of fine particles of the rubber-containing polymer (B). The thermoplastic resin composition according to claim 1, wherein the rubber-containing polymer (B) is a multilayer structure polymer having at least one rubber layer therein. The thermoplastic resin composition according to claim 3, wherein the polymer constituting the outermost layer of the multilayer structure polymer is a polymer containing (i) a glutaric anhydride structural unit represented by the following general formula (1). .

(In the above formula, R ¹ and R ² are the same or different and represent any one selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms.) The thermoplastic resin composition according to claim 3 or 4, wherein the polymer constituting the rubbery layer of the multilayer structure polymer is a polymer containing an alkyl acrylate unit and a substituted or unsubstituted styrene unit. The thermoplastic resin (A) is represented by the following general formula (1): (i) glutaric anhydride structural unit 10 to 50% by weight, (ii) unsaturated carboxylic acid alkyl ester unit 50 to 90% by weight, (iii) The thermoplastic resin composition according to any one of claims 1 to 5, which is a thermoplastic resin having 10% by weight or less of an unsaturated carboxylic acid unit.

(In the above formula, R ¹ and R ² are the same or different and represent any one selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms.) The thermoplastic resin (A) is a copolymer having (iv) 10% by weight or less of other vinyl monomer units in addition to the units (i), (ii) and (iii) above. Item 7. The thermoplastic resin composition according to Item 6. The thermoplastic resin (A) is produced by heat-treating a copolymer (a) containing (ii) an unsaturated carboxylic acid alkyl ester unit and (iii) an unsaturated carboxylic acid unit in a heat treatment apparatus. The thermoplastic resin composition according to any one of claims 1 to 7, wherein the composition is a thermoplastic resin composition. The rubber-containing polymer (B) latex obtained in the polymerization step of the rubber-containing polymer (B) is (volume average particle diameter measured by laser diffraction method of the rubber-containing polymer (B) latex) × 5 The thermoplastic resin (A) and the rubber-containing polymer (B) according to any one of claims 1 to 8, which are melt-kneaded with the thermoplastic resin (A) after being filtered through a filter having an absolute filtration accuracy of 10 µm. Method for producing thermoplastic resin composition by blending The molded article which consists of a thermoplastic resin composition in any one of Claims 1-8. The molded article according to claim 10, wherein the molded article is a film or a sheet.