JP2006335902A - Thermoplastic resin composition and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which is excellent in transparency, heat resistance, impact resistance, toughness and flow property and hardly induces color deterioration caused by compounding a rubber component. <P>SOLUTION: The thermoplastic resin composition contains 0.001-5 pts.wt. monophosphite compound (C) against 100 pts.wt. resin composition comprising a thermoplastic polymer (A) having (i) 25-50 wt.% glutaric anhydride structural unit of formula (1) (wherein R<SP>1</SP>and R<SP>2</SP>are identical to or different from each other and are each a hydrogen atom or a 1-5C alkyl group), (ii) 50-75 wt.% unsaturated alkyl carboxylate unit and (iii) ≤10 wt.% unsaturated carboxylic acid unit and a rubber-containing polymer (B). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition that is excellent in transparency, heat resistance, impact resistance, and toughness, and that is particularly less susceptible to coloring deterioration due to the blending of rubber components and excellent in fluidity.

  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. On the other hand, although PC resin is excellent in heat resistance and impact resistance, it has large birefringence, which is an optical distortion, causes optical anisotropy in the molded product, and has excellent 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, maleimide monomers are expensive and have 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 is disclosed (Patent Documents 3, 4, and 4). 5, 6, 7). However, in the methods disclosed in these patent documents, although mechanical properties such as impact resistance are improved, there is a problem that coloring and transparency of the resin composition are remarkably impaired. 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)

  It is an object of the present invention to provide a thermoplastic resin composition that is excellent in transparency, heat resistance, impact resistance, and toughness, and that is particularly excellent in fluidity with little deterioration of coloration due to rubber component blending. .

That is, the present invention
[1] (i) 25 to 50% by weight of a glutaric anhydride structural unit represented by the following general formula (1), (ii) 50 to 75% by weight of an unsaturated carboxylic acid alkyl ester unit, and (iii) an unsaturated carboxylic acid 0.001 to 5 weight of monophosphite compound (C) with respect to 100 weight parts of resin composition comprising thermoplastic polymer (A) having 10% by weight or less of acid unit and rubber-containing polymer (B) Containing a thermoplastic resin composition.

（上記式中、Ｒ^１、Ｒ^２は、同一または相異なる水素原子または炭素数１〜５のアルキル基を表す。）

(In the above formula, R ¹ and R ² represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.)

  [2] The thermoplastic resin composition according to [1], wherein the weight ratio of the thermoplastic polymer (A) and the rubber-containing polymer (B) is in the range of 99/1 to 50/50.

  [3] The thermoplastic polymer (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). ] Or the thermoplastic resin composition according to [2].

  [4] The thermoplastic resin composition according to any one of [1] to [3], wherein the monophosphite compound (C) has a molecular weight of 300 to 2,000.

  [5] The monophosphite compound is a cyclic monophosphite compound represented by the following general formula (2) or a monophosphite compound represented by the following general formula (3) [1] ] The thermoplastic resin composition in any one of [4].

（上記式中、Ｒ^３はｔ−ブチル基またはｔ−アミル基を示し、Ｒ^４は炭素原子数１〜９のアルキル基を示し、Ｒ^５は水素原子または炭素数１〜９のアルキル基を示し、Ｒ^６は炭素原子数１〜３０のアルキル基、置換もしくは非置換アリール基を表す。）

(In the above formula, R ³ represents a t-butyl group or a t-amyl group, R ⁴ represents an alkyl group having 1 to 9 carbon atoms, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. R ⁶ represents an alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group.)

（上記式中、Ｒ^７、Ｒ^８は同一または相異なる炭素原子数１〜３０のアルキル基または置換もしくは非置換アリール基を表す。）

(In the above formula, R ⁷ and R ⁸ represent the same or different alkyl groups having 1 to 30 carbon atoms or substituted or unsubstituted aryl groups.)

  [6] The heat according to any one of [1] to [5], wherein the rubber-containing polymer (B) is a multilayer structure polymer having at least one rubber layer therein. Plastic resin composition.

  [7] The thermoplastic resin composition according to [6], wherein the polymer constituting the outermost layer of the multilayer structure polymer contains a glutaric anhydride-containing unit represented by the general formula (1).

  [8] The thermoplastic resin composition according to [6] or [7], wherein the polymer constituting the rubbery layer of the multilayer polymer contains an alkyl acrylate unit and a substituted or unsubstituted styrene unit. .

  [9] A copolymer (a) containing (ii) an unsaturated carboxylic acid alkyl ester unit and (iii) an unsaturated carboxylic acid unit is heat-treated in a heat treatment apparatus, and (i) the following general formula (1) (Ii) an unsaturated carboxylic acid alkyl ester unit of 50 to 75% by weight, and (iii) an unsaturated carboxylic acid unit of 10% by weight or less. (A) is manufactured, and then 0.001 to 5 weights per 100 parts by weight of the total amount of the rubbery polymer (B) and the thermoplastic polymer (A) and the rubbery polymer (B). A method for producing a thermoplastic resin composition, wherein a part of the monophosphite compound (C) is added and melt kneaded.

（上記式中、Ｒ^１、Ｒ^２は、同一または相異なる水素原子または炭素数１〜５のアルキル基を表す。）

(In the above formula, R ¹ and R ² represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.)

  [10] A copolymer (a) containing an unsaturated carboxylic acid alkyl ester unit and (iii) an unsaturated carboxylic acid unit is heat-treated in a heat treatment apparatus, and (i) the following general formula (1) (Ii) an unsaturated carboxylic acid alkyl ester unit of 50 to 75% by weight, and (iii) an unsaturated carboxylic acid unit of 10% by weight or less. When producing (A), the rubber-containing polymer (B) and the total amount of the thermoplastic polymer (A) and the rubber-containing polymer (B) are 100 parts by weight in the middle of the heat treatment. A method for producing a thermoplastic resin composition, in which 0.001 to 5 parts by weight of a monophosphite compound (C) is added and melt-kneaded.

（上記式中、Ｒ^１、Ｒ^２は、同一または相異なる水素原子または炭素数１〜５のアルキル基を表す。）

(In the above formula, R ¹ and R ² represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.)

  [11] The amount of the rubber-containing polymer (B) added is in the range of 99/1 to 50/50 by weight ratio of the thermoplastic polymer (A) and the rubber-containing polymer (B) [9] Or the manufacturing method of the thermoplastic resin composition as described in [10].

  [12] A molded article comprising the thermoplastic resin composition according to any one of [1] to [8] or the thermoplastic resin composition obtained by the production method according to any one of [9] to [11].

  [13] The molded product according to [11], wherein the molded product is any one of a spectacle lens, a film, and a sheet.

  According to the present invention, a thermoplastic resin composition having excellent transparency and excellent heat resistance, impact resistance, and toughness, in particular, little deterioration of coloration due to the blending of rubber components can be obtained. The thermoplastic resin composition of the present invention Moldings and films containing transparent, impact and heat-resistant parts, video equipment related parts, optical recording or optical communication related parts, information equipment related parts, automobiles and other transportation equipment related parts, It is extremely useful for applications such as medical equipment related parts and building material related parts.

  Hereinafter, the thermoplastic polymer of the present invention will be specifically described.

  As described above, the thermoplastic polymer (A) of the present invention is represented by the following general formula (1).

（上記式中、Ｒ^１、Ｒ^２は、同一または相異なる水素原子または炭素数１〜５のアルキル基を表す。）
で表されるグルタル酸無水物含有単位を含有する熱可塑性重合体である。

(In the above formula, R ¹ and R ² represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.)
It is a thermoplastic polymer containing the glutaric anhydride containing unit represented by these.

  Among them, a copolymer having (i) a glutaric anhydride-containing unit represented by the above general formula (1) and (ii) an unsaturated carboxylic acid alkyl ester unit is preferable.

  The content of the glutaric anhydride-containing unit (i) represented by the general formula (1) in the thermoplastic polymer (A) of the present invention is preferably 100% by weight of the thermoplastic polymer (A). It is 25 to 50% by weight, more preferably 30 to 45% by weight. When the glutaric anhydride-containing unit is less than 25% by weight, not only the heat resistance improving effect is reduced, but also birefringence characteristics (optical isotropy) and solvent resistance tend to be lowered.

  The content of the unsaturated carboxylic acid alkyl ester unit (ii) in the thermoplastic polymer (A) of the present invention is preferably 50 to 75% by weight in 100% by weight of the thermoplastic polymer (A). Preferably it is 55 to 70% 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 thermoplastic polymer (A) of the present invention. In infrared spectroscopy, glutaric anhydride containing units, absorption of 1800 cm ^-1 and 1760 cm ^-1 are characteristic can be distinguished from unsaturated carboxylic acid units and unsaturated carboxylic acid alkyl ester unit. 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-containing 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 peak. Α-methyl group hydrogen of methacrylic acid, methyl methacrylate and glutaric anhydride ring compound, peak of 1.6 to 2.1 ppm is hydrogen of methylene group of polymer main chain, peak of 3.5 ppm is methyl methacrylate Carboxylic acid ester (—COOCH ₃ ) hydrogen, 12.4 ppm peak is the hydrogen of carboxylic acid methacrylic acid. In addition to the above, in the case of a copolymer containing styrene as another copolymer component, hydrogen of an aromatic ring of styrene is seen at 6.5 to 7.5 ppm, and the copolymer is similarly obtained from the spectral ratio. The composition can be determined.

  The thermoplastic polymer of the present invention further contains (iii) an unsaturated carboxylic acid unit and / or (iv) another vinyl monomer unit in addition to the units (i) and (ii) above. can do. Here, (iv) the other vinyl monomer unit is a copolymerizable vinyl monomer unit that does not belong to any of the above (i) to (iii).

  The content of the unsaturated carboxylic acid unit (iii) contained in 100% by weight of the thermoplastic polymer (A) of the present invention is preferably 10% by weight or less, that is, 0 to 10% by weight, more preferably. 0 to 5% by weight, most preferably 0 to 1% by weight. When the unsaturated carboxylic acid unit (iii) exceeds 10% by weight, colorless transparency and residence stability tend to be lowered.

  The content of the other vinyl monomer units (iv) is preferably 10% by weight or less, that is, in the range of 0 to 10% by weight in 100% by weight of the thermoplastic polymer (A). As the other vinyl monomer unit (iv), 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.

  The unsaturated carboxylic acid unit (iii) preferably has a structure represented by the following general formula (4).

（ただし、Ｒ^９は水素または炭素数１〜５のアルキル基を表す）

(However, R ⁹ represents hydrogen or an alkyl group having 1 to 5 carbon atoms.)

  The unsaturated carboxylic acid alkyl ester unit (ii) preferably has a structure represented by the following general formula (5).

（ただし、Ｒ^１０は水素または炭素数１〜５のアルキル基を表し、Ｒ^１１は炭素数１〜６の脂肪族もしくは脂環式炭化水素基、または１個以上炭素数以下の数の水酸基もしくはハロゲンで置換された炭素数１〜６の脂肪族もしくは脂環式炭化水素基を示す）

(However, R ¹⁰ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and R ¹¹ represents an aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms, or a hydroxyl group having 1 or more carbon atoms inclusive. A C1-C6 aliphatic or alicyclic hydrocarbon group substituted with a halogen)

  The thermoplastic polymer (A) preferably has a weight average molecular weight of 30,000 to 150,000, more preferably 50,000 to 130,000, and particularly preferably 70,000 to 110,000. 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).

  In terms of heat resistance, the thermoplastic polymer (A) used in the present invention preferably has a glass transition temperature (Tg) of 130 ° C. or higher. The glass transition temperature is more preferably 140 ° C. or higher, and particularly preferably 150 ° 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 thermoplastic polymer (A) used in the present invention has a yellowness index value of 5 or less, and the coloration is extremely suppressed. In a more preferred embodiment, it is 4 or less, and in a most preferred embodiment, it is 3 or less. Colorless. Thereby, the yellowness of the thermoplastic resin composition of the present invention containing the thermoplastic polymer (A) can also be 5 or less, more preferably 4 or less, most preferably 3 or less, and extremely excellent colorlessness. It is preferable because a molded product or a film having the above can be obtained. When the yellowness value of the thermoplastic polymer (A) is large, a part of the thermoplastic polymer (A) has undergone thermal decomposition, and the heat of the present invention containing the thermoplastic polymer (A). The mechanical properties of the plastic resin composition tend to decrease. Also in this respect, it is preferable that the yellowness of the thermoplastic polymer (A) is in the above range. Here, the yellowness index means that the thermoplastic polymer (A) or the thermoplastic resin composition of the present invention is injection molded, and the resulting 1 mm-thick molded product is SM according to JIS-K7103. It is the value measured using the color computer (made by Suga Test Instruments).

  Such a thermoplastic polymer (A) containing the glutaric anhydride-containing unit represented by the general formula (1) of the present invention can be basically produced by the method shown below. That is, the unsaturated carboxylic acid monomer and the unsaturated carboxylic acid alkyl ester monomer that give the glutaric anhydride-containing unit (i) represented by the general formula (1) by the subsequent heating step are copolymerized, A copolymer (a) is obtained. In that case, when the said other vinyl monomer unit (iv) is included, you may copolymerize the vinyl monomer which gives this unit. 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, whereby a thermoplastic polymer (A) is obtained. Can be manufactured. In this case, typically, the copolymer (a) is heated to cause a dehydration reaction between the carboxyl groups of two adjacent unsaturated carboxylic acid units (iii), or to the adjacent unsaturated carboxylic acid. The dealcoholization reaction between the acid unit (iii) and the unsaturated carboxylic acid alkyl ester unit (ii) produces one unit of the (i) glutaric anhydride-containing unit.

  As the unsaturated carboxylic acid monomer used in this case, any unsaturated carboxylic acid monomer that can be copolymerized with another vinyl compound can be used. As a preferable unsaturated carboxylic acid monomer, the following general formula (6)

（ただし、Ｒ^９は水素または炭素数１〜５のアルキル基を表す）
で表される化合物、マレイン酸、および無水マレイン酸の加水分解物などが挙げられる。

(However, R ⁹ represents hydrogen or an alkyl group having 1 to 5 carbon atoms.)
And a hydrolyzate of maleic anhydride and maleic anhydride.

  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 an unsaturated carboxylic acid unit (iii) having a structure represented by the general formula (2) when copolymerized.

  Moreover, what is represented by following General formula (7) can be mentioned as a preferable example of an unsaturated carboxylic acid alkylester monomer.

（ただし、Ｒ^１０は水素または炭素数１〜５のアルキル基を表し、Ｒ^１１は炭素数１〜６の脂肪族もしくは脂環式炭化水素基、または１個以上炭素数以下の数の水酸基もしくはハロゲンで置換された炭素数１〜６の脂肪族もしくは脂環式炭化水素基を示す）

(However, R ¹⁰ represents hydrogen or an alkyl group having 1 to 5 carbon atoms, and R ¹¹ represents an aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms, or a hydroxyl group having 1 or more carbon atoms inclusive. A C1-C6 aliphatic or alicyclic hydrocarbon group substituted with a halogen)

  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 an unsaturated carboxylic acid alkyl ester unit (ii) having a structure represented by the general formula (3) 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. This other vinyl monomer gives the other vinyl monomer unit (iv) when copolymerized. 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.

  As a polymerization method of the copolymer (a), a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, precipitation polymerization or the like basically by radical polymerization can be used. Solution polymerization, bulk polymerization, suspension polymerization, and precipitation polymerization are preferred in terms of fewer impurities.

  About polymerization temperature, it is preferable to superpose | polymerize at the polymerization temperature of 95 degrees C or less from a viewpoint of a color tone. Furthermore, in order to further suppress coloring after the heat treatment, a preferable polymerization temperature is 85 ° C. or lower, and particularly preferably 75 ° C. or lower. The lower limit of the polymerization temperature is not particularly limited as long as the polymerization proceeds, but is preferably 50 ° C. or higher, more preferably 60 ° C. or higher from the viewpoint of productivity in consideration of the polymerization rate. For the purpose of improving the polymerization yield or polymerization rate, the polymerization temperature can be raised as the polymerization proceeds. Also in this case, it is preferable to control the upper limit temperature to be raised to 95 ° C. or lower, and it is preferable to perform the polymerization start temperature at a relatively low temperature of 75 ° C. or lower. The polymerization time is not particularly limited as long as it is a sufficient time to obtain the required degree of polymerization, but is preferably in the range of 60 to 360 minutes, particularly preferably in the range of 90 to 180 minutes from the viewpoint of production efficiency.

  In the present invention, the preferred proportion of these monomer mixtures used in the production of the copolymer (a) is such that the total amount of the monomer mixture is 100% by weight and the unsaturated carboxylic acid monomer is 15 to 50% by weight. %, More preferably 20 to 45% by weight, and the unsaturated carboxylic acid alkyl ester monomer is 50 to 85% by weight, more preferably 55 to 80% 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 15% by weight, when the thermoplastic polymer (A) is produced by heating the copolymer (a), the general formula (1) The amount of the glutaric anhydride-containing unit (i) represented is reduced, and the heat resistance improving effect of the thermoplastic polymer (A) tends to be reduced. On the other hand, when the content of the unsaturated carboxylic acid monomer (iii) exceeds 50% by weight, the unsaturated copolymer is produced when the thermoplastic polymer (A) is produced by heating the copolymer (a). The carboxylic acid unit (iii) tends to remain in a large amount, and the colorless transparency and residence stability of the thermoplastic polymer (A) tend to decrease.

  As described above, the thermoplastic polymer (A) of the present invention preferably has a weight average molecular weight of 30,000 to 150,000. The thermoplastic polymer (A) having such a molecular weight is obtained by controlling the copolymer (a) to 30,000 to 150,000 in a weight average molecular weight in advance during the production of the copolymer (a). Can be achieved.

  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.

  The method for producing a thermoplastic polymer (A) containing a glutaric anhydride-containing unit by heating the copolymer (a) in the present invention, performing an intramolecular cyclization reaction by dehydration and / or dealcoholization, Although there is no particular 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 it is a temperature at which an intramolecular cyclization reaction is caused by dehydration and / or dealcoholization, but it is preferably in the range of 180 to 320 ° C., particularly preferably 200 to 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 polymer 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.

  In the present invention, by incorporating the rubber-containing polymer (B) into the thermoplastic polymer (A), excellent impact resistance can be obtained without greatly impairing the excellent properties of the thermoplastic polymer (A). Can be granted.

  In the present invention, it has been found that there is a correlation between the morphology and color tone of the thermoplastic resin composition, and coloring is remarkably suppressed by controlling the aggregation state of the rubber-containing polymer. The thermoplastic resin composition of the present invention has a ratio (X / Y) of the number of agglomerated rubber-containing polymers (X) to the number of agglomerated rubber-containing polymers (Y) is 0.5. It is characterized by the following. In this case, the agglomerated state refers to a case where the rubber layers described later are in contact with each other in two adjacent rubber-containing polymers, and in other cases, that is, both are separated or If the dots are in contact, it is determined that they are not agglomerated. About the said determination and measurement of X and Y, it is performed from the photograph image | photographed using the 20,000 times transmission type | mold microscope picture about a thermoplastic resin composition. In this case, since the cross section of the particle is observed in the photograph, it is determined that the adjacent two particles are aggregated when the contact portion of the rubber layer is not a point but a line. X indicates the total number of rubber-containing polymers involved in aggregation. That is, when five particles are aggregated to form one aggregate, the calculation is performed as five particles. About the value of (X / Y), 0.5 or less is preferable, More preferably, it is 0.3 or less, More preferably, it is 0.1 or less. There is no particular limitation on the lower limit, and it is preferable that there is no aggregation.

  The rubber-containing polymer (B) is composed of a layer containing one or more rubber-like polymers and one or more layers made of different polymers, and one or more layers of rubber inside. Graft copolymer obtained by copolymerizing a monomer mixture composed of vinyl monomers in the presence of a so-called core-shell type multi-layer structure polymer having a layer containing a polymer and a rubbery polymer A coalescence or the like can be preferably used, but a multilayer structure polymer is particularly preferable because of its excellent transparency and little coloration.

  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) A multilayer structure polymer having a layer) is preferable.

  In the multilayer structure polymer of the present invention, the kind of the rubber layer is not particularly limited as long as it is composed of a polymer component having rubber elasticity. 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, a rubber obtained by crosslinking a copolymer composed of a crosslinking component such as a divinylbenzene unit, an allyl acrylate unit, and a butylene glycol diacrylate unit is also 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.

  In the multilayer structure polymer containing the rubber polymer of 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, an unsaturated glycidyl group-containing unit, From polymers containing one or more types of units such as aliphatic vinyl units, aromatic vinyl units, vinyl cyanide units, maleimide units, unsaturated dicarboxylic acid units, unsaturated dicarboxylic anhydride units, and other vinyl units. There may be mentioned at least one selected. 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, a polymer containing an unsaturated carboxylic acid alkyl ester unit and an unsaturated carboxylic acid unit is used as the outermost layer as the rubbery polymer (B) to be subjected to melt kneading with the thermoplastic polymer (A). Most preferably, a multilayer structure 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-containing 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-containing unit represented by the general formula (1) in the outermost layer is obtained. Thereby, the multilayer structure polymer containing the glutaric anhydride-containing unit represented by the general formula (1) is well dispersed in the thermoplastic copolymer (A) serving as the continuous phase (matrix phase). Therefore, it is considered that the thermoplastic resin composition of the present invention can exhibit extremely high transparency as well as improved mechanical properties such as impact resistance.

  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). In which the core layer is a butyl acrylate / styrene copolymer and the outermost layer is methyl methacrylate / glutaric anhydride represented by the general formula (1) Product containing unit / methacrylic acid copolymer, core layer is dimethylsiloxane / butyl acrylate copolymer and outermost layer is methyl methacrylate polymer, core layer is butanediene / styrene copolymer and outermost layer Is a methyl methacrylate polymer, and the core layer is a butyl acrylate polymer and the outermost layer is a methyl methacrylate polymer.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 composed of methyl methacrylate / glutaric anhydride-containing units 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-containing 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.

  About the average particle diameter of the multilayer structure polymer of this invention, it is preferable that they are 0.01 micrometer or more and 1000 micrometers or less. The average particle diameter is more preferably 0.02 μm or more and 100 μm or less, further preferably 0.05 μm or more and 10 μm or less, and most preferably 0.05 μm or more and 1 μm or less. If it is less than the above range, the impact strength of the resulting thermoplastic composition tends to decrease, and if it exceeds the above range, transparency may decrease. The average particle size of the multilayer structure polymer can be calculated from a Guinier plot or a transmission electron micrograph by small angle light scattering measurement.

  In the multilayer structure polymer of the present invention, the weight ratio of the core to the shell is preferably 50% by weight or more and 90% by weight or less, and more preferably 60% by weight or more, based on the whole multilayer structure polymer. 80% by weight or less is more preferable.

  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 Co., Ltd., “Paralloid (registered trademark)” manufactured by Kureha Chemical Industry , “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.

  Further, specific examples of the rubber-containing graft copolymer used as the rubber-containing polymer (B) of the present invention include an unsaturated carboxylic acid ester monomer (its specific example) in the presence of the rubber polymer. Examples are the same as described above), unsaturated carboxylic acid monomers (specific examples are the same as described above), aromatic vinyl monomers (specific examples are the same as described above), and as necessary A graft copolymer obtained by (co) polymerizing a monomer (mixture) selected from one or more of other vinyl monomers copolymerizable with these (specific examples are the same as those described above). Can be mentioned.

  Diene rubber, acrylic rubber, ethylene rubber and the like can be used as the rubbery polymer used for the graft copolymer. Specific examples include polybutadiene, styrene-butadiene copolymer, block copolymer of styrene-butadiene, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, polyisoprene, butadiene-methyl methacrylate copolymer. , Butyl acrylate-methyl methacrylate copolymer, butadiene-ethyl acrylate copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-isoprene copolymer, and ethylene-methyl acrylate A copolymer etc. are mentioned. These rubbery polymers can be used alone or in a mixture of two or more.

  The weight average particle diameter of the rubbery polymer constituting the graft copolymer in the present invention is preferably in the range of 0.1 to 0.5 μm, particularly 0.15 to 0.4 μm. If it is less than the above range, the impact strength of the resulting thermoplastic composition tends to decrease, and if it exceeds the above range, transparency may decrease. The weight average particle diameter of the rubber polymer is the sodium alginate method described in “Rubber Age, Vol. 88, p. 484-490 (1960), by E. Schmidt, P. H. Biddison”, that is, sodium alginate. By using the fact that the diameter of the polybutadiene particles to be creamed differs depending on the concentration of the cream, it can be measured by a method of determining the particle size of 50% cumulative weight fraction from the weight proportion of cream and the cumulative weight fraction of sodium alginate concentration. .

  The graft copolymer in the present invention is a rubbery polymer in the presence of 10 to 80% by weight, preferably 20 to 70% by weight, more preferably 30 to 60% by weight. It is obtained by copolymerizing 90% by weight, preferably 30 to 80% by weight, more preferably 40 to 70% by weight. When the ratio of the rubbery polymer is less than the above range or exceeds the above range, the impact strength and the surface appearance may be lowered.

  The graft copolymer may contain an ungrafted copolymer that is produced when the monomer mixture is graft copolymerized with the rubbery polymer. From the viewpoint of impact strength, the graft ratio is preferably 10 to 100%. Here, the graft ratio is a weight ratio of the grafted monomer mixture to the rubbery polymer. Further, the intrinsic viscosity of the ungrafted copolymer measured at 30 ° C. is preferably 0.1 to 0.6 dl / g from the viewpoint of the balance between impact strength and moldability. .

  The intrinsic viscosity of the graft copolymer according to the present invention measured at 30 ° C. is not particularly limited, but 0.2 to 1.0 dl / g has a balance between impact strength and moldability. It is preferably used from the viewpoint, and more preferably 0.3 to 0.7 dl / g.

  There is no restriction | limiting in particular in the manufacturing method of the graft copolymer in this invention, It can obtain by well-known polymerization methods, such as block polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.

  Moreover, since the thermoplastic resin composition excellent in transparency can be obtained when each refractive index of a thermoplastic polymer (A) and a rubber-containing polymer (B) is approximated, it is preferable. Specifically, the difference in refractive index between the two is preferably 0.05 or less, more preferably 0.02 or less, and particularly preferably 0.01 or less. In order to satisfy such a refractive index condition, a method for adjusting the monomer unit composition of the thermoplastic polymer (A) and / or a rubbery polymer used for the rubbery polymer (B) Or the method of preparing the composition of a monomer etc. are mentioned.

  In addition, the refractive index difference said here is the value measured by the method shown below. In the solvent in which the thermoplastic polymer (A) is soluble, the thermoplastic resin composition of the present invention is sufficiently dissolved under appropriate conditions to form a cloudy solution, which is insoluble in the solvent-soluble portion by an operation such as centrifugation. Separate into parts. After refining the soluble part (part containing the thermoplastic polymer (A)) and the insoluble part (part containing the rubbery polymer (B)), the measured refractive index (23 ° C., measurement wavelength: 550 nm). ) Is defined as the difference in refractive index.

  In addition, the copolymer composition of the thermoplastic polymer (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 using the solvent. To analyze.

  In this invention, it is preferable that the weight ratio at the time of mix | blending a thermoplastic polymer (A) and a rubber-containing polymer (B) is the range of 99 / 1-50 / 50, Furthermore, 99 / 1-1 A range of 60/40 is more preferable, and a range of 99/1 to 70/30 is particularly preferable.

  When producing the thermoplastic resin composition of the present invention, a method is used in which the thermoplastic polymer (A) and the rubber-containing polymer (B) are heated, melted and mixed under an appropriate shear field. In order to suppress agglomeration of the rubber-containing polymer particles in the thermoplastic resin composition to be produced, it is preferable to melt and knead so that the shearing force is not excessively applied at a relatively low temperature and a low rotational speed. Specifically, when the resin temperature in the kneading zone is T, the temperature is controlled in the range of (Tg of thermoplastic polymer (A) + 100 ° C.) ≦ T ≦ (1% decomposition temperature of rubber-containing polymer (B)). Further, it is more preferable to control within the range of (Tg of the thermoplastic polymer (A) + 120 ° C.) ≦ T ≦ (0.5% decomposition temperature of the rubber-containing polymer (B)). Here, the 1% decomposition temperature of the rubber-containing polymer (B) is 100 to 450 ° C. using a differential thermogravimetric simultaneous measurement apparatus (TG / DTA-200, manufactured by Seiko Denshi Kogyo Co., Ltd.) in nitrogen. This is the temperature when the weight reduction rate reaches 1% when the weight before heating is 100% by the heating test conducted in the temperature range of 20 ° C./min. When the resin temperature is lower than the range of the present invention, the melt viscosity becomes extremely high, and melt kneading becomes virtually impossible, which is not preferable. On the other hand, when the resin temperature is higher than the range of the present invention, re-aggregation and coloring of the rubber-containing polymer (B) become remarkable, which is not preferable.

  By containing the monophosphite compound (C) used in the present invention, decomposition of the rubber-containing polymer (B) is suppressed, and a significant coloring suppression and fluidity improvement effect can be obtained.

  The monophosphite compound (C) used in the present invention is an organic phosphite ester having one phosphorus atom and three organic groups bonded in the molecule, and has a molecular weight of 300 to 2000 from the viewpoint of heat resistance. More preferably, the molecular weight is more preferably in the range of 350-1500, and most preferably in the range of 400-1000. When the molecular weight is 300 or less, it tends to volatilize during melt-kneading, and it is difficult to obtain the effect of suppressing coloration and improving fluidity. When the molecular weight is 2000 or more, there is a problem that high transparency is easily obtained. Furthermore, although there are forms such as liquid or solid as properties, there is no restriction in use, and in the case of liquid, the viscosity is preferably in the range of 1 to 10000 mPa · s, and further the viscosity is in the range of 2 to 7000 mPa · s. More preferably, the viscosity is most preferably in the range of 5 to 5000 mPa · s. Alternatively, in the case of solid properties, the melting point is preferably 60 to 220 ° C, more preferably 80 to 210 ° C, and most preferably 100 to 200 ° C. Furthermore, a cyclic monophosphite compound (C) represented by the following general formula (2) in which two or more of the three oxygen atoms of the organic phosphite are bonded to an aromatic residue, or It is preferably a monophosphite compound (C) represented by the following general formula (3) in which at least one of the three oxygen atoms of the organic phosphite is bonded to an aromatic residue.

（上記式中、Ｒ^３はｔ−ブチル基またはｔ−アミル基を示し、Ｒ^４は炭素原子数１〜９のアルキル基を示し、Ｒ^５は水素原子または炭素数１〜９のアルキル基を示し、Ｒ^６は炭素原子数１〜３０のアルキル基、置換もしくは非置換アリール基を表す。）

(In the above formula, R ³ represents a t-butyl group or a t-amyl group, R ⁴ represents an alkyl group having 1 to 9 carbon atoms, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. R ⁶ represents an alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group.)

In the general formula (2), the alkyl group having 1 to 9 carbon atoms represented by R ⁴ includes methyl, ethyl, propyl, isopropyl, butyl, i-butyl, t-butyl, isobutyl, amyl, t-amyl. , Fuxyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, tertiary nonyl and the like. Examples of the alkyl group having 1 to 9 carbon atoms represented by R ⁵ include methyl, ethyl, propyl, isopropyl , butyl, i- butyl, t- butyl, isobutyl, amyl, t-amyl, Fukishiru, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, tert-nonyl and the like, as shown in ^{R 6} Examples of the alkyl group having 1 to 30 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, i-butyl, t Butyl, isobutyl, amyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, tertiary nonyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, Examples of substituted or unsubstituted aryl groups such as triacontyl include phenyl, 4-methylphenyl, 2-hydroxyphenyl, 4-hydroxyphenyl, 2-t-butylphenyl, 3-methyl-4-hydroxyphenyl, and 3,5-dimethyl. -4-hydroxyphenyl, 3-t-butyl-4-hydroxyphenyl, 3-t-butyl-4-hydroxy-6-methylphenyl, 2,4-di-t-butylphenyl, 2,5-di-t-butyl And phenyl.

（上記式中、Ｒ^７は炭素原子数１〜３０のアルキル基または置換もしくは非置換アリール基を示し、Ｒ^８はＲ^７は炭素原子数１〜３０のアルキル基、置換もしくは非置換アリール基を表す。）

(In the above formula, R ⁷ represents an alkyl group or a substituted or unsubstituted aryl group having 1 to 30 carbon atoms, R ⁸ is R ⁷ is an alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group To express.)

In the above general formula (3), the alkyl group having 1 to 30 carbon atoms represented by R ⁷ or R ⁸ is methyl, ethyl, propyl, isopropyl, butyl, i-butyl, t-butyl, isobutyl, amyl, t -Amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, tertiary nonyl, decyl, isodecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, triacontyl, etc., substituted or unsubstituted The aryl group includes phenyl, 4-methylphenyl, 2-hydroxyphenyl, 4-hydroxyphenyl, 2-t-butylphenyl, 3-methyl-4-hydroxyphenyl, 3,5-dimethyl-4-hydroxyphenyl, 3 -T-butyl-4-hydroxyl Sulfonyl, 3-t-butyl-4-hydroxy-6-methylphenyl, 2,4-di-t-butylphenyl, 2,5-di-t-butylphenyl and the like.

While R ⁷ is not particularly limited as the combination of ^{R 8,} the same aryl groups ^{R 7} and ^{R 8} each other, ^{R 7} and ^{R 8} are different aryl group, ^{R 8} in ^{R 7} is an alkyl group or an aryl group A combination in which R ⁷ and R ⁸ are the same aryl group, R ⁷ is an aryl group, and R ⁸ is an alkyl group can be particularly preferably used.

  Specific phosphite compounds (C) include triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (2-t-butyl). Phenyl) phosphite, tris (2,5-t-butylphenyl) phosphite, tris (mixed mono and di-nonylphenyl) phosphite, tris (2-t-butyl-4-methylphenyl) phosphite, tris (2-t-butyl-5-methylphenyl) phosphite, tris (2-t-butyl-4,6-dimethylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) 4,4 ′ -Biphenylene phosphonite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4 - butylidene - bis (3-methyl -6-t-butylphenyl - di - tridecyl) phosphite, and the like.

  Among these, tris (2-t-butylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (2,5-t-butylphenyl) phosphite, 2,2- Methylene bis (4,6-di-t-butylphenyl) octyl phosphite can be used particularly preferably. These specific phosphite compounds (C) can be used alone or in combination of two or more.

  The monophosphite compound (C) used in the present invention can be used in combination with a hindered phenol compound or a thioether compound. By using at least one kind of hindered phenol-based compound and thioether-based compound, decomposition of the rubber-containing polymer (B) is further suppressed, and a significant color tone improving effect is obtained.

  Specific hindered phenolic compounds having a molecular weight of 400 or more are preferred, and specifically, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propione. -To], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5- t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylene (3,5-di-t-butyl-4-hydroxyhydrocinnamamide), 2-t-butyl-6- ( 3′-t-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methyl) ) Propionyloxy} -1,1-dimethylethyl] -2,4,8,10-pyro [5.5] undecane.

  Specific thioether compounds include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-lauryl thiopropionate). ), Pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3 -Stearyl thiopropionate).

  As a method for producing the thermoplastic resin composition of the present invention, a copolymer (a) containing (ii) an unsaturated carboxylic acid alkyl ester unit and (iii) an unsaturated carboxylic acid unit is heated in a heat treatment apparatus. Processed thermoplastic polymer having 25-50 wt% of glutaric anhydride structural units, (ii) 50-75 wt% of unsaturated carboxylic acid alkyl ester units, and (iii) 10 wt% or less of unsaturated carboxylic acid units ( When A) is produced, 0.001 to 5 parts by weight of phosphine is contained with respect to 100 parts by weight of the total amount of the rubbery polymer (B), the thermoplastic polymer (A), and the rubbery polymer (B). A method of adding a phyto compound (C) simultaneously with the copolymer (a) and melt-kneading, a process of producing the thermoplastic polymer (A), and a rubber-containing polymer (B) in the middle of the heat treatment Thermoplastic polymer (A And a method of adding 0.001 to 5 parts by weight of a phosphite compound (C) to 100 parts by weight of the total amount of the rubber-containing polymer (B) and melt-kneading, and producing a thermoplastic polymer (A) After that, the thermoplastic polymer (A), the rubber-containing polymer (B), the thermoplastic polymer (A), and the rubber-containing polymer (B) are added in an amount of 0.001 to 5 to 100 parts by weight. Examples thereof include a method of melt-kneading a part by weight of the phosphite compound (C).

  Among these, in the process of producing the thermoplastic polymer (A), the sum of the rubber-containing polymer (B), the thermoplastic polymer (A) and the rubber-containing polymer (B) in the middle of the heat treatment. A method of adding 0.001 to 5 parts by weight of a phosphite compound (C) with respect to 100 parts by weight and melt-kneading, after producing a thermoplastic polymer (A), a thermoplastic polymer (A), 0.001 to 5 parts by weight of the phosphite compound (C) with respect to 100 parts by weight of the total amount of the rubbery polymer (B), the thermoplastic polymer (A), and the rubbery polymer (B). A melt kneading method can be preferably used. In the method of adding at the same time as the copolymer (a), the phosphite compound (C) is easily hydrolyzed by a large amount of water produced during the reaction, and the coloration of the rubber-containing polymer (B) cannot be significantly suppressed. It is not preferable.

  There are no restrictions on the heat treatment apparatus that can be used, for example, a single screw extruder, a twin screw extruder, a twin / single screw combined continuous kneading extruder, a triaxial extruder, a continuous or batch kneader kneader, etc. It can be preferably used.

  Further, the thermoplastic polymer and thermoplastic resin composition of the present invention are not limited to the purpose of the present invention, and other thermoplastic resins such as polyethylene, polypropylene, acrylic resin, polyamide, polyphenylene sulfide resin, polyether ether Further contains at least one selected from thermosetting resins such as ketone resins, polyesters, polysulfones, polyphenylene oxides, polyacetals, polyimides, polyetherimides, such as phenol resins, melamine resins, polyester resins, silicone resins, epoxy resins, etc. Can be made. Also, lubricants and plasticizers such as higher fatty acids, acid esters and acid amides, higher alcohols, montanic acid and its salts, esters, half esters, stearyl alcohol, stearamide and ethylene wax, phosphorous acid Anti-coloring agents such as salts and hypophosphites, halogen-based flame retardants, phosphorus-based and silicone-based non-halogen flame retardants, nucleating agents, amine-based, sulfonic acid-based, polyether-based anti-static agents, pigments Additives such as colorants such as dyes and optical brighteners may be optionally added. However, in light of the characteristics required by the application to be applied, it is preferable to add the additive within a range where the color of the additive does not adversely affect the thermoplastic polymer and the transparency is not lowered.

  The thermoplastic resin composition of the present invention is excellent in mechanical properties and molding processability, and can be melt-molded. Therefore, extrusion molding, injection molding, press molding, etc. are possible, and films, sheets, tubes, It can be used after being molded into a rod or other molded article having any desired shape and size.

  A well-known method can be used for the manufacturing method of the film which consists of a thermoplastic resin composition 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 casting 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 product or film of the present invention is particularly excellent in transparency and heat resistance, so as a video equipment-related part, a photographing lens such as a camera, VTR, projection TV, finder, filter, prism, Fresnel lens, etc. Various optical disc (VD, CD, DVD, MD, LD, etc.) substrates, various disc substrate protective films, optical disc player pickup lenses, optical fibers, optical switches, optical connectors, etc. Liquid crystal display, flat panel display, plasma display light guide plate, Fresnel lens, polarizing plate, polarizing plate protective film, retardation film, light diffusion film, viewing angle widening film, reflective film, antireflection film, antiglare film, brightness improvement the film, Rhythm sheet, pickup lens, conductive film for touch panel, cover, etc., transportation equipment related parts such as automobile, tail lamp lens, head lamp lens, inner lens, amber cap, reflector, extension, side mirror, room mirror, side visor, instrument needle , Glazing typified by instrument covers, window glass, etc., as medical equipment related parts, spectacle lenses, spectacle frames, contact lenses, endoscopes, optical cells for analysis, etc. It is extremely useful for applications such as lighting covers, signboards, translucent sound insulation walls, and bathtub materials.

  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 polymer (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 in a reactor and reacted. The inside of the vessel was kept 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 obtained 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 capacity 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 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 polymerization rate of this copolymer (a-1) was 98%.
Methacrylic acid 28 parts by weight Methyl methacrylate 72 parts by weight t-dodecyl mercaptan 1.2 parts by weight 2,2′-azobisisobutyronitrile 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 polymer (A-1). The reaction was carried out while purging nitrogen from the hopper at a rate of 10 L / min.

The results obtained thermoplastic polymer (A-1) was analyzed with an infrared spectrophotometer, both the absorption peaks at 1800 cm ^-1 and 1760 cm ^-1 was confirmed, the thermoplastic polymer (A-1 ) To form glutaric anhydride units. 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 polymer (A-2) A methyl methacrylate / acrylamide copolymer suspending agent (the following method) was placed in a stainless steel autoclave having a capacity of 5 liters and equipped with a baffle and a foudra-type stirring blade. 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, and the reactor was heated to 70 ° C. while substituting nitrogen gas. The reaction is continued until the monomer is completely converted to a polymer and is obtained as an aqueous solution of methyl acrylate and acrylamide copolymer (the resulting aqueous solution was used as a suspending agent). A solution dissolved in 165 parts of exchange water was supplied, stirred at 400 rpm, and 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 polymerization rate of this copolymer (a-2) was 98%.
Methacrylic acid 15 parts by weight Methyl methacrylate 85 parts by weight t-dodecyl mercaptan 0.6 parts by weight 2,2′-azobisisobutyronitrile 0.4 parts by weight.

  Next, a pellet-shaped thermoplastic polymer (A-2) was obtained by using the obtained bead copolymer (a-2) in the same manner as in the preparation of (A-1).

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 of 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. The polymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to obtain a rubber-containing polymer (B-1) having a two-layer structure. The 1% decomposition temperature of the polymer particles in nitrogen was 295 ° C.

Reference Example 4: Production of rubber-containing polymer (B-2) Polybutadiene (weight average particle diameter 0.35 μm) 50 parts by weight (in terms of solid content)
Potassium oleate 0.5 parts by weight Glucose 0.5 parts by weight Sodium pyrophosphate 0.5 parts by weight Ferrous sulfate 0.005 parts by weight Deionized water 120 parts by weight The temperature was raised to ° C. The polymerization was started when the internal temperature reached 65 ° C., and 50 parts by weight of a mixture comprising 70 parts by weight of styrene, 30 parts by weight of acrylonitrile and 0.3 parts by weight of t-dodecyl mercaptan was continuously added dropwise over 5 hours. In parallel, an aqueous solution consisting of 0.25 parts by weight of cumene hydroperoxide, 2.5 parts by weight of potassium oleate and 25 parts by weight of pure water was continuously added dropwise over 7 hours to complete the reaction. The obtained graft copolymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to obtain a graft copolymer (B-2). This graft copolymer (B-2) had a graft ratio of 45%, an acetone-soluble methyl ethyl ketone solvent, and an intrinsic viscosity at 30 ° C. of 0.36 dl / g. The 1% decomposition temperature of the polymer particles in nitrogen was 280 ° C.

[Examples 1-7, Comparative Examples 1-8]
A thermoplastic polymer (A), a rubber-containing polymer (B) and a monophosphite compound (C) having the copolymer composition shown in Table 1 were blended in the proportions shown in Table 2, and a twin screw extruder TEX30 (L /D=44.5, manufactured by Nippon Steel Co., Ltd.) and kneaded at a set temperature of 280 ° C. and a screw rotation speed of 100 rpm to obtain a pellet-shaped thermoplastic resin composition. For Examples 1 to 5, Comparative Examples 1 to 3, and Comparative Examples 6 to 8 containing the rubber-containing polymer (B-1), the thermoplastic resin composition is dispersed in tetrahydrofuran and centrifuged. After the rubbery polymer was isolated, was analyzed with an infrared spectrophotometer, both confirmed absorption peak at 1800 cm ^-1 and 1760 cm ^-1, glutaric anhydride units in the rubber-like polymer It was confirmed that it formed.

After drying the obtained pellet-shaped thermoplastic resin composition for 10 hours with a hot air dryer set at 80 ° C., a screw in-line type 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.) + 150 ° C. of thermoplastic polymer (A)
Mold temperature: 80 ℃
Molding cycle: Injection time 5 seconds / cooling time 10 seconds (80 mm × 80 mm × 1 mm thickness test piece)
Molding cycle: injection time 15 seconds / cooling time 20 seconds (127 mm × 12.7 mm × 3.2 mm thickness test piece)
Molding cycle: injection time 15 seconds / cooling time 20 seconds (64 mm × 12.7 mm × 3.2 mm thickness test piece)
Molding pressure: Pressure to fill the mold with all the resin (molding lower limit pressure) + 1MPa

[Example 8]
100 parts by weight of the bead-shaped copolymer (a-1) obtained in Reference Example 1 and 0.2 parts by weight of lithium acetate were mixed with a twin-screw extruder TEX30 (L / D = 44.5, manufactured by Nippon Steel Co., Ltd.). Intramolecular cyclization reaction is performed at a set temperature of 285 ° C. and a screw rotation speed of 100 rpm, and 25 parts by weight of a rubber-containing polymer (B) and a monophosphite system using a side feeder from an intermediate position in the middle of the heat treatment 0.25 parts by weight of the compound (C) was added and kneaded to obtain a pellet-shaped thermoplastic resin composition.

  After drying the obtained pellet-shaped thermoplastic resin composition for 10 hours with a hot air dryer set at 80 ° C., a screw inline type 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 above conditions.

[Example 9]
Biaxial extrusion of 100 parts by weight of the thermoplastic polymer (A-1) pellets obtained in Reference Example 1, 25 parts by weight of the rubber-containing polymer (B) and 0.25 parts by weight of the monophosphite compound (C) Using a machine TEX30 (L / D = 44.5, manufactured by Nippon Steel Co., Ltd.), the mixture was kneaded at a set temperature of 285 ° C. and a screw rotation speed of 100 rpm to obtain a pellet-shaped thermoplastic resin composition.

  After drying the obtained pellet-shaped thermoplastic resin composition for 10 hours with a hot air dryer set at 80 ° C., a screw inline type 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 above conditions.

[Comparative Example 9]
100 parts by weight of the bead-shaped copolymer (a-1) obtained in Reference Example 1, 0.2 part by weight of lithium acetate, 25 parts by weight of a rubbery polymer (B), and a monophosphite compound (C) Intramolecular cyclization reaction and rubber kneading at a set temperature of 285 ° C. and a screw speed of 100 rpm using a twin screw extruder TEX30 (L / D = 44.5, manufactured by Nippon Steel Co., Ltd.) with 0.25 parts by weight. Simultaneously, a pellet-shaped thermoplastic resin composition was obtained.

  After drying the obtained pellet-shaped thermoplastic resin composition for 10 hours with a hot air dryer set at 80 ° C., a screw inline type 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 above conditions.

  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 the glass transition temperature of the thermoplastic polymer (A) + 150 ° C. to obtain a molded product of 80 mm × 80 mm × 1 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 Index (YI)
The thermoplastic resin composition pellets of the present invention were injection molded at the glass transition temperature of the thermoplastic polymer (A) + 150 ° C. to obtain a test piece of 80 mm × 80 mm × 1 mm thickness. The YI value of the obtained molded product was measured using an SM color computer (manufactured by Suga Test Instruments Co., Ltd.) according to JIS-K7103.

(3) Thermal deformation temperature The thermoplastic resin composition pellets of the present invention were injection-molded at a glass transition temperature of the thermoplastic polymer (A) + 150 ° C., and a 127 mm × 12.7 mm × 3.2 mm thick test piece was obtained. Obtained. 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 polymer (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 impact characteristics were evaluated.

(5) Flowability The thermoplastic resin composition pellets of the present invention are sheared at a glass transition temperature of the thermoplastic polymer (A) + 150 ° C. using a Capillograph type 1C (die diameter φ1 mm, die length 5 mm) manufactured by Toyo Seiki Co., Ltd. The apparent melt viscosity at 1216 cm ⁻¹ was measured.

(6) Lens moldability The thermoplastic resin composition pellets of the present invention were injection molded at the glass transition temperature of the thermoplastic polymer (A) + 150 ° C. to obtain a φ75 mm model meniscus lens shape injection molded product. The weld length of the resulting model meniscus lens-shaped injection-molded product that appeared at the flow end (portion farthest from the gate) was measured.

(7) High-speed tensile elongation The thermoplastic resin composition pellets of the present invention were press-molded at the glass transition temperature of the thermoplastic polymer (A) + 150 ° C. to obtain a film molded product having a thickness of 100 μm. The obtained film molded product was cut into a strip shape (100 mm × 12.7 mm), and a high-speed tensile test (tensile speed: 500 mm / min, span: 50 mm) was used to measure the tensile elongation.

  From the result of Examples 1-7, the thermoplastic resin composition of this invention is excellent in high transparency, heat resistance, and impact resistance by mix | blending a monophosphite type compound, especially by rubber | gum component mixing | blending. It can be seen that the coloring is extremely small and the fluidity is excellent. The welded length of the model meniscus lens-shaped injection molded product is small, and a good molded product is obtained. The tensile elongation of the strip-shaped press film in the high-speed tensile test is also excellent.

  On the other hand, when no monophosphite compound is added (Comparative Examples 1, 4, and 5), it can be seen that the color tone is greatly deteriorated and the fluidity is not improved. Furthermore, depending on the rubber type, the impact property is also lowered.

  When a large amount of the monophosphite compound is added (Comparative Example 2), the color tone is good, but the transparency and impact value tend to decrease.

  Further, when a diphosphite compound having a polyhydric alcohol residue structure is added (Comparative Example 3), although the color tone, transparency, and impact value are good, the fluidity tends to deteriorate significantly.

  Further, when the copolymer composition of the thermoplastic polymer (A) is outside the scope of the present invention (Comparative Examples 6 and 7), high heat resistance cannot be obtained, and the heat resistance is significantly reduced. Recognize.

  The thermoplastic resin composition of the present invention has a high degree of transparency even when compared with PMMA (Comparative Example 8), is less colored, has excellent fluidity, and has excellent heat resistance, impact resistance, and toughness. It turns out that it can become a material to have together.

  From the results of Examples 1 and 9, after the production of the thermoplastic polymer (A), the rubbery polymer (B) and the monophosphite base (C) were blended later to achieve high transparency. It can be seen that this is a production method that provides a thermoplastic resin composition that is excellent in heat resistance, heat resistance, and impact resistance, and that is particularly less colored due to the incorporation of a rubber component and that has excellent fluidity. Furthermore, from the result of Example 8, when the thermoplastic polymer (A) is first produced, the rubber-containing polymer (B) and the monophosphite compound (C) are blended from the middle of the heat treatment. It can be seen that this is a production method that provides a thermoplastic resin composition that is excellent in high transparency, heat resistance, and impact resistance and that is particularly less colored due to the incorporation of a rubber component and that has excellent fluidity.

  On the other hand, in the case of Comparative Example 9, at the time of producing the thermoplastic polymer (A), the rubbery polymer (B) and the monophosphite compound (c) are blended simultaneously with the bead copolymer (a). It can be seen that in the method for producing a thermoplastic resin composition, the transparency is lowered, the color tone is deteriorated, and the fluidity is not improved. Furthermore, depending on the rubber type, the impact property is also lowered.

Claims (13)

(I) glutaric anhydride structural unit represented by the following general formula (1): 25 to 50% by weight, (ii) unsaturated carboxylic acid alkyl ester unit: 50 to 75% by weight, (iii) unsaturated carboxylic acid unit: 10 The monophosphite compound (C) is contained in an amount of 0.001 to 5 parts by weight with respect to 100 parts by weight of the resin composition comprising the thermoplastic polymer (A) and the rubbery-containing polymer (B) having a weight percent or less. Thermoplastic resin composition.

(In the above formula, R ¹ and R ² represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.) The thermoplastic resin composition according to claim 1, wherein the weight ratio of the thermoplastic polymer (A) and the rubber-containing polymer (B) is in the range of 99/1 to 50/50. The thermoplastic polymer (A) is a copolymer having 10% by weight or less of (iv) other vinyl monomer units in addition to the units (i), (ii) and (iii) above. Or the thermoplastic resin composition of 2. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the monophosphite compound (C) has a molecular weight of 300 to 2,000. The monophosphite compound is a cyclic monophosphite compound represented by the following general formula (2) or a monophosphite compound represented by the following general formula (3). The thermoplastic resin composition according to any one of the above.

(In the above formula, R ³ represents a t-butyl group or a t-amyl group, R ⁴ represents an alkyl group having 1 to 9 carbon atoms, and R ⁵ represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms. R ⁶ represents an alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group.)

(In the above formula, R ⁷ and R ⁸ represent the same or different alkyl groups having 1 to 30 carbon atoms or substituted or unsubstituted aryl groups.) The thermoplastic resin composition according to any one of claims 1 to 5, wherein the rubber-containing polymer (B) is a multilayer structure polymer having at least one rubber layer therein. object. The thermoplastic resin composition according to claim 6, wherein the polymer constituting the outermost layer of the multilayer structure polymer contains a glutaric anhydride-containing unit represented by the general formula (1). The thermoplastic resin composition according to claim 6 or 7, wherein the polymer constituting the rubber layer of the multilayer polymer contains an alkyl acrylate unit and a substituted or unsubstituted styrene unit. (Ii) A copolymer (a) containing an unsaturated carboxylic acid alkyl ester unit and (iii) an unsaturated carboxylic acid unit is heat-treated in a heat treatment apparatus, and (i) represented by the following general formula (1): A thermoplastic polymer (A) having 25 to 50% by weight of a glutaric anhydride structural unit, (ii) 50 to 75% by weight of an unsaturated carboxylic acid alkyl ester unit, and (iii) 10% by weight or less of an unsaturated carboxylic acid unit Then, 0.001 to 5 parts by weight of the rubber-containing polymer (B) and 100 parts by weight of the total amount of the thermoplastic polymer (A) and the rubber-containing polymer (B). A method for producing a thermoplastic resin composition in which a phosphite compound (C) is added and melt kneaded.

(In the above formula, R ¹ and R ² represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.) (Ii) A copolymer (a) containing an unsaturated carboxylic acid alkyl ester unit and (iii) an unsaturated carboxylic acid unit is heat-treated in a heat treatment apparatus, and (i) represented by the following general formula (1): A thermoplastic polymer (A) having 25 to 50% by weight of a glutaric anhydride structural unit, (ii) 50 to 75% by weight of an unsaturated carboxylic acid alkyl ester unit, and (iii) 10% by weight or less of an unsaturated carboxylic acid unit In the middle of the heat treatment, the rubber-containing polymer (B) and the total amount of the thermoplastic polymer (A) and the rubber-containing polymer (B) are 100 parts by weight. A method for producing a thermoplastic resin composition in which 0.001 to 5 parts by weight of a monophosphite compound (C) is added and melt kneaded.

(In the above formula, R ¹ and R ² represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms.) The addition amount of the rubber-containing polymer (B) is in the range of 99/1 to 50/50 in terms of the weight ratio of the thermoplastic polymer (A) and the rubber-containing polymer (B). A method for producing a thermoplastic resin composition. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 8 or the thermoplastic resin composition obtained by the production method according to any one of claims 9 to 11. The molded article according to claim 12, wherein the molded article is any one of a spectacle lens, a film, and a sheet.