JP2004292812A - Thermoplastic resin composition, molded article and film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition having high grade thermal resistance, mechanical properties, colorlessness, moldability and solvent-resistance, and moreover, additionally having high grade transparency and optical isotropy. <P>SOLUTION: The thermoplastic resin composition comprises (A) a thermoplastic polymer containing a unit containing glutaric acid anhydride and represented by formula (1) (wherein, R<SP>1</SP>and R<SP>2</SP>are same or differently H or a 1-5C alkyl) and (B) a gum-containing polymer and satisfies following (I) and/or (II). (I) The total light transmittance per 2 mm thickness of the thermoplastic resin composition is ≥90%; (II) the thermoplastic polymer (A) has 30,000-150,000 weight-average molecular weight and ≥130°C glass transition temperature. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a thermoplastic resin composition which is extremely excellent in heat resistance, colorlessness, fluidity, and mechanical properties, and in a more preferred embodiment, excellent transparency, and a molded article and a film containing the thermoplastic resin composition. It is.

  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 components such as optical materials, home electric appliances, OA equipment, and automobiles. And is used in a wide range of fields.

  In recent years, these resins have become widely used, especially for higher performance optical materials such as optical lenses, prisms, mirrors, optical disks, optical fibers, liquid crystal display sheets or films, and light guide plates. The optical properties, moldability, and heat resistance required for the products have also become higher.

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

  However, although 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, PC resin is excellent in heat resistance and impact resistance, but has a large birefringence, which is an optical distortion, causes optical anisotropy to occur in molded products, and has poor moldability, scratch resistance, and solvent resistance. There was a problem that it was extremely poor.

  Therefore, for the purpose of improving the heat resistance of PMMA, a resin in which a maleimide monomer or a maleic anhydride monomer or the like is introduced as a heat-resistance-imparting component has been developed. However, the maleimide monomer is expensive and has low reactivity, and maleic anhydride has a problem of poor thermal stability.

As a method of solving these problems, a glutaric anhydride-containing unit obtained by heating a copolymer containing an unsaturated carboxylic acid monomer unit using an extruder to cause a cyclization reaction is contained. A copolymer is disclosed (see Patent Documents 1 and 2). Further, as a method for improving mechanical properties such as impact resistance, a method of adding a rubbery-containing polymer to a copolymer containing a glutaric anhydride-containing unit has been disclosed (see Patent Documents 3 to 6). ). However, in the methods disclosed in these patent documents, mechanical properties such as impact resistance may be improved to some extent, but mechanical properties such as impact resistance, tensile elongation at break, heat resistance, fluidity, and color tone (Colorless), a composition excellent in solvent resistance and the like was not obtained. Further, there is a problem that the transparency of the resin composition is remarkably reduced, and a problem that the photoelastic coefficient (birefringence) of the resin composition, that is, the optical anisotropy is large. A material having good mechanical properties such as good impact resistance while having properties (transparency and optical isotropy) has not been obtained.
JP-A-49-85184 (page 1-2, Example) JP-A-1-103612 (Page 1-2, Example) JP-A-60-67557 (page 1-2, Example) JP-A-60-120732 (page 1-2, Example) JP-A-4-277546 (page 1-2, Example) JP-A-5-186659 (page 1-2, Example)

  Therefore, the present invention provides a thermoplastic resin composition having high heat resistance and mechanical properties, as well as moldability (fluidity), colorlessness, and solvent resistance. An object of the present invention is to provide a required thermoplastic resin composition having high colorless transparency and optical isotropy.

  The present invention provides (A) a thermoplastic polymer containing a glutaric anhydride-containing unit represented by the following general formula (1),

(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.)
And (B) a thermoplastic resin composition containing a rubbery-containing polymer and satisfying the following (I) and / or (II):
(I) the total light transmittance per 2 mm thickness of the thermoplastic resin composition is 90% or more;
(II) The thermoplastic polymer (A) has a weight average molecular weight of 30,000 to 150,000 and a glass transition temperature of 130 ° C. or more.

  Further, the present invention is a molded article and a film containing the thermoplastic resin composition.

  According to the present invention, a thermoplastic resin composition having high heat resistance and mechanical properties, as well as moldability (flowability), colorlessness, and solvent resistance, and in a more preferred embodiment, in addition to these, recently required in addition to these. Thus, a thermoplastic resin composition having high colorless transparency and optical isotropy can be obtained.

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

As described above, the thermoplastic polymer (A) used in the present invention has the following general formula (1)
(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.)
Is a thermoplastic polymer containing a glutaric anhydride-containing unit represented by the formula:

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

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

  Further, 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.

The determination of the respective component units in the thermoplastic polymer (A) of the present invention generally has an infrared spectrophotometer or a proton nuclear magnetic resonance ⁽¹ H-NMR) measuring machine is used. 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 assignment of the spectrum measured in dimethyl sulfoxide heavy solvent has a peak of 0.5 to 1.5 ppm. The hydrogen of the α-methyl group of methacrylic acid, methyl methacrylate and the glutaric anhydride ring compound, the peak at 1.6 to 2.1 ppm is the hydrogen of the methylene group of the polymer main chain, and the peak at 3.5 ppm is that of methyl methacrylate. Hydrogen of carboxylic acid ester (—COOCH ₃ ), the peak at 12.4 ppm is hydrogen of carboxylic acid of methacrylic acid. In addition, 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 found at 6.5 to 7.5 ppm, and the copolymer is similarly determined from the spectral ratio. The composition can be determined.

  Further, the thermoplastic polymer of the present invention further contains an unsaturated carboxylic acid unit (iii) and / or (iv) other vinyl monomer units in addition to the units (i) and (ii). can do. Here, (iv) other vinyl monomer units are copolymerizable vinyl monomer units that do 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 0-5% by weight, most preferably 0-1% by weight. When the amount of the unsaturated carboxylic acid unit (iii) exceeds 10% by weight, colorless transparency and retention stability tend to decrease.

  Further, the content of the other vinyl monomer unit (iv) is preferably 10% by weight or less, that is, 0 to 10% by weight based on 100% by weight of the thermoplastic polymer (A). The other vinyl monomer unit (iv) is preferably a vinyl monomer unit containing no aromatic ring. In the case of an aromatic vinyl monomer unit such as styrene, if the content is high, colorless transparency, optical isotropy, and solvent resistance tend to decrease, so that it is 5% by weight or less, that is, 0 to 5% by weight. And more preferably 0 to 3% by weight.

  The unsaturated carboxylic acid unit (iii) preferably has a structure represented by the following general formula (2).

(However, R ³ 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 (3).

(However, R ⁴ represents hydrogen or an alkyl group having 1 to ⁵ carbon atoms, and R ⁵ represents an aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms or a hydroxyl group or halogen having 1 or more carbon atoms or less.) Represents an aliphatic or alicyclic hydrocarbon group having 1 to 6 carbon atoms substituted with
Further, 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 in this range, coloring during heating degassing in the subsequent step can be reduced, a polymer having a small yellowness can be obtained, and the mechanical strength of a molded article can be increased. . In addition, the weight average molecular weight referred to in the present invention indicates a weight average molecular weight as an absolute molecular weight measured by multi-angle light scattering gel permeation chromatography (GPC-MALLS).

  In addition, the thermoplastic polymer (A) preferably has a glass transition temperature (Tg) of 130 ° C. or higher from the viewpoint of heat resistance. The glass transition temperature is more preferably 140 ° C. or higher, and particularly preferably 150 ° C. or higher. The upper limit is usually about 170 ° C. 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 (DSK-7 manufactured by Perkin Elmer).

  The thermoplastic polymer (A) thus obtained has a very low yellowness (Yellowness Index) value of 5 or less, and coloring is extremely suppressed. In a more preferred embodiment, it is 4 or less, and in the most preferred embodiment, it is 3 or less. It is colorless. As a result, the thermoplastic resin composition of the present invention containing the thermoplastic polymer (A) can also have a yellowness of 5 or less, more preferably 4 or less, and most preferably 3 or less. It is preferable because a molded article or a film having the following can be obtained. When the thermoplastic polymer (A) has a large yellowness value, a part of the thermoplastic polymer (A) is thermally decomposed, and the thermoplastic polymer (A) of the present invention containing the thermoplastic polymer (A) is decomposed. The mechanical properties of the plastic resin composition tend to decrease. Also in this respect, the yellowness of the thermoplastic polymer (A) is preferably in the above range. In addition, the yellowness (Yellowness Index) here means that the thermoplastic polymer (A) or the thermoplastic resin composition of the present invention is injection-molded, and the obtained molded product having a thickness of 2 mm is subjected to SM according to JIS-K7103. It is a YI value measured using a color computer (manufactured by Suga Test Instruments Co., Ltd.).

  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 following method. That is, an unsaturated carboxylic acid monomer and an unsaturated carboxylic acid alkyl ester monomer that give the glutaric anhydride-containing unit (i) represented by the above general formula (1) in a subsequent heating step are copolymerized, A copolymer (a) is obtained. In that case, when the other vinyl monomer unit (iv) is contained, a vinyl monomer giving the unit may be copolymerized. The obtained copolymer (a) is heated in the presence or absence of a suitable catalyst to cause an intramolecular cyclization reaction by dealcoholization and / or dehydration, thereby converting the thermoplastic polymer (A). Can be manufactured. In this case, typically, by heating the copolymer (a), a dehydration reaction between the carboxyl groups of two adjacent unsaturated carboxylic acid units (iii) or an adjacent unsaturated carboxylic acid unit The dealcoholation reaction between the acid unit (iii) and the unsaturated carboxylic acid alkyl ester unit (ii) produces one unit of the aforementioned (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. Preferred unsaturated carboxylic acid monomers include compounds represented by the following general formula (4), maleic acid, and hydrolysates of maleic anhydride. In particular, acrylic acid and methacrylic acid are preferred because of their excellent thermal stability, and methacrylic acid is more preferred. These can be used alone or in combination of two or more. 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.

(However, R ³ represents hydrogen or an alkyl group having 1 to 5 carbon atoms)
Preferred examples of the unsaturated carboxylic acid alkyl ester monomer include those represented by the following general formula (5).

(However, R ⁴ represents hydrogen or an alkyl group having 1 to ⁵ carbon atoms, and R ⁵ represents an aliphatic group or an alicyclic hydrocarbon group having 1 to 6 carbon atoms. Here, R ⁵ is one or more. It may be substituted with a hydroxyl group or a halogen having a number of carbon atoms or less.)
Of these, acrylates and / or methacrylates 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. .

  Preferred specific 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, acrylate 6-penta Droxyhexyl, 2,3,4,5,6-pentahydroxyhexyl methacrylate, 2,3,4,5-tetrahydroxypentyl acrylate and 2,3,4,5-tetrahydroxypentyl methacrylate and the like. Of these, methyl methacrylate is most preferably used. One or more of these can be used.

  In the production of the copolymer (a) used in the present invention, other vinyl monomers may be used as long as the effects of the present invention are not impaired. This other vinyl monomer gives the above-mentioned other vinyl monomer unit (iv) when copolymerized. Preferred specific examples of other vinyl monomers include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene and pt-butylstyrene. Vinyl monomer, vinyl cyanide monomer 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, propyl 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. A monomer containing no aromatic ring can be more preferably used in terms of transparency, optical isotropy, and solvent resistance. These can be used alone or in combination of two or more.

  As the polymerization method of the copolymer (a), a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be basically used by radical polymerization. Solution polymerization, bulk polymerization, and suspension polymerization are particularly preferred in that they have less impurities.

  Regarding the polymerization temperature, from the viewpoint of color tone, it is preferable to carry out the polymerization at a polymerization temperature of 95 ° C. or lower. In order to further suppress the coloring after the heat treatment, the preferable polymerization temperature is 85 ° C or lower, 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, and 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 the polymerization rate, it is possible to raise the polymerization temperature as the polymerization proceeds. Also in this case, it is preferable to control the upper limit temperature at which the temperature rises to 95 ° C. or lower, and it is preferable to perform the polymerization at a relatively low temperature of 75 ° C. or lower. The polymerization time is not particularly limited as long as it is a time sufficient to obtain a required degree of polymerization, but is preferably in the range of 60 to 360 minutes, and particularly preferably in the range of 90 to 180 minutes from the viewpoint of production efficiency.

  In the present invention, the preferable ratio of these monomer mixtures used in the production of the copolymer (a) is 15 to 50% by weight based on 100% by weight of the entire monomer mixture. %, 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 copolymerizable vinyl monomers 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 producing the thermoplastic polymer (A) by heating the copolymer (a), the above-mentioned general formula (1) The amount of the generated glutaric anhydride-containing unit (i) is reduced, and the effect of improving the heat resistance of the thermoplastic polymer (A) tends to decrease. On the other hand, when the content of the unsaturated carboxylic acid monomer (iii) exceeds 50% by weight, 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 retention stability of the thermoplastic polymer (A) tend to decrease.

  In addition, 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 can be obtained by controlling the copolymer (a) to 30,000 to 150,000 in weight average molecular weight in advance during the production of the copolymer (a). Can be achieved.

  Regarding the method for controlling the molecular weight of the copolymer (a), for example, the amount of a radical polymerization initiator such as an azo compound or a peroxide, or an alkyl mercaptan, carbon tetrachloride, carbon tetrabromide, dimethylacetamide, dimethylformamide, It can be controlled by the amount of a chain transfer agent such as triethylamine added. In particular, a method of controlling the amount of the alkyl mercaptan which is a chain transfer agent can be preferably used in view of the stability of polymerization, ease of handling, and the like.

  Examples of the alkyl mercaptan used in the present invention include, for example, n-octyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, n-octadecyl mercaptan and the like, among which t-dodecyl mercaptan, n-Dodecyl mercaptan is preferably used.

  The amount of addition of these alkyl mercaptans is not particularly limited as long as it is controlled to the specific molecular weight of the present invention. 0.3 to 5.0 parts by weight, preferably 0.8 to 5.0 parts by weight, more preferably 0.9 to 4.0 parts by weight, based on 100 parts by weight of the total amount of the mixture. More preferably, the amount is 1.0 to 3.0 parts by weight. For example, when t-dodecyl mercaptan is used, it is particularly effective in the range of 1.0 to 3.0 parts by weight, and when n-dodecyl mercaptan is used, 0.6 to 2.0 parts by weight. Is particularly effective in the range of

  The method for producing a thermoplastic polymer (A) containing a glutaric anhydride-containing unit by heating the copolymer (a) in the present invention and performing an intramolecular cyclization reaction by dehydration and / or dealcoholation includes: 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 under vacuum is preferable. When an intramolecular cyclization reaction is caused by heating in the presence of oxygen, the yellowness tends to deteriorate. Therefore, it is preferable to sufficiently replace the system with an inert gas such as nitrogen. As a particularly preferred apparatus, for example, a single-screw extruder equipped with a "Unimelt" type screw, a twin-screw extruder, a triple-screw extruder, or a continuous or batch kneader-type kneader can be used. Machine can be preferably used. Further, an apparatus having a structure into which an inert gas such as nitrogen can be introduced is more preferable. For example, as a method of introducing an inert gas such as nitrogen into the twin-screw extruder, a method of connecting a pipe of an inert gas flow of about 10 to 100 liter / min from the upper part and / or the lower part of the hopper may be mentioned. .

  In addition, the temperature for heat devolatilization by the above-mentioned method is not particularly limited as long as an intramolecular cyclization reaction is caused by dehydration and / or dealcoholation, but is preferably in a range of 180 to 300 ° C, particularly preferably 200 to 300 ° C. 280 ° C. range.

  In addition, the time for heat devolatilization at this time can be appropriately set according to a desired copolymer composition, but is usually preferably 1 minute to 60 minutes, more preferably 2 minutes to 30 minutes, and particularly preferably 3 minutes. -20 minutes. The length / diameter ratio (L / D) of the screw of the extruder is preferably 40 or more in order to secure a heating time for causing a sufficient intramolecular cyclization reaction to proceed using the extruder. 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 at the time of heat molding, and there is a tendency for silver and bubbles to be seen in the molded product, and molding retention. Sometimes the color tone tends to deteriorate.

  Further, in the present invention, as a catalyst for promoting the cyclization reaction to glutaric anhydride when the copolymer (a) is heated by the above method or the like, at least one selected from acids, alkalis and salt compounds is added. can do. The addition amount is preferably about 0.01 to 1 part by weight based on 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, and ammonium hydroxide salts. Further, examples of the salt compound catalyst include metal acetate, metal stearate, and metal carbonate. However, it is preferable to add the catalyst within a range in which the color of the catalyst does not adversely affect the coloring of the thermoplastic polymer and the transparency does not decrease. Among them, a compound containing an alkali metal can be preferably used because it exhibits an excellent reaction promoting effect with a relatively small amount of addition. Specifically, hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, sodium methoxide, sodium ethoxide, sodium phenoxide, potassium methoxide, potassium ethoxide, alkoxide compounds such as potassium phenoxide, lithium acetate And organic carboxylate such as sodium acetate, potassium acetate and sodium stearate. Especially, 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 significantly impairing the excellent properties of the thermoplastic polymer (A). Can be given. (B) The rubber-containing polymer is composed of a layer containing one or more rubbery polymers and one or more layers composed of a polymer different from that, and one or more layers of rubber therein. Copolymerization of a monomer mixture composed of a vinyl monomer or the like in the presence of a so-called core-shell type multilayer polymer (B-1) having a structure having a layer containing a rubbery polymer, or a rubbery polymer Grain copolymer (B-2) or the like can be preferably used.

  The number of layers constituting the core-shell type multilayer polymer (B-1) used in the present invention may be two or more, and may be three or more or four or more. It is preferably a multilayer polymer having one or more rubber layers (core layers).

  In the multilayer polymer (B-1) of the present invention, the type of the rubber layer is not particularly limited as long as it is composed of a polymer component having rubber elasticity. For example, a rubber composed of an acrylic component, a silicone component, a styrene component, a nitrile component, a conjugated diene component, a urethane component or a polymer obtained by polymerizing an ethylene component, a propylene component, an isobutene component, or the like can be used. Preferred rubbers include, for example, acrylic components such as ethyl acrylate units and butyl acrylate units, silicone components such as dimethylsiloxane units and phenylmethylsiloxane units, styrene components such as styrene units and α-methylstyrene units, and acrylonitrile units. It is a rubber composed of a nitrile component such as a methacrylonitrile unit and a conjugated diene component such as a butanediene unit and an isoprene unit. Further, a rubber composed of a combination of two or more of these components is also preferable. For example, (1) a rubber composed of an acrylic component such as an ethyl acrylate unit or a butyl acrylate unit and a silicone component such as a dimethylsiloxane unit or a phenylmethylsiloxane unit; (2) an ethyl acrylate unit or a butyl acrylate unit; (3) An acrylic component such as an ethyl acrylate unit or a butyl acrylate unit and a conjugated diene component such as a butanediene unit or an isoprene unit. Constituent rubber, and (4) acrylic components such as ethyl acrylate units and butyl acrylate units, silicone components such as dimethylsiloxane units and phenylmethylsiloxane units, and styrene components such as styrene units and α-methylstyrene units And the like. Of these, rubbers containing an alkyl acrylate unit and a substituted or unsubstituted styrene unit are most preferred in terms 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 (B-1) of the present invention, the type of the layer other than the rubber layer is not particularly limited as long as the layer is composed of a thermoplastic polymer component. Is also preferably a polymer component having a high glass transition temperature. Examples of the polymer having thermoplasticity 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, and cyanated. Polymers containing one or more units selected from vinyl units, maleimide units, unsaturated dicarboxylic acid units, and other vinyl units are exemplified. Above all, a polymer containing an unsaturated carboxylic acid alkyl ester unit is preferable, and in addition, it contains one or more units selected from an unsaturated glycidyl group-containing unit, an unsaturated carboxylic acid unit and an unsaturated dicarboxylic anhydride unit. Are preferred.

  The monomer used as the raw material for the unsaturated carboxylic acid alkyl ester unit is not particularly limited, but alkyl acrylate or alkyl methacrylate is preferably used. 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 Ethyl, dimethylaminoethyl methacrylate, ethylaminopropyl methacrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, and the like.From the viewpoint that the effect of improving impact resistance is large, methyl acrylate or methacrylic acid is used. Methyl acid are preferably used. These units may 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 a hydrolyzate of maleic anhydride. In particular, acrylic acid and methacrylic acid are preferred because of their excellent thermal stability, and methacrylic acid is more preferred. These can be used alone or in combination of two or more.

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

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

  In addition, ethylene, propylene, butadiene, and the like can be used as a monomer that is a raw material of the aliphatic vinyl unit. Examples of the monomer as a raw material of 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, and the like can be used as a monomer as a raw material of the vinyl cyanide unit. Examples of the monomer serving as a raw material of the maleimide unit include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, and N- (p-maleimide). Bromophenyl) maleimide and N- (chlorophenyl) maleimide can be used. As a monomer which is a raw material of the unsaturated dicarboxylic acid unit, maleic acid, monoethyl maleate, itaconic acid, phthalic acid and the like can be used. Examples of the monomer as a raw material of the above-mentioned other 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 and 2-styryl-oxazoline. These monomers can be used alone or in combination of two or more.

  In the multilayer polymer (B-1) containing the rubbery polymer according to the present invention, the type of the outermost layer (shell layer) includes an unsaturated carboxylic acid alkyl ester unit, an unsaturated carboxylic acid unit, and an unsaturated glycidyl group-containing. Unit, an aliphatic vinyl unit, an aromatic vinyl unit, a vinyl cyanide unit, a maleimide unit, an unsaturated dicarboxylic acid unit, an unsaturated dicarboxylic anhydride unit and at least one selected from polymers containing other vinyl units and the like. One type is mentioned. Among them, at least one selected from an unsaturated carboxylic acid alkyl ester unit, an unsaturated carboxylic acid unit, an unsaturated glycidyl group-containing unit and an unsaturated dicarboxylic anhydride unit is preferable. Polymers containing unsaturated carboxylic acid alkyl ester units and unsaturated carboxylic acid units are most preferred.

  In the present invention, when the outermost layer in the above-mentioned multilayer polymer (B-1) is a polymer containing an unsaturated carboxylic acid alkyl ester unit and an unsaturated carboxylic acid unit, the above-mentioned present invention is applied by heating. In the same manner as in the production of the thermoplastic copolymer (A), it has been found that the intramolecular cyclization reaction proceeds to generate the glutaric anhydride-containing unit represented by the general formula (1). Therefore, a multilayer structure polymer (B-1) having a polymer containing an unsaturated carboxylic acid alkyl ester unit and an unsaturated carboxylic acid unit in the outermost layer is blended with the thermoplastic copolymer (A), and the appropriate conditions are applied. By heating and kneading, a multilayer polymer (B-1) containing the glutaric anhydride-containing unit represented by the general formula (1) in the outermost layer is obtained. This makes it possible for the multilayer structure polymer (B-1) to be well dispersed without agglomeration in the thermoplastic copolymer (A) serving as a continuous phase (matrix phase). It is considered that a very high degree of transparency can be exhibited together with the improvement of mechanical properties such as impact resistance of the thermoplastic resin composition.

  As the monomer which is a raw material of the unsaturated carboxylic acid alkyl ester unit, alkyl acrylate or alkyl methacrylate is preferable, and methyl acrylate or methyl methacrylate is more preferably used.

  Further, as a monomer which is a raw material of the unsaturated carboxylic acid unit, acrylic acid or methacrylic acid is preferable, and methacrylic acid is more preferably used.

  Preferred examples of the multilayer polymer (B-1) of the present invention include a core layer of butyl acrylate / styrene copolymer, and an outermost layer of methyl methacrylate / glutaric acid represented by the general formula (1). A copolymer comprising an anhydride-containing unit, wherein the core layer is a butyl acrylate / styrene copolymer and the outermost layer is methyl methacrylate / the glutaric anhydride-containing unit represented by the general formula (1) / Methacrylic acid copolymer, core layer of dimethylsiloxane / butyl acrylate copolymer and outermost layer of methyl methacrylate polymer, core layer of butanediene / styrene copolymer and outermost layer of methyl methacrylate Polymers and those in which the core layer is a butyl acrylate polymer and the outermost layer is a methyl methacrylate polymer, and the like. Here, “/” indicates copolymerization. Further, a preferable example is one in which one or both of the rubber layer and the outermost layer is a polymer containing a glycidyl methacrylate unit. Among them, the core layer is a butyl acrylate / styrene polymer, the outermost layer is a copolymer of methyl methacrylate / glutaric anhydride-containing unit represented by the above general formula (1), and the core layer is an acrylic resin. A butyl acrylate / styrene copolymer in which the 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 is possible to approximate the refractive index with the thermoplastic copolymer (A) and to obtain a good dispersion state in the resin composition, and to exhibit transparency that can satisfy the demand for higher sophistication in recent years. Therefore, it can be preferably used.

  The number average particle diameter of the multilayer polymer (B-1) of the present invention is preferably 0.01 μm or more from the viewpoint of impact strength of the obtained thermoplastic resin composition, and is preferably 1000 μm or less from the viewpoint of transparency. Further, the thickness 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.

  In the multilayer structure polymer (B-1) 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 with respect to the whole multilayer structure polymer. , 60% by weight or more and 80% by weight or less.

  As the multilayer structure polymer of the present invention, a commercially available product satisfying the above-mentioned conditions may be used, or it may be prepared and used by a known method.

  Commercial products of the multilayer polymer include, for example, "METABLEN (registered trademark)" manufactured by Mitsubishi Rayon Co., Ltd., "KANEACE (registered trademark)" manufactured by Kanegafuchi Chemical Industry Co., Ltd., and "PARALOID (registered trademark)" manufactured by Kureha Chemical Industry Co., Ltd. "Acryloid (registered trademark)" manufactured by Rohm and Haas Co., Ltd., "Staphyroid (registered trademark)" manufactured by Ganz Kasei Kogyo, and "Parapet (registered trademark) SA" manufactured by Kuraray Co., Ltd. More than one species can be used.

  Specific examples of the rubber-containing graft copolymer (B-2) used as the rubber-containing polymer (B) in the present invention include, in the presence of a rubber-like polymer, an unsaturated carboxylic acid ester Graft copolymer obtained by copolymerizing a monomer mixture of a monomer, an unsaturated carboxylic acid monomer, an aromatic vinyl monomer, and another vinyl monomer copolymerizable therewith, if necessary. Is mentioned.

  As the rubbery polymer used for the graft copolymer (B-2), diene rubber, acrylic rubber, ethylene rubber and the like can be used. Specific examples include polybutadiene, styrene-butadiene copolymer, styrene-butadiene block copolymer, acrylonitrile-butadiene copolymer, butyl acrylate-butadiene copolymer, polyisoprene, and 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 And copolymers. 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 (B-2) in the present invention is preferably in the range of 0.1 to 0.5 μm, particularly preferably 0.15 to 0.4 μm. When the amount is less than the above range, the impact strength of the obtained thermoplastic resin composition tends to decrease. When the amount exceeds the above range, transparency may decrease. The weight average particle size of the rubbery polymer is determined by the sodium alginate method described in `` Rubber Age, Vol. 88, p. 484-490 (1960), by E. Schmidt, PHBiddison '', that is, by the concentration of sodium alginate. Utilizing the fact that the particle diameters of polybutadiene to be creamed are different, it can be measured by a method of determining the particle diameter at a cumulative weight fraction of 50% from the cumulative weight fraction of the creamed weight ratio and the sodium alginate concentration.

  The graft copolymer (B-2) in the present invention may be 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, (Mixture) It is obtained by copolymerizing 20 to 90% by weight, preferably 30 to 80% by weight, more preferably 40 to 70% by weight. If the proportion of the rubbery polymer is less than the above range or exceeds the above range, impact strength and surface appearance may be reduced.

  In addition, the graft copolymer (B-2) may include a non-grafted copolymer generated when the monomer mixture is graft-copolymerized with the rubbery polymer. From the viewpoint of impact strength, the graft ratio is preferably from 10 to 100%. Here, the graft ratio is a weight ratio of the grafted monomer mixture to the rubbery polymer. In addition, the intrinsic viscosity of the non-grafted copolymer measured at 30 ° C. in a methyl ethyl ketone solvent 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 vinyl copolymer (B-2) measured at 30 ° C. of the vinyl copolymer (B-2) in the present invention is not particularly limited. It is preferably used from the viewpoint of balance with the properties, and more preferably 0.3 to 0.7 dl / g.

  The method for producing the graft copolymer (B-2) in the present invention is not particularly limited, and it can be obtained by a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.

  Further, it is preferable that the respective refractive indexes of the thermoplastic polymer (A) and the rubber-containing polymer (B) are similar, since a thermoplastic resin composition having excellent transparency can be obtained. Specifically, the difference between the two refractive indices 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) a method of adjusting each monomer unit composition ratio of the thermoplastic polymer, and / or (B) a rubber material used for the rubber-containing polymer are used. A method of adjusting the composition ratio of the union or the monomer may be used.

  The difference in the refractive index referred to here means that the thermoplastic resin composition of the present invention is sufficiently dissolved in a solvent in which the thermoplastic polymer is soluble under appropriate conditions (A) to form a cloudy solution, which is then centrifuged. And the like, the solvent-soluble portion and the insoluble portion were separated, and the soluble portion ((A) thermoplastic polymer) and the insoluble portion ((B) rubber-containing polymer) were purified and measured. The difference in refractive index (23 ° C., measurement wavelength: 550 nm) is shown.

  In the resin composition, the copolymer composition of (A) the thermoplastic polymer and (B) the rubber-containing polymer is obtained by separating each component from the soluble component and the insoluble component using the above-described solvent. Can be analyzed.

  In the present invention, the weight ratio of the thermoplastic polymer (A) to the rubber-containing polymer (B) is preferably in the range of 99/1 to 50/50, and more preferably 99/1 to 60/40. Is more preferable, and the range of 99/1 to 70/30 is most preferable.

  The total light transmittance of the thermoplastic resin composition of the present invention is 90% or more, preferably 92% or more. Thereby, it has extremely excellent transparency. The upper limit of the total light transmittance is usually about 94%.

  In the thermoplastic resin composition of the present invention, the haze value (turbidity), which is one of the indexes indicating transparency, is preferably 3% or less, more preferably 1% or less. This has a high degree of transparency. The lower limit of the haze value is usually about 0.5%.

  The total light transmittance and the haze of the thermoplastic resin composition are values obtained by measuring a molded product having a thickness of 2 mm obtained by injection molding in accordance with JIS-K7361 and JIS-K7136.

Further, the photoelastic coefficient of the thermoplastic resin composition of the present invention is preferably 5 × 10 ⁻¹² Pa ⁻¹ or less, more preferably 4 × 10 ⁻¹² Pa ⁻¹ or less. Thereby, it has extremely excellent optical isotropy. Further, the lower limit of the photoelastic coefficient is usually about 2 × 10 ⁻¹² Pa ⁻¹ . The photoelastic coefficient referred to here is a stress (σ) when a non-oriented film having a thickness of about 100 μm (100 ± 5 μm) obtained by a casting method is uniaxially stretched 1.5 times and this The stretched film was irradiated with a laser beam at 23 ° C. using an ellipsometer (manufactured by Otsuka Electronics Co., Ltd., LCD cell gap inspection device RETS-1100) at an angle of 90 ° with respect to the film sample surface, and transmitted light at 633 nm. It is a value calculated by the following formula based on the measured retardation (Re) and the thickness (d) at 23 ° C. of the stretched film.

Photoelastic coefficient = Re (nm) / d (nm) / σ (Pa)
The thermoplastic resin composition of the present invention preferably has a heat distortion temperature of 100 ° C. or higher, more preferably 110 ° C. or higher, and particularly preferably 115 ° C. or higher. Thereby, it has extremely excellent heat resistance. The upper limit of the heat distortion temperature is usually about 140 ° C. Here, the heat distortion temperature refers to a value obtained by measuring a molded product having a thickness of 6.4 mm obtained by injection molding in accordance with ASTM D648.

  Further, the thermoplastic polymer of the present invention, the thermoplastic resin composition, other thermoplastic resins, for example, polyethylene, polypropylene, acrylic resin, polyamide, polyphenylene sulfide resin, polyether ether, as long as the object of the present invention is not impaired. Ketone resins, polyesters, polysulfones, polyphenylene oxides, polyacetals, polyimides, polyetherimides, and the like, further contain at least one selected from thermosetting resins such as phenolic resins, melamine resins, polyester resins, silicone resins, and epoxy resins. Can be done. Also, hindered phenol-based, benzotriazole-based, benzophenone-based, benzoate-based, and cyanoacrylate-based ultraviolet absorbers and antioxidants, lubricants and plasticizers such as higher fatty acids, acid esters, and acid amides, and higher alcohols , Montanic acid and its salts, its esters, its half esters, release agents such as stearyl alcohol, stearamide and ethylene wax, coloring inhibitors such as phosphites and hypophosphites, halogen-based flame retardants, phosphorus-based And an additive such as a silicone-based non-halogen flame retardant, a nucleating agent, an amine-based, sulfonic acid-based, polyether-based antistatic agent, and a coloring agent such as a pigment. However, in view of the characteristics required by the application to which the composition is applied, it is preferable to add the additive within a range in which the color of the additive does not adversely affect the thermoplastic polymer and the transparency does not decrease.

  In the present invention, as a method of blending (A) the thermoplastic polymer and (B) the rubber-containing polymer, (A) the thermoplastic polymer and other optional components are blended in advance, and usually at 200 to 350 ° C. A method of uniformly kneading and melt-mixing with a single screw or twin screw extruder is preferably used. A method in which the components (A) and (B) are mixed in a solution of a solvent that dissolves both components and then the solvent is removed can also be used.

  Further, as a method for producing the thermoplastic resin composition of the present invention, after previously blending the above-mentioned copolymer (a) and (B) a rubber-containing polymer, usually at 200 to 350 ° C., uniaxial or biaxial extrusion is performed. By uniformly kneading and kneading with a machine, the conversion of the copolymer (a) into the thermoplastic polymer (A) by the cyclization reaction described above can be performed, and at the same time, the component (B) can be blended. At this time, a cyclization reaction can also be performed at the same time when the copolymer comprising an unsaturated carboxylic acid monomer unit and an unsaturated carboxylic acid alkyl ester monomer unit is partially contained in the component (B). .

  The thermoplastic resin composition of the present invention has excellent mechanical properties and moldability, and can be melt-molded, so that extrusion molding, injection molding, press molding, and the like 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.

  Known methods can be used for the method for producing a film made of the thermoplastic resin composition of the present 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 pressing method can be used. In the case of the production method by the inflation method or the T-die method, an extruder-type melt extruder equipped with a single-screw or twin-screw extrusion screw can be used. The melt extrusion temperature for producing the film of the present invention is preferably from 150 to 350C, more preferably from 200 to 300C. When melt kneading is performed using a melt extruder, it is preferable to use a vent to perform melt kneading under reduced pressure or melt kneading under a nitrogen stream from the viewpoint of suppressing coloration. When the film of the present invention is produced by a casting method, solvents such as tetrahydrofuran, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, and 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-mentioned solvents, and using a bar coater, a T-die, a T-die with a bar, a die coat, or the like to form a heat-resistant film such as polyethylene terephthalate. It can be produced by casting on a flat plate or a curved plate (roll) such as a film, a steel belt or a metal foil and using a dry method of evaporating and removing the solvent or a wet method of solidifying the solution with a coagulating liquid.

  The molded product or film thus obtained can be used in various applications such as housings of electric / electronic parts, automobile parts, mechanical mechanism parts, OA equipment, home electric appliances and the like, and their parts, general miscellaneous goods by utilizing its excellent heat resistance. Can be used.

  In particular, because of their excellent transparency and heat resistance, various components such as cameras, VTRs, projection lenses such as cameras, VTRs and projection TVs, viewfinders, filters, prisms, Fresnel lenses, etc. Liquid crystal display, flat panel display, plasma display as information equipment related parts such as optical disk (VD, CD, DVD, MD, LD, etc.) substrates, various disk substrate protection films, optical disk player pickup lenses, optical fibers, optical switches, optical connectors, etc. Light guide plate, Fresnel lens, polarizing plate, polarizing plate protective film, retardation film, light diffusion film, viewing angle widening film, reflection film, antireflection film, antiglare film, brightness enhancement film, prism sheet, pickup lens Tail lamp lenses, headlamp lenses, inner lenses, amber caps, reflectors, extensions, side mirrors, room mirrors, side visors, instrument needles, instrument covers, windows, etc. Medical device related parts such as glazing represented by glass; spectacle lenses, spectacle frames, contact lenses, endoscopes, analytical optical cells, etc .; building material related parts: daylighting windows, road translucent boards, lighting covers, signboards It is extremely useful for applications such as light-transmitting sound insulating 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. Prior to the description of each example, methods for measuring various physical properties used in the examples are described.

(1) Weight average molecular weight (absolute molecular weight)
The thermoplastic polymer (A) was dissolved in dimethylformamide to obtain a measurement sample. Gel permeation chromatograph (pump: 515, Waters, column: TSK-gel-GMH _XL , Tosoh) equipped with a DAWN-DSP type multi-angle light scattering photometer (Wyatt Technology) using dimethylformamide as a solvent. Was used to determine the weight average molecular weight (absolute molecular weight).

(2) Glass transition temperature (Tg)
Using a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer), the measurement was performed at a heating rate of 20 ° C./min in a nitrogen atmosphere.

(3) Heat Deformation Temperature The thermoplastic resin composition of the present invention is injection-molded at a glass transition temperature of the thermoplastic polymer (A) + 150 ° C. to obtain a 127 mm × 12.7 mm × 6.4 mm plate-shaped test piece. Obtained. Using the obtained plate-shaped test piece, the deflection temperature under load was measured according to ASTM D648 (load: 1.82 MPa), and the heat resistance was evaluated.

(4) Transparency (total light transmittance, haze)
The thermoplastic resin composition of the present invention was injection-molded at a glass transition temperature of the thermoplastic polymer (A) + 150 ° C. to obtain a molded product of 70 mm × 70 mm × 2 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 article were measured to evaluate the transparency.

  When measuring a molded product having a thickness of not more than 2 mm, the molded product may be crushed once, and a molded product of 70 mm × 70 mm × 2 mm may be molded under the above conditions and measured.

(5) Izod impact strength (Izod impact value)
The thermoplastic resin composition of the present invention was injection-molded at a glass transition temperature of the thermoplastic polymer (A) + 150 ° C. to obtain a 12.7 mm thick notched test piece according to ASTM D-256. Using the obtained test piece, Izod impact strength was measured at 23 ° C. in accordance with ASTM D-256 to evaluate impact properties.

(6) Elongation at break The thermoplastic resin composition of the present invention is supplied to a 40 mm diameter vented single screw extruder equipped with a 200 mm wide T-die for film production, and extruded at 280 ° C at a rate of 10 kg / h. Thus, a film having a thickness of 0.1 mm was obtained. An ASTM-1 dumbbell was punched out of the obtained film to prepare a test piece, and the tensile elongation at break was measured in accordance with JIS K-7113.

(7) Photoelastic coefficient The thermoplastic resin composition of the present invention was dissolved in methyl ethyl ketone to obtain a 25% by weight solution. Using the obtained solution, a non-oriented film having a thickness of about 100 μm (100 ± 5 μm) was obtained by a casting method. The non-oriented film was uniaxially stretched 1.5 times at the glass transition temperature of the thermoplastic resin (A) + 5 ° C at a rate of 0.5 mm / sec, and the stress (σ) was measured. The stretched film is irradiated with a laser beam at an angle of 90 ° to the film sample surface at 23 ° C. using an ellipsometer (manufactured by Otsuka Electronics Co., Ltd., LCD cell gap inspection device RETS-1100) according to ASTM D542. Then, the retardation (Re) of the transmitted light at 633 nm was measured. Further, the thickness (d) at 23 ° C. of the stretched film was measured using a Mitutoyo Digimatic Indicator, and the photoelastic coefficient was calculated from the following formula based on the thickness.

Photoelastic coefficient = Re (nm) / d (nm) / σ (Pa)
(8) Refractive index, refractive index difference Acetone is added to the thermoplastic resin composition of the present invention, and after refluxing for 4 hours, the mixture is centrifuged at 9,000 rpm for 30 minutes to be insoluble in the acetone-soluble component (A component). (B component). These were each dried under reduced pressure at 60 ° C. for 5 hours. Each of the obtained solids was press-formed at 250 ° C. to form a film having a thickness of 0.1 mm, and the refractive index at 23 ° C. and a wavelength of 550 nm was measured with an Abbe refractometer (DR-M2 manufactured by Atago Co., Ltd.). It was measured. The absolute value of the difference between the refractive index of the component A and the refractive index of the component B was defined as the refractive index difference.

(9) Composition of each component The acetone-soluble component (component A) separated and extracted in (8) above was measured by ¹ H-NMR at 30 ° C. in heavy dimethyl sulfoxide to determine the composition of each copolymerized unit. Was done. The acetone-insoluble fraction was separated and extracted in the above (8) (B component), infrared spectroscopy, by the presence or absence of the absorption peak of 1800 cm ^-1 and 1760 cm ^-1 which is a characteristic peak of glutaric anhydride containing units The formation of glutaric anhydride-containing units was confirmed.

(10) Yellowness Index (YI)
The thermoplastic polymer (A) or the thermoplastic resin composition of the present invention was injection-molded at a glass transition temperature of the thermoplastic polymer (A) + 150 ° C to obtain a 70 mm x 70 mm x 2 mm molded product. 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.

  When measuring a molded product having a thickness of not more than 2 mm, the molded product may be crushed once, and a molded product of 70 mm × 70 mm × 2 mm may be molded under the above conditions and measured.

(11) Fluidity For the thermoplastic resin composition of the present invention, the melt index (MI value) at a temperature: the glass transition temperature of the thermoplastic polymer (A) + 150 ° C. and a load: 37.3 N according to the ISO-R1133 method. It was measured.

(12) Solvent resistance The thermoplastic resin composition of the present invention is injection-molded at a glass transition temperature of the thermoplastic polymer (A) + 150 ° C., and as a test piece, 12.5 mm × 125 mm × 1 shown in FIG. A plate-shaped molded product 1 of 0.6 mm was obtained. After fixing the molded product along the curved surface 3 of the 1/4 elliptical jig 2 as shown in FIG. 1, a wax remover ("Wax Remover CPC" manufactured by Yushiro Chemical Co., Ltd.) or toluene / A mixed solvent of methyl isobutyl ketone (MIBK) = 50/50% by weight was applied to the entire surface of the molded article. After being left for 24 hours in an environment of 23 ° C., the presence or absence of cracks and their positions were confirmed. FIG. 1 is a schematic view of a 1/4 elliptical jig and a plate-like molded product in this evaluation. The shortest axial length (X) of the crack occurrence position was measured, and the critical strain τ (%) was calculated by the following equation. Judged.

τ = b / 2a ² [1- (a ² -b ² ) X ² / a ⁴ ] ^-3/2 × t × 100
τ: Critical strain (%)
a: Long axis of the jig (127 mm)
b: Short axis of jig (38.1 mm)
t: thickness of test piece (1.6 mm)
X: The shortest axial length (mm) of the crack occurrence position.

<Reference example (1) Synthesis of copolymer (a)>
(A-1)
20 parts by weight of methyl methacrylate, 80 parts by weight of acrylamide, 0.3 parts by weight of potassium persulfate and 1500 parts by weight of ion-exchanged water were charged into a reactor, and the reactor was maintained at 70 ° C. while substituting with nitrogen gas. The reaction was continued until the monomer was completely converted to a polymer, to obtain an aqueous solution of a methyl methacrylate / acrylamide copolymer. The resulting aqueous solution was used as a suspending agent. A solution prepared by dissolving 0.05 parts by weight of the above-mentioned methyl methacrylate / acrylamide copolymer suspension in 165 parts by weight of ion-exchanged water was placed in a stainless steel autoclave having a capacity of 5 liters and equipped with a baffle and a Fowler type stirring blade. The mixture was supplied, stirred at 400 rpm, and the system was replaced with nitrogen gas. Next, the following mixture was added while stirring the reaction system, and the temperature was raised to 70 ° C. The time when the internal temperature reached 70 ° C. was defined as the start of polymerization, and was maintained for 180 minutes to complete the polymerization. Thereafter, the reaction system was cooled, the polymer was separated, washed, and dried according to a usual method, to obtain a bead-like copolymer (a-1). The polymerization rate of this copolymer (a-1) was 98%, and the weight average molecular weight was 90,000.
27 parts by weight of methacrylic acid 73 parts by weight of methyl methacrylate 1.5 parts by weight of t-dodecylmercaptan 0.4 parts by weight of 2,2'-azobisisobutyronitrile

(A-2)
Copolymer (a-2) was obtained in the same manner as in (a-1), except that the amount of t-dodecyl mercaptan, which is a chain transfer agent, was changed to 2.0 parts by weight. The polymerization rate was 97%, and the weight average molecular weight was 70,000.

(A-3)
A copolymer (a-3) was obtained in the same manner as in (a-1), except that the amount of t-dodecyl mercaptan, which is a chain transfer agent, was changed to 1.2 parts by weight. The polymerization rate was 97%, and the weight average molecular weight was 130,000.

(A-4)
A copolymer (a-4) was obtained by the same production method as in (a-1) except that the charged compositions of the monomer mixture and the chain transfer agent were changed as follows. The polymerization rate was 95%, and the weight average molecular weight was 100,000.
Methacrylic acid 15 parts by weight Methyl methacrylate 75 parts by weight Styrene 10 parts by weight n-dodecyl mercaptan 1.5 parts by weight (a-5)
A copolymer (a-5) was obtained in the same manner as in (a-1), except that the addition amount of t-dodecyl mercaptan as a chain transfer agent was changed to 0.4 part by weight. The polymerization rate was 97%, and the weight average molecular weight was 220,000.

<Reference Example (2) Production of thermoplastic copolymer (A)>
The additives shown in Table 1 were blended with 100 parts by weight of the various copolymers (a) obtained in Reference Example (1), and a twin-screw extruder (TEX30 (manufactured by Nippon Steel Corporation, L / D = 44.5) was used. While nitrogen was purged from the hopper at a rate of 10 L / min, an intramolecular cyclization reaction was performed at a screw rotation speed of 100 rpm, a raw material supply amount of 5 kg / h, and a cylinder temperature of 290 ° C. A copolymer (A) was obtained.

Next, the pellets dried at 100 ° C. for 3 hours were supplied to an injection molding machine (M-50AII-SJ, manufactured by Meiki Seisakusho) to form each test piece. The molding conditions were as follows: molding temperature: glass transition temperature + 150 ° C., mold temperature: 80 ° C., injection speed: 90 cm ³ / sec, injection time: 10 seconds, cooling time: 30 seconds, molding pressure: the mold was completely filled with resin. Pressure (forming lower pressure limit) + 1 MPa.

Table 1 shows the composition of each copolymer component and the results of various property evaluations determined by ¹ H-NMR.

<Reference Example (3) Rubber-Containing Polymer (B)>
(B-1-1)
120 parts by weight of deionized water, 0.5 parts by weight of potassium carbonate, 0.5 parts by weight of dioctyl sulfosuccinate, and 0.005 parts by weight of potassium persulfate are charged into a glass container (5 liter capacity) equipped with a cooler, and a nitrogen atmosphere is charged. After stirring under the following conditions, 53 parts by weight of butyl acrylate, 17 parts by weight of styrene, and 1 part by weight of allyl methacrylate (crosslinking agent) were charged. The mixture was 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 parts by weight of potassium persulfate was continuously added over 90 minutes, and further kept 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 rubbery polymer (B-1-1) having a two-layer structure. The number average particle diameter of the polymer particles measured by an electron microscope was 155 nm.

(B-1-2)
A rubbery polymer having a two-layer structure (B-1-1) was prepared in the same manner as in (B-1-1), except that the composition of the charged mixture of the shell was changed to 30 parts by weight of methyl methacrylate and 0.005 parts by weight of potassium persulfate. B-1-2) was obtained. The number average particle diameter of the polymer particles measured by an electron microscope was 150 nm.

(B-1-3)
"METABLEN (registered trademark) W377" (core: acrylic polymer, shell: methyl methacrylate polymer) manufactured by Mitsubishi Rayon Co., Ltd. was used. The number average particle diameter of the polymer particles measured by an electron microscope was 150 nm.

(B-2)
50 parts by weight of polybutadiene (weight average particle diameter 0.35 μm) (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 composed of 70 parts by weight of styrene, 30 parts by weight of acrylonitrile and 0.3 part by weight of t-dodecylmercaptan were continuously dropped 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 dropped in 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). The graft ratio of this graft copolymer (B-2) was 45%, and the intrinsic viscosity at 30 ° C. of an acetone-soluble methyl ethyl ketone solvent was 0.36 dl / g.

[Examples 1 to 7, Comparative Examples 1 to 4]
The thermoplastic polymer (A) obtained in the above Reference Example (2) and the rubbery polymer (B) obtained in the Reference Example (3) were blended at the composition ratio shown in Table 2, and were subjected to twin screw extrusion. Using a machine (TEX30 (manufactured by Nippon Steel Corporation, L / D = 44.5)), the mixture was kneaded at a screw rotation speed of 150 rpm and a cylinder temperature of 280 ° C. to obtain a pellet-shaped thermoplastic resin composition. The pellets dried for 3 hours were subjected to an injection molding machine (M-50AII-SJ, manufactured by Meiki Seisakusho) to mold each test piece under the following molding conditions: molding temperature: glass transition temperature of thermoplastic polymer (A) +150. ° C, mold temperature: 80 ° C, injection speed: 90 cm ³ / sec, injection time: 10 seconds, cooling time: 30 seconds, molding pressure: pressure at which the resin is completely filled in the mold (minimum molding pressure) + 1 MPa. Was.

  In Comparative Examples 2 and 3, PMMA ("Delpet (registered trademark) 80N" (manufactured by Asahi Kasei Corporation)) was used instead of the thermoplastic polymer (A). Table 3 shows the evaluation results of test pieces obtained by injection molding using “Iupilon (registered trademark) S3000” (manufactured by Mitsubishi Engineering-Plastics Corporation) under the same molding conditions as above.

  From the results of Examples 1 to 5 and Comparative Examples 1 to 4, the thermoplastic resin composition of the present invention has high heat resistance and mechanical properties, as well as excellent colorless transparency, and high optical isotropy, It turns out that it has solvent resistance. Above all, it can be seen that the addition of (B) a rubber-containing polymer having a specific glutaric anhydride-containing unit makes it possible to achieve both higher transparency and mechanical properties such as impact resistance.

  Further, when the refractive index of (A) the thermoplastic copolymer is not close to that of the (B) rubber-containing polymer (Example 6), or (A) the thermoplastic copolymer contains a considerable amount of aromatic compound such as styrene. When a group-group-containing component is contained (Example 7), a composition having characteristics having a balance of mechanical properties, heat resistance, fluidity, colorlessness, and solvent resistance is obtained although transparency is reduced. It can be seen that it can be obtained.

  On the other hand, when the molecular weight of the thermoplastic copolymer (A) is extremely high (Comparative Example 1), the fluidity is poor, the color tone upon heating and melting is remarkably deteriorated, the transparency is reduced, and the colorlessness is high. Transparency cannot be obtained.

  Furthermore, the thermoplastic resin composition of the present invention has high colorless transparency and excellent heat resistance and impact resistance even when compared with PMMA (Comparative Examples 2 and 3) and PC (Comparative Example 4). It can be seen that a material having both optical isotropy and solvent resistance can be obtained.

  According to the present invention, a thermoplastic resin having high heat resistance and mechanical properties, as well as high colorless transparency, optical isotropy, moldability (fluidity), and solvent resistance required in recent years. A resin composition can be obtained.

  In addition, molded articles and films containing the thermoplastic resin composition of the present invention are excellent in transparency and heat resistance, and are therefore used in video equipment-related parts, optical recording or optical communication-related parts, information equipment-related parts, automobiles, and the like. It is extremely useful for applications such as transportation equipment-related parts, medical equipment-related parts, and building material-related parts.

FIG. 1 is a schematic view of a 1/4 elliptical jig and a plate-like molded product in the solvent resistance evaluation of the example.

Claims (18)

(A) a thermoplastic polymer containing a glutaric anhydride-containing unit represented by the following general formula (1),
And (B) a thermoplastic resin composition containing a rubbery polymer and satisfying the following (I) and / or (II):
(I) the total light transmittance per 2 mm thickness of the thermoplastic resin composition is 90% or more;
(II) The thermoplastic polymer (A) has a weight average molecular weight of 30,000 to 150,000 and a glass transition temperature of 130 ° C. or more.

(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 total light transmittance per 2 mm thickness of the thermoplastic resin composition is 90% or more. The thermoplastic resin composition according to claim 1, wherein the thermoplastic polymer (A) has a weight average molecular weight of 30,000 to 150,000 and a glass transition temperature of 130 ° C or higher. The thermoplastic resin composition according to any one of claims 1 to 3, wherein haze per 2 mm in thickness is 3% or less. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the heat distortion temperature is 100C or higher. The thermoplastic polymer (A) contains (i) 25 to 50% by weight of a glutaric anhydride-containing unit represented by the above general formula (1), and (ii) 50 to 75% by weight of an unsaturated carboxylic acid alkyl ester unit. The thermoplastic resin composition according to any one of claims 1 to 5, which is a copolymer contained therein. The thermoplastic polymer may further comprise (iii) 10% by weight or less of unsaturated carboxylic acid units and / or (iv) other vinyl monomer units in addition to the units (i) and (ii). The thermoplastic polymer according to claim 6, which is a copolymer containing 10% by weight or less. (iv) The thermoplastic polymer according to claim 7, wherein the content of the aromatic vinyl monomer unit among other vinyl monomer units is 5% by weight or less. The thermoplastic resin composition according to any one of claims 1 to 8, wherein a difference in refractive index between (A) the thermoplastic polymer and (B) the rubbery polymer is 0.02 or less. The thermoplastic resin composition according to claim 9, wherein the difference in the refractive index between (A) the thermoplastic polymer and (B) the rubbery polymer is 0.01 or less. The thermoplastic resin composition according to any one of claims 1 to 10, wherein (B) the rubber-containing polymer is a multilayer polymer (B-1) having one or more rubber layers therein. (B-1) The thermoplastic resin composition according to claim 11, wherein the multilayer structure polymer has a number average particle size of 0.05 to 1 µm. (B-1) The thermoplastic resin composition according to claim 11, wherein the polymer constituting the outermost layer of the multilayer polymer contains a glutaric anhydride-containing unit represented by the general formula (1). (B-1) The thermoplastic resin composition according to claim 11, wherein the polymer constituting the rubbery layer of the multilayer polymer contains an alkyl acrylate unit and a substituted or unsubstituted styrene unit. (B-1) The multilayer structure polymer contains the glutaric anhydride-containing unit represented by the general formula (1) in the polymer constituting the outermost shell layer, and forms the inner rubbery layer. The thermoplastic resin composition according to claim 11, wherein the polymer contains an alkyl acrylate unit and a substituted or unsubstituted styrene unit. The thermoplastic resin composition according to claim 1, having a photoelastic coefficient of 5 × 10 ⁻¹² Pa ⁻¹ or less. A molded article comprising the thermoplastic resin composition according to any one of claims 1 to 16. A film comprising the thermoplastic resin composition according to claim 1.

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