JP2009096938A - Thermoplastic resin composition, molded product, and film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film suitable for optical application such as a retardation film excellent in heat resistance and transparency. <P>SOLUTION: The thermoplastic resin composition comprises 1-100 pts.wt. of a multilayered polymer B having one or more rubbery layers inside based on 100 pts.wt. of an acrylic thermoplastic polymer A with a glass transition temperature 120°C or more, and satisfies the following conditions (I) and (II): (I) an average particle diameter of the multilayered polymer B having one or more rubbery layers inside is 0.1-1 μm; and (II) an average particle diameter of the multilayered polymer B given after heating retention of the thermoplastic resin composition for one hour at the glass transition temperature +130°C of the acrylic thermoplastic resin composition A is 100 μm or less. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  In the present invention, a multilayer polymer having a rubbery layer is dispersed well in a thermoplastic resin and is excellent in toughness and heat resistance. The present invention relates to an excellent thermoplastic resin composition, and a molded article and a film containing the thermoplastic resin composition.

  Acrylic resins typified by polymethyl methacrylate (hereinafter referred to as PMMA) take advantage of its transparency and dimensional stability and are used in a wide range of parts including optical materials, household electrical equipment, OA equipment, and automobiles. Although used in the field, there is a problem that heat resistance and toughness are not sufficient. 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, although both show an increase in glass transition temperature (Tg), There was a problem that it was inferior in thermal stability when kept at high temperature. Furthermore, as a toughness improving agent, it has been practiced for a long time to add a rubber component (see Patent Document 1), but a general rubber component has low heat resistance, especially when it stays at high temperatures. There was a problem of generating a large amount of cracked gas.

As a method for solving these problems, a method of adding a rubber-containing polymer to a copolymer containing a glutaric anhydride-containing unit has been disclosed (see Patent Documents 2 to 4).
However, in the rubber component disclosed in these patent documents, fine dispersion is insufficient with the aggregation of the rubber component during the molding process by heating and melting. Therefore, there are few defects in surface smoothness, toughness, and appearance. In particular, in recent years, there has been a problem that it is insufficient as an optical material that requires optical properties such as higher transparency. In other words, resin compositions that have mechanical properties such as toughness, especially surface smoothness after molding by heat-melting spray and few defects in appearance, and have excellent optical properties have been known so far. There wasn't.
Japanese Examined Patent Publication No. 54-18298 (Page 1-2, Examples) JP-A-4-277546 (Page 1-2, Examples) JP 2000-178399 A (page 1-2, Examples) JP-A-2004-298812 (page 1-2, Examples)

  The present invention provides a thermoplastic resin composition having excellent toughness and optical properties, good dispersibility of a multilayer polymer having a rubbery layer, and particularly excellent retention stability that retains excellent dispersibility even after heat retention. The task is to do.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have specifically dispersed in an acrylic thermoplastic polymer by using a multilayer polymer having a rubbery layer having a specific chemical structure. The present invention has been found.

That is, the present invention
[1] 1 to 100 parts by weight of a multi-layer polymer (B) having one or more rubber layers inside with respect to 100 parts by weight of an acrylic thermoplastic polymer (A) having a glass transition temperature of 120 ° C. or higher. A thermoplastic resin composition containing and satisfying the following (I) and (II):
(I) The average particle diameter of the multilayer polymer (B) having one or more rubbery layers inside is 0.1 to 1 μm;
(II) The average particle diameter of the multilayer polymer (B) after the thermoplastic resin composition is heated and retained for 1 hour at the glass transition temperature of the acrylic thermoplastic polymer (A) + 130 ° C. is 100 μm or less,
[2] The acrylic thermoplastic polymer (A) having a glass transition temperature of 120 ° C. or higher is a copolymer containing (i) a glutaric anhydride-containing unit represented by the following general formula (1). The thermoplastic resin composition as described in [1] above,

(However, R ¹ and R ² are the same or different and represent any one selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms.)
[3] An acrylic thermoplastic polymer (A) having a glass transition temperature of 120 ° C. or higher is (i) 15 to 50% by weight of a glutaric anhydride-containing unit represented by the general formula (1) (ii) The thermoplastic resin composition according to the above [2], which is a copolymer having 50 to 85% by weight of a saturated carboxylic acid alkyl ester unit and (iii) 10% by weight or less of an unsaturated carboxylic acid unit,
[4] The above [1] to [3], wherein the polymer constituting the rubber layer of the multilayer polymer (B) is a copolymer containing an alkyl acrylate unit and a substituted or unsubstituted styrene unit. ] The thermoplastic resin composition according to any one of
[5] The polymer constituting the rubber layer of the multilayer polymer (B) is a polyfunctional monomer with respect to a total of 100 parts by weight of alkyl acrylate units and substituted or unsubstituted styrene units. 2 to 20 parts by weight of a copolymer obtained by copolymerizing the thermoplastic resin composition according to the above [4],
[6] The polymer constituting the rubber layer of the multilayer polymer (B) contains allyl groups with respect to a total of 100 parts by weight of the alkyl acrylate unit and the substituted or unsubstituted styrene unit. The thermoplastic as described in [5] above, which is a polymer obtained by copolymerizing 1 to 10 parts by weight of a functional monomer and 1 to 10 parts by weight of a polyfunctional monomer having no allyl group. Resin composition,
[7] The polymer constituting the rubber layer of the multilayer polymer (B) contains allyl groups with respect to a total of 100 parts by weight of the alkyl acrylate unit and the substituted or unsubstituted styrene unit. [5] or [6] above, which is a polymer obtained by copolymerizing 1 to 10 parts by weight of a functional monomer and 4 to 10 parts by weight of a polyfunctional monomer having no allyl group The thermoplastic resin composition according to the description,
[8] The thermoplastic resin composition according to the above [6] or [7], wherein the polyfunctional monomer containing an allyl group is allyl acrylate and / or allyl methacrylate,
[9] Any of the above [1] to [8], wherein the polymer constituting the outermost shell layer of the multilayer polymer (B) contains a glutaric anhydride containing unit represented by the following general formula (1) The thermoplastic resin composition according to

(However, R ¹ and R ² are the same or different and represent any one selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms.)
[10] A molded article comprising the thermoplastic resin composition according to any one of [1] to [9],
[11] A film comprising the thermoplastic resin composition according to any one of [1] to [9].

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

  The acrylic thermoplastic polymer (A) used in the present invention is a thermoplastic polymer obtained by polymerizing at least one unsaturated carboxylic acid and / or unsaturated carboxylic acid ester, and its glass transition temperature. Must be 120 ° C. or higher.

In addition, the glass transition temperature said here is a glass transition temperature measured with the temperature increase rate of 20 degree-C / min using the differential scanning calorimeter (DSC-7 type | mold by Perkin Elmer).
Preferable examples of the acrylic thermoplastic polymer (A) having a glass transition temperature of 120 ° C. or higher include an acrylic copolymer containing a cyclic structural unit in its molecular main chain. The cyclic structural unit is not particularly limited, but is preferably a maleic anhydride unit, a maleimide unit, a glutaric anhydride-containing unit, a glutarimide unit, a lactone unit, or a lactam unit, and a glutar represented by the following general formula (1) An acrylic thermoplastic polymer containing an acid anhydride-containing unit can be used particularly preferably.

(However, R ¹ and R ² are the same or different and represent any one selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms.)
Among them, (i) an acrylic copolymer having 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 acrylic copolymer is preferably 25 to 50% by weight in 100% by weight of the acrylic copolymer. More preferably, it is 30 to 45% by weight. When the glutaric anhydride content unit is less than 25% by weight, not only the effect of improving the heat resistance is reduced, but also the birefringence characteristics and the solvent resistance tend to be lowered.

  The content of the unsaturated carboxylic acid alkyl ester unit (ii) in the acrylic copolymer is preferably 50 to 75% by weight, more preferably 55 to 70% in 100% by weight of the acrylic copolymer. % By weight. In addition to the above units (i) and (ii), it can further contain (iii) an unsaturated carboxylic acid unit and / or (iv) other vinyl monomer units. 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 acrylic copolymer 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 unsaturated carboxylic acid unit (iii) exceeds 10 weight%, there exists a tendency for the dimensional stability by moisture absorption to fall.

  The content of the other vinyl monomer units (iv) is preferably in the range of 10% by weight or less, that is, in the range of 0 to 10% by weight in 100% by weight of the acrylic copolymer. 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 and the solvent resistance tend to decrease, so the content is 5% by weight or less, that is, in the range of 0 to 5% by weight. It is preferable that it is 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 any one selected from hydrogen and 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 any one selected from hydrogen and an alkyl group having 1 to 5 carbon atoms, and R 5 is an unsubstituted or substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms and a carbon number substituted with a hydroxyl group or halogen. Any one selected from 3 to 6 alicyclic hydrocarbon groups)

  Such an acrylic copolymer containing the glutaric anhydride-containing unit represented by the general formula (1) 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. An acrylic copolymer containing the glutaric anhydride-containing unit can be produced. 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 (4)

(However, R ³ represents any one selected from hydrogen and 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 (5) can be mentioned as a preferable example of an unsaturated carboxylic-acid alkylester monomer.

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

  Of these, acrylic acid alkyl esters and / or methacrylic acid alkyl 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. .

  Preferable 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, 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. Of these, 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 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 particularly preferable 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, the acrylic resin containing the glutaric anhydride-containing unit represented by the general formula (1) is obtained by heating the copolymer (a). When producing a copolymer, the amount of the glutaric anhydride-containing unit (i) represented by the general formula (1) is reduced, and the heat resistance improvement effect of the copolymer tends to be reduced. . On the other hand, when the content of the unsaturated carboxylic acid monomer (iii) exceeds 50% by weight, the glutaric anhydride contained in the general formula (1) is contained by heating the copolymer (a). When producing an acrylic copolymer containing units, there is a tendency that a large amount of unsaturated carboxylic acid units (iii) remain and contains glutaric anhydride-containing units represented by the above general formula (1) There is a tendency that the dimensional stability due to moisture absorption of the acrylic copolymer is reduced.

  Further, the copolymer (a) is heated, and (a) dehydration and / or (b) intramolecular cyclization reaction is carried out by dealcoholization to produce an acrylic thermoplastic polymer containing glutaric anhydride-containing units. The method is not particularly limited, but a method of manufacturing through a heated extruder having a vent or a method of manufacturing in an inert gas atmosphere such as in a nitrogen stream or in an apparatus that can be heated and devolatilized under vacuum is preferable. . Among them, 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 substitute the inside of 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, a three screw extruder, a continuous or batch kneader type kneader, etc. can be used. The machine can be preferably used.

  The temperature for the devolatilization by the above method is not particularly limited as long as it is a temperature at which an intramolecular cyclization reaction occurs due to (i) dehydration and / or (b) dealcoholization, but preferably in the range of 180 to 300 ° C. In particular, a range of 200 to 280 ° C. is preferable.

  In addition, the time for heating and devolatilization in this case is not particularly limited and can be appropriately set according to the desired copolymer composition, but is usually 1 minute to 60 minutes, preferably 2 minutes to 30 minutes, especially 3 to 3. A range of 20 minutes is preferred. In particular, the ratio of the screw diameter (D) to the screw length (L) of the screw (L / D) in order to ensure sufficient heating time for the intramolecular cyclization reaction to proceed using the extruder. Is preferably 40 or more. When an extruder with a short L / D is used, a large amount of unreacted unsaturated carboxylic acid units remain, so that dimensional stability due to moisture absorption tends to decrease. The upper limit is preferably 110 or less from the viewpoint of structure such as mechanical strength of the extruder.

  Further, among the extruders, by using a biaxial / uniaxial composite continuous kneading extruder, there is a tendency to obtain a thermoplastic polymer that is extremely colorless and excellent in mechanical properties, so that it can be preferably used. . Here, the biaxial / single-shaft combined continuous kneading extruder is a biaxial screw portion in which a first shaft and a second shaft in which a screw portion is formed are arranged in parallel in an extruder casing, and a biaxial screw A single screw portion in which a first shaft extended from the screw portion is disposed, and a flow rate adjusting mechanism is provided in a communication portion between the biaxial screw portion and the single screw portion, and the casing communicates with the biaxial screw portion. A twin-screw / single-shaft composite continuous kneading extruder having a raw material supply port and a discharge port communicating with the end of the extended first shaft, and as a commercially available extruder of this type Is an “HTM type extruder” manufactured by CTE. When the copolymer (a) as a raw material is heated in a continuous manner and the cyclization reaction proceeds, due to the progress of the reaction, the melt viscosity increases, and the heat generated by the shearing of the extrusion apparatus increases. There is a tendency for coloring due to thermal decomposition of the molecular main chain to increase. Further, the shear heat generation becomes larger when melt kneading with a twin screw than with a single screw. On the other hand, from the viewpoint of reaction rate, it is preferable to melt and knead with a twin screw. From the above, by using a specific twin-screw / single-screw composite continuous kneading extruder, in the initial reaction stage where the melt viscosity is relatively low, the melt viscosity is secured while ensuring a sufficient reaction speed with a twin screw. In the late stage of the reaction, where the heat treatment is relatively high, the thermal decomposition of the molecular main chain is suppressed by heat treatment with a single screw part that suppresses shearing heat generation, and thus the resulting acrylic system containing glutaric anhydride-containing units The thermoplastic polymer (A) is presumed to be excellent in color tone and mechanical properties.

  When the copolymer (a) is heated using the extruder, the cylinder temperature of the extruder is preferably set to 200 to 320 ° C, more preferably 220 to 310 ° C.

  Furthermore, in the present invention, when the copolymer (a) is heated by the above method or the like, one or more of acid, alkali and salt compounds may be added as a catalyst for promoting the cyclization reaction to glutaric anhydride. it can. The addition amount is not particularly limited, and is preferably about 0.01 to 1 part by weight per 100 parts by weight of the copolymer (a). There are no particular restrictions on the types of these acids, alkalis, and salt compounds, and examples of the acid catalyst include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, phosphoric acid, phosphorous acid, phenylphosphonic acid, and methyl phosphate. It is done. Examples of the basic catalyst include metal hydroxides, amines, imines, alkali metal derivatives, alkoxides, ammonium hydroxide salts and the like. Furthermore, examples of the salt-based catalyst include metal acetates, metal stearates, metal carbonates, and the like. However, it is necessary to add in a range where the color possessed by the catalyst does not adversely affect the coloring of the thermoplastic polymer and the transparency is not lowered. Among them, an alkali metal-containing compound (alkali metal compound) 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, among which sodium hydroxide, sodium methoxide, lithium acetate and sodium acetate can be preferably used.

In addition, an infrared spectrophotometer or a proton nuclear magnetic resonance ( ¹ H-NMR) measuring instrument is generally used for quantification of each component unit in the acrylic thermoplastic polymer 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, for example, in the case of a copolymer consisting of a glutaric anhydride-containing unit, methacrylic acid, and methyl methacrylate, the spectral assignment in a dimethyl sulfoxide heavy solvent is 0.5 to 1. 5 ppm peak is hydrogen of α-methyl group of methacrylic acid, methyl methacrylate and glutaric anhydride ring compound, 1.6 to 2.1 ppm peak is hydrogen of methylene group of polymer main chain, 3.5 ppm peak is Copolymer composition can be determined from hydrogen of methacrylic acid carboxylic acid ester (—COOCH ₃ ) and a peak of 12.4 ppm from hydrogen of carboxylic acid of methacrylic acid and the integral ratio of the spectrum. In addition to the above, when styrene is contained as another copolymer component, hydrogen of the aromatic ring of styrene is found at 6.5 to 7.5 ppm, and the copolymer composition is similarly determined from the spectral ratio. be able to.

  The acrylic thermoplastic polymer (A) of the present invention preferably has a weight average molecular weight of 30,000 to 200,000, more preferably 50,000 to 150,000. In addition, the weight average molecular weight as used in the field of this invention shows the weight average molecular weight in the absolute molecular weight measured by multi-angle light scattering gel permeation chromatography (GPC-MALLS).

  The acrylic thermoplastic polymer (A) needs to have a glass transition temperature (Tg) of 120 ° C. or higher in terms of heat resistance. The glass transition temperature is more preferably 130 ° C. or higher, and particularly preferably 140 ° 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 glass transition temperature of the component (A) can be adjusted by the content of the cyclic structural unit when an acrylic copolymer having a cyclic structural unit is used as the component (A), and is increased by increasing this. be able to.

  In the present invention, the acrylic thermoplastic polymer (A) is made to contain the multilayer polymer (B) having one or more rubber layers in the acrylic thermoplastic polymer (A). Excellent toughness can be imparted without significantly impairing the excellent properties of the steel. As the multilayer polymer (B) having one or more rubbery layers inside, it is composed of a layer containing one or more rubbery polymers, and one or more layers composed of different polymers, In addition, a multilayer structure polymer called a so-called core-shell type having a structure containing one or more rubber-like polymers inside can be preferably used.

  The number of layers constituting the multilayer structure polymer (B) used in the present invention may be two or more, and may be three or more or four or more. It is necessary to be a multilayer structure polymer having a layer (core layer).

  In the multilayer structure polymer (B) 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, acrylic monomer, silicone monomer, styrene monomer, nitrile monomer, conjugated diene monomer, urethane monomer, ethylene monomer, propylene monomer And rubbers composed of polymerized isobutene monomers and the like. 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 made of a polymer composed of nitrile units such as acrylonitrile units and methacrylonitrile units, and conjugated diene units such as butanediene units and isoprene units. A rubber composed of a combination of two or more of these components is also preferred. For example, (1) rubber made of a copolymer 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. Rubber made of a copolymer composed of acrylic units such as units and butyl acrylate units and styrene units such as styrene units and α-methylstyrene units, (3) such as ethyl acrylate units and butyl acrylate units Rubber made of a copolymer composed of acrylic units and conjugated diene units such as butanediene units and isoprene units, and (4) acrylic units such as ethyl acrylate units and butyl acrylate units, dimethylsiloxane units and phenyl Silicone such as methylsiloxane units Rubber consisting of a copolymer composed of styrene-based unit such as units and styrene units and α- methyl styrene units and the like. Of these, rubbers made of a copolymer containing acrylic acid alkyl ester units and substituted or unsubstituted styrene units are most preferred from the viewpoint of transparency and mechanical properties.

  In addition to these components, a rubber obtained by copolymerizing a polyfunctional monomer having two or more double bonds can be preferably used. Examples of the polyfunctional monomer used in the present invention include ethylene glycol diacrylate, propylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, ethylene glycol dimethacrylate, and propylene glycol. Dimethacrylate, alkylene glycol di (meth) acrylate such as 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, polyvinylbenzene such as divinylbenzene and trivinylbenzene, and α, β containing allyl groups -Unsaturated monocarboxylic acid or dicarboxylic acid allyl ester, methallyl ester, triallyl cyanurate, triallyl isocyanurate, etc., alone or as a mixture be able to.

  Among them, it is preferable in terms of residence stability and toughness to use a polyfunctional monomer containing an allyl group and a polyfunctional monomer not having an allyl group, particularly as a polyfunctional monomer containing an allyl group. Allyl acrylate and allyl methacrylate are preferable, and it is preferable to use alkylene glycol di (meth) acrylate in combination as a polyfunctional monomer having no allyl group.

  The addition amount of the polyfunctional monomer is preferably 2 to 20 parts by weight for the purpose of the present invention, in order to suppress aggregation due to heat retention and to impart toughness to the acrylic thermoplastic resin. It is preferably 20 parts by weight, particularly 5 to 20 parts by weight.

  Among them, 1 to 10 parts by weight, preferably 2 to 10 parts by weight of a polyfunctional monomer containing an allyl group, and 1 to 10 parts by weight, preferably 2 to 10 parts by weight of a polyfunctional monomer having no allyl group. It is particularly preferable to use 10 parts by weight, more preferably 4 to 10 parts by weight.

  In the multilayer structure polymer (B) 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 it is more glass than the rubber layer. A polymer component having a high transition temperature 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 toughness 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 toughness is great. 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, and the effect of improving toughness is great. From the viewpoint, 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 (B) containing the rubbery polymer of the present invention, the type of the outermost layer (shell layer) is an unsaturated carboxylic acid alkyl ester unit, an unsaturated carboxylic acid unit, an unsaturated glycidyl group-containing unit, At least one selected from polymers containing aliphatic vinyl units, aromatic vinyl units, vinyl cyanide units, maleimide units, unsaturated dicarboxylic acid units, unsaturated dicarboxylic anhydride units, and other vinyl units. Is mentioned. Among these, 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-based unit is preferable. Polymers containing unsaturated carboxylic acid alkyl ester units and unsaturated carboxylic acid units are most preferred. Moreover, it is also preferable to include in the composition a multilayer structure polymer (B) having a polymer having a unit in common with the component (A) as the outermost layer.

  Moreover, when the outermost layer in the multilayer structure polymer (B) is a polymer containing an unsaturated carboxylic acid alkyl ester unit and an unsaturated carboxylic acid unit, the acrylic heat of the present invention described above is heated. As in the production of the plastic polymer (A), the intramolecular cyclization reaction proceeds to produce a glutaric anhydride-containing unit represented by the general formula (1). Accordingly, the multilayered structure polymer (B) 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 acrylic thermoplastic polymer (A), and under appropriate conditions. The multilayer polymer (B) containing the glutaric anhydride-containing unit represented by the general formula (1) in the outermost layer is obtained by heat melting and kneading. As a result, the multilayered structure polymer (B) can be favorably dispersed in the acrylic thermoplastic polymer (A) to be a continuous phase (matrix phase) without agglomeration. It is considered that extremely high transparency can be expressed with improvement in mechanical properties such as toughness of the plastic resin composition. Such an effect is particularly remarkable when an acrylic copolymer containing a glutaric anhydride-containing unit is used as the component (A).

  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 preferred example of the multilayer structure polymer (B) of the present invention, the core layer is butyl acrylate / styrene copolymer, the outermost layer is methyl methacrylate / glutaric anhydride represented by the general formula (1). What is a copolymer composed of contained units, the core layer is butyl acrylate / styrene copolymer, the outermost layer is methyl methacrylate / glutaric anhydride-containing unit represented by the above general formula (1) / 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 methyl methacrylate polymer And those in which the core layer is a butyl acrylate polymer and the outermost layer is a methyl methacrylate polymer. Here, “/” indicates copolymerization.

Moreover, in order to confirm the presence or absence of the cyclic structure represented by the general formula (1) in the multilayer structure polymer (B) of the present invention, an infrared spectrophotometer is used. In infrared spectroscopy, for example, glutaric anhydride 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. Moreover, each copolymer composition can be quantified with a proton nuclear magnetic resonance ( ¹ H-NMR) measuring instrument. For example, in the case of a copolymer consisting of a glutaric anhydride unit, methacrylic acid, and methyl methacrylate, the attribution of the spectrum in dimethyl sulfoxide heavy solvent is 0.5 to 1.5 ppm and the peaks are methacrylic acid and methyl methacrylate. And the hydrogen of the α-methyl group of the glutaric anhydride ring compound, the peak of 1.6 to 2.1 ppm is the hydrogen of the methylene group of the polymer main chain, the peak of 3.5 ppm is the carboxylate ester of methyl methacrylate (—COOCH ₃ ) Hydrogen, peak of 12.4 ppm can determine copolymer composition from hydrogen of carboxylic acid of methacrylic acid and integral ratio of spectrum. In addition to the above, when styrene is contained as another copolymer component, hydrogen of the aromatic ring of styrene is found at 6.5 to 7.5 ppm, and the copolymer composition is similarly determined from the spectral ratio. be able to.

  In the multilayer structure polymer (B) of the present invention, the weight ratio of the rubber layer and the layers other than the rubber layer is 30% by weight or more and 90% by weight or less of the rubber layer with respect to the entire multilayer structure polymer. Further, it is preferably 40% by weight or more and 80% by weight or less, more preferably 50% by weight or more and 75% by weight or less.

When the outermost monomer mixture is polymerized to the rubber layer, the (co) polymer that forms the rubber layer and the (co) polymer that forms the outer layer are covalently bonded, so-called graft copolymerization. However, a (co) polymer that forms the outermost non-grafted layer may also be included. From the viewpoint of residence stability and toughness, the graft ratio is preferably 20 to 100%, more preferably 30 to 90%, and particularly preferably 40 to 80%. Here, the graft ratio is the weight ratio of the grafted monomer mixture to the polymer forming the rubber layer. The ungrafted (co) polymer is calculated from the following formula by extracting from the multilayer polymer (B) with an organic solvent in which the copolymer forming the outermost layer such as tetrahydrofuran is dissolved and measuring the weight. I can do it.
Graft rate (%) = (weight of monomer mixture of outermost layer−weight of organic solvent extraction) / total weight of monomer mixture of rubbery layer × 100

  In addition, the weight average molecular weight of the non-grafted (co) polymer is preferably from 5 to 150,000, and particularly from 6 to 130,000 is preferably used from the viewpoint of the balance between toughness and moldability.

  The production method of the multilayer structure polymer (B) in the present invention is not particularly limited, and known polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization can be used. Is preferred.

Regarding the emulsion polymerization method which is a preferred polymerization method of the multilayer structure polymer (B) of the present invention, after adding deionized water, an emulsifier and a polymerization initiator to the reaction vessel, each monomer and polyfunctional monomer It is preferable to add a predetermined amount of (crosslinking agent or grafting agent) alone or in a mixture of two or more and polymerize at a predetermined temperature.
The monomer / water charge ratio (weight ratio) is preferably monomer / water = 1/1 to 1/10, more preferably 1/2 to 1/9.

  As the polymerization initiator, an azo compound, peroxide, persulfate, perborate, or the like can be used. In particular, water-soluble inorganic initiators such as persulfates and perborates, or combinations thereof with sulfites, hydrogen sulfites, thiosulfates, and the like can be used as redox initiators.

  As the emulsifier, long-chain fatty acid alkali (earth) metal salts, alkylbenzene sulfonates, long-chain alkyl sulfates, dialkylsulfosuccinates, and the like can be preferably used.

  In addition, for the purpose of controlling the molecular weight during the production of the multilayer structure polymer (B), for example, a chain transfer agent such as an alkyl mercaptan compound, carbon tetrachloride, carbon tetrabromide, dimethylacetamide, dimethylformamide, triethylamine or the like is added. Can do.

  About polymerization temperature, 20-120 degreeC is preferable, More preferably, 30-100 degreeC, Especially 40-90 degreeC is preferable at the point of molecular weight control. The polymerization time is not particularly limited, but is usually 30 minutes to 10 hours, and 1 hour to 8 hours is particularly preferable in terms of productivity.

  In emulsion polymerization, a monomer, an emulsifier, an initiator, a chain transfer agent, and the like can be added by any known method such as a batch addition method, a divided addition method, or a continuous addition method. In addition, the polymer latex obtained by the emulsion polymerization method can be handled as a powder by coagulating it by a known method such as spray drying method, acid addition coagulation method, salt addition coagulation method, freeze coagulation method, and drying. .

  About the average particle diameter of the multilayer structure polymer (B) of this invention, it is required to be 0.1 micrometer or more and 1 micrometer or less. Further, the average particle diameter is more preferably 0.1 μm or more and 0.8 μm or less, further preferably 0.1 μm or more and 0.6 μm or less, and most preferably 0.15 μm or more and 0.5 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. Here, the average particle size means that a 1% by weight tetrahydrofuran dispersion of the multilayer structure polymer (B) is prepared, and the dispersion is used, using a laser diffraction scattering particle size distribution analyzer LS230 manufactured by BECKMAN COULTER. The measured volume average particle diameter is shown.

  Moreover, since the thermoplastic resin composition excellent in transparency can be obtained when each refractive index of (A) acrylic thermoplastic polymer and (B) multilayer structure polymer is approximate, 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) a method for adjusting the composition ratio of each monomer unit of the acrylic thermoplastic polymer, and / or (B) a rubber material used for the multilayer structure polymer Examples thereof include a method for adjusting the composition ratio of the polymer or monomer.

  In addition, the refractive index difference said here is the value measured by the method shown below. (A) The thermoplastic resin composition of the present invention is sufficiently dissolved under suitable conditions in a solvent in which the acrylic thermoplastic polymer is soluble to form a cloudy solution. And insoluble parts. After refining this soluble part (part containing (A) acrylic thermoplastic polymer) and insoluble part (part containing (B) multilayer structure polymer), the measured refractive index (23 ° C., measurement wavelength: 550 nm) as a difference in refractive index.

  In addition, the copolymer composition of (A) acrylic thermoplastic polymer and (B) multilayer structure polymer in the resin composition is obtained by separating each component after the separation operation of the soluble component and the insoluble component by the solvent. It is possible by analyzing individually.

  As a commercial product of a multilayer structure polymer, for example, “Metablene (registered trademark)” manufactured by Mitsubishi Rayon Co., Ltd., “Kaneace (registered trademark)” manufactured by Kaneka Chemical Industry Co., Ltd., “Paralloid (registered trademark)” manufactured by Kureha Chemical Industry Co., Ltd. , “Acryloid (registered trademark)” manufactured by Rohm and Haas, “Staffyroid (registered trademark)” manufactured by Gantz Kasei Kogyo Co., Ltd., and “Parapet (registered trademark) SA” manufactured by Kuraray Co., Ltd. More than seeds can be used.

  In the present invention, the (B) multilayer structure polymer is preferably in the range of 1 to 100 parts by weight, and more preferably in the range of 1 to 70 parts by weight with respect to 100 parts by weight of the (A) acrylic thermoplastic polymer. More preferably, it is most preferably in the range of 1 to 45 parts by weight.

  The thermoplastic resin composition of the present invention needs to have an average particle size (average aggregated particle size) of 100 μm or less after heat retention. Further, it is preferably 80 μm or less, particularly 50 μm or less. The average agglomerated particle diameter after heat retention as used herein means that the thermoplastic resin composition is allowed to stand still in a test tube at a glass transition temperature of the acrylic thermoplastic polymer (A) + 130 ° C. for 1 hour ( After carrying out a retention test with no stirring, a 10 wt% tetrahydrofuran dispersion was prepared, and the volume average particle size measured using a laser diffraction scattering particle size distribution analyzer LS230 manufactured by BECKMAN COULTER was used. Show. The average agglomerated particle diameter after heat retention is a value measured after performing a retention test on the thermoplastic resin composition containing the acrylic thermoplastic polymer (A) and the multilayer polymer (B), preferably, The average agglomerated particle diameter measured after a residence test of a thermoplastic resin composition in which 20 parts by weight of the multilayer polymer (B) was blended with 100 parts by weight of the acrylic thermoplastic polymer (A) was This value is preferably 100 μm or less.

  Furthermore, in the present invention, hindered phenol-based, benzotriazole-based, benzophenone-based, benzoate-based and cyanoacrylate-based UV absorbers and antioxidants, higher fatty acids and acid ester-based compounds, Acid amides, lubricants and plasticizers such as higher alcohols, montanic acid and salts thereof, esters thereof, half esters thereof, release agents such as stearyl alcohol, stearamide and ethylene wax, phosphites and hypophosphites Addition of anti-coloring agents such as, halogen-based flame retardants, phosphorus-based and silicone-based non-halogen-based flame retardants, nucleating agents, amine-based, sulfonic acid-based, polyether-based anti-static agents, pigments and other colorants An agent may optionally be included.

  In the present invention, (A) an acrylic thermoplastic polymer, (B) a multilayer structure polymer, and a method of blending other additives as required, include (A) an acrylic thermoplastic polymer and other optional components. After blending in advance, a method of uniformly melting and kneading with a single-screw or twin-screw extruder at 200 to 350 ° C. is preferably used. Moreover, the method of removing a solvent after mixing in the solution of the solvent which can melt | dissolve (A) component, (B) component, etc. can also be used.

  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.

  In this invention, a well-known method can be used for the manufacturing method of a film. That is, a production method such as an inflation method, a T-die method, a calendar method, a cutting method, a solution casting method, an emulsion method, or a hot press method can be used. Preferably, a T-die method, a cast method or a hot press method can be used. In the case of a production method using an inflation method or a T-die method, an extruder type melt extrusion apparatus equipped with a single screw or twin screw can be used. The melt extrusion temperature for producing the film of the present invention is preferably 150 to 350 ° C, more preferably 200 to 300 ° C. Moreover, when melt-kneading using a melt-extrusion apparatus, it is preferable to perform the melt-kneading under reduced pressure or the melt-kneading under nitrogen stream from a viewpoint of coloring suppression. When the film of the present invention is produced by the casting method, solvents such as tetrahydrofuran, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone can be used. Preferred solvents are acetone, methyl ethyl ketone, N-methylpyrrolidone and the like. The film is prepared by dissolving the thermoplastic resin composition of the present invention in one or more of the above solvents, and using the solution with a bar coater, a T die, a T die with a bar, a die coat, etc. It can be produced by casting on a flat plate or curved plate (roll) such as a film, steel belt, or metal foil and using a dry method in which the solvent is removed by evaporation, or a wet method in which the solution is solidified with a coagulating liquid.

  Moreover, in this invention, even if it is the film which extended | stretched the film (non-orientation) obtained by the said method, it can be used preferably. Above all, when used as a retardation film that provides functions such as widening the viewing angle of liquid crystal displays and sharpening of color contrast, when used as a retardation film, it should be stretched and oriented at least in a uniaxial direction, and controlled to a specific retardation value useful as a retardation film. Is preferred.

  Here, for the stretching, a known stretching method can be used. For example, as the uniaxial stretching method, transverse uniaxial stretching by a tenter method, longitudinal uniaxial stretching between rolls, rolling between rolls and the like are preferable. The stretching conditions are not particularly limited, but the stretching temperature is usually 10 to 60 degrees higher than the glass transition temperature of the resin used, more preferably 20 to 50 degrees higher, and the stretching ratio is usually 1.1 in terms of surface magnification. -4 times, more preferably 1.5-3 times.

  The thickness of the film of the present invention is 10 to 200 μm, more preferably 15 to 170 μm, and particularly preferably 20 to 150 μm.

  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.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Each measurement and evaluation was performed by the following method.

(1) A weight average molecular weight / molecular weight distribution polymer was dissolved in tetrahydrofuran to prepare a measurement sample. Gel permeation chromatograph (pump: model 515, manufactured by Waters, column: TSK-gel-GMHXL, manufactured by Tosoh Corporation) equipped with a DAWN-DSP type multi-angle light scattering photometer (manufactured by Wyatt Technology) using tetrahydrofuran as a solvent. ) Was used to measure the weight average molecular weight (absolute molecular weight) and the number average molecular weight (absolute molecular weight).

(2) Each component composition In heavy dimethyl sulfoxide, 1H-NMR was measured at 30 ° C. to determine the composition of each copolymer unit.

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

(4) Average particle size of multilayer structure polymer (B) A 1 wt% tetrahydrofuran dispersion of the multilayer structure polymer (B) was prepared, and using this dispersion, a laser diffraction scattering particle size distribution measuring device manufactured by BECKMAN COULTER The volume average particle diameter measured using LS230 was measured.

(5) Graft rate 2 g of the multilayer structure polymer (B) was weighed, extracted in a 200 g tetrahydrofuran solvent with stirring at 60 ° C. for 10 hours, and centrifuged at 10,000 rpm for 60 minutes. This operation was repeated three times, and the insoluble content of the tetrahydrofuran solvent was taken out and weighed to calculate from the following formula.
Graft rate (%) = (weight of monomer mixture of outermost layer−weight of organic solvent extraction) / total weight of monomer mixture of rubbery layer × 100

(6) Rubber dispersibility The thermoplastic resin composition was subjected to a 40 mmφ vented single screw extruder, extruded from a T-die for film production having a width of 200 mm at a speed of 20 kg / h at 280 ° C., and subjected to a polishing roll. A film having an average film thickness of about 40 μm was obtained. In the obtained film, a 10 cm square (100 cm 2) at an arbitrary location is put on a fluorescent lamp, and the number of foreign matters observed visually is counted. X and Table 2 show.

(7) Transparency (haze)
The film having an average thickness of 40 μm was measured for haze (cloudiness) (%) at 23 ° C. using a direct reading haze meter manufactured by Toyo Seiki Co., Ltd., and the transparency was evaluated.

(8) Tensile Breaking Elongation The obtained film having an average thickness of 40 μm is cut into a strip-shaped sample of 127 mm × 12.7 mm, the tensile breaking elongation is measured according to ASTM D-638, and the tensile breaking before heating residence The elongation is shown in Table 2.

(9) Retention stability 3 g of the obtained thermoplastic resin composition pellets were left standing in a test tube (no stirring) for 1 hour at a glass transition temperature of the acrylic thermoplastic polymer (A) + 130 ° C. After carrying out the residence test, a 10% by weight tetrahydrofuran dispersion was prepared, and the volume average particle diameter was measured using a laser diffraction scattering particle size distribution measuring device LS230 manufactured by BECKMAN COULTER. In addition, the sample after the retention test was press-pressed at 260 ° C. to obtain a 40 μm-thick film, cut into a strip-shaped sample of 127 mm × 12.7 mm, and measured for tensile elongation at break according to ASTM D-638. The subsequent tensile elongation at break is shown in Table 2.

Reference Example (1) Synthesis of Copolymer (a) (a-1)
The following mixed substances were supplied to a stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra-type stirring blade, and the system was bubbled with nitrogen gas at 10 L / min for 15 minutes while stirring at 250 rpm. Next, nitrogen gas was flowed at a flow rate of 5 L / min, and the reaction system was heated to 80 ° C. while stirring. When the internal temperature reached 80 ° C., the polymerization was started. The internal temperature was maintained at 80 ° C. for 90 minutes, and after raising the temperature to 95 ° C., the polymerization was further continued for 90 minutes to complete the polymerization. The reaction system was cooled to room temperature, and the resulting slurry was treated with a centrifuge “LAC-21” (product of Matsumoto Machine Sales Co., Ltd.) for 2 hours while flowing nitrogen gas, and copolymer (a-1) And the organic solvent were separated. The polymer recovery rate by the centrifuge processing was almost 100%. The reslurry washing was repeated 3 times with hot water at 80 ° C. and dried at 80 ° C. for 12 hours to obtain a powdery copolymer (a-1). The copolymer (a-1) had a polymerization rate of 62% and a weight average molecular weight of 130,000.
Methacrylic acid 25 parts by weight Methyl methacrylate 75 parts by weight Butyl acetate 600 parts by weight n-Heptane 200 parts by weight Lauryl peroxide 0.5 parts by weight

Reference Example (2) Production of Acrylic Thermoplastic Polymer (A) Containing Glutaric Anhydride-Containing Unit (A-1)
100 parts by weight of the copolymer (a-1) obtained in Reference Example (1) was blended with 0.2 parts by weight of lithium acetate as a catalyst, and a 38 mmφ biaxial / uniaxial composite continuous kneading extruder (HTM38 (CTE, L / D = 47.5, vent part: 2 places) While purging nitrogen from the hopper part at an amount of 10 L / min, the screw rotation speed was 75 rpm, the raw material supply rate was 10 kg / h, An intramolecular cyclization reaction was performed at a cylinder temperature of 290 ° C. to obtain a pellet-shaped thermoplastic polymer (A-1), which was then dried at 80 ° C. for 8 hours and quantified by ¹ H-NMR. The copolymer component composition was glutaric anhydride-containing unit: 32% by weight, methyl methacrylate unit: 64% by weight, methacrylic acid unit: 4% by weight, and glass transition temperature was 138 ° C.

Reference Example (3) Other Acrylic Thermoplastic Polymer (A-2)
Except having changed the mixed material into the following, it superposed | polymerized like (a-1) of the reference example (1), and obtained the copolymer (A-2). ^The composition of each copolymer component determined by ¹ H-NMR was N-cyclohexylmaleimide unit: 25% by weight and methyl methacrylate unit: 75%. The glass transition temperature was 130 ° C.
N-cyclohexylmaleimide 50 parts by weight Methyl methacrylate 50 parts by weight t-dodecyl mercaptan 0.4 part by weight Lauryl peroxide 0.3 part by weight

Reference Example (4) Preparation of Multilayer Polymer Containing Rubber Layer (B-1)
The following composition was added as an initial adjustment solution in a glass container (capacity 5 liters) with a cooler.
Deionized water: 120 parts by weight Potassium carbonate: 0.5 parts by weight Dioctyl sulfosuccinate: 0.5 parts by weight Potassium persulfate: 0.05 parts by weight

While stirring the initial adjustment solution under a nitrogen atmosphere, the following composition for forming a rubbery layer was added and reacted at 70 ° C. for 30 minutes to obtain a rubbery polymer.
Butyl acrylate: 75 parts by weight Styrene: 25 parts by weight Allyl methacrylate: 0.5 parts by weight 1,4-butylene glycol diacrylate: 3 parts by weight

The following composition forming a layer (outermost layer) other than the rubbery layer shown in Table 1 was continuously added at 70 ° C. for 90 minutes while stirring, and held for another 90 minutes after the addition was completed. An outer layer was formed.
Methyl methacrylate: 30 parts by weight Methacrylic acid: 12 parts by weight Deionized water: 20 parts by weight Potassium persulfate: 0.1 parts by weight

  The polymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered and dried to obtain a multilayer polymer (B-1) having an average particle size of 0.17 μm.

(B-2) to (B-10)
Multilayer polymers (B-2) to (B-10) were obtained in the same manner as (B-1) except that the monomer species and amount used were changed as described in Table 1. Abbreviations in Table 1 are as follows.
AMA: allyl methacrylate TCA: triallyl cyanurate BGDA: 1,4-butylene glycol diacrylate MMA: methyl methacrylate MAA: methacrylate CHMI: N-cyclohexylmaleimide

(B-11)
The following composition was added as an initial adjustment solution in a glass container (capacity 5 liters) with a cooler.
Deionized water: 120 parts by weight Sodium pyrophosphate decahydrate: 0.1 part by weight Sodium polyoxyethylene alkyl ether sulfate: 0.5 part by weight (“Latemul E-118” manufactured by Kao Corporation)
Potassium persulfate: 0.03 parts by weight

While stirring the initial adjustment solution under a nitrogen atmosphere, the following composition forming the innermost layer was added and reacted at 80 ° C. for 30 minutes.
Methyl methacrylate: 22 parts by weight Styrene: 3 parts by weight

The following composition which forms a rubbery layer was then added with stirring and reacted at 80 ° C. for 30 minutes to obtain a rubbery polymer.
Butyl acrylate: 75 parts by weight Styrene: 25 parts by weight Allyl methacrylate: 2 parts by weight 1,4-butylene glycol diacrylate: 5 parts by weight Deionized water: 50 parts by weight Potassium persulfate: 0.1 parts by weight

The following composition forming a layer (outermost layer) other than the rubbery layer shown in Table 1 was continuously added at 70 ° C. for 90 minutes while stirring, and held for another 90 minutes after the addition was completed. An outer layer was formed.
Methyl methacrylate: 39 parts by weight Methacrylic acid: 14 parts by weight Deionized water: 40 parts by weight Potassium persulfate: 0.1 parts by weight

  The polymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to obtain a multilayer polymer (B-11) having an average particle size of 0.17 μm.

Examples 1-6, Comparative Examples 1-4
Reference Example (5) Production of Thermoplastic Resin Composition The acrylic thermoplastic polymer (A) obtained in the above Reference Examples (2) and (3) and the multilayer polymer (B) containing a rubbery layer are shown. 1 with a composition ratio shown in FIG. 1 and using a twin screw extruder TEX30 (L / D = 44.5) manufactured by Nippon Steel Co., Ltd., while purging nitrogen at an amount of 10 L / min from the hopper, The mixture was kneaded at 100 rpm, a raw material supply rate of 10 kg / hour, and a cylinder temperature of 280 ° C. to obtain a pellet-shaped thermoplastic resin composition.

2 g of the obtained thermoplastic resin composition pellets were weighed, extracted in a 200 g tetrahydrofuran solvent with stirring at 60 ° C. for 10 hours, and centrifuged at 10,000 rpm for 60 minutes. This operation was repeated three times, removed insoluble content of a tetrahydrofuran solvent, determined by 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, glutaric Formation of acid anhydride-containing units was confirmed.

  From Examples 1 to 9 and Comparative Examples 1 and 2, the (B) thermoplastic resin composition having excellent dispersion stability as defined in the present invention is difficult to agglomerate even after heat retention with respect to the dispersibility of the multilayer structure polymer. (A) has the same kind of outermost layer structure as the acrylic thermoplastic polymer, and can be obtained by using a specific amount of a polyfunctional monomer. It can be seen that high mechanical properties and toughness are maintained even after retention. In particular, it can be seen that it is preferable to use a polyfunctional monomer containing an allyl group and a polyfunctional monomer not containing an allyl group in combination as the polyfunctional monomer.

Claims (11)

Containing 100 to 100 parts by weight of an acrylic thermoplastic polymer (A) having a glass transition temperature of 120 ° C. or higher, containing 1 to 100 parts by weight of a multilayer polymer (B) having one or more rubber layers inside; And a thermoplastic resin composition satisfying the following (I) and (II):
(I) The average particle diameter of the multilayer polymer (B) having one or more rubbery layers inside is 0.1 to 1 μm;
(II) The average particle diameter of the multilayer polymer (B) after the thermoplastic resin composition is heated and retained for 1 hour at the glass transition temperature of the acrylic thermoplastic polymer (A) + 130 ° C. is 100 μm or less. The acrylic thermoplastic polymer (A) having a glass transition temperature of 120 ° C. or higher is a copolymer containing (i) a glutaric anhydride-containing unit represented by the following general formula (1): The thermoplastic resin composition according to claim 1.

(However, R ¹ and R ² are the same or different and represent any one selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms.) The acrylic thermoplastic polymer (A) having a glass transition temperature of 120 ° C. or higher is obtained by converting (i) a glutaric anhydride-containing unit represented by the general formula (1) from 15 to 50% by weight (ii) an unsaturated carboxylic acid. The thermoplastic resin composition according to claim 2, which is a copolymer having 50 to 85% by weight of an alkyl ester unit and (iii) 10% by weight or less of an unsaturated carboxylic acid unit. The polymer constituting the rubber layer of the multilayer polymer (B) is a copolymer containing an alkyl acrylate unit and a substituted or unsubstituted styrene unit. Thermoplastic resin composition. The polymer constituting the rubber layer of the multilayer polymer (B) is a polyfunctional monomer in an amount of 2 to 100 parts by weight based on a total of 100 parts by weight of an alkyl acrylate unit and a substituted or unsubstituted styrene unit. The thermoplastic resin composition according to claim 4, wherein the thermoplastic resin composition is a copolymer obtained by copolymerization of 20 parts by weight. The polymer constituting the rubber layer of the multilayer polymer (B) is a polyfunctional monomer containing an allyl group with respect to a total of 100 parts by weight of an alkyl acrylate unit and a substituted or unsubstituted styrene unit. 6. The thermoplastic resin composition according to claim 5, which is a polymer obtained by copolymerizing 1 to 10 parts by weight of a monomer and 1 to 10 parts by weight of a polyfunctional monomer having no allyl group. The polymer constituting the rubber layer of the multilayer polymer (B) is a polyfunctional monomer containing an allyl group with respect to a total of 100 parts by weight of an alkyl acrylate unit and a substituted or unsubstituted styrene unit. The thermoplastic resin composition according to claim 6, which is a polymer obtained by copolymerizing 1 to 10 parts by weight of a monomer and 4 to 10 parts by weight of a polyfunctional monomer having no allyl group. The thermoplastic resin composition according to claim 6, wherein the polyfunctional monomer containing an allyl group is allyl acrylate and / or allyl methacrylate. The thermoplastic polymer according to any one of claims 1 to 8, wherein the polymer constituting the outermost shell layer of the multilayer polymer (B) contains a glutaric anhydride-containing unit represented by the following general formula (1). Resin composition.

(However, R ¹ and R ² are the same or different and represent any one selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms.) The molded article containing the thermoplastic resin composition in any one of Claims 1-9. The film containing the thermoplastic resin composition in any one of Claims 1-9.