JP2008106225A - Thermoplastic polymer and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic polymer with a glutaric anhydride-containing unit that has a high grade of heat resistance, a color tone and transparency, as well as excellent tensile characteristics and retention of tensile strength after moist heat treatment as compared to conventional polymers. <P>SOLUTION: This thermoplastic polymer has a glutaric anhydride-containing unit, wherein the content of a polymer having a molecular weight of 4 times the weight average molecular weight of the polymer or higher remains equal to a specific value or less. The method for manufacturing the polymer characterized by producing an original copolymer by a copolymerization in the presence of a specific chain transfer agent is also disclosed. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermoplastic polymer containing a glutaric anhydride-containing unit having a high degree of heat resistance, color tone, and transparency, and excellent in tensile strength retention ratio after conventional heat treatment, tensile properties and wet heat treatment, and production thereof It is about the method.

  Amorphous resins such as polymethyl methacrylate (hereinafter referred to as “PMMA”) and polycarbonate (hereinafter referred to as “PC”) make use of transparency and dimensional stability of optical materials, household electrical appliances, office automation equipment, automobiles, and the like. It is used in a wide range of fields including parts.

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

  At present, these transparent resins are also used as lamp members for automobiles such as tail lamps and head lamps.In recent years, tail lamp lenses, inner lenses, There is a tendency to reduce the distance between various lenses such as headlamps and shield beams and the light source and to reduce the thickness of the parts, and excellent molding processability and melt retention stability are required. In addition, since the vehicle is used under severe conditions, the shape change and physical property change under high temperature and humidity are small, and excellent scratch resistance, weather resistance, and oil resistance are also required.

  However, although PMMA resin has excellent transparency and weather resistance, there is a problem that heat resistance is 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, and has optical anisotropy in the molded product, molding processability, melt residence stability, and heat and humidity resistance. There were problems such as poor aging, scratch resistance and oil resistance.

  Therefore, for the purpose of improving the heat resistance of PMMA, a copolymer in which a maleimide monomer or a maleic anhydride monomer is introduced as a heat resistance imparting component has been developed. However, the maleimide monomer and maleic anhydride monomer have low reactivity with methyl methacrylate, and the copolymer into which these are introduced has a problem of poor thermal stability and poor color tone.

  As a method for solving these problems, a copolymer containing an unsaturated carboxylic acid unit is obtained by heating a copolymer containing an unsaturated carboxylic acid unit by a cyclization reaction using an extruder. Coalescence is disclosed (for example, Patent Document 1). However, the copolymer having a glutaric anhydride-containing unit obtained by heat-treating the copolymer using an extruder has a problem that it is markedly colored.

  Moreover, the method of manufacturing the copolymer containing a glutaric anhydride containing unit is disclosed by heating the polymer solution containing an unsaturated carboxylic acid unit under vacuum (refer patent document 2). However, in the methods described in these publications, in order to remove the solvent completely under vacuum, heat treatment for a long time is required at a high temperature, and much labor and energy are required. there were. Further, when a polymer containing an unsaturated carboxylic acid monomer is produced in a solution, it is necessary to increase the polymerization temperature in order to obtain a high polymerization rate. However, the coloration-suppressing effect of the copolymer containing the resulting glutaric anhydride-containing unit is not sufficient, and does not satisfy the recent demand for more colorlessness (advanced color tone). Further, the copolymer was not sufficient in terms of tensile properties required for use in thin-walled molded products such as films and tensile strength after wet heat treatment.

  Therefore, as disclosed in Patent Document 3, a copolymer containing a specific unsaturated carboxylic acid unit is produced under specific polymerization conditions, and then the copolymer is heat-treated, whereby color tone, transparency and retention are obtained. A thermoplastic polymer containing a glutaric anhydride-containing unit having excellent stability and a method for producing the same have been proposed. According to the technique proposed in Patent Document 3, the coloring and retention stability of the obtained thermoplastic polymer is greatly improved, but the optical lens, prism, mirror, optical disk, optical fiber, liquid crystal display sheet / film, polarizing plate, In order to be used for higher performance optical materials such as light guide plates, further improvements in color tone, transparency, tensile properties and tensile strength during wet heat are required, and unmelted so-called fish eyes, etc. A thermoplastic polymer with less foreign matter has been desired.

  Further, a thermoplastic polymer having a specific weight average molecular weight and molecular weight distribution and containing a glutaric anhydride-containing unit excellent in color tone, transparency, heat resistance, moldability, optical isotropy and solvent resistance is obtained. It has been proposed (see Patent Document 4). However, even with the technique proposed in Patent Document 4, the tensile properties required for use in thin molded articles such as films and the tensile strength after wet heat treatment are still not sufficient, and a thermoplastic polymer with less unmelted foreign matter. Was desired.

  On the other hand, regarding polymer production methods, generally, PMMA resin, (meth) acrylic acid ester monomer copolymer (also referred to as AC resin), polystyrene (hereinafter also referred to as PS resin), acrylonitrile-styrene copolymer When a coalescence (hereinafter also referred to as AS resin), acrylonitrile-styrene-butadiene resin (hereinafter also referred to as ABS resin), etc. are produced industrially, most of them are produced by bulk polymerization, suspension polymerization, and emulsion polymerization. Only a small part is produced by solution polymerization.

  Bulk polymerization, suspension polymerization, and emulsion polymerization are convenient production methods for mass production. In suspension polymerization and emulsion polymerization, water-based polymerization methods such as methacrylic acid and acrylic acid are used. It is difficult to copolymerize a highly water-soluble unsaturated monomer having a carboxyl group such as maleic acid or itaconic acid, and a homopolymer of the unsaturated monomer having a high water-solubility is formed to form a film. There was a problem that later became unmelted foreign matter. Furthermore, in bulk polymerization, suspension polymerization, and emulsion polymerization, it is extremely difficult to control the polymerization rate, and it is difficult to suppress the formation of a macromolecular weight (defined as a polymer having a weight average molecular weight of 8 times or more in the present invention). is there. For this reason, these macromolecular substances are mixed as foreign substances in the polymer, and when processed into a film or molded product, there are cases where defects (such as fish and fish eyes) with this macromolecular substance as the core may occur. The tensile properties, especially when processed into a thin molded article such as a film, tend to decrease due to the presence of macromolecular weight. Therefore, polymers produced by bulk polymerization, suspension polymerization, and emulsion polymerization may be limited in use in optical applications that require a high degree of transparency and uniformity and applications that require tensile properties. There was a point.

  On the other hand, in solution polymerization, productivity decreases, but copolymerization at a low concentration allows bulk polymerization, suspension polymerization, emulsion polymerization ratio, macromolecular weight, and homopolymer of the unsaturated monomer having high water solubility. Although there is a tendency to suppress the formation, when copolymerizing a monomer mixture containing an unsaturated carboxylic acid monomer, the formation suppression of the macromolecular weight is not sufficient, and the color tone and the melt retention stability are not satisfactory. It has been relatively difficult to suppress the production of adversely affected low molecular weight substances (for example, polymers having a molecular weight of 5000 or less). Further, in solution polymerization, it is very difficult to separate and recover the produced copolymer from the organic solvent solution, and there is a problem that much labor and energy are required.

  As a method for solving such problems, a thermoplastic polymer having a glutaric anhydride-containing unit derived from a precursor polymer produced by precipitation polymerization has been proposed (see Patent Document 5). According to this patent document, by the precipitation polymerization, the ratio of the suspension polymer product and the formation of the macromolecular substance can be suppressed, and a thermoplastic polymer in which the amount of unmelted foreign matter is greatly reduced can be obtained. Since it contains more than a specific value, further improvement in tensile properties and tensile strength retention after wet heat treatment has been demanded. In addition, in precipitation polymerization, when the polymerization rate is improved from the viewpoint of productivity, the amount of low molecular weight (for example, a polymer having a molecular weight of 5000 or less) that tends to adversely affect the color tone and melt retention stability tends to increase. It was in.

Non-Patent Documents 1 and 2 disclose a precipitation polymerization method using a solvent containing an aromatic group such as benzene or toluene for copolymerization of an unsaturated carboxylic acid monomer. However, according to the study by the present inventors, when a monomer mixture containing an unsaturated carboxylic acid monomer and an unsaturated carboxylic acid alkyl ester is copolymerized using the above-mentioned solvent, there is a problem in the monomer mixture. The dimerization of the saturated carboxylic acid monomer occurs remarkably, forming a partially heterogeneous phase and unavoidable chain transfer to the solvent, the copolymer composition of the resulting copolymer, molecular weight, It was found that it was difficult to precisely control the molecular weight distribution and to reduce the content of high molecular weight substances and low molecular weight substances (for example, polymers having a molecular weight of 5000 or less), and in particular, the molecular weight distribution became extremely large. .
JP-A-49-85184 (page 1-2, Examples) JP-A-60-120707 (Page 1-2, Examples) JP 2004-002711 A (page 1-2, Examples) JP 2004-292281 A (page 1-2, detailed description of the invention) JP 2006-124438 A (Claims) Die Angewandte Makromolekuare Chemie 11 (1970) p53-62 Journal of Polymer Science: Polymer Letters Edition, Vol.18 (1980), p241-248

  Accordingly, the present invention provides a thermoplastic polymer containing a glutaric anhydride-containing unit that has high heat resistance, color tone, and transparency, and is superior in conventional ratio, tensile characteristics, and tensile strength retention after wet heat treatment, and its It is an object to provide a manufacturing method.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention are thermoplastic polymers containing glutaric anhydride-containing units, which are four times or more the value of the weight average molecular weight of the thermoplastic polymers. A thermoplastic polymer with a molecular weight of less than a specific value has a high heat resistance, color tone and transparency, and is superior in conventional ratio, tensile properties and tensile strength retention after wet heat treatment. The present invention has been found.

  That is, the present invention relates to [1] (i) a thermoplastic polymer containing a glutaric anhydride-containing unit represented by the following general formula (1), and a gel permeation chromatography method of the thermoplastic polymer: A thermoplastic polymer characterized in that the content of the polymer having a molecular weight of 4 times or more of the value of the weight average molecular weight obtained by the method is 3.0% by weight or less.

(However, R ¹ and R ² are the same or different and represent any one selected from a hydrogen atom and an organic residue having 1 to 20 carbon atoms.)
[2] The thermoplastic polymer as described in [1], wherein the glass transition temperature is 120 ° C. or higher.
[3] The thermoplastic polymer as described in [1] or [2], wherein the thermoplastic polymer has a weight average molecular weight of 30000 or more.
[4] The thermoplastic polymer is a copolymer having (i) a glutaric anhydride-containing unit represented by the general formula (1) and (ii) an unsaturated carboxylic acid ester unit. The thermoplastic polymer according to any one of [1] to [3].
[5] The thermoplastic polymer is converted into (ii) dehydration and / or (b) depolymerization to a raw copolymer (A) containing (ii) an unsaturated carboxylic acid ester unit and (iii) an unsaturated carboxylic acid unit. The thermoplastic polymer according to any one of [1] to [4], which is obtained by performing an intramolecular cyclization reaction by an alcohol reaction.
[6] A chain transfer agent containing a mercaptocarboxylic acid ester and / or an aromatic thiol is added to the monomer mixture containing the unsaturated carboxylic acid ester monomer and the unsaturated carboxylic acid monomer, and in the presence or absence of a solvent. A production method for producing an original copolymer (A) comprising (ii) an unsaturated carboxylic acid ester unit and (iii) an unsaturated carboxylic acid unit by copolymerization in the presence thereof.
[7] The method for producing an original copolymer (A) according to [6], wherein the chain transfer agent is a chain transfer agent containing a mercaptocarboxylic acid ester.
[8] The content of the polymer having a molecular weight of 4 times or more of the value of the weight average molecular weight obtained by the gel permeation chromatography method of the original copolymer (A) is 3.0% by weight or less. [6] or [7] characterized in that the method for producing an original copolymer (A) according to [7].
[9] In a solvent in which the original copolymer (A) containing (ii) an unsaturated carboxylic acid ester unit and (iii) an unsaturated carboxylic acid unit is 1 g / 100 g or less in solubility of the original copolymer (A) In any one of [6] to [8], obtained by copolymerizing a monomer mixture comprising an unsaturated carboxylic acid ester monomer and an unsaturated carboxylic acid monomer. The manufacturing method of the original copolymer (A) of description.
[10] By subjecting the original copolymer (A) obtained in any one of [6] to [9] to an intramolecular cyclization reaction by (i) dehydration and / or (b) dealcoholization reaction. A method for producing a thermoplastic polymer, comprising producing a thermoplastic polymer containing (i) a glutaric anhydride-containing unit represented by the following general formula (1):

(However, R ¹ and R ² are the same or different and represent any one selected from a hydrogen atom and an organic residue having 1 to 20 carbon atoms.)

[11] The method for producing a thermoplastic polymer, wherein the thermoplastic polymer according to [10] is the thermoplastic polymer according to any one of [1] to [4].
[12] A thermoplastic resin composition, wherein the thermoplastic polymer according to any one of [1] to [5] further contains a rubber-containing polymer (C).
[13] A molded article or film obtained by processing the thermoplastic polymer according to any one of [1] to [5] or the thermoplastic resin composition according to [12].

  The thermoplastic polymer of the present invention has high heat resistance, color tone and transparency, and is excellent in conventional ratio, tensile characteristics and tensile strength retention after wet heat treatment. Therefore, the thermoplastic polymer of the present invention can be suitably used for various applications such as optical materials, machine-related parts, precision machine-related parts, electrical equipment housings, information equipment-related parts and the like.

  Hereinafter, the thermoplastic polymer of the present invention and the production method thereof will be specifically described.

  The thermoplastic polymer of the present invention is a thermoplastic polymer containing (i) a glutaric anhydride-containing unit represented by the general formula (1), and gel permeation chromatography of the thermoplastic polymer. The content of the polymer having a molecular weight of 4 times or more of the value of the weight average molecular weight obtained by the method is 3.0% by weight or less.

Here, in the general formula (1), R ¹ and R ² are the same or different, and are any one selected from a hydrogen atom and an organic residue having 1 to 20 carbon atoms. The organic residue having 1 to 20 carbon atoms is not particularly limited, and may be linear, branched or cyclic, and may contain a hetero atom in the structure. R ¹ and R ² are preferably the same or different and are each a hydrogen atom, an unsubstituted or halogen-substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or halogen or aliphatic hydrocarbon group. A substituted aromatic group having 6 to 20 carbon atoms, an unsubstituted or substituted alicyclic hydrocarbon group having 3 to 20 carbon atoms substituted with a halogen or an aliphatic hydrocarbon group, and a hydroxyalkyl group having 1 to 20 carbon atoms R ¹ and R ² are more preferably the same or different and are a hydrogen atom, an unsubstituted or substituted C1-C6 aliphatic hydrocarbon group substituted with halogen, unsubstituted or A phenyl group substituted with a halogen or an aliphatic hydrocarbon, an unsubstituted or substituted alicyclic hydrocarbon group of 3 to 6 carbon atoms with a halogen or an aliphatic hydrocarbon group, and carbon A group selected from 1-6 hydroxyalkyl group, more preferably a R ^1, R ^2, identical or different different and is any one selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms, Particularly preferred is the case where R ¹ and R ² are both methyl groups.

  A polymer having a molecular weight 4 times or more the value of a weight average molecular weight (hereinafter sometimes referred to as Mw) obtained by gel permeation chromatography of the thermoplastic polymer (hereinafter sometimes referred to as a high molecular weight body). ) Is preferably 2.7% by weight or less, more preferably 2.5% by weight or less, still more preferably 2.0% by weight or less, particularly preferably 1.5% by weight or less, and most preferably 1.4% by weight or less. The content of the polymer having a molecular weight of 4 times or more of the value of the weight average molecular weight in the present invention is a value calculated from the weight fraction in the molecular weight distribution diagram obtained by the gel permeation chromatography method described below. It is. A thermoplastic polymer is dissolved in dimethylformamide to form a 0.3% by weight measurement sample solution, and dimethylformamide is used as a solvent at a temperature of 23 ° C. at a DAWN-DSP type multi-angle light scattering photometer (manufactured by Wyatt Technology) ) With a gel permeation chromatograph (pump: Model 515, manufactured by Waters, column: TSK-gel-GMHXL, manufactured by Tosoh Corporation, flow rate: 0.8 ml / min), and then obtained. For the absolute molecular weight distribution curve (the horizontal axis is the logarithm of molecular weight, and the vertical axis is plotted by normalizing the mole fraction so that the peak area is 1), it is 4 times the value of the weight average molecular weight The ratio of the total peak area of the polymer having the above weight average molecular weight to the total peak area is the high molecular weight content (% by weight). And ask.

  When the polymer having a molecular weight of 4 times or more of the value of the weight average molecular weight exceeds 3.0% by weight, the presence of this polymer decreases the tensile properties, that is, the balance between tensile strength and tensile elongation. In addition, the tensile strength retention after wet heat treatment tends to decrease, which is not preferable.

  The lower limit of the weight average molecular weight of the thermoplastic polymer of the present invention is not particularly limited, but is preferably 10,000 or more, more preferably 20,000 or more, still more preferably 30,000 or more, and particularly preferably 40,000 or more. Most preferably, it is 45000 or more. The upper limit of the weight average molecular weight is not particularly limited, but is preferably 1000000 or less, more preferably 200000 or less, further preferably 150,000 or less, particularly preferably 115000 or less, and most preferably 110,000 or less. is there. The lower limit of the molecular weight distribution of the thermoplastic polymer of the present invention is not particularly limited, but is preferably 1.05 or more, more preferably 1.1 from the viewpoint of improving the fluidity of the thermoplastic polymer of the present invention. Or more, more preferably 1.2 or more, particularly preferably 1.3 or more, and most preferably 1.4 or more. The upper limit of the molecular weight distribution is not particularly limited, but is usually preferably 10.0 or less, preferably 5.0 or less from the viewpoint of impact resistance and tensile strength, and more preferably 3.0 or less. Further, it is preferably 2.85 or less, particularly preferably 2.7 or less, and most preferably 2.5 or less. The molecular weight distribution in the present invention refers to the weight average molecular weight (absolute molecular weight) and the number average molecular weight (absolute molecular weight) measured by the gel permeation chromatography method, and the weight average molecular weight (absolute molecular weight) / number average molecular weight ( (Absolute molecular weight).

  The lower limit of the content of the (i) glutaric anhydride-containing unit in the thermoplastic polymer of the present invention is not particularly limited, but is 5% by weight or more in 100% by weight of the thermoplastic copolymer from the viewpoint of improving heat resistance. It is preferably 10% by weight or more, more preferably 13% by weight or more, particularly preferably 15% by weight or more, and most preferably 20% by weight or more. (I) The upper limit of the content of the glutaric anhydride-containing unit is not particularly limited, and may be 100% by weight in 100% by weight of the thermoplastic copolymer. Or less, more preferably 70% by weight or less, still more preferably 60% by weight or less, particularly preferably 50% by weight or less, and most preferably 45% by weight or less.

  Although not essential, it is preferable that the thermoplastic polymer contains (ii) an unsaturated carboxylic acid ester unit from the viewpoint of improving moldability. (Ii) The lower limit of the content of the unsaturated carboxylic acid ester unit is not particularly limited, but is preferably 20% by weight or more, more preferably 30% by weight or more, based on 100% by weight of the monomer mixture. More preferably 40% by weight or more, particularly preferably 50% by weight or more, and most preferably 55% by weight or more. The upper limit of the content of the unsaturated carboxylic acid ester unit is not particularly limited, but is preferably 95% by weight or less, more preferably 90% by weight or less, still more preferably 87% by weight or less, particularly preferably. 85% by weight or less, and most preferably 80% by weight or less.

  Further, the thermoplastic polymer of the present invention may contain (iii) an unsaturated carboxylic acid unit and / or another vinyl monomer unit capable of copolymerization.

  In the present invention, when the thermoplastic polymer is derived from an intramolecular cyclization reaction of the original copolymer (A), (i) dehydration and / or (b) dealcoholization reaction of the original copolymer (A). By controlling the reaction rate, the amount of (iii) unsaturated carboxylic acid unit contained in the thermoplastic polymer can be adjusted. When the thermoplastic polymer contains (iii) an unsaturated carboxylic acid unit, the upper limit of the content of (iii) the unsaturated carboxylic acid unit is not particularly limited, but is preferably 50% by weight or less, More preferably, it is 30 weight% or less, More preferably, it is 10 weight% or less, Especially preferably, it is 5 weight% or less, Most preferably, it is 3 weight% or less. That is, (iii) the content of the unsaturated carboxylic acid unit is preferably in the range of 0 to 50% by weight, more preferably in the range of 0 to 30% by weight, and still more preferably in the range of 0 to 10% by weight. Particularly preferably, it is in the range of 0 to 5% by weight, and most preferably in the range of 0 to 3% by weight. The smaller the amount of (iii) unsaturated carboxylic acid units in the thermoplastic polymer, the more the tensile strength retention after wet heat treatment tends to be improved. In particular, (iii) the content of unsaturated carboxylic acid units is 0. The range of ˜2% by weight is preferable from the viewpoint of the tensile strength retention after wet heat treatment. (Iii) In order to control the amount of the unsaturated carboxylic acid unit within the above preferred range, (iii) at least a part of the acid of the unsaturated carboxylic acid unit remaining in the thermoplastic polymer is blocked by an esterification reaction or the like. It is also preferably used. In addition, the upper limit of the content of other copolymerizable vinyl monomer units is not particularly limited, but is 75% by weight or less from the viewpoint of color tone, transparency, optical isotropy, and chemical resistance. It is preferably 35% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less. That is, the content range of the other copolymerizable vinyl monomer units is preferably in the range of 0 to 75% by weight, more preferably in the range of 0 to 35% by weight, and still more preferably in the range of 0 to 75% by weight. It is in the range of 10% by weight, particularly preferably in the range of 0 to 5% by weight. In particular, when an aromatic vinyl monomer unit such as styrene is contained, if the content is too large, the color tone, transparency, optical isotropy and chemical resistance tend to decrease.

  In addition, an infrared spectrophotometer or a nuclear magnetic resonance (1H-NMR, 13C-NMR) measuring instrument is generally used for quantification of each component unit in the thermoplastic polymer and the original copolymer (A) of the present invention. However, in the present invention, quantification is performed by 13C-NMR method. In the 13C-NMR method, each of the obtained thermoplastic polymer and original copolymer (A) is dissolved in deuterated pyridine at a concentration of 600 mg / 3 g, and a Varian, UNITY INOVA 500 type NMR measuring machine is used. The measurement core 13C, TMS as a reference, observation frequency 125.7 MHz, integration number 30000 times, the thermoplastic polymer at a temperature of 15 ° C., the original copolymer (A) at a temperature of 25 ° C., respectively Measurements were made. In the 13C-NMR spectrum of the thermoplastic polymer of the present invention, (i) the peak of the carbonyl group of the acid anhydride of the glutaric anhydride-containing unit is observed split into a chemical shift range of 170.50 to 174.40 ppm. , (Ii) The peak of the carbonyl group of the unsaturated carboxylic acid ester unit is observed by splitting the chemical shift in the range of 174.60 to 179.43 ppm depending on the sequence and tacticity, and (iii) the unsaturated carboxylic acid unit The peak of the carbonyl group is observed by splitting into a chemical shift range of 179.15 to 182.00 ppm depending on the sequence and tacticity. Here, (ii) the peak of the carbonyl group of the unsaturated carboxylic acid ester unit and (iii) the peak of the carbonyl group of the unsaturated carboxylic acid unit partially overlap, but the 13C-NMR spectrum of the thermoplastic polymer of the present invention (Ii) The peak of the carbonyl group of the unsaturated carboxylic acid ester unit occupies the portion where the peak of the carbonyl group of the unsaturated carboxylic acid ester unit and (iii) the peak of the carbonyl group of the unsaturated carboxylic acid unit overlap. Since the ratio is negligibly small compared to the ratio of (iii) the peak of the carbonyl group of the unsaturated carboxylic acid unit, in the 13C-NMR of the thermoplastic polymer of the present invention, (ii) the unsaturated carboxylic acid ester unit The peak of the carbonyl group of the chemical shift ranges from 174.60 to 179.14 ppm, (iii) unsaturated Peak of the carbonyl group of the carboxylic acid units, then the range of chemical shifts 179.15～182.00Ppm, shall determine the composition of each of these integrated values.

  In 13C-NMR of the original copolymer (A) of the present invention, (ii) the peak of the carbonyl group of the unsaturated carboxylic acid ester unit has a chemical shift range of 176.00 to 179.43 ppm depending on the sequence and tacticity. (Iii) The peak of the carbonyl group of the unsaturated carboxylic acid unit is observed by splitting into a chemical shift range of 179.15 to 182.00 ppm depending on the sequence and tacticity, and (ii) The peak of the carbonyl group of the unsaturated carboxylic acid ester unit and (iii) the peak of the carbonyl group of the unsaturated carboxylic acid unit partially overlap, but (iii) the peak of the carbonyl group of the unsaturated carboxylic acid ester unit and (iii) In the portion where the peak of the carbonyl group of the saturated carboxylic acid unit overlaps, (ii) Since the ratio of the carbonyl group peak of the rubonate unit is (iii) negligibly small compared to the ratio of the carbonyl group peak of the unsaturated carboxylic acid unit, in the present invention, (ii) the unsaturated carboxylic acid unit The peak of the carbonyl group of the acid ester unit is in the range of chemical shift 176.00 to 179.14 ppm, and the peak of the carbonyl group of the unsaturated carboxylic acid unit is in the range of chemical shift 179.15 to 182.00 ppm. Each composition is determined from these integrated values. When the 13C-NMR spectrum of the original copolymer (A) and the thermoplastic polymer of the present invention was measured in deuterated pyridine, (i) content of glutaric anhydride-containing unit, (iii) Content of saturated carboxylic acid unit, (ii) type of unsaturated carboxylic acid ester unit used, (iii) type of unsaturated carboxylic acid unit used, difference in water content contained in deuterated pyridine solution, In the 13C-NMR spectrum of each of the original copolymer (A) and the thermoplastic polymer of the present invention due to the influence of a minute error derived from a measuring instrument for each measurement, (ii) of unsaturated carboxylic acid ester units The chemical shift of each peak top of the carbonyl group peak and (iii) the carbonyl group peak of the unsaturated carboxylic acid unit is observed to be shifted (moved) within a range of about 0.2 ppm (each peak Tsu difference in chemical shift between the flop almost no change). Therefore, in this case, the shift of each chemical shift is taken into consideration (for example, when the chemical shift of each peak top of 13C-NMR carbonyl of the original copolymer is shifted to the high magnetic field side by 0.10 ppm, (ii) ) The peak of the carbonyl group of the unsaturated carboxylic acid ester unit has a chemical shift in the range of 175.90 to 179.04 ppm. (Iii) The peak of the carbonyl group of the unsaturated carboxylic acid unit has a chemical shift of 179.05 to 181.90 ppm. The respective compositions are determined from these integral values as a range of), and the compositions are obtained.

In the infrared spectroscopy, (i) glutaric anhydride containing units, absorption of 1800 cm ^-1 and 1760 cm ^-1 are characteristic, (iii) unsaturated carboxylic acid unit and (ii) an unsaturated carboxylic acid A distinction can be made from ester units. In the 1H-NMR method, for example, in the case of a copolymer consisting of a glutaric anhydride containing unit, methacrylic acid, and methyl methacrylate, the attribution of the spectrum in dimethyl sulfoxide heavy solvent is 0.5 to 1.5 ppm. Peak of methacrylic acid, methyl methacrylate and glutaric anhydride ring compound α-methyl group hydrogen, 1.6-2.1 ppm peak of polymer main chain methylene group hydrogen, 3.5 ppm peak of methacrylic acid Since the peak of 12.4 ppm of hydrogen of carboxylic acid ester of methyl acid (—COOCH ₃ ) is observed as hydrogen of carboxylic acid of methacrylic acid, the copolymer composition can be determined from the integral ratio of these spectra. In addition to the above, when styrene is contained as another copolymerization component, hydrogen in 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. can do.

  The glass transition temperature of the thermoplastic polymer of the present invention is not particularly limited, but is preferably 110 ° C. or higher, more preferably 120 ° C. or higher, from the viewpoint of practical heat resistance. In a more preferred embodiment, the glass transition temperature is 125 ° C. or higher, and more preferably 130 ° C. or higher. Further, the upper limit is not particularly limited, but is preferably 200 ° C. or less, more preferably 180 ° C. or less, still more preferably 170 ° C. or less, and particularly preferably 160 ° C. or less from the viewpoint of workability. It is. The glass transition temperature here is a glass transition temperature measured at a heating rate of 20 ° C./min using a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer).

  In a preferred embodiment, the thermoplastic polymer produced by the production method of the present invention preferably has a yellowness index value of 50 or less, more preferably 10 or less, and still more preferably 5 The coloration is particularly preferably 4 or less, and the color tone is suppressed, and in the most preferred embodiment, the color tone is extremely high as 2 or less. In the above, the yellowness is a value obtained by measuring the YI value of a 1 mm-thick molded product injection-molded at a glass transition temperature + 140 ° C. according to JIS-K7103. The lower limit of the yellowness is not particularly limited and is preferably as low as possible, but is usually about 1.

Further, regarding the thermoplastic polymer and the original copolymer (A) of the present invention, in a film having a thickness of 100 ± 5 μm, when this film was observed with an optical microscope and the number of foreign matters was confirmed, 10 was randomly selected. The number of foreign matters of 10 μm or more per 1 mm square unit area when the average value is evaluated as the number of foreign matters per 1 mm square unit area (pieces / mm ² ) Although there is no limit, it is preferably 1000 or less, more preferably 15 or less, further preferably 10 or less, particularly preferably 3 or less, and most preferably 0. Here, a film having a thickness of 100 ± 5 μm can be produced by solution casting and melt casting. For example, the solution casting method is a method in which the thermoplastic polymer of the present invention is dissolved in methyl ethyl ketone at a concentration of 25% by weight at room temperature with stirring for 24 hours, and the resulting thermoplastic polymer solution is cast on a glass plate. After that, a drying process is performed at 50 ° C. for 20 minutes and then at 80 ° C. for 30 minutes to form a film having a thickness of 100 ± 5 μm. In addition, when this film was observed with an optical microscope to confirm the number of foreign matters, when counting the number of foreign matters of 10 μm or more per 1 mm square unit area, it was observed at 10 points at random per sample. Then, counting of the number of foreign matters is repeated, and the average value is evaluated as the number of foreign matters per 1 mm square unit area (pieces / mm ² ). Specific examples of the optical microscope used for confirming the foreign matter include a differential interference reflection microscope (Nikon Corporation ECLIPSE LV100D). The optical microscope is used to observe the surface of a film having a thickness of 100 ± 5 μm, The number of irregularities derived from foreign matters is counted as the number of foreign matters.

  The foreign matters in the present invention are those other than disturbing foreign matters such as inorganic substances and organic substances mixed from the outside in the production process, and the macromolecular substances, ionomers and unsaturated carboxylic acids produced during the production of the original copolymer (A) of the present invention. By-products such as unit homopolymers, dispersion stabilizers, heat stabilizers, antioxidants and initiators, various additives used in the production process, or insoluble and / or non-melting components due to these alterations, and Among insoluble components and / or non-melting components including by-products such as macromolecular compounds, ionomers, and low molecular weight compounds produced when obtaining a thermoplastic polymer by an intramolecular cyclization reaction from the original copolymer, At least one. As a method for distinguishing foreign matters from other foreign matters excluding disturbance foreign matters mixed from the outside, for example, a method of measuring microscopic IR for each foreign matter and confirming characteristic absorption can be mentioned. There is no particular limitation on the method for obtaining the original copolymer (A) in which the foreign matter is less than or equal to the above-mentioned preferable content (the number of foreign matters of 10 μm or more per 1 mm square unit area is 1000 or less). It is preferable to use continuous bulk polymerization, solution polymerization, precipitation polymerization, continuous precipitation polymerization and a combination of these polymerization methods, and more preferably, precipitation polymerization is performed in the organic solvent (E) of the present invention.

The melt viscosity of the thermoplastic polymer of the present invention is not particularly limited, but is measured at a glass transition temperature + 150 ° C. using a plunger type capillary rheometer (Capillograph type 1C manufactured by Toyo Seiki Seisakusho), and a shear rate of 5 viewpoint of melt viscosity at a shear rate of 5 s ^-1 obtained by extrapolating seconds ^-1 (Pa · s) is preferably in the range of 10~100000Pa · s, improvement of melt filterability and melt film properties Is more preferably in the range of 100 to 10000 Pa · s, still more preferably in the range of 100 to 5000 Pa · s, and particularly preferably in the range of 100 to 2000 Pa · s.

  The method for producing the thermoplastic polymer containing the (i) glutaric anhydride-containing unit of the present invention is not particularly limited. For example, a monomer capable of forming a glutaric anhydride ring by polymerization, such as methacrylic anhydride, and the necessity A method obtained by (co) polymerizing an unsaturated carboxylic acid ester monomer and / or other vinyl monomer in the presence of a chain transfer agent containing a mercaptocarboxylic acid ester and / or an aromatic thiol, for example, Monomers that are precursors of unsaturated carboxylic acids such as tert-butyl acrylate and tert-butyl methacrylate were (co) polymerized in the presence of a chain transfer agent containing a mercaptocarboxylic acid ester and / or an aromatic thiol. Although there is a method obtained by intramolecular cyclization later, it is 4 times the value of the weight average molecular weight in the obtained thermoplastic polymer. Points to exhibit the effect of the content of the polymer having a molecular weight of above 3.0% by weight or less and preferably controlling the present invention, and be manufactured by the two steps described below in terms of industrial property are preferred. That is, in the case where it contains an unsaturated carboxylic acid ester monomer and an unsaturated carboxylic acid monomer that give a glutaric anhydride containing unit in a later step, and other vinyl monomer units, the unit And a step of producing a raw copolymer (A) (first step) by copolymerization with a vinyl-based monomer that gives the raw copolymer, and then the raw copolymer (A) in the presence of a suitable catalyst or It is a production method comprising a step (second step) in which an intramolecular cyclization reaction is carried out by (a) dehydration and / or (b) dealcoholization, preferably by heating in the absence. In this case, typically, the carboxyl group of two (iii) unsaturated carboxylic acid units is dehydrated by heating the original copolymer (A), or adjacent (iii) unsaturated carboxylic acid units. And (ii) 1 unit of the (i) glutaric anhydride-containing unit is produced by elimination of the alcohol from the unsaturated carboxylic acid ester unit.

  The original copolymer (A) of the present invention is a copolymer comprising (ii) an unsaturated carboxylic acid ester unit and (iii) an unsaturated carboxylic acid unit. (Ii) The unsaturated carboxylic acid ester unit is preferably represented by the following general formula (2), and (iii) the unsaturated carboxylic acid unit is preferably represented by the following general formula (3). .

(However, R ³ represents any one selected from hydrogen and an organic residue having 1 to 20 carbon atoms, and R ⁴ represents an organic residue having 1 to 22 carbon atoms)

(However, R ⁵ represents any one selected from hydrogen and an organic residue having 1 to 20 carbon atoms)

Here, the organic residue having 1 to 20 carbon atoms of R ³ is not particularly limited, and may be linear, branched, or cyclic, and may contain a hetero atom in the structure. R ³ is preferably a hydrogen atom, an unsubstituted or halogen-substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or aromatic group having 6 to 20 carbon atoms substituted with a halogen or an aliphatic hydrocarbon group. R ³ is a group selected from an aliphatic group, an unsubstituted or substituted alicyclic hydrocarbon group having 3 to 20 carbon atoms substituted with a halogen or an aliphatic hydrocarbon group, and a hydroxyalkyl group having 1 to 20 carbon atoms; More preferably, it is a hydrogen atom, an unsubstituted or halogen-substituted aliphatic hydrocarbon group having 1 to 6 carbon atoms, a phenyl group that is unsubstituted or substituted with halogen or an aliphatic hydrocarbon, an unsubstituted or halogen or aliphatic carbonized alicyclic hydrocarbon group having 3 to 6 carbon atoms which is substituted by a hydrogen radical, and a group selected from hydroxyalkyl group having 1 to 6 carbon atoms, further good as R ³ Properly it is either selected from alkyl groups of 1 to 5 hydrogen atoms and carbon atoms, and especially preferably a methyl group.

The organic residue having 1 to 22 carbon atoms of R ⁴ is not particularly limited, and may be linear, branched or cyclic, and may contain a hetero atom in the structure. R ⁴ is preferably an unsubstituted or halogen-substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic group having 6 to 20 carbon atoms by halogen or an aliphatic hydrocarbon group, It is any one selected from unsubstituted or substituted alicyclic hydrocarbon groups having 3 to 22 carbon atoms and substituted with halogen or aliphatic hydrocarbon groups, and hydroxyalkyl groups having 1 to 20 carbon atoms. It is selected from a group selected from a substituted or halogen-substituted alkyl group having 1 to 6 carbon atoms, a phenyl group that is unsubstituted or substituted by halogen or an alkyl group, a cyclohexyl group, and a hydroxyalkyl group having 1 to 6 carbon atoms. a group, more preferably an unsubstituted or halogen-substituted alkyl group having 1 to 6 carbon atoms, particularly preferably as R ^4, An alkyl group of prime 1-6, unsaturated carboxylic acid ester unit represented by the general formula (2) is particularly preferably an unsaturated carboxylic acid alkyl ester unit having 1 to 6 carbon atoms.

In the general formula (3), the organic residue having 1 to 20 carbon atoms of R ⁵ is not particularly limited, and may be linear, branched, or cyclic, and may contain a hetero atom in the structure. R ⁵ is preferably hydrogen, unsubstituted or halogen-substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, unsubstituted or substituted with halogen or aliphatic hydrocarbon group and having 6 to 20 carbon atoms. And a group selected from an alicyclic hydrocarbon group having 3 to 20 carbon atoms which is unsubstituted or substituted with a halogen or an aliphatic hydrocarbon group, and more preferably a hydrogen atom, unsubstituted or substituted with a halogen An alkyl group having 1 to 6 carbon atoms, a phenyl group unsubstituted or substituted with a halogen or an alkyl group, and an alicyclic hydrocarbon group having 3 to 6 carbon atoms that is unsubstituted or substituted with a halogen or an aliphatic hydrocarbon group More preferably selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms, and particularly preferably a methyl group.

  The original copolymer (A) of the present invention may contain one or more of (ii) an unsaturated carboxylic acid ester unit and (iii) an unsaturated carboxylic acid unit.

  Although there is no restriction | limiting in particular as a method to obtain the said original copolymer (A), The unsaturated carboxylic ester monomer represented by following General formula (4) and the unsaturated represented by following General formula (5) It is preferably obtained by copolymerizing a monomer mixture comprising a carboxylic acid monomer. That is, in the method, the unsaturated carboxylic acid ester unit represented by the general formula (2) contained in the original copolymer (A) is an unsaturated carboxylic acid ester represented by the following general formula (4). The unsaturated carboxylic acid unit represented by the general formula (3) derived from the copolymerization of the monomers and contained in the original copolymer (A) is an unsaturated carboxylic acid represented by the following general formula (5). Derived from acid monomers.

(However, R ⁶ represents any one selected from hydrogen and an organic residue having 1 to 20 carbon atoms, and R ⁷ represents any one selected from organic residues having 1 to 22 carbon atoms.)

(However, R ⁸ represents any one selected from a hydrogen atom and an organic residue having 1 to 20 carbon atoms)

In the general formula (4), the organic residue having 1 to 20 carbon atoms of R ⁶ is not particularly limited, and may be linear, branched or cyclic, and includes a hetero atom in the structure. But you can. R ⁶ is preferably a hydrogen atom, an unsubstituted or halogen-substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic group having 6 to 20 carbon atoms substituted with halogen or an aliphatic hydrocarbon group. A group selected from an alicyclic hydrocarbon group having 3 to 20 carbon atoms substituted with an aromatic group, unsubstituted or halogen or an aliphatic hydrocarbon group, more preferably a hydrogen atom, unsubstituted or substituted with a halogen From an alkyl group having 1 to 6 carbon atoms, an unsubstituted or phenyl group substituted with halogen or an alkyl group, an unsubstituted or substituted halocyclic hydrocarbon group having 3 to 6 carbon atoms with a halogen or an aliphatic hydrocarbon group Any one selected, more preferably any one selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms, and particularly preferably a methyl group.

The organic residue having 1 to 22 carbon atoms of R ⁷ is not particularly limited, and may be linear, branched or cyclic, and may contain a hetero atom in the structure. R ⁴ is preferably an unsubstituted or halogen-substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted or substituted aromatic group having 6 to 20 carbon atoms by halogen or an aliphatic hydrocarbon group, Any one selected from unsubstituted or substituted alicyclic hydrocarbon group having 3 to 22 carbon atoms and substituted with halogen or aliphatic hydrocarbon group, and hydroxyalkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom A group selected from an unsubstituted or halogen-substituted alkyl group having 1 to 6 carbon atoms, a phenyl group unsubstituted or substituted with a halogen or alkyl group, a cyclohexyl group, and a hydroxyalkyl group having 1 to 6 carbon atoms is a group, more preferably a hydrogen atom, an unsubstituted or halogen-substituted alkyl group having 1 to 6 carbon atoms, particularly preferred as R ⁷ Or an unsaturated carboxylic acid ester monomer represented by the general formula (4) is an unsaturated carboxylic acid alkyl ester monomer having 1 to 6 carbon atoms. It is particularly preferred.

In the general formula (5), the organic residue having 1 to 20 carbon atoms of R ⁸ is not particularly limited, and may be linear, branched, or cyclic, and may contain a hetero atom in the structure. R ³ is preferably hydrogen, unsubstituted or halogen-substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, unsubstituted or substituted with halogen or aliphatic hydrocarbon group and having 6 to 20 carbon atoms. Group, unsubstituted or a group selected from alicyclic hydrocarbon group having 3 to 20 carbon atoms substituted by halogen or aliphatic hydrocarbon group, more preferably a hydrogen atom, unsubstituted or halogen-substituted carbon An alkyl group having 1 to 6 carbon atoms, a phenyl group that is unsubstituted or substituted with halogen or an alkyl group, an alicyclic hydrocarbon group that has 3 to 6 carbon atoms that is unsubstituted or substituted with a halogen or an aliphatic hydrocarbon group, carbon Any one selected from hydroxyalkyl groups having 1 to 6 carbon atoms, more preferably any one selected from hydrogen atoms and alkyl groups having 1 to 5 carbon atoms, most preferably It is preferably a methyl group.

  Specific examples of the unsaturated carboxylic acid ester monomer represented by the general formula (4) are not particularly limited. For example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, and acrylic acid n- Propyl, n-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-methacrylic acid Butyl, n-hexyl acrylate, n-hexyl methacrylate, lauryl acrylate, lauryl methacrylate, dodecyl acrylate, dodecyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, A Stearyl bromate, stearyl methacrylate, octadecyl acrylate, octadecyl methacrylate, phenyl acrylate, phenyl methacrylate, benzyl acrylate, benzyl methacrylate, allyl acrylate, allyl methacrylate, trifluoroethyl acrylate, trifluoromethacrylate Ethyl, chloromethyl acrylate, chloromethyl methacrylate, 2-chloroethyl acrylate, 2-chloroethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxy methacrylate Propyl, 2,3,4,5,6-pentahydroxyhexyl acrylate, 2,3,4,5,6-pentahydroxyhexyl methacrylate, ethyl hexyl acrylate, meta Ethyl hexyl acrylate, 2,3,4,5-tetrahydroxypentyl acrylate, 2,3,4,5-tetrahydroxypentyl methacrylate, aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, methacryl Examples include ethylaminopropyl acid, phenylaminoethyl methacrylate, and cyclohexylaminoethyl methacrylate. Of these, methyl methacrylate and ethyl methacrylate are preferable, and methyl methacrylate is particularly preferable from the viewpoint of excellent optical characteristics and thermal stability. These may be used alone or as a mixture of two or more.

  Further, the unsaturated carboxylic acid monomer is not particularly limited, but any unsaturated carboxylic acid monomer that can be copolymerized with other vinyl compounds can be used. Preferred unsaturated carboxylic acid monomers include maleic anhydrides such as maleic acid, itaconic acid, monomethyl maleate and monoethyl maleate in addition to compounds represented by the above general formula (5) such as acrylic acid and methacrylic acid. Acid hydrolysates, metal salts of these unsaturated carboxylic acid monomers, and the like are mentioned. Among them, acrylic acid and methacrylic acid are particularly preferable in terms of excellent thermal stability, and methacrylic acid is more preferable. . One or more of these can be used. Moreover, as a metal ion of the said metal salt, potassium, lithium, sodium, calcium, zinc etc. can be used, for example, There is no restriction | limiting in particular. In the original copolymer (A) of the present invention, (ii) the lower limit of the content of the unsaturated carboxylic acid ester unit is not particularly limited and may be at least partially contained, preferably 5% by weight or more, More preferably, it is 20 weight% or more, More preferably, it is 40 weight% or more, Especially preferably, it is 50 weight% or more, Most preferably, it is 55 weight% or more. (Ii) The upper limit of the content of the unsaturated carboxylic acid ester unit is not particularly limited, but is preferably 95% by weight or less, more preferably 90% by weight or less, still more preferably 87% by weight or less, Especially preferably, it is 85 weight% or less, Most preferably, it is 84 weight% or less. On the other hand, the lower limit of the content of the (iii) unsaturated carboxylic acid unit is not particularly limited, but is preferably 5% by weight or more, more preferably 10% by weight or more, and further preferably 13% by weight or more. Yes, particularly preferably 15% by weight or more, and most preferably 16% by weight or more. (Iii) The upper limit of the content of the unsaturated carboxylic acid unit is not particularly limited, but is preferably 95% by weight or less, more preferably 80% by weight or less, still more preferably 60% by weight or less, Preferably it is 50 weight% or less, Most preferably, it is 45 weight% or less. (Ii) When the content of unsaturated carboxylic acid units is 5% by weight or more, the amount of (i) glutaric anhydride-containing units produced by heating the original copolymer (A) increases, and heat resistance is improved. The effect and tensile strength tend to increase. On the other hand, when the content of (iii) unsaturated carboxylic acid units is 95% by weight or less, after the cyclization reaction by heating of the original copolymer (A), (iii) the residual amount of unsaturated carboxylic acid units is There is a tendency to decrease, and the tensile strength retention rate and melt residence stability after wet heat treatment tend to be improved.

  Further, the original copolymer (A) can contain other vinyl monomer units within a range not impairing the effects of the present invention. At this time, the other vinyl monomer unit (A) in the original copolymer is preferably introduced by copolymerizing the other vinyl monomer. Preferable specific examples of other vinyl monomers include fragrances such as styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, and pt-butylstyrene. Group vinyl monomers, vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, ethacrylonitrile, glycidyl (meth) acrylate, glycidyl itaconate, allyl glycidyl ether, styrene-p-glycidyl ether, p- Glycidyl styrene, maleic anhydride, dimethyl maleate, diethyl maleate, itaconic anhydride, 1,2-dimethyl maleic anhydride, phenyl maleic anhydride, maleimide, N-methylmaleimide, N-ethylmaleimide, Nn-propyl Maleimide, N-isopropylmale N-cycloalkylmaleimide such as amide, Nn-butylmaleimide, N-isobutylmaleimide, N-tert-butylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-alkyl-substituted phenylmaleimide, acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, (meth) acrylic acid 2- Diethylaminoethyl, 2-dibutylaminoethyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, phenylaminoethyl (meth) acrylate , Cyclohexylaminoethyl (meth) acrylate, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallylamine, N-methylallylamine, p-aminostyrene, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2 -Acroyl-oxazoline, 2-styryl-oxazoline, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy 2-methyl-1-propene, cis-5-hydroxy-2-pentene, trans-5-hydroxy-2-pentene, 4-dihydroxy-2-butene, ethylene, propylene, vinyl chloride, vinyl acetate, propenyl acetate, Isopropenyl acetate, vinyl benzoate , Polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polytetramethylene glycol methacrylate, allyl alcohol, methallyl alcohol, methyl 2- (hydroxymethyl) acrylate, ethyl 2- (hydroxymethyl) acrylate and α- And methylene-γ-butyrolactone. These may be used alone or in combination of two or more.

  The original copolymer (A) of the present invention is not particularly limited as long as it can be derived from the thermoplastic polymer of the present invention. However, the original copolymer (A) of the present invention is not limited to the thermoplastic polymer. Polymer having a molecular weight of 4 times or more the value of the weight average molecular weight of the original copolymer (A) of the present invention obtained by gel permeation chromatography carried out under the same conditions as the gel permeation chromatography The content of the polymer having a molecular weight of at least 4 times the value of the weight average molecular weight of the thermoplastic polymer of the present invention is controlled to be 3.0% by weight or less. This is preferable. The content of the polymer having a molecular weight of 4 or more times the value of the weight average molecular weight of the original copolymer (A) of the present invention is preferably 3.0% by weight or less, more preferably 2.7% by weight. More preferably, it is 2.0% by weight or less, particularly preferably 1.5% by weight or less, and most preferably 1.4% by weight or less.

  The upper limit of the weight average molecular weight (absolute molecular weight) of the original copolymer (A) of the present invention is not particularly limited, but the fluidity of the original copolymer (A) and the intramolecular cyclization reaction thereof From the viewpoint of fluidity at the time of melt processing of the thermoplastic resin composition of the present invention obtained by adding the thermoplastic resin of the present invention and further the rubbery polymer (C), it is preferably 1000000 or less, more preferably It is 200000 or less, More preferably, it is 150,000 or less, Especially preferably, it is 115000 or less, Most preferably, it is 110,000 or less. The lower limit of the weight average molecular weight is not particularly limited, but is preferably 10,000 or more, more preferably 20000 or more, and further preferably 30000 or more, particularly preferably from the viewpoint of impact resistance and melt residence stability. Is 40000 or more, most preferably 45000 or more.

  The molecular weight distribution (weight average molecular weight (absolute molecular weight) / number average molecular weight (absolute molecular weight)) of the original copolymer (A) is not particularly limited, but the lower limit of the molecular weight distribution is that of the original copolymer (A) of the present invention. From the viewpoint of good fluidization, it is preferably 1.05 or more, more preferably 1.1 or more, still more preferably 1.2 or more, particularly preferably 1.3 or more, and most preferably 1. .4 or more. The upper limit of the molecular weight distribution is not particularly limited, but is usually preferably 10.0 or less, and preferably 5.0 or less from the viewpoint of impact resistance and tensile strength of the thermoplastic polymer of the present invention to be obtained. More preferably, it is 3.0 or less, More preferably, it is 2.85 or less, Especially preferably, it is 2.7 or less, Most preferably, it is 2.5 or less.

  The production method of the original copolymer (A) of the present invention is not particularly limited, and a method obtained by copolymerization of an unsaturated carboxylic acid ester monomer and an unsaturated carboxylic acid monomer, such as tert-butyl acrylate, A method obtained by (co) polymerization of an unsaturated carboxylic acid precursor monomer such as tert-butyl methacrylate with an unsaturated carboxylic acid ester monomer, and then converting the precursor into an unsaturated carboxylic acid unit. (Ii) a method of obtaining a (co) polymer containing unsaturated carboxylic acid ester units and (iii) a method obtained by partial hydrolysis of unsaturated carboxylic acid ester units, (iii) containing unsaturated carboxylic acid units Examples include a method of partially esterifying a (co) polymer, and a molecular weight that is 4 times or more the value of the weight average molecular weight obtained by gel permeation chromatography. The content of the polymer from the viewpoint and productivity aspects are preferably controlled to 3.0% by weight or less of a method for obtaining the (co) polymerization of the unsaturated carboxylic acid monomers are more preferred. Further, the method for controlling the content of the polymer having a molecular weight of 4 times or more of the value of the weight average molecular weight to 3.0% by weight or less is not particularly limited, but the mercaptocarboxylic acid ester and / or aromatic is not particularly limited. It is preferable to obtain a chain transfer agent containing a chain transfer agent containing a thiol and (co) polymerization in the presence or absence of a solvent, more preferably a chain transfer agent containing a mercaptocarboxylic acid ester. It is obtained by (co) polymerization in the presence or absence of a solvent. Since the original copolymer (A) of the present invention contains (iii) an unsaturated carboxylic acid unit, preferably 5% by weight or more, for example, the original copolymer (A) is obtained by (co) polymerization of an unsaturated carboxylic acid. When obtained, a polymer having a molecular weight of 4 times or more the value of the weight average molecular weight containing a large amount of unsaturated carboxylic acid units or containing only unsaturated carboxylic acid units due to association of unsaturated carboxylic acids. The content of a polymer having a molecular weight of 4 times or more of the value of the weight average molecular weight is 3.0% by weight or less by (co) polymerization in the presence of the chain transfer agent. It can be preferably controlled. Further, in addition to the method of adding the chain transfer agent at the time of copolymerization, it is also preferable to combine a method of controlling the polymerization temperature to an optimum value in the initial stage of polymerization and the latter half of the polymerization and / or a method of controlling the monomer concentration by adding additional monomers .

In the present invention, the chain transfer constant at 60 ° C. for a methyl methacrylate monomer chain transfer agent is, for example, “POLYMER HANDBOOK FOURTH EDITION, J. BRANDRUUP, EH IMMERGUT, and EA GRULKE, II / 97˜ 159, WILEY INTERSCIENCE (1999) ”and“ Radical polymerization (I), written by Otsu, p. 126, 127, Kagaku Dojin (1971) ”can be referred to. The chain transfer constant at 60 ° C. for the methyl methacrylate monomer chain transfer agent is partly listed in TABLE 5 of “POLYMER HANDBOOK FOURTH EDITION, II / 97 to 159”. elimination rate of chain transfer agent) / (rate of disappearance of monomer) = d [X] / d [M] = C x [X] / [M], i.e. Cx = dlog [X] / dlog [M], by also In the present invention, in the present invention, the following Mayo formula (“FR Mayo, C. Walling, Chem. Rev., 46 , 191 (1950)”, “Introduction to New Polymer Chemistry, 1st Report, Higashimura et al., p.60, Chemical Doujin (1995) "), and the chain transfer constant Cx is obtained.
1 / P _n = 1 / P _n0 + C _x [X] / [M]
Here, [X] is the concentration of the chain transfer agent, [M] is the concentration of the monomer, and _Pn is the number average polymerization degree of the polymer when polymerized in the presence of the chain transfer agent. P _n0 is the number average degree of polymerization of the polymer when polymerized in the absence of the chain transfer agent. C _x is the sum of these chain transfer constants when a plurality of chain transfer agents are used. Before use, methyl methacrylate was passed through a column packed with activated alumina to remove the polymerization inhibitor, dehydrated with calcium hydride, and distilled under reduced pressure. AIBN (2,2′-azobisisobutyronitrile) is purified by recrystallization in methanol. After the inside of the 20 ml test tube is degassed, a nitrogen atmosphere is set, methyl methacrylate is charged, and then 0.3% by weight of AIBN is added as a polymerization initiator based on the weight of the charged methyl methacrylate. In addition to the case where the chain transfer agent is not added, it is arbitrarily changed by 5 points in the range of 0.05 to 1.50% by weight with respect to the weight of methyl methacrylate charged with the chain transfer agent. Add chain transfer agent. Before the polymerization, after purging with nitrogen for 15 minutes and under a nitrogen atmosphere, bulk polymerization of methyl methacrylate at 60 ° C. in the presence of each concentration of the chain transfer agent (because no solvent is used, the chain transfer constant for the solvent is The chain transfer constant to the initiator can be regarded as zero because AIBN is used). The polymerization is terminated by rapidly cooling before the polymerization rate reaches 5%, the contents are dissolved in acetone at a constant concentration, an acetone solution of this concentration is sampled, and a gas chromatograph (GC-14B, manufactured by Shimadzu Corporation, Column: Residual concentration of chain transfer agent is determined by measurement using capillary column DB-5) manufactured by J & W. On the other hand, after adding a small amount of hydroquinone as a polymerization inhibitor to the acetone solution, it is reprecipitated with 20 times methanol, further washed twice with methanol, and then vacuum dried at 50 ° C. for 48 hours to obtain a polymer. About this polymer, a weight is measured and a polymerization rate is determined, and it obtains by performing a gel permeation chromatograph measurement about _Pn and _Pn0 on the following conditions. That is, each polymer obtained was dissolved in tetrahydrofuran for HPLC measurement at a concentration of 0.2% by weight (the mobile phase was also tetrahydrofuran), and gel permeation chromatograph (pump: 515 type, manufactured by Waters, column: TSKgel). Using GMHHR-H (30) and TSKgel Multipore HXL-M (directly connected, manufactured by Tosoh Corporation), measurement is performed at 30 ° C. and a flow rate of 1 ml / min. At a column temperature of 30 ° C., an ultraviolet detector is used as a detector, and conversion is performed using eight monodisperse polymethyl methacrylate standard reagents having a molecular weight in the range of 2400 to 1580000 to obtain a weight average molecular weight and a number average molecular weight. Plot [S] / [M] on the horizontal axis and 1 / _Pn on the vertical axis to obtain the slope of the obtained straight line (C _x ). The chain transfer constant at 60 ° C. with respect to the chain transfer agent of methyl methacrylate monomer And

  The sequence of each monomer unit in the original copolymer (A) of the present invention is particularly limited as long as it is a sequence that can be derived from a thermoplastic polymer containing at least a part of (i) a glutaric anhydride-containing unit. The original copolymer (A) may be a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, or a combination thereof, but a random copolymer or an alternating copolymer may be used. It tends to be excellent in mechanical properties such as thermal stability, color tone, and tensile strength after wet heat treatment, and is more preferably a random copolymer. The polymerization method is not particularly limited, and conventionally known polymerization methods such as suspension polymerization, emulsion polymerization, bulk polymerization, solution polymerization and precipitation polymerization, and combinations of known polymerization methods such as bulk suspension polymerization, for example, Polymerization in a supercritical fluid such as supercritical carbon dioxide is preferably used, and these polymerizations may be either batch type or continuous type. In particular, from the viewpoint of reducing foreign matters in the polymer (A) and the thermoplastic polymer of the present invention, particularly unmelted polymer, and achieving low foreign matters required for optical material applications, bulk polymerization, continuous bulk polymerization, solution Polymerization, precipitation polymerization, continuous precipitation polymerization, and a combination of these polymerization methods are preferred, and precipitation polymerization is particularly preferred from the viewpoints of achieving low foreign matter and reducing labor and time in polymer purification.

Precipitation polymerization is, for example, polymerization in a solvent in which the monomer mixture that is the raw material of the original copolymer (A) is dissolved, but the solubility of the original copolymer (A) is 1 g / 100 g or less. Can be defined as Such a solvent is not particularly limited, and water and / or an organic solvent can be used. From the viewpoint of making the composition distribution of the original copolymer (A) more uniform, an organic solvent is preferable, Among them, an organic solvent (E) having a solubility parameter in the range of 11.9 to 17.6 MPa ^1/2 is preferable. Here, the “solubility of the original copolymer (A)” means the amount of the original copolymer (A) dissolved in 100 g of the solvent after being stirred at 23 ° C. for 24 hours.

  In precipitation polymerization in the production of the original copolymer (A), it is preferable to copolymerize a monomer mixture comprising an unsaturated carboxylic acid ester monomer and an unsaturated carboxylic acid monomer in an organic solvent (E). However, the charged monomer concentration calculated by [mass of all monomers charged into the polymerization system] / [mass of all monomers charged into the polymerization system + mass of organic solvent (E) in the polymerization system] is 10.0. % From the viewpoint of the color tone of the thermoplastic polymer obtained by intramolecular cyclization of the original copolymer (A), particularly the color tone after high-temperature treatment at 300 ° C. or higher, more preferably 17.0. % Or more, more preferably 17.5% or more, particularly preferably 18.0% or more, and most preferably 20.0% or more. The upper limit of the charged monomer concentration is not particularly limited, but is preferably 40.0% or less, more preferably 36.0% or less, particularly preferably 33.0% or less, and most preferably Is 31.0% or less.

In the present invention, the lower limit of the solubility parameter of the organic solvent (E) is more preferably 12.9 MPa ^1/2 or more, further preferably 14.0 MPa ^1/2 or more, and particularly preferably 15.4 MPa ^1/2. Above, most preferably 15.8 MPa ^1/2 or more. The upper limit of the solubility parameter is more preferably 17.4 MPa ^1/2 or less, still more preferably 17.3 MPa ^1/2 or less, and particularly preferably 17.2 MPa ^1/2 or less.

The organic solvent (E), the single solvent of solubility parameter in the range of 11.9~17.6MPa ^1/2, solubility parameter include a mixed solvent in the range of 11.9～17.6MPa ^1/2 Can do. Mixed solubility parameter as the mixed solvent is in the range of 11.9～17.6MPa ^1/2, for example, the solubility parameter of two or more single solvents in the range of 11.9～17.6MPa ^1/2 solvent, solubility parameter within one or more single solvents ranging 11.9～17.6MPa ^1/2, further solubility parameter of one or more organic solvents not in the range 11.9～17.6MPa ^1/2 And a mixed solvent in which the solubility parameter as a mixed solvent is adjusted to a range of 11.9 to 17.6 MPa ^1/2 .

The organic solvent (E) can be used as a single solvent as long as the solubility parameter is in the range of 11.9 to 17.6 MPa ^1/2 . For example, aliphatic hydrocarbons, One or more selected from acid esters, ketones, ethers, alcohols, aldehydes, lactones, aromatic compounds, polar aprotic solvents, carbonate compounds, and halogen compounds are preferred.

  Here, as the organic solvent (E), examples of the aliphatic hydrocarbon that can be used as a single solvent include linear hydrocarbons having 5 to 12 carbon atoms and aliphatic hydrocarbons having side chains. Specific examples include n-pentane, neopentane, n-hexane, isohexane, n-heptane, perfluoroheptane, n-octane, isooctane, 2-ethylhexane, n-nonane, isononane, n-decane, undecane, dodecane, Preferred examples include 2,4-dimethylpentane, 2,3-dimethylpentane, and various isomers thereof, and one or more of these can be used, and among these, the viewpoint of residence stability of the original copolymer To n-hexane and n-decane are more preferable.

  Examples of alicyclic hydrocarbons that can be used alone or as an organic solvent (E) include cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, trans-decalin, cis-decalin, t-butylcyclohexane, and perfluoromethylcyclohexane. Preferred examples include cyclohexane substitutes and isomers thereof, and one or more of these can be used. Among these, cyclohexane is more preferred.

  Carboxylic acid esters that can be used alone or as the organic solvent (E) include isobutyl formate, amyl formate, formic acid-n-hexyl, 2-butoxyethyl acetate, 2- (2-butoxyethoxy) ethyl acetate, and isopropyl acetate. 1-methoxy-2-propyl acetate, n-butyl acetate (hereinafter sometimes simply referred to as butyl acetate), isobutyl acetate, acetic acid-sec-butyl, acetic acid-tert-butyl, acetic acid 3-methoxybutyl, 3-methoxy-3-methylbutyl acetate, amyl acetate, acetic acid-n-hexyl, acetic acid-n-heptyl, acetic acid-n-octyl, acetic acid-n-nonyl, ethyl propionate, propionate-n-propyl, isopropyl propionate , Propionate-n-butyl, isobutyl propionate, amyl propionate, propion -N-hexyl, methyl butyrate, ethyl butyrate, butyric acid-n-propyl, butyric acid isopropyl, butyric acid-n-butyl, butyric acid isobutyl, butyric acid amyl, butyric acid-n-hexyl, isoamyl acetate, acetic acid-sec-amyl Methyl acetate), 2-methylbutyl acetate, 1,3-dimethylbutyl acetate, 1-methylamyl acetate, 2-methylamyl acetate and 3-methylamyl acetate, isoamyl formate, formate-sec-amyl, formate-2- Formic acid esters such as methylbutyl, 1-methylamyl formate, 2-methylamyl formate and 3-methylamyl formate, methyl isobutyrate, ethyl isobutyrate, propyl isobutyrate, butyl isobutyrate, isobutyl isobutyrate, sec-butyl isobutyrate, isobutyric acid Isobutyric acid ester such as amyl and isoamyl isobutyrate , Butyrate esters such as isoamyl butyrate, sec-amyl butyrate, 2-methylbutyl butyrate, 1-methylamyl butyrate, 2-methylamyl butyrate and 3-methylamyl butyrate, methyl valerate, ethyl valerate, propyl valerate, isopropyl valerate Butyl valerate, isobutyl valerate, valeric acid-sec-butyl, amyl valerate, isoamyl valerate, valerate-sec-butyl, 2-methylbutyl valerate, 1-methylamyl valerate, 2-methylamyl valerate and melamine Valeric acid esters such as 3-methylamyl acid, methyl isovalerate, ethyl isovalerate, propyl isovalerate, isopropyl isovalerate, butyl isovalerate, isobutyl isovalerate, isovaleric acid-sec-butyl, isovaleric Amyl herbate, isoamyl isovalerate, isovaleric acid-sec-butyl, isoyoshi Isovaleric acid esters such as 2-methylbutyl herbate, 1-methylamyl isovalerate, 2-methylamyl isovalerate and 3-methylamyl isovalerate, isobutyl 2-ethylbutyrate, ethyl octanoate, diisodecyl phthalate, dibutoxy phthalate Preferred examples include ethyl, butyl stearate, butyl isostearate and various isomers thereof, and one or more of these can be used.

  As the organic solvent (E), ketones that can be used alone are 4-methoxy-4-methyl-2-pentanone, methyl isobutyl ketone, ethyl isobutyl ketone, methyl n-hexyl ketone, diisobutyl ketone, and methyl nonyl ketone. (2-undecanone), methylhexyl ketone, methyl amyl ketone (2-heptanone), methyl isoamyl ketone, methyl-sec-amyl ketone, ethyl amyl ketone, propyl amyl ketone, diisopropyl ketone, 4,6-dimethyl-2-heptanone and Preferred examples include isobutyl isopropyl ketone, and one or more of these can be used.

  Preferred examples of the ether that can be used alone as the organic solvent (E) include diisopropyl ether, diethyl ether, ethyl isobutyl ether, butyl ether, propyl ether, and dihexyl ether. One or more of these may be used. it can. Preferred examples of the alcohol that can be added as the organic solvent (E) include isononyl alcohol, isodecanol, isotridecanol, and lauryl alcohol, and one or more of these can be used.

In addition, as described above, the organic solvent (E) may further contain other solvents in addition to the organic solvent that can be used as the single solvent in the range where the solubility parameter is 11.9 to 17.6 MPa ^1/2. It can be prepared by adding. Examples of the carboxylic acid ester that can be used as a mixture with an organic solvent that can be used alone as the organic solvent (E) include carboxylic acid esters other than those exemplified above, such as isopropyl formate and formic acid. -N-butyl, formic acid-n-propyl, methyl acetate, ethyl acetate, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, triacetin, -n-propyl acetate, propionic acid Preferable examples include methyl, and one or more of these can be used.

  As a ketone that can be used as a mixture with a solvent that can be used alone as the organic solvent (E), a straight chain having 1 to 20 carbon atoms or a ketone other than a ketone that can be used alone as the organic solvent (E) or Branched or cyclic ketones, and specific examples include acetone, methyl ethyl ketone, acetylacetone, 4-methoxy-4-methyl-2-pentanone, methyl-n-butyl ketone, and cyclohexanone. The above can be used.

  Examples of ethers that can be used as a mixture with a solvent that can be used alone as the organic solvent (E) include diphenyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and triethylene glycol. Monobutyl ether, tetraethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol Monome Preferred examples include ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. One or more of these can be used.

  Examples of the alcohol that can be used as a mixture with a solvent that can be used alone as the organic solvent (E) include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butyl alcohol, tert-butanol, 3 -Methoxybutanol, 1,3-butanediol, allyl alcohol, amyl alcohol, isoamyl alcohol, 1-methylbutanol, 2-methylbutanol, neopentyl alcohol, hexanol, isohexanol, cyclohexanol, 2-ethylhexanol, methyl amyl alcohol , Heptanol, isoheptanol, octanol, isooctanol, nonanol, isononanol, decanol, methyl isobutyl carbinol, methyl carbitol, ethanol Lucalbitol, propyl carbitol, butyl carbitol, diisobutyl carbinol, 4-hydroxy-4-methyl-2-pentanone, 3,5,5-trimethyl-1-hexanol, nonyl alcohol, ethylene glycol, 1,3-butylene glycol 2,4-diethylpentanediol, butylethylpropanediol, octanediol and the like diols and isomers thereof, and one or more of these can be used.

  Examples of the aromatic compound that can be used as a mixture with a solvent that can be used alone as the organic solvent (E) include benzene, toluene, xylene, trimethylbenzene, and the like, and one or more of these can be used. it can.

  Examples of the aldehyde that can be used in combination with a solvent that can be used alone as the organic solvent (E) include butyraldehyde and isobutyraldehyde, and one or more of these can be used.

  Examples of the lactone that can be used as a mixture with a solvent that can be used alone as the organic solvent (E) include γ-butyrolactone, α-methyl-γ-butyrolactone, α-methylene-γ-butyrolactone, and the like. One or more of these can be used.

  Examples of polar aprotic solvents that can be used in combination with a solvent that can be used alone as the organic solvent (E) include dioxane, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, dimethylacetamide, and acetonitrile. One or more of these can be used.

  Examples of the carbonate compound that can be used as a mixture with a solvent that can be used alone as the organic solvent (E) include dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, and the like. Can be used.

  Examples of the halogen compound that can be used as a mixture with a solvent that can be used alone as the organic solvent (E) include fats that can be added as the organic solvent (E) and other organic solvents other than the organic solvent (E). In addition to one or more halides selected from aromatic hydrocarbons, carboxylic acid esters, ketones, ethers, alcohols, aromatic compounds, polar aprotic solvents, carbonate compounds, halogenated compounds, dichloromethane, chloroform, carbon tetrachloride, dichloroethylene , Trichloroethylene, tetrachloroethylene, chlorobenzene, dichlorobenzene, trichlorobenzene, hexafluoroisopropanol and the like, and one or more of these can be used. Moreover, in this invention, the organic solvent (E) can contain free acids, such as an acetic acid, various stabilizers, a water | moisture content, etc. in the range which does not impair the effect of this invention.

  The organic solvent (E) is more preferably selected from aliphatic hydrocarbons, alicyclic hydrocarbons, carboxylic acid esters, and ketones from the viewpoint of the color tone of the obtained original copolymer (A) and thermoplastic polymer. More preferably, it contains at least an alicyclic hydrocarbon, particularly preferably a mixture of an alicyclic hydrocarbon and a carboxylic acid ester, and the alicyclic hydrocarbon is cyclohexane. Is most preferred. Cyclohexane is preferably higher in purity, but may contain benzene, methylcyclohexane, cycloparaffin and the like. Regarding the mixture of the alicyclic hydrocarbon and the carboxylic acid ester preferably used as the organic solvent (E), the mixing ratio of the alicyclic hydrocarbon is not particularly limited. From the viewpoint of reducing the content of the following low molecular weight substances, the lower limit thereof is preferably 27% by weight or more, more preferably 30% by weight or more, still more preferably 35% by weight or more, and particularly preferably. Is 40% by weight or more, most preferably 45% by weight or more, and the upper limit of the blending ratio of the alicyclic hydrocarbon is preferably 90% by weight or less, more preferably 80% by weight or less. As an organic solvent (E), carboxylic acid esters preferably used in combination with alicyclic hydrocarbons include acetic acid-n-propyl, isopropyl acetate, and acetic acid-n-butyl (hereinafter sometimes referred to as butyl acetate) , Isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, 3-methoxy-3-methylbutyl acetate, amyl acetate and isoamyl acetate are particularly preferred.

In addition, by using the organic solvent (E) in the precipitation polymerization, the deposited polymer adheres to the reaction vessel wall, the reaction vessel bottom, and the stirring blade during the polymerization of the original copolymer (A), and the precipitated polymers It is possible to highly prevent the coarsening due to the coalescence. Furthermore, the original copolymer (A) can be taken out very easily as a powder. In the recovery of the particles of the original copolymer (A) after the solid-liquid separation of the slurry of the original copolymer (A) after polymerization, the effect of the organic solvent (E) is used to recover the original copolymer (A). The dispersibility of the particles is greatly improved.

From the viewpoint of improving the melt residence stability at a high temperature and the melt residence stability in the presence of air of the original copolymer (A) obtained through the second step, the polymerization method in the first step is a polymerization initiator. Is preferably obtained by a precipitation polymerization method using an organic solvent (E) having a solubility parameter in the range of 11.9 to 17.6 MPa ^{1/2 in} the presence or absence of The concentration of charged monomer calculated by the following equation: [mass of all monomers charged to 1] / [mass of all monomers charged in polymerization system + mass of organic solvent (E) in polymerization system] is in the range of 17.0 to 40.0%. It is more preferable to satisfy the above simultaneously. As described above, precipitation polymerization at a high monomer concentration, which is difficult to achieve by using a specific organic solvent (E) and difficult to continue stirring by coalescence and / or agglomeration of the precipitated polymer in the conventional precipitation polymerization, is performed. By carrying out the process, the obtained original copolymer (A) is excellent in the above-mentioned characteristics, and is obtained by subjecting the original copolymer to (i) dehydration and / or (b) intramolecular cyclization reaction by dealcoholization. The resulting thermoplastic polymer is greatly excellent in resistance to moist heat aging.

  In the copolymerization, the concentration of the charged monomer is not particularly limited, but is preferably 5% or more from the viewpoint of productivity, and the resistance to moist heat aging of the thermoplastic polymer obtained by intramolecular cyclization reaction is preferable. From the viewpoint, the lower limit is more preferably 17.5% or more, further preferably 18.0% or more, particularly preferably 20.0% or more, and most preferably 25.0% or more. . On the other hand, the upper limit of the monomer concentration is more preferably 36.0% or less, still more preferably 33.0% or less, and particularly preferably 31.0% or less. In this way, by performing precipitation polymerization using the organic solvent (E) and setting the charged monomer concentration to 17.0 to 40.0%, association of unsaturated carboxylic acid monomers during the polymerization is performed. It is possible to control the degree of.

  The polymerization temperature in the first step can be arbitrarily set, but the polymerization is preferably performed at a polymerization temperature of 380 ° C. or lower, more preferably 180 ° C. or lower, and further preferably 120 ° C. or lower. Particularly preferably, it is 95 ° C. or less, and most preferably 90 ° C. or less. The lower limit of the polymerization temperature is not particularly limited as long as the polymerization proceeds, but is preferably 40 ° C. or higher, more preferably 60 ° C. or higher from the viewpoint of productivity in consideration of the polymerization rate. The polymerization time is not particularly limited as long as it is a time sufficient to obtain a necessary polymerization rate.

  The preferred ratio of the monomer mixture comprising the unsaturated carboxylic acid ester monomer and the unsaturated carboxylic acid monomer used in the production of the original copolymer (A) as the first step is not particularly limited. The lower limit of the unsaturated carboxylic acid monomer is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 13% by weight or more, based on the monomer mixture as 100% by weight. Especially preferably, it is 15 weight% or more, Most preferably, it is 16 weight% or more. The upper limit of the unsaturated carboxylic acid monomer is preferably 95% by weight or less, more preferably 80% by weight or less, still more preferably 60% by weight or less, and particularly preferably 50% by weight or less. Most preferably, it is 45% by weight or less. The lower limit of the unsaturated carboxylic acid ester monomer is preferably 5% by weight or more, more preferably 20% by weight or more, still more preferably 40% by weight or more, based on 100% by weight of the monomer mixture. And particularly preferably 50% by weight or more, and most preferably 55% by weight or more. The upper limit of the unsaturated carboxylic acid ester monomer is not particularly limited, but is preferably 95% by weight or less, more preferably 90% by weight or less, still more preferably 87% by weight or less, and particularly preferably 85% or less. % By weight or less, most preferably 84% by weight or less. When other vinyl monomers copolymerizable with these are used, the upper limit of the other vinyl monomers is not particularly limited, but is preferably 75% by weight or less, more preferably 35% by weight or less. More preferably 10% by weight or less, particularly preferably 5% by weight or less. That is, the preferred range of the other vinyl monomer is in the range of 0 to 75% by weight, more preferably in the range of 0 to 35% by weight, still more preferably in the range of 0 to 10% by weight. Preferably it is the range of 0 to 5 weight%. When the amount of the unsaturated carboxylic acid monomer is 5% by weight or more, the amount of (i) glutaric anhydride-containing units produced by heating the original copolymer (A) increases, and the effect of improving heat resistance is large. Tend to be. When the amount of the unsaturated carboxylic acid monomer is 95% by weight or less, after the cyclization reaction by heating of the original copolymer (A), (iii) the residual amount of the unsaturated carboxylic acid unit tends to decrease, There is a tendency that the tensile strength retention and the melt residence stability after wet heat treatment are improved.

  In addition, these monomer mixtures may be charged in an organic solvent at once and copolymerized, or may be copolymerized while being added in portions or sequentially. More preferably, for the purpose of reducing the composition distribution of the monomer units constituting the original copolymer to be produced, there is a method in which the weight composition ratio in the monomer mixture is arbitrarily set and divided addition or sequential addition is performed. Can be mentioned. The dissolved oxygen concentration in the polymerization solution in the first step is not particularly limited, but is preferably lower, for example, more preferably 5 ppm or less, but in the present invention, the dissolved oxygen concentration in the polymerization solution exceeds 5 ppm. Even if it is a case, by using the chain transfer agent containing a mercaptocarboxylic acid ester and / or aromatic thiol, the original copolymer (A) excellent in conventional ratio, color tone, transparency and thermal stability is obtained. Therefore, the dissolved oxygen concentration management can be simplified and the amount of nitrogen used can be reduced. The dissolved oxygen concentration in the present invention is measured by measuring the oxygen concentration in the solution at the start of the polymerization when the polymerization vessel internal temperature reached a predetermined polymerization temperature using a DO meter B-505 manufactured by Iijima Electronics Co., Ltd. is there.

  In the copolymerization of the original copolymer (A) of the present invention, a polymerization initiator is not essential, and may be thermal polymerization, polymerization using UV radiation, polymerization using ionizing radiation, etc., but polymerization is performed from the viewpoint of the polymerization rate. It is preferable to use an initiator. Examples of the polymerization initiator include a photopolymerization initiator, an ionic polymerization initiator, and a radical polymerization initiator. From the viewpoint of productivity, it is preferable to use a radical polymerization initiator. As the radical polymerization initiator, all known initiators can be used, for example, those described in known product catalogs of initiator manufacturers such as Nippon Oil & Fats Co., Ltd., Wako Pure Chemical Industries, Ltd. Among them, 2,2'-azobisisobutyronitrile, 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-azobis-2,4-dimethyl Azo compounds such as valeronitrile, 2,2′-azobis-2-methylbutyronitrile, lauroyl peroxide, benzoyl peroxide, t-butylperoxyneodecanate, t-butylperoxypivalate, t-butyl Suitable organic peroxides such as peroxy-2-ethylhexanoate, t-butylperoxybenzoate, and dicumyl peroxide It is possible to use.

  The amount of the polymerization initiator used is preferably 0.001 to 5.0 parts by weight, more preferably 0.001 to 2.0 parts by weight, based on the amount of the monomer mixture used for copolymerization. More preferably, it is 0.01 to 1.5 parts by weight.

  In addition, when the thermoplastic polymer of the present invention is derived from the original copolymer (A), the content of the polymer having a molecular weight of 4 times or more the value of the weight average molecular weight of the thermoplastic polymer of the present invention is If it becomes 3.0 weight% or less, there is no restriction | limiting in an original copolymer (A) and its manufacturing method, However, It is preferable to add a chain transfer agent at the time of the copolymerization. For each of the original copolymer (A) and the thermoplastic polymer derived from the original copolymer (A), a polymer having a molecular weight 4 times or more the value of the weight average molecular weight (hereinafter simply referred to as a high molecular weight polymer) The chain transfer agent preferably includes a mercaptocarboxylic acid ester and / or an aromatic thiol as the chain transfer agent, A chain transfer agent containing a mercaptocarboxylic acid ester is more preferable from the viewpoint of both maintaining the color tone after heat treatment of the original copolymer (A) and the thermoplastic polymer of the present invention and reducing the content of the high molecular weight product. is there.

  During copolymerization of the original copolymer (A), a polymer having a molecular weight of at least 4 times the value of the weight average molecular weight of the thermoplastic polymer of the present invention tends to be formed due to the association of unsaturated carboxylic acid monomers. However, by using a chain transfer agent containing a mercaptocarboxylic acid ester and / or an aromatic thiol, the production of the polymer can be suppressed.

  The chain transfer constant at 60 ° C. with respect to the chain transfer agent of the methyl methacrylate monomer of the chain transfer agent containing a mercaptocarboxylic acid ester is not particularly limited, but when compared between mercaptocarboxylic acid esters, From the viewpoint of reducing the content of a polymer having a molecular weight 4 times or more of the average molecular weight value, the chain transfer constant value is preferably 0.20 or more, more preferably 0.40 or more, More preferably, it is 0.60 or more, Especially preferably, it is 0.70 or more, Most preferably, it is 0.75 or more. Although there is no restriction | limiting in particular as an upper limit of the chain transfer constant of the chain transfer agent containing a mercaptocarboxylic acid ester, Preferably it is 700 or less from a viewpoint of the handleability at the time of superposition | polymerization adjustment, and productivity, More preferably, it is 50.0 or less. More preferably 10.0 or less, particularly preferably 5.00 or less, and most preferably 4.00 or less.

  The mercaptocarboxylic acid ester is not particularly limited. For example, n-octyl thioglycolate, isooctyl thioglycolate, 2-ethylhexyl thioglycolate, methyl thioglycolate, ethyl thioglycolate, n-propyl thioglycolate Thioglycolate such as n-butyl thioglycolate, dodecyl thioglycolate, n-butyl thioglycolate, methyl 2-mercaptopropionate, ethyl 2-mercaptopropionate, n-butyl 2-mercaptopropionate, 3 -Methyl mercaptopropionate, ethyl 3-mercaptopropionate, n-propyl 3-mercaptopropionate, isopropyl 3-mercaptopropionate, n-butyl 3-mercaptopropionate, 3-mercaptopropion tert-butyl, isobutyl 3-mercaptopropionate, n-pentyl 3-mercaptopropionate, isoamyl 3-mercaptopropionate, sec-amyl 3-mercaptopropionate (1-methylbutyl 3-mercaptopropionate), 3-mercapto 2-methylbutyl propionate, 1,3-dimethylbutyl 3-mercaptopropionate, neopentyl 3-mercaptopropionate, 1-methylamyl 3-mercaptopropionate, 2-methylamyl 3-mercaptopropionate, 3-mercaptopropionate 3- Methyl amyl, tert-amyl 3-mercaptopropionate, n-hexyl 3-mercaptopropionate, cyclohexyl 3-mercaptopropionate, n-heptyl 3-mercaptopropionate, 3-mer 2,4-dimethylpentyl ptopropionate, 2,3-dimethylpentyl 3-mercaptopropionate, methoxymethyl 3-mercaptopropionate, ethoxymethyl 3-mercaptopropionate, butoxymethyl 3-mercaptopropionate, 3-mercaptopropion Methoxyethyl acid, ethoxyethyl 3-mercaptopropionate, butoxyethyl 3-mercaptopropionate, methoxypropyl 3-mercaptopropionate, ethoxypropyl 3-mercaptopropionate, butoxypropyl 3-mercaptopropionate, methoxy 3-mercaptopropionate Butyl, ethoxybutyl 3-mercaptopropionate, butoxybutyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, 3-mercaptotop N-octyl lopionate, isooctyl 3-mercaptopropionate, tert-octyl 3-mercaptopropionate, nonyl 3-mercaptopropionate, isononyl 3-mercaptopropionate, tert-nonyl 3-mercaptopropionate, 3-mercaptopropionic acid Decyl, isodecyl 3-mercaptopropionate, undecyl 3-mercaptopropionate, n-dodecyl 3-mercaptopropionate, tert-dodecyl 3-mercaptopropionate, isododecyl 3-mercaptopropionate, tridecyl 3-mercaptopropionate, 3- Tetradecyl mercaptopropionate, pentadecyl 3-mercaptopropionate, hexadecyl 3-mercaptopropionate, octadecyl 3-mercaptopropionate, 3-me Isooctadecyl captopropionate, oleyl 3-mercaptopropionate, palmitoleyl 3-mercaptopropionate, linoleyl 3-mercaptopropionate, linolenyl 3-mercaptopropionate, phenyl 3-mercaptopropionate, benzyl 3-mercaptopropionate, 3 -Mercaptopropionic acid esters such as allyl mercaptopropionate, halides such as their fluoro compounds, and mercaptocarboxylic acid esters such as 2-mercaptoethyl octanoic acid ester can be preferably used. Although there is no restriction | limiting in particular as aromatic thiol, For example, benzenethiol, m-bromobenzenethiol, p-bromobenzenethiol, m-chlorobenzenethiol, p-chlorobenzenethiol, 1-naphthalenethiol, 2-naphthalenethiol, benzylthiol And aromatic thiols such as m-toluenethiol and p-toluenethiol can be preferably mentioned, and one or more of these can be used. The chain transfer agent containing a mercaptocarboxylic acid ester and / or an aromatic thiol is more preferably a chain transfer agent containing a mercaptocarboxylic acid ester, and more preferably a mercapto such as a thioglycolic acid ester and / or a mercaptopropionic acid ester. It is a chain transfer agent containing a carboxylic acid ester, particularly preferably a chain transfer agent containing a mercaptopropionic acid ester, and it is also preferable to use one or more of these in combination. Particularly preferred as the mercaptopropionic acid ester are methyl 3-mercaptopropionate, n-butyl 3-mercaptopropionate, n-dodecyl 3-mercaptopropionate, isooctyl 3-mercaptopropionate and 2-ethylhexyl 3-mercaptopropionate. Yes, the affinity with the unsaturated carboxylic acid ester monomer and the unsaturated carboxylic acid monomer at the time of copolymerization is improved, and more than 4 times the value of the weight average molecular weight in the obtained original copolymer (A) Most preferred are methyl 3-mercaptopropionate, n-butyl 3-mercaptopropionate and 2-ethylhexyl 3-mercaptopropionate from the viewpoint of reducing the content of the polymer having a molecular weight of 5 and the handling property. In consideration of the color tone (yellowness) and odor reduction after treating the original copolymer (A) and the thermoplastic polymer at a high temperature of 300 ° C. or higher, mercaptocarboxylic acid esters are preferable to aromatic thiols. By using a mercaptocarboxylic acid ester, more preferably a mercaptopropionic acid ester, the odor peculiar to the mercaptan at the time of manufacture is reduced or zero, and the working environment is improved. Particularly preferred aromatic thiols are benzenethiol and 2-naphthalenethiol, and most preferred is 2-naphthalenethiol. The addition method of the chain transfer agent of the present invention is not particularly limited, such as batch addition or divided addition, and one or more chain transfer agents containing no mercaptocarboxylic acid ester and / or aromatic thiol are used in combination. It can also be used.

  In addition, in the original copolymer (A) and the thermoplastic polymer of the present invention, it is preferable that a residue of a chain transfer agent containing a mercaptocarboxylic acid ester and / or an aromatic thiol is contained at least at a terminal. It is preferable from the viewpoint of suppression, and further, from the viewpoint of the color tone (yellowness) after heat treatment such as 250 ° C. or higher, it is more preferable that the mercaptocarboxylic acid ester residue is contained at least at the terminal from the aromatic thiol.

  Further, by using a chain transfer agent containing a mercaptocarboxylic acid ester and / or an aromatic thiol, a smaller amount is used compared to the case of using a chain transfer agent not containing a mercaptocarboxylic acid ester and / or an aromatic thiol. Additives exhibit low molecular weight and are more rapid-acting, so the unreacted residual amount of the chain transfer agent in the original copolymer (A) can be converted to chain transfer without mercaptocarboxylic acid ester and / or aromatic thiol. Compared with the case where an agent is used, it can be reduced or zero, and the thermal stability is improved. In addition, since the addition of a smaller amount is effective, the concentration of the chain transfer agent in the latter half of the polymerization is lowered, and the amount of low molecular weight products having a molecular weight of 5000 or less can be reduced. In particular, by using a chain transfer agent containing a mercaptocarboxylic acid ester, it is possible to suppress the formation of high molecular weight substances and the formation of low molecular weight substances while maintaining a high color tone (yellowness) after heat treatment such as 250 ° C. or higher. Can be achieved. In addition, when a mercaptocarboxylic acid ester is used as a chain transfer agent in the copolymerization of an unsaturated carboxylic acid ester monomer and an unsaturated carboxylic acid monomer, the unsaturated carboxylic acid ester monomer and the unsaturated carboxylic acid monomer Since it has excellent affinity with the polymer, even when compared to the case of using an alkyl mercaptan having a larger chain transfer constant value than the mercaptocarboxylic acid ester as a chain transfer agent, the formation of a high molecular weight polymer and low molecular weight are suppressed. It tends to be excellent in suppressing body formation.

  In this case, the unreacted residual amount of the chain transfer agent in the chain transfer agent original copolymer (A) and the thermoplastic polymer was measured by gas chromatography (GC-14B, manufactured by Shimadzu Corporation, column: It can be quantified by using a capillary column DB-5 manufactured by J & W. The unreacted residual amount in this case is not particularly limited, but is preferably 20000 ppm or less and preferably 5000 ppm or less with respect to 100% by weight of the original copolymer (A) and the thermoplastic polymer, respectively. More preferably, it is 3000 ppm or less, Especially preferably, it is 1000 ppm or less, Most preferably, it is the range of 0-300 ppm. In this way, by reducing or zeroing the unreacted residual amount in the original copolymer (A), the unreacted residual amount in the derived thermoplastic polymer is also reduced or zeroed. There is a tendency for thermal stability to improve.

In addition, the terminal group of the original copolymer (A) and the thermoplastic polymer is not particularly limited, but when a mercaptocarboxylic acid ester residue, particularly a mercaptopropionic acid ester residue is included in at least a part of the terminal group ,
The thermal stability is improved, and water generated by (i) dehydration and / or (b) dealcoholization reaction by intramolecular cyclization reaction when heat-treated at a temperature of 300 ° C. or higher, for example, 340 ° C. and / or There is a tendency that the amount of gas generated by polymer decomposition other than alcohol can be reduced.

In the copolymerization of the original copolymer (A), the polymerization yield is not particularly limited, but from the viewpoint of productivity, the polymerization yield is preferably 50% or more, more preferably 60% or more, More preferably, it is 70% or more, particularly preferably 75% or more, and most preferably 80% or more. By improving the polymerization yield of the original copolymer (A), the content of a polymer having a value four times or more the weight average molecular weight (hereinafter sometimes referred to as high molecular weight) also tends to increase. . This tendency is particularly large in solution polymerization and precipitation polymerization, and in particular, in the copolymerization of an unsaturated carboxylic acid ester monomer and an unsaturated carboxylic acid monomer, it is remarkable when using solution polymerization and precipitation polymerization. Even when the polymerization yield is improved to 60% or more, which is the more preferable value, by using a chain transfer agent containing a mercaptocarboxylic acid ester and / or an aromatic thiol, the content of the high molecular weight substance is 3.0. It can be reduced to not more than wt%. Further, by using a chain transfer agent containing a mercaptocarboxylic acid ester and / or an aromatic thiol, more preferably a chain transfer agent containing a mercaptocarboxylic acid ester, a chain transfer containing no mercaptocarboxylic acid ester and / or aromatic thiol is used. Compared with the case where an agent is used, the molecular weight can be adjusted (adjusted on the low molecular weight side) by adding a small amount (comparison in terms of the number of moles of chain transfer agent to be added), and the molecular weight distribution can be further narrowed. Conventionally, polymers obtained by precipitation polymerization and solution polymerization tend not to show a large difference when compared with the content of polymers having a molecular weight of 10,000 or less, compared with polymers obtained by suspension polymerization and bulk polymerization products. However, when focusing only on the content of a polymer having a molecular weight of 5000 or less, which has a lower molecular weight, this content tends to be relatively high. Therefore, after polymerization, it was necessary to carry out washing with water and / or a solvent to reduce the content of the polymer having a molecular weight of 5000 or less. However, a chain transfer agent containing a mercaptocarboxylic acid ester and / or an aromatic thiol was used. By using it, the content of the polymer having a molecular weight of 5000 or less in the polymer obtained by precipitation polymerization or solution polymerization can be reduced even without washing. In a polymerization system including a solvent such as precipitation polymerization or solution polymerization, a polymer having a molecular weight of 5000 or less is likely to be formed in the latter half of the polymerization when the monomer concentration in the system is lowered, but contains a mercaptocarboxylic acid ester and / or an aromatic thiol. By using a chain transfer agent, the concentration of the chain transfer agent in the system in the latter half of the polymerization can be reduced or zero, and the amount of low molecular weight products produced can be reduced. In particular, a chain transfer agent containing a mercaptocarboxylic acid ester and / or an aromatic thiol when polymerized using an organic solvent (E) having a solubility parameter in the range of 11.9 to 17.6 MPa ^1/2 , More preferably, a chain transfer agent containing a mercaptocarboxylic acid ester, more preferably a chain transfer agent containing a mercaptopropionic acid ester, is used, so that a chain transfer agent containing no mercaptocarboxylic acid ester and / or aromatic thiol (for example, an alkyl mercaptan) is used. As compared with the case of using), it exhibits a remarkable rapid effect, and can reduce the amount of polymer produced more than four times the weight average molecular weight and the amount of low-molecular weight polymer having a molecular weight of 5000 or less. This tendency increases as the polarity of the organic solvent (E) decreases, and the production amount of a polymer (high molecular weight) having a value equal to or more than four times the weight average molecular weight, which has conventionally been difficult to achieve by precipitation polymerization. And the production amount of a low molecular weight body (low molecular weight body) having a molecular weight of 5000 or less can be suppressed.

  In other words, the affinity between a mercaptocarboxylic acid ester and / or a chain transfer agent containing an aromatic thiol and a monomer mixture comprising an unsaturated carboxylic acid ester monomer and an unsaturated carboxylic acid monomer is As compared with the affinity between the organic solvent (E) and the chain transfer agent containing an aromatic thiol and / or an aromatic thiol, the higher it is, the more difficult it is in conventional precipitation polymerization, solution polymerization, particularly precipitation polymerization. It is estimated that the production of molecular weight and low molecular weight can be suppressed. For example, when a mixed solvent of a carboxylic acid ester such as butyl acetate and an aliphatic hydrocarbon or alicyclic hydrocarbon is used as the organic solvent (E), the amount of the carboxylic acid ester in the organic solvent (E) decreases (organic The lower the polarity of the solvent (E), the more the chain transfer agent containing the mercaptocarboxylic acid ester and / or aromatic thiol, the unsaturated carboxylic acid ester monomer and the unsaturated carboxylic acid monomer. The affinity with the resulting monomer mixture is improved, and the production of high molecular weight and low molecular weight substances can be suppressed.

  In addition, regarding the polarity of the organic solvent (E) described here, the magnitude of the polarity can generally be compared by the solubility parameter, but when the alicyclic hydrocarbon represented by cyclohexane is handled as the organic solvent (E). Unlike the case of using aliphatic hydrocarbons such as hexane and heptane, the solubility parameter is the actual polarity (polarity for monomer mixture consisting of unsaturated carboxylic acid ester monomer and unsaturated carboxylic acid monomer) Since the value is too large to match, care must be taken. Therefore, when an alicyclic hydrocarbon typified by cyclohexane is used as the organic solvent (E), the amount of polymer produced and a molecular weight of 5000 or less, estimated from its solubility parameter, is at least four times the weight average molecular weight. There exists a tendency to express a big effect rather than the inhibitory effect of the production amount of low molecular weight body. Further, in the present invention, an anionic system such as n-dodecylbenzenesulfonic acid, diisobutylene / maleic anhydride copolymer, a cationic system such as octadecylamine acetate, polyoxyethylene sorbitan, and the like within the range not impairing the effects of the present invention. Nonionic surfactants such as monooleate and polyoxyethylene monooleate can also be used as the dispersant. Among them, a nonionic surfactant can be preferably used for reasons such as little coloring.

  In the present invention, when producing the original copolymer (A) by precipitation polymerization, an organic solvent containing the original copolymer (A) obtained by copolymerization in an organic solvent (E) which is a preferred polymerization solvent. Regarding the slurry, the ratio of the original copolymer (A) in the total weight of the previous slurry in the slurry at the stage where the copolymerization is completed is not particularly limited, but is preferably 5% by weight or more from the viewpoint of productivity. More preferably, it is 10% by weight or more, more preferably 14% by weight or more, particularly preferably 16% by weight or more, and most preferably 20% by weight or more.

  The organic solvent slurry can be separated and fractionated from the original copolymer (A) and the organic solvent (E) by, for example, solid-liquid separation using a centrifuge, and if necessary, an organic solvent ( The original copolymer (A) containing about several percent of E) is dried by a shelf dryer, a conical dryer, a centrifugal dryer, or the like, so that the original copolymer (A) containing no organic solvent (E) ) Can also be produced.

  More simply, if possible, the organic copolymer (E) can be recovered as a dry polymer simultaneously with recovering the original copolymer (A) with a spray dryer.

  The number average particle size of the primary particles of the original copolymer (A) is not particularly limited, but the improvement of the extraction effect of residual monomers and oligomers in the particles by the organic solvent (E) during polymerization and the particles after polymerization From the viewpoint of improving the drying efficiency, it is preferably in the range of 0.05 to 40000 μm, more preferably in the range of 0.1 to 5000 μm, still more preferably in the range of 0.1 to 500 μm, particularly preferably. It is the range of 0.1-10.0 micrometers, Most preferably, it is the range of 0.1-5.0 micrometers. The raw copolymer having a number average particle size in the above range also has an advantage that the washing efficiency is improved in washing with water that is preferably carried out as necessary prior to the second step of carrying out the intramolecular cyclization reaction. .

  In the present invention, the organic solvent slurry containing the original copolymer (A) copolymerized in the specific organic solvent (E) of the present invention obtained in the first step (hereinafter referred to as the original copolymer slurry). The following washing step can be carried out prior to the molecular cyclization reaction in the second step. That is, after solid-liquid separation of the original copolymer (A) slurry, the obtained original copolymer (A) cake (the original copolymer cake used in the washing step is preferably an organic solvent (E) Water and / or an organic solvent is added to and washed, and solid-liquid separation is performed again from the washing solution to obtain the original copolymer (B), and then the original copolymer (B) is used. The second step is performed. The main cleaning is preferably performed once from the viewpoint of simplification of the manufacturing process, but can be performed multiple times with water and / or an organic solvent, if necessary. These washings can also be carried out alternately. In the present invention, it is preferable to wash with at least water from the viewpoints of particle size control after washing, dispersibility after solid-liquid separation, drying efficiency, and dispersibility after drying. Although there is no restriction | limiting in particular as an organic solvent used for washing | cleaning, The thing with the solubility with respect to this organic solvent of an original copolymer is 1 g / 100ml or less is preferable, regardless of a single solvent and a mixed solvent, The raw material obtained through washing | cleaning From the viewpoint of solid-liquid separation of the copolymer, handling properties and drying efficiency during drying, and the color tone (yellowness) of the thermoplastic polymer and the thermoplastic resin composition of the present invention, the organic solvent (E) is most preferable. .

  By the washing step, the original copolymer (B) particles having a small volume of volatile components and excellent handling properties can be obtained, and the thermoplastic polymer of the present invention obtained through the second step can be obtained. The color tone can be improved. Here, the upper limit of the volatile content in the cake of the original copolymer (B) after solid-liquid separation is not particularly limited, but is preferably 90% by weight or less, more preferably 60% by weight or less. is there. When the above copolymer cake obtained by copolymerization in a specific organic solvent (E) is washed as described above, the number average particle size of the original copolymer (B) is not particularly limited. Controlled in the range of ~ 100,000 μm, preferably in the range of 1 to 40000 μm, more preferably in the range of 1 to 5000 μm, still more preferably in the range of 1 to 3000 μm, and particularly preferably in the range of 2 to 2000 μm. Is done. In the original copolymer (B) obtained by subjecting the original copolymer to a washing step, the particle diameter increases, and in the operations such as drying prior to the second step and the second step, the handling property of the particles is improved. Excellent. In the washing step, if there is an organic solvent (E) remaining in the original copolymer cake and / or an organic solvent (E) added at the time of washing, aggregation of particles of the original copolymer may occur. The degree is controlled, and the particle diameter can be controlled in the above preferable range.

  There are no particular restrictions on the method of solid-liquid separation of the slurry of the original copolymer (A) in the first filtration, and ordinary centrifuges, pressure filters, suction filters, vibration filters, belt filters, etc. By using it preferably, a cake of the original copolymer (A) can be obtained.

  When water is added to the cake of the original copolymer (A) obtained by separation and fractionation by the first filtration, the raw copolymer (A) is washed by heating with stirring, and the polymer particles are removed. Agglomeration can be performed and the particles can be controlled within the specific range. The amount of water added at the time of washing is not particularly limited, but is preferably 100 to 2000 parts by weight, more preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the cake obtained by the first filtration. More preferably, it is 200 to 600 parts by weight. If the amount of water added is 100 parts by weight or more, the cleaning effect tends to increase. If the amount of water added is 2000 parts by weight or less, the wastewater treatment load tends to decrease.

The lower limit of the concentration of the original copolymer (A) in the cleaning liquid is not particularly limited, but is preferably 0.1% by weight or more, more preferably 1% by weight or more, and further preferably from the viewpoint of productivity. It is 10% by weight or more, particularly preferably 12% by weight or more, and most preferably 15% by weight or more. The upper limit of the concentration of the original copolymer (A) in the cleaning liquid is not particularly limited, but is preferably 50% by weight or less, more preferably 40% by weight or less, and still more preferably 30% by weight or less. is there. Here, the concentration of the original copolymer (A) in the cleaning liquid is calculated as follows.
Concentration (% by weight) of the original copolymer in the cleaning liquid = 100 × (1−α / 100) × (the amount of cake (parts by weight) of the original copolymer (A)) / (of the original copolymer (A) Cake amount (parts by weight) + water addition amount (parts by weight)).
α: Volatile content (% by weight) of the original copolymer (A) cake

Note that the volatile content (% by weight) in the cake of the original copolymer (A) is obtained when the cake is subjected to heat treatment in a vacuum dryer at 130 ° C. until the volatile components are completely distilled off. It is a value calculated from the weight change of the following formula.
Volatile content (% by weight) in cake of original copolymer (A) = weight reduction rate (%) = [(weight before heat treatment−weight after heat treatment) / weight before heat treatment] × 100.

  In the present invention, the washing temperature and the solid-liquid separation temperature after washing (second filtration temperature) are not particularly limited as long as the water and / or organic solvent to be used does not become a solid. The subsequent solid-liquid separation temperature is preferably in the range of 5 to 200 ° C. The lower limit of the washing temperature is more preferably 20 ° C. or higher, further preferably 50 ° C. or higher, particularly preferably 60 ° C. or higher, and most preferably 70 ° C. or higher. The upper limit of the washing temperature is more preferably 150 ° C. or less, still more preferably 120 ° C. or less, particularly preferably 110 ° C. or less, and most preferably 100 ° C. or less. The upper limit of the solid-liquid separation temperature (second filtration temperature) after washing is more preferably 80 ° C. or less, and still more preferably 70, from the viewpoint of the melt residence stability of the obtained original copolymer (B). ° C or less, particularly preferably less than 50 ° C, and most preferably 40 ° C or less. The lower limit of the solid-liquid separation temperature (second filtration temperature) after washing is preferably 5 ° C or higher, more preferably 10 ° C or higher, still more preferably 15 ° C or higher, particularly preferably 20 ° C or higher. is there. By setting the washing temperature and the second filtration temperature to 5 ° C. or higher, the washing effect tends to increase.

  The apparatus for carrying out the washing operation is not particularly limited as long as the washing temperature can be controlled within the above range, and an autoclave or the like equipped with a normal stirrer can be used. It is possible to preheat the slurry of the original copolymer and / or the water added to it during the washing.

  The method of solid-liquid separation (second filtration) of the water slurry obtained by the above washing operation is not particularly limited as long as it can be filtered at the above temperature, and is a normal centrifuge, pressure filtration. However, from the viewpoint of reducing the volatile matter after solid-liquid separation and reducing the load of the subsequent drying step, centrifugal separation is particularly preferable. . By carrying out the washing method of the present invention, the volatile content of the original copolymer (B) after the second filtration is preferably 80% by weight or less, more preferably 70% by weight or less, still more preferably 50% by weight. The load of the subsequent drying process can be reduced.

  Further, if necessary, by drying the original copolymer (B) cake containing water and / or organic solvent obtained by the above washing operation with a shelf dryer, a conical dryer, a centrifugal dryer or the like. It is also possible to produce a raw copolymer (B) that does not contain an organic solvent (E).

  The number average particle size in the present invention is observed with a scanning electron microscope (SEM) at 150 times or 10,000 times, and the particle size is analyzed (image software (Scion Corporation) image analysis software “Scion”). Image ”) represents the number average particle size calculated.

  Further, the oxygen concentration in the gas phase in the cleaning system and the dissolved oxygen concentration in the cleaning liquid at the time of cleaning are not particularly limited, and water and / or an organic solvent usually used in the process such as ion-exchanged water is used in the normal air However, from the viewpoint of the color tone of the original copolymer (B) after washing, and the stability of melt retention at a high temperature of the original copolymer (B), the oxygen concentration in the gas phase in the washing system is preferably 800,000 ppm. Or less, more preferably 100,000 ppm or less, still more preferably 10,000 ppm or less, particularly preferably 1000 ppm or less, and most preferably close to 0 ppm or 0 ppm. The dissolved oxygen concentration in the cleaning liquid at the time of cleaning is not particularly limited, but is preferably 100 ppm or less, more preferably 20 ppm or less, further preferably 10 ppm or less, particularly preferably 6 ppm or less, and most preferably It is as close as possible to 0 ppm or 0 ppm. In order to control the oxygen concentration in the gas phase in the cleaning system and the dissolved oxygen concentration in the cleaning liquid within the above preferable ranges, it is preferable to perform the cleaning in an inert gas atmosphere. More specifically, a method of passing an inert gas in a cleaning container and / or a cleaning liquid, a method of pressurizing and filling an inert gas into a cleaning container before starting cleaning (a method of repeating pressure filling and degassing), A method of filling an inert gas after degassing the inside of the hermetic washing container before charging the raw copolymer can be exemplified. In addition, although there is no restriction | limiting as an inert gas, Especially nitrogen, helium, neon, argon etc. are mentioned.

  In the second step in the present invention, that is, the original copolymer (A) or the original copolymer (B) is heated, and (i) dehydration and / or (b) dealcoholization reaction is carried out by (i) dehydration and (i) ) There is no particular limitation on the method for producing the thermoplastic polymer containing the glutaric anhydride-containing unit, and it is produced by passing through a heated extruder having a vent, in an inert gas atmosphere such as in a nitrogen stream, or A method of producing in an apparatus that can be heated and devolatilized under vacuum, or a method of intramolecular cyclization by heating devolatilization treatment, heat treatment or the like in the presence or absence of a cyclization catalyst in a solution can be performed. At this time, if an intramolecular cyclization reaction is carried out by heating in the presence of oxygen, the yellowness tends to deteriorate, so it is more preferable to sufficiently substitute the interior 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, and the like can be used. It is a twin screw extruder or a twin screw / single screw combined continuous kneading extruder. In particular, by using a biaxial / uniaxial composite continuous kneading extruder, there is a tendency to obtain a thermoplastic copolymer excellent in color tone, transparency and mechanical properties, and therefore, 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 raw copolymer as a raw material is heat-treated in a continuous manner to advance the cyclization reaction, the heat generated by shearing of the extruder increases due to the increase in melt viscosity as the reaction proceeds, and the molecular main There is a tendency for coloring due to thermal decomposition of the chains 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 when the reaction temperature 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, so that the obtained (i) glutaric anhydride-containing unit is It is presumed that the thermoplastic polymer contained is particularly excellent in color tone and mechanical properties.

  In addition, the temperature at which devolatilization is performed by the above method is not particularly limited as long as (i) dehydration and / or (b) intramolecular cyclization reaction is caused by dealcoholization, but the lower limit is 140 ° C. or higher. More preferably, the temperature is 180 ° C. or higher, more preferably 200 ° C. or higher. Further, the productivity is improved by increasing the amount of intramolecular cyclization treatment per hour, and the intramolecular cyclization reaction is promoted to remain. From the viewpoint of reducing the amount of carboxylic acid and further improving the thermal stability (maintaining color tone after heat treatment), the lower limit of the temperature during the intramolecular cyclization reaction is particularly preferably 300 ° C. or more, and most preferably the lower limit is 310 ° C. That's it. On the other hand, the upper limit of the temperature during the intramolecular cyclization reaction is preferably 380 ° C. or less, more preferably 360 ° C. or less, and particularly preferably 350 ° C. or less. Therefore, the cylinder temperature of the extruder when the original copolymer (A) or the original copolymer (B) is heated and devolatilized using an extruder is also preferably set within the above preferable range.

  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. Usually, it is 1 minute to 300 minutes, preferably 1 minute to 60 minutes, more preferably A range of 2 minutes to 30 minutes, particularly 3 minutes to 20 minutes is preferable. 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. Although there is no restriction | limiting in particular, It is preferable that it is 20 or more, More preferably, it is 30 or more, Especially preferably, it is 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 the reaction proceeds again during the heat molding process, and there is a tendency for silver and bubbles to be seen in the molded product and molding retention. Sometimes the color tends to deteriorate significantly.

  Furthermore, in the present invention, when heating the original copolymer (A) or the original copolymer (B) by the above method or the like, it is not essential, but as a catalyst for promoting the cyclization reaction to glutaric anhydride, One or more of acid, alkali and salt compounds can be added. When the cyclization catalyst is added, the upper limit of the addition amount is not particularly limited, but is preferably 10 parts by weight or less with respect to 100 parts by weight of the original copolymer (A) or the original copolymer (B). More preferably, it is 1 part by weight or less. Further, there are no particular restrictions on the types of these acids, alkalis, and salt compounds. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, acetic acid, propionic acid, benzoic acid, acrylic acid, methacrylic acid, maleic anhydride, maleic acid, p- Examples include toluenesulfonic acid, phosphoric acid, phosphorous acid, phenylphosphonic acid, and methyl phosphate. Examples of the basic catalyst include metal hydroxides, amines, imines, alkali metal derivatives, alkoxides, ammonium hydroxide 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, sodium methoxide, sodium ethoxide, sodium phenoxide, potassium methoxide, potassium ethoxide and alkoxide compounds such as potassium phenoxide, lithium acetate And organic carboxylates such as sodium acetate, potassium acetate and sodium stearate. Sodium hydroxide, sodium methoxide, lithium acetate and sodium acetate can be preferably used. These alkali metal compounds can be preferably used either as hydrates or anhydrides, particularly preferably lithium acetate or lithium acetate anhydride. The cyclization catalyst is not essential, and a thermoplastic polymer can be obtained without using the cyclization catalyst by adjusting the thermal history, stirring pressure and vacuum degree.

  Furthermore, when producing the thermoplastic polymer of the present invention, hindered phenol-based, benzotriazole-based, benzophenone-based, benzoate-based and cyanoacrylate-based UV absorbers and antioxidants, as long as the object of the present invention is not impaired. Higher fatty acids, acid esters and acid amides, lubricants and plasticizers such as higher alcohols, montanic acid and its salts, esters, half esters, stearyl alcohol, stearamide and ethylene wax, mold release agents, phosphorous acid Anti-coloring agents such as salts and hypophosphites, halogen-based flame retardants, phosphorus-based and silicone-based non-halogen flame retardants, nucleating agents, amine-based, sulfonic acid-based, polyether-based anti-static agents, pigments An additive such as a colorant may be optionally contained. However, it is necessary to add in a range where the color of the additive does not adversely affect the thermoplastic polymer of the present invention and the transparency is not lowered.

  The thermoplastic polymer of the present invention preferably further contains a rubber-containing polymer (C) from the viewpoint of improving impact resistance. The rubber-containing polymer (C) is composed of a layer containing one or more rubber-like polymers and one or more layers made of different polymers, and one or more layers of the rubber-like polymer inside. A so-called core-shell type multilayer structure polymer having a layer containing a polymer, or a graft copolymer obtained by copolymerizing a monomer mixture composed of a vinyl monomer in the presence of a rubbery polymer Etc. can be preferably used, but a multilayer structure polymer is particularly preferable because of its excellent transparency and low coloring.

  The number of layers constituting the multilayer structure polymer may be two or more, and may be three or more or four or more. A multilayer having one or more rubber layers (core layers) inside. A structural polymer is preferred. In the multilayer polymer, 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 monomers, silicone monomers, styrene monomers, nitrile monomers, conjugated diene monomers, monomers that form urethane bonds, ethylene monomers, propylene monomers Examples thereof include rubbers formed by polymerizing monomers and isobutene monomers. Preferred rubbers include, for example, acrylic units such as ethyl acrylate units and butyl acrylate units, silicone units such as dimethylsiloxane units and phenylmethylsiloxane units, styrene units such as styrene units and α-methylstyrene units, It is a rubber composed of nitrile units such as acrylonitrile units and methacrylonitrile units, and conjugated diene units such as butadiene units and isoprene units. A rubber composed of a combination of two or more of these components is also preferred. For example, rubber composed of acrylic units such as ethyl acrylate units and butyl acrylate units, and silicone units such as dimethylsiloxane units and phenylmethylsiloxane units, acrylic units such as ethyl acrylate units and butyl acrylate units And rubber composed of styrene units such as styrene units and α-methylstyrene units, acrylic units such as ethyl acrylate units and butyl acrylate units, and conjugated diene units such as butanediene units and isoprene units. Rubber, acrylic units such as ethyl acrylate units and butyl acrylate units, silicone units such as dimethylsiloxane units and phenylmethylsiloxane units, and styrene units such as styrene units and α-methylstyrene units. Examples include rubbers that are made. Among these, a rubber which is an acrylate containing an acrylic acid alkyl ester unit and a substituted or unsubstituted styrene unit is most preferable from the viewpoint of transparency and mechanical properties. In addition to these components, rubber obtained by crosslinking a copolymer composed of a crosslinkable component is also preferable. Such a crosslinkable component is not particularly limited, and examples of the corresponding monomer include divinylbenzene, allyl acrylate, allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, butylene glycol diacrylate, 1, 3 -Polyfunctional monomers such as butylene dimethacrylate, tetraethylene glycol diacrylate, triallyl cyanurate, triallyl isocyanurate and pentaerythritol tetraacrylate are exemplified, and these may be used alone or in combination of two or more. Can do.

  In the multilayered polymer, 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. However, the layer having a higher glass transition temperature than the rubber layer. A coalescence component is preferred. Polymers having thermoplastic properties include unsaturated carboxylic acid ester units, unsaturated carboxylic acid units, unsaturated glycidyl group-containing units, unsaturated dicarboxylic acid anhydride units, aliphatic vinyl units, aromatic vinyl units, vinyl cyanide. Examples thereof include polymers containing one or more units selected from units, maleimide units, unsaturated dicarboxylic acid units, and other vinyl units. Among them, a polymer containing an unsaturated carboxylic acid 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. A polymer is more preferred.

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

  There is no restriction | limiting in particular as a monomer used as the raw material of the said unsaturated carboxylic acid unit, A hydrolyzate of acrylic acid, methacrylic acid, maleic acid, and also maleic anhydride etc. are mentioned. In particular, acrylic acid and methacrylic acid are preferable from the viewpoint of excellent thermal stability, and methacrylic acid is more preferable. These can be used alone or in combination.

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

  Moreover, ethylene, propylene, butadiene, etc. can be used as a monomer used as the raw material of the said aliphatic vinyl unit. Examples of the monomer used as a raw material for the aromatic vinyl unit include styrene, α-methylstyrene, 1-vinylnaphthalene, 4-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, and 2-ethyl. -4-Benzylstyrene, 4- (phenylbutyl) styrene, halogenated styrene and the like can be used. Acrylonitrile, methacrylonitrile, ethacrylonitrile, etc. can be used as a monomer as a raw material for the vinyl cyanide unit. Examples of the monomer used as a raw material for the maleimide unit include maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N- (p- Bromophenyl) maleimide and N- (chlorophenyl) maleimide can be used. As a monomer used as the raw material of the unsaturated dicarboxylic acid unit, maleic acid, maleic acid monoethyl ester, itaconic acid, phthalic acid, and the like can be used. Examples of other monomers used as a raw material for vinyl units include acrylamide, methacrylamide, N-methylacrylamide, butoxymethylacrylamide, N-propylmethacrylamide, N-vinyldiethylamine, N-acetylvinylamine, allylamine, and methallylamine. N-methylallylamine, p-aminostyrene, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2-acryloyl-oxazoline, 2-styryl-oxazoline, and the like can be used. These monomers can be used alone or in combination of two or more. There is no restriction | limiting in particular as a manufacturing method of a rubber-containing polymer (C), Any of ionic polymerization and radical polymerization may be sufficient, However, Radical polymerization is preferable. In the copolymerization, for the purpose of controlling the molecular weight, although not essential, for example, n-octyl mercaptan, n-decyl mercaptan, n-butyl mercaptan, t-dodecyl mercaptan, n-dodecyl mercaptan, n-tetradecyl mercaptan, and Chain transfer agents such as alkyl mercaptans such as n-octadecyl mercaptan, carbon tetrachloride, carbon tetrabromide, dimethylacetamide, dimethylformamide, triethylamine, mercaptocarboxylic acid, mercaptocarboxylic acid ester and aromatic thiol can be added. Among the chain transfer agents, mercaptocarboxylic acid esters and / or aromatics from the viewpoint of the tensile strength retention rate during wet heat of the thermoplastic resin composition of the present invention obtained by adding the rubber-containing polymer (C). It is particularly preferable to use a chain transfer agent containing a thiol, more preferably a chain transfer agent containing a mercaptocarboxylic acid ester. Examples of such a chain transfer agent include those exemplified as the chain transfer agent preferably used during the production of the original copolymer (A).

  The rubbery polymer (C) of the present invention has a multilayer structure, and the outermost layer (shell layer) includes an unsaturated carboxylic acid alkyl ester unit, an unsaturated carboxylic acid unit, and an unsaturated glycidyl group as described above. Polymers containing one or more units such as units, aliphatic vinyl units, aromatic vinyl units, vinyl cyanide units, maleimide units, unsaturated dicarboxylic acid units, unsaturated dicarboxylic anhydride units, and other vinyl units And at least one selected from the above. Among these, at least one selected from polymers containing unsaturated carboxylic acid alkyl ester units, unsaturated carboxylic acid units, unsaturated glycidyl group-containing units, unsaturated dicarboxylic acid anhydride units, and the like is preferable.

  Multilayer structure polymer having outermost layer of polymer containing unsaturated carboxylic acid alkyl ester unit and unsaturated carboxylic acid unit as rubbery polymer (C) to be used for melt kneading with the thermoplastic polymer of the present invention Most preferably, is used.

  When the outermost layer is a polymer containing an unsaturated carboxylic acid ester unit and an unsaturated carboxylic acid unit, by heating, the intramolecular cyclization reaction is performed in the same manner as in the production of the copolymer of the present invention described above. As a result, a glutaric anhydride-containing unit represented by the general formula (1) is generated. Therefore, the outermost layer is heated to the outermost layer by heating when the multilayer structure polymer having an unsaturated carboxylic acid alkyl ester unit and a polymer containing an unsaturated carboxylic acid unit is blended with the thermoplastic copolymer and melt-kneaded. A multilayer structure polymer containing the glutaric anhydride-containing unit represented by the general formula (1) is obtained. Thereby, the multilayer structure polymer containing the glutaric anhydride-containing unit represented by the general formula (1) is well dispersed in the copolymer of the present invention which becomes a continuous phase (matrix phase). It becomes possible, and it is considered that extremely high transparency can be exhibited with improvement in mechanical properties such as impact resistance of the thermoplastic resin composition of the present invention.

  The monomer used as the raw material for the unsaturated carboxylic acid ester unit here is preferably an unsaturated carboxylic acid alkyl ester, more preferably an acrylic acid alkyl ester or a methacrylic acid alkyl ester, and more preferably methyl acrylate or methyl methacrylate. Is more preferably used.

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

  As a preferable example of the rubber-containing polymer (C) to be contained in the thermoplastic resin composition of the present invention, the core layer is butyl acrylate / styrene copolymer, and the outermost layer is methyl methacrylate / the above general formula ( 1) a copolymer comprising glutaric anhydride-containing units represented by 1), a core layer is represented by butyl acrylate / styrene copolymer, and an outermost layer is represented by methyl methacrylate / formula (1). Glutaric anhydride-containing unit / methacrylic acid copolymer, core layer is dimethylsiloxane / butyl acrylate copolymer and outermost layer is methyl methacrylate polymer, core layer is butanediene / styrene copolymer And those whose outermost layer is a methyl methacrylate polymer and those whose core layer is a butyl acrylate polymer and whose outermost layer is a methyl methacrylate polymer. It is. Here, “/” indicates copolymerization. Furthermore, a preferable example is one in which either one or both of the rubber layer and the outermost layer is a polymer containing a glycidyl methacrylate unit. Among them, the core layer is a butyl acrylate / styrene polymer, the outermost layer is a copolymer composed of methyl methacrylate / glutaric anhydride-containing units represented by the general formula (1), and the core layer is an acrylic. A butyl acid / styrene copolymer whose outermost layer is methyl methacrylate / glutaric anhydride-containing unit represented by the general formula (1) / methacrylic acid polymer is a continuous phase (matrix phase). It is possible to approximate the refractive index with the copolymer of the present invention, and to obtain a good dispersion state in the resin composition. It can be preferably used.

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

  In the multilayer structure polymer of the present invention, the weight ratio of the core to the shell is preferably 10% by weight or more and 90% by weight or less with respect to the whole multilayer structure polymer, and the core layer is 30% by weight. As mentioned above, it is more preferable that it is 90 weight% or less, and it is especially preferable that a core layer is 50 weight% or more and 80 weight% or less.

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

  Commercially available products of the multilayer structure polymer include, for example, “Metablene (registered trademark)” manufactured by Mitsubishi Rayon Co., “Kaneace (registered trademark)” manufactured by Kaneka Corporation, “Paralloid (registered trademark)” manufactured by Kureha Chemical Industry Co., Ltd., Rohm and "Acryloid (registered trademark)" manufactured by Haas, "Staffyroid (registered trademark)" manufactured by Gantz Kasei Kogyo Co., Ltd., and "Parapet (registered trademark) SA" manufactured by Kuraray Co., Ltd. Can be used.

  Further, specific examples of the rubber-containing graft copolymer used as the rubber-containing polymer (C) include an unsaturated carboxylic acid ester monomer (the specific examples thereof are described above) in the presence of the rubber-like polymer. ), Unsaturated carboxylic acid monomers (specific examples thereof are the same as those described above), aromatic vinyl monomers (specific examples thereof are the same as those described above), and if necessary, Examples thereof include graft copolymers obtained by (co) polymerizing monomers (mixtures) selected from one or more kinds of other copolymerizable vinyl monomers (specific examples thereof are the same as those described above).

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

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

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

  The graft copolymer may contain an ungrafted copolymer that is produced when the monomer mixture is graft copolymerized with the rubbery polymer. From the viewpoint of impact strength, the graft ratio is preferably 10 to 100%. Here, the graft ratio is a weight ratio of the grafted monomer mixture to the rubbery polymer. Further, the intrinsic viscosity measured at 30 ° C. of a methylethylketone solvent of the ungrafted copolymer is not particularly limited, but 0.1 to 2.0 dl / g is a balance between impact strength and moldability. It is preferably used from the viewpoint.

  In the present invention, the intrinsic viscosity of the graft copolymer in the methyl ethyl ketone solvent measured at 30 ° C. is not particularly limited. It is preferably used, more preferably 0.2 to 2.0 dl / g.

  The method for producing the graft copolymer in the present invention is not particularly limited, and may be a known polymerization method such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization, or a combination of these polymerization methods such as bulk suspension polymerization. Obtainable.

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

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

Regarding the copolymer composition and molecular weight distribution of the thermoplastic polymer of the present invention and the rubbery-containing polymer (C) in the thermoplastic resin composition, the separation operation of the soluble component and the insoluble component by the above solvent is performed. Later, each component is analyzed individually. Further, regarding the thermoplastic resin composition of the present invention, a film having a thickness of 100 ± 5 μm was prepared by solution casting or melt casting, and the surface of this film was observed with a differential interference reflection microscope (ECLIPSE LV100D manufactured by Nikon Corporation). At that time, observation was randomly performed at 10 points, and the count of the number of foreign matters (the number of irregularities derived from internal foreign matters) was repeated, and the average value was evaluated as the number of foreign matters per 1 mm square unit area (pieces / mm ² ). The number of foreign matters of 10 μm or more per 1 mm square unit area is not particularly limited, but is preferably 1000 or less, more preferably 15 or less, even more preferably 10 or less, and particularly preferably Is 3 or less, most preferably 0. Here, the foreign matter excludes disturbance foreign matter.

  In the present invention, the weight ratio when the thermoplastic polymer of the present invention and the rubber-containing polymer (C) are blended is not particularly limited, but is preferably in the range of 99/1 to 40/60. The range is more preferably in the range of / 1 to 50/50, still more preferably in the range of 99/1 to 60/40, and particularly preferably in the range of 99/1 to 70/30.

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

  Although there is no restriction | limiting in particular as glass transition temperature of the thermoplastic resin composition of this invention, From a viewpoint of practical heat resistance, Preferably it is 110 degreeC or more, More preferably, it is 120 degreeC or more. In a more preferred embodiment, the glass transition temperature is 125 ° C. or higher, and more preferably 130 ° C. or higher. Moreover, there is no restriction | limiting in particular as an upper limit, However, Usually, it is 200 degrees C or less, Preferably it is 160 degrees C or less. The glass transition temperature here refers to the glass transition temperature observed when the thermoplastic resin composition is measured at a heating rate of 20 ° C./min using a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer). Among these, it refers to the glass transition temperature of the matrix of the thermoplastic resin composition, not the glass transition temperature of the rubber polymer. In the present invention, in addition to the rubber-containing polymer (C), a monophosphite compound can be further contained. Thereby, since decomposition | disassembly of a rubber-containing polymer (C) is suppressed and a significant coloring suppression and a fluid improvement effect are acquired, it can use preferably.

The monophosphite compound used in the present invention is an organic phosphite ester having one phosphorus atom and three organic groups bonded in the molecule, and preferably has a molecular weight of 300 to 2000 from the viewpoint of heat resistance. Furthermore, it is more preferable that it is the range of molecular weight 350-1500, and it is most preferable that it is the range of molecular weight 400-1000 especially. When the molecular weight is 300 or less, it tends to volatilize during melt-kneading, and it is difficult to obtain the effect of suppressing coloration and improving fluidity. When the molecular weight is 2000 or more, there is a problem that high transparency is easily obtained. Furthermore, although there are forms such as liquid or solid as properties, there is no restriction in use, and in the case of liquid, the viscosity is preferably in the range of 1 to 10000 mPa · s, and further the viscosity is in the range of 2 to 7000 mPa · s. More preferably, the viscosity is most preferably in the range of 5 to 5000 mPa · s. Alternatively, in the case of solid properties, the melting point is preferably 60 to 220 ° C, more preferably 80 to 210 ° C, and most preferably 100 to 200 ° C. Further, a cyclic monophosphite compound in which two or more of the three oxygen atoms of the organic phosphite are bonded to an aromatic residue, or the three oxygen atoms of the organic phosphite Of these, a monophosphite compound in which at least one of them is bonded to an aromatic residue is preferable. Specific phosphite compounds include triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tris (2-t-butylphenyl) phos Phyto, tris (2,5-t-butylphenyl) phosphite, tris (mixed mono and di-nonylphenyl) phosphite, tris (2-t-butyl-4-methylphenyl) phosphite, tris (2- t-butyl-5-methylphenyl) phosphite, tris (2-t-butyl-4,6-dimethylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylenephos Phonite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4′-buty Den - bis (3-methyl -6-t-butylphenyl - di - tridecyl) phosphite, and the like.
Among these, tris (2-t-butylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (2,5-t-butylphenyl) phosphite, 2,2- Methylene bis (4,6-di-t-butylphenyl) octyl phosphite can be used particularly preferably. These specific phosphite compounds can be used alone or in combination of two or more.

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

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

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

  As a method for producing a resin composition containing a rubber-containing polymer (C) and, if necessary, a phosphite-based compound in the thermoplastic polymer of the present invention, the raw copolymer (A) of the present invention is heated. When the copolymer of the present invention is produced by heat treatment in a processing apparatus, 0.001 to 5 weights with respect to 100 parts by weight of the total amount of the rubber-containing polymer (C) and the original copolymer (A). Part of the phosphite compound at the same time as the original copolymer (A) and melt-kneading, the process for producing the thermoplastic polymer of the present invention, and the rubber-containing polymer (C) in the middle of the heat treatment After adding the 0.001 to 5 parts by weight of the phosphite compound and melt kneading to 100 parts by weight of the total amount of the base copolymer (A) and the thermoplastic polymer of the present invention, Total amount of thermoplastic polymer and rubber-containing polymer (C) of the present invention 100 A method in which melt-kneading the phosphite compound of 0.001 to 5 parts by weight relative to the amount portion thereof.

  The heat treatment apparatus that can be used is not particularly limited, and examples thereof include a single screw extruder, a twin screw extruder, a twin / single screw composite continuous kneading extruder, a triaxial extruder, a continuous or batch kneader kneader, and the like. It can be preferably used.

The melt viscosity of the thermoplastic resin composition of the present invention comprising the rubber-containing polymer (C) is not particularly limited, but a plunger type capillary rheometer (Capillograph type 1C manufactured by Toyo Seiki Seisakusho) is used. it was measured at a temperature of the glass transition temperature of + 0.99 ° C., a melt viscosity at a shear rate of 5 s ^-1 obtained by extrapolating the shear rate of 5 s ^-1 (Pa · s) is in the range of 10~100000Pa · s From the viewpoint of improving melt film-forming properties and melt filterability, it is more preferably in the range of 100 to 20000 Pa · s, still more preferably in the range of 100 to 5000 Pa · s, and particularly preferably 100 to 2000 Pa · s. It is the range of s.

  The thermoplastic polymer of the present invention and further the thermoplastic resin composition containing the rubber-containing polymer (C) may contain other thermoplastic resins such as polyethylene and polypropylene as long as the object of the present invention is not impaired. , Olefin resins such as ethylene-propylene copolymer, ethylene-propylene-diene copolymer and poly (4-methyl-1-pentene), acrylic resins such as polymethyl methacrylate, polystyrene, styrene-methyl methacrylate Halogen-containing resins such as copolymers, styrene-acrylonitrile copolymers, aromatic vinyl resins such as styrene-methyl methacrylate-acrylonitrile copolymers, acrylonitrile-butadiene-styrene block copolymers, vinyl chloride, chlorinated vinyl resins, etc. Resin, polyamide, polyphenylene sulfide resin, poly -Ether ether ketone resin, for example, polyester resin such as polyethylene naphthalate, polycarbonate polysulfone, polyphenylene oxide, polyacetal, polyimide, polyetherimide, polyethersulfone; polyoxybenzylene; polyamideimide, etc., polybutadiene rubber, acrylic rubber One or more selected from rubber polymers such as ABS resin and ASA resin blended with, for example, thermosetting resins such as phenol resin, melamine resin, polyester resin, silicone resin, and epoxy resin can be further contained. Also, lubricants and plasticizers such as higher fatty acids, acid esters and acid amides, higher alcohols, montanic acid and its salts, esters, half esters thereof, stearyl alcohol, stearamide and ethylene wax, phosphorous acid Anti-coloring agents such as salts and hypophosphites, halogen-based flame retardants, phosphorus-based and silicone-based non-halogen flame retardants, nucleating agents, amine-based, sulfonic acid-based, polyether-based anti-static agents, pigments Additives such as colorants such as dyes and fluorescent brightening agents may be optionally added. However, in light of the characteristics required by the application to be applied, it is preferable to add the additive within a range where the color of the additive does not adversely affect the thermoplastic polymer and the transparency is not lowered.

  The thermoplastic resin composition comprising the thermoplastic polymer of the present invention and further the rubbery polymer (C) is excellent in mechanical properties and molding processability, and can be melt-molded. Injection molding, press molding, and the like are possible, and a film, sheet, tube, rod, or other molded body having any desired shape and size can be used.

  A well-known method can be used for the manufacturing method of the film which consists of the thermoplastic polymer of this invention, and a thermoplastic resin composition. That is, production methods such as an inflation method, a T-die method, a calendar method, a cutting method, a casting method, an emulsion method, and a hot press method can be used. Preferably, an inflation method, a T-die method, a casting method or a hot press method can be used. In the case of a production method using an inflation method or a T-die method, an extruder type melt extrusion apparatus equipped with a single screw or twin screw can be used. The melt extrusion temperature for producing the film of the present invention is preferably 150 to 380 ° C, 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. Alternatively, a biaxially stretched film may be used. In the case of biaxial stretching, the mechanical strength is improved and the film performance is improved. When the film of the present invention is used as an optical film, an increase in retardation can be suppressed even when stretched by mixing other thermoplastic resins, and optical isotropy can be maintained. Further, in order to stabilize the optical isotropy and mechanical properties of the film, heat treatment (annealing) or the like can be performed after the stretching treatment.

  In addition, a T-die is attached to the tip of a conventionally known single-screw extruder or twin-screw extruder, and a film made of the thermoplastic polymer or thermoplastic resin composition of the present invention extruded into a film shape is taken up by a winding roll. When obtaining a roll film, the temperature of the take-up roll may be adjusted as appropriate to perform uniaxial stretching in the extrusion direction, simultaneous biaxial stretching in the direction perpendicular to the extrusion direction, and sequential biaxial stretching. it can. The film made of the thermoplastic polymer and thermoplastic resin composition of the present invention may be an unstretched film or a stretched film, but stretched, preferably biaxially stretched, toughness of the film, There exists a tendency for the bending resistance of a film to improve further. Here, the lower limit of the draw ratio is not particularly limited, but is preferably 1.1 times or more, more preferably 1.2 times or more, still more preferably 1.3 times or more, and particularly preferably 1 The upper limit of the draw ratio is not particularly limited, but is preferably 5.0 times or less, more preferably 4.0 times or less, still more preferably 3.5 times or less, Especially preferably, it is 3.0 times or less. Moreover, it is also possible to stabilize the phase difference and mechanical properties of the film by performing a heat treatment (annealing treatment) after stretching the film. Also, other thermoplastic resins can be mixed in order to adjust the phase difference and optical isotropy to desired ones. Furthermore, it is also possible to use the thermoplastic polymer and the thermoplastic resin composition of the present invention as a multilayer laminate having a surface layer, an inner layer or the like, or as a solution for coating.

A molded article or film obtained by processing the thermoplastic polymer and the thermoplastic resin composition of the present invention, for example, melt processing or processing with a solution, has high heat resistance, color tone, transparency, and fluidity. Taking advantage of its excellent impact resistance and melt retention stability, it can be used for various applications such as optical materials, electrical and electronic parts, automotive parts, mechanical mechanism parts, housings and their parts, general miscellaneous goods, More specifically, electrical equipment housings, OA equipment housings, various covers, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, light Pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, micro Electronic and electronic parts such as headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer-related parts; VTR parts, Representative for TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Household, office electrical product parts, office computer related parts, telephone related parts, facsimile related parts, copying machine related parts, cleaning jigs, oilless bearings, stern bearings, underwater bearings, various bearings, motors Parts, machine-related parts represented by products, lighters, typewriters, etc., optical equipment represented by microscopes, binoculars, cameras, watches, precision machine-related parts; various valves such as alternator terminals, alternator connectors, IC regulators, exhaust gas valves , Various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear Sensor, throttle position sensor, crankshaft position sensor, air flow meter, thermostat base for air conditioner, heating hot air flow control valve, radiator motor Brush holders for starters, water pump impellers, turbine vanes, wiper motor parts, dust distributors, starter switches, starter relays, transmission wire harnesses, window washer nozzles, air conditioner panel switch boards, coils for fuel-related solenoid valves, fuses Connectors, horn terminals, electrical component insulation plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters and ignition device cases. In addition, because of its excellent transparency and heat resistance, it is used as a component for optical recording / communications, such as imaging equipment for cameras, VTRs, projection TVs, viewfinders, filters, prisms, Fresnel lenses, etc. Various optical disk (VD, CD, DVD, MD, LD, etc.) substrates, various disk substrate protective films, optical disk player pickup lenses, optical fibers, optical switches, optical connectors, and other information equipment related parts such as liquid crystal displays, flat panel displays, plasmas Display light guide plate, Fresnel lens, polarizing plate, polarizer protective film, retardation film, light diffusion film, viewing angle widening film, reflection film, antireflection film, antiglare film, brightness enhancement film, prism sheet, pickup lens , Light guide films for touch panels, covers, etc., as parts related to transportation equipment such as automobiles, tail lamp lenses, head lamp lenses, inner lenses, amber caps, reflectors, extensions, side mirrors, room mirrors, side visors, instrument needles, instrument covers , Glazing typified by window glass, etc. as medical equipment related parts, spectacle lenses, spectacle frames, contact lenses, endoscopes, optical cells for analysis, etc., as building material related parts, lighting windows, road translucent plates, lighting covers It can also be applied to signboards, translucent sound insulation walls, bathtub materials, etc., and is extremely useful for these various applications. Among them, the thermoplastic resin composition containing the thermoplastic polymer and rubber-containing polymer (C) of the present invention has high heat resistance, color tone and transparency, and has a tensile ratio after conventional heat treatment, tensile properties and wet heat treatment. Since it is excellent in strength retention, it can be preferably used for optical film applications such as an optical compensation film. In the present invention, a polarizer protective film, a retardation film, a light diffusion film, a viewing angle widening film, a reflection film, an antireflection film, an antiglare film, a brightness enhancement film and the like are collectively referred to as an optical compensation film. Moreover, when using the thermoplastic resin composition containing the thermoplastic polymer or rubber-containing polymer (C) of the present invention, or a thermoplastic resin composition further blended with other resins as a polarizer protective film. Can use an easy-adhesion layer between the polarizer and the adhesive layer is not particularly limited. For example, a conventionally known one can be suitably used.

  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) Weight average molecular weight / molecular weight distribution The obtained original copolymer or thermoplastic polymer is dissolved in dimethylformamide to form a 0.3% by weight measurement sample solution, and dimethylformamide as a solvent at a temperature of 23 ° C. A gel permeation chromatograph equipped with a DAWN-DSP type multi-angle light scattering photometer (manufactured by Wyatt Technology) (pump: model 515, manufactured by Waters, column: TSK-gel-GMHXL, manufactured by Tosoh Corporation, flow rate: The weight average molecular weight and the molecular weight distribution were measured as absolute molecular weight using data processing software “ASTRA” (manufactured by Wyatt Technology) as data processing. The molecular weight distribution was calculated by weight average molecular weight (absolute molecular weight) / number average molecular weight (absolute molecular weight). In the Reference Examples, Examples and Comparative Examples, the weight average molecular weight (hereinafter sometimes referred to as Mw) is rounded off to the nearest hundred and the significant figures are rounded to the thousands, and the molecular weight distribution (hereinafter referred to as Mw). / May be described as / Mn) is rounded off to the second decimal place and rounded to the second decimal place.

(2) Content of polymer (high molecular weight) having a weight average molecular weight 4 times or more of the value of weight average molecular weight, content of polymer (low molecular weight) having a molecular weight of 5000 or less. A polymer or thermoplastic polymer is dissolved in dimethylformamide to form a 0.3 wt% measurement sample solution, and dimethylformamide as a solvent at a temperature of 23 ° C., a DAWN-DSP type multi-angle light scattering photometer (Wyatt Technology). Data processing as a data processing using a gel permeation chromatograph (pump: 515 type, manufactured by Waters, column: TSK-gel-GMHXL, manufactured by Tosoh Corp., flow rate: 0.8 ml / min) Using software "ASTRA" (manufactured by Wyatt Technology), weight average molecular weight, molecular weight fraction as absolute molecular weight Absolute molecular weight distribution chart in which the cloth is measured and the area is normalized to 1 (the horizontal axis is the logarithm of the molecular weight, and the vertical axis is the molar fraction scaled so that the peak area is 1. That is, each molecular weight range The peak area occupied by Next, this absolute molecular weight distribution diagram is printed on a sheet having a constant thickness, and an area occupied by a polymer having a molecular weight of four times or more of the weight average molecular weight value is cut out from the peak area of the absolute molecular weight distribution diagram. The mass of the part is measured and expressed as a ratio (% by weight) to the mass of the part representing the total peak area. That is, the content (% by weight) of a polymer having a molecular weight of 4 times or more of the weight average molecular weight value = {(having a molecular weight of 4 times or more of the weight average molecular weight value in the peak area of the absolute molecular weight distribution diagram) Mass of the portion occupied by the polymer) / (mass of the portion representing the total peak area in the absolute molecular weight distribution diagram)} × 100. Similarly, the ratio of the total peak area of polymers having a molecular weight of 5000 or less to the total peak area was determined as the low molecular weight content (% by weight).

(3) Chain transfer constant at 60 ° C. for methyl methacrylate monomer chain transfer agent The chain transfer constant at 60 ° C. for methyl methacrylate monomer chain transfer agent is “POLYMER HANDBOOK FOURTH EDITION, J. BRANDRUP, E.H. References: IMMERGUT and EA GRULKE, II / 97-159, WILEY INTERSCIENCE (1999) and "Radical polymerization (I), Otsu, p. 126, 127, Kagaku Dojin (1971)" The chain transfer constant at 60 ° C. for the methyl methacrylate monomer chain transfer agent is partly listed in TABLE 5 of “POLYMER HANDBOOK FOURTH EDITION, II / 97-159”. Further, the following equation (rate of disappearance of a chain transfer agent) / (rate of disappearance of monomer) = d [X] / d [M] = C x [X] / [M], i.e. Cx = dlog [X] / dlog [M] and the following Mayo equation can also be measured. In the present invention, the following Mayo equation (“FR Mayo, C. Walling, Chem. Rev., 46 , 191 (1950)”, “ The chain transfer constant Cx was determined using the new polymer chemistry introduction 1st report, Higashimura et al., P. 60, Kagaku Dojin (1995). 1 / P _n = 1 / P _n0 + C _x [X] / [M], where [X] is the concentration of the chain transfer agent, [M] is the concentration of the monomer, and P _n is in the presence of the chain transfer agent The number average degree of polymerization of the polymer when polymerized. P _n0 is the number average degree of polymerization of the polymer when polymerized in the absence of the chain transfer agent. After the inside of the 20 ml test tube was degassed, it was put under a nitrogen atmosphere and charged with methyl methacrylate. Next, 0.3% by weight of azobisisobutyronitrile (AIBN) based on the weight of charged methyl methacrylate was added as a polymerization initiator. Here, before use, methyl methacrylate was passed through a column packed with activated alumina, the polymerization inhibitor was removed, dehydrated with calcium hydride and distilled under reduced pressure, and AIBN was recrystallized in methanol. The purified product was used. In addition to the system in which no chain transfer agent was added, each of the five systems in which the chain transfer agent was arbitrarily changed by 5 points in the range of 0.05 to 1.50% by weight with respect to the weight of the charged methyl methacrylate, Before the polymerization, nitrogen was purged for 15 minutes under a nitrogen atmosphere, and then bulk polymerization of methyl methacrylate was carried out at 60 ° C. in the presence of each concentration of chain transfer agent and in the absence of the chain transfer agent. The polymerization was terminated by quenching before the polymerization rate reached 5%. By dissolving the content in acetone at a constant concentration, sampling an acetone solution of this known concentration, and measuring using a gas chromatograph (GC-14B, Shimadzu Corporation column: J & W capillary column DB-5), The residual concentration of chain transfer agent was determined. On the other hand, after adding a small amount of hydroquinone as a polymerization inhibitor to the acetone solution, it was reprecipitated with 20 times methanol, further washed twice with methanol, and then vacuum dried at 50 ° C. for 48 hours to obtain a polymer. For this polymer, the polymerization rate was confirmed by measuring the weight, and P _n and P _n0 were determined by performing gel permeation chromatography under the following conditions. That is, the polymer was dissolved in tetrahydrofuran for HPLC measurement at a concentration of 0.2% by weight, and gel permeation chromatograph (pump: model 515, manufactured by Waters, column: TSKgel GMHHR-H was used using tetrahydrofuran as a mobile phase. (30) and TSKgel Multipore HXL-M were directly connected, manufactured by Tosoh Corporation), and measurement was performed at 30 ° C. and a flow rate of 1 ml / min. The column temperature was 30 ° C., an ultraviolet detector was used as the detector, and eight monodispersed polymethyl methacrylate standard reagents having a molecular weight of 2400 to 1580000 were used for the calibration curve. Plot [S] / [M] on the horizontal axis and 1 / _Pn on the vertical axis to obtain the slope of the obtained straight line (C _x ). The chain transfer constant at 60 ° C. with respect to the chain transfer agent of methyl methacrylate monomer It was.

(4) Each component composition Each of the obtained original copolymer and thermoplastic polymer was dissolved in deuterated pyridine at a concentration of 600 mg / 3 g, and measured using a Varian Inc. unity INOVA500 NMR measuring machine. The core 13C was measured using TMS as a reference, the observation frequency was 125.7 MHz, the number of integration was 30000 times, the original copolymer was measured at a temperature of 25 ° C., and the thermoplastic polymer was measured at a temperature of 15 ° C. In the 13C-NMR spectrum of the thermoplastic polymer, (i) the peak of the carbonyl group of the acid anhydride of the glutaric anhydride-containing unit is observed split into a chemical shift range of 170.50 to 174.40 ppm, and (ii ) The peak of the carbonyl group of the unsaturated carboxylic acid ester unit is observed by splitting the chemical shift in the range of 174.60 to 179.43 ppm depending on the sequence and tacticity, and (iii) the carbonyl group of the unsaturated carboxylic acid unit. The peak of ## STR4 ## is observed by splitting the chemical shift in the range of 179.15 to 182.00 ppm depending on the sequence and tacticity, and (iii) the peak of the carbonyl group of the unsaturated carboxylic acid ester unit and (iii) the unsaturated carboxylic acid The peak of the carbonyl group of the acid unit is observed to partially overlap, but (ii In the portion where the peak of the carbonyl group of the unsaturated carboxylic acid ester unit and (iii) the peak of the carbonyl group of the unsaturated carboxylic acid unit overlap, the ratio of the peak of the carbonyl group of the unsaturated carboxylic acid ester unit is ( iii) The peak of the carbonyl group of the unsaturated carboxylic acid unit is negligibly small compared to the proportion occupied by the peak of the carbonyl group of the unsaturated carboxylic acid unit. Therefore, in the present invention, the peak of the carbonyl group of the unsaturated carboxylic acid ester unit has a chemical shift of 174.60. The range of ˜179.14 ppm, (iii) the peak of the carbonyl group of the unsaturated carboxylic acid unit was in the range of 179.15 to 182.00 ppm of chemical shift, and the respective compositions were determined from these integrated values. In the 13C-NMR of the original copolymer (A), (ii) the peak of the carbonyl group of the unsaturated carboxylic acid ester unit is split into a chemical shift range of 176.00 to 179.43 ppm depending on the sequence and tacticity. (Iii) The peak of the carbonyl group of the unsaturated carboxylic acid unit is observed by splitting the chemical shift in the range of 179.15 to 182.00 ppm by the sequence and tacticity, and (ii) the unsaturated carboxylic acid unit The peak of the carbonyl group of the acid ester unit and (iii) the peak of the carbonyl group of the unsaturated carboxylic acid unit partially overlap, but (iii) the peak of the carbonyl group of the unsaturated carboxylic acid ester unit and (iii) the unsaturated carboxylic acid In the part where the peak of the carbonyl group of the unit overlaps, (ii) Since the ratio of the peak of the carbonyl group of the acid ester unit is negligibly small compared to the ratio of the peak of the carbonyl group of the unsaturated carboxylic acid unit (iii), in the present invention, (ii) the unsaturated carboxylic acid ester The peak of the carbonyl group of the unit has a chemical shift in the range of 176.00 to 179.14 ppm, and the peak of the carbonyl group of the unsaturated carboxylic acid unit has a chemical shift in the range of 179.15 to 182.00 ppm. Each composition was determined from the integrated value. When the 13C-NMR spectrum of the original copolymer (A) and the thermoplastic polymer of the present invention was measured in deuterated pyridine, (i) content of glutaric anhydride-containing unit, (iii) Content of saturated carboxylic acid unit, (ii) type of unsaturated carboxylic acid ester unit used, (iii) type of unsaturated carboxylic acid unit used, difference in water content contained in deuterated pyridine solution, In the 13C-NMR spectrum of each of the original copolymer (A) and the thermoplastic polymer of the present invention due to the influence of a minute error derived from a measuring instrument for each measurement, (ii) of unsaturated carboxylic acid ester units The chemical shift of each peak top of the peak of the carbonyl group and (iii) the peak of the carbonyl group of the unsaturated carboxylic acid unit is observed within a range of about 0.2 ppm. Therefore, in this case, the composition was obtained in consideration of the shift (movement) of each chemical shift.

(5) Solubility Parameter The solubility parameter δ (MPa ^1/2 ) employed in the present invention is “POLYMER HANDBOOK FOURTH EDITION”, J. MoI. BRANDRUP, E.I. H. IMMERGUT, and E.I. A. Data described in TABLE 7 of GRULKE, VII / 675-714, WILEY INTERSCIENCE (1999) was adopted. Moreover, regarding the organic solvent not described in TABLE7, it was calculated and adopted by the method of Small described in the literature. Note that the Small method employs the cohesive energy constant F (MPa ^1/2 · cm ³ / mol) of specific atoms and atomic groups by the Small method given in TABLE 2 of the above-mentioned literature, and the density is s ( g / cm ³ ), the basic molecular weight is M (g / mol), and the solubility parameter δ (MPa ^1/2 ) is calculated by δ = (sΣF) / M. Note that 1 (MPa ^1/2 ) = 2.046 (cal / cm ³ ) ^1/2 .

  Further, the solubility parameter δ in the case of a mixture composed of two or more kinds of organic solvents is calculated by the following formula from the molar fraction Xi (%) of each solvent component in the mixed organic solvent and the solubility parameter δi of each solvent component. did. δ = Σ (δi × Xi / 100)

(6) Content of Volatile Content in Cake The original copolymer cake after the first filtration following the polymerization and the original copolymer cake after the second filtration were respectively placed in a vacuum dryer under reduced pressure (10 Torr), 130 Vacuum drying was carried out until the volatile components were completely distilled off at 0 ° C., the change in weight was measured, and the weight reduction rate calculated from the following formula was evaluated as the volatile content.
Volatile content (% by weight) = weight reduction rate (% by weight) in the original copolymer cake after the first filtration or in the original copolymer cake after the second filtration = [(weight before heat treatment− Weight after heat treatment) / weight before heat treatment] × 100.

(7) Yellowness (Yellowness Index (YI value))
Each of the pellet-like thermoplastic polymer and thermoplastic resin composition obtained in the examples or comparative examples was vacuum-dried at 80 ° C. for 8 hours, and then an injection molding machine (Miki Seisakusho M-50AII-SJ) was used. Then, injection molding was carried out with the molding temperature being the glass transition temperature of each of the thermoplastic polymer and the thermoplastic resin composition + 140 ° C. and the mold temperature being 80 ° C. to obtain a molded product having a thickness of 1 mm. The YI value of the obtained 1 mm-thick molded product was measured according to JIS-K7103 using an SM color computer (manufactured by Suga Test Instruments Co., Ltd.).

(8) Transparency (total light transmittance)
For each of the thermoplastic polymer and the thermoplastic resin composition, the total light transmittance (%) at 23 ° C. of a 1 mm-thick molded product obtained by the same operation as in the above (7) was directly read by Toyo Seiki Co., Ltd. It measured using the haze meter and evaluated transparency.

(9) Glass transition temperature (Tg)
Each of the thermoplastic polymer and the thermoplastic resin composition was measured using a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer) at a temperature increase rate of 20 ° C./min in a nitrogen atmosphere.

(10) Tensile strength, tensile elongation Each of the pellet-shaped thermoplastic polymer and thermoplastic resin composition obtained in Examples or Comparative Examples was vacuum-dried at 80 ° C. for 8 hours, and rotated in the same direction with a screw diameter of 25 mm. Using a twin screw extruder (HK-25D (41D) manufactured by Parker Corporation), a T-die having a slit gap of 0.5 mm (melting and kneading temperature is the glass transition temperature of each of the thermoplastic polymer and the thermoplastic resin composition used). The temperature of the take-up roll was cooled to 130 ° C., and a film having a thickness of 80 μm was formed. The thickness of the film was measured according to JISK7130. Next, the obtained film was punched into a JIS No. 3 dumbbell shape in the longitudinal direction of the film, and JIS K7127 was used at a tensile speed of 100 mm / min using a tensile tester (Tensilon UTM-100 manufactured by Toyo Baldwin (currently Orientec)). The tensile strength (tensile breaking strength) and tensile elongation (tensile breaking elongation) were measured according to the above. Measurement was performed on 10 samples, and an average value was used.

(11) Tensile strength retention after wet heat treatment The JIS No. 3 dumbbell-shaped film obtained in (10) above is subjected to wet heat treatment in a constant temperature and humidity chamber at 60 ° C. and 90% RH for 500 hours, and then the tensile rate. The tensile strength (tensile breaking strength) is measured at 100 mm / min according to JIS K7127, and the tensile strength retention rate (%) relative to the tensile strength (tensile breaking strength) before wet heat treatment is determined as a thermoplastic polymer or thermoplastic resin. Determined for each of the compositions. Tensile strength retention after wet heat treatment (%) = (Tensile rupture strength after wet heat treatment / Tensile rupture strength before wet heat treatment) × 100

(12) Polymerization yield: The raw copolymer slurry obtained by polymerizing the monomer mixture is subjected to reduced pressure (10 Torr) in a vacuum dryer from the raw copolymer cake obtained by solid-liquid separation. Thereafter, the heat treatment was carried out at 130 ° C. to completely remove volatile components, and the polymerization yield was calculated from the following formula. Here, the raw copolymer does not include those adhering to the stirring blade and / or the wall during polymerization. In the present invention, unless otherwise specified, vacuum drying refers to carrying out under a pressure of 10 Torr using a vacuum dryer (DP-32 manufactured by Yamato Scientific Co., Ltd.).
Polymerization yield (%) = [total weight of original copolymer obtained after heat treatment / total weight of charged monomer mixture] × 100

  (13) Slurry concentration: After completion of polymerization of the raw copolymer, the slurry containing the raw copolymer was sampled while uniformly stirring the system. The slurry was subjected to heat treatment in a vacuum dryer under reduced pressure (10 Torr) to completely remove volatile components, and the slurry concentration was calculated from the respective weights before and after the heat treatment. Slurry concentration (% by weight) = [(total weight of slurry before heat treatment−weight of raw copolymer after complete removal of volatile components from slurry) / total weight of slurry before heat treatment] × 100

  About the chain transfer agent used in the reference example, the chain transfer constants at 60 ° C. with respect to the chain transfer agent of methyl methacrylate monomer are summarized in Table 1.

Reference example 1
Polymerization step (first step): production of original copolymers (a-1) to (a-13) Reference example 1: original copolymer (a-1)
A mixed material of (a) below is supplied to a stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra-type stirring blade, dissolved while stirring at 250 rpm, and the system is filled with nitrogen gas at 10 L / min. Bubbled for 15 minutes. Next, nitrogen gas was flowed at a flow rate of 5 L / min, and the reaction system was heated to 90 ° C. while stirring. The following mixed substances (b) were sequentially added over 40 minutes and kept for another 100 minutes, and then the polymerization was terminated to obtain a slurry of the original copolymer (a-1). The polymerization yield was 80% and the slurry concentration was 17.8%. The charged monomer concentration was 22.2%. After cooling the slurry of the obtained original copolymer (a-1) to 40 ° C., qualitative filter paper No. 1 was subjected to suction filtration to obtain a cake of the original copolymer (a-1). The resulting cake fine particles are not scattered in the air, are not coalesced between particles, are not attached to the inner wall of the suction filter, have excellent dispersibility of the particles after filtration, and are excellent in handling properties. there were. Subsequently, it vacuum-dried at 130 degreeC for 12 hours, and obtained the powdery original copolymer (a-1). As a result of SEM observation, the obtained original copolymer (a-1) had a number average particle diameter of 3.8 μm. Mw was 72000, and molecular weight distribution (Mw / Mn) was 2.08. The copolymer composition of the original copolymer (a-1) is methyl methacrylate unit (MMA) / methacrylic acid unit (MAA) (weight% ratio) = 72/28. In the molecular weight distribution diagram, it is 4 times Mw. The content of a polymer having a molecular weight of 288000 or more, which is a value, is 1.6% by weight, and the content of a polymer having a molecular weight of 5000 or less (hereinafter sometimes referred to as a low molecular weight product) is 0.5 % By weight.
Mixed substance (I):
Methacrylic acid 25 parts by weight Methyl methacrylate 75 parts by weight Butyl acetate 190 parts by weight Cyclohexane 140 parts by weight 3-Mercaptopropionic acid 2-ethylhexyl 1.1 parts by weight Mixed substance (b):
Butyl acetate 20 parts by weight Lauroyl peroxide 0.8 parts by weight.

Reference Example 2: Original copolymer (a-2)
A mixed material of (a) below is supplied to a stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra-type stirring blade, dissolved while stirring at 250 rpm, and the system is filled with nitrogen gas at 10 L / min. Bubbled for 15 minutes. Next, nitrogen gas was flowed at a flow rate of 5 L / min, and the reaction system was heated to 90 ° C. while stirring. The following mixed substances (b) were sequentially added over 40 minutes, and after maintaining for another 100 minutes, the polymerization was terminated to obtain a slurry of the original copolymer (a-2). The polymerization yield was 74% and the slurry concentration was 14.8%. The charged monomer concentration was 20.0%. After cooling the obtained slurry of the original copolymer (a-2) to 40 ° C., it was centrifuged with a centrifuge “LAC-21” (product of Matsumoto Machine Sales Co., Ltd.) while flowing nitrogen gas, A cake of the original copolymer (a-2) was obtained. Subsequently, it vacuum-dried at 110 degreeC for 15 hours, and obtained the powdery original copolymer (a-2). The number average particle diameter of the obtained original copolymer (a-2) was 4.4 μm as a result of SEM observation. Mw was 130,000 and molecular weight distribution (Mw / Mn) was 2.45. The copolymer composition of the original copolymer (a-2) is MMA / MAA (weight% ratio) = 72/28, and in the molecular weight distribution diagram, a polymer having a molecular weight of 520000 or more, which is four times Mw. The content of the polymer having a molecular weight of 5000 or less was 0.5% by weight.
Mixed substance (I):
Methacrylic acid 25 parts by weight Methyl methacrylate 75 parts by weight butyl acetate 280 parts by weight Hexane 100 parts by weight n-butyl 3-mercaptopropionate 0.14 parts by weight Mixed substance (b):
Butyl acetate 20 parts by weight Lauroyl peroxide 0.8 parts by weight.

Reference Example 3: Original copolymer (a-3)
A mixed material of (a) below is supplied to a stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra-type stirring blade, dissolved while stirring at 250 rpm, and the system is filled with nitrogen gas at 10 L / min. Bubbled for 15 minutes. Next, nitrogen gas was flowed at a flow rate of 5 L / min, and the reaction system was heated to 90 ° C. while stirring. The following mixed substances (b) were sequentially added over 40 minutes, and after maintaining for another 100 minutes, the polymerization was terminated to obtain a slurry of the original copolymer (a-3). The polymerization yield was 80% and the slurry concentration was 17.8%. The charged monomer concentration was 22.2%. After cooling the slurry of the obtained original copolymer (a-3) to 30 ° C., it was centrifuged with a centrifuge “LAC-21” (product of Matsumoto Machine Sales Co., Ltd.) while flowing nitrogen gas, A cake of the original copolymer (a-3) was obtained. Subsequently, it vacuum-dried at 110 degreeC for 15 hours, and obtained the powdery original copolymer (a-3). As a result of SEM observation, the obtained original copolymer (a-3) had a number average particle size of 3.4 μm. Mw was 70000, and molecular weight distribution (Mw / Mn) was 2.04. The copolymer composition of the original copolymer (a-3) is MMA / MAA (weight% ratio) = 77/23, and the polymer having a molecular weight of 280000 or more, which is 4 times Mw in the molecular weight distribution diagram The content of the polymer having a molecular weight of 5000 or less was 0.5% by weight.
Mixed substance (I):
Methacrylic acid 19 parts by weight Methyl methacrylate 81 parts by weight Butyl acetate 155 parts by weight Cyclohexane 175 parts by weight 3-Mercaptopropionic acid 2-ethylhexyl 1.1 parts by weight Mixed substance (b):
Butyl acetate 20 parts by weight Lauroyl peroxide 0.8 parts by weight.

Reference Example 4: Original copolymer (a-4)
A mixed material of (a) below is supplied to a stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra-type stirring blade, dissolved while stirring at 250 rpm, and the system is filled with nitrogen gas at 10 L / min. Bubbled for 15 minutes. Next, nitrogen gas was flowed at a flow rate of 5 L / min, and the reaction system was heated to 95 ° C. while stirring. The following mixed substances (b) were sequentially added over 90 minutes, and after maintaining for another 60 minutes, the polymerization was terminated. Here, the charged monomer concentration was 16.7%. The obtained slurry was cooled to 40 ° C., and then treated with a centrifuge “LAC-21” (product of Matsumoto Machine Sales Co., Ltd.) for 2 hours while flowing nitrogen gas to separate the organic solvent. It vacuum-dried at 130 degreeC for 15 hours, and obtained the powdery original copolymer (a-4). The polymerization yield of this original copolymer (a-4) was 77%, and the slurry concentration was 12.9%. As a result of SEM observation, the obtained original copolymer (a-4) had a number average particle diameter of 5.0 μm. Mw was 100,000, and molecular weight distribution (Mw / Mn) was 2.38. The copolymer composition of the original copolymer (a-4) for the comparative example is MMA / MAA (weight% ratio) = 72/28, and in the molecular weight distribution diagram, the molecular weight is 400000 or more, which is four times Mw. The content of the polymer having 1.9 was 1.9% by weight, and the content of the polymer having a molecular weight of 5000 or less was 0.5% by weight.
Mixed substance (I):
Methacrylic acid 11 parts by weight Methyl methacrylate 39 parts by weight Butyl acetate 355 parts by weight Heptane 125 parts by weight 3-Mercaptopropionic acid n-butyl 0.3 part by weight Mixed substance (b):
Methacrylic acid 11 parts by weight Methyl methacrylate 39 parts by weight Butyl acetate 20 parts by weight 2,2′-Azobis-2,4-dimethylvaleronitrile 0.5 part by weight.

Reference Example 5: Original copolymer (a-5)
A mixed material of (a) below is supplied to a stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra-type stirring blade, dissolved while stirring at 250 rpm, and the system is filled with nitrogen gas at 10 L / min. Bubbled for 15 minutes. Next, nitrogen gas was flowed at a flow rate of 5 L / min, and the reaction system was heated to 90 ° C. while stirring. The following mixed substances (b) were sequentially added over 40 minutes, and after maintaining for another 100 minutes, the polymerization was terminated to obtain a slurry of the original copolymer (a-5). The polymerization yield was 86% and the slurry concentration was 23.2%. The charged monomer concentration was 27.0%. After cooling the slurry of the obtained original copolymer (a-5) to 40 ° C., it was centrifuged with a centrifuge “LAC-21” (product of Matsumoto Machine Sales Co., Ltd.) while flowing nitrogen gas, The cake fine particles obtained do not scatter in the air, adhere to each other, do not adhere to the inner wall of the suction filter, have excellent dispersibility of the particles after filtration, and have excellent handling properties. It was. Subsequently, it vacuum-dried at 110 degreeC for 15 hours, and obtained the powdery original copolymer (a-5). As a result of SEM observation, the obtained original copolymer (a-5) had a number average particle diameter of 3.4 μm. Mw was 100,000, and molecular weight distribution (Mw / Mn) was 2.15. The copolymer composition of the original copolymer (a-5) is MMA / MAA (weight% ratio) = 83/17, and in the molecular weight distribution diagram, a polymer having a molecular weight of 400,000 or more, which is four times Mw. The content of the polymer having a molecular weight of 5000 or less was 0.5% by weight.
Mixed substance (I):
Methacrylic acid 14 parts by weight Methyl methacrylate 86 parts by weight Butyl acetate 93 parts by weight Cyclohexane 162 parts by weight 2-Mercaptopropionic acid 2-ethylhexyl 0.7 parts by weight Mixed substance (b):
Butyl acetate 15 parts by weight Lauroyl peroxide 0.8 parts by weight.

Reference Example 6: Raw copolymer (a-6)
A mixed material of (a) below is supplied to a stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra-type stirring blade, dissolved while stirring at 250 rpm, and the system is filled with nitrogen gas at 10 L / min. Bubbled for 15 minutes. Next, nitrogen gas was flowed at a flow rate of 5 L / min, and the reaction system was heated to 95 ° C. while stirring. The following mixed substances (b) were sequentially added over 90 minutes, and after maintaining for another 60 minutes, the polymerization was terminated. Here, the charged monomer concentration was 16.7%. The obtained slurry was cooled to 40 ° C., and then treated with a centrifuge “LAC-21” (product of Matsumoto Machine Sales Co., Ltd.) for 2 hours while flowing nitrogen gas to separate the organic solvent. It vacuum-dried at 130 degreeC for 15 hours, and obtained the powdery original copolymer (a-6). The polymerization yield of this original copolymer (a-6) was 75%, and the slurry concentration was 12.5%. As a result of SEM observation, the obtained original copolymer (a-6) had a number average particle diameter of 5.0 μm. Mw was 95000 and molecular weight distribution (Mw / Mn) was 2.51. The copolymer composition of the original copolymer (a-6) is MMA / MAA (weight% ratio) = 72/28, and the polymer having a molecular weight of 380000 or more which is a value four times Mw in the molecular weight distribution diagram The content of the polymer having a molecular weight of 5000 or less was 0.8% by weight.
Mixed substance (I):
Methacrylic acid 11 parts by weight Methyl methacrylate 39 parts by weight Butyl acetate 355 parts by weight Heptane 125 parts by weight 3-Mercaptopropionic acid n-octyl 0.4 parts by weight Mixed substance (b):
Methacrylic acid 11 parts by weight Methyl methacrylate 39 parts by weight Butyl acetate 20 parts by weight 2,2′-Azobis-2,4-dimethylvaleronitrile 0.5 part by weight.

Reference Example 7: Raw copolymer (a-7)
A mixed material of (a) below is supplied to a stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra-type stirring blade, dissolved while stirring at 250 rpm, and the system is filled with nitrogen gas at 10 L / min. Bubbled for 15 minutes. Next, nitrogen gas was flowed at a flow rate of 5 L / min, and the reaction system was heated to 90 ° C. while stirring. The following mixed substances (b) were sequentially added over 40 minutes, and after maintaining for another 100 minutes, the polymerization was terminated to obtain a slurry of the original copolymer (a-7). The polymerization yield was 80% and the slurry concentration was 17.8%. The charged monomer concentration was 22.2%. After cooling the slurry of the obtained original copolymer (a-7) to 30 ° C., it was centrifuged with a centrifuge “LAC-21” (product of Matsumoto Machine Sales Co., Ltd.) while flowing nitrogen gas. A cake of the original copolymer (a-7) was obtained. Subsequently, it vacuum-dried at 110 degreeC for 15 hours, and obtained the powdery original copolymer (a-7). As a result of SEM observation, the obtained original copolymer (a-7) had a number average particle diameter of 2.8 μm. Mw was 70000, and molecular weight distribution (Mw / Mn) was 2.02. The copolymer composition of the original copolymer (a-7) is MMA / MAA (weight% ratio) = 77/23, and the polymer having a molecular weight of 280000 or more, which is 4 times Mw in the molecular weight distribution diagram. The content of the polymer having a molecular weight of 5000 or less was 0.4% by weight.
Mixed substance (I):
Methacrylic acid 19 parts by weight Methyl methacrylate 81 parts by weight Butyl acetate 85 parts by weight Cyclohexane 245 parts by weight 3-Mercaptopropionic acid 2-ethylhexyl 0.8 parts by weight Mixed substance (b):
Butyl acetate 20 parts by weight Lauroyl peroxide 0.8 parts by weight.

Reference Example 8: Raw copolymer (a-8)
A mixed material of (a) below is supplied to a stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra-type stirring blade, dissolved while stirring at 250 rpm, and the system is filled with nitrogen gas at 10 L / min. Bubbled for 15 minutes. Next, nitrogen gas was flowed at a flow rate of 5 L / min, and the reaction system was heated to 85 ° C. while stirring. The following mixed substances (b) were sequentially added in 70 minutes, and further maintained at 85 ° C. for 120 minutes. Then, the polymerization was terminated to obtain a slurry of the original copolymer (a-8). The polymerization yield was 79% and the slurry concentration was 13.9%. The charged monomer concentration was 17.5%. After cooling the slurry of the obtained original copolymer (a-8) to 40 ° C., it was centrifuged with a centrifuge “LAC-21” (product of Matsumoto Machine Sales Co., Ltd.) while flowing nitrogen gas. The cake fine particles obtained do not scatter in the air, adhere to each other, do not adhere to the inner wall of the suction filter, have excellent dispersibility of the particles after filtration, and have excellent handling properties. It was. Subsequently, it vacuum-dried at 130 degreeC for 15 hours, and obtained the powdery original copolymer (a-8). As a result of SEM observation, the obtained original copolymer (a-8) had a number average particle diameter of 2.4 μm. Mw was 100,000, and molecular weight distribution (Mw / Mn) was 2.00. The copolymer composition of the original copolymer (a-8) is MMA / MAA (weight% ratio) = 76/24, and in the molecular weight distribution diagram, a polymer having a molecular weight of 400,000 or more, which is four times Mw. The content of the polymer having a molecular weight of 5000 or less was 0.3% by weight.
Mixed substance (I):
Methacrylic acid 19 parts by weight Methyl methacrylate 81 parts by weight Butyl acetate 47 parts by weight Cyclohexane 403 parts by weight 3-Mercaptopropionic acid 2-ethylhexyl 0.44 parts by weight Mixed substance (b):
Cyclohexane 20 parts by weight Lauroyl peroxide 0.8 parts by weight.

Reference Example 9: Raw copolymer (a-9)
A mixed material of (a) below is supplied to a stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra-type stirring blade, dissolved while stirring at 250 rpm, and the system is filled with nitrogen gas at 10 L / min. Bubbled for 15 minutes. Next, nitrogen gas was flowed at a flow rate of 5 L / min, and the reaction system was heated to 90 ° C. while stirring. The following mixed substances (b) were sequentially added over 40 minutes, and after maintaining for another 100 minutes, the polymerization was terminated to obtain a slurry of the original copolymer (a-9). The polymerization yield was 79% and the slurry concentration was 17.5%. The charged monomer concentration was 22.2%. After cooling the slurry of the obtained original copolymer (a-9) to 40 ° C., qualitative filter paper No. 1 was subjected to suction filtration to obtain a cake of the original copolymer (a-9). The resulting cake fine particles are not scattered in the air, are not coalesced between particles, are not attached to the inner wall of the suction filter, have excellent dispersibility of the particles after filtration, and are excellent in handling properties. there were. Subsequently, it vacuum-dried at 130 degreeC for 12 hours, and obtained the powdery original copolymer (a-9). As a result of SEM observation, the obtained original copolymer (a-9) had a number average particle diameter of 3.9 μm. Mw was 70000, and molecular weight distribution (Mw / Mn) was 1.95. The copolymer composition of the original copolymer (a-9) is methyl methacrylate unit (MMA) / methacrylic acid unit (MAA) (weight% ratio) = 72/28. The content of the polymer having a molecular weight of 280000 or more, which is the value, was 1.3% by weight, and the content of the polymer having a molecular weight of 5000 or less was 0.4% by weight.
Mixed substance (I):
Methacrylic acid 25 parts by weight Methyl methacrylate 75 parts by weight Butyl acetate 190 parts by weight Cyclohexane 140 parts by weight 2-Naphthalenethiol 0.5 parts by weight Mixed substance (b):
Butyl acetate 20 parts by weight Lauroyl peroxide 0.8 parts by weight.

Reference Example 10: Original copolymer (a-10)
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 85 ° C. while stirring. When the internal temperature reached 85 ° C., the polymerization was started. The internal temperature was maintained at 85 ° C. for 90 minutes, heated to 90 ° C. over 30 minutes, and then maintained for another 90 minutes to complete the polymerization. The reaction system was cooled to room temperature to obtain a polymer solution having no insoluble precipitate. The powder obtained by dropping the polymer solution into a large amount of ion-exchanged water is vacuum-dried at 130 ° C. for 30 hours to completely remove ethylene glycol monoethyl ether as a polymerization solvent, and the original copolymer (a-10) Got. The polymerization yield of the obtained original copolymer (a-10) was 80%, the weight average molecular weight was 65000, and the molecular weight distribution (Mw / Mn) was 2.22. The copolymer composition of the original copolymer (a-10) is MMA / MAA (weight% ratio) = 72/28, and in the molecular weight distribution diagram, a polymer having a molecular weight of 260000 or more, which is a value four times Mw. The content of the polymer having a molecular weight of 5000 or less was 0.7% by weight.
Methacrylic acid 27 parts by weight Methyl methacrylate 73 parts by weight Ethylene glycol monoethyl ether 150 parts by weight 3-mercaptopropionic acid n-butyl 0.14 parts by weight 2,2′-azobis-2,4-dimethylvaleronitrile 0.3 weights Department.

Reference Example 11: Original copolymer (a-11)
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 85 ° C. while stirring. When the internal temperature reached 85 ° C., the polymerization was started. The internal temperature was maintained at 85 ° C. for 90 minutes, heated to 90 ° C. over 30 minutes, and then maintained for another 90 minutes to complete the polymerization. The reaction system was cooled to room temperature to obtain a polymer solution having no insoluble precipitate. The powder obtained by dropping the polymer solution into a large amount of ion-exchanged water is vacuum-dried at 130 ° C. for 30 hours to completely remove ethylene glycol monoethyl ether as a polymerization solvent, and the original copolymer (a-11) Got. The polymerization yield of the obtained original copolymer (a-11) was 80%, the weight average molecular weight was 65000, and the molecular weight distribution (Mw / Mn) was 2.12. The copolymer composition of the original copolymer (a-11) is MMA / MAA (weight% ratio) = 72/28, and in the molecular weight distribution diagram, a polymer having a molecular weight of 260000 or more, which is a value four times Mw. The content of the polymer having a molecular weight of 5000 or less was 0.4% by weight.
Methacrylic acid 27 parts by weight Methyl methacrylate 73 parts by weight Ethylene glycol monoethyl ether 150 parts by weight 2-naphthalenethiol 0.07 parts by weight 2,2′-azobis-2,4-dimethylvaleronitrile 0.3 parts by weight

Reference Example 12: Raw copolymer (a-12)
Into a stainless steel autoclave with a capacity of 5 liters and equipped with a baffle and a foudra-type stirring blade, a methyl methacrylate / acrylamide copolymer suspension (prepared by the following method: 20 parts by weight of methyl methacrylate, 80 parts by weight of acrylamide) Then, 0.3 parts by weight of potassium persulfate and 1500 parts by weight of ion-exchanged water are charged into the reactor, and the reactor is maintained at 70 ° C. while being replaced with nitrogen gas. The solution is obtained as an aqueous solution of methyl methacrylate and acrylamide copolymer until the conversion is completed (the obtained aqueous solution was used as a suspending agent). The mixture was stirred and the system was replaced with nitrogen gas. Next, the following mixed substances were added while stirring the reaction system, and the temperature was raised to 70 ° C. The time when the internal temperature reached 70 ° C. was set as the start of polymerization, and kept for 180 minutes to complete the polymerization. Thereafter, the reaction system was cooled, the polymer was separated, washed, and dried in accordance with a usual post-treatment method in suspension polymerization to obtain a bead-shaped raw copolymer (a-12). The polymerization yield of this original copolymer (a-12) was 98%, the weight average molecular weight was 90000, and the molecular weight distribution was 1.65. The copolymer composition of the original copolymer (a-12) is MMA / MAA (weight% ratio) = 72/28, and in the molecular weight distribution diagram, a polymer having a molecular weight of 360000 or more, which is four times Mw. The content of the polymer having a molecular weight of 5000 or less was 0.1% by weight.
Methacrylic acid 27 parts by weight Methyl methacrylate 73 parts by weight 3-Mercaptopropionic acid 2-ethylhexyl 0.5 part by weight 2,2′-azobisisobutyronitrile 0.4 part by weight.

Reference Example 13: Raw copolymer (a-13)
The following mixed substances were added to a stainless steel autoclave having a capacity of 5 liters and equipped with a baffle and a foudra-type stirring blade while stirring the reaction system, and the temperature was raised to 90 ° C. The time when the internal temperature reached 90 ° C. was set as the start of polymerization, and kept for 90 minutes. The polymerization yield of the original copolymer (a-13) at this time was 60%, and this monomer solution was extracted from the lower extraction port of the autoclave and reprecipitated and filtered with 10 times equivalent of heptane. Subsequently, it vacuum-dried at 120 degreeC for 24 hours, and obtained the original copolymer (a-13). The weight average molecular weight was 60000, and the molecular weight distribution was 1.69. The copolymer composition of the original copolymer (a-13) is MMA / MAA (weight% ratio) = 72/28, and in the molecular weight distribution diagram, a polymer having a molecular weight of 240,000 or more, which is four times Mw. The content of the polymer having a molecular weight of 5000 or less was 0.1% by weight.
Methacrylic acid 26 parts by weight Methyl methacrylate 74 parts by weight 3-Mercaptopropionic acid 2-ethylhexyl 0.7 parts by weight Lauroyl peroxide 0.05 parts by weight.

Production of Original Copolymers (a-14) to (a-18) for Comparative Example Reference Example 14: Original Copolymer (a-14) for Comparative Example
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 85 ° C. while stirring. The time when the internal temperature reached 85 ° C was set as the polymerization start, the internal temperature was maintained at 85 ° C for 60 minutes, the temperature was raised to 95 ° C over 30 minutes, and then maintained at 95 ° C for 30 minutes to complete the polymerization. An example raw copolymer (a-14) was obtained. The polymerization yield was 62%. The charged monomer concentration was 10.0%. The resulting slurry of the original copolymer (a-14) for Comparative Example was cooled to 40 ° C. 1 was subjected to suction filtration and vacuum dried at 130 ° C. for 12 hours to obtain a powdery original copolymer (a-14) for a comparative example. As a result of observing the obtained original copolymer for comparison (a-14) with SEM, the number average particle diameter was 5.5 μm. Moreover, Mw by GPC measurement was 140000, and molecular weight distribution (Mw / Mn) was 3.32. The copolymer composition of the original copolymer (a-14) for the comparative example is MMA / MAA (weight% ratio) = 72/28, and in the molecular weight distribution chart, the molecular weight is 560000 or more which is a value four times Mw. The content of the polymer having a molecular weight of 4.2% was 4.2% by weight, and the content of the polymer having a molecular weight of 5000 or less was 1.6% by weight.
Methacrylic acid 25 parts by weight Methyl methacrylate 75 parts by weight Butyl acetate 675 parts by weight n-Heptane 225 parts by weight Laurol peroxide 0.8 parts by weight n-dodecyl mercaptan 0.2 parts by weight

Reference Example 15: Original copolymer for comparison (a-15)
A mixed material of (a) below is supplied to a stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra-type stirring blade, dissolved while stirring at 250 rpm, and the system is filled with nitrogen gas at 10 L / min. Bubbled for 15 minutes. Next, nitrogen gas was flowed at a flow rate of 5 L / min, and the reaction system was heated to 95 ° C. while stirring. The following mixed substances (b) were sequentially added over 90 minutes, and after maintaining for another 60 minutes, the polymerization was terminated. Here, the charged monomer concentration was 16.7%. The obtained slurry was cooled to 40 ° C., and then treated with a centrifuge “LAC-21” (product of Matsumoto Machine Sales Co., Ltd.) for 2 hours while flowing nitrogen gas to separate the organic solvent. It vacuum-dried at 130 degreeC for 15 hours, and obtained the raw copolymer (a-15) for powdery comparative examples. The polymerization yield of the original copolymer (a-15) for this comparative example was 77%. As a result of SEM observation, the obtained raw copolymer for comparative example (a-15) had a number average particle diameter of 5.0 μm. Mw was 100,000, and molecular weight distribution (Mw / Mn) was 3.08. The copolymer composition of the original copolymer (a-15) for Comparative Example is MMA / MAA (weight% ratio) = 72/28, and in the molecular weight distribution diagram, the molecular weight is 400000 or more, which is 4 times the value of Mw. The content of the polymer having 4.9 was 4.9% by weight, and the content of the polymer having a molecular weight of 5000 or less was 2.0% by weight.
Mixed substance (I):
Methacrylic acid 11 parts by weight Methyl methacrylate 39 parts by weight Butyl acetate 355 parts by weight Heptane 125 parts by weight n-Butyl mercaptan 0.5 parts by weight Mixed substance (b):
Methacrylic acid 11 parts by weight Methyl methacrylate 39 parts by weight Butyl acetate 20 parts by weight 2,2′-Azobis-2,4-dimethylvaleronitrile 0.5 part by weight.

Reference Example 16: Original copolymer for comparison (a-16)
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 85 ° C. while stirring. When the internal temperature reached 85 ° C., the polymerization was started. The internal temperature was maintained at 85 ° C. for 90 minutes, heated to 90 ° C. over 30 minutes, and then maintained for another 90 minutes to complete the polymerization. The reaction system was cooled to room temperature to obtain a polymer solution having no insoluble precipitate. The powder obtained by dropping the polymer solution into a large amount of ion-exchanged water was vacuum-dried at 130 ° C. for 24 hours to obtain an original copolymer (a-16) for a comparative example. The polymerization yield of the obtained original copolymer (a-16) for Comparative Example was 80%, the weight average molecular weight was 65000, and the molecular weight distribution (Mw / Mn) was 3.11. The copolymer composition of the original copolymer (a-16) for Comparative Example is MMA / MAA (weight% ratio) = 72/28, and in the molecular weight distribution diagram, a molecular weight of 260,000 or more, which is 4 times the value of Mw. The content of the polymer having a molecular weight of 4.0 was 4.0% by weight, and the content of the polymer having a molecular weight of 5000 or less was 2.1% by weight.
Methacrylic acid 27 parts by weight Methyl methacrylate 73 parts by weight Ethylene glycol monoethyl ether 150 parts by weight n-butyl mercaptan 0.2 parts by weight 2,2′-azobis-2,4-dimethylvaleronitrile 0.3 parts by weight

Reference Example 17: Original copolymer for comparison (a-17)
Into a stainless steel autoclave with a capacity of 5 liters and equipped with a baffle and a foudra-type stirring blade, a methyl methacrylate / acrylamide copolymer suspension (prepared by the following method: 20 parts by weight of methyl methacrylate, 80 parts by weight of acrylamide) Then, 0.3 parts by weight of potassium persulfate and 1500 parts by weight of ion-exchanged water are charged into the reactor, and the reactor is maintained at 70 ° C. while being replaced with nitrogen gas. The solution is obtained as an aqueous solution of methyl methacrylate and acrylamide copolymer until the conversion is completed (the obtained aqueous solution was used as a suspending agent). The mixture was stirred and the system was replaced with nitrogen gas. Next, the following mixed substances were added while stirring the reaction system, and the temperature was raised to 70 ° C. The time when the internal temperature reached 70 ° C. was set as the start of polymerization, and kept for 180 minutes to complete the polymerization. Thereafter, the reaction system was cooled, the polymer was separated, washed, and dried in accordance with ordinary methods to obtain a bead-shaped original copolymer (a-17) for comparative example. The polymerization yield of this comparative copolymer (a-17) was 98%, the weight average molecular weight was 90000, and the molecular weight distribution was 1.79. The copolymer composition of the original copolymer (a-17) for Comparative Example is MMA / MAA (weight% ratio) = 72/28, and in the molecular weight distribution diagram, a molecular weight of 360000 or more, which is 4 times the value of Mw. The content of a polymer having a molecular weight of 3.6 was 3.6% by weight, and the content of a polymer having a molecular weight of 5000 or less was 0.2% by weight.
Methacrylic acid 27 parts by weight Methyl methacrylate 73 parts by weight n-dodecyl mercaptan 0.8 part by weight 2,2′-azobisisobutyronitrile 0.4 part by weight.

Reference Example 18: Original copolymer for comparison (a-18)
A mixed material of (a) below is supplied to a stainless steel autoclave having a capacity of 20 liters and equipped with a baffle and a foudra-type stirring blade, dissolved while stirring at 250 rpm, and the system is filled with nitrogen gas at 10 L / min. Bubbled for 15 minutes. Next, nitrogen gas was flowed at a flow rate of 5 L / min, and the reaction system was heated to 95 ° C. while stirring. The following mixed substances (b) were sequentially added over 90 minutes, and after maintaining for another 60 minutes, the polymerization was terminated. Here, the charged monomer concentration was 16.7%. The obtained slurry was cooled to 40 ° C., and then treated with a centrifuge “LAC-21” (product of Matsumoto Machine Sales Co., Ltd.) for 2 hours while flowing nitrogen gas to separate the organic solvent. It vacuum-dried at 130 degreeC for 15 hours, and obtained the powdery original copolymer (a-18). The polymerization yield of this original copolymer (a-18) was 72%, and the slurry concentration was 12.0%. As a result of SEM observation, the obtained original copolymer (a-18) had a number average particle diameter of 5.0 μm. Mw was 100,000, and molecular weight distribution (Mw / Mn) was 2.92. The copolymer composition of the original copolymer (a-18) is MMA / MAA (weight% ratio) = 72/28, and in the molecular weight distribution diagram, a polymer having a molecular weight of 400000 or more, which is 4 times Mw. The content of the polymer having a molecular weight of 5000 or less was 1.6% by weight.
Mixed substance (I):
Methacrylic acid 11 parts by weight Methyl methacrylate 39 parts by weight Butyl acetate 355 parts by weight Heptane 125 parts by weight n-pentyl mercaptan 0.45 parts by weight Mixed substance (b):
Methacrylic acid 11 parts by weight Methyl methacrylate 39 parts by weight Butyl acetate 20 parts by weight 2,2′-Azobis-2,4-dimethylvaleronitrile 0.5 part by weight.

  Table 2 summarizes the copolymerization results of Reference Examples 1 to 18. In Table 2, the content of a polymer having a molecular weight 4 times or more of the value of Mw is shown as the content (% by weight) of a high molecular weight, and the content of a polymer having a molecular weight of 5000 or less The content (% by weight) is shown.

  From Table 2, from the comparison of Reference Examples 1 to 13 for Examples and Reference Examples 14 to 18 for Comparative Examples, a chain transfer agent containing a mercaptocarboxylic acid ester and / or an aromatic thiol was used during copolymerization. In the raw copolymers (A) of Reference Examples 1 to 13, the content of the polymer (high molecular weight) having a molecular weight 4 times or more the value of the weight average molecular weight is controlled to 3.0% by weight or less. I understand. Further, from the comparison of Reference Examples 1 to 8 and Reference Examples 14, 15 and 18 for Comparative Examples, particularly in precipitation polymerization, when a mercaptocarboxylic acid ester was used as a chain transfer agent, compared with a case where an alkyl mercaptan was used. Thus, it was found that both the content of the high molecular weight substance and the content of the low molecular weight substance are greatly reduced. Among them, the alkyl mercaptan used in Reference Example 18 for Comparative Example has a larger chain transfer constant value than the mercaptocarboxylic acid ester used in Reference Examples 1 to 8, but when used for copolymerization of the original copolymer, It was found that the content of the high molecular weight material and the content of the low molecular weight material of the original copolymer of Reference Example 18 for Comparative Example were larger than the ratio of the original copolymer (A) of Reference Examples 1 to 8.

  In addition, when compared between those polymerized by the same polymerization method, mercaptocarboxylic acid esters and / or aromatic thiols are not included by using a chain transfer agent containing mercaptocarboxylic acid esters and / or aromatic thiols. It can be seen that the molecular weight can be adjusted (adjusted on the low molecular weight side) by adding a small amount (compared by the number of moles added), and the molecular weight distribution can be narrowed more than when a chain transfer agent is used. Conventionally, polymers obtained by precipitation polymerization and solution polymerization tend to contain a relatively large amount of polymers having a molecular weight of 5000 or less compared to polymers obtained by suspension polymerization or bulk polymerization. Although it was necessary to carry out washing with a solvent and reduce the polymer content, a chain transfer agent containing a mercaptocarboxylic acid ester and / or an aromatic thiol, more preferably a chain transfer containing a mercaptocarboxylic acid ester It can be seen that the content of the polymer having a molecular weight of 5000 or less in the polymer obtained by precipitation polymerization or solution polymerization can be reduced by using an agent even without washing.

Washing step Reference Example 19: Original copolymer (B) (b-1)
The slurry of the original copolymer (a-1) obtained in Reference Example 1 was subjected to solid-liquid separation at 40 ° C. with a pressure filter (manufactured by Mitsubishi Chemical Corporation), and the raw copolymer (a-1) Got a cake. The obtained cake was dried at 130 ° C. for 12 hours in a vacuum dryer, and the volatile content was determined. As a result, it was 75% by weight. Subsequently, after the inside of the stainless steel washing tank provided with the baffle and the fowler type stirring blade is made a nitrogen atmosphere, the cake obtained after the solid-liquid separation is supplied into the washing tank, and 400 parts by weight with respect to 100 parts by weight of the cake. Part by weight of ion-exchanged water was added, and the system was bubbled with nitrogen gas at 10 L / min for 30 minutes while stirring at 25 ° C. and a rotational speed of 250 rpm. Next, while the mixture is continuously stirred at 250 rpm, the temperature is raised to 80 ° C. over 60 minutes while flowing nitrogen gas at a flow rate of 5 L / min, and 90 minutes from the time when the internal temperature reaches 80 ° C. A washing operation was performed. Subsequently, the obtained slurry was cooled to 40 ° C. and then supplied to a centrifuge “LAC-21” (manufactured by Matsumoto Machine Sales Co., Ltd.), and centrifuged at a rotational speed of 1000 rpm and 30 ° C. . The obtained raw copolymer (b-1) cake has a volatile content of 50% by weight, and further dried at 130 ° C. for 12 hours to completely distill off the volatile matter, thereby forming a particulate raw copolymer. The union (b-1) was obtained. The number average particle diameter calculated by observing at 150 times with SEM and analyzing the image of the particle diameter was 250 μm. Moreover, Mw by GPC measurement was 73000, and molecular weight distribution (Mw / Mn) was 1.92. The copolymer composition of the original copolymer (b-1) was MMA / MAA (weight% ratio) = 72/28. In the molecular weight distribution diagram, the content of a polymer having a molecular weight of 292,000 or more, which is 4 times Mw, is 1.6% by weight, and the content of a polymer having a molecular weight of 5000 or less is 0.3% by weight. Met.

Reference Example 20: raw copolymer for comparative example (b-2)
The slurry of the original copolymer (a-14) for Comparative Example obtained in Reference Example 14 was subjected to solid-liquid separation (first filtration) at 40 ° C. with a pressure filter (manufactured by Mitsubishi Chemical Corporation), and compared. A cake of the original copolymer (a-14) was obtained. The obtained cake was dried in a vacuum dryer at 130 ° C. for 12 hours, and the volatile content was determined to be 78% by weight. Subsequently, the obtained cake was supplied to a stainless steel washing tank equipped with a baffle and a foudra-type stirring blade, and 400 parts by weight of ion-exchanged water was added to 100 parts by weight of the cake. Stirring was started at. While continuously stirring this mixture at 250 rpm, the temperature was raised to 80 ° C. over 60 minutes, and a washing operation was performed for 90 minutes from the time when the internal temperature reached 80 ° C. Then, after cooling the slurry of the obtained copolymer (b-2) for comparative examples to 40 degreeC, it supplies to centrifuge "LAC-21" (Matsumoto machine sales Co., Ltd. product). Centrifugation was performed at a rotation speed of 1000 rpm and 30 ° C. The volatile content of the obtained original copolymer (b-2) cake for Comparative Example was 57% by weight. This cake was further dried under vacuum at 130 ° C. for 12 hours. As a result, 2.2 wt% of butyl acetate remained, and further vacuum dried at 130 ° C. for 12 hours. A copolymer (b-2) was obtained. The number average particle size calculated by observing with a SEM at 150 times and analyzing the particle size by image analysis was 650 μm. Moreover, Mw by GPC measurement was 141000, and molecular weight distribution (Mw / Mn) was 3.25. The copolymer composition of the original copolymer for comparison (b-2) was MMA / MAA (weight% ratio) = 72/28. In the molecular weight distribution diagram, the content of the polymer having a molecular weight of 564,000 or more, which is 4 times the value of Mw, is 4.2% by weight, and the content of the polymer having a molecular weight of 5000 or less is 0.6% by weight. Met.

  Table 3 shows a summary of the cleaning results of Reference Example 19 for Examples and Reference Example 20 for Comparative Examples. In Table 3, the content of a polymer having a molecular weight 4 times or more of Mw is shown as the content of a high molecular weight product, and the content of a polymer having a molecular weight of 5000 or less is shown as the content of a low molecular weight product. .

  From Table 3, it can be seen from Reference Example 19 and Reference Example 20 for Comparative Example that the particle diameter is controlled to a specific range that is easy to handle after washing in water. By performing the washing, it is possible to reduce the content of low molecular weight substances having a molecular weight of 5000 or less, but it is found that there is no effect in reducing the content of high molecular weight substances. In addition, since the raw copolymer of Reference Example 20 for Comparative Example does not use a chain transfer agent containing mercaptocarboxylic acid ester and / or aromatic thiol as a chain transfer agent, washing is performed after precipitation polymerization. Moreover, it turns out that the low molecular weight body is included rather than the original copolymer of the reference examples 1-5 for the Example of Table 2 which has not implemented washing | cleaning after precipitation polymerization, and the reference examples 7-9.

Reference Example 21: Production of rubber-containing polymer (c-1) 120 parts by weight of ion-exchanged water, 0.5 parts by weight of potassium carbonate, 0.5% dioctyl sulfosuccinate in a glass container (capacity 5 liters) with a cooler Part by weight and 0.005 part by weight of potassium persulfate were charged, and after stirring in a nitrogen atmosphere, 51 parts by weight of butyl acrylate, 19 parts by weight of styrene and 1 part by weight of allyl methacrylate (crosslinking agent) were charged. These mixtures were reacted at 70 ° C. for 30 minutes to obtain a core layer polymer. Next, a mixture of 21 parts by weight of methyl methacrylate, 9 parts by weight of methacrylic acid and 0.005 part by weight of potassium persulfate was continuously added over 90 minutes, and the mixture was further maintained for 90 minutes to polymerize the shell layer. The polymer latex was coagulated with sulfuric acid, neutralized with caustic soda, washed, filtered, and dried to obtain a rubber-containing polymer (c-1) having a two-layer structure. The 1% decomposition temperature of the polymer particles in nitrogen was 295 ° C. The number average particle diameter of the polymer particles measured with an electron microscope was 150 nm.

Examples 1 to 14: Production of thermoplastic polymer (second step), (d-1) to (d-14)
100 parts by weight of each of the original copolymers ((a-1) to (a-13)) and the original copolymers (B) (b-1) obtained in Reference Examples 1 to 13 and Reference Example 19 Then, 0.13 parts by weight of lithium acetate (anhydride) was blended as a catalyst, and a 38 mmφ biaxial / uniaxial composite continuous kneading extruder (HTM38 (manufactured by CTE, L / D = 47.5, vent part: 2 Pellets obtained by carrying out an intramolecular cyclization reaction at a screw rotation speed of 75 rpm, a raw material supply speed of 15 kg / h, and a cylinder temperature of 340 ° C. while purging nitrogen from the hopper at a rate of 10 L / min. Was dried for 16 hours with a hot air drier set at 80 ° C. to obtain pellet-shaped thermoplastic polymers ((d-1) to (d-14)), and the results are shown in Table 4.

Example 15: Production of thermoplastic polymer (second step), (d-15)
100 parts by weight of the original copolymer (a-1) is blended with 0.13 parts by weight of lithium acetate (anhydride) as a catalyst, and a 38 mmφ biaxial / uniaxial composite continuous kneading extruder (HTM38 (manufactured by CTE) L / D = 47.5, vent part: 2 places) While purging nitrogen from the hopper part at an amount of 10 L / min, screw rotation speed 75 rpm, raw material supply speed 10 kg / h, cylinder temperature 290 ° C. Intramolecular cyclization reaction was performed, and the obtained pellets were dried for 16 hours with a hot air dryer set at 80 ° C. to obtain a pellet-shaped thermoplastic polymer (d-15). It was shown to.

Comparative Examples 1 to 5 and Comparative Example 7: Production of thermoplastic polymer for comparative example (second step), (e-1) to (e-5) and (e-7)
Lithium acetate (anhydride) as a catalyst was added to 100 parts by weight of each of the original copolymers (a-14) to (a-17) for comparative examples and the original copolymer (b-2) for comparative examples. 13 parts by weight was blended and fed to a 38 mmφ biaxial / uniaxial composite continuous kneading extruder (HTM38 (CTE, L / D = 47.5, vent part: 2 locations). Nitrogen was supplied from the hopper part. While purging at a rate of 10 L / min, an intramolecular cyclization reaction was performed at a screw rotation speed of 75 rpm, a raw material supply speed of 15 kg / h, and a cylinder temperature of 340 ° C., and the resulting pellets were set in a hot air dryer set at 80 ° C. After drying for a time, pellet-shaped thermoplastic polymers ((e-1) to (e-5) and (e-7)) for comparative examples were obtained, and the results are shown in Table 4.

Comparative Example 6: Production of thermoplastic polymer for comparative example (second step), (e-6)
0.13 parts by weight of lithium acetate (anhydride) as a catalyst was blended with 100 parts by weight of the original copolymer (a-14) for comparison, and a 38 mmφ biaxial / uniaxial composite continuous kneading extruder (HTM38 (CTE, L / D = 47.5, vent: 2 places) While purging nitrogen from the hopper 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., and the obtained pellets were dried for 16 hours with a hot air drier set at 80 ° C. to give a pellet-shaped thermoplastic polymer (e-6) for a comparative example. The results are shown in Table 4.

  From the comparison of Examples 1-15 and Comparative Examples 1-7, the thermoplastic polymer of the present invention having a molecular weight of not more than 4% of the weight average molecular weight is not more than 3.0%. It has been found that while having excellent heat resistance, color tone and transparency, it has both high tensile elongation and tensile strength, and is excellent in tensile strength retention after wet heat treatment. Further, in Comparative Examples 1 to 5 and Comparative Example 7, since the intramolecular cyclization reaction is performed at a high temperature of 340 ° C., the thermoplastic polymer of Comparative Example 6 in which the intramolecular cyclization reaction is performed at a temperature of 290 ° C. Compared with, the intramolecular cyclization reaction of the original copolymer (A) is equal to or greater than 1.5 times as long as the feed rate is 1.5 times (the melt feed time in HTM38 is shortened by increasing the feed rate) This increases the production amount per hour by 1.5 times and improves the productivity, but on the other hand the color tone after melt-kneading is greatly reduced. However, the thermoplastic polymers of Examples 1 to 13 use a chain transfer agent containing a mercaptocarboxylic acid ester and / or an aromatic thiol, more preferably a chain transfer agent containing a mercaptocarboxylic acid ester, at the time of copolymerization. In comparison with the thermoplastic polymers of Comparative Examples 1 to 5 and Comparative Example 7 using a chain transfer agent containing no mercaptocarboxylic acid ester and / or aromatic thiol, It was found to have an excellent color tone. Further, the thermoplastic polymers of Examples 1 to 3, Example 5 and Examples 7 and 8, which were subjected to precipitation polymerization using a mercaptopropionic acid ester as a chain transfer agent and a charged monomer concentration of 17.0% or more, It was found that the color tone was particularly excellent even after high temperature treatment at 340 ° C.

Examples 16 to 29: Production of thermoplastic resin composition The thermoplastic polymers (d-1) to (d-14) and the rubber-containing polymer (C) were blended in the proportions shown in Table 5 to give a twin-screw extruder. Using TEX30 (L / D = 44.5, manufactured by Nippon Steel Co., Ltd.), kneading was performed at a set temperature of 280 ° C. and a screw rotation speed of 100 rpm, and pellets obtained by pelletizing were dried for 16 hours in a hot air dryer set at 80 ° C. Thus, a pellet-shaped thermoplastic resin composition was obtained. These thermoplastic resin compositions were dispersed in tetrahydrofuran and centrifuged to isolate the rubber-containing polymer, and then analyzed using an infrared spectrophotometer. As a result, both were 1800 cm ⁻¹ and 1760 cm. ^An absorption peak was confirmed at ^-1, and it was confirmed that a glutaric anhydride-containing unit was formed in the rubber-containing polymer.

Comparative Examples 8 to 13: Production of thermoplastic resin compositions for comparative examples Thermoplastic polymers (e-1) to (e-5) and (e-7) and a rubber-containing polymer (c-1) Blended in the proportions shown in Table 4 and kneaded using a twin screw extruder TEX30 (L / D = 44.5, manufactured by Nippon Steel Co., Ltd.) at a set temperature of 280 ° C. and a screw rotation speed of 100 rpm, pellets obtained by pelletizing were obtained. It dried for 16 hours with the hot air dryer set to 80 degreeC, and obtained the thermoplastic resin composition for pellets-like comparative examples. These thermoplastic resin compositions were dispersed in tetrahydrofuran and centrifuged to isolate the rubber-containing polymer, and then analyzed using an infrared spectrophotometer. As a result, both were 1800 cm ⁻¹ and 1760 cm ^{−. An} absorption peak was confirmed in ^1, and it was confirmed that a glutaric anhydride-containing unit was formed in the rubber-containing polymer.

Example 30
100 parts by weight of the original copolymer (a-1) obtained in Reference Example 1 and 0.13 parts by weight of lithium acetate (anhydride) were added to a twin-screw extruder TEX30 (L / D = 44.5, manufactured by Nippon Steel) ) At a set temperature of 285 ° C. and a screw rotation speed of 100 rpm, and 25 parts by weight of the rubber-containing polymer (c-1) is added from the intermediate position in the middle of the heat treatment using a side feeder. The mixture was added and kneaded, and the resulting pellet was dried for 16 hours with a hot air dryer set at 80 ° C. to obtain a pellet-shaped thermoplastic resin composition. The thermoplastic resin composition was dispersed in tetrahydrofuran and centrifuged to isolate the rubber-containing polymer and then analyzed using an infrared spectrophotometer. As a result, both were 1800 cm ⁻¹ and 1760 cm. ^An absorption peak was confirmed at ^-1, and it was confirmed that a unit containing glutaric anhydride was formed in the rubber-containing polymer.

  Table 5 summarizes the results of Examples 16 to 30 and Comparative Examples 8 to 13.

  From the comparison of Examples 16 to 30 and Comparative Examples 8 to 13, the thermoplastic resin compositions of Examples 16 to 30 in which the rubber-containing polymer (C) is added to the thermoplastic polymer of the present invention have heat resistance. It was found that while maintaining the color tone and transparency, it has excellent tensile strength and tensile elongation, and excellent tensile strength retention after wet heat treatment. In particular, when a mercaptocarboxylic acid ester is used as a chain transfer agent, it has been found that color tone, tensile properties, and tensile strength retention after wet heat treatment can be combined.

Claims (14)

(I) A thermoplastic polymer containing a glutaric anhydride-containing unit represented by the following general formula (1), wherein the value of the weight average molecular weight obtained by gel permeation chromatography of the thermoplastic polymer A thermoplastic polymer characterized in that the content of a polymer having a molecular weight of 4 times or more is 3.0 wt% or less.

(However, R ¹ and R ² are the same or different and represent any one selected from a hydrogen atom and an organic residue having 1 to 20 carbon atoms.) The thermoplastic polymer according to claim 1, wherein the glass transition temperature is 120 ° C or higher. The thermoplastic polymer according to claim 1 or 2, wherein the thermoplastic polymer has a weight average molecular weight of 30000 or more. The thermoplastic polymer is a copolymer having (i) a glutaric anhydride-containing unit represented by the general formula (1) and (ii) an unsaturated carboxylic ester unit. Item 4. The thermoplastic polymer according to any one of Items 1 to 3. The thermoplastic polymer is subjected to (ii) dehydration and / or (b) dealcoholization reaction to a raw copolymer (A) containing (ii) an unsaturated carboxylic acid ester unit and (iii) an unsaturated carboxylic acid unit. The thermoplastic polymer according to any one of claims 1 to 4, wherein the thermoplastic polymer is obtained by performing an intramolecular cyclization reaction. A chain transfer agent containing a mercaptocarboxylic acid ester and / or an aromatic thiol is added to the monomer mixture containing the unsaturated carboxylic acid ester monomer and the unsaturated carboxylic acid monomer, and in the presence or absence of a solvent. A production method for producing an original copolymer (A) comprising copolymerization (ii) an unsaturated carboxylic acid ester unit and (iii) an unsaturated carboxylic acid unit. The method for producing an original copolymer (A) according to claim 6, wherein the chain transfer agent is a chain transfer agent containing a mercaptocarboxylic acid ester. The content of the polymer having a molecular weight of 4 times or more of the value of the weight average molecular weight obtained by the gel permeation chromatography method of the original copolymer (A) is 3.0% by weight or less. The manufacturing method of the original copolymer (A) of Claim 6 or 7. In a solvent in which the original copolymer (A) containing (ii) an unsaturated carboxylic acid ester unit and (iii) an unsaturated carboxylic acid unit is not more than 1 g / 100 g in solubility in the original copolymer (A), The raw co-polymer according to any one of claims 6 to 8, which is obtained by copolymerizing a monomer mixture comprising a saturated carboxylic acid ester monomer and an unsaturated carboxylic acid monomer. Manufacturing method of union (A). By subjecting the original copolymer (A) obtained in any one of claims 6 to 9 to an intramolecular cyclization reaction by (i) dehydration and / or (b) dealcoholization reaction, the following general formula ( (I) A method for producing a thermoplastic polymer comprising producing a thermoplastic polymer containing a glutaric anhydride-containing unit represented by 1).

(However, R ¹ and R ² are the same or different and represent any one selected from a hydrogen atom and an organic residue having 1 to 20 carbon atoms.) A method for producing a thermoplastic polymer, wherein the thermoplastic polymer according to claim 10 is the thermoplastic polymer according to any one of claims 1 to 4. A thermoplastic resin composition, wherein the thermoplastic polymer according to any one of claims 1 to 5 further contains a rubbery polymer (C). The molded article formed by processing the thermoplastic polymer of any one of Claims 1-5, or the thermoplastic resin composition of Claim 12. The molded article according to claim 13, wherein the molded article is a film.