WO2006068193A1

WO2006068193A1 - Thermoplastic resin composition and molded article

Info

Publication number: WO2006068193A1
Application number: PCT/JP2005/023519
Authority: WO
Inventors: Madoka Furuta
Original assignee: Toagosei Co., Ltd.
Priority date: 2004-12-24
Filing date: 2005-12-21
Publication date: 2006-06-29
Also published as: KR20070106493A; TWI388605B; JP4645809B2; JP2006176711A; CN101061183A; TW200631987A

Abstract

Disclosed is a thermoplastic resin composition containing a thermoplastic resin (A) having a functional group reactive with epoxy groups, a polymer (B) having an epoxy group and a catalyst (C) for accelerating reactions of the functional group reactive with epoxy groups and the epoxy group. The content of the polymer (B) is set at 0.1-5 parts by mass per 100 parts by mass of the thermoplastic resin (A), while the content of the catalyst (C) is set at from 1.0 × 10-6 to 50 × 10-6 parts by mass per 100 parts by mass of the thermoplastic resin (A). Also disclosed is a molded article obtained by molding, for example extrusion molding the thermoplastic resin composition.

Description

Specification

Thermoplastic resin composition and molded article

Technical field

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic resin composition mainly composed of a condensation polymer such as a polyester resin and a molded product thereof, and more specifically, a thermoplastic resin that provides a molded product that exhibits excellent dimensional stability. The present invention relates to a composition and a molded article thereof.

Background art

[0002] Condensation polymers such as polyester resins exhibit excellent mechanical strength and are used in various fields such as bottles, sheets, and films. In particular, polyester resins are widely used as food packaging materials such as bottles and blister packs because they exhibit excellent transparency and hygiene. In recent years, the movement to collect and reuse waste resin has become active in consideration of the reduction of environmental impact, and in particular, the amount of collected and recycled polyethylene terephthalate (hereinafter referred to as PET) resin bottles. Usage is increasing year by year. The main demand for recycled PET resin products is egg pack sheets, clothes and power. This is a fiber for tapping. However, while the amount of recycled PET resin recovered has increased, the demand for recycled products such as sheets and fibers has been stagnant.

[0003] Therefore, there is a demand for the development of new products that should increase the demand for recycled PET resin products. Originally, PET resin is suitable for molded products having a small diameter such as fibers and molded products having a small cross-sectional area such as a film because of its low melt viscosity and low melt tension. However, PET resin has a large diameter or large cross-sectional area because a draw-down phenomenon occurs during molding when its melt tension is excessively low and a molded product with a desired size cannot be obtained. In particular, it is not suitable for extruded products. Furthermore, PET resin is prone to uneven thickness due to the drawdown phenomenon during vacuum forming. Therefore, the low viscosity and low melt tension inherent in PET resin are barriers to the development of new products. Furthermore, since recycled PET resin has a lot of heat history, and the hydrolysis of recycled PET resin proceeds, the melt viscosity and melt tension of recycled PET resin are lower than virgin PET resin. . Therefore, it is extremely difficult to develop new products using recycled PET resin. [0004] As methods for increasing the melt viscosity and melt tension of PET resin and recycled PET resin, Patent Literature 1 and Patent Literature 2 disclose a method of blending a polymer having an epoxy group with PET resin. Patent Documents 3 and 4 disclose a method of blending a compound containing an epoxy group and an organic alkali metal salt into a PET resin.

[0005] According to the methods described in Patent Document 1 and Patent Document 2, the melt viscosity and melt tension of the polyester resin can be increased, and the drawdown of the polyester resin during molding can be improved. However, in these methods, depending on the reaction conditions between the polymer containing an epoxy group and the polyester resin, the reaction may be insufficient. For this reason, it is necessary to add a large amount of a polymer containing an epoxy group to the thermoplastic resin composition. In this case, for example, a cross-linked product of a polyester resin and an epoxy group-containing polymer is generated during melt-kneading in an extrusion molding machine, so that appearance defects such as fish eyes are likely to occur in the obtained molded product. There was a problem.

[0006] According to the methods described in Patent Document 3 and Patent Document 4, by using a compound containing an epoxy group and an organic alkali metal salt in combination, the reactivity between them and the polyester resin is increased. Can do. However, depending on the reaction conditions between the epoxy group-containing compound and the organic alkali metal salt and the polyester resin, there is a problem that the viscosity of the thermoplastic resin composition decreases.

Patent Document 1: Japanese Patent No. 2675718

Patent Document 2: Pamphlet of International Publication No. 03Z066704

Patent Document 3: Republished Patent WO01 / 094443

Patent Document 4: Japanese Unexamined Patent Application Publication No. 2004-155968

Disclosure of the invention

Problems to be solved by the invention

[0007] An object of the present invention is to provide a thermoplastic resin composition having a high melt viscosity and melt tension, which gives a molded product exhibiting excellent dimensional stability. Another object of the present invention is to provide a molded product that exhibits excellent dimensional stability.

Means for solving the problem [0008] In one embodiment of the present invention, a thermoplastic resin composition is provided. The thermoplastic resin composition has reactivity with a thermoplastic resin (A) having a functional group having reactivity with an epoxy group, a polymer (B) having an epoxy group, and an epoxy group. And a catalyst (C) that promotes the reaction of the functional group and the epoxy group. The content of the polymer (B) is set to 0.:! To 5 parts by mass per 100 parts by mass of the thermoplastic resin (A). The content of catalyst (C), that is set to the thermoplastic resin (A) 100 parts by mass of per 1. 0 X 10 one ^⁶ ~ 50 X 10- ⁶ parts by weight.

[0009] The thermoplastic resin (A) is preferably at least one selected from the group consisting of a polyester resin, a polycarbonate resin, a polyamide resin, a polyphenylene ether resin, and a polylactic acid resin.

[0010] The polymer) is preferably a vinyl polymer having an epoxy group. The average number of epoxy groups in the polymer) is preferably 1.2 or more per molecule of the polymer (B), and the number average molecular weight of the polymer (B) is preferably 300 to 30000.

[0011] The catalyst (C) is preferably a metal carboxylate compound, more preferably a metal benzoate salt or a metal stearate salt.

[0012] The thermoplastic resin composition further comprises a compound (D) different from the thermoplastic resin (A), having one carboxynole group, and the content of the compound (D) (a) 100 parts by mass of per ^{0. 3 X 1CT 6 ~: 10} X 10_ Shi preferred that it is set to ⁶ parts by Les.

[0013] The compound (D) is preferably benzoic acid or stearic acid.

[0014] In one embodiment of the present invention, the thermoplastic resin composition has a master batch, and the master batch includes a part of the thermoplastic resin (soot), a polymer (soot), a catalyst (C), and The thermoplastic resin composition is preferably prepared by mixing the master batch containing the compound (D) and the remainder of the thermoplastic resin (熱). In this case, the content of the thermoplastic resin (Α) is 30 to 30 parts per 100 parts by mass in total of the thermoplastic resin (）), polymer), catalyst (C), and compound (D) in the masterbatch. It is preferably set to 85 parts by mass and the total content of the polymer (IV), the catalyst (C), and the compound (D) is set to 15 to 70 parts by mass.

[0015] In one embodiment of the present invention, the thermoplastic resin composition is a thermoplastic resin different from the thermoplastic resin (樹脂). It further contains a plastic resin (E), and among the thermoplastic resins (A) and (E), only the thermoplastic resin (A) has a functional group having reactivity with an epoxy group. It is preferable to have a masterbatch. In this case, the master batch contains the polymer (B), the catalyst (C), the compound (D), and the thermoplastic resin (E), and is heated by mixing the master batch with the thermoplastic resin (A). It is preferable that a plastic resin composition is prepared. Further, the polymer (B), the catalyst (C) and the polymer (B), the catalyst (C), the compound (D), and the thermoplastic resin (E) in the master batch per 100 parts by mass in total. And the total content of the compound (D) is preferably set to 15 to 70 parts by mass, and the content of the thermoplastic resin (E) is preferably set to 30 to 85 parts by mass.

[0016] The thermoplastic resin (E) is preferably at least one selected from the group consisting of a polyolefin resin and a polystyrene resin.

[0017] In another aspect of the present invention, there is provided a molded product obtained by molding the thermoplastic resin composition.

[0018] In still another aspect of the present invention, a molded article obtained by extrusion molding of the thermoplastic resin composition is provided.

Brief Description of Drawings

FIG. 1 is a graph showing the relationship between the concentration of catalyst (C) (aluminum stearate) in the thermoplastic resin composition according to the embodiment and the moldability (die swell evaluation).

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, embodiments of the present invention will be described in detail. In the present invention, acrylic and methacryl are combined with (meth) acrylic resin.

[0021] The thermoplastic resin composition according to the present embodiment includes a thermoplastic resin (A) having a functional group having reactivity with an epoxy group, a polymer (B) having an epoxy group, and an epoxy group. Containing a reactive functional group and a catalyst (C) that promotes the reaction of the epoxy group.

[0022] The thermoplastic resin (A) is a main component of the thermoplastic resin composition and is responsible for the basic performance of a molded product obtained by molding the thermoplastic resin composition. Specific examples of functional groups having reactivity with epoxy groups include carboxyl groups, hydroxyl groups, amide groups, and amino groups. Can be mentioned. Examples of thermoplastic resin (A) include polyester resin, polyamide resin, polycarbonate resin, polylactic acid resin, poly-strength prolatatone resin, polybutylene succinate resin, poly (butylene succinate / adipate) resin, polyphenylene sulfide resin , Polyetherketone resin, polyetherimide resin, cellulose resin, carboxylic acid modified polyolefin resin, carboxylic acid modified styrene 'butadiene' styrene (SBS) resin, and carboxylic acid modified styrene.ethylene.butadiene.styrene (SEBS) resin. Can be mentioned. The thermoplastic resin (A) may be a recovered thermoplastic resin waste collected and reused, that is, a recycled thermoplastic resin. The thermoplastic resin (A) is a polyester resin, a polycarbonate resin, or a polyamide resin that is preferred by at least one selected from the group consisting of a polyester resin, a polycarbonate resin, a polyamide resin, a polyphenylene ether resin, and a polylactic acid resin. Polylactic acid resins and polyester resins (including recycled polyester resins) in which these recycled resins are more preferred are even more preferable.

[0023] Specific examples of the polyester resin include a condensation polymer or copolymer having a dicarboxylic acid unit and a diol unit as constituent units. Specific examples of the raw material used for forming the dicarboxylic acid unit include an aromatic dicarboxylic acid and a diallyl ester or diallyl ester thereof. Specific examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalenoic acid, naphthalene 1,4-dicarboxylic acid, naphthalene 2,6-dicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diphenyldicarboxylic acid and 4,4'-diphenyletherenocarboxylic acid. Along with these, aliphatic dicarboxylic acids or diallyl esters or diallyl esters thereof may be used as raw materials. Specific examples of the aliphatic dicarboxylic acid include dartaric acid, adipic acid, sebacic acid, oxalic acid, and succinic acid.

[0024] Specific examples of raw materials used to form diol units include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6- Hexanediol, decamethylene glycol, 1,4-cyclohexane dimethanol, 2,2_bis (4-hydroxyphenyl) propane, polyethylene glycol, poly 1,3-propylene glycol, and polytetramethylene glycol All I can get lost.

[0025] The polyester resin is preferably a crystalline homopolyethylene terephthalate resin or a crystalline copolyester resin. The crystalline homopolyethylene terephthalate resin and the crystalline copolyester resin are terephthalic acid units and / or dicarboxylic acid units. It contains isophthalic acid units and contains ethylene glycol units as diol units. The polyester resin is preferably an amorphous copolyester resin. The amorphous copolyester resin contains terephthalic acid units as dicarboxylic acid units, ethylene glycol units and 1,4-cyclohexene as diol units. Includes sandimethanol units. Furthermore, polyester resins include aromatic polyester resins such as polybutylene terephthalate and polyethylene 2,6 naphthalate, and aliphatic polyester resins such as polylactic acid resin.

Or a biodegradable polyester resin. These may constitute a polyester resin alone, or two or more may be combined to form a polyester resin.

[0026] The polymer) plays a role of increasing the melt viscosity and melt tension of the thermoplastic resin composition. The polymer) is obtained by a polymerization reaction of two types of butyl monomers, and only one of the two types of vinyl monomers has an epoxy group. Specific examples of the vinyl monomer having an epoxy group include glycidyl (meth) acrylate, (meth) acrylate ester having a cyclohexene oxide structure, and (meth) aryl glycidyl ether. The butyl monomer having an epoxy group is preferably glycidyl (meth) acrylate.

[0027] Of the two types of bulle monomers, specific examples of the bur monomer having no epoxy group include an alkyl group having 1 to 22 carbon atoms (the alkyl group may be a straight chain). (Meth) acrylic acid alkyl ester, (meth) acrylic acid methoxyethyl, (meth) acrylic acid polyalkylene glycol ester, (meth) acrylic acid alkoxyalkyl ester, (meth) Acrylic acid hydroxyalkyl ester, (meth) acrylic acid dialkylaminoalkyl ester, (meth) acrylic acid benzyl ester, (meth) acrylic acid phenoxyalkyl ester, (meth) acrylic acid isobornyl ester, and (meth) Examples include silyl alkaryl silylalkyl ester. Specific examples of the (meth) acrylic acid alkyl ester having an alkyl group having carbon atoms of :! to 22 include (meth) acrylic acid. Methylol, (meth) acrylic acid ethyl, (meth) acrylic acid propyl, (meth) acrylic acid butyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid cyclohexyl, and (meth) acrylic acid Stearyl is mentioned.

[0028] Bull monomers that do not have an epoxy group are (meth) acrylamide, (meth) acryl dial quinoleamide, bull esters, bull ethers, (meth) aryl ethers, or aromatic bull monomers. But you can use olefin monomer. Specific examples of the butyl esters include vinyl acetate, and specific examples of the aromatic vinyl monomer include styrene and α-methylstyrene. Specific examples of aolefin monomers include ethylene and propylene. These may be used alone or in combination of two or more.

[0029] The composition of the bull monomer in the polymer (B) is selected according to the object of the present invention and the function required for the molded article of the thermoplastic resin composition. For example, when transparency is particularly required for a molded product, it is preferable to select a vinyl monomer as the bull monomer in the polymer) with a refractive index close to that of the thermoplastic resin (A). Les. When the thermoplastic resin (A) is polyethylene terephthalate (refractive index: about 1.565), an aromatic bull monomer having a high refractive index may be selected as a bull monomer having no epoxy group. preferable. Specific examples of the aromatic vinyl monomer include styrene and α-methylstyrene. When flexibility is particularly required for a molded article, it is preferable to select a bull monomer having a low glass transition temperature as a bull monomer having no epoxy group. Specific examples of the bull monomer having a low glass transition temperature include butyl (meth) acrylate and ethyl (meth) acrylate. When the polymer) functions as a compatibilizer, for example, when the polymer (Β) is a polyethylene terephthalate レート polyolefin blend composition or a polycarbonate / polyolefin blend composition, It is preferable to select an olefin fin monomer as a monomer. Specific examples of the olefin fin monomer include ethylene, propylene, and butadiene.

[0030] The polymer (Β) contains 1 to 70% by weight of a bully monomer unit having an epoxy group and 30 to 99% by weight of a bully monomer unit having no epoxy group. Contained at a ratio of It contains a butyl monomer unit having an epoxy group that is preferable to be contained in a proportion of 5 to 60% by mass, and a bulle monomer unit having no epoxy group in a proportion of 40 to 95% by mass. It contains 10 to 50% by mass of bulle monomer units having an epoxy group, which is more preferable, and a proportion of 50 to 90% by mass of bulle monomer units having no epoxy group. It is more preferable to contain. When the content of the butyl monomer unit having an epoxy group is less than 5% by mass, the polymer) cannot sufficiently increase the melt tension of the thermoplastic resin composition. May occur and the molded product may not be molded into the desired shape. When the content of the butyl monomer unit having an epoxy group exceeds 70% by mass, the thermoplastic resin composition is formed in the molding machine by an excessive crosslinking reaction between the thermoplastic resin (A) and the polymer (B). It may become a cross-linked product and the molded product may not be molded into the desired shape.

[0031] The average number of epoxy groups in the polymer (B) is preferably 1.2 or more per molecule of the polymer (B) 1.5 to: 100 is more preferable 2.0 ~ 50 are more preferred. Polymer (B) The average number of epoxy groups per molecule is determined by the following formula (1).

[0032] Average number of epoxy groups = a X b / 100c (1)

In the formula (1), a represents the proportion (% by mass) of butyl monomer units having an epoxy group contained in the polymer (B), b represents the number average molecular weight of the polymer (B), and c represents It represents the molecular weight of a vinyl monomer having an epoxy group.

[0033] When the average number of epoxy groups in the polymer) is less than 1.2, the polymer) cannot sufficiently increase the melt viscosity and melt tension of the thermoplastic resin composition. In some cases, the occurrence of the drawdown phenomenon cannot be suppressed.

[0034] The number average molecular weight of the polymer (B) is preferably 300 to 30000 force, more preferably 350 to 25,000 force, and more preferably 400 to 20000 force. When the number average molecular weight of the polymer (B) is less than 300, the average of the number of epoxy groups that the polymer (B) has becomes low, so that the polymer (B) has a melt viscosity and a melt of the thermoplastic resin composition. The tension may not be increased sufficiently. When the number average molecular weight of the polymer (B) exceeds 30000, the average number of epoxy groups contained in the polymer (B) becomes high, so that the thermoplastic resin composition causes an excessive crosslinking reaction in the molding machine. As a result, the moldability of the thermoplastic resin composition may deteriorate. [0035] The polymer (B) is produced by any polymerization method such as a bulk polymerization method, a solution polymerization method, and an emulsion polymerization method. The polymer (B) is preferably produced by a continuous bulk polymerization method, and more preferably produced by a high temperature continuous bulk polymerization method. Polymerization temperature of polymer (B) ί 130 ~ 350. C force is preferable, 150 to 330 ^o C force is preferable to S <, 170 to 270 ^o C force is more preferable. Within the above polymerization temperature range, a polymer (B) having a desired molecular weight can be obtained by using a radical polymerization initiator or a chain transfer agent without using a radical polymerization initiator or a chain transfer agent. ) Can be obtained efficiently. When the polymerization temperature is less than 130 ° C, a large amount of radical polymerization initiator or chain transfer agent is required to obtain the desired molecular weight, so the resulting polymer (B) contains a large amount of impurities. easy. Therefore, problems such as coloring and off-flavor may occur in the thermoplastic resin composition and the molded product. When the polymerization temperature exceeds 350 ° C, the polymer (B) may be thermally decomposed, and thus the polymer (B) may not be obtained efficiently.

[0036] The high-temperature continuous polymerization of the polymer (B) is performed according to a known method disclosed in, for example, JP-A-57-502171, JP-A-59-6207, or JP-A-60-215007. Done. For example, in the case of polymer (B), a reactor capable of being pressurized is set to a predetermined temperature under pressure, and then a mixture of bully monomers comprising each bully monomer and, if necessary, a polymerization solvent is used. It is produced by supplying the reactor at a constant feed rate and recovering the polymerization reaction solution in an amount equivalent to the feed amount of the vinyl monomer mixture. A polymerization initiator may be blended in the vinyl monomer mixture as necessary. The amount of the polymerization initiator is preferably from 0.00: to 2 parts by mass per 100 parts by mass (% by mass) of the vinyl monomer mixture. The pressure during the production of the polymer (B) depends on the reaction temperature, the mixture of vinyl monomers used, and the boiling point of the solvent, and the pressure does not affect the reaction. Any pressure can be used as long as the temperature can be maintained. The residence time of the mixture of vinyl monomers in the reactor is preferably:! -60 minutes, more preferably 2-40 minutes. If the residence time is less than 1 minute, the vinyl monomer may not react sufficiently. When the residence time exceeds 60 minutes, the productivity of the polymer (B) may deteriorate.

[0037] The content of the polymer (B) in the thermoplastic resin composition is 0.:! To 5 parts by mass, preferably 0.3 to 3 parts by mass per 100 parts by mass of the thermoplastic resin (A). Masugu 0.5-2 parts by mass are more preferred That's right. When the content of the polymer (B) is less than 0.1 part by mass, the polymer (B) cannot sufficiently increase the melt tension of the thermoplastic resin composition, and thus the dimensional stability of the molded product is low. . When the content of the polymer (B) exceeds 5 parts by mass, a crosslinked product is formed during molding of the thermoplastic resin composition, so that the gloss of the molded product is lowered and the molded product becomes opaque.

[0038] The catalyst (C) plays a role of promoting a reaction between a functional group having reactivity with an epoxy group and an epoxy group. A specific example of the catalyst (C) is not particularly limited as long as it is a compound that plays the above role, and is preferably a metal salt compound. Specific examples of the metal salt compound include organic fatty acid metal salts, aromatic carboxylic acid metal salts, acidic pyrophosphates, phosphoric acid metal salts, metal salts of acidic phosphates, and metal chlorides.

[0039] Specific examples of the organic fatty acid metal salt include sodium stearate, calcium stearate, aluminum stearate, magnesium stearate, zinc stearate, lead stearate, cadmium stearate, lithium stearate, barium stearate. , Zinc laurate, zinc ricinoleate, zinc 2-ethylhexohexanoate, aluminum 12-hydroxystearate, and zinc 12-hydroxystearate. Specific examples of the aromatic carboxylic acid metal salt include sodium benzoate, calcium benzoate, magnesium benzoate, and aluminum benzoate. Specific examples of acidic pyrophosphates include sodium pyrophosphate, potassium pyrophosphate, aluminum pyrophosphate, and sodium dihydrogen pyrophosphate. Specific examples of the metal phosphate include sodium phosphate, aluminum phosphate, and calcium phosphate. Specific examples of the acid phosphate metal salt include sodium stearyl phosphite, calcium stearyl phosphite, aluminum stearyl phosphite, and zinc stearyl phosphite. Specific examples of metal chlorides include chlorides such as sodium chloride, calcium chloride, magnesium chloride, and zinc chloride.

[0040] The catalyst (C) is preferably an organic fatty acid metal salt, an aromatic carboxylic acid metal salt, or a metal salt of an acidic phosphate because it has good compatibility with the thermoplastic resin (A). Particularly preferred are zinc stearate, aluminum stearate, barium stearate, or sodium benzoate. [0041] The content of the catalyst (C) of the thermoplastic resin composition, the thermoplastic resin (A) 100 parts by mass of those or 1.0 X 10 50 X 10- ⁶ parts by weight (1.0 50 mass ppm) and a, 2.0 X 10 35 X 10- ⁶ parts by weight (2.0 35 mass ppm), more preferably les. When the content of the catalyst (C) is less than 1.0 X 10 — ⁶ parts by mass, the melt tension of the thermoplastic resin composition cannot be sufficiently increased, and thus the dimensional stability of the molded product is low. When the content of the catalyst (C) is more than 50 X 10- ⁶ parts by weight, rather because the melt tension and melt viscosity of the thermoplastic resin composition is lowered, low dimensional stability of the molded article. Therefore, the content of the catalyst (C) is a very important condition for the present invention.

[0042] In addition to the components (A) and (C), the thermoplastic resin composition has a compound (D) (hereinafter referred to as carboxy) having one carboxyl group and different from the thermoplastic resin (A). The compound (D) and les.) Are preferably further contained.

[0043] The carboxyl compound (D) adjusts the melt viscosity and melt tension of the thermoplastic resin composition, and is caused by gelation of the thermoplastic resin composition before or during the molding of the thermoplastic resin composition. It plays a role in preventing the occurrence of molding defects. Here, the carboxyl compound (D) does not include a thermoplastic resin (A) having one carboxynole group, for example, a polyester resin having a carboxyl group and a hydroxyl group as terminal groups.

[0044] The carboxyl group of the carboxyl compound (D) can sufficiently prevent the occurrence of defects during molding. Therefore, it is preferable that all or part of the carboxyl group does not form a salt with a metal. That is, it is preferable that at least a part of the carboxyleno group is in an acid state. Specific examples of metals include sodium, potassium, magnesium, and calcium.

[0045] Specific examples of the carboxyl compound (D) include a lower aliphatic carboxylic acid compound, a higher aliphatic carboxylic acid compound, and an aromatic carboxylic acid compound. Specific examples of the lower aliphatic carboxylic acid compound include acetic acid, butyric acid, isobutyric acid, pentanoic acid, and isopentanoic acid. Specific examples of the higher aliphatic carboxylic acid compound include decanoic acid, undecanoic acid, lauric acid, palmitic acid, oleic acid, and stearic acid. Specific examples of the aromatic carboxylic acid compound include benzoic acid, methylbenzoic acid, 4-ethylbenzoic acid, 2,4-dimethylbenzoic acid, o-tolylacetic acid, m-tolylacetic acid, p-trilelic acid. Examples include lucacetic acid, 2_phenylbutyric acid, 4_phenylbutyric acid, 1_naphthoic acid, and 2_naphthoic acid. The carboxyl compound (D) is preferably benzoic acid or stearic acid. Monofunctional carboxylic acid anhydrides such as benzoic anhydride, butyric anhydride, hexanoic anhydride, and propionic anhydride are converted to compounds having one carboxynole group by hydrolysis, so that carboxyl compounds (D) include. Dihydric carboxylic acid anhydrides, such as phthalic anhydride and maleic anhydride, are not included in the carboxyl compound (D) because they are converted into compounds having two carboxyl groups by hydrolysis.

[0046] The carboxyl compound (D) is preferably a carboxylic acid compound having 5 or more carbon atoms, and more preferably an aromatic carboxylic acid compound. When the carboxyl compound (D) is an aromatic carboxylic acid compound, the carboxyl compound (D) has good compatibility between the thermoplastic resin (A) and the polymer (B), which are components of the thermoplastic resin composition. It is easy to make the molded product homogeneous.

[0047] The boiling point of the carboxynole compound (D) is preferably 100 ° C or higher, more preferably 150 ° C or higher, and further preferably 200 ° C or higher. When the boiling point of the carboxyl compound (D) is less than 100 ° C., the carboxyl compound (D) is easily diffused during the heating and melting process in the production of the thermoplastic resin composition. Therefore, it becomes difficult to control the content of the carboxyl compound (D) in the thermoplastic resin composition, and the working environment may be inappropriate.

[0048] carboxyl compound in the thermoplastic resin composition content of (D), the thermoplastic resin (A) 100 parts by mass of per 0.3 X 10 10 X 10- ⁶ parts by weight (0.3 10 mass ppm) preferably 0. 5 X 10 5 X 10- ⁶ weight咅B (0. 5 5 mass ppm) Ca than preferred les. When the content of the force Norebokishinore compound (D) is less than 0. 3 X 10- ⁶ parts by weight, since the cross-linked product when forming the shape of the thermoplastic resin composition is produced, the gloss of the molded article is lowered molding The product may become opaque. Karubokishinore compound (D) if the content exceeds 10 X 10_ ⁶ parts by weight of, since the melt tension and melt viscosity of the thermoplastic resin composition is lowered, there is a possibility that the dimensional stability of the molded article is lowered .

[0049] The thermoplastic resin composition includes an extender pigment, a color pigment, a plasticizer, a thermoplastic resin (A), a polymer (B), a catalyst (C), and, if necessary, a carboxyl compound (D). You may contain the well-known component which can be mix | blended with a fluidity modifier, a crystal nucleating agent, and other thermoplastic resins. [0050] The thermoplastic resin composition is obtained by mixing the thermoplastic resin (A), the polymer (B), the catalyst (C) and, if necessary, the carboxyl compound (D) by any method. It is done. For example, the thermoplastic resin composition can be obtained by mixing the raw materials with an extruder or a kneader. Specific examples of the extrusion molding machine include a single screw extruder, a mating type parallel parallel twin screw extruder, a mating type different direction parallel shaft twin screw extruder, a mating type different direction oblique axis twin screw extruder, Non-matching twin screw extruders, incomplete mating twin screw extruders, conida single screw extruders, planetary gear extruders, transfer mix extruders, ram extruders, and roller extruders. Prior to the mixing, the raw materials may be premixed by using, for example, a hen shell mixer or a tumbler. The shape of each raw material of the thermoplastic resin composition may be a pellet shape, a powder shape, or a liquid shape.

[0051] A polymer (B), a catalyst (C), and, if necessary, a carboxyl compound (D) are prepared in advance as a master batch mixed with a certain amount of a thermoplastic resin, and the master batch and the thermoplastic resin ( A thermoplastic resin composition may be produced by mixing with A). Hereinafter, this production method is referred to as a master batch method. The masterbatch method is preferable because the catalyst (C) and the carboxyl compound (D), which are relatively small components, are easily mixed uniformly in the thermoplastic resin composition. The thermoplastic resin used in the preparation of the masterbatch may be part of the thermoplastic resin (A), or may be a thermoplastic resin (E) different from the thermoplastic resin composition (A). Both a part of the resin (A) and the thermoplastic resin (E) may be used. When the thermoplastic resin used for the preparation of the masterbatch contains the thermoplastic resin (E), the thermoplastic resin composition further contains the thermoplastic resin (E). Of the thermoplastic resins (A) and (E), only the thermoplastic resin (A) has a functional group having reactivity with an epoxy group.

[0052] The preparation of the masterbatch and the production of the thermoplastic resin composition by mixing the masterbatch and the remainder of the thermoplastic resin (A) may be performed using the extruder or kneader exemplified above. .

[0053] When the thermoplastic resin used in the preparation of the masterbatch is part of the thermoplastic resin (A), in the preparation process of the masterbatch, the thermoplastic finally blended into the thermoplastic resin composition A part of the total amount of resin (A) is used. Thermoplasticity in masterbatch Resin (A) content is based on 100 parts by mass of the total content of thermoplastic resin (A), polymer (B), catalyst (C), and, if necessary, carboxyl compound (D) in the masterbatch. 30 to 85 parts by weight is preferred 40 to 80 parts by weight is more preferred 45 to 75 parts by weight is even more preferred. On the other hand, the total content of the polymer (B), the catalyst (C) and, if necessary, the carboxyl compound (D) in the masterbatch is the thermoplastic resin (A), polymer (

B), the catalyst (C) and, if necessary, the total content of the carboxylenole compound (D) is preferably 15-70 parts by mass per 100 parts by mass, more preferably 20-60 parts by mass, 25-55 parts by mass Is more preferable.

[0054] By using such a masterbatch, the melt viscosity and melt tension of the thermoplastic resin composition are particularly high, and as a result, a molded product exhibiting excellent dimensional stability can be obtained.

[0055] When a thermoplastic resin composition is produced by using a masterbatch containing a portion of the thermoplastic resin (A), the balance of the thermoplastic resin (A) mixed with the masterbatch is the final amount In particular, it is obtained by subtracting the amount of the thermoplastic resin (A) used for preparing the masterbatch from the total amount of the thermoplastic resin (A) contained in the thermoplastic resin composition.

[0056] When the thermoplastic resin used in the preparation of the masterbatch is a thermoplastic resin (E), the content of the thermoplastic resin (E) in the masterbatch is the thermoplastic resin (E) in the masterbatch. , Polymer (B), catalyst (C), and, if necessary, the total content of carboxyl compound (D) is preferably 30 to 85 parts by mass, preferably 40 to 80 parts by mass per 100 parts by mass. More preferred is 45 to 75 parts by mass. On the other hand, polymer (B), catalyst (

C) and, if necessary, the total content of carboxyl compounds is determined by calculating the thermoplastic resin (E), polymer (B), catalyst (C), and optionally carboxylic acid compound (

The total content of D) is preferably 15 to 70 parts by mass per 100 parts by mass, more preferably 20 to 60 parts by mass, and even more preferably 25 to 55 parts by mass.

[0057] By using such a master batch, the melt viscosity and melt tension of the thermoplastic resin composition are particularly high, and as a result, a molded product exhibiting excellent dimensional stability can be obtained. [0058] When the thermoplastic resin composition is produced by using a masterbatch containing the thermoplastic resin (E) instead of the thermoplastic resin (A), the thermoplastic resin (A) mixed with the masterbatch The amount of is equal to the total amount of the thermoplastic resin (A) contained in the thermoplastic resin composition.

[0059] When the thermoplastic resin used in the preparation of the masterbatch is both a part of the thermoplastic resin (A) and the thermoplastic resin (E), the thermoplastic resin (A) in the masterbatch and The total content of (E) is equal to the content of thermoplastic resin (A) or (E) in each masterbatch. The thermoplastic resin used for the preparation of the masterbatch can particularly enhance the above-mentioned properties of the thermoplastic resin composition. Therefore, it is preferable that a part or all of the thermoplastic resin is the thermoplastic resin (A). .

[0060] Specific examples of the thermoplastic resin (E) used for preparing the masterbatch include polyolefin resin, styrene resin, and acrylic resin. Specific examples of polyolefin resins include low density polyethylene resin, high density polyethylene resin, polypropylene resin, ethylene / propylene copolymer, ethylene acetate butyl copolymer, and polyethylene / ethyl acrylate copolymer. Specific examples of the styrene resin include polystyrene resin, acrylonitrile 'styrene copolymer, methyl methacrylate' styrene copolymer, and acrylonitrile 'butadiene' styrene copolymer. Specific examples of the acrylic resin include polymethyl methacrylate resin. The thermoplastic resin (E) is preferably a polyolefin resin or a polystyrene resin.

[0061] The thermoplastic resin composition is used for production of various molded articles by an extrusion molding machine or an injection molding machine. Molded products obtained from the thermoplastic resin composition include, for example, extruded products such as sheets and films, calendered products, deformed extruded products such as pipes and baseboards, injection molded products, and blow molded products such as bottles. , Foam molded products, and drawn molded products.

[0062] Since the thermoplastic resin composition exhibits excellent drawdown resistance, the method of producing a molded product from the thermoplastic resin composition by extrusion molding effectively utilizes the characteristics of the thermoplastic resin composition. It is preferable to use. Specific examples of the molded product obtained by extrusion molding include a transparent sheet, a transparent film, and a deformed product.

[0063] Examples and comparative examples of the present invention will be described below, but the present invention is limited to the following examples. Not determined.

Example

[0064] (Production of polymer 1)

The temperature of an oil jacket in a pressurized stirred tank reactor (capacity: 1 liter) equipped with an oil jacket was raised to 200 ° C. On the other hand, 69 parts by mass of styrene (hereinafter referred to as St), 30 parts by mass of glycidyl metatalylate (hereinafter referred to as GMA), 1 part by mass of methyl metatalylate (hereinafter referred to as MMA), A monomer mixture consisting of 15 parts by mass of xylene 15 parts by mass and 0.5 parts by mass of ditertiary butyl peroxide (hereinafter referred to as DTBP) as a polymerization initiator was prepared and added to the raw material tank. It was. Next, the monomer mixed solution was continuously supplied from the raw material tank to the reactor, and the reaction solution was continuously collected from the outlet of the reactor so that the mass of the content solution in the reactor was constant at about 580 g. The supply rate of the monomer mixture during continuous supply was set to 48 g / min, and the residence time of the monomer mixture was set to 12 minutes. Furthermore, the temperature in the reactor during continuous feeding was maintained at about 210 ° C.

[0065] After 36 minutes had passed since the temperature in the reactor was stabilized, volatile components were removed from the recovered reaction solution, and recovery of polymer 1 containing almost no volatile components was started. The volatile components were removed from the reaction solution using a thin film evaporator. The pressure of the thin film evaporator was maintained at 30 kPa and the temperature was maintained at 250 ° C. Volatile components were removed from the reaction solution for 180 minutes, and about 7 kg of Polymer 1 was recovered.

[0066] The number average molecular weight of polymer 1 (hereinafter referred to as Mn and R) obtained by polystyrene conversion determined from a gel permeation chromatograph (hereinafter referred to as GPC) is 2900. The weight average molecular weight of 1 (hereinafter referred to as Mw) was 9900. The average number of epoxy groups contained in one molecule of the polymer (hereinafter referred to as “Fn”) was 6.1.

(Production of polymer 2)

38 parts by mass St, 8 parts by mass butyl acrylate (hereinafter referred to as BA), 25 parts by mass GMA, 29 parts by mass MMA, 15 parts by mass xylene, and 0.3 parts by mass DTBP A polymer 2 was produced in the same manner as the polymer 1 except that the monomer mixture was used. The Mn of the polymer 2 in terms of polystyrene determined by GPC was 2900, and Mw was 10800. The Fn of polymer 2 was 5.1. (Production of polymers 3 and 4)

Polymers 3 and 4 were produced in the same manner as for Polymer 1 except that the monomer composition was changed as shown in Table 1 below. Table 1 shows the Mn, Mw, and Fn of the polymers 3 and 4.

[0067] [Table 1]

[0068] (Preparation of master batch:! -17)

As a masterbatch thermoplastic resin (hereinafter also referred to as vehicle), Easter 6763 (hereinafter referred to as PET-G) manufactured by Eastman Chemical Co., which is an amorphous copolyester resin, was used. 69. 927 parts by weight of PET—30 parts by weight of polymer 1 and 0.075 parts by weight of zinc stearate were prepared and then uniformly premixed using a Henschel mixer. Next, each component was melt-kneaded using the same-direction parallel-shaft twin-screw extruder (ST-40, manufactured by Plastics Engineering Laboratory) to prepare Masterbatch 1. Also, master batches 2 to 17 were prepared by the same method as master batch 1 except that the types and amounts of raw materials were changed as shown in Table 2 below.

[0069] [Table 2]

Thermoplastic resin (A) Polymerization * (B) Catalyst (C- 1) Catalyst (C-2 Carle's xyl f compound (D) Master

Usage Amount Usage Summer Usage Amount Usage 惫 Usage Amount Batch Type Type Type Type Type

(Weighing part) (Material S part) Placement part) (Mass part) (Mass part)

1 PET-G 69.925 Polymer 1 30 St-At 0.075 ― ― ― ―

2 PET-G 69.97 Polymer 1 30 St-AI 0.03 ― ― One

3 PET-G 69.99 Polymer 1 30 St-AI 0.01 ― ― ― ―

4 PET-G 69.97 Polymer 1 30 St-2n 0.03 ― ― ―

5 PET-G 69.95 Polymer 1 30 An- Na 0.05 ― ― ― ―

6 PET-G 69.99 Polymer 1 30 Low-Na 0.01 ― ― ― ―

7 PET-G 69.96 Polymer 1 30 An- Na 0.03 St-Zn 0,003 An-acid 0.007

8 PET-G 64.96 Polymer 2 35 A-0.03 St-Zn 0.003 St-acid 0.007

9 PET-G 64,964 Polymer 2 35 A-0.03 St-Zn 0.003 St-acid 0.003

10 PET-G 64.967 Polymer 3 35 An- Na 0.03 St-Zn 0.003 ― ―

11 PET-G 64.957 Polymer 3 35 A-Na 0.03 St-Zn 0.003 st-acid 0.01

12 PET-G 69.977 Polymer 1 30 An- Na 0.02 St-Zr 0.003 ― ―

13 PET-G 65 Polymer 1 35 ― ― ― ― ―

14 PET-G 65 polymer 2 35 ― ― ― ― ― ― t5 PET-G 65 polymer 3 35 ― ― ― ― ― ―

16 PET-G 69.997 Polymer 1 30 St-Zn 0.003 ― ― ― ―

17 PET-G 69.85 Polymer 1 30 St-At 0.15 One--One

PET-G: Eastman Chemical Company Amorphous Copolyester Resin Easter 6763

St-AI: Aluminum oxalate «SA made by Chemical Industry Co., Ltd.

St-Zn: Zinc stearate Sakai Chemical Industry W SZ

An-Na: Benzoic acid a Fushimi Pharmaceutical Co., Ltd.

An-acid: Benzoic acid Fushimi Pharmaceutical Co., Ltd.

St-acid: powdered stearic acid

[0070] (Production of thermoplastic resin composition 1)

Use the same direction parallel to axis biaxial extruder, carried formulated as shown in Table 3 below Example:! ~ 1 ₄ of the thermoplastic resin composition, and are formulated as shown in Table 4 Comparative Example: Thermoplastic compositions of! ~ 7 were prepared at 280 ° C. In Table 3 and Table 4, "Quantity (X 10 ^_f parts by weight)" is the quantity of component corresponding to the column indicates the numerical X 10- ⁶ parts by der Rukoto in this column.

[0071] [Table 3]

Play _pET Yono pet recycling taste »YPR clear pellets

SUALIN »Aluminum Sakai Chemical Industry SA

Stearin »Zinc << Chemical Industry Legs >> SZ

: Na benzoate Fushimi »藥 ^^ Made

Benzoic acid Fushimi Pharmaceutical

Powder Thealine » [0072] [Table 4]

R-PET: PET recycled from recycled PET (W »YPR clear pellets

St-AJ Stearin »Aluminum Sakai Chemical Industry Co., Ltd. SI SA

St-Zn: Tearic acid Sft «CZ by Chemical Industry

安 ~ Na ：安 & 番麵 Na Fushimi glaze, made

A-: Sabanban St Fushimi Pharmaceutical

St-acid: powder Aric acid

[0073] (Evaluation of moldability of thermoplastic resin composition 1)

The melt viscosity and die swell of each of the thermoplastic resin compositions of Examples 1 to 14 and Comparative Example 17 were measured using a capillary rheometer (Capillograph Model 1C, manufactured by Toyo Seiki Co., Ltd.). In this measurement, together with the pore size used die thickness of 10mm with a lmm, sets the measured temperature to 280 ° C, it was and set the shear rate 182sec ^{_ 1.} The die swell indicates the thickness of the thermoplastic resin composition extruded from the hole of the die, and the larger this value, the easier it is to produce a molded product with better dimensional stability. Examples:! To 14 and Comparative Example 17 The melt viscosity and die swell measurement results of each thermoplastic resin composition are shown in Table 5 below.

[0074] [Table 5]

Viscosity (Pa-s) Daisu I (mm)

Example Ί 617 1.41

Implementation 伢 2 1279 1.52

Implementation 伢 3 664 1.52

Example 4 939 1.63

Example 5 1475 1.67

Example 6 1003 1.71

Example 7 1118 1.76

Implementation 1001 1.90

Implementation defeat 9 1212 1.96

Example 10 380 1.09

Implementation 伢 392 392 1.15

Implementation 伢 12 696 1.37

Example Ϊ3 393 1.02

Example 14 472 1.04

Comparison 1 183 0.82

Comparative Example 2 338 1.34

Comparative Example 3 8Ϊ2 1.79

Comparative Example 4 316 1.04

Comparative Example 5 6t0 1.20

Comparative Example 6 653 1.31

Comparative Example 7 325 1.00

[0075] As shown in Table 5, in Examples:! To 3, those die swells were larger than those in Comparative Example 1, and thus it was confirmed that the melt tension was increased as compared with Comparative Example 1. . In addition, as shown in FIG. 1, in Examples in which the polymer 1 was used as the polymer):! To 3 and Comparative Examples 1 and 6, the concentration of aluminum stearate as the catalyst (C) was 5 × 10 - ⁶ parts by der Ru example 1, the concentration of 25 X 10_ ⁶ parts by mass in an exemplary 2, and example 3 the concentration is 5 X 10- 6 weight parts 37. Daisuueru the same concentration There 0 that X 10- ⁶ Comparative example 2 and the same concentration of parts by weight is larger than that of Comparative example 6 is a 75 X 10_ ⁶ parts by weight was confirmed. In Figure 1, "(X 10- ⁶ parts by mass)" indicates that the concentration of aluminum stearate are each numerical value X 10_ ⁶ parts by weight of the horizontal axis in FIG.

[0076] In Examples 5 to 7 and 12, even when zinc stearate, sodium benzoate, or sodium benzoate and zinc stearate were used as the catalyst (C), the same significant increase as in Example 1 was observed. A viscous effect was confirmed.

[0077] In Examples 8 and 9 in which the polymer 2 was used as the polymer), the thickening effect by the catalyst-added gel was improved as compared with Comparative Example 3 in which the polymer 2 was similarly used. Is confirmed It was.

[0078] In Examples 10 and 11 in which the polymer 3 was used as the polymer (B), the thickening effect by the catalyst addition was improved as compared with Comparative Example 4 in which the polymer 3 was similarly used. Has been confirmed.

[0079] In Examples 13 and 14 in which the polymer 4 was used as the polymer (B), the thickening effect by the catalyst addition was improved as compared with Comparative Example 7 in which the polymer 4 was similarly used. Has been confirmed.

(Manufacture of thermoplastic resin composition 2)

Using the same direction parallel shaft twin screw extruder, the thermoplastic resins of Example 15 and Comparative Examples 8 and 9 blended as shown in Table 6 below were prepared at 200 ° C.

(Evaluation of moldability of thermoplastic resin composition 2)

The melt viscosity and die swell of each of the thermoplastic resin compositions of Example 15 and Comparative Examples 8 and 9 were measured using a capillary rheometer (Capillograph 1C type manufactured by Toyo Seiki Co., Ltd.). In this measurement, a die having a hole diameter of 1 mm and a thickness of 10 mm was used, the measurement temperature was set to 200 ° C, and the shear rate was set to 182 sec- ¹ . Table 6 below shows the measurement results of melt viscosity and diewell of the thermoplastic resin compositions of Example 15 and Comparative Examples 8 and 9.

[0080] [Table 6]

PLA: Polylactic acid resin Toyoda Motor Corp. PLA # 5403

St-Zn: Zinc stearate Sakai Chemical Industry Co., Ltd. SZ

[0081] As shown in Table 6, the melt viscosity of Example 15 containing polymer 1 and zinc stearate as catalyst (C) was as follows: Comparative Example 8 containing no polymer 1 and catalyst (C); It was confirmed that it was higher than that of Comparative Example 9 containing polymer 1 but not containing catalyst (C).

Claims

The scope of the claims

[1] Reaction of a thermoplastic resin (A) having a functional group having reactivity with an epoxy group, a polymer (B) having an epoxy group, a functional group having reactivity with an epoxy group, and an epoxy group The content of the polymer () containing the catalyst (C) that promotes the polymerization is set to 0.:! To 5 parts by mass per 100 parts by mass of the thermoplastic resin (A), and the content of the catalyst (C) is , the thermoplastic resin (a) 100 parts by mass of per 1. 0 X 10 one ^⁶ ~ 50 X 10- ⁶ thermoplastic resin composition which is set in parts by weight.

[2] The thermoplastic resin (A) is at least one selected from the group consisting of a polyester resin, a polycarbonate resin, a polyamide resin, a polyphenylene ether resin, and a polylactic acid resin. Thermoplastic resin composition.

[3] The thermoplastic resin composition according to [1], wherein the polymer (B) is a vinyl polymer having an epoxy group.

[4] The average number of epoxy groups in the polymer (B) is 1.

2. The thermoplastic resin composition according to claim 1, wherein the number is two or more.

[5] The thermoplastic resin composition according to claim 1, wherein the polymer (B) has a number average molecular weight of 300 to 30,000.

6. The thermoplastic resin composition according to claim 1, wherein the catalyst (C) is a carboxylic acid metal salt compound.

7. The thermoplastic resin composition according to claim 6, wherein the catalyst (C) is a benzoic acid metal salt compound or a stearic acid metal salt compound.

[8] The thermoplastic resin composition further comprises a compound (D) different from the thermoplastic resin (A), having one carboxylate group, and the content of the compound (D) is: thermoplastic resin (a) 100 parts by mass of per 0. 3 X 10 one ⁶ ~ 10 X thermoplastic resin composition according to claim 1 which is set to 10 ⁶ parts by weight.

[9] The thermoplastic resin composition according to claim 8, wherein the compound (D) is benzoic acid or stearic acid.

[10] The thermoplastic resin composition has a master batch, and the master batch contains a part of the thermoplastic resin (A), a polymer (B), a catalyst (C), and a compound (D). And that trout The thermoplastic resin composition is prepared by mixing the tarbatch and the remainder of the thermoplastic resin (A),

The total content of the thermoplastic resin (A), polymer (B), catalyst (C), and compound (D) in the masterbatch is 30-85 per 100 parts by mass. The thermoplastic resin composition according to claim 8, wherein the thermoplastic resin composition is set to 15 parts by mass and the total content of the polymer (B), the catalyst (C), and the compound (D) is set to 15 to 70 parts by mass. .

[11] The thermoplastic resin composition further contains a thermoplastic resin (E) different from the thermoplastic resin (A), and among the thermoplastic resins (A) and (E), a thermoplastic resin ( Only A) has a functional group having reactivity with an epoxy group, and the thermoplastic resin composition has a masterbatch. The masterbatch includes the polymer (B), the catalyst (C), the compound ( D), and a thermoplastic resin (E), a thermoplastic resin composition is prepared by mixing the masterbatch and the thermoplastic resin (A),

Polymer (B), catalyst (C), and compound per 100 parts by mass of the total content of polymer (B), catalyst (C), compound (D), and thermoplastic resin (E) in the masterbatch The thermoplastic resin composition according to claim 8, wherein the total content of (D) is set to 15 to 70 parts by mass, and the content of the thermoplastic resin (E) is set to 30 to 85 parts by mass. object.

12. The thermoplastic resin composition according to claim 11, wherein the thermoplastic resin (E) is at least one selected from the group consisting of a polyolefin resin and a polystyrene resin.

[13] Claim: A molded product obtained by molding the thermoplastic resin composition according to any one of! To 12.

[14] A molded article obtained by extrusion molding of the thermoplastic resin composition according to any one of claims 1 to 12.