JP2010180365A - Thermoplastic resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition in which a fluororesin and a thermoplastic resin free of fluorine are uniformly dispersed. <P>SOLUTION: The thermoplastic resin composition comprises: a fluororesin having at least one functional group selected from the group consisting of a carbonyl group, an olefin group and an amino group at the main-chain terminal or side-chain terminal of the polymer; a thermoplastic resin free of fluorine having a reactive functional group at the main-chain terminal or side-chain terminal of the polymer; and a multifunctional compound. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a thermoplastic resin composition and a molded article.

Fluororesin is excellent in properties such as slidability, heat resistance, chemical resistance, weather resistance, and electrical properties, and is used in a wide range of fields such as automobiles, industrial machinery, OA equipment, and electrical and electronic equipment. On the other hand, there is a problem that the mechanical strength is generally insufficient, the specific gravity is large, and the cost is high. Therefore, it is known to use a resin mixture (resin blend) in which non-fluorine thermoplastic resin is added to fluororesin in order to give mechanical strength to fluororesin, to reduce specific gravity, and to reduce price. It has been. However, since the fluororesin and the non-fluorine thermoplastic resin have poor affinity and cannot be mixed evenly by simply melt-kneading the two, the mechanical properties are not sufficiently improved even if the non-fluorine thermoplastic resin is mixed. There is a problem.

As a composition in which the dispersibility of these two resins is improved, Patent Document 1 discloses that a fluorine-containing ethylenic polymer having a reactive functional group at the main chain terminal and / or side chain terminal and a non-bonding site. A resin composition comprising a fluorothermoplastic resin, in which a reactive functional group and a bond-forming site are bonded, is described.

Patent Document 2 discloses a resin comprising a fluoropolymer having a reactive functional group at the main chain end and / or side chain end and a non-fluorine thermoplastic resin having a fuel permeability coefficient of 5 g · mm / m ² · day or less. A composition is described.

JP 2003-176394 A JP 2006-328195 A

However, the conventional technology has not completely overcome the incompatibility between the fluororesin and the non-fluorine-containing thermoplastic resin, and further improvement in dispersibility has been demanded.

In view of the current situation, an object of the present invention is to provide a thermoplastic resin composition in which a fluororesin and a fluorine-free thermoplastic resin are uniformly dispersed.

The present invention relates to a fluororesin having at least one functional group selected from the group consisting of a carbonyl group, an olefin group and an amino group at the main chain terminal or side chain terminal of the polymer, and at the main chain terminal or side chain terminal of the polymer. The present invention relates to a thermoplastic resin composition comprising a fluorine-free thermoplastic resin having a reactive functional group and a polyfunctional compound.

Fluorine-free thermoplastic resin is hydroxyl group, silanol group, carboxyl group, ester group, carbonate group, haloformyl group, formyl group, amino group, amide group, imide group, mercapto group, thiolate group, thiol group, sulfonic acid group It preferably has at least one reactive functional group selected from the group consisting of oxazolyl group, epoxy group and glycidyl group.

The polyfunctional compound has at least one reactive functional group selected from the group consisting of carbonyl group, carboxyl group, haloformyl group, amide group, olefin group, amino group, isocyanate group, hydroxy group and epoxy group. preferable.

The polyfunctional compound is preferably an aromatic amine compound.

The polyfunctional compound is preferably an aromatic amine compound having at least one substituent selected from the group consisting of a fluoroalkyl group and a fluorophenyl group.

It is preferable that the mass ratio of the fluororesin and the fluorine-free thermoplastic resin is 80:20 to 20:80.

The fluororesin is at least one selected from the group consisting of a copolymer composed of ethylene and tetrafluoroethylene, a copolymer composed of chlorotrifluoroethylene and tetrafluoroethylene, and a copolymer composed of tetrafluoroethylene and hexafluoropropylene. Preferably it is a seed.

The fluorine-free thermoplastic resin is preferably at least one selected from the group consisting of polyester, polycarbonate, modified polyolefin, and ethylene / vinyl alcohol copolymer.

The present invention also relates to a molded article comprising the thermoplastic resin composition.

The present invention is described in detail below.

Since the thermoplastic resin composition of the present invention contains a fluororesin having a specific functional group, a fluorine-free thermoplastic resin having a reactive functional group, and a polyfunctional compound, it is inherently inferior in affinity. The fluororesin and the non-fluorine-containing thermoplastic resin are uniformly dispersed in the thermoplastic resin composition. Therefore, the fluororesin and the non-fluorine-containing thermoplastic resin are each very high without impairing the excellent characteristics of each. A molded product having mechanical strength can be obtained.

In the thermoplastic resin composition of the present invention, the fluororesin, the non-fluorine-containing thermoplastic resin and the polyfunctional compound may be present alone without bonding with each molecule, and the respective functional groups react with each other. By doing so, they may exist in combination with each other, or may exist in combination with those that exist alone.

It is preferable that the fluororesin, the fluorine-free thermoplastic resin, and the polyfunctional compound are bonded to each other by reacting each functional group. The polyfunctional compound functions to uniformly mix the fluororesin and the non-fluorine-containing thermoplastic resin by reacting with the functional group of the fluororesin or the reactive functional group of the non-fluorine-containing thermoplastic resin. It is guessed.

The polyfunctional compound is a compound having two or more reactive functional groups of the same or different types in one molecule.

The polyfunctional compound has at least one reactive functional group selected from the group consisting of carbonyl group, carboxyl group, haloformyl group, amide group, olefin group, amino group, isocyanate group, hydroxy group and epoxy group. preferable.

Specific examples of the polyfunctional compound include
Hexamethylenediamine carbamate, N, N′-dicinnamylidene-1,6-hexamethylenediamine, 4,4′-bis (aminocyclohexyl) methanecarbamate, 4,4′-diaminodiphenyl ether [4,4′-DPE], 2 , 2-bis [4- (4-aminophenoxy) phenyl] propane [BAPP], p-phenylenediamine, m-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, N, N′-dimethyl- 1,4-phenylenediamine, 4,4′-methylenedianiline, dianilinoethane, 4,4′-methylene-bis (3-nitroaniline), 4,4′-methylene-bis (2-chloroaniline), diaminopyridine , Melamine, 4-aminophenol, 3,4'-diaminodiphenyl ether [3,4'-DPE], 2,4,4′-triaminodiphenyl ether [TADE], 2,3′-diaminodiphenyl ether [2,3′-DPE], 2,5-bis (4-aminophenoxy) -biphenyl [P-TPE-Q] 1,4-bis (4-aminophenoxy) -2,3,5-trimethylbenzene [TMBAB], 4,4′-diamino-2- (trifluoromethyl) diphenyl ether [TFDPE], and other amine compounds,
Triallyl cyanurate, triallyl isocyanurate [TAIC], trimethallyl isocyanurate, TAIC prepolymer, triacryl formal, triallyl trimellitate, N, N′-n-phenylenebismaleimide, dipropargyl terephthalate, diallyl phthalate , Tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1,3,5-tris (2,3,3-trifluoro-2-propenyl) -1,3,5-triazine- 2,4,6-trione), tris (diallylamine) -S-triazine, triallyl phosphite, N, N-diallylacrylamide, 1,6-divinyldodecafluorohexane, hexaallylphosphoramide, N, N, N ', N'-tetraa Rutetraphthalamide, N, N, N ′, N′-tetraallylmalonamide, trivinyl isocyanurate, 2,4,6-trivinylmethyltrisiloxane, tri (5-norbornene-2-methylene) cyanurate, tri Olefin compounds such as allyl phosphite,
Epoxy compounds such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, polyfunctional epoxy resin,
2,2-bis (4-hydroxyphenyl) propane [bisphenol A], 2,2-bis (4-hydroxyphenyl) perfluoropropane (hereinafter referred to as bisphenol AF), resorcin, 1,3-dihydroxybenzene, 1, 7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxystilbene, 2,6-dihydroxyanthracene, hydroquinone, catechol, 2,2- Bis (4-hydroxyphenyl) butane [bisphenol B], 4,4-bis (4-hydroxyphenyl) valeric acid, 2,2-bis (4-hydroxyphenyl) tetrafluorodichloropropane, 4,4′-dihydroxydiphenyl Sulfone, 4,4'-dihydroxy Hydroxy compounds such as sidiphenyl ketone, tri (4-hydroxyphenyl) methane, 3,3 ′, 5,5′-tetrachlorobisphenol A, 3,3 ′, 5,5′-tetrabromobisphenol A, etc. It is done.

The polyfunctional compound is N, N′-dicinnamylidene-1,6-hexamethylenediamine, 4,4′-DPE, BAPP, bisphenol AF, 3,4′-DPE, TADE, 2,3′-DPE, P -It is preferable that it is at least 1 sort (s) selected from the group which consists of TPE-Q, TMBAB, and TFDPE.

The polyfunctional compound is preferably an aromatic amine compound from the viewpoint of excellent affinity with a fluororesin, and at least one substituent selected from the group consisting of a fluoroalkyl group and a fluorophenyl group. It is more preferable that it is an aromatic amine compound having

These polyfunctional compounds may be used alone or in any combination with polyfunctional compounds having other structures.

The polyfunctional compound is particularly preferably an aromatic asymmetric polyfunctional compound from the viewpoint that the increase in melt viscosity of the thermoplastic resin composition is small, foaming during molding can be suppressed, and moldability is excellent. .

The aromatic asymmetric polyfunctional compound is an organic compound having at least one aromatic ring in one molecule and having two or more reactive functional groups of the same or different types. A compound having an unsymmetrical structure. Even if the reactive functional groups possessed by the compounds having an asymmetric structure are of the same type, the reactivity differs from each other due to the difference in the bonding position in the molecule. N, N′-dicinnamylidene-1,6-hexamethylenediamine, 4,4′-DPE, BAPP, bisphenol AF and the like are compounds having an aromatic ring and having two or more amino groups or hydroxyl groups. The symmetric polyfunctional compound is not included in the aromatic asymmetric polyfunctional compound.

Examples of the aromatic asymmetric polyfunctional compound include 3,4′-diaminodiphenyl ether [3,4′-DPE], 2,4,4′-triaminodiphenyl ether [TADE], 2,3′-diaminodiphenyl ether [ 2,3′-DPE], 2,5-bis (4-aminophenoxy) -biphenyl [P-TPE-Q], the following chemical formula

2,2-bis (3,4'-hydroxyphenyl) perfluoropropane represented by the following general formulas (1) to (3)

(In the formula, R ¹ represents an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group, and when having a plurality of R ^{1 s} , they may be the same or different.)
And a diamine compound represented by the following general formula (4):

(In the formula, each R ² is the same or different and represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a fluoroalkyl group having 1 to 3 carbon atoms, and at least one of the four R ² is fluoroalkyl. Group.)
It is preferable that it is at least 1 sort (s) selected from the group which consists of diamine compound represented by these.

Examples of the diamine compound represented by the general formulas (1) to (3) include 1,4-bis (4-aminophenoxy) -2,3,5-trimethylbenzene [TMBAB] and the like. Examples of the diamine compound represented by (4) include 4,4′-diamino-2- (trifluoromethyl) diphenyl ether [TFDPE].

The aromatic asymmetric polyfunctional compound is preferably a diamine compound having a fluoroalkyl group or a fluorophenyl group from the viewpoint of excellent affinity with a fluororesin, and 2,2-bis (3,4′- More preferably, it is at least one selected from the group consisting of hydroxyphenyl) perfluoropropane and the diamine compounds represented by the general formulas (1) to (4), and is selected from the group consisting of TMBAB and TFDPE. More preferably, it is at least one.

The polyfunctional compound is preferably 0.05 to 10.0 parts by mass, and preferably 0.06 to 5.0 parts by mass with respect to 100 parts by mass of the fluororesin and the fluorine-free thermoplastic resin. If the blending amount of the polyfunctional compound is too small, the fluororesin and the fluorine-free thermoplastic resin may not be sufficiently mixed. If the blending amount is too large, the polyfunctional compound is not sufficiently dispersed and the mechanical properties of the molded product are deteriorated. There is a risk of lowering or foaming during molding.

The fluororesin has at least one functional group selected from the group consisting of a carbonyl group, an olefin group, and an amino group at the main chain end or side chain end of the polymer.

A carbonyl group is a functional group having —C (═O) —.

Specifically, for example,
Carbonate group [—O—C (═O) —OR ³ (wherein R ³ is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms including an etheric oxygen atom) ],
A haloformyl group [—C (═O) X ¹ , X ¹ is a halogen atom],
Formyl group [—C (═O) H],
Formula: —R ⁴ —C (═O) —R ⁵ (wherein R ⁴ is a divalent organic group having 1 to 20 carbon atoms, and R ⁵ is a monovalent group having 1 to 20 carbon atoms. An organic group of
Formula: —O—C (═O) —R ⁶ (wherein R ⁶ is an alkyl group having 1 to 20 carbon atoms or an alkyl group having 2 to 20 carbon atoms including an etheric oxygen atom) A group represented by
Carboxyl group [—C (═O) OH],
An alkoxycarbonyl group [—C (═O) OR ⁷ (wherein R ⁷ is a monovalent organic group having 1 to 20 carbon atoms)],
Carbamoyl group [—C (═O) NR ⁸ R ⁹ (wherein R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms) )],
Acid anhydride bond [—C (═O) —O—C (═O) —],
An isocyanate group [—N═C═O],
Etc.

Specific examples of R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Specific examples of R ⁴ include a methylene group, —CF ₂ — group, —C ₆ H ₄ — group, and specific examples of R ⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, Examples thereof include a butyl group. Specific examples of R ⁷ include methyl group, ethyl group, propyl group, isopropyl group, butyl group and the like. Specific examples of R ⁸ and R ⁹ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a phenyl group.

Among these carbonyl groups, at least one selected from the group consisting of a carboxyl group, a haloformyl group, an alkoxycarbonyl group, and a carbonate group from the viewpoint of ease of introduction into a fluororesin and reactivity with other materials. And at least one selected from the group consisting of —COOH, —OC (═O) OCH ₂ CH ₂ CH ₃ , —COF, and —OC (═O) OCH (CH ₃ ) _2. More preferably.

An olefin group is a functional group having a carbon-carbon double bond. As the olefin group, the following formula:
-CR ¹⁰ = CR ¹¹ R ¹²
(Wherein R ¹⁰ , R ¹¹ and R ¹² may be the same or different and are a hydrogen atom, a fluorine atom or a monovalent organic group having 1 to 20 carbon atoms). functional group can be mentioned _{that, -CF = CF 2, -CH =} CF 2, it is preferably at least one -CF = CHF, selected from the group consisting of -CF = CH ₂ and -CH = CH ₂ .

An amino group is a monovalent functional group obtained by removing hydrogen from ammonia, primary or secondary amine. As an amino group, the following formula:
-NR ¹³ R ¹⁴
(Wherein, R ¹³ and R ¹⁴ may be the same or different and are a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms). , —NH ₂ , —NH (CH ₃ ), —N (CH ₃ ) ₂ , —NH (CH ₂ CH ₃ ), —N (C ₂ H ₅ ) ₂ , and —NH (C ₆ H ₅ ) It is preferably at least one selected from the group consisting of

The number of terminal groups of the fluororesin can be measured by the methods described in JP-B-37-3127 and WO99 / 45044. For example, when an infrared absorption spectrum analysis of a fluororesin film sheet is performed using an infrared spectrophotometer and the number of functional groups is measured from an absorption band having a frequency specific to the functional group, for example, the —COF terminal is 1884 cm ^{− 1} absorption bands, -COOH ends are absorption bands of 1813 cm ^-1 and 1775 cm ^-1 , -COOCH ₃ ends are absorption bands of 1795 cm ^-1 , -CONH ₂ ends are absorption bands of 3438 cm ^-1 , -CH ₂ OH ends are The absorption band at 3648 cm ^−1, the —CF═CF ₂ end can be calculated from the absorption band at 1790 cm ⁻¹ .

The method for introducing the functional group into the fluororesin is not particularly limited. For example, a method of copolymerizing a monomer having the functional group at the time of fluororesin polymerization, the functional group or a functional group that can be converted to the functional group. A method of polymerizing using a polymerization initiator having a polymer, a method of introducing the above functional group into a fluororesin by a polymer reaction, a method of thermally decomposing a polymer main chain in the presence of oxygen, a strong shear force such as a twin screw extruder And a method for converting the terminal of the fluororesin using a device capable of adding.

Monomers having the above functional groups include (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, citraconic anhydride, mesaconic acid And aliphatic unsaturated carboxylic acids such as mesaconic anhydride, aconitic acid, and aconitic anhydride.

The number of functional groups of the fluororesin is preferably 20 to 5000 per 1 million carbon atoms constituting the fluororesin, more preferably 30 to 4000, and 40 to 3000. Further preferred. If the number is less than 20, the compatibility between the fluororesin and the fluorine-free thermoplastic resin tends not to be improved, and if it exceeds 5000, foaming tends to occur in the molded product.

The fluororesin having the functional group used in the present invention is not only composed of molecules having the functional group at one end, both ends or side chains of the main chain in one polymer, It may be a mixture of a molecule having the functional group at one end, both ends or side chains of the main chain, and a molecule not containing the functional group.

Although it does not specifically limit as said fluororesin, It is preferable that it is a fluororesin containing at least 1 type of fluorine-containing ethylenic polymer. The fluorinated ethylenic polymer preferably has a structural unit derived from at least one fluorinated ethylenic monomer. Examples of the fluorine-containing ethylenic monomer include tetrafluoroethylene [TFE], formula (5):
CF ₂ = CF-R _f ¹ (5)
(In the formula, R _f ¹ represents —CF ₃ or —OR _f ^2. R _f ² represents a perfluoroalkyl group having 1 to 5 carbon atoms.)
One or more perfluoroolefins such as perfluoroethylenically unsaturated compounds represented by: chlorotrifluoroethylene [CTFE], trifluoroethylene, hexafluoroisobutene, vinylidene fluoride [VdF], vinyl fluoride Equation (6):
^{_{CH 2 = CX 2 (CF 2}} ) n X 3 (6)
(In the formula, X ² represents a hydrogen atom or a fluorine atom, X ³ represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 1 to 10.)
And the like.

The fluororesin may have a structural unit derived from a monomer copolymerizable with the fluorine-containing ethylenic monomer. Examples of such a monomer include those other than the fluoroolefin and perfluoroolefin. Non-fluorine ethylenic monomers can be mentioned. Examples of the non-fluorine ethylenic monomer include ethylene, propylene, and alkyl vinyl ethers. Here, the alkyl vinyl ether refers to an alkyl vinyl ether having an alkyl group having 1 to 5 carbon atoms.

The fluororesin is easy to process the thermoplastic resin composition, and the resulting molded product has excellent heat resistance, chemical resistance and oil resistance.
(1) Ethylene / TFE copolymer consisting of ethylene and TFE [ETFE]
(2) TFE and equation (5):
CF ₂ = CF-R _f ¹ (5)
(In the formula, R _f ¹ represents —CF ₃ or —OR _f ^2. R _f ² represents a perfluoroalkyl group having 1 to 5 carbon atoms.)
A copolymer comprising one or more perfluoroethylenically unsaturated compounds represented by the formula, for example, a copolymer [PFA] comprising TFE and perfluoro (alkyl vinyl ether) [PAVE] or TFE and hexafluoropropylene Copolymer comprising [HFP] [FEP]
(3) TFE, ethylene and formula (5):
CF ₂ = CF-R _f ¹ (5)
(Wherein, R _f ¹ is —CF ₃ or —OR _f ² , and R _f ² is a perfluoroalkyl group having 1 to 5 carbon atoms). Ethylene-TFE-HFP copolymer, ethylene-TFE-perfluoroethylenically unsaturated compound copolymer (4) polyvinylidene fluoride [PVDF]
(5) Copolymer comprising CTFE and TFE [CTFE / TFE copolymer]
It is preferable that the fluorine-containing ethylenic polymer represented by (1), (2), or (5) is more preferable.

The fluororesin is preferably at least one selected from the group consisting of ETFE, CTFE / TFE copolymer, PFA and FEP, and is selected from the group consisting of ETFE, CTFE / TFE copolymer and FEP. More preferably, it is at least one kind.

ETFE
ETFE is preferable in terms of improving mechanical properties and fuel barrier properties. The content molar ratio of the TFE unit to the ethylene unit is preferably 20:80 to 90:10, more preferably 38:62 to 85:15, and particularly preferably 37:63 to 80:20.

ETFE may be a copolymer composed of TFE, ethylene, and a monomer copolymerizable with TFE and ethylene. As the copolymerizable monomer, the following formulas CH ₂ = CX ⁴ R _f ³ , CF ₂ = CFR _f ³ , CF ₂ = CFOR _f ³ , CH ₂ = C (R _f ³ ) ₂
(Wherein, X ⁴ represents a hydrogen atom or a fluorine atom, and R _f ³ represents a fluoroalkyl group which may contain an etheric oxygen atom)
Among them, a fluorine-containing vinyl monomer represented by CH ₂ = CX ⁴ R _f ³ is preferable, and CH ₂ in which R _f ³ is a fluoroalkyl group having 1 to 8 carbon atoms. The fluorine-containing vinyl monomer represented by = CX ⁴ R _f ³ is more preferable.

Specific examples of the fluorine-containing vinyl monomer represented by the above formula include 1,1-dihydroperfluoropropene-1, 1,1-dihydroperfluorobutene-1, 1,1,5-trihydroperfluoropentene-1. 1,1,7-trihydroperfluoroheptene-1,1,1,2-trihydroperfluorohexene-1,1,1,2-trihydroperfluorooctene-1,2,2,3 3,4,4,5,5-octafluoropentyl vinyl ether, perfluoro (methyl vinyl ether), perfluoro (propyl vinyl ether), hexafluoropropene, perfluorobutene-1, 3,3,3-trifluoro-2- (trifluoromethyl) propene -1,2,3,3,4,4,5,5- heptafluoro-1-pentene _(CH 2 = CFC ₂ CF ₂ CF ₂ H), and the like.

The monomer copolymerizable with TFE and ethylene may be an aliphatic unsaturated carboxylic acid such as itaconic acid or itaconic anhydride described above.

The monomer copolymerizable with TFE and ethylene is preferably 0.1 to 10 mol%, more preferably 0.1 to 5 mol%, and more preferably 0.2 to 4 mol% with respect to the fluorine-containing ethylenic polymer. Is particularly preferred.

CTFE / TFE copolymer The CTFE / TFE copolymer preferably has a CTFE / TFE unit molar ratio of CTFE: TFE = 2: 98 to 98: 2 and 5:95 to 90:10. It is more preferable. If the CTFE unit is less than 2 mol%, the chemical permeability tends to deteriorate and the melt processing tends to be difficult, and if it exceeds 98 mol%, the heat resistance and chemical resistance during molding may deteriorate.

CTFE / TFE copolymer, CTFE, TFE, and may be a copolymer comprising CTFE and TFE monomer copolymerizable with _{ethylene, VdF, HFP, CF 2 =} CF-OR f 4 (Wherein R _f ⁴ represents a perfluoroalkyl group having 1 to 5 carbon atoms.) Represented by perfluoro (alkyl vinyl ether) [PAVE], CX ⁵ X ⁶ = CX ⁷ (CF ₂ ) _n X ⁸ (Wherein X ⁵ , X ⁶ and X ⁷ are the same or different and represent a hydrogen atom or a fluorine atom, X ⁸ represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 2 to 10) And a vinyl monomer represented by CF ₂ ═CF—OCH ₂ —Rf ⁵ (wherein Rf ⁵ represents a perfluoroalkyl group having 1 to ⁵ carbon atoms). Perfluorovinyl Examples include ether derivatives, among which PAVE is preferable.

The PAVE is selected from the group consisting of perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], and perfluoro (butyl vinyl ether). It is preferably at least one, and more preferably at least one selected from the group consisting of PMVE, PEVE and PPVE.

As the alkyl perfluorovinyl ether derivative, those in which Rf ⁵ is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF ₂ = CF—OCH ₂ —CF ₂ CF ₃ is more preferable.

The CTFE / TFE copolymer has a monomer unit derived from CTFE and a monomer copolymerizable with TFE in an amount of 0.1 to 10 mol%, and a total of CTFE units and TFE units of 90 to 99.99. It is preferably 9 mol%. If the copolymerizable monomer unit is less than 0.1 mol%, the moldability, environmental stress crack resistance and stress crack resistance tend to be inferior, and if it exceeds 10 mol%, the chemical solution has low permeability, heat resistance, machine It tends to be inferior in characteristics and productivity.

FEP
FEP is particularly preferable in that it has excellent heat resistance and exhibits excellent fuel barrier properties. Although it does not specifically limit as FEP, It is preferable that it is a copolymer which consists of 70-99 mol% of TFE units and 1-30 mol% of HFP units, 80-97 mol% of TFE units, and 3-20 mol% of HFP units. More preferably, it is a copolymer comprising If the TFE unit is less than 70 mol%, the mechanical properties tend to decrease, and if it exceeds 99 mol%, the melting point becomes too high and the moldability tends to decrease.

FEP may be a copolymer comprising TFE, HFP, and a monomer copolymerizable with TFE and HFP, and the monomer is exemplified as a monomer copolymerizable with CTFE and TFE. Monomer may be used. As the monomer, perfluoro (alkyl vinyl ether) [PAVE] represented by CF ₂ = CF—OR _f ⁴ (wherein R _f ⁴ represents a perfluoroalkyl group having 1 to 5 carbon atoms). , CX ⁵ X ⁶ = CX ⁷ (CF ₂ ) _n X ⁸ (wherein X ⁵ , X ⁶ and X ⁷ are the same or different and represent a hydrogen atom or a fluorine atom, and X ⁸ represents a hydrogen atom, fluorine represents an atom or a chlorine atom, n represents a vinyl monomer represented by the representative.) the integer from 2 to 10, _{and, CF 2 = CF-OCH 2} -Rf 5 ( wherein, Rf ⁵ is 1 to carbon atoms 5 represents a perfluoroalkyl group, and the like. Among them, PAVE is preferable.

The PAVE is selected from the group consisting of perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], and perfluoro (butyl vinyl ether). It is preferably at least one, and more preferably at least one selected from the group consisting of PMVE, PEVE and PPVE.

As the alkyl perfluorovinyl ether derivative, those in which Rf ⁵ is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF ₂ = CF—OCH ₂ —CF ₂ CF ₃ is more preferable.

FEP has 0.1 to 10 mol% of monomer units derived from monomers copolymerizable with TFE and HFP, and 90 to 99.9 mol% of TFE units and HFP units in total. Is preferred. If the copolymerizable monomer unit is less than 0.1 mol%, the moldability, environmental stress crack resistance and stress crack resistance tend to be inferior, and if it exceeds 10 mol%, the chemical solution has low permeability, heat resistance, machine It tends to be inferior in characteristics and productivity.

PFA
PFA is particularly preferable in that it has excellent heat resistance and exhibits excellent fuel barrier properties. Although it does not specifically limit as PFA, It is preferable that it is a copolymer which consists of 70-99 mol% of TFE units and 1-30 mol% of PAVE units, 80-97 mol% of TFE units, and 3-20 mol% of PAVE units. More preferably, it is a copolymer comprising If the TFE unit is less than 70 mol%, the mechanical properties tend to decrease, and if it exceeds 99 mol%, the melting point becomes too high and the moldability tends to decrease.

The PAVE is selected from the group consisting of perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], and perfluoro (butyl vinyl ether). It is preferably at least one, more preferably at least one selected from the group consisting of PMVE, PEVE and PPVE, and even more preferably PMVE.

PFA may be a copolymer composed of TFE, PAVE, and a monomer copolymerizable with TFE and PAVE, and the monomer is exemplified as a monomer copolymerizable with CTFE and TFE. Monomer may be used. HFP, CX ⁵ X ⁶ = CX ⁷ (CF ₂ ) _n X ⁸ (wherein X ⁵ , X ⁶ and X ⁷ are the same or different and represent a hydrogen atom or a fluorine atom, and X ⁸ represents a hydrogen atom, represents a fluorine atom or a chlorine atom, a vinyl monomer n is represented by the representative.) the integer from 2 to 10, _{and, CF 2 = CF-OCH 2} -Rf 5 ( wherein, Rf ⁵ is C 1 -C An alkyl perfluorovinyl ether derivative represented by ˜5).

As the alkyl perfluorovinyl ether derivative, those in which Rf ⁵ is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF ₂ = CF—OCH ₂ —CF ₂ CF ₃ is more preferable.

PFA has a monomer unit derived from a monomer copolymerizable with TFE and PAVE in an amount of 0.1 to 10 mol%, and a total of TFE unit and PAVE unit is 90 to 99.9 mol%. Is preferred. If the copolymerizable monomer unit is less than 0.1 mol%, the moldability, environmental stress crack resistance and stress crack resistance tend to be inferior, and if it exceeds 10 mol%, the chemical solution has low permeability, heat resistance, machine It tends to be inferior in characteristics and productivity.

The melting point of the fluororesin is preferably 150 to 340 ° C, more preferably 150 to 330 ° C, and further preferably 170 to 320 ° C. If the melting point of the fluororesin is less than 150 ° C., the heat resistance may be lowered. If the melting point exceeds 340 ° C., the functional group is thermally deteriorated under the melting condition of the fluororesin, so that the fluororesin and the fluorine-free material are not contained. There is a possibility that compatibility with the thermoplastic resin may not be improved.

When the thermoplastic resin composition of the present invention is used for fuel applications such as a fuel tube, a fuel hose, a fuel container, and a fuel container sealing material, the fuel permeability coefficient when the fluororesin sheet is used is 20 (g · ^{mm) /} preferably (m 2 · day) or less, 15 (g · ^{mm) /} more preferably (m 2 · day) or less, 10 (g · mm) / (m 2 · Day) or less, more preferably 5 (g · mm) / (m ² · day) or less. The lower limit value of the fuel permeability coefficient is not particularly limited, and the lower the value, the better. When the fuel permeation coefficient exceeds 20 (g · mm) / (m ² · day), the fuel permeation resistance is low. Therefore, in order to suppress the fuel permeation amount, it is necessary to increase the thickness of the molded product. Economically unfavorable. Note that the lower the fuel permeation coefficient, the better the fuel permeation prevention capability. On the other hand, when the fuel permeation coefficient is large, the fuel easily permeates, so it is not suitable as a molded product such as a fuel tube.

The fuel permeability coefficient is measured by a method according to the cup method in the moisture permeability test method for moisture-proof packaging materials. Here, the cup method is a moisture permeability test method defined in JIS Z 0208, and is a method for measuring the amount of water vapor that passes through a membranous substance of a unit area in a certain time. In the present invention, the fuel permeation coefficient is measured according to this cup method. As a specific method, CE10 (toluene / isooctane / ethanol = 45/45/10 vol%) as a simulated fuel is placed in a SUS container (open area: 1.26 × 10 ⁻³ m ² ) having a volume of 20 mL. Put 18 mL, and set the sheet-like test piece in the container open part and seal it to make a test body. The test specimen is placed in a thermostatic device (60 ° C.), the weight of the test specimen is measured, and when the weight loss per unit time becomes constant, the fuel permeability is obtained by the following formula.

Although it does not specifically limit as a manufacturing method of the said fluororesin, The method as described in Unexamined-Japanese-Patent No. 2005-298702, international publication 2005/100420 pamphlet, etc. can be mention | raise | lifted.

The fluorine-free thermoplastic resin is a polymer having no fluorine atom bonded to a carbon atom constituting the main chain, and has at least one reactive functional group at the main chain end or side chain end of the polymer. .

Examples of the reactive functional group include a hydroxyl group (hydroxyl group), a silanol group, a carboxyl group, an ester group, a carbonate group, a haloformyl group (—C (═O) X ¹ , X ¹ is a halogen atom), and a formyl group (—C (= O) H), at least one selected from the group consisting of amino group, amide group, imide group, mercapto group, thiolate group, thiol group, sulfonic acid group, oxazolyl group, epoxy group, and glycidyl group Preferably there is. The carboxyl group and sulfonic acid group may be acid type or salt type.

Examples of the fluorine-free thermoplastic resin include polyester, polycarbonate, polyolefin, modified polyolefin, ethylene / vinyl alcohol copolymer, polyphenylene sulfide, acrylic, vinyl acetate, vinyl chloride, styrene, polyurethane, acrylonitrile butadiene styrene. Copolymer [ABS], polyether ether ketone [PEEK], polyether sulfone [PES], polysulfone, polyether phenyl oxide [PPO], polyacetal, polyether imide, silicone resin, epoxy resin, phenol resin, unsaturated Examples thereof include polyester and cellophane.

The fluorine-free thermoplastic resin is preferably at least one selected from the group consisting of polyester, polycarbonate, modified polyolefin, and ethylene / vinyl alcohol copolymer.

Polyesters include polyethylene terephthalate [PET], polybutylene terephthalate [PBT], polytrimethylene terephthalate [PTT], polyethylene naphthalate [PEN], polybutylene naphthalate [PBN], parahydroxybenzoic acid / ethylene terephthalate copolymer. , Hydroxynaphthoic acid / parahydroxybenzoic acid copolymer, biphenol / parahydroxybenzoic acid / phthalic acid copolymer, and the like.

The modified polyolefin resin preferably has at least one functional group selected from the group consisting of a carbonyl group, an amino group, an oxazolyl group, a glycidyl group, an epoxy group, a hydroxyl group, and a silanol group. These functional groups may be located at either the main chain end or the side chain, or may be located at both the main chain end and the side chain, or only at either one end. Also good.

A hydrogen atom bonded to a nitrogen atom such as a carbonyl group or an amino group may be substituted with a hydrocarbon group such as an alkyl group.

The functional group may be introduced by copolymerizing an unsaturated monomer having the functional group, or introduced by polymerizing an olefin using a chain transfer agent or a polymerization initiator having the functional group. May be. Alternatively, an unsaturated monomer having a functional group may be graft-polymerized by melt-mixing an unsaturated monomer having a functional group and a polyolefin resin in the presence of a radical generator.

Examples of the modified polyolefin resin include propylene homopolymer, propylene-ethylene block copolymer, low density polyethylene, medium density polyethylene, high density polyethylene, and ultra high density polyethylene, maleic acid modified, epoxy modified, glycidyl modified, amine (NH ₂ ) modified and the like.

The modified polyolefin resin is preferably a polyolefin resin having a carboxyl group or an acid anhydride group introduced therein. Further, the unsaturated monomer includes acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, aconitic acid and anhydrides thereof. At least one selected from the above is preferable, and maleic anhydride is particularly preferable.

The ethylene / vinyl alcohol copolymer is preferably a copolymer composed of 10 to 60 mol% ethylene and 90 to 40 mol% vinyl alcohol, from 20 to 50 mol% ethylene and 80 to 50 mol% vinyl alcohol. More preferably, it is a copolymer. Further, it may contain a third component, and the third component is an α-olefin such as propylene, isobutylene, 4-methylpentene-1, 1-hexene, 1-octene; vinyl acetate, vinyl propionate , Vinyl esters of versatic acid, vinyl esters of pivalic acid, vinyl esters of valeric acid, vinyl esters of capric acid, vinyl esters of benzoic acid; unsaturated carboxylic acids such as itaconic acid, methacrylic acid, acrylic acid, maleic anhydride Or a derivative thereof (eg, salt, ester, nitrile, amide, anhydride, etc.); vinylsilane compound such as vinyltrimethoxysilane; unsaturated sulfonic acid or salt thereof; N-methylpyrrolidone; Of ethylene and vinyl alcohol Relative to the amount is preferably 10 mol% or less.

In the thermoplastic resin composition of the present invention, the mass ratio of the fluororesin and the non-fluorine-containing thermoplastic resin is preferably 80:20 to 20:80. If the amount of the fluororesin is too large, a molded product having sufficient mechanical strength may not be obtained. If the amount of the fluorine-free thermoplastic resin is too large, the properties of the fluororesin may not be fully utilized.

The thermoplastic resin composition of the present invention comprises inorganic fillers such as calcium carbonate, talc, celite, clay, titanium oxide, carbon black, barium sulfate, pigments, flame retardants, lubricants, light stabilizers, weathering stabilizers, antistatic agents. An agent, an ultraviolet absorber, an antioxidant, a release agent, a foaming agent, a fragrance, an oil, a softening agent, and the like may be contained within a range that does not affect the effects of the present invention.

The thermoplastic resin composition of the present invention is obtained by mixing a fluororesin, a fluorine-free thermoplastic resin and a polyfunctional compound under melting conditions. For example, a method in which a fluororesin, a fluorine-free thermoplastic resin and a polyfunctional compound are simultaneously melt-kneaded, a fluororesin and a polyfunctional compound are first melt-kneaded, and then a fluorine-free thermoplastic resin is added and further melt-kneaded. A method of melt-kneading a fluorine-free thermoplastic resin and a polyfunctional compound first, followed by further adding a fluorine resin and further melt-kneading, a fluorine resin and a fluorine-free thermoplastic resin melt-kneading first, Then, the method of adding a polyfunctional compound and melt-kneading is mentioned.

Moreover, it is preferable that each molecule | numerator of a fluororesin, a fluorine-free thermoplastic resin, and a polyfunctional compound has couple | bonded from the point which mechanical strength improves. Here, bonding means that a covalent bond, an ionic bond and / or a hydrogen bond are formed between the respective molecules of the fluororesin, the fluorine-free thermoplastic resin and the thermoplastic resin. The covalent bond refers to, for example, a chemical bond formed by a reaction between a reactive functional group possessed by a fluororesin and a fluorine-free thermoplastic resin.

Mixing can be performed using a commonly used Banbury mixer, pressure kneader, extruder, or the like. Among these, it is preferable to mix using an extruder, and it is especially preferable to mix using a twin-screw extruder at the point which accelerates | stimulates reaction of each molecule | numerator efficiently. In this case, the fluorine resin and the fluorine-free thermoplastic resin are mixed more uniformly.

The melting condition means a temperature at which the fluororesin and the fluorine-free thermoplastic resin melt. The melting temperature varies depending on the glass transition temperature and the melting point of each of the fluororesin and the fluorine-free thermoplastic resin, but is preferably 120 to 400 ° C, more preferably 150 to 350 ° C. If the temperature is lower than 120 ° C, the fluororesin and the fluorine-free thermoplastic resin may not be sufficiently mixed. If the temperature exceeds 400 ° C, the fluorine-free thermoplastic resin tends to be thermally deteriorated.

The melt flow rate (MFR) of the thermoplastic resin composition of the present invention is preferably 0.5 to 150 g / 10 minutes and more preferably 1 to 100 g / 10 minutes in a temperature range of 200 to 300 ° C. preferable. If the MFR is less than 0.5 g / 10 minutes or exceeds 150 g / 10 minutes, injection molding tends to be difficult.

The thermoplastic resin composition of the present invention preferably has a fuel permeability of 5 g · mm / m ² · day or less when considering use in fuel peripheral parts, and preferably 3 g · mm / m ² · day. More preferably, it is more preferably 1 g · mm / m ² · day or less. Here, measurement of fuel permeability is carried out by the cup method using CE10 (toluene / isooctane / ethanol = 45/45/10 vol%) as a simulated fuel.

The thermoplastic resin composition of the present invention can be molded using a general molding method or molding apparatus. As the molding method, for example, any method such as injection molding, extrusion molding, compression molding, blow molding, calender molding, vacuum molding and the like can be adopted, and the resin composition of the present invention can be used depending on the purpose of use. Although it is molded into a molded product having an arbitrary shape, it is preferably molded by injection molding from the viewpoint of ease of production.

A molded article made of the thermoplastic resin composition is also one aspect of the present invention.

The molded article of the present invention may be a sheet or a film, and may be a laminate having a layer made of the thermoplastic resin composition and a layer made of another material. In the conventional molded product, it was necessary to separately provide a layer having excellent fuel permeability and a layer having excellent heat resistance, impact resistance, and strength, and to share the functions. However, according to the thermoplastic resin composition, It can also be expected to provide excellent fuel permeability and excellent heat resistance, impact resistance and strength in this layer.

The thermoplastic resin composition and a molded product comprising the thermoplastic resin composition are tubes, hoses: automotive fuel piping tubes or hoses, automotive radiator hoses, brake hoses, air conditioning hoses, wire coating materials, optical fiber coatings. Films and sheets for materials, etc .: Sliding members that require high chemical resistance, such as diaphragms for diaphragm pumps and various packings, agricultural films, linings, weatherproof covers, laminated steel sheets used in the construction and home appliance fields, etc. Etc. Tanks: Used as various molded products such as automobile radiator tanks, chemical bottles, chemical tanks, bags, chemical containers, and gasoline tanks.

Since the thermoplastic resin composition of the present invention has the above-described configuration, the fluororesin and the fluorine-free thermoplastic resin are uniformly dispersed, and molding with excellent chemical resistance, heat resistance, slidability, etc. Goods can be obtained.

Next, the present invention will be described with reference to examples, but the present invention is not limited to such examples.

<Test piece preparation>
Using the thermoplastic resin compositions produced in the examples and comparative examples, compression molding was performed under the conditions of 280 ° C. and 5 MPa with a hot press machine to produce a sheet-like test piece having a thickness of 2 mm, and then a dumbbell for tensile test. A test specimen and a strip test specimen for Izod test were prepared by cutting.

<Izod strength measurement>
The notched Izod impact value at 23 ° C. was measured according to ASTM D256 using an Izod impact tester (manufactured by Ueshima Seisakusho Co., Ltd.) using the test piece prepared by the method described above.

<Measurement of tensile strength at break and tensile elongation at break>
Using the dumbbell-type test piece produced by the above-described method, a tensile test was conducted at a speed of 50 mm / min using a Tensilon universal testing machine (manufactured by A & D). Elastic modulus and tensile elongation at break were determined.

<Measurement of specific gravity>
The specific gravity was measured according to ASTM D792 using the thermoplastic resin compositions produced in the examples and comparative examples.

<Functional group analysis by infrared absorption spectrum>
A sheet having a thickness of 0.15 to 0.30 mm was prepared by the above method, and an infrared absorption spectrum was analyzed using a Perkin-Elmer FT-IR spectrometer 1760X (manufactured by PerkinElmer). The obtained infrared absorption spectrum was analyzed using Perkin-Elmer Spectrum for windows Ver. The baseline was automatically determined using 1.4C, and the absorbance of a predetermined peak was measured. The film thickness was measured using a micrometer.

<Measurement of composition of fluororesin copolymer>
The copolymer composition of the fluororesin was determined from ¹⁹ F-NMR and fluorine elemental analysis.

<Measurement of melting point of fluororesin>
Using a Seiko differential scanning calorimeter [DSC], the melting peak when the temperature was raised at a rate of 10 ° C./min was recorded, and the temperature corresponding to the maximum value was taken as the melting point.

<Measurement of melt flow rate (MFR)>
Using a melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.), at each measurement temperature, the mass (g) of the polymer flowing out per unit time (10 minutes) from a nozzle having a diameter of 2 mm and a length of 8 mm under a 5 kg load was measured. .

<Production example>
In the examples and comparative examples, the following materials were used.

(Fluorine resin)
Fluororesin (I-1): CTFE / TFE copolymer monomer composition having —OC (═O) OCH ₂ CH ₂ CH ₃ group is CTFE / TFE / perfluoro (propyl vinyl ether) = 77/21/2 (mol) ratio). Mp 245 ° C. The MFR at 297 ° C. is 30 g / 10 min. The number of —OC (═O) OCH ₂ CH ₂ CH ₃ groups is 160 (per 1 million carbon atoms).

Fluororesin (I-2): FEP having a -COOH group
The monomer composition is TFE / HFP / perfluoro (propyl vinyl ether) = 91.9 / 7.7 / 0.4 (molar ratio). Melting point 260 ° C. The MFR at 297 ° C. is 6.9 g / 10 min. The number of —COOH groups is 480 (per 1 million carbon atoms).

Fluororesin (I-3): ETFE having —OC (═O) OCH ₂ CH ₂ CH ₃ Group
The monomer composition is TEF: Et: HFP: HF-Pe = 40.8: 44.8: 13.9: 0.5 mol%. Melting point: 162.5 ° C. The MFR at 297 ° C. is 30 g / 10 min. The number of —OC (═O) OCH ₂ CH ₂ CH ₃ groups is 300 (per 1 million carbon atoms).

(Fluorine-free thermoplastic resin)
The following resins were used.
Thermoplastic resin (II-1): Maleic acid-modified ultra-low density polyethylene, manufactured by Mitsui Chemicals, trade name “Admer NF528”
Thermoplastic resin (II-2): Polybutylene terephthalate, manufactured by Toray Industries, Inc., trade name “Trecon 1401 X06”

Examples 1-14
Fluorine resin, fluorine-free thermoplastic resin, and polyfunctional compound are supplied to the twin-screw extruder at the ratio (parts by mass) shown in Table 1, and melt-kneaded under conditions of a cylinder temperature of 280 ° C. and a screw rotation speed of 300 rpm. And the pellet of the thermoplastic resin composition was manufactured, respectively. Tables 1 and 2 show the results of producing test pieces by the above-described method using the obtained pellets of the thermoplastic resin composition and measuring specific gravity, tensile breaking strength, tensile breaking elongation, and Izod strength. .

Comparative Examples 1-5
A test piece was prepared in the same manner as in the example except that a polyfunctional compound was not used and only a fluororesin and a fluorine-free thermoplastic resin were used. The evaluation results are shown in Table 3.

The thermoplastic resin composition of the present invention can be used for various molded product applications that require chemical resistance, heat resistance, slidability, and the like.

Claims (9)

A fluororesin having at least one functional group selected from the group consisting of a carbonyl group, an olefin group and an amino group at the main chain end or side chain end of the polymer;
A fluorine-free thermoplastic resin having a reactive functional group at the main chain end or side chain end of the polymer; and
Polyfunctional compounds,
A thermoplastic resin composition comprising: Fluorine-free thermoplastic resin is hydroxyl group, silanol group, carboxyl group, ester group, carbonate group, haloformyl group, formyl group, amino group, amide group, imide group, mercapto group, thiolate group, thiol group, sulfonic acid group The thermoplastic resin composition according to claim 1, which has at least one reactive functional group selected from the group consisting of oxazolyl group, epoxy group, and glycidyl group. The polyfunctional compound has at least one reactive functional group selected from the group consisting of a carbonyl group, a carboxyl group, a haloformyl group, an amide group, an olefin group, an amino group, an isocyanate group, a hydroxy group, and an epoxy group. The thermoplastic resin composition according to 1 or 2. The thermoplastic resin composition according to claim 1, 2 or 3, wherein the polyfunctional compound is an aromatic amine compound. The thermoplastic resin composition according to claim 4, wherein the polyfunctional compound has at least one substituent selected from the group consisting of a fluoroalkyl group and a fluorophenyl group. The thermoplastic resin composition according to claim 1, 2, 3, 4, or 5, wherein the mass ratio of the fluororesin and the fluorine-free thermoplastic resin is 80:20 to 20:80. The fluororesin is at least one selected from the group consisting of a copolymer composed of ethylene and tetrafluoroethylene, a copolymer composed of chlorotrifluoroethylene and tetrafluoroethylene, and a copolymer composed of tetrafluoroethylene and hexafluoropropylene. The thermoplastic resin composition according to claim 1, which is a seed. The fluorine-free thermoplastic resin is at least one selected from the group consisting of polyester, polycarbonate, modified polyolefin, and ethylene / vinyl alcohol copolymer, 8. 1, 2, 3, 4, 5, 6 or 7. Thermoplastic resin composition. A molded article comprising the thermoplastic resin composition according to claim 1, 2, 3, 4, 5, 6, 7 or 8.