JP4661205B2 - Fluorine-containing copolymer composition and molded article comprising the same - Google Patents

Description

  The present invention relates to a fluorine-containing copolymer composition and a molded article comprising the same.

  Polyamides such as polyamide 6 and polyamide 66 are excellent in heat resistance, chemical resistance, rigidity, wear resistance, moldability, etc., and are therefore used in various applications as engineering plastics. In particular, it has excellent wear resistance, is hard to seize even in a non-lubricated state, has low noise, and is excellent in lightness and corrosion resistance, so it is used in many sliding parts such as bearings, gears, bushes, spacers, rollers, and cams. Has been.

  However, when the polyamide is used for the sliding portion, it may be worn at the same time as it melts due to a temperature rise due to frictional heat. In addition, polyamides are required to be improved because they cause dimensional changes and deterioration of physical properties due to water absorption.

  Polyamide 46 produced from 1,4-diaminobutane and adipic acid has a high melting point of 290 ° C., high crystallinity, and excellent wear resistance compared to polyamide 6 and the like. A composition in which ultrahigh molecular weight polyethylene is blended with polyamide 46 to further improve the wear resistance has been proposed (see, for example, Patent Document 1). However, since polyamide 46 has higher water absorption than polyad 6 and the like, and has large dimensional changes and physical property changes, it cannot be used in applications such as the automobile field.

A composition excellent in wear resistance obtained by blending fluorine oil with semi-aromatic polyamide has been proposed (see, for example, Patent Document 2). However, the composition was not sufficiently durable against abrasion.
Although a composition of a fluororesin and polyamide 12 has been proposed (see, for example, Patent Document 3), the composition has low water absorption but has insufficient wear resistance.

JP-A-8-134348 JP 2004-107525 A JP 2003-176394 A

  The object of the present invention is a fluorine-containing copolymer composition that is excellent in wear resistance and durability, and is excellent in low water absorption, dimensional stability, mechanical strength, heat resistance, chemical resistance, weather resistance, gas barrier properties, etc. And a molded article comprising the same.

The present invention relates to a repeating unit (a) based on tetrafluoroethylene and / or chlorotrifluoroethylene, a repeating unit (b) based on a fluorine monomer (excluding tetrafluoroethylene and chlorotrifluoroethylene), and an acid anhydride. A repeating unit (c) based on a monomer having a product residue and a polymerizable unsaturated bond, wherein (a) is 50 to 99.89 mol with respect to ((a) + (b) + (c)) %, (B) 0.1 to 49.99 mol%, and (c) 0.01 to 5 mol% of the fluorine-containing copolymer (A) , polyamide 66, polyamide 46, polyamide 6T, polyamide MXD6 and containing the one or more thermoplastic polyamides selected from polyamides 9T (B), the mass ratio of the fluorocopolymer (a) / polyamide (B) is 90 / 10-10 90 der is, the fluorine-containing copolymer (A), tetrafluoroethylene and / or chlorotrifluoroethylene, the fluorine monomer, and a monomer having a polymerizable unsaturated bond and the acid anhydride residue, A fluorine-containing copolymer composition characterized by being obtained by radical copolymerization of

  The present invention also provides a molded article obtained by molding the fluorine-containing copolymer composition.

  The fluorine-containing copolymer composition of the present invention has a small friction coefficient and is excellent in wear resistance and durability. In addition, it has excellent low water absorption, dimensional stability, mechanical properties, heat resistance, chemical resistance, weather resistance, and gas barrier properties.

  The fluorine-containing copolymer (A) in the present invention is a repeating unit (a) based on tetrafluoroethylene (hereinafter referred to as TFE) and / or chlorotrifluoroethylene (hereinafter referred to as CTFE), a fluorine monomer (however, A repeating unit (b) based on (excluding TFE and CTFE)) and a repeating unit (c) based on a monomer having an acid anhydride residue and a polymerizable unsaturated bond.

As the fluorine monomer in the present invention, fluoroolefin such as vinyl fluoride, vinylidene fluoride (hereinafter referred to as VdF), trifluoroethylene, hexafluoropropylene (hereinafter referred to as HFP), CF ₂ = CFOR ¹ (here , R ¹ may be a perfluoroalkyl group that may contain an oxygen atom having 1 to 10 carbon atoms.), CF ₂ = CFOR ² SO ₂ X ¹ (R ² may contain an oxygen atom having 1 to 10 carbon atoms) An alkyl group, X ¹ is a halogen atom or a hydroxyl group.), CF ₂ = CFOR ³ CO ₂ X ² (wherein R ³ is a perfluoroalkyl group which may contain an oxygen atom having 1 to 10 carbon atoms, X ² is hydrogen) atom or alkyl group having 3 or less carbon _{atoms.), CF 2 = CF (} CF 2) p OCF = CF 2 ( wherein, p is 1 Is ^{_{2.), CH 2 = CX}} 3 (CF 2) q X 4 ( wherein, ^{X 3} represents a hydrogen atom or a fluorine atom, q is from 2 to 10 integer, ^{X 4} is a hydrogen atom or a fluorine atom.) And perfluoro (2-methylene-4-methyl-1,3-dioxolane) and the like.

Preferably, it is one or more selected from the group consisting of VdF, HFP, CF ₂ = CFOR ¹ and CH ₂ = CX ³ (CF ₂ ) _q X ⁴ , more preferably CF ₂ = CFOR ¹ or CH ₂ = CX ³ (CF ₂ ) _q X ⁴ .
CF ₂ = CFO ¹ includes CF ₂ = CFOCF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₂ CF ₃ , CF ₂ = CFO (CF ₂ ) ₈ F, and the like. Can be mentioned. _Preferably, a _{CF 2 = CFOCF 2 CF 2 CF} 3.
As CH ₂ = CX ³ (CF ₂ ) _q X ⁴ , CH ₂ = CH (CF ₂ ) ₂ F, CH ₂ = CH (CF ₂ ) ₃ F, CH ₂ = CH (CF ₂ ) ₄ F, CH ₂ ═CF (CF ₂ ) ₃ H, CH ₂ ═CF (CF ₂ ) ₄ H, and the like. Preferably, CH ₂ ═CH (CF ₂ ) ₄ F or CH ₂ ═CH (CF ₂ ) ₂ F.

As the monomer having an acid anhydride residue and a polymerizable unsaturated bond (hereinafter also referred to as AM monomer) in the present invention, itaconic anhydride (hereinafter referred to as IAH) and citraconic anhydride (hereinafter referred to as CAH). ), 5-norbornene-2,3-dicarboxylic acid anhydride (hereinafter referred to as NAH), maleic anhydride and the like. Preferably, it is at least one selected from the group consisting of IAH, CAH and NAH, more preferably IAH or CAH.
When at least one selected from the group consisting of IAH, CAH and NAH is used, acid anhydride can be used without using a special polymerization method (see JP-A-11-19312) required when maleic anhydride is used. A fluorine-containing copolymer containing a residue is more preferable because it can be easily produced.

  In the fluorine-containing copolymer (A) in the present invention, (a) is 50 to 99.89 mol% and (b) is 0.1 to 49 with respect to ((a) + (b) + (c)). .99 mol% and (c) is 0.01 to 5 mol%. Preferably, the repeating unit (a) is 50 to 99.4 mol%, the repeating unit (b) is 0.5 to 49.9 mol%, the repeating unit (c) is 0.1 to 3 mol%, and more Preferably, the repeating unit (a) is 50 to 98.9 mol%, the repeating unit (b) is 1 to 49.9 mol%, and the repeating unit (c) is 0.1 to 2 mol%.

  When the content of the repeating units (a), (b) and (c) is in this range, the fluorinated copolymer (A) is excellent in heat resistance and chemical resistance, and the fluorinated copolymer composition is Excellent wear resistance. When the content of the repeating unit (b) is within this range, the fluorine-containing copolymer is excellent in moldability and mechanical properties such as stress crack resistance. When content of a repeating unit (c) exists in this range, a fluorine-containing copolymer (A) is excellent in adhesiveness with a polyamide (B).

In addition, the fluorine-containing copolymer in the present invention includes a repeating unit based on dicarboxylic acid such as itaconic acid, citraconic acid, 5-norbornene-2,3-dicarboxylic acid, maleic acid, etc., obtained by hydrolysis of AM monomer. May be included. When the repeating unit based on the dicarboxylic acid is contained, the content of the repeating unit (c) represents the total amount of the repeating unit based on the AM monomer and the repeating unit based on the dicarboxylic acid.
In the fluorine-containing copolymer of the present invention, ((a) + (b) + (c)) with respect to all repeating units is preferably 60 mol% or more, more preferably 65 mol% or more, and most preferably 68 mol% or more. preferable.

The fluorine-containing copolymer (A) in the present invention includes a repeating unit (d) based on a non-fluorine monomer (excluding an AM monomer) in addition to the repeating units (a), (b) and (c). It is also preferable to contain.
Examples of the non-fluorine monomer include olefins having 3 or less carbon atoms such as ethylene (hereinafter referred to as E) and propylene (hereinafter referred to as P), vinyl esters such as vinyl acetate (hereinafter referred to as VOA), ethyl vinyl ether, and cyclohexyl. And vinyl ethers such as vinyl ether. E, P or VOA is preferable. More preferably, it is E.
When the repeating unit (d) is contained, the content thereof is preferably such that the molar ratio of ((a) + (b) + (c)) / (d) is 100/5 to 100/90, 5-100 / 80 is more preferable, and 100 / 10-100 / 65 is most preferable.

Preferable specific examples of the fluorine-containing copolymer (A) in the present invention include TFE / CF ₂ = CFOCF ₂ CF ₂ CF ₃ / IAH copolymer, TFE / CF ₂ = CFOCF ₂ CF ₂ CF ₃ / CAH copolymer. Copolymer, TFE / HFP / IAH copolymer, TFE / HFP / CAH copolymer, TFE / VdF / IAH copolymer, TFE / VdF / CAH copolymer, TFE / CH ₂ = CH (CF ₂ ) ₄ F / IAH / E copolymer, TFE / CH ₂ ═CH (CF ₂ ) ₄ F / CAH / ethylene copolymer, TFE / CH ₂ ═CH (CF ₂ ) ₂ F / IAH / E copolymer, TFE / _{CH 2 = CH (CF 2)} 2 F / CAH / E _{copolymer, CTFE / CH 2 = CH (} CF 2) 4 F / IAH / E _{copolymer, CTFE / CH 2 = CH (} CF 2) 4 F / CAH / E copolymer, CTFE / CH ₂ ═CH (CF ₂ ) ₂ F / IAH / E copolymer, CTFE / CH ₂ ═CH (CF ₂ ) ₂ F / CAH / E copolymer, etc. .

  The fluorine-containing copolymer (A) in the present invention may have a functional group such as an ester group, a carbonate group, a hydroxyl group, a carboxyl group, a carbonyl fluoride group, or an acid anhydride as a polymer terminal group. The blend (A) and the polyamide (B) are preferable because they are mixed well. The polymer end group is preferably introduced by appropriately selecting a radical polymerization initiator, a chain transfer agent and the like used in the production of the fluorine-containing copolymer (A).

  The melt viscosity of the fluorine-containing copolymer (A) used in the present invention is an MFR (Melt Flow Rate) value at 230 ° C. to 350 ° C. measured by the method described in Examples, and is 0.5 to 100 g / 10. Minute, preferably 1 to 30 g / 10 minutes, and most preferably 5 to 20 g / 10 minutes. The MFR value is a measure of the molecular weight. When this value is large, the molecular weight is low, and when it is small, the molecular weight is large. If it is small, the moldability and the appearance of the molded product are not sufficient, and if it is large, the mechanical strength is low. Within this range, a molded product obtained by molding the composition is excellent in smoothness, mechanical properties and gas barrier properties.

  There is no restriction | limiting in particular as a manufacturing method of the fluorine-containing copolymer (A) in this invention, The polymerization method using a radical polymerization initiator is used. Examples of the polymerization method include bulk polymerization, solution polymerization using an organic solvent such as fluorinated hydrocarbon, chlorohydrocarbon, fluorinated chlorohydrocarbon, alcohol, hydrocarbon, an aqueous medium, and an appropriate organic solvent as necessary. Examples include suspension polymerization to be used, emulsion polymerization using an aqueous medium and an emulsifier, and solution polymerization is particularly preferable.

As a radical polymerization initiator, the temperature at which the half-life is 10 hours is preferably 0 ° C. to 100 ° C., more preferably 20 to 90 ° C. Specific examples include azo compounds such as azobisisobutyronitrile, non-fluorine diacyl peroxides such as isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide and lauroyl peroxide, peroxydicarbonates such as diisopropylperoxydicarbonate, tert - butyl peroxypivalate, tert- butylperoxy isobutyrate, tert- butyl peroxy ester peroxy acetate, _{etc., 2} (where _{(Z (CF 2) r COO} ), Z represents a hydrogen atom, a fluorine atom or a chlorine atom , R is an integer of 1 to 10.) Fluorine-containing diacyl peroxide such as a compound represented by formula (I), inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate.

  In the present invention, it is also preferable to use a chain transfer agent in order to control the melt viscosity of the fluorinated copolymer. Chain transfer agents include alcohols such as methanol and ethanol, chlorofluorohydrocarbons such as 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane, Hydrocarbons such as pentane, hexane, and cyclohexane are listed. In addition, it is preferable to use a chain transfer agent having a functional group such as an ester group, a carbonate group, a hydroxyl group, a carboxy group, or a carbonyl fluoride group because an adhesive polymer terminal group is introduced into the fluorine-containing copolymer. Examples of the chain transfer agent include acetic acid, acetic anhydride, methyl acetate, ethylene glycol, propylene glycol and the like.

The polymerization conditions are not particularly limited, and the polymerization temperature is preferably 0 to 100 ° C, more preferably 20 to 90 ° C. The polymerization pressure is preferably from 0.1 to 10 MPa, more preferably from 0.5 to 3 MPa. The polymerization time is preferably 1 to 30 hours.
The concentration of the AM monomer during the polymerization is preferably 0.01 to 5%, more preferably 0.1 to 3%, and most preferably 0.1 to 1% with respect to all monomers. When the concentration of the AM monomer is too high, the polymerization rate tends to decrease. Within the above range, the polymerization rate during production is moderate, and the resulting fluorinated copolymer (A) is excellent in adhesion to the polyamide (B). During the polymerization, as the AM monomer is consumed in the polymerization, it is preferable to supply the consumed amount into the polymerization tank continuously or intermittently to maintain the concentration of the AM monomer within this range.

  As the polyamide (B) in the present invention, polyamide 6 (PA6), polyamide 66 (PA66), polyamide 46 (PA46), polyamide 11 (PA11), polyamide 12 (PA12), polyamide 610 (PA610), polyamide 612 (PA612) ), Polyamide 6/66 copolymer (PA6 / 66), polyamide 6/66/610 copolymer (PA6 / 66/610), polyamide MXD6 (MXD6), polyamide 6T, polyamide 9T, polyamide 6 / 6T copolymer The above thermoplastic polyamide is preferable. Among these, one or more thermoplastic polyamides selected from PA66, PA46, polyamide 6T, MXD6, and polyamide 9T are preferable. Further, PA46 or / and polyamide 9T are most preferable. T means terephthalic acid. When these polyamides are used, the fluorine-containing copolymer composition is excellent in mechanical strength and heat resistance, low water absorption, dimensional stability, chemical resistance, weather resistance and the like.

It is also preferable that the polyamide (B) in the present invention has its polymer chain end sealed with a sealant.
As the end-capping agent, a compound having one functional group having reactivity with the terminal amino group or carboxyl group of the polyamide (B) is preferable. In particular, monocarboxylic acids or monoamines that are excellent in reactivity, stability of the sealed end, and the like are more preferable, and monocarboxylic acids that are excellent in handleability are most preferable. In addition, acid anhydrides such as phthalic anhydride, isocyanates, acid halides, esters, monoalcohols, and the like can be used.

  Specific examples of the monocarboxylic acid include aliphatic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid. Monocarboxylic acids, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, aromatic monocarboxylic acids such as methylnaphthalenecarboxylic acid, and mixtures thereof Etc. Among them, it is excellent in reactivity, stability at the sealing end, and inexpensive, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid and Benzoic acid is preferred.

  Specific examples of the monoamine include aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, Examples include alicyclic monoamines such as dicyclohexylamine, aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine, and mixtures thereof. Of these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline, which have a high boiling point, are excellent in reactivity, are excellent in stability at the sealing end, and are inexpensive, are preferable.

  The polyamide (B) used in the present invention preferably has an MFR value of 0.5 to 200 g / 10 min at 230 ° C. to 350 ° C., more preferably 1 to 100 g / 10 min, and 3 to 50 g / 10 min. Is most preferred. Within this range, the molded article has excellent smoothness and excellent mechanical properties.

  The fluorine-containing copolymer composition of the present invention preferably further contains an inorganic filler (C). Specific examples of the inorganic filler (C) include fibrous fillers (glass fiber, carbon fiber, boron fiber, aramid fiber, liquid crystal polyester fiber, stainless steel microfiber, etc.), powdery fillers (talc, mica, graphite, Molybdenum disulfide, polytetrafluoroethylene, calcium carbonate, silica, silica alumina, alumina, titanium dioxide, etc.), conductive filler (carbon blacks such as carbon nanotubes, carbon nanohorns, acetylene black, ketjen black), low melting point Metal etc. are mentioned.

  These inorganic fillers may be used alone or in combination of two or more. The content of the inorganic filler (C) in the fluorine-containing copolymer composition is such that (fluorine-containing copolymer (A) + polyamide (B)) / inorganic filler (C) is 90/10 to 50 / in mass ratio. 50 is preferable. Within this range, the fluorine-containing copolymer composition is excellent in mechanical properties and conductivity.

  As said fibrous filler, the glass fiber, carbon fiber, and aramid fiber which are excellent in the reinforcement effect and sliding property are preferable, and an aramid fiber and carbon fiber are more preferable. As the powder filler, talc, mica, molybdenum disulfide and graphite, which are excellent in slidability, are preferable.

As the conductive filler, a carbon-based conductive filler is preferable. The carbon-based conductive filler is preferably a carbon-based conductive filler having a BET specific surface area of 50 to 1000 m ² / g and a DBP oil absorption of 100 ml / 100 g to 1000 ml / 100 g, and a BET specific surface area of 60. More preferably, it is ˜600 m ² / g and the DBP oil absorption is 150 to 1000 ml / 100 g. If the BET specific surface area is too small, the conductivity is low, and if it is too large, the conductive filler aggregates, and the surface smoothness of the molded product obtained by molding the fluorine-containing copolymer is not sufficient. If the DBP oil absorption is too small, the conductivity is low, and if it is too large, the surface smoothness of the molded product obtained by molding the fluorine-containing copolymer is not sufficient. Within this range, the conductivity is excellent, and the molded product obtained by molding is excellent in surface smoothness.

  The carbon nanotube and the carbon nanohorn have a diameter of 3.5 to 70 nm, preferably an aspect ratio of 5 to 200, more preferably a diameter of 5 to 60 nm, and an aspect ratio of 5 to 200, Most preferably, the diameter is 10 to 55 nm and the aspect ratio is 10 to 100. When it is in this range, the molded product is excellent in surface smoothness. The carbon black preferably has an average particle size of 3.5 to 70 nm, more preferably 5 to 50 nm, and most preferably 10 to 40 nm. When it is in this range, the molded product is excellent in surface smoothness.

The volume resistivity of the carbon-based conductive filler is preferably ^{1 × 10 -4 ~1 × 10 2} Ω / cm, more preferably ^{1 × 10 -4 ~10Ω / cm,} 1 × 10 -4 ~1Ω / cm is Most preferred.

  As for the inorganic filler (C), the filler alone may be blended in the fluorine-containing copolymer composition, and the fluorine-containing copolymer (A), the polyamide (B), the fluorine-containing copolymer (A) and the polyamide are preliminarily prepared. A master batch dispersed in a thermoplastic resin other than (B) may be prepared, and a predetermined amount may be blended using the master batch.

  As a method for producing a fluorine-containing copolymer composition containing an inorganic filler (C), a method of dry blending with a fluorine-containing copolymer composition (A) and a polyamide (B), and melt-kneading using an extruder Methods and the like. Of these, the method of melt kneading using an extruder is preferred from the viewpoint of ease of operation. The extruder used is preferably a twin screw type, and the melt kneading temperature is preferably 280 to 380 ° C. The residence time is preferably 10 seconds or more and 10 minutes or less. The screw rotation speed is preferably 50 rpm or more and 1500 rpm or less.

  The fluorine-containing copolymer composition of the present invention preferably contains another polymer other than the fluorine-containing copolymer (A) and the polyamide (B) as long as the characteristics thereof are not significantly impaired. The content of the other polymer is preferably 30% by mass or less with respect to the total mass of the fluorine-containing copolymer composition.

  Other polymers include polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polycaprolactone, phenoxy resin, polysulfone, polyethersulfone, polyetherketone, polyetheretherketone, polyetherimide, polyamide 6, polyamide 66, Polyamide 11, polyamide 12, polyamide 610, polyphenylene oxide, polyphenylene sulfide, polytetrafluoroethylene, ABS, PMMA, polypropylene, polyethylene, polybutadiene, butadiene-styrene copolymer, ethylene-propylene copolymer, EPDM, styrene-butadiene block Copolymer, butadiene-acrylonitrile copolymer, acrylic rubber, styrene-maleic anhydride copolymer , Styrene - phenylmaleimide copolymer and the like.

  Examples of the molding method of the fluorine-containing copolymer composition of the present invention include injection molding, extrusion molding, press molding, blow molding, calendar molding and the like. The said shaping | molding method is suitably selected according to the kind of intended molded product, a use, a shape, etc., You may combine these 2 or more types.

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.
The copolymer composition, melting point, MFR, abrasion resistance, water absorption, and fuel barrier properties of the fluorinated copolymer were measured by the following methods.
[Copolymerization Composition of Fluorine-Containing Copolymer] Calculated by using melt NMR analysis, fluorine content analysis and infrared absorption spectrum analysis.

  [Melting Point (° C.)] Using a DSC apparatus manufactured by Seiko Denshi, the melting peak when the temperature was raised at a rate of 10 ° C./min was recorded, and the temperature (° C.) corresponding to the maximum value was defined as the melting point (Tm).

[MFR (g / 10 min)] Using a Techno Seven melt indexer, the mass (g) of the polymer flowing out in 10 minutes as a unit time from a nozzle with a diameter of 2 mm and a length of 8 mm under various temperatures and 5 kg load was measured. did. The measurement temperature was 230 ° C to 350 ° C.
[Abrasion resistance] A sliding test was performed with a rotary friction and abrasion tester for 24 hours at a metal resistance (SMC45), a load of 0.294 MPa, and a speed of 30 m / min. The amount of wear after 24 hours was measured. In addition, the coefficient of dynamic friction was determined. The smaller the amount of wear, the better the wear resistance.

[Water absorption (%)] A JIS No. 1 dumbbell-shaped test piece was prepared, and the mass increase when the test piece was immersed in water at 23 ° C. for 24 hours was measured, and the ratio (%) to the mass before immersion was calculated. The water absorption rate was used.
[Fuel permeability (g · mm / m ² · d)] An SUS container having a volume of about 20 ml is filled with a test fuel (CE10; toluene: isooctane: ethanol = 45: 45: 10 (volume ratio)), After the opened one side was sealed with a test film, the fuel permeability at the time when the mass change per 24 hours was kept constant at 60 ° C. was calculated.

[Example 1]
The polymerization tank equipped with a stirrer with an internal volume of 94 liters was degassed, and 71.3 kg of 1-hydrotridecafluorohexane (hereinafter referred to as HTFH), 1,3-dichloro-1,1,2,2,3 -20.4 kg of pentafluoropropane (manufactured by Asahi Glass Co., Ltd., AK225cb, hereinafter referred to as AK225cb), 562 g of CH ₂ = CH (CF ₂ ) ₂ F, and 4.45 g of IAH were charged, and the inside of the polymerization tank was brought to 66 ° C. The temperature was raised and the pressure was increased to 1.5 MPa / G with an initial monomer mixed gas of 89/11 at a molar ratio of TFE / E. As a polymerization initiator, 1 L of a 0.7% HTFH solution of tert-butylperoxypivalate was charged to initiate polymerization. A monomer mixed gas of 59.5 / 40.5 molar ratio of TFE / E was continuously charged so that the pressure was constant during the polymerization. Further, CH ₂ ═CH (CF ₂ ) ₂ F in an amount corresponding to 3.3 mol% and IAH in an amount corresponding to 0.8 mol% are continuously added to the total number of moles of TFE and E charged during the polymerization. I was charged. 9.9 hours after the start of polymerization, when 7.28 kg of the monomer mixed gas was charged, the temperature in the polymerization tank was lowered to room temperature and purged to normal pressure.

The obtained slurry-like fluorine-containing copolymer 1 was put into a 200 L granulation tank charged with 77 kg of water, and the solvent was distilled off and removed while raising the temperature from room temperature to 105 ° C. with stirring. did. By drying the obtained granulated product at 150 ° C. for 15 hours, 6.9 kg of the granulated product 1 of the fluorinated copolymer 1 was obtained. The copolymer composition of the fluorinated copolymer 1 was changed to TFE. 93.5 / 5.7 / 0.8 / 62.9 (molar ratio of polymer units based on / CH ₂ ═CH (CF ₂ ) ₂ F / polymer units based on IAH / polymer units based on E Molar ratio). The melting point was 230 ° C., and the MFR at 280 ° C. was 20 g / 10 minutes.
Using an extruder, the granulated product 1 was melted and extruded under the conditions of 280 ° C. and a residence time of 2 minutes to produce pellets 1 of the fluorinated copolymer 1.

  2.5 kg of pellets 1, 5.0 kg of polyamide 66 (manufactured by Asahi Kasei Co., Ltd., REONA 1500X11, hereinafter referred to as PA-1) as a polyamide, and glass fiber (chopped strand 830A, manufactured by Asahi Fiber Glass Co., Ltd., hereinafter GF830A) as an inorganic filler. 2.5 kg of pre-blended, and then using a twin screw extruder (manufactured by Toshiba Machine Co., Ltd.) under the conditions of screw diameter 35 mm, L / D = 30, cylinder temperature 310 to 340 ° C., and rotation speed 400 rpm. Below, the fluorine-containing copolymer composition 1 was obtained by melt-kneading. The evaluation results of the fluorine-containing copolymer composition 1 are shown in Table 1.

[Example 2]
In Example 1, except that 3.5 kg of pellet 1 and 4.0 kg of polyamide 46 (manufactured by DSM Japan Engineering Plastics, STANY TW441, hereinafter referred to as PA-2) as polyamide and 2.5 kg of GF830A are used. In the same manner as in Example 1, a fluorinated copolymer composition 2 was obtained. The evaluation results of the fluorinated copolymer composition 2 are shown in Table 1.

[Example 3]
The polymerization tank used in Example 1 was degassed, and 902 kg of AK225cb, 0.216 kg of methanol, 31.6 kg of CF ₃ = CFOCF ₂ CF ₂ CF ₃ and 0.43 kg of IAH were charged, and the inside of the polymerization tank was 50. The temperature was raised to 0 ° C., and TFE was charged until the pressure reached 0.38 MPa. As a polymerization initiator solution, 50 mL of a 0.25% AK225cb solution of di (perfluorobutyryl) peroxide was charged to initiate polymerization. TFE was continuously charged so that the pressure was constant during the polymerization. During the polymerization, the polymerization initiator solution was appropriately added to keep the TFE feed rate substantially constant. A total of 120 mL of the polymerization initiator solution was charged. Further, IAH in an amount corresponding to 1 mol% of continuously fed TFE was continuously charged. At the time when 7.0 kg of TFE was charged 6 hours after the start of polymerization, the inside of the polymerization tank was cooled to room temperature, and unreacted TFE was purged.
The obtained slurry-like fluorine-containing copolymer 2 is put into a 200 L granulation tank charged with 75 kg of water, and granulated while distilling and removing the solvent while raising the temperature from room temperature to 105 ° C. with stirring. did. The obtained granulated product was dried at 150 ° C. for 5 hours to obtain 7.5 kg of the granulated product 2 of the fluorinated copolymer 2.
The copolymer composition of the fluorinated copolymer 2 is as follows. Polymer unit based on TFE / CF ₂ = polymer unit based on CFOCF ₂ CF ₂ CF ₃ / polymer unit based on IAH = 97.7 / 2.0 / 0.3 ( Molar ratio). The melting point was 292 ° C., and the MFR at 320 ° C. was 15 g / 10 min.

  Using an extruder, the granulated product 2 was melted under conditions of 320 ° C. and a residence time of 2 minutes, and extruded to prepare pellets 2 of the fluorinated copolymer 2. Instead of pellet 1, 4.6 kg of pellet 2 and 5.4 kg of PA-2 were used, and a fluorinated copolymer composition 3 was obtained in the same manner as in Example 2 except that glass fiber was not used. The evaluation results of the fluorinated copolymer composition 3 are shown in Table 1.

[Example 4]
Example 3 was used except that 3.3 kg of pellet 2 and 6.7 kg of polyamide 9T containing 33% glass fiber as polyamide (Kuraray Co., Ltd., Genesta G2330, hereinafter referred to as PA-3) were used. A fluorinated copolymer composition 4 was obtained. The evaluation results of the fluorinated copolymer composition 4 are shown in Table 1.

[Comparative Example 1]
As pellet 3, 2.5 kg of TFE / perfluoro (propyl vinyl ether) copolymer (Asahi Glass Co., Ltd., FluonPFA P-63P, melting point 290 ° C., MFR at 370 ° C. is 6 g / 10 min), 5.0 kg of PA-2 A fluorinated copolymer composition 5 was obtained in the same manner as in Example 1 except that 2.5 kg of GF830A was used. The evaluation results of the fluorinated copolymer composition 5 are shown in Table 1.

[Comparative Example 2]
3.3 kg of pellet 2, 6.7 kg of polyamide 12 (manufactured by Ube Industries, 3030JI6L, hereinafter referred to as PA-4) as polyamide, and fluorine-containing copolymer as in Example 3 except that GF830A was not used A combined composition 6 was obtained. The evaluation results of the fluorinated copolymer composition 6 are shown in Table 1.

Since the fluorine-containing copolymer composition of the present invention is excellent in wear resistance, heat resistance, chemical resistance, mechanical strength, wear resistance, moldability, etc., bearings, gears, bushes, spacers, rollers, cams, etc. Suitable for applications such as sliding parts. In addition, since it has excellent fuel barrier properties, it can be applied to applications such as automobile fuel system parts such as pipes, tubes, connectors, tanks and bottles.

Claims (3)

A repeating unit (a) based on tetrafluoroethylene and / or chlorotrifluoroethylene, a repeating unit (b) based on a fluorine monomer (excluding tetrafluoroethylene and chlorotrifluoroethylene), and an acid anhydride residue; Containing a repeating unit (c) based on a monomer having a polymerizable unsaturated bond, wherein (a) is 50 to 99.89 mol% with respect to ((a) + (b) + (c)), (b ) Is 0.1 to 49.99 mol%, and (c) is 0.01 to 5 mol%, and polyamide 66, polyamide 46, polyamide 6T, polyamide MXD6 and polyamide 9T containing the one or more thermoplastic polyamides selected (B), the mass ratio of the fluorocopolymer (a) / polyamide (B) is 90 / 10-10 / 90 der The fluorine-containing copolymer (A) is a radical copolymer of tetrafluoroethylene and / or chlorotrifluoroethylene, the fluorine monomer, and a monomer having the acid anhydride residue and a polymerizable unsaturated bond. A fluorine-containing copolymer composition characterized by being obtained . The fluorine-containing copolymer composition further contains an inorganic filler (C), and the content of the inorganic filler (C) is (fluorine-containing copolymer (A) + polyamide (B)) / inorganic filler ( The fluorine-containing copolymer composition according to claim 1 , wherein the mass ratio of C) is 90/10 to 50/50 . A molded article formed by molding the fluorine-containing copolymer composition according to claim 1.