WO2020013314A1 - Thermoplastic resin composition and method for producing same - Google Patents

Abstract

Provided is a thermoplastic resin composition comprising a fluororesin (A) and a crosslinked fluororubber (B). The fluororesin (A) is a copolymer that contains chlorotrifluoroethylene units and tetrafluoroethylene units and that has at least one functional group selected from the group consisting of carbonyl groups, olefin groups, and amino groups at a terminus or termini of a polymer main chain or of a polymer side chain. The crosslinked fluororubber (B) is provided by dynamically crosslinking a fluororubber (b) with a polyamine compound (c) having a thermal decomposition temperature of 210°C or higher and a crosslinking promoter (d) in the presence of the fluororesin (A) and under a melting condition for the fluororesin (A). The mass ratio between the fluororesin (A) and the fluororubber (b) (fluororesin (A)/fluororubber (b)) for the thermoplastic resin composition is less than 70/30 and at least 20/80.

Description

Thermoplastic resin composition and method for producing the same

The present disclosure relates to a thermoplastic resin composition and a method for producing the same, a molded product, a laminate, a fuel hose, a fuel tube, and a fuel sealing material.

開 発 The development of thermoplastic resin compositions that achieve both fuel barrier properties and flexibility has been promoted. For example, Patent Document 1 discloses a thermoplastic resin composition containing a fluororesin (A) and a cross-linked fluororubber (B), wherein the fluororesin (A) has a carbonyl group or an olefin at a main chain terminal or a side chain terminal of the polymer. A cross-linking fluororubber (B) in the presence of a fluororesin (A) under the melting conditions of the fluororesin (A). A thermoplastic resin composition which is dynamically cross-linked together with c) has been proposed.

International Publication No. 2009/020182

開 示 An object of the present disclosure is to provide a thermoplastic resin composition having a reduced tensile modulus without significantly impairing fuel barrier properties.

According to the present disclosure, it is a thermoplastic resin composition containing a fluororesin (A) and a crosslinked fluororubber (B), wherein the fluororesin (A) contains a chlorotrifluoroethylene unit and a tetrafluoroethylene unit, and A copolymer having at least one functional group selected from the group consisting of a carbonyl group, an olefin group and an amino group at a main chain terminal or a side chain terminal of the polymer, wherein the crosslinked fluororubber (B) is a fluororesin In the presence of (A), the fluororubber (b) is mixed with a polyamine compound (c) having a thermal decomposition temperature of 210 ° C. or higher and a crosslinking accelerator (d) under the melting conditions of the fluororesin (A). Wherein the mass ratio (fluororesin (A) / fluororubber (b)) of the fluororesin (A) to the fluororubber (b) is less than 70/30, The thermoplastic resin composition is provided at least.

(4) The fluororubber (b) is preferably a vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene-based fluororubber.

Further, according to the present disclosure, a thermoplastic resin composition containing a fluororesin (A) and a crosslinked fluororubber (B), wherein the fluororesin (A) contains a chlorotrifluoroethylene unit and a tetrafluoroethylene unit. When an infrared absorption spectrum analysis is performed on a molded article which is a copolymer and is formed from the thermoplastic resin composition, the absorption peak at 3451 cm ^-1 is higher than the height of the absorption peak at 2360 cm ^-1. the ratio of height [K1] is, is 0.001 or more, and, with respect to the height of the absorption peak appearing in 3035Cm ^-1, the ratio of the height of the absorption peaks appearing in 1722 cm ^-1 [K2] is 0.3 As described above, a thermoplastic resin composition having a tensile modulus of 250 MPa or less is provided.

Further, according to the present disclosure, there is provided the method for producing a thermoplastic resin composition, wherein the fluororubber (b) is melted under the melting conditions of the fluororesin (A) in the presence of the fluororesin (A). A method for producing a thermoplastic resin composition comprising a step of dynamically crosslinking with a polyamine compound (c) having a thermal decomposition temperature of 210 ° C. or higher and a crosslinking accelerator (d).

According to the present disclosure, there is also provided a molded article formed from the above thermoplastic resin composition.

According to the present disclosure, there is also provided a laminate including a thermoplastic resin layer (W) formed from the above thermoplastic resin composition and an elastomer layer (X) formed from the elastomer composition.

The elastomer composition may be acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, blend rubber of acrylonitrile-butadiene rubber and acrylic rubber, chlorinated polyethylene, fluorine rubber, It is preferable to contain at least one elastomer selected from the group consisting of epichlorohydrin rubber, ethylene-propylene rubber, chlorosulfonated polyethylene rubber, silicone rubber and acrylic rubber.

It is preferable that the elastomer composition contains at least one compound selected from the group consisting of an onium salt, an amine compound and an epoxy resin.
Further, according to the present disclosure, there is provided a fuel hose or a fuel tube made of the above-mentioned molded article or the above-mentioned laminate.
Further, according to the present disclosure, there is provided a fuel sealing material comprising the above-mentioned molded product or the above-mentioned laminate.

According to the present disclosure, it is possible to provide a thermoplastic resin composition having a reduced tensile modulus without significantly impairing fuel barrier properties.

Hereinafter, specific embodiments of the present disclosure will be described in detail, but the present disclosure is not limited to the following embodiments.

熱 The thermoplastic resin composition of the present disclosure includes a fluororesin (A) and a crosslinked fluororubber (B).

The thermoplastic resin composition according to one embodiment of the present disclosure is characterized in that the crosslinked fluororubber (B) is a fluororesin (b) in the presence of the fluororesin (A) under the melting conditions of the fluororesin (A). It is dynamically crosslinked with a polyamine compound (c) having a thermal decomposition temperature of 210 ° C. or higher and a crosslinking accelerator (d). Thus, by using a specific polyamine compound in the dynamic crosslinking treatment, it is possible to obtain a thermoplastic resin composition having a reduced tensile modulus without greatly impairing the fuel barrier property. Further, the obtained thermoplastic resin composition has a relatively small compression set.

Further, the thermoplastic resin composition according to an embodiment of the present disclosure has a height of an absorption peak appearing at 2360 cm ⁻¹ when a molded article formed from the thermoplastic resin composition is subjected to infrared absorption spectrum analysis. for, the ratio of the height of the absorption peaks appearing in 3451cm ^-1 [K1] is, it is 0.001 or more, and, with respect to the height of the absorption peak appearing in 3035Cm ^-1, the height of the absorption peak appearing in 1722 cm ^-1 Is not less than 0.3 and the tensile modulus is not more than 250 MPa. As described above, the thermoplastic resin composition of the present disclosure exhibits a characteristic absorption peak, thereby obtaining a thermoplastic resin composition having a reduced tensile modulus without significantly impairing the fuel barrier property. Can be Further, the obtained thermoplastic resin composition has a relatively small compression set.

The ratio [K1] is preferably 0.003 or more, more preferably 0.005 or more, and the upper limit is not limited, but is usually 1.500 or less, and the ratio [K2] is preferably 0.4 or more, more preferably 0.5 or more, particularly preferably 1.0 or more, and most preferably 1.5 or more. The upper limit is not limited, but is usually 5.0 or less. is there.

The ratio [K1] and the ratio [K2] can be calculated by the following method. The thermoplastic resin composition is placed in a mold having a diameter of 120 mm, set in a press machine heated to 300 ° C., and melt-pressed at a pressure of about 2.9 MPa to produce a thermoplastic resin sheet. The infrared absorption spectrum of this thermoplastic resin sheet is measured by a transmission method using a Fourier transform infrared spectrophotometer [FT-IR], and the ratios [K1] and [K2] are calculated by the following equations.
Ratio [K1] = H1a / H1b
Ratio [K2] = H2a / H2b
H1a: 3475cm ^-1 and 3415cm absorbance 3451Cm ^-1 when the straight line connecting the respective absorbance was to baseline ^-1 height H1b: When the straight line connecting the respective absorbance 2680Cm ^-1 and 2030Cm ^-1 and a baseline absorbance of the height of the 2360 cm ^-1 H2a: 1760 cm ^-1 and 1660cm absorbance 1722 cm ^-1 when a straight line connecting the respective absorbance was to baseline ^-1 height H2b: each absorbance 3170Cm ^-1 and 2900 cm ^-1 Absorbance height of 3035 cm ^-1 when the connecting straight line is used as the baseline

The thermoplastic resin composition exhibiting a characteristic absorption peak is preferably prepared by subjecting a fluororubber (b) to a thermal decomposition temperature under the melting conditions of the fluororesin (A) in the presence of the fluororesin (A). Is dynamically crosslinked with a polyamine compound (c) having a temperature of 210 ° C. or higher and a crosslinking accelerator (d) to obtain a crosslinked fluororubber (B). Based on the type of bond belonging to each absorption peak, the larger the ratio [K1], the more the crosslinked structure formed by the reaction between the functional group of the fluororesin (A) and the polyamine compound (c) was formed. This means that the larger the ratio [K2], the more double bonds are formed in the main chain of the fluororubber (b), and the formed double bonds react with the polyamine compound (c). This is presumed to mean that many crosslinked structures were formed. That is, it is considered that the crosslink density in the thermoplastic resin composition can be estimated from the ratio [K1] and the ratio [K2]. Regardless of the validity of such a guess, the thermoplastic resin composition according to an embodiment of the present disclosure may have a fuel barrier property and a tensile modulus of elasticity when the ratio [K1] and the ratio [K2] are within the above ranges. Excellent balance and low compression set.

The tensile modulus is preferably 230 MPa or less, more preferably 200 MPa or less. The lower limit of the tensile modulus is not particularly limited, but may be 30 MPa or more.

The tensile modulus can be measured by the following method. The thermoplastic resin composition is placed in a mold having a diameter of 120 mm, set in a press heated to 300 ° C., and melt-pressed at a pressure of about 2.9 MPa to produce a thermoplastic resin sheet having a thickness of 0.5 mm. I do. From the obtained thermoplastic sheet, a dumbbell-shaped test piece having a distance between marked lines of 3.18 mm is punched out using an ASTM {D638} Type V dumbbell. Using the obtained dumbbell-shaped test piece, a tensile test was performed at 25 ° C. at a tensile speed of 50 mm / min at 25 ° C. using an autograph (AGS-J 5 kN manufactured by Shimadzu Corporation) according to ASTM D638. Find the modulus of elasticity.

In the thermoplastic resin composition of the present disclosure, the dispersion structure in which the crosslinked fluororubber (B) is dispersed in the fluororesin (A) is also considered from the viewpoint of the balance between the fuel barrier properties and the tensile elastic modulus and the compression set. And the average dispersed particle size of the crosslinked fluororubber (B) is preferably 5 μm or less.

The average dispersed particle diameter is preferably 2 μm or less, more preferably 1 μm or less, and the lower limit is not particularly limited, but may be 0.01 μm or more.

The average dispersed particle diameter refers to an image obtained by using any of an atomic force microscope (AFM), a scanning electron microscope (SEM), a transmission electron microscope (TEM), or a combination thereof. It is the average value of the equivalent circle diameters which were analyzed by image analysis software “ImageJ”, and 20 arbitrary particles of the dispersed phase were selected and calculated. For example, when the AFM is used, the difference obtained from the surface information of the continuous phase fluororesin (A) and the dispersed phase crosslinked fluororubber (B) is obtained as a bright and dark image. When SEM is used, the contrast is enhanced so that the cross-linked fluororubber (B) of the dispersed phase is clarified with respect to the image obtained as the reflected electron image or the secondary electron image, or the contrast is adjusted. By performing the above adjustment on the image, the crosslinked rubber particle diameter of the dispersed phase can be read as in the case of the AFM. In the case of a TEM, the diameter of the crosslinked rubber particles of the dispersed phase can be read in the same manner as in the AFM or the SEM by adjusting the contrast of the obtained image and / or adjusting the brightness or both of the image as in the SEM. These may be selected for each thermoplastic polymer composition so as to be more easily confirmed.

In the thermoplastic resin composition of the present disclosure, the mass ratio of the fluororesin (A) to the fluororubber (b) (fluororesin (A) / fluororubber (b)) is less than 70/30, and 20/80. That is all. The mass ratio is preferably 66/34 or less, preferably 30/70 or more, and more preferably 45/55 or more, from the viewpoint of the balance between the fuel barrier property and the tensile elastic modulus and compression set. is there. If the amount of the fluororesin (A) is too small, the fuel barrier property may be insufficient, and if it is too large, the tensile modulus and the compression set may be too large.

In the thermoplastic resin composition of the present disclosure, the mass ratio (fluororesin (A) / crosslinked fluororubber (B)) between the fluororesin (A) and the crosslinked fluororubber (B) is less than 70/30, / 80 or more. The mass ratio is preferably 65/35 or less, preferably 30/70 or more, and more preferably 45/55 or more, from the viewpoint of the balance between the fuel barrier property and the tensile modulus and compression set. is there. If the amount of the fluororesin (A) is too small, the fuel barrier property may be insufficient, and if it is too large, the tensile modulus and the compression set may be too large.

In the present disclosure, the mass ratio of the fluororesin (A) to the crosslinked fluororubber (B) in the thermoplastic resin composition may be, for example, the mass of the fluororesin (A) used to prepare the thermoplastic resin composition. And the sum of the respective masses of the fluororubber (b), the polyamine compound (c) and the crosslinking accelerator (d).

In the thermoplastic resin composition of the present disclosure, the volume ratio of the fluororesin (A) to the fluororubber (b) (fluororesin (A) / fluororubber (b)) is determined by the fuel barrier property, the tensile modulus, and the compression. From the viewpoint of the balance with the permanent set, the ratio is preferably 69/31 or less, more preferably 63/37 or less, preferably 18/82 or more, more preferably 28/72 or more, and further preferably 42/58 or more. If the amount of the fluororesin (A) is too small, the fuel barrier property may be insufficient, and if it is too large, the tensile modulus and the compression set may be too large.

In the thermoplastic resin composition of the present disclosure, the volume ratio between the fluororesin (A) and the crosslinked fluororubber (B) (fluororesin (A) / crosslinked fluororubber (B)) is determined by the fuel barrier property and the tensile modulus. From the viewpoint of balance with compression set, it is preferably 68/32 or less, more preferably 63/37 or less, preferably 18/82 or more, and more preferably 27/73 or more. It is preferably at least 42/58. If the amount of the fluororesin (A) is too small, the fuel barrier property may be insufficient, and if it is too large, the tensile modulus and the compression set may be too large.

In the present disclosure, the volume ratio between the fluororesin (A) and the crosslinked fluororubber (B) in the thermoplastic resin composition is, for example, the mass of the fluororesin (A) used for preparing the thermoplastic resin composition. , The value obtained by dividing the mass of the fluororubber (b) by its specific gravity, the value obtained by dividing the mass of the polyamine compound (c) by its specific gravity, and the mass of the crosslinking accelerator (d) by its specific gravity. It can be calculated from the ratio to the sum of the values divided by. In the thermoplastic resin composition of the present disclosure, when the crosslinked fluororubber (B) is isotropically and uniformly dispersed in the fluororesin (A), the fluororesin (A) and the crosslinked fluororubber (B ) Can be determined from an image obtained by using any of an atomic force microscope (AFM), a scanning electron microscope (SEM), a transmission electron microscope (TEM), or a combination thereof, It can also be calculated by calculating the area ratio between the fluororesin (A) in the phase and the crosslinked fluororubber (B) in the dispersed phase, and raising it to the 1.5th power.

The fuel permeability coefficient of the thermoplastic resin composition of the present disclosure is preferably 30 (g · mm) / (m ² · day) or less, and more preferably 25 (g · mm) / (m ² · day) or less. It is. The lower limit of the fuel permeability coefficient is not particularly limited, but is 4 (g · mm) / (m ² · day) or more in consideration of the balance between the fuel barrier property, the tensile modulus, and the compression set. Good.

The fuel permeability coefficient can be measured by the following method. The thermoplastic resin composition is placed in a mold having a diameter of 120 mm, set in a press machine heated to 300 ° C., and melt-pressed at a pressure of about 2.9 MPa to produce a thermoplastic resin sheet. 18 mL of CE10 (toluene / isooctane / ethanol = 45/45/10% by volume) as a simulated fuel was placed in a SUS container (open area: 1.26 × 10 ⁻³ m ² ) having a volume of 20 mL, and the mixture was thermoplastic. A resin sheet is set on the container opening and sealed to prepare a test specimen. The specimen is placed in a thermostat (60 ° C.), the mass of the specimen is measured, and when the mass loss per unit time becomes constant, the fuel permeability coefficient is determined by the following equation.

Fluororesin (A)
The fluororesin (A) is a copolymer containing chlorotrifluoroethylene (CTFE) units and tetrafluoroethylene (TFE) units.

The content of CTFE units in the fluororesin (A) is further improved by the balance between fuel barrier properties, tensile elastic modulus and compression set, and a thermoplastic resin composition having excellent heat resistance is obtained. It is preferably from 10 to 90 mol%, more preferably from 15 to 60 mol%, even more preferably from 18 to 40 mol%, based on the unit. If the CTFE unit is too small, the fuel barrier properties may be insufficient, and if too large, the heat resistance may be insufficient. On the other hand, the content of the TFE unit in the fluororesin (A) is further improved by the balance between the fuel barrier property, the tensile elastic modulus and the compression set, and a thermoplastic resin composition excellent in heat resistance is obtained. It is preferably from 10 to 90 mol%, more preferably from 40 to 85 mol%, even more preferably from 60 to 82 mol%, based on the monomer unit. If the TFE unit is too small, the heat resistance may be insufficient, and if it is too large, the fuel barrier property may be insufficient.

In the fluororesin (A), the content ratio of the CTFE unit and the TFE unit is more excellent due to the balance between the fuel barrier property, the tensile modulus and the compression set, and a thermoplastic resin composition having excellent heat resistance can be obtained. The molar ratio is preferably 10/90 to 90/10, more preferably 15/85 to 60/40, and still more preferably 18/82 to 40/60.

The fluororesin (A) is more excellent in the balance of fuel barrier properties, tensile modulus and compression set, and a thermoplastic resin composition having excellent heat resistance and crack resistance can be obtained. Therefore, the CTFE unit, the TFE unit, Further, those containing a monomer (α) unit derived from a monomer (α) copolymerizable with CTFE and TFE are preferable.

The monomer (α) is not particularly limited as long as it is a monomer copolymerizable with CTFE and TFE, and ethylene, vinylidene fluoride (VdF), CF ₂ ＣＦCF—ORf ¹ (where Rf ¹ Is a perfluoro (alkyl vinyl ether) (PAVE) represented by a perfluoroalkyl group having 1 to 8 carbon atoms, CX ¹ X ² = CX ³ (CF ₂ ) _n X ⁴ (wherein X ¹ and X ² And X ³ are the same or different and each is a hydrogen atom or a fluorine atom; X ⁴ is a hydrogen atom, a fluorine atom or a chlorine atom; n is an integer of 1 to 10); CF ₂ ＣＦCF And alkyl perfluorovinyl ether derivatives represented by —OCH ₂ —Rf ² (wherein Rf ² is a perfluoroalkyl group having 1 to 5 carbon atoms). At least one selected from the group consisting of vinyl monomers and alkyl perfluorovinyl ether derivatives is preferred, and at least one selected from the group consisting of PAVE and hexafluoropropylene (HFP) is more preferred.

The PAVE is preferably a perfluoro (alkyl vinyl ether) represented by CF ₂ ＣＦCF—ORf ³ (where Rf ³ represents a perfluoroalkyl group having 1 to 5 carbon atoms). Fluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE), perfluoro (propyl vinyl ether) (PPVE), perfluoro (butyl vinyl ether), etc., among which the group consisting of PMVE, PEVE and PPVE At least one selected from the above is preferable.

As the alkyl perfluorovinyl ether derivative, those in which Rf ² 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.

In the fluororesin (A), a thermoplastic resin composition which is more excellent in balance between fuel barrier properties, tensile elastic modulus and compression set, and is also excellent in heat resistance and crack resistance can be obtained. The total content of CTFE units and TFE units is preferably 90 to 99.9 mol%, more preferably 95 to 99.5 mol%, and the monomer (α) unit is Preferably it is 0.1 to 10 mol%, more preferably 0.5 to 5 mol%. If the amount of the monomer (α) is too small, the moldability and crack resistance may be insufficient. If the amount is too large, the fuel barrier property and the heat resistance may be insufficient.

含有 The content of each monomer unit of the above-mentioned fluororesin (A) can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis according to the type of monomer.

The melting point of the fluororesin (A) is preferably from 150 to 340 ° C., since a thermoplastic resin composition having more excellent balance between fuel barrier properties, tensile elastic modulus and compression set and excellent heat resistance can be obtained. The temperature is more preferably 215 to 290 ° C, further preferably 225 to 280 ° C, and particularly preferably 235 to 260 ° C. The melting point is a temperature corresponding to a melting peak when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimeter [DSC]. If the melting point is too low, the heat resistance may be insufficient, and if it is too high, the molding temperature may be high, and a part of the polyamine compound (c) may be decomposed to cause molding failure.

The melt flow rate (MFR) of the fluororesin (A) is preferably 0.01 to 100 g / 10 minutes. The MFR was measured using a melt indexer (manufactured by Toyo Seiki Seisaku-Sho, Ltd.) at 297 ° C. under a load of 5 kg under a load of 5 mm, from a nozzle having a diameter of 2 mm and a length of 8 mm per unit time (10 minutes). Obtained by measuring.

The fluororesin (A) is a copolymer 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 the side chain terminal of the polymer.

The carbonyl group is a functional group having —C (＝ O) —.

Specifically, for example,
Carbonate group [—OC (＝ 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 ⁵ , X ⁵ 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 organic group having 1 to 20 carbon atoms. Which is an organic group of)
Formula: —OC (＝ 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 (where R ⁷ is a monovalent organic group having 1 to 20 carbon atoms)],
A carbamoyl group [—C (＝ O) NR ⁸ R ⁹ (wherein R ⁸ and R ⁹ may be the same or different and are a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms) )],
Acid anhydride bond [-C (= O) -OC (= O)-],
Isocyanate group [-N = C = O],
And so on.

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 the above R ⁴ include a methylene group, a —CF ₂ — group, and a —C ₆ H ₄ — group. Specific examples of R ⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, Butyl group and the like. Specific examples of R ⁷ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Further, 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, a phenyl group and the like.

Among these carbonyl groups, a thermoplastic resin composition having a more excellent balance of fuel barrier properties, tensile elastic modulus and compression set can be obtained, and carboxyl group, haloformyl group, alkoxy group can be easily introduced into fluororesin. It is preferably at least one selected from the group consisting of a carbonyl group and a carbonate group, and includes —COOH, —OC (＝ O) OCH ₂ CH ₂ CH ₃ , —COF and —OC (（O) OCH (CH ₃ It is more preferable that at least one selected from the group consisting of ₂ ) is used.

An olefin group (Olefinic 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). And at least one selected from the group consisting of —CF ＝ CF ₂ , —CH ＝ CF ₂ , —CF ＝ CHF, —CF ＝ CH _2, and —CH ＝ CH ₂ .

An amino group is a monovalent functional group obtained by removing hydrogen from ammonia, a primary or secondary amine. As the amino group, the following formula:
-NR ¹³ R ¹⁴
(In the formula, R ¹³ and R ¹⁴ may be the same or different and each is 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 ) At least one selected from the above is preferable.

The number of functional groups of the fluororesin (A) can be measured by infrared absorption spectrum analysis, for example, by the method described in JP-B-37-3127 and WO 99/45044. it can. When the infrared absorption spectrum analysis of the film sheet of the fluororesin (A) is performed using an infrared spectrophotometer and the number of the functional groups is measured from the absorption band of the frequency specific to the functional group, for example, the -COF terminal is 1884 cm. ^-1 absorption band, -COOH terminal is 1813 cm ^-1 and 1775 cm ^-1 absorption bands, -COOCH ₃ terminal is 1795 cm ^-1 absorption band, -CONH ₂ terminal is 3438 cm ^-1 absorption band, -CH ₂ OH terminal Can be calculated from the absorption band at 3648 cm ^-1 , -CF = CF ₂ end at 1790 cm ^-1 , and the end containing a carbonate group [—OC (＝ O) O—] from the absorption band at 1810 to 1815 cm ⁻¹ . The absorbance of the peak appearing in each absorption band can be determined, for example, by measuring the obtained infrared absorption spectrum in Perkin-Elmer Spectrum for windows Ver. It can be measured by automatically determining the baseline using 1.4C.

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 during the polymerization of the fluororesin, the functional group or a functional group that can be converted to the functional group. Method of polymerizing using a polymerization initiator having, 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 of converting the terminal of the fluororesin using a device capable of adding the compound.

Examples of the monomer having the functional group include (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, and mesaconic anhydride. And unsaturated aliphatic carboxylic acids such as aconitic acid and aconitic anhydride.

The number of the functional groups of the fluororesin (A) is determined by the following: a thermoplastic resin composition having a better balance between fuel barrier properties, tensile modulus and compression set can be obtained, and foaming during molding can be avoided. It is preferably 20 to 5,000, more preferably 30 to 4,000, and even more preferably 40 to 3,000 per million carbon atoms constituting A).

In addition, the fluororesin (A) having the above functional group used in the present disclosure is not limited to one composed of only a molecule having the above functional group at one end, both ends or side chains of a main chain in one polymer. A mixture of a molecule having the above functional group at one end, both ends or side chains of the main chain of the polymer and a molecule not containing the above functional group may be used.

Crosslinked fluoro rubber (B)
The crosslinked fluororubber (B) is a polyamine compound (c) having a thermal decomposition temperature of 210 ° C. or higher under the melting conditions of the fluororesin (A) in the presence of the fluororesin (A). It is preferable that the resin is dynamically crosslinked with the crosslinking accelerator (d).

Dynamic crosslinking treatment refers to dynamically crosslinking non-crosslinked fluororubber (b) simultaneously with melt kneading using a Banbury mixer, a pressure kneader, an extruder, or the like. Among these, an extruder such as a twin-screw extruder is preferable because a high shearing force can be applied. By dynamically performing the crosslinking treatment, the phase structure of the fluororesin (A) and the crosslinked fluororubber (B) can be controlled.

架橋 Cross-linking treatment under melting conditions means cross-linking treatment at a temperature not lower than the melting point of the fluororesin (A). The temperature of the crosslinking treatment is preferably equal to or higher than the melting point of the fluororesin (A), more preferably equal to or lower than 330 ° C, and still more preferably equal to or lower than 320 ° C. As long as the temperature is equal to or higher than the melting point of the fluororesin (A), the temperature may be 150 ° C or higher, but is preferably 220 ° C or higher, more preferably 260 ° C or higher. By setting the kneading temperature in the above range, the fluororesin (A) and the crosslinked fluororubber (B) can be sufficiently kneaded, and at the same time, the thermal degradation of the uncrosslinked fluororubber (b) can be suppressed.

In the thermoplastic resin composition of the present disclosure, a crosslinked fluororubber (B) is obtained by performing dynamic crosslinking with a specific polyamine compound (c). Even in the case of performing crosslinking, crosslinking of the uncrosslinked fluororubber (b) sufficiently proceeds, and the fluororesin (A) and the crosslinked fluororubber (B) are sufficiently dispersed in each other.

In the thermoplastic resin composition of the present disclosure, the fluororesin (A) may form a continuous phase and the crosslinked fluororubber (B) may form a dispersed phase, or the fluororesin (A) and the crosslinked fluororubber ( Although B) may form a co-continuous phase structure, it is preferred that the fluororesin (A) forms a continuous phase and the crosslinked fluororubber (B) forms a dispersed phase. A part of the structure in which the fluororesin (A) forms a continuous phase and the crosslinked fluororubber (B) forms a dispersed phase includes a co-continuous phase of the fluororesin (A) and the crosslinked fluororubber (B). A structure may be included.

Even when the uncrosslinked fluororubber (b) forms a matrix at the initial stage of dispersion, if the uncrosslinked fluororubber (b) is changed to the crosslinked fluororubber (B) by the crosslinking reaction, the crosslinked fluororubber (B) becomes Has a higher melt viscosity than the uncrosslinked fluororubber (b), the crosslinked fluororubber (B) forms a dispersed phase, or the fluororesin (A) and the crosslinked fluororubber (B) form a co-continuous phase structure Will do.

The crosslinked fluororubber (B) is obtained by crosslinking an uncrosslinked fluororubber (b).

The fluororubber (b) is preferably at least one selected from the group consisting of a perfluororubber, a partially fluorinated rubber, and a fluorinated thermoplastic elastomer, and more preferably a partially fluorinated rubber.

The fluororubber (b) preferably has, for example, a Mooney viscosity ML (1 + 10) of 10 to 100 measured at 100 ° C. The Mooney viscosity ML (1 + 10) can be measured using an ALPHA TECHNOLOGIES Co., Ltd. Mooney viscometer MV2000E in accordance with ASTM D-1646.

As the fluorine rubber (b), VdF fluorine rubber, TFE / propylene fluorine rubber, TFE / propylene / VdF fluorine rubber, ethylene / HFP fluorine rubber, ethylene / HFP / VdF fluorine rubber, ethylene / HFP / TFE And fluorocarbon rubber. Among them, it is preferably at least one selected from the group consisting of VdF-based fluororubber and TFE / propylene-based fluororubber, and more preferably VdF / TFE / HFP-based fluororubber.

The VdF-based fluororubber is preferably a copolymer comprising 20 to 85 mol% of VdF and 80 to 15 mol% of at least one other monomer copolymerizable with VdF. More preferably, it is a copolymer comprising 25 to 80 mol% of VdF and 75 to 20 mol% of at least one other monomer copolymerizable with VdF.

Examples of the at least one other monomer copolymerizable with VdF include TFE, HFP, fluoroalkyl vinyl ether, CTFE, trifluoroethylene, trifluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, and hexafluoroisobutene. , Vinyl fluoride, a general formula (1): a fluoromonomer represented by CH ₂ ＣＦCFRf ¹¹ (wherein Rf ¹¹ is a linear or branched fluoroalkyl group having 1 to 12 carbon atoms), a general formula (2) : A fluoromonomer represented by CH ₂ ＣＨCH— (CF ₂ ) _n —X ²¹ (where X ²¹ is H or F, and n is an integer of 3 to 10), and a monomer that provides a crosslinking site Non-fluorinated monomers such as ethylene, propylene and alkyl vinyl ether And the like. These can be used alone or in any combination. Among these, at least one selected from the group consisting of TFE, HFP, fluoroalkyl vinyl ether and CTFE is preferred. As the fluoroalkyl vinyl ether, perfluoro (alkyl vinyl ether) represented by CF ₂ ＣＦCF—ORf ⁴ (where Rf ⁴ represents a perfluoroalkyl group having 1 to 5 carbon atoms) is preferable.

Examples of the monomer that provides a crosslinking site include, for example, a compound represented by the following general formula (3):
_{^{CX 6 2 = CX 6 -Rf 5}} CHR 31 X 31 (3)
(In the formula, X ⁶ may be the same or different, and a hydrogen atom, a fluorine atom or —CH ₃ , Rf ⁵ represents a fluoroalkylene group, a perfluoroalkylene group, a fluoropolyoxyalkylene group or a perfluoroalkyl group. A polyoxyalkylene group, R ³¹ is a hydrogen atom or —CH ₃ , and X ³¹ is an iodine atom or a bromine atom), iodine or bromine-containing monomer represented by general formula (4):
CF ₂ ＣＦCFO (CF ₂ CF (CF ₃ ) O) _m (CF ₂ ) _n -X ⁴¹ (4)
(Wherein, m is an integer of 0 to 5, n is an integer of 1 to 3, and X ⁴¹ is a cyano group, a carboxyl group, an alkoxycarbonyl group, or a bromine atom). These can be used alone or in any combination.

Specific examples of the VdF-based fluororubber include VdF / HFP-based rubber, VdF / TFE / HFP-based rubber, VdF / CTFE-based rubber, VdF / CTFE / TFE-based rubber, and VdF / fluoro represented by the general formula (1). Examples include monomer-based rubber, VdF / fluoromonomer / TFE-based rubber represented by the general formula (1), VdF / PMVE-based rubber, VdF / PMVE / TFE-based rubber, and VdF / PMVE / TFE / HFP-based rubber. As the fluoromonomer rubber represented by VdF / general formula (1), at least one selected from the group consisting of VdF / CH ₂ ＣＦCFCF ₃ rubber and VdF / CH ₂ ＣＦCFCF ₃ / HFP rubber is used. VdF / TFE / CH ₂ ＣＦCFCF ₃ rubber is preferably used as the VdF / fluoromonomer / TFE rubber represented by the general formula (1).

The VdF / CH ₂ ＣＦCFCF ₃ rubber has a VdF unit / CH ₂ ＣＦCFCF ₃ unit molar ratio of preferably 40/60 to 99.5 / 0.5, more preferably 50/50 to 85 /. Fifteen.

The TFE / propylene-based fluororubber has a molar ratio of TFE unit / propylene unit of preferably 45/55 to 70/30.

The VdF / HFP fluororubber preferably has a VdF unit / HFP unit molar ratio of 80/20 to 65/35.

The VdF / TFE / HFP fluororubber preferably has a molar ratio of VdF unit / TFE unit / HFP unit of (25 to 65) / (15 to 45) / (20 to 40).

含有 The content of each monomer unit of the above-mentioned fluororubber (b) can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis according to the type of monomer.

Polyamine compound (c)
The thermoplastic resin composition of the present disclosure includes a polyamine compound (c) having a thermal decomposition temperature of 210 ° C or higher. The polyamine compound (c) is a compound having two or more amino groups in one molecule. The polyamine compound (c) not only functions as a crosslinking agent for the fluororubber (b), but also reacts with the functional group of the fluororesin (A), thereby reducing the tensile elastic modulus without greatly impairing the fuel barrier property. It is estimated that the obtained thermoplastic resin composition is obtained.

When a polyamine compound having a thermal decomposition temperature that is too low is used, a part of the polyamine compound is decomposed in the production process of the thermoplastic resin composition, so that not only does the crosslinking of the fluororubber (b) not sufficiently proceed, but also the fuel barrier property is greatly impaired. Thus, a thermoplastic resin composition having a reduced tensile modulus cannot be obtained. The thermal decomposition temperature of the polyamine compound (c) is 210 ° C. or higher, preferably 250 ° C. or higher, and more preferably 275 ° C. or higher. The upper limit of the thermal decomposition temperature is not particularly limited, but is usually 400 ° C. or lower.

The above-mentioned thermal decomposition temperature is the temperature at which the weight loss reaches 1% of the initial weight in thermogravimetric analysis [TG] of the polyamine compound (heating rate 10 ° C / min, under dry air).

Specific examples of the polyamine compound (c) include 2,2-bis [4- (4-aminophenoxy) phenyl] propane (hereinafter, referred to as BAPP) and 2,2-bis [4- (4-amino Phenoxy) phenyl] hexafluoropropane (hereinafter referred to as 6FBAPP), bis [4- (4-aminophenoxy) phenyl] sulfone (hereinafter referred to as BAPS), 4,4'-diaminodiphenylsulfone (hereinafter referred to as DDS) ), 3,3'-diaminodiphenylsulfone (hereinafter referred to as 3,3'-DAS), 4,4 '-[(1,3-phenylene) bis (dimethylmethylene)] bisaniline (hereinafter referred to as bisaniline-M) 4,4 ′-[(1,4-phenylene) bis (dimethylmethylene)] bisaniline (hereinafter referred to as bisaniline-P), 1,4-bi (4-aminophenoxy) -2-phenylbenzene (hereinafter, referred to as P-TPE-Q), 1,4-bis (4'-aminophenoxy) -2,3,5-trimethylbenzene (hereinafter, referred to as TMBAB) ), 1,3-bis (4-aminophenoxy) benzene (hereinafter referred to as TPE-R), tris (4-aminophenyl) methane, tetrakis (4-aminophenyl) methane and the like. These polyamine compounds (c) may be used alone or in any combination with the polyamine compound (c) having another structure. Among them, a thermoplastic resin composition having a more excellent balance of fuel barrier properties, tensile elastic modulus and compression set can be obtained, so that BAPP, 6FBAPP, BAPS, DDS, 3,3′-DAS, P-TPE-Q , Bisaniline-P, TMBAB, and TPE-R are preferred, BAPP, 6FBAPP, BAPS, DDS, 3,3'-DAS, and P-TPE-Q are more preferred, and BAPP is even more preferred.

The compounding amount of the polyamine compound (c) is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the fluororubber (b). If the compounding amount is too small, the crosslinking reaction of the fluororubber (b) and the reaction with the functional group of the fluororesin (A) do not sufficiently proceed, and the thermal barrier property, the tensile elastic modulus, and the balance of compression set are excellent. There is a possibility that a plastic resin composition cannot be obtained. On the other hand, if the compounding amount is too large, the dispersion of the polyamine compound (c) becomes insufficient, and there is a possibility that molding defects such as foaming may occur and fuel barrier properties may decrease. The blending amount of the polyamine compound (c) is more preferably 0.5 to 5 parts by mass, and still more preferably 1 to 5 parts by mass.

は In addition, in the thermoplastic resin composition of the present disclosure, the polyol crosslinking agent or the polyhydroxy compound is preferably 1 part by mass or less based on 100 parts by mass of the fluororubber (b). If the amount of the polyol crosslinking agent or the polyhydroxy compound is too large, the crosslinking reaction of the fluororubber (b) by the polyamine compound (c) and the reaction with the functional group of the fluororesin (A) are inhibited, and the fuel barrier property, the tensile elastic modulus and There is a possibility that a thermoplastic resin composition having an excellent balance of compression set may not be obtained. The content of the polyol crosslinking agent or the polyhydroxy compound is more preferably 0.1 part by mass or less based on 100 parts by mass of the fluororubber (b), and further preferably it is not contained at all.

Crosslinking accelerator (d)
As the crosslinking accelerator (d) used together with the polyamine compound (c), a crosslinking accelerator conventionally used for promoting crosslinking of a polyol crosslinking system can be used.

Specifically, an onium compound can be used as the crosslinking accelerator (d). The onium compound is not particularly limited, and examples thereof include ammonium compounds such as quaternary ammonium salts, phosphonium compounds such as quaternary phosphonium salts, oxonium compounds, sulfonium compounds, cyclic amines, and monofunctional amine compounds. Among these, a quaternary ammonium salt or a quaternary phosphonium salt is preferable, and a quaternary ammonium salt is more preferable.

The quaternary ammonium salt is not particularly limited. For example, 8-methyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 8-methyl-1,8-diazabicyclo [5. 4.0] -7-undecenium iodide, 8-methyl-1,8-diazabicyclo [5.4.0] -7-undecenium hydroxide, 8-methyl-1,8-diazabicyclo [5 .4.0] -7-undecenium methyl sulfate, 8-ethyl-1,8-diazabicyclo [5.4.0] -7-undecenium bromide, 8-propyl-1,8-diazabicyclo [5 .4.0] -7-undecenium bromide, 8-dodecyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 8-dodecyl-1,8-diazabicyclo [ .4.0] -7-undecenium hydroxide, 8-eicosyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 8-tetracosyl-1,8-diazabicyclo [5 .4.0] -7-undecenium chloride, 8-benzyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride (hereinafter referred to as DBU-B), 8-benzyl- 1,8-diazabicyclo [5.4.0] -7-undecenium hydroxide, 8-phenethyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 8- (3 -Phenylpropyl) -1,8-diazabicyclo [5.4.0] -7-undecenium chloride and the like. Among these, DBU-B is preferable from the viewpoint of crosslinkability and physical properties of the crosslinked product.

The quaternary phosphonium salt is not particularly limited, and examples thereof include tetrabutylphosphonium chloride, benzyltriphenylphosphonium chloride (hereinafter, referred to as BTPPC), benzyltrimethylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl -2-methoxypropylphosphonium chloride, benzylphenyl (dimethylamino) phosphonium chloride, methyltriphenylphosphonium bromide, allyltriphenylphosphonium bromide, (bromomethyl) triphenylbromide, tetraphenylphosphonium bromide and the like. BTPPC is preferred from the viewpoint of crosslinkability and physical properties of the crosslinked product.

塩 素 Further, as a crosslinking accelerator, a chlorine-free crosslinking accelerator disclosed in JP-A-11-147891 can be used.

The compounding amount of the crosslinking accelerator (d) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the fluororubber (b). Preferably it is 0.1 to 1.0 part by mass. If the amount of the crosslinking accelerator (d) is too small, the crosslinking reaction of the fluororubber (b) by the polyamine compound (c) and the reaction with the functional group of the fluororesin (A) do not sufficiently proceed, and the fuel barrier property and the tensile elasticity There is a possibility that a thermoplastic resin composition having an excellent balance between the modulus and the compression set may not be obtained. On the other hand, if the amount is too large, poor dispersion occurs, and there is a possibility that a thermoplastic resin composition which is still more excellent in balance with the fuel barrier property, tensile modulus and compression set may not be obtained.

The crosslinked fluororubber (B) can be used in addition to the polyamine compound (c) and the crosslinking accelerator (d) because a thermoplastic resin composition having a better balance between fuel barrier properties, tensile elastic modulus and compression set can be obtained. It is also preferred that the resin is dynamically cross-linked with an acid acceptor.

As the acid acceptor, magnesium oxide, magnesium hydroxide, barium hydroxide, magnesium carbonate, barium carbonate, quicklime, slaked lime, calcium carbonate, calcium silicate, calcium stearate, zinc stearate, calcium phthalate, calcium phosphite, tin oxide And basic tin phosphite, and among them, magnesium oxide is preferable.

The compounding amount of the acid acceptor is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and further preferably 0 to 10 parts by mass with respect to 100 parts by mass of the fluororubber (b). 0.5 to 6 parts by mass.

熱 The thermoplastic resin composition of the present disclosure also preferably has conductivity in order to prevent accumulation of static charge and ignition. From this viewpoint, the thermoplastic resin composition of the present disclosure preferably contains a conductive material such as carbon black and acetylene black. The conductive material is preferably 0.01 to 20% by mass, more preferably 1 to 18% by mass, and still more preferably 5 to 15% by mass, based on the thermoplastic resin composition of the present disclosure. .

Further, the thermoplastic resin composition of the present disclosure includes other polymers such as polyethylene, polypropylene, polyamide, polyester, and polyurethane; inorganic fillers such as talc, celite, clay, titanium oxide, carbon black, and barium sulfate; and pigments. , Flame retardants, lubricants, light stabilizers, weathering stabilizers, antistatic agents, UV absorbers, antioxidants, mold release agents, foaming agents, fragrances, oils, softeners, etc. It can be added in a range that does not affect.

The present disclosure relates to a method for producing the above-mentioned thermoplastic resin composition, wherein a fluororubber (b) is thermally decomposed at a melting temperature of the fluororesin (A) in the presence of the fluororesin (A). The present invention also relates to a method for producing a thermoplastic resin composition including a step of dynamically cross-linking together with a polyamine compound (c) having a temperature of 210 ° C. or higher and a cross-linking accelerator (d).

The above-mentioned step is also a step of kneading the fluororubber (b) and the crosslinking accelerator (d) to obtain a fluororubber composition, wherein the fluororesin (A) and the fluororesin (A) Kneading the polyamine compound (c) to obtain a fluororesin composition, and kneading the fluororesin composition and the fluororubber composition at a temperature equal to or higher than the melting point of the fluororesin (A). be able to.

The above-mentioned step is also a step of kneading the fluororubber (b) and the crosslinking accelerator (d) to obtain a fluororubber composition, wherein the fluororesin (A) and the fluororesin (A) A step of kneading the fluororubber composition to obtain a thermoplastic resin composition intermediate, and the step of mixing the thermoplastic resin composition intermediate and the polyamine compound (c) at a temperature not lower than the melting point of the fluororesin (A). And a step of kneading.

The above-mentioned step is also a step of kneading the fluororubber (b), the polyamine compound (c) and the crosslinking accelerator (d) to obtain a fluororubber composition, and a temperature higher than the melting point of the fluororesin (A). And a step of kneading the fluororubber composition and the fluororesin (A). At this time, if necessary, a solid solution in which the polyamine compound (c) and the crosslinking accelerator (d) are once melted to lower the melting point may be used.

In any of the steps, in the last kneading step, the fluororubber (b) is dynamically crosslinked, and a thermoplastic resin composition containing the fluororesin (A) and the crosslinked fluororubber (B) can be obtained.

に も For any of the above kneading, a Banbury mixer, a pressure kneader, an extruder, or the like can be used.

Molded Article The molded article of the present disclosure is formed from the above-described thermoplastic resin composition. The shape of the molded article is not particularly limited, and examples include a tube, a hose, a sheet, and a film.

The above-mentioned molded product can be manufactured by using a general molding method or molding apparatus. As a molding method, for example, any method such as injection molding, extrusion molding, compression molding, blow molding, calender molding, and vacuum molding can be adopted.

Further, the method of manufacturing the molded article, in order to fly out moisture and oligomers and the like adhering to the surface of the thermoplastic resin composition and obtain a stable molded article without poor appearance, the method of manufacturing the molded article includes the above-mentioned thermoplastic resin composition. It is preferable to include a step of heating and drying the thermoplastic resin composition before the step of molding. The heating and drying temperature is preferably 80 ° C. or higher, more preferably 110 ° C. or higher, even more preferably 130 ° C. or higher, and particularly preferably 150 ° C. or higher. The heating and drying temperature is preferably not more than the melting point of the fluororesin (A), more preferably not more than 230 ° C, further preferably not more than 210 ° C, and particularly preferably not more than 200 ° C.

揮 発 After the molded article is manufactured, the obtained molded article can be heated to remove volatile components in the molded article.

Laminate The laminate of the present disclosure includes a thermoplastic resin layer (W) formed from the above thermoplastic resin composition and an elastomer layer (X) formed from the elastomer composition.

The elastomer composition contains an elastomer. Examples of the elastomer include acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, acrylonitrile-butadiene rubber and acrylic rubber. Blended rubber, chlorinated polyethylene, fluorine rubber, epichlorohydrin rubber, ethylene-propylene rubber, chlorosulfonated polyethylene rubber, acrylic rubber, silicone rubber, butyl rubber, styrene-butadiene rubber, ethylene-vinyl acetate copolymer, α, Examples include β-unsaturated nitrile-conjugated diene copolymer rubber and hydrides of α, β-unsaturated nitrile-conjugated diene copolymer rubber.

The above elastomer composition includes acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, blend rubber of acrylonitrile-butadiene rubber and acrylic rubber, chlorinated polyethylene, fluorine rubber, It is preferable to contain at least one elastomer selected from the group consisting of epichlorohydrin rubber, ethylene-propylene rubber, chlorosulfonated polyethylene rubber, silicone rubber and acrylic rubber. Above all, the elastomer composition is selected from the group consisting of acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, fluorine rubber and epichlorohydrin rubber in terms of heat resistance, oil resistance, weather resistance and extrusion moldability. More preferably, it contains at least one kind of elastomer, and more preferably, it contains fluorine rubber.

Examples of the fluorine rubber contained in the elastomer composition include VdF fluorine rubber, TFE / propylene fluorine rubber, TFE / propylene / VdF fluorine rubber, ethylene / HFP fluorine rubber, ethylene / HFP / VdF fluorine rubber, Ethylene / HFP / TFE-based fluororubber and the like can be mentioned. Among them, at least one selected from the group consisting of VdF-based fluororubber and TFE / propylene-based fluororubber is preferable, and selected from the group consisting of VdF / HFP-based fluororubber and VdF / TFE / HFP-based fluororubber. It is more preferable that at least one of them is used. The VdF / TFE / HFP fluororubber preferably has a molar ratio of VdF unit / TFE unit / HFP unit of (25 to 65) / (15 to 45) / (20 to 40).

The elastomer composition contains at least one compound selected from the group consisting of an onium salt, an amine compound, and an epoxy resin from the viewpoint of improving the adhesive strength between the thermoplastic resin layer (W) and the elastomer layer (X). Is preferred.

The onium salt is not particularly limited, and includes, for example, quaternary ammonium salts, quaternary phosphonium salts, oxonium salts, sulfonium salts, cyclic amines, and monofunctional amine compounds. And quaternary phosphonium salts.

と し て The quaternary ammonium salt is not particularly limited, and may be, for example, a compound represented by the formula (5):

(Wherein R is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and X ⁻ is a monovalent anion), a compound represented by the formula (6):

(Wherein R is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and X ⁻ is a monovalent anion), a compound represented by the formula (7):

(Wherein three Rs may be the same or different and are a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and X ⁻ is a monovalent anion) A compound represented by the formula (8):

(Wherein n is an integer of 0 to 50), and a compound represented by the formula (9):

And the like.

R in the formula (5) is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. Examples of the monovalent organic group having 1 to 30 carbon atoms include, but are not particularly limited to, an aliphatic hydrocarbon group, a benzyl group, a phenethyl group, and a 3-phenylpropyl group. In the formula (5), X ⁻ represents a halogen ion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), OH ⁻ , RO ⁻ , HCOO ⁻ , RCOO ⁻ , C ₆ H ₅ O ⁻ , ROSO ₃ ⁻ , RSO ₃ ^- (R is a monovalent organic group). As the compound of the formula (5), specifically, 8-methyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 8-methyl-1,8-diazabicyclo [5. 4.0] -7-undecenium iodide, 8-methyl-1,8-diazabicyclo [5.4.0] -7-undecenium hydroxide, 8-methyl-1,8-diazabicyclo [5 .4.0] -7-undecenium methyl sulfate, 8-ethyl-1,8-diazabicyclo [5.4.0] -7-undecenium bromide, 8-propyl-1,8-diazabicyclo [5 .4.0] -7-undecenium bromide, 8-dodecyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 8-dodecyl-1,8-diazabicyclo [5.4] .0] -7- Ndecenium hydroxide, 8-eicosyl-1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 8-tetracosyl-1,8-diazabicyclo [5.4.0] -7 -Undecenium chloride, DBU-B, 8-benzyl-1,8-diazabicyclo [5.4.0] -7-undecenium hydroxide, 8-phenethyl-1,8-diazabicyclo [5.4. 0] -7-undecenium chloride, 8- (3-phenylpropyl) -1,8-diazabicyclo [5.4.0] -7-undecenium chloride, 1,8-diazabicyclo [5.4.0] ] -7-Undecenium phthalate, 1,8-diazabicyclo [5.4.0] -7-undecenium tosylate, 1,8-diazabicyclo [5.4.0] -7-undecenium Phenolate, 1,8-diazabicyclo [5.4.0] -7-undecenium naphthoate, 1,8-diazabicyclo [5.4.0] -7-undecenium octanoate, 1,8-diazabicyclo [5.4.0] -7-undecenium oleate, 1,8-diazabicyclo [5.4.0] -7-undecenium formate, 1,8-diazabicyclo [5.4.0]- 7-undecenium chloride and the like.

R in the formula (6) is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. Examples of the monovalent organic group having 1 to 30 carbon atoms include, but are not particularly limited to, an aliphatic hydrocarbon group and a benzyl group. In the formula (6), X ⁻ represents a halogen ion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), HCO ₃ ⁻ , OH ⁻ , RO ⁻ , HCOO ⁻ , RCOO ⁻ , C ₆ H ₅ O ⁻ , ROSO ₃ ⁻ , RSO ₃ ⁻ (R is a monovalent organic group) and the like. Specific examples of the compound of the formula (6) include 1,8-diazabicyclo [4.3.0] -5-nonenium phthalate and 1,8-diazabicyclo [4.3.0] -5-none. 1,8-diazabicyclo [4.3.0] -5-nonenium phenolate, 1,8-diazabicyclo [4.3.0] -5-nonenium naphthoate, 1,8-diazabicyclo [ 4.3.0] -5-nonenium octanoate, 1,8-diazabicyclo [4.3.0] -5-nonenium oleate, 1,8-diazabicyclo [4.3.0] -5- Nonenium formate, 1,8-diazabicyclo [4.3.0] -5-nonenium chloride and the like can be mentioned.

In the formula (7), three Rs are the same or different and are each a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. Examples of the monovalent organic group having 1 to 30 carbon atoms include, but are not particularly limited to, an aliphatic hydrocarbon group, an aryl group such as a phenyl group, and a benzyl group. Specifically, for example, an alkyl group having 1 to 30 carbon atoms such as —CH ₃ , —C ₂ H ₅ , and —C ₃ H ₇ ; —CX ⁷¹ ₃ , —C ₂ X ⁷¹ ₅ , and —CH ₂ X ^{71 _{, -CH 2 CX 71 3, -CH}} 2 C 2 X 71 5 halogen atom-containing alkyl group having 1 to 30 carbon atoms, such as ^{(X 71} is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom); a phenyl group; Benzyl group; phenyl group or benzyl group in which 1 to 5 hydrogen atoms have been substituted with fluorine atoms such as —C ₆ F ₅ and —CH ₂ C ₆ F ₅ ; —C ₆ H _5-n (CF ₃ ) _n And a phenyl group or a benzyl group in which 1 to 5 hydrogen atoms have been substituted with -CF ₃ , such as -CH ₂ C ₆ H _5-n (CF ₃ ) _n (n is an integer of 1 to 5). . Equation (10):

May contain a nitrogen atom. In the formula (7), X ⁻ represents a halogen ion (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ ), HCO ₃ ⁻ , OH ⁻ , RO ⁻ , HCOO ⁻ , RCOO ⁻ , C ₆ H ₅ O ⁻ , ROSO ₃ ⁻ , RSO ₃ ⁻ (R is a monovalent organic group) and the like.

Among them, the compounds represented by the formula (5), the formula (6), the formula (7) or the formula (8) from the viewpoint that the adhesive strength between the thermoplastic resin layer (W) and the elastomer layer (X) is good. Is preferred. Examples of the compound represented by the formula (5) include DBU-B, 1,8-diazabicyclo [5.4.0] -7-undecenium naphthoate, and 1,8-diazabicyclo [5.4.0] -7. -Undecenium phenolate, 1,8-diazabicyclo [5.4.0] -7-undecenium phthalate, or 1,8-diazabicyclo [5.4.0] -7-undecenium formate More preferably, it is DBU-B or 1,8-diazabicyclo [5.4.0] -7-undecenium formate. As the compound represented by the formula (7), a compound in which three Rs in the formula (7) are an alkyl group or a benzyl group having 1 to 20 carbon atoms and X ⁻ is Cl ⁻ is more preferable, and the compound represented by the formula (11) ):

The compound represented by is more preferred. In the compound represented by the formula (8), n is more preferably an integer of 0 to 10, more preferably an integer of 1 to 5, from the viewpoint of dispersibility at the time of kneading with rubber. preferable.

ＤＢOf these, DBU-B is particularly preferred.

The quaternary phosphonium salt is not particularly restricted but includes, for example, tetrabutylphosphonium chloride, BTPPC, benzyltrimethylphosphonium chloride, benzyltributylphosphonium chloride, tributylallylphosphonium chloride, tributyl-2-methoxypropylphosphonium chloride, benzylphenyl (dimethylamino) ) Phosphonium chloride and the like, and among these, BTPPC is preferred from the viewpoint of good adhesion between the thermoplastic resin layer (W) and the elastomer layer (X).

Also, quaternary ammonium salts, solid solutions of quaternary phosphonium salts and bisphenol AF, and the compounds disclosed in JP-A-11-147891 can be used.

The amount of the onium salt is preferably 0.1 to 10.0 with respect to 100 parts by mass of the elastomer, since sufficient adhesiveness can be obtained and good dispersion of the onium salt in the elastomer composition can be obtained. Parts by mass, more preferably 0.2 to 8.0 parts by mass, even more preferably 0.3 to 7.0 parts by mass.

The amine compound is not particularly restricted but includes, for example, hexamethylenediamine carbamate, N, N'-dicinnamylidene-1,6-hexamethylenediamine (hereinafter referred to as V3), 4,4'-bis (aminocyclohexyl) methane carbamate Such as aliphatic polyamine compound derivatives, 4,4′-diaminodiphenyl ether (hereinafter, referred to as 4,4′-DPE), BAPP, 6FBAPP, BAPS, DDS, 3,3′-DAS, P-TPE-Q, Bisaniline-M, bisaniline-P, TMBAB, TPE-R, p-phenylenediamine, m-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, N, N'-dimethyl-1,4-phenylenediamine 4,4'-methylenedianiline, dianilinoethane, 4,4'-methyl Down - bis (3-nitroaniline), 4,4'-methylene - bis (2-chloroaniline), diaminopyridine, an aromatic polyamine compound such as melamine may be used. Among them, V3, 4,4'-DPE, BAPP, 6FBAPP, BAPS, DDS, 3,3'-DAS, from the viewpoint of good adhesion between the thermoplastic resin layer (W) and the elastomer layer (X). , P-TPE-Q, bisaniline-M, bisaniline-P, TMBAB, and TPE-R are preferred, and V3, 4,4'-DPE, BAPP, 6FBAPP, P-TPE-Q, bisaniline-M, bisaniline-P, TMBAB and TPE-R are more preferred.

The compounding amount of the amine compound is preferably 0.1 to 10.0 with respect to 100 parts by mass of the elastomer since sufficient adhesiveness is obtained and good dispersibility of the amine compound in the elastomer composition is obtained. Parts by mass, more preferably 0.2 to 8.0 parts by mass, even more preferably 0.3 to 7.0 parts by mass.

(4) Examples of the epoxy resin include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a polyfunctional epoxy resin. Of these, bisphenol A type epoxy resin has the formula (12):

And the like. Here, n in the formula (12) is preferably 0.1 to 3, and more preferably 0.1 to 3, since sufficient adhesiveness is obtained and good dispersibility of the epoxy resin in the elastomer composition is obtained. Is 0.1 to 0.5, more preferably 0.1 to 0.3.

The amount of the epoxy resin is preferably from 0.1 to 20.0 parts by mass, more preferably from 0.3 to 2 parts by mass, per 100 parts by mass of the elastomer, since sufficient adhesiveness and flexibility of the elastomer layer (X) can be obtained. 15.0 parts by mass is more preferable, and 0.5 to 10.0 parts by mass is more preferable.

Elastomer layer (X) can be either unvulcanized rubber or vulcanized.

と し て As the vulcanizing agent, any vulcanizing agent used for ordinary elastomers can be used. For example, sulfur vulcanizing agents, peroxide vulcanizing agents, polythiol vulcanizing agents, quinoid vulcanizing agents, resin vulcanizing agents, metal oxides, diamine vulcanizing agents, polythiols, 2-mercaptoimidazoline , Vulcanizing agents such as polyol vulcanizing agents and polyamine vulcanizing agents. Among them, peroxide vulcanizing agents, polyol vulcanizing agents, polyamine vulcanizing agents, etc. From the viewpoint of the mechanical properties of rubber, polyol vulcanizing agents are more preferable from the viewpoint of improving the adhesive strength between the thermoplastic resin layer (W) and the elastomer layer (X).

The amount of the vulcanizing agent to be compounded in the elastomer composition is preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the elastomer, since an appropriate vulcanization density and an appropriate compression set can be obtained. Parts, more preferably 0.5 to 8 parts by mass.

In addition, the elastomer composition may contain ordinary additives, if necessary, such as fillers, processing aids, plasticizers, coloring agents, stabilizers, vulcanization aids, adhesion aids, and acid acceptors. , A release agent, a conductivity-imparting agent, a thermal conductivity-imparting agent, a surface non-adhesive, a flexibility-imparting agent, a heat resistance improving agent, and various additives such as a flame retardant can be blended. One or more different conventional vulcanizing agents or vulcanization accelerators may be blended.

The elastomer composition generally comprises an elastomer, an onium salt, an amine compound and / or an epoxy resin, and other compounding agents such as a vulcanizing agent, a vulcanization aid, a co-vulcanizing agent, a vulcanization accelerator, and a filler. It can be obtained by kneading using a used rubber kneading apparatus. As a rubber kneading device, a roll, a kneader, a Banbury mixer, an internal mixer, a twin screw extruder, or the like can be used.

In particular, when a polyol-based vulcanizing agent is used as the vulcanizing agent, the melting point of the vulcanizing agent / vulcanization accelerator is often relatively high, so that the vulcanizing agent / vulcanizing agent is dispersed uniformly in the rubber. A method in which a sulfur accelerator is kneaded while being melted at a high temperature of 120 to 200 ° C. using a closed kneader such as a kneader, and then other compounding agents such as a filler are kneaded at a relatively low temperature. Is preferred. There is also a method in which a vulcanizing agent and a vulcanization accelerator are once melted and uniformly dispersed using a solid solution having a lowered melting point.

Vulcanization conditions may be appropriately determined depending on the type of the vulcanizing agent to be used, but usually calcination is performed at a temperature of 150 to 300 ° C. for 1 minute to 24 hours.

The vulcanization method includes steam vulcanization, which is a commonly used method, as well as vulcanization under normal pressure, increased pressure, reduced pressure, in air, and under any conditions. The reaction can be performed.

The laminate of the present disclosure is manufactured by laminating a sheet-like thermoplastic resin layer (W) and a sheet-like elastomer layer (X) before vulcanization, setting the mold in a mold, heat-pressing and vulcanizing and bonding. can do. Further, the thermoplastic resin layer (W) and the elastomer layer (X) are simultaneously extruded in two layers by an extruder, or the inner layer and the outer layer are extruded by extruding the outer layer on the inner layer by two extruders. Can also be manufactured by extruding a laminate made of an extruder into an integrated body, and then vulcanizing and bonding.

The laminate of the present disclosure may have a two-layer structure of a thermoplastic resin layer (W) and an elastomer layer (X), or a laminate in which an elastomer layer (X) is laminated on both sides of a thermoplastic resin layer (W). It may be one in which a thermoplastic resin layer (W) is laminated on both sides of the elastomer layer (X). For example, a three-layer structure of elastomer layer (X) -thermoplastic resin layer (W) -elastomer layer (X) or thermoplastic resin layer (W) -elastomer layer (X) -thermoplastic resin layer (W) may be used. Further, it may have a multilayer structure of three or more layers in which a polymer layer (Y) other than the elastomer layer (X) and the thermoplastic resin layer (W) is adhered, or the elastomer layer (X) and the thermoplastic resin layer ( A polymer layer (Z) may be provided on one side or both sides of a three-layer structure in which a polymer layer (Y) other than W) is adhered. The polymer layer (Y) and the polymer layer (Z) may be the same or different.

積 層 The laminate of the present disclosure may have a polymer layer (Y) on one or both sides of a three-layer structure of an elastomer layer (X) -a thermoplastic resin layer (W) -an elastomer layer (X).

ゴ ム The polymer layers (Y) and (Z) may be rubber layers (Y1) or (Z1) other than the elastomer layer (X). As the rubber layer (Y1) or (Z1), a non-fluorinated rubber layer (Y1a) or (Z1a) formed from a non-fluorinated rubber can be used. Non-fluorinated rubber is preferred because of its good cold resistance and its excellent cost. The non-fluorine rubber layer (Y1a) and the non-fluorine rubber layer (Z1a) may be formed from the same non-fluorine rubber, or may be formed from different non-fluorine rubbers. The laminate of the present disclosure may be laminated in the order of the elastomer layer (X), the thermoplastic resin layer (W), and the non-fluororubber layer (Y1a). Further, it further includes a non-fluorinated rubber layer (Z1a), the non-fluorinated rubber layer (Z1a), the elastomer layer (X), the thermoplastic resin layer (W), and the non-fluorinated rubber layer (Y1a) in this order. ) -Thermoplastic resin layer (W) -non-fluorine rubber layer (Z1a) -non-fluorine rubber layer (Y1a) or elastomer layer (X) -thermoplastic resin layer (W) -non-fluorine rubber layer (Y1a) ) -Non-fluorinated rubber layer (Z1a).

Specific examples of the non-fluorine rubber include, for example, acrylonitrile-butadiene rubber (NBR) or its hydride (HNBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), butadiene rubber (BR), and natural rubber (NR) , Diene rubbers such as isoprene rubber (IR), ethylene-propylene-termonomer copolymer rubber, silicone rubber, butyl rubber, epichlorohydrin rubber, acrylic rubber, chlorinated polyethylene (CPE), acrylonitrile-butadiene rubber and vinyl chloride Polyethylene blend (PVC-NBR), ethylene propylene diene rubber (EPDM) and the like. Further, a rubber obtained by mixing these non-fluorine rubbers and fluorine rubbers at an arbitrary ratio can also be used. As the non-fluorinated rubber, a diene rubber or an epichlorohydrin rubber is preferable from the viewpoint of good heat resistance, oil resistance, weather resistance, and extrusion moldability. More preferably, it is NBR, HNBR or epichlorohydrin rubber. The rubber layer (Y1) is preferably made of NBR, HNBR or epichlorohydrin rubber. The rubber layer (Z1) is made of acrylonitrile-butadiene rubber, epichlorohydrin rubber, chlorinated polyethylene (CPE), polyblend of acrylonitrile-butadiene rubber and vinyl chloride (PVC-NBR), It is preferable that it is made of propylene diene rubber (EPDM), acrylic rubber, or a mixture thereof. In addition, you may mix | blend a vulcanizing agent and other compounding agents also in the unvulcanized rubber composition which forms the rubber layers (Y1) and (Z1).

(4) In order to further improve the adhesiveness between the thermoplastic resin layer (W) and the elastomer layer (X), the thermoplastic resin layer (W) may be subjected to a surface treatment as needed. The type of the surface treatment is not particularly limited as long as it is a treatment method capable of bonding, and for example, a discharge treatment such as a plasma discharge treatment or a corona discharge treatment, and a metal sodium / naphthalene liquid treatment by a wet method. And so on. Further, a primer treatment is also suitable as the surface treatment. The primer treatment can be performed according to a conventional method. When the primer treatment is performed, the surface of the thermoplastic resin layer (W) that has not been subjected to the surface treatment can be treated. However, the thermoplastic resin layer (W) is treated with a plasma discharge treatment, a corona discharge treatment, a metal sodium / naphthalene liquid treatment, or the like. It is more effective if the surface of the resin layer (W) is further treated with a primer.

The thermoplastic resin composition, molded article and laminate of the present disclosure are excellent in balance between fuel barrier properties and tensile elasticity, have small compression set, and are excellent in heat resistance and crack resistance. It can be used for any purpose.

For example, the main components of automobile engines, main motion system, valve train, lubrication / cooling system, fuel system, intake / exhaust system, etc., drive system transmission system, chassis steering system, brake system, etc. Gaskets and non-contact and contact type packings (self-sealing) such as basic electrical components, control electrical components, and equipment electrical components that require heat resistance, oil resistance, fuel oil resistance, LLC resistance, and steam resistance. Seals such as packings, piston rings, split-ring type packings, mechanical seals, oil seals, etc.), bellows, diaphragms, hoses, tubes, electric wires, etc. are provided.

Specifically, it can be used for the applications listed below.

Gaskets such as cylinder head gaskets, cylinder head cover gaskets, oil pan packing, general gaskets, seals such as O-rings, packings, timing belt cover gaskets, hoses such as control hoses, anti-vibration rubber for engine mounts, and hydrogen on the engine body Sealing materials for high-pressure valves in storage systems.

Shaft seals such as crankshaft seals and camshaft seals of the main motion system.

。 Valve stem seals for engine valves and other valve systems.

Engine oil cooler hose, oil return hose, seal gasket, etc. for lubrication and cooling systems, water hose around radiator, vacuum pump oil hose for vacuum pump, etc.

Fuel hoses, fuel tubes, fuel seal materials, and other fuel-related materials for fuel systems. Fuel hoses or fuel tubes include filler (neck) hoses, fuel supply hoses, fuel return hoses, fuel hoses such as vapor (evaporation) hoses, fuel tank in-tank hoses, fuel piping tubes, carburetor control hoses, etc. . Examples of fuel sealing materials include fuel pump oil seals, fuel tank fuel sender seals, filler seals, tank packing, etc., fuel piping tube connector O-rings, etc., fuel injector injector cushion rings, injector seal rings, etc. Injector O-rings, carburetor flange gaskets, etc. Other fuel-related components include fuel pump diaphragms, valves, etc., fuel tank in-tank fuel pump mounts, fuel injection device pressure regulator diaphragms, check valves, etc., carburetor needle valve petals, acceleration pump pistons, etc. Valve seats and diaphragms for air control equipment (CAC). Among them, they are suitable as fuel hoses or fuel tubes, and particularly suitable as filler neck hoses or fuel supply hoses. Further, it is also suitable as a fuel sealing material, and particularly suitable as a fuel sender seal.

Throttle such as intake manifold packing of exhaust manifold, exhaust manifold packing, diaphragm of EGR (circulation during exhaust), control hose, emission control hose, diaphragm of BPT, afterburn prevention valve seat of AB valve, etc. Throttle body packing, turbocharger turbo oil hose (supply), turbo oil hose (return), turbo air hose, intercooler hose, turbine shaft seal, etc.

ＡＴTransmission related transmission seals, oil seals, O-rings, packings, torque converter hoses, etc. AT transmission oil hoses, ATF hoses, O-rings, packings, etc.

Power steering oil hoses for steering systems.

Brake oil seals, O-rings, packing, brake oil hoses, master back air valves, vacuum valves, diaphragms, etc., master cylinder piston cups (rubber cups), caliper seals, boots, etc.

チ ュ ー ブ Tubes of harness exterior parts, such as insulators and sheaths of electric wires (harness) of basic electrical parts.

被覆 Coating materials for various sensor wires for control system electrical components.

Electrical components such as O-rings, packings, cooler hoses, and exterior wiper blades for car air conditioners.

For vehicles other than automobiles, for example, oil, chemical, heat, steam or weather-resistant packing, O-rings, hoses, other sealing materials, diaphragms, valves, etc. in transportation such as ships and aircraft. Similar packing in plant, O-rings, seals, diaphragms, valves, hoses, rolls, tubes, chemical resistant coatings, linings, similar packing in food plant equipment and food equipment (including household products), O- Rings, hoses, seals, belts, diaphragms, valves, rolls, tubes, similar packings in nuclear plant equipment, O-rings, hoses, seals, diaphragms, valves, tubes, similar packings in general industrial parts, O-rings, hoses, sealing materials, diaphragms Arm is suitable valves, rolls, tubes, linings, mandrels, electric wires, flexible joints, belts, rubber plates, weather strips, the application to a roll blade PPC copying machine.

Further, in the application of food rubber sealing material, there is a problem that flavor and rubber fragments are mixed into food in the conventional rubber sealing material, but by using the molded product of the present disclosure, this problem can be improved and preferably Can be used. Because it has chemical resistance, low elution, and low fragrance, in the medical and chemical fields, oil-, chemical-, heat-, steam- or weather-resistant sealing materials, lids, belts, rolls, hoses, tubes, Applicable to films, coatings, linings, joints, containers and the like. In the general industrial field, it can be suitably used for rubber rolls, O-rings, packings, sealing materials, and the like, for the purpose of improving the strength, slipperiness, chemical resistance, and permeability of rubber materials. In particular, it is suitable for use in packing lithium ion batteries because both chemical resistance and sealing can be maintained simultaneously. In addition, it can be suitably used in applications requiring slidability due to low friction.

Among these, the thermoplastic resin composition of the present disclosure, molded articles and laminates are preferably used as a fuel hose or fuel tube because of their excellent balance between fuel barrier properties and tensile modulus, and fillers. It is particularly suitably used as a neck hose or a fuel supply hose. That is, the molded article and the laminate are preferably a fuel hose or a fuel tube, and particularly preferably a filler neck hose or a fuel supply hose. In particular, the thermoplastic resin composition of the present disclosure, molded articles and laminates, since the fuel barrier properties and tensile elasticity are compatible at a high level, while absorbing the vibration while suppressing the evaporation of fuel. In addition, noise is hardly generated, and fluctuation (pulsation) of fuel pressure can be attenuated. Therefore, the thermoplastic resin composition, molded article, and laminate of the present disclosure are suitably used as a fuel hose or a fuel tube to be mounted on an automobile.

Among them, the thermoplastic resin compositions, molded articles and laminates of the present disclosure are excellent in the balance between fuel barrier properties, tensile modulus and compression set, and are therefore used for fuels for mounting on automobiles. It is suitably used as a sealing material, and is particularly preferably used as a fuel sender seal.

Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims.

Next, embodiments of the present disclosure will be described with reference to examples, but the present disclosure is not limited to the examples.

各 Each numerical value in the examples was measured by the following method.

Monomer composition ¹⁹ Measured by F-NMR analysis.

Using a melting point 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 defined as the melting point.

Melt flow rate (MFR)
Using a melt indexer (manufactured by Toyo Seiki Seisaku-sho, Ltd.), 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 load of 5 kg at 297 ° C. was measured.

Mooney viscosity The Mooney viscosity was measured using a Mooney Viscometer Model MV2000E manufactured by ALPHA TECHNOLOGIES, in accordance with ASTM D-1646.

Infrared absorption spectrum analysis (production of thermoplastic resin sheet)
The thermoplastic resin composition is placed in a mold having a diameter of 120 mm, set in a press machine heated to 300 ° C., melt-pressed at a pressure of about 2.9 MPa, and has a thickness of 0.25 mm, 0.5 mm or A thermoplastic resin sheet having a thickness of 2.0 mm was obtained.

(Calculation of ratio of height of absorption peak)
For a thermoplastic resin sheet having a thickness of 0.25 mm, an infrared absorption spectrum was measured by a transmission method using a Fourier transform infrared spectrophotometer [FT-IR], and a ratio [K1] and a ratio [K2] were obtained by the following equations. ] Was calculated.
Ratio [K1] = H1a / H1b
Ratio [K2] = H2a / H2b
H1a: 3475cm ^-1 and 3415cm absorbance 3451Cm ^-1 when the straight line connecting the respective absorbance was to baseline ^-1 height H1b: When the straight line connecting the respective absorbance 2680Cm ^-1 and 2030Cm ^-1 and a baseline absorbance of the height of the 2360 cm ^-1 H2a: 1760 cm ^-1 and 1660cm absorbance 1722 cm ^-1 when a straight line connecting the respective absorbance was to baseline ^-1 height H2b: each ^absorbance 3170Cm ^-1 and 2900 cm ^-1 Absorbance height of 3035 cm ^-1 when the connecting straight line is used as the baseline

Evaluation of fuel barrier properties (fuel permeability coefficient)
18 mL of simulated fuel CE10 (toluene / isooctane / ethanol = 45/45/10% by volume) was placed in a SUS container (open area: 1.26 × 10 ⁻³ m ² ) having a volume of 20 mL, and the above method was performed. The thermoplastic resin sheet having a thickness of 0.25 mm prepared in the above was set in a container open part and sealed to obtain a test specimen. The specimen was placed in a thermostat (60 ° C.), the weight of the specimen was measured, and when the weight loss per unit time became constant, the fuel permeability coefficient was determined by the following equation.

Tensile Modulus A dumbbell-shaped test piece having a distance between mark lines of 3.18 mm is punched out from a thermoplastic resin sheet having a thickness of 0.5 mm produced by the above method using an ASTM D638 Type V dumbbell. Using the obtained dumbbell-shaped test piece, a tensile test was performed at 25 ° C. at a tensile speed of 50 mm / min at 25 ° C. using an autograph (AGS-J 5 kN manufactured by Shimadzu Corporation) according to ASTM D638. The elastic modulus was measured.

Number of functional groups of fluororesin The infrared absorption spectrum of the fluororesin sheet was analyzed using a Fourier transform infrared spectrophotometer [FT-IR]. 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 peak derived from the carbonyl group of the carbonate group [—OC (＝ O) O—] appears in the absorption band at 1810 to 1815 cm ⁻¹ .

In accordance with JIS K6262, the thermoplastic resin sheets produced by the above method were laminated to produce test specimens having a thickness of 3.8 ± 0.1 mm, and at the temperature and time shown in Table 1, A 25% compression was performed and the compression set was measured.

下 記 In Examples and Comparative Examples, the following materials were used.

Fluororesin:
_{-OC (= O) OCH CTFE /} TFE copolymer having 2 _CH 2 CH ₃ groups. The monomer composition was CTFE / TFE / perfluoro (propyl vinyl ether) = 21.0 / 76.2 / 2.8 (molar ratio). 245 ° C. MFR at 297 ° C. is 19 g / 10 min. —OC (＝ O) OCH ₂ CH ₂ CH ₃ groups are 80 (per 10 ⁶ carbon atoms). The tensile modulus is 610 MPa. The fuel permeability coefficient is 0.4 (g · mm) / (m ² · day).

Fluorine rubber (b-1):
A VdF / TFE / HFP copolymer having a monomer composition of VdF / TFE / HFP = 58/22/20 (molar ratio). The Mooney viscosity ML (1 + 10) at 100 ° C. is 45.
Fluorine rubber (b-2):
A VdF / TFE / HFP copolymer having a monomer composition of VdF / TFE / HFP = 50/20/30 (molar ratio). The Mooney viscosity ML (1 + 10) at 121 ° C. is 50.

Polyamine compound: BAPP (pyrolysis temperature: 315 ° C)
Crosslinking accelerator: DBU-B
Acid acceptor: magnesium oxide

Comparative Example 1
(Step 1)
BAPP, DBU-B and magnesium oxide were added to the fluororubber (b-1) and kneaded to obtain a fluororubber composition (b-1 (a)).
(Step 2)
The above-mentioned fluororesin is charged into Labo Plast Mill (manufactured by Toyo Seiki Seisaku-Sho, Ltd.), and the fluororubber composition (b-1 (a)) is added. The operation was stopped to obtain a thermoplastic resin composition. At this time, the temperature of the thermoplastic resin composition was 280 ° C. Table 1 shows the blending amounts of the respective materials and the results of various measurements.

Examples 1 and 2
A thermoplastic resin composition was obtained in the same manner as in Comparative Example 1, except that the blending amounts of the respective materials were changed as described in Table 1. Table 1 shows the blending amounts of the respective materials and the results of various measurements.

Comparative Example 2
In step 1, except that the fluororubber (b-2) was used in place of the fluororubber (b-1), DBU-B was not added, and 0.60 parts by mass of BAPP was further added in step 2. In the same manner as in Comparative Example 1, a thermoplastic resin composition was obtained. Table 1 shows the blending amounts of the respective materials and the results of various measurements.

Comparative Example 3
In step 1, a thermoplastic resin composition was prepared in the same manner as in Comparative Example 1 except that the fluororubber (b-2) was used in place of the fluororubber (b-1) and DBU-B was not added. Got. Table 1 shows the blending amounts of the respective materials and the results of various measurements.

Claims (10)

1. A thermoplastic resin composition containing a fluororesin (A) and a crosslinked fluororubber (B),
   The fluororesin (A) contains a chlorotrifluoroethylene unit and a tetrafluoroethylene unit, and at least one selected from the group consisting of a carbonyl group, an olefin group and an amino group at a main chain terminal or a side chain terminal of the polymer. Is a copolymer having a functional group of
   A crosslinked fluororubber (B) is a polyamine compound (c) having a thermal decomposition temperature of 210 ° C. or higher under the melting conditions of the fluororesin (A) in the presence of the fluororesin (A). And a crosslinking accelerator (d), which is dynamically cross-linked.
   A thermoplastic resin composition wherein the mass ratio of the fluororesin (A) to the fluororubber (b) (fluororesin (A) / fluororubber (b)) is less than 70/30 and 20/80 or more.
2. The thermoplastic resin composition according to claim 1, wherein the fluororubber (b) is a vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene fluororubber.
3. A thermoplastic resin composition containing a fluororesin (A) and a crosslinked fluororubber (B),
   The fluororesin (A) is a copolymer containing a chlorotrifluoroethylene unit and a tetrafluoroethylene unit,
   For molded articles formed from the thermoplastic resin composition, when the infrared absorption spectrum analysis, to the height of the absorption peak appearing in 2360 cm ^-1, the ratio of the height of the absorption peaks appearing in 3451cm ^-1 [K1 ] it is, is 0.001 or more, and, with respect to the height of the absorption peak appearing in 3035Cm ^-1, the ratio of the height of the absorption peaks appearing in 1722 cm ^-1 [K2] is, is 0.3 or more,
   A thermoplastic resin composition having a tensile modulus of 250 MPa or less.
4. A method for producing a thermoplastic resin composition according to any one of claims 1 to 3, wherein
   In the presence of the fluororesin (A), the fluororubber (b) is melted together with a polyamine compound (c) having a thermal decomposition temperature of 210 ° C. or higher and a crosslinking accelerator (d) under the melting conditions of the fluororesin (A). A method for producing a thermoplastic resin composition, comprising a step of dynamically crosslinking.
5. (4) A molded article formed from the thermoplastic resin composition according to any one of (1) to (3).
6. A laminate comprising a thermoplastic resin layer (W) formed from the thermoplastic resin composition according to any one of claims 1 to 3, and an elastomer layer (X) formed from the elastomer composition.
7. The elastomer composition may be acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, blend rubber of acrylonitrile-butadiene rubber and polyvinyl chloride, blend rubber of acrylonitrile-butadiene rubber and acrylic rubber, chlorinated polyethylene, fluorine rubber, 7. The laminate according to claim 6, comprising at least one elastomer selected from the group consisting of epichlorohydrin rubber, ethylene-propylene rubber, chlorosulfonated polyethylene rubber, silicone rubber and acrylic rubber.
8. The laminate according to claim 6 or 7, wherein the elastomer composition contains at least one compound selected from the group consisting of an onium salt, an amine compound, and an epoxy resin.
9. [4] A fuel hose or fuel tube comprising the molded article according to claim 5, or the laminate according to any one of claims 6 to 8.
10. (4) A fuel sealing material comprising the molded product according to (5) or the laminate according to any one of (6) to (8).