JP2003176394A - Thermoplastic resin composition, laminated resin molded product, multilayer molded product, and fluorine-containing resin molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which comprises (Y) a fluorine-containing ethylenic polymer and (Z) a fluorine-free thermoplastic resin and has improved mechanical characteristics, improved adhesive force and stability, and further improved liquid chemical permeability. <P>SOLUTION: This thermoplastic resin composition comprising (Y) the fluorine- containing ethylenic polymer and (Z) the fluorine-free thermoplastic resin is characterized in that (Y) the fluorine-containing ethylenic polymer has reactive functional groups at main chain terminals and/or side chain terminals and that (Z) the fluorine-free thermoplastic resin comprises a fluorine-free polymer having bond-forming sites which have a property for forming bonds to the reactive functional groups. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin having a structure in which a fluorine-containing ethylenic polymer and a non-fluorine-containing thermoplastic resin have a uniformly mixed structure without showing incompatible multiphase morphology. The present invention relates to a resin composition, a laminated resin molded product, a multilayer molded product, and a fluorine-containing resin molded product using the thermoplastic resin composition.

[0002]

2. Description of the Related Art Conventionally, fluororesins are high in heat resistance, oil resistance / chemical resistance, chemical liquid permeation resistance, weather resistance, surface characteristics such as low friction and non-adhesiveness, and electrical insulation. It is used in various applications where functions are required. In particular, the fluorinated ethylenic polymer has been widely used in recent years because it has improved moldability of polytetrafluoroethylene.

On the other hand, however, the fluorine-containing ethylenic polymer generally has insufficient mechanical strength and dimensional stability and is expensive in price. Therefore, in order to maximize the advantages of the fluorine-containing ethylenic polymer and to minimize the disadvantages, various studies have been conducted on adhesion with other thermoplastic resins, lamination, compounding, and the like.

However, since the fluorine-containing ethylenic polymer originally has a low surface free energy, it is difficult to adhere it to another material (base material), and even if an attempt is made to adhere it by heat fusion or the like, the adhesive strength is low. The reliability for adhesion was not sufficient because of insufficient or uneven adhesion strength.

As a method for adhering the fluorine-containing ethylenic polymer to another material, 1. A method of physically roughening the surface of the base material by sandblasting, etc. 2. A method of performing surface treatment such as sodium etching, plasma treatment, and photochemical treatment on the fluorine-containing ethylenic polymer, Although a method of adhering using an adhesive has been studied, the above 1 and 2 require a pretreatment step for adhering, which complicates the process and deteriorates productivity. Further, the type and shape of the base material are limited. Problems (coloring, scratches, etc.) are likely to occur in the appearance of the obtained laminate.

With respect to the above item 3, various studies have been made on adhesives. However, general hydrocarbon adhesives have inadequate adhesive strength and insufficient heat resistance themselves, and when used for fluororesins that generally require molding and processing at high temperatures. On the other hand, peeling or coloring due to thermal decomposition occurs. Furthermore, the oil resistance and chemical resistance are insufficient,
Reliability cannot be maintained because the adhesive strength cannot be maintained due to changes in the environment.

Therefore, it has been studied to use a mixture (resin blend) of a fluorine-containing ethylenic polymer and a mating material as a bonding material instead of a general hydrocarbon-based bonding agent (for example, US Pat. No. 4,886,689). , JP-A-4-140588, JP-A-5-220906, and republication 9
5-11940, Patent 2973860, Japanese Patent Laid-Open No. 2001-2001
108163). However, these resin blend adhesive materials have a problem that the fluorine-containing ethylenic polymer and other materials are essentially incompatible.

Since the fluorine-containing ethylenic polymer and other materials are essentially incompatible, the mixed state of these resin blend adhesive materials is essentially an unstable system. Therefore, the polymorphic morphology changes significantly with slight changes in the conditions during mixing and lamination, and the adhesive force also changes accordingly, resulting in narrow molding conditions and insufficient reliability of adhesion. Often brought.

Further, since the fluorine-containing ethylenic polymer and other materials are essentially incompatible, the resin blend is inferior in mechanical properties, and therefore, even when the laminated body is peeled off, mechanical properties As a result, the peeling progressed due to the cohesive failure of the adhesive layer, which is inferior to the above. Furthermore, the resistance to permeation of chemicals, in particular the resistance to permeation of fuel when used in fuel systems, is considerably inferior despite the mixture with fluororesins. This is also considered to be because the fluorine-containing ethylenic polymer and the other material are incompatible systems.

In order to solve the problem that the fluorine-containing ethylenic polymer and other materials are essentially incompatible, the affinity between the fluorine-containing ethylenic polymer and other materials is improved. For this purpose, a so-called compatibilizer is often added as a third component (for example, JP-A-62-218446, JP-A-3-62853, JP-A-1).
-165647, JP-A-1-197551, JP-A-1-1975
263144, JP 64-11109 A, JP 1-9
8650, JP-A-1-110550).

However, in all of these examples, substantially all,
A non-fluorine-based compatibilizer synthesized by utilizing the excellent affinity between PVdF and a carbonyl group-containing polymer such as an acrylic polymer is used, and the fluorine-containing ethylenic polymer is limited to PVdF. . Further, in the affinity improving method using such a compatibilizing agent, there is a problem in that the chemical resistance and heat resistance of the compatibilizing agent itself are inferior to those of the resin of the main component, so that the physical properties of the molded article are deteriorated. .

There is also an attempt of a composition using a fluoropolymer having a reactive functional group. For example, JP-A-62-1
05062, JP-A-63-254155, JP-A-63-
264672 and the like are given as one of those examples. However, in these examples, the fluoropolymer having a functional group-containing fluoropolymer is obtained as an oily substance, and a low molecular weight polymer that is difficult to define as a resin is only exemplified, and its addition effect is It is considered that the degree of lubricity improvement of the matrix polymer is limited.

As another example of trial of a composition using a fluoropolymer containing a reactive functional group, WO94 / 13
738, Republished 95-29956, Republished 95-337
82, etc., but in these examples, the functional group is a hydroxyl group, an epoxy group, or a carboxyl group, and the fluoropolymer to be applied is a perfluoro resin, or
It has a relatively high melting point, and the mating material resin to be mixed was limited to heat resistant resin.

[0014]

SUMMARY OF THE INVENTION The object of the present invention is to solve the problem of the incompatible system of the above-mentioned conventional resin blend adhesive materials, improve the mechanical properties, and improve and stabilize the adhesive strength. Furthermore, it is intended to improve the chemical liquid resistance. Further, it is an object of the present invention to provide a resin alloy-based adhesive material capable of firmly adhering to a base material particularly by a heating and melting adhering step, and a laminate comprising the same. Furthermore, an object of the present invention is to provide a resin alloy that can be used not only as an adhesive but also as a single structural body by improving mechanical properties.

[0015]

The present invention provides a thermoplastic resin composition comprising a fluorine-containing ethylenic polymer (Y) and a non-fluorine-containing thermoplastic resin (Z), wherein the fluorine-containing ethylenic polymer ( Y) has a reactive functional group at the main chain terminal and / or side chain terminal, and the non-fluorine thermoplastic resin (Z) is made of a non-fluorine polymer having a bond-forming site, The bond forming site has a bond forming property with the reactive functional group, which is a thermoplastic resin composition.

The present invention provides a laminated resin molded product obtained by laminating a layer (A) made of a fluorine-containing ethylenic polymer, an intermediate layer (B) and a layer (C) made of a thermoplastic non-fluorine resin in this order. The layer (B) is a laminated resin molded body characterized by comprising the thermoplastic resin composition.

The present invention is a multi-layer molded product comprising the above-mentioned laminated resin molded product. The present invention is a fluorine-containing resin molded product characterized by comprising the above thermoplastic resin composition. The present invention will be described in detail below.

The thermoplastic resin composition of the present invention is a thermoplastic resin composition comprising a fluorine-containing ethylenic polymer (Y) and a non-fluorine-containing thermoplastic resin (Z), wherein the above-mentioned fluorine-containing ethylenic polymer ( Y) has a reactive functional group at the main chain terminal and / or side chain terminal, and the non-fluorine thermoplastic resin (Z) is made of a non-fluorine polymer having a bond-forming site, The bond-forming site is characterized by having a bond-forming property with the reactive functional group.

As will be described later, the thermoplastic resin composition of the present invention is incompatible with the fluorine-containing ethylenic polymer (Y) and the non-fluorine-containing thermoplastic resin (Z) in at least the obtained molded article. Will not have. This incompatibility is realized, for example, in a thermoplastic resin composition obtained by producing the fluorine-containing ethylenic polymer (Y) and the non-fluorine thermoplastic resin (Z) by melt-kneading or the like. You may be able to.

The fluorine-containing ethylenic polymer (Y) in the present invention has a reactive functional group at the main chain terminal and / or the side chain terminal. Examples of the reactive functional group include a hydroxyl group, an epoxy group, a carbonyldioxy group [-O
-C (= O) -O-], carboxyl group, haloformyl group [-C (= O) -X; X is a halogen atom], alkoxycarbonyl group, acid anhydride, isocyanate group and the like can be used. Is.

The reactive functional group preferably has a carbonyl group [-C (= O)-]. Examples of those having a carbonyl group include functional groups or bonds having a carbonyl group. In the present specification, the above-mentioned “functional group or bond having a carbonyl group”
Is referred to as a “carbonyl group-containing group”.

The above-mentioned carbonyl group-containing group is particularly contained in a polyamide resin which will be most commonly used as a counterpart material for constituting a thermoplastic resin composition, that is, a non-fluorine-containing thermoplastic resin (Z). It can basically react with functional groups such as amide groups and amino groups. Examples of the carbonyl group-containing group include a carbonyldioxy group,
Examples thereof include a haloformyl group, a formyl group (aldehyde group), an acyl group (ketone group), a carboxyl group, an alkoxycarbonyl group, an acid anhydride and an isocyanate group. These carbonyl group-containing groups generally have good reactivity. As the carbonyl group-containing group, a carbonyldioxy group and a haloformyl group are preferable because they can be easily introduced and have high reactivity with a polyamide resin.

In the present specification, the carbonyl group-containing group is an amide bond [-NH-C (= O)-], an imide group [-C (= O) -NH-C (= O)-], urethane. Bond [-NH-C (= O) -O-], urea group [-NH-C
(= O) -NH-] is not included. They are,
Although it has a carbonyl group, unlike the carbonyl group-containing groups exemplified above including a carbonyldioxy group, it has poor reactivity and, for example, is basically one that cannot react with a polyamide resin. be able to.

The carbonyldioxy group in the fluorine-containing ethylenic polymer (Y) according to the present invention is --O as described above.
The group represented by -C (= O) -O-, and the group containing the carbonyldioxy group is specifically -OC.
Examples of the structure include a (═O) O—R group (R is an organic group or a Group VII element). Examples of the organic group include a C1 to C20 alkyl group and a C2 to C20 alkyl group having an ether bond. The former is preferably a C1 to C10 alkyl group. What is represented by -OC (= O) OR is -OC.
_{(= O) OCH 3, -OC} (= O) OC 3 H 7, -O
_{C (= O) OC 8 H} 17, -OC (= O) OCH 2 CH
Etc. ₂ CH ₂ OCH ₂ CH ₃ are preferred.

The haloformyl group in the fluorine-containing ethylenic polymer (Y) in the present invention is --COY as described above.
(Y is a halogen element), and -CO
F, -COCl, etc. are illustrated.

The fluorinated ethylenic polymer (Y) in the present invention has a carbonyl group-containing group in its polymer chain, but the embodiment in which the polymer chain has the above carbonyl group-containing group is not particularly limited. Group-containing groups may be attached to the polymer chain ends or side chains. More specifically, for example, when the carbonyl group-containing group is a carbonyldioxy group or a haloformyl group, (1)
Fluorine-containing ethylenic polymer (Y) having only carbonyldioxy group at the polymer chain terminal or side chain, (2) Fluorine-containing ethylenic polymer having only haloformyl group at polymer chain terminal or side chain (Y), and , (3) Fluorine-containing ethylenic polymer (Y) having a carbonyldioxy group and a haloformyl group at the polymer chain terminal or side chain, and any of these may be used. Among them, those having a carbonyl group-containing group at the polymer chain end are heat resistant,
It is preferable because the mechanical properties and the chemical resistance are not significantly deteriorated or the productivity and the cost are advantageous.

The carbonyl group is preferably derived from peroxide. Peroxycarbonate [-O-C (= O) -O-O-C (= O) -O-]
Chain containing a carbonyl group-containing group such as or a peroxy ester [-O-C (= O) -O-], or using a polymerization initiator having a functional group that can be converted into a carbonyl group-containing group When the method of introducing a carbonyl group-containing group at the terminal is used, the carbonyl group is derived from peroxide. Such a method of introducing a carbonyl group-containing group is a preferred embodiment because it is very easy to introduce and the amount of introduction is also easy to control. In the present invention, the carbonyl group-containing group derived from peroxide means a carbonyl group-containing group directly or indirectly derived from a functional group contained in peroxide.

The number of carbonyl groups in the above-mentioned fluorine-containing ethylenic polymer (Y) can be appropriately selected depending on the type, shape, and use of the mating material to be melt-mixed, the form of the polymer and the molding method. Is preferably 3 to 1000 per 1 × 10 ⁶ carbon atoms in the main chain of the fluorinated ethylenic polymer (Y). The number of carbonyl groups is 1 × the number of carbon atoms in the main chain
If it is less than 3 per 10 ⁶ pieces, it may not sufficiently react with the partner material for melt mixing. Further, when the number exceeds 1,000, a gas or the like is generated due to a chemical change of the carbonyl group due to the melt mixing and the subsequent molding operation, which may adversely affect the physical properties of the thermoplastic resin composition. A more preferred lower limit is 3, and a more preferred upper limit is 500,
A more preferred lower limit is 10, and a more preferred upper limit is 300.
It is an individual. The content of carbonyl group in the fluorine-containing ethylenic polymer (Y) can be measured by infrared absorption spectrum analysis.

Therefore, when the fluorine-containing ethylenic polymer (Y) in the present invention has, for example, a carbonyldioxy group and / or a haloformyl group, and if it has only a carbonyldioxy group, the carbonyl The number of dioxy groups is 3 to 1 per 10 ⁶ carbon atoms in the main chain.
The number of haloformyl groups is 1000, and if the number of haloformyl groups is 1000, the main chain carbon number is 1 × 10 ^6.
It is 3 to 1000 per one, and if it has both a carbonyldioxy group and a haloformyl group, the total number of these groups is 3 to 100 per main chain carbon number of 1 × 10 ^6.
It is preferably 0.

When the total number of carbonyldioxy groups and / or haloformyl groups is less than 3 per 1 × 10 ⁶ carbon atoms in the main chain of the fluorine-containing ethylenic polymer (Y), sufficient adhesive force is obtained. May not be expressed, and 1000
When the number exceeds the limit, the gas generated by the chemical change of the carbonyldioxy group or the haloformyl group may adversely affect the physical properties of the thermoplastic resin composition during the bonding operation. From the viewpoint of heat resistance and chemical resistance, the more preferable lower limit is 3, the more preferable upper limit is 500, the still more preferable lower limit is 10, and the still more preferable upper limit is 300.

If 20 or more haloformyl groups, which are particularly excellent in reactivity with the polyamide resin, are present per 1 × 10 ⁶ main chain carbon atoms of the fluorine-containing ethylenic polymer (Y), a carbonyl group is present. Even if the total content is less than 150 per 1 × 10 ⁶ carbon atoms in the main chain, sufficient reactivity can be exhibited with respect to the partner material for melt mixing.

The number of carbonyl groups per 1 × 10 ⁶ carbon atoms in the main chain of the above-mentioned fluorine-containing ethylenic polymer (Y) is a carboxyl group formed by decomposition of a haloformyl group when a haloformyl group is present. Is generally included. The haloformyl group may be decomposed into a carboxylic acid by, for example, heating when molding the above-mentioned fluorine-containing ethylenic polymer (Y), or over time. Therefore, when the fluorinated ethylenic polymer (Y) in the layer (B) composed of the above-mentioned thermoplastic resin composition in the laminated resin molded product of the present invention described later has a haloformyl group, Generally, a carboxyl group generated by decomposition is contained, but such a carboxyl group is also contained as the number of carbonyl groups per 1 × 10 ⁶ carbon atoms in the main chain of the fluorine-containing ethylenic polymer (Y).

In the fluorinated ethylenic polymer (Y) of the present invention, a fluorinated ethylenic polymer containing no carbonyl group-containing group may be present. In this case, the thermoplastic resin composition of the present invention is used. The main chain carbon is 1 as a total in the whole fluorine-containing ethylenic polymer (Y)
It is sufficient to have a carbonyl group in an abundance ratio having a number within the above range per × 10 ⁶ pieces.

The type and structure of the fluorine-containing ethylenic polymer (Y) in the present invention can be appropriately selected depending on the purpose, application, method of use, etc., but among them, the melting point is 120 to 27.
Those at 0 ° C. are preferred. When such a polymer is melt-mixed with the non-fluorine thermoplastic resin (Z),
In particular, it is advantageous because the reactivity between the carbonyl group-containing group and the counterpart material can be sufficiently exhibited. As the melting point of the fluorine-containing ethylenic polymer (Y), even if the non-fluorine-containing thermoplastic resin (Z) having relatively low heat resistance is melt-mixed, the mating material is decomposed. The temperature is more preferably 230 ° C. or lower, further preferably 210 ° C. or lower so as not to accelerate.

Regarding the molecular weight of the fluorinated ethylenic polymer (Y) in the present invention, the fluorinated ethylenic polymer (Y) can be molded at a temperature not higher than the thermal decomposition temperature, and the obtained molded product is the same as the fluorinated ethylenic polymer (Y). The range is preferably such that excellent mechanical properties and chemical resistance can be exhibited. Specifically, the melt flow rate [MFR] is used as an index of the molecular weight, and it is about 230 to 3 which is a molding temperature range of general fluororesins.
MFR at a temperature in the range of 50 ° C is 0.5 to 100 g
/ 10 minutes is preferable.

The fluorine-containing ethylenic polymer (Y) in the present invention is a fluorine-containing ethylenic polymer having a reactive functional group bonded to the main chain terminal and / or side chain terminal, as described above. The reactive functional group is preferably a carbonyl group or a carbonyl group-containing group. The structure of the main chain and / or side chain of such a fluorine-containing ethylenic polymer (Y) is generally a homopolymer chain or copolymer having a repeating unit derived from at least one fluorine-containing ethylenic monomer. A polymer chain consisting of a chain and formed by polymerizing only a fluorine-containing ethylenic monomer, or a polymer chain obtained by polymerizing a fluorine-containing ethylenic monomer and an ethylenic monomer having no fluorine atom. You may

The above-mentioned fluorine-containing ethylenic monomer is an olefinically unsaturated monomer having a fluorine atom, and specifically, tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, vinyl fluoride, etc. hexafluoropropylene, the hexa fluoro isobutene, equation ^{_{(2): CH 2 = CX}} 1 (CF 2) n X 2 (2) ( wherein, ^{X 1} is -H or -F, ^{X 2} is -H, -F Or-
Cl and n are integers of 1-10. ) And monomers such as perfluoro (alkyl vinyl ethers).

The above-mentioned ethylenic monomer having no fluorine atom is preferably selected from ethylenic monomers having 5 or less carbon atoms so as not to deteriorate heat resistance and chemical resistance. Specifically, ethylene, propylene, 1-butene,
2-butene, vinyl chloride, vinylidene chloride and the like can be mentioned.

The composition of the fluorine-containing ethylenic monomer and the fluorine-free ethylenic monomer is 10 to 100 mol% of the fluorine-containing ethylenic monomer and no fluorine atom. The amount ratio of the ethylenic monomer may be 0 to 90 mol%, and for example, the fluorine-containing ethylenic monomer 30 to
The amount ratio may be 100 mol% to 0 to 70 mol% of an ethylenic monomer having no fluorine atom. The ethylenic monomer having no fluorine atom as described above is an optional monomer component and may not be used.

In the fluorine-containing ethylenic polymer (Y) in the present invention, the weight, the combination, the composition ratio and the like of the fluorine-containing ethylenic monomer and the ethylenic monomer having no fluorine atom are selected. The melting point or glass transition point of the coalescence can be adjusted, and it can be either resinous or elastomeric. The properties of the fluorine-containing ethylenic polymer (Y) can be appropriately selected depending on the purpose and application of adhesion and the purpose and application of the laminate.

The fluorinated ethylenic polymer (Y) in the present invention is a carbonyldioxy group-containing fluorinated ethylenic polymer containing tetrafluoroethylene as an essential monomer component in terms of heat resistance and chemical resistance. A coalescence is preferable, and a carbonyldioxy group-containing fluorine-containing ethylenic copolymer containing a vinylidene fluoride unit as an essential component is preferable from the viewpoint of molding processability. In the present specification, the fluorinated ethylenic polymer (Y) having a carbonyldioxy group is
It may be referred to as a "carbonyldioxy group-containing fluorine-containing ethylenic polymer" or a "carbonyldioxy group-containing copolymer".

Preferred specific examples of the fluorine-containing ethylenic polymer (Y) in the present invention include a carbonyldioxy group-containing fluorine-containing ethylene in which the polymer chain is a polymer chain formed by essentially polymerizing the following monomers. Copolymer (I)
To (V) and the like: (I) a copolymer obtained from a monomer component containing tetrafluoroethylene and ethylene, (II) tetrafluoroethylene, and the following general formula (1) CF ₂ = ^CF-Rf 1 (1) (wherein, .Rf Rf ¹ is representative of a -CF ₃ or-ORF ^2
2 represents a perfluoroalkyl group having 1 to 5 carbon atoms. )
A copolymer obtained from a monomer component containing a perfluoroethylenically unsaturated compound represented by

(III) A copolymer obtained from a monomer component containing vinylidene fluoride, (IV) A copolymer obtained from a monomer component containing the following a, b and c: a. Tetrafluoroethylene 19-90 mol%, preferably 20-70 mol% b. Ethylene 9-80 mol%, preferably 20-60 mol% c. 1 to 72 mol%, preferably 1 to 60 mol%, of the perfluoroethylenically unsaturated compound represented by the general formula (1), and (V) obtained from a monomer component containing the following d, e and f. Copolymers. d. 15-60 mol% of vinylidene fluoride e. Tetrafluoroethylene 35-80 mol% f. Hexafluoropropylene 5-30 mol%

All of the above copolymers (I) to (V) are preferable in that they are particularly excellent in heat resistance, chemical resistance, weather resistance, electric insulation and non-adhesiveness. Those having an oxy group are more preferable. The monomer component of each of the copolymers (I) to (V) may be composed of only the above-mentioned monomer, or may be a copolymer of the above-mentioned monomer and the above-mentioned monomer. It may contain other polymerizable monomers.

When the copolymer (I) has, for example, a carbonyl group-containing group in its side chain, the remaining monomer component excluding the monomer having a carbonyl group-containing group is tetrafluoroethylene 20- 90 mol% (for example, 20 to 60)
Mol%), ethylene 10 to 80 mol% (eg 20 to 6)
And a carbonyldioxy group-containing copolymer having a polymer chain consisting of 0 to 70 mol% of a monomer copolymerizable therewith. The tetrafluoroethylene and the monomer copolymerizable with ethylene are optional components and may not be included in the monomer component.

Examples of the copolymerizable monomer include hexafluoropropylene, chlorotrifluoroethylene, the monomer represented by the general formula (2), perfluoro (alkyl vinyl ether) s, propylene and the like. Usually, one or more of these are used. Such a fluorine-containing ethylenic polymer (Y) is particularly preferable because it is excellent in heat resistance, chemical resistance, weather resistance, electric insulation and non-adhesiveness.

Among the above copolymers (I), among others,
(I-1) having a polymer chain obtained from a monomer component consisting of 62 to 80 mol% of tetrafluoroethylene, 20 to 38 mol% of ethylene, and 0 to 10 mol% of a monomer copolymerizable therewith. Carbonyldioxy group-containing copolymer, (I-2) tetrafluoroethylene 20-8
It has a polymer chain obtained from a monomer component consisting of 0 mol%, ethylene 10 to 80 mol%, hexafluoropropylene 0 to 30 mol%, and a monomer 0 to 10 mol% copolymerizable therewith. The carbonyldioxy group-containing copolymer maintains the excellent performance of the tetrafluoroethylene / ethylene copolymer, and its melting point can be made relatively low, so that the adhesiveness with other materials can be maximized. It is preferable in terms. In the present specification, the above copolymer (1) may be referred to as “tetrafluoroethylene / ethylene copolymer”.

Examples of the copolymer (II) include, for example,
(II-1) Tetrafluoroethylene 65-95 mol
%, Preferably 75 to 95 mol%, and hexafluor
Propylene 5-35 mol%, preferably 5-25 mol
Having a polymer chain derived from a monomer component consisting of
Carbonyldioxy group-containing copolymer, (II-2) tet
Lafluoroethylene 70 to 97 mol% and CF_Two=
CFORf^Two(Rf^TwoIs a C1-C5 perfluoroa
Rutile group) obtained from a monomer component consisting of 3 to 30 mol%
Carbonyldioxy group-containing copolymer having a polymer chain
Combined, (II-3) tetrafluoroethylene, hexaf
Luoropropylene, CF_Two= CFORf^Two(Rf^TwoIs above
The same as the above), a polymer chain obtained from a monomer component
A carbonyl group-containing copolymer having
Luoropropylene and CF _Two= CFORf^TwoAnd the sum is
A copolymer or the like, which is 5 to 30 mol% of the monomer component, is preferable.
Yes.

The above-mentioned copolymer (II-2) and the above-mentioned copolymer (II-3) are also perfluoro-based copolymers,
Among the fluoropolymers, heat resistance, chemical resistance, water repellency,
Most excellent in non-adhesiveness and electrical insulation.

As the above-mentioned copolymer (III), for example, when the side chain has a carbonyl group-containing group, the remaining monomer component excluding the monomer having the carbonyl group-containing group is vinylidene fluoride 15 ~ 99 mol%, tetrafluoroethylene 0-80 mol%, and hexafluoropropylene and / or chlorotrifluoroethylene 0-3
Examples thereof include a carbonyldioxy group-containing copolymer having a polymer chain obtained from a monomer component of 0 mol%.

The above-mentioned copolymer (III) is, for example, a polymer chain obtained from a monomer component consisting of (III-1) 30 to 99 mol% of vinylidene fluoride and 1 to 70 mol% of tetrafluoroethylene. Carbonyldioxy group-containing copolymer having (III-2) vinylidene fluoride 60 to 90 mol%, tetrafluoroethylene 0
-30 mol% and chlorotrifluoroethylene 1-
A carbonyldioxy group-containing copolymer having a polymer chain obtained from a monomer component consisting of 20 mol%, (III
-3) A carbonyldioxy group-containing copolymer having a polymer chain obtained from a monomer component consisting of 60 to 99 mol% of vinylidene fluoride, 0 to 30 mol% of tetrafluoroethylene, and 5 to 30 mol% of hexafluoropropylene. Polymer, (III-4) 15-60 mol% of vinylidene fluoride, 35-80 mol% of tetrafluoroethylene, and
Examples thereof include a carbonyldioxy group-containing copolymer having a polymer chain obtained from a monomer component consisting of 5 to 30 mol% of hexafluoropropylene.

The method for producing the fluorine-containing ethylenic polymer (Y) in the present invention is not particularly limited, and the ethylenic monomer having a carbonyl group-containing group is used as the target fluorine-containing ethylenic polymer (Y). It can be obtained by copolymerizing with a fluorine-containing ethylenic monomer having a combined type and composition.

The ethylenic monomer having a carbonyl group-containing group is preferably perfluoroacrylic acid fluoride, 1-fluoroacrylic acid fluoride, acrylic acid fluoride, 1-trifluoromethacrylic acid fluoride, perfluorobutenoic acid. Examples thereof include fluorine-containing monomers such as acrylic acid, methacrylic acid, acrylic acid chloride, and vinylene carbonate.

Various methods can be adopted for obtaining the fluorine-containing ethylenic polymer (Y) having a carbonyl group-containing group at the main chain terminal of the polymer chain, but peroxides, particularly peroxycarbonate and The method of using peroxyester as a polymerization initiator can be preferably adopted in terms of cost efficiency, heat resistance, chemical resistance and the like. According to this method, a carbonyl group-containing group derived from peroxide, for example, a carbonyldioxy group derived from peroxycarbonate, an ester group derived from peroxyester, or a haloformyl group obtained by converting these functional groups. Can be introduced at the end of the main chain of the polymer chain. Of these polymerization initiators, when peroxycarbonate is used, the polymerization temperature can be lowered,
It is more preferable because the side reaction does not accompany the initiation reaction.

The above-mentioned peroxycarbonate has the following general formula

[0056]

[Chemical 1]

(In the formula, R and R'are the same or different,
Linear or branched monovalent saturated hydrocarbon group having 1 to 15 carbon atoms, or 1 to 1 carbon atom having an alkoxy group at the terminal
15 represents a linear or branched monovalent saturated hydrocarbon group, R ″ is a linear or branched divalent saturated hydrocarbon group having 1 to 15 carbon atoms, or an alkoxy group at the end Represents a linear or branched divalent saturated hydrocarbon group having 1 to 15 carbon atoms. The compound represented by) is preferably used.

Among them, diisopropyl peroxycarbonate, di-n-propyl peroxydicarbonate, t-butyl peroxyisopropyl carbonate,
Bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate and the like are preferable.

The amount of the initiator such as peroxycarbonate or peroxyester used depends on the kind of the desired polymer (composition, etc.), the molecular weight, the polymerization conditions and the kind of the initiator used, but it can be obtained by polymerization. The amount is preferably 0.05 to 20 parts by weight, particularly 0.1 to 10 parts by weight, based on 100 parts by weight of the fluorine-containing ethylenic polymer (Y).

As the polymerization method, suspension polymerization in an aqueous medium in which a fluorine-based solvent is used industrially and peroxycarbonate or the like is used as a polymerization initiator is preferable as the polymerization method, but other polymerization methods such as solution polymerization are preferable. Emulsion polymerization, bulk polymerization, etc. can also be adopted. In suspension polymerization, a fluorinated solvent may be used in addition to water. Hydrochlorofluoroalkanes (for example, C
H ₃ CClF ₂ , CH ₃ CCl ₂ F, CF ₃ CF ₂ CC
1 ₂ H, CF ₂ ClCF ₂ CFHCl), chlorofluoroalkanes (for example, CF ₂ ClCFClCF ₂ CF)
₃ , CF ₃ CFClCFClCF ₃ ), perfluoroalkanes (eg, perfluorocyclobutane, CF _3).
CF ₂ CF ₂ CF ₃ , CF ₃ CF ₂ CF ₂ CF ₂ C
_{F 3, CF 3 CF 2 CF} 2 CF 2 CF 2 CF 3) can be used, inter alia perfluoroalkanes are preferable. The amount of the fluorine solvent used is preferably 10 to 100% by weight with respect to water from the viewpoints of suspending property and economy.

The polymerization temperature is not particularly limited, and is 0 to 100 ° C.
Good. The polymerization pressure is appropriately determined according to other polymerization conditions such as the type and amount of the solvent used, the vapor pressure, the polymerization temperature, etc., but may be usually 0 to 9.8 MPaG.

In order to adjust the molecular weight, usual chain transfer agents, for example, hydrocarbons such as isopentane, n-pentane, n-hexane and cyclohexane; alcohols such as methanol and ethanol; carbon tetrachloride, chloroform and methylene chloride. , Halogenated hydrocarbons such as methyl chloride can be used. The content of the terminal carbonyldioxy group or ester group can be controlled by adjusting the polymerization conditions, and can be controlled by the amount of peroxycarbonate or peroxyester used, the amount of chain transfer agent used, the polymerization temperature, etc. .

Various methods can be adopted for obtaining the fluorine-containing ethylenic polymer (Y) having a haloformyl group at the terminal of the polymer molecule. For example, the fluorine-containing ethylenic polymer having the above-mentioned carbonyldioxy group or ester group at the terminal can be used. It can be obtained by heating the ethylenic polymer (Y) to thermally decompose (decarboxylate) it. The heating temperature varies depending on the type of carbonyldioxy group or ester group and the type of fluorine-containing ethylenic polymer (Y), but the polymer itself is 27
0 ° C or higher, preferably 280 ° C or higher, particularly preferably 3
It is preferable to heat so as to be not lower than 00 ° C., and the upper limit of the heating temperature is preferably not higher than the thermal decomposition temperature of a site other than the carbonyldioxy group or the ester group of the fluorine-containing ethylenic polymer (Y), Specifically, 400 ° C or lower,
More preferably, it is 350 ° C. or lower.

The non-fluorine thermoplastic resin (Z) of the present invention is
It is composed of a non-fluorine polymer having a bond-forming site. Examples of the non-fluorine-based polymer include polyester, polyamide, polyphenylene sulfide,
Acrylic, vinyl acetate, polyolefin, vinyl chloride, polycarbonate, styrene, polyurethane,
Acrylonitrile butadiene styrene copolymer [AB
S], polyimide, polyamide imide, polyether polyether ketone [PEEK], polyether sulfone [PES], polysulfone, polyether phenyl oxide [PPO], polyaramid, polyacetal, polyetherimide, silicone resin, epoxy resin, phenol Resin, amino resin, unsaturated polyester, cellophane, etc. are mentioned.

The bond-forming site has a bond-forming property with the reactive functional group of the fluorine-containing ethylenic polymer (Y). As such a bond-forming site,
It may be a bond such as an amide bond existing in the main chain like a polyamide resin described later, or a functional group having a main chain and / or a side chain, or both of them. Good.

The bond-forming site is not particularly limited as long as it has a bond-forming property with the reactive functional group, and the most preferred carbonyl group-containing reactive functional group of the fluorine-containing ethylenic polymer (Y). From the viewpoint of reactivity with a group and heat resistance, a hydroxyl group, an epoxy group, a carboxyl group, an alkoxycarbonyl group, an acid anhydride, an amide bond, an amino group and a sulfonamide group are preferable, and among them, an amide bond and an amino group. Is more preferable.

As the non-fluorine thermoplastic resin (Z), a polyamide resin, a bond forming site-containing polyolefin resin, polyvinyl alcohol, a polyurethane resin, a polyester resin, a polysiloxane, a polyarylene oxide, a polyarylene sulfide is used. And the like, and a polyamide resin and a bond-forming site-containing polyolefin resin are preferable.

The above polyamide-based resin has characteristics such as high strength, high toughness, light weight, excellent workability, and particularly flexibility, and is particularly preferable as a material for compensating for the drawbacks of the fluororesin in general. With the polyamide-based resin in the present invention,
Amide bond [-NH-C] as a repeating unit in the molecule
A polymer having (= O)-]. Examples of such a resin include resins in which the majority of amide bonds are bonded to an aliphatic or alicyclic structure.

Examples of such polyamide resins include ring-opening polymerization of cycloaliphatic lactams; condensation of aliphatic diamines with aliphatic dicarponic acid or aromatic dicarponic acid; condensation polymerization of amino acids; Examples thereof include polyamide-based resins synthesized by copolymerization of a so-called dimer acid containing a dicarboxylic acid having 36 carbon atoms obtained by quantification as a main component and a short-chain dibasic acid, and a so-called nylon resin can be given. Specifically, for example, polymers of nylon 6, nylon 66, nylon 11, nylon 12, nylon 610, nylon 612, nylon 6/66, nylon 66/12, nylon 46 and metaxylylenediamine / adipic acid, and , And blends thereof.

The polyamide resin according to the present invention may have a structure having no amide bond as a repeating unit, which is block- or graft-bonded to the molecule.
Examples of such resins include AB block type polyether ester amides and polyamide elastomers which are polyether amide elastomers having a polyamide component as a crystalline hard segment and a polyether as a soft segment. Are obtained, for example, from the condensation reaction of lauryl lactam with dicarboxylic acids and tetramethylene glycol.

The types of carbon numbers of the polyamide of the hard segment and the carbon numbers of the soft segment and their ratios, or the molecular weight of each block can be freely designed from the viewpoint of flexibility and elastic recovery.

The method for incorporating the above functional group into the polyamide resin is not particularly limited, and the copolymerizable monomer having the above functional group is copolymerized with the polyamide resin to the above content. Or a plasticizer having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an ester group and a sulfonamide group, or a functional group having compatibility with a polyamide resin and having these functional groups. The polymer having may be blended so as to have the above-mentioned functional group content.

Examples of the polymer having compatibility with the above polyamide-based resin and having the above functional group include, for example, ester and / or carboxylic acid modified olefin resin (ethylene /
Methyl acrylate copolymer, ethylene / acrylate copolymer, ethylene / methyl acrylate / maleic anhydride copolymer, ethylene / ethyl acrylate copolymer, propylene / maleic anhydride copolymer, etc.), ionomer resin, polyester resin, Examples thereof include phenoxy resin, ethylene-propylene-diene copolymer, and polyphenylene oxide.

Examples of the polyamide resin having a structure having no amide bond as a repeating unit include, for example, nylon 6-polyester copolymer, nylon 6-polyether copolymer, nylon 12-polyester copolymer. Examples thereof include a polyamide-based resin elastomer such as a coalesced material and a nylon 12-polyether copolymer. These polyamide resin elastomers are block copolymers of a nylon resin oligomer and a polyester resin oligomer or a polyether resin oligomer via an ester bond or an ether bond. Examples of the polyester resin oligomer include polycaprolactone and polyethylene adipate, and examples of the polyether resin oligomer include polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like.
Particularly preferred embodiments are nylon 6-polytetramethylene glycol copolymer, nylon 12-polytetramethylene glycol copolymer and the like.

By the way, generally, a polyamide resin easily causes a decomposition reaction by being heated at the time of molding,
In order to suppress the generation of low molecular weight substances such as monomers or gelation, and to suppress the coloring due to oxidation, etc., usually, a monocarboxylic acid or its derivative is added at the time of polymerization. Thus, so-called end-capping is widely performed to reduce the concentration of terminal amino groups. Therefore, polyamide resins having a terminal amino group concentration of generally less than 10 equivalents / 10 ⁶ g are widely used. However, in the case where the polyamide resin and the fluorine-containing ethylenic polymer (Y) containing a reactive functional group are melt-kneaded, the reaction may not proceed sufficiently in some cases. When this phenomenon was examined, when the terminal amino group concentration of the polyamide resin was less than 10 equivalent / 10 ⁶ g, the reaction with the layer (A) composed of the fluorine-containing ethylenic polymer was insufficient. However, it was found that the reaction was remarkably improved when the terminal amino group concentration was increased.

On the other hand, it was also found that when this value exceeds 60 equivalents / 10 ⁶ g, the mechanical properties of the molded product are inferior, and the molded product is easily colored during storage and inferior in handling property. Therefore, in the present invention, the preferred lower limit of the terminal amino group concentration of the polyamide resin is 10 equivalents / 10 ⁶ g, and the preferred upper limit is 60 equivalents / 10 ⁶ g. A more preferred lower limit is 10 equivalents / 10 ⁶ g, and a more preferred upper limit is 50 equivalents / 10 ⁶ g. A more preferred lower limit is 15 equivalents / 10 ⁶ g, and a more preferred upper limit is 35 equivalents / 10 ⁶ g.

In the present invention, the polyamide resin is
The preferred upper limit of the terminal carboxyl group concentration is 80 equivalents / 1
0⁶It is g. 80 equivalent / 10⁶Even if it exceeds g,
As long as the concentration of mino groups is within the above range, sufficient reaction will be expressed.
However, the molecular weight of the resin is not always sufficient
In some cases, the terminal carboxyl group concentration is 80 equivalent / 10
⁶Avoid such problems by setting g or less
It A more preferable upper limit is 70 equivalents / 10⁶g and
The preferred upper limit for the amount is 60 equivalents / 10⁶It is g.

In the present invention, the polyamide resin is preferably selected so that its melting point is 130 ° C. or higher. If the melting point is less than 130 ° C, the thermoplastic resin composition formed may be inferior in mechanical properties, heat resistance and the like. A more preferred lower limit is 150 ° C and a more preferred upper limit is 300 ° C. A more preferred lower limit is 150
C., and a more preferable upper limit is 270.degree.

The above-mentioned bond-forming site-containing polyolefin resin is a copolymer obtained by polymerizing ethylene with a monomer having a functional group (y) for forming a bond-forming site. As the monomer, glycidyl acrylate, glycidyl methacrylate, maleic anhydride, acrylic acid, methacrylic acid, vinyl acetate and / or vinyl alcohol are preferable.

Examples of the polyolefin resin containing a bond-forming site include polyethylene, polystyrene, polypropylene, polybutene, and ethylene / vinyl acetate copolymer [E
VA], ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / ethyl acrylate / maleic anhydride copolymer, and the like, which have a bond-forming site. Among them, polyethylene is preferable. Is preferred.

Since the polyvinyl alcohols having various vinyl acetate contents and saponification degrees are commercially available, the polyvinyl acetate content X (mol%) and the saponification degree Y (%) of the methyl ester are among them. , X × Y / 100 ≧
It suffices to select one that satisfies 7.0. Examples of polyvinyl alcohol that can be used in the present invention include:
Eval F101 (trade name, manufactured by Kuraray Co., Ltd.) has a vinyl acetate content of 68 mol% and a saponification degree of 95%.
Y / 100 is 64.6. Mersen H6051 (trade name, manufactured by Tosoh Corporation) has a vinyl acetate content of 11.2 mol% and a saponification degree of 100%, so that X × Y / 100 is 1.
It becomes 1.2. Technolink K200 (trade name, manufactured by Taoka Chemical Co., Ltd.) has a vinyl acetate content of 11.2 mol% and a saponification degree of 85%, and therefore X × Y / 100 is 9.52.

As the polysiloxane, those generally known as silicone resins can be used. As the polyarylene oxide, polyphenylene oxide [PPO] is preferable, and those generally known as PPO can be used. As the polyallylene sulfide, polyphenylene sulfide [PPS] is preferable, and one generally known as PPS can be used. In the present specification, the “arylene” in the polyarylene oxide and the polyarylene sulfide is a
It means rylene, not allylene.

As described above, the thermoplastic resin composition of the present invention comprises the fluorine-containing ethylenic polymer (Y) and the non-fluorine-containing thermoplastic resin (Z). The embodiment of the thermoplastic resin composition which is a mixture of (Y) and the non-fluorinated thermoplastic resin (Z) includes (a) the fluorine-containing ethylenic polymer (Y) and the non-fluorinated thermoplastic resin (Z). Both are powders, powders that are mixed at room temperature until homogeneous,
(B) Fluorine-containing ethylenic polymer (Y) and non-fluorinated thermoplastic resin (Z) are both pellets, and pellets obtained by mixing these pellets at room temperature until they are homogeneous, (c) Fluorine-containing ethylenic polymer (Y) and a non-fluorine thermoplastic resin (Z) are extruded in the form of pellets after pre-mixing, or the fluorinated ethylenic polymer (Y) and the non-fluorine thermoplastic resin (Z) in the melt extrusion step. ) Are mixed into a pellet form, and the final pellets of the fluorine-containing ethylenic polymer (Y) and the non-fluorine-containing thermoplastic resin (Z) have not reached the final reaction state. Which are pelletized through the same steps as (d) and (c), and in the resulting pellets, the fluorinated ethylenic polymer (Y) and the non-fluorinated thermoplastic resin (Z) are The final anti Such as those reached state and the like.

In the present specification, the "final reaction state" means when the fluorine-containing ethylenic polymer (Y) and the non-fluorine thermoplastic resin (Z) are melt-mixed at a necessary and sufficient temperature and time. Means the state of reaching. Above (a)-(d)
Among them, in (a) to (c), a fluorine-containing ethylenic polymer (Y) and a non-fluorine-containing thermoplastic resin (Z) are used in the step of molding the obtained thermoplastic resin composition into a molded product. It is intended to bring about the reaction of (1) and bring it to the final reaction state.

As described above, the thermoplastic resin composition of the present invention has a bond-forming property having a bond-forming property between the fluorine-containing ethylenic polymer (Y) having a reactive functional group and the reactive functional group. Since it is composed of a non-fluorine-containing thermoplastic resin (Z) having a moiety, at least a molded product obtained from the above-mentioned thermoplastic resin composition has the above-mentioned fluorine-containing ethylenic polymer (Y) and the above-mentioned non-fluorine-containing thermoplastic resin. There can be no polymorphic morphology created by incompatibility with (Z).

In the present specification, the above-mentioned “polymorphic morphological structure” is used.
The term means a state in which a certain component has a multiphase structure in which it is dispersed in the form of particles in a matrix composed of other components. Such multiphase morphology is a common condition in incompatible multiphase systems. It can be said that the above-mentioned multiphase morphology is a non-uniform system like the multiphase structure in the transmission electron microscope image of FIG.

Although the mechanism by which the thermoplastic resin composition of the present invention results in the absence of the polymorphic morphological structure is not clear, the formation of a bond between the reactive functional group and the bond-forming site. It is thought to be due to. in this case,
The fluorine-containing ethylenic polymer (Y) forms a bond with the non-fluorine thermoplastic resin (Z).

It is considered that the bond between the reactive functional group and the bond forming site is usually formed by reacting the reactive functional group with the bond forming site. Although a bond by such a reaction is preferable, for example, a bond that does not depend on a so-called chemical reaction such as a hydrogen bond may be further formed. In this case, the above-mentioned fluorine-containing ethylenic polymer (Y) is one that has reacted with the non-fluorine-containing thermoplastic resin (Z).

The reaction between the reactive functional group and the bond-forming site usually occurs when the thermoplastic resin composition is produced, for example, when it is heated to a temperature of 260 ° C. or higher by, for example, melt kneading. It is thought that
The degree of reaction is preferably such that the moldability is not impaired before molding, and depending on the amount of the reactive functional group and the bond-forming site, it is preferable that the above-mentioned final reaction state is not reached. There is also. The thermoplastic resin composition of the present invention may or may not have such a multi-phase morphological structure before molding, but at the time of molding, at least by heating, the above-mentioned reaction usually occurs. Since the functional group reacts with the bond-forming site, the resulting molded article has no multiphase morphological structure.

As described above, in the thermoplastic resin composition of the present invention, the above-mentioned fluorine-containing ethylenic polymer (Y) may form a bond with the non-fluorine-containing thermoplastic resin (Z). The above-mentioned fluorine-containing ethylenic polymer (Y) may also be one that has been reacted with a non-fluorine-containing thermoplastic resin (Z).

Due to the absence of the above-mentioned multiphase morphological structure, the molded product has a mechanical strength superior to that of the resin composition in which the multiphase morphology is present in the incompatible type, and it is used as an adhesive material. Thereby, a laminate having more excellent adhesive strength can be obtained, and in terms of chemical permeation resistance, it is superior to the incompatible resin composition.

The thermoplastic resin composition of the present invention is used for producing a molded product. The thermoplastic resin composition of the present invention can be used to mold any of a molded product having a multi-layer structure including a layer made of the thermoplastic resin composition and a molded product having a single-layer structure made of only the thermoplastic resin composition. It is also preferably used for forming a body.

Examples of the molded article having the above-mentioned multi-layered structure include a layer (a) having an adhesive property with the fluorine-containing ethylenic polymer (Y), a layer (b) comprising the thermoplastic resin composition of the present invention, and Examples include a molded product in which the non-fluorine thermoplastic resin (Z) and the layer (c) having adhesiveness are laminated.

The resin forming the layer (a) is not particularly limited as long as it has a strong adhesiveness with the fluorine-containing ethylenic polymer (Y), and the resin forming the layer (c) is a non-fluorine-containing heat. The resin forming the layer (a) is a fluorine-containing resin from the viewpoint that it is possible to avoid mixing of extra functional groups, additives, etc., as long as it has a strong adhesiveness with the plastic resin (Z). A resin which is made of the same type of resin as the ethylenic polymer (Y) and is compatible with and adheres to each other is preferable. Those that adhere to are preferred. Examples of the molded body having such a multilayer structure include a laminated resin molded body described later, and the laminated resin molded body is one of the present inventions.

The laminated resin molding of the present invention comprises a layer (A) made of a fluorine-containing ethylenic polymer, an intermediate layer (B),
And a layered resin molded product in which a layer (C) made of a thermoplastic non-fluorine resin is laminated in this order, wherein the layer (B) is made of the thermoplastic resin composition. To do.

In the present specification, the "fluorine-containing ethylenic polymer" means an ethylenic polymer having a fluorine atom bonded to a carbon atom forming the main chain. The polymer belonging to the fluorine-containing ethylenic polymer,
It may be the same as or different from the above-mentioned polymer belonging to the fluorine-containing ethylenic polymer (Y). In the present specification, the "thermoplastic non-fluorine resin" means
It means a thermoplastic resin having no fluorine atom in the molecule. The resin belonging to the above-mentioned thermoplastic non-fluorine resin may be the same as the resin belonging to the above-mentioned non-fluorine thermoplastic resin (Z), or may be different.

In the laminated resin molded product, the thermoplastic resin composition is composed of two kinds of resins, a fluorine-containing ethylenic polymer (Y) and a non-fluorine-containing thermoplastic resin (Z). The combined layer (Y) and the above-mentioned layer (A) having adhesiveness can be firmly adhered, and
The non-fluorine thermoplastic resin (Z) and the above-mentioned layer (C) having adhesiveness can be firmly adhered.

The fluorine-containing ethylenic polymer is not particularly limited as long as it has a strong adhesiveness with the fluorine-containing ethylenic polymer (Y), and the thermoplastic non-fluorine resin is a non-fluorine thermoplastic resin (Z). Is not particularly limited as long as it has a strong adhesiveness with. The fluorine-containing ethylenic polymer is preferably a polymer of the same kind as the fluorine-containing ethylenic polymer (Y) and compatible with each other, since it is possible to avoid mixing of extra functional groups and additives. The plastic non-fluorine resin is preferably the same type of resin as the non-fluorine thermoplastic resin (Z) and is compatible with and adheres thereto.

Further, when the fluorine-containing ethylenic polymer and the fluorine-containing ethylenic polymer (Y) are the same kind of polymer, and the thermoplastic non-fluorine resin and the non-fluorine thermoplastic resin (Z) are the same kind of resin. When the laminated resin molded product of the present invention is used for automobile fuels, chemicals, tubes, hoses, tanks, and bottles for beverages, the heat resistance, oil resistance, chemical resistance, and low chemical permeability of fluororesins are generally possessed. It is preferable that the layer (A) is an inner layer from the viewpoint of utilizing such characteristics as described above. In addition, when the multilayer laminate is used for the above-mentioned applications, in order to compensate for the defects of general fluororesins,
It is preferable to use a polyamide resin having high strength and high toughness as the non-fluorine thermoplastic resin (Z) and the thermoplastic non-fluorine resin. In this case, the layer (C) is the outer layer.

The layer (A) and / or the layer (C) in the laminated resin molded product according to the present invention may contain various organic or inorganic additives to impart conductivity. It may have an inorganic filler such as carbon or metal powder for improving the wear resistance of the laminate, or an organic material for use as a plasticizer, a heat-resistant material, an impact modifier or the like.

The fluorine-containing ethylenic polymer forming the layer (A) can be appropriately selected from the fluorine-containing ethylenic polymer (Y) described above as the material for the thermoplastic composition, but the reactive functional group is used. It need not have a group. As the fluorine-containing ethylenic polymer, a tetrafluoroethylene / ethylene-based copolymer [ETFE-based copolymer] is preferable because it has excellent chemical resistance, fuel permeation resistance, and low temperature impact resistance. In the present invention, the "ETFE-based copolymer" means a copolymer obtained from a monomer component containing tetrafluoroethylene and ethylene. When the fluorine-containing ethylenic polymer formed above is an ETFE copolymer, the fluorine-containing ethylenic polymer (Y)
Although the same as the above-mentioned copolymer (I) may be used as a preferable one, it is not necessary to have a reactive functional group.

The layer (A) is a mixture of various fillers such as inorganic powder, glass fiber, carbon fiber, metal oxide and carbon within a range that does not impair the performance depending on the purpose and use. May be. In addition to the filler, the layer (A) may be a mixture of a pigment, an ultraviolet absorber, and any other additive. The layer (A) may be a mixture of other fluororesin, thermoplastic resin, thermosetting resin or the like, synthetic rubber, etc. in addition to the additive. It is possible to improve mechanical properties, weather resistance, impart design properties, prevent static electricity, improve moldability, and the like. The layer (A) is particularly preferable if it is blended with a conductive material such as carbon black or acetylene black, because it is advantageous for preventing static charge accumulation in the fuel piping tube or hose.

The layer (A) comprises the above-mentioned fluorine-containing ethylenic polymer and other components optionally blended, and the layer (A) is, if necessary, electrically conductive. The term "conductive" used in the present invention means, for example,
When a flammable fluid such as gasoline continuously contacts an insulator such as resin, electrostatic charge may accumulate and cause ignition, but the electrical characteristics are such that this electrostatic charge does not accumulate. Means having, for example, SAEJ226
In 0, the surface resistance is defined to be 10 ⁶ Ω / □ or less. When the layer (A) is made electrically conductive, the content of the electrically conductive material is preferably 20% by weight or less in the composition to form the layer (A), and 15% by weight.
The following is more preferable. The lower limit may be an amount that can impart the above surface resistance value.

The thermoplastic resin composition for the layer (B) is excellent in adhesiveness with the layer (A) and adhesiveness with the layer (C), and thus the fluorine-containing ethylenic polymer (Y). Is preferably the above-mentioned copolymer (IV).

As the thermoplastic non-fluorine resin forming the layer (C), a polyamide resin is preferable. The polyamide-based resin can be appropriately selected from the polyamide-based resins described above as the material of the thermoplastic composition, but when this multilayer molded article is molded by extrusion molding or blow molding, it is represented by relative viscosity. The molecular weight is preferably 1.8 or more, more preferably 2.0 or more. If it is less than 1.8, the moldability during molding may be poor, and the mechanical properties of the obtained molded product may be poor.
On the other hand, the upper limit is preferably 4.0 or less. 4.
If it exceeds 0, it is difficult to polymerize the resin itself and the moldability during the above-mentioned molding may be impaired. The relative viscosity is measured according to JIS K6810.

The polyamide-based resin used as the thermoplastic non-fluorine resin is used in order to prevent the decomposition reaction due to heating during molding to generate a low molecular weight product or gelation, and to prevent oxidation. In order to suppress coloring due to the like, the terminal amino group concentration is 10 to 60 equivalents /
It is preferably 10 ⁶ g.

Since the polyamide resin used as the thermoplastic non-fluorine resin has a sufficient molecular weight, the terminal carboxyl group concentration is preferably 80 equivalents / 10 ⁶ g or less.

As the above polyamide-based resin, when the laminated resin molding of the present invention is used for applications requiring toughness such as tubes and hose moldings, nylon 6, nylon 66, nylon is used. 11, nylon 12,
Nylon 610, Nylon 612, Nylon 6/66,
Nylon 66/12, Nylon 6-Polyester Copolymer, Nylon 6-Polyether Copolymer, Nylon 12
-Polyester copolymer and / or nylon 12-
It is preferably a polyether copolymer, such as nylon 11, nylon 12, nylon 610, nylon 61.
2, Nylon 6-polyether copolymer or Nylon 12-polyether copolymer is more preferable. Among them, nylon 11 and nylon 12 are more preferable.

The layer (C) may further contain a plasticizer, another resin or the like within a range not impairing the object of the present invention. The plasticizer can soften the resin composition and improve the low temperature mechanical properties of the resin laminate (eg, tube or hose). Moreover, the impact resistance of a resin laminated body (for example, a tube or a hose) can be improved by compounding another resin.

The above plasticizer is not particularly limited, and examples thereof include hexylene glycol, glycerin, β-naphthol, bisphenol compounds such as dibenzylphenol, octylcresol and bisphenol A, octyl p-hydroxybenzoate, p-hydroxybenzoate. Acid 2-ethylhexyl, p-hydroxybenzoic acid peptyl, p-
Ethylene oxide and / or propylene oxide adduct of hydroxybenzoic acid, ε-caprolactone, phosphoric acid ester compound of phenols, N-methylbenzenesulfonamide, N-ethylbenzenesulfonamide,
Examples thereof include N-butylbenzenesulfonamide, toluenesulfonamide, N-ethyltoluenesulfonamide, N-cyclohexyltoluenesulfonamide and the like.

As the other resin that can be blended in the layer (C), those having excellent compatibility are preferable, and examples thereof include ester- and / or carboxylic acid-modified olefin resins and acrylic resins (particularly acrylic resins having a glutarimide group). Resin), ionomer resin, polyester resin, phenoxy resin, ethylene / propylene / diene copolymer, polyphenylene oxide and the like.

The layer (C) may further contain a colorant, various additives and the like within a range not impairing the object of the present invention. Examples of the additive include an antistatic agent,
Flame retardants, heat stabilizers, UV absorbers, lubricants, mold release agents, crystal nucleating agents, reinforcing agents (fillers) and the like can be mentioned.

The laminated resin molding of the present invention has the above-mentioned layer (A).
Is preferably an ETFE-based copolymer, and the layer (B) is a thermoplastic resin composition in which the fluorine-containing ethylenic polymer (Y) is the above-mentioned copolymer (IV). Is preferred, and as the layer (C),
A polyamide resin is preferable.

The laminated resin molding of the present invention comprises at least
The layer (A) and the layer (C) are formed by laminating the layer (B) as an adhesive layer. For this, it is possible to apply a manufacturing method in which constituent layers including the layer (A), the layer (C) and the layer (B) are sequentially or co-extruded, a manufacturing method by thermocompression bonding of a molded body, and the like. Therefore, a good adhesion state is formed between the constituent layers including the layer (A), the layer (C), and the layer (B). The above-mentioned manufacturing can use a molding machine of a thermoplastic resin which is usually used, for example, an injection molding machine, a compression molding machine, a blow molding machine, an extrusion molding machine, etc., and can be manufactured into various shapes such as sheet, tube and the like. Is. In the case of forming a multilayer molded product such as a multilayer tube, a multilayer hose, and a multilayer tank, a molding method such as multilayer coextrusion molding, multilayer blow molding, multilayer injection molding can be applied. Of these, extrusion molding, particularly multi-layer coextrusion molding, is preferable for molding tubes, hoses, sheets and the like, and blow molding can be suitably used for molding hollow articles such as cylindrical shapes. Further, the formed sheet can be laminated with another base material to manufacture a lining body.

The molding conditions vary depending on the type of carbonyl group, especially carbonyldioxy group, the type of fluorine-containing ethylenic polymer (Y), the type of fluorine-containing ethylenic polymer, etc., but in extrusion or blow molding Is
It is suitable to heat so that the cylinder temperature is 200 ° C. or higher. The upper limit of the heating temperature is below the temperature at which adverse effects such as foaming due to thermal decomposition of the fluorine-containing ethylenic polymer (Y), the fluorine-containing ethylenic polymer, the non-fluorine thermoplastic resin (Z) and the thermoplastic non-fluorine resin can be suppressed. Is preferably 400 ° C. or lower, and particularly preferably 350 ° C. or lower.

In addition, when the laminated resin molding has a complicated shape or when heat bending is performed after molding,
In order to eliminate the residual strain of the obtained laminated resin molded body, the above laminated resin molded body is melt-extruded, and the formed laminated resin molded body has the lowest melting point of the resins constituting the laminated resin molded body. It is also possible to heat treat for 0.01 to 10 hours at a temperature lower than the melting point to obtain a desired laminated resin molded body. By adopting this manufacturing method, it is considered that residual strain is eliminated, and unreacted substances near the layer interface react, and these can be combined to further increase the adhesive strength of the laminated resin molded body. This heat treatment is 60 ° C or higher,
Furthermore, it is preferable to carry out at 80 ° C. or higher.

In the present invention, the initial interlayer adhesive force between the layer (A) made of a polyamide resin and the layer (B) is 2
It can be 0 N / cm or more.

At this time, the layer (A), the layer (B) and the layer (C) may undergo decomposition or reaction of functional groups to some extent by heating, but they are melt-extruded as described above. The laminated resin molded body is also the laminated resin molded body of the present invention.

The laminated resin molding of the present invention has the above-mentioned layer (B).
May have a thickness of less than 0.5 mm. When the layer having a better fuel permeation resistance than the layer (B) is the layer (A) or the layer (C), the layer (B) can be thin. The range may be less than 1.5 times the total thickness of the layer (B) and the layer (C). Therefore, the layer (B) can make the adhesive layer thin, which is economically advantageous.

The laminated resin molding of the present invention further comprises a layer (D) made of a fluororesin laminated on the surface of the layer (A) opposite to the surface on which the layer (B) is laminated. May be The layer (D) made of the fluororesin may contain a conductive material in order to impart conductivity, if necessary. In this case, the blending amount of the conductive material may be the amount that can impart conductivity, and may be the above blending ratio.

The fluororesin is not particularly limited,
Any melt-moldable fluororesin can be used, for example, tetrafluoroethylene / fluoro (alkyl vinyl ether) copolymer [PFA], tetrafluoroethylene / hexafluoropropylene copolymer [FE]
P], ethylene / tetrafluoroethylene copolymer [E
TFE], polychlorotrifluoroethylene [PCTF
E], ethylene / chlorotrifluoroethylene copolymer [ECTFE] and the like. Further, the above-mentioned fluorine-containing ethylenic polymer (Y) may be used. Among these, it is excellent in flexibility, low temperature impact resistance, heat resistance, etc. while maintaining low fuel permeability, and is suitable for producing fuel pipe tubes, hoses, etc. by simultaneous multi-layer extrusion with polyamide resin. There is a melt flow rate of 2
It is 0.5 to 100 g / 10 minutes at 30 to 350 ° C. The fluorine-containing ethylenic polymer in the layer (A) and the fluororesin in the layer (D) may be the same or different, but are preferably the same type from the viewpoint of adhesiveness.

In the present invention, the layer (A) containing no conductive material and the layer (D) containing a conductive material may be laminated. In this case, the blending amount of the conductive material may be the amount that can impart conductivity, and may be the above blending ratio. In this case, the above-mentioned fluororesin can be used as the fluororesin forming the layer (D), and may be the same or different kind of fluororesin as the layer (C).

The laminated resin molding of the present invention further comprises a protective layer (E) laminated on the surface of the layer (C) opposite to the surface on which the layer (B) is laminated. The layer (E) may be made of thermoplastic resin or rubber. The layer (E) is the layer (A) or the layer (B).
And a layered product comprising the layer (C) and the layer (D), which is optionally provided, are coextruded at the same time or are formed by coating in a separate step.

The multilayer molded article of the present invention is characterized by comprising the above laminated resin molded article. Examples of the multilayer molded article include: tubes, hoses: tubes or hoses for automobile fuel piping, automobile radiator hoses, brake hoses,
Films and sheets for air conditioner hoses, wire coatings, optical fiber coatings, etc .: Sliding members such as diaphragms of diaphragm pumps and various packings that require high chemical resistance, agricultural films, linings, weatherproof covers, construction and Laminated steel plates and other tanks used in the field of home appliances, such as automobile radiator tanks, chemical bottles,
Chemical tanks, bags, chemical containers, gasoline tanks, etc. Others: Flange gaskets for carburetors, various automotive seals such as O-rings for fuel pumps, chemical-related seals such as seals for chemical pumps and flow meters, seals for hydraulic equipment, etc. In addition to various mechanical seals, etc., it may be bellows, spacers, rollers, electronic / electrical parts, etc.

Among them, in a preferred embodiment, for example, (i) the layer (C) is the outer layer, the layer made of the above thermoplastic resin composition is the layer (B), and a conductive material may be contained. A tube or hose having at least a three-layer structure having the layer (A) as an inner layer, particularly a tube or hose for automobile fuel piping or a hose (ii) layer (C) as an outer layer, and a layer comprising the above thermoplastic resin composition as a layer (B), at least a four-layer tube or hose having the layer (A) as the inner layer and the layer (D) that may contain a conductive material as the innermost layer, especially for automobile fuel piping or chemical solution tube or A hose is mentioned.

In the above aspects (i) and (ii), from the viewpoint of fuel resistance, the MFR of the layer in contact with the fuel is kept low, especially when a conductive material is blended. For example, when measured at 297 ° C., 100 g / 10 minutes or less, preferably 40 g / 10
50 g / min when measured at 265 ° C.
It may be 10 minutes or less, preferably 20 g / 10 minutes or less.

The above-mentioned multilayer molded article is preferably a film, a hose, a tube, a bottle or a tank, more preferably an automobile fuel pipe tube or an automobile fuel pipe hose.

In addition, in the above-mentioned embodiment, the attachability,
Only the layer (C) or all layers may be processed into a bellows shape or a spiral shape for the purpose of impact absorption and the like.
Further, for example, necessary parts such as a connector can be added, or an L shape or a U shape can be formed by bending.

The fluororesin molded article of the present invention comprises the above thermoplastic resin composition. The fluororesin molded article of the present invention can be used alone. in this case,
The fluorine-containing resin molded product is preferably used as a film, a hose, a tube, a bottle or a tank, and more preferably used as an automobile fuel pipe tube or an automobile fuel pipe hose.

The fluorine-containing resin molded product of the present invention may be used by being laminated with another layer. In this case, for example, it may be the same as the laminate described above as the laminated resin molded product of the present invention or the multilayer molded product of the present invention, or may be a laminated product of a different aspect. Examples of the laminate using the fluorine-containing resin molded product of the present invention include the following, which can be preferably used as a tube, for example.

Specific preferred examples of the laminated tube using polyamide include: i) (B1) Layer made of the fluororesin molded article of the present invention (C1) A laminated body made of a layer made of polyamide resin is formed into a tube shape. A laminated tube characterized by the fact that (B1) forms an inner layer; ii) (B1) a layer made of the fluororesin molded article of the present invention (A1) a layer made of ETFE (C1) A laminated tube in which a laminated body made of a layer made of a polyamide resin is formed into a tubular shape, wherein the layer (A1) made of ETFE forms the innermost layer;

Iii) (B1) Layer made of the fluororesin molded article of the present invention (C1) A laminated tube formed by forming a laminate made of a layer made of a polyamide resin into a tubular shape, wherein (B1) is an inner layer. Iv) (B1) Layer made of the fluororesin molded article of the present invention (A2) Layer made of PVdF or VdF copolymer (C1) Made of polyamide resin A laminated tube formed by forming a laminated body of layers into a tubular shape, wherein the layer (A2) made of PVdF or VdF copolymer forms the innermost layer;

V) (C1) Layer made of polyamide resin (B1) Layer made of fluorine-containing resin molded article of the present invention (C1) Layered body made of polyamide resin is formed into a tube shape. A laminated tube or the like, in which (B1) is located in an intermediate layer of two layers of the polyamide resin (C1), and the like.

The same fillers, reinforcing agents, and additives as described above can be added within a range that does not impair the intended characteristics of each layer of these laminates. Especially when used for fuel pipes and chemical tubes,
A filler that imparts conductivity is preferably added to the fluoropolymer layer of the inner layer. The fluororesin molded article of the present invention can be formed into a required shape by various post-processing. For example, it is possible to add necessary parts such as a connector or the like, or to form it into an L shape, a U shape, or a corrugated tube shape by bending.

Further, as a preferred specific example of the laminate using the fluororesin molded product of the present invention, a laminate comprising (B1) a layer composed of the fluororesin molded product and (D1) a layer composed of polyethylenes It is the body. The polyethylenes (D1) preferably have a functional group having reactivity or affinity with the above-mentioned carbonyldioxy group or haloformyl group. Specifically, epoxy-modified polyethylene,
Ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ethylene / maleic anhydride copolymer,
Ethylene / acrylic acid copolymer is a preferred example. Similar to the above, these laminates can be formed into various shapes. Among them, in the case of a tank shape, for example, it can be used as a gasoline tank for automobiles, which has been resinified in recent years, and has improved fuel permeability. It can and can be given heat resistance.

Specifically, i) (B1) layer comprising the fluorine-containing resin molded article of the present invention (D1) comprising a layer comprising polyethylenes, and (B1) being the inner layer side, the laminate has a tank shape. What is molded; ii) (D1) layer composed of polyethylene (B1) layer composed of the fluororesin molded article of the present invention (D1) composed of polyethylene, between (B1) and (D1) two layers Preferable examples include those in which the positioned laminate is formed in a tank shape.

Further, when the layer comprising the fluororesin molded article of the present invention and the polyethylene is formed into a bottle shape, for example, the chemical resistance of the fluoroethylenic polymer (Y) is Can be used as a bottle for semiconductors. Specific examples include i) (B1) a layer made of the fluororesin molded article of the present invention (D1) a layer made of polyethylenes, and a laminate in which (B1) is located on the inner layer side is formed into a bottle shape. Those are preferable.

The method for producing a laminate using the layer comprising the fluorine-containing resin molded article of the present invention is as follows:
It is appropriately selected depending on the type and shape of the organic material. For example, a method of producing a film made of the fluororesin molded article of the present invention using the above-mentioned thermoplastic resin composition, superposing it with an organic material, and laminating by heat activation by heating as described above, or an organic material On the above, the thermoplastic resin composition is in the form of a paint such as a water level or an organic solvent dispersion, an organic solvent soluble material, and a powder, and a method of applying and heat activating by heating, an insert molding method, or the above When laminating the thermoplastic resin composition and the melt-moldable thermoplastic polymer, a coextrusion method or the like can be adopted. By these methods, a laminate using the layer comprising the fluororesin molded article of the present invention can be molded into a shape such as a hose, pipe, tube, sheet, seal, gasket, packing, film, tank, roller, bottle, container and the like. .

As a method for producing these laminates, the thermoplastic resin composition having a carbonyl group-containing group and the thermoplastic fluororesin are molded at the molding temperature, that is, the resin temperature at the molding has respective crystal melting points or glass transition points. It is characterized in that it is formed by coextrusion at a temperature exceeding it. That is, by simultaneous melt extrusion, adhesion of the thermoplastic resin composition and the thermoplastic fluororesin, and at the same time, molding into the desired shape can be achieved simultaneously and continuously, resulting in excellent productivity and good adhesion performance. preferable.

The above various laminated bodies may have a jacket layer for the purpose of protection, antifouling, insulation, impact absorption, etc. as the outermost layer. The jacket layer is
For example, a resin, a natural or synthetic rubber, or the like is used and co-extruded at the same time as the resin laminate, or formed by coating in a separate step. It is also possible to reinforce with metal or the like.

[0141]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, below, the measurement of various parameters was performed as follows. (1) Measurement of composition of fluorine-containing ethylenic polymer It was measured by ¹⁹ F-NMR analysis.

(2) Measurement of melting point (Tm) Using a Seiko type DSC device, the melting peak when the temperature was raised at a rate of 10 ° C./min was recorded, and the temperature (° C.) corresponding to the maximum value was measured as the melting point (Tm). ).

(3) MFR (Melt Flow Ra)
Measurement of te) Using a melt indexer manufactured by Toyo Seiki Seisaku-sho, Ltd., the weight (g) of the polymer flowing out from a nozzle having a diameter of 2 mm and a length of 8 mm in 10 minutes as a unit time was measured under various temperatures and under a load of 5 kg.

(4) Measurement of the number of carbonyldioxy groups A white powder of the obtained fluorine-containing ethylenic polymer or a cut piece of melt-extruded pellet was compression molded at room temperature to a thickness of 0.05 to 0.2 mm. I made a film. By infrared absorption spectrum analysis of this film, a peak to which a carbonyl group of a carbonyldioxy group [-OC (= O) O-] is assigned appears at an absorption wavelength of 1809 cm ^-1 (νC = O), and its νC = O peak. The absorbance of was measured. The number (N) of carbonyldioxy groups per 10 ⁶ carbon atoms in the main chain was calculated by the following formula (i). N = 500 AW / εdf (i) A: Absorbance of νC = O peak in carbonyldioxy group [-OC (= O) O-] ε: Carbonyldioxy group [-OC (= O) O- ] Molar extinction coefficient of νC = O peak [unit: l · cm
⁻¹ · mol ⁻¹ ]. From the model compound, ε = 170. W: Average molecular weight of monomer calculated from monomer composition d: Density of film [g / cm ³ ] f: Thickness of film [mm] Infrared absorption spectrum analysis was performed using Perkin-El.
It was performed by scanning 40 times using a mer FTIR spectrometer 1760X (manufactured by Perkin Elmer). The obtained IR spectrum was analyzed by Perkin-Elme.
r Spectrum for Windows Ve
r. Automatically determine the baseline at 1.44C 1
The absorbance of the peak at 809 cm ^-1 was measured. The thickness of the film was measured with a micrometer.

(5) Measurement of number of fluoroformyl groups Main chain carbon number 10 ^{6 of the} obtained fluorine-containing ethylenic polymer
The number (N) of fluoroformyl groups per piece was measured and calculated by infrared absorption spectrum analysis in the same manner as the above-mentioned measurement of the number of carbonyldioxy groups.

(6) Measurement of adhesive strength of multi-layer tube A test piece of 1 cm width was cut out from the tube, a part of the sample was peeled off, fixed on the outer layer, the inner layer and the chuck, and 25 mm / min with a Tensilon universal testing machine. At the speed of
An 80 ° peel test was performed, and the average of the maximum 5 points in the elongation-tensile strength graph was determined as the adhesive strength between layers.

(7) Measurement of fuel permeation rate A test fuel (C was added to a SUS container having a volume of about 20 ml).
M15; toluene: isooctane: methanol = 32.
5: 32.5: 15 [volume ratio]), and the opened one side was sealed with a sample sheet, but the fuel permeation rate was measured from the change in weight at 60 ° C.

Synthesis Example 1Containing carbonyldioxy group
Synthesis of fluorine ethylenic polymer Pour 380 L of distilled water into the autoclave and thoroughly fill it with nitrogen.
After substitution, 1-fluoro-1,1-dichloroethane
75 kg, hexafluoropropylene 155 kg,
-Fluoro (1,1,5-trihydro-1-pente
0.5 kg was charged, the inside of the system was 35 ° C., the stirring speed was 20
It was kept at 0 rpm. Then add tetrafluoroethylene
Press in up to 0.7 MPa, then continue to add ethylene.
Press-fit to 1.0 MPa, then di-n-propylpa
-Add 2.4 kg of oxydicarbonate to start polymerization
Started Since the system internal pressure decreases as the polymerization progresses,
Trafluoroethylene / ethylene / hexafluoropro
Pyrene = 40.5 / 44.5 / 15.0 mol% mixed gas
Continuously supplied to maintain the system pressure at 1.0 MPa.
It was And perfluoro (1,1,5-trihydro
-1-Pentene) is continuously used for a total amount of 1.5 kg.
Then, stirring was continued for 20 hours. And release the pressure
After returning the pressure to atmospheric pressure, wash the reaction product with water, dry and
200 kg of powder of the base resin (1) was obtained. Fluororesin
Table 1 shows the physical properties of (1).

Synthesis Example 2Carbonyldioxy group-containing ET
Synthesis of FE-based copolymer Pour 380 L of distilled water into the autoclave and thoroughly fill it with nitrogen.
After substitution, 1-fluoro-1,1-dichloroethane
325 kg, perfluoro (1,1,5-trihydrate
(1-pentene) 0.9 kg was charged, and the system was cooled to 35
The temperature was kept at ℃ and the stirring speed was 200 rpm. Then Tetrav
Luoroethylene is pressed up to 0.86MPa and further pulled
Next, pressurize ethylene to 0.90 MPa, and then
3.5 kg of di-n-propyl peroxydicarbonate
Was charged to start the polymerization. System pressure as polymerization progresses
Is reduced, tetrafluoroethylene / ethylene =
Continuous supply of 64.8 / 35.2 mol% mixed gas
Then, the system pressure was maintained at 0.90 MPa. And par
Fluoro (1,1,5-trihydro-1-pentene)
Also, the total amount of 9.1 kg was continuously charged at 24:00.
The stirring was continued for a while. Then, the pressure was released and returned to atmospheric pressure.
After that, the reaction product is washed with water and dried to obtain ethylene / tetraflu
200 kg of ethylene oxide [ETFE] copolymer powder
Got This ETFE copolymer is used as a fluororesin (2).
The physical properties are shown in Table 1.

Synthesis Example 3ETF containing fluoroformyl group
Synthesis of E-based copolymer Fluorine resin (2) powder was added to a single-screw extruder (Tanabe Plastic
KU Machine Co., Ltd., VS50-24) (L / D = 24)
Liu diameter: 50 mm), cylinder temperature 30
Extrusion at 0-320 ℃, resin temperature near the die 320 ℃
Then, pellets of fluororesin (3) were obtained. Fluorine tree
Table 1 shows the physical properties of the fat (3).

Synthesis Example 4Fluorine-containing materials that do not have reactive functional groups
Synthesis of elemental ethylene polymer Fluorine resin (1) powder 95kg, pure water 100L 50
Put in a 0L stainless steel autoclave and add 28%
Add 7 kg of monia water and stir at 80 ° C for 5 hours.
Heated for a while. Take out the powder of the contents, wash with water and dry.
Thus, 93 kg of fluororesin (4) powder was obtained. Fluorine tree
Table 1 shows the physical properties of the fat (4).

Synthesis Example 5ETF without reactive functional group
Synthesis of E-based copolymer Using a powder of fluororesin (2), the same procedure as in Synthesis Example 4
Thus, powder of fluororesin (5) was obtained. Fluororesin (5)
The physical properties are shown in Table 1.

[0153]

[Table 1]

Processing Example 1Containing carbonyldioxy group
Melt kneading of fluorine ethylenic polymer and polyamide Laboplastomi made by Toyo Seiki Seisakusho Co., Ltd. set at 260 ° C
32.4g of fluororesin (1) in a mixer
Polyamide 12 (manufactured by Ube Industries, Ltd., trade name: UBE
3030B) 23.2 g was added, and 10 rpm was applied for 2 minutes.
After pre-kneading, the melt-kneading was performed at 50 rpm for 8 minutes.
Thus, a thermoplastic resin composition (6) was obtained.

Example 1Electron microscopy of thermoplastic resin composition
Mirror image observation Cool the thermoplastic resin composition (6) with liquid nitrogen,
A sample is created by cutting with a rotome, and the accelerating voltage is 20
A transmission electron microscope image was taken at 0 kV. Obtained electricity
A child microscope image is shown in FIG.

Comparative Example 1Fluorine-containing materials that do not have reactive functional groups
Of a resin composition comprising an ethylenic polymer and a polyamide
Electron microscope image observation Other than using fluororesin (1) instead of fluororesin (1)
Was obtained in the same manner as in Processing Example 1 to obtain a resin composition (7).
Then, a transmission electron microscope image of this resin composition (7) was obtained.
It photographed like Example 1. Figure of the obtained electron microscope image
2 shows.

Example 2Containing carbonyldioxy group
Thermoplastic resin composed of fluorine ethylenic polymer and polyamide
Tensile test of fat composition 260 after finely cutting the thermoplastic resin composition (6)
Put it in a 100mmφ mold preheated to ℃ and set it at 260 ℃.
Set on the specified press machine, and after preheating for 5 minutes,
20 kgf / cm^TwoCompression molding for 20 seconds, thickness 1
A sheet of mm was obtained. No. 5 test piece obtained using a punching blade
Dumbbell punched from the sheet, Tensilon universal testing machine
In, a tensile test is performed at a speed of 10 mm / min.
Tensile strength at break and elongation at tensile at 10 were determined.
The results are shown in Table 2.

Comparative Example 2Containing no fluorine containing reactive functional groups
Resin composition comprising fluorine ethylenic polymer and polyamide
Tensile test Replace the thermoplastic resin composition (6) with the resin composition (7)
A sheet was obtained in the same manner as in Example 2 except that it was used.
After that, the tensile strength at break and the elongation at tensile break were determined. result
Is shown in Table 2.

[0159]

[Table 2]

From Table 2, in Example 2 using the thermoplastic resin composition (6) of the present invention, as compared with Comparative Example 2 in which the fluorine-containing ethylenic polymer has no reactive functional group, the tensile strength at break point is higher. Since the tensile elongation at break was high and the standard deviation was small, it was found that these high strengths were stably obtained.

Reference Example 1Carbonyldioxy group-containing ET
Thermoplastic resin group consisting of FE-based copolymer and polyamide
Making pellets of products Fluorine resin (2) powder was added to a single-screw extruder (Tanabe Plastic
Ku Machinery, product number: VS50-24, L / D = 24,
Clew diameter: 50mm), cylinder temperature 2
Extrusion at 10-280 ℃, resin temperature near die at 280 ℃
Then, pellets of fluororesin (2) were prepared. This
Fluororesin (2) pellets and commercially available polyamide 12
(Ube Industries, Ltd., trade name: UBE3030B)
Pre-mixed with 7: 3 by weight of pellets
Is a Toyo Seiki Seisakusho Lab Plastomill twin-screw extruder
(Screw diameter: 25 mm), put into the cylinder temperature
At a temperature of 200-260 ℃, resin temperature of 260 ℃ near the die
Extrusion is performed to obtain pellets of the thermoplastic resin composition (8).
Created.

Reference Example 2ETF without reactive functional group
Pellet of E-based copolymer The fluororesin (5) is used instead of the fluororesin (2).
In the same manner as in Reference Example 1, the resin composition (9)
Created a set.

Example 3Creating a multi-layer tube 3 types 3 layers tube with multi-manifold die
Using the extruder, the outer layer of the tube is
Do 12 (manufactured by Ube Industries, Ltd., trade name: UBE3035
MI1), the intermediate layer is the thermoplastic resin composition (8), and the inner layer is
Commercially available ETFE (manufactured by Daikin Industries, trade name: NEOFLON
ETFE EP-610AS)
In addition, polyamide 1 is used as an extruder for the outer layer, the middle layer and the inner layer.
2. With thermoplastic resin composition (8) and EP-610AS
To supply a tube with an outer diameter of 8 mm and an inner diameter of 6 mm.
Was molded. Molding condition and evaluation result of the obtained tube
Is shown in Table 3. Delamination is the interface at the interface between the outer and middle layers.
It happened as a face destruction. Peel strength (adhesive strength) is 3
It reached 3.5 N / cm. Appearance of peeled surface caused by peeling
Had no surface roughness and was smooth.

Comparative Example 3Creating a multi-layer tube Resin as an intermediate layer instead of the thermoplastic resin composition (8)
Same as Example 3 except that the composition (9) is supplied.
The tube was continuously molded. Molding conditions and obtained
Table 3 shows the evaluation results of the tubes. Peeling is the middle layer
Occurred as a cohesive failure. Peel strength (adhesive strength)
It was 24.5 N / cm. Outside the peeled surface caused by peeling
The view was rough.

[0165]

[Table 3]

From Table 3, it is considered that in Comparative Example 3 in which the fluorine-containing ethylenic polymer has no reactive functional group, the tensile strength of the intermediate layer was weak because cohesive failure of the intermediate layer occurred, and While the adhesive strength was weak, in Example 3 using the thermoplastic resin composition (8) of the present invention, the tensile strength inside the intermediate layer was strong because it was broken at the interface between the outer layer and the intermediate layer. Therefore, it was found that the adhesive strength was high.

Example 4ETF containing fluoroformyl group
Thermoplastic resin composition comprising E-based copolymer and polyamide
Measurement of fuel permeability of sheets obtained from objects If fluororesin (3) is used instead of fluororesin (1)
The thermoplastic resin composition (1
0) finely cut and preheated to 280 ° C 100mmφ
Put it in the mold of the machine and set it in the press machine set at 280 ℃.
And after preheating for another 5 minutes, 37kgf / cm^Two20
Compression molding was performed for 2 seconds to obtain a sheet having a thickness of 0.5 mm.
The fuel permeability was measured using this sheet. The results are shown in Table 4.
Shown in.

Comparative Example 4ETF without reactive functional group
Obtained from a resin composition comprising an E-based copolymer and polyamide
Sheet fuel permeability measurement Resin composition (9) in place of the thermoplastic resin composition (10)
Create a sheet in the same manner as in Example 4 except that
Then, the fuel permeability was measured. The results are shown in Table 4.

[0169]

[Table 4]

From Table 4, in Comparative Example 4 in which the fluorine-containing ethylenic polymer does not have a reactive functional group, the fuel permeation resistance was inferior, while the thermoplastic resin composition (1
It was found that in Example 4 using 0), the fuel permeation resistance was excellent.

[0171]

Since the thermoplastic resin composition of the present invention has the above-mentioned constitution, it is superior in mechanical strength to a resin composition using a fluorine-containing ethylenic polymer having no reactive functional group, A layer made of a fluororesin and a layer made of a thermoplastic resin which are adjacent to each other can be more strongly adhered to each other, and the fuel permeation resistance is also excellent.

[Brief description of drawings]

FIG. 1 is a transmission electron microscope image in Example 1.

FIG. 2 is a transmission electron microscope image in Comparative Example 1.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 23/00 C08L 23/00 77/02 77/02 101/00 101/00 (72) Inventor Takahiro Kitahara No. 1 Nishiichitsuya, Settsu-shi, Osaka Prefecture Yodogawa Manufacturing Co., Ltd. (72) Inventor Eiji Fujita No. 1 Nishiichitsuya, Settsu-shi, Osaka Prefecture Yodogawa Manufacturing Co., Ltd. (72) Inventor Tetsuo Shimizu Osaka Prefecture Settsu City Nishihitotsuya No. 1 No. 1 Daikin Industries Ltd. Yodogawa Plant in the F-term (reference) 4F071 AA14 AA26 AA27 AA29 AA43 AA51 AA53 AA55 AA62 AA67 AF15 AF21 AH19 BC01 BC05 BC07 4F100 AK01A AK01B AK03B AK03C AK04A AK17D AK18A AK18B AK21B AK21C AK25B AK25C AK41B AK41C AK46B AK46C AK48B AK48C AK51B AK51C AK54B AK54C AK57B AK57C AL01A AL05A AL05B AL05C AN02E AS00E BA03 BA04 BA05 BA07 BA10A BA10C BA10D BA10E DA02 DA11 GB16 GB32 JA04A JA04B JB16A JB16B JB16C JB16E JG01A JL11 YY00A YY00B 4J002 BB06X BB07X BB08X BB09X BD14W BD15W BE02X CF00X CH07X CK02X CL01X CL03X CL01X CL03X CL01X CL03X CL01X

Claims (38)

[Claims] 1. A thermoplastic resin composition comprising a fluorinated ethylenic polymer (Y) and a non-fluorinated thermoplastic resin (Z), wherein the fluorinated ethylenic polymer (Y) has a main chain terminal and / Or having a reactive functional group at the side chain terminal, the non-fluorine thermoplastic resin (Z) is composed of a non-fluorine polymer having a bond-forming site,
The thermoplastic resin composition, wherein the bond-forming site has a bond-forming property with the reactive functional group. 2. The thermoplastic resin composition according to claim 1, wherein the fluorinated ethylenic polymer (Y) forms a bond with the non-fluorinated thermoplastic resin (Z). 3. The thermoplastic resin composition according to claim 1 or 2, wherein the fluorine-containing ethylenic polymer (Y) is reacted with the non-fluorine thermoplastic resin (Z). 4. The thermoplastic resin composition according to claim 1, which does not have a multi-phase morphological structure. 5. The thermoplastic resin composition according to claim 1, wherein the reactive functional group has a carbonyl group. 6. The carbonyl group is 3 to 100 per 1 × 10 ⁶ carbon atoms in the main chain of the fluorine-containing ethylenic polymer (Y).
The thermoplastic resin composition according to claim 5, which is 0 in number. 7. The thermoplastic resin composition according to claim 5, wherein the carbonyl group is derived from peroxide. 8. The thermoplastic resin composition according to claim 5, 6 or 7, wherein the reactive functional group is a carbonyldioxy group and / or a haloformyl group. 9. The fluorine-containing ethylenic polymer (Y) has a melting point of 120 to 270 ° C.
The thermoplastic resin composition according to 3, 4, 5, 6, 7 or 8. 10. The fluorine-containing ethylenic polymer (Y) is
It is obtained from a monomer component containing tetrafluoroethylene and ethylene.
The thermoplastic resin composition according to 6, 7, 8 or 9. 11. The fluorine-containing ethylenic polymer (Y) is
Tetrafluoroethylene, and the following general formula _{(1) CF 2 = CF-} Rf 1 (1) ( wherein, .Rf Rf ¹ is representative of a -CF ₃ or-ORF ^2
2 represents a perfluoroalkyl group having 1 to 5 carbon atoms. )
A compound obtained from a monomer component containing a perfluoroethylenically unsaturated compound represented by:
The thermoplastic resin composition according to 4, 5, 6, 7, 8 or 9. 12. The fluorine-containing ethylenic polymer (Y) is
Tetrafluoroethylene 19-90 mol%, ethylene 9
80 mol%, and the following general formula _{(1) CF 2 = CF-} Rf 1 (1) ( wherein, .Rf Rf ¹ is representative of a -CF ₃ or-ORF ^2
2 represents a perfluoroalkyl group having 1 to 5 carbon atoms. )
Perfluoroethylenically unsaturated compounds 1 to 7
The thermoplastic resin composition according to claim 1, which is obtained from a monomer component containing 2 mol%. 13. The fluorine-containing ethylenic polymer (Y) is
It is obtained from a monomer component containing 15 to 60 mol% of vinylidene fluoride, 35 to 80 mol% of tetrafluoroethylene, and 5 to 30 mol% of hexafluoropropylene. The thermoplastic resin composition according to 5, 6, 7, 8 or 9. 14. The non-fluorine thermoplastic resin (Z) is a polyamide resin, 1, 2, 3, 4, 5, 6,
The thermoplastic resin composition according to 7, 8, 9, 10, 11, 12 or 13. 15. The polyamide resin is nylon 6, nylon 66, nylon 11, nylon 12, nylon 6
10, nylon 612, nylon 6/66, nylon 6
The thermoplastic according to claim 14, which is 6/12, a nylon 6-polyester copolymer, a nylon 6-polyether copolymer, a nylon 12-polyester copolymer, and / or a nylon 12-polyether copolymer. Resin composition. 16. The polyamide resin is nylon 11,
Nylon 12, nylon 610, nylon 612, nylon 6-polyether copolymer, or nylon 12-
The thermoplastic resin composition according to claim 14, which is a polyether copolymer. 17. The polyamide resin having a terminal amino group concentration of 10 to 60 equivalents / 10 ⁶ g.
The thermoplastic resin composition according to 4, 15 or 16. 18. The thermoplastic resin composition according to claim 14, 15, 16 or 17, wherein the polyamide resin has a terminal carboxyl group concentration of 80 equivalent / 10 ⁶ g or less. 19. The non-fluorinated thermoplastic resin (Z) is a bond-forming site-containing polyolefin resin.
The thermoplastic resin composition according to 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13. 20. The bond forming site-containing polyolefin resin is a copolymer obtained by polymerizing a monomer having a functional group (y) for forming a bond forming site and ethylene. 20. The thermoplastic resin composition according to claim 19, wherein the monomer is glycidyl acrylate, glycidyl methacrylate, maleic anhydride, acrylic acid, methacrylic acid, vinyl acetate and / or vinyl alcohol. 21. The non-fluorine thermoplastic resin (Z) is made of polyvinyl alcohol, polyurethane resin, polyester resin, polysiloxane, polyphenylene oxide or polyphenylene sulfide, 5, 6, 7, 8, 9, 10, 11,
The thermoplastic resin composition according to 12 or 13. 22. A laminated resin molded product in which a layer (A) made of a fluorine-containing ethylenic polymer, an intermediate layer (B) and a layer (C) made of a thermoplastic non-fluorine resin are laminated in this order. And the layer (B) is formed by:
3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 1
3, 14, 15, 16, 17, 18, 19, 20 or 2
1. A laminated resin molded product comprising the thermoplastic resin composition described in 1. 23. The laminated resin molding according to claim 22, wherein the layer (A) has conductivity. 24. The layer (A) is made of an ethylene / tetrafluoroethylene-based copolymer, and the layer (C) is
24. The laminated resin molding according to claim 22 or 23, which is made of a polyamide resin. 25. The polyamide resin is nylon 6, nylon 66, nylon 11, nylon 12, nylon 6
10, nylon 612, nylon 6/66, nylon 6
The laminated resin according to claim 24, which is 6/12, a nylon 6-polyester copolymer, a nylon 6-polyether copolymer, a nylon 12-polyester copolymer, and / or a nylon 12-polyether copolymer. Molded body. 26. The polyamide resin is nylon 11,
Nylon 12, nylon 610, nylon 612, nylon 6-polyether copolymer, or nylon 12-
The laminated resin molded product according to claim 24, which is a polyether copolymer. 27. The polyamide resin has a terminal amino group concentration of 10 to 60 equivalents / 10 ⁶ g.
The laminated resin molded article according to 4, 25 or 26. 28. The laminated resin molded product according to claim 24, 25, 26 or 27, wherein the polyamide resin has a terminal carboxyl group concentration of 80 equivalents / 10 ⁶ g or less. 29. The thermoplastic resin composition according to claim 11, wherein the thermoplastic resin composition is 22, 23, 24, 25, 26,
27. The laminated resin molded product according to 27 or 28. 30. A layer (D) comprising a fluororesin
Is laminated on the surface of the layer (A) opposite to the surface on which the layer (B) is laminated.
The laminated resin molded article according to 5, 26, 27, 28 or 29. 31. The laminated resin molded product according to claim 30, wherein the layer (D) contains a conductive material. 32. Further, the protective layer (E) is laminated on the surface of the layer (C) opposite to the surface on which the layer (B) is laminated. ) Is made of a thermoplastic resin or rubber.
5, 26, 27, 28, 29, 30 or 31. 33. Claims 22, 23, 24, 25, 2
A multilayer molded article comprising the laminated resin molded article according to 6, 27, 28, 29, 30, 31, or 32. 34. The multilayer molded article according to claim 33, which is a film, a hose, a tube, a bottle or a tank. 35. The multilayer molded article according to claim 34, which is a tube for automobile fuel piping or a hose for automobile fuel piping. 36. Claims 1, 2, 3, 4, 5, 6, 7,
8, 9, 10, 11, 12, 13, 14, 15, 16,
A fluorine-containing resin molded article comprising the thermoplastic resin composition according to 17, 18, 19, 20 or 21. 37. The fluororesin molded article according to claim 36, which is a film, a hose, a tube, a bottle or a tank. 38. The fluororesin molded article according to claim 37, which is a tube for automobile fuel piping or a hose for automobile fuel piping.