JP2008031350A - Thermoplastic elastomer body for fuel line hose and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic elastomer body for fuel line hoses having excellent flexibility and fuel permeation resistance. <P>SOLUTION: The thermoplastic elastomer body for the fuel line hoses is obtained by dynamically cross-linking (B) a cross-linkable rubber such as an acrylonitrile-butadiene rubber in a thermoplastic elastomer composition consisting essentially of (A) a polyamide resin having amino groups at the terminals, the (B), (C) an uncross-linked rubber having functional groups reactive with amino groups in the (A) and (D) a phenol resin-based cross-linking agent composed of at least one of a phenol resin having a specific chemical structure and a brominated phenol resin in which the hydroxy group thereof is brominated with the (D). In the thermoplastic elastomer body for the fuel line hoses, an island structure 2 consisting essentially of the (B) and fine particles 3 consisting essentially of the (C) are dispersed in a matrix 1 composed of the (A), respectively. The average particle diameter of the island structure 2 is set within the range of ≥0.1 to <1 μm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a thermoplastic elastomer body for a fuel hose and a method for producing the same, and more specifically, fuel for automobiles [gasoline, alcohol-mixed gasoline (gasohol), alcohol, hydrogen, light oil, dimethyl ether, LPG, CNG, etc.] The present invention relates to a thermoplastic elastomer body for a fuel hose and a method for producing the same.

  Conventionally, a blend rubber (NBR-PVC) of acrylonitrile-butadiene rubber (NBR) and polyvinyl chloride (PVC) has been used as a material for a fuel hose such as a gasoline fuel hose (Patent Document 1). This blend rubber (NBR-PVC) is excellent in gasoline permeation resistance and ozone resistance. However, since the fuel system hose contains PVC, which is an environmentally hazardous substance, there is a concern about the generation of chlorine compounds when the hose is incinerated and discarded, and the low temperature (in an extremely cold region of about −30 ° C.). There is also a problem that the hose sealability during use is inferior.

  On the other hand, when a gasoline permeation resistance level that cannot be dealt with by the above blend rubber or the like is required, a resin type hose such as a polyamide resin is usually used instead of a rubber type. As this resin-type hose, for example, a hose using a thermoplastic elastomer composition in which a polyamide resin is used as a matrix (sea structure) and NBR is dispersed therein as an island structure is proposed (Patent Document 2). . This hose contains no chlorine-generating substances such as PVC in its material, and is made of polyamide resin as a matrix, so that it has excellent gasoline permeation resistance and NBR is dispersed in the matrix. Therefore, it is possible to ensure a certain degree of flexibility. However, simply dispersing NBR in the matrix has a limit in obtaining desired flexibility while ensuring gasoline permeation resistance and the like, and there is still room for improvement.

  Therefore, in order to solve the above problems, the present inventors dispersed island structures such as NBR in a specific polyamide resin matrix and dispersed fine particles mainly composed of non-crosslinked rubber such as acrylic rubber. A thermoplastic elastomer was proposed (Patent Document 3).

Japanese Patent No. 2932980 JP 2001-49037 A JP 2006-77090 A

  However, since the thermoplastic elastomer described in Patent Document 3 is cross-linked using sulfur or organic peroxide, there is room for improvement in terms of flexibility, and sufficiently meets the requirements for high flexibility. I couldn't.

  The present invention has been made in view of such circumstances, and an object of the present invention is to provide a thermoplastic elastomer for a fuel hose that is excellent in flexibility and fuel permeation resistance and a method for producing the same.

In order to achieve the above object, the present invention comprises the following (A) to (D) as essential components, and (B) in the thermoplastic elastomer composition in which the weight ratio of (B) is higher than (A). (D) A thermoplastic elastomer body for a fuel hose that is dynamically cross-linked by (D), wherein (A) is a matrix comprising (B) as a main component, and (C) is a main component. The first gist is a thermoplastic elastomer for a fuel hose in which fine particles to be dispersed are dispersed and the average particle size of the island structure is set in a range of 0.1 μm or more and less than 1 μm.
(A) A polyamide resin having an amino group at the terminal.
(B) At least one crosslinked rubber selected from the group consisting of acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, butyl rubber and halogenated butyl rubber.
(C) Non-crosslinked rubber having a functional group that reacts with the amino group in (A).
(D) A phenol resin-based crosslinking agent comprising at least one of a phenol resin represented by the following general formula (1) and a brominated phenol resin whose hydroxyl group is brominated.

  The present invention also relates to a method for producing the thermoplastic elastomer body for a fuel hose, wherein (A) and (C) are kneaded and reacted to form fine particles mainly composed of (C). Then, the manufacturing method of the thermoplastic elastomer body for fuel type hoses which mixes this with (B) and (D) and dynamically bridge | crosslinks (B) by (D) makes it a 2nd summary.

  The inventors conducted further experiments on the content of the patent document 3 relating to the inventor's own application in order to improve flexibility and the like, and replaced the conventional sulfur crosslinking agent and peroxide crosslinking agent. Thus, the inventors have found that dynamic crosslinking using a specific phenol resin-based crosslinking agent is extremely effective, and reached the present invention. That is, using a phenol resin-based cross-linking agent composed of at least one of the phenol resin represented by the general formula (1) and a brominated phenol resin whose hydroxyl group is brominated, kneading is performed while kneading a cross-linked rubber such as NBR. When cross-linking is carried out, the cross-linking speed becomes very slow, so that the cross-linked rubber tends to be pulverized and fine. Therefore, the surface area of the island structure (dispersed phase) mainly composed of crosslinked rubber dispersed in the matrix (sea structure: continuous phase) made of a specific polyamide resin is increased, and the flexibility of the thermoplastic elastomer body is increased. It seems to improve.

  In the present invention, dynamic crosslinking refers to crosslinking performed when the thermoplastic elastomer composition is mixed and stirred in a kneader such as a mixer or kneader, and is generally distinguished from mold crosslinking performed using a normal mold. It is synonymous with what is called “dynamic crosslinking”.

  The thermoplastic elastomer body for a fuel hose of the present invention uses a phenol resin-based crosslinking agent comprising at least one of a phenol resin represented by the general formula (1) and a brominated phenol resin whose hydroxyl group is brominated. As a result, the crosslinking speed becomes very slow, and this crosslinking agent is used for dynamic crosslinking while kneading a crosslinked rubber such as NBR, so that the crosslinked rubber is pulverized and made fine (the crosslinked rubber as a main component). The average particle size of the island structure is 0.1 μm or more and less than 1 μm). Therefore, the surface area of the island structure (dispersed phase) mainly composed of cross-linked rubber, which is dispersed in a matrix (sea structure: continuous phase) made of a specific polyamide resin, increases the flexibility of the thermoplastic elastomer body. Improves. As a result, the absorption performance with respect to vibration transmission from the engine and the chassis is improved, the absorption performance of the fluid pressure fluctuation in the hose is also improved, and the vibration of the hose can be suppressed. Further, the insertion property when the fuel system hose is assembled to the pipe is also improved. In addition, the thermoplastic elastomer body according to the present invention has a matrix made of a polyamide resin having an amino group at the end, so that it has excellent resistance to fuel permeation of various gases, oils, gasoline, etc., and non-crosslinked rubber to the matrix. Is excellent in flexibility, impact resistance, low temperature property and the like. Further, in the present invention, since the weight ratio of the inexpensive and rich rubber property of the crosslinked rubber (island structure component) is larger than that of the polyamide resin having a terminal amino group (matrix component), the cost is low, Excellent compression set characteristics. Therefore, the hose formed by this thermoplastic elastomer body can exhibit excellent performance in applications as a fuel-based hose.

  Moreover, a softness | flexibility further improves that the compounding quantity of the said specific phenol resin type crosslinking agent is the said specific range.

  Further, when the weight mixing ratio of the polyamide resin and the crosslinked rubber is set within a specific range, the compression set characteristics are further improved.

  When the non-crosslinked rubber is a rubber having at least one functional group selected from the group consisting of an epoxy group, a maleic anhydride group, and a carboxyl group, fine particles mainly composed of the non-crosslinked rubber in the matrix The stability becomes higher and the product quality becomes better.

  Moreover, when the compounding quantity of the said non-crosslinked rubber is set to the specific range, it will become more excellent in a softness | flexibility etc.

  When the average particle size of the fine particles mainly composed of the non-crosslinked rubber is 1 μm or less, it is possible to suppress a decrease in physical properties (breaking point strength and the like).

  Further, after kneading (A) and (C) and reacting both to form fine particles mainly composed of (C), (B) and (D) are mixed with (B). When dynamically crosslinked by (D), a desired thermoplastic elastomer body for a fuel hose excellent in flexibility and the like can be efficiently produced.

  Next, embodiments of the present invention will be described in detail.

  The thermoplastic elastomer for a fuel hose of the present invention comprises a polyamide resin having a terminal amino group (component A), a specific crosslinked rubber (component B), and a functional group that reacts with the amino group in the component A. A non-crosslinked rubber (C component) having a phenol resin-based crosslinking agent (D component) composed of at least one of a specific phenol resin and a brominated phenol resin as essential components, and a weight ratio of the specific crosslinked rubber (B component) However, the specific crosslinked rubber (B component) in the thermoplastic elastomer composition more than the specific polyamide resin (A component) is dynamically crosslinked using the specific phenol resin-based crosslinking agent (D component). It will be.

  In the present invention, in a matrix (sea structure: continuous phase) made of a specific polyamide resin (component A), an island structure (dispersed phase) mainly composed of a specific crosslinked rubber (component B) and a specific non- Fine particles mainly composed of a crosslinked rubber (component C) are dispersed, and the average particle size of the island structure is set in a range of 0.1 μm or more and less than 1 μm. These are features of the present invention. is there.

  The specific polyamide resin (component A) is not particularly limited as long as it has an amino group at the terminal. For example, lactam polymer, diamine and dicarboxylic acid condensate, amino acid polymer, Examples include copolymers and blends. Specific examples of the specific polyamide resin (component A) include polyamide 6, polyamide 11, polyamide 12, polyamide 610, polyamide 612, a copolymer of polyamide 6 and polyamide 666, or a blend thereof. Used.

  The crosslinked rubber (B component) used together with the specific polyamide resin (component A) is acrylonitrile-butadiene rubber (NBR), hydrogenated acrylonitrile-, in that it is crosslinked with a specific phenol resin-based crosslinking agent (component D). Butadiene rubber (H-NBR), butyl rubber (IIR), halogenated butyl rubber [brominated butyl rubber (Br-IIR), chlorinated butyl rubber (Cl-IIR), etc.] are used. These may be used alone or in combination of two or more.

  As described above, the weight ratio of the crosslinked rubber (component B) is not particularly limited as long as it is larger than the weight ratio of the specific polyamide resin (component A), but the mixing ratio of the component A and the component B is In terms of weight ratio, the range of A component / B component = 45/55 to 10/90 is preferable, and the range of A component / B component = 30/70 to 45/55 is particularly preferable. That is, if it is within such a range, it is more excellent in compression set and the like without being inferior in fuel permeation resistance.

  Next, the non-crosslinked rubber (C component) used together with the A component and the B component reacts with the amino group of the specific polyamide resin (A component) in the elastomer body. Depending on the agent (component D), one that causes little or no crosslinking reaction is used. Examples of the functional group that reacts with the amino group in the specific polyamide resin (component A) include an epoxy group, a maleic anhydride group, and a carboxyl group. These may be used alone or in combination of two or more. Specific examples of the non-crosslinked rubber (component C) having a functional group that reacts with an amino group in the specific polyamide resin (component A) include acrylic rubber, epoxidized natural rubber, maleic acid-modified EPDM, and maleic acid. Examples thereof include modified NBR. These may be used alone or in combination of two or more. Among these, acrylic rubber is preferable because it is easy to achieve a decrease in flexibility.

  The blending amount of the specific non-crosslinked rubber (C component) is not particularly limited, but a total of 100 parts by weight of the specific polyamide resin (A component) and the specific crosslinked rubber (B component) (hereinafter, “ In the range of 1 to 30 parts, particularly preferably in the range of 5 to 20 parts. That is, when the blending amount of the specific non-crosslinked rubber (component C) is set within the above range, the flexibility and the like are further improved.

  Next, as the dynamic crosslinking agent used together with the components A to C, the phenol resin represented by the following general formula (1) and its hydroxyl group (preferably, a terminal hydroxyl group) were brominated. A phenol resin-based cross-linking agent (component D) composed of at least one of brominated phenol resins is used.

In the general formula (1), preferably, Q is —CH ₂ —O—CH ₂ —, m is 0 or a positive integer of 1 to 10, and R is an organic group having less than 20 carbon atoms. Particularly preferably, m is 0 or a positive integer of 1 to 5, and R is an organic group having 4 to 12 carbon atoms.

  Among the specific phenol resin-based crosslinking agents (component D), alkylphenol formaldehyde resins, methylolated alkylphenol resins, and brominated alkylphenol resins are more preferable, and alkylphenol formaldehyde resins are particularly preferable.

  The specific phenol resin-based crosslinking agent (D component) can be produced by a usual method, for example, by condensing an alkyl-substituted phenol or an unsubstituted phenol with an aldehyde, preferably formaldehyde, in an alkaline medium, Or it can manufacture by condensing bifunctional phenol dialcohol. Or a commercially available phenol resin can also be used.

  Specific examples of the specific phenol resin-based crosslinking agent (D component) include alkylphenol formaldehyde resins (Taoka Chemical Industries, Inc., Tactrol 201), brominated alkylphenol formaldehyde resins (Taoka Chemical Industries, Inc., Tacrol 250-I), Examples thereof include brominated alkylphenol formaldehyde resin (Taoka Chemical Industry Co., Ltd., Tactrol 250-III).

  The compounding amount of the specific phenol resin-based crosslinking agent (component D) is in the range of 1 to 10 parts with respect to a total of 100 parts of the specific polyamide resin (component A) and the specific crosslinked rubber (component B). The range of 2 to 5 parts is particularly preferable. That is, if the amount of component D is less than 1 part, dynamic crosslinking is insufficient, and various physical properties such as compression set tend to be reduced. Conversely, if it exceeds 10 parts, crosslinked rubber ( This is because the average particle size of the island structure having (B component) as a main component is 1 μm or more and the flexibility tends to decrease.

  In addition to the components A to D, the thermoplastic elastomer composition may contain a filler, a reinforcing agent, a processing aid, a conductive agent, a crosslinking accelerator, an antiaging agent, a plasticizer, and the like as appropriate. There is no problem.

  The thermoplastic elastomer body for a fuel hose of the present invention can be produced, for example, as follows. That is, a specific polyamide resin (component A) and a specific non-crosslinked rubber (component C) are blended, and a high temperature (about 200 ° C.) using a kneader such as a kneader, a Banbury mixer, a roll, or a twin-screw kneader. Kneading and reacting both, and kneading is continued until fine particles containing C as a main component are formed (preferably 10 to 30 minutes). This reaction can be confirmed by an increase in viscosity during kneading. Next, a specific cross-linked rubber (B component) and a specific phenol resin-based cross-linking agent (D component) are blended therein, or the specific cross-linked rubber (B component) and a specific phenol resin are blended therein. A premixed mixture of a system cross-linking agent (component D) is blended, and other components such as a filler are blended as necessary, and kneading is continued at a high temperature (about 200 ° C. (preferably 2 to 5). And the above-mentioned specific crosslinked rubber (component B) can be obtained by dynamically crosslinking with a specific phenol resin-based crosslinking agent (component D).

  The thermoplastic elastomer body for a fuel hose of the present invention thus obtained has a specific crosslinked rubber (B) in a matrix 1 made of a specific polyamide resin (component A), for example, as shown in FIG. The island structure 2 having a component as a main component and the fine particles 3 having a specific non-crosslinked rubber (component C) as a main component are each dispersed. The fine particles 3 are not limited to a specific non-crosslinked rubber (component C). For example, as shown in an enlarged portion A of FIG. The polyamide resin 5 may adhere to the surface of 3 or the polyamide resin 5 may be taken into the fine particles 3. The matrix 1 made of the specific polyamide resin (component A) may contain other components such as a filler in addition to the polyamide resin 5.

  In the thermoplastic elastomer for a fuel hose of the present invention, the average particle size of the island structure 2 mainly composed of a specific crosslinked rubber (component B) is in the range of 0.1 μm or more and less than 1 μm from the viewpoint of flexibility. It is set and is preferably in the range of 0.5 μm or more and less than 1 μm. That is, when the average particle size of the island structure 2 is 1 μm or more, the flexibility is inferior.

  Here, the average particle diameter of the island structure 2 can be measured, for example, based on micrographs taken with a scanning electron microscope (SEM), a scanning probe microscope (SPM), an actual microscope, or the like. If the shape of the island structure 2 is not uniform, such as an elliptical sphere (spherical sphere) instead of a true sphere, the simple average value of the longest diameter and the shortest diameter is calculated for the island structure. The particle size.

  Moreover, the average particle diameter of the fine particles 3 mainly composed of the specific non-crosslinked rubber (component C) is preferably 1 μm or less, particularly preferably in the range of 0.5 to 1 μm. It is preferable to set the average particle size in such a range because a decrease in physical properties (breaking strength, etc.) can be suppressed.

  The average particle diameter of the fine particles 3 can also be measured according to the method for measuring the average particle diameter of the island structure 2.

  For example, when the fuel hose has a single layer structure, the thermoplastic elastomer body for a fuel hose of the present invention is used for the layer (single layer), and the fuel hose has a multilayer structure of two or more layers. In this case, it is used for an arbitrary layer (preferably, the innermost layer).

  And the fuel system hose of the said single layer structure can be produced by extruding and molding the thermoplastic elastomer composition which uses the said AD component as an essential component in a hose shape, for example. According to this manufacturing method, the island structure mainly composed of the specific cross-linked rubber (component B) has a shape that is flat from the spherical shape in the extrusion direction when formed into a hose shape. In addition, in the manufacturing method of the said hose, you may use a mandrel as needed.

  The multi-layer fuel system hose is formed, for example, on the outer peripheral surface of the single-layer structure fuel system hose directly or via an intermediate layer such as a reinforcing yarn layer or the like. It can produce by doing.

  The total thickness of the fuel system hose is not particularly limited, and is usually in the range of 1.5 to 12 mm, and the inner diameter of the fuel system hose is usually in the range of 5 to 50 mm.

  Next, examples will be described together with comparative examples. However, the present invention is not limited to these examples.

[Example 1]
A polyamide resin (component A) and an acrylic rubber (component C) are kneaded at 200 ° C. using a twin-screw kneader, the components A and C are reacted, and the average of fine particles mainly composed of component C Kneading was continued until the particle size became 1 μm or less (about 15 minutes). Next, NBR (component B), phenolic resin crosslinking agent (component D), and the remaining components (zinc oxide, stearic acid, vulcanization accelerator) are simultaneously charged into the kneader at 200 ° C. NBR (component B) was dynamically crosslinked (3 minutes). Next, this (thermoplastic elastomer body) was made into a 2 mm thick sheet using a roll and press molded at 230 ° C. for 5 minutes to prepare a sample sheet (120 mm × 120 mm × 2 mm thick).

[Examples 2-7, Comparative Examples 1-6]
A sample sheet was prepared in the same manner as in Example 1 except that the types and amounts of the components were changed as shown in Tables 1 and 2 below.

The materials shown in Table 1 and Table 2 are as follows.
[Polyamide resin (component A)]
Polyamide 11 (manufactured by Arkema, Rilsan BESN P20)
[NBR (component B)]
Nipol DN202 manufactured by Zeon Corporation (AN amount: 31% by weight)
[Acrylic rubber (C component)]
Nipol AR12, manufactured by Nippon Zeon
[Phenolic resin crosslinking agent (component D)]
Alkylphenol formaldehyde resin (Taoka Chemical Industry Co., Ltd., tack roll 201)
[Zinc oxide]
2 types of zinc oxide [stearic acid] manufactured by Mitsui Mining & Smelting Co., Ltd.
Made by Kao, Lunac S30
〔sulfur〕
Sulfax T-10, manufactured by Karuizawa Smelter
[Sulfur-based vulcanization accelerator]
Nouchira TT-G manufactured by Ouchi Shinsei Chemical Co., Ltd.
[Organic peroxide]
Peroximon F-40, manufactured by Nippon Oil & Fats Co., Ltd.

  Using the example product and the comparative product thus obtained, each characteristic was evaluated according to the following criteria. These results are shown in Tables 1 and 2 above.

[Average particle size of island structure]
The cross section of the sample sheet was observed with a micrograph taken with a scanning electron microscope (SEM) (manufactured by JEOL Ltd., JSM-6390), and the average particle size of the island structure was measured. As mentioned earlier, if the shape of the island structure is not uniform, such as an elliptical sphere (a sphere with an elliptical cross section) instead of a true sphere, the simple average value of the longest diameter and the shortest diameter Is the grain size of the island structure.

[Normal Properties] Using the sample sheet, the strength at break (TB) and the elongation at break (EB) were measured according to JIS K6251.

〔Hardness〕
The hardness of the sample sheet was measured according to JIS K6253. In the evaluation, a sample having a hardness of less than 85 was evaluated as ◯, a sample having a hardness of 85 or more and less than 90 was evaluated as Δ, and a sample having a hardness of 90 or more as ×.

[Gasoline permeability resistance (cup method)]
As shown in FIG. 2, a flanged SUS cup (inner diameter φ: 66 mm, cup height D: 40 mm) 20 was prepared, and FUEL C (toluene / isooctane = 50/50 wt%) was used as a test fuel. ) 100 cc. Next, the sample sheet (sample) 10 was placed on the flange portion 21 of the SUS cup 20, and was further fixed with the holding bolt 13 with the packing 12 through the wire mesh (16 mesh) 11. What was assembled in this way was turned upside down and put into a 40 ° C. oven. And the cup weight was measured every day, and the amount of decrease (permeation amount Q) was calculated. Based on this value, the transmission coefficient (mg · mm / cm ² · day) was calculated according to the following formula (1). In the evaluation, those having the above transmission coefficient of less than 25 (mg · mm / cm ² · day) were evaluated as ◯, and those having a transmission coefficient of 25 (mg · mm / cm ² · day) or more as x.

  From the above results, each of the example products was excellent in strength at break (TB) and elongation at break (EB), in addition to good hardness and flexibility, and excellent in gasoline permeability resistance. It should be noted that when H-NBR, IIR, Br-IIR, Cl-IIR is used in place of NBR which is a specific crosslinked rubber (component B), an excellent effect equivalent to that of the example product can be obtained. Confirmed by experiment. Moreover, it replaces with the alkylphenol formaldehyde resin (Taoka Chemical Industry Co., Ltd. product, Tackol 201) which is a phenol resin type crosslinking agent (D component), or brominated alkylphenol formaldehyde resin (Taoka Chemical Industry Co., Ltd. product, Tactrol 250-I), or bromine. It was confirmed by experiments that an excellent effect equivalent to that of the product of Example was obtained even when the alkylphenol formaldehyde resin (Takaki roll 250-III, manufactured by Taoka Chemical Co., Ltd.) was used.

  On the other hand, the product of Comparative Example 1 had a shorter dynamic crosslinking time than the product of Example 1, so that the average particle size of the island structure was large (1 μm) and the flexibility was inferior. Further, the product of Comparative Example 2 was inferior in flexibility because of sulfur crosslinking, and the product of Comparative Example 3 was inferior in flexibility because of peroxide crosslinking. The reason for this is not clear, but in the case of sulfur cross-linking or peroxide cross-linking, compared to the resin cross-linking using the phenol resin cross-linking agent of the example, the cross-linking speed is fast, and the island structure mainly composed of cross-linked rubber Since the particle size of is larger than that of the example product, it is assumed that the flexibility is inferior to that of the example product. The product of Comparative Example 4 was inferior in flexibility because it did not contain a non-crosslinked rubber (component C) having a functional group that reacts with an amino group in the polyamide resin (component A). The product of Comparative Example 5 was inferior in flexibility because the weight ratio of NBR (component B) was smaller than that of the polyamide resin (component A). The product of Comparative Example 6 could not be molded because it did not contain a polyamide resin (component A).

  The thermoplastic elastomer body for a fuel hose of the present invention is, for example, a fuel hose such as a transport hose for a fuel such as an automobile (gasoline, alcohol-mixed gasoline (gasohol), alcohol, hydrogen, light oil, dimethyl ether, LPG, CNG, etc.) Used for.

It is a schematic diagram which shows the dispersion state of each material in the thermoplastic elastomer body for fuel type hoses of this invention. It is explanatory drawing which shows the test method of gasoline permeation resistance (cup method).

Explanation of symbols

1 Matrix 2 Island Structure 3 Fine Particle 4 Non-crosslinked Rubber 5 Polyamide Resin

Claims (7)

A fuel system comprising the following (A) to (D) as essential components, and (B) in the thermoplastic elastomer composition in which the weight ratio of (B) is higher than that of (A) is dynamically crosslinked by (D) A thermoplastic elastomer body for a hose, wherein an island structure mainly composed of (B) and fine particles mainly composed of (C) are dispersed in a matrix composed of (A). A thermoplastic elastomer body for a fuel hose, wherein the average particle size of the structure is set in a range of 0.1 μm or more and less than 1 μm.
(A) A polyamide resin having an amino group at the terminal.
(B) At least one crosslinked rubber selected from the group consisting of acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-butadiene rubber, butyl rubber and halogenated butyl rubber.
(C) Non-crosslinked rubber having a functional group that reacts with the amino group in (A).
(D) A phenol resin-based crosslinking agent comprising at least one of a phenol resin represented by the following general formula (1) and a brominated phenol resin whose hydroxyl group is brominated.

  The thermoplastic elastomer body for a fuel system hose according to claim 1, wherein the blending amount of (D) is set in the range of 1 to 10 parts by weight with respect to 100 parts by weight of the total of (A) and (B). .   The thermoplastic fuel for a fuel system hose according to claim 1 or 2, wherein a weight mixing ratio of (A) and (B) is set in a range of (A) / (B) = 45/55 to 10/90. Elastomer body.   The non-crosslinked rubber (C) is a rubber having at least one functional group selected from the group consisting of an epoxy group, a maleic anhydride group and a carboxyl group. Thermoplastic elastomer for fuel hoses.   The blending amount of (C) is set in a range of 1 to 30 parts by weight with respect to a total of 100 parts by weight of (A) and (B). Thermoplastic elastomer for fuel hoses.   The thermoplastic elastomer body for a fuel hose according to any one of claims 1 to 5, wherein an average particle size of the fine particles containing (C) as a main component is 1 µm or less.   It is a manufacturing method of the thermoplastic elastomer body for fuel type hoses as described in any one of Claims 1-6, Comprising: Said (A) and (C) are knead | mixed, both are made to react, and (C) is a main component. (B) and (D) are mixed with this, and (B) is dynamically cross-linked by (D). A method for producing a thermoplastic elastomer body for a fuel hose, comprising:

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