JPH09112756A - Hose - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hose which has higher thermal resistance and is superior in flexibility compared with a conventional hose. SOLUTION: In a hose having at least an inner tube, a reinforcing layer, and an outer tube, a hose is formed by containing thermal plasticity resin component containing polypropylene having syndiotactic structure 10wt.% or more and elastomer component of 10-85wt.% per all polymer component weight and, when the volume rate of the thermal plasticity resin component and the viscosity in a mixed condition are set to ϕm and ηm respectively and the volume rate and viscosity of the elastomer component are set to ϕd and ηd respectively, at least, such an thermal plasticity elastomer composition as having the value of an equation α=(ϕd/ϕm)×(ηm/ηd) 1 or less is used as its outer tube.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hose using a thermoplastic elastomer composition, more particularly 100
The present invention relates to a heat resistant hose having both good heat softening resistance up to a high temperature range of ℃ or higher and flexibility applicable to complicated piping.

[0002]

2. Description of the Related Art A hose in which an inner tube, a reinforcing layer and an outer tube are laminated in this order in a tubular shape is known, and the inner tube and the outer tube are made of vulcanized rubber or resin, and the reinforcing layer is made of fiber, steel or A steel wire of stainless steel or the like or a steel wire obtained by plating them with zinc or brass or the like and braided into a blade shape or a spiral shape and subjected to an adhesion treatment such as rubbering as required has been used. However, a so-called rubber hose using rubber for the inner and outer pipes requires a vulcanization process, which complicates the manufacturing process, and a so-called resin hose using a thermoplastic resin for the inner and outer pipes has a hose that is inferior in hardness and inferior in flexibility.
There was a problem that the heat resistance was inferior due to softening under heat at temperatures above ℃. As a proposal for solving such a problem, polyolefin resin, polyvinyl chloride resin, polyamide resin,
There is a hose using a thermoplastic elastomer in which a vulcanized rubber is dispersed in a thermoplastic resin such as a polyester resin (see, for example, JP-A-6-64102). However,
For example, in recent years construction machines have been aiming to be smaller and lighter and to increase the output, so the temperature of the oil flowing in the hose for hydraulic piping will rise more and more, and it has higher heat resistance and is also applicable to complex piping. It is required to have flexibility. At present, a typical structure of a hose for hydraulic piping is exemplified by a polyamide (or polyester) elastomer inner tube / reinforcement / urethane outer tube as an example. In this case, the urethane material used for the outer tube is 120
There was a large decrease in physical properties when heated at ℃, and there was a problem in practical use when used at high temperatures. In addition, polyamide (or polyester) elastomer, which is an inner tube material, has high rigidity because of its high rigidity, and has a problem that the hose is broken (kinked) and cannot be used for complicated piping.

[0003]

SUMMARY OF THE INVENTION Therefore, the present invention eliminates the above-mentioned problems of the prior art, and has high heat resistance and heat softening performance as compared with the conventional hose and excellent flexibility, as well as a rubber hose. It is an object to provide a hose that does not require the necessary vulcanization process.

[0004]

According to the present invention, in a hose having at least an inner tube, a reinforcing layer and an outer tube, a thermoplastic resin component containing 10% by weight or more of polypropylene having a syndiotactic structure and an elastomer component are included. When the volume fraction φm of the thermoplastic resin component and the melt viscosity ηm under the mixing conditions, the volume fraction φd of the elastomer component and the melt viscosity ηd are defined as α = (φd / φm) × (ηm / ηd) There is provided a heat resistant hose using at least an outer tube of the thermoplastic elastomer composition having a value of 1 or less.

In a preferred embodiment of the present invention, as the elastomer component, ethylene / propylene / diene copolymer rubber (EPDM), acrylonitrile / butadiene copolymer rubber (NBR), hydrogenated NBR (H-NB).
R), chloroprene rubber (CR), acrylic rubber (AC
M), ethylene acrylic acid ester copolymer (AE
M), at least one elastomer selected from the group consisting of chlorosulfonated polyethylene rubber (CSM) and chlorinated polyethylene rubber (CM).

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the structure, operation and effect of the present invention will be described in detail. Syndiotactic polypropylene has been known to exist for a long time, but the conventional low temperature polymerization method using a catalyst composed of vanadium compounds and ethers and organoaluminum, a so-called Ziegler-Natta catalyst, has poor syndiotactic properties and syndiotactic polypropylene. It is hard to say that it represents the characteristics of
Furthermore, the copolymer of ethylene and propylene was hard to call crystalline polypropylene. On the other hand, J. A. According to EWEN et al., It is the first time to obtain a polypropylene having good tacticity such that the syndiotactic pentad fraction exceeds 0.7 by a catalyst composed of a transition metal catalyst component having an asymmetric ligand and an aluminoxane, a so-called methanecene catalyst. Discovered (J. Am. Chem. Soc., 110, 6255-6256, 1988).

As the catalyst suitable for synthesizing the polypropylene having the substantially syndiotactic structure to be blended in the thermoplastic elastomer composition according to the present invention, the compounds described in the above-mentioned documents can be exemplified, but the catalysts having different structures can be exemplified. However, when a propylene homopolymer was produced, the syndiotactic pentad fraction of the resulting polymer (A. Zambelll et al.
Macromolecules, 6, 687 (1973), same 8, 925 (1975))
Any catalyst system can be used as long as it gives a polymer having a relatively high tacticity of about 0.7 or more. For example, a catalyst system composed of a transition metal compound having an asymmetric ligand and an organoaluminum is effective.

Examples of suitable catalyst systems include isopropyl (cyclopentadienyl-1-fluorenyl) hafnium dichloride and isopropyl (cyclopentadienyl-1-fluorenyl) zirconium dichloride described in the above literature, Examples of the organic aluminum include aluminoxane and alkylaluminum, and examples of the aluminoxane include those in which alkylaluminum is condensed with water. Methylaluminoxane is particularly effective, and the degree of polymerization is 5 or more, preferably 10 or more. Stuff is used.

The preferable ratio of aluminoxane to the transition metal catalyst component is 10 to 1,000,000.
The molar ratio is usually 50 to 5,000. Further, a combination of an alkylaluminum and a stable anion or a compound that generates the stable anion can be used.

The polymerization conditions are not particularly limited,
A solvent polymerization method using an inert medium, a bulk polymerization method substantially free of an inert medium, and a gas phase polymerization method can also be used. The polymerization temperature is generally -100 to 200 ° C., and the polymerization pressure is generally atmospheric pressure to 100 kg / cm ² .
The pressure is preferably −100 to 100 ° C. and atmospheric pressure to 50 kg / cm ² .

In the polymerization, ethylene or an α-olefin having 4 or more carbon atoms such as butene-1, pentene-1, hexene-1, and heptene-1 is used in an amount of 10% by weight or less with respect to 90% by weight or more of propylene. It is possible to copolymerize with 4-methylpentene-1 and the like, and if it is more than 10% by weight, the characteristics of the composition such as heat distortion resistance, heat softening resistance, and moldability are unfavorable.

The syndiotactic pentad fraction of the syndiotactic polypropylene homopolymer used in the present invention is preferably 0.7 or more, particularly preferably 0.
If it is 85 or more and less than 0.7, heat distortion resistance, heat softening resistance and molding processability are poor.

The thermoplastic resin component of the thermoplastic elastomer composition according to the present invention contains 10% by weight or more, preferably 1% by weight.
It is composed of 5 to 95% by weight of polypropylene having a syndiotactic structure and another thermoplastic resin. If the content of polypropylene having a syndiotactic structure is less than 10% by weight, the thermoplastic elastomer composition lacks flexibility and heat distortion resistance, and conversely if it exceeds 95% by weight, heat distortion resistance and other desired properties are obtained. Since the control of (oil resistance, heat deterioration resistance, permeation resistance, etc.) becomes insufficient, it is preferably 95% by weight or less. In a general thermoplastic resin, heat resistance and flexibility are in a proportional relationship, and as the heat distortion temperature rises, the resin becomes more rigid, but it is synthesized by the above method. The syndiotactic polypropylene is a material having flexibility and high heat resistance and heat distortion resistance, and is the most suitable material for producing the thermoplastic elastomer composition having heat resistance of the present invention. I can say.

Examples of the other thermoplastic resin constituting the thermoplastic elastomer composition of the present invention include the following thermoplastic resins and any of these or any resin mixture containing them. The thermoplastic resin to be used preferably has a melting point of 140 ° C. or higher because the finished hose has poor heat resistance when the melting point is 140 ° C. or lower. Specifically, polyolefin resins (eg, isotactic polypropylene, ethylene propylene copolymer, high density polyethylene (HDPE), ultra high molecular weight polyethylene (UHMWPE), etc., polyamide resins (eg, nylon 6 (N6), nylon 66) (N66), nylon 46
(N46), Nylon 11 (N11), Nylon 12
(N12), nylon 610 (N610), nylon 6
12 (N612), nylon 6/66 copolymer (N6 /
66), nylon 6/66/610 copolymer (N6 / 6
6/610), nylon MXD6 (MXD6), nylon 6T, nylon 6 / 6T copolymer, nylon 66 / P
P copolymer, nylon 66 / PPS copolymer, polyester resin (eg polybutylene terephthalate (P
BT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, polyoxyalkylene diimidic acid / polybutyrate terephthalate Aromatic polyester such as copolymer), polynitrile resin (eg polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, methacrylonitrile / styrene) / Butadiene copolymer),
Polymethacrylate resin (for example, polymethyl methacrylate (PMMA), polyethyl methacrylate), polyvinyl resin (for example, vinyl acetate (EVA), polyvinyl alcohol (PVA), vinyl alcohol / ethylene copolymer (EVOH), polychlorination Vinylidene (PVD
C), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer), cellulose resin (eg cellulose acetate, cellulose acetate butyrate), fluorine resin (eg polyvinylidene fluoride) (PVDF), polyvinyl fluoride (P
VF), polychlorofluoroethylene (PCTFE),
Tetrafluoroethylene / ethylene copolymer (ETF
E)), imide resin (for example, aromatic polyimide (P
I)) etc. can be mentioned.

The elastomer component constituting the thermoplastic elastomer composition according to the present invention may be, for example, the following elastomers and any mixture of these or compositions containing these as the main components. For example, diene rubber and its hydrogenated products (for example, NR, IR,
Epoxy natural rubber, SBR, BR, (high cis BR and low cis BR), NBR, hydrogenated NBR, hydrogenated SBR),
Olefin rubber (for example, ethylene propylene rubber (E
PDM, EPM), maleic acid modified ethylene propylene rubber (M-EPM), IIR, isobutylene and aromatic vinyl or diene monomer copolymer, acrylic rubber (A
CM), ionomers), halogen-containing rubbers (eg Br
-IIR, C1-IIR, bromide of isobutylene paramelstyrene copolymer (Br-IPMS), CR, hydrin rubber (CHR), chlorosulfonated polyethylene (CMS), chlorinated polyethylene (CM), maleic acid modified chlorinated Mention may be made of one or more blends of polyethylene (M-CM)).

The elastomer component according to the present invention contains a reinforcing agent, a filler, a softening agent, an antiaging agent, a processing aid, etc. in order to improve the fluidity under heat, heat resistance, physical strength and cost of the elastomer. The necessary amount of the compounding agent usually added to the elastomer can be added.

The ratio of the thermoplastic resin component and the elastomer component constituting the thermoplastic elastomer composition according to the present invention is not particularly limited, but preferably 10 to 85% by weight of the elastomer component relative to the thermoplastic resin component, More preferably, it is 20 to 85% by weight. When the blending amount of the thermoplastic resin component is large, the rubber elasticity of the resulting thermoplastic elastomer composition is excessively impaired and the heat softening resistance is impaired. That is, the effect of the elastomer component tends not to be obtained. On the other hand, if the amount is too small, the melt flowability of the thermoplastic elastomer composition is poor, making molding processing difficult.If the amount is too small, the thermoplastic resin component as the continuous phase physically binds the elastomer component as the dispersed phase. Kneading cannot be done easily because kneading cannot be done.

When the specific thermoplastic resin and the elastomer have different compatibility, it is preferable to use a suitable compatibilizing agent as the third component to compatibilize the two. By mixing the compatibilizing agent into the system, the interfacial tension between the thermoplastic resin component and the elastomer component decreases, and as a result, the diameter of the rubber particles forming the dispersion layer becomes fine, so the characteristics of both components are It will be expressed more effectively. Such a compatibilizer is generally a thermoplastic resin component, a copolymer having both or one structure of an elastomer component, or an epoxy group, a carboxyl group, a carbonyl group capable of reacting with the thermoplastic resin component or the elastomer component. , A copolymer having a halogen group, an amino group, an oxazoline group, a hydroxyl group and the like. These may be selected depending on the types of the thermoplastic resin component and the elastomer component to be mixed, but the commonly used ones are hydrogenated products of styrene-butadiene-styrene copolymer (SE
BS) and maleic acid modified products thereof, EPDM / styrene or EPDM / acrylonitrile graft copolymers and maleic acid modified products thereof, styrene / maleic acid copolymers, and reactive phenoxine. The amount of the compatibilizer to be blended is not particularly limited, but is preferably a polymer component (sum of thermoplastic resin and elastomer) 1
0.5 to 10 parts by weight is preferable with respect to 00 parts by weight.

In the present invention, the thermoplastic elastomer composition contains 10% by weight of syndiotactic polypropylene.
The thermoplastic resin component containing the above and the above-mentioned specific elastomer component (in the case of rubber, unvulcanized product containing no vulcanizing agent) are melt-kneaded by a twin-screw kneading extruder or the like to form a continuous phase (matrix). It can be produced by dispersing an elastomer component (domain) in a thermoplastic resin. At this time, the syndiotactic polypropylene and the other thermoplastic resin may be mixed in advance with an extruder or the like, or may be blended in the form of pellets and mixed with the elastomer component. You may knead 3 components simultaneously. The elastomer component is preferably vulcanized, and in that case, it is preferable to dynamically vulcanize the elastomer component by adding a vulcanizing agent while kneading. The dynamic vulcanization conditions can be according to conventional methods. For example, sulfur-based, organic peroxide-based, metal oxide-based, phenol, quinone dioxime and the like can be used for vulcanization at a temperature of 150 ° C to 250 ° C. Vulcanization conditions (temperature, time) and the like may be appropriately determined according to the composition of the added elastomer component and are not particularly limited. As the vulcanizing agent, a general rubber vulcanizing agent (crosslinking agent) can be used. Specific examples of the sulfur-based vulcanizing agent include powdered sulfur, precipitable sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, alkylphenol disulfide, and the like. 4 phr (parts by weight per 100 parts by weight of elastomer component (polymer))
The degree may be used.

The organic peroxide-based vulcanizing agents include:
Benzoyl peroxide, t-butyl hydroperoxide, 2,4-dichlorobenzoyl peroxide,
Examples thereof include 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 2,5-dimethylhexane-2,5-di (peroxylbenzoate).
About 1 to 15 phr may be used. Further, examples of the phenolic resin-based vulcanizing agent include a bromide of an alkylphenol resin, a mixed crosslinking system containing a halogen donor such as tin chloride and chloroprene and an alkylphenol resin, and the like. Good.

In addition, zinc white (about 5 phr),
Magnesium oxide (about 4 phr), litharge (10
20 phr), p-quinone dioxime, p-dibenzoylquinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrosobenzene (2-10 phr)
Degree) and methylenedianiline (about 0.2 to 10 phr).

[0022] If necessary, a vulcanization accelerator may be added. Examples of the vulcanization accelerator include common vulcanization accelerators such as aldehyde / ammonia, guanidine, thiazole, sulfenamide, thiuram, dithioate, and thiourea, for example, 0.5 to 2 phr. The degree may be used.

Specifically, the aldehyde / ammonia-based vulcanization accelerator is hexamethylenetetramine, etc .; the guadinine-based vulcanization accelerator is diphenylguadinine, etc .; and the thiazole-based vulcanization accelerator is dibenzo. Thiazyl disulfide (DM), 2-mercaptobenzothiazole and its Zn salt, cyclohexylamine salt and the like; as the sulfenamide vulcanization accelerator, cyclohexylbenzothiazyl sulfenamide (CBS),
N-oxydiethylenebenzothiazyl-2-sulfenamide, Nt-butyl-2-benzothiazolesulfenamide, 2- (thymolpolynyldithio) benzothiazole and the like; , Tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, tetramethylthiuram monosulfide (TMTM), dipentamethylenethiuram tetrasulfide, etc .; as dithioate-based vulcanization accelerators, Zn-dimethyldithiocarbamate; Zn-
Thiourea such as diethyldithiocarbamate, Zn-di-n-butyldithiocarbamate, Zn-ethylphenyldithiocarbamate, Tc-diethyldithiocarbamate, Cu-dimethyldithiocarbamate, Fe-dimethyldithiocarbamate, pipecoline pipecolyldithiocarbamate and the like; Examples of the vulcanization accelerator include ethylenethiourea, diethylthiourea and the like;

As the vulcanization accelerating aid, general auxiliaries for rubber can be used in combination, for example, zinc white (about 5 phr), stearic acid, oleic acid and their Zn salts (2 to 5). 4 phr) or the like may be used.

Further, various compounding agents (excluding the vulcanizing agent) to the thermoplastic resin component or the elastomer component may be added during the kneading, but it is preferable to mix them in advance before the kneading. The kneader used for kneading the thermoplastic resin component and the elastomer component is not particularly limited, and examples thereof include a screw extruder, a kneader, a Banbury mixer, and a twin-screw kneading extruder. Above all, it is preferable to use a twin-screw kneading extruder for the kneading of the thermoplastic resin component and the elastomer component and the dynamic vulcanization of the elastomer component. Further, two or more kinds of kneaders may be used and kneading may be sequentially performed. As a condition for melt-kneading, the temperature may be equal to or higher than the temperature at which the thermoplastic resin component melts. The shear rate during kneading is 100.
It is preferably ⁰ to 7500 Sec ^-1 . The total kneading time is preferably 30 seconds to 10 minutes, and when a vulcanizing agent is added, the vulcanization time after the addition is preferably 15 seconds to 5 minutes. In the above method, the kneaded and produced thermoplastic elastomer composition is a usual thermoplastic resin molding method, for example,
It can be formed by injection molding, extrusion molding or the like.

By the way, in the present invention, the volume fraction of the thermoplastic resin component forming the continuous phase containing syndiotactic polypropylene is φm, and the melt viscosity during melt kneading is ηm,
On the other hand, calculate the volume fraction of the elastomer component forming the dispersed phase by φ
d, where ηd is the melt viscosity under the same conditions, α =
It is necessary to knead both [φd / φm] × [ηm / ηd] at a volume fraction such that the value is smaller than 1. This is because when the microstructure of the produced thermoplastic elastomer composition has a value of α of less than 1, the thermoplastic resin component exists as a continuous phase and the elastomer component exists as a dispersed phase. According to the method, molding can be performed, but when α is 1 or more, the relationship between the continuous phase and the dispersed phase is reversed, so that the prepared thermoplastic elastomer composition does not show the flow of the thermoplastic resin and Because it will be impossible.

In the hose of the present invention, the reinforcing layer is
There is no particular limitation. It may be formed in a blade shape or a spiral shape. Further, the material used may be a thread or a wire. As the reinforcing yarn, vinylon fiber, rayon fiber, polyester fiber,
Examples of the threads include nylon fibers and aromatic polyamide fibers. More specifically, the polyester fiber is exemplified by polyethylene terephthalate (manufactured by Toray Industries, Inc .: Tetron), which is generally suitably used. Examples of nylon fibers include nylon 6 and nylon 66 (manufactured by Asahi Kasei Corp .: Leona). Further, as the reinforcing wire, a hard steel wire is exemplified,
More specifically, a steel wire plated with brass or zinc for the purpose of preventing rust and imparting adhesiveness is exemplified.

The hose according to the present invention can be manufactured, for example, as follows. The thermoplastic elastomer composition for an inner pipe of the present invention or any resin composition as required is extruded onto a mandrel to which a release agent has been applied in advance to form a resin inner pipe. Thereafter, on the inner pipe, if necessary, an adhesive is applied or arranged in a sheet form for adhesion with a reinforcing layer or formed by a crosshead extruder, and then a reinforcing yarn or a reinforcing yarn is formed by using a braiding machine. Braiding one or more layers of reinforcing steel wire. An adhesive layer such as an adhesive may be provided between the reinforcing layers. If necessary, after braiding, an adhesive layer such as an adhesive is formed for adhesion with the outer tube, and a thermoplastic elastomer composition for the outer tube is formed thereon using a crosshead extruder suitable for extruding the composition for the outer tube. The material is extruded to form an outer tube.

As the adhesive to be placed on the inner pipe and on the reinforcing layer or between the reinforcing layers, an incyanate type adhesive, a phenol resin type adhesive, an epoxy resin type adhesive and a urethane type adhesive can be used. Adhesives are preferred.
After the inner pipe, the reinforcing layer and the outer pipe are formed in this manner, the mandrel is finally pulled out to obtain the hydraulic hose of the present invention. In this manufacturing method, a mandrel is used when manufacturing the hose, but a normal rubber hose or rubber /
Since there is no vulcanization step required when manufacturing a hose with a resin composite structure, there is no shrinkage deformation due to heat during vulcanization or deformation due to pressure during vulcanization, so the dimensional accuracy of the hose is easy to maintain. Of course, it can be manufactured without using a mandrel unless precision is strictly required.

[0030]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but it goes without saying that the technical scope of the present invention is not limited to these Examples.

Examples 1-12 and Comparative Examples 1-7 1. Synthesis of syndiotactic polypropylene Isopropyl (cyclopentadienyl-1-fluorenyl) obtained by lithiation of isopropylcyclopentadienyl-1-fluorene synthesized according to a conventional method, reaction with zirconium tetrachloride and recrystallization ) Zirconium dichloride 0.2 g and methylaluminoxane (polymerization degree 16.1) 30 manufactured by Toyo Akzo Co., Ltd.
Polymerization was carried out in an autoclave with an internal volume of 200 liters at a polymerization pressure of 3 kg / cm ² -G and 20 ° C. for 2 hours, followed by deashing with Meknol and methyl acetoacetate, washing with an aqueous hydrochloric acid solution, and then filtering As a result, 5.6 kg of syndiotactic polypropylene was obtained. This polypropylene is ¹³
According to C-NMR, the syndiotactic pentad fraction was 0.935.

2. Preparation of Elastomer Component According to the formulation of the masterbatch shown in Table I, rubber and various compounding agents were charged into an internal Banbury mixer, and
The elastomer component was prepared by mixing at 0 ° C. for 5 minutes.
Then, the elastomer component is rolled to a thickness of 2.5 with a rubber roll.
The sheet was taken out in mm, pelletized with a rubber pelletizer, and kneaded with a thermoplastic resin component using a biaxial kneading extruder.

[0033]

[Table 1]

3. Preparation of Thermoplastic Elastomer Syndiotactic polypropylene and other thermoplastic resins are dry blended, and this is used as a thermoplastic resin component in the first input port of a biaxial kneader to knead, and then the elastomer component is It was charged from the charging port of 2, added into the thermoplastic resin component, and kneaded. Then, the vulcanization system was charged from the third charging port, the kneading temperature was 230 ° C., and the shear rate was 23.
At 00S ^-1 , the mixture was kneaded and extruded in a strand form, and the strand was cooled with water and cooled, and then pelletized with a pelletizer for resin to obtain a thermoplastic elastomer composition.

4. Measurement of Physical Properties Physical properties of the obtained composition, thermoplastic resin component and elastomer component were measured by the following methods, and the results are shown in Table II. (1) Melt viscosity In advance, a small single-screw extruder was used to melt-knead syndiotactic polypropylene and other thermoplastic resin components at a ratio shown in Examples and Comparative Examples at 210 ° C. and pelletize the thermoplastic components. I saved it. Next, each thermoplastic resin component and elastomer component prepared by the above method (excluding vulcanization system)
About Capillary Rheometer Shear Rate 115
Melt viscosity was measured using an orifice of 1 mm diameter × 10 mm length at 0 s ⁻¹ and 210 ° C. temperature. Unit: Poise.

5. Preparation of Hose A polyamide elastomer (DAIAMIDO PAE / E47 (Dial Huls)) was used as the resin for the inner tube, a polyester thread was used as the reinforcing material, and the thermoplastic elastomer composition shown in Table I was used for the outer tube. Outer diameter 17.5
mm resin hose was manufactured.

6. Test of hose characteristics The following tests were performed on the hose obtained above. The results are shown in Table II. (1) Flexibility test: A hose is bent along an arc having a predetermined radius and the bending force is measured. The bending radius is measured from 10 times (10D) the outer diameter of the hose, and the bending force is sequentially measured up to 3 times (n = 2). The numerical value at the specified radius (4 times) is read from the curve obtained by plotting the relationship between the bending force and the bending radius obtained as a result. The flexibility of the hose should be 4kgf or less. (2) Heat resistance test: Metal fittings are attached to both sides of a 300 mm long hose, and oil is sealed to make a sealed state. This hose 12
It was put in a 0 ° C. oven for 3 days, and then taken out and the leakage of oil from the metal fitting and the appearance were observed. ◯: No oil leakage appearance abnormality. (3) Impulse test: The test was performed according to SAE J188 Type 1. (Oil: Auto multi oil (Idemitsu), 120 ° C) ○: At pressure of 210 kgf / cm ² , impulses of 1,000,000 times were given, and there were no abnormalities such as metal fittings missing or body breakage.

Example 12 The resin for the outer tube of Example 10 was used as the resin for the inner tube,
For the outer tube, using the thermoplastic elastomer composition having the composition shown in Table II, resin hoses were prepared in the same manner as in Examples 1 to 11, and the same tests as above were carried out. The results are shown in Table II.

The compounding agents used in the examples and comparative examples of the present invention are as follows. ZnO: Zinc Hua No. 3 (Shodo Kagaku) Sulfur: Powdered Sulfur (Karuizawa Smelter) Trimercaptotriazine: ZISNET-F (Sankyo Kasei) DM: Noxceller DM (Ouchi Emerging Chemicals) MDCA: 2 Mercaptobenzothiazole Dicyclohexylamine salt (Ouchi Shinko Chemical Co., Ltd.) Zn St: Zinc stearate (Jodo Chemical) Butanetetracarboxylic acid: BTC (Mitsui Toatsu Fine) NA22: Sunmix 22-80E (Sanshin Chemical Co., Ltd.) N11: Nylon 11 (Rilsan) BESNO TL (Atochem) N6: Nylon 6 (CM1010) (Toray) Isotactic PP (MJ170) (Tokuyama) LDPE (SHOREX M171) (Showa Denko)

[0040]

[Table 2]

[0041]

[Table 3]

[0042]

[Table 4]

In Examples 1 to 11 and Comparative Examples 1 to 7, the inner tube and the reinforcing material were the same, and it was evaluated how the hose characteristics were changed by changing the material of the outer tube. When the product of the volume ratio and the viscosity ratio of the thermoplastic resin component and the elastomer component and α exceeds 1,
Since the phase structure of the thermoplastic elastomer produced is reversed and the elastomer component becomes a matrix,
During the dynamic addition of the vulcanization system, so-called "burning" occurs, in which the elastomer component is vulcanized (crosslinked), kneading becomes impossible, and the outer tube material cannot be produced. On the other hand, even if α is 1 or less, if the thermoplastic resin component exceeds 90% by weight (Comparative Example 1), the flexibility of the hose is poor, which is not preferable. Regarding the thermoplastic resin component and the elastomer component other than syndiotactic polypropylene, within the scope of the present invention, the type has no selectivity, and a thermoplastic elastomer composition can be constituted, and (vulcanization of Examples 5 to 11) thereof. As the system, it is sufficient to use one that matches the elastomer component.
Nylon 6 and isotactic P as thermoplastic components
The thermoplastic elastomers (Comparative Examples 4 and 5) prepared by using only a material having high heat resistance and a high Young's modulus such as P have insufficient flexibility, and are not flexible as LDPE as the thermoplastic resin. Although a thermoplastic elastomer (Comparative Example 6) produced by using a resin having a low heat resistance or a hose (Comparative Example 7) using polyurethane as an outer tube has high flexibility but lacks heat resistance. It is difficult to use as a heat resistant hose. Furthermore, when a similar hose is made by using the thermoplastic elastomer composition used in the outer tube of Example 10 for the inner tube as in Example 12, a hose that is more flexible than the hose made of the polyamide elastomer inner tube. Becomes

[0044]

As shown in the results of Table II, according to the present invention, by kneading the thermoplastic resin component containing 10% by weight or more of syndiotactic polypropylene and the elastomer component, high heat resistance and flexibility are obtained. A hose having excellent properties can be obtained.

Continuation of front page (72) Inventor Daisuke Irai, 2-1, Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber Co., Ltd. Hiratsuka Factory

Claims (3)

[Claims] 1. A hose having at least an inner tube, a reinforcing layer and an outer tube, which comprises a thermoplastic resin component containing 10% by weight or more of polypropylene having a syndiotactic structure and an elastomer component. Thermoplastic elastomer composition in which the value of α = (φd / φm) × (ηm / ηd) is 1 or less, where volume fraction φm and melt viscosity ηm under mixing conditions, volume fraction φd of elastomer component and melt viscosity ηd A heat-resistant hose with at least its outer tube. 2. The elastomer component is ethylene / propylene / diene copolymer rubber (EPDM), acrylonitrile / butadiene copolymer rubber (NBR), hydrogenated NBR.
(H-NBR), chloroprene rubber (CR), acrylic rubber (ACM), ethylene acrylate copolymer (AEM), chlorosulfonated polyethylene rubber (CS)
The hose according to claim 1, comprising at least one elastomer selected from the group consisting of M) and chlorinated polyethylene rubber (CM). 3. The hose according to claim 1, wherein the thermoplastic resin has a melting point of 140 ° C. or higher.