JPH1052887A - Laminate of olefin thermoplastic elastomer composition layer and fiber-reinforced layer and hose using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve interlayer adhesive properties of a laminate of a layer of composition of thermoplastic elastomer containing polyolefin thermoplastic resin and a fiber-reinforced layer. SOLUTION: The elastomer is obtained by interposing at least one type of thermoplastic adhesive resin selected from the group consisting of maleic anhydride modified polyolefin resin, epoxy modified polyolefin resin and polyester resin between a layer of thermoplastic elastomer composition obtained by mixing at least partly crosslinked elastomer component with polyolefin thermoplastic resin and a fiber-reinforced layer, and adhesively integrating it by hot melting.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a maleic anhydride-modified layer between a layer of a thermoplastic elastomer composition comprising a polyolefin-based thermoplastic resin and an elastomer component at least partially cross-linked, and a fiber reinforcing layer. The present invention relates to a laminated body excellent in adhesion formed by interposing at least one kind of thermoplastic adhesive resin selected from a polyolefin resin, an epoxy-modified polyolefin resin and a polyester-based resin by heat fusion, and a hose using the same.

[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. In these hoses, the inner tube and the outer tube are made of vulcanized rubber, urethane, polyester or nylon. The reinforcing layer is braided with braided fibers such as nylon, polyester, rayon, vinylon, and aramid fibers in a braided or spiral shape, and each layer is bonded using a rubber cement or urethane-based adhesive. Have been.

[0003]

However, a so-called rubber hose using rubber for the inner and outer tubes requires a vulcanization step, which complicates the manufacturing process, and a so-called resin hose using only a thermoplastic resin for the inner and outer tubes is difficult. However, there is a problem that the hose is hard and inferior in flexibility, and a kink phenomenon occurs when the hose is bent. As a proposal to solve this problem,
Thermoplastics in which a vulcanized rubber phase, at least a part of which is crosslinked, is dispersed in a thermoplastic resin such as a polyolefin-based thermoplastic resin, a polyvinyl chloride-based thermoplastic resin, a polyamide-based thermoplastic resin, or a polyester-based thermoplastic resin. A hose using an elastomer composition has been proposed (for example, see JP-A-6-64102).

[0004] Among these thermoplastic elastomer compositions, a thermoplastic elastomer composition comprising a polyolefin-based thermoplastic resin mixed with an elastomer component having at least a part thereof crosslinked is highly flexible and has a high flexibility. And a material suitable for the outer tube. However, good adhesion to both a fiber reinforcing layer composed of fibers such as polyester, nylon, rayon and the like and a thermoplastic elastomer composition comprising a polyolefin-based thermoplastic resin and an elastomer component at least a part of which is crosslinked. Adhesives exhibiting properties have not yet been developed.

For example, surface activation techniques such as corona discharge machining, ultraviolet irradiation, flame treatment, and strong acid treatment are known as methods for improving the adhesion of a polyolefin-based thermoplastic resin which is a main component of the thermoplastic elastomer composition. I have. However, in these methods, it is not only difficult to secure the adhesion level required for a durable product such as a hose made of the thermoplastic elastomer composition, but also these surface treatment methods are applied to a hose production line. This not only makes the process extremely complicated, but also makes it extremely expensive and not practical. Therefore, an object of the present invention is to eliminate the above-mentioned problems of the prior art and to blend the thermoplastic elastomer composition comprising a polyolefin-based thermoplastic resin and an elastomer component at least a part of which is crosslinked, and a fiber reinforcing layer. It is an object of the present invention to provide a laminate using a thermoplastic adhesive resin showing good adhesion to any of the above, and a hose using the same.

[0006]

According to the present invention, there is provided a resin composition comprising a layer of a thermoplastic elastomer composition comprising a polyolefin-based thermoplastic resin and an elastomer component having at least a part thereof crosslinked, and a fiber reinforcing layer. A laminated body excellent in adhesion formed by bonding at least one thermoplastic adhesive resin selected from a maleic anhydride-modified polyolefin resin, an epoxy-modified polyolefin resin and a polyester-based resin to form a bonded body by means of heat fusion, and The used hose is provided.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention uses a thermoplastic adhesive resin such as a modified polyolefin-based resin or a polyester-based resin and blends an elastomer component at least partially cross-linked to a polyolefin-based thermoplastic resin. It has succeeded in obtaining a laminate of a layer of a thermoplastic elastomer composition and a fiber reinforced layer.
The thermoplastic adhesive resin is interposed between the fiber reinforcing layers, between the fiber reinforcing layers or between the fiber reinforcing layer and the outer tube, and fusion bonding is performed under a thermal reaction, and high adhesion can be obtained between any of the above layers. As a result, the durability of the hose can be significantly improved. Further, it becomes possible to adhere a thermoplastic elastomer composition obtained by blending at least a part of a crosslinked elastomer component to a polyolefin-based thermoplastic resin which is a hardly-adhesive material.

In the present invention, maleic anhydride or epoxy-modified polyolefin resin or polyester resin is used as the thermoplastic adhesive resin. Examples of the polyolefin resin modified here include polypropylene resins such as isotactic, syndiotactic, and random or block copolymers with ethylene or the like (P
P), high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LL)
DPE) or a general polyolefin-based resin such as ethylene-ethyl acrylate copolymer (EEA) or ethylene-methyl acrylate copolymer (EMA).

The method for modifying these polyolefin-based resins with maleic anhydride or epoxy is not particularly limited, and is performed by a conventionally known method. For example, a maleic anhydride-modified polypropylene resin is prepared by a single screw extruder. Alternatively, it can be obtained by adding 1% by weight of maleic anhydride and 0.05% by weight of peroxide to polypropylene and kneading the mixture using a twin-screw kneading extruder, followed by a grafting reaction.
The polyester resin used here is obtained by polycondensation of a polyhydric alcohol and a polycarboxylic acid, and other copolymer components mainly containing terephthalic acid and 1,4-butanediol. For example, a polyester resin into which a carboxylic acid such as isophthalic acid, adipic acid or sebacic acid or a polyhydric alcohol such as ethylene glycol has been introduced can be preferably used. Furthermore, polyester-based block copolymer elastomers using these polyester-based resins as hard segments and polycaprolactam, polytetramethylene glycol or the like as soft segments may be used, and are preferably used. Further, as the thermoplastic adhesive resin, a blend resin of a maleic anhydride-modified polyolefin resin and / or an epoxy-modified polyolefin resin and a polyester resin can be more preferably used. The weight ratio of the blend resin may be within a range in which the effect as the blend resin is exhibited, but the weight ratio of the maleic anhydride-modified polyolefin resin and the epoxy-modified polyolefin resin is 9%.
A ratio of 5/5 to 5/95 is preferred. Furthermore, blends of a maleic anhydride-modified polyolefin resin and / or an epoxy-modified polyolefin resin and a polyester resin may require improvement in physical properties in terms of compatibility. In this case, the maleic anhydride-modified polyolefin resin and the epoxy resin may be used. A blend resin of a modified polyolefin resin and a polyester resin can be preferably used from the viewpoint of improving physical properties. In particular, one of the maleic anhydride-modified polyolefin resin or the epoxy-modified polyolefin resin is a modified resin of a polypropylene resin or a polyethylene resin, and the other is a modified resin of an ethylene-acrylate copolymer. In that respect, that is, one of them can be preferably used because it functions as a so-called compatibilizer.

Further, in order to obtain more preferable adhesion in the present invention, the maleic anhydride-modified polyolefin resin or the epoxy-modified polyolefin resin may have 230
° C, load 2.16 kgf, orifice diameter 1 mm, and melt index measured under the conditions of 10 minutes: 5.0 g /
It is preferably a modified resin of a polypropylene resin for 10 minutes or less, and more preferably a melt index of 3 to 0.5 g / 10 minutes. Further, in the maleic anhydride-modified polyolefin resin or the epoxy-modified polyolefin resin, a polyethylene resin having a melt index of 5.0 g / 10 minutes or less measured at 190 ° C., a load of 2.16 kgf, an orifice diameter of 1 mm, and 10 minutes is used. It is preferably a modified resin having a melt index of 3
More preferably, it is 0.1 g / 10 min.

In order to obtain more preferable adhesion in the present invention, the maleic anhydride-modified polyolefin resin or the epoxy-modified polyolefin resin may have
C., a load of 2.16 kgf, an orifice diameter of 1 mm, and a melt index of 6.0 g / measurement for 10 minutes.
It is preferably a modified resin of an ethylene / acrylate copolymer for 10 minutes or more, and more preferably the melt index is in the range of 9.0 to 20.0 g / 10 minutes. In order to obtain more preferable adhesion in the present invention, the polyester resin has a melt index of 20.0 g / 10 measured at 190 ° C., a load of 2.16 kgf, an orifice diameter of 1 mm, and 10 minutes.
Minutes or less, and more preferably a melt index of 15 g / 10 minutes or less.

In the present invention, a heat is obtained by blending an elastomer component, at least a part of which is crosslinked, with a polyolefin-based thermoplastic resin used as, for example, an inner tube and / or an outer tube of a hose used as a layer to be bonded. As the plastic elastomer composition, for example, a composition obtained by blending a component obtained by crosslinking at least a part of an elastomer component of the following type with a polyolefin-based thermoplastic resin such as polypropylene, polyethylene, and ethylene / vinyl acetate copolymer is used. .

That is, as the elastomer of the elastomer component, for example, a diene rubber or a hydrogenated product thereof (eg, NR, IR, epoxidized natural rubber, SBR, BR)
(High cis BR, low cis BR), NBR, hydrogenated NBR,
Hydrogenated SBR) or olefin rubber (eg, ethylene propylene rubber (EPDM, EPM), maleic acid-modified ethylene propylene rubber (M-EPM), IIR, isobutylene and aromatic vinyl or diene monomer copolymer, acrylic rubber (ACM ), Ionomers) and halogen-containing rubbers (e.g., Br-IIR, Cl-IIR,
Brominated isobutylene and p-methylstyrene copolymer (Br-IPMS), CR, hydrin rubber (CHC, C
HR), chlorosulfonated polyethylene (CSM), chlorinated polyethylene (CM), maleic acid-modified chlorinated polyethylene (M-CM), and the like, or a mixture thereof.

In addition to the above-mentioned elastomers, the above-mentioned elastomer components include reinforcing agents, fillers, softeners, aging agents for improving the fluidity, heat resistance, physical strength and cost of the elastomers when heated. Any necessary compounding agent such as an inhibitor and a processing aid which is added to a usual elastomer can be added in a required amount.

The ratio of the thermoplastic resin component to the elastomer component constituting the thermoplastic elastomer composition according to the present invention is not particularly limited, but preferably, the ratio of the elastomer component to the thermoplastic resin is 10%. ~ 90% by weight. When the blending amount of the thermoplastic resin is large, the rubber elasticity of the obtained thermoplastic elastomer composition is reduced, and the heat softening resistance is also reduced. Conversely, if the amount is too small, the melt fluidity of the thermoplastic elastomer composition decreases, and molding and processing become difficult.If the amount is too small, the thermoplastic resin component as a continuous phase physically removes the elastomer component as a dispersed phase. There is a tendency for kneading to be difficult because it cannot be covered.

The elastomer component in the thermoplastic elastomer composition according to the present invention is at least partially crosslinked. The crosslinking of the elastomer component is carried out by melt-kneading the thermoplastic resin and the elastomer component containing no crosslinking agent by a twin-screw kneading extruder or the like, and dispersing the elastomer component in the thermoplastic resin forming a continuous phase (matrix). It is preferable to perform a dynamic cross-linking by adding and kneading a cross-linking agent for cross-linking the elastomer component while dispersing as ()). The dynamic cross-linking is not limited to the above-mentioned method, and any conventional method can be used. For example, sulfur-based, organic peroxide-based, metal oxide-based, phenolic resin, quinone dioxime, etc. ° C
It can be crosslinked at ~ 300 ° C.

The conditions for crosslinking (temperature, time, etc.) may be appropriately determined according to the composition of the elastomer component to be added.
There is no particular limitation. As the cross-linking agent, the above-mentioned ones are used, and more specifically, as a sulfur-based cross-linking agent, powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, alkylphenol disulfide, etc. Is exemplified. The addition amount may be, for example, about 0.5 to 4 parts by weight based on 100 parts by weight of the elastomer. Examples of the organic peroxide crosslinking agent include benzoyl peroxide, t-butyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-dimethyl-di (t-butylperoxy) hexane, , 5-dimethylhexane-2,5-di (peroxyl benzoate) and the like. For example, about 1 to 15 parts by weight based on 100 parts by weight of the elastomer may be used. Examples of the phenolic resin-based cross-linking agent include brominated alkylphenol resins and mixed cross-linking systems containing a halogen donor such as tin chloride and chloroprene and an alkylphenol resin. Good.

Others include zinc white (about 5 parts by weight),
Magnesium oxide (about 4 parts by weight), resir (10 to 10 parts by weight)
About 20 parts by weight), p-quinone oxime, p-dibenzoylquinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrobenzene (about 2 to 10 parts by weight), methylene dianiline (0.2 to 10 parts by weight). Parts by weight)
Is exemplified. If necessary, a crosslinking accelerator may be added. Aldehyde-based, ammonia-based,
General substances such as guanidine, thiazole, sulfenamide, thiuram, dithioate, and thiourea may be added, for example, in an amount of about 0.5 to 2 parts by weight. Further, a general cross-linking accelerator may be added. The various additives (excluding the crosslinking agent) to the thermoplastic resin or the elastomer may be added during the kneading or may be mixed before the kneading.

In the present invention, as the kneader used for kneading the thermoplastic resin and the elastomer component, the above-described twin-screw kneading extruder is more preferable for dynamic crosslinking, but a screw extruder, a kneader, a Banbury mixer and the like can be used. And may be used for kneading. Moreover, you may knead sequentially using two or more types of kneaders.

As conditions for the above-mentioned melt-kneading, the temperature may be at least the temperature at which the thermoplastic resin is melted, and the shear rate during kneading is preferably 1000 to 7500 sec ^-1 .
The kneading time is preferably from 30 seconds to 10 minutes, and when a crosslinking agent is added, the crosslinking time after addition is preferably from 15 seconds to 5 minutes. Thermoplastic elastomer composition kneaded by the above method, a normal thermoplastic resin molding method, for example,
It can be formed by injection molding, extrusion molding or the like.

The fiber reinforcing layer which is another layer to be bonded in the present invention is not particularly limited. Organic fibers such as nylon, vinylon, rayon, polyester, and aramid fibers are preferably used as the reinforcing fibers. Further, in the hose according to the present invention, the fiber reinforcing layer may be formed by braiding in a braided shape or a spiral shape, or may be formed by cutting a fiber woven fabric into a tape shape and winding it in a spiral shape. It may be a fiber reinforced layer, and its form is not particularly limited.

Further, the structure of the hose according to the present invention is not particularly limited, but at least one of the inner tube and the outer tube is blended with an elastomer component at least a part of which is crosslinked with a polyolefin thermoplastic resin. A thermoplastic elastomer composition is used. Also,
At least one fiber reinforcing layer is disposed between the inner pipe and the outer pipe. Further, the thermoplastic adhesive resin of the present invention may be disposed between a fiber reinforcing layer and a thermoplastic elastomer composition obtained by blending at least a part of an elastomer component which is at least partially cross-linked to a polyolefin-based thermoplastic resin. is necessary. If this is not the case, the adhesion between the thermoplastic elastomer composition and the fiber reinforcing layer will be insufficient, resulting in a significant loss of hose durability. When the hose of the present invention has two or more fiber reinforced layers, it is more preferable to dispose the thermoplastic adhesive resin according to the present invention between the fiber reinforced layers from the viewpoint of the withstand pressure of the hose. In the hose of the present invention, a thermoplastic elastomer composition other than the present invention or another resin can be disposed on either the inner tube or the outer tube as necessary. In this case, the bonding between the fiber reinforcing layer and these other thermoplastic elastomer compositions and other resin layers is performed by using an isocyanate-based, phenolic-based, epoxy-based, or urethane besides the thermoplastic adhesive resin of the present invention. A system adhesive can be used.

The hose according to the present invention can be manufactured, for example, as follows. That is, a thermoplastic elastomer composition for an inner tube or a thermoplastic resin as required is extruded onto a mandrel to which a mold release agent has been previously applied to form an inner tube. Thereafter, an adhesive layer is formed on the inner tube. When the thermoplastic adhesive resin of the present invention is used, it is possible to form an adhesive layer by performing melt extrusion simultaneously with the inner tube.
Further, a fiber reinforcing layer is formed thereon. The fiber reinforcing layer may be formed by the above method. When there are a plurality of fiber reinforcing layers, an adhesive layer is formed between the reinforcing layers as necessary. Further, an adhesive layer is formed thereon, and the outer tube is formed by extrusion similarly to the inner tube. In the case of the method of forming the thermoplastic adhesive resin of the present invention between the fiber reinforcement layer and the outer tube, the thermoplastic resin or the thermoplastic elastomer composition forming the thermoplastic adhesive resin and the outer tube is simultaneously melt-extruded. May be. The desired hose can be obtained by removing the mandrel after forming the hose in this way.

Although a mandrel is used in the above-described method of manufacturing a hose, the hose of the present invention does not require a vulcanization step for crosslinking rubber as in a normal rubber hose or a rubber / resin composite structure hose. Since there is no need for shrinkage deformation due to heat during heating or deformation due to pressure applied during heating, it is easy to maintain the dimensional accuracy of the hose, so use a mandrel unless strict dimensional accuracy is required. Needless to say, it can be manufactured without using any other method.

[0025]

EXAMPLES The present invention will be further described with reference to the following examples, but it goes without saying that the scope of the present invention is not limited to these examples.

1. Preparation of Thermoplastic Adhesive Resin As shown in Table I, thermoplastic adhesive resins Nos. 1-22 were obtained according to a conventional method. For the modification of the resin, maleic anhydride or an epoxy compound (glycidyl methacrylate) was used.

[0027]

[Table 1]

Adhesive resin No. Nos. 1-3 are polypropylene modified with maleic anhydride, and the adhesive resin N
o. Nos. 4 to 6 are obtained by modifying high-density polyethylene with maleic anhydride. Adhesive resin No. Nos. 7 to 9 were obtained by modifying linear low-density polyethylene with maleic anhydride. Nos. 10 to 12 are low-density polyethylenes modified with maleic anhydride. Nos. 13 to 15 are those modified with maleic anhydride with an ethylene / ethyl acrylate copolymer. Adhesive resin No. Nos. 16 to 18 are epoxy-modified ethylene / ethyl acrylate copolymers. Adhesive resin No.
Nos. 19 to 22 are copolymerized polyester resins. 22 is a block copolymerized polyester resin.

Examples 1 to 22 and Comparative Example 1 As shown in Table I, the thermoplastic adhesive resin No. 1
Polyester fiber woven fabric (vertical yarn 1000)
d, a weft 1000d, a density of 50 × 50 fibers / 5cm plain woven fabric) and a thermoplastic elastomer composition (polypropylene-based thermoplastic resin, PP, blended with EPDM rubber as an elastomer component as a dispersed phase in a crosslinked state) A thermoplastic elastomer composition having a weight ratio of PP / EPDM rubber composition of 45/55,
P was composed of RB121D manufactured by Tokuyama Corporation, and EPDM was composed of EPT4070 manufactured by Mitsui Petrochemical Co., Ltd.). EPDM rubber composition is EPDM100
Parts by weight are composed of 60 parts by weight of HAF carbon black, 20 parts by weight of paraffinic oil, 5 parts by weight of zinc white, and 1 part by weight of stearic acid. In addition, PP and EPD
As a dynamic vulcanizing system during biaxial kneading of the M composition, 0.5 parts by weight of sulfur, 1 part by weight of a vulcanization accelerator BZ (zinc di-n-butyldithiocarbamate) per 100 parts by weight of a rubber polymer, 0.5 parts by weight of a vulcanization accelerator TRA (dipentamethylenethiuram tetrasulfide), 0.5 parts by weight of a vulcanization accelerator TT (tetramethylthiuram disulfide), CZ (N-cyclohexyl-2-vulcanization accelerator) 1 part by weight of benzothiazyl sulfenamide) was added and dynamically vulcanized to prepare a thermoplastic elastomer composition. Adhesive test piece sandwiches thermoplastic adhesive resin sheet between polyester fabric and sheet of thermoplastic elastomer composition, 230 ° C
After pressurizing at 10 kgf / cm2 for 2 minutes and cooling to room temperature, it was cut into strips having a width of 25 mm, and the peel adhesion strength was measured as a peel test piece. The results are shown in Table I.

[0030]

[Table 2]

As a comparative example, a commercially available adhesive, a moisture-curable urethane-based adhesive (trade name: Tyrite 7411, manufactured by Lord Far East Co., Ltd.) was used. In this case, the adhesive was applied to both the polyester fiber woven fabric and the sheet of the thermoplastic elastomer composition, and then the two were laminated and moisture-cured for one week before the test. Using this test piece, the peel adhesion was measured in the same manner as in the example. The results are shown in Table I. The peel adhesion test was measured at room temperature (25 ° C.) and in an atmosphere at 100 ° C.

From the results in Table I, it can be seen that the urethane-based adhesive, which is a known adhesive of the comparative example, easily breaks at the interface on the thermoplastic elastomer side, and hardly obtains an adhesive strength. On the other hand, it can be seen that when the thermoplastic adhesive resin of the present invention is used, the adhesive strength is clearly improved as compared with the conventional urethane-based adhesive.

In the thermoplastic adhesive resin of the present invention, the modified polypropylene resin (Examples 1 to 3) was measured at 230 ° C., a load of 2.16 kgf, an orifice diameter of 1 mm, and 10 minutes. Those having a melt index of 5.0 g / 10 minutes or less, especially at 100 ° C.
It can be seen that the adhesive strength in a high-temperature atmosphere is more preferable. In the thermoplastic adhesive resin of the present invention, the modified resin of the polyethylene resin (Examples 4 to 1)
2) Those having a melt index of 5.0 g / 10 minutes or less measured at 190 ° C., a load of 2.16 kgf, an orifice diameter of 1 mm, and 10 minutes have high adhesive strength especially in a high-temperature atmosphere at 100 ° C. It turns out that it is more preferable. Further, from Examples 13 to 18, in the modified resin of the ethylene / acrylate copolymer, at 190 ° C.,
The melt index measured under the conditions of a load of 2.16 kgf, an orifice diameter of 1 mm, and 10 minutes is 6.0 g / 10.
It can be seen that more than a minute gives more favorable adhesion. Further, from Examples 19 to 22, the polyester resin gives a more preferable adhesion at a melt index of 20.0 g / 10 minutes or less measured at 190 ° C., a load of 2.16 kgf, an orifice diameter of 1 mm, and a measurement condition of 10 minutes. You can see that.

Examples 23-36 As further shown in Table II, the thermoplastic adhesive resin N obtained above
o. Using 1,19 and 22, and an epoxy-modified ethylene methyl acrylate (EMA) as a compatibilizer, the effect of a blend system of a modified polyolefin-based resin and a polyester-based resin was confirmed. As in the previous example, the polyester fiber woven fabric and the thermoplastic elastomer composition (PP /
(EPDM-based thermoplastic elastomer composition). The adhesive test piece is sandwiched between a sheet of polyester fabric and a sheet of the thermoplastic elastomer composition, pressed at 230 ° C. for 2 minutes at 10 kgf / cm ² , cooled to room temperature, and cut into strips of 25 mm width. The peel adhesion strength was measured as a peel test piece. The results are shown in Table II. The peel adhesion test was performed at room temperature (2
5 ° C) and 100 ° C. It can be seen that particularly when the blend adhesive resin of the modified polyolefin resin and the polyester resin, which is the thermoplastic adhesive resin of the present invention, is used, the adhesive strength at 100 ° C. is particularly excellent.

Examples 37 to 85, Comparative Examples 2 to 3 and Reference
Using a thermoplastic adhesive resin 1 to 36 of Reference Example Tables I and table II,
A hose having a structure shown in Table II was manufactured, and a breaking pressure and a durability test of the obtained hose were performed. The structure of this hose is a thermoplastic elastomer composition in which an acrylic rubber (ACM) partially crosslinked with a copolyester thermoplastic resin (COPE) is dispersed as a disperse phase in an inner tube (COPE is Hytrel manufactured by Toray Industries, ACM is Japan Using Zeon AR997 7
The reinforcing layer is formed by braiding polyester fibers (1500d / 4) into a braided shape and arranging two layers. Further, as the outer tube, a polypropylene, which is the polyolefin-based thermoplastic resin of the present invention, is used. A thermoplastic elastomer composition (PP / EPDM) in which EPDM rubber as an elastomer component is blended as a dispersed phase in a crosslinked state.
The composition weight ratio is 45/55, PP is Tokuyama PB
121D, EPDM is EPT407 manufactured by Mitsui Petrochemical Co., Ltd.
0) in the same manner as described above. The test results for these hoses are also shown in Table III. Further, in Comparative Example 2, between the inner tube and the outer tube, and in Comparative Example 3, between the inner tube, the fiber reinforced layer, and the outer tube, a moisture-curable urethane which is an ordinary commercially available adhesive is used. System adhesive (trade name Tyrite 7411 manufactured by Road Far East Co., Ltd.)
Is used. The results are shown in Table III. further,
A general resin hose generally used as a reference example was manufactured at the same time and subjected to a test.

[0036]

[Table 3]

[0037]

[Table 4]

[0038]

[Table 5]

[0039]

[Table 6]

[0040]

[Table 7]

[0041]

[Table 8]

[0042]

[Table 9]

[0043]

[Table 10]

The hose destruction test was performed according to JIS K6349.
Was measured at 100 ° C. in accordance with the pressure resistance test (destructive test). The durability test was performed in accordance with SAE J188 Type 1. Oil is auto mulch oil and temperature 1
One million times of repetitive impact pressure was applied at 20 ° C. and pressure of 210 kgf / cm 2, and after the completion, the damage condition of the hose fitting mounting portion and the main body was confirmed. In addition, durability was evaluated by the number of repeated impacts that led to the destruction of those that did not reach 1,000,000 times.

From Table III, it can be seen that Comparative Example 2 is inferior in the adhesiveness between the outer tube and the fiber reinforcing layer, so that the hose breaking pressure and the durability are inferior to those of ordinary resin hoses. on the other hand,
It can be seen that the examples of the present invention clearly show superior performance in both hose breaking pressure and durability than Comparative Examples 2 and 3. Further, from Examples 37 to 41, in the thermoplastic adhesive resin of the present invention, the modified resin of the polypropylene resin has a temperature of 230 ° C., a load of 2.16 kgf,
It can be seen that those having an orifice diameter of 1 mm and a melt index of 5.0 g / 10 minutes or less measured under the measurement conditions of 10 minutes are more preferable in terms of hose durability. Further, from Examples 42 to 56, in the thermoplastic adhesive resin of the present invention, the modified resin of polyethylene resin
The melt index measured under the conditions of 0 ° C., a load of 2.16 kgf, an orifice diameter of 1 mm and 10 minutes is 5.0 g.
It can be seen that a sample having a length of / 10 minutes or less is more preferable in terms of hose durability. Also, from Examples 57 to 66, ethylene
In the modified resin of the acrylate copolymer,
190 ° C, load 2.16kgf, orifice diameter 1mm and 1
5. Melt index measured under 0 minute measurement condition is 6.
It can be seen that 0 g / 10 min or more gives more preferable hose durability.

Further, from the results of Examples 67 to 71, in the case of the polyester resin, at 190 ° C. under a load of 2.16.
It can be seen that a hose with a melt index of 20.0 g / 10 minutes or less measured under the conditions of kgf, an orifice diameter of 1 mm, and 10 minutes gives more preferable hose durability.

When the urethane adhesive is interposed between the fiber reinforced layers in Comparative Example 3 when there are two fiber reinforced layers, and the fiber caused by the impregnation and curing of the adhesive into the fiber reinforced layer is obtained. Although the breaking pressure and durability of the hose deteriorated due to fatigue, the breaking pressure of the hose was further increased by interposing the thermoplastic adhesive resin of the present invention between the fiber reinforcing layers. Example 39, Example 4
Example 2 and Example 44, Example 47 and Example 49, Example 52
It can be seen from the comparison of Example 54 with Example 54, Example 57 and Example 59, Example 62 and Example 64, and Example 67 and Example 69.

Further, the use of the thermoplastic adhesive resin of the present invention on the inner tube side instead of the urethane-based adhesive further increases the breaking pressure of the hose.
Example 44 and Example 45, Example 49 and Example 50, Example 54 and Example 55, Example 59 and Example 60, Example 64 and Example 65, Example 69 and Example 70, respectively It can be seen from the comparison.

Examples 72 to 85 are hoses in which the adhesive resin which is a blend of the modified polyolefin resin and the polyester resin of the present invention is interposed between the outer tube and the fiber reinforcing layer. The results of Examples 72 to 77 show that when the ratio of maleic anhydride-modified PP to the copolymerized polyester resin is in the range of 95/5 to 5/95, both the breaking pressure and the durability of the hose are excellent. Examples 78-81 are
It can be seen that the use of an adhesive resin to which epoxy-modified EMA was added as a compatibilizer further improved the breaking pressure of the hose. In Examples 82 to 85, a block copolymerized polyester resin was used as the polyester resin, and an adhesive resin to which epoxy-modified EMA was added as a compatibilizer was used. It can be seen that the breaking pressure of the hose was further improved.

[0050]

As described above, according to the present invention,
Hose inner tube / fiber reinforced layer, fiber reinforced layer / fiber reinforced layer,
By using the thermoplastic adhesive resin between any of the fiber reinforcing layer and the outer tube, a desired high adhesive strength is obtained, and the hose durability is improved. In addition, by being able to use thermal reactions,
It is possible to adhere a thermoplastic elastomer composition obtained by blending an elastomer component obtained by at least partially cross-linking a polyolefin-based thermoplastic resin which is a hardly-adhesive material.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location B32B 27/36 B32B 27/36 F16L 11/04 F16L 11/04 (72) Inventor Osamu Ozawa Kanagawa 2-1 Oitai, Hiratsuka-shi Yokohama Rubber Co., Ltd. Hiratsuka Factory (72) Inventor Katsuhiro Tanaka 2-1 Oiwake, Hiratsuka-shi, Kanagawa Yokohama Rubber Co., Ltd. Hiratsuka Factory (72) Inventor Yoshihiro Soeda Hiratsuka, Kanagawa Prefecture No.2-1 Oiwake Yokohama Rubber Co., Ltd. Hiratsuka Factory (72) Inventor Takashi Sato No.2-1 Oiwake Hiratsuka-shi, Kanagawa Prefecture Yokohama Rubber Hiratsuka Factory

Claims (13)

[Claims] 1. A maleic anhydride-modified polyolefin resin, epoxy-modified between a layer of a thermoplastic elastomer composition comprising a polyolefin-based thermoplastic resin and an elastomer component at least a part of which is crosslinked, and a fiber reinforcing layer. A laminate formed by interposing at least one kind of thermoplastic adhesive resin selected from the group consisting of a polyolefin resin and a polyester-based resin and bonding them together by heat melting. 2. The thermoplastic adhesive resin is a blend of a maleic anhydride-modified polyolefin resin and / or an epoxy-modified polyolefin resin and a polyester resin, wherein the maleic anhydride-modified polyolefin resin and the epoxy-modified polyolefin resin are mixed with a polyester resin. The laminate according to claim 1, wherein the weight ratio of the resin is from 95: 5 to 5:95. 3. The method according to claim 1, wherein the maleic anhydride-modified polyolefin resin or the epoxy-modified polyolefin resin is at 230 ° C.
The melt index measured under the conditions of a load of 2.16 kgf, an orifice diameter of 1 mm, and 10 minutes is 5.0 g / 10.
2. A modified resin of a polypropylene resin of not more than 1 minute.
Or the laminate according to 2. 4. The method according to claim 1, wherein the maleic anhydride-modified polyolefin resin or the epoxy-modified polyolefin resin has a temperature of 190 ° C.
The laminate according to claim 1 or 2, wherein the laminate is a modified resin of a polyethylene resin having a melt index of 5.0 / 10 minutes or less measured under a measurement condition of a load of 2.16 kgf, an orifice diameter of 1 mm, and 10 minutes. 5. The method according to claim 1, wherein the maleic anhydride-modified polyolefin resin or the epoxy-modified polyolefin resin is at 190 ° C.
The melt index measured under the conditions of a load of 2.16 kgf, an orifice diameter of 1 mm, and 10 minutes is 6.0 g / 10.
3. The laminate according to claim 1, wherein the laminate is a modified resin of an ethylene / acrylate copolymer of at least one minute. 4. 6. The polyester resin has a melt index of 20.0 g / 10 measured at 190 ° C., a load of 2.16 kgf, an orifice diameter of 1 mm, and 10 minutes.
3. The laminate according to claim 1, wherein the laminate is a polyester resin having a molecular weight of not more than 3 minutes. 7. A hose having an inner tube and an outer tube and at least one fiber reinforcing layer, wherein at least one of the inner tube and the outer tube is at least partially crosslinked with a polyolefin-based thermoplastic resin. A thermoplastic elastomer composition obtained by blending components, selected from at least a maleic anhydride-modified polyolefin resin, an epoxy-modified polyolefin resin and a polyester resin between at least the thermoplastic elastomer composition layer and the fiber reinforcing layer. A hose that is bonded and integrated by heat fusion with at least one thermoplastic adhesive resin interposed. 8. The hose according to claim 7, wherein the hose has a plurality of fiber reinforced layers and is selected from a maleic anhydride-modified polyolefin resin, an epoxy-modified polyolefin resin and a polyester resin between the fiber reinforced layers. 8. The hose according to claim 7, wherein at least one kind of thermoplastic adhesive resin is interposed to bond and integrate the fiber reinforced layers by heat melting. 9. The thermoplastic adhesive resin is a blend of a maleic anhydride-modified polyolefin resin and / or an epoxy-modified polyolefin resin and a polyester-based resin, wherein the maleic anhydride-modified polyolefin resin and the epoxy-modified polyolefin resin are mixed with a polyester-based resin. The hose according to claim 7 or 8, wherein the weight ratio of the resin is from 95: 5 to 5:95. 10. The method according to claim 1, wherein the maleic anhydride-modified polyolefin resin or the epoxy-modified polyolefin resin is 230 or less.
° C, load 2.16 kgf, orifice diameter 1 mm, and melt index measured under the conditions of 10 minutes: 5.0 g /
The hose according to claim 7, wherein the hose is a modified resin of a polypropylene resin for 10 minutes or less. 11. The method according to claim 1, wherein the maleic anhydride-modified polyolefin resin or the epoxy-modified polyolefin resin is 190 or less.
° C, load 2.16 kgf, orifice diameter 1 mm, and melt index measured under the conditions of 10 minutes: 5.0 g /
The hose according to claim 7, 8 or 9, which is a modified resin of polyethylene resin for 10 minutes or less. 12. The method according to claim 11, wherein the maleic anhydride-modified polyolefin resin or the epoxy-modified polyolefin resin is 190 or less.
C., a load of 2.16 kgf, an orifice diameter of 1 mm, and a melt index of 6.0 g / measurement for 10 minutes.
10. The hose according to claim 7, which is a modified resin of an ethylene / acrylate copolymer for 10 minutes or more. 13. The melt index of the polyester resin measured at 190 ° C., a load of 2.16 kgf, an orifice diameter of 1 mm, and 10 minutes is 20.0 g / 10.
10. A polyester resin having a molecular weight of not more than 10 minutes.
The hose described in.