JP2987391B2 - Laminate of synthetic resin and rubber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel laminate of synthetic resin and rubber, and to a field in which the characteristics of synthetic resin and rubber are effectively used, such as a fuel hose and a packing material. Tubular or plate which is a useful industrial material to use
The present invention relates to a laminar laminate.

[0002]

2. Description of the Related Art A fuel hose for an automobile engine is an effective field of application of a laminate of a synthetic resin and rubber. Burning
It is necessary that the hose for feed be imparted with flexibility by utilizing rubber elasticity, and be imparted with gasoline corrosion resistance and gasoline permeation resistance. For this purpose, a fuel hose with an outer rubber layer made of a fluorine resin or nylon resin with good gasoline permeability is used as the inner layer.
Has been developed and used.

However, since the fluororesin and rubber are difficult to adhere to each other, surface corona treatment, plasma treatment, metal sodium treatment and the like are performed, and they are integrated using an organic siloxane-based or epoxy resin-based adhesive. (For example, JP-B-57-38272, JP-A-5-17771, JP-A-5-44874, etc.), the adhesive force is not sufficient with an organic siloxane-based resin, and the epoxy-based resin adhesive becomes hard when the adhesive layer is cured.
There is a disadvantage that it becomes difficult to follow the bending of the fuel hose , and finally cracks occur, resulting in peeling or breakage of the inner layer of the fluororesin.

[0004] As a measure to prevent the deterioration of the outer rubber layer of the fuel hose due to sour gasoline, the inner rubber layer must be covered by two layers.
And a blend polymer containing an acrylic rubber and a fluororesin in the inner layer and a blend polymer containing epichlorohydrin rubber in the outer layer (Japanese Patent Laid-Open Publication No. 1-1).
No. 59245) or a mixture of a blended polymer of acrylic rubber and fluororesin for the inner tube rubber layer and acrylonitrile-butadiene rubber for the outer tube rubber layer
No. 218347), which utilizes a means of blending oil-resistant fluororesin with rubber.

On the other hand, epoxidized rubber is obtained by reacting a rubber latex with a peroxide acid to add an epoxy group to the skeleton of a rubber molecule, and utilizes the low rolling resistance and good wet grip properties of this rubber. Attention has been focused on improving the performance of treads, inner tubes, inner liners, and the like of passenger car tires.

[0006] In such an automobile tire, a method of producing a rubber composite material by disposing an epoxidized rubber between two rubber layers containing no epoxy group is described.
It is proposed in Japanese Patent Application Laid-Open No. 2-229834.

Further, in order to obtain a rubber composition having a high modulus as a tire tread base composition and a tire wire coat composition, it has been proposed in Japanese Patent Application Laid-Open No. 2-107628 to react epoxidized rubber with nylon at a high temperature. ing.

[0008]

DISCLOSURE OF THE INVENTION The present invention improves the problem of the conventional interfacial adhesion, that is, the performance deterioration of the laminate due to interfacial peeling, interfacial cracking, interfacial deterioration, etc., in a laminate of synthetic resin and rubber. To develop a powerful means of laminating thin resin layers such as fluororesin, which has better gasoline resistance than a blend polymer of fluororesin and rubber,
The present invention focuses on the use of the epoxidized rubber and conducts various studies. In particular, the present invention is intended to be applied to a laminated body of a synthetic resin and a rubber, which has extremely high oil resistance and excellent durability.

[0009]

The first object of the present invention is to provide a laminate of a synthetic resin layer and a rubber layer, wherein an interface adhesive layer between the synthetic resin layer and the rubber layer is epoxidized. A laminate of a synthetic resin and a rubber, which is a rubber or a blend of an epoxidized rubber and a rubber.

[0010] Claim 2 is an interface between the synthetic resin layer and the rubber layer.
Epoxy rubber for the surface adhesive layer is made of natural rubber, isoprengo
Rubber, butadiene rubber, styrene-butadiene rubber, nitrite
Ril rubber, ethylene-propylene-diene rubber or d.
One type of epoxidation degree of picrohydrin rubber of 2 to 50 mol%
Or a laminate of synthetic resin and rubber as a mixture of two or more
It is.

The raw materials of the epoxidized rubber are natural rubber and synthetic rubber, for example, natural rubber (NR), styrene butadiene rubber (SBR), butadiene rubber (BR), acrylonitrile butadiene rubber (NBR), chloroprene rubber (C
R), butyl rubber (IIR), ethylene / propylene rubber (EPT), isoprene rubber (IR), acrylic rubber (AC
M), fluoro rubber (FPM), chlorosulfonated polyethylene (CSM), NBR and polyvinyl chloride blend rubber (NBR / P
VC), epichlorohydrin rubber (CO, ECO) and the like, but are not limited thereto. Generally, NR, IR, BR, SBR, NBR, EPT epoxidized rubber is suitable from the viewpoint of physical properties and performance, and the epoxidation degree is 2 to 60 mol%, preferably 5 to 55 mol%. . If it is less than 2 mol%, the adhesiveness cannot be improved by epoxidation.
When blending with rubber, it adheres to the inner wall of the blender, making mechanical blending difficult.

Other rubbers to be mixed with the epoxidized rubber include SBR, BR, NBR, CR, IIR, EPT (EPDM), IR, ACM, N
R, Si, FPM, CSM, CO, ECO, etc., but not particularly limited thereto. If oil resistance is required, NBR, C
O, ECO , NBR / PVC are used.

As the rubber substance, those similar to the above-mentioned epoxidized rubber material or the rubber substance blended with the epoxidized rubber can be used. For example, SBR, BR, NBR, CR, II
R, EPT, IR, ACM, NR, Si, FPM, CSM, NBR / PVC, CO,
ECO and the like, but not particularly limited thereto. However, when oil resistance is required, NBR, NBR / PVC, CO,
ECO or the like is used.

In the laminate of the synthetic resin and the rubber, the synthetic resin to be laminated with the rubber substance includes a fluororesin, a nylon resin, a polyester resin, an ethylene-vinyl acetate copolymer, a polyolefin resin such as polyethylene and polypropylene, Polyvinyl chloride resin and the like can be mentioned. Among them, when a fuel hose is used, a laminate with an oil-resistant resin such as various fluorine resins and nylon resins is most preferable.

The fluororesin mentioned here includes the following. That is, polytetrafluoroethylene (PTF
E), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer (EPE) ,
Tetrafluoroethylene-ethylene copolymer (ETFE),
Polychlorotrifluoroethylene (CTFE), chlorotrifluoroethylene-ethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer Coalescing (TH
V). In particular, from the viewpoint of molding process, physical properties and performance, tetrafluoroethylene-ethylene copolymer (ETF
E), a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV) is desirable.

Examples of the nylon resin include nylon 6, nylon 66, nylon 11, nylon 12, etc.
When bending properties such as hoses are required, nylon 11 and nylon 12 are desirable.

As the epoxy curing agent to be mixed at the same time as the epoxidized rubber, a polyamine-based or acid anhydride-based one is used. For example, for polyamines, diethylene triamine (DETA), triethylene tetramine (TET)
A), tetraethylenepentamine (TEPA), diethyleneaminopropylamine (DEPA), polyamide polyamines, dimethylcyclohexylamine (DMCA), mensendiamine (MDA), isophoronediamine (IPDA), N-aminoethylpiperazine (N -AEP), 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5)
Undecane adduct (ATU adduct), bis (4-amino-3-methylcyclohexyl) methane (laromin C-26)
0, trade name of BASF), bis (4-aminocyclohexyl)
Methane (Wandamine HM, brand name of Nippon Rika), meta-xylene diamine (m-XDA) diaminodiphenylmethane (DD
M), diaminodiphenylsulfone (DDS), m-phenylenediamine (m-PDA), dicyandiamide (Dicy),
Adipic dihydrazide (AADH), etc., and acid anhydrides include phthalic anhydride (PA), tetrahydrophthalic anhydride (THPA), hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MeTHPA), methylhexa Hydrophthalic anhydride (MeHHPA), methylnadic anhydride (MNA), dodecyl succinic anhydride (DDSA), chlorendic anhydride (HET), pyromellitic anhydride (PMDA),
Benzophenone tetracarboxylic anhydride (BTDA), ethylene glycol bis (anhydrotrimate) (TME
G), methylcyclohexenetetracarboxylic anhydride (M
CTC), trimellitic anhydride (TMA), polyazelain anhydride (PAPA) and the like are used. Although not particularly limited, the viscosity of diaminediphenylmethane (DDM) for polyamines and methylhexahydrophthalic anhydride for acid anhydrides are easily kneaded into the epoxidized rubber.

As the curing accelerator for the epoxy curing agent, the above-mentioned amine-based curing agent itself serves as an accelerator, and the same applies to an acid anhydride-based curing agent. Used. Imidazoles, imidazolines, DBUs 1,8-diazabicyclo (5,4,0) undecene-
7, benzyldimethylamine (BDMA), 2,4,6 trisdimethylaminomethylphenol (DMP-30, Kayaku Nuuri trade name), 2PTA lauryl dimethylamine, metal acetylacetonate, tin octylate, triphenylphosphine, tetra Phenylphosphonium-tetraphenylporate, amine imide and the like.

As described above, the laminated body of synthetic resin and rubber is prepared by first adhering epoxidized rubber itself or a blend of epoxidized rubber and rubber itself as a rubber layer to be laminated on the synthetic resin layer. Laminate without any intervening agent. The rubber layer is made of 0.25-0. Anhydrous sodium carbonate so that the epoxidized rubber and rubber can be processed smoothly.
Prevent scorch by adding about 3phr. In addition to anhydrous sodium carbonate, magnesium oxide, calcium stearate, zinc carbonate, etc. can also be used to adjust the pH. Next, regarding the vulcanization method, a conventional vulcanization method may be used, but a low sulfur vulcanization method using less sulfur and a large amount of a vulcanization accelerator is used. Furthermore, the above epoxy curing agent, epoxy curing accelerator, etc. are blended and kneaded at about 100 ° C. or lower to obtain an epoxidized rubber composition. If necessary, normal rubber is added and kneaded.

[0020]

When the epoxidized rubber is used as an interfacial adhesive between the synthetic resin layer and the rubber layer, it is harder to cure as compared with the case where only the epoxy adhesive is used, and no crack is generated. The adhesive strength is already exhibited before curing, so that the initial adhesiveness is excellent. By adjusting the degree of epoxidation and blending with other rubbers, the hardness and other properties of the adhesive layer can be changed.

The synthetic resin layer is an inner tube of a fluororesin hose, the rubber layer is an outer tube of the hose, and the synthetic resin layer and the rubber layer are
Of the interfacial bonding layer is a tubular laminate is a blend of epoxidized natural rubber and NBR / PVC rubber, excellent characteristics resistant
It becomes a fuel hose that exhibits oiliness . Gasoline car
For fuel hoses and the like, complicated bending processing is performed with a mandrel, but if an epoxy curing agent is selected, the synthetic resin and the rubber layer will already adhere to each other even when not vulcanized and the interface will not peel off even when deformed. This is very advantageous because an adhesive force is obtained.

[0022]

EXAMPLE 1 As a synthetic resin layer 1 shown in FIG. 1, a sheet of nylon 6 having a thickness of 2.1 mm and a size of 200 mm × 200 mm was used.
Epoxy degree 50 ± 2 mol% as rubber layer 2 on this sheet
Of epoxy natural rubber (ENR-50, manufactured by Malaysia Rubber Institute) and kneading sheet (10 mm thick)
It was vulcanized and bonded at 60 ° C. for 7 minutes to obtain a plate-shaped laminate 3. When the delamination test of the plate-like laminate 3 was performed according to JIS K6301, the structure of the rubber layer 2 was destroyed, and no delamination was observed. This has excellent performance as an anti-vibration plate. On the other hand, as a comparative example, NR was used instead of ENR-50, and the vulcanized product of the compound without addition of tetrahydrophthalic anhydride did not provide the adhesive strength of the laminate and easily delaminated. .

Example 2 FIG.Hose for fuelFluorine resin for synthetic resin layer 1 of inner tube
Tetrafluoroethylene-hexafluoropropylene-
Extrusion using vinylidene fluoride copolymer (THV)
Extruded at 230 ° C with a machine to a diameter of 30 mm and a thickness of 0.2 mm.
Of the outer tube is treated as corona discharge
NBR / PVC blend rubber of Formulation Example 2 and epoxidation degree 50 ± 2
Formulation based on a 100: 30 blend of mol% ENR-50
Extrude the product at 80 ° C and make the rubber layer 3mm thick.Tubular laminateMake 4
Done. Formulation Example 2 NBR / PVC 100 ENR-50 30 Zinc white flower 5 Stearic acid 1 White carbon 40 Carbon black 40 Plasticizer (phthalic acid) 20 Vulcanization accelerator (Sulfenamide) 1.9 Iow 1.7Methyl hexahydrophthalic anhydride 23  262.6 ThisTubular laminate4 into the mandrel and direct steam vulcanization
At 6Kgf / cm^TwoFor 20 minutes. Same as Example 1
In the delamination test, the structure of the rubber layer 2 was destroyed and the delamination was performed.
There was no separation. As a comparative example, ENR-
Formulated without 50 and methyl hexahydrophthalic anhydride
The same treatment is applied to peel off between layers.
The result was shown.

Example 3 As a synthetic resin layer, tetrafluoroethylene-ethylene copolymer (ETFE) was used instead of the THV of Example 2, and as a rubber layer, epichlorohydrin rubber was used instead of the ENR / NBR / PVC blend of Example 2. (Epchromer C, trade name of DAISO Co., Ltd.) and an epoxidized natural rubber having a degree of epoxidation of 25 ± 2 mol% (ENR-25, manufactured by Malaysia Rubber Institute) were used as a composition of the following Formulation Example 3. A tubular laminate 4 shown in FIG. 2 was manufactured in the same manner as in 2. This product also showed no adhesive peeling phenomenon between the synthetic resin layer and the rubber layer, and showed excellent adhesive strength. In view of the properties of the laminate, it has good oil resistance to alcohol-mixed gasoline.

Example 4 Nylon 11 was used as a synthetic resin layer, and a blend of epoxidized NBR and NBR (50:50) having an epoxidation degree of 25 ± 3 mol% was used as a compound of a rubber layer according to Formulation Example 4. Shown in 2
A tubular laminate 4 was manufactured, and the same results as in Example 2 were obtained.

Example 5-8 In the combination of each synthetic resin layer and each rubber layer shown in Table 1, as the interfacial adhesive layer 5, the one of the above-mentioned formulation example 1-4 composed of a blend of epoxidized rubber and rubber was used. The laminate shown in FIGS. 3 and 4 was obtained. These were all structural destruction of the interface adhesive layer.

[0027]

[Table 1]

Example 9 Nylon 6 as synthetic resin layer 2.1 mm thick 200 mm × 2
As a rubber layer, a epoxidized natural rubber having a degree of epoxidation of 50 ± 2 mol% (ENR-5
A plate-like laminate 3 shown in FIG. 1 was obtained in the same manner as in Example 1 using a kneaded sheet of a rubber compound mainly composed of (0). Also,
Using nylon 6 as the synthetic resin layer, using NBR as the rubber layer, and as the interfacial adhesive layer 5 between them,
Using a sheet with a thickness of 0.5 mm, heat and press the plate shown in Fig. 3
A laminate 3 was obtained. When a peeling test was performed on these two plate-shaped laminates in the same manner as in Example 1, all the structural failures in the rubber layer 2 were found to be broken.

[0029]

The laminate of the synthetic resin and rubber of the present invention is
With the above configuration, the interlayer adhesion between the synthetic resin layer and the rubber layer, which are originally easily peeled off, is improved, and in most cases, a strong bond that causes structural destruction of the rubber layer is obtained. It has become possible to provide fuel hoses , packings, diaphragms, etc. with further improved gasoline resistance, alcohol gasoline resistance, and sour gasoline resistance.

Further, since the rubber layer has excellent initial adhesion before vulcanization, it is difficult to use a complicated gasoline automobile using a mandrel .
An excellent product can be provided at a low cost even in the processing of the fuel hose .

[Brief description of the drawings]

FIG. 1 is a sectional view of a plate-shaped laminate.

FIG. 2 is a sectional view of a tubular laminate.

FIG. 3 is a cross-sectional view of a plate-shaped laminate.

FIG. 4 is a sectional view of a tubular laminate.

[Explanation of symbols]

 1 Synthetic resin layer 2 Rubber layer 3Plate laminate  Four Tubular laminate 5 Interface adhesive layer

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) B32B 1/00-35/00 C08J 5/12 F16L 11/04-11/12

Claims (3)

(57) [Claims] 1. A laminate of a synthetic resin layer and a rubber layer, wherein the interfacial adhesive layer between the synthetic resin layer and the rubber layer is epoxidized rubber or a blend of epoxidized rubber and rubber. Laminate of synthetic resin and rubber. 2. The degree of epoxidation of the epoxidized rubber of the interfacial adhesive layer of natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, nitrile rubber, ethylene-propylene-diene rubber or epichlorohydrin rubber.
2. The composition according to claim 1 , which is a mixture of 2 to 50 mol% of one or more kinds.
Laminate of a synthetic resin and rubber mounting. 3. The synthetic resin layer is an inner tube of a fluororesin hose, the rubber layer is an outer tube of the hose, and the synthetic resin layer is a rubber layer.
A laminate of synthetic resin and rubber, which is a tubular laminate in which the interfacial adhesive layer is a blend of epoxidized natural rubber and NBR / PVC rubber .