JPH0872203A - Laminate of resin and rubber - Google Patents

Abstract

PURPOSE: To simply produce a laminate of a resin and rubber without generating a problem from an aspect of working environment by laminating and bonding a rubber compsn. prepared by adding an alkoxysilane compd. represented by formula to a rubber component and a resin to which surface modifying treatment is applied without interposing an adhesive between them to bond a resin layer and a rubber layer. CONSTITUTION: A rubber compsn. is prepared by adding an alkoxysilane compd. represented by formula (wherein R<1> and R<2> are an arbitrary functional group and R<3> and R<4> are a hydrocarbon group) to a rubber component. If necessary, a reinforcing agent, a filler, a vulcanizer and the like are compounded with the rubber component. Plasma discharge treatment, corona discharge treatment or ultraviolet irradiation treatment is applied to a resin based on a polyamide resin to perform modifying treatment. This unvulcanized rubber compsn. and the resin subjected to modifying treatment are laminated without interposing an adhesive between them. The whole is vulcanized by a heat press to obtain a laminate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin-rubber laminate which can be firmly bonded to an unvulcanized rubber and a resin and can be used for various purposes.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
As one of the methods for producing a laminated body in which a resin and a rubber are adhered, after cleaning the resin surface, an undercoat adhesive (primer) is applied and dried (cured if necessary) as necessary,
Further, there is a method of applying (overcoating) adhesive and drying it, and then extruding unvulcanized rubber, laminating it by injection or the like, and vulcanizing the rubber by heat or the like in a mold.

However, in this method, it is necessary to control the concentration of the adhesive for uniformly applying the undercoating and topcoating adhesives dissolved in the solvent and the control of the coating process, and also the drying process of the solvent. It requires heat and heat, and the process is very troublesome. Furthermore, the use of organic solvents used in most adhesives is not preferable in the work environment, and
If the surface of the resin is uneven, it is difficult to apply the adhesive uniformly.

Therefore, in the above laminate, it is desired to improve the adhesiveness between the resin layer and the rubber layer.

The present invention has been made in view of the above circumstances.
An object of the present invention is to provide a laminate of a resin and a rubber, in which the resin layer and the rubber layer can be well adhered to each other and which can be produced by a simple process without any problem in the working environment.

[0006]

Means and Actions for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, added an alkoxysilane compound represented by the following general formula (1) to a rubber component. By laminating and bonding the unvulcanized rubber composition and a resin which has been subjected to a surface modification treatment, particularly a plasma treatment, a corona discharge treatment, or a modification treatment by ultraviolet irradiation, and vulcanizing the resin and the rubber, It was found that it can be easily and firmly adhered without using an adhesive, and that it is possible to produce a laminate of resin and rubber in a simple process, with high productivity and without problems in the working environment, The present invention has been completed.

[0007]

Embedded image (However, in the formula, R ¹ and R ² represent arbitrary functional groups, and R ³ and R ⁴
Represents a hydrocarbon group. )

Therefore, according to the present invention, a rubber composition obtained by adding an alkoxysilane compound represented by the above general formula (1) to a rubber component and a surface-modified resin are not interposed via an adhesive. Provided is a laminate of resin and rubber, which is laminated and laminated.

The present invention will be described in more detail below. The laminate of the resin and rubber according to the present invention is a rubber composition obtained by adding an alkoxysilane compound represented by the above general formula (1) to a rubber component. And a resin which has been subjected to a surface modification treatment are laminated and adhered.

Examples of the rubber component as the main component of the rubber composition include natural rubber, isoprene rubber, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, butadiene rubber, chloroprene rubber, butyl rubber, ethylene propylene diene rubber. , Silicone rubber, fluororubber, isobutylene paramethylstyrene copolymer rubber (partially brominated paramethylstyrene), chlorosulfonated polyethylene rubber, etc., but especially acrylonitrile butadiene copolymer rubber, isobutylene paramethyl Styrene copolymer rubber (partially brominated of paramethylstyrene) and chlorosulfonated polyethylene rubber are preferable.

Next, as the alkoxysilane compound,
The one represented by the following general formula (1) is used.

[0012]

[Chemical 3] (However, in the formula, R ¹ and R ² represent arbitrary functional groups, and R ³ and R ⁴
Represents a hydrocarbon group. )

Here, R ¹ and R ² are arbitrary functional groups, such as an alkyl group such as a methyl group, an ethyl group and a propyl group, an alkoxy group such as a methoxy group and an ethoxy group, an aminoalkyl group and a mercaptoalkyl group. , Halogenated alkyl groups, vinyl groups, vinylalkyl groups, methacryloxyalkyl groups, and the like, but are not limited thereto.

R ³ and R ⁴ are each a hydrocarbon group and an alkyl group such as a methyl group or an ethyl group, that is, --O.
R ^3, -OR ⁴ is a methoxy group, an alkoxy group such as ethoxy groups.

The alkoxysilane compound of formula (1) may be dialkoxysilane, trialkoxysilane or a mixture of both. Specific examples of the alkoxysilane compound include tetramethoxysilane, tetraethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ.
-Methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ -(2-aminoethyl)-
Examples include aminopropylmethyldimethoxysilane, γ-anilinopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, It is not limited to these. Among these, those containing an amino group as a functional group, for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane, γ- (2 −
Aminoethyl) -aminopropylmethyldimethoxysilane, γ-anilinopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane and N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane are preferable. Used.

The amount of the above-mentioned alkoxysilane compound is
0.05 to 5 parts by weight, particularly 0.05 to 1 part by weight is preferable with respect to 100 parts by weight of the rubber component, and sufficient adhesive force may not be obtained if the amount is less than 0.05 parts by weight.
If it exceeds 5 parts, the material cost may increase and the workability in the rubber kneading machine may be deteriorated.

When the above-mentioned rubber component is blended with the alkoxysilane compound of the above formula (1), it can be added and mixed by a usual method. However, for the purpose of improving workability, it is once mixed with silica or the like, and then mixed. May be mixed with the rubber component at.

In the present invention, the rubber composition may be composed of only the above rubber component and alkoxysilane compound, but if necessary, carbon black, silica, clay,
Reinforcing agents such as silicic acid, fillers such as calcium carbonate and mica, vulcanizing agents such as sulfur, peroxide and zinc oxide, vulcanization accelerators, vulcanization aids, antioxidants, plasticizers, etc. be able to. In addition, the addition amount of these optional components can be a normal amount within a range that does not impair the effects of the present invention.

Next, as the resin, polyethylene, polypropylene, polyvinyl chloride, polystyrene, ABS resin, ethylene vinyl acetate copolymer resin, acrylic resin,
Vinylidene chloride resin, polyurethane resin, unsaturated polyester resin, epoxy resin, phenol resin, polycarbonate, polyamide resin, polyimide resin, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, ionomer resin, etc. may be any, and blends of these resins It may be a modified product. In particular, a polyamide resin and a blend of a polyamide resin and another resin are preferably used.

It is preferable to adopt plasma discharge treatment, corona discharge treatment or ultraviolet irradiation treatment as the modification treatment of the resin. Here, these treatments can be performed according to a conventional method, but the conditions for the plasma discharge treatment are:
Argon, helium, and nitrogen are more preferable as the atmosphere gas at a pressure of 1 to 100,000 pascals. The discharge frequency, the discharge output, and the treatment time are preferably adjusted appropriately according to the shape and size of the treatment device, but normally, the frequency is 13.56 MHz, the output is 10 to 1000 watts, and the treatment time is about 5 seconds to 10 minutes. is there.

The corona discharge treatment is usually carried out in the air because of the simplicity of the apparatus, but in order to improve the treatment effect and enhance the adhesiveness, an inert gas such as argon gas, oxygen, nitrogen, etc. The treatment may be carried out in such a gas atmosphere, or the treatment may be carried out while spraying these gases in the vicinity of the electrodes. Particularly, when corona discharge treatment is performed in nitrogen gas, the treatment effect is high, the running cost is relatively low, and there is an advantage that ozone treatment which is generated when performing corona discharge treatment in air is not necessary. Therefore, in the present invention, this method is most preferably adopted as a method for modifying the resin.

The frequency of the corona discharge treatment can be appropriately adjusted, but from the viewpoint of treatment effect and efficiency, it is usually 5 kHz or higher, and particularly preferably 20 to 30 kHz. If it is lower than 5 kHz, it is difficult to perform stable and uniform treatment, and the power consumption increases, which may increase the power cost and shorten the durability of the electrode.

The discharge output and the treatment time may be appropriately adjusted according to the material, shape and size of the object to be treated, the shape and size of the electrode, etc., but usually 50 to 5000 watts,
About 1 to 60 seconds is preferable.

As a light source for the ultraviolet irradiation treatment, a mercury lamp, a halogen lamp, an excimer lamp, an excimer laser or the like is used. The treatment may be performed in air, but may be performed in a nitrogen gas atmosphere. The light source output and irradiation time are not particularly limited, and the type of light source, characteristics, processing atmosphere,
It may be appropriately adjusted according to the distance to the object to be processed, the material, shape and the like of the object to be processed.

In the present invention, a laminate can be obtained by laminating the above-mentioned unvulcanized rubber composition and the modified resin without interposing an adhesive and vulcanizing them by hot pressing or the like. . In this case, the vulcanization conditions are not particularly limited, but may be 130 to 180 ° C. for 5 minutes to 5 hours.

[0026]

EFFECT OF THE INVENTION The resin-rubber laminate of the present invention can be produced by firmly adhering the resin and rubber to each other without using an adhesive such as a solvent type, and by a simple process without a problem in the working environment. It can be manufactured with good properties and can be widely used in various applications such as resin-rubber laminated hoses, anti-vibration rubber, and air springs.

[0027]

EXAMPLES The present invention will be specifically described below by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Examples and Comparative Examples] Two types of resins, 6.66 copolymerized nylon (Ube Kosan Co., Ltd. 5033) and 12 nylon (Ube Kosan Co., Ltd. 3035), were respectively formed into 150 micron thick films by T-die extrusion. I pushed it out.

Next, as shown in Table 1, the film was subjected to plasma treatment, corona treatment (1), corona treatment (2) and ultraviolet irradiation treatment by the following methods. Plasma treatment : External electrode type 10 × 25 cm with a spacing of 1
Using a high frequency power source (SKN-05P) and a matching box (MB-500) manufactured by Japan High Frequency Co., Ltd. in an argon gas atmosphere with a pressure of 0.7 torr in a glass vacuum container equipped with a 5 cm parallel plate electrode, 13 .56 MH
Plasma treatment was performed for 3 minutes at z and an output of 100 W. Corona treatment (1) : From an electrode having a length of 100 mm and a width of 4 mm and a surface of which is coated with Teflon (trademark of DuPont of PTFE) having a thickness of 1 mm, and a ground electrode having a size of 150 × 150 mm and arranged at a distance of 5 mm from the electrode. A corona-treated electrode and a corona power supply HV05-2 manufactured by TANTEC were used to discharge in air at an output of 80 W, and the nylon film was passed through the discharge at a speed of 1 m / min. Corona treatment (2) : The entire corona-treated electrode has a volume of 180 × 180 × 900 mm and a gas inlet port of 100.
It was placed in a container equipped with a 0.5 mm film entrance / exit. Next, nitrogen gas at a flow rate of 1 liter / min was flowed through the gas inlet for 5 minutes to replace the air in the container with nitrogen gas. In this state, the nylon film was treated under the same conditions as the corona treatment (1). Ultraviolet irradiation treatment : Using a dielectric barrier type excimer ultraviolet lamp (model number VES20-172) manufactured by Ushio Inc., a nylon film was placed in the air at a distance of 5 mm from the irradiation window, and the film surface was exposed to ultraviolet rays for 5 minutes. . Untreated : A comparative product which was not subjected to any surface modification treatment was prepared.

[0030]

[Table 1]

Next, rubber compositions (unvulcanized) of 8 kinds of compositions shown in Tables 2 and 3 were prepared, sheeted to a thickness of 3 mm, and the surface-treated nylon film was treated with rubber. The combination shown in Table 4 is attached so that the side is on the side, and the pressure is 5 kgf / cm ² and the temperature is 1 by hot pressing.
It was vulcanized at 40 ° C. for 80 minutes.

The vulcanized resin (nylon) -rubber laminate was cut into a width of 12 mm, and the autograph manufactured by Shimadzu Corporation was used to draw nylon-by a T-peel method at a pulling speed of 50 mm / min.
The adhesive force between the rubbers was measured. The results are shown in Table 4.

As shown in Table 4, it was confirmed that the resin (nylon) -rubber laminate according to the present invention has excellent adhesiveness.

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

[Table 4]

Claims (4)

[Claims] 1. A rubber composition obtained by adding an alkoxysilane compound represented by the following general formula (1) to a rubber component and a surface-modified resin are laminated and pasted without an adhesive. A laminated body of resin and rubber, which is characterized by being combined. Embedded image (However, in the formula, R ¹ and R ² represent arbitrary functional groups, and R ³ and R ⁴
Represents a hydrocarbon group. ) 2. The laminate according to claim 1, wherein the surface modification treatment is plasma treatment, corona discharge treatment or ultraviolet irradiation treatment. 3. The laminate according to claim 1, wherein the alkoxysilane compound has an amino group. 4. The laminate according to claim 1, wherein the main component of the resin is a polyamide resin.