JPS60193650A - Nylon resin laminated rubber material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a nylon resin laminated rubber material in which a nylon resin coating is extremely strongly bonded to a rubber base material.

[Prior art]

It has been proposed to improve the friction and abrasion characteristics, adhesiveness, appearance, etc. of a rubber material by laminating a synthetic resin coating layer on the surface of the molded rubber material. (For example, a cleaning blade for electrophotographic photoreceptors that has improved abrasion resistance by adhering a hard resin film to the surface of the rubber elastic body of the base using double-sided adhesive tape or an appropriate adhesive. No. 56-55979). Today, this laminated structure takes advantage of the inherent properties of rubber materials, such as elasticity.

Furthermore, there is a strong desire for the development of technology to highly improve its physical and chemical properties. For example, the characteristics required for important safety parts used in automobile brakes and engines, or functional parts used in various office equipment and home appliances, are
This is because they are becoming increasingly strict and sophisticated from the standpoint of maintenance-free maintenance. The realization of a laminated material that satisfies these strict requirements is largely due to the adhesive strength and durability (adhesive life) between the molded rubber material and the resin coating, as well as the characteristics of the coating-forming resin.

However, in conventional synthetic resin laminated rubber materials, the adhesive force between the molded rubber material and the resin coating was not sufficient. In addition, minute gaps are formed in the laminated parts, and the effect of preserving the base rubber material from the influence of the outside world, such as chemical action, becomes very weak, and the effect of simply reducing frictional resistance, adhesion, or However, only simple effects such as improved wear resistance were obtained. In response to this, the present applicant has proposed a wiping blade in which an adhesion-strengthening treatment layer and a resin coating layer are laminated on the surface of a rubber elastic core material. The adhesion-strengthening layer is formed by subjecting the stone surface to chlorination treatment, chromic acid etching treatment, or plasma etching treatment, while the resin layer is made of a resin that has wear resistance and a low coefficient of friction and is soluble in organic solvents. It is to be selected. The proposed composite structure with this adhesive treatment layer not only has excellent abrasion resistance, but also eliminates the need for adhesive tape or adhesive, resulting in a highly durable structure that is less prone to flaking due to long-term wiping movements of the blade. Obtains a wiping blade. However, there is still room for improvement as a laminated rubber material that can be used in other applications that require more severe performance than the wiping blade. Therefore, the applicant has conducted extensive research in order to realize a combination of rubber material, adhesive strength-strengthening treatment agent, and synthetic resin that can sufficiently withstand applications such as important safety parts and provide the strongest adhesive strength. .

[Purpose of the invention]

The present invention provides a composite rubber material consisting of a combination of a rubber material layer, a surface treatment layer, and a synthetic resin layer that can provide the strongest adhesive strength.

The aim is to realize various important safety parts and functional parts that can fully guarantee the required performance.

[Structure of the invention]

This invention achieves the above object.
A rubber material layer containing butadiene copolymer rubber (hereinafter referred to as NBI) as a main component, an adhesion-strengthening layer whose surface is etched with chromic acid, and a nylon layer formed through this adhesive-strengthening layer. This is a nylon resin laminated rubber material consisting of a resin coating layer.

The rubber raw material forming the rubber material layer of this invention is mainly composed of NB, such as extremely high nitrile.

A single raw material of high nitrile, medium high nitrile, medium nitrile and low nitrile NBR or a mixture of these NH1 (vinyl chloride resin, modified phenol resin, chloroprene rubber, chlorinated rubber, etc.).

The adhesion-strengthening layer of the present invention is formed by molding the above-mentioned NBR or a mixture with other polymers into a desired product shape, and etching the surface with chromic acid.

The nylon resin coating layer of this invention is made of soluble nylon (°
For example, Toshi product name rcM4000JrCM4001
J, etc.) in an organic solvent such as methanol or a mixture of methanol and water.

It is carried out by a dipping method, a spray method, a brushing method, a casting method, etc. Or again. A method may also be used in which a nylon film is placed on an NB molded material and then heated and pressure welded.

In this invention, the bonding strength with the nylon resin is improved by etching NBi with chromic acid.

As shown in the examples below, it is not clear why the acrylonitrile group (
It is also conceivable that CH,=C)icN,) is oxidized by chromic acid and changed to a carboxyl group (COOH), and that not only physical bonding force but also chemical bonding force acts strongly with the nylon resin.

Hereinafter, an experimental example will be described in which the characteristics of the rubber material constructed according to the present invention were compared with those of other constructions.

[Experimental Example 1] During adhesion test between rubber material layer and resin layer, nitrile NBR was used as the rubber raw material and the thickness was 211K.

A rectangular test piece with a width of 20 mm and a length of 1100 W was molded. The obtained rubber material was treated with chromic anhydride 4007.
, sulfuric acid 400.9, water 21! After immersion treatment at 40°C for 2 minutes in an etching solution consisting of soluble nylon "6M
A test piece as a nylon resin laminated rubber material according to the present invention was prepared by applying a nylon resin coating to a thickness of about 30 μm by dipping using a 10 wt % methanol solution of 4,000 μm (hereinafter referred to as sample A). On the other hand, for comparison.

With the combination of rubber material and coating resin shown in Table 0-1,
A sample that had been similarly etched with chromic acid was prepared.

Table 1 However, NR: Natural rubber BR: Butadiene rubber EPI) M: Ethylene or propylene φ diene copolymer rubber Diallyl phthalate resin coating: Immersed in a 10 wt% acetone solution.

Polycarbonate resin coating: Immersed in 10 wt% chloroform solution.

Polyimide resin coating: Immersed in a 10wt thihalophenol solution of biphenyltetracarboxylic acid polyimide.

The results of comparing the adhesive strength of each sample A-P above are shown below.
Table 2] shows the results. However, the adhesive strength was evaluated using data from a cross-cut test and a fir durability test.

Cross-cut test (1st supplementary angle base test): This shows the initial adhesion, and 100 I ml+!
Attach Nichiban Cellotape R1 to the cut corner. When the tape is removed by hand, it is indicated by the number of resin coatings that did not peel off together with the tape.

For example, if the number of peeled stitches is 0, it is 100/100, if it is 10, it is 90/100. Fir durability test: This shows the adhesive durability. The test piece is attached to a fir movement testing machine, and the test piece is repeated 120 times per minute. This figure shows the peeling state of the resin corrugator when a fir motion is applied.

Table 2 [Table 3] shows the results of the adhesion test for the rubber-resin combinations in Table 1, where the surface treatment was chlorination treatment. However, for chlorination, water 111 sodium hypochlorite 4
0 m/, in a chlorinated solution consisting of 8 ml of hydrochloric acid at 40°C.
It was immersed for a minute.

Table-3 [Table-4] shows 1 for each rubber-resin combination in Table-1.
Although the surface treatment was plasma etching treatment, the results of an adhesion test are shown. However, for plasma etching, the pressure is 0.5 Torr, the flow rate is 50 ccΔnin, and the power is 10
The test was performed by generating oxygen plasma at 0 W and treating the sample for 10 minutes.

Table 4 From the results shown in Tables 1 to 4 above, a certain degree of adhesive strength is observed even in combinations other than those of the present invention. For example, from the cross-cut test results, it can be said that the initial adhesive strength is good. However, the durability according to the fir durability test results is poor. Against this.

According to combination A of the present invention, not only the initial adhesion but also the durability are very improved.

In other words, the rubber material itself is damaged before the peeling phenomenon occurs, and the adhesive strength and adhesive life of the nylon resin material A configured according to the present invention are significantly superior to those of other configurations. That is clear.

[Experimental Example 2] Oil Resistance Test In order to evaluate the oil resistance of the nylon resin laminated rubber material according to the present invention, various samples having the configurations shown in [Table 5] were prepared.

Table 5 However, the adhesion-strengthening treatment layer for the resin-coated specimens (sample a-i) was formed by the same chromic acid etching treatment as in [Experimental Example-1].

The oil resistance test was an immersion test according to JIS K6301 (vulcanized rubber physical testing method), and the volume change rate of a No. 3 dumbbell-shaped test piece is shown in [Table 6].

Table 6 (Volume change rate Q) Test conditions: Fuel C (fuel oil resistance evaluation) 40°C x 1
20 hours rot foil (Plasticizer extractability evaluation) 120℃ x 120 hours Taka3oi1 (swellability evaluation) 120℃ x 120 hours The resin-covered sample of rubber mainly composed of NBR (sample d-i) showed no volume change. was not recognized. On the other hand, those using NR, BR, or EPDM cannot be said to have good oil resistance at this level, although there are differences depending on the presence or absence of a nylon resin layer. That is, N11. ．． 81(, gPDM
By laminating nylon resin layers, the swelling can be suppressed by about 1/2, but this cannot be said to fully take advantage of the characteristics of laminating nylon resin. .

[Experimental Example 3] Ozone Resistance Test Using various samples a to 0 configured in the same manner as Table 5 of Experimental Example 2, ozone based on JI8K 6301 to 16 was used. However, the test piece was formed in the shape of a No. 1 dumbbell.

Ozone concentration: 5ρpphm Temperature: 40°C Sample elongation rate: 20% Measurement of time from crack generation to cutting Table 7 The ozone resistance of sample d-i according to the configuration of the present invention is extremely excellent. Note that sample C (rubber EPDM).

Chromic acid etching treatment, nylon resin coating) and sample o
(EPDM rubber material only) shows great ozone resistance of the rubber material itself.

[Experimental Example 4] Heat resistance test Using each sample a to 0 configured in the same manner as Experimental Examples 2 to 3,
The results of the air heating aging test in JISK 6301-6 aging test are shown in [Table 8].

The measured value is the hardness change (degrees) of the sample after 72 hours at 120℃
, tensile strength change (%), and elongation change (chi).

Table 8 The heat resistance of sample d-i having the structure according to the present invention is much better than other samples.

[Experimental Example 5] Gas permeability test Various samples a - o constructed in the same manner as in Experimental Example 2 (oil resistance test) (however, the test piece size was 100 mm in diameter)
A8'rMIJ-1
Based on the "434r gas permeability test method", the permeation amount of fluorocarbon gas (C (42F, 2) in the thickness direction (crdl cr& ・24 hours, a
trn, p) and obtained the results shown in [Table 9].

As is clear from each of the above experimental examples 2 to 5, the permeation amount of fluorocarbon gas for the sample d%i having the structure according to the present invention is much smaller than that for other samples. This is because the adhesion with the nylon resin layer formed through the chromic acid etched adhesion-strengthening layer is extremely high.

There is no possibility of oil, oxygen, ozone or fluorocarbon gases entering through the gaps between the layers. Therefore, it has excellent oil resistance, heat resistance, ozone resistance, and gas barrier properties, but on the other hand, other samples lacked adhesive strength and could not completely prevent intrusion through the gaps between the laminated layers. The effect of laminating resin waste has been halved.

[Experimental Example 6] Friction Coefficient Measurement Test The friction coefficient was determined using each sample a to o constructed in the same manner as in Experimental Examples 2 to 5.

1 (Using an EIDON-14 type surface resistance tester (manufactured by Shinraikagaku), a load of 50.9 is applied to the sample through a sapphire hemisphere with a diameter of 2n.The sample in that state is pulled at a speed of 5.
The load applied to the sapphire hemisphere when moved at 0 w/min was measured and the friction coefficient was determined by Table 10.The reduction in frictional resistance due to the nylon resin coating layer is remarkable.

〔Effect of the invention〕

As explained above, according to the nylon resin laminated rubber material of the present invention, a product with a very strong adhesive force between the molded rubber material and the resin coating and a long service life can be obtained. Moreover, it not only improves physical and mechanical properties, but also improves chemical properties such as oil resistance, ozone resistance, gas permeability, heat resistance, etc. because the molded rubber base material retains moisture by strengthening adhesive strength. could also be significantly improved. Therefore, it can be applied with sufficient reliability to functional parts and important safety parts that require strict III performance.

The following products can be considered as products to which this invention can be applied.

b) Cleaning blades used in photosensitive copying machines, etc., which require low coefficient of friction, wear resistance, ozone resistance, etc.

) Rolling diaphragms for coolers and air conditioners that require fluorocarbon gas barrier properties, secondary ozone properties, bending resistance, etc.

c) Oil hoses for automobile engines that require oil resistance, heat resistance, ozone resistance, etc.

2) Seal members such as sliding O-rings that require oil resistance, heat resistance, low friction resistance, wear resistance, etc.

e) Pulp materials that require oil resistance, heat resistance, non-adhesiveness, and abrasion resistance.

Claims (1)

[Claims] A rubber material layer whose main component is acrylonitrile-butadiene copolymer rubber, an adhesion-strengthening layer in which the surface of the rubber material layer is treated with chromic acid etching treatment, and a nylon resin coating layer formed through this adhesive-strengthening treatment layer. A nylon resin laminated rubber material characterized by: