JPH01271238A - Manufacture of rubber/fiber composite - Google Patents

Abstract

PURPOSE:To obtain a rubber/fiber composite whose adhesion is favorable, by a method wherein a radical is caused to occur on the surface through plasmic treatment, over which a compound capable of performing radical polymerization, a latex compound and further rubber are imparted for vulcanization. CONSTITUTION:Plasma is applied to the surface of a fiber such as a synthetic fiber and a radical and/or a peroxide is caused to occur over a fiber surface. Then a mixture of a compound, which is capable of performing radical polymerization, such as N, N'-methylene bisacrylic amide and a latex compound such as SBR is imparted over the radical or the peroxide. When rubber is imparted further over an imparted surface of the mixture for vulcanization, the radical on the surface is bonded with a polymericable matter through heating. In succession, the radical polymerization progresses between the same and latex and between the latex and rubber. Therefore, strong joint is formed between the fiber and rubber and becomes a rubber/fiber composite whose adhesion is favorable.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for manufacturing a strongly bonded rubber/fiber composite.

(Prior Art) In order to improve the adhesion between fibers and rubber, attempts have been made to add various functional groups to the surfaces of fibers.

The method involves applying a polymerizable compound with a functional group such as epoxy or isocyanate to the fiber surface, and then
Radicals, which are the starting points for graft polymerization, can be created on the surface or inside of the fibers using methods such as heating to fix them on the fiber surface, or using radiation, electron beams, ultraviolet rays, low-temperature plasma, or chemical polymerization initiators on the fiber surface. There is a method of graft polymerizing a radically polymerizable monomer during or after formation.

However, the above-mentioned method of thermally hardening functional groups has many troubles such as staining of rollers and the like during processing, and has poor operability. In addition, in the method of graft polymerization while forming radicals by plasma irradiation, a large amount of homopolymer is generated, the grafting rate is extremely low, and the chamber wall inside the plasma generator is also contaminated, so stable processing cannot be achieved. That's difficult.

Further, a similar problem occurs in graft polymerization in which radicals are generated and then grafted.

Furthermore, in these methods, Weakbou is added to the fiber surface.
ndary 1 ayer (W, B, L) may occur, making it difficult to obtain good adhesion.

(Problems to be Solved by the Invention) The present invention efficiently utilizes the radical Q-bar fourth side generated on the fiber surface by plasma treatment, etc. This is to obtain strong contact with sea rubber, and is intended to solve the conventional problems in both operability and effectiveness.

(Means for Solving the Problems) The present invention involves generating radicals or peroxides on the fiber surface, and then attaching a mixture of a radically polymerizable compound and a latex compound to the fiber surface. This is a method for producing a rubber e-fiber composite, which is characterized in that the mixture is then coated with rubber on the same surface and vulcanized.

The fibers of the present invention include synthetic fibers such as polyamide, polyester, and polyr-grill; natural fibers such as 1" fiber, silk, cotton, and linen; and semi-synthetic fibers such as 1)-Yo' and acete-1. Contains.・: Among these, it has the greatest effect on synthetic fibers.

Fibers such as fibers include cotton, fibers, slivers, threads, fabrics, knitted fabrics, felt fibers, etc.

What is a compound capable of radical polymerization in the present invention?

A compound whose polymerization proceeds by radical reaction,
N,N'-methylenebisacrylamide.

Having two or more unsaturated bonds, such as methylene bismethacrylamide, acrylamide methyloluric acid E, N, N-diallylacrylamide diacrylic T-midoglymexazal adduct, pentaerythritol triacrylate,
Hydrophilic Vt is preferable.

In addition, the labnox compounds according to the present invention include SBR, B, rubiridine, and chloroI cosulfonated polyXdi! Each time, select a latex such as non-woven material that is highly compatible with the adhesive rubber. 1. use.

Although there is no particular limitation on the method of generating radicals or bar 4 oxides on the fiber surface of the present invention, low-temperature plasma treatment is practical, and plasma discharge is generated by applying high-temperature plasma. Among them, glow discharge, which allows for uniform treatment, is preferable.The reduced pressure condition, C, is preferably 0.01''15 torr, and the treatment time is preferably 1 second to 10 minutes.The apparatus used, It also depends on the fiber to be treated.

In addition, the gases used are N21 He, Ar+ CO2
1C011 (20, air. 02. NH3, etc. are mentioned, and gases such as NH3 + 02 are particularly preferred.

The rubber used in the present invention refers to natural rubber or synthetic rubber that can be vulcanized from sulfur or non-sulfur, and includes diene rubber, olefin rubber, and the like.

Examples of the tsene rubber include polyisoprene, polybutadiene, SBR, NBR, etc., and examples of the olefin rubber include ethylene-propylene rubber, butyl rubber, and the like.

(Function) Plasma is irradiated onto the fiber surface to generate radicals or peroxide on the fiber surface, and then the mixture of the vinyl compound and latex described above is applied to the surface of the fiber. Due to the heat during vulcanization, the radicals on the fiber surface -L and the vinyl compound form a bond through a radical reaction, and furthermore, the latex on the vinyl compound,
In addition, radical polymerization proceeds between the latex and the rubber, and between the vinyl compound and the rubber.1 As a result, it becomes possible to obtain a strong bond between the fiber and the rubber.

For this reason as well, it is preferable to use a beer compound having two unsaturated bonds.

(Example) Example 1 Processed yarn fabric (500 denier, 96 filaments) made of 100% polyester was mixed with 20 g of nonionic activator.
/e, Soda ash 20g/Ite 80″C x 40 minutes scouring,
After thoroughly washing with water, it was dried.

! Low temperature plasma treatment conditions Air: Air 20cc/min Depressurization degree: 0.5 torr Applied voltage: 2kv Frequency: L3.56 MHz Processing time: 30 seconds Next, the following treatment liquid was applied to this treated fabric.

Chlorosulfonated polyethylene latex: 10 parts (Nisprene L-450: 5! Tetsu Kagaku Kogyosha! 2) Water
= 10 parts N, N'-methylenebisacrylamide: 0.1 After immersing the fabric in the above mixed solution, apply a treatment liquid of 40% based on the weight of the fabric with a mangle, then roll it up and heat it to 80% by heat setter.
Drying was performed at ℃ for 3 minutes. Thereafter, it was cut into 15cm squares and used for an adhesion test.

Rubber used for adhesion test with rubber: EPDM (manufactured by Sumitomo Chemical Industries: Esplen) After this EPDM rubber was made to a thickness of 1■■, it was cut into 15 cm squares, and the above treated cloth was scissored from above and below to perform vulcanization. .

Vulcanization conditions Temperature: 150°C Pressure crab 10 kg/c ■3 Time: 30 minutes To measure the adhesive strength, after cutting into 2.5 cm width, the strength was measured by T-peeling with Tensilon (Toyo Baldwin 5J). .

The peeling conditions were as follows.

Tensile speed = 50%/win Environmental temperature and humidity = 20°C 160% R1 (Example 2 Other conditions were exactly the same as in Example 1, and a vinyl compound was treated with an acrylamide glyoxazal compound adduct in Example 1. A similar test was conducted.

Comparative Example 1 A test similar to Example 1 was conducted under the same conditions as in Example 1 except that the base fabric was not irradiated with plasma.

Comparative Example 2 A test similar to Example 1 was conducted under the same conditions as in Example 1 except that no vinyl compound was added to the treatment liquid.

Comparative Example 3 Using a fabric that had been refined in the same manner as in Example 1, plasma graft polymerization was performed under the following conditions.

Gaseous Niacrylic Acid 5 cc/min Degree of Decompression: Q
, 3 torr Applied voltage: 2 kV Frequency: 13.58 MHz Processing time = 30 seconds or less was performed in the same manner as in Example 1.

The above test results are summarized in Table 1.

Table 1 As is clear from the results in Table 1, good adhesion was not obtained when plasma was not irradiated or when no vinyl compound was added even after irradiation.

That is, it can be seen that good adhesion between the polyester fabric and the rubber can be obtained only when the radicals generated on the polyester surface by plasma irradiation form a bond with the vinyl compound through a radical reaction. In addition, in the method of plasma graft polymerization, the vinyl compound after polymerization has few vinyl groups and bonding with latex or rubber is difficult to occur, so that good engraftment cannot be obtained. This also shows that plasma graft polymerization is undesirable because unsaturated bonds necessary for adhesion are consumed.

It can also be seen that a vinyl compound with one unsaturated bond is not preferable because the unsaturated bond is quickly consumed.

(Effects of the Invention) According to the present invention, radicals or peroxide generated on the fiber surface by low-temperature plasma irradiation, etc. efficiently react with the vinyl compound, and further radical polymerization can occur between the vinyl compound, latexka, and rubber. becomes.

As a result, a strong bond can be formed between the fibers and the rubber, making it possible to obtain a rubber fiber 11 composite with significantly improved adhesion.

Patent applicant: Toyobo Co., Ltd.

Claims (1)

[Claims] After generating radicals and/or peroxide on the fiber surface, a mixture of a radically polymerizable compound and a latex compound is applied to the fiber surface, and then rubber is applied to the mixture-applied surface and vulcanized. A method for producing a rubber/fiber composite, characterized by: