JPH03167372A - Polyester fiber for composite material with chlorosulfonated polyethylene and chloroprene-acrylic rubber - Google Patents

Abstract

PURPOSE:To improve the adhesivity of polyester fiber to a special polar rubber by treating an aromatic polyester fiber, etc., with a treating agent containing a specific compound and treating the product with a treating liquid produced by compounding a specific chlorophenol compound to alkylresorcin-formalin- rubber latex. CONSTITUTION:The adhesivity of a linear aromatic polyester fiber or aromatic polyamide fiber to chlorosulfonated polyethylene and chloroprene acrylic rubber can be improved by treating the fiber with the 1st treating liquid containing (A) a polyoxide compound, (B) a blocked polyisocyanate compound and (C) a rubber latex and then with the 2nd treating liquid produced by compounding an alkylresorcin.formalin.rubber latex(AFL) with (D) a chlorophenol compound produced by the cocondensation of p-chlorophenol and resorcinol with formaldehyde and having a molecular weight distribution corresponding to the ratios of the formula I (dinuclear compound), formula II (trinuclear compound) and formula III (tetranuclear compound) of (5-10):(5-15):(90-15). The weight ratio of AFL/D is 65/35-75/25.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a linear aromatic polyester fiber that has dramatically improved adhesion to two types of rubber at the same time.

That is, chlorosulfonated polyethylene (hereinafter referred to as CSP)
Abbreviated as E) and chloroprene acrylic rubber (CRAG)
It relates to polyester fibers that have extremely high adhesion to both rubbers in composite molded products with (hereinafter referred to as "rubber rubber"), and is used in applications such as rubber boats where two types of rubber materials are laminated via a polyester base fabric. It is something.

Prior Art Linear aromatic polyester fibers have high strength and high Young's modulus, and are widely used in rubber reinforcing composites and the like. By the way, in recent years, polyester fibers, which are excellent reinforcing fiber materials, have come to be used as reinforcing materials for even higher performance special rubbers. When adhering to this special rubber, the surface of linear aromatic polyester fibers is inactive, and at present there is no adhesion technology that can withstand long-term use.

As the linear aromatic polyester fiber, a polyester fiber whose main constituent is a repeating unit represented by the following general formula is preferably used, and especially a glycol whose main constituent is at least one type of glycol selected from ethylene glycol and tetramethylene glycol. A certain amount of polyester is preferably used.

{OC4 朕coo (cBO). O+ (r+ is an integer of 2 to 6.) The polyepoxide compound used in the first treatment agent of the present invention has at least two or more epoxy groups in one molecule. It is a compound containing 0.2 g equivalent or more per 100 g, and is a reaction product of polyhydric alcohols such as ethylene glycol, glycerol, sorbitol, pentaerythritol, and polyethylene glycol with halogen-containing eboxides such as shrimp chlorohydrin, and resorcinol. ·Screw(
4-Hydroxyphenyl> Reaction products of polyhydric phenols such as dimethylmethane, phenol/formaldehyde resin, resorcinol/formaldehyde resin and the above halogen-containing epoxides, oxidizing unsaturated compounds with peracetic acid or hydrogen peroxide, etc. The resulting polyepoxide compounds include 3,4-epoxycyclohexene epoxide, 3,4-epoxycyclohexenemethyl-3,4-epoxycyclohexenemethyl rupoxylate, and bis(3,4-epoxy-6-methyl). Among these, reaction products of polyhydric alcohols and epichlorohydrin, that is, polyglycidyl ether compounds of polyhydric alcohols, are particularly preferred because they exhibit excellent performance.Such polyepoxide compounds It is usually best to use it as an emulsion. To make an emulsion or a solution, for example, such a polyepoxide compound can be used as it is, or if necessary, dissolved in a small amount of a solvent, and then mixed with a known emulsifier such as an alkynolebenze diluent. Emulsify or dissolve using sodium lephonate, dioctinolesulfosuccinate sodium salt, nonylphenol ethylene oxide adduct, etc.

Next, the blocked polyisocyanate compound used in the first treatment agent of the present invention is an addition compound of a polyisocyanate compound and a blocking agent, and upon heating, the blocked components are liberated to produce an active polyisocyanate compound. It is something. As polyisocyanate compounds,
For example, tolylene diisocyanate, metaphenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenylisocyanate, triphenylmethane triisocyanate, etc., or these polyisocyanates and compounds having two or more active hydrogen atoms, such as trimethylolpropane, Examples include polyalkylene glycol adduct polyisocyanates containing terminal incyanate groups, which are obtained by reacting hentaerythritol and the like at a molar ratio of isocyanate groups (-NGO) to hydroxyl groups (-OH) exceeding 1. In particular, aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, and polymethylene polyphenylisocyanate are preferred because they exhibit excellent performance.

Examples of blocking agents include phenols such as phenol, thiophenol, cresol, and resorcinol, aromatic secondary amines such as diphenylamine and xylidine, phthalic acid imides, lactams such as cabrolactam, acetoxime, methyl ethyl ketoxime, etc. Oximes, acidic sodium sulfite, and the like can be used.

The rubber latex is nitrile butadiene rubber latex or chloroprene acrylic rubber latex, and these are used alone.

The first processing agent contains the above-mentioned polyeboxide compound (A), blocked polyisocyanate compound (B), and rubber latex (C), and (A). (B). (C) The weight ratio of each component is (A) / [(A) + (B)] is 0,0
5~0.9, (C)/[(A)+(B)] is 0.5~
It is desirable to use it so that it becomes l5. Especially (A
) / [(Al + (B)] is 0.1 to 0.5, (
C) It is preferable to mix so that /((A)+(B)) is in the range of 1 to 1O.Here, (A)/[(A)
+(B)] outside the above range, the state of rubber adhesion to the fibers tends to deteriorate and the adhesiveness tends to decrease. (C)
If /[(A)+(B)] is smaller than the above range, the treated fibers will become hard, which may lead to a decrease in shapeability, workability, and fatigue resistance of hoses etc. during use; If it exceeds this range, the adhesiveness will decrease.

The total solid concentration including the polyepoxide compound {A}, blocked polyisocyanate compound (B) and rubber latex (C) is used in a range of 1 to 30ffi1%, preferably 3 to 15% by weight based on the weight of the fiber. . If the concentration is too low, the adhesion will decrease, while if the concentration is too high, it will become hard and the moldability, workability, and fatigue resistance will decrease.

A dispersant when using the first treatment composition as an aqueous dispersion,
That is, an appropriate amount of the surfactant is 0 to 15% by weight, more preferably 10% by weight or less, based on the total solid content of the first treatment agent, and if it exceeds the above range, it tends to impair adhesion. .

The second treatment agent of the present invention is a composition containing resorcinol/formalin/rubber latex, and the resorcinol/formalin/rubber latex used here is usually called RFL, which is a combination of resorcinol and formaldehyde. Molar ratio 1=0.5 to 1:4, especially 1:1 to 1:2
It is preferable to use the range of .

As a rubber latex, it is necessary to adhere to both CSPE and CRAG at the same time, and excellent performance is shown when nitrile butadiene rubber latex (NBR latex) or chloroprene acrylic rubber latex (OR latex) is used alone. .

The blending ratio of resorcinol/formalin and rubber latex also depends on the blending ratio of the special chlorophenol compound (D) described below. It is desirable that the solid content ratio be in the range of 1:7 to 1:9. If the ratio of rubber latex is too small, the treated fiber material will become hard, resulting in poor moldability, workability, and fatigue resistance.

On the other hand, if it is too large, satisfactory performance cannot be obtained.

The blending ratio of the above-mentioned RFL and special chlorophenol compound (D) is RFL/(D) = 65/35 to 75/25.
[Weight ratio] is preferred. If it is outside this range, the adhesiveness with highly polar special rubber will decrease. The special chlorophenol compound (D) used here is a compound obtained by co-condensing parachlorophenol and resorcin with formaldehyde, and is a dinuclear (n), trinuclear (I[I> , the proportion of tetranuclear bodies or more (IV) is 5 to 10
It is a special chlorophenol compound having a molecular weight distribution of: 5 to 15: 90-75.

In the present invention, resorcin formaldehyde <RF)
By blending a specific rubber latex with a specific chlorophenol compound, compared to the case of using conventional RF and a specific rubber latex alone, the effect of halogen in the adhesive improves the adhesion of fibers and adhesion. CSPE, C which is rubber
The compatibility (affinity) with the functional groups in RAG during vulcanization is increased, and good adhesion between the fibers and the matrix rubber is expressed in the molded rubber composite. In the molecular weight distribution of the compound, the proportion of compounds having four or more nuclear bodies is high, that is, it is assumed that the crosslinking density of the adhesive layer is high because the molecular weight is high.

This is effective when different rubbers are adhered on both sides of the rubber composite reinforced aromatic polyester fabric, such as for rubber boats. In other words, adhesive volister is particularly effective when using chloroprene acrylic rubber (CRAG) with low gas permeability on one side and chlorosulfonated polyethylene (CSPE) with excellent light resistance, ozone resistance, and oxidation resistance on the other side. It provides fiber.

The above-mentioned second processing agent is preferably adjusted to have a solid content of 10 to 20% by weight.

In order to attach the first treatment agent and the second treatment agent to the fiber material, any method such as contact with a roller, application by spraying from a nozzle, or immersion in a solution can be adopted. The amount of solid content deposited on the fiber material is preferably 0.5 to 5% by weight as the first treatment agent composition and 1 to 5% by weight as the second treatment agent composition. In order to control the amount of solid content adhering to the fibers, means such as squeezing with a press roller, scraping with a scraper, blowing off with air, suction, beating with a beater, etc. may be used.

In the present invention, after the fibers are treated with a first treatment agent, they are dried and heat treated preferably at a temperature of 180 to 200°C, and then treated with a second treatment agent to a temperature of 120°C or higher, preferably at a temperature of 180 to 200°C.
Dry and heat treat at a temperature of 80 to 200°C. If the temperature of drying and heat treatment is too low, the adhesion with the matrix rubber will be low, while if it is too high, a part of the adhesive composition, especially the rubber latex, will deteriorate and become unusable.

Effects of the Invention The fiber of the present invention has better moldability with rubber than conventional fibers.
That is, the present invention provides a highly practical rubber composite that has excellent processability and adhesion with polar chloroprene acrylic rubber and chlorosulfonated polyethylene.

Example Hereinafter, the present invention will be specifically explained with reference to Examples.

In addition, in the example! IJM adhesive strength, T adhesive strength, etc. are values determined as follows. This figure shows the adhesive strength between a fabric that has been subjected to a single-strength process and rubber. The thickness between the fabrics is 0. Sandwich the rubber sheet of 4++++a,
Furthermore, rubber sheets with a thickness of 1 mm+ were placed on both sides, under almost no pressure (less than 5 kg/a1l in gauge pressure), 160
℃ or 180℃ for 5 minutes, then 2. 5
The composite was cut into 4 cm pieces, the fabrics on both sides were held in a T-shape, and peeled off at a speed of 200 mm 2 /min. The force required for peeling was expressed in kg/inch. The peeling status at that time was also evaluated by visual judgment.

Examples 1 to 4, Comparative Examples 1 to 8 6 g of Denacol EX-611 (manufactured by Nagase Sangyo ■, sorbitol polyglycidyl ether) as a surfactant,
Add 4 g of Neocol SW-30 (manufactured by Kogyo Seiyaku tII, 30% aqueous solution of dioctyl sulfosuccinate sodium l1 salt) and dissolve uniformly.
14 g of P (manufactured by DuPont ■, 4.4-diphenylmethane diisocyanate phenol block), 4 g of Neocol SW-30 and 42 g of water were mixed in a ball mill for 24 hours.
The aqueous dispersion obtained by time mixing and decachloroprene Radex LA-50 (manufactured by Denki Kagaku Kogyo 11, 2
- Add 100 g of an emulsified water dispersion of a chloro-1,3-butadiene polymer (solid content concentration 50%) and mix uniformly. Alternatively, add 125 g of Nippol 1562 (manufactured by Nippon Zeon 0*, emulsified water dispersion of nitrile butadiene polymer, solid content concentration 40%) and mix uniformly. The obtained liquid mixture is used as a first treatment agent.

Also, 10% caustic soda aqueous solution 13. 5g with water 70.
In addition to 5 g, 17 g of resorcin and 14.9 g of formalin (37% aqueous solution) were added to the aqueous solution obtained by stirring well.
Add and stir thoroughly to disperse. Add this solution to 20-2
The mixture is left in an atmosphere at 5° C. for 2 to 3 hours to allow initial condensation of resorcin and formalin. Next, add Denkaku Kloprene Latex LA-50 <manufactured by Denki Kagaku Kogyo ■, emulsified water dispersion of 2-chloro-1,3-butadiene polymer, 50% concentration by weight) into 360 g or Nippor 1562. (Nippon Zeon ■, emulsified water dispersion of nitrile butadiene polymer, 40% concentration by weight) Add the above-prepared resorcin-formalin initial condensate solution to 450 g while stirring slowly. A special chlorophenol compound with a certain molecular weight distribution obtained by co-condensing chlorophenol and resorcin with formaldehyde (phenol
The ratio of nuclear bodies, 3-nuclear rests, 4-nuclear bodies or more is 7:9:8
217 g of a 40% ammonia aqueous dispersion (Crystal name: Tamanol KP904L, manufactured by Arakawa Chemical Industries, Ltd.) and 217 g of water were thoroughly stirred and mixed and dispersed.

Add water to obtain an appropriate concentration. The obtained liquid mixture is used as a second treatment agent.

500 denier/250 filament of polyester fiber 38 vertically, 5 pieces/inch, horizontal 41 pieces/inch
A plain weave fabric was obtained with a density of .

After immersing this in the first treatment agent, it is squeezed with a mangle at a pressure of 1.0 kg/1, dried at 130°C for 2 minutes, and then aged at 200°C for 2 minutes. Next, it was immersed in a second treatment agent, dried at 130°C for 2 minutes, and then treated with a second treatment agent.
Maturing at 00°C for 2 minutes. The solid content of the first treatment agent was 2.6% by weight and the solid content of the second treatment agent was 3.6% by weight on the treated polyester fabric.

Between the thus obtained treated polyester products, CRAG
Alternatively, unvulcanized rubber of CSPE was sandwiched and vulcanized at 160°C or 180°C for 5 minutes.

The above experiment was repeated with various weight ratios of RFL and special chlorophenol compound (D) as shown in Table 1. Experiments were also conducted in which latex was varied at the optimum ratio. The experimental results are shown in Table 1.

Claims (1)

[Scope of Claims] Linear aromatic polyester fibers or aromatic polyamide fibers are treated with a first treatment agent containing a polyepoxide compound (A), a blocked polyisocyanate compound (B) and a rubber latex (C), and then an alkyl A fiber made by treating resorcin formalin rubber latex (AFL) with a second treatment agent containing a special chlorophenol compound (D), in which the special chlorophenol compound (D) converts parachlorophenol and resorcin into formaldehyde. It is a co-condensed compound, and the ratio of binuclear bodies (II), trinuclear bodies (III), and tetranuclear bodies or more (IV) represented by the following structural formula is 5 to 10:5 to 15:90 to 75. It is a special chlorophenol compound with a molecular weight distribution, and the blending ratio in the second treatment agent is AFL/D = 65/35 to 75/2.
5 [weight ratio], and the rubber latex is nitrile butadiene rubber latex or chloroprene acrylic rubber latex, a polyester fiber for a composite material with chlorosulfonated polyethylene and chloroprene acrylic rubber. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV)