JPS59125975A - Surface treatment of fiber by using treating liquid excellent in precipitation stability and storage stability - 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 The present invention describes surface treatment of fibers using a resorcin formaldehyde resin aqueous solution and latex (hereinafter abbreviated as RFL liquid) for the purpose of improving the adhesive strength between fibers and rubber or resin. The present inventors have developed REL using sulfohalogenated polymer latte and kusu (sulfohalogenated polymer aqueous dispersion) as latex.
We investigated the treatment and found that when performing a heat treatment called baking at a high temperature of 20 (Ic or higher) on the fibers taken out by dipping them in the RFL liquid, we found that by adding and using a zinc compound or a magnesium compound in the RFL liquid, The adhesive force between the surface-treated fibers and rubber or resin is improved, and the effect of zinc oxide is especially large. Furthermore, zinc oxide is prepared in advance as an aqueous dispersion in order to prevent precipitation. The present invention relates to an improvement of this patent application No. 57-162886.

Specifically, when using zinc oxide, which is particularly effective when performing high-temperature baking treatment, the zinc oxide must be obtained by a wet manufacturing method and have an average particle size of 1.5μ or less, particularly preferably 1.0μ or less. The present invention relates to a method for surface treatment of fibers using a surface treatment liquid characterized by extremely excellent sedimentation stability.

Wet-processed zinc oxide can generally be obtained by adding an alkali to an aqueous zinc salt solution, and the manufacturing methods thereof are described in Japanese Patent Publication No. 55-10546, Japanese Unexamined Patent Application Publication No. 57-149827, and the like. Zinc oxide produced by the wet process is manufactured in an aqueous solution, so the particle size is much smaller than that produced by the dry process, and is less than 1μ, for example, an average particle size of 0.3-0.5μ, which cannot be obtained at all with the dry process. Since zinc oxide with an ultra-fine W diameter can be easily obtained and directly obtained as an aqueous solution, it is very suitable for addition to RFL liquid. That is, it has less sedimentation than a dry product, does not require pulverization or water dispersion, and is very advantageous in terms of cost. Of course, powdered zinc oxide manufactured by wet process is also commercially available, but when ice crystals are used, although it has the feature of less sedimentation, there are few cost advantages such as water dispersion. Therefore, the general method for adding and using it is to directly add it to the RFL liquid, but it is also possible to use a method in which the RFL liquid is prepared after adding it to an aqueous resorcinol-formaldehyde resin liquid or sulfohalogenated polymer latex.

Examples will be shown below, but the present invention is not limited thereto.

Reference Examples Dry zinc oxide aqueous dispersion with an average particle size of 2.0 μm (Sample A) and wet zinc oxide aqueous dispersion with an average particle size of 0.6 μm (Sample 13)
) (Both solids content: 30%) Comparative Example Example 1 When zinc oxide is used for Rk'L treatment, zinc oxide can be added to the resorcinol formalin resin liquid, or to the sulfohalogenated polymer latex. There are methods such as adding zinc oxide to the RFL liquid. Here, we will consider the case where zinc oxide is added to the sulfohalogenated polymer latex in advance and then used for adjusting the RFL liquid.
The results of examining its zinc oxide sedimentation properties are shown.

26 f of zinc oxide (solid content 30%) was added per 200 f of Nisprene 181L-450 (solid content 40%), which is a sulfohalogenated polymer latex, and stirred. , 40 inside
- was collected. After leaving it at room temperature for a certain period of time, collect approximately 6-liter solution from each sedimentation tube from a depth of 20.4 mm, weigh approximately 5 f into a 100-meter beaker with a known weight, and measure with an accuracy of 0.1 square meters. The amount collected was weighed.

This was diluted to 50% by adding about 7% of hydrochloric acid and water, and the weight was determined to be constant. Take the furnace solution 20- to a 200-cm beaker, neutralize it with Kayai soda aqueous solution, add acetic acid-ammonium acetate buffer Ht o -t of pH 5.0 and water to bind it to about 100-cm, and use xyler orange aqueous solution as an indicator. The EDTA sample examples and reference examples show that the zinc oxide referred to in the present invention has very little sedimentation and has excellent sedimentation stability.

Example 2 The adhesive strength between ethylene propylene rubber and 6.6 nylon was measured using the present invention, and the results are shown below.

Water 242. Of, caustic soda 0.79, resorcinol 1
1. Of, 37% formalin 16.21 mixture was aged at room temperature for 15 hours to prepare a resorcin formaldehyde resin aqueous solution. sulfohalogenated polymer latte,
7x (Nisprene [phase] L-4507 solid content 40%)
256.4f, water 165.0y, zinc oxide aqueous dispersion (solid content 30%) 84. fM was mixed with the above resorcin formaldehyde resin aqueous solution to prepare an RFL solution.

A 1260 denier 6.6 nylon twin thread cord was gently dipped once in the RFL liquid without stirring the RFL liquid, and then baked in an oven.

The following compounded ethylene propylene rubber compound is used as an adherend,
After obtaining a sample for the H test by press vulcanization at 150°C for 30 minutes, the tensile speed was 800 m/min, ASTM
Measured according to D-2188-72.

FEE Bra, Ri 50 Paraffin oil lO Saliva lead flower 5 Stearic acid 1 Vulcanization accelerator) Sokunol ■rT l Sokunol ■λ10.5 Sulfur 1 What was used in the appetizer reference example B Comparison example This example is RF
If the dry zinc oxide (sample A) is used immediately after adjusting the L liquid, the amount of zinc oxide in the RFL liquid will decrease due to the sedimentation phenomenon, and the effect of preventing adhesive strength from decreasing during high-temperature baking will be impaired. On the other hand, wet zinc oxide (sample B) with a small particle size can maintain the effect of preventing the adhesive strength from decreasing during high temperature baking. RFL that can be baked at high temperatures and has excellent storage stability by using zinc oxide as referred to in the present invention.
It became possible to obtain a liquid and greatly extend the period of practical use.

Claims (1)

[Claims] Precipitation characterized in that when performing surface treatment of natural fibers or synthetic fibers using a liquid mixture consisting of an aqueous resorcinol-formaldehyde resin liquid and an aqueous dispersion of a sulfohalogenated polymer, a sulfohalogenated polymer is added and used in combination with the liquid mixture. A method of surface treating fibers using a treatment liquid with excellent stability and storage stability.