JPS596952B2 - Tsuukiseibou watermelon couhouhou - Google Patents

Description

[Detailed description of the invention] The present invention relates to a breathable waterproofing method for cloth, paper, etc.

Furthermore, by attaching a water-swellable substance and a hydrophobic substance to the fiber surface of cloth or paper, the object is to obtain waterproof cloth, waterproof paper, etc. that have excellent water pressure resistance without impairing breathability.

The so-called breathable waterproof fabric, which attaches hydrophobic substances to the fiber surface to give it water repellency and leaves voids such as the weave intact, allowing air and water vapor to pass through, is used for umbrella fabric, raincoats, and skiing. It is used for applications such as anorax.

Currently, as a temporary waterproof treatment method, there are methods using oil, paraffin, aluminum acetate, metal soap, etc. alone or in combination.This method is easy to process and inexpensive, but it is temporary. You can only get the effect.

Semi-permanent methods include a method using zirconium salts of fatty acids and a method using silicone resin, and for cellulose fibers, a method using ethylene urea derivatives that has a permanent effect by chemically bonding with the hydroxyl groups of cellulose fibers. Methods include methods using pyridinium compounds of higher fatty acids, methods using chromium complex compounds of other higher fatty acids, methods using co-condensation of higher fatty acid amide methylol and methylolated melamine, methods using alkyl ketene dimers, methods using organic fluorine compounds, etc. It has been put into practical use.

However, the conventional treatment methods as described above still have insufficient waterproof function, and the inventors of the present invention have arrived at the present invention as a result of various studies.

That is, in the present invention, in the presence of water, the mixing ratio is 100:5.
It is characterized by depositing polyvinyl alcohol and zirconium chloride mixed in a ratio of ~100:100 (by weight), and then treating with an aqueous solution or a water-alcohol solution of an alkali metal salt of a higher fatty acid having 10 to 20 carbon atoms. The present invention relates to a breathable waterproofing method.

Conventional treatment methods involve attaching or bonding a hydrophobic substance to the surface of the fibers, which is expected to achieve waterproofing due to its water repellency. However, a waterproof fabric with even better breathability can be obtained.

That is, the conventional breathable waterproof fabric using a treatment agent has the disadvantage that it can only be applied to lengths and fabrics with relatively small voids such as interwoven spaces, where the waterproof function is expected to occur only due to the water-repellent action of the hydrophobic substance.

On the other hand, the treated fabric according to the present invention has a composition consisting of a water-repellent substance and a water-swellable substance, so it is not only suitable for fabrics with small pores but also for fabrics with large pores. It has the function of blocking water.

Also, in addition to this functional feature, is there a processing operation? It is extremely simple, does not require heating or baking, and is highly durable. It has the following characteristics: it can be obtained with high air permeability, it is relatively inexpensive, and it can also be used as a water-resistant glue.

The processing agent used in the present invention is an aqueous solution (A) obtained by mixing water-soluble polyvinyl alcohol, which is a water-swellable substance (but water-insoluble), and zirconium chloride in the presence of water;
and (A) an aqueous solution or water-alcoholic solution of an alkali metal salt of a higher fatty acid (B
), and the treatment is completed by dipping a cloth or the like in (A), draining the liquid, dipping it in (B), and then air-drying or heating-drying.

In the above operation, methods such as coating or spraying may be used instead of dipping.

Polyvinyl vinyl used to create the above-mentioned treatment agent (A):-)
Ly7/lz coals include those with a saponification degree of 77 to 99 mol%, a polymerization degree of 300 to 2700, or copolymers whose main component is vinyl alcohol units and which are soluble in water. .

Examples of zirconium chlorides include zirconium tetrachloride (Zrcl4) and oxyfM cyvconium (Zrcl4).
Zrocl・8H2o), etc.

The ratio of zirconium chloride to polyvinyl alcohol is 100:5 to 100:100 (weight ratio), preferably 100:10 to 100:60.

This is because if the zirconium chloride content is less than the above ratio, the degree of crosslinking of polyvinyl alcohol is small (sufficient water resistance cannot be obtained), and if the ratio is too high, the degree of crosslinking of polyvinyl alcohol is too high and the water swelling property is poor. This is because it becomes small and difficult to express its intended function.

In addition, the appropriate concentration of polyvinyl alcohol in water varies depending on the thickness of the cloth, water absorption, etc., but it is approximately
It is about 10% by weight.

The alkali metal salt of higher fatty acid of the present invention has 1 carbon number.
Examples include metal salts such as potassium and sodium salts of 0 to 20 fatty acids.

Preferably << is potassium salt or sodium salt of palmitic acid, oleic acid, or stearic acid having 16 to 18 carbon atoms.

If the number of carbon atoms is less than 10, sufficient water resistance will not be observed, and if the number of carbon atoms exceeds 20, the solubility will be low and a sufficient treatment effect will not be observed.

In addition, the concentration of these substances in water is not particularly limited, but is usually 0.0 in relation to the treatment effect and the solubility of the salt.
The amount is about 5 to 5% by weight, and even if there is some precipitated insoluble matter, there is no problem in the treatment.

Further, in order to increase the permeability to (A) and cloth, these salts may be used as a water-alcohol solution with a small amount of methanol or ethanol added.

After soaking the cloth in the treatment agent (A) used in the present invention and draining the liquid, 1
It is also possible to obtain a breathable waterproof fabric by heating and drying at temperatures above 00°C, but there are drawbacks such as damage to or coloring of the filter fabric, which may be due to the effects of dehydrochlorination of zirconium chloride, resulting in water repellency. is also not enough.

In addition, a breathable waterproof fabric can also be obtained by soaking the fabric in (A), draining the liquid, then dipping it in an aqueous solution of a base of ≧ 1, such as caustic soda or ammonia, or a basic salt such as sodium acetate, and drying it. However, it has low water repellency and becomes wet in a short period of time, which poses a practical problem.

On the other hand, when treated with (B), a dramatic improvement in water repellency was observed due to the formation of higher fatty acids due to the gelation effect of (A) and the neutralization effect of dehydrochlorination, and the above-mentioned problems were also resolved. Ta.

As a result, the waterproof function of the treated fabric is almost entirely water repellent on the fiber surface when the contact water pressure is low. It is thought that when the water pressure becomes high and reaches the fiber bundle, the swelling of the gelled polyvinyl alcohol on the fiber surface and the swelling of the gelled polyvinyl alcohol inside the fiber bundle closes the voids in the weave, blocking water flow. It will be done.

Although the above description has mainly been about waterproofing cloth, it goes without saying that the present invention can be similarly applied to waterproofing paper and the like.

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

Examples 1 to 5, Comparative Examples 1 to ;'3 150 gr of water was added to 20 gr of polyvinyl alcohol with a degree of polymerization of 1750 and a degree of saponification of 88%, and the mixture was heated at 80°C with stirring.
Dissolved in a water bath.

Cool this to near room temperature, and add 50% zirconium tetrachloride.
12g of a solution obtained by reacting and dissolving in water at a concentration of
was added, and water was further added to prepare a treatment agent (A) with a total amount of 700 gr.

Separately, 0.2% aqueous solutions of sodium capric acid, sodium myristate, sodium palmitate, sodium stearate, and sodium arachinate were each prepared.

Furthermore, a relatively coarse mesh bleached cotton cloth with a width of 20 x 20 c/rL was coated with a polyoxyethylene nonylphenol surfactant (
Product Name: Score Roll 900, Kao Soap Product) 2gr
A cloth (hereinafter abbreviated as desizing treated cloth) was prepared by immersing the fabric in a solution of 1 g of sodium carbonate and 1 Vc of water, stirring at a liquid temperature of 80° C. for 30 minutes to remove desizing, and then washing and drying with water.

This desizing treated cloth was dipped in the treatment agent (A), pulled up and drained, then dipped in the above-mentioned aqueous sodium cabrate solution, pulled up and drained, and then air-dried at room temperature.

Samples were also prepared using the above-mentioned sodium myristate solution, sodium palmitate solution, sodium stearate solution, and sodium arachinate solution instead of the sodium cabrate aqueous solution.

Furthermore, as a comparative example, after immersing in treatment agent (A), the liquid was pulled up and drained. The product was heat treated in a dryer at 110°C for 20 minutes, immersed in treatment agent (A), pulled up, and after draining the liquid.
One that was immersed in a 1% caustic soda aqueous solution, pulled up, washed with water, and air-dried, and one that was immersed in treatment agent (A), pulled up, and drained.
．． A sample was prepared by immersing it in a 2% sodium caprylate aqueous solution, pulling it up, and air-drying it.

Water repellency when water is dripped onto the surface of each sample, water repellency after 1 hour immersion in 40°C water, and fabric area 10
1crr from one side of 2c4 (1 1.4crrLφ)
Table 1 shows the results of evaluating water leakage to the opposite side (waterproofing) and air permeability in a dry state when the water pressure was lowered to 100 at a speed of 100 t/min and kept at that level for 5 minutes. Shown below.

? Examples 6 to 8, Comparative Examples 4 to 6 540 gr of water was added to 60 gr of polyvinyl alcohol having a degree of polymerization of 1750 and a degree of saponification of 98.5%, and the mixture was dissolved in a water bath at 90°C while stirring.

Cool this solution to near room temperature (100 gr each)
Divide the mixture and add to each a 50% aqueous solution obtained by reacting and dissolving zirconium oxychloride in water in the proportions shown in Table 2 in terms of Zrocl, and further adjust the polyvinyl alcohol concentration in the solution to 3%. Adjustments were made by adding water.

The same desizing cloth as described in Example 1 was immersed in each of these solutions, pulled up and drained, and then 0.3
% sodium balmitate aqueous solution and pulled up to 50°C.
The sample was dried in a dryer.

Table 2 shows the results of evaluating each sample using the same method as in Examples 1 to 5.

Examples 9 and 10 Polyvinyl alcohol 1 with a degree of polymerization of 550 and a degree of saponification of 88%
Add 90 gr of water to 0 gr and heat to 80°C while stirring.
Dissolve in a water bath, then cool to near room temperature, add 8 gr of an aqueous solution obtained by dissolving zirconium oxychloride in water at a concentration of 50%, and add water to bring the total amount to 300 gr. Two types of nylon cloth, one with a relatively coarse weave and one with a relatively dense weave, which had been subjected to the same desizing treatment as described in Example 1, were dipped into the solution, pulled up and drained, and then stearin Acid power')2
A sample was prepared by immersing the sample in a solution containing 100 gr of gr and ethyl alcohol, pulling it up, and drying it at 50°C.

Comparative Examples 7 and 8 15g of Poron MH, which is a silicone emulsion type fiber treatment agent, and 15g of Catalyst RZ-2.
(all products of Shin-Etsu Silicone) and diluted with water to 300g (3% resin content).The same desizing cloth as described in Example 9, IO was dipped in this solution and pulled up. Drain the liquid and then dry in a dryer at 150℃ for 1
This was heat treated for 5 minutes and used as a sample.

This sample was evaluated for air permeability when dry and water repellency after being immersed in water at 40° C. for 1 hour using the same evaluation method as described in Example 1.

In addition, the test area is 1 0 2 c4 (1 1.4 (1771
φ) from one side Mizumi 1 crrt/rnin
When the water pressure decreases at a speed of , and the water column reaches 50mm, just like that! The water pressure resistance is determined by the water pressure resistance when the water pressure is maintained for 5 minutes, and the height of the water column when water starts leaking from three places on the opposite side when the water pressure is increased at the same speed.
It is listed in the table.

Claims (1)

[Claims] 1 Mixing ratio 10025-1 on cloth or paper in the presence of water
Aeration characterized by depositing polyvinyl alcohol and zirconium chloride mixed at a ratio of 0:100 (by weight), and then treating with an aqueous solution or a water-mono-alcoholic solution of an alkali metal salt of a higher fatty acid having 10 to 20 carbon atoms. Waterproofing method.