JPS5851064B2 - Sen'izairiyounokaishitsushiagehouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a modified finish for textile materials, and more specifically, it provides textile materials with durable and excellent water and oil repellency, antistatic properties, and recontamination prevention properties during washing. The purpose of this invention is to provide a modified finishing method that allows for improved finishing.

Conventional finishing methods for imparting water and oil repellency to textile materials include perfluoroalkyl group-containing polymers or copolymers of these with compounds such as acrylic esters and maleic anhydride, or vinyl chloride, Treatment with copolymers such as alkyl vinyl ethers is known.

However, the finished products obtained by treatment with copolymers as described above have the following drawbacks.

One of them is that it has good repellency against oil-based dirt and oil, but it is highly charged with static electricity, which makes it easy for airborne dust and dirt to adhere to it.

Furthermore, even if it exhibits water-repellent and oil-repellent properties in the air, it lacks hydrophilicity, so it easily absorbs dirt in water, leading to recontamination when it is washed.

For the purpose of preventing the above-mentioned static electricity, a treatment method using an antistatic agent in combination has been attempted, but in this method, the antistatic agent is only mixed with water/oil repellent, and it is difficult to wash or dry. Since the antistatic agent flows out during cleaning, a durable antistatic effect cannot be obtained.

In addition, anti-water and oil-repellent polymer compounds containing hydrophilic functional groups in the main chain that are effective in preventing static electricity have also been proposed; You can only get something moderate.

Furthermore, products treated with conventional water- and oil-repellent agents have the disadvantage of losing flexibility and becoming rough and hard to the touch.

For this reason, there are restrictions on the use of products treated with conventional water and oil repellents.

The present inventors have solved the drawbacks of conventional water and oil repellent treatments as described above, and have also achieved durable antistatic properties and recontamination during washing, which were not possible with conventional water and oil repellent treatments. The present invention was arrived at as a result of various studies aimed at imparting anti-repellent properties to fiber materials in line with water-repellent and oil-repellent properties.

That is, the present invention provides a copolymer of 20 to 40% by weight of acrylate containing a perfluoroalkyl group having 3 to 15 carbon atoms and 80 to 60% by weight of acrylic acid or methacrylic acid, and polyethylene glycol having an average molecular weight of 500 to 2,000. The amount of diglycidyl ether to the above copolymer is 0.5 to 1.
Durable water and oil repellency can be achieved by treating the fiber material with an aqueous solution or an organic solvent solution that is blended at a weight ratio of 5% and a catalytic amount of a base or alkali, and then heat-treated. This is a finishing method for modifying textile materials, which can impart antistatic properties and anti-recontamination properties during washing to textile materials.

As the acrylate containing a perfluoroalkyl group having 3 to 15 carbon atoms in the present invention, various conventionally known compounds can be used.

For example, CF3 (CF2)? (CH2)1□0COCH-
CH2゜CF3(CH2)4CH20COCH=CH2
-(CF3)2CF(CF2)6(CH2)60COC
H=CH2.

(CF3)2CF(CF2)[1(CH2)30COC
H=CH2゜(CF3)2CF(CF2)6(CH2)
20COCH=CH2.

CF3 (CF2) 7 (CH2) 3COCH=
Examples include things like CH2.

In this case, H(CF2)1oCH20COCH=CH2
There are also fluoroalkyl acrylates, but as is well known, the above-mentioned perfluoroalkyl acrylates have better water and oil repellency.
~40% by weight and 80-60% acrylic or methacrylic acid
By copolymerizing the water repellent and
A compound capable of imparting oil repellency can be obtained.

Such copolymers can be produced by various conventionally known polymerization reaction methods, such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization,
It can be obtained by other known methods.

By increasing the coelectric ratio of acrylic acid or methacrylic acid to perfluoroalkyl acrylate in excess as described above, hydrophilicity and flexibility can be imparted to the copolymer.

The polyethylene glycol diglycidyl ether used in combination with the above copolymer in the present invention has an average molecular weight of 5.
The weight ratio of the copolymer to the copolymer is 0.5 or more and 1.5 or less, preferably 0.7 or more and 1.2 or less.

The excellent effects of the present invention can be obtained by blending and using this polyethylene glycol diglycidyl ether in the weight ratio according to the weight ratio of the copolymer.

Therefore, the combination of the copolymer and polyethylene glycol diglycidyl ether is the most important component of the present invention, and the combination of these specific compounds provides excellent drainage and oil repellency that could not be obtained by conventional methods. At the same time, it provides durable antistatic properties and anti-recontamination properties during washing.

Moreover, the texture of the treated material does not become rough and hard, and the flexibility can be maintained as it is.

It is believed that such remarkable effects are achieved by the chemical bonding between the copolymer and polyethylene glycol diglycidyl ether.

In other words, the epoxy groups of polyethylene glycol diglycidyl ether used together with the perfluoroalkyl acrylate copolymer are chemically bonded to the carboxyl groups in the copolymer, resulting in durable and excellent antistatic properties and washability. It is possible to obtain recontamination prevention properties along with water and oil repellency.

If the average molecular weight of polyethylene glycol diglycidyl ether is outside the range of 500 to 2,000, the above chemical bond cannot be effectively obtained.

In addition, when used in combination at a ratio other than the above, for example, if the perfluoroalkyl acrylate copolymer is used in excess, antistatic properties and anti-recontamination properties during washing can be obtained in the same way as treatments with conventional water and oil repellents. On the other hand, if polyethylene glycol diglycidyl ether is present in excess, the water and oil repellency will be poor.

In order to effectively form a chemical bond between the perfluoroalkyl acrylate copolymer and polyethylene glycol diglycidyl ether, the present invention uses a base or alkali as a catalyst in addition to the above-mentioned substances.

As the base or alkali as the catalyst, those conventionally known as reaction accelerators between hand poxy groups and organic acids can be used.

For example, primary amines such as methylamine, ethylamine, and benzylamine, secondary amines such as dimethylamine and diethylamine, tertiary amines such as trimethylamine and triethylamine, quaternary ammonium salts, phenylenediamine, piperidine, etc. Known aromatic amines such as aromatic amines can be used.

Furthermore, known alkalis such as sodium hydroxide, potassium hydroxide, and sodium bicarbonate can be used.

The added amount of bases and alkalis used as catalysts may be 1 to 5% by weight; if the added amount is less than 1% by weight, a sufficient effect cannot be obtained, and if it is 5% by weight or more, 5% by weight or less is sufficient.
It is possible to obtain exactly the same effect as when compounding by weight %.

The above-mentioned compounded composition according to the present invention can be prepared into any form such as an aqueous emulsion or an organic solvent solution aerosol according to a conventionally known method.

For example, in addition to an aqueous emulsion, an aerosol type can be created by dissolving it in an organic solvent such as acetone, methyl ethyl ketone, diethyl ether, trichlorethylene, or tetrachloroethylene, or by adding a propellant such as dichlorodifluoromethane or cellfluorotrichloromethane to these solutions. It can also be adjusted to

The blended composition liquid adjusted to various forms in this way can be processed by any method depending on the type and form of the fiber material to be processed.

For example, when treating a fabric in the form of an aqueous emulsion or an organic solvent solution, conventional coating methods such as dipping and coating can be employed.

The effects of the present invention can be obtained by heat-treating the fiber material treated with or attached to the blended composition liquid at a temperature below the melting point of the fiber material.

The method according to the invention is applicable to cellulosic fibers such as cotton, recycled cellulose, animal natural fibers such as wool and silk, and synthetic fibers such as polyamide, polyester and polyacrylonitrile.

Examples of the present invention are shown below.

The measurement of water repellency in the following examples is based on JISL1005.
For oil repellency, drop a certain amount of a composition of n-hebutane and Nujol at various mixing ratios as shown in Table 2 onto the test object, and apply the liquid after 3 minutes. The drop retention property was expressed as oil repellency.

The antistatic property was measured using a static honest meter.
The half-life of the test object to which a voltage of 0,000 volts was applied was measured at a temperature of 20° C. and a relative humidity of 40%.

The recontamination prevention property during washing was determined by stirring in a contaminated solution having the composition shown in Table 3 at a bath ratio of 1:30 and a temperature of 40°C for 10 minutes, followed by washing with water at 20°C. The degree of contamination of the test object was determined using a contamination gray scale.

That is, it was classified into five grades, with those without contamination being ranked as 5th grade and those with severe contamination being ranked as 1st grade.

The mixture was stirred for 7 minutes at a bath ratio of 1:30 and a temperature of 20° C. in perclean containing 0.01% by weight of Genbclean (a cleaning agent manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), followed by dehydration and drying.

For washing, use a household electric washing machine and process in a water bath containing 0.2% by weight of the detergent New Beads (manufactured by Kao Sekiken Co., Ltd.) at a temperature ratio of 1:30 and a temperature of 40°C for 5 minutes, then leave it at room temperature for 5 minutes. After washing with water (overflow) for 10 minutes, it was dehydrated and dried.

Durability was shown by the measured values for the above items after dry cleaning and washing 10 times.

EXAMPLES AND COMPARATIVE EXAMPLES In the examples, cotton, nylon 6'6, polyester, and polyacrylonyl l-IJ plain woven fabrics were scoured in a conventional manner.

In addition, in the examples, a blended composition of perfluoroalkyl acrylate copolymer/polyethylene glycol diglycidyl ether/base or alkali as a catalyst was prepared as an aqueous emulsion, and the various test cloths described above were immersed in this at room temperature. The liquid was removed by post-mangling, dried at 80° C. for 2 minutes, and then subjected to dry heat treatment.

The dry heat treatment temperature is 150℃ for cotton, 160℃ for nylon 66 and polyester, and 130℃ for polyacrylonitrile.
'C, and the processing time is 1 minute each.

Table 5 shows the water repellency, oil repellency, antistatic property, anti-recontamination properties, etc. of various fibers treated as described above with the copolymerization ratio and compounding ratio of the copolymer shown in Table 4. and 6 are summarized.

(However, DC-dry cleaning) As shown in the above examples, the method according to the present invention is a simple processing method that has water resistance, oil repellency, antistatic property, and recontamination prevention method that is resistant to washing and dry cleaning. It has the advantage that it can be applied to a wide range of textile materials and that the treated finished product has a soft texture.

The method according to the present invention can be said to have extremely high practical value from an industrial standpoint.

Claims (1)

[Claims] 1 Polyethylene glycol diglycidyl ether having an average molecular weight of 500 to 2000 is added to a copolymer of 20 to 40% by weight of acrylate containing a perfluoroalkyl group having 3 to 15 carbon atoms and 80 to 60% by weight of acrylic acid or methacrylic acid. The fiber material is treated with an aqueous solution or an organic solvent solution in which a catalytic amount of a base or alkali is added to the copolymer at a weight ratio of 0.5 to 1.5, followed by heat treatment. A method for modifying and finishing a fiber material, characterized by subjecting it to.