JPH02104770A - Treating agent for synthetic fiber - Google Patents

Abstract

PURPOSE:To obtain the title treating agent capable of giving fabrics treated therewith little discoloration and excellent feel and antistatic nature by reaction of polyethyleneimine of specified molecular weight with an epoxy compound at specified molar ratio followed by addition of a specified number of moles of ethylene oxide. CONSTITUTION:Polyethyleneimine 200-50000 in molecular weight is reacted with an epoxy compound of the formula (R is 9-26C alkyl) at the molar ratio 0.05-0.8 per H atom linked to the nitrogen atom in said polyethyleneimine, and 50-300mols of ethylene oxide and/or propylene oxide is added to 1mol of the above reaction product, thus obtaining the objective treating agent. When needed, this agent may be quaternarized. Textiles treated in a solution of this treating agent are excellent in feel, giving antistatic performance of high resistance to washing, being little in discoloration by heating, and also having low skin-irritating effect.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Application of the Invention) The present invention relates to a treatment agent for synthetic fibers that causes extremely low skin irritation and has excellent texture and antistatic properties.

(Prior art and its problems) Synthetic fibers are hydrophobic due to their chemical structure, so static electricity is generated during the fiber manufacturing process from spinning to weaving, processing processes such as dyeing, and during wearing. The damage caused by static electricity does not only reduce productivity in the manufacturing process and cause discomfort due to clinging, but it can also cause disasters such as fire.Furthermore, the suction power of static electricity attracts dust and dirt, causing fibers to It is also a big problem that stains on fabrics and textiles.

For synthetic fibers that tend to generate static electricity, many methods are being used to prevent static electricity from being generated, or to quickly discharge static electricity even if it occurs, so that it does not become charged.

Some of these methods use conductive monomers or polymers, but most involve kneading surfactants or surfactant compounds into synthetic fibers, or using them to coat the surface of synthetic fibers. A method is being taken to deal with it.

Surfactants used as antistatic agents in synthetic fibers include sulfate ester salt type, phosphate ester salt type anionic surfactants, quaternary ammonium salt type cationic surfactants, betaine type amphoteric surfactants, Also, polyethylene glycol type, polyhydric alcohol ester type nonionic surfactants, etc. are generally known. However, in terms of the durable antistatic effect, the coating is removed by repeated washing or mechanical force, reducing the effect, and the effect is slow to regenerate, resulting in only a very temporary effect. I can't get it.

In addition, a method for producing a permanent antistatic agent obtained by reacting a polyethylene glycolamine derivative or its hydrochloride with a compound having two epoxy groups has been reported ((1) Japanese Patent Publication No. 38-17898, (2) 38-21
850). In addition, the present inventors first reacted a compound having one epoxy group with a polyamine or polyethyleneimine, and then reacted an ethylenically unsaturated monomer therewith with a Michael addition reaction, and saponified the resulting reaction product. Fiber treatment agent using ampholytic surfactant (A)
9) and a treatment agent for fibers using a urethane resin obtained by reacting the amphoteric surfactant <A) with a compound (B) having an isocyanate group ((5) JP-A-59-17337
8) was reported.

However, although the method (11, (2)) can provide a durable antistatic effect due to friction, etc., the surface treatment film is hard, so it is not flexible and does not have a soft texture, and the hydrophobic group Therefore, it has low water resistance and is easily washed away by washing or contact with water.

In addition, the processing agents (3) and (4) are likely to be colored easily by heating and have anionic groups, but they have a hard texture (lack of slimy feel) and have poor compatibility when used for kneading. ,
The drawback is that the antistatic effect tends to deteriorate after repeated washing, and the durability is not sufficient.

In addition, the treatment agent (5) has a urethane bond, so it has a high antistatic effect and is sufficiently durable, but the fibers after treatment are hard and have low flexibility, so skin care professionals have conducted intensive studies. As a result, we have arrived at the present invention.

The present invention applies a compound represented by the general formula (where R is an alkyl group having 9 to 25 carbon atoms) to polyethyleneimine having a molecular weight of 200 to 50,000, per hydrogen atom bonded to a nitrogen atom in the molecule. in a molar ratio of 0.05 to 0.8, and then add 50 to 300 moles of ethylene oxide or/and propylene oxide to 1 mole of the reaction product, that is, the present invention. Treatment agents for synthetic fibers are
Using polyethyleneimine (hereinafter referred to as "rPEI") having a molecular weight of 200 to 50,000 represented by the formula (1), the compound represented by the general formula (1) is added in a molar ratio per active hydrogen in the molecule. A hydrophobic group is introduced into PEI by reacting at a ratio of 0.05 to 0.8, and then ethylene oxide or propylene oxide is reacted at a ratio of 50 to 300
Obtained by molar reaction. To react an epoxy compound represented by formula 11 with PEI, stir polyethyleneimine and react the epoxy compound in the presence of an inert gas with
The mixture is quenched at 150°C for 1 to 4 hours, and then the reaction is carried out at the same temperature for 2 to 6 hours to obtain a reaction product. This reaction can be carried out by mixing the above raw materials as they are, but it can also be carried out in an organic solvent. The molecular weight of PEI is 200-5
Those with a value of 0.000 are used as they are in the reaction.

The organic solvents used here include benzene, toluene,
Examples include xylene, methanol, ethanol, isopropyl alcohol, butanol, n-hexane, chloroform, and carbon tetrachloride.

The PEI used here has a molecular weight of 200 to 50,000
However, if the molecular weight is 200 or less, the texture of the resulting fiber treatment agent is excellent, but the antistatic properties are poor, and in particular, the amount of charge increases significantly with repeated washing, resulting in poor durability. The effect of sex is low.

In addition, when the molecular weight is 50,000 or more, the resulting fiber treatment agent has excellent antistatic properties and does not show any decrease in effectiveness even after repeated washing, but has a poor texture and
It does not provide any flexibility or sliminess, and is easily colored. As described above, antistatic properties and texture vary depending on the molecular weight of PEI. Therefore, in order to have both properties in a well-balanced and satisfactory manner, it is preferable that the molecular weight of PEI falls within the range of 200 to 50,000, and further, that the molecular weight falls within the range of 600 to 20,000.
More favorable results are obtained.

Next, PEI with a molecular weight of 200 to 50,000 is added with the general formula (1
) in a molar ratio of 0.05 to 1 hydrogen atom bonded to the nitrogen atom in the PEI molecule.
If the molar ratio is 0.05 or less when reacting at a ratio of 0.8, the resulting fiber treatment agent will have high hydrophilicity, the antistatic performance will be significantly reduced by washing, and a durable effect will not be obtained. Also, the texture is not good.

In addition, when the molar ratio exceeds 0.8, the hydrophilicity becomes too low and the antistatic property decreases, and the effect of repeated washing is completely lost.Even if quaternization treatment is performed to compensate for this, Not enough effect. In addition, the texture becomes hard and flexibility is lost.

Ethylene oxide (hereinafter referred to as rEOJ) or propylene oxide (hereinafter referred to as rPOJ) is added to the reaction product of PEI and an epoxy compound obtained above. moles of EO or and P.

The zero reaction, in which the reaction is carried out by blowing in at a temperature of 100 to 180°C, proceeds without a catalyst, but it can also be carried out in the presence of an alkaline catalyst such as caustic soda or caustic potash. E
When the number of added moles of OlPO is 50 or less, the molecular weight of PET is small, and the molar ratio of the epoxy compound is small,
Although it has wood-loving properties, its texture and antistatic properties are significantly reduced by washing. When the molecular weight of PEI is large and the molar ratio of the epoxy compound is large, the hydrophilicity decreases, and the hydrophilicity of the resulting treatment agent is lost, so that the desired texture and antistatic properties cannot be obtained.

In addition, when the number of added moles of EO and PO exceeds 300, P
If the molecular weight of EI is small and the molar ratio of the epoxy compound is small, the hydrophilicity will be high, but the antistatic properties and texture will be poor. The texture is poor, the flexibility is poor, and the initial effect of antistatic properties is slightly inferior, but the decline is large after repeated washing.

The addition reaction product obtained as described above can be directly dispersed in water and used for fiber treatment, but it is necessary to improve its hydrophilicity, uniformly disperse it in water, and improve its adsorption onto the fiber surface. In order to achieve this, the amine structure may be quaternized using an inorganic or organic acid.

Inorganic acids used here include hydrochloric acid, sulfuric acid, nitric acid, etc., and organic acids include formic acid, acetic acid, lactic acid, etc.

The synthetic fiber treatment agent of the present invention is used to treat synthetic fibers such as polyester, nylon, polyacrylonitrile, polyurethane, polyethylene, and polypropylene.
A similar effect can be obtained by using a blended fiber of polyester and cotton. For these fibers, the treatment agent of the present invention is
After dispersing it in water, the surface of the fiber is treated by immersing it or spraying it on the fiber, and then dried. However, without dispersing it in water, use this treatment agent as it is or dilute it with an organic solvent. The effect can also be obtained by kneading it in the fiber spinning process and then spinning it. In the case of surface treatment, the amount of adhesion is preferably 0.1 to 5% based on the weight of the dry fiber in terms of anhydride. When the treatment is carried out by kneading, it is preferably 1 to 20% based on the weight of the fiber in terms of active ingredients.

As described above, by treating synthetic fibers using the synthetic fiber treatment agent of the present invention, it is possible to impart excellent texture and antistatic properties to the fibers, and also to adhere to the fiber surfaces and prevent heat treatment. , resulting in less coloring and extremely low skin irritation. At the same time, compared to conventional fiber treatment agents, these effects are less likely to deteriorate due to repeated washing.

The present invention will be explained in detail below with reference to Examples.

〔Example〕

Test example, as shown in Table 1: 1) Molecular weight of PEI, 1i
) The reaction molar ratio of the epoxy compound per hydrogen atom bonded to the nitrogen atom in one molecule of PE, iii) The number of added moles of ethylene oxide (1) to iii) was synthesized to synthesize reactants (lI&ll to 15). , 5% of each of these
An aqueous solution or dispersion was prepared. The stability of these aqueous solutions was measured. Next, nylon fabric was immersed in these aqueous solutions and squeezed to a squeezing rate of 50%.
It was dried at ℃ for 1 hour to obtain a treated cloth. This treated cloth was heated at 20°C.
After storing it for 48 hours under 40% RH (relative humidity),
The amount of charge and texture were measured. After the measurement, the treated cloth was subjected to repeated washing tests, and the treated cloth after the repeated washing test was dried 10 times and 30 times, and then placed under the same conditions as above to measure the amount of charge. Table 1 shows these results.
Shown below.

The test method is as follows: iii. Stability of solution: 11 hl to 14 ml of reactant is placed in a 100-meter stoppered measuring cylinder.
Collect 5 g of each sample, add 95% of distilled water to it, and place it in a thermostatic water bath at 20°C for 1 hour.

After shaking it for 1 minute, it was allowed to stand at 20° C. for 2 hours, and the stability of the solution was visually judged according to the following criteria.

O:i3 No clear aqueous solution or separation was observed.

Δ: Slightly fine particles were suspended or precipitated in the solution.

×: Agglomerated particles of fine particles are floating or precipitated in the solution, and the solution is non-uniform.

(2) Electrification amount (frictional charging voltage) Using a Kyoto University Kaken type rotary static tester (manufactured by Koa Shokai), a sample that had been conditioned for 48 hours at 20°C and 4o%RH was measured in the same atmosphere under a load soo g and a rotation speed. The sample was charged at 400 rpm and a voltage of 100 V for 60 seconds using Kanakin No. 3 cotton cloth, and the charging voltage at that time was measured.

(3) Texture A handling test conducted by 10 panel testers was conducted to judge the softness and squeakiness of the fibers after treatment, ranking them from 5 to 1 based on the following criteria.

5: 9 to 10 people judged that the softness was good and there were no creaks.

4 Near - 8 people judged the softness to be good and no squeaks.

3: 5 to 6 people judged that the softness was good and there were no creaks.

2: 3 to 4 people judged that the softness was good and there were no creaks.

l: 0 to 2 people judged the softness to be good and no creaks.

(4) Washing test The washing test was carried out using a reversible electric washing machine, using Miyoshi New Jump (synthetic detergent) at a ratio of 2 g/l as a detergent, washing at 40°C for 5 minutes, then rinsing with warm water (1 rinse at room temperature). minutes)
- Rinse with cold water (2 minutes at room temperature) -> dehydration as one wash, repeat drying 10 times, then 30 times, and then subject to the above test.

Examples 1 to 5, Comparative Examples 1 to 3 Table 2 shows that each of the reaction products (Examples 1 to 5) obtained by carrying out the reaction in the same manner as shown in Table 1 was added to a 5% aqueous solution.
A polyester woven fabric was dipped, pulled up and squeezed to a squeezing rate of 50%, and then dried at 100°C for 30 minutes. After drying, the woven fabric was placed at 20°C and 40% RH for 48 hours, and the charge amount and texture were measured in the same manner as in the test example, and the washing test was repeated 10.30 times in the same manner as in the test example. After the washing test was repeated and the woven fabric was dried, the amount of charge was measured under the same conditions. Comparative examples include jetanol aminostearic acid jetanolamide (Comparative Example 1) and distearyldimethylammonium chloride (Comparative Example 2).
), polyoxyethylene ether (1=10) sorbitan monostearate (Comparative Example 3), a polyester woven fabric was treated under the same conditions as in the example and measured in the same manner. A repeated washing test was also conducted in the same manner.

The treated fabrics (before washing) treated in Examples (5 points) and Comparative Examples (3 points) used here were tested for heat coloring properties and skin irritation.

The method is as follows.

(5) Heat colorability The woven fabric after the treatment was compared with the untreated woven fabric, and the presence or absence of discoloration was determined with the naked eye according to the following criteria.

○: Almost no coloring is observed.

Δ: Slight coloring is observed.

×: Significant coloration.

(6) Skin irritation A 0.6% aqueous solution was prepared for each sample, and a test cloth was immersed in this solution, squeezed to 100%, and dried to obtain a test cloth. Each test cloth was applied to the inside of the upper arm of 20 adult men and women.
The skin was covered with two pieces of gauze and fixed, and 24 hours later, the presence or absence of skin changes was visually determined.

〔Effect of the invention〕

As explained above, the treatment agent for synthetic fibers of the present invention is produced by reacting polyethyleneimine of a specific molecular weight with a specific molar ratio of an epoxy compound per active hydrogen bonded to nitrogen in the molecule. By using the reaction product obtained by the addition reaction of several EO or PO, an extremely stable treatment agent solution can be obtained, and the synthetic fibers treated with this solution have excellent texture and antistatic properties. grant,
Furthermore, it has the characteristic of imparting properties that reduce the deterioration of antistatic properties due to repeated washing, and compared to conventional cationic and nonionic processing agents, it has less thermal coloring properties, thus discoloring the fibers. It has the following effects: it has very little risk of causing skin irritation, and has low skin irritation.

Patent applicant Miyoshi Yushi Co., Ltd.

Claims (1)

[Claims] 1. For each hydrogen atom bonded to a nitrogen atom in polyethyleneimine having a molecular weight of 200 to 50,000, there is a general formula ▲ mathematical formula, chemical formula, table, etc. ▼...・・・・・・
・・・・・・・・・(1) (where R is an alkyl group having 9 to 26 carbon atoms) is reacted at a molar ratio of 0.05 to 0.8, and then the reaction 50 to 300 ethylene oxide or propylene oxide per mole of product
The addition reaction product obtained by molar addition reaction is directly
Or a processing agent for synthetic fibers, which is characterized in that it is used after being quaternized.