JPH0423030B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a durability treatment agent for synthetic fibers. Synthetic fibers are hydrophobic due to their chemical structure, so static electricity may occur during manufacturing, processing, and use, resulting in reduced productivity, accidents, discomfort, and
Combined with the fact that they are susceptible to electric shocks and lack of water absorption, they are prone to attracting dust from the air and becoming dirty while on display or being worn. Various methods have been proposed to improve these methods, but in general, inexpensive and easy-to-work surfactants are the main agents, antistatic agents, water absorbents, antifouling agents, etc. are used depending on the purpose. However, these materials are prone to rusting, many do not have sufficient antistatic performance under low humidity conditions, and when used on polyester fibers, they have drawbacks such as a significant decrease in color fastness. Furthermore, the biggest drawback is that the antistatic performance is completely lost after one wash. In other words, since the original properties of synthetic fibers return after one wash, it is currently impossible to prevent static electricity damage during wear, especially in the case of clothing. For this reason, there has been a strong demand for durable antistatic agents and durable antistatic processed products.
As yet, nothing has been found that can sufficiently achieve these objectives. Therefore, in order to deal with this current situation, the present inventors have conducted extensive research and have found that polyethyleneimine, which has an average molecular weight of 300 to 100,000 and has active hydrogen obtained by polymerizing ethyleneimine, has the general formula (However, in the formula, R is H or an alkyl group having 1 to 26 carbon atoms) is subjected to an addition reaction with an alkylene oxide, and then the reaction product is subjected to a Michael addition reaction with an ethylenically unsaturated monomer, and the resulting product is obtained. Synthetic fibers are treated with a combination of an amphoteric polymer compound obtained by saponifying a reaction product with an acid or alkali and a compound having at least two epoxy groups, and preferably by heat treatment. We have invented the ability to provide antistatic performance and water absorbency at the same time. Furthermore, the fiber treatment agent of the present invention can be used alone or in combination with various processing aids such as softeners, hard finishing agents, water repellents, etc. However, at the same time, the processed knits, fabrics, or dyed products thereof do not deteriorate in color fastness or weather fastness, and do not discolor, discolor, or fade due to aging, and are satisfied in all aspects. The present invention has now been completed based on the discovery that the present invention is a fiber treatment agent that can be used as a fiber treatment agent. Here, the polyethyleneimine used in the synthesis of the amphoteric polymer compound of the present invention has an average molecular weight of 300 to 10
Polyethyleneimine with 1,000 active hydrogens is used. Commercially available products can be used as the polyethyleneimine, such as polyethyleneimine.
Examples include the Epomin (registered trademark, manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.) series. The ethylenically unsaturated monomers used in the present invention include alkyl acrylates, alkyl methacrylates, acrylnitrile, methacrylnitrile, alkyl crotonates, alkyl itaconates, alkyl maleates, and alkyl fumarates. Examples include esters, and these may be used alone or in combination of two or more. The alkyl group used here preferably has 1 to 5 carbon atoms. In addition, acids used in the present invention include sulfuric acid, hydrochloric acid, nitric acid, etc., and alkalis include sodium hydroxide, potassium hydroxide, lithium hydroxide,
Examples include calcium hydroxide and magnesium hydroxide, and these acids or alkalis may be used alone or in combination. Next, as the epoxy compound having at least two epoxy groups used in the present invention, 1,3-
bis(1,2-epoxypropoxy)benzene,
1,4-bis(1,2-epoxypropoxy)benzene, 2,2-bis(P-1,2-epoxypropoxyphenyl)propane, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, glycerol diglycidyl ether , sorbitol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol triglycidyl ether, pentaerythritate tetraglycidyl ether, and novolac type polyepoxy compounds. The amphoteric polymer compound used in the present invention can be synthesized according to Japanese Patent Application No. 56-69877.
For example, this can be done as follows. First, polyethyleneimine and epoxy alkane are reacted at 50 to 150° C. for 1 to 30 hours to perform an addition reaction, and this reaction is performed either by mixing the above raw materials as they are or in an organic solvent. Then, the Michael addition reaction between the poly-N-β-hydroxyalkyl polyethyleneimine obtained above and the ethylenically unsaturated monomer is carried out without or in a solvent at 50 to 150°C for 1 to 20 hours. This completes the process. Furthermore, the subsequent saponification reaction is carried out at 90 to 120° C. for 1 hour or more with an acid or alkali in an amount of 1.0 to 1.2 times the mole of the ethylenically unsaturated monomer used.
This reaction is also carried out without or in a solvent to obtain an amphoteric polymer compound. The synthetic fiber treatment agent of the present invention uses an amphoteric polymer compound and a compound having at least two epoxy groups in combination, and the weight ratio of the amphoteric polymer compound and the compound having at least two epoxy groups is 1 to 30:
It is preferable to use 1. The fiber treatment agent of the present invention can be applied to general synthetic fiber knitted fabrics, but especially polyester, polyamide,
Effective for acrylic fiber knitted fabrics, and in practical use 0.1 to 5.0 (wt) as an active ingredient for knitted fabrics.
% fiber treatment agent alone or as a mixed aqueous solution, emulsified dispersion, or solvent-based solution with other processing aids, applied by dipping, spraying, etc., dried, preferably, and then heat-treated. Therefore, excellent and durable antistatic properties and water absorption properties can be imparted at the same time. The amount of charge, half-life, fastness to abrasion, rust prevention, texture, and water repellency shown in the test examples using the fiber treatment agent of the present invention were measured by the following measuring methods. (1) Electrification amount (frictional charging voltage) Using a Kyoto University Kaken type rotary stack tester (manufactured by Koa Shokai), a sample that had been condensed for 48 hours at 20℃ and 40%RH was subjected to a load of 500g in the same atmosphere. It was charged with Kanakin No. 3 cotton cloth for 60 seconds at a rotational speed of 4000 rpm and a voltage of 100 V, and the charging voltage at that time was measured. (2) Half-life: 20 using Honest Meter (manufactured by Shishido Shokai)
A sample that had been conditioned for 48 hours at ℃ and 40% RH was charged in the same atmosphere with an applied voltage of 10 kV and an application time of 4 seconds, and the time until the voltage was reduced by half was measured. (3) Fastness to friction Measured using a friction tester type according to the method of JIS L-0849. (4) Rustability: 0.3% insect pin (Lion Pin Needle Co., Ltd. No. 50)
After being immersed in an aqueous hydrochloric acid solution for 5 minutes, thoroughly washed with distilled water, and air-dried, it is passed through two folds made by folding two sheets of undyed, antistatic-treated polyester Amsen fabric. In this case, eight holes are created for each pin. Pass 12 pins per sample and
The cloth was left in a desiccator at 75% RH for 48 hours, and the number of rusted holes among the holes in the cloth was measured, and the number of rusted holes out of a total of 96 holes per sample was displayed. (5) Texture The original fabric treated with a texture-adjusting resin was used as the standard, and the following three grades were determined based on handling. ○ Same hardness as standard △ Slightly harder than standard × Significantly harder than standard (6) Water repellency Measured using the spray method according to JIS L-1079. (7) Washing test The washing test was carried out using a reversible electric washing machine, using Miyoshi Newspaper detergent at a rate of 2g/washing at 40℃ for 5 minutes → spin-drying → rinsing (2 minutes at room temperature) → spin-drying → rinsing. (2 minutes at room temperature)
→Dehydration was repeated once after washing. (8) Water absorption Measured according to method A of JIS L-1096. Next, examples of the present invention will be shown, but these are given for illustrative purposes and are not intended to specifically limit the present invention. Example 1 Polyethyleneimine (manufactured by Nippon Shokubai Chemical Co., Ltd., Epomin SP-110, average molecular weight: approximately 1000)
Synthesized using 24 parts of C _12-14 epoxy alkane (manufactured by Daicel Corporation), 35 parts of methyl acrylate, and 45 parts of 30% caustic soda aqueous solution in accordance with the synthesis method of patent application No. 1987-69877. Amphoteric polymer compounds
A 50% aqueous solution of Na salt was obtained. That is, _C12-14 -epoxyalkane was added dropwise over 1 hour at 80-85°C under stirring of polyethyleneimine and a nitrogen gas flow, and the aging reaction was carried out for 4 hours.
It was added dropwise over 1 hour, Michael addition reaction was carried out, aging reaction was carried out for 3 hours, and then 95~
Heating to 100℃, adding a caustic soda aqueous solution dropwise over 2 hours to carry out a saponification reaction and aging at the same temperature for 2 hours, then adding 60 parts of pure water to create a 50% aqueous solution of Na salt of an amphoteric polymer compound. I got it. Add 50 parts of this aqueous solution and 1 part of ethylene glycol diglycidyl ether (epoxy equivalent: 73) to 1249 parts of water.
% plus 2% fiber treatment agent bath was obtained. Example 2 Using 28.4 parts of polyethyleneimine (Epomin SP-018, average molecular weight: about 1800), 27.2 parts of C _12-14 epoxy alkane, 39.6 parts of dimethyl maleate, and 184.8 parts of 20% potassium hydroxide aqueous solution, Example 1 The amphoteric polymer compound K
A 30% aqueous solution of the salt was obtained. 80 parts of this aqueous solution and 20 parts of polyethylene glycol diglycidyl ether (epoxy equivalent: 500) were added to 1865 parts of water to obtain a 2.2% fiber treatment bath. Example 3 23.7 parts of polyethyleneimine (Epomin SP-003, average molecular weight: approximately 300), C _16-18 epoxy alkane
44.6 parts, acryloniloryl 20.4 parts, 35% hydrochloric acid 40.2 parts
An amphoteric polymer compound was obtained by synthesizing in the same manner as in Example 1. 17 parts of this compound and 8 parts of pentaerythritate tetraglycidyl ether (epoxy equivalent: 80) were mixed into
A bath of 1225 parts of 70 (Vol%) solution plus 2% fiber treatment agent was obtained. Example 4 54.1 parts of polyethyleneimine (Epomin SP-006, average molecular weight: approximately 600), C _12-14 epoxy alkane
77.7 parts of methyl methacrylate, 50.3 parts of 25% caustic soda aqueous solution, and 80.5 parts of a 25% caustic soda aqueous solution were used.
An aqueous solution was obtained. 107 parts of this aqueous solution and 6.1 parts of glycerol triglycidyl ether (epoxy equivalent: 140)
1 part was added to 1261.9 parts of isopropanol/water = 30/70 (Vol%) solution to obtain a 2% fiber treatment agent bath. Example 5 44.0 parts of a 50% solution of the sodium salt of the amphoteric polymer compound of Example 1, 2.5 parts of 2.2-bis(P-1,2-epoxypropoxyphenyl)propane (epoxy equivalent: 190) in isopropanol/water = 30/70
In addition to 1178.5 parts of (Vol%) solution, a bath of 2% fiber treatment agent was obtained. Example 6 Potassium salt of the amphoteric polymer compound of Example 2
Add 60.6 parts of a 30% solution and 8.4 g of polypropylene glycol diglycidyl ether (epoxy equivalent: 280) to water.
A bath of 1261 parts plus 2% fiber treatment agent was obtained. Example 7 26.3 parts of the amphoteric polymer compound of Example 3 and N,
1.5 parts of N, ^N1 , ^N1 -tetraglycidyl metaxylylene diamine (epoxy equivalent: 100) were added to 1362.2 parts of methanol to obtain a 2% fiber treatment agent bath. Example 8 98.5 parts of a 20% aqueous solution of the sodium salt of the amphoteric polymer compound of Example 5 and 1,3-bis(1,2 epoxypropoxy)benzene (epoxy equivalent: 111)
4.4 parts and isopropanol/water = 30/70 (Vol%)
In addition to 1102.1 parts of solution, a bath of fiber treatment agent was obtained. Example 9 23.7 parts of polyethyleneimine (Epomin SP-300, average molecular weight: approximately 30,000), 9.9 parts of _C16 - _C18 epoxyalkane, 29.9 parts of methyl acrylate, 25%
Synthesis was carried out in the same manner as in Example 1 using 58.5 parts of NaOH to obtain a 20% aqueous solution of Na salt of an amphoteric polymer compound. 65 parts of this aqueous solution and 10 parts of polyethylene glycol diglycidyl ether (epoxy equivalent: 300) were added to 1225 parts of water to obtain a 2% fiber treatment bath. Example 10 23.7 parts of polyethyleneimine (Epomin P-1020, average molecular weight: approximately 100,000), 78.6 parts of toluene, C ₁₂ −
Using 42.1 parts of _C14 epoxy alkane, 5.9 parts of acrylic acid methyl ester, and 11.6 parts of 25% NaOH, a reaction was carried out in the same manner as in Example 1 to form an amphoteric polymer compound.
A 15% aqueous solution of Na salt was obtained. 153.3 parts of this aqueous solution and 3 parts of glycerol triglycidyl ether (epoxy equivalent: 140) were added to 1143.7 parts of an isopropanol/water (30:70 volume ratio) mixed solution to obtain a 2% fiber treatment agent bath. Test Example 1 A dyed polyester cloth was immersed in the solution of the fiber treatment agent obtained in Examples 1 to 10, and squeezed to a squeezing rate of 100%.
Dry at 120℃ for 3 minutes, heat treat at 180℃ for 1 minute,
The obtained processed cloth was tested for the items shown in Table 1, and the results shown in Table 1 were obtained. Comparative Example A is a commercially available permanent antistatic agent for synthetic fibers (polyethylene glycol acrylate),
Comparative Example B is a commercially available antistatic agent for synthetic fibers (quaternary ammonium salt type surfactant) Test Example 2 The dyed cloth used in Test Example 1 was immersed in a bath with the following composition, and the dye was treated under the same conditions as Test Example 1. Table 2 shows the results of tests on the processed fabrics obtained. Fiber treatment agent bath 1000 parts Sumitex Resin M-3 (melamine resin manufactured by Sumitomo Chemical Co., Ltd.) 10 parts Sumitex Accelerator ACX (Sumitomo Chemical Co., Ltd.)
(amine catalyst manufactured by Asahi Glass Co., Ltd.) 1 part Asahi Guard AG-730 (fluorine resin manufactured by Asahi Glass Co., Ltd.) 20 parts Soflon S-05 (softener manufactured by Miyoshi Yushi Co., Ltd.) 5 parts Fiber treatment agent bath Using Examples 1-3 and 6,
Comparative Examples A and B are the same as Test Example 1,
It was used in place of the fiber treatment agent bath having the above composition at a concentration of 2 wt% in terms of active ingredients.

【table】

【table】

[Table] Test Example 3 Acrylic fiber knit was immersed in the bath of the fiber treatment agent obtained in Examples 1 to 3, 4, and 6, and the squeezing rate was 120%.
The fabric was squeezed, dried at 90 DEG C. for 5 minutes, and finished and set at 130 DEG C. for 1 minute.The resulting processed fabric was tested for the items shown in Table 3, and the results shown in Table 3 were obtained. In Comparative Examples A and B, baths were prepared using the same baths as in Test Example 1, each containing 2 wt% of the active ingredient.

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Claims (1)

[Scope of Claims] 1 Polyethyleneimine having active hydrogen and having an average molecular weight of 300 to 100,000 obtained by polymerizing ethyleneimine has the general formula (However, in the formula, R is H or an alkyl group having 1 to 26 carbon atoms) is subjected to an addition reaction with an alkylene oxide, and then the reaction product is subjected to a Michael addition reaction with an ethylenically unsaturated monomer, and the resulting product is obtained. 1. A treatment agent for synthetic fibers, characterized in that an amphoteric polymer compound obtained by saponifying a reaction product with an acid or an alkali and a compound having at least two epoxy groups are used together. 2 The ethylenically unsaturated monomer is an acrylic acid alkyl ester, a methacrylic acid alkyl ester, a crotonic acid alkyl ester, an itaconic acid alkyl ester, a maleic acid alkyl ester, a fumaric acid alkyl ester (all of the above alkyl groups have 1 to 5 carbon atoms) ), acrylonitrile, and methacrylonitrile.