JP2006282701A - Detergent composition for nylon-containing textile article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent for nylon-containing textile articles which can well deterge oily dirt off and can sufficiently prevent dirt redeposition. <P>SOLUTION: The detergent composition for nylon-containing textile articles comprises a hydrophilic polyamide having polyalkylene glycol residues in the main chain and a polyoxyalkylene alkyl ether. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a detergent composition for nylon-containing textiles used as a detergent for nylon-containing textiles.

Nylon fibers are excellent in properties such as tensile strength and friction strength, and are therefore very often used in textile products (for example, clothing).
The nylon fiber has excellent characteristics as described above, but has strong hydrophobicity, so when used in clothing, etc., the oily soil does not drop well in washing using water as a medium. A part of the detached dirt is liable to adhere to the clothing again (recontamination property).
Such recontamination often causes yellowing or darkening of clothing.

  Therefore, there are cleaning agents containing various agents for preventing recontamination (for example, zeolite, polycarboxylate, carboxymethylcellulose, polyethylene glycol, etc.) and agents for removing oily dirt (for example, various surfactants, etc.). It is used (for example, patent document 1 etc.).

  However, even if a detergent containing the above-mentioned various chemicals is used in clothing containing nylon fibers, the oily dirt is well removed and a detergent that sufficiently prevents re-contamination has not been obtained. is there.

  Therefore, there is a demand for a cleaning composition that can easily remove oily stains and sufficiently prevent re-contamination from clothing containing nylon fibers.

JP-A-5-194987

  In view of the above problems and demands, an object of the present invention is to provide a cleaning composition for a nylon-containing fiber product that can easily remove oily dirt and sufficiently prevent re-contamination.

  As a result of earnest research to solve the above problems, the inventors of the present invention have solved the above problems with the following cleaning composition comprising a predetermined drug for preventing recontamination and a predetermined drug for removing oily dirt. The inventors have found what can be done and have completed the present invention.

  That is, the present invention provides a cleaning composition for nylon-containing textiles, comprising a hydrophilic polyamide having a polyalkylene glycol residue in the main chain and a polyoxyalkylene alkyl ether.

  The oily soil is removed by the polyoxyalkylene alkyl ether, and the soil once removed by the hydrophilic polyamide is prevented from adhering to the nylon fiber again.

In the present invention, the hydrophilic polyamide is composed of ε-caprolactam, dicarboxylic acid, and polyethylene oxide diamine, and the polyoxyalkylene constituting the polyoxyalkylene alkyl ether contains 1 to 10 propylene oxide. It is preferable to have 4 to 16 moles of mol and ethylene oxide.
With such a configuration, oily dirt is removed and the dirt once removed is prevented from adhering to the nylon fiber again.

Furthermore, in the present invention, the hydrophilic polyamide is composed of ε-caprolactam, dicarboxylic acid, and polyethylene oxide diamine, and the polyoxyalkylene alkyl ether is an ethylene oxide adduct of a higher alcohol and HLB7˜ 14 is preferable.
Such a configuration is effective for removing general dirt (for example, water-soluble dirt, oil-soluble dirt) and prevents the dirt once dropped from adhering to the nylon fiber again.

The cleaning composition for nylon-containing textiles according to the present invention has good oily soil removal and can sufficiently prevent re-contamination.
Moreover, since the cleaning composition for nylon-containing textiles according to the present invention sufficiently prevents recontamination, the yellowing and darkening of clothing can be greatly reduced.

Hereinafter, the cleaning composition for nylon-containing fiber products of the present invention will be described.
The detergent composition for nylon-containing textiles of the present invention comprises a hydrophilic polyamide having a polyalkylene glycol residue in the main chain and a polyoxyalkylene alkyl ether.

Examples of the hydrophilic polyamide having a polyalkylene glycol residue in the main chain include, for example, polyalkylene glycol having a molecular weight of 200 to 5,000, polyethylene glycol having a molecular weight of about 200 to 4,000, and acrylonitrile or methacrylonitrile to Michael. After the addition, the diamine represented by the formula (1) or the polyalkylene oxide diamine represented by the formula (2) obtained by hydrogenation is condensed with a dicarboxylic acid component, or further lactams (ε-caprolactam) And polyamides formed by copolymerization with other polyamide-forming monomers such as alkylenediaminoalkanoates.
Examples of the dicarboxylic acid include adipic acid, sebacic acid, azelaic acid, and the like.

(式中、R1は炭素数２〜４の低級アルキレン基、例えばエチレン基、プロピレン基、ブチレン基を表し、R2は水素原子又はメチル基を表し、nは２〜１００の整数を表す。)

(In the formula, R1 represents a lower alkylene group having 2 to 4 carbon atoms, such as an ethylene group, a propylene group, or a butylene group, R2 represents a hydrogen atom or a methyl group, and n represents an integer of 2 to 100.)

(式中、R3は炭素数２〜４の低級アルキレン基、例えばエチレン基、プロピレン基、ブチレン基を表し、nは２〜１００の整数を表す。)

(In the formula, R3 represents a lower alkylene group having 2 to 4 carbon atoms, such as an ethylene group, a propylene group, or a butylene group, and n represents an integer of 2 to 100.)

Hydrophilic polyamides having polyalkylene glycol residues in the main chain are primarily linear and generally have a number average molecular weight in the range of 1,000 to 20,000, preferably 5,000 to 15,000. Further, the content of the polyalkylene glycol residue is not less than the amount necessary for imparting hydrophilicity to the polyamide, and the amount can be changed according to the constituent components of the polyamide. Is 30% by weight or more, preferably 40% by weight or more.
Examples of the hydrophilic polyamide having a polyalkylene glycol residue in the main chain include those obtained by condensing polyethylene oxide diamine and adipic acid and further copolymerizing ε-caprolactam with the condensate. .

The polyoxyalkylene alkyl ether is obtained by adding an alkylene oxide to an alcohol having an alkyl group with an average carbon number of 10 to 18, and the alcohol is preferably a primary or secondary alcohol, May be linear or branched.
Examples of the alkylene oxide include ethylene oxide and propylene oxide.
Examples of the polyoxyalkylene alkyl ether include polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether and the like. Among these, polyoxyethylene polyoxypropylene alkyl ether is exemplified. Is preferred.

As the polyoxyethylene polyoxypropylene alkyl ether, those obtained by adding 4 to 16 mol of ethylene oxide and 1 to 10 mol of propylene oxide are used. There is no restriction | limiting in particular in the aspect of superposition | polymerization with the said ethylene oxide and the said propylene oxide, Block polymerization or random polymerization may be sufficient.
Foaming can be suppressed by using the polyoxyethylene polyoxypropylene alkyl ether.

  In order to synthesize the polyoxyethylene polyoxypropylene alkyl ether, for example, a predetermined amount of an aliphatic alcohol is charged, and then solid or aqueous solution sodium hydroxide (potassium hydroxide) serving as a catalyst is charged, followed by nitrogen substitution. And dehydrating under reduced pressure in the temperature range from room temperature to 110 ° C. Next, a predetermined amount of alkylene oxide (a mixture of propylene oxide and ethylene oxide) is introduced and added at 80 to 180 ° C. In the addition reaction operation of alkylene oxide, it is preferable to perform an operation (aging operation) for continuing the reaction until a predetermined pressure is reduced and the pressure is reduced after introducing a predetermined amount of alkylene oxide. An appropriate amount of a known acid is added to the obtained reaction crude product to neutralize the catalyst, and the desired polyoxyethylene polyoxypropylene alkyl ether can be obtained.

The polyoxyalkylene alkyl ether is obtained by adding ethylene oxide to a higher alcohol, and has an HLB value of 7 to 14, preferably 11 to 13.
When the HLB value of the polyoxyalkylene alkyl ether is 7 to 14, as general soil, for example, water-soluble soil, sweat, urine components (sodium chloride, urea, etc.), food components (starch, sugar, (Fruit juices, salts, etc.) and oil-soluble stains are also effective in removing animal and vegetable oils (sebum, food oils) and mineral oils (machine oil, grease, wax, etc.).
The HLB value is calculated by the Griffin method.

  Examples of the higher alcohol include linear or branched primary or secondary alcohols having 10 to 18 carbon atoms, preferably 12 to 15 carbon atoms.

The number of moles of ethylene oxide added to the higher alcohol is 4 to 16 moles, preferably 7 to 12 moles, of ethylene oxide per mole of the higher alcohol.
When the amount of ethylene oxide to be added is less than 4 moles, there is a possibility that the detergency with respect to water-soluble dirt is deteriorated.
Moreover, when the ethylene oxide to add exceeds 16 mol, there exists a possibility that the detergency with respect to oil-soluble dirt may deteriorate.
In addition, as a method of adding the ethylene oxide to the higher alcohol, a conventionally known method can be used.

The polyoxyalkylene alkyl ether has a number average molecular weight of 200 to 1,600, preferably 300 to 900.
If the number average molecular weight is in the range of 200 to 1,600, the detergency is good.

The blending amount of the hydrophilic polyamide and the polyoxyalkylene alkyl ether in the cleaning composition for nylon-containing textiles of the present invention is such that the polyoxyalkylene alkyl is 0.005 to 0.1% by weight of the hydrophilic polyamide. The ether is 0.05 to 1% by weight, and preferably 0.1 to 0.5% by weight of the polyoxyalkylene alkyl ether with respect to 0.01 to 0.03% by weight of the hydrophilic polyamide.
If it exists in the range of the said compounding quantity, detergency will improve.

  The cleaning composition for nylon-containing fiber products of the present invention may be used in combination with one or more cleaning agents selected from an anionic cleaning agent, a powder cleaning agent containing soda ash, and the like, if necessary.

  Examples of the anionic detergent include ether carboxylic acids having a hydrocarbon group having 8 to 24 carbon atoms or salts thereof ((poly) oxyethylene (degree of polymerization = 1 to 100) sodium lauryl ether sulfate, etc.), 8 to 8 carbon atoms. Ether sulfate ester salt having 24 hydrocarbon groups [(poly) oxyethylene (degree of polymerization = 1-100) sodium lauryl sulfate, etc.], sulfosuccinate ester salt having 8 to 24 carbon atoms [mono or dialkyl Sulfosuccinic acid ester di or monosodium, (poly) oxyethylene (degree of polymerization = 1-100) mono or dialkyl sulfosuccinic acid ester di or monosodium], (poly) oxyethylene (degree of polymerization = 1-100) coconut oil fatty acid monoethanol Sodium amidosulfate, carbonization with 8 to 24 carbon atoms Sulfate having a basic group [sodium dodecylbenzenesulfonate, etc.], phosphate ester salt having a hydrocarbon group having 8 to 24 carbon atoms [sodium lauryl phosphate, (poly) oxyethylene (degree of polymerization = 1-100) Sodium lauryl ether phosphate etc.], fatty acid salts [sodium laurate, triethanolamine laurate, etc.], acylated amino acid salts [coconut oil fatty acid methyl taurine sodium, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine, N-coconut oil fatty acid acyl-sodium L-glutamate, sodium lauroylmethyl-β-alanine, etc.].

  Examples of the powder detergent include those containing soda ash, sodium metasilicate, sodium tripolyphosphate, and the like.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.

(Measurement method of number average molecular weight)
[Measurement of number average molecular weight of hydrophilic polyamide]
The number average molecular weight of the hydrophilic polyamide is a value converted by standard [name of standard substance used to prepare a calibration curve: polystyrene] by GPC method. Specifically, Tosoh Co., Ltd. (model name: HLC-8020) was used as the GPC body, a column temperature of 40 ° C., a pump flow rate of 0.5 ml / min, and a detector: RI (differential refractometer).
It was determined from the standard substance-converted molecular weight using a calibration curve of the standard substance having a known molecular weight (a calibration curve was created at 15 points of molecular weights of 266 to 1,000,000).
Column used: Shodex Asahipak GF-310HQ
Mobile phase: Tetrahydrofuran Sample concentration: 0.2% (w / v), Injection volume: 20 μl
[Number average molecular weight measurement of polyoxyalkylene alkyl ether]
The number average molecular weight of the polyoxyalkylene alkyl ether is a value converted by standard [name of standard substance used to prepare a calibration curve: polystyrene] by GPC method. Specifically, Shimadzu Corporation model name LC-VP was used as the GPC body, column temperature 25 ° C., pump flow rate 1 ml / min, and detector: RI (differential refractometer).
It was determined from the standard substance-converted molecular weight using a calibration curve of the standard substance having a known molecular weight (a calibration curve was created at 15 points of molecular weights of 266 to 1,000,000).
Column used: Megapak GEL 201F
Mobile phase: Tetrahydrofuran Sample concentration: 3% (w / v), Injection volume: 100 μl

(Measurement method of HLB value)
HLB = (molecular weight of hydrophilic group portion / molecular weight of surfactant) × 100/5.
However, a propylene glycol group shall not be contained in a hydrophilic group part or a hydrophobic group part.

(Production of contaminated cloth: Dascon stain)
Put 600g of Φ1mm glass beads in a 1L beaker, 2.5g of mineral oil (petroleum hydrocarbon: density 0.85g / cm ³ , flash point 140 ° C or higher, kinematic viscosity around 8) and contaminants (sand on the entrance mat) After collecting the dirt such as 145 mesh sieve and adding 2.5g of fine contaminants), put it into a cotton knitted fabric contamination tester (manufactured by Koa Shokai Co., Ltd.) and rotate it forward 5 times. For 5 minutes and reverse rotation for 5 minutes to attach a stain to the nylon jersey fabric to prepare a contaminated cloth.

(Cleaning method)
Using the contaminated cloth with a Terg-O-Tometer washer, the bath ratio was set to 1:30, the detergent was added and washed with warm water at 50 ° C. for 8 minutes, then at 30 ° C. After rinsing with warm water for 3 minutes twice, dehydration was performed.
The bath ratio of 1:30 means that water is used 30 times with respect to the cloth 1 by weight.

(Recontamination test)
Nylon jersey white cloth was put together during the washing test, and the washed nylon jersey blank and blank nylon jersey white cloth were compared.

(Evaluation method of cleaning power)
1) The cleaning rate was calculated by the following formula.
Cleaning rate (%) = [(R3-R2) / (R1-R2)] × 100
R1: Surface reflectance of raw white cloth before contamination
R2: Surface reflectance of contaminated cloth
R3: Surface reflectance of the contaminated cloth after washing 2) The recontamination property was calculated by the following formula.
Recontamination (%) = [(Ra−Rb) ÷ Rb] × 100
Ra: Surface reflectance of white cloth
Rb: Surface reflectance after recontamination test The surface reflectance of raw white cloth, contaminated cloth, etc. was measured using “TC-1500SX type” manufactured by Tokyo Denshoku.

The dascon stain cleaning rate and the recontamination rate were measured using a system in which a hydrophilic polyamide and a polyoxyalkylene alkyl ether were used in combination and a system in which the hydrophilic polyamide was not used in combination.
Each formulation was shown in Example 1 and Comparative Examples 1 to 3.

Example 1
In a targotometer washer, 33 g of the contaminated cloth, 1 L of hot water at 50 ° C. and hydrophilic polyamide (manufactured by Toray Fine Chemical Co., Ltd., polyethylene oxide diamine adipate-ε-caprolactam polymer, trade name: “P-70” ) 0.01% by weight with respect to 1 L of the warm water and polyoxyalkylene alkyl ether (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkyl lauryl ether, trade name: “DKS NL-Dash 408”) 0.05% by weight was added and washed at 100 rpm for 8 minutes. Thereafter, the washed contaminated cloth was rinsed with 1 L of warm water of 30 ° C. for 3 minutes. This rinsing was performed twice, and after dehydration, the cleaning rate and the recontamination rate of the dirty cloth after washing were determined. The results are shown in Table 1.
The HLB of “DKS NL-Dash408” was 12.0.

(Comparative Example 1)
The same operation as in Example 1 was performed using only warm water without using hydrophilic polyamide and polyoxyalkylene alkyl ether, and the dascon stain cleaning rate and the recontamination rate were determined. The results are shown in Table 1.

(Comparative Example 2)
As a hydrophilic polyamide (trade name: “P-70”, manufactured by Toray Fine Chemical Co., Ltd.), the same operation as in Example 1 was performed using only 0.01% by weight with respect to 1 L of the hot water, and the dascon dirt cleaning rate And the recontamination rate was determined. The results are shown in Table 1.

(Comparative Example 3)
The same operation as in Example 1 was performed using only 0.05% by weight of polyoxyalkylene alkyl ether (Daiichi Kogyo Seiyaku Co., Ltd., trade name: “DKS NL-Dash 408”) with respect to 1 L of the warm water. The dascon dirt cleaning rate and the recontamination rate were determined. The results are shown in Table 1.

(Comparative Example 4)
As hydrophilic polyamide (trade name: “P-70”, manufactured by Toray Fine Chemical Co., Ltd.), 0.01% by weight with respect to 1 L of the warm water, and an anionic activator (produced by Daiichi Kogyo Seiyaku Co., Ltd. The same operation as in Example 1 was performed using 0.05 wt% of olefin sulfonic acid soda (trade name: “Neogen AO90”) with respect to 1 L of the warm water, and the dascon stain cleaning rate and the recontamination rate were determined. The results are shown in Table 1.

The dascon stain cleaning rate and the recontamination rate were measured by changing the HLB value of the polyoxyalkylene alkyl ether used in the cleaning composition for nylon-containing textiles of the present invention.
Hereinafter, each formulation was shown in Examples 2 to 6 and Comparative Examples 4 to 10.

(Example 2)
In a targotometer washer, 33 g of the contaminated cloth, 1 L of warm water at 50 ° C. and hydrophilic polyamide (manufactured by Toray Fine Chemical Co., Ltd., polyethylene oxide diamine adipate-ε-caprolactam polymer, trade name “P-70”) 0.01% by weight with respect to 1 L of the warm water and 0.2% by weight with respect to 1 L of the warm water as a polyoxyalkylene alkyl ether (Daiichi Kogyo Seiyaku Co., Ltd., trade name “Neugen ET-65”). Was added and washed at 100 rpm for 8 minutes. Thereafter, the washed contaminated cloth was rinsed with 1 L of warm water of 30 ° C. for 3 minutes. This rinsing was performed twice, and after dehydration, the cleaning rate and the recontamination rate of the dirty cloth after washing were determined. The results are shown in Table 2. The HLB value of “Neugen ET-65” was 7.9.

(Example 3)
The same operation as in Example 1 was performed using “Neugen ET-95” instead of “Neugen ET-65”. The results are shown in Table 2. The HLB value of “Neugen ET-95” was 10.5.

Example 4
The same operation as in Example 1 was performed using “Neugen ET-115” instead of “Neugen ET-65”. The results are shown in Table 2. The HLB value of “Neugen ET-115” was 12.1.

(Example 5)
The same operation as in Example 1 was performed using “Neugen ET-135” instead of “Neugen ET-65”. The results are shown in Table 2. The HLB value of “Neugen ET-135” was 13.3.

(Example 6)
The same operation as in Example 1 was performed using “Neugen ET-165” instead of “Neugen ET-65”. The results are shown in Table 2. The HLB value of “Neugen ET-165” was 14.5.

(Comparative Example 5)
The same operation as in Example 1 was performed using only warm water without using hydrophilic polyamide and polyoxyalkylene alkyl ether, and the dascon stain cleaning rate and the recontamination rate were determined. The results are shown in Table 2.

(Comparative Example 6)
The same operation as in Example 1 was performed using only “P-70” as the hydrophilic polyamide, and the dascon stain cleaning rate and the recontamination rate were determined. The results are shown in Table 2.

(Comparative Example 7)
The same operation as in Example 1 was carried out using only “Neugen ET-65” as the polyoxyalkylene alkyl ether, and the dascon stain cleaning rate and the recontamination rate were determined. The results are shown in Table 2.

(Comparative Example 8)
The same operation as in Example 1 was performed using only “Neugen ET-95” as the polyoxyalkylene alkyl ether, and the dascon stain cleaning rate and the recontamination rate were determined. The results are shown in Table 2.

(Comparative Example 9)
The same operation as in Example 1 was performed using only "Neugen ET-115" as the polyoxyalkylene alkyl ether, and the dascon stain cleaning rate and the recontamination rate were determined. The results are shown in Table 2.

(Comparative Example 10)
The same operation as in Example 1 was performed using only “Neugen ET-135” as the polyoxyalkylene alkyl ether, and the dascon stain cleaning rate and the recontamination rate were determined. The results are shown in Table 2.

(Comparative Example 11)
The same operation as in Example 1 was performed using only “Neugen ET-165” as the polyoxyalkylene alkyl ether, and the dascon stain cleaning rate and the recontamination rate were determined. The results are shown in Table 2.

When the detergent composition for nylon-containing textiles of the present invention and powder detergent were used in combination, the dascon stain cleaning rate and the recontamination rate were measured.
Hereinafter, each formulation was shown in Example 7 and Comparative Example 11.

(Example 7)
In a targotometer washer, 33 g of the contaminated cloth, 1 L of warm water at 50 ° C. and hydrophilic polyamide (manufactured by Toray Fine Chemical Co., Ltd., polyethylene oxide diamine adipate-ε-caprolactam polymer, trade name “P-70”) As a powder detergent (sodium ash 40% by weight, sodium metasilicate 9 hydrate 15% by weight, sodium tripolyphosphate 25% by weight, polyoxyalkylene alkyl ether “DKS NL- Dash 408 ”20 wt% mixture) was added at 0.1 wt% to 1 L of the warm water and washed at 100 rpm for 8 minutes. Thereafter, the washed contaminated cloth was rinsed with 1 L of warm water of 30 ° C. for 3 minutes. This rinsing was performed twice, and after dehydration, the cleaning rate and the recontamination rate of the dirty cloth after washing were determined. The results are shown in Table 3.

(Comparative Example 12)
In a targotometer washer, 33 g of the contaminated cloth, 1 L of warm water at 50 ° C. and hydrophilic polyamide (manufactured by Toray Fine Chemical Co., Ltd., polyethylene oxide diamine adipate-ε-caprolactam polymer, trade name “P-70”) 0.01% by weight with respect to 1 L of the warm water and as a powder detergent (soda ash 40% by weight, sodium metasilicate 9 hydrate 15% by weight, sodium tripolyphosphate 25% by weight, anionic detergent “Neogen AO90” 20 0.1% by weight of 1% of the warm water was added and washed at 100 rpm for 8 minutes. Thereafter, the washed contaminated cloth was rinsed with 1 L of warm water of 30 ° C. for 3 minutes. This rinsing was performed twice, and after dehydration, the cleaning rate and the recontamination rate of the dirty cloth after washing were determined. The results are shown in Table 3.

  It has been found that the use of hydrophilic polyamide and polyoxyalkylene alkyl ether in combination improves the removal of oily stains and prevents them from being soiled again with stains once removed.

Claims (3)

  A detergent composition for nylon-containing textiles, comprising a hydrophilic polyamide having a polyalkylene glycol residue in the main chain and a polyoxyalkylene alkyl ether.   The hydrophilic polyamide is composed of ε-caprolactam, dicarboxylic acid and polyethylene oxide diamine, and the polyoxyalkylene constituting the polyoxyalkylene alkyl ether contains 1 to 10 moles of propylene oxide and 4 to 4 ethylene oxide. It has 16 mol, The cleaning composition for nylon containing textiles of Claim 1 characterized by the above-mentioned. The hydrophilic polyamide is composed of ε-caprolactam, dicarboxylic acid and polyethylene oxide diamine, and the polyoxyalkylene alkyl ether is
The detergent composition for nylon-containing textiles according to claim 1, which is an ethylene oxide adduct of a higher alcohol and is HLB7-14.