JPH10212496A - Cleanser for laundry, and laundering - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cleanser for laundry capable of effectively preventing resoiling of a material to be washed when washing, and useful for a polyester fiber product, a complex fiber product of the polyester and cotton by including a specific polyester resin and a surfactant. SOLUTION: This cleanser for laundry includes (A) a polyester resin of formula I [R<1> is HO or HO(R<2> O)a ; R<2> is a 2-3C alkylene; (a) is 1-200; (b) is 2-100; R<3> is H or a group of formula II], (preferably having 1,000-200,000 weight average molecular weight) preferably of 0.5-5wt.%, and (B) a surfactant such as an alkylbenzenesulfonate, preferably of 7-30wt.%. When washing a soiled material, the laundry is preferably carried out by adding the polyester of the formula I to washing.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a laundry detergent and a washing method. More specifically, the present invention relates to a laundry detergent for washing polyester fiber products and polyester / cotton composite fiber products, which can effectively prevent re-contamination of an object to be washed by dirt released in a washing liquid. And a washing method.

[0002]

2. Description of the Related Art It is known that when washing contaminants, the object to be washed is re-contaminated by dirt once detached from the object to be washed. Various anti-redeposition agents are being investigated. For example,
Carboxymethylcellulose, hydroxymethylcellulose and the like are typical examples, and are used in many detergents as anti-redeposition agents. However, the effect is weak for polyester fiber products and polyester / cotton composite fiber products, etc., and when the stain is severe, the object to be washed is re-contaminated during washing, and as a result, a satisfactory cleaning effect cannot be obtained. Has often occurred.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a laundry detergent and a washing method capable of improving the effect of preventing re-staining of polyester fiber products and polyester / cotton composite fiber products. Things.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, by causing a polyester resin having a specific structure to be present in the washing liquid, a polyester fiber product or polyester It has been found that re-contamination during washing of cotton / composite fiber products can be effectively prevented, and based on this finding, the present invention has been completed. That is, the present invention provides (1) a laundry detergent comprising a polyester resin represented by the general formula [1] and a surfactant;

Embedded image (Wherein, R ¹ is HO— or HO (R ² O) a-, R ² is an alkylene group having 2 to 3 carbon atoms, and R ² O
May be only one kind, or two kinds of R ² O may be added in random or block form, a is 1 to 200, and in the same molecule, a is all the same and also, may be different, b is 2~100, R ³
Is a hydrogen atom or a group represented by the general formula [2]. )

Embedded image (2) The weight average molecular weight of the polyester resin is 1,000
The laundry detergent according to item (1), which is from ~ 200,000.
(3) a washing method characterized by adding a polyester resin represented by the general formula [1] to a washing liquid when washing contaminants;

Embedded image (Wherein, R ¹ is HO— or HO (R ² O) a-, R ² is an alkylene group having 2 to 3 carbon atoms, and R ² O
May be only one kind, or two kinds of R ² O may be added in random or block form, a is 1 to 200, and in the same molecule, a is all the same and also, may be different, b is 2~100, R ³
Is a hydrogen atom or a group represented by the general formula [2]. )

Embedded image And (4) the polyester resin has a weight average molecular weight of 1,
(3) The washing method according to item (3), wherein the washing method is 000 to 200,000.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The laundry detergent of the present invention contains a polyester resin represented by the general formula [1].

Embedded image In the general formula [1], R ¹ is HO— or HO (R ² O) a
And R ² is an alkylene group having 2 to 3 carbon atoms;
R ³ is a hydrogen atom or a group represented by the general formula [2].

Embedded image The polyester resin represented by the general formula [1] used in the present invention comprises an aromatic dicarboxylic acid or a derivative thereof and a general formula H
From glycol represented by ^{O- (R 2 O) a-} H, can be prepared by known methods. As the aromatic dicarboxylic acid, terephthalic acid, isophthalic acid and phthalic acid can be mentioned, and as the derivatives thereof, for example, lower alkyl esters such as dimethyl ester, diethyl ester, dipropyl ester and dibutyl ester of these dicarboxylic acids And chlorides of these dicarboxylic acids, and phthalic anhydride.
One of these aromatic dicarboxylic acids or derivatives thereof can be used alone, or two or more thereof can be used in combination.

The glycol represented by the general formula HO- (R ² O) a-H includes, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, ethylene oxide having hydroxyl groups at both ends. And a propylene oxide random or block copolymer. One of these glycols can be used alone, or two or more can be used in combination. In the general formula [1], a is 1 to 200, more preferably 1 to 15
0. When a exceeds 200, the viscosity of the polyester resin represented by the general formula [1] becomes too high, and there is a possibility that handling becomes difficult. In the general formula [1], a may be all the same or different in the same molecule. The polyester resin represented by the general formula [1] in which all a are the same is obtained by reacting, for example, dimethyl ester such as terephthalic acid, isophthalic acid, and phthalic acid with polyethylene glycol having a certain molecular weight, and removing methanol. It can be produced by carrying out a transesterification reaction accompanied by polymerization and the like. In the same molecule, a polyester resin represented by the general formula [1] in which a repeating unit in which a is 1 and a repeating unit in which a is several tens to one hundred and several tens is, for example, terephthalic acid, isophthalic acid, It can be produced by reacting a dihydroxyethyl ester such as phthalic acid with polyethylene glycol having a certain molecular weight, and performing a transesterification reaction involving deethylenglycol to polymerize. In the general formula [1], b is 2 to
100, and more preferably 2 to 30. b is 1
If it exceeds 00, the viscosity of the polyester resin represented by the general formula [1] may become too high, and handling may not be easy.

In the present invention, the weight average molecular weight of the polyester resin represented by the general formula [1] is from 1,000 to 2
Preferably 10,000, and 10,000 to 5
More preferably, it is 0.000. If the weight average molecular weight of the polyester resin is less than 1,000, the effect of preventing re-staining may not be sufficiently exhibited. If the weight average molecular weight of the polyester resin exceeds 200,000, the viscosity of the polyester resin may be too high and handling may not be easy. The weight average molecular weight of the polyester resin can be determined by gel permeation chromatography using monodisperse polyethylene glycol of known molecular weight as a measurement standard substance. The polyester resin represented by the general formula [1] used in the present invention is, for example, Nicepol PR-86, Nicepol PRS, Nicepol PR-333, Nicepol PR-555 [each of which is Nichika Chemical Co., Ltd.]. It is commercially available. In the laundry detergent of the present invention, the content of the polyester resin represented by the general formula [1] is not particularly limited, but is usually 0.1.
-10% by weight, preferably 0.5-5% by weight
Is more preferable. When the content of the polyester resin represented by the general formula [1] is less than 0.1% by weight,
There is a possibility that a sufficient recontamination prevention effect may not be exhibited. The greater the amount of the polyester resin represented by the general formula [1] in the detergent, the greater the effect of preventing recontamination. However, the content of the polyester resin represented by the general formula [1] is 10% by weight. If it exceeds, the performance balance as a detergent may be lost. The laundry detergent of the present invention contains a surfactant. There is no particular limitation on the surfactant used, for example, alkyl benzene sulfonate, α-olefin sulfonate, polyoxyethylene alkyl sulfate, anionic surfactant such as alkyl sulfate, polyoxyethylene alkyl ether, Nonionic surfactants such as polyoxyethylene aryl ether can be mentioned.

[0008] In the laundry detergent of the present invention, the content of the surfactant is not particularly limited and can be appropriately selected according to the form of the detergent such as a powder detergent and a liquid detergent. %, More preferably from 7 to 30% by weight. In the laundry detergent of the present invention, if necessary, components other than the polyester resin represented by the general formula [1] and the surfactant can be contained. Such components include, for example, softeners, foaming agents, antifoaming agents, builders, optical brighteners, bleaching agents,
Enzymes and the like can be mentioned. Examples of the softener include a cationic surfactant such as distearyl dimethyl ammonium chloride. Examples of the foaming agent include N, N-di (alkanol) alkaneamide, amine oxide and the like.
Examples of the builder include polyphosphate, silicate, carbonate, sulfate, and zeolite.
Examples of the fluorescent whitening agent include a diaminostilbene whitening agent, a bisstilbene whitening agent, and a coumarin whitening agent. Examples of the bleaching agent include perborate and percarbonate. Examples of the enzyme include amylase, lipase, and cellulase, in addition to protease.

In the washing method of the present invention, when washing contaminants, the polyester resin represented by the general formula [1] is added to the washing liquid.

Embedded image In the general formula [1], R ¹ is HO— or HO (R ² O) a
And R ² is an alkylene group having 2 to 3 carbon atoms;
R ³ is a hydrogen atom or a group represented by the general formula [2].

Embedded image In the general formula [1], a is 1 to 200, more preferably 1 to 150. When a exceeds 200,
The viscosity of the polyester resin represented by the general formula [1] may be too high, and handling may not be easy.
In the general formula [1], a may be all the same or different in the same molecule. In the general formula [1], b is 2 to 100, more preferably 2 to 30. If b exceeds 100, the viscosity of the polyester resin represented by the general formula [1] may be too high, and handling may not be easy. In the method of the present invention, the weight average molecular weight of the polyester resin represented by the general formula [1] is preferably from 1,000 to 200,000, more preferably from 10,000 to 50,000. If the weight average molecular weight of the polyester resin is less than 1,000, the effect of preventing re-staining may not be sufficiently exhibited. If the weight average molecular weight of the polyester resin exceeds 200,000, the viscosity of the polyester resin may be too high and handling may not be easy. In the method of the present invention, the method for preparing the washing liquid is not particularly limited, and the washing liquid can be prepared by dissolving a commonly used commercially available powder detergent, liquid detergent, or the like in water. Although the concentration of the detergent in the washing liquid is not particularly limited, it is usually preferably from 0.02 to 1.0% by weight.

In the method of the present invention, the concentration of the polyester resin represented by the general formula [1] to be added to the washing liquid is not particularly limited, but is usually 0.1 to 10 per 100 parts by weight of the detergent in the washing liquid. Parts by weight, more preferably 0.5 to 5 parts by weight. In the method of the present invention,
The temperature of the washing solution is not particularly limited and can be appropriately selected depending on the material to be washed, the state of contamination, and the like. Usually, it is preferably room temperature to 90 ° C, more preferably 40 to 80 ° C. Is more preferable. There is no particular limitation on the washing machine used for carrying out the method of the present invention, and a commercially available known washing machine can be used, and a program mounted on the washing machine is used for the material of the article to be washed, the state of contamination, and the like. They can be appropriately selected and used according to the requirements. According to the laundry detergent and the laundry method of the present invention, it is possible to effectively prevent re-contamination of the article to be washed during washing, particularly, polyester fiber products,
It is effective for preventing re-contamination of polyester-based washing articles such as polyester / cotton composite fiber products.

[0011]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. The re-contamination prevention property was evaluated by the following method. (1) Artificially contaminated cloth Myristic acid 10.4 parts by weight, palmitic acid 1.4 parts by weight, oleic acid 3.8 parts by weight, tristearin 8.1 parts by weight, triolein 8.1 parts by weight, cholesterol 4.3 Parts by weight, 0.9 parts by weight of cholesterol stearate, 5.2 parts by weight of paraffin wax, 5.2 parts by weight of squalene,
Tamagawa C class compressed carbon 0.5 parts by weight, Kanto loam 47.4
Parts by weight and 4.7 parts by weight of triiron tetroxide were dispersed in 1,1,1-trichloroethane at a weight ratio of 1: 100, and a cotton cloth was immersed in the liquid, and a pickup rate of 100% by a mangle. % And squeezed and air-dried. The reflectance of the artificially stained cloth is about 30%.
Met. (2) Prevention of re-contamination Under the following washing conditions, a polyester jersey and a white cloth of polyester / cotton (65/35) broad were put into the same bath as the artificially stained cloth, and a washing test was conducted. The rate is measured using a reflectometer [color meter CM-53D, Murakami Color Research Laboratory Co., Ltd.], and the recontamination rate is determined by the following equation. [Washing conditions] Detergent concentration 0.1% by weight Washing temperature 60 ° C Washing time 20 minutes Rinse time 1 minute Bath ratio 1:25 Treatment machine Rounder-o-meter [manufactured by Daiei Kagaku Seiki Seisakusho] [Recontamination rate] Recontamination rate = {(R ₀ −R ₁ ) / R ₀ } × 100 (%) where R ₀ is the reflectance of the white cloth before washing, and R ₁ is the reflectance of the white cloth after washing. The smaller the value of the recontamination rate,
Good recontamination prevention. Production Example 1 A reaction vessel was charged with 272 g of dimethyl terephthalate, 116 g of dimethyl isophthalate, 250 g of ethylene glycol and 0.1 g of zinc acetate, and heated to 170-1.
The reaction was carried out at 80 ° C. for 3 hours to obtain about 480 g of a mixture of di (hydroxyethyl) terephthalate and di (hydroxyethyl) isophthalate. Next, 280 g of this ester mixture, 820 g of polyethylene glycol (molecular weight: 4,000) and 0.5 g of antimony trioxide were charged into another reaction vessel, and the mixture was heated and heated.
The reaction was carried out at a temperature of 15 ° C. under a reduced pressure of about 15 mmHg for 3 hours to obtain about 1,000 g of a polyester resin. The weight average molecular weight of this polyester resin was determined by gel permeation chromatography [Tosoh
As a result of measurement using high-speed GPC, HLC-8120 type, standard substance for measurement: polyethylene glycol, manufactured by
000. 100 g of this polyester resin was dissolved in a mixed solvent of 10 g of isopropyl alcohol and 890 g of water to obtain an aqueous solution A of the polyester resin. Production Example 2 150 g of terephthalic acid di (hydroxyethyl) ester, 150 g of terephthalic acid di (hydroxypropyl) ester, and polyethylene glycol (molecular weight: 4,
000) and antimony trioxide (1.0 g) were charged, heated and heated, and reacted at 240 to 250 ° C. under a reduced pressure of about 5 mmHg for 2 hours, and further reacted at 260 ° C. and a reduced pressure of about 2 mmHg for 30 minutes. 800 g of a polyester resin was obtained. The weight average molecular weight of this polyester resin was about 15,000 as measured by gel permeation chromatography in the same manner as in Production Example 1. This polyester resin 1
00g, isopropyl alcohol 10g and water 890g
To obtain an aqueous solution B of a polyester resin. Example 1 Nonylphenol-ethylene oxide 8 mol adduct 50
Parts by weight, sodium dodecylbenzenesulfonate 20 parts by weight, soda ash 430 parts by weight, sodium tripolyphosphate 50
By weight, 130 parts by weight of sodium metasilicate, 300 parts by weight of sodium sulfate and 20 parts by weight of an aqueous solution of a polyester resin A were mixed to prepare a laundry detergent. Using this laundry detergent,
An evaluation of the anti-recontamination property was performed. The recontamination rate was 7.1% for the polyester jersey and 7.2% for the polyester / cotton broad. Example 2 A laundry detergent was prepared in the same formulation as in Example 1, except that the amount of soda ash was 400 parts by weight and the amount of the aqueous solution A of the polyester resin was 50 parts by weight. Using this laundry detergent, the evaluation of the anti-redeposition property was performed. The recontamination rate was 4.4% for the polyester jersey and 4.8% for the polyester / cotton broad. Example 3 Nonylphenol-ethylene oxide 8 mol adduct 23
0 parts by weight, 20 parts by weight of sodium dodecylbenzenesulfonate, 20 parts by weight of an aqueous solution B of a polyester resin and 73 parts of water
0 parts by weight were blended to prepare a laundry detergent. Using this laundry detergent, the evaluation of the anti-redeposition property was performed. The recontamination rate was 8.8% for the polyester jersey and 7.1% for the polyester / cotton broad. Example 4 A laundry detergent was prepared in the same formulation as in Example 3, except that the amount of the aqueous solution B of the polyester resin was 50 parts by weight and the amount of water was 700 parts by weight. Using this laundry detergent, the evaluation of the anti-redeposition property was performed. The recontamination rate was 5.3% for polyester jersey and 5.9% for polyester / cotton broad. Comparative Example 1 A laundry detergent was prepared in the same composition as in Example 1 except that the aqueous solution A of the polyester resin was not blended and the amount of soda ash was changed to 450 parts by weight. Using this laundry detergent, the evaluation of the anti-redeposition property was performed. The recontamination rate was 10.2% for polyester jersey and 9.2% for polyester / cotton broad. Comparative Example 2 The amount of water was 75 without mixing the aqueous solution B of the polyester resin.
A laundry detergent was prepared with the same formulation as in Example 3 except that the amount was 0 parts by weight. Using this laundry detergent, the evaluation of the anti-redeposition property was performed. The recontamination rate was 9.4% for the polyester jersey and 8.8% for the polyester / cotton broad. Table 1 shows the composition of the detergents of Examples 1 to 4 and Comparative Examples 1 and 2 and the evaluation results of the anti-redeposition property.

[0012]

[Table 1]

Examples 1 to 4 using the laundry detergent of the present invention
In Comparative Example 1, the resoil ratio was low for both polyester jersey and polyester / cotton broad, and good anti-soil repellency was exhibited, while Comparative Example 1 using a detergent containing no polyester resin was used. In Nos. 2 to 2, the recontamination rate was high and the recontamination prevention property was poor. In particular, in a polyester jersey made of 100% polyester fiber, the effect of preventing re-contamination by the polyester resin is remarkably exhibited. Example 5 Washing was performed under the above-mentioned washing conditions by adding 5% by weight of an aqueous solution A of a polyester resin to a powder detergent [Siroc AN-55, Nikka Kagaku Co., Ltd.], and the re-staining prevention property was evaluated. . The recontamination rate was 2.5% for polyester jersey and 3.1% for polyester / cotton broad. Comparative Example 3 Washing was performed under the above washing conditions using only a powder detergent [Silok AN-55, Nichika Chemical Co., Ltd.] without adding a polyester resin, and the re-contamination prevention property was evaluated. The recontamination rate was 7.6% for polyester jersey and 6.2% for polyester / cotton broad. Example 6 Instead of the powder detergent [Siroc AN-55, Nichika Chemical Co., Ltd.], the powder detergent [Siroc W-800, Nika Chemical Co., Ltd.]
, And the re-contamination prevention property was evaluated in the same manner as in Example 5, except that the aqueous solution B of the polyester resin was used instead of the aqueous solution A of the polyester resin. The recontamination rate was 2.4% for polyester jersey and
The cotton broad was 2.6%. Comparative Example 4 Instead of the powder detergent [Siroc AN-55, Nichika Chemical Co., Ltd.], the powder detergent [Siroc W-800, Nika Chemical Co., Ltd.]
The evaluation of re-contamination prevention was carried out in the same manner as in Comparative Example 3 except that was used. The recontamination rate was 6.5% for polyester jersey and 5.7% for polyester / cotton broad. Example 7 The same procedure as in Example 5 was repeated except that a liquid detergent [Sunfriend VS, Nika Chemical Co., Ltd.] was used instead of the powder detergent [Siroc AN-55, Nika Chemical Co., Ltd.]. The pollution prevention properties were evaluated. The recontamination rate was 3.
0% and the polyester / cotton broad was 3.6%. Comparative Example 5 The same procedure as in Comparative Example 3 was repeated except that a liquid detergent [Sunfriend VS, Nika Chemical Co., Ltd.] was used instead of the powder detergent [Siroc AN-55, Nika Chemical Co., Ltd.]. The pollution prevention properties were evaluated. The recontamination rate was 9.
6% and 8.2% polyester / cotton broad. Example 8 Recontamination was performed in the same manner as in Example 6, except that a liquid detergent [Lipotol OK, Nika Chemical Co., Ltd.] was used instead of the powder detergent [Siroc W-800, Nika Chemical Co., Ltd.]. The prevention was evaluated. The recontamination rate was 2.8 for the polyester jersey.
% And the polyester / cotton broad was 3.9%. Comparative Example 6 Recontamination was performed in the same manner as in Comparative Example 3 except that a liquid detergent [Lipotol OK, Nika Chemical Co., Ltd.] was used instead of the powder detergent [Siroc AN-55, Nika Chemical Co., Ltd.]. The prevention was evaluated. The recontamination rate was 8.5 for the polyester jersey.
% And the polyester / cotton broad was 7.8%. Table 2 shows the results of Examples 5 to 8 and Comparative Examples 3 and 6.

[0014]

[Table 2]

The results of Examples 5 to 8 in which washing was performed by the method of the present invention in which a polyester resin was added to the washing liquid were compared with Comparative Examples 3 to 8 in which washing was performed without adding the polyester resin.
In comparison with the results of Example 6, when the same detergent was used, the re-staining ratio of the polyester resin-added example was lower in both the polyester jersey and the polyester / cotton broad, and the washing method of the present invention showed that It can be seen that recontamination of the washing can be effectively prevented.

[0016]

According to the laundry detergent and the washing method of the present invention, it is possible to effectively prevent re-contamination of the article to be washed during washing. The detergent and washing method of the present invention are particularly effective for polyester fiber products and polyester / cotton composite fiber products.

Claims (4)

[Claims] 1. A laundry detergent comprising a polyester resin represented by the general formula [1] and a surfactant. Embedded image (Wherein, R ¹ is HO— or HO (R ² O) a-, R ² is an alkylene group having 2 to 3 carbon atoms, and R ² O
May be only one kind, or two kinds of R ² O may be added in random or block form, a is 1 to 200, and in the same molecule, a is all the same and also, may be different, b is 2~100, R ³
Is a hydrogen atom or a group represented by the general formula [2]. ) 2. A polyester resin having a weight average molecular weight of 1,
The laundry detergent according to claim 1, wherein the amount is from 000 to 200,000. 3. A washing method comprising adding a polyester resin represented by the general formula [1] to a washing liquid when washing contaminants. Embedded image (Wherein, R ¹ is HO— or HO (R ² O) a-, R ² is an alkylene group having 2 to 3 carbon atoms, and R ² O
May be only one kind, or two kinds of R ² O may be added in random or block form, a is 1 to 200, and in the same molecule, a is all the same and also, may be different, b is 2~100, R ³
Is a hydrogen atom or a group represented by the general formula [2]. ) 4. A polyester resin having a weight average molecular weight of 1,
The washing method according to claim 3, wherein the number is from 000 to 200,000.