JPH07316590A - Agent for preventing color migration and restaining and detergent composition - Google Patents

Abstract

PURPOSE:To obtain a composition containing a water-soluble polymer comprising a (co)polymer of a specific amino group-containing monomer, effective for washing colored clothes and white clothes in the same bath, not requiring to select the kind of a surfactant, and not causing the problem of iron adsorption. CONSTITUTION:The preventing agent comprises a water-soluble polymer having repeating structural units derived from an amino group-containing monomer of formula I,II, III or IV (R1 to R3 are H, 1-4C alkyl, alkenyl, etc., or are bound to each other to form a ring; X is a counter ion), or formula V (R4 is H, 1-4C alkyl, alkenyl, etc.,) or its equivalent units. In the copolymer of (A) an amino group-containing monomer with (B) another monomer, the copolymerization molar ratio of the components A/B is preferably 100/0 to 50/50 (especially 100/0 to 80/20).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to color transfer that cannot be avoided when washing colored clothing and white clothing in the same bath, or dirt that has once fallen during washing adheres to clothing again. TECHNICAL FIELD The present invention relates to an additive that effectively prevents redeposition development that contaminates due to contamination, and a detergent composition containing the additive.

[0002]

2. Description of the Related Art A phenomenon in which a dye of a color clothing transfers to a white clothing when the color clothing and the white clothing are washed in the same bath is a well-known problem, and its solution is desired. It is rare. In particular, in recent years, the problem of color transfer has become serious due to the simplification of the dyeing process in order to reduce the cost of clothing and the increase in the number of overseas products with immature dyeing technology. .

Heretofore, several solutions to color transfer have been proposed. West German Patent No. 12
No. 24698 discloses a color transfer preventing effect of a cationic surfactant. However, it is impossible to simultaneously add a cationic surfactant to a clothes detergent mainly composed of an anionic surfactant, which is currently the mainstream. In addition, when a cationic surfactant is used, there is a problem that stains once dropped by washing, particularly oil stains, adhere to clothes again and cause redeposition, and there is also a problem that iron in tap water is adsorbed to clothes. .

In addition, polyvinylpyrrolidone (P
It has been known that VP) has an effect of preventing transfer (color transfer), but no other effect has been found and it has not been put to practical use. On the other hand, there is also a problem of re-contamination in which dirt that has once dropped during washing adheres to and contaminates clothes again. Currently, polyvinyl alcohol is mainly used as a redeposition preventing agent, but it has no effect of preventing color transfer.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides an additive capable of sufficiently preventing color transfer and redeposition without selecting the kind of the surfactant, and a detergent composition containing the additive. is there.

[0006]

The color transfer / recontamination inhibitor of the present invention is a polymer of an amino group-containing monomer, or a copolymer of an amino group-containing monomer with another monomer copolymerizable with the monomer. Or an equivalent thereof or a post-treated product thereof, which is represented by the general formula (I), (II) or (III)
Or (IV) or a water-soluble polymer having a repeating structural unit represented by the general formula (V) of Chemical formula 4 and derived from an amino group-containing monomer or an equivalent thereof.

[0007]

[Chemical 3] (AB represents a unit of a molecule constituting the main chain of the polymer, and the nitrogen N may be bonded to any position of AB including the terminal of AB directly or through a methylene group. Good R ₁ : hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkenyl group or a hydroxyalkyl group R ₂ : hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkenyl group or a hydroxyalkyl group, and R ₁ and R ₂ are R ₃ may be linked to form a ring: hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkenyl group or a hydroxyalkyl group X: a counter ion)

[0008]

[Chemical 4] (A-N-B: represents a unit of a molecule that contains nitrogen N and constitutes the main chain of the polymer, and the nitrogen N includes A-B end as well as A-
R ₄ which may be located at any position of B: hydrogen or an alkyl group having 1 to 4 carbon atoms, an alkenyl group, a hydroxyalkyl group or an aminoalkyl group) Further, the detergent composition of the present invention has the above-mentioned color. It is characterized by containing a transfer / recontamination preventive agent.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The color transfer / recontamination inhibitor of the present invention is
In a bent shape, it is composed of a water-soluble polymer obtained by polymerizing an amino group-containing monomer. This polymerization method is not particularly limited, such as addition polymerization represented by vinyl monomers and polycondensation represented by amino acid monomers. The amino group-containing monomer may be directly polymerized by polymerization, or by polymerization and subsequent post-treatment, the following general formulas (I), (II) and (III)
Alternatively, (IV) or the repeating constitutional unit represented by the general formula (V) of Chemical formula 6 is introduced into the polymer.

[0010]

[Chemical 5] (AB represents a unit of a molecule constituting the main chain of the polymer, and the nitrogen N may be bonded to any position of AB including the terminal of AB directly or through a methylene group. Good R ₁ : hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkenyl group or a hydroxyalkyl group R ₂ : hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkenyl group or a hydroxyalkyl group, and R ₁ and R ₂ are R ₃ may be linked to form a ring: hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkenyl group or a hydroxyalkyl group X: a counter ion)

[0011]

[Chemical 6] (A-N-B: represents a unit of a molecule that contains nitrogen N and constitutes the main chain of the polymer, and the nitrogen N includes A-B end as well as A-
R ₄ which may be located at any position of B: hydrogen or an alkyl group having 1 to 4 carbon atoms, an alkenyl group, a hydroxyalkyl group or an aminoalkyl group)

The above general formula (II) represents a salt of the general formula (I) or a quaternary ammonium compound, and a typical salt (counter ion) is a hydrochloride (chloride). Further, the general formula (IV) is a salt of the general formula (III) or a fourth compound.
It represents a primary ammonium compound, and as a salt (counter ion), a hydrochloride (chloride) is typical.

The hydroxyalkyl group in the above general formula can be introduced by addition of alkylene oxide to nitrogen having active hydrogen. The average number of added moles is not particularly limited, but is preferably 1 to 3 moles.

Specific examples of the amino group-containing monomer include:
Monomers represented by the following general formulas (VI) and (VII) or quaternary ammonium compounds thereof, or intramolecular dehydrated cyclized compounds of the general formula (VI), ethyleneimines of the general formula (VIII) or others A typical example thereof is a derivative of.

[0015]

[Chemical 7] (N: integer 0 to 8 R ₁ : hydrogen, alkyl group having 1 to 4 carbon atoms, alkenyl group or hydroxyalkyl group R ₂ : hydrogen, alkyl group having 1 to 4 carbon atoms, alkenyl group or hydroxyalkyl group , R ₁ and R ₂ may combine to form a ring R _{4 is} hydrogen or an alkyl group having 1 to 4 carbon atoms, an alkenyl group, a hydroxyalkyl group or an alkenyl group)

The general formula (VI) is α-amino acids,
For example, n = 4 is aminocaproic acid. Also,
The terminal amino group and carboxylic acid are dehydrated to form a ring, and ε-caprolactam is the amino acid monomer. These amino acid monomers form a water-soluble polymer by polycondensation.

In the above general formula (VI), n is an integer of 0-8, preferably 2-5. R ₁ and R ₂ are each hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkenyl group or a hydroxyalkyl group, preferably hydrogen,
A methyl group, an ethyl group, a hydroxyethyl group, and a hydroxypropyl group. Specifically, R ₁ / R ₂ = H / H, H
/ CH ₃ , CH ₃ / CH _{3 and the} like.

The above general formula (VII) is aminoethylene (vinylamine), R ₁ and R ₂ are hydrogen, and the number of carbon atoms is 1 to 4
Is an alkyl group, an alkenyl group or a hydroxyalkyl group, preferably hydrogen, a methyl group or an ethyl group. Specifically, R ₁ / R ₂ = H / H, H / CH ₃ , CH ₃
/ CH _{3 and the} like.

In the above general formula (VII), those in which both R ₁ and R ₂ are hydrogen are aminoethylene (= vinylamine), but vinylamine is not known as a monomer.
Therefore, vinylamine units are introduced into the polymer by post-treatment after polymerization using the derivative. Specifically, for example, it is subjected to polymerization as a derivative (vinylamine-N, N-dicarboxylate diethyl) N-substituted with ethyl carboxylate, hydrolyzed after the polymerization, and a structural unit derived from vinylamine is introduced into the polymer. To do.

A structural unit derived from aminoethylene can also be introduced by radically polymerizing N-vinylformamide and then hydrolyzing it with an acid or a base.

The above general formula (VIII) forms polyethyleneimine or a derivative thereof by ring-opening polymerization, and when R ₄ bonded to nitrogen N is other substituent, it is more effective in preventing color transfer. Is big. Also, R bound to nitrogen
_{When 4} is hydrogen, since this hydrogen is active hydrogen, it can be substituted by adding hydroxyalkyl groups such as hydroxyethyl group and hydroxypropyl group by post-treatment with oxyalkylenes. These vinyl-based monomers form a water-soluble polymer by addition polymerization.

The water-soluble polymer of the present invention may be a homopolymer of the above-mentioned amino group-containing monomer or a copolymer of two or more kinds of amino group-containing monomers, and at least one kind of amino group-containing monomer. And a copolymer of this monomer with another monomer that can be copolymerized.

Other copolymerizable monomers include ethylene, vinylpyrrolidone, acrylic acid, acrylamide, vinyl alcohol, allyl alcohol, vinylbenzene sulfonate, and addition polymerization type monomers.
Examples thereof include vinylbenzenecarboxylic acid.

For example, a product obtained by aminating polyethylene after polymerization is equivalent to polyaminoethylene or a copolymer of an aminoethylene unit and an ethylene unit, and exhibits the same effects as the present invention. It is equivalent and is included in the present invention described in the claims. Further, an aminated product of polypropylene is equivalent to polyallylamine or a copolymer of allylamine and propylene.

The amount of amination is determined by a titration method for examining the fraction by neutralization titration, infrared spectroscopy, determination of the structural ratio by NMR, a dye is prepared with a coupling reagent and nitrous acid, and measured by a colorimetric method. You can control.

As the other copolymerizable monomer of the polycondensation type, various amino acids such as aminocarboxylic acid or glutamic acid and arginine represented by the following general formula (IX) are used.

[0027]

[Chemical 8] (N: integer from 0 to 8)

In the copolymer of (a) the amino group-containing monomer and (b) another monomer used in the present invention,
The copolymerization ratio is a molar ratio of (a) / (b) = 100/0 to 50.
The range of / 50 is suitable, and (a) / (b) = 100/0 to 70/30, and more preferably 100/0 to 80/20.

The typical copolymers or homopolymers of the present invention (when m / n = 100/0) are shown below. The water-soluble nylons (Toray (AQ Nylon Co., Ltd.), polyethyleneamines of general formula (XI), polyallylamines of general formula (XII) of Chemical formula 10, polyethyleneimines of general formula (XIII), polydiallyl of general formula (XIV) Dimethylammonium chlorides can be mentioned.

[0030]

[Chemical 9]

[0031]

[Chemical 10]

The above general formulas (X), (XI), (XII),
In any of (XIII) and (XIV), the copolymerization ratio m
/ N is preferably 100/0 to 50/50, preferably 100/0 to 70/30, more preferably 100/0.
It is 0 to 80/20. In the above general formula (XIII),
R is a hydroxyethyl group, a hydroxypropyl group, or the like.

Further, polyethyleneamines and water-soluble nylons may be in the form of salts such as hydrochloride. Furthermore, it is important that the polymer of the present invention is water-soluble, and even a polymer having an amino group-containing monomer as a constituent unit will not exhibit the effects of the present invention if it is not water-soluble.

The water-soluble polymer of the present invention preferably has a weight average molecular weight of 150 to 5,000,000, and preferably 500 to 1,000,000. The anti-transfer and anti-soil redeposition agent of the present invention may be formulated alone and used separately from the detergent composition at the time of washing, or by adding a predetermined amount to the preliminary detergent composition. It may be a detergent composition (detergent composition of the present invention) in which color transfer / recontamination is prevented.

The detergent composition of the present invention comprises a surfactant,
Builders and other detergent ingredients may be included. The surfactant is preferably added in an amount of 5 to 50% by weight, and an anionic surfactant, a nonionic surfactant and the like are used.

Examples of the anionic surfactant include the following. 1) A straight-chain alkylbenzene sulfonate having an alkyl group having an average carbon number of 8 to 16; 2) an α-olefin sulfonate having an average carbon number of 10 to 20; 3) a lower fatty acid having 8 to 22 carbon atoms in a fatty acid residue Alkyl ester sulfonate,

4) Alkyl sulphate having an average carbon number of 10 to 20; 5) Ethylene oxide having an average of 10 to 20 straight or branched chain alkyl or alkenyl group and an average of 0.5 to 8 mol. Alkyl ether sulfate or alkenyl ether sulfate added with 6) Saturated or unsaturated fatty acid salt having an average carbon number of 10 to 22. Alkali metal salts such as sodium and potassium are usually suitable as counterions in these anionic surfactants.

The following are examples of nonionic surfactants. 1) An EO-added nonionic surfactant (alkyl ether ethoxylate) obtained by adding 6 to 25 mol of ethylene oxide (EO) on average to a primary or secondary alcohol having 8 to 18 carbon atoms.

2) An average of 10 to 2 ethylene oxide (EO) in a primary or secondary alcohol having 8 to 18 carbon atoms.
An EO-PO-added nonionic surfactant obtained by adding 5 mol and 1 to 10 mol of propylene oxide (PO). 3) Fatty acid polyoxyethylene alkyl ether represented by Chemical formula 6

[0040]

[Chemical 11] n: shows the number of moles of ethylene oxide added, 5 to 3 on average
Number of 0 R ₃ : alkyl group having 1 to 5 carbon atoms)

This nonionic surfactant is an alkyl ether of an ethylene oxide adduct of a fatty acid in which ethylene oxide is added between ester bonds, and ethylene oxide is added to the fatty acid by a conventional method, and then alkyl ether is formed. The presence of a catalyst composed of magnesium oxide to which one or more metal ions selected from, for example, trivalent aluminum ions, gallium ions, indium ions, thallium ions, and divalent manganese ions are added. It can also be produced by a one-step method in which a fatty acid alkyl ester and ethylene oxide are reacted below (JP-A-4-279552).

4) A sugar ester nonionic surfactant comprising an ester of a fatty acid having 6 to 18 carbon atoms and a monosaccharide having 5 to 6 carbon atoms or a monoalkyl ether thereof. 5) A sugar alkyl ether-based nonionic surfactant represented by Chemical formula 7.

[0043]

Embedded image R ₁ O (CH ₂ CH ₂ O) n (Z) x (R ₁ : alkyl group having 8 to 18 carbon atoms n: 0 to 12 Z: sugar residue having 5 to 6 carbon atoms x: 1 2-10)

6) Alkanolamides of fatty acids having 8 to 18 carbon atoms. 7) Alkyl (C8-18) dimethylamine oxide.

Examples of the builders and other detergent components include inorganic builders such as sodium tripolyphosphate and sodium pyrophosphate; aluminosilicate (zeolite), sodium citrate, sodium ethylenediaminetetraacetate, nitrilotriacetate. , Sodium polyacrylate, sodium acrylate-sodium maleic anhydride copolymer, calcium ion trapping builder such as polyacetal carboxylate; sodium carbonate,
Alkali builders such as potassium carbonate and silicates; Sulfites, sulfates; Recontamination inhibitors such as polyethylene glycols; Enzymes such as proteases, lipases, cellulases, amylases; Softening agents such as quaternary ammonium salts, bentonites; Bleaching Agents, fluorescent agents, fragrances, dyes and the like can be used. The detergent composition of the present invention preferably contains 0.1 to 10% by weight of a color transfer / recontamination inhibitor, preferably 0.5 to 5% by weight.

[0046]

According to the present invention, the problems of color transfer and redeposition during washing can be effectively prevented, and further, the problem of iron adsorption as in the case of using a cationic surfactant occurs. Nor.

[0047]

EXAMPLES The effects of the present invention will be described more specifically below with reference to examples. Prior to this, the evaluation method used in the examples will be shown. The dyed cloth and white cloth used for the color transfer / recontamination experiment are shown below.

1) Dyeing cloth As a standard dyeing cloth, cotton (weaving is knit), reactive dye (Sumitomo Chemical Co., Ltd.), Sumifix Supra blue (BL)
UE BRF Color Index REACTIVE
BLUE 221) was used. These are dyeing density 4
% (Owf.) Was used as a standard cloth.

2) White cloth As a white cloth, Yuka Kyofu (test cloth specified by the Japan Oil Chemistry Association) was used (a polyester jersey was also added at the time of the recontamination experiment). Using this test cloth, a dye transfer (color transfer) / recontamination experiment was conducted.

1. Color transfer experiment evaluation method Assuming complaints from consumers regarding color transfer 40
℃, 1 hour, additive concentration 500ppm (when combined with detergent,
Detergent concentration 5000ppm, bath ratio 20 times (dyed cloth 100
The experiment was conducted with g + white cloth 10 g + balanced cotton cloth 140 g / 5 L detergent solution). 25 white cloths that have been transferred after the end
After rinsing and dehydration with 30 L of water at 30 ° C. for 3 minutes and drying with an iron, it was visually evaluated (evaluated in blue). Evaluation score Criteria A No migration is observed. B Very slightly recognized. C Clearly transfer is observed. D Violent migration is observed.

2. Recontamination Evaluation Method A shirt with worn skin was used as dirt for recontamination evaluation. 25
The test was conducted at 10 ° C. for 10 minutes, detergent usage 833 ppm (standard usage concentration), and bath ratio 30 times (recontamination evaluation cloth (cotton 10 g, polyester 10 g) + wearing shirt 980 g / 30 L detergent solution). After the completion, the recontamination evaluation cloth was rinsed and dehydrated for 3 minutes, dried with an iron, and visually evaluated (evaluated by darkening). Evaluation score Criteria A No recontamination is observed. B Very slightly recognized. C Clearly recontamination is observed. D Violent recontamination is observed.

Example Using the water-soluble polymers made of the polymers shown in Table 1, color transfer and redeposition were evaluated, and the results are shown in the same table. Here, as the detergent, a commercially available detergent having the following composition (weight basis) was used. α-Sulfo fatty acid methyl ester sodium 10% α-olefin sulfonate sodium 5% Linear alkylbenzene sulfonate sodium 10% Zeolite 25% Carbonate 40% Nonionic surfactant 5% Enzyme 2% Fluorescent agent, water balance etc.

In the table, α-amino-ε-caprolactam / ε-caprolactam was AQ nylon of Toray Industries, Inc., polyethyleneimine and its derivatives were samples of Nippon Shokubai Co., Ltd., and others were synthesized. .
Each of these polymers was completely water-soluble at the concentration used.

Further, ethyleneamine and vinyl alcohol units were polymerized using the respective precursors, hydrolyzed after the polymerization, and introduced into the polymer as ethyleneamine units and vinyl alcohol units as repeating units.

[0055]

TABLE 1 Type and evaluation results Evaluation results color shift Ri recontamination Sample No. High content child polymer aqueous detergent systems detergent systems 1 * ¹ PVA water-soluble polymer D D B 2 * ¹ PAA- Na D D B 3 Am ε Cp / ε Cp (50/50) B C B 4 Am ε Cp / ε Cp (70/30) A B A 5 Am ε Cp / ε Cp (80/20) A B A 6 PAm ε Cp A A A A 7 dMeAm ε Cp / ε Cp ( 80/20) A A A 8 AmεCp / Glc (80/20) A A A 9 AmεCp / Glt (80/20) A A A 10 AmεCp / Arg (80/20) A A A A 11 AmEt / Et (80 / 20) B B A 12 PAmEt A A A 13 AmEt / VA (80/20) A A A 14 AmEt / AA-Na (80/20) A A A 15 PAlAm A B B B 16 PAlAm ・ HCl B B B B 17 PdAldMeAm · Cl A A B 18 PEtIm B B B 19 PEtIm · HEt A A A 20 PEtIm · HPr A A A * 1) sample No1,2 the comparative example, another embodiment PVA: polyvinyl alcohol PAA-Na: polyacrylic acid Sodium AmεCp / εCp (50/50): α-amino-ε-
Caprolactam / ε-caprolactam copolymer, copolymerization ratio in parentheses (hereinafter the same) PAmεCp: poly α-amino-ε-caprolactam dMeAmεCp / εCp: α-dimethylamino-ε-
Caprolactam / ε-caprolactam copolymer AmεCp / Glc: α-amino-ε-caprolactam / glycine copolymer AmεCp / Glt: α-amino-ε-caprolactam / glutamic acid copolymer AmεCp / Arg: α-amino-ε- Caprolactam / arginine copolymer AmEt / Et: aminoethylene / ethylene copolymer PAmEt: polyaminoethylene AmEt / VA: aminoethylene / vinyl alcohol copolymer AmEt / AA-Na: aminoethylene / sodium acrylate copolymer PAlAm: Polyallylamine PAlAm · HCl: Polyallylamine hydrochloride PdAldMeAm · Cl: Polydiallyldimethylammonium chloride PEtIm: Polyethyleneimine PEtIm · HEt: Polyethyleneimine · hydroxy Ethyl adduct PEtIm · HPr: polyethyleneimine Hydroxypropyl adduct

Claims (2)

[Claims] 1. A polymer of an amino group-containing monomer, or a copolymer of an amino group-containing monomer with another monomer copolymerizable with the monomer, or an equivalent or post-treatment of these, Of the general formulas (I), (II) and (II
(1) or (IV) or a water-soluble polymer having a repeating constitutional unit represented by the general formula (V) of Chemical formula 2 and derived from an amino group-containing monomer or an equivalent thereof, Anti-pollution agent. [Chemical 1] (AB represents a unit of a molecule constituting the main chain of the polymer, and the nitrogen N may be bonded to any position of AB including the terminal of AB directly or through a methylene group. Good R ₁ : hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkenyl group or a hydroxyalkyl group R ₂ : hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkenyl group or a hydroxyalkyl group, and R ₁ and R ₂ are R ₃ which may be linked to form a ring: hydrogen, an alkyl group having 1 to 4 carbon atoms, an alkenyl group or a hydroxyalkyl group X: a counter ion) (A-N-B: represents a unit of a molecule that contains nitrogen N and constitutes the main chain of the polymer, and the nitrogen N includes A-B end as well as A-
R ₄ which may be located at any position of B: hydrogen or an alkyl group having 1 to 4 carbon atoms, an alkenyl group, a hydroxyalkyl group or an aminoalkyl group) 2. A detergent composition comprising the water-soluble polymer according to claim 1.