JP2003096660A - Method for bleaching textile product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method by which better bleaching effects are obtained when a two-part type bleaching agent is used. SOLUTION: An acidic agent A containing hydrogen peroxide and a specific bleaching activator is mixed with an alkaline agent B containing a specified acid, its ionized substance or a salt thereof at a specific concentration in a specified mass ratio to prepare a mixture at a specific pH. A textile product is then coated or dipped in the resultant mixture or its diluted liquid, or the mixture or the diluted liquid is applied to a wash liquid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bleaching method for textile products using a two-pack type liquid bleaching agent.

[0002]

BACKGROUND OF THE INVENTION Problems such as stains on food spills and yellowing on underwear are stains that cannot be removed with ordinary detergents, and therefore, a bleaching agent is generally used in combination,
Methods such as using a detergent containing a bleach are used. Bleach can be divided into chlorine-based bleach and oxygen-based bleach, but chlorine-based bleach is limited in the fibers that can be used,
Oxygen-based bleaching agents, which do not have these drawbacks, are in widespread use because they cannot be used for colors and patterns and have a unique odor. As the oxygen-based bleaching agent, sodium percarbonate, sodium perborate, or the like, which can generate a peracid species when dissolved in water, may be used, and hydrogen peroxide may be used.
Sodium percarbonate, sodium perborate, etc. are used in powder form of bleaching agents or bleaching detergents. In the method of use, liquid bleaching agents using hydrogen peroxide are applied directly to specific stains or parts such as spots. Because you can
It has become popular recently.

When a liquid bleach is used, a predetermined amount of the liquid bleach is set aside in a cap and applied to a textile product, which is then washed or, like the powder type bleach, is put directly into a washing machine. Target. Such a method obtains a bleaching effect by using it together with an alkaline washing liquid, but the bleaching effect was insufficient.

Therefore, in order to make up for the above-mentioned drawbacks of the liquid oxygen bleaching agent, studies have been made on a bleaching agent composition containing various peroxo acid bleaching precursors and organic peroxo acids as bleaching activators. For example, JP-A-62-23089
No. 7 discloses a liquid bleaching composition in which particles of a bleaching activator that produces an organic peracid are dispersed in an acidic aqueous solution containing hydrogen peroxide. In addition, JP-A-7-7
No. 0593 discloses a fluid aqueous liquid detergent composition having a substantially water-insoluble organic peroxo acid. Further, the inventors of the present invention disclose a liquid bleaching composition in which a specific surfactant and a bleaching activator are combined in JP-A-6-207196 and JP-A-7-82591.

On the other hand, in addition to a means for enhancing the bleaching power by using a bleach activator, research has been conducted on a two-pack type liquid bleaching agent for the purpose of enhancing bleaching performance and storage stability. For example, JP-A-3-140400 and JP-A-6-16
6892 and Japanese Patent Application Laid-Open No. 9-157693 disclose a bleaching agent composition comprising an agent A containing hydrogen peroxide and an agent B containing a bleaching activator. These techniques are superior in bleaching effect to the case where a liquid oxygen bleaching agent containing hydrogen peroxide as a main base is used alone, but it is not yet at a satisfactory level. In addition, JP-A-9-4899
No. 7, JP-A-9-157693, JP-A-3-
Japanese Patent No. 140400 discloses a bleaching agent composition comprising agent A containing hydrogen peroxide and agent B containing an alkaline agent, but the bleaching detergency is not at a satisfactory level.
This is because hydrogen peroxide, the bleach activator, and the alkaline agent exert influence on each other, so that it is difficult to prepare a two-component type.

Therefore, the inventors of the present invention disclosed in Japanese Patent Laid-Open No. 9-4899.
Japanese Patent No. 7 provides a two-component liquid bleaching composition comprising an agent A containing hydrogen peroxide, a bleach activator and an amphoteric surfactant and an agent B containing an alkaline agent. Although this technique has an excellent bleaching effect, it has not exhibited its bleaching effect sufficiently.

An object of the present invention is to provide a bleaching method capable of obtaining an excellent bleaching effect on textiles when a two-pack bleaching agent is used.

[0008]

The present invention contains 0.05 to 10% by mass of hydrogen peroxide and 0.05 to 10% by mass of a bleach activator having an ester group, an imide group or a nitrile group. One kind selected from agent A, which is an aqueous composition having a pH of 1.0 to 7.0 at 20 ° C., and carbonic acid, phosphoric acid, carboxylic acid, phosphonic acid, phosphonocarboxylic acid, and ionized products or salts thereof. The above content is 0.5 to 10 mass% in terms of acid form, and the pH at 20 ° C is 8.
5 to 13.5 is an aqueous composition and agent B in a mass ratio of A
Agent / B agent = 20/1 by mixing within the range of 10/1 to 1/10
After preparing a mixed solution having a pH of 8.0 to 13.0 at 0 ° C., the mixed solution (hereinafter, referred to as AB mixed solution) or a diluted solution thereof (a diluted solution of a composition containing water is preferable). The present invention relates to a method for bleaching a textile product, which is applied to a textile product.

In the present invention, "apply" means either of the following two. (1) Applying or spraying the AB mixed solution directly onto part or all of the textile product, or impregnating the AB mixed solution with the textile product. (2) Directly coating or spraying a diluted solution obtained by diluting the AB mixed solution with water or a washing solution containing at least a surfactant, or spraying the AB mixed solution with water or at least Impregnating a textile product with a diluting liquid diluted with a washing liquid containing a surfactant. (In this case, even if the AB mixed solution is added to water or a washing liquid impregnated with the textile product, or the AB mixed solution is administered while the water or the washing liquid is administered to the textile product. Good.)

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Since the agent A which is an aqueous composition used in the present invention has a good bleaching effect, hydrogen peroxide is preferably contained in an amount of 0.05 to 10% by mass, more preferably 0. 1 to 8% by mass, particularly preferably 0.5 to 6% by mass.

The agent A is preferably a bleaching activator having an ester group, an imide group or a nitrile group, and is preferably 0.05.
-10 mass%, more preferably 0.1 to 7 mass%, still more preferably 0.1 to 5 mass%. Preferable bleach activator having an ester group includes alkanoyloxybenzene sulfonate, alkanoyloxybenzene carboxylic acid or a salt thereof, and bleach activator having an imide group includes tetraacetylethylenediamine. Examples of the bleach activator having a nitrile group include compounds described in JP-A No. 1-068347. Among them, the most preferable bleach activator includes an alkanoyloxybenzene sulfonic acid type bleach activator and an alkanoyloxybenzene carboxylic acid type bleach activator, and particularly has 6 to 1 carbon atoms.
Alkanoyloxybenzenesulfonic acid having 4, preferably 7 to 13 alkanoyl groups or 6 to 6 carbon atoms
Alkanoyloxybenzenecarboxylic acids having 14, preferably 7 to 13 alkanoyl groups or salts thereof are preferred. Specific preferred examples include octanoyloxy-p-benzenesulfonic acid and nonanoyloxy-
p-benzenesulfonic acid, 3,5,5-trimethylhexanoyloxy-p-benzenesulfonic acid, decanoyloxy-p-benzenesulfonic acid, dodecanoyloxy-p-benzenesulfonic acid, octanoyloxy-o-
Or -p-benzenecarboxylic acid, nonanoyloxy-o
-Or-p-benzenecarboxylic acid, 3,5,5-trimethylhexanoyloxy-o- or -p-benzenecarboxylic acid, decanoyloxy-o- or -p-benzenecarboxylic acid, dodecanoyloxy-o- Alternatively, -p-benzenecarboxylic acid and salts thereof can be mentioned. As the salt, sodium salt, potassium salt and magnesium salt are preferable, and sodium salt is particularly preferable from the viewpoint of solubility.

As the bleach activator, among these, nonanoyloxy-p-benzenesulfonic acid, decanoyloxy-p-benzenecarboxylic acid, nonanoyloxy-p-benzenecarboxylic acid, 3,5,5-trimethylhexanoyloxy -P-Benzenecarboxylic acid, dodecanoyloxy-p-benzenesulfonic acid and salts thereof are preferable from the viewpoint of lipophilic stain bleaching effect.

The pH of agent A at 20 ° C. is 1.0.
-7.0, preferably 1.5-6.5, more preferably 2.0-6.0. It is preferable to use an acid agent in order to adjust to such a pH. In the present invention, the acid agent refers to a compound that makes the pH of the aqueous solution acidic by addition, and examples of the acid agent for adjusting the pH include nitric acid, sulfuric acid, phosphoric acid, boric acid, phosphonic acid, and phosphonocarboxylic acid. Acids, carboxylic acids, polycarboxylic acids and aminocarboxylic acids are preferred. Of these, specifically preferred compounds include sulfuric acid, orthophosphoric acid, metaphosphoric acid, inorganic acids selected from boric acid, ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, and ethane-1. -Hydroxy-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, aminopoly (methylenephosphonic acid), Phosphonic acid selected from polyethylene polyamine poly (methylenephosphonic acid), 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, and phosphono selected from α-methylphosphonosuccinic acid. Carboxylic acid, nitrilotriacetic acid,
Iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid,
Aminopolyacetic acid selected from hydroxyethyliminodiacetic acid, triethylenetetramine hexaacetic acid, and dienecoric acid,
Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid,
Malic acid, oxydisuccinic acid, gluconic acid, carboxymethyl succinic acid, a polycarboxylic acid selected from carboxymethyl tartaric acid, particularly preferred compounds are sulfuric acid, boric acid and ethane-1-hydroxy-1,1-diphosphonic acid, ethane. It is one or more selected from -1,1-diphosphonic acid.

These may be used as sequestering agents described below. The compounding amount of the acid agent in the agent A is added within a range satisfying the pH condition, but from the viewpoint of storage stability, 10% by mass or less, and further 0.1 to 5% by mass.
Is preferably added in the range.

An alkaline agent may be added to the agent A of the present invention as long as the above pH condition is satisfied. In the present invention, the alkaline agent refers to a compound that exhibits alkalinity when added to ion-exchanged water. In the present invention, it is preferably used for pH adjustment, and alkali metal hydroxide is preferable.

In the present invention, agent A and agent B are mixed and used as a two-component bleaching agent. However, a small amount of agent B is mixed with agent A and the pH is increased during mixing. There is a concern that gas will be generated. Therefore, it is preferable that the agent A of the present invention has the ability to suppress pH fluctuation with respect to alkali. For that purpose, it is preferable to add an acid agent having a buffering ability among the above-mentioned acid agents or a salt thereof, and specifically, phosphoric acid, boric acid, phosphonic acid, phosphonocarboxylic acid, or carboxylic acid in the agent A is mixed. The concentration of acid and polycarboxylic acid, their ionized products, and salts thereof contained in one or more agents A is defined, and the concentration when counted as an acid form is 0.001 to 5% by mass. , Preferably 0.1 to 3% by mass, more preferably 0.1 to 1% by mass,
Most preferably, it is 0.1 to 0.5% by mass. Since the chlorine ion in the agent A reduces the stability of hydrogen peroxide, the content of chlorine ion due to hydrochloric acid or chlorine salt is suppressed, and the chlorine ion is 0.2 mass% or less in the agent A, and further, It is preferably 0.02% by mass or less, and particularly preferably substantially not contained.

The water used in the agent A of the present invention is preferably distilled water or ion-exchanged water. From the viewpoint of storage stability, water is preferably 50 to 99% by mass, and more preferably 60 to 95% by mass in the agent A.

The agent B of the present invention has a pH at 20 ° C. of 8.5 to 13.5, preferably 9.0 to 13.5, more preferably 9.5 to 11.5, and most preferably 10.0.
.About.11.0. In order to achieve such a pH, the agent B is blended with an alkaline agent. Examples of the alkaline agent include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, phosphates, phosphonates and borates. Examples thereof include silicates, carboxylates, conjugated bases of compounds having a phenolic hydroxyl group or an enolic hydroxyl group, and ammonia, monoethanolamine, diethanolamine, triethanolamine, and other amine derivatives. Among them, the preferable one is
Mention may be made of sodium carbonate and potassium carbonate. The alkaline agent is added in a concentration satisfying the pH condition, but from the viewpoint of storage stability, it is preferably added in an amount of 20% by mass or less, more preferably 1 to 15% by mass.

An acid agent may be added to the agent B of the present invention as long as the pH condition is satisfied. In the present invention, the acid agent refers to a compound that makes the pH of the aqueous solution acidic by adding it, and may be a salt such as a strong acid weak base.

By the way, the pH of the AB mixed solution at 20 ° C. is
The mixture is mixed at a ratio of 8.0 to 13.0, preferably 9.0 to 11.0 so as to be alkaline, but unilaterally increasing the mixing ratio of the agent B means bleaching in the AB mixed solution. It is not preferable because the concentration of hydrogen peroxide as a seed is lowered. For that purpose, it is preferable that the agent A is superior to the agent A in suppressing pH fluctuation in the alkaline region due to the agent B. In this regard, in the agent B of the present invention, the concentration of one or more of carbonic acid, phosphoric acid, carboxylic acid, phosphonic acid and phosphonocarboxylic acid, ionized products thereof, and salts thereof in the agent B is When counted as a form, it is required to be 0.5 to 10% by mass, preferably 1.0 to 8.0% by mass, and more preferably 2 to 5% by mass.

In the present invention, the pH of the AB mixed solution is 8.0 to 1 at 20 ° C. when the agents A and B are mixed in equal proportions by mass ratio.
A and B such that the amount is 3.0, particularly 9.0 to 11.0.
It is preferably a combination of agents. In order to satisfy such conditions, in the present invention, it is preferable to use an alkali metal carbonate as the alkali agent, and it is particularly preferable to add potassium carbonate. The alkali metal carbonate is blended so that the carbonic acid concentration in the system will be 1.5 to 5.0 mass%.

The water used in the agent B of the present invention is preferably distilled water or ion-exchanged water. Further, from the viewpoint of storage stability, the content of water in the agent B is preferably 50 to 99% by mass, preferably 60 to 95% by mass.

In the present invention, it is preferable to add a surfactant to the agent A and / or agent B for the purpose of enhancing the bleaching cleaning effect. The surfactant is preferably one or more selected from nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants.

As the nonionic surfactant, the compound of the general formula (1) is preferable. R ¹ -T-[(R ² O) _a -H] _b (1) [wherein R ¹ has 6 to 18 carbon atoms, preferably 10 to ¹ carbon atoms]
6 is an alkyl group or an alkenyl group, R ² is an alkylene group having 2 or 3 carbon atoms, and is preferably an ethylene group. a represents a number of 2 to 200, preferably 4 to 50, particularly preferably 5 to 20. T is -O-, -CON-
Or -N-, and when T is -O-, b is 1.
B is 2 when T is -CON- or -N-. ].

The following compounds may be mentioned as specific examples of the compound of the general formula (1). ^{_{R 1 -O- (C 2 H 4}} O) r -H (1-a) wherein, R ¹ is the same meaning as defined above. r is a number of 2 to 200, preferably 3 to 100, more preferably 4 to 20. ] ^{_{R 1 -O- (C 2 H 4}} O) s - (C 3 H 6 O) t -H (1-b) wherein, R ¹ is the same meaning as defined above. s and t are each independently a number of 2 to 15, preferably 2 to 10, and ethylene oxide and propylene oxide may be random or block adducts. ]

[0026]

[Chemical 1]

In the present invention, among these, especially (1-a)
And nonionic surfactants selected from (1-b) are preferred.

As the cationic surfactant, a mono-long chain alkyl (or alkenyl) tri-short chain alkyl type cationic surfactant represented by the following general formula (2) is preferable.

[0029]

[Chemical 2]

[Wherein R ³ is an alkyl group or an alkenyl group having 8 to 18 carbon atoms, preferably 10 to 18 carbon atoms, particularly preferably 10 to 16 carbon atoms, and R ⁴ , R ⁵ and R ⁶ are the same or different. It may be an alkyl group having 1 to 3 carbon atoms.
X ⁻ is an anion, preferably a halogen ion, having 1 carbon atom
Is an alkylsulfuric acid ester ion having 3 to 3 carbon atoms, a fatty acid ion having 1 to 12 carbon atoms, and an aryl sulfonate ion having 1 to 3 substituents having 1 to 3 carbon atoms. ].

Examples of the anionic surfactant include an alkyl group or an alkenyl group having 10 to 18 carbon atoms, preferably 10 to 16 carbon atoms, particularly preferably 10 to 15 carbon atoms, and --SO.
Anionic surfactants having ₃ M groups and / or -OSO ₃ M groups [M: counterion] are preferred. Specifically, alkylbenzene sulfonic acid having the above carbon number, alkyl (or alkenyl) sulfuric acid ester, polyoxyalkylene alkyl (or alkenyl) ether sulfuric acid ester, olefin sulfonic acid, alkane sulfonic acid, α-sulfo fatty acid, α-sulfo fatty acid Esters and their salts are preferred. Among these, alkyl (or alkenyl) sulfuric acid esters having an alkyl group or alkenyl group having 10 to 16 carbon atoms, an alkyl group or alkenyl group having 10 to 16 carbon atoms, and ethylene oxide (hereinafter referred to as EO) average The number of added moles is 1 to 6, preferably 1 to
4, particularly preferably 1 to 3, polyoxyethylene alkyl (or alkenyl) ether sulfate, or alkylbenzene sulfonic acid having 10 to 15 carbon atoms,
And it is preferable to blend one or more selected from these salts. As the salt, sodium salt, potassium salt,
Ammonium salt and alkanolamine salt are preferable from the viewpoint of storage stability.

As the amphoteric surfactant, the following general formula (3) is used.
Or a compound selected from the compounds of formula (4) is preferred.

[0033]

[Chemical 3]

[In the formula, R ⁷ is a linear alkyl group or alkenyl group having 8 to 16 carbon atoms, preferably 10 to 16 carbon atoms, particularly preferably 10 to 14 carbon atoms, and R ⁸ and R ⁹ are each 1 carbon atoms. ~ 3 alkyl groups or hydroxyalkyl groups. R ¹⁰ is an alkylene group having 1 to 5 carbon atoms, preferably 2 or 3. A is -COO-, -CONH-, -OC
A group selected from O-, -NHCO-, and -O-, and c
Is a number of 0 or 1, preferably 1. ]

[0035]

[Chemical 4]

[In the formula, R ¹¹ is an alkyl group or an alkenyl group having 9 to 23 carbon atoms, preferably 9 to 17 carbon atoms, particularly preferably 10 to 16 carbon atoms, and R ¹² is 1 to 6 carbon atoms, preferably 1 to 6 carbon atoms. 4, particularly preferably 2 or 3 alkylene groups. B is -COO-, -CONH-, -OCO-, -N
HCO-, a group selected from -O-, and d is 0 or 1.
, Preferably 0. R ¹³ and R ¹⁴ are each an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, preferably a methyl group, an ethyl group or a hydroxyethyl group, and R ¹⁵ is a carbon number which may be substituted with a hydroxy group. To 5, preferably 1 to 3 alkylene groups. D
Is a group selected from —SO ₃ ⁻ and —OSO ₃ ⁻ , and —SO ₃ ⁻ is particularly preferable from the viewpoint of bleaching cleaning effect. ]. The amine oxide type amphoteric surfactant is preferable to be blended with the agent B because a more excellent bleaching power can be obtained.

The agent A used in the present invention contains 0.5 to 20% by mass of a nonionic surfactant from the viewpoint of the bleaching cleaning effect.
Furthermore, 1 to 15% by mass, and a cationic surfactant of 0.0
It is preferable to contain 5 to 5% by mass, and further 0.1 to 3% by mass. Further, the agent A is an amphoteric surfactant 0 to 10% by mass.
Can be included.

The agent B used in the present invention contains a nonionic surfactant in an amount of 0.5 to 50% by mass, and further 1 in terms of cleaning effect.
-40% by mass, and 0.5-50 anionic surfactant.
It is preferably contained in an amount of 1% by mass, more preferably 1 to 40% by mass.
Further, the agent B can contain 0 to 20% by mass of an amphoteric surfactant, and further 0.5 to 10% by mass.

A solvent may be added to the agent A and / or agent B used in the present invention for the purpose of enhancing the cleaning effect. As the solvent, (i) a monohydric alcohol having 1 to 5 carbon atoms, (i
i) a polyhydric alcohol having 2 to 12 carbon atoms, (iii) a compound represented by the following general formula (5), (iv) a compound represented by the following general formula (6), (v) the following general The compound represented by Formula (7) is mentioned.

[0040]

[Chemical 5]

[Wherein R¹⁶And R¹⁷Is the hydrogen source
Child, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or benzyl
R group, but R¹⁶And R¹⁷When both become hydrogen atoms
Excluding cases. g is a number from 0 to 10 and h is a number from 0 to 10.
Except that both g and h are 0. R¹⁸as well as
R¹⁹Are each an alkyl group having 1 to 3 carbon atoms. R
²⁰Represents an alkyl group having 1 to 8 carbon atoms. ].

Examples of the monohydric alcohol having 1 to 5 carbon atoms (i) include ethanol, propyl alcohol and isopropyl alcohol. These low grade (C1-C1
5) Stability of the system at low temperatures can be further improved by blending alcohol.

Examples of the polyhydric alcohol having 2 to 12 carbon atoms (ii) include isoprene glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,8-octanediol and 1,9-nonanediol. , Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin and the like.

The compound (iii) has 1 to 10 carbon atoms when R ¹⁶ and R ¹⁷ are alkyl groups in the general formula (5).
4 is particularly preferred. Further, in the general formula (5), g and h of the average addition mole number of EO and propylene oxide are numbers of 0 to 10 (excluding the case where both s and t are 0). The order of addition is not particularly limited, and may be random addition. Specific examples of the compound (iii) include ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, Polyoxyethylene (p = 2-3) Polyoxypropylene (p = 2-3)
Examples thereof include glycol dimethyl ether (p represents the average number of moles added), polyoxyethylene (p = 3) glycol phenyl ether, phenyl carbitol, phenyl cellosolve, and benzyl carbitol. this house,
Propylene glycol monomethyl ether, diethylene glycol monobutyl ether, and polyoxyethylene (p = 1 to 4) glycol monophenyl ether are preferable from the viewpoints of detergency and feeling of use.

As the compound of (iv), 1,3-
Dimethyl-2-imidazolidinone, 1,3-diethyl-
2-Imidazolidinone is exemplified as a suitable one,
Alkyl glyceryl etherification as the compound of (v)
Compound, preferably R ²⁰Is an al having 3 to 8 carbon atoms
It is a compound of the kill group.

Of these, water-soluble solvents (i), (ii), (iii) and (v) are preferable in order to satisfy the properties of the present invention, particularly ethanol, isopropyl alcohol,
Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin,
A solvent selected from isoprene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, pentyl glyceryl ether, octyl glyceryl ether, and polyoxyethylene (p = 1 to 4) glycol monophenyl ether is preferable.

The agent A and / or agent B used in the present invention contains such a solvent in an amount of 0.1 to 10% by mass, and further 0.3%.
.About.7% by mass, particularly 0.5 to 5% by mass is preferable.

The agent A and / or agent B used in the present invention is an alkali metal salt of a homopolymer of acrylic acid, methacrylic acid or maleic acid or a copolymer thereof,
It is preferable to contain an alkali metal salt of a copolymer of these with a copolymerizable unsaturated compound. Specifically, using poly (ethylene glycol) as a standard substance in gel permeation chromatography, sodium acrylate (or potassium) or sodium polymethacrylate (or potassium) with a weight average molecular weight of 3,000 to 30,000, a weight average molecular weight. Molecular weight is 20,0
00-100,000, preferably 50,000-8
10,000 sodium (or potassium) salts of polyacrylic acid-maleic acid copolymers are good. In the case of polyacrylic acid-maleic acid copolymer, the polyacrylic acid / maleic acid is in a mass ratio of 5/5 to 9/1, and further 6
/ 4 to 8/2 is preferable from the viewpoint of cleaning effect. Agent A and /
Alternatively, the agent B is 0.1 to 20% by mass, more preferably 0.5 to 10% by mass of such a polymer component in the agents A and B.
From the viewpoint of the bleaching effect, it is preferable to contain it in an amount of mass%.

The viscosities of agents A and B at 20 ° C. are both 3 to 300 mPa · s, and further 4 to 200 m.
Pa · s is preferable in terms of usability.
In order to adjust to such a viscosity, a viscosity adjusting agent can be added to the agent A and / or the agent B. Examples of the viscosity modifier include benzenesulfonic acid which may be substituted with 1 to 3 alkyl groups having 1 to 3 carbon atoms or hydroxy groups, which are the above hydrotropes, and have a molecular weight of 3,000.
Polymer thickeners such as polyethylene glycol, polypropylene glycol, carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose and xanthan gum of 100,000 and clay minerals such as montmorillonite can be used. Such a viscosity modifier is
0 to 10% by mass in the agent A and / or agent B, and further 0.01 to
It is preferable that the content is 5% by mass.

Further, the agents A and / or B of the present invention include
It is preferable to add a sequestering agent. The sequestering agent used in the present invention includes the following (C1)
Examples include (C9), and among them (C3) and (C
6), at least one selected from (C7) and (C8) is preferable, and at least one selected from (C3)
Seeds are more preferred. (C1) Phosphates such as tripolyphosphoric acid, orthophosphoric acid and hexaphosphoric acid, or alkali metal salts or alkanolamine salts (C2) Phosphoric acid compounds such as phytic acid, alkali metal salts or alkanolamine salts (C3) thereof, ethane -1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and Derivatives thereof, phosphonic acids such as ethanehydroxy-1,1,2-triphosphonic acid phosphonic acid or alkali metal salts or alkanolamine salts thereof, (C4) 2-phosphonobutane-1,2-dicarboxylic acid,
1-phosphonobutane-2,3,4-tricarboxylic acid, α
-Phosphonocarboxylic acids such as methylphosphonosuccinic acid or their alkali metal salts or alkanolamine salts (C5) amino acids such as aspartic acid, glutamic acid, glycine or their alkali metal salts or alkanolamine salts (C6) nitrilotriacetic acid , Aminopolyacetic acid such as iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraminehexaacetic acid and dienecoric acid, or their alkali metal salts or alkanolamine salts (C7) Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid, carboxyme Carboxylic acid such as tartaric acid, polycarboxylic acid or alkali metal salt or alkanolamine salt thereof (C8) Alkali metal salt of aluminosilicic acid represented by zeolite A or alkanolamine salt (C9) aminopoly (methylenephosphonic acid) or the same Alkali metal salt or alkanolamine salt, or polyethylene polyamine poly (methylenephosphonic acid) or its alkali metal salt or alkanolamine salt.

Such a sequestering agent is contained in the agent A and / or the agent B in a total amount of 0 to 10% by mass, and further 0.01%.
˜5% by mass, and particularly preferably 0.01 to 1% by mass.

Further, to the agent A and / or agent B of the present invention, in addition to the above-mentioned components, known components which are usually added can be added. For example, it is preferred to use known magnesium sulfate, magnesium silicate, magnesium chloride, magnesium oxide, magnesium salts such as magnesium hydroxide, and silicates such as sodium silicate as a stabilizer for hydrogen peroxide. These compounds can also be blended as an alkaline agent. Furthermore, it is preferable to add anti-redeposition agents such as carboxymethyl cellulose, polyvinyl pyrrolidone, and polyethylene glycol, if necessary.

The agent A and / or agent B of the present invention may further contain various compounds. For example, barbituric acid, which is known as a stabilizer for hydrogen peroxide,
Uric acid, acetanilide, aminopolycarboxylic acids represented by oxyquinoline and phenacetin, and DL
-Α-tocopherol, gallic acid derivative, butylated hydroxyanisole (BHA), 2,6-di-tert-
Butyl-4-methylphenol (BHT) or the like is preferably added. These stabilizers are preferably contained in the agent A and / or the agent B in a total amount of 0 to 5% by mass, more preferably 0.01 to 3% by mass.

Further, the agents A and / or B of the present invention preferably contain a substance known as a discoloration preventing agent. Examples of such substances include phenylalanine, histidine,
Examples thereof include amino acids or salts thereof such as lysine, tyrosine and methionine, amino or imide compounds such as hydroxyiminodiacetic acid, copolymers of acrylonitrile and at least one monomer copolymerizable with acrylonitrile having a quaternary ammonium group. Although amino acids have optical isomers, the optical isomers do not participate in the effect of the present invention. Therefore, it is also possible to use chemically synthesized amino acids.

Furthermore, in the agents A and / or B of the present invention, as a fluorescent whitening agent for increasing the bleaching effect on the bleached fiber, Tinopearl CBS (manufactured by Ciba Geigy),
Chino Pearl SWN (manufactured by Ciba Geigy) and color
Optical brighteners such as index optical brighteners 28, 40, 61, 71, etc., and conventionally known enzymes (cellulase, amylase, protease, for improving bleaching performance,
It is preferable to add a lipase) as needed.

Further, the agents A and / or B of the present invention include
It is preferable to add an appropriate amount of various trace additives such as colorants such as dyes and pigments, fragrances, silicones, bactericides, and ultraviolet absorbers.

The agents A and / or B of the present invention include
A hydrotrope agent may be blended for the purpose of improving the stability and freeze-restoration property of the liquid at a low temperature and preventing the liquid separation at a high temperature. As such a hydrotrope, a short-chain alkylbenzene sulfonate represented by toluene sulfonate, xylene sulfonate, etc., ethanol, ethylene glycol, propylene glycol, hexylene glycol, glycerin, etc. are generally used. Representative alcohols and polyhydric alcohols are preferable. The hydrotrope agent is preferably blended in the agent A and / or the agent B in a total amount of 0 to 30% by mass.

In the bleaching method of the present invention, the AB mixed solution is (1) directly coated or sprayed with the AB mixed solution on a part or all of the fiber product, or by impregnating the AB mixed solution with the fiber product, or (2) A solution obtained by diluting an AB mixed solution with water or a washing solution containing at least a surfactant is directly applied or sprayed on a part or all of a textile product, or the AB mixed solution is mixed with water or at least an interface. It is applied to textiles by impregnating the textiles with a diluting solution diluted with a wash liquor containing an activator. In the case of (2), AB is added to the one in which the textile product is impregnated with water or washing liquid.
A method of adding the mixed solution or a method of administering the AB mixed solution while administering water or a washing solution to the textile product may be used.

That is, it is possible to obtain an unprecedented excellent bleaching effect by using a mixture of the specific composition A and the composition B in advance. In addition, the method of (2) applies to the one in which the textile product is impregnated with water or washing liquid.
The method of adding the B mixed solution or the method of administering the AB mixed solution while administering the water or the washing solution to the textile product is included, but the most preferred method of (2) is
It is preferable to administer the textile product to a solution in which the AB mixed solution is thoroughly mixed with water or a washing solution.

The mixing ratio of agents A and B at the time of use is, by mass ratio, agent A / agent B = 1/10 to 10/1, further 1/5 to 5 /.
It is preferably set within the range of 1 from the viewpoint of the bleaching cleaning effect.

A container used for such a two-component bleaching agent is, for example, a container provided with a discharging section capable of simultaneously discharging the A agent and the B agent, and the A agent and the B agent are respectively stored in different storage sections. It is also possible to use a possible integrated container or a connected container in which a container capable of containing the agent A and a container capable of containing the agent B are joined by a member capable of joining them. In addition, the integrated container and the connected container (hereinafter referred to as a two-component container) are
The ratio of the discharge amounts of agent A and agent B is a mass ratio of agent A / agent B = 1/1.
It is preferable to adjust the shape of each discharge part so that it becomes 0 to 10/1, preferably 1/5 to 5/1. The discharge amount can be adjusted by a known method by adjusting the viscosities of the agents A and B and the opening area and shape of the discharge portion.

The two-part container has an opening area A of the discharge portion.
The area ratio of the agent discharge part and the B agent discharge part is 1/10 to 10 /.
1, preferably 1/5 to 5/1 is preferable for adjusting the discharge amount. It may be measured twice or more times, but from the viewpoint of convenience, it is preferable that agent A and agent B are mixed at a designed specific ratio in one measuring operation. Figure 1 shows an example of
Or the thing of FIG. 2 is mentioned.

In FIG. 1, (11) and (12) are agent A or agent B storage portions, in which either agent A or agent B is stored in the other. Each housing is separated by the partition wall (13). Reference numeral (14) is an ejecting portion capable of ejecting the agent A and the agent B at the same time. The cap (1-1) of this container is designed to be screwed with the discharge part (14) and also has a function of measuring the content.

In FIG. 2, (21) and (22) are accommodating portions for the agent A or the agent B. The agent A is accommodated in one of them and the agent B is accommodated in the other, and these are joint portions of (23). It is joined.
Reference numeral (24) is an ejecting portion capable of ejecting the agent A and the agent B at the same time. This container also has the same cap (2-
1) is used.

Although many other bottle shapes are conceivable, those shown in FIGS. 3 and 4 may be used.
The container of FIG. 3 is the container of FIG. 1 provided with a grip portion (handle) (32), and the inside is divided into two chambers by a partition wall (31), one of which is A agent and the other of which is B agent. Is housed,
The liquids are not mixed. By pouring with the handle (32), the agent A and the agent B are mixed at a designed specific ratio from the start of use to the end of use and then poured into the measuring container. The cap (3-1) similar to that shown in FIG. 1 is also used for this container.

A container as shown in FIG. 4 can also be used. The inside of the container is divided into two chambers by a partition wall (41), and as in FIG. 3, agent A is contained in one side and agent B is contained in the other side, and the respective liquids are not mixed. . By pouring by holding the handle (42), the agent A and the agent B are mixed at a designed specific ratio from the start of use to the end and then poured into a measuring container. A cap (4-1) similar to that shown in FIG. 1 is also used for this container.

Further, as shown in FIG. 5, the cap (5-1) which is more convenient and easy to store can be used as shown in FIGS. As shown in FIGS. 1 to 5, the one that also serves as the cap of the container has a relatively low viscosity (20
It is suitable when agents A and B of about mPa · s) are used, and the agents A and B may be weighed by a weighing device other than the cap of the container, for example, as shown in FIG. As described above, it is possible to use a weighing machine (6-1) having a lid that also serves as weighing and mixing. Such a scale is particularly suitable for a mixed liquid having a relatively high viscosity (100 mPa · s or more).

[0068]

INDUSTRIAL APPLICABILITY As described above, in the present invention, by using a mixed solution in which agent A and agent B are sufficiently mixed for bleaching a textile product, an excellent bleaching effect which has never been obtained can be obtained.

[0069]

【Example】

[0070]

Example Using the agent A of Table 1 and the agent B of Table 2, the bleaching effect in coating cleaning and immersion cleaning was evaluated by the following methods.

(1) Coating and Washing (1-1) Method of Example 100 parts of agent A shown in Table 1 and 100 parts of agent B shown in Table 2 were used.
ml was prepared. 20 parts in total of the obtained agents A and B
The mixture was placed in a 100 ml beaker at a ratio (mass ratio) shown in Tables 3 and 4 so that the amount became ml, and the beaker was shaken to mix for 10 seconds, and immediately, using a micropipette, two types prepared as described below. 1 ml of each of the test cloths [bilirubin-contaminated cloth (corresponding to model dirt of lipophilic stain) and tea-contaminated cloth (corresponding to model dirt of hydrophilic stain)], and left for 1 hour. Five test cloths (5 bilirubin-contaminated cloths and 5 tea-contaminated cloths) were prepared for each method.

After being left to stand, five test cloths were washed with 1 L of a washing liquid in which a commercial detergent (Attack) was dissolved at a concentration of 0.0667% for 10 minutes using a Terg-o-meter. Processed. At this time, 5 test cloths were treated in the same beaker. After washing, the test cloth was thoroughly rinsed under running water (tap water) and dried at room temperature. The bleaching rate of the dried test cloth was calculated according to the following formula, and the average value of 5 test cloths was obtained. The results are shown in Table 3.
It was shown to.

(1-2) Method of Comparative Example Weighed with a micropipette at a ratio shown in Table 3 so that the total amount of application of the agent A of Table 1 and the agent B of Table 2 was 1 mL, The agents A and B were separately and directly applied to the test cloth and left for 1 hour. After that, the washing treatment was carried out in the same manner as in the above-mentioned Example, and after rinsing and drying, the bleaching rate of five test cloths was averaged. The results are shown in Table 3.

(2) Immersion cleaning (2-1) Method of Example 100 parts of A agent shown in Table 1 and 100 parts of B agent shown in Table 2 were used.
ml was prepared. 20 parts in total of the obtained agents A and B
At a ratio (mass ratio) shown in Tables 3 and 4 so that the mixture becomes ml, the mixture was placed in a 100 ml beaker and shaken for 10 seconds to mix, and then 20 ml of tap water at 20 ° C. was dissolved in 20 ml of the mixed solution. , An aqueous medium (AB mixed solution) was obtained. Five test cloths were put in the obtained aqueous medium and immersed for 30 minutes. After the immersion, the test cloth was thoroughly rinsed under running water (tap water) and dried at room temperature. The bleaching rate of the test cloth after drying,
The calculation was performed in the same manner as the above-mentioned coating cleaning, and the average value of 5 test cloths was obtained. The results are shown in Table 3.

(2-2) Method of Comparative Example Each of the agents A and B was weighed with a micropipettor at a ratio shown in Table 3 so that the total amount of the agents A and B was 20 mL, and A 20 without mixing agent and agent B
It was dissolved in 2 L of tap water at 0 ° C. After that, the treatment was performed under the same conditions as in the method of the above-mentioned example, and the average of the bleaching rates of the five test cloths was obtained. The results are shown in Table 3.

<Bleach rate calculation method>

[0077]

[Equation 1]

The reflectance is ND-30 manufactured by Nippon Denshoku Industries Co., Ltd.
Measured using a 460 nm filter at 0A.

<Test cloth> (1) Bilirubin-contaminated cloth Bilirubin (reagent manufactured by Merck) 0.03 g is added to 100 m.
It was dissolved in 1 of chloroform. 0.06 ml of this bilirubin-chloroform solution was evenly dropped onto a cotton cloth of 5 cm × 5 cm and dried at room temperature to obtain a bilirubin-contaminated cloth.

(2) Black tea-contaminated cloth 160 g of Nitto black tea (yellow package) was boiled in 6 L of ion-exchanged water for about 15 minutes and then filtered with bleached bleached cotton. 600 sheets cut into 5 cm were dipped. After standing overnight, the cloth was taken out, washed with running water, dehydrated and dried at room temperature to obtain a black tea-contaminated cloth.

[0081]

[Table 1]

1) 1-Hydroxyethylidene-1,1-
Diphosphonic acid 2) Polyoxyethylene lauryl ether (EO average addition mole number 10) 3) Polyoxyethylene lauryl ether (EO average addition mole number 6) 4) N-tetradecyl-N, N, N-trimethylammonium chloride 5) N -Lauryl-N, N-dimethyl-N- (2-hydroxy-1-sulfopropyl) ammonium sulfobetaine 6) sodium lauroyloxybenzenesulfonate 7) sodium decanoyloxybenzenesulfonate 8) sodium nonanoyloxybenzenesulfonate 9) Nonanoyloxybenzenecarboxylic acid 10 Isonanoyloxybenzenecarboxylic acid 11) Decanoyloxybenzenecarboxylic acid

[0083]

[Table 2]

12) Sodium polyacrylate (weight average molecular weight 10,000) 13) Carbopol 676 (manufactured by BF Goodrich) 14) Sodium polyoxyethylene lauryl ether sulfate (EO average added mole number 2) 15) Alkyl (carbon) Numbers 12 to 15) Sodium benzene sulfonate

[0085]

[Table 3]

[Brief description of drawings]

FIG. 1 is a schematic view showing an example of a two-component type container containing an agent A and an agent B.

FIG. 2 is a schematic diagram showing another example of a two-component type container containing an agent A and an agent B.

FIG. 3 is a schematic diagram showing another example of a two-component type container containing an agent A and an agent B.

FIG. 4 is a schematic diagram showing another example of a two-component type container containing an agent A and an agent B.

FIG. 5 is a schematic diagram showing an example of a measuring instrument for agents A and B.

FIG. 6 is a schematic view showing another example of a measuring instrument for agents A and B.

FIG. 7 is a schematic diagram showing an example of a two-component container equipped with the measuring device of FIG.

FIG. 8 is a schematic diagram showing another example of a two-component type container equipped with the measuring device of FIG.

FIG. 9 is a schematic diagram showing an example of a container that separately stores an agent A and an agent B.

[Explanation of symbols]

(11): Agent A storage section (12): Agent B container (13): Partition wall (14): Discharge part (1-1): Cap

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C11D 7/54 C11D 7/54 17/08 17/08 (72) Inventor Masataka Maki 1334 Minato, Wakayama, Wakayama Prefecture Kao Corporation Laboratory F-term (reference) 4H003 AB19 AB31 AC08 AD05 AE05 BA14 DA01 EA08 EA16 EB07 EB09 EB12 EB14 EB22 EB24 EB30 ED02 EE04 FA28 FA30 FA43

Claims (3)

[Claims] 1. A pH of 20 ° C. containing 0.05 to 10% by mass of hydrogen peroxide and 0.05 to 10% by mass of a bleach activator having an ester group, an imide group or a nitrile group. Content of one or more selected from carbonic acid, phosphoric acid, carboxylic acid, phosphonic acid, phosphonocarboxylic acid, and their ionized compounds or salts in an acid form. The agent B, which is an aqueous composition having a pH of 8.5 to 13.5 at 20 [deg.] C. of 0.5 to 10% by mass, is A agent / B agent = 10/1 by mass ratio. A method for bleaching a textile product, which comprises mixing within a range of 1/10 to prepare a mixed solution having a pH of 20 to 13.0 at 20 ° C., and then applying the mixed solution or a diluted solution thereof to a textile product. 2. The bleaching method according to claim 1, wherein the pH of the mixture obtained by mixing the agents A and B in equal amounts by mass ratio at 20 ° C. is 8.0 to 13.0. 3. The method for bleaching a textile product according to claim 1, wherein the bleaching activator is one or more compounds selected from alkanoyloxybenzenesulfonate, tetraacetylethylenediamine and alkanoyloxybenzenecarboxylic acid.