JPH0782591A - Liquid bleaching agent composition - Google Patents

Abstract

PURPOSE:To obtain a liquid bleaching agent compsn. which has a high bleaching capability under alkaline, neutral, and acidic conditions and a high storage stability by compounding a nonionic surfactant, H2O2, a specific bleaching activator, and a specific compd. CONSTITUTION:This compsn. contains a nonionic surfactant, H2O2, a bleaching activator of the formula: R<1>COL [wherein R<1> is 1-20C alkyl, alkenyl, or a 6-18C aryl group optionally substd. by 1-12C alkyl group; and L is a group selected from groups of formulas I-VI (wherein M is a cationic group; X-is an anionic group; R<2> is 2-3C alkylene; R<3> to R<5> are each 1-10C alkyl, hydroxyalkyl, etc.; and m is 0-20)], and a quaternary ammonium compd. of formula VII (wherein R<6> to R<9> are each OH, alkenyl, etc.) or an anionic compd. of the formula: R<10>Z (wherein R<10> is R<1>; and Z is COOM, etc.) provided that when L of the activator is a group selected from groups of formulas I to IV, then the compd. of formula VII is contained in the compsn. and when L is a group of formula V or VI, then the compd. of the formula: R<10>Z is contained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid bleaching composition, and more specifically, it contains a bleaching activator which reacts with hydrogen peroxide to produce an organic peracid, thereby improving storage stability. An excellent liquid bleach composition.

[0002]

BACKGROUND OF THE INVENTION Bleaching agents are classified into chlorine-based bleaching agents and oxygen-based bleaching agents, but chlorine-based bleaching agents are limited in the fibers that can be used, and are used for colors and patterns. Oxygen-based bleaching agents, which do not have these drawbacks, have recently become remarkably prevalent due to their inability and their unique odor. Among the oxygen-based bleaching agents, sodium percarbonate and sodium perborate are used as powder bleaching agents, and hydrogen peroxide is used as a liquid bleaching agent.

However, these oxygen-based bleaching agents have a weaker bleaching power than chlorine-based bleaching agents, and usually various bleaching activators are used together. Examples of these bleach activators include O-acetylated compounds represented by glucose pentaacetate (GPAC), N-acylated compounds represented by tetraacetylethylenediamine, and acid anhydrides represented by maleic anhydride. can give. Furthermore, the inventors of the present invention have disclosed JP-A-63-233969 and JP-A-63-3.
As illustrated in Japanese Patent No. 1566, Japanese Patent Application Laid-Open No. 64-68347, Japanese Patent Application Laid-Open No. 1-190654, and the like,
It has been found that a compound that reacts with hydrogen peroxide to form an organic peracid having a quaternary ammonium group is extremely excellent as a bleach activator. Further, examples of organic peracid precursors having an anionic group are illustrated in JP-B-63-12520.

These bleach activators are compounds which react with hydrogen peroxide to produce an organic peracid even under relatively mild conditions such as washing conditions. Unstable. For this reason, it is usually difficult to use these bleach activators as components of liquid bleaching compositions, and mixtures of solid persalts with dry particles of these bleach activators to keep them dry. It is generally used as a composition consisting of

A liquid bleaching composition containing a bleaching activator which produces an organic peracid is disclosed in JP-A-62-2308.
Japanese Patent Laid-Open No. 97 discloses a composition obtained by dispersing a solid bleaching activator in an acidic aqueous solution containing hydrogen peroxide, which has excellent storage stability and exhibits activity at low temperatures. However, since the bleach activator was in a dispersed state in this composition, the bleach activator was precipitated and separated during storage, and the appearance of the product was remarkably impaired. Further, this composition has a problem that the bleaching activator is gradually decomposed by being stored in an aqueous solution, and a satisfactory bleaching power cannot be obtained at the time of use.

Further, in this composition, since the bleach activator is not dissolved in the composition but is present in a dispersed state, the bleach activator remains undissolved during actual bleaching. When it adheres to the bleached product, the dye in that part is discolored.

[0007] Therefore, the problem to be solved by the present invention is not only alkaline, but also shows high bleaching performance not only under neutral or acidic conditions, but also has extremely excellent storage stability, and further causes decolorization of dyes in fibers. No liquid bleach composition is provided.

[0008]

As a result of intensive studies, the present inventors have found that the above problems can be solved by combining four specific components, and have completed the present invention.

That is, the present invention provides the following component (a):
The present invention provides a liquid bleaching composition containing the component (b), the component (c) and the component (d). Component (a): Nonionic Surfactant (b) Component: Hydrogen Peroxide (c) Component: Bleach Activator Represented by General Formula (I) R ¹ COL (I) [wherein R ¹ : It represents an aryl group having 6 to 18 carbon atoms which may be substituted with an alkyl group having 1 to 20 carbon atoms, an alkenyl group or an alkyl group having 1 to 12 carbon atoms.

[0010]

[Chemical 6]

Here, M represents a cation group, and X ⁻ represents an anion group. R ² represents an alkylene group having 2 to 3 carbon atoms, R ³ , R ⁴ and R ⁵ represent an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group or an alkenyl group, or an alkyl group having 1 to 12 carbon atoms. It represents an aryl group having 6 to 18 carbon atoms which may be substituted with a group. R ³ , R ⁴ and R ⁵ may be the same or different from each other. m shows the number of 0-20. Component (d): quaternary ammonium compound represented by the general formula (II) or an anionic compound represented by the general formula (III)

[0012]

[Chemical 7]

[Wherein R ⁶ , R ⁷ , R ⁸ and R ^{9 are a} hydroxyl group and R ²⁰ CON
H- group or R ²¹ COO- represents an optionally substituted alkyl group or alkenyl group having 1 to 20 carbon atoms, or substituted with an alkyl group having 1 to 12 carbon atoms And optionally represents an aryl group having 6 to 18 carbon atoms or a benzyl group having 7 to 19 carbon atoms. Here, R ²⁰ and R ²¹ are the same or different and each represents an alkyl group having 1 to ²¹ carbon atoms.
R ⁶ , R ⁷ , R ⁸ and R ⁹ may be the same or different. X ^-: The meanings of the. R ¹⁰ Z (III) [wherein R ¹⁰ represents an alkyl group or an alkenyl group having 1 to 20 carbon atoms, or has 6 to 12 carbon atoms which may be substituted with an alkyl group having 1 to 12 carbon atoms] 18 aryl groups are shown.

[0014]

[Chemical 8]

A group represented by: Where Y is -CH ₂ COO
Represents a group represented by M, -SO ₃ M or -PO ₃ M, R ² , m and
M has the above-mentioned meaning. However, in the component (c), in the compound represented by the general formula (I), the L 3 group is

[0016]

[Chemical 9]

In the case of the group represented by the formula (d), the component (d) is a compound represented by the general formula (II), and among the compounds represented by the general formula (I) in the component (c), L Basis

[0018]

[Chemical 10]

In the case of a group represented by the formula (wherein R ² , R ³ , R ⁴ , R ⁵ , m, X ^- have the above meanings), the component (d) is represented by the general formula (III) Is a compound represented by.

The present invention will be described in detail below.

[Component (a)] The nonionic surfactant used as the component (a) of the present invention is not particularly limited, but may be polyoxyethylene alkyl or alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher grades. Examples thereof include fatty acid alkanolamides, sucrose fatty acid esters, alkyl glucosides, glycerin higher fatty acid esters, and polyoxyethylene higher fatty acid esters. Among these, polyoxyethylene alkyl (or alkenyl) ethers represented by the following general formula (IV) are particularly preferable.

R ¹¹ -O- (R ² O) _n -H (IV) [In the formula, R ¹¹ represents an alkyl group or an alkenyl group having 8 to 24 carbon atoms.

R ² : Shows the above meaning. ].

[Component (c)] The component (c) of the present invention is a bleaching activator, and the bleaching activator used is limited to those having an ionic group represented by the general formula (I). . Specific examples of these include the following compounds.

[0025]

[Chemical 11]

These may be used alone or as a mixture of two or more.

[Component (d)] In the present invention, as the component (d), a quaternary ammonium compound represented by the general formula (II) or an anionic compound represented by the general formula (III) is used. Is used.

<Quaternary Ammonium Compound (II)> Fourth
Examples of the quaternary ammonium compound (II) are as follows.

[0029]

[Chemical 12]

[0030]

[Chemical 13]

<Anionic Compound (III)> The following is an example of the anionic compound (III).

1) Alkylbenzene sulfonates having an alkyl group having 8 to 20 carbon atoms 2) Having an alkyl group or an alkenyl group having 8 to 20 carbon atoms, and the addition mole number of ethylene oxide and / or propylene oxide is 1 to 20. Alkyl or alkenyl ether sulfates 3) C8-20 olefin sulfonates 4) C8-20 alkane sulfonates 5) C8-20 saturated or unsaturated fatty acid salts 6) C8 Alkyl or alkenyl groups having 1 to 20 alkyl groups or alkenyl groups and 1 to 20 added moles of ethylene oxide and / or propylene oxide 7) α having an alkyl group or alkenyl group having 8 to 20 carbon atoms -Sulfo fatty acid salts 8) α-sulfo fatty acid esters having an alkyl group or an alkenyl group having 8 to 20 carbon atoms It is below. Of these, the following compounds are particularly preferable.

[0033]

[Chemical 14]

[0034] _{C 12 H 25 - (OC 2} H 4) m 'OSO 3 Na, C 14 H 29 - (OC 2 H 4)
_{m 'OSO 3 Na, C 16} H 33 - (OC 2 H 4) m' OSO 3 Na, C 18 H 37 - (OC 2 H 4) m '
OSO ₃ Na, C ₁₂ H ₂₅ -OSO ₃ Na, C ₁₄ H ₂₉ -OSO ₃ Na, C ₁₆ H ₃₃ -OSO
_{3 Na, C 18 H 37 -OSO} 3 Na, C 12 H 25 - (OC 2 H 4) m 'OCH 2 COONa,
_{C 14 H 29 - (OC 2} H 4) m 'OCH 2 COONa, C 16 H 33 - (OC 2 H 4) m' OCH 2 CO
_{ONa, C 18 H 37 - (} OC 2 H 4) m 'OCH 2 COONa, C 11 H 23 COONa, C
₁₃ H ₂₇ COONa, C ₁₅ H ₃₁ COONa, C ₁₇ H ₃₅ COONa (wherein m ′ is a number from 1 to 20).

[Liquid Bleaching Agent Composition] The liquid bleaching agent composition of the present invention contains the component (a) in an amount of 0.5 to 30% by weight, preferably 5 to 30% by weight.
25% by weight, 0.3 to 30% by weight of component (b), preferably
It contains 0.5 to 20% by weight. In addition, (c) component and (d)
As the combination of the components, in the component (c), the L group in the compound represented by the general formula (I) is

[0036]

[Chemical 15]

In the case of the group represented by the formula (d), the compound represented by the general formula (II) is selected as the component (d), and among the compounds represented by the general formula (I) in the component (c), L But

[0038]

[Chemical 16]

In the case of the group represented by the formula (d), the component (d) has the general formula
The compound represented by (III) is selected.

The liquid bleach composition of the present invention contains the component (c).
The content of the component (d) is 0.5 to 20% by weight, preferably 0.5 to 10% by weight, and the component (d) is 0.5 to 20% by weight, more preferably 0.5 to 15% by weight. The ratio (weight ratio) of component (c) / component (d) is preferably 1/1 to 1/20. When the quantitative relationship is satisfied in the present invention, the object of the present invention is better achieved.

The liquid bleaching composition of the present invention is basically prepared by dissolving or dispersing the components (a) to (d) in water, but the liquid is stabilized and frozen at a low temperature. A hydrotrope agent may be added for the purpose of improving the properties and preventing liquid separation at 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 examples include alcohols and polyhydric alcohols. The hydrotrope agent can be incorporated in the bleaching composition in an amount of about 0 to 30% by weight.

If desired, a chelating agent may be added to the liquid bleaching composition of the present invention. As the chelating agent, (1) a phosphoric acid compound such as phytic acid or an alkali basic salt or alkanolamine salt thereof (2) ethane-1,1-diphosphonic acid, ethane-1,1,
2-triphosphonic acid, ethane-1-hydroxy-1,1
-Diphosphonic acid and its derivatives, ethanehydroxy-
Phosphonic acids such as 1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid, or their alkali metal salts or alkanolamine salts (3) 2-phosphonobutane- 1,2-dicarboxylic acid, 1-
Phosphonobutane-2,3,4-tricarboxylic acid, phosphonocarboxylic acid such as α-methylphosphonosuccinic acid, or an alkali metal salt or alkanolamine salt thereof (4) Amino acid such as aspartic acid, glutamic acid, glycine or the alkali thereof Metal salts or alkanolamine salts (5) Nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid,
Aminopolyacetic acid such as triethylenetetramine hexaacetic acid and diencoric acid or their alkali metal salts or alkanolamine salts (6) Diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid , Oxydisuccinic acid, gluconic acid, carboxymethyl succinic acid, carboxymethyl tartaric acid, and other organic acids, or their alkali metal salts or alkanolamine salts (7) Alkali metal salts of aluminosilicate represented by zeolite A or alkanolamine salts (8) ) Aminopoly (methylenephosphonic acid) or its alkali metal salt or alkanolamine salt, or polyethylenepolyamine poly (methylenephosphonic acid) or its alkali metal salt or alkanolamine salt .

The amount of such a chelating agent is 0.0005 to 5% by weight, preferably 0.01 to 1 based on the liquid bleaching composition.
Weight percent is preferred.

Further, the liquid bleaching composition of the present invention may further contain various compounds. For example, phosphoric acid, which is known as a stabilizer of hydrogen peroxide, barbituric acid, uric acid, acetanilide, aminopolycarboxylic acids represented by oxyquinoline and phenacetin, and DL-α-tocopherol, a gallic acid derivative, Butylated hydroxyanisole (BHA), 2,6-di-tert
-Butyl-4-methylphenol (BHT) and the like can be added. The addition amount of these stabilizers depends on the concentration of hydrogen peroxide, but is usually about 0 to 5%, preferably
It is preferable to contain 0.01 to 3%.

Further, the liquid bleaching composition of the present invention may contain a substance known as an anti-fading agent. Such substances include phenylalanine, histidine,
Amino acids and amino acid salts such as lysine, tyrosine and methionine, and amino or imide compounds such as hydroxyiminodiacetic acid, and one or more monomers copolymerizable with acrylonitrile and acrylonitrile having a quaternary ammonium group. And the like. 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.

In order to increase the bleaching effect on white fiber, Tinopal CBS is used as a fluorescent whitening agent.
[Made by Ciba-Geigy], Chino Pearl SW
Optical brighteners such as N (manufactured by Ciba Geigy) and color index optical brighteners 28, 40, 61, 71 may be added in an amount of 0 to 5%.

Further, it is possible to add a thickener in an amount of 0 to 20% for the purpose of increasing the viscosity of the composition and improving the usability. Generally, polyacrylic acid salts, acrylic acid-maleic acid copolymers, carboxymethylcellulose derivatives, synthetic polymers such as methylcellulose and hydroxymethylcellulose, natural polymers such as xanthan gum, guar gum and kerzan, and water-swelling clay minerals such as montmorillonite and bee gum. And so on. In addition, JP-A 1-319
It is also possible to impart viscoelastic rheological properties by combining an amphoteric surfactant and an anionic surfactant as described in JP-A-600.

Further, the liquid bleach composition of the present invention further comprises coloring agents such as dyes and pigments, perfumes, silicones,
Various trace additives such as bactericides, ultraviolet absorbers and inorganic electrolytes can be added in appropriate amounts (about 0 to about 2% each). As the dye, an acid dye having hydrogen peroxide resistance in an acid solution is particularly preferable.

In the composition of the present invention, conventionally known enzymes (cellulase, amylase, protease, lipase, etc.) can be added, if necessary, in order to improve the bleaching performance.

The pH of the liquid bleach composition of the present invention is preferably 6 or less, more preferably 3.5 or less. In order to adjust the pH, inorganic acids such as sulfuric acid and phosphoric acid, organic acids such as toluenesulfonic acid and benzenesulfonic acid are used, and the above chelating agents and anionic surfactants are used in the acid form. It is advisable to add it or adjust it with a caustic alkali such as sodium hydroxide or potassium hydroxide if necessary.

The liquid bleaching composition of the present invention contains at least one selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid, and alkali metal salts thereof and alkaline earth metal salts thereof (eg, NaCl, Na ₂ SO ₄ , H ₃ PO _4, etc.) may be contained in an amount of 0 to 5% by weight.

[0052]

EFFECTS OF THE INVENTION According to the present invention, liquid bleaching that exhibits high bleaching performance not only under alkaline conditions but also under neutral or acidic conditions, has excellent storage stability, and does not cause decolorization of dyes in fibers. An agent composition can be provided.

[0053]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 9 and Comparative Examples 1 to 4 (a-1) to (a-2) shown below as the component (a) and (c-1) to (c-4) shown as the component (c). , (D-1) to (d-5) shown below as the component (d) and a chelating agent (e-1) were used to prepare a liquid bleaching composition with the composition shown in Table 1, and each bleaching composition was prepared. The effect, storage stability and decolorization test were conducted. The composition shown in Table 1 was adjusted to pH 2 with 0.5N sulfuric acid aqueous solution.

[0055]

[Chemical 17]

[0056]

[Chemical 18]

<Evaluation of Storage Stability> The amount of the bleach activator which forms an organic peracid in the sample was measured, and the effective bleach activator residual rate was calculated by the following formula.

[0058]

[Equation 1]

<Method of measuring bleaching performance> 40 ml of the bleaching agent composition shown in Table 1 was added to a 2 liter aqueous solution containing 0.133% commercial detergent solution (pH = 10.2), and a black tea-contaminated cloth prepared as follows was prepared. Five pieces were soaked for 15 minutes each. Then, it was rinsed with tap water and dried, and the bleaching rate was calculated by the following formula. * Bleaching rate of black tea contaminated cloth

[0060]

[Equation 2]

The reflectance is NDR-1 manufactured by Nippon Denshoku Industries Co., Ltd.
It was measured using a 460 nm filter at 01DP.

* Preparation method of black tea-contaminated cloth 80 g of Nitto black tea (yellow package) was boiled in 3 liters of ion-exchanged water for about 15 minutes, rubbed with de-squeezed bleached cotton, and soaked with cotton cloth # 2003. Boiled for about 15 minutes. As it was, it was taken out of the heat, left to stand for about 2 hours to be naturally dried, washed with water until the washing liquid became colorless, dehydrated, pressed, and made into a test piece of 10 cm × 10 cm, which was used for the experiment.

<Decolorization test> Naphthol dye (undercoating agent; Naphthol AS, color developing agent; Fast Red GBas on a petri dish)
Prepare a cotton cloth (10 cm x 10 cm) dyed in e). 0.133%
40 ml of the bleaching agent composition shown in Table 1 was added to a 2 liter aqueous solution containing a commercially available detergent solution (pH = 10.2), and 5 sheets of each were immersed for 30 minutes each, and then rinsed with tap water and dried. This operation was repeated 20 times, and the degree of decolorization was evaluated according to the following 4 grades.

◎… No bleaching at all ○… Slightly thin, but not noticeable at all △… Partly bleaching ×… Discoloration spreads over the entire cloth

[0065]

[Table 1]

[0066]

[Table 2]

In Tables 1 and 2,% means% by weight, and balance means the amount of balance to make 100 as a whole.
The “liquid state” is the state immediately after preparation.

Claims (1)

[Claims] 1. A liquid bleaching composition containing the following component (a), component (b), component (c) and component (d). Component (a): Nonionic Surfactant (b) Component: Hydrogen Peroxide (c) Component: Bleach Activator Represented by General Formula (I) R ¹ COL (I) [wherein R ¹ : It represents an aryl group having 6 to 18 carbon atoms which may be substituted with an alkyl group having 1 to 20 carbon atoms, an alkenyl group or an alkyl group having 1 to 12 carbon atoms. [Chemical 1] Where M is a cation group and X ^- is an anion group. R ² represents an alkylene group having 2 to 3 carbon atoms, R ³ , R ⁴ and R ⁵ represent an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group or an alkenyl group, or an alkyl group having 1 to 12 carbon atoms. It represents an aryl group having 6 to 18 carbon atoms which may be substituted with a group. R ³ , R ⁴ and R ⁵ may be the same or different from each other. m shows the number of 0-20. Component (d): quaternary ammonium compound represented by the general formula (II) or an anionic compound represented by the general formula (III) [In the formula, R ⁶ , R ⁷ , R ⁸ and R ^{9 are} : a hydroxyl group, a group represented by R ²⁰ CONH- or a group represented by R ²¹ COO-, which has 1 to 20 carbon atoms and may be substituted. It represents an alkyl group or an alkenyl group, or may be substituted with an alkyl group having 1 to 12 carbon atoms, or an aryl group having 6 to 18 carbon atoms or 7 to 19 carbon atoms in total.
The benzyl group of is shown. Here, R ²⁰ and R ²¹ are the same or different and each represents an alkyl group having 1 to ²¹ carbon atoms. R ⁶ , R ⁷ , R ⁸ and
R ⁹ may be the same or different from each other. X ^-: The meanings of the. R ¹⁰ Z (III) [wherein, R ¹⁰ represents an alkyl group or an alkenyl group having 1 to 20 carbon atoms, or a total carbon number of 6 to which may be substituted with an alkyl group having 1 to 12 carbon atoms] 18 aryl groups are shown. [Chemical 3] Represents a group represented by. Where Y is -CH ₂ COOM, -SO ₃ M or
A group represented by —PO ₃ M is shown, and R ² , m and M have the above-mentioned meanings. However, in the component (c), in the compound represented by the general formula (I), the L group is In the case of the group represented by, the component (d) is a compound represented by the general formula (II), and in the compound represented by the general formula (I) in the component (c), the L group is Chemical 5] (In the formula, R ² , R ³ , R ⁴ , R ⁵ , m and X ⁻ have the above meanings.) In the case of the group (d), the component (d) has the general formula (I
It is a compound represented by II).