JPH07197099A - Bleacher composition and bleaching detergent composition - Google Patents

Abstract

PURPOSE:To obtain a bleacher composition having good storage stability. CONSTITUTION:This bleacher composition comprises coated sodium percarbonate prepared by separately spraying a boric acid solution and an alkali metal silicate solution on sodium percarbonate particles and drying the particles and contains an bleaching activator represented by the formula (wherein R1 is a 2-20C hydrocarbon group which may be substituted; R2 is hydrogen or a lower alkyl; R3 is a bivalent hydrocarbon residue; and M is hydrogen or a counter ion forming a salt).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bleaching agent composition having good storage stability and a bleaching detergent composition containing the same.

[0002]

2. Description of the Related Art Currently, bleaching agents and bleaching detergents for clothing are
Sodium percarbonate and sodium perborate are mainly used as bleaching bases. However, since sufficient bleaching performance cannot be obtained with only these bases, organic peracid precursors such as TAED (tetraacetylethylenediamine), PAG (pentaacetylglucose) and OOBS (sodium octanoyloxybenzenesulfonate). Came to be used together. These organic peracid precursors react with hydrogen peroxide compounds such as sodium percarbonate to generate organic peracids with high bleaching effects, while effectively removing stains such as food stains and yellowing adhering to clothes. Causes embrittlement of the fiber,
In particular, when it is sprinkled on the fibers of the colored pattern together with the detergent component and left as it is, when it is dipped and washed, there is a problem that the dye of the fiber is also discolored at the same time. As a means for solving these problems, Japanese Examined Patent Publication No. 57-30188
Using amino acids described in Japanese Patent Publication No. 60-40
A method using an acylated amino acid described in Japanese Patent No. 544 has been proposed.

On the other hand, Japanese Patent Application No. 5-17945
The acyloxyanilide derivative, which is a novel bleaching activator described in the specification No. 4, is recognized to have an effect of preventing fading of dyes of fibers. However, the acyloxyanilide derivative-based bleach activator described above is still insufficient in terms of storage stability.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a bleaching composition having good storage stability.

[0005]

The bleaching composition of the present invention is characterized by containing the following components (A) and (B). (A) Sodium percarbonate coated by spraying sodium percarbonate particles separately with a boric acid solution and an alkali metal silicate solution and drying. (B) A bleaching activator represented by the general formula (I) shown below.

[0006]

[Chemical 2] (The abbreviations in the formula represent the following: R ₁ : a hydrocarbon group having 2 to 20 carbon atoms which may have a substituent R ₂ : a hydrogen atom or a lower alkyl group R ₃ : a divalent hydrocarbon Residue M: hydrogen atom or counter ion forming a salt)

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The sodium percarbonate as the component (A) used in the present invention is obtained by separately spraying sodium percarbonate particles with a boric acid solution and an alkali metal silicate solution and then coating them. This coating is obtained by spraying sodium percarbonate particles with a boric acid solution and an alkali metal silicate solution separately from two or more spray nozzles, simultaneously or sequentially. The solvent of boric acid and alkali metal silicate is preferably water in terms of solubility, safety and cost.

As boric acid as a coating agent, orthoboric acid, metaboric acid, tetraboric acid, etc. are used. The coating amount of boric acid is usually 0.3 to 20% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 8% by weight, particularly preferably 2 with respect to the base sodium percarbonate particles. ~
8% by weight.

As the alkali metal silicate, sodium metasilicate, sodium orthosilicate, water glass 1
No.2, No.3 sodium salt, potassium metasilicate,
One or more of potassium orthosilicate and the like can be used. Of these, water glasses No. 1, No. 2, No. 3 and No. 3 are liquid and are preferable from the viewpoint of convenience in use. The coating amount of the alkali metal silicate as a coating agent is 0.1 to 1 in terms of SiO ₂ with respect to the sodium percarbonate particles as a base.
It is 0% by weight, preferably 0.2 to 7% by weight, particularly preferably 0.3 to 5% by weight. In addition to the above coating agent, a stabilizer such as a conventionally known chelating agent may be used in combination with the coating agent.

Coated sodium percarbonate particles (hereinafter
The particle size of the coated sodium percarbonate) is 100 to 2
000 μm is suitable, and preferably 200 to 1500
μm. Boric acid and alkali metal silicate (SiO ₂
(Conversion) is not particularly limited, but 10: 1 to 1:
5 (weight ratio), preferably 8: 1 to 1: 2 (weight ratio),
It is particularly preferably 5: 1 to 1: 1 (weight ratio).

The coating amount of the coated sodium percarbonate of the present invention is preferably 40 to 90% by weight based on the whole bleaching composition. As the bleach activator which is the component (B) of the present invention,
An acyloxyanilide derivative-based bleaching activator having a structure represented by the general formula (I) is used.

Acyloxyanilide derivative-based bleach activator
In the general formula (I) representing ₁Has 2 to 20 carbon atoms
Alkyl group, alkenyl group, cycloalkyl group, ara
Shows hydrocarbon groups such as alkyl and aryl groups.
The hydrocarbon group may or may not have a substituent.
Good. R₁In, an alkyl group or an alkenyl group is
It may be linear or branched. Also, cycloalk
Examples of the radical group include a cyclopentyl group and a cyclohexyl group.
Examples of the aralkyl group include a silyl group and the like.
And aryl groups.
Is, for example, a phenyl group, a tolyl group, a xylyl group, a naphthyl group.
Examples thereof include a chill group.

When R ₁ has a substituent, examples of the substituent include an alkoxyl group and a quaternary ammonium group. Further, as long as the object of the present invention is not impaired, these substituents may be added together with these substituents, or It may be substituted with, for example, a hydroxyl group, an amino group, a halogen atom, a carboxyl group, a carboalkoxyl group, a sulfonic acid group, or a salt thereof in the absence of a substituent. R ₂ is a hydrogen atom or a lower alkyl group, and examples of such an alkyl group include a methyl group, an ethyl group, a propyl group and a butyl group.

R ₃ is a divalent hydrocarbon residue such as an alkylene group, an alkenylene group or an arylene group, and the alkylene group is a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group or a hexylene group. And the like, examples of the alkenylene group include a vinylene group, examples of the arylene group include a phenylene group,
Examples thereof include naphthylene group. The carboxyl group bonded to R ₃ may be in either an acid state or a salt state. That is, M in the general formula (I) is a counter ion forming a hydrogen atom or an alkali metal salt such as sodium and potassium, an alkaline earth metal salt such as magnesium, a substituted or unsubstituted ammonium salt and the like. .

The blending amount of the bleaching activator as the component (B) can be set arbitrarily, but it is 0.3 to 60% by weight in the bleaching agent composition.
It is suitable to be blended, and it is particularly preferable to blend in an amount of 0.5 to 40% by weight. The bleaching agent composition of the present invention can be obtained by mixing both components (A) and (B) described above, and further prepared by a conventional method by adding other known components shown below, if necessary. be able to. For example, a bleaching agent composition is prepared by adding an anionic surfactant, a nonionic surfactant, an inorganic / organic builder, an enzyme, a colorant, a fragrance, a fluorescent agent, etc. to both the components (A) and (B). You can

Furthermore, a bleaching detergent composition can be prepared by blending the component (A) and the component (B) with a detergent composition for clothing or the like. The bleaching detergent composition may contain known components such as a surfactant, an inorganic salt, a chelate builder, an anti-soil redeposition agent, an enzyme, a fluorescent agent, a fragrance and a coloring agent which are generally added.

As the anionic surfactant, a linear or branched alkyl (average carbon chain length 8 to 18) benzene sulfonate, a long chain alkyl (average carbon chain length 10 to 20) sulfonate, a long chain olefin (average Carbon chain length 10-20)
Sulfonate, long-chain monoalkyl (average carbon chain length 10
20) Sulfate ester salt, polyoxyethylene long-chain alkyl (average carbon chain length 10 to 16) Ether sulfate ester salt, polyoxyethylene alkyl (average carbon chain length 6 to 1)
2) Phenyl ether sulfate ester salt, long-chain monoalkyl, dialkyl or sesquialkyl phosphate, polyoxyethylene monoalkyl, dialkyl or sesquialkyl phosphate, etc. are used. These anionic surfactants may be added in an acid state, or may be added as an alkali metal salt such as sodium or potassium, an amine salt, an ammonium salt or the like.

The nonionic surfactant has about 8 carbon atoms.
24 higher alcohols, polyhydric alcohols, fatty acids, fatty acid amides, fatty amines, alkylphenols and n
-The alkylene oxide adduct of synthetic alcohol obtained by oxidizing paraffin or α-olefin is used.
As the alkylene oxide, ethylene oxide, propylene oxide and butylene oxide are used. Specifically, POE (p = 10) lauryl ether, POE
_{(P = 9) C 12 ~C} 14 secondary alkyl ether, POE
(P = 15) hexyl decyl ether, POE (p = 2
0) nonyl phenyl ether, POE (p = 11) stearyl ether, POE (p = 10) glyceryl monostearate, POE (p = 10) isostearyl ether, POE (p = 50) trimethylolpropane, PO
E (p = 30) hydrogenated castor oil, POE (p = 60) hydrogenated castor oil monolaurate, POE (p = 20) sorbitan monooleate, POE (p = 30) glyceryl triisostearate, POE (p = 20) ) glyceryl monostearate, POE (p = 6) stearylamine, lauroyl diethanolamide, POE (p = 10) stearyl amide, POE (p = 9) POP (p = 5) C 12 ~
C ₁₄ secondary alkyl ether and the like. POE is polyoxyethylene, POP is polyoxypropylene,
p represents the average number of moles of alkylene oxide added.

Examples of inorganic salts include carbonates, sulfates, silicates and the like. As the chelate builder, tripolyphosphate, ethylenediaminetetraacetate, diethylenetriaminepentaacetate, nitrilotriacetate, an inorganic phosphorus compound represented by 1-hydroxyethane-1,1-diphosphonate, a general formula of the following chemical formula 3 Examples thereof include polyphosphonic acids represented by the compounds represented by (III) to (VI), organic phosphates represented by phytic acid, (meth) acrylic acid-based polymers, and zeolite.

[0020]

Embedded image N (CH ₂ PO ₃ H ₂ ) ₃ (III) (H ₂ O ₃ PCH ₂ ) ₂ N (CH ₂ ) m N (CH ₂ PO ₃ H ₂ ) ₂ (IV) (In the formula, m = 2 to 6 and n = 1 to 2 are shown)

Anti-recontamination agents include polyvinyl alcohol, carboxymethyl cellulose and the like, and enzymes include protease, cellulase, amylase, alkaline lipase and the like. Tinopal as a fluorescent whitening agent to increase the bleaching effect on white fiber
CBS [made by Ciba-Geigy], Chinopearl SWN [made by Ciba-Geigy] and color brightening agents such as color index fluorescent whitening agents 28, 40, 61 and 71 are added. Good. It is preferable to add 1 to 40% by weight of the coated sodium carbonate as the component (A) in the bleaching detergent composition. The bleaching activator as the component (B) is usually 0.3 to 20% by weight, and preferably 0.5 to 10% by weight.

[0022]

INDUSTRIAL APPLICABILITY According to the present invention, the storage stability can be improved by combining the coated sodium percarbonate obtained by separately spraying the boric acid solution and the alkali metal silicate solution with a specific bleach activator. Good bleaching agent compositions and bleaching detergent compositions are obtained.

[0023]

EXAMPLES The present invention will be specifically described below with reference to examples, but the invention is not limited to these examples. Prior to this, the method for evaluating the storage stability (effective oxygen residual rate) and the method for producing the coated sodium percarbonate used in the examples are shown below.

(1) Effective oxygen residual rate A glass bottle was filled with 100 g of the bleaching agent composition or bleaching detergent composition, and after sealing, 45 ° C., 85% RH (16 hours) and 25 ° C., 60% RH (8 After storage for 30 days under the conditions of (1 hour), the amount of available oxygen was measured, and the residual ratio of available oxygen was calculated by the following formula 1 to evaluate the storage stability of sodium percarbonate.

[0025]

[Equation 1]

(2) Method for producing sodium percarbonate coated with boric acid and silicate The following sodium percarbonates (a) to (g) were produced.
Of these, (a) to (d) are the coated sodium percarbonates of the present invention, (e) and (f) are comparative sodium percarbonates, and (g) is an untreated untreated percarbonate for control. It is sodium.

(A) 8 kg of sodium percarbonate having an average particle size of 500 μm was placed on a perforated plate of a fluidized bed dryer having two spray nozzles, and hot air of 100 ° C. was sent from below to bring the sodium percarbonate into a fluidized state. I kept it. 40 cm from perforated plate
A 15% boric acid aqueous solution at 90 ° C. was sprayed at a flow rate of 80 g / min from the spray nozzle at the upper position, and at the same time 4
20 g of 90 ° C. water glass No. 1 aqueous solution (15% concentration as SiO ₂ ) from another spray nozzle located 0 cm above
Sprayed at a flow rate of / min. Spraying of both solutions was continued for 33.3 minutes while flowing with hot air. [The amount of boric acid with respect to sodium percarbonate is 5.0%, and the amount of water glass is 1.25.
% (As SiO ₂ )]. During this time, the temperature of sodium percarbonate was maintained in the range of 50 to 70 ° C. After stopping spraying of both solutions, air blowing was continued for another 10 minutes to obtain the coated sodium percarbonate (a) of the present invention. (B) The concentration of the water glass No. 1 aqueous solution is changed to SiO ₂ .
A coated sodium percarbonate (b) of the present invention was obtained in the same manner as in (a) except that the amount of boric acid was 5.0% with respect to sodium percarbonate, and the amount of water glass was 0.1%. 62%].

(C) The same procedure as in (a) was carried out except that the spraying was as follows. 90 ° C from spray nozzle 15
% Boric acid aqueous solution at a flow rate of 100 g / min for 26.7 minutes, then stop the boric acid aqueous solution spraying [the amount of boric acid to sodium percarbonate corresponds to 5.0%], and then perform another spraying. Water glass No. 1 aqueous solution (S
6. Concentration of 15% as iO ₂ ) at a flow rate of 100 g / min.
After spraying for 7 minutes [the amount of water glass relative to sodium percarbonate corresponds to 1.3% (as SiO ₂ )], the coated sodium percarbonate (c) of the invention was obtained.

(D) A coated sodium percarbonate (d) was obtained in the same manner as in (c) except that the aqueous solution of water glass No. 1 was first sprayed and then the aqueous boric acid solution was sprayed. In addition,
The obtained coated sodium percarbonate of the present invention had an average particle size of 500 to 1700 μm. (E) A coated sodium percarbonate (e) of a comparative example was obtained in the same manner as in (c) except that the water glass No. 1 aqueous solution was not sprayed.

(F) A coated sodium percarbonate (f) as a comparative example was obtained in the same manner as in (c) except that the aqueous boric acid solution was not sprayed. (G) Sodium percarbonate before coating used in (a) was used as it was without treatment, and was used as a control sodium percarbonate (g). Examples 1 to 12 In the bleaching agent composition shown in Table 1, sodium percarbonate of (a) to (g) and 2- (4-octanoyloxyphenyl) aminocarbonylbenzoic acid which is a bleaching activator were used. Table 2 shows the residual ratio of available oxygen in each case. Further, the residual rates of available oxygen in the bleaching detergent compositions shown in Tables 3 and 4 are shown in Tables 5 and 6.

[0031]

[Table 1] Table 1: Bleaching agent composition (% by weight) Bleaching agent A Bleaching agent B Bleaching agent C Sodium percarbonate 50 60 70 Bleaching activator 10 10 10 LAS-Na 1.0-1.0 Nonionic surfactant-0.5 0.5 NTA-3Na 3.0-Acrylic acid polymer-3.0-Enzyme 0.5-0.5 Calcium sulfate hemihydrate 1.0-1.0 Perfume 0.1-0.1 Fluorescent agent-0.1 0.1 Sodium carbonate balance Residual bleach activator: 2- (4 over octanoyloxy phenyl) aminocarbonyl benzoic acid LAS-Na: a linear alkyl (C ₁₀ -C ₁₄₎ benzene sulfonate, sodium nonionic surfactant: POE (p = 9) secondary alkyl (C ether NTA: nitrilotriacetic Sodium acetate Acrylic acid-based polymer: Acrylic acid / maleic acid copolymer (Molecular weight 50000) Enzyme: Protease (Novo Industry Co .; Alcala Ze 6.0T) fluorescent agent: Tinopal CBS over X (manufactured by Ciba-Geigy)

[0032]

Table 2: Storage stability in bleach composition Effective oxygen residual rate (%) Sodium percarbonate Bleach A Bleach B Bleach C Example 1 a 99 99 96 96 Example 2 b 99 99 95 Example 3 c 99 98 96 Example 4 d 99 98 95 Comparative Example 1 e 72 69 58 Comparative Example 2 f 66 61 54 Comparative Example 3 g 55 51 47 Bleach Activator: 2- (4 octanoyloxyphenyl)
Aminocarbonylbenzoic acid

[0033]

[Table 3] Bleach activator: 2- (4 octanoyloxyphenyl)
Aminocarbonylbenzoic acid AOS-Na: C₁₄~ C₁₈Α-olefin sulfonic acid
Sodium LAS-Na: Linear alkyl (C_Ten~ C₁₄) Benz
Sodium Ruphonate AS-Na: C₁₂~ C₁₅Alkylsulfate AES-Na (p = 3): Polyoxyethylene C₁₂~ C
₁₅Sodium alkyl ether sulfate Soap: C₁₄~ C₁₈Saturated fatty acid sodium PEG # 6000: polyethylene glycol (molecular weight 6
000) Chinopearl CBS-X: Optical brightening agent (Ciba Geigy)
Made)

[0034]

[Table 4] Table 4: High bulk density bleaching detergent composition (bulk conductivity: 0.78 g / cc) Composition (% by weight) Detergent C Detergent D Detergent E α-SF-Na--15 AOS-K- 158 LAS -K-20 3 LAS-Na 22 --- AS-Na 10 --- AES-Na (p = 3) 3 --- Soap 1 11 1 Nonionic surfactant 5 5 5 PEG # 6000 11 1 1 Zeolite (4A type) 20 20 20 Sodium silicate 10 5 4 Sodium carbonate 10 10 20 Potassium carbonate-5 5 5 Sodium percarbonate 10 10 10 Bleach activator 1 5 7 Tinopearl CBS-X 0.2 0.2 0.2 Water balance Residual bleaching Activator: 2- (4-octanoyloxyphenyl) aminocarbonylbenzoic acid α-SF-Na: C _{14 to} C ₁₆ sodium sulfonate of saturated fatty acid methyl ester AOS-K: C _{1 4} -C ₁₈ of α over potassium olefin sulfonate LAS-Na: a linear alkyl (C ₁₀ ~C ₁₄₎ sodium benzenesulfonate LAS-K: a linear alkyl (C ₁₀ ~C ₁₄₎ potassium benzenesulfonate AS-Na : C _{12 to} C ₁₅ sodium alkylsulfate AES-Na (p = 3): polyoxyethylene C _{12 to} C
₁₅ alkyl ether sulfate sodium soap: C ₁₄ -C ₁₈ saturated fatty acid sodium nonionic surfactant: alkyl (C ₁₃₎ ether ethoxylate (ethylene oxide average addition molar number = 15) PEG # 6000: polyethylene glycol (molecular weight 6
000) Chinopearl CBS-X: optical brightener (manufactured by Ciba Geigy)

[0035]

Table 5: Storage stability in conventional bleaching detergent composition Effective oxygen residual rate (%) Sodium percarbonate Detergent A Detergent B Example 5 a 75 78 Example 6 b 73 75 Example 7 c 74 75 Example 8 d 75 77 Comparative example 4 e 50 50 Comparative example 5 f 10 12 Comparative example 6 g 11 Bleach activator: 2- (4-octanoyloxyphenyl) aminocarbonylbenzoic acid

[0036]

Table 6: Storage stability in high bulk density bleaching detergent compositions Effective oxygen residual rate (%) Sodium percarbonate Detergent C Detergent D Detergent E Example 9 a 84 84 85 Example 10 b 80 81 81 Example 11 c 81 82 82 Example 12 d 84 84 85 Comparative Example 7 e 57 59 70 Comparative Example 8 f 10 10 12 Comparative Example 9 g 1 1 3 Bleach Activator: 2- (4-octanoyloxyphenyl) aminocarbonyl benzoic acid

Examples 13 to 20 Sodium percarbonate a and bleach activators I to V shown in Table 7
III was added to Bleach A, Detergent B, and Detergent C, and the storability was evaluated. The results are shown in Table 8.

[0038]

[Table 7]Table 7: Bleach activators used symbol Bleach activator I 2- (4-Propionyloxyphenyl) aminocarbonylbenzoic acid II 3- (4-Octanoyloxyphenyl) aminocarbonylpropionic acid III 2- (4-octanoyloxyphenyl) aminocarbonyl potassium benzoate IV 2- ( 4-benzoyloxyphenyl) aminocarbonylbenzoic acid V 2- (4-octanoyloxyphenyl) aminocarbonylbenzoic acid sodium VI VI 3- (4-octanoyloxyphenyl) aminocarbonylpropionic acid magnesium VII 2- (4-octa Noyl glycooxyphenyl) aminocarbonylbenzoic acid VIII 2- (4- (4-trimethylaminobutanoyl) oxyphenyl) amino Carbonyl sodium benzoate

[0039]

[Table 8] Table 8: Evaluation result of storability Effective oxygen residual rate (%) Bleach activator Bleach A Detergent B Detergent D Example 13 I 99 77 85 Example 14 II 99 76 85 85 Example 15 III 99 76 83 Example 16 IV 99 78 85 85 Example 17 V 99 75 82 Example 18 VI 99 77 85 Example 19 VII 99 78 84 Example 20 VIII 99 77 85

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mieko Inami 1-3-7 Main Office, Sumida-ku, Tokyo Lion Corporation

Claims (2)

[Claims] 1. A sodium percarbonate coated with (A) sodium percarbonate particles separately sprayed with a boric acid solution and an alkali metal silicate solution and dried (B). ) A bleaching activator represented by (The abbreviations in the formula represent the following: R ₁ : a hydrocarbon group having 2 to 20 carbon atoms which may have a substituent R ₂ : a hydrogen atom or a lower alkyl group R ₃ : a divalent hydrocarbon Residue M: a hydrogen atom or a counter ion which forms a salt), a bleaching composition. 2. A bleaching detergent composition comprising the bleaching agent composition according to claim 1.