JPH02173198A - Granular bleaching detergent composition of high bulk density - Google Patents

Abstract

PURPOSE:To obtain the subject composition, containing an anionic surfactant, particulate peroxide, bleaching activator and enzyme at a specific ratio, excellent in preservation stability and capable of exhibiting high bleaching effects even after preservation for a long period. CONSTITUTION:The objective composition, containing (A) 3-40wt.% anionic surfactant, such as straight-chain alkylbenzenesulfonate, alpha-olefinsulfonate or alkyl sulfate, (B) 2-20wt.% particulate peroxide, capable of releasing hydrogen peroxide in an aqueous solution and having 250-1000mum particle diameter, (C) 0.01-10wt.% bleaching activator consisting of tetraacetylethylenediamine, nonanoyloxybenzenesulfonate, etc., and (D) 0.01-3wt.% enzyme, such as especially preferably alkaline lipase, capable of exhibiting high activity within an alkaline region and having 0.5-1.2g/cc bulk density.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a bleaching detergent composition with excellent storage stability.

Clothes detergent containing bleaching agent can be used to remove sebum stains from clothes, as well as tea, coffee, and fruit juice.

It has become popular in recent years because it can remove stains such as blood.

There are two types of bleach: oxidized and reduced. Oxidized bleach is commonly used because of its superior bleaching effect. Oxidizing bleaches are further classified into chlorine-based and oxygen-based bleaches, but the former has disadvantages such as not being able to be used on colored and patterned items because it discolors and fades the items being washed, and having a unique unpleasant odor.

Oxygen bleaches, on the other hand, are superior to chlorine bleaches in that they can be used over a wider range of applications and do not have unpleasant odors like chlorine bleaches, making them suitable as household bleaches.

However, oxygen bleaches generally have inferior bleaching blades compared to chlorine bleaches, and have the drawback of requiring a considerably long treatment time to obtain a sufficient bleaching effect.

For this reason, bleaching agents based on peroxides such as percarbonates and perborates have traditionally been used in bleaching agents such as tetraacetylethylenediamine (TAED) and tetraacetylglycoluril (TAED).
GU), pentaacetylglucose (PAG), and other bleaching activators have been used in combination to enhance the bleaching effect. However, bleaching detergents containing these activators have a problem in that their bleaching and cleaning performance deteriorates after storage. This problem was particularly noticeable in detergent compositions to which enzymes were added for the purpose of enhancing detergency.

On the other hand, conventional laundry detergents add a bulking agent (usually glauber's salt is used) that hardly contributes to cleaning performance to the composition, and then dry it by spray drying to obtain a bulk density of 0.3 g.
It was manufactured as bead-like hollow particles of about 1.0 cm/cc.

However, since such detergents have a light specific gravity, transportation costs are high, and they require a considerable amount of space to store and display.Furthermore, even in ordinary households, it is difficult to store them.
It was difficult to measure.

Therefore, recently, a method for manufacturing high bulk density granular detergent that can be used as a detergent with a small amount of detergent has been proposed (Japanese Unexamined Patent Application Publication No. 1983-1999).
-96698), and is also covered with cloth.

The object of the present invention is to provide a detergent composition that has excellent storage stability and exhibits a high bleaching and cleaning effect even after long-term storage.

Structure of the Invention The high bulk density granular bleaching detergent composition of the present invention comprises the following (a)
, (b), (c) and (d).

(a) Anionic surfactant = 3 to 40% by weight.

(b) Particle size 250-1 to release hydrogen peroxide in aqueous solution
000 μm granular peroxide 2-20% by weight.

(c) Bleach activator: 0.01-10% by weight.

(d) Enzyme: 0.01-3% by weight.

The present invention will be explained in more detail below.

Examples of the anionic surfactant of the (,) component include the following.

1) Straight-chain alkylbenzene sulfonate having an alkyl group with an average carbon number of 8 to 16; 2) α-olefin sulfonate having an average carbon number of 10 to 20; 3) An aliphatic residue having an average carbon number of 8 to 22. Sulfonate of fatty acid lower acyl ester, 4) Alkyl sulfate having an average carbon number of 10 to 20, 5) Having a linear or branched alkyl group or alkenyl group having an average of 10 to 20 carbon atoms, with an average of 0.5 Alkyl ether sulfate or alkenyl ether sulfate to which ~8 moles of ethylene oxide have been added; 6) Saturated or unsaturated fatty acid salt having an average carbon number of 10 to 22.

7) α-sulfo fatty acid salt represented by the following general formula.

R-CHC02Y S○, Z (In the formula, Y is an alkyl group having 1 to 30 carbon atoms or a counter ion, Z is a counter ion, and R is an alkyl group having 10 to 22 carbon atoms.) These anionic surfactants As the counter ion, an alkali metal salt such as sodium or potassium is usually suitable.

Component (a), an anionic surfactant, is present in the detergent composition at 3%.
-40% by weight, preferably 8-20% by weight.

If the amount is less than 3% by weight, sufficient detergency cannot be obtained, while if it exceeds 40% by weight, manufacturing becomes difficult.

Particulate peroxides that produce hydrogen peroxide in an aqueous solution of component (b) include percarbonate, perborate monohydrate and tetrahydrate, as well as pyrophosphate, citrate, sodium sulfate, Hydrogen peroxide adducts of urea and 1-lium silicate are preferred.

The peroxide has a particle size of 250 to 1000 μl, preferably 5
It is used in the form of granules of 00 to 1000 μm. If the particle size is less than 250 μm, storage stability will deteriorate;
If it exceeds .mu.m, the object to be washed will adhere to the cloth5, and the quality of the cleaning blade will decrease.

Component (b) granular peroxide is present in the detergent composition at a concentration of 2 to 20%.
It is blended in an amount of 4% to 15% by weight.

Component (c) bleach activators include tetraacetylethylenediamine, tetraacetylglycoluril, pentaacetylglucose, nonanoyloxybenzene sulfonate, and hydrogen atom of the 27th amino group in the heterocycle is substituted with a halogen atom. Nitrogen-containing heteroalicyclic compounds and the like are used. As the halogen bonded to the nitrogen atom of this nitrogen-containing heteroalicyclic compound, any of chlorine, bromine, and iodine can be used, but chlorine is particularly desirable from the cost standpoint.
Specific examples include the following.

1-chloro-piperidine 1-chloro-2-methyl-piperidine 1-chloro-3,5-dimethyl-piperidine 1-chloroisonipecotic acid 1-chloro-2,2,6,6-titramethylpiperidine 1- Chloro-2,2,6-trimethyl-6-isobutylpiperidine 1-chloro-4-oxo-2,2,6,6-titramethylpiperidine 1-chloro-4-oxo-2,2,6-drimethyl-
6-n-hexylpiperidine 6-chloro-6-aza-7,7-dimethyl-9-oxo-spiro[4,5]decane 1-chloro-1-aza-2,2-dimethyl-4-oxo-spiro (5,5) Undecane 1-chloro-4-hydroxy-2,2,6,6-tetramethylbiperidine: 1-chloro-4-hydroxyimino-2,2,6゜6-
Chitramethylpiperidine 1-chloro-1-aza-2,2-dimethyl-4-hydroxyimino-spiro(5,5)undecane 1-chloro-
4-Hydroxy-4-cyano-2,2゜6.6-tetramethylbiperidine 1-chloro-1-aza-2,2-dimethyl-4-hydroxy-4-cyano-spiro(5,5)undecane 1-chloro-4-amino-4-cyano-2,2,6゜6-titramethylpiperidine 1-0-(1'-chloro-2', 2', 6', 6
'-tetramethyl-4'-piperidyl)glycoside 1-
Chloro-2,2,6,6-titramethyl-4-piperidylphosphate 1-chloro-2,2,6,6-tetramethyl-4-isocyanate Piperidine 1-chloro-4-(N-(2-hydroxyethyl) methylamino)-2,2,6,6-titramethylpiperidine 1-chloro-4-(N-(2,3-dihydroxypropyl)methylamino)-2,2,6,6-titramethylpiperidine 1 -chloro-4-(N-(2-dihydroxyethyl)butylamino)-2,2,6,6-titramethylpiperidine 1-chloro-4-(N-(2,3-dihydroxypropyl)butylamino)- 2,2,6,6-Titramethylpiperidine -Chloro-4-(N,N-bis(2-hydroxyethyl)amino)-2,2,6,6-Titramethylpiperidine 1-Chloro-4-(N -(2-hydroxyethyl)-N
-(2,3-dihydroxypropyl)amino]-2゜2
．． 6.6-Tetramethylpiperidine 1-chloro-4-(N-acetyl-N-methylamino)
-2,2,6,6-tetramethylpiperidine 1-chloro-4-[N-acetyl-N-butylamino)-2,2,
6,6-Titramethylpiperidinetrimethyl-(1-chloro-2,2,6,6-tetramethyl-4-piperidyl)ammonium para-toluenesulfonate dimethyl-(1-chloro-2,2,6,6-tetramethyl -4-piperidyl)ammonium chloride dimethyl-(1-chloro-2,2,6,6-titramethyl-4-
piperidyl) ammonium acetate methyl-(2-hydroxyethyl) = (1-chloro 2.2,6.6-tetramethyl-4-piperidyl) ammonium chloride di(2-hydroxyethyl)-(1-chloro-2,2゜6.6-tetramethyl-4-piperidine) ammonium chloride spiro(4,5)-8-chloro-2-hydroxymethyl-7,7,9,9-tetramethyl-8-aza-1゜4-
Dioxadecane 1-chloro-4-methoxy-2,2,6,6-titramethylpiperidine 1-chloro-4-(N,N-bis(sodiumoxytriponylmethyl)amino)-2,2,6,6-titramethyl Piperidine 1-Chloromorpholine 1-Chloro-hexamethyleneimine 1-chloro-E-caprolactam 1-chloro-2,2,7,7-titramethyl-1゜4-
Diazacyclohebutan-5-one (c) component bleach activator is present in the detergent composition at a concentration of 0.01
-10% by weight, preferably 0.1-6% by weight.

(d) Component enzymes include protease, lipase,
Cellulases, amylases, and the like, particularly those showing high activity in the alkaline region, such as alkaline lipase, are preferred.

The enzyme component (d) is blended in the detergent composition in an amount of 0.01 to 3% by weight, preferably 0.1 to 2% by weight.

The high bulk density granular bleaching detergent composition of the present invention comprises the above (a)
, (b), (c), and (d), optional components such as other surfactants and builders may be contained.

As the nonionic surfactant, the following are suitable.

(1) An EO-added nonionic surfactant prepared by adding an average of 4 to 25 moles of ethylene oxide (EO) to a primary or secondary alcohol having 8 to 18 carbon atoms.

(2) EO-P○ addition type nonionic interface in which an average of 4 to 25 moles of ethylene oxide (EO) and an average of 3 to 15 moles of propylene oxide (po) are added to a primary or secondary alcohol having 8 to 18 carbon atoms. Activator.

In addition, zeolite, inorganic builders such as sodium tripolyphosphate and sodium pyrophosphate, sodium citrate, sodium ethylenediaminetetraacetate, nitrilotriacetate, sodium polyacrylate, sodium acrylate-sodium maleate anhydride copolymer, polyacetal carboxylate, etc. calcium ion scavenging builder,
Alkali builders such as carbonates and silicates, anti-recontamination agents such as carboxymethyl cellulose lene glycol, rinse improvers such as soaps, viscosity modifiers such as para-toluene sulfonates, toluene sulfonates, xylene sulfonates, and urea. , 4th
Softeners such as grade ammonium salts and bentonite, fluorescent agents, fragrances, and pigments can be used.

The detergent composition of the present invention has a bulk density of 0 by granulating the above components.
．． It is obtained by forming a high bulk density composition of 5 to 1 to 2 g/cc. This granulation method is as follows:
As described in JP-A-96698 and JP-A-62-597, each detergent raw material is kneaded and mixed with a kneader, crushed and granulated with a crusher such as a cutter mill type, and further processed into water-insoluble fine powder. Obtained by mixing the bodies. Alternatively, a high bulk density granular detergent composition can also be produced by spray-drying a portion of the detergent components in advance and kneading and mixing this spray-dried product with other detergent components. (b) component, (c) component, (d)
The components may be added to the granular detergent obtained as described above by a method such as powder mixing.

I'm in trouble According to the invention: (a) an anionic surfactant.

By combining (b) granular peroxide with a specific particle size, (c) bleach activator, and (d) enzyme to create a granular detergent with high bulk density, it has a much better shelf life than conventional bleaching detergents. Stability can be achieved and a high bleaching and cleaning effect can be exhibited even after long-term storage.

Hereinafter, the effects of the present invention will be specifically explained with reference to Examples, but prior to that, the evaluation method used in the Examples will be explained.

(1) Preservation of detergent Fill a carton with the bleaching detergent composition and store it in a constant temperature room at 45℃ for 1 hour.
It was stored for 4 days.

(2) How to make natural collar cloth Cut cotton cloth (cotton broadcloth No. 60) into 13 cm x 13 cm.

Sew the two short sides of the cut fabric together with a seam allowance of Lcm.
Make a collar cloth of x 24cm. The collar cloth is fixed to the collar of work clothes or shirts and worn for 2 to 7 days to cause contamination. Among the contaminated cloths, cloths with symmetrical stains were selected, cut in half, and used for experiments.

(3) One half of the contaminated fabric was washed with a standard detergent (detergent with no bleach or other bleach-activating agents added), and the other half was washed with the detergent of the present invention.

In advance, add 0.0% detergent to 4' DH water IQ at 25°C.
Put 20 pieces of collar cloth in a detergent solution containing 83 g of detergent, wash for 10 minutes at 120 rpm with a turbo meter, and wash for 3 minutes.
Evaluation was performed after rinsing for minutes and drying.

(4) Method for evaluating bleaching and cleaning power after washing Half-cut fabrics washed with the standard detergent and half-cut fabrics washed with the detergent of the present invention were visually evaluated. and.

The cleaned cloths were ranked based on the S+ semi-dirty cloth, which was ranked in 10 stages, and the relative cleaning power was expressed when the cleaning power of the standard detergent was set as 100.

Example 1 A high bulk density granular bleaching detergent (bulk density: 0.78 g/cc) having the composition shown in Tables 1 to 3 below was produced.

The components listed in the table below are kneaded in a kneader, and the resulting intimate mixture pellets (2 cm square) and A-type zeolite (sodium aluminosilicate) are crushed using a crusher (Speed Mill N manufactured by Okayama Seiko Co., Ltd.).
D-30 type). At this time, 15° C. cold air was introduced together with the crushed material at a ratio of 15Q/kg of crushed material. The crusher has 300 crushing blades with a diameter of 15 cm in 4 cross stages.
The screen was rotated at Orpm, and the screen used was a punching metal with a diameter of 2IIIIII and a porosity of 20%.

Next, the obtained crushed product and A-type zeolite 1- with an average primary particle size of 3 μm were fed into a transfer drum (D = 30 cmφ, 560 cm) at a ratio of 97:3, and the coated product was prepared at 30 rpm and residence time for 5 minutes. It was discharged. However, sodium percarbonate (average particle size 700 μm) [component (b)], bleach activator [component (C)], and enzyme [component (d)] were powder blended.

In addition, a bleaching agent [component (b)] and a bleach activator [(C
A high bulk density bleaching detergent was produced in the same manner as above except that component ) was not blended, and was used as a reference detergent.

Regarding the bleaching and cleaning effects of the examples of the present invention shown in each table,
The bleaching detergency after storage was evaluated in comparison with a standard detergent, and the results are shown in Tables 1 to 3.

(Leaving space below) LAS-; Straight-chain alkyl (
C engineering. ~□4) Potassium benzenesulfonate *4) Soap; CtJ~, 8 saturated fatty acid sodium ×
5) Adduct of alkyl (C13) ethoxylate with 15 moles of ethylene oxide on average *6) TMP-C1; 1-chloro-4-hydroxy-
2,2,6,6-titramethylpiperidine *7) TAED; Tetraacetylethylenediamine×
8) Alkaline protease manufactured by HNovo, Alcalase 4.0T*1) AS-; C engineering 2-1. Potassium alkyl sulfate*2) AES-Na (EOi5 =
3): Sodium polyoxyethylene Cl2-05 alkyl ether sulfate (average number of added moles of ethylene oxide: 3) ×3) Alkaline lipase i manufactured by Nova, Rivolase 30T*1) Alkaline cellulase; manufactured by NOν0, Cellzyme 5P-227 comparative example Granular detergent with the composition shown in Table 3 below (high bulk density 20.33g/
cc) was prepared by spray drying. however.

Sodium percarbonate (average particle size 700 μm) and TAE
D and alkaline protease were powder mixed after spray drying. In addition, a standard detergent having the composition shown in Table 4 below was prepared without powder mixing of sodium percarbonate and TAED.

Table-4 = Detergent composition (T%) Regarding this conventional detergent, standard detergent (bleach).

When the bleaching detergency after storage was evaluated with the amount of bleach (no bleach activator added) as 100, it was 100.

Claims (1)

[Claims] 1. (a) Anionic surfactant: 3 to 40% by weight, (b
) Particle size 250-100 to release hydrogen peroxide in aqueous solution
0 μm granular peroxide: 2-20% by weight, (c) bleach activator: 0.01-10% by weight and (d
) A high bulk density granular bleaching detergent composition containing 0.01 to 3% by weight of an enzyme.