JPH03215599A - Bleaching detergent composition - Google Patents

Abstract

PURPOSE:To improve a bleaching and cleaning effect by incorporating a nonionic surfactant, a zeolite, a peroxide, an org. peroxy acid precursor and a specified copolymer. CONSTITUTION:A bleaching detergent compsn. comprising 8-35wt.% (hereinbelow described as %) nonionic surfactant (A) (e.g. a polyoxyethylene alkyl ether with an alkyl group of a mean carbon number of 10-20 and 1-30mol of ethylene oxide added thereto), 20-60% synthetic crystalline zeolite (B), 5-20% peroxide (C) generating H2O2 in a water-soluble soln. (e.g. sodium perborate hydrate), 1-10% org. peroxy acid precursor (D) reacting with H2O2 of formula I, II, etc., to give an org. peroxy acid having a group of formula III, 1-5% copolymer (E) with the units of formula IV [wherein M is H, alkali (alkaline earth) metal, a (substd.) ammonium] in the molecule and an average mol.wt. of 800-1,000,000 (e.g. a maleic acid-acrylic acid copolymer) and 0.5-2% bleaching stabilizer (F) [e.g. aminotri(methylene)phosphonic acid] and which does not contain 0.1% or more phosphate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a bleaching detergent composition. [Prior art and problems to be solved by the invention] Peroxides that generate hydrogen peroxide in an aqueous solution, such as sodium percarbonate and sodium perborate, are widely used as bleaching bases in bleaching detergent compositions. There is.

This oxygen bleach has weaker bleaching power than chlorine bleach.
Various bleach activators are used in combination.

These bleach activators include nitriles such as acetonitrile, glucose pentaacetate (GPAC), etc.
Examples include O-acetylated products such as 0-acetylated products such as Tetraacetylethylenediamine (TAED), N-acetylated products such as tetraacetylethylenediamine (TAED), and acid anhydrides such as maleic anhydride. However, the bleaching power was still insufficient.

As a result of research by the present inventors, Japanese Patent Application Laid-Open No. 63-23396
No. 9, JP-A-63-315666, JP-A-6
4-68347, JP-A-1-190654, etc., compounds that react with hydrogen peroxide to produce an organic peracid having a 1N group are extremely excellent as bleach activators. has been found.

An object of the present invention is to provide a bleach cleaning composition that maximizes the performance of this bleach activator.

[Means to solve the problem]

As a result of further studies, the present inventors discovered that a nonionic zeolite detergent containing a maleic acid cobolimer was optimal, and completed the present invention.

That is, the present invention provides: (a) nonionic activator 8 to 35% by weight
(b) Zeolite 20 to 60% by weight (c) 5 to 20% by weight of peroxide that generates hydrogen peroxide in an aqueous solution (d) Reacts with hydrogen peroxide to produce an organic peracid having a 1N group. 1 to 10% by weight of the organic peracid precursor produced (e) The following general formula - CH - CH COOM COOM (in the formula, the gate represents H, an alkali metal, an alkaline earth metal, ammonium, or substituted ammonium) in the molecule. The purpose of the present invention is to provide a bleaching detergent composition containing 1 to 5% by weight of a copolymer containing a unit represented by the following formula and containing no more than 0.1% by weight of phosphate.

Examples of the nonionic surfactant which is component (a) of the present invention include polyoxyalkylene alkyl (or alkenyl) ether whose hydrophobic group has a hydrocarbon group having 8 to 22 carbon atoms, polyoxyethylene alkylphenyl ether, and higher fatty acid alkanolamide. or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycosides, fatty acid glycerin monoesters, alkyl amine oxides, etc. In particular, the following nonionic surfactants are preferably used.

(1) having an alkyl group with an average carbon number of 10 to 20, and 1 to
Polyoxyethylene alkyl ether with 30 moles of ethylene oxide added.

(2) having an alkyl group with an average carbon number of 9 to 12, and 1 to 2
Alkylphenyl ether with 5 moles of ethylene oxide added.

(3) An alkyl glycoside represented by the following general formula.

R(OCtH4). G, (wherein, R is an alkyl group having 9 to 14 carbon atoms, and X is O to 2
, G is glucose, fructose, maltose or sucrose residue M, and y is a number from 1 to 4, preferably from 1.2 to 3. ) The nonionic active agent is incorporated in the composition in an amount of 8 to 35% by weight, preferably 10 to 25% by weight.

The zeolite which is the component (b) of the present invention has the following (1)
~(I[[) is a crystalline or non-crystalline aluminosilicate.

(I) Crystalline aluminosilicate x (M'
zO or M”0) ・A1zOz ・V(Si(b)
・h(HzO) [In the formula, i゛ is an alkali metal atom, ゜゛ is an alkaline earth metal atom that can be exchanged with calcium,
LL represents the number of moles of each component, generally 0.7≧X
≧1.5, 0.8≦y≦6, and y is any positive number. ] (II) As the detergent builder, those represented by the following general formula are particularly preferred.

NazO ・AlzOi 'n (SiOz) - w
(HzO) [In the formula, n represents a number from 1.8 to 3.0, and a circle represents a number from 1 to 6. ] (III) Amorphous aluminosilicate X (
M'20) ・A1zCh ・y(SiOz) ・w(
HzO> [In the formula, '' represents a sodium and/or potassium atom, and X+y+1 represents the number of moles of each component in the following numerical range.

0.7<x≦1.2, 1.6≦y≦2.8, 1 is any positive number. ] Particularly preferred are synthetic crystalline zeolites typified by zeolite A.

Zeolite is blended in the composition in an amount of 20 to 60% by weight, preferably 30 to 50% by weight.

The bleaching detergent composition according to the present invention has a phosphate content of 0.
It is a so-called phosphorus-free detergent containing 1% by weight or less.

Peroxides that generate hydrogen peroxide in an aqueous solution, which is component (c) of the present invention, include sodium carbonate/hydrogen peroxide adduct, urea/hydrogen peroxide adduct, and 4NazSO4' 2
Examples include 8zOz'NaCI, sodium perborate hydrate, sodium perborate tetrahydrate, sodium peroxide, calcium peroxide, and the like. Among these, particularly preferred are sodium carbonate/hydrogen peroxide adduct, sodium perborate hydrate, and sodium perborate tetrahydrate. Peroxide is incorporated into the composition in an amount of 5 to 20% by weight.

Reacts with the hydrogen peroxide used in the present invention to form a
Examples of the organic peracid precursor (d) that generates an organic peracid having 1N-1 group include those disclosed in JP-A-63-233969.
No. Publication, Japanese Patent Application No. 1982-26789, Japanese Patent Application No. 1983-
Organic peracid precursors such as those disclosed in JP-A-315666, JP-A-64-68347, JP-A-1-190654, etc. can be used.

Suitable examples of such organic peracid precursors include acyl compounds represented by the following general formula.

RZ ”+-(A)-T{B),-N2(linking group)-C-(leaving group) group, A is (1- -NHC- -C
NH00 CH3 CH. B is {CH2h, {OCH2CH2}-, or {OC
HCH2h (m is preferably 1 to 12, particularly preferably 1 to 5, n
is preferably from 1 to 10, particularly preferably from 1 to 5. ). a, b
are a=o, b=o, or a=1, b=1. Rz and R3 are C1-2 alkyl groups.

The linking group is not particularly limited, but for example, an alkylene group, a cycloalkylene group, a phenylene group, an alkylenephenylene group, an oxyalkylene group (-CH2
C}120 − ), etc.

The leaving group is not particularly limited, but for example, O (wa) glycerin residue, (power) sugar derivative residue, (R,. R8 is an alkyl group, Rll+ R, is H or an alkyl group, R , represents an alkylene group, an alkenyl group, and Y represents R2H or 1C-(linking group)-N-iR.
Matashiyo 110 R3 represents an alkali metal).

In the general formula of the organic peracid precursor, X- is an inorganic or organic counterion, but is the leaving group? Doesn't exist.

In the general formula L (I[[), the linking group is -(cHz)
t~1■ Particularly -(c}1.), ~, -, where the leaving group is (a), (mouth). (c), (2), (f). (}), (
It is represented by the structural formula of wa), (power), (yo), (yu) (re), where R is C, ~2 alkyl group, R6, R is H or C
+~2 alkyl group, R8 is a C1-2 alkyl group, P
, is preferably an alkylene group with CI~3,
Compounds represented by the structural formulas (Y) and (Y) are particularly desirable.

Also useful are nitrile compounds represented by the following general formula.

R R NCCHzN”(cHz)nN”CHzCN 2X
RR (wherein R is an alkyl group having 1 to 3 carbon atoms, X is an organic or inorganic anion, and is an integer of 1 to 16).

) Among these bleach activators, the following are particularly desirable:

CH3 (a) R1 N ゛1C H 2 )/C0 (leaving group) CH3 CH. (mouth) R+-C-NH(cHz)-NCHZ)/ -co-
(Leaving group) 11 0 CH. CH3 (c) R, -NHC- (cH2). N only CHz)z -CO-
(Leaving group) II 0 CHff CH3 (2) R. 0 (cIIZ). Ni(cHZ)/C0 (Leaving group) C113 CH3 (E) R+-C-(QC}IzC}Iz)-N-CHz)l-
CO- (leaving group) 11 0 Cl{3 ■ [In the formula, R. , I@ are the same as above, l is an integer of 1 to 10, and the leaving group is the same as above (Y). It is a group represented by (Yu). ] In the present invention, the organic peracid precursor is blended in the composition in an amount of ~10% by weight.

The following general formula CH is present in the molecule used in the present invention.
The copolymer (e) containing a unit represented by CH COOM COOM (in the formula, H represents H, an alkali metal, an alkaline earth metal, ammonium, or substituted ammonium) is generally (anhydrous) maleic. It is synthesized by a copolymerization reaction between acid and other copolymerizable monomers, and examples of other copolymerizable monomers used in this reaction include acrylic acid, crotonic acid, isocrotonic acid, aconitic acid, itaconic acid, and citraconic acid. Acid, fumaric acid, methacrylic acid, α-hydroxyacrylic acid, vinylphosphonic acid, sulfonated maleic acid, diisobutylene, styrene, methyl vinyl ether, ethylene, propylene, isobutylene, pentene,
Examples include butadiene, isoprene, vinyl acetate (and vinyl alcohol when hydrolyzed after copolymerization), acrylic esters, etc., but are not particularly limited. Among the above copolymerizable monomers, it is preferable to use one or more of acrylic acid, methacrylic acid, ethylene, isobutylene, diisobutylene, styrene, vinyl acetate, and pentene.

In the present invention, the copolymer (e) has an average molecular weight of 80
0 to 1,000,000 is used, preferably 7,000 to 200,000, particularly preferably 7.0
00 to 100,000 is used.

Further, the copolymerization ratio of maleic acid (anhydride) and other copolymerizable monomers in copolymer (e) is not particularly limited, but
Preferably (anhydrous) maleic acid/other copolymerizable monomers.
1/100 to 90/10, particularly preferably 20/80
The copolymerization ratio is in the range of ~60/40.

In the present invention, the copolymer (e) is blended in the composition in an amount of 1 to 5% by weight.

The organic peracid precursor (d) used in the present invention has excellent bleaching performance itself, but the organic peracid that is produced after reaction with the peroxide, which is the actual bleaching species, is a variety of organic peracids. Factors, for example, coexisting formulation components (surfactants, builders, etc.), mixed impurities (for example, decomposition catalysts such as heavy metals)
be influenced by.

In the present invention, in order to eliminate these effects, the ingredients (
a), (b), (c), but also in conventional types of organic peracid precursors, various efforts have been made to eliminate this effect. For example, Tokuko Sho 53-
5273, JP 52-73905, JP 55-52397, JP 551371.
No. 99, JP 56-149499, JP 60-106895, U.S. Patent No. 4529534
The use of various bleach stabilizers is disclosed in the patent specification and the like. Such bleach stabilizers include aminotri(methylenephosphonic acid), 1-hydroxyethylidene-1,1-
Diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenediaminepenta (methylenephosphonic acid) and their salts, 2-phosphonobutane-1,2
Examples include salts of phosphonocarboxylic acids such as monodicarboxylic acids, salts of amino acids such as aspartic acid and glutamic acid, and aminopolyacetic acid salts such as nitrilotriacetate, ethylenediaminetetraacetate, and diethylenetriaminepentaacetate. In the present invention, these conventionally used bleach stabilizers are
It is also effective to add 0.5 to 2% by weight to the composition.

The bleaching detergent composition of the present invention has an average molecular weight of 4000 to 20.
By adding 1 to 5% by weight of 000 polyethylene glycol, an enhanced bleaching effect can be obtained more stably. Polyethylene glycol is a very advantageous component as it also has anti-recontamination and anti-caking effects.

The main balance of the composition of the present invention is a silicate such as sodium silicate;
These include alkaline agents such as soda carbonate and potassium carbonate, recontamination inhibitors such as polyvinylpyrrolidone and carboxymethylcellulose, enzymes such as protease, lipase, and cellulase, fluorescent dyes, and fragrances. The silicate is preferably blended in an amount of 3 to 20% by weight.

Others: alkylbenzene sulfonate, alkyl ether sulfate, alkyl sulfate, α-olefin sulfonate, α-sulfo fatty acid salt or ester salt, higher fatty acid salt, carboxybetaine, sulfobetaine, di-long chain alkyl quaternary ammonium salt It is also possible to use other surfactants together, but the amount of these other surfactants is 50% by weight or less, preferably 30% by weight based on the nonionic surfactant.
It should be kept below.

Furthermore, the composition of the present invention contains an anti-caking agent, an antioxidant,
A bluing agent, a pigment, a solubilizer, an enzyme activity enhancer, etc. can be added as necessary.

〔Example〕

Next, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Various phosphorus-free bleaching detergents having the component compositions shown in Table 1 were prepared,
A bleach cleaning performance test was conducted for each.

The organic peracid precursors AC used above are shown below.

A: B: C: CH3 CH, NC-CHz-N'-{CHz) b-N2CHz-C
N-2 CICH3 CHI In addition to these, tetraacetylethylenediamine (TAED) and sodium n-nonanoyloxybenzene sulfonate (NOBS) were used as organic peracid precursors for comparison.

Further, copolymers A, B, and C (all sodium salts) used in the above bleach cleaning agent are shown below.

A: Maleic acid/acrylic acid copolymer (monomer ratio 30/70, average molecular weight 70.000) B: Maleic acid/isobutylene copolymer (monomer ratio 50
/50, average molecular weight 10,000) C: Maleic acid/ethylene copolymer (monomer ratio 50/50, average molecular weight 25,000)
*Preparation of tea-contaminated cloth: Add 10 Pluck Bond tea bags (2
0g) with 50g of sugar and boil for 10 minutes.

After that, take out the tea bag and add 1! Make it. After cooling, it is placed in a vat, and a 10 x 551 desizing cloth is dipped for 10 seconds on each side, passed through a roller, and air-dried to obtain a tea-stained cloth.

*Preparation of red wine-tainted cloth: Put red wine (RIOJA 'Siglo'') directly into a vat, soak a 8x50cm cloth for 10 seconds on each side, pass it through a roller, and dry naturally to obtain a red wine-stained cloth.

Wash the contaminated cloth obtained above with various bleach detergents for evaluation. The washing conditions at this time were: Temperature: 20'C Bath ratio: 1/60 Detergent concentration: 0.0833% Water quality: Tap water tergotometer = 10 minutes.

The reflectance of the washed contaminated cloth was measured using Nippon Denshoku Kogyo's NDR-1.
Using 01DP, the reflectance measurement wavelength was set to 460 for black tea contaminated cloth.
Cloths stained with locks and red wine were measured at 520 ■, and the washing bleaching rate was determined using the following method to evaluate the bleaching performance. The evaluation results are shown in Table 2.

As shown in Table 2, the bleaching detergent according to the present invention exhibited particularly superior bleaching and cleaning performance than the comparative product.

Example 2 Various bleach cleaning agents having the component compositions shown in Table 3 were prepared, and the bleach cleaning tests for each were conducted in the same manner as in Example 1.

Table 3 Note) *: Comparative Example The organic peracid precursor D used above is shown in . In addition to these, tetraacetylethylenediamine (TAED) and sodium n-nonanooxybenzenesulfonate (NOBS) were used as acid precursors for comparison. In addition, the copolymer used for the above bleaching and cleaning process is shown below. Engineering: Freic acid/methacrylic acid copolymer sodium salt (monomer ratio 70/30, average molecular weight 50,000) (monomer ratio 50/50, average molecular weight 7,000)
The cleaning conditions are: Temperature: 30°C Bath ratio: 1/60 Detergent concentration: 0
．． 15% Water 1f: 8゜RoH Tergotometer 215
It was a minute.

The evaluation results are shown in Table 4.

table 4 The underlined part corresponds to the product of the present invention Conclusion Fruit As shown in Table 4, Bleached washing according to the present invention showed particularly superior bleaching and cleaning performance compared to comparative products.

Claims (1)

[Claims] 1 (a) 8 to 35% by weight of a nonionic activator (b) 20 to 60% by weight of zeolite (c) 5 to 2% of a peroxide that generates hydrogen peroxide in an aqueous solution
0% by weight (d) 1 to 10% by weight of an organic peracid precursor that reacts with hydrogen peroxide to produce an organic peracid having ▲ mathematical formulas, chemical formulas, tables, etc. ▼ groups (e) The following in the molecule: General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, M represents H, alkali metal, alkaline earth metal, ammonium, substituted ammonium.) A bleaching detergent composition containing 5% by weight of phosphate and not more than 0.1% by weight of phosphate.