JPH03215600A - 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 or V [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 which does not contain 0.1% or more phosphate and 1% alkali metal silicate.

Description

[Detailed description of the invention] C Industrial application field] TECHNICAL FIELD This invention relates to bleach cleaning compositions.

(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, 0-acetylated products such as glucose pentaacetate (GPAC), N-acetylated products such as tetraacetylethylenediamine (TAED), and maleic anhydride. Examples include acid anhydrides represented by acids, but even when these activators are used in combination, the bleaching power is 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
It has been found that compounds that react with hydrogen peroxide to produce an organic peracid having a 1N group, such as those exemplified in No. 468347 and JP-A No. 1-190654, are extremely effective as bleach activators. It's being served.

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 substantially no silicate, containing a maleic acid-based or acrylic acid-based polymer or copolymer, is optimal for low-temperature cleaning. The present invention has now been completed.

That is, the present invention provides: (a) nonionic activator 8 to 35% by weight
b) Zeolite 20-60% by weight (c
) Peroxides 5-2 that generate hydrogen peroxide in 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 a 1N group (e) The following general formula or C H z in the molecule A polymer or copolymer containing a unit represented by 11C H COOM (wherein H represents H, an alkali metal, an alkali metal, ammonium, or substituted ammonium)
The present invention provides a bleaching detergent composition which contains 1 to 5% by weight of phosphates, does not contain 0.1% by weight or more of phosphates, and does not contain 1% by weight or more of alkali metal silicate salts.

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, and the like. 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) Alkyl glycoside represented by the following general formula.

R (QCAH4). G, (wherein, R is an alkyl group having 9 to 14 carbon atoms, and X is O to 2
, G is a glucose, fructose, maltose or sucrose residue, and y is a number of 1 to 4, preferably 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 (1) of the present invention is the following (I)
) to (III) are crystalline or non-crystalline aluminosilicates.

(1) Crystalline aluminosilicate represented by the following formula.

x (M'20 or gate '0)・AI20.・y(SiO
■)・Ga(11■0) [In the formula, 1゜ is an alkali metal atom, 1'゛ is an alkaline earth metal atom that can be exchanged with calcium, X+y+1 represents the number of moles of each component, and generally 0.7≧χ≧1.5, 0.8≦y≦6, and 1 is any positive number. ] (II) As the detergent builder, those represented by the following general formula are particularly preferred.

NazO + A1z03'n(SiOz)' w(
HzO) [In the formula, n represents a number from 1.8 to 3.0, and one represents a number from 1 to 6. ] (1) Amorphous aluminosilicate represented by the following formula.

x(M'20)・AIzO3・y(SiOz)・w(H
zO) [In the formula, ゛ represents a sodium and/or potassium atom, and X+L represents the number of moles of each component in the following numerical range.

0.7<x≦1.2, 1.6≦y≦2.8, W 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 C 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, 4NazSOa.
2 HzOz ・NaC1, sodium perborate hydrate, sodium perborate tetrahydrate, sodium peroxide,
Examples include calcium peroxide. Among these, especially sodium carbonate/hydrogen peroxide adduct, sodium perborate} I
Preferred are Jium 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 produces an organic peracid having a -N''- group include those disclosed in JP-A No. 63233969, Japanese Patent Application No. 26789-1982, and JP-A No. 63-1989.
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 general formula 2 below.

R2 R, -(8)? {B)b-N2(linking group)-C-(leaving group) ~14 linear or branched alkyl groups, A is -0- -NH(,- -CN
HI1 00 CH3 0 0 0 0?
H3 B is {CH2}-, {OCH■CHzh or {OCH
CHzh (m is preferably 1 to 12, particularly preferably 1 to 5, and n is preferably 1 to 10, particularly preferably 1 to 5). a, b are a=o. b=o, or a=1, b=1.

R2 and R3 are C, ~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
CH20 − ), etc.

The leaving group is not particularly limited, but for example, 0 (wa) glycerin residue (power) sugar derivative residue, (Rs, Re is an alkyl group, R6+ R7 is H or an alkyl group, R is an alkylene group, alkenyl group, Y is R
2 ■ or 1C- (linking group) represents N'R+. Formerly H or 1 {O 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 above general formula (III), the linking group is -(c}IZ
L~1■-, especially -(cHz)+~5-, and the leaving group is (
A), (mouth) 1 (c), (2). (to), (g), (
It is represented by the structural formula of wa), (power), (yo), (yu), (re), where R is a C, ~2 alkyl group, R6, R? is H or C. -2 alkyl group, R8 is 01-2 alkyl group,
Compounds in which R is a C1-3 alkylene group are desirable, and compounds represented by the structural formulas (Y) and (Y) are particularly desirable.

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

RR (In the formula, R is an alkyl group having 1 to 3 carbon atoms, X is an organic or inorganic anion, and n is an integer of 1 to 16.) Among these bleach activators, the following are particularly desirable: This is represented by each 2 of .

CH3 (a) Rl-“ACHz)/-co-c leaving group)C
H3 CH3 (mouth) R+-C-NH(cHz)+-N'-(cHz)/-C
O-(leaving group) 111 0 C}! , CHi (c) R+-NHC-(cHz)mN'-(cHz)/-CO
-(leaving group) 11 0 CI, CH. (2) R,0 (cHz)-N2(cHz)z-CO (leaving group) CH3 CH3 (e) Rl-C- (OCHzCHz) ,N-JC}12)
/ -CO- (leaving group) 11 0 CH. [In the formula, , is the same as above, p is an integer of 1 to 10, and the leaving group is a group represented by (Y) and (TA) above.

] In the present invention, the spinal acid precursor is blended in the composition in an amount of 1 to 10% by weight.

The molecule used in the present invention contains the following general formula -CH-
A polymer or copolymer containing a unit represented by CH-COOM COOM or CHt-C}I-COOM (wherein, H represents H, an alkali metal, an alkaline earth metal, ammonium, or substituted ammonium) (
e) is generally synthesized by a polymerization reaction of acrylic acid or (anhydride) maleic acid, a copolymerization reaction of both, or a copolymerization reaction with other copolymerizable monomers. Examples of copolymerized heptanomers include crotonic acid, isocrotonic acid, aconitic acid, itaconic acid,
Citraconic acid, fumaric acid, methacrylic acid, alpha-hydroxyacrylic acid, vinylphosphonic acid, sulfonated maleic acid, diisobutylene, styrene, methyl vinyl ether, ethylene, propylene, isobutylene, pentene, putadiene, isoprene, vinyl acetate (and after copolymerization) Examples include vinyl alcohol (in the case of hydrolysis %E), acrylic esters, etc., but are not particularly limited. Among the above copolymerizable monomers, it is preferable to use one or more of methacrylic acid, ethylene, isobutylene, diisobutylene, styrene, vinyl acetate, and pentene.

In the present invention, the polymer or copolymer (e) used has an average molecular weight of 800 to 1,000,000, preferably 7. 000 to 200,000, particularly preferably 7,000 to 100,000.

Further, the copolymerization ratio of acrylic acid or (anhydrous) maleic acid and other copolymerized heptanomers in the copolymer is not particularly limited, but preferably acrylic acid or (anhydrous) maleic acid/other copolymerized monomer-1 /100~90/
The copolymerization ratio is preferably in the range of 10/10, particularly preferably 20/80 to 60/40.

In the present invention, the polymer or 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 produced after reaction with peroxide, which is the actual bleaching species, is affected by various factors,
For example, coexisting ingredients (surfactants, builders, etc.)
, affected by contaminating impurities (e.g. decomposition catalysts such as heavy metals).

In the present invention, in order to eliminate these effects, the compounded 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 55-13719
9, JP-A-56-149499, JP-A-Sho 6
No. 0-106895, US Pat. No. 4,529,534, etc. disclose the use of various bleach stabilizers.

Such bleach stabilizers include aminotri(methylenephosphonic acid), ■-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid) and salts thereof; Salts of phosphonocarboxylic acids such as 2-phosphonobutane-1,2-dicarboxylic acid, salts of amino acids such as aspartic acid and glutamic acid, aminopolyacetic acid salts such as nitrilotriacetate, ethylenediaminetetraacetate, diethylenetriaminepentaacetate, etc. Can be mentioned. In the present invention, it is also effective to add 0.5 to 2% by weight of these conventionally used bleach stabilizers to the composition.

The main balance of the composition of the present invention is an alkaline agent such as soda carbonate or potassium carbonate, a recontamination preventive agent such as polyvinyl pyrrolitone or carboxymethyl cellulose, protease, reverse,
These include enzymes such as cellulase, fluorescent dyes, and fragrances.

In general cleaning agents, a(MzO)H b(SiOz)C formula is used as an alkali agent, skeleton forming agent, stabilizer, and dispersant, where b/a = 0.5 to 4, and h is an alkali metal. . ] Alkali metal silicate salts represented by are often used,
In the bleach cleaning agent of the present invention, the cleaning performance at low temperatures has been successfully improved by controlling the content of alkali metal silicate to 1% by weight or less.

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.

Others include alkylbenzene sulfonates, alkyl ether sulfates, alkyl sulfates, α-olefin sulfonates, α-sulfo JJR fatty acid salts or ester salts, higher fatty acid salts, carboxyhetaines, sulfobetaines, di-long chain alkyl sulfonates, Other surfactants such as quaternary ammonium salts can also be used in combination, but the amount of these other surfactants is 50% by weight or less, preferably 3% by weight based on the nonionic surfactant.
It should be kept below 0% by weight.

Furthermore, the composition of the present invention contains an anti-caking agent, an antioxidant,
A blue tint, 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 by the dry blending method by Niichi Gu (enzymes, sodium percarbonate, and organic peracid precursors were blended by powder heating), and each bleaching agent was A cleaning performance test was conducted.

table 1 note)* ;ratio comparison example The organic peracid precursors AC used above are shown below.

A: B: C: CH3 CH. NC-CH2-N2-(cHz)b-NiCHz-CN
・2C1CH3 CH. In addition to these, tetraacetylethylenediamine (TAED) and sodium n-nonanoyloxyhenzenesulfonate (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)
A: Maleic acid/isobutylene copolymer (monomer ratio 5
0/50, average molecular weight 10,000) U: Acrylic acid polymer (average molecular weight 8.000) Kantanpo Jyo Shichitaki Mebrow 2
0g) with 50g of sugar and boil for 10 minutes. After that, remove the tea bag and reduce the total amount to 11. After cooling, it is placed in a vat, and a 10 x 55 cm 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 artificially contaminated cloth: A 10 cm x 10 cm cotton cloth was contaminated with oil and fat having the composition shown below and a trace amount of carbon plank to prepare an artificially contaminated cloth.

Cottonseed oil 60% Cholesterol 10% Oleic acid 10% Palmitic acid 10% Liquid and solid paraffin 10% The contaminated cloth obtained above is washed with various evaluation bleaching detergents. The cleaning conditions for the tea-contaminated cloth at this time were: Temperature: 20°C Bath ratio: 1/60 Detergent concentration:
0.0833% Water quality: Tap water tergotometer:
It was 10 minutes.

Further, the washing conditions for the artificially contaminated cloth were as follows: Temperature: to'c Bath ratio: 1/60 Detergent concentration: 0.0833% Water it: Tap water Tergotometer: 10 minutes.

The reflectance of the original fabric and 460 μs before and after washing was measured using a self-recording colorimeter (manufactured by Shimadzu Corporation), and the washing bleaching rate was calculated using the following formula to evaluate the bleaching performance. It was.

The evaluation results are shown in Table 2.

still, Artificially contaminated fabrics were tested with organic peracid precursors A-C only.

As shown in Results Table 2, the bleach cleaning agent according to the present invention exhibited particularly superior bleach cleaning performance compared to the comparative product, and was also excellent in cleaning performance at low temperatures.

Example 2 Various bleaching detergents having the component compositions shown in Table 3 were spray-dried (enzymes, sodium perborate, and organic peracid precursors were mixed in powder form).
The bleach cleaning tests were conducted in the same manner as in Example 1.

弗 3 note) ; Comparative example Organic peracid precursor D used above, Shown below.

E is hereinafter referred to as D: In addition to these, tetraacetylethylenediamine (TAED) and sodium n-nonanoyloxybenzenesulfonate (NOBS) were used as organic peracid precursors for comparison.

In addition, the copolymer used in the above bleach cleaning agent is shown below.

(Monomer ratio 30/70, average molecular weight 50,000)
E: Maleic acid/vinyl acetate copolymer potassium salt (monomer ratio 50/50, average molecular weight 7,000) The conditions for cleaning black tea contaminated cloth are: Temperature: 30°C Bath ratio: 1/60 Detergent concentration: 0
．． 15% water quality 28° DH tergotometer: 15 minutes.

In addition, the washing conditions for artificially contaminated cloth are: Temperature: 15°C Bath ratio: 1/60 Detergent concentration:
0.15% Water quality 28゜DH Tergotometer: 15
It was a minute. The artificially contaminated fabric was tested using only organic peracid precursors D and E.

The evaluation results are shown in Table 4.

Table 4 Underlined portions correspond to products of the present invention Results As shown in Table 4, the bleach cleaning agent of the present invention exhibited particularly superior bleach cleaning performance compared to the comparative product, and was also excellent in low-temperature cleaning performance.

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. ▼ Or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, M represents H, alkali metal, alkaline earth metal, ammonium, substituted ammonium.) Polymer or copolymer containing the unit 1
~5% by weight, and does not contain 0.1% by weight or more of phosphates and does not contain 1% by weight or more of alkali metal silicate salts.