JPH0321700A - Bleaching agent or bleaching detergent composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition containing hydrogen peroxide, etc., organic peracid precursor and maleic acid-based copolymer with synergistically enhanced bleaching and detergent effects. CONSTITUTION:The objective composition containing (A) hydrogen peroxide or a peroxide capable of generating the hydrogen peroxide in an aqueous solution (preferred examples; sodium carbonate hydrogen peroxide adduct and sodium perborate monohydrate), (B) an organic peracid precursor capable of forming an organic peracid having a group expressed by formula I in the molecule {preferred example; an acyl compound expressed by formula II [R1 is 1-18C alkyl; A is -O-, formula III, etc.; B is -(CH2)m-, formula IV, etc., (m is 1-12; n is 1-10); both a and b are 0 or 1; R2 and R3 are 1-2C alkyl} and (C) a copolymer (e.g. maleic acid/acrylic acid copolymer or maleic acid/isobutylene copolymer) containing units expressed by formula V [M is H, alkaline (earth) metal or (substituted) ammonium] in the molecule.

Description

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

[Problems that the prior art and invention are trying to solve 1] Chlorine bleach has limitations on the types of fibers that can be used, cannot be used on colored or patterned fabrics, and has a unique odor. Oxygen bleaches, which do not have these drawbacks, have recently become very popular.

As the oxygen bleach, sodium percarbonate and sodium perborate are particularly used from the viewpoint of bleaching performance and stability.

Oxygen bleach has weaker bleaching power than chlorine bleach, and 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 O-acetylated products such as Tetraacetylethylenediamine (TAHD), N-acylated products such as tetraacetylethylenediamine (TAHD), 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
It has been found that compounds having one Nt- group introduced into the molecule are excellent as bleach activators, as exemplified in Publication No. 4-68347 and Japanese Patent Application No. 14243/1983. , even better bleaching/cleaning performance is required.

[Means to solve the problem]

As a result of further intensive studies, the present inventors discovered that the bleaching/cleaning performance can be synergistically enhanced by using a maleic acid copolymer in combination with a compound in which a 1N''- group has been introduced into the molecule. The invention has been completed.

That is, the present invention provides (a) hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution; (b) an organic peracid having one Nt- group that reacts with hydrogen peroxide; and (C) the following general formula (1) C II-C in the molecule.
I! - + 1 (+) COOM
COOM (In the formula, H represents an alkali metal, an alkaline earth metal, ammonium, or substituted ammonium.) Bleach or bleach cleaning agent composition containing a copolymer containing a unit represented by COOM It provides:

Peroxides that generate hydrogen peroxide in an aqueous solution, which is a precept (a) of the present invention, include sodium carbonate/hydrogen peroxide adduct, sodium tripolyphosphate/hydrogen peroxide adduct, and sodium pyrophosphate.・Hydrogen peroxide adduct, urea/hydrogen peroxide adduct, 4NatSO4' 211zO. '
Examples include 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 1~95 in Kumikaimono.
% by weight is added.

Reacts with the hydrogen peroxide used in the present invention to form a
Examples of organic peracid precursors (b) that can be used to treat organic peracids having 1N"- groups include, for example, JP-A-632
Publication No. 33969, Japanese Patent Application No. 62-267987,
Patent Application No. 1983-14243, Japanese Patent Application No. 63-3156
Organic peracid precursors such as those disclosed in JP-A No. 66, JP-A-63-258447, JP-A-64-68347, etc. can be used.

Suitable examples of such organic peracid precursors include acyl compounds represented by general 2 (2) below.

R,? H. B is -{CHzh 1iOCH. CII■】7 or →O
C H C II h (m is preferably 1 to 12, particularly preferably l 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, and 6 R2 and R3 are C1-2 alkyl groups.

The linking group is not particularly limited, and includes, for example, an alkylene group, a cycloalkylene group, a phenylene group, or an alkylenephenylene group.

The leaving group is not particularly limited, but for example, R. 0 In formula (2), R1 is C+~18, especially C1~. Straight chain or branch C11, Kyl group, R, alkylene group, alkenylene group, R2 Y represents H or -C- (linking group) -N2R1. The gate is I
I O R, 1 {or represents an alkali metal. ).

In the general formula (2), X- is an inorganic or organic group (wa) a glycerin residue. (force) sugar derivative residue, (Rs,
Rs is an alkyl group, R. ,R? Is it 11 or Al? In the general formula (2), the linking group is -(c11■)1-,2 especially -(Clh),-5-, and the leaving group is (i)1(mouth),
(c) It is represented by the structural formula of (ii), (he), (t), (wa), (force), (yo), (y), and R5 is an alkyl group of cl to 2, Rl ,,R? is H or CI-t (D alkyl group, R[l is an alkyl group of CI-2, R is Cl~3
Compounds having an 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 (3).

11 R (In the formula, R is an alkyl group having I to 3 carbon atoms, X is an organic or inorganic anion, and n is an integer of 1 to 16.) In the present invention, the peroxide (a) and the organic Peracid precursor (b) is peroxide/organic peracid precursor -99.9/0.
It is used in a molar ratio of 1 to 20/80.

In the molecule used in the present invention, the following general formula (1) C I
I − CI1 + 1 (1)
COOM COOM (In the formula, H1 represents an alkali metal, an alkali earth metal, ammonium, or substituted ammonium.) A copolymer (C) containing a unit represented by (C) is generally composed of maleic acid (anhydride) and is synthesized by a copolymerization reaction with other copolymer monomers. Examples of other copolymer monomers used in this reaction are acrylic acid, crotonic acid, isocrotonic acid, aconintic acid, and itaconic acid. acids, citraconic acid, fumaric acid, methacrylic acid, alpha hydroxyacrylic acid, vinylphosphonic acid, sulfonated maleic acid, diisobutylene, styrene, methyl vinyl ether, ethylene, brobylene, isobutylene, pentene, butadiene, isoprene, vinyl acetate (and When hydrolyzed after polymerization, vinyl alcohol), acrylic esters, etc. may be used, but there are no particular limitations. Among the above copolymers, it is preferable to use one or more of acrylic acid, methacrylic acid, ethylene, isobutylene, diisobutylene, styrene, vinyl acetate, and bentene.

In the present invention, the above copolymer (C) has an average molecular weight of 80
0 to 1,000,000 is used, preferably 7,000 to 200,000.

Further, the copolymerization ratio of maleic acid (anhydride) and other copolymerizable monomers in the copolymer (C) is not particularly limited, but
Preferably (anhydrous) maleic acid/other copolymerizable monomer=
The copolymerization ratio ranges from 1/100 to 90/10.

In the present invention, the copolymer (C) is 0.5 to
It is blended in an amount of 8% by weight, preferably 1 to 5% by weight.

The organic peracid precursor (b) 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. , affected by decomposition catalysts such as heavy metals.

Although the present invention uses a maleic acid copolymer to eliminate this effect, various efforts have been made to eliminate this effect with conventional types of organic peracid precursors. For example, Japanese Patent Publication No. 53-5273, Japanese Patent Application Laid-Open No. 73905-1982, Japanese Patent Application Publication No. 55-5239
Publication No. 7, JP-A-55-137199, JP-A-5
6-14'3499, JP 60-1068
No. 95, US Pat. No. 4,529,534, etc. disclose the use of various bleach stabilizers.

In addition, the bleach or bleach cleaning agent composition of the present invention includes the above (
In addition to the essential parts of a) to (C), the following various surfactants can be used in combination.

Anionic surfactants include alkylbenzene sulfonates, alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, α-olefin sulfonates, α-sulfo fatty acid salts or ester salts, alkanesulfonates, saturated or unsaturated Fatty acid salt, alkyl or alkenyl ether carboxylate, amino acid type surfactant, N-acylamino acid type surfactant, alkyl or
Examples include rukenyl phosphate ester or a salt thereof.

Examples of amphoteric surfactants include carboxy type or sulfobetaine type amphoteric surfactants, and examples of nonionic surfactants include polyoxyalkylene alkyl or alkenyl ethers, polyoxyethylene alkylphenyl ethers, and higher fatty acid alkanol alcohols. Examples of nonionic surfactants include hydrogen oxide or its alkylene oxide adducts, sucrose fatty acid esters, alkyl glycosides, fatty acid glycerin monoesters, and alkylamine oxides, and examples of cationic surfactants include quaternary ammonium salts.

In addition, the bleaching agent or bleaching detergent of the present invention may contain conventional auxiliary additives, such as phosphates such as crystalline aluminosilicate, tripolyphosphate, and pyrophosphate, aminotri(methylenephosphonic acid), l Monohydroxyethylidene-1.1
- Diphosphonic acid, ethylene diξtetra (methylene phosphonic acid), diethylene triamine penta (methylene phosphonic acid) and their salts, salts of ethane-1,1-diphosphonic acid, 2-phosphonobutane-1,2-dicarboxylic acid, etc. Carboxylic acid salts, amino acid salts such as aspartic acid and glutamic acid, aminopolyacetic acid salts such as nitrilotriacetate and ethylenediaminetetraacetate, polymer electrolytes such as polyacrylic acid and polyaconitic acid, polyethylene glycol, polyvinyl alcohol, polyvinyl Non-dissociated polymers such as pyrrolidone, polyacetal carboxylic acid polymers described in JP-A-54-52196, birgoose and divalent metal ion scavengers such as salts of organic acids such as diglycolic acid and oxycarboxylic acid salts; Alkaline agents or inorganic electrolytes such as silicates, carbonates, sulfates, etc., JP-A-60-22
Recontamination prevention agents such as layered silicates, polyvinylpyrrolidone, and carboxymethyl cellulose described in Publication No. 7895, 7
Enzymes such as o-tease, lipase, cellulase, anti-caking agents such as para-toluene sulfonate, sulfosuccinate, talc, calcium silicate, peroxide stabilizers such as magnesium silicate, tertiary butylated hydroxyl.・Antioxidants such as luene and distyrenated cresol,
It may contain fluorescent dyes, blue tints, fragrances, etc., but these are not particularly limited and may be blended according to the purpose.

〔Example〕

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

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

Xiahang washing agent agent (wt%) Soap (beef tallow) 2 Fluorescent dye 0. 2 total 1 0
0 The organic peracid precursors A-C used above are shown below.

A: Hekai zeolite (type 4A) No. 1 sodium silicate sodium carbonate 25 5 l0 B: Enzyme (protease) Sodium percarbonate 0.5 10 Glauber's salt 2 C: CH3 NC-CH. -N 呵CH. ). ? HiIN2Cll■-CN・2CI CL C}13 In addition to these, tetraacetylethylene diξane (TAED) and sodium n-nonanoyloxybenzenesulfonate (NOBS) were used as organic peracid precursors for comparison. there was.

Further, copolymers ① to ② (all sodium salts) used in the above bleach cleaning agent are shown below.

I: Maleic acid/acrylic acid copolymer (monomer ratio 30/70, average molecular weight 70,000)
■: Maleic acid/acrylic acid copolymer (monomer ratio 45/55, average molecular weight 50,000)
■: Maleic acid/isobutylene copolymer (monomer ratio 5
0/50, average molecular weight 10.000) ■: Maleic acid/ethylene copolymer (monomer ratio 50/50, average molecular weight 25,000)
I went to meet you and tried fat *Creating black tea contaminated cloth: Water 11! ．． Then, 10 tea bags (20g) made by Brunck Pond and sand tJ! Boil 50g for 10 minutes. Then remove the tea bag and bring the total volume to 1 liter. 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 red wine stained 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.

The contaminated cloth obtained above is washed with various bleaching detergents for evaluation. The cleaning conditions at this time are: Temperature: 20°C Bath ratio: l/60 Detergent concentration:
0.833% Water quality: Tap water tergotometer = 1
It was 0 minutes.

The reflectance of the washed contaminated cloth was measured using NDI1- manufactured by Nippon Denshoku Kogyo ■.
Using 101DP, the reflectance measurement wavelength was set to 46 for black tea contaminated cloth.
The washing bleaching rate was determined using the following formula and the bleaching performance was evaluated. The results are shown in Table-1.

Anti-ITΦ Example 2 of Japanese anti-IR hand-to-hand rule til+ Various phosphorous bleaching detergents with the following ingredient compositions were prepared,
Each bleach cleaning performance test was conducted in the same manner as in Example 1.

Standard Aα Natsuide Shark Cap (wt%) Straight-chain alkylbenzenesulfonic acid pentasodium (C=12) α-Sulfohydrogenated beef tallow fatty acid 5 methyl ester sodium Higher alcohol ether iA617 Pentasodium (C=14, EO=2) Higher alcohol Ethoxylate 2 (C=12,
EO=8) Sodium tripolyphosphate soda ash No. 2 Sodium silicate Sodium nitrate borate monohydrate Enzyme Organic peracid precursor (D-F) Copolymer (V~■) 1.8 Fluorescent dye 0 .2 Total 100
The organic peracid precursor DF used above is shown below.

D: E: CI! Cell+7-NQC}Iz) zCOOCH2CHz
SOff-CIlz F: CH3 CI13 In addition to these, tetraacetylethylenediamine (TAED) and sodium n-nonanoyloxybenzenesulfonate (NOBS) were used as organic peracid precursors for comparison.

Further, copolymers V to ① (all sodium salts) used in the above bleach cleaning agent are shown below.

V: Maleic acid/acrylic acid copolymer (monomer ratio 30/70, average molecular weight 50,000)
■: Maleic acid/methacrylic acid copolymer (monomer ratio 50/50, average molecular weight 1,500) ■: Maleic acid/styrene copolymer (monomer ratio 50/50, average molecular weight @ 7,000 >
■: Maleic acid/vinyl acetate copolymer (monomer ratio 50/50, average molecular weight 7,000) The cleaning conditions are: Temperature: 35°C Bath ratio: 1/60 Detergent concentration: 1
．． 5% Water quality 28°Dtl (Ca/Mg=2/1)
Tergotometer: 15 minutes.

The evaluation results are shown in Table-2.

? Example 3 Various bleaching detergents having the following two ingredients (Mikai) were prepared, and the bleaching and cleaning performance tests for each were conducted on tea-stained cloth in the same manner as in Example 1.

Tan hollowed down ■U and precept, = (weight%) Soap (beef tallow) 2.0 Gokai Zeolite (Type 4A) Magnesium silicate sodium carbonate Awn, Salt Sodium perborate tetrahydrate Organic peracid precursor (G, H) 3 5. 2. 11. 8. 20. 3. fluorescent dye water minutes Isako 1 Note U Help L 0.5 remainder (weight%) Sodium tripolyphosphate Combined zeolite (4A type) sodium metasilicate Sodium perborate hydrate 3 5. 1 5. 5. 8. fluorescent dye water minutes total Organic peracid precursor G used above, 0.2 remainder 100 H below Shown below.

G: lJ: CI3 CH, NC-CIlz-N'-(CIlz) z-N''CI{
z-CN ・2 Br-CI. C}I
．． In addition to these, tetraacetylethylenediamine (TAED) and sodium n-nonanoyloxybenzenesulfonate (NOBS) were used as organic peracid precursors for comparison.

In addition, the copolymer ■~''1?1 (
All sodium salts) are shown below.

■: Maleic acid/acrylic acid copolymer (monomer ratio 30/70, average molecular weight 70,000'
) X: Maleic acid/diisobutylene copolymer (monomer ratio 50/50, average molecular weight 7,000)
X Detergent concentration: Formulation 1...0.9%, Formulation 2...0.6
% Water quality: 16° DI (Ca/Mg=2/1) Rank-o-meter: 30 minutes.

The evaluation results are shown in Table-3.

-U As shown in Examples 1 to 3, the bleach cleaning agent according to the present invention exhibited particularly superior bleach cleaning performance than the comparative product.

Example 4 Bleaching agents having the compositions shown below were prepared, and a bleaching performance test on black tea stained cloth was conducted in the same manner as in Example 1.

(Weight %) Sodium percarbonate 85 Bleach concentration: 0.5% (1.5 g / 300ml
! ) Water quality: Tap water Time: 30 minutes immersion bleaching.

The evaluation results are shown in Table-4.

Total 100 In addition to these, tetraacetylethylenediamine (TAED) and sodium n-nonanoyloxybenzenesulfonate (TAED) were used as organic peracid precursors for comparison.
NOBS) was used.

The bleaching conditions were as follows: Temperature: 2o'c Bath ratio: 300d, 5 pieces of contaminated cloth = E As shown in Table 4, the bleaching agent of the present invention showed particularly superior bleaching performance than the comparative product. .

Claims (1)

[Scope of Claims] 1 (a) Hydrogen peroxide or a peroxide that generates hydrogen peroxide in an aqueous solution (b) Reacts with hydrogen peroxide and has a ▲ mathematical formula, chemical formula, table, etc. ▼ group An organic peracid precursor that generates an organic peracid; A bleach or bleach cleaning composition comprising a copolymer containing a unit represented by: metal, ammonium, substituted ammonium.