JPS6011079B2 - bleach detergent composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to bleaching detergent compounds, particularly solid bleaching detergent compositions suitable for use at virtually all laundry temperatures.

When washing and/or bleaching textiles, for example alkali metal perslates, percarbonates, perphosphates, persilicates, sodium hydrogen peroxide, etc. are used on the textiles to be treated. It is well known to utilize compositions that specifically contain inorganic peroxy compounds that have a bleaching effect. However, laundry detergent and/or bleach compositions containing such inorganic peroxy compounds have a bleaching effect of 8.
They generally have the disadvantage that they are relatively low at temperatures below 0qo and virtually null at temperatures below 60qo, so when using these compositions in domestic washing machines where the wash water temperature does not exceed 70qo. Difficulties arise. It is known to add organic bleach activators for peroxy compounds to compositions of this type, so that the active oxygen contained in the peroxy compounds becomes effective even at temperatures below 8-0.

Such compositions are believed to function by generating organic peroxyacids, such as peroxyacetic acid, during use. The fundamental problem with this type of system is that it generates peroxyacid in situ;
Production difficulties arise under practical conditions. U.S. Patent No. 412-95 discloses bleach compositions containing phthaloyl peroxide and sodium pershelate.

Phthaloyl peroxide is a peroxyacid precursor that is hydrolyzed or perhydrolyzed in an aqueous medium to yield monoperoxyphthalic acid or diberoxyphthalic acid. Further, detergent and/or bleach compositions containing organic peroxyacids such as diberoxyphthalic acid are described in, for example, British Patent No. 1387167, British Patent No. 1456591, and U.S. Patent No. 4,100,095. It is.

GB 1269677 describes percarboxylic acids such as perbenzoic acid and inorganic persulfates, especially mixed salts K
A bleach composition comprising HS04, K2S04, Ice HS05 is disclosed.

It is an object of the present invention to provide bleaching detergent compositions with improved bleaching effectiveness at virtually all washing temperatures.

It has now been discovered that the above objectives can be achieved by using a synergistic mixture of solid organic peroxy acid compounds, inorganic peroxy compounds that generate 02 in solution, and stabilizing sequestering agents.

Thus, solid bleaching characterized in that it consists essentially of a detergent active compound, a solid organic peroxy acid compound, an inorganic peroxy compound that generates hydrogen peroxide in solution, and a stabilizing sequestering agent as defined below. Detergent compositions are provided by the present invention.

The organic peroxy acid compounds used in the present invention should be solid at room temperature and preferably have a melting point of at least 5000.

Such peroxy acid compounds have the general formula: (wherein R is an alkylene group having 1 to 16 carbon atoms or an arylene group having 6 to 8 carbon atoms, and Y is hydrogen, halogen, alkyl, aryl, or an anion in an aqueous solution. organic peroxy acids and their water-soluble salts.

The Y group can be, for example, or (where M is H or a water-soluble salt-forming cation)
can be included.

Organic peroxy acids and their salts that can be used in the present invention are 1
It can contain one peroxy group or two peroxy groups, and can be either aliphatic or aromatic.

When the organic peroxyacid is aliphatic, the unsubstituted acid has the general formula: where Y can be CH, CH, or, and n can be an integer from 1 to 12. can be expressed.

Peroxyazelaic acid (n=7) is most preferred among compounds of this type, particularly diberoxyazelaic acid. Other preferred examples of compounds of this type are:
They are diberoxyadipic acid and diberoxysebacic acid. When the organic peroxyacid is aromatic, the unsubstituted acid can be represented by the general formula: where Y is, for example, hydrogen, halogen, alkyl or.

The bellcarboxyl group and the Y group can be present in any relative position around the aromatic residue.

The ring and/or Y group (if alkyl) are
Optional non-interfering substituents such as halogen or sulfonate groups
t). Examples of suitable aromatic peroxy acids and their salts include monoberoxyphthalic acid, diberoxyterephthalic acid, 4-chlorodiberoxyphthalic acid, m-chloroberoxybenzoic acid, p-nitroberoxybenzoic acid and diberoxybenzoic acid. Contains oxyisophthalic acid. Preferred aromatic peroxy acids are monoperoxyphthalic acid and diberoxysophthalic acid. The amount of organic peroxy acid compound included in the compositions of the invention generally ranges from 1 to 25% by weight, preferably from 2 to 1% by weight.

The inorganic peroxy compound that can be used in the present invention is a compound that liberates hydrogen peroxide in an aqueous solution.

Examples of such inorganic peroxy compounds include persylates,
There are perortho, perpyro, and perpolyphosphates, as well as percarbonates, and persulfate salts, especially alkali metal persulfate salts, are desirable because they are easily available as commercial products. They are 4
It can exist in hydrated as well as partially dehydrated states to the lowest hydrated state. The amount of inorganic peroxy compound included in the compositions of the invention is generally in the range of 2 to 4% by weight, preferably 5 to 3% by weight.

Sequestering agents that can be used in the present invention should have the ability to stabilize bleaching agents by preventing interdegradation reactions between peroxy acids and inorganic peroxy compounds.

Examples of such sequestering agents have the following general formulas 1, 2 and m: where n is an integer from 0 to 4 and x is H or an alkali metal, an alkali metal or an ammonium cation) [where n is 0
is an integer of ~2, X is H or an alkali metal, alkaline earth metal or ammonium cation, and Y=
CH2C00X or CQP03×2, Z=CH2CO
OX or C-P03×2 (×=H or alkali, alkali metal or ammonium cation)] (wherein n' is 1 to 3, and × is day, or an alkali metal, alkali metal or ammonium cation) These sequestrants (metal or ammonium cations) are disclosed in Dutch Patent Application No. 790,714 and British Patent No. 1,392,284.

The amount of sequestering agent included in the compositions of the invention is generally in the range of 0.05 to 5% by weight, preferably 0.1 to 2% by weight.

The bleaching detergent compositions of the present invention also include at least one detergent active compound, which compound may be anionic, cationic, nonionic or amphoteric in character;
The amount is generally about 3% to about 4% by weight, preferably 10% by weight.
~35 weight.

Mixtures of the above detergent active compounds are generally used, and mixtures of anionic and nonionic detergent active compounds are commonly used. Typical detergent active compounds are water soluble or dispersible salts of various organic acids.

The cations in such salts are typically alkali metals such as sodium and, less preferably, potassium, although other cations such as ammonium and substituted ammonium can be used if desired. Examples of suitable organic acids include alkylbenzenes having from about 8 to about 2 carbon atoms in the alkyl chain, such as p-dodecylbenzenesulfonic acid and straight mirror alkyl (C,o-C,5)benzenesulfonic acids. Sulfonic acids; mixtures of sulfonic acids obtained by reacting linear and branched olefins having from about 8 to about 22 carbon atoms, especially linear "cracked wax" or "Ziegler" Q-olefins, with sulfur trioxide. ; reaction of alkanes having about 8 to about 22 carbon atoms with sulfur dioxide/oxygen or sulfur dioxide/chlorine (in the latter case, followed by hydrolysis); or reaction of bisulfites with about 8 to about 22 carbon atoms; Alkyl sulfonic acids obtained by addition to olefins, especially "cracked waxes" or "Ziegler"Q-olefins; alkyl sulfuric acids obtained by reaction of aliphatic alcohols having from about 8 to about 22 carbon atoms with sulfur trioxide. reacting a 1 mole amount of an aliphatic alcohol having from about 6 to about 18 carbon atoms with about 1 to about 15 moles of ethylene oxide or a suitable mixture of ethylene oxide and propylene oxide, and then reacting the alkoxylated alcohol with sulfur trioxide; alkyl ether sulfuric acid obtained by oxidation to give the required acid; and natural and synthetic aliphatic carboxylic acids, especially tallow, coconut oil, palm oil,
There are carboxylic acids derived from natural sources such as palm kernel oil and peanut oil. Examples of suitable nonionic detergent-active compounds include alkyl groups containing about 6 to 12 carbon atoms, which may be of either straight-chain or branched structure, such as polymerized propylene, diisobutylene, octene,
condensates of alkylphenols (derived from dodecene or nonene) with about 5 to 25 moles of ethylene oxide per mole of alkylphenols; by reacting ethylene oxide with the reaction product of ethylene diamine and excess propylene oxide The resulting condensate contains from about 40 to about 8% by weight polyoxyethylene and about 5% by weight polyoxyethylene.
000 to about 11,000; condensates of straight or branched aliphatic alcohols having 8 to 18 carbon atoms and ethylene oxide, for example containing about 6 to 30 moles of ethylene oxide per mole of coconut alcohol. Palm alcohol-ethylene oxide condensate; general formula R, R2R3
Long mirror tertiary amine oxides, such as dimethyl, corresponding to N→○, where R is an alkyl group having about 8 to 18 carbon atoms, and R2 and R3 are each a methyl, ethyl or hydroxyethyl group. Dodecylamine oxide, dimethyloctylamine oxide, dimethylhexadecylamine oxide and N-pis(hydroxyethyl)dodecylamine oxide; general formula RR'R''P→○ (wherein R is alkyl or alkenyl having about 10 to 18 carbon atoms) or a monohydroxyalkyl group, R' and R'' each being an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms), such as a long mirror tertiary phosphine oxide, such as dimethyldodecylphosphine. oxide, dimethyltetradecyl Z phosphine oxide, ethylmethyltetradecylphosphine oxide, dimethylsterylphosphine oxide, ethylpropylcetylphosphine oxide, diethyldodecylphosphine oxide, pis(hydroxymethyl)dodecylphosphine oxide, bis( 2-hydroxyethyl)dodecylphosphine oxide, 2-hydroxypropylmethyltetradecylphosphine oxide, dimethyloleylphosphine oxide and dimethyl-2-hydroxydodecylphosphine oxide; and the general formula RR'→○ (wherein R is alkyl, alkenyl, B- or Q-mo/hydroxyalkyl group, or an alkyl group containing 1 or 2 further oxygen atoms in the chain or 8- or Q-monohydroxyalkyl group, and 1 carbon atoms and R' is a methyl, ethyl or alkyl group), such as dodecylmethyl sulfoxide, tetradecylmethyl sulfoxide, 3-hydroxytridecylmethyl sulfoxide, 2 -hydroxydodecylmethylsulfoxide, 3-hydroxy-4-dodecyloxybutylmethylsulfoxide, 2-hydroxy-3-decyloxypropylmethylsulfoxide, dodecylethylsulfoxide, 2-hydroxydodecylethylsulfoxide and dodecyl-2-hydroxyethylsulfoxide.

Examples of suitable amphoteric detergent active compounds are those in which the aliphatic group is straight or branched, one of the aliphatic substituents contains about 8 to 1 needle carbon atoms, and one is anionic. aliphatic secondary and tertiary amine derivatives containing water solubilizing groups such as sodium 3-dodecylaminopropionate,
Sodium 3-dodecylaminopropanesulfonate and sodium N-2-hydroxydodecyl-N-methyltaurate; and wherein the aliphatic group is straight or branched and one of the aliphatic substituents has about 8 to 1 aliphatic quaternary ammonium compounds, sulfonium compounds and phosphonium compound derivatives containing a solid carbon atom and one containing an anionic water-solubilizing group, e.g.
-(N,N-dimethyl-N-hexadecyl ammonium)propane-1-sulfonate betaine, 3-(N,N
-dimethyl-N-hexadecyl ammonium)-2-hydroxypropane-1-sulfonate betaine, 3-(
dodecylmethylsulfonium) propane-1-sulfonate betaine and 3-(cetylmethylphosphonium)
Ethanesulfonate betaine.

Additional examples of suitable detergent active compounds commonly used in the art can be found in Schwanz and Peny,
Sumace Active A saddle nts, Volume
``InterscleMe 1949 edition'' and ``S
mfaceActive A history nP, Volmme
0'' (Interscience 9th edition), and the disclosures of these documents should be referred to as part of this specification.

From the above description, it can be seen that in a more particular aspect of the invention, the bleaching detergent composition comprises a: 3-4% by weight, preferably 10-35% by weight of detergent active compounds, bl-25% by weight, preferably is 2-1% by weight of a collective organic peroxy acid compound, c 2-4% by weight, preferably 5-3% by weight of an inorganic peroxy compound, and d o. 05-5% by weight, preferably 0.1-2% by weight of stabilizing sequestering agent.

Generally, detergent compositions of the present invention will include one or more detergent builders.

Typically, the total amount of detergent builder included in the detergent compositions of the present invention will be from about 5% to about 7% by weight of the detergent composition. Many detergent builders are known and those skilled in the art of formulating fabric laundry detergent compositions should be familiar with these materials. Examples of known detergent pilders include sodium tripolyphosphate; sodium orthophosphate; sodium pyrophosphate; sodium trimetaphosphate; sodium ethane-1-hydroxy-1,1-diphosphonate; sodium carbonate; sodium lotus; sodium citrate; acetate; sodium nitrilotriacetate; sodium ethylenediaminetetraacetate; long-chain dicarboxylic acids, such as straight mirrors (C,o
~ C) Sodium salts of succinic acid and malonic acid; Q
-Sulfonated long chain monocarboxylic acid sodium salt:
By polymerization or copolymerization of sodium salts of polycarboxylic acids, i.e. unsaturated carboxylic acids and their anhydrides, such as maleic, acrylic, itaconic, methacrylic, crotonic and aconitic acids and anhydrides of these acids. the respective sodium salts of the acids obtained or also obtained by copolymerization of the acids and acid anhydrides mentioned above with small proportions of other monomers, such as vinyl chloride, vinyl acetate, methyl methacrylate, methyl acrylate and styrene; Also included are modified starches, such as those oxidized with sodium hypochlorite, in which some anhydroglucose units have opened to form dicarboxylic units. Furthermore, the detergent composition of the present invention includes:
Any of the ingredients used in conventional detergent compositions can be included, and the dosages can be any of those conventionally used in conventional detergent compositions.

Examples of these additional ingredients include foam enhancers such as coconut oil monoethanolamide and palm kernel oil monoethanolamide, foam control agents, inorganic salts such as sodium sulfate and magnesium sulfate, sodium carboxymethyl cellulose. There are anti-redeposition agents such as, as well as fragrances, colorants, fluorescent agents, corrosion inhibitors, fungicides and enzymes, which are usually included in only small proportions. The bleaching detergent of the present invention is preferably in the form of fine particles, and may be a free-flowing powder or an agglomerate.

Methods commonly used or proposed for the preparation of particulate detergent compositions, such as dry mixing or slurry preparation followed by spray drying or spray cooling, followed by solid organic peroxy acids. Compound,
The bleaching detergent compositions of the present invention can be prepared by dry blending photosensitive ingredients such as a synergistic mixture of inorganic peroxy chloride and sequestering agents.

Other conventional techniques to minimize undesirable and undesirable interactions between bleach and other detergent composition components, such as noodleization, granulation, tabletting, etc., may be used as appropriate. can. The present invention will be explained below with reference to examples.

Example 1 Bleaching tests on tea stains were carried out using spray-dried detergent powder bases as follows, to which various amounts of bleach were added.

Powder base composition Weight% Sodium alkylbenzenesulfonate 18.4 Coconut fatty acid monoethanolamide 3.5 Sodium triphosphate
40.3 Sodium toluene sulfonate 2.3 Alkaline sodium silicate
12.7 Sodium sulfate
12.2 Wednesday
EI
△ measured with repho spectroreflectometer
It is expressed by the R side X value, which is shown in the following table.

DPAA = Diberoxyazelaic acid perslate = Sodium perslate tetrahydrate Sequestering agent = Ethylenediaminetrimethylenephosphonic acid Table 1 Table lb Example 0 Using the spray-dried detergent powder base of Example 1, A bleaching test was conducted on tea stains by adding different bleaching systems.

In each case, the mystery composition contains an amount of peroxyacid (PA) to give 0.9 mmol of [COOO-] in solution.
), if used, 1% by weight of sodium pershelate (P
erb. ), and if used, 0.2% ethylenediaminetetra (methylenephosphonic acid) as a sequestering agent, "EDTMP".

Table 2a Table 2b Table 2c Table 2d. 2e Table 2f Table 2g Table 2h Example m Using the spray-dried detergent powder base of Example 1 and adding 2% by weight of diberoxyazelaic acid (DPAA) 1 to
A bleaching test on tea stains was carried out by adding sodium peroxide tetrahydrate and 0.2% by weight of a sequestering agent.

The sequestrants used were as follows. Seq. 1(i)
= ethylenediaminetetra(methylenephosphonic acid)Se
c. 1(ii) = diethylenetriaminebenzene (methylenephosphonic acid) Sec. 1(iii)=triethylenetetraminehexa(methylenephosphonic acid) Sec. b =
A capping agent of formula 0, where n=1, X=day and Y=Z=C ratio COOHSec. m sequestering agent of formula m, where n = 1 and The results of the bleaching test are shown in the table below.

, Table 3a Table 3b Table 3c Table 3d Table 3e

Claims (1)

Claims: 1. A solid bleaching detergent composition suitable for use at virtually any laundry temperature comprising a detergent active compound and a solid organic peroxy acid compound, comprising: a 3-40% by weight detergent active compound; ( where X is H or an alkali metal, alkaline earth metal or ammonium cation)
]; or a compound with the general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (wherein n is an integer from 0 to 4, and X is H or an alkali metal, alkaline earth metal or ammonium cation); Compound; General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, n is an integer from 0 to 2;
3X_2; Z is CH_2COOX or CH_2
b 1-25% by weight of a solid organic peroxy acid compound which is PO_3X_2; c 2-40% by weight of an inorganic peroxy compound that generates hydrogen peroxide in solution; and d
0.05-5% by weight, general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (where n is 1-3, and X is H or an alkali metal, alkaline earth metal or ammonium cation) ); and a stabilizing sequestering agent selected from the group consisting of: 2 (a) 10 to 35% by weight of the above detergent active compounds; (
b) 2 to 10% by weight of the above organic peroxy acid compound; (
A solid bleaching detergent composition according to claim 1, comprising: c) 5 to 30% by weight of the inorganic peroxy compound; and (d) 0.1 to 2% by weight of the stabilizing sequestering agent. 3. A solid bleaching detergent composition according to claim 1 or 2, wherein the organic peroxy acid compound is a compound having a melting point of at least 50°C. 4. The solid bleaching detergent composition according to claim 3, wherein the peroxy acid compound is diperoxyazelaic acid, monoperoxyphthalic acid, diperoxyisophthalic acid, or a water-soluble salt thereof.