JPH02107699A - Detergent composition - Google Patents

Abstract

PURPOSE: To provide a fabric washing detergent composition improved in re- attachment preventing property by containing a surface active agent system, a dipicolinic acid compound, and a grout copolymer in specified ratios.

CONSTITUTION: This composite contains (A) 2-50 (wt)% of a detergent active system containing anionic, nonionic, cationic, amphoteric or zwitterionic surfactant, (B) 0.5-60% of a compound represented by the formula (R is H, Cl, Br, OH, amino, alkyl-substituted amino, carboxyl or 1-4C alkyl) and/or its water-soluble or water-dispersible salt, and (C) 0.1-3% of a grout copolymer of (i) each oxide of PE, PP or polybutylene and (ii) (partially saponified) vinyl acetate in a weight ratio of 1:0.2-1:10.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION FIELD OF INDUSTRIAL APPLICATION The present invention relates to an acid compound for textile laundry detergents with improved anti-redeposition properties.

BACKGROUND OF THE INVENTION AND PRIOR ART The re-deposition of dirt removed from washed articles back onto the laundry itself is a well-known problem, of particular importance for textiles, and many solutions have been proposed to this problem. ing. Classically, sodium carpo dimethyllerulose was incorporated into textile laundry detergent compositions, and this compound is now also used in '1. Copolymers, copolymers of acrylic acid and maleic anhydride and homopolymers of acrylic acid have been proposed in the patent literature, for example British Patent No. 1269848 (Procter &
Gamble) and No. 1460893 (Uni
1ever).

European Patent Publication No. 219048 (SF to B) discloses the use of a graft copolymer of polyalyalene oxide and vinyl acetate as an anti-blackening agent during washing and post-washing treatment of synthetic fiber products. .

The inventors of the present invention have discovered that a detergent composition containing the Granod copolymer of this invention and used in combination with Dibiny monophosphate exhibits a remarkable improvement in the ability to suspend and prevent soil re-deposition on polyester fabrics. .

The use of dipicolinic acid, its salts and derivatives as detergent builders is disclosed in British Patent Application No. 1342095 (Uni 1e
ver) and the tee opening.

definition of invention The detergent composition provided by the present invention consists of the following:

(a) a detersive active system comprising one or more anionic, nonionic, cationic, zwitterionic or amphoteric surfactants with 2=50=nfli%; fb) 0.5-60 tt% , general formula ■: (wherein R is a hydrogen atom, a chlorine atom, a bromine atom, a hydroxyl group, an amino group, an alkyl-substituted amino group, a carboxyl υ, or a C1
-4 alkyl group, and (c) 0.1 to 3% by weight,
(1) Graft copolymer of each oxide of polyethylene, polypropylene or polybutylene and (white) vinyl acetate (partially saponified as appropriate), the weight ratio of (1) and (11) is 1:
0.2 to 1:10.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a detergent composition comprising three specific ingredients, namely a surfactant system, a dipicolinic acid compound and a granod copolymer, which composition may be further combined with other conventional detergents. Ingredients may also be included, such as other builders, bleach systems, antifoam systems, fluorescent agents, inorganic salts, and other materials well known in the art in the manufacture of detergents. The compositions of the invention may take any suitable form, such as powder, liquid or bar.

Surfactant system In the composition of the present invention, the total amount of cleaning active substances (surfactants)
+ is -50% to 2, preferably 5 to 40Φ61%
It is.

The compositions of the present invention may include one or more soapy or non-soap anionic, nonionic, cationic, zwitterionic or amphoteric surfactants, or combinations thereof. A large number of suitable cleaning active compounds are available commercially in the literature, eg Schwartz, Parry and Be.
rch-73"5urfac-Active Age
nts and Deter(lonts) Volume 1 and Volume 2.

Preferred cleaning active compounds that may be used are soaps and J+ soap anions and co-L ion synthetic W surfactants.

Anionic synthetic surfactants are well known to those skilled in the art. Examples include argylbenzenesulfone Flu, especially straight-chain Aal, where the alkyl chain is Cg''□Cls in length, esdernalium sulfate; olefin sulfonates, alkanesulfonates, dialkyl sulfosuccinates;
and fatty acid 1 star sulfonate.

Suitable ionic ascending detergent compounds that may be used include, in particular, compounds with hydrophobic groups and reactive hydrogen atoms, such as aliphatic alkylene oxides, acids, amides or fulkylene phenols, Especially J-tylene'A1
It is a product obtained by reacting with cyto alone or by adding pyrene oxide. Specific nonionic detergent compounds include argyl (c) phenol-ethylene oxide condensates, condensation products of ethylene tertiary sites and linear or branched aliphatic or secondary alcohols (c), and argyl (c) phenol-ethylene oxide condensates; [There is a product obtained by condensing ethylene oxide with the reaction product of cobylene oxide and nibrendiamine.

Other so-called nonionic detergent compounds include long-chain tertiary amine oxides, tertiary phosphine oxides, and dialkyl sulfonyl oxides.

Particularly preferably primary and secondary alcohols 1
-1 in particular C1215 ethyl- and ni-al]yls ethyl-silated with an average of 5 to 20 moles of ethylene oxide per cell of I alcohol.

Containing one or more fatty acid soaps is desirable. Preferred are sodium soaps derived from naturally occurring fatty acids, such as those of coconut oil, beef tallow, sunflower oil or hydrogenated rapeseed oil.

A preferred type of detergent composition suitable for use in η machines (most automated weaving processes) contains both anionic and nonionic surfactants and has a Φ suspension of at least 0.67:1, preferably 1 :1, and more preferably 1:1 to 10:
It is within the range up to 1. UiM may also be present if desired.

The dipicolinic acid compound [formula (T) in the acid form or in the form of a completely or partially neutralized salt (a5 below) is referred to as a dipicolinic acid compound. .5~6
0% M present.

Preferably R in the formula represents hydrogen, ie the compound is dipicolinic acid itself or a salt thereof 1 Another preferred compound is a compound in which R is a hydroxyl group.

The compound is conveniently in the form of an alkali metal salt, more preferably a 1-licum salt. However, any suitable soluble fb i1 cation may be employed.

As mentioned above, these compounds are known detergent virgoos. These compounds are used as neutralizing builders in the compositions of the invention, but may also be used in combination with one or more other builders.

In a preferred embodiment of the invention, a dipicolinic acid compound is used with a crystalline or amorphous alkali metal aluminosilicate salt. Aluminosilicates are preferred (10 to 60 heavy FI
I% (7) if te, even better i L < 4,1
Present at 2 O-bo wt% instep. In this embodiment of the invention, the dipicolinic acid compound is suitably present in a relatively low Ql, for example 1 to 10 w%.

The alkali metal aluminosilicate (preferably brylium) used in the embodiments of the present invention may be crystalline or amorphous, or a mixture thereof, and has the general formula: %.

These materials must contain some bound water and have a calcium ion exchange capacity of at least about 50 zl of Ca0zl. A preferred sodium aluminosilicate contains 8102 units of L5-3.5 (in the above formula). Both amorphous and crystalline image quality products can be easily produced by the reaction of zitorium silicate and sodium aluminate, as described in the literature.

Suitable crystalline aluminosilicate ±1-lium ion exchange detergent builders are described, for example, in British Patent No. 1473201 (
1lenkel) and No. 1429143 (Pr.
Octer & Gamble). Preferred puttrium aluminosilicates of this type include the well-known commercially available ZEL-A-[Delta]-[Delta] and X, and mixtures thereof. Particularly preferred is zeolite 4Δ.

Other builders may be included in the compositions of the present invention as necessary or desired, including suitable or inorganic water-soluble builders or water-insoluble builders, which are readily within the purview of the detergent formulator. Inorganic builders present include alkali metal ortho-, pyro-, and tripoly-phosphate (generally pyrothorium) salts; organic builders include nitri[+1-lyacetate, citric resistant 1 and callevoxy]. There is methyl 1:cisuccinate. The items listed here are not intended to be trivial. The level of total I11 in detergent virgoo is generally in the range of 20 to 80,000 to 1%.

In 11 preferred embodiments of the present invention, the composition contains less than 101% inorganic phosphate builder, and more preferably is substantially free of inorganic phosphate.

Graft Copolymers The Graf 1-copolymers used in the compositions of the present invention are described in European Patent Publication No. 1, T Publication No. 2190118 (BASr). The copolymer has a molecular weight (number average) of 2000
Graph 1 ~ 100,000 polyalkylene A1 site is made with acid-resistant vinyl that may be partially saponified, and at this time, the weight ratio of polyalkylene A1 site and vinyl acetate is 1:02.
Obtained as 1:10. Vinyl acetate, for example, may be saponified at a rate of up to 15%. Polyalkylene A
One site contains a structural intermediate consisting of ethylene oxide, propylene oxide and/or butylene oxide, with polyethylene A oxide being preferred.

Preferably, the polyalkylene oxide is 4000 to -5
0000: j''-14'1 is equal to E1, and the weight ratio of polyalkylene oxide and vinyl acetate is 1:05.
No 〒1:6r. Especially good, good [yo, molecule 4ti]
From 2000 to 50000 poly L Brene A oxide)
The ratio of polyethylene oxide and vinyl acetate in the Φ combination to be prepared is 1:05 to 1:6.

Substances that fall within this definition are based on polyethylene oxide with a molecule a16000 (corresponding to the 136+i position of ethylene oxide), contain about 3 parts of vinyl acetate per 1% part of polyethylene oxide, and contain - The molecular weight of itself is 24,000, which is 5 from B A SF.
It is commercially available as okalan™ HP22.

The weight of the polymer present in the composition of the invention is from 0.1 to 31
1'i % by weight, preferably 0.3 to 1% by weight.

Optional Ingredients As well as the above-mentioned ingredients, namely surfactant systems, dipicolinic acid compounds, their respective builders and graft copolymers, other non-components known to be suitable for inclusion in detergent compositions are also included. Interfering components may also be included in the compositions of the invention.

For example, the detergent compositions of the present invention may optionally contain a bleach system. Preferred are bleaching peroxy compounds, such as inorganic persalts or peroxyacids, which may be used in combination with additional activators to improve the bleaching action in low temperature laundering. A skilled detergent manufacturer will have no difficulty in selecting a suitable bleach system by applying normal principles.

Other substances which may be present in the detergent compositions of the present invention include sodium silicates, fluorescent agents, unsalted salts such as sodium sulfate, silicates, suitable foaming agents or foaming agents, pigments and fragrances. can be mentioned. Also, this enumeration is not intended to be exhaustive.

Preparation of Detergent Compositions The detergent compositions of the present invention may be prepared by any suitable method. To produce detergent powders, it is appropriate to spray dry a slurry of non-thermosensitive, compatible components and then spray or later compound the components unsuitable for processing via the slurry. A skilled detergent formulator will generally be able to readily determine which ingredients should be included in the slurry and which ingredients should be subsequently formulated or sprayed.

Granod copolymers are available as a 20% solids solution which is stable at slurry processing temperatures and can be incorporated into slurries without problems, provided the pl+ is maintained below 12.

Similarly, dipicolinic acid compounds can typically be included in the slurry.

The present invention will now be illustrated by way of a limited example.
Unless otherwise specified, parts and percentages are manual parts and 1 ■ presentation hundred minutes - r
It is.

EXAMPLES Four detergent compositions of the following formulation C were prepared by conventional slurry preparation methods, spray drying methods and post-formulation methods.

Percent chain sodium alkylbenzenesulfonate nonionic surfactant 7EO Zeolite 4△ (hydrate group 1 9.0 Alkaline sodium silicate Sodium sulfate Sodium carbonate Sodium carboxymethyl cellulose Fluorescent agent 0.7 Zitorium perborate - water Salt tetraacedelethylenediamine (76% fine #I) Enzyme granules DPA (sodium dibiphosphate) Graft copolymer (Sokalan 1IP22) Water and minor components 0 or 2.0 0 or 0.5 100, 4 up to 0 Details of the composition are shown in the table below.

The soil suspension (prevention of redeposition) properties of the compositions were compared using the following procedure. Two clean, unwashed 1η new polyester test cloths, together with five dirty cloths, were heated at 60°C in a turbotometer at a ratio of about 50:1.
Wash in hard water (French hardness)? i' L/, wash 1
Solution 71 contained test detergent composition 49/ρ.

The stained cloth was exposed to a series of different stains such as clay, oil, fat, protein and ink. I replaced the soiled cloth with a new soiled cloth (with the same range of soiling) every 8 washing cycles, and repeated the washing 4 cycles nine more times.

The fouling rate of two fresh fabrics was measured before washing and after 10 wash cycles. The decrease in reflectance of washed items after 10 washes is shown below. 8) The lower the rate of decrease, the smaller the reattachment that has occurred.

−Song Yiichino Example Change in reflectance (ΔRne) A Control
-6, OB 0.5%5okalan flP22
-7.0G 2.0X
DPA -3,810,5%5okalan+
2.0χDPΔ -2,2 Composition C is a comparative example, while Composition 1 is an example of the present invention. The graft copolymer 5okalan 1IP22 had no significant effect on redeposition. Sodium dipicolinate had a somewhat substantial beneficial effect on reattachment, but the effect was very conspicuously enhanced by the presence of graft coalescence.

Claims (3)

[Claims] (1) A detergent composition consisting of the following. (a) a detersive active system comprising from 2 to 50% by weight of one or more anionic, nonionic, cationic, zwitterionic or amphoteric surfactants; (b) from 0.5 to 60% by weight. , General formula I: ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is a hydrogen atom, a chlorine atom, a bromine atom, a hydroxyl group,
(representing an amino group, an alkyl-substituted amino group, a carboxyl group or a C_1_-_4-alkyl group) and/or a water-soluble or water-dispersible salt thereof,
and (c) 0.1 to 3% by weight of a graft copolymer of (i) polyethylene, polypropylene or polybutylene oxide and (ii) vinyl acetate (optionally partially saponified).
and (ii) in a weight ratio of 1:0.2 to 1:10. (2) The detergent composition according to claim 1, further comprising 10 to 60% by weight of a crystalline or amorphous sodium aluminosilicate builder. (3) The graft copolymer (c) has a molecular weight (number average) of 2
000 to 100,000 polyalkylene oxide is grafted with vinyl acetate (partially saponified as appropriate) at a weight ratio of 1:0.2 to 1:10.
The detergent composition according to claim 1 or 2.