JPS61108697A - Polymer-containing detergent composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polymer-containing detergent compositions, and more particularly to textile laundry detergent compositions containing small amounts of organic polymers to prevent soil redeposition.

The re-deposition of dirt removed from washed articles onto these articles is known to be a particularly serious problem with textiles, and a number of solutions have been suggested. Sodium carboxymethylcellulose has traditionally been incorporated into compositions for cleaning textile products, and this compound is still in use today. Very recently, copolymers of ethylene or vinyl methyl ether with maleic anhydride, copolymers of acrylic acid with maleic anhydride, and homopolymers of acrylic acid have been patented (Brocter & Gamble, UK). 1.269.848 and Unilever UK Patent No. 1.460.89) and is widely used in practice.

It has now been discovered that a new class of polymers exhibits useful anti-redeposition effects and can be used in fabric laundry detergent compositions to reduce fabric ashing. Furthermore, these new types of aggregates also have the advantage that they can aid in the structuring of detergent powder compositions and their dispersibility.

The detergent composition provided by the present invention comprises a detergent active compound and an anti-redeposition polymer, which anti-redeposition polymer has the general formula: % formula % (wherein R is a hydrogen atom, a carboxyl group, Alternatively, an ethylene compound of the general formula: %C, where R' can be taken together with carboxyl groups on adjacent carbon atoms to form an anhydride, and R' is a hydrogen atom or a methyl or ethyl group, is R' is a hydrogen atom, a straight-chain or branched alkyl group having 1 to 18 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms.

It can be an aryl group, an alkaryl group or a group of the general formula Ox, in which X is a hydrogen atom or a straight-chain or branched alkyl group having 1 to 4 carbon atoms. , RII is a group of the general formula Ox, where X has the flavor described above.

The polymer formed by this reaction has the general formula (I): NL if R' is other than a hydrogen atom, and the polymer of the above formula and the general formula (I) if R' is a hydrogen atom. : (υ2h BON”' CO!H [in the formula, R
, R' and RII have the meanings given above, and m and n are integers.] It is expected to be a mixture of 01 species.

The carboxyl group in the above formula may be bonded to the C atom adjacent to the P atom.

Polymers of the above type are disclosed in British Patent Nos. 1,458.23 and 1.595,688 (Tever-Geigy), where the polymers are used for industrial purposes. (For example, industrial boilers, steam powered converters,
Scaling inhibitors have been suggested for use in applications such as cooling water systems and water desalination). However, only a limited range of polymers have been disclosed for the white or brightness
It has been found that a) is not suitable for use in detergent compositions as an effective anti-redeposition aid to improve retention. This range applies to acrylic acid or its equivalent monomer (i.e. ethylene compound monomer)
and the reducing phosphorus-containing compound in a ratio of 10:1 to 60:1. The preferred range is 12:1 to 35:1.

Polymers outside this range, particularly those having a ratio of less than 10:1, are not effective as anti-redeposition agents.

Preferably each of R, R' and R' represents a hydrogen atom and RII represents OH. These compounds can be added to the composition in acid form or in salt form, such as the sodium salt. However, if large amounts of sodium ions are present in the detergent composition, it is inevitable that the monomer will be present as a sodium salt upon use.

One embodiment of the present invention combines these into aqueous claracha.
aher) into detergent compositions, either by mixing with the other components of the slurry and spray drying, or by adding them to the composition along with heat-sensitive ingredients, such as sodium peroxide, after the spray drying step. can do.

The amount of the polymer to be incorporated into the detergent composition in order to obtain the anti-redeposition effect is from 0.1 to 10% by weight, preferably from 0.5 to 3% by weight, based on the composition.

Furthermore, these polymers can also be incorporated into liquid detergent compositions.

The exact chemical nature of the detergent composition incorporating the polymer is not particularly critical as this anti-redeposition effect is common. These compositions always contain detergent actives and generally also detergent builder compounds. The remaining ingredients will vary depending on whether the composition is a liquid or a powder. The amount of detergent active compound present in the composition generally ranges from about 3 to 5.0 l-Ji%, but can be greater if the composition is provided in the form of a non-aqueous liquid composition.

However, the invention is particularly advantageous for detergent compositions with low phosphate builder contents, for example up to 25% by weight, especially detergent compositions containing less than 20% by weight of sodium tripolyphosphate.

If the detergent composition is a powder, the polymer added to the aqueous detergent slurry before spray drying may be a structuring agent.
rant ). This is important if sodium tripolyphosphate and/or sodium silicate is present in insufficient amounts for proper organization.

If the detergent composition is a liquid, the composition of the detergent builder compound will generally include anionic and nonionic surfactants, possibly an aqueous substance or a co-solubilizing agent, e.g. antioxidants, fluorescers, etc. Contains minor ingredients such as agents, colorants and fragrances. However, if you pay attention to the dissolution characteristics,
It is also quite possible to incorporate detergent builders into liquid compositions.

Sometimes it may be necessary to use highly soluble salts, such as the potassium salts and triethanolammonium salts. The builder compound may be dissolved in the liquid medium or suspended in the medium if it is structured.

Powdered detergent compositions generally include a conventional two-component system comprising a sexual and/or cationic surfactant, a detergent builder, a sodium silicate as a powder structuring agent, a corrosion inhibitor and a polymer as disclosed in the present invention. It consists of minor heat-stable ingredients such as anti-redeposition agents, antioxidants and fluorescent agents. Compounds with poor thermal stability, such as oxygen bleach
(sodium ilIII acid hydrate and/or tetrasalt and sodium percarbonate)2 bleaching precursors such as tetraacetylethylenediamine and sodium nonanoyloxybenzenesulfonate, enzymes and fragrances are mixed with the spray-dried portion to form a single homogeneous form a powdered composition.

The properties of the anionic detergent active compounds used in the compositions of the invention are not critical. The compounds are suitable surfactants for use in detergent compositions, such as primary and secondary alkyl (jlt) salts.

Examples include secondary alkanesulfonates, olefinsulfonates and alkylarylsulfonates, especially the sodium salts of these compounds and soaps, ie salts of fatty acids derived from natural substances. Anionic detergent active compounds are generally present in detergent compositions of the present invention at about 3 to 30 hit%, preferably about 5 to 15% by weight of the composition.
It exists with a lid. Approximately 3 oii of anionic surface active ingredients
A composition containing a large amount of S is difficult to process and is industrially expensive.

The compositions of the present invention can also, and usually do, contain nonionic surfactants. Preferred nonionic surfactants are ethoxylated alcohols because they are cost-effective and environmentally safe, but other nonionic surfactants such as long-chain alkanolamides may also be used. It is also possible to use Suitable ethoxylated alcohols contain from 5 to
C ethoxylated with 25 moles of ethylene oxide,
-C, primary and secondary alcohols.

Nonionic surfactants may be used in amounts of from about 3 to about 20 weight percent when present alone in the composition, and from about 1 to about 15 hits when present with anionic surfactants. can.

If the composition contains detergent builders, carbonates, especially sodium carbonate or orthophosphates, pyrophosphates, tripolyphosphates or mixtures thereof are suitable as detergent builders. A particularly preferred phosphate builder is a mixture of sodium tripolyphosphate and sodium orthophosphate.

However, other organic or inorganic precipitants or sequestrant builders can be used alone or in admixture or with or without co-K or phosphate builders. These include, for example, alkali metal amine carboxylates such as sodium nitrilotriacetate and sodium ethylenediaminetetraacetate, alkali metal ether carboxylates such as sodium oxydiacetate, sodium carboxymethyloxysuccinate, carboxymethyloxymalonic acid, etc. Included are congeners, alkali metal citrates, alkali metal melitates, and salts of polymeric carboxylic acids such as sodium polymaleate, copolyethylene maleate, polyitaconate, and polyacrylate. When sodium carbonate is used as a detergent builder, the presence of a species of calcium carbonate having a surface area of at least about 10 m''/1 as described in British Patent No. 1,437,950 is preferred. It's advantageous.

Other types of detergent builders which may be used alone or in admixture with other builders are cation exchange materials, in particular those described in eg British Patent No. 1,429,443 or Dutch Patent Application No. 7,403,381. Sodium aluminosilicate as described in .

Preferred materials of this type have the formula: % Formula % and are amorphous or crystalline and generally have bound water in an amount of about 10 to 30%, depending on the drying conditions used. Of course, such sodium aluminosilicate materials should be extremely fine so that they adhere to the textiles only minimally during laundering.

Recently, there has been a growing trend in many countries to impose regulations to reduce or completely replace the amount of sodium tripolyphosphate in textile laundry products.

As a result, some of the valuable secondary effects of sodium tripolyphosphate were lost, such as soil redeposition inhibition and fabric ashing, powder texturing and powder dispersibility.

All of these effects can be remedied to some extent by using the polymers of the invention.

Water-insoluble aluminosilicate cation exchange materials, such as zeolites, are present at higher levels (as corrosion inhibitors and/or Silicic acid (as a curing agent) poses the problem of IJum depositing on textiles and forming insoluble substances. To overcome this problem, the amount of alkali metal silicate in compositions of this type is kept below the standard level, i.e., below about 41%, unless the amount of sodium silicate is insufficient. The powder cannot be properly organized. In this case, the polymers according to the invention can also be used to compensate for the lack of silicate as structuring aid.

Accordingly, the polymers of the present invention are particularly advantageous as anti-redeposition agents in powder compositions containing less than about 4 Ni% alkali metal silicate material.

The total amount of detergent bitters used in the composition generally ranges from about 10% to about 60% by weight of the composition, preferably from about 15% to about 50% by weight, and in combination with the detergent builder used. The normal ratio with detergent active compounds is generally from about 3:l to
Approximately 1=2.

Furthermore, in addition to the above-mentioned components, the detergent composition of the present invention may include:
Conventional optional additives may also be included in amounts commonly used in detergent compositions. Examples of these additives include foam suppressants;
One combination other than one according to the invention, such as the well-known homopolymers of acrylic acid or its salts, salt-release bleaches such as the alkali metal salts of trichloroisocyanuric acid and dichloroisocyanuric acid, softeners such as quaternary ammonium salts, Included are anti-ashing agents, starches, inorganic salts such as sodium silicates and sodium sulfates, and fluorescent agents, which are generally present in very small amounts, fragrances, dyes such as proteases and amylases, fungicides and colorants. Generally, detergent compositions are prepared at an alkaline pH (generally between pH 9 and 1).
1), which is achieved in particular by the presence of alkaline salts such as sodium silicates, such as meta-5 neutral or alkaline silicates, preferably in amounts up to about 15% by weight. .

Hereinafter, the present invention will be explained with reference to examples, in which parts and parts are by weight unless otherwise specified.

(The following is a blank space) Example 1 The anti-redeposition effects of three types of compositions containing various polymers were tested. First, a solution containing 497 parts of the detergent composition shown below in water having a French hardness of 40' was prepared.

Weight% Dodecylbenzenesulfonic acid 6
．． 0C14-11i “BO nonionic surfactant
2.0 Hardened Sodium Stearate
3.0 Sodium tripolyphosphate
7.5 Sodium orthophosphate
7.5 Alkaline sodium silicate
7.0 Sodium perborate
200 Sodium Sulfate
20.0 Sodium carboxymethyl cellulose 0.5 Polymer C (see Table 1) 1.0 100.0 To these three test compositions, the polymers shown in Table 1 below were added @ Table 1 1 Not added 0 Using each of these compositions, a white cotton monitor was
Cleaning test 11E stained with MPA 101 (black ink/olive oil) in the presence of cloth (Tergot
cmter) (Washing conditions were as follows: Temperature: 60C Washing time: 20 minutes submersion time = 5 minutes rinsing time = 2 times of 1 minute each This washing operation was performed 6 times, each washing After the cycle, the reflectance of the cotton monitor was measured according to the Tanebe method and the results are shown in Table 2. $2 Table A 14.6 17.3 18.7 Not measured
21.8 23. OB 9.0 10.8 12
．． 7 11111 Not determined 16.1 16.5C1,9
2,23,2 Not measured 4.6 5.3 As can be seen from these results, the change in reflectance of the cotton monitor washed with Composition C (i.e., the composition according to the present invention) Comparative composition A containing no anti-redeposition polymer or composition B containing both SCMC and Soka-1an CP5 (this is probably the best combination currently known in the detergent art) lower than either.

Example 2 Chill=r)meter〇 In a laundry experiment, the stain re-deposition prevention effects of three different polymers were evaluated using various soiled test cloths and article pieces (cut from towels stained with tea). compared. In addition, the following composition was used as a basic detergent powder.
I used it.

The washing conditions were the same as those used in Example 1.

Weight - Sodium dodecylbenzenesulfonate
9.0 Sodium tripolyphosphate (STP)
25.0 Sodium carbonate
5.0 alkaline sodium silicate
6.0 Sodium Carboxyl Methyl Cellulose 0
．． 5 Sodium sulfate 2
5.0 perboric acid) IJium tetrahydrate (post-administration)
15.0 Polymer Tatami 1.
0100.0 The STP decomposition rate at the time of manufacture was 30.

”N combination (a1 = dry acrylic acid/hypophosphorous acid copolymer (
25: 1) Polymer (b1 = commercially available polyacrylic sheet (t) a-
Natrol ■34] 3 combination (cl = dry acrylic a!/maleic acid copolymer (Natrol) ■(:'p
5 BA8F) Table 3 below shows the ranking of the polymers that showed the best effect after 3, 6 and 9 rinses. The symbol 〉 means that the one coalescence on the left is much better than the one coalescence on the right.

Table 3 As can be seen from the above results, one coalescence (al
The compositions using C1 are generally superior to other compositions containing polymers (BL or C1).

Example 3 Polymer (a), polymer [bl and polymer (
The re-deposition prevention effect of C1 was compared. The laundry was washed in a two-tank washing machine, and the resulting soiled washing liquid was used as a contamination source in the subsequent Chill Hitometer ■ adhesion experiment. The washing conditions were as follows.

Temperature 2 600 Washing time: 20 minutes Submerging time: 5 minutes Rinse time: 2 times for 1 minute each with dirty washing liquid gll! ! ! :French hardness 40' Polymer added: 110 for the product Preparation of washing liquid: 4 x 2.5 kliJ of soiled material was placed in the same 35] demineralized water using a tergotometer ■The same product without the polymer to be used in the experiment The basic product was washed for 20 minutes at 8 liters using 41/liter.

The results of the Chill Hitometer ■ adhesion experiment in Table 4 show the change in reflectance (-ΔR) of a white cotton monitor: Table 4 - Each horizontal shelf of ΔR values was obtained from one patch of soil solution. and another batch was now used for each of the next four washes. Comparisons of the effectiveness of various polymers, laundry compositions, etc. can only be made within the scope of one experiment and should not be compared between different experiments since each patch of laundry liquid used is different.

The above data shows that when polymer (a) of the present invention is used, polymer (b) (i.e. polyacrylate) and polymer (
This shows that it is the most effective compared to C) (that is, a combination of acrylic acid and maleic acid).

Example 4 In a terbitometer test, the effect of acrylic acid/hypophosphorous acid copolymer (25:1), i.e., the Example 201 polymer (a), and the effect of Tukaran CP5 (BASF), i.e., the Example 20 polymer ( The effect of c) was compared in conventional anionic/nonionic compositions containing various builders.

Washing conditions: Product usage amount 2 41/L Temperature: 60C Washing time = 20 minutes Immersion time: 5 minutes Rinse time: 2 x 1 minute Soiled Cloth 2 EMPA 1 (11 (fi juice/
Oh! Changes in the reflectance of the cotton monitor measured after washing six times are shown in Table 5 below.

The above results also show that the change in reflectance of cotton monitors washed with a composition containing polymer (a) (i.e., the composition of the present invention) after washing with a composition containing polymer (c) outside the range of the present invention. It is clear that the quality of the cotton monitor is also lower.

Example 5 In this example, the effect of polymer level in a detergent powder composition on soil re-deposition was tested in a tergotometer wash experiment.

The detergent powder composition was essentially the same as that used in Example 1, except that the level of copolymer (in this case dry acrylic acid/hypophosphorous acid copolymer having a ratio of 25:1) was reduced to 0. ~
The concentration was varied within the range of 1.4'ii%, and this was lightened with sodium sulfate.

Washing conditions: Temperature: 60°C Washing time: 20 minutes Submersion time = 5 minutes Rinse time: 2 x 1 stain Fabric: EMPA 101 re-deposition monitor; Combed white cotton product usage amount 2
Hardness: French hardness 40° The results are shown in Table 6 below.

1 combination -00,50,81,11゜4 JR1B after 3 washes, 5 11.4 8.0 5,6
5.3 Example 6 An experiment was conducted regarding re-deposition at the initial stage of washing.

In the early stages of washing, the product concentration is low. This is due to the limited dissolution rate of product ingredients and the mechanical loss of powder to the bottom of the washer. This tergotometer
In an experiment, a product containing 31 amounts of polymer was
f/ was used. This is nominally 51 using 1% coalescence.
This mimics the initial washing at 1 f/l (European conditions), but with only 1 f/l of product and a much higher proportion of polymer dissolved together. The washing time was set to 5 minutes.

Example 20 containing 23 sodium tripolyphosphate
In the basic product composition, polymer (a) of Example 2 (
MW 6200) and almost the same molecule it (MW 61.00
) compared with polyacrylic material.

These results, shown in Table 7 below, show the change in reflectance (-JR)'fc of the cotton monitor after washing three times.

Table 7 Table 11.9 5.9 7.5 11.6 6,3 7,1 11.2 7,0 8.8 10.7 6,5 8゜1 These results also indicate that the polymer of the present invention (This shows that products containing &J are superior to products containing polyacrylates outside the scope of the present invention.

Claims (8)

[Claims] (1) Comprising a detergent active compound and an anti-redeposition polymer,
Said polymer has 1) the general formula: CHR=CR'CO_2H, where R is a hydrogen atom, a carboxyl group, or can be taken together with a carboxyl group at an adjacent carbon atom to form an anhydride, and R' is 2) General formula: ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R'' is a hydrogen atom, having 1 to 18 carbon atoms. A straight-chain or branched alkyl group, a cycloalkyl group having 5 to 12 carbon atoms, an aryl group, an alkaaryl group or a group of the general formula OX, where X is a hydrogen atom or
is a straight-chain or branched alkyl group having ~4 carbon atoms), R''' is a group having the general formula OX (wherein X has the above meaning)
The polymer is produced by reacting with a reducing phosphorus-containing compound, and when R'' is other than a hydrogen atom, the general formula is: and when R'' is a hydrogen atom, the polymer of the above formula and the general formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R, R' and R'' have the above meanings. and m and n are integers such that the ratio of the ethylene compound monomer to the reducible phosphorus-containing compound is from 10:1 to 60:1). Composition. (2) The detergent composition according to claim 1, wherein the ratio of the ethylene compound monomer to the reducing phosphorus-containing compound is 12:1 to 35:1. (3) The anti-redeposition polymer is present in an amount of 0.1 to 10% by weight of the total composition.
The detergent composition according to item 1 or 2. (4) A detergent composition according to claim 3, characterized in that the amount of anti-redeposition polymer is 0.5 to 3% by weight of the composition. (5) A detergent composition according to any one of claims 1 to 4, further comprising a detergent builder in an amount of 10 to 60% by weight of the composition. (6) A detergent composition according to claim 5, characterized in that it contains up to 25% by weight of phosphate builder. (7) The detergent composition according to claim 6, characterized in that it contains less than 20% by weight of sodium tripolyphosphate builder. 8. The detergent composition of claim 5, further comprising an alkali metal silicate in an amount less than about 4% by weight of the total composition.