DE1901632A1 - laundry detergent - Google Patents

Description

laundry detergent

The present invention "relates to laundry detergents of tissues.

When soil is removed from fabrics during laundering, there is usually a tendency for the soil to appear before the end of the wash Washing to re-peel the fabric, around this tendency to counteract it, it has been proposed to introduce so-called "dirt-carrying substances" into the washing solutions « Such soil release agents are usually polymeric in nature; the most common is sodium carboxymethyl cellulose While this compound has been used in the treatment of cotton -with rather satisfactory results may, it is less useful for the treatment of fabrics that are at least partially made of synthetic fibers, im Special nylon, are made, and made of polyester => fabrics "

It has now been found that certain water-soluble or = dispersible synthetic copolymers are effective dirt-carrying substances, especially for treatment of polyester fabric o

According to the invention, a detergent intended for washing fabrics contains a water-soluble or “dispersing”

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COPY

available copolymer of the general formula

?1 ?

ι ι

G C -

I I

COOX COOX

wherein R ^ is a hydrogen, chlorine or bromine atom or represents a lower alkyl group;

R ₂ and R,

Represent hydrogen, chlorine or bromine atoms or lower alkyl groups; or R _{2 is} a nitro group (-HO ₂ ) or an araino group or a substituted amino group (-N (Rg) ₂ ), wherein each Rg represents a hydrogen atom or a lower alkyl group, and R 1 represents a hydrogen atom;

R4 represents a hydrogen atom or a lower alkyl group is;

Rk represents a hydrogen = ·, chlorine or bromine atom or a hydroxy group (-0H) or an amino group or a substituted amino group (-N (Rg) ₂ ), in which each Rg represents a hydrogen atom or a lower alkyl group;

and X is a hydrogen atom or an esterifying group ₉ which is a lower alkyl group or a benzyl group or a substituted benzyl group, the degree of esterification, as defined below, being within the range from 5 to 75 ° _f

or a salt of it,

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• t

Under the term "lower alkyl group" in the definitions was used for groups of the formula (I), an aliphatic group with 1-5 carbon atoms is to be understood here «, If the copolymer is made from a substituted benzyl ester of maleic acid, the substituting Groups in the benzene ring can be non-reactive groups that are small enough not to be affected by steric hindrance To prevent adsorption of the copolymers on fabrics, z "Β" one or more hydroxyl groups, amino or substituted amino groups or lower alkyl groups.

The invention also encompasses a method of washing a fabric, particularly one containing synthetic fibers Fabric, by contacting the fabric with an aqueous solution of the detergent so

The copolymers used according to the invention can be carried out by solution or suspension polymerization using are produced by free radical catalysts. or the monomers can be used in the absence of any diluent to be reacted with each other, the usual Reaction partners are styrene or a substituted styrene and a partial ester of maleic acid or a substituted maleic acid ο The copolymers can through Reaction between styrene or a substituted styrene and maleic anhydride or a substituted maleic anhydride with subsequent hydrolysis and partial esterification of the anhydride groups, but this process is of much less practical interest because of the difficulty in obtaining an adequate degree of esterification to achieve"

The monomers used to prepare the copolymers are preferably used in approximately equimolar amounts brought together to implement, because even if an excess of one or the other monomer is used, tend but the copolymers produced to it, from about

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To consist of equimolar amounts of the monomer units so that the excess unpolymerized monomer is subsequently removed must o However, in the grain according to the invention » Positions used copolymers do not contain exactly equi »molar proportions of monomer units, since the appropriate choice of the degree of esterification compensates for Changes in water solubility or dispersibility of the copolymers, which are based on fluctuations in the relative proportions of the monomer units, create can.

For economic reasons, it is generally preferred superiors ^ "in making the copolymers unsubsti- ψ tuiertes styrene and a partial ester of maleic unsubstituted use. In this case, R ₁ , R ₂ * Rz, Rj and Rc in the formula (I) represent hydrogen atoms or at least predominantly hydrogen atoms, it being possible for minor amounts of substituted styrenes or the partial esters of substituted maleic acids to be present in the monomeric materials used. However, when it is desired to use a partial ester of a substituted maleic acid, the most readily available compounds are those in which the substituting groups are methyl groups, e.g. B. the partial esters of citraconic acid »Various substituted styrenes are available and, if desired, can be used in the preparation of the copolymers; Examples of such substituted styrenes are as follows:

o-, m- and p-chlorostyrene,
o-, m- and p-aminostyrene,
2,3-dichlorostyrene (and other isomers), alpha, beta- and beta, beta-bromostyrene, 2-hydroxy-beta-nitrostyrene and 4-hydroxy-3-nitrostyrolo,

The copolymers used according to the invention can be small Amounts of monomer units include that from

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sources other than styrene, substituted styrenes, partial ester derived from maleic acid or partial esters of substituted maleic acid, since copolymerizable monomers are impurities be present in the reactants before the copolymerization or can be added to them.

The use of partial esters of the copolymers according to the invention is necessary to achieve the optimum balance between hydrophobic and hydrophilic properties to achieve dirt-carrying capacity, especially for treatment hydrophobic fibers, to create «copolymers, which are unesterified, are too water-soluble» during the fully esterified copolymers are water-insoluble «Normally the half esters of maleic acids are used to produce the copolymers, but during the Copolymerization or use can hydrolyze some of the ester groups or esterify some of the caboxyl groups so that the copolymers are not exactly half-esterified.

In the context of the present invention, the degree of esterification is given as a percentage, the esterification * degree of the half ester as 50 $ and that of the fully esterified Product than 100 $ ig · takes »Generally speaking, it is preferred to use copolymers that contain one Have degree of esterification between $ 25 and $ 62.5. In particular for treatment of polyester fabrics it has been found that the optimum results can be obtained by using copolymers which have a degree of esterification of 25 ~ Own 50%.

The molecular weights of the copolymers also influence their dirt-bearing properties. Because the molecular weights are directly related to the specific viscosities of solutions of the copolymers in the case of other than very low concentrations of the copolymers in the solution »

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are average, the molecular weights for the purposes of the present description are conveniently measured and expressed as the viscosities of 1% (weight / volume) solutions of the copolymers in acetone O ₉ 13 *

The amounts of the copolymers which are used as soil suspending agents in the detergents may vary widely, although usually not used more than about 5 Gew.?$o "preferential catfish, an amount of 0.5 to 4, z" B . 1 = 2 percent, ° J> _o thus, if such a composition in aqueous solution at a concentration of about 0.4 percent, $ £ _o, as is customary in general, is applied, the concentration of interpolymer in the aqueous Washing liquor approximately in the range 0.002-0.016% by weight. If a lower concentration of a detergent is used in a washing liquor, it may be desirable to increase the proportion of the copolymer in the agent *

In general, it is preferred that the soil-carrying-Misehpolymerisat in the detergent in an amount to use ₉ which during use in aqueous solution has a concentration managed the interpolymer of at least 0.004 wt _o $ That is z _o B _0, that the concentration of interpolymer in detergent preferably at least 1 wt. ^ is, when the detergent itself is applied with a concentration in water of 0.4 wt _o $.

The inventive detergents may mild detergent or heavy-duty detergents, liquid or solid "While a mild detergent for washing fabrics by hand at relatively low temperatures meant _t sindρ are coarse detergent for use in washing machines at higher temperatures provided

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• «« w · ν f meet

Ί-

The detergents may the same contained as washing active substances, any anionic, nonionic, cationic or amphoteric active compounds or mixtures "Many such compounds are known and HanöeiTo The most commonly used detergent-active compounds are anionic, z" B ₀ soaps, alkyl benzenesulfonates, alkyl sulfates, alkane sulfonates, olefin sulfonates and like "Hichtionische detergent active sub ~ punch are also common and show -special utility in the so-called schwachechäumenden detergents which sindο primarily for use in automatic washing machines which are sensitive to foam, intended Cationic and amphoteric active substances, Z ₀ B ₀ quaternary Ammoniunwerbindungen or sulfobetaine compounds, are less common, generally for reasons of economy, but they too can, if desired, be used to satisfaction in the compositions according to the invention »

The amounts of detergent compound or compounds in the compositions according to the invention can be within a wide range vary, but will generally be in the range of about 10-60 Gewo # »The proportions of the quantities of Active washing compound or compounds to those of the dirt-carrying copolymer are therefore normally at least 2 ϊ 1 "and can be up to 100: 1 and go beyond that.

Apart from the detergent active compounds and the soil carrying copolymers can compositions of the invention any of the conventional additives for laundry detergents, including, for _o B _n builders, inorganic salts, hydrotropes, germicides, optical brighteners, dyes and Enzymeο The compositions may also contain other soil suspending substances for the treatment of hydrophilic fibers, Z ₀ B. Hatriumcarboxymethylcellulose containing <,

The following examples describe the production of suitable

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! Neter dirt-carrying copolymers for use in the Agents according to the invention ο All data on parts and percentages are weight data, unless otherwise stated is.

(A) Copolymer of styrene and methyl hydrogen maleylxate "

The copolymer was prepared by mixing equimolar amounts of styrene and methyl hydrogen maleatate with 0.5 # based on the weight of the monomers, di-tert-butyl peroacid as the reaction initiator. The mixture was quickly heated to 120 ° C. by placing it in a vessel immersed in an oil bath at this temperature. Due to the exothermic nature of the reaction, the temperature of the mixture rose to 150 ° C. within 10 minutes, with the styrene refluxing that RUokfließen had ceased, the temperature was raised to abzudeetillleren non-umgesetete monomers \, and then allowed to solidify the product, after which it was finely ground in a ball mill. the copolymer had a epezifisohe viscosity of 0.264 and a degree of esterification of 26.5 # »

(B) Copolymer of styrene oma xthyl hydrogen malexate.

The copolymer was replaced by a solution polymerization '- prepared tion process, whereby 42 g of styrene and 58 g Äthylhydrogenmalei * mt under reflux for 1 1/2 hours, were heated in 100 g of benzene long, using 0.8 g of azo-bieisobutyro- nitrile (AZBN) as reaction initiator After the polymerization, most of the benzene was distilled off and the product was dried in a vacuum oven at 60.degree. C. for 1 hour. This creates "copolymer had a viscosity of epezifieohe Ö, Ö78 and a degree of esterification yon 47 f> * ·

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ORfGJNAt: INiSPECTED

• · · f

(C) Copolymer of styrene and iS / thylhydrogenraaleieat.

The mixed polymer was produced by Itösunge polymerisation, 42 g of styrene, 58 g of ethyl hydrogenraalate, 1.5 g tertiary dodeoyl mercaptan and 1.0 g of AZBN were heated under reflux in 100 g of xylene for 2 hours at 140 ° C »Das The copolymer produced had a specific viscosity of 0.09 and a degree of esterification of 41 #

(D) Mieohpolymerisat of styrene and Isopropylhydrogenmalejesat «

The copolymer was obtained by the solution polymerization used for the preparation of the copolymer (B) using 39.7 g of styrene, 60.3 g of isopropylhydrogenmaloJASS and 0.8 g of AZBIf. That generated The copolymer had a specific viscosity of 0.139 and a degree of esterification of 42%

(E) Copolymer of styrene and n-butylhydrogenmaleJÄat.

The mixed polymer was prepared in the manner used for the preparation of misoh polymer B (A), the methyl hydrogen maleic acid being replaced by an equimolar amount of n-butyl hydrogen maleic acid. The copolymer had a specific viscosity of 0.233 and a degree of esterification of 33.5 ^ ₀

(F) Copolymer of styrene and n-butyl hydrogen malainate »

The copolymer was produced by suspension polymerization, 32.8 g of styrene and 67.2 g of n-butyl hydrogen maleate and 0.8 g of AZBN to 400 ml of a 0.05% solution von Gohsenol GH 17 (a polyvinyl alcohol) in distilled water were added. The respondents were while stirring. Heated for 1 1/2 hours at 80 ° C, then

909836 / U33 ORIGINAL INSPECTED

• a · 4

J. · 4Θ »* -

the temperature increased to 90 ° C and the reaction participants heated for a further 2 1/2 hours. The suspension was filtered through muslin in order to obtain the copolymer as small spheres, which were washed with distilled water , dried in air for 15 hours and then dried in a vacuum oven at about 45 G for 1 hour. The copolymer produced had a specific viscosity of 0.219 and a degree of esterification of 57.5 #.

(G) Copolymer of styrene and amyl hydrogen maleate.

The copolymer was used in the production of Copolymer (A) applied manner prepared, the methyl hydrogen malejiffate by an equimolar amount of Amylhydrogenmale ^ nat was replaced. The copolymer produced had a specific viscosity of 0.163 and a degree of esterification of 38 #.

(H) copolymer of styrene and Benzylhydrogenmaleinat _o

The copolymer was prepared by 33 g styrene and 66 g Benzylhydro ^ ii.i - i "ii" |? F * c were added + 100 g of benzene reli * fc - ?; i Z Stusiuvn under reflux and using was heated by 0.4 g of AZBN as initiator _e The benzene was then distilled off and the residue was dried in a vacuum oven for 2 hours at 60 ° C. The copolymer produced had a specific viscosity of 0.159 and a degree of esterification of 51 $> *

(I) Copolymer of styrene and isopropyl hydrogen citraconate

The copolymer was prepared by solution polymerization, as used for the preparation of copolymer (B), using 5.2 g of benzoyl peroxide as initiator. The copolymer produced had a specific viscosity of 0.086 and a degree of esterification of 59.5 % .

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ORIGINAL fNSPECTED

·· · ir

• · · IC

Γ Γ ΓΙ

irr <c

ti r ι. ι

(J) Copolymer of p-chlorostyrene and Ieopropyl hydrogenraaleiiTat

Copolymer was prepared by solution polymerization, such as applied for the production of copolymer (B) prepared "with the use of 4.6 g of p-chlorostyrene, 5,3 g lBopropylhydrogenmaleJ" nat and 0.08 g of AZBN ₀ The Hieohpolymerisat produced had a viscosity spezifisohe of 0.096 and a degree of esterification of 42.5 # «>

The Sober Carrying Properties of the Copolymers (A) .bis (J) were found by the following method All data on ropes and percentages are weight data, unless otherwise stated:

The following ingredients became a number more aqueous WJeungen prepares:

Percentages Orobwasohmittel (branded goods) 0.4

eynthetisohes sebum 0.05

Carbon Black (sold under the brand name Monarch 74) 0.005

Mixed polymer 0.008

The above gross waeon means possessed the following approximate Sueanoenetting:

Percentages

Sodium dodeoylbenzenesulfonate 20th Sodium tripolyphosphate 35 Coconut ethanolamide 3 alkaline silicate (anhydrous) 11th Sodium toluene sulfonate 2 Sodium sulfate 10

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f ♦

Percentages Sodium carboxymethyl cellulose 0.65 Sodium perborate. 9

Water to 100

The synthetic sebum was a mixture of organic compounds and had the following approximate composition:

Percentages Fatty acid triglycerides 40 Fatty acids 20

Wax 25

Paraffins 2

Squalene 9

Cholesterol 4

Each of the aqueous solutions was prepared from a dispersion of 0.01 $> of the carbon black and 0.1 $ of the sebum in a 0.8 #igen aqueous solution of the detergent powder, which strength after the addition of the interpolymer in a 0.2 $ (wt ./Vol.) Solution in sodium hydroxide solution (pH 11) has been diluted to the desired concentration

Sections, approximately 5 cm square, of polyester fabric were washed with stirring in a Tergotometer, with 400 ml each of the aqueous solutions were applied for 10 minutes at 60 ° C, and then rinsed in hard water (24 ° H) «

The light reflections of each of the sewing sections in front of and after washing were determined using a reflectometer "Colorcord" with a green filter · Von 2 readings were taken for each fabric section and the percentage soil carrying capacity was taken from the average of the Results calculated using the following equation:

R-Ro

Carry dirt « _x ioo #,

Rf - Ro

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where R is the reflection of the fabric washed using a mixed polymer,

Rf the reflection of the pure fabric and

Ro is the reflection of the fabric washed without the use of mixed polymer

The results obtained are summarized in Table I below:

Table I. Copolymer used dirt-carrying capacity

A 32.8

B 33.2

0 20.5 D 39.3 E 36.4 P 11.8 G 17.5 H 15.6

1 10.3 J 28.0

It's mind to-that the applied heavy-duty detergents üfatriumcarboxyme thy! Cellulose as a dirt wear substance for cotton fabric contained "The soil-carrying capacity of Natriumcarboxymethyloellulose relative to polyester fabric is 0 i>, can was.sich show by reacting the above experiments using one washing powder with and one without sodium oarboxymethyl cellulose.

The difference between the soil-carrying capacity of the copolymers (B) and (C) shows the favorable influence of the Use of copolymers with a higher specific viscosity, since the other properties of the misohpolymer

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Risate roughly the same were o In similar catfish shows the difference between the results when using the copolymers (E) and (F) the advantage of results from the use of copolymers with a relatively low degree of esterification.

To the effect of the application of the copolymers as A series of experiments was carried out to determine soil-carrying substances in various types of detergents using the same conditions as above except that the soot concentration was varied in some cases »

The results obtained are from the below Table II shows:

Table II

Branded detergent mixed polymer soot concentrate dirt »

tration in # wearing ability ($)

Soap powder

non-ionic washing powder

liquid heavy duty detergent

liquid mild detergent

Powder detergent for mild detergents

schwaohsohäumendee Powder (for automatic washing machines)

O, 01 9.6 O, 005 7.6 O, 005 17.2 0, 0025 16.5 0, 0025 22.0

0.005

24.6

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In each of these cases, valuable improvements were achieved by using the copolymers as soil-carrying substances, but the soil-carrying capacity of the different copolymers in the different types of detergents varies considerably.

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Claims (1)

Claims Detergent for washing fabrics, characterized by » that it is a water-soluble or water-dispersible copolymer of the general formula COOX COOX wherein R _{1 represents} a hydrogen, chlorine or bromine atom or a lower alkyl group; R ₂ and R represent hydrogen, chlorine = or bromine atoms or lower alkyl groups; or R _{2 is} a nitro group (-NO ₂ ) or an amino group or a substituted amino group (-N (Rg) ₂ ), in which each Rg is a hydrogen atom or a lower alkyl group, and R 1 is a hydrogen atom; 'R4 is a hydrogen atom or a lower alkyl group; R ^ represents a hydrogen, chlorine or bromine atom or a hydroxy group (-OH) or an amino group or a substituted amino group (-N (Rg) ₂ ), in which each R _{6 represents} a hydrogen atom or a lower alkyl group; 909836 / U33 and X is a hydrogen atom or an esterifying group, the group is a lower alky! or is a benzyl or substituted benzyl, wherein the Vereeterungsgrad, as defined, within the range from 5 to 75 & liegt5 or contains a salt thereof « 2ο detergent according to claim 1 _p, characterized in that it does not contain more than about 5 wt .- ^% of the copolymer o Detergent according to Claims 2 _9, characterized in that it contains 0 ₉ 5 to 4% by weight of the copolymer 4ο detergent according to one of the preceding claims, characterized in that the copolymer has a degree of esterification of about 25 to about 62.5 fo «, 5ο detergent according to claim 4, characterized in that that daö copolymer has a degree of esterification of about 25 to about 50 $. Detergent according to one of the preceding claims « characterized in that the copolymer has a specific viscosity of at least 0.13 7ο detergent according to one of the preceding claims, characterized in that it contains a copolymer obtained by copolymerization of styrene and a maleic acid partial ester is produced «, Detergent according to claim 7, characterized in that the partial ester of maleic acid is a half ester » 9ο Detergent according to claim 7 or 8, characterized in that the ester is an alkyl hydrogen maleate in which the alkyl group contains 1 - 5 carbon atoms ^ or benzyl hydrogen maleate is 909836 / U33 10. Use of the detergent according to one of the Claims 1 to 9 for washing fabric, in particular such fabric that at least is partly made of synthetic fibers. 11. Use according to claim 10, characterized in that such an amount of detergent is used that a copolymer concentration of about 0.002 % to about 0.016 % ₉ based on the weight of the washing liquor is given. 90983 6 / U33