DE2238275A1 - DETERGENT MIXTURE - Google Patents

Description

Detergent mixture ■ (Priority: August 3, 1971, Japan, No. 46-58545)

The invention relates to detergent mixtures, in particular detergent mixtures, which are especially suitable for washing machines and which have an anionic or nonionic surface-active Agent and a new water-soluble salt of a cyclopentene-maleic anhydride copolymer or contain its derivative;

In recent years there have been various improvements in the design and operation of electrical Washing machines proposed that show the tendency towards a fully automatic washing machine. According to the development Of these new and improved washing machines there has been a demand for a novel type in the art reinforced a detergent mixture that can wash a wide variety of fibers at the same time without any fiber damage to cause and also an excellent waxing effect even with relatively weak mechanical forces

7/1237

exposure shows. "

V / ash compositions generally consist of a surface-active one Agents and a builder for improving or promoting the activity of the surface active agent along with a small amount of a dirt repositioning inhibitor, a bleach, fluorescent Dye, sizing agent and the like.

Representative examples of builders used in this field for the formation of detergent mixtures include inorganic builders such as carbonates, bicarbonates, phosphates, polyphosphates, and borates Alkali metal siclicates; organic builders, such as alkali metal salts and ammonium salts of aminocarboxylic acids, for example of ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). The most used One of these builders is sodium tripolyphosphate (hereinafter referred to as "STP"), which is typical of condensed polyphosphates is.

Such condensed polyphosphates, exemplified by STP, show excellent build-up efficacy, they have however some drawbacks that. must be improved or eliminated if they are to be incorporated into a wax mixture should be used. The polyphosphates are clearly expressed when they are in a detergent mixture are incorporated, often by hydrolysis in their aqueous solution converted into lower condensed polyphosphates, causing them a loss of activity as a builder suffer and therefore the reduction in detergency of the detergent mixture. Also tend wastewaters that contain such polyphosphates, though

3 η ·) ν, η ν / 1 ·> 3 7

_ 3 -

them in rivers and / or. Drainage systems to encourage the growth of duckweeds, which leads to pollution and destroys the beauty of nature. The other organic or inorganic Due to their inherently low activity, builders give a detergent mixture containing them, only poor washing effectiveness.

The invention is based on extensive experiments on the possibility of determining the amount of sodium tripolyphosphate used to reduce or avoid the use of this polyphosphate. It was unexpected found that the above-mentioned disadvantages of the known builders are alleviated or avoided can, if a water-soluble salt of a copolymer of cyclopentene o5cr its lower-alkyl-substituted as a building material Derivative and maleic anhydride is used. Such a cyclopentene-maleic anhydride copolymer or copolymers of the cyclopentene derivative with maleic anhydride is also referred to below as PM resin or PM-II resin derivative.

The invention therefore relates to a detergent mixture which contains a surfactant and a builder and is characterized in that as a surfactant Agent means an anionic or nonionic surface-active agent and, as a builder, a water-soluble one Salt of a copolymer of cyclopenienes or a lower-alkyl-substituted cyclopentene derivative with maleic anhydride is present.

The invention makes detergent mixtures with advantageous properties, as well as new compounds accessible,

3 0 "■ '/ / 1? Γ! 7

which are suitable as building materials for a detergent mixture.

The detergent mixtures according to the invention have excellent properties Washing effectiveness and are very satisfactory in terms of their effect not to irritate the skin excellent antistatic effect on the washed materials as well as their superior inhibitor effect the reaping of dirt.

Other objects, features and advantages of the invention are apparent from the following description and claims evident.

The water-soluble substances which are suitable as builders according to the invention Salts of PM resin and PM resin derivatives are new compounds that are in the form of white powders. to preferred examples of these salts include the corresponding alkali metal salts, for example the sodium, potassium and lithium salts and the corresponding ammonium salts.

PM resin and PM resin derivatives which can be used as starting materials for the builder according to the invention in a simple manner by copolymerizing cyclopentene or its lower-alkyl substitution derivatives with maleic anhydride at a temperature of 50-150 ° C in the presence of a radical polymerization initiator such as a peroxide, for example, benzoyl peroxide, azobisisobutyronitrile or the like and an organic solvent such as acetone, benzene and the like. This reaction is illustrated by the following reaction scheme:

R radical generator

as polymer

0 = * Nn / ^Ä 0 ion initiator

309807/1237

In this formula, R represents a hydrogen atom or a lower alkyl group preferably having 1 to 5 carbon atoms, for example a methyl, ethyl, n-propyl, _r, isopropyl, η-butyl, sec-butyl, tert-butyl , n-pentyl group or the like, and η an integer from 1 to 15. The PM resin and PM resin derivatives thus obtained are white powders having an average molecular weight of 350 to 2000 and a softening point of 200 to 260 Own ° C ». The cyclopentene used or its lower-alkyl substitution derivative can be prepared by hydrogenation of cyclopentadiene or its lower-alkyl substitution derivative, for example by using a nickel-containing catalyst and gaseous hydrogen.

The water-soluble salts of the PM resin or PM resin derivative can be obtained by reacting the PM resin or PM resin derivative, which has been prepared as above, can be obtained with alkali, for example with an aqueous solution of Alkali metal hydroxide, ammonium hydroxide, or alkali metal carbonate as illustrated by the following reaction scheme will.

/ Λ MOH /

Λ nrJBT> /

or

In the above formula, R and η have the meaning given, M denotes an alkali metal atom, for example sodium, potassium or lithium or an ammonium ion and M 'denotes Alkali metal atom, for example sodium, potassium or lithium /, In the above reaction, the one to be used

3 Ö ^E ", Π Π 7/1? 3 7

2238775

aqueous solution have a concentration up to saturation, but it can usually have a concentration of 20 to 50 percent by weight of the alkali metal hydroxide and ammonium hydroxide and the saturation concentration for Have alkali metal carbonate. The alkali metal hydroxide, ammonium hydroxide or alkali metal carbonate can be used in one An amount equivalent to that of the maleic anhydride component of the PM resin and PM resin derivative may be used. The reaction is carried out with stirring at room temperature for about 30 minutes, leaving a transparent reaction mixture is obtained. The reaction temperature can advantageously be increased to 120 to 130 ° C. in order to increase the reaction time abbreviate. The reaction mixture obtained is then subjected to distillation under reduced pressure and / or heated to 120 to 130 ° G to remove water therefrom. This creates the desired water-soluble salt of the PM resin or PM resin derivative b. The product is in the form of a white powder, its aqueous Solution has an alkalinity corresponding to pH 9-10 at a concentration of 0.05 percent by weight.

Representative examples of anionic surface-active agents which are used in the detergent mixture according to the invention Sodium linear alkylbenzenesulfonates can be used, for example (hereinafter referred to as "LAS"), sodium α-olefinsulfon & te (hereinafter referred to as "AOS"), Sodium alkylbenzenesulfonates (hereinafter referred to as "ABS") and the like.

Examples of the alkyl group in LAS and ABS and of the C ^ -olefin in AOS are alkyl groups and α-olefins, respectively with 10 to 20 carbon atoms, which can be present alone or in the form of a mixture.

Representative examples of nonionic surface-active agents that are used in the detergent mixture according to the invention

jft ί ·

can be used are "for example polyoxyethylene nonylphenyl ether with 8 moles of linked ethylene oxide units per mole, (hereinafter referred to as "POENE-8"), polyoxyethylene nonylphenyl ether with 20 moles of linked ethylene oxide units per mole (hereinafter referred to as "POENE-20") and similar connections.

Has water-soluble salt of PM resin or PM resin derivative Can be used as a builder on its own or in a mixture with another compound that is suitable as a builder will. It can be specifically stated that the inorganic building materials, such as STP, which have certain components, are advantageous can be used in a reduced amount when the novel builder according to the invention together is used with them.

The detergent mixture according to the invention can in a simple manner by mixing the components, that is to say one surfactant, the water-soluble salt of the invention and additives such as an inhibitor for dirt redressing, a bleach and the like. The inventive water-soluble salt can be mixed in in an amount that is usually achieved with the use of common builders, is suitable, namely in an amount of 10 to 90 percent by weight, preferably 40 to 60 percent by weight, based on the detergent mixture.

The detergent mixture according to the invention shows a high detergency, as is shown by the following examples. In these examples, the detergency D was determined according to the general detergency test described below.

309007/1237

method determines:

Pieces of cotton knit fabric (thread number 60) were made desized and then artificially soiled by keeping them in contact with a person's skin to be natural to receive contaminated substances. The test substances obtained were tested for 10 minutes at 25 ° C. in a Tergotometer at a bath ratio of 30 (grams of fabric / gram of aqueous Detergent solution). In this method, the reflectivity of the test fabric before soiling (Ro), the reflectivity of the soiled test fabric measured before washing (Rs) and the reflectivity of the soiled test fabric after washing (Rw) and from the The values measured in this way became the detergency D (? S) according to calculated using the following equation:

The invention will now be illustrated by the following examples, without it being restricted to them

4-

example 1

1.) Production of the FM resin

0.5 mol (34g) cyclopentene, 0.5 mol (49g) maleic anhydride, 1 g of benzoyl peroxide and 100 ml of acetone were placed in a * glass-lined autoclave with a capacity of 200 ml. The reaction was then carried out at 80 ° C for 2.5 hours carried out. After the completion of the reaction, the reaction mixture became cooled and then precipitated from methanol, followed by filtering and drying. 65g of the PM resin obtained, which was in the form of a white powder and an average molecular weight of 1500 and had a softening point of 250 to 260 ° C.

30 9 B Π 7/1 737

- 9 -

2.) Production of the sodium salt of PM resin

80 g of the PM resin obtained by way of illustration were placed in 160 g of a 25% strength aqueous solution of sodium hydroxide and then stirred. A transparent reaction mixture was obtained after 30 minutes. The reaction mixture thus obtained was distilled using an evaporator under reduced pressure of about 20mmHg to obtain the To remove water, and then another distillation using a vacuum pump under reduced pressure of 3mm Subjected to Hg to completely remove residual water. As a result, white powdered sodium salt of PM resin became obtained in $ 99 yield.

3.) Production of K and NH , salt from PM resin

The procedure described above under 2.) was repeated, with the modification that 25 $ aqueous solutions of potassium hydroxide and ammonium hydroxide (twice the molar amount of the maleic anhydride component of the PM resin) were each used in place of the aqueous solution of sodium hydroxide. It was powdery K salt of PM resin and NH salt of PM resin in the form of a white powder with yields of 99% and $ 98, respectively obtain,

Example 2

1.) Manufacture of methyl PM resin

1.0 mole (82 g) methylcyclopentene, 1.0 mole (98 g) maleic anhydride were dissolved in 200 ml of benzene and 3.6 g of benzoyl peroxide were added. The reaction continued for 2.5 hours carried out at 80 ° C with stirring. It was observed that the viscosity of the reaction system increased with the progress the response increased. After the completion of the reaction was

'3 0 9 Π Π 7/1 2 3 7

the reaction mixture cooled to room temperature and in
36Og of methanol were added, whereby a white substance was deposited. The white matter was isolated by filtration and dried to obtain 140 g of methyl PM resin, which has an average molecular weight of 1,600 and a softening point of 200 to 230 ° C
would have.

2.) Preparation of the sodium salt of methyl PM resin

90 g of the methyl PM resin obtained above was placed in 160 g of a 25% strength aqueous solution of sodium hydroxide and heated with stirring at 50 ° C. for about 10 minutes, whereby a liquid transparent reaction mixture was obtained. The reaction mixture was subjected to distillation using an evaporator at a reduced pressure of about 200 mm Hg * and then further distilled using a vacuum pump under a reduced pressure of about 1 mm Hg to completely remove water
Product obtained in $ 99 yield.

3.) Production of the potassium salt of methyl PM resin

The procedure described under 2.) was repeated, with the modification that an aqueous solution of potassium hydroxide (twice the molar amount of the maleic anhydride component of the methyl PM resin) instead of the aqueous Solution of sodium hydroxide was used. A white product was obtained.

Example 3

1.) Production of n-propyl PM resin

Essentially the same procedure was carried out as described in Example 2 under 1.),

* to remove water

3 O ^; . μ fi V / 1 7 3 7

with the modification that equimolar proportions of n-propylcyclopentene and maleic anhydride were used. The product thus obtained was in the form of a white powder and had an average molecular weight of 1750 and and a softening point of 185 to 200 ° C.

2.) Production of the sodium salt of n-propyl PM resin

0.5 mole (55g) of n-propyl PM resin was in 420g of a 16.7 $ aqueous solution of sodium carbonate (0.5 mol Sodium carbonate) and heated with stirring for 15 minutes to 50 ° C, whereby a liquid transparent Reaction mixture was obtained. The reaction mixture was evaporated under reduced pressure of Distilled 20mm Hg to remove water, followed by another distillation using a Subjected to vacuum pump at reduced pressure of about 1mm Hg to completely remove the water. While the evolution of gaseous carbonic acid was observed as the reaction proceeded. The product you want was obtained in torrn of a white powder in a yield of $ 97.

Example 4

1.) - Production of ethyl-j isopropyl, η-butyl and n-pentyl PM resin .

Essentially the same procedure was used as in Examples 1, 2 or 3 under 1.) is described, with the modification that the corresponding substituents containing the above Cyclopentene derivatives in an equimolar amount, based on maleic anhydride, were used. The achieved

3 0 8 3 η 7/1? 37

Results are shown in Table I below.

Table I.

Received
PM resin
derivative Appearance Soften
ungpunkt
Approx By-
, cut
Molecular
weight Ethyl PM resin white, powdery 190-205 1700 Ie opropyl-PM-Harζ - dito - 185-195 1750 n-butyl PM resin - dito - 175-190 1700 n-pentyl PM resin - dito - 170-180 1600 2.) Manufacturing the sodium salts of Ethyl, isopropyl,

η-butyl and n-pentyl PM resin

Essentially the same procedure followed repeated as described under 2.) in Examples 2 and 3, with the modification that each of the above-obtained PM resin derivatives and an aqueous solution of sodium hydroxide (twice the molar amount of maleic anhydride dee PM resin derivatives) were used. The desired sodium salts were each obtained in the form of a white powder.

3.) Production of the NH , salt of ethyl PM resin

α 4

Essentially the same procedure as described under 2.) in Example 2 was repeated, with except that ethyl PM resin and an aqueous solution of ammonium hydroxide were used. The desired Obtained NH.-salt in the form of a white powder.

309807/1237 originally inspected

Example 5

A detergency test was carried out according to the above general test method carried out at 100 rpm of the test device. In doing so, LAS was used as an anionic surfactant Medium, POERE-8 as a nonionic surfactant Agents and water-soluble salts of PM resin and PM resin derivatives (which are polyelectrolytes) and sodium tripolyphosphate are used as builders. Compartment the After washing, the test fabrics were squeezed to remove moisture and then dried at room temperature. The formulation of each test detergent liquid is given below.

The results are summarized in the following table II, in which the washing effectiveness of different detergent formulations with the specified German degree of hardness (DH) is shown.

309807/1237

! Table II

Detergent formulation

Washing efficiency D (*)

hardness

hardness

hardness

* water Solution tön Solution of 0.05 * PM Hara Na Salt 33.8 33.0 32.0 Watery Solution of Solution of 0.04 # READ 41.9 35.1 33.0 watery Solution of Solution of
0 £ 3 * STP 0.04 # POI ^ E-80 51.8 33.3 28 ". 8 * watery Solution of Solution of 0.04 # POENE-8 + 0.05 * STP 61.3 55.7 52.7 ** watery aqueous solution of
Resin Na Salt Solution of 0.0496 POENE-8 + 0.05 * PM- 65.3 56.3 55-7 ♦ * # watery aqueous solution of
PM resin sodium salt Ο, Ο49δ LAS + 0.05 * STP 71.6 60.0 58.8 -K- * watery
Na-SaIz 0.04 * LAS + 0.05 * PM resin 81.8 65.6 36.3 * »* watery
Na-SaIz + 0.04 * LAS + Oß25 * PM resin 80.6 65.0 55.5 * # * watery
E-SaIz 0.04 * LAS + 0.05 * PM resin 81.1 65.4 45.6 * ♦♦ watery
NH salt 0.04 * LAS + 0.05 * PM resin 74.1 70.2 40.3 * # * 0.04 * LAS + 0, Q54.8fthjrl- 65.3 60.3 38.7 ♦♦♦ 76.9 60.4 51.2

Table II

CD CCJ

Detergent recipe READ + $ 0.05 methyl, Washing effectiveness: 59.2 ' D (Si) hardness
20 ° DH
39.1 *** aqueous solution of 0.04 #
PM resin K salt READ + 0.05 # ethyl - Hardness. 'Hardness
0 ° DH 15 ° DH
72.4 68.3 58.4 50.1, *** aqueous solution of $ 0.04
PM resin sodium salt READ ₊ 0, OSf. ItW- 75.1 57.4 37.2 *** aqueous solution of $ 0.04 READ +. $ 0.05 n-propyl 63.1 57.3 48.9 *** watery. Solution of $ 0.04
PM resin sodium salt READ + 0.0596 isopropyl 73.5 55.3 48.5 *** aqueous solution of $ 0.04
PH resin sodium salt READ + 0.059 ^ n-butyl- 73.2 54.5. 46.1 *** "aqueous solution of ^: OyG4 #
"" ^ -HarZ-Na-SaIζ "' READ + n-pentyl-PM- 71.9 44.9 ' *** =, "^ aqueous solution of 0.049 ^
■. Resin-Na-Salt ·.% -, ■ 70.3 '

VJl

OJ

NJ

cn

2238775

Notes: 1.) Blank samples (reference examples) are marked with "*",

Comparative examples with "* ♦" and examples according to the invention with "***". 2.) "$>" means percent by weight, based on the aqueous solution of the detergent mixture.

As can be seen from the above results, the sodium salt of PM resin, as such, exhibits detergent activity to a certain extent and a detergent mixture containing this water-soluble salt as a detergent builder Containing LAS or POENE-80, shows excellent washing efficacy, which is much more noticeable in soft water is. Even in very hard water, however, the detergent mixture according to the invention can be the same or a higher one Determine degree of washing effectiveness.

The new water-soluble salts of the described copolymers are stable in the form of an aqueous solution and have practically satisfactory properties in terms of their lack of irritant effect on the skin and show excellent antistatic effect on the washed materials and superior soil redraw inhibitory effectiveness. In addition, these are PM resin and the PM resin derivatives in a simpler and more economical way Way available due to recent developments in the petroleum industry.

As can be seen from the above description, a detergent mixture is available according to the invention which is particularly well suited for fully automatic electric washing machines is because a very good washing effectiveness is achieved by using a small amount of the detergent mixture, which according to the invention is a novel water-soluble Contains mixed salt of a copolymer, regardless of the kind and type of nonionic or used anionic surfactants.

309807/1237

Claims (8)

Claims 1. detergent mixture containing a surface-active Agent and a builder, characterized in that as a surface-active agent anionic or nonionic surfactant and, as a builder, a water-soluble salt a. copolymer of cyclopentene or one with a ' lower alkyl group substituted cyclopentene with Maleic anhydride is present. 2. detergent mixture according to claim 1, characterized in that g e k e η η drawing Not that it contains an alkali metal or ammonium salt as the water-soluble salt of the copolymer. - 3- detergent mixture according to claim 1 or 2, characterized in that it contains a copolymer of a • substituted with a lower alkyl group cyclopentene with maleic anhydride, the lower alkyl group being a methyl, ethyl, n-propyl, isopropyl, η-butyl - or n-pentyl group. 4. Detergent mixture according to Claims 1 to 3, characterized in that the builder is in an amount of 10 to 90 percent by weight based on 309307/1237 - sir - At the detergent mixture is present. 5. detergent mixture according to claims 1 to 4, characterized
marked that the copolymer present as a builder has an average molecular weight of 350 to 2000. 6. detergent mixture according to claims 1 to 5 »thereby
characterized in that it contains an additional builder in addition to the water-soluble salt of the copolymer. 7. detergent mixture according to claim 6, characterized in that it is used as an additional builder Contains sodium tripolyphosphate. 8. Water soluble copolymer salt of the formula in which R is a hydrogen atom or a lower alkyl group, M is an alkali metal or ammonium ion and η is an integer from 1 to 15 inclusive. 309807/1? 37