CH647544A5 - LAUNDRY CLEANING ITEM. - Google Patents

Description

The object of the invention is to provide a laundry cleaning article which enables excellent cleaning, which can give laundry advantageous properties, such as antistatic properties, fabric softening and inhibition of dye transfer, and which enables improved release of its active components into the washing solution; the bleeding out of the active components from the substrate sheets should also be minimized without the release of the active components in the washing solution being impaired thereby.

The laundry cleaning article according to the invention has the features specified in claim 1. Preferred embodiments of the article have the features set out in claims 2-11.

All percentages, parts and ratios relate to the weight, unless stated otherwise.

Substrate component

The articles of the present invention contain a water-insoluble, wet strength substrate that carries an effective amount of a detergent formulation, which is further defined herein. The exact amount of detergent preparation carried by the substrate depends on the respective substrate materials and the active materials contained in the preparation. Preferred articles carry 3 to 120, preferably 20 to 80 g of the detergent preparation. The detergent preparation can be loaded onto the substrate material in any way known in the art, such as coating or impregnation. Particularly preferred substrates are sandwich-like articles in which at least one of the substrate sheets used has an air permeability of at least about 280 liters / min / 930 cm 2.

The substrates used here are water-insoluble and are solid or practically solid materials. They can have a dense or open structure, preferably the latter. Examples of suitable materials that can be used here as a substrate include water-insoluble particulate materials (such as certain silicas, silicon dioxide, clays and aluminum silicates), foam,

Foil, sponge, paper, woven cloth and nonwoven cloth. The term "cloth" used here means woven or non-woven fabrics or wipes that are used as a substrate to keep them from the term

To differentiate between "fabric", which means the textiles to be washed. Absorption capacity, thickness or fiber density are not limitations of the substrates that can be used here, as long as the substrates are sufficient. Have wet strength so that they retain their structural relationship throughout the washing and drying cycles in which they are used. Furthermore, the substrates must have certain thermal stability properties, i.e. they should not melt or ignite at temperatures below 150 ° C, preferably about 220 ° C, to enable their use in automatic tumble dryers. The substrates used here are preferably wet-strength papers or nonwoven cloths.

Paper substrates that can be used here encompass the wide range of known paper structures and are not limited to particular paper-making fibers or wood pulps. Therefore, the fibers can be derived from softwood, hardwood, or annual plants (e.g. bagasse, cereals, straw, and the like), and wood pulps such as bleached or unbleached kraft cellulose, sulfite cellulose, soda wood, or mixtures thereof can be used. In addition, all paper types with the necessary wet strength and thermal stability are suitable as paper substrates.

A specific example of a paper substrate preferred here is a two-ply paper with a basis weight of about 85 g / m 2, which is made, for example, from a mixture of ground wood and bleached kraft wood pulp. Another example is the absorbent, multi-ply material suitable as towel paper according to US Pat. Nos. 3,686,025 and 3,414,459.

Preferred nonwoven substrates can generally be defined as adhesively bonded fibrous products which have a web-shaped or carded fiber structure or contain fiber mats in which the fibers are randomly distributed or more or less orderly deposited. Natural or synthetic fibers, e.g. Wool,

Silk, jute, hemp, cotton, linen, sisal or ramie or fibers from rayon, cellulose esters, polyvinyl derivatives, polyolefins, polyamides or polyesters with different diameter or denier values, generally up to about 10 deniers, can be used.

The substrates used here can have very different shapes. For example, the substrate can be present as a particulate solid, as a pillow, ball or pad, or it can be a sheet or section of tissue or nonwoven. If the substrate is paper or nonwoven, it can be in the form of single sheets of the desired length and width, or it can be a continuous, roll-like web of the desired width, from which web individual pieces are then separated.

The detergent preparation carried by the substrate contains 5 to 95%, preferably 10 to 90% and in particular 15 to 85%, of surfactant mixture (a). The weight ratio of nonionic surfactant (i) to cationic surfactant (ii) in the mixture (a) is in the range from 5: 3 to 300: 1, preferably 5: 3 to 100: 1 and in particular 5: 3 to 50: 1 ; ratio values of 5: 3 to 10: 1, in particular 5: 3 to 5: 1, e.g. about 5: 2.

Non-ionic surfactant (i)

Known surfactants of this type which have HLB values from 5 to 17 and can be incorporated individually or in a mixture, preferably together with the preferred non-ionic alcohol described below, can be used as nonionic surfactants for component (i) -Ethoxylate surfactants. Examples of suitable surfactants (i)

are described in U.S. Patent Nos. 3,717,630 and 3,332,880.

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Non-limiting examples of suitable nonionic surfactants (i) include polyethylene oxide condensates of alkylphenols, condensates of straight or branched primary or secondary aliphatic alcohols with 1 to 25 moles of ethylene oxide, condensates of ethylene oxide with a hydrophobic formed by condensation of propylene oxide and propylene glycol Base and condensates of ethylene oxide with the product resulting from the reaction of propylene oxide and propylenediamine.

Preferred non-ionic surfactants (i) are biodegradable and have the formula R (OC2H4) “OH, where R is a primary or secondary alkyl chain of 8 to 22 C atoms, preferably 10 to 20 C atoms, and n has an average value of 2 to 9, preferably 4 to 7. The surfactants of component (i) have HLB values (hydrophilic-lipophilic balance) from 5 to

17, preferably from 6 to 15. The HLB criterion is described in more detail in “Nonionic Surfactants” by M.J. Schick, Marcel Dekker, Inc., 1966, pages 607-613.

Particularly preferred nonionic surfactants (i) contain: condensate of CIO alcohol with 3 moles of ethylene oxide; Tallow alcohol condensate with 9 moles of ethylene oxide; Condensate of coconut alcohol with 5 moles of ethylene oxide; Condensate of coconut alcohol with 6 moles of ethylene oxide; Condensate of Ci2_i3 with 6.5 mol of ethylene oxide, if appropriate after removal of all of the lower ethoxylate and the non-ethoxylated fractions; Ci2_ [3 alcohol condensate with 3 moles of ethylene oxide treated to remove the lower ethoxylate and non-ethoxylated fractions; Condensate of C | 4_i5 alcohol with 2.25 moles of ethylene oxide or condensate of C] 4_ | 5 alcohol with 7 moles of ethylene oxide.

If component (i) is a mixture of a preferred non-ionic alcohol ethoxylate surfactant with other types of non-ionic surfactants, the ratio of preferred surfactant (i) [or surfactants (i)] to the remaining non- Ionic surfactants of component (i) preferably in the range from about 1: 1 to about 5: 1. Specific examples of surfactant mixtures (i) suitable according to the invention include a mixture of condensate of CI4_i5 alcohol with 3 moles of ethylene oxide (“Neodol” 45-3) and condensate of C14-15 alcohol with 9 moles of ethylene oxide (“Neodol” 45-9) in a ratio of about 1: 1 to about 3: 1; a mixture of condensate of Cio alcohol with 3 moles of ethylene oxide together with the condensate of a secondary cis alcohol with 9 moles of ethylene oxide ("Tergìtol" 15-S-9) in a ratio of about 1: 1 to about 4: 1; a mixture of "Neodol" 45-3 and "Tergitol" 15-S-9 in a ratio of about 1: 1 to about 3: 1 and a mixture of "Neodol" 45-3 with the condensation product of myristyl alcohol with 10 moles of ethylene oxide in a ratio of about 1: 1 to about 3: 1.

Preferred non-ionic surfactant mixtures (i) contain alkyl glyceryl ether compounds together with the preferred non-ionic alcohol ethoxylate surfactants. Glyceryl ethers of the formula are particularly preferred

R-0 (CH2CH20) nCH2CH2CH20H

I.

OH

wherein R is an alkyl or alkenyl group from about 8 to about

18, preferably about 8 to 12 carbon atoms or an alkaryl group with about 5 to 14 carbon atoms in the alkyl chain, and n is zero to about 6, together with one of the preferred nonionic alcohol ethoxylate surfactants defined above in a ratio of alcohol ethoxylate to glyceryl ether of about -1: 1 to about 4: 1, in particular about 7: 3. Glyceryl ethers of the type useful as component (i) for the invention are described in Belgian Patent No. 849,807 and in U.S. Patent No. 4,098,713.

Cationic surfactant (ii)

The cationic surfactants used as component (ii) have the composition specified in claim 1. The special cationic component (ii) depends to a large extent on the nonionic component (i) to be used in the system and is chosen such that it is at least water-dispersible, preferably water-soluble, when mixed with the latter. The term “water-dispersible” means that the cationic (ii) and non-ionic surfactants (i) remain dispersed in the washing solution during the washing process even in the presence of any anionic components contained in the preparation. Mixtures of the cationic materials defined above can also be used as component (ii). Small amounts of other cationic substances can be tolerated in such mixtures.

Preferred cationic surfactants (ii) contain only one cationic group Y, namely

> 7- C -

-N - or - C + I

X 1

0 n - c -

»

however, surfactants (ii) which contain 2 or 3 cationic groups Y of the formulas (1) to (7) are also suitable.

If the surfactant (ii) has only one group R ', it preferably contains three groups R2, namely as methyl groups. Preferred preparations of this type with a single long chain include those in which R1 is a Cio to C2o alkyl group. Particularly preferred preparations of this group include Cn-alkyltrimethylammonium halides and Ci4-alkyltrimethylammonium halides.

In order to be sufficiently water soluble or water dispersible, the cationic surfactant (ii) must meet the following chain length criteria. If the molecule contains three or more R1 groups, only one of the R 'chains can have a length of more than 12 carbon atoms. In this case, it is preferred that an R2 group is present and a methyl group. In these preparations, it is preferred that R1 is a Cs to Cn alkyl group. Particularly preferred cationic surfactants (ii) with three long chains include trioctylmethylammonium halide and tridecylmethylammonium halide.

A particularly preferred type of the cationic component is described in Japanese Patent Application No. 53/79228. Particularly preferred cationic surfactants of this type are the choline ester derivatives of the following formula:

o ch3

R3-c-o-ch2ch2-n + -ch3 x "

in which R3 is straight or branched alkyl or alkenyl or alkylphenyl with 5 to 30 C atoms, and those in which the ester bridge in the above formula is replaced by an inverted ester, an amide or an inverted amide bond.

Particularly preferred examples of this type of cationic surfactants (ii) include stearoylcholine ester quat.-ammonium halide (R3 = Cn-alkyl), palmitoylcholine line ester quat.-ammonium halide (R3 = cis alkyl), myristoylcholine ester quat. -ammonium halides (R3 = Cn-alkyl),

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Lauroylcholinester ammonium halides (R3 = Ci i-alkyl) and tallow alcohol cholinester quat.-ammonium halides (R3 = Ci5- to Cn-alkyl).

Further preferred cationic components of the Cho-line ester type correspond to the structural formula given below, in which p can be 2 to 20.

o o ch3

R3-0-C- (C »2) pC-0-CH2CH2-N + -CH3 x"

CH3 O or CH3

x "CH3- + N-CH2-CH2-0-C- (CH2) p-C-0-CH2-CH2-N + -CH3 X

ch3 CH3

In addition to the advantages of the other cationic surfactants described here, the choline ester type of cationic component (ii) is desirable if its R3 chain is not too branched and it is biodegradable with respect to both its long alkyl chain and its nitrogen-containing portion.

Another type of preferred biodegradable cationic surfactants for use in component (ii) is described in Japanese Patent Application No. 53-79227. Preferred embodiments of this type are choli nesters, the formulas of which are given below, in which t is zero or 1, y is 1 to 20, R4 is Cs to C2oalkyl or alkenyl and X is an anion which the compound at least makes water dispersible, preferably chloride, bromide or iodide.

0 C1I3

CH3-R4-0 (CH2CH20) y- (CH2) t-C-0-CH2-CH2-N + -CH3 X ~

, CH3

0 CH3

CH, -R4-0 (CH-CHO0) -C-CH, -N + -CH, X ~ j t i y * •, j

The above types of preferred surfactants (ii) when used in the formulations of the present invention provide excellent removal of particulate, body, and greasy-oily soils. In addition, the detergent preparations prevent static charges, have a softening effect on the laundry items washed with them and inhibit the transfer of certain dyes in the washing solution. Furthermore, these cationic surfactants (ii) are biologically expedient as long as the molecules do not contain any highly branched sections, since both their long-chain alkyl segments and their nitrogen segments are sufficiently biodegradable. To the extent that this type of biodegradable cationic surfactant (ii) is used, the detergent preparations in the wash solution preferably have a pH of not more than about 11, preferably less than about 10, in order to minimize the hydrolysis of the cationic surfactant (ii).

Solubilization Aid (B)

The preparations used in the articles of the present invention also contain 1 to 30%, preferably 3 to 25% and particularly preferably 5 to 20% solubilizing auxiliaries, each based on the weight.

This agent or its components should or should be non-ionic or cationic in order to be compatible with the nonionic / cationic surfactant mixture (a), and must or must have a solubility at 38 ° C. in water of at least 20% by weight. -% and preferably have at least 25 wt .-%. In addition, the agent (b) or its components must be selected so that it completely dissolves in water at 38 ° C. in no more than 2 minutes and preferably not more than about 1 minute. These criteria are important in order to achieve a suitable release of the active components from the substrate. For example, sodium chloride, which is highly soluble and thus meets the first criterion, does not show the rapid dissolution rate necessary to meet the second criterion and is therefore not suitable for use in articles of the present invention.

Without being bound by theory, it is assumed

that when the solubilization aid is quickly dissolved

(b) the interface between the washing solution and the surfactant mixture (a) is increased in the washing solution, which increases the transition of the mixture (a) from the substrate into the washing system. Preferred solubilization aids (b) are selected from choline chloride, ammonium chloride, phenylmethylammonium chloride, sucrose, glucose, polyethylene glycol with a molecular weight of 1000 to 6000, preferably about 4000, and mixtures of these substances. Particularly preferred solubilization aids (b) are choline chloride, sucrose, glucose, polyethylene glycol with a molecular weight of 1000 to 6000, preferably about 4000, and mixtures thereof. Solubilizing aids that meet the above solubility criteria and are also hygroscopic, such as choline chloride, are particularly preferred for use in articles of the present invention.

Preferred detergent preparations from components (a) and (b) which are used in substrate articles of the present invention additionally contain as agents

(c) against bleeding 2 to 20% by weight, preferably 5 to 17 and in particular 5 to 15% by weight, of clay, silicon dioxide, amide or soap material with an average particle size of not greater than about 3.0 micrometers . Preferred agents (c) are silicas, clays and mixtures of these substances. It has been found that when these substances with the particle sizes specified here are incorporated into the detergent preparations used for the present invention, the undesired bleeding of the active components during storage is minimized. Such bleeding is advantageously kept as low as possible since it can result in a loss of active material and disadvantages in terms of both appearance and handling. Preferred means (c)

are those with an average particle size of not larger than approximately 2.5 micrometers, in particular not larger than approximately 2 micrometers. Particularly preferred materials of this type include “Zeosyl” 200, a silicon dioxide material with average agglomerated particle sizes of about 2 microns, commercially available from J.M. Huber Corporation; “Bentone” 27, a bento-nit clay material with an average particle size of about 0.8 microns, commercially available from N.L. Industries; "Quso" G30, a silicate material with an average particle size of about 1 to 2 microns and a surface area of about 300 m2 / g, commercially available from the Philadelphia Quartz Company, and mixtures of these materials. Sodium stearate and ammonium stearate are examples of soaps useful in the present invention as an anti-bleeding agent (c), while myristamide and behenamide are examples of useful amides. When using these agents (c) in the articles of the present invention, it is convenient that these agents

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can be incorporated together with the solubilization aids (b) defined above to ensure that the detergent preparation thickened by the agent (c) is released into the washing solution sufficiently quickly.

In particularly preferred embodiments, the detergent preparation contained in the article also contains as component (d) about 2 to about 25%, preferably about 2 to about 16% and particularly preferably about 3 to about 10% of a fatty amide surfactant. With respect to the surfactant mixture (a), the ratio of component (a) to optional component (d) is in the range from about 5: 1 to about 50: 1, preferably between about 8: 1 and about 25: 1. The addition of component (d) leads to an excellent dirt particle removal effect and to improved properties with regard to avoiding redeposition of dirt, as described in the European patent application 78200067.3.

The detergent preparation can furthermore contain such optional components as are generally found in detergent preparations, in each case in the usual proportions, as long as these components are compatible with the nonionic and cationic components.

For example, the preparations can contain up to about 15%, preferably up to about 5%, and in particular 0.1 to 2%, of a foam suppressing component. Typical foam suppressants include long chain fatty acids as described in U.S. Patent No. 2,954,347 and combinations of certain non-ionic components with these as described in U.S. Patent No. 2,954,348. Other foam suppressant components useful in the formulations of the present invention include the silicone foam control agents described in U.S. Patent No. 3,933,679, the self-emulsifying silicone foam suppressant described in Belgian Patent No. 847,268, and those disclosed in U.S. Pat. U.S. Patent No. 4,056,481 described microcrystalline waxes and alkyl phosphate esters such as monostearyl phosphate and monooleyl phosphate.

Other auxiliary components that can be incorporated into the articles of the present invention in the usual proportions of use for such components (ie from 0 to about 40%) include anionic, zwitterionic and ampholytic co-surfactants, detergent builders, bleaching agents, bleach activators, soil suspending agents, corrosion inhibitors , Dyes, fillers, optical bleaches, germicides, pH adjusting agents, enzymes, enzyme stabilizers, perfumes, fabric softening components, antistatic agents and the like. Because of the numerous and varied uses of the articles of the present invention, certain types of components such as detergent builders, antistatic agents, fabric softeners and germicides may not be necessary in a given formulation.

Examples of co-surfactants and detergent builders as can be used in preparations of the present invention can be found in US Pat. No. 3,717,630 and in Japanese Patent Application No. 53-79227. However, these components, especially the anionic surfactants, should be tested with the respective surfactant mixture (a) to ensure that they are compatible.

The use of the laundry cleaning article of the present invention provides a convenient and effective method of cleaning soiled fabrics. At least one article, together with laundry, is introduced into an automatic washing machine, preferably at the beginning of the washing cycle, and left in until the washing cycle has ended. During this process, which involves movement of the wash solution, the wash-active components and fabric conditioning agents are quickly and completely released into the wash solution and act on the tissues washed therewith. If the article also contains any textile conditioning components that can be activated in the dryer, e.g. in U.S. Patent Nos. 4,095,946 and 4,113,630, laundry and articles are placed in an automatic dryer to release the drying conditionable fabric conditioning components, which provide further benefits to the laundry.

The following non-limiting examples illustrate the invention.

Example I

The ability of various substrate articles to release active components into a wash solution was tested in the following manner. Detergent preparations of the compositions given below were prepared by mixing the components in the proportions indicated:

Together

Components

% By weight

men

settlement

o ch

A

Il 1. J _

c17h35-c-0-ch2ch2-n -ch3 cl

26.6

c «3

Condensate from coconut alcohol

with 5 moles of ethylene oxide

52.5

Ammonia amide

7.4

Borax -10 H2O

13.5

B

as A above, plus choline chloride (6.4 g)

-10

C.

as A above, plus choline chloride (9.6 g)

-13

D

as A above, plus Zeosyl 200 (3.4 g)

- 5th

E

as A above, plus Zeosyl 200 (3.4 g) and

- 4.5

Choline chloride (7.1 g)

~ 9.5

F

as A above, plus Bentone 27 (10.1 g)

-13.5

G

like A above, plus Bentone 27 (10.1 g) and

-12

Choline chloride (7.5 g)

- 9

Laundry cleaning articles were produced with each of these preparations by placing about 65 g of the preparation on one side of a 20 x 28 cm sheet of "Scott 8050 Industriai Towel" (technical paper towel) with an air permeability of about 4 liters / min / cm 2, a basis weight of about 100 g / m2 and a thickness of 1.1 mm were distributed. A second sheet of paper towel was placed on top of the coated side of the first sheet and the edges sewn together so that the detergent formulation was included in the article. Pairs of the article were then placed in a Kenmore automatic washing machine with 2.5 to 2.7 kg of mixed laundry. The washing machine was operated in a gentle motion wash cycle using 83 liters of water (26 ° C tap water from the city of Cincinnati with a total hardness corresponding to 135 to 170 mg) with a cold water rinse. At the end of the washing operation, the articles were removed and the amount of active material released from the article was visually estimated. The values obtained are shown in the following table.

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Run

composition

% Active material solved from article (visual estimate)

I.

A

20%

B

95%

II

A

10%

C.

95%

III

D

10%

E

80%

IV

F

10%

G

80%

Tri-Cio-methylammonium chloride or by cationic components of the following formulas:

C14H29 "C

Br

10th

These data show the surprising increase in the rate and completeness of the release of the detergent preparation from the substrate using solubilizing aid.

Substantially similar results of the release of the components are obtained when the choline chloride used as a solubilizing aid in the above preparations, in whole or in part, by equivalent amounts of ammonium chloride, phenylmethylammonium chloride, sucrose, glucose, polyethylene glycol with a molecular weight of 1000 to 6000, in particular about 4000, or mixtures of these components is replaced.

Similar results are also obtained if the non-ionic component used above is replaced by the condensation product from Cio-alcohol with 3 mol ethylene oxide, the condensation product from coconut alcohol with 6 mol ethylene oxide, the condensation product from coconut alcohol with 7 mol ethylene oxide, the condensation product from Ci2_i3 -Alcohol with 6 moles of ethylene oxide, the condensation product of C14-15 alcohol with 7 moles of ethylene oxide or the condensation product of C] 2-i3 alcohol treated with 3 moles of ethylene oxide to remove lower ethoxylate and non-ethoxylated fractions.

Excellent results are also obtained when the detergent preparations used nonionic surfactant to cationic surfactant in a ratio of about 100: 1.70: 1.50: 1.35: 1.25: 1.20: 1, 15: 1.10 : 1.5: 1.4: 1.3: 1, 20: 7.20: 9.2: 1 or 5: 3 included.

Similar results are also obtained when the nonionic component is obtained by a mixture of the condensation product of C14-15 alcohol with 3 moles of ethylene oxide together with the condensation product of Ci4_i 5 alcohol with 7 moles of ethylene oxide with a ratio of low ethoxylated nonionic surfactant to higher ethoxylated non-ionic surfactant of about 2: 1,

a mixture of the condensation product from Ci4_i5 alcohol with 3 moles of ethylene oxide together with the condensation product of myristyl alcohol with 10 moles of ethylene oxide in a ratio of low-ethoxylated non-ionic surfactant to higher-ethoxylated non-ionic surfactant of about 1: 1 or a mixture of the condensation product from coconut alcohol 5 moles of ethylene oxide together with an alkyl glyceryl ether of the formula

20th

n - ch.

^ I

/ <"° a2

CH3 CHH29

o ch3

C16H33 ^ - ° -CH2CH2- + rCH3 Br "

ch "

Çh3

hoc_h .- + n-c_h.oh cl ~ 2 4, 2 4

C12H25

o 0 ch3

25 c12h25-o-c-ch2ch2-c-o-ch2ch2- + n-ch3 cl "

CH,

30 ch3 O.0 CH3

Br "ch3- + n-cii2ch2" 0-c- (ch2) 12-c-0-ch2ch2 "n + -ch3 Br ch., Ch,

° ch3

C10H2r ° - (CH2CH2O) 10 ^ -CH2-f "CH3 C1"

ch,

Example II

Using the preparations given below, which were included in the amounts specified in substrate articles, the release properties of various articles of the present invention were investigated according to the method and with the article structure as described in Example I. The percentage of the total detergent preparation released into the wash solution was calculated by weighing the substrate article prior to its introduction into the washing machine and weighing again after use in the washing cycle and drying. The data obtained are summarized in the following table:

C12H25-OCH2CH-CH2OH

OH

is replaced in a ratio of alcohol ethoxylate to glyceryl ether of about 7: 3.

Substantially similar release results are also obtained if the cationic component is replaced by Ci2-trimethylammonium chloride, Ci4-trimethylammonium bromide, di-Cio-dimethylammonium bromide, DÌ-C12-dimethylammonium chloride, Tri-Cs-methylammonium bromide,

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composition

component

Gram / item weight%

% Active material released from article

C17H35-C- ° -CH2CH2

CH3 + '

• n-ch, i y ch,

Cl

13.8

Condensation product from coconut alcohol with 5 moles

20.4

79.4

Ethylene oxide

29.8

43.6

Ammonia amide

4.2

6.1

Borax-5 H2O

6.0

8.8

Brightener (anionic)

0.8

1.2

Zeosyl 200

6.7

9.9

Choline chloride

6.8

10.0

B

as A above, but with Zeosyl 200 and

6.7

8.8

95.7

Choline chloride

15.3

20.0

C.

as A above, but with Zeosyl 200 and

4.2

6.4

70.8

Choline chloride

6.5

10.0

D

as A above, but with Zeosyl 200 and

4.2

5.7

92.0

Choline chloride

14.7

20.0

These values demonstrate the excellent release of the detergent components into the wash solution that is achieved using substrate articles of the present invention.

Example III

According to the procedure described in Example I and with the article structure described there, the detergents were released. , components determined from the articles specified below. After the washing process, the percentage of active components released from the substrate articles was determined visually. The results are summarized in Table 3o below:

Component - gram / article weight% active material composition of articles released

_ _

a c17h35-c-o-ch2ch2- + n-ch3 cl "13.8 28.9 20

ch3

Condensation product from coconut alcohol with 5 moles

Ethylene oxide 29.8 62.5

Brightener (anionic) 0.8 1.7

Zeosyl 200 3.3 6.9 choline chloride

B as A above, but with Zeosyl 200 and 3.3 6.2 90

Choline chloride 5.3 10.0

C as A above, but with Zeosyl 200 and 3.3 5.5

Choline chloride 11.9 20.0

These values demonstrate the excellent release results obtained using the articles of the present invention, as well as the need to use the solubilizing aids described herein when the articles of the present invention contain components to minimize component bleeding.

Example IV

The bleeding properties of the active components from the substrate articles described below were tested in the following manner. Detergent preparations with the basic composition given below, but with different types of components to prevent bleeding, were produced by mixing the components in the proportions indicated. The bleeding-preventing materials tested were Zeosyl 200, a silica with an average agglomerated particle size of about 2 microns, Bentone 27, a bensonite clay with an average particle size of 0.8 micron, Quso G30, a silicate material with an average particle size from about 1 to 2 microns and Zeolite A, a sodium aluminum silicate material with an average particle size of about 4 microns.

55

Component wt .-% gram / article o ch3

c1_h, c-c-o-ch, ch _- + n-ch ci ~ 20.4 11.9

gQi / OO C & x J

ch3

Condensation product from coconut alcohol with 5 moles

Ethylene oxide 50.9 29.8

65 brightener (anionic) 1.4 0.8

Ammonia amide 7.1 4.2

Borax-5 H2O 10.2 6.0

Bleeding component 10.0 5.8

9

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Substrate articles, each of which contained one of the above components against bleeding, were produced by coating one side of the paper material from Example I with about 58.5 g of the particular detergent preparation given and sewing according to Example I with a second sheet.

The bleeding characteristics of each article were determined by simulating the storage of a stack of the articles in a carton pack. Each substrate was placed on the top of a piece of cardboard and loaded with a cube-shaped plexiglass block with an edge length of 10 cm from above. A weight of 100 g was placed on the plexiglass block and the substrate was stored at 27 ° C. under 60% relative atmospheric humidity for two weeks. At the end of the storage period, the diameter of the circle of the non-ionic components bled onto the piece of cardboard was measured. A circle with a diameter of more than 13 cm is assessed as an indication of excessive bleeding under these test conditions. The data obtained are summarized in the following table.

Thickener particle size (micrometer) bleeding (cm)

in a ratio of alcohol / ethoxyate to glyceryl ether of about 7: 3.

Substantially similar results are also obtained when the cationic component is replaced by:

5 Ci2-trimethylammonium chloride, Ci4-trimethylammonium bromide, Di-Cio-dimethylammonium bromide, Di-Cn-dimethyl-ammonium chloride, Tri-Cs-methylammonium bromide, Tri-Cio-methylammonium chloride or cationic components of the following formulas:

10th

N - CH_

S I

C14H29 "Cv + I Br N - CH_

5 / \ 2

CH, C, .H_ "

20 '°? H3

C16H33 "C" ° "CH2CH2" + N_CH3 Br

Zeosyl 200 Bentone 27 Quso G30 Zeolite A

2.0 0.8

1.0 to 2.0 4.0

1.67 1.18 1.67 2.26

25th

These values demonstrate the benefits, expressed as minimal component bleeding, obtained by using certain types of anti-bleeding agents described herein.

Similar results are also obtained if the non-ionic component used above is completely or partially replaced by the condensation product from Cio-alcohol with 3 moles of ethylene oxide, the condensation product from coconut alcohol with 6 moles of ethylene oxide, the condensation product from coconut alcohol with 7 moles of ethylene oxide, that Condensation product from C | 2_i3 alcohol with 6.5 mol ethylene oxide, the condensation product from C | 4 ^ i5 alcohol with 7 mol ethylene oxide, the condensation product from CI2_i3 alcohol with 3 mol ethylene oxide, treated to remove the low-ethoxylated and non-ethoxylated fractions, or mixtures of these surfactants.

Excellent results are also obtained if the detergent preparation included in the article contains the nonionic surfactant in a ratio to the cationic surfactant of about 100: 1.70: 1, 50: 1.40: 1.35: 1.25: 1.15: 1, 5: 1, 4: 1.10: 3.20: 7.20: 9.2: 1 or 5: 3.

Similar results are also obtained when the nonionic component is replaced by a mixture of the condensation product of Ci4_i5 alcohol and 3 moles of ethylene oxide together with the condensation product of Ci4_i5 alcohol and 7 moles of ethylene oxide in a ratio of the low ethoxylated nonionic surfactant to higher ethoxylated non-ionic surfactant of about 2: 1, a mixture of the condensation product of C14_i 5-alcohol and 3 moles of ethylene oxide together with the condensation product of myristyl alcohol and 10 moles of ethylene oxide in a ratio of the lower ethoxylated non-ionic surfactant to the higher ethoxylated non-ionic surfactant of about 1: 1 or a mixture of the condensation product of coconut alcohol and 5 moles of ethylene oxide with an alkylglyceryl ether of the formula

C12H25-OCH2CH-CH2OH

OH

O O CH3

C12H25-0 "C" CH2C "2 ~ ^" 0 "CI12CH2 ~ + ^ ~ CH3 C1"

CH,

CH

ch

Br CH, - N-CH, CH, -0-c- (CH _) ._- C-0-CH_CH „-N -CH, Br

35 S% Z A t J

CH,

CH,

0 ch3

c10H21 ~ ° ~ (CH2CH2O) 10 ~ ^ ~ CH "N + _CH3 c1 ~

CII,

45

Example V

A paper towel sheet as in Example I is coated with about 50 50 g of a preparation of the composition given below. The preparation is produced by intimately mixing the non-ionic and cationic surfactants with one another at a temperature of approximately 80 ° C. to form a thick paste and then adding the remaining components.

component

% By weight

0 ch3

60 c17h35-c-o-ch2ch2- + n-ch3 Cl "

CH3

Condensation product from coconut alcohol with 5 moles of ethylene oxide 65 zeosyl 200 choline chloride

Minor fractions (means to suppress foaming, perfume, brightener, etc.)

25.7

50.7 9.S.

11.8

Rest to 100

647 544

10th

A second sheet of paper towel is placed on the top of the coated side of the first sheet and sewn to the edges so that the preparation is enclosed between the substrate sheets. This article provides a convenient method of introducing the detergent preparation into the wash solution and has excellent properties as evidenced by the rate of release of the detergent components into the wash solution and minimization of component bleeding during storage.

A substrate article can also be coated by coating one side of a 28 x 28 cm sheet of blow-molded polypropylene with a thickness of about 0.74 mm, a basis weight of about 70 g / m2 and an air permeability of about 2 liters / min / cm 2 about 60 g of the detergent preparation described above, placing an identical substrate sheet on the coated sheet and heat sealing the edges of the two substrates to include the detergent preparation in the article.

20th

Example VI

An article of the present invention containing the detergent formulation below is made according to the procedure described in Example V. This article shows an excellent cleaning of the greasy-oily and particulate soiling when used in the automatic washing process and has excellent component release properties and a minimum of component bleeding from the substrate sheets during storage. 30th

Example V, procedure described above. This article, when used in a normal automatic washing cycle, gives virtually complete release of the detergent formulation from the substrates and shows minimal bleeding of the surfactant components from the substrate materials during storage. In addition, the article provides excellent cleaning of particulate and greasy-oily soiling and has the effect that the items washed with it are softened, protected against static charge and the dye transfer is inhibited.

component

% By weight

component

% By weight

0 ch3

C17H35_C ~ ° ~ CH2CH2 "+ N ~ CH3 C1 ~

21.4

ch3

Condensation product from coconut alcohol

with 5 moles of ethylene oxide

42.2

Ammonia amide

5.9

Borax * 10 H2O

10.9

Zeosyl 200

9.1

Choline chloride

10.5

35

o ch3

C12H25 ~ (C2H40) 7-CH2-C- ° -C2H4_ + N-ci13 c1 ~ 18.3

cn3

Condensation product from coconut alcohol with 5 moles of ethylene oxide 43.7

Lauramide 4.0

Borax-5 H2O 10.0

Zeosyl 200 9.1

Choline chloride 10.0 minor components (means to suppress the

Foaming, perfume, brightener etc.) rest to 100

Example VIII

An article of the present invention containing the detergent formulation below is made according to the procedure described in Example V, above. When used in automatic washing mode, this article gives an excellent release of the detergent preparation and a minimum of component bleeding during storage.

component

% By weight

Example VII

An article of the present invention, which contains the detergent preparation specified below, is according to the in

Dicoconut alkyldimethylammonium bromide 19 condensation product from Ci4_I5 alcohol with 7 moles of ethylene oxide 48

Ammonia amide 6

45 Bentone 27 10

Choline chloride 11 minor components (means to suppress the

Foaming, perfume, brightener etc.) rest to 100

G

Claims (10)

647 544 2nd PATENT CLAIMS 1. Laundry cleaning article, characterized by a water-insoluble, wet-strength substrate which carries an effective amount of a detergent preparation which contains (a) 5 to 95% by weight of a surfactant mixture (i) non-ionic surfactant with an HLB value of 5 to 17, and (ii) cationic surfactant, the molecule of which consists of (A) 1 to 3 identical or different cationic groups Y which are optionally connected to one another by divalent radicals R1 and are selected from those of the formulas (1) to (7) below (1) (2) (3) (4) (5) (6) -N- \ ✓ • - C- \ N - C -P- -N- (C2H40) pH I. .C. * C! ^ wherein p is 1 to 20 m N C. 'V, ■ 0 * O R r20 -c-o-, -o-c-, -c-n-, -n-c- -0-, (C) zero to 7 groups R2, each representing an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms or a benzyl group, at most one group R2 in the molecule being benzyl, and 5 (D) an anionic part Z which brings about the electrical neutrality of the molecule, the cationic surfactant (ii) in admixture with the nonionic surfactant (i) being at least water-dispersible and the weight ratio of the nonionic surfactant (i) to the cationic surfactant (ii ) is in the range from 5: 3 to 300: 1, and (b) 1 to 30% by weight of non-ionic or cationic solubilizing aid which has a solubility of at least 20% by weight in water at 38 ° C. and completely dissolves in water at 38 ° C. in no more than 2 minutes . 's 2. Article according to claim 1, characterized in that the detergent preparation contains 3 to 25 wt .-% of the solubilization aid (b). 3. Article according to claim 1 or 2, characterized in that the solubilization aid (b) at 38 ° C in water 20 water has a solubility of at least 25 wt .-% and completely dissolves in water at 38 ° C in no more than 1 min. 4. Article according to one of the preceding claims, characterized in that the solubilization aid (b) is selected from choline chloride, ammonium chloride, phenyl 25 methylammonium chloride, sucrose, glucose, polyethylene glycol with a molecular weight of 1000 to 6000 and mixtures thereof. 5. Article according to one of the preceding claims, characterized in that the solubilization aid 30 (b) is hygroscopic. 6. Article according to one of the preceding claims, characterized in that the detergent preparation contains 10 to 90% by weight of the surfactant mixture (a), the weight ratio of nonionic surfactant (i) to cationic 35 surfactant (ii) is 5: 3 to 50: 1. 7. Article according to one of the preceding claims, characterized in that the non-ionic surfactant (i) has the formula R (OC2H4) nOH, in which R is a primary or secondary alkyl chain having 8 to 22 C atoms and n is a medium 4o is worth from 2 to 9. 8. Article according to one of the preceding claims, characterized in that in the cationic surfactant (ii) Z an anion selected from halide, methyl sulfate, hydroxide and nitrate and Y is selected from 45 -n- » -c. \ ✓ N - / + c - Vain which any free carbon, nitrogen, sulfur or phosphorus atom valences are occupied by hydrogen atoms, (B) 1 to 7 monovalent or divalent organic groups R1, each containing a straight or branched alkyl or alkenyl group which is optionally substituted with up to three phenyl groups and is optionally interrupted by up to four identical or different structures from the group -N- (c2h40) ph « 50 where R1 contains 8 to 54 carbon atoms and can also contain up to 20 ethoxy groups, and where no more than one group R1 can contain more than 12 carbon atoms if the molecule of the cationic surfactant contains 3 or more groups R1, 9. Article according to one of the preceding claims, characterized in that the detergent preparation also contains 2 to 20 wt .-% of an agent (C) against bleeding, which is selected from silicas, clays, 55 amides, soaps and mixtures thereof with average Particle sizes no larger than 3.0 microns. -10. Article according to claim 9, characterized in that the anti-bleeding agent (c) is selected from silicon dioxide materials with an average particle size of about 2 microns, bentonite clay materials with an average particle size of about 0.8 microns, silicate materials with an average particle size of 1 to 2 microns and mixtures of these materials. 65 11. Article according to one of the preceding claims, characterized in that the substrate is paper, woven, knitted or nonwoven and carries 3 to 120 g of the detergent preparation. 3rd 647 544 The convenience or effectiveness of laundry cleaning articles in the form of substrates which contain certain amounts of detergent preparation and are introduced as a whole into automatic washing machines is known. Examples of such articles are described in U.S. Patents 4,095,946, 4,118,525 and 4113,630. Furthermore, in the published European patent applications Nos. 78200065.7 and 78200064.0 detergent preparations are described which contain mixtures of defined non-ionic and cationic surfactants and offer excellent removal of particulate and greasy-oily soiling. It would be desirable to combine the excellent cleaning action of these detergent preparations with the advantages of substrate articles. Various problems must be overcome for such a combination, including the rapid and complete release of the surfactant mixture from the substrate into the washing solution, so that the cleaning effects obtained during the relatively short automatic washing cycle of an automatic washing machine can be maximized and losses of surfactant component can be minimized. Furthermore, it is desirable to minimize the bleeding out of the surfactant mixture, in particular the nonionic component, from or through the substrate sheets when the articles are stored.