FI64395B - TVAETTILLSATSPRODUKT - Google Patents

Description

I- ----- Ί KU RELEASE PUBLICATION

^ ^ UTLÄGGNINGSSKRIFT 64 395 C Pr.tor.tti nyörnclty 10 11 1933 (45) Γt c 'lolr.t ^ ^ ^ (51) Ky.lk. ^ lnt.CI.3 C 11 D 7/54 FINLAND— »FINLAND (21) P * t * nttlh.k.mu * - Ptt »nt» n * ölinlng 772939 (22) HtkemlsplIvS - An * öknlnpd »g 05.10.77 (23) AlkupilvI —Glltlghettd.j 05.10.77 (41) Tullut to the public - Blivlt offeitllj 07, Oi. 78 fetontti- ja reklrtarlhallltu, Nihti ^ j. date of publication -? Q 07 8 ^

Patent- och register * tyr «l * en x 'Ansökan utlagd och uil.jkrlften publlcarad 7 1. J

(32) (33) (31) Requested «uoiksui — Bejlrd prlorltst O6.lO.76 01.02.77, i3.O5.77 England-England (GB) I1I9I / 76, 1670/77, 20213/77 (71) The Procter & Geunble Company, 301 East Sixth Street, Cincinnati,

Ohio I5202, USA (72) Gianfranco Luigi Spadini, Ponteland, Newcastle upon iyne,

Ian David Tolliday, Gosforth, Newcastle upon iyne,

Alan Campbell McRitchie, Blyth, Northumberland,

This invention relates to a detergent additive preparation which can be used in aqueous washing solutions. Such formulations can be added to improve the removal of bleachable stains to wash solutions containing conventional inorganic persalt detergent products.

Textile materials, especially materials made of vegetable fibers such as cotton or linen and articles made therefrom, are generally washed by contacting the materials with a washing liquid containing conventional detergent ingredients such as soaps or synthetic detergents as well as various excipients, alkali salts and bleaching agents.

In the most common method of treating textiles with bleachable stains, the textile washing solution is heated from room temperature to close to the temperature of boiling water, i. Above 85 ° C, and kept at this temperature for some time before cooling, after which the textiles are removed.

2 64395

Inorganic salt bleaching compounds, i.e. sodium perborate and sodium percarbonate, which are usually added to detergents, have a good bleaching ability at 85 ° C and above, but deteriorate rapidly at lower temperatures, namely 70 ° C and below, so that full bleaching performance is not achieved unless the washing temperature not high enough. Modern automatic washing machines are equipped with a program of steps including a heating step above 85 ° C (so-called "cooking washing"), but they also have programs with washing steps at a lower temperature to allow the treatment of colored and synthetic fabrics. As the use of these fabrics has become more widespread and due to the publicity surrounding energy saving measures, efforts have been made to increase the use of such low temperature cycles at the expense of kitchen washing. A consistent consequence is the continuing need for products with good bleaching performance in the temperature range of 70 ° C and below, both to maintain washing performance during periods of low temperature and to use expensive materials as efficiently as possible.

For many years, low temperature effective bleaches have been known, most of which are capable of releasing organic peracids as bleaches.

Examples of detergent compositions containing this type of bleach are provided by Reichert et al., U.S. Pat. 2,362,401, issued November 7, 1944 to Moeyer, U.S. Pat. No. 3,639,248, issued February 1, 1972; 836,988 and No. 855.735.

These and other similar publications recommend combining an organic activator with a mixture that reacts with an inorganic peroxy bleach component in a wash solution to release an organic peroxy bleach component, usually peroxyacid. This type of peroxy bleach is more effective than the inorganic peroxy bleach in the lower temperature part of the washing operation. However, the formulation of such products containing combinations of organic peroxy compound activators and inorganic peroxy bleaches has proved difficult because during storage in the presence of moisture absorbed into the mixture prior to use, these substances react to give 3 64395 organic peroxy compounds, which decompose. As a result, the effectiveness of the product is reduced.

Various methods have been proposed to obtain the stability of organic peroxy bleaches or their activators in detergent compositions, such as the use of separate packages such as Woods, U.S. Pat. 3532634, issued October 6, 1970; encapsulation such as Woods (supra), Lund &

Neilsen, U3 Patent No. U.S. Pat. No. 3,49787 and Neilsen; 3494786, both published February 10, 1970; coating such as Seheifer et al., U.S. Pat. 3441507, issued April 29, 1969; and granulation such as Moyer et al., U.S. Pat. 3639248, published February 1, 1972. All of these methods seek to stabilize an organic peroxy bleach or activator thereof in the vicinity of a detergent product to provide the convenience of using one product, although the use is limited by a fixed amount of bleach component for each detergent component in each detergent use. Attempts to improve the stability of the peroxy bleach or its activator in prior art blends resulted in a significant inhibition of bleach release into solution, thus reducing efficiency and increasing costs.

Thus, one disadvantage of products made in the prior art has been that they are expensive compositions in composition, resulting in unnecessary and potentially wasteful use of bleach under certain conditions.

A further disadvantage of the previous products has been the difficulty of preventing damage to the color of the fabric, in particular staining, due to the textile coming into direct contact with the insoluble organic peroxy bleach particles themselves and / or with the locally present sites in the immediate vicinity of the activator particles.

Yet another disadvantage associated with previous product grades has been that they can damage human skin and internal tissues as a result of improper use or accidental inhalation under conditions in which the reaction of an inorganic persalt and an organic activator can occur, resulting in a highly reactive organic peroxy bleach species. Accordingly, it is an object of the present invention to combat these disadvantages by mixing a bleach activator with an additive product in which the activator is chemically and physically stable and spatially isolated from an inorganic peroxy bleach, the product being suitable for addition to a desired amount of conventional detergent mixtures are used. The present invention also seeks to maximize the effectiveness of the bleach by producing a bleach activator in the form of a product from which the activator dissolves very rapidly in an aqueous washing liquid.

The invention also relates to a preparation to be added in a washing process, which is suitable for promoting the removal of bleachable dirt, in particular at temperatures of 70 ° C and below, when added to a solution containing inorganic peroxy salts.

SUMMARY OF THE INVENTION The detergent additive preparation of the present invention is characterized in that it consists of a flexible sheet-like support having a non-particulate solid coated and / or impregnated in water (a) with 0.1 to 30 parts by weight of an organic peroxy compound -activator per part by weight of carrier, (b) 0-20 parts by weight of one or more treatment or release agents per part by weight of carrier, (c) 0-5 parts by weight of organic chelating agent per part by weight of carrier, and (d) 0-20 parts by weight of surfactant per part by weight of the carrier, and (e) if desired, other conventional detergent components which do not react with the activator.

The process for preparing a detergent additive preparation according to the invention is characterized in that it comprises the steps of forming the peroxy compound Tor into a liquid mass, combining said liquid mass with a solid non-particulate support body so that the treated surface of the latter becomes as close as possible. large, and converting said mass to a solid. The solid, non-particulate body is impregnated with said mass and said mass is brought into a solid form.

As used herein, an organic peroxy compound activator means any organic compound capable of reacting with an inorganic peroxygen-containing compound in aqueous solution to form an organic peroxy compound having a bleaching power of at least equivalent to the inorganic peroxygen-containing compound under the same conditions at 70 ° C. and at a temperature below this.

64395 For the purposes of this invention, priority is given to substances whose required titer in the perhydrolysis test defined below corresponds to at least 2.0 milliliters of 0.01 molar sodium thiosulphate solution.

Likewise, the terms inorganic peroxy bleach and inorganic persalt used herein are intended to cover salts such as alkali metal perborates, percarbonates, persilicates and perpyrophosphates which produce hydrogen peroxide in aqueous solution, rather than compounds which permeate persulphates, e.g. other peroxy species.

For the purposes of this invention, a water-releasing combination means a combination that is capable of being dispersed by water by dissolving, dispersing, extracting, softening or melting.

In a preferred aspect of the invention, the organic peroxy compound activator or each of a portion of a mixture of such activators is selected from the group consisting of anhydrides, esters, oximes and N-acylated compounds. The activator is essentially one or more N-acylated compounds having the structural formula f? CH, - C yC - CH,> - (ch2 »x - <CH, - or - CH, 3 4 4 3 where x can be 0 or an integer from 1 to 6 and is closest to 1, 2 or 6. Also primarily the body is in the form of a flexible disk carrier with a weight ratio of activator to carrier in the range of 10: 1 to 1:10.

The additive preparations according to the invention are designed to be added to a washing machine with stained fabrics, or to drum machines programmed at the beginning of the main washing stage. In this case, the activator and the inorganic peroxy-bleach compounds contained in the washing mixture do not come into contact with each other until in the washing liquid. The addition of an activator to the wash liquor in a water-dispersible combination with a non-particulate solid avoids the stability concerns associated with mixing peroxygen bleach activators with conventional granules, blends 64395 and also allows the user to control whether or not to use low temperature bleaching. the amount of peroxy bleach. The additive formulations of this invention are also safer for the user when the key components are physically separated from each other and substantially affect the accidental inhalation of the combination.

Thanks to the present invention, the peroxy compound activator also dissolves more rapidly in the washing liquid compared to the rate achieved with earlier granular products, and this, in turn, increases the rate of conversion to the organic peroxy bleach type. Thus, the overall efficiency of the organic peroxy compound is improved and the annoying catalase effects on the bleaching efficiency of the remaining inorganic peroxy bleach are reduced. The primary object of the invention is to provide an effective means of removing dirt on fabrics in an advantageous manner, whereby various stains, including stains caused by grease and oil, and stains can be removed.

Detailed description of the invention

As already stated above, the additive preparation according to the invention comprises two components, namely the water-releasable combination of the organic peroxy-compound activator with a carrier, non-particulate solid.

Organic peroxy compound activator

Organic peroxy compound activators, i.e. the inorganic persalt activators by which they are commonly known, are well known in the art and have been extensively described in the literature.

Examples of various peroxy compound activator groups include a) anhydrides; These may be aliphatic, aromatic or mixtures thereof and may be derivatives of mono- or polycarboxylic acids. The primary aliphatic anhydrides have various aliphatic groups having 1 to 12 carbon atoms and the aliphatic mixed anhydrides must not have more than 20 carbon atoms. Specific 7 64395 aliphatic anhydrides include acetic acid, propionic acid, butyric acid, heptanoic acid, nonanoic acid, acetic acid-hexadecanoic acid, acetic acid-stearic acid and butyric acid-myristic acid anhydrides ·

Aromatic anhydrides can be substituted or unsubstituted, with preferred examples being benzoic acid, phthalic acid and pyrometallic anhydrides and their halo, nitro and alkoxy analogs containing nucleosubstitutes such as 2,4-dichlorobenzoic anhydride and anhydride anhydride, -metoksibentsoehappoanhydridi.

Mixtures of aliphatic and aromatic anhydrides are also useful in the context of this invention, provided that they do not contain more than 12 carbon atoms per molecule, examples being benzoic acid-acetic anhydride and benzoic acid-propionic anhydride. Other useful anhydrides include cyclic anhydrides such as maleic anhydride, succinic acid, glutaric acid, adipic acid and itaconic acid anhydrides, and polymeric anhydrides such as polyadipic acid and polyazelaic acid polyanhydrides. j

HO0C - (CH0) - C - 0 - C - (CH0) - C - 0 - C - (CH0) - COOH

2 p 2 p 2 p a where p is closest to 4-7 and q has a value of 5-15, closest to 7-8.

Reichert discloses in U.S. Pat. 236401, published November 7, 1944, on the use of certain organic anhydrides as perborate activators in detergent compositions # b) Esters

Esters suitable as peroxy compound activators in the context of this invention include the N-substituted acids of mono- and disaccharides of mono- and disaccharides having a single hydroxy substituent and unsubstituted phenols, substituted aliphatic alcohols in which the substituent group is electronically attracted . Phenyl esters of both aromatic and aliphatic mono- and dicarboxylic acids are useful. The acyl group of aliphatic esters may have 1 to 20 carbon atoms, examples being phenyl acetate, phenyl laurate, phenyl myristate, phenyl palmitate and phenyl stearate. Of these, o-acetoxy-benzoic acid and methyl-o-acetoxybenzoate are particularly preferred. Examples of phenyl aliphatic dicarboxylic acid esters are diphenyl succinate, diphenylazelate and diphenyl adipate. Aromatic barriers include phenyl benzoate, diphenyl phthalate and diphenyl isophthalate.

A specific example of an ester of a substituted aliphatic alcohol is trichloroethyl acetate. Examples of saccharide esters are glucose pentaacetate and sucrose octaacetate. An example of a hydroxylamine ester is acetylacetohydroxamic acid.

These and other esters suitable for use as peroxy compound activators in the context of this invention are described extensively in GB Patent Publication Nos. 836,988 and 839,715.

An additional ester group is formed by acylphenol sulfonates and acylalkylphenol sulfonates. Examples of the above are sodium acetylphenol sulfonate (alternatively sodium p-acetoxybenzenesulfonate) and sodium benzoylphenol sulfonate (alternatively sodium p-benzoyloxybenzenesulfonate). Examples of acylalkylphenol sulfonates are sodium 2-acetoxy-5-dodecylbenzenesulfonate, sodium 2-acetoethoxy-5-hexylbenzenesulfonate and sodium 2-acetoxycaprylenesulfonesulfonate. The preparation and use of these and analogous compounds are described in GB Patent Publication Nos. 963,135 and 1,147,871.

Acetylated esters of phosphoric acid have also been proposed as organic peroxy compound activators, for example diethyl monoacetyl orthophosphate and diacetylethyl orthophosphate.

The general formula for esters of imidic acids is

.NH

0X

9 64395 wherein X is substituted or unsubstituted C 1 -C 4 alkyl or aryl and Y may be the same as X and may also be -NH 2. An example of a compound in this group is ethyl benzimidate wherein Y is CgH5 and X is ethyl.

Other specific esters include p-acetoxyacetophenone and 2,2-di- (4-hydroxyphenyl) propane diacetate. The latter is a diacetate derivative of 2,2-di (4-hydroxyphenyl) propane, more commonly known as Bisphenol A, which is an intermediate in the preparation of polycarbonate resins. Bisphenol A diacetate and methods for its preparation are described in DE Publication No. 1,260,479, published February 8, 1968, in the name of the applicant VEB Chemiefaserwerk Schwarza "Wilhelm Piesh" o) Imides

Imides suitable as organic peroxy compound activators within the scope of this invention are compounds of the formula 0X0 1 R 1 -CNC-R 2 wherein R 1 and R 2, which may be the same or different, are independently selected from a C 1 -C 4 alkyl group. or an aryl group and X is an alkyl, aryl or acyl radical (either carboxyl or sulfone). Typical are compounds in which R 1 is a methyl, ethyl, propyl or phenyl group, although preferred are compounds in which R 2 is also methyl, examples of such compounds being N, N-diacetylaniline, N, N-diacetyl-p-chloroanine and N, N-diacetyl-p-toluidine. Each of R 1 and R 2 may be taken together with X to form a heterocyclic ring having a nitrogen atom. An illustrative group of compounds having this type of structure are N-acyl lactams in which a nitrogen atom is attached to two acyl groups, one of which is also attached to the nitrogen atom at the other position via a hydrocarbyl bond. A particularly preferred example of a compound in this group is N-acetyl-caprolactam. The bond of the acyl group involved in the formation of the heterocyclic ring may itself contain a heteroatom, e.g. an oxygen atom, and the N-acyl saccharides form one of this group of typical activators.

10 64395

Examples of cyclic imides in which the reactive center is a sulfone radical are N-benzenesulfonylphthalimide, N-methanesulfonylsuccinimide and N-benzenesulfonylsuccinimide. These and other N-sulfonylimides useful herein are described in GB Patent No. 1,242,287.

Combinations between nitrogen atoms and three acyl groups occur in N-acylated dicarboxylic acid imides such as N-acylphthalimides, N-acylsuccinimides, N-acyladipine imides and N-acylglutarimides. Imides of the type mentioned above are described in GB Patent Publication No. 855,735.

Further, two primary groups of substances in this class are compounds in which X of the above formula is either another diacylated nitrogen atom, i. substituted hydrazines, or a bifunctional hydrocarbyl group such as a C 1 -C 6 alkylene group further having a diacylated nitrogen atom as a substituent, i.e. tetraacylated alkylenediamines.

Particularly preferred compounds are N, N, N ', N'-tetraacetylated compounds of formula 8o I. Il CH3 ~ L \ ^ "CH3

N - (CHn) - N

/ 2 x 'v.

CH 2 - (r - CH, 3 «III 3 where x can be 0 or an integer from 1 to 6; examples are tetraacetylmethylenediamine (TAMD) where x = 1, tetraacetylethylenediamine (TAED) where x = 2, and tetraacetylhexamethylenediamine (TAHD), where x = 6. When x = 0, the compound is tetraacetylhydrazine (TAH) TAHD and TAMD are particularly preferred due to their low melting points (59 ° C and 83 ° C, respectively). ), which facilitates their processing into the additive preparations of the present invention, as described below.These and analogous compounds are described in GB Patent Publication Nos. 907,356, 907,357 and 907,358.

11

Acylated glycouryls form an additional group of compounds that contain imidiperoxy compound in the general class of activators. The general formula for these substances is rro - «r xS - ° £" 'R "" wherein at least two of the R groups correspond to acyl radicals having from 2 to 8 carbon atoms in the structure. Acylated glycouryls are described in GB Patent Nos. 1,246,338, 1,246,339, 1,246,817 and 1,247,429.

Other imide-type compounds suitable for use in the present invention as peroxy compound activators include the N- (halobenzoyl) imides disclosed in GB Patent No. 1,247,857, a primary example of which is Nm-chlorobenzoylsuccinimide, and polyimides. having an N-linked-tu-COOR group, e.g. N-methoxycarbonylphthalimide, disclosed in GB Patent No. 1,244,200.

N-acyl and N, N'-diacyl derivatives of urea are also peroxy compound activators useful for the purposes of this invention, especially N-acetyldimethylurea, N, N'-diacetylethylene urea and N, N'-diacetyldimethylurea. Compounds of this type are disclosed in NL Patent Application No. 6,504,416, published October 10, 1966.

Other urea derivatives with inorganic per salt activating properties include the mono- or di-N-acylated azolinones disclosed in GB Patent No. 1,379,530.

12 64395

Acylated hydantoin derivatives are also included in this general group of organic peroxy compound activators. Hydanthines may contain, for example, lower alkyl groups as substituents and one or both nitrogen atoms may be acylated. Examples of this type of compound are N-acetylhydantoin, N, N-diacetyl, 5,5-dimethylhydantoin, 1-phenyl, 3-acetylhydantoin and 1-cyclohexyl, 3-acetylhydantoin. These and similar compounds are described in GB Patent Publication Nos. 965,672 and 1,112,191.

Another class of imide-type nitrogen compounds are N, N-diacylmethylenediformamides, with Ν, Ν-diacetylmethylenediformamide being preferred. This compound and other similar compounds are disclosed in GB Patent No. 1,106,666.

d) Cyano compounds

As a further group of organic compounds suitable as peroxy compound activators within the scope of this invention are those having the general formula

X-C ~ .N

wherein X may be a substituted or unsubstituted alkyl or aryl group or may be -C - A, wherein A is -OR or -NR, R0, R 1 is 1 <1 10 and R E is each lower alkyl, or a substituted or unsubstituted aryl group.

This class of compounds differs from most other peroxy compound activators in that their reaction with inorganic per salts forms a peroxy species other than peroxyacids.

When X is a substituted or unsubstituted alkyl or aryl group, the compounds are nitriles, which may be of the mono- or polyfunctional type and whose potency increases with increasing number of cyano groups, provided that the compounds remain slightly water-soluble. Specific examples of organic nitriles are phthalenitrile, benzonitrile, tetramethylenenitrile, malonitrile, ethylenediaminotetraacetic acid dinitrile, nitrilotriacetic acid nitrile and succinonitrile. These and other similar compounds useful herein are extensively described in GB Patent Publication No. 802,035.

13 64395

Compounds of the above formula wherein X is -COOR or -CONR1R2 are disclosed in DE Application No. 2,647,978, published April 28, 1977.

e) Imidazoles N-acylimidazoles and the corresponding five-membered ring systems form an additional series of compounds useful as inorganic peroxy compound activators. Specific examples are N-acetylbenzimidazole, N-benzoylimidazole and its chlorine and methyl analogues. Compounds of this type are disclosed in GB Patent Publication Nos. 1,234,762, 1,313,765 and 1,395,760.

f) Oximes

Oximes, and in particular acylated oximes, also form a useful group of organic peroxy compound activators suitable for the purposes of this invention. Oximes are derivatives of hydroxylamine from which they can be prepared by reacting it with aldehydes and ketones to give aldoximes and ketoximes, respectively. Acyl groups may be C 1 -C 2 aliphatic or aromatic in nature, with the preferred acyl groups being acetyl, propionyl, lauroyl, myristyl and benzoyl. Compounds with more than one carbonyl group can react with more than one equivalent of hydroxylamine, and compounds of the most common class of dioximes that are derivatives of 1,2-diketones and ketone aldehydes, such as dimethylglyoxime

CH0-C ... N-OH

CH3- e · --- N-OH

Acylated derivatives of this compound are particularly valuable as organic peroxy compound activators, for example diacetyldimethylglyoxime, dibenzoyldimethylglyoxime and phthaloyldimethylglyoxime.

64395 14 g) Carbonates

Substituted and unsubstituted aliphatic, aromatic and alicyclic esters of carboxylic acid and pyrocarboxylic acid have also been proposed as organic peroxy compound activators. Typical examples of such esters are p-carboxyphenylethyl carbonate, sodium p-sulfophenylethyl carbonate, sodium p-sulfophenyl-n-propyl carbonate and diethyl pyrocarbonate. The use of such esters as inorganic persalt activators in detergent compositions is disclosed in GB Patent No. 970,950.

In addition to the above classes of compounds, a number of other substances can be used as organic peroxy compound activators, including triacylguanidines of the formula

O

B

N - C - R

O f. 0

R - I - N * ^ S'SsN - I - R

i A

wherein R is alkyl, mainly acetyl or phenyl, prepared by acylation of a guanidine salt. Other classes of compounds include acylsulfonamides, e.g., N-phenyl-N-acetylbenzenesulfonamide, which are described in GB Patent No. 1,003,310, and triazine derivatives, such as the compounds described in GB Patent Publication No. 1 104,891 and No. 1,410,555. Particularly preferred examples of triazine derivatives are 2,4,6-trihydroxy-1,3,5-triazine, 2-chloro-4,6-dimethoxy-S-triazine and 2,4 di- and triazole-style derivatives of -dichloro-6-methoxy-S-triazine. Also useful are piperazine derivatives such as 1,4-diacylated-2,5-diketopiperazine described in GB Patent Nos. 1,339,256 and 1,339,257, as well as water-soluble alkyl and aryl chloroformates such as methyl, ethyl and phenyl chloroformates described in GB.

15 64395

Of the above classes of activators, the preferred classes are those which produce peroxycarboxylic acid when reacted with an inorganic persalt. Preferred classes are, in particular, anhydrides, imides, oximes and esters, in particular phenol esters and imides.

Specific preferred materials include methyl o-acetoxybenzoate, sodium p-acetoxybenzenesulfonate, Bisphenol A di-acetate, tetraacetylethylenediamine, tetraacetylhexamethylenediamine and tetraacetylmethylenediamine.

Although color deterioration of a type of fabric known as "spot staining" is minimized and in most cases effectively eliminated by the use of additional products of this invention, it has been found that under very severe conditions, especially when washing very dirty fabrics, color deterioration can still occur with certain peroxy compounds. activators, most notably the use of perbenzoic acid generating activators as a bleaching agent.

Surprisingly, however, it has been found that this possibility of color fading can be mainly counteracted if such perbenzoic acid activators are used in admixture with rapidly perhydrolysing peracetic acid activators, peracetic acid-Akt activator or 10 to 10: 1, mainly between 5: 1 and 1: 5.

Although the mechanism of action of anti-fading of the mixture is not clearly known, it is believed that the mixture effectively inhibits catalase activity in the wash liquor. Catalase is known to destroy hydrogen peroxide produced by inorganic perveachers, which are usually mixed with detergent products and, in the practice of this invention, are believed to prevent conditions in which a less desirable type of organic bleach is formed.

Peroxybenzoic acid is a more potent bleaching agent than peracetic acid, i. it has a higher oxidation potential and thus, in order to maximize the effectiveness, the relative proportion of peracetic acid in the bleach mixture must be kept to a minimum in order to prevent discoloration of the fabrics to be washed in the solutions containing the additive preparations according to the invention.

16 64395

As mentioned above, it has been found that color fading can be satisfactorily prevented if the weight ratio of perbenzoic acid activator (s) to peracetic acid activator (s) is in the range of 10: 1 to 1:10, mainly between 5: 1 1: 5, with a ratio of about 1: 1 being most suitable. In this regard, it should be noted that the conversion of a peroxy compound activator to a peroxyacid compound may not always be quantitative, depending on the nature of the activator, and the reaction conditions under which the conversion takes place, in particular time and temperature.

It should be noted that mixtures with a weight ratio of perbenzoic acid activators to peracetic acid activators of less than 1:10 are satisfactory, although slightly weaker in terms of bleaching performance, and due to their poor performance, color fading damage is minimal. However, the advantages provided by the improved bleaching potential of perbenzoic acid with a low risk of color fading can best be achieved by using the additive formulations of this invention with activator mixtures in the ratios mentioned above.

The amount of peroxy compound activator applied to the support is arranged so that the weight ratio of activator to support is in the range of 30: 1 to 1:10, more usually between 10: 1 and 1:10. Most preferably, the weight ratios of activator to carrier are in the range of 8: 1 to 1: 2 and most preferably in the range of 5: 1 to 1: 1.

The amount of use of an organic peroxy compound activator will, of course, depend on a number of factors, such as the amount of fabric in the machine, the desired level of bleaching power, the amount of inorganic persalt in the conventional detergent product and the use of the detergent product. In the case of inorganic peroxygen bleaches, the amount of oxygen available in the solution is, for convenience, sought to be between 50 ppm and 350 ppm with a view to the use of high-performance washing facilities. However, when using organic peroxy bleaches, the amount of oxygen obtained with the organic peroxy compound must be in the range of 10 ppm to 80 ppm. This available amount of oxygen must be maintained during the normal wash cycle, i.e. 15-25 minutes depending on the specific wash cycle used.

For a machine with an available liquid capacity of 20 to 30 liters, such an available amount of oxygen requires that 1 g to 20 g of the organic peroxy compound activator be fed, assuming that the conversion takes place quantitatively. This figure increases in proportion to the decrease in conversion power. Primarily, a single carrier unit should be able to receive this amount of Akti and any amounts of diluents and additives that must be added to the product, although the number of units used to deliver the desired amount of activator is optional. Normally, the weight of the activator per feed is in the range of 3-10 g, mainly 4-6 grams.

Carrier The present invention requires that the peroxy compound activator be in a water-releasable combination with a carrier having a non-integral solid. The carrier itself may be water-soluble or water-insoluble, and in the latter case it should be structurally sufficiently intact under per salt conditions to be recovered from the machine at the end of the wash cycle. Structures that disperse in water, i.e. breaking into insoluble, separate fibers or particles in an aqueous medium are not considered satisfactory for the purposes of this invention.

Water-soluble materials include certain cellulose ethers, alginates, polyvinyl alcohol, and water-soluble polyvinylpyrrolidone polymers that can be formed into nonwoven and woven fibrous structures. Suitable water-insoluble substances include, for example, natural and synthetic fibers, foam products, sponge preparations and films.

The carrier can be in any of a number of physical forms such as plates, blocks, rings, spheres, rods, or tubes. Such forms must be suitable for the consumer's usual use, i.e. it must be possible to add them to the washing liquid in measurable quantities, such as individual plates, blocks or spheres and in equal lengths of rods or tubes. Certain such carrier types may be designed for single use or multiple use, and may be loaded with an organic peroxyacid activator such that the weight ratio of activator to carrier does not exceed 3 U: 1.

One such product is formed by a spongy material having such an amount of organic peroxy compound activator encapsulated in bulk that the bleaching effect is maintained over several wash cycles. Such a reusable product 18 64395 can be prepared by impregnating a sponge, ball or block body with about 20 grams of activator and any additives. In use, the activator diffuses from the porous detergent of the sponge and reacts with the inorganic peroxygen bleach. Such a stuffed sponge can be used in conventional washing machines to handle multiple batches of fabric, and has the advantage that it can remain in the washing machine after use.

Other devices and articles that can be used for dispensing an organic peroxy compound activator into a wash liquor are described in the patents: Dillarstone, U.S. Patent 3,736,668, issued June 5, 1973: Cornpa et al., U.S. Patent 3,701,202, issued October 31, 1972; Furgal, U.S. Patent 3,634,947, issued January 18, 1972; Hoeflin, U.S. Patent 3,633,538, issued January 11, 1972, and Rumsey, U.S. Patent 3,435,537, issued April 1, 1969.

A highly preferred related product is an organic peroxy compound activator in a water-releasable combination with a sheet, which must be flexible to be able to adapt to the movements of the fabrics in the washing machine and to facilitate its handling in the manufacture of the product. The plate is preferably water permeable, i.e. water can pass from one surface of the plate to the opposite surface, and in the case of film-type carriers, it is desirable that the plate be perforated. The most preferred carrier form is a sheet made of a woven or nonwoven fabric or a thin cellular plastic material. The woven fabric sheets may be a fabric made of uniformly strong natural product fibers or synthetic fibers with a low number of fibers per unit length, such as is used, for example, in surgical dressings, or of a type known as a cheesecloth. The load capacity of the plate-like carriers limits the amount of activator that can be applied to the plate, with the maximum amount corresponding to an weight ratio of Akti to plate of about 10: 1.

A highly desirable feature of the additive formulations of this invention for use in laundry is that they do not interfere with the mechanical operation of the washing machines in which they are placed. Most household washing machines are of the rotating perforated drum type, li 64395 19 where the perforation extends over the entire circumferential surface. In this type of device, the structure and mode of operation of the drum prevent the possibility of the flow of liquid in the machine being blocked. Some older type machines use a stirrer in a stationary vessel equipped with a circulating fluid system. In order to avoid obstruction of the fluid flow in this type of machine, it may be necessary for the carrier to be provided with slots or perforations, especially in the form of a plate. Plate structures of this type are described in U.S. Patent Nos. 3,944,694 and 3,956,556 to McQueary, issued March 16, 1976 and May 11, 1976, respectively.

A desirable property of a carrier for use in the present invention is that it is absorbent in nature. It is known that most substances are able to absorb liquid matter to some extent; however, as used herein, the term "absorbent" refers to a substance that has an absorbent capacity (i.e., an amount corresponding to the ability of the carrier to absorb and retain fluid) to such an extent that it absorbs about 12 times its weight of water.

Absorbency assays are performed using capacity testing methods described in U.S. Pat. Federal Specification UU-T595b modified as follows: 1) tap water is used instead of distilled water; 2) the specimen is kept immersed for 30 seconds instead of 3 minutes; 3) the drain time is 15 seconds instead of 1 minute; and 9) the test piece is immediately weighed with a torsion balance with the corners of the horizontal cup bent upwards.

The absorbency values are then calculated according to the formula given in said publication. Based on this test, plain, dense, bleached paper (e.g., kraft paper or 2 bond paper with an initial weight of about 0.05 kg / m 2 has an absorbency of 3.5 to 4; commercially available plain towel paper has a value of 5 to 6; and the value of commercial double towel paper traded is 7 to about 9.5.

64395 The term "free space" may also be used to define the carrier of the present invention. Free space, also referred to as "cavity volume", as used herein means an unfilled space in a structure. For example, in some multi-ply paper structures, there are protrusions between the layers, with the ends of the layers being together and joined together; in such a paper structure, the non-compressed portion between the layers has a void volume corresponding to the free space, as well as between the fibers and the paper sheet itself. A nonwoven fabric also has such a space between all its fibers. The free space of a nonwoven fabric or paper having the designed physical dimensions can be varied by modifying the fiber density of the paper or nonwoven fabric. In carriers with a very large amount of free space, the fiber density is generally low; in high-density carriers, there is usually little free space. In the preferred carriers of this invention, the amount of free space, based on the total volume of the carrier structure, is up to about 90%.

As mentioned above, suitable materials that can be used as a carrier in the present invention include sponges, paper, and woven and nonwoven fabrics. The primary carriers for the detergent additive preparations used in this case are cellulose-based, non-perforated and non-perforated nonwoven fabrics.

A suitable carrier is, in particular, a compressible, laminated, calendered, multilayer absorbent paper structure. The paper structure has mainly 2 or 3 layers and a total basis weight of 0.02 to 0.15 kg / m 2 and absorbency values in the range of 7-10. The basis weight of each layer of the primary paper structure is about 0.01 to 0.05 2 kg / m 2, and the paper structure may be formed by layers having the same or different basis weights. Each ply is made primarily of shirred, or otherwise stretchable, paper having a shrinkage percentage of about 15% to 40% and a tensile strength in the machine direction (MD) and transverse direction (CD) of about 15 to 235 g / paper width-2 den cm. The two outer layers of the 3-ply paper structure or both layers of the 2-ply paper are patterned with identical repeating patterns of about 2.5 to 31 distinct protrusions / cm 2 that rise to a height of about 0.025 to 1.0 cm 2. above the surface of the unpatterned paper sheet. About 10% to 60% of the surface of the paper plate is raised. The ends outside the raised portions of each layer (i.e., the ends outside the patterned paper sheet surface) are joined and bonded together with an adhesive to form a primary paper structure having a compression modulus of about 30 to 125 cm g / cm (200 to 800 inches). grams per cubic inch) and the MD and CD values obtained with the Handle-O-Meter (HOM) are about 10 to 310.

Compression modulus values that determine the compressive deformation properties of a paper structure whose opposite surfaces are loaded using compression, HOM values that indicate the stiffness or processability of the paper structure, MD and CD-H0M values that refer to HOM values obtained in the machine direction and across of the paper structure samples tested in the direction, the methods by which these values are determined, the equipment used, and a more detailed description of the paper structure in question herein as well as the method of making it can be found in Edward R. Wells U.S. Pat. 3414459, published December 3, 1968,

Preferred nonwoven carriers useful in the context of the invention can be generally defined as gluing bonded fibrous or filamentary products having a woven or carded fibrous structure (where fiber strength allows carding) or are fibrous mats in which the fibers or filaments are randomly distributed. the order of the fibers in the carded fabric, where there is often a partial orientation of the fibers as well as a completely random orientation) or substantially parallel. The fibers or filaments may be natural products (e.g. wool, silk, wood pulp, jute, hemp, cotton, linen, sisal, or ramie), synthetic (e.g. artificial silk, cellulose, esters, polyvinyl derivatives, polyolefins, polyamides, polyamides, ) or mixtures of the above materials.

Go Stamps used to make woven fabrics do not form part of this invention and as they are. well known in the art, they are not described in more detail here. Such fabrics are usually made by air or water precipitation methods, in which the fibers or filaments are first cut from long strands to the desired length, directed into a flow of water or air, and then deposited on a screen through which fibrous air or water is passed. The precipitated fibers or filaments are then bonded together by gluing, dried, cured, and otherwise treated as desired to form a nonwoven fabric. Nonwovens made of polyesters, polyamides, vinyl resins and other thermoplastic fibers can be bonded by braiding, i. the fibers are applied to a flat surface and bonded (melted) together by heating or chemical reactions.

The desired absorption properties are particularly easily achieved by using non-woven fabrics and are only achieved by increasing the thickness of the fabric, i. by superimposing a plurality of carded fabrics or mats until the thickness is appropriate to achieve the required absorption properties, or by allowing the fibers to deposit on the screen into a suitably thick layer. Fibers of any diameter or denier can be used for this purpose (usually up to about 10 denier) because the free space between each fiber makes the thickness of the fabric directly dependent on the absorbent capacity of the fabric, further enhancing the particular suitability of the nonwoven fabric for impregnation with peroxyacid or capillary impregnation. Thus, any required thickness can be used to achieve the desired suction capacity.

The choice of binder resins used in the manufacture of woven tower fabrics can be used to provide carriers with a variety of desirable properties. For example, the absorbency of the fabric can be increased, decreased, or regulated by using a hydrophilic binder resin, a hydrophobic binder resin, or a mixture thereof, respectively, in the fiber bonding step. In addition, the use of a hydrophobic binder resin, when used alone or as a major compound in a mixture of hydrophobic and hydrophilic resins, provides nonwovens that are particularly useful as carriers when the activator carrier combinations disclosed herein are used in an automated manner.

When La lana is a nonwoven fabric made of fibers that Oval saos turiee t the screen randomly or in a random order of n 23 64395, the blends are excellent strength in all directions and do not tend to tear or separate when used in a washing machine.

The nonwoven fabric is mainly water-precipitated or air-precipitated and is made of cellulosic fibers, in particular fibers made of regenerated cellulose or artificial silk lubricated with a common textile lubricant. The fibers are mainly 0.48-5.1 cm long and 1.5 to 5 denier thick (denier is an internationally recognized unit of yarn equivalent to the weight of a 9,000 meter long wire in grams). Preferably, the fibers are oriented at least in part randomly, in particular substantially randomly, and are bonded together by an adhesive with a hydrophobic or predominantly hydrophobic binder resin, in particular a non-ionic self-curing acrylic polymer or polymers. Most suitably, the fabric has about 70% by weight fiber and 30% by weight binder resin polymer and a basis weight of about 12-120 g / m 2, preferably 24-72 g / m 2. A suitable example is an air-precipitated nonwoven fabric having 70% regenerated cellulose (American Viscose Corporation) and 30% hydrophobic binder resin (Rhoplex HA-8 on one side of the fabric, Rhoplex HA-16 on the other side;

Rohm & Haas, Inc.). The fabric has a thickness of 0.10 to 0.13 mm, a basis weight of about 29 grams per square meter, and an absorbency of 5. The fabric, which is 30.5 cm long and 21.2 cm wide, weighs about 1.78 grams. The fibers are 0.64 cm in length, 1.5 denier in thickness, and are oriented mainly randomly. The fibers are lubricated with sodium oleate.

A further example of a carrier is a water-precipitated nonwoven fabric supplied as a technical product by C.H. Dexter Co., Inc. The fibers are regenerated cellulose, about 1 cm long, 1.5 denier thick, and lubricated with a similar normal textile lubricant. The fibers comprise about 70% by weight of the nonwoven fabric and are oriented mainly randomly; the amount of binder resin (HA-8) is about 30% by weight of the fabric. The carrier is about 0.10 mm thick and has a basis weight of about 29 grams per square meter and an absorbency of 5.7. The 30.5 cm long and 21.2 cm wide fabric weighs about 1.66 grams.

64395 24

Perforated nonwoven carriers are also useful for the purposes of this invention. The openings spread between the opposing surfaces are usually in series and are formed during the doping of the fibers in the manufacture of the support. Examples of open weaving tower carriers are disclosed in U.S. Patent Nos. 3,741,724, 3,930,086, and 3,750,237.

A particularly suitable example is a perforated nonwoven carrier manufactured by Chicopee Manufacturing Co., Milltown, New Jersey, USA, code SK 650 WFX 577, and is a blend of polyester and wood chips with a basis weight of 50 granules / square meter and approximately 13 openings. per square centimeter.

Another preferred example of perforated nonwoven carriers is a carrier manufactured by Chicopee Manufacturing Co. code AK 30 ML 1379, made of regenerated cellulose board with 3,0 denier fibers bound with Rhoplex RA 8 (fiber to binder ratio 70:30), with a basis weight of 40 g / m and 17 openings / cm.

The open fabrics used for the purposes of the invention usually have 10-20 openings / cm, mainly 12-18 openings / cm.

A further class of carrier materials useful in the present invention is absorbent sponge material in the form of a sheet. The term "absorbent sponge material" is intended to include three-dimensional absorbent materials such as 'gas-expanded sponges', natural sponges, and fiber-assembled structures such as those described in U.S. Patent Nos. 3,311,115 and 3,430,630.

One particularly suitable material of this type is a hydrophilic polyurethane foam product in which the intercellular walls of the interior of the foam product have been broken by reticulation. Foam products of this type are described in detail in U.S. Patent No. 3,794,029 to Dulle. A preferred example of a foam product of this type is a hydrophilic 3 polyurethane foam product having a density of about 0.036 g / cm 3 and a cell count of 8-40 cells / cm. preferably about 24-31 cells / cm, and manufactured by Scott Paper Company, Eddystone, 25 6 4 3 9 5

Pennsylvania, USA, under the registered trademark "Hydrofoam".

The size and shape of the carrier plate are optional and are determined mainly by factors relating to the appropriateness of its use. Thus, the plate must not be so small that it sticks to the cracks or washable fabrics of the machine, or so large that it is difficult to pack and take from the container in which it is sold. Acceptable for the purposes of this invention are sheets having an area of 129 to 1290 cm, with a primary area of 516 to 774 cm 2.

Optional components

In addition to the peroxy compound activator, one or more other substances may be applied to the carrier, either alone or in combination with the activator.

The type and number of such optional functional components are limited only by the requirements that they not react with the activator (if the optional substances are used in close contact with the activator) and by the factors limiting the loading of the carrier. As will be described in more detail below, substances capable of reacting with the activator may be mixed with the additive products of this invention, but it is essential that the activator be spatially separated from them, i. placed in the position of the applicant where there are no or mainly no other reactive substances. Private optional components may be added in amounts corresponding to the weight ratios of the component to the carrier of 20: 1. For manufacturing and product aesthetic reasons, the total weight of optional components per plate is normally considered to be no more than 10 times the weight of the plate, and ideally less than 5 times the weight of the plate, with no more than 3 times the weight of the individual components.

One factor that determines the acceptable amount of optional ingredient to be added is its physical properties, i. whether it is a liquid or a solid and if it is a solid, whether it is crystalline or waxy and whether its melting point or softening point is high or low.

64395 26

The most preferred optional components are solid, water-soluble or water-dispersible organic excipients of a waxy nature with a softening point higher than | 40 ° C and a melting point lower than 80 ° C for easy handling.

If the peroxy compound activator itself does not have these properties, e.g. as a solid with a high melting point, it is recommended to add one or more of the above-described excipients to facilitate preparation and / or release the activator from the carrier when adding the latter to the washing liquid. The primary excipients act as plasticizers or thickeners when adding activators to or on the carrier, and ideally are non-hygroscopic solids which are mixed with the activators and melted to obtain mixtures having a viscosity of up to 5000 centipoise at 50 ° C.

Typical solids include polyvinylpyrrolidone having a molecular weight of 44,000 to 700,000, most preferably 500,000 to 700,000, tallow alcohol ethoxylates having 5 to 30 ethylene oxide groups per mole of alcohol, C 1-4 fatty acids, and certain esters and amides thereof, Sorbitan esters and polyethylene glycols having a molecular weight of> 4000. As mentioned above, the preferred substances are substances with a low hygroscopicity, in particular saturated fatty acids having a carbon atom.

In a preferred aspect of the invention, when one or more specified nonionic surfactants or surfactants (described below) are added to remove grease and oil, the nonionic surfactant or surfactants may act as processing aids, thus reducing the amount of processing aid required, or even eliminating the need for it altogether.

Some compounds which are peroxy compound Akt activators themselves, such as methyl o-acetoxybenzoate, polyazelaic acid polyanhydride having a molecular weight of 1,000 to 2,000 and succinic acid dinitrile, have the necessary properties as processing aids and can be used as such. Paraffin-free can also be used to a small extent. When the process aid ·> L La «* i oi.» any other effect in the product, such as 64395 27 as a surfactant component of a degreasing surfactant mixture, its amount in the mixture is such that the weight ratio of activator to process aid is in the range of 20: 1-1: 3, the latter value for economic reasons. However, the weight ratio of activator to process aid may be as low as 1:10 when the process aid has other functional properties such as surfactant properties. A further class of materials useful as process aids are polyacrylamides with a molecular weight of> 500,000, which are thixotropic water-soluble polymers that can retain water in the solid state. The organic peroxy compound activator can be dissolved or dispersed in the aqueous mixture of polymer. The mixture is then added to the carrier fabric and precipitated to impregnate / coat the carrier, after which it cures into a solid yet water-soluble gel. This particular class of substances is particularly valuable in the application of organic peroxy compound Akti carriers to water-soluble carriers such as polyvinyl alcohols, which tend to lose their water solubility when exposed to higher temperatures.

As indicated above, the organic excipient may act as a release agent to facilitate the release of activators from the carrier when the product is added to the wash liquor. Process aids are generally also suitable as release aids, but some substances, most notably C8-C4 fatty acids and polyethylene glycols with a molecular weight of 4,000-6,000, are particularly effective when used to such an extent that the weight of the activators and release agent is 20% by weight. : 1 to 1: 2, especially 4: 1 to 1: 1. The benefits of the release aid are most clearly seen with water-insoluble activators such as 2,2-di- (4-hydroxylenyl) -propane diacetate.

A further type of release aid is one that is applied to the carrier either during the preparation of the carrier or before the carrier is loaded with the activator and other ingredients.

Excipients of this type are usually fluorocarbon or silicone polymers which are suitable for modifying the surface properties of the carrier so as to facilitate the release of the active ingredients after contact with water. Hydrofluorocarbon 28 64395 treatment solutions, products FC 807 and 808, manufactured by 3M-Company, Minneapolis, Minnesota, promote release when used to such an extent that the weight ratio of carrier to solid fluorocarbon is in the range of 500: 1 to 50: 1, mainly about 300: 1.

In addition to the optional ingredients mentioned above, which are important primarily for adding and releasing the activator to the carrier, surfactant ingredients of the carrier that are neither inorganic bleaches nor compounds that react with the activators may be added as a mixture with the activator. Thus, surfactants, foaming modifiers, chelating agents, anti-precipitating and dirt suspending agents, optical brighteners, bactericides, anti-fading agents, enzymatic agents, fabric softeners, antistatic agents, perfumes and bleaches can be added to this invention. using additional products, taking into account the constraints imposed on the applicant.

The surfactant may be any one or more surfactants selected from the classes of anionic, nonionic, zwitterionic, amphoteric and cationic surfactants and mixtures thereof. Anionic surfactants may be of natural or synthetic origin; the nonionic surfactants may be of the semi-polar or alkylene oxide type, and the cationic surfactants may be amine salts, quaternary nitrogen and phosphorus compounds, and ternary sulfonium compounds. Specific examples of each of these classes of compounds are set forth in U.S. Patent No. 3,929,678 to Laughlin & Heuring, issued December 30, 1975.

However, it has been found that the detergent additive products prepared in accordance with this invention are particularly suitable for the addition of non-ionic surfactants useful for removing grease and oil stains. Typical nonionic surfactants of this tend to be difficult to mix with conventional detergents due to their physical properties. The spray-drying of granular detergents containing nonionic surfactants has caused degassing problems during manufacture because, due to some of the elionic structures and granular detergents formed therein, the background properties tend to be less than satisfactory.

By mixing such nonionic agents with the additive products of the present invention, they can be utilized in a wash liquor without compromising the assembly or handling of conventional detergent granules, and the advantage of further pretreating oil and grease stains by direct application of the additive product to the stains.

In a preferred aspect of the invention, the detergent additive product therefore contains at least one nonionic surfactant having an HLB in the range of 8.0-17.0, most preferably 9.5-15.5 and selected from the group consisting of condensation products of ethylene oxide with a hydrophobic with an organic molecule containing reactive hydrogen.

Hydrophilicity-lipophilicity balance, or HLB, is a widely accepted measure of surfactant polarity and its relative affinity for an aqueous medium or hydrocarbon medium. The concept, originally developed by W.C. Griffin (J. Soc. Cosmetic Chemists 1 (1949) 311 allows numerical values to be given for surfactants, the scale being such that the hydrophilicity increases with increasing HLB value. For ethylene oxide-containing nonionic surfactants, the HLB value can be expressed as HLB = E / 5, where E corresponds to the percentage by weight of ethylene oxide in the compound.

Organic molecules having the desired hydrophobicity and having a reactive hydrogen atom include straight and side chain primary and secondary aliphatic C 1 -C 4 alkyl alcohols, C 12 -C 4 alkyl phenols.

Examples of suitable nonionic surfactants are: straight chain C 1 -C 6 alcohol (E ~) 10 ° C. -C-, r-alcohol (E-) J.4 ib s C, ,, - C, «-alcohol (Er) 11 1 o u

Cn-C. .alcohol (L.) 9 li b side-chain C 1-4 C 1-4 alcohol (E 2) straight-chain sC, η-C 1-4 alcohol (E,) sC -C 1-6 Alcohol (Lu) coconut fatty acid (L 2) oleic fatty acid (LL) straight chain C 1-6 alkylphenol (Lg) 30 64395

C 1-4 alkylphenol (Eg)

C 1-4 alkylphenol (Eg)

C8-alkylphenol (Eg) sorbitan monooleate (E, -) sorbitan trioleate (Egg) sorbitan monostearate (Eg) sorbitan tristearate (E ^ g).

Particularly preferred substances are primary straight-chain and side-chain primary alcohol ethoxylates having 7 to 20 ethylene oxide groups per mole of alcohol / such as (-3.4 to 15-straight chain alcohols condensed with 7 to 15 moles of ethylene oxide prepared by Shell Oil Co. under the trademark "Neodol" and C ^ gC ^ ^ g side chain alcohols manufactured by Liquichimica SA under the trademark "Lial".

The amount of the nonionic surfactant mixture is such that the weight ratio of nonionic surfactant to carrier is in the range of 20: 1 to 1: 5, preferably between 10: 1 and 1: 2, and preferably between 5: 1 - 1: 1. In preferred embodiments, when using nonwoven sheet carriers having a planar area of 2 to about 645 cm and a basis weight of the sheet of about 3 grams, the amount of nonionic surfactant applied thereto is in the range of 5 to 15 grams per sheet.

When the nonionic surfactant is a liquid at normal temperature, its physical mixing can occur in several ways. When the carrier is a non-plate-shaped fungal body, the body can be impregnated directly, either with the surfactant alone or in combination with the other components of the formulation mixture, using methods known in the art, which are described in more detail below. When the carrier is a nonwoven material or a piece in the form of a foamed sheet, it is recommended that the Pirita active material be mixed with a combinatorial non-hygroscopic material having a higher melting point, such as the processing aids described above, to obtain a waxy solid with a surfactant. the substance is in the form of a solid solution and / or as a dispersed phase. Due to their melting point range and waxy nature, polyethylene glycols with a molecular weight of UUIJO are suitable for this purpose, although due to their hygroscopicity under extremely humid conditions, it results in very high moisture binding if such glycols are used in significant amounts. Other useful materials include C 1 -C 4 fatty acid alkanolamides. However, the preferred substances are higher fatty acids, in particular C 1-4 saturated fatty acids, which are used in such an amount that the weight ratio of fatty acid to nonionic component of the surfactant is in the range of 1: 5 to 4: 1, mainly between 1: 3 and 3: 2 and preferably between 2: 3 and 1: 1.

When the surfactant is solid at normal temperature but melts at a temperature of less than about 100 ° C, most preferably less than about 80 ° C, the surfactant itself can be used as a medium for adding other non-liquid components to the carrier. Examples of this type of surfactant are richly ethoxylated nonionic compounds such as tallow alcohol or primary N-alcohol (E1).

Other optional ingredients include foaming agents, which may be of the foaming enhancing, foaming stabilizing, or foaming-reducing type. Examples of the first type are C 1 -C 6 fatty acid amides Da alkanolamides; examples of the second type are C 1 -C 4 alkyl-di-smallalkylamine oxides and of the third type are C 2 -C 6 -C 1-4 fatty acids, certain ethylene oxide-propylene oxide copolymers such as the "Pluronic" series, silicones, silica-silicone mixtures, microcrystalline waxes, and any mixtures of the foregoing.

Preferred antifoaming additives are described in U.S. Patent 3,933,672, issued January 2, 1976 to Barlotta et al., Which are incorporated herein by reference, which are related to antifoaming silicone. Representative of the silicon compound may be alkylated polysiloxanes such as silica aerogels and xerogels and various types of hydrophobic silicas. The silicone material can be described by a siloxane having the formula: (wherein X is from about 20 to about 2,000, and R and R 'are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl and phenyl Polydimethylsiloxanes (R and R 'are methyls) having a molecular weight in the range of about 200 to about 200,000 and above are all useful as foaming control agents.Other suitable silicone materials in which the side chain groups R and R' are alkyl, aryl, or alkyl and aryl hydrocarbyl mixed groups are useful foaming control properties Examples of such materials include diethyl, acropyl, dibutyl, methyl, ethyl, phenylmethyl, polysiloxanes, and the like, with other useful controls being silicone types. a mixture of the alkylated siloxane referred to above and solid silica may be used as such. by attaching silicone to the surface of solid silica. The preferred silicone-based foam control agent is hydrophobic silanized (preferably trimethylsilacinated) silica having a particle size in the range of about 10 millimicrons to 20 millimicrons and a specific surface area greater than about 50 m 2 / g, thoroughly mixed with about 500 millimeters of dimethylsilicone liquid. about 200,000, with a weight ratio of silicone to silanized silica ranging from about 19: 1 to about 1: 2. The silicone-containing antifoam agent is most preferably added as a release agent to a water-soluble or water-dispersible, substantially non-surfactant detergent-impermeable carrier.

Particularly useful antifoaming agents are the self-emulsifying silicone-based antifoaming agents described in U.S. Patent No. 4,075,118.

An example of such a compound is DB-544, manufactured by Dow Corning as a technical product, which is a siloxane / glycol copolymer.

The foaming modifiers described above are added up to about 5% by weight, mainly 0.1-2% by weight of the mixture of cationic and nonionic surfactants.

Chelating agents which may be added include citric acid, nitrilotriacetic and ethylenediaminetetraacetic acids and their salts, organic phosphonate derivatives 64395 33 such as the compounds disclosed by Diehl, in U.S. Patent No. 3,213,030, issued October 19, 1965. , Roy, U.S. Patent No. 3,433,021, issued January 14, 1968,

Gedge, U.S. Patent No. 3,292,121, issued January 9, 1968, Bersworth, U.S. Patent No. 2,599,807, issued June 10, 1952, and carboxylic acid excipients, such as those disclosed in Diehl. In U.S. Patent No. 3,308,067, J

published March 7, 1967.

The primary chelating agents are nitrilotriacetic acid (NTA), nitrilotrimethylene phosphonic acid (NTMP), ethylenediaminetetramethylenephosphonic acid (EDTMP) and diethylenetriamine pentamethylenephosphonic acid (DETPMP), and , mainly 5: 1 to 1: 5 and most preferably 3: 1 to 1: 1.

Some polybasic acids have been found to enhance the bleaching effect of the organic peroxyacids formed when the products of this invention are used with a conventional detergent composition, such as EDTMP, NTMP and DETPMP. However, not all chelating polybasic acids are useful in this regard, with certain weakly chelating polybasic acids, most notably amber, and glutaric acid proving to be effective.

A wide variety of fabric softeners and antistatic agents can be included among the optional compounds. Examples of cationic nitrogen compounds are di-C1- (C1-C18-alkyl), di-CE-C1-6-alkyl quaternary ammonium salts, imidazolinium salts and, for non-nitrogenous substances, sorbitan esters of C1-6-C1-6 fatty acids, and the primary fabric softener and antiseptic suitable for addition to the additive formulations of this invention is described in U.S. Patent No. 3,936,537 to R. Baskerville & FG Schiron, issued February 3, 1976. No. 3,936,537 of this type, issued February 3, 1976. described in DE-A-2 516 104, published October 30, 1975.

The primary enzymatic agents are technically available amylases, and neutral and time-consuming proteases, which are usually added to detergent mixtures. Due to their heat sensitivity, these substances require that the addition takes place at or near room temperature 31 * 64395 and thus addition to the melt of activator and other additives is not possible. Accordingly, enzymatic agents are best used in methods in which the activator is applied to a support using a solvent or slurry.

Optical brighteners may be of the anionic or non-ionic type and are added in an amount of 0.05 to 1.0 grams per plate, preferably 0.1 to 0.5 grams per plate. Preferred examples are anionic agents available under the tradenames "Tinopa EMS" from Ciba Geigy S.A. and Blankophor MBBN, available from Farbenfabrik Bayer AG.

Catalysts used herein include products that improve bleach efficiency, such as certain salts of transition element metals, such as those disclosed in U.S. Patent No. 3,532,634 to Wood.

The compositions mentioned herein contain the activator in a water-releasing combination with a solid, non-particulate carrier. The carrier is mainly absorbent and the activator is absorbed therein. Activator application can be performed in any conventional manner, and several methods are known in the art. The activator may, for example, be sprayed in liquid form onto the carrier as it is prepared. When the activator is in liquid form, this may be in the form of a melt, and it is highly recommended that Akti activators melt at a lower temperature than where they decompose on heating. Alternatively, when the activator is solid at normal temperature, liquid forms such as solutions in organic solvents which evaporate after application and slurries or suspensions in which the finely divided solid is in water or other liquid medium may be used.

As previously mentioned, inorganic peroxy bleaches and other substances reactive with organic peroxy compound activators may be added to the additive formulations of this invention provided that the activator and bleach are spatially separated.

In those embodiments of the patent in which the activator and the inorganic peroxygen bleach are added to the same carrier at physically separate sites, a convenient method of application is to precipitate the corresponding melts, suspensions or solutions on the carrier as separate strips. The bleach is mainly applied as a dispersion of solid ingredients in a molten process aid (as described above) at a temperature in the range of HC ° -60 ° C. Using this technique, a pressure ratio of bleach to carrier of up to 15: 1 can be obtained. This load is achievable with cellular carriers, but for fibrous carriers of this type the weight ratio is in practice limited to about 5: 1. In addition, the load limitations on the absorbency of the carrier surface area required to add the activator may limit the amount of bleach to less than 6: 1. Provision must also be made for the bleaching strips or areas and the corresponding activating strips or areas to separate during transport and / or storage. This is possible by placing layers of material between the carrier layers or by forming patterns of the material to be precipitated which do not simultaneously accumulate on the carrier.

When the support is impregnated, it is believed that the surfaces of the pores or fibers forming the support are also coated, and a highly desirable aspect in view of the support is that this allows a thorough coating of the peroxy compound activator to be formed. The term "coating" means applying one support to the surface of another; "impregnation" is intended to mean that penetration occurs throughout the support structure, both inside and outside. One factor that affects the absorption capacity of a particular carrier is the free space it contains. Accordingly, when applied to an absorbent carrier, the activator penetrates the free space and is therefore considered impregnated. In a low absorbency carrier, such as a single ply kraft or bond paper, the free space is limited; such a plaintiff is therefore referred to as "close". Thus, when a small portion of the carrier penetrates the tight limited available free space of the carrier, the majority of the remaining activator does not penetrate and remains on the surface of the carrier, so this is considered to be coated.

In one method of preparing an activator-impregnated sheet-like support, the activator is applied to an absorbent paper or nonwoven fabric by a method commonly referred to as filling. The activator is applied to the support mainly in liquid form and the activators which are normally solid at room temperature must first be melted and / or treated as a solvent. Methods of melting the activator and / or treating the activator as a solvent are known and are readily performed to provide a satisfactorily treated support.

In this method, the activator in liquid form is placed in a kettle or trough that can be heated, if necessary, to keep the activator in liquid form. Any desired additive is then added to the liquid activator. The apparatus then forms a roll of absorbent carrier so that it can be released freely. As the carrier discharges from the roll, it travels downwards and, while submerged, passes through a boiler or trough with a liquid activator at such a slow rate that sufficient impregnation is possible. The impregnated carrier then travels at the same speed upward and through a pair of rollers that squeeze out excess bath fluid. The impregnated support is then cooled to room temperature, after which it can be folded, cut or perforated into pieces of the same length, and then packaged and / or used.

The rolls used are similar to "press rolls" used in the paper or papermaking industry; they can be made of hard rubber or steel. The rollers are essentially adjustable so that the gap between their opposing surfaces can be adjusted to control the amount of activator fluid applied to the carrier.

In a preferred embodiment of the invention, the activator in liquid form is injected onto the absorbent carrier as it opens. The opened carrier tissue is arranged to slide on top of a syringe nozzle formed by a horizontally positioned tube formed into a slit extending over its upper surface. The molten organic peroxy compound activator and any additives mixed therein are pressed through the gap onto the support and the excess liquid is then pressed out using press rolls. The melt temperature used is in the range of 40 ° -80 ° C, mainly between 4-5 ° "65 ° C and the viscosity of the molten substance must be less than 5000 centipoise at 50 ° C, mainly not more than 500 centipoise.

Other variations include the use of metallic "wedge" rolls with an activator sprayed onto the front or feed surfaces, 37 64395, which allows the absorbent paper to be treated, usually on one side only, just before it gets between the rolls where excess liquid is squeezed out. This variation further allows the use of metal rollers that can be heated to keep the activator in the liquid phase. A further method involves the individual layers of multilayer paper, the number of which may be a separate treatment of the desired size, and the subsequent joining of the layers with a known bonding adhesive mixture; thus a composition is obtained, the second outer side of which can be treated, but which nevertheless has several other layers, each surface of which has been treated.

In the preferred method of preparing the products of this invention, a mixture of molten activator and any additive is applied to the carrier. In order to obtain a mixture with suitable properties, i. in order to solidify over a wide range of temperatures in order to form a waxy rather than a crystalline solid, some activators suitable for the purposes of the invention must be mixed with a plasticizer or thickener. For this purpose, Peroxy Compound Activators can be divided into three groups of different types of substances, namely: (a) substances which are liquids at temperatures up to 25 ° C or which are solid, melting between 25 ° C and 40 ° C; is between 40 ° C and 95 ° C, (c) solids with a melting point above 95 ° C.

For the group of high melting point substances, it is recommended that the melting point be lower than 150 ° C, although substances with a melting point up to 250 ° C may be treated as a dispersion in the melt of another substance. Of course, it should be noted that the organic peroxy compound activator must not decompose to a significant extent at temperatures below its melting point.

The table below shows the melting points of several peroxyacid activators suitable for use in the present invention: 38 64395 __Substance Sand_N-acetylcaprolactam liquid N-methyldiacetamide liquid acetic anhydride liquid benzoylimidazole liquid ethyl-o-acetoxybenzoxy

benzyl o-acetoxybenzoate 2 5 ° C

benzoic anhydride 40 ° C

methyl o-acetoxybenzoate 49 ° C

p-acetoxy-acetophenone 52 ° C

polyazelaine polyanhydride 5 5 ° C

meripinic acid dinitrile 55 ° C

tetraacetylhexamethylenediamine 59 ° C

2,2-di- (4-hydroxyphenyl) propane diacetate 79 ° C

1-cyclohexyl, 3-acetylhydantoin 86 ° C

tetraacetylmethylenediamine 94-4 ° C

phenyl o-acetoxybenzoate 97 ° C

N-acetylimidazole 102 ° C

diacetyldimethylglyoxime 112 ° C

triacetylguanidine 112 ° C

O-acetoxybenzoic acid 135 ° C

1-phenyl-3-acetylhydantoin 14 7 ° C

tetraacetylethylenediamine 14 8 ° C

tetraacetylglycouril 237 ° C

sodium acetylphenol sulfonate very high.

Liquid and low melting point peroxy compound activators require a higher melting water-soluble or dispersible organic excipient with a higher melting point range than where it softens and melts. The purpose of this excipient is to allow a mixture with the desired viscosity / temperature properties to be obtained. As previously mentioned, such a substance must also be non-hygroscopic in nature. examples of such substances are polyvinylpyrrolidone having a molecular weight of 44,000 to 700,000 and polyazelin polyanhydride (itself an activator) having a molecular weight of 1,000 to 2,000 and polyethylene glycols having a molecular weight greater than 39,6395 to about 4,000. Other useful substances include sorbitan esters of fatty acids such as myristic, stearic and arachidic acids and non-hygroscopic ethoxylated tallow alcohol derivatives.

The amount of high melting point processing aid used will, of course, depend on the amount of peroxy compound activator used, its melting point and its solubility in the excipient. The weight ratio of excipient to activator may be 10: 1, although obstacles due to the type of carrier used may limit the allowable load on the carrier to be less than this value.

High melting point peroxy compound activators require an excipient that lowers the melting point of the mixture to the desired range, i. between 40 ° C and 80 ° C, mainly between 45 ° C and 65 ° C. The excipient must be non-hygroscopic and the activator must dissolve in the excipient or be able to form a permanent dispersion with it. A mixture in which part of the activator is dissolved and the rest is dispersed in suspension is completely satisfactory. Capable of doing so are the substances mentioned above in combination with C12-C20 fatty waxes and some of their water-soluble and water-dispersible esters.

As indicated above, the weight ratio of excipient to activator may be up to 10: 1, but may be limited to less than this value due to obstacles due to the loading of the carrier.

For activators that melt within the optimum range, i. between 40 ° C and 80 ° C, the inorganic excipient is not necessarily required as a processing aid in the primary process for the manufacture of the products according to the present invention. Such agents can be melted and applied directly to the carrier, and can themselves be used as carriers for other components of the products, such as solid, chelating agents, or liquid nonionic surfactants. Still, excipients of a waxy nature may still be used to rationalize the treatment, e.g., to reduce dust to ensure rapid release and dissolution of the activator in the aqueous medium, and / or to modify the surface properties of the treated support.

In use, the additional products of this invention are added to the wash liquor at the point in the washing process where the formation of the organic perox bleach - ° 64395 is most significant. Optimal results are obtained in practice, regardless of the washing cycle used, when the additive preparations of this invention are fed to the machine at the same time as the fabrics. For machines where the program includes a prewash phase, it is recommended to add the additive preparation at the beginning of the main wash phase.

The invention is described in the following exemplary embodiments of the invention, in which parts and percentages are parts by weight and percentages by weight unless otherwise stated. Reference herein to a test method for determining the effectiveness of a peroxy compound activator in forming an organic peroxy bleach relates to the method set forth below.

Activator perhydrolysis test 1 mmol of peroxy compound activator * is added to a stirred solution of sodium perborate tetrahydrate (0.9 g), sodium pyrophosphate decahydrate (1.25 g), EDTA (35 ppm) and 0.25 g of sodium tetrapropylene benzene perbenzate benzene benzene and maintained at 25 ° C by means of a circulating water bath and stirred mechanically.

ίί) *

My water-soluble activation can be added directly.

Other substances may first be dissolved in 10 ml of a suitable solvent which does not react with the substances present, e.g. 1,4-dioxane. In such cases, the amount of distilled water must be reduced to 4 to 90 ml.

Within twenty minutes of the addition of the activator, at least one 10 ml sample is taken from the mixture and each sample is added to a mixture of crushed ice from distilled water and distilled water (100 g) and glacial acetic acid (15 ml). Potassium iodide (0.05 g) is added and the mixture is immediately diluted with 0.01 molar sodium thiosulphate solution using an iodine indicator (‘Iotect’, manufactured by British Drug Houses Limited) to the first endpoint (blue / black-► colorless). Activators with a required titer greater than 2 ml of 0.01 molar sodium thiosulfate are preferred agents for the purposes of this invention.

64395

Example 1

Methyl o-acetoxybenzoate (MOAB) (m.p. 49 ° C) was melted and maintained at 60 ° C. A roll of randomly assembled regenerated cellulose fibers, 3 denier thick, bonded with a polyvinyl acetate binder (70% cellulose, 30% solid binder) was used to make a carrier sheet / * 2 3 cm x 28 cm (9 "x 11") _ 7 with a basis weight was 1.9 g / plate.

The support was impregnated by immersion in the melt and excess activator was removed by passing the plate through a pair of rollers, one of which was rubberized and the other of which was heated and made of stainless steel. The plate was then cooled to solidify the activator and weighed and found to weigh 6.0 g / plate, i.e. the weight ratio of activator to carrier was 3.1: 1. The plate felt rumbling and could be easily formed into a roll with a diameter of M-cm.

Plates prepared according to the above example were used in an experiment comparing the bleaching performance of the three products. The three products were: A. Commercially available granular detergent with 28% sodium perborate.

B. 'Normal' low temperature bleach washing preparation with mixture A, of which 10% sodium perborate has been replaced by 6% commercially available organic peroxy compound activator and 4% sodium sulphate.

C. Mixture A in the plate of Example 1.

Each product was added to a washing machine with 1.8 kg of dirty clothes in 30 liters of water with a hardness of 18 Clark degrees to give a product concentration of 0.50%. Based on this, 9 grams of activator was added to product B, and 6.0 g of MOAB was compared on a plate added with product C.

Fabrics made of white cotton and polyester-cotton blend (50/50) were soiled with wine and tea stains and the soiled fabrics were added to the machines and washed using each recipe mixture at 40 ° C and 60 ° C, respectively, for 15 and 25 minutes. In each experiment, both mixtures B and C produced significantly better dirt removal than mixture A, and mixture C did not differ significantly from mixture B.

1.2 64395 This result shows that the additive preparation of the present invention, when added to a conventional washing liquid, provides a bleaching effect equivalent to that of a detergent mixture containing an inorganic peroxygen bleach and a normal organic peroxygen bleach activator. Moreover, this bleaching effect is achieved without the appearance of point color fading points associated with the use of granular organic peroxygen bleach products.

Results comparable to the bleaching results obtained with the above-mentioned product C are obtained when using plates in which methyl o-acetoxybenzoate has been replaced by benzoic anhydride, phenylbenzoate or maleic anhydride.

Example 2

A methyl-o-acetoxybenzoate melt was prepared and applied using the technique of Example 1 to a support consisting of 100% non-bleached, randomly assembled synthetic silk fibers having a thickness of 5.5 denier and bonded with an ethyl acrylate binder (Rhoplex HA8). (70% fibers, 30% binder) to give a basis weight of 1.55 grams per plate / 23cm x 28cm (9 "x 11"). After the excess melt was removed from the support and allowed to cool, the amount of activator was found to be 3.9 g, i.e. the weight ratio of activator to carrier was 2.5: 1. The record felt rattling.

A satisfactory product is obtained when the synthetic silk fiber carrier is replaced by a hydrophilic polyurethane foam sheet made of "Hydrofoam" (registered trademark) having a density of 0.036 g / cm and a cell number of 24-31 cells / cm.

Example 3 At 70 ° C, a melt was prepared consisting of a mixture of 50% o-acetoxybenzoic acid (m.p. 135 ° C) in 5 ° C myristic acid. The melt was applied using the method of Example 1 to a nonwoven support of 100% unbleached, randomly assembled artificial silk fibers with a thickness of 3.0 denier bound with ethyl acrylate binder (Rhople HA8) (70% fibers, 90% binder), whereby the basis weight was 1.6 g / plate. After cooling, the amount of melt was found to be 5 g per plate, thus the ratio of activator to support was 1.6: 1. The treated plate was smooth and flexible.

4 3 64395

Products with satisfactory properties are obtained when the melt is formed from a dispersion of 50% phenyl-o-acetoxybenzoate in 50% polyethylene glycol 6000; 40% diacetyldimethylglyoxime, 60% polyethylene glycol 6000; 75% tetraacetylmethylenediamine, 25% polyvinylpyrrolidone having a molecular weight of 700,000; 40% o-acetoxybenzoic acid, 60% myristic acid; 30% tetraacetylglycouril, 70% myristic acid; 60% phthalic anhydride, 40% polyazelaic polyanhydride having a molecular weight of 1500. Bleaching properties equivalent to the product C of Example 1 are obtained when using sheets in a washing liquid containing a detergent containing sodium perborate or percarbonate.

Example 4

A mixture of 85% methyl o-acetoxybenzoate and 15% polyethylene glycol 6000 was prepared and melted at 60 ° C. The melt was pumped into a nozzle of the press, the orifice of which extended horizontally laterally under the moving carrier material of Example 2, which was unscrewed at a speed of 24.4 m / min. The melt was compressed from the mouthpiece so that the support could be impregnated over its entire width, and the spread of the molten material was further aided by guiding the treated support between a pair of rollers placed downstream immediately after the nozzle. The treated support tissue was cooled by passing it over additional cooling rolls before being collected on a storage roll and removed from the section and

O

for packaging. 0.064 m per plate area was filled to 6.1 g, i.e. the ratio of activator to carrier was 3.3: 1.

A satisfactory product is obtained when the activator charge is added to 13.2 g, i.e. the ratio of activator to carrier is increased to 8.5: 1. A smooth waxy product is also obtained with a melt with a total weight of 7 g of a mixture of 10% MOAB and 90% sorbitan monostearate, i.e. the ratio of activator to carrier is 1: 2.2 and the ratio of activator to excipient is 1: 9. Comparable results are obtained when methyl o-acetoxybenzoate is replaced by succinic dinitrile, maleic anhydride or polyazelaic acid polyanhydride.

Satisfactory products are also obtained when the sorbitan monostearate is replaced by a mixture of 60% tallow alcohol condensed with 30 moles of ethylene oxide, 20% dithalyldimethylammonium chloride and 20% sorbitan monostearate.

Example 5

Otherwise, the same procedure as in Example 4 was followed, but the melt contained a mixture of 86.5% methyl o-acetoxybenzoate and 13.5% myristic acid. The filling was 6.6 g / 0.064 m, from which the ratio of activator to carrier was 3.1: 1.

The fabric felt smooth and waxy and was very flexible.

Example 6

The procedure of Example 5 was otherwise followed, but the melt contained a mixture of 86.5% methyl o-acetoxybenzoate 2 and 13.5% myristic acid. The filling was 6.6 g / 0.064 m giving an activator to carrier ratio of 2.6: 1; and the product is flexible.

Addition of 0.5% succinic acid granules to the above melt gives a product with a smoother tissue surface. The methyl-o-acetoxybenzoate-myristic acid melt is replaced with a melt of 25% N-acetylcaprolatam and 75% myristic acid (solid at 40 ° C) to give a smooth waxy product containing the same amount of melt.

Example 7

Otherwise, the procedure of Example 3 was followed, but the myristic acid was replaced with a mixture of equal parts of sorbitan monostearate and polyethylene glycol 6000. A smooth flexible sheet preparation with 5 grams of melt per sheet, i. the ratio of activator to carrier was 1.6: 1.

Similar results were obtained by replacing 4.5 parts of the myristic acid of Example 3 with 4.5 parts of paraffin wax having a melting point of 55 ° C.

Example 8

A mixture of 95% methyl o-acetoxybenzoate and 5% polyvinylpyrrolidone having a molecular weight of 700,000 was melted to give a liquid having a viscosity at 60 ° C of about 170 centipoise. To this mixture was added 0.1% by weight of perfume and kept melted at 60-70 ° C in an electrically heated bath. The carrier fabric was arranged to run continuously so that the fold of the roll 45 64395 was directed to impregnate the fabric down into the bath and then up from the bath, whereby the fabric was pulled through the bath by a pair of adjustable tension rollers placed above the bath. One roll was rubberized and the other was made of stainless steel and had to be heated.

The carrier was a nonwoven 100% regenerated cellulose fabric made of 3 denier thick fibers and bonded with polyvinyl acetate (70% fibers, 30% binder) to give a basis weight of 1.55 grams / 0.065 m. The fabric thickness was 0.127 mm.

At a hot roll temperature of 55-70 ° C and a tissue feed rate of 1 meter / minute, a plate-like product with a filling of 6 g of 0.064 m, i.e. the ratio of activator to carrier was 3, -7: 1. After cooling, the plate-like product felt smooth and flexible in the hands.

Example 9

A mixture of 75 parts of benzoic anhydride (BAN), m.p. 40 ° C, and 25 parts of tetraacetylglycouril (TAGU) (m.p. 237 ° C) were stirred and heated to 60 ° C to form a molten dispersion in which BAN formed a continuous phase. The mixture was then passed through a Premier '84 * colloid mill (manufactured by Premier Colloid Mills Ltd, Walton-on-Thames, Surrey England) to produce a product flow with a particle size of less than 50 as determined by microscopic examination of the product. The finely divided dispersion was fed into a trough formed by a horizontal gap of a pair of transport rollers, which rolls were heated to keep the dispersion molten. 25.4 cm wide roll made by randomly assembling regenerated cellulose fibers with a thickness of 3 denier and bonding with a polyvinyl acetate binder (70% cellulose, 30% solid 2 binder) and a basis weight of 1 , 55 g / 0.065 m, was impregnated by feeding downwards through the melt and into the tightening gap.

As the plate passed through the tightening gap, any excess activator mixture was removed from the carrier roll, which was then cooled to solidify the activator, cut into 64.5 2 cm plates, and weighed. Each plate was found to be filled with 8.0 g (46 64395 i.e. the weight ratio of activator to carrier was 3: 1). The plates felt smooth. The detergent additive preparation prepared by the above method was tested as follows.

Three separate 3.6 ka bundles of dirty fabrics, including shirts and underwear, were washed at 60 ° C in 20 liters of water with a hardness of 18 ° H (molar ratio Ca: Mg = 5: 1) using a technically available detergent, with 25% sodium perborate bleach at a concentration of 0.7% in the wash liquor. Each bundle contained strips of colored fabrics known to be bleach-sensitive. An additive preparation plate described above was added to one washing liquid, a similar plate containing 6 g of BAN alone was added to the second washing liquid, and a third liquid served as a control liquid to which no additive preparation was added.

Examination of visually washed and dried, bleach-sensitive colored strips gave the following results, the relative color difference between the washed strip and the unwashed strip being indicated on a scale of 1 to 10.

On this scale, 10 means complete loss of color, 1 means no color difference, control 2 control + 6 g BAN 8 control + 6 g BAN + 2 g TAGU 3.

It can be seen that the addition of a rapidly perhydrolysing peracetic acid activator significantly reduces the tendency of the bleach-sensitive colors to fade than the berpentose acid bleach additive used in the treatment. Similar results are obtained if benzoic anhydride is replaced by N-benzoylbenzimidazole, N-benzoylimidazole, phenylbenzoate, m-chlorophenylbenzoate or N, N-dibenzoylaniline. Similar results are obtained if tetraacetylglycouryl is replaced by methyl o-acetoxybenzoate, tetraacetylmethylenediamine, N-acetylcaproactam, sodium p-acetoxybenzenesulfonate or diacetyldimethylglyoxime.

Example 10 Preparation of 2,2-di- (4-hydroxyphenyl) propane diacetate 228 g (1 mole) of 2,2-di- (4-hydroxyphenyl) propane * 7 64395 (Bisphenol A, manufactured by Shell Chemical Co., Manchester, England) was dissolved at 20 ° C in a liter of glacial acetic acid. To the solution was added 1 ml of 98% sulfuric acid, and 255 g (2.5 moles) of acetic anhydride were added slowly over 30 minutes with stirring. At the end of the addition, the product was poured into excess water and the resulting precipitate was filtered, washed with water and dried. The product had a melting point of 79-80 ° C and a peak in the IR spectrum at a wavelength of 1750 cm -1, which is typical of the acetyl group. NMR spectroscopic examination showed the presence of two acetyl groups.

The previously described perhydrolysis test was performed using 0.228 g (1 mmol) of the above product and the titre of a sample taken 5 minutes after the addition of the activator to the sodium perborate solution was 3.9 ml of 0.1 norm sodium thiosulfate solution.

100 g of Bsiphenol A diacetate prepared as described above and 100 g of polyethylene glycol 6000 were mixed and heated to about 90 ° C to form a melt. This was then applied to a support plate made of regenerated cellulose with a basis weight of 1.65 g using the technique of Example 9 to give a fill of 11.0 g, i. the ratio of activator to carrier was 3.33: 1.

The Bisphenol A diacetate of the above example is replaced by a 50:50 mixture of Bisphenol A diacetate and N-benzoyl imidazole (m.p. 202 ° C) which is treated as a melt dispersion for comminution in a Premier colloid mill to a particle size of less than 50%. , u before it is applied to the carrier. An equivalent product is obtained.

In the example above, similar results are obtained if polyethylene glycol 6000 is replaced by stearic acid, with tallow alcohol condensed with 25 moles of ethylene oxide or a mixture thereof.

Example 11 50 parts of tetraacetylethylenediamine (m.p. 148 ° C, 10 parts of benzoic anhydride (m.p. 90 ° C) and 90 parts of stearic acid (m.p. 69 ° C) are formed by first melting stearic acid and benzoic anhydride together at 75 ° C. Following the procedure of Example 9, a sheet product with a fill of 10 g / 0.065 m is prepared with a ratio of 64395 activator to carrier and 1: 5 perbenzoic acid to peracetic acid activators.

Example 12

The activator-processing aid mixture of Example 11 is applied to a hydrophilic polyurethane foam sheet having a density of about 0.036 g / cm 2 and a cell number of 24 to 31 cells / cm (Hydrofoam, manufactured by Scott Paper Co., Eddystone, Pennsylvania, USA). The basis weight of plate 2 is 2 g / 0.065 m and the weight ratio of activator to carrier is 5: 1, with a ratio of perbenzoic acid to peracetic acid activators of 1: 5.

Example 13

A weaving board (25.4 cm x 25.4 cm) containing 70% by weight of regenerated cellulose fibers and 30% by weight of ethyl acrylate binder and having a basis weight of 1.6 g / sheet was impregnated at 55 ° C with the mixture , containing 5 g of sodium para-acetoxybenzenesulfonate, 1 g of ethylenediaminetetramethylenephosphonic acid and 5 g of lauric acid, and adding the remaining ingredients to form a slurry in which the plate was then immersed. The impregnated plate was then guided between a pair of rollers to remove excess mixture. The filling was 11 g, i.e. the weight ratio of activator to carrier was 3.12: 1.

If sodium o-acetoxybenzenesulphonate is replaced by a 50:50 mixture of benzoic anhydride and methyl o-acetoxybenzoate or tetraacetylethylenediamine, Bisphenol A diacetate, 1,3,5-triacetyl-2,4,6-triazine, p- acetoxyacetophenone or diacetyldimethylglyoxime, an equivalent product is obtained.

If EDTMP is replaced by NTMP, succinic acid or diethylenetriaminopentamethylenephosphonic acid, similar results are obtained.

Example 14

Following the procedure of Example 13, a mixture of 5 g of Bisphenol A diacetate, 5 g of polyethylene glycol 6000 and 1 g of ethylenediaminetetramethylenephosphonic acid was followed and applied to a 25.4 cm x 25.4 cm regenerated cellulose plate carrier to give a base weight of 1.6 g. g / plate. The sheet product felt smooth and flexible in type.

49 64 3 9 5

Example 15

According to the present invention, detergent additive preparations A and B

prepared using the method of Example 13 as follows.

A B

EDTMP 1 g EDTHP 1.5 g TAED 4 g TAED 5 g

Stearic acid 2 g Lauric acid 3 g TAE g 5 2 g TAE25 3 g methyl vinyl ether maleic anhydride copolymer, molecular weight _ 250 000_1 g _ 9 g 13.5 g

Applicant: Applicant:

Nonwoven Regenerated Nonwoven Regenerated Cellulose Fibreboard made from cellulose is a fiberboard having a weight of 30 weight (1.5 denier) with 30% by weight of a% by weight of ethyl acrylate binder and ethyl acrylate binder. Basic weight 1.6 g / weight 3.25 g / 0.065 m.

0.065 m2.

In either case, a melt is prepared from the carboxylic acid and the alcohol ethoxylate, and the other ingredients are added thereto as a dispersion, after which the mixture is applied to a carrier.

Example 16 50 parts of tetraacetylhexamethylenediamine (TAHD) are melted at 70 ° C and mixed with 50 parts of Dobanlo (RTM) 45E15 and 10 parts of the sodium salt of ethylenediaminetetramethylenephosphonic acid. This mixture is used to isopregise a nonwoven fibrous support using the method of Example 4 to give a detergent additive composition having a composition of TAHD 5 g.

Dobanol 45E15 5 g EDTMP 1 g

Carrier 1.58 g (weight ratio of activator to carrier 7.1: 1).

so 64395

The carrier contains 100% unbleached, randomly assembled synthetic silk fibers with a thickness of 5.5 denier and bonded together with an ethyl acrylate binder (Rhoplex HA8) (70% fibers, 30% binder); so that the basic weight is 1.55 a / 0.065 m2.

The like product is obtained by using a carrier made of 100% unbleached randomly assembled artificial silk fibers of a thickness of 3,0 denier and a basis weight of 1,6 g / l.

0.065 m2.

An equivalent product is obtained if EDTMP is replaced by diethylenetriaminopentamethylenephosphonic acid (DETPMP) or nitrile trimethylenephosphonic acid (NTMP).

Example 17

A nonwoven board (30.5 cm x 25.4 cm) bonded with a polyester wood particle blend manufactured by Chicopee Manufacturing Co., Milltown, New Jersey, USA under the code name SK 650 WFX 577, having a basis weight of 50 g / square meter, was impregnated with a mixture of 5 g of TAED and 1 g of EDTMP dispersed in a mixture of 6 g of Dobanol 45E7 and 6 g of polyethylene glycol 6000 using the method of Example 4. The impregnated product was rigid enough to support itself from one corner when held in a horizontal position and felt smooth waxy.

Satisfactory product was also obtained when the support was replaced by a polyurethane foam sheet (22.9 cm x 10.2 cm) with a density of 20 kg / 3 m and a thickness of 3 mm with a product filling of 18 grams.

Products similar to the above are obtained if TAED is replaced by any of the following compounds: p-acetoxyacetophenone, 1,3,5-triacetyl-3,4,6-triazine, diacetyldimethylglyoxime, 2,2-di- (4-hydroxyphenyl) propanediacetate, tetra- acetylhexamethylenediamine, tetraacetylhydrazine, methyl o-acetoxy benzoate, tetraacetylglycouryl or N-acetylcaprolactam.

Similar results are obtained if polyethylene glycol 6000 is replaced by sorbitan tristearate.

Claims (29)

51 64395 A detergent additive preparation which can be used in aqueous washing solutions, characterized in that it consists of a flexible plate-like support with a non-particulate solid body coated and / or impregnated with a water-releasing (a) 0.1 to 30% by weight. with one part by weight of an organic peroxy compound activator per part by weight of the carrier, (b) 0-20 parts by weight of one or more treatment or release agents per part by weight of the carrier, (c) 0-5 parts by weight of an organic chelating agent per part by weight of the carrier per part by weight, and (d) 0 to 20 parts by weight of surfactant per part by weight of the carrier, and (e) if desired, with other conventional detergent components which do not react with the activator, Detergent additive preparation according to Claim 1, characterized in that the organic peroxy compound activator is such that, 20 minutes after it has been prepared, at 25 ° C, an aqueous solution containing 0.002 mol per liter of sodium perborate has a content of 1.8 g / liter. , sodium pyrophosphate 2.5 g / liter, sodium alkylbenzenesulfonate 0.5 g / liter and EDTA 35 ppm, 10 ml of this solution releases iodine from the acidified potassium iodide solution at 0 ° C so that. it requires at least 2.0 ml of 0.01 molar sodium thiosulphate solution to neutralize it, using starch as an indicator. Detergent additive preparation according to Claim 1 or 2, characterized in that the weight ratio of activator to carrier is in the range from 10: 1 to 1:10. Detergent additive preparation according to any one of Claims 1 to 3, characterized in that the weight ratio of activator to carrier is in the range from 8: 1 to 1: 2. Detergent additive preparation according to any one of Claims 1 to 4, characterized in that the organic peroxy compound activator is an anhydride, ester, imide or oxime. Detergent additive preparation according to Claim 5, characterized in that the peroxy compound activator is a mixture in which the weight ratio of peroxybenzoic acid to peroxyacetic acid activators is in the range from 1:10 to 10: 1, Detergent additive preparation according to Claim 6, characterized in that the peroxybenzoic acid activator and the peroxyacetic acid activator are present in a weight ratio in the range from 5: 1 to 1: 5. Detergent additive preparation according to Claim 5, characterized in that the organic peroxy compound activator is chosen from C 1 -C 6 aliphatic acyl imides, aryl acyl imides, their N-substituted derivatives, and aliphatic or aromatic mono- and dicarboxylic acids having a C 1 -C 8 alkyl group in the acyl radical or radicals. Detergent additive preparation according to Claim 8, characterized in that the melting point of the organic peroxy compound activator is in the range from 25 ° C to 150 ° C. Detergent additive preparation according to Claim 9, characterized in that the melting point of the organic peroxy compound activator is in the range from 0 ° C to 95 ° C. Detergent additive preparation according to any one of claims 1 to 10, characterized in that it contains one or more conventional active detergent components selected from the group consisting of foam modifiers, anti-settling agents and dirt suspending agents, fabric softeners and antistatic agents. substances, enzymes, perfumes, colorants, optical brighteners and bleach catalysts, the weight ratio of any such active ingredient to carrier not exceeding 20: 1. Detergent additive preparation according to any one of Claims 1 to 11, characterized in that the weight ratio of the total weight of the peroxy compound activator to components (b) to (e) is in the range from 500: 1 to 1:15. Detergent additive preparation according to Claims 11 and 12, characterized in that the surfactant is a condensation product of an alkylene oxide and an organic hydrophobic residue having a reactive hydrogen atom, the surfactant having an HLB value in the range from 8.0 to 17.0. , Detergent additive preparation according to Claim 13, characterized in that the nonionic surfactant is a substantially linear alcohol ethoxylate having 7 to 20 ethylene oxide groups per mole of alcohol, Detergent additive preparation according to any one of Claims 11 to 14, characterized in that the chelating agent is a polybasic acid selected from the group consisting of citric acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, substituted amino-ethylene, unsubstituted and unsubstituted alkyl and glutaric acid and their alkali metal and ammonium salts and, to such an extent that the weight ratio of chelating agent to carrier is in the range of 5: 1 to 1:20, A detergent additive preparation according to claim 15, characterized in that the polybasic acid or its alkali metal or ammonium salt is selected from the group consisting of nitrilotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriamine and merentaric acid the weight ratio of polybasic acid to carrier is in the range of 1: 1 to 1:20, Detergent additive preparation according to any one of Claims 11 to 16, characterized in that the treatment aid is a solid water-soluble or water-dispersible organic aid with a softening point higher than 40 ° C and a melting point lower than 80 ° C, an activator and an excipient with a weight ratio in the range of 20: 1 to 1: 3, A detergent additive preparation according to claim 17, characterized in that the treatment aid is selected from the group consisting of polyvinylpyrrolidone having a molecular weight of 44,000 to 700,000 and having 5 to 30 ethylene oxide groups per mole of alcohol, fatty acids and their esters and amides, and polyethylene glycols with a molecular weight of y4000, Detergent additive preparation according to Claim 14, characterized in that the C18-C18-saturated fatty acid is added in such an amount that the ratio of the nonionic part of the mixture of fatty acid and surfactant is in the range from 1: 5 to 4: 1, 511 64395 A detergent additive preparation according to any one of claims 5 to 19, characterized in that the flexible sheet is water-soluble, Detergent additive preparation according to Claims 5 to 19, characterized in that the flexible sheet is formed from a water-insoluble foamed or fibrous material. Detergent additive preparation according to Claim 21, characterized in that the flexible board is a nonwoven fibreboard, A detergent additive preparation according to claim 22, characterized in that the fibreboard is formed by a nonwoven material, at least part of which is synthetic, bonded with a water-insoluble binder. Detergent additive preparation according to Claim 23, characterized in that the plate is formed in such a way that the openings extend between the two surfaces of the plate, in which the plate has 10 to 18 openings / cm and the base of the plate is 40 to 60 g / m 2, A detergent additive preparation according to any one of the preceding claims, further characterized in that it contains an inorganic persalt in a water-releasing combination with a carrier, but positioned so that the organic peroxy compound activator is spatially separated from the inorganic persalt so that it does not come into contact with it. before adding the additive preparation to the washing liquid. A detergent additive preparation according to claim 25, characterized in that the inorganic persalt and the peroxy compound activator are arranged in the carrier body as separate strips, A process for preparing a washing additive preparation according to claim 1, characterized in that it comprises the steps of forming a peroxy compound activator into a liquid mass, combining said liquid mass with a solid non-particulate support body so as to maximize the treated surface area of the latter, and solidifying said mass, A process for preparing a detergent additive preparation according to claim 27, wherein the melting point of the organic peroxy-compound activator is higher than 95 ° C, characterized in that a molten mixture of the activator and a non-hygroscopic organic solid is formed. having a melting point of less than 80 ° C, with a melting point of the molten mixture in the range of 40 ° C to 80 ° C, precipitating the molten mixture on a fibreboard to impregnate the sheet, and cooling the impregnated sheet to convert the mixture to a solid, 56 64395