JPS6311396B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF THE INVENTION This invention relates generally to removing stains from textiles, and more particularly to laundry additive products containing organic peroxy compound precursors. Products of this type can be added to laundry solutions containing conventional inorganic persalt-containing detergent products to improve the removal of bleachable stains. BACKGROUND OF THE INVENTION Textile materials, particularly materials made from vegetable fibers such as cotton or linen, and products made from these materials are generally treated with conventional cleaning ingredients such as soaps or synthetic detergents, as well as various builders, alkaline These materials are cleaned by contacting them with a cleaning solution containing salts and bleaching compounds. The most common method of treating textiles with bleachable stains involves heating the liquid containing the product from ambient temperature to a temperature close to that of boiling water, i.e. 85°C.
After heating to above ℃ and maintaining this temperature for some time, cooling and taking out the product. At temperatures of 85°C or higher, the inorganic persalt bleaching compounds often contained in detergents, namely sodium perborate and sodium percarbonate, have high bleaching performance, but this performance decreases at lower temperatures. ,
That is, at or below 70°C, there is a rapid drop-off so that the full benefits of the bleach are not obtained unless the wash temperature is high enough. Modern automatic washing machines are equipped with a program cycle that includes a heating stage (so-called "boil wash") to temperatures above 85 °C, but these machines also have a program cycle for handling dyed and synthetic fabrics. Includes a low temperature wash cycle program. As the use of these types of fabrics increases and as energy saving measures become more common, there is a tendency to use less boiling water and more low temperature cycles. Therefore, there is an increasing need for products that have excellent bleaching ability in the temperature range of 70° C. or below, in order to preserve laundry performance in low temperature cycles and to make the most efficient use of expensive ingredients. Bleaching agents that are effective at low temperatures have been known for many years, most of which are capable of releasing organic peracids as bleaching species. Examples of detergent compositions containing this type of bleach are disclosed in US Pat. According to these and other similar disclosures, an organic precursor material is included in the formulation which reacts with the inorganic peroxy bleach component in the wash liquor to form an organic peroxy bleach species, typically a peroxy acid. occurs. This peroxy bleach species is more effective than inorganic peroxy bleaches in the low temperature portion of the laundry operation. However, as products containing such combinations of organic peroxy compound precursors and inorganic peroxy bleaches absorb moisture during storage prior to use, these materials react to form organic peroxy species. It became clear that distribution was difficult because it generated and decomposed. As a result, the efficiency of the product is reduced. Various methods have been proposed to obtain satisfactory stability of organic peroxy bleaches or their precursors in detergent compositions. For example, US Patent No. 3532634
3,49787 and 3,494,786, as described in U.S. Pat.
There are coating methods, such as those described in US Pat. No. 3,441,507, as well as granulation methods, such as those described in US Pat. No. 3,639,248. All of these methods involve the use of organic peroxy bleach in a detergent environment to produce a single product, although they involve the limitation of using a certain level of bleaching species relative to other ingredients in each detergent application. Or we aim to stabilize its precursor. Attempts to improve the stability of peroxy bleach or its precursors in conventional compositions have been accompanied by significant limitations in the amount of bleach released into solution and thus also reduced efficiency and increased cost. Summer. Thus, one drawback of prior art products has been the unnecessary use of bleaching agents in certain circumstances and the formation of expensive compositions that can have deleterious effects. Another disadvantage of conventional products is the direct contact of the fabric with insoluble particles of the organic peroxy bleach itself and/or localized concentration of the organic peroxy bleach in the vicinity of the precursor particles. As a result, it has been difficult to prevent damage to the color of the fibers, especially fine spot staining. One drawback with conventional products has been the risk of damage to human skin and internal tissues. This results from misuse or accidental ingestion under conditions where the reaction between the inorganic persalt and the organic precursor occurs to produce highly reactive organic peroxy bleach species. It is therefore an object of the present invention to include bleach precursors in certain additive products, in which the precursors are chemically and physically stable and free from inorganic peroxides. Spatial separation from the bleaching agent allows this product to be added to textiles at any level desired, before or after the washing operation using conventional detergent compositions, to eliminate these drawbacks. to avoid. The present invention also seeks to increase the efficiency of the bleaching species by providing a bleach precursor product in which the precursor dissolves very rapidly into the wash water. It is an object of the present invention to provide an additive product that exhibits excellent bleachable stain removal performance at temperatures of 70°C or less when added to solutions containing inorganic peroxy salts. SUMMARY OF THE INVENTION According to one embodiment of the invention, a substrate in the form of a non-granular solid article is combined with b an organic peroxy compound precursor for release by water, in which case the precursor and the substrate The weight ratio of
A laundry additive in the range of 30:1 to 1:10 is provided. In another embodiment of the invention, a method for making a laundry additive includes the steps of: forming a peroxy compound precursor into a fluid; impregnating a solid, non-particulate article with the fluid; and coagulating the animal. As used herein, an organic peroxy compound precursor is a compound that reacts with an inorganic peroxy acid-containing compound in an aqueous solution to bleach at least an equivalent amount of the inorganic peroxy compound at a temperature of 70°C or lower under the same conditions. It means an organic compound that can produce an organic peroxy compound with performance. Preferred materials for the purposes of this invention are at least 2.0 ml in the perhydrolysis described below.
This substance requires a titer of 0.01M sodium thiosulfate. Also, as used herein, the terms inorganic peroxy bleaches and inorganic persalts refer to alkali metal perborates, which produce hydrogen peroxide in aqueous solution, rather than compounds such as persulfates and permanganates, which produce other peroxy species. Refers to salts such as percarbonate, persilicate and perpyrophosphate. For the purposes of this invention, combining to be released by water means combining to be releasable by water, by dissolving, dispersing, leaching, softening or melting. In a preferred embodiment of the invention, the organic peroxy compound precursors forming each component of the organic peroxy compound precursor or mixture of these precursors are selected from the group consisting of anhydrides, esters, oximes and N-acylated compounds. It can be done. Preferably, the precursor has one or more of the following structures:
- is an acetylated compound: Here, x is 0 or any integer between 1 and 6, most preferably 1, 2 or 6. Also preferably, the article is a flexible sheet substrate and the weight ratio of the precursor to the substrate is 10:1.
It should be within the range of ~1:10. The additive products of the present invention are configured to be introduced into a washing machine with the soiled fabric or into a programmed drum machine early in the main wash cycle. That is, the precursor and inorganic peroxy bleaching compound contained in the laundry composition do not come into contact with each other except in the laundry liquor. Stability improvements in the inclusion of peroxy bleach precursors in conventional granular formulations can be achieved by delivering the precursor in combination with a non-particulate solid article and water for release into the wash liquor. You can avoid problems,
It also allows the user to decide whether or not to perform low temperature bleaching and to control the level of organic peroxy bleach used. The additive product according to the invention also increases user safety by physically separating the main components and by greatly increasing the difficulty of accidental ingestion of the combination. It is something to do. The present invention also allows for enhanced rates of dissolution of peroxy compound precursors in aqueous solutions compared to those obtained with conventional granular products, which also increases the rate of conversion to organic peroxy bleaching species. It is intended to improve. This improves the coalescence performance efficiency of organic peroxy compounds and reduces the deleterious catalase effect on the bleaching performance of residual inorganic peroxy bleaches. In a particularly preferred embodiment of the present invention,
The present invention provides an effective means for removing stains on fabrics from a wide range of stains, including stains caused by oils and fats and proteins. DETAILED DESCRIPTION OF THE INVENTION As noted above, the invention, in its broadest form, consists of two components. That is, a non-particulate solid article as a substrate and an organic peroxy compound precursor combined therewith for release by water. Organic Peroxy Compound Precursors Organic peroxy compound precursors, like inorganic persalt activators, are well known and widely described in the literature. Examples of various classes of peroxy compound precursors are listed below. a Anhydride The anhydride can be aliphatic, aromatic or a mixture thereof and can be derived from mono- or polycarboxylic acids. Preferred aliphatic anhydrides each have aliphatic groups containing from 1 to 12 carbon atoms, and mixed aliphatic anhydrides should not contain more than 20 carbon atoms. Specific aliphatic anhydrides include:
These are the anhydrides of acetic acid, propionic acid, butyric acid, heptanoic acid, nonanoic acid, acetic acid-hexadecanoic acid, acetic acid-stearic acid and butyric acid-myristic acid. Aromatic anhydrides may be substituted or unsubstituted, preferred examples thereof being benzoic, phthalic and pyromellitic anhydrides, and their nuclear substituted halo, nitro and alkoxy analogs such as 2, These are 4-dichlorobenzoic anhydride, m-chlorobenzoic anhydride, and p-methoxybenzoic anhydride. Mixed aliphatic-aromatic anhydrides also contain 12
It can be used in the present invention as long as it does not contain more than 1 carbon atom. Examples are benzoic acid-acetic anhydride and benzoic acid-propionic anhydride. Examples of other useful anhydrides include cyclic anhydrides,
Examples are anhydrides of maleic acid, succinic acid, glutaric acid, adipic acid, itaconic acid, and polymeric anhydrides such as polyadipic acid polyanhydrides and polyazelaic salt polyanhydrides of the formula: Here, p preferably has a value in the range of 4 to 7, and q has a value in the range of 5 to 15, preferably 7 to 8. US Pat. No. 2,362,401 describes the use of certain organic anhydrides as perborate activators in detergent compositions. This document is added here as a reference. b Esters In the present invention, esters suitable as peroxy compound precursors include monovalent substituted and unsubstituted phenols, substituted aliphatic alcohols with electron-withdrawing substituents, esters of monosaccharides and disaccharides, and esters of hydroxylamine. N-substituted derivatives, as well as esters of imidic acids. Phenyl esters of aromatic and aliphatic mono- and di-carboxylic acids can be used. Aliphatic esters have 1 to 20 carbon atoms in the acyl group, examples are phenyl acetate, phenyl laurate,
phenyl myristate, phenyl palmitate and phenyl stearate. Among these, o-acetoxybenzoic acid and methyl-o-
Particularly preferred is acetoxybenzoate. Diphenyl succinate, diphenyl azelate and diphenyl adipate are examples of phenyl aliphatic dicarboxylic acid esters. Examples of aromatic esters are phenylbenzoate, diphenyl phthalate and diphenyl isophthalate. A specific example of an ester of a substituted aliphatic alcohol is trichloroethyl acetate. Examples of sugars are glucose pentaacetate and sucrose octaacetate. A typical ester of hydroxyamine is acetylacetohydroxamic acid. These and other esters suitable for use as peroxy compound precursors in the present invention are described in British Patent Nos. 836988 and 839715.
No. 1, which is fully described in No. 1, which is hereby incorporated by reference. Other groups of esters are acyl phenolsulfonates and acylalkylphenolsulfonates. An example of the former is sodium acetylphenol sulfonate (or sodium
p-acetoxybenzenesulfonate) and sodium benzoylsulfonate (also called sodium-p-benzoyloxybenzenesulfonate). Examples of acylphenol alkyl sulfonates are sodium-2-acetoxy-5-dodecylbenzenesulfonate, sodium-2-acetoxy-5-hexylbenzenesulfonate and sodium-2-acetoxy-5-hexylbenzenesulfonate.
2-acetoxy-caprylbenzenesulfonate. The preparation and uses of these and similar compounds are described in British Patent Nos. 963135 and 963135.
No. 1147871. Both of these will be added as references. Acylated esters of phosphoric acid are also recommended as organic peroxy compound precursors. Examples are diethyl monoacetyl orthophosphate and diacetyl ethyl orthophosphate. The ester of imide acid has the following general formula. Here, X is substituted or unsubstituted C ₁ -C ₂₀ alkyl or aryl, Y is the same as X,
It can also be -NH ₂ . An example of this class of compounds is ethylbenzimidate, which is
In that case Y is C ₆ H ₅ and X is ethyl. Other specific esters are p-acetoxyacetophenone and 2,2-di-(4-hydroxyphenyl)propane diacetate. This last substance is 2, commonly known as bisphenol A, an intermediate in the production of polycarbonate resins.
It is a diacetate derivative of 2-di(4-hydroxyphenyl). German patent publication (DAS) for bisphenol A diacetate and its production method
No. 1260479, the disclosure of which is incorporated by reference. c Imide An imide suitable as an organic peroxy compound precursor in the present invention is a compound of the following formula. Here, R ₁ and R ₂ are the same or different groups, each selected from a C ₁ -C ₄ alkyl group or an aryl group, and X is an alkyl group, an aryl group, or an acyl group (carboxyl group or sulfone group). It is. In typical compounds, R ₁ is a methyl group,
Compounds are ethyl, propyl or phenyl groups, and preferred compounds are those in which R ₂ is also a methyl group; examples of such compounds are N,N-diacetylaniline, N,N-diacetyl- p-chloroaniline and N,N-diacetyl-p-toluidine. Either R ₁ or R ₂ and X can form a heterocycle containing a nitrogen atom. A typical class with this type of structure is N-acyllactams, in which the nitrogen atom is bonded to two acyl groups, one of which is also bonded to the second nitrogen via a hydrocarbyl bond. be. A particularly preferred example of this class is N-
Acetyl caprolactam. The linkage of the acyl group that forms the heterocycle itself contains a heteroatom, such as oxygen, and N-acyl sugars are a class of precursors of this type. Examples of cyclic imides where the reactive center is a sulfonic acid are N-benzenesulfonylphthalimide,
N-methanesulfonyl succinimide and N-
It is benzenesulfonyl succinimide. These and other N-
Sulfonylimides are disclosed in GB 1242287, which is incorporated by reference. The bond of the nitrogen atom to the three acyl groups is N
- Occurs in N-acylated dicarboxylic acid imides such as acylphthalimide, N-acyl succinimide, N-acyl adipimide and N-acyl glutarimide. An imide of the above type is described in British Patent No. 855735, the description of which is incorporated by reference. Two other preferred groups of substances of this class are those in the above formula in which X is a second diacylated nitrogen atom, i.e. substituted hydrazines, or
C ₁ further substituted by a diacylated nitrogen atom
- Difunctional hydrocarbyl groups such as C ₆ alkylene groups, ie, tetraacylated alkylene diamines. Particularly preferred compounds are N, N, N',
It is an N'-tetraacetylated compound. Here, x is 0 or an integer from 1 to 6. Examples are tetraacetylmethylenediamine (TAMD) when x=1, tetraacetylethylenediamine (TAED) when x=2, and tetraacetylhexamethylenediamine (TAHD) when x=6.
It is. If x=0, this compound is tetraacetylhydrazine (TAH). TAHD and
TAMD has a low melting point (59℃ and 83℃ respectively)
Therefore, it is particularly preferred, and as described later, it can be easily treated in the detergent of the present invention. These compounds and analogs are described in GB 907356, GB 907357 and GB 907358, the description of which is incorporated by reference. Acetylated glucouryl constitutes another group of compounds that fall within the general class of imidoperoxy compound precursors of the present invention. This type of material has the following general formula: At least two of the R groups here are acyl groups having 2 to 8 carbon atoms in their structure. A preferred compound is tetraacetylglycouryl, where all R groups are CH ₃ CO- groups. Acetylated glycouryl is disclosed in British Patent No. 1246338;
It is described in No. 1246339, No. 124817, and No. 1247429, and this description will be added as a cited document. Other imide-type compounds suitable for use as peroxy compound precursors in the present invention are N-(halobenzoyl)imides disclosed in British Patent No. 1247857, a preferred example of which is N-
-m-chlorobenzoyl succinimide,
British Patent No. 1244200 also discloses polyimides containing N-bonded-COOR groups, such as N
-Methoxycarbonylphthalimide. Both British patent specifications are included as references. N-acyl and N,N'-diacyl derivatives of urea are also suitable peroxy compound precursors for the purposes of the present invention, in particular N-acetyldimethylurea,
N,N′-diacetylethyleneurea and N,
N′-diacetyldimethylurea can be used. Compounds of this type are described in Dutch Patent Application No. 6504416.
No. (published October 10, 1966), which is included as a reference. Other urea derivatives with inorganic persalt activating properties are the mono- or di-N-acylated azolinones disclosed in GB 1379530. Acylated hydantoin derivatives also fall within this general class of organic peroxy compound precursors. Hydantoins can be substituted, for example by lower alkyl groups, and can be acylated at one or both nitrogen atoms. Examples of this type of compound are:
These are N-acetylhydantoin, N,N-diacetyl-5,5-dimethylhydantoin, 1-phenyl-3-acetylhydantoin and 1-cyclohexyl-3-acetylhydantoin.
These compounds and similar compounds are covered by British Patent No.
Described in No. 965672 and No. 1112191,
Add this as a reference. Other classes of imide-type nitrogen compounds are N,N-
diacylmethylene diformamide, N,
N-diacetyl methylene diformamide is the preferred compound. This material as well as similar compounds are described in GB 1106666, which is incorporated by reference. d Cyano Compounds Another class of organic compounds suitable as peroxy compound precursors in the present invention are compounds having the following general formula. X-C≡N where X is a substituted or unsubstituted alkyl group or aryl group, or

It can be [expression]. Here, A is -OR or _-NR1R2 , and each _R1 and _R2 is a lower alkyl group or a substituted or _{unsubstituted} aryl group. This class of compounds differs from most other peroxy compound precursors in that reaction with inorganic persalts forms peroxy species other than peroxy acids. When X is a substituted or unsubstituted alkyl or aryl group, the compound is a nitrile, which may be monofunctional or polyfunctional;
The efficiency also increases as the number of cyano groups increases, as long as the compound retains some level of water solubility. Examples of organic nitriles are phthalonitrile, benzonitrile, tetramethylene dinitrile, malonitrile, ethylenediaminotetraacetic acid dinitrile, nitrilotriacetic acid nitrile and succinonitrile. These and other similar compounds that can be used in the present invention are fully described in GB 802,035, which is incorporated by reference. In the above formula, X is -COOR or -
The compound where CONR ₁ R ₂ is
No. 2647978, which is incorporated by reference. e Imidazole N-acylimidazoles and similar five-membered ring compounds constitute another group of inorganic peroxy compound precursors that can be used in the present invention. Particular examples thereof are N-acetylbenzimidazole, N-benzoylimidazole and its chloro- and methyl-analogs. Compounds of this type are described in GB 1234762, GB 1311768 and GB 1395760, which are incorporated by reference. f Oxime Oxime and certain acetylated oximes also include
Oximes, a class of organic peroxy compound precursors that can be used for the purposes of the present invention, are derivatives of hydroxylamine which, upon reaction with aldehydes and ketones, give aldoximes and ketoximes, respectively.
The acyl group is _C1 - _C12 aliphatic or aromatic,
Preferred acyl groups are acetyl, propionyl, lauroyl, myristyl and benzoyl groups. Compounds containing more than one carbonyl group can react with more than one equivalent of hydroxylamine, the most common class of dioximes being 1,2
- those derived from diketones and ketotic aldehydes, such as dimethylglyoxime. Acetylated derivatives of this compound are particularly useful as organic peroxy compound precursors, examples of which are diacetyldimethylglyoxime, dibenzoyldimethylglyoxime and phthaloyldimethylglyoxime. g Carbonates Substituted and unsubstituted aliphatic, aromatic and cycloaliphatic esters of carbonic and pyrocarbonic acids have also been proposed as organic peroxy compound precursors. Typical examples of this type of ester are p-carboxylphenylethyl carbonate, sodium-p-sulfophenylethyl carbonate, sodium-p-
-sulfophenyl-n-propyl carbonate and diethylpyrocarbonate. The use of esters of this type as organic persalt activators in detergent compositions is described in British Patent No. 970,950, which is incorporated by reference. In addition to the above classes, a number of other materials can be used as organic peroxy compound precursors, including the triacylguanidines of the formula: Here, R is an alkyl group produced by acylation of a guanidine salt, preferably an acetyl group or a phenyl group. Other classes of compounds include acylsulfonamides, e.g. British Patent No. 1003310
N-phenyl-N-acetylbenzenesulfonamide disclosed in British Patent No.
There are triazine derivatives such as those disclosed in Nos. 1104891 and 1410555. Examples of particularly preferred triazine derivatives include 2,4,6-trihydroxy-1,3,5-triazine, 2-chloro-4,
6-dimethoxy-S-triazine and 2,4-
Dichloro-6-methoxy-S-triazine di-
and triacetyl derivatives. UK patent no.
Piperazine derivatives such as the 1,4-diacylated 2,5-diketopiperazines described in British Patent No. 1339256 and British Patent No. 1339257, as well as water-soluble piperazine derivatives such as the methyl, ethyl and phenyl chloroformates described in British Patent No. 1242106 The same can be used as alkyl and aryl chloroformates. All of the foregoing documents are hereby incorporated by reference. Among the above classes of activators, a preferred class is one that yields peroxycarboxylic acids upon reaction with inorganic persalts. Particularly preferred classes are anhydrides, imides, oximes and esters, particularly preferred are phenolic esters and imides. Examples of preferred substances include methyl-o-acetoxybenzoate, sodium-p-acetoxybenzenesulfonate, bisphenol-A
- diacetate, tetraacetylethylenediamine, tetraacetylhexamethylenediamine and tetraacetylmethylenediamine. The type of color damage to fabrics known as "pinpoint spotting" is minimized and in many cases virtually eliminated as a result of the use of the additives of this invention; Under severe conditions, especially when the fabrics being laundered are excessively soiled, the use of certain peroxy compound precursors may be insufficient, especially when using precursors that generate perbenzoic acid as the bleaching species. , it was discovered that color damage still occurs. However, it is surprising that if such a perbenzoic acid precursor is used in admixture with a rapidly perhydrolyzable peracid precursor, the weight ratio of peracetic acid precursor to perbenzoic acid precursor is 1: It has been discovered that a ratio of 10 to 10:1, preferably 5:1 to 1:5, significantly reduces the risk of such fading. Although the mechanism of action of the mixture in reducing the fading effect is not clear, it is believed that the mixture is effective in inhibiting catalase activity in the wash liquor. Catalase is known to destroy the hydrogen peroxide produced by the inorganic per-bleach agents commonly found in detergents, and this catalase, in the case of the present invention, reduces the form of the desired organic bleaching species. It is thought to create conditions. Peroxybenzoic acid is a stronger bleaching agent than peracetic acid. That is, it has a higher oxidation potential and therefore, to maximize performance, the proportion of peracetic acid in the bleach species mixture should be It should be kept to the minimum level necessary to avoid fading of the fabrics used. As mentioned above, the weight ratio of perbenzoic acid precursor to peracetic acid precursor is 10:1 to 1:10, preferably 5:1.
It has been discovered that satisfactory reduction in fading can be obtained within the range of ~1:5. The most desirable ratio is about 1:1. In this regard, it should be noted that the conversion of peroxy compound precursors to peroxy acid species is not necessarily quantitative and depends on the nature of the precursor as well as the reaction conditions under which the conversion occurs, in particular time and temperature. It is recognized that mixtures of perbenzoic acid precursor and peracetic acid precursor in a weight ratio of less than 1:10 are also satisfactory in terms of bleaching action, although the efficiency is slightly reduced, and that they have a low risk of fading damage. However, in the additive according to the invention, the advantage of high bleaching potential of perbenzoic acid with low risk of fading is best realized with a precursor mixture in the proportions mentioned above. The amount of peroxy compound precursor added to the substrate is such that the precursor:substrate ratio is in the weight ratio range of 30:1 to 1:10, more generally 10:1 to 1:10. Preferably, this weight ratio is between 8:1 and
The range is 1:2, most preferably 5:1 to 1:1. Of course, the level of organic peroxy compound precursor used depends on many factors. For example, the size of the fabric insert in the washing machine, the desired bleaching performance level, the amount of inorganic persalts in typical detergent compositions, and the use of the laundry product, bleaching of organic peroxy species derived from precursors. efficiency as well as the efficiency of conversion of precursors to peroxy species. In the case of inorganic peroxy bleaches, for heavy-duty detergent purposes, the available oxygen level in the solution is
It is normal to set the content to 50ppm to 350ppm (by weight). However, when organic peroxy bleaches are used, the available oxygen level provided by the organic peroxy compound should be within the range of 10 ppm to 80 ppm. This available oxygen level should be achieved within the normal wash cycle time, ie, within 15 to 25 minutes, depending on the particular wash cycle used. For washing machines with a working liquid capacity of 20-30l,
To achieve this available oxygen level, 1 g to 20 g of organic peroxy compound precursor with quantitative conversion is required.
need to be added. This number increases inversely as conversion efficiency decreases. Preferably, it should be possible to accommodate this level of precursor and any other auxiliaries and additives required to be included in the product in a single base unit. However, it is a matter of choosing the number of units used to deliver a given amount of precursor. in principle,
The amount of precursor used at one time is 3 to 10 g, preferably 4 to 10 g.
It is in the range of 6g. Substrate According to the present invention, the peroxy compound precursor is
It must be combined with a substrate consisting of a non-particulate solid article in such a way that it can be released by water. The substrate itself may be water-soluble or water-insoluble, but in the latter case it should retain sufficient structural integrity under the washing conditions to be recovered from the machine at the end of the wash cycle. It is. Water-disintegratable structures for the purposes of the present invention, ie structures that disintegrate into discrete insoluble fibers or particles in an aqueous medium, are considered unsatisfactory. Water-soluble materials include certain cellulose ethers, alginates, polyvinyl alcohol, and water-soluble polyvinylpyrrolidone polymers that can be formed into nonwoven or woven structures. Also suitable water-insoluble materials include, but are not limited to, natural or synthetic fibers, foams, sponges and films. The base material is sheet, block, ring, ball,
It can take any of a number of physical shapes, such as a rod or a tube. Such a shape should allow the user to use it as a unit. i.e. discrete sheets, blocks or balls, or unit lengths of rods or tubes, etc.
It must be possible to add measured amounts into the washing liquid. Some of these substrates are
Can be used once or multiple times,
It is also possible to deposit organic peroxyacid precursors up to a 30:1 weight ratio of precursor:substrate. Articles of this type can also be formed into sponge materials releasably encapsulating sufficient organic peroxy compound precursors to produce a bleaching action over several washing cycles. This multi-use article can be made by impregnating a sponge ball or block with about 20 grams of the precursor and other adjuvants. During use, this precursor leaches through the pores of the sponge into the wash liquor and reacts with the inorganic peroxy bleach. Such a encapsulated sponge has the advantage that it can be used to process several loads of fabrics in a conventional washing machine and can be left in the washing machine after use. Other devices and articles suitable for use in dispensing organic peroxy compound precursors into laundry fluids include those described in the following patent specifications. US Pat. No. 3,736,668, US Pat. No. 3,701,202, US Pat. No. 3,634,947, US Pat. No. 3,633,538, US Pat. No. 3,435,537. Highly preferred articles of the present invention include a flexible sheet and an organic peroxy compound precursor that are hydrated to be compatible with the movement of the fabric in the washing machine and to facilitate manipulation during manufacture of the product. Preferably, the sheet is water permeable. That is, water should be able to pass from one side of the sheet to the other, and in the case of a film-type substrate, a porous sheet is desirable. The most preferred substrate form is a sheet of woven or nonwoven fabric or a thin sheet of spongy plastic material. The woven sheet can be in the form of low fiber count/unit length plain weave natural or synthetic fibers, such as those used in dressings or of the type known as cheese kris. Due to the limit of the amount of adhesion on sheet-type substrates,
The amount of precursor that can be added to the sheet is limited. That is, the maximum ratio is limited to a precursor:sheet weight ratio of about 10:1. The highly desirable properties of the laundry additives of the present invention are:
The additive should not interfere with the mechanical operation of the washing machine. Most household washing machines are of the rotary perforated drum type, and the entire outer peripheral surface is provided with perforations. In this type of device, problems of liquid flow obstruction to the machine are avoided due to the drum construction as well as the mode of operation. Some older models of washing machines use an agitator in a stationary tank with a recirculating fluid system. In order to prevent liquid blockage in machines of this type, it may be necessary to provide slits or pores in the substrate, especially in the sheet type.
This type of sheet structure is disclosed in US Pat. Nos. 3,944,694 and 3,956,556, respectively, the disclosures of which are incorporated by reference. A desirable property of the substrate used in the present invention is that it is absorbent in nature. It is known that most substances can absorb liquid substances to some extent. However, as used herein, the term "absorbent" refers to a material that has the ability to absorb up to approximately 12 times its weight in water (i.e., a value that indicates the ability of a substrate to absorb and retain liquid). ). The absorption capacity value is determined by the absorption capacity last method described in Federal Standard UU-T595b, modified as follows. 1. Use tap water instead of distilled water. 2. The specimen is immersed for 30 seconds instead of 3 minutes. 3 Drainage time is 15 seconds instead of 1 minute. and 4. The sample pieces are immediately weighed on a screw balance with a pan with a cambered edge. Therefore, the absorption capacity value is calculated using the formula shown in the above standard. According to this test, 1 ply,
Dense bleached paper (e.g. 270m ² (3000 sq ft)
Kraft or bond paper with a basis weight of about 14 Kg (about 32 pounds) has an absorbent capacity of 3.5 to 4. Commercially available household 1-ply towel paper has a value of 5-6. In addition, commercially available 2-ply household towel paper has a
~ with a value of approximately 9.8. The substrate of the present invention can be referred to as "free space". As used herein, "free space"
Alternatively, "void volume" shall mean the unfilled space within the structure. For example, a multi-ply paper structure is made by butting and joining the protrusions of plies with protrusions, but this type of paper structure is made by connecting the protrusions of plies that do not have protrusions, and the paper sheet itself. It has a void volume of free space between the fibers. Also, nonwoven fabrics have such spaces between each of their fibers. The free space of a nonwoven or paper with specific physical dimensions can be varied by changing the density of the fibers of the paper or nonwoven. Substrates with a large proportion of free space generally have a low fiber density. High density substrates, on the other hand, have a low amount of free space. Preferred substrates in the present invention are those having up to about 90% free space relative to the total volume of the substrate structure. As mentioned above, suitable materials that can be used as substrates in the present invention are especially sponges, paper and woven and non-woven fabrics. Preferred substrates for the laundry additive products of the invention are also comprised of cellulose fibers, particularly non-woven fabrics with or without apertures. More specifically, one example of a suitable substrate is a compressible, layered, calendered, multi-ply absorbent paper structure. Preferably, this paper structure has 2
or 3 ply, with a basis weight of about 6 to about 40 Kg (14 to 90 lbs.) per 270 m ² (3000 sq. ft.) and an absorbent capacity value in the range of 7 to 10. Each ply of the preferred paper structure has a basis weight of about 7 to 30 pounds per ³⁰⁰⁰ square feet; It can be made to consist of ply. Each ply has a crepe percentage of approximately 15% to 40% and a crepe percentage of approximately 100 to 100 ^per square inch of paper width
Preferably, it is made of crepe paper or other extensible paper with a 1500g machine direction (MD) tensile strength and cross machine direction (CD) resistance. The outer two-ply of a three-ply paper structure or each ply of a two-ply paper structure extends from about 0.25 to about 10 mm (about 0.010 inch to about 0.40 inch) above the non-embossed side of the paper sheet.
It is embossed with an identical repeating pattern of approximately 16 to 200 discrete protrusions per 6.5 cm ² (inch 2) of height.
Approximately 10% to 60% of the paper sheet surface is embossed. The distal ends of the projections of each ply (i.e., the ends opposite from the unembossed paper sheet side) are butted together and glued together, thereby providing a compressive modulus of approximately 200 to 800 grams ^per square inch. and about 10 to 130 "handle meters"
(HOM) resulting in a paper structure exhibiting favorable MD and CD values. Compression modulus value that defines the compressive deformation characteristics of a paper structure subjected to compressive loads on both sides, HOM value related to the stiffness or texture of the paper structure,
MD and CDHOM values, which refer to HOM values obtained from paper structure samples tested in the machine direction and cross-machine direction, methods for determining these values, equipment used, further detailed description of preferred paper structures, and Its manufacturing method is covered by a US patent.
Described in No. 3414459. This US patent specification is incorporated by reference. Preferred nonwoven substrates for use herein generally have a web structure or a carded fibrous structure (the fiber strength of which is suitable to enable carding), or fibers or filaments are The fibers or filaments may be arranged in an accidental or random manner (i.e. fiber arrangement in a carded web, where there is often a partial orientation of the fibers, as well as a completely random orientation) or where the fibers or filaments are substantially aligned. It can be defined as a fiber or filament product that consists of a fiber mat bonded with an adhesive. Natural fibers or filaments (e.g. wool, silk, wood pulp,
jute, hemp, cotton, linen, sisal or ramie), synthetic (eg rayon, cellulose, esters, polyvinyl derivatives, polyolefins, polyamides or polyesters) or mixtures of any of the foregoing. The method of manufacturing the nonwoven fabric is not part of the present invention and is a known technique, so it will not be described in detail. Generally, this type of fabric is made by air or water fiber placement, in which the fibers or filaments are first cut to the desired length from a long strand, passed through an air or water stream, and then When air or water containing the fibers is passed through the screen, the fibers or filaments deposited on the screen are glued together,
It is dried, cured, or otherwise treated as desired to form a nonwoven fabric. Nonwoven fabrics made of polyester, polyamide, vinyl resin, and other thermoplastic fibers can be spunbonded. That is, fibers can be spun onto a flat surface and bonded (melted) together by thermal or chemical reactions. The absorption properties desired in the present invention are easily obtained, especially with non-woven fabrics, by simply increasing the thickness of the fabric, i.e. by layering several carded webs or mats to a sufficient thickness to obtain the required absorption properties. , or alternatively by depositing a sufficient thickness of fibers on a screen. Any diameter or denier of fibers (generally up to about 10 denier) can be used. This is because it is the free space between each fiber that relates the thickness of the fabric to its absorption capacity, and it is this free space that makes the nonwoven fabric suitable for impregnation with peroxy compound precursors by cross-action or capillary action. This is because. That is, any thickness necessary to achieve the required absorbent capacity can be used. The selection of binder resins used in the production of nonwoven fabrics allows the creation of substrates with a variety of desirable properties. For example, the absorbent properties of the fabric can be increased, decreased, or controlled by the use of hydrophilic binder resins, hydrophobic binder resins, or mixtures thereof, respectively, in the fiber bonding step. Moreover, the hydrophobic binder resin, when used alone or as the main component of a hydrophobic/hydrophilic mixture, allows the precursor/substrate combination according to the invention to be used in automatic washing machines. The present invention provides a nonwoven fabric that is particularly effective as a substrate when If the substrate is a non-woven fabric consisting of fibers arranged haphazardly or randomly on the screen,
The composition exhibits excellent strength in all directions and has no tendency to burst or separate when used in a washing machine. Preferably, the nonwoven fabric is water-laid or air-laid with fibers made of cellulose fibers, particularly recycled cellulose or rayon, and these fibers are lubricated with standard textile lubricants. Preferably, these fibers are about 5
mm to approximately 50mm (3/16″ to 2″) long, and 1.5 to 2″ long.
5 denier (a denier corresponds to the weight in grams of a length of 9000 meters; it is an internationally recognized unit of measurement for a strip). Preferably, these fibers are at least partially accidentally oriented, in particular largely incidentally oriented, and are bonded by a hydrophobic or substantially hydrophobic binder resin, especially a non-ionic self-linking acrylic polymer. Glue them together. Desirably, the fabric contains 70% fiber and 30% binder resin polymer (by weight) and has a fiber content of from about ¹⁰ to about 100, preferably from about 20 to about 60, per square yard.
It has a basis weight of g. A suitable example is 70% recycled cellulose (American Viscose Corporation) and 30% hydrophobic binder resin (Rhoplex HA-8 on one side of the fabric;
Rhoplex HA−16 Rohm & Haas, Inc) on the other side
It is an air-laid nonwoven fabric containing This cloth is about 0.10
It has a length of ~0.13 mm (4-5 mils), a basis weight of approximately 24 g/0.8 m ² (square yard), and an absorption capacity of 6. The weight of a 0.3 m (1 foot) length of approximately 21 cm (8 1/3") wide cloth is approximately 1.78 g. The fiber is approximately 6 mm.
(1/4") long, 1.5 denier, and substantially randomly oriented. The fibers are lubricated with sodium oleate. Examples of other substrates include CHDexter Co., Inc., Inc. The fibers are recycled, approximately 10 mm (approximately 3/8") long, approximately 1.5 denier, and are lubricated with a similar standard textile lubricant. There is. The fibers are approximately 70% non-woven
% by weight and are substantially randomly oriented. The binder resin (HA-8) constitutes approximately 30% by weight of the nonwoven. The base is approximately 0.1 mm (approximately 4 mils) thick,
It has a basis weight of approximately 24g per 0.8m ² (square yard) and an absorption capacity of 5.7. One foot of nonwoven fabric approximately 21 cm (8 1/3") wide has a weight of approximately 1.66 g. For purposes of this invention, nonwoven substrates having openings may be used. Apertures on both sides of the substrate are in principle formed in a pattern during the laydown of the fibers to produce the substrate. Examples of nonwoven substrates with apertures are shown in U.S. Pat. No. 3,741,724;
3930086 and 3750237, the disclosures of which are incorporated by reference. A particularly suitable example of an apertured nonwoven substrate is Chicopee
Manufacturing Co., Ltd. under the code name SK650WFX577 and consists of a polyester/wood pulp mixture with a basis weight of 50 g/m ² and approximately 13 openings per square cm. Also from Chicopee Manufacturing Co.,
Another preferred example of an apertured nonwoven substrate, available under the code name AK30ML1379, is a recycled cellulose sheet made of 3.0 denier fibers bonded with a Rhoplex RA8 binder (70:30 fiber:binder ratio) and 40 g It has a basis weight of /cm2 and openings of 17 pieces/cm2. In general, the apertured nonwoven fabric that constitutes the object of the present invention is
10-20 pieces/sq m, preferably 12-18 pieces/sq cm
It has an opening. Another class of substrate materials that can be used in the present invention is a sheet of absorbent foam material.
"Absorbent foam" refers to "gas foam foam," natural sponge, U.S. Pat.
3430630 is intended to include three-dimensional intraabsorbent materials such as composite fiber structures such as those disclosed in US Pat. No. 3,430,630. These US patent specifications are incorporated by reference.
Particularly suitable materials of this type are hydrophobic polyurethane foams in which the internal cell walls of the foam are broken by reticulation. This type of form is
U.S. Patent No. 3,794,029 (add as reference)
is described in detail. A preferred example of this type of foam has a density of about 0.596 grams ^per cubic inch, with 20 to 100 cells per inch;
preferably have a cell count of about 60-80 cells;
Hydrophilic polyurethane foam available under the trademark "Hydrofoam" from Scott Paper Company (Pennsylvania, USA). The size and shape of the substrate sheet is a matter of preference, determined primarily by factors related to its convenience in use. That is, the sheet should not be so small that it becomes trapped in the crevices of the machine or the width of the cloth being washed, nor should it be so large that it can be easily placed in or removed from a container for sale. For purposes of this invention, approximately 130 to approximately 1300 cm ² (20
Sheets with an area of between about 510 and 780 ^cm2 (80 to 200 cm2) are desirable;
120 square inches). Optional Components In addition to the peroxy compound precursor, one or more other substances can be added to the substrate, either separately or in combination with the precursor. The type and level of such optional functional components are limited only by the nonreactivity requirements for the precursor (if the optional material is added in intimate contact with the precursor) and the coverage limits of the substrate. be done. As will be discussed in more detail below, substances capable of reacting with the precursor can be included in the additives of the present invention, provided that the precursor is spatially separated therefrom, i.e. free from other reactants,
Alternatively, it is important that the material be placed at a substantially free location on the substrate. Each optional ingredient can be included in an amount corresponding to a 20:1 optional ingredient:substrate weight ratio. However, for processing reasons and product appearance reasons, the total weight per sheet of optional ingredients is
As a general rule, a maximum of 10 times the weight of the sheet is maintained, ideally less than 5 times the sheet material, and each component is present in less than 3 times the weight of the sheet. One factor that determines the acceptable level of inclusion of an optional ingredient is its physical characteristics: whether it is a liquid or a solid, and if solid, whether it is crystalline or waxy. , have a low or high melting point or softening point. The most preferred optional ingredient is 40% for ease of processing.
A waxy solid water-soluble or water-dispersible organic adjuvant with a softening point above 80°C and a melting point below 80°C. If the peroxy compound precursor does not have such properties because it is a solid with a high melting point, it may be used as an auxiliary agent to facilitate release of the precursor from the substrate when it is introduced into the washing liquid. It is preferable to contain one or more kinds of organic adjuvants as described above.
Preferred adjuvants serve as plasticizers or thickening agents when the precursor is included in or on the substrate;
Ideally, it is a non-hygroscopic solid and is melted when mixed with the precursor to yield a mixture having a viscosity of up to 5000 chinch poise at 50°C. Typical solid adjuvants have a molecular weight of 44,000 to 700,000,
Preferably 500,000 to 700,000 polyvinylridone,
Tallow alcohol ethoxylate containing 5 to 30 ethylene oxide groups per mole of alcohol, C12-
C18 fatty acids and certain esters and amides thereof, sorbitan esters of _C16 - _C18 fatty acids, and polyethylene glycols with a molecular weight greater than 4000. As mentioned above, preferred materials are those of low hygroscopicity, especially _C14 - _C18 saturated fatty acids. In preferred embodiments of the invention (described below) that include one or more nonionic surfactants for oil and grease removal, the nonionic surfactant(s) serve as a processing aid, thereby adding Reduce or eliminate the need for processing aids. Methyl-0-acetoxybenzoate, molecular weight
Some compounds that are themselves peroxy compound precursors, such as 1000-2000 polyazelaic acid polyanhydride and succinic acid dinitrile, have the necessary properties for use as processing aids and are used as such. I can do things. Parafine wax can also be used in small amounts. When the processing aid has no other function in the product, such as the surfactant component of a grease and stain removal surfactant mixture, its content level should be such that the precursor:processing aid weight ratio is 20:1 to 1:3. It is desirable to keep the ratio within the range of , and the latter ratio is for economic reasons. However, if the processing aid has other functional properties such as surface activity, this precursor:processing aid weight ratio can be as low as 1:10. Another class of materials that can be used as processing aids are polyacrylamides with a molecular weight greater than 500,000, which are thixotropic water-soluble polymers that can retain water in the solid state. The organic peroxy compound precursor can be dissolved or dispersed within the aqueous paste of the polymer. This paste is then applied to the substrate web and impregnated/coated onto the substrate surface where it hardens as a solid, but water-soluble gel. This class of materials is particularly effective for attaching organic peroxy compound precursors to water-soluble substrates such as polyvinyl alcohol, which tend to lose water solubility when exposed to high temperatures. As mentioned above, the organic adjuvant serves as a release aid and helps release the precursor from the substrate when the product of the invention is added to the cleaning solution. In general, substances that serve as processing aids are also suitable as release aids, but a few substances, especially _C16 - _C18 fatty acids and polyethylene glycols with molecular weights between 4000 and 6000, are precursors: release aid weight. Ratio 20:1~1:
2, especially when used in amounts ranging from 4:1 to 1:1. 2,2-G-(4-
The effect of release aids is particularly pronounced for water-insoluble precursors such as hydroxyphenyl)propane diacetate. Other types of release aids are those that are added to the substrate during manufacture of the substrate or prior to depositing the precursor and other components on the substrate. This type of adjuvant is a fluorinated hydrocarbon or silicone which alters the surface properties of the substrate to facilitate release of the active ingredient when in contact with water. Fluorocarbon treatment solutions available from 3M Company as FC807 and 808 have a substrate/fluorocarbon solids weight ratio of 500:1 to 50:1, preferably about 300:
When applied to a substrate in an amount of 1:1, it provides an excellent release effect. In addition to the optional ingredients described above that serve to deposit and release the precursor onto the substrate, detergent ingredients other than inorganic bleaches as well as compounds reactive to the body may be mixed with the precursor and added to the substrate. can. That is, surfactants, foam modifiers, chelating agents,
The present invention applies anti-resettling agents, soil suspending agents, optical brighteners, bactericidal agents, anti-tarnishing agents, enzyme substances, fabric softeners, antistatic agents, fragrances, and bleaching catalysts within the limits of the amount of adhesion on the substrate. can be introduced into the cleaning solution using additive products. The surfactant can be one or more surfactants selected from the anionic, nonionic, zwitterionic, amphoteric and cationic classes and mixtures thereof. Anionic surfactants can be natural or synthetic, nonionic surfactants can be semipolar or alkylene oxide types, and cationic surfactants can be amine salts,
Quaternary nitrogen and phosphorus compounds and tertiary sulfonium compounds can be included. Examples of each of these classes are disclosed in US Pat. No. 3,929,678, which is incorporated by reference. However, laundry additive products made in accordance with the present invention are particularly suitable for containing nonionic surfactants effective in removing grease stains. This type of nonionic surfactant tends to be difficult to incorporate into conventional detergents because of its physical properties. The spray-drying process of granular detergents containing non-ionic surfactants creates gas generation problems during production due to the volatility of a few non-ionic fractions;
Also, granular detergents made using it tend to have unsatisfactory flow characteristics. The inclusion of such non-ionic agents in the additive products of the present invention allows the creation of non-ionic interfaces of this type in the wash liquor without the difficulties associated with granular formulation or processing of conventional detergent particles. An activator can be added,
Another advantage is that the product containing this nonionic surfactant can be applied to greasy stains by hand in advance to treat the stains. Accordingly, in a preferred embodiment of the invention, the HLB ranges from 8.0 to 17.0, most preferably from 9.5 to 15.5, and consists of a condensation product of ethylene oxide and a hydrophobic organic molecule having a reactive hydrogen. Contains at least one nonionic surfactant selected from the group. Hydrophilic/Lipophilic Balance or HLB is a widely accepted measurement of the polarity of a surfactant and its relative affinity for aqueous or hydrocarbon media. This kind of concept was first introduced in WC
Developed by Griffin, it is possible to give a numerical value for a surfactant substance, and the scale is set such that hydrophilicity increases with increasing HLB value. For nonionic surfactants containing ethylene oxide, their HLB value is HLB
It can be displayed as =E/5. where E is the weight percent of ethylene oxide in the compound. Organic molecules with desired hydrophobicity and reactive hydrogen atoms can be used in linear and branched chain configurations in primary and secondary structures.
Includes _C9 - _C15 aliphatic alcohols and _C12 - _C18 alkylphenols. Examples of nonionic surfactants suitable for use in the present invention are as follows. Linear C ₁₄ −C ₁₅ alcohol (E ₇ ) C ₁₄ −C ₁₅ 〃 (E ₅ ) C ₁₂ −C ₁₃ 〃 (E ₆ ) C ₉ −C ₁₁ 〃 (E ₅ ) Branched C ₁₀ −C ₁₃ 〃 (E ₄ ) Linear s-C ₁₁ -C ₁₅ 〃 (E ₅ ) s-C ₁₁ -C ₁₅ 〃 (E ₇ ) s-C ₁₁ -C ₁₅ 〃 (E ₉ ) Coconut fatty acid (E ₅ ) Olein Fatty acid (E ₁₀ ) Linear C ₈ alkylphenol (E ₅ ) C ₈ 〃 〃 (E ₈ ) C ₉ 〃 〃 (E ₆ ) C ₉ 〃 〃 (E ₉ ) Sorbitan monooleate (E ₅ ) Sorbitan trioleate (E ₂₀ ) Sorbitan monostearate (E ₄ ) Sorbitan tristearate (E ₂₀ ) Particularly preferred substances are
Primary linear and branched chain, primary alcohol ethoxylates containing ~20 ethylene oxide groups, such as condensation products of _C14 - _C15 linear alcohols with 7 to 15 moles of ethylene oxide. , for example Shell
It is condensed with ethylene oxide, available under the trademark "Neodol" from Oil Co., and _C10 - _C13 branched chain alcohol, available under the trademark "Lial" from Liquichimica SA. The amount of the nonionic surfactant mixture is such that the surfactant:basis weight ratio is between 20:1 and 1:5, preferably
10:1 to 1:2, most preferably 5:1 to 1:1
so that it is within the range of When using a nonwoven sheet substrate having a planar area of about 650 cm ² (about 100 square inches) and a basis weight of about 3 g/sheet, the nonionic surfactant loading ranges from 5 to 15 g/sheet. If the nonionic surfactant is liquid at room temperature,
Its physical inclusion can be carried out in various ways. If the substrate consists of a non-sheet reticulated foam article,
The surfactant alone or with other formulation ingredients can be directly impregnated into the article using methods known in the art and described below. When the substrate comprises a nonwoven material or a sheet-like foam article, the surfactant is mixed with a high melting point compatible non-hygroscopic material such as the processing aids described above to form a wax-like solid;
Preferably, the surfactant is present in the solid solution and/or as a dispersed phase. Polyethylene glycols with a molecular weight greater than 4000 are suitable for this purpose because of their melting points and waxy properties. However, due to its hygroscopic nature in extremely humid conditions, this glycol becomes highly hygroscopic when used in significant quantities. Also useful for this purpose are _C12 - _C18 fatty acid alkanolamides. Preferred articles, however, are higher fatty acids, especially C ₁₆ -C ₁₈ saturated fatty acids, in which the weight ratio of fatty acid:nonionic component of the surfactant is between 1:5 and 4:1, preferably between 1:3 and 1:3.
It is used in an amount ranging from 3:2, most preferably from 2:3 to 1:1. If the surfactant is solid at room temperature but melts at temperatures below about 100°C, preferably below about 80°C, this surfactant may be used to incorporate other non-liquid components into the substrate. The agent itself can be used as a vehicle. Tallow alcohol ( _E25 )
or surfactants containing highly ethoxylated non-ions such as _C14 - _C15 primary alcohols ( _E15 ) are examples of this type. Other optional ingredients are foam modifying agents, which can be foaming agents, foam stabilizers, or antifoaming agents. Examples of the first type are _C12 - _C18 fatty acid amides and alkanolamides, and examples of the second type are C12 _-C18 fatty acid amides and alkanolamides.
C ₁₆ alkyl di-lower alkyl amine oxides; examples of the third type are certain ethylene oxide-propylene oxide copolymers such as the C ₂₀ -C ₂₄ fatty acid "Pluronic" series, silicones, silica silicone blends, crystalline waxes, triazines and mixtures of any of the foregoing. Preferred antifoam additives are described in conjunction with silicone foam control agents in US Pat. No. 3,933,672. Add this document as a reference. Silicone materials can be represented by alkylated polysiloxane materials such as silica aerogels and xerogels and various types of hydrophobic silica. Silicone materials can be described as siloxanes of the formula: where X is from about 20 to about 2000, and R and R' are each an alkyl or aryl group, especially methyl, ethyl, propyl, butyl and phenyl. All polydimethylsiloxanes (R and R' are methyl) having molecular weights in the range of about 200 to about 200,000 or greater are effective as foam control agents. Side chain groups R and R' are alkyl, aryl,
Other suitable silicones that are or are mixed alkyl/aryl hydrocarbyl groups exhibit effective foam control properties. Examples of this similar ingredient are dielu, dibropyl, dibutyl, methyl,
Ethyl-, phenylmethyl-, polysiloxanes and the like. Yet another example of an effective silicone foam control agent is a mixture of the aforementioned alkylated siloxanes and solid silica. Mixtures of this type are made by adhering silicone to the surface of solid silica. Preferred silicone foam control agents include hydrophobic silanized (most preferably trimethylsilanized) silica having a particle size in the range of about 10 millimicrons to 20 millimicrons and a specific surface area of about 50 m ² /g or greater. It is typified by a dimethyl silicone fluid having a molecular weight in the range of 500 to about 200,000 intimately mixed in a silicone:silanized silica weight ratio of about 19:1 to about 1:2.
Silicone defoamers are water-soluble or water-dispersible,
It is contained releasably in a substantially non-surfactant, detergent-impermeable bulk. Particularly effective antifoam agents are the self-emulsifying silicone antifoam agents described in US Patent Application No. 622,303 (incorporated by reference). An example of this type of compound is DB-544, available from Dow Corning, which is a siloxane/glycol copolymer. Foam modifiers such as those described above are included at levels up to about 5%, preferably about 0.1 to 2%, by weight of the cationic-nonionic surfactant mixture. Chelating agents that can be included in the products of the present invention include citric acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, and salts thereof, as well as U.S. Pat.
Organic phosphonic acid derivatives as described in No. 2599807;
and carboxylic acid builders such as those described in US Pat. No. 3,308,067, all of which are incorporated by reference. Preferred chelating agents are etrylotriacetic acid (NTA), nitrilotrimethylenephosphonic acid (NTMP), ethylenediaminetetramethylenephosphonic acid (EDTMP) and diethylenetriaminepentamethylenephosphonic acid (DETPMP);
Substrate/chelating agent amount ratio from 20:1 to 1:5, preferably from 5:1 to 1:5, most preferably from 3:1
They are contained in a ratio of 1:1. It has been discovered that certain polybasic acids enhance the bleaching effect of organic perochic acids that occur when the products of the present invention are used with conventional detergent compositions. Examples are EDTMP, NTMP and DETPMP. However, not all chelating polyacids are effective in this regard, but a few weakly chelating polyacids are effective, especially succinic acid and glutaric acid. Antistatic agents can be added as optional ingredients to a wide range of fabric softeners. Examples of cationic nitrogen compounds are di- _C16 - _C18 alkyl, _C1 - _C4 alkyl,
Non-nitrogen substances such as quaternary ammonium salts, imidazolinium salts, and sorbitan esters of _C16 - _C18 fatty acids are preferred emollients and electrostatics suitable for inclusion in the additive products of the present invention. Inhibitors are described in US Pat. No. 3,936,537. Compounds of this type are disclosed in DE 2516104, which is incorporated by reference. Preferred enzymatic materials include commercially available amylases and neutral and alkaline proteases commonly contained in detergents. Because of their heat sensitivity, these materials must be included at or near room temperature and therefore cannot be added to the melt of precursors and other solvents. Therefore, it is most desirable to add the enzyme material during the process of applying the precursor to the substrate as a solvent or slurry. Optical brighteners are anionic or nonionic and are added at a level of 0.05 to 1.0 g per sheet, preferably 0.1 to 0.5 g per sheet. Preferred examples are those available from Ciba Geigy SA under the trademark "Tinopal EMS" and
Anionic materials such as "Blanko phor MBBN" obtained from Farbenfabriken Bayer AG. Catalysts used in the present invention may also include catalysts such as those described in U.S. Pat. No. 3,532,634.
It enhances the efficiency of bleaching species such as a few transition metal salts. The compositions of the present invention include a precursor water-dissociatively bound to a solid, non-granular substrate. Preferably, the substrate is absorbent and the precursor is impregnated therein. Application of the precursor can be carried out in any manner, many methods being known. For example, the liquid precursor can be sprayed during manufacture of the substrate.
If the precursor is liquid, it can be a melt, and it is highly preferred that the precursor melt at a temperature below that at which it decomposes when heated. If the precursor is solid at room temperature, it may be used in liquid form, such as a solution in an organic solvent that evaporates after application, or a slurry or suspension dispersed as a finely divided solid in an aqueous medium or its liquid medium. Can be done. As previously stated, inorganic peroxy bleaches and other substances reactive with organic peroxy compound precursors may be included in the additive products of the present invention, as long as the precursor and bleach are spatially separated. can be contained in In embodiments in which the precursor and inorganic peroxy bleach are contained as physically separate locations on the same substrate, a convenient practice is to apply the respective melts, suspensions or solutions to the substrate. It is attached as a separate band on top. Preferably, the bleach is applied as a solid particle dispersion in a melt processing aid as described above at a temperature in the range of 40°C to 60°C. Using this technique, bleach:substrate weight ratios of up to 15:1 can be obtained. While this coverage level is achieved with cellular substrates, fibrous substrates are practically limited to a weight ratio of about 5:1.
Furthermore, the amount of bleach is limited to 6:1 or less as it is limited by the substrate surface area required due to the inclusion of the precursor. Also, means must be provided for separating the bleach band and the corresponding band of precursor during transport and/or storage of the product. This is accomplished by interposing a layer of deposited material between each layer of the substrate, or by creating a pattern of deposited material that does not match the stack of substrates. When impregnating a substrate, it is believed that the very surface of the pores or fibers that make up the substrate will be coated, and the formation of a broad coverage of the peroxy compound precursor is a highly desirable property of the substrate.
The term "coating" means joining one substrate to the surface of another. "Impregnation" means permeability throughout the interior and exterior of the substrate structure. One factor that influences the absorption capacity of a given substrate is its free space. Therefore, when a precursor is applied to an absorbent substrate, it penetrates into the free space and the substrate is therefore considered to be impregnated. Free space in low grade absorbent substrates such as 1-ply kraft or bond papers is very limited. Therefore, such a substrate is called "dense". That is, while a small portion of the precursor penetrates into the limited free space of the dense substrate, a large amount of the remainder of the precursor does not penetrate into the interior of the substrate, but remains on its surface and forms a coating. considered to be. One method of making a sheet-like substrate impregnated with a precursor consists in applying the precursor to an absorbent paper or nonwoven fabric by a process commonly known as padding. In that case, the precursor is applied to the substrate in liquid form, and the precursor, which is solid at room temperature, is first melted and/or solvent treated. Methods of melting and/or solvent treating precursors are known. It can be easily carried out to obtain a satisfactorily treated substrate. In this method, a liquid precursor is placed in a pan or trough and heated if necessary to maintain the precursor in a liquid state. Next, desired additives are added to this liquid precursor. The roll of absorbent substrate is then attached to the device so that it can be freely rolled out. As the substrate is pumped out, it is impregnated by passing it downwardly through the pan or trough containing the liquid precursor at a rate as low as to provide sufficient impregnation. The substrate then advances upwardly at the same speed, passing between a pair of rollers that squeeze out excess solution. The substrate thus impregnated is cooled to room temperature, after which it is folded, cut to length or perforated, and then packaged and/or used. Said rollers are similar to "squeeze rolls" used in papermaking technology and can be made of hard rubber or steel. Preferably, the rollers are adjustable so that the gap between their respective surfaces can be adjusted to control the amount of precursor liquid on the substrate. In a preferred embodiment of the invention, the liquid pre-drive is sprayed onto the extruded absorbent substrate. The substrate web to be rolled out is arranged to slide over a spray nozzle, which consists of a horizontally arranged tube with a slit formed along the upper surface of the tube. A molten slurry of the precursor and additives mixed therewith is forced through the slit into the substrate, and a squeeze roller is then used to squeeze out excess liquid. 40°~80°C, preferably
Melt temperatures in the range 45° to 65°C are employed, and the molten material is less than 5000 centipoise at 50°C;
It should also preferably have a viscosity of less than 500 centipoise. Another implementation uses metal "nip" rollers and the precursor is sprayed onto the introduction or inlet faces of these rollers. This method uses absorbent paper,
Usually only one side of it can be treated just before it enters the rollers, by which the excess liquid is squeezed out. The method may further utilize a metal roller that is heated to such an extent that the precursor remains in a liquid state. Yet another method is to treat each of the desired number of plies of multi-ply paper separately and then adhere the plies using known adhesives. This method consists of several plies, each treated on both sides, making it possible to create a composite structure with only one side treated. In a preferred method of making products of the invention, a mixture of molten active and optional additives is added to a substrate. In order to obtain a mixture with suitable properties, i.e. a mixture which solidifies in a certain temperature range to give a waxy solid rather than a crystalline solid, it is possible to plasticize a few actives suitable for the purpose of the invention. It is necessary to add a thickening agent or thickening agent. For this reason,
The peroxy compound precursors of the invention can be classified into three types: a) those which are liquid at temperatures up to 25°C;
Things that melt between ℃ and 40℃, b Solids that melt between 40℃ and 95℃, c Solids that melt at 90℃ or higher. For solid groups that melt at high temperatures,
Preferably, its melting point is less than 150°C. However, substances with melting points up to 250°C can also be treated by dispersing them in melts of other substances. Of course, it is clear that the organic peroxy precursor should not decompose significantly at temperatures below its melting point. The melting points of a number of peroxyacid precursors suitable for use in the present invention are shown in the table below.

【table】

Table: In the case of liquid and low-melting peroxy compound precursors, water-soluble or water-dispersible organic auxiliaries with high softening and melting points are required. This adjuvant helps produce a mixture with the desired viscosity/temperature properties. As mentioned above, this type of material must also be non-hygroscopic. Examples of substances of this type are polyvinylpyrrolidone with a molecular weight of 44,000-700,000, and polyazelaic anhydride (as such in the active form) with a molecular weight of 1,000-2,000 and
It is a polyethylene glycol with a molecular weight of Other materials that may be used include sorbitan esters of long chain fatty acids such as myristic acid, stearic acid, and arachidic acid, and non-hygroscopic ethoxylate derivatives of tallow alcohol. Of course, the level of high melting point processing aid used will depend on the level of peroxy precursor used, its melting point, and its degree of solubility in the aid. Although limited by the type of reference material used, adjuvant:precursor ratios can reach 10:1 by weight. The high melting point peroxy precursor can bring the melting point of the mixture to the desired range, i.e. from 40°C to 80°C, preferably from 45°C to
It is necessary to mix with an adjuvant to lower the temperature to 65℃. This adjuvant must be non-hygroscopic and
The precursor must also dissolve in this adjuvant and form a stable fractional system with it.
A mixture in which a portion of the precursor is dissolved and the remainder is dispersed as a suspension is highly desirable. Substances suitable for such purposes include those mentioned above, as well as C _12
-C20 fatty acids and a few water-soluble and water-dispersible esters thereof. As in the case described above, the adjuvant:precursor weight ratio can take a value up to 10:1, but may be limited to a value less than this due to limitations on the amount of adhesion on the substrate. In the case of precursor materials with melting points in the optimum range, ie from 40 DEG to 80 DEG C., no organic auxiliaries are necessary as processing aids in the preferred method of manufacturing the products according to the invention. Precursor materials of this type can be applied in the molten state immediately prior to the precursor and can even be used as carriers for other components such as solid chelating agents or liquid non-ionic surfactants. .
However, in order to increase the rate of release and dissolution of the precursor in the aqueous medium and/or to modify the surface properties of the treated substrate, for example to make the process more reliable by reducing dusting, A waxy adjuvant may also be used. When used, the additive product according to the invention is introduced into the washing liquor at the point in the washing process where the formation of organic peroxy bleaching species is most valuable. In practice, regardless of the wash cycle used, best results are obtained when the product of the invention is introduced into the washing machine at the same time as the fabrics. In the case of washing machines that include a main wash cycle, it is preferred to add the product of the invention at the beginning of the main wash cycle. The invention will now be illustrated by some non-limiting examples. In these examples, parts and percentages are by weight unless otherwise specified. A test method for evaluating the efficiency of peroxy precursors to form organic peroxy bleach species is described below. Perhydrolysis test of activators Sodium perborate tetrahydrate (0.9 g) and pyrophosphate decahydrate were added in 500 ml of distilled water maintained at 25°C by a circulating water bath and mechanically stirred. Sodium (1.25g), EDTA (35ppm), and 0.25
1 mmol of peroxy compound precursor is added to a solution of 10 g of sodium tetrapropylene benzene sulfonate. Water-soluble precursors can be added directly. Other precursors can be predissolved in 10 ml of a suitable solvent that does not react with the bleach species (eg 1,4-dioxane). In such cases, the amount of distilled water should be reduced to 490ml. Within 20 minutes of adding the precursor, withdraw at least one 10 ml aliquot and add each aliquot into a mixture of crushed distilled water ice and distilled water (100 g) and glacial acetic acid (15 ml). Potassium iodide (0.05 g) was added and the mixture was diluted with a 0.01 molar solution of sodium thiosulfate using an iodine indicator (Iotect, available from Britain, Drugs, Haus, Limited). Immediately titrate to one endpoint (blue/black → colorless). Precursors that require a timer of 2 ml or more of 0.01 M sodium thiosulfate are preferred materials for purposes of this invention. Example 1 Methyl-0-acetoxybenzoate (MOAB) (melting point 49°C) was melted and kept at 60°C.
Approximately 23 cm x approx. 3 denier gauge regenerated cellulose fibers are randomly arranged and bonded with polyvinyl acetate binder (70% cellulose, 30% binder solids).
A base sheet of 28 cm (9 inches x 11 inches) was prepared. This base sheet has a basis weight of 1.9 g/sheet. The substrate was immersed in the melt to saturate it, and the sheet was passed between a pair of rolls, one with a rubber surface and the other heated with stainless steel, to remove excess precursor. The sheet was then cooled to solidify the precursor, and its weight was measured. The weight gain was 6.0 g/sheet, ie, the weight ratio of precursor to substrate was 3.1:1. The sheet had a crisp feel and could be formed into rolls with a diameter of 4 cm without difficulty. A test was conducted using the sheet obtained in the above example. The test compared the bleaching effectiveness of three products. The three products mentioned above are as follows. A. A commercially available granular laundry detergent containing 28% sodium perborate. B. A "standard" low temperature bleach laundry product consisting of Formulation A replacing 10% sodium perborate with 6% commercially available organic peroxy compound precursor + 4% sodium sulfate. C. Formulation A with sheet of Example 1. 18 to give each product a product concentration of 0.50%
Approximately 4 pounds of soiled clothing in 30 liters of Clark water was added to a washing machine. On this basis, Product B added 9 g of the precursor and was compared to Product C, which had a sheet that added 6.0 g of MOAB on the sheet. White cotton coupons and 50/50 polyester-cotton blend coupons were stained with wine and tea, the resulting stained coupons were added to the above laundry items, and each preparation was washed at 40°C and Washed at 60°C for 15 and 25 minutes. In each test, Formulation B and C both showed significantly better stain removal effectiveness than Formulation A, and Formulation C was not significantly different from Formulation B. The above results demonstrate that representative additive products of the present invention, when added to conventional laundry detergent solutions, provide bleaching efficacy equivalent to detergent formulations containing inorganic peroxy bleaches and standard organic peroxy bleach precursors. It turns out that. Furthermore, the above bleaching effects are obtained without the micro-speckled color defects that are associated with granular organic peroxy bleach products. Sheets using benzoic anhydride, phenylbenzoate or maleic anhydride instead of methyl-0-acetoxybenzoate also give bleaching effects comparable to the results with product C above. Example 2 A melt of methyl-0-acetoxybenzoate was prepared and 5.5 denier 100% unbleached rayon fibers were randomly placed in an ethyl acrylate binder (Rhoplex HA8) (70% fiber, 30% binder). The above solvent body was applied in the manner described in Example 1 to a substrate having a basis weight of 1.55 g per 11 inches x 9 inches (28 cm x 23 cm) obtained by bonding with the following methods. After removing excess molten material from the substrate and leaving it to cool, the amount of precursor deposited was 3.9
It was hot at g. That is, the precursor:substrate weight ratio is
The ratio was 2.5:1. This sheet had a crisp feel. Instead of the above rayon fiber substrate, 60 to 80 cells/2.5 cm (1 inch) with a density of 0.596 g/16.4 cm ³ (cubic inch) made from “Hydrofoam” (registered trademark) Satisfactory products were also obtained using hydrophilic polyurethane foams with a Example 3 A melt consisting of 50% 0-acetoxy-benzoic acid (melting point 135°C) dispersed in 50% myristic acid was
Prepared at a temperature of °C. 3.0 denier 100% unbleached rayon fibers randomly arranged with ethyl acrylate binder (Rhoplex HA8) (70% fiber, 30%
The above melt was applied in the manner of Example 1 to a nonwoven substrate having a basis weight of 1.6 g/sheet obtained by bonding with a bonding agent). The amount of melt deposited after cooling was 5 g/sheet. That is, the precursor to substrate ratio is
The ratio was 1.6:1. The treated sheet was smooth and flexible. A product with satisfactory properties is obtained when the melt consists of the dispersion in the proportions shown below. i.e. 50% phenyl-0-acetoxybenzoate dispersion in 50% polyethylene glycol 6000, 60
% 40% diacetyldimethylglyoxime dispersion in polyethylene glycol 6000, 75% tetraacetylmethylenediamine dispersion in 25% polyvinylpyrrolidone with molecular weight 700000 60% 40% myristic acid 0
- Acetoxybenzoic acid dispersion 70% in myristic acid
30% Tetraacetyl Glycouryl Dispersion Molecular Weight
1500 is a 60% phthalic anhydride dispersion in 40% polyazelaic anhydride. When the above sheet is used in sodium perborate-containing laundry liquors or percarbonate-containing laundry detergents, bleaching results comparable to Product C of Example 1 are obtained. Example 4 A mixture of 85% methyl-0-acetoxybenzoate and 15% polyethylene glycol 6000 was prepared and melted at 60°C. The above molten material is spread about 24m/
The web of substrate material of Example 2 was pumped through an extrusion nozzle having an elongated opening extending horizontally into the underside of the web, which was being unwound at a rate of 80 feet per minute. extruding the melt so as to penetrate the entire base material;
Spreading of the molten mass was further aided by passing the treated substrate through a pair of rolls located immediately downstream of the extrusion nozzle. The treated substrate web was further cooled by passing over chill rolls before being collected into storage spools and transferred for cutting and packaging. The deposition amount was 6.1 g per 580 cm ² (99 square inches) of sheet area, i.e. the precursor:substrate ratio was
It was 3.3:1. The amount of precursor deposited is 13.2 g, i.e., precursor:
Satisfactory products are obtained if the substrate ratio is increased to 8.5:1. When using a melt with a total weight of 7 g consisting of a blend of 10% MOAB and 90% sorbitan monostearate, i.e. a precursor:substrate ratio of 1:2.2 and a precursor:adjuvant ratio of 1:9, smooth A wax-like product is obtained. Equivalent results can be obtained by using dinitrile succinate, maleic anhydride or polyazelaic anhydride instead of methyl-0-acetoxybenzoate. Satisfactory products are also obtained by replacing sorbitan monostearate with a mixture consisting of 60% tallow alcohol condensed with 30 moles of ethylene oxide, 20% ditallowyldimethylammonium chloride and 20% sorbitan monostearate. Example 5 A procedure similar to Example 4 was carried out except that a melt consisting of a blend of 86.5% methyl-0-acetoxybenzoate and 13.5% myristic acid was used. The resulting coverage was 6.6 g/580 cm ² (99 cubic inches) and the precursor:substrate ratio was 3.1:1. The resulting web had a smooth, waxy feel and was very flexible. Example 6 The procedure of Example 5 was followed except that a melt consisting of a blend of 86.5% methyl-0-acetoxybenzoate and 13.5% myristic acid was used. The resulting coverage was 6.6 g/580 cm ² (99 square inches), the precursor:substrate ratio was 2.6:1, and the product was flexible. When 0.5% g of succinic acid is added to the above melt,
A product with a smoother surface structure can be obtained. 25% N-acetylcaprolactam-75% myristic acid melt (solid at 40°C) instead of the above methyl-0-acetoxybenzoate-myristic acid melt
A smooth wax-like product with the same amount of melt coverage is obtained. Example 7 The method of Example 3 was otherwise followed except that myristic acid was replaced by a mixture of equal parts of sorbitan monostearate and polyethylene glycol 6000. The amount of adhesion is 5 g of melt/sheet, i.e.
A smooth and flexible sheet product was obtained with a precursor:substrate ratio of 1.6:1. Similar results were obtained by replacing 4.5 parts of myristic acid in Example 3 with 4.5 parts of paraffin wax having a melting point of 55°C. Example 8 A mixture of 95% methyl-0-acetoxybenzoate and 5% polyvinylpyrrolidone of molecular weight 700,000 was melted to a liquid having a viscosity of about 170 centipoise at 60°C. In an electric heating bath
0.1% by weight of perfume was added to the above mixture, which remained molten at a temperature of 60° to 70°C. A continuous web substrate is prepared and soaked into the web by placing the loop of the roll downward into the bath and pulling upwardly, and by means of a pair of adjustable pinch rolls located above the bath. The web was pulled out of the bath. One roller had a rubber surface and the other was heated stainless steel. The substrate was formed from 3 denier gauge fibers and bonded with polyvinyl acetate (70%
It consisted of a 100% recycled cellulose nonwoven web (fiber, 30% binder) and had a basis weight of 1.55 g/580 cm ² (99 square inches). The thickness of the cloth above is approximately 0.1mm
(0.005 inch). At a heating roll temperature of 55° to 70°C and a web feed rate of 1 m/min, the deposit amount was 6 g/580 cm ² (99
sq. in.), i.e., the precursor/substrate ratio is 3.7:
A sheet product of No. 1 was obtained. By cooling, a sheet product with a smooth and flexible texture was obtained. Example 9 75 parts of benzoic anhydride (BAN) with a melting point of 40°C and tetraacetyl glycouril (TAGU) (with a melting point of
(237°C) 25 parts of the mixture were blended and heated to 60°C to form a molten dispersion with BAN as the continuous phase. Next, the above mixture was processed using a "Premier "84" Colloid Mill".
mill) (manufactured by Premier, Colloid, Mill, Limited. Walton-on-Thames, Surly, England). This mill is
The product is arranged to deliver a stream of product having a particle size of no greater than 50μ under microscopic examination. The milled dispersion was fed into a channel formed by the nip of a pair of horizontal drive rolls that were heated to maintain the dispersion in a molten state. 3 denier gauge regenerated cellulose fibers randomly arranged and bonded with polyvinyl acetate binder (70% cellulose, 30% binder solids), basis weight 1.55 g/650 cm ²
An approximately 25 cm (10 inch) wide rolled sheet of (100 square inch) material was impregnated by passing it downward through the melt and into the nip. The sheet was passed through a nip to remove any excess precursor mixture from the base roll, then the precursor was cooled, cut into 25 cm square (10 inch square) sheets and weighed. Each sheet had a coverage of 8.0 g, ie, a 3:1 weight ratio of precursor to substrate. The sheet had a smooth feel. The laundry additive products obtained by the above method were tested as follows. Three bundles of 4 kg each (8 kg) including shirts and underwear
lb) of soiled clothes with a 0.7% concentration of washing liquid.
Washing was carried out at 60°C in 20 liters of 18°H water (Ca:Mg=5:1 mol) using a commercially available detergent containing 25% sodium perborate bleach. Each bundle contained colored coupons known to be sensitive to bleach.
Add the additive product sheet described above to one wash solution, add a similar sheet holding only 6g of BAN to the second wash solution, and add no additive product at all to the third wash solution. This was used as a standard comparison. Visual test results of washed and dried bleach-sensitive color specimens were as follows: The results are expressed as a color difference on a scale of 1 to 10 compared to the color of the sample before washing. On the scale: 10 indicates complete discoloration and 1 indicates no perceptible color difference. Standard Comparison 2 Standard Comparison + 6g BAN 8 Standard Comparison + 6g BAN + 2g TAGU 3 A rapidly perhydrolyzing peracetic acid precursor is found to significantly reduce the tendency of bleach-sensitive colored fabrics to fade when processed with perbenzoic acid bleach-added products. . Instead of benzoic anhydride, N-benzoylbenzimidazole, N-benzoylimidazole,
Similar results can be obtained using phenylbenzoate, m-chlorophenylbenzoate or N,N-dibenzoylaniline. Similar results can be obtained by using methyl-0-acetoxybenzoate, tetra-aceptylmethylenediamine, N-acetylcaprolactam, sodium p-acetoxybenzenesulfonate or diacetyldimethylglyoxime instead of tetraacetylglycouril. . Example 10 Production of 2,2-di(4-hydroxyphenyl)propane diacetate 228 g (1 mol) of 2,2-di(4-hydroxyphenyl)propane (bisphenol A manufactured by Ciel, Chemical, Corporation) (BisphenolA),
Manchester, England) was dissolved in 1 liter of glacial acetic acid at 20°C. One milliliter of 98% sulfuric acid was added to the above solution, and 255 g (2.5 moles) of acetic anhydride was slowly added over 30 minutes with stirring. After the addition was complete, the product obtained was poured into excess water and the resulting precipitate was separated, washed with water and dried. The product has a melting point of 79-80℃ and its IR
The spectrum is 1750cm ^-1 which is a characteristic of acetyl group.
It showed a peak at the wavelength of . NMR spectroscopy is 2
showed the presence of two acetyl groups. 0.228 g (1 mmol) of the above product was subjected to the perhydrolysis test specified above. 0.1N Sodium Thiosulfate 3.9 for samples taken 5 minutes after adding the precursor into the sodium perborate solution
A titer of milliliter was obtained. 100 g of bisphenol A diacetate prepared as above and polyethylene glycol 6000
100g of each were mixed and heated to about 90°C to form a melt. The resulting melt was then applied in the manner of Example 9 to a regenerated cellulose substrate having a basis weight of 1.65 g, resulting in a coverage of 11.0 g, i.e. a precursor/substrate ratio.
I got 3.33:1. Instead of bisphenol A diacetate in the above example, bisphenol A diacetate and N-
50 with benzoylimidazole (melting point 202 °C):
The mixture is milled as a molten dispersion in a Premier Colloid Mill to a particle size of less than 50 microns before application to the substrate. Equivalent products are obtained. Similar results can be obtained by using stearic acid, tallow alcohol condensed with 25 moles of ethylene oxide, or a mixture thereof in place of polyethylene glycol 6000 in the above example. Example 11 50 parts of tetraacetylethylenediamine (TAED) (melting point 148°C), 10 parts of benzoic anhydride (melting point 40°C) and 40 parts of stearic acid (melting point 69°C)
°C), make a blend by first dissolving stearic acid and benzoic anhydride at a temperature of 75 °C, then adding TAED. Following the method of Example 9,
A sheet is prepared with a coverage of 10 g/650 cm ² (100 square inches) and a precursor:substrate ratio of 4:1 and a perbenzoic acid precursor:peracetic acid precursor of 1:5. Example 12 The precursor-processing aid blend of Example 11 was
Density of 0.6g/ ^16cm3 (cubic inch) and approx.
Applicable to hydrophilic polyurethane foam of 80 cells/2.5 cm (inch length) ("Hydroform" manufactured by Scotto, Paper, Co., Ltd., Ed. Easton, Benzylvania, USA). The sheet has a basis weight of 2 g/650 cm ² (100 square inches), a 5:1 precursor:substrate weight ratio, and a 1:5 perbenzoate:peracetic acid precursor. Example 13 5 g of para-acetoxybenzenesulfonic acid is applied to a 25 cm x 25 cm (10 inch x 10 inch) nonwoven sheet of 1.6 g/sheet basis weight of 70% by weight regenerated cellulose fibers and 30% ethyl acrylate binder. 55 of sodium, 1 g ethylenediaminetetramethylenephosphonic acid and 5 g lauric acid
The mixture at 0.degree. The impregnated sheet was then passed between a pair of rolls to remove excess mixture. Amount of adhesion
At 11 g, a precursor:substrate weight ratio of 3.12:1 was obtained. Instead of sodium 0-acetoxybenzenesulfonate, a 50/50 mixture of benzoic anhydride and methyl-0-acetoxybenzoate, or tetraacetylethylenediamine, bisphenol A diacetate, 1,3,5-triacetyl 2,4, Equivalent products can be obtained using 6-triazine, p-acetoxyacetophenone or diacetyldimethylglyoxime. Similar results can be obtained by using NTMP, succinic acid or diethylenetriaminopentamethylenephosphonic acid instead of EDTMP. Practical Practice 14 A blend of 5 g bisphenol A diacetate, 5 g polyethylene glycol 6000 and 1 g ethylenediaminetetramethylenephosphonic acid was prepared according to the method of Example 13 and had a basis weight of 1.6 g/
The sheet was applied onto a 25 cm x 25 cm (10 inch x 10 inch) regenerated cellulose sheet substrate. The sheet product had a smooth, flat structure and flexibility. Example 15 Detergent additive products A and B according to the invention consist of the following according to the method of Example 13: A EDTMP 1g TAED 4g Stearic acid 2g TAE ₂₅ 2g 9g Substrate: Nonwoven regenerated cellulose fiber sheet containing 30% by weight ethyl acrylate binder. Basis weight
1.6 g/650 cm ² (100 square inches) B EDTMP 1.5 g TAED 5 g Lauric acid 3 g TAE ₂₅ 3 g Methyl vinyl ether maleic anhydride copolymer (molecular weight 250000) 1 g 13.5 g Substrate: Non-woven regenerated cellulose with 30% by weight ethyl acrylate binder fiber sheet. (1.5
In ^each case, a melt of the carboxylic acid and alcohol ethoxylate is prepared, the remaining ingredients are combined into a dispersion, and then applied to the substrate. Example 16 50 parts of tetraacetylhexamethylene diamine (TAHD) are melted at 70° C. and mixed with 50 parts of “Dovanol) 45E15” and 10 parts of ethylenediaminetetramethylenephosphonic acid sodium salt.
The above mixture is used to impregnate a nonwoven fibrous substrate according to the method of Example 4 to obtain a detergent additive product having the composition shown below. TAHD 5g Dovanol 45E15 5g EDTMP 1g Substrate 1.58g (precursor:substrate weight ratio 7.1:1) The substrate is made of 5.5 denier 100% unbleached rayon fibers arranged in random order with an ethyl acrylate binder (Rhoplex HA ₈ ). It has a bonded (70% fiber, 30% binder) basis weight of 1.55 g/650 cm ² (100 square inches). A base made of randomly arranged 3.0 denier 100% unbleached rayon fibers, basis weight 1.6 g/650 cm ²
A similar product can be obtained by replacing it with (100 square inches). Equivalent products can be obtained by replacing EDTMP with diethylenetriaminopentamethylenephosphonic acid (DETPMP) or nitrilotrimethylenephosphonic acid (NTMP). Example 17 Chicopee Manufacturing Co., Ltd.
(Milltown, New Jersey, USA) code name SK650WF x 577 polyester wood pulp bonded mixture approximately 30cm x 25cm
(12 inches x 10 inches) non-woven sheet with a basis weight of 50
1 g of EDTMP dispersed in a mixture of 6 g of "Dovanol 45E7" and 6 g of polyethylene glycol 6000,
and 5 g of TAED according to the method of Example 4. The resulting soaked product was sufficiently hard to be self-supporting when held horizontally at one end and had a smooth waxy feel. Instead of the above substrate, density 20Kg/m ² and thickness 3
Satisfactory products were also obtained using polyurethane foam measuring approximately 20 cm x 9 cm (9 inches x 4 inches). The coating weight of the product was 18 g/sheet. The same product as above can be obtained by replacing the above TAED with any one of the following. p-acetoxyacetophenone, 1,3,5-triacetyl-3,4,6-triazine, diacetyldimethylglyoxime, 2,2-di-(4-hydroxyphenyl)propane diacetate, tetraacetylhexamethylene Diamines, tetraacetylhydrazine, methyl-o-acetoxybenzoate, tetraacetylglycouryl, or N-acetylcaprolactam Similar results can be obtained by using sorbitan tristearate in place of polyethylene glycol 6000.

Claims (1)

[Scope of Claims] 1. characterized by including the following a and b:
Laundry additive products. a. a substrate consisting of a flexible sheet-like article, and b. an organic peroxy compound precursor in combination with the same to be released by water. However, the weight ratio of this precursor substrate is within the range of 30:1 to 1:10. 2. A laundry additive product according to claim 1, wherein the weight ratio of precursor:substrate is in the range of 10:1 to 1:10. 3. Claim 1 or 2, wherein the precursor:substrate weight ratio is in the range of 8:1 to 1:2.
Laundry additive products as described in any of the paragraphs. 4. A laundry additive product according to any one of claims 1 to 3, wherein the organic peroxy compound precursor is selected from the group consisting of anhydrides, esters, imides, and oximes. 5 Peroxy compound precursor is 1:10 to 10:
consisting of a mixture of peroxybenzoic acid precursor and peroxyacetic acid precursor in a weight ratio within the range of 1;
A laundry additive product according to claim 4. 6. A laundry additive product according to claim 5, wherein the peroxybenzoic acid precursor and the peroxyacetic acid precursor are present in a weight ratio ranging from 5:1 to 1:5. 7 The organic peroxy compound precursor is a C ₁ -C ₈ aliphatic acylimide, an arylacyl imide, an N-substituted derivative thereof, and an aliphatic or aromatic mono-
and phenol esters of dicarboxylic acids (however, acyl groups include C ₁ to C ₆ alkyl groups)
A laundry additive product according to claim 4 selected from the group consisting of: 8 The organic peroxy compound precursor is heated to 25°C or
A laundry additive product according to claim 7 having a melting point in the range of 150°C. 9 Organic peroxy compound precursor at 40°C to 95°C
9. A laundry additive product according to claim 8, having a melting point in the range of . 10 Processing and release aids, surfactants, chelating agents, foam modifiers, anti-resettling agents and soil suspending agents, fabric softeners and antistatic agents, enzymes, fragrances, colorants, optical brighteners , and a bleaching catalyst, wherein the weight ratio of each functional component to the substrate does not exceed 20:1. A laundry additive product according to any of clause 9. 11. The laundry additive product of claim 10, wherein the weight ratio of peroxy compound precursor to total functional component is in the range of 500:1 to 1:15. 12 The surfactant is a condensation product of an alkylene oxide and an organic hydrophobic residue having a reactive hydrogen, and the surfactant has an HLB in the range of 8.0 to 17.0.
A laundry additive product according to any one of claims 10 or 11, having the following: 13. The laundry additive product of claim 10, wherein the nonionic surfactant is a substantially linear alcohol ethoxylate containing 7 to 20 ethylene oxide groups per mole of alcohol. . 14. The chelating agent consists of a polybasic acid selected from the group consisting of citric acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, substituted or unsubstituted alkylene and aminoalkylene phosphonic acids, succinic acid, and glitaric acid, and the alkali metal and ammonium 14. A laundry additive product according to any of claims 10 to 13, wherein the salt is present such that the chelating agent:substrate weight ratio ranges from 5:1 to 1:20. 15 The polybasic acid or its alkali metal or ammonium salt is selected from the group consisting of nitrilotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, succinic acid, and glutaric acid, and the polybasic acid:substrate weight ratio 15. A laundry additive product according to claim 14, wherein is present in an amount within the range of 1:1 to 1:20. 16. The processing aid is a solid water-soluble or water-dispersible organic adjuvant with a softening point above 40°C and a melting point below 80°C, and the weight ratio of precursor to adjuvant is from 20:1 to 1. A laundry additive product according to any one of claims 10 to 15, within the range of: 17 The processing aid is 5 to 1 mole of alcohol.
Molecular weight 44,000 containing 30 ethylene oxide groups
17. The laundry additive product of claim 16 selected from the group consisting of polyvinyl pyrrolidone of 700,000, _C12 to _C18 fatty acids and their esters and amides, and polyethylene glycol with a molecular weight greater than 4000. . 18 C ₁₆ -C ₁₈ saturated fatty acids with a ratio of fatty acid to nonionic portion of the surfactant mixture of 1:5 to 4:1.
14. The laundry additive product of claim 13, wherein the laundry additive product is contained at a level within the range of . 19. A laundry additive product according to any of claims 1 to 18, wherein the flexible sheet is water-soluble. 20. A laundry additive product according to any of claims 1 to 18, wherein the flexible sheet is comprised of a water-insoluble foam or fibrous material. 21. The laundry additive product according to claim 1, wherein the flexible sheet is a fibrous nonwoven sheet. 22. The laundry additive product of claim 21, wherein the fibrous sheet is comprised of a non-woven material, at least a portion of which is synthetic and bound by a water-insoluble binder. . 23 The sheet is formed with openings penetrating both sides thereof, with 10 to 18 openings per square cm, and the basis weight of the sheet is 40 to 60 g/cm2.
23. A laundry additive product according to claim 22, wherein ^m2 . 24 further contains an inorganic persalt in combination with the substrate for release by the water such that the inorganic persalt does not come into contact with the organic peroxy compound precursor until the additive product is introduced into the wash liquor. 24. A laundry additive product according to any one of claims 1 to 23, wherein the laundry additive products are arranged spatially separated on the substrate. 25. The laundry additive product of claim 24, wherein the inorganic persalt and the organic peroxy compound precursor are disposed in separate bands on the substrate article. 26. forming a peroxy compound precursor into a fluid, and combining the fluid with a solid substrate article such that the treatment surface of the substrate is maximized;
and solidifying the fluid. a. a substrate consisting of a flexible sheet-like article, and b. an organic peroxy compound precursor in water-released combination therewith. However, this precursor to substrate weight ratio is 30:1.
It is within the range of 1:10 to 1:10. 27 The organic peroxy compound precursor has a melting point exceeding 95°C, and the precursor and the
forming a molten mixture with a non-hygroscopic organic solid having a lower melting point, such that the molten mixture has a melting point in the range of 40°C to 80°C; and forming the molten mixture into a fibrous sheet. and cooling the impregnated sheet to solidify the mixture. .