FI73736B - TVAETTILLSATSPRODUKT OMFATTANDE EN FAST TVAETTILLSATSKOMPOSITION OCH ETT FLEXIBELT ENKELSIKTAT SKIVLIKNANDE PERFORERAT UNDERLAG. - Google Patents

Abstract

Laundry additive products comprising a solid laundry additive composition and a flexible, sheet-like apertured substrate carrying a water-releasable coating of the laundry additive composition. The substrate has an aperture density of from about 10 to 30 apertures per sq cm and the apertures have a width of from about 0.5 to 5mm and a length of from about 0.8 to 5mm. The product comprises areas of uncoated aperture and areas within the coating covers the apertures and extends between opposing surfaces of the substrate. The ratio of areas of uncoated to coated apertures is from about 15:1 to 1:3. The weight ratio of composition:substrate is at least 5:1. The additive products combine a high loading of composition together with excellent flexibility, product release, feel and storage characteristics.

Description

! 73736

The present invention relates to laundry additive products comprising a water-insoluble flexible single-layer plate-like perforated substrate and a solids deposited on or impregnated with the substrate. The additive products according to the invention 10 are used for cleaning clothes or other fabrics or for improving the washing smell.

Laundry additive products based on water-insoluble substrates are now known in the art. For example, U.S. Patent 3,442,692, Gaiser, May 6, 1969, describes a method for softening fabrics and reducing static electricity in a washer or dryer using a fabric finisher on a substrate. GB 1 586 769 20 describes a laundry additive product comprising a precursor of an organic peroxy compound in combination with a solid product, in particular a plate-like, water-insoluble substrate. U.S. Patent 4,170,565; Flesher et al., Relates to a fabric cleaning product which provides for the sequential release of surfactant ingredients and which consists of a surfactant composition between two water-insoluble substrate layers of a specified air permeability.

A key requirement for a laundry additive product on a substrate, especially one to be used in laundry and the like as a detergent or detergent additive, is the ability to store a relatively large amount of laundry additive composition on the substrate while providing rapid and complete release of the additive composition during the wash. This is in contrast to cleaning cloth products, which are used for washing and rubbing hard surfaces such as dishes and table tops, where physical rubbing during use ensures that the correct amount of cleaning composition 5 is released for the cleaning operation. Such products are generally designed for multiple repetitive uses and are therefore formulated to release only a small portion of the amount of cleaning composition in a single application of the product.

In order to achieve a rapid release of the laundry additive composition, it has generally been found desirable to use a substrate having a low basis weight. Particularly suitable in this respect are single-layer substrates on or on which the laundry additive composition 15 is impregnated. The result is a high load and a low basis weight of the substrate for laundry additive products with an optimal, undoubtedly high composition in normal laundry use: substrate-to-weight ratio (referred to herein as the load ratio).

However, from the point of view of handling, product appearance and storage properties, a number of difficult problems arise in the design of laundry additive products with high load ratios. The first and most important problem is that the flexibility of the substrate deteriorates rapidly with a high load ratio, and the product becomes more and more rigid and more like a slab. This is not only inconvenient for consumers, but also creates handling problems associated with peeling the composition from the board, as well as manufacturing and packaging problems associated with folding the product into a form that is space-consuming and comfortable to use. If, on the other hand, the additive composition is made sufficiently soft and malleable to avoid flexibility problems, the products become quite sticky and uncomfortable to the touch, and the associated handling and storage problems (adhesion of layers, etc.) become worse.

It has now been found that by selecting certain laundry-5 laundry additive compositions having certain melting properties, as well as certain plate-like perforated substrates having a certain size and density of holes, and coating the substrate so that the composition covers and fills only a portion of the substrate holes, laundry-10 sun additive products can be made which at the same time meet the requirements of high load, good release properties and excellent flexibility and product comfort.

Thus, the present invention relates to a laundry additive product having a high composition: substrate ratio associated with excellent flexibility properties, which product does not feel sticky and is easy to manufacture, use and store, and which product can be used in laundry to effectively clean clothes and other fabrics. and easily or to improve the washing result.

The invention relates to a laundry additive product comprising a) a solid laundry additive composition having a softening temperature of at least about 35 ° C and containing at least about 40% by weight of water-soluble or dispersible organic binders having a final melting point of less than 85 ° C; and b) a flexible single-layer plate-like torn substrate having a hole density of about 10 to 2 30 about 30 holes / cm and having an average hole width of about 0.5 to about 5 mm and a length of about 0.8 to about 5 mm, wherein is a water - releasing coating consisting of a laundry additive composition, wherein the weight ratio of the composition to the substrate is at least 5: 1.

The laundry additive composition according to the invention is characterized in that the substrate has areas where the holes are uncoated and areas where the coating covers the holes and extends between opposite surfaces of the substrate, the area of the uncoated holes and the area of the coated holes. from 15: 1 to 1: 3.

As for the substrate, the density of the holes is preferably from about 13 to about 26, more preferably from about 16 to about 22 23 holes / cm, it has a basis weight of n> in 10 to about 70 2 2 g / m 2, more preferably from about 20 to about 50 g / n, and contains hydrophobic binder resins from about L2 to about 25, more preferably from about 16 to 22% by weight of the total substrate. The holes 10 themselves are generally symmetrical about the longitudinal axis (i.e., have mirror symmetry) and have an average width of about 0.7 to about 2.5 mm and a length of about 1.7 to about 4 mm.

On the other hand, the surface area of the holes is preferably from about 0.7 to 2 to about 7 mm, more preferably from about 0.8 to about 3.5 mm, and the length to width ratio is at least 1: 1 and preferably at most about 6: 1, most preferably up to about 4: 1. These parameters are very advantageous in providing the best possible ratio of uncoated and coated hole areas and complete filling of the coated holes between opposite surfaces of the substrate.

The holes in the substrate may be elongate in shape (generally, for example, oval or diamond-shaped), with holes having a width of about 0.8 to about 1.5 mm and a length of about 2 to about 3.5 mm. However, in preferred embodiments, the holes are square in shape with a side length object of about 1 to about 2.5 mm. As used herein, "length" means the length of the major longitudinal axis (i.e., the longest axis) and the "width" is the largest dimension perpendicular to said axis 30. As for the load ratio (i.e., weight to composition: substrate ratio), it is preferably at least about 6: 1, more preferably at least 7: 1. In addition, the ratio of uncoated to a range of coated holes in the final product is preferably from about 6: 1 to about 1: 2, more preferably from about 4: 1 to about 1: 1.

The laundry additive composition preferably contains at least about 50%, more preferably about 60% organic binders; each of which, in turn, preferably has a final melting temperature below about 75 ° C, more preferably below about 70 ° C. The softening temperature of the laundry additive composition itself is preferably at least about 40 ° C, especially at least about 50 ° C.

In preferred embodiments, the laundry additive product contains at least about 5% by weight, preferably at least about 15% by weight of the composition of a water-soluble or water-dispersible organic binder having an onset temperature of at least 35 ° C and finally melting below about 85 ° C: in. The binder is preferably polyethylene glycol having a molecular weight greater than about 1000, a fatty acid or ester or amide thereof, polyvinylpyrrolidone1 having a molecular weight of about 40,000 to about 700,000, or a C 1-4 fatty alcohol ethoxylated from about 14 to about 700,000. With 100 moles of ethylene oxide.

In order to provide the best possible flexibility and comfort combined with excellent dispersibility in water at a high load ratio, polyethylene glycols having a molecular weight greater than about 4000, preferably greater than about 7000 are highly preferred, with these materials preferably containing at least about 40 S, more preferably at least about 50% organic binder.

The laundry additive products of the invention suitably contain at least about 5%, preferably at least about 20% of an additive composition which is an organic detergent which is an anionic, nonionic or cationic surfactant or a mixture thereof. Preferred nonionic surfactants are those having a final melting point below about 85 ° C and which form part of a binder consisting of organic substances. Preferred cationic surfactants have an onset melting point of at least about 35 ° C and may either form part of the organic binder or be dispersed in the organic binder. Preferred anionic surfactants have a final melting point above about 100 ° C and are dispersed in the organic binder.

Other active solids may also be present dispersed in the organic binder, in particular inorganic or organic peroxy bleaches, preferably at least about 5% by weight of the amount of the additive composition, and / or precursors of organic peroxyacid bleaches, preferably at least about 2% by weight. % of the amount of additive composition. Other suitable active ingredients include detergent enzymes, fluorescents, photo-activators, complexing agents, bleach catalysts and foaming agents.

The laundry additive products of the invention will be discussed in detail below.

Preferred substrates for use herein are perforated nonwoven fabrics, which can be generally defined as gluing bonded fibrous or filamentary products having a woven or carded fleece structure (where the strength of the fiber is suitable for carding), or which consist of fibreboards in which the fibers or filaments are randomly distributed, i.e., in a random order (i.e., an order of fibers in a carded fabric that often exhibits partial orientation of the fibers as well as a completely random orientation) or approximately parallel.

7 73736

The fibers or filaments may be natural fibers (for example, wool, silk, wood pulp, jute, hemp, cotton, linen, sisal or ramie), synthetic fibers (for example, rayon, cellulose, ester fiber, polyvinyl derivatives of any kind, polyolefins, polyamides or polyesters) or polyesters. mixtures of the above.

Nonwovens are generally made by air or water layering methods, in which the fibers or filaments are first cut into pieces of suitable length from long strands, passed into an air or water stream, and then deposited on a wire through which the fibrous air or water is passed. The layered fibers or filaments are then bonded together by gluing, dried, cured, and otherwise treated as desired to form a nonwoven fabric.

The nonwoven fabric is preferably made of cellulose fibers, especially regenerated cellulose or rayon, which are lubricated with a conventional textile lubricant such as sodium oleate. The fibers preferably have a length of about 4 to about 50 nm, especially about 8 to about 20 mm, and a thickness of about 1 to about 5 denier (denier is an internationally accepted unit for measuring yarns and corresponds to a weight of 9000 m of yarn in 25 grams). The fibers are preferably at least partially randomly oriented, in particular substantially completely random, and are bonded together by a hydrophobic or substantially hydrophobic binder resin, in particular a nonionic self-crosslinking acrylic polymer or polymers. In highly preferred embodiments, the fabric contains from about 75% to about 88%, especially from about 78% to about 84% fiber, and from about 12% to about 25%, especially from about 16% to about 22% hydrophobic binder resin, and has a basis weight of from about 10% to about 70%, preferably 3,73736 20-50 g / m2. Suitable hydrophobic binder resins include ethyl acrylate resins such as Primal HA24 and Rhoplex HA8 and HAI 6 (Rohm and Haas, Inc) and mixtures thereof.

5 The holes in the substrate, which extend from one surface of the substrate to another, are normally in a regular order and are formed during the deposition of the fibers during the manufacture of the substrate. Examples of perforated nonwoven fabrics are provided in U.S. Patent Nos. 3,741,724, 3,930,086 10 and 3,750,237.

An example of a nonwoven substrate suitable in this context is a board made of regenerated cellulose in which 1.5 denier fibers are bonded together with a Rhoplex HA8 binder (fiber: binder-15 material ratio of about 77:23) and having a basis weight of about 35 g / m 2 and the number of holes is about 17 pcs / cm. The holes are generally oval in shape and are arranged in parallel. The width of the holes is about 0.9 mm and the length is about 2.5 mm measured in a stress-free space. Another highly preferred substrate based on 1.5 denier fibers of regenerated cellulose bonded with Rhoplex HA8 binder has a fiber: binder ratio of about 82:18, a basis weight of about 35 g / m 2 and about 22 holes / cm. In this example, the holes are generally square in shape and have a width (untensioned) of about 1.1 mm. In this example, the holes are arranged in parallel.

The size and shape of the base plate of each product unit is optional and is mainly determined by ease of use. Thus, the plate 30 should not be so small that it gets caught in the slots of the machine or washable clothes, or so large that it is cumbersome to pack and unpack from the sales package. Suitable for the purposes of this invention are sheets having an area of about 130 to about 1300 cm, preferably 2 3? the surface area αία is about 520 to about 780 cm.

II

9,73736

The laundry additive composition is solid at ambient temperatures (25 ° C and below) and preferably has a softening temperature of at least about 35 ° C, more preferably at least about 40 ° C, especially at least about 50 ° C. Softening temperatures] a means the temperature at which a change occurs from a plastic run to a viscous run; at ambient temperatures, the composition is thus in the form of a malleable solid and has a non-zero tensile strength. The hardness of the compositions at ambient temperatures can be determined by conventional methods, for example by a method according to IP49 using a penetrometer (or a technically equivalent method according to ASTM-D5 or BS4691). Thus, the preferred compositions for use in accordance with the invention have a penetration depth of less than about 10 (measured in tenths of a millimeter), more preferably less than about 7, at a load of 100 a at 25 ° C after 15 s as measured by IP49. On the other hand, the softening temperature of the composition is , where the penetration depth of 20 to 15 s according to IP49 exceeds about 30.

The laundry additive composition according to the invention contains a binder formed by organic substances having certain melting properties. Melting temperatures are measured using a Dupont 910 DSC equipped with a mechanical cooling system and an R90 thermal analyzer as follows: A 5-10 mg sample of organic material free of free water and solvents is sealed in a crucible using a blank as a reference. the crucible. The sample is first heated to melt and then rapidly cooled (about 20-30 ° C / min) to -70 ° C. Thermal analysis is then performed at a heating rate of 10 ° C / min using sufficient gain of the Δ T signal (i.e., the temperature difference between the sample and the reference crucible-vertical axis) to obtain a ratio of endothermic peak: north-35 noise greater than 10: 1. The end point of melting is then the temperature corresponding to the intersection of the tangent of the steepest part of the endothermic curve at the end of the endothermic curve and the horizontal line parallel to the temperature axis of the sample at the highest temperature endothermic peak.

The melting end point of the organic substances forming the binder is below about 85 ° C. In addition, the laundry additive compositions of the invention preferably contain at least about 5% of a binder composition of 10 organic materials having a melting end point of less than about 85 ° C, preferably less than about 80 ° C; particularly preferably below about 70 ° C, and a melting onset temperature of at least 35 ° C, preferably at least 40 ° C, particularly preferably at least 50 ° C. The onset of melting temperature 15 can likewise be measured thermoanalytically as described above, and you maintain the temperature of the sample at the point where the basic curve intersects the steepest part of the tangent to the lower endotherm temperature of the endothermic curve.

All kinds of detergent ingredients can be added to the laundry additive compositions of the invention. The additive products may suitably contain from about 5% to about 100%, preferably from about 20% to about 100%, more preferably from about 35% to about 75% of an organic detergent which is an anionic, nonionic or cationic surfactant or a mixture thereof. Anionic surfactants are preferably from about 7% to about 38% by weight, more preferably from about 15% to about 30% by weight of the composition, nonionic surfactants from about 8% to about 32% by weight, more preferably from about 12% to about 30% by weight. 25% by weight of the composition, and cationic surfactants from about 5% to about 30% by weight, more preferably from about 8% to about 20% by weight of the composition.

The anionic surfactant may be any of the 35 or more such substances conventionally used in laundry detergents. U-73736 Suitable synthetic anionic surfactants are water-soluble alkyl benzene sulfonates, alkyylisul-sulfates, alkyl polyethoxy ether sulphates, parafiinisulfo-sulfonates, o <-olefiinisulfonaatit, -sulfokarboksylaatit ^ 5 and their esters, alkyl, fatty acid monoglyceride sulfates and sulfonates, alkyl-lifenolipolyetoksieetterisulfaatit, 2-acyloxy alkane -1-sulfonate and β-alkyloxyalkane sulfonate.

A particularly well-suited group of organic surfactants includes water-soluble salts of organic sulfur-containing reaction products, especially alkali metal, ammonium or alkanolammonium salts having from about 2 to 22, especially about 10 to 20, alkyl atoms in the molecule. or an alkyl-15 aryl group and a sulfonic acid or sulfuric acid ester group. (The term "alkyl" includes the alkyl portion of acyl groups). Examples of such a group of synthetic detergents which form part of the detergent compositions of this invention include sodium and potassium alkyl sulfates, especially those obtained by sulfation of higher alcohols having 3 to 18 carbon atoms and prepared by reduction of tallow or coconut oil glycerides. , and sodium and potassium alkylbenzene sulfonates in which the alkyl group contains about 9-15, especially about 25 11-13, carbon atoms in a straight or branched chain, for example those described in U.S. Patent Nos. 2,220,099 and 2,477,383, and those prepared by straight chain alkylbenzenes obtained by alkylation with chloroparaffins (using aluminum trichloride catalysis) or alkylation with straight-chain olefins (using hydrogen fluoride catalysis). Of particular interest are straight-chain alkylbenzene sulfonates having an average alkyl group size of 11.8 carbon atoms and abbreviated as gLAS, and 35 methyl alkyl sulfates in which the alkyl group is branched and contains 12 to 15 carbon atoms.

Other anionic detergent compounds useful in the present invention include sodium (C 10-18 alkyl) glyceryl ether sulfonates, especially ethers of higher alcohols from tallow and coconut oil, sodium coconut oil fatty acid monoglyceride sulfonates and sulfates, and sodium ca. 10 ethylene oxide units and wherein the alkyl group contains about 8-12 10 carbon atoms.

Other anionic detergent compounds useful in this invention include water-soluble salts or esters of β-sulfonated fatty acids having a fatty acid moiety of about 6 to 20 carbon atoms and an ester group of about 15 to 10 carbon atoms, water-soluble salts of 2-acyloxyalkane-1-sulfonic acids having an acyl group of about -9 carbon atoms and an alkane moiety of about 9-23 carbon atoms; alkyl ether sulfonates having an alkyl group of about 10 to 18, especially about 12 to 16, carbon atoms and containing about 1 to 12, especially 1 to 4, and most especially 1 to 4, ethylene oxide units; water-soluble olefin sulfonates containing about 12 to 24, preferably about 14 to 16, carbon atoms, especially those prepared by reaction with sulfur trioxide followed by neutralization under conditions such that any sulfones present are hydrolyzed to the corresponding hydroxyalkanesulfonates; water-soluble paraffin sulfonates containing about 8 to 24, especially 14 to 18, carbon atoms; and β-alkyloxyalkane sulfonates having an alkyl group of about 1 to 3 carbon atoms and an alkane moiety of about 8 to 20 carbon atoms.

The alkane chains of the above-mentioned non-soap surfactants may be derived from natural sources, such as coconut oil 35 or tallow, or may be prepared synthetically.

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13 73736 as a character using the Ziegler or Oxo process. Water solubility can be achieved using an alkali metal, ammonium or alkanolammonium cation, with sodium being preferred. Suitable fatty acid soaps include carbon atoms of higher fatty acids having from about 8 to about 24, preferably from about 10 to about 22, and most preferably from about 16 to about 22, alkyl salts with common alkali metals (sodium, potassium) and ammonium and alkanol ammonium salts. Suitable fatty acids can be obtained from natural sources such as soybean oil, castor oil, tallow, tran and fish oils, lard and other animal fats, and mixtures thereof. Fatty acids can also be prepared synthetically (for example, by oxidizing crude oil or hydrogenating carbon monoxide using the Fischer-Tropsch method). Suitable acids include rosin acids such as rosin and tall oil rosin acids. Naphthenic acids are also suitable. Sodium and potassium soaps can be prepared directly by saponifying fats or oils or by neutralizing 20 fats of free fatty acids prepared by separate manufacturing methods. Particularly useful are the sodium and potassium salts of fatty acid mixtures derived from tallow and hydrogenated fish oil.

Particularly suitable in this invention are mixtures of anionic surfactants, especially mixtures of surfactant sulfonates and sulfates in a weight ratio of about 5: 1 to 1: 5, preferably about 5: 1 to 1: 1, and even more preferably about 5: 1 -1.5: 1. Particularly preferred is an alkyl benzene sulfonate in which the alkyl radical contains 9 to 15, in particular 11 to 13, carbon atoms and the cation is an alkali metal, preferably sodium, and either an alkyl sulphate containing 10 to 20, preferably 12 to 18, carbon atoms or ethoxy sulphate. wherein the alkyl radical contains from about 10 to 20, preferably from about 10 to 16, carbon atoms, and the average degree of ethoxylation of ____ to 73736 14 is from 1 to 6, and which contains a mixture of an alkali metal cation, preferably sodium.

Surfactants useful in the present invention include condensation products of ethylene oxide with a hydrophobic group to form a surfactant having a hydrophilic-lipophilic balance (HLB) of approximately 8-17, preferably about 9.5-13.5 and even more preferably about 10-12.5. The hydrophobic moiety may be aliphatic or aromatic in nature, and the length of the polyoxyethylene group condensed with each hydrophobic group can be readily adjusted to provide a water-soluble compound in which the desired balance exists between the hydrophilic moieties and the hydrophobic moieties.

1. Examples of suitable nonionic surfactants are: 1) Condensation products of alkylphenol and polyethylene oxide, for example those obtained by condensing alkylphenols having an alkyl group of 6 to 12 carbon atoms as a straight or branched chain with ethylene oxide in the presence of 3-30, preferably 5-14 moles, per mole of alkylphenol. The alkyl substituent present in such compounds may be derived from, for example, polymerized propylene, diisobutylene, octene or nonene. Other examples are dodecylphenol condensed with 9 moles of ethylene oxide per mole of condensed phenol, dinonylphenol condensed with 11 moles of ethylene oxide per mole of phenol, nonylphenol and diisooctylphenol condensed with 13 moles of condensed phenol.

2) Condensation products of primary or secondary aliphatic alcohols containing 8 to 24 carbon atoms in either a straight or branched chain with ethylene chloride of about 2 to 40 moles, preferably 2 to 9 15 73736 moles, per mole of alcohol. Preferably, the aliphatic alcohol contains 9 to 12 carbon atoms and is ethoxylated with 2 to 9, preferably 3 to 8, moles of ethylene oxide per mole of aliphatic alcohol. Preferred surfactants are prepared from primary alcohols that are either linear (such as those derived from natural fats or those prepared by the Ziegler process from ethylene oxide, such as myristyl, cetyl and stearyl alcohol) or partially branched, such as Lutensols, Dobanols and Neodols. 25% of 2-methyl substituents (Lutensol is the trade name of BASF, Dobanol and Neodol of Shell), or Synperonic with a 50% 2-methyl substitution (Synperonic is the trade name of ICI), or primary alcohols with the structure 15 is more than 50% branched and sold by Liquichimica under the trade name Lial. Specific examples of nonionic surfactants within the scope of the invention are Dobanol 45-4, Dobanol 45-7, Dobanol 45-9, Dobanol 91-2.5, Dobanol 91-3, Dobanol 91-4, Dobanol 91-6 , 20 Dobanol 91-8, Dobanol 23-6.5, Synperonic 6, Synperonic 14, condensation products of coconut alcohol having 10 to 14 carbon atoms in the alkyl moiety with ethylene oxide averaging 5 to 12 moles per mole of alcohol, and tallow alcohol having the hydrocarbon moiety has 16 to 22 carbon atoms, 25 condensation products with ethylene oxide averaging 7 to 12 moles per mole of alcohol. Secondary linear alkyl ethoxylates, especially those of the Tergitol series having an alkyl group of about 9 to 15 carbon atoms and containing up to about 30 to about 11, especially about 3 to 9, ethoxy groups per molecule are also suitable for the compositions of this invention.

3) Compounds formed by the condensation of ethylene oxide with a hydrophobic base, which in turn is formed by the condensation of propylene oxide with propylene glycol.

_ _ .. TT- 16 7 3 7 3 6

The molecular weight of the hydrophobic moiety is generally in the range of about 1500-1800. Such synthetic nonionic detergents are available under the tradename "Pluronic" and are supplied by Wyandotte Chemicals Cor-5 poration.

Particularly preferred nonionic surfactants suitable for use in this invention are ethoxylates of primary C 1-4 alcohols containing 3-8 moles of ethylene oxide per mole of alcohol, especially primary C 1-4 alcohols containing 6-8 moles of ethylene oxide. per mole of alcohol.

Cationic surfactants suitable for use in this invention include quaternary ammonium surfactants and surfactants that are semi-polar in nature, for example, amine oxides.

Suitable amine oxide surfactants have the general formula I

20 2 2 R r R -t 1 «+ U 2 R -N - (CH ~).-N - R (I)

I L

Wherein R * is a linear or branched alkyl or alkenyl group having 8 to 20 carbon atoms, each R 2 is independently C 1-6 alkyl or C 1 -C 12 alkyl, wherein n is 2 or 3; 1 to 7, and i is an integer from 1 to 6 and j is 0 or 1, the total number of CnH2nO groups in the molecule being at most 7.

In a preferred form, R 1 contains 10 to 14 carbon-2 atoms and each R is independently methyl or - (C H O) H, where m is 1 to 3, and the total number of C O groups in the molecule is at most 5, preferably 35. up to 3. In a highly preferred form, j is 2 1 6 and each R is methyl and R is C 1-2 2 ~ a - * - alkyl · 17 73736

Another suitable amine oxide group is formed by bis-amine oxides having the following substituents: 1: 1R: C 1-6 -glylalkyl; palmityl, oleyl, stearyl 2 R: hydroxyethyl i: 2 or 3

A specific example of this preferred bis-amine oxide group is N- (hydrogenated C 1-6 -glylalkyl) -10 N, N, N'-tri (2-hydroxyethyl) -propylene-1,3-diaminine oxide .

Quaternary ammonium surfactant compounds suitable for use in the composition of this invention may be defined by general formula II

15 R4 Γ R4 - | R is -N + - (CH 2). - N + - R 4 Z (II), 2 i 14 u RLRJ j 3 2Q wherein R is a linear or branched alkyl, alkenyl or alkylaryl group having 8 to 12 carbon atoms -4 group, each R is independently C 1-4 alkyl, alkylaryl having 1 to 4 carbon atoms in the alkyl moiety, or - (CH 2 O) H where n is 2 or 3 and m is 1-7, and i is 25 is an integer from 1 to 6, and j is 0 or 1, the total number of CnH2nO groups in the molecule being at most 7, and wherein Z represents the amount of counter anion such that the molecule is electrically neutral.

* 3

In a preferred form, R contains 10 to 14 carbon atoms 4 2Φ and each R is independently methyl or

- (C H., O) H, where m is 1-3, the total number of C H »O groups -n 2n m J n 2n J

in a molecule having a maximum of 5, preferably a maximum of 4. In a highly preferred form, j is O, R is 3 methyl, hydroxyethyl or hydroxypropyl and R is 2-C12-4alkyl. Particularly preferred surfactants in this group are alkyltrimethylammonium salts, C 1-4 alkyltrimethylammonium salts, cocoalkyltrimethylammonium salts, coconut alkyldimethyl (hydroxypropyl) ammonium salts and C 1-4 alkylmethyldioxy (hydroxyethyl) hydroxyethyldi (hydroxyethyl) methyl.

Another useful group of cationic compounds are the diammonium salts of formula 34 wherein II is 1, R is E 2, 2-14-3 ^ 2, each R is methyl, hydroxyethyl or hydroxypropyl, and i is 2 or 3. In a particularly preferred surfactant of this type, R is coconut alkyl, R is methyl and i is 3.

The laundry additive products according to the invention may also contain various active solid ingredients dispersed in an organic binder, in particular genomic bleaches and precursors of organic peroxyacid bleaches. Suitable inorganic peroxy bleaches include sodium perborate mono- and tetrahydrate, sodium percarbonate, sodium persilicate, urea and hydrogen peroxide adducts, and clathrate 4 Na 2 SO 4: 2H 2 O 2 NaCl. Suitable organic bleaches include peroxylauric acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid, diperoxydodecanoic acid, diperoxyazelaic acid, mono- and diperoxyphthalic acid and mono- and diperoxydiphthalic acid.

Suitable peroxyacid bleach precursors in this connection are described in GB 2,040,983; particularly preferred are peracetic acid bleach precursors such as tetraacetylethylenediamine, sodium p-acetoxybenzenesulfonate, tetraacetylglycoyl, pentaacetylglucose, octaacetyl lactose and methyl O-acetoxybenzoate. Bleach precursors may be added to the substrate at a precursor to substrate ratio of about 30: 1 to about 1:10, preferably from about 8: 1 to 1: 2, while bleaching agents may be added to the substrate at a bleach: substrate ratio of about 30: 1. 1 to about 1: 4, preferably about 10: 1 to about 1: 1. To improve stability, the bleach precursor and the bleach can be added to sites on the substrate that are physically separated.

All kinds of other laundry detergent ingredients, foaming regulators, fluorescents, photoactivators, enzymes, complexing agents, fabric softeners and anti-static agents, dirt suspending agents, etc. may be added to the compositions of the invention, including as part of a binder or organic binder. .

Suitable foaming control agents include microcrystalline waxes having a melting point of about 65 to about 100 ° C, a molecular weight of about 400 to 1000, and a penetration value of at least 6 measured at 77 ° C in accordance with ASTM-D1332; The iconic foam regulator of U.S. Patent No. 3,933,672, especially polydimethylsiloxanes having a molecular weight of about 200 to about 200,000 and a kinematic viscosity of about 20 to about 2,000,000 mra / s, is preferred; 20,000 to about 30,000 mm / s, and mixtures of siloxanes and hydrophobic silanized (preferably trimethylsilanated) silica having a particle size of about -9-9 10 x 10 m to about 20 x 10 m, and a specific surface area greater than 2 about 50 m / g; as well as self-emulsifying defoamers, which are described in DE-A-2 646 126.

Suitable fluorescents for use in this connection include e.g. Blackophor MBBH (Bayer AG) and Tinopal CBS and EMS (Ciba Geigy). Suitable photoactivators are described in EP application 82 300 309; very preferred substances are zinc phthalocyanine tri- and tetrasulfonates.

Useful chelating agents include citric acid, nitrolotriacetic and ethylenediaminetetraacetic acids and their salts, organic phosphonate derivatives, such as those described in U.S. Patent 3,213,030 (Diehl, October 19, 1965), 35 U.S. Patent 3,433,021 (Roy, 14,111,191). , U.S. Pat. No. 3,272,121 (January 9, 1968) and U.S. Pat. No. 2,599,807 (Bersworth, June 10, 1952), and carboxylic acid building salts, such as those described in U.S. Pat. 3,308,067 (Diehl, March 7, 1967). Preferred chelating agents include e.g. nitrile-acetic acid (NTA), nitrile-methylenephosphonic acid (NTMP), ethylenediaminetetramethylenephosphonic acid (EDTMO) and diethylenetriamine pentamethylenephosphonic acid (DETPMP): 1: about 1, about 1: - about 1: 5 and most preferably 3: 1 to 1: 1.

Anti-reuptake and dirt suspending agents are also preferred ingredients of the additive product of the invention. Cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose are examples of dirt suspending agents, and suitable anti-reuptake agents include homo- or copolymeric polycarboxylic acids or their salts having at least two carboxyl groups separated by two carboxyl groups.

Highly preferred polymeric polycarboxylic acids are copolymers of maleic acid or maleic anhydride and methyl vinyl ether, ethyl vinyl ether, ethylene or acrylic acid having a molecular weight of 12,000 to 1,500,000.

Suitable polymeric polycarboxylic acids are described in more detail in EP 63,017.

In a method of making the laundry detergent adhesive products of the invention, a laundry detergent composition is applied in a molten stream to a moving substrate at a rate of about 100 to about 400 g / m, preferably about 120 to about 320 g / m, so that no more than 70% of the substrate holes are covered. 35 not more than 45%.

The coated substrate is then

II

2i 7 3736 passing through application devices adjusted to level and apply the coating to the substrate so that almost no coating is removed from the substrate.

The melt temperature is generally about 35 to about 85 ° C, preferably about 40 to about 75 ° C, more preferably about 50 to about 70 ° C, and the solids dispersed in the melt preferably have a particle size of less than about 250, more preferably less than about 100. um. In preferred embodiments, the melt is applied from a gap of less than about 400, preferably about 150 to about 300, between two heated rollers rotating in different directions as the substrate moves against the direction of rotation of the other roll, thereby transferring the melt to the substrate by a sweeping mechanism. The substrate then passes through leveling and spreading devices formed, for example, from a pair of plates mounted on opposite sides of the substrate at a distance of less than about 300 microns, preferably from about 120 microns to about 220 microns apart. The coated substrate is finally dried in a stream of air.

The invention is illustrated by the following examples, in which proportions and percentages are parts and percentages by weight, unless otherwise stated.

The abbreviations used in the examples have the following meanings: LAS: Linear C 1-4 alkylbenzenesulfonate 2 12 / 14AS: Natl inm-Cj 2_24 ~ a1'-alkyl isulfate TAE: Cured tallow alcohol which is ethoxylated.

n J

with n moles of ethylene oxide / 1 mole of alcohol 30 C 1-4 alkyl: C 1-4 alkyl trimethyl;

Dobanol 45-E-7: Primary C 1-4 alcohol condensed with ethylene oxide (7 mol), marketed by Shell PEG: Po] ethylene glycol (molecular weight usually given separately) 73736 22 TAED: Tetraacetylethylenediamine PAG : Pentaacetylglucose AOBS: Sodium p-acetoxybenzenesulfonate

Silicone / silica: 85?> Polydimethylsiloxane, 15%

D

silanized silica

Porphine: Tri / tetra-sulphonated zinc phthalocyanine

Gantrez AN119: Maleic anhydride-vinyl methyl ether copolymer believed to have an average molecular weight of 240,000, marketed by GAF. This material was prehydrolyzed with NaOH before addition.

Perborate: Anhydrous sodium perborate bleach with the empirical formula NaBCl 2 -H 2 Cl 2 EDTA: Sodium ethylenediamine tetraacetate

Clarifier 1: Disodium 4,4'-bis (2-morpholine-4-aniline-s-triazin-6-ylamino) -stilbene-2: 2'-disulfonate

Clarifier 2: Disodium 4,4'-bis (2-sulfonate styryl) -20 biphenyl DETPMP: Diethylenetriaminepenta (methylenephosphonic acid), marketed by Monsanto under the trade name Dequest 2060 EDTMP: Ethylenediamine tetra (methylenephosphonic acid, marketed by Monsanto)

Dequest 2041

Substrate 1: A nonwoven fabric comprised of 100% unbleached, crimped 1.5 denier rayon fibers bonded together with 23% polyacylate binder; basis weight 35 g / m 2; 17 oval-2 aa holes / cm; hole width 0.9 mm; hole length 2.5 mm

Substrate 2: A nonwoven fabric comprised of 100% unbleached, crimped, 1.5 denier rayon fibers bonded together with 18% polyacylate • 2 binder; basis weight 35 g / m 2; 2 22 square holes / cm; side length 1.1 mm.

5 Examples 1-6

The laundry additive products according to the invention are prepared as follows. For each product, the ingredients of the laundry additive composition are mixed together at a temperature of about 65 ° C and passed through a mill 10 (Fryma Colloid Mill, Model MK95-R / MZ 80R, manufactured by MM Process Equipment Ltd of MM House, Frogmore Road, Hemel Hempstead, Hertfordshire, United Kingdom ), in which the refining surfaces are adjusted to a distance of about 180 μm from each other. The melt is then passed to a temperature of 76 ° C through a pair of counter-rotating rollers at a distance of 250, and transferred to a substrate moving in the opposite direction to one of the rolls by wiping. The coated substrate is finally passed between two stationary plates spaced 180 μm apart, cooled with air and cut into plates measuring 35 x 23 cm.

Examples _1 2_3 4 5 6 25 LAS -3--5- c12 / i4AS 5 3 6 3 3 8 TAEoc - 3 4 25 C12TMAB 2 4 3 -3

Dobanol 45E7 53 545- 30 PEG 8000 5 5 7 6 7 8 TAED 5 - - PAG -3--3- AOBS - - 1

Silicone / silica 0.3 0.2 0.2 0.2 0.3 0.3 35 Porphine - 0.2 - 0.3

Gantrez AN119 0.3 - - 0.8 - 0.5 24 73 7 3 6

Examples _1 2_3_4_5 6

Perborate - -5-- EDTA - - - 0.2 5 Brightener 1 - 0.3 0, .1 - 0.2 0.1

Brightener 2 0.1 0.1 - 0.2 - 0.3 DETPMP 0.5 1 - - 0.8 1 EDTMP - - 1.5 0.5

Humidity 0.8 0.5 0.6 0.2 0.5 0.7 10 Substrate 1 2.8 2.8 - 2.8 - -

Substrate 2 - - 2,3 - 2,82,8 Percentage of coated holes 40 33 45 50 42 55 15 The above products are effective laundry detergents that combine a high composition: substrate ratio for excellent flexibility, product release, comfort and preservation ] yvyysominaisuuksiin.

Claims (12)

A detergent product comprising a) a solid detergent composition having a softening temperature of at least 35 ° C and containing at least 40% by weight of a water-soluble or dispersible binder of organic materials and having a melt final temperature of less than 85 ° C, and b) a flexible, single-layer disc-like perforated substrate having an opening density of 10 - 30 openings / 2 cm disc, the openings having an average width of 0.5 - 5 mm and a length of 0.8 - 8 mm, and the substrate supports a water-adhering layer of the laundry additive composition, each weight ratio of composition to substrate being at least 5: 1, characterized in that the substrate comprises surfaces with uncovered openings and surfaces where one covers the openings and extends between the opposite surfaces of the substrate, the ratio of surfaces having 20 uncovered openings to surfaces having covered openings being 15: 1 - 1: 3. Product according to Claim 1, characterized in that the substrate has an opening density 2 of about 13 - 26, travel preferably about 16 - 23 openings / cm 25. Product according to claim 1 or 2, characterized in that the openings have an average of 2 an area of about 0.7 - 7 mm and a length: width ratio of 1: 1 - about 6: 1, preferably 1: 1 - about 4: 1. Product according to any of claims 1-3, characterized in that the openings are elongated and have an average width of about 0.8 - 1.5 mm and an average length of about 2 - 3.5 mm, or in Generally they are square with a side length of about 1 - 2.5 mm. 3. Product according to any one of claims 1-4, characterized in that the substrate has a 2 basis weight of about 10 - 70 g / m and contains the hydrophobic binder resin in an amount of about 12-25%, preferably about 16-2. %. Il 29 73736 Product according to any one of claims 1-5, characterized in that the additive composition contains at least about 50% by weight, preferably at least about 60% by weight of organic binders with a melting end temperature below about 75 ° C, preferably lower than about 70 ° C, and the detergent composition has a softening temperature of at least about 40 ° C, preferably at least about 50 ° C. Product according to any one of claims 1-6, characterized in that the weight ratio between composition and substrate is at least about 6: 1, preferably at least about 7: 1, and that the ratio of surfaces with uncovered openings to areas with covered openings are about 6: 1 - 1: 2, preferably about 4: 1 - 1: 1. Product according to any one of claims 1-7, characterized in that the additive composition comprises at least 5%, preferably at least 15% of a water-soluble or water-dispersible organic binder, with an initial melt temperature of at least about 35 ° C and a melt end temperature below about 85 ° C. 9. A product according to claim 8, characterized in that the binder is a polyethylene glycol having a molecular weight exceeding about 1000, a C₂ 2 “C C fatty acid or an ester or amide thereof, a polyvinylpyrrolidone having a molecular weight. between about 40,000 and about 700,000 or a C1-C6 fatty alcohol which has been oxidized with about 14-100 moles of ethylene oxide. Product according to claim 8 or 9, characterized in that the binder comprises at least about 40% by weight, preferably at least about 50% by weight of a polyethylene glycol having a molecular weight exceeding about 4000. Product according to any one of claims 1-10, characterized in that the additive composition comprises at least about 5% by weight, preferably about 20% by weight of an organic detergent, which is an