JPS5941398A - Laundry additive product - 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

[Detailed description of the invention]

FIELD OF THE INVENTION This invention relates to laundry additive products. More particularly, the present invention provides laundry additives that clean fabrics or other fabrics or provide supplementary IM benefits to additive products consisting of water-insoluble substrates and laundry additive compositions that are tested or impregnated into the substrate. Regarding the product. Laundry additive products based on water-insoluble substrates are now well known in the art. For example, U.S. Pat.
, 422,692 discloses a method of softening and controlling static electricity on fabrics in a layer washer or dryer using a fabric conditioning composition coated onto a substrate. GB 1,586.769 teaches a toiletry additive product containing an organic peroxy compound precursor in combination with a solid article, particularly a sheet-like water-insoluble substrate. U.S. Patent No. 4,170,565
The present invention relates to a fabric cleaning article that results in the sequential release of a surface-active ingredient comprising a surface-active composition contained between two layers of a water-insoluble substrate of limited air permeability. In particular, the MW of laundry additive products based on substrates for use as detergents or detergent additives for cleaning fabrics, etc. is that a relatively large amount of the laundry additive composition can be placed on the substrate and at the same time washing can be carried out. sometimes the ability to achieve rapid and complete withdrawal (release) of the additive composition. It is used for cleaning and scrubbing hard surfaces, such as dishes and counter surfaces, and relies on physical linen and scrubbing during use to ensure the release of the cleaning composition of the spear suitable for cleaning operations. Contrast with type articles. These articles are generally designed for multiple repeated uses and are therefore formulated to remove only a small amount of the entire cleaning composition during a single use of the additive. To achieve rapid N'desorption of laundry additive compositions,
It has been found that it is generally desirable to utilize a substrate with a low surface area. From this point of view, monolayer substrates impregnated or supported with a coating of the keratin additive composition are particularly suitable. Therefore, as a result of multi-longitudinal loading and low substrate basis it,
A cleaning TTD additive product with optimal performance for general cleaning applications necessarily has a composition-to-substrate ratio (referred to herein as the loading ratio) of 6. However, from the standpoint of processing, product aesthetics and storage properties, the production of toiletry additive products with high loading ratios creates a number of difficult-to-manage complications. First of all, the flexibility of the substrate decreases rapidly even with loading ratio, and the product becomes increasingly stiff and cardboard-like. This is not only disliked by consumers;
Processing problems associated with flaking the composition from the sheet and folding the article into a form that is compact and convenient for use. This creates manufacturing problems and packaging delays associated with rolling. On the other hand, if the additive composition is made sufficiently flexible and plastic to reduce readability problems, the article will be quite viscous, uncomfortable to touch, and difficult to handle and store. The interstitial Mfi (blocking phenomenon, etc.) becomes increasingly important. Laundry additive compositions of limited melting properties and sheet-like apertured substrates of limited aperture size and density. By selecting and coating the substrate so that only a limited percentage of the substrate opening is framed and filled, the mutual benefit of loading, good release characteristics, and excellent flexibility and product feel properties can be achieved. It has now been found that it is possible to provide a toiletry additive product which satisfies the constraints at the same time; the product is thus non-viscous when handled, and is easy to manufacture, use and store, and Excellent product flexibility properties that can effectively and conveniently clean stains and other fabrics in washing tub operations or provide additional cleaning benefits; and -) a favorable composition to substrate ratio. To provide washing liquid additive products that In accordance with the present invention: (a) a water-bathable or water-dispersible matrix of organic material having a bath melting temperature of less than about 65°C; a solid detergent additive composition having, and lb)
a flexible sheet-like apertured substrate (1c;
The average opening size is about 0.5+++a+ to about 511111
of width and a length of from about 0.8 urts to about 5 urts, the substrate has a water releasable coating 8 of the laundry additive composition loaded thereon and the coating opening area and the coating opening the opening. It has a region that covers and extends between the facing layers i6+ of the base body, and the area ratio of the uncovered opening to the core opening I11 is about 15; 1 to about 1=3
111α, and the composition to substrate weight ratio is at least about 5:1). The substrate preferably contains from about 13 to about 26 per cu2
, more preferably about 16 to about Z openings, about 10 to about 70 g/m , more preferably about 4) to
about! ld) from about 12 to about 5 g/m of the front and total substrate.
N M %, more preferably about 16 to about 22 mBi%
There is a reputation for hydrophobic pongee resin. The apertures themselves are generally symmetrical about the longitudinal axis (i.e., they have mirror symmetry) and preferably have an average width of about 0.7 to about 2.51 #II+ and about 1 It has a length of .7 mm to about 4 mm. On the other hand, the area of the opening is preferably about 0. υ
Fake 2 to about 7IIIM2, more preferably about Q, 8111
Koji 2~J5#ll11 and the length to temperature ratio is from 1:1 to preferably about 6:1, more preferably about 4=1. These parameters are highly preferred from the standpoint of achieving an optimum area ratio of uncoated to coated apertures and complete filling of the coated apertures from one side of the substrate to the other. The substrate aperture can be elongated in shape (e.g., generally oval or diamond-shaped), in which case the aperture preferably has a width of about QJ3111111 to about 1.5+++ m and a width of about QJ3111111 to about 3.5111 m. It has a length. but,
In a preferred embodiment, the opening is generally square with a side dimension of about 1 to 2.5 squares. As used herein, [length 1 is the dimension of the major (i.e., longest) longitudinal axis! and 1 width is the largest dimension perpendicular to this axis. The loading ratio (i.e., the weight ratio of composition to substrate) is preferably at least about 6:1, and more preferably less than 7:1. Additionally, the ratio of uncovered open areas to coated open areas in the final product is preferably at least about 6:1, and more preferably less than 7:1. The area ratio of 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 comprises at least about 50 organic polymers. %, more preferably at least about 60%. Each of these preferably has a melt completion temperature of less than about 75°C, more preferably less than about 70°C. The laundry additive composition itself desirably has a softening temperature of at least about 40°C, particularly at least about □□□°C. In a preferred embodiment, the toiletry additive product comprises at least about 50% of the composition a water-soluble or water-dispersible organic binder having a melt onset temperature of at least 3.5'C and a melt completion temperature of less than about 85'C. Preferably the binder contains polyethylene glycol with a molecular weight greater than about 1000, 012-C18 fatty acids or their esters and amides thereof, .000
selected from polyvinylpyrrolidine with a molecular weight in the range of from about 700,000 to about 14 to about 100 moles of ethylene oxide ethoxylated CI4 to C24 fatty alcohols. Dilyethylene glycol having a molecular weight greater than about 4,000 (and preferably greater than about 7,000) for optimal flexibility and feel properties combined with excellent water dispersibility at high loading ratios. are highly preferred. These materials are preferably low in organic binders (about 40%
, more preferably at least about 50%. The toiletry additive products of the present invention suitably contain at least about 5%, preferably at least about 20% of the additive composition of anionic surfactants, nonionic surfactants, cationic surfactants and mixtures thereof. Contains an organic detergent selected from: Preferred nonionic surfactants have a melt completion temperature of less than about 85°C and constitute a portion of the matrix of organic material. Preferred cationic surfactants have bath melt onset temperatures of at least about 35°C and can form part of the organic binder or be dispersed in the organic matrix. Preferred anionic surfactants have melt completion temperatures greater than about 100°C and are dispersed in the organic matrix. Other functional solid components, particularly preferably inorganic or organic peroxy whitening agents, which make up at least about 50% of the additive composition and/or preferably less than about 2'% of the additive composition. The constituent organic peroxyacid bleach precursors can also be present as a dispersion in an organic matrix.Other suitable functional ingredients are, for example, detergent enzymes, sintering agents, photoactive agents, total ion sequestrants, egg white catalysts. , and anti-foam agents.The following details the toiletry additive products of the present invention.Preferred substrates for use in the present invention are webs or carded fibrous structures (the fiber strength is sufficient to produce carding). or the fibers or filaments are distributed in a haphazard or random arrangement (i.e., a completely random distribution orientation as well as an arrangement of fibers within a carded structure where there is often a partial blend of fibers). An open nonwoven fabric can generally be defined as an adhesively bonded fiber-like or filament-like product consisting of a substantially aligned fiber-like mat of fibers or filaments.・Jute, hemp, cotton, linen, sisal, or ramie), synthetic materials (e.g., rayon, cellulose, ester, polyvinyl vj
Exclusively polyolefin 1.1? It can be a mixture of either lyamide, or polyester) or its predecessors. Generally, nonwoven fabrics are produced by air or water forming methods, in which fibers or filaments are first cut to the desired length from a strand, passed through a water or air stream, and then deposited on a screen; Air or water carrying fibers is passed through the screen. The deposited fibers or filaments are then adhesively bonded together, dried, cured, and otherwise treated as desired to produce the nonwoven fabric. Preferably, the nonwoven fabric is made from cellulose fibers, particularly regenerated cellulose or rayon, which have been inked with standard textile lubricants, such as sodium oleate. Preferably the fibers have a length of from about 4 to about 100 cm, especially about 100%
um to about 201 denier, and F denier, which is about 1 to about 5 denier, is a yarn length of 9000 m (
g) is an internationally recognized unit (thread scale) equivalent to Preferably the fibers are at least partially haphazardly oriented, in particular substantially haphazardly oriented, and are coated with a hydrophobic or substantially -F hydrophobic binder resin, in particular a non-ionic self-crosslinking acrylic polymer or an offshore polymer. are joined together tangentially. In highly preferred embodiments, the fabric has about 75 to about 8 slji of fibers, particularly about 78 to about 84 slji, and about 12 to about 5 slji of hydrophobic binder resin.
It consists of about 16 to about 22 blood scales, and has a weight of about 0 to about 70, preferably about 50 g/m2. A suitable hydrophobic binder resin is an ethyl acrylate resin, such as Primal HA 240.
Rhoplex HA 8 and HA
lfi (Roam End Hearth Inc.) and their mixed proboscis. The substrate openings extending between opposite surfaces of the substrate are usually patterned and the laydown of fibers to produce the substrate (
It is formed at the time of lay-down). Exemplary apertured nonwoven substrates are described in U.S. Pat. No. 3,741,724, 3
, 930, No. 086 Mei Holil Book and No. 3, 7
50, 237. An example of an apertured nonwoven substrate suitable for the present invention is about 35 g/m
1,57' bonded with Roblex HA8 bonding agent with a tsubo seam and 1 (: 17 openings per JR)
It is a regenerated cellulose sheet of Neil fibers (fiber to binder ratio of approximately 77:23). The openings are generally oval in shape and in a side-by-side arrangement. The aperture has a width of about 0.9 mm and a length of about 2.5 mm measured in a relaxed state. Another highly preferred substrate is 1.5 denier regenerated cellulose fiber paste with a Robrex HA8 binder at a fiber to binder ratio of about 82:18, about 35 g/m
It has an area of 20 tsubo and approximately 22 openings per 112 square meters. In this example, the aperture is generally square with a width (relaxation) of approximately 1.1+II+x. The openings are again arranged in a side-by-side arrangement. The size and shape of the base sheet for each unit of product is a matter of choice and is determined primarily by factors related to convenience of use. As such, the sheets must not be so small that they become trapped in the crevices of the washing machine or the fabric being washed, or so large that they are difficult to dispense and package from containers for sale. . For purposes of this invention, planar area sheets of from about 130 cm2 to about 1300 cIn2 are acceptable, with preferred areas ranging from about 520 cIn2 to about 780 cIn2. The T111 additive composition is in solid form at ambient temperature (below 25°C) and preferably has a temperature of at least about 35°C.
°C1 more preferably at least about 40 °C, especially less than (
Both have a softening temperature of about 50'C. Softening temperature means the temperature at which plastic flow characteristics transition to viscous flow characteristics. Therefore, at room temperature, the composition assumes the form of a plastic solid with non-zero yield stress. The hardness of the composition at room temperature is determined by standard methods such as the IP490 penetrometer paced technique (or the technically equivalent ASTM-D5 or B546
91). Thus, preferred additive compositions for use in the present invention have an IP49 of about 1 (measured in tens of tenths of an inch) after 15 seconds at 5° C. under a load of 100 g. , more preferably have a penetration of less than about 7, while the softening temperature of the composition is IP49.
The temperature is taken such that the penetration level exceeds approximately 1.5 mm in 15 seconds. The laundry additive composition of the present invention consists of seven trixes of organic materials with limited melting properties. The melt completion temperature is measured using a DuPont 910 differential scanning calorimeter with an R90 thermal analyzer and mechanical cooling attachment as follows. Capture 5-1000 samples of organic material without free water or solvent in a hermetically sealed pan. Use the empty pan as a reference. The sample is first heated until melted and then quickly cooled to -70°C (at about ˜30°C/min). Then, using sufficient amplification of the signal (i.e., temperature difference between sample and reference - vertical 114i1) to obtain an endothermic peak signal to fundamental noise ratio better than 10:1. , thermal analysis 1 (1'
A heating rate of c/min is carried out. The melt completion temperature is the temperature corresponding to the intersection of the tangent to the steepest part of the endothermic curve at the high temperature end of the endotherm and the horizontal line parallel to the sample temperature 4A11 through the highest temperature endothermic peak. M) The organic material comprising IJ Lux has a melt completion temperature of less than about 85°C. Additionally, the detergent additive products of the present invention have a common temperature of less than 85°C, preferably less than about 8()°C, especially less than about 10°C, and a temperature of at least 35°C.
°C, preferably less than 40 °C, especially at least 50 °C
At least about 5 layers of the composition preferably contain a binder, defined as an organic material having a bath melt onset temperature of C. The bath melt onset temperature can also be determined by the thermal analysis;
It is then determined to be the sample temperature at the intersection of the baseline and the tangent to the steepest slope portion of the endotherm closest to the cold end of the endotherm. The toiletry additive products of the present invention can be supplemented with all laundry and cleaning ingredients. Preferably, the additive product contains about 50 organic detergents selected from anionic surfactants, nonionic surfactants, cationic surfactants and mixtures thereof.
% to about 100%, preferably about 100% to about 100%, more preferably about 15 to about 75%. The anionic surfactant preferably accounts for about 7 to about 384 (t) of the composition.
#, %, preferably constitutes about 15 to about + tm%,
The nonionic surfactant constitutes about 8 to about 32 1% by weight of the composition, more preferably about 12 to about 25 itl%;
and the cationic surfactant is about 5 to about 30 parts by weight of the composition.
1%, more preferably about 8 to about 1% of the weight. Anionic surfactants are commonly used in laundry detergents.
It can be any of more than one species. Suitable synthetic anionic surfactants include alkylbenzenesulfonic acids,
Alkyl sulfuric acid, alkyl polyethoxyether sulfuric acid, paraffin sulfonic acid, α-olefin sulfonic acid, (1
- Aqueous solutions of sulfocarboxylic acids and their esters, alkylglyceryl ether sulfonic acids, fatty acid monoglycerides ttM, fatty acid monoglycerides sulfonic acids, alkylphenol polyethoxyether sulfates, 2-acyloxyalkane-1-sulfonic acids, and β-alkyloxyalkanesulfonic acids It is natural salt. Particularly suitable S= anionic surfactants include, for example, alkyl or alkaryl groups and sulfonic acid ester groups or values having in their molecular structure from about 8 to about 22 carbon atoms, especially from about 1 to about 211 carbon atoms. Water-soluble salts of organic sulfuric acid reaction products having fermentation ester groups, especially alkali alkaline salts, ammonium salts and alkanol ammonium salts (the alkyl moiety of the acyl group is encapsulated in the 1゛alkyl 1 candy). Examples of synthetic detergents of this group which form part of the detergent compositions of the present invention are high-grade synthetic detergents produced by combining sodium alkyl sulfates and potassium alkyl mtH, sometimes with tallow or coconut oil. Those obtained by converting alcohol (C8 to 18 carbon atoms) into mt (1R), and those obtained by converting alcohol (C8 to 18 carbon atoms) into mt (1R), and those in which the alkyl group has a linear or branched chain structure (d has about 9 to about 15 carbon atoms, especially about 11 to about 13 carbon atoms) Sodium alkylbenzenesulfonates and potassium alkylbenzenesulfonates with
f-No. 2.220.099 and No. 2.477
．． No. 383 and those produced from alkylbenzenes obtained by alkylation with linear chlorozorafins (using aluminum trichloride catalysts) or linear olefins (using hydrogen fluoride catalysts). be. Linear straight-chain alkylbenzene sulfonates (abbreviated as C11,
8LAS) Oyohi CI2-15 methyl branched alkyl sulfate is of particular value. Other anionic detergent compounds are, for example, sodium C1°-18 alkyl glyceryl ether sulfonates, especially ethers of madder grade alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglycerides sulfonates and coconut oil. fatty acid moiety/sodium ceride aate; and alkylphenol ethylene oxide ether 4 containing about 1 to about 10 units of ethylene oxide per molecule and having an alkyl group of about 8 to about 12 carbon atoms.
18 sodium or potassium salt. Other anionic detergent compounds useful in the present invention include, for example, water-soluble esters of α-sulfonated fatty acids having 6 to 20 carbon atoms in the fatty acid group and 1 to 10 carbon atoms in the ester group. Salt, water-soluble salt of 2-acyloxyalkane-l-sulfonic acid having 2 to 9 carbon atoms in the acyl group and about 9 to about 13 carbon atoms in the alkane moiety; Argyl ether sulfates having a target lθ~18, especially about 12-16 and having about 1-12 moles, typically 1-6 moles, typically 1-4 moles of ethylene oxide; carbon numbers 12-24, preferably Approximately 14 to 1
6, especially those produced by reaction with trioxide and neutralization under conditions such that the sultone present is hydrolyzed to the corresponding hydroxyalkanesulfonate; carbon number 8
~21, a water-soluble salt of ξ rough insulfonic acid having 14 to 18 at r, and 1 to 3 carbon atoms in the alkyl group
It is a β-alkyloxyalkane sulfonate having a carbon number of 8 to 2 () in the alkane moiety. The alkane chains of the non-soap anionic surfactants can be derived from natural products, such as coconut oil or tallow, or can be produced synthetically, using, for example, the Ziegler or Oxo methods. Water solubility can be achieved by using alkali metal, ammonium or alkanol ammonium cations. Sodium is preferred. Suitable fatty acid soaps include the usual alkali metal bases (sodium salts, potassium salts), ammonium, and It can be selected from salts and alkylol ammonium salts. Suitable fatty acids are obtained from natural sources, such as soybean oil, castor oil, tallow, whale oil, and fish oils, greases, RaF and mixtures thereof. Fatty acids can also be produced synthetically (eg by oxidation of petroleum or by hydrogenation of carbon monoxide by the Fischer-Tropsch process). Resin acids, such as those in rosin and toll, are suitable. Nanthenic acid is also suitable. N) IJum soap and potassium soap are produced by saponifying oils and fats in 1. Alternatively, it can be produced by neutralizing free fatty acids produced in another manufacturing process. Particularly useful are the sodium and potassium salts of mixtures of fatty acids derived from tallow and hydrogenated fish oils. Mixtures of anionic surfactants, particularly with a ratio of about 5=1 to about 1:5, preferably about 5=1 to about 1:1, more preferably about 5=1 to about 1.5:1. Mixtures of sulbonate and sulfate surfactants are particularly preferred according to the invention. Alkylbenzene sulfonates having 9 to 15 carbon atoms and 11 to 13 carbon atoms in the alkyl group (
The cation is an alkali metal, preferably sodium), and the alkyl group has 10 to 12 carbon atoms, preferably 12 carbon atoms.
Alkyl sulfate having ~18 carbon atoms or having 10 to 20 carbon atoms in the alkyl group. preferably has 10 to 16,
Particular preference is given to mixtures with ethoxysulfates having an average degree of ethoxylation of from 1 to 6 and containing an alkali metal cation, preferably sodium. Nonionic surfactants useful in the present invention have an average hydrophilic-lipophilic balance (HL
B) is a condensation product of ethylene oxide and a hydrophobic moiety to give a surfactant having the following properties. The hydrophobic moiety can be aliphatic or aromatic, and the length of the polyoxyethylene group that is fused with a particular hydrophobic group is determined by the water content with the desired balance between hydrophilic and hydrophobic elements. can be easily tailored to produce compounds. Examples of suitable nonionic surfactants are: 1. Polyethylene oxide condensates of alkylphenols, e.g. 6 to 6 carbon atoms in either linear or branched configuration.
Condensates of alkylphenols having alkyl groups having 12 and ethylene oxide (the ethylene oxide being present in a value equal to 3 to 30 mol, preferably 5 to 14 mol, per mole of alkylphenol). Alkyl substituents within this yuzu compound can be derived from, for example, polymerized propylene, diisobutylene, octene and nonene. Another example is dodecylphenol condensed with 9 moles of ethycine oxide per mole of phenol, 1
Per mole dinonylphenol condensed with 11 moles of ethylene oxide, nonyphenol and diisooctylphenol condensed with 13 moles of ethylene oxide. 2. A primary or secondary aliphatic alcohol having 8 to 7 carbon atoms in either a straight chain, branched or branched configuration, 2 to about 40 mol per mol of alcohol, preferably 2 to about 9 mol condensate of with ethylene oxide. Preferably, the aliphatic alcohol has 9 to 18 carbon atoms and 2 to 9 mol, preferably 3 to 9 mol per mol of aliphatic alcohol.
Ethoxylated with 8 moles of ethylene oxide. Preferred surfactants are door-like primary alcohols, such as those derived from natural fats or produced from ethylene by the Ziegler process, such as myristyl alcohol,
cetyl alcohol, stearyl alcohol), or partially branched primary alcohols, such as rutinols with about 5 2-methyl branches (1, ut, ens
ols), Doba-nolg and Neodols (Rutinsol is a BASF trade name, Dopanol and Neodol are Shell trade names), or 2-methyl branches of about 5
Synperonics (Synp
eronic8; Synperonic is a trade name of ICI) or Liquitimica with the trade name Real (Li
It is produced from a primary alcohol that has a more branched chain structure than the N)ti sold under a+). Specific examples of nonionic surfactants falling within the scope of the present invention include Dopanol 45-4, )'Panol 45-7, Dopanol 45-9
, tonosinol 91-2.5, dopanol 91-3, dopanol 91-4, rpanol 91-6, dopanol 9
1-8, Dopanol 23-6.5, Synperonic 6,
Synperonic 14, a condensate of coconut alcohol and an average of 5 to 12 moles of ethylene oxide per mole of alcohol (the coconut alkyl moiety has 10 to 14 carbon atoms)
It is a condensate of Oyohitaro alcohol and an average of 7 to 12 moles of ethylene oxide per mole of alcohol (the taro portion essentially consists of 16 to 22 carbon atoms). Secondary linear alkyl ethoxylates, especially Tervi tols having 9 to 15 carbon atoms in the alkyl group and up to about 11, especially about 3 to 9, ethoxy residues per molecule A series of ethoxylates are also suitable in the present compositions. 3. A compound produced by condensing ethylene oxide with a hydrophobic paste produced by condensing propylene oxide and propylene glycol. The molecular weight of the hydrophobic moiety generally falls within the range of about 1500-1800. Nonionic synthetic detergents of this type can be purchased under the trade name PL+-R6YLIC J, supplied by Wyandotte Chemicals Co., Ltd. Particularly preferred nonionic surfactants for use in the present invention are 09-C15 primary alcohol ethoxylates containing from 3 to 8 moles of ethylene oxide per mole of alcohol, especially from 96 to 8 moles of ethylene oxide per mole of alcohol. It is a C12-C15 primary alcohol containing. Cationic surfactants suitable for use in the present invention are, for example, quaternary ammonium surfactants and semipolar surfactants, such as amine oxides. Suitable surfactants of the amine oxide type have the general formula 1 (wherein R1 is a linear or branched alkyl or alkenyl group having from 8 carbon atoms and the valleys R2 are independently C
selected from 1-4 alkyl and -(CnH2nO)mH, i is an integer from 1 to 6, j is 0 or 1, n is 2 or 3, and m is 1 to 7, and the molecule The total number of CnH2n0 groups within is 7 or less). In a preferred embodiment, R has 10 to 14 carbon atoms and the valleys R2 independently represent methyl and -(CnH2n
O)rrl)I (wherein m is 1 to 3 and the sum of CnH2n0 groups in the molecule is 5 or less, preferably 3 or less). In a highly preferred embodiment, j is O and each R2 is methyl;
and R is C12-C14 alkyl. Another suitable type of amine oxide building block is represented by bis-amine oxy r with the following 1a substituent: j: IR, tallow C16-C18 alkyl, nonlumityl, 1
. Oleyl, stearyl rt2, hydroxyethyl 1:2 or 3 A particular example of this preferred class of bis-amine oxides is N-hydrogenated 016-C18 talloalkyl-N,
N',N'-)su(2-hydroxyethyl)-zolopyrene-1,3-diamine oxide. Suitable quaternary ammonium surfactants for use in the present compositions have the general formula: , and the valley R4 is independently C1-4 alkyl, C1-4
selected from alkaryl and -(CnlI2nO)mH, i is an integer from 1 to 6, j is O or 1, n is 2 or 3, and m is 1 to 7, and the molecule The sum of CI, H2nO groups within is 7 or less, and 2 represents the number of counteranions that provide electroneutrality). In a preferred embodiment, R3 has 10 to 14 carbon atoms and each R4 is independently methyl and (CnH2n
O)rll) (in the formula 1, m is 1 to 3, and the sum of CnH2n0 groups in the molecule is 5 or less, preferably 3 or less). In a highly preferred embodiment, j is 0, R4 is selected from methyl, hydroxyethyl and hydroxypropyl, and R3 is C12-C14 alkyl. Particularly preferred surfactants for this glaze include, for example, C12 alkyltrimethylammonium salts, C14 alkyltrimethylammonium salts,
Coconut alkyltrimethylammonium salt, coconut alkyltrimethylhydroxyethylammonium salt; rum salt, coconut alkyldimethylhydroxyzolobyl ammonium salt, and CI2 alkyldihydroxyethylmethylammonium salt. Another useful hepatic cationic compound has the formula ■ (where j is 1
, R3 is C12-C17, alkyl, @R
4 is methyl, hydroxymethyl or hydroxypropyl and i is 2 or 3). In this particularly preferred surfactant, R3 is coconut alkyl, R4 is methyl, and the number is 3. `` duds '' laundry additive products are organic polymers ) IJ Lux dispersed ``! Yuzu functional solid components can be included, particularly peroxy bleaches and organic peroxy bleach precursors. Suitable inorganic peracid complexing agents are, for example, sodium perborate hydrate and tetrahydrate, sodium percarbonate, sodium persilicate and urea-hydrogen peroxide adducts and the clathrates 4Na2SO4: 2H202: lNaC1
It is. Suitable organic whitening agents are, for example, peroxylauric acid, peroxyoctanoic acid, peroxynonanoic acid, peroxytecanic acid, diperoxide dodecanedioic acid, diperoxyazelaic acid, mono- and diperoxyphthalic acid and mono- and diperoxy It is isophthalic acid. Suitable peroxyacid bleach precursors in the present invention are disclosed in Laikokutoku Wf No. 2,040,983 and include peracetic acid bleach precursors such as tetraacetylmethylenediamine, tetraacetylmethylenediamine, tetraacetylmethylenediamine,
Tetraacetylhexylene diamine, sodium p-acetoxybenzenesulfonate, tetraacetylglycouril, pentaacetylglucose, octaacetyllactose, and methyl 0-acetoxybenzoate are highly preferred. The bleach precursor can be applied to the substrate at a precursor-to-substrate ratio of about 3t):1 to about 1:10, preferably about 8=1 to about 1:2, while the bleaching agent is applied to the substrate at a bleach-to-substrate ratio of Approximately 30:1 to about 1:4, preferably about 10:1 to about 1:1 can be applied. For improved stability, the bleach precursor and bleach can be incorporated at a physically separate location from the substrate. The compositions of the present invention may contain all other toiletry ingredients, such as antifoams, stimulants, photoactive agents, enzymes, sequestrants, fabric softeners and It can be supplemented with anti-fouling agents, dirt suspending agents, etc. Suitable antifoam agents include, for example, a melting point in the range of about (55°C to about 100°C), a molecular weight in the III+! microcrystalline wax having a silicone antifoam agent disclosed in U.S. Pat. No. 3,933,672, particularly from about 200 to about 20
0,000 and about 21) to about 2
．． 000.000 mrrt/s, preferably about 30
00 to about 30,000 nQ/s, and a particle size in the range of about 10 millimicrons to about 4) millimicrons and about 50 m/g.
a mixture of hydrophobic silanized (preferably trimethylsilanized) silica and siloxane having a specific surface area of 100% or more; and a self-emulsifying foam suppressor as described in German Patent No. 2,646.126. The stimulant suitable for the present invention is, for example, Black Obol (
131ackopl+or) MBBH (Bayer ACE) and Tinopal (1'1nnpal)
CBS and EMS (Chipa Geigy). Suitable photoactive agents are disclosed in European Application No. 82300309, and highly preferred substances are

[111 Lead phthalocyanine tri and tetrasulfonate. Chelating agents that can be incorporated include, for example, citric acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and their salts, organic phosphonate derivatives, such as U.S. Pat.
, 213,030, U.S. Patent No. 3,433,0
No. 21 Ming #i1+1 die, U.S. Patent No. 3,292,121
and those disclosed in U.S. Pat. No. 2,599,807, and Cal 7I? acid builder salt,
An example is that disclosed in U.S. Pat. No. 3,308,067. Preferred chelating agents are, for example, nitrilotriacetic acid fi (NTA), nitrilotrimethylene phosphonic acid fi (NTMP), ethylenediaminetetramethylene phosphonic acid V (EDTMP) and diethylenetriaminepentamethylenephosphonic acid (iTPMP).
), and these have a weight ratio of substrate + 1 chelating agent within the range of about 1:5, preferably about 5
=1 to about 1:5, most preferably 3:1 to 1:1. Anti-redeposition and soil suspending agents also constitute preferred components of the additive products of this invention. Cellulose derivatives, such as methylcellulose, caly1? Hydroxymethyl cellulose and hydroxyethyl cellulose are examples of soil suspending agents, and suitable anti-reprinting agents are polycarboxylic or co-polycarbons in which at least two carboxyl groups are present separated by up to 2 carbon atoms. acid or their salts. A highly preferred polymeric polycarboxylic acid is a copolymer of maleic acid or maleic anhydride with methyl vinyl ether, ethyl vinyl ether, ethyl vinyl ether, ethylenyl acrylic acid, with one copolymer ranging from 12,000 to 1,500,000 It has molecular emesis. Suitable 1. 'c iN molecule polycal d? A further description of acid is found in European patent application no.
76. No. 9 is given in Specification No. 9. In the method of manufacturing the anti-layer additive product of the present invention, bath melt washing 7
Transfer the θIL of the M additive composition onto the substrate from about 100 to about 400 grams, preferably from about 120 to about 3 grams per square meter of substrate.
Approximately 20% of the open area of the substrate is dispensed with a 20g application rate.
Below, preferably about 45% or less is a nuclide. Thereafter, the coated substrate is passed through a smoothing distribution device d arranged to distribute and smooth the coating onto the At body without substantially removing the material to be coated from the substrate. The temperature of the bath melt generally ranges from about 5°C to about 85°C) 7fl
preferably from about 0°C to about 75°C, more preferably from about 51°C to about 10°C, and the average particle size of the solids dispersed in the bath melt is preferably less than about 250 microns; More preferably less than about 100 microns. In a preferred embodiment, the melt is dispersed from the nip of a pair of counter-rotating heated rollers having a nip setting of less than about 400 microns, preferably from about 150 to about 300 microns. (positioning the substrate to move oppositely to and in contact with one of the rollers)
, thereby causing the melt to be transferred to the substrate by a smearing action. The substrate is then passed through a smoothing distribution device, such as a pair of plates fixed opposite the substrate at a spacing of less than about 300 microns, preferably from about 120 to about 220 microns. Finally, the coated substrate is allowed to cool in a stream of air. The invention is illustrated in the following non-limiting examples. Sections and sections are to scale unless otherwise noted. In the examples, the abbreviations used have the following meanings: LAS s m-shaped C12 alkylbenzene sulfonate C12/14AS: C12-C14 alkyl sodium sulfate TAEn' hardened tallow alcohol ethoxylated with n moles of ethyleneoxy P per mole of alcohol CI2Cl2T: Ct2 alkyltrimethylammonium zolomide dopanol 45- E-7: 014-C1 condensed with 7 moles of ethylene oxide commercially available by Shell
5 Primary Alcohol PEG: , IP Liethylene Glycol (molecular weight is usually as follows) TAED: Tetraacetylethylenediamine PAG
: Hentaacetylglucose AOBS : p-acetoxybenzenesulfone Sodium silicone/silica: Boridimethylsiloxane 85,
Silanized silica 15% Porphine: )/Tetrasulfonated zinc phthalocyanine Gantrez AN119: G
A maleic anhydride/vinyl methyl ether copolymer believed to have an average molecular weight of 240,000 sold by AF. This material was pre-hydrolyzed with NaOH before addition. Perborate: Anhydrous sodium perborate with empirical formula NaBO2.H2O2 Brightener EDTA: Sodium ethylenediaminetetraacetate Brightener 1: 4,4'-bis(2-morpholino-4-anilino-5-) riazine- 6-ylamino)stilbene-
2: 2'-disulfone F'l2f) IJ rum brightener 2; disodium 4,4'-bis(2-sulfo, +
-)-Styryl) biphenyl DETPMP: Product name Duquess by Monsando (new test)
Diethylene diamine penta(methylene phosphonic acid) commercially available as 2060 EDTMP: Ethylene diamine tetra(methylene phosphonic acid) commercially available as Duquest 2041 by Monsanto Substrate 1: , lr Reacrylate binder 23q6 1.5 denier unbleached crimped rayon fibers bonded with
Non-woven fabric made from 00chi; tsubo! 35 g/m2;
17 oval openings per 1α2: opening width 0.9
+rjIIl; opening length J51+lI insect substrate 2: 1 bonded with polyacrylate binder 18
, non-woven fabric formed from 100 strands of 5-denier unwhitened crimped rayon fiber; 35 g/m2; 1 cm
22 square openings per 2 - side dimensions 1,1
+s+i Examples 1-6 The cleaning additive products of the present invention are manufactured as follows. For each product, the ingredients of the toiletry additive composition are mixed at a temperature of about 65°C and in a fryer colloid mill (Ii
'ryma Co11oid Mill) Model M K
95-R/MZ 811R (M M Process Equipment Ltd., UK 13). The bath melt was then passed through a 250 micron nip setting and heated to 76°C in the opposite direction. The coated substrate is fed into a pair of rotating rolls and transferred by smearing to a substrate moving counter to one of the rollers.Finally, the coated substrate is passed between a pair of stationary plates having a spacing of approximately 180 microns. Let it dry (Lice) and dry it 35x
Cut into sheets of 23 Llll size. 1 2 LAS
3C12,/14A S 5 3
T A E25 3C12
TMA B 2 -dopanol 4
5E7 5 3PEG 8000
5 5TAED
5-PAG
3AOBS
--Silicone/silica
0.3 0.2 porphyne
0.2 Gauntlets AN119 0.
3 - Perborate -- EDTA -- Brightener 1
0.3 Brightener 2 0.1 0.1 DETP
MP O,51EDTMP
-- Moisture 0.8 0.5 Substrate 1 2.8 2.8 Substrate 2
- - Cover opening hole 4033 3 4 5 6-
-5 -6
3 3 8--4 4 3 35
4 5 -7
6 7 8- -
3 -- 1 ・-
-0,20,20゜3 0.3 - - - 0.3-
0.8 0.5-
5 --- ---
0.2 - -0.1
0,2 0.1-0.2
0.3 --0.8 1 1.5 0.5 ---0.6
0,2 0,5 0.7-
2.8 - -2.8
2,8 2.845 5
0 42 55 The product is an effective cleaning detergent that combines a unique composition's body-to-substrate ratio with excellent flexibility, product release, feel and storage properties. Applicant's agent Kiyoshi Inomata

Claims (1)

[Claims] 1', (a) EO-type water-soluble or water-dispersible polymer having a melting completion temperature lower than 85°C) IJ
consisting of at least 4 () members and at least 35
A solid laundry additive composition having a softening temperature of °C, and t
b) Flexible sheet-like apertured substrate with an opening density of 1 (J-31 per sheet) (the openings are semi-averaged with Q, a width of 511111 to 511113 and Q
, f3111+lI to 5111111, the substrate is supported with a water-releasable substance of the laundry additive composition and the area of the undamaged opening and the coating covers the opening and the opposite surface of the substrate the area ratio of uncoated openings to coated openings is from 15:1 to 1=3, and the weight ratio of composition to substrate is at least 5:1). A fluid bed additive product characterized by: 2. The substrate is about 13 to about 2 fi per sheet l cm
2. A product according to claim 1, characterized in that it has an open area density of from about 16 to about 23, preferably from about 16 to about 23. 3. The opening is about 0.7 to about 7111111 on average
A product according to claim 1 or 2, characterized in that it has an area and length cutting width ratio of 1:1 to about 6:1, preferably 1:1 to 4:1. . 4. The opening has an average width of about Q, 8111111 to about 1.5 mm, and about 2111th to about 3°5 n1l.
It is an elongated shape with a length of 11 #lJ~
The body made of any one of claims 1 to 3, characterized in that it is generally square with sides M of about 2.5 #1 m, weighs about 10 to about 10 g. /m2 Tsubotoshi and about 12 pieces to about 'L! 5 sections, preferably about 16
% to about 22% of the hydrophobic binder tree B'#δM. Group 4 1st to 4th
Products mentioned in any of the songs. The wash additive composition comprises at least about 50%, preferably less than 6%, of an organic matrix material having a bath melt completion temperature of less than about 75°C, preferably less than about 70"C; Product according to any one of claims 1 to 5, characterized in that it exhibits a softening width a of H1°C, preferably at least about 50°C. The weight ratio is at least about 6=11
Preferably at least about 7=1 and not+Jj
i lj 1ji The area ratio of the J bottom part to the covered open bottom part is approximately 6:
7. A product according to any one of claims 1 to 6, characterized in that the ratio is from 1 to about 1:2, preferably from about 4:1 to about 1.1. 8. Low (both about 35℃ melting start temperature and about 85℃
A water-soluble or water-dispersible binder with a melt onset temperature lower than 5%, preferably less than 1%
8. A product according to any of claims 1 to 7 characterized by 5%. 9. Polyethylene glycols in which the binder has a molecular weight greater than about 1000, 012-c18 fatty acids and their esters and amides, about 40,000 to about 700
, 000, and c14-c24 fatty alcohols ethoxylated with about 14 to about 100 moles of ethylene oxide. . 10. A product according to claim 8 or 9, characterized in that the binder consists of at least about 40%, preferably at least about 50%, of polyethylene glycol having a molecular weight higher than about 4,000. . 11, at least about 5% organic detergent selected from anionic surfactants, nonionic surfactants, cationic surfactants and mixtures thereof, preferably at least about 44%;
Claims 1 to 1 characterized by %
Products listed in any of item 0. 12. At least about 5 inorganic or organic peroxy whitening agents
12. A product according to any one of claims 1 to 11, characterized by at least 2% of an organic peroxyacid bleaching agent precursor and/or an organic peroxyacid bleaching agent precursor.