JPS5829840B2 - Fuhakuno Conditioning Tokusei Omotsu Senzai Soseibutsu - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to detergent compositions which, in addition to conventional organic surface-active ingredients, contain substantially water-insoluble particulate material.

Modern detergent compositions, machinery, and auxiliary chemical additives, such as fabric softeners, washers, and dryers, are inordinately directed toward achieving benefits other than the explicit goal of clean laundry. .

The benefits that we strive to give to fabrics that go through the entire cycle from washing to drying include fluffiness, flexibility, waist,
There is reduced static charge, wrinkle resistance, ease of ironing, and improved appearance.

There is currently no single product or machine process that achieves all of these benefits simultaneously.

For example, current fabric softeners impart flexibility to fabrics (in fact, this flexibility is most similar to the tactile sensation of smoothness; it is the softness of the fabric caused by the fabric's increased bulk). (can be distinguished from ), suppresses static electricity charging.

Modern washers and dryers, through sophisticated cycle and temperature control, can significantly improve the degree to which fabrics wrinkle.

Other products such as the well-known laundering paste (optionally in combination with particulate organic ingredients having a melting point below the ironing temperature) improve crease permanence and ease of ironing when applied after a wash cycle. give the benefit of
Also, the waist or glue on the fabric gives an effect.

However, the detergent composition of the present invention simultaneously provides all of the above benefits through laundering.

That is, the detergent compositions of the present invention provide the aforementioned benefits during the wash cycle through certain physicochemical interactions at the fiber or yarn level that are not fully understood.

These benefits are due in large part to the coexistence of the water-insoluble particulate material and the organic surfactant described below.

Detergent compositions containing various particulate materials with specific functions are known in the art.

An example is a scrubbing detergent composition containing water-insoluble particulate material, often with a particle size in the range of about 50-100 microns and a hardness of about 7 on the Mohs hardness scale.

It has long been known that large amounts of starch, through its gel-forming properties, impart desirable physical properties to bar soaps.

The properties of starch as a binder, flocculant, film former, and inert diluent have also been exploited in granular detergent compositions.

Starch and starch derivatives can be prepared by the pri ring method (pri ring method).
They are also used in large amounts in synthetic detergent compositions to improve the efficiency of the lling process, i.e., the efficiency of forming granular detergents from an aqueous medium in which the detergent is synthesized or redissolved in the aqueous medium. There is.

Thermoplastic particulate materials are also known in the art and are used primarily in conjunction with laundry operations as fabric finishing agents, ironing aids, and glueing agents.

These substances soften or melt, for example during ironing, thereby gluing the fabric.

It is also known that certain clay materials with exchangeable calcium and magnesium ions can be deposited on fabrics to impart softening properties to the fabrics.

Clay deposition as described above is commonly expressed by contacting the fabric to be treated with an aqueous suspension of clay (see, e.g., U.S. Pat. Nos. 3,033,699 and 3,594,221). ).

U.S. Patent Application No. 271943 (filed on July 14, 1972), No. 27912.7 (filed on August 9, 1972), No. 305416 (filed on November 10, 1972), and No. 305417 (filed on November 10, 1972). No. 333104 (filed on February 16, 1973), and No. 337331 (filed on March 2, 1973) contain clay in detergent and softening compositions. It is described that it is used.

However, the above-mentioned prior art techniques are directed towards achieving specific functions and objectives, and they are based on the properties of the particulate material, namely water insolubility, shape, integrity, particle size, hardness, exchangeable alkaline earth metal ions, etc. The physical properties of water-insoluble particulate materials suitable for use in the compositions of the present invention are essentially different with respect to the presence and melting point (softening temperature).

In any event, prior art detergent compositions containing the particulate materials described above do not provide the fabric conditioning benefits of the compositions of the present invention and often tend to impart a harsh feel or stiffness to the fabric. There is.

It is therefore an object of the present invention to provide a detergent composition containing a water-insoluble particulate material, which provides fabrics treated with it with improved wrinkle resistance, ease of ironing, fabric flexibility, antistatic properties, and crease resistance. An object of the present invention is to provide a detergent composition that provides ease of washing, increased fabric drapeability, and appearance benefits.

A further object of the invention is to obtain enhanced tactile and appearance properties at least comparable to those produced by the use of rinse softeners imparted after conventional washing, i.e. during the rinsing operation. The object of the present invention is to provide a detergent composition that can simultaneously clean and condition fabrics.

By using certain particulate materials which, when present in conjunction with organic surfactants, can provide desirable fabric benefits, the foregoing objectives can be achieved and which can also clean fabrics and at the same time impart a series of Desirable characteristics (
Wrinkle resistance, ease of ironing, fabric flexibility,
Detergent compositions are also formulated that can provide antistatic properties, ease of creasing, enhanced fabric drapability, and appearance benefits.

SUMMARY OF THE INVENTION The present invention provides detergent compositions that can simultaneously clean fabrics and impart desirable fabric properties to the fabrics.

Such compositions include the following ingredients: (a) from about 2 to about 995% by weight of an organic surfactant selected from the group consisting of anionic, nonionic, zwitterionic and amphoteric detergents and mixtures thereof; and (b) about 0 substantially water-insoluble particulate material selected from the group consisting of surface-modified starch, glass beads, glass small hollow spheres, and mixtures thereof, having the following characteristics:
．． 05 to about 10% by weight: (1) average particle size in the range of about 1 to about 50 microns; (11) shape with anisotropy of about 5:1 to 1:1; (about 5.5 on the 110 Mohs hardness scale) (1v) a melting point greater than about 150°C; and (v) substantially free of exchangeable calcium and magnesium ions.

From a method standpoint, the present invention relates to a method of treating fabrics to clean and at the same time provide wrinkle resistance, ease of ironing, softness, antistatic properties and appearance benefits.

Such a method comprises treating the fabric in an aqueous solution containing the following ingredients: (a) an organic surface selected from the group consisting of anionic, nonionic, zwitterionic and amphoteric detergents and mixtures thereof; from about 10 to about 10,000 ppm of active agent: and (b) a substantially water-insoluble particulate material selected from the group consisting of surface-modified starch, glass beads, glass small hollow spheres, and mixtures thereof, having the following characteristics: Approximately 0
．． 2 to about 1000 ppm: (1) Average particle size ranging from about 1 to about 50 microns: (1]) Shape with anisotropy of about 5:1 to 1:1 (less than about 5.5 on the 110 Mohs hardness scale) (IV) a melting point greater than about 150°C; and (v) substantially no exchangeable calcium and magnesium ions.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to detergent compositions that are capable of cleaning fabrics and at the same time imparting desirable fabric properties to the fabrics.

These compositions include (1) an organic surfactant and (2) a substantially water-insoluble particulate material as defined herein.

Unless otherwise specified, percentages are percentages by weight.

Suitable essential organic surface-active ingredients for use in the compositions of the invention are selected from the group consisting of anionic, nonionic, zwitterionic and amphoteric detergents and mixtures thereof.

The component ranges from about 2 to about 99.5%, preferably from about 4 to about 60%.
, more preferably in an amount of about 6 to about 40%.

Examples of suitable surface-active compounds for use in accordance with the invention include: Anionic detergents and water-soluble soaps.

Suitable soaps include the sodium, potassium, ammonium and hyalkanol ammonium salts (eg, mono-, di-, and triethanolammonium salts) of higher fatty acids (Cto''C2□).

Particularly useful are the sodium and potassium salts of fatty acid mixtures derived from coconut oil and beef tallow, ie, the sodium and potassium soaps of beef tallow and coconut oil.

The anionic synthetic detergent is a water-soluble organic sulfuric acid reaction product having in its molecular structure an alkyl group containing about 8 to about 22 carbon atoms and a moiety selected from the group consisting of a sulfonic acid ester moiety and a sulfuric acid ester moiety. There are also salts, especially alkali metal salts.

(The term alkyl includes the alkyl portion of higher acyl moieties).

Examples of synthetic detergents of this type which form part of the preferred built detergent compositions of the present invention include: sodium and potassium salts of alkyl sulfates, especially those prepared by reducing the glycerides of tallow or coconut oil. higher alcohol (
obtained by sulfating Ca-Cl8): sodium and potassium salts of alkylbenzene sulfonic acids, the alkyl group containing from about 9 to about 2 carbon atoms in a linear or branched configuration. salts of linear straight-chain alkylbenzene sulfonic acids in which the alkyl group has an average number of carbon atoms of about 11.8, such as those of the type described in U.S. Pat. are particularly useful (called C1□, 8LAS); sodium alkyl glyceryl ether sulfonates, especially those which are ethers of higher alcohols derived from beef tallow and coconut oil; coconut oil fatty acid monoglyceride sulfones. Sodium acid and coconut oil fatty acid monoglyceride sodium sulfate; sodium and potassium salts of alkylphenol ethylene oxide ether sulfate, containing from about 8 to about 8 alkyl groups with about 1 to about 10 units of ethylene oxide per molecule.
Containing about 12 carbon atoms.

Nonionic phosphate surfactants are also useful in the present invention.

These are surface-active substances with substantial detergent ability, in which the anionic solubilizing group attached to the hydrophobic moiety is a phosphorus oxyacid.

The more common solubilizing groups are thermal, -8O4H and -5O3
It is H.

Alkyl phosphate esters such as (R-O)2PO2H and ROPO3H2 (where R represents an alkyl chain containing from about 8 to about 20 carbon atoms) are useful in the present invention.

These phosphoric acid esters can be modified by incorporating 1 to about 40 units of alkylene oxide, such as ethylene oxide, into the molecule.

The general formula for these modified phosphate-based anionic detergents is as follows: where R is an alkyl group containing about 8 to 20 carbon atoms, or an alkylphenyl group, where R is an alkyl group containing about 8 to 20 carbon atoms;
20 carbon atoms), M is hydrogen,
A soluble cation such as sodium, potassium, ammonium or substituted ammonium, where n is an integer from 1 to about 40.

Another class of suitable anionic organic detergents useful in this invention include the salts of 2-acyloxyalkane-1-sulfonic acids.

These salts have the following general formula: where R1 is an alkyl group having about 9 to about 23 carbon atoms (
(together with the two carbon atoms in the formula form an alkane group), R2 is alkyl having from 1 to about 8 carbon atoms, and M is a water-soluble cation.

The water-soluble cation M in the above structural formula can be, for example, an alkali metal cation (eg sodium, potassium, lithium), ammonium or substituted ammonium cation.

Specific examples of substituted ammonium cations include methyl-,
Dimethyl and trimethyl-ammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations, and those derived from alkyl amines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.

Specific examples of β-acyloquine-alkane-1-sulfonates useful in the present invention, i.e., 2-acyloxy-alkane-1-sulfonates, include: Sodium 2-acetoxytridecane-1-sulfonate. salt, 2
-Potassium salt of propionyloxy-tetradecane-1-sulfonic acid, 2-butanoyloxy-tetradecane-
Lithium salt of 1-sulfonic acid, sodium salt of 2-pentanoyloxy-pentadecane-1-sulfonic acid, 2-
Sodium salt of acetoxy-hexadecane-1-sulfonic acid, potassium salt of 2-octanoyloxy-tetradecane-1-sulfonic acid, sodium salt of 2-acetoxy-hebutadecane-1-sulfonic acid, 2-acetoxy-octadecane- i - Lithium salt of sulfonic acid, potassium salt of 2-acetoxy-nonadecane-1-sulfonic acid, 2
-acetoxy-lancosan-1-sulfonic acid nonodium salt, sodium salt of 2-propionyloxy-tocosan-1-sulfonic acid, isomers thereof.

β-Acyloxy-alkane preferred in the present invention
The salt of 1-sulfonic acid has R1 of about 12 in the above formula.
Alkali metal salts of β-acetoxy-alkane-1-sulfonic acids corresponding to alkyls having ~16 carbon atoms; these salts are preferred from the point of view of their excellent cleaning properties and ready availability. .

Representative examples of the β-acetoxyalkanesulfonates mentioned above are described in Belgian Patent No. 650,323, which describes the preparation of certain 2-acyloxyalkanesulfonic acids.

Similarly, U.S. Patent Nos. 2,094,451 and 20,862
No. 15 describes certain salts of β-acetoxyalkanesulfonic acids.

These documents are hereby incorporated by reference.

Owing to their excellent cleaning properties and their insensitivity to hard water (Ca+ and Mg++ ions), other types of anionic detergent compounds used in the present invention
It is an alkylated α-sulfocarboxylate containing about 23 carbon atoms and having the following general formula: where R is C8-C20 alkyl and M is a water-soluble cation as described above, preferably is a sodium ion and R' is a short chain alkyl such as methyl, ethyl, propyl, and butyl.

These compounds are made by esterifying commercially available alpha-sulfonated carboxylic acids using standard techniques.

Specific examples of the alkylated α-sulfocarboxylates used in the present invention include: methyl-α-ammonium sulfopalmitate, ethyl-α-sulbostearif['Jethanolammonium, methyl-α-ammonium].
Sodium sulfopalmitate, sodium ethyl-α-sulfopalmitate, sodium butyl-α-sulfostearate, potassium methyl-α-sulbolaurate, lithium methyl-α-sulfolaurate, and mixtures thereof.

Yet another class of anionic organic detergents are the β-alkyloxyalkanesulfonates.

These compounds have the following general formula: where R1 is a straight chain alkyl group having 6 to 20 carbon atoms and R2 is a lower alkyl group having 1 to 3 carbon atoms, preferably 1 carbon atom. group, and M is a water-soluble cation as described above.

β-alkyloxyalkanesulfonates, which are less susceptible to hard water (calcium ions), useful in the present invention to provide excellent cleanliness levels under domestic laundry conditions;
Thus, specific examples of 2-alkyloxyalkane-sulfonates include: potassium β-methoxydecanesulfonate, sodium 2-methoxytridecanesulfonate, potassium 2-ethoxytetradecylsulfonate, 2-inpropoxyhexane. Sodium decylsulfonate, lithium 2-t-butoxytetradecylsulfonate, sodium β-methquin octadecylsulfonate, and ammonium β-n-propoxydodecylsulfonate.

Further examples of non-soap anionic synthetic detergents falling within the scope of the present invention include reaction products of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide, wherein the fatty acids are For example, those derived from coconut oil; sodium or potassium salts of fatty acid amides of methyldauride, the fatty acids being derived from, for example, coconut oil.

Other anionic synthetic detergents of this type are U.S. Pat.
No. 6921, No. 2486922, and No. 239627
It is described in each specification of No. 8.

Further examples of non-soap anionic synthetic detergents that fall within the scope of the present definition include compounds containing two anionic functional groups.

These are called dianion detergents.

Suitable dianionic detergents are disulfonates, disulfonates, or mixtures thereof, and have the following general formula: R(803)2M2, R(804)2M2, R(SO3) (5O4) M2 where is an acyclic aliphatic hydrocal group having 15 to 20 carbon atoms, and M is a mizucho solubilizing cation.

Examples include disodium 1,2-alkyldisulfate from CI5 to C20, dipotassium 1,2-alkyldisulfonate from C15 to C20, dipotassium 1,2-alkyldisulfate from CI5 to C20, and disodium 9-hexadecyldisulfate. , 1,2-alkyl disulfonic acid disodium having CI5 to C20, (1) disodium 9-stearyl disulfate, and disodium 6,10-octadecyl disulfate.

The disulfonate or aliphatic portion of the disulfonate is substantially linear, thereby imparting desirable biodegradable properties to the detergent compound.

The water-solubilizing cations mentioned above are the conventional cations known in the detergent industry, namely alkali metal cations, ammonium cations, as well as IIA, IIB, rlIA, IV of the periodic table.
There are metals of groups A and IVB (excluding boron).

Preferred water-solubilizing cations are sodium and potassium.

These dianionic detergents are described in more detail in British Patent No. 1,151,392.

Furthermore, there is a type of anionic synthetic detergent called succinamate.

Examples of this type include disodium N-octadecylsulfosuccinamic acid, tetrasodium N-(1,2-dicarboxyethyl)-N-octadecylsulfosuccinamic acid, cyamyl ester of sodium sulfosuccinate, and sodium sulfosuccinate. and dioctyl ester of sodium sulfosuccinate.

Preferred surfactants for use in the compositions of this invention include alkyl ether sulfates and "'olefin sulfonates."

Preferred alkyl ether sulfates have the following general formula: where R is an alkyl or alkenyl having about 10 to about 20 carbon atoms, X is from 1 to 30**, and M is an alkali metal (sodium , lithium, potassium), ammonium, amines and substituted ammoniums.

Examples of the amines include lower C1-4 alkyl amines,
and mono-, di- and trimethanols and ethanolamines.

Particularly preferred are alkyl ether sulfates in the above formula in which R has about 14 to about 18 carbon atoms and X has an average value of about 1 to about 6.

Specific examples of particularly preferred classes are sodium coconut oil alkyl ethylene glycol ether sulfate, sodium tallow alkyl triethylene glycol ether sulfate, sodium tallow alkyl pentaoxyethylene sulfate, ammonium tetradecyl pentaoxyethylene sulfate, and ammonium lauryl hexaoxyethylene sulfate.

Particularly preferred alkyl ether sulfate components have an average of 12 to 16 carbon atoms, preferably about 14 to 5 carbon atoms (
arithmetic mean) carbon chain length, and ethylene oxide about 1 to 4;
Preferably it has an average (arithmetic mean) degree of ethoxylation of about 2 to 3 molar.

Such a mixture is a mixture of c1□-13 compounds of about 0.0.
05-5% by weight, mixture of CI4-15 compounds about 55-5%
70% by weight, mixture of C16-1□ compounds about 25-40
Weight % and CI8-1. The mixture of compounds consists of about 0.1-5% by weight.

In addition, such preferred alkyl ether sulfate mixtures include about 15-25% by weight of compounds with a degree of ethoxylation of O and about 50-25% by weight of compounds with a degree of ethoxylation of 1-4.
65% by weight, about 12-22% by weight of a mixture of compounds with a degree of ethoxylation of 5-8 and about 0.5-10% by weight of a mixture of compounds with a degree of ethoxylation greater than 8.

Examples of alkyl ether sulfate mixtures falling within the ranges specified above are listed in Table 1.

Preferred "olefin sulfonates" useful in the present invention have from about 12 to about 24 carbon atoms.

The component is made by sulfonating an alpha-olefin with uncomplexed sulfur dioxide, followed by neutralization under conditions such that any sultone present is hydrolyzed to the corresponding hydroquine-alkanesulfonate.

The α-olefin as a starting material is preferably 14 to 16
It has carbon atoms.

The preferred α-olefin sulfonates mentioned above are described in detail in US Pat. No. 3,332,88Q.

The US Patent Specification is hereby incorporated by reference.

The α-olefin sulfonates may be represented as a single species or as a mixture of structurally different sulfonation products.

Preferred mixtures are described in US Pat. No. 3,332,880, cited above.

One example of such a mixture consists essentially of about 30 to about 70% by weight of component A, about 20 to about 70% by weight of component B, and about 70% by weight of component C.
from about 2 to about 15% by weight, where (a) component A is a double bond regioisomeric mixture of a water-soluble salt of an alkene-1-sulfonic acid containing from about 20 to about 24 carbon atoms; , and the positional isomer mixture is α-β
About 10 to about 25% unsaturated isomers, about 30 to about 70% β-γ unsaturated isomers, and about 5 to about 2 γ-δ unsaturated isomers
5%, and about 5 to about 10% δ-ε unsaturated isomers;
(b) Component B is a water-soluble salt mixture of trifunctionally substituted sulfur-containing saturated aliphatic compounds containing from about 20 to about 24 carbon atoms, the functional units being hydroxyl and sulfonate groups; The sulfonate group is always on the terminal carbon, the hydroxyl group is attached to a carbon atom at least two carbon atoms away from the terminal carbon atom, and at least 90% of the hydroxyl substitution is on the 3-, 4-, and 5-positions. (e) Component C comprises about 30 to 95 water-soluble salts of alkene disulfonates containing about 20 to about 24 carbon atoms;
%, and from about 5 to about 70% of a water-soluble salt of a hydroxysulfonate containing from about 20 to about 24 carbon atoms, the alkene disulfonate having a sulfonic acid group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom that is no more than about 6 carbon atoms away from the terminal carbon atom, and the alkene double bond is between the terminal carbon atom and about the 7th carbon atom; The hydroxydisulfonate has a sulfonate group attached to a terminal carbon atom, a second sulfonate group attached to an internal carbon atom that is no more than about 6 carbon atoms away from the terminal carbon atom, and It is a saturated aliphatic compound having a hydroxyl group attached to a carbon atom that is no more than about 4 carbon atoms away from the point of attachment of the second sulfonate.

Particularly preferred for use in the composition of the present invention are 3-4
-1 and 5-hydroxyalkyl sulfonates and mixtures thereof.

Specific examples of the hydroxy-sulfonates include the thorium salts of the following: 3-hydroxy-n-denyl 1
-sulfonic acid, 3-hydroxy-n-dotecyl-1-sulfonic acid, 3-hydroxy-n-tetradecyl-1-sulfonic acid, 3-hydroxy-n-hexadecyl-1-sulfonic acid, 3-hydroxy-n-octadecyl- 1-Sulfonic acid, 3-hydroxy-n-eicosyl-1-sulfonic acid, 3-hydroxy-n-tocosyl-1-sulfonic acid, 3-hydroxy-n--r) Cucosyl-1-sulfonic acid, 4-hydroxy- n-decyl-1-sulfoheptaic acid, 4
-human oki'/-n-dotesyl-1-sulfonic acid,
4-Hydroxy-n-tetradecyl-l sulfonic acid, 4
-Hydroquine-n-hexadecyl-1-sulfonic acid, 4
-Hydroxy-n-: A-cutatesyl-1-sulfonic acid, 4-hydroxy-n-eicosyl-1-sulfonic acid, 4-hydroxy-n-)cosyl-1-sulfonic acid,
4-hydroxy-n-tetracosyl-1-sulfonic acid,
5-hydroxy-n-decyl-1-sulfonic acid, 5-hydroxy-n-dodecyl-1-sulfonic acid, 5-hydroxy-n-tetradecyl-1-sulfonic acid, 5-hydroxy-n-hexadecyl-1-sulfonic acid , 5-hydroxy-n-ophtatecyl-1-sulfonic acid, 5-hydroxy-n-eicosyl-1-sulfonic acid, 5-hydroxy-n
-tocosyl-1-sulfonic acid, and 5-hydroxy-n
-tetragosyl-1-sulfonic acid.

Among these desirable types, 4-hydroquine substitutes are
Preferred for use, for example, with 3-hydroxy- and 5-hydroxy-compounds.

This means that in these two-component systems 4-hydroxy is present in an amount greater than 50% by weight of the active detergent ingredients.

Nonionic Synthetic Detergents Most commonly, nonionic surfactants are compounds made by the condensation of an alkylene oxide (hydrophilic) with an organic hydrophobic compound (usually aliphatic or alkyl aromatic).

The chain length of the hydrophobic or polyoxyalkylene moiety that is condensed with any particular hydrophobic compound can be easily adjusted to yield a water-soluble compound with the desired balance between hydrophilic and hydrophobic components. .

Other types of nonionic surfactants are amines,
It is a so-called polar nonionic substance derived from phosphine oxide or sulfoxide.

Examples of suitable nonionic surfactants include:

(1) Condensate of polyethylene oxide and alkylphenol.

These compounds include condensation products of ethylene oxide with alkylphenols having alkyl groups containing about 6 to 12 carbon atoms in a straight-chain or branched-chain configuration, the ethylene oxide containing 5 Some are present in amounts of ~25 moles.

Alkyl substituents in such compounds are derived from, for example, polymerized propylene, diisobutylene, octene, or nonene.

Examples of this type of compound include a condensate of nonylphenol and about 95 moles of ethylene oxide per mole of nonylphenol, a condensate of dodecylphenol and about 12 moles of ethylene oxide per mole of totsylphenol, a condensate of dinonylphenol and dinonylphenol Condensate of di-isooctylphenol and di-isooctylphenol with about 15 moles of ethylene oxide per mole
There are about 15 moles of condensate with ethylene oxide per mole.

Commercially available nonionic surfactants of this type include Igepal CO-610, available from GAF Corporation, and Triton, available from CI-Music Company. Triton) X-45, X-1
14, X100 and X-102.

(2) Condensation product of aliphatic alcohol and ethylene oxide.

The alkyl chain of the aliphatic alcohol may be straight or branched and generally contains about 8 to about 22 carbon atoms.

Examples of such ethoxylated alcohols include about 6
A condensation product of 1 mole of ethylene oxide and 1 mole of tridecanol, a condensation product of myristyl alcohol and about 10 moles of ethylene oxide per mole of myristyl alcohol, a condensation product of ethylene oxide and a coconut oil fatty alcohol, wherein the coconut oil A mixture of fatty alcohols in which the alcohol has an alkyl chain of 10 to 14 carbon atoms, containing about 6 moles of ethylene oxide per mole of the condensate alcohol, and about 9 moles of ethylene oxide and coconut oil as described above. There are condensation products with alcohol.

Examples of commercially available nonionic surfactants of this type include Tergitol 15-S-9, available from Union Carbide Corporation;
Neodol sold by Chemical Company (
Neodol) 23-6. '5 and the Kyro EOB sold by The Brocter & Gamble Company.

(3) A condensation product of ethylene oxide and a hydrophobic base formed by the condensation of propylene oxide and propylene glycol.

The hydrophobic portion of these compounds has a molecular weight of about 1500-1 soo and exhibits thermal water insolubility.

Adding a polyoxene ethylene moiety to this hydrophobic moiety results in
The overall tendency is to increase the water solubility of the molecule, preserving the liquid character of the condensation product up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product.

An example of this type of compound is certain commercially available Pluoronic surfactants (sold by Wiandotte Chemicals Corporation).

). (4) A condensation product of ethylene oxide and a product produced by the reaction of propylene oxide and ethylenediamine.

The hydrophobic base of this product consists of the reaction product of ethylene diamine and an excess of propylene oxide, and the base has a molecular weight of about 2,500 to about 3,000.

This base is prepared such that the condensation product has from about 40 to about 80% by weight polyoxyethylene and from about 5,000 to about 11,000% by weight.
It is condensed with ethylene oxide to the extent that it has a molecular weight of .

Examples of nonionic surfactants of this type include certain commercially available Tetronic surfactants.
nic) compound (sold by Wiandtute Chemicals Corporation).

(5) A surfactant (amine oxide surfactant) having the following general formula: where R1 is about 10 to about 28 carbon atoms, 0 to about 2 hydroxyl groups, and O to about 5 ethers. is an alkyl group containing a bond, and a small portion of R1 is about 10 to about 18
an alkyl group containing from 1 to about 3 carbon atoms and containing no ether linkage, each R2 and R3 being selected from the group consisting of an alkyl group containing from 1 to about 3 carbon atoms and a hydroxyalkyl group .

Specific examples of amine oxide surfactants include: dimethyldodecylamine oxide, diethyltetradecylamine oxide, ethylmethyltetradecylamine oxide, cetyldimethylamine oxide, dimethylstearylamine oxide, cetyl ethyl fluoropyramine. oxide, diethyldodecylamine oxide, diethyltetradecylamine oxide, diglopyrdodecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, bis-(2-hydroquinethyl)
-3-dodecoxy1-hydroxypropylamine oxide, (2-hydroxypropyl)methyltetradecylamine oxide, dimethyloleylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide,
and the corresponding decyl, hexadecyl and octadecyl analogs of each of the above compounds.

(6) A surfactant having the following general formula (phosphine oxyto surfactant): where R1 is about 10 to about 28 carbon atoms, 0 to about 2 hydroxyl groups, and O to about 5 ethers. is an alkyl group containing a bond, and at least a portion of R1 is about 10 to about 18
an alkyl group containing from 1 to about 3 carbon atoms and containing no ether linkage, each R2 and R3 being selected from the group consisting of an alkyl group containing from 1 to about 3 carbon atoms and a hydroxyalkyl group .

Specific examples of phosphine oxyto surfactants include:

Dimethyldodecylphosphine oxide, dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide, dimethylsterylphosphine oxide, cetyl ethylpropylphosphine oxide, diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide, Dipropyldodecylphosphine oxide, dipropyldodecylphosphine oxide, bis-(hydroxymethyl)-dodecylphosphine oxide, bis(2-
hydroxyethyl)dodecylphosphine oxide, (2
-hydroxypropyl)methyltetradecylphosphine oxide, dimethyloleinphosphine oxide, and dimethyl-(2-hydroxydodecyl)phosphine oxide and the corresponding decyl, hexadecyl, and octadecyl congeners of each of the above compounds.

(7) A surfactant having the following general formula (sulfoxide surfactant): where R1 is about 10 to about 28 carbon atoms, 0 to about 5 ether linkages, and O to about 2 hydroxyl substitutions. at least a portion of R1 is an alkyl group containing about 10 to about 18 carbon atoms and contains no ether linkages, and R2 is an alkyl group containing 1 to 3 carbon atoms and 0-2 It is an alkyl group containing hydroxyl groups.

Specific examples of sulfoxide surfactants include octadecylmethyl sulfoxide, dodecylmethyl sulfoxide, tetradecylmethyl sulfoxide, 3-hydroxytridecylmethyl sulfoxide, 3-methoxytridecylmethyl sulfoxide, 3-hydroxy-4-dodecoxybutylmethyl sulfoxide. , octadecyl (2-hydroxyethyl) sulfoxide, and human decylethyl sulfoxide.

Among all the types of nonionic surfactants mentioned above,
Preferred nonionic surfactants include:
Nonylphenol and about 9.0% per mole of nonylphenol.
Condensation products of 5 moles of ethylene oxide, condensation products of coconut fatty alcohols with about 6 moles of ethylene oxide per mole of coconut fatty alcohols, condensation products of tallow fatty alcohols with about 11 moles of ethylene oxide per mole of tallow fatty alcohols. product, and the condensation product of a secondary fatty alcohol containing about 15 carbon atoms with about 9 moles of ethylene oxide per mole of the fatty alcohol.

Amphoteric synthetic detergents Amphoteric synthetic detergents are derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines, in which the aliphatic group is linear or branched, and the aliphatic substituents are One is about 8 ~
Containing 18 carbon atoms, at least one of the aliphatic substituents contains an anionic water solubilizing group such as carboxy, sulfonate, sulfato.

Examples of compounds falling within this definition are sodium 3-(dodecylamino)gropionate, sodium 3-(dodecylamino)furopane-1-sulfonate, sodium 2-(dodecylamino)ethyl sulfate, 2-(dimethylamino)sodium ) Sodium octadecanoate, disodium 3-(N-carboxymethyldodecylamino)-propane-1-sulfonate, disodium octadecyl-iminodiacetate, sodium salt of ■-carboxymethyl-2-undecylimidazole, and N-N -Bis(2-hydroxyethyl)-2-sulfato-3-dodecoxyprobylamine sodium salt.

Sodium 3(dotecylamino)furopane-1-sulfonate is preferred.

Zwitterionic synthetic detergents Zwitterionic surfactants are generally referred to as derivatives of secondary and tertiary aminos, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. can.

The cationic atom of the fourth compound can be part of a heterocycle.

All of these compounds have at least one straight or branched aliphatic group containing about 3 to 18 carbon atoms, and at least one aliphatic substituent is an anionic water-solubilizing group, e.g. Contains carboquine, sulfonate, sulfate, phosphato, or phosphono.

Examples of various zwitterionic surfactants that may be used in the present invention are: Compounds corresponding to the following general formula, where R1 contains from about 8 to about 18 carbon atoms and optionally about 10 alkyl, alkenyl or hydroxyalkyl containing up to 1 to 3 ethylene and/or glyceryl moieties, Yl is nitrogen, phosphorus or sulfur, and R2 is an alkyl or monocontaining alkyl containing 1 to 3 carbon atoms. is hydroxyalkyl,
is I when Yl is S, and is I when Yl is N or P
2, R3 is alkylene or hydroxyalkylene containing 1 to about 5 carbon atoms, and Z
is a carboxy, sulfonate, sulfate, phosphate or phosphonate group.

An example of this type of zwitterionic surfactant is 3-(N-
N-dimethyl-N-hexadecyl ammonio)-furopane-1-sulfonate, 3-(N-N-dimethyl N-hexadecyl ammonio)-2-hydroxypropane-1
-sulfonate, 2-(N-N dimethyl-N-dodecyl ammonio)acetate, 3-(N-N-dimethyl-N
-dodecyl ammonio)propionate, 2-(N-N
-dimethyl-N-ophtatecylammonio)ethane-1
-sulfate, 3-(P-P-dimethyl-P-dodecylphosphonio)propane-1-sulfonate, 2(S-
Methyl-5-t-hexadecylsulfonio)ethane-1
-sulfonate, 3-(S-methy/L/-8-dodecyl ammonio)propionate, 4-(S-methyl-8
-tetradecylsulfonio)butyrate, 3-(N-N
-dimethyl-N-4-tothycenylammonio)propane-1-sulfonate, 3-(N-N-dimethyl-N-2
-jetoxyhexadecyl ammonio) 70 pans-1-
phosphate, and 3-(N-N-dimethyl-N-4-
Glyceryl dodecyl ammonio) propionate.

Preferred compounds of this type from a commercial point of view are 3(N-N-dimethyl-N-hexadecyl ammonio)-2-hydroxypropane-1-sulfonate, 3-(N-N-dimethyl-N-alkylammonio), t )-2-hydroxypropane-1-sulfonate (the alkyl group of which is derived from tallow fatty alcohol), 3-(N-N-dimethyl N-hexadecyl ammonio)furopane-1-sulfonate, 3-(N -N-dimethyl-N-tetradecylammonio)furopane-1-sulfonate, 3-(N-N
-dimethyl-N-alkylammoni, t)-2-hydroxypropane-1-sulfonate, the alkyl group of which is derived from the middle distillate of a coconut fatty alcohol;
3-(N-N-simethyl-N-dodecyl ammonio)-
2-hydroxypropane-1-sulfone), 4-(N
・N-dimethyl-N-tetradecylammonio)butane-1-sulfonate, 4-(N-N-dimethyl-N-hexadecylammonio)butane-1-sulfonate, 4
-(N-N-dimethyl-N-hexadecyl ammonio)
butyrate, 6-(N·N-dimethyl-N-ophtatecylammonio)hexanoate, 3-(N-N-dimethyl-N-eicosylammonio)-3-methylpropane-1-sulfonate, and 6-( N-N-dimethyl-N
-hexadecylammonio)hexanoate.

Means for preparing numerous surfactant compounds of this class are disclosed in U.S. Pat.
2 and 3529521 and German Patent No. 101
It is described in each specification of No. 8421.

All such specifications are hereby incorporated by reference.

A compound having the following general formula, where R4 is an alkyl, cycloalkyl, aryl, aralkyl or alkaryl group containing 10 to 20 carbon atoms, and M is aminocarbonyl, carbonylamino, carbonyloxy, aminocarbonylamino, A divalent group selected from the group consisting of a thio group and a substituted amino derivative thereof, R6 and R8 are an alkylene group containing 1 to 12 carbon atoms, and R6 is an alkylene group containing 1 to 10 carbon atoms.
alkyl or hydroxyalkyl containing carbon atoms, R7 is a group of R6, R4-M-R, and -
R8COOMe (in the formula, R4, R6, R6 and R8 are as described above, and Me is a monovalent salt-type cation).

Compounds of this type include N-N-bis(oleylamidepropyl)-N-methyl-Ncarboxymethylammonium betaine, N-N-bis(stearamidopropyl)-N-methylN-carboxymethylammoniumbetaine, -(stearamidopropyl)-N-dimethyl N-J ruboxymethylammonium betaine N-
N-bis(oleylamidepropyl)-N(2-hydroxyethyl)-N-carboxymethylammonium betaine, and N-N-bis(stearamidepropyl)-
There is N-(2-hydroxyethyl)-N-carboxymethylammonium betaine.

This type of zwitterionic surfactant is described in U.S. Pat.
No. 5719 and DAS No. 1018421.

A compound having the following general formula, where R9 is an alkyl group, RIO is a hydrogen atom or an alkyl group, and the total number of carbon atoms in Ro and Rlo is 8 to 16; in this case, R71, R1° and R13 is each an alkyl group or a hydroxyalkyl group, or R1□
and R12 and R13 are bonded together to form a heterocycle, and n is 1 or 2.

Examples of suitable zwitterionic surfactants of this type include r and delta hexadecylpyridinosulfobetaine, gamma and delta hexadecyl r-picolinosulfobetaine, r and delta
These include tetradecylpyridinosulfobetaine and hexadecyltrimethylammoniosulfobetaine.

The preparation of such zwitterionic surfactants is described in South African Patent Application No. 6915788.

Compounds having the following general formula, where R14 is an alkaryl methylene group containing about 8 to 24 carbon atoms in the alkyl chain, and R15 is 1 to 7
selected from the group consisting of alkyl and hydroxyalkyl groups containing R14 carbon atoms;
R16 is alkyl or hydroxyalkyl containing 1 to 7 carbon atoms, R1 is alkylene or hydroxyalkylene containing 1 to 7 carbon atoms, and Zl is from the group consisting of sulfonates, carboquines, and sulfates. It is the chosen one.

An example of this type of zwitterionic surfactant is 3-(
N-dodecylbenzyl-N-N-dimethylammonio)
Propane-1-sulfonate, 4-(N-Mdecylbenzyl-N-N-dimethylammonio)butane-1-sulfonate, 3-(N-hexadecylbenzyl-N-N-
dimethylammonio)propane-1-sulfone), 3
-(N-dodecylbenzyl-N-N-dimethylammonio)propionate, 4-(N-hexadecylbenzyl-N-N-dimethylammonio)butyrate), 3-(N
Tetradecylbenzyl N-N-dimethylammonio)
Furopane-1-sulfate, 3-(N-dodecylbenzyl-N-N-dimethylammonio)-2-hydroxypropane-1-sulfonate, 3-CM-N-di(dodecylbenzyl)-N-methylammonio]furopane- 1-
sulfonate, 4-CN-N-di(hexadecylbenzyl)-N-methylammonio]butyrate, and 3-(
There is N.N-di(tetradecylbenzyl)-N-methylammonioyo-2-hydroxypropane-1-sulfonate.

Zwitterionic surfactants of this type and methods for their preparation are described in U.S. Pat.
It is described in each specification of No. 4.

All of these specifications are incorporated herein by reference.

Compounds having the general formula: R18 haalkylphenyl, cycloalkylphenyl or alkenylphenyl groups containing from 8 to 20 carbon atoms in the alkyl, cycloalkyl or alkenyl moiety; , and R20 are each an aliphatic group containing 1 to 5 carbon atoms, and R2
□ and R2° are each an aliphatic group, a hydrogen atom, or a hydroxyl group containing □ to 3 carbon atoms, and R23 is an alkylene group containing 2 to 4 carbon atoms.

An example of this type of zwitterionic surfactant is 3-(
N-dodecylphenyl-N-N-dimethylammonio)
Propane-1-sulfonate, 4(N-hexadecylphenyl-N-N-dimethylammonio)butane-1-sulfonate, 3(N-tetradecylphenyl-N-N-
dimethylammonio)-3,3-dimethylpropane-1
Sulfonate and 3-(N-dodecylphenyl N-N-
dimethylammonio)-3-hydroxypropane-1-
There are sulfonates.

Compounds of this type are described in detail in GB 970,883 and GB 1,046,252.

These specifications are hereby incorporated by reference.

Of all the types of zwitterionic surfactants mentioned above,
A preferred compound is 3-(N-N-dimethyl-N-
alkylammonio)-furopane-1-sulfonate and 3-(N-N-dimethyl-N-alkylammonio)
-2-hydroxypropane-1-sulfonate (the average chain length of the alkyl group in these same compounds is 14.8 carbon atoms), 3-(N-N-dimethyl-N-hexadecyl ammonio) ) furopane-1-sulfonate,
3-(N-N-dimethyl-N-hexadecyl ammonio)-2-hydroxypropane-1-sulfonate, 3-
(N-dodecylbenzyl-N-N-dimethylammonio)-furopane-1-sulfonate, (N-dodecylbenzyl-N-N-dimethylammonio)acetate, 3-
(N-dodecylbenzyl-N-N-dimethylammonio)propione), 6-(N-dodecylbenzyl-N.
N-dimethylammonio)hexanoate, and (N-
N-dimethyl-N-hexadecyl ammonio)acetate.

The substantially water-insoluble particulate component that may be used in the compositions of the present invention is selected from the group consisting of surface-modified starch, glass beads, glass small hollow spheres and mixtures thereof and is defined by the following set of properties: (1) About i, o to about 50 μ, preferably about 5 to 30
Average particle size of μ; (2) Shape with anisotropy of approximately 5:1 to 1:1: (3)
(4) a melting point (softening temperature) greater than about 150° C.; and (5) substantially free of exchangeable calcium and magnesium ions.

In the compositions of the present invention, the particulate component is used in an amount of about 0.05 to about 10%, preferably about 0.1 to about 6%, more preferably about 0.2 to about 4%.

Exceeding the above upper limit may reduce or even eliminate the benefits of the fabrics listed above to the extent that fabrics treated with such compositions develop undesirable stiffness and poor hand feel.

The substantially water-insoluble particulate component has an average particle size of about 1 to about 50
μ, preferably in the range of about 5 to about 30 μ.

Although it is not possible to explain exactly why a particle size in the specified range is necessary, the particle size limitation is limited by the diameter of the available (commercially available) textile fibers, which are mostly about 1
(in the range of 0 to about 30μ).

Therefore, the previously listed fabric benefits are not provided when using water-insoluble particulate materials having an average particle size greater than about 50 microns.

On the other hand, if water-insoluble particulate materials having an average particle size of less than about 1 micron are used, some of the individual benefits described above may be obtained under certain circumstances, but the conventional compositions of the present invention may not be as effective. You will never get the overall fabric benefit that you would get by using it.

The substantially water-insoluble particulate component is further characterized by anisotropy (axial ratio) of about 5=1 to 1:1.

Particle size is determined by measuring the projected area of the water-insoluble particles, ie, the linear dimension of this projected area.

In other words, the major and medial axes of particles lying freely at the most stable surface are normally horizontal and the minor axes are vertical.

In that connection, the term ``major axis'' refers to the maximum overall length of the particle, ``median axis refers to the maximum dimension of the particle in the direction perpendicular to the long axis, and ``minor axis refers to the plane containing the major and intermediate axes. Represents the maximum dimension in the vertical direction.

Anisotropy refers to the ratio of major to minor axes for a particular particulate material.

Particulate materials with anisotropy within the range of about 3:1 to about 1.1:1 are preferred for use in the compositions of the present invention.

Ad■nees 1nOPTI by P. Barer and V. E.-Co55lett, published by ACADEMIC PRESS, 1969.
CAL and ELECTRONMICRO8C
See also OPY), Volume 3.

This document is hereby incorporated by reference.

The essential particulate component for use in the present invention has a hardness of less than about 5.5 on the Mohs hardness scale.

The hardness so measured is a measure of the crush resistance of the particulate material.

It is known to be a very good indicator of the wear properties of particulate components.

Examples of substances arranged in increasing order of hardness according to the Mohs hardness scale are: h (hardness)-1: talc;
Dried filter press cake, soapstone, wax, agglomerated salt crystals; h-2 stone, rock salt, general crystalline salt,
Barite, chalk, earth sulfur; h-4: fluorite, soft phosphate, magnesite, limestone; h-5:! Jite, hard phosphate, hard limestone, chromite, bauxite; h-6: feldspar, titanite, amphibite; h-7: quartz, granite; h-8 nidbars; h-9: corundum , diamond; and h-10: diamond.

Suitable particulate materials have a hardness of less than about 5.5 on the Mohs hardness scale.

Although some of the benefits of fabrics may be obtained with particulate materials having a Mohs hardness of, for example, 7, in terms of overall benefits the particulate materials are not suitable for use in the compositions of the present invention.

As can be seen, moderately hard particles can cause damage to the fibers and yarns and have an adverse effect on the fabric, especially through the cumulative effects that occur during multiple washing operations.

The substantially water-insoluble particulate material is heated to approximately 150°C (300”F
) has a melting point exceeding

Particulate materials with melting points below that temperature do not provide the benefits of fabrics.

This is because they tend to melt during ironing and thus spread throughout the fabric, thereby giving it stiffness (this is commonly known as gluing).

This in itself is undesirable in the context of the present invention, so the particulate material must be such that it maintains its integrity and shape under ironing conditions, ie at about 150°C.

This is because such properties are essential to achieving the fabric benefits derived by using the compositions of the present invention.

Moreover, since the function of the particulate material in the context of the present invention depends on its integrity, shape, hardness, etc., as explained in detail above, the particulate material must be substantially water-insoluble.

However, it should be recognized that a small portion, such as less than 20%, of the particulate component may be water-dispersible and/or water-soluble without significantly reducing the performance benefits.

The water-insoluble particulate material is substantially free of exchangeable calcium and magnesium ions.

As can be seen, the presence of exchangeable alkaline earth metal ions such as calcium and magnesium in the particulate material increases its hydrophilic character.

This results in an enhanced swelling property, thus impeding the uniform and stable incorporation of particulate matter into the fiber structure.

As a result, particulate materials having exchangeable calcium and magnesium ions in their structure contribute to achieving some of the fabric's benefits, but reduce the fabric's ability to achieve the overall benefits described above.

Starch derivatives such as surface-modified starches having hydrophobic moieties that react with starch molecules to form ester and ether bonds are particularly preferred for use in the compositions of the present invention.

This starch derivative, as a result of its chemical modification,
It is water repellent and therefore substantially water insoluble.

Such starch derivatives are commercially available under the trade name DRY.
- National Starch Products Co. (Na
tional 5tarch Products
Co, available from ).

DRY-PLO starch has an average particle size of about 9-11 microns.

Other substantially water-insoluble particulate materials suitable for use in the compositions of the present invention include:
Merson & Cumingl Inc.), and (5) is manufactured by Catafuto Corporation (Ct.
It is manufactured by APHOTE Corporation.

See also: (1) Technical Data.

Sheet Forepate Fron” (TechnicalD
ate 5 sheets for ”Teflon
) 7 A; and Brochure Typical Properties Commons All Granular Teflon FFE-Fluorocarbon Resin (Typic
alProperties Common to
All Granular Teflon FFE
-Fluorocarbon Re5ins)”
AA 43044 (both published by DuPont); (2
) Catalog of Small Glass Beads (Cat
alog of Small Glass Beads
) C Microbeads Division, Katafuto Corporation (Microbeads Divi
sion.

Published by Cataphote Corporation], especially document MB-III-D S-5/72;
MB-IV-DS-5/72; MB-V-LP
-5/72; and MB-VI [LP-5/72; and (3) Technical Information Florasure Concerning Ecospheres, Hollow Glass and Ceramic Microspheres, Microballoons
on Brochureconcerning ECC
08PHER, ES@, hollowglass a
nd ceramic m1crospheres.

MICROBALLOONS) (Emernon &
(Published by Cumming).

Each of the above documents is incorporated herein by reference.

Other substantially water-insoluble particulate ingredients used in the compositions of the invention, in addition to the essential parameters defined in the claims, include particulate starch having a swelling power of less than about 15 at a temperature of 65°C. It is.

Avoid modifying the granular starch to the extent that it may lose its hard shape and become more soluble by gelation, derivatization, or degradation to the extent that the starch becomes unsuitable for use in the present invention. Should.

Potential or gelling starches with a swelling power of more than about 15 at 65° C. are less suitable as they tend to lose their individual shape and thus flow into the fibers, thereby imparting undesirable stiffness to the fabric.

The above swelling power was determined by Cereal Chem, 36.
Harry W, L, pp. 534-544 (1959)
It is obtained according to the method described in the paper of each et al.

10 g of starch are suspended in 180 ml of distilled water in a centrifuge bottle with an internal volume of 25071 Ll.

The suspension was poured into a small stainless steel preparation tank [width 1.9 CI].
rL (0,75 inch), height 3.8 crI'L (15
inch)] at just enough speed (i.e. 200 rpm) to keep the starch completely suspended.
) and stir mechanically.

This low speed avoids shearing the swollen and fragile granules and thus solubilizing the starch.

The bottle is lowered into a temperature controlled water bath maintained at 65°C (±0.1°C) and held for 30 minutes, with low speed stirring continued during this period.

The bottle is then removed, wiped dry, and placed on a twister.

The stirrer is removed and the total weight of water present is 200.
Rinse with enough distilled water to remove water (including water in raw starch) and pour the washings into the bottle.

The bottle is capped, shaken gently, and then centrifuged at 2200 rpm (or 700 times gravity) for 15 minutes.

Remove the clear supernatant from the precipitation paste by 6.35 mm (0.
, 25 inches).

A known small amount of this supernatant is evaporated to dryness in a steam bath and then dried in a vacuum oven at 120° C. for 4 hours.

Calculate the percentage of soluble matter extracted from starch on a dry basis.

The residual aqueous layer above the precipitated starch paste is then siphoned off as quantitatively as possible.

Measure the weight of the bottle and paste by twisting it,
The swelling power is calculated as the weight of settled paste per y of starch on a dry basis.

Starches with a swelling power of more than 15 at 65°C are not suitable for use in the compositions of the invention.

Although the final selection of a starch that meets the requirements of the present invention will depend on the starting material and also on the process conditions, such as bleaching, degradation, and isolation, imparted to the particular species, a suitable starch may be For example, it is obtained from corn, wheat, and rice.

General potato starch and tapioca starch are 65
It has a swelling power of more than 15° C. and is therefore not suitable for use in the compositions of the invention.

More complete documentation on water-insoluble starches, their preparation and isolation from various raw materials is well known [e.g.
The Starch Industry (THE 5TAR) by J. W. Knight, Pergamon Press, 1969.
CHINDUSTRY, Knight J.W.
pergamonPress London (19
69))].

However, as discussed below, and without being limited as a result thereof, the parameters of the particulate material used in the compositions of the present invention are essential to the extent that said characteristics directly contribute to beneficial fabric properties.

These critical limitations on the properties of particulate materials were initially determined by practical experiments.

Although there is no theoretical interpretation of these critical limitations, it is clear that particulate matter interacts with the fabric at the fiber level to impart the previously listed benefits to the fabric as a whole.

In this regard, it should be noted that fabrics essentially consist of an assembly of flexible microfibers arranged in a somewhat ordered geometric alignment.

The individual fibers within the assembly are usually in a bent or twisted configuration and are in varying contact with adjacent fibers.

When the assembly is deformed, each fiber moves relative to each other, and this relative movement contributes considerably to the characteristic softness of the fabric.

The extent to which a particular fabric recovers when the deforming force is removed is determined in large part by the nature of the interactions of the individual fibers that make up the fabric.

The fibers of the fabric are viscoelastic and therefore recover slowly from strain; however, the multiple points of contact between the fibers provide frictional binding, which further impedes the recovery process.

In most fabric structures, the contact area between fibers is likely less than 1% of the total fiber area.

It is generally estimated that the force per point of contact is in the range of 1 to 10 dynes.

Our hypothesis, which seeks to explain the efficacy of particulate matter in imparting the associated effects of wrinkle resistance, ease of ironing, flexibility, antistatic benefits and improved appearance, can be accepted because of the fabric's According to the above point of view.

For the purpose of conceptualizing this hypothesis, it will be described as the "ball bearing effect" below.

The above concepts are useful in elucidating the interaction between particulate matter and fabric matrix under conditions of applied deformation forces.

Microscopic analysis and contamination techniques have shown that the fabrics treated according to the invention are characterized by having loose particulate matter intimately dispersed in a permanent manner in the interstices of the fiber matrix. The located particulate material appears to act in a ball bearing manner to reduce interfiber forces during deformation of the fabric as a whole.

Its major effect is enhanced viscoelastic recovery (more effective against wrinkles)
and a reduction in the forces occurring at the fiber-to-fiber contact points (ironing ease effect).

This concept allows, as already mentioned above, to limit the particle size.

This is because most commercially available textile fibers have diameters that fall within the range of about 10 to about 30 microns.

Therefore, in order for the particulate material to be effective in the present invention, it should preferably be comparable in diameter to the textile fibers.

The aforementioned benefits likewise relate to the particulate matter present at points within the interstices of the individual fiber threads.

Microscopic examination of a cross-section of the fabric threads shows that the threads of the fabric treated according to the invention have a larger diameter than the threads of similar fabrics, which are distinguished by the absence of particulate matter.

As can be seen, the particulate matter located in the spaces between the fibers effectively spreads the yarn (apparently increases the bulk), thus making the fabric softer and fluffier.

It is clear that the antistatic benefit is related to the change in resistivity of the fabric matrix containing the particulate material.

For example, the coexistence of chemically modified granular starch, such as DRYFLO starch, increases the equilibrium moisture content of the matrix, thereby reducing its resistivity and thus its charging.

The particulate material can be mixed with a pre-prepared detergent or sprayed onto a pre-prepared detergent formulation immediately before packaging.

In all cases, however, the above-mentioned mixing step follows the L-displacement step, for example the heating step, which may change the inherent granular integrity of the granular material.

Detergent builder salts are also advantageously used in the compositions of the invention.

Suitable builder salts may be inorganic or organic and may be selected from a variety of known builder salts.

The builders are normally used in amounts of about 10% to about 60%, preferably about 10% to about 40%.

The weight ratio of organic surfactant to detergent builder salt is usually about 20:1 to 1:20. Preferably it is 10:1 to 1:10.

Suitable alkaline inorganic builder salts include alkali metal carbonates, aluminates, phosphates, polyphosphates and silicates.

Specific examples of these salts include the sodium or potassium salts of tripolyphosphoric, aluminic, carbon, phosphoric, and hexametaphosphoric acids.

Suitable organic builder salts include alkali metal, ammonium and substituted ammonium salts of polyphosphonic, polyacetic, and polycarboxylic acids.

Polyphosphonates include, in particular, the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic acid, and the sodium and potassium salts of ethane-1,1,2-triphosphonic acid. There are sodium and potassium salts.

Other examples include ethane-2-carboxyto-1-diphosphonic acid, hydroxymethane diphosphonic acid, carbonyl diphosphonic acid, ethane-1-hydroxy-1,1,2
-triphosphonic acid, ethane-2-hydroxy-1・1・
Each water-soluble salt of 2-triphosphonic acid, probanto 1,3,3-tetraphosphonic acid, propane-1,1,2,3-tetraphosphonic acid [sodium salt, potassium salt, ammonium salt and substituted ammonium salt (hereinafter referred to as sodium salt, potassium salt, ammonium salt and substituted ammonium salt] In the text, substituted ammonium includes mono-, di-, and triethanolammonium cations).

Examples of these polyphosphonic acid compounds are described in British Patent No. 10.
No. 26366, No. 1035913, No. 1129687
No. 1,136,619, and No. 1,140,980.

Polyacetic acid-based builder salts suitable for use in the present invention include the sodium, potassium, lithium, ammonium, and substituted ammonium salts of the following acids: ethylenediaminetetraacetic acid, N(2-hydroxyethyl)-
Ethylenediaminetriacetic acid, N-(2-hydroxyethyl)-nitrilodiacetic acid, diethylenetriaminepentaacetic acid, 1,2-diaminocyclohexanetetraacetic acid and nitrilotriacetic acid.

The trisodium salts of each of the acids listed above are generally preferred.

Polycarboxylic acid-based builder salts suitable for use in the present invention consist of water-soluble salts of polymerized aliphatic polycarboxylic acids, such as those described in US Pat. No. 3,308,067.

The patent specification is hereby incorporated by reference.

Preferred detergent builder salts suitable for use in the compositions of the invention include the water-soluble salts of: (1) aminopolycarboxylate, (2) ether polycarboxylate, (3) citric acid, and ( 4) Aromatic polycarboxylates derived from benzene.

These preferred detergent builder salts preferably contain from about 10 to
It is used in an amount of about 40%.

The water-soluble amino-polycarboxylate compound described above has the following structural formula, and each M is selected from hydrogen and a salt-forming cation.

These materials include water-soluble amino-polycarboxylates such as the sodium and potassium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid and N-(2-hydroxyethyl)nitrilodiacetic acid.

Particularly preferred are water-soluble salts of nitrilotriacetic acid.

The above water-soluble "ether polycarboxylate" has the following general formula.

It is the chosen one.

Specific examples of this type of carboxylates include: water-soluble salts of oxydiacetic acid with the general formula of the formula water-soluble salts of oxydisuccinic acid with the general formula of carboxy A water-soluble salt of methyloxysuccinic acid A water-soluble salt of furantetracarboxylic acid having the following general formula and a water-soluble salt of tetrahycarboxylic acid having the following general formula Dofurantetra The above salt-forming cation M is: Examples are alkali metal cations such as potassium, lithium and sodium, and ammonium and ammonium derivatives.

Water-soluble polycarboxylic acid-based builder salts derived from citric acid are another preferred class of builders for use in the present invention.

Citric acid (this is 2-hydroxy-propane-1.2.
3-)! Citric acid (also known as J carboxylic acid) has the general formula * Although citric acid occurs naturally in the free state, large amounts of citric acid are produced as a by-product of extracting sugar from sugar beets, for example. .

For use in the compositions of the present invention, it is desirable to use acids and partially neutralized ones, so that the neutralizing cations are preferably alkali metal ions such as sodium, potassium, lithium, ammonium cations, etc. and substituted ammonium cations, such as mono-, di-, and trimethanolammonium and mono-, di-, and triethanolammonium cations.

Water-soluble salts of mellitic acid, benzenepentacarboxylic acid, and mixtures thereof are other preferred classes of polycarboxylate builders for use in the compositions of the present invention.

A particular aspect of the invention is a method for simultaneously cleaning and imparting beneficial properties to fabrics.

For that purpose, suitable treatment solutions typically contain one of the following components and amounts: Organic surfactants and particulate materials suitable for use in embodiments of the method include embodiments of the compositions of the invention. It is the same as one that meets the requirements of

The materials are described in detail above.

In a preferred method embodiment, in addition to the requisite organic surfactant and particulate material described above, from about 50 to about 6000 p.
The fabric is treated in an aqueous solution containing detergent builder salts, preferably from about 50 to 4000 ppm.

The aqueous laundry liquors used to carry out the method of the invention are made, for example, by adding to a substantially aqueous medium a laundry formulation corresponding to the detergent composition of the invention.

However, similar results can be obtained by adding the individual components to an aqueous medium.

As an example, a granular detergent composition containing all ingredients except the particulate material (which is added separately) can be added to an aqueous medium.

It is also possible to make detergent compositions containing active ingredients and other conventional ingredients by adding particulate material with bulking agents such as sodium sulfate or with builders such as sodium carbonate.

The essential ingredients included in the detergent formulations of the invention are described in detail in the text above.

Other optional ingredients such as detergent builder salts are also described in detail.

However, in the finished detergent formulation of the present invention, in addition to the above-mentioned components, it is also possible to add a number of other optional detergent composition ingredients that make the product more effective and more attractive.

Thus, for example, organic and inorganic peroxy bleaching compounds can be included in these compositions in amounts of about 5% to about 40%.

Peroxy bleaching compounds can be any conventional inorganic and organic ingredients known to be satisfactory for inclusion in detergent compositions for that purpose.

Examples of inorganic peroxy bleaching compounds include the alkali metal salts of perboric acid, percarbonic acid, persilicic acid, persulfuric acid, and perphosphoric acid.

As is well known, perborates can have different degrees of hydration.

Often the tetrahydrate form is used, but for certain purposes it is possible to incorporate perborates with a lesser degree of water of hydration, such as 1 mole, 2 moles, or 3 moles of water of hydration. is desirable.

Organic peroxy bleaches can likewise be used.

Similar ingredients can also be mixed in as is.

That is, they may be preformed or they may be made at the point of use, for example by addition of any peroxy bleach suitable for use with an organic peroxy bleach activator.

Particular examples of organic peroxy bleaching compounds are water-soluble salts of chimono and di-peroxy acids such as perazelaic acid, monoperoxyphthalic acid, diperoxyterephthalic acid, and 4-chlorodiperoxyphthalic acid.

Preferred aromatic peracids include the water-soluble salts of diperisophthalic acid, m-chloroperbenzoic acid, and p-nitrobenzoic acid.

If the peroxy bleach compound should be made on-site,
The precursors, ie, peroxy bleach and peroxygen activator, should be added separately to the detergent composition.

As mentioned above, peroxygen bleaches can be represented by all oxygen bleaches commonly used in detergent technology, ie organic and inorganic.

The activators are represented by all oxygen activators known to be suitable for use in detergent technology.

Specific examples of preferred activators include acylated glycol lauryls.
les), tetraacetylmethylenediamine, tetraacetylethylenediamine, triacetylin cyanurate and benzoylimidazole.

An acid anhydride activator having at least one double bond between α and α1 carbon atoms relative to the carbonyl group of the acid anhydride group can also be used similarly.

Examples are phthalic anhydride and maleic anhydride.

If the peracid is made on-site, the molar ratio of peroxygen bleach to bleach activator is preferably about 5:1 to 1:2, especially 2
=1 to 1:1.2.

Other components of the detergent compositions used in the present invention include foam control agents such as foam enhancers and foam suppressants, discoloration inhibitors, soil suspending agents, buffering agents, additional enzymes, and brightening agents. , fluorescent brighteners, fragrances, dyes and mixtures.

Foam enhancers can be represented, for example, by jetanolamide.

Silicones, hydrogenated fatty acids, and hydrophobic alkylene oxide condensates can be used in similar compositions to suppress foaming, or more generally to control foaming.

Benzotriazole and ethylenethiourea can be used as discoloration inhibitors.

Carboxymethylcellulose is a well known soil suspending agent.

In addition to the initial proteolytic components, various enzymes such as amylase can be added as well.

The additional ingredients described above, when used in the compositions of the present invention, are employed at conventional concentrations.

As mentioned above, there is no criticality regarding the combination of the above-mentioned components in the preparation of the detergent composition of the present invention, other than that the particulate components ultimately take the form of discrete particles in the washing liquid.

As mentioned above, if the composition is in granular or flake form, the particulate material is simply mixed in dry form or sprayed from an unheated aqueous dispersion.

In the case of liquid detergent compositions, the particulate ingredients are likewise simply added in the appropriate proportions.

In order to evaluate the detergent compositions of the present invention, it was necessary to perform certain tests on fabrics treated according to the present invention.

These test methods are described below.

Antistatic Test Bundles of blended fabric (approximately 53% pure cotton: 1.2% 65/35 polyester/cotton blend; 17% nylon; 18% Dacron) containing the test laundry composition (as described below) Wash for 10 minutes in a small agitator washing machine containing 7.571 (2 cans) of aqueous laundry liquid.

The washing temperature is 38°C (100”F) and the water hardness is 3.
．． It has an artificial hardness of 454 rIll (7 grains) per 7851 (1 gallon).

The bundle contains 5% by weight of washing liquid.

The bundle was centrifugally dehydrated and 3.7851 (1 gallon)
38°C (100'F) with a hardness of 54m9 (7 grains)
Water 7.571: Rinse for 2 minutes.

The fabric is then dried in a commercial dryer. The electrostatic charge on each fabric is then measured by standard standing techniques in a Faraday cage.

Then, the total area of the entire surface of the fabric (two sides of the fabric) (
Calculate the sum of the absolute value of static charge on all the fabrics in the bundle divided by 0.83677+'' (1 square yard).

This is the so-called "static value".
e ) ” (Vlo, 836yy? (1 square yard)
], which correlates with the macroscopic observation of the effects of electrostatic charges on the textile surface, i.e., positive shock, sparks, and clinging of the textile.

According to tests on the above fabric bundles, approximately 1.5V1
Fabrics with a static electricity value smaller than 0.836 Tn' (1 square yard) do not cling due to static electricity, and have a static electricity value of 4.5
Fabrics with static values greater than V/0.836 yrt (1 square yard) exhibit significant static cling.

Wrinkle Resistance Test Bundles of blended fabric (approximately 53% pure cotton; 12% 65/35 polyester/cotton blend; 17% nylon; 18% Dacron) containing the test laundry composition (as described below) Wash for 10 minutes in a small agitator washing machine containing 7.571 (2 guns) aqueous laundry solution.

Washing temperature is 38°C (100'F) and water hardness is 3
．． It has an artificial hardness of 454 ■ (7 grains) per 7851 (■ gallon).

The bundle was centrifugally dehydrated and 3.7851 (1 gallon)
Rinse for 2 minutes in water 7.5713 at 38° C. (below 100) with a hardness of 54 ■ (7 grains).

The fabric is then dried in a commercial dryer.

The degree of wrinkling in a particular piece of fabric is then measured by placing the fabric on a flat, movable surface inside a light-tight box.

A faint beam of light from a light source above the fabric is applied to the fabric at a 90° angle.

As the mounted fabric is moved through a predetermined path, a small photovoltaic cell fixed adjacent to a stationary light source responds to the scattered light at a 45° angle to the fabric surface.

Plotting the light intensity measured by the photocell against the length of the path across the fabric results in a profile (curve) that is a replica of the surface of the test fabric at every measured point.

That is, a smooth, unwrinkled fabric will result in an essentially constant straight line of light intensity, whereas a wrinkled fabric will produce a series of peaks and minima.

The ratio of the absolute distance traveled by the fabric to the length of the plotted curve is quantitatively related to the degree of wrinkling.

Ease of Ironing Test Bundles of blended fabrics (approximately 53% pure cotton; 12% 65/35 polyester/cotton blend; 17% nylon; 18% Dacron) were treated with test laundry compositions (described below). Aqueous laundry liquid containing 7.571! Wash for 10 minutes in a small agitator washing machine containing (2 guns).

Washing temperature is 38°C (100'F) and water hardness is 3
．． 454 m9 (7 grains) per 7851 (1 gallon)
It is an artificial hardness.

The bundle contains 5% by weight of washing liquid.

The bundle was centrifugally dehydrated and 3.7851 (1 gallon)
38℃ (below 100) with a hardness of 541ng (7 grains)
Rinse for 2 minutes in 7.5773ml of water.

The fabric is then dried in a commercial dryer. The ease of ironing of each fabric is then determined using an iron with ironing equipment but otherwise conventional.

In short, the iron uses an internal detector to
Measures the amount of effort required by a layperson to give the surface of the test fabric a subjectively smooth appearance.

The total amount of work required to achieve this look is a function of the force applied to the iron (measured) and the distance the iron traverses the plane of the fabric (measured).

These tests are also performed by a layman on untreated controls.

Flexibility (related to bulk), ease of creasing,
Other tests such as fabric drapeability, fragrance and general condition of cleanliness were subjectively evaluated by a panel of experts on unlabeled controls.

The laundry detergent composition and laundry method of the present invention will be illustrated by the following examples.

Base Composition The above base composition is made by mixing all ingredients except the particulate material in a clarifier and spray drying to form the particulate material.

These granules are then homogeneously mixed with the granular material.

The composition is then used at a product concentration of 0.12% to launder the soiled fabric in a standard manner.

The fabric is cleaned and dried and its performance is then evaluated by testing the fabric for wrinkle resistance and ease of ironing as described above.

The test fabric showed reduced wrinkles and stiffness compared to the control fabric.
Shows easier ironing, increased flexibility, reduced static charge and improved appearance.

When the particulate materials described below are incorporated into the base composition described above at the specified concentrations described above, the benefits described in the previous section are obtained.

The anionic surfactant of the base composition described above is added to an equivalent amount of 2-
Acetoxytridecane-1-sulfonic acid, methyl-α-
Also when replacing sodium sulfopalmitate, sodium β-methoxyoctadecyl sulfonate, sodium coconut alkyl ethylene glycoether sulfonate, and sodium sulfate of the reaction product of 1 mole tallow fatty alcohol and 3 moles ethylene oxide, respectively. Substantially the same fabric benefits are obtained.

The anionic surfactant of the base composition is about 9.5 equivalents per mole of nonylphenol and nonylphenol.
Condensation products of coconut fatty alcohol with about 6 moles of ethylene oxide per mole of coconut fatty alcohol, Condensation products of beef tallow fatty alcohol with about 11 moles of ethylene oxide per mole of tallow fatty alcohol The product, a condensation product of a secondary fatty alcohol containing about 15 carbon atoms, with about 9 moles of ethylene oxide per mole of said fatty alcohol, 3-(N-
N-dimethyl-N-alkylammonio)propane-1
-sulfonate, or 3-(N-N-dimethyl-N-
alkylammonio)2-hydroxy-furopane-1-
sulfonate (in both compounds the average chain length of the alkyl group is 14.8 carbon atoms), 3-(N-N
Dimethyl-N-hexadecyl ammonio)propane-1
-sulfonate, 3-(N-N-dimethyl-N-hexadecyl ammonio)-2-hydroxypropane-1-sulfone-), 3-(N-dodecylbenzyl-N-N-dimethylammonio)-propane- 1-sulfonate, 3
-(N-doa'silbenzyl-N-N-dimethylammonio)acetate, 3-(N-dodecylbenzyl-N-
N-dimethylammonio)propionate, 6-(N-dodecylbenzyl-N-N-dimethylammonio)hexanoate, 2-(N-N-dimethylN-hexadecylammonio)acetate, and 3-(Mdecylamino)-
Substantially equal flexibility, wrinkle resistance, ease of ironing, antistatic properties, and appearance benefits are obtained when each is replaced with sodium propane-1-sulfonate.

Substantially the same results are obtained when using particulate materials and mixtures thereof at the following concentrations: 0.2.0.4.0.6
．． 0.9, ■, 2.1.4.2.2.6.3, 5.4.
2.6.017.5, and 9.0%.

Example ■ Make a laundry detergent product with the following composition: (1) A soap mixture consisting of 90% beef tallow soap and 10% coconut slaked soap.

(2) Sodium salt of ethoxylated tallow alkyl sulfate having an average of about 3 ethylene oxide units per molecule.

(3) Sodium salt of a linear alkylbenzenesulfonic acid having an average alkyl chain length of about 12 carbon atoms.

DRY-PLO" starch is mixed in a clarifier and spray dried to form a granular soap base composition.

This soap base composition has an average particle size of 10 microns.
Add 1.0% by weight of DRYFLO” starch.

The above composition is added to an aqueous wash liquor at 38°C (100″F) at a concentration of about 0.12% by weight.

The composition dissolves quickly and the "DRY-P LO" starch particles are uniformly and independently dispersed throughout the wash liquor.

Fabrics washed with said liquid are cleaned and at the same time have the same properties as above, except that they do not contain starch components, with respect to wrinkle resistance, ease of ironing, flexibility, antistatic properties and appearance as determined by the above-mentioned tests, among others. benefits compared to a control fabric washed exactly the same way.

Substantially the same results are obtained when the "DRY-PLO" starch is replaced by an equivalent amount of particulate material selected from Nigaras small hollow spheres (Ecosphere), poly(tetrafluoroethylene) (Molykoat 522) ), poly(urea formaldehyde), poly(methyl methacrylate) (syndiotactic form), glass beads PF-
128, glass beads PF-12T, poly(melamine formaldehyde-urea formaldehyde), glass beads (Unisphere), glass beads PF-12
R, PO+) (styrene divinylbenzene), glass beads PF-11° These particulate materials have the average particle size and melting point described in Examples 1 to 2.

Example■ A laundry cycle type for fabrics (thro) with the following composition.
ugh-the-wash-cycle) ]
Making the conditioning additive: This additive is used in the treatment of fabrics with detergent base granules having the following composition.

The conditioning additive described above is combined with the detergent base granules described above prior to dissolving the mixture in the wash liquor;
Or add it separately to the washing liquid.

In both cases, the product concentration based on the sum of both is 0.
12% by weight, thus conditioning additives are 0.05% by weight and detergent base granules are 0.07% by weight.

Fabrics treated with the laundry fluids of the present invention exhibit superior fabric properties compared to those obtained by similar processes containing comparable concentrations of detergent compositions known in the art.

Claims (1)

[Scope of Claims] 1. A detergent composition having fabric conditioning properties comprising: (a) a detergent composition selected from the group consisting of anionic detergents, non-ionic detergents, zwitterionic detergents and amphoteric detergents, and mixtures thereof; from about 2% to about 99.5% by weight of an organic surfactant; and (b) a substance selected from the group consisting of surface-modified starch, glass beads, glass small hollow spheres, and mixtures thereof, having the following characteristics: Particulate material that is insoluble in water
．． 05 to about 10% by weight: (1) Average particle size in the range of about 1 to about 50μ: (11) Shape with anisotropy of about 5:1 to 1:1; (*n) about 5 on the Mohs hardness scale (IV) a melting point greater than about 150°C; and (V) substantially free of exchangeable calcium and magnesium ions.