JPS62121799A - Cloth softening antistatic detergent composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to detergent compositions based on clay softeners and cationic antistatic properties. More specifically, the present invention relates to a method for producing a washing detergent powder composition 1 composition containing a detergent surfactant, a clay softener, and a water-soluble diammonium salt antistatic agent, and its use in washing textile materials. .

Powdered detergent compositions containing detergent surfactants (anionic, nonionic, etc.) along with clay softeners and cationic antistatic agents such as quaternary ammonium compounds, quaternary diammonium compounds, etc. It is well known. What are the typical patent documents in this field?

U.S. Patent No. 3.862.058 (2 A/7 Yules (N
irschl) etc.]; No. 3.886.075 [Bennrdino); No. 3.9
No. 15,882 [Nirschl et al.]; No. 15,882 [Nirschl et al.]; 1.948.7
No. 90 [Speaman et al.]; No. 4
, No. 203.851 [Ramachandra y (Ramac
handran ) ] ; UK Patent Application No. 2.141
, 152Al Ramachiendraran).

Other patent examples relating to clay fabric treatment compositions include U.S. Pat.
h ) ] and! No. 4,062.647, [St-A (
5tonn) etc.] is allo.

The use of bentonite for softening textiles is known from British Patent Nos. 401.41!1 and 461,221.

Although known clay softener-detergent compositions provide satisfactory cleaning and softening performance, they do not sufficiently reduce the electrostatic load with washed fabrics to a level acceptable to the average consumer. Generally difficult.

Generally, attempts to incorporate antistatic agents in amounts that provide acceptable levels of antistatic performance result in an overall reduction in cleaning, whitening, and softening performance. This decrease in overall performance parameters may occur when the cationic antistatic agent is removed under conditions that cause surface changes in the clay softener or due to physical changes in the clay component, cationic antistatic agent component, detergent component, and other components of the composition. Either addition to the composition under conditions such that mixing simply occurs has been observed.

Accordingly, it is an unexplored object to provide clay softener compositions that include compounds that reduce electrostatic loading.

Another object of the present invention is a detergent composition containing a water-soluble diammonium compound antistatic agent and having antistatic performance as a spray-dried bead that is compatible with a clay mineral fabric softener and a method for making the spray-dried bead. The goal is to provide the following.

Another object of the present invention is to provide a pilgoo-added clay softener detergent powder composition that has antistatic properties that are acceptable to consumers without adversely affecting the cleaning, whitening or softening performance of the detergent composition. That's true.

Yet another object of the invention is to uniformly and homogeneously distribute the antistatic agent into the composition by adding the water soluble diammonium salt cationic antistatic agent to the composition as a component of the clarification mixture to be spray dried. It is an object of the present invention to provide a clay softener-detergent powder composition in which the clay softener is incorporated and the clay softener is subsequently added to the spray-dried beads or granules.

These and other objects of the present invention will be readily understood from the following detailed description and preferred embodiments, and include spray-dried beads to be incorporated into clay softener detergent compositions as antistatic cationic compounds, particularly with clay softeners. Or as one component of granules, the linear formula +11 [wherein Ro is about 12 to about 50 carbon atoms]
is an aliphatic hydrocarbon; each of RRR, R and R6 has 1 to 213 carbon atoms.
45 22 aliphatic hydrocarbon groups (however, the total number of carbon atoms in the aliphatic hydrocarbon group including R1 is about 75 or less, and R2-
and the following formula: CH3 (CHOH0) (CHCH20), H2m (in the formula, m and n are 0 or a positive number regardless of each other,
The sum of m+n from all R2-R6 groups is at least 2
independently selected from the group consisting of alkanol groups having 60 or less from (with the proviso that R2-
At least one of the R6 groups is the above alkanol group)
, R7 is C2-C5 lower alkylene or substituted 02-
Achieved by using a water-soluble diammonium salt, such as C5 lower fullkylene, where K is a number from 1 to 20, and X is a water-soluble salt-forming anion. be done.

Useful diammonium compounds of formula +11 are water soluble and stable over a wide range of pH values and elevated temperatures, so they can be added directly to the clarification mixture as an aqueous solution along with other softener-detergent composition components and spray dried. By doing so, the diammonium salt antistatic agent can be evenly and homogeneously incorporated into the spray-dried granules or beads. This uniform'J! As a result of JK dispensing, favorable levels of antistatic performance can be obtained using lower levels of antistatic compounds without adversely impacting other detergent properties, including cleaning performance, whitening performance and softening performance. Never.

As long as it is used in the specification and claims.

The term "water soluble" means that the antistatic diammonium compound is soluble in at least 5% by weight of water at 20° C. or less (both forming a stable dispersion). is soluble in water to an extent of at least 10% by weight.Formula 111
Because the diammonium salt antistatic agents are available or can be prepared as organic solvent-free water bath liquids or as dispersions, they can be easily and safely handled in powder processing plants and are It can be easily clutched and spray dried as a component of duty detergency enhancing granules or powdered flushing detergent compositions.

A typical heavy duty detergency enhancing composition comprising spray dried beads containing a water soluble antistatic agent of Formula +11 can include the following ingredients.

A preferred method of manufacturing heavy duty detergency enhancing granules or powder softener-detergent compositions involves mixing the antistatic agent of formula (1) and other pH-insensitive, heat-stable ingredients in a clarifier and spraying. dries to form spray-dried beads;
These beads are pH sensitive and/or heat sensitive. Alternatively, the components of the composition that react with the cationic antistatic agent, anionic surfactant or other components of the spray indigo-dried peas or granules are homogeneously mixed or sprayed over. Examples of components that can be added later and mixed with the spray-dried beads include, for example, bleach, clay softeners, enzymes, fragrances, nonionic surfactants, and the like. , llll formulation methods are well known in the art, and a person skilled in the art can easily determine optimal formulation conditions.

The detergent composition can include one or more surfactants selected from the group consisting of anionic detergents, nonionic detergents, amphoteric detergents, and zwitterionic detergents. Synthetic organic detergents that can be used in the practice of the present invention include 7 Yuba A, tsu (
Surfactants and Detergents (5u
rface ACtiVe Agents arxID
eter-gents) J (Inter-science Publishing
ers), published in 1958, volume 311. The relevant disclosure of this document is hereby incorporated by reference. The surfactant detergent compound(s) is in the range of about 95% by weight of the total detergent composition, more preferably in the range of about 1-70% by weight, WK 5-50% by weight of the total detergent composition. be.

Preferably, the detergent compositions of the present invention employ one or more anionic detergent compounds as the primary surfactant. It is preferred to supplement the anionic detergent, if desired, with other types of surfactants, preferably non-ionic detergents, especially when used in combination with detergent builder salts.

Anionic surfactants useful in the present invention include carbon atoms ranging from 8 to 26 carbon atoms per molecule. Preferred are surface-active compounds containing an organic hydrophobic group having 10 to 18 carbon atoms and at least one water-solubilizing group selected from the group consisting of sulfonates, sulfates, carboxylates, phosphonates and phosphates.

Examples of suitable anionic detergents include water-soluble salts of higher fatty acids containing 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms (
Examples include soaps such as sodium salts, potassium salts, ammonium salts, and alkanol ammonium salts) or salts. Suitable fatty acids are obtained from oils and waxes of animal or vegetable origin, such as tallow, grease, coconut oil and mixtures thereof. Particularly useful are fatty acid mixtures derived from coconut oil and tallow, such as sodium palm soap and potassium palm soap.

The anionic class of detergents also includes water-soluble sulfated and sulfonated detergents having aliphatic radicals (preferably alkyl) of 8 to 26 degrees and preferably about 12 to 22 carbon atoms. (The term "L alkyl" includes the alkyl portion of the K-class acrylic radical.) Examples of sulfonated anionic detergents include those in which the straight or branched higher alkyl group has 10 to 10 carbon atoms.
Higher alkyl mononuclear aromatic compounds such as higher alkyl benzene sulfonate which is 16? 1: Group sulfonates, such as sodium, potassium, and ammonium salts of higher alkylbenzenesulfonates, higher alkyltoluenesulfonates, and higher alkylphenolsulfonates.

Other suitable anionic detergents include olefin sulfonates, including long axis alkenesulfonates, 1t-n hydroquine alkanesulfonates, or mixtures of alkenesulfonates and hydroquine alkanesulfonates. Olefin sulfonate detergent.

For example, 2RCH=CHR' (in the formula, R is 6 to 6 carbon atoms)
8 to 25 carbon atoms, such as olefins having 25 higher alkyl groups (R' represents an alkyl group of 1 to 17 carbon atoms or hydrogen). Preferably 12 to 2 carbon atoms
Long 1j olefin containing 1 and sulfur trinitride (SO2)
It can be prepared in a conventional manner by forming a mixture of the sultone and the alkenesulfonic acid by reaction with the sulfonate and then treating the mixture to convert the sultone to the sulfonate. Other examples of sulfate or sulfonate detergents are paraffin sulfonates having 10 to 20 carbon atoms or preferably about 15 to 20 carbon atoms.

-Paraffin sulfonates+ are prepared by reaction of long chain α-olefins with bisulfite.

Sulparaffin sulfone-111 with sulfonate groups distributed in the paraffin chain, U.S. Pat. No. 2.506.
280, No. 2, 5 (No. 17,088, No. 3.260,
No. 741, No. 3,672.188 and German Patent No. 7
No. 55.1196.

Other suitable anionic detergents have the formula: % formula % [wherein R represents a fatty alkyl group having 10 to 18 carbon atoms and 1 m has a value of about 2 to 6 (approximately μ to a bar of the number of carbon atoms in the R group) (preferably) and 1M is a salt-forming cation such as an alkali metal, ammonium, lower alkyl-amino or di-alkanolamino. It is a higher alkylbenzene sulfonate having 15 higher alkyl groups. The proportion of ethylene oxide in the polyethoxylated higher alkanol sulfate is 2 to 5 ethylene oxide groups per mole of anionic detergent.
The amount is preferably mol, and particularly when the higher alkanol has 11 to 15 carbon atoms, it is most preferably 3 mol of ethylene oxide group. To maintain the desired hydrophilic-lipophilic balance, the ethylene oxide content of the detergent is approximately 2 moles per mole of detergent when the carbon atom content of the alkyl chain is in the lower range of 10 to 18 carbon atoms. If the higher alkanol has 16 to 18 carbon atoms in the higher end of the carbon number range, the number of ethylene oxide groups can be 4 or 5. In this case, it can be increased to about 8 to 9. Similarly, salt-forming cations can be adjusted for best solubility. M is a suitable solubilizing metal or radical, but most often may be alkali gold F4 (e.g. S11um) or ammonium. When lower alkylamino or alkanol groups are used, the alkyl groups and alkanols usually contain from 1 to 4 carbon atoms, and the amines and alkanolamines include, as in monoethanolamine, diisopropanolamine and trimethyleneamine, They are 111-substituted, 2-substituted and 6-substituted. Preferred polyethoxymolated alcohol sulfate detergents 5hell Chemical Company
Color available and Neodol®
It is sold as 25-58.

The most preferred water-soluble anionic detergent compounds are ammonium salts, substituted ammonium salts (e.g. mono-; salts) and alkaline earth metal salts (e.g. calcium and magnesium salts). Among the anionic detergents, the most preferred example is linear sodium alkylbenzene sulfonate (LABS), especially in which the alkyl group is
l 2 or 15 straight chain alkyl radicals.

Anionic surfactants can generally constitute the major detergent ingredient and preferably account for 60-100% of the total surfactant ingredients. Anionic detergents account for at least 50% of the total surfactant detergent ingredients, preferably at least 60%
, particularly preferably a small amount (from 70% to about 99%,
Preferably it accounts for up to 90%, particularly preferably about 80%.

The anionic surfactant component is generally preferably included as a component of the antistatic agent-containing spray-dried beads and is added to the clarification mixture as an aqueous solution or dispersion, particularly preferably as a highly concentrated aqueous slurry.

Nonionic Surfactants The next most preferred class of surfactant detergents are nonionic synthetic organic detergent compounds.

Nonionic synthetic organic detergents are characterized by the presence of organic hydrophobic groups and organic hydrophilic groups and are typically produced by the condensation of organic aliphatic or alkyl aromatic hydrophobic compounds with ethylene oxide (hydrophilic). Hydrophobic compounds with carboxyne, hydroxy, amide or amino groups with free hydrogen attached to the nitrogen atom can indeed be condensed with ethylene oxide or its polyhydrate products (polyethylene glycols) to form nonionic detergents. . The length of the hydrophilic or polyoxyethylene chains can be easily adjusted to obtain the desired balance between hydrophilic and hydrophobic groups.

The nonionic detergent used has an alkanol with a carbon number of 8 to 22,
It is preferably a polylower alkoxylated higher alkanol in which the number of moles of the lower alkylene/oxide (having 2 or 6 carbon atoms) is 3 to 20. Among these substances, higher alkanols are higher fatty alcohols having 11 to 15 carbon atoms, and each mole contains 7 lower alkyl alcohols.
It is preferable to use a substance containing 5 to 15 groups.

Preferably, the lower alkoxy 7 groups are ethoxy,
In this case, it is preferable to mix broboki 7.

When present, broboki 7 is usually a minor component (less than 50%). Typical examples of such compounds are those in which the alkanol has 12 to 15 carbon atoms and contains 7 ethylene oxide groups per mole. 7 and Neodol 25-6.5. The former is a condensation product of a higher fatty alcohol mixture having an average of 12 to 15 carbon atoms and about 7 moles of ethylene oxide.

In the latter case, the higher fatty alcohol has 12 to 16 carbon atoms, and the average number of ethylene oxide groups per mole is 6.5.
It is. The corresponding mixture. Higher alcohol @1
This is Ding Silkar. Other examples of such detergents are Ter
product tol (registered trademark) 15-2-7 and Tergit
ol 15-S-9. Both of these companies are owned by Union Carbide Co.
It is a linear sulfuric acid heptalate produced by the company Rporation. The former is a mixed ethoxylation product of a linear secondary alkanol having 11 to 15 carbon atoms and 7 moles of ethylene oxide, and the latter is a similar product but reacted with 9 moles of ethylene oxide.

Highly preferred nonionic detergents for use in the present invention are likewise ethylene oxide condensation products of higher fatty alcohols, where the higher fatty alcohol has 14 to 15 carbon atoms and the number of ethylene oxide groups per mole is about 11. A high molecular weight non-ionic detergent, such as Neodol 45-11. Such products are also manufactured by Shell Chemical Company.

Of the total surfactant detergent ingredients in the detergent composition, the non-f-on surfactants may comprise up to about 70% by weight, preferably about 50% by weight.
It may be present in an amount of up to 61%, more preferably up to about 40%, particularly preferably up to about 15% by weight. usually,
If a nonionic surfactant is used, it is present in an amount of at least 1%, preferably at least 10%, particularly preferably up to at least 60% of the total weight of the entire surfactant detergent component. In the unsoftened detergent composition as a whole, the nonionic surfactant compounds are present in an amount of about 0.1 to 20% by weight, preferably 0.6 to 15% by weight, particularly preferably 0.6 to 1% by weight.
It is usually present in an amount within the range of 0% by weight.

Since nonionic surfactants are often weakly soluble in water or form viscous solutions or gels when added to water, they are usually used as solutions in organic solvents, for example alone or in ethanolic solutions with water or isopropylene. It is commonly obtained as Patur solution. Therefore, if a nonionic surfactant compound is obtained as a solution in its organic solvent, it cannot be incorporated into ready-made spray-dried beads rather than as part of the clarification mixture used to form spray-dried beads or granules. Add it later. Additionally, nonionic surfactant compounds can be used either in their pure liquid form (most nonionic surfactants are liquid at ambient temperature) or as an aqueous solution. It may be desirable to add the compound to the spray-dried beads later.

Betaines and sulfobetaines having the following formulas are also useful: where R8 is an alkyl group of 8 to 18 carbon atoms, and R9 and RIG independently represent an alkyl or hydroxyalkyl group of about 1 to 40 carbon atoms. , R11 has 1 or more carbon atoms
represents an alkylene or hydroxyalkylev group of 4,
Y represents a carbon atom or a s20 group; an alkyl group has one or more intermediate bonds, such as an amide, ether, or polyether bond, or a hydroxyl or halogen group that does not substantially affect the hydrophobicity of the group; can include non-functional substituents such as. When representing a Y-added carbon atom,
The detergent is called betaine. When Y represents an S:O group, it is called detergent-1 sulfobetaine.

Amphoteric detergents are also suitable for the present invention. Amphoteric detergents are well known in the art, and a number of practical detergents of this class are disclosed in Surfactants and Detergents, supra. Examples of suitable amphoteric detergents include alkyl beta-iminodipropionates, RN<G2H
, GOOM >2; - rlkyl beta mininopropionate, RN(H)C□H,C00M, and long chain imidazole derivatives having the general formula: It is an acyclic hydrophobic group of 8 to 18, and M is a cation that neutralizes the charge of the anion. Particular practical amphoteric detergents include undeflucycloimidinium-ethoxyethionate-2-nithionic acid, dodecyl beta-alanine, and 2-trimethylaminolafric acid inner salt.

The amounts of zwitterionic synthetic organic detergents and amphoteric synthetic organic detergents, if present in the compositions of the present invention, are not critical and can be selected depending on the desired result. Generally, 10,000 or both of these classes of detergent ingredients can be used in place of all or a portion of the anionic organic detergent surfactants and/or nonionic organic detergent surfactants within the J. .

As with anionic and nonionic surfactant compounds, one skilled in the art will know whether zwitterionic and amphoteric surfactants should be included as a component of the clarification mixture to form spray-dried beads or granules, and whether the shear The spray-dried beads should then be added to the final heavy-duty detergent composition to form a detergent composition that can be easily resolved. Briefly, when obtained as an aqueous solution, it is preferably added to the clarification mixture, and when obtained in an organic solvent, it is added subsequently to the spray-dried beads.

The clay softener can be selected from clay softeners known in the art to impart flexibility to washable fabrics. A preferred clay is a green clay material.

The green clay type clay used in the present invention is characterized by a layered structure that can swell or swell in the presence of water, increasing its volume by a factor of 0 and forming a peachy gelatinous material. There are two classes of green clays: in the first class, aluminum oxide is present in a 7-silicate crystal lattice, #.

In the 2 class, magnesium oxide is present in a hepta-silicate crystal lattice. Iron in the crystal lattice of green clay.

Atomic substitution by magnesium, sodium, potassium, calcium, etc. occurs. It is customary to distinguish between clays based on the main cation. For example, a sodium clay is a clay in which the cations are primarily sodium.

All green clays used in the compositions of the present invention are commercially available.

Such clays include, for example, montmorillonite, poA
t Con
).

nontronite, hectorite, savonite,
There are 5auconite and vermiculite. Such clays are manufactured by, for example, Georgia Kaolin Go,
) (2:x--Jah 7-state, Elizabeth) T
hixogeL,? 1&1 (rThixo-Je
lJ also) and Gelwhite GP; -r
yt Rika 7 a:r.

American Co11oid Co.
) (i+) / i state, su-1'-) kara c7)
Volclay BC and VOIC1ayil'E, 5
It is available under various trademarks such as 25. It should be recognized that such green clay type minerals obtained under the trade name @ are composed of a mixture of various individual minerals. Such mixtures of green clay materials are suitable for non-inventive uses.

In the compositions of the present invention, clay softeners which are also preferred are sodium or base softeners, such as bentonite clays.
It is aluminum silicate, which is an s ion. Among bentonite clays, Wyoming clay (commonly referred to as Western bentonite or Wyoming bentonite) is particularly preferred.

A preferred swellable bentonite is manufactured by Benton Clay Co., an affiliate of the Georgia Kaolin Company.
It is sold under the trade name CMineral Co11o1d by C1ay Company) as industrial hentonite.

It is the same as that previously sold under the trademark Th1xo-Jel. These substances are bentonites whose quality has been improved through beneficiation, and the most advantageous bentonite is Th1xo-Jel & 1.2.37i.
[MlnenLI C01lO1d corresponding to 4 &
It is available as HJ No. 101 etc. Such ridges have a pH value in the range 8-94 (6% concentration in water), a maximum free water content of about 8% and a specific gravity of 2.6, with respect to the powder grade, a low (both about 85 % (preferably 100%) is 2
Pass through a 00 mesh US Coupe 7 Lees sheep (74 micron diameter aperture). More specifically, the bentonite is such that essentially all (at least 90%, preferably 95%) of the particles pass through a 1i325'/-b (US Sheep Series) (44 micron diameter aperture).
Particularly preferred are clays in which all the particles pass through a very large gap. The swelling property of bentonite in water is usually in the range of 5-15 ml/l, and ↑9 degrees at 6% concentration in water is usually 8-50 centibore.
Instead of using lcid hair) night, general purpose bentonite powder 525 from American Colloids, Inc.'s Industrial Division is used.
Products such as those sold as meshes may also be used. This means that at least 95% of it is finer than 525 mesh or 4.4 microns in diameter (wet particle size) and at least 96% of it is finer than 200 mesh or 7 microns in diameter.
Finer than 4 microns (dry particle size). Such hydrated aluminum silicates consist primarily of montmorillonite (at least 90%) with small amounts of fluorite, biotite, and selenite. Typical analytical values on an "anhydrous" basis are: 63.05% clica, 21.5% alumina, 3.5% ferrous ion (as Fe203), ferrous (,t
y (as FeO) 0.4%, magnesium (as MgO and °C) 2.7%, sodium and potassium (as Na2O and C) 2.6%, force k'/') A (as CaO) 0.7%, Water of crystallization (as H2O) 5.6% and trace elements 0.7%.

Western bentonite is preferred, but exchangeable monovalent metals (
It is also possible to use other bentonites, such as those produced in Italy, which have a relatively small proportion of sodium and potassium, and which have been treated with an alkaline substance such as sodium carbonate to increase their cation exchange capacity. In order for the clay to be sufficiently swellable and exhibit good softening and dispersibility in aqueous suspensions, the Na2O content of the bentonite should be at least about 0.5%, preferably at least 1%, more preferably at least It is thought to be 2%. Preferred swellable bentonites of type 1 are Laviosa and W.
sold under the trade name Winkelmann (for example, Laviosa A G B and Winkelmann
G-15>.

Other clay minerals can of course also be used in the present invention, such that they are always capable of imparting textile material K "softness".

Preferred clays for use in the present invention are "fine," ie, have a viscosity that is imperceptible to the senses of touch.

Fine clay has a particle size of less than about 50 microns; the clay used in the present invention has a particle size range of about 5 microns to about 50 microns.

The clay softener compound is present in the detergent composition from about 1 to about 50% by weight, preferably from about 2 to 60% by weight, based on the total composition;
Particularly preferably present at a level of 4-20% by weight.

In the present invention, clay softeners are added later to the antistatic agent-containing spray-dried beads or granules to avoid interactions (e.g., ion exchange) between the clay mineral particles and the cationic diammonium compound antistatic agents. is highly preferred. Thus, as a result of the tartutting and spray drying operation, the diammonium compound is homogeneously and very finely distributed in the spray-dried beads, and the subsequently added components contact the spray-dried beads under substantially anhydrous conditions. Therefore, no ion exchange actually occurs between the clay softener and the cationic diammonium salt antistatic agent.

The clay softener can provide the desired softening effect when used in the detergent compositions of the present invention in amounts customary for cleaning detergent compositions, e.g., in an amount of about 1 to 1 cup per wash load. exist in such amounts.

Detergent Builder - The detergent compositions of the present invention optionally, but preferably contain at least one detergent builder of the type commonly used in detergent compositions. Useful builders include common inorganic water-soluble builder salts such as phosphates, pyrophosphates,
Water-soluble salts include orthophosphates, polyphosphates, tripolyphosphates, silicates, carbonates, bicarbonates, phorates, and sulfates. Organic virgoos include water-soluble organic phosphonates, polyphosphonates, polyhydroxysulfonates, polyacetates, and aminopolyacetates.

These include carboxylates, polycarboxylates, succinates, phytates, etc.

Particular examples of inorganic phosphates are potassium and sodium tripolyphosphates, pyrophosphates and hexametaphosphates. Organic polyphosphonates are, in particular, for example the sodium and potassium salts of ethane-1-hydroxy-1°1-diphosphonic acid and the sodium and potassium salts of ethane-1,1,2-)liphosphonic acid. Examples of these and other phosphorus builder compounds are listed in U.S. Patent No. 3.213.
．． No. 050, No. 2.422,021, No. 3,422,
No. 157 and No. 5.400.167.

Pentasodium tripolyline and tetrasodium birophosphate are the preferred water-soluble inorganic builders.

Special examples of non-phosphorous inorganic virions are water-soluble inorganic carbonates, bicarbonates, and silicates. Carbonates of alkali metals (e.g. sodium and potassium).

Particularly preferred for the present invention are bicarbonates and silicates.

Water-based organic builders are also useful. For example, Arca +1
Metal, ammonium, and substituted ammonium acetates, carboxylates, polycarboxylates, polyhydroxysulfonates are useful builders in the compositions and methods of this invention. Specific examples of acetate and polycarboxylic acid salts include ethylenediaminetetraacetic acid, nitrilotriacetic acid, benzene polycarboxylic acid (i.e., pentacarboxylic acid, tetracarboxylic acid), carboxylmethoxysuccinate and sodium, potassium citric acid. , lithium, ammonium and substituted ammonium salts.

Other organic builder salts used in the present invention include MeIJ
) including water-soluble alkali metal salts of acids, U.S. Pat.
There are polycarboxylate materials described in No. 264.105. Water-soluble salts of polycarboxylene polymers and copolymers, such as those described in U.S. Pat. No. 3,3 El 8,067, are also suitable for the present invention. ing.

It is popular to use water-soluble builders, especially silicic acid complexes, and also sodium aluminum silicate complexes such as zeolites (eg Zeolite 4A). In this zeolite molecule, the monovalent cation is sodium and the porosity is approximately 4.
It is A. The production of this type of zeolite is described in US Pat. No. 3,114,605. Zeolites are amorphous or crystalline and have water of hydration, as is well known in the art.

It is also possible to use mixtures of organic and/or inorganic virgoos. Such bilgoo mixtures are disclosed in Canadian Patent No. 755.058 and are, for example, ternary mixtures of sodium tripolyphosphate, trisodium nitrilotriacetate and ethane-1-hydroxy-1,1-diphosphonate. The alkali metal salts of the inorganic and organic multivalent anion builder salts are preferred for use in the present invention from an economical point of view. It should be appreciated that water-soluble salts may also find use in the present invention.

Builder salts, including inorganic and organic detergent bilgoux salts, are usually used in clarification mixtures (along with antistatic diammonium compounds, antistatic agents, anionic surfactants, etc.).
The spray-dried beads or m-granules of the present invention include a builder salt content of about 5% to about 90% by weight, preferably about 15% by weight, based on the weight of the spray-dried beads. ~65% by weight, particularly preferably about 20-55% by weight. Therefore, after mixing the later portions, the detergent builder salt content in the final composition is approximately 2-801i! based on the total composition. %,
Preferably 10-70% by weight, particularly preferably 20-50%
The weight should be i%.

Diammonium Compound Antistatic Agent The antistatic compound used in the present invention has a water solubility, particularly a small amount of diammonium compound (5% by weight in both cases).

The diammonium compound is preferably capable of forming a stable and transparent solution or dispersion in water at 25°C containing at least 10ti-%.

The diammonium compounds used in the present invention to reduce static charge build-up are water-soluble compounds having the general formula +11: where R1 is an aliphatic hydrocarbon having from about 12 to about 50 carbon atoms; and R6 are each an aliphatic hydrocarbon group having 1 to 22 carbon atoms (R.

The total number of carbon atoms in all aliphatic hydrocarbon groups, including
and the following formula: % formula %) (carp, m and n are 0 or a positive number regardless of each other, and all (the sum of m+n from R2-R6 groups is at least 2 and not more than 30) (provided that at least one of R2-R6 is the above-mentioned alkanol group): R is 02- C5 lower alkylene or substituted lower 02
~C5 is a divalent bond radical such as alkylene, K is a number from 1 to 20, and X is an aqueous δ salt-forming anion.

Preferred compounds of formula 11+ are those having one or two, preferably a single, long carbon chain group (ie, 12 or more carbon atoms). Therefore, 1 formula (R8− in 11
A preferred definition of R6 is as follows; R1 has 1 carbon number
6 to 22 straight or branched chains.

and saturated or unionized aliphatic hydrocarbon groups (i.e.
straight-chain or branched alkyl, alkenyl or alkynyl), and R2-R6 are carbon atoms 1-16. Preferably 1-12
゜Particularly preferably 1 to 6 alkyl or alkenyl (
However, the total carbon number of all aliphatic hydrocarbon groups in R1-R6 is about 50 or less, preferably about 65 or less, and R2-
Two or less groups, preferably one or less of R6 has a carbon number of 12
more preferably, none of R2-R6 has more than 12 carbon atoms) and the following formula: The sum of R60m-4-n is selected independently from the group consisting of alkanol groups having from at least 5 to 25, preferably 15 or less, with the proviso that
At least one group, preferably at least two groups among R2-R6 are the above-mentioned alkanol groups); R7 is, for example, ethylene (-CH20H2-), propylene (-CH2CH2CH2-), isopropylene (
-CHOH(CH3)OH2-), butylene(-CH2
Alkylene having 2 to 4 carbon atoms such as GH2CH2CH2-), or one or more substituents such as hydroxyl, 01-C1 lower alkyl, hydroxy lower <c, -c, >alkyl, etc. 2) exist. This is a substituted product of alkylene.

Preferably -OHOH- or -CH2CH2C)i2
−.

Most preferably -CI(2C,!(20H2-).

K is 1 to 10, preferably 1 to 5, particularly preferably 1 to 5.
It is 5.

X is, for example, a halide (eg bromide, chloride or iodide), sulfate, methosulfate, ethosulfate, hydroxide.

Water-soluble salt-forming anions such as acetate, propionate, or other similar inorganic or organic solubilizing monovalent anions.

Examples of preferred R0 groups are stearyl, tallow hydrocarbons, hydrogenated tallow hydrocarbons, eicoflu, soybean hydrocarbons, and the like.

Examples of preferred alkyl and alkenyl groups for R2-R6 are methyl, ethyl, propyl, isopropyl n-butyl,
These include t-butyl, n-butenyl, octyl, 1-octyl, and the like. Particularly preferred are methyl, ethyl, propyl and isopropyl. Most preferred are methyl and ethyl.

Examples of preferable alkanol groups for R2-R6 are ethanol (n=0.m=1), propatool (ill=Q, n:
1), ethoxy-, propoquine-0 and mixed (ethoxy)(propoquine) ethanol and/or propatool, e.g. (CH2CH20) m'H (m is 2-4
); (OH20H20)m+(CH(OH3)OH20),
+ (ya' and n' are each a number from 1 to 4, m
I + 'n I is 2 to 6). For mixed ethoxyalkanol groups, the order of addition of ethoxy and propoxy groups is not important;
Either a block of ethoxylic groups or a block of propoxy groups can be bonded to the N atom of the diammonium compound. Alternatively, it is considered that the ethoxy groups and propoxy groups are randomly distributed. Thus, as is well known in the art, the distribution of ethoxy and propoxy groups is such that 11'4 It is thought that it is determined by the order.

Particular examples of compounds of formula (1) which are commercially available or readily prepared by conventional methods include: etc., and the corresponding ethosulfates, no1lides.

It is a water-soluble salt such as acetate.

The above compound (2) (N-methyl-N-(2-hydroxyethyl)-N-tallowalkyl-N'-methyl-N'-
His(2-hydroxyethyl)-propylene diammonium methyl sulfate is particularly preferred. cono compound k
Rewo Chemicals G.
It is a clear liquid solution with 55% solids dissolved. Rewoquat D Q 55 has a free amine content of less than 2% by weight and has a pH within the range of 3.5-5 (1% aqueous solution). This compound can be prepared in the usual manner by 1 e.g. N-methyl-N-IU fatty alkyl-N
It can be produced by reacting 1 mole of '-methylpropylene diamine with 3 moles of ethylene oxide and then quaternizing the resulting compound with methyl sulfate.

Ethoxylation with more than 6 moles of ethylene oxide produces the corresponding highly ethoxylated compounds.

It is an important aspect of the invention that the diammonium salt antistatic agent has a certain degree of water solubility, but is not so water soluble that it is difficult to eliminate from the wash liquor during use of the detergent-softener composition. It is a characteristic. Generally, a solubility of up to about 50% by weight at 25° C. is sufficient to provide the necessary static charge suppression power on washed fabrics.

The aqueous solution or dispersion (free of organic solvents) of the diammonium salt antistatic agent may contain other pH-insensitive heat-stable components,
For example, builders, fillers, anionic surfactants, pH
The modifier, water, etc. are added to the clarification mixture and the mixture is then spray dried by conventional methods. The amount of antistatic agent in the clarification mixture is such that the spray-dried beads or granules contain an antistatic agent of formula tl) from about 0.4 to 15%, preferably from 1 to 12%, particularly preferably from 1 to 12%, based on the weight of the beads. The amount is such that it contains about 2-12%. The antistatic agent is completely homogeneously and finely distributed in the spray-dried beads,
It effectively exhibits its antistatic function without interfering with other functional components.

Next, spray dry beads containing antistatic agent, clay softener and other ingredients, such as nonionic surfactants.

Bleach, enzymes, fragrances and other pH or heat sensitive and/or water insoluble ingredients are intimately mixed to produce the final softener-detergent antistatic composition. The amounts of spray-dried beads and subsequent ingredients are such that the final composition contains the following amounts of essential ingredients:
Fill with filler and water.

Optional Ingredients It is desirable to use inert, water-soluble filler salts in the cleaning compositions of the present invention. A preferred filler salt is an alkali metal sulfate, such as potassium or sodium sulfate. Particularly preferred is sodium sulfate. The amount of filler is generally up to 5% of the weight of the composition, for example 0.1-2%, especially KO05-1%.

The detergent of the present invention can contain various adjuvants. Generally, these include perfume 9 colorants (e.g. pigments and dyes), bleaches (e.g. sodium borate), bleach activators, #A whiter stabilizers, suspending agents or soil suspending agents (e.g. carboquine). alkali metal salts of methylcellulose), optical brighteners (e.g. anionic, cationic, or non-ionic brighteners), foaming stabilizers (e.g. alkanolamides), blowing agents, bactericidal agents, anti-tarnishing agents, pH Regulators, enzymes, etc. Glidants (commonly referred to as flow aids) can also be used to maintain particulate compositions as free-flowing beads or powders. Starch conductors and special clays are commercially available as additives to enhance the flowability of sticky or pasty granular compositions. Two such clay additives are currently commercially available under the trade names [5atintOne J and "Microsil". Small amounts of bound and free water may also be present in the detergent composition so as not to adversely affect the flow properties of the granular or powder composition.

The water content is usually 1 to 15%, preferably 5% of the total composition.
~12%, most preferably 8-12%. Within these proportions, well-flowing granules, powders or granular products result; these can be prevented from becoming too dusty by adjusting particle size and moisture content. .

A suitable range of detergent additives is: Enzyme 0.2
~1%, about 0-15% preservatives, preferably 2-8%, anti-foaming agents and foam suppressants 0-15%.

Preferably from 0 to 8% (e.g. 0.1 to 5%), stain @ internal grinding or anti-settling agents and anti-yellowing agents from 0 to 10%, preferably from 0.5 to 6%1 Colorants, fragrances, brighteners and bluing agent from 0 to about 2% by total weight, preferably from about 1% (e.g. 0.2 to 0.8%), p) l regulator and pH buffering agent from 0 to about 2%;
5%, preferably 0 to about 2%, bleach 0 to about 40%, preferably 0 to about 25% (e.g., 2 to 20%), WI whitener stabilizer and bleach activator low about 15% , preferably 0
~10% (e.g. 0.1-8%). When choosing an adjuvant.

It is selected to be compatible with the main component of the detergent composition.

Whatever the form of the washing detergent, its use in the washing process is essentially the same. The granular composition is usually washed in an automatic washing machine (under water, the concentration in the washing water is about 0.05-1.5%, usually 0.1-1.2%).
Add so that it is within the range of . The water to which this is added has a medium or low hardness of 1, e.g. 50 to 12 as carnocum carbonate.
Although a hardness of 0 m) pm is preferred, both soft water and hard water can be used effectively. Water temperature is 20℃~1
00℃, but the fabric or the item being washed may deteriorate)
Withstands high temperatures without fading, and can be used at temperatures between 60°C and 100°C.
It is preferable that it is ℃. If low temperature washing is desired, the temperature can be kept between 20 and 40°C.

In the above detergent composition concentration, the pH of the water to be washed is usually on the alkaline side, for example 7 to 12. Preferably 8~
11. Special VC 9-10. The weight ratio of items to be washed:washing water is usually about 1:4 to 1:50, preferably 1:1.
0-1;50.

The following examples illustrate the invention without limiting it. All parts and percentages are by weight unless otherwise indicated.

Example 1 A primary composition is formed by first molding Klj [fog-dried beads and subsequently adding component (a).

(A) Spray dried beads part water
6
．． 8-hydrogenated fish oil or tallow fatty acid 2.8
NaOH (55,7%) 1.6 Tap water 11.5 Sodium silicate (40%) 99 Na O: 310□ Anionic surfactant 1&0 Optical brightener 0.2 Sodium carboxylic methyl cellulose 0.7 Tripolyphosphoric acid Pentasodium 66.4 Rewoquat
D Q 55 (5C 1% dichotinum 4.7nium compound) Sodium sulfate (anhydrous) 0.7 1 Linear dodecylbenzene nasal phonate (as an aqueous slurry) 2 Stilbene brightener, Ryo 4. High δ degree grain 6 After drying 6
4.2 parts Components added later (B) Part Sodium perborate 15.0 Blue bentonite clay lump 16.0 Enzyme 0.5 Magnesium silicate/DTPA mixture A2 0.2 Potassium methyl siliconate ( 50%) 0.6 Nonionic surfactant 6.0 Duet787 (Fragrance) 0.5 Spray-dried beads (A) 64.24
C14""CI5 fatty alcohol ethoxylated with 11 moles of diethylene oxide in the final composition
The concentration of evoquat D Q 55 is 1.65%.

The same composition was made for comparison, except that Rewoqu
atDQ55 was not used. Each composition was tested for static charge suppression power on four types of fabrics (acrylic, polyester, polyester/cotton blend, nylon).

Table 1 below reports the results of electrostatic charge values obtained by Bauman's instrumental method. In Table 2.

Electrostatic charge position ((〕= from no charge to 5 highly electrostatic load)
I will report the judgment result by the unrelated Satoshi and Monkeji.

All data were obtained after washing at 60°C and drying for 40 minutes at full dryer power in a M1ele dryer. Single instrument readings were taken after conditioning at 20° C. and 40% relative humidity. The composition of the present invention was mixed into a commercially available softener-detergent powder composition (tallow trimethylammonium chloride 2).
%, sitallo methylamine salt 4%). The results of the second test series are also shown in Tables 1 and 2.

The softening, detergency and whitening ratings of the composition of the present invention (A+B) were unfavorable for these performance parameters when compared to the A+B composition that does not carry HeWOqua'u D Q 55 antistatic agent. ρ) It was shown that there is no.

Example 2 In Example 1, the same amount of Rewo as used for component A
When it was used in place of component B added from quat D Q 55'l Flt-, the static charge suppressing power was reduced.

Example 6 Following the same general procedure as Example 1, the following compositions are prepared: Sodium Nitridecylbenzenesulfonate 15.
0 Pentasodium Tripolyphosphate 63.0 INaO: 2.4SiO2
7.0 Sodium sulfate
4.0 optical brightener (Tlrlopal 58M)
0.2Na carboxymethylcellulose 0.25Rewoquat D Q
55 1.8NaOH(4
0%) 1.75 subtotal 63.0 Ingredients added later B Thixogel & 1 Clay 1
8.0 Sodium perborate 14.
0 Enzyme 0.5 Potassium Methyl Siliconate 0.6 Nonionic Surfactant 6.0 Magnesium Silicate/DTPA Mixture A 2 0
．． 5Duet 787
0.6 Subtotal 57.0 Condensation L with 9 moles of ethylene oxide per 11 moles
, □~C15 fatty alcohol.

Example 4 Following the same general procedure as in Example 1, the following compositions are prepared: Sodium Nitripolyphosphate 43.3 Sodium Silicate 5.8 Sodium Sulfate 10. .

Rewoquat D Q 55
2. ONa carboquine methylcellulose
0.5 Subtotal 80.0 Nonionic surfactant 6.0 Optical brightener 0.2 Enzyme
. , 6 Fragrance 0.2 Gelwhlte G P 13.0 Subtotal 20.0 Total 100.0 1 1.2 Sodium tallow alkyl sulfate: Sodium dobuflubenzenesulfonate 2 Coconut oil alcohol ethoxylate (external) 5 people)

Claims (1)

[Claims] 1. An antistatic detergent composition in solid form that is compatible with a clay mineral fabric softener, comprising: (a) an anionic synthetic detergent, a nonionic synthetic detergent, a zwitterion; at least one pH- and heat-insensitive detergent compound selected from the group consisting of synthetic detergents, amphoteric detergents, and mixtures thereof; (b) at least one pH- and heat-insensitive inorganic or organic detergent builder salt; (c) The following general formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (1) [In the formula, R_1 is an aliphatic hydrocarbon having about 12 to about 30 carbon atoms; R_2, R_3 , R_4, R_5, and R_6 each is an aliphatic hydrocarbon group having 1 to 22 carbon atoms (the total number of carbon atoms of all aliphatic hydrocarbon groups including R_1 is approximately 75 or less, and each of R_2 to R_6 groups is The number of carbon atoms in the three groups or less is greater than 12) and the alkanol group of the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, m and n are 0 or a positive number regardless of each other, The sum of m and n from all R_2 to R_6 groups is at least 2 but not more than 30) (provided that at least one of R_2 to R_6 is ), R_7 is, for example, C
_2-C_5 lower alkylene or substituted C_2-C_5
is a divalent bond radical such as lower alkylene; K is a number from 1 to 20; X is a water-soluble salt-forming anion; and (d) Antistatic detergent compositions comprising spray-dried beads of a homogeneous mixture of any one or more pH- and heat-insensitive detergent additives, fillers, and water. 2. The antistatic detergent composition according to claim 1, wherein at least one type of detergent compound is an anionic synthetic detergent, and at least one type of detergent builder salt is an inorganic polyphosphate builder salt. 3. In formula (1), R_1 is a straight chain or branched alkyl, alkenyl or alkynyl group having 16 to 22 carbon atoms, and R_2 to R_
6 is alkyl or alkenyl having 1 to 16 carbon atoms (however, the total number of carbon atoms in all aliphatic hydrocarbon groups R_1 to R_6 is about 50 or less, and the number of carbon atoms in 2 or less groups in R_2 to R_6 is less than 12) ) and the following formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. (However, at least one group of R_2 to R_6 is the above-mentioned alkanol group), and R_7 has 2 to 4 carbon atoms. Alkylene or alkylene having 2 to 4 carbon atoms having a substituent selected from the group consisting of hydroxyl, C_1-C_4 lower alkyl and hydroxy lower (C_1-C_4) alkyl, and K is a number from 1 to 10. The antistatic detergent composition according to item 1. 4, R_2 to R_6 are independently alkyl or alkenyl having 1 to 6 carbon atoms, or the above-mentioned alkanol group (provided that the total number of carbon atoms of all the aliphatic hydrocarbon groups R_1 to R_6 is about 35 or less, and alkanol Group R_2
~The sum of m+n from all of R_6 is 15 or less)
, R_7 is -CH_2CH_2- or -CH_2CH_
The antistatic detergent composition according to claim 2, wherein 2CH_2- and K is 1. 5. The following composition: about 10% to about 60% by weight of the at least one detergent compound; about 5% to about 90% by weight of the at least one detergent builder salt; about 0.4% to about 15% by weight of the antistatic agent; and a detergent. An antistatic detergent composition according to claim 1, comprising additives, fillers, and about 0 to about 50% water by weight. 6. Based on weight, the following composition: about 15% to about 40% linear higher alkylbenzene-sulfonate anionic synthetic detergent, about 5% to 55% zeolite builder, about 1% to 12% of the diammonium compound antistatic agent, and about 1% to 12% pH neutral 2. The antistatic detergent composition of claim 1 comprising about 5-40% of at least one element selected from the group consisting of sensitive and heat-stable detergent additives, fillers, moisture, and mixtures thereof. 7. The following composition based on weight: linear higher alkylbenzene sulfonate anionic synthetic detergent composition from about 15 to about 40%, inorganic polyphosphate detergent builder from about 15 to 65%, said diammonium compound antistatic agent from about 1 to 12%. %, and from about 5 to 40% of at least one element selected from the group consisting of pH-insensitive and heat-stable detergent additives, fillers, moisture, and mixtures thereof. detergent composition. 8. A patent in which the linear higher alkylbenzene sulfonate is dodecylbenzene sulfonate, the polyphosphate detergent builder is pentasodium tripolyphosphate, and the diammonium compound is a compound having the following formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ The antistatic detergent composition according to claim 7. 9. An antistatic softening detergent composition comprising a clay softener mixed with the spray-dried antistatic detergent composition of claim 1. 10. The following composition: (A) about 1 to about 95% by weight of at least one detergent compound selected from the group consisting of anionic synthetic detergents, nonionic synthetic detergents, amphoteric synthetic detergents, zwitterionic synthetic detergents, and mixtures thereof. (B) Clay mineral fabric softener about 1 to about 50% by weight (C)
about 2% to about 80% by weight of at least one type of detergent builder, and (D) the following formula (1): ▲Mathematical formula, chemical formula, table, etc.▼(1) [In the formula, R_1 has a carbon number of about 12 to about 30 is an aliphatic hydrocarbon, and each of R_2, R_3, R_4, R_5 and R_6 is
An aliphatic hydrocarbon group having 1 to 22 carbon atoms (however, the total number of carbon atoms in all aliphatic hydrocarbon groups including R_1 is approximately 75 or less, and the number of carbon atoms in 3 or less groups among R_2 to R_6 groups is 1
2) and the following formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, m and n are 0 or a positive number regardless of each other, and the sum of m + n from all R_2 to R_6 groups is R_7 is a C_2 to C_5 lower alkylene or a substituted C_2 ~C_5 is a divalent bond radical, such as lower alkylene, K is a number from 1 to 20, and X is a water-soluble salt-forming anion. and (E) at least one detergent additive, a filler and from 0 to about 50% water by weight. 11. The diammonium compound of formula (1) is the diammonium compound, an anionic surfactant, a detergent builder salt,
and one of the spray-dried beads consisting of optional pH-insensitive and heat-stable detergent additives, fillers and mixtures thereof.
11. The composition of claim 10, wherein said clay fabric softener is present as a component in the composition and is homogeneously mixed with said spray dried beads. 12. In formula (1), R_1 is a straight or branched alkyl, alkenyl or alkynyl having 16 to 22 carbon atoms, and R_2 to R_6
is an alkyl or alkenyl having 1 to 16 carbon atoms (the total number of carbon atoms of all aliphatic hydrocarbon groups R_1 to R_6 is about 5
0 or less, and the number of carbon atoms in two or less groups of R_2 to R_6 is greater than 12) and the following formula: ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, m and n are 0 regardless of each other. or is a positive number,
The sum of m+n from all of the alkanol groups R_2 to R_6 is from at least 3 to 25 or less). R_7 is alkylene having 2 to 4 carbon atoms, or hydroxyl, C_1 to C_4 lower alkyl and hydroxyl lower (
11. The composition of claim 10, wherein the composition is alkylene having 2 to 4 carbon atoms and having a substituent selected from the group consisting of C_1 to C_4) alkyl; and K is a number from 1 to 10. 13, R_2 to R_6 have 1 to 6 carbon atoms regardless of each other
is an alkyl or alkenyl group or the above-mentioned alkanol group (provided that the total number of carbon atoms in all of the aliphatic hydrocarbon groups R_1 to R_6 is about 35 or less, and the alkanol group R_
The sum of m+n from all of 2 to R_6 is 15 or less), R_7 is -CH_2CH_2- or -CH_2CH_
13. The composition according to claim 12, wherein 2CH_2- and K is 1. 14. The composition according to claim 10, wherein the diammonium compound antistatic agent has a mathematical formula, a chemical formula, a table, etc.▼.