JPH03146600A - Granular detergent composition containing compound incorporated in microemulsion base gel - Google Patents

Abstract

PURPOSE: To obtain the subject composition which is slowly released when brought into contact with water or when its temperature is raised, and is low- cost and easily handleable by comprising detergent components with particles of a microemulsion base gel in which a compound is occluded.

CONSTITUTION: This composition comprises 0.5-15 wt.% surfactant (A) desirably comprising a 10-12C linear alkylbenzenesulfonate salt, 10-90 wt.% water, 0-80 wt.% oil (C) and 0.5-20 wt.% gelling agent (D) comprising gelatin or a polyacrylate and particles (E) of a microemulsion base gel in which a compound such as a lustering agent or a perfume is occluded.

COPYRIGHT: (C)1991,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a granular composition containing at least one encapsulated ingredient.

[Conventional technology and problems]

Granular detergent compositions are well known in the art and their ingredients are described in various publications. It is also known that it is desirable not to include some of these components in these compositions, at least in free form and not at excessively high levels.

There are several reasons for that. That is, for example, in the case of detergent compositions containing oxygen, human safety becomes an issue.

Another example is the appearance of the finished product. Dyes tend to "bleed" in granular detergent compositions, resulting in a product appearance that is unacceptable to consumers.

Brighteners also pose a problem, especially in concentrated powder detergents (ie even at high levels of ingredient content). This is because rapid release into the wash water causes "spots" on the laundry.

Yet another example is perfume. In order to increase the residual fragrance of laundered clothes, it is desirable to increase the perfume loading of detergent compositions. However, if excessively high levels of fragrance are included, the composition will have a strong odor, which is also undesirable to the consumer.

Additionally, some of the basic agents used in the preparation of the compositions have unpleasant inherent odors, and it is also undesirable to incorporate them as free components.

Therefore, many methods have been proposed, including all kinds of encapsulation techniques in which the components are "surrounded" by a coating material. These techniques are effective in the sense that certain components are "isolated" and completely separated from the rest of the composition.

However, for the production of detergent compositions, a new problem arises in that these encapsulates are brittle, ie they tend to rupture when subjected to mild mechanical stress. This problem,
It becomes even more sensitive when processing on an industrial scale.

As a solution, systems have been created in which the components to be isolated are "entrapped" within a matrix rather than being encapsulated within a coating.

That is, the system consists of dispersed component droplets that are isolated within a continuous matrix. Such systems are clearly much less sensitive to mechanical stress.

European Patent Application No. 0.028.118 describes a system in which volatile components are encapsulated in a special polymeric matrix.

However, the substrate releases volatile components when exposed to the atmosphere, making it unsuitable for use in detergent compositions.

Additionally, this system is limited to volatile materials.

US Pat. No. 4,184,099 describes a system in which volatile components are encapsulated in a polyamide resin. The system is configured such that slow release of the components is initiated by an increase in the melt temperature of the resin. Therefore, it cannot function in detergent compositions used at low temperatures.

Furthermore, this system is limited to volatile components. This technology also requires complex processing steps.

US Pat. No. 4,209,417 describes perfume particles and detergent compositions containing the same. According to this patent, forming an aqueous suspension of perfume, polymer and emulsifier;
It is then poured onto a surface for drying. The resulting dry film is ground to form particles.

This manufacturing process is complex and time consuming. Additionally, particle formation requires special care to contain the desired particle size. Detergent compositions containing such particles are made by mixing the base powder with the particles, thus resulting in a non-homogeneous powder.

U.S. Pat. No. 4,339,356 describes the process of emulsifying a perfume in water with a polymer and then contacting it with a wettable powder material. A free-flowing granular material containing perfume is thus obtained. This granular material can then be mixed with a granular detergent composition.

PCT application PCT/CH35100154 describes a process for producing microemulsions and transforming them into gel-like forms. This gel is used in the cosmetic or pharmaceutical field.

[Purpose of the invention]

It is an object of the present invention to provide detergent compositions containing encapsulated compounds.

Another object of the present invention is to provide a detergent composition in which the encapsulated compound is gradually released when it comes into contact with water or when the temperature increases.

Yet another object of the present invention is to provide a detergent composition that can incorporate any compound, whether water-soluble or oil-soluble.

Yet another object of the present invention is to provide a detergent composition that can be manufactured at low cost using conventional ingredients.

Yet another object of the invention is to provide a detergent composition in which the system encapsulating the compounds is not fragile to mechanical stress and is therefore easy to handle.

Yet another object of the invention is to provide homogeneous compositions containing such encapsulated compounds.

It is also an object of the present invention to provide a simple process for producing such detergent compositions.

[Summary of the invention]

The present invention provides granular detergent compositions containing compounds encapsulated in microemulsion-based gels.

Microemulsion-based gels contain the remainder of the detergent composition (
manufactured separately from the base powder). The final product is obtained by co-milling this gel and the base powder. Alternatively, the gel is co-milled with the base powder or with any powder materials before mixing.

[Detailed description of the invention]

Microemulsion-based gels have at least four components,
That is, it includes water, ura, an encapsulated compound, and a gelling agent.

The first step in preparing the gel is to mix water and oil in a weight ratio of about 1.4 to about 4:1 water:oil.

According to the invention, any oil can be used, including:

Fatty substances of vegetable or animal origin, such as fatty acid esters, mineral oils, fuel oils and lubricants as hydrocarbons derived from petroleum and their products, - volatile oils or essential oils.

Hydrocarbons ranging from light paraffins to heavy mineral oils are preferred. These are commercially available under the trademark 15OPARR, and particularly preferred are straight or branched chain hydrocarbons of 10 to 24 carbon atoms.

A two-phase system is obtained by mixing oil and water.

The second stage is the compound to be encapsulated (hereinafter referred to as “compound”).
). Compounds reach either of the two phases mentioned above depending on their hydrophilic or hydrophobic nature.

According to the present invention, any compound is encapsulated regardless of its chemical nature.

Importantly, if the compound itself is an oil or oil mixture, this can be mixed directly with water. In other words, the above-mentioned number of floors is not required. This is the case, for example, when the compound is a fragrance.

At this stage, the system consists of an aqueous phase and an oil phase;
one of which contains (or consists of) a compound
.

The third step is the addition of surfactants into the system to obtain a stable microemulsion. According to the present invention, an anionic surfactant, a nonionic surfactant,
Any surfactant can be used, such as cationic surfactants, Zwitter ionic surfactants, or mixtures thereof.

Synthetic anionic surfactants can be represented by the general formula R503M. wherein R1 is selected from the group consisting of straight chain or branched alkyl groups containing from about 8 to about 24 carbon atoms and alkylphenyl groups containing from about 9 to about 15 carbon atoms in the alkyl group. represents a hydrocarbon group. M is typically a cation-forming salt selected from the group consisting of sodium, potassium, ammonium and mixtures thereof.

Preferred synthetic anionic surfactants contain 9 in the alkyl group.
Water-soluble salts of alkylbenzenesulfonic acids containing from 1 to 15 carbon atoms. Other preferred synthetic anionic groups are water soluble salts of alkyl sulfates or alkyl polyethoxylate ether sulfates, wherein the alkyl groups are from about 8 to about 24, preferably from about 10 to about 1
It contains 8 carbon atoms and about 1 to about 20, preferably about 1 to about 12 ethoxy groups. Other suitable anionic surfactants are disclosed in US Pat. No. 4,170,565.

Nonionic surfactants are conventionally prepared by condensing ethylene oxide with a hydrocarbon having a reactive hydrogen atom, such as a hydroxyl, carboxyl, or amide group, in the presence of an acidic or basic catalyst; Compounds of formula.

RA(CH2CH20)nH where R is a hydrophobic moiety, A is a group having a reactive hydrogen atom, and n is the average number of ethylene oxide moieties. R typically contains about 8 to about 22 carbon atoms.

The aforementioned compounds can also be formed by condensation of propylene oxide and low molecular weight compounds. n is usually 2 and about 24
It fluctuates between.

The hydrophobic moiety of the nonionic compound is preferably about 8 to
It is a primary or secondary, straight chain or branched aliphatic alcohol having about 24, more preferably about 12 to about 20 carbon atoms. A more complete disclosure of suitable nonionic surfactants is found in US Pat. No. 4,111,855. Mixtures of nonionic surfactants are preferred.

Zvitta ionic surfactants are aliphatic moieties, linear or branched, in which one aliphatic substituent contains from about 8 to about 24 carbon atoms and the other substituent contains at least an anionic water-soluble group. Derivatives of quaternary ammonium, phosphonium and sulfonium compounds. Particularly preferred Zwitter ionic materials are the ethquinated sulfonic acids and ammonium sulfates described in U.S. Pat. Nos. 3,925,262 and 3,929,678.

Semipolar nonionic surfactants are selected from the group consisting of one alkyl or hydroxyalkyl moiety of about 8 to about 28 carbon atoms; Contains water-soluble amine oxides containing two moieties in which carbon atoms are optionally bonded in a cyclic manner.

Suitable anionic synthetic surfactant salts are selected from the group consisting of sulfonates and sulfates.

Similar anionic detergents are known in the detergent industry and include
It is widely used in commercially available detergents. Preferred anionic synthetic water-soluble sulfonic acids and sulfates have alkyl groups in their molecular structure containing from about 8 to about 22 carbon atoms.

Examples of such preferred anionic surfactant salts include reaction products obtained by sulfation of C8-18 fatty alcohols derived from tallow and coconut ura, alkylbenzene sulfones in which the alkyl group contains about 9 to 15 carbon atoms. acid salts, sodium alkyl glyceryl ether sulfonates, ether sulfates of fatty alcohols derived from tallow and coconut curds, sulfuric acid and sulfonate coconut fatty acid monoglycerides, and paraffins having from about 8 to about 22 carbon atoms in the alkyl chain. It is a water-soluble salt of sulfonic acid. For example, U.S. Patent No. 3.332,88
Sulfonic acid olefin surfactants such as those described in more detail in No. 0 may also be used. Anionic synthetic sulfonate and/or sulfate neutralizing cations are represented by the usual cations widely used in detergent technology, such as sodium and potassium.

In this case, particularly preferred anionic synthetic surfactant components are represented by water-soluble salts of alkylbenzenesulfonic acids, preferably sodium alkylbenzenesulfonates having about 10 to 13 carbon atoms in the alkyl group.

Preferred classes of nonionic ethoxylates are 12-15
Fatty alcohols with carbon atoms and fatty alcohols 1
It is represented by about 4 to 10 moles per mole of condensation product with ethylene oxide.

A suitable size for this class of ethoxylates is C
condensation product of a 12-Cl3 oxo alcohol with 7 moles of ethylene oxide per mole of alcohol, a condensation product of a narrow-cut C oxo alcohol with 7 or 9 moles of ethylene oxide per mole of fatty 4-15 (oxo)alcohol; Condensation products of narrow-cut C oxo alcohols with 6.5 moles of ethylene oxide per mole of fatty (oxo)al 2-H alcohol and a degree of ethoxylation within the range of 5 to 8 (
Contains the condensation product G-14 of coconut fatty alcohols. Fatty oxo alcohols are primarily linear, but depending on the processing conditions and the raw olefin, they can have short molecular chains, particularly methyl branches.

Degrees of branching in the range of 15% to 50% (wt%) are often found in commercial oxo alcohols.

Preferred nonionic ethoxylate compounds are also represented by mixtures of two distinct ethoxylated nonionic surfactants having different degrees of ethoxylation.

For example, a nonionic ethoxylated surfactant containing 3 to 7 moles of ethylene oxide per mole of hydrophobic moiety and a second ethoxylated species having 8 to 14 moles of ethylene oxide per mole of hydrophobic moiety. blend. A preferred nonionic ethoxylate mixture is 5
About 3-7 per mole of C12-15 oxo alcohols and fatty oxo alcohols with up to 0% branching by weight
C with low ethoxylates as condensation products with moles of ethylene oxide and with up to 50% by weight branching
Contains a high ethoxylate as a condensation product of an oxo alcohol and about 8 to 14 moles of ethylene oxide per mole of B-19 oxo alcohol.

Examples of suitable cationic surfactants are quaternary ammonium compounds of the formula RIR2R3R4N+X. Here, R is a C alkyl group 1 12-20 or a hydroxyalkyl group, R2 is a Cl-4 alkyl group, a C alkyl group, a hydroxy dialkyl group, or a Cl-4 hydroxyalkyl group, R
3 and R4 are each a Cl-4 alkyl group, a hydroxyalkyl group, a CG-8 aryl group or an alkylaryl group, and X is a halogen. Preferred compounds are monolinear quaternary ammonium compounds (ie, compounds in which R2 in the above formula is a Cl-4 alkyl group or a hydroxyalkyl group).

The exact nature and amount of surfactant added to the system
It must be determined such that a stable microemulsion is obtained.

By "stable microemulsion" is meant the formation of micelles or liquid-crystalline dispersions that do not immediately separate into separate devices upon standing.

The final step in gel formation is the addition of a gelling agent.

Suitable gelling agents for use in this case are polymeric thickeners, including natural rubber. Suitable natural rubbers include gum arabic and the like. Suitable polymers include water-soluble polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, poly(ethylene oxide), agarose and other polysaccharides, cellulose derivatives such as methyl-, ethyl-, propyl-
and cellulose ethers such as butyl cellulose ether, butyl hydroxybutyl cellulose ether, gelatin and pectin, starch, gum arabic, poly(acrylic acid) and its derivatives, polyacrylamide, styrene maleic anhydride, poly(vinyl methyl ether, maleic anhydride) , amorphous poly(vinyl methyl ether), poly(vinyl 2-methoxyethyl ether) poly(vinyl sulfonic acid) or its sodium salt, poly(4-vinyl-phthalic acid) and low molecular weight melamine formaldehyde.

Natural gum and gelatin are preferred, with gelatin being most preferred in this case.

In the gelling step, it is necessary to heat the mixture to a temperature equal to or higher than the melting point of the gelling agent before or during the addition of the gelling agent. This is the case when the gelling agent is polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, agarose or other polysaccharides, gelatin or starch.

In practice, the mixture is heated before the addition of the gelling agent and then the gelling agent is added gradually while the mixture is kept at the same temperature and stirred. When the entire amount of gelling agent has been added, the mixture is allowed to cool to ambient temperature with stirring.

Polyacrylic acid and its derivatives, polyacrylamide, styrene maleic anhydride, poly(vinyl methyl
ether (maleic anhydride), amorphous poly(vinyl methyl ether), poly(vinyl 2-methoxy ethyl ether), poly(vinyl sulfonic acid) or its sodium salt, poly(4-vinyl-phthalic acid) and low molecular weight melamine forms. When using an aldehyde, one starts with the mixture at an acidic pH before the addition of the gelling agent and increases the pH to neutralize the mixture after the addition of the gelling agent to induce gel formation.

It is also preferable to gently stir the mixture during this step. In this case, in addition to pH neutralization, heating of the mixture is also recommended.

Also, some gelling agents do not require any additional processing. That is, it is sufficient to simply add the gelling agent while stirring the mixture. This is the case when using polyethylene oxide, all cellulose derivatives, pectin or gum arabic.

In this case, the type of gelling agent added is not specified. In practice, depending on the amount of gelling agent added, the final mixture has a viscosity ranging from liquid to gel. Ideally, a non-flowing sticky mixture with a rubber-like consistency should be obtained.

The gel is then co-milled with a conventional granular detergent composition (base powder) so that the grinding action forms the gel into sticky small particles and coats it with the base powder.

Co-milling refers to any mechanical action that grinds the gel together with the base powder or the powdered materials mentioned above.

Any granular detergent composition containing any known ingredients can be used in the present invention. That is, the present invention is not limited to any particular detergent composition. Granular detergent composition refers to any composition in granular form that is used to clean fabrics or other materials.

Such compositions are described, for example, in EP 0 219 314
EPo 220 024, EP 0 133
804° EP O12491B.

A granular detergent composition is thus obtained containing the compound encapsulated in a microemulsion-based gel.

The final appearance of the product depends on the size of the granules and can be adjusted by changing the grinding parameters.

In other embodiments, the gel can be co-milled with any powder materials prior to co-milling or mixing with the base powder. Indeed, such an embodiment is convenient when using materials such as clays or zeolites which are commercially available in powdered form.

Before mixing the gel with the base powder or the powdered materials mentioned above, it may be preferable to first cut the gel into fine pieces in order to ensure efficient mixing of both components.

Upon use of the detergent composition, the encapsulated ingredients are released into the wash liquor upon dilution and/or heating.

〔Example〕

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

Examples A representative granular detergent composition containing a microemulsion-based gel encapsulating a fragrance is prepared as follows.

a. The gel contains the following components.

Ingredients heavy ffi 96 water
55 fragrance
30 Linear alkylbenzene sulfonate 5 Gelatin (bloom strength 240) 10 Mix water and perfume and add surfactant to obtain a stable microemulsion.

Heat the mixture to about 50° C. and add gelatin while stirring.

The mixture is then allowed to cool to room temperature while stirring.

b Separately prepare a base granular detergent composition containing the following ingredients:

Anionic surfactant (linear alkylbenzene sulfonate) 6
Weight% fatty acids
1.5 Nonionic surfactant
6 Olide (Builder) 22 Sodium carbonate 12
．． 5 silicate
4.5 Sodium sulfate
13.0 Soil reprecipitation prevention agent (polymer) 3.0 Perborate 18.
0 water
9.0 Others
The 4,5 gel and base detergent composition are co-milled at a detergent nigel weighting of approximately 6,1.

A granular detergent composition containing approximately 5% encapsulated fragrance is thus obtained.

Example 2 A detergent composition is obtained in the same manner as in the previous example except that the gel contains the following components.

Ingredients Weight% Fragrance 62
Linear alkylbenzene sulfonate 1.
5 water 2
8 gelatin (bloom strength 240)
8.5 Co-milling the granular detergent and gel with a detergent nigel weighting of about 6:1 to obtain a detergent composition containing about 10% encapsulated fragrance.

Example 3 A granular detergent similar to the previous example and a gel containing:
, 1 to obtain a detergent composition.

Ingredients Weight % Brightener: BIankophor (trademark of Bayer) 9-linear alkylbenzene sulfonate 4.5 Water
37.5 ura: l5opar H (trademark of Exxon) 41 gelatin (bloom strength 240) 8.0 gel is obtained as follows.

Mix water and ura, and cool the brightener.

Introduce a surfactant and obtain a stable microemulsion.

Heat the mixture to about 45°C and add the gelatin without stirring.

Allow the mixture to cool while stirring and strain the gel.

Claims (1)

[Scope of Claims] 1. A granular detergent composition containing conventional detergent ingredients, further comprising particles of a microemulsion-based gel encapsulating a compound. 2. The microemulsion base gel encapsulating the above compound comprises: - the above compound in an amount of 0.5% to 80% by weight of the entire composition; - a surfactant in an amount of 0.5% to 15% by weight of the entire composition; - 10% to 90% by weight of the total composition water; - 0% to 80% oil by weight of the total composition; - 0.5% to 20% gel by weight of the total composition. The detergent composition according to claim 1, further comprising a curing agent. 3. The detergent composition according to claim 2, wherein the weight ratio of water to oil is in the range of 1:4 to 4:1. 4. Claim 2, wherein the surfactant is a linear C_1_0-C_1_3 alkylbenzene sulfonate.
or 3. The detergent composition according to any one of 3. 5. Claim 2, wherein the gelling agent is gelatin.
, 3 or 4. The detergent composition according to any one of . 6. The detergent composition according to claim 1, 2, 3 or 4, wherein the gelling agent is polyacrylate. 7. The detergent composition according to any one of claims 1 to 6, wherein the encapsulated compound is a fragrance. 8. The detergent composition according to any one of claims 1 to 7, wherein the encapsulated compound is a brightener. 9. a. mixing water, oil and compound; b. adding surfactant to obtain a stable microemulsion; c. gelling agent to obtain a non-flowing gel. A method for producing a granular detergent composition according to any one of claims 1 to 8, comprising the steps of: d) co-milling the gel and base powder. 10. a. mixing water, oil and compound; b. adding a surfactant to obtain a stable microemulsion; c. a gelling agent to obtain a non-flowing gel. d. co-milling the gel and powder material; e. step d.
A method for producing a granular detergent composition according to any one of claims 1 to 8, characterized in that it comprises the step of co-milling or mixing the product of and the base powder. 11.Claim 9 or 10, characterized in that step c comprises: - adding gelatin and stirring while heating the mixture to about 50°C; and - cooling the mixture to room temperature while stirring. The method described in any of the above. 12. wherein step c comprises: - adding polyacrylate to the mixture at acidic pH while gently stirring and heating to about 50°C; and - neutralizing the pH of said mixture. 9
or the method according to any one of 10.