JP2859403B2 - Granular detergent composition containing compound embedded in microemulsion-based gel - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a granular composition containing at least one component contained therein.

[Conventional technology and problems]

Granular detergent compositions are known in the art, the components of which are described in various documents. It is also known that it is desirable for these compositions to contain at least some of these components, not in free form, but at excessively high levels.

There are several reasons. That is, for example, in the case of a detergent composition containing oxygen, safety of the human body becomes a problem.

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 cause problems, especially in concentrated powders (ie even high levels of component content). This is because rapid release into the washing water causes "spots" on the laundry.

Yet another example is a fragrance. It is desirable to increase the perfume loading of the detergent composition to increase the residual fragrance of the washed garment. However, if too high a level of perfume is included, the composition has a strong odor, which is also undesirable for consumers.

Also, some basic drugs used in the preparation of the compositions have an unpleasant inherent odor, and it is not desirable to combine them as free components.

As such, a number of methods have been proposed, including all types of encapsulation techniques where the components are "enclosed" by a coating material. These techniques are effective in that they "isolate" certain components and completely separate them from other parts of the composition.

However, a new problem arises with respect to the production of detergent compositions in that these encapsulates are brittle, ie they tend to break when subjected to light mechanical stress. This problem becomes more acute in industrial scale processing.

The solution has been to create a system in which the components to be sequestered are "entrapped" in a matrix rather than encapsulated in a coating. That is, the system consists of dispersing isolated droplets of components in a continuous matrix. Such a system is clearly much less sensitive to mechanical stress.

EP 0,028,118 describes a system in which volatile components are embedded in a special polymer matrix. However, they are not suitable for use in detergent compositions because the substrate releases volatile components when exposed to the atmosphere. Furthermore, this system is limited to volatile substances.

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

Further, the system is limited to volatile components. In addition, this technique is based on complicated processing steps.

U.S. Pat. No. 4,209,417 describes perfume particles and detergent compositions containing them. According to this patent, an aqueous suspension of perfume, polymer and emulsion is formed and then poured onto a surface for drying. The resulting dried film is ground to form particles.

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

U.S. Pat. No. 4,339,356 describes a process in which a fragrance is emulsified with a polymer in water and then contacted with a hydratable powdered material. In this way, a free-flowing granular material containing a fragrance is obtained. This granular material can then be mixed with the granular detergent composition.

PCT application PCT / CH85 / 00154 describes the preparation of a microemulsion and the process of transforming it into a gel.
This gel is used in the cosmetic or pharmaceutical fields.

[Object of the Invention] An object of the present invention is to provide a detergent composition containing a compound to be included.

It is another object of the present invention to provide a detergent composition which is gradually released when the above-mentioned encapsulated compound comes into contact with water or when the temperature rises.

It is yet another object of the present invention to provide a detergent composition that can be encapsulated with any compound, whether a water-soluble or oil-soluble material.

Still another object of the present invention is to provide a detergent composition that can be manufactured at low cost using ordinary components.

It is yet another object of the present invention to provide a detergent composition in which the compound-encapsulating system is not brittle to mechanical stress and is therefore easy to handle.

Yet another object of the present invention is to provide a homogeneous composition containing such an embedded compound.

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

[Summary of the Invention]

The present invention provides a granular detergent composition containing a compound embedded in a microemulsion base gel.

The microemulsion base gel is manufactured separately from the rest of the detergent composition (base powder). The final product is
It is obtained by co-grinding this gel and base powder. Alternatively, the gel is co-ground with any powdered material before co-ground or mixed with the base powder.

[Specific description of the invention]

The microemulsion base gel contains at least four components: water, oil, encapsulated compound and gelling agent.

The first step in making the gel involves mixing water and oil in a weight ratio of about 1: 4 to 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 its products; volatile oils or essential oils.

Hydrocarbons in the range from light paraffins to heavy mineral oils are preferred. It is marketed under the trademark ISOPAR ^R, is a particularly preferred are 10 to 24 carbon atoms linear or branched chain hydrocarbon.

 Mixing oil and water results in a two-phase system.

The second step consists in adding the compound to be encapsulated (hereinafter referred to as "compound"). The compound reaches one of the two phases described above, depending on its hydrophilicity or hydrophobicity.

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

Importantly, if the compound itself is an oil or oil mixture, it can be mixed directly with water. That is, the first step 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 to add a surfactant into the system to obtain a stable microemulsion. According to the present invention, any surfactant can be used, such as an anionic surfactant, a nonionic surfactant, a cationic surfactant, a Zwitterionic surfactant or a mixture thereof.

Synthetic anionic surfactants can be represented by the general formula R ¹ SO ₃ M. Wherein R ¹ is selected from the group consisting of a straight or branched alkyl group containing from about 8 to about 24 carbon atoms and an alkylphenyl group containing from about 9 to about 15 carbon atoms in the alkyl group. Represents a hydrocarbon group.
M is a cation-forming salt typically selected from the group consisting of sodium, potassium, ammonium and mixtures thereof.

Preferred synthetic anionic surfactants are water-soluble salts of alkyl benzene sulfonic acids containing 9 to 15 carbon atoms in the alkyl group. Another preferred synthetic anionic group is a water-soluble salt of an alkyl sulfate or an alkyl polyethoxylate ether sulfate, wherein the alkyl group contains about 8 to about 24, or about 10 to about 18 carbon atoms, and It contains from 1 to about 20, preferably from about 1 to about 12 ethoxy groups. Other suitable anionic surfactants are disclosed in U.S. Patent No. 4,170,565.

Nonionic surfactants are conventionally produced by condensing ethylene oxide with a reactive hydrogen atom, such as a hydrocarbon having a hydroxyl, carboxyl, or amide group, in the presence of an acidic or basic catalyst, and Including compounds of the formula:

RA (CH ₂ CH ₂ O) _n H where R is a hydrophobic moiety, A is a group having a reactive hydrogen atom, or n is the average number of ethylene oxide moieties. R typically contains from about 8 to about 22 carbon atoms. The above compounds can also be formed by the condensation of propylene oxide with low molecular weight compounds. n is usually about 2 and about
It fluctuates between 24.

The hydrophobic moiety of the nonionic compound is preferably about 8
Primary or secondary, straight or branched aliphatic alcohols having from about 24 to about 24, more preferably from about 12 to about 20 carbon atoms. A more complete disclosure of suitable nonionic surfactants is described in U.S. Patent No. 4,111,855. Mixtures of nonionic surfactants are desirable.

Zwitterionic surfactants are those in which the aliphatic moiety is linear or branched and one of the aliphatic substituents is about 8%.
Derivatives of fatty quaternary ammonium, phosphonium and sulfonium compounds containing from about 24 to about 24 carbon atoms, with the other substituent containing at least an anionic water-soluble group. Particularly preferred zwitterionic materials are the ethoxylated sulfonic acids and ammonium sulfate described in US Pat. Nos. 3,925,262 and 3,929,678.

Semipolar nonionic surfactants are selected from the group consisting of one alkyl or hydroxyalkyl moiety and from about 8 to about 28 carbon atoms and contain 1 to 3 carbon atoms, and contain from 1 to 3 carbon atoms. Includes water-soluble amine oxides containing two moieties where the carbon atoms are optionally connected in a ring.

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 are widespread in commercial detergents. Preferred anionic synthetic water-soluble sulfonic acids and sulfates have about 8
It has an alkyl group containing from about 22 to about 22 carbon atoms.

Examples of such preferred anionic surfactant salts are the reaction products obtained by the sulfation of _C8-18 fatty alcohols derived from tallow and coconut oil, alkylbenzene sulfones in which the alkyl group contains from about 9 to 15 carbon atoms. Acid glyceryl ether sodium sulfate, fatty acid ether sulfates derived from tallow and coconut oil, sulfuric acid and sulfonic acid coconut fatty acid monoglycerides, and about 8 to about
It is a water-soluble salt of paraffinsulfonic acid having about 22 carbon atoms. For example, sulfonated olefin surfactants as described in more detail in U.S. Pat. No. 3,332,880 may be used. Neutralizing cations of anionic synthetic sulfonates and / or sulfates are represented by common cations widely used in detergent technology, such as sodium and potassium.

In this case, a particularly preferred anionic synthetic surfactant is represented by a water-soluble salt of an alkylbenzene sulfonic acid, preferably a sodium alkylbenzene sulfonate having about 10 to 13 carbon atoms in the alkyl group.

A preferred class of nonionic ethoxylates is represented by the condensation products of fatty alcohols having 12 to 15 carbon atoms with about 4 to 10 moles of ethylene oxide per mole of fatty alcohol. Suitable sp. Ethoxylates in this class, C ₁₂ -C ₁₅ condensation product of oxo alcohols and alcohol per mole 7 moles of ethylene oxide,
Narrow cut C _14-15 oxo alcohol and fat (oxo)
Condensation products of 7 or 9 moles of ethylene oxide per mole of alcohol, condensation products of narrow cut _C12-13 oxo alcohol with 6.5 moles of ethylene oxide per mole of fatty (oxo) alcohol, and ranges from 5 to 8 And _C10-14 coconut fatty alcohol condensation products having a degree of ethoxylation (mol EO / mol of fatty alcohol) within.
Fatty oxo alcohols are mainly linear, but can have a certain degree of branching, particularly short molecular chains such as methyl branches, depending on the processing conditions and the starting olefin.

A degree of branching in the range of 15% to 50% (wt%) is often found in commercial oxo alcohols.

Also preferred nonionic ethoxylate compounds are represented by a mixture of two separate 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. Preferred non-ionic ethoxylate mixtures are
Low ethoxylates as condensation products of up to 50% by weight of branched _C12-15 oxo alcohols with about 3 to 7 moles of ethylene oxide per mole of fatty oxo alcohols, and up to 50% by weight of C _16-19 oxo alcohol and about 8 ~ per mole of branched oxo alcohol
High ethoxylate as a condensation product with 14 moles of ethylene oxide.

Examples of suitable cationic surfactants are of the formula _{R 1 R 2 R 3 R 4} N + X - is a quaternary ammonium compound of the. Here, R ₁ is a C _12-20 alkyl group or a hydroxyalkyl group, R ₂ is a C _1-4 alkyl group or a C _12-20 alkyl group or a hydroxyalkyl group or a C _1-4 hydroxyalkyl group, and R ₃ and R ₄ is each
C _1-4 alkyl group or hydroxyalkyl group or C _6-8
An aryl group or an alkylaryl group, or X ^- is a halogen. Preferred compounds are mono-linear quaternary ammonium compounds (ie, compounds wherein R ₂ is a C _1-4 alkyl group or a hydroxyalkyl group in the above formula).

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

By "stable microemulsion" is meant that, upon standing, micelles or liquid-crystal dispersions are formed that do not immediately separate into separate devices.

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

Gelling agents suitable for use in this case are polymer thickeners, including natural rubber. Suitable natural gums include gum arabic and the like. Suitable polymers are water-soluble polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone,
Poly (ethylene oxide), agarose and other polysaccharides, cellulose derivatives such as methyl-, ethyl-, propyl- and butyl cellulose ethers, cellulose ethers such as butylhydroxybutyl 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, including poly (4-vinyl-phthalic acid) and low molecular weight melamine formaldehyde.

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

In the gelling step, it is necessary to heat the mixture to a temperature above 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 gradually added while maintaining the mixture at the same temperature and stirring. When all of the gelling agent has been added, the mixture is allowed to cool to room 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-methoxyethyl ether), poly (vinyl sulfonic acid) or its sodium salt, poly (4-vinyl-phthalic acid) and low molecular weight melamine form If an aldehyde is used, start with a mixture having an acidic pH prior to the addition of the gelling agent and adjust the pH to neutralize the mixture after the addition of the gelling agent.
To induce gel formation. During this step, the mixture is preferably stirred gently. In this case, in addition to neutralizing the pH, heating the mixture is also recommended.

Also, some gelling agents do not require any additional processing. That is, it is only necessary to 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 amount of the gelling agent to be added is not specified.
In practice, depending on the amount of gelling agent added, the final mixture will have a viscosity in the range from liquid to gel. Ideally, a non-flowing sticky mixture having a rubber-like consistency should be obtained.

Next, the gel is converted to a normal granular detergent composition (base powder).
And the gel formed into small sticky particles by the crushing action is covered with the base powder.

Co-milling refers to any mechanical action of grinding a gel with a base powder or the aforementioned powdered materials.

Any granular detergent composition containing any known component can be used in the present invention. That is, the present invention is not limited to any particular detergent composition. A granular detergent composition refers to any granular composition used to clean a fabric or other material. Such compositions are, for example, EP 0 219 314, EP 0 220
024, EP 0 133 804 and EP 0 124 913.

Thus, a granular detergent composition containing the compound embedded in the microemulsion base gel is obtained.

Since the final appearance of the product depends on the size of the granules, it can be adjusted by changing the grinding parameters.

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

Prior to mixing the gel with the base powder or the aforementioned powdered materials, it may be preferable to first cut the gel into fine pieces to ensure efficient mixing of both components.

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

〔Example〕

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

Example 1 A representative granular detergent composition comprising a microemulsion base gel containing a perfume is prepared as follows.

a. The gel contains the following components: Ingredient weight% water 55 Perfume 30 Linear alkylbenzene sulfonate 5 Gelatin (Bloom strength 240) 10 Mix water and perfume and add surfactant to obtain stable microemulsion.

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

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

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

Anionic surfactant (linear alkylbenzene sulfonate) 6% by weight Fatty acid 1.5 Nonionic surfactant 6 Zeolite (builder) 22 Sodium carbonate 12.5 silicate 4.5 Sodium sulfate 13.0 Soil reprecipitation inhibitor (polymer) 3.0 Perboric acid Salt 18.0 Water 9.0 Others 4.5 Co-mill the gel and base detergent composition at a detergent: gel weight ratio of about 6: 1.

In this way, a granular detergent composition containing about 5% of perfume is obtained.

Example 2 A detergent composition is obtained in the same manner as in the above example except that the gel contains the following components. Ingredient % by weight Perfume 62 Linear alkylbenzene sulfonate 1.5 Water 28 Gelatin (Blues intensity 240) 8.5 Granular detergent and gel are co-ground at a detergent: gel weight ratio of about 6: 1 to obtain about 10% of fragrance perfume The resulting detergent composition is obtained.

Example 3 The same granular detergent as in the previous example and a gel containing:
A detergent composition is obtained by co-milling at a weight ratio of 6: 1. Ingredient % by weight Brightener: Blankophor (Bayer trademark) 9 Linear alkylbenzene sulfonate 4.5 Water 37.5 Oil: Isopar H (Exxon trademark) 41 Gelatin (Bloom strength 240) 8.0 A gel is obtained as follows.

 Mix water and oil, and add brightener.

Introduce a surfactant to obtain a stable microemulsion.

Heat the mixture to about 45 ° C. and add the gelatin with stirring.

 The mixture is allowed to cool with stirring to give a gel.

Claims (11)

(57) [Claims] The microemulsion base gel containing the compound further comprises particles of the compound, the microemulsion base gel containing the compound comprising: 0.5% to 80% by weight of the total composition of the compound; 0.5% to 15% surfactant by weight of the total composition; 10% to 90% water by weight of the total composition; 0% to 80% oil by weight of the total composition; A granular detergent composition containing a usual detergent component, comprising 0.5% to 20% by weight of a gelling agent based on the whole product. 2. The detergent composition according to claim 1, wherein the weight ratio of water to oil is in the range of 1: 4 to 4: 1. 3. The detergent composition according to claim 1, wherein the surfactant is a linear C ₁₀ -C ₁₃ alkylbenzene sulfonate. 4. The detergent composition according to claim 1, wherein the gelling agent is gelatin. 5. The detergent composition according to claim 1, wherein the gelling agent is a polyacrylate. 6. The detergent composition according to claim 1, wherein the compound contained is a fragrance. 7. The detergent composition according to claim 1, wherein the compound contained is a brightener. 8. Mixing water, oil, and compound; b. Adding a surfactant to obtain a stable microemulsion; c. The method for producing a granular detergent composition according to any one of claims 1 to 7, further comprising: adding a gelling agent; and d. Co-milling the gel and the base powder. 9. Mixing water, oil and compound; b. Adding a surfactant to obtain a stable microemulsion; c. Adding a gelling agent; d. Co-milling the gel and the powdered material; e. Co-milling or mixing the product of step d with the base powder. A method for producing the granular detergent composition according to any one of 1 to 7. 10. The method of claim 1 wherein step (c) comprises: adding the gelatin while heating the mixture to about 50 ° C. and stirring; and cooling the mixture to room temperature while stirring. 10. The method according to any of 8 or 9. 11. The method of claim 11, wherein the step c) comprises: adding the polyacrylate while gently stirring the mixture at acidic pH and heating to about 50 ° C .; and neutralizing the pH of the mixture. 10. A method according to claim 8 or claim 9, wherein