JP2007161915A - Liquid detergent composition containing capsule particles - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition with uniformly and stably dispersed capsule particles in the liquid with the self-thixotropy of the detergent composition and further having high detergent power suitable for a hard surface with favorable storage stability and good appearance. <P>SOLUTION: The liquid detergent composition contains capsule particles with a viscosity ratio of 5 or over at 6 rpm/60 rpm, is composed of (a) 5-30 mass% of a non-soap anionic surfactant, (b) 1-10 mass% of a semipolar surfactant shown by general formula (I), (c) 0.1-10 mass% of an 8-24C straight/branched chain higher alcohol and/or at least one fatty acid, (d) 0.01-20 mass% of the capsule particles, and is characterized by (e) exhibiting 1,000-5,000 mPa s viscosity at 60 rpm of the composition determined by Brookfield viscometer at 25°C. In the formula, R<SB>1</SB>represents an 8-18C, more preferably a 10-14C straight or branched alkyl or alkenyl group, R<SB>2</SB>and R<SB>3</SB>represent each a 1-3C alkyl or hydroxyalkyl group, R<SB>4</SB>represents a 1-4C alkyl group, A represents a group selected from a group of -CONH-, -NHCO-, -COO-, -OCO- or -O- and n represents a number of 0 or 1. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a liquid detergent composition suitable mainly for hard surfaces such as kitchens. More specifically, the thixotropic property of the detergent composition itself enables uniform and stable dispersion of capsule particles in the liquid, and has excellent detergency. The present invention relates to a capsule particle-containing liquid detergent composition having good storage stability and appearance.

In general, kitchen utensils, kitchen utensils, and the surroundings of a sink are usually violently soiled by various stains such as foods and oils, proteins and starch used during cooking. It is desired that these stains be removed as composite stains with various additives as well as surfactants.
There is also a demand for a cleaning composition containing a new active ingredient that cannot be constituted by a surfactant alone, such as a skin conditioning agent that gives a change in scent during cleaning and moisturizes the hand skin.

  However, in order to realize these effects, simply blending the active ingredient directly into the composition causes various adverse effects such as deactivation of the effect due to compatibility and turbidity and separation of the appearance due to incompatibility.

  Therefore, it is known that it is an effective method to include the active ingredient in a solid film that is not compatible with a cleaning composition such as a capsule or a polymer so that the active ingredient can be stably held (for example, patents). Reference 1 and 2). Furthermore, by dispersing and stabilizing such capsule particles, it is possible to draw consumer interest by attracting appearance interest and visually recognizing the appeal effect.

However, in order to constitute a liquid cleaning composition in which capsule particles are dispersed and stabilized as in Patent Documents 1 and 2 above, capsule particles are usually blended in large amounts and dispersed by electrostatic repulsion between the particles, Although we tried to increase the viscosity with a high molecular weight polymer and adjust the capsule specific gravity and liquid specific gravity, these technologies improve the dispersion stability to some extent, but the long-term stability and temperature changes such as sedimentation Non-uniformization occurred and was not sufficient.
Therefore, in order to stabilize the dispersion of particles, it is ideal to impart thixotropic properties to the composition. This “thixotropic property” means that when the shear stress is low or zero, it has a large viscosity, and conversely, when the shear stress is high, the viscosity is low and fluidity as a liquid detergent can be secured. Refers to viscosity characteristics.

In order to impart such viscosity characteristics, examples in which natural or synthetic polymer compounds are used in many capsule particle-containing compositions are disclosed. However, in these capsule particle-containing compositions, although dispersion stability of the particles is improved, the manufacturing process in accordance with the characteristics of the polymer compound is complicated, which is not efficient.
In addition, as described above, these polymer compounds are greatly affected by solutes, and the components and the amount that can be blended are limited, so that it is difficult to improve the oil and fat detergency of the composition itself. Furthermore, with synthetic polymer compounds, safety due to residual monomers is always a problem.

Accordingly, the present inventors have developed a composition capable of imparting shear thinning by forming a lamellar liquid crystal using a non-soap anionic surfactant, a semipolar surfactant such as amine oxide, and a specific oil component. In addition, the capsule particles can be dispersed and stabilized without using a polymer compound, and the above-mentioned problems can be solved while improving the oil and fat detergency by liquid crystal formation.
So far, research has been conducted on detergents using various lamellar liquid crystal states. However, liquid detergent compositions having shear thinning viscosity and liquid detergent compositions due to the properties of liquid crystal molecules that have strong interactions. Few examples have been applied to liquid detergent compositions to which capsule particles have been added.

For example, by blending a primary alcohol sulfate, an alkoxylated nonionic surfactant and a specific electrolyte, it is officially recognized as a stable hard surface detergent including a continuous aqueous phase, a dispersed lamellar phase and a dispersed suspended phase. Structured liquid compositions (see, for example, Patent Document 3) are known.
However, this structured liquid composition is intended to stabilize the dispersion of water-insoluble particles, and does not describe anything about the oil / fat detergency of the composition itself required for a hard surface cleaning composition. The technical idea is different from the present invention.
Further, a cleaning composition suitable as a manual dishwashing composition for the purpose of stabilizing the bead particles and the solubility of the agent is known (for example, see Patent Document 4). The structure of the surfactant itself is not described at all, and the technical idea is different from the present invention.
JP-A-63-137746 (Claims, Examples, etc.) Japanese Patent Laid-Open No. 63-137996 (Claims, Examples, etc.) JP-T 8-501120 (Claims, Examples, etc.) JP 2005-526174 A (Claims, Examples, etc.)

  The present invention has been made in view of the above-mentioned problems of the prior art and intends to solve this problem. The thixotropic property of the cleaning composition itself allows the capsule particles to be uniformly and stably dispersed in the liquid, and is suitable for hard surfaces. An object of the present invention is to provide a capsule particle-containing liquid detergent composition having excellent high detergency and excellent storage stability and appearance.

  As a result of intensive studies to solve the above-described conventional problems, the present inventors have included a specific amount of a non-soap anionic surfactant and a semipolar surfactant such as amine oxide, and a specific oil component. By combining a specific amount of the above, the above-mentioned capsule particle-containing liquid cleaning suitable for a hard surface having a thixotropic property, dispersing and stabilizing the capsule particles, and without deteriorating the storage stability and having a higher detergency The present inventors have found that an agent composition can be obtained and have completed the present invention.

That is, the present invention includes (a) 5-30% by mass of a non-soap anionic surfactant, (b) 1-10% by mass of a semipolar surfactant represented by the general formula (I), and (c) carbon. A linear alcohol / branched higher alcohol having a number of 8 to 24 and / or at least one fatty acid is contained in an amount of 0.1 to 10% by mass, and (d) 0.01 to 20% by mass of capsule particles. (E) Capsule particles characterized in that the viscosity at 60 rpm of the composition measured by a Brookfield viscometer at 25 ° C. is 1000 to 5000 mPa · s, and the viscosity ratio at 6 rpm / 60 rpm is 5 or more. In the liquid detergent composition containing.

  According to the present invention, there is provided a capsule particle-containing liquid detergent composition that has thixotropic properties, uniformly and stably disperses capsule particles in a liquid, has excellent detergency on a hard surface, and has good storage stability and appearance. Is done.

Hereinafter, embodiments of the present invention will be described in detail.
The capsule particle-containing liquid detergent composition of the present invention comprises (a) 5 to 30% by mass of a non-soap anionic surfactant and (b) 1 to 10 mass of a semipolar surfactant represented by the general formula (I). %, (C) 0.1 to 10% by mass of at least one of a higher alcohol and / or a fatty acid having a straight chain / branched structure having 8 to 24 carbon atoms, and (d) capsule particles 0.01 (E) the viscosity at 60 rpm of the composition according to a Brookfield viscometer at 25 ° C. is 1000 to 5000 mPa · s, and the viscosity ratio at 6 rpm / 60 rpm is 5 or more. It is characterized by this.

Examples of the non-soap anionic surfactant (a) used in the present invention include polyoxyalkylene alkyl ether sulfates, alkylbenzene sulfonates, alkyl sulfates, α-olefin sulfonates, and alkyl ether carboxylates. , Alkane sulfonates, α-sulfo fatty acid salts, amide ether carboxylates, sulfosuccinates, amino acid anionic surfactants, and the like. These are at least one (each alone or in combination of two or more). Can be contained. Examples of the salt to be used include metal salts such as sodium, potassium, magnesium and calcium, ammonium salts, and mono-, di- and tri-lower alkanolamine salts.
The reason why the anionic surfactant of the component (a) is limited to the non-soap type is to further exhibit the effects of the present invention in a wide pH range, particularly in a neutral region (pH 5 to 8).

Among these non-soap anionic surfactants of component (a), preferably the hydrophobic group structure is branched / secondary / alkenyl for achieving detergency and viscosity characteristics of the present invention. Those containing at least one sulfuric acid / sulfonic acid type anionic surfactant containing any of the groups are desirable.
More preferably, it contains at least one selected from polyoxyalkylene alkyl ether sulfates, alkyl sulfates, and alkane sulfonates having a branched / secondary alkyl structure. Moreover, from the point of a detergency, Preferably it is C8-C18, More preferably, C10-C16 is desirable. Among these, the most preferred is a polyoxyethylene alkyl ether sulfate having 10 to 16 carbon atoms in order to achieve both detergency and storage stability, and the average added mole number of the oxyethylene group is preferably 0.1. To 5, more preferably 0.3 to 4. Further, the addition molar distribution of the oxyethylene group may be either a narrow distribution as disclosed in JP-A No. 2001-172698 or a wide distribution.

The content of these non-soap anionic surfactants of the component (a) is 5 to 30% by mass (hereinafter simply referred to as “%”) with respect to the total amount of the liquid detergent composition for the purpose of maintaining foam. ), Preferably 8 to 25%, more preferably 10 to 20%.
When the content of the component (a) is less than 5%, the foam persistence is inferior. On the other hand, when it exceeds 30%, the viscosity is increased and the fluidity is lost.

また、上記式（Ｉ）中のＲ¹は、単独のアルキル基又はアルケニル基でもよく、異なるアルキル基又はアルケニル基を有する混合アルキル基又はアルケニル基でもよい。また、その構造は直鎖又は分枝、もしくはそれらの混合でもよい。その炭素数は、洗浄力の点から、好ましくは８〜１６、更に好ましくは１０〜１４が望ましい。また、更なる洗浄力の点からアルキルジメチルアミンオキシド／アルキルアミドプロピルジメチルアミンオキシドが好ましく、特に好ましくは、炭素数が１０〜１４であるアルキルジメチルアミンオキシドを含有することが望ましい。 Examples of the semipolar surfactant of the component (b) used in the present invention include those represented by the following general formula (I), and these can be used alone or in combination of two or more.

R ¹ in the above formula (I) may be a single alkyl group or alkenyl group, or a mixed alkyl group or alkenyl group having different alkyl groups or alkenyl groups. The structure may be linear or branched, or a mixture thereof. The carbon number is preferably 8 to 16 and more preferably 10 to 14 from the viewpoint of detergency. Further, alkyldimethylamine oxide / alkylamidopropyldimethylamine oxide is preferable from the viewpoint of further detergency, and it is particularly preferable to contain alkyldimethylamine oxide having 10 to 14 carbon atoms.

The content of the semipolar surfactant as the component (b) is 1 to 10%, preferably 1 to 8%, and more preferably 2 to 6% with respect to the total amount of the liquid detergent composition. It is desirable.
If the content of component (b) is less than 1%, the detergency cannot be reduced and lamellar liquid crystal cannot be formed. On the other hand, if it exceeds 10%, the viscosity becomes high and the fluidity is lost. Absent.

  In addition, since the semipolar surfactant of the component (b) causes a change in charge depending on the pH and the interaction with the component (a) may change, the pH is preferably in the present invention, It is desirable to adjust to 5.5 to 7.5, and more preferably to 6.0 to 7.0. When the pH is less than 5.5, the interaction with the component (a) is too strong, so that gelation or solidification is likely to occur. When the pH is greater than 7.5, the interaction becomes too weak. A stable lamellar liquid crystal may not be formed.

The component (c) used in the present invention contains a stable lamellar liquid crystal and further improves the detergency, and contains a straight chain / branched structure having 8 to 24 carbon atoms. Higher alcohol and / or at least one fatty acid.
Specifically, commercially available Saffol 23 (manufactured by Sasol, C12 / C13 = 50% / 50%, linearity: 50% (the linearity is the proportion of the linear alkyl alcohol in the raw alcohol) )), Dyadol 13 (Mitsubishi Chemical Corporation, C13: 100%, linearity 50%), Neodol 23 (Shell, C12 / C13 = 40% / 60%, Linearity 80%) Branched and linear mixed primary alcohol, branched primary alcohol such as Isophor 12 (Sasol, C12: 100%) tridecanol (Kyowa Hakko, C13: 100%), 1-decanol, Linear alcohols such as coconut oil higher alcohol, branched / linear secondary alcohols such as 2-decanol, and lauric acid and oleic acid having saturated / unsaturated alkyl chains as fatty acids Linoleic acid, linolenic acid, palmitic acid, stearic acid, at least one of isostearic acid.

Preferably, it is desirable to contain at least one branched or secondary higher alcohol from the viewpoint that the high shear viscosity can be lowered while maintaining the viscosity ratio (further improving the fluidity). Particularly preferably, a branched higher alcohol is more desirable if it has 10 to 16 carbon atoms in terms of detergency. When the number of carbon atoms is less than 8, the effect of improving the detergency is poor and the odor tends to worsen. When the number of carbon atoms exceeds 24, the effect of improving the detergency is poor, and the melting point Therefore, the composition may not be compatible with each other.
Suitable examples include branched and linear mixed primary alcohols such as Saffol 23, Diador 13 and Neodol 23, secondary alcohols such as 2-decanol, and branched types 1 such as Isophor 12 and tridecanol. Grade alcohol is preferred. Particularly preferred are branched primary alcohols such as isophor 12 and tridecanol.

The content of these components (c) is 0.1 to 10%, preferably 0.5 to 5%, more preferably 1 to 3% with respect to the total amount of the liquid detergent composition. desirable.
If the content of component (c) is less than 0.1%, a stable lamellar liquid crystal cannot be formed. On the other hand, if it exceeds 10%, solidification or emulsification occurs, which is not preferable.

  In the present invention, capsule particles are contained as the component (d). The capsule particles suitable for use in the present invention are not particularly limited as long as they are ordinary capsule particles used in a liquid detergent composition, and capsule particles disclosed in many prior arts can be used. Also, the capsule particles as defined herein can be produced using various methods known in the art.

  The method for producing the capsule particles of the component (d) to be used is not particularly limited, and examples thereof include film resin, coating with water repellent powder, encapsulation, microencapsulation, and the like. -Chemical methods such as in situ polymerization method, coacervation method, interfacial precipitation method, submerged drying method, physicochemical method such as orifice method, mechanical method such as spray drying method, dry mixing method, etc. It is done.

  Specifically, a coacervate method in which two types of aqueous colloidal solutions containing an anionic polymer such as gum arabic, alginate, and carboxymethyl cellulose and the other containing a cationic polymer such as gelatin are mixed. For example, the capsule may be a polyurea / polyurethane resin wall film. Examples of the resin film agent for coating include natural polymers such as gelatin, agar, gellan gum, curdlan, sodium alginate, carrageenan, polyvinyl alcohol, sodium polyacrylate, polysodium methacrylate, polymethyl methacrylate, poly Synthetic polymers such as ethyl methacrylate, nylon, urethane, epoxy resin, melamine resin, phenol resin, waxes such as carnauba wax, rice wax, candelilla wax, beeswax, hardened palm oil, hardened rapeseed oil, beef tallow, lard And fats such as hardened soybean oil. These may be used alone or in combination of two or more.

Further, the capsule particles may have any shape. More preferably, the capsule particles are substantially rounded, more preferably substantially spherical.
The capsule particles used in the present invention preferably have an average diameter of 100 to 5000 μm, more preferably 500 to 4000 μm, and most preferably 800 to 3000 μm.
Further, the specific gravity of the capsule particles is preferably as close to the liquid specific gravity as possible from the viewpoint of dispersion stability. In the present composition, the specific gravity of the capsule particles is preferably 0.5 to 1.5, more preferably 0.7 to 1.3 at 20 ° C.

  It is desirable that the capsule particle of component (d) used in the present invention is dissolvable, pulverizable, squeezable, or burstable, and can release any active ingredient carried in the capsule particle. Most preferably, the capsule particles are dissolved by contact with the washing water to be used during washing, or are crushed by friction with the inside of the washing tool and the object to be washed while using the washing tool such as a sponge. Desirably, squeezed or ruptured.

Examples of the contents (core substance) of the capsule particles include fragrances, oil agents capable of skin conditioning, moisturizers, sensory agents, enzymes, and bleaching agents.
As a fragrance | flavor, 1 type, or 2 or more types of the mixing | blending fragrance | flavor containing a synthetic fragrance | flavor and a natural fragrance | flavor from animals and plants, a natural fragrance | flavor, and / or a synthetic | combination fragrance | flavor can be used. For example, as a synthetic fragrance, “Initial fragrance chemistry and product knowledge” written by Motoichi Into in 1996 published by Chemical Industry Daily, 1969 MONTCLAIR, N.I. J. et al. Fragrances described in the publication “STEFEN Arctander” “Perfume and Flavor Chemicals” can be used. As natural fragrances, the fragrances described in “Scent Encyclopedia” edited by Japan Fragrance Association can be used.

  As the oil agent, for example, vegetable oils and fats, animal fats and oils, hydrocarbons, alcohols and esters thereof, peel and fruit oils, silicone, and the like can be used. Among these, examples of preferable skin conditioning agents include aloe vera and oils such as sunflower, aloe vera, grape seed, jojoba.

  Examples include humectants such as glycerin that replenish skin lipids, and vitamins that effectively provide skin nutrients that promote skin health, especially vitamins E and A, and vitamin precursors such as niacinamide.

  Examples of the agent that provides a sensation to the skin surface include menthol and peppermint, frescolate, thymol and the like.

  Examples of the enzyme include Alkalase, Savinase, Esperase, Everase, Cannase, Termamyl, Duramil, and Steinzym (Steinzym). Nordicsk Bioindustry), Maxatase, Maxcal, Maxapem (Genencore).

  Bleaching agents include organic and inorganic compounds that dissolve in water to generate hydrogen peroxide, peroxyacids and salts thereof, and mixtures thereof. Examples of the hydrogen peroxide source include organic peroxides such as alkali metal peroxides and urea peroxides, inorganic peroxides such as alkali metal perborates, percarbonates and perphosphates. . Examples of peroxy acids include organic peracids such as peracetic acid and salts thereof, perbenzoic acid and salts thereof, and inorganic peracids such as persulfates. Among these, sodium percarbonate and sodium perborate are preferable.

Such capsule particles of component (d) may be used singly or in combination of two or more, and it is sufficient to contain an effective amount according to the type and characteristics. In general, it is necessary to be 0.01 to 20% with respect to the total amount of the cleaning composition, preferably 0.1 to 15%, particularly preferably 0.3 to 10% is selected. Is done.
When the content of the capsule particles of the component (d) is less than 0.01%, the content effect cannot be obtained. On the other hand, if the content exceeds 20%, the effect may not change.

  The liquid detergent composition of the present invention has (e) a viscosity at 25 rpm of 60 rpm (25 ° C.) measured by a Brookfield viscometer of 1000 to 5000 mPa · s, and a viscosity ratio of 6 rpm / 60 rpm. (25 ° C.) is required to be 5 or more, and in order to ensure further fluidity as a liquid detergent composition, the viscosity at 60 rpm is preferably 1000 to 4500 mPa · s, more preferably 1000 to 4000 mPa.・ S is desirable.

In the present invention, the “6 rpm / 60 rpm viscosity ratio” is a ratio of the viscosity due to a low shear force of 6 rpm and a high shear force of 60 rpm. The larger this value, the greater the difference in viscosity due to the change in shear rate, that is, a composition having a high viscosity with a low shear force and a low viscosity with a high shear force. A low shearing force, that is, a high viscosity in a state close to static, can give a rich image and a high-class appearance. Moreover, in the particle | grain compounding system, sedimentation of particle | grains can be suppressed. However, high shear force, that is, when trying to take out from a bottle or the like during use, it is very difficult to discharge if the viscosity is as it is, so that viscosity property that can reduce viscosity with high shear force, that is, thixotropy is given. Is very important.
In the present invention, in order to have more preferable thixotropy, it is desirable that the 6 rpm / 60 rpm viscosity ratio is 5.2 or more, more preferably 5.5 or more and 7.0 or less.
If this viscosity ratio is less than 5, not only the thixotropy is lowered, but also phase separation occurs at room temperature, and freezing may occur at a low temperature of -5 ° C.

In the present invention, in order to set the viscosity range of 60 rpm and the viscosity ratio of 6 rpm / 60 rpm to the above range (5 or more), it is important to form a stable lamellar liquid crystal that does not cause separation.
In order to form the stable lamellar liquid crystal, it is desirable to first form the lamellar liquid crystal by the components (a) and (b). The mass ratio of the component (a) and the component (b) (hereinafter described as a / b) is preferably a / b = 1 to 6, particularly preferably a / b = 2 to 5. It is desirable. However, the lamellar liquid crystal containing only the components (a) / (b) causes phase separation (water separation) at room temperature and freezing at −5 ° C. By adding the component (c) to this lamellar liquid crystal, a stable and thixotropic lamellar liquid crystal can be formed. This phenomenon is caused by the strong interaction between the component (a) and the component (b), and the (c) component becomes wedge-shaped and gives flexibility to the densely aligned lamellar liquid crystal. Is considered to have changed to a structure that can be retained. The change of the lamellar liquid crystal can be observed with a polarizing microscope, and a bright image having no regularity can be confirmed only with the components (a) and (b), but by adding the component (c), a typical cross It changes into a Nicole statue. In order to satisfy the thixotropy and high / low temperature stability at the same time, the mass ratio of the component (a), the component (b) and the component (c) [hereinafter a / b / c (a ÷ b ÷ c), and so on] Preferably, a / b / c = 1 to 4, particularly preferably a / b / c = 1 to 3.

The capsule particle-containing liquid cleaning composition of the present invention can contain other components (arbitrary components) in addition to the above components (a) to (d), but the range in which the effects of the present invention are not impaired, particularly the purpose. It is important to make it contain in the range which does not impair the structural viscosity.
Examples of other components that can be used include amphoteric surfactants and inorganic salts.

This amphoteric surfactant and inorganic salt may have an auxiliary effect in exhibiting the viscosity characteristics of the liquid cleaning composition of the present invention, and may be contained to the extent that the target viscosity characteristics are not impaired. it can.
Examples of amphoteric surfactants that can be used include at least one of alkylbetaines, alkylhydroxysulfobetaines, alkylamidopropylbetaines, imidazolium betaines, N-alkylamino acids, and the like.
Examples of inorganic salts include alkali metals such as sodium and potassium, alkaline earth metals such as magnesium and calcium, and transition metals such as manganese and zinc, sulfates, hydrochlorides, nitrates, carbonates and hydroxides. It is done.
In particular, those having a high auxiliary effect, preferably, amphoteric surfactants are preferably alkylbetaines, alkylhydroxysulfobetaines, and alkylamidopropylbetaines, and inorganic salts include sodium, magnesium, calcium, and zinc. Of these, sulfates, hydrochlorides and nitrates are preferred.
The total content of these amphoteric surfactants and inorganic salts is preferably 0 to 8%, more preferably 0 to 5%, based on the total amount of the liquid detergent composition.

In the present invention, it is desirable to contain an organic carboxylic acid as an auxiliary effect in achieving the desired viscosity characteristics. Examples thereof include glycolic acid, citric acid, ascorbic acid, acetic acid, glutamic acid, oxalic acid, fumaric acid, maleic acid, malic acid, MGDA, EDTA, and salts thereof. Preferred are polyvalent carboxylic acids containing two or more carboxyl groups and salts thereof, and particularly preferred are citric acid, MGDA, EDTA and salts thereof. Moreover, you may use these in combination of 2 or more types.
The content of these organic carboxylic acids is preferably 0.5 to 8%, more preferably 1 to 5%, based on the total amount of the liquid detergent composition.

In the present invention, it is further desirable to contain a nonionic surfactant and a hydrotrope from the viewpoint of further detergency and further storage stability at low temperatures.
It should be noted that if these contents are large, molecular aggregates are solubilized and structural viscosity may be lost.
Examples of the nonionic surfactant that can be used include polyoxyalkylene alkyl ether, fatty acid alkanolamide, sorbitan fatty acid ester, polyoxyethylene acyl ester, alkyl polyglycoside, fatty acid glycoside ester, fatty acid methyl glycoside ester, alkyl methyl gluca There may be mentioned at least one kind such as mid.
Examples of the hydrotrope include aromatic sulfonic acids, aromatic carboxylic acids and salts thereof, hydrocarbons having 10 to 16 carbon atoms, monohydric alcohols having 1 to 5 carbon atoms, and polyhydric acids having 4 to 12 carbon atoms. Examples thereof include at least one kind of polyhydric alcohol, polyalkylene glycol having a molecular weight of 200 to 2000, glycerin, sorbitol and the like.

  These nonionic surfactant and hydrotrope component can be contained to such an extent that the intended viscosity characteristics are not impaired. Preferably, the total content is 0 to 0 with respect to the liquid detergent composition. It is 10%, preferably 0 to 8%, and more preferably 0 to 5%.

  Other optional components that can be used include water-insoluble particles such as abrasives, bactericides such as polylysine, glutaraldehyde, benzalkonium chloride, geraniol, pearling agents, plant extracts, pH adjusters, pigments, Antioxidants, fragrances, fragrance solubilizers, and the like can be appropriately contained as long as the effects of the present invention are not impaired. As the solvent, water (purified water, ion exchange water, pure water, ultrapure water, normal water, clean water, etc.) is usually used.

As long as the capsule particle-containing liquid detergent composition of the present invention contains the components (a) to (d) and the viscosity and viscosity ratio of the composition can be set within the above ranges, the production method thereof is It is not specifically limited, For example, it can manufacture with the mixing stirring apparatus using the line mixer which mixes by a batch type to the stirring tank provided with the stirring blade, or mixes and dilutes in-line.
In the present invention, gelation may occur when the non-soap-type anionic surfactant (a) and the semipolar surfactant (b) are directly mixed. Originally, it is generally solubilized with a hydrotrope such as ethanol, alkylene glycol, polyalkylene glycol, etc. However, since such a method may not effectively exert the effects of the present invention, the component (a) This can be avoided by adding a pH adjuster in advance such that the pH after mixing the non-soap anionic surfactant and the semipolar surfactant of component (b) is 5.5 to 7.5. it can. Furthermore, it is also desirable to add the remaining water to the non-soap anionic surfactant as the component (a) and dilute it beforehand in order to prevent gelation. In addition, in the capsule particles of the component (d), if the solid is directly mixed with the other components, foam biting occurs, so it is desirable to mix with water and add it as an aqueous dispersion. It is desirable to add component (c) after stirring them.
As described above, it is desirable to add the remaining water, the component (a), the pH adjuster, the component (b) and, if necessary, the other components with stirring, and then add the component (d) and the component (c).

In this invention comprised in this way, (a) 5-30 mass% of non-soap anionic surfactant, (b) 1-10 mass% of semipolar surfactant shown by general formula (I), (C) 0.1 to 10% by mass of at least one of higher alcohols and / or fatty acids having a straight chain / branched structure having 8 to 24 carbon atoms, and (d) 0.01 to 20 masses of capsule particles. (E) the viscosity at 60 rpm of the composition measured at 25 ° C. by a Brufield field viscometer is 1000 to 5000 mPa / s, and the viscosity ratio at 6 rpm / 60 rpm is 5 or more, Capsule particle-containing liquid detergent composition having thixotropy, uniform and stable dispersion of capsule particles in the liquid, excellent detergency, good storage stability and good appearance can be obtained.
In addition, the capsule particle-containing liquid detergent composition of the present invention is suitable for cleaning hard surfaces such as kitchen utensils and cooking utensils, and functional particles such as abrasives as well as capsule particles. It is also very effective for stabilizing the dispersion.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to the following Example etc.

[Examples 1 to 10 and Comparative Examples 1 to 3]
As the capsule particles, capsule particles A to C obtained by the following production method were used.
Various liquid detergent compositions (the balance was adjusted with purified water, the total amount was 100% by mass) were prepared by the following production method according to the composition shown in Table 1 below.
The various liquid detergent compositions thus obtained were evaluated for the viscosity of 60 rpm, the viscosity ratio of 6 rpm / 60 rpm, the cleaning power, the low temperature dispersion stability, the high temperature dispersion stability, and the structural viscosity of the composition by the following test methods and the like. . These results are shown in Table 1 below. In addition, the compounding quantity of Table 1 is the mass% (100 mass% of total quantity), and the composition adjusted pH 6.7 with the concentrated sulfuric acid (pure reagent).

[Method for producing capsule particles]
(Method for producing capsule A)
A fragrance composition containing 10% by mass of ethyl butyrate, 10% by mass of ethyl caproate, 10% by mass of 1-hexanol, 5% by mass of amyl acetate, and 65% by mass of fragrance A disclosed in JP-A No. 2003-129086. Dissolve 2.3 g of terephthaloyl chloride and 20 g of hexamethylene diisocyanate in 150 g, then disperse in 750 g of an aqueous solution containing 7.5 g of polyvinyl alcohol, add 46 g of 2% aqueous sodium hydroxide at 20 ° C., and stir for 10 minutes. Then, 14 g of hexamethylenediamine was added to the dispersion to obtain capsule particles having a specific gravity of 0.95 to 1.20 and an average diameter of 1000 to 2000 μm.

(Method for producing capsule B)
In 460 g of distilled water, 12 g of gelatin (made by Nitta Gelatin, type CLV, isoelectric point pH 4.9) and 5 g of sodium alginate (manufactured by Kibun Food Chemifa Co., Duck Algin NSPLL) are mixed and dissolved as a membrane material. The mixture was stirred while maintaining at 40 ° C. Next, 53 g of Steinzyme L (manufactured by Novozymes) as a core substance was added to the reaction solution little by little and dispersed sufficiently, and then the pH of this reaction solution was adjusted with acetic acid, phase-separated, and A capsule membrane (coacervate) was deposited on Thereafter, the temperature of the reaction system was adjusted to 30 ° C. to gel the capsule membrane. The pH of the reaction solution was adjusted to 3.8 to make the capsule membrane insoluble in water. Furthermore, the reaction solution temperature was gradually cooled to 10 ° C. to solidify the capsule membrane. The reaction solution and the coacervate were separated by filtration, washed with distilled water at 10 ° C., filtered and dried with cold air (25 ° C.) while rotating on a hemispherical pan in an open system, with a specific gravity of 0.90 to 1 .15, capsule particles having an average diameter of 1000 to 2000 μm were obtained.

(Method for producing capsule C)
11 g of vitamin E and 24 g of edible fat / corn oil were dissolved by heating to 120 ° C., and then cooled to 70 ° C. to prepare an oil phase. Separately, 250 g of gelatin [made by Nitta Gelatin Co., Ltd.] 40 g in 120 g of water was added, heated to 70 ° C. and dissolved to prepare an aqueous phase. Next, the oil phase in the dissolution tank was kept at 70 ° C., and the water phase was added to the oil phase and stirred well to form an O / W emulsion. This O / W emulsion was encapsulated by a submerged curing method and then dried to obtain capsule particles having a specific gravity of 0.90 to 1.10 and an average diameter of 1000 to 2000 μm.

[Manufacturing methods of various liquid detergent compositions]
Purified water (remaining water) and the component (a) were charged into a stirring tank (a 2 L glass beaker equipped with a 45 ° inclined paddle blade with a diameter of 6 cm and a width of 1 cm) and stirred until dissolved. A pH adjuster (concentrated sulfuric acid) was added and stirred, and then component (b) and other components were added and stirred until the whole became uniform. Next, the component (d) dispersed in purified water (concentration 30 to 50% by mass) is mixed, and then the component (c) is added and stirred until the whole becomes uniform and constant viscosity. A cleaning composition was obtained.
In addition, temperature was 25 degreeC and the rotation speed of the stirrer was changed in the range of 400-700 rpm according to the physical property and quantity of a solution.

(Measurement method of 60 rpm viscosity and 6 rpm / 60 rpm viscosity ratio)
The obtained various liquid cleaning compositions were filled in 90 g of PS11 bottles and adjusted to 25 ° C. in a thermostatic bath. Using a Brookfield viscometer, no. A 4-rotor was installed, and a sample solution set at a constant temperature was set. First, the rotation speed of the rotor was set to 60 rpm, and the viscosity after 30 seconds was measured.
Next, the rotation speed was set to 6 rpm, and the viscosity after 300 seconds was measured. The viscosity ratio of 6 rpm / 60 rpm was calculated from the numerical values obtained from these.

(Evaluation method of cleaning power)
3 g of beef tallow was weighed on a frying pan having a diameter of 28 cm, heated for 10 minutes at high heat, and left at 20 ° C. for 6 hours as a severely soiled hydrophobic surface stain. Take 38 g of tap water and 2 g of the detergent composition in a dishwashing sponge of 11.5 cm x 7.5 cm x 3 cm, rub it by hand several times, and then use this contaminated frying pan at 25 ° C in tap water at home. Wash as done. After washing, the rinse was thoroughly rinsed with tap water, and the cleaning power was evaluated based on the following evaluation criteria by the touch feeling when the contaminated surface of the frying pan was touched by hand.
Evaluation criteria:
◎: No matter where the frying pan is touched, there is no oil film, and no oily residue is felt.
○: When the bottom and side surfaces of the frying pan are touched, there is no film due to oil, and no luster due to residual oil is felt, but a slight luster remains at the corners.
Δ: When the bottom surface of the frying pan is touched, there is no film due to oil, and there is no feeling of sliminess due to residual oil, but there is still luster on the sides and corners.
X: It can be seen that the whole frying pan is slippery and oil is clearly remaining.

(Evaluation method for low temperature stability)
90 g of the composition was filled into a 100 ml glass bottle (PS11), and the state when stored in a thermostatic bath at −5 ° C. for 30 days was evaluated according to the following evaluation criteria.
Evaluation criteria:
◎: 6 rpm / 60 rpm viscosity ratio after storage is within −0.2 compared to initial viscosity ratio ○: 6 rpm / 60 rpm viscosity ratio after storage is 5 or more Δ: Partially frozen or partially separated transparent phase (within 3 mm) × : Freezing and separation

(High temperature stability evaluation method)
90 g of the composition was filled in a 100 ml glass bottle (PS11), and the state when stored in a thermostatic bath at 50 ° C. for 30 days was determined according to the following evaluation criteria.
Evaluation criteria:
A: 6 rpm / 60 rpm viscosity ratio after storage is within −0.2 compared to initial viscosity ratio ○: 6 rpm / 60 rpm viscosity ratio after storage is 5 or more Δ: Partially separated transparent phase (within 3 mm) ×: Separated transparent phase Yes

(Evaluation method of capsule particle dispersion stability)
90 g of the composition was filled into a 100 ml glass bottle (PS11), and the dispersion state of the capsule particles when stored in a thermostatic bath at 50 ° C. for 30 days was determined according to the following evaluation criteria.
Evaluation criteria:
○: Uniformly distributed Δ: Sedimentation is observed in the upper layer (less than 10 mm from the upper layer)
×: 10 mm or more settled from the upper layer

(Confirmation of lamellar liquid crystal, observation with polarizing microscope)
The composition was observed at a magnification of 600 using a polarizing microscope under orthogonal polarization conditions to examine whether or not a crossed Nicol image indicating the presence of lamellar liquid crystal appeared, and evaluated according to the following evaluation criteria.
Evaluation criteria:
◎: Crossed Nicols can be seen all over ○: Crossed Nicols can be seen in part △: Crossed Nicols can hardly be seen ×: Crossed Nicols can not be seen at all

* 1 to * 13 in Table 1 are as follows.
* 1: B-AES (2) In sample S-3 disclosed in Japanese Patent Application Laid-Open No. 2001-172698, the alcohol used was Safol 23 (Sasole, C12 / C13 = 55% / 45%, linearity 50% )) C12-13 alkylethoxysulfate sodium having a wide EO distribution range (average EO chain length of 2 mol)
* 2: N-AES (2) In sample S-1 disclosed in Japanese Patent Laid-Open No. 2001-172698, the alcohol used was Neodol 23 (Chell / C12 / C13 = 40% / 60%, linearity 80% )) C12-13 alkylethoxysulfate sodium having a narrow EO distribution width (average EO chain length of 2 mol)
* 3: AOS C14 alpha olefin sulfonic acid Na
* 4: AO Lauryl-N, N-dimethylamine oxide (Lion Corporation)
* 5: Isofol12 branched C12 alcohol (Sasol Corporation)
* 6: Isofol16 branched C16 alcohol (Sasol Corporation)
* 7: Neodol 23 linear branched mixed C12-13 alcohol (manufactured by Shell, C12 / C13 = 40% / 60%, linear ratio 80%))
* 8: LPB lauric acid amidopropyl dimethyl acetate betaine (trade name: Softazoline LPB, manufactured by Kawaken Fine Chemical Co., Ltd.)
* 9: MgSO ₄ magnesium sulfate heptahydrate * 10: AE (8) polyoxyethylene lauryl ether [average EO addition mole number 8 mol Raw material alcohol: Neodol 23 (manufactured by Shell, C12 / C13 = 40% / 60% , Linearity 80%)]
* 11: ZnSO ₄ zinc sulfate heptahydrate * 12: Fragrance Fragrance composition A described in JP-A-2002-327194, Tables 4 to 11
* 13: Pigment Yellow No. 203

  As is apparent from the results of Table 1 above, Examples 1 to 4 containing the components (a) to (d) and having a viscosity of 60 rpm and a viscosity ratio of 6 rpm / 60 rpm by the Brookfield viscometer are within the scope of the present invention. 10 includes capsule particles having a fluid structural viscosity and excellent detergency, low-temperature stability, high-temperature stability, and capsule particle dispersion stability, as compared with Comparative Examples 1 to 3 that are outside the scope of the present invention. It was found to be a liquid detergent composition.

Claims (1)

(A) 5 to 30% by mass of a non-soap anionic surfactant, (b) 1 to 10% by mass of a semipolar surfactant represented by the following general formula (I), and (c) 8 to 24 carbon atoms A linear alcohol / branched higher alcohol and / or 0.1 to 10% by mass of a fatty acid and (d) 0.01 to 20% by mass of capsule particles, (e) Capsule particle-containing liquid detergent composition, characterized in that the viscosity at 60 rpm of the composition measured by Brookfield viscometer at 25 ° C. is 1000 to 5000 mPa · s and the viscosity ratio of 6 rpm / 60 rpm is 5 or more. object.