JPH101695A - Concentrated liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a concentrated liquid detergent composition, improved in reduction of packaging containers, facility of carrying, a rise in efficiency, etc., of distribution and excellent even in detergency, fluidity, finishing properties of a hydrophobic surface and stability with time. SOLUTION: This concentrated liquid detergent composition is a high- concentration isotropic composition having 40-90wt.% content of the whole surfactants, good in fluidity and further comprising the following components (A), (B) and (C): (A) 10-85wt.% polyalkylene glycol type nonionic surfactant, (B) 5-45wt.% surfactant isotropic agent component, having functions to make the component A isotropic and selected from semipolar, amphoteric and cationic surfactants and (C) 0.0-3wt.% one or more mono- or sesquiterpenic hydrocarbons.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a reduction in the number of packaging containers,
The present invention relates to a concentrated liquid detergent composition having improved detergency, mildness, fluidity, and excellent finish of a hydrophobic surface, which is improved in portability, distribution efficiency, and the like.

[0002]

2. Description of the Related Art Conventionally, surfactants such as lyotropic liquid crystals represented by hexagonal liquid crystals and lamellar liquid crystals have been used in a specific concentration range, generally in a high concentration region, regardless of whether they are ionic or non-ionic. It is known to form a high-viscosity, high-order association structure. For example, one of the representative anionic surfactants, alkyl ethoxy sulfate salt, forms a liquid crystal that has no fluidity in a highly concentrated aqueous solution, and polyethylene, which is a typical nonionic surfactant, Glycol monoalkyl ethers also form highly viscous liquid crystals over a fairly wide concentration range in highly concentrated aqueous systems (Mitchell DJ et al., J. Chem.
Soc., Faraday Trans. 79, 975 (1983)).

[0003] This property is that the conventional surfactant concentration is 5 ~
In the case of a 25% by weight aqueous liquid detergent, there was no effect. However, in recent years, the reduction of packaging containers has led to resource savings, environmental protection, and ease of carrying and use by consumers. In addition, it is a serious problem in realizing a high concentration of a liquid detergent, which has been inevitably required due to needs of the times such as distribution efficiency. That is, when the concentration of the surfactant is increased, a highly viscous high-order association structure having extremely low fluidity is formed, so that the handling properties within the range acceptable to consumers, the dispersibility upon dilution, and the ease of use Still, it was difficult to provide foam performance. In addition, it was impossible to produce such a high-viscosity composition.

[0004] As a method of realizing a detergent composition having a high surfactant concentration, a method of adding a lower alcohol such as ethanol as a hydrotroping agent has been conventionally known, and it is actually used in many liquid detergents. However, hydrotropes composed of such lower alcohols do not have surfactant activity, so if added in an excessive amount, they may impair the original high washing performance and emulsification performance of surfactants. there were. Therefore, there has been a strong demand for the development of a method that can replace the addition of a lower alcohol-based hydrotrope.

However, the formation of such a high-viscosity association phase is a property common to almost all surfactants. Conversely, the formation of a high-viscosity association phase has a hydrophobic group and a hydrophilic group in the molecule, and the formation of micelles and the like. This is a phenomenon derived from the essence of a surfactant, which expresses many functions by forming a coalescence. For this reason, it has been extremely difficult to suppress the formation of this phase while maintaining high surface activity and cleaning performance by a conventionally known method, but development of a new technology that can solve this technical problem has been developed. Was what many researchers and engineers aspired to.

[0006] Polyalkylene glycol type nonionic surfactants are surfactants that are commonly used as detergents and emulsifiers. The polyalkylene glycol-type nonionic surfactant forms micelles that control interfacial properties such as washing in a dilute aqueous solution, but has an optically anisotropic property such as hexagonal liquid crystal and lamellar liquid crystal in a high concentration aqueous solution. It is well known to form lyotropic liquid crystals having high viscosity and poor fluidity. 40 to 70% by weight of a polyalkylene glycol type nonionic surfactant
Hexagonal liquid crystal, which is easy to form in concentrated aqueous solution of, is a kind of infinite aggregate, and a string-like aggregate in which countless surfactant molecules are associated in a cylindrical shape is densely packed in a hexagonal system when viewed in cross section. You are. Since the string-like aggregate can also be spatially entangled, the degree of freedom is very small from the viewpoint of the motility of the system. Therefore, hexagonal liquid crystals have a very high viscosity and no fluidity. on the other hand,
Polyalkylene glycol type nonionic surfactant is 7
A lamellar liquid crystal which is easy to form in a concentrated aqueous solution of 0 to 90% by weight is also a kind of infinite aggregate, in which a myriad of surfactant molecules are spread two-dimensionally in a plate shape, and the flat plate has a hydrophobic base surface. In this case, the hydrophilic base surface faces the hydrophilic base surface, and has a layered structure. The water present in the lamella liquid crystal is very small, and even if it exists, most of it is different from ordinary free water. Also, since the packing between the surfactant molecules is dense, the lamellar liquid crystal also has a very high viscosity.

For this surfactant, a method of adding a lower alcohol such as ethanol as a hydrotrope to break the liquid crystal structure in a high-concentration aqueous solution has been conventionally known. As described above, since it does not have surface activity, when added in an excessive amount, the problem of impairing the high cleaning performance and emulsification performance of the original polyalkylene glycol type nonionic surfactant and the like. there were.

The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems. As a result, the concentrated liquid containing the following two components (A) and (B) as essential components first. A cleaning composition, that is, a polyalkylene glycol type nonionic surfactant which is the component (A) of the present invention, and a polyalkylene glycol type nonionic surfactant which is the component (B) of the present invention. At the time of mixing, the value of the intermolecular interaction parameter β determined by the following formula (1) is as small as -1.0 to 1.0, and the polyalkylene glycol-type nonionic surfactant is formed in a high-concentration aqueous solution. The present invention has proposed a concentrated liquid detergent composition containing at least one or more isotropic agent components having an action of optically isolating a higher-order association structure and having a water content of 50% by weight or less.

Β = ln (αD ₁₂ / χ ₁ D ₁ ) / (1-χ ₁ ) ²

２ ₁ ² ln (αD ₁₂ / χ ₁ D ₁ ) = (1−χ ₁ ) ² ln
[(1-α) D ₁₂ / (1- { ₁ ) D ₂ ]} wherein β is (A) in the mixed micelle in the solution phase.
Is the interaction parameter between the molecule of the polyalkylene glycol-type nonionic surfactant and the molecule of the (B) isotropic agent component, where α is (A) the polyalkylene glycol-type nonionic surfactant in the solution phase. of the total amount of surfactant (B) and isotropic agent, represents the mole fraction of (a) polyalkylene glycol type nonionic surfactant, chi ₁ solves the above equation (2) The required mole fraction of (A) polyalkylene glycol type nonionic surfactant in the total amount of (A) polyalkylene glycol type nonionic surfactant and isotropic agent in the mixed micelles Wherein D ₁ , D ₂ and D ₁₂ are (A) the critical micelle concentration of the polyalkylene glycol type nonionic surfactant, (B) the critical micelle concentration of the isotropic agent, and a mixed system at a predetermined α. of Indicates the critical micelle concentration. ｝

[0009] This concentrated liquid detergent composition exhibits good performance with respect to the detergency of a propylene cup to which artificial fats and oils are adhered, the foaming power by shaking a graduated glass tube, and the mild property by protein denaturation. I do. On the other hand, in the cleaning of hard surfaces such as various dishes, cookware and home-use glass and ceramics which are one practical use of such a detergent composition, in recent years, the conventional foam performance It has been pointed out that there is a problem in the finish of the hydrophobic surface in addition to the cleaning performance and the mild performance. That is, for example, if a polypropylene bat with oil is washed with a sponge soaked in detergent, rinsed and dried as it is, hydrophobic detergent or oil remaining in the polypropylene bat,
Further, the finish of the surface of the bat made of polypropylene may be impaired by the adhesion of the metal salt or the like.
The concentrated liquid detergent was not sufficiently satisfactory with respect to the finish of the hydrophobic surface.

[0010]

The present invention has been widely used in a wide variety of fields such as household goods and chemicals which have solved the above-mentioned problems. In addition, the present invention saves resources by reducing the number of packaging containers, protects the environment and protects consumers. In response to the needs of the times, such as ease of carrying, ease of use, and more efficient distribution, we realized a high concentration of liquid detergents and made effective use of polyalkylene glycol-type nonionic surfactants. A liquid detergent composition having a high concentration and fluidity, in particular, improves the finish of a hydrophobic surface, and is also excellent in detergent performance such as detergency, mildness, fluidity, and stable over time. It is an object to provide a highly concentrated liquid detergent composition.

[0011]

According to the present invention, there is provided a high-concentration isotropic composition having good flowability and having a total surfactant content of 40 to 90% by weight. )component,
There is provided a concentrated liquid detergent composition comprising the component (B) and the component (C). (A) Polyalkylene glycol-type nonionic surfactant 10 to 85% by weight (B) Semipolar surfactant, amphoteric surfactant, and cationic surfactant having an action to make component (A) isotropic. (C) one or more terpene-based hydrocarbons selected from monoterpene-based hydrocarbons and sesquiterpene-based hydrocarbons
0.01 to 3% by weight

That is, the present invention relates to a method for blending the component (B), a isotropic agent having a specific structure and properties, with the component (A), a polyalkylene glycol type nonionic surfactant. The polyalkylene glycol-type nonionic surfactant is destroyed in the lyotropic liquid crystal structure formed in the high-concentration aqueous solution, and after utilizing the isotropic effect of obtaining a high-concentration detergent composition having good fluidity, The concentrated liquid detergent composition containing the component (A) and the component (B) is further mixed with one or more terpene-based hydrocarbons selected from the component (C) monoterpene-based hydrocarbons and sesquiterpene-based hydrocarbons. , 0.01 to 3% by weight and a total surfactant content of 40 to 90% by weight to obtain a high-concentration liquid detergent composition having excellent hydrophobic surface finish. Is It has been made based on the novel finding that.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The first feature of the present invention is that (A) 10 to 85% by weight of a polyalkylene glycol type nonionic surfactant and (B) 5 to 45% by weight of an isotropic agent component. And (C) a liquid detergent composition containing 0.01 to 3% by weight of a terpene-based hydrocarbon as an essential component, wherein the total surfactant content is 40 to 90% by weight. As described above, by setting the total surfactant content to a high concentration of 40 to 90% by weight, various types of tableware that are optically isotropic, have low viscosity, and have high fluidity, and are used at the same time, Excels in foaming and persistence when washing hard surfaces such as glass and ceramics used in cookers and dwellings, and is excellent in cleaning pottery dishes and glass containers, and also reduces distribution costs and packaging materials. Thus, a flowable, high-concentration, isotropic liquid detergent composition having a large effect on environmental preservation can be obtained. In the present invention, as described above, the total surfactant content is 40 to 90% by weight, preferably 50 to 80% by weight, and 60 to 8% by weight.
0% by weight is more preferred.

Further, the second feature of the present invention is that (A)
A combination of the polyalkylene glycol type nonionic surfactant, the (B) isotropic agent component, and the (C) terpene-based hydrocarbon. By blending the component (C) in this manner, for example, the finish of a hydrophobic surface such as a polypropylene surface can be improved,
Moreover, it can be stably maintained over time.

In the present invention, the content of the component (A), which is a main component that exerts the cleaning function of the liquid detergent composition, is from 10 to 85% by weight, preferably from 20 to 60% by weight, more preferably from 20 to 60% by weight. Is 30 to 50% by weight. Also,
The content of the component (B) having the effect of isolating the component (A) is 5 to 45% by weight, preferably 10 to 4% by weight.
0% by weight, more preferably 15 to 35% by weight. . The mixing ratio of (A) the polyalkylene glycol type nonionic surfactant and (B) the isotropic agent component is as follows:
It is particularly preferred that the ratio be 8: 2 to 4: 6. If the content of the component (A) or the component (B) is too low, or if the content is too close to one of the components, the effect of disturbing the orientation of the activator molecules due to mixing is insufficient, so that it is completely optically isotropic. And the viscosity may not be sufficiently reduced. Further, the above-mentioned (C), which has the effect of improving the finish and the stability over time.
The content of the component is 0.01 to 3% by weight, and preferably 0.1 to 2% by weight. The content of the component (C) is 0.
If the amount is less than 01% by weight, the desired improvement in finish cannot be sufficiently exhibited, while if it exceeds 3% by weight, coloring and low-temperature stability are unfavorably deteriorated.

Hereinafter, each component will be described in detail. First, the polyalkylene glycol-type nonionic surfactant component (A) of the present invention is a known surfactant that is commonly used as a detergent or an emulsifier as described above. Specific examples of preferred structures include a polyalkylene glycol type nonionic surfactant represented by the following general formula (1).

Embedded image R ¹ —O— (AO) n—R ² (1) wherein R ¹ is a linear or branched alkyl or alkenyl group having 8 to 18 carbon atoms, preferably It is a linear or branched alkyl group having 10 to 14 carbon atoms, and more preferably an aliphatic hydrocarbon having 9 to 12 carbon atoms.
Specific examples include an octyl group, a decyl group, a dodecyl group, a tetradecyl group and an oleyl group. R ² is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group. AO is a linear or branched oxyalkylene group having 2 to 4 carbon atoms, and an oxyethylene group and an oxypropylene group are particularly preferable. Furthermore, n represents a number of 3 to 25, and 7 to 15
Is particularly preferred. )

Specific examples of the polyalkylene glycol type nonionic surfactant represented by the general formula (1) used in the present invention include polyethylene glycol dodecyl ether having an average degree of polymerization of oxyethylene groups of 5, Polyethylene glycol dodecyl ether having an average degree of polymerization of oxyethylene groups of 10, polyethylene glycol dodecyl ether having an average degree of polymerization of oxyethylene groups of 15, polyethylene glycol dodecyl ether having an average degree of polymerization of oxyethylene groups of 25, and an average of oxyethylene groups Polyethylene glycol decyl ether having a degree of polymerization of 7, polyethylene glycol tetradecyl ether having an average degree of polymerization of oxyethylene groups of 15, polyethylene glycol oleyl ether having an average degree of polymerization of oxyethylene groups of 15,
Dodecyl ether of polyethylene glycol polypropylene glycol copolymer having an average degree of polymerization of oxypropylene groups of 5 and oxyethylene groups of 10, polyethylene glycol monomethyl dodecyl ether having an average degree of polymerization of oxyethylene groups of 5 and oxyethylene group Polyethylene glycol monomethyl dodecyl ether having an average degree of polymerization of 10 and an average degree of polymerization of oxyethylene groups of 15
Polyethylene glycol monomethyl dodecyl ether, polyethylene glycol monomethyl dodecyl ether having an average degree of polymerization of oxyethylene groups of 25, polyethylene glycol monomethyl decyl ether having an average degree of polymerization of oxyethylene groups of 7, and polyethylene having an average degree of polymerization of oxyethylene groups of 15 Glycol monomethyltetradecyl ether, polyethylene glycol monomethyl oleyl ether having an average degree of polymerization of oxyethylene groups of 15, polyethylene glycol polypropylene glycol monomethyl dodecyl ether having an average degree of polymerization of oxypropylene groups of 5, and an average degree of polymerization of oxyethylene groups of 10, and the like. But are not limited to these.

Next, the (B) isotropic agent component used in the present invention will be described. The isotropic agent component (B) used in the present invention has a value of the intermolecular interaction parameter β obtained by the above formula (1) of -1 when mixed with a polyalkylene glycol type nonionic surfactant. It is a compound that is as small as 0.0 to 1.0 and is capable of optically isolating a higher-order association structure formed by a polyalkylene glycol-type nonionic surfactant in a high-concentration aqueous solution.

As described above, in order to collapse the lyotropic liquid crystal structure of (A) the polyalkylene glycol-type nonionic surfactant component, the polyalkylene glycol-type nonionic surfactant molecule and the isotropic agent are used. Not only that the components are well compatible, but also the interaction between the two molecules is very important. That is, if an attractive interaction between both molecules acts strongly, even if there is an effect of disturbing the orientation of the molecules by a geometric steric effect by mixing, even if there is an effect of disturbing the orientation of the molecules by the attractive intermolecular interaction. Since the packing becomes denser, the resulting liquid crystal formation is promoted, the system is not isotropic, the viscosity remains high and the handling properties are not improved. Therefore, in order for the disorder of packing and orientation due to geometric steric effects to act preferentially when mixed, an isotropic agent having a small attractive interaction between molecules is required. This intermolecular interaction is called Rose
n Proposed by MJ et al. (Rosen MJ, J. Colloid Interfac
e Sci., 86, 164 (1982)), which can be estimated by the β parameter, an interaction parameter in micelles formed in a dilute solution. That is, when two different surfactants are mixed, attractive or repulsive interactions occur between the molecules different from those when the same molecules are adjacent to each other, so that the surface adsorption phenomenon and the critical micelle concentration alone Changes occur that cannot be considered from the behavior of the system alone. This change,
When analyzed using the following equations (1) and (2), which are derived based on the Gibbs free energy equation, the interaction between two different molecules is positive for repulsive interaction,
The attractive interaction can be quantified as a negative value, and the stronger the interaction, the larger the absolute value. Therefore, in the present invention, an isotropic agent having no repulsive interaction and having a small attractive interaction is preferable as the compatibility with the polyalkylene glycol-type nonionic surfactant becomes poor, that is, β Those having a small absolute value are preferred.

Β = ln (αD ₁₂ / χ ₁ D ₁ ) / (1-χ ₁ ) ²

２ ₁ ² ln (αD ₁₂ / χ ₁ D ₁ ) = (1−χ ₁ ) ² ln
[(1-α) D ₁₂ / (1- { ₁ ) D ₂ ]} wherein β is (A) in the mixed micelle in the solution phase.
Is the interaction parameter between the molecule of the polyalkylene glycol-type nonionic surfactant and the molecule of the (B) isotropic agent component, where α is (A) the polyalkylene glycol-type nonionic surfactant in the solution phase. of the total amount of surfactant (B) and isotropic agent, represents the mole fraction of (a) polyalkylene glycol type nonionic surfactant, chi ₁ solves the above equation (2) The required mole fraction of (A) polyalkylene glycol type nonionic surfactant in the total amount of (A) polyalkylene glycol type nonionic surfactant and isotropic agent in the mixed micelles Wherein D ₁ , D ₂ and D ₁₂ are (A) the critical micelle concentration of the polyalkylene glycol type nonionic surfactant, (B) the critical micelle concentration of the isotropic agent, and a mixed system at a predetermined α. of Indicates the critical micelle concentration. ｝

The β value of the intermolecular interaction parameter with the polyalkylene glycol-type nonionic surfactant molecule determined by the above formula (1) is small, from -1.0 to 1.0.
In the case where those in the range of 0 are mixed, the polyalkylene glycol-type nonionic interface is formed by the action of geometric randomization without causing attractive interaction that promotes the structuring of the aggregate when mixed. The activator can effectively disrupt higher-order association structures such as lyotropic liquid crystals formed in highly concentrated aqueous solutions.

The isotropic agent component (B) used in the present invention comprises:
Compounds having an alkyl group having 8 to 14 carbon atoms in the molecule are particularly preferred. In that case, the carbon number of the alkyl group is 10
The number is more preferably from 12 to 12, and specific examples include, but are not limited to, an octyl group, a decyl group, a dodecyl group, and a tetradecyl group. If the alkyl group is too short, it may not be completely compatible with the polyalkylene glycol type nonionic surfactant at the molecular level, or the surface activity may be reduced, and functions such as detergency may be impaired. On the other hand, if the length is too long, the attractive interaction between the hydrophobic groups becomes too strong when mixed with the polyalkylene glycol-type nonionic surfactant, so that it does not destroy the higher-order structure of the lyotropic liquid crystal. Rather, they often promote structuring.

As the isotropic agent component (B) used in the present invention, a compound having a sterically bulky polar group containing a nitrogen atom in the molecule is particularly preferred. Specific examples of the polar group include, but are not limited to, an amine oxide group, a carboxybetaine group, a sulfobetaine group, an amidopropylcarboxybetaine group, a trimethylammonium halide group, a pyridinium halide group, and the like. . The driving force in which a polyalkylene glycol-type nonionic surfactant forms a high-viscosity higher-order structure such as a lyotropic liquid crystal is used. Because of the orientation, the polar group of the isotropic agent component (B) is sterically bulky, so that the polyalkylene glycol type nonionic surfactant molecule which forms a lyotropic liquid crystal when mixed is used. This is preferable because the effect of disturbing the orientation is large. Further, the polyalkylene glycol group, which is a polar group of the polyalkylene glycol-type nonionic surfactant, has ether oxygen which has been anionically polarized, so that it strongly hydrates with water in an aqueous solution, and apparently as a polar group, It is known to exhibit cationic behavior (Rosen MJ, J. Colloid Interface Sci., 95, 443).
(1983)). Therefore, when mixed with a molecule having an anionic polar group, the attractive interaction between the molecules acts strongly through water, so that the polyalkylene glycol type nonionic surfactant is used in a highly concentrated aqueous solution. It promotes a higher-order structure of the lyotropic liquid crystal to be formed. Therefore,
(B) The isotropic agent component preferably has a polar group containing a cationically charged nitrogen atom in the molecule.

In the present invention, (B) the isotropic agent component comprises:
Although they can be used alone, they can be used preferably even if two or more kinds are mixed. In that case, the mixing ratio of the two (B) isotropic agent components is 2: 8 to 8:
Particularly preferred is 2. Some specific examples of preferred isotropic agent components used in the present invention are shown below, but the present invention is not limited to these.

In the present invention, an amine oxide derivative represented by the following general formula (2) is a compound that is very preferable as an isotropic agent component.

Embedded image (Where R^ThreeIs an alkyl group having 6 to 13 carbon atoms.
More preferably, it has 6 to 11 carbon atoms. Also, R^FourAnd R^FiveIs
A methyl group, an ethyl group or a hydroxyethyl group,
A methyl group is particularly preferred. Y is a methylene group or
-CH_Two-C (= O) -NH-C_TwoH_Four-, -CH_Two-C
(= O) -NH-C_ThreeH₆-, -CH_Two-C (= O) -N
HC_FourH₈-. The amine oxide derivative represented by the general formula (2) is preferred.
Specific examples include decyldimethylamine oxide,
Dodecyl dimethylamine oxide, tetradecyl dimethyl
Amine oxide, coconut oil alkyl dimethylamine oxy
Sid, dodecyldiethylamine oxide, dodecyldie
Tanolamine oxide, amide ethyl dodecanoate
Tylamine oxide, dodecanoic acid amidopropyl dimethyl
Amine oxide, dodecanoic acid amide butyl diethanol
Lamine oxide and the like.

In the present invention, a betaine derivative represented by the following general formula (3) is also a very preferable compound as an isotropic agent component.

Embedded image (Wherein, R ₆ is an alkyl group having ₆ to 13 carbon atoms, preferably an alkyl group having 6 to 11 carbon atoms.
₇ and R ₈ are a methyl group, an ethyl group or a hydroxyethyl group, and a methyl group is particularly preferred. Y ′ is a methylene group or —CH ₂ —C (＝ O) —NH—C ₂ H
_{4 -, - CH 2 -C (} = O) -NH-C 3 H 6 -, - CH 2
—C (＝ O) —NH—C ₄ H ₈ —. Furthermore, Z
Represents a carboxymethyl group, a 2-carboxyethyl group, 3-
A sulfonylpropyl group or 2-hydroxy- (3-
Sulfonyl) -propyl group. Preferred specific examples of the betaine derivative represented by the general formula (3) include octylcarboxybetaine, dodecylcarboxybetaine, amide amidoethylcarboxybetaine, amidopropylcarboxybetaine dodecanoate, decylsulfobetaine, dodecylsulfobetaine,
Dodecylsulfohydroxybetaine and the like.

Further, in the present invention, a quaternary ammonium salt derivative represented by the following general formula (4) is also a very preferable compound as an isotropic agent component.

Embedded image ^{R 9 -W + · Q -.} (4) ( wherein, R ⁹ is an alkyl group of 8 to 14 carbon atoms, preferably an alkyl group having 8 to 12 carbon atoms also, W
⁺ Represents a trialkylammonium group having 1 to 4 carbon atoms such as trimethylammonium and triethylammonium, or a substituted or unsubstituted pyridinium group, and a trimethylammonium group, a triethylammonium group, a tributylammonium group, and a pyridinium group are particularly preferable. Furthermore, Q ^- is a monovalent anion such as a halogen anion such as chlorine or bromine or a methylsulfate anion. Preferred specific examples of the quaternary ammonium salt derivative represented by the general formula (4) include octyltrimethylammonium chloride, decyltrimethylammonium chloride, dodecyltrimethylammonium chloride, decyltrimethylammonium bromide, dodecyltrimethylammonium bromide, dodecyltriethylammonium Bromide, decyltributylammonium chloride, decylpyridinium chloride, dodecylpyridinium bromide, octylpyridinium methyl sulfate and the like.

As described above, the (A) polyalkylene glycol type nonionic surfactant and the (B) isotropic agent component, which were previously proposed by the present applicant, were mixed with 50% by weight.
The two-component concentrated liquid detergent composition containing the following water as an essential component is optically isotropic, has a low viscosity,
It has high fluidity and demonstrates good performance against the cleaning power of a propylene cup with artificial oil and fat stains, the foaming power by shaking a graduated glass tube, and the mild property by protein denaturation. For example, if a polypropylene vat with oil is washed with a sponge soaked in detergent, rinsed and then dried as it is, adhesion of hydrophobic detergent and oil remaining on the polypropylene vat, as well as its metal salts, etc. Accordingly, there is a problem that the finish of the surface of the bat made of polypropylene is impaired. The concentrated liquid detergent composition of the present invention is optically isotropic and has a low viscosity by the (A) polyalkylene glycol type nonionic surfactant and (B) the isotropic agent component. Without impairing the feature of high fluidity, since (C) a terpene-based hydrocarbon is further added as an essential component, it satisfies the foaming performance, cleaning performance, mildness, and the surface of the polypropylene bat. Excellent finish.

The component (C) used in the present invention includes terpene hydrocarbons selected from monoterpene hydrocarbons and sesquiterpene hydrocarbons contained in vegetable aromatic oils. Examples of the monoterpene hydrocarbon include D- or L-limonene contained in orange oil, lemon oil, etc., α- or β-pinene contained in terpin oil, etc., α-terpineol contained in pine oil, etc. Examples of the sesquiterpene-based hydrocarbon include ferro-oil, clover oil, and kaoliofrain, which are often contained in cananga oil, and sedren. Each of these terpene-based hydrocarbons can be used alone or in combination of two or more. It is possible to mix as it is orange oil, terpin oil and pine oil. Among the terpene-based hydrocarbons of the component (C) of the present invention, D-limonene is particularly preferred from the viewpoint of blending stability. In the present invention, orange oil, terpine oil, and pine oil containing the monoterpene-based hydrocarbon and / or sesquiterpene hydrocarbon as the component (C) can be used as they are.

As described above, the present invention relates to (A) the polyalkylene glycol type nonionic surfactant 10 to 10
85% by weight, (B) 5 to 45% by weight of an isotropic component and (C) 0.01 to 3% by weight of a terpene-based hydrocarbon as essential components, and a total surfactant content of 40 to 90% by weight.
As a result, it is optically isotropic, has low viscosity and high fluidity, and at the same time, maintains detergency, foaming performance and mildness, and has excellent hydrophobic surface finish and stability over time. A highly concentrated isotropic liquid detergent composition is obtained.

Further, the concentrated liquid detergent composition of the present invention comprises:
In addition to the essential components, it is optically isotropic, has low viscosity,
It can be used in combination with other surfactants as long as the characteristic of high fluidity is not impaired. Specific examples include water-soluble amides such as coconut oil fatty acid diethanolamide, palm kernel oil fatty acid monoethanolamide, lauric acid diethanolamide, and oleic acid dimethanolamide. Also, polyoxyethylene sorbitan esters (ethylene oxide addition molar number of 1 to 10) of the C ₆ -C _16, sorbitan esters of C ₆ ~C _16, C ₆ ~C
₁₆ sorbitol esters, C ₆ -C ₁₆ sucrose fatty acid esters, C ₆ -C ₁₆ methyl glucoside esters, C ₆
Methylmannoside esters -C _16, C ethyl glucoside ester of ₆ -C _16, N- methyl glucamides of C ₆ -C _16, cyclic N- methyl glucamide of C ₆ ~C _16, C ₆ ~C
Examples thereof include ₁₆ alkyl glucosides, C ₆ -C ₁₆ alkyl polyglucosides, and C ₆ -C ₁₆ alkyl glyceryl ethers. Furthermore C ₁₀ -C ₁₈ polyoxyethylene alkyl sulfates (ethylene oxide addition mole number 0.5 to 8), alpha olefin sulfonates C ₁₀ -C _18, alkyl benzene sulfonates, C
Alkyl ether carboxylates of _{10 ~C 18,} C _{8 ~C 18}
Acyl amino acid salts and the like. Further, the concentrated liquid detergent composition of the present invention may contain various additives other than the above-mentioned surfactants, if necessary. That is, a compounding agent to be blended in a household detergent within a range not to impair the purpose of the present invention, for example, an inorganic or organic builder, an enzyme, a bleaching agent, a bleaching activator, a humectant, a viscosity modifier, a hydrotropic agent, Preservatives, bactericides, antioxidants, fragrances, water-soluble polymers, water-soluble inorganic compounds, pigments, ultraviolet absorbers,
Etc. can be blended. Here, as the hydrotropic agent, since an excellent effect on the fluidity and low-temperature stability of the composition is obtained, an alcohol-based low-molecular-weight organic compound having a molecular weight of 150 or less, such as ethanol or propylene glycol, is added in an amount of 6% by weight. % Can be used.

[0031]

Next, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

As examples and comparative examples, the compositions shown in Table 1 were prepared using the following compounds, and their optical properties, fluidity, finish on hydrophobic surfaces, and coloring of detergent compositions were prepared. And the low-temperature stability, and the β value between the components (A) and (B) were measured by the following methods. The results are shown in Table 1.

Group A: polyalkylene glycol type nonionic surfactant C ₁₀ EO ₅ : C ₁₀ H ₂₁ O (C ₂ H ₄ O) ₅ H C ₁₂ EO ₁₅ : C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₁₅ H C ₁₂ PO ₃ EO ₁₀ : C ₁₂ H ₂₅ O (C ₃ H ₆ O) ₃ (C ₂ H
₄ O) ₁₀ H B group: isotropic agent component C ₁₂ DMAX: dodecyl dimethylamine oxide C ₁₂ APCBE: amidopropyl carboxybetaine dodecanoate C ₁₀ TMAC: decyl trimethyl ammonium chloride C ₁₂ PBR: dodecyl pyridinium bromide Group C: terpene -Based hydrocarbon D-limonene α-pinene Orange oil: Main component D-limonene Terpin oil: Main component α, β-pinene Kananga oil: Main component α, β-calyolefin Cedarwood oil: Main component cedrene Group D: Hydrotrope agent EtOH: ethanol coconut oil DEA: coconut oil fatty acid diethanolamide C ₁₂ DEA: lauric acid diethanolamide _{C 12 AES 5: C 12 H} 25 O (C 2 H 4 O) 5 SO 3 Na C 14 AOS: C 14 alpha olefin sulfonate Acid sodium salt

<Optical Properties> 5 g of each composition was placed in a 10-ml test tube with a screw opening, set between two polarizing plates with a 90 ° inclination shift, and the state when the light of a fluorescent lamp was transmitted was observed. However, it was determined as follows. Isotropic: There is no ordered structure in the system, so no light passes through and it looks black. Anisotropy: An ordered structure such as hexagonal liquid crystal and lamellar liquid crystal exists in the system, so that the system shows anisotropy, and light appears to shine brightly through a polarizing plate. <Β value> For (A) a polyalkylene glycol type nonionic surfactant, (B) a single aqueous solution of the isotropic agent component, and a mixed aqueous solution of both components at various molar ratios,
The surface tension at various concentrations was measured and the resulting surface tension −
The critical micelle concentration (CMC) was determined from the inflection point of the concentration curve. Next, the values were substituted into the following mathematical expressions (1) and (2) to calculate an interaction parameter: β. The surface tension of each aqueous solution was measured using a pendant drop type surface tensiometer: PD-Z manufactured by Kyowa Interface Science Co., Ltd.

Β = ln (αD ₁₂ / χ ₁ D ₁ ) / (1-χ ₁ ) ²

２ ₁ ² ln (αD ₁₂ / χ ₁ D ₁ ) = (1−χ ₁ ) ² ln
[(1-α) D ₁₂ / (1- { ₁ ) D ₂ ]} wherein β is (A) in the mixed micelle in the solution phase.
Is the interaction parameter between the molecule of the polyalkylene glycol-type nonionic surfactant and the molecule of the (B) isotropic agent component, where α is (A) the polyalkylene glycol-type nonionic surfactant in the solution phase. of the total amount of surfactant (B) and isotropic agent, represents the mole fraction of (a) polyalkylene glycol type nonionic surfactant, chi ₁ solves the above equation (2) Molar of (A) polyalkylene glycol type nonionic surfactant in the total amount of (A) polyalkylene glycol type nonionic surfactant and (B) isotropic agent required in mixed micelle Where D ₁ , D ₂ and D ₁₂ are (A) the critical micelle concentration of the polyalkylene glycol-type nonionic surfactant, (B) the critical micelle concentration of the isotropic agent, and the predetermined α, respectively. Mixed in Indicates the critical micelle concentration of the combined system. (5) <Fluidity> 5 g of each composition was placed in a 10-ml test tube with a screw opening, and the state when the test tube was turned upside down at room temperature was observed. ：: The composition had good fluidity and immediately flowed to the opposite side. Δ: Viscosity was slightly high and flowed slowly. X: There is no fluidity and it does not fall from the upper part of the test tube. <Finishing Property of Hydrophobic Surface> An aqueous solution containing 0.05% of a detergent composition was prepared, and 3 liters of the aqueous solution was 30 cm in diameter.
After putting the mixture into a 12 cm deep vat and compressing the sponge containing air in the liquid at a liquid temperature of 25 ° C. 10 times, the foam was lathered, and then 0.5 g of beef tallow was applied to each of the polypropylene vats. The front surface is rubbed with a sponge 10 times and the back surface is rubbed 5 times, rinsed with running water, and dried to evaluate the finish. Evaluation of finish of hydrophobic surface 5 points: No stain at all. 4 points: Slight dirt. 3 points: The whole is thinly stained. 2 points: Partially thick dirt remains. 1 point: Many stains remain. <Coloring property and low-temperature stability of detergent composition> 80 cc of the detergent composition is placed in a 100 cc sample bottle, and the lid is kept at 5 ° C, and after 4 weeks, its appearance change, liquid separation property, etc. are visually observed. evaluate. ：: Neither appearance change nor liquid separation. ×: Change in appearance or liquid separation is observed.

[0035]

[Table 1- (1)]

[0036]

[Table 1- (2)]

As is clear from Table 1, the concentrated liquid detergent composition of the present invention is optically isotropic, has good fluidity,
Moreover, it can be seen that this is an excellent cleaning composition having excellent finish on the hydrophobic surface. Therefore, the concentrated liquid detergent composition of the present invention is a kitchen detergent, a food detergent, a body shampoo, a shampoo, and other household detergents.
From cleaning agents for skin hair to cleaning agents for hard surfaces,
It is suitable as a multipurpose concentrated liquid detergent for business use, and its volume is significantly reduced compared to conventional products, so it is extremely useful for environmental protection by reducing distribution costs and packaging materials. is there.

[0038]

As described above, the concentrated liquid detergent composition of the present invention comprises (A) 10 to 85% by weight of a polyalkylene glycol type nonionic surfactant, (B) an isotropic agent component 5
-45% by weight and (C) terpene hydrocarbon 0.0
1 to 3% by weight, and the total surfactant content is 40 to 9%.
0% by weight of a very high concentration surfactant composition,
Despite such a high concentration, it is optically isotropic, has a low viscosity, has a high fluidity, and has extremely good handling properties. Therefore, it is very effective in reducing environmental costs by reducing distribution costs and packaging materials, and the (B) isotropic agent component of the present invention comprises (A) a polyalkylene glycol-type nonionic interface. Since it is a compound that does not impair the excellent cleaning performance and emulsification performance, which is the advantage of the activator, and also the hard water resistance, the concentrated liquid detergent composition also exhibits excellent cleaning performance, emulsification performance, and hard water resistance can do. Further, by blending (C) a terpene-based hydrocarbon, the surface finish of the hydrophobic surface is excellent. As described above, the concentrated liquid detergent composition of the present invention has extremely high safety to the environment and the human body, such as kitchen detergents, food detergents, body shampoos, shampoos, and other household detergents. From skin hair cleanser,
Especially for hard surface cleaners, whether for home use or business use,
It can be applied as a versatile concentrated liquid detergent.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tomomichi Okano 1-7-3 Honjo, Sumida-ku, Tokyo Inside Lion Corporation

Claims (1)

[Claims] 1. A high-concentration isotropic composition having good flowability and a total surfactant content of 40 to 90% by weight, wherein the composition comprises the following components (A), (B), and ( A concentrated liquid detergent composition comprising component (C). (A) Polyalkylene glycol-type nonionic surfactant 10 to 85% by weight (B) Semipolar surfactant, amphoteric surfactant, and cationic surfactant having an action to make component (A) isotropic. (C) one or more terpene-based hydrocarbons selected from monoterpene-based hydrocarbons and sesquiterpene-based hydrocarbons
0.01 to 3% by weight