JP6071722B2 - Liquid composition - Google Patents

Description

  The present invention relates to a liquid composition.

Examples of the liquid composition containing the surfactant include a liquid cleaning agent for textile products.
In liquid detergents for textile products, those using a nonionic surfactant as a main cleaning component and those using a combination of a nonionic surfactant and an anionic surfactant are widely used.
In recent years, due to the growing awareness of environmental issues, the size of the detergent container has been reduced for the purpose of reducing the amount of waste. Along with this, the liquid detergent has been concentrated (higher concentration of surfactant). ) Is progressing. On the other hand, some liquid detergents for textile products have a low surfactant concentration. For example, a liquid bleach that is a representative product that assists in washing performance in washing can be mentioned.

Examples of the method of using the liquid cleaning agent for textile products include a method of performing a cleaning process on the entire clothing or a method of applying the cleaning process to a soiled part of a laundry object.
When the liquid cleaning agent is applied to a soiled part and used, it is important that the retention of the liquid cleaning agent at the application part is good in order to enhance the effect of the application cleaning property.
At this time, in a composition having a high surfactant concentration, the viscosity can be easily increased, so that it is easy to realize good retention at the application site of the composition. However, since it is difficult to increase the viscosity of a composition having a low surfactant concentration, there is a problem that it is difficult to improve the retention at the application site of the composition.

In order to solve this problem, the following methods (1) to (5) have been proposed.
(1) A method of using a polymer compound as a component for increasing viscosity (thickener) (see, for example, Patent Document 1),
(2) A method using a specific aromatic compound as a thickener (see Patent Document 2),
(3) A method using a nonionic surfactant whose HLB is limited to a very narrow range (see Patent Document 3),
(4) A method of using two types of specific nonionic surfactants together (see Patent Document 4),
(5) A method of using a specific nonionic surfactant and an anionic surfactant in combination at a specific ratio (see Patent Document 5).

JP 11-193399 A JP 2004-256714 A JP 2001-288497 A JP 2001-181695 A JP-A-11-293283

However, in the methods as described in Patent Documents 1 to 5, in order to increase the viscosity of a liquid composition having a low surfactant concentration, a low versatility raw material is required, or a liquid accompanying aging. It is difficult to ensure stability, and there is a problem that separation or the like is likely to occur particularly under high temperature (40 ° C. or higher) or low temperature (−5 ° C.) storage conditions.
The present invention has been made in view of the above circumstances, and in a composition having a low surfactant concentration, the viscosity can be easily increased by utilizing a highly versatile raw material, and the storage stability is good. It is an object to provide a liquid composition.

As a result of intensive studies, the present inventors provide the following means in order to solve the above problems.
That is, the liquid composition of the present invention comprises 1% by mass or more and 10% by mass of (a) component: a nonionic surfactant represented by the following general formula (a-1) and having an HLB of 10.5 to 13.5. %, (B) component: an anionic surfactant, (c) component: a water-soluble divalent metal salt, and the mass ratio represented by (a) component / (b) component is 1. ~ 6.

［式中、Ｒは炭素数８〜１８のアルキル基又はアルケニル基を示し、ｎはオキシエチレン基の平均繰返し数を示す。］

[Wherein, R represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, and n represents the average number of repeating oxyethylene groups. ]

  The liquid composition of the present invention has a composition having a low surfactant concentration, and can easily increase the viscosity by utilizing a highly versatile raw material, and has good storage stability.

<Liquid composition>
The liquid composition of the present invention comprises (a) component: a nonionic surfactant having an HLB of 10.5 to 13.5 represented by the general formula (a-1), and (b) component: an anionic interface. Contains an activator and component (c): a water-soluble divalent metal salt.
This liquid composition exhibits a viscosity higher than that in the composition in which the component (c) is not blended (not blended) from the liquid composition, preferably easily exhibits a viscosity of 2 times or more, and The viscosity can be 10 times or more.
The use of the liquid composition is not particularly limited, for example, for textile products, for kitchens for processing dishes and vegetables, etc .; for hard surfaces for processing toilets, walls, bathrooms, etc .; For example, the human body for treating hair or the like. Among them, it is useful as a liquid detergent for textile products, and specifically, a liquid detergent for clothes, a liquid bleach for clothes, a liquid pretreatment laundry aid for clothes (for example, a water-soluble film made of polyvinyl alcohol, etc. It is useful for liquid capsule detergents or laundry aids wrapped in a film typified by Among these, it is particularly useful for liquid bleach for clothing, and is most useful for liquid bleach for clothing containing hydrogen peroxide. The liquid composition of the present invention has good retention at the application site. For this reason, by applying the liquid composition of the present invention directly on the soiled part of the laundry object, the effect of the application cleaning property is enhanced. In addition, in the liquid capsule type formulation wrapped in the film, the viscosity of the liquid inside the capsule is high, so that the liquid viscosity observed when the shear rate with respect to the solution is low and high, respectively, is greatly different (thixotropic) Since the liquid leakage caused by the deterioration or dissolution of the film surface can be suppressed, it is preferable.

((A) component: specific nonionic surfactant)
The component (a) in the present invention is a nonionic surfactant represented by the following general formula (a-1) and having an HLB of 10.5 to 13.5.

［式中、Ｒは炭素数８〜１８のアルキル基又はアルケニル基を示し、ｎはオキシエチレン基の平均繰返し数を示す。］

[Wherein, R represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, and n represents the average number of repeating oxyethylene groups. ]

In the formula (a-1), the alkyl group and alkenyl group in R may be linear or branched. Of these, R is preferably a linear or branched alkyl group.
The alkyl group and the alkenyl group in R have 8 to 18 carbon atoms, preferably 10 to 16 carbon atoms, and more preferably 12 to 14 carbon atoms.

In the formula (a-1), n represents the average number of repeating oxyethylene groups _(CH 2 CH 2 O).
n is preferably 5 to 9, more preferably 5.5 to 8.5, still more preferably 6 to 8, and most preferably 6 to 7.
The component (a) is a mixture of molecules having different (CH ₂ CH ₂ O) repeating numbers, as can be seen from the fact that n represents the average number of repeating oxyethylene groups.

In addition, from the viewpoint of the usefulness of the present invention, among the components (a), a narrow ratio indicating a distribution ratio of a compound (ethylene oxide adduct) having a different number of repeating oxyethylene groups is less than 50% by mass. Preferably, it is less than 45% by mass, more preferably 20% by mass or more and less than 45% by mass, particularly preferably 25% by mass or more and less than 45% by mass, and 30 to 45% by mass. Is most preferred.
In the case of using the component (a) having a narrow ratio of less than 45% by mass and a composition having a low surfactant concentration, it has heretofore been difficult to increase the viscosity. Therefore, the present invention is particularly useful when the component (a) having a narrow rate of less than 45% by mass is used.

  In the present specification, the “narrow ratio” refers to a value represented by the following formula (S) indicating the distribution ratio of ethylene oxide adducts having different numbers of repeating oxyethylene groups, that is, the number of moles of ethylene oxide added.

［式中、ｐ_ｍａｘは全体のエチレンオキシド付加体中に最も多く存在するエチレンオキシド付加体のエチレンオキシドの付加モル数を示す。ｉはエチレンオキシドの付加モル数を示す。Ｙｉは全体のエチレンオキシド付加体中に存在するエチレンオキシドの付加モル数がｉであるエチレンオキシド付加体の割合（質量％）を示す。］

[ _Wherein , p _max represents the number of moles of ethylene oxide added in the ethylene oxide adduct most abundant in the entire ethylene oxide adduct. i represents the number of moles of ethylene oxide added. Yi represents the ratio (% by mass) of the ethylene oxide adduct having an i added mole number of ethylene oxide present in the entire ethylene oxide adduct. ]

For example, when p _max = 6 and the ratio of the ethylene oxide adduct having n in the range of 4 to 8 in the general formula (a-1) contained in the whole component (a) is 35% by mass, The narrow rate is 35% by mass.
The narrow rate of the component (a) can be controlled by, for example, the method for producing the component (a). Specifically, as a production method thereof, a method in which an alkylene oxide is addition-polymerized to an alcohol or a fatty acid alkyl ester using a surface-modified composite metal oxide catalyst (JP 2000-144179 A, JP 2000-061304 A). No. gazette).

The HLB of the component (a) is 10.5 to 13.5, preferably 11 to 13.5, more preferably 11.5 to 13, and further preferably 11.5 to 12.5.
When the HLB of the component (a) is out of the range of 10.5 to 13.5, it is difficult to obtain the effect of increasing the viscosity of the liquid composition.
In addition, when the liquid bleaching agent is used, particularly when washing is performed by application, if the HLB of the component (a) is less than 10.5, the solubility in water is lowered, and the washing performance may be lowered. Alternatively, the initial appearance is deteriorated, white turbidity occurs at a low temperature, or separation occurs at a high temperature, which is not preferable in terms of the appearance of the product. On the other hand, when the HLB of the component (a) exceeds 13.5, the affinity for oil stains is lowered, and the cleaning performance tends to be lowered.
As an example, the component (a) includes those in which R in the formula (a-1) is an alkyl group having 12 carbon atoms (C12), those in which R is an alkyl group having 14 carbon atoms (C14), In the formula (a-1), when n is 5, the HLB is 10.5, and when n is 6, the HLB is 11. When 5, n is 7, HLB is 12.3, when n is 8, HLB is 12.9, and when n is 9, HLB is 13.4.
In the present invention, "HLB of nonionic surfactant" C. Values are shown using the method by Griffin (for details, see J. Soc. Cosmetic Chemists, 1949, page 1 311). In polyoxyethylene alkyl ether, it is calculated | required by following Formula: HLB = mass fraction (%) / 5 of an oxyethylene group.
When using 2 or more types of (a) component, it shall require that the average value of those HLB exists in the range of 10.5-13.5.

(A) A component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
In the liquid composition, the content of the component (a) is 1% by mass or more and less than 10% by mass, preferably 1% by mass or more and less than 8% by mass, more preferably 1% by mass or more and less than 5% by mass. It is particularly preferably 1.5% by mass or more and less than 4% by mass.
In the present invention, when the content of the component (a) is less than 10% by mass, the viscosity of the composition having a relatively low surfactant concentration is easily increased in total with the content of the component (b). be able to.
When the content of the component (a) is 1% by mass or more, the effect of increasing the viscosity is obtained. In addition, for example, when cleaning is performed by application using a liquid bleaching agent, high cleaning performance is exhibited against stains and the like.

((B) component: anionic surfactant)
The component (b) in the present invention is an anionic surfactant. By using the component (b) in combination with the component (a) and the component (c), the effect of increasing the viscosity can be obtained.
Examples of the component (b) include alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, olefin sulfonate, alkane sulfonate, saturated fatty acid salt, unsaturated fatty acid salt, Examples include alkyl ether carboxylates, alkenyl ether carboxylates, α-sulfo fatty acid salts, α-sulfo fatty acid ester salts, and the like.
Among these, alkylbenzene sulfonates are more preferable, and among them, alkylbenzene sulfonates having 10 to 20 carbon atoms are particularly preferable.
(B) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.

In the present invention, “mass ratio represented by component (a) / component (b)” represents the ratio of the mass of component (a) to the mass of component (b) in the liquid composition.
In the liquid composition of the present invention, the mixing ratio of the component (a) to the component (b) is such that the mass ratio represented by the component (a) / component (b) is 1 to 6, preferably 1.25. It is -5, More preferably, it is 1.25-3.5, More preferably, it is 1.25-2.5, Most preferably, it is 1.5-1.75.
When the mass ratio represented by the component (a) / component (b) is 6 or less, the effect of increasing the viscosity is easily obtained. In addition, separation with time is less likely to occur, and the storage stability of the liquid composition is increased. On the other hand, when the mass ratio represented by the component (a) / component (b) is 1 or more, transparency of the appearance of the liquid composition is easily ensured.

In the liquid composition, the content of the component (b) is preferably 0.3 to 7% by mass, more preferably 0.5 to 5% by mass, and particularly preferably 1 to 4% by mass.
When the content of the component (b) is less than the preferred lower limit value, it is difficult to obtain the effect of increasing the viscosity. In addition, separation may occur particularly under high temperature storage conditions. On the other hand, even if the preferable upper limit is exceeded, the effect of increasing the viscosity is hardly changed, and it is not preferable in that the surfactant concentration becomes high.

Further, the total amount of the surfactant in the liquid composition of the present invention is preferably 1.5% by mass or more, more preferably 2% by mass or more, and the upper limit is preferably 10% by mass or less, more preferably 10% by mass. %, More preferably 7.5% by mass or less, particularly preferably 5% by mass or less, and most preferably less than 5% by mass.
In view of the fact that it has been difficult to increase the viscosity of a composition having a low surfactant concentration so far, the present invention is particularly useful in a composition in which the total amount of the surfactant is not more than a preferable upper limit.
When the total surfactant amount is at least the preferred lower limit value, the effect of increasing the viscosity is easily obtained, and the usability at the time of coating becomes better. In addition, the staying property at the application site is increased. For example, when a liquid bleaching agent is used, the cleaning performance is further improved.

((C) component: water-soluble divalent metal salt)
In the present invention, the component (c) is a water-soluble divalent metal salt and serves as a thickener (viscosity modifier). Further, the combined use of the component (c) increases the cleaning power in addition to the increase in the viscosity of the liquid composition.
Examples of the divalent metal constituting the component (c) include magnesium, calcium, zinc, and the like, and magnesium is preferable because the effect of increasing the viscosity is higher. In addition, when hydrogen peroxide is blended, magnesium is preferable from the viewpoint of improving the stability of hydrogen peroxide in the liquid composition.
Examples of the component (c) include inorganic salts of divalent metals.
Specific examples of inorganic salts of divalent metals include divalent metal sulfates, hydrogen sulfates, phosphates, hydrogen phosphates, carbonates, hydroxides, and chlorides.

  Specific examples of the component (c) include magnesium sulfate, magnesium hydrogen sulfate, magnesium phosphate, magnesium hydrogen phosphate, magnesium hydroxide, magnesium chloride, basic magnesium carbonate, and other water-soluble magnesium inorganic salts; calcium hydroxide, Water-soluble calcium inorganic salts such as calcium carbonate, calcium bicarbonate, calcium nitrate, calcium chloride, calcium sulfate, calcium phosphate; zinc nitrate, zinc sulfide, zinc sulfate, zinc chloride, zinc phosphate, zinc cyanide, zinc perchlorate And water-soluble zinc salts. Among these, a water-soluble magnesium inorganic salt is preferable, and magnesium sulfate is particularly preferable from the viewpoint of the effect of increasing viscosity and cost.

(C) A component may be used individually by 1 type and may be used in combination of 2 or more types as appropriate.
In the liquid composition, the content of the component (c) is preferably 0.01 to 1% by mass.
In view of obtaining a higher effect of increasing the viscosity, the content of the component (c) is preferably 0.05% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.25% by mass or more. Especially preferably, it is 0.30 mass% or more, Most preferably, it is 0.35 mass% or more.
On the other hand, the content of the component (c) is preferably 0.75% by mass or less from the viewpoint of ensuring the transparency of the appearance of the liquid composition and suppressing separation under high temperature or low temperature storage conditions. Preferably it is 0.65 mass% or less, More preferably, it is 0.60 mass% or less, Most preferably, it is 0.55 mass% or less.

In the present invention, “(b) component / molar ratio represented by divalent metal” means the ratio of the number of moles of component (b) to the number of moles of divalent metal derived from component (c) in the liquid composition. Represents.
In the liquid composition of the present invention, the mixing ratio of the component (b) and the component (c) is preferably 0.5 to 4, more preferably 0 in terms of the molar ratio represented by the component (b) / divalent metal. .9 to 2.5, and more preferably 1.3 to 2.
When the molar ratio represented by (b) component / divalent metal is not less than the preferred lower limit, separation with time is less likely to occur, and the storage stability of the liquid composition is enhanced. On the other hand, when the molar ratio is less than or equal to the preferable upper limit value, the effect of increasing the viscosity is easily obtained.

(solvent)
The liquid composition of the present invention preferably contains water as a solvent from the viewpoints of ease of preparation, solubility in water when used, and the like.
The water to be used is preferably ion-exchanged water or distilled water from which metal ions such as heavy metals dissolved in water are removed from the viewpoint of stability over time of the liquid composition, and a liquid bleach containing hydrogen peroxide. Is particularly preferred.
In the liquid composition, the content of water is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 85 to 95% by mass with respect to the total mass of the liquid composition.
If the water content is at least the preferred lower limit, the liquid stability of the liquid composition with time will be better, while if it is less than the preferred upper limit, it will be good from the viewpoint of usability.

As the solvent, in addition to water, a water-miscible organic solvent may be used.
“Water-miscible organic solvent” refers to an organic solvent that dissolves 50 g or more in 1 L of ion-exchanged water at 25 ° C. The water-miscible organic solvent is not particularly limited as long as it becomes a uniform solution when mixed with water, and among them, a monohydric alcohol having 2 to 4 carbon atoms, a polyhydric alcohol having 2 to 4 carbon atoms, and glycol. Examples include ether.
Examples of the monohydric alcohol having 2 to 4 carbon atoms include ethanol, 1-propanol, 2-propanol, 1-butanol and the like.
Examples of the polyhydric alcohol having 2 to 4 carbon atoms include ethylene glycol, propylene glycol, butylene glycol, glycerin and the like.
Examples of the glycol ether include ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether and the like.

(Optional component)
In the liquid composition of the present invention, other components other than the components (a) to (c) described above may be blended depending on the application within a range not impairing the effects of the present invention.
Other components are not particularly limited, and include sequestering agents, hydrogen peroxide, radical trapping agents, thickeners other than component (c), pH adjusters, surface actives other than components (a) and (b). Agents, stabilizers, function-imparting agents, bleaching agents other than hydrogen peroxide, bleach activators, soil release agents, dispersants, recontamination inhibitors, fluorescent agents, solvents, and fragrances.

-(D) component: Metal sequestering agent In the liquid composition of this invention, it is preferable to further contain (d) component: Metal sequestering agent. By containing the component (d), the separation of the liquid composition under storage conditions on the high temperature side or the low temperature side is further suppressed. The blending of the component (d) is particularly useful when the temperature during storage is higher, and even under storage conditions on the higher temperature side, separation of the liquid composition is suppressed, resulting in longer-term liquid stabilization. It is valid. Further, when a liquid bleach containing hydrogen peroxide is used, the stability of hydrogen peroxide is further improved.
Examples of the component (d) include the following (d1) to (d7).
(D1) a phosphoric acid compound selected from phosphoric acid, tripolyphosphoric acid, phytic acid and salts thereof;
(D2) ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethanehydroxy-1,1,2-triphosphonic acid, ethane- A phosphonic acid compound selected from 1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid and salts thereof;
(D3) a phosphonocarboxylic acid compound selected from 2-phosphonobutane-1,2-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, α-methylphosphonosuccinic acid and salts thereof,
(D4) an amino acid compound selected from aspartic acid, glutamic acid, glycine and salts thereof;
(D5) nitrilotriacetic acid, iminodiacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, 2-hydroxyethyliminodiacetic acid, triethylenetetraaminehexaacetic acid, An aminopolyacetic acid compound selected from diencoric acid and salts thereof,
(D6) an organic acid selected from diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid and carboxymethyltartaric acid, or Its salt,
(D7) Aminopoly (methylenephosphonic acid), polyethylenepolyaminepoly (methylenephosphonic acid) or a salt thereof.

Among these, as the component (d), (d2), (d5), (d6), and (d7) are more preferable, and among them, ethane-1,1-diphosphonic acid, ethane-1,1,2- More preferred are triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid; citric acid; ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminediacetic acid, 2-hydroxyethyliminodiacetic acid, or sodium salts thereof.
In the case of a liquid bleach containing hydrogen peroxide, (d2) is preferred as the component (d), and ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane- 1-hydroxy-1,1-diphosphonic acid is particularly preferred.

(D) A component may be used individually by 1 type and may be used in combination of 2 or more type as appropriate.
In the liquid composition, the content of the component (d) is preferably 0.01 to 1% by mass, more preferably 0.1 to 0.9% by mass, and still more preferably 0.1 to 0.5% by mass. %, Particularly preferably 0.15 to 0.4% by mass, and most preferably 0.2 to 0.35% by mass.
When the content of the component (d) is less than the preferred lower limit, separation tends to occur under high temperature side or low temperature side storage conditions. On the other hand, when the content of the component (d) exceeds the preferable upper limit value, the effect of increasing the viscosity tends to be difficult to obtain. In addition, in a liquid bleach containing hydrogen peroxide, the amount is excessive in order to suppress decomposition of hydrogen peroxide, and in addition, it is not preferable from the viewpoint of cost.

-(E) component: Hydrogen peroxide In the liquid composition of this invention, bleaching performance is provided by containing (e) component. The liquid composition containing the component (e) has an increased viscosity, whereby the residence time of the liquid composition in the coating part becomes longer and the bleaching effect is further enhanced.
In the liquid composition, the content of the component (e) is preferably 0.1 to 10% by mass from the viewpoint of enhancing the bleaching performance, particularly improving the bleaching effect during washing by coating.

-Radical trap agent As a radical trap agent which can be used for the liquid composition of this invention, Preferably a phenol type radical trap agent is mentioned.
In particular, in a liquid bleach containing hydrogen peroxide, it is preferable to use a phenol-based radical trapping agent together with the component (d) because decomposition of hydrogen peroxide is sufficiently suppressed when the pH is 5 or more. . Moreover, when a liquid bleaching agent is applied to clothing or the like due to misuse or the like and is left for a long time, damage to clothing or the like is suppressed by containing a phenol-based radical trapping agent.
The phenol radical trapping agent is phenol or a phenol derivative. Preferable examples of the phenol derivative include a compound having a phenolic OH group, an ester derivative of a phenolic OH group, an ether derivative of a phenolic OH group, and the like. Note that a substituent may be bonded to the benzene ring, and the substitution position may be any of the ortho position, the meta position, and the para position.
The “ester derivative of a phenolic OH group” refers to a compound having an ester group formed by an ester reaction of a hydrogen atom of a phenolic OH group with a fatty acid having about 1 to 3 carbon atoms.
The “etheric derivative of a phenolic OH group” is a group in which a hydrogen atom of a phenolic OH group is substituted with an aryl group such as an alkyl group having 1 to 5 carbon atoms or a phenyl group to form an ether bond The compound which has is shown.
Especially, as a radical trap agent, the phenol type radical trap agent which has a phenolic OH group is more preferable. Among them, a more preferable one is that the redox potential (OP) ₀ described in “GE Penketh, J. Appl. Chem”, pages 7,512 to 521 (1957) is 1.25V. The following compounds are particularly preferred, and are compounds of 0.75 V or less. Among these, dimethoxyphenol, catechol, hydroquinone, 4-methoxyphenol, dibutylhydroxytoluene (BHT) and the like are preferable, and 4-methoxyphenol is most preferable.
In the liquid composition, the content of the radical trapping agent is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass, from the viewpoints of hydrogen peroxide decomposition inhibitory effect and economy. It is.

-Thickener In the liquid composition of this invention, you may use thickeners other than (c) component.
Examples of the thickener include carboxylic acid polymers such as polyacrylic acid, acrylic acid-maleic acid copolymer, acrylic acid-methacrylic acid copolymer, carboxyvinyl polymer; polyalkylene glycol such as polyethylene glycol or polypropylene glycol or the like Alkyl esters; xanthan gum, guar gum, carboxymethylcellulose, methylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, hydroxybutylmethylcellulose, cationized cellulose, xylose polyvinyl alcohol, and other natural sugar polymers; poly (N-vinylacetamide), Examples thereof include polyurethane.
However, in the present invention, a thickener other than the component (c) may not be used from the viewpoint of ease of securing liquid stability (viscosity change due to aging decomposition of the thickener during storage, etc.). preferable.

-PH adjuster The pH adjuster which can be used for the liquid composition of this invention is not specifically limited, Inorganic acids, organic acids, such as hydrochloric acid and a sulfuric acid; Potassium hydroxide, sodium hydroxide, ammonia or its derivative, alkanol Examples include bases such as amines (monoethanolamine, diethanolamine, triethanolamine, etc.), sodium carbonate, and potassium carbonate.
Of the bases, sodium hydroxide is preferred. Among the acids, inorganic acids are preferable from the viewpoint of the effect of increasing viscosity, and sulfuric acid is particularly preferable among them.
A pH adjuster may be used individually by 1 type, and may be used in combination of 2 or more types as appropriate.
In addition, in the liquid bleach containing hydrogen peroxide, when a compound containing chloride ions such as hydrochloric acid is blended, the concentration of chloride ions in the liquid bleach is 0 from the viewpoint of hydrogen peroxide stability. 0.02% by mass or less is preferable.

The pH of the liquid composition of the present invention is preferably 1 to 6.5, more preferably 2 to 6, even more preferably 2 to 5.5, and particularly preferably 2.5. ~ 5, most preferably 2.5-4.5.
If the pH of the liquid composition is less than the preferred lower limit, separation tends to occur under storage conditions on the high temperature side, and the effect of increasing viscosity may be difficult to obtain. On the other hand, when the pH of the liquid composition exceeds the preferable upper limit, immediately after preparation of the liquid composition, the appearance tends to be turbid, and the precipitate may precipitate. In particular, liquid bleach containing hydrogen peroxide tends to decompose during storage.
In the present invention, the pH of the liquid composition is adjusted by adding an electrode of the pH meter to the composition adjusted to 25 ° C. using a pH meter (product name: HM-30G, manufactured by Toa DKK Corporation). The value measured by reading the value after minutes is shown.

The viscosity of the liquid composition of the present invention is preferably 15 to 300 mPa · s, more preferably 15 to 150 mPa · s, and further preferably 30 to 100 mPa · s.
When the viscosity of the liquid composition is equal to or higher than the preferred lower limit, it becomes easy to apply the laundry object to the soiled part, and the liquid composition can be easily measured. On the other hand, when the viscosity of the liquid composition is less than or equal to the preferable upper limit value, bubbles are less likely to be formed when filling a packaging container or refilling a product bottle, and workability is further improved.
In the present invention, the viscosity of the liquid composition is measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) at a measurement temperature of 25 ° C. and a rotor number of No. 1 (less than 100 mPa · s) or no. 2 (100 mPa · s or more), the rotation number is set to 60 rpm, and the value measured by reading the scale 60 seconds after the start of rotor rotation is shown.

In the liquid composition of the present invention, the component (c) serves as a thickener (viscosity modifier), and the composition (c) is not blended (not blended) (that is, the component (a) and ( b) can be adjusted to a viscosity higher than the viscosity of the composition obtained by dissolving the component and an optional component in a solvent, and can be easily adjusted to a viscosity of preferably twice or more.
When the viscosity of the liquid composition of the present invention is V1, and the viscosity of a composition in which the component (c) is not blended (not blended) in the liquid composition of the present invention is V0, it is represented by V1 / V0. The ratio is preferably 2 or more, more preferably 4 to 40, still more preferably 7 to 20, and particularly preferably 8 to 15.
If the ratio represented by V1 / V0 is equal to or greater than the preferable lower limit value, the usability at the time of coating becomes better. In addition, the retention at the application site is increased, and the cleaning performance is further improved. On the other hand, if the ratio represented by V1 / V0 is equal to or less than the preferable upper limit value, it is easy to perform filling into a packaging container, refilling into a product bottle, and the like.
In the liquid composition of the present invention, the composition in which the component (c) is not blended (not blended) has a viscosity V0 of preferably 3 mPa · s or more and less than 15 mPa · s, more preferably Is in the range of 4 to 10 mPa · s, more preferably in the range of 4 mPa · s to less than 10 mPa · s.

(Method for producing liquid composition)
The liquid composition of the present invention is prepared by mixing a solvent, a component (a), a component (b), a component (c), and optional components as necessary.
As a method for producing the liquid composition, for example, a production method having a dissolving step of dissolving the component (a), the component (b) and the component (c) in a solvent is suitable.
In particular, when the liquid composition is produced, it is easy to maintain the uniformity of the raw material mixture and the production efficiency is excellent. Therefore, in the dissolution step, the component (a) and the component (b) are mixed in the solvent. Then, it is preferable to add and mix the component (c). Thereby, a liquid composition having a transparent and uniform appearance at 25 ° C. and having an increased viscosity can be easily obtained.
Specifically, a mixture is obtained by adding and mixing (a) component, (b) component, and an arbitrary component according to a use etc. in part or all of a solvent. Next, the liquid composition is mixed by adding the component (c) to the resulting mixture, adjusting the pH by adding a pH adjuster, and adding the remainder of the solvent if mixed, and mixing. can get.
The method for adding the component (c) to the mixture is not particularly limited, and the component (c) itself may be added or may be added as a component solution (c).

The liquid composition of the present invention has a viscosity of a composition having a low surfactant concentration by mixing the component (a) and the component (b) at a specific ratio and using the component (c) together. An increase is possible.
This is because the aggregate (mixed micelle) formed by the component (a) having a specific HLB and the component (b) is easily changed to a structure having an increased number of associations by the addition of the component (c); In addition, it is presumed that the force for associating the surfactant molecules is particularly strong due to the electrical interaction between the component (b) and the component (c).
In addition, when the liquid composition of the present invention is directly applied to the soiled part of the laundry object, the retention of the liquid composition at the application part is good, so that the effect of the application cleaning property is enhanced. In addition, according to the liquid composition of the present invention, it is possible to improve applicability at the time of use and reduce foaming at the time of refilling or filling.

  Moreover, in this invention, (c) component which is water-soluble salt is mix | blended as a thickener (viscosity modifier). For this reason, it is hard to produce the viscosity change by the influence of temperature, and the storage stability of a liquid composition is favorable. In addition, component (c) is a highly versatile raw material compared to other thickeners (polymer compounds, aromatic compounds, etc.), and is advantageous in terms of cost.

Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. In this example, “%” indicates “% by mass” unless otherwise specified. In addition, the components such as surfactants have a mass% value as a pure component, and when an inorganic metal salt is used as a hydrate, the mass% value as a pure inorganic metal salt component excluding water molecules. Is described.
The composition of the liquid composition of each example is shown in Tables 1-4.
The raw materials used in this example are as follows.

<Raw materials>
((A) component)
a-1: BRE6, polyoxyethylene alkyl ether (R ¹ in the formula (a-1) = alkyl group having 12,14 carbon atoms, n = 6), HLB 11.6, narrow ratio 39.9% by mass; Product name “Leox CL-60”, manufactured by Lion Corporation.
a-2: BRE7, polyoxyethylene alkyl ether (R ¹ in the formula (a-1) = alkyl group having 12,14 carbon atoms, n = 7), HLB12.3, narrow ratio 42.5% by mass; Product name “Leox CL-70”, manufactured by Lion Corporation.
a-3: BRE8, polyoxyethylene alkyl ether (R ¹ in the formula (a-1) = C12, C14 alkyl group, n = 8), HLB 12.9, narrow ratio 41.5% by mass; Product name “Leox CL-80-90”, manufactured by Lion Corporation.
a-4: NRE7, polyoxyethylene alkyl ether (R ¹ in the formula (a-1) = alkyl group having 12,14 carbon atoms, n = 7), HLB12.3, narrow ratio 93.8% by mass; Synthetic product.

[Synthesis Method of a-4]
A composite oxide catalyst of Mg, Al, and Mn (Mg: Al: Mn (atomic ratio) = 0.56: 0.26: 0) manufactured according to Example 1 described in JP-A-2000-061304 .18) was used to synthesize a-4.
That is, 0.5 g of the composite oxide catalyst, 2.5 mL of 0.5 N potassium hydroxide ethanol solution, and 410 g of an alcohol mixture (mass ratio C12OH / C14OH = 75/25) were charged into a 4 L autoclave. The catalyst was reformed. Next, after the inside of the autoclave was replaced with nitrogen, the temperature was raised, 590 g of ethylene oxide was introduced, and the reaction was carried out with stirring while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa or less. Further, the reaction solution was cooled to 80 ° C., and after adding 100 g of water and 5 g of activated clay and diatomaceous earth as filter aids, the catalyst was filtered off to obtain a-4.

((A ′) component: comparative component of component (a))
a′-1: BRE4, polyoxyethylene alkyl ether (R ¹ in the formula (a-1) = an alkyl group having 12,14 carbon atoms, n = 4), HLB 9.5, narrow ratio 47.8% by mass Product name “Leox CL-40”, manufactured by Lion Corporation.
a′-2: BRE12, polyoxyethylene alkyl ether (R ¹ in the formula (a-1) = an alkyl group having 12,14 carbon atoms, n = 12), HLB 14.6, narrow ratio 40.0% by mass Product name “LMAL-90”, manufactured by Lion Chemical Co., Ltd.

((B) component)
b-1: A product obtained by neutralizing a linear alkylbenzene sulfonic acid (trade name “Lypon LH-200”, manufactured by Lion Corporation) with sodium hydroxide.

(Component (c))
c-1: Magnesium sulfate MgSO ₄ , molecular weight 246.48; trade name “genuine first grade magnesium sulfate heptahydrate”, manufactured by Junsei Chemical Co., Ltd.
c-2: Basic magnesium carbonate (MgCO ₃ ) ₄ · Mg (OH) ₂ · 5H ₂ O, molecular weight 485.5; trade name “pure first grade basic magnesium carbonate (heavy)”, manufactured by Pure Chemical Co., Ltd.
c-3: Magnesium chloride MgCl ₂ , molecular weight 95.3; trade name “genuine first grade magnesium chloride (anhydrous)”, manufactured by Junsei Chemical Co., Ltd.
c-4: Zinc sulfate ZnSO ₄ , molecular weight 161.45; trade name “genuine first grade zinc sulfate heptahydrate”, manufactured by Junsei Chemical Co., Ltd.
c-5: calcium sulfate CaSO ₄ , molecular weight 136.14; trade name “genuine first grade calcium sulfate dihydrate”, manufactured by Junsei Chemical Co., Ltd.

((C ′) component: comparative component of (c) component)
c′-1: sodium sulfate Na ₂ SO ₄ , molecular weight 142.04; trade name “sodium sulfate deer first grade”, manufactured by Kanto Chemical Co., Inc.

(Optional component)
d-1: 1-hydroxyethane-1,1-diphosphonic acid, trade name “BRIQUEST 'ADPA”, manufactured by Rhodia.
e-1: Hydrogen peroxide, trade name “hydrogen peroxide”, manufactured by Mitsubishi Gas Chemical Co., Ltd.
Methoxyphenol: p-methoxyphenol, trade name “MQ-F”, manufactured by Kawaguchi Chemical Industry Co., Ltd.
pH adjuster: 0.1N sodium hydroxide aqueous solution, 0.1N sulfuric acid aqueous solution.
Ion exchange water.

<Manufacture of liquid composition>
According to the compositions shown in Tables 1 to 4 (compounding components, content in the liquid composition (mass% display)), the liquid compositions of the respective examples were prepared by the following production methods.
When there is a blank in the table, the blending component is not blended.
The “appropriate amount” indicating the content of the pH adjuster is a pH adjuster (0.1N aqueous sodium hydroxide solution added to adjust the pH (25 ° C.) of the liquid composition to the pH value shown in the table, or , 0.1N sulfuric acid aqueous solution).
The pH of the liquid composition is a value after 2 minutes by placing the electrode of the pH meter into the composition adjusted to 25 ° C. using a pH meter (product name: HM-30G, manufactured by Toa DKK Corporation). Was measured by reading.
The “remainder” indicating the content of ion-exchanged water means the amount added so that the total amount (% by mass) of all the components included in the liquid composition is 100% by mass.

[Method for producing liquid composition]
Example 1
First, a part of ion-exchanged water and a-2 and b-1 were added to a 500 mL beaker and mixed. Next, d-1 and methoxyphenol were added and mixed therein, and then ion-exchanged water was added so that the total amount up to here was 80 parts by mass, and mixed to prepare a mixed solution.
Next, e-1 was added to the mixed solution and mixed, and then the c-1 itself was mixed little by little. Subsequently, after adjusting pH, adding a pH adjuster, the remaining ion exchange water was added and mixed so that the whole quantity might be 100 mass parts, and the liquid composition was obtained.

(Examples 2-11, 13-17)
According to the composition shown in Tables 1 and 2, a liquid composition was obtained in the same manner as in Example 1.

(Example 12)
A liquid composition was obtained in the same manner as in Example 1 according to the composition shown in Table 2, except that a-2 was changed to a-1.

(Example 18)
A liquid composition was obtained in the same manner as in Example 1 according to the composition shown in Table 2, except that d-1 was not blended (not blended).

(Example 19)
A liquid composition was obtained in the same manner as in Example 1 according to the composition shown in Table 3, except that a-2 was changed to a-1 and d-1 was not blended (not blended).

(Examples 20 to 22)
According to the composition shown in Table 3, a liquid composition was obtained in the same manner as in Example 12.

(Example 23)
A liquid composition was obtained in the same manner as in Example 20 according to the composition shown in Table 3, except that c-1 was changed to c-2.

(Example 24)
A liquid composition was obtained in the same manner as in Example 1 except that c-1 was changed to c-3 and e-1 and methoxyphenol were not blended (not blended).

(Example 25)
A liquid composition was obtained in the same manner as in Example 1 according to the composition shown in Table 3, except that c-1 was changed to c-4.

(Example 26)
A liquid composition was obtained in the same manner as in Example 1 according to the composition shown in Table 3, except that c-1 was changed to c-5.

(Example 27)
A liquid composition was obtained in the same manner as in Example 1 according to the composition shown in Table 3, except that a-2 was changed to a-3 and d-1 was not blended (not blended).

(Example 28)
A liquid composition was obtained in the same manner as in Example 1 according to the composition shown in Table 3, except that a-2 was changed to a-4.
However, Example 28 is a reference example.

(Example 29)
A liquid composition was obtained in the same manner as in Example 1 according to the composition shown in Table 3, except that d-1 was not blended (not blended).

(Comparative Example 1)
A liquid composition was obtained in the same manner as in Example 1 according to the composition shown in Table 4, except that b-1 and c-1 were not blended (not blended).

(Comparative Example 2)
A liquid composition was obtained in the same manner as in Example 1 according to the composition shown in Table 4 except that b-1 was not blended (not blended).

(Comparative Example 3)
A liquid composition was obtained in the same manner as in Example 1 according to the composition shown in Table 4 except that c-1 was not blended (not blended).

(Comparative Example 4)
A liquid composition was obtained in the same manner as in Example 1 according to the composition shown in Table 4 except that b-1 was not blended (not blended) and c-1 was changed to c′-1.

(Comparative Example 5)
A liquid composition was obtained in the same manner as in Example 1 according to the composition shown in Table 4 except that a-2 was changed to a'-1.

(Comparative Example 6)
A liquid composition was obtained in the same manner as in Example 1 according to the composition shown in Table 4 except that a-2 was changed to a'-2.

(Comparative Examples 7 and 8)
According to the composition shown in Table 4, a liquid composition was obtained in the same manner as in Example 1.

(Comparative Example 9)
A liquid composition was obtained in the same manner as in Example 1 according to the composition shown in Table 4 except that a-2 was not blended (not blended).

<Evaluation>
About the liquid composition of each example, the viscosity, storage stability, and detergency were each evaluated by the evaluation method shown below. The results are shown in Tables 1-4.

[Viscosity of liquid composition]
A 300 mL tall beaker was filled with 300 mL of the liquid composition of each example, and the temperature was adjusted to 25 ° C. in a water bath.
Thereafter, using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.), the measurement temperature was 25 ° C., and the rotor number was No. 1 (less than 100 mPa · s) or no. 2 (100 mPa · s or more), the number of revolutions was set to 60 rpm, and the scale (V1) of each liquid composition was measured by reading the scale 60 seconds after the start of rotor rotation.
Moreover, the viscosity (V0) of the composition which (c) component was not mix | blended (not mix | blended) in the liquid composition of each example was measured like the said viscosity (V1).
Then, the ratio of the viscosity (V1) to the viscosity (V0), that is, the ratio represented by V1 / V0 was calculated to obtain the viscosity change rate.
A larger value of this ratio (V1 / V0) means that the effect of increasing the viscosity is higher.

[Storage stability of liquid composition (1)]
100 mL of the liquid composition is placed in a transparent glass bottle (wide-mouth bottle: PS-No. 11), sealed with a lid closed, and in this state in a thermostatic bath set at 40 ° C. and −5 ° C. for one week. I saved it.
Thereafter, the appearance of the contents of the glass bottle was visually observed at room temperature (25 ° C.) within 1 minute after the glass bottle filled with the liquid composition was taken out from each thermostat. Moreover, about the liquid composition of each example, the external appearance before the storage start (initial stage) for 1 week was observed visually. At that time, the storage stability of the liquid composition was evaluated based on the following evaluation criteria.
Evaluation criteria for appearance before start of storage (initial stage) A: Transparent and uniform appearance.
X: Cloudiness, precipitation or separation was observed.
Evaluation criteria for appearance after storage for 1 week (40 ° C., 1 W, −5 ° C., 1 W) A: Transparent and uniform appearance.
○: Slightly turbid but no separation, no problem.
X: Separation was observed.
In addition, “-” in the table indicates that the appearance evaluation after storage for one week is not evaluated for the example in which the evaluation of the appearance before the start of storage (initial) is x.

[Detergency of liquid composition]
1) Manufacture of ra oil contaminated cloth 0.015 mL of ra oil (manufactured by S & B) was dropped onto a polyester tropical cloth (3 cm × 3 cm) and dried to obtain ra oil contaminated cloth.
2) Cleaning experiment 0.24 mL of the same liquid composition was applied to each of the five luller oil-contaminated cloths, and left for 5 minutes (coating bleaching). Then, the washing | cleaning process was performed using Terg-O-Tometer (product name, the product made by U.S. Testing).
The cleaning process is 120 rpm, water temperature 15 ° C, tap water, bath ratio 30 (adding a white cotton shirt so that the total amount of cloth including 5 pieces of la oil contaminated cloth is 30 g per 900 g of water. ), Using a commercially available detergent (Top NANOX manufactured by Lion Corporation, the detergent concentration of 333 ppm (mass basis)), washed for 10 minutes, then dehydrated for 1 minute, rinsed with running water for 2 minutes, This was done by dehydrating for 1 minute.
3) Evaluation of detergency After drying the litter oil-contaminated cloth after the washing treatment, the washing rate (%) was determined by the following formula using a reflectometer (Σ90 manufactured by Nippon Denshoku). In the following formula, the raw fabric refers to a polyester tropical fabric that has not been subjected to the contamination treatment described above.
Washing rate (%) = {(reflectance of ra oil contaminated cloth−reflectance of ra oil contaminated cloth after washing treatment) / (reflectance of ra oil contaminated cloth−reflectance of raw cloth)} × 100
The detergency was determined by the following formula from the determined cleaning rate. In addition, the washing | cleaning rate used for the following type | formula is an average value of five sheets of luller oil-contaminated cloth. In the formula, “when the liquid composition is not applied” means that the above 2) cleaning experiment is performed without applying the liquid composition to the litter oil-contaminated cloth.
Detergency (%) = (cleaning rate when liquid composition is applied / cleaning rate when liquid composition is not applied) × 100
A larger value of the detergency (%) means higher detergency.

  From the results shown in Tables 1 to 4, the liquid compositions of Examples 1 to 29 to which the present invention was applied utilized a highly versatile raw material (water-soluble divalent metal salt) in a composition having a low surfactant concentration. Thus, it can be seen that the viscosity can be easily increased and the storage stability is good.

[Storage stability of liquid composition (2)]
For the liquid compositions of Example 3 and Example 29, the same evaluation as the above-mentioned [Storage stability of liquid composition (1)] was further placed in a thermostatic bath set at a temperature of 50 ° C. for 1 week. It changed into the conditions to preserve | save and performed by the same evaluation criteria as the evaluation criteria ((double-circle), (circle), x) about the external appearance after the said 1 week preservation | save).
As a result, the evaluation of the appearance after storage was ◎ when the liquid composition of Example 3 was used, and ◯ when the liquid composition of Example 29 was used.
From this evaluation result, by containing the component (d) in addition to the components (a) to (c), the separation of the liquid composition is suppressed even under severer storage conditions on the higher temperature side, and the liquid stability It can be seen that

Claims (4)

(A) Component: Nonionic which is represented by the following general formula (a-1), has an HLB of 10.5 to 13.5 , and a narrow ratio represented by the following (S) formula is less than 50% by mass. 1% by weight or more and less than 10% by weight of surfactant,
(B) component: an anionic surfactant;
(C) component: 0.2% by mass or more of a water-soluble divalent metal salt,
A liquid composition, wherein a mass ratio represented by (a) component / (b) component is 1 to 6.

[Wherein, R represents an alkyl group or alkenyl group having 8 to 18 carbon atoms, and n represents the average number of repeating oxyethylene groups. ]

[ _Wherein , p _max represents the number of moles of ethylene oxide added in the ethylene oxide adduct most abundant in the entire ethylene oxide adduct. i represents the number of moles of ethylene oxide added. Yi represents the ratio (% by mass) of the ethylene oxide adduct having an i added mole number of ethylene oxide present in the entire ethylene oxide adduct. ] 2. The liquid composition according to claim 1, wherein the molar ratio represented by component (b) / [divalent metal derived from component (c)] is 2.5 or less. The liquid composition according to claim 1 or 2, which has a pH of 2.5 to 4.5. Viscosity is 15-300 mPa * s, The liquid composition of any one of Claims 1-3 characterized by the above-mentioned.