JP2009185253A - Liquid detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid detergent composition in which an AG (alkyl glycoside type surfactant), an AES (polyoxyethylene alkylether sulfuric ester type surfactant) obtained by using a linear alcohol, e.g. a natural alcohol as raw alcohol and an AO (amine oxide type surfactant) are combined and which has high detergent performance and excellent storage stability at a low temperature. <P>SOLUTION: The liquid detergent composition contains, by mass, (a) 4-35% specified AG compound represented by general formula (1): R<SP>1a</SP>-(OR<SP>1b</SP>)<SB>s</SB>G<SB>t</SB>, (b) 1-25% mixture containing a specified polyoxyalkylene alkylsulfuric ester salt represented by general formula (2): R<SP>2a</SP>O-(PO)<SB>m1</SB>(EO)<SB>n1</SB>SO<SB>3</SB>M, wherein the average addition molar number m of propylene oxide is >0 and <1 and the average addition molar number n of ethylene oxide is >0 and ≤3, (c) 0.3-10% specified AO, (d) a hydrotropic agent, and (e) a phase stabilizer selected from organic solvents, and water. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a liquid detergent composition, and more particularly to a liquid detergent composition containing an alkyl glycoside as a main surfactant. Uses include clothing and hard surfaces, and in particular, it relates to a liquid detergent composition suitable for cleaning hard surfaces such as around kitchens, especially tableware and cooking utensils.

  In addition to dirt from the original ingredients, tableware detergents include cooking oils and seasonings, denatured proteins produced by cooking, charred and gelatinized carbohydrates, etc., dishes, frying pans, pans, grilled fish, and other cooking It adheres to instruments and forms dirt that is difficult to remove with water alone. In particular, since dirt due to oil can easily be felt from the fingertips and the degree of wiping, the user tends to be nervous with respect to the removal of dirt. In recent years, dishwashing detergents for hand-washing have been improved by increasing the content of surfactants in order to improve the cleanability due to oil stains. However, the increased ability to remove oil stains can also affect the oil content of the hand skin. Although the skin quality varies from person to person, manufacturers have made diligent efforts to minimize the impact on the hand skin. For example, a cleaning agent using an alkyl glycoside surfactant (hereinafter sometimes referred to as AG) mild to the hand skin as the main surfactant is mentioned.

Examples of techniques using alkyl glycosides as liquid detergents include Patent Documents 1 to 5 and the like. In general, alkyl glucoside type detergents are excellent in foaming and rinsing properties, but from the viewpoint of improving detergency, polyoxyethylene alkyl ether sulfate type surfactants (hereinafter sometimes referred to as AES) and amine oxides. It has been proposed to use a type surfactant (hereinafter sometimes referred to as AO). For example, Patent Literature 6 or Patent Literature 7 describes a detergent for tableware containing AES and AO as a detergent having AG as a main surfactant.
Japanese Patent Laid-Open No. 10-25498 JP-T 8-502540 Japanese National Patent Publication No. 8-501817 JP-A-5-148494 JP 2000-26889 A JP 2000-109900 A JP 2005-325167 A

  Since the detergent with AG as the main surfactant has insufficient detergency alone, AES and AO are used in combination as described above. When AO is blended, it is difficult to maintain low temperature stability, and the contents of AES and AO are limited. Increasing the number of moles of ethylene oxide added to AES can improve the stability problem, but as a result, the hydrophilicity is increased and the detergency against oil is impaired. By the way, although AG has a hydrophilic part derived from sugar, attention is paid because it is a base material that can cover all of the constituent components with a naturally-derived raw material by using the alkyl group of the lipophilic part derived from natural fats and oils. Has been. However, as described above, the problem with the AG-based detergent is that it is difficult to stably mix the combined system of AES and AO as described above. On the other hand, this problem is particularly caused by blending AG having an alkyl group derived from natural fats and oils. Great effect on cleaning agents. Moreover, although the alkyl group of AES and AO can be derived from natural fats and oils, in this case, the low-temperature stability is further lowered, and the limitation of the blending concentration becomes severe. The reason is that when fatty acids, alcohols and amines generally obtained from natural fats and oils such as coconut oil are used as raw materials, the alkyl group becomes linear, and the carbon atom of the alkyl group bonded to the hydrophilic part Since it has a structure having a primary carbon atom, in other words, a hydrophilic group at the end of the alkyl chain, it is presumed that it has the property of being easily crystallized compared with a synthetic surfactant in which a branched alkyl group is mixed. The

  In addition, from the public opinion that the recent influence of carbon dioxide on the environment is concerned, there is a demand for a technique for using not only fossil fuels but also surfactants derived from natural oils and fats. Therefore, an object of the present invention is to provide a liquid detergent composition having high detergency and excellent storage stability at low temperatures while using AG, AO and AES, and further, a natural surfactant. Another object of the present invention is to obtain an AG-based cleaning agent having excellent cleaning power and stability.

  The present inventors have examined in detail the cleaning behavior of AES for the purpose of applying AG and AES, and further AO, as liquid cleaning agents. As a result, an AES surfactant having a structure in which 1 mol of ethylene oxide is added to alcohol (single addition number distribution) and a structure in which 2 mol of ethylene oxide is added to alcohol (single addition number distribution is single) It was found that the AES-type surfactant (1) had the highest detergency. On the other hand, the reaction of adding ethylene oxide to alcohol is known to have a wide distribution of the number of moles of ethylene oxide added in the product. Is obtained in an amount of about 15 to 20% by mass, and about 30% by mass of unreacted alcohol is present in the reaction product. AES obtained by sulfating such an ethylene oxide adduct contains about 30% by mass of an alkyl sulfate ester salt (sometimes referred to as AS), and a complex of AS and AO precipitates at a low temperature. I found out that it was bad. This is a particular problem in AES having a linear alkyl group. As described above, increasing the average number of moles of ethylene oxide added can reduce the amount of AS after sulfation and improve the stability. On the other hand, 1 mole effective for detergency It was found that even adducts and even 2 molar adducts were reduced, resulting in a decrease in detergency. In the production of oxyalkylene alkyl ether sulfates, the present inventors have reduced the amount of unreacted alcohol by first adding a small amount of propylene oxide to the alcohol, and then adding ethylene oxide, resulting in excellent stability. It was found that the property and detergency can be obtained. This is presumably because the reaction proceeds without reducing the proportion of 1 mol of adduct and 2 mol of adduct by addition of propylene oxide to alcohol first. Also, when propylene oxide is first added to the alcohol, a pseudo-branched structure is formed by the alkyl group and the oxypropylene group bonded thereto, contributing to stability by moderately loosening the packing property between the surfactants. This is considered to have led to the present invention.

The present invention contains (a) a compound represented by the following general formula (1) [hereinafter referred to as component (a)] in an amount of 4 to 35% by mass, and (b) a compound represented by the following general formula (2). Wherein the average addition mole number m of propylene oxide and the average addition mole number n of ethylene oxide in the mixture are 0 <m <1, 0 <n ≦ 3, respectively (hereinafter referred to as component (b) 1-25 mass%, (c) an amine oxide surfactant having a hydrocarbon group having 8 to 18 carbon atoms and an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms [ (Hereinafter referred to as “component (c)”) is selected from 0.3 to 10% by mass, (d) hydrotrope (hereinafter referred to as “component (d)”) and (e) organic solvent (hereinafter referred to as “component (e)”). Liquid detergent containing phase stabilizer and water On Narubutsu.
R ^1a- (OR ^1b ) _s G _t (1)
[Wherein, R ^1a represents an alkyl group having 8 to 16 carbon atoms, and R ^1b represents an alkylene group having 2 to 4 carbon atoms. G represents a group derived from a reducing sugar. s shows the number of 0-5 by average addition mole number, and t shows the number of 1-3 by average condensation degree. ]
R ^2a O— (PO) _m1 (EO) _n1 SO ₃ M (2)
[In the formula, R ^2a is an alkyl group having 8 to 18 carbon atoms, PO and EO are a propyleneoxy group and an ethyleneoxy group, respectively, m1 and n1 represent the added mole number of PO or EO, each of 0 or more. Is an integer. M is a cation. ]

  When the liquid detergent composition of the present invention is used in combination with AG, AES, and AO, the AES and AO can be stably blended even in a system with a large amount of AG, and further, raw alcohol of AG, AO, and AES As a natural raw material, that is, using a raw material in which the raw material alcohol is occupied by a compound having a linear alkyl group, a liquid detergent having high detergency and excellent low-temperature storage stability can be obtained.

  First, each component contained in the liquid detergent composition of the present invention will be described.

The component (a) of the present invention is an alkyl glycoside surfactant of the general formula (1).
R ^1a- (OR ^1b ) _s G _t (1)
[Wherein, R ^1a represents an alkyl group having 8 to 16 carbon atoms, and R ^1b represents an alkylene group having 2 to 4 carbon atoms. G represents a group derived from a reducing sugar. s shows the number of 0-5 by average addition mole number, and t shows the number of 1-3 by average condensation degree. ]

In the general formula (1), R ^1a is preferably a linear alkyl group having 10 to 14 carbon atoms. It may be a naturally occurring alkyl group. In this case, the alkyl group is a straight chain, and the carbon atom of R ^1a bonded to the oxygen atom is a primary carbon atom. Further, s is preferably 0 to 3, more preferably 0 to 2, and particularly preferably 0. R ^1b is preferably an ethylene group.

  In the general formula (1), G is a group derived from a reducing sugar, and more specifically a glycoside group. The reducing sugar as a raw material may be either aldose or ketose, and examples thereof include triose, tetrose, pentose, and hexose having 3 to 6 carbon atoms. Specific examples of aldose include apiose, arabinose, galactose, glucose, lyxose, mannose, galose, aldose, idose, talose and xylose, and examples of ketose include fructose. In the present invention, among these, aldopentose or aldohexose having 5 or 6 carbon atoms is particularly preferred, and glucose is most preferred.

  In general formula (1), t represents the average degree of condensation of sugars, preferably a number of 1 to 2, particularly a number of 1 to 1.5.

The compound of the general formula (1) can be easily synthesized by acetalizing or ketalizing the above sugar and R ^1a — (OR ^1b ) _s —OH using an acid catalyst. In the case of an acetalization reaction, a hemiacetal structure or a normal acetal structure may be used.

The component (b) of the present invention is a mixture containing a compound represented by the following general formula (2), and the average added mole number m of propylene oxide and the average added mole number n of ethylene oxide in the mixture are respectively 0 <m <1, 0 <n ≦ 3.
R ^2a O— (PO) _m1 (EO) _n1 SO ₃ M (2)
[In the formula, R ^2a is an alkyl group having 8 to 18 carbon atoms, PO and EO are a propyleneoxy group and an ethyleneoxy group, respectively, m1 and n1 represent the added mole number of PO or EO, each of 0 or more. Is an integer. M is a cation. ]

The component (b) of the present invention can obtain a sufficient effect even when a surfactant derived from a natural alcohol is used. In that case, R ^2a is a straight chain, and the naturally occurring alcohol has a hydroxy group at the end, so that propylene oxide or ethylene oxide is added thereto, so that it is bonded to the oxygen atom of propylene oxide or ethylene oxide. The carbon atom of R ^2a is the first carbon atom. Of course, in the case of alkyl sulfates or salts, the hydroxy group at the terminal of R ^2a is sulfated, which likewise becomes the first carbon atom.

  m and n are the average number of moles added in the mixture of the compound calculated from m1 and n1 of the compound represented by the general formula (2). By the way, in the production of the component (b) compound, in the present invention, it is important to first add propylene oxide. Examining the ease of addition of ethylene oxide and propylene oxide to alcohol shows that propylene oxide is easier to add. That is, by adding propylene oxide first, it becomes possible to reduce the proportion of unreacted alcohol, so the content of the alkyl sulfate ester or salt thereof, in which the unreacted alcohol is finally sulfated, To reduce. When the addition rate of propylene oxide is increased, the proportion of surfactants having a pseudo-branched structure due to propylene oxide increases, and as a result, the packing property between the active agents is disturbed due to steric hindrance and the detergency is reduced. To do. Therefore, the average number of moles of propylene oxide represented by m is limited to less than 1, preferably the lower limit is 0.1 or more, that is, 0.1 ≦ m, more preferably 0.15 or more, that is, 0.15. ≦ m, and the upper limit is preferably 0.8 or less, that is, m ≦ 0.8, and more preferably 0.6 or less, that is, m ≦ 0.6.

  In the component (b) of the present invention, propylene oxide (hereinafter sometimes referred to as PO) is added to alcohol, and then ethylene oxide (hereinafter sometimes referred to as EO) is added. Those obtained by adding 1 mol and 2 mol of EO, that is, compounds having n1 = 1 and n1 = 2 among the compounds represented by the general formula (2) are most effective in terms of cleaning performance. Therefore, it is desirable to add ethylene oxide so that the ratio of 1 mol and 2 mol becomes high. Accordingly, in the present invention, the average added mole number n of EO is preferably 2.5 or less, that is, n ≦ 2.5, more preferably 2.3 or less, that is, n ≦ 2.3, most preferably 2. In the following, that is, n ≦ 2. The lower limit of n is preferably 0.5 or more, that is, 0.5 ≦ n, more preferably 1 or more, that is, 1 ≦ n.

  Hereinafter, m1 and n1 in the general formula (2) will be described. In the present invention, the component (b) is 0 <m <1, 0 <n ≦ 3, and the ratio of the compounds represented by m1 = 0 and n1 = 0 is limited so that the low-temperature stability is achieved. Property is improved, and sufficient detergency can be obtained. Further, in compounds other than n1 = 0 (where m1 ≠ 0), the oxypropylene group has a quasi-branching element of an alkyl chain. The role is thought to improve low temperature stability.

  In the present invention, the ratio of the compound of m1 = n1 = 0 in the component (b), that is, the alkyl sulfate ester or a salt thereof is preferably 28% by mass or less, more preferably 26% by mass or less, most preferably 24 It is below mass%.

  In the component (b) of the present invention, the content of the compound of m1 ≧ 2 is preferably 15% by mass or less, more preferably 10% by mass or less in the component (b). Compounds with m1 ≧ 2 reduce detergency.

  When propylene oxide is reacted with alcohol, propylene oxide tends to react with unreacted alcohol more easily than subsequent reaction after PO once reacted with alcohol. Therefore, when propylene oxide is reacted at a ratio of m <1, a large amount of m1 = 1 compounds are produced, and a small amount of m1 ≧ 2 is produced. In particular, when propylene oxide is reacted at a ratio of m ≦ 0.6, the production of a compound of m1 ≧ 2 is easily suppressed to 15% by mass or less, particularly 10% by mass or less. Care should be taken in selecting the catalyst to limit compounds with m1 ≧ 2. In addition, as a method of reliably suppressing the formation of the compound of m1 ≧ 2, a method of adding propylene oxide in the presence of excess alcohol is conceivable. In this case, it is necessary to remove excess unreacted alcohol by distillation before reacting ethylene oxide.

  As the compound constituting the component (b), an oxypropylene alkyl ether sulfate or a salt thereof, that is, a compound having m1 = 1 and n1 = 0 is preferably 4 to 50% by mass, more preferably in the component (b). It is 10-40 mass%.

  Furthermore, in the present invention, as described above, as the compound constituting the component (b), it is preferable that there are many compounds having 1 or 2 ethylene oxide groups. Therefore, the compound of n1 = 1 and n1 = 2 is preferably 25 to 45% by mass, more preferably 28 to 40% by mass in the component (b). The compound in the remaining component (b) is a compound having n1 of 3 or more.

  The upper limit of m1 is preferably 3 or less, and therefore component (b) is preferably composed of a compound of 0 ≦ m1 ≦ 3. The upper limit of n1 is preferably 10 or less, and therefore component (b) is preferably composed of a compound of 0 ≦ n1 ≦ 10. In the present invention, in particular, a compound of 0 ≦ n1 ≦ 5 in terms of detergency Is a mixture occupying 85% by mass or more of the component (b).

  M in the general formula (2) is a cation group that forms a salt, and examples thereof include alkali metal ions, ammonium ions, and alkanol ammonium groups such as a monoethanol ammonium group. Examples of the alkali metal include sodium, potassium, and lithium. Among these, sodium and potassium are more preferable.

  In addition, in this invention, description (mass% and mass ratio) regarding the mass which concerns on (b) component is mass (in acid conversion) when M in the general formula (2) of (b) component is assumed to be a hydrogen atom. Ratio).

  The component (b) may contain a compound that is not sulfated in the production thereof, but in the present invention, the compound is treated as a nonionic surfactant.

The component (b) can be produced as follows.
Step (I): Step of adding propylene oxide to alcohol, preferably linear primary alcohol Step (II): Step of adding ethylene oxide to the propylene oxide adduct obtained in the above step (I) Step (III): The step of sulfating and then neutralizing the alkoxylate obtained in the above step (II)

  In the step (I), propylene oxide is added to the alcohol having 8 to 18 carbon atoms. The addition ratio is such that propylene oxide is added at a ratio represented by m in the general formula (2) per mole of the alcohol. .

  In step (II), ethylene oxide is added on average to the propylene oxide adduct obtained in step (I). It is made to react with the ratio of ethylene oxide of the ratio shown by n in General formula (2) with respect to alcohol.

  As a method for carrying out the steps (I) and (II), a conventionally known method can be used. That is, an autoclave is charged with 0.5 to 1 mol% of KOH as a catalyst, and the mixture is heated and dehydrated, and a predetermined amount of propylene oxide and ethylene oxide are respectively added at a temperature of about 120 to 160 ° C. Can be manufactured. At this time, the addition form is block addition, and propylene oxide addition [step (I)] and ethylene oxide addition [step (II)] are performed in this order. The autoclave to be used is preferably provided with a stirring device, a temperature control device, and an automatic introduction device.

  Step (III) is a step of sulfating and then neutralizing the alkoxylate obtained in the above step (II). Examples of the sulfation method include methods using sulfur trioxide (liquid or gas), sulfur trioxide-containing gas, fuming sulfuric acid, chlorosulfonic acid, and the like, and particularly prevent the generation of waste sulfuric acid and waste hydrochloric acid. From the viewpoint, a method in which sulfur trioxide is continuously supplied in a gaseous or liquid state simultaneously with the alkoxylate is preferable.

  As a method for neutralizing the sulfate, batch type, which performs neutralization while adding and stirring the sulfate to a predetermined amount of neutralizer, and continuously supplying the sulfate and neutralizer into the pipe, stirring and mixing Examples include a loop type in which neutralization is performed by a machine, but the neutralization method is not limited in the present invention. Examples of the neutralizing agent used here include an aqueous alkali metal solution, aqueous ammonia, and triethanolamine, but an aqueous alkali metal solution is preferred, and sodium hydroxide is more preferred.

  The component (c) of the present invention is an amine oxide surfactant having a hydrocarbon group having 10 to 18 carbon atoms and an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms. The amine oxide type surfactant exhibits excellent oil stain cleaning power when used in combination with the component (b) AES. As the amine oxide type surfactant, a compound represented by the following general formula (3) is preferable.

(Wherein R ^3a is a hydrocarbon group having 10 to 18 carbon atoms, R ^3b is an alkylene group having 1 to 3 carbon atoms, and R ^3c and R ^3d are alkyl groups or hydroxyalkyl having 1 to 3 carbon atoms. X is a group selected from —COO—, —CONH—, and —O—, and o is a number of 0 or 1.)

Among the compounds represented by the general formula (3), R ^3a is preferably an alkyl group or an alkenyl group having 10 to 16 carbon atoms, more preferably 10 to 14 carbon atoms. An alkyl group structure obtained from natural fats and oils may be used, and a straight chain is preferred from the viewpoint of using natural raw materials. As a particularly preferred compound, R ^3a is a lauryl group (or lauric acid residue) and / or a myristyl group (or myristic acid residue), R ^3c and R ^3d are both methyl groups, and o = 0 And R ^3a is a lauryl group (or lauric acid residue) and / or a myristyl group (or myristic acid residue), R ^3c and R ^3d are both methyl groups, and o = 1 , X is —CONH— or —O—, and R ^3b is a compound of a propylene group or a hydroxypropylene group.

In the present invention, R ^3a may be a single alkyl (or alkenyl) chain or a mixed alkyl group (or alkenyl group) having different alkyl (or alkenyl) chains. In the latter case, those having a mixed alkyl (or alkenyl) chain derived from a vegetable oil selected from palm oil and palm kernel oil are preferred. Specifically, the cleaning effect is such that the molar ratio of lauryl group (or lauric acid residue) / myristyl group (or myristic acid residue) is 95/5 to 20/80, preferably 90/10 to 30/70. From the point of view, it is preferable.

  The liquid detergent composition of the present invention contains a phase stabilizer selected from (d) a hydrotrope agent and (e) an organic solvent.

  As the hydrotrope agent of component (d), alkylbenzene sulfonates having 1 to 3 alkyl groups having a maximum carbon number of 3 or less are preferred, specifically toluene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid, and These sodium, potassium or magnesium salts are good, and p-toluenesulfonic acid is particularly good.

  As the organic solvent of the component (e), first, (i) an alcohol having 1 to 3 carbon atoms, (ii) a glycol or glycerin having 2 to 4 carbon atoms, and (iii) an alkylene glycol unit having 2 to 4 carbon atoms. Examples thereof include di- or trialkylene glycol, (iv) monoalkoxy (methoxy, ethoxy, propoxy, butoxy), phenoxy or benzooxy ether of di- or tetraalkylene glycol having 2 to 4 carbon atoms in the alkylene glycol unit.

  Specifically, (i) is ethanol, isopropyl alcohol, (ii) is ethylene glycol, propylene glycol, glycerin, isoprene glycol, (iii) is diethylene glycol, dipropylene glycol, (iv) is propylene glycol monomethyl ether , Propylene glycol monoethyl ether, diglycol monobutyl ether, phenoxyethanol, phenoxytriethylene glycol, and phenoxyisopropanol, and a water-soluble organic solvent selected from these is preferable. In particular, ethanol, propylene glycol, dipropylene glycol, butyl diglycol, phenoxyethanol, phenyl glycol, and phenoxyisopropanol are preferable.

  Moreover, polyalkylene glycol can be used as an organic solvent. Polyalkylene glycol is useful as an anti-gelling agent [hereinafter sometimes referred to as component (e-1)], for example, an anti-gelling polymer described in JP-A-11-513067, particularly polypropylene. It is preferable to blend glycol from the viewpoint of viscosity control and storage stability. Polypropylene glycol preferably has a weight average molecular weight of 600 to 5000, more preferably 1000 to 4000. The weight average molecular weight can be determined using a light scattering method, and a dynamic light scattering photometer (DLS-8000 series, Otsuka). It can be measured by an electronic company etc.).

  Further, for the purpose of suppressing the formation of a polymer film of the activator that can be formed at the gas-liquid interface of the cleaning composition, an ethylene oxide adduct of glycerin (the average number of moles of added ethylene oxide is preferably 5 to 120) (e-1). You may mix | blend as a component.

  The liquid detergent composition of the present invention includes, as other components, a nonionic surfactant other than component (a), an anionic surfactant other than component (b), and an amphoteric surfactant other than component (c). One or more surfactants selected from agents [hereinafter referred to as component (f). ] Is preferably used in combination for stability and cleaning properties.

Preferred examples of the nonionic surfactant include monoalkyl (poly) glyceryl ethers having a branched chain alkyl group having 6 to 12 carbon atoms. In particular, those represented by the following general formula (4) are preferable.
R ⁴ —O—X (4)
[Wherein, R ⁴ is a branched alkyl group having 8 to 12 carbon atoms, preferably a group selected from 2-ethylhexyl, isononyl, and isodecyl, and X is CH ₂ CH (OH) CH ₂ OH. . ]

Preferable nonionic surfactants include polyoxyethylene alkyl ethers in which ethylene oxide is added to a branched or linear primary or secondary alcohol having 8 to 20 carbon atoms. What is shown by following General formula (5) especially is preferable.
R ⁵ —O (EO) _r H (5)
[Wherein, R ⁵ is a primary linear alkyl group, branched alkyl group or secondary alkyl group having an average carbon number of 8 to 20, preferably 8 to 18. EO is an ethyleneoxy group, and r is 5 to 20 as an average added mole number. ]

Preferable nonionic surfactants include polyoxyethylene polyoxypropylene alkyl ethers in which propylene oxide and ethylene oxide are added to a branched or linear primary or secondary alcohol having 8 to 20 carbon atoms. The oxyethylene group and the oxypropylene group may be block or random, and the order is not limited. Particularly preferred are those represented by the following general formula (6).
R ⁶ —O [(EO) _p / (PO) _q ] H (6)
[Wherein R ⁶ is a primary alkyl group having 8 to 20 carbon atoms, preferably 8 to 18 carbon atoms. EO represents ethylene oxide and PO represents propylene oxide. p is 3 to 15 as an average added mole number, and q is 1 to 5 as an average added mole number. EO and PO may be random addition or EO addition followed by PO addition and vice versa. ]

  As the amphoteric surfactant, sulfobetaine and carbobetaine can be used.

  As the anionic surfactant, an anionic surfactant having an alkyl group having 10 to 20 carbon atoms and having a sulfate group or a sulfonate group is preferable. Specific examples include linear alkyl benzene sulfonates, α-sulfo fatty acid ester salts, α-olefin sulfonates, alkane sulfonates, and fatty acid salts.

  The liquid detergent composition of the present invention includes a sequestering agent [hereinafter referred to as component (g)] as citric acid, malic acid, EDTA (ethylenediaminetetraacetic acid), tartaric acid, lactic acid, gluconic acid, and nitrogen atoms of amino acid compounds. An aminopolycarboxylic acid having at least one carboxymethyl group bonded thereto (for example, MGDA (methylglycine diacetic acid)) and salts thereof may be blended. The salt can include sodium, potassium, and alkanolamine, but may be blended as a separate component alkali agent.

  In the liquid detergent composition of the present invention, as other components, for example, antibacterial / antifungal agents known under trade names such as proxel and caisson, disinfectants such as zinc salts, silver salts, polylysine, phenoxyethanol, sulfuric acid Water-soluble inorganic salts such as magnesium, reducing agents such as sulfites, antioxidants such as BHT and ascorbic acid, thickening polymers such as xanthan gum, guar gum and carrageenan, polymer dispersants such as polyacrylic acid polymers, Compounds known to be incorporated in liquid detergents such as enzymes such as protease, amylase and lipase, foaming agents, coloring agents, and fragrances can be incorporated.

  In the liquid detergent composition of the present invention, the balance is water, which is essentially an essential component. In view of liquid stability, water is preferably distilled water or ion-exchanged water.

  Next, the blending ratio of the above components in the liquid detergent composition of the present invention will be described. The component (a) of the present invention is contained in the composition in an amount of 4 to 35% by mass, but in the present invention, it is a system having a large AG content such as 10% by mass or more, and further 15% by mass or more. Even at low temperature stability. The upper limit is particularly preferably 30% by mass or less. From the viewpoint of detergency, it is not less than the lower limit value and from the viewpoint of low temperature stability, it is not more than the upper limit value.

  The component (b) of the present invention is contained in the composition in an amount of 1 to 20% by mass, preferably 1.5 to 15% by mass, more preferably 1.5 to 10% by mass. From the viewpoint of detergency, it is not less than the lower limit value and from the viewpoint of low temperature stability, it is not more than the upper limit value. The content of the component (b) is a concentration when M in the general formula (1) is assumed to be a hydrogen atom.

  (C) A component is 0.3-10 mass% in a composition, Preferably it is 0.5-10 mass%, More preferably, 1.5-10 mass% is contained. In terms of detergency, it is not less than the lower limit value and not more than the upper limit value in terms of low temperature stability.

  Content in the composition of the hydrotrope agent which is (d) component of this invention becomes like this. Preferably it is 1-10 mass%, More preferably, it is 1.5-7.5 mass%.

  The content in the composition of the organic solvent which is the component (e) of the present invention is preferably 0 to 30% by mass, more preferably 1.5 to 15 as an amount excluding the component (e-1) described later. % By mass. The content of ethanol in the composition is preferably 0 to 7.5% by mass, and the other solvent is one or more selected from propylene glycol, dipropylene glycol, butyl diglycol, phenoxyethanol, phenyl glycol, and phenoxyisopropanol. However, the total amount of one or more solvents selected from propylene glycol, dipropylene glycol, butyl diglycol, phenoxyethanol, phenyl glycol, and phenoxyisopropanol is 0 to 25% by mass in the composition. be able to.

  Moreover, content in the composition of the polyalkylene glycol which is (e-1) component among (e) component becomes like this. Preferably it is 0-5 mass%, More preferably, it is 0-3 mass%. In the case of polypropylene glycol, it is preferable to add 0 to 2% by mass in the composition. Moreover, in the case of the ethylene oxide adduct of glycerol, it is preferable to mix | blend 0-1 mass% in a composition.

  The component (f) is preferably contained in the composition in an amount of 0.5 to 25% by mass, more preferably 1 to 20% by mass. Further, a nonionic surfactant other than the component (a) is contained in the composition. It is preferable to contain 5 to 15% by mass in terms of emulsifying power and foaming power, and it is preferable in terms of foaming power and low-temperature stability to contain 1 to 15% by weight of an amphoteric surfactant. An anionic surfactant other than the component (b) can be blended. For example, α-olefin sulfonate having 8 to 16 carbon atoms, α-sulfo fatty acid (8 to 16 carbon atoms) lower alkyl (1 carbon atom) -3) Ester salts, fatty acid salts, alkylbenzene sulfonates, alkane sulfonates can be mentioned. Examples of the salt include sodium salt, potassium salt, magnesium salt, and alkanolamine salt, and particularly sodium salt, potassium salt, and magnesium salt can be mentioned from the viewpoint of viscosity. However, the sulfonic acid-based anionic surfactant may be less than 5% by mass, more preferably 3% by mass or less, particularly 2.5% by mass or less in the composition from the viewpoint of mildness of AG against hand skin. preferable.

  In the present invention, the total amount of the surfactant including the component (a), the component (b), the component (c) and the component (f) is preferably 10 to 60% by mass, more preferably 10 to 50% by mass, Further, the ratio of AG to the total amount of surfactant (the ratio of AG in the total amount of surfactant) is set according to the properties of the intended cleaning agent, but in the present invention, it is 20% by mass or more, more preferably 25% by mass or more, In particular, it can be 40% by mass or more, and ES and AO can be stably blended even in such a blending system in which AG is the main surfactant. In addition, the upper limit of this AG ratio is 90 mass% or less from a cleaning power.

  The component (g) is contained in the composition in an amount of 0.05 to 8% by mass, preferably 0.1 to 5% by mass. This concentration is the concentration when the counter ion is assumed to be a hydrogen ion.

  Although the water of the present invention is the balance, it is blended in an amount of not more than 85% by mass and 80-30% by mass in consideration of other components in the composition.

  The pH of the liquid detergent composition of the present invention is preferably 4.5 to 9, more preferably 5.5 to 8 at 25 ° C. The lower limit is determined in terms of low-temperature stability, considering that the amine oxide of component (c) changes its degree of cationization depending on pH, and component (b) is acidic and unstable. The upper limit is determined in terms of sex. When adjusting pH to acid, in addition to inorganic acids such as hydrochloric acid and sulfuric acid, chelating agents such as citric acid and hydrotropes may be used. As alkali agents, in addition to alkanolamines, alkali metals may be used. Hydroxides may be used. In addition, pH is measured by the method of the below-mentioned Example.

  The viscosity of the liquid detergent composition of the present invention is preferably 10 to 1000 mPa · s, more preferably 25 to 500 mPa · s, from the viewpoint of liquid dischargeability. The viscosity is measured with a Brookfield viscometer at 20 ° C. The rotor is no. No. 2 is used and rotated at a rotational speed of 60 r / min, and the viscosity 60 seconds after the start of rotation is taken as the viscosity of the liquid detergent composition.

<Examples 1-4 and Comparative Examples 1-2>
A liquid detergent composition was prepared using the following components (a), (b), (c) and the like and the components shown in Table 2. At that time, the pH was adjusted using 48% sodium hydroxide (shown as “+” in Table 2). The measuring method of pH is as follows. After the adjustment, the detergency and low-temperature stability of these compositions were evaluated by the following methods. The results are also shown in Table 2. The components (a), (b) (including some comparative compounds), (c), etc. used are as follows.

(A) Component AG1: The composition of the alkyl group is C ₉ / C ₁₀ / C ₁₁ = 19/45/36 (mass ratio), n-isomer / iso-isomer = 85/15 mixed alkyl and glucoside average condensation degree 1.3 alkyl glucoside AG2: the alkyl group is a straight chain derived from nature, and the glucoside average is a mixed alkyl having an alkyl group composition of C ₈ / C ₁₀ / C ₁₂ = 50/35/15 (mass ratio) Alkyl glucoside with a condensation degree of 1.3

(B) Component / ES1: 0.4 mol of PO and 1.5 mol of EO are added to natural alcohol having an alkyl chain of C ₁₂ : C ₁₄ = 73: 27 (mass ratio), and then sulfur trioxide is added. Sulfated and neutralized with sodium hydroxide (10% diluted with water until neutralized until pH 11).
ES2: 0.6 mol of PO and 1.5 mol of EO were added to natural alcohol having an alkyl chain of C ₁₂ : C ₁₄ = 73: 27 (mass ratio), and then sulfated with sulfur trioxide, water Neutralized with sodium oxide (10% diluted with water until neutralized to pH 11).
· ES3: alkyl chain derived alcohol of C _12, 0.4 mol addition of PO, After 2.0 mols of EO, sulfated with sulfur trioxide, and neutralized with sodium hydroxide (10% in water It was neutralized until the pH of the diluted one was 11.)
ES4: 2.0 mol of EO was added to natural alcohol having an alkyl chain of C ₁₂ : C ₁₄ = 73: 27 (mass ratio), then sulfated with sulfur trioxide and neutralized with sodium hydroxide (water Neutralized until diluted to 10% with 10% dilution)
ES5: 4.0 moles of EO added to natural alcohol with C ₁₂ alkyl chain, then sulfated with sulfur trioxide and neutralized with sodium hydroxide (pH of 11 diluted with water is 11) Neutralized).
Details of ES1 to ES5 are shown in Table 1. The natural alcohol described above is composed only of a compound having a linear alkyl group.

(C) Component-AO1: N-lauryl-N, N-dimethylamine oxide (e-1) component-GLY1: Glycerin ethylene oxide adduct (number average molecular weight 1000)
(F) Component / Sulfobetaine: Lauryldimethylsulfobetaine

<Measurement method of pH>
A pH measuring composite electrode (HORIBA glass sliding sleeve type) was connected to a pH meter (HORIBA pH / ion meter F-23), and the power was turned on. A saturated potassium chloride aqueous solution (3.33 mol / L) was used as the pH electrode internal solution.

  Next, pH 4.01 standard solution (phthalate standard solution), pH 6.86 (neutral phosphate standard solution), and pH 9.18 standard solution (borate standard solution) were each filled in a 100 ml beaker. It was immersed in a constant temperature bath at 30 ° C. for 30 minutes. The pH measurement electrode was immersed in a standard solution adjusted to a constant temperature for 3 minutes, and calibration was performed in the order of pH 6.86 → pH 9.18 → pH 4.01.

  A sample (liquid detergent composition) was filled in a 100 ml beaker and adjusted to 25 ° C. in a constant temperature bath at 25 ° C. The pH measurement electrode was immersed in a sample adjusted to a constant temperature for 3 minutes, and the pH was measured.

<Detergency test>
1 g of model oil stain in which 0.1% by weight of pigment (stan red) is uniformly mixed with rapeseed oil and a polypropylene dish (C-39 PP meat dish made by Kanto Plastic Industry Co., Ltd.) Model contaminated tableware. Commercially available sponges (manufactured by Sumitomo 3M: Scotch Bright) were impregnated with 1.0 g of the liquid detergent composition shown in Table 2 and 30 g of tap water and bubbled by hand 2-3 times. Using this, the model-contaminated tableware was scrubbed, and the number of dishes that could be washed (checked whether or not the tableware could be washed with or without the presence of oily stains on the tableware) was determined.

<Low temperature stability>
100 ml of the liquid detergent composition shown in Table 2 was put into a PET bottle (Takemoto Container Co., Ltd., PEM-100), stored at -7.5 ° C. for 10 days, and the change in the appearance of the liquid was cleared immediately after preparation. In comparison with the uniform state, the evaluation was made according to the following criteria.
No change in appearance ... ○
Appearance changes such as gelation, separation, and precipitation formation.

<Formulation example>
Examples of other liquid detergent compositions of the present invention include formulation examples shown in Table 3. These compositions have detergency and low temperature stability suitable for hard surfaces.

The components in the table are the same as in Example 1 and some of them are as follows.
PPG-1000: Polypropylene glycol having a weight average molecular weight of 1000 Fatty acid (C12): Fatty acid having 12 carbons Nonionic 1: Alkyl group is sec-C12-14 alkyl group, polyoxyethylene having an average EO addition mole number of 3.3 Alkyl ether / nonion 2: polyoxyethylene alkyl ether / proxel BDN having an alkyl group of sec-C12-14 alkyl group and an average EO addition mole number of 7: 1,2-benzisothiazolin-3-one

Claims (3)

(A) 4 to 35% by mass of a compound represented by the following general formula (1), (b) a mixture containing a compound represented by the following general formula (2), the average of propylene oxide in the mixture 1 to 25% by mass of a mixture in which the added mole number m and the average added mole number n of ethylene oxide are 0 <m <1 and 0 <n ≦ 3, respectively (c) a hydrocarbon group having 8 to 18 carbon atoms, An amine oxide type surfactant having an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms is selected from 0.3 to 10% by mass, (d) a hydrotrope agent and (e) an organic solvent. A liquid detergent composition containing a phase stabilizer and water.
R ^1a- (OR ^1b ) _s G _t (1)
[Wherein, R ^1a represents an alkyl group having 8 to 16 carbon atoms, and R ^1b represents an alkylene group having 2 to 4 carbon atoms. G represents a group derived from a reducing sugar. s shows the number of 0-5 by average addition mole number, and t shows the number of 1-3 by average condensation degree. ]
R ^2a O— (PO) _m1 (EO) _n1 SO ₃ M (2)
[In the formula, R ^2a is an alkyl group having 8 to 18 carbon atoms, PO and EO are a propyleneoxy group and an ethyleneoxy group, respectively, m1 and n1 represent the added mole number of PO or EO, each of 0 or more. Is an integer. M is a cation. ] The liquid detergent composition of Claim 1 whose ratio of the compound whose m1 and n1 in general formula (1) are both 0 is 28 mass% or less in (b) component. Further, as the component (f), a nonionic surfactant other than the component (a), an anionic surfactant other than the component (b), and an amphoteric surfactant other than the component (c) 1 The liquid detergent composition according to claim 1 or 2, comprising at least one kind of surfactant, wherein the total amount of the surfactant is 10 to 60% by mass.