JP7624811B2 - Cleaning composition - Google Patents

Description

The present invention relates to a cleaning agent composition and a method for improving cleaning power.

Since residential cleaners are used in a variety of places and situations in the living environment, the dirt they can remove varies widely, from easy-to-remove dirt such as dust and food spills to extremely difficult dirt such as denatured oil stains. For this reason, the optimal cleaner is proposed for each place and situation of use. For example, strong alkaline cleaners are generally used for kitchen cleaners that can remove denatured oil stains, while cleaners with lower surfactant concentrations are used for less soiling such as on tables and windows, which do not leave unpleasant streaks or slimy feeling when wiped.

Patent Document 1 discloses a liquid detergent composition containing (a) 0.1 to 50% by weight of a glyceryl ether of a specific formula having an alkyl group having 5 carbon atoms, (b) 0.01 to 30% by weight of an anionic surfactant, a nonionic surfactant or an amphoteric surfactant, and water.
Patent Document 2 discloses a liquid detergent composition containing (a) 0.1 to 50% by weight of a glyceryl ether represented by a specific formula, (b) 0.001 to 10% by weight of a terpene hydrocarbon, (c) 0.01 to 30% by weight of a surfactant, (d) 0.01 to 30% by weight of a builder or alkaline agent, and water.
Patent Document 3 discloses a detergent composition containing (A) an amphoteric surfactant, (B) an anionic surfactant, (C) mono-2-ethylhexyl glyceryl ether or mono-2-ethylhexanoic acid glyceride, and (D) water, wherein the detergent composition is an isotropic surfactant continuous phase at 25° C. or a multiphase system in which an isotropic surfactant continuous phase and another phase coexist.
Patent Document 4 discloses a liquid cleaning agent composition for hard surfaces that contains a specific alkanolamide compound and a surfactant such as a sugar-based surfactant under specific conditions.
Patent Document 5 discloses a cleaning method in which an aqueous composition containing 0.01 to 2 mass % of a surfactant such as an alkylglycoside-type nonionic surfactant, 4 to 15 mass % of ethanol, and water is made into a foam and applied to an object to be cleaned.
Patent Document 6 discloses a cleaning composition for hard surfaces which contains (A) a monoalkyl glyceryl ether having an alkyl group with 3 to 8 carbon atoms, (B) a specific compound represented by general formula (1), (C) amines, (D) a polyvalent carboxylic acid and/or a salt thereof having a molecular weight of 40 to 400, (E) a surfactant (excluding (A) and (B)), and water, in which the (A)/(B) mass ratio, the (A)+(B) content, the (C)/(D) mass ratio, and the (C)+(D) content are each within a specific range, and the pH at 20° C. is 9.5 to 11.5.
Patent Document 7 discloses a neutral detergent composition for hard surfaces, which contains (A) a hydrocarbon having 6 to 16 carbon atoms, (B) a cationic surfactant, (C) at least one surfactant selected from nonionic surfactants and amphoteric surfactants, and water.
Patent Document 8 discloses a cleaning composition for hard surfaces, which contains (A) an alkyl or alkenyl succinic acid or a salt thereof having an alkyl or alkenyl group with 12 carbon atoms and an alkyl or alkenyl succinic acid or a salt thereof having an alkyl or alkenyl group with 14 carbon atoms, (B) a water-soluble organic solvent, (C) an amine compound, and water, and in which the mass ratio of surfactants other than component (A)/(A) is less than 1.

Japanese Patent Application Publication No. 11-189790 Japanese Patent Application Publication No. 11-256200 JP 2004-182760 A JP 2002-294281 A JP 2004-107655 A JP 2008-45108 A JP 2010-37515 A JP 2008-44993 A

The cleaning power of detergents using surfactants generally tends to be good when they are alkaline, but since objects to be cleaned in the living environment include not only hard surfaces such as glass and tiles, but also metals such as wood and iron, detergents that do not damage these are required, and neutral detergents are preferable in consideration of irritation to the body, etc. Therefore, detergents that are neutral and have excellent cleaning power are useful in this industry, and in particular, detergents with liquid pH close to neutral that have excellent cleaning power against oily stains attached to hard surfaces are desired.
Generally, the cleaning power of a detergent that uses a surfactant tends to improve with an increased amount of surfactant. However, if there is too much surfactant, when wiping the surface after application to a hard surface, more of the surfactant will remain behind as wiping streaks, or the remaining surfactant may affect the feel of the surface, such as making the surface slimy, resulting in a poor finish.

The present invention provides a cleaning composition that has excellent cleaning power against oily stains and provides excellent finish, such as less streaking and stickiness after cleaning.

The present invention provides a cleaning agent composition comprising: (a) a surfactant having one or more hydrocarbon groups each having from 11 to 18 carbon atoms (hereinafter referred to as component (a)); (b) a nonionic compound having one or more hydrocarbon groups each having from 1 to 10 carbon atoms and having a δph of from 2 to 17 (hereinafter referred to as component (b)); and water,
The composition contains, as the component (a), (a1) one or more surfactants selected from a betaine type surfactant and an amine oxide type surfactant [hereinafter referred to as component (a1)],
The proportion of the (a1) component in the (a) component is 60 mass% or more,
the mass ratio (b)/(a) of the content of the component (a) to the content of the component (b) is 0.01 or more and less than 0.5;
The pH at 25°C is 5 or more and 9 or less.
The present invention relates to a cleaning composition.

The present invention also provides a method for improving the detergency of a detergent composition containing component (a) and water against oily stains, comprising the steps of:
The component (b) is blended so that the mass ratio of the content of the component (a) to the content of the component (b), that is, (b)/(a), is 0.01 or more and less than 0.5;
As the component (a), the component (a1) is blended so that the ratio of the component (a1) in the component (a) is 60 mass% or more.
This relates to a method for improving cleaning power.

The present invention provides a cleaning composition that has excellent cleaning power against oily stains and has excellent finish, such as less wiping streaks and sliminess after cleaning, and a method for improving cleaning power.

The detergent composition of the present invention has excellent detergency against oily stains, and has good finish after cleaning, such as less wiping streaks and sliminess after cleaning hard surfaces. The reason why such effects are exhibited is not necessarily clear, but it is considered as follows.
The surfactant (a1) of the present invention, which is one or more surfactants selected from betaine type surfactants and amine oxide type surfactants, has a very excellent cleaning power against oily stains, but when cleaning a hard surface, when wiping after cleaning, it has been found that the fine particles remaining on the hard surface diffusely reflect visible light and are recognized as wiping streaks. It has also been found that these fine particles are generated by the precipitation of the components of the cleaning agent such as the component (a1), the precipitation of hardness components contained in the dilution water, and the adhesion of sand, dust, etc.
The nonionic compound having a specific δph, which is the component (b) of the present invention, can quickly adsorb and penetrate into the oily soil interface, and can assist the action of the component (a1) against oily soil. In the present invention, it is presumed that by using a predetermined amount of the component (b) for the component (a) containing a predetermined amount of the component (a1), the cleaning action of the component (a1) can be helped, the cleaning power can be improved, and the remaining oily soil can be reduced, so that high cleaning power and excellent finish can be imparted.

<Cleaning agent composition>
The cleaning composition of the present invention contains a surfactant having one or more hydrocarbon groups having from 11 to 18 carbon atoms as component (a), and contains, as component (a1), one or more surfactants selected from betaine surfactants and amine oxide surfactants. The hydrocarbon group of component (a) is preferably a group selected from an alkyl group having from 11 to 18, preferably 14, carbon atoms, and an alkenyl group having from 11 to 18, preferably 14, carbon atoms. Component (a) has one or more hydrocarbon groups having from 11 to 18, preferably 1 to 4, more preferably 3 or less, and even more preferably 2 or less, each of which has a carbon number of from 11 to 18.

Of the (a1) components, the betaine surfactant is a betaine surfactant having one or more hydrocarbon groups with 11 to 18 carbon atoms, preferably 14 or less, and specific examples include surfactants represented by the following general formula (a1-1).

[In the formula, R ¹¹ is an alkyl or alkenyl group having from 11 to 18, preferably from 14, carbon atoms, and R ¹² is an alkylene group having from 1 to 6 carbon atoms. A is a group selected from -COO-, -CONH-, -OCO-, -NHCO-, and -O-, and p is the number 0 or 1. R ¹³ and R ¹⁴ are alkyl or hydroxyalkyl groups having from 1 to 3 carbon atoms, and R ¹⁵ is an alkylene group having from 1 to 5 carbon atoms which may be substituted with a hydroxy group. B is a group selected from -SO ₃ ^- , -OSO ₃ ^- , and -COO-. ^]

In general formula (a1-1), the number of carbon atoms in R ¹¹ is preferably 11 or 12. A is preferably -COO- or -CONH-, more preferably -CONH-. The number of carbon atoms in R ¹² is preferably 2 or 3, and R ¹³ and R ¹⁴ are preferably methyl groups.

As the betaine type surfactant of the component (a1), one or more selected from alkyl carboxy betaine, alkyl amido carboxy betaine, alkyl sulfo betaine, alkyl hydroxy sulfo betaine, alkyl amido hydroxy sulfo betaine, and alkyl amino fatty acid salt are preferred. As the component (a1), one or more selected from alkyl amido propyl-N,N-dimethyl acetate betaine, alkyl-N,N-dimethyl-2-hydroxypropyl sulfo betaine, alkyl amido propyl-N,N-dimethyl-2-hydroxypropyl sulfo betaine, and alkyl amido propyl-N,N-dimethyl-propyl sulfo betaine are more preferred. These alkyl groups have 11 to 18 carbon atoms, preferably 14 or less. As the component (a1), one or more selected from lauric acid amido propyl-N,N-dimethyl acetate betaine, hydroxy lauryl sulfo betaine, lauryl-N,N-dimethyl-2-hydroxypropyl sulfo betaine, and lauric acid amido propyl-N,N-dimethyl-2-hydroxypropyl betaine are even more preferred. The (a1) component may contain two or more types of betaine surfactants.

Preferred betaine type surfactants include betaines such as alkyl (carbon number 11 to 18, preferably 14 or less)-N,N-dimethyl acetate betaine, fatty acid (fatty acid carbon number 12 to 19, preferably 15 or less) amidopropyl-N,N-dimethyl acetate betaine, alkyl (carbon number 11 to 18, preferably 14 or less)-N,N-dimethylethane sulfobetaine, alkyl (carbon number 8 to 18, preferably 10 to 18, preferably 14 or less)-N,N-dimethyl-2-hydroxypropyl sulfobetaine, fatty acid (fatty acid carbon number 12 to 19, preferably 15 or less) amidopropyl-N,N-dimethyl-2-hydroxypropyl sulfobetaine, and alkyl (carbon number 11 to 18, preferably 14 or less) carboxymethyl hydroxyethyl imidazolium betaine.

Among the (a1) components, the amine oxide surfactant is an amine oxide surfactant having one or more hydrocarbon groups with 11 to 18 carbon atoms, preferably 14 or less, such as an amine oxide having one alkyl or alkenyl group with 11 to 18 carbon atoms, preferably 14 or less, and specifically, a surfactant represented by the following general formula (a1-2):

[In the formula, R ²¹ is an alkyl or alkenyl group having 11 or more and 18 or less, preferably 14 or less, carbon atoms, R ²² is an alkylene group having 1 to 3 carbon atoms, A is a group selected from -COO-, -CONH-, -OCO-, and -NHCO-, p is the number 0 or 1, and R ²³ and R ²⁴ are each an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms.]

In general formula (a1-2), the number of carbon atoms in R ²¹ is preferably 11 or 12. A is preferably -COO- or -CONH-, more preferably -CONH-. The number of carbon atoms in R ²² is preferably 2 or 3, and R ²³ and R ²⁴ are preferably methyl groups.

Specific examples of amine oxides include N-lauryl-N,N-dimethylamine oxide, N-myristyl-N,N-dimethylamine oxide, N-lauroylaminopropyl-N,N-dimethylamine oxide, and N-myristylaminopropyl-N,N-dimethylamine oxide. N-lauryl-N,N-dimethylamine oxide (lauryl dimethylamine oxide), N-myristyl-N,N-dimethylamine oxide, and lauric acid amide propyl dimethylamine oxide are preferred, and N-lauryl-N,N-dimethylamine oxide and N-myristyl-N,N-dimethylamine oxide are preferred from the viewpoint of cleaning power for oily stains.

Surfactants other than component (a1) [hereinafter referred to as component (a2)] include nonionic surfactants, anionic surfactants, cationic surfactants, etc., from the viewpoints of improving cleaning and wiping properties, controlling foam quality, etc.

Nonionic surfactants include, but are not limited to, polyoxyethylene (addition mole number of ethylene oxide is 6 to 30) alkyl (carbon number 11 to 18, preferably 14 or less) ethers, polyoxyethylene (addition mole number of ethylene oxide is 1 to 6) alkyl (carbon number 11 to 18, preferably 14 or less) polyglycerin ethers, fatty acid (fatty acid carbon number 12 to 19, preferably 15 or less) alkanolamides, polyoxyethylene alkyl (carbon number 11 to 18, preferably 14 or less) amines, fatty acid (fatty acid carbon number 12 to 19, preferably 15 or less) glycerin monoesters, sorbitan fatty acid (fatty acid carbon number 12 to 19, preferably 15 or less) esters, sucrose fatty acid (fatty acid carbon number 12 to 19, preferably 15 or less) esters, alkyl or alkenyl (carbon number 11 to 18, preferably 14 or less) glycosides, etc.

Examples of the alkyl or alkenyl (having 11 to 18, preferably 14 or less, carbon atoms) glycoside include surfactants represented by the following general formula (a2-1).
R ³¹ (OR ³² ) _x G _y (a2-1)
[In the formula, R ³¹ represents a linear or branched alkyl or alkenyl group having 11 to 18 carbon atoms, preferably 14 or less, R ³² represents an alkylene group having 2 to 4 carbon atoms, G represents a residue derived from a reducing sugar having 5 or 6 carbon atoms, x represents an average number of 0 to 5, and y represents an average number of 1 to 10.]

In the above general formula (a2-1), the alkyl group or alkenyl group, preferably the alkyl group, represented by R ³¹ has 11 to 18 carbon atoms, preferably 14 or less, from the viewpoint of improving cleaning power and wiping ability. The alkylene group represented by R ³² has 2 to 4 carbon atoms from the viewpoint of solubility. The residue derived from a reducing sugar having 5 or 6 carbon atoms, represented by G, has a structure determined by the monosaccharide or disaccharide or higher sugar used. Examples of raw materials for the residue represented by G include monosaccharides such as glucose, galactose, xylose, mannose, lyxose, arabinose, fructose, or mixtures thereof, and examples of disaccharides or higher include maltose, xylobiose, isomaltose, cellobiose, gentibiose, lactose, sucrose, nigerose, turanose, raffinose, gentianose, menzitose, or mixtures thereof. Among these, preferred raw materials are glucose and fructose among monosaccharides, and maltose and sucrose among disaccharides or higher, in view of their availability and low cost.

In the above general formula (a2-1), x has an average value of 0 or more and 5 or less, preferably 2 or less, more preferably 1 or less, and even more preferably 0.
The average value of y in the above general formula (a2-1) is 1 or more, preferably 1.1 or more, more preferably 1.2 or more, and 10 or less, preferably 2 or less, more preferably 1.8 or less, and even more preferably 1.6 or less. The value of y (degree of sugar condensation) can be measured by ^1H -NMR.
Furthermore, when the average value of y in the above general formula (a2-1) is greater than 1, that is, when the glycoside has two or more sugar chains as hydrophilic groups, the bonding mode of the sugar chains can include any mixture of 1-2, 1-3, 1-4, 1-6 bonds, α-, β-pyranoside bonds, furanoside bonds, and mixed bonding modes thereof.

Examples of anionic surfactants include, but are not limited to, anionic surfactants having a polyoxyalkylene group. For example, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, polyoxyalkylene alkyl aryl ether sulfate, polyoxyalkylene alkenyl aryl ether sulfate, polyoxyalkylene monoalkyl ether phosphate, polyoxyalkylene dialkyl ether phosphate, polyoxyalkylene monoalkenyl ether phosphate, polyoxyalkylene dialkenyl ether phosphate, polyoxyalkylene monophenyl ether phosphate, polyoxyalkylene diphenyl ether phosphate, polyoxyalkylene alkyl ether carboxylate, polyoxyalkylene alkenyl ether carboxylate, polyoxyalkylene alkyl ether acetate, polyoxyalkylene alkenyl ether acetate, etc. The number of carbon atoms of these alkyl or alkenyl groups is 11 to 18, preferably 14 or less. In addition, polyoxyethylene is preferable as the polyoxyalkylene. The average number of moles of oxyalkylene groups, such as oxyethylene groups, added is 0.1 or more, preferably 0.5 or more, and 5 or less, preferably 3 or less. Examples of salts include alkali metal salts, ammonium salts, and alkanolamine salts.

The amount of the anionic surfactant may be adjusted in consideration of the finish after wiping. In the present invention, for example, the content of the anionic surfactant in the composition may be 10% by weight or less, further 5% by weight or less, or further 0% by weight, relative to component (a). In other words, the cleaning composition of the present invention may not contain an anionic surfactant.

Examples of cationic surfactants include alkyl (e.g., having 11 to 16 carbon atoms, preferably 14 or less) trimethylammonium salts, dialkyl (e.g., having 11 to 16 carbon atoms, preferably 14 or less) dimethylammonium salts, triethanolamine difatty acid ester quaternary salts, fatty acid (e.g., having 12 to 17 carbon atoms, preferably 14 or less) monoester monoamide salts of N-hydroxyethyl-N-methyl-propanediamine, alkyl (e.g., having 11 to 16 carbon atoms, preferably 14 or less) benzyldimethylammonium salts, alkyl (e.g., having 11 to 16 carbon atoms, preferably 14 or less) pyridinium salts, etc.

The cationic surfactant may have bactericidal properties.
The cationic surfactant may be represented by the following general formula (a2-2):

[Wherein,
R ⁴¹ is an alkyl group having 11 to 16 carbon atoms, preferably 14 or less.
R ⁴² is a group selected from the group consisting of a methyl group, an ethyl group, and an alkyl group having 6 to 16 carbon atoms, preferably 14 or less,
R ⁴³ is a methyl group or an ethyl group;
R ⁴⁴ is a group selected from the group consisting of a methyl group, an ethyl group, and a benzyl group;
L ⁻ is a counter ion.

In general formula (a2-2), R ⁴¹ is an alkyl group having 11 or more and 16 or less, and preferably 14 or less, carbon atoms.
In addition, in general formula (a2-2), R ⁴² is a group selected from the group consisting of a methyl group, an ethyl group, and an alkyl group having 6 to 16 carbon atoms, preferably a methyl group, an ethyl group, or an alkyl group having 8 to 14 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.
In addition, in general formula (a2-2), R ⁴³ represents a methyl group or an ethyl group, and a methyl group is preferable.
In addition, in general formula (a2-2), R ⁴⁴ is a group selected from the group consisting of a methyl group, an ethyl group, and a benzyl group, preferably a methyl group or a benzyl group, and more preferably a benzyl group.
In general formula (a2-2), ^L- is a counter ion and may be an anionic group selected from the group consisting of a halide ion such as a chloride ion or a bromide ion, an alkyl sulfate ion having from 1 to 5 carbon atoms, an alkyl-substituted benzenesulfonate ion having an alkyl group having from 1 to 3 carbon atoms as a substituent, and an alkyl phosphate ion having from 6 to 18 carbon atoms. ^L- is preferably an anionic group selected from the group consisting of a chloride ion, a bromide ion, and an alkyl sulfate ion having from 1 to 5 carbon atoms.

From the viewpoint of improving wiping properties, the (a2) component is preferably a nonionic surfactant, more preferably an alkyl glycoside, even more preferably an alkyl glycoside having an alkyl group with 11 to 18 carbon atoms, preferably 14 or less, and even more preferably a glycoside having an alkyl group with 12 carbon atoms, such as lauryl glycoside.

Component (a) is preferably a surfactant that does not have a hydrocarbon group with 19 or more carbon atoms.

In terms of cleaning power and finish, the cleaning composition of the present invention has a ratio of component (a1) in component (a) of 60% by mass or more, more preferably 65% by mass or more, and preferably 99% by mass or less, more preferably 90% by mass or less, even more preferably 80% by mass or less, and even more preferably 77% by mass or less.

From the viewpoint of achieving both oil-stain cleaning power and a good finish, the cleaning composition of the present invention contains component (a1) in an amount of preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass.

From the viewpoint of achieving both oil stain cleaning power and a good finish, the detergent composition of the present invention contains component (a) in an amount of preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass.

Component (b) is a nonionic compound having one or more hydrocarbon groups with 1 to 10 carbon atoms and a δph of 2 to 17. Component (b) is believed to exhibit higher mobility in aqueous solution than component (a), and is therefore believed to quickly adsorb to and penetrate the surface of modified oils and the like. The hydrocarbon group of component (b) is preferably an alkyl group with 1 to 10 carbon atoms, or an alkenyl group with 1 to 10 carbon atoms. Component (b) has one or more hydrocarbon groups with 1 to 10 carbon atoms, preferably one to four, more preferably three or less, and even more preferably two or less.

The (b) component is preferably a nonionic compound that does not have a hydrocarbon group having 11 or more carbon atoms, for example, a hydrocarbon group having 11 to 18 carbon atoms.

δph of component (b) is the polar term of Hansen's solubility parameter, and is defined as δph = (δp ² + δh ² ) ^1/2 . Here, δp is a term indicating the dipole-dipole force between molecules, and δh is a term indicating the hydrogen bond force between molecules. δp and δh can be obtained from the van Krevelen diagram. In this case, RF Fedors: Polym. Eng. Sci., 14, (2), 147-154 (1974) and KE Meusburger: "Pesticide Formulations: Innovations and Developments", Chapter 14 (Am. Chem. Soc.), 151-162 (1988) can be referred to. The nonionic compound of component (b) may be a compound that does not exhibit ionicity when dissolved in water.

For component (b), a nonionic compound with a δph of 2 or more and 17 or less is used from the viewpoint of having high permeability to modified oils. From the viewpoint of having high permeability to modified oils, the δph of component (b) is preferably 3 or more, more preferably 7 or more, and preferably 16 or less, more preferably 15.5 or less. From the viewpoint of cleaning power, the δph of component (b) is preferably 2 or more, preferably 5 or more, and preferably 12 or less, more preferably 10 or less. From the viewpoint of finish, the δph of component (b) is preferably 13 or more and 17 or less.

Examples of component (b) include alcohols, ethers, ketones, aldehydes, esters, and combinations of these compounds having the above δph. The detergent composition may contain one or more types of component (b). Ethers include glycol ethers and glyceryl ethers. Examples of nonionic compounds of component (b) having a δph of 2 to 17 are given below. In the following examples, alkyl and alkenyl groups unless otherwise specified have a carbon number selected from 1 to 11.

Examples of alcohols include isopropyl alcohol, butylpropanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, 2-ethyl-1-hexanol, cyclohexanol, benzyl alcohol, 3-methyl-3-methoxybutanol, phenoxyethanol, and phenoxyisopropanol. These alcohols may be used alone or in combination of two or more.

Among the ethers, examples of glycol ethers include alkylene glycol monoalkyl or alkenyl ethers in which the number of carbon atoms in the alkyl group is 1 to 4 or the number of carbon atoms in the alkenyl group is 2 to 4, and the number of carbon atoms in the alkylene group is 2 to 4. From the viewpoint of good cleaning power and finish, examples of the alkylene glycol monoalkyl or alkenyl ether include propylene glycol monoalkyl ethers in which the number of carbon atoms in the alkyl group is 1 to 4, and ethylene glycol monoalkyl ethers in which the carbon atoms in the alkyl group is 1 to 4.

Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-normal propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-normal butyl ether, propylene glycol monoisobutyl ether, and propylene glycol mono-tertiary butyl ether.

Examples of glycol ethers include dipropylene glycol monoalkyl ethers. Examples of dipropylene glycol monoalkyl ethers include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-normal propyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol mono-normal butyl ether, dipropylene glycol monoisobutyl ether, and dipropylene glycol mono-tertiary butyl ether.

Moreover, examples of the glycol ether include compounds represented by the following general formula (b1).
R ⁵¹ -O-(CH ₂ CH(CH ₃ )O) _n -H (b1)
[In the formula, R ⁵¹ is an alkyl group having 1 to 4 carbon atoms or an alkenyl group having 2 to 4 carbon atoms, and n is a number of 1 to 3.]
Preferably, n is 2.

Preferred glycol ethers are propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-normal propyl ether, propylene glycol mono-normal butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-normal propyl ether, and dipropylene glycol mono-normal butyl ether.

The glycol ethers may be used alone or in combination of two or more types.

As the glycol ether, propylene glycol monoalkyl ethers in which the alkyl group has 1 to 4 carbon atoms, and propylene glycol monomethyl ether are more preferred. When propylene glycol monomethyl ether is used, either 1-methoxy-2-propanol or its isomer 2-methoxy-1-propanol may be used, or a mixture of the two may be used.

Among the ethers, glyceryl ethers include monoglyceryl ethers having a hydrocarbon group with 6 to 10 carbon atoms, such as a linear or branched alkyl group.

Among the ethers, examples of glyceryl ethers include compounds represented by the following general formula (b2).
R ⁷¹ -O-(CH ₂ CH(OH)CH ₂ O) _r -H (b2)
[In the formula, R ⁷¹ is a hydrocarbon group having 6 to 10 carbon atoms, and r is the average number of moles added and is a number of 1 to 4.]

In general formula (b2), R ⁷¹ is preferably an alkyl group, more preferably a branched alkyl group. R ⁷¹ is preferably a 2-ethylhexyl group or an isodecyl group, more preferably a 2-ethylhexyl group. r is preferably 1 or more and 3 or less, more preferably 1 or more and 2 or less, and even more preferably 1. An even more preferred compound is one in which R ⁷¹ is a 2-ethylhexyl group and r is 1.

The ester is, for example, an ester compound having a hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include esters of monohydric alcohols having 1 to 10 carbon atoms and fatty acids having 1 to 10 carbon atoms. Specific examples of the ester include compounds of the general formula (b3).

[In the formula, R ⁶¹ and R ⁶² each represent a hydrocarbon group having 1 to 10 carbon atoms.]

In the general formula (b3), R ⁶¹ and R ⁶² are each a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group include an alkyl group and an alkenyl group, and the alkyl group is preferable. The total carbon number of R ⁶¹ and R ⁶² is preferably 2 to 9.

As the compound of general formula (b3), an ester compound in which R ⁶¹ is a hydrocarbon group having 3 to 10 carbon atoms, R ⁶² is a hydrocarbon group having 1 to 4 carbon atoms, and the total number of carbon atoms of R ⁶¹ and R ⁶² is 5 to 8 is preferable.
As the compound of general formula (b3), an ester compound selected from an ester compound in which R ⁶¹ is a hydrocarbon group having 3 to 10 carbon atoms and R ⁶² is a hydrocarbon group having 1 carbon atom, and an ester compound in which R ⁶¹ is a hydrocarbon group having 3 to 8 carbon atoms and R ⁶² is a hydrocarbon group having 2 to 3 carbon atoms is more preferable.

Representative examples of ester compounds are given below, but are not limited to these.

Methyl esters include methyl acetate, methyl propionate, methyl butyrate, methyl valerate, methyl caproate (methyl hexanoate), methyl enanthate, methyl caprylate, methyl pelargonate, and methyl caprate.

Ethyl esters include ethyl acetate, ethyl propionate, ethyl butyrate, ethyl valerate, ethyl caproate, ethyl enanthate, ethyl caprylate, ethyl pelargonate, and ethyl caprate.

Propyl esters include propyl acetate, propyl propionate, propyl butyrate, propyl valerate, propyl caproate, propyl enanthate, propyl caprylate, propyl caprylate, propyl pelargonate, propyl caprate, isopropyl acetate, isopropyl propionate, isopropyl butyrate, isopropyl valerate, isopropyl caproate, isopropyl enanthate, isopropyl caprylate, isopropyl caprylate, isopropyl pelargonate, and isopropyl caprate.

Butyl esters include butyl acetate, butyl propionate, butyl butyrate, butyl valerate, butyl caproate, butyl enanthate, butyl caprylate, butyl pelargonate, butyl caprate, isobutyl acetate, isobutyl propionate, isobutyl butyrate, isobutyl valerate, isobutyl caproate, isobutyl enanthate, isobutyl caprylate, isobutyl pelargonate, and isobutyl caprate.

From the viewpoint of cleaning properties against modified oils, the ester is preferably a methyl ester, an ethyl ester, or a propyl ester. That is, an ester having an alkyl group having 1 to 3 carbon atoms is preferred. Specifically, one or more selected from methyl caproate, methyl caprylate, methyl caprate, ethyl caproate, ethyl caprylate, and propyl caproate are preferred, one or more selected from methyl caproate, methyl caprylate, and methyl caprate are more preferred, and methyl caproate is even more preferred.

Preferred (b) component includes alkyl glyceryl ethers and further monoalkyl glyceryl ethers having a δph of 2 to 17 and an alkyl group having 6 to 10 carbon atoms. The cleaning composition of the present invention preferably contains, as component (b), alkyl glyceryl ethers and further monoalkyl glyceryl ethers having a δph of 2 to 17 and an alkyl group having 6 to 10 carbon atoms.

From the viewpoint of finish quality, the cleaning composition of the present invention has a mass ratio (b)/(a) of the content of component (a) to the content of component (b) of 0.01 or more, preferably 0.05 or more, more preferably 0.1 or more, and less than 0.5, preferably less than 0.50, more preferably 0.4 or less, and even more preferably 0.3 or less.

From the viewpoint of finish quality, the cleaning composition of the present invention has a mass ratio (b)/(a1) of the content of the component (a1) to the content of the component (b) that is preferably 0.01 or more, more preferably 0.05 or more, and preferably 0.3 or less, more preferably 0.2 or less.

From the viewpoint of improving the detergency against modified oils, the detergent composition of the present invention contains the components (a) and (b) in a total amount of preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less.

From the viewpoint of improving the cleaning power against modified oils and improving the finish, the detergent composition of the present invention contains component (a) in an amount of preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less.

The detergent composition of the present invention may optionally contain a nonionic compound with a δph of less than 2 or more than 17, but the content may be 30% by mass or less, further 20% by mass or less, and further 10% by mass or less, based on the (b) component, from the viewpoint of the cleaning power of the modified oil.

The cleaning composition of the present invention contains water. The water content is, for example, 80% by mass or more, further 90% by mass or more, and 99% by mass or less, further 97% by mass or less. The cleaning composition of the present invention is a liquid.

The cleaning composition of the present invention may contain other optional ingredients such as antioxidants, preservatives, thickeners, rust inhibitors, pH adjusters, colorants, fragrances, and bactericides. The amount of the optional ingredients is limited in consideration of the finish after wiping.

In the present invention, the amount of the sequestering agent in the composition may be 10% by mass or less, further 5% by mass or less, further 3% by mass or less, or even 0% by mass, based on the (a) component. In other words, the cleaning agent composition of the present invention may not contain a sequestering agent. The sequestering agent whose content is limited in this way may be a sequestering agent selected from polycarboxylic acids such as citric acid, malic acid, tartaric acid, succinic acid, methylglycine diacetate, glutamic acid diacetate, hydroxyethyliminodiacetate, ethylenediaminedisuccinic acid, nitrilotriacetate, 1,3-propanediaminetriacetate, 1,3-diamino-2-hydroxypropanetetraacetate, glycoletherdiaminetetraacetate, ethylenediaminetetraacetate, diethylenetriaminepentaacetate, triethylenetetraaminehexaacetate, dihydroxyethylglycine, and hydroxyethylethylenediaminetriacetate, dicarboxymethylglutamic acid, and tripolyphosphoric acid.

As the fragrance, a single fragrance component may be used, or a fragrance composition containing multiple fragrance components in a specific ratio may be used. As the fragrance component, those described in "Chemistry of Fragrances" (by Akaboshi Ryoichi, published by the Chemical Society of Japan, Industrial Chemistry Series, September 16, 1983), "Synthetic Fragrances Chemistry and Product Knowledge" (by Indo Genichi, published by Chemical Daily, March 6, 1996), and "Fundamentals of Fragrances and Fragrance Blending" (by Nakajima Mototaka, published by Sangyo Tosho Co., Ltd., June 21, 1995) may be used. Specifically, one or more types selected from hydrocarbon-based fragrances, alcohol-based fragrances, ether-based fragrances, aldehyde-based fragrances, ketone-based fragrances, ester-based fragrances, lactone-based fragrances, cyclic ketone-based fragrances, and nitrogen-containing fragrances may be mentioned, preferably one or more types selected from hydrocarbon-based fragrances, alcohol-based fragrances, and aldehyde-based fragrances.

The cleaning composition of the present invention has a pH at 25°C of 5 or more, preferably 6 or more, and 9 or less, preferably 8 or less. Such a pH is preferable in consideration of the effect on the object to be cleaned, and the cleaning composition of the present invention can achieve both excellent cleaning power and finish quality within this pH range.

The cleaning composition of the present invention has a viscosity at 25°C of preferably 1 mPa·s or more, more preferably 2 mPa·s or more, and preferably 1000 or less, more preferably 300 mPa·s or less. This viscosity is measured using an Ubbelohde viscometer (manufactured by Shibata Scientific Machinery Co., Ltd.).

The cleaning composition of the present invention is suitable as a cleaning composition for hard surfaces. The cleaning composition of the present invention can be applied to, for example, hard surfaces in ordinary households such as kitchens, bathrooms, and toilets, and hard surfaces in various industrial facilities such as food processing plants. In particular, it can be suitably applied to hard surfaces such as kitchens, living rooms, cooking utensils, and food processing plants that are prone to adhesion of oil stains. A cleaning composition for wiping and cleaning hard surfaces is one of the preferred aspects of the present invention.

The cleaning composition of the present invention is preferably used by spraying or applying it to an object, for example, a hard surface having oily stains or the like. A spray means can be used for spraying or applying. The present invention provides a cleaning product in a spray container, which is formed by filling the cleaning composition of the present invention into a container equipped with a sprayer, and further a cleaning product for hard surfaces in a spray container.

In the spray-container-packed cleaning agent article of the present invention, the container equipped with a sprayer into which the cleaning agent composition of the present invention is filled may be a manual spray device that does not use a propellant, such as a trigger-type spray container or a pump-type spray container, or an aerosol that uses a propellant. The container equipped with the sprayer is preferably a trigger-type spray that can spray or apply the contents in the form of droplets or foam, and more preferably a trigger-type spray equipped with a mechanism for spraying the contents in the form of droplets or a mechanism for forming foam (foam-forming mechanism).

When a trigger-type spray equipped with a mechanism for spraying the detergent composition of the present invention in the form of droplets is used in the spray-container-packed detergent article of the present invention, the nozzle diameter of the spray container containing the composition is preferably 0.1 mm or more, more preferably 0.3 mm or more, and preferably 2 mm or less, more preferably 1 mm or less, in order to facilitate spraying, ensure that the sprayed droplets are not rough, are not sprayed in a straight line, and prevent the spray area from becoming extremely narrow.
When using a trigger-type spray equipped with a mechanism for spraying in the form of droplets, the spray-contained cleaning article of the present invention sprays preferably 0.1 mL or more, more preferably 0.3 mL or more, and preferably 5 mL or less, more preferably 2 mL or less of the composition in one operation.

When using a trigger-type spray equipped with a foam-forming mechanism in the spray-container-packaged cleaning article of the present invention, it is preferable to use one having a spin element and a liquid passage plate with several rod-shaped protrusions installed in a circular space with a diameter of 4 to 8 mm. Here, the spin element is a mechanism that gives a spin to the flow of liquid through the spin element and finally sprays it from a nozzle, and for detailed structure, reference can be made to JP-A-8-332422, FIG. 4(b) of JP-A-8-108102, FIG. 1 of JP-A-2002-68265, etc.

When using a trigger-type spray equipped with a foam-forming mechanism, the spray-contained cleaning article of the present invention sprays, in one operation, preferably 0.5 mL or more, more preferably 1 mL or more, and preferably 30 mL or less, more preferably 15 mL or less, and even more preferably 5 mL or less of the composition.

The liquid passage plate, another component of the foam-forming mechanism, has preferably 3 to 8 rod-shaped protrusions installed in a circular space with a diameter of 5 to 7 mm, and when the plate is viewed in plan, the rod-shaped protrusions are preferably rectangular with a width of 0.8 to 1.2 mm and a length of 2 to 4 mm. Furthermore, the area occupied by the rod-shaped protrusions in relation to the space excluding the rod-shaped protrusions is preferably 30 area% or more, more preferably 40 area% or more, and preferably 90 area% or less, more preferably 80 area% or less, and even more preferably 70 area% or less. By installing such a liquid passage plate, the adhesion and retention of foam on the vertical surface is improved.

The container of the spray-container-packaged cleaning agent article of the present invention can be a commonly used container. For example, it can be obtained from raw materials such as polyethylene, polypropylene, or polyethylene terephthalate, and can be manufactured by blow molding or the like. The thickness of the container may differ between the bottom and sides, and is preferably 0.01 to 2 mm, and the container capacity is preferably 100 to 1000 mL. For ease of handling, the amount of liquid cleaning agent composition filled into the container is preferably 200 to 500 mL. Furthermore, the liquid is filled while leaving a reasonable amount of space.

<How to improve cleaning power>
The present invention relates to a method for improving the detergency against oily stains of a detergent composition containing (a) a surfactant having one or more hydrocarbon groups having from 11 to 18 carbon atoms (hereinafter referred to as component (a)) and water, the method comprising the steps of:
(b) a nonionic compound having one or more hydrocarbon groups having 1 to 10 carbon atoms and a δph of 2 to 17 (hereinafter referred to as component (b)) is blended in such a way that the mass ratio (b)/(a) of the content of component (a) to the content of component (b) is 0.01 or more and less than 0.5,
As the component (a), (a1) one or more surfactants selected from a betaine type surfactant and an amine oxide type surfactant [hereinafter referred to as component (a1)] are blended in such a way that the ratio of component (a1) in the component (a) is 60 mass% or more;
A method for improving cleaning power is provided.
The matters described in the description of the cleaning composition of the present invention can be appropriately applied to the method for improving detergency of the present invention. Specific examples and preferred examples of the components (a) and (b) are also the same as those in the cleaning composition of the present invention. In addition, the contents of each component described in the description of the cleaning composition of the present invention can be applied to the method for improving detergency of the present invention by replacing them with the blending amounts.
The present invention has discovered that, when an object is cleaned with a detergent composition containing a surfactant and water, the cleaning power of the detergent composition, in particular the cleaning power for oily stains, is improved by using a predetermined amount of component (a1) as a surfactant and using component (b) in a predetermined mass ratio to component (a).

How to clean hard surfaces
The cleaning composition of the present invention is suitable for cleaning hard surfaces. According to the present invention, there is provided a method for cleaning a hard surface, which comprises wiping and cleaning the hard surface using the cleaning composition of the present invention.

The cleaning composition and cleaning article in a spray container of the present invention are suitable as a wet wiping composition or wet wiping article. That is, they are suitable for light cleaning of hard surfaces (various objects, floors, walls, ceilings, etc.) in living areas such as living rooms, rooms, kitchens, bathrooms, and toilets. In this case, the composition of the present invention does not foam, become slimy, or leave marks, has excellent finish, and dries quickly, so there is no need to wipe with water (twice). The present invention provides a method for cleaning hard surfaces in which the cleaning composition of the present invention is applied to the hard surface and then wiped to clean it. In the wipe-off cleaning, it is preferable to remove the composition applied to the hard surface from the hard surface using a cloth, dustcloth, nonwoven fabric, etc.

The cleaning composition of the present invention can also be used as a cleaning article by impregnating a substrate. A cleaning article in which a substrate is impregnated with the composition for wiping and cleaning hard surfaces of the present invention is preferred from the viewpoint of ease of cleaning work.

The matters described for the cleaning composition of the present invention can be appropriately applied to the method for cleaning hard surfaces of the present invention.

In the method for cleaning a hard surface of the present invention, it is preferable to fill a spray container with the detergent composition of the present invention, spray the foam, and apply the foam to dirt on the hard surface. In the method for cleaning a hard surface of the present invention, the above-mentioned detergent article in a spray container of the present invention can be used.
In the method for cleaning a hard surface of the present invention, it is preferable to apply the cleaning composition of the present invention to a hard surface and then leave it to stand for a predetermined time, for example, 10 seconds or more, further 0.5 minutes or more, further 1 minute or more, and 5 minutes or less, further 3 minutes or less, further 2 minutes or less.
In the method for cleaning a hard surface of the present invention, wiping and cleaning of the hard surface can be performed using a suitable wiping material, such as a sheet, a brush, a mop, etc. The wiping material may contain fibers such as natural fibers and synthetic fibers.
In the method for cleaning a hard surface of the present invention, the hard surface after wiping and cleaning may be rinsed with water or the like.

An example of the method for cleaning hard surfaces of the present invention is a method for cleaning hard surfaces in the home, i.e., kitchens, dining tables, wooden floors, furniture, exteriors of home appliances, bathrooms, toilets, mirrors, glass, washstands, stoves, car interiors, etc., in a predetermined amount, for example, about 6 mL per 1 ^m2 , of the detergent composition of the present invention, and then the composition is wiped off using a support, for example, a support that is dry or impregnated with a formulation liquid, water, etc. For wiping, it is preferable to remove the composition suitable for hard surfaces from the hard surface using a cloth, dustcloth, nonwoven fabric, kitchen paper, tissue paper, etc. In this case, since the composition of the present invention has excellent finish and dries quickly, there is no need to wipe with water (twice).

The cleaning compositions shown in Table 1 were prepared and the following evaluations were carried out. The results are shown in Table 1.

[Evaluation of cleaning power]
Rapeseed oil (FUJIFILM Wako Pure Chemical Industries, Ltd.) denatured by heating at 180°C for 6 hours was sprayed onto a stainless steel top plate (JIS G4305, SUS304, 8 cm x 12 cm x 1.0 mm, manufactured by Engineering Test Service Co., Ltd.). The amount of adhesion was set ^to 0.1 mg/cm2, assuming the amount of dirt in an actual field. The detergent composition was sprayed once (10 mg/ ^cm2 ) onto the stainless steel surface, and then wiped off with a sheet of kitchen paper (Elleair Super Absorbent Kitchen Towel, manufactured by Daio Paper Co., Ltd.). The oil stain cleaning rate was calculated from the difference in mass of the stainless steel top plate before and after wiping. The cleaning rate was calculated from cleaning rate = (1 - [(A2) - (A0)] / [(A1) - (A0)]) x 100. In the formula, A0 is the mass (g) of the stainless steel top plate before dirt is attached, A1 is the mass (g) of the stainless steel top plate with dirt attached, and A2 is the mass (g) of the stainless steel top plate after wiping and cleaning. Mass measurements were performed using an AB204-S analytical balance manufactured by Mettler Toledo. The cleaning power was evaluated from the obtained cleaning rate according to the following evaluation criteria.
5 points: cleaning rate is more than 97% and less than 100% 4 points: cleaning rate is more than 95% and less than 97% 3 points: cleaning rate is more than 90% and less than 95% 2 points: cleaning rate is more than 80% and less than 90% 1 point: cleaning rate is less than 80%

[Evaluation of finish (slippery/sticky)]
In the evaluation of the cleaning power, after wiping with kitchen paper, four panelists (researchers in the relevant field in their 20s and 30s) touched the stainless steel surface with their fingers and judged it according to the following criteria. Table 1 shows the average value of the four panelists.
5 points: Almost no stickiness or sliminess 4 points: Stickiness or sliminess remains, but is not noticeable 3 points: Slight stickiness or sliminess remains, but is not noticeable 2 points: Stickiness or sliminess remains, but is noticeable 1 point: Significant stickiness or sliminess remains

[Evaluation of finish (wiping streaks)]
In the evaluation of the cleaning power, after wiping with kitchen paper, and before the evaluation of sliminess and stickiness, the finish of the stainless steel surface was visually observed by four panelists (researchers in the relevant field in their 20s and 30s) and judged according to the following criteria. The average value of the four panelists is shown in Table 1.
5 points: Almost no streaks left 4 points: Slight streaks left but not noticeable 3 points: Slight streaks left but not noticeable 2 points: Streaks left but noticeable 1 point: Significant streaks left

The ingredients in the table are as follows:
・Lauryl-2-hydroxypropyl sulfobetaine: Amphitol 20HD, manufactured by Kao Corporation ・Lauryl amidopropyl betaine: Amphitol 20AB, manufactured by Kao Corporation ・Lauryl betaine: Amphitol 20BS, manufactured by Kao Corporation ・Lauryl dimethylamine oxide: Amphitol 20N, manufactured by Kao Corporation ・Lauryl aminopropyl dimethylamine oxide: Softazoline LAO, Kawaken Fine Chemical Co., Ltd. ・Lauryl glycoside: Mydol 12, manufactured by Kao Corporation ・2-Ethylhexyl glyceryl ether: Penetol GE-EH, manufactured by Kao Corporation

Claims (3)

A hard surface cleaning composition comprising: (a) 0.1% by mass or more and 3% by mass or less of a surfactant having one or more hydrocarbon groups each having from 11 to 18 carbon atoms [hereinafter referred to as component (a)]; (b) an alkyl glyceryl ether having an alkyl group having from 6 to 10 carbon atoms [hereinafter referred to as component (b)]; and water,
The composition contains, as the component (a), (a1) one or more surfactants selected from a betaine type surfactant and an amine oxide type surfactant [hereinafter referred to as the component (a1)] and (a2) an alkyl glycoside,
The proportion of the (a1) component in the (a) component is 60 mass% or more,
the mass ratio (b)/(a) of the content of the component (a) to the content of the component (b) is 0.1 or more and less than 0.5;
The pH at 25°C is 5 or more and 9 or less.
A cleaning composition for hard surfaces. The cleaning composition for hard surfaces according to claim 1 , which is for wiping and cleaning hard surfaces. A method for improving the detergency against oily stains of a hard surface cleaner composition containing 0.1% by mass or more and 3% by mass or less of (a) a surfactant having one or more hydrocarbon groups having from 11 to 18 carbon atoms (hereinafter referred to as component (a)) and water, comprising the steps of:
(b) an alkyl glyceryl ether having an alkyl group with 6 to 10 carbon atoms (hereinafter referred to as component (b)) is blended in such a way that the mass ratio (b)/(a) of the content of component (a) to the content of component (b) is 0.1 or more and less than 0.5;
As the component (a), (a1) one or more surfactants selected from a betaine type surfactant and an amine oxide type surfactant [hereinafter referred to as component (a1)] and (a2) an alkyl glycoside are blended so that the ratio of component (a1) in the component (a) is 60 mass% or more;
How to improve cleaning power.