JPH11286699A - Liquid detergent composition for hard body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compsn. causing little damage to a washed surface and improvemed in detergency washing power, anti-restaining ability, and the feel of finish by contg. an anionic surfactant, a specific cationic surfactant, and a water-soluble polymer. SOLUTION: A compsn. comprises a blend of 0.1-30 wt.%, pref. 0.5-20 wt.% of an anionic surfactant such as an alkylbenzene sulfonate salt, an anionic surfactant having a polyoxyalkylene group, or the like; 0.05-15 wt.%, pref. 0.1-10 wt.% of the cationic surfactant having a 6-22C alkyl group of formula I, formula II, or the like (wherein R1 is 6-20C linear or branched alkyl or alkenyl; R2 is methyl, 6-20C linear or branched alkyl or alkenyl; R3 is 6-20C alkyl or alkenyl; and X is halogen or an alkylsulfonic acid moiety); 0.01-10 wt.%, pref. 0.1-8 wt.% of a water-soluble polymer; and water, with having a pH adjusted to 3-12, pref. 5-12, and especially pref. 6-11.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to the present invention, which exhibits excellent detergency, especially for dirt on hard objects such as floors and furniture, and has excellent anti-recontamination properties and a feeling of finish on cleaning tools. The present invention relates to a liquid detergent composition for a hard body which is hardly damaged by the liquid.

[0002]

2. Description of the Related Art Nonionic surfactant-based detergents are widely used as residential detergents for floors and the like because of their excellent detergency.
However, such cleaning agents use the rags used for cleaning,
When cleaning and removing dirt attached to a cleaning tool such as a brush, there is a problem that dirt dispersed in the cleaning liquid adheres to the cleaning tool again.

[0003] Further, a cleaning agent is required not only to have a detergency but also to not damage a substrate to be cleaned. For example, depending on the solvent used in the cleaning agent, A, which has recently been widely used as a material for various structures,
When washing a plastic base represented by a base material made of a styrene resin such as a BS resin or a base material in which a styrene resin is used in combination with another material such as a metal and a glass, there is a possibility that they may be damaged. . Furthermore, in order to use as a cleaning agent for a house, it is also an important factor that the wiping is not required twice and that the finished feeling such as no stickiness is good.

[0004] The present invention is a hard material having excellent detergency, excellent finish feeling after use, prevention of recontamination of cleaning tools, and no damage to plastic substrates. An object of the present invention is to provide a liquid cleaning composition for body use.

[0005]

Means for Solving the Problems The present inventors have found that when the following components (a), (b) and (c) are combined, the above object can be achieved by synergistic action thereof, and the present invention has been completed. did.

[0006] The present invention relates to (a) anionic surfactant.
1 to 30% by weight, (b) 0.05 to 15% by weight of a cationic surfactant having an alkyl group having 6 to 22 carbon atoms, and (c) 0.01 to 10% by weight of a water-soluble polymer. Provided is a liquid cleaning composition for hard bodies.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION As the anionic surfactant (a) used in the present invention, alkyl benzene sulfonate, anionic surfactant having a polyoxyalkylene group, alkyl or alkenyl sulfate, olefin sulfonate, One or more selected from saturated or unsaturated fatty acid salts, α-sulfofatty acids or α-sulfofatty acid esters, and diphenyl ether disulfonic acid type anionic surfactants can be mentioned. As the anionic surfactant of the component (a), the following are preferable among these from the viewpoint of detergency.

Polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, polyoxyalkylene alkyl aryl ether sulfate, polyoxyalkylene alkenyl aryl ether sulfate, polyoxyalkylene mono- or dialkyl ether phosphate, polyoxyalkylene Alkylene mono or dialkenyl ether phosphate, polyoxyalkylene mono or diphenyl ether phosphate, polyoxyalkylene alkyl ether carboxylate, polyoxyalkylene alkenyl ether carboxylate, polyoxyalkylene alkyl ether acetate, polyoxyalkylene alkenyl Ether acetate, polyoxyalkylene alkyl amide ether carboxylate, polyoxyalkylene alkenyl amide Rukarubon salt, and the like. The alkyl group or alkenyl group in these anionic surfactants preferably has 4 to 26 carbon atoms, and particularly preferably has 8 to 24 carbon atoms. Further, these alkyl groups or alkenyl groups may be linear or branched. Examples of the polyoxyalkylene group in the anionic surfactant include a polyoxyethylene group, a polyoxypropylene group, and a polyoxybutylene group.
Polyoxyethylene groups and polyoxypropylene groups are preferred. The number of moles of the polyoxyalkylene group added is 1
-20, preferably 1-10. Further, examples of the salt in the anionic surfactant include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium and magnesium, ammonium salts, mono-, di-, and trialkanolamine salts.

A diphenyl ether disulfonic acid type anionic surfactant represented by the following general formula:

[0010]

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[In the formula, R ¹¹ and R ¹² represent a straight-chain or branched-chain alkyl or alkenyl group having 6 to 22 carbon atoms or a hydrogen atom (provided that R ¹¹ and R ¹² are simultaneously hydrogen atoms) ), M and M 'represent a hydrogen atom, an alkali metal atom, an ammonium group or an alkanol-substituted ammonium group].

The content of the component (a) in the composition of the anionic surfactant is from 0.1 to 30% by weight, preferably from 0.5 to 20% by weight, particularly preferably from 1 to 20% by weight.
20% by weight. When the content is 0.1% by weight or more, sufficient detergency can be imparted, and when the content is 30% by weight or less, finishability is enhanced and wiping twice can be unnecessary.

As the cationic surfactant of the component (b) used in the present invention, a quaternary ammonium salt is preferable, and among these, a quaternary ammonium salt is particularly preferable. One or more selected from the following is preferred.

[0014]

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In the formula, R ¹ represents a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms, and R ² represents a methyl group or a linear or branched alkyl group having 6 to 20 carbon atoms. Or R ³ represents an alkenyl group, and R ³ has 6 to 2 carbon atoms.
0 represents a linear or branched alkyl or alkenyl group, and X represents a halogen atom or an alkyl sulfate residue. ]

[0016]

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Wherein R ⁴ represents a linear or branched alkyl or alkenyl group having 1 to 30 carbon atoms, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁶ represents It represents a linear or branched alkyl or alkenyl group having 1 to 30 carbon atoms, an aralkyl group, an aryl group, a group represented by the following general formula (5) or (6), and q represents the number of cations. . ]

[0018]

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Wherein R ⁷ represents a linear or branched alkyl or alkenyl group having 1 to 30 carbon atoms, R ⁸ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, ',
n and n ′ each represent a number of 0 to 3, p, m and m ′ represent a number of 0 or 1 (provided that l, m and n or l ′, m ′ and n ′ are simultaneously 0) Never.),
A is the following formula

[0020]

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Wherein X represents a halogen atom or an alkylsulfuric acid residue. ]

[0022]

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Wherein R ⁹ represents a linear or branched alkyl or alkenyl group having 6 to 20 carbon atoms, and R ¹⁰ is represented by a methyl group or — (CH ₂ CH ₂ O) _m H. represents a residue, m is a number of average 1 to 4, Y is _{- (C 2 H 4 O)} n
H or _{- (C 3 H 6 O)} l H ( wherein, n represents 1-4 on average
And 1 represents the number of 1 to 4 on average. ),
X represents a halogen atom or an alkyl sulfate residue].

In the general formula (1), the chain length of the linear or branched alkyl or alkenyl group represented by R ¹ or R ² is from 6 to 20, preferably from 6 to 14 from the viewpoint of detergency.
And particularly preferably 6 to 12, and more preferably 6 to 11. As R ¹ or R ² , a linear or branched alkyl group having the above carbon number is preferable, and a linear alkyl group is particularly preferable. Further, a dialkyl (or dialkenyl) dimethyl quaternary ammonium salt in which both R ^{1 and} R ² are an alkyl group or an alkenyl group having the above carbon number is preferable. When R ² is a methyl group, R ¹ is preferably a linear or branched alkyltrimethyl quaternary ammonium salt having the above carbon number.

In the general formula (2), the chain length of the linear or branched alkyl or alkenyl group represented by R ³ is from 6 to 20 from the viewpoint of detergency, preferably from 6 to 14, Particularly preferably, it is 6 to 12, and more preferably, 6 to 11. R ³ is preferably a straight-chain or branched-chain alkyl group having the above carbon number, and particularly preferably a straight-chain alkyl group.

The details of each substituent (including the general formulas (5) and (6)) in the general formula (3) are as follows.
Chain length of the alkyl or alkenyl group of a straight-chain or branched-chain represented by R ⁴ is 1 to 30, preferably 5 to 19
And particularly preferably 5 to 15, and more preferably 7 to 11. R ⁴ is preferably a straight-chain or branched-chain alkyl group having the above carbon number, and particularly preferably a straight-chain alkyl group.

R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a pentyl group. R ⁵ is preferably a hydrogen atom.

R ⁶ is a linear or branched alkyl or alkenyl group having 1 to 30 carbon atoms, an aralkyl group,
An aryl group represents a group represented by the general formula (5) or (6). When R ⁶ is a linear or branched alkyl or alkenyl group, a linear alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group is particularly preferable. As the aralkyl group represented by R ⁶ , a benzyl group, a phenethyl group and the like are preferable, and a benzyl group is particularly preferable. The aryl group represented by R ⁶ is preferably a phenyl group.

R ⁷ has the same meaning as R ^4, and R ⁸ has the same meaning as R ⁵ . l, l'n and n 'are the numbers of 1-3, but the number of 1-2 is preferable.

The cationic surfactant represented by the general formula (3) is preferably a quaternary ammonium salt represented by the following general formulas (3a) to (3f).
The quaternary ammonium salt represented by (3b) or (3c) is particularly preferred.

[0031]

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[Wherein R ⁴ , R ⁵ and R ⁶ have the same meaning as in the general formula (3), and y and z each represent a number of 1-6. In the general formulas (3a) to (3f), y is preferably a number of 1 to 3,
Is particularly preferred.

In the general formula (4), the linear or branched alkyl or alkenyl group represented by R ⁹ has a chain length of 6 to 20.
However, it is preferably 6 to 14, and particularly preferably 6 to 12.

Among Xs representing the counter ions represented by the general formulas (1) to (4), the halogen atom includes a bromine atom, an iodine atom and a chlorine atom, and the alkyl sulfate residue includes Methanesulfonic acid, ethanesulfonic acid and the like can be mentioned. Among these, a halogen atom is preferable, and a chlorine atom and a bromine atom are particularly preferable.

The content of the cationic surfactant (b) in the composition is from 0.05 to 15% by weight, preferably from 0.1 to 10% by weight, particularly preferably from 0.1 to 10% by weight. 5% by weight. When the content is 0.05% by weight or more, sufficient detergency can be imparted, and when the content is 15% by weight or less, finishability is enhanced and wiping twice can be unnecessary.

The water-soluble polymer of the component (c) used in the present invention is not particularly limited, but is preferably an anionic polymer. Examples of the anionic polymer include polyacrylic acid, polymaleic acid, carboxymethyl cellulose, acrylic acid-maleic anhydride copolymer, maleic anhydride-diisobutylene copolymer, maleic anhydride-vinyl acetate copolymer, naphthalene sulfonate formalin condensate and the like. One or more selected from salts of the following, among these, polyacrylates,
Polymaleic acid salts, acrylic acid-maleic anhydride copolymers are particularly preferred.

The content of the water-soluble polymer of the component (c) in the composition is from 0.01 to 10% by weight, preferably from 0.1 to 8% by weight, particularly preferably from 0.1 to 8% by weight.
6% by weight. When the content is 0.01% by weight or more, sufficient detergency can be imparted, and when the content is 10% by weight or less, product cost can be reduced while maintaining sufficient detergency.

The liquid detergent composition for a hard body of the present invention may further comprise, if necessary, an alkaline agent such as amino alcohol, ethanol, isopropanol, or the like, in addition to the above components.
Ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin,
Solvents such as isoprene glycol, propylene glycol monomethyl ether and propylene glycol monoethyl ether, thickeners, pigments, coloring agents, fragrances, bactericides, preservatives, and the like can be blended.

The liquid cleaning composition for a hard body of the present invention contains water together with the above components, and has a pH of preferably 3 to 12, particularly preferably 5 to 12,
More preferably, it is 6-11.

The liquid cleaning composition for a hard body of the present invention can be applied to various cleaning applications. The term "hard body" as used in the present invention refers to a substance that retains a certain shape, regardless of whether it is planar or three-dimensional, as long as it can be washed. The degree of hardness is not limited. Tile, ceramics, enamel, plastic, fiber reinforced plastic, rubber, metal, tile, brick, concrete,
In addition to fixed objects such as floors, stairs, and walls made of cement, glass, wood, and the like, various devices, instruments, tools, furniture, tableware, and the like made of them can be used in general. Therefore, the liquid cleaning composition for a hard body of the present invention is a floor cleaning agent, a furniture cleaning agent, a bathroom cleaning agent, a kitchen cleaning agent, a tableware cleaning agent, a cleaning agent for a fully automatic washing machine washing tub. ,
It can be applied as a cleaning agent for drainage pipes, a cleaning agent for small articles in kitchens and toilets, and the like.

[0041]

EXAMPLES Examples 1 to 6 and Comparative Examples 1 to 4 Liquid cleaning compositions for hard bodies having the compositions (in% by weight) shown in Table 1 were produced. The following compounds were used as compounds 1 to 4 shown in Table 1. Compound 1: C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₄ SO ₃ Na Compound 2: C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₃ CH ₂ COONa Compound 3: C ₁₂ H ₂₅ OSO ₃ Na Compound 4 : for _{C 12 H 25 O (C 2} H 4 O) 6 -H each of these compositions, by the following methods, oily soil cleaning properties, finish properties, anti-redeposition properties, was tested substrate damaging. Table 1 shows the results.

(Oil-based dirt-cleaning property) A dirt having the following composition was applied to 1 L of a liquid cleaning composition for a hard body, and was 10 × 10 cm.
Of the artificially contaminated cloth of No. 1, and a non-contaminated cloth of the same size so that the bath ratio becomes 1/60, and washed with a tergotometer at 100 rpm under the following conditions. <Soil composition> Cottonseed oil 60% by weight Cholesterol 10% by weight Oleic acid 10% by weight Liquid and solid paraffin 10% by weight Palmitic acid 10% by weight <Washing conditions> Washing time: 10 minutes Composition concentration: 0.5% by weight Water temperature : 20 ° C. Water hardness: 4 ° DH Rinsing: 5 minutes with tap water The detergency was determined from the following equation by measuring the reflectance of the original cloth before and after the cleaning. In addition, carbon black was mixed as an indicator, and the reflectance was measured using a colorimeter. The display is the average value of the cleaning rates of 12 sheets.

[0043]

(Equation 1)

(Finish feeling) One minute when five panelists wiped the flooring of the room kept at 25 ° C. with 0.5% by weight of the liquid cleaning composition for hard bodies. The finished feeling (stickiness) was evaluated on a three-point scale according to the following criteria. The display is the average score of five people. 3: No stickiness at all. 2: There is a slight sticky feeling. 1: There is considerable stickiness.

(Prevention of re-contamination) In a 1 L beaker, stain liquid (2.5 g / L of a product passed through a 200-mesh sieve of Kanuma Akadama soil)
) And dispersed with a glass rod while gradually adding the composition (0.5% by weight).
Adjusted to ° C. Next, this solution was put into a sample cup of a tergotometer, and then a test cloth (10 × cotton broad cloth was used).
(3 pieces cut to 10 cm) and put them in at 100 rpm.
Stirred for 0 minutes to contaminate. Thereafter, the test cloth was taken out, rinsed with running water, dried after pressing. The reflectance of such a test cloth was measured with NDR-10DP manufactured by Nippon Denshoku Industries Co., Ltd. using a 460 nm filter, and the re-contamination prevention rate was obtained from the following equation, and the re-contamination prevention property was evaluated. As the water, tap water having a hardness of 4 ° DH was used. The display is an average value of three sheets.

[0046]

(Equation 2)

(ABS resin damage suppression) 230 × 35 ×
A 2 mm ABS resin (Mitsubishi Monsanto) test piece was prepared. This test piece was fixed as shown in FIG. 1 in accordance with the surface shape of a pipe made of vinyl chloride resin having a diameter of 276 mm, and was strained as shown in FIG.
%). The distortion rate was calculated from the following equation: distortion rate (%) = (IL) × 100 / L (the definitions of I and L in the equation are shown in FIG. 2). Next, the test piece thus strained, that is, subjected to stress, was subjected to 10 times (one reciprocation) with a commercially available tissue paper (1 g dry weight) impregnated with 1.7 g of the liquid detergent composition. Was wiped once). Then, after standing at 20 ° C. and 65% RH for 24 hours, the state of the test piece surface was visually observed, and the base material damage suppression was evaluated according to the following criteria. ：: No abnormality ×: Cracks occurred

[0048]

[Table 1]

[0049]

The liquid detergent composition for a hard body of the present invention comprises:
Due to the synergistic action of the components (a), (b) and (c), excellent detergency, re-contamination prevention and substrate damage suppression are obtained together with the detergency.

[Brief description of the drawings]

FIG. 1 is a perspective view for explaining a method of a substrate damage test.

FIG. 2 shows an ABS for explaining a method of a substrate damage test.
It is sectional drawing of a resin test piece.

Claims (5)

[Claims] 1. Anionic surfactant (a) 0.1 to 30
(B) 0.05 to 15% by weight of a cationic surfactant having an alkyl group having 6 to 22 carbon atoms and (c) 0.01 to 10% by weight of a water-soluble polymer. Liquid cleaning composition for body. 2. The cationic surfactant of component (b) is at least one selected from those represented by the following general formulas (1), (2), (3) and (4). The liquid cleaning composition for a hard body according to claim 1. Embedded image [Wherein, R ¹ represents a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms, and R ² represents a methyl group or a linear or branched alkyl or alkenyl group having 6 to 20 carbon atoms. R ³ represents a linear or branched alkyl or alkenyl group having 6 to 20 carbon atoms, and X represents a halogen atom or an alkyl sulfate residue. ] [Wherein, R ⁴ represents a linear or branched alkyl group or alkenyl group having 1 to 30 carbon atoms, R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁶ represents 1 carbon atom. To 30 linear or branched alkyl or alkenyl groups, aralkyl groups, aryl groups, groups represented by the following general formula (5) or (6), and q represents the number of cations. ] [In the formula, R ⁷ represents a linear or branched alkyl group or alkenyl group having 1 to 30 carbon atoms, R ⁸ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, l, l ′, n And n ′ each represent a number of 0 to 3, and p, m and m ′ each represent 0 or 1.
(However, l, m and n or l ′, m ′ and n ′ do not become 0 at the same time), and A is the following formula: And X represents a halogen atom or an alkyl sulfate residue. ] [Wherein, R ⁹ represents a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms, and R ¹⁰ represents a methyl group or-
(CH ₂ CH ₂ O) represents a residue represented by _m H, m is a number of average 1 to 4, Y is _{- (C 2 H 4 O)} n H or - (C ₃
H ₆ O) _l H (where n represents an average of 1 to 4;
Indicates an average number of 1 to 4. ) And X represents a halogen atom or an alkyl sulfate residue. ] 3. An anionic surfactant (a) comprising an alkyl benzene sulfonate, a polyoxyalkylene group-containing anionic surfactant, an alkyl or alkenyl sulfate, an olefin sulfonate, a saturated or unsaturated fatty acid salt, The liquid detergent composition for a hard body according to claim 1 or 2, wherein the composition is at least one selected from α-sulfofatty acids or α-sulfofatty acid esters and diphenyl ether disulfonic acid type anionic surfactants. 4. The liquid cleaning composition for a hard body according to claim 1, wherein the water-soluble polymer as the component (c) is an anionic polymer. 5. The water-soluble polymer of component (c) is polyacrylic acid, polymaleic acid, carboxymethylcellulose, acrylic acid-maleic anhydride copolymer, maleic anhydride-diisobutylene copolymer, maleic anhydride-
The liquid detergent composition for a hard body according to any one of claims 1 to 4, wherein the composition is at least one selected from a vinyl acetate copolymer, a naphthalene sulfonate formalin condensate, and a salt thereof.