JPH07157796A - Cleaning agent composition for hard surface - Google Patents

Abstract

PURPOSE:To obtain the composition containing a specific anionic surfactant, a water-soluble solvent and a polysaccharide, having not only wiping properties and residual properties after wiping but also hardly dripping in use of a sprayer, excellent diffusion of liquid in liquid spraying and excellent cleaning power. CONSTITUTION:This composition contains (A) 0.01-20wt.% of a diphenyl ether disulfonic acid type anionic surfactant, (B) 0.1-50wt.% of a water-soluble solvent and (C) 0.01-5wt.% of a polysaccharide. The component A is an anionic surfactant of formula I or II (R<1> and R<2> are each a 5-15C alkyl or alkenyl; M<1> and M<2> are an anionic metal, ammonium or an alkanol-substituted ammonium) and the component C is any of xanthan gum, carrageenan and locust bean gum. Further the composition preferably contains (D) an amine compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a detergent composition for hard surfaces, and more particularly, it has an excellent wiping property, has a small amount of unwiping residue, has a good finish, and has an excellent cleaning power for stains, particularly modified oil and fat stains. Further, the present invention relates to a cleaning composition for hard surfaces, which is less likely to cause foam dripping when used in a trigger type sprayer and has good liquid diffusibility.

[0002]

2. Description of the Related Art Conventionally, as a cleaning composition for hard surfaces, the following ones are properly used according to the type and degree of stains. That is to say, for hand stains that are relatively lightly soiled and unmodified oil stains, a surfactant / solvent-based detergent is a fat and oil that has been altered by the effects of heat around the kitchen, sunlight, oxygen in the air, etc. A detergent / solvent / alkaline cleaner is mainly used for dirt and the like.

However, when these cleaning agents are used, since the surface active agent and the alkaline agent remain on the surface to be cleaned, wiping marks remain after cleaning and the finish is insufficient. It was necessary to rinse thoroughly with water, which was complicated.

As an attempt to solve such a problem, Japanese Unexamined Patent Publication (Kokai) No. 2-29498 discloses that anionic surfactants, terpene hydrocarbon solvents and water-soluble divalent metal salts are essential components and they are excellent in detergency. , A liquid detergent composition for household use, which is safe for the human body, has a small influence on a substrate, and does not require rinsing, is disclosed. However, when the glass surface or the like was washed with this product, although it was considerably improved in terms of finish, it was necessary to further improve it in practical use. In addition, Japanese Patent Publication No. 62-501570 discloses a detergent composition for hard surfaces, which comprises a glycoside surfactant, a solvent, a water-soluble detergent and a builder, but this also shows unwiping residue. Therefore, sufficient rinsing was necessary.

Further, Japanese Patent Application Laid-Open No. 4-85400 proposes a liquid detergent composition comprising a specific anionic activator and a specific amphoteric activator, which has a high detergency and has a small amount of unwiping residue. Due to the high foaming property of the activator, bubbles were excessively formed during wiping, and the wiping property (wiping workability) was not good. On the other hand, alkyl diphenyl ether type surfactants having two sulfonic acid groups in one molecule have been widely used for a wide range of applications such as emulsifiers during polymer production, fiber dyeing process agents, agricultural chemical dispersants and crude oil sludge dispersants. . However, there is no known example used as a detergent for hard surfaces in a surfactant / solvent / amine compound system.

Under these circumstances, the present inventors have found that when a diphenyl ether disulfonic acid type anionic surfactant is combined with a water-soluble solvent, the wiping property is good, there are no traces of unwiping, and the cleaning power is excellent. It was found that a cleaning agent for hard surfaces can be obtained, and a patent application was previously filed (Japanese Patent Application No. 5-8
4754).

By the way, most of conventional cleaning agents for hard surfaces have a low solution viscosity, and when used on a non-horizontal surface such as a kitchen or bathroom wall, a window glass, and a ventilation fan with a sprayer, liquid drips immediately. There was a drawback that it was not easy to use. Further, the liquid drip reduces the time for which the cleaning agent stays in the dirty portion, and as a result, the cleaning power originally possessed by the cleaning agent is not fully exerted.

Therefore, attempts have been made to increase the viscosity of the cleaning agent for the purpose of prolonging the residence time of the solution on the non-horizontal plane (for example, JP-A-60-173098 and JP-A-62-1197). JP-A-63-90600, JP-A-63-189491).

Most of the sprayers currently in use are of a foam type and a mist type which can be switched (trigger type). What has good diffusivity is desired.

[0010]

The object of the present invention is that the wiping property is good, there are no traces of unwiping residue, bubbles do not easily drip when used in a trigger type sprayer, and the liquid diffusibility is good, Another object of the present invention is to provide a hard surface cleaner composition having excellent detergency.

[0011]

Therefore, the present inventors have variously studied the combination of various thickeners with respect to the combined system of the above-mentioned diphenyl ether disulfonic acid type anionic surfactant and a water-soluble solvent, and It was found that there was no foam dripping when blended, and the diffusibility of the liquid was good, and the present invention was completed.

That is, the present invention provides the following component (A),
(B) and (C): (A) diphenyl ether disulfonic acid type anionic surfactant (B) water-soluble solvent (C) a detergent composition for hard surfaces containing a polysaccharide.

The component (A) of the present invention is not particularly limited as long as it is a diphenyl ether disulfonate, but it is one selected from the anionic surfactants represented by the following general formulas (1) and (2). Alternatively, two or more kinds are preferable.

[0014]

[Chemical 2]

[In the formula, R ¹ and R ² represent a linear or branched alkyl or alkenyl group having 5 to 15 carbon atoms, and M 1
¹ and M ² represent an alkali metal, ammonium group or alkanol-substituted ammonium group]

R ¹ and R ² in the formula are each 5 carbon atoms.
It is a straight-chain or branched-chain alkyl or alkenyl group having 15 to 15 carbon atoms, but an alkyl group having 8 to 14 carbon atoms, particularly an alkyl group having 12 to 14 carbon atoms is preferable from the viewpoints of detergency and a small amount of unwiping residue. . Specific examples of particularly preferable R ¹ and R ² include a decyl group, a dodecyl group, and a tetradecyl group. M ¹ and M ² are an alkali metal such as sodium and potassium, an ammonium group, or an alkanol-substituted ammonium group such as monoethanolammonium and diethanolammonium. Of these, an alkali metal, particularly sodium or potassium, is preferable. The two compounds (1) and (2) as the component (A) have a weight ratio of (1) / (2) = 100/0 to 25.
It is preferable to use it at a compounding ratio of / 75, especially 95/5 to
It is preferable to use the compounding ratio of 70/30.

The above compound (1) and compound (2)
Can be obtained by a usual method in which alkylation is carried out by Friedel-Crafts reaction of diphenyl ether, followed by sulfonation with sulfur trioxide or the like in a solvent of dichloromethane, followed by neutralization. However, the alkylation reaction with diphenyl ether may selectively occur at the para position, but depending on the reaction conditions such as the amount of the alkylating reagent used, different alkylation numbers and orientation positions may be obtained. However, even if this reaction mixture is used, as long as the compounds represented by the formulas (1) and (2) are contained as the main components, no particular problem occurs.

The water-soluble solvent of the component (B) used in the present invention not only improves the cleaning power when used in combination with the component (A), but also improves the wiping property and prevents the unwiping residue. And is not particularly limited as long as it is a water-soluble solvent, but it is a compound represented by the following general formulas (3) to (5), a dihydric alcohol having 4 to 12 carbon atoms and a dihydric alcohol having 1 to 5 carbon atoms. One or more water-soluble solvents selected from monohydric alcohols are preferable.

[0019]

[Chemical 3]

[In the formula, R ³ and R ⁴ each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R ³ and R ⁴
Except when both are hydrogen atoms. m represents an integer of 0 to 3 and n represents an integer of 0 to 3, except when both m and n are 0. R ⁵ and R ⁶ represent an alkyl group having 1 to 3 carbon atoms. R ⁷ represents an alkyl group having 1 to 3 carbon atoms]

In the water-soluble solvent represented by the above general formula (3), R ³ and R ⁴ represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 4 carbon atoms is particularly preferable. . Further, in the formula (3), m and n of the average addition mole number of ethylene oxide (EO) and propylene oxide (PO) are preferably 0 to 3, respectively. Further, the order of adding these is not particularly limited,
It may be randomly added. Specific examples of the compound (3) include ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol dimethyl ether, Polyoxyethylene (p = 1) Polyoxypropylene (p = 1)
Glycol dimethyl ether (p represents the average number of moles added) and the like.

Of these compounds (3), the compounds represented by the following general formula (3 ') are preferable from the viewpoints of detergency and ease of wiping.

[0023]

[Chemical 4]

[In the formula, R ³ ′ and R ⁴ ′ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, except when both R ³ ′ and R ⁴ ′ are hydrogen atoms. m'and n'are 0
An integer of 3 is shown, except when m'and n'are both 0 and when m '= 1 and n' = 0.] As specific examples thereof, propylene glycol monomethyl ether, diethylene glycol monobutyl ether and the like can be given. Can be mentioned.

As the compound represented by the general formula (4), 1,3-dimethyl-2-imidazolidinone,
1,3-Diethyl-2-imidazolidinone is exemplified as a preferable example, and as the compound represented by the general formula (5), 3-methoxy-3-methylbutanol, 3-ethoxy-3-methylbutanol and the like are preferable. . Examples of the dihydric alcohol having 4 to 12 carbon atoms include isoprene glycol and 2,2,4-trimethyl-1,3-pentanediol. Further, examples of the monohydric alcohol having 1 to 5 carbon atoms include methanol, ethanol, isopropanol, and the like. By blending these lower alcohols, the stability of the system at low temperatures can be further improved.

The polysaccharide of the component (C) used in the present invention acts as a thickener, but by combining with the component (A) and the component (B), it is used particularly in a trigger type sprayer. In this case, the usability is improved, and the detergency on a non-horizontal surface is improved. The polysaccharide is not particularly limited as long as it is a polysaccharide usually used as a thickener, and examples thereof include xanthan gum, carrageenan, locust bean gum, alginates and cellulose derivatives. These polysaccharides can be used alone or in combination of two or more. Among these, xanthan gum, carrageenan,
It is preferred to use locust bean gum, especially xanthan gum. Xanthan gum is the Xanthomonas campestris.
It is a heteropolysaccharide obtained by the fermentation action of tris), and a commercially available product can be used. The polysaccharides used in the present invention include natural polysaccharides and modified polysaccharides.

In the hard surface cleaner composition of the present invention, the blending amounts of the component (A), the component (B) and the component (C) are not particularly limited. The effect of can be further improved. The component (A) is 0.01 to 20% by weight (hereinafter simply referred to as “%”) in the total amount of the composition from the viewpoint of detergency, wiping property and finishing property, and further 0.01 to 10%, particularly 0.1 to 3% is preferably blended, and the component (B) is 0.1 to 5 in the total amount of the composition mainly from the viewpoints of detergency and finish.
0%, more preferably 1 to 30%, particularly preferably 1 to 20% is preferably blended, and the component (C) is 0.01 to 5% in the total amount of the composition from the viewpoint of thickening and usability in a sprayer. Further, it is preferable to add 0.01 to 1%, particularly 0.03 to 0.5%.

The hard surface cleaner composition of the present invention may optionally contain an amine compound (D) for the purpose of improving the cleaning power. The amine compound is not particularly limited, but for example, ammonia, monoethanolamine, diethanolamine, N-
Methyl propanol, N- (β-aminoethyl) ethanolamine, diethylenetriamine, morpholine, N-
Examples thereof include ethylmorpholine. Among these, monoethanolamine and morpholine are particularly preferable.

The blending amount of these amine compounds (D) is not particularly limited, but from the viewpoint of enhancing the detergency, it is 0.01 to 30%, more preferably 0.01 to 20%, and especially 0.1.
05-10% is preferable.

The hard surface cleaner composition of the present invention may be used, if necessary, within a range that does not impair the effects of the present invention.
A surfactant other than the above component (A) can be added. Such a surfactant is not particularly limited, but one or more selected from the group consisting of nonionic, anionic and amphoteric surfactants are preferable. Specific examples include the following.

Examples of the anionic surfactant include alkylbenzene sulfonates, alkylene oxide-added alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, fatty acid salts, alkylene oxide-added alkyls. Or alkenyl ether carboxylates, α
-Sulfo fatty acid salts and their esters and the like. Examples of the counterion of the anionic surfactant include alkali metals such as sodium and potassium, ammonium salts, and alkanol-substituted ammonium salts such as monoethanolammonium, diethanolammonium and triethanolammonium.

As the nonionic surfactant, polyoxyalkylene alkyl or alkenyl ethers, polyoxyalkylene alkylphenyl ethers, sucrose fatty acid esters, fatty acid glycerin esters, amine oxides, higher fatty acid alkanolamides or the like. Examples thereof include alkylene oxide adducts and alkyl glycosides represented by the following general formula (10).

[0033]

[Chemical 5] R ²¹ (OR ²² ) _x G _y (10)

[In the formula, R ²¹ represents a linear or branched alkyl group, alkenyl group or alkylphenyl group having 8 to 18 carbon atoms, R ²² represents an alkylene group having 2 to 4 carbon atoms, and G represents A residue derived from a reducing sugar having 5 to 6 carbon atoms, x represents a number having an average value of 0 to 5, and y represents a number having an average value of 1 to 10]

In the general formula (10), x has an average value of 0 to
The value of 5 controls the water solubility and crystallinity of the composition of the present invention. That is, the higher the x, the higher the water solubility and the lower the crystallinity. The preferred value of x is 0
2 and particularly preferably 0. On the other hand, when the average value of y is greater than 1, that is, when y contains a surfactant represented by the general formula (10) having a sugar chain of two or more sugars as a hydrophilic group, the binding mode of the sugar chain is 1 -2, 1-3, 1-
It is possible to include 4,1-6 bonds, as well as α-, β-pyranoside or furanoside bonds and any mixtures thereof having mixed binding modes. The average value of y in the general formula (10) is 1 to 10, preferably 1 to
3, and more preferably 1 to 1.5, and even more preferably the average value is 1.1 to 1.4. The measurement method of y is based on the proton NMR method.

R ²¹ in the general formula (10) has 8 carbon atoms.
It is an alkyl group, an alkenyl group, or an alkylphenyl group having a linear or branched chain of 18 carbon atoms, but from the viewpoint of improving the solubility, foaming property and detergency, it is preferably 10 to 1 carbon atoms.
4 is an alkyl group. R ²² is an alkylene group having 2 to 4 carbon atoms, and preferably 2 to 3 carbon atoms from the viewpoint of water solubility. Further, the structure of G is determined by a monosaccharide or a raw material of two or more sugars. As the raw material of G, glucose, fructose, galactose, xylose, mannose, lyxose, arabinose and the like, and mixtures thereof, etc. For 2 sugars or more, maltose, xylobiose, isomaltose, cellobiose,
Examples thereof include gentibiose, lactose, sucrose, nigerose, turanose, raffinose, gentianose, melezitose and the like, and mixtures thereof. Among these, preferred monosaccharide raw materials are glucose and fructose from the viewpoints of their availability and cost, and maltose and sucrose for two or more sugars. Among these, glucose and maltose are particularly preferable from the viewpoint of easy availability.

As the amphoteric surfactant, for example, carbon number 1
And sulfobetaine and carbobetaine having a straight-chain or branched-chain alkyl group or alkenyl group having 22 to 22 and amidosulfobetaine and amidocarbobetaine having a straight-chain or branched-chain alkyl group having 8 to 24 carbon atoms.

In the present invention, among the surfactants other than the component (A), higher fatty acid alkanolamides or their alkylene oxide adducts, amine oxides, and alkyls are used from the viewpoint of improving detergency or wiping property. Glycosides and alkylamidocarbobetaines are preferable, and of these, alkylglycosides are particularly preferable.

When the surfactant other than the component (A) is blended, the blending amount thereof is preferably from 0.01 to 0.01 in the composition.
It is 20%, more preferably 0.05 to 10%, and particularly preferably 0.05 to 5%.

In addition to the above-mentioned components, the detergent composition for hard surfaces of the present invention may further contain an ordinary dispersant, chelating agent, or a dispersant in order to further improve the storage stability of the system at low temperatures.
Fragrances, dyes, pigments, preservatives and the like can be added within a range that does not impair the effects of the present invention.

As a particularly preferable compounding system of the detergent composition for hard surfaces of the present invention, the component (A) is 0.01 to 10%,
(B) component 1 to 30%, (C) component 0.01 to 1%, amine compound (D) 0.01 to 20%, alkylglycoside surfactant 0.05 to 10% is there.

The detergent composition for hard surfaces of the present invention can be produced by mixing the above components and water by a conventional method.

The detergent composition for hard surfaces of the present invention is preferably filled in a sprayer, particularly a trigger type sprayer capable of switching between foam and mist, and its usage is sprayed directly onto the portion to be cleaned. However, a wiping method is preferable. Further, the composition of the present invention is used for cleaning stains on hard surfaces such as glass, enamel, stainless steel, iron, aluminum and the like, plastics, pottery, and the like. , Oil stains, burnt stains, dirt and sand dust, dust, and composite stains of these.

[0044]

EFFECT OF THE INVENTION The detergent composition for hard surfaces of the present invention has a high detergency itself, especially a detergency for modified oil and fat stains, and also has an excellent wiping property, less unwiping residue and good finish. Also, when used in a sprayer, the liquid does not drip easily on the vertical surface and has good liquid diffusion properties.

[0045]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention.

Example 1 Evaluation of detergency, wiping-off property, wiping-off property, dullness of bubbles on vertical surface, and diffusibility of liquid: A cleaning composition for hard surface having the composition shown in Table 1 was prepared, Using this, the detergency, the wiping-off property, the wiping-off property, the dullness of bubbles on the vertical surface, and the liquid diffusibility were evaluated by the following evaluation methods. The results are shown in Table 1.

Evaluation Method of Detergency, Wipeability, and Wiping Residualness: [Detergency] A model stain was obtained by forcibly attaching tar stains on a slide glass. The model dirt was permeated into each cleaning solution for 3 seconds, washed with water, and then sensory evaluated according to the following evaluation criteria. ○: Good stain removal. Δ: There are places where stains do not come off. X: Almost no stain is removed.

[Wipeability] On a window glass of an actual home,
Each washing solution was sprayed with a commercial sprayer for 3 cc and wiped with a dry towel. The amount of bubbles dragged during wiping and the speed at which the bubbles disappeared were sensory-evaluated according to the following evaluation criteria. ○: It is difficult to drag bubbles when wiped with a towel. (While wiping, the bubbles disappear immediately) △: When wiping with a towel, some bubbles are dragged. (While wiping, the bubbles are hard to disappear immediately) ×: When wiping with a towel, the bubbles are dragged. (While wiping, bubbles do not disappear)

[Evaluation of Wiping Remaining Property (Finishing Property)] After the wiping-off property was evaluated, the wiping mark remaining property was evaluated by the following sensory evaluation. ○: There are almost no remaining traces of wiping. Δ: The trace of wiping remains slightly. X: A trace of wiping remains.

[Difficulty of Dripping of Bubbles on Vertical Surface] Each cleaning liquid was sprayed into a 1 cc foam on a window glass of an actual household with a commercially available sprayer, and the dripping resistance of bubbles was evaluated according to the following evaluation criteria. The evaluation was performed. ◯: Almost no bubbles drip. Δ: Bubbles gradually sag. X: Bubbles drip immediately.

[Diffusion of Liquid] The spread of the liquid when sprayed in a mist with a commercially available sprayer was carried out by sensory evaluation as follows. A: Spreads very well. ○: Spreads well. Δ: Does not spread very much. X: Does not spread.

[0052]

[Table 1]

As is clear from Table 1, the composition of the present invention has not only wiping-off property and unwiping property (finishing property) but also
It can be seen that when used in a sprayer, bubbles do not easily drip, the liquid has good diffusibility when sprayed in liquid form, and the cleaning power is also excellent.

Claims (5)

[Claims] 1. Cleaning of a hard surface containing the following components (A), (B) and (C): (A) diphenyl ether disulfonic acid type anionic surfactant (B) water-soluble solvent (C) polysaccharide. Agent composition. 2. The following components (A), (B) and (C): (A) diphenyl ether disulfonic acid type anionic surfactant 0.01 to 20% by weight (B) water-soluble solvent 0.1 to 50 % (C) Polysaccharide 0.01 to 5% by weight, a hard surface cleaner composition. 3. The component (A) has the following general formulas (1) and (2): [Wherein, R ¹ and R ² represent a linear or branched alkyl or alkenyl group having 5 to 15 carbon atoms, and M ¹ and M ² represent an alkali metal, ammonium group or alkanol-substituted ammonium group] 1 or 2 selected from the anionic surfactants mentioned above.
A cleaning composition for hard surfaces according to claim 1. 4. The cleaning composition for hard surfaces according to claim 1, wherein the component (C) is one or more selected from xanthan gum, carrageenan and locust bean gum. 5. The cleaning composition for hard surfaces according to claim 1, further comprising (D) an amine compound.