JPH0438796B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a liquid cleanser composition that has excellent cleaning and polishing power, does not damage surfaces to be cleaned, and has excellent rinsing properties. [Prior Art and Problems] Cleansers target stains such as denatured or burnt oil stains, water stains and slimy stains on sinks, and soap scum stains on bathtubs. In addition, the material of the target surface is a metal surface such as stainless steel, or glass fiber reinforced plastic (FRP) used in bathtubs.
There are many things that are easily damaged. Conventional cleansers cannot be expected to have sufficient cleaning power against these various stains and to provide a glossy finish without damaging the surface to be cleaned. Silica stone and calcium carbonate, which have been widely used in the past, have an average particle size of 15 μm or more, and those with a particle diameter of less than 15 μm are less likely to scratch the target surface, but are not used because they reduce polishing performance. Liquid cleansers using zeolite as an abrasive are also known (see JP-A-51-50909 and JP-A-55-5947). However, although zeolite is excellent in that it does not easily damage the surface to be cleaned, its abrasive power is poor, and its use as an abrasive has not become widespread. Furthermore, it is empirically known that the average particle size of the abrasive material also affects the rinsability after cleaning. In general, the smaller the average particle size, the more likely it is to remain on the surface to be cleaned, and the more likely the surface will be whitened when drying, and the finish was not completely satisfactory. [Means for Solving the Problems] The present inventors have developed a method that has sufficient cleaning power and polishing power against a wide range of commonly found stains as described above.
As a result of intensive research in order to obtain a liquid cleanser that provides excellent rinsing properties and a glossy finish without damaging the surface to be cleaned, we have developed a liquid cleanser composition containing an ethylene oxide adduct of an alkylbenzene sulfonate and a secondary alcohol. The present inventors have discovered that it is effective to mix an abrasive material having a specific crystal type and a terpene hydrocarbon in a specific amount in an object, and have completed the present invention. That is, the present invention contains (A) an alkylbenzene sulfonate (B) an ethylene oxide adduct of a secondary alcohol (A) + (B) = 2 to 8% by weight, and furthermore, (C) at least 30 A water-insoluble abrasive material consisting of an interpenetrating aluminosilicate in which the above crystals form an aggregate 3 to 40% by weight (D) Contains 0.01 to 3% by weight of a terpene hydrocarbon selected from monoterpenes and sesquiterpenes The present invention provides a liquid cleanser composition characterized by the following. As the alkylbenzene sulfonate as component (A) used in the present invention, the alkyl group has 8 to 8 carbon atoms.
A linear or branched alkylbenzene sulfonate of 23 is preferred, and counterions include alkali metals, alkaline earth metals, alkanolamines, ammonia, and the like. The ethylene oxide adduct of secondary alcohol used in the present invention (B) is preferably one in which the alkyl group has 8 to 22 carbon atoms, and the average number of moles of ethylene oxide added is preferably 3 to 15. is 7 to 12. The total amount of component (A) and component (B) is 2 to 8% by weight (hereinafter abbreviated as %). If it is less than 2%, foaming power, emulsifying and dispersing power, etc. will be insufficient, and if it exceeds 8%, the viscosity will become too high, which is not preferable. In order to stably disperse the abrasive, the weight ratio of component (A) and component (B) is 25≧(A)/(B).
It is desirable that it be >0.5. The crystalline aluminosilicate used as a water-insoluble abrasive in the present invention is an interpenetrating type in which cubic crystals interpenetrate each other to form an aggregate of at least 30 or more. The average particle size is preferably 3 to 12μ, and less than 5% of the particles are preferably 40μ or more. Further, one side of the cubic crystals forming the aggregate is usually 0.2 to 5 μm, and preferably the corners and edges are rounded. In this way, it forms an aggregate and has many corners,
It is preferable to have an appropriate particle size, and this is thought to be because the number of contact points between the abrasive and dirt is large, or because the force transmission efficiency is good. Even if the particle size of conventionally used silicon dioxide, calcium carbonate, etc. is adjusted, it is not possible to obtain a product that satisfies both sufficient cleaning power and less damage to the surface to be cleaned. This is thought to be due to its shape. In addition, even with crystalline aluminosilicate, a single cubic shape cannot provide sufficient cleaning power and less damage, regardless of the particle size, and even if aggregates are formed, the number of aggregates is small. However, it is not possible to obtain products that are equally satisfactory in terms of cleaning power and low scratch resistance. The above-mentioned crystalline aluminosilicate can be obtained by hydrothermal crystallization by mixing an aqueous sodium aluminate solution and an aqueous sodium silicate solution (Japanese Patent Laid-Open No. 59-26917
(see publication). In producing the crystalline aluminosilicate, a high concentration solution of 30 to 70% by weight is used as the sodium aluminate aqueous solution, and a high concentration solution of 35 to 50% by weight is used as the sodium silicate aqueous solution, and, The composition of the mixed solution is the molar ratio; 1.0 to 2.0
The aluminosilicate slurry may be produced in such a manner that it has Na ₂ O: 1 Al ₂ O ₃ : 1.5 to 2.5 SiO ₂ : 15 to 30 H ₂ O. If the concentration of the aqueous solution is too low, sufficient aggregates will not be formed, and if the concentration is too high, the particles will become coarse. The interpenetrating crystalline aluminosilicate obtained in this way may be blended with the detergent component as it is as a slurry, or may be blended after drying and powdering. It is difficult to stabilize the dispersion of laundry detergents that have a large particulate content and do not have sufficient abrasive power. On the other hand, those with many coarse grains tend to damage the target surface. Therefore, by using component (C) having a particle size distribution within the range shown in FIG. 1, a liquid cleanser composition with the best dispersion stability, detergency, and non-scratch property can be obtained. In preparing the particle size distribution curve shown in FIG. 1, the particle size was selected using a Coulter Counter (manufactured by Coulter Electronics). Curve X defines the limit for smaller particle sizes, and curve X' defines the limit for larger particle sizes. Component (D) used in the present invention includes monoterpene hydrocarbons or sesquiterpene hydrocarbons contained in plant aromatic oils. Examples of monoterpene hydrocarbons include D- or L-limonene contained in orange oil, lemon oil, etc., α- or β-pinene contained in terpine oil, etc., and sesquiterpene hydrocarbons include: fern oil,
Examples include caryophyllene and cedrene, which are abundantly contained in clover oil and cananda oil. Each terpene hydrocarbon selected from moleterpene and sesquiterpene can be used not only individually as component (D) of the present invention, but also in combination of two or more, and furthermore, orange oil, terpene, etc. Oil or pine oil can also be incorporated into the composition of the present invention. The blending amount of component (D) is in the range of 0.01 to 3% by weight, preferably 0.5 to 2% by weight in the liquid cleanser composition. If this amount is less than 0.01% by weight, the desired improvement in rinsability will be insufficient, while if it exceeds 3% by weight, the coloring properties and low-temperature stability of the liquid cleanser composition will deteriorate, which is not preferred. In the present invention, surfactants that can be used in addition to component (A) and component (B) include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. are used, particularly preferred are anionic and nonionic surfactants. The anionic surfactants used in the present invention include ordinary sulfonate-based anionic surfactants, sulfate-based anionic surfactants,
Phosphate-based anionic surfactants are used. Examples of the sulfonate-based anionic surfactants include long-chain alkyl ( _C8 - _C22 ) sulfonates, long-chain olefin ( _C8 - _C22 ) sulfonates, and the like.
Examples of sulfate-based anionic surfactants include long-chain monoalkyl ( _C8 - _C22 ) sulfate ester salts, polyoxyethylene (1-6 mol) long-chain alkyl ( _C8 - _C22 ) ether sulfate ester salts. , polyoxyethylene (1-6 mol) alkyl (C ₈ ~
C ₁₈ ) phenyl ether sulfate salts, etc.
In addition, as the phosphate-based anionic surfactant, long-chain monoalkyl, dialkyl or sesqui(each alkyl group has 8 to 22 carbon atoms) phosphate, polyoxyethylene (1 to 6 mol) monoalkyl , dialkyl or sesqui (each alkyl group has 8 to 22 carbon atoms) phosphates, and aliphatic carboxylates having 8 to 22 carbon atoms. Cations as counter ions of these anionic surfactants include alkali metal ions such as sodium and potassium, alkanolamine ions such as monoethanolamine, diethanolamine, and triethanolamine. As the anionic surfactant of the present invention, sulfonate surfactants are preferred because of their strong resistance to hydrolysis. Nonionic surfactants include polyoxyethylene (1 to 20 mol), long chain alkyl (primary C ₈
~ _C22 ) Ether, polyoxyethylene (1~20
mole) alkyl ( _C8 - _C18 ) phenyl ether,
Oxyalkylene adducts such as polyoxyethylene polyoxypropylene block copolymers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, and the like are used. In the present invention, the dispersion stabilizer has 3 to 3 carbon atoms.
8 di- or tricarboxylic acids or salts thereof can be added. Specific examples of di- or tricarboxylic acids having 3 to 8 carbon atoms or salts thereof are malonic acid, malic acid, tartaric acid, citric acid, L-aspartic acid or salts thereof. The amount of di- and tricarboxylic acid or its salt is
Preferably 0.1-5%, more preferably 0.5-3%
It is. In carrying out the present invention, sodium silicate, such as sodium silicate No. 1, sodium silicate No. 2, sodium silicate No. 3, sodium silicate No. 4, sodium orthosilicate, sodium sesquisilicate, sodium metasilicate, magnesium sulfate, chloride, etc. If an alkaline earth metal salt such as calcium is used in combination, the dispersion stability will be further improved. In addition, silicon dioxide, aluminum oxide, aluminum hydroxide, magnesium oxide, titanium oxide, silicon carbide, calcium carbonate, calcium phosphate, chromium oxide, corundum, emery, silica, quartz sand, calcium oxide, etc. may be used within a range that does not impair the effects of the present invention. site, dolomite, vinyl chloride,
Polymer beads such as polystyrene, polyethylene, ABS, etc. may be added, and if necessary,
Alkali agents, solvents, hydrotropic agents, bactericidal agents, fragrances, pigments, dyes, etc. can be optionally added. Examples of alkali agents include organic alkali agents such as ammonia, monoethanolamine, diethanolamine, triethanolamine, and morpholine, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, sodium carbonate, sodium pyrophosphate, and sodium tripolyphosphate. Sodium borate or the like or their potassium salts can be used. Examples of solvents include aliphatic monohydric alcohols such as ethyl alcohol and butyl alcohol, ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, or their lower aliphatic alcohols (methyl, ethyl,
) and ethers such as propyl and butyl. As the hydrotrope, paratoluene sulfonate, xylene sulfonate, cumene sulfonate, urea, etc. can be used. The pH of the liquid is adjusted from neutral to alkaline to exhibit excellent cleaning power. [Effects of the Invention] The liquid cleanser composition of the present invention has excellent cleaning power against a wide variety of stains, from denatured oil and burnt stains to soap scum stains in bathtubs, without damaging the surface to be cleaned. , has abrasive power and has excellent rinsing properties. [Example] The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples. Example 1 Liquid cleanser compositions shown in Table 1 were prepared, and the cleaning power, scratch resistance, and rinsability of each composition were evaluated as follows. <Test method> Γ Cleaning power 1 A 3 x 8 cm iron test piece with oil-denatured stains was coated with 1.0 g of rapeseed oil/carbon black (weight ratio: 5/1) and denatured at 150°C for 130 minutes. It was used. The evaluation method was to take 1 g of sample, wash it 30 times with a load of 1 kg/30 cm ² using a urethane sponge, and then calculate the relative cleaning rate from the weight loss rate.
A five-level evaluation was performed as shown below. Relative cleaning rate (%) 5...81-100 4...61-80 3...41-60 2...21-40 1...0-20 (Relative cleaning rate (%); Polishing cleaning of commercial product A power
It was set at 50. ) Commercial product A; LAS (sodium dodecylbenzene sulfonate) 2.5% Lauric acid diethanolamide 4% Calcium carbonate (average particle size 20μ) 50% Water Balance 2 Bathtub stains Bathtub stains that cannot be removed by scrubbing are attached. The FRP bathtub was cleaned by scrubbing it with a sponge impregnated with a cleaning agent, and the effects were observed with the naked eye. Relative cleaning rate (%) 5...81-100 4...61-80 3...41-60 2...21-40 1...0-20 (Relative cleaning rate (%); Polishing cleaning of commercial product A power
It was set at 50. ) Γ Scratch Resistance 1 g of sample was taken and the FRP surface and stainless steel surface, which are the materials of bathtubs and buckets, were washed 30 times with a urethane sponge, and then the presence or absence of scratches was visually observed and evaluated. 〇...Does not hurt ○△...Usually there is no problem, but if rubbed too hard, it will hurt a little △...It will hurt a little ×...It will hurt Γ Rinseability Pour 10g of liquid cleanser composition onto a sponge,
Rub it evenly on the inside surface of an FRP bathtub (inner volume 70cm x 60cm x 60cm) for 3 minutes, then immediately rinse with a shower (flow rate 200ml/sec) for 1 minute. After sufficiently drying, observe the condition of the FRP surface with the naked eye. (Evaluation criteria) A: No whitening at all. B: Slight whitening is observed. C: Significant whitening is observed.

[Table] Example 2 A liquid cleanser composition having the following composition was prepared and tested for relative detergency, scratch resistance, rinsability, and low temperature stability. The results are shown in Table 2. [Composition] Sodium dodecylbenzenesulfonate
4 parts by weight Palm kernel oil fatty acid diethanolamide 3 Softanol 120 Note ¹⁾ 0.5 Crystalline aluminosilicate (interpenetrating type, number of aggregates >
30, average particle size 7μ) 20 Calcium carbonate (average particle size 10μ) 30 Plant aromatic oil (see Table 2) 0.5 Water Balance amount Note 1 Ethylene oxide adduct of linear secondary alcohol ( _C12-14 ) (= 12), [manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.] The low temperature stability was evaluated as follows. Low-temperature stability The liquid cleanser composition is filled into a 300 ml transparent polyester bottle and left in a constant temperature room at -5°C for 10 days. After standing, visually observe the condition of the liquid inside. (Evaluation Criteria) A: No change at all B: Slight separation of liquid. C: There was considerable liquid separation.

【table】 [Brief explanation of drawings]

FIG. 1 is a diagram showing a particle size distribution curve of crystalline aluminosilicate blended into a liquid cleanser composition.

Claims (1)

[Scope of Claims] 1 (A) contains an alkylbenzene sulfonate (B) an ethylene oxide adduct of a secondary alcohol (A) + (B) = 2 to 8% by weight, and (C) at least 30% by weight. A water-insoluble abrasive material consisting of an interpenetrating aluminosilicate formed by an aggregate of 3 to 40% by weight (D) Contains 0.01 to 3% by weight of a terpene hydrocarbon selected from monoterpenes and sesquiterpenes. A liquid cleanser composition characterized by: 2 The aluminosilicate has a particle size distribution curve of
In the particle size distribution curve shown in the figure, two curves X,
The liquid cleanser composition according to claim 1, having a particle size distribution that lies within the region delimited by X'.