JPH1036888A - Liquid detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liq. detergent compsn. which is excellent in scale-cleaning power and foaming properties and does not leave behind sliminess after rinsing by compounding a specific aminopolycarboxylic acid (salt), a surfactant, a solvent, and water in a specified wt. ratio. SOLUTION: An aminopolycarboxylic acid (salt) used is represented by formula I [wherein R1 and R2 are each independently H or -(CH2 )n COOH (wherein n is 1-3)[ (e.g. aspartic acid-N-acetic acid) and compounded in an amt. of 0.1-20wt.%. An anionic, cationic, amphoteric, or nonionic surfactant can be used without any specific limitation and is compounded in an amt. of 0.1-10wt.%. A solvent used, though not specifically limited, is pref. one represented by the formula: R1 O (C2 H4 O)m (C3 H6 O)n }H (wherein R1 is a 1-4C alkyl or phenyl; and m and n are each 0-3) (e.g. ethylene glycol monobutyl ether) and is compounded in an amt. of 0.1-30wt.%. The rest is water and the pH is 5-11.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a liquid detergent composition.

[0002]

2. Description of the Related Art Dirt adhering to equipment such as a bathtub or a washing place in a bathroom, and equipment such as a hot tub, a stool, and a sward is
It is composed of a mixture of fatty acid metal salts (mainly calcium salts) called free water, free fatty acids, glycerides, and organic substances such as nitrogen-containing compounds and inorganic substances such as mud. Conventionally, acidic or alkaline cleaning agents have been known as such cleaning agents for removing dirt. The acidic cleaning agent is composed of a composition containing an acidic substance, hydroxycarboxylic acid, a surfactant, and a water-soluble solvent (JP-A-52-77111). However, although such an acidic cleaning agent has a cleaning effect, it has a defect of damaging the surface of a hard material such as a tile joint or an aluminum sash. On the other hand, when an alkaline cleaning agent is used, there is a drawback that the effect of removing dirt is insufficient and the material is unfavorably affected. Furthermore, there still remains a problem that hands of a person who actually uses the cleaning agent become rough. On the other hand, Japanese Patent Application Laid-Open No. 52-76308 and
JP-A-6-22397 and JP-A-63-51500 disclose a hard surface cleaning agent comprising a combination of a surfactant and a metal ion sequestering agent, and a hard surface cleaning agent comprising a combination of a surfactant, a metal ion sequestering agent and a solvent. A surface cleaner is disclosed. However, these cleaning agents are not sufficient in terms of detergency and foaming properties when actually used,
Further, even after rinsing after use, there still remains a problem that a feeling of sliminess remains on the surface.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an excellent cleaning effect on scale stains attached to equipment and utensils in a bathroom, as well as excellent foaming properties when using a detergent.
In addition, it is an object of the present invention to provide a liquid detergent composition that does not leave a feeling of sliminess on the cleaning surface after rinsing and running after using the detergent.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have combined a specific aminopolycarboxylic acid, a surfactant and a solvent, and at the same time, adjusted the pH of the composition.
Was found to solve the above-mentioned problem by adjusting the value within a predetermined range, and completed the present invention.

That is, the present invention relates to (A) a compound represented by the general formula (I)

Embedded image (Wherein, R ₁ and R ₂ represent a hydrogen atom or — (CH ₂ ) _n C
Indicates an OOH group. N in this group is an integer of 1 to 3;
₁ and R ₂ are not simultaneously hydrogen atoms. ) Or a salt thereof 0.1 to 20
% By weight, (B) 0.1 to 10% by weight of a surfactant,
A liquid detergent composition comprising (C) 0.1 to 30% by weight of a solvent and (D) a balance of water and having a pH of 5 to 11 is provided.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION One of the components constituting the liquid detergent composition of the present invention has the general formula (1)

Embedded image (Wherein, R ₁ and R ₂ represent a hydrogen atom or — (CH ₂ ) _n C
Indicates an OOH group. N in this group is an integer of 1 to 3;
₁ and R ₂ are not simultaneously hydrogen atoms. ) Or a salt thereof (component A). Specific aminopolycarboxylic acids include aspartic acid-N-acetic acid, aspartic acid-N-propionic acid, aspartic acid-N-butyric acid, aspartic acid-N,
N-diacetic acid, aspartic acid-N, N-dipropionic acid, aspartic acid-N, N-dibutyric acid, aspartic acid-N-acetic acid-N-propionic acid, aspartic acid-N-
Acetic acid-N-butyric acid and the like can be mentioned. These aminocarboxylic acids are not limited to the acid form, but neutralize a part or all of the carboxyl groups with potassium hydroxide, sodium hydroxide, ammonium hydroxide, and monoethanolamine, diethanolamine, morpholine, and the like. Then, it is also possible to mix as an aminopolycarboxylate as a water-soluble salt.

The amount of the component (A) to be added to the detergent composition is as follows:
It is in the range of 0.1-20% by weight, preferably 1-10% by weight. If the amount is less than 0.1% by weight, the detergency is insufficient, and the interaction with the components (B) and (C) is not sufficient. On the other hand, if the compounding amount exceeds 20% by weight, no remarkable compounding effect is observed and it is uneconomical.

[0008] One of the components constituting the liquid detergent composition of the present invention is a surfactant (component B). As the surfactant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or the like can be used, and is not particularly limited. Specific examples are as follows, and these can be used alone or in combination of two or more. (1) Anionic surfactant Specific examples of anionic surfactant include alkyl sulfate, alkyl polyoxyethylene sulfate, alkylbenzene sulfonate, α-olefin sulfonate, fatty acid salt, ether carboxylate, Monoalkyl phosphates and the like can be mentioned. Counter ions (cations) of these anionic surfactants include alkali metal ions, alkaline earth metal ions, alkanolamine ions, ammonium ions and the like. (2) Cationic surfactant Specific examples of the cationic surfactant include an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, an alkylammonium salt, and an alkylbenzyldimethylammonium salt. Examples of the counter ion (anion) of these cationic surfactants include halogen. (3) Amphoteric surfactant Specific examples of the ampholytic surfactant include alkyl carboxy betaines, alkyl sulfo betaines, and the like. (4) Nonionic surfactant Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty acid diethanolamide, amine oxide, amidoamine oxide and the like.

The amount of the surfactant (B) added to the detergent composition is 0.1 to 10% by weight, preferably 0.1 to 10% by weight.
It is in the range of 5-7% by weight. When the amount of the surfactant is 0.
If it is less than 1% by weight, the dispersing and solubilizing effects on the scale are weak, and the interaction with the components (A) and (C) is not sufficient. On the other hand, if the compounding amount exceeds 10% by weight, no special effect of improving the detergency is brought about, and instead the foam is depleted and the rinsing property is deteriorated.

[0010] One of the components constituting the liquid detergent composition of the present invention is a solvent (component C). Although the solvent is not particularly limited, the following general formula (II) R ₁ O ｛(C ₂ H ₄ O) m (C ₃ H ₆ O) n｝ H (II) (wherein R ₁ is Represents an alkyl group having 1 to 4 carbon atoms or a benzene ring; m and n are each an integer of 0 to 3; these are not simultaneously 0; , Which is a polyoxyalkylene chain in which an oxyethylene group and an oxypropylene group are bonded in a random and / or block manner.). Specific examples of the solvent represented by general (II) include ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol diethylene glycol monobutyl ether, dipropylene glycol ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, and triethylene glycol monobutyl ether. Phenyl ether and the like can be mentioned.

The ratio of the solvent as the component (C) to the detergent composition is 0.1 to 30% by weight, preferably 5 to 1%.
5% by weight. If the amount is less than 0.1% by weight, the detergency is insufficient and the interaction with the components (A) and (B) is not sufficient. On the other hand, if the blending amount exceeds 30% by weight, no remarkable blending effect is observed and it is uneconomical. The solvent may be used alone or in combination of two or more.

The pH of the liquid detergent composition of the present invention is 5 to 5.
11, preferably in the range of 6-9. When the pH of the composition is less than 5 or more than 11, sufficient results can be obtained in terms of detergency and foaming property, and a composition which does not adversely affect the object to be washed cannot be obtained. In order to adjust the pH to this range, the pH can be adjusted with an alkali agent such as sodium hydroxide, potassium hydroxide, ammonium hydroxide and the like, and an acidic substance such as sulfuric acid and meta-xylene sulfonic acid.

In the present invention, the components used in the cleaning agent can be appropriately compounded as required. These components are used in combination with the components (A), (B) and (C) to improve the performance of these components, and to improve the properties of the entire detergent. Some are added to make it work. Optional components added in combination with component (A), components (B) and (C) to enhance the performance of these components include sequestering agents. Specific examples of sequestering agents include ethylenediaminetetraacetic acid,
Aminocarboxylic acids such as diethylenetriaminepentaacetic acid, N-hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetrapropionic acid, triethylenetetraminehexaacetic acid, ethyleneglycoldietherdiaminetetraacetic acid, cyclohexane-1,2-diaminetetraacetic acid, and acetic acid and adipine Acid, glycolic acid, diglycolic acid, monochloroacetic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid,
Lower carboxylic acids such as oxalic acid, malic acid, gluconic acid, carboxymethylsuccinic acid and carboxymethyltartaric acid are exemplified. These sequestrants are not limited to the acid form, but include potassium hydroxide, sodium hydroxide,
It is also possible to neutralize a part or all of the carboxyl groups with ammonium hydroxide, monoethanolamine, diethanolamine, morpholine, or the like, and mix them into a water-soluble salt. By adding the sequestering agent, an effect of further improving the detergency against scale can be obtained, and furthermore, rinsing after use, which has been a problem when using the sequestering agent instead of the component (A). It can solve the slimy feeling that remains after flowing.
The sequestering agent may be used in an amount of 0.1 to 60% by weight, preferably 10 to 40% by weight, based on the aminopolycarboxylic acid or a salt thereof.

The optional components added to improve the properties of the entire cleaning agent include lower alcohols, lower alkylbenzene sulfonic acids or salts thereof which are blended to maintain the liquidity at low or high temperatures. And hydrotropes such as ethylene glycol, bactericides, preservatives and fungicides, fragrances, pigments, antioxidants, thickeners, ultraviolet absorbers and the like. The compound used for these optional components is not particularly limited as long as it is a compound usually used for a detergent.

Examples of the fragrance include hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons and aromatic hydrocarbons, alcohols such as aliphatic alcohols, terpene alcohols and aromatic alcohols, and aliphatic ethers and aromatic ethers. Oxides such as ethers, aliphatic oxides and terpenes, aldehydes such as aliphatic aldehydes, terpene aldehydes, hydrogenated aromatic aldehydes, thioaldehydes and aromatic aldehydes, aliphatic ketones, terpene ketones, hydrogen Ketones such as fluorinated aromatic ketones, aliphatic cyclic ketones, non-benzene-based aromatic ketones and aromatic ketones, acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids, hydrogenated aromatic carboxylic acids Acids such as acid and aromatic carboxylic acid, acid amide Lactones such as aliphatic lactone, macrocyclic lactone, terpene lactone, hydrogenated aromatic lactone and aromatic lactone, aliphatic ester, furan carboxylic acid ester, aliphatic cyclic carboxylic acid ester, cyclohexyl carboxylic acid ester , Terpene carboxylate, aromatic carboxylate and other esters, nitrous musks, nitriles, amines, pyridines, quinolines, pyrroles, indole and other nitrogen-containing compounds, and other natural fragrances from animals and plants 1
Seeds or a mixture of two or more kinds could be used.

Next, the main specific fragrance names which can be used in the present invention are listed. Aldehydes C ₆ -C ₁₂ , anisaldehyde, acetal R, acetophenone, acetylsedren, adoxal, allyl amyl glycolate,
Allyl cyclohexane propionate, alpha damascon, beta damascon, delta damascon, ambrette lid, ambroxane, amylcinamic aldehyde, amylcinnamaldehyde dimethyl acetal, amyl valerinate, amyl salicylate, isoamyl acetate, isoamyl salicylate, Auranthiol, acetyljugenol, bacdanol, benzyl acetate, benzyl alcohol, benzyl salicylate, bergamyl acetate, bornyl acetate, butyl butyrate, para-tert-butylcyclohexanol, para-tert-butylcyclohexyl acetate, ortho-tert- Butylcyclohexanol, benzaldehyde, benzyl formate, caryophyllene, cash Orchid, carvone, cedroambar, cedrol acetate, cedrol, celestrid, cinamic alcohol, cinamic aldehyde, cis jasmon, citral, citral dimethyl acetal, citrasall, citronellal, citronellol, citronellyl acetate, citoneryl formate, citronellil Nitrile, cycla set, cyclamen aldehyde, cycla prop, caron, coumarin,
Cinnamyl acetate, delta C ₆ -C ₁₃ lactones, dimethyl benzyl carbinol, dihydrojasmonate, dihydro linalool, dihydromyrcenol, Jimetoru, Jimirusetoru, diphenyl oxide, Echiruwanirin, Yugenoru, Furuiteto, Fen steel alcohol, phenylethyl phenylacetate, Garaki solid, gamma C ₆ -C ₁₃ lactone, geraniol,
Geranyl acetate, geranyl formate, geranyl nitrile, hedion, helional, heliotropin, cis-3-hexenol, cis-3-hexenyl acetate, cis-3-hexenyl salicylate, hexylcinnamic aldehyde, hexyl salicylate, hyacinth Dimethyl acetal, hydrotropic alcohol, hydroxycitronellal, indole, ionone, isobornyl acetate, isocyclocitral, iso E super, isojugenol, isononyl acetate, isobutyl quinoline, jasmar, jasmolactone, jasmofilan, koabon, Rigstral, lilial, lime oxide, limonene,
Linalool, linalool oxide, linalyl acetate, liral, manzanate, mayol, menthanyl acetate, menthsonate, methyl anthranilate, methyl jugenol, menthol, alpha methyl ionone, beta methyl ionone, gamma methyl ionone, methyl isojugenol , Methyl lavender ketone,
Methyl salicylate, muguealdehyde, mugol,
Musk TM-II, Musk 781, Musk C14, Musk T, Musk ketone, Musk Tibetin, Musk Mosken,
Mirac aldehyde, methyl phenyl acetate, nerol, neryl acetate, nopir acetate, nopyl alcohol, neobergamate, oakmoss
1. Oribbon, Oxyphenylone, Paracresil Methyl Ether, Pentalid, Phenylethyl Alcohol, Phenylethyl Acetate, Alpha Pinene, Lubafuran, Rosephenone, Rose Oxide, Sandaroa, Sandella, Santa Rex, Styril Real Acetate, Styril Real Propionate, terpineol, terpinyl acetate, tetrahydrolinalool, tetrahydrolinalyl acetate, tetrahydrogeraniol, tetrahydrogeranyl acetate, tonalid, traseolide, tripral, thymol, varnish, verdox, yayala, anise Oil, bay oil,
Boad rose oil, cananga oil, cardamom oil, cassia oil, cedarwood oil, orange oil, mandarin oil, tangerine oil, basil oil, nutmeg oil, citronella oil, clove oil, coriander oil, elemi oil, eucalyptus oil, fennel oil, galvanum oil , Geranium oil, hiba oil, cypress oil, jasmine oil, lavandin oil, lavender oil, lemon oil, lemongrass oil, lime oil, neroli oil, oak moss oil, octocia oil, patchouli oil, peppermint oil, perilla oil, petitgren oil, Pine oil, rose oil, rosemary oil, camphor oil, fragrance oil, clary sage oil, sandalwood oil, spearmint oil, spike lavender oil, star anise oil, thyme oil, tonka bean tincture, turpentine oil, crocodile bean tincture, vetiver Oil, ylang-ylang oil, grapefruit oil, yu Oil, benzoin, Pell - balsam, Torr - balsam, tuberose oil, Musukuchinki,
Castorium tincture, civet tincture, ambergris tincture. Further, diethyl phthalate, dipropylene glycol, benzyl benzoate, isopropyl myristate, hacoline and the like can be used as a solvent or a retaining agent for the fragrance.

[0017]

EXAMPLES Specific examples of the cleaning composition of the present invention will now be described. In order to confirm the effects of the examples, a cleaning power test of the cleaning agent against scale stains, a foaming test of the cleaning agent, a test of the degree of sliminess after rinsing the cleaning agent, and a test of the effect of the cleaning agent on the object to be washed were performed. Was. The operation contents and evaluation method of these tests are as follows. (1) Detergency test of detergent against scale stains A polypropylene bathtub with a scale attached that cannot be easily removed by rubbing (used for 2 months)
, A liquid detergent composition (stock solution) is sprinkled, and the surface of the tub is rubbed back and forth five times with a urethane sponge under a load of about 20 g / cm ² , and the stain removal state is visually judged according to the following criteria. The criteria are as follows. 5 points: Very good stain removal. 4 points: Stain removal is good. 3 points The stains are uneven. 2 points: Slight stain removal. 1 point: Almost no dirt is removed.

(2) Defoaming Test of Detergent The detergent composition was sprinkled with 2.5 ml of the detergent composition on the upper side of a 1 m × 50 cm stainless steel plate placed vertically, and a wiping pressure of 10
The sample was rubbed back and forth five times with a sponge having a water content of 250% at g / cm ² , and the state of foam was visually judged. The criteria are as follows. ：: Good foaming. Δ: Bubbling is slightly good. ×: Foaming is not good.

(3) Degree of slimyness test after rinsing the detergent 2.5 m1 of the detergent composition was sprinkled on the upper side of a stainless steel plate of 1 m × 50 cm vertically installed, and a wiping pressure of 10
After rubbing back and forth five times with a sponge having a water content of 250% at g / cm ² and blowing bubbles with a cleaning agent with a shower having a water amount of 150 ml per second, the degree of sliminess of the plate surface is organoleptically evaluated according to the following criteria. did. The criteria are as follows. ：: Not slim at all. Δ: Slightly slimy. X: Slimy.

(4) Influence Test of Detergent on Washable Material A joint and an aluminum plate were immersed in the detergent composition for 24 hours, and the surface condition was visually judged according to the following criteria. The criteria are as follows. ：: No change was observed at all. Δ: Slight change is observed. X: A change is clearly observed.

Examples 1 to 7 and Comparative Examples 1 to 5 Examples 1 to 7 of the liquid detergent composition of the present invention are shown in Table 1. Table 2 shows Comparative Examples 1 to 5. In order to confirm the effects of the examples and comparative examples of the present invention, a cleaning power test of the cleaning agent against the descaling, a foaming test of the cleaning agent, a degree test of sliminess after rinsing the cleaning agent, and a cleaning of the object to be washed. The effect of the agent was tested. Table 1 also shows the results of this test.
And Table 2.

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

[Table 3- (1)]

[0025]

[Table 3- (2)]

[0026]

[Table 3- (3)]

[0027]

[Table 3- (4)]

[0028]

[Table 3- (5)]

[0029]

[Table 3- (6)]

[0030]

[Table 3- (7)]

[0031]

[Table 3- (8)]

[0032]

[Table 3- (9)]

[0033]

[Table 3- (10)]

[0034]

[Table 3- (11)]

As is evident from Table 1 above, the liquid detergent compositions containing the components of the present invention in a predetermined amount and having a pH within a predetermined range all show excellent performance. On the other hand, as shown in the results of Table 2, the liquid detergent composition containing no aspartic acid-N, N-diacetic acid (Comparative Example 3) exhibited a detergency against scale, foaming property of the detergent, and detergent. It can be seen that the degree of sliminess after rinsing was inferior. Further, the liquid detergent composition containing no surfactant component (Comparative Example 4) is inferior in detergency against scale and foaming property of the detergent,
The liquid detergent composition containing no diethylene glycol-based solvent component (Comparative Example 5) is inferior in detergency against scale. Further, when the pH is not within the predetermined range, the effect on the object to be washed is inferior even though the detergency against the scale is relatively excellent (Comparative Examples 1 and 2).

[0036]

Industrial Applicability The liquid detergent composition of the present invention exhibits particularly excellent detergency against scale stains attached to bathroom equipment and utensils, has excellent foaming properties when using a detergent, and is rinsed. It shows an excellent performance that no slimy feeling is left on the cleaning surface after flowing.

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[Procedure amendment]

[Submission date] September 5, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0022

[Correction method] Change

[Correction contents]

[0022]

[Table 1]

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0023

[Correction method] Change

[Correction contents]

[0023]

[Table 2]

Claims (1)

[Claims] (A) General formula (I) (Wherein, R ₁ and R ₂ represent a hydrogen atom or — (CH ₂ ) _n C
Indicates an OOH group. N in this group is an integer of 1 to 3;
₁ and R ₂ are not simultaneously hydrogen atoms. ) Or a salt thereof 0.1 to 20
(B) 0.1 to 10% by weight of a surfactant, (C) 0.1 to 30% by weight of a solvent, and (D) a balance of water, and the pH is 5 to 11. Liquid detergent composition.