KR960004485B1 - Liquid detergent composition - Google Patents

Abstract

This is new cleaner composition The cleaner which comprises anionic 0.1-20wt.%, nonionic 0.1-40wt.% and cationic surfactant 0.1-10wt.%, contains D-limonene 0.1-10wt.%, poly(1-vinyl-2-pyrrolidone) 0.1-3wt.% and tetrabenzo-tetraazapropine deriv 0.01-0.1wt.%. The anionic surfactant is one kind or its mixture selected from sulfate, sulfonate, phosphate and carboxylate, nonionic surfactant is selected from polyalkylene addition, amine oxide, mono- and diethanol amide type, and cationic surfactant is from C8-C16 alkyltrimethyl ammonium chloride, bromide, and ketylsulfate.

Description

Liquid Detergent Composition

The present invention relates to a liquid detergent composition.

More specifically, the present invention is characterized by containing 0.1 to 10% by weight of di-limonene, 0.1 to 3% by weight of 1-vinyl-2-pyrrolidone polymer and 0.01 to 0.1% by weight of tetrabenzo-tetraazapropene derivative. It relates to a liquid detergent composition.

Liquid detergents that have been used in conventional laundry washing can be divided into two types, namely, the case of using a surfactant and a water-soluble organic builder and the case of using a surfactant and an inorganic builder.

In US Pat. No. 4560492, hydroxyethyl ethylene diamine triacetate composition was used as an organic builder to improve cleaning power, but no satisfactory effect was obtained in oily or stained contamination.

In addition, U.S. Patent No. 4561998 used anionic surfactants, cationic surfactants and fatty acids to increase the cleaning power against oil pollution, but the overall cleaning power was insufficient due to the neutral pH.

In US Patent 4605509 European Patent 0459077 A1, zeolite was used as a builder, but unsatisfactory results were obtained due to lower solubility at low temperatures, residue formation and phase anxiety of the product.

The present inventors have studied to compensate for these drawbacks, and found that the liquid detergent composition contains di-limidene, 1-vinyl-2-pyrrolidone polymer and tetrabenzo-tetraazapropine derivative, so that the washing ability is excellent and washing is possible. To prevent the dyeing of the dye generated during the development, to minimize the foaming to improve the rinsing, and to invent a liquid detergent composition in which bleaching of stain contamination occurs during daylight drying.

The present invention comprises 0.1 to 10% by weight of di-limonene, 0.1 to 3% by weight of 1-vinyl-2-pyrrolidone polymer and 0.01 to 0.1% by weight of tetrabenzo-tetraazapropene derivative. To a composition. The liquid detergent composition according to the present invention may further contain 0.1 to 20% by weight of anionic surfactant, 0.1 to 40% by weight of nonionic surfactant and 0.1 to 10% by weight of cationic surfactant.

Di-limonene contained in the liquid detergent of the present invention is a monocyclic terpen which is usually obtained as a by-product from citrus juice preparation. It is obtained by steam distillation of citrus peel and pulp from citrus juice production, with about 94-98% being oily. Di-limonene is almost completely harmless to the human body and the environment, and is particularly useful as a solvent for oil pollution such as milk, chocolate, lipstick and the like. The content of di-limonene is 0.1 to 10% by weight, preferably 1 to 5% by weight. When di-limonene is used in an amount of 0.1 wt% or less, it does not have an effect as a solvent, and when 10 wt% or more is used, it acts as a contamination itself.

The present invention also uses a 1-vinyl-2-pyrrolidone polymer to prevent dye transfer of laundry desorbed during washing and to prevent reattachment of general contamination, which is particularly a garment dye that occurs when using tetrabenzo-tetraazapropine derivatives. It significantly reduces the phenomenon. The 1-vinyl-2-pyrrolidone polymer is contained in the composition in an amount of 0.1 to 3% by weight, preferably 0.1 to 0.5% by weight. In 0.1 wt% or less, there is almost no effect, and in 3 wt% or more, a viscosity increase of the composition occurs.

Tetrabenzo-tetraazapropine derivatives are used in the present invention as photobleach and fluorescence brightening aid. It absorbs light energy in the presence of water to generate free radicals and oxidize stains and microorganisms. It is contained 0.01 to 0.1% by weight, preferably 0.1 to 0.08% by weight in the composition. At 0.01 wt% or less, there is little effect, and at 0.1 wt% or more, dyeing occurs in the garment during washing.

The anionic surfactant used in the present invention preferably contains 0.1 to 20% by weight, preferably 1 to 10% by weight of one or two or more mixtures of the anionic surfactants of the following (1) and (2). At 0.1 wt% or less, there is little effect, and at 20 wt% or more, proper mixing with nonions is difficult.

(1) sulfonate

Linear or branched alkyl (average carbon chain length 10 to 19) benzenesulfonate long chain alkyl (average carbon chain length 12 to 18) sulfonate, long chain olefin (average carbon length 10 to 20) sulfonate and the like.

(2) sulfate

Long chain mono alkyl (average carbon chain length 10-18), sulfuric acid ester salt, polyoxy ethylene long chain alkyl (average carbon chain length 10-16), ether sulfate ester salt, polyoxy ethylene alkyl (average carbon chain length 6-12), Phenyl ether sulfate ester salts and the like.

The nonionic surfactant used in the present invention is not particularly limited, but specifically, polyoxyethylene (P = 9) C ₁₂ -C ₁₄ alkyl ether, polyoxyethylene (P = 12) C ₁₀ -C ₁₂ alkyl ether, poly Polyoxy alkylene long chain alkyl ethers represented by oxyethylene (P = 20), C ₁₆ alkyl ether, polyoxyethylene (P = 10) polyoxy propylene (P = 5), C ₁₂ -C ₁₄ alkyl ether, and the like. , Polyoxyethylene (P = 9), C ₁₂ -C ₁₄ secondary alkyl ether, polyoxyethylene (P = 5), C ₁₂ -C ₁₄ secondary alkyl ether, polyoxyethylene (P = 7), C ₁₂ -C ₁₄ secondary alkyl ether polyoxyethylene (P = 12), C ₁₀ -C ₁₂ secondary alkyl ether, polyoxyethylene (P = 7), polyoxypropylene (P = 5) secondary With polyoxyalkylene long chain secondary alkyl ethers represented by alkyl ethers, polyoxyethylene (P = 8) nonylphenol ether, polyoxyethylene (P = 15) polyoxypropylene (P = 4) nonylphenyl ether Polyoxyethylene alkylphenyl ethers represented, polyoxyalkylene block polymers represented by polyoxyethylene (P = 20) polyoxypropylene (P = 15) block polymers, palm fatty acid diethanol amides, oleic acid trimethanolamides, 1 type, or 2 or more types of mixtures, such as a higher fatty acid alkanolamide or its alkylene oxide adduct which are represented by lauric acid monoethanolamide etc. can be mentioned.

The content of the nonionic surfactant is 0.1 to 40% by weight, preferably 10 to 35% by weight. It is hardly effective at 0.1 weight% or less, and it is difficult to use it by viscosity increase at 40 weight% or more. In particular, in the case where a mixed number of ethylene oxide added moles is used, when 7 to 20 moles of nonionic surfactant and 3 to 5 moles of nonionic surfactant are mixed from 9: 1 to 1: 9, the low temperature of cloud point decreases. Detergency build up appears.

The cationic surfactant used in the present invention is a quaternary ammonium surfactant and has the following general formula.

[R2 (OR3) y] [R4 (OR3) y] 2R5N + X-

Wherein R 2 is an alkyl or alkylbenzyl group having 8 to 18 carbon atoms in the alkyl chain. Each R 3 consists of -CH ₂ CH _2- , CH ₂ CH (CH ₃ )-, CH ₂ CH (CH ₂ OH)-, -CH ₂ CH ₂ CH ₂ -and mixtures thereof. Each R 4 is selected from C ₁ -C ₄ alkyl C ₁ -C ₄ hydroxyalkyl, benzyl, a cyclic structure formed by the association of two R 4 groups, and the like. R5 should be the same as R4, or the alkyl chain should have 18 or less carbon atoms plus R2 and R5. Each y is from 0 to 10 and the sum of the y values is from 0 to 15. X can be any valid anion. Of these, preferably as alkyl quaternary ammonium surfactants, especially single long chain alkyl surfactants are suitable. Specifically chloride, bromide and methyl sulfate C ₈ -C ₁₆ alkyltrimethyl ammonium salts, C ₈ -C ₁₆ alkyl di (hydroxyethyl) -methylammonium salts, C ₈ -C ₁₆ alkyl oxypropyl trimethyl ammonium salts and the like. Their content is 0.1 to 10% by weight, preferably 1 to 5% by weight. It is hardly effective at 0.1 wt% or less, and at 10 wt% or more, it is difficult to use due to problems such as TKD solubility with anion and rise of the cloud point of non-ion. In particular, when mixed with an anionic surfactant in a molar ratio of 1: 1 to 5: 1, an increase in the prevention of reattachment and a detergency by the formation of the complex are improved.

In the liquid detergent composition of the present invention, it is possible to use a water-soluble organic enhancer, a hydrocrop agent, a fluorescent brightener, a incense burner, etc. as necessary.

Generally as a water-soluble organic enhancer, amine polycarboxylic acids, such as sodium citrate, ethylene diamine tetra acetate, the penta sodium salt of diethylene triamine penta acetic acid, etc. are used.

Hydrotropes act as low temperature phase stabilization, solubilization and so on.In general, alcohols and polyols represented by short-chain alkylbenzene sulfonates such as toluene sulfonate and xylene sulfonate, ethanol, ethylene glycol, propylene glycol, and the like Ryu.

Fluorescent whitening agents include Tinopal CBS-X (Ciba-Geigy), Tinopal SWN (Ciba-Geigy) or color-index fluorescent whitening agents 28, 40, 61 and 71.

The above-mentioned additives can be arbitrarily blended as needed, and besides, it can be used to exhibit similar effects.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely based on an Example.

EXAMPLE

To combine the components shown in Table 1 to prepare a liquid detergent composition.

* (P2) in the table indicates the average number of moles of ethylene oxide added.

Evaluation method of cleaning power, rinsing property, dyeing degree, dyeing property and phase safety of the liquid detergent composition having the composition shown in Table 1 is as follows.

(1) cleaning power

1) Conditions

① Contaminated cloth: Polyester / Cotton (6/4), Cotton

② Washing machine: Terg-O-Tometer, 100rpm, 25 ℃, 10 minutes

③ Washing condition: Water hardness (50ppm, 100ppm, CaCO ₃ )

Detergent concentration 1g / ι

2) evaluation

Whiteness measurement with a colorimeter (Japanese color ∑80).

※ formula

o; Raw cloth s; Contaminant w; Cleaning cloth

(2) degree of dye

In the same conditions as the cleaning power test method, colored cloth and cotton white cloth are used instead of contaminated cloth. After washing, visually determine the degree of dye transfer of cotton bags.

(3) rinsing property

Add 4ι water and 4ι detergent into 8ι container, compare 10 the volume after quenching 10 times using blue towel after dissolution. 3 replicates (after no detergent)

(4) dyeability

300 ml of detergent stock solution in 1ι container, cotton cloth immersion (2 hours). After immersion, rinse, dry after daylight and visually determine the dyeing in UV.

(5) phase stability

Each sample was stored at 50 ° C in a constant temperature and humidity chamber for 1 month, and then visually judged.

As shown in Table 1, it can be seen that the compositions of Examples 1 to 7 show superior cleaning power, rinsing property, dyeing degree, and dye stability compared to those of Comparative Examples 1 to 3.

Claims (8)

In a detergent composition containing an anionic surfactant, a nonionic surfactant and a cationic surfactant, 0.1 to 10% by weight of di-limonene (hereinafter, based on the total weight of the composition), 0.1 to 3% by weight of 1-vinyl-2-pyrrolidone polymer % And 0.01 to 0.1% by weight of a tetrabenzo-tetraazapropene derivative. The method of claim 1, characterized in that it contains 1 to 5% by weight of di-limonene, 0.1 to 0.5% by weight of 1-vinyl-2-pyrrolidone polymer, and 0.01 to 0.08% by weight of tetrabenzo-tetraazapropene derivative. Liquid detergent composition. The liquid detergent composition according to claim 1, which contains 0.1 to 20% by weight of anionic surfactant, 0.1 to 40% by weight of nonionic surfactant, and 0.1 to 10% by weight of cationic surfactant. The liquid detergent composition according to claim 3, wherein the anionic surfactant is one or a mixture of two or more selected from sulfates, sulfonates, phosphates and carbonates. 4. The liquid detergent composition according to claim 3, wherein the nonionic surfactant is one or a mixture of two or more selected from polyalkylene addition type, amine oxide type, mono and diethanol amide type. The nonionic surfactant according to claim 5, wherein the nonionic surfactant having 7 to 20 moles of ethylene oxide added moles and the nonionic surfactant having 3 to 5 moles of ethylene oxide is mixed at 9: 1 to 1: 9 in the nonionic surfactant. Liquid detergent composition. 4. The method of claim 3, wherein the cationic surfactant is one, or a mixture of two or more selected from chloride, bromide and ketyl sulfate C ₈ -C ₁₆ alkyltrimethyl ammonium salts, C ₈ -C ₁₆ alkyl di (hydroxyethyl) methyl ammonium salts. Liquid detergent composition characterized in. The liquid detergent composition according to claim 3, wherein the cationic surfactant is mixed with the anionic surfactant in a molar ratio of 1: 1 to 1: 5.