KR20020030181A - Mild composition of cleaning material for clothing - Google Patents

Abstract

PURPOSE: Provided is a non-pollution detergent composition for mild clothes, which is excellent in water-washing effect for wool, silk, and flax clothes, shrinkage-resistant effect, washing ability, and stability and dose not give stimulation to human bodies. CONSTITUTION: The non-pollution detergent composition comprises: 5-30wt% of D-limonene as a natural detergent; 5-15wt% of N-acyl sarcosinate and alkyl ether sulfate as washing accelerators; 10-20wt% of at least two compounds, selected from the group consisting of polyoxyethylene alkyl ether, multivalent-alcohol alkyl polyether, alkylether carboxylate, polyoxyethylene-polyoxypropylene alkyl ether, as dispersing emulsifiers; 2-5wt% of long chained alkyl succinic dibasic acid salt and polyoxyethylene high fatty acid ester as solubilizing agents; functional auxiliaries containing 3-5wt% of polyethylene glycol, 1-5wt% of high fatty acid soap, 1-5wt% of alkanol amide, 1-10wt% of glycol ether, 1-10wt% of at least one of ethanol, ethylene glycol, propylene glycol, 0.05-1wt% of citric acid or EDTA-4Na, 0.01-2wt% of at least one of carboxymethyl cellulose-sodium(CMC-Na) or CMC-Ca, polyvinyl pyrrolidone, carbopol, water-soluble chitosan.

Description

Mild composition of cleaning material for clothing

The present invention relates to a mild non-polluting detergent composition for garments, and more particularly, natural physiologically rinsable dilimonene, a cleaning accelerator, a dispersing emulsifier and a solubilizer as a main component, if necessary, by mixing a specific adjuvant in a specific ratio It is not only excellent in water washing effect on hair, silk and hemp garments that could not be washed by water, but also washable by immersion method, which has been used so far. A mild, non-polluting detergent composition for garments characterized by a new composition which is free of irritation and is excellent in both detergency and stability.

Conventional garment cleaners include solid laundry soaps based on sodium high fatty acid salts (soaps), straight chain high alkyl sulfonates (LAS), long chain alkylbenzene sulfonates (ABS), alpha olefin sulfonates (AOS) and alpha sulfones. Mineral emulsifiers such as higher fatty acid methyl ester salts, powdered synthetic detergents composed mainly of animal and vegetable raw materials, such as higher fatty acids and higher fatty alcohols, have been mainly composed. These detergents can effectively wash oily secretions such as skin secretions, dust, municipal soot and organic synthetic oils attached to clothing, protein components such as dead skin cells, and starch components such as various food residues, especially in synthetic clothing. Synthetic fibers such as polyester, nylon, and acrylic fiber fabrics, or blended fibers thereof, also show great washing effects.

However, with the improvement of the standard of living of the people, the trend of using the clothing has been to prefer the garment made of natural fiber rather than the synthetic fiber. It was hoped that this could be possible, and with the changing environmental awareness, much attention has been paid to the problem of water pollution on existing washing methods.

Conventional laundry detergents are mainly composed of mineral synthetic detergents and emulsifiers, and when washing, it is necessary to replenish mechanical energy such as rotational friction force or impact caused by water in the washing machine. Since yam is a fiber having weak water resistance, shape deformation and shrinkage are inevitable. For this reason, in the past, such natural fiber garments were left to dry cleaners to ritual dry cleaning. However, these methods are also difficult to solve the environmental problems and waste disposal methods due to the use of dry cleaning agents.

So far, the dry cleaning method used in the laundry is dry washing method using petroleum solvents and mineral emulsifiers for high-quality garments, which are mainly wool, silk fabrics, and hemp fabrics, and perchlorethylene as a petroleum solvent. This is typically used. Recently, it is pointed out in developed countries, including the United States, that the dry cleaning method causes water pollution problems in terms of environmental friendliness due to the physical and chemical properties of perchlorethylene which is generally used. Perchlorethylene is poorly hydrolyzed and has teratogenicity and carcinogenicity. It is known as environmental pollutant since it was published in the Sigma-Aldrich Library of the United States. Considering the toxicity by inhalation, there is a very serious contamination problem. In addition, the disposal of perchlorethylene after the used treatment is not specifically prepared, so it always remains as a soil, river, and air pollutant, which implies the problem of environmental pollution. Therefore, the inventors of the present invention are essentially harmless to the human body and have no problem of causing environmental pollution in order to solve the pollution problem of the dry cleaning agent used in the laundry and the laundry at the same time, there is no problem of causing shrinkage of clothes by washing with water Innovative mild detergent-free detergent compositions have been developed that can solve problems such as shape deformation.

The present invention uses dilimonene, which is a solvent extracted from natural products, as a natural detergent, amino acid surfactants as anionic surfactants as cleaning accelerators, nonionic surfactants as dispersing emulsifiers, and dibasic acids as solubilizers. By changing the washing style of existing detergents, it is possible to obtain the washing effect of dry cleaning at home easily, so that it is possible to do mild pollution-free washing without deformation or shrinkage of clothing.

The natural dilimonene used as a natural solvent in the present invention is an extract of natural citrus peel and is a by-product obtained by distillation extraction from orange fruit peel produced in large quantities in the United States, Australia, Brazil and Europe. Dilimonene is a kind of optically active terpenoids in terms of chemical structure, and has a degreasing rate having a unique inherent odor due to its structural characteristic of having an orientation structure similar to that of benzene with 10 carbon atoms. It is a pollution-free material that has its own very high decontamination capability from perchlorethylene, which has been obtained from petroleum solvents. Dirimonene is also used for industrial applications, fragrances in food industry or cosmetics, depending on the content of normal aldehydes such as octanal, nonanal, decanal and linanol, and part of the deodorant composition as in Patent Publication No. 90-6854. It is also used for uses, such as a component. Since dilimonene has a high boiling point above 154 ℃, it is a chemically stable liquid and is classified as GRAS (Generally Recognized As Safe) by the FDA. . Examples of applying such dilimonene as a cleaning agent are registered in US Pat. Nos. 4,511,488 and 4,620,937, UK Pat. No. 1,603,047, Korean Patent No. 1996-0011675, and the like.

In particular, unlike the conventional dry cleaning agent used in the mild non-polluting detergent composition for clothes, a mild non-polluting composition for clothes without shrinkage or deformation when used for immersion water washing is not known until now, In the method of use, mechanical rotational force or external physical force using air bubbles was always required. In general, solid contaminants can explain the washability by the electrostatic energy action of desorption from the substrate, but desorb the contaminants by differential distances by inducing the adsorption form between the contaminant particles and the substrate into the hydrated form of the dispersed phase by the surfactant. Let's do it. From this point on, the pollutants are washed away by the mechanical rotational kinetic energy of the washing machine, the dispersion effect of water, and the ultrasonic waves. When washing using a mechanical device, that is, a washing machine, heavy energy is provided to the laundry, that is, clothing by the kinetic energy of the rotor in the tank, thereby inevitably causing shrinkage and deformation of the clothes. Therefore, the detergent composition dissolves the contaminants by immersion of a pollution-free natural detergent rather than the removal of the contaminants by mechanical rotational kinetic energy in the washing machine, thereby separating the contaminants and preventing the resorption, thereby providing a shrinkage effect. The discharged cleaning liquid minimizes water pollution, so that the dry cleaning effect of the laundry can be achieved by sufficiently immersing at home.

Experimental research results to overcome the above-mentioned defects of the conventional products in the present invention as a main component of di-limene, a natural orange orange extract, a cleaning accelerator, a dispersing emulsifier and a solubilizing agent, and as a supplement, higher fatty acid salts, polyhydric alcohols and alkaca as necessary When manufacturing a mild non-polluting detergent composition blended with Nolamide in a specific ratio and washing it by dipping, it improves the washing efficiency and maintains the shape stability after washing for pure wool, silk and cotton fabrics and these mixed fabrics. It is biodegradable and pollution-free.

Known basic laundry, laundry detergent is divided into weak alkaline detergent and neutral detergent. The weak alkaline detergent is used for general clothing such as cotton and blended fibers, and animal fibers such as wool and silk and acetate fibers use neutral detergent. If a weak alkaline detergent is used on clothing intended to use a neutral detergent, it may cause shrinkage, deformation, or discoloration. Therefore, a neutral detergent should be used. Since light clothes such as ivory or pastel are easily discolored, use a neutral detergent. Should be used and washed. It is also recommended to wash wool with a mild detergent at 30 ℃ or below for fragile wool or silk which is easy to discolor. Therefore, in the present invention, the pH of the composition is maintained at about 7 to minimize the shrinkage and damage to the silk, hair and hemp clothing, which is a natural fiber during washing, thereby improving the washing effect and also improving the ion balance (ion). Due to the balance effect, the irritation to the skin is greatly reduced, and it is possible to prevent contact dermatitis and skin keratinization due to excessive degreasing of the skin. In addition, due to the low foaming force, especially at low temperatures, the rinsing effect is further improved.

In general, the liquid laundry detergent used for laundry washing is composed of main components such as surfactant component and enzyme component, and auxiliary components such as bleaching and fluorescent whitening component, and most of the liquid is alkaline to increase the activity of the enzyme. Since the liquid is alkaline and contains enzymes, it is impossible to prevent damage to high-quality clothing, and the enzyme and bleaching components may alter the tissues of the garment, cause damage to skin proteins, and even be a carcinogen. Is known to be dangerous to humans.

An object of the present invention is to solve the above-mentioned shortcomings, mild surfactant component which is the basic component of laundry washing and orange oil extracted from natural products, rinsing improvement component to improve the residual detergent feeling during washing and prevent re-fouling adhesion Alkaline, which adds ingredients to prevent clothing and skin damage at the same time, and also maintains alkalinity to aid washing conditions such as enzyme performance during washing, is not added to avoid tissue deformation and damage to skin proteins in clothing. To provide a mild liquid neutral detergent composition that can protect clothing and skin. Furthermore, by eliminating the use of surfactants containing benzene nuclei in the detergent composition used to wash various clothes, the low biodegradability eliminates the pollution factors that greatly increase the BOD (biological oxygen demand) in rivers and rivers. It is to solve the problems that cause the destruction of the ecosystem. Thus, in the present invention, as a main raw material of the natural dilimonene, washing accelerator, dispersing emulsifier and solubilizer to improve the washability and to eliminate water pollution after washing, there is no shrinkage and shape deformation after washing of the mother and dog fabrics and maintain stability It is an object of the present invention to provide a mild detergent-free detergent composition that can be preserved.

In addition, the object of the present invention is to dissolve the conventional liquid in the form of gel in a separate spoon, etc., uncomfortable to stir loose, while the dissolution in water easily dissolves in water and does not form an insoluble precipitate that induces irritation to the human body. It is a microemulsion type that provides a unique low-viscosity liquid composition that improves hydrolysis, dispersibility, and rinsability, and neutralizes liquid pH, which is essential for washing natural fibers, to prevent deformation, shrinkage, and discoloration of clothing. .

Hereinafter, the configuration of the present invention in detail.

The most suitable viscosity of the inherent low viscosity liquid composition, which prevents form deformation, shrinkage and discoloration of the garment, is the spindle number 2 of the Brookfield viscometer, 2.5 rpm, 20^°C Condition is 500 ~ 2000 cps.

Detergent composition of the present invention comprises the following components.

(1) Dilimonene extracted by steam distillation from skins of oranges, lemons, etc.

(2) N-acyl sarcosinate and polyoxy ethylene ether sulfate ester salts as cleaning accelerators

(3) Copolymers of polyoxyethylene alkyl ethers, polyhydric alcoholic alkyl polyethers, alkyl ether carboxylates and ethylene glycol-propylene glycol as dispersing emulsifiers

(4) Long-chain alkyl succinate dibasic acid salts and polyoxyethylene higher fatty acid esters as solubilizers

(5) supplements by function

① Softener: polyhydric higher alcohol

② Rinse enhancer: High grade fatty acid salt

③ viscosity and fluidity regulator: alkanol amide

④ Solventization Accelerator: Glycol Ethers

⑤ Hydro trough agent: Ethanol, ethylene glycol, propylene glycol

⑥ Water-soluble cleaning enhancer: citrate, ethylene diamine tetra acetate

⑦ Anti-fouling agent: carboxy methyl cellulose salt, polyvinyl pyrrolidone, carbopol, water soluble chitosan

In the above-described composition of the present invention, dilimonene is preferably 5 to 30% by weight, more preferably 10 to 20% by weight. If dirimonene is used less than 5% by weight, sufficient cleaning effect by dipping method cannot be obtained, and when excessively used, it is more than 30% by weight because it is easy to cause morphological deformation and discoloration phenomenon in laundry for clothes and it is inferior in water dispersibility. It is not good to do.

In addition, 5 to 15% by weight of N-acylated sacosinate and ethoxylated vegetable fatty acid sulfate, which are a protein surfactant, is used as a cleaning accelerator. When the content is less than 5% by weight, the active component of the protein is offset by alkyl ether sulfate. The skin irritation can not be alleviated more, and if it exceeds 15% by weight, due to excessive cleaning promotion, rather than the emulsion dispersion of the non-ionic surfactant is poor, the phase stabilization at room temperature cannot be achieved.

The dispersing emulsifiers include alkyl groups in polyoxyethylene alkyl ethers, which are nonionic surfactants, with ethylene oxide adducts of primary, secondary or tertiary alcohols, polyhydric alcoholic alkyl ethers, polyoxyethylene-propylene alkyl ethers and anionic surfactants. Alkyl ether carboxylates are used, which contains nonionic surfactants as main cleaners and anionic surfactants together to increase complex synergistic efficiency in decontamination, as well as interfaces with benzene rings that adversely affect the human body and the environment. By excluding the active agent, biodegradability can be further improved. 10 to 20% by weight of two or more mixtures selected from these negative and nonionic surfactants are used. These dispersing emulsifiers can replace some of the functions of each other's interfacial properties, but lack accuracy and mix them in proportions depending on the type of surfactant. Only when we can expect a big synergy. Here, if the dispersion emulsion stability in consideration of less than 10% by weight or more than 20% by weight, the stability of the dispersion dispersion stability according to the HLB and the stability for a long time to lose stability.

Solubilizers are a very important factor in cleaning. 2-5% by weight of the alkyl succinic dibasic acid salt and polyoxyethylene higher fatty acid ester prepared in the present patent should be prohibited from excessive use as re-infiltration of oil contaminants is possible when cleaning using more than 5% by weight. .

As an additive, it is used as a softening agent. Polyethylene glycol, a polyhydric alcohol, is used to increase the synergistic effect of cleaning, so it should be used in small amounts. As the oligomer has various physical properties depending on the molecular weight, the average molecular weight is about 350 to 700. The range is most effective and 3.0 to 5.0% by weight relative to the total weight is suitable. In addition, if the average molecular weight is 350 or less, it may cause a problem in the dispersion emulsion stability of the product may have the adverse effect of separating the two layers. If the added amount is 3.0 wt% or less, there is no effect on the fiber flexibility, and if it exceeds 5.0 wt%, there is a defect that remains as a residue after washing.

1 to 5% by weight of a fatty acid soap of sodium and potassium salts or triethanolamine selected from coconotic acid, talc acid, oleic acid, tauric acid, myristic acid, palmitic acid and stearic acid using a higher fatty acid salt as a rinsing enhancer. When using less than 1% by weight of the rinsing effect is low, when more than 5% by weight of the solid phase transition by fatty acid soap occurs.

Alkanol amides are used as viscosity and rheology modifiers

General formula of alkanol amide

RCONHm (C ₂ H ₄ OH) n R: C _９ ~ C ₁₇ (RCO = coconoyl, lauroyl,

myristoyl, palmitoyl, stearoyl, oleoyl)

m + n = 2 m = 0, 1 n = 1, 2

1 to 5% by weight is used as a highly biodegradable nonionic surfactant used as a skin protection agent which is very excellent in bubble stability, has a large thickening effect and alleviates skin irritation. If it is more than%, the liquidity is rapidly lost.

Generally, higher fatty acids and organic amines are used to control the viscosity and to determine the pH level. However, diethanol amine and triethanol amine among the organic amine compounds have a high solidification point and are easily solidified. At this time, yellowing tends to occur due to promoting oxidation of D-Limonene and heating of higher fatty acids oleic acid and stearic acid. The pH level also depends on the composition of the formulated surfactant, making it difficult to neutralize the appropriate viscosity and pH with higher fatty acids and organic amine compounds. Therefore, the acidity is often lowered by organic acids.

In the present invention, through a number of tests it was possible to obtain a viscosity and a neutral pH designed by the appropriate amount of alkanol amide (Alkanol amide).

And glycol ethers are used as a solvation promoter.

General Formula of Glycol Eter

The ether and hydroxyl groups are shared in the molecule to allow the mixing of water and organic solvent as a non-toxic solvent. When using 1 to 10% by weight is less than 1% by weight is incompatible with water-insoluble material is poor, more than 10% by weight may cause deformation and discoloration of laundry clothes should be careful.

As a hydrotroping agent, volatile solvents such as ethanol, ethylene glycol and propylene glycol are used in the present invention. Selecting them appropriately has a great effect on viscosity control, gel inhibition, low temperature stabilization, increased solubilization and wettability. If 1 to 10% by weight is used but less than 1% by weight, there is a fear of causing precipitation or floating phenomenon of insoluble content. If it exceeds 10% by weight, there is a tendency to offset the fragrance of di limonene and dry the laundry quickly, but the viscosity is drastically lowered, which may affect the consumer's perception of the cleaning power. In addition, it is very effective at low temperatures in winter and does not freeze up to -20 ℃.

As water soluble cleaning enhancers, sodium and potassium citrate and chelating agents, ethylene diamine tetra acetate (EDTA-4 Na), are used to conceal calcium and magnesium metal ions from aqueous solutions, and to speed up the dissolution of detergent compositions in hard water. Increase and improve cleaning performance. 0.05 to 1.0% by weight is used and below 0.05% by weight, insoluble precipitates of calcium and magnesium are formed, and the coagulum may settle on the fiber, which may cause unpleasant irritation to the fabric wearer. not.

Sodium and calcium salts of carboxy methyl cellulose (CMC-Na, CMC-Ca), polyvinyl pyrrolidone (PVP), Carbopol (Carbopol Type No 934, 940, 941) and water-soluble chitosan (hydroxy) Chitosan, hydroxy propyl chitosan, carboxy methyl chitosan) from 0.01 to 2.0% by weight of the component selected from because it can also have a clothing color protection function. If the amount is less than 0.01% by weight, the effect is weak and more than 2.0% by weight, it is difficult to maintain the liquid state due to the problem of pH control and increase in viscosity due to the polymer.

In addition to the above components, if necessary, preservatives, fungicides, antifoaming agents, antioxidants, pH adjusting agents, pigments, UV absorbers, ironing enhancers, softeners, and dirt suspensions, which are product quality stabilizers and functional binders, without degrading the performance of the present invention. , Enzymes and the like can be added. However, antimicrobial agents, antistatic agents, fragrances and deodorants are not deposited on the clothes or penetrated into the overlaid parts of the clothes at the washing stage of the washing process, and are lost in the discarded washing liquid or washing water, so that such loss is avoided. To be effective, it is considered reasonable and environmentally friendly to apply them separately, either in the rinsing step or better.

The components introduced above will be described in more detail as follows.

Component (1) is dirimonene, which is a non-polar solvent, so that dry cleaning is washed with a non-polar solvent. Among them, D-Limonene is 1-methyl cyclohexane, whose molecular formula is C ₁₀ H ₁₆ , has strong cleaning ability, and according to recent research, its use is also considered for sterilization cleaning and CFC replacement.

The said (2) component is a compound of following General formula (A) or (B) as N-acyl sacosinate and polyoxy ethylene ether sulfate ester salt as a washing | cleaning promoter.

(A) R ₁ -CONHCH ₂ COOM ₁

R ₁ = fatty acid hydrocarbon of Cocoyl, Lauroyl, Stearoyl, Glutamine

M ₁ = Na, triethanolamine (TEA)

(B) R _2- (OCH ₂ CH ₂ ) _n OSO ₃ M ₂

R ₂ = alkyl group of C ₁₀ ~ C ₁₆

n = 2 to 5

M ₂ = Na, TEA, ammonium

Here, sodium lauryl ether sulfate of the anionic surfactant is a nonionic surfactant mixed with polyoxyethylene (20) sobitan laurate can reduce the irritation to the skin.

The component (3) is a copolymer of (C), (D), (E) and (F) of polyoxyethylene alkyl ether, polyhydric alcoholic alkyl polyether, alkyl ether carboxy salt and ethylene glycol-propylene glycol as a dispersing emulsifier. Compound.

(C) R ₃ -O (CH ₂ CH ₂ O) _n H

R ₃ = alkyl group of primary, secondary and tertiary alcohol

primary = lauryl (C ₁₂ H ₂₅ ), oleyl (C ₁₈ H ₃₅ )

mixture of hydrocarbons with secondary = C ₁₂ to C ₁₄

tertiary = tridecyl (C ₁₃ H ₂₇ )

n = 5 to 12

COR ₄ = lauroyl, palmitoyl, stearoyl, oleoyl

m + n = 10-20

(E) R ₅ -O (CH ₂ CH ₂ O) _n CH ₂ COOM ₅

R ₅ = alkyl group of C ₆ ~ C ₁₄

n = 3 to 12

M ₅ = Na, K

R ₆ = C ₆ ~ C ₁₂ linear alkyl group

m = 1 to 10 n = 1 to 15

m + n = 10 to 16

The said (4) component is a compound of long-chain alkyl succinic-acid dibasic acid salt and polyoxyethylene higher fatty acid ester (G) or (H) as a solubilizer.

Self-synthetic products

sodium 2-alkenyl succinate

R ₇ = alkenyl of C ₈ to C ₁₆

(H) R ₈ COO (CH ₂ CH ₂ O) _n H

R ₈ = coconoyl plant fatty acid

(Mixture of lauric acid, myristic acid, capuryl acid, capuronic acid)

n = 5 to 13

In conclusion, the mild non-polluting detergent composition provided by the present invention contains 20 to 35% by weight of the surfactant composition composed of nonionic and anionic surfactants in specific fatty acid components extracted from natural plants, based on the total weight of the product. The ratio of the nonionic surfactant and the anionic surfactant may be 1: 5 to 5: 1 or preferably 5: 5 to 6: 4 and the amount of the auxiliary may be up to 30% by weight of the composition, but preferably the total The adjuvant will not exceed 20% by weight and more preferably in the range of 1 to 15% by weight.

Hereinafter, specific embodiments of the present invention will be described. It is not limited by the embodiments described in the present invention.

Next, according to the blending weight ratio of Table 1, it is added according to the application characteristics, and the organic solvent-free detergent composition mildly mixed by dispersing emulsion homogeneous stirrer (AG1HOMO MIXER) for 20 to 30 minutes at 50 ~ 60 ℃ temperature and 1000 ~ 3000 rpm conditions Examples 1 to 5 were prepared respectively.

TABLE 1

Example

Note ¹⁾ D-Limonene [CAS NO. 5989-27-5] Florida Chemicals, USA

²⁾ Sarcosinate CN-30 [sodium N-cocoyl sarcosinate] manufactured by Nikko Chemicals, Japan

³⁾ MIAMI L-30 [sodium lauroyl sarcosinate] product of Miwon Corporation

⁴⁾ HICOLIN SPES [sodium lauryl ether sulfate] Taedong Chemical Co., Ltd.

⁵⁾ MONOPOL LE 1017 [POE lauryl ether] Dongnam Synthetic

⁶⁾ Isodol TW-20 [POE sorbitan mono laurate] Ilchi Chemical Co., Ltd.

⁷⁾ ECTD-6NEX [sodium POE Tridecyl ether acetate] Japan NIHON SURFACTANT Co., Ltd.

⁸⁾ Poly Tergent SL-62 [Alkoxylated linear alcohol] manufactured by BASF, USA

⁹⁾ self-synthesized products [sodium alkenyl succinate]

¹⁰⁾ Koremul CFA-5 [POE coconut fatty ester]

¹¹⁾ Konix PEG-400 [polyethylene glycol] product of Korea Polyol Co., Ltd.

¹²⁾ universal soap

¹³⁾ sunfom CDE [coconut fatty acid diethanol amide] Sunjin Chemical Co., Ltd.

¹⁴⁾ Butyl Carbitol [diethylene glycol monobutyl ether] manufactured by Union Carbide of USA

¹⁵⁾ Ethylene Glycol Samsung Petrochemical Co., Ltd. Products

¹⁶⁾ EDTA-4Na [Disodium Ethylene Diamine Tetra Acetate] manufactured by Miwon Corporation

¹⁷⁾ carbopol [carboxypolymethylene CAS No. 9007-20-9] BFGoodrich, USA

Following the mixing ratio of the following Table 2, after the addition of each component at a temperature of 50 ~ 60 ℃ at a speed of 1000 ~ 3000rpm for 20 to 30 minutes mixed sufficiently in a dispersion emulsion homogeneous stirrer compared to the conventional laundry detergent composition 6 to 10, respectively Manufacture.

TABLE 2

Comparative example

¹⁸⁾ Isopar-H [USA Exxon co.]

¹⁹⁾ Actrek-1047 [USA Exxon co.]

²⁰⁾ Hostapur STS [Germany Hoechst co.]

²¹⁾ RCS-48 [USA BASF co.]

²²⁾ Dobanol 91-8 [USA Shell comp.]

²³⁾ NPE-5 [Aekyung Fine Chemical Co., Ltd.]

²⁴⁾ BHT [Jinyang Hwasung Co., Ltd.]

²⁵⁾ Everlase, Termamyl, Lipolase, Alcalase, Celluclast [Denmark Novo Nordisk co.]

Experimental Example 1

Storage stability test

Examples 1 to 5 and Comparative Examples 6 to 10 were prepared using the ingredient ratios described in Tables 1 and 2, and the pH was adjusted to 7 (error 0.2) with NaOH and citric acid, and then placed in a 250 ml reagent bottle for 8 hours at low temperature (-20 ° C.). Storage stability was evaluated after 3 cycles of 8 hours at room temperature (25 ℃) and 8 hours at high temperature (50 ℃). This stability evaluation was evaluated by dividing into three states as follows.

○: Stable state with little change in viscosity and no phase separation

△: change of phase temperature, salt formation and cloud suspended matter

×: Viscosity rapidly rises, loses fluidity and phase separation occurs

TABLE 3

Stability

In the product stability, if the total weight percent of the nonionic surfactant is more than the appropriate range and the distribution is wide or the mixing ratio with the anionic surfactant is not correct, the liquid phase becomes cloudy or the phase separation occurs due to the lowering or rising of the phase temperature (CP). It can be seen.

Experimental Example 2

Using the detergent composition described in Tables 1 and 2 as a sample, the results of the washing force test for the fabric of the test cloth for each fabric type were measured and shown in Table 4 below. Although the cleaning power should be compared and evaluated by the same immersion method as in actual use, it is considered reasonable to actually evaluate the washing effect on the contamination table under severe conditions using an internationally recognized cleaning device.

The cleaning power evaluation test method described in Table 4 is as follows.

1. Cut the contaminated cloth to 10 × 12 cm ² .

2. Measure the whiteness (Wb) of the cut dirt using a colorimeter ^* (R _s ).

3. Set the water temperature of Terg -o -tometer ^** to 20 ° C.

4. Set the rpm of the Terg -o -tometer to 100.

5. D.I. Add 1 liter of water.

6. Make the hardness of water in the vessel 50ppm based on CaCO ₃ .

7. When the temperature of vessel reaches 20 ℃, add sample and dissolve for 3 minutes.

8. After dissolution, add 2 10 × 12 cm ² soiled cloths to the vessel.

9. Wash at 100 rpm for 10 minutes.

10. After washing, rinse twice with tap water.

11. Rinse and dry naturally.

12. After drying, measure the whiteness (Wb) by using a colorimeter on the contaminated cloth (R _w ).

At this time, the amount of detergent required for 1 l of water is a commercial product and is used as the manufacturer's recommended amount (0.5 ml / l).

Note) ^* : Hunterlab Color Difference Meter, Model D25

^** : US Testing Company Products

The Terg-O-Tometer is a small multi-unit washer that simulates the action of a stirrer-type home washer. Four units can be used to compare four detergents simultaneously, or they can be tested in pairs (two units are used for each wash).

After the experiment, R _s and R _w are substituted into the Kubellda-Munk equation to obtain the washing power. (See pages 64 and later in Surfactant series vol. 20 Detergency.)

[Equation 1]

Kubellda-Munk equation

R _s is the reflectance of the contaminated cloth, R _w is the reflectance after washing, and R _o is the reflectance of the original cloth.

Parent contaminant: Empa 107 (Testfabrics, Inc. Swiss)

Silk contaminated cloth: stain gray fabric sample as Empa contaminated cloth as standard

Cotton contaminant: Empa 101 (Testfabrics, Inc.Swiss)

TABLE 4

Detergency (%)

As shown in Table 4, the cleaning property of each fabric of the contaminated cloth is generally evaluated to have good cleaning power of 50% or more. Examples 1 to 5 generally had excellent cleaning power as shown in Table 3, but Comparative Examples 6 to 9 were found to have poor cleaning power. In the case of Comparative Example 10, the result of the conventional dry cleaning method is the same as the result of the composition of the present invention, which means that the detergent of the present invention can be used safely at home.

Experimental Example 3

Using the cleaning composition of Table 1 and Table 2 as a sample, the shrinkage effect after washing on the fabric of each test piece type was measured, and the results are shown in Table 5 below.

Preparation Fabric: Wool, Silk Polyester, Acetate

Pretreatment: washing with water (2g / l powder detergent at 20 ℃) and drying after rinsing (30 minutes at 65 ℃)

Fabric Size: 9 × 9 cm ²

Washing method: As in Experiment 1, 0.5 ml / l of each sample was added to each fabric of Examples 1 to 5 and Comparative Examples 6 to 9, and 20 minutes at room temperature, 1 hour, 24 hours, and 50 ° C. Dip by the conditions such as minutes, dehydrate and dry in the natural wind before ironing.

In the case of Comparative Example 10.

1) First run: Put the test piece together with 150 ml of perchloroethylene, 1.5 ml dry cleaning detergent and 100 oral in a steel cylinder, close the lid and insert it into a rhodiometer for 10 minutes at room temperature. Pull out.

2) Secondary operation: Put only 150ml of perchloroethylene and run again for 10 minutes, then remove the solution.

3) Third run: After repeating the second run, take out the test piece, sandwich it between paper towels, press the solution out, and dry it in air. This specimen is finished in one of the following ways.

-Hand pressing: pre-soaked with water and covered with a moist muslin fabric dehydrated to have moisture equivalent to about 75% of the dry weight, and then pressed until it is dried with an iron at 135-150 ℃.

-Steam Pressing: It can produce 448 ~ 482㎪ (65 ~ 75㎰i) vapor pressure. For smooth fabrics, hot bed or smooth metal press must be used. For rough crepe fabrics, press on cloth is applied. Should be used. Lower the front of the machine and let it touch the specimen, steaming for 5 to 10 seconds.

Shrinkage (%) = [(length after test-length before test) / length before test] × 100

TABLE 5

Shrinkage (%)

The shrinkage ratios of the compositions of Examples 1 to 5 were tested by the immersion method, all of which resulted in good results regardless of the type of the fabric test piece. On the other hand, the compositions of Comparative Examples 6 to 9 had a change in the form shrinkage rate after washing by the immersion method for the woolen fabric and the acetate fabric, and it can be seen that the shrinkage rate is significantly increased with the immersion time rather than the effect on the temperature of the laundry. Comparative Example 10 shows almost similar results as compared with the use of the composition of the present invention as a result of the conventional dry cleaning method. As a result, when the washing is usually carried out at room temperature for about 15 minutes, when fully immersed in about 1 hour, as shown in Table 5, the shrinkage ratio of the cleaning composition of the present invention is much lower than that of Comparative Examples 6 to 9, indicating that the shrinkage effect is excellent. Able to know.

Experimental Example 4

Using the detergent compositions described in Tables 1 and 2 as samples, the antifouling test for each fabric was measured according to ASTM D 4265-98, and the results are shown in Table 6 below.

1) Preparation Fabric: Wool (Empa 107 used in Experimental Example 2), Cotton (Empa 101 used in Experimental Example 2)

2) Pretreatment: Water washing (2g / l powder detergent at 20 ℃) and natural drying after rinsing.

3) Fabric Size: 10 × 12cm ²

4) Pollutants: coffee, red wine, car oil, grape juice

5) Pollution method: Drop 0.2 ml (5 drops) of contaminants into the washed contaminated cloth and dry for 3 minutes at 65 ℃ after 20 minutes.

6) Washing method: In case of Examples 1 to 5 and Comparative Examples 6 to 9, 0.5 ml / L of each sample was added to the prepared fabric, and after 20 minutes of immersion, dehydration and natural drying were performed. Comparative Example 10 is the same as in [Experimental Example 3].

[Equation 2]

Outlander (SRI) =

c: laundered untreated cloth, w: laundered untreated cloth

L: reflectance,

a: red / green, b: yellow / blue

SRI: STAIN REMOVAL INDEX

TABLE 6

Room water

As a result of the antifouling test results, Comparative Examples 6 to 10 showed relatively good cleaning effects in the case of contaminants, which are coffee, red wine and grape juice, except for all being automobile oil. And the compositions of Examples 1 to 5 also showed a better washing effect than that of Comparative Examples 6 to 10, thereby showing the performance of the laundry detergent sufficiently in view of the shrinkage effect and antifouling results.

Experimental Example 5

In order to measure the stability of the environmental friendliness to the laundry composition described in Tables 1 and 2, it was measured according to KSM 2714 (test method for biodegradability of synthetic detergent) as an environmental affinity test according to water pollution. The results are shown in Table 7 in terms of biodegradability (%) after 7-8 days.

TABLE 7

Biodegradability (%)

※ The sample using perchloroethylene of Comparative Example 10 could not be cultured by active sludge and could not be measured by KSM 2714. In this case, if there is no microorganism in the sample or if it is not sufficiently present, biodegradation does not occur. At this time, the microorganism should be added to the dilution water (plant dilution water) and expressed as biochemical oxygen demand (BOD). Perchlorethylene is regulated as a specific water hazardous substance here.

As shown in Table 7, in Examples 1 to 5, the biodegradability (%) was 99.6 or more, and very good results were obtained. In Comparative Examples 6 to 9, biodegradability was lower than that of Examples. In particular, in the case of Comparative Example 10, even if the washing ability results in a rather good result shows a serious problem in biodegradability.

Experimental Example 6

Skin irritation test

The detergent compositions of Examples 1 to 5 and Comparative Examples 6 to 10 described in Tables 1 and 2 above were subjected to comparative tests of stimulation for each detergent by the In-Vitro irritation test (Zein test), which is a skin irritation test.

The results are shown in the protein denaturation rate in Table 8.

Zein test is a test that measures the degree of dissolution by dissolving Zein, a protein extracted from yellow corn, with detergent solution (nitrogen quantitative method) to measure skin irritation.

Test Methods

① Add 80 ml of detergent solution to Erlenmyer flask, stir to 37 ℃ and add Zein 5g.

② Heat and stir in water bath at 37 ℃ for 1 hour.

③ Transfer to centrifuge tube and centrifuge at 4000rpm for 10 minutes.

④ Aliquot 5 ~ 20g of sample (supernatant) into 100ml Kjeldahl flask.

⑤ Add Thiotab 7.4g (7g potassium sulfate + 0.21g copper sulfate + 0.21g titanium dioxide).

⑥ After adding 10 ml of sulfuric acid, transfer to Kjeldahl digestion unit heated at over 400 ℃.

⑦ Add a total of 10ml of hydrogen peroxide solution to prevent bubbles from overflowing.

⑧ Continue to heat until the solution color is clear and clearish greenish blue.

⑨ After cooling slowly in air, dilute distilled water by adding 75 ml. The color of the solution is light blue.

⑩ Transfer the digested sample solution to the distillation flask and place it in the distillation unit. Boric acid traps are added with 75 ml of 4% boric acid.

40 40ml of 40% NaOH is added to NaOH addition funnel and slowly poured into distillation flask.

Re Water reservoir Add 300ml of water and heat to generate steam. The duct through which steam passes is warmed with cotton wool.

증류 Stop distillation until the volume of boric acid trap is about 100ml. The color of the boric acid trap changes from purple to light green.

Bor Titrate Boric acid from Boric acid trap obtained by distillation of ammonia with 0.5N HCl. The end point is the original index dark pink (purple).

From the amount of HCl consumed and the amount of the initial Zein solution sample, find the N% of Zein dissolved in the detergent solution.

Perform blank test in the same way as this test and subtract from this test result.

TABLE 8

Protein denaturation rate (N%)

N% in detergent solution = [V (HCl) × N (HCl) × 14 × 100] / [100 × M (Zein solution)]-blank test

As shown in the results, the protein denaturation rate of each sample detergent in Table 8 is very irritating because the detergents of Examples 1 to 5 differ in degree compared to Comparative Examples 6 to 10, but show good results.

So far, all the results of Test Examples 1 to 6, the mild pollution-free detergent composition according to the present invention has obtained excellent results in terms of skin irritation and stability as well as sufficient cleaning function by immersion method.

As described above, the mild non-polluting detergent composition of the present invention has obtained excellent cleaning power by using a raw material obtained mostly from nature without using a benzene ring-containing surfactant, and in particular, by keeping the liquidity neutral without adding an enzyme By minimizing human irritation during use and reducing water pollution by increasing biodegradability after use, cotton fabrics and chemical fibers can be used in the same way as general clothing washing. Natural clothing has the innovative effect of washing without worrying about deformation and shrinkage.

Claims (5)

5-30% by weight of dilimonene with natural detergents; 5-15% by weight of N-acyl sacosinate and alkyl ether sulfate as a cleaning promoter; As dispersing emulsifier a compound which is polyoxyethylene alkyl ether, polyhydric alcoholic alkylpolyether, alkylether carboxylate, polyoxyethylene-polyoxypropylene alkylether, 10 to 20% by weight in combination of two or more; 2 to 5% by weight of long-chain alkyl succinic dibasic acid salts and polyoxyethylene higher fatty acid esters as solubilizers; As functional aids, polyethylene glycol is used as a softening agent in the range of 3 to 5% by weight with an average molecular weight of 350 to 700, 1 to 5% by weight of a higher fatty acid salt (Soap) as a rinse improver, and 1 to 5 alkanolamide as a viscosity and fluidity regulator. % By weight, 1 to 10% glycol ether as solvation promoter, 1 to 10% by weight using one or more of ethanol, ethylene glycol, propylene glycol as hydrotropes, citric acid salt or ethylenediaminetetraacetic acid salt (EDTA- 4Na) 0.05 to 1.0% by weight, sodium and calcium salts of carboxymethylcellulose (CMC-Na, CMC-Ca), polyvinyl pyrrolidone (PVP) and carbopol (Type No 934, 940, 941) and one or more of water-soluble chitosan (hydroxy ethyl chitosan, hydroxy propyl chitosan, carboxy methyl chitosan) to 0.01 to 2.0 wt%; Mild pollution-free detergent composition comprising a. The method according to claim 1, wherein the general formula of N-acyl sacosinate of the cleaning accelerator R ₁ -CONHCH ₂ COOM ₁ (R ₁ is a fatty acid hydrocarbon of Cocoyl, Lauroyl, Steeoyl, Glutamine and M ₁ is sodium or triethanolamine) , alkyl ether sulfates general formula of _{R 2 - (OCH 2 CH 2} ) nOSO 3 M 2 (R 2 is an alkyl group of carbon atoms, C ₁₀ ~ C1 _16, n is from 2 to 5 M ₂ is sodium, triethanolamine, Ammonium) mild pollution-free detergent composition. The general formula of polyoxyethylene alkyl ether as a component of the dispersing emulsifier is R ₃ -O (CH ₂ CH ₂ O) n H (R ₃ is linear or branched alkyl of primary, secondary, tertiary alcohol. The alkyl group of the primary alcohol is lauryl (C ₁₂ H ₂₅ ) or oleyl (C ₁₈ H ₃₅ ), the alkyl group of the secondary alcohol is a mixture of hydrocarbons of C ₁₂ ~ C ₁₄ , the alkyl group of the tertiary alcohol Tridecyl (C ₁₃ H ₂₇ ) and n is 5-12), General Formulas of Polyhydric Alcoholic Polyalkyl Ethers (Wherein COR ₄ is lauroyl, palmitoyl, stearoyl and oleoyl, m + n is 10-20), General formula of the alkyl ether carboxylate R ₅ -O (CH ₂ CH ₂ O) nCH ₂ COOM ₅ (wherein R ₅ is straight and branched alkyl having C ₆ to C ₁₄ carbon atoms, n is 3 to 12, M ₅ is sodium and potassium) Metal ions), General formulas of the above polyoxyethylene-polyoxypropylene alkyl ethers M is 1 to 10, n is 1 to 15, and the sum of m and n is 10 to 16.) Mild pollution-free detergent composition, characterized in that. The general formula of the long chain alkyl succinic acid dibasic acid salt according to claim 1 (Wherein R ₇ is alkenyl having C ₈ -C ₁₆ carbon atoms), General formula of the polyoxyethylene higher fatty acid ester is R ₈ COO (CH ₂ CH ₂ O) nH (Wherein R ₈ is a mixture of lauric acid, myristic acid, capuric acid, capuronic acid which are coconoyl plant fatty acids, and n is 5 to 13) Mild pollution-free detergent composition, characterized in that. The general formula of alkanol amide according to claim 1, wherein said viscosity and fluidity regulator is RCONHm (C ₂ H ₄ OH) n (Wherein RCO is a higher fatty acyl group having a C _{10 to} C ₁₈ coconoyl, lauroyl, myristoyl, palmitoyl, stearoyl, oreoyl, m is 0 to 1, n is 1 to 2) The sum of m and n is 2), General Formulation of Glycol Ethers as the Solvation Promoters (Wherein R is an alkyl group having _{1 to 8} carbon atoms and m and n are integers of 1 to 3) Mild pollution-free detergent composition, characterized in that.