KR100356983B1 - Mild composition of cleaning material for clothing - Google Patents

Abstract

The present invention relates to a mild detergent-free detergent composition for clothing, and more particularly to a mild detergent-free detergent composition for clothing which comprises a main component of a natural vegetable cleansing dimolimene, a cleaning accelerator, a dispersion emulsifier and a solubilizing agent, In addition to being excellent in water washing effect on wool, silk and hemp clothes which could not be washed by water, it is possible to wash by dipping method unlike the one used so far, Is characterized by a novel composition which is free of irritation and excellent in both cleaning and stability.

Description

The present invention relates to a mild detergent composition for clothing,

The present invention relates to a mild detergent-free detergent composition for clothing, and more particularly to a mild detergent-free detergent composition for clothing which comprises a main component of a natural vegetable cleansing dimolimene, a cleaning accelerator, a dispersion emulsifier and a solubilizing agent, In addition to being excellent in water washing effect on wool, silk and hemp clothes which could not be washed by water, it is possible to wash by dipping method unlike the one used so far, And a novel composition which is excellent in both cleaning property and stability.

Conventional detergents for clothes include solid laundry soaps composed mainly of sodium high fatty acid salts (soap), LAS (straight chain high alkyl sulfonate), ABS (long chain alkylbenzene sulfonate), AOS (alpha olefin sulfonate) Mineral based emulsifiers such as higher fatty acid methyl ester salts, and powdery synthetic detergents composed mainly of high-fatty acids and higher fatty alcohols such as same-vegetable raw materials and various functionalities. These detergents can effectively wash starch components such as skin secretions, dust, urban sooty water and organic synthetic oils, protein components such as skin keratin and various food waste attached to clothes, Synthetic fibers such as polyester, nylon and acrylic fiber fabrics, and blend fibers thereof.

However, as the standard of living improved, the tendency to use clothing made preference to clothing made of natural fibers rather than synthetic fibers, so that the pure clothes, pure silk fabrics, And the environmental awareness change has paid great attention to the problem of water pollution in existing washing methods.

Conventional detergents for clothes use mineral synthetic detergent and emulsifier as main components, and when washing, it is necessary to supplement mechanical energy such as rotational friction or impact caused by water in the washing machine. In this case, Because of the low water resistance of the fibers, the shape and deformation and shrinkage can not be serious. Due to this problem, in the past, such clothes made of natural fibers have been laundered and laundered by dry cleaning. However, this method is also a difficult problem to solve environmental problems and waste disposal methods due to the use of dry cleaning agents.

Until now, the dry cleaning method in dry cleaning method is dry washing method using petroleum solvent and mineral emulsifying agent for high quality garments such as pure wool, pure silk fabrics and pure wool fabrics. Perchlorethylene is used as a petroleum- Are typically used. Recently, it has been pointed out in the developed countries including the United States that the laundry cleaning method using the dry cleaning causes the problem of the water pollution in the environment-friendly aspect because of the characteristic of the physico-chemical properties of the perchlorethylene generally used. The perchlorethylene system is known to be an environmental pollutant since it was released from the Sigma-Aldrich Library in the United States because of its low hydrolysis ability to water and its teratogenic and carcinogenic properties. It is known that toxicity of solvents remaining in clothes after washing and volatile substances Considering toxicity by inhalation, it has a very serious contamination problem. Also, since disposal of spent perchlorethylene is not specifically provided, it remains as a source of soil, river and air pollutants, and poses problems of environmental pollution. Therefore, the inventors of the present invention have found that there is no problem that it is fundamentally non-toxic to the human body and causes no environmental pollution in order to simultaneously solve the contamination problem of the dry cleaning which is used in the conventional cleaning agent and the dry cleaner, It is possible to solve the problems such as deformation, deformation, and the like of a non-polluting detergent composition for an innovative mild clothing.

The present invention relates to the use of D limonene, a solvent obtained by extracting natural products, as a natural acid detergent, in which amino acid surfactants, which are anionic surfactants, are used as cleaning accelerators, nonionic surfactants as dispersing emulsifiers, and dibasic acids as solubilizers And it is possible to change the washing style of the conventional detergent so that it is possible to easily obtain the washing effect of dry cleaning at home, thereby enabling the mild pollution-free washing without the shape deformation or contraction of the clothes.

The natural diphtheria limonene used as a natural solvent in the present invention is a by-product obtained by distillation extraction from an orange fruit husk mass-produced in the USA, Australia, Brazil and Europe as an extract of natural citrus skin. D limonene is a kind of terpenoid system having optical activity from the viewpoint of chemical structure, and has a degree of carbonization of hydrocarbon of 10 and a degree of degreasing with inherent intrinsic fragrance due to its structural characteristic having an orientation structure similar to benzene It is a non-polluting substance which has a relatively high decontamination ability than perchlorethylene which has been obtained from petroleum solvent and has been used so far. Dymolonene is also used for industrial application, food industry or fragrance of fragrance according to the content of octal, nonanal, decanal and linanol, which are normal aldehydes. Part of deodorant composition as in Patent Publication No. 90-6854 It is also used as a constituent component. D limonene is a chemically stable liquid because it has a high boiling point above 154 ° C. It is classified as Generally Recognized As Safe (GRAS) according to the FDA (Food and Drug Administration) . Examples of applications of such a dimolimene as a cleaning agent are listed in U.S. Patent Nos. 4,511,488 and 4,620,937, British Patent 1,603,047, and U.S. Patent Publication No. 1996-0011675.

In particular, in mild non-polluting detergent compositions for clothing, a mild pollution-free laundry composition for clothing which is free from shrinkage or deformation when used in a soaking method is not known until now, unlike the dry- In the method of use, external physical force using mechanical rotation or air bubbles was always required. Generally, solid contaminants can explain the washability due to the electrostatic energy action of desorbing from the substrate. However, the adsorption form between the contaminant particles and the substrate is induced to the hydrated form of the dispersed phase by the surfactant, . From this point on, the energy required to move the contaminants from the substrate to the infinite distance is washed by the mechanical rotational kinetic energy of the washing machine, the water dispersion effect, and the ultrasonic waves. If washing is performed using a mechanical device, that is, a washing machine, the kinetic energy of the rotor in the water tank provides excessive energy to the laundry, that is, the clothing, which causes shrinkage and deformations of the clothes. Therefore, the detergent composition dissolves the contaminants by the immersion method of the non-polluting natural detergent instead of removing the contaminants by the mechanical rotational kinetic energy in the washing machine, thereby separating the contaminants and preventing the re-adsorption, The discharged cleaning liquid minimizes the water pollution, so that the dry cleaning effect in the laundry can be sufficiently effected by the dipping method even at home.

In order to overcome the deficiencies of the above-mentioned conventional products in the present invention, it has been experimentally determined that D limonene, which is a natural orange orange extract, a cleaning accelerator, a dispersion emulsifier and a solubilizing agent are used as main components and, if necessary, a higher fatty acid salt, A non-polluting detergent composition for a mild garment mixed with Nomamide is prepared and washed by the dipping method to improve the cleaning efficiency, as well as to maintain the shape stability after washing on pure wool, pure silk and pure wool and mixed fabrics thereof It is possible to perform pollution-free washing with high biodegradability.

Known basic laundry, laundry detergent is classified into weak alkaline detergent and neutral detergent. The weak alkaline detergent is used for general clothing such as cotton, blend fiber, and animal and silk animal fiber and acetate fiber are neutral detergent. If a weak alkaline detergent is used in a garment that is made of neutral detergent, it may cause shrinkage, deformation, discoloration, etc. Therefore, it is necessary to use a neutral detergent. Since light color clothing such as ivory color or pastel is easily discolored, It should be washed and used. It is also recommended to wash with a neutral detergent at 30 ° C or less for wool and easy-to-discard silk. Therefore, in the present invention, the pH of the composition is maintained to be neutral to about 7, thereby minimizing shrinkage and damage to natural fibers, -balance effect, the skin irritation is greatly reduced, and contact dermatitis and skin keratinization due to excessive skin skimming can be prevented. In addition, the low bubble power further improves the rinsing effect particularly at low temperatures.

Generally, liquid laundry detergent used for clothes washing is composed of main components such as surfactant component and enzyme component, auxiliary components such as bleaching and fluorescent whitening component, and most of the components are liquid alkaline in order to increase the activity of the enzyme. Since the liquid is alkaline and contains an enzyme, it can not prevent the damage of high-grade clothes. The enzyme component and the bleaching component have a risk of deforming the tissue of the garment and cause damage to the skin protein. Furthermore, Is known to be dangerous to the human body.

The object of the present invention is to solve the above-described disadvantages, and it is an object of the present invention to provide a laundry detergent composition which is excellent in a mild detergent component which is a basic component of clothes washing and an orange oil component extracted from a natural product, Alkali agents that maintain the alkalinity in order to prevent clothing and skin damage at the same time by adding ingredients and to assist washing conditions such as enzymatic performance during washing are not added to avoid tissue deformation and damages of skin proteins To provide a mild liquid detergent composition capable of protecting clothing and skin. Furthermore, since the surfactant containing benzene nucleus is not used in the detergent composition used for washing various clothes, it is possible to eliminate pollution factors that increase the BOD (biological oxygen demand) of the river or the river due to low biodegradation And to solve the problems that cause destruction of ecosystem. Thus, the present invention improves the washability by using natural dyes limonene, a cleaning promoter, a dispersion emulsifier and a solubilizing agent as raw materials, and eliminates water pollution after washing. Further, The present invention provides a mild non-polluting detergent composition for clothing which can be preserved.

Further, it is a further object of the present invention to provide a cosmetic composition which is easy to dissolve and disperse in water and which does not form an insoluble precipitate that causes irritation to the human body, Is a microemulsion type having a high water-solubility, a good dispersibility and a good rinsability, and a pH of a liquid phase which is essential for washing of natural fibers is made neutral so as not to cause shape deformation, shrinkage and discoloration of clothes .

Hereinafter, the configuration of the present invention will be described in detail.

The most suitable viscosity of the inherent low viscosity liquid composition so as not to cause shape deformation, shrinkage and discoloration of the garment is obtained using a Brookfield viscometer spindle No. 2, 2.5 rpm, 20^°C Lt; / RTI >

The detergent composition of the present invention comprises the following components.

(1) Dipolinene extracted from water-vapor distillation from the peel of orange, lemon, etc.,

(2) N-acyl sarcosinate and polyoxyethylene ether sulfate ester salt as a cleaning accelerator

(3) As a dispersion emulsifier, a polyoxyethylene alkyl ether, a polyhydric alcohol alkyl polyether, a copolymer of an alkyl ether carboxy salt and ethylene glycol-propylene glycol

(4) Solubilizing agent The long-chain alkyl succinic acid dibasic acid salt and the polyoxyethylene higher fatty acid ester

(5) Functional supplements

① Softener: high-valency alcohol

② Rinsing agent: High fatty acid salt

③ Viscosity and flow control agent: Alkanolamide

④ Solubility accelerator: glycol ethers

⑤ Hydrotropes: Ethanol, ethylene glycol, propylene glycol

⑥ Water-soluble cleansing enhancer: citrate, ethylenediamine tetraacetate

⑦ Re-contamination adhesion preventive agent: Carboxymethyl cellulose salt, polyvinyl pyrrolidone, carbopol, water-soluble chitosan

In the above-mentioned composition of the present invention, the dimolimene is preferably 5 to 30% by weight, more preferably 10 to 20% by weight. If dimolimene is used in an amount of less than 5% by weight, a sufficient washing effect by the dipping method can not be obtained. If it is used in excess, the form is deformed and discolored in washing for clothing, It is not good to.

As the cleaning accelerator, 5-15 wt% of N-acylated saccharin acid, a kind of amino acid, which is a protein surfactant, and sulfate of ethoxylated vegetable fatty acid are used. When the amount is less than 5 wt%, the active ingredient of the protein is offset by the alkyl ether sulfate The skin irritation can not be further alleviated. If the amount exceeds 15% by weight, the emulsion dispersibility of the nonionic surfactant is deteriorated due to excessive cleansing promotion, so that phase stabilization at room temperature can not be expected.

As the dispersion emulsifier, a polyoxyethylene alkyl ether, which is a nonionic surfactant, may be used in which an alkyl group is substituted with an ethylene oxide adduct of a primary, secondary or tertiary alcohol, a polyhydric alcohol alkyl ether and a polyoxyethylene-propylene alkyl ether and an anionic surfactant An alkyl ether carboxy salt is used, which is a non-ionic surface active agent and contains an anionic surfactant to increase the efficiency of compound uptake in decontamination, as well as an interface with a benzene ring which adversely affects the human body and the environment The biodegradability can be further improved by excluding the activator. These dispersing and emulsifying agents may be used in place of a mixture of two or more selected from the above-mentioned non-ionic surfactants. However, these dispersing emulsifiers may partially substitute for their interfacial functions, but they lack accuracy and are mixed at a certain ratio depending on the type of surfactant A great synergy effect can be expected only in the city. In consideration of stability of dispersion emulsification, if it is less than 10% by weight or exceeds 20% by weight, stability of emulsion dispersion stability according to HLB is not balanced and it is lost in stability for a long time.

Solubilizers are a very important factor in cleaning. When the alkyl succinic acid dibasic acid salt and the polyoxyethylene higher fatty acid ester prepared in this patent are used in an amount of 2 to 5% by weight and more than 5% by weight, the oil contamination can be re-infiltrated, .

Polyethylene glycol which is a polyol as a softener is used as an adjuvant, and it is added to increase synergistic effect of cleaning. Therefore, it should be used in a small amount. It has various average physical properties such as an average molecular weight of 350 to 700 Is most effective, and it is appropriate that the total weight is in the range of 3.0 to 5.0% by weight. In addition, when the average molecular weight is less than 350, there is a case where the stability of the dispersion and emulsion of the product is deteriorated and the two layers are separated from each other. If the addition amount is less than 3.0 wt%, the fiber flexibility is not significantly affected. If the addition amount is more than 5.0 wt%, the fiber 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 coconut acid, tallow acid, oleic acid, tauric acid, myristic acid, palmitic acid and stearic acid, When the content is 1 wt% or less, the rinsing effect is low. When the content is 5 wt% or more, solid phase transition is caused by the fatty acid soap.

Use alkanolamide as a viscosity and flow control agent

The general formula of Alkanol amide

RCONHm (C ₂ H ₄ OH) n R ₉ to 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 non-ionic surfactant having excellent biodegradability, which is used as a skin protecting agent which is excellent in foam stability and has a large thickening effect and alleviates skin irritation. When it is 1% by weight or less, %, The liquidity is rapidly lost.

Generally, high fatty acid and organic amine compound control viscosity and set pH level. Diethanol amine and triethanol amine among organic amine compounds are easy to solidify because of high freezing point, so preliminary melting is required when using liquid detergent. At this time, there is a tendency to accelerate oxidative action of D-Limonene and yellowing of acid liquor due to heating of oleic acid and stearic acid, which are higher fatty acids. Since the pH level is also dependent on the composition of the surfactant compounded, it is difficult to make the viscosity and pH neutral with higher fatty acids and organic amine compounds. Therefore, the acidity is often lowered with organic acids.

In the present invention, it has been found through numerous tests that the viscosity and neutral pH designed in an appropriate amount of Alkanol amide can be preferably obtained.

And glycol ethers as solvation accelerators.

The general formula of the glycol ether (Glycol Eter)

It shares the ether group and the hydroxyl group in the molecule and makes it possible to mix water and organic solvent as a non-toxic solvent. 1 to 10% by weight is used. When it is less than 1% by weight, miscibility of water-insoluble matters becomes poor. If it exceeds 10% by weight, it may cause deformation and discoloration of laundry clothes.

As the hydrotrope agent, ethanol, ethylene glycol and propylene glycol which are volatile solubilizers are used in the present invention. It is suitably selected to exhibit a great effect on viscosity control, gel inhibition, phase stabilization at low temperature, increase in solubilization and wettability. 1 to 10% by weight is used, and if it is 1% by weight or less, there is a risk of causing precipitation or floating of the insoluble inclusion. If it exceeds 10% by weight, the fragrance of the dithymonane is canceled and the laundry tends to dry quickly, but the viscosity may be drastically lowered, which may affect the consumer's perception of the cleaning power. Also, it is not frozen up to -20 ° C with very effective stability at low temperatures in winter.

A chelating agent such as sodium and potassium citrate and ethylenediaminetetraacetate (EDTA-4 Na) is used as a water-soluble cleaning enhancer, which can conceal calcium and magnesium metal ions from the aqueous solution, and the dissolution rate of the detergent composition in hard water And improves cleaning performance. 0.05 to 1.0% by weight is used. When the amount is less than 0.05% by weight, an insoluble precipitate of calcium and magnesium is formed, and the coagulated material precipitates on the fibers to give an unpleasant stimulus to the wearer. not.

(CMC-Na, CMC-Ca), polyvinylpyrrolidone (PVP), carbopol (Carbopol Type No 934, 940, 941) and water-soluble chitosan Chitosan, hydroxypropyl chitosan, carboxymethyl chitosan) is used in an amount of 0.01 to 2.0% by weight, so that a garment color protection function can be also provided. When the content is less than 0.01% by weight, the effect is insufficient. When the content is more than 2.0% by weight, it is difficult to maintain the liquid state due to pH control problems and viscosity increase due to the polymer.

In addition to the above components, if necessary, additives such as a preservative, a bactericide, a defoamer, an antioxidant, a pH adjuster, a pigment, an ultraviolet absorber, a ironing improver, a softening agent, a soil suspension agent , Enzymes and the like can be added. However, since antibacterial agents, antistatic agents, fragrances and deodorants are largely lost in washing liquids or washing liquids that are not deposited in clothes or infiltrated into the overlapping portions of clothes during the washing step of the washing process, It is considered rational and environmentally friendly to apply separately at the rinsing stage or better to give the effect.

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

The above-mentioned component (1) is a non-polar solvent which is used as a non-polar solvent to minimize the change in the texture of a garment in a home. Among them, D-Limonene is 1-methylcyclohexane, its molecular formula is C ₁₀ H _16, and it has strong cleaning ability. According to recent research reports, its use is also being investigated for sterilization cleaning and CFC replacement.

The component (2) is a compound represented by the following general formula (A) or (B) as an N-acyl sarcosinate and a polyoxyethylene ether sulfate ester salt as a cleaning accelerator.

(A) R ₁ -CONHCH ₂ COOM ₁

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

M ₁ = Na, TEA (triethanolamine)

(B) R ₂ - (OCH ₂ CH ₂ ) _n OSO ₃ M ₂

R ₂ = C ₁₀ -C ₁₆ alkyl group

n = 2 to 5

M ₂ = Na, TEA, ammonium

Here, sodium lauryl ether sulfate, an anionic surfactant, can be used as a nonionic surfactant to alleviate the irritation to the skin when polyoxyethylene (20) sobitan laurate is mixed.

(C), (D), (E) and (F) of polyoxyethylene alkyl ether, polyhydric alcohol alkyl polyether, alkyl ether carboxylate and ethylene glycol-propylene glycol as the dispersion emulsifier. ≪ / RTI >

(C) R ₃ -O (CH ₂ CH ₂ O) _n H

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

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

secondary = a mixture of hydrocarbons with 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 = an alkyl group having ₆ to ₁₄ carbon atoms

n = 3 to 12

M ₅ = Na, K

R ₆ = a straight chain alkyl group of C ₆ to C ₁₂

m = 1 to 10 n = 1 to 15

m + n = 10 to 16

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

Self-synthesis product

sodium 2-alkenyl succinate

R ₇ = C ₈ -C ₁₆ alkenyl

(H) R ₈ COO (CH ₂ CH ₂ O) _n H

R ₈ = coconoyl vegetable fatty acid

(A mixture of lauric acid, myristic acid, caprylic acid, caproic acid)

n = 5 to 13

In conclusion, the mild detergent composition for mild clothing provided by the present invention contains 20 to 35% by weight, based on the total weight of the product, of a surfactant composition composed of a nonionic and an anionic surfactant in a specific fatty acid component extracted from a natural plant The ratio of the nonionic surfactant to the anionic surfactant may be from 1: 5 to 5: 1, or preferably from 5: 5 to 6: 4, and the content of the adjuvant may be up to 30% by weight of the composition, The adjuvant will not exceed 20% by weight, more preferably from 1 to 15% by weight.

Hereinafter, specific embodiments of the present invention will be described. The present invention is not limited to the embodiments described herein.

The composition was added in accordance with the application characteristics according to the compounding ratio of the following Table 1, sufficiently mixed with a dispersing emulsification homogenizer (AG1HOMO MIXER) at a temperature of 50 to 60 DEG C and 1000 to 3000 rpm for 20 to 30 minutes to prepare a mild detergent- Were prepared in the same manner as in Examples 1 to 5, respectively.

[Table 1]

Example

Note ¹⁾ D-Limonene [CAS NO. 5989-27-5] US Florida chemical products

²⁾ Sarcosinate CN-30 [sodium N-cocoyl sarcosinate] Japan Nikko chemicals

³⁾ MIAMI L-30 [sodium lauroyl sarcosinate] MIWON Co., Ltd.

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

⁵⁾ MONOPOL LE 1017 [POE lauryl ether] manufactured by Dongnam Chemical Co., Ltd.

⁶⁾ Isodol TW-20 [POE sorbitan mono laurate]

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

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

⁹⁾ Synthesized product [sodium alkenyl succinate]

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

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

¹²⁾ Universal soap

¹³⁾ sunfom CDE [coconut fatty acid diethanol amide]

¹⁴⁾ Butyl Carbitol [diethylene glycol monobutyl ether] Made by Union Carbide, USA

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

¹⁶⁾ EDTA-4Na [Disodium Ethylene Diamine Tetra Acetate]

¹⁷⁾ carbopol [carboxypolymethylene CAS No. < / ^RTI > 9007-20-9] Products of BFGoodrich, USA

The components were charged at a temperature of 50 to 60 ° C at a rate of 1,000 to 3,000 rpm for 20 to 30 minutes in a dispersive emulsification homogenizer so as to give a comparative detergent composition composition of 6 to 10 .

[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 Hwaseong Corporation]

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

[Experimental Example 1]

Storage stability test

After preparing the compounds of Examples 1 to 5 and Comparative Examples 6 to 10 at the ratios shown in Tables 1 and 2, the mixture was adjusted to pH 7 (error: 0.2) with NaOH and citric acid and placed in a 250 ml vial, , 8 hours at room temperature (25 ℃) and 8 hours at high temperature (50 ℃) for 3 cycles. These stability evaluations were classified into three states as follows.

?: Stable state in which viscosity change is small and phase separation does not occur

△: Change in phase temperature and formation of salting-out and cloudy substances in the cloud

X: Viscosity suddenly increased to lose fluidity and phase separation occurs

[Table 3]

Stability

When the total weight% of the nonionic surfactant is more than the proper range and the distribution ratio is wider or the blend ratio with the anionic surfactant is not proper in the stability of the product, the former temperature (CP) is lowered or the liquid phase becomes cloudy or phase separation occurs .

[Experimental Example 2]

The detergent compositions shown in Tables 1 and 2 were used as samples to measure the cleaning power test results on the fabric of the test fabrics. Although it is necessary to compare and evaluate the detergency using the same dipping method as in actual use, it is considered to be a practical method to reliably evaluate the washing effect on the contamination table under harsh conditions using an internationally recognized washing device.

The cleaning force evaluation test method shown in Table 4 is as follows.

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

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

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

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

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

6. Allow the hardness of the water in the vessel to be 50 ppm based on CaCO ₃ .

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

8. After dissolution, add 2 pieces of contaminated tissue cut into 10 × 12 cm ² to the vessel.

9. Rinse with 100 rpm for 10 minutes.

10. After rinsing, rinse twice with tap water.

11. Rinse and dry naturally.

12. Measure the whiteness (Wb) using a colorimeter after the drying (R _w )

At this time, the amount of detergent required for 1 liter of water is the commercial product, which is recommended by the manufacturer (0.5 ml / l).

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

^** : US Testing Company Products

The TERG-O-TO-Meter is a small, multi-unit washer that simulates the operation of an agitator-type home washer. Four units can be used to compare four detergents simultaneously or to test in pairs (two units for each wash).

After the experiment, R _s and R _w are substituted into the Kubellda-Munk equation to obtain the washing power. (See page 64 of 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, R _o is the reflectance of the pre-

Moisture contamination: Empa 107 (Testfabrics, Inc. Swiss)

Silk Contamination: Gray fabric sample is spotted as a standard material like Empa contaminated cloth

Cotton contamination type: Empa 101 (Testfabrics, Inc.Swiss)

[Table 4]

Cleaning power (%)

As shown in Table 4, it is generally evaluated that the cleanability of the fabric is 50% or more, and that the fabric has good cleaning power. As shown in Table 3, Examples 1 to 5 had excellent cleaning power as a whole but Comparative Examples 6 to 9 showed poor cleaning power. In the case of Comparative Example 10, it is the same as the result of the composition of the present invention as a result of the conventional dry-cleaning method, which means that the detergent of the present invention can be used with confidence even at home

[Experimental Example 3]

Table 1 and Table 2 show the results of shrinkage after washing with respect to the fabric of each test piece. The results are shown in Table 5 below.

Preparation Fabric: Mo, cotton, polyester, acetate

Pretreatment: Washing (2 g / l powdered detergent at 20 캜) and drying after rinsing (65 캜 for 30 minutes)

Fabric size: 9 × 9 cm ²

Washing method: As in Experimental Example 1, each detergent composition was put into each of the fabrics of Examples 1 to 5 and Comparative Examples 6 to 9 at a rate of 0.5 ml / l of each sample, followed by incubation at room temperature for 20 minutes, 1 hour, Min and so on, dewatering and drying in a natural way.

In the case of Comparative Example 10.

1) Primary operation: The test piece is placed in a steel cylinder with 150 ml of perchlorethylene, 1.5 ml of dry cleaning detergent and 100 mouths, and the cap is closed. The test piece is put in a radionometer and operated at a room temperature of 25 ° C for 10 minutes. Take it out.

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

3) Tertiary operation: After the second operation is repeated, take out the specimen, place it between the paper towels, press the solution out, and dry in the air. This test piece is finished in one of the following ways.

- Hand Pressing: Wet in water beforehand and cover with dehydrated, moistened muslin cloth to have a moisture equivalent to about 75% of the dry weight, then press it to dry at 135-150 ° C iron.

- Steam pressing: Use a hot bed or smooth metal surface press to produce a steam pressure of 448 ~ 482㎪ (65 ~ 75㎰i). For creased fabrics with a rough surface, Should be used. Lower the front of the machine to touch the specimen and shoot the steam for 5 to 10 seconds.

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

[Table 5]

Shrinkage (%)

The shrinkage percentage of the compositions of Examples 1 to 5 was measured by the dipping method. On the other hand, the compositions of Comparative Examples 6 to 9 showed a change in shape shrinkage after washing by the dipping method for wool and acetate fabrics, and the shrinkage rate was greatly increased according to immersion time, rather than the influence on the temperature of the laundry. In Comparative Example 10, as a result of the conventional dry-cleaning method, almost the same results were obtained as compared with the use of the composition of the present invention. 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 listed in Tables 1 and 2 as a sample, the antifouling property of each fabric was measured according to ASTM D 4265-98, and the results are shown in Table 6 below.

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

2) Pretreatment: Washing (2g / l powdery detergent at 20 ℃) and natural drying after rinsing.

3) Fabric size: 10 × 12cm ²

4) Contaminants: coffee, red wine, automobile oil, grape juice

5) Pollution method: 0.2 ml (5 drops) of pollutant was dropped in the washed pollution pellets. After 20 minutes, it was dried at 65 ° C for 3 minutes

6) Washing method: For each of Examples 1 to 5 and Comparative Examples 6 to 9, 0.5 ml / l of each sample was added to the preparation fabric, dipped for 20 minutes, and dehydrated and dried naturally. In the case of Comparative Example 10, the same as in [Experimental Example 3].

&Quot; (2) "

Antifouling Index (SRI) =

c: contaminated fabric washed, w: fabric cleaned after contamination

L: reflectance,

a: red / green, b: yellow / blue

SRI: STAIN REMOVAL INDEX

[Table 6]

Antifouling Index

As a result of the antifouling test as described above, all of Comparative Examples 6 to 10 showed relatively good cleaning effect in case of contaminants such as coffee, red wine and grape juice, except for the case of automobile oil. Also, the compositions of Examples 1 to 5 exhibited better washing effects than those of Comparative Examples 6 to 10, showing the performance of the laundry detergent sufficiently in view of the shrinkage effect and the stain resistance index.

[Experimental Example 5]

In order to measure the stability of the environmental friendliness to the laundry compositions shown in Tables 1 and 2, environmental compatibility test according to water quality contamination was performed according to KSM 2714 (biodegradability test method of synthetic detergent). The results are shown in Table 7 as the biodegradability (%) after 7-8 days.

[Table 7]

Biodegradability (%)

* The perchlorethylene-used sample of Comparative Example 10 could not be cultured with KSM 2714 because the activated sludge could not be cultured. If there is no microorganism in the sample, or if it does not exist sufficiently, biological degradation does not occur. In this case, the microorganism should be added to the diluted water (expressed as BOD) and labeled as Biochemical Oxygen Demand (BOD). Here, perchlorethylene is regulated as a specific water hazardous substance.

As shown in Table 7, in Examples 1 to 5, the degree of biodegradation (%) was 99.6 or more and excellent results were obtained. In Comparative Examples 6 to 9, the degree of biodegradation was poor. In particular, in the case of Comparative Example 10, even if the washing ability has somewhat excellent results, it shows a serious problem on the degree of biodegradation.

[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 were tested for irritancy by a detergent with an in-vitro irritation test (Zein test) as a skin irritation test.

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

Zein test is a test that measures the extent of dissolution of Zein, a protein extracted from yellow corn, in detergent solution (nitrogen determination method) to measure skin irritation

Test Methods

① Add 80 ml of detergent solution into an Erlenmeyer flask and add 5 g of Zein at 37 ℃.

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

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

④ Collect 5 ~ 20 g of sample (supernatant) in 100 ml Kjeldahl flask.

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

⑥ Add 10 ml of sulfuric acid and transfer to a Kjeldahl digestion unit heated to 400 ° C or higher.

7. Add a total of 10 ml of hydrogen peroxide so that the bubbles do not overflow in 1 ml increments.

⑧ After the bubble sinks, continue heating until the solution color becomes clear and clear greenish blue.

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

⑩ Transfer the disassembled sample solution to a distillation flask and install it in the distillation unit. Boric acid trap is prepared by adding 75 ml of 4% boric acid.

⑪ Add 40 ml of 40% NaOH to the NaOH addition funnel and slowly pour into a distillation flask.

⑫ Water reservoir 300 ml of water is added and heated to generate steam. The duct through which the steam passes is kept warm with a cotton swab.

⑬ Distill and stop until the volume of the boric acid trap reaches about 100 ml. At this time, the color of the boric acid trap changes from purple to green.

⑭ Titrate the boric acid of the boric acid trap obtained by distilling ammonia with 0.5N HCl. The ending point should be the original index dark pink (purple).

Determine the N% of Zein dissolved in the detergent solution from the amount of HCl consumed and the amount of Zein solution sample initially.

Take the blank test in the same way as this test and subtract it from the test results.

[Table 8]

Protein modification rate (N%)

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

As can be seen from the results, the protein denaturation ratios of the sample detergents in Table 8 are as good as those of the detergents of Examples 1 to 5 in comparison with the comparative samples 6 to 10, indicating that they are less irritating.

All the results of Test Examples 1 to 6 up to now show that the mild detergent composition for clothes according to the present invention has excellent washing ability as well as excellent skin irritation and stability even by the dipping method.

As described above, the mild pollution-free detergent composition of the present invention obtained excellent detergency by using the raw material obtained from most of the naturally occurring surfactants without using the surfactant containing the benzene ring among the components. In particular, By minimizing human stimulation during use and increasing the biodegradability after use to reduce water pollution, cotton fabrics and chemical fibers can be used at home in the same manner as ordinary clothes washing. The dipping method, which is the main point of the present invention, There is an innovative effect that you can wash with confidence without worrying about shape deformation and contraction of natural clothes.

Claims (5)

5 to 30% by weight of D limonene as a natural detergent; 5 to 15% by weight of an N-acyl saccharin acid salt and an alkyl ether sulfate salt as a cleaning accelerator; 10 to 20% by weight, as a dispersion emulsifier, of a polyoxyethylene alkyl ether, a polyhydric alcohol alkyl polyether, an alkyl ether carboxy salt, and a polyoxyethylene-polyoxypropylene alkyl ether in combination of two or more; 2 to 5% by weight of solubilizing agent long chain alkyl succinic acid dibasic acid salt and polyoxyethylene higher fatty acid ester; As the auxiliary agent for the functional group, 3 to 5% by weight of polyethyleneglycol as a softening agent in an average molecular weight range of 350 to 700, 1 to 5% by weight of a higher fatty acid salt (Soap) as a rinsability improver, 1 to 10% by weight of a glycol ether as a solubilization accelerator, 1 to 10% by weight of a glycol ether as a hydrotrope agent, 1 to 10% by weight of at least one of ethanol, ethylene glycol and propylene glycol as an aqueous enhancer, and citrate or ethylenediamine tetraacetate (EDTA- (CMC-Na, CMC-Ca), polyvinylpyrrolidone (PVP) and carbopols (Type No 934, 940, 940) as carboxymethylcellulose as re- 941) and 0.01 to 2.0% by weight of one or more of water-soluble chitosan (hydroxyethylchitosan, hydroxypropylchitosan, carboxymethylchitosan); Wherein the detergent composition is a mild detergent composition. 3. The cleaning accelerator according to claim 1, wherein the general formula of the N-acyl sarcosinate of the cleaning accelerator is R ₁ -CONHCH ₂ COOM ₁ (R ₁ is a fatty acid hydrocarbon of Cocoyl, Lauroyl, Steaeoyl, 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). ≪ / RTI > The composition according to claim 1, wherein the general formula of the polyoxyethylene alkyl ether which is a component of the dispersion emulsifier is R ₃ -O (CH ₂ CH ₂ O) nH (R ₃ represents a linear or branched alkyl of primary, secondary or 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 to C ₁₄ , Tridecyl (C ₁₃ H ₂₇ ) and n is 5 to 12, The general formula of the polyhydric alcohol alkyl polyether (COR ₄ is lauroyl, palmitoyl, stearoyl and oleoyl, and m + n is 10 to 20) The general formula of the alkyl ether carboxy salt _{R 5 -O (CH 2 CH 2} O) nCH 2 COOM 5 ( However, R ₅ is an alkyl of straight-chain carbon atoms, C ₆ ~C ₁₄ and a side chain, n is from 3 to 12, M ₅ is sodium, potassium, Metal ions) The general formula of the polyoxyethylene-polyoxypropylene alkyl ether M is from 1 to 10, n is from 1 to 15, and the sum of m and n is from 10 to 16.) By weight based on the total weight of the composition. The composition according to claim 1, wherein the general formula of the long-chain alkyl succinic acid dibasic acid salt (Provided that R ₇ is C ₈ -C ₁₆ alkenyl) The 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, capric acid and caproic acid which are coconut plant fatty acids, and n is 5 to 13) By weight based on the total weight of the composition. The method according to claim 1, wherein the general formula of the alkanolamide as the viscosity and flow control agent _{RCONHm (C 2 H 4 OH)} n RCO is a higher fatty acyl group having _{1 to 2} carbon atoms, such as coconoyl, lauroyl, myristoyl, palmitoyl, stearoyl, or oleoyl having a carbon number of _{10 to 18} , m is 0 to 1, , The sum of m and n is 2) As the solvation accelerator, the general formula of the glycol ether (Provided that R is an alkyl group having _{1 to 8} carbon atoms and m and n are an integer of 1 to 3) By weight based on the total weight of the composition.