KR100570329B1 - A transparent stick-type spot cleaning enzyme composition - Google Patents

Abstract

The present invention relates to a solid transparent partial enzyme detergent composition which is directly applied to a contaminated portion of a garment at the first stage of a washing cycle. The present invention relates to a copolymer of carboxymethylcellulose, acrylic acid and maleic acid salt as a builder component. It is characterized by containing.

Description

Transparent stick-type spot cleaning enzyme composition             

The present invention relates to a transparent stick-type partial enzyme cleaner composition which is used by directly applying to a contaminated specific part of a garment at a previous stage of a washing cycle.

Formulations of partial washes as pre-washing pretreatments currently on the market are commercially available. It is a liquid detergent that is designed to be applied to a specific part of clothing by attaching a sponge such as glue, a high viscosity liquid, a brush attached, a gas compressed spray, a pump spray type, etc. have. The present invention relates to a formulation that solves the inconvenience of use due to breakage or deformation of a brush or sponge by applying a detergent directly to a garment without using a sponge or a brush, in particular, in the form of a solid stick such as a lipstick. will be.

An important factor to be considered in such stick-type partial cleaners is that the product properties should have a hardness that conforms to the shape of the container when using the product and can give a cleaning effect. do. In addition, the physical properties and usability at the time of manufacture should be maintained continuously. Hardness suitable for this purpose should be rubbed on the contaminated part of the garment, the film will be formed, lumped or too hard to be applied so that it cannot be applied well and does not apply excessively to the garment. In order to solve these problems, much research has been conducted on stick type cleaners. In particular, European Patent No.0205999 relates to a mixture of stearic acid and various salts in order to have a suitable hardness and dropping point, and US Pat. No. 5384060 uses Na ₂ HCO ₃ to have stability and proper physical properties for enzymes. For that product. However, the above patents all use stearic acid as a main material, which does not greatly help cleaning ability, and is only used as a main material to make product properties into a stick form, and thus has a disadvantage in that cleaning ability may be degraded or economic efficiency may be reduced. . Also, most of the products on the market are opaque.

In order to improve the disadvantages of the prior art, the present inventors have conducted a lot of research to develop a transparent solid stick type partial enzyme cleaner having a suitable hardness and dropping point and excellent usability by appropriately adjusting the mixing ratio of anions and nonions. As the main cleaning system, an alkyl polyoxyethylene ether sulfate ester salt and an alpha olefin sulfonate as an anionic surfactant and a linear alkylbenzene sulfonate and an alkyl polyoxyethylene ether as a nonionic surfactant were used. In addition, propylene glycol is added to improve product stability, dropping point and usability by suppressing the occurrence of film with excipients, preventing re-contamination, improving washing power, enhancing the effect of puss, and maintaining proper physical properties during distribution and use. CMC and a copolymer of acrylic acid and maleic acid salt were used.

In the present invention, the mixing ratio of the nonionic surfactant and the anionic surfactant was about 15% by weight: about 33% by weight in order to exert an excellent cleaning effect on partially smeared contamination and to maintain hardness and usability. More specifically, the mixing ratio of the alkyl polyoxyethylene ether which is a nonionic surfactant and the alkyl polyoxyethylene ether sulfate ester salt which is an anionic surfactant, an alpha olefin sulfonate, and a linear alkylbenzene sulfonate is 5: 5: 5: 1, respectively. In the case of much deviation from the blending ratio (approximately 5 to 10% by weight), the phase stability tends to drop sharply, or the viscosity and usability tend to fall significantly. In addition, the more deviating from the compounding ratio, the transparency of the product may be lowered. The composition of the present invention is 5 to 20% by weight of alkyl polyoxyethylene ether, 5 to 20% by weight of alkyl polyoxyethylene ether sulfate ester salt, 5 to 20% by weight of alpha olefinsulfonate salt and 1 to 5 linear alkylbenzenesulfonate salt Contains weight percent. The total content of the anionic surfactant and the nonionic surfactant used in the present invention is 16 to 65% by weight of the composition, preferably 30 to 55% by weight. When the total content of the surfactant is 16% by weight or less of the composition, it is difficult to expect sufficient washing power, and when the amount is over 65% by weight, the composition becomes unstable, which is not preferable.

As the nonionic surfactant used in the detergent composition of the present invention, in addition to polyoxyethylene alkyl ether, sugar fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, fatty acid alkanolamide is preferable. In particular, it is preferable to use polyoxyethylene alkyl ethers of the general formula (I):

RO (CH ₂ CH ₂ O) nH (Ⅰ)

In the above formula,

R is an alkyl group having 6 to 22 carbon atoms,

n is an integer of 5-25.

Suitable n in the present invention is an integer from 7 to 9. The alkyl group of the polyoxyethylene alkyl ether is preferably branched or linear, but is preferably linear from the viewpoint of biodegradability.

The nonionic surfactant used in the present invention is 5 to 20% by weight in the detergent composition. More preferably, it is 10-20 weight%. Suitable anionic surfactants for the present invention include olefinsulfonates having 12 to 24 carbon atoms, wherein the olefinsulfonates are sodium alkenesulfonates obtained by neutralizing them with strong alkalis with a mixture of alkenesulfonic acids and sultones obtained by sulfonating alpha olefins with sulfuric anhydride. And hydroxyalkanesulfonic acid sodium salt. The alpha olefin which is a raw material of an olefin sulfonate is a C12-C24, Preferably it is a C1-C18 monoolefin, A linear chain olefin is preferable. For example, 1-dodeken, 1-hexadekene, 1-octadeken and the like. The alpha olefin sulfonate used in the present invention is 5 to 25% by weight, preferably 10 to 20% by weight in the detergent composition.

As the anionic surfactant used in the present invention, the linear alkylbenzenesulfonate salt is used in an amount of 1 to 5%, preferably 3 to 5% by weight. If it is out of this range, the washing power is lowered or the transparency is significantly reduced. The alkyl polyoxyethylene ether sulfate ester salt used as an anionic surfactant in the present invention is prepared by adding oxyethylene to alcohol, making sulfate ester with anhydrous sulfuric acid, neutralizing with strong alkali, and having 8 to 16 carbon atoms. Suitable carbon number for use in the present invention is about 12. Also, 3 to 7 moles of added oxyethylene may be used, but preferably 5 moles is suitable.

In the present invention, 5 wt% to 15 wt%, preferably 10 to 15 wt% of propylene glycol is added to improve product stability and usability, and prevents re-fouling adhesion, improves washing power, and improves the effect of pus only. In order to remove traces such as stains due to the strong washing of the CMC and copolymers of acrylic acid and maleic acid salt was used to improve the shortcomings left after using the existing product.

In the present invention, 1 to 8% by weight, preferably 3 to 6% by weight of CMC is used, 1 to 10% by weight of the copolymer of acrylic acid and maleate, and 1 to 10% by weight of the fatty acid salt.

As the fatty acid salt used in the detergent composition of the present invention, at least one saturated or unsaturated fatty acid having 6 to 22 carbon atoms and at least one salt selected from sodium, potassium, monoethanolamine and diethanolamine are preferable, and sodium and potassium salts are particularly preferred. desirable. Fatty acid salts are obtained by neutralization reactions of fatty acids with alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, monoethanolamine, diethanolamine, but saponification reaction of these alkaline substances with fatty acid esters such as natural fats and oils. It can also be obtained by The fats and oils used at this time may include natural fats and oils such as tallow, sunny, pork, fish oil, palm oil, palm kernel oil, palm oil, rapeseed oil, soybean oil and sunflower oil, or oils prepared by deoxidizing, decoloring and curing. have. Or as a fatty acid, the fatty acid obtained by hydrolyzing said fat or oil and what prepared this fatty acid by methods, such as distillation, fractionation, and hardening, can be used. Fatty acid salt used in the present invention is 1 to 10% by weight in the detergent composition. Preferably 3 to 8% by weight is suitable. Fatty acid salts have an effect as a detergent and an effect of lowering bubbles during rinsing after washing to facilitate rinsing.

Examples of the water-soluble excipient used in the detergent composition of the present invention include silicates, carbonates, bicarbonates, sulfates, sulfites and borates. In consideration of load on the environment and washability, silicates and carbonates such as sodium silicate and sodium carbonate are preferable.

The copolymer used in the present invention is 1 to 10% by weight of the detergent composition, preferably 3 to 6% by weight.

As the solubilizer, ethanol, sodium toluene sulfate, propylene glycol and the like may be used, and may contain 1 to 30% by weight, and in the present invention, in particular, 5 to 15% by weight of propylene glycol is preferably considered in consideration of physical properties and usability in the solubilizer. 8 to 12% by weight.

As enzymes that can be used in the present invention, proteases, lipases, amirases, cellulases and the like can be used. Industrially, for example, NOVO's ALKALASE, ESPERASE, SAVINASE and the like can be used. Particularly preferred is an enzyme that has been surface treated with an inert material to prevent dust generation and to increase storage stability. Appropriate addition amount of the enzyme is 0.5 to 3.5% by weight in the detergent composition, more preferably 0.3 to 1.5% by weight.

In the case of enzymes, there is a suitable pH range for stability, and beyond this range the stability is significantly lower. The preferred pH range is 7.5 to 9.5, and useful pH buffers in this range include boric acid and the like and contain 0.05 to 3 weight percent.

Hereinafter, the present invention will be described in detail through examples.

Example 1

Change of Compounding Ratio and Physical Property of Surfactant

Changes in Physical Properties of Alkyl Polyoxyethylene Ether and Alkyl Polyoxyethylene Ether Sulfate Contents ingredient A B C D E F G Alkyl polyoxyethylene ether (9EO) 0 5 10 15 20 25 30 Alkyl polyoxyethylene ether sulfate ester 30 25 20 15 10 5 0 Alpha olefin sulfonates 15 15 15 15 15 15 15 Straight chain alkylbenzene sulfonate 3 3 3 3 3 3 3 Propylene glycol 10 10 10 10 10 10 10 Fatty acid salt 5 5 5 5 5 5 5 Copolymer 3 3 3 3 3 3 3 Boric acid 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Carboxymehyl cellulose (CMC) 3 3 3 3 3 3 3 enzyme One One One One One One One Others (carbonates, silicates, sulfites, etc.) 5 5 5 5 5 5 5 water Balance Balance Balance Balance Balance Balance Balance Feeling + ++ ++++ ++++ +++ ++ + Dropping Point (℃) 40-50 38-45 42-50 50-58 45-50 35-43 30-35 Product transparency + + ++ ++ +++ +++ ++

week; ※ 1) The alpha olefin sulfonate was prepared from 30%. The fatty acid salt is sodium salt of Uji Fatty Acid Co., Ltd., polyoxyethylene alkyl ether (9EO) is LA-9 of Ilchi Chemical, copolymer is CP-5 of BASF Corporation, and enzyme (2.5L of alcalase from NOVO). Indicates.

      2) Measurement of the feeling of use: Put the product prepared as described above in a cylindrical container with a diameter of about 2cm and rub the contaminated part of the garment at room temperature after manufacturing the product to lump the detergent, applicability of the garment and rinsing property after use. Evaluated as follows.

++++: No clumping of detergent, degree of application and good rinsing after use, no residue or film

+++: There is no clumping of detergent and the degree of application and rinsing after use is good, but debris and film occur.

++: The degree of lumping or application of detergent and poor rinsing after use, resulting in debris and coating

+: Not available (fully solid or near liquid)

      3) Transparency of the product: Manufactured in a cylindrical shape of about 2cm as described above, measure the following in the light of white A4 paper painted red, yellow, and black by 1cm width on the back.

+++: Color is clearly distinguished, ++: Can be distinguished +: Not distinguished

As can be seen in Table 1 of Example 1, when the content of other surfactants and excipients is constant, the change in physical properties according to the content of alkylpolyoxyethylene ether and alkylpolyoxyethylene ether sulfate esters is equivalent to the amount of alkylpolyoxyethylene ether. It can be seen that at 5 to 25% by weight, more preferably at 10 to 20% by weight, the physical properties and usability are excellent, and the alkylpolyoxyethylene ether sulfate is excellent at 10 to 20% by weight.

After the preparation according to Table 1 above, the results of evaluating the cleaning power are as follows.

    * Cleanability Evaluation of Table 1

    -Method: Comparison of cleaning power between 1 type of sponge-type partial cleaner and 7 prescription products

    -Washing machine: Terg-o-Tometer (Korea Science Technology)

    -Washing conditions: rotation speed (120 rpm), temperature (25 ℃), washing time (10 minutes), rinsing (3 minutes, 2 times)

    -Washing water: tap water (hardness: 53 ppm)

    -Detergent concentration: 1.0 Gr / l

    -Contaminated Cannon: EMPA-104, JIS Contaminated Cannon

    Evaluation: Relative comparison of the above preparations with an average value of the cleaning power of commercial liquid thickeners is 100.

Detergency Evaluation division Liquid detergent average Formulation A Formulation B Formulation C Formulation D Formulation E Formulation F Pharmaceutic G EMPA-104 100 82 85 98 101 105 110 99 JIS Pollutant 100 80 90 97 102 104 108 98

Also in the washing power experiment for the formulation of Table 1, it can be seen that the improvement of the washing power is difficult when biased to either of the alkyl polyoxyethylene ether and the alkyl polyoxyethylene ether sulfate ester salt.

Example 2

 (Changes in Physical Properties by Surfactant Mixing Ratio)

Changes in Properties of Alpha-Olefin Sulfonate and Straight Alkylbenzenesulfonate Mixtures ingredient A B C D E F G Alkyl polyoxyethylene ether (9EO) 15 15 15 15 15 15 15 Alkyl polyoxyethylene ether sulfate ester 15 15 15 15 15 15 15 Alpha olefin sulfonates 0 5 10 15 20 25 30 Straight chain alkylbenzene sulfonate 30 20 10 8 5 2 0 Propylene glycol 10 10 10 10 10 10 10 Fatty acid salt 5 5 5 5 5 5 5 Copolymer 3 3 3 3 3 3 3 Boric acid 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Carboxymethyl cellulose (CMC) 3 3 3 3 3 3 3 enzyme One One One One One One One Others (carbonates, silicates, sulfites, etc.) 5 5 5 5 5 5 5 water Balance Balance Balance Balance Balance Balance Balance Feeling + ++ ++++ ++++ ++++ ++ + Dropping Point (℃) 35-45 35-40 38-42 50-60 45-55 42-50 45-55 Product transparency + + + ++ ++ +++ +++

week; ※ 1) The alpha olefin sulfonate was prepared from 30%. The fatty acid salt is sodium salt of Uji Fatty Acid Co., Ltd., polyoxyethylene alkyl ether (9EO) is LA-9 of Ilchi Chemical, copolymer is CP-5 of BASF Corporation, and enzyme (2.5L of alcalase from NOVO). Indicates.

      2) Measurement of the feeling of use: Table 1 of Example 1. Same as method

      3) Product transparency: Table 1 of Example 1 above. Same as method

The cleaning power test results for the prescription of Table 3 of Example 2 are as follows.

Detergency results in Table 3 division Liquid detergent average Formulation A Formulation B Formulation C Formulation D Formulation E Formulation F Pharmaceutic G EMPA-104 100 105 102 100 101 102 100 98 JIS Pollutant 100 102 100 98 100 100 99 97

As can be seen in Table 3 of Example 1, the change according to the mixing ratio of the alpha olefin sulfonate and the linear alkylbenzene sulfonate in a state where the content of other surfactants and excipients is constant is prepared rather than shifted to any Han family preparation C, D, E In part, satisfactory results were obtained in both physical properties and cleaning power. In addition, it can be seen that the higher the content of the linear alkylbenzenesulfonate, the lower the transparency of the product.

Example 3

Measurement of physical property change according to propylene glycol and CMC content ingredient A B C D E F G G Alkyl polyoxyethylene ether (9EO) 15 15 15 15 15 15 15 15 Alkyl polyoxyethylene ether sulfate ester 15 15 15 15 15 15 15 15 Alpha olefin sulfonates 0 5 10 15 20 25 30 30 Straight chain alkylbenzene sulfonate 30 20 10 8 5 2 0 0 Propylene glycol 10 10 10 10 0 5 10 20 Fatty acid salt 5 5 5 5 5 5 5 5 Copolymer 3 3 3 3 3 3 3 3 Boric acid 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Carboxymethyl cellulose (CMC) 0 2 4 8 3 3 3 3 enzyme One One One One One One One One Others (carbonates, silicates, sulfites, etc.) 5 5 5 5 5 5 5 5 water Balance Balance Balance Balance Balance Balance Balance Balance Feeling + +++ ++++ ++ + ++ ++++ ++ Product transparency + +++ ++++ + ++++ ++++ +++ ++

week; ※ 1) The alpha olefin sulfonate was prepared from 30%. The fatty acid salt is sodium salt of Uji Fatty Acid Co., Ltd., polyoxyethylene alkyl ether (9EO) is LA-9 of Ilchi Chemical, copolymer is CP-5 of BASF Corporation, and enzyme (2.5L of alcalase from NOVO). Indicates.

      2) Measurement of feeling of use: Table 1 of Example 1). Same as method

      3) Product transparency: Table 1 of Example 1). Same as method

As can be seen in Table 5 of Example 3, it can be seen that the feeling of use varies depending on the content of CMC and propylene glycol, and the content of CMC is 2 to 4% by weight, and propylene glycol is about 5 to 15. . The effects on the copolymers of enzymes, acrylic acid and maleic acid salts are generally well known, and therefore, the attachment to a prescription experiment is omitted.

The present invention configured as described above adds 10 to 15% by weight of propylene glycol to the cleaning composition to improve product stability and usability, and prevents re-fouling adhesion, improves cleaning power, and enhances the effect of squirting, so that only specific parts are strong. In order to remove traces such as stains by washing, using a copolymer of CMC and acrylic acid and maleic acid salt has the effect of improving the disadvantage that the traces remain after use of existing products.

Claims (13)

16 to 65% by weight of nonionic and anionic surfactants, 1 to 30% by weight of solubilizers, 1 to 10% by weight of fatty acid salts, 1 to 8% by weight of carboxymethyl cellulose (CMC), 0.5 to 3.5% by weight of enzymes, acrylic acid A transparent stick type partial detergent composition consisting of 1 to 10% by weight of a copolymer of maleic acid, 5% by weight of water-soluble excipient, 0.05 to 3% by weight of pH buffer, and a residual amount of water. The transparent stick type partial detergent composition according to claim 1, wherein the nonionic surfactant is alkylpolyoxyethylene ether. The transparent stick-like portion according to claim 2, wherein the alkylpolyoxyethylene ether is added with 9 to 12 moles of ethylene oxide to a primary or secondary alcohol having 8 to 16 carbon atoms and has a composition ratio of 5 to 25% by weight in the detergent composition. Detergent composition. The transparent stick type partial detergent composition according to claim 3, wherein the composition ratio of the alkyl polyoxyethylene ether is 10 to 20% by weight in the detergent composition. The transparent stick type partial detergent composition according to claim 1, wherein the anionic surfactant comprises an alkyl polyoxyethylene ether sulfate ester salt, an alpha olefin sulfonate salt and a linear alkylbenzene sulfonate salt. The transparent stick type partial detergent composition according to claim 5, wherein the alkylpolyoxyethylene ether sulfate ester salt has an ethylene oxide added molar number of 3 to 7. 7. The transparent stick type partial detergent composition according to claim 6, wherein the alkylpolyoxyethylene ether sulfate ester salt has an ethylene oxide added mole number of 5. The transparent stick type partial detergent composition according to claim 5, wherein the alpha olefin sulfonate has 14 to 18 carbon atoms. The compounding ratio of alkyl polyoxyethylene ether: alkyl polyoxyethylene ether sulfate ester salt: alpha olefin sulfonate: linear alkylbenzene sulfonate is 10 to 20% by weight: 10 to 20% by weight: 10 to 20% by weight : Transparent stick type partial detergent composition which is 3 weight%. 10. The transparent compound according to claim 9, wherein the compounding ratio of alkyl polyoxyethylene ether: alkyl polyoxyethylene ether sulfate ester salt: alpha olefin sulfonate: linear alkylbenzene sulfonate is 15% by weight: 15% by weight: 15% by weight: 3% by weight. Stick type partial detergent composition. The transparent stick type partial detergent composition according to claim 1, wherein the fatty acid salt is a saturated or unsaturated fatty acid having 6 to 22 carbon atoms and the composition ratio is 2 to 7 wt% in the detergent composition. The transparent stick type partial detergent composition according to claim 11, wherein the fatty acid salt is sodium or potassium salt. The detergent composition of claim 1, wherein the CMC has a composition ratio of 2 to 6 wt% in the detergent composition and the copolymer of acrylic acid and maleic acid salt has a composition ratio of 2 to 5 wt% in the detergent composition.