JP2014214304A - Concentrated liquid detergent composition containing alkyl sulfonic acid salt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve characteristics of alkyl sulfonic acid salt (SAS) whose demand is sluggish in spite of having distinguished biodegradability and ecological properties.SOLUTION: A prior anion-rich and sub-non-ionic combination is completely reversed focusing of a nonionic surfactant without changing a composition as two main constituents of SAS and a fatty acid ester type (including an ether) which is a typical one of non-ionic surfactants to form an amine neutralized substance composed mainly of the fatty acid ester. Adding a buffer action thereto, the dilution degree by water becomes about 5-13 times. 10-30 wt% of SAS and 30-65 wt% of fatty acid ester are mixed to maintain a neutral region (pH5-8) and to correct, maintain, and stabilize regularity of a viscosity by water, thereby the detergent have characteristics, appearance, detergency, finish, and ecological properties.

Description

Field of Invention

  The present invention includes a surfactant having an active ingredient of up to about 85% in the neutral range and other auxiliary ingredients, and is composed mainly of an alkyl sulfonate (hereinafter referred to as SAS) that is appropriately diluted with water and used for this purpose. Detergents that are diluted with water up to about 13 times and have the constant stability inherent in the present invention, with less variation in viscosity and appearance, and reverse use of the greatest weakness of SAS as the greatest feature. It is about.

  Post-war (after 1945) detergents are the four major anionic components LAS (alkylbenzenes hereinafter referred to as LAS), soap (referred to as FAS), higher alcohol sulfate (AS) or ether sulfate (referred to as AES). Since these are advantageous in terms of the environment and characteristics, heavy detergents utilizing their maximum characteristics have been used in reverse. The concept of the present invention relates to a composition with reasonable conditions of the water dilution type.

  After the war, neutral detergents with concentrations of surfactants (about 15 to 30%) such as SAS, AES, and AOS (alpha olefin sulfonate) appeared, and they were transferred from soap to neutral detergents. Especially after Showa 30th, it appeared to remove pests attached to the surface of vegetables and fruits.

  Among them, the German IG (EG) group uses light radiant energy (hν) as an initiator, and directly sulfonates n-paraffin, which is a raw material, to provide biodegradability and water solubility at low temperatures. It was the best and featured alkyl sulfonic acid surfactant. However, there was anxiety about stickiness under the initial constant composition, and since there was no heavy texture, it shifted to other raw materials, and there was only one support for the feeling of use compared to anionic LAS, AS, AES. . However, by devising this, the present invention was newly developed by working on the development of a neutral dishwashing detergent that takes eco-characteristics and touch into consideration.

  The present inventor in this regard observed the actual situation on December 17, 2009, and applied for a weakly acidic to neutral patent containing a new zwitterionic surfactant relating to SAS. Even if it does not contain a zwitterionic surfactant, it has led to the formation of an effective detergent with the same type of SAS as the main axis. The characteristics of zwitterion have the power to produce the best results at the isoelectric point, exhibit the detergency, and cost reduction is the best, but it feels unsatisfactory for users who use the neutral type. However, dishes such as vegetables, fruits and silk / wool can be washed. Also, by containing 60% or more of moisture depending on how the raw materials are used, increasing the amount of amphoteric active agent also increases the existing moisture in it, resulting in changes in viscosity and appearance, and the same feel as other products. This has been accomplished and the present invention has been completed by changing the way of thinking.

In addition, SAS is used together with AA (fatty acid alkanolamide, hereinafter referred to as AA) for products having an active ingredient of 15% to 30%, and some are commercially available, but even compared to LAS, AES, AS, etc. The feeling of use was bad, and the popularity as a product was low due to the added cost.
In addition, products such as hypochlorite (NaOCl), solvent, cleanser, etc. have not been able to take advantage of the characteristics of SAS components and are unsuitable for handling.

Therefore, the present inventor procured SAS materials from a German manufacturer and tried to review the progress of experiments in the past in earnest.
SAS was the first development of the same kind of AOS (α-olefin sulfonate) in Japan in 1990 around the TO reactor. However, it was powdery and strongly hygroscopic, making it difficult to commercialize it. Since the concept (eco), which is the theme of the 21st century, began to attract attention, the manufacturer who developed the product closely examined and commercialized the SAS, but there were many more problems, but the SAS was forgotten from history. However, after technological innovation such as the combined use of surfactants in recent years, the major goal is to use LAS and AES in combination with other factors, and major manufacturers are again seeing elements for studying new applications.

Problems to be solved by the present invention

  In recent years, it has become necessary to develop products that meet GHS, PRTR, and MSDS regulations and the Containers and Packaging Recycling Law, etc. in detergents. Reconsidered for fruition, and as referred to in the attached table, I recalled an innovative change that upgraded the power of SAS, LAS, AES, AS, soap (FS) As a result, we reviewed as much as possible the causes, quality, and characteristics of the production and use of SAS compared to, and examined and examined from the performance aspect.

  First, as a representative of each anionic type and nonionic type, controlling moisture and pH, and pursuing the best situation while changing the content and ratio, LAS and AA, AES and AA, which are conventional formulas. Specializing in SAS with a combination of soap and AA, SAS and AA, a critical difference from other anions was found to open the scope of the present invention.

  The original appeal of SAS is not only biodegradability, but also acid resistance, alkali resistance, and especially chlorine bleaching (NaOCl system), SAS is the only excellent, and stability (compatibility with chlorine ions) is outstanding. The inventor himself was related to Japanese Patent Application No. 58-234099 (which was finally registered) on December 12, 1983. It was known as other chlorinated and alkaline components such as other alkyl phenyl ethers (ie, benzene ring with an alkyl group attached to a sulfonate salt), but with the nonylphenol (NP) in the 1990s the vice president of the United States After consulting with the manufacturer what was named “Environmental Hormone” in Colborn's “Stolen Future” called Algoa and the second Rachel Carson, the company has further focused on SAS R & D. At the time, the most recent data reviewed by the Nikko headquarters in Japan at the time was 30 days after the start of the experiment. Was beyond the scope of prediction.

Therefore, the present invention has found out a mechanism for resolving the characteristics of the SAS by using the weak points of the SAS in terms of practical points for realization, and the present invention will become a leading role in the 21st century as an anionic surfactant. Appropriately, it has been realized because it has been necessary to continue to monitor SAS in Japan since its development in 1990, and to develop a situation of the composition utilizing the weaknesses of SAS itself. Several times during development, "SAS + nonion combination" was simply prescribed, but the present invention has no stickiness depending on the concentration range of SAS, and if it dissolves immediately, it does not have a clear and clear viscous activity. From the viewpoint of those skilled in the art, the detergent has a pale feeling of use and generally has a weak feeling that it has little effect, and the solution to this problem has become a standard for activating SAS. On the other hand, SAS is a biodegradable, TLm, BOD, LD ₅₀ , and other anionic systems that have been compared for safety since 1990. AES, AS, APS (alkyl phosphate), and soap (higher fatty acids, It was proved again that the SAS data are clearly good for (alkalates) and the like. (Manufacturer names are Bayer, Hoechst, BASF, Japan Mining)

The road to the specific composition of the present invention is composed of anionic and nonionic representatives since 1960, and the types of anionic representatives after the war (S20) are (1) soap, palm fatty acid potassium. (Liquid), soap (solid)
(2) Higher alcohol, sulfate (AS) or ether sulfate (AES)
(3) There are two types, linear (LAS) and branched (ABS), which are alkylbenzene sulfonic acids. LSA is mainly used for environmental considerations. (4) The alkyl sulfonic acid (SAS) of the present invention is There are n-paraffins obtained by petroleum refining, and there are AOS and MAP. (AOS: α-olefin sulfonate soda) (MAP: sodium alkyl phosphate)
In particular, the use ratios of (1) to (4) were more than 90% of the production of all anions.
Therefore, the following sample was newly created, and its viscosity and appearance were scrutinized. (See (Table 2))

上記表は各メーカーのデータから引用したものを一つの目安とし参照して表を作製した。
テスト条件は各サンプルを −１５℃→０℃→２０℃→４０℃→２０℃を経由した（２日間）ファイナル２０℃の外観と粘度を調査したもの。
粘度では単にＣＰ→ｍＰａ・ｓ（２０℃）
テストの外観 ○−殆んど変わらない、微黄色透明液 △−白色状、微濁
×−混濁、分離状液 ※テストの外観は３人の合計で評価したFirst, the trend of the raw material composition was traced by specifying the ratio of (1) to (4) to 80% and AA to 20%, and (1) to (4) to 20% and AA to 80%. . The active ingredient of this anion + nonion used 15% and 30% aqueous solution plus PG (propylene glycol) 5%.

The above table was created by referring to the data quoted from each manufacturer as a guide.
The test conditions were those in which the appearance and viscosity of the final 20 ° C. were examined for each sample via −15 ° C. → 0 ° C. → 20 ° C. → 40 ° C. → 20 ° C. (2 days).
The viscosity is simply CP → mPa · s (20 ° C)
Appearance of test ○-Almost unchanged, slightly yellow transparent liquid △-White, slightly turbid
×-Turbidity, separated liquid * Test appearance was evaluated by a total of three people

From the above, it has been found that the SAS treated with AA as the main axis has a stable structural viscosity regardless of humidity and temperature.
Based on this result, stability and moldability are sought by combining a SAS and a nonionic surfactant as much as possible in advance, and in the meaning of the present invention, it is a coincidence. Three types of AA (higher alcohol), AE (ethoxylate), and AG (alkyl glycoside) were prepared and tested at a ratio of 80%: 20% for the combination comparison of surfactant, SAS, and each raw material.

各供試液６種の２０％水溶液を作製、ｐＨ７．０値とし、ＰＧ．５％を添加調合した液を各サンプルとして、温度変化（−１５℃〜０℃〜２０℃〜４０℃）による保存状態を観察した。The list of test solutions (component ratios) was as follows.

A 6% 20% aqueous solution of each test solution was prepared, and the pH was set to 7.0. The storage state by temperature change (-15 degreeC-0 degreeC-20 degreeC-40 degreeC) was observed for the liquid which added and prepared 5% as each sample.

不、良の外観を３人のモニターにより目視観察し、トータル評価で示している
表に明示してまとめた結果、本発明のＳＡＳとＡＡの存在と融合が、極めて有意性の高い組み合わせであることを証明している

As a result of visually observing poor and good appearances with three monitors and clearly summarizing them in the table shown in the total evaluation, the presence and fusion of SAS and AA of the present invention is a highly significant combination. Prove that

Means to solve the problem

Thus, the constitution method of the present invention is strictly limited to the following range, and the remarkable result can be confirmed.
(1) SAS (anion) 10-30% (2) AA (nonion) 30-65%
The total of (1) and (2) is 60 to 85% (3) Polyhydric alcohol 5 to 15%
(4) 0.5% to 5% of carboxylic acid having OH as a neutralizing agent (α-HA (hydroxyamide)
(5) It is a liquid substance containing SAS with a moisture content of less than 10% and exhibits a stable effect.

Compared to those containing betaine zwitterions previously filed by the present applicant (December 19, 2009), the present invention has a good workability and is easy to make the viscosity uniform. The product contains a lot of moisture, the formulation is restricted, the price of zwitterion is 50 to 200% higher, and as you can see from the actual results, it has a disadvantageous result as a detergent compound Yes.
In addition, the product bottle contents for 30 years have been distributed in the range of 300 to 800 ml, and even if the content components have evolved, they are marketed in the same standard, the user uses the undiluted solution as it is, and the container repeats the pattern of waste. It is.

  The product of the present invention maintains the viscosity and colloid-forming ability of the surfactant even when the stock solution is diluted 10 to 12 times with water at the time of use, and is as follows in an actual test. Applying mayonnaise or butter on a stainless steel plate and comparing it with a 10-fold diluted product of the present invention (viscosity is 144 mPa · s at 13510 times the stock solution) and a commercially available major product for comparison, As a result of adding a detergent, mixing well, and rinsing with water afterwards, the stainless steel stains resulted in excellent results.

  The same thing is to mark the oily marker and attach each detergent to remove the product of the present invention so that it peels off. Several times faster. This is because water, dirt, and detergent are in a well-balanced triangle, and the action of Vanthof's water electrolyte has been successful. In other words, there is a deviation in which the water of the water that is the center of the detergency does not fully function with the force of the surfactant alone.

（Ａ）は本発明の代表の原液を蒸留水で５、１０倍位に水希釈して粘度を調べた。
１〜５倍〜１０倍〜１５倍の希釈粘度の値を調べたが数値は変化しなかった。
（Ｂ）は大手市販品を参考品とした。

In (A), a representative stock solution of the present invention was diluted with distilled water 5 to 10 times, and the viscosity was examined.
The dilution viscosity values of 1 to 5 times to 10 times to 15 times were examined, but the numerical values did not change.
(B) used a large commercial product as a reference product.

The present invention places importance on this viscosity constancy, and confirms the unexpectedness of developing the performance and situation of the composition of the present invention.
That is, if the combination of SAS and AA, the water content and the ratio thereof are boldly reformed, an unexpected plus alpha effect will occur.
In this regard, as described in “1979 Yuka Tokiwa Bunkatsu Detergent Report”, surfactants have a synergistic effect due to their combination, ratio and ingenuity, which is just proof of this.

  It goes without saying that the constituent requirements of the present invention include several applications under the conditions of the preceding paragraph. For example, not only AA and coconut oil fatty acid, but also other plant fatty acids and alkanols include ethanol or less isopropyl alcohol, butyl alcohol, and similar compounds contained therein. In addition to this, the salt neutralized with hydroxycarboxylic acid (α-HC) promotes the specificization of structural viscosity, and the buffering action (Bach effect) is also added, so that the effect can be realized.

  In addition, it is widely used for other skin products (L ascorbic acid (VC), sodium alginate, aspartate, PVP, styrene maleic anhydride, retinal, ceramide, sage extract, aloe extract, lecithin, Elastin, eucalyptus, rose mari, titri oil, citrus oil, other herb extracts (referenced by materials of the Japanese Society of Aromatherapy, 1999.2.28), etc. (For example, colloidal silica, colloidal alumina, humic acid, white carbon, hydroxyapatite, ammonite, illuminite, vitamins, lycopene, nicotinic acid, pantothenic acid, β-carotene, glycine, cysteine) It has the property of accepting the ingredients of the ingredients as appropriate. From toxic components and harmful substances such as anti-biological disorder reactions (allergy -, atopic -, virus, etc.) it is possible to reduce the.

  This is due to the fact that the anionic system called SAS is superior in coexistence with other substances, especially compared to other anions, and this is also a feature of the present invention.

Effects of the present invention

  As described above, the present invention can produce a detergent group having an unlimited combination from the wide durability and versatility of SAS, and achieves the following effects. In the case of a conventional kitchen detergent, the container has been disposable for the past 30 years, and the method of using the product has not changed much, but the surfactant of the component is over 10% for the purpose of improving the competitiveness of the cleaning power with other companies. Is used in large quantities up to about 50%, and speeding of washing is also required. For example, it is mixed with a defoaming agent of a substance not directly related to washing, and it quickly defoams, but there are components such as attached residue. Unnecessary enhancements have been made. For this reason, it is expected that excessive drainage will cause water pollution during drainage.

In the present invention, the active ingredient of the surfactant is first made 80% or more, and diluted and adjusted to 5 to 12 times with water to reduce the packing state. 30% or more reduction in materials, distribution costs, etc. Excellent, highly concentrated and environmentally friendly due to dilution type, but does not decrease cleaning power and performance, maintains its viscosity even after dilution, changes viscosity and feel We were able to use it without any delay, and we were able to obtain more reliable product results.
It can be used as it is not only for kitchen detergents of JIS-K3370, which is a feature of the concept of the present invention, but also for neutral laundry detergents (including silk and wool fibers) such as living, sports equipment, wood and leather products. I notice that. In addition, the product is excellent in penetrating power, hydrophilic power and finish, and can be easily and widely used for soiled parts in various applications.

Hereinafter, specific physical properties of the product of the present invention and the conventional comparative product will be clearly verified.
The test liquid products shown in the table were prepared as Example 1, and the following tests were performed to confirm the significance.

Invention Products 1-5 The significance of the present invention was verified with respect to I appearance and II viscosity using the conventional comparative products (1) to (6).
The verification was conducted by preparing a 5-fold, 10-fold, and 15-fold water dilutions for each test solution.
The preservation | save state by the temperature change (24 hx30) of normal temperature --15 degreeC-0 degreeC-20 degreeC-40 degreeC was observed.
I. Appearance The results of a visual sensory test conducted by three monitors are shown in the table below.
○ There is almost no difference from the initial
△ Some semi-turbidity and signs of thickening are seen, but there is no problem
X There is a sign of separation or cohesion II. viscosity
<Viscosity> Unit-mPa · s (Reference CP)

  In the following, the two remarkable results of the present invention surpassed great significance, and their unexpectedness exceeded expectations. This is not only the behavior of each component in water, but also the ratio and temperature of water, especially in the water, making use of structural viscosity, which results in a balance with skin care, speed rinse, foam break-up, and surfactant. We consider that it is a devised way of subtly distributing and acting on homeostasis.

Formula for calculating the deviation rate for obtaining the deviation rate of the viscosity for the present invention and the conventional comparative example product, for example,
Dilution factor: 5 times, 10 times, 15 times 160, 150, 124, 160, -124, / 160, = 23%
Comparative Example Test Solution (1). 60, 51, 30, 60, -30, / 60, = 50%

５倍から１５倍の粘度の偏差率の数値、それが小さい程粘度がある事が証明される。
上記のごとく比較例は約２５％を超え本発明との明確な有意性を露見した 。
以上、本発明品は比較例品に比べ、２倍以上の実用優位性のある差を示した。

The numerical value of the deviation rate of the viscosity from 5 times to 15 times, the smaller the value, the more the viscosity is proved.
As described above, the comparative example exceeded about 25% and revealed a clear significance with the present invention.
As described above, the product of the present invention showed a difference in practical advantage of more than twice that of the comparative product.

Foaming and Detergency Test In order to test the detergency (simplified method), special hard water for comparison test when using the product of the present invention and a commercial product is prepared next.
A mixture of 5.0 g of CaCl ₂ 2H ₂ O (calcium chloride) and 10.0 g of MgSO ₄ (magnesium) per 1 l of water is used as a hard water test solution, and 100 ml of water is added to a 200 ml glass beaker.
Next, as representatives of the sample test solution of the present invention, two kinds of “10 of 1” and “10 of 4” in which test solutions 1 and 4 were diluted 10 times, and two major manufacturers A company and B company each These four types were compared in the following usage situation, and the actual usage state of the detergency was tested as a reference.

結果、本発明品は分散状態が良く、油分の剥がれもよい状態か見られた。As a first test method, 3 ml of a commercial product oil was applied to each of a stainless steel plate (SUS304 thickness 0.5 mm) of about 50 cm ² (7.1 × 7.1), and 3 ml of the test solution detergent was added to each of them. Mix the test solution lightly with the same force to obtain a cloudy state. Next, water is applied to the bat, each plate is passed through the water twice, and the ratio of the remaining cleaning amount (white turbid area) to the plate is calculated. In the second test, 4 mirror surfaces (5 × 5 cm) 25 cm ² were uniformly applied using beef tallow (head), left for 3 minutes, 4 g of the test solution was dropped into this, and lightly mixed 3 Leave for about 5 to 5 minutes. Thereafter, each specimen is passed through the vat in water at 10 ° C. three times, and the residue after washing is calculated.

As a result, it was seen that the product of the present invention was in a well-dispersed state and a good oil-peeling state.

評価、本発明品はコロイダル状況を形成して、表面張力が降下し、浸透力に優れ、洗浄力がアップする結果と考察した。

Evaluation, the product of the present invention was considered to be a result of forming a colloidal situation, a decrease in surface tension, excellent penetrating power, and increased detergency.

テスト法は１０％液をとかし、分散させて１００ｍｌ注入して、常温で３０分以内静置してからその外観を比較した。
評価は官能（外観）テストにて３名によるモニターの視覚を４段階評価とした。
◎ 全く濁りなし （水と同じ）
○ 若干白い泡や未積物が停滞している
△ 少し白濁して数種の層が混在している
× 白濁し沈殿物など分離している
以上の結果から、本発明に特化、調合したものは極めて意外な結果を出すことを供試液でその数の制限を調べて記すことができた。It is clear from this result that the aqueous solution of the present invention changed into a colloidal shape and added refraction and diffuse reflection of light, and a sensory test (visual method discovered by Weber of 18th century German psychologist Weber and his disciple Feucht was found. This was done based on Feucht's Law "). Moreover, it confirmed by the following method that it was the big characteristic of hard water resistance as a 1st characteristic of this invention.

In the test method, a 10% solution was dissolved, 100 ml was dispersed and injected, and allowed to stand within 30 minutes at room temperature, and then the appearance was compared.
The evaluation was based on a 4-step evaluation of the visual perception by three persons in a sensory (appearance) test.
◎ No turbidity (same as water)
○ Slightly white bubbles and unstacked products are stagnant. △ Slightly cloudy and several layers are mixed. × Cloudy and precipitates are separated. From the above results, specialized and formulated in the present invention. It was possible to note that the result was extremely surprising with the test solution.

洗浄率はスライドガラスのマーカーが乖離している割合を目測で算出した。
（数値が大きいほどよく落ちている）
（その２）磁製皿（１０ｃｍ）にラー油＋クロロホルム（カーボンプラソで着色）で作成した汚れ液を調整して常温で６０分放置してから２０℃の水中に各供試液（本発明品６〜１０，）を円状に塗布後、各々３枚ずつ×１３枚（３９枚）を２４時間放置してから２０℃の水中に供試液（本発明品６〜１０、比較例品▲７▼〜▲１１▼、大手市販製品Ａ・Ｂ）の１０％液を侵入させて３０分つけこみ、その時の洗浄率を平均値（ｎ＝３）で示した。Using the sample created in Example 2, the following test was performed.
I. Detergency test (Part 1) 3 slides (11 types + 2 types = 13 types) each of which were colored with an oily marker (black) on a slide glass (70 x 15 mm) and left at 30 ° C for 4 hours x 3 = 39 types (n = 3) were prepared, and the test power was examined by changing the test solution to a 10-fold solution (the product of the present invention was further diluted 10-fold).

The cleaning rate was calculated by visual measurement of the rate at which the slide glass marker was dissociated.
(The larger the number, the better)
(Part 2) Prepare a soil solution prepared with lara oil + chloroform (colored with carbon plastic) on a porcelain dish (10 cm), leave it at room temperature for 60 minutes, and then put each test solution in the water at 20 ° C. 10)), and 3 x 13 sheets (39 sheets) each were allowed to stand for 24 hours, and then the test solution in the water at 20 ° C. (invention product 6-10, comparative product 7) (11) A 10% solution of a major commercial product A / B) was infiltrated for 30 minutes, and the cleaning rate at that time was shown as an average value (n = 3).

数値が大きい程洗浄力が優れている

The larger the value, the better the cleaning power

Results of surface tension drop Surface tension (Nm) (JISK-3362)
Samples for the test solution are indicated by the present invention products 5 to 9, conventional comparative products (7) to (11), 0.5% of major commercial products A and B, and n-3 of 2%.

結果、本発明の供試液６〜１０は泡切れが早いことが証明された。
本発明品は水による希釈タイプであっても、大手市販品に対しても遜色無く十分に対応出来、容器、運搬、包装資材などの減量化に寄与する事を確信した。IV Foam Test ・ Examples are products of the present invention (6 ・ 7 ・ 8 ・ 9 ・ 10), comparative products (▲ 7 ▼ ・ ▲ 8 ▼ ・ ▲ 9 ▼ ・ ▲ 10 ▼ ・ ▲ 11 ▼)・ Test method: 1 ml of the sample solution is added to 1 liter of water, and two major companies (A and B) also put 100 ml each into a measuring cylinder with a stopper, and 100 ml of this water once and twice. Each of the three times was stirred 150 times, and the situation of each type of foam was observed.

As a result, it was proved that the test liquids 6 to 10 of the present invention were quickly foamed.
Even if the product of the present invention is a dilution type with water, it is possible to cope with large commercial products without inferiority, and we are convinced that it contributes to the reduction of containers, transportation, packaging materials, etc.

Claims (3)

(1) Alkyl sulfonate having the following structural formula (hereinafter referred to as SAS)

(2) (a) × (1-5) = (b) where (b)> (a) 60-85 wt%
(3) 3 to 15 wt% of 1 to polyhydric alcohol
(4) Concentrated liquid detergent composition comprising less than about 10% water and adjusting the stock solution to pH 5-8 and comprising the essential components of the above-mentioned items (1) to (4) mainly comprising alkylsulfonate . It SAS is an alkyl sulfonates _{C 15} center (MW about 300 to 330) AA is dialkanolamide of coconut oil fatty acid.   The blending amount of SAS and AA is in the range of 60 to 85 wt%. As 1 to polyhydric alcohol, ethanol, IPA, butanol, PG, DPG, glycerin, sorbitol, pentaerythritol, maltitol, salicylic acid, gallic acid, It is selected from HG, 1-3BG, benzyl alcohol, phenoxyethanol, and diglycerin and has one or more combined use.