JP4790154B2 - Non-body cleaner - Google Patents

Description

【００２５】
実施例４（合成例４：トレハロースのドデシルエーテル体の合成）
実施例３では1-クロロドデカンを使用したが、1-ブロモドデカンを使用しても多少反応率は低下するが目的とするトレハロースのドデシルエーテル体を合成することができる。トレハロース（無水和物）３４２ｍｇとジメチルスルホキシド５ｍｌを反応容器内に加え、１００℃で３０分攪拌した後に、アルゴン雰囲気下、表２に示す水酸化カリウム及び１−ブロモドデカンを加え１００℃で３時間攪拌を行った。反応後溶液のトレハロース含量を高速液体クロマトグラフィー（HPLC）にて定量し、トレハロースの反応率を算出した。結果は表２の通りである。
【００２６】
【表２】

【００２７】
実施例５（合成例５：トレハロースのドデシルエーテル体の合成）
実施例３では溶媒としてジメチルスルホキシドを使用したが、他の極性有機溶媒を使用してもわずかではあるが目的とするトレハロースのドデシルエーテル体を合成することができる。トレハロース（無水和物）３４２ｍｇと表３に示す溶媒５ｍｌを反応容器内に加え１００℃で３０分攪拌した後に、アルゴン雰囲気下、水酸化カリウム８４ｍｇ（１．５ｍｍｏｌ）及び１−クロロドデカン１１８μｌ（０．５ｍｍｏｌ) を加え１００℃で３時間攪拌を行った。反応後溶液のトレハロース含量を高速液体クロマトグラフィー（HPLC）にて定量し、トレハロースの反応率を算出した。結果は表３の通りである。
【００２８】
【表３】

【００２９】
実施例６（合成例６：トレハロースのアルキルエーテル体の合成）
これまではトレハロースのドデシルエーテル化についてであったが、他のアルキルエーテル体も同じく合成することができる。
トレハロース（無水和物）３４２ｍｇとジメチルスルホキシド５ｍｌを反応容器内に加え、１００℃で３０分攪拌した後に、アルゴン雰囲気下、水酸化カリウム８４ｍｇ (１．５ｍｍｏｌ) 及び表４に示すアルキルクロライド０．５ｍｍｏｌを加え１００℃で３時間攪拌を行った。反応後溶液のトレハロース含量を高速液体クロマトグラフィー（HPLC）にて定量し、トレハロースの反応率を算出した。結果は表５の通りである。
【００３０】
【表４】

【００３１】
上記実施例で得られたトレハロースのアルキルエーテル体を用いて下記非身体用洗浄剤を調製した。
【００３２】
実施例７
実施例１のトレハロースドデシルエーテルを用い、下記に示す処方に従って、非身体用洗浄剤を調製した。尚、トレハロースドデシルエーテルはスプレードライヤーを用いて噴霧乾燥した微粉末を用い、製品はハイスピードカッターを用いて各成分を機械的に混合して製品とした。尚、洗浄試験の洗剤濃度としては０．１５％にて実施した。
【００３３】

【００３４】
比較例１
実施例７でトレハロースドデシルエーテルの代わりにトレハロースを用いた他は全て実施例７と同様にして製品を得た。
【００３５】
実施例８
実施例１のトレハロースドデシルエーテルを用い、下記に示す処方に従って、非身体用液体洗浄剤を調製した。尚、洗浄試験は洗浄剤を適量、汚染布に塗布して行った。
【００３６】

【００３７】
比較例２
実施例８でトレハロースの代わりに精製水を用いた他は全て実施例８と同様にして製品を得て、試験を行った。
【００３８】
実施例および比較例の評価結果を下記に示す。
【００３９】

【００４０】
上記の結果より、本発明の実施例は比較例と比べてより洗浄力に優れ，かつ洗いあがりの感触に優れていることは明らかである。
【００４１】
【発明の効果】
以上のことから、本発明は、炭素数が１〜２４であるアルキル基、または炭素数３〜２４のアルケニル基で、その平均置換数が１〜８であるトレハロースのアルキルエーテル体及び／又はトレハロースのアルケニルエーテル体およびトレハロースを含有することで、洗浄力に優れ、洗いあがりの感触に優れることを特徴とする非身体用洗浄剤が得られることは明らかである。
【図面の簡単な説明】
【図１】トレハロースドデシルエーテル体（１．１置換体）の起泡力および泡安定性試験の結果を示す図である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a non-body cleaning agent for clothes, bedding, etc., characterized by excellent detergency and excellent feeling after washing.
[0002]
[Prior art]
Conventionally, it is known that an alkyl derivative of trehalose is blended in a detergent as disclosed in JP-A-8-157491.
[0003]
[Problems to be solved by the invention]
However, there is no report on the blending properties of trehalose alkyl ether and alkenyl ether detergents, and there is no report on the use in combination with a similar compound, trehalose. On the other hand, there are few non-body cleaning agents that can satisfy the cleaning power and the feeling of washing clothes and the like.
[0004]
[Means for Solving the Problems]
The inventors of the present invention provide an alkyl ether having 1 to 24 carbon atoms or an alkenyl group having 3 to 24 carbon atoms and an average ether number of 1 to 8 and an alkyl ether of trehalose and / or an alkenyl ether of trehalose. Focusing on the fact that the body (hereinafter referred to as “trehalose alkyl ether body”) has excellent pH and thermal stability, and has good surface chemical characteristics, the results of examining the blending characteristics into the detergent, The present invention was completed by finding that a non-body cleaning agent having excellent detergency and excellent feeling of washing can be obtained by blending trehalose with a trehalose alkyl ether.
[0005]
That is, according to the first aspect of the present invention, (a) an alkyl ether body of trehalose having an alkyl group having 1 to 24 carbon atoms or an alkenyl group having 3 to 24 carbon atoms and an average substitution number of 1 to 8, and It is a non-body cleaning agent characterized by containing an alkenyl ether form of trehalose and / or (b) trehalose.
[0006]
The second aspect of the present invention is: (a) an alkyl ether having 1 to 24 carbon atoms, or an alkenyl group having 3 to 24 carbon atoms and an alkyl ether of trehalose having an average substitution number of 1 to 8 and / or A non-body cleansing agent comprising an alkenyl ether of trehalose, (b) trehalose, and (c) a non-trehalose surfactant.
[0007]
The third aspect of the present invention is: (a) an alkyl ether having 1 to 24 carbon atoms, or an alkenyl group having 3 to 24 carbon atoms and an alkyl ether of trehalose having an average substitution number of 1 to 8 and / or A non-body washing agent characterized by containing an alkenyl ether of trehalose, (b) trehalose, (c) a non-trehalose surfactant, and (d) an enzyme.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Trehalose in the present invention is also called mycose and is a non-reducing saccharide having glucose as a constituent sugar, and corresponds to 1-O-α-D-glucopyranosyl-α-D-glucopyranoside. The trehalose used for synthesis in the present invention is preferably an anhydride. In the present invention, trehalose to be blended with the detergent may be an anhydride, a hydrate, or may be blended in a premixed state with a trehalose alkyl ether or the like.
[0009]
The trehalose alkyl ether or alkenyl ether used in the non-body cleaning agent of the present invention is the trehalose alkyl ether or alkenyl ether. All or part of the eight hydroxyl groups of trehalose have hydroxyl groups. The alkyl group having 1 to 24 carbon atoms and the alkenyl group having 3 to 24 carbon atoms (aliphatic group having an unsaturated bond) are etherified and substituted, preferably 6 to 6 carbon atoms. 20 alkyl groups and alkenyl groups that are etherified and substituted and whose average substitution number is in the range of 1 to 8 can be used. An average number of substitutions of less than 1.0 is preferably within the range, meaning unpurified containing unsubstituted trehalose. Further, when the average number of substitutions is 1.2 or more, the properties as an emulsifier are exhibited although it depends on the alkyl chain length or alkenyl chain length. In this case, it can be used as a liquid detergent. In the present invention, a linear or branched alkyl group or an alkenyl group having 3 to 24 carbon atoms is substituted in the range of 1 to 24 carbon atoms. Since the effect | action as an agent can be acquired notably, it is preferable.
The number of substituents can be measured using, for example, proton NMR (each magnetic resonance spectrum).
[0010]
The method for obtaining trehalose alkyl ether and alkenyl ether in the non-body detergent of the present invention is described in detail in the examples below. For example, (1) sodium methoxy in a reaction solvent such as propylene glycol In the presence of an alkali such as sodium stearate, a surfactant such as sodium stearate, and an alkyl bromide having 1 to 24 carbon atoms, an alkyl halide such as alkyl chloride, or an alkenyl having 3 to 24 carbon atoms depending on the number of substitutions. A method of producing an ether derivative by reacting an alkenyl halide such as bromide or alkenyl chloride, (2) using sodium hydride or sodium methoxide in an aprotic solvent such as dimethyl sulfoxide or N, N-dimethylformamide. Alkoxide on the hydroxyl group of trehalose Then, an ether derivative is produced by reacting an alkyl halide such as an alkyl bromide having 1 to 24 carbon atoms or an alkyl chloride, or an alkenyl halide having 3 to 24 carbon atoms, or an alkenyl halide such as an alkenyl chloride, depending on the number of substitutions. (3) using an aprotic solvent such as dimethyl sulfoxide and N-methylpyrrolidinone, and an alkyl halide having 1 to 24 carbon atoms and / or an alkenyl halide having 3 to 24 carbon atoms according to the number of substitutions. And trehalose together with an alkali such as sodium hydroxide, potassium hydroxide, calcium oxide, or sodium alkoxide such as sodium methoxide, preferably with sodium hydroxide or potassium hydroxide, which is an alkali that provides a high reaction yield. Reacted ether derivative In particular, the production method (3) is preferable because the yield is good and a general-purpose raw material can be used as the raw material to be used, and the cost can be reduced. In all methods, it is preferable to use an inert gas such as argon or nitrogen during the reaction. Further, the situation of alkyl etherification and alkenyl etherification at this time is preferably analyzed using proton NMR after separating the obtained synthesized product with a column.
[0011]
As the conditions during the production, the reaction temperature is preferably 70 to 150 ° C. in the method (1), the reaction time is, for example, 120 ° C. for 1 to 8 hours, and the reaction temperature is preferably 20 in the method (2). ˜100 ° C., the reaction time is, for example, 45 ° C., 5-60 hours, and in the method (3), the reaction temperature is preferably 60-150 ° C., and the reaction time is, for example, 100 ° C., 1-8 hours. The raw material ratio is preferably 0.5 to 6 equivalents of alkyl halide or alkenyl halide with respect to 1 equivalent of trehalose. For the solution after the reaction is completed, the reaction solvent is removed under reduced pressure and warming conditions, etc., and the residue is precipitated by adding (1) a solvent in which ether derivatives such as ethyl acetate and toluene are not so soluble, and (2) silica gel or the like. It can be purified by a method of removing impurities using a column packed with. Unreacted trehalose can be removed by the method (2) above, and can be separated and removed using a solvent in which an ether derivative such as isopropanol dissolves and trehalose does not dissolve. If necessary, the reaction by-product salt can be removed with a desalting resin or the like.
[0012]
Examples of the dosage form of the non-body cleaning agent of the present invention include liquids, creams, gels, solids, powders, sheets and the like, clothes, bedding, kitchens, floors, baths, contact lenses, etc. Cleaning agents. In addition to the trehalose alkyl ether as an essential component, non-body detergents include conventionally known surfactants, moisturizers, preservatives, pH adjusters, chelating agents, fragrances, dyes, bleaches, salts A builder, a solvent, a sticking agent, an enzyme, a fluorescent agent, a reducing agent and the like can be appropriately blended. In particular, in the case of a non-body cleaning agent, a higher detergency is required, so that it is preferably used in combination with a non-trehalose surfactant. Furthermore, more effective cleaning can be performed when used in combination with an enzyme.
[0013]
The blending ratio when blending the alkyl ether form of trehalose and / or the alkenyl ether form of trehalose with the non-body cleanser of the present invention is 0.01 to 45% by mass relative to the total amount of the non-body cleanser. Is preferable, and 0.1 to 40% by mass is more preferable. When used as a powder or solid detergent, it is preferable to use an alkyl ether of trehalose which is spray-dried alone or as a mixture. One or more of trehalose alkyl ether and trehalose alkenyl ether can be used in combination. In addition, the blending ratio of trehalose is preferably 0.01 to 20% by mass with respect to the total amount of the non-body cleaning agent in terms of anhydride, from the viewpoint of feeling after washing.
[0014]
In the present invention, it is preferable to use a non-trehalose surfactant in combination, but as the non-trehalose surfactant, an anionic, nonionic or cationic amphoteric surfactant is used, and a nonionic surfactant is particularly preferably used. More specifically, fatty acid soap, α-acyl sulfonate, alkyl sulfonate, alkyl allyl sulfonate, alkyl naphthalene sulfonate, alkyl sulfate, alkyl ether sulfate, alkyl amide sulfate, alkyl phosphate, alkyl Anionic surfactants such as amide phosphate, linear alkylbenzene sulfonate, α-olefin sulfonate, alkyloyl alkyl taurate, N-acyl amino acid salt, sulfosuccinate, perfluoroalkyl phosphate, chloride Alkyltrimethylammonium chloride, stearyltrimethylammonium chloride, stearyltrimethylammonium bromide, cetostearyltrimethylammonium chloride, distearyldimethylammonium chloride, stearyldimethylbenzylammonium chloride, bromide Cationic surfactants such as behenyl trimethyl ammonium, nonionic surfactants such as lauric acid alkanolamide, POE sorbitan fatty acid ester, POE glycerin fatty acid ester, POE fatty acid ester, polyether-modified silicone, carboxybetaine type, amide betaine type, Examples include amphoteric surfactants such as sulfobetaine type, hydroxysulfobetaine type, amide sulfobetaine type, phosphobetaine type, aminocarboxylate type, imidazoline derivative type, and amidoamine type. Natural surfactants such as sugar surfactants such as saponins, alkyl glucosides and sugar fatty acid esters can also be used. As a compounding quantity of a non-trehalose type surfactant, 0.5-45 mass% is preferable with respect to the total amount of a formulation.
[0015]
In the present invention, it is preferable to use an enzyme in combination. However, the enzyme is not particularly limited as long as it is generally used as a detergent. For example, a proteolytic enzyme, an alkaline protease, a hydrolase, an oxidase, a reductase, a transferase, Examples include lyase, ligase, synthetase, and isomerase, and proteolytic enzymes are preferred. Moreover, it is also possible to mix | blend an enzyme stabilizer with an enzyme. As a compounding quantity of an enzyme, 0.01-3 mass% is preferable with respect to the total amount of a formulation.
[0016]
In the present invention, sodium citrate, sodium ethylenediaminetetraacetate, sodium polyacrylate, a chelating agent such as zeolite, a recontamination inhibitor such as carboxymethylcellulose and polyethylene glycol, a viscosity modifier, a quaternary ammonium salt, bentonite, A softener such as smectite can be used. Examples of the viscosity modifier include urea, ethyl alcohol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerin, diglycerin, sorbitol, malbitol, raffinose, xylitol, mannitol, hyaluronic acid and its It is also possible to use salts, glycols such as polyethylene glycol and polyglycerin, polyhydric alcohols and polysaccharides.
[0017]
Antibacterial and antiseptic agents include paraoxybenzoic acid alkyl esters, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, and the like, and antibacterial agents include benzoic acid, salicylic acid, coal acid, sorbic acid, alkyl paraoxybenzoate. Esters, parachlorometacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, triclosan, photosensitizer, phenoxyethanol, and the like can be blended.
[0018]
【Example】
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
Moreover, the evaluation method about the non-body washing | cleaning agent obtained by the Example and the comparative example is shown below.
[0019]
[Foaming power and foam stability test]
An aqueous solution of trehalose dodecyl ether (1.1-substituted product) was prepared, and its foaming power and foam stability were evaluated by the Tjujuniko-Kassjanowa method (TK method). As a test method, 5 ml of a 1.0 to 0.005 mass% aqueous solution of trehalose dodecyl ether was foamed in the apparatus for 1 minute, and the volume of the foam at that time was measured to determine the foaming power. . Moreover, it was left to stand for 5 minutes after that, the foam volume was measured again, and this was made into foam stability. The results are shown in FIG.
[0020]
[Evaluation method of cleaning power and feel]
Eriaka contaminated cloth was produced according to JISK3371. The clothing was worn for 2 days.
The detergency test was performed by a method of evaluating the degree of soiling by visual judgment after the above-mentioned Eriaka contaminated cloth was washed using a stirring type detergency tester. Moreover, the touch of the contaminated cloth when touched with a hand was evaluated using a panel.
[0021]
Example 1 (Synthesis Example 1: Synthesis of dodecyl ether form of trehalose)
In a 200 ml eggplant flask dried inside under reduced pressure, 1.53 g of sodium stearate, 3.42 g of trehalose (anhydrous), 20 ml of propylene glycol (dried with molecular sieve), 1-bromododecane 4 .79 ml and sodium methoxide 1.08 g were added, and the mixture was stirred at 120 ° C. for 3 hours under an argon atmosphere.
The reaction solution was heated to 130 ° C. under reduced pressure to remove most of propylene glycol and the like, isopropanol was added to the residue, and the mixture was refluxed at 90 ° C. for 2 hours. After filtration of the suspension, the filtrate was concentrated and purified by silica gel flash chromatography to obtain 412 mg of white crystals. When this sample was dissolved in heavy water and proton NMR was measured, it was confirmed that it was a dodecyl ether of trehalose in which a dodecyl group was bonded to any one of the eight hydroxyl groups of a trehalose molecule by an ether bond. .
[0022]
Example 2 (Synthesis Example 2: Synthesis of dodecyl ether form of trehalose)
After adding 200 mg of sodium hydride and 10 ml of dimethyl sulfoxide to an absolutely dried 200 ml eggplant flask, 1.71 g of trehalose (anhydrous) dissolved in 12 ml of dimethyl sulfoxide was added. After 3 hours, 1.71 g of trehalose (anhydrous) dissolved in 12 ml of dimethyl sulfoxide was added to the homogenized solution, and then 1.2 ml of 1-bromododecane was gradually added dropwise and stirred at 45 ° C. for 43.5 hours. .
The reaction solution was extracted by adding n-hexane and methanol, and most of methanol and dimethyl sulfoxide were removed while heating the methanol phase to 110 ° C. under reduced pressure. Isopropanol was added to the residue and refluxed at 90 ° C. for 4 hours, followed by filtration. The filtrate was concentrated and purified by silica gel flash chromatography to obtain 1.535 g of cream crystals. The number of substituted dodecyl groups was 1-4.
[0023]
Example 3 (Synthesis Example 3: Synthesis of dodecyl ether form of trehalose)
According to the following reaction method, synthesis of dodecyl trehalose was attempted by changing the alkali used, the amount used, and 1-chlorododecane and the amount used as shown in Table 2. 342 mg of trehalose (anhydrous) and 5 ml of dimethyl sulfoxide were added to the reaction vessel and stirred at 100 ° C. for 30 minutes, and then each alkali and 1-chlorododecane were added in an argon atmosphere and stirred at 100 ° C. for 3 hours. The trehalose content of the solution after the reaction was quantified by high performance liquid chromatography (HPLC), and the reaction rate of trehalose was calculated. The results are shown in Table 1. KOH and NaOH were used in the form of pellets that were lightly crushed with a mortar.
[0024]
[Table 1]

[0025]
Example 4 (Synthesis Example 4: Synthesis of dodecyl ether form of trehalose)
In Example 3, 1-chlorododecane was used, but even if 1-bromododecane was used, the desired trehalose dodecyl ether can be synthesized although the reaction rate is somewhat reduced. 342 mg of trehalose (anhydrous) and 5 ml of dimethyl sulfoxide were added to the reaction vessel and stirred at 100 ° C. for 30 minutes, and then added with potassium hydroxide and 1-bromododecane shown in Table 2 in an argon atmosphere at 100 ° C. for 3 hours. Stirring was performed. The trehalose content of the solution after the reaction was quantified by high performance liquid chromatography (HPLC), and the reaction rate of trehalose was calculated. The results are shown in Table 2.
[0026]
[Table 2]

[0027]
Example 5 (Synthesis Example 5: Synthesis of dodecyl ether form of trehalose)
In Example 3, dimethyl sulfoxide was used as a solvent, but the desired trehalose dodecyl ether can be synthesized even if other polar organic solvents are used. After adding 342 mg of trehalose (anhydrate) and 5 ml of the solvent shown in Table 3 to the reaction vessel and stirring at 100 ° C. for 30 minutes, 84 mg (1.5 mmol) of potassium hydroxide and 118 μl of 1-chlorododecane (0 0.5 mmol) was added and the mixture was stirred at 100 ° C. for 3 hours. The trehalose content of the solution after the reaction was quantified by high performance liquid chromatography (HPLC), and the reaction rate of trehalose was calculated. The results are shown in Table 3.
[0028]
[Table 3]

[0029]
Example 6 (Synthesis Example 6: Synthesis of alkyl ether form of trehalose)
Until now, it was about dodecyl etherification of trehalose, but other alkyl ethers can be synthesized as well.
342 mg of trehalose (anhydrous) and 5 ml of dimethyl sulfoxide were added to the reaction vessel and stirred at 100 ° C. for 30 minutes. Then, under an argon atmosphere, 84 mg (1.5 mmol) of potassium hydroxide and 0.5 mmol of alkyl chloride shown in Table 4 were used. And stirred at 100 ° C. for 3 hours. The trehalose content of the solution after the reaction was quantified by high performance liquid chromatography (HPLC), and the reaction rate of trehalose was calculated. The results are shown in Table 5.
[0030]
[Table 4]

[0031]
The following non-body cleaning agents were prepared using the trehalose alkyl ethers obtained in the above examples.
[0032]
Example 7
Using the trehalose dodecyl ether of Example 1, a non-body washing agent was prepared according to the formulation shown below. For trehalose dodecyl ether, fine powder spray-dried using a spray dryer was used, and the product was obtained by mechanically mixing each component using a high-speed cutter. The detergent concentration in the cleaning test was 0.15%.
[0033]

[0034]
Comparative Example 1
A product was obtained in the same manner as in Example 7 except that trehalose was used instead of trehalose dodecyl ether in Example 7.
[0035]
Example 8
Using the trehalose dodecyl ether of Example 1, a non-body liquid detergent was prepared according to the formulation shown below. The cleaning test was performed by applying an appropriate amount of a cleaning agent to a contaminated cloth.
[0036]

[0037]
Comparative Example 2
A product was obtained and tested in the same manner as in Example 8 except that purified water was used instead of trehalose in Example 8.
[0038]
The evaluation results of Examples and Comparative Examples are shown below.
[0039]

[0040]
From the above results, it is clear that the examples of the present invention are superior in cleaning power and feel in washing up as compared with the comparative examples.
[0041]
【The invention's effect】
From the above, the present invention is an alkyl ether of trehalose and / or trehalose having an alkyl group having 1 to 24 carbon atoms or an alkenyl group having 3 to 24 carbon atoms and an average substitution number of 1 to 8. It is apparent that a non-body cleaning agent characterized by having an excellent detergency and a feeling of being washed out can be obtained by containing the alkenyl ether body and trehalose.
[Brief description of the drawings]
FIG. 1 is a graph showing the results of foaming ability and foam stability test of trehalose dodecyl ether (1.1-substituted product).

Claims (3)

(A) an alkyl ether having 1 to 24 carbon atoms, or an alkenyl group having 3 to 24 carbon atoms and an average substitution number of 1 to 8 and an alkyl ether form of trehalose and / or an alkenyl ether form of trehalose, ( b) A non-body cleaning agent containing trehalose. (A) an alkyl ether having 1 to 24 carbon atoms or an alkenyl group having 3 to 24 carbon atoms and an average substitution number of 1 to 8 and an alkyl ether of trehalose and / or an alkenyl ether of trehalose, ( A non-body cleaning agent comprising b) trehalose and (c) a non-trehalose surfactant. (A) an alkyl ether having 1 to 24 carbon atoms, or an alkenyl group having 3 to 24 carbon atoms and an average substitution number of 1 to 8 and an alkyl ether form of trehalose and / or an alkenyl ether form of trehalose, ( A non-body cleansing agent comprising: b) trehalose, (c) a non-trehalose surfactant, and (d) an enzyme.

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