JP2019172764A - Liquid detergent composition - Google Patents

Abstract

To provide a liquid detergent composition that exhibits high detergency without applying heat or physical force.SOLUTION: Provided is a liquid detergent composition comprising (A) component, (B) component and (C) component, and in which the (A) component is an anionic surfactant, the (B) component is a particular compound, the (C) component is at least one selected from the group consisting of amphoteric surfactant and amine oxide-type surfactant, and the mass ratio represented by the (A) component/(B) component is 0.06 to 45.SELECTED DRAWING: None

Description

  The present invention relates to a liquid detergent composition.

  As a method of washing the objects to be washed such as tableware and cooking utensils (hereinafter generally referred to as “tableware”), a liquid cleaning agent is directly taken in a washing tool such as a sponge and the objects to be washed are rubbed with the washing tool. Alternatively, a method of preparing a diluted solution by diluting a dishwashing detergent with water, taking the diluted solution in a cleaning tool such as a sponge, and rubbing the object to be washed with the cleaning tool can be used.

  For example, Patent Literature 1 proposes a hard surface cleaning composition containing a specific acetal derivative, a surfactant, a builder, and water. According to the composition of patent document 1, a high detergency can be exhibited.

JP-A-8-3590

  However, with the liquid cleaning agent of Patent Document 1, it is necessary to rub the object to be cleaned in order to exhibit high cleaning power.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid detergent composition that exhibits high detergency without applying heat or physical force.

式（Ｂ−Ｉ）中、Ｒ^１は炭素数１〜１４の直鎖のアルキル基、炭素数１〜１４の分岐鎖のアルキル基、炭素数１〜１４の直鎖のアルケニル基、炭素数１〜１４の分岐鎖のアルケニル基、炭素数１〜１４の直鎖のヒドロキシアルキル基、炭素数１〜１４の分岐鎖のヒドロキシアルキル基、又は水素であり、Ｒ^２、及びＲ^３はそれぞれ独立に、炭素数１〜５の直鎖のアルキル基、炭素数１〜５の分岐鎖のアルキル基、炭素数１〜５の直鎖のアルケニル基、炭素数１〜５の分岐鎖のアルケニル基、又は水素である。
［２］ 前記（Ａ）成分が、下記式（Ａ−Ｉ）で表される化合物（Ａ１）、及び下記式（Ａ−ＩＩ）で表される化合物（Ａ２）からなる群から選択される少なくとも１種を含む、［１］に記載の液体洗浄剤組成物。
Ｒ^４−Ｏ−［（ＰＯ）_ｐ／（ＥＯ）_ｑ］−ＳＯ_３ ⁻ １／Ｘ・Ｍ^＋ ・・・（Ａ−Ｉ）
Ｒ^５−Ｃ_６Ｈ_４−ＳＯ_３ ⁻ １／Ｙ・Ｚ^＋ ・・・（Ａ−ＩＩ）
式（Ａ−Ｉ）中、Ｒ^４は炭素数８〜１８の直鎖又は分岐鎖のアルキル基を表し；ＰＯはオキシプロピレン基を表し；ＥＯはオキシエチレン基を表し；ｐはＰＯの平均繰り返し数を表し、０≦ｐ≦１であり；ｑはＥＯの平均繰り返し数を表し、０≦ｑ≦５であり；［（ＰＯ）_ｐ／（ＥＯ）_ｑ］においてＥＯ及びＰＯはランダム付加であってもよくブロック付加であってもよく；Ｍ^＋は対イオンであり；ＸはＭ^＋の価数である。
式（Ａ−ＩＩ）中、Ｒ^５は、炭素数８〜１８の直鎖又は分岐鎖のアルキル基を表し；Ｚ^＋は対イオンであり；ＹはＺ^＋の価数である。
［３］ 前記（Ｂ）成分が、前記式（Ｂ−Ｉ）中、Ｒ^１が炭素数１〜１４の直鎖のヒドロキシアルキル基、又は炭素数１〜１４の分岐鎖のヒドロキシアルキル基を表し；Ｒ^２、及びＲ^３はそれぞれ独立に炭素数１〜５の直鎖のアルキル基、又は炭素数１〜５の分岐鎖のアルキル基を表す化合物（Ｂ１）を含有する、［１］又は［２］に記載の液体洗浄剤組成物。
［４］ さらにノニオン界面活性剤（Ｄ）を含む、［１］〜［３］のいずれか一項に記載の液体洗浄剤組成物。
［５］ 前記（Ｄ）成分が、下記式（Ｄ−Ｉ）で表される化合物（Ｄ１）を含む、［４］に記載の液体洗浄剤組成物。
Ｒ^１１−Ｘ−［（ＥＯ）_ｓ／（ＰＯ）_ｔ］−Ｒ^１２ ・・・（Ｄ−Ｉ）
式（Ｄ−Ｉ）中、Ｒ^１１は炭素数６〜２２の炭化水素基を表し；Ｘは２価の連結基を表し；Ｒ^１２は水素原子、炭素数１〜６のアルキル基又は炭素数２〜６のアルケニル基を表し、ＥＯはオキシエチレン基を表し、ＰＯはオキシプロピレン基を表し、ｓはＥＯの平均繰り返し数を表し、３〜１００の数であり、ｔはＰＯの平均繰り返し数を表し、０〜６の数であり、［（ＥＯ）_ｓ／（ＰＯ）_ｔ］においてＥＯ及びＰＯはランダム付加であってもよくブロック付加であってもよい。
［６］ 前記（Ｄ）成分／前記（Ｂ）成分で表される質量比が３〜１００である、［４］又は［５］に記載の液体洗浄剤組成物。
［７］［１］〜［６］のいずれか一項に記載の液体洗浄剤組成物が、容器に収容されてなる、液体洗浄剤組成物製品。 The liquid detergent composition of the present invention includes the following aspects.
[1] Including (A) component, (B) component, and (C) component,
The component (A) is an anionic surfactant,
The component (B) is a compound represented by the following formula (BI),
The component (C) is at least one selected from the group consisting of amphoteric surfactants and amine oxide surfactants,
The liquid detergent composition whose mass ratio represented by said (A) component / said (B) component is 0.06-45.

In Formula (BI), R ¹ is a linear alkyl group having 1 to 14 carbon atoms, a branched alkyl group having 1 to 14 carbon atoms, a linear alkenyl group having 1 to 14 carbon atoms, or 1 carbon atom. A branched chain alkenyl group having 1 to 14 carbon atoms, a linear hydroxyalkyl group having 1 to 14 carbon atoms, a branched chain hydroxyalkyl group having 1 to 14 carbon atoms, or hydrogen, and R ² and R ³ are each independently A linear alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 1 to 5 carbon atoms, a linear alkenyl group having 1 to 5 carbon atoms, a branched alkenyl group having 1 to 5 carbon atoms, or Hydrogen.
[2] The component (A) is at least selected from the group consisting of the compound (A1) represented by the following formula (AI) and the compound (A2) represented by the following formula (A-II). The liquid detergent composition according to [1], comprising one kind.
_{^{R 4 -O - [(PO)}} p / (EO) q] -SO 3 - 1 / X · M + ··· (A-I)
R ⁵ —C ₆ H ₄ —SO ₃ ^— 1 / Y · Z ⁺ ... (A-II)
In formula (AI), R ⁴ represents a linear or branched alkyl group having 8 to 18 carbon atoms; PO represents an oxypropylene group; EO represents an oxyethylene group; p represents an average repeat of PO Q represents the average number of repetitions of EO and 0 ≦ q ≦ 5; in [(PO) _p / (EO) _q ], EO and PO were random additions. It may be a block addition; M ⁺ is a counter ion; and X is the valence of M ⁺ .
In formula (A-II), R ⁵ represents a linear or branched alkyl group having 8 to 18 carbon atoms; Z ⁺ is a counter ion; Y is a valence of Z ⁺ .
[3] the component (B) represents the formula (B-I) in a linear hydroxyalkyl group of ^{R 1} is 1 to 14 carbon atoms, or a hydroxyalkyl group of branched 1 to 14 carbon atoms Each of R ² and R ³ independently contains a compound (B1) representing a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 1 to 5 carbon atoms, [1] or [ 2].
[4] The liquid detergent composition according to any one of [1] to [3], further comprising a nonionic surfactant (D).
[5] The liquid detergent composition according to [4], wherein the component (D) includes a compound (D1) represented by the following formula (DI).
_{^{R 11 -X - [(EO)}} s / (PO) t] -R 12 ··· (D-I)
In the formula (DI), R ¹¹ represents a hydrocarbon group having 6 to 22 carbon atoms; X represents a divalent linking group; R ¹² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number Represents an alkenyl group of 2 to 6, EO represents an oxyethylene group, PO represents an oxypropylene group, s represents an average number of repetitions of EO, is a number of 3 to 100, and t is an average number of repetitions of PO Represents a number from 0 to 6, and in [(EO) _s / (PO) _t ], EO and PO may be random addition or block addition.
[6] The liquid detergent composition according to [4] or [5], wherein a mass ratio represented by the component (D) / the component (B) is 3 to 100.
[7] A liquid detergent composition product, wherein the liquid detergent composition according to any one of [1] to [6] is contained in a container.

  The liquid detergent composition of the present invention can exhibit high detergency without applying heat or physical force.

It is a front view which shows an example of the liquid cleaning composition product of this invention. It is a front view which shows the other example of the liquid cleaning composition product of this invention.

≪Liquid detergent composition≫
The liquid detergent composition of the present invention comprises (A) component, (B) component, and (C) component.

<(A) component>
The component (A) is an anionic surfactant. Specifically, linear alkylbenzene sulfonate, α-sulfo fatty acid ester salt, α-olefin sulfonate; linear or branched alkyl sulfate ester salt; linear or branched alkyl ether sulfate ester or alkenyl Ether sulfate ester salt; linear or branched alkane sulfonate, and the like. Examples of these salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as magnesium, and alkanolamine salts such as monoethanolamine and diethanolamine.

The component (A) includes at least one selected from the group consisting of the compound (A1) represented by the following formula (AI) and the compound (A2) represented by the following formula (A-II). It is preferable.
^{_{R 4 -O - [(PO)}} p / (EO) q] -SO 3 - 1 / X · M + ··· (A-I)
R ⁵ —C ₆ H ₄ —SO ₃ ^— 1 / Y · Z ⁺ ... (A-II)
In formula (AI), R ⁴ represents a linear or branched alkyl group having 8 to 18 carbon atoms; PO represents an oxypropylene group; EO represents an oxyethylene group; p represents an average repeat of PO Q represents the average number of repetitions of EO and 0 ≦ q ≦ 5; in [(PO) _p / (EO) _q ], EO and PO were random additions. It may be a block addition; M ⁺ is a counter ion; and X is the valence of M ⁺ .
In formula (A-II), R ⁵ represents a linear or branched alkyl group having 8 to 18 carbon atoms; Z ⁺ is a counter ion; Y is a valence of Z ⁺ .

In formula (AI), R ⁴ is a linear or branched alkyl group having 8 to 18 carbon atoms, preferably 10 to 16 carbon atoms, more preferably 12 to 14 carbon atoms. R ⁴ is preferably an alkyl group derived from a vegetable oil raw material in terms of detergency and environment. Suitable fats and oils include palm kernel oil, coconut oil and the like.
p represents the average number of repetitions of PO, 0 ≦ p ≦ 1, and more preferably p = 0.
q represents the average number of repetitions of EO, 0 ≦ q ≦ 5, preferably 0 ≦ q ≦ 4, and more preferably 0 ≦ q ≦ 2.
M ⁺ is a counter ion. For example, any ion that is an alkali metal, alkaline earth metal, ammonium, or alkanolamine ion that can form a water-soluble salt may be used. Examples of the alkali metal include sodium and potassium. Examples of the alkaline earth metal include calcium, magnesium, and zinc. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine.
X is the valence of M ⁺ and is preferably 1 to 2.

In formula (A-II), R ⁵ is a linear or branched alkyl group having 8 to 18 carbon atoms, preferably 10 to 14 carbon atoms.
Z ⁺ is a counter ion, and examples thereof include those described for M ⁺ .
Y is the valence of Z ⁺ and is preferably 1 or 2.

  Specific examples of the component (A) include linear alkyl (C10-14) benzenesulfonic acid sodium salt, polyoxyethylene (1) linear alkyl (C12) sulfate ester sodium salt, polyoxyethylene (2) linear alkyl (C12) sulfate sodium salt, polyoxyethylene (3) linear alkyl (C12) sulfate sodium salt, polyoxypropylene (0.4) polyoxyethylene (1.5) linear alkyl (C12) sodium sulfate Salt, polyoxyethylene (1) linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) sulfate sodium salt, polyoxyethylene (2) linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) ) Sodium sulfate ester salt, polyoxyethylene (3) linear alkyl (C12 / 1 = 75/25; derived from natural fats and oils) sulfate sodium salt, polyoxypropylene (0.4) polyoxyethylene (1.5) linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) sulfate sodium salt Etc.

Especially, since the effect of the present invention is particularly easily obtained, linear alkyl (C10-14) benzenesulfonic acid sodium salt, polyoxyethylene (1) linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) ) Sulfate sodium salt, polyoxyethylene (2) linear alkyl (C12 / 14 = 75/25; derived from natural fats and oils) Sulfate sodium salt, polyoxyethylene (3) linear alkyl (C12 / 14 = 75/25 Preferably derived from natural fats and oils) sodium sulfate ester salt and alkyl (C12) sodium sulfate ester salt.
Here, for example, “polyoxyethylene (1)” means that the average number of repeating oxyethylene groups is 1 (the average number of added moles of ethylene oxide is 1).
“C12 / 14 = 75/25; derived from natural fats and oils” means a mixture of a compound having a linear alkyl group having 12 carbon atoms and a compound having a linear alkyl group having 14 carbon atoms (mixing ratio: by mass ratio). 75/25) and a linear alkyl group derived from natural fats and oils.

(A) A component may be used individually by 1 type and may use 2 or more types together.
(A) As for content of a component, 0.5-30 mass% is preferable with respect to the total mass of a liquid detergent composition, 1-20 mass% is more preferable, and 3-10 are more preferable.
When the content of the component (A) is within the above range, the penetrating power against dirt is easily improved, and the usability is easily improved.

<(B) component>
The component (B) is a compound represented by the following general formula (BI).

In Formula (BI), R ¹ is a linear alkyl group having 1 to 14 carbon atoms, a branched alkyl group having 1 to 14 carbon atoms, a linear alkenyl group having 1 to 14 carbon atoms, or 1 carbon atom. A branched chain alkenyl group having 1 to 14 carbon atoms, a linear hydroxyalkyl group having 1 to 14 carbon atoms, a branched chain hydroxyalkyl group having 1 to 14 carbon atoms, or hydrogen, and R ² and R ³ are each independently A linear alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 1 to 5 carbon atoms, a linear alkenyl group having 1 to 5 carbon atoms, a branched alkenyl group having 1 to 5 carbon atoms, or Hydrogen.

Component (B), expressed in the formula (B-I), a linear hydroxyalkyl group of ^{R 1} is 1 to 14 carbon atoms, or a hydroxyalkyl group of branched carbon atoms 1 to 14; ^{R 2} and, Preferably, each R ³ independently contains a compound (B1) representing a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 1 to 5 carbon atoms.

Specific examples of the component (B) include 1,3-dioxolane, 2-methyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane, 2,2-dimethyl-1,3-dioxolane- 4-methanol, 2-isobutyl-2-methyl-1,3-dioxolane-4-methanol, 2,2-dimethyl-1,3-dioxolane-4-ethanol, 2,2-dimethyl-1,3-dioxolane- 4-propanol, 2,2-dimethyl-1,3-dioxolane-4-butanol, 2,2-dimethyl-1,3-dioxolane-4-pentanol, 2,2-dimethyl-1,3-dioxolane-4 -Hexanol, 2,2-dimethyl-1,3-dioxolane-4-heptanol, 2-isobutyl-2-methyl-1,3-dioxolane-4-propanol, 2-iso Tyl-2-methyl-1,3-dioxolane-4-butanol, 2-isobutyl-2-methyl-1,3-dioxolane-4-pentanol, 2-isobutyl-2-methyl-1,3-dioxolane-4 -Hexanol, 2-isobutyl-2-methyl-1,3-dioxolane-4-heptanol and the like.
Of these, 2-isobutyl-2-methyl-1,3-dioxolane-4-methanol and 2,2-dimethyl-1,3-dioxolane-4-methanol are preferred because the effects of the present invention are particularly easily obtained. .

(B) A component may be used individually by 1 type and may use 2 or more types together.
The content of the component (B) is preferably 0.2 to 8% by mass, more preferably 0.5 to 6% by mass, and still more preferably 1 to 4% by mass with respect to the total mass of the liquid detergent composition. .
When the content of the component (B) is within the above range, it is easy to improve the penetrating power against dirt.

The mass ratio (hereinafter also referred to as “A / B ratio”) represented by component (A) / component (B) is 0.06 to 45, preferably 0.4 to 16, and 1 to 7.5. More preferred.
When the A / B ratio is within the above range, it is easy to improve the permeation cleaning power against dirt.

<(C) component>
Component (C) is at least one selected from the group consisting of amphoteric surfactants and amine oxide surfactants.
Examples of amphoteric surfactants include betaine-type surfactants such as alkyldimethylaminoacetic acid betaine, fatty acid amidopropyldimethylaminoacetic acid betaine, alkylhydroxysulfobetaine, and fatty acid amidohydroxysulfobetaine.
Among them, a betaine amphoteric acid selected from the group consisting of fatty acid (8 to 22 carbon atoms) amidopropyldimethylaminoacetic acid betaine and fatty acid (8 to 22 carbon atoms) amidopropylhydroxysulfobetaine having a fatty acid amide group. A surfactant is preferred.
As fatty acid (carbon number 8 or more, 22 or less) amidopropyldimethylaminoacetic acid betaine, lauric acid amidopropyldimethylaminoacetic acid betaine and coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine are more preferable.
As the component (C), a betaine amphoteric surfactant having an alkyl group having preferably 8 to 22 carbon atoms, more preferably 10 to 18 carbon atoms, and further preferably 12 to 16 carbon atoms is preferable.
Specifically, lauric acid amidopropyldimethylaminoacetic acid betaine (Energy Coal L-30B, manufactured by Lion), coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine (Tego Betaine L7, manufactured by Evonic) and the like can be mentioned.

As the amphoteric surfactant, a compound represented by the following general formula (CI) is preferably used.
_{^{R 2 - (A) p -N}} + (-R 3) (- R 4) -R 5 -R 6 ... (C-I)
In the formula (CI), R ² represents a linear or branched alkyl group having 8 to 18 carbon atoms, and R ³ and R ⁴ are each independently an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms. A represents —C═O (—NH—X) —, X represents an alkylene group having 1 to 4 carbon atoms, p is a number of 0 or 1, and R ⁵ represents 1 to 2 carbon atoms. And R ⁶ represents —CO ₂ ^— or —SO ₃ ^— .

  Examples of the amine oxide type surfactant include alkylamine oxide and alkylamidopropyldimethylamine oxide. Of these, preferred are compounds represented by the following formula (C-II).

In the formula (C-II), R ¹⁰ is a linear alkyl group having 8 to 18 carbon atoms, a branched alkyl group having 8 to 18 carbon atoms, a linear alkenyl group having 8 to 18 carbon atoms, or A branched alkenyl group having 8 to 18 carbon atoms, and R ⁷ and R ⁸ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms; ⁹ is an alkylene group having 1 to 4 carbon atoms, B is —CONH—, —NHCO—, —COO—, —OCO— or —O—, and r is a number of 0 or 1.

In the alkyl group and alkenyl group of R ¹⁰ , the carbon number is 8 to 18, and preferably 10 to 14.
R ⁷ and R ⁸ are each independently an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. . R ⁷ and R ⁸ are more preferably both methyl groups.
r is a number of 0 or 1, and 0 is preferable.

  Specific examples of the amine oxide surfactant include lauryl dimethyl amine oxide, coconut alkyl dimethyl amine oxide, lauryl diethyl amine oxide, and alkyl dimethyl amine oxides such as n-dodecyl dimethyl amine oxide; lauric acid amide propyl amine oxide, etc. And alkanoylamidoalkyldimethylamine oxides. Of these, alkyldimethylamine oxides are more preferable.

(C) A component may be used individually by 1 type and may use 2 or more types together.
The content of the component (C) is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, and 0.2 to 1% by mass with respect to the total mass of the liquid detergent composition. Further preferred.
When the content of the component (C) is within the above range, it is easy to improve the permeation cleaning power against dirt.

<(D) component>
Component (D) is a nonionic surfactant.
As the component (D), polyoxyalkylene type nonionic surfactant, alkylphenol, alkylene oxide adduct such as higher amine, polyoxyethylene polyoxypropylene block copolymer, fatty acid alkanolamine, fatty acid alkanolamide, polyhydric alcohol fatty acid ester or The alkylene oxide adduct, polyhydric alcohol fatty acid ether, alkyl (or alkenyl) amine oxide, alkylene oxide adduct of hydrogenated castor oil, sugar fatty acid ester such as sorbitan fatty acid ester, N-alkyl polyhydroxy fatty acid amide, alkyl glycoside, etc. Can be mentioned.

Among these, the component (D) is preferably a polyoxyalkylene type nonionic surfactant in terms of viscosity and liquid stability.
Examples of the polyoxyalkylene type nonionic surfactant include a compound represented by the following general formula (DI) (hereinafter sometimes referred to as “compound (D1)”).
^{_{R 11 -X - [(EO)}} s / (PO) t] -R 12 ··· (D-I)

In the formula (DI), R ¹¹ is a hydrocarbon group having 6 to 22 carbon atoms, X is a divalent linking group, R ¹² is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number. 2 to 6 alkenyl groups, EO represents an oxyethylene group, PO represents an oxypropylene group, s represents an average number of repetitions of EO, is a number of 3 to 100, and t is an average number of repetitions of PO Represents a number from 0 to 6.

In formula (DI), the carbon number of the hydrocarbon group for R ¹¹ is 6 to 22, preferably 8 to 22, and more preferably 10 to 18. The hydrocarbon group for R ¹¹ may be linear or branched, and may or may not have an unsaturated bond.
Examples of —X— include —O—, —COO—, —CONH— and the like.
The number of carbon atoms of the alkyl group in R ¹² is 1 to 6, 1 to 3 are preferred.
The number of carbon atoms of the alkenyl group for R ¹² is 2-6, preferably 2-3.

The compound (D1) in which —X— is —O—, —COO— or —CONH— is a primary or secondary higher alcohol (R ¹¹ —OH), higher fatty acid (R ¹¹ —COOH) or higher obtain a fatty acid amide ^(R 11 -CONH) as a raw material. ^{R 11} in these raw materials is the same as ^{R 11} in formula (D-I).

s is the number of 3-100 showing the average repeating number (namely, average addition mole number of ethylene oxide) of EO, and 5-50 are preferable. If the value exceeds the upper limit, the HLB value becomes too high, and the cleaning power against oil stains may be reduced. If it is less than the said lower limit, there exists a possibility of producing deterioration of the raw material odor of (D) component itself.
t is a number from 0 to 6 representing the average number of repetitions of PO (that is, the average number of moles of propylene oxide added), preferably 0 to 3. If it exceeds the above upper limit, the liquid stability of the cleaning composition at a high temperature tends to decrease.

  When t is 1 or more, that is, when compound (D1) has EO and PO, the addition method of ethylene oxide and propylene oxide is not particularly limited, and for example, a random addition method or a block addition method may be used. Block addition methods include, for example, a method of adding propylene oxide after adding ethylene oxide, a method of adding propylene oxide after adding propylene oxide, a method of adding ethylene oxide, adding propylene oxide, and then adding ethylene oxide. The method of doing is mentioned.

As the compound (D1), in particular, a compound in which —X— is —O— (alcohol type nonionic surfactant), or —X— is —COO—, and R ¹² is an alkyl having 1 to 6 carbon atoms. And a compound (fatty acid alkyl (alkenyl) ester) which is a group or an alkenyl group having 2 to 6 carbon atoms is preferred.

If -X- is ^-O-, and the carbon number of ^{R 11} is preferably 10 to 22, more preferably from 10 to 20, more preferably 10 to 18. When -X- is -O-, R ¹² is preferably a hydrogen atom.

If -X- is ^-COO-, the carbon number of ^{R 11} is preferably 9 to 21, 11 to 21 is more preferable. When -X- is -COO-, R ¹² is preferably an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

  As the compound (D1) in which —X— is —O— or —COO—, for example, Diadol (trade name, C13 (C represents the number of carbon atoms; the same shall apply hereinafter) manufactured by Mitsubishi Chemical Corporation), Shell, Inc. 12 mol equivalent or 15 mol equivalent of ethylene oxide was added to alcohol such as Neodol (trade name, mixture of C12 and C13) manufactured by Sasol and Safol 23 (trade name, mixture of C12 and C13) manufactured by Sasol. A product obtained by adding 12 or 15 moles of ethylene oxide to a natural alcohol such as CO-1214 or CO-1270 (trade name) manufactured by Procter & Gamble Co .; obtained by trimerizing butene 7 mole equivalent of ethylene oxide was added to C13 alcohol obtained by subjecting the resulting C12 alkene to the oxo process. (Trade name: Lutensol TO7, manufactured by BASF); 9 mol equivalent of ethylene oxide added to C10 alcohol obtained by subjecting pentanol to garvet reaction (trade name: Lutensol XP90, manufactured by BASF); 7 mol equivalent of ethylene oxide added to C10 alcohol obtained by subjecting pentanol to garvet reaction (trade name: Lutensol XL70, manufactured by BASF); C10 alcohol obtained by subjecting pentanol to garvet reaction In contrast, 6 mole equivalent of ethylene oxide added (trade name: Lutensol XA60, manufactured by BASF); 5 mole equivalent, 7 mole equivalent or 9 mole equivalent or a secondary alcohol having 12 to 14 carbon atoms 15 moles of ethylene oxide (Product name: Softanol 50, Softanol 70, Softanol 90, Softanol 150, manufactured by Nippon Shokubai Co., Ltd.); Palm fatty acid methyl (lauric acid / myristic acid = 8/2) is alkoxylated Examples include those obtained by adding 15 moles of ethylene oxide (polyoxyethylene coconut fatty acid methyl ester (EO 15 moles)) using a catalyst.

(D) A component may be used individually by 1 type and may use 2 or more types together.
When the liquid detergent composition of the present invention contains the component (D), the content of the component (D) is preferably 0.02 to 0.5% by mass with respect to the total mass of the liquid detergent composition, 0.04-0.3 mass% is more preferable, and 0.06-0.2 mass% is further more preferable.
When the content of the component (D) is within the above range, sufficient penetrating detergency can be easily obtained simply by contacting the dirt for a short time.

When the liquid detergent composition of the present invention contains the component (D), the mass ratio represented by the component (D) / component (B) (hereinafter also referred to as “D / B ratio”) is preferably 3 to 105. 5.5 to 52 is more preferable, and 9 to 34 is more preferable.
When the D / B ratio is within the above range, sufficient penetrating detergency can be easily obtained simply by contacting the dirt for a short time.

<Other ingredients>
The liquid detergent composition of the present invention may contain optional components other than the components (A) to (D). The type and amount of the optional component are not particularly limited as long as they do not impair the gist of the present invention, and components blended in a known liquid detergent can be applied. Examples of such optional components include thickening polymers, liquid stabilizers, pH adjusters, and water.

  Examples of the thickening polymer include cellulose, polycarboxylic acid, polyacrylic acid, polyamine, polyalkyleneimine, and starch. Among these, from the viewpoint of usability, a cellulose polymer is preferable, and a carboxymethyl cellulose polymer is more preferable.

  Examples of the liquid stabilizer include citric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, gluconic acid, ascorbic acid, methylglycine diacetic acid, iminodisuccinic acid, and glutamic acid diacetic acid. You may use as a salt type | mold, In that case, as a kind of counterion, transition metals, such as alkali metals, such as sodium, alkaline-earth metals, such as magnesium, and zinc are mentioned. Among these, from the viewpoint of liquid stability, citric acid or a salt thereof is preferable, and in the case of a salt form, the counter ion is more preferably sodium.

  Examples of the pH adjuster include sodium hydroxide, hydrochloric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, monoethanolamine, diethanolamine, triethanolamine, and ammonia.

The pH of the liquid detergent composition of the present invention at 25 ° C. is preferably 6 or more, more preferably 8 or more, and still more preferably 10 or more. When the pH is within the above range, the liquid stability is maintained and the permeation cleaning power against dirt is easily improved.
Further, the pH is preferably 12.5 or less from the viewpoint of safety.
In this invention, pH (25 degreeC) of a liquid cleaning composition shows the value measured by the method based on JISZ8802: 1984 "pH measuring method".

The liquid detergent composition of the present invention preferably has a viscosity of 500 to 10,000 mPa · s, more preferably 1000 to 5000 mPa · s.
When the viscosity is within the above range, the liquid detergent composition can be easily discharged using the discharge container, and the usability can be easily improved.
The viscosity is a value obtained by measuring a liquid detergent composition at 25 ° C. with a B-type viscometer. Viscosity measurement conditions are as follows.
Measurement condition:
[rotor]
The rotor number and rotor rotation speed corresponding to the viscosity of the measurement object are as follows.
・ Viscosity is less than 500 mPa · s: Rotor No. 2. Rotation speed 60rpm.
・ Viscosity of 500 mPa · s or more and less than 2000 mPa · s: Rotor No. 3. Rotation speed 60rpm.
・ Viscosity is 2000 mPa · s or more and less than 10000 mPa · s: Rotor No. 4, 60 rpm.
・ Viscosity is 10000 mPa · s or more and less than 50000 mPa · s: Rotor No. 4, rotation speed 12rpm.
[Read numerical values]
60 seconds after the rotor starts rotating.

≪Manufacturing method≫
It does not restrict | limit especially as a manufacturing method of the liquid cleaning composition of this invention. For example, it is manufactured by mixing the components (A) to (C), water as a solvent, and the component (D) and optional components as necessary.

≪How to use≫
As a method of using the liquid cleaning composition of the present invention, a liquid cleaning composition or a diluted liquid of the liquid cleaning composition is accommodated in a discharge container, and an appropriate amount of the liquid cleaning composition is washed from the discharge container. Adhere to the object, leave it for a certain period of time and rinse with water (wash without rubbing), or take the liquid detergent composition or diluted liquid of the liquid detergent composition on a cleaning tool such as a sponge, and wash the object with the cleaning tool. Examples include rubbing and rinsing with water (rubbing). In particular, it can be preferably used for washing without rubbing.
When washing without rubbing, the time for allowing the liquid detergent composition of the present invention to adhere to the object to be washed and standing still is preferably 15 to 60 seconds, and more preferably 30 to 60 seconds. If the standing time is within the above range, it is easier to improve the permeation cleaning power against dirt.
The use of the liquid detergent composition of the present invention is not particularly limited. For example, it can be used for washing textile products, washing dishes, washing bathrooms, and washing toilets. Among these, it is preferable to use for dishwashing.

≪Liquid detergent composition product≫
The liquid detergent composition product of the present invention is obtained by accommodating the liquid detergent composition of the present invention in a container.
FIG. 1 is a front view showing an example of the liquid detergent composition product of the present invention. The liquid detergent composition product 1 of FIG. 1 is a trigger type spray container including a container body 100 that houses the liquid detergent composition 10 and a support body 110.
The pipe 108 extends from the support body 110 into the container body 100, and the tip of the pipe 108 penetrates into the liquid cleaning composition 10. The operating lever 120 is incorporated in the support body 110. A cap 120 that can be opened and closed is provided at the tip of the support body 110.

For example, when the liquid cleaning composition product 1 is used without being rubbed, the cap 120 is opened, and the tip of the support body 110 is directed toward the object to be cleaned. When the operating lever 120 is pushed toward the pipe 108, the liquid cleaning composition 10 is sucked up through the pipe 108 and discharged from the tip of the support body 110. The discharged liquid cleaning composition 10 adheres to the object to be cleaned. Washing can be carried out without rubbing by rinsing the article to which the liquid detergent composition 10 adheres after standing for a certain period of time and rinsing with water.
The discharged liquid cleaning composition 10 is preferably in the form of foam. Since it is easy to adhere to the dirt of the object to be washed due to the foam, it is easy to improve the usability and the permeation cleaning power.

  The light transmittance of at least a part of the container body 100 is preferably 10% or more. Thereby, the residual amount of the liquid cleaning composition 10 can be visually recognized from the outside. In this specification, the light transmittance is a value in the wavelength region of 200 to 700 nm, and the transmission spectrum and the transmittance are measured using a Hitachi U-3310 type spectrophotometer (60 mmΦ integrating sphere accessory device). Can be obtained.

The container body 100 is preferably a plastic container.
Constituent materials for plastic containers include polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycyclohexylene dimethylene terephthalate (PCT), polyacetal (POM), polyethylene naphthalate. (PEN), polystyrene (PS), acrylonitrile / butadiene / styrene resin (ABS), cellulose propionate (CP), polyarylate, polycarbonate, acrylonitrile / styrene copolymer resin (AS), and the like.

  FIG. 2 is a front view showing another example of the liquid detergent composition product of the present invention. The liquid detergent composition product 2 in FIG. 2 is a squeeze-type spray container including a container body 100a that contains the liquid detergent composition 10a and a cap 140.

For example, when the liquid detergent composition product 2 is used without being rubbed, the cap 140 is removed, and the tip of the container body 100a is directed toward the object to be cleaned. The side surface of the container main body 100a is pushed inward, and the liquid cleaning composition 10a is discharged from the tip of the container main body 100a. The discharged liquid cleaning composition 10a adheres to the object to be cleaned. Washing can be performed without rubbing by rinsing the article to which the liquid detergent composition 10a adheres after standing for a certain period of time and rinsing with water.
It is preferable that the liquid cleaning composition 10a to be discharged is foamy. Since it is easy to adhere to the dirt of the object to be washed due to the foam, it is easy to improve the usability and the permeation cleaning power.

The light transmittance of at least a part of the container body 100a is preferably 10% or more. Thereby, the residual amount of the liquid cleaning composition 10a can be visually recognized from the outside.
The container body 100a is preferably a flexible container. “Flexibility” means that the container is flexibly deformed without being damaged when the pressure in the container is changed.
As the flexible container, a plastic container is preferable.
Examples of the constituent material of the plastic container include the same materials as those described in the container main body 100.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples.

The unit of the blending amount in the table is “mass%”, and all the components indicate the amount in terms of pure content.
A blank in the table indicates that the component is not blended.
“Balance” means that water is blended so that the total blending amount (mass%) of all blending components contained in the composition of each example is 100 mass%.
Below, the component shown in the table | surface is demonstrated.

<(A) component>
A-1: sodium linear alkylbenzene sulfonate (carbon number of alkyl group: 10 to 14, purity 50%), in formula (A-II), R ⁵ is alkyl group having 10 to 14 carbon atoms, Y is 1 , Z ⁺ is a sodium ion (Lypon LS-250, manufactured by Lion Specialty Chemicals).
A-2: Sodium lauryl sulfate (purity 33%) (Sannool LM-1130, manufactured by Lion Specialty Chemicals), in formula (AI), R ⁴ is a dodecyl group, p is 0, q is 0, and X is 1, a compound in which M ⁺ is a sodium ion.
A-3: sodium polyoxyethylene alkyl ether sulfate (carbon number of alkyl group: 12 and 14 and the ratio is 12: 14 = 75: 25 derived from natural alcohol. Average number of EO addition moles 2, purity 70%) (New Japan) Rika Shinoline SPE-1250), a compound in which R ⁴ is an alkyl group having 12 to 14 carbon atoms, p is 0, q is 2, X is 1 and M ⁺ is a sodium ion in the formula (AI).

<(B) component>
B-1: 2-isobutyl-2-methyl-1,3-dioxolane-4-methanol (Augio Clean Plus purity 99.5%, manufactured by Rhodia Polyamida e Specialidades Ltd.), in the formula (BI), R ¹ is A compound in which a hydroxymethyl group, R ² is an isobutyl group, and R ³ is a methyl group.
B-2: 2,2-dimethyl-1,3-dioxolane-4-methanol (Augio Clean Multi purity 99.5%, manufactured by Rhodia Polyamida e Specialidades Ltd.), in formula (B-1), R ¹ is hydroxymethyl A compound wherein R ² is a methyl group and R ³ is a methyl group;
-B-3: 1,3-dioxolane (Kanto Chemical Co., Inc. purity 98%), a compound in which R ¹ is hydrogen, R ² is hydrogen, and R ³ is hydrogen in the formula (BI).
B-4: 2,2-dimethyl-1,3-dioxolane (98% purity by Kanto Chemical Co., Inc.), in formula (BI), R ¹ is hydrogen, R ² is a methyl group, and R ³ is methyl A compound that is a group.

<(C) component>
C-1: Palm oil alkyldimethylamine oxide (manufactured by Toho Chemical Industry, Katchinal AOC, purity 30%), in formula (C-II), R ⁶ is an alkyl group having 12 to 16 carbon atoms, r is 0, R ^A compound in which ⁷ is a methyl group and R ⁸ is a methyl group.
C-2: Lauryldimethylamine oxide (manufactured by Lion Specialty Chemicals, Kadenax DM12D-W (C), purity 33%), in formula (C-II), R ⁶ is a dodecyl group, r is 0, R ⁷ Is a methyl group, and R ⁸ is a methyl group.
C-3: Coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine (Evonic, Tego Beta L7, purity 30%) In the formula (CI), R ² is an alkyl group having 11 to 15 carbon atoms, and A is − C═O (—NH—X) —, X is — (CH ₂ ) ₃ —, R ³ is a methyl group, R ⁴ is a methyl group, R ⁵ is —CH ₂ —, and R ⁶ is —CO ₂ ^— . Compound.

<(D) component>
D-1: Polyoxyethylene / polyoxypropylene copolymerized alkyl ether (carbon number of alkyl group: 6 to 16, manufactured by Dow Chemical, Ecosurf SA-7, purity 96%).
D-2: Alkyl polyglycoside (manufactured by BASF, Glucopon 650 EC, carbon number of alkyl group: 12-14, purity 51.5%).
D-3: Coconut oil fatty acid diethanolamide (manufactured by Kawaken Fine Chemicals, Amizole CDE-G).
-D-4: 2-ethylhexyl glyceryl ether (Nippon Surfactant Kogyo, Nicoguard 88).
D-5: MGA, N-methyl coconut oil fatty acid glucamide (manufactured by Clariant, Glucopure DEG purity 63%).

<Optional component>
Citrate: Trisodium citrate dihydrate (Wako Pure Chemical Industries, Ltd. purity 99%).
-CMC: sodium carboxymethylcellulose (CMC1260 purity 99.7% made by Daicel Chemical Industries).
PH adjuster: sodium hydroxide (manufactured by Kanto Chemical Co., Inc., sodium hydroxide), sulfuric acid (sulfuric acid manufactured by Kanto Chemical Co., Ltd.).

<Preparation of liquid detergent composition>
1000 g of a liquid detergent composition having the composition shown in the table was prepared by the following procedure.
Add the components (A), (B), and (C) to the 1L beaker, and if necessary, add the (D) component and optional components, and add ion-exchanged water so that the total amount becomes 95% by mass. The mixture was stirred with a three-one motor (product name: FBL600, manufactured by Shinto Kagaku) until uniform. After adding a suitable amount of pH adjusting agent so that the pH at 25 ° C. is 10.5, ion-exchanged water is added so that the total amount becomes 100% by mass, and the mixture is stirred until uniform, and a liquid detergent composition Got.
The pH was adjusted to 25 ° C., and a glass electrode type pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) was used to immerse the glass electrode directly in the composition for 1 minute. The pH shown later was measured.

[Penetration cleaning power evaluation test method 1]
In order to improve the visibility of Nissin salad oil (mixed edible rapeseed oil and soybean oil. Made by Nisshin Oilio), the one with uniform dissolution of Sudan IV to 0.1% by weight is used for evaluation. It was. 0.5 g of the prepared dirt using a poly dropper while being lightweight with an electronic balance against a polyethylene lid (Iwasaki Kogyo Co., Ltd., Rustro Neokeeper 870 mL) having a groove 3 mm wide and 3 mm deep. Was applied uniformly and allowed to stand at room temperature of 25 ° C. for 1 hour. 4 mL of each example and comparative example was applied uniformly to the above-mentioned dirt adhesion groove using a pipetter and allowed to stand for 60 seconds. After the above, the grooves were thoroughly rinsed with running water at a flow rate of 25 ° C. and a flow rate of 6 L / min, the remaining dirt was visually confirmed, and evaluated in five stages according to the following evaluation criteria.
[Evaluation criteria]
A: There is no residue of dirt.
A: There is almost no remaining dirt.
○: The remaining dirt is very small.
Δ: Slightly remaining dirt.
X: The residue of dirt is very much.

[Penetration cleaning power evaluation test method 2]
In order to improve the visibility of Nissin salad oil (mixed edible rapeseed oil and soybean oil. Made by Nisshin Oilio), the one with uniform dissolution of Sudan IV to 0.1% by weight is used for evaluation. It was. 0.5 g of the prepared dirt using a poly dropper while being lightweight with an electronic balance against a polyethylene lid (Iwasaki Kogyo Co., Ltd., Rustro Neokeeper 870 mL) having a groove 3 mm wide and 3 mm deep. Was applied uniformly and allowed to stand at room temperature of 25 ° C. for 1 hour. 4 mL of each of the examples and comparative examples were uniformly applied to the above-mentioned dirt adhesion groove using a pipetter and allowed to stand for 15 seconds. After the above, the grooves were thoroughly rinsed with running water at a flow rate of 25 ° C. and a flow rate of 6 L / min, the remaining dirt was visually confirmed, and evaluated in five stages according to the following evaluation criteria.
[Evaluation criteria]
A: There is no residue of dirt.
A: There is almost no remaining dirt.
○: The remaining dirt is very small.
Δ: Slightly remaining dirt.
X: The residue of dirt is very much.

[Comprehensive evaluation]
Based on the evaluation results of [Penetration Detergency Evaluation Test Method 1] and [Penetration Detergency Evaluation Test Method 2], the following evaluation criteria were used for evaluation in five stages. ◎◎, ◎, ○ and △ are acceptable.
[Evaluation criteria]
A: Both the evaluation results of [Osmotic cleaning power evaluation test method 1] and [Osmotic cleaning power evaluation test method 2] are AA.
A: The evaluation result of [Penetration Detergency Evaluation Test Method 1] is ◎, and the evaluation result of [Penetration Detergency Evaluation Test Method 2] is any of ◎, ◯, or Δ.
A: The evaluation result of [Osmotic cleaning power evaluation test method 1] is ◎.
(Triangle | delta): The evaluation result of [osmotic cleaning power evaluation test method 1] is O.
X: The evaluation result of [Penetration cleaning power evaluation test method 1] is Δ or ×.

The liquid detergent compositions of Examples 1 to 26 to which the present invention was applied were excellent in the permeation cleaning power against dirt.
(A) The comparative example 1 which does not contain a component was inferior to the osmotic cleaning power with respect to dirt.
The comparative example 2 which does not contain (B) component was inferior to the osmotic cleaning power with respect to dirt.
(C) The comparative example 3 which does not contain a component was inferior to the osmotic cleaning power with respect to dirt.
Comparative Example 4 having an A / B ratio exceeding 45 was inferior in the permeation cleaning power against dirt.
The comparative example 5 whose A / B ratio is less than 0.06 was inferior in the permeation detergency against dirt.

1, 2, Liquid detergent composition product 10, 10a Liquid detergent composition 100, 100a Container body 108 Pipe 110 Support body 120 Actuating lever 130, 140 Cap

Claims (7)

(A) component, (B) component, and (C) component are included,
The component (A) is an anionic surfactant,
The component (B) is a compound represented by the following formula (BI),
The component (C) is at least one selected from the group consisting of amphoteric surfactants and amine oxide surfactants,
The liquid detergent composition whose mass ratio represented by said (A) component / said (B) component is 0.06-45.

In Formula (BI), R ¹ is a linear alkyl group having 1 to 14 carbon atoms, a branched alkyl group having 1 to 14 carbon atoms, a linear alkenyl group having 1 to 14 carbon atoms, or 1 carbon atom. A branched chain alkenyl group having 1 to 14 carbon atoms, a linear hydroxyalkyl group having 1 to 14 carbon atoms, a branched chain hydroxyalkyl group having 1 to 14 carbon atoms, or hydrogen, and R ² and R ³ are each independently A linear alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 1 to 5 carbon atoms, a linear alkenyl group having 1 to 5 carbon atoms, a branched alkenyl group having 1 to 5 carbon atoms, or Hydrogen. The component (A) is at least one selected from the group consisting of a compound (A1) represented by the following formula (AI) and a compound (A2) represented by the following formula (A-II) The liquid detergent composition of Claim 1 containing.
_{^{R 4 -O - [(PO)}} p / (EO) q] -SO 3 - 1 / X · M + ··· (A-I)
R ⁵ —C ₆ H ₄ —SO ₃ ^— 1 / Y · Z ⁺ ... (A-II)
In formula (AI), R ⁴ represents a linear or branched alkyl group having 8 to 18 carbon atoms; PO represents an oxypropylene group; EO represents an oxyethylene group; p represents an average repeat of PO Q represents the average number of repetitions of EO and 0 ≦ q ≦ 5; in [(PO) _p / (EO) _q ], EO and PO were random additions. It may be a block addition; M ⁺ is a counter ion; and X is the valence of M ⁺ .
In formula (A-II), R ⁵ represents a linear or branched alkyl group having 8 to 18 carbon atoms; Z ⁺ is a counter ion; Y is a valence of Z ⁺ . Wherein component (B) represents the formula (B-I) in the hydroxyalkyl group ^{R 1} is a linear 1 to 14 carbon atoms, or a hydroxyalkyl group of branched carbon atoms 1 to 14; ^{R 2} And R ³ each independently contains a compound (B1) representing a linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group having 1 to 5 carbon atoms. Liquid detergent composition.   Furthermore, the liquid cleaning composition as described in any one of Claims 1-3 containing a nonionic surfactant (D). The liquid cleaning composition of Claim 4 in which the said (D) component contains the compound (D1) represented by a following formula (DI).
_{^{R 11 -X - [(EO)}} s / (PO) t] -R 12 ··· (D-I)
In the formula (DI), R ¹¹ represents a hydrocarbon group having 6 to 22 carbon atoms; X represents a divalent linking group; R ¹² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a carbon number Represents an alkenyl group of 2 to 6, EO represents an oxyethylene group, PO represents an oxypropylene group, s represents an average number of repetitions of EO, is a number of 3 to 100, and t is an average number of repetitions of PO Represents a number from 0 to 6, and in [(EO) _s / (PO) _t ], EO and PO may be random addition or block addition.   The liquid cleaning composition of Claim 4 or 5 whose mass ratio represented by the said (D) component / (B) component is 3-100.   A liquid detergent composition product, wherein the liquid detergent composition according to any one of claims 1 to 6 is contained in a container.

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