JP2019189690A - Liquid detergent for clothing - Google Patents

Liquid detergent for clothing Download PDF

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JP2019189690A
JP2019189690A JP2018080935A JP2018080935A JP2019189690A JP 2019189690 A JP2019189690 A JP 2019189690A JP 2018080935 A JP2018080935 A JP 2018080935A JP 2018080935 A JP2018080935 A JP 2018080935A JP 2019189690 A JP2019189690 A JP 2019189690A
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liquid detergent
clothing
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JP7250432B2 (en
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真一 花田
Shinichi Hanada
真一 花田
知美 小熊
Tomomi Oguma
知美 小熊
弘嗣 小倉
Hirotsugu Ogura
弘嗣 小倉
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Lion Corp
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Lion Corp
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Abstract

To provide a liquid detergent for clothing good in liquid stability, excellent in detergency, and excellent in effect for suppressing expansion of dirt when applied to an article to be cleaned and stood.SOLUTION: There is provided a liquid detergent for clothing containing a nonionic surfactant A and polyoxyalkylene alkylether sulfuric acid or a salt thereof B, the A component contains one or more kind selected from a group consisting of a compound represented by the following formula (i), a compound represented by the following formula (ii), and a compound represented by the following formula (iii), of 1 mass% or more, and having a mass ratio of A/B of 2.5 or less.SELECTED DRAWING: None

Description

本発明は、衣料用液体洗浄剤に関する。   The present invention relates to a liquid cleaning agent for clothing.

液体洗浄剤は、衣類に付着した汚れに直接塗布できるため、落ちにくい部分的な皮脂汚れや油汚れの除去において効果を発揮しやすい。
特許文献1には、特定のノニオン界面活性剤(オキシエチレン基の平均付加モル数が5〜8であるポリオキシエチレンアルキルエーテル)を含む液体洗浄剤を、皮脂による黒ずみ汚れに塗布し、5分間放置した後に、粉末洗剤溶液で洗濯した例が記載されている。
Since the liquid cleaning agent can be directly applied to dirt adhered to clothing, it is easy to exert an effect in removing partial sebum dirt and oil dirt that are difficult to remove.
In Patent Document 1, a liquid detergent containing a specific nonionic surfactant (polyoxyethylene alkyl ether having an average addition mole number of oxyethylene groups of 5 to 8) is applied to dark stains by sebum for 5 minutes. An example of washing with a powder detergent solution after standing is described.

特開2005−132898号公報JP 2005-132898 A

しかし特許文献1の方法は必ずしも充分ではなく、さらなる洗浄力の向上が求められる。
そこで本発明者等は洗浄力の向上を期待して、特許文献1の液体洗浄剤を汚れ部分に塗布してから洗濯するまでの放置時間を長くしたところ、汚れ部分が洗濯前よりも拡がってしまうことを知見した。
また液体洗浄剤には、液体の状態を維持できる安定性(液安定性)が要求される。
本発明は、液安定性が良好で、洗浄力に優れ、被洗物に塗布してから放置したときの汚れの拡がりを抑える効果(汚れの拡がり防止性)に優れる衣料用液体洗浄剤を目的とする。
However, the method of Patent Document 1 is not always sufficient, and further improvement in cleaning power is required.
Therefore, the present inventors expect the improvement of the cleaning power, and when the standing time from the application of the liquid detergent of Patent Document 1 to the soiled part until the washing is increased, the soiled part spreads more than before washing. I found out.
In addition, the liquid detergent is required to have stability (liquid stability) capable of maintaining a liquid state.
The present invention is directed to a liquid detergent for clothing that has excellent liquid stability, excellent cleaning power, and excellent effect of suppressing the spread of dirt when left on the object after being applied to the object to be washed (prevention of spread of dirt). And

本発明者らは鋭意検討により、特定のエステル型ノニオン界面活性剤とポリオキシアルキレンアルキルエーテル硫酸又はその塩とを組み合わせることにより、上記課題を解決できることを見出した。
本発明は以下の態様を有する。
The present inventors have intensively studied and found that the above problems can be solved by combining a specific ester-type nonionic surfactant with polyoxyalkylene alkyl ether sulfate or a salt thereof.
The present invention has the following aspects.

[1](A)成分:ノニオン界面活性剤、及び(B)成分:ポリオキシアルキレンアルキルエーテル硫酸又はその塩、を含み、前記(A)成分が、(A1)成分:下記式(i)で表される化合物、下記式(ii)で表される化合物、及び下記式(iii)で表される化合物からなる群から選ばれる1種以上、を含み、衣料用液体洗浄剤の総質量に対して、前記(A1)成分の含有量が1質量%以上であり、前記(B)成分の含有量に対する前記(A)成分の含有量の質量比を表す(A)/(B)が2.5以下である、衣料用液体洗浄剤。   [1] Component (A): a nonionic surfactant, and (B) component: polyoxyalkylene alkyl ether sulfuric acid or a salt thereof, wherein (A) component is (A1) component: represented by the following formula (i) One or more selected from the group consisting of a compound represented by the following formula (ii), a compound represented by the following formula (iii), and the total mass of the liquid detergent for clothing The content of the component (A1) is 1% by mass or more, and (A) / (B) representing the mass ratio of the content of the component (A) to the content of the component (B) is 2. Liquid detergent for clothes which is 5 or less.

Figure 2019189690
Figure 2019189690

式(i)において、Xは水素原子または−C(O)Rであり、R、Rは独立して炭素数7〜19の炭化水素基であり、AOはオキシエチレン基またはオキシプロピレン基の少なくとも一方であり、m1はAOの平均繰返し数を表し、3〜20の数である。 In the formula (i), X is a hydrogen atom or —C (O) R 2 , R 1 and R 2 are independently a hydrocarbon group having 7 to 19 carbon atoms, and AO is an oxyethylene group or oxypropylene It is at least one of the groups, and m1 represents the average number of repetitions of AO and is a number of 3 to 20.

Figure 2019189690
Figure 2019189690

式(ii)において、Y〜Yは独立して水素原子または−C(O)Rであり、Y〜Yの少なくとも1つは−C(O)Rであり、Rは炭素数9〜19の炭化水素基であり、AOはオキシエチレン基またはオキシプロピレン基の少なくとも一方であり、m2〜m4はAOの平均繰返し数を表し、独立して0〜15の数である。 In formula (ii), Y 1 to Y 3 are independently a hydrogen atom or —C (O) R 3 , at least one of Y 1 to Y 3 is —C (O) R 3 , and R 3 Is a hydrocarbon group having 9 to 19 carbon atoms, AO is at least one of an oxyethylene group or an oxypropylene group, m2 to m4 represent the average number of repetitions of AO, and are independently a number of 0 to 15 .

Figure 2019189690
Figure 2019189690

式(iii)において、Z〜Zは独立して水素原子または−C(O)Rであり、Rは炭素数11〜21の炭化水素基であり、AOはオキシエチレン基またはオキシプロピレン基の少なくとも一方であり、m5〜m7はAOの平均繰返し数を表し、独立して0以上の数であり、m5+m6+m7は5〜100の数であり、R、R、Rは独立して−(CH10−又は−(CHCH=CH(CH)−である。 In formula (iii), Z 1 to Z 3 are independently a hydrogen atom or —C (O) R 7 , R 7 is a hydrocarbon group having 11 to 21 carbon atoms, and AO is an oxyethylene group or an oxy group It is at least one of propylene groups, m5 to m7 represent the average number of AO repetitions, and are independently 0 or more, m5 + m6 + m7 is a number of 5 to 100, and R 4 , R 5 and R 6 are independent to - (CH 2) 10 - or - (CH 2) 7 CH = CH (CH 2) - a.

[2]衣料用液体洗浄剤の総質量に対して、界面活性剤の総質量が40質量%以下である、[1]の衣料用液体洗浄剤。
[3](A2)成分:下記式(iv)で表されるポリオキシエチレンアルキルエーテル、の含有量が、衣料用液体洗浄剤の総質量に対して5質量%以下である、[1]または[2]の衣料用液体洗浄剤。
11−O−(EO)−H ・・・(iv)
式(iv)において、R11は炭素数8〜18の炭化水素基であり、EOはオキシエチレン基であり、sはEOの平均繰り返し数を表し、2〜13の数である。
[2] The liquid detergent for clothing according to [1], wherein the total mass of the surfactant is 40% by mass or less based on the total mass of the liquid detergent for clothing.
[3] Component (A2): The content of the polyoxyethylene alkyl ether represented by the following formula (iv) is 5% by mass or less based on the total mass of the liquid detergent for clothing, [1] or [2] Liquid detergent for clothes.
R 11 —O— (EO) s —H (iv)
In the formula (iv), R 11 is a hydrocarbon group having 8 to 18 carbon atoms, EO is an oxyethylene group, s represents an average number of repetitions of EO, and is a number of 2 to 13.

[4]界面活性剤の総質量に対して、前記(A1)成分及び前記(B)成分の合計の含有量が30質量%以上である、[1]〜[3]のいずれかの衣料用液体洗浄剤。
[5]前記(B)成分の含有量に対する前記(A1)成分の含有量の質量比を表す(A1)/(B)が2.5以下である、[1]〜[4]のいずれかの衣料用液体洗浄剤。
[6]前記(A1)成分が前記式(i)で表される化合物であり、前記(A1)/(B)が0.05〜2.5である、[5]の衣料用液体洗浄剤。
[7]前記(A1)成分が前記式(ii)で表される化合物であり、前記(A1)/(B)が0.05〜2.5である、[5]の衣料用液体洗浄剤。
[8]前記(A1)成分が前記式(iii)で表される化合物であり、前記(A1)/(B)が0.1〜2である、[5]の衣料用液体洗浄剤。
[4] For clothing according to any one of [1] to [3], wherein the total content of the component (A1) and the component (B) is 30% by mass or more with respect to the total mass of the surfactant. Liquid cleaning agent.
[5] Any of [1] to [4], wherein (A1) / (B) representing a mass ratio of the content of the component (A1) to the content of the component (B) is 2.5 or less. Liquid detergent for clothing.
[6] The liquid detergent for clothes according to [5], wherein the component (A1) is a compound represented by the formula (i), and the (A1) / (B) is 0.05 to 2.5. .
[7] The liquid detergent for clothes according to [5], wherein the component (A1) is a compound represented by the formula (ii) and the (A1) / (B) is 0.05 to 2.5. .
[8] The liquid detergent for clothing according to [5], wherein the component (A1) is a compound represented by the formula (iii) and the (A1) / (B) is 0.1 to 2.

本発明の衣料用液体洗浄剤は、液安定性が良好で、洗浄力及び汚れの拡がり防止性に優れる。   The liquid detergent for clothes of the present invention has good liquid stability, and is excellent in cleaning power and stain spread prevention.

≪衣料用液体洗浄剤≫
本発明の衣料用液体洗浄剤(以下、「液体洗浄剤」ともいう。)は、(A)成分と、(B)成分を含む。(A)成分は少なくとも(A1)成分を含む。
≪Liquid detergent for clothing≫
The liquid detergent for clothes of the present invention (hereinafter also referred to as “liquid detergent”) includes (A) component and (B) component. The component (A) includes at least the component (A1).

<(A)成分>
[(A1)成分]
(A)成分はノニオン界面活性剤であり、(A1)成分は、下記式(i)で表される化合物(以下、化合物(i)という。)、下記式(ii)で表される化合物(以下、化合物(ii)という。)、及び下記式(iii)で表される化合物(以下、化合物(iii)という。)からなる群から選ばれる1種以上である。
<(A) component>
[(A1) component]
The component (A) is a nonionic surfactant, and the component (A1) is a compound represented by the following formula (i) (hereinafter referred to as compound (i)), a compound represented by the following formula (ii) ( Hereinafter, it is at least one selected from the group consisting of compound (ii)) and a compound represented by the following formula (iii) (hereinafter referred to as compound (iii)).

Figure 2019189690
Figure 2019189690

[化合物(i)]
式(i)において、Xは水素原子または−C(O)Rであり、R、Rは独立して炭素数7〜19の炭化水素基であり、AOはオキシエチレン基(以下、EOともいう。)またはオキシプロピレン基(以下、POともいう。)の少なくとも一方であり、m1はAOの平均繰返し数を表し、3〜20の数である。
、Rである炭化水素基は飽和でもよく不飽和でもよい。直鎖状または分岐状のアルキル基またはアルケニル基が好ましく、アルキル基がより好ましい。
、Rの炭素数は12〜18が好ましい。
m1は6〜18が好ましく、8〜16がより好ましい。
AOがEOとPOである場合、EOとPOとは混在して配列していてもよい。
[Compound (i)]
In the formula (i), X is a hydrogen atom or —C (O) R 2 , R 1 and R 2 are independently a hydrocarbon group having 7 to 19 carbon atoms, and AO is an oxyethylene group (hereinafter, Or oxypropylene group (hereinafter also referred to as PO), and m1 represents the average number of repetitions of AO, and is a number of 3 to 20.
The hydrocarbon groups as R 1 and R 2 may be saturated or unsaturated. A linear or branched alkyl group or alkenyl group is preferable, and an alkyl group is more preferable.
As for carbon number of R < 1 >, R < 2 >, 12-18 are preferable.
m1 is preferably 6 to 18, and more preferably 8 to 16.
When AO is EO and PO, EO and PO may be mixed and arranged.

(A1)成分が化合物(i)である場合、液体洗浄剤の総質量に対して、化合物(i)の含有量は1質量%以上であり、2〜7質量%が好ましく、4〜7質量%がより好ましい。上記範囲の下限値以上であると洗浄力に優れ、上限値以下であると液安定性と汚れの拡がり防止性に優れる。   When the component (A1) is the compound (i), the content of the compound (i) is 1% by mass or more, preferably 2-7% by mass, and 4-7% by mass with respect to the total mass of the liquid detergent. % Is more preferable. When it is at least the lower limit of the above range, the detergency is excellent, and when it is not more than the upper limit, the liquid stability and the spread prevention property are excellent.

Figure 2019189690
Figure 2019189690

[化合物(ii)]
式(ii)において、Y〜Yは独立して水素原子または−C(O)Rであり、Y〜Yの少なくとも1つは−C(O)Rであり、Rは炭素数9〜19の炭化水素基であり、AOはEOまたはPOの少なくとも一方であり、m2〜m4はAOの平均繰返し数を表し、独立して0〜15の数である。
である炭化水素基は飽和でもよく不飽和でもよい。直鎖状または分岐状のアルキル基またはアルケニル基が好ましく、アルキル基がより好ましい。
の炭素数は12〜18が好ましい。
m2+m3+m4は2〜60が好ましく、6〜30がより好ましい。
AOがEOとPOである場合、EOとPOとは混在して配列していてもよい。
〜Yの1つが−C(O)Rであり、残りの2つが水素原子が好ましい。
[Compound (ii)]
In formula (ii), Y 1 to Y 3 are independently a hydrogen atom or —C (O) R 3 , at least one of Y 1 to Y 3 is —C (O) R 3 , and R 3 Is a hydrocarbon group having 9 to 19 carbon atoms, AO is at least one of EO and PO, m2 to m4 represent the average number of repetitions of AO, and are independently a number of 0 to 15.
The hydrocarbon group as R 3 may be saturated or unsaturated. A linear or branched alkyl group or alkenyl group is preferable, and an alkyl group is more preferable.
The number of carbon atoms of R 3 is 12 to 18 is preferred.
As for m2 + m3 + m4, 2-60 are preferable and 6-30 are more preferable.
When AO is EO and PO, EO and PO may be mixed and arranged.
One of Y 1 to Y 3 is —C (O) R 3 , and the remaining two are preferably hydrogen atoms.

(A1)成分が化合物(ii)である場合、液体洗浄剤の総質量に対して、化合物(ii)の含有量は1質量%以上であり、2〜10質量%が好ましく、4〜6質量%がより好ましい。上記範囲の下限値以上であると洗浄力に優れ、上限値以下であると液安定性に優れる。   When the component (A1) is the compound (ii), the content of the compound (ii) is 1% by mass or more, preferably 2 to 10% by mass, with respect to the total mass of the liquid detergent. % Is more preferable. When it is at least the lower limit of the above range, the detergency is excellent, and when it is at most the upper limit, the liquid stability is excellent.

Figure 2019189690
Figure 2019189690

[化合物(iii)]
式(iii)において、Z〜Zは独立して水素原子または−C(O)Rであり、Rは炭素数11〜21の炭化水素基であり、AOはEOまたはPOの少なくとも一方であり、m5〜m7はAOの平均繰返し数を表し、独立して0以上の数であり、m5+m6+m7は5〜100の数であり、R、R、Rは独立して−(CH10−又は−(CHCH=CH(CH)−である。
である炭化水素基は飽和でもよく不飽和でもよい。直鎖状または分岐状のアルキル基またはアルケニル基が好ましく、アルキル基がより好ましい。
の炭素数は11〜17が好ましい。
m5+m6+m7は5〜80が好ましく、10〜60がより好ましい。
AOがEOとPOである場合、EOとPOとは混在して配列していてもよい。
〜Zは水素原子が好ましい。
[Compound (iii)]
In formula (iii), Z 1 to Z 3 are each independently a hydrogen atom or —C (O) R 7 , R 7 is a hydrocarbon group having 11 to 21 carbon atoms, and AO is at least EO or PO. On the other hand, m5 to m7 represent the average number of repetitions of AO, independently a number of 0 or more, m5 + m6 + m7 is a number of 5 to 100, and R 4 , R 5 , R 6 are independently-( CH 2) 10 - or - (CH 2) 7 CH = CH (CH 2) - a.
The hydrocarbon group as R 7 may be saturated or unsaturated. A linear or branched alkyl group or alkenyl group is preferable, and an alkyl group is more preferable.
The number of carbon atoms in R 7 is preferably 11 to 17.
As for m5 + m6 + m7, 5-80 are preferable and 10-60 are more preferable.
When AO is EO and PO, EO and PO may be mixed and arranged.
Z 1 to Z 3 are preferably hydrogen atoms.

(A1)成分が化合物(iii)である場合、液体洗浄剤の総質量に対して、化合物(iii)の含有量は1質量%以上であり、1〜5質量%が好ましく、1〜3質量%がより好ましい。上記範囲の下限値以上であると洗浄力に優れ、上限値以下であると液安定性に優れる。   When the component (A1) is the compound (iii), the content of the compound (iii) is 1% by mass or more, preferably 1 to 5% by mass, and preferably 1 to 3% by mass with respect to the total mass of the liquid detergent. % Is more preferable. When it is at least the lower limit of the above range, the detergency is excellent, and when it is at most the upper limit, the liquid stability is excellent.

(A1)成分は、上記化合物(i)、(ii)または(iii)のいずれか1種でもよく、2種以上を併用してもよい。
(A)成分(ノニオン界面活性剤)の総質量に対する、(A1)成分の総質量(化合物(i)〜(iii)の合計の質量)の比を表す(A1)/(A)は、0.5以上が好ましく、0.7以上がより好ましく、0.9以上が特に好ましい。
化合物(i)〜(iii)のうち化合物(i)が特に好ましく、(A1)成分は、少なくとも化合物(i)を含むことが好ましい。
(A1)成分の総質量に対して、化合物(i)が50質量%以上であることが好ましく、70質量%以上がより好ましく、90質量%がさらに好ましく、100質量%が最も好ましい。
The component (A1) may be any one of the above compounds (i), (ii) or (iii), or two or more of them may be used in combination.
(A1) / (A) representing the ratio of the total mass of the component (A1) (the total mass of the compounds (i) to (iii)) to the total mass of the component (A) (nonionic surfactant) is 0. 0.5 or more is preferable, 0.7 or more is more preferable, and 0.9 or more is particularly preferable.
Of the compounds (i) to (iii), the compound (i) is particularly preferable, and the component (A1) preferably includes at least the compound (i).
The compound (i) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass, and most preferably 100% by mass with respect to the total mass of the component (A1).

[(A2)成分]
液体洗浄剤は(A)成分として、下記(A2)成分を含んでもよい。
(A2)成分:式(iv)で表されるポリオキシエチレンアルキルエーテル。
11−O−(EO)−H ・・・(iv)
式(iv)において、R11は炭素数8〜18の炭化水素基であり、EOはオキシエチレン基であり、sはEOの平均繰り返し数を表し、2〜13の数である。
[(A2) component]
The liquid detergent may contain the following component (A2) as the component (A).
(A2) Component: Polyoxyethylene alkyl ether represented by the formula (iv).
R 11 —O— (EO) s —H (iv)
In the formula (iv), R 11 is a hydrocarbon group having 8 to 18 carbon atoms, EO is an oxyethylene group, s represents an average number of repetitions of EO, and is a number of 2 to 13.

液体洗浄剤を被洗物に塗布してから放置したときの汚れの拡がりを抑える点で、(A2)成分の含有量は少ない方が好ましい。
具体的には、衣料用液体洗浄剤の総質量に対して(A2)成分の含有量が5質量%以下であることが好ましい。
すなわち、液体洗浄剤は、(A2)成分を含まない態様、又は液体洗浄剤の総質量に対する(A2)成分の含有量が0超5質量%以下である態様が好ましい。
上記(A2)成分の含有量の上限は1質量%以下がより好ましく、0.5質量%以下がさらに好ましい。
(A1)成分の総質量に対する、(A2)成分の総質量の比を表す(A2)/(A1)は、0.8以下が好ましく、0.5以下がより好ましく、0.1以下がさらに好ましく、0が特に好ましい。
It is preferable that the content of the component (A2) is small from the viewpoint of suppressing the spread of dirt when the liquid detergent is applied to the object to be washed and left standing.
Specifically, the content of the component (A2) is preferably 5% by mass or less with respect to the total mass of the liquid detergent for clothing.
In other words, the liquid detergent preferably has an aspect that does not contain the component (A2) or an aspect in which the content of the component (A2) with respect to the total mass of the liquid detergent is greater than 0 and not more than 5% by mass.
The upper limit of the content of the component (A2) is more preferably 1% by mass or less, and further preferably 0.5% by mass or less.
(A2) / (A1) representing the ratio of the total mass of the component (A2) to the total mass of the component (A1) is preferably 0.8 or less, more preferably 0.5 or less, and further preferably 0.1 or less. 0 is particularly preferable.

[(A3)成分:他のノニオン界面活性剤]
(A3)成分は、(A1)成分、(A2)成分のいずれにも該当しない、他のノニオン界面活性剤である。液体洗浄剤は、(A3)成分の1種以上を含有してもよい。(A3)成分として、液体洗浄剤において公知のノニオン界面活性剤が使用できる。
液体洗浄剤の総質量に対して、(A3)成分の含有量は10質量%以下が好ましく、5質量%以下がより好ましく、1質量%以下がさらに好ましい。ゼロでもよい。
[(A3) component: other nonionic surfactant]
The component (A3) is another nonionic surfactant that does not correspond to either the component (A1) or the component (A2). The liquid detergent may contain one or more components (A3). As the component (A3), a known nonionic surfactant can be used in the liquid detergent.
The content of the component (A3) is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less with respect to the total mass of the liquid detergent. Zero is acceptable.

<(B)成分>
(B)成分は、ポリオキシアルキレンアルキルエーテル硫酸又はその塩である。
ポリオキシアルキレンアルキルエーテル硫酸塩としては、下記式(v)で表される化合物(v)が挙げられる。
21−O−[(EO)/(PO)]−SO ・・・(v)
式(v)において、R21は、炭素数8〜20の直鎖状又は分岐鎖状のアルキル基であり、kはEOの平均繰り返し数を表し、0以上の数であり、nはPOの平均繰り返し数を表し、0〜6の数であり、Mは対カチオンである。
式(v)におけるk=0、n=0である成分(b0)の含有量は、(B)成分の総質量に対して35〜55質量%であることが好ましい。
<(B) component>
The component (B) is polyoxyalkylene alkyl ether sulfuric acid or a salt thereof.
Examples of the polyoxyalkylene alkyl ether sulfate include a compound (v) represented by the following formula (v).
R 21 -O - [(EO) k / (PO) n] -SO 3 - M + ··· (v)
In the formula (v), R 21 is a linear or branched alkyl group having 8 to 20 carbon atoms, k represents an average number of EO repeats, is a number of 0 or more, and n is PO. Represents the average number of repeats, a number from 0 to 6, and M + is a counter cation.
The content of the component (b0) where k = 0 and n = 0 in the formula (v) is preferably 35 to 55% by mass with respect to the total mass of the component (B).

21は、炭素数10〜20の直鎖又は分岐鎖のアルキル基が好ましく、炭素数12〜14の直鎖又は分岐鎖のアルキル基がより好ましい。
kは0〜5が好ましく、0.5〜3がより好ましい。nは0〜3が好ましく、0がより好ましい。k+nは1〜5が好ましい。
塩としては、ナトリウム、カリウム等とのアルカリ金属塩、モノエタノールアミン、ジエタノールアミン等とのアルカノールアミン塩等が挙げられる。
R 21 is preferably a linear or branched alkyl group having 10 to 20 carbon atoms, and more preferably a linear or branched alkyl group having 12 to 14 carbon atoms.
k is preferably 0 to 5, and more preferably 0.5 to 3. n is preferably 0 to 3, and more preferably 0. k + n is preferably 1 to 5.
Examples of the salt include alkali metal salts with sodium, potassium and the like, alkanolamine salts with monoethanolamine, diethanolamine and the like.

液体洗浄剤に含まれる(B)成分は、1種でもよく、2種以上でもよい。
液体洗浄剤の総質量に対して、(B)成分の含有量は1〜20質量%が好ましく、2〜15質量%がより好ましく、3〜10質量%がさらに好ましい。上記範囲の下限値以上であると汚れの拡がり防止性に優れ、上限値以下であると液安定性に優れる。また上記範囲内であると優れた洗浄力が得られやすい。
The component (B) contained in the liquid detergent may be one type or two or more types.
The content of the component (B) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and further preferably 3 to 10% by mass with respect to the total mass of the liquid detergent. When it is at least the lower limit of the above range, the spread of dirt is excellent, and when it is at most the upper limit, the liquid stability is excellent. Moreover, it is easy to acquire the outstanding cleaning power as it is in the said range.

液体洗浄剤において、(B)成分の含有量に対する(A)成分の含有量の質量比を表す(A)/(B)は2.5以下であり、0.05〜2.4が好ましく、0.1〜2.0がより好ましく、0.1〜1.5がさらに好ましく、0.1〜1.0が特に好ましい。
上記範囲の上限値以下であると汚れの拡がり防止性に優れる。また液安定性に優れる。下限値以上であると、洗浄力に優れる。
In the liquid detergent, (A) / (B) representing the mass ratio of the content of the component (A) to the content of the component (B) is 2.5 or less, preferably 0.05 to 2.4, 0.1-2.0 are more preferable, 0.1-1.5 are still more preferable, and 0.1-1.0 are especially preferable.
When the amount is not more than the upper limit of the above range, the spread of dirt is excellent. Moreover, it is excellent in liquid stability. When it is at least the lower limit, the cleaning power is excellent.

(A1)成分が化合物(i)である場合、(A)/(B)は0.05〜2.5が好ましく、0.1〜2.0がより好ましく、0.4〜1.5がさらに好ましく、0.5〜1.0が特に好ましい。
(A1)成分が化合物(ii)である場合、(A)/(B)は0.05〜2.5が好ましく、0.1〜2.0がより好ましく、0.4〜1.5がさらに好ましく、0.5〜1.0が特に好ましい。
(A1)成分が化合物(iii)である場合、(A)/(B)は0.1〜2.0が好ましく、0.1〜1.0がより好ましく、0.1〜0.4がさらに好ましく、0.1〜0.3が特に好ましい。
また、(A1)/(b0)は、5.0以下が好ましく、0.1〜4.0がより好ましく、0.2〜3.0がさらに好ましく、0.2〜2.0が特に好ましい。
When the component (A1) is the compound (i), 0.05 to 2.5 is preferable, (A) / (B) is more preferably 0.1 to 2.0, and 0.4 to 1.5 is Further preferred is 0.5 to 1.0.
When component (A1) is compound (ii), (A) / (B) is preferably 0.05 to 2.5, more preferably 0.1 to 2.0, and 0.4 to 1.5. Further preferred is 0.5 to 1.0.
When the component (A1) is compound (iii), (A) / (B) is preferably 0.1 to 2.0, more preferably 0.1 to 1.0, and 0.1 to 0.4. Further preferred is 0.1 to 0.3.
Further, (A1) / (b0) is preferably 5.0 or less, more preferably 0.1 to 4.0, further preferably 0.2 to 3.0, and particularly preferably 0.2 to 2.0. .

<(C)成分:他の界面活性剤>
(C)成分は、(A)成分、(B)成分のいずれにも該当しない、他の界面活性剤である。液体洗浄剤は、(C)成分の1種以上を含有してもよい。(C)成分として、(B)成分以外のアニオン界面活性剤(高級脂肪酸又はその塩を除く)、カチオン界面活性剤、両性界面活性剤、アミンオキシド型界面活性剤が挙げられる。これらは液体洗浄剤において公知の界面活性剤が使用できる。
<(C) component: other surfactant>
Component (C) is another surfactant that does not fall under either component (A) or component (B). A liquid detergent may contain 1 or more types of (C) component. Examples of the component (C) include anionic surfactants other than the component (B) (excluding higher fatty acids or salts thereof), cationic surfactants, amphoteric surfactants, and amine oxide surfactants. These may be known surfactants in liquid detergents.

液体洗浄剤の総質量に対して、界面活性剤の総質量は40質量%以下が好ましく、3〜30質量%がより好ましく、5〜20質量%がさらに好ましく、7〜15質量%が特に好ましい。
上記範囲の下限値以上であると洗浄力に優れる。また汚れの拡がり防止性に優れる。上限値以下であると液安定性に優れる。
The total mass of the surfactant is preferably 40% by mass or less, more preferably 3 to 30% by mass, further preferably 5 to 20% by mass, and particularly preferably 7 to 15% by mass with respect to the total mass of the liquid detergent. .
When it is at least the lower limit of the above range, the cleaning power is excellent. It also has excellent anti-smudge properties. If it is below the upper limit, the liquid stability is excellent.

液体洗浄剤の総質量に対して、(C)成分の含有量は10質量%以下が好ましく、5質量%以下がより好ましく、1質量%以下がさらに好ましい。ゼロでもよい。
界面活性剤の総質量に対して、(A1)成分及び(B)成分の合計の含有量は30質量%以上が好ましく、40質量%以上がより好ましく、60質量%以上がさらに好ましく、80質量%以上が特に好ましく、100質量%が非常に好ましい。
The content of the component (C) is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less with respect to the total mass of the liquid detergent. Zero is acceptable.
The total content of the component (A1) and the component (B) is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 60% by mass or more, and 80% by mass with respect to the total mass of the surfactant. % Or more is particularly preferable, and 100% by mass is very preferable.

<水>
液体洗浄剤は水を含むことが好ましい。液体洗浄剤の総質量に対して水の含有量は、洗浄剤の調製のしやすさ、および外観安定性の点で50〜95質量%が好ましく、60〜90質量%がより好ましい。
<Water>
The liquid detergent preferably contains water. The content of water with respect to the total mass of the liquid detergent is preferably 50 to 95% by mass, more preferably 60 to 90% by mass in terms of ease of preparation of the detergent and appearance stability.

<任意成分>
液体洗浄剤は、上記(A)〜(C)成分及び水以外に、液体洗浄剤の分野で公知の成分を、任意成分として含有してもよい。
例えば、有機溶媒、高級脂肪酸又はその塩、消泡剤、金属イオン捕捉剤(キレート剤)、酵素、アルカリ剤、pH調整剤、酸化防止剤、防腐剤、風合い向上剤、移染防止剤、再汚染防止剤、パール剤、ソイルリリース剤、ハイドロトロープ剤、着香剤、着色剤、乳濁化剤、蛍光剤、エキス等が挙げられる。
<Optional component>
In addition to the above components (A) to (C) and water, the liquid detergent may contain components known in the field of liquid detergent as optional components.
For example, organic solvents, higher fatty acids or salts thereof, antifoaming agents, metal ion scavengers (chelating agents), enzymes, alkali agents, pH adjusters, antioxidants, preservatives, texture improvers, dye transfer inhibitors, Antifouling agents, pearl agents, soil release agents, hydrotropes, flavoring agents, coloring agents, emulsifying agents, fluorescent agents, extracts and the like can be mentioned.

pH調整剤としては、塩酸、硫酸、リン酸等の無機酸、水酸化ナトリウム、水酸化カリウム、アルカノールアミン、アンモニア等が挙げられる。これらのなかでも、液安定性の点から、硫酸、水酸化ナトリウム、水酸化カリウム、アルカノールアミンが好ましく、硫酸、水酸化ナトリウムが好ましい。pH調整剤は、1種を単独で用いてもよく、2種以上を併用してもよい。   Examples of the pH adjuster include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, sodium hydroxide, potassium hydroxide, alkanolamine, and ammonia. Among these, sulfuric acid, sodium hydroxide, potassium hydroxide, and alkanolamine are preferable from the viewpoint of liquid stability, and sulfuric acid and sodium hydroxide are preferable. A pH adjuster may be used individually by 1 type, and may use 2 or more types together.

有機溶媒は、液体洗浄剤の分野において公知のものを使用できる。
例えば、エタノール、1−プロパノール、2−プロパノール、1−ブタノール等の炭素数2〜4の一価アルコール;エチレングリコール、プロピレングリコール、ブチレングリコール、トリエチレングリコール、テトラエチレングリコール、平均分子量約200〜5000のポリエチレングリコール、メトキシポリエチレングリコール、グリセリン等の炭素数2〜4の多価アルコール;及び
エチレングリコールモノブチルエーテル、エチレングリコールモノヘキシルエーテル、エチレングリコールモノフェニルエーテル、プロピレングリコールモノフェニルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、ダイセル社製セルトールEDGAC(ジエチレングリコールモノエチルエーテルアセテート)等のグリコールエーテル系溶剤が挙げられる。
特に、エタノール、グリセリンは塗布放置時の拡がりへの寄与が小さいためが好ましい。
As the organic solvent, those known in the field of liquid detergents can be used.
For example, C2-C4 monohydric alcohols such as ethanol, 1-propanol, 2-propanol, 1-butanol; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, tetraethylene glycol, average molecular weight of about 200 to 5000 C 2-4 polyhydric alcohols such as polyethylene glycol, methoxy polyethylene glycol, glycerin; and ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol Monobutyl ether, Certol EDGAC (diethylene glycol monoethyl ether acetate manufactured by Daicel Corporation) And glycol ether solvents such as tate).
In particular, ethanol and glycerin are preferred because they contribute little to spreading when left uncoated.

液体洗浄剤の総質量に対して有機溶媒の含有量は、0〜15質量%が好ましく、5〜12質量%がより好ましい。有機溶媒を含有させると液の外観安定性が向上しやすい。有機溶媒の含有量が上記範囲の上限値以下であると汚れの拡がり防止性に優れる。
有機溶媒以外の任意成分の合計の含有量は特に限定されないが、液体洗浄剤の総質量に対し、20質量%以下が好ましく、10質量%以下がより好ましく、7質量%以下がさらに好ましい。
液体洗浄剤の各成分の含有量の合計は、100質量%を超えない。
0-15 mass% is preferable and, as for content of an organic solvent with respect to the total mass of a liquid detergent, 5-12 mass% is more preferable. When an organic solvent is contained, the appearance stability of the liquid is easily improved. When the content of the organic solvent is not more than the upper limit of the above range, the spread of dirt is excellent.
The total content of optional components other than the organic solvent is not particularly limited, but is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 7% by mass or less based on the total mass of the liquid detergent.
The total content of each component of the liquid detergent does not exceed 100% by mass.

液体洗浄剤の25℃におけるpHは、塗布放置時の衣類への影響を防止しやすい点で5〜9が好ましく、6〜8がより好ましい。液体洗浄剤のpHは、必要に応じて、pH調整剤を添加することにより調整できる。
本明細書におけるpHは、測定対象を25℃とし、pHメーター(製品名:HM−30G、東亜ディーケーケー株式会社製)により測定される値を意味する。
The pH of the liquid detergent at 25 ° C. is preferably 5 to 9 and more preferably 6 to 8 from the viewpoint of easily preventing the influence on clothes when left uncoated. The pH of the liquid detergent can be adjusted by adding a pH adjuster as necessary.
The pH in this specification means a value measured by a pH meter (product name: HM-30G, manufactured by Toa DKK Co., Ltd.) with a measurement target at 25 ° C.

<製造方法>
本発明の液体洗浄剤は、従来公知の液体洗浄剤の製造方法に準じて製造することができる。例えば、分散媒である水の一部に、pH調整剤を除く各成分を加えて混合した後、必要に応じてpH調整剤を添加してpHを調整した後、水の残部を加えて全体量を100質量%として、液体洗浄剤とする。
<Manufacturing method>
The liquid detergent of the present invention can be produced according to a conventionally known method for producing a liquid detergent. For example, after adding and mixing each component excluding the pH adjuster to a part of the water as the dispersion medium, adjusting the pH by adding a pH adjuster as necessary, and then adding the rest of the water The amount is set to 100% by mass to obtain a liquid detergent.

<使用方法>
本発明の液体洗浄剤は汚れの拡がり防止性に優れるため、液体洗浄剤を被洗物に直接塗布し、放置した後に洗濯を行う方法(塗布洗浄)に好適である。洗濯の方法としては、例えば、本発明の液体洗浄剤とは別の洗剤を単独で又は漂白剤や柔軟剤と共に水に入れた洗浄液を用い、前記放置後の被洗物を洗浄液に入れて洗濯機で洗濯する方法が挙げられる。
液体洗浄剤を被洗物に塗布した後、洗濯するまでの放置時間は、塗布洗浄することによる効果が充分に得られ易い点で、30分以上が好ましく、180分以上が好ましく、360分以上がさらに好ましい。特に、本発明の液体洗浄剤は汚れの拡がり防止性に優れるため、従来よりも放置時間を長くできるという利点を有する。例えば、24時間以上でもよい。
<How to use>
Since the liquid cleaning agent of the present invention is excellent in preventing spread of dirt, it is suitable for a method (coating and cleaning) in which the liquid cleaning agent is directly applied to an object to be washed and then washed after standing. As a washing method, for example, a detergent different from the liquid detergent of the present invention is used alone or a washing liquid in water together with a bleaching agent and a softening agent is used. The method of washing with a machine is mentioned.
The standing time until washing after application of the liquid detergent to the object to be washed is preferably 30 minutes or more, preferably 180 minutes or more, and preferably 360 minutes or more from the viewpoint that the effect of coating and washing can be sufficiently obtained. Is more preferable. In particular, the liquid cleaning agent of the present invention has an advantage that the standing time can be made longer than before because it is excellent in preventing spread of dirt. For example, it may be 24 hours or more.

以下、実施例を示して本発明を詳細に説明するが、本発明は以下の記載によって限定されるものではない。   EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description.

(使用原料)
<(A1)成分>
A1−i:ポリエチレングリコールジオレート(式(i)において、Xが−C(O)R、RとRがそれぞれ−C1733、AOがEO、m1が12である化合物)、商品名「イオネット DO−600」、三洋化成工業社製。
A1−ii:イソステアリン酸PEG−8グリセリル(式(ii)において、Yが−C(O)R、YとYがそれぞれ水素原子、Rが−C1735、AOがEO、m2+m3+m4=8である化合物)、商品名「ユニオックス GM−8IS」、日油社製。
A1−iii:ポリオキシエチレン硬化ヒマシ油(式(iii)において、RとRとRがそれぞれ−(CH10−、AOがEO、ZとZとZがそれぞれ水素原子、m5+m6+m7=20である化合物)、商品名「ブラウノンCW−20−90」、青木油脂工業社製。
(Raw materials used)
<(A1) component>
A1-i: Polyethylene glycol diolate (in the formula (i), X is —C (O) R 2 , R 1 and R 2 are each —C 17 H 33 , AO is EO, and m1 is 12), Product name “Ionet DO-600”, manufactured by Sanyo Chemical Industries.
A1-ii: PEG-8 glyceryl isostearate (in the formula (ii), Y 1 is —C (O) R 3 , Y 2 and Y 3 are each a hydrogen atom, R 3 is —C 17 H 35 , and AO is EO. , M2 + m3 + m4 = 8), trade name “Uniox GM-8IS”, manufactured by NOF Corporation.
A1-iii: polyoxyethylene hydrogenated castor oil (in formula (iii), R 4 , R 5 and R 6 are each — (CH 2 ) 10 —, AO is EO, Z 1 , Z 2 and Z 3 are each hydrogen. Atom, m5 + m6 + m7 = 20 compound), trade name “Brownon CW-20-90”, manufactured by Aoki Oil & Fat Co., Ltd.

<(A2)成分>
A2−1:ポリオキシエチレンアルキルエーテル(式(iv)において、R11が炭素数12〜14のアルキル基、sが6である)、品名「LMAF−90」、ライオン社製。
<(A2) component>
A2-1: Polyoxyethylene alkyl ether (in formula (iv), R 11 is an alkyl group having 12 to 14 carbon atoms and s is 6), product name “LMAF-90”, manufactured by Lion Corporation.

<(B)成分>
B−1:AES。ポリオキシアルキレンアルキルエーテル硫酸塩(ポリオキシエチレンラウリルエーテル硫酸ナトリウムとポリオキシエチレンミリスチルエーテル硫酸ナトリウムとの混合物、EOの平均付加モル数1)。式(v)におけるR21が炭素数12及び14の直鎖状のアルキル基、kが1、nが0、Mがナトリウムであり、B−1全体に対するkが0かつnが0である化合物(成分(b0))の割合が43質量%である。下記調製例1の方法で合成したもの。
<(C)成分(比較例)>
C−1:直鎖アルキルベンゼンスルホン酸ナトリウム(LAS)、商品名「ライポンLS−250」、ライオン社製。
<(B) component>
B-1: AES. Polyoxyalkylene alkyl ether sulfate (mixture of sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene myristyl ether sulfate, average addition mole number of EO 1). A compound in which R 21 in formula (v) is a linear alkyl group having 12 and 14 carbon atoms, k is 1, n is 0, M is sodium, k is 0 and n is 0 with respect to the whole B-1. The proportion of (component (b0)) is 43% by mass. Synthesized by the method of Preparation Example 1 below.
<Component (C) (Comparative Example)>
C-1: Sodium linear alkylbenzene sulfonate (LAS), trade name “Lypon LS-250”, manufactured by Lion Corporation.

<任意成分>
グリセリン:商品名「化粧品用グリセリン」、阪本薬品工業社製。
やし脂肪酸:商品名「椰子脂肪酸(PKO)TC」、日油社製。
イソオクチル酸2−エチルヘキシル(2H08)商品名「イソオクチル酸2-エチルヘキシル」ライオン社製。
クエン酸:商品名:「無水クエン酸」、扶桑化学工業社製。
酵素:商品名「Medley Core」 Novozymes社製。
MEA:商品名「モノエタノールアミン」、日本触媒社製。
香料:特開2003‐268398号公報の表7〜14に記載の香料組成物A。
色素:商品名「緑色3号」、癸巳化成社製。
水:精製水。
<Optional component>
Glycerin: Trade name “glycerin for cosmetics”, manufactured by Sakamoto Pharmaceutical Co., Ltd.
Palm Fatty Acid: Trade name “Zushi Fatty Acid (PKO) TC”, manufactured by NOF Corporation.
2-ethylhexyl isooctylate (2H08), trade name “2-ethylhexyl isooctylate” manufactured by Lion Corporation.
Citric acid: Trade name: “Citric anhydride”, manufactured by Fuso Chemical Industry Co., Ltd.
Enzyme: Trade name “Medley Core” manufactured by Novozymes.
MEA: trade name “monoethanolamine”, manufactured by Nippon Shokubai Co., Ltd.
Perfume: Perfume composition A described in Tables 7 to 14 of JP-A-2003-268398.
Dye: Trade name “Green No. 3”, manufactured by Hatake Kasei Co., Ltd.
Water: Purified water.

[調製例1:(B−1)成分の合成]
容量4Lのオートクレーブ中に、原料アルコールとしてP&G社製の商品名CO1270アルコール(炭素数12のアルコールと炭素数14のアルコールとの質量比75/25の混合物)400gと、反応用触媒として水酸化カリウム触媒0.8gとを仕込み、該オートクレーブ内を窒素で置換した後、攪拌しながら昇温した。続いて、温度を180℃、圧力を0.3MPa以下に維持しながらエチレンオキシド91gを導入し、反応させることによりアルコールエトキシレートを得た。
ガスクロマトグラフ:Hewlett−Packard社製のGC−5890と、検出器:水素炎イオン化型検出器(FID)と、カラム:Ultra−1(HP社製、L25m×φ0.2mm×T0.11μm)と、を用いて分析した結果、得られたアルコールエトキシレートは、エチレンオキシドの平均付加モル数が1.0であった。また、エチレンオキシドが付加していない化合物(最終的に成分(b0)となるもの)の量が得られたアルコールエトキシレート全体に対して43質量%であった。
次に、上記で得たアルコールエトキシレート237gを、攪拌装置付の500mLフラスコに採り、窒素で置換した後、液体無水硫酸(サルファン)96gを、反応温度40℃に保ちながらゆっくりと滴下した。滴下終了後、1時間攪拌を続け(硫酸化反応)、ポリオキシエチレンアルキルエーテル硫酸を得た。次いで、これを水酸化ナトリウム水溶液で中和することによりB−1を得た。
[Preparation Example 1: Synthesis of component (B-1)]
In an autoclave with a capacity of 4 L, 400 g of a trade name CO1270 alcohol (mixture of 75/25 mass ratio of 12-carbon alcohol and 14-carbon alcohol) manufactured by P & G as raw material alcohol and potassium hydroxide as a reaction catalyst After charging 0.8 g of the catalyst and replacing the inside of the autoclave with nitrogen, the temperature was raised with stirring. Subsequently, while maintaining the temperature at 180 ° C. and the pressure at 0.3 MPa or less, 91 g of ethylene oxide was introduced and reacted to obtain an alcohol ethoxylate.
Gas chromatograph: GC-5890 manufactured by Hewlett-Packard, Detector: Hydrogen flame ionization detector (FID), Column: Ultra-1 (manufactured by HP, L25m × φ0.2mm × T0.11 μm), As a result, the alcohol ethoxylate obtained had an average addition mole number of ethylene oxide of 1.0. Further, the amount of the compound to which ethylene oxide was not added (final component (b0)) was 43% by mass with respect to the total alcohol ethoxylate obtained.
Next, 237 g of the alcohol ethoxylate obtained above was placed in a 500 mL flask equipped with a stirrer and replaced with nitrogen, and 96 g of liquid sulfuric anhydride (sulfane) was slowly added dropwise while maintaining the reaction temperature at 40 ° C. After completion of dropping, stirring was continued for 1 hour (sulfation reaction) to obtain polyoxyethylene alkyl ether sulfuric acid. Subsequently, B-1 was obtained by neutralizing this with sodium hydroxide aqueous solution.

(実施例1〜17、比較例1〜4)
表1、2に示す組成で、各成分を水に加え、混合して各例の液体洗浄剤を調製した。
表中の配合量は純分換算値である。表中に配合量が記載されていない成分は、配合されていない。pH調整剤の含有量「適量」は、各例の液体組成物の25℃におけるpHを7に調整するのに要した量である。水の含有量「バランス」は、液体組成物に含まれる全成分の合計が100質量%となるように加えられる残部を意味する。
共通成分は以下の組成である。液体洗浄剤の総質量に対して、共通成分の総質量は3.95001質量%である。
共通成分の組成:やし脂肪酸1.0質量%、イソオクチル酸2−エチルヘキシル0.5質量%、クエン酸1.3質量%、酵素0.1質量%、MEA1.0質量%、香料0.05質量%、色素0.00001質量%。
各例の液体洗浄剤について、下記の方法で洗浄力、汚れの拡がり防止性、外観安定性を評価した。結果を表に示す。
(Examples 1-17, Comparative Examples 1-4)
With the compositions shown in Tables 1 and 2, each component was added to water and mixed to prepare a liquid detergent for each example.
The compounding amount in the table is a pure conversion value. A component whose blending amount is not described in the table is not blended. The content “appropriate amount” of the pH adjuster is an amount required to adjust the pH at 25 ° C. of the liquid composition of each example to 7. The water content “balance” means the balance added so that the total of all components contained in the liquid composition is 100 mass%.
The common component has the following composition. The total mass of the common components is 3.95001 mass% with respect to the total mass of the liquid detergent.
Composition of common components: palm fatty acid 1.0% by mass, 2-ethylhexyl isooctylate 0.5% by mass, citric acid 1.3% by mass, enzyme 0.1% by mass, MEA 1.0% by mass, fragrance 0.05 Mass%, pigment 0.00001 mass%.
About the liquid cleaning agent of each example, the cleaning power, the spreading | diffusion prevention property, and external appearance stability were evaluated by the following method. The results are shown in the table.

[洗浄力の評価(固体脂洗浄力)]
(1)汚垢布の作製と洗浄
5cm×5cmに裁断したB.V.D. GOLD 綿100% 丸首半袖Tシャツ(谷頭商店)を未汚垢布(汚れ付着前)とする。未汚垢布に、牛脂をクロロホルムで5倍に希釈し0.02%のカーボン粒子を添加したものを0.050mL滴下し、室温にて2〜3時間風乾したものを油汚れ汚垢布(洗浄前)とした。
油汚れ汚垢布5枚のそれぞれに対し、評価対象の液体洗浄剤を0.300mLずつ塗布し、6時間静置したものを試験布とした。
その後、15℃の水道水900mLと市販の洗剤(商品名「トップ スーパーNANOX」、ライオン社製)0.3gを入れたTerg−O−Tometer(UNITED STATES TESTING社製)に、上記試験布5枚を入れ、120rpmで10分間洗浄した(浴比20倍)。
その後、洗浄後の試験布5枚を取り出し、2槽式洗濯機(品番「CW−C30A1型」三菱電機社製)で3分間流水すすぎをし、1分間脱水した後、風乾したものを洗浄後の油汚れ汚垢布とした。
[Evaluation of detergency (solid fat detergency)]
(1) Fabrication and cleaning of soiled cloth B. Cut to 5 cm × 5 cm V. D. GOLD 100% cotton Round neck short-sleeved T-shirt (Tanigami Shoten) is used as an unstained cloth (before soiling). To an unsoiled cloth, 0.050 mL of beef tallow diluted 5 times with chloroform and added with 0.02% carbon particles was added dropwise and air-dried at room temperature for 2-3 hours. Before washing).
A test cloth was prepared by applying 0.300 mL of the liquid cleaning agent to be evaluated to each of the five oil-stained dirt cloths and allowing them to stand for 6 hours.
Thereafter, 5 pieces of the test cloth were added to Terg-O-Tometer (manufactured by UNITED STATES TESTING) containing 900 mL of 15 ° C. tap water and 0.3 g of a commercial detergent (trade name “Top Super NANOX”, manufactured by Lion). And washed for 10 minutes at 120 rpm (bath ratio 20 times).
Then, 5 test cloths after washing are taken out, rinsed with running water for 3 minutes in a 2-tank washing machine (product number “CW-C30A1”, manufactured by Mitsubishi Electric Corporation), dehydrated for 1 minute, and then air-dried The oil-stained dirt cloth.

(2)固体脂洗浄力の評価
測色色差計(商品名「SE2000」、日本電色社製)を用い、未汚垢布(B.V.D. GOLD 綿100% 丸首半袖Tシャツ(谷頭商店))、及び洗浄前後の油汚れ汚垢布についての反射率をそれぞれ測定し、下記式(I)により洗浄率(%)を求めた。
洗浄率(%)=(洗浄前の汚垢布のK/S−洗浄後の汚垢布のK/S)/(洗浄前の汚
垢布のK/S−未汚垢布のK/S)×100 ・・・(I)
[式(I)中、K/Sは、(1−R/100)/(2R/100)であり、Rは、洗浄前の汚垢布、洗浄後の汚垢布又は未汚垢布の反射率(%)を表す。また、Kは吸光係数、Sは散乱係数、Rは絶対反射率をそれぞれ表す。]
この洗浄率の値が大きいほど、洗浄力が高いことを意味する。
5枚の試験布の洗浄率の平均値を算出し、下記の基準で洗浄力を評価した。洗浄率の平均値が55%以上であるとき合格と判定する。
(評価基準)
◎:洗浄率の平均値が75%以上。
○:洗浄率の平均値が65%以上75%未満。
△:洗浄率の平均値が55%以上65%未満。
×:洗浄率の平均値が55%未満。
(2) Evaluation of solid fat detergency Using a colorimetric color difference meter (trade name “SE2000”, manufactured by Nippon Denshoku Co., Ltd.), unstained cloth (BVD GOLD 100% cotton round neck short sleeve T-shirt (Tanigami) The reflectance of the oil stain soil cloth before and after washing was measured, and the washing rate (%) was determined by the following formula (I).
Washing rate (%) = (K / S of soiled cloth before washing−K / S of soiled cloth after washing) / (K / S of soiled cloth before washing−K / S of unstained cloth) ) × 100 (I)
[In the formula (I), K / S is (1-R / 100) 2 / (2R / 100), and R is a dirt cloth before washing, a dirt cloth after washing, or an unstained cloth. Represents the reflectance (%). K represents an extinction coefficient, S represents a scattering coefficient, and R represents an absolute reflectance. ]
A larger value of the cleaning rate means higher cleaning power.
The average value of the cleaning rate of the five test cloths was calculated, and the cleaning power was evaluated according to the following criteria. When the average value of the cleaning rate is 55% or more, it is determined to be acceptable.
(Evaluation criteria)
A: The average value of the cleaning rate is 75% or more.
○: The average value of the cleaning rate is 65% or more and less than 75%.
Δ: The average value of the cleaning rate is 55% or more and less than 65%.
X: The average value of the cleaning rate is less than 55%.

[汚れの拡がり防止性の評価(塗布後12時間放置)]
(1)油汚れ汚垢布の作製
12cm×17cmに裁断したB.V.D. GOLD 綿100% 丸首半袖Tシャツ(谷頭商店)に、0.03質量%のオイルレッドを含んだ、オレイン酸やトリオレイン等を混合した皮脂モデル汚垢油をクロロホルムで希釈し、5cm間隔で6箇所に50μLずつ滴下し、室温にて1時間乾燥させたものを油汚れ汚垢布とした。
(2)洗浄方法と拡がり防止性の評価
油汚れ汚垢布の油を滴下した部分に、評価対象の液体洗浄剤を300μLずつ塗布し、12時間静置したものを試験布とした。
次いで、全自動洗濯機(ハイアール)に、試験布と、市販の洗剤(商品名「トップ スーパーNANOX」、ライオン社製)5gを入れ、さらに5枚のB.V.D. GOLD 綿100% 丸首半袖Tシャツ(谷頭商店)を入れて、低水位設定にて洗浄し、風乾したものを洗浄後の試験布とした。
液体洗浄剤を塗布する前の油汚れ汚垢布(対照)、及び洗浄後の試験布について、楕円状に広がった油汚れの長軸の長さを拡がり径として測定した。汚垢油を滴下した6箇所の拡がり径の平均値を算出し、下記の基準で汚れの拡がり防止性を評価した。
洗浄後の試験布における拡がり径の平均値をA(mm)、対照における拡がり径の平均値をB(mm)とするとき、A−Bを「拡がり径の平均値の差」とする。「拡がり径の平均値の差」が7mm未満であるとき合格と判定する。
(評価基準)
◎:拡がり径の平均値の差が3mm未満。
○:拡がり径の平均値の差が3mm以上5mm未満。
△:拡がり径の平均値の差が5mm以上7mm未満。
×:拡がり径の平均値の差が7mm以上。
[Evaluation of preventing spread of dirt (left for 12 hours after application)]
(1) Production of oil-stained dirt cloth B. Cut to 12 cm × 17 cm V. D. GOLD 100% Cotton Short-sleeved T-shirt (Tanigami Shoten) Dilute sebum model soil oil mixed with oleic acid, triolein, etc. containing 0.03% by mass of oil red with chloroform, 6 A 50 μL aliquot was dropped onto the spot and dried at room temperature for 1 hour to obtain an oily soiled cloth.
(2) Evaluation of cleaning method and spread prevention property 300 μL of the liquid cleaning agent to be evaluated was applied to the portion of the oil-stained and dirty cloth where oil was dropped, and the test cloth was left for 12 hours.
Next, a test cloth and 5 g of a commercially available detergent (trade name “Top Super NANOX”, manufactured by Lion Corporation) are placed in a fully automatic washing machine (Haier). V. D. GOLD 100% cotton Round neck short-sleeved T-shirt (Tanigami Shoten) was put, washed at a low water level setting, and air-dried to obtain a test cloth after washing.
The length of the major axis of the oil stain spread in an elliptical shape was measured as the spread diameter of the oil stain soil cloth (control) before application of the liquid detergent and the test cloth after washing. The average value of the spread diameters at six locations where the soil oil was dropped was calculated, and the spread prevention property of the dirt was evaluated according to the following criteria.
When the average value of the spread diameter in the test cloth after washing is A (mm) and the average value of the spread diameter in the control is B (mm), A−B is “difference in the average value of the spread diameter”. When the “difference in the average value of the spread diameters” is less than 7 mm, it is determined as acceptable.
(Evaluation criteria)
(Double-circle): The difference of the average value of a spread diameter is less than 3 mm.
○: The difference in the average value of the spread diameter is 3 mm or more and less than 5 mm.
(Triangle | delta): The difference of the average value of a spread diameter is 5 mm or more and less than 7 mm.
X: The difference of the average value of a spread diameter is 7 mm or more.

[液安定性の評価]
透明のガラス製瓶に、各例の液体洗浄剤40gをそれぞれ充填し、蓋を閉めて密封した。この状態で−5℃の恒温槽に24時間静置して保存した。
24時間の保存の後、液の外観を目視で観察し、下記の基準で液体洗浄剤の外観安定性を評価した。
(評価基準)
○:配合直後無色透明で、−5℃保存後も無色透明であり流動性がある。
△:配合直後無色透明で、−5℃保存後析出又は濁りが認められた。
×:配合直後から沈殿又は分離が認められた。
[Evaluation of liquid stability]
A transparent glass bottle was filled with 40 g of the liquid cleaning agent of each example, and the lid was closed and sealed. In this state, it was stored in a -5 ° C constant temperature bath for 24 hours.
After storage for 24 hours, the appearance of the liquid was visually observed, and the appearance stability of the liquid detergent was evaluated according to the following criteria.
(Evaluation criteria)
○: Colorless and transparent immediately after blending, and colorless and transparent after storage at −5 ° C. and fluidity.
Δ: colorless and transparent immediately after blending, precipitation or turbidity was observed after storage at −5 ° C.
X: Precipitation or separation was observed immediately after blending.

Figure 2019189690
Figure 2019189690

Figure 2019189690
Figure 2019189690

表1、2に示すように、実施例1〜17は、洗浄力及び液安定性が良好であり、液体洗浄剤を塗布して長時間放置したときの汚れの拡がり防止性に優れていた。
(A1)成分を含有しない比較例1は、洗浄力が劣った。
(B)成分を含有しない比較例2は、液安定性が悪かったため、他の評価は行わなかった。
(B)成分の代わりに、(C)成分を配合した比較例3は、汚れの拡がり防止性が劣った。
(A1)成分と(B)成分を含むものの、(A)/(B)が2.5を超える比較例4は汚れの拡がり防止性が劣った。
As shown in Tables 1 and 2, Examples 1 to 17 had good detergency and liquid stability, and were excellent in preventing spread of dirt when the liquid detergent was applied and left for a long time.
Comparative Example 1 containing no component (A1) was inferior in detergency.
Since Comparative Example 2 containing no component (B) had poor liquid stability, no other evaluation was performed.
The comparative example 3 which mix | blended (C) component instead of (B) component was inferior in the spreading | diffusion prevention property of dirt.
Although the component (A1) and the component (B) were included, Comparative Example 4 in which (A) / (B) exceeded 2.5 was inferior in the spread of dirt.

Claims (3)

(A)成分:ノニオン界面活性剤、及び
(B)成分:ポリオキシアルキレンアルキルエーテル硫酸又はその塩、を含み、
前記(A)成分が、
(A1)成分:下記式(i)で表される化合物、下記式(ii)で表される化合物、及び下記式(iii)で表される化合物からなる群から選ばれる1種以上、を含み、
衣料用液体洗浄剤の総質量に対して、前記(A1)成分の含有量が1質量%以上であり、
前記(B)成分の含有量に対する前記(A)成分の含有量の質量比を表す(A)/(B)が2.5以下である、衣料用液体洗浄剤。
Figure 2019189690
式(i)において、Xは水素原子または−C(O)Rであり、R、Rは独立して炭素数7〜19の炭化水素基であり、AOはオキシエチレン基またはオキシプロピレン基の少なくとも一方であり、m1はAOの平均繰返し数を表し、3〜20の数である。
Figure 2019189690
式(ii)において、Y〜Yは独立して水素原子または−C(O)Rであり、Y〜Yの少なくとも1つは−C(O)Rであり、Rは炭素数9〜19の炭化水素基であり、AOはオキシエチレン基またはオキシプロピレン基の少なくとも一方であり、m2〜m4はAOの平均繰返し数を表し、独立して0〜15の数である。
Figure 2019189690
式(iii)において、Z〜Zは独立して水素原子または−C(O)Rであり、Rは炭素数11〜21の炭化水素基であり、AOはオキシエチレン基またはオキシプロピレン基の少なくとも一方であり、m5〜m7はAOの平均繰返し数を表し、独立して0以上の数であり、m5+m6+m7は5〜100の数であり、R、R、Rは独立して−(CH10−又は−(CHCH=CH(CH)−である。
(A) component: nonionic surfactant, and (B) component: polyoxyalkylene alkyl ether sulfuric acid or a salt thereof,
The component (A) is
(A1) component: one or more selected from the group consisting of a compound represented by the following formula (i), a compound represented by the following formula (ii), and a compound represented by the following formula (iii) ,
The content of the component (A1) is 1% by mass or more with respect to the total mass of the liquid detergent for clothing,
A liquid detergent for clothing, wherein (A) / (B) representing the mass ratio of the content of the component (A) to the content of the component (B) is 2.5 or less.
Figure 2019189690
In the formula (i), X is a hydrogen atom or —C (O) R 2 , R 1 and R 2 are independently a hydrocarbon group having 7 to 19 carbon atoms, and AO is an oxyethylene group or oxypropylene It is at least one of the groups, and m1 represents the average number of repetitions of AO and is a number of 3 to 20.
Figure 2019189690
In formula (ii), Y 1 to Y 3 are independently a hydrogen atom or —C (O) R 3 , at least one of Y 1 to Y 3 is —C (O) R 3 , and R 3 Is a hydrocarbon group having 9 to 19 carbon atoms, AO is at least one of an oxyethylene group or an oxypropylene group, m2 to m4 represent the average number of repetitions of AO, and are independently a number of 0 to 15 .
Figure 2019189690
In formula (iii), Z 1 to Z 3 are independently a hydrogen atom or —C (O) R 7 , R 7 is a hydrocarbon group having 11 to 21 carbon atoms, and AO is an oxyethylene group or an oxy group It is at least one of propylene groups, m5 to m7 represent the average number of AO repetitions, and are independently 0 or more, m5 + m6 + m7 is a number of 5 to 100, and R 4 , R 5 and R 6 are independent to - (CH 2) 10 - or - (CH 2) 7 CH = CH (CH 2) - a.
衣料用液体洗浄剤の総質量に対して、界面活性剤の総質量が40質量%以下である、請求項1に記載の衣料用液体洗浄剤。   The liquid cleaning agent for clothing according to claim 1, wherein the total mass of the surfactant is 40% by mass or less based on the total mass of the liquid cleaning agent for clothing. (A2)成分:下記式(iv)で表されるポリオキシエチレンアルキルエーテル、の含有量が、衣料用液体洗浄剤の総質量に対して5質量%以下である、請求項1または2に記載の衣料用液体洗浄剤。
11−O−(EO)−H ・・・(iv)
式(iv)において、R11は炭素数8〜18の炭化水素基であり、EOはオキシエチレン基であり、sはEOの平均繰り返し数を表し、2〜13の数である。
The content of (A2) component: polyoxyethylene alkyl ether represented by the following formula (iv) is 5% by mass or less based on the total mass of the liquid detergent for clothing. Liquid detergent for clothing.
R 11 —O— (EO) s —H (iv)
In the formula (iv), R 11 is a hydrocarbon group having 8 to 18 carbon atoms, EO is an oxyethylene group, s represents an average number of repetitions of EO, and is a number of 2 to 13.
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