JP5891073B2

JP5891073B2 - Method for producing solid detergent composition

Info

Publication number: JP5891073B2
Application number: JP2012051050A
Authority: JP
Inventors: 利哉森川
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 2012-03-07
Filing date: 2012-03-07
Publication date: 2016-03-22
Anticipated expiration: 2032-03-07
Also published as: JP2013185062A

Description

本発明は、固形洗浄剤組成物に関する。 The present invention relates to a solid detergent composition.

機械練石鹸は、石鹸基剤をプロッダーと呼ばれる押出機で棒状に成型された後、型打機でさらに成型されて製造される。プロッダーは、押出しスクリュー部とその先端部に蜂の巣状の多孔プレートと、先細になったコニカル部を有し、石鹸基剤がここを通ると、一度、ヌードル状になり、次にコニカル部で圧縮されて、棒状に押出される。このように石鹸は、ヌードル状になった石鹸基剤が圧着して形成される。この結果、石鹸の使用中におこる膨潤、乾燥が繰り返されると、ヌードル同士の圧着面から、ひび割れが生じることが知られている。
このような石鹸のひび割れを抑制するため、種々の高分子物質を配合した石鹸が検討されている（例えば、特許文献１、特許文献２、特許文献３）。 Mechanical kneaded soap is manufactured by forming a soap base into a rod shape using an extruder called a pudder and then molding the soap base using a stamping machine. The pudder has an extruded screw part, a honeycomb-shaped perforated plate at its tip, and a tapered conical part. Once the soap base passes through it, it becomes noodle once and then compressed in the conical part. And extruded into a rod shape. As described above, the soap is formed by press-bonding a noodle-shaped soap base. As a result, it is known that when swelling and drying that occur during the use of soap are repeated, cracking occurs from the pressure-bonding surface between the noodles.
In order to suppress such cracking of soap, soaps containing various polymer substances have been studied (for example, Patent Document 1, Patent Document 2, and Patent Document 3).

特開昭４８−２５７０７号公報JP-A-48-25707 特開昭５７−１１５５００号公報JP 57-115500 A 特開昭５８−１６７７００号公報JP 58-167700 A

しかしながら、高分子化合物を配合すると、石鹸本来のさっぱり感が損なわれるという問題があった。
また、石鹸は、膨潤、乾燥を繰り返し行っている間に、石鹸の結晶形が変化して、泡立ちが低下しやすい。このように、最後まできれいな外観で性能を低下させずに使用することに課題があった。
さらに、石鹸は、すすぎ時に、水道水中のカルシウムイオン等と反応して水不溶性のスカムを形成する。このスカムは、洗面器等のプラスチック製品や排水溝の蓋等に付着して乾燥すると、取れにくくなり、浴室等を汚してしまうという問題がある。 However, when a polymer compound is blended, there is a problem that the original refreshing feeling of the soap is impaired.
In addition, soap repeatedly changes its crystal form during repeated swelling and drying, and foaming tends to decrease. As described above, there has been a problem in using it without degrading performance with a beautiful appearance to the end.
Furthermore, the soap reacts with calcium ions or the like in tap water to form a water-insoluble scum at the time of rinsing. When this scum adheres to a plastic product such as a wash basin or a lid of a drainage groove and dries, it becomes difficult to remove and there is a problem that the bathroom or the like is soiled.

本発明は、使用途中でのひび割れが抑制され、繰り返し使用した後においても十分な泡立ちが得られ、しかも浴室等を汚しにくくする、機械練製法で得られる固形洗浄剤組成物を提供することを課題とする。 The present invention provides a solid detergent composition obtained by a mechanical kneading method, in which cracking during use is suppressed, sufficient foaming is obtained even after repeated use, and the bathroom is not easily soiled. Let it be an issue.

本発明者らは、脂肪酸ナトリウム塩と、特定の分布を有するアルキルエーテルカルボン酸又はその塩、及び水を特定の割合で組み合わせて用いれば、前記課題を解決した固形洗浄剤組成物が得られることを見出した。 When the present inventors use a fatty acid sodium salt, an alkyl ether carboxylic acid having a specific distribution or a salt thereof, and water in combination at a specific ratio, a solid detergent composition that solves the above problems can be obtained. I found.

本発明は、次の成分（Ａ）、（Ｂ）及び（Ｃ）：
（Ａ）脂肪酸ナトリウム塩６５〜９５質量％、
（Ｂ）一般式（１） The present invention includes the following components (A), (B) and (C):
(A) Fatty acid sodium salt 65-95 mass%,
(B) General formula (1)

（式中、Ｒ¹は炭素数４〜２２のアルキル基を示し、ｎは０〜２０の数を示し、Ｍは水素原子、アルカリ金属、アルカリ土類金属、アンモニウム又は有機アンモニウムを示す）
で表されるアルキルエーテルカルボン酸又はその塩であって、Ｒ¹の平均炭素数が１０．８〜１２．８であり、ｎ＝０の成分を９．６質量％を超え２７質量％以下、ｎ＝１の成分とｎ＝２の成分を合計で２１質量％以上４０質量％未満含むアルキルエーテルカルボン酸又はその塩３〜１５質量％、
（Ｃ）水
を含有し、機械練製法で得られる固形洗浄剤組成物を提供するものである。 (In the formula, R ¹ represents an alkyl group having 4 to 22 carbon atoms, n represents a number of 0 to 20, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, or organic ammonium).
In which the average carbon number of R ¹ is 10.8 to 12.8, and the component of n = 0 exceeds 9.6% by mass and is 27% by mass or less, an alkyl ether carboxylic acid or a salt thereof containing 3 to 15% by mass of a component of n = 1 and a component of n = 2 in total of 21% by mass or more and less than 40% by mass,
(C) A solid detergent composition containing water and obtained by a mechanical kneading method is provided.

本発明の固形洗浄剤組成物は、さっぱりとした使用感で、使用途中でひび割れが抑制され、繰り返し使用しても泡立ちが良好で、しかもスカムの分散性に優れ、浴室等を汚しにくくするものである。 The solid detergent composition of the present invention has a refreshing feeling, cracks are suppressed during use, foaming is good even after repeated use, and scum is highly dispersible, making it difficult to stain bathrooms, etc. It is.

本発明で用いる成分（Ａ）の脂肪酸としては、炭素数８〜２２のものが好ましく、更に１２〜１８のものが好ましい。成分（Ａ）の脂肪酸は、牛脂、豚脂等の動物性油脂；パーム核油、パーム油、ヤシ油、ヒマシ油、大豆油、綿実油、ナタネ油、ヒマワリ油等の植物性油脂から得られるものを、１種又は２種以上組み合わせて用いることもできる。また、これらを基剤とした石鹸素地を使用することができる。これらのうち、製造コストの点からパーム核油、パーム油、ヤシ油から得られる脂肪酸が好ましく、さらにパーム核油、パーム油から得られる脂肪酸が好ましい。また、石鹸の泡立ちの観点から、ラウリン酸の比率の多いパーム核油と、石鹸の溶け崩れ性の観点から、パーム油を精製して得られた高融点成分であるパームステアリン油と呼ばれる固体脂（パーム油から低融点成分であるパームオレインとよばれる液状のものを除いた残りの脂肪酸）を組合せて得られる脂肪酸ナトリウム塩を用いるのが好ましい。
なお、パーム核油の好ましい脂肪酸組成としては、起泡性の観点から、ラウリン酸５０〜６０質量％、ミリスチン酸１０〜２０質量％、オレイン酸８〜１５質量％を含有するものが挙げられる。
パームステアリン油の好ましい脂肪酸組成は、溶け崩れの抑制の観点から、パルミチン酸５０〜７０質量％、ステアリン酸を３〜８質量％及びオレイン酸２５〜３５質量％を含有するものが挙げられる。
パーム核油とパームステアリン油の質量割合は、起泡性、溶け崩れの抑制の観点から、（パーム核油）／（パームステアリン油）＝９０／１０〜１０／９０が好ましく、８５／１５〜１５／８５が更に好ましく、５０／５０〜２０／８０が更に好ましい。 As the fatty acid of component (A) used in the present invention, those having 8 to 22 carbon atoms are preferred, and those having 12 to 18 carbon atoms are more preferred. The fatty acid of component (A) is obtained from animal fats and oils such as beef tallow and lard; vegetable oils such as palm kernel oil, palm oil, coconut oil, castor oil, soybean oil, cottonseed oil, rapeseed oil and sunflower oil Can be used alone or in combination of two or more. Moreover, the soap base based on these can be used. Of these, fatty acids obtained from palm kernel oil, palm oil, and palm oil are preferable from the viewpoint of production cost, and fatty acids obtained from palm kernel oil and palm oil are more preferable. Moreover, from the viewpoint of soap foaming, a solid fat called palm stearin oil, which is a high melting point component obtained by refining palm oil from the viewpoint of soap core oil with a high ratio of lauric acid and the melting property of soap It is preferable to use a fatty acid sodium salt obtained by combining (remaining fatty acid excluding a liquid oil called palm olein which is a low melting point component from palm oil).
In addition, as a preferable fatty acid composition of palm kernel oil, what contains 50-60 mass% of lauric acids, 10-20 mass% myristic acid, and 8-15 mass% oleic acid from a foamable viewpoint is mentioned.
The preferable fatty acid composition of palm stearin oil includes those containing 50 to 70% by mass of palmitic acid, 3 to 8% by mass of stearic acid, and 25 to 35% by mass of oleic acid from the viewpoint of suppression of melting and collapsing.
The mass ratio of palm kernel oil and palm stearin oil is preferably (palm kernel oil) / (palm stearin oil) = 90/10 to 10/90, and 85/15 to 85% from the viewpoints of foamability and suppression of dissolution. 15/85 is more preferable, and 50/50 to 20/80 is more preferable.

成分（Ａ）の脂肪酸ナトリウム塩は、１種又は２種以上を用いることができ、石鹸の成形性、泡立ち、の点から、全組成中に６５〜９５質量％含有され、好ましくは６８〜９０質量％、更に好ましくは、７０〜８７質量％含有される。 The fatty acid sodium salt of component (A) can be used alone or in combination of two or more, and is contained in an amount of 65 to 95% by mass, preferably 68 to 90%, from the viewpoint of soap moldability and foaming. It is contained by mass%, more preferably 70 to 87 mass%.

本発明で用いる成分（Ｂ）のアルキルエーテルカルボン酸又はその塩は、一般式（１）で表されるものである。
式中、Ｒ¹は炭素数４〜２２のアルキル基であり、炭素数６〜２０のアルキル基、更に炭素数８〜１８のアルキル基が好ましく、炭素数８〜１６、更には炭素数１０〜１６のアルキル基がより好ましい。また、Ｒ¹のアルキル鎖は、直鎖又は分岐鎖のいずれでも良いが、起泡性の点から、直鎖アルキル基が好ましい。また、Ｒ¹の平均炭素数は１０．８〜１２．８であり、好ましくは１０．８〜１２．５であり、より好ましくは１２．１〜１２．４である。この範囲内であれば、起泡性及び泡質の点で優れるので好ましい。
また、Ｒ¹は２種以上のアルキル基を含むことが好ましく、一番含有量の多いアルキル鎖長を有する成分が５５質量％以上９７質量％未満であるのが好ましく、６０〜９５質量％がより好ましく、さらに７０〜９５質量％であるのが、泡量及び泡質に優れるので好ましい。 The alkyl ether carboxylic acid of component (B) or a salt thereof used in the present invention is represented by the general formula (1).
In the formula, R ¹ is an alkyl group having 4 to 22 carbon atoms, preferably an alkyl group having 6 to 20 carbon atoms, more preferably an alkyl group having 8 to 18 carbon atoms, 8 to 16 carbon atoms, and further 10 to 10 carbon atoms. 16 alkyl groups are more preferred. The alkyl chain of R ¹ may be either a straight chain or a branched chain, but a straight chain alkyl group is preferred from the viewpoint of foamability. The average carbon number of R ¹ is 10.8 to 12.8, preferably 10.8 to 12.5, and more preferably 12.1 to 12.4. If it is in this range, it is preferable in terms of foamability and foam quality.
R ¹ preferably contains two or more alkyl groups, and the component having the largest alkyl chain length is preferably 55% by mass or more and less than 97% by mass, and 60 to 95% by mass. More preferably, it is preferably 70 to 95% by mass because the foam amount and foam quality are excellent.

また、式中、ｎは０〜２０の数を示し、０〜１２がより好ましい。なお、ｎは、エチレンオシキシドの付加モル数を示すが、成分（Ｂ）の組成中の平均付加モル数（ｎの平均値）は、泡立ちが良好で使用途中でのひび割れを抑制する点から、１．５〜１０が好ましく、２．５〜６．４がより好ましく、２．５〜３．７がさらに好ましく、２．５〜３．４がさらに好ましく、２．８〜３．４がさらに好ましく、２．８〜３．１がさらに好ましい。
成分（Ｂ）のアルキルエーテルカルボン酸又はその塩は、一般式（１）において、ｎ＝０の成分を９．６質量％を超え２７質量％以下、好ましくは９．８〜２７質量％、より好ましくは９．９〜２７質量％、更に好ましくは９．９〜１６質量％、より好ましくは９．９〜１５質量％含むものである。この範囲内とすることにより、泡量、泡質に優れ、さっぱりとした使用感になり、使用途中でひび割れが抑制され、繰り返し使用しても泡立ちが良好で、スカムの分散性に優れ、浴室等を汚しにくくする。
さらに、ｎ＝１の成分とｎ＝２の成分を合計で２１〜４０質量％未満、好ましくは２７〜３７質量％、より好ましくは２７〜３６．５質量％、さらに好ましくは３５〜３６．１質量％含むのが、泡質、泡量の観点から好ましい。 Moreover, in formula, n shows the number of 0-20, and 0-12 are more preferable. In addition, although n shows the addition mole number of ethylene oxyoxide, the average addition mole number (average value of n) in the composition of a component (B) is from the point which foaming is favorable and suppresses the crack in the middle of use. 1.5 to 10 is preferable, 2.5 to 6.4 is more preferable, 2.5 to 3.7 is more preferable, 2.5 to 3.4 is more preferable, and 2.8 to 3.4 is more preferable. More preferred is 2.8 to 3.1.
In the general formula (1), the alkyl ether carboxylic acid of the component (B) or a salt thereof is more than 9.6% by mass and less than 27% by mass, preferably 9.8 to 27% by mass, compared with the component of n = 0. Preferably it contains 9.9-27 mass%, More preferably, it is 9.9-16 mass%, More preferably, it contains 9.9-15 mass%. By making it within this range, it is excellent in foam amount and foam quality, and it has a refreshed feeling of use, cracking is suppressed during use, foaming is good even after repeated use, excellent scum dispersibility, bathroom Makes it hard to get dirty.
Furthermore, the total of n = 1 component and n = 2 component is less than 21 to 40% by mass, preferably 27 to 37% by mass, more preferably 27 to 36.5% by mass, and further preferably 35 to 36.1. It is preferable from the viewpoint of the foam quality and the amount of foam to contain mass%.

また、式中、Ｍとしては、水素原子；ナトリウム、カリウム等のアルカリ金属；カルシウム、マグネシウム等のアルカリ土類金属；アンモニウム；モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン由来のアンモニウムなどが挙げられる。これらの中で、起泡性、経時での着色のなさの点から、アルカリ金属が好ましい。 In the formula, M represents a hydrogen atom; an alkali metal such as sodium or potassium; an alkaline earth metal such as calcium or magnesium; an ammonium; an ammonium derived from an alkanolamine such as monoethanolamine, diethanolamine or triethanolamine; Can be mentioned. Among these, alkali metals are preferable from the viewpoints of foamability and lack of coloration with time.

成分（Ｂ）のアルキルエーテルカルボン酸又はその塩は、一般式（１）中、ｎ＝０、１、２、３、４の成分の質量割合が、Ｒ¹の組成のうち最大含有量のアルキル鎖長成分において、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：０．９９〜３．５０：０．８９〜３．００：０．７６〜３．００：０．６３〜１．５２であることが、起泡性、洗浄性、すすぎ後のさっぱり感の両立性の点から、好ましい。 In the general formula (1), the alkyl ether carboxylic acid of the component (B) or a salt thereof is an alkyl having the maximum content in the composition of R ¹ in which the mass ratio of the components of n = 0, 1, 2, 3, 4 In the chain length component, (n = 0 component mass): (n = 1 component mass): (n = 2 component mass): (n = 3 component mass): (n = 4 component mass) = 1: 0.99 to 3.50: 0.89 to 3.00: 0.76 to 3.00: 0.63 to 1.52 is foaming property, detergency, and refreshing feeling after rinsing From the viewpoint of compatibility, it is preferable.

また、一般式（１）中、ｎ＝０の成分を９．９質量％以上１２質量％未満含み、Ｒ¹の組成のうち最大含有量のアルキル鎖長成分において、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：１．５３〜１．８７：１．５９〜２．２５：１．３３〜２．１６：１．１４〜１．５２となるか、又は、ｎ＝０の成分を１２質量％以上１７質量％以下含み、Ｒ¹の組成のうち最大含有量のアルキル鎖長成分において、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：０．９９〜１．３４：０．８９〜１．４０：０．７６〜１．２３：０．６３〜１となるのが、泡質、泡量の観点から好ましい。 Further, in the general formula (1), the component of n = 0 include less than 9.9 wt% 12 wt%, in the alkyl chain length components of the maximum content of the composition of R ^1, the (n = 0 component mass ): (Mass of n = 1 component): (mass of n = 2 component): (mass of n = 3 component): (mass of n = 4 component) = 1: 1.53-1.87: 1. 59 to 2.25: 1.33 to 2.16: 1.14 to 1.52, or 12 to 17% by mass of the n = 0 component, and the maximum among the compositions of R ¹ In the alkyl chain length component of content, (mass of n = 0 component): (mass of n = 1 component): (mass of n = 2 component): (mass of n = 3 component): (n = 4 component) Mass) = 1: 0.99 to 1.34: 0.89 to 1.40: 0.76 to 1.23: 0.63 to 1 is preferable from the viewpoints of foam quality and foam amount.

さらに、一般式（１）中、ｎ＝０の成分を９．９〜１１．５質量％含み、Ｒ¹の組成のうち最大含有量のアルキル鎖長成分において、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：１．５８〜１．８４：１．７２〜２．１７：１．４９〜２．００：１．１４〜１．５２となるか、又は、一般式（１）中、ｎ＝０の成分を１３〜１５質量％含み、Ｒ¹の組成のうち最大含有量のアルキル鎖長成分において、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：１．００〜１．３１：０．９３〜１．３４：０．７９〜１．１８：０．６３〜１となるのが、泡質、泡量の点から好ましい。 Further, in the general formula (1), the component of n = 0 contains 9.9 to 11.5% by mass, and in the alkyl chain length component of the maximum content in the composition of R ¹ , (mass of n = 0 component) : (N = 1 component mass): (n = 2 component mass): (n = 3 component mass): (n = 4 component mass) = 1: 1.58-1.84: 1.72 To 2.17: 1.49 to 2.00: 1.14 to 1.52, or, in the general formula (1), the component of n = 0 is contained in an amount of 13 to 15% by mass, and the composition of R ¹ In the maximum alkyl chain length component, (n = 0 component mass): (n = 1 component mass): (n = 2 component mass): (n = 3 component mass): (n = Mass of four components) = 1: 1.00 to 1.31: 0.93 to 1.34: 0.79 to 1.18: 0.63 to 1 in terms of foam quality and amount of foam To preferred.

成分（Ｂ）において、一般式（１）中、Ｒ¹は炭素数４〜２２のアルキル基であり、Ｒ¹の平均炭素数は１０．８〜１２．８であり、また、一番含有量の多いアルキル鎖長を有する成分が５５質量％以上９７質量％未満であり、更に、ｎは０〜２０の数を示し、ｎの付加モル数の平均値は、１．５〜１０、さらには２．５〜６．４であり、ｎ＝０の成分を９．８〜２７質量％、ｎ＝１の成分とｎ＝２の成分を合計で２７〜３７質量％含有することが好ましい。また、式中、Ｍとしては、水素原子、ナトリウム、カリウム、アンモニウムが好ましい。このようにすることで、起泡性を早めることができる。 In the component (B), in the general formula (1), R ¹ is an alkyl group having 4 to 22 carbon atoms, the average carbon number of R ¹ is 10.8 to 12.8, and the most content The component having a large alkyl chain length is 55% by mass or more and less than 97% by mass, n represents a number of 0 to 20, and the average value of the number of added moles of n is 1.5 to 10, It is 2.5-6.4, It is preferable to contain 9.8-27 mass% of the component of n = 0, and 27-37 mass% of the component of n = 1 and the component of n = 2 in total. In the formula, M is preferably a hydrogen atom, sodium, potassium, or ammonium. By doing in this way, foamability can be accelerated.

成分（Ｂ）において、一般式（１）中、Ｒ¹は炭素数６〜２０のアルキル基が好ましく、Ｒ¹の平均炭素数は１０．８〜１２．８であり、また、一番含有量の多いアルキル鎖長を有する成分が５５質量％以上９７質量％未満であり、更に、ｎは０〜２０の数を示し、ｎの平均値は、２．５〜３．７であり、ｎ＝０の成分を９．８〜２７質量％、ｎ＝１の成分とｎ＝２の成分を合計で２７〜３７質量％含有することが好ましい。また、式中、Ｍとしては、水素原子、ナトリウム、カリウム、アンモニウムが好ましい。このようにすることで、起泡性を早めることができる。 In the component (B), in the general formula (1), R ¹ is preferably an alkyl group having 6 to 20 carbon atoms, and the average carbon number of R ¹ is 10.8 to 12.8. The component having a large alkyl chain length is 55% by mass or more and less than 97% by mass, n represents a number from 0 to 20, the average value of n is 2.5 to 3.7, and n = It is preferable to contain 9.8 to 27% by mass of 0 component and 27 to 37% by mass in total of n = 1 component and n = 2 component. In the formula, M is preferably a hydrogen atom, sodium, potassium, or ammonium. By doing in this way, foamability can be accelerated.

成分（Ｂ）において、一般式（１）中、Ｒ¹は炭素数８〜１８のアルキル基であり、Ｒ¹の平均炭素数は１０．８〜１２．８であり、また、一番含有量の多いアルキル鎖長を有する成分が５５質量％以上９７質量％未満であり、更に、ｎは０〜２０の数を示し、ｎの平均値は、２．５〜３．４であり、ｎ＝０の成分を９．９〜２７質量％、ｎ＝１の成分とｎ＝２の成分を合計で２７〜３６．５質量％含有することが好ましい。また、式中、Ｍとしては、水素原子、ナトリウム、カリウム、アンモニウムが好ましい。このようにすることで、泡質、泡量を向上させることができる。 In the component (B), in the general formula (1), R ¹ is an alkyl group having 8 to 18 carbon atoms, the average carbon number of R ¹ is 10.8 to 12.8, and the most content The component having a large alkyl chain length is 55% by mass or more and less than 97% by mass, n represents a number of 0 to 20, and the average value of n is 2.5 to 3.4. It is preferable to contain 9.9 to 27% by mass of 0 component and 27 to 36.5% by mass in total of n = 1 component and n = 2 component. In the formula, M is preferably a hydrogen atom, sodium, potassium, or ammonium. By doing in this way, foam quality and the amount of foam can be improved.

成分（Ｂ）において、一般式（１）中、Ｒ¹は炭素数８〜１６のアルキル基であり、Ｒ¹の平均炭素数は１０．８〜１２．５であり、また、一番含有量の多いアルキル鎖長を有する成分が６０〜９５質量％であり、更に、ｎは０〜２０の数を示し、ｎの平均値は、２．８〜３．４であり、ｎ＝０の成分を９．９〜１６質量％、ｎ＝１の成分とｎ＝２の成分を合計で２７〜３６．５質量％含むものが好ましい。また、式中、Ｍとしては、水素原子、ナトリウム、カリウム、アンモニウムが好ましい。このようにすることで、泡量、泡質を向上させることができる。 In the component (B), in the general formula (1), R ¹ is an alkyl group having 8 to 16 carbon atoms, the average carbon number of R ¹ is 10.8 to 12.5, and the most content The component having a large alkyl chain length is 60 to 95% by mass, n represents a number of 0 to 20, the average value of n is 2.8 to 3.4, and n = 0 Is preferably 9.9 to 16% by mass and contains 27 to 36.5% by mass in total of n = 1 and n = 2. In the formula, M is preferably a hydrogen atom, sodium, potassium, or ammonium. By doing in this way, foam amount and foam quality can be improved.

成分（Ｂ）において、一般式（１）中、Ｒ¹は炭素数１０〜１６のアルキル基であり、Ｒ¹の平均炭素数は１２．１〜１２．４であり、また、一番含有量の多いアルキル鎖長を有する成分が７０〜９５質量％であり、更に、ｎは０〜２０の数を示し、ｎの平均値は、２．８〜３．１であり、ｎ＝０の成分を９．９〜１５質量％、ｎ＝１の成分とｎ＝２の成分を合計で３５〜３６．１質量％含むものが好ましい。また、式中、Ｍとしては、水素原子、ナトリウム、カリウム、アンモニウムが好ましい。このようにすることで、泡量、泡質、を向上させることができる。 In the component (B), in the general formula (1), R ¹ is an alkyl group having 10 to 16 carbon atoms, and the average carbon number of R ¹ is 12.1 to 12.4. The component having a large alkyl chain length is 70 to 95% by mass, n represents a number of 0 to 20, the average value of n is 2.8 to 3.1, and n = 0 Is preferably 9.9 to 15% by mass and contains 35 to 36.1% by mass in total of n = 1 and n = 2. In the formula, M is preferably a hydrogen atom, sodium, potassium, or ammonium. By doing in this way, the amount of foams and foam quality can be improved.

なお、本発明の成分（Ｂ）において、Ｒ¹のアルキル鎖長の分布、Ｒ¹の平均アルキル鎖長、ｎ＝０の成分量、ｎの平均付加モル数、ｎ＝０、１、２、３、４の成分の質量割合は、一般式（１）で表されるアルキルエーテルカルボン酸をガスクロマトグラフィーによる分析を行い、以下のようにして求める。 Incidentally, in the components of the present invention (B), the distribution of alkyl chain length of R ^1, the average alkyl chain length of R ^1, components of n = 0, average addition mole number of n, n = 0, 1, 2, The mass ratio of the components 3 and 4 is determined as follows by analyzing the alkyl ether carboxylic acid represented by the general formula (1) by gas chromatography.

〔Ｒ¹のアルキル鎖長の分布〕
ガスクロマトグラフィーより得られるピーク面積のうち、ｎ＝０モルに相当する各アルキル鎖長のピーク面積を求め、それらの総和を１００とし、各アルキル鎖長分布の百分率を求めた。ｎ＝１〜３モルにおいても同様に計算し、ｎ＝０〜３モルの各アルキル鎖長分布の百分率の値を平均し、Ｒ¹のアルキル鎖長の分布を求めた（これより、Ｒ¹の組成のうち最も多く含有するアルキル基成分を特定できる）。 [Distribution of alkyl chain length of R ¹ ]
Of the peak areas obtained by gas chromatography, the peak area of each alkyl chain length corresponding to n = 0 mol was determined, and the sum of these was determined as 100, and the percentage of each alkyl chain length distribution was determined. also calculated similarly in n = 1 to 3 mol, and the average value of the percentage of each alkyl chain length distribution of n = 0 to 3 mol, determined the distribution of alkyl chain length of R ¹ (from which, R ¹ The alkyl group component containing the largest amount of the composition can be specified).

〔Ｒ¹の平均アルキル鎖長〕
上記のようにして求めたＲ¹のアルキル鎖長の分布より、各成分の割合を求め、得られた割合に対応するアルキル鎖長分の炭素数を各々掛け、これらの総和を得た。これを平均アルキル鎖長とした。 [Average alkyl chain length of R ¹ ]
From the distribution of the alkyl chain length of R ¹ determined as described above, the ratio of each component was determined, and the carbon number corresponding to the alkyl chain length corresponding to the ratio thus obtained was multiplied to obtain the sum of these. This was defined as the average alkyl chain length.

〔ｎ＝０の成分量、ｎ＝１の成分とｎ＝２の成分の合計量〕
Ｒ¹の組成のうち、最も多く含有するアルキル鎖長を特定し、その成分のｎ＝０〜１０に相当するガスクロマトグラフィーの面積を合計した。その合計量を１００％として、ｎ＝０の成分量、ｎ＝１の成分とｎ＝２の成分の合計量を算出した。 [Component amount of n = 0, total amount of component of n = 1 and component of n = 2]
Among the compositions of R ¹ , the most abundant alkyl chain length was specified, and the areas of gas chromatography corresponding to n = 0 to 10 of the components were totaled. The total amount was set to 100%, and the total amount of n = 0, n = 1 and n = 2 was calculated.

〔ｎの平均付加モル数〕
Ｒ¹の組成のうち最も多く含有するアルキル鎖長を特定し、その成分のｎ＝０〜１０に相当するガスクロマトグラフィーの面積を合計した（ｎが１１以上のものは微量であり、計算から除いた）。その合計量を１として、ｎ＝０〜１０の各々の割合を求めた。この割合に、各々の付加モル数を掛け、これらの合計をｎの平均付加モル数とした。 [Average number of moles of n added]
The most alkyl chain length contained in the composition of R ¹ was specified, and the areas of the gas chromatography corresponding to n = 0 to 10 of the components were totaled (the ones with n of 11 or more are trace amounts. Excluded). The total amount was set to 1, and the ratio of each of n = 0 to 10 was obtained. This ratio was multiplied by the number of moles added, and the sum of these was taken as the average number of moles added.

〔ｎ＝０、ｎ＝１、ｎ＝２、ｎ＝３、ｎ＝４の成分の質量割合〕
ＥＯ付加モル数の異なる各成分の質量割合に関しては、ガスクロマトグラフィーにより得られるピーク面積から、上記に示した方法でＲ¹のアルキル鎖長の分布を求め、Ｒ¹の組成のうち最大含有量のアルキル鎖長成分を特定し、その最大成分のｎ＝０、ｎ＝１、ｎ＝２、ｎ＝３、ｎ＝４の面積比から特定した。 [Mass ratio of components of n = 0, n = 1, n = 2, n = 3, n = 4]
Regarding the mass ratio of each component having a different number of EO addition moles, the distribution of the alkyl chain length of R ¹ is obtained from the peak area obtained by gas chromatography by the method described above, and the maximum content of the composition of R ¹ The alkyl chain length component was identified from the area ratio of n = 0, n = 1, n = 2, n = 3, and n = 4 of the maximum component.

成分（Ｂ）のアルキルエーテルカルボン酸又はその塩は、さっぱりとした使用感、使用途中でのひび割れの抑制、繰り返し使用したときの泡立ちの良好性、スカムの分散性に優れるため浴室等を汚しにくくする点から、前記のような組成を有するものであり、泡質とさっぱり感の観点から、酸として、全組成中に３〜１５質量％含有され、好ましくは５〜１０質量％含有される。 Component (B) alkyl ether carboxylic acid or its salt has a refreshing feeling of use, suppression of cracks during use, good foaming when used repeatedly, and excellent dispersibility of scum, making it difficult to stain bathrooms, etc. In view of the above, it has the composition as described above. From the viewpoint of foam quality and refreshing feeling, the acid is contained in an amount of 3 to 15% by mass, preferably 5 to 10% by mass in the total composition.

本発明において、成分（Ａ）と成分（Ｂ）の質量割合（Ｂ）／（Ａ）は、さっぱりとした使用感、使用途中でのひび割れの抑制、繰り返し使用したときの泡立ちの良好性、スカムの分散性に優れるため浴室等を汚しにくくする点から、０．０３４〜０．２３が好ましく、さらに０．０３〜０．２１が好ましい。 In the present invention, the mass ratio (B) / (A) of the component (A) and the component (B) is a refreshing feeling of use, suppression of cracking during use, good foaming when repeatedly used, scum Since it is excellent in dispersibility, 0.034 to 0.23 is preferable, and 0.03 to 0.21 is more preferable from the viewpoint of making the bathroom and the like difficult to soil.

本発明で用いる成分（Ｃ）の水は、溶媒として使用され、全組成中に１〜１８質量％、更に５〜１５質量％含有されるのが好ましい。 The component (C) water used in the present invention is used as a solvent and is preferably contained in the total composition in an amount of 1 to 18% by mass, and more preferably 5 to 15% by mass.

本発明の固形洗浄剤組成物は、更に、通常の石鹸組成物に用いられる成分、例えば、抗菌剤、香料、キレート剤、顔料、染料、油剤等を含有することができる。 The solid detergent composition of the present invention can further contain components used in ordinary soap compositions, such as antibacterial agents, fragrances, chelating agents, pigments, dyes, oils and the like.

本発明の固形洗浄剤組成物は、機械練製法により製造される。
機械練製法は、通常の方法であれば良く、例えば、まず、けん化法や脂肪酸中和法で得られた、水分８〜１５質量％程度を含む石鹸用素地に、香料、色素などを加え、成分が均一になるまでミキサーで混合する。その後、３本ロール（カレンダーロール）で石鹸素地粒を粉砕し、さらに均一になるように混練する。その後、プロッダー（押出機）で棒状に押出された後、一個の大きさに切断され、型打、包装の工程を経て、固形洗浄剤組成物を得ることができる。
本発明の固形洗浄剤組成物は、固形洗浄剤組成物を混練する工程と、押出機で棒状に押出す工程とを備える製造法により、製造されるのが好ましい。 The solid detergent composition of the present invention is produced by a mechanical kneading method.
The mechanical kneading method may be a normal method. For example, first, a fragrance, a pigment or the like is added to a soap base containing about 8 to 15% by mass of water obtained by a saponification method or a fatty acid neutralization method, Mix with a mixer until the ingredients are uniform. Thereafter, the soap base grains are pulverized with three rolls (calendar rolls) and kneaded so as to be even. Then, after extruding into a rod shape with a pudder (extruder), it is cut into one size, and a solid detergent composition can be obtained through stamping and packaging processes.
The solid detergent composition of the present invention is preferably produced by a production method comprising a step of kneading the solid detergent composition and a step of extruding it in a rod shape with an extruder.

本発明の固形洗浄剤組成物を用いて皮膚を洗浄する方法は、例えば、以下のとおりである。すなわち、本発明の固形洗浄剤組成物を身体、つまり顔、手足、胴体などの身体皮膚部に適量を適用し、泡立てて洗浄した後、シャワー等の温水を利用してすすぐ方法である。また、タオル、スポンジ、ブラシ等の洗浄補助具に適量を適用し、泡立てて洗浄することもできる。 The method for washing the skin using the solid detergent composition of the present invention is, for example, as follows. That is, the solid cleaning composition of the present invention is a method of applying an appropriate amount to the body, that is, the body skin such as the face, limbs, and torso, washing with foaming, and then rinsing using hot water such as a shower. In addition, an appropriate amount can be applied to cleaning aids such as towels, sponges, brushes, etc., and foamed for cleaning.

〈測定方法〉
本発明において、アルキルエーテルカルボン酸のアルキル組成、ＥＯ付加モル分布及び各成分の比率は、ガスクロマトグラフィー（ＧＣ）により、以下の分析方法で測定した。 <Measuring method>
In the present invention, the alkyl composition, EO addition molar distribution, and ratio of each component of the alkyl ether carboxylic acid were measured by gas chromatography (GC) by the following analytical method.

（ＧＣ分析条件）
ＧＣ機器；アジレントテクノロジー社製、７８９０Ａ
カラム；アジレントテクノロジー社製、ＤＢ−５
（３０ｍ、内径０．２５mm、膜厚０．２５μｍ）
検出器；ＦＩＤ
キャリア；ヘリウムガス、１mL／min
昇温条件；１００℃から３２５℃まで５℃／minで昇温。その後、３５分間３２５℃を保持。 (GC analysis conditions)
GC equipment; Agilent Technologies, 7890A
Column; manufactured by Agilent Technologies, DB-5
(30m, inner diameter 0.25mm, film thickness 0.25μm)
Detector; FID
Carrier; helium gas, 1mL / min
Temperature rising condition: Temperature raised from 100 ° C. to 325 ° C. at 5 ° C./min. Then, hold 325 ° C. for 35 minutes.

（サンプルの前処理方法）
アルキルエーテルカルボン酸１５０mgをメタノール５０mLで溶解した。また、固形洗浄剤組成物については、アルキルエーテルカルボン酸として１５０mgとなるよう採取し、メタノール５０mLで溶解した。なお、固形洗浄剤組成物がポリオキシエチレンアルキルエーテル硫酸塩などの強アニオン性の界面活性剤を含む場合、それらが２５０mg以下となるように採取した。この溶液１mLを採取して、あらかじめメタノール４mLでコンディショニングを行った固相カートリッジ（Biotage製、Isolute SAX、１g、３mL、500-0100-B）に適用し、１０mL丸底試験管に通過液を捕集した。その後、ギ酸４．６ｇに１００mLのメタノールを加えた溶液６mLで溶出し、溶出液についても同じ試験管に捕集した。捕集した溶液は、５０℃に加温したブロックヒーターに設置し、窒素ガスを吹き込み、１mL程度まで濃縮した後、さらに室温下で窒素ガスを吹き込み乾燥させた。そこに、ジアゾメタン−エーテル溶液２mLを加え、攪拌しながら室温下で１０分間放置し誘導体化を行った。その後、室温下で窒素ガスを吹き込み、５００μＬ以下になるまで濃縮した後、クロロホルムを加えて５００μＬとし、ＧＣ分析に供した。
なお、ジアゾメタン−エーテル溶液は、ジアゾメタン生成装置（宮本理研工業製、ＧＭ−５０）を用い、以下の手順で調製した。第１と第２の受け器、第２と第３の受け器をシリコンゴム栓およびテフロン（登録商標）製チューブで連結する。第２の受け器に、Ｎ−メチル−Ｎ'−ニトロ−Ｎ−ニトロソグアニジン０．８ｇを採取し、２．５mLのイオン交換水を加えた。第３の受け器に、ｔ−ブチルメチルエーテル１０mLを採取した。第１、第２、第３の受け器を氷冷した。続いて第２の受け器に、プラスチックシリンジを備え付け、このシリンジ中に水酸化ナトリウム２０ｇをイオン交換水１００mLに溶解させた溶液３mLを入れた。この水酸化ナトリウム水溶液をゆっくりと滴下してジアゾメタンガスを生成させ、第１の受け器側から静かに窒素ガスを吹き込み、第３の受け器のｔ−ブチルメチルエーテルに溶解させて、ジアゾメタン−エーテル溶液を得た。
上記サンプルの前処理における試薬は、以下のものを使用した。
メタノール（関東化学製、高速液体クロマトグラフィー用、25183-1B）
ギ酸（和光純薬工業製、試薬特級、066-00461）
クロロホルム（関東化学製、鹿１級、07278-01）
Ｎ−メチル−Ｎ’−ニトロ−Ｎ−ニトロソグアニジン（関東化学製、鹿1級、25596-51）
ｔ−ブチルメチルエーテル（関東化学製、鹿特級、04418-00）
水酸化ナトリウム（和光純薬工業製、特級、196-13761） (Sample pretreatment method)
150 mg of alkyl ether carboxylic acid was dissolved in 50 mL of methanol. Moreover, about the solid cleaning composition, it extract | collected so that it might become 150 mg as alkyl ether carboxylic acid, and melt | dissolved in 50 mL of methanol. When the solid detergent composition contained a strong anionic surfactant such as polyoxyethylene alkyl ether sulfate, the solid detergent composition was collected so as to be 250 mg or less. Take 1 mL of this solution and apply it to a solid-phase cartridge (Biotage, Isolute SAX, 1 g, 3 mL, 500-0100-B) that has been conditioned in advance with 4 mL of methanol, and collect the passing solution in a 10 mL round bottom test tube. Gathered. Thereafter, elution was performed with 6 mL of a solution obtained by adding 100 mL of methanol to 4.6 g of formic acid, and the eluate was also collected in the same test tube. The collected solution was placed in a block heater heated to 50 ° C., blown with nitrogen gas, concentrated to about 1 mL, and further blown with nitrogen gas at room temperature to dry. Thereto, 2 mL of a diazomethane-ether solution was added, and the mixture was allowed to stand at room temperature for 10 minutes with stirring for derivatization. Thereafter, nitrogen gas was blown at room temperature, and the mixture was concentrated to 500 μL or less, and then chloroform was added to make 500 μL, which was subjected to GC analysis.
In addition, the diazomethane-ether solution was prepared in the following procedures using the diazomethane production | generation apparatus (Miyamoto Riken Kogyo make, GM-50). The first and second receivers and the second and third receivers are connected with a silicone rubber stopper and a Teflon (registered trademark) tube. In a second receiver, 0.8 g of N-methyl-N′-nitro-N-nitrosoguanidine was collected and 2.5 mL of ion exchange water was added. In a third receiver, 10 mL of t-butyl methyl ether was collected. The first, second and third receivers were ice-cooled. Subsequently, a plastic syringe was attached to the second receiver, and 3 mL of a solution in which 20 g of sodium hydroxide was dissolved in 100 mL of ion-exchanged water was placed in this syringe. This sodium hydroxide aqueous solution is slowly added dropwise to produce diazomethane gas, and nitrogen gas is gently blown from the first receiver side, dissolved in t-butyl methyl ether of the third receiver, and diazomethane-ether A solution was obtained.
The following reagents were used in the sample pretreatment.
Methanol (manufactured by Kanto Chemical, for high performance liquid chromatography, 25183-1B)
Formic acid (manufactured by Wako Pure Chemical Industries, reagent special grade, 066-00461)
Chloroform (manufactured by Kanto Chemical, deer grade 1, 07278-01)
N-methyl-N'-nitro-N-nitrosoguanidine (manufactured by Kanto Chemical, deer grade 1, 25596-51)
t-Butyl methyl ether (manufactured by Kanto Chemical, deer special grade, 04418-00)
Sodium hydroxide (Wako Pure Chemical Industries, special grade, 196-13761)

〈製造例〉
本発明の枠練り石鹸組成物に用いる成分（Ｂ）のアルキルエーテルカルボン酸は、例えば、以下のようにして製造することができる。なお、断りのない限り「％」は質量％を示す。 <Production example>
The component (B) alkyl ether carboxylic acid used in the frame kneaded soap composition of the present invention can be produced, for example, as follows. Unless otherwise indicated, “%” indicates mass%.

製造例１
攪拌および温度調節機能を備えたステンレス製オートクレーブに、ラウリルアルコール［商品名：カルコール２０９８、花王製］１１４４ｇ（６．１４モル）、ミリスチルアルコール［商品名：カルコール４０９８、花王製］６０．２ｇ（０．２８１モル）、水酸化カリウム２．６８ｇ（０．０４７８モル）を仕込み、減圧脱水を行った。次いで、エチレンオキサイド（ＥＯ）９９６ｇ（２２.６モル）を１５５℃にて導入し、反応温度１５５℃、反応圧力０.４ＭＰａで２時間反応を行った。反応終了後、８０℃、６kPaの減圧条件で３０分間攪拌し、未反応のエチレンオキサイドを除去した後、窒素を導入し常圧にし、４.８２ｇ（０.０４８２モル）の９０％乳酸をオートクレーブ内に加え、８０℃で３０分間攪拌し、ＥＯ付加モル数３.５５モルのアルキルエトキシレート（以下、「生成ＡＥ」ともいう）を得た。
攪拌機能、温度調節機能及び酸素ガス導入管を取り付けたガラス製反応容器に、上記生成物９０ｇ（０．２モル）と、４８％水酸化ナトリウム水溶液１６．７ｇ（水酸化ナトリウムとして０．２モル）、パラジウム−白金−ビスマス系触媒（活性炭にパラジウム４％、白金１％及びビスマス５％を担持、含水率５０％）０．９ｇ、水４９４．４ｇをそれぞれ仕込んだ。攪拌条件下、液温を７０℃まで昇温し、酸素を２７モル％（対生成ＡＥ／時間）の割合で吹き込みながら、反応温度７０℃で３．５時間接触酸化反応をさせた。反応率は８９％であった。
反応終了後、反応液から触媒を濾別し、アルキルエーテルカルボン酸Ｎａ塩の水溶液を得た。続いて、３５％塩酸を加え、分液操作を実施し、アルキルエーテルカルボン酸を得た。これをＥＣ１とする。 Production Example 1
In a stainless steel autoclave equipped with stirring and temperature control functions, 1144 g (6.14 mol) of lauryl alcohol [trade name: Calcoal 2098, manufactured by Kao], 60.2 g (0 trade name: Calcoal 4098, manufactured by Kao) .281 mol) and 2.68 g (0.0478 mol) of potassium hydroxide were added and dehydration under reduced pressure was performed. Next, 996 g (22.6 mol) of ethylene oxide (EO) was introduced at 155 ° C., and the reaction was carried out at a reaction temperature of 155 ° C. and a reaction pressure of 0.4 MPa for 2 hours. After completion of the reaction, the mixture was stirred for 30 minutes at 80 ° C. under reduced pressure of 6 kPa to remove unreacted ethylene oxide, and then nitrogen was introduced to normal pressure, and 4.82 g (0.0482 mol) of 90% lactic acid was autoclaved. In addition, the mixture was stirred at 80 ° C. for 30 minutes to obtain an alkyl ethoxylate (hereinafter also referred to as “produced AE”) having an EO addition mole number of 3.55 mol.
In a glass reaction vessel equipped with a stirring function, temperature control function and oxygen gas introduction tube, 90 g (0.2 mol) of the above product and 16.7 g of 48% aqueous sodium hydroxide solution (0.2 mol as sodium hydroxide) ), Palladium-platinum-bismuth catalyst (supporting 4% palladium, 1% platinum and 5% bismuth on activated carbon, water content 50%) 0.9 g and 494.4 g water, respectively. Under stirring conditions, the liquid temperature was raised to 70 ° C., and a catalytic oxidation reaction was carried out at a reaction temperature of 70 ° C. for 3.5 hours while blowing oxygen at a rate of 27 mol% (vs. production AE / hour). The reaction rate was 89%.
After completion of the reaction, the catalyst was filtered off from the reaction solution to obtain an aqueous solution of alkyl ether carboxylic acid Na salt. Subsequently, 35% hydrochloric acid was added, and a liquid separation operation was performed to obtain an alkyl ether carboxylic acid. This is EC1.

ガスクロマトグラフィーの分析の結果、ＥＣ１は、一般式（１）において、Ｍ＝Ｈ、Ｒ¹はラウリル基／ミリスチル基＝９５／５、平均炭素数は１２．１、ｎの平均値は２．８、ｎ＝０の成分を１４．７質量％含み、ｎ＝１の成分とｎ＝２の成分の合計量は３６．１質量％であった。
また、ＥＯ付加モル数の異なる各成分の比率に関しても、Ｒ¹の組成のうち最大成分の測定値から算出した結果、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：１．２２：１．２３：１．０６：０．８３であった。 As a result of analysis by gas chromatography, EC1 is M = H in the general formula (1), R ¹ is lauryl group / myristyl group = 95/5, the average carbon number is 12.1, and the average value of n is 2. 8, The component of n = 0 was contained 14.7 mass%, and the total amount of the component of n = 1 and the component of n = 2 was 36.1 mass%.
In addition, regarding the ratio of each component having a different number of EO addition moles, as a result of calculation from the measured value of the maximum component of the R ¹ composition, (n = 0 component mass): (n = 1 component mass): ( n = 2 mass of component): (mass of n = 3 component): (mass of n = 4 component) = 1: 1.22: 1.23: 1.06: 0.83.

製造例２
製造例１に倣い、デシルアルコール［商品名：カルコール１０９８、花王製］、ラウリルアルコール［商品名：カルコール２０９８、花王製］、ミリスチルアルコール［商品名：カルコール４０９８、花王製］、セチルアルコール［商品名：カルコール６０９８、花王製］を質量比１０／７０／１５／５に混合した原料にＥＯを反応させ、ＥＯ付加モル数３．５５モルのアルキルエトキシレートを得た。これを実施例１同様、酸化反応を行い、得られたアルキルエーテルカルボン酸塩を塩酸処理することにより、アルキルエーテルカルボン酸を得た。 Production Example 2
Following production example 1, decyl alcohol [trade name: Calcoal 1098, manufactured by Kao], lauryl alcohol [trade name: Calcoal 2098, manufactured by Kao], myristyl alcohol [trade name: Calcoal 4098, manufactured by Kao], cetyl alcohol [trade name] : Calcoal 6098, manufactured by Kao] at a mass ratio of 10/70/15/5 was reacted with EO to obtain an alkyl ethoxylate having 3.55 mol of EO added. This was subjected to an oxidation reaction as in Example 1, and the resulting alkyl ether carboxylate was treated with hydrochloric acid to obtain an alkyl ether carboxylic acid.

ガスクロマトグラフィーの分析の結果、一般式（１）において、Ｍ＝Ｈ、Ｒ¹はデシル基／ラウリル基／ミリスチル基／パルミチル基=１０／７０／１５／５、平均炭素数は１２．３、ｎの平均値は３．３、ｎ＝０の成分を１５．２質量％含み、ｎ＝１の成分とｎ＝２の成分の合計量は３１．４質量％であった。
また、ＥＯ付加モル数の異なる各成分の比率に関しても、Ｒ¹の組成のうち最大成分の測定値から算出した結果、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：１．０７：１．００：０．８５：０．６７であった。 As a result of analysis by gas chromatography, in general formula (1), M = H, R ¹ is decyl group / lauryl group / myristyl group / palmityl group = 10/70/15/5, average carbon number is 12.3, The average value of n was 3.3 and 15.2% by mass of n = 0 components, and the total amount of n = 1 and n = 2 components was 31.4% by mass.
In addition, regarding the ratio of each component having a different number of EO addition moles, as a result of calculation from the measured value of the maximum component of the R ¹ composition, (n = 0 component mass): (n = 1 component mass): ( n = 2 mass of component): (n = mass of 3 component): (mass of n = 4 component) = 1: 1.07: 1.00: 0.85: 0.67.

製造例３
攪拌、温度調節機能を取り付けたガラス製反応容器に、ラウリルアルコール３７２ｇ（２．００モル）を仕込み、攪拌条件下、液温を７０℃まで昇温させ、モノクロロ酢酸ナトリウム２５６ｇ（２．２０モル）及び水酸化ナトリウム８８ｇ（２．２０モル）を分割して加えながら、５時間反応を行った。反応終了後、析出物を濾別し、続いて３５％塩酸を加え、酸型化し、アルキルエーテルカルボン酸を得た（一般式（１）において、Ｍ＝Ｈ、Ｒ１はラウリル基、ｎ＝０）。 Production Example 3
372 g (2.00 mol) of lauryl alcohol was charged into a glass reaction vessel equipped with stirring and temperature control functions, the liquid temperature was raised to 70 ° C. under stirring conditions, and 256 g (2.20 mol) of sodium monochloroacetate. The reaction was carried out for 5 hours while adding 88 g (2.20 mol) of sodium hydroxide in portions. After completion of the reaction, the precipitate was separated by filtration and subsequently acidified by adding 35% hydrochloric acid to obtain an alkyl ether carboxylic acid (in the general formula (1), M = H, R1 is a lauryl group, n = 0 ).

製造例４
製造例１に倣い、デシルアルコールを原料にＥＯを反応させ、ＥＯ付加モル数３.５５モルのアルキルエトキシレートを得た。これを実施例１同様、酸化反応を行い、得られたアルキルエーテルカルボン酸塩を塩酸処理することにより、アルキルエーテルカルボン酸を得た。
ガスクロマトグラフィーの分析の結果、一般式（１）において、Ｍ＝Ｈ、Ｒ¹はデシル基、ｎの平均値は３．１、ｎ＝０の成分を１６質量％含み、ｎ＝１の成分とｎ＝２の成分の合計量は３７質量％であった。 Production Example 4
Following Production Example 1, EO was reacted with decyl alcohol as a raw material to obtain an alkyl ethoxylate having 3.55 moles of EO added. This was subjected to an oxidation reaction as in Example 1, and the resulting alkyl ether carboxylate was treated with hydrochloric acid to obtain an alkyl ether carboxylic acid.
As a result of gas chromatography analysis, in general formula (1), M = H, R ¹ is a decyl group, n has an average value of 3.1, n = 0 contains 16% by mass, and n = 1 The total amount of n = 2 components was 37% by mass.

製造例５
製造例１に倣い、ラウリルアルコールを原料にＥＯを反応させ、ＥＯ付加モル数３.５５モルのアルキルエトキシレートを得た。これを実施例１同様、酸化反応を行い、得られたアルキルエーテルカルボン酸塩を塩酸処理することにより、アルキルエーテルカルボン酸を得た。
ガスクロマトグラフィーの分析の結果、一般式（１）において、Ｍ＝Ｈ、Ｒ¹はラウリル基、ｎの平均値は３．１、ｎ＝０の成分を１６質量％含み、ｎ＝１の成分とｎ＝２の成分の合計量は３７質量％であった。
また、ＥＯ付加モル数の異なる各成分の比率に関しても、Ｒ¹の組成のうち最大成分の測定値から算出した結果、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：１．１９：１．１３：０．９４：１であった。 Production Example 5
Following Production Example 1, EO was reacted with lauryl alcohol as a raw material to obtain an alkyl ethoxylate having 3.55 moles of EO added. This was subjected to an oxidation reaction as in Example 1, and the resulting alkyl ether carboxylate was treated with hydrochloric acid to obtain an alkyl ether carboxylic acid.
As a result of analysis by gas chromatography, in general formula (1), M = H, R ¹ is a lauryl group, n has an average value of 3.1, n = 0 contains 16% by mass, and n = 1 The total amount of n = 2 components was 37% by mass.
In addition, regarding the ratio of each component having a different number of EO addition moles, as a result of calculation from the measured value of the maximum component of the R ¹ composition, (n = 0 component mass): (n = 1 component mass): ( n = 2 mass of component): (mass of n = 3 component): (mass of n = 4 component) = 1: 1.19: 1.13: 0.94: 1.

製造例６
製造例１に倣い、ミリスチルアルコールを原料にＥＯを反応させ、ＥＯ付加モル数３.５５モルのアルキルエトキシレートを得た。これを実施例１同様、酸化反応を行い、得られたアルキルエーテルカルボン酸塩を塩酸処理することにより、アルキルエーテルカルボン酸を得た。
ガスクロマトグラフィーの分析の結果、一般式（１）において、Ｍ＝Ｈ、Ｒ¹はミリスチル基、ｎの平均値は３．１、ｎ＝０の成分を１６質量％含み、ｎ＝１の成分とｎ＝２の成分の合計量は３７質量％であった。 Production Example 6
According to Production Example 1, EO was reacted with myristyl alcohol as a raw material to obtain an alkyl ethoxylate having 3.55 moles of EO added. This was subjected to an oxidation reaction as in Example 1, and the resulting alkyl ether carboxylate was treated with hydrochloric acid to obtain an alkyl ether carboxylic acid.
As a result of analysis by gas chromatography, in general formula (1), M = H, R ¹ is a myristyl group, n has an average value of 3.1, n = 0 contains 16% by mass, and n = 1 The total amount of n = 2 components was 37% by mass.

製造例７
製造例１に倣い、ラウリルアルコール、セチルアルコールを質量比２０／８０に混合した原料にＥＯ付加し、ＥＯ付加モル数３.５５モルのアルキルエトキシレートを得た。これを実施例１同様、酸化反応を行い、得られたアルキルエーテルカルボン酸塩を塩酸処理することにより、アルキルエーテルカルボン酸を得た。
ガスクロマトグラフィーの分析の結果、一般式（１）において、Ｍ＝Ｈ、Ｒ¹はラウリル基／パルミチル基＝２０／８０、ｎの平均値は３．１、ｎ＝０の成分を１６質量％含み、ｎ＝１の成分とｎ＝２の成分の合計量は３７質量％であった。 Production Example 7
Following Production Example 1, EO was added to a raw material in which lauryl alcohol and cetyl alcohol were mixed at a mass ratio of 20/80 to obtain an alkyl ethoxylate having 3.55 moles of EO added. This was subjected to an oxidation reaction as in Example 1, and the resulting alkyl ether carboxylate was treated with hydrochloric acid to obtain an alkyl ether carboxylic acid.
As a result of analysis by gas chromatography, in general formula (1), M = H, R ¹ is lauryl group / palmityl group = 20/80, n average value is 3.1, and n = 0 is 16% by mass. In addition, the total amount of the n = 1 component and the n = 2 component was 37% by mass.

製造例８
製造例１に倣い、ラウリルアルコールを原料にＥＯ反応させ、ＥＯ付加モル数４．０５モルのアルキルエトキシレートを得た。これを製造例１同様、酸化反応を行い、得られたアルキルエーテルカルボン酸塩を塩酸処理することにより、アルキルエーテルカルボン酸を得た。 Production Example 8
Following Production Example 1, lauryl alcohol was subjected to EO reaction as a raw material to obtain an alkyl ethoxylate having 4.05 moles of EO added. This was subjected to an oxidation reaction as in Production Example 1, and the resulting alkyl ether carboxylate was treated with hydrochloric acid to obtain an alkyl ether carboxylic acid.

ガスクロマトグラフィーの分析の結果、一般式（１）において、Ｍ＝Ｈ、Ｒ¹はラウリル基、ｎの平均値は３．５、ｎ＝０の成分を１１．４質量％含み、ｎ＝１の成分とｎ＝２の成分の合計量は３０．６質量％であった。
また、ＥＯ付加モル数の異なる各成分の比率に関しても、Ｒ¹の組成のうち最大成分の測定値から算出した結果、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：１．３１：１．３８：１．２５：１．０６であった。 As a result of analysis by gas chromatography, in general formula (1), M = H, R ¹ is a lauryl group, n has an average value of 3.5, and n = 0 contains 11.4% by mass, n = 1 The total amount of the components and n = 2 was 30.6% by mass.
In addition, regarding the ratio of each component having a different number of EO addition moles, as a result of calculation from the measured value of the maximum component of the R ¹ composition, (n = 0 component mass): (n = 1 component mass): ( n = 2 mass of component): (mass of n = 3 component): (mass of n = 4 component) = 1.1.31: 1.38: 1.25: 1.06.

製造例９
攪拌および温度調節機能を備えたステンレス製オートクレーブに、ラウリルアルコール［商品名：カルコール２０９８、花王製］１１４４ｇ（６．１４モル）、ミリスチルアルコール［商品名：カルコール４０９８、花王製］６０．２ｇ（０．２８１モル）、水酸化カリウム２．６ｇ（０．０４７８モル）を仕込み、減圧脱水を行った。次いで、エチレンオキサイド（ＥＯ）７１８ｇ（１６．３モル）を１５５℃にて導入し、反応温度１５５℃、反応圧力０.４ＭＰａで２時間反応を行った。反応終了後、冷却し、８０℃、６kPaの減圧条件で３０分間攪拌し、未反応のエチレンオキサイドを除去した後、窒素を導入し常圧にし、４.８２ｇ（０.０４８２モル）の９０％乳酸をオートクレーブ内に加え、８０℃で３０分間攪拌し、ＥＯ付加モル数２.５５モルのアルキルエトキシレートを得た。
攪拌、温度調節機能を取り付けたガラス製反応容器に、上記生成物６００ｇ（２．００モル）を仕込み、攪拌条件下、液温を７０℃まで昇温し、モノクロロ酢酸ナトリウム２５６ｇ（２．２０モル）及び水酸化ナトリウム８８ｇ（２．２０モル）を分割して加えながら、５時間反応を行った。反応終了後、３５％塩酸をｐＨが２．８になるまで加え、酸型化し油層を分取し、アルキルエーテルカルボン酸を得た。これをＥＣ６とする。 Production Example 9
In a stainless steel autoclave equipped with stirring and temperature control functions, 1144 g (6.14 mol) of lauryl alcohol [trade name: Calcoal 2098, manufactured by Kao], 60.2 g (0 trade name: Calcoal 4098, manufactured by Kao) .281 mol) and 2.6 g (0.0478 mol) of potassium hydroxide were added and dehydration under reduced pressure was performed. Subsequently, 718 g (16.3 mol) of ethylene oxide (EO) was introduced at 155 ° C., and the reaction was carried out at a reaction temperature of 155 ° C. and a reaction pressure of 0.4 MPa for 2 hours. After completion of the reaction, the mixture was cooled and stirred at 80 ° C. under a reduced pressure of 6 kPa for 30 minutes to remove unreacted ethylene oxide, then nitrogen was introduced to normal pressure, and 4.82 g (0.0482 mol) of 90% Lactic acid was added to the autoclave and stirred at 80 ° C. for 30 minutes to obtain an alkyl ethoxylate having 2.55 mol of EO added.
A glass reaction vessel equipped with stirring and temperature control functions was charged with 600 g (2.00 mol) of the above product, the temperature of the solution was raised to 70 ° C. under stirring conditions, and 256 g (2.20 mol) of sodium monochloroacetate was added. ) And 88 g (2.20 mol) of sodium hydroxide were added in portions, and the reaction was carried out for 5 hours. After completion of the reaction, 35% hydrochloric acid was added until the pH reached 2.8 to convert it into an acid form, and the oil layer was separated to obtain an alkyl ether carboxylic acid. This is EC6.

ガスクロマトグラフィーの分析の結果、一般式（１）において、Ｍ＝Ｈ、Ｒ¹はラウリル基／ミリスチル基＝９４／６、平均炭素数は１２．１、ｎの平均値は３．１、ｎ＝０の成分を９．９質量％含み、ｎ＝１の成分とｎ＝２の成分の合計量は３５．４質量％であった。
また、ＥＯ付加モル数の異なる各成分の比率に関しても、Ｒ１の組成のうち最大成分の測定値から算出した結果、（ｎ＝０成分の質量）：（ｎ＝１成分の質量）：（ｎ＝２成分の質量）：（ｎ＝３成分の質量）：（ｎ＝４成分の質量）＝１：１．６５：１．９２：１．７４：１.３２であった。 As a result of analysis by gas chromatography, in general formula (1), M = H, R ¹ is lauryl group / myristyl group = 94/6, average carbon number is 12.1, average value of n is 3.1, n = 0% component was included, and the total amount of the n = 1 component and the n = 2 component was 35.4% by mass.
In addition, regarding the ratio of each component having a different number of EO addition moles, as a result of calculation from the measured value of the maximum component of the composition of R1, (n = 0 component mass): (n = 1 component mass): (n = Mass of 2 components) :( mass of n = 3 components) :( mass of n = 4 components) = 1: 1.65: 1.92: 1.74: 1.32.

実施例中、ＥＣ２に関しては、製造例５、製造例６、製造例７で得られたアルキルエーテルカルボン酸を、各々質量割合で７８．７５／１５／６．２５の比で混合し、ＥＣ２とした。 In the examples, regarding EC2, the alkyl ether carboxylic acids obtained in Production Example 5, Production Example 6 and Production Example 7 were mixed at a mass ratio of 78.75 / 15 / 6.25, respectively. did.

実施例中、ＥＣ３に関しては、製造例２、製造例３で得られたアルキルエーテルカルボン酸を、各々質量割合で９０／１０の比で混合し、ＥＣ３とした。 In the examples, regarding EC3, the alkyl ether carboxylic acids obtained in Production Example 2 and Production Example 3 were mixed at a mass ratio of 90/10 to obtain EC3.

実施例中、ＥＣ４に関しては、製造例１で得られたＥＣ１と製造例４で得られたアルキルエーテルカルボン酸を、各々質量割合で４０／６０の比で混合し、Ｅ４とした。 In the examples, regarding EC4, EC1 obtained in Production Example 1 and the alkyl ether carboxylic acid obtained in Production Example 4 were mixed at a mass ratio of 40/60 to obtain E4.

実施例中、ＥＣ５に関しては、製造例２、製造例８で得られたアルキルエーテルカルボン酸を、各々質量割合で４０／６０の比で混合し、ＥＣ５とした。 In the examples, regarding EC5, the alkyl ether carboxylic acids obtained in Production Example 2 and Production Example 8 were mixed at a mass ratio of 40/60 to obtain EC5.

実施例中、ＥＣ７に関しては、製造例１で得られたＥＣ１と市販のＡＫＹＰＯＲＬＭ４５（花王社製）を、各々質量割合で５０／５０の比で混合し、ＥＣ７とした。 In the examples, regarding EC7, EC1 obtained in Production Example 1 and commercially available AKYPO RLM45 (manufactured by Kao Corporation) were mixed at a mass ratio of 50/50 to obtain EC7.

実施例中、ＥＣ８に関しては、製造例１で得られたＥＣ１と市販のＡＫＹＰＯＲＬＭ１００ＮＶ（花王社製）を、各々質量割合で５０／５０の比で混合し、ＥＣ８とした。 In the examples, regarding EC8, EC1 obtained in Production Example 1 and commercially available AKYPO RLM100NV (manufactured by Kao Corporation) were mixed at a mass ratio of 50/50 to obtain EC8.

なお、実施例で使用した成分（Ｂ）の構成は、表１に示すとおりである。
また、実施例で使用した市販のアルキルエーテルカルボン酸（ＡＫＹＰＯＲＬＭ４５（花王社製））の平均ＥＯ付加モル数は、各社販売元のカタログ値、ホームページで公開されている値を参考にした。不明なアルキル組成、ｎ＝０の成分量、ｎ＝１の成分とｎ＝２の成分の合計量に関しては、上記方法で分析した。 In addition, the structure of the component (B) used in the Example is as showing in Table 1.
Moreover, the average EO addition mole number of the commercially available alkyl ether carboxylic acid (AKYPO RLM45 (made by Kao company)) used in the Example referred to the catalog value of each company vendor, and the value currently published on the homepage. The unknown composition, the amount of n = 0, and the total amount of n = 1 and n = 2 were analyzed by the above method.

実施例１〜１３、比較例１〜４
表２に示す組成の固形洗浄剤組成物を製造し、固形性、泡立ち、ひび割れ、浴室の汚れ及びさっぱり感を評価した。結果を表２に併せて示す。
なお、表２中の「水」の含有量は、石鹸用素地、４８％ＮａＯＨ水溶液に含まれるものである。 Examples 1-13, Comparative Examples 1-4
A solid detergent composition having the composition shown in Table 2 was produced, and the solidity, foaming, cracking, bathroom dirt and refreshing feeling were evaluated. The results are also shown in Table 2.
In addition, the content of “water” in Table 2 is included in the soap base and the 48% NaOH aqueous solution.

（製造方法）
石鹸用素地に表２に示す他の成分を添加し、石鹸用素地と他の成分の合計が４００ｇになるようにし、愛工舎製作所製の「ＫＥＮＭＩＸ Chef」ミキサーで１０分間混合した。次に、日本化工機社製の３本ロールで一回処理し、混合物が均一になるように混練した。その後、日本化工機製のラボプロッダー（プロッダーには、直径４mmの穴が８５個開いた外径６９mmの蜂の巣状の多孔プレートを使用）を用いて押出成型を行い、固形洗浄剤組成物を得た。 (Production method)
The other ingredients shown in Table 2 were added to the soap base so that the total of the soap base and other ingredients was 400 g, and mixed for 10 minutes with a “KENMIX Chef” mixer manufactured by Aikosha Seisakusho. Next, it processed once with the three roll made by Nippon Chemical Industry Co., Ltd., and knead | mixed so that a mixture might become uniform. Then, extrusion molding was performed using a lab plodder manufactured by NIPPON KIKOH KIKI (a 69 mm outer honeycomb perforated plate having 85 holes 4 mm in diameter was used as the pudder) to obtain a solid detergent composition.

（評価方法）
（１）固形性：
押出成型した固形洗浄剤組成物の表面に、ハンディータイプの硬度計（KOUBUNSHI KEIKI, CO, LTD、ASKER硬度計、タイプＣ）を押し付け、その最大値を測定した。３箇所を測定し、その平均値を石鹸硬度とした。結果を以下の基準で示した。なお、この硬度が５０以上であれば、型打ちできると評価される。 (Evaluation method)
(1) Solidity:
A handy type hardness tester (KOUBUNSHI KEIKI, CO, LTD, ASKER hardness tester, type C) was pressed against the surface of the extruded solid detergent composition, and the maximum value was measured. Three places were measured and the average value was taken as soap hardness. The results are shown by the following criteria. In addition, if this hardness is 50 or more, it is evaluated that stamping is possible.

（２）泡立ち：
押出成型した５０ｇの固形洗浄剤組成物を１日５ｇずつ使用し、残った１０ｇの固形洗浄剤組成物について評価した。残った１０ｇの固形洗浄剤組成物を、４０℃、２５０mLの水が入った直径約６５mm、高さ２５０mmのシリンダーに入れ、直径５０mmの攪拌羽を取り付けたＲＥＶＥＲＳＥＳＴＩＲＲＥＲ（アルプ社製、モデルＲ−１０２型）を目盛り３で５分間攪拌（３０秒毎に回転方向を反対に変更し、合計で５分間攪拌）し、その後の泡量（mL）を測定した。なお、製造直後の固形洗浄剤組成物の泡量は、いずれの実施例、比較例においても１９０mL以上であり、良好であった。 (2) Foaming:
Extruded 50 g of the solid detergent composition was used 5 g per day, and the remaining 10 g of the solid detergent composition was evaluated. The remaining 10 g of the solid detergent composition was put into a cylinder having a diameter of about 65 mm and a height of 250 mm containing 250 mL of water at 40 ° C., and REVERSE STIRRER (model R-manufactured by Alp Co., Ltd.) equipped with a stirring blade having a diameter of 50 mm. 102 type) was stirred for 5 minutes on scale 3 (changing the direction of rotation opposite every 30 seconds and stirring for a total of 5 minutes), and the amount of foam (mL) thereafter was measured. In addition, the foam amount of the solid detergent composition immediately after manufacture was 190 mL or more in any of Examples and Comparative Examples, which was good.

（３）ひび割れ：
１cm×１cm の口金で押出成型し、長さ５cmで切断し、角柱の固形洗浄剤組成物を得た。これを、２５℃の水中に４時間浸漬した後、室温で２４時間乾燥させ、固形洗浄剤組成物の長面４面に発生したひび割れの本数を測定した。 (3) Cracks:
Extrusion molding was performed with a 1 cm × 1 cm 2 die, and the product was cut with a length of 5 cm to obtain a solid cleaning composition of a prism. This was immersed in water at 25 ° C. for 4 hours and then dried at room temperature for 24 hours, and the number of cracks generated on the four long surfaces of the solid detergent composition was measured.

（４）浴室の汚れ（石鹸汚れ付着量）
得られた固形洗浄剤組成物を２０ＨＤ硬水に溶かし、６％水溶液を調製した。この水溶液（４０℃）をフォーマー容器（１６０mL；ＹＦ−９４１３、吉野工業社製）に充填し、色Ｅ１（Ｌ１，ａ１，ｂ１）を測定した肌模型（肌模型Ｎｏ．１０Ａ（４０代）＃ＢＬＡＣＫ、表面ノーマル、ビューラックス製）の上に、１プッシュして泡（０．８５−０．９５ｇ）を塗布した。なお、色の測定には、色彩色差計（ミノルタ製、ＣＲ−３００）を用いた。泡を塗布したまま肌模型を、５０℃の乾燥機内に入れ、約１時間の放置をして、乾燥させた。その後、肌模型を乾燥機から取り出し、室温に戻し、スポイト（２mL）を用いて、２０ＨＤ硬水２mLが肌模型の表面に行きわたるようにしてすすいだ。３回すすいだ後、紙（ソフトプロワイパーS150、大王製紙社製）を用いて、肌模型上の水分を軽く拭い取った。更に、５分間、肌模型を自然乾燥させた後、肌模型の色Ｅ２（Ｌ２，ａ２，ｂ２）を測定した。３箇所を測定し、その平均値をＥ２とした。Ｅ１とＥ２の色差ΔＥ１２を、汚れの付着量とした。ΔＥ１２は、以下の式より計算した。
ΔＥ１２が小さいほど、石鹸汚れがつきにくいことを示す。
ΔＥ１２＝√[（Ｌ２-Ｌ１）²+（ａ２-ａ１）²＋（ｂ２−ｂ１）²] (4) Bathroom dirt (soap dirt adhesion amount)
The obtained solid detergent composition was dissolved in 20 HD hard water to prepare a 6% aqueous solution. A skin model (skin model No. 10A (40's) #) filled with this aqueous solution (40 ° C.) in a former container (160 mL; YF-9413, manufactured by Yoshino Kogyo Co., Ltd.) and measured for color E1 (L1, a1, b1) On top of (BLACK, surface normal, manufactured by Beaulux), one push was applied to apply foam (0.85-0.95 g). A color difference meter (manufactured by Minolta, CR-300) was used for color measurement. With the foam applied, the skin model was placed in a dryer at 50 ° C. and left to dry for about 1 hour. Thereafter, the skin model was taken out of the dryer, returned to room temperature, and rinsed using a dropper (2 mL) so that 2 mL of 20 HD hard water could reach the surface of the skin model. After rinsing three times, the moisture on the skin model was gently wiped off using paper (Soft Pro Wiper S150, manufactured by Daio Paper Co., Ltd.). Furthermore, after naturally drying the skin model for 5 minutes, the color E2 (L2, a2, b2) of the skin model was measured. Three places were measured and the average value was defined as E2. The color difference ΔE12 between E1 and E2 was defined as the amount of dirt adhered. ΔE12 was calculated from the following equation.
The smaller ΔE12, the harder the soap stains.
ΔE12 = √ [(L2−L1) ² + (a2−a1) ² + (b2−b1) ² ]

（５）さっぱり感：
プロッダー出口の口金口径を面取りし、４０mm×１５mmの大きさにして石鹸を押出し、長さ６０mmに切断して評価用の固形洗浄剤組成物を調製した。この固形洗浄剤組成物を、４０℃の水道水で十分泡立てた後、前腕部を１０秒間洗浄し、同じく４０℃の水道水の流水下ですすいだ。専門パネル５名により、すすぎの際のさっぱり感を官能評価し、「さっぱり感を感じた」専門パネルの人数で示した。 (5) Refreshing feeling:
The base diameter of the outlet of the pudder was chamfered, the size was set to 40 mm × 15 mm, the soap was extruded, and cut into a length of 60 mm to prepare a solid detergent composition for evaluation. This solid detergent composition was sufficiently bubbled with tap water at 40 ° C., then the forearm was washed for 10 seconds, and rinsed under running tap water at 40 ° C. A sensory evaluation of the refreshing feeling during rinsing was performed by five specialist panels, and the number was indicated by the number of expert panels who “feel refreshed”.

Claims

The following components (A), (B) and (C):
(A) Fatty acid sodium salt 65-95 mass%,
(B) General formula (1)

(In the formula, R ¹ represents an alkyl group having 10 to 16 carbon atoms, n represents a number of 0 to 20, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, or organic ammonium)
Wherein R ^{1 has} an average carbon number of 10.8 to 12.8, an average value of n is 2.5 to 6.4, and n = 0 An alkyl ether carboxylic acid or a salt thereof containing 3 to 15% by mass of 9.8 to 27% by mass of a component of n = 1 and a component of n = 2 and 27 to 36.1% by mass
(C) The manufacturing method of a solid detergent composition provided with the process of knead | mixing the solid detergent composition containing water, and the process extruded to a rod shape with an extruder.

The method for producing a solid detergent composition according to claim 1, wherein the component (A) is a fatty acid sodium salt obtained from palm kernel oil and palm stearin oil.

The method for producing a solid detergent composition according to claim 1 or 2, wherein the component (A) is a fatty acid sodium salt soap base obtained from palm kernel oil and palm stearin oil.

In the component (B), in the general formula (1), R ¹ is an alkyl group having 10 to 16 carbon atoms, an average value of n is 2.5 to 3.7, and a component of n = 0 is 9. the process according to claim 1 solid detergent composition according to any one of 3 containing 9 to 27 wt%.

In the component (B), in the general formula (1), R ¹ is an alkyl group having 10 to 16 carbon atoms, any one of claims 1-4 average value of n is 2.5 to 3.4 1 The manufacturing method of the solid cleaning composition of description.

In the component (B), in the general formula (1), R ¹ is an alkyl group having 10 to 16 carbon atoms , an average carbon number is 10.8 to 12.5, and an average value of n is 2.8 to 3.4 a and the component of n = 0 9.9 to 16 wt%, claim 1-5 where the n = 1 and a component in which n = 2 in total comprising 27 to 36.1 wt% A method for producing the solid detergent composition according to claim 1.

In the component (B), in the general formula (1), the alkyl chain length components of the maximum content of the composition of R ^1, (n = 0 component of the mass) mass :( n = 1 component) :( n = 2 component mass): (n = 3 component mass): (n = 4 component mass) = 1: 0.99 to 3.50: 0.89 to 3.00: 0.76 to 3.00: the process according to claim 1 solid detergent composition according to any one of 6 to be 0.63 to 1.52.

In component (B), in general formula (1), R ¹ contains two or more alkyl groups, and the component having the largest alkyl chain length is 55% by mass or more and less than 97% by mass. method for manufacturing a solid detergent composition according to any one of 1-7.

In the component (B), in the general formula (1), in the alkyl chain length component having the maximum content in the composition of R ^1, a component of n = 0 is contained in an amount of 9.9% by mass to less than 12% by mass, (n = 0 component mass): (n = 1 component mass): (n = 2 component mass): (n = 3 component mass): (n = 4 component mass) = 1: 1.53-1. 87: 1.59 to 2.25: 1.33 to 2.16: 1.14 to 1.52, or 12 to 17% by mass of n = 0, and R ¹ In the composition having the maximum alkyl chain length in the composition, (mass of n = 0 component): (mass of n = 1 component): (mass of n = 2 component): (mass of n = 3 component): ( n = 4 weight component) = 1: 0.99 to 1.34: 0.89 to 1.40: 0.76 to 1.23: 0.63 to 1 and consisting claim 1-8 either 1 Method for manufacturing a solid detergent composition.

A method for rinsing the skin after applying and washing the solid detergent composition obtained by the production method according to any one of claims 1 to 9 on a body skin part.