MXPA06007360A - Carboxamide derivative, processes for producing the same, and detergent composition - Google Patents

Abstract

A carboxamide derivative having a reduced amide ester content;processes for producing the carboxyamide derivative;and a detergent composition containing the carboxamide derivative and having excellent low-temperature stability. One of the processes, which is for producing a carboxamide derivative, comprises reacting a carboxamide with hydrogen peroxide, the carboxamide being one having an amide ester content of 0.02 to 0.18%by mass produced by a carboxamide production process comprising a carboxamide synthesis step in which a fatty acid ester is reacted with 1.20 to 1.60 mol of a diamine per mol of the ester to synthesize a carboxamide. The other process for producing a carboxamide derivative comprises reacting the carboxamide with any of monohaloalkylcarboxylic acids and salts thereof. The carboxamide derivative provided is one produced by either of the carboxamide derivative production processes. In a preferred embodiment, the carboxamide derivative is an amide amine oxide or an amide betaine.

Description

CARBOXAMIDE DERIVATIVE, PROCESS TO PRODUCE THE SAME, 1 COMPOSITION DETERGENT Technical field The present invention relates to: a carboxamide derivative having reduced ester amide content; an efficient production method thereof; and a detergent composition which includes the carboxamide derivative produced by the production method and which has excellent stability at low temperature.

Environment of the technique. The carboxamide is used in hair conditioners, and is used as an intermediate of a carboxamide derivative such as betaine amide and amine oxide to amine. In particular, a carboxamide derivative is widely used for cleaning agents such as hair shampoo and kitchen detergent, cosmetic materials and beauty products, since it is less irritating to the skin and has favorable biodegradability.

The carboxamide is usually produced by condensing a fatty acid or an ester thereof with a diamine at a reaction temperature of 80 ° C to 200 ° C and under normal or reduced pressure. It is also known that a can be obtained. amide amine oxide as a carboxamide derivative, oxidizing the carboxamide with hydrogen peroxide, and it is known that betaine amide can be obtained as a carboxamide derivative through the ionization of the carboxamide with monohaloalkylcarboxylic acid and a salt thereof.

For example, it is considered that the amount of diamine used for the production of high purity carboxamide is preferably 0.83 times per mole at 1.25. . times per mole, and more preferably 1.0 times per mole to 1.2 times per mole, with respect to the amount of a fatty acid or an ester thereof (Literature, of Patent 1). It is also known that an addition of organic phosphonic acid to produce amide amide oxide produces a composition which includes amine amide oxide with superior preservation stability at a high temperature of 50 ° C in terms of color and fragrance (Patent Literature). 2) . 0 However, sedimentation occurs during the preservation of amide amide oxide at low temperature, which is obtained by reacting hydrogen peroxide with the carboxamide obtained by reacting a fatty acid ester with 1.20 times per mole or less, with respect to the ester. of 5 fatty acid, of one diamine, one amino betaine, which is. obtains by reacting the carboxamide with a monohaloalkylcarboxylic acid or a salt thereof. This causes problems such as a decreased commercial value of amide amide oxide and amide betaine, as well as reduced low temperature stability of a detergent composition using them.

Patent Literature 1: [0017] in Japanese Laid-Open Patent Application (JP-A) No. 349542. Patent Literature 2: [0022] and [0023] in the JP-A No. 11-152260.

The present invention aims to solve conventionally existing problems to achieve the following. That is, the present invention is directed to provide: a carboxamide derivative. having reduced content of amide ester; an 'efficient production method' thereof, and a 'detergent composition which includes the carboxamide derivative produced through the production method and which has excellent stability at low temperature.

The inventors of the present invention found, as a result of a desire to perform tests to solve the problems, that the reduced low temperature stability of a carboxamide derivative was derived from an amide ester included in the carboxamide as a by-product. They also found that by increasing the mole ratio of diamine to the fatty acid ester by producing the carboxamide by reacting the fatty acid ester and the diamine, the collateral reaction of the amide ester could be suppressed and produce a carboxamide having superior to low stability temperature and, as a result, made the following 'invention.

The present invention is based on the findings of the inventors of the present invention, and the means for solving the problems are as follows: <1> a method for producing carboxamide which includes a process for synthesizing the carboxamide, where the carboxamide is synthesized by reacting a fatty acid ester represented by the General Formula (1) below, with a diamine represented by the Formula General (2) below to a molar ratio of diamine to . fatty acid ester from 1.20 to 1.60; and the carboxamide includes 0.02% by mass at 0.18% by mass of the amide ester represented by the. General Formula (3) below: Rx-COOR2 General Formula (1) wherein, in the General Formula (1) above, R1 represents any of a straight chain or branched chain alkyl group, an alkenyl group and a hydroxyalkyl group having a carbon number of from five to 23; and R2 represents a straight chain or branched chain alkyl group having a carbon number, from one to four; : 'S :: X': '': -. 0. '' x * 3, 'V:' '• "• • -' -: A -: '-SH2N- (CH¿) n-N General Formula (2) yy -' / 'xx;: -" v' :: sV '• -: P -y: .- -; -? where, in the General Formula (2) above, R3 and R4 are the same or different and represent an alkyl group having a carbon number of one to four; and n represents an integer from two to four; Y General Formula (3) wherein, in the General Formula (3) above, R1 and R5 represent any of a straight chain or branched chain alkyl group, an alkenyl group and a hydroxyalkyl group having a carbon number of from five to 23; and n represents an integer from two to four. < 2 > A method for producing a carboxamide derivative including a process for producing a carboxamide derivative represented by the General Formula (4) below, by reacting the carboxamide produced with the method for producing carboxamide according to < 1 > and hydrogen peroxide: 10 R3 R ^ CONH-ÍGHa ^ - - ^ 0: General Formula (4) wherein, in the General Formula (4), R1 represents any of a straight chain or branched chain alkyl group, an alkenyl group and a hydroxyalkyl group having a carbon number of from five to 23; ^ R3 and R4 are. the same or different, representing an alkyl group having a carbon number of one to four; and n represents an integer from two to four. 20. < 3 > A method for producing a carboxamide derivative including a process for producing a carboxamide derivative represented by the General Formula (6) below, the carboxamide produced by the method reacting to produce carboxamide according to < 1 > and any of a monohaloalkylcarboxylic acid represented by Structural Formula (5) below and a salt thereof: YR6COOZ General Formula (5) where, in the General Formula (5), Y represents a halogen atom; R6 represents a straight chain or branched chain alkylene group having a carbon number of one to three; and Z represents any of a hydrogen atom and an alkali metal atom; Y to (6) wherein, in the General Formula (6), R1 represents any of a straight chain or branched chain alkyl group, an alkenyl group and a hydroxyalkyl group having a carbon number of from five to 23; R3 and R4 are the same or different, representing an alkyl group having a carbon number of one to four; and n represents an integer from two to four. < 4 > The method for producing a carboxy derivative according to any of < 2 > a < 3 > , wherein the content of amide ester represented by the General Formula (3) below in the carboxamide derivative is 0.05% by mass or less: • ... P. - '"P .'- -XX O- •' or" '. •••• -x - '' '' ': -: A • -' '. "-". "' II - = 'General Formula (3) K-GONH-? CHsk-Q-CR where, in the General Formula (3) above, R1 and R5 represents any of a straight chain or branched chain alkyl group, an alkenyl group and a hydroxyalkyl group having a carbon number of five to 2. 3; and n represents an integer from two to four. < 5 > A carboxamide derivative produced by any of the methods for producing a carboxamide derivative according to < 2 > a < 4 > . < 6 > The carboxamide derivative according to < 5 > , wherein the carboxamide derivative is amide amide oxide. < 7 > The carboxamide derivative according to < 5 > , wherein the carboxamide derivative is amide betaine. < 8 > A detergent composition that includes a. carboxamide derivative according to < 5 > a < 7 > .

Best way to carry out the invention. (Method to produce carboxamide). A method for producing carboxamide of the present invention includes a process for synthesizing the. carboxamide, and also includes other processes according to the requirements.

. Process of carboxamide synthesis. The process for synthesizing the carboxamide is to synthesize the carboxamide through a reaction of fatty acid ester with diamine.

Ester. of fatty acid. Examples of the fatty acid ester include the fatty acid esters represented by the General Formula (1) below: R1-COOR2 General Formula (1) 0 wherein, in the General Formula (1) above, R1 represents any of a straight chain or branched chain alkyl group, an alkenyl group and a hydroxyalkyl group having a carbon number- of five to 5 23; and R2 represents a straight chain or branched chain alkyl group having a carbon number of one to four.

The fatty acid esters are not particularly restricted and may be appropriately selected according to the applications, and examples thereof include: methyl ester, ethyl ester or vegetable oil glyceride or animal oil fatty acid, and a mixture thereof. same. Among these, a higher fatty acid with R2 is preferable as an alkyl group having a carbon number of one to four and a lower alkyl ester thereof, and those with R1 as a straight chain alkyl group having a number of carbons from nine to 21 and R2 as a methyl group.

The vegetable oil or the animal oil fatty acid are not particularly restricted - and can be appropriately selected according to the applications. Examples thereof include: caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, erucic acid, 12-hydroxystearic acid, coconut oil fatty acid, seed fatty acid cotton, corn oil fatty acid, hydrogenated tallow, babassu palm oil fatty acid, palm kernel oil fatty acid, soybean oil fatty acid, "flaxseed oil fatty acid, oil fatty acid beaver, fatty acid from olive oil, fatty acid from whale fat oil and fatty acid from palm oil.

Diamine. . Examples of diamine include Tas diamines represented by the General Formula (2) below: . . . .. .. -. . General Formula (2) where, in the General Formula (2) above, R3 and R4 are the same or different and represent an alkyl group having a carbon number of one to four; and n represents an integer from two to four.

The diamines are not particularly restricted and can be selected appropriately according to the applications. Examples thereof include: dimethylaminopropylamine, dimethylaminoethylamine, diethylaminopropylamine, diethylaminoethylamine, dibutylaminopropylamine, dibutylaminoethylamine, dipropylated inopropylamine and dipropylaminoethylamine. Among these, dimethylaminopropylamine and diethylaminoethylamine are favorably used.

In the process of synthesis of the carboxamide, the reaction temperature is preferably from 80 ° C to 220 ° C, more preferably from 100 ° C to 200 ° C, and even more favorably from 160 ° C to 200 ° C. The reaction time is preferably from 3 hours to 20 hours, and more preferably from five hours to 10 hours.

In the process of synthesis of the carboxamide, the molar ratio of the diamine to the fatty acid ester is preferably 1.20 to 1.60, and. more preferably from 1.25 to 1.40.

When the molar ratio exceeds 1.60, the reflux range of the diamine during the reaction increases considerably, and the reaction temperature can not be maintained from 160 ° C to 200 ° C, which can slow down the reaction. In addition, the concentration of active ingredients becomes low, and productivity can be reduced. When the molar ratio is less than 1.20, the content of amide ester produced as a byproduct during the reaction increases, and this can adversely affect the low temperature stability of the carboxamide mentioned hereinafter.

Here, the productivity of the carboxamide can be obtained with the following equation: productivity (g / (g «h)) = solid content concentration (% by mass) / time required to achieve the conversion rate of 99.5% (h).

The diamine can be charged in the initial step of the reaction, or it can be delivered by dripping from the gas phase or introduced into the reaction solution during the reaction. Also, to suppress the __ distillation • of the reactive amine, the diamine can be charged so that the molar ratio of the diamine to the ester is from 0.3 to 1.0 and reacted at a temperature of 150 ° C to 170 ° C, and then, with the rest of the diamine delivered by drip, the system can. be heated to a temperature of 170 ° C to 220 ° C and cured by aging until the amount of unreacted diamine is reduced.

The process of synthesis of the carboxamide can be carried out under a reduced pressure, at a normal pressure or under increased pressure.

The process of synthesis of the carboxamide can be carried out under the presence of an alkaline catalyst, such as sodium methoxide. The presence of the alkaline catalyst can reduce the reaction temperature or shorten the reaction time.

In the above process, the fatty acid ester and the diamine react to produce the carboxamide.

Other processes The other processes are not particularly restricted and can be appropriately selected according to the applications. Favorable examples thereof include a distillation process and a recovery process.

The distillation process is a process to distill a lower alcohol produced as a by-product in the synthesis process of the carboxamide.

There is no particularly restricted method for distillation, and it can be appropriately selected from among the methods hitherto known according to the applications. For example, in the process of synthesis of the carboxamide, the temperature can be controlled above the boiling point of the lower alcohol and below the boiling point of the diamine by means of a condenser. Here, it is preferable to blow an inert gas such as nitrogen gas, to promote distillation.

- In the above process, the lower alcohol is distilled from the reaction solution.

The recovery process is a process to distill and recover unreacted diamine after the completion of the carboxamide synthesis process. The diamine recovered in the recovery process can be reused in the synthesis process of the carboxamide.

. There is not a particularly restricted recovery method and it can be selected appropriately from the methods hitherto known according to the applications. For example, recovery can be carried out under reduced pressure or with a descending nitrogen blowing method.

In the above process, the unreacted diamine can be recovered from the reaction solution.

Like the other processes, by distilling only the lower alcohol and refluxing the unreacted diamine, the carboxamide can be produced efficiently in the process of carboxamide synthesis.

Carboxamide The carboxamide of the present invention is produced by the method for producing carboxamide of the present invention. The carboxamide includes an amide ester as a by-product.

Specifics of the carboxamide include: decanoic acid dimethylaminopropylaminamididamide, dimic acid dimethylaminoethylamide, decanoic acid diethylaminoethylamide, decanoic acid diethylaminopropylamide, decanoic acid dibutylaminopropylamide, lauric acid dimethylaminopropylamide, lauric acid dimethylaminoethylamide, lauric acid diethylaminoethylamide, diethylaminopropylamide lauric acid, dibutylaminopropylamide lauric acid, myristic acid dimethylaminopropylamide, myristic acid dimethylaminoethylamide, myristic acid diethylaminoethylamide, myristic acid diethylaminopropylamide, myristic acid dibutylaminopropylamide, palmitic acid dimethylaminopropylamide, palmitic acid dimethylaminoethylamide, palmitic acid diethylaminoethylamide, palmitic acid diethylaminopropylamide, palmitic acid dibutylaminopropylamide, stearic acid dimethylaminopropylamide, dimethylaminoethyl amide of stearic acid, diethylaminoethylamide of stearic acid, diethylaminopropylamide of stearic acid, dibutylaminopropylamide of stearic acid, dimethylaminopropylamide of oleic acid, dimethylaminoethylamide of oleic acid, diethylaminoethylamide of oleic acid, diethylaminopropylamide of oleic acid, dibutylaminopropylamide of oleic acid, dimethylaminopropylamide of fatty acid of coconut oil, coconut oil fatty acid dimethylaminoethylamide, coconut oil fatty acid diethylaminoethylamide, coconut oil fatty acid diethylaminopropylamide, coconut oil fatty acid dibutylaminopropylamide, hardened tallow dimethylaminopropylamide, hardened tallow dimethylaminoethylamide, hardened tallow diethylaminoethylamide, hardened tallow diethylaminopropylamide, hardened tallow dibutylaminopropylamide, behenic acid dimethylaminopropylamide, behenic acid dimethylaminoethylamide, behenic acid diethylaminoethylamide or, behenylic acid diethylaminopropylamide, behenyl acid dibutylaminopropylamide, isostearic acid dimethylaminopropylamide, isostearic acid dimethylaminoethylamide, isostearic acid diethylaminoethylamide, diethylaminopropylamide, iiskstearic acid, and dibutylaminopropylamide, isostearic acid.

The carboxamide can be stored as a solid at room temperature or as a liquid after heating. Preferably it is sealed with nitrogen to suppress color degradation.

Examples of the amide ester include the amide esters represented by the General Formula (3) below: General Formula (3) wherein, in the General Formula (3), R1 - and R5 represent any of a straight chain or branched chain alkyl group, an alkenyl group and a hydroxyalkyl group having a carbon number of from 5 to 2. 3; and n represents an integer from one to four.

The specific examples of the amide esters include the amide esters represented by the General Formulas (7) to (13): OR 11 General Formula (12) 7H35-CONH ~ (CH2) 3- OR- C- C17H35 General Formula (13) The content of amide ester in the carboxamide is preferably 0.02% by mass to 0.18% by mass. The increased content thereof may adversely affect the "low temperature stability of the carboxamide derivative mentioned below.

When a mixture of fatty acid esters is used as the fatty acid ester, the length of the alkyl chain of the amide ester is not that of a single chain, but a mixture of the lengths of the alkyl chains of the esters of fatty acid used.

Method for producing the carboxamide derivative. A method for producing a carboxamide derivative of the present invention is carried out through a reaction of the carboxamide and hydrogen peroxide.The method for reacting the carboxamide and the hydrogen peroxide is not particularly restricted and can be appropriately selected from the methods hitherto known according to the applications.

It is preferable that the hydrogen peroxide be dissolved in a solvent and used as a solution, and it is more preferable that the solution be an aqueous solution.

Preferable examples of the solvent include - one or more types of solvents selected at least from water and alcohols.

The alcohols are not particularly restricted and can be appropriately selected according to the applications. Examples thereof include ethanol, 2-propanol and propylene glycol. Among these, 2-propanol and ethanol can be favorably used, since they can increase the concentration of the active ingredient concentration of a carboxamide derivative generated.

The amount of solvent used is not particularly restricted insofar as it satisfies the stirring and mixing of the reaction products; it can be appropriately selected according to the applications. Since the concentration of the active ingredient of the carboxamide derivative in a reaction product is preferably from 10% by mass to 50% by mass, and more preferably from 15% by mass to 40% by mass, it is preferable that the amount of solvent used is sufficient for the concentration of the active ingredient. When the amount used is very small, the mixing state of the products of the reaction is uneven, and the mixture can be turned into a gel. When too large a quantity is used,. the concentration of the carboxamide derivative decreases and productivity can be reduced.

The molar ratio of the hydrogen peroxide to the carboxamide is preferably from 0.9 to 1.4, more preferably from 1.0 to 1.3, and even more preferably from 1.02 to 1.10. The small molar ratio of hydrogen peroxide increases the reaction time as well as the carboxamide content, and the large molar ratio of hydrogen peroxide increases the amount of hydrogen peroxide remaining after the reaction and tends to cause collateral reaction. Therefore, the too large or too small molar ratio of hydrogen peroxide is not preferable.

The concentration of hydrogen peroxide in the hydrogen peroxide solution is preferably 5% by mass to 60% by mass, and more preferably from 8% by mass to 45% by mass. When the concentration of hydrogen peroxide is too high, self-decomposition of hydrogen peroxide may occur, as well as a local reaction. On the other hand, when the concentration of hydrogen peroxide is too small, the concentration of. carboxamide with respect to the solvent is too high, impairing fluidity and possibly reducing productivity. It is preferable that the charged amount of the hydrogen peroxide solution satisfy the molecular relationship. Also, the carboxamide and the hydrogen peroxide can be replenished during the reaction.

After replenishment of hydrogen peroxide, the state of agitation is preferably maintained to improve the conversion range of the carboxamide.

The temperature during the replenishment of the hydrogen peroxide and stirring are preferably maintained above the temperature at which the reactants can be stirred and mixed, or also below the decomposition temperature of the carboxamide derivative, Preferably, this temperature is for example 50 °. C at 100 ° C, and more preferably from 80 ° C to 90 ° C. Also preferably stirring is maintained for 30 minutes to 20 hours, and more preferably from one hour to eight hours.

The carboxamide and the hydrogen peroxide can be reacted under an increased pressure or a normal pressure.

Also, when a large amount of hydrogen peroxide has remained unreacted in the reaction product after the completion of the reaction, the carboxamide can be added, or a decomposition reaction selected from the methods hitherto known can be performed according to the invention. with the requirements. Examples of decomposition reaction methods include a method of adding sodium hydroxide.

A method for producing a carboxamide derivative of the present invention can also be carried out by reacting the carboxamide and one of the monohaloalkylcarboxylic acids represented by the formula General (5) below and a salt thereof: YR6COOZ General Formula (5) wherein, in the General Formula (5), Y represents a halogen atom, R6 represents a straight chain or branched chain alkylene group having a carbon number of one to three, and Z represents any of a hydrogen atom and an alkali metal atom.

The method for reacting the carboxamide and any of the monohaloalkylcarboxylic acids and a salt thereof is not particularly restricted and can be appropriately selected from the methods hitherto known according to the applications. Examples thereof include a method for mixing the carboxamide and any of the monohaloalkylcarboxylic acids and the salt thereof with water for reaction. Here, the reaction is preferably carried out at a sustained pH in the range of 8 to 13 by means of an alkali such as sodium hydroxide. The reaction temperature is also preferably established in the range of 50 ° C to 100 ° C. The reaction can be carried out under an increased pressure or a normal pressure.

The monohaloalkylcarboxylic acid and a salt thereof are preferably dissolved in a solvent and used as a solution, and the solution is more preferably an aqueous solution.

Preferable examples of the solvent include one or more types of solvents selected at least from water and alcohols.

The alcohols are not particularly restricted and can be appropriately selected according to the applications. Examples thereof include ethanol, 2-propanol and propylene glycol. - The monohaloalkylcarboxylic acid and a salt thereof are not particularly restricted and can be selected. properly according to the applications. Examples thereof include: monochloroacetic acid, monobromoacetic acid, monochloropropionic acid ,. monobromopropionic acid, sodium salts thereof and potassium salts thereof. Among these, monochloroacetic acid salts are particularly preferable.

The molar ratio of the monohaloalkylcarboxylic acid or salt thereof to the carboxamide is preferably 1 to 1.3, and more preferably 1 to 1.15.

Derived from carboxamide. A carboxamide derivative of the present invention can be produced by means of the method for producing a carboxamide derivative of the present invention.

Favorable examples of the carboxamide derivative include: the amine amide oxides represented by the General Formula (4), which can be produced by reacting the carboxamide and the hydrogen peroxide; and the amide betaines represented by the General Formula (6), which can be produced with any, of the monohaloalkylcarboxylic acids and a salt thereof. l (4) .- where, in the General Formula (4), R1 represents any of: a straight chain or branched chain alkyl group, an alkenyl group and a hydroxyalkyl group having a carbon number of from five to 23; R3 and R4 are the same or different, representing an alkyl group having a carbon number of one to four; Y ? represents an integer from two to four.

General Formula (6) wherein, in the General Formula (6), R1 represents any of: a straight chain or branched chain alkyl group, an alkenyl group and a hydroxyalkyl group having a carbon number of from five to 23; R3 and R4 are the same or different, representing an alkyl group having a carbon number of one to four; and n represents an integer from two to four.

Examples of the carboxamide derivative other than the amide amide oxides and the amide betaines include a quaternary amide salt and an amide carboxylate.

The carboxamide derivatives include the amide ester represented by the General Formula (3) above as a by-product. The content of amide ester in the carboxamide derivative is preferably small and, more specifically, is preferably 0.05% by mass or less.

When the content exceeds 0.05% by mass, the amide ester can not be solubilized and precipitated in the solution including the carboxamide derivative, and the solution can become cloudy with precipitation. As for the amide propyl lauryl ester of lauric acid, although this depends on the length of the chain, the precipitation of the amide ester does not dissolve until it is heated to 30 ° C or more, and especially during the winter the solution becomes turbid during preservation, due to precipitation, unless heated and stored. When the content is 0.05% by mass or less, the carboxamide derivative with superior stability at low temperature can be obtained, without precipitation during preservation at a low temperature of, for example 0 ° C.

The carboxamide derivative produced by means of a method for producing the carboxamide derivative of the present invention and using the carboxamide produced by the method for producing the carboxamide of the present invention, produces a reduced content of the amide ester and higher than low stability temperature. Thus, it can be used favorably for a detergent composition of the present invention described below.

Detergent composition A detergent composition of the present invention includes the carboxamide derivative produced by means of the method for producing the carboxamide derivative of the present invention, and further includes other components according to the requirements.

Favorable examples of the carboxamide derivative included in the detergent composition include the amide amide oxides and the amide betaines of the present invention.

The other components are not particularly restricted and are appropriately selected from among the components known up to now that have been conventionally used for a detergent composition according to the applications. Examples thereof include anionic surface agents, nonionic surface agents and amphoteric surface agents.

The anionic surface agents are not particularly restricted and can be appropriately selected according to the applications. Examples thereof include: polyoxyethylene alkyl sulfates, alkylbenzene sulfonates, alkyl sulfates, α-olefin sulfonates, alkyl ether carboxylates, alkane sulfonates, fatty acid sulfo salts, soaps, amide ether carboxylates , sulfosuccinates, fatty acid salts, alkyl ether carboxylates, acyl glutamates, acyl sarcosinates, N-methyl-β-alanine salts and acylmethyl taurates.

The nonionic surface agents are not particularly restricted and can be appropriately selected according to the applications. Examples thereof include: polyoxyethylene alkyl ethers such as polyoxyethylene (12) lauryl ether, polyoxyethylene (12) decyl ether, polyoxyethylene (15) lauryl ether, polyoxyethylene (15) myristyl ether, . polyoxyethylene (20) lauryl, polyoxyethylene (20) myristyl ether and polyoxyethylene (30) lauryl ether; alkyl polyglycosides; alkanolamides such as capric acid monoethanolamide, capric acid diethanolamide, lauric acid monoethanolamide, lauric acid diethanolamide, acid monoethanolamide. mystic, - myristic acid diethanolamide, coconut fatty acid monoethanolamide and coconut fatty acid diethanolamide; polyoxyethylene monoethanolamides such as polyoxyethylene (2) lauric monoethanolamide; N-5 methylglucamide ester and alkyl amine oxide.

The amphoteric surface agents are not particularly restricted and can be appropriately selected according to the applications. Examples thereof include: alkylamide betaines, alkyl acetic acid betaines, alkyl hydrosulfobetaines, alkyl imidazolinium betaines, and alkyl aminopropionic acid. The other components include: high polymer silicone compounds, organic acids or salts thereof such as citric acid, malic acid and lactic acid; amino acids such as glutamic acid, glycine and alanine; polymers. anionic; cationic polymers, amphoteric polymers; nonionic polymers; disinfectants; higher alcohols; Hydrocarbons; natural oils; ester oils; antioxidants; metal sequestrants; colorants; flavors; solvents such as ethanol and carbitol derivatives; polyols; and fatty acids: These other components can be used alone or in combination of two or more types.

A . The detergent composition of the present invention includes the carboxamide derivative with low content of the amine ester of the present invention, and has a favorable stability at low temperature as well as superior detergency and foaming power. Therefore, it can be favorably used for various types of detergents, especially hair shampoo, body shampoo, face wash, hair treatment, kitchen detergent and various detergents for household cleaning.

The present invention is illustrated in detail with reference to the examples given below, but these should not be construed as limiting the present invention.

Example 1. Production of carboxamide. Synthesis process of the carboxamide. In a 1 liter four-neck flask equipped with a stirrer, a thermometer and a reflux condenser, 352 g of methyl ester of lauric acid were charged.

(PASTELL M-12 with a molecular weight of 214, manufactured by Lion Oleochemical Co., Ltd.), and the bottle was purged twice with nitrogen (returning from a reduced pressure of 6.7 kPa to a normal pressure with nitrogen). Then it was heated to 180 ° C, and 202 g of N, N-dimethyl-1,3-propanediamine (hereinafter called DMAPA), which had the molar ratio to the methyl ester of lauric acid of 1.20, were delivered drip from 190 ° C to 200 ° C for four hours. Then, it was cured by aging from 190 ° C to 200 ° C for five hours, and the carboxamide was obtained. The carboxamide was dimethylaminopropylamide lauric acid.

Distillation process and recovery process. Warm water at a temperature of 80 ° C was run through the reflux condenser, and methanol was distilled as a by-product in the process of carboxamide synthesis. The unreacted DMAPA was also recovered through partial condensation and returned to the reactor.

Measurement of the conversion range of the fatty acid ester to carboxamide. The amount of unreacted lauric acid methyl ester was measured with a gas chromatographic analysis.

(GC) based on the following GC conditions, and the conversion range of methyl ester from lauric acid to carboxamide was calculated. The time required for the conversion rate to reach 99.5% was 6.2 hours.

GC conditions. The HP-5860 was used as the chromatographic apparatus of - gas, and DB-17 (0.25 mm diameter x 30 m length, with a film thickness of 0.25 μm and manufactured by J &W) was used as the column. The temperature of the column was initially 60 ° C and was increased to a range of 5 ° C / min until it reached 280 ° C. Then, the system was maintained at 280 ° C for 40 minutes. The injection temperature was 280 ° C; the temperature of the detector was 280 ° C; the carrier gas was helium; the division ratio fu-of 1:10, the detector was FID; the concentration of the sample was 2% by mass (2-propanol); and the injection amount was 1 μL.

Measurement of solid concentration. The solid concentration of the reaction mixture was measured based on the following solid content analysis conditions. The solid concentration was 93.5% by mass » Conditions of solid content analysis. The PD 600 (manufactured by Kett Electric Laboratory) was used as the apparatus, and the analysis was carried out at a temperature of 105 ° C for 60 minutes. The amount of the sample was 2 g. The amount of solid was also calculated through the solids content (% by mass) = 100 - volatile content (% by mass).

Measurement of the amount of amide ester.

The reaction mixture was depressurized at 2.0 kPa at 190 ° C - and covered for one hour to remove unreacted DMAPA. Then, it was cooled to 90 ° C to recover the reaction mixture. The content of amide ester in this reaction mixture was calculated with the GC-MS analysis based on the following GC-MS analysis conditions. Here, the amide ester develops its peak in the chromatogram GC 54.3 minutes after the peaks of methyl laurate (18.2 minutes) and of C 2 -carboxamide (35.1 minutes). The content of the amide ester (C ??H23CONH (CH2) 3OCOCuH23, with a molecular weight of 439) was 0.18% by mass (area% GC).

Conditions of the GC-MS analysis. HP-6890/5972 was used as a gas chromatographic apparatus, and DB-17 (0.25 mm diameter x 30 m length, with a film thickness of 0.25 μm, manufactured by J &W) was used as the column. .. The temperature in the column was initially 60 ° C and was increased to a range of 5 ° C / min until it reached 280 ° C. Then the system was maintained at 280 ° C for 40 minutes. The injection temperature was 280 ° C; the temperature of the detector was 280 ° C; helium was injected as a carrier gas, at a rate of 1.0 mL / min; The method was adopted as an ionization method; and the ionization voltage was 70 eV. The partition ratio was 1:10; - the concentration of the sample was 2% by mass (2-propanol); and the injection amount was -1 μL.

Example 2. Production of carboxamide. The carboxamide was produced in the same manner as in Example 1, except that 340 g of lauric acid methyl ester and 211 g of N, N-dimethyl-1,3-propanediamine (DMAPA) were used at a molar ratio of DMAPA to lauric acid methyl ester of 1.30 in Example 1. The carboxamide was dimethylaminopropylamide of lauric acid.

The DMAPA was added dropwise to the methyl ester of lauric acid at 190 ° C to 195 ° C for four hours.

Then, it was cured by aging at 190 ° C to 195 ° C for three hours. Serial measurements of the unreacted methyl ester were taken, and it was found that the time for the 99.5% conversion range was 6.1 'hours. The concentration of the solid in the reaction mixture was 90.5% by mass. Then, the reaction mixture was depressurized and capped in the same manner as in Example 1 to recover the product of the reaction. The content of amide ester in the reaction product was analyzed with gas chromatography, and found to be 0.05% per loop.

Example 3. Production of the carboxamide. The carboxamide was produced in the same manner as in Example 1, except that 237 g of lauric acid methyl ester and 310 g of N, N-dimethyl-1,3-propanediamine (DMAPA) were used at a molar ratio of DMAPA to the methyl ester of lauric acid of 1.60 in Example 1. The carboxamide was dimethylaminopropylamide of lauric acid.

The DMAPA was delivered ppr drip to the methyl ester of lauric acid at 190 ° C to 195 ° C for four hours. When the DMAPA was delivered by drip and the reflow range of the unreacted DMAP increased, the heat went down to the latent heat of vaporization of the DMAPA. For the. Therefore, it was not possible to increase the temperature above 170 ° C. Then, the system was cured by aging at 170 ° C for two hours. Serial measurements of unreacted lauric acid methyl ester were taken, and the time to the 99.5% conversion range was found to be 5.3 hours. The concentration of the solid in the reaction mixture was 82.4% by mass. Then, the reaction mixture was depressurized and plugged in the same manner as in Example 1 to recover the product of the reaction. The content of amide ester in the reaction product was analyzed with gas chromatography, and found to be 0.02% by mass.

Example 4. Production of carboxamide. The carboxamide was produced in the same manner as in Example 1, except that 222 g of capric acid methyl ester and 337 g of N, N-dimethyl-1,3-propanediamine (DMAPA) were used at a molar ratio DMAPA to the methyl ester of capric acid of 1.20 in Example 1. The carboxamide was dimethylaminopropylamide of capric acid.

The DMAPA is. delivered by drip to capric acid methyl ester at 190 ° C to 200 ° C for four hours, and - the system was cured by aging for four hours. Serial measurements of unreacted methyl ester were taken, and it was found that the time for the 99.5% conversion range was 6.2 hours. The concentration of the solid in the reaction mixture was 92.8% by mass. Then, the reaction mixture was depressurized and capped-in the same manner as in Example 1 to recover the product of the reaction. The content of amide ester in the reaction product was analyzed with gas chromatography, and found to be 0.15% by mass.

Comparative Example 1. Production of carboxamide. The carboxamide was produced in the same manner as in Example 1, except that 364 g of lauric acid methyl ester and 191 g of N, N-dimethyl-1,3-propanediamine (DMAPA) were used at a molar ratio of DMAPA to the lauric acid methyl ester of 1.10 in Example 1. The carboxamide was dimethylaminopropylamide of lauric acid.

The DMAPA was drip-fed to the methyl ester of lauric acid at 190 ° C to 200 ° C for four hours, and the system was cured by aging at 170 ° C for four hours. Serial measurements of the unreacted methyl ester were taken, and it was found that the time for the 99.5% conversion range was 7.8 hours. The concentration of the solid in the reaction mixture was '96.7% by mass. Then, the reaction mixture was depressurized and capped in the same manner as in Example 1 to recover the product of the reaction. The content of amide ester in the reaction product was analyzed with gas chromatography, and found to be .0.4% by. dough.

Comparative Example 2 Production of carboxamide. The carboxamide was produced in the same manner as in Example 1, except that 293 g of lauric acid methyl ester and 238 g of N, N-dimethyl-1,3-propanediamine (DMAPA) were used at a molar ratio of DMAPA to the lauric acid methyl ester of 1.70 in Example 1. The carboxamide was dimethylaminopropylamide of lauric acid.

The DMAPA was delivered dropwise to the methyl ester of lauric acid for four hours. During this operation, the amount of DMAP unreacted increased, and also increased the reflow range of DMAPA. Since the temperature was brought to the latent heat of vaporization of the DMAPA, the temperature could not be increased above 160 ° C at the end of the delivery of the DMAPA While the system was cured by aging for four hours, serial measurements of the unreacted methyl ester were taken, and the time for the 99.5% conversion range was found to be 6.2 hours. The concentration of the solid in the reaction mixture was 80.1% by mass. Then, the reaction mixture was depressurized and capped in the same manner as in Example 1 to recover the product of the reaction. The content of amide ester in the reaction product was analyzed with gas chromatography, and found to be 0.02% by mass.

The results of the measurements of Examples 1 to 4 and Comparative Examples 1 and 2 are shown in Table 1.

Also for Examples 1 to 4 and Comparative Examples 1 and 2, the productivity of the carboxamide was calculated based on the following equation: productivity (g / (g * h)) = concentration of the solid content (% by mass ) / time required to achieve the conversion rate of 99.5% (h).

Table 1.

In Table 1, DMAPA represents N, N-dimethyl-l, 3-propanediamine.

'The results in Table 1 indicate the . decrease in the amide ester as a by-product as the molar ratio of the diamine "with respect to the fatty acid ester increased, and it was found that carboxamide with low amide ester content could be obtained, ie, from 0.02% by mass to 0.18% In addition, it was found that the carboxamide could be obtained efficiently in Examples 1 to 4 with greater productivity than in the Examples by mass, when the reaction was carried out with a molar ratio of diamine to diamine from 1.20 to 1.60. comparative 1 to 2.

With respect to Comparative Example 2, the amide ester content of 0.02% by mass was observed when the molar ratio of diamine to the fatty acid ester was 1.70. However, unreacted DMAPA, as well as the reflow range of DMAPA, increased in the process of carboxamide synthesis, resulting in significantly lower productivity. Therefore, it was found that the preferable molar ratio was 1.20 to 1.60.

Example 5. Production of carboxamide derivative. In a four-liter jar of 1 liter, equipped with a stirrer, a thermometer and a reflux condenser, 200 g of the dimethylaminopropylamide were charged. lauric acid produced in Example 1 (the molecular weight was calculated based on the amine value of 285, and the amount of 0.18% by mass of amide ester) as carboxamide and 345 g of purified water, so that the Active ingredients accounted for 30% by mass. Then, a The commercial product of 45% by mass of hydrogen peroxide was diluted with purified water to 15.6% by mass, and while the mixture was stirred, 200 g of the prepared hydrogen peroxide (1.05 molar ratio with respect to the amine) at 75 ° C for two hours.

After completing the delivery, the system was cured by aging at 85 ° C for five hours, and a reaction product was obtained which included amide amide oxide as a carboxamide derivative.

. The amount of unreacted lauric acid dimethylaminopropylamide in the obtained reaction product was measured with HPLC based on the following HPLC analysis conditions. It was found that the unreacted carboxamide content was 0.15% by mass. • HPLC analysis conditions. A differential refractometer (Rl) detector and a UV detector were used as detectors, and as a column a Capcell Pak SCX UG80 (4.6 mm diameter x 150 m length, with a film thickness of 5 μm, manufactured by Shiseido, Co., Ltd.). A mobile cell was an aqueous methanol solution with a molar ratio of MeOH to water of 8 to 2, including 0.2% by mass of NaC104 and 0.2% by mass of C1CH2C00H; the temperature of the column was 40 ° C; the flow range was 0.75 mL / min; Y. the injection amount was 10 μL.

The concentration of active ingredient (concentration of amide amide oxide in the reaction product) was also analyzed by means of. Potentiometric titration using a solution of N / 5 hydrochloric acid and 2-propanol and found to be 30.2% by mass. In addition, GC analysis was performed in the same manner as in Example 1 to measure the amine ester at .30% by mass of amide amide oxide, and it was found to be 0.05% by mass.

Example 6. Production of the carboxamide derivative. A reaction product was obtained which included amide amide oxide as a carboxamide derivative in the same manner as in Example 5, except that they were used 200 g of lauric acid dimethylaminopropylamide - produced in Example 3 (calculated molecular weight based on the amine value of 285, and amount of ester is amidated of 0.02% by mass) and that 300 g of purified water and 103 g of 24.3% by mass of hydrogen peroxide were used . in Example 5.

The concentration of the unreacted lauric acid dimethylaminopropylamide in the obtained reaction product was 0.24% by mass. Also the concentration of the active ingredient (concentration of amide amide oxide in the product of the reaction) was 35.3% by mass. In addition, GC analysis was performed in the same manner as in Example 1 to measure the content of amide ester in the 35% solution of amide amide oxide, and it was found to be 0.006% by mass.

Example 7 Production of the carboxamide derivative. A reaction product was obtained which included amide amide oxide as a carboxamide derivative, in the same manner as in Example 5, except that 200 g of the capric acid dimethylaminopropylamide produced in Example 4 was used (calculated molecular weight with base on the amine value of 256, and amount of amide ester of 0.15% by mass) and that 146 g of purified water and 103 g of 24.3% by mass of hydrogen peroxide were used in Example 5.

The concentration of dimethylaminopropylamide of unreacted capric acid in the product of the reaction was 0.26% by mass. Also the concentration - of the active ingredient (concentration of amide amide oxide in the reaction product) was 39.8% by mass.

In addition, a GC analysis was performed in the same way as in • Example 1 for measuring the ester * content of amide in the 40% amide amide oxide solution, and it was found to be 0.04% by mass.

Comparative Example 3. Production of the carboxamide derivative. A reaction product was obtained which included amide amide oxide as a derivative of the carboxamide, in the same manner as in Example 5, except that 200 g of the lauric acid dimethylaminopropylamide produced in Comparative Example 1 was used (weight molecular calculated on the basis of the amine value of .285, and amount of amide ester of 0.0% by mass) and that 345 g of purified water and 200 g of 15.6% by mass of hydrogen peroxide were used in the Example 5.

The concentration of dimethylaminopropylamide of unreacted lauric acid in the obtained reaction product was 0.14% per unit. Also, the concentration of the active ingredient (concentration of amide amide oxide in the product of the reaction) was 30.1% by mass. In addition, GC analysis was performed in the same manner as in Example 1 to measure the content of amide ester in the 40% amide amide oxide solution, and it was found to be 0.11% by mass.

Comparative Example 4. Production of the carboxamide derivative. A reaction product was obtained which included amide amide oxide as a derivative of the carboxamide, in the same manner as in Example 5, except that 100 g of the lauric acid dimethylaminopropylamide produced in Comparative Example 1 was used and that 504 g of purified water and 100 g of 15.6% by mass of hydrogen peroxide were used in Example 5.

The concentration of dimethylaminopropylamide of unreacted lauric acid in the reaction product • obtained was 0.09% by mass. Also, the concentration of the active ingredient (concentration of amide oxide 'amine in the product of the reaction) was 15.1% by mass.

In addition, GC analysis was performed in the same manner as in Example 1 to measure the content of amide ester in the 15% solution of amide amide oxide, and it was found to be 0.06% by mass.

The results of the measurements of Examples 5 to 7 and Comparative Examples 3 to 4 are shown in Table 2.

Also, amide amide oxides produced as a carboxamide derivative in Examples "5 to 7 and Comparative Examples 3 to 4 were preserved at 0 ° C for one week, and stability at low temperature after preservation was evaluated. The appearance of amide amide oxide was visually observed for its transparency, and the stability at low temperature was recorded as "Good" or "NB." The results "are shown in Table 2.

Table 2 The results in Table 2 indicate that the content of the amide ester exceeding 0.05% by mass in an aqueous solution of 15% by mass to 40% by mass of amide amine oxide precipitated the amide ester during preservation at low temperature and clouded the appearance, but that the amide ester content of 0.5% by mass or less resulted in superior stability at low temperature.

Example 8. Production of the carboxamide derivative. In a 1-liter, four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, 150 g of the lauric acid dimethylaminopropylamide produced in Example 1 was charged (the molecular weight was calculated based on the value of amine of 285, and the amount of 0.18% by mass of amide ester) as carboxamide, 399 g of purified water, 66 g of sodium monochloroacetate (manufactured by Kanto Chemical Co., Inc., molecular weight of 116.5) and 2.7 g of 30% by mass of sodium hydroxide (manufactured by Kanto Chemical Co., Inc.) so that the active ingredients accounted for 30% by mass. Then, the system was cured by aging at 85 ° C to 90 ° C for five hours, and a reaction product was obtained which included propyl betaine amide as a carboxamide derivative.

The solids concentration of the obtained reaction product was measured, and it was found to be 35.4% by mass. The sodium chloride content was also measured by means of silver nitrate titration; The concentration of sodium chloride was 5.1% by mass, and the concentration of the active ingredient (concentration - of amide propyl betaine in the product of the reaction) was 30.3% by mass. In addition, the product of the reaction was extracted by the following extraction method with petroleum ether. After evaporating to dryness, the extract was diluted with 2-propanol. Then a GC analysis was performed in the same manner as in Example 1 to measure the content of amide ester in the propyl betaine amide, and it was found to be 0.05% by mass. " Extraction method by petroleum ether. The extraction by petroleum ether was carried out based on the analysis methods according to the standards of the cosmetic ingredients.

First, 10 g of a sample was weighed and dissolved by adding 100 mL of water and 100 L of ethanol. The solution was transferred to a separation hopper, and extracted three times, each with 50 mL of petroleum ether. The petroleum ether extract was combined, and the mixture was washed three times, each with 50 mL of water. Then the petroleum ether was distilled with an evaporator, to obtain an evaporated and dry material.

Comparative Example 5. Production of the carboxamide derivative. A reaction product was obtained which included propyl betaine amide as a carboxamide derivative, performing a reaction in the same manner as in the Example 8, except for 150 g of lauric acid dimethylaminopropylamide which were produced in Comparative Example 1 (molecular weight calculated on the basis of the amine value of 285, and amount of amide ester of 0.40% by mass) as the carboxamide in Example 8.

The concentration of solids of the obtained reaction product was measured, and it was found to be 35.5% by mass. The sodium chloride content was also measured by titration with silver nitrate; the sodium chloride concentration was 5.1% by mass, and the - concentration of the active ingredient (concentration of amide propyl betaine in the product of the reaction) was 30.4% by mass. In addition, the product of the reaction was extracted by means of the petroleum ether extraction method. After evaporating to dryness, the extract was diluted with 2-propanol. Then a GC analysis was performed in the same manner as in Example 1 to measure the content of amide ester in the propyl betaine amide, and it was found to be 0.11% by mass, The results of Example and Comparative Example 5 are shown in Table 3.

The amide propyl betaines as a carboxamide derivative that were produced in Example 8 and Comparative Example 5 were preserved at 0 ° C for one week, and stability at low temperature was evaluated after preservation. The appearance of propyl betaine amide was visually observed for its transparency, and the stability at low temperature was recorded as "Good" or "NB". The results are shown, in Table 3.

Table 2 The results in Table 3 indicate that, when the content of amide ester in the carboxamide was 0.40% by mass, the content of amide ester was 0.11% by mass in the propyl betaine amide produced with the carboxamide, giving as The amide ester precipitation during the preservation at low temperature, but the amide ester content in the carboxamide of. 0.18% by mass can reduce the amide ester content of 0.05% by mass in the propyl betaine amide produced with the carboxamide, resulting in superior stability at low temperature.

Example 9. Composition of kitchen detergent. As a detergent composition with a carboxamide derivative of the present invention, a kitchen detergent composition was prepared by mixing the following: 10% by mass of amide amide oxide produced in Example 5; 15% by mass of sodium lauryl ether sulfate (C? 2AESNa, manufactured by Lion Corp., with average number of moles added of 3); 10% by mass of C? 2 POE alkali ether (manufactured by Lion Corp. with average number of moles added of 15); 5% by mass of C ?2 fatty acid diethanol amide (manufactured by Lion Oleochemical Co., Ltd.); 1% by mass of PEG1000 (manufactured by Lion Chemical Co., Ltd.); 3% by mass of ethanol (manufactured by Kanto Chemical Co., Inc.); 1% by mass of sodium benzoate (manufactured by Kanto Chemical Co., Inc.); and 5% by mass of p-toluene sulfonic acid (manufactured by Kanto Chemical Co., Inc.). The pH of the composition * obtained kitchen detergent was adjusted to 6.6.

Comparative Example 6. Detergent composition for kitchen. As a detergent composition with a carboxamide derivative of the present invention, a kitchen detergent composition was prepared by mixing the following: % by mass of amide amide oxide produced in the Comparative Example 3; 15% by mass of sodium lauryl ether sulfate (Ca2AESNa, manufactured by Lion Corp, with an average number of moles added of 3); 10% by mass of C? 2 POE. Alkali ether (manufactured by Lion Corp. with average number of moles added of 15); 5% by mass of dietanol amide Ci2 of fatty acid (manufactured "by Lion Oleochemical Co., Ltd.); 1% by mass of PEG1000 (manufactured by Lion Chemical Co., Ltd.); 3% by mass of ethanol (manufactured by Kanto Chemical Co., Inc.); 1% by mass of sodium benzoate (manufactured by: Kanto Chemical Co., Inc.); and 5% by mass of p-toluene sulfonic acid (manufactured by Kanto Chemical Co., Inc.). The pH of the obtained kitchen detergent composition was adjusted to 6.6.

The detergent compositions for kitchen Example 9 and Comparative Example 6 were "tested and evaluated for their detergency, their foaming and their stability at low temperature, as follows.The results are shown in Table 4.

Detergency Testing method. A 10 cm x 15 cm Tupper are container was evenly covered with 1 g of beef tallow, and a severely oily, hydrophobic dirt was formed. Then, 38 g of water, as well as 2 g of the kitchen detergent composition of Example 8 or Comparative Example 3 were placed in a 11.5 cm x 7.5 cm x 3 cm dishwashing sponge, and the sponge was squeezed by hand for some time. minutes Then the Tupperware container greased at 25 ° C was cleaned in the same way as it is used in household cleaning. After cleaning, rinsed well with water.

Evaluation method. After cleaning, the greased surface of the Tupperware container was touched with the hand, and a sensory evaluation for touch was performed based on the following criteria.

Evaluation criteria. A: The Tupperware container was completely clean to the chirp, and there was no greasy part due to residual oil. B: the flat surface of the .Tupperware container was completely clean to the chirp and there was no residual oil, but the edges and corners remained slightly greasy. C: The whole Tupperware container was fatty, and it was clear that the oil remained.

Foamed Testing method. In a 11.5 cm x 7.5 cm x 3 cm dishwashing sponge, 38 g of water as well as 2 g of kitchen detergent composition of Example 8 or Comparative Example 3 were placed, and the sponge was hand squeezed for a few minutes.

Evaluation method. The foaming of the detergent composition for the kitchen was visually observed in the dishwashing sponge after having been squeezed by hand, and a sensory evaluation was carried out based on the following criteria.

Evaluation criteria. A: Foam well, with good foam quality B: Some foam C: Strongly foamed Stability at low temperature. Testing method. The kitchen detergent composition of Example 9 and Comparative Example 6 were filled respectively into 100 mL glass bottles. These were frozen by preserving them in a thermostat at -20 ° C for one day, and then they were thawed and 'stored in a thermostat at 0 ° C for one day. This series of operations was considered as a cycle, and this cycle was repeated three times.

Evaluation method.

After the completion of the three cycles, the appearance of each detergent composition for the kitchen was visually observed and a sensory evaluation was carried out based on the following criteria.

Evaluation criteria. A: Uniformly transparent C: turbid or with precipitation.

Table 4 The results in Table 4 indicate that the kitchen detergent composition of Example 9, which includes amide amide oxide produced in Example 5 having low amide ester content, - produced superior detergency, foaming and stability at low temperatures. On the other hand, the kitchen detergent composition of Comparative Example 6, which includes amide amide oxide produced in Example 3, having high amine ester content, produced inferior stability at low temperature.

Example 10. Shampoo for hair. As a detergent composition with a carboxamide derivative of the present invention, a hair detergent composition was prepared by mixing the following: 20% by amine oxide amine oxide produced in Example 5; 10% by mass of sodium lauryl ether sulfate (C? 2AESNa; manufactured by .Lion Corp, with an average number of moles added of 3); 3% by mass of coconut fatty acid diethanolamide (manufactured by Lion Oleochemical Co., Ltd.); 20% by mass of propyl betaine amide of lauryl acid, liquid (manufactured by Lion Corp.); 2.0% by mass of cellulose, cationized (manufactured by Lion Corp.); 2.5% by mass of 5 ethylene glycol distearate > (manufactured by Ipposha Oil Industries Co., Ltd.); and 0.1% by fragrance mass. The pH of the hair shampoo obtained was adjusted to 6.0.

Comparative Example 7. 10. Shampoo for hair. A hair shampoo detergent composition was prepared in the same manner as in Example 10, except that amide amide oxide produced in Comparative Example 3 was used in Example 10. 15 The following test was performed on the shampooes for the hair of Example 10 and Comparative Example 7, and evaluated for foaming quality and low temperature stability. The results are shown in Table 5. 0 Foam quality. The hair shampoos of Example 10 and Comparative Examples were diluted so that the content of surface agent was reduced to 5% by mass, 5 and hair was washed with 5 L of the diluted shampooes.

At this point, sensory evaluations were made for foam quality based on the following criteria.

Evaluation criteria. A: Creamy B: Something creamy C: Not creamy Stability at low temperature. The hair shampoos of Example 10 and Comparative Example 7 were filled respectively into 100 mL glass bottles. These were frozen by preserving them in a thermostat at -20 ° C for one day, and then they were thawed and stored in a thermostat at 0 ° C for one day. This series of operations was considered as a cycle, and this cycle was repeated three times. After the completion of the. three cycles, the appearance of each shampoo was observed visually at 0 ° C, and the sensory evaluation was performed based on the following criteria.

Evaluation criteria. A: Uniformly transparent C: cloudy or with precipitation Table 5 The results in Table 5 indicate that the hair shampoo of Example 10, which included amide amide oxide produced in Example 5, which had 'low amide ester content, produced superior foaming quality and stability at low temperature. On the other hand, the shampoo of Comparative Example 7 which includes the amide amide oxide produced in Comparative Example 3, which has high amide ester content, produced lower stability at low temperature.

Industrial applicability A carboxamide derivative produced using a method for producing a carboxamide derivative of the present invention, and using the carboxamide produced with a production method with a method for producing the carboxamide of the present invention, produces low amide ester content and stability superior at low temperature; therefore, it is favorably used for a detergent composition. Also, a detergent composition including a carboxamide derivative of the present invention has a favorable stability at low temperature and superior detergency and foaming power. Therefore, it can be favorably used for various types of detergents, especially shampoo for hair, body shampoo, face wash, hair treatment, kitchen detergent and various household cleaning detergents.

Claims (8)

1. Method for producing carboxamide, comprising a process for synthesizing the carboxamide, wherein the carboxamide is synthesized by reacting a fatty acid ester represented by the General Formula (1) below with a diamine represented by the General Formula (2) below to a molar ratio of the diamine to the fatty acid ester of 1.20 to 1.60; and the carboxamide comprises 0.02% by mass at 0.18% by mass of the amide ester represented by the General Formula (3) below: Ra-C00R2 General Formula (1) wherein, in the General Formula (1) above, R1 represents any of a straight chain or branched chain alkyl group, an alkenyl group and a hydroxyalkyl group having a carbon number of from five to 23; and R2 represents a straight chain or branched chain alkyl group having a carbon number of one to (2) where, in the General Formula (2) above, R3 and R4 are the same or different and represent an alkyl group having a carbon number of one to four; and n represents an integer from two to four; and '' A .'- A- ÁPP. ,.; "'. .. Q;' -:; ::: S. '•'" ': - - -.:- "X-.":'; - 'S. X.XS: S || pX - '-' "• '' • _ = R ^ -CON.H -; (CH2)? r-0rrCR: .X_- General Formula (3) where, in the General Formula (3) above, R1 and R5 represent any of a straight chain alkyl group Chain, branched, an alkenyl group and a hydroxyalkyl group having a carbon number of five to 2. 3; and n represents an integer from two to four. 2. A method for producing a carboxamide derivative comprising a process for producing a carboxamide derivative represented by the General Formula. (4) below, reacting the carboxamide-produced with the method to produce carboxamide according to the claim 1 and hydrogen peroxide: 'p p-. ::: ^ ',;? • /.; "- -: '' '- -' -i V", P - .- -'P-! A ... p '. "-' S: R ^ CONH- (C.H2) n- N ^? - O General Formula (4):? Y: '; " TO .; R4: • '••.' '• -. . • - wherein, in the General Formula (4), R1 represents any of a straight chain or branched chain alkyl group, an alkenyl group and a hydroxyalkyl group having a carbon number of from five to 23; R3 and R4 are the same or different, representing an alkyl group having a carbon number of one to four; and n represents an integer from two to four. 3. A method for producing a carboxamide derivative comprising a process for producing a carboxamide derivative represented by the general formula (6) below, the carboxamide produced by the method for producing carboxamide according to claim 1 and any of an onoalkylcarboxylic acid represented by Structural Formula (5) below and a salt thereof: YR6COOZ General Formula (5) wherein, in the General Formula (5), Y represents a halogen atom; R6 represents a straight chain or branched chain alkylene group having a carbon number of one to three; and Z represents any of a hydrogen atom and an alkali metal atom; Y to (6) where, in the General Formula (6), R1. represents any of a straight chain or branched chain alkyl group, an alkenyl group and a hydroxyalkyl group having a carbon number of from five to 23; R3 and R4 are the same or different, representing an alkyl group having a. carbon number one to four; and n represents an integer from two to four. 4. Method for producing a carboxamide derivative according to any of claims 2 to 3, wherein the content of amide ester represented by the General Formula (3) below is 0.05% by mass or less: | R ..- - General Formula (3) K-.CONH- (CH2) n-O-CR ~ wherein, in the General Formula (3) above, R1 and R5 represent any of a straight chain or branched chain alkyl group, an alkenyl group. and a hydroxyalkyl group having a carbon number of five to

2. 3; and n represents an integer from two to four. 5. A carboxamide derivative produced by any of the methods for producing a carboxamide derivative according to claims 3 to 4. 6. Carboxamide derivative according to claim 5, wherein the carboxamide derivative is amide amide oxide. 7. A carboxamide derivative according to claim 5, wherein the carboxamide derivative is amide betaine. 8. Detergent composition comprising the carboxamide derivative according to any of claims 5 to 7.