JPH0860183A - Detergent composition for hard surface - Google Patents

Abstract

PURPOSE: To obtain a detergent composition for hard surfaces excellent in detergency and finishing performance, weakly stimulant to skin and containing a specific 2-hydroxypropanediamine derivative, a salt thereof or a quaternary derivative thereof, a metal ion sequestering agent, an alkali agent, a water soluble solvent, etc. CONSTITUTION: This detergent composition excellent in detergency and finishing performance and weakly stimulant to skin comprises 0.1-50wt.% of (A) a 2- hydroxypropanediamine derivative, its salt or a quaternary derivative thereof expressed by formula I [R<1> and R<2> are each a 6-36C alkyl or alkenyl; X is hydroxyl, a 1-6C alkyl or a substituted alkyl with sulfonic acid or carboxyl, or an alkenylene; Y<1> is sulfonic acid residue or sulfuric acid residue, Y<2> is hydroxyl, sulfuric acid residue or carboxyl; Y<2> is hydroxyl, sulfuric acid residue or a group expressed by formula II; (n) is 0 or 1] and 0.01-50wt.% of (B) >=1 agents selected from a metal ion sequestering agent, an alkali agent, a water soluble solvent, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hard surface cleaner composition, and more particularly to a hard surface cleaner composition which is excellent in detergency and finish and has less irritation to the skin.

[0002]

2. Description of the Related Art Conventionally, as a cleaning composition for hard surfaces, the following ones are properly used according to the type and degree of stains. That is to say, for hand stains that are relatively lightly soiled and unmodified oil stains, a surfactant / solvent-based detergent is a fat and oil that has been altered by the effects of heat around the kitchen, sunlight, oxygen in the air, etc. A detergent / solvent / alkaline cleaner is mainly used for dirt and the like.

However, many of these detergents have a problem that they are very irritating to the skin during use. Due to such problems, various detergents for hard surfaces have been developed, which contain a surfactant having a low irritation to the skin.

[0004]

However, these conventional detergents have not been able to sufficiently satisfy both the detergency and the low skin irritation. Therefore, an object of the present invention is to provide a detergent composition for hard surfaces, which has excellent detergency and finish, and is less irritating to the skin.

[0005]

Under such circumstances, the present inventor has conducted diligent studies, and as a result, the 2-hydroxypropanediamine derivative represented by the following general formula (1) was added to a sequestering agent, an alkaline agent or a water-soluble agent. If a solvent is blended, it is found that a cleansing agent having excellent cleaning power for stains on hard surfaces such as kitchens, toilets, bathrooms, etc., good finish, and not irritating to the skin can be obtained, The present invention has been completed.

That is, the present invention provides the following components (A) and (B): (A) the following general formula (1);

[0007]

[Chemical 3]

[In the formula, R ¹ and R ² are the same or different and each represents a linear or branched alkyl or alkenyl group having 6 to 36 carbon atoms, and X is substituted with a hydroxyl group, a sulfonic acid group or a carboxyl group. Optionally represents an alkylene or alkenylene group having 1 to 6 carbon atoms, Y ¹ represents a sulfonic acid group, a sulfuric acid residue or a carboxyl group, Y ² represents a hydroxyl group, a sulfuric acid residue or the following formula (2);

[0009]

[Chemical 4]

A 2-hydroxypropanediamine derivative represented by a group represented by the formula, n is 0 or 1], a salt thereof or a quaternary compound thereof, (B) a sequestering agent, an alkali agent and a water-soluble solvent. 1 or 2 selected from
The present invention provides a hard surface cleaner composition containing one or more species.

2-hydroxy used as component (A)
Cypropanediamine derivative, its salt or its quaternary compound
It is used as a cleaning active ingredient and has the formula (1)
Medium, R ¹And R²A straight chain having 6 to 36 carbon atoms or
Examples of the branched chain alkyl group include hexyl group and heptyl group.
Group, octyl group, nonyl group, decyl group, undecyl group,
Dodecyl group, tridecyl group, tetradecyl group, pentadecyl group
Syl group, hexadecyl group, heptadecyl group, octadecyl
Group, nonadecyl group, eicosyl group, heneicosyl group
Group, docosyl group, tricosyl group, tetracosyl group, etc.
List straight chain alkyl groups and these branched chain alkyl groups
be able to. In addition, a straight or branched chain having 6 to 36 carbon atoms
Examples of the alkenyl group include hexenyl group and heptenyl group.
Group, octenyl group, nonenyl group, decenyl group, dodecenyl
Group, undecenyl group, tridecenyl group, tetradecenyl group
Group, pentadecenyl group, hexadecenyl group, heptade
Cenyl group, octadecenyl group, nonadecenyl group, eico
Cenyl group, heneicosenyl group, docosenyl group, trico
Linear alkenyl groups such as cenyl and tetracocenyl groups
And these branched alkenyl groups.
R¹And R²Among these, carbon numbers of 6 to 2
4 alkyl groups or alkenyl groups, especially 6 to 2 carbon atoms
4 alkyl group is further an alkyl group having 6 to 18 carbon atoms
Is preferred.

Examples of the alkylene or alkenylene group having 1 to 6 carbon atoms represented by X in the formula (1) include methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group and methylethylene. Group, ethylethylene group, ethenylene group, propenylene group, butenylene group, pentenylene group, hexenylene group and the like. Of these, those having 1 to 4 carbon atoms are preferable, those having 1 to 3 carbon atoms are more preferable, and methylene group,
Particularly preferred are ethylene group, trimethylene group and ethenylene group.

A hydroxyl group (-OH), a sulfonic acid group (-SO ₃ H) or a carboxyl group (-COOH) may be substituted on these alkylene or alkenylene groups (provided that X ¹ described later is a hydroxyl group or Carboxyl group may be substituted), but 1 to 4 of these substituents may be substituted singly or in combination of two or more.

The hydroxyl-substituted alkylene or alkenylene group includes 1-hydroxyethylene group, 2-hydroxyethylene group, 1,2-dihydroxyethylene group,
1-hydroxytrimethylene group, 2-hydroxytrimethylene group, 3-hydroxytrimethylene group, 1,2-dihydroxytrimethylene group, 1,3-dihydroxytrimethylene group, 1,2,3-trihydroxytrimethylene group , 1-hydroxytetramethylene group, 2-hydroxytetramethylene group, 3-hydroxytetramethylene group,
4-hydroxytetramethylene group, 1,2-dihydroxytetramethylene group, 1,3-dihydroxytetramethylene group, 1,4-dihydroxytetramethylene group, 2,
3-dihydroxytetramethylene group, 2,4-dihydroxytetramethylene group, 3,4-dihydroxytetramethylene group, 1,2,3-trihydroxytetramethylene group, 2,3,4-trihydroxytetramethylene group,
1,3,4-trihydroxytetramethylene group, 1,
Examples thereof include a 2,3,4-tetrahydroxytetramethylene group, and among these, a 1,2-dihydroxyethylene group, a 1-hydroxyethylene group, a 2-hydroxyethylene group, and a 2-hydroxytrimethylene group are particularly preferable.

The sulfonic acid group-substituted alkylene or alkenylene group includes 1-sulfoethylene group, 2-sulfoethylene group, 1-sulfotrimethylene group, 2-sulfotrimethylene group, 3-sulfotrimethylene group, 1-sulfo group. Tetramethylene group, 2-sulfotetramethylene group, 3-sulfotetramethylene group, 4-sulfotetramethylene group,
Examples thereof include a 1,3-disulfotetramethylene group, a 1,4-disulfotetramethylene group, a 2,3-disulfotetramethylene group and a 2,4-disulfotetramethylene group, and among them, 1- A sulfoethylene group and a 2-sulfoethylene group are particularly preferable.

The alkylene or alkenylene group substituted with a carboxyl group is a 1-carboxyethylene group,
Examples thereof include a 2-carboxyethylene group, a 1-carboxytrimethylene group, a 2-carboxytrimethylene group, a 3-carboxytrimethylene group and a 1-carboxytetramethylene group.

Examples of the alkylene or alkenylene group substituted with a hydroxyl group and a carboxyl group include 2-carboxy-1-hydroxytrimethylene group, 2-carboxy-1,3-dihydroxytrimethylene group and 2-carboxy-2-hydroxytrimethylene group. Examples thereof include a methylene group and a 3-carboxy-2,4-dihydroxytetramethylene group. Among these, 2-carboxy-2-hydroxytrimethylene group is preferable.

Examples of the alkylene or alkenylene group substituted with a hydroxyl group and a sulfonic acid group include 1-hydroxy-2-sulfoethylene group, 2-hydroxy-1-sulfoethylene group, 1-hydroxy-2-sulfotrimethylene group, 1-hydroxy-3-sulfotrimethylene group,
2-hydroxy-1-sulfotrimethylene group, 2-hydroxy-3-sulfotrimethylene group, 1,2-dihydroxy-3-sulfotrimethylene group, 1,3-dihydroxy-2-sulfotrimethylene group, 1- Hydroxy-2-
Examples thereof include a sulfotetramethylene group, a 1-hydroxy-4-sulfotetramethylene group, a 2-hydroxy-4-sulfotetramethylene group and a 3-hydroxy-4-sulfotetramethylene group.

The compound represented by the general formula (1) is
Sulfonic acid group (-SO ₃ H), can form salts between the various basic substances because it has a sulfuric acid residue (-OSO ₃ H) or carboxyl group (-COOH). Examples thereof include alkali metal salts, alkaline earth metal salts, amine salts, basic amino acid salts, ammonium salts and the like. Specifically, sodium, potassium, lithium, magnesium, calcium,
Examples thereof include salts with trimethylamine, triethylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine, lysine, arginine, choline, ammonia and the like, and among these, alkali metal salts, particularly sodium salts are preferable. In addition,
Since the compound (1) has a tertiary amino group, the proton is coordinated on the nitrogen atom of the tertiary amino group, the tertiary amino group becomes an ammonium cation, and a sulfonic acid group, a sulfuric acid residue or The carboxyl group may have a quaternary salt structure in which a sulfonate anion, a sulfate anion or a carboxy anion is formed.

If necessary, the compound (1) can be made into a quaternized compound. Specifically, the compound (1f) in which two nitrogen atoms in the formula (1) are quaternized is used. Can be mentioned.

[0021]

[Chemical 5]

[In the formula, R ³ and R ⁴ are a sulfonic acid group, an alkyl or alkenyl group having 1 to 6 carbon atoms which may be substituted with a carboxyl group or a hydroxyl group, a benzyl group or-(R ⁵ O) _m H (Here, R ⁵ represents an alkylene group having 2 to 4 carbon atoms, and m represents a number of 1 to 50).

Examples of the alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, a carboxyl group or a sulfonic acid group include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and a pentyl group. , Hexyl group, hydroxyethyl group, 1,2-dihydroxypropyl group,
Examples thereof include a carboxymethyl group and a 2-hydroxy-3-sulfopropyl group. Specific examples of the group represented by the group — (R ⁵ O) _m H include a polyoxyethylene group and a polyoxypropylene group, with m = 1 to 20 being preferred. The quaternary compound of the compound (1) has the formula (1)
It can exist when n in is 0.

The compound (1) is produced, for example, according to the following reactions a to c.

[0025]

[Chemical 6]

[Wherein A ¹ and A ² represent a halogen atom, X ¹ represents an alkylene or alkenylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group or a carboxyl group, and Y ³ represents a sulfone. An acid group or a carboxyl group, and R ¹ and R ² are the same as above]

That is, the amine derivative (6) obtained by the reaction of two amines ((3) and (4)) with epihalohydrin (5) is reacted with compound (7) or a salt thereof to give compound (1a). ) Is manufactured.

Reactions of two amines with epihalohydrin are described, for example, in US Pat. No. 3,017,258 or 365.
Follow No. 4158.

The reaction of the amine derivative (6) with the compound (7) or a salt thereof is carried out, for example, in the presence of an inert solvent at 20-15.
The reaction is carried out at 0 ° C., preferably 40 to 100 ° C., by reacting the amine derivative (6) with 1 to 10 times mol, preferably 2 to 5 times mol of the compound (7) or a salt thereof. Here, examples of the halogen atom represented by A ² of the compound (7) include a chlorine atom, a bromine atom and an iodine atom, and among these, a chlorine atom is more preferable. Specific examples of the compound (7) or a salt thereof include sodium chloroacetate, sodium 3-chloro-2-hydroxypropanesulfonate, sodium 3-chloropropionate, and 4
-Chloro-n-butyric acid sodium etc. are mentioned, Of these, sodium chloroacetate and sodium 3-chloro-2-hydroxypropane sulfonate are more preferable. Examples of the inert solvent used herein include polar solvents such as water, methanol, ethanol, isopropanol, dimethylformamide, and dimethylsulfoxide, and these can be used alone or in combination of two or more. However, among them, water, a lower alcohol or a mixed solvent of water and a lower alcohol is preferable.

In this reaction, the amine derivative (6)
On the other hand, when the compound (7) is used in excess, the following quaternary compound (1f ') is produced.

[0031]

[Chemical 7]

[Wherein R ¹ , R ² , X ¹ and Y ³ are the same as above]

After the completion of this reaction, 1 mol of the compound (7) was added to the reaction mixture, in addition to the desired compound (1a), an inorganic salt, unreacted amine derivative (6) and amine derivative (6). The compound and unreacted compound (7) may be contained. In this case, the reaction mixture can be purified by the following method, unless the reaction mixture can be used as it is. As a purification method, for example, a conventional method such as a solvent fractionation method, an ion exchange chromatography method, a recrystallization method or an electrodialysis method can be adopted. The obtained target product may be isolated as a free base, or may be isolated in the form of a desired salt by salt exchange by a usual means such as neutralization with a desired base substance.

[0034]

Embedded image

[In the formula, R ⁶ and R ⁷ are the same or different and each represents an alkyl group or an alkenyl group which may be substituted with a hydrogen atom, a hydroxyl group or a carboxyl group,
Y ² ′ represents a hydroxyl group or a sulfuric acid residue, and R ¹ , R
² and X ¹ are the same as above]

That is, the amine derivative (6) is reacted with the epoxy compound (8), the resulting amino alcohol (9) is reacted with the sulfuric acid esterifying agent (10), and neutralized with a basic substance if desired. , Compound (1b)
Is manufactured.

The reaction between the amine derivative (6) and the epoxy compound (8) is carried out, for example, in an inert solvent, preferably 1
0 to 200 ° C, particularly preferably 130 to 180 ° C,
It is preferably carried out by reacting the amine derivative (6) with the epoxy compound (8) in a molar amount of 2 to 5 times.
The inert solvent used in this reaction is not particularly limited as long as it is an aprotic solvent, but in view of price and solubility, lower hydrocarbons, aromatic hydrocarbons, ethers And halohydrocarbons are preferred.
Further, this reaction is preferably carried out in a pressure resistant vessel such as an autoclave in consideration of the boiling points of the epoxy compound (8) and the inert solvent used. Epoxy compound (8)
As these, ethylene oxide, propylene oxide, and butylene oxide are preferable because they are inexpensive, and ethylene oxide is particularly preferable.

Then, the reaction of the amino alcohol (10) thus obtained with the sulfuric acid esterifying agent (10) such as ClSO ₃ H or SO ₃ is carried out in an inert solvent or without a solvent at -7.
It is preferably carried out in the temperature range of 5 ° C to 150 ° C. ClSO ₃ H
The amount of or SO ₃ used is preferably 1 to 3 times the mol of the amino alcohol (10). In addition, after the completion of this reaction, in a neutralization reaction performed as necessary, a desired amount of sodium hydroxide, potassium hydroxide, or the like depending on the desired degree of neutralization.
Basic substances such as lithium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia, trimethylamine, triethylamine, tributylamine, alkanolamines (monoethanolamine, diethanolamine, triethanolamine, etc.), lysine, arginine, choline, etc., preferably hydroxylated It can be carried out by reacting an alkali metal hydroxide such as sodium or potassium hydroxide.

In the reaction between the amine derivative (6) and the epoxy compound (8) in the above reaction, a small amount of the following formula:

[0040]

[Chemical 9]

In the reaction of the amino alcohol (9) with the sulfuric acid esterifying agent (10), the compound represented by

[0042]

[Chemical 10]

The compound represented by may be produced as a by-product. This reaction product can be used as it is for various uses, but when a higher purity one is required, an ordinary method such as recrystallization, column chromatography,
It can also be used after being purified by distillation or the like.

[0044]

[Chemical 11]

[In the formula, R ⁸ represents a hydrogen atom or an alkyl group which may have a substituent, and R ¹ , R ² , X ¹ and Y ² ′ are the same as the above]

That is, the amine derivative (6) is reacted with a lactone or an oxycarboxylic acid, the resulting amide alcohol (11) is reacted with a sulfuric acid esterifying agent (10), and, if desired, neutralized with a basic substance. To produce compound (1c).

The reaction of the amine derivative (6) with a lactone or an oxycarboxylic acid is carried out, for example, in an inert solvent or without a solvent, preferably 20 to 180 ° C., particularly preferably 4
It is preferable to carry out the reaction by reacting the amine derivative (6) with a lactone or oxycarboxylic acid in a molar amount of 2 to 5 times at 0 to 150 ° C. The inert solvent used in this reaction is not particularly limited as long as it is an aprotic solvent, but in view of price and solubility, lower hydrocarbons, aromatic hydrocarbons, ethers Kind,
Halohydrocarbons and the like are preferable. As the lactones and oxycarboxylic acids used in this reaction, γ-lactone, δ-lactone, glycolic acid, lactic acid, α-hydroxy acid and their methyl esters, ethyl esters and the like are preferable because they are inexpensive.

The amide alcohol (11) thus obtained and a sulfuric acid esterifying agent (10) such as ClSO ₃ H or SO ₃
The reaction with is carried out in an inert solvent or without a solvent at -75 ° C to 1
It is preferably carried out in the temperature range of 50 ° C. The amount of ClSO ₃ H or SO ₃ used is preferably 1 to 3 times the mol of the amide alcohol (11). After the completion of this reaction, the neutralization reaction, which is carried out if necessary, can be carried out in the same manner as in the case of the reaction b.

In the reaction of the amine derivative (6) with lactones or oxycarboxylic acids during the above reaction, a small amount of the following formula;

[0050]

[Chemical 12]

A compound represented by the following formula is formed as a by-product, and in the reaction between the amide alcohol (11) and the sulfuric acid esterifying agent, the following formula:

[0052]

[Chemical 13]

The compound represented by may be produced as a by-product. This reaction product can be used as it is for various uses, but when a higher purity one is required, an ordinary method such as recrystallization, column chromatography,
It can also be used after being purified by distillation or the like.

[0054]

Embedded image

[In the formula, R ⁹ and R ¹⁰ represent a hydrogen atom, an alkyl group or an alkenyl group which may have a substituent, and X ² represents a sulfonic acid which may be substituted by a hydroxyl group or a carboxyl group. 1 to 6 carbon atoms substituted by a group
Represents an alkylene group of Y ² ″ is a hydroxyl group or the following formula (12);

[0056]

[Chemical 15]

And R ¹ , R ² , X and X ¹ are the same as defined above.

That is, the amine derivative (6) is reacted with an acid anhydride, a dicarboxylic acid or an ester thereof, and when an ester is used, it is further hydrolyzed and, if necessary, neutralized with a basic substance to give a compound. (1d) can be produced. Further, when -CH = CH- is present in X ^{1 of} the obtained compound (1d), it is reacted with a sulfonating agent such as SO ₃ , sodium sulfite, sodium hydrogen sulfite and the like, and if necessary, a base. Compound (1e) is produced by neutralizing with a volatile substance.

The reaction between the amine derivative (6) and the acid anhydride can be carried out, for example, in the presence of an anhydrous inert solvent at 20 to 150 ° C.
It is preferably carried out at 40 to 100 ° C. by reacting an amine derivative (6) with a 1.0 to 5.0-fold molar amount of acid anhydride. Examples of the anhydrous inert solvent used here include ether, tetrahydrofuran, benzene, pyridine and the like. In this reaction, the hydroxyl group of the amine derivative (6) reacts with the acid anhydride to obtain a compound in which Y ² ″ is a group represented by the above formula (12) in the formula (1d).

The reaction of the amine derivative (6) with the dicarboxylic acid or its ester can be carried out, for example, in an inert solvent,
It is preferably carried out at 40 to 180 ° C., preferably 80 to 150 ° C., by reacting the amine derivative (6) with a dicarboxylic acid or an ester thereof in a molar amount of preferably 2.0 to 5.0 times. This reaction is preferably carried out while removing the produced alcohol or water. As the inert solvent used in this reaction, hexane, benzene,
Examples thereof include toluene and xylene.

In the dicarboxylic acid ester, examples of the alkyl group or alkenyl group represented by R ⁹ and R ¹⁰ in the formula include those having 1 to 5 carbon atoms, and among these, a methyl group is preferable. , And an ethyl group is preferable.

When the dicarboxylic acid ester is used here, a production intermediate represented by the general formula (14) is obtained, which is then hydrolyzed, for example, in a hydrous alcohol under an acid or base catalyst. It is necessary to disassemble.

[0063]

Embedded image

[In the formula, R ¹¹ and R ¹² represent an alkyl or alkenyl group corresponding to R ⁹ or R ¹⁰ , and R ¹ , R ² and X ¹ are the same as the above]

Next, the reaction of the compound (1d) having —CH═CH— in X ¹ with a sulfonating agent such as SO ₃ , sodium sulfite or sodium hydrogen sulfite is carried out, for example, in water at 30 to 100 ° C. , Preferably 40 to 80 ° C., 1.0 to 6.0 times mol, preferably 2.0 to 5.0 times mol of SO ₃ , sodium sulfite or sodium bisulfite with respect to the compound (1d) at pH 4; It is preferable to carry out the reaction at a rate of 0 to 11.0, preferably 5.0 to 8.0.

The neutralization reaction of the obtained compounds (1d) and (1e) can be carried out in the same manner as in the above reaction b. Further, in these reactions, a compound in which only one amino group is amidated is produced as a by-product as in the case of the reaction b and the reaction c, but the reaction product can be used as it is for various purposes. However, when a higher-purity product is required, it can be purified by a conventional method, for example, recrystallization, column chromatography, electrodialysis, etc., and then used.

In the general formula (1), when n = 0, a quaternizing agent is reacted with this to give a compound (2) in which two nitrogen atoms in the compound (1) are quaternized. 1
f) is obtained. As the quaternizing agent, an alkyl (alkenyl) halide having 1 to 6 carbon atoms, which may be substituted with a sulfonic acid group, a carboxyl group or a hydroxyl group,
Examples thereof include benzyl halide, alkylene oxide or salts thereof. Of these, alkyl halides are more preferable. Here, as the alkyl group, a methyl group, an ethyl group,
Examples thereof include n-propyl group, n-butyl group and isopropyl group, and examples of halogen include chlorine, bromine and iodine. Of these, methyl chloride is particularly preferable.

The amount of the component (A) is not particularly limited, but is usually 0.1 to 5 from the viewpoint of detergency and skin irritation.
0% by weight (hereinafter, simply indicated by%), but 0.01 to
30% is preferable, and 0.03 to 10% is particularly preferable.
Further, it is preferably set to 0.05 to 7%.

As the sequestering agent of the component (B) used in the present invention, any sequestering agent which is usually used can be used and is not particularly limited, but examples thereof include the following. To be

(1) Alkali metal salts or alkanolamine salts of phosphoric acid compounds such as orthophosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, metaphosphoric acid, hexametaphosphoric acid and phytic acid. (2) ethane-1,1-diphosphonic acid, ethane-1,
1,2-triphosphonic acid, ethane-1-hydroxy-
Alkali metal salts of phosphonic acids such as 1,1-diphosphonic acid and its derivatives, ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid and methanehydroxyphosphonic acid Or an alkanolamine salt. (3) 2-phosphonobutane-1,2-dicarboxylic acid, 1
-Phosphonobutane-2,3,4-tricarboxylic acid, α-
Alkali metal salts or alkanolamine salts of phosphonocarboxylic acids such as methylphosphonosuccinic acid. (4) Alkali metal salts or alkanolamine salts of amino acids such as aspartic acid, glutamic acid and glycine. (5) Alkali metal of aminopolyacetic acid such as nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, hydroxyethylenediamineacetic acid, diethylenetriaminepentaacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetraminehexaacetic acid, dienecoric acid Salt or alkanolamine salt. (6) Alkali metals of organic acids such as diglycolic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, citric acid, lactic acid, tartaric acid, oxalic acid, malic acid, oxydisuccinic acid, gluconic acid, carboxymethylsuccinic acid, carboxymethyltartaric acid Salt or alkanolamine salt. (7) Alkali metal salt or alkanolamine salt of aluminosilicate represented by zeolite A. (8) Aminopoly (methylenephosphonic acid) and its alkali metal salt or alkanolamine salt, and polyethylenepolyamine poly (methylenephosphonic acid) and its alkali metal salt or alkanolamine salt.

Particularly, hydroxycarboxylic acid such as citric acid or malic acid, condensed phosphoric acid such as pyrophosphoric acid, aminocarboxylic acid such as ethylenediaminetetraacetic acid or hydroxyethylenediamineacetic acid, or sodium salt thereof,
Alkali metal salts such as potassium salts, ammonium salts, alkanolamine salts and the like and water-soluble salts thereof are preferred. The sequestering agents may be used alone or in admixture of two or more.

The amount of the sequestering agent is not particularly limited, but is usually 0.01 to 50%, preferably 0.5 to 20%, particularly preferably 1 to 20% from the viewpoint of detergency.

As the alkaline agent of the component (B) used in the present invention, amine compounds are preferable, and one or more selected from the amine compounds represented by the following general formulas (15) to (18) are particularly preferable.

[0074]

[Chemical 17]

[Wherein R ¹³ , R ¹⁶ , R ¹⁸ , R ²⁰ , R ²² ,
R ²⁴ and R ²⁵ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁹ , R ²¹ and R ²³ each represent a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. A group or a hydroxyalkyl group having 2 to 3 carbon atoms]

Examples of the compound represented by the general formula (15) include ammonia, monoethanolamine, diethanolamine, N-methylpropanol and the like. Examples of the compound represented by the general formula (16) include N- (β-aminoethyl) ethanolamine. Examples of the compound represented by the general formula (17) include diethylenetriamine. Examples of the compound represented by the general formula (18) include morpholine and N-ethylmorpholine. Among these, monoethanolamine and morpholine are particularly preferable.

The blending amount of the alkaline agent is not particularly limited, but is usually 0.01 to 50% from the viewpoint of detergency, preferably 0.5 to 20%, particularly preferably 1 to 2%.
It is 0%.

The water-soluble solvent of the component (B) used in the present invention is not particularly limited, but those represented by the following general formulas (19) to (22) are preferable.

[0079]

Embedded image

[Wherein R ²⁶ represents a saturated or unsaturated linear or branched alkyl group having 3 to 8 carbon atoms, a phenyl group or a benzyl group, and r and s each represent an integer of 0 to 4] , And 1 ≦ r + s ≦ 4. However, r ×
When s ≠ 0, the added ethylene oxide group and propylene oxide group are arranged arbitrarily]

Specific examples of the solvent represented by the general formula (18) include diethylene glycol monobutyl ether,
Propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, di- (propylene ethylene glycol) -monobutyl ether, phenyl glycol, phenyl diglycol, benzyl glycol, benzyl diglycol and the like can be mentioned. These are 1
One kind may be used, or two or more kinds may be mixed and used.

[0082]

[Chemical 19]

[In the formula, R ²⁷ and R ²⁸ represent the same or different alkyl groups having 1 to 6 carbon atoms]

Specific examples thereof include 1,8-dimethyl-2-imidazolidinone and 1,3-diethyl-2-imidazolidinone as preferable ones.

[0085]

Embedded image

[In the formula, R ²⁹ represents an alkyl group having 1 to 6 carbon atoms]

Specific examples of these include 3-methoxy-
3-Methylbutanol and 3-ethoxy-3-methylbutanol are preferred.

[0088]

[Chemical 21] HO-R ³⁰ -OH (22)

[In the formula, R ³⁰ represents a hydrocarbon group having 4 to 12 carbon atoms]

Specific examples of these include 3-methyl-
1,3-butanediol, 2,2,4-trimethyl-
Preferred examples include 1,3-pentanediol, 2-ethyl-1,3-hexanediol, 1,9-nonanediol, and 1,8-octanediol. These may be used alone or in combination of two or more.

The blending amount of the water-soluble solvent is not particularly limited, but is usually 0.1 to 50% from the viewpoint of detergency, preferably 0.5 to 20%, particularly preferably 1 to 20%. .

When the component (B) is added to the component (A),
The optimum combination differs depending on the type and degree of dirt on the hard surface to be cleaned. For example, for relatively mild stains on hands, unmodified grease stains, etc., component (A)
A detergent composition in which a water-soluble solvent is added as the component (B) is excellent in detergency and finish. For oil stains and the like that have deteriorated due to the action of heat, sunlight, oxygen in the air, etc. around the kitchen, a detergent composition containing an alkaline agent in the component (A) is effective in terms of detergency and finish. It is excellent, and it is more effective if it further contains a water-soluble solvent. Dirt in the toilet bowl around the toilet, metal soap in the bathroom,
Especially for fatty acid calcium stains, etc., component (A)
The detergent composition in which the sequestering agent is blended with is excellent in detergency, and it is more effective if a water-soluble solvent is further blended. For stains in the toilet bowl around the toilet, metal soap in the bathroom, especially fatty acid calcium stains, the detergent composition containing the component (A) with a sequestering agent is superior in terms of detergency. Further, it is effective to add a water-soluble solvent.

The hard surface cleaner composition of the present invention may contain, if necessary, within a range not impairing the effects of the present invention.
Surfactants other than the above can be added. Such a surfactant is not particularly limited, but is selected from the group consisting of nonionic, anionic and amphoteric surfactants.
One kind or two or more kinds is preferable. Specifically, the following are mentioned.

Examples of the anionic surfactant include alkylbenzene sulfonates, alkylene oxide-added alkyl or alkenyl ether sulfates, alkyl or alkenyl sulfates, olefin sulfonates, alkane sulfonates, fatty acid salts, alkylene oxide-added alkyls. Or alkenyl ether carboxylates, α
-Sulfo fatty acid salts and esters thereof, diphenyl ether disulfonic acids and the like. Examples of the counterion of the anionic surfactant include alkali metals such as sodium and potassium, ammonium salts, and alkanol-substituted ammonium salts such as monoethanolammonium, diethanolammonium, and triethanolammonium.

Examples of the nonionic surfactant include polyoxyalkylene alkyl or alkenyl ethers, polyoxyalkylene alkylphenyl ethers, sucrose fatty acid esters, fatty acid glycerin esters, amine oxides, higher fatty acid alkanolamides or the like. Examples thereof include alkylene oxide adducts and alkyl glycosides represented by the following general formula (23).

[0096]

[Chemical Formula 22] R ³¹ (OR ³² ) _t G _u (23)

[Wherein R ³¹ represents a linear or branched alkyl group, alkenyl group or alkylphenyl group having 8 to 18 carbon atoms, R ³² represents an alkylene group having 2 to 4 carbon atoms, and G represents A residue derived from a reducing sugar having 5 to 6 carbon atoms, t represents a number having an average value of 0 to 5, and u represents a number having an average value of 1 to 10]

In the general formula (23), t has an average value of 0 to
The value of 5 controls the water solubility and crystallinity of the composition of the present invention. That is, the higher t, the higher the water solubility and the lower the crystallinity. The preferred value of t is 0
2 and particularly preferably 0. On the other hand, when the average value of u is greater than 1, that is, when it contains a surfactant represented by the general formula (23) having a sugar chain of two or more sugars as a hydrophilic group, the binding mode of the sugar chain is 1 -2, 1-3, 1-
It is possible to include 4,1-6 bonds, as well as α-, β-pyranoside or furanoside bonds and any mixtures thereof having mixed binding modes. The average value of u in the general formula (23) is 1 to 10, preferably 1 to
3, and more preferably 1 to 1.5, and even more preferably the average value is 1.1 to 1.4. The measurement method of y is based on the proton NMR method.

R ³¹ in the general formula (23) has 8 carbon atoms.
It is an alkyl group, an alkenyl group, or an alkylphenyl group having a linear or branched chain of 18 carbon atoms, but from the viewpoint of improving the solubility, foaming property and detergency, it is preferably 10 to 1 carbon atoms.
4 alkyl group. R ³² is an alkylene group having 2 to 4 carbon atoms, and preferably 2 to 3 carbon atoms from the viewpoint of water solubility. Further, the structure of G is determined by a monosaccharide or a raw material of two or more sugars. As the raw material of G, glucose, fructose, galactose, xylose, mannose, lyxose, arabinose and the like, and mixtures thereof, etc. For 2 sugars or more, maltose, xylobiose, isomaltose, cellobiose,
Examples thereof include gentibiose, lactose, sucrose, nigerose, turanose, raffinose, gentianose, melezitose and the like, and mixtures thereof. Among these, preferred monosaccharide raw materials are glucose and fructose from the viewpoints of their availability and cost, and maltose and sucrose for two or more sugars. Among these, glucose is particularly preferable from the viewpoint of easy availability. Furthermore, 1 mol adduct of pentaerythritol isostearyl glycidyl ether, 1 mol adduct of sorbitol isostearyl glycidyl ether, 1 mol adduct of mannitol 2-octyldodecyl glycidyl ether, 1 mol of methylglucoside isostearyl glycidyl ether. Nonionic interface having at least one long-chain branched alkyl group or alkenyl group and at least three hydroxyl groups in one molecule such as a mole adduct, a 1 mole adduct of diglycerin / isostearyl glycidyl ether, and phytantriol. Activators may be mentioned.

Examples of the amphoteric surfactant include, for example, 1 carbon atom.
And sulfobetaine and carbobetaine having a linear or branched alkyl group or alkenyl group of -22.

In the present invention, among these surfactants, diphenyl ether disulfonic acids, higher fatty acid alkanol amides or their alkylene oxide adducts, amine oxides, alkyl glycosides, among these surfactants, from the viewpoint of improving detergency or wiping property. , Sulfobetaines or carbobetaines are preferred, and among these, diphenyl ether disulfonic acids and alkyl glycosides are particularly preferred.

The blending amount of these surfactants in the composition is 0.01 to 20%, preferably 0.0
5 to 10%, particularly preferably 0.05 to 5%. If the content of the surfactant is less than 0.01%, it is meaningless to fully exhibit the surface activity, and if it exceeds 20%, no further effect is expected.
% Is not required.

The detergent composition for hard surfaces of the present invention comprises, in addition to the above-mentioned components, other conventional dispersants, fragrances, dyes, and, if necessary, further improved storage stability of the system at low temperatures.
Pigments, preservatives and the like can be added within a range that does not impair the effects of the present invention.

The detergent composition for hard surfaces of the present invention can be produced by mixing the above components and water by a conventional method.

[0105]

The present invention will be further described with reference to examples, but the present invention is not limited to these examples.
Prior to the description of the examples, the component (A) used in each example
A synthesis example of will be described.

Synthesis Example 1 Bis- (1,3-decylamino) propane-in a reaction vessel
2-Ol 40.2g (0.108mol), ethanol 260g, and water 100g were put, and it heated up at 50 degreeC. To this, 50.3 g of sodium monochloroacetate (0.432
Was added to a solution of 100 g of ethanol in 70 g of water, and the mixture was reacted under reflux for 20 hours while maintaining the pH at 8 to 10 with an aqueous sodium hydroxide solution. After completion of the reaction, the solvent was distilled off and the residue was dissolved in chloroform to remove insoluble unreacted sodium monochloroacetate and by-produced salts such as sodium chloride. This was followed by silica gel column chromatography purification by thin layer chromatography to give a single spot, 2,6-didecyl-4-hydroxy-2,6-diaza-1,7-heptanedicarboxylic acid 2
3 g was obtained as a white powder (isolated yield 44%).

This product was analyzed by HPLC (column: RP-1
8 (manufactured by Merck), eluent methanol / H ₂ O = 80 /
A single peak was given in 20 measurements. Below ¹ H-
The NMR data is shown.

[0108]

[Chemical formula 23]

Synthesis Example 2 40 g (0.13 mol) of bis- (1,3-octylamino) propan-2-ol and 15 ethanol in a reaction vessel.
0 g and 70 g of water were added and the temperature was raised to 50 ° C. Add 52 g (0.44 mol) of sodium monochloroacetate to 100 g.
Of ethanol and 70 g of water dissolved in water,
The reaction was carried out for 26 hours under reflux while maintaining the pH at 8 to 10 with an aqueous sodium hydroxide solution. After completion of the reaction, the solvent was distilled off,
It was dissolved in chloroform and insoluble unreacted sodium monochloroacetate and by-produced salts such as sodium chloride were removed. This was followed by silica gel column chromatography purification by thin layer chromatography to give a single spot, 2,6-dioctyl-4-hydroxy-
19 g of 2,6-diaza-1,7-heptanedicarboxylic acid
(Isolated yield 34%) was obtained as a white powder.

This product was analyzed by HPLC (column: RP-1
8 (manufactured by Merck), eluent methanol / H ₂ O = 80 /
A single peak was given in 20 measurements. Below ¹ H-
The NMR data is shown.

[0111]

[Chemical formula 24]

Synthesis Example 3 Bis- (1,3-decylamino) propane-in a reaction vessel
2-Ol 31.8g (0.086mol), ethanol 244g, and water 51g were put, and it heated up at 75 degreeC. To this, a solution of 76.7 g (0.390 mol) of sodium 3-chloro-2-hydroxypropane-1-sulfonate dissolved in 361 g of water was added, and a sodium hydroxide aqueous solution was added.
The temperature was maintained at 75 ° C for 20 hours while maintaining the pH at 8-10. After completion of the reaction, the solvent was distilled off under reduced pressure, crystallized from water-ethanol, washed with acetone, desalted by electrodialysis, and freeze-dried to give 4,8-didecyl-.
2,6,10-trihydroxy-4,8-diaza-1,
37.3 g of 11-undecanedisulfonic acid (0.057
Mol) was obtained as a white powder.

This product was analyzed by HPLC (column: RP-1
8 (manufactured by Merck); eluent; methanol / water = 80 /
A single peak was given in 20 measurements. ¹ H below
-NMR data (where a-i represents the site in the following chemical formula that gives each signal).

[0114]

[Chemical 25]

Synthesis Example 4 Preparation of 3,7-didodecyl-3,7-diaza-1,5,9-nonanetriol: In an autoclave having a volume of 1 liter, 50.2 g (0) of 15-hydroxy-13,17-diazanononacosan. (0.12 mol) and 500 ml of xylene were added and the temperature was raised to 155 ° C. Ethylene oxide 2
2 g (0.5 mol) was injected and the mixture was kept at 155 ° C. for 6 hours for reaction. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain 60 g (yield 99%) of the title compound as a viscous liquid.

Mass spectrometry (FAB ionization method) m / z = 515 (M + H) + (M = C ₃₁ H ₆₆ O
₃ N ₂ ), ¹ H-NMR (CDCl ₃ ): δ (ppm), 0.85 (triplet line, 6H, a), 1.21 (wide singlet line, 36H, b), 1.45 (pentuplet) Line, 4H, c), 2.41-2.70 (complex multiline, 12H, de.
g), 3.57 (triplet line, 4H, h), 3.75 (quintet line, 1H, f),

[0117]

[Chemical formula 26]

Synthesis Example 5 Preparation of 3,7-didodecyl-5-hydroxy-3,7-diaza-1,9-nonanedisulfate: 3,7-didodecyl-3,7 obtained in Synthesis Example 4 in a reaction vessel. -Diaza-
18 g (0.035 mol) of 1,5,9-nonanetriol and 135 ml of dichloromethane were added, and under a nitrogen stream,
While cooling with ice, 5.1 ml (0.077 mol) of chlorosulfonic acid was added dropwise. Then, the temperature was gradually returned to room temperature, and hydrochloric acid and dichloromethane generated using nitrogen were removed. N-Butanol was added to the residue to dissolve it, washed with water, and then the solvent was distilled off under reduced pressure to obtain 24.8 g of a solid. Next, this solid is dissolved in water and 1N sodium hydroxide aqueous solution is used.
The pH was adjusted to 7. After that, desalting was carried out by a desalting apparatus (Micro Acylyzer G3, manufactured by Asahi Kasei Co., Ltd.), and further dried by a freeze dryer to obtain 17.2 g (yield 85
%) As a white powder.

It was confirmed by thin layer chromatography (developing solvent: chloroform / methanol = 3/1) that this compound had a single spot (Rf = 0.5). A ¹ H-NMR (solvent: CDCl ₃ ) chart of this compound is shown in FIG. Furthermore, the IR spectrum of this compound was as follows.

IR (KBr tablet method, cm ^-1 ): 3600-
3200 (νO-H), 1390, 1192 (νS = O).

Synthesis Example 6 Sodium 3,7-didodecyl-3,7-diaza-1,
Preparation of 5,9-nonanetrisulfate: 3,7-didodecyl-3,7-diaza-obtained in Synthesis Example 4 was placed in a reaction vessel.
18 g (0.035 mol) of 1,5,9-nonanetriol and 150 ml of dichloromethane were added, and under a nitrogen stream.
While cooling with ice, 7.7 ml (0.115 mol) of chlorosulfonic acid was added dropwise. Then, the temperature was gradually returned to room temperature, and hydrochloric acid and dichloromethane generated using nitrogen were removed. Water was added to the residue to dissolve it, and the pH was adjusted to 7 with a 1N aqueous sodium hydroxide solution. After that, desalting was performed using a desalting device (Micro Acylyzer G3, manufactured by Asahi Kasei Co., Ltd.), and the desalting was further dried using a freeze dryer to obtain 26.7 g of the title compound
(Yield 97%) was obtained as a white powder.

As a result of measurement by thin layer chromatography (developing solvent: chloroform / methanol = 1/1), this compound was confirmed to be a single spot (Rf = 0.3). In addition, ¹ H-NMR of this compound (solvent: D ₂
O) chart is shown in FIG. Furthermore, the IR spectrum of this compound was as follows.

IR (KBr tablet method, cm ^-1 ): 1390,
1186 (νS = O)

Synthesis Example 7 Preparation of 5,9-didodecyl-4,10-dioxo-5,9-diaza-1,7,13-tridecanetriol: 15-hydroxy-13,17-diazanonacosane 9 was placed in a reaction vessel. 0.5 g (0.02 mol) and γ-butyrolactone 11.7 g (0.13 mol) were added, the temperature was raised to 160 ° C., and the temperature was maintained for 5 hours for reaction. After completion of the reaction, column chromatography (silica gel 500 g,
Purification with a developing solvent: chloroform / methanol = 97/3) gave 6 g (yield 45%) of the title compound as a viscous liquid.

Mass spectrometry (FAB ionization method) m / z = 600 (M + H) + (M = C ₃₅ H ₇₀ O ₅ N ₂ ) ¹ H-NMR (CDCl ₃ ): δ (ppm) 0.87 (triplet line) , 6H, a), 1.23 (wide singlet, 36H, b), 1.53 (quintet, 4H, c), 1.85 (quintet, 4H, h), 2.40-2. .52 (wide line, 4H, g), 3.28 to 3.40 (wide line, 8H, de), 3.65 (triple line, 4H, i), 4.03 (wide line) , 1H, f)

[0126]

[Chemical 27]

Synthesis Example 8 Disodium 5,9-didodecyl-7-hydroxy-
Production of 4,10-dioxo-5,9-diaza-1,13-tridecanedisulfate: 5,9-didodecyl-4,10-dioxo-5,9-obtained in Synthesis Example 7 in a reaction vessel
Diaza-1,7,13-tridecanetriol 6g
(0.01 mol), pyridine 4.5 g (0.06 mol)
And 50 ml of dichloromethane were added thereto, and 3 ml (0.02 mol) of chlorosulfonic acid was added dropwise while cooling with ice under a nitrogen stream. Then, 0-5 degreeC was maintained and stirring was continued for 4 hours.
After completion of the reaction, it was treated with 11 g (0.06 mol) of sodium methylate (28% methanol solution). next,
The solvent was distilled off under reduced pressure, the residue was dissolved in water, and desalted by electrodialysis. By freeze-drying this aqueous solution, 3.3 g (41% yield) of the title compound was obtained as a white powder.

As a result of measurement by thin layer chromatography (developing solvent: chloroform / methanol = 2/1), this compound was confirmed to be a single spot (Rf = 0.3). In addition, ¹ H-NMR of this compound (solvent: C
The DCl ₃ ) chart is shown in FIG. Furthermore, the IR spectrum of this compound was as follows.

IR (KBr tablet method, cm ^-1 ): 3620
~ 3300 (νO-H), 1690, (νC = O), 139
2,1188 (νS = O)

Synthesis Example 9 Preparation of 3,7-didodecyl-2,8-dioxo-3,7-diaza-1,5,9-nonanetriol: 15-hydroxy-13,17-diazanononacosane 1 in a reaction vessel
Add 0.7 g (0.03 mol), 50 ml of toluene and 7.1 ml (0.07 mol) of ethyl glycolate, and add 100
The temperature was raised to 0 ° C., and stirring was continued for 7.5 hours while driving out the ethanol produced by the nitrogen stream. After the reaction was completed, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (silica gel 200 g, developing solvent: chloroform / methanol = 100/1) to give 13 g of the title compound.
(96% yield) was obtained as a viscous liquid.

Mass spectrometry (FAB ionization method) m / z = 543 (M + H) + (M = C ₃₁ H ₆₂ O ₅ N ₂ ) ¹ H-NMR (CDCl ₃ ): δ (ppm) 0.82 (triplet line) , 6H, a), 1.28 (wide singlet, 36H, b), 1.49 to 1.60 (wide multiplet, 4H, c), 3.18 (triplet, 4H, d), 3.
48 (multiple lines, 4H, e), 4.05 (wide multiple lines,
1H, f), 4.20 (single line, 4H, g)

[0132]

[Chemical 28]

Synthesis Example 10 Disodium 3,7-didodecyl-5-hydroxy-
Preparation of 2,8-dioxo-3,7-diaza-1,9-nonanedisulfate: 3,7 obtained in Synthesis Example 9 in a reaction vessel
-Didodecyl-2,8-dioxo-3,7-diaza-
10.8 g (0.02 mol) of 1,5,9-nonanetriol and 50 ml of dichloromethane were added, and 2 ml of 3 ml (0.04 mol) of chlorosulfonic acid was added while cooling with ice under a nitrogen stream.
It was added dropwise over 0 minutes. Then, the temperature was gradually returned to room temperature, and hydrochloric acid and dichloromethane generated by a nitrogen stream were removed. Water was added to the residue to dissolve it, and the pH was adjusted to 7 with a 1N aqueous sodium hydroxide solution. The aqueous solution was desalted by electrodialysis and then freeze-dried to obtain 11.8 g (yield 79%) of the title compound as a white powder.

As a result of measurement by thin layer chromatography (developing solvent: chloroform / methanol = 3/1), this compound was confirmed to be a single spot (Rf = 0.2). In addition, ¹ H-NMR of this compound (solvent: D ₂
O) chart is shown in FIG. Furthermore, the IR spectrum of this compound was as follows.

IR (KBr tablet method, cm ^-1 ): 3600
~ 3200 (νO-H), 1658 (νC = O), 138
5, 1195 (νS = O)

Synthesis Example 11 Preparation of trisodium 3,7-didodecyl-2,8-dioxo-3,7-diaza-1,5,9-nonanetrisulfate: 3,7 obtained in Synthesis Example 9 in a reaction vessel. -Didodecyl-2,8-dioxo-3,7-diaza-1,5,9-
28 g (0.05 mol) of nonanetriol and 100 ml of dichloromethane were added, and 11 ml (0.16 mol) of chlorosulfonic acid was added dropwise while cooling with ice under a nitrogen stream. Then, the temperature was gradually returned to room temperature, and hydrochloric acid and dichloromethane generated by a nitrogen stream were removed. Water was added to the residue to dissolve it, and the pH was adjusted to 7 with a 1N aqueous sodium hydroxide solution. This aqueous solution was desalted by electrodialysis and then freeze-dried to give 28 g of the title compound (yield: 66
%) As a white powder.

As a result of measurement by thin layer chromatography (developing solvent: chloroform / methanol = 1/1), this compound was confirmed to be a single spot (Rf = 0.3). In addition, ¹ H-NMR of this compound (solvent: D ₂
O) chart is shown in FIG. Furthermore, the IR spectrum of this compound was as follows.

IR (KBr tablet method, cm ⁻¹ ): 139
0, 1185 (νS = O), 1660 (νC = O).

Synthesis Example 12 Bis- (1,3-decylamino) propan-2-ol 22.2 g (0.06 mol), succinic anhydride 13.2 g (0.12 mol) and anhydrous ether 300 were placed in a reaction vessel.
ml was added and refluxed for 5 hours. After completion of the reaction, ether was distilled off under reduced pressure to give 4,8-didecyl-3,9-
Dioxo-6-hydroxy-4,8-diaza-1,11
34 g (0.06 mol) of undecanedicarboxylic acid were obtained as a glassy solid.

The compound was adjusted to pH 10 with sodium hydroxide.
The ones adjusted to (column: R
P-18 (Merck), eluent methanol / water = 8
A single peak was given in the 0/20 measurement. Below, ¹
1H-NMR data are shown.

¹ H-NMR (CDCl ₃ ): δ (ppm)
TMS standard 0.88 (triple line, 6H, a), 1.26 (wide singlet, 28H, b), 1.47 (wide singlet, 4H,
c), 2.64 (complex multiline, 8H, gh), 3.
3 to 3.9 (complex multi-line, 9H, df)

[0142]

[Chemical 29]

Synthesis Example 13 Bis- (1,3-decylamino) propan-2-ol 17.04 g (0.04 mol), maleic anhydride 7.8 g (0.08 mol) and anhydrous ether 20 were placed in a reaction vessel.
0 ml was added and the mixture was refluxed for 3 hours. After completion of the reaction, ether was distilled off under reduced pressure to obtain 25 g (0,0) of 4,8-didodecyl-3,9-dioxo-6-hydroxy-4,8-diaza-1,10-undecene-1,11-dicarboxylic acid. 0.04 mol) was obtained as a glassy solid.

The compound of the present invention adjusted to pH 7 with sodium hydroxide was used in HPLC measurement (column: RP
-18 (Merck), eluent methanol / water = 75
A single peak was given in the / 25 measurement. Below, ¹ H
-Indicates NMR data.

¹ H-NMR (CDCl ₃ ): δ (ppm)
TMS standard 0.89 (triple line, 6H, a), 1.27 (wide singlet, 36H, b), 1.56 (wide singlet, 4H,
c), 3.25-3.58 (complex multiline, 8H, d.
e), 3.8-3.95 (complex multiline, 1H, f),
6.1 to 6.65 (complex multi-line, 4H, gh)

[0146]

Embedded image

Synthesis Example 14 10.65 g (0.025 mol) of bis- (1,3-dodecylamino) propan-2-ol, 100 ml of toluene and 17.1 ml (0.1 mol) of diethyl tartrate were placed in a reaction vessel. The reaction was carried out at 80 ° C. for 20 hours while removing generated ethanol. After completion of the reaction, excess diethyl tartrate was removed by washing with water, and the toluene layer was dried over anhydrous sodium sulfate. Then, by drying under reduced pressure, 4,8-didodecyl-3,9-dioxo-1,2,6,10,11-pentahydroxy-4,8
-Ethyl diaza-1,11-undecane dicarboxylate 1
8 g (0.024 mol) (97%) were obtained as a viscous liquid. The ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ ): δ (ppm)
TMS standard 0.89 (triple line, 6H, a), 1.2-1.3 (complex multiplex line, 42H, bj), 1.63 (wide singlet, 4H, c), 3.52 (Wide singlet, 8H, d.
e), 3.7-4.1 (complex multiline, 5H, i.
f), 4.6-4.85 (complex multiline, 4H, g.
h)

[0149]

[Chemical 31]

Synthesis Example 15 4,8-Didodecyl-3,9-dioxo-1,2,6,10,11-pentahydroxy-4, obtained in Synthesis Example 14
Ethyl 8-diaza-1,11-undecanedicarboxylate was dissolved in 50 ml of water-ethanol (1: 1), 2 g (0.05 mol) of sodium hydroxide was added, and the mixture was added at 10 ° C at 10 ° C.
Stir for hours. After completion of the reaction, ethanol in the mixed solution was distilled off under reduced pressure, and the aqueous solution was freeze-dried to give 4,8
-Didodecyl-3,9-dioxo-1,2,6,10,
11-pentahydroxy-4,8-diaza-1,11-
Sodium undecanedicarboxylate (quantitative) was obtained as a white powder.

This compound had an IR spectrum (KBr tablet method) of 3000-3700 cm ^-1 (νO-H), 1
Absorption was observed at 500-1800 cm ^-1 (νC = O).

Synthesis Example 16 12.78 g (0.03 mol) of bis- (1,3-dodecylamino) propan-2-ol, 100 ml of toluene and 30 ml (0.12 mol) of triethyl citrate were placed in a reaction vessel, The reaction was carried out at 100 ° C. for 25 hours while removing generated ethanol. After completion of the reaction, toluene was distilled off under reduced pressure, the residue was purified by silica gel column chromatography, and 5,9-didodecyl-4,10-
25 g (0.028 mol) of ethyl dioxo-2,7,12-trihydroxy-5,9-diaza-1,2,12,13-tridecanetetracarboxylate was obtained as a white powder. The ¹ H-NMR data is shown below.

¹ H-NMR (CDCl ₃ ): δ (pp
m) TMS standard 0.9 (triple line, 6H, a), 1.3 (complex multiplex line,
48H, b. j), 1.65 (wide singlet, 4H,
c), 2.7-2.9 (complex multiline, 8H, g.
h), 3.45 (wide singlet, 8H, de), 3.
85-4.3 (complex multi-line, 9H, if)

[0154]

[Chemical 32]

Synthesis Example 17 5,9-didodecyl-4,10-dioxo-2,7,12-trihydroxy-5,9-diaza-1,2,12,13-tridecanetetra obtained in Synthesis Example 16 22 g (0.025 mol) of ethyl carboxylate was added to water-ethanol (1:
1) Dissolve in 50 ml and 2 g of sodium hydroxide (0.05
Mol) was added and the mixture was stirred at 60 ° C. for 5 hours. After completion of the reaction, ethanol in the mixed solution was distilled off under reduced pressure, 2 g of sodium hydroxide was further added to the aqueous solution, and freeze-dried to give 5,9-didodecyl-4,10-dioxo-2,
7,12-trihydroxy-5,9-diaza-1,2,
Sodium 12,13-tridecanetetracarboxylate (quantitative) was obtained as a white powder.

This compound had an IR spectrum (KBr tablet method) of 3000-3700 cm ^-1 (νO-H), 1
Absorption was observed at 500-1800 cm ^-1 (νC = O).

Synthesis Example 18 4,8-didodecyl-obtained in Synthesis Example 13 was placed in a reaction vessel.
3,9-dioxo-6-hydroxy-4,8-diaza-
1,10-undecene-1,11-dicarboxylic acid 21.
8 g (0.035 mol) and sodium sulfite 9.7 g
70 ml of an aqueous solution of (0.077 mol) was added, the pH of the reaction mixture was maintained at 5 to 6, and the mixture was stirred at 60 ° C. for 2 hours. After completion of the reaction, the reaction solution was adjusted to pH 7 with a 1N aqueous sodium hydroxide solution, and excess sodium sulfite was removed by electrodialysis. Then, it is freeze-dried and 4,8-didodecyl-
30 g of sodium 3,9-dioxo-6-hydroxy-1,11-dicarboxy-4,8-diaza-1,11-undecanedisulfonate was obtained as a white powder. The following formula obtained by treating this compound with 1N hydrochloric acid

[0158]

[Chemical 33]

4,8-didodecyl-3,9-
Dioxo-6-hydroxy-1,11-dicarboxy-
4,8-diaza-1,11-undecanedisulfonic acid showed m / z = 7 as a result of mass spectrometry (FAB ionization method).
A peak of 83 (M + H) was shown. Also, ¹ H-N
The results of MR are as follows.

¹ H-NMR (CDCl ₃ ): δ (pp
m) TMS standard 0.88 (triple line, 6H, a), 1.26 (wide singlet, 36H, b), 1.54 (wide singlet, 4H,
c), 2.74 (complex multiline, 2H, g), 3.25.
~ 3.9 (complex multi-line, 11H, d.e.f.h)

Synthesis Example 19 20 g (0.058 mol) of 9-hydroxy-7,11-diaza-tricosane and 13 g of succinic anhydride were placed in a reaction vessel.
(0.130 mol) and 300 ml of anhydrous ether,
Refluxed for 5 hours. After completion of the reaction, insoluble excess succinic anhydride was removed by filtration, and the ether layer was washed with water. The ether was distilled off under reduced pressure to give a viscous transparent liquid of 4-dodecyl-8-hexyl-3,9-dioxo-6-hydroxy-4,8-diaza-1,11-undecanedicarboxylic acid 30 g ( 0.055 mol) was obtained.

The compound was adjusted to pH 10 with sodium hydroxide.
The ones adjusted to (column: R
P-18 (manufactured by Merck), eluent methanol / water = 8
A single peak was given in the 0/20 measurement. ¹ H below
-Indicates NMR data.

¹ H-NMR (CDCl ₃ ): δ (pp
m) TMS standard 0.89 (triple line, 6H, a), 1.26 (wide singlet, 24H, b), 1.43 (wide singlet, 4H,
c), 2.60 (complex multiline, 8H, gh), 3.
29-3.87 (complex multi-line, 9H, df)

[0164]

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Synthesis Example 20 Bis- (1,3-dodecylamino) propan-2-ol 21.3 g (0.05 mol), succinic anhydride 16.5 g (0.15 mol) and anhydrous ether 300 were placed in a reaction vessel.
ml was added and refluxed for 5 hours. After the reaction was completed, ether was distilled off under reduced pressure to give 6- (3-carbohydroxy-propanoxy) -4,8-didodecyl-3,9-dioxo-4,8-diaza-1,11-undecanedicarboxylic acid. 37.8 g (quantitative) was obtained.

This compound was analyzed by HPLC (column: RP-
18 (manufactured by Merck), eluent methanol / water = 90 /
A single peak was given in the 10,50 mM ammonium acetate assay.

¹ H-NMR (CDCl ₃ ): δ (pp
m) TMS standard 0.89 (triple line, 6H, a), 1.28 (wide singlet, 24H, b), 1.55 (wide singlet, 4H,
c), 2.24 to 2.82 (complex multiline, 12H,
g. h), 2.90 to 3.83 (complex multiline, 9H,
d. e. f)

[0168]

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IR (KBr): 3560, 2940, 2
860, 1730, 1630, 1560 cm ^-1

Synthesis Example 21 Bis- (1,3-decylamino) propane-in a reaction vessel
2-Ol 40.2g (0.108mol), ethanol 260g, and water 100g were put, and it heated up at 50 degreeC. To this, sodium monochloroacetate 62.9 g (0.540
Was added to a solution of 150 g of isopropanol dissolved in 150 g of isopropanol and 100 g of water, and the mixture was reacted under reflux for 30 hours while keeping the pH at 8 to 10. After completion of the reaction, the solvent was distilled off and the residue was dissolved in chloroform to remove insoluble unreacted sodium monochloroacetate and by-produced salts such as sodium chloride. After that, it was purified by silica gel column chromatography until a single spot was obtained by thin layer chromatography, and 2,6-didecyl-4-hydroxy-2,6-diaza-1,1,7,7-heptanetetra was obtained. 20 g of carboxylic acid
Was obtained as a white powder (isolated yield 31%). This product was analyzed by HPLC (column: RP-18 (manufactured by Merck)),
Eluent methanol / water = gave a single peak in the 80/20 measurement. The ¹ H-NMR data is shown below.

¹ H-NMR (D ₂ O): δ (ppm) D ₂
O standard (4.75) 0.82 (triple line, 6H, a), 1.24 (wide singlet, 28H, b), 1.57 (wide singlet, 4H,
c), 2.99 to 3.32 (complex multiline, 8H,
d), 3.58 (wide singlet, 8H, f), 4.02
(Wide singlet, 1H, e)

[0172]

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Synthesis Example 22 10 g (0.023 mol) of 2,6-dioctyl-4-hydroxy-2,6-diaza-1,7-heptanedicarboxylic acid obtained in Synthesis Example 2 and 20 g of methanol were placed in a reaction vessel. The temperature was raised to 50 ° C. 8.4g of methyl iodide
(0.06 mol) was added, and the mixture was reacted at 60 ° C for 14 hours. After completion of the reaction, the solvent was distilled off and desalted by electrodialysis,
By freeze-drying, 2,6-dimethyl-2,6-
Dioctyl-4-hydroxy-2,6-diaza-1,7
-9.5 g of heptane dicarboxylic acid (isolated yield 90%)
Obtained as a white powder. The ¹ H-NMR data is shown below.

¹ H-NMR (D ₂ O): δ (ppm) D ₂
O standard (4.75) 0.82 (triple line, 6H, a), 1.22 (wide singlet, 20H, b), 1.59 (wide singlet, 4H,
c), 3.02 (single line, 6H, e), 3.05-3.
30 (complex multi-line, 8H, d), 3.94 (single line,
4H, f), 4.11 (wide singlet, 1H, g),

[0175]

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Test Example 1 The irritation to the skin was examined by the following method. (Test method) After shaving the hair on the flank of a guinea pig (n = 5), 30 mg of a 10% sample solution was applied in a circular shape having a diameter of about 2 cm (total 8 times). After the application was repeated once a day for 4 days, the condition of the applied skin part was evaluated. Judgment was performed by a 5-step evaluation, and the average number of guinea pigs was calculated.

[0177]

[Table 1]

[0178]

[Table 2]

From Table 2, it was revealed that the compound (1) was obviously weaker in skin irritation than triethanolamine lauryl sulfate.

Example 1 A detergent composition for hard surfaces having the composition shown in Table 3 was prepared, and a window glass of a household with hand stains, stains, and tar stains was actually washed. The evaluation was performed by the following evaluation method.

(Evaluation Method of Detergency and Finishing Property) 2 ml of the cleaning liquid was sprayed with a commercially available sprayer, wiped off with a dry towel, and then sensory evaluation was performed according to the following evaluation criteria.

Evaluation Criteria: Detergency ○: Dirt drops by 80% or more. Δ: Dirt drops by 30% or more and less than 80%. X: Almost no dirt is removed.

-Finishability ◯: Almost no wiping lines. Δ: Some wiping marks remain. X: Wiping lines remain.

[0184]

[Table 3]

Examples 2 to 7 Cleaning compositions for hard surfaces having the compositions shown in Table 4 were prepared, and the detergency was evaluated by the following evaluation methods.

(Evaluation method) Tempura oil was added at 200 to 220 ° C.
After heating for 20 hours at 100 ° C., the oil was deteriorated by treating for 10 hours while blowing air at 100 ° C. 5 g of this deteriorated oil was applied to the surface of the stainless steel plate and left at room temperature for 1 month. Each composition was dropped on this stain, left for 5 minutes, and then
After wiping off with a dry towel, sensory evaluation was performed according to the following evaluation criteria.

Detergency ⊚: Stain removal is very good. ◯: Stain removal is good. Δ: There are places where stains do not come off. X: Almost no dirt is removed.

[0188]

[Table 4]

Examples 8 to 10 The cleaning compositions for hard surfaces shown in Table 5 were prepared, and the cleaning power was evaluated by the following evaluation methods.

(Evaluation method) The evaluation of the detergency was carried out by applying a load of about 500 g to a urethane sponge containing a cleaning agent for evaluation, using a cast iron enamel bath with bath stains that would not be removed by rubbing. The state of removal of stains on the bath surface after rubbing 5 times back and forth was visually evaluated in the following 5 grades.

Detergency 5: Stain removal is very good. 4: Good stain removal. 3: There is uneven stain removal. 2: The stain is slightly removed. 1: Almost no dirt is removed.

Further, the foamability (slipperiness) when rubbing with a sponge was also evaluated.

[0193]

[Table 5]

Examples 11 to 15 The cleaning compositions for hard surfaces shown in Table 6 were prepared, and the detergency was evaluated by the following evaluation methods.

(Evaluation method) 10 g of each composition was applied to a non-washed toilet bowl for urinals in an actual household, which was rubbed 10 times with a brush having a branch, and a sensory evaluation was performed according to the following evaluation criteria.

Detergency: Good stain removal. Δ: Stain removal is slightly good. X: Almost no dirt is removed.

[0197]

[Table 6]

From Examples 1 to 15, the cleaning composition for hard surfaces of the present invention was used in various hard surfaces such as hand stains, mud, glass with tar stains, kitchen areas with oil stains, bathrooms, toilets and the like. It can be seen that the detergency for surface stains is excellent, and the finishability and foam slipperiness are good.

[0199]

The detergent composition for hard surfaces of the present invention has excellent cleaning power for stains on hard surfaces such as kitchen areas, bathrooms, toilets, window glass, etc., has good finishing properties, and is not irritating to the skin. There are few.

[Brief description of drawings]

FIG. 1 is a ¹ H-NMR chart of the compound obtained in Synthesis Example 5.

FIG. 2 is a ¹ H-NMR chart of the compound obtained in Synthesis Example 6.

FIG. 3 is a ¹ H-NMR chart of the compound obtained in Synthesis Example 8.

FIG. 4 is a ¹ H-NMR chart of the compound obtained in Synthesis Example 10.

FIG. 5 is a ¹ H-NMR chart of the compound obtained in Synthesis Example 11.

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[Procedure amendment]

[Submission date] September 2, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0085

[Correction method] Change

[Correction content]

[0085]

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Claims (6)

[Claims] 1. The following components (A) and (B): (A) The following general formula (1); [In the formula, R ¹ and R ² are the same or different and have 6 to 3 carbon atoms.
6 represents a linear or branched alkyl or alkenyl group of 6, X represents an alkylene or alkenylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, a sulfonic acid group or a carboxyl group, and Y ¹ represents a sulfone. Represents an acid group, a sulfuric acid residue or a carboxyl group, Y ² is a hydroxyl group,
Sulfate residue or the following formula (2); A 2-hydroxypropanediamine derivative represented by the following formula, wherein n represents 0 or 1], a salt or a quaternary derivative thereof, (B) a sequestering agent, an alkali agent and a water-soluble solvent. A hard surface cleaner composition containing one or more. 2. The hard surface cleaner composition according to claim 1, wherein in the component (A), Y ¹ is a sulfonic acid group or a sulfuric acid residue, and Y ² is a hydroxyl group or a sulfuric acid residue. 3. The hard surface cleaner composition according to claim 1, wherein in the component (A), Y ¹ is a carboxyl group, and Y ² is a hydroxyl group or a group represented by the above formula (2). 4. In the component (A), R ¹ and R ² are
The cleaning composition for hard surfaces according to claim 1, which is a linear or branched alkyl or alkenyl group having 6 to 24 carbon atoms. 5. The hard surface cleaner composition according to claim 1, wherein the component (A) is in the form of a free base or a salt. 6. A hard surface according to any one of claims 1 to 5, which contains 0.1 to 50% by weight of the component (A) and 0.01 to 50% by weight of the component (B). Cleaning composition.