JPH08109398A - Detergent composition for hard surface - Google Patents

Abstract

PURPOSE: To obtain a detergent composition useful for cleaning the surroundings of kitchen, bathroom, window glass, etc., having excellent cleaning power and finishing properties and low irritation to skin, by blending a specific tris(3- aminopropyl)amine derivative with a sequestering agent and an alkali agent or a water-soluble solvent. CONSTITUTION: This detergent composition for hard surface contains (A) a compound of the formula [R is a (OH-substituted) 1-24C (branched) alkyl or alkenyl; A is an (OH, carboxyl or sulfonic group substituted) 1-6C (branched) alkylene or alkenylene; Y<1> is carboxyl, sulfonic group or sulfuric acid residue; Y<2> is OH, sulfuric acid residue or a group of the formula -OCO-A-COOH; (n) is 0 or 1], its salt or quaternized substance and (B) a sequestering agent, an alkali agent or a water-soluble solvent. The contents of the components A and B are 0.1-50wt.% and 0.01-50wt.%, respectively.

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 these circumstances, the present inventors have conducted diligent studies, and as a result, as a result, the tris (3-aminopropyl) amine derivative represented by the general formula (1) described below was added to a sequestering agent and an alkaline agent. Or, if a water-soluble solvent is added, it is possible to obtain an excellent cleaning agent that has excellent cleaning power for stains on hard surfaces around kitchens, toilets, bathrooms, etc., has good finish, and is not irritating to the skin. The present invention has been completed and 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]

Embedded image

[In the formula, R represents a linear or branched alkyl group or alkenyl group having 1 to 24 carbon atoms which may be substituted with a hydroxyl group, and A represents a hydroxyl group, a carboxyl group or a sulfonic acid group. Represents a linear or branched alkylene group having 1 to 6 carbon atoms or an alkenylene group which may be substituted, Y ¹ represents a carboxyl group, a sulfonic acid group or a sulfuric acid residue, and Y ² represents a hydroxyl group,
A sulfuric acid residue or a group -OCO-A-COOH is shown, and n is 0 or 1. ] A hard material containing one or more selected from tris (3-aminopropyl) amine derivatives represented by the following, salts or quaternary compounds thereof, (B) sequestering agents, alkaline agents and water-soluble solvents. A cleaning composition for surfaces is provided.

The compound having a structure close to that of the compound (1) used in the present invention is a compound having a 2-hydroxypropanediamine structure (US Pat. No. 3,654,158).
U.S. Pat. No. 3,607,884, U.S. Pat. No. 4,982.
000, JP-A-1-233264, JP-A-2-22
No. 3515), but these compounds are
In addition to having a diamine structure, it does not have an anionic functional group such as a carboxyl group, a sulfonic acid group, a sulfuric acid residue, etc., and is greatly different in structure and function from the compound of the present invention.

Tris (3-) used as the component (A)
The aminopropyl) amine derivative, a salt thereof or a quaternary compound thereof is used as a cleaning active ingredient, and is a linear or branched chain which may be substituted with a hydroxyl group represented by R in the general formula (1). Specific examples of the alkyl group or alkenyl group having 1 to 24 carbon atoms include the following.

Examples of the straight chain alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, Henicosyl, docosyl, tricosyl and tetracosyl can be mentioned, and examples of the branched chain alkyl group include groups such as methylhexyl, ethylhexyl, methylheptyl, ethylheptyl, methylnonyl, methylundecyl, methylheptadecyl, hexyldecyl and octyldecyl. Can be mentioned.

Examples of the straight chain alkenyl group include ethenyl, propenyl, butenyl, pentenyl, hexenyl,
Heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl,
Examples thereof include groups such as pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icosenyl, henicosenyl, docosenyl, tricosenyl, and tetracosenyl, and examples of the branched chain alkenyl group include, for example, methylhexenyl, ethylhexenyl, methylheptenyl, ethylheptenyl, methylnonenyl, methylnonenyl. Mention may be made of groups such as cenyl, methylheptadecenyl, hexyldecenyl, octyldecenyl and the like.

As the linear or branched alkyl group substituted with a hydroxyl group, the substitution position of the hydroxyl group is not particularly limited, and examples thereof include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, Hydroxyheptyl, hydroxyoctyl, hydroxynonyl, hydroxydecyl, hydroxyundecyl, hydroxydodecyl, hydroxytridecyl, hydroxytetradecyl,
Hydroxypentadecyl, hydroxyhexadecyl, hydroxyheptadecyl, hydroxyoctadecyl, hydroxynonadecyl, hydroxyicosyl, hydroxyhenicosyl, hydroxydocosyl, hydroxytricosyl, hydroxytetracosyl, hydroxymethylhexyl, hydroxyethylhexyl, hydroxymethyl Examples thereof include groups such as heptyl, hydroxyethylheptyl, hydroxymethylnonyl, hydroxymethylundecyl, hydroxymethylheptadecyl, hydroxyhexyldecyl, and hydroxyoctyldecylbutyl.

The linear or branched alkenyl group substituted with a hydroxyl group is not particularly limited in the substitution position of the hydroxyl group, and examples thereof include hydroxyethenyl, hydroxypropenyl, hydroxybutenyl, hydroxypentenyl, hydroxyhexenyl and hydroxy. Heptenyl, hydroxyoctenyl, hydroxynonenyl, hydroxydecenyl, hydroxyundecenyl, hydroxydodecenyl, hydroxytridecenyl, hydroxytetradecenyl, hydroxypentadecenyl, hydroxyhexadecenyl, Hydroxyheptadecenyl, hydroxyoctadecenyl, hydroxynonadecenyl, hydroxyicosenyl, hydroxyhenicosenyl, hydroxydocosenyl, hydroxytricosenyl, hydroxytetracosenyl, hydroxy Groups such as methylhexenyl, hydroxyethylhexenyl, hydroxymethylheptenyl, hydroxyethylheptenyl, hydroxymethylnonenyl, hydroxymethylundecenyl, hydroxymethylheptadecenyl, hydroxyhexyldecenyl, hydroxyoctyldecenyl. Can be mentioned.

Of these, R is a linear or branched C 6-24 alkyl or alkenyl group,
Further, a linear or branched alkyl group having 6 to 12 carbon atoms, particularly a linear alkyl group having 6 to 10 carbon atoms is preferable.

Specific examples of the linear or branched alkylene group having 1 to 6 carbon atoms or alkenylene group which may be substituted by the hydroxyl group, carboxyl group or sulfonic acid group represented by A in the general formula (1) The following can be cited as examples.

As the alkylene or alkenylene group,
For example, methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group,
Methylethylene group, ethylethylene group, ethenylene group,
Examples thereof include a propenylene group, a butenylene group, a pentenylene group and a hexenylene group. Of these, those having 1 to 4 carbon atoms are preferable, those having 1 to 3 carbon atoms are more preferable, and methylene group, ethylene group, trimethylene group and ethenylene group are particularly preferable.

The alkylene or alkenylene group may be substituted with a hydroxyl group (-OH), a sulfonic acid group (-SO ₃ H) or a carboxyl group (-COOH), and these substituents may be one kind or two kinds. One to four may be substituted by combining two or more species.

The hydroxy-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.

Examples of the alkylene or alkenylene group substituted with a sulfonic acid group include a 1-sulfoethylene group, a 2-sulfoethylene group, a 1-sulfotrimethylene group, a 2-sulfotrimethylene group, a 3-sulfotrimethylene group and a 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. Among these, 1-carboxyethylene group and 2-carboxyethylene group are preferable.

Examples of the alkylene or alkenylene group substituted with a hydroxy group and a carboxyl group include 2-carboxy-1-hydroxytrimethylene group, 2-carboxy-1,3-dihydroxytrimethylene group and 2-carboxy-2-hydroxytrimethylene group. Methylene group, 3-carboxy-
2,4-dihydroxytetramethylene group and the like can be mentioned. Among these, 2-carboxy-2-hydroxytrimethylene group is preferable.

Examples of the alkylene or alkenylene group substituted with a hydroxy 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 Examples thereof include a 2-sulfotetramethylene group, a 1-hydroxy-4-sulfotetramethylene group, a 2-hydroxy-4-sulfotetramethylene group and a 3-hydroxy-4-sulfotetramethylene group.

The compound (1) is a sulfonic acid group (-SO
₃ H), sulfuric acid residue (-OSO ₃ H) or carboxyl group (-COO
Since it has H), it can form salts with various basic substances. Examples thereof include alkali metal salts, alkaline earth metal salts, amine salts, basic amino acid salts, ammonium salts and the like. Specifically, sodium, potassium,
Examples thereof include salts with lithium, magnesium, calcium, trimethylamine, triethylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine, lysine, arginine, choline and ammonia. Among these, alkali metal salts, particularly sodium. Salt is preferred. Compound (1)
Has a tertiary amino group, n in the formula (1) is 0.
In the case of, the proton is coordinated on the nitrogen atom of the tertiary amino group, the tertiary amino group becomes an ammonium cation, and the sulfonic acid group, the sulfuric acid residue or the carboxyl group is converted to the sulfonic acid anion, the sulfuric acid anion or It may also have a quaternary salt structure that becomes a carboxy anion.

If necessary, the compound (1) can be made into a quaternized compound. Specifically, all or part of the four nitrogen atoms in the formula (1) are quaternized. Compounds. The group that can be bonded onto the nitrogen atom for the quaternization has 1 to 6 carbon atoms which may be substituted with a hydroxyl group, a carboxyl group or a sulfonic acid group.
Alkyl group, benzyl group or-(R ⁷ O) _m H (wherein R ⁷
Represents an alkylene group having 2 to 4 carbon atoms, and m represents a number of 1 to 50). Here, 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group and a hexyl group. , A hydroxyethyl group, a 1,2-dihydroxypropyl group, a carboxymethyl group, a carboxypropyl group, a 3-sulfo-2-hydroxypropyl group and the like. Specific examples of the group represented by the group-(R ¹ O) _m H include a polyoxyethylene group and a polyoxypropylene group, with m = 1 to 20 being preferable. The quaternary compound of the compound (1) can be present when n in the formula (1) is 0.

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

[0027]

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

That is, the tris (3-amino-2-hydroxypropyl) amine derivative (2) 'is converted to the compound (3).
Alternatively, compound (1a) is produced by reacting a salt thereof.

The reaction of the compound (2) 'with the compound (3) or a salt thereof is carried out, for example, in the presence of an inert solvent at 20 to 150.
C., preferably 40 to 100.degree. C., at a pH of 8 which is 3 to 10 times mol of compound (3) or a salt thereof with respect to compound (2) '.
It is carried out by reacting while keeping at 10.
Here, examples of the halogen atom represented by A ² of the compound (3) 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 (3) or a salt thereof include sodium chloroacetate and 3
-Sodium chloro-2-hydroxypropane sulfonate, sodium 3-chloropropionate, 4-chloro-
Examples thereof include sodium n-butyrate, and of these, sodium chloroacetate and sodium 3-chloro-2-hydroxypropanesulfonate are more preferable. Examples of the inert solvent used here include water, methanol, ethanol, isopropyl alcohol, dimethylformamide, polar solvents such as dimethylsulfoxide, and the like.
These may be used alone or in combination of two or more, and among them, water, a lower alcohol or a mixed solvent of water and a lower alcohol is preferable. In this reaction, when the compound (3) is used in excess of the compound (2) ',
A compound in which all or part of the nitrogen atoms in formula (1) are quaternized is produced.

After the completion of this reaction, in addition to the desired compound (1a), the reaction mixture contains an inorganic salt, unreacted compound (2) ', compound (2)' and compound (3) in an amount of 1 mol or 2; It may contain a compound to which a mole has been added and an unreacted compound (3). 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. The basic substance used here includes sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, ammonia, trimethylamine, triethylamine, tributylamine, alkanolamine (monoethanolamine, diethanolamine, triethanolamine). Etc.), lysine, arginine, choline, etc., among which sodium hydroxide,
Alkali metal hydroxides such as potassium hydroxide are preferred.

[0032]

[Chemical 4]

[In the formula, R, A ¹ and Y ² have the same meanings as described above, and R ³ and R ³ ′ are the same or different and each is an alkyl group which may be substituted with a hydrogen atom or a hydroxyl group or a carboxyl group. Alternatively, it represents an alkenyl group, and Y
² 'represents a hydroxyl group or a sulfuric acid residue. ]

That is, the tris (3-amino-2-hydroxypropyl) amine derivative (2) 'is reacted with the epoxy compound (4), the resulting compound (5) is reacted with a sulfuric esterification agent, and if desired, a base is added. The compound (1b) is produced by neutralizing with a volatile substance.

The reaction between the compound (2) 'and the epoxy compound (4) is carried out, for example, in an inert solvent, preferably 100 to 2
It is preferable to carry out the reaction by reacting the compound (2) 'with the epoxy compound (4) in a molar ratio of 3 to 7 times at 00 ° C, particularly preferably 130 to 180 ° 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 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 (4) and the inert solvent used. As the epoxy compound (4),
Ethylene oxide, propylene oxide, and butylene oxide are preferable because they are inexpensive, and ethylene oxide is particularly preferable.

Next, the reaction of the compound (5) thus obtained with a sulfuric acid esterifying agent such as ClSO ₃ H and SO ₃ is carried out in an inert solvent or without a solvent at -75 ° C to 150 ° C. It is preferable to carry out in the temperature range of. The amount of ClSO ₃ H or SO ₃ used is preferably 3 to 8 times mol of the compound (5). In addition, after the completion of this reaction, the same basic substance as that used in [reaction a] can be used in the neutralization reaction that is carried out if necessary.

In the first step of the above reaction b, 3
There may be a by-product of the reaction of only one or two of the reaction points. This reaction product can be used as it is, but if a higher purity product is required, it can be purified by a conventional method, for example, recrystallization, column chromatography, distillation or the like, and then used. Further, in the second stage, a compound in which all or some of the 6 reaction points are reacted is produced depending on the amount of ClSO ₃ H or SO ₃ used. This reaction product can be used as it is for various purposes, but when a higher purity is required, it can be appropriately fractionated and purified by the same method as described above.

[0038]

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[In the formula, R, A ¹ and Y ² ′ have the same meanings as described above, and R ⁴ represents a hydrogen atom or an alkyl group which may have a substituent. ]

That is, the compound (2) 'is reacted with a lactone or a hydroxycarboxylic acid, the resulting amide alcohol (6) is reacted with a sulfuric acid esterifying agent, and the compound (2) is neutralized with a basic substance if desired. 1c)
Is manufactured.

The reaction of the compound (2) 'with a lactone or a hydroxycarboxylic acid is carried out, for example, in an inert solvent or without a solvent, preferably 20 to 180 ° C., particularly preferably 4
It is preferably carried out by reacting the compound (2) ′ with a lactone or hydroxycarboxylic acid in a molar ratio of 3 to 7 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 lactones and oxycarboxylic acids used in this reaction, γ-lactone, δ-lactone, glycolic acid,
Lactic acid, α-hydroxy acid and their methyl esters,
Ethyl ester and the like are preferable.

The reaction of the amide alcohol (6) thus obtained with a sulfuric acid esterifying agent such as ClSO ₃ H and SO ₃ is carried out in an inert solvent or without a solvent at a temperature of −75 ° C. to 150 ° C. It is preferable to carry out in the range. The amount of ClSO ₃ H or SO ₃ used is preferably 3 to 8 times the molar amount of the amide alcohol (6). 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 reactions a and b.

In the first step of the above reaction c, 3
There may be a case where a compound that has reacted at only one or two of the reaction points is produced as a by-product. This reaction product can be used as it is, but if a higher purity product is required, it can be purified by a conventional method, for example, recrystallization, column chromatography, distillation or the like, and then used. Further, in the second stage, a compound in which all or some of the 6 reaction points are reacted is produced depending on the amount of ClSO ₃ H or SO ₃ used. This reaction product can be used as it is for various purposes, but when a higher purity is required, it can be appropriately fractionated and purified by the same method as described above.

[0044]

[Chemical 6]

[In the formula, R and A ¹ have the same meanings as described above, R ⁵ and R ⁶ represent a hydrogen atom or an optionally substituted alkyl group or alkenyl group, and A ² represents a hydroxyl group. Alternatively, it represents a linear or branched alkylene group having 1 to 6 carbon atoms, which may be substituted with a carboxyl group and is substituted with a sulfonic acid group, and Y ² ″ is a hydroxyl group or a group —OCO-A ¹ —COOH. And Y ² ″ ″ represents a hydroxyl group or a group —OCO—A ² —COOH.]

That is, the compound (2) 'is reacted with an acid anhydride, a dicarboxylic acid or an ester thereof, and when an ester is used, the ester site thereof is further hydrolyzed and, if necessary, neutralized with a basic substance. Therefore, the compound (1
d) or its salt can be prepared. In addition, when -CH = CH- is present in A ^{1 of} the obtained compound (1d),
The compound (1e) of the present invention is produced by reacting this with a sulfonating agent such as SO ₃ , sodium sulfite and NaHSO ₃ , and neutralizing with a basic substance if necessary.

The reaction of the compound (2) 'with an acid anhydride is carried out, for example, in the presence of an anhydrous inert solvent at 20 to 150 ° C, preferably 40 to 100 ° C, preferably to the compound (2)'. It is preferably carried out by reacting 3 to 8 times by mole of acid anhydride. Examples of the anhydrous inert solvent used here include ether, tetrahydrofuran, benzene, pyridine and the like. In addition, in this reaction, all or a part of three hydroxyl groups at the 2-position depending on the excess amount of the acid anhydride reacts with the acid anhydride to form a group -OCO.
Can be converted to -A ¹ -COOH.

The reaction of the compound (2) 'with the dicarboxylic acid or its ester is carried out, for example, in an inert solvent at 40
It is preferable to carry out at ~ 180 ° C, preferably 80-150 ° C, by reacting the compound (2) 'with a dicarboxylic acid or its ester in a molar amount of preferably 3 to 6 times. This reaction is preferably carried out while removing the produced alcohol or water. Examples of the inert solvent used in this reaction include hexane, benzene, toluene, xylene and the like.

In the dicarboxylic acid ester, examples of the alkyl group or alkenyl group represented by R ⁵ and R ⁶ 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 (7) is obtained, which is then subjected to, for example, hydrous alcohol under acid or base catalysis. Hydrolysis is required.

[0051]

[Chemical 7]

[In the formula, R and A ¹ have the same meanings as described above, and R ′ represents an alkyl group or an alkenyl group corresponding to R ⁵ or R ⁶ . ]

Next, the reaction of the compound (1d) having —CH═CH— in A ¹ with a sulfonating agent such as SO ₃ , sodium sulfite and sodium bisulfite is carried out, for example, in water at 30 to 100 ° C. , Preferably 40 to 80 ° C., 1 to 8 times mol, preferably 1 to 3 times mol of SO ₃ , sodium sulfite, sodium hydrogen sulfite and the like with respect to —CH═CH— group in the compound (1d), It is preferable to carry out the reaction at a pH of 4.0 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 reactions a to c. In addition, in these reactions, a compound in which only one or two amino groups are amidated, a compound in which only one or two hydroxyl groups are esterified, and the like are produced as by-products, but reaction products are used as they are. It can also be used for. However, when a higher-purity product is required, it can be used after being appropriately fractionated and purified by a conventional method such as recrystallization, column chromatography, electrodialysis and the like.

[0055]

Embedded image

[Wherein R and Y ³ have the same meanings as described above, A ³ represents an alkenylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group or a carboxyl group, and A ^3
4 represents an alkylene group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group or a carboxyl group, and Y ³ ′ represents the same or different, a hydrogen atom, a carboxyl group, a sulfonic acid group or an alkoxycarbonyl group. However, neither of the two Y ³ ′ is a hydrogen atom. ]

That is, the compound (2) 'is reacted with the olefin compound (8), and when an ester is used as the compound (8), the ester site is further hydrolyzed, and if necessary, a basic substance is added to the intermediate. Compound (1f) or a salt thereof can be produced by solvation. The reaction between the compound (2) ′ and the olefin compound (8) is carried out, for example, in the presence of an inert solvent at 20 to 80 ° C., preferably room temperature to 60 ° C., and 3 to 6 times as much as the compound (2) ′. It is preferably carried out by reacting a mole of the olefin compound (8). Examples of the inert solvent used here include methanol, ethanol, isopropyl alcohol, ether, tetrahydrofuran, benzene, pyridine and the like. Particularly when carboxylic acid is used as the olefin compound (8), pyridine is preferably used. When an ester is used as the olefin compound (8), it is necessary to hydrolyze the ester portion of the obtained compound in, for example, hydrous alcohol under an acid or base catalyst.

In the general formula (1), when n = 0, a quaternizing agent is reacted with this to cause all or part of the four nitrogen atoms in the compound (1) to be converted to the fourth atom.
A graded compound, for example, a compound represented by the following formula (1) ′ is obtained.

[0059]

[Chemical 9]

[In the formula, R, A, Y ¹ and Y ² have the same meanings as described above, and Z is an alkyl group having 1 to 6 carbon atoms which may be substituted with a sulfonic acid group, a carboxyl group or a hydroxyl group. Or alkenyl group, benzyl group or group-
(R ⁷ O) _m H (R ⁷ and m are the same as defined above). ]

The quaternizing agent has 1 to 6 carbon atoms which may be substituted with a hydroxyl group, a carboxyl group or a sulfonic acid group.
Alkyl halides, benzyl halides, alkylene oxides and salts thereof. Of these, alkyl halides are more preferable. Here, examples of the alkyl group include a methyl group, ethyl group, n-propyl group, n-butyl group, and isopropyl group, and examples of the halogen include chlorine, bromine, and iodine. Of these, methyl chloride is particularly preferable.

The tris (3-amino-2-hydroxypropyl) amine derivative (2) 'used as the starting material for the compound (1) in the reactions a to e can be produced, for example, according to the following reaction formula. .

[0063]

[Chemical 10]

[In the formula, X has the same meaning as described above, and R ¹
And R ² are the same or different and represent a linear or branched alkyl group or alkenyl group having 1 to 24 carbon atoms, which may be substituted with a hydrogen atom or a hydroxyl group. That is, a reaction of halohydrin compound (b) obtained by reacting ammonia gas or ammonia water with epihalohydrin (a), or an epoxy compound (c) obtained by reacting this with a basic compound and an amine compound (d) Thus, the compound (2) is obtained, and the compound (2) 'in which R ¹ is a hydrogen atom and R ² is R in the general formula (2) is the compound (2)'. This compound (2) is a novel compound not described in the literature.

In the above-mentioned production method, the halogen atom represented by X of epihalohydrin (a) used for the synthesis of halohydrin compound (b) includes, for example, chlorine, bromine and iodine, preferably chlorine. The reaction of ammonia with epihalohydrin (a) is carried out, for example, in the absence of a solvent or in a solvent inert to the reaction such as lower alcohol, ether, aromatic hydrocarbon or a mixture thereof, preferably −20 to 100 ° C., particularly preferably Can be performed at 0 to 50 ° C. Further, when using ammonia water, preferably without solvent or in a lower alcohol solvent,
Perform at 0-50 ° C. The amount ratio of ammonia and epihalohydrin (a) to be used can be set as appropriate, but it is preferable to use epihalohydrin (a) in an amount of 3 to 6 times the molar amount of ammonia.

As the basic compound used for the subsequent synthesis of the epoxy compound (c), for example, alkali metal hydroxides, alkali metal carbonates, amines and the like are preferable,
Particularly, sodium hydroxide and potassium hydroxide are preferable. The reaction of the halohydrin compound (b) with the basic compound is carried out, for example, in a solvent inert to the reaction such as water, a lower alcohol or a mixture thereof, preferably at 0 to 80 ° C, particularly preferably at 20 to 60 ° C. be able to. The amount ratio of the halohydrin compound (b) and the basic compound used can be appropriately set, but it is preferable to use the basic compound in an amount of 2 to 5 times the molar amount of the halohydrin compound (b).

The reaction of the halohydrin compound (b) or epoxy compound (c) thus obtained with the amine compound (d) can be carried out, for example, in the absence of a solvent or in a lower alcohol, ether, aromatic hydrocarbon or In a solvent inert to the reaction such as a mixture thereof, preferably 40 to 150
C., particularly preferably 60 to 100.degree. The amount ratio of each compound used in the reaction can be appropriately set, but in general, the amine compound (d) is 3 to 20 times mol relative to the halohydrin compound (b) or the epoxy compound (c), It is particularly preferable to use 3 to 10 times the molar amount.

In the compound (2) thus obtained, in the general formula (2), R ¹ is a hydrogen atom and R ² is R.
The compound (2) ′ of the formula (1) is useful as a starting material for the compound (1) in the reactions a to d as described above, but also in the compound of the general formula (2) in which R ¹ and R ² are not hydrogen atoms, By reacting this with the compound (3), the quaternary compound (1a) ′ can be produced in one step and is useful as a raw material thereof.

[0069]

[Chemical 11]

[In the formula, A ¹ and Y ³ have the same meanings as described above, and R ¹ ′ and R ² ′ represent an alkyl group or an alkenyl group corresponding to R ¹ and R ² , respectively. ]

The blending 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 without any particular limitation. 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 a 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.

[0077]

[Chemical 12]

[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.

[0082]

[Chemical 13]

[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.

[0085]

Embedded image

[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.

[0088]

[Chemical 15]

[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.

[0091]

[Chemical 16] 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 compounding 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 that does not impair 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).

[0099]

[Chemical 17] 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 alkanolamides or their alkylene oxide adducts, amine oxides and alkyl glycosides are used from the viewpoint of improving the 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.

In addition to the above-mentioned components, the detergent composition for hard surfaces of the present invention may further contain a conventional dispersant, a fragrance, a dye, in order to further improve the storage stability of the system at low temperature.
Pigments, preservatives and the like can be added within a range that does not impair the effects of the present invention.

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

[0108]

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 Epichlorohydrin (0.93 mol) and 100 ml of ethanol were placed in a reaction vessel, 25% aqueous ammonia (20.4 ml) was added dropwise at room temperature, and the temperature was kept at 45 to 50 ° C. for about 3 hours. It was made to react. Then, after removing excess epichlorohydrin, octylamine (2.7 mol) was added, and
The reaction was carried out at 0 to 90 ° C for 10 hours. After completion of the reaction, excess octylamine was removed, the product obtained as crystals of hydrochloride was dissolved in xylene, washed with aqueous sodium hydroxide solution and washed with water, and tris (4-aza-2-hydroxydodecyl) amine Was obtained (165 g, yield 96%).

This compound gave a single peak in gas chromatography (SE-52, 1%, 0.5 m). ^{The 1} H-NMR spectrum is as follows.

¹ H-NMR (CDCl ₃ ): δ (ppm) 0.9 (9H, triplet, a) 1.3 (30H, wide singlet, b) 1.5 (6H, wide singlet, c) 2.4-2.7 (18H , Complex multiplet, d, e, g) 3.8 (3H, quintuplet, f)

[0112]

Embedded image

Synthesis Example 2 Epichlorohydrin (0.93 mol) and 100 ml of ethanol were placed in a reaction vessel, 25% aqueous ammonia (20.4 ml) was added dropwise at room temperature, and the temperature was kept at 45 to 50 ° C. for about 3 hours. It was made to react. Then, after removing excess epichlorohydrin, hexylamine (2.7 mol) was added,
The reaction was carried out at 0 to 90 ° C for about 8 hours. After completion of the reaction, excess hexylamine was removed, the product obtained as crystals of the hydrochloride was dissolved in xylene, washed with an aqueous solution of sodium hydroxide and washed with water to give tris (4-aza-2-hydroxydecyl) amine. Was obtained in an amount of 126 g (yield 86%).

This compound gave a single peak (RT = 15.5 min) in gas chromatography (SE-52, 1%, 0.5 m). ^{The 1} H-NMR spectrum is as follows.

¹ H-NMR (CDCl ₃ ): δ (ppm) 0.85 (9H, triplet, a) 1.3 (18H, wide singlet, b) 1.45 (6H, quintet, c) 2.4-2.8 (18H , Complex multiplet, d, e, g) 3.75 (3H, quintuplet, f)

[0116]

[Chemical 19]

Synthesis Example 3 Epichlorohydrin (1.35 mol) and 100 ml of ethanol were placed in a reaction vessel, 25% aqueous ammonia (20.4 ml) was added dropwise at room temperature, and the temperature was kept at 45 to 50 ° C. for about 3 hours. It was made to react. Then, after removing excess epichlorohydrin, 2- (ethylamino) ethanol (2.
7 mol) was added and the mixture was reacted at 80 to 90 ° C. for about 5 hours.
After completion of the reaction, excess 2- (ethylamino) ethanol was removed, the product obtained as crystals of the hydrochloride was dissolved in xylene, washed with aqueous sodium hydroxide solution, washed with water, and tris (4-aza-4). -Ethyl-2,6-dihydroxy)
122 g (yield 90%) of amine was obtained.

This compound was analyzed by gas chromatography (S
E-52, 1%, 0.5 m) gave a single peak. ¹ H-NMR is as follows.

¹ H-NMR (CDCl ₃ ): δ (ppm) 1.0 (9H, triplet, c) 2.4-2.7 (24H, complex multiplet, b, d, e, g) 3.4 (6H, triplet , a) 3.7 (3H, quintet, f)

[0120]

Embedded image

Synthesis Example 4 Tris (4-aza-2-hydroxydodecyl) amine (28.6 g, 0.05 mol) and ethanol (50 ml) were placed in a reaction vessel, the temperature was raised to 70 ° C., and sodium chloroacetate (17.5 g) was added. A 40% (0.15 mol) aqueous solution was added dropwise, and the reaction was carried out at 70 ° C. for 19 hours while adjusting the pH to 9 to 10 with an aqueous sodium hydroxide solution. During this reaction, 23.3 g (0.2 mol) of sodium chloroacetate was added in several portions.

The reaction mixture was concentrated under reduced pressure, n-butanol was added to the residue and the mixture was washed with water. The n-butanol layer was dried to obtain tris (4-aza-2-hydroxy-4-carboxymethyldodecyl) amine (31.8 g, yield 85%).

As a result of mass spectrometry (FAB ionization method) of this compound, a peak of m / z = 747 (M + H) was shown.

¹ H-NMR (D ₂ O): δ (ppm) 0.94 (9H, triplet, a) 1.36 (30H, wide singlet, b) 1.49 (6H, wide singlet, c) 2.35 to 2.75 ( 18H, complex multiplet, d, e, g) 3.18 (6H, wide singlet, h) 3.83 (3H, quintet, f)

[0125]

[Chemical 21]

Synthesis Example 5 Tris (4-aza-2-hydroxydodecyl) amine (28.6 g, 0.05 mol) and ethanol (50 ml) were placed in a reaction vessel and the temperature was raised to 70 ° C., followed by 3-chloro-2-
Sodium hydroxypropane sulfonate 32.8g
An aqueous solution (0.15 mol) was added dropwise, and the reaction was carried out at 70 ° C for 20 hours while adjusting the pH to 9 to 10 with sodium hydroxide. During this reaction, 43.7 g (0.2 mol) of sodium 3-chloro-2-hydroxypropanesulfonate was added to 5
It was added in portions.

The reaction mixture was concentrated under reduced pressure, n-butanol was added to the residue, and the mixture was washed with water. The n-butanol layer was dried to obtain tris (4-aza-2,6-dihydroxy-4-octyl-7-sulfoheptyl) amine (43.5 g, yield 88.2%).

As a result of mass spectrometry (FAB ionization method) of this compound, a peak of m / z = 987 (M + H) was shown.

¹ H-NMR (D ₂ O): δ (ppm) 0.86 (9H, triplet, a) 1.30 (30H, wide singlet, b) 1.64 (6H, wide singlet, c) 2.50 to 2.95 ( 24H, complex multiplet, d, e, g, h) 3.06 (6H, wide singlet, j) 4.00 (3H, quintet, f) 4.35 (3H, quintet, i)

[0130]

[Chemical formula 22]

Synthesis Example 6 Tris (4-aza-2-hydroxydodecyl) amine 28.6 g (0.05 mol), succinic anhydride 15.0 g (0.15 mol) and chloroform 100 ml were placed in a reaction vessel.
Was charged and refluxed for 4 hours. Chloroform in the reaction mixture was distilled off under reduced pressure, n-butanol was added to the residue, and the mixture was washed with water until the washings showed no acidity, and the n-butanol layer was dried to tris (4-aza-4-octyl-). 5-oxy-
43 g of 2-hydroxy-7-hexacarboxy) amine
(Yield 98.6%) was obtained.

The obtained tris (4-aza-2-hydroxy-4-octyl-5-oxy-2-hydroxy-7-)
Carboxyhexyl) amine was suspended in water, adjusted to pH 7 with an aqueous solution of sodium hydroxide and dissolved, and the solution was dried by freeze-drying to give tris (4-aza-2-hydroxy-).
4-octyl-5-oxy-7-carboxyhexyl)
The sodium salt of the amine was obtained.

As a result of mass spectrometry (FAB ionization method) of the acid form obtained by treating this compound with 1N hydrochloric acid, m / z =
It showed a peak at 873 (M + H).

¹ H-NMR (D ₂ O): δ (ppm) 0.93 (9H, triplet, a) 1.30 (30H, wide singlet, b) 1.59 (6H, wide singlet, c) 2.35 to 2.95 ( 30H, complex multiplet, d, e, g, h, i) 4.06 (3H, quintet, f)

[0135]

[Chemical formula 23]

Synthesis Example 7 Tris (4-aza-2-hydroxydecyl) was placed in a reaction vessel.
Amine 24.4 g (0.05 mol), maleic anhydride 1
4.7 g (0.15 mol) and 100 ml of ether were added, and the mixture was refluxed for 6 hours. The reaction mixture was washed with water until the washing liquid showed no acidity, and the ether layer was distilled off. The residue was mixed with an aqueous solution of 20.2 g (0.16 mol) of sodium sulfite and reacted at 60 ° C. for 4 hours while keeping the pH at 5-6. After completion of the reaction, the pH was adjusted to 7 with an aqueous sodium hydroxide solution, and excess sodium sulfite was removed by electrodialysis.

After that, freeze-drying treatment was performed, and Tris (4
45.2 g (yield 85.0%) of sodium salt of -aza-7-carboxy-4-hexyl-2-hydroxy-5-oxo-7-sulfohexyl) amine was obtained.

¹ H-NMR (D ₂ O): δ (ppm) 0.90 (9H, triplet, a) 1.32 (18H, wide singlet, b) 1.50 (6H, wide singlet, c) 2.25 to 3.30 ( 6H, complex multiplet, d, e, g, h, i) 4.02 (3H, quintet, f)

[0139]

[Chemical formula 24]

Synthetic Example 8 28.6 g (0.05 mol) of tris (4-aza-2-hydroxydodecyl) amine and 21.5 g (0.25 mol) of γ-butyrolactone were placed in a reaction vessel, and the temperature was set to 160 ° C.
The temperature was raised to and the reaction was performed for 5 hours. After completion of the reaction, purification by column chromatography (silica gel 500 g, developing solvent: chloroform / methanol = 100: 1) was performed, and tris (4-aza-2,8-dihydroxy-4-octyl-5-oxooctyl) amine 34. 7 g (yield 83.
6%) was obtained.

33.2 g (0.04 mol) of tris (4-aza-2,8-dihydroxy-4-octyl-5-oxooctyl) amine obtained above and 150 ml of dichloromethane were placed in a reaction vessel, and a nitrogen stream was introduced. Under ice-cooling, a dichloromethane solution of 8 ml (0.12 mol) of chlorosulfuric acid was gently added dropwise. Then, the temperature was gradually returned to room temperature, and hydrochloric acid and dichloromethane generated by a nitrogen stream were removed. Pour the residue into water and adjust the pH to 7 with aqueous sodium hydroxide.
Adjusted to. This aqueous solution was desalted by electrodialysis and lyophilized to give 44.5 g of sodium salt of tris (4-aza-2-hydroxy-4-octyl-5-oxo-8-sulfoxyoctyl) amine (yield 98 %) Was obtained.

¹ H-NMR (D ₂ O): δ (ppm) 0.89 (9H, triplet, a) 1.34 (30H, wide singlet, b) 1.55 (6H, wide singlet, c) 2.55 to 3.35 ( 36H, complex multiplet, d, e, g, h, i, f) 3.98 (3H, quintuplet, f)

[0143]

[Chemical 25]

Synthesis Example 9 Tris (4- (4)) obtained in the same manner as in Synthesis Example 8 was placed in a reaction vessel.
Add 41.5 g (0.05 mol) of aza-2,8-dihydroxy-4-octyl-5-oxooctyl) amine and 150 ml of dichloromethane, and add 20 ml (0.3 mol) of chlorosulfuric acid under a nitrogen stream while cooling with ice. Of dichloromethane solution was gently added dropwise. Then, the temperature was gradually returned to room temperature, and hydrochloric acid and dichloromethane generated by a nitrogen stream were removed. Pour the residue into water and add sodium hydroxide solution.
The pH was adjusted to 7. This aqueous solution was desalted by electrodialysis and freeze-dried to give tris (4-aza-4-).
71.4 g (yield 99%) of sodium salt of octyl-5-oxo-2,8-disulfoxyoctyl) amine was obtained.

¹ H-NMR (D ₂ O): δ (ppm) 0.92 (9H, triplet, a) 1.36 (30H, wide singlet, b) 1.57 (6H, wide singlet, c) 2.45 to 3.40 ( 36H, complex multiplet, d, e, g, h, i, f, j) 4.18 (3H, quintuplet, f)

[0146]

[Chemical formula 26]

Synthesis Example 10 Tris (4-aza-2-hydroxydecyl) was placed in a reaction vessel.
Amine 24.4 g (0.05 mol), glycolic acid 19
g (0.25 mol) and 100 ml of xylene were added, and the produced water was fractionated and refluxed for 15 hours. The reaction mixture was washed with water to remove excess glycolic acid, and the xylene layer was concentrated under reduced pressure. The residue was decolorized and purified by column chromatography (silica gel 300 g, developing solvent: chloroform / methanol = 80: 1) and tris (4-aza-2,6-dihydroxy-4-hexyl-5-oxohexyl) amine 33 g (yield Rate 99.7%).

33 g (0.05 mol) of tris (4-aza-2,6-dihydroxy-4-hexyl-5-oxohexyl) amine obtained above and 150 ml of dichloromethane were placed in a reaction vessel, and the mixture was put under a nitrogen stream. A dichloromethane solution of 10 ml (0.15 mol) of chlorosulfuric acid was gently added dropwise while cooling with ice. Then, the temperature was gradually returned to room temperature, and hydrochloric acid and dichloromethane generated by a nitrogen stream were removed. The residue was poured into water and the pH was adjusted to 7 with an aqueous sodium hydroxide solution. This aqueous solution was desalted by electrodialysis and freeze-dried to give tris (4-aza-2-hydroxy-).
4-hexyl-5-oxo-6-sulfoxyhexyl)
47.4 g (yield 98.0%) of sodium salt of amine was obtained.

¹ H-NMR (D ₂ O): δ (ppm) 0.88 (9H, triplet, a) 1.30 (18H, wide singlet, b) 1.53 (6H, wide singlet, c) 2.50 to 3.35 ( 24H, complex multiplet, d, e, g, h) 3.88 (3H, quintuplet, f)

[0150]

[Chemical 27]

Synthesis Example 11 Tris (4- (4)) obtained in the same manner as in Synthesis Example 7 was placed in a reaction vessel.
33.1 g (0.05 mol) of aza-2,6-dihydroxy-4-hexyl-5-oxohexyl) amine and 150 ml of dichloromethane were added, and 20 ml (0.3 mol) of chlorosulfuric acid was added while cooling with ice under a nitrogen stream. Of dichloromethane solution was gently added dropwise. Then, the temperature was gradually returned to room temperature, and hydrochloric acid and dichloromethane generated by a nitrogen stream were removed.

The residue was poured into water and the pH was adjusted to 7 with an aqueous sodium hydroxide solution. The aqueous solution was desalted by electrodialysis and freeze-dried to give 61.5 g of sodium salt of tris (4-aza-4-hexyl-5-oxo-2,6-disulfoxyhexyl) amine (yield 96.
5%).

¹ H-NMR (D ₂ O): δ (ppm) 0.90 (9H, triplet, a) 1.32 (18H, wide singlet, b) 1.55 (6H, wide singlet, c) 2.60 to 3.35 ( 24H, complex multiplet, d, e, g, h) 4.00 (3H, quintuplet, f)

[0154]

[Chemical 28]

Synthesis Example 12 57.2 g (0.1%) of tris (4-aza-2-hydroxydodecyl) amine was placed in an autoclave having a volume of 1 liter.
Mol) and 500 ml of xylene were added and the temperature was raised to 155 ° C., 22 g (0.5 mol) of ethylene oxide was injected, and the reaction was carried out for 6 hours while maintaining the temperature at 155 ° C. After completion of the reaction, the solvent was distilled off under reduced pressure, and tris (4-aza-2,
6-dihydroxy-4-octylhexyl) amine 70
g (yield 99%) was obtained.

In a reaction vessel, 35.2 g (0.05 mol) of tris (4-aza-2,6-dihydroxy-4-octylhexyl) amine obtained above and dichloromethane 15 were added.
Add 0 ml and chlorosulfuric acid 10 ml under nitrogen flow while cooling with ice.
A dichloromethane solution of (0.15 mol) was gently added dropwise. Then, the temperature was gradually returned to room temperature, and hydrochloric acid and dichloromethane generated by a nitrogen stream were removed. The residue was poured into water and the pH was adjusted to 7 with an aqueous sodium hydroxide solution.
This aqueous solution was desalted by electrodialysis and freeze-dried to tris (4-aza-2-hydroxy-4-octyl-).
6-Sulfoxyhexyl) amine 50.3 g (yield 9
9.6%).

¹ H-NMR (D ₂ O): δ (ppm) 0.91 (9H, triplet, a) 1.35 (30H, wide singlet, b) 1.50 (6H, wide singlet, c) 2.50 to 3.40 ( 24H, complex multiplet, d, e, g, h, i) 3.89 (3H, quintet, f)

[0158]

[Chemical 29]

Synthesis Example 13 Tris (4- (4)) obtained in the same manner as in Synthesis Example 9 was placed in a reaction vessel.
Aza-2,6-dihydroxy-4-octylhexyl)
35.2 g (0.05 mol) of amine and 150 ml of dichloromethane were added, and a dichloromethane solution of 20 ml (0.3 mol) of chlorosulfuric acid was gently 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.

The residue was poured into water and the pH was adjusted to 7 with an aqueous sodium hydroxide solution. This aqueous solution is desalted by electrodialysis and freeze-dried to tris (4-aza-4-).
65.5 g (yield 99.5%) of the sodium salt of octyl-2,6-disulfoxyhexyl) amine was obtained.

¹ H-NMR (D ₂ O): δ (ppm) 0.89 (9H, triplet, a) 1.30 (30H, wide singlet, b) 1.53 (6H, wide singlet, c) 2.65 to 3.40 ( 30H, complex multiplet, d, e, g, h, i) 3.95 (3H, quintet, f)

[0162]

Embedded image

Synthesis Example 14 Tris (4-aza-2-hydroxydodecyl) amine 28.6 g (0.05 mol), ethyl acrylate 17.4 ml (0.16 mol) and ethanol 100 were placed in a reaction vessel.
ml was added and reacted at room temperature for 2 days. The reaction mixture was dried under reduced pressure. Put the residue in a reaction vessel, ethanol / water =
Dissolve with 50 ml of 2/1 mixed solvent, and add sodium hydroxide 6
g (0.15 mol) was added, and the mixture was stirred at room temperature for 2 hours.

The reaction mixture was concentrated under reduced pressure, water was added to form an aqueous solution, and the pH was adjusted to 7. This aqueous solution is desalted by electrodialysis and freeze-dried to give tris (4-
35.6 g (yield 90.3%) of aza-2-hydroxy-4-octyl-6-carboxyhexyl) amine were obtained.

¹ H-NMR (D ₂ O): δ (ppm) 0.91 (9H, triplet, a) 1.33 (30H, wide singlet, b) 1.50 (6H, wide singlet, c) 2.30 to 3.00 ( 30H, complex multiplet, d, e, g, h, i) 3.85 (3H, quintuplet, f)

[0166]

[Chemical 31]

Synthesis Example 15 Tris (4-aza-2-hydroxydodecyl) amine 28.6 g (0.05 mol), dimethyl maleate 20.0 ml (0.16 mol) and ethanol 10 were placed in a reaction vessel.
0 ml was added and reacted at room temperature for 2 hours. The reaction mixture was dried under reduced pressure.

[0168] Put the above residue in a reaction vessel, and put in ethanol /
It was dissolved in 50 ml of a mixed solvent of water = 2/1, 12 g (0.3 mol) of sodium hydroxide was added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was concentrated under reduced pressure and water was added to adjust the pH to 7 as an aqueous solution. This aqueous solution was desalted by electrodialysis and freeze-dried to obtain 47.2 g of sodium salt of tris (4-aza-2-hydroxy-4-octyl-5,6-dicarboxyhexyl) amine (yield). 92.3%).

¹ H-NMR (D ₂ O): δ (ppm) 0.93 (9H, triplet, a) 1.35 (30H, wide singlet, b) 1.53 (6H, wide singlet, c) 2.35 to 3.20 ( 24H, complex multiplet, d, e, g, i) 3.45 (3H, complex multiplet, h) 3.90 (3H, quintuplet, f)

[0170]

Embedded image

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.

[0172]

[Table 1]

[0173]

[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 cleaning 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, and its cleaning power and finishing property were evaluated. The evaluation was performed by the following evaluation method.

(Evaluation Method of Detergency and Finishing Property) The cleaning liquid was sprayed with 2 ml of a commercially available sprayer, wiped with a dry towel, and then sensory-evaluated 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.

Finishing quality: Almost no wiping lines. Δ: Some wiping marks remain. X: Wiping lines remain.

[0179]

[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.

[0183]

[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 in a cast iron enamel tub having stains on the bath 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: Very good stain removal. 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.

[0188]

[Table 5]

Examples 11 to 15 The cleaning compositions for hard surfaces shown in Table 6 were prepared, and the cleaning power 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.

[0192]

[Table 6]

From Examples 1 to 15, the cleaning composition for hard surfaces of the present invention was prepared by using various hard materials such as glass with dirt on hands and dirt, 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.

[0194]

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.

Claims (6)

[Claims] 1. The following components (A) and (B): (A) The following general formula (1); [In the formula, R represents a linear or branched alkyl group or alkenyl group having 1 to 24 carbon atoms which may be substituted with a hydroxyl group, and A represents a hydroxyl group, a carboxyl group or a sulfonic acid group. May be a linear or branched alkylene group having 1 to 6 carbon atoms or an alkenylene group, Y ¹ is a carboxyl group, a sulfonic acid group or a sulfuric acid residue, and Y ² is a hydroxyl group, a sulfuric acid residue or a group. Represents -OCO-A-COOH, and n represents 0 or 1. ] A hard material containing one or more selected from tris (3-aminopropyl) amine derivatives represented by the following, salts or quaternary compounds thereof, (B) sequestering agents, alkaline agents and water-soluble solvents. Surface cleaning composition. 2. Y ¹ is a sulfonic acid group or a sulfuric acid residue, and Y ² is a hydroxyl group or a sulfuric acid residue.
A cleaning composition for hard surfaces according to claim 1. 3. The cleaning composition for hard surfaces according to claim 1, wherein Y ¹ is a carboxyl group and Y ² is a hydroxyl group or -OCO-A-COOH. 4. The cleaning composition for hard surfaces according to claim 1, wherein R 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.