WO2014203642A1

WO2014203642A1 - Cleaning agent composition

Info

Publication number: WO2014203642A1
Application number: PCT/JP2014/062411
Authority: WO
Inventors: 将基森田; 紗菜伊藤; 健黒瀬; 薫朝日
Original assignee: 株式会社ニイタカ
Priority date: 2013-06-18
Filing date: 2014-05-08
Publication date: 2014-12-24
Also published as: CN105339479A; KR20160020413A; PH12015502791A1; JPWO2014203642A1

Abstract

This cleaning agent composition is characterized by containing the following (A) and (B) components: (A) a nonionic surfactant having a structure represented by general formula (1) on an end thereof; and (B) a chlorine agent contained in the amount of 4 wt% or more (pure content) of the 100 wt% of the cleaning agent composition. (In the formula, R¹ represents a hydrogen atom or an alkyl group, R² and R³ represent hydrocarbon groups which may contain an ether bond and may form a ring, AO represents an oxyalkylene group which may be identical or different, and n represents the average number of added moles of the oxyalkylene group, and is a number between 1 and 400, inclusive.)

Description

Cleaning composition

The present invention relates to a cleaning composition.

A cleaning agent composition for an automatic dishwasher may be mixed with a chlorine agent for the purpose of bleaching or sterilizing dirt. As the chlorinating agent, a salt such as dichloroisocyanuric acid (including an aqueous solution containing the above salt) that can generate hypochlorous acid or chlorous acid is known.

It is known that when both a nonionic surfactant and a chlorine agent are present in the cleaning composition, both react to deactivate both the nonionic surfactant and the chlorine agent. Therefore, it is common that the nonionic surfactant and the chlorinating agent are not allowed to coexist.

Patent Document 1 discloses a blocked polyalkylene oxide block copolymer nonionic surfactant that does not contain a functional group susceptible to oxidation by a chlorine agent (hypochlorite bleach).

JP-A-2-43299

Patent Document 1 discloses a nonionic surfactant having a structure that does not contain a hydroxyl group at the terminal by blocking the alkylene oxide terminal with a methyl group. It is described that this nonionic surfactant is more stable in the presence of a chlorinating agent than an unblocked parent molecule.

Patent Document 1 discloses a method of reacting a potassium potassium salt of polyol with dimethyl sulfate in the presence of sodium hydroxide as a method for blocking the alkylene oxide terminal with methyl.

The present inventors evaluated the chlorine stability by mixing a terminal methyl-blocked nonionic surfactant obtained by the reaction described in Patent Document 1 with a chlorine agent. Then, although its chlorine stability is higher than that of a nonionic surfactant whose end is not blocked, it is not sufficient, and a part of the nonionic surfactant and the chlorine agent react and decompose. There was found.
The present inventors have obtained that the terminal methyl-blocked nonionic surfactant is obtained by a substitution reaction between a hydroxyl group and a methyl group, so that all of the hydroxyl groups are not substituted with methyl groups, and some of them are hydroxyl groups. It was assumed that the chlorine stability was insufficient due to the residual groups.
In addition, it is desirable not to use dimethyl sulfate because it is a very dangerous compound, and it was considered necessary to have a safer method for blocking the end of alkylene oxide.
Further, the above-described reaction using dimethyl sulfate has a problem that purification is required because a by-product is generated by the substitution reaction.
As described above, in the detergent composition containing both the nonionic surfactant and the chlorine agent, the chlorine concentration is low because the chlorine stability is poor even if the bleaching property and the bactericidal property are improved by blending many chlorine agents. There was a problem that a cleaning composition having the expected bleaching and bactericidal properties could not be obtained.

The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a cleaning composition having high chlorine stability, containing a chlorine agent and a nonionic surfactant. .

As a result of intensive studies on the structure of a nonionic surfactant having higher chlorine stability, the present inventors have found that a nonionic surfactant having an acetal structure containing an oxygen atom at the end of an alkylene oxide at its end is particularly The inventors have found that it exhibits high chlorine stability in neutral and alkaline environments, and have arrived at the present invention.

That is, the cleaning composition of the present invention is characterized by containing the following components (A) and (B).
(A) Nonionic surfactant having a structure represented by the general formula (1) at the terminal (B) Chlorine agent of 4% by weight or more in a pure content with respect to 100% by weight of the detergent composition

(Wherein R ¹ is a hydrogen atom or an alkyl group, R ² and R ³ are hydrocarbon groups that may contain an ether bond, R ² and R ³ may form a ring, and AO is the same Or an oxyalkylene group which may be different, and n represents the average number of added moles of the oxyalkylene group and is a number of 1 to 400.)

The nonionic surfactant (A) has an acetal structure (AO—C (R ¹ ) (R ² ) —O—R ³ ) containing an oxygen atom at the end of the alkylene oxide at its terminal.
One of the two oxygen atoms constituting the acetal structure is an oxygen atom derived from a hydroxyl group present at the end of the alkylene oxide.
The acetal structure is unstable under acidic conditions and generates a hydroxyl group, but is stable under neutral and alkaline conditions. Also, the acetal structure does not react with chlorinating agents. Therefore, in the cleaning composition of the present invention, the concentration of the chlorinating agent (effective chlorine concentration) is unlikely to decrease, and high chlorine stability can be exhibited in neutral and alkaline environments.
As a result, it is possible to obtain a cleaning composition having high bleaching and bactericidal properties by containing 4% by weight or more of pure chlorine in 100% by weight of the cleaning composition.

In addition, the acetal structure in this specification is a concept including both an acetal in which R ¹ is a hydrogen atom and a ketal in which R ¹ is an alkyl group.

Moreover, foaming is reduced by having a structure in which the terminal is blocked so that the hydroxyl group at the terminal of the alkylene oxide does not remain. Surfactants with low foaming are suitable for use in detergents for automatic dishwashers.

In the cleaning composition of the present invention, it is desirable that the content of the chlorinating agent is the same as or greater than the content of the nonionic surfactant.
In the cleaning composition of the present invention, the ratio of the content of the chlorine agent to the content of the nonionic surfactant is chlorine agent / nonionic surfactant = 1-100. desirable.

In the cleaning composition of the present invention, it is desirable that the nonionic surfactant has a structure represented by the general formula (2) at the terminal.

(Where m is an integer of 3 or more)

In the cleaning composition of the present invention, it is desirable that the nonionic surfactant has a structure represented by the general formula (3) at the terminal.

In the cleaning composition of the present invention, it is desirable that the nonionic surfactant has a structure represented by the general formula (4) at the terminal.

(In the formula, X is an alcohol residue or an alkylphenol residue.)

In the cleaning composition of the present invention, the chlorinating agent is sodium chlorinated isocyanurate, potassium chlorinated isocyanurate, trichloroisocyanuric acid, sodium hypochlorite, calcium hypochlorite and hypochlorous acid. It is desirable that it is at least one selected from the group consisting of potassium.

It is desirable that the cleaning composition of the present invention further contains (C) an alkaline agent.
By blending an alkali agent, a detergent composition having a high detergency can be obtained.
Moreover, the nonionic surfactant (A) mix | blended with the cleaning composition of this invention is stable under alkalinity.
Under alkalinity, when a hydroxyl group is present at the end of the nonionic surfactant, the hydroxyl group tends to be oxidized and anionized to increase foaming properties. The acetal structure possessed by the nonionic surfactant (A) is stable even under alkalinity, and since it is anionized and does not increase foaming properties, the cleaning composition of the present invention can be used even under alkalinity. It has an advantageous effect that the foamability can be kept low.
In addition, if a hydroxyl group is present at the end of the alkylene oxide of the nonionic surfactant (A), the hydroxyl group may be oxidized under the alkalinity to become a carboxyl group and discoloration may occur, but the end may have an acetal structure. If this is the case, this reaction does not occur, so discoloration is suppressed.

In the cleaning composition of the present invention, the alkaline agent is at least selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium orthosilicate, potassium orthosilicate, sodium metasilicate, potassium metasilicate and hydrates thereof. One type is desirable.
These alkali agents are particularly suitable for making a cleaning composition suitable for cleaning oily soil.

In the cleaning composition of the present invention, the nonionic surfactant undergoes an addition reaction with respect to the hydroxyl group at the end of the alkylene oxide of the nonionic surfactant having a structure represented by the general formula (5) at the end. It is desirable to be manufactured by providing the terminal with an acetal structure represented by the general formula (1).

The acetal structure can be generated by an addition reaction to the hydroxyl group at the end of the alkylene oxide, but since this addition reaction has a high reaction rate, the end can be blocked so that the hydroxyl group at the end of the alkylene oxide does not remain.
Further, no by-product is generated.
Therefore, it is unlikely that the surfactant contained in the cleaning composition contains a hydroxyl group at the end, and chlorine stability can be reliably ensured.

In the cleaning composition of the present invention, the addition reaction is desirably a reaction for adding dihydropyran to a hydroxyl group under an acid catalyst.

The cleaning composition of the present invention can exhibit both the cleaning effect by the surfactant and the bleaching and bactericidal effects by the chlorine agent.
Moreover, the cleaning composition of the present invention has less foaming and is suitable for use in a cleaning agent for automatic dishwashers.

FIG. 1 is a graph showing the change over time in the effective chlorine residual rate in the chlorine stability tests of Examples 5 and 6 and Comparative Example 3. FIG. 2 is a graph showing the change over time in the effective chlorine residual ratio in the chlorine stability test of Example 7 and Comparative Example 4.

The cleaning composition of the present invention comprises the following components (A) and (B).
(A) Nonionic surfactant having a structure represented by the general formula (1) at the terminal (B) Chlorine agent of 4% by weight or more in a pure content with respect to 100% by weight of the detergent composition

The structure represented by the general formula (1) is an acetal structure.
The acetal structure is a structure that is used as a protecting group for a hydroxyl group. By making the hydroxyl group terminal an acetal structure, deactivation of the chlorine agent due to the reaction of the hydroxyl group with the chlorine agent can be prevented.

The acetal structure can be generated by an addition reaction to the hydroxyl group at the alkylene oxide terminal. Since this addition reaction has a high reaction rate, the end can be blocked so that the hydroxyl group at the end of the alkylene oxide does not remain.
That is, the nonionic surfactant (A) having a hydroxyl group end blocked with an acetal structure is compared with a surfactant having a hydroxyl group end blocked with another protecting group (such as a methyl group) by a substitution reaction. It can be said that it is advantageous for exhibiting the effect of “high chlorine stability when coexisting with a chlorine agent”.
In addition, the acetal structure has a feature that it is highly stable in an alkaline environment. Therefore, compared with a surfactant in which the hydroxyl group end is blocked with another protecting group such as a benzyl group or an acetyl group, the acetal structure is more effective in an alkaline environment. It can be said that it is advantageous to exhibit the effect of “low foaming property”.

R ² in the general formula (1) is a hydrocarbon group that may contain an ether bond. R ² may be an alkylene group consisting only of carbon and hydrogen, or may be an alkylene group containing an ether bond.
Further, R ² itself may contain a cyclic structure, and examples of the cyclic structure include a cyclohexane ring, a benzene ring, a naphthalene ring and the like.
When R ² itself contains a cyclic structure, R ² and R ³ may form a ring so that the terminal of the structure represented by the general formula (1) may be a condensed ring.

A desirable structure as an acetal structure contained in the general formula (1) is a structure represented by the following general formula (2).

(Where m is an integer of 3 or more)
The structure represented by the general formula (2) is a structure in which R ² and R ³ form a ring in the general formula (1).

Moreover, among the structures included in the general formula (2), it is desirable that the terminal has a structure represented by the general formula (3).

The structure represented by the general formula (3) is a structure in which m is 4 in the general formula (2).
Further, among the structures represented by the general formula (3), a more desirable structure is a structure (tetrahydropyranyl ether) in which R ¹ is H.
Tetrahydropyranyl ether is preferable because it is highly stable in neutral and alkaline environments, and dihydropyran as a raw material for the acetal structure is inexpensive and easily available.
As will be described later, this structure can be obtained by adding dihydropyran to a hydroxyl group under an acid catalyst.
In the present specification, dihydropyran means 3,4-dihydro-2H-pyran (DHP) represented by the following formula (6).

As the acetal structure represented by the general formula (1), in addition to the structures having the rings represented by the general formulas (2) and (3), the following formulas (7), (8), ( The structure represented by 9) is also included.

The structure represented by the formula (7) can be obtained by adding 2,3-dihydro-1,4-dioxin represented by the following formula (10) to the hydroxyl group under an acid catalyst.

The structure represented by the formula (8) can be obtained by adding 2,3-dihydrofuran represented by the following formula (11) to a hydroxyl group under an acid catalyst.

The structure represented by the formula (9) is an example of a structure in which, in the general formula (1), R ² includes a cyclic structure in R ² itself, and the terminal of the structure represented by the general formula (1) is a condensed ring. It is.
This structure can be obtained by adding 2,3-benzofuran represented by the following formula (12) to a hydroxyl group under an acid catalyst.

Examples of the acetal structure represented by the general formula (1) include a structure having no ring in addition to a structure having a ring.
A desirable structure when the acetal structure included in the general formula (1) does not have a ring is a structure in which R ¹ in the general formula (1) is an alkyl group.
R ¹ is not particularly limited as long as it is a linear or branched alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

R ² and R ³ in the general formula (1) are not particularly limited as long as R ¹ is a hydrocarbon group, regardless of whether or not R ¹ is an alkyl group, and are linear or branched alkyl groups. , Cyclic hydrocarbon groups, aromatic hydrocarbon groups and the like.
Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, and a benzyl group.
R ² and R ³ may be a hydrocarbon group containing an ether bond.

Moreover, among the structures in which R ¹ is an alkyl group in the general formula (1), it is particularly desirable that the terminal has a structure represented by the following general formula (13).

The structure represented by the general formula (13) is a structure in which R ¹ and R ² are both methyl groups and R ³ is an ethyl group in the general formula (1).

The structure represented by the general formula (13) has a 2-ethoxypropyl group at the end, and can be obtained by adding 2-ethoxypropene to a hydroxyl group under an acid catalyst.

Examples of other specific structures include structures represented by the following general formulas (14) to (19).

The structure represented by the general formula (14) is a structure in which R ¹ is a methyl group, R ² is an ethyl group, and R ³ is a methyl group in the general formula (1).
The above structure is obtained by adding 2-methoxy-1-butene to a hydroxyl group under an acid catalyst.

The structure represented by the general formula (15) is a structure in which R ¹ is a methyl group, R ² is a pentyl group, and R ³ is a methyl group in the general formula (1).
The above structure is obtained by adding 2-methoxy-1-heptene to a hydroxyl group under an acid catalyst.

The structure represented by the general formula (16) is a structure in which R ¹ is a methyl group, R ² is a methyl group, and R ³ is a cyclohexyl group in the general formula (1).
The above structure can be obtained by adding 2-cyclohexyloxy-1-propene to a hydroxyl group under an acid catalyst.

The structure represented by the general formula (17) is a structure in which R ¹ is a methyl group, R ² is a methyl group, and R ³ is a phenyl group in the general formula (1).
The above structure is obtained by adding 2-phenoxy-1-propene to a hydroxyl group under an acid catalyst.

The structure represented by the general formula (18) is a structure in which R ¹ , R ² , and R ³ are all methyl groups in the general formula (1).
The above structure is obtained by adding 2-methoxypropene to a hydroxyl group under an acid catalyst.

The structure represented by the general formula (19) is a structure in which R ¹ and R ² are both methyl groups and R ³ is a benzyl group in the general formula (1).
The above structure can be obtained by adding benzylisopropenyl ether to a hydroxyl group under an acid catalyst.

Moreover, among the structures included in the general formula (1), it is desirable that the terminal has a structure represented by the general formula (20).

The structure represented by the general formula (20) is a structure in which R ¹ is a hydrogen atom, R ² is a methyl group, and R ³ is an ethyl group in the general formula (1).

The structure represented by the general formula (20) has an ethoxyethyl group at the end, and can be obtained by adding ethyl vinyl ether to a hydroxyl group under an acid catalyst.

Examples of AO (oxyalkylene group) include oxyethylene group (EO), oxypropylene group (PO), and oxybutylene group. The nonionic surfactant (A) may contain only one type of oxyethylene group, oxypropylene group, or oxybutylene group, and a plurality of types thereof are included. Also good. The unit of the repeating structure of the oxyethylene group, oxypropylene group, or oxybutylene group is not particularly limited.

The average added mole number n of AO in the nonionic surfactant (A) is 1 to 400, the preferred lower limit value of n is 3, more preferred lower limit value is 5, and the preferred upper limit value is 100, more preferred. The upper limit value is 50, the more preferable upper limit value is 30, and the still more preferable upper limit value is 15.
Preferable examples of the range of n are 3 to 100, 5 to 50, 3 to 30, or 5 to 15.
Usually, the nonionic surfactant (A) is a mixture of a plurality of compounds having different addition mole numbers n of AO. Although the added mole number of AO contained in each molecule of the nonionic surfactant (A) is an integer value, the measured value when the added mole number of AO is measured is that of the nonionic surfactant (A). Since it is measured as the average value of the number of moles of AO contained in each molecule, this is the average number of moles added.
Further, the nonionic surfactant (A) may be a mixture of a plurality of compounds having different types of AO.

The nonionic surfactant (A) is characterized by having an acetal structure represented by the general formula (1) at the terminal, and the structure of the whole nonionic surfactant is represented by the following general formula (4). It is desirable to have the structure shown by these.

(X is an alcohol residue or an alkylphenol residue.)

Among X in the general formula (4), preferred specific examples of the alcohol residue include octyl alcohol residue, 2-ethylhexyl alcohol residue, decyl alcohol residue, isodecyl alcohol residue, lauryl. Residue of alcohol, residue of dodecyl alcohol, residue of tridecyl alcohol, residue of myristyl alcohol, residue of tetradecyl alcohol, residue of pentadecyl alcohol, residue of cetyl alcohol, residue of hexadecyl alcohol , Isohexadecyl alcohol residue, heptadecyl alcohol residue, stearyl alcohol residue, octadecyl alcohol residue, isostearyl alcohol residue, elaidyl alcohol residue, oleyl alcohol residue, linoleyl Residue of alcohol, Elide Linoleil Resol residue, linolenyl alcohol residue, elide linolenyl alcohol residue, ricinoleyl alcohol residue, nonadecyl alcohol residue, arachidyl alcohol (eicosanol) residue, octyldodecyl alcohol Residue, heneicosanol residue, behenyl alcohol (1-docosanol) residue, erucyl alcohol residue, tricosanol residue, lignoceryl alcohol (1-tetracosanol) residue, pentacososa Residue of anol, residue of seryl alcohol, residue of 1-heptacosanol, residue of montanyl alcohol (1-octacosanol), residue of 1-nonacosanol, residue of myricyl alcohol (1-triacontanol) 1-Hentriacontanol residue, 1-Dotriacontanol residue, Residues such as the benzyl alcohol (1-tetra-triacontanol) and the like.
Preferable specific examples of the alkylphenol residue include nonylphenol residue, dodecylphenol residue, octylphenol residue, octylcresol residue and the like.
The nonionic surfactant (A) may be a compound having only one of these residues as X, or may be a mixture of a plurality of compounds having different X.

In addition, the nonionic surfactant (A) may have an acetal structure at both ends, and may have a structure represented by the following general formula (21).

(Wherein R ¹ and R ⁴ are a hydrogen atom or an alkyl group, R ² , R ³ , R ⁵ and R ⁶ are hydrocarbon groups which may contain an ether bond, R ² and R ³ , R ⁵ and R Each of ⁶ may form a ring, AO is an oxyalkylene group which may be the same or different, and n represents the average number of added moles of the oxyalkylene group and is a number from 1 to 400. )

A nonionic surfactant having an acetal structure at both ends can be obtained by acetalizing the hydroxyl group of (poly) alkylene glycol having hydroxyl groups at both ends of the molecule.
Examples of the (poly) alkylene glycol include polyethylene glycol in which AO is an oxyethylene group, and polypropylene glycol in which AO is an oxypropylene group. Further, AO has a structure of HO— (PO) _o1- (EO) _p1- (PO) _q1 —H (where o1, p1 and q1 are integers of 1 or more) (for example, Pluronic (BASF Japan) Co., Ltd.), HO- (EO) _o2- (PO) _p2- (EO) _q2 -H (where o2, p2 and q2 are integers of 1 or more) (for example, Braunon ( Aoki Yushi Kogyo Co., Ltd.)) and the like.
The average added mole number n of AO as a (poly) alkylene glycol having hydroxyl groups at both ends of the molecule is 1 to 400, preferably n is 3 to 300, and n is 5 to 200. Is more preferable.

Specific examples of the surfactant having the structure represented by the general formula (21) include a structure represented by the following formula (22) in which both ends are tetrahydropyranyl ethers.

This structure is obtained by adding 2 mol of dihydropyran to 1 mol of a surfactant having hydroxyl groups at both ends, such as polyethylene glycol.
Other specific examples of the surfactant having the structure represented by the general formula (21) include a structure in which both ends are dioxanyl groups (see general formula (7)), and both ends are tetrahydrofuranyl ether (general formula (8)), a structure in which both ends are 2-ethoxyethyl groups (see general formula (20)), a structure in which both ends are 2-ethoxypropyl groups (see general formula (13)), etc. Can be mentioned.

Hereinafter, the manufacturing method of a nonionic surfactant (A) is demonstrated.
First, a nonionic surfactant having a structure represented by the following general formula (5) is prepared as a starting material.

As the nonionic surfactant having the structure represented by the general formula (5), a commercially available surfactant can be used. For example, the product name “Emarumin” (manufactured by Sanyo Chemical Industries), the product name “Wonder Surf” (manufactured by Aoki Yushi Kogyo Co., Ltd.), the product name “Brownon” (manufactured by Aoki Yushi Kogyo Co., Ltd.), and the product name “Fine Surf” (Aoki Oil & Fats Co., Ltd.), trade name "Adecanol" (made by ADEKA), trade name "Pull la fuck" "Pluronic" (made by BASF Japan), trade name "Neugen" (Daiichi Kogyo Seiyaku Co., Ltd.) Product name), “Peletex” (manufactured by Miyoshi Oil & Fat Co., Ltd.) and the like.

The hydroxyl group is blocked by performing an addition reaction on the hydroxyl group at the end of the alkylene oxide of the nonionic surfactant to obtain an acetal structure represented by the general formula (1).
The specific procedure of the addition reaction varies depending on the acetal structure obtained by addition reaction to the hydroxyl group. For example, the structure represented by the general formula (3) and R ¹ is H (tetrahydropyranyl ether) It can be obtained by reacting dihydropyran (DHP) at the hydroxyl group terminal of the surfactant with an acid catalyst in an organic solvent.

Examples of the acid catalyst include p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, pyridinium p-toluenesulfonate, trifluoromethanesulfonic acid, sulfuric acid, hydrochloric acid, and an acidic ion exchange resin. Of these, p-toluenesulfonic acid is desirable because it is easy to handle and inexpensive.

As the organic solvent used in the above reaction, a general organic solvent can be used, and methylene chloride, chloroform, acetonitrile, tetrahydrofuran (THF), toluene, chlorobenzene, methyl tert-butyl ether and the like can be used.

The reaction is completed by neutralization of the acid catalyst. Although it does not specifically limit as a base used for neutralization, Powder, such as sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, or those solutions etc. can be used.

The reaction conditions can be appropriately determined depending on the type and amount of the starting material. For example, when reacting 60 to 70 g of polyoxyethylene lauryl ether as a nonionic surfactant in 25 to 100 ml of methylene chloride solution, Dihydropyran sufficient to react with all hydroxyl groups of ethylene lauryl ether (1-10 times molar ratio to polyoxyethylene lauryl ether) and 1-10 mol% p-toluenesulfonic acid as acid catalyst After stirring at room temperature for 0.5 hours to overnight (10 hours), sodium bicarbonate is added to terminate the reaction, and after filtration, the solvent and unreacted dihydropyran are distilled off. It is done.

The concentration of the nonionic surfactant (A) in the cleaning composition of the present invention is not particularly limited, but is preferably 0.1 to 40% by weight, and preferably 0.5 to 25% by weight. % Is more desirable, and 0.5 to 10% by weight is even more desirable.

The cleaning composition of the present invention contains a chlorine agent (B). Examples of the chlorine agent (B) include chlorinated isocyanurates (chlorinated isocyanurate sodium, chlorinated isocyanurate potassium, etc. ), Trichloroisocyanuric acid, hypochlorite (sodium hypochlorite, potassium hypochlorite, calcium hypochlorite, etc.).
Moreover, 1 type in these chlorine agents may be used, and 2 or more types may be used together.
Since the nonionic surfactant (A) contained in the cleaning composition of the present invention does not have a hydroxyl group at its end and has an acetal structure, the acetal structure does not react with the chlorine agent (B). Inactivation of the chlorine agent (B) in the cleaning composition is prevented.
The concentration of the chlorine agent in the cleaning composition is 4% by weight or more in 100% by weight of the cleaning composition, and the cleaning composition having such a high concentration of chlorine has high bleaching. And bactericidal properties.
The upper limit of the concentration of the chlorinating agent is desirably 50% by weight, and more desirably 30% by weight.
When a plurality of types of chlorinating agents are used, the concentration of the chlorinating agent is determined as a total value of the concentration of each chlorinating agent.
In addition, it is desirable that the content of the chlorinating agent (B) with respect to the content of the nonionic surfactant (A) is the same or greater, and the ratio of the content of the chlorinating agent to the content of the nonionic surfactant is The chlorine agent / nonionic surfactant is preferably 1 to 100, more preferably 1 to 20, and further preferably 1 to 6.
A detergent composition containing a relatively large amount of chlorine agent can exhibit high bleaching and bactericidal properties.

As the alkali agent (C), an alkali metal or alkaline earth metal salt can be used, and the kind thereof is not particularly limited, but sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, hydrogen carbonate. Sodium, potassium hydrogen carbonate, sodium metasilicate, sodium sesquisilicate, sodium orthosilicate, potassium metasilicate, potassium sesquisilicate, potassium orthosilicate and the like are desirable.
These alkaline agents may be hydrated.
Among these, at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium orthosilicate, potassium orthosilicate, sodium metasilicate, potassium metasilicate, and hydrates thereof is desirable. When these alkali agents are used, an alkali cleaner having a high detergency can be obtained.
Moreover, 1 type in these alkaline agents may be used and 2 or more types may be used together.
The concentration of the alkaline agent (C) in the cleaning composition of the present invention is not particularly limited, but is preferably 2 to 95% by weight, more preferably 30 to 95% by weight, More desirably, it is 45 to 95% by weight.
When a plurality of types of alkali agents are used, the concentration of the alkali agent is determined as a total value of the concentrations of the respective alkali agents.

The pH of the detergent composition of the present invention is not particularly limited, but from the viewpoint of the stability of the terminal acetal structure of the nonionic surfactant (A), it may be in a neutral to alkaline range. desirable.
In the case of a neutral detergent composition, the pH is desirably 6 or more and less than 9, and in the case of a weakly alkaline detergent composition, the pH is desirably 9 or more and less than 12, and is strongly alkaline. When it is set as a cleaning composition, it is desirable that pH is 12 or more.
The pH may be measured using a commercially available pH meter or the like. For example, the pH can be measured using a model D-21 manufactured by Horiba, Ltd.

In the cleaning composition of the present invention, the nonionic surfactant and the chlorine agent coexist stably in the above liquid state, so that both the cleaning effect by the nonionic surfactant, the bleaching by the chlorine agent, and the bactericidal effect are exhibited. Can be made. In addition, a cleaning composition that is made alkaline by adding an alkali agent can further exert a cleaning effect on oil stains and the like due to the alkali agent.

The detergent composition of the present invention is blended in a detergent composition such as a polymer dispersant (D), a chelating agent (E), a solvent / process agent (F), a solubilizer (G), etc., as necessary. Other components may be contained. Moreover, you may contain surfactant other than nonionic surfactant (A).
Examples of the polymer dispersant (D) include polyacrylic acid, polyaconitic acid, polyitaconic acid, polycitraconic acid, polyfumaric acid, polymaleic acid, polymethaconic acid, poly-α-hydroxyacrylic acid, polyvinylphosphonic acid, and sulfonated polymaleic acid. Olefin-maleic acid copolymer, maleic anhydride diisobutylene copolymer, maleic anhydride styrene copolymer, maleic anhydride methyl vinyl ether copolymer, maleic anhydride ethylene copolymer, maleic anhydride ethylene crosslink copolymer Polymer, maleic anhydride acrylic acid copolymer, maleic anhydride vinyl acetate copolymer, maleic anhydride acrylonitrile copolymer, maleic anhydride acrylic ester copolymer, maleic anhydride butadiene copolymer, maleic anhydride Isoprene copolymer, anhydrous Poly-β-ketocarboxylic acid, itaconic acid, ethylene copolymer, itaconic acid aconitic acid copolymer, itaconic acid maleic acid copolymer, itaconic acid acrylic acid copolymer, malon derived from rain acid and carbon monoxide Examples include methylene acid copolymer, itaconic acid fumaric acid copolymer, ethylene glycol ethylene terephthalate copolymer, vinyl pyrrolidone vinyl acetate copolymer, and metal salts thereof. Of these, sodium polyacrylate (average molecular weight Mw = 3,000 to 30,000), polymaleic acid-sodium acrylate, olefin-sodium maleate copolymer, etc. are preferably used from the viewpoint of cost and economy. It is done.
Examples of the chelating agent (E) include ethylenediaminetetraacetic acid (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), 2-phosphonobutane-1,2,4-tricarboxylic acid, Ethylenediaminesuccinic acid (EDDS), hydroxyethyliminodiacetic acid (HIDA), glutamic acid diacetic acid (GLDA), methylglycine diacetic acid (MGDA), aspartic acid diacetic acid (ASDA), tripolyphosphoric acid, polyacrylic acid and their salts ( Sodium salts, potassium salts, etc.), polyaspartic acid compounds represented by the following formula (23), iminodisuccinic acid compounds represented by the following formula (24), iminodiacetic acid represented by the following formula (25) System compounds.

[In Formula (23), M is the same or different and is —H, —Na, —K or —NH ₄ . s and t are integers]

[In formula (24), M is the same or different and is —H, —Na, —K or —NH ₄ . ]

[In formula (25), M is the same or different and is —H, —Na, —K or —NH ₄ . ]

The concentration of the chelating agent in the cleaning composition is not particularly limited, but is preferably 0 to 80% by weight, more preferably 0 to 70% by weight, and 15 to 50% by weight. More desirably.
Examples of the solvent (F) include water and commonly used organic solvents. The process agent (F) is an extender when the dosage form is solid, and preferably has a neutral pH, and examples thereof include sodium sulfate (sodium salt), powdered silica, and 12-hydroxystearic acid.
Examples of the solubilizer (G) include xylene sulfonic acid, cumene sulfonic acid, caprylic acid, octylic acid and salts thereof, alkyl diphenyl ether disulfonate, and the like.

The dosage form of the cleaning composition of the present invention may be either liquid or solid (tablet, powder, etc.) and is not limited to liquid.
When the cleaning composition is solid and the pH of the cleaning composition cannot be measured directly, the pH of the cleaning composition is a state where 10 g of the cleaning composition is mixed with 90 g of water (the concentration of the cleaning composition). Is 10% by weight).

Examples for more specifically explaining the present invention are shown below, but the present invention is not limited to these examples.

(Production Example 1) Production of (A-1) As a nonionic surfactant, a polyoxyalkylene alkyl ether having 1 to 400 oxyalkylene groups and having a hydroxyl group at the end of alkylene oxide (Co., Ltd.) 20 g of dihydropyran (DHP) and 1 mol% of paratoluenesulfonic acid as a catalyst were added to a solution of ADEKA, Adecanol B722 (140 g) in methylene chloride (50 ml), and the mixture was stirred overnight (10 hours) at room temperature. . Sodium bicarbonate was added to terminate the reaction, and after filtration, the solvent and unreacted dihydropyran were distilled off to obtain the desired product.
The obtained product is a nonionic surfactant (A-1) having an acetal structure at the end, which is obtained by reacting the hydroxyl group at the end of the nonionic surfactant with DHP.

(Production Example 2) Production of (A-2) As a nonionic surfactant, a polyoxyalkylene alkyl ether having 1 to 400 oxyalkylene groups and having a hydroxyl group at the end of alkylene oxide (Co., Ltd.) To a methylene chloride solution (50 ml) of ADEKA, Adecanol BO-922) (110 g), 18 g of ethyl vinyl ether and 1 mol% of paratoluenesulfonic acid as a catalyst were added, and the mixture was stirred overnight (10 hours) at room temperature. Sodium bicarbonate was added to terminate the reaction, and after filtration, the solvent and unreacted ethyl vinyl ether were distilled off to obtain the desired product.
The obtained product is a nonionic surfactant (A-2) having an acetal structure at the terminal, which is obtained by reacting the hydroxyl group at the terminal of the nonionic surfactant with ethyl vinyl ether.

(Production Example 3) Production of (A-3) As a nonionic surfactant, a polyoxyalkylene alkyl ether having 1 to 400 oxyalkylene groups and having a hydroxyl group at the end of alkylene oxide (Co., Ltd.) 17 g of 2,3-dihydrofuran and 1 mol% of p-toluenesulfonic acid as a catalyst were added to a solution of ADEKA, Adecanol B-2020 (300 g) in methylene chloride (50 ml), and overnight (10 hours) at room temperature. And stirred. Sodium hydrogencarbonate was added to terminate the reaction, and after filtration, the solvent and unreacted 2,3-dihydrofuran were distilled off to obtain the desired product.
The obtained product is a nonionic surfactant (A-3) having an acetal structure at the terminal, which is obtained by reacting the terminal hydroxyl group of the nonionic surfactant with 2,3-dihydrofuran. is there.

(Production Example 4) Production of (A-4) As a nonionic surfactant, a polyoxyalkylene alkyl ether having 1 to 400 oxyalkylene groups and having a hydroxyl group at the end of alkylene oxide (Co., Ltd.) 21 g of 2,3-dihydro-1,4-dioxin and 1 mol% of p-toluenesulfonic acid as a catalyst were added to a solution of ADEKA, Adecanol B-2030) (280 g) in methylene chloride (50 ml), and overnight (10 Time) and stirred at room temperature. Sodium bicarbonate was added to terminate the reaction, and after filtration, the solvent and unreacted 2,3-dihydro-1,4-dioxin were distilled off to obtain the desired product.
The resulting product is a nonionic surfactant having an acetal structure at the end (reaction of a hydroxyl group at the end of the nonionic surfactant with 2,3-dihydro-1,4-dioxin ( A-4).

(Production Example 5) Production of (A-5) As a nonionic surfactant, a polyoxyalkylene alkyl ether having a oxyalkylene group in the range of 1 to 400 and having a hydroxyl group at the end of alkylene oxide (first To 20 ml of dihydropyran (DHP) and 1 mol% of p-toluenesulfonic acid as a catalyst were added to a methylene chloride solution (50 ml) of Neugen XL-40) (100 g) manufactured by Kogyo Seiyaku Co., Ltd. overnight (10 hours). Stir at room temperature. Sodium bicarbonate was added to terminate the reaction, and after filtration, the solvent and unreacted dihydropyran were distilled off to obtain the desired product.
The resulting product is a nonionic surfactant (A-5) having an acetal structure at the end, which is obtained by reacting the hydroxyl group at the end of the nonionic surfactant with DHP.

(Production Example 6) Production of (A-6) As a nonionic surfactant, 80 g of a polyalkylene glycol having hydroxyl groups at both ends of the molecule (trade name: Pluronic RPE 2520) was prepared. 10 g of ethyl vinyl ether and 1 mol% of p-toluenesulfonic acid as a catalyst were added to the solution (50 ml), and the mixture was stirred overnight (10 hours) at room temperature. Sodium bicarbonate was added to terminate the reaction, and after filtration, the solvent and unreacted ethyl vinyl ether were distilled off to obtain the desired product.
The obtained target product is a nonionic surfactant (A-6) having an acetal structure at both molecular ends obtained by reacting hydroxyl groups at both molecular ends of the polyalkylene glycol with ethyl vinyl ether. .
Pluronic RPE 2520 has a structure in which AO is HO— (PO) _o3 — (EO) _p3 — (PO) _q3 —H (o3, p3 and q3 are integers of 1 or more), and EO and PO Is a polyalkylene glycol having a molar ratio of EO: PO = 2: 8.

(Production Example 7) (A-7)
In Production Example 6, instead of polyalkylene glycol (trade name: Pluronic RPE 2520), another polyalkylene glycol (trade name: Blaunon P 174) was used instead of ethyl vinyl ether, except that DHP was used. The expected product is obtained.
The obtained target product is a nonionic surfactant (A-7) having an acetal structure at both molecular ends obtained by reacting hydroxyl groups at both molecular ends of the polyalkylene glycol with DHP.
Incidentally, BLAUNON P 174 is, AO is _{_{HO- (EO) o7 - (PO}} ) p7 - (EO) q7 has the structure of -H (o7, p7 and q7 is an integer of 1 or more), EO and PO Is a polyalkylene glycol having a molar ratio of EO: PO = 4: 6.

(Comparative Production Examples 1 to 5)
The following surfactants were prepared as surfactants used in the evaluation test described below.
(Comparative Production Example 1) Surfactant (A'-1)
A polyoxyalkylene alkyl ether having an oxyalkylene group in the range of 1 to 400 and having a hydroxyl group at the end of the alkylene oxide (manufactured by ADEKA Corporation, Adecanol B722).
(Comparative Production Example 2) Surfactant (A'-2)
A polyoxyalkylene alkyl ether having an oxyalkylene group in the range of 1 to 400 and having a hydroxyl group at the end of the alkylene oxide (manufactured by ADEKA Corporation, Adecanol BO922).
(Comparative Production Example 3) Surfactant (A'-5)
Polyoxyalkylene alkyl ether having 1 to 400 oxyalkylene groups and having a hydroxyl group at the end of alkylene oxide (Daiichi Kogyo Seiyaku Co., Ltd., Neugen XL-40).
(Comparative Production Example 4) Surfactant (A'-6)
As a nonionic surfactant, polyalkylene glycol having a hydroxyl group at both molecular ends (trade name: Pluronic RPE 2520).
(Comparative Production Example 5) Surfactant (A'-7)
As a nonionic surfactant, a polyalkylene glycol having a hydroxyl group at both molecular ends (trade name: Blaunon P 174).
Surfactants (A′-1), (A′-2), (A′-5), (A′-6) and (A′-7) are the surfactants produced in the production examples ( A-1), (A-2), (A-5), (A-6) and (A-7).

(Preparation of cleaning composition)
The detergent compositions of Examples 1-28 and Comparative Examples 1-10 were prepared using the surfactants prepared in the above Production Examples and Comparative Production Examples.
The formulations of the cleaning compositions of Examples 1 to 28 are shown in Table 1-1 and Table 1-2, and the formulations of the cleaning compositions of Comparative Examples 1 to 10 are shown in Table 2, respectively.

(Measurement of pH)
For the cleaning compositions of Examples 1 to 4, 8 to 26, and Comparative Examples 1, 2, and 5 to 8, they were mixed with water so that the concentration of the cleaning composition was 10% by weight, and a pH meter The pH was measured using (H-21, D-21 type).
For the detergent compositions of Examples 5 to 7, 27 and 28 and Comparative Examples 3, 4, 9, and 10, a pH meter (H-21, D-21 type) was used with respect to the stock solution of the detergent composition. Was used to measure pH.
The evaluation results are shown in Table 1-1, Table 1-2, and Table 2.

(Observation of appearance (presence of discoloration))
For the cleaning composition of each Example and Comparative Example, the cleaning composition immediately after preparation of the cleaning composition and after the cleaning composition was stored at 45 ° C./15 days or 45 ° C./30 days. The color change was confirmed visually. The evaluation results are shown in Table 1-1, Table 1-2, and Table 2.
○: No discoloration is observed.
X: Obvious discoloration was observed.

(Foam suppression test)
The antifoaming property test was done about the cleaning composition of each Example and the comparative example.
The cleaning composition immediately after preparation of the cleaning composition or the cleaning composition after storage at 45 ° C. for 30 days is transferred to an automatic dishwasher of Hobart's single tank conveyor type. Each was added so that the concentration was 0.05% by weight, and operated at 60 ° C. for 2 minutes, and the bubble height immediately after the operation was measured. The evaluation results are shown in Table 1-1, Table 1-2, and Table 2.
○: The foam height is less than 1 cm, which is preferable for use in an automatic dishwasher.
Δ: Bubble height of 1 cm or more and less than 5 cm, and can be used in an automatic dishwasher.
X: Foam height of 5 cm or more, which is not preferable for use in an automatic dishwasher.

(Detergency test)
Detergency tests were performed on the cleaning compositions of each Example and Comparative Example.
In the cleaning power test, the detergent composition is added so that the concentration of the detergent composition is 0.05% by weight with respect to the amount of water in the automatic dishwasher, and the automatic dishwasher is used to wash the dirt. This was done by evaluating the appearance.
As an automatic dishwasher, a door type washer made by Hoshizaki was used, and washing conditions were a washing time of 60 seconds and a washing temperature of 60 ° C.
As dirt to be cleaned, a glass coated with composite dirt (a mixture of protein, starch and oil) was used. The evaluation results are shown in Table 1-1, Table 1-2, and Table 2.
(Double-circle): The adhesion of dirt is not seen.
○: Almost no dirt is observed.
Δ: A light cloudy stain is observed.
X: Obvious residue of dirt is observed.

(Chlorine stability test)
A chlorine stability test was conducted on the cleaning compositions prepared in each of the examples and comparative examples.
The effective chlorine concentration was measured by the iodine titration method shown below.
To about 1 g of the cleaning composition, 50 mL of an aqueous potassium iodide solution (concentration of about 2% by weight), 0.3 g of aluminum sulfate 13-14 hydrate, and 10 mL of acetic acid were added and mixed thoroughly to obtain a mixture. Produced. Next, the mixture was titrated with a 0.1 M aqueous sodium thiosulfate solution, and the point at which the brown color disappeared and became colorless was defined as the end point. Based on the dropping amount of the aqueous sodium thiosulfate solution at that time, the effective chlorine concentration was calculated by the following formula (1).
Effective chlorine concentration [%] = Amount of sodium thiosulfate dropped in water [mL] × 0.3546 / Amount of detergent composition collected [g] (1)

The effective chlorine concentration was measured by the above method immediately after preparation of the cleaning composition (0 day), after storage at 45 ° C / 30 days, after 45 ° C / 15 days, after 45 ° C / 6 days, and then at 25 ° C / 45. The test was carried out after daily storage or after storage at 25 ° C. for 4 days.
Table 1-1, Table 1-2 and Table 2 show that immediately after preparation and after storage at 45 ° C / 30 days, after 45 ° C / 15 days, after 45 ° C / 6 days, after 25 ° C / 45 days The amount of effective chlorine after storage at 25 ° C. for 4 days and the decrease rate of effective chlorine between immediately after preparation and after storage were shown.

From these evaluation results, it can be seen that the detergent compositions of Examples 1 to 28 containing a surfactant having an acetal structure at the end and a chlorine agent have no discoloration, less foaming, and high detergency.

For the chlorine stability test, Example 1 and Comparative Example 1, Example 3 and Comparative Example 2, Example 5, 6 and Comparative Example 3, Example 7 and Comparative Example 4 differed only in the type of surfactant. Example 27 and Comparative Example 9 are evaluated in comparison with Example 28 and Comparative Example 10, respectively.
In Table 3 and FIG. 1, the table | surface and graph which show the time-dependent change of the effective chlorine residual rate in the chlorine stability test of Example 5, 6 and the comparative example 3 were shown.
In Table 4 and FIG. 2, the table | surface and graph which show the time-dependent change of the effective chlorine residual rate in the chlorine stability test of Example 7 and Comparative Example 4 were shown.

When comparing the comparative example and the comparative example, the cleaning composition of each example containing a surfactant having an acetal structure at the end had a lower reduction rate of effective chlorine.
From these results, it was found that a detergent composition containing a surfactant having an acetal structure at the terminal is excellent in chlorine stability.

Claims

A cleaning composition comprising the following components (A) and (B):
(A) Nonionic surfactant having a structure represented by the general formula (1) at the terminal (B) Chlorine agent of 4% by weight or more in a pure content with respect to 100% by weight of the detergent composition

(Wherein R 1 is a hydrogen atom or an alkyl group, R 2 and R 3 are hydrocarbon groups that may contain an ether bond, R 2 and R 3 may form a ring, and AO is the same Or an oxyalkylene group which may be different, and n represents the average number of added moles of the oxyalkylene group and is a number of 1 to 400.)
The cleaning composition according to claim 1, wherein the content of the chlorinating agent is the same as or greater than the content of the nonionic surfactant.
The ratio of the content of the chlorinating agent to the content of the nonionic surfactant is
The cleaning composition according to claim 2, wherein the chlorine agent / nonionic surfactant is 1 to 100.
The cleaning composition according to any one of claims 1 to 3, wherein the nonionic surfactant has a structure represented by the general formula (2) at a terminal.

(Where m is an integer of 3 or more)
The said nonionic surfactant is a cleaning composition of Claim 4 which has a structure shown by General formula (3) at the terminal.
The cleaning composition according to any one of claims 1 to 5, wherein the nonionic surfactant has a structure represented by a general formula (4) at a terminal.

(In the formula, X is an alcohol residue or an alkylphenol residue.)
The chlorinating agent is at least one selected from the group consisting of sodium chlorinated isocyanurate, potassium chlorinated isocyanurate, trichloroisocyanuric acid, sodium hypochlorite, calcium hypochlorite and potassium hypochlorite. The cleaning composition according to any one of claims 1 to 6, which is a seed.
The cleaning composition according to any one of claims 1 to 7, further comprising (C) an alkaline agent.
9. The alkaline agent is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium orthosilicate, potassium orthosilicate, sodium metasilicate, potassium metasilicate, and hydrates thereof. Cleaning composition.
The nonionic surfactant is subjected to an addition reaction with respect to the hydroxyl group at the end of the alkylene oxide of the nonionic surfactant having the structure represented by the general formula (5) at the terminal to thereby generate the general formula (1 The cleaning composition according to any one of claims 1 to 9, which is produced by providing an acetal structure represented by
The cleaning composition according to claim 10, wherein the addition reaction is a reaction of adding dihydropyran to a hydroxyl group under an acid catalyst.