JP5879005B2 - Nonionic surfactant and method for producing nonionic surfactant - Google Patents

Description

The present invention relates to a nonionic surfactant and a method for producing a nonionic surfactant.

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 British Patent No. 1052301

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 2 discloses a surfactant obtained by reacting vinyl ether or dihydropyran with alcohol as a low-foaming surfactant.

The inventors of the present invention evaluated the chlorine stability by mixing the surfactants described in Patent Documents 1 and 2 with a chlorine agent. As a result, it was found that the chlorine stability was higher than that of a nonionic surfactant whose end was not blocked, but it was not sufficient.
Moreover, in order to use with an automatic dishwasher, it is necessary to suppress foaming. However, the surfactants described in Patent Documents 1 and 2 are insufficient in foaming suppression, and there is room for improvement. .

The present invention has been made to solve the above-described problems, and provides a nonionic surfactant having high chlorine stability when coexisting with a chlorine agent and having an excellent foaming suppression effect. The purpose is to do.

As a result of intensive studies on the structure of a nonionic surfactant having high chlorine stability when coexisting with a chlorinating agent and having a high bubbling suppression effect, the present inventors have determined that the portion acting as a hydrophobic group has 16 carbon atoms. It has been found that by using the above hydrocarbon group and the alkylene oxide terminal having a cyclic acetal structure, the characteristics satisfying both high chlorine stability and foaming suppression effect when coexisting with a chlorinating agent are exhibited. I came up with it.

（一般式（１）中、Ｒ^１は置換基を有してもよい炭素数１６以上の炭化水素基、Ｒ^２は水素原子またはアルキル基、Ｒ^３はエーテル結合を含んでもよい炭化水素基であって炭素原子及び酸素原子と環構造を形成しており、上記環構造を形成する炭素原子には水素原子以外の置換基が結合していてもよく、ＡＯは、同一又は異なってもよいオキシアルキレン基であり、ｎは、オキシアルキレン基の平均付加モル数を表し、１〜４００の数である。） That is, the nonionic surfactant of the present invention is represented by the following general formula (1).

(In the general formula (1), R ¹ is a hydrocarbon group having 16 or more carbon atoms which may have a substituent, R ² is a hydrogen atom or an alkyl group, and R ³ is a hydrocarbon group which may contain an ether bond. And a carbon atom and an oxygen atom form a ring structure, a substituent other than a hydrogen atom may be bonded to the carbon atom forming the ring structure, and AO may be the same or different An alkylene group, and n represents the average number of moles added of the oxyalkylene group, and is a number from 1 to 400.)

The nonionic surfactant of the present invention has an acetal structure at its end.
One of the two oxygen atoms forming the acetal structure is an oxygen atom derived from a hydroxyl group that was present at the end of the alkylene oxide. Another oxygen atom forming the acetal structure forms a ring structure with the hydrocarbon group R ³ and the adjacent carbon atom.
This acetal structure can be produced by an addition reaction to the hydroxyl group at the end of the alkylene oxide. If the terminal of the surfactant is a hydroxyl group, the chlorine stability when coexisting with the chlorinating agent is low and foaming is high, but the terminal has an acetal structure to increase chlorine stability and suppress foaming. .
The high chlorine stability and foaming suppression effect due to the terminal acetal structure are more suitably exhibited by making R ¹ a hydrocarbon group having 16 or more carbon atoms which may have a substituent.
The high chlorine stability and foaming suppression effect by the nonionic surfactant of the present invention is remarkably superior to the chlorine stability and low foaming property in the surfactant where R ¹ is a hydrocarbon group having less than 16 carbon atoms. ing.

In addition, the acetal structure is unstable under acidic conditions and generates a hydroxyl group again, but is stable under neutral and alkaline conditions. Therefore, the nonionic surfactant of the present invention can exhibit high chlorine stability and foaming suppression effect in neutral and alkaline environments.
In addition, the acetal structure in this specification is a concept including both an acetal in which R ² is a hydrogen atom and a ketal in which R ² is an alkyl group.

In addition, if the hydroxyl group at the end of the alkylene oxide remains, the hydroxyl group may be oxidized under the alkalinity to become a carboxyl group and discoloration may occur, but the end is blocked so that the hydroxyl group at the end of the alkylene oxide does not remain. When this is done, this reaction does not occur, and discoloration is suppressed.

In the nonionic surfactant of the present invention, R ¹ is preferably a hydrocarbon group having 16 to 22 carbon atoms which may have a substituent.

（Ｒ^４は環構造を形成する炭素原子のいずれかに結合する水素原子又は置換基であって、Ｒ^４は複数個存在していてもよい。） The nonionic surfactant of the present invention is preferably represented by the following general formula (2).

(R ⁴ is a hydrogen atom or substituent bonded to any of the carbon atoms forming the ring structure, and a plurality of R ⁴ may be present.)

The structure represented by the general formula (2) is a structure in which the ring structure in the general formula (1) is a 6-membered ring, and the substituent R ⁴ is bonded to any of the carbon atoms forming the 6-membered ring.

（Ｒ^４は環構造を形成する炭素原子のいずれかに結合する水素原子又は置換基であって、Ｒ^４は複数個存在していてもよい。） The nonionic surfactant of the present invention is preferably represented by the following general formula (3).

(R ⁴ is a hydrogen atom or substituent bonded to any of the carbon atoms forming the ring structure, and a plurality of R ⁴ may be present.)

The structure represented by the general formula (3) is a structure in which the ring structure in the general formula (1) is a 5-membered ring, and the substituent R ⁴ is bonded to any of the carbon atoms forming the 5-membered ring.

（一般式（４）中、Ｒ^１は置換基を有してもよい炭素数１６以上の炭化水素基、ＡＯは、同一又は異なってもよいオキシアルキレン基であり、ｎは、オキシアルキレン基の平均付加モル数を表し、１〜４００の数である。） The method for producing a nonionic surfactant of the present invention comprises adding the above general formula (1) to the hydroxyl group of the alkylene oxide terminal of the nonionic surfactant represented by the following general formula (4). It is characterized by synthesizing a nonionic surfactant represented by

(In General Formula (4), R ¹ is a hydrocarbon group having 16 or more carbon atoms which may have a substituent, AO is an oxyalkylene group which may be the same or different, and n is an oxyalkylene group. This represents the average number of moles added and is a number between 1 and 400.

In the method for producing a nonionic surfactant of the present invention, the hydroxyl group terminal is blocked by an acetal structure by performing an addition reaction, not a substitution reaction, on the hydroxyl group of the alkylene oxide terminal.
Therefore, a non-ionic surfactant in which no by-product is generated and no hydroxyl group remains at the terminal can be produced. Moreover, the nonionic surfactant which has high chlorine stability and a foaming suppression effect can be manufactured, without using dangerous compounds like a dimethyl sulfate.

In the method for producing a nonionic surfactant of the present invention, the addition reaction is preferably a reaction in which dihydropyran or 2,3-dihydrofuran is added to a hydroxyl group under an acid catalyst.

The nonionic surfactant of the present invention has a high foaming suppression effect and is excellent in chlorine stability.
In addition, the method for producing a nonionic surfactant of the present invention produces a nonionic surfactant that is free of by-products and that has a high foaming suppression effect and excellent chlorine stability. be able to.

FIG. 1 is a graph showing the change over time in the effective chlorine residual rate in a chlorine stability test.

（一般式（１）中、Ｒ^１は置換基を有してもよい炭素数１６以上の炭化水素基、Ｒ^２は水素原子またはアルキル基、Ｒ^３はエーテル結合を含んでもよい炭化水素基であって炭素原子及び酸素原子と環構造を形成しており、前記環構造を形成する炭素原子には水素原子以外の置換基が結合していてもよく、ＡＯは、同一又は異なってもよいオキシアルキレン基であり、ｎは、オキシアルキレン基の平均付加モル数を表し、１〜４００の数である。） The nonionic surfactant of the present invention is represented by the following general formula (1).

(In the general formula (1), R ¹ is a hydrocarbon group having 16 or more carbon atoms which may have a substituent, R ² is a hydrogen atom or an alkyl group, and R ³ is a hydrocarbon group which may contain an ether bond. And a carbon atom and an oxygen atom form a ring structure, and a substituent other than a hydrogen atom may be bonded to the carbon atom forming the ring structure, and AO may be the same or different An alkylene group, and n represents the average number of moles added of the oxyalkylene group, and is a number from 1 to 400.)

In the nonionic surfactant of the present invention, R ¹ is a hydrocarbon group having 16 or more carbon atoms which may have a substituent. This part usually functions as a hydrophobic group.
R ¹ may be any of a chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, and an aromatic hydrocarbon group, and the carbon chain may be linear or branched. The carbon chain may or may not have an unsaturated bond.
Among these, a chain aliphatic hydrocarbon group is desirable compared to an aromatic hydrocarbon group (for example, a nonylphenyl group or the like) in relation to environmental regulations.

R ¹ has 16 or more carbon atoms, preferably 16 to 30 carbon atoms, and more preferably 16 to 22 carbon atoms.
Examples of the hydrocarbon group having 16 or more carbon atoms include a structure which is a residue obtained by removing a hydroxyl group from an alcohol having 16 or more carbon atoms.
More desirable examples of alcohols having 16 or more carbon atoms include cetyl alcohol, hexadecyl alcohol, isohexadecyl alcohol, heptadecyl alcohol, stearyl alcohol, octadecyl alcohol, isostearyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, Elide linoleyl alcohol, linoleyl alcohol, elide linoleyl alcohol, ricinoleyl alcohol, nonadecyl alcohol, arachidyl alcohol (eicosanol), 2-octyldodecan-1-ol, heneicosanol, behenyl alcohol (1 -Docosanol), erucyl alcohol, tricosanol, lignoceryl alcohol (1-tetracosanol), pentacosanol, seryl alcohol, 1 Heptacosanol, Montanyl alcohol (1-octacosanol), 1-nonacosanol, myricyl alcohol (1-triacontanol), 1-hentriacontanol, 1-dotriacontanol, gedyl alcohol (1-tetratriacontanol) Etc.
R ¹ may have a substituent, and the substituent is preferably halogen (F—, Cl—, Br— or I—). R ¹ may contain an ether bond.
The non-ionic surfactants of the present invention may be a compound having only one kind of these hydrocarbon groups as R ^1, be a mixture of a plurality of compounds having different R ¹ Good.

In addition, R ² in the general formula (1) is preferably a hydrogen atom, but when R ² is an alkyl group, it is not particularly limited as long as it is a linear or branched alkyl group. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

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

The average addition mole number n of an oxyalkylene group is 1 to 400, and a preferable range of n is 3 to 100, and a more preferable range is 5 to 50.
When the nonionic surfactant is a mixture of a plurality of compounds having different numbers of added moles of AO, the number of added moles of AO contained in each of the molecules of the nonionic surfactant is an integer value. Since the measured value when the added mole number is measured is an average value of the added mole number of AO contained in each of the molecules of the nonionic surfactant, this is regarded as the average added mole number.

The desirable lower limit of the proportion of oxyethylene groups contained in the oxyalkylene group is 30 mol%, the more desirable lower limit is 65 mol%, and the more desirable lower limit is 78 mol%. A desirable upper limit of the proportion of oxyethylene groups is 100 mol%.
When the ratio of the oxyethylene group is 30 mol% or more, the hydrophilicity of the oxyalkylene group portion is increased, and a structure suitable as the structure of the hydrophilic group portion is obtained.
Since the nonionic surfactant of the present invention has a portion having a large R ¹ carbon number of 16 or more and high hydrophobicity, it is also desirable to have only a highly hydrophilic oxyethylene group as an oxyalkylene group.

The ratio of the oxyethylene group contained in the oxyalkylene group includes an oxyethylene group (EO) as an AO (oxyalkylene group) and an oxyethylene group (PO) and / or an oxybutylene group (BO). "[X / (x + y + z)] x 100 (%)" using the average addition mole number x of oxyethylene groups, the average addition mole number y of oxypropylene groups, and the average addition mole number z of oxybutylene groups contained in The value represented.

In the structure represented by the general formula (1), R ³ forms a ring structure with the adjacent carbon atom and oxygen atom, and this ring structure becomes a part of the acetal structure, so that the terminal has a cyclic acetal structure. It can be said that it is a structure.

（Ｒ^４は環構造を形成する炭素原子のいずれかに結合する水素原子又は置換基であって、Ｒ^４は複数個存在していてもよい。）

（Ｒ^４は環構造を形成する炭素原子のいずれかに結合する水素原子又は置換基であって、Ｒ^４は複数個存在していてもよい。） The ring structure is preferably a 6-membered ring structure represented by the following general formula (2) or a 5-membered ring structure represented by the following general formula (3).

(R ⁴ is a hydrogen atom or substituent bonded to any of the carbon atoms forming the ring structure, and a plurality of R ⁴ may be present.)

(R ⁴ is a hydrogen atom or substituent bonded to any of the carbon atoms forming the ring structure, and a plurality of R ⁴ may be present.)

Examples of the substituent (R ⁴ ) other than a hydrogen atom bonded to any of the carbon atoms forming the ring structure include an alkyl group (methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.) or halogen (F-, Cl-, Br- or I-) is desirable.

The acetal structure is a structure used as a protecting group for a hydroxyl group, and by making the hydroxyl group terminal an acetal structure, R ¹ is a hydrocarbon group having 16 or more carbon atoms which may have a substituent. In addition, the chlorine stability can be increased, and the foaming suppression effect can be exhibited.

Since the acetal structure is a stable structure under neutrality and alkalinity, it can be a surfactant suitable for use in neutral and alkaline detergent compositions.
Moreover, an acetal structure can be produced | generated by addition reaction with respect to the hydroxyl group of 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 acetal structure has the characteristics of “high stability in neutral and alkaline environments” and “the hydroxyl group does not remain because it is formed by addition reaction”.

Examples of the protecting group for protecting the hydroxyl group used in the field of organic synthesis include protecting groups other than the acetal structure (for example, methyl group, benzyl group, acetyl group, trimethylsilyl group, etc.). However, the protecting group other than the acetal structure is characterized by “high stability in neutral and alkaline environments” which is a characteristic of the acetal structure, or “the hydroxyl group does not remain because it is formed by addition reaction”. Since either of the features is not satisfied, it is not suitable as a structure for blocking the hydroxyl group terminal. That is, the surfactant of the present invention in which the hydroxyl group end is blocked with an acetal structure has an advantageous effect not found in the surfactant in which the hydroxyl group end is blocked with another protecting group.

テトラヒドロピラニルエーテルは、中性及びアルカリ性環境下での安定性が高く、また、アセタール構造の原料となるジヒドロピランが安価で入手しやすいため、好ましい。
この構造は、後述するように、酸触媒下でヒドロキシル基にジヒドロピランを付加させることにより得られる。
なお、本明細書におけるジヒドロピランとは３，４−ジヒドロ−２Ｈ−ピラン（ＤＨＰ）を意味する。 Of the 6-membered ring structure of the surfactant represented by the general formula (2), a more desirable structure is a ring structure in which R ² and R ⁴ are all hydrogen atoms as shown in the following general formula (5) ( Tetrahydropyranyl ether).

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 this specification, dihydropyran means 3,4-dihydro-2H-pyran (DHP).

この構造は、後述するように、酸触媒下でヒドロキシル基に２，３−ジヒドロフランを付加させることにより得られる。 Of the five-membered ring structure of the surfactant represented by the general formula (3), a more desirable structure is a structure in which R ² and R ⁴ are all hydrogen atoms as shown in the following general formula (6) (tetrahydrofuran Nyl ether).

As will be described later, this structure can be obtained by adding 2,3-dihydrofuran to a hydroxyl group under an acid catalyst.

Examples of the structure of the surfactant contained in the general formula (1) include structures represented by the following general formulas (7) and (8).

The structure represented by the formula (7) is a structure in which R ³ is an alkylene group containing an ether bond in the general formula (1), and a 2,3-dihydro-1,4-dioxin ( 1,4-dioxene).
Structure represented by the formula (8) are the compounds of formula (1), a structure R ³ contains a cyclic structure R ³ itself, an example of a structure in which ends of the structure represented by the general formula (1) is condensed It is.
This structure is obtained by adding 2,3-benzofuran to a hydroxyl group under an acid catalyst.

（一般式（４）中、Ｒ^１は置換基を有してもよい炭素数１６以上の炭化水素基、ＡＯは、同一又は異なってもよいオキシアルキレン基であり、ｎは、オキシアルキレン基の平均付加モル数を表し、１〜４００の数である。） Hereinafter, the manufacturing method of the nonionic surfactant of this invention is demonstrated.
First, as a starting material, a nonionic surfactant having a structure represented by the following general formula (4) is prepared at the terminal.

(In General Formula (4), R ¹ is a hydrocarbon group having 16 or more carbon atoms which may have a substituent, AO is an oxyalkylene group which may be the same or different, and n is an oxyalkylene group. This represents the average number of moles added and is a number between 1 and 400.

As the nonionic surfactant having the structure represented by the general formula (4), a commercially available surfactant can be used. For example, the product name “Emarumin” (manufactured by Sanyo Chemical Industries), the product name “Brownon” (manufactured by Aoki Yushi Kogyo Co., Ltd.), the product name “Fine Surf” (manufactured by Aoki Yushi Kogyo Co., Ltd.), the product name “Adekanol” (Made by ADEKA Co., Ltd.), trade names "Pulla fuck" "Pluronic" (made by BASF Japan), trade name "Neugen" (made by Daiichi Kogyo Seiyaku Co., Ltd.), trade name "Peletex" (made by Miyoshi Oil & Fats Co., Ltd.) Can be mentioned.

Further, by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to a commercially available nonionic surfactant, the average number of moles of oxyalkylene group added and the ratio of the oxyethylene group contained in the oxyalkylene group can be determined. You may use it after adjusting.
Examples thereof include a method of adding propylene oxide and / or butylene oxide to a commercially available nonionic surfactant having only an oxyethylene group as an oxyalkylene group.

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 a structure represented by the general formula (1).
The specific procedure of the addition reaction varies depending on the acetal structure obtained by addition reaction with a hydroxyl group. For example, the structure represented by the general formula (5) (tetrahydropyranyl ether) is a hydroxyl group of a nonionic surfactant. It can be obtained by reacting dihydropyran (DHP) at the base end with an acid catalyst in an organic solvent.
As a substance used for the addition reaction, dihydropyran or 2,3-dihydrofuran is desirable.

Examples of the acid catalyst include p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, pyridinium p-toluenesulfonate, trifluoromethanesulfonic acid, sulfuric acid, hydrochloric acid, acidic ion exchange resin, and the like. 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 neutralizing 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 50 to 100 g of brownon EN1507 as a nonionic surfactant is reacted in 25 to 100 ml of methylene chloride solution, 7 to 30 g of dihydropyran and 1 to 10 mol% of p-toluenesulfonic acid as an acid catalyst were added and stirred at room temperature for 0.1 hour to overnight (10 hours), and then sodium bicarbonate was added to react. There is a method in which the solvent is distilled off after completion and filtration.

Subsequently, an example of a cleaning composition using the nonionic surfactant of the present invention will be described.
For example, (A) a nonionic surfactant of the present invention and (B) a chlorine agent can be blended in the cleaning composition. When it is set as an alkaline cleaning composition, (C) an alkali agent can be contained.

The concentration of the nonionic surfactant (A) in the cleaning composition is not particularly limited, but is preferably 0.1 to 5.0% by weight.
When a plurality of types of surfactants are used, the concentration of the surfactant is determined as a total value of the concentrations of the respective surfactants.

Examples of the chlorinating agent (B) include chlorinated isocyanurates (sodium chlorinated isocyanurate, potassium chlorinated isocyanurate, 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.
The nonionic surfactant of the present invention does not have a hydroxyl group at its terminal and has an acetal structure, and the acetal structure does not react with the chlorinating agent (B). Therefore, the chlorinating agent ( Inactivation of B) is prevented. As a result, the cleaning composition can exhibit both the cleaning effect by the surfactant and the bleaching and sterilizing effects by the chlorine agent.
The concentration of the chlorine agent in the cleaning composition is not particularly limited, but is preferably 0.1 to 30% by weight in 100% by weight of the cleaning composition, and preferably 4.0 to 4.0%. 20% by weight is more desirable.
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.

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 silicate, sodium metasilicate, sodium orthosilicate, potassium silicate and the like are desirable.
These alkaline agents may be hydrated.
Among these, at least one selected from the group consisting of potassium hydroxide, sodium orthosilicate, potassium orthosilicate, sodium metasilicate, potassium metasilicate, and hydrates thereof is desirable. This is because the use of these alkali agents makes it easy to increase the pH to more than 12.
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 90% by weight, more preferably 5 to 80% by weight, More desirably, it is 12 to 80% 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 cleaning composition desirably has a pH of 12 or higher, more preferably 13 or higher.
A detergent composition having a high pH of 12 or more is particularly effective as an alkaline detergent for removing oil stains and the like. Since the terminal acetal structure of the nonionic surfactant of the present invention contained in the detergent composition is stable even under such a high pH, the chlorine stability is high, and the alkaline absorptive effect is high. It can be set as a cleaning composition. Further, since both the nonionic surfactant and the chlorine agent are stably present under a high pH, both the cleaning effect against oil stains by the surfactant and the bleaching and bactericidal effects by the chlorine agent can be exhibited.
The pH may be measured using a commercially available pH meter or the like, and can be measured using, for example, D-21 type manufactured by Horiba, Ltd.

The detergent composition is blended with the detergent composition such as a polymer dispersant (D), a chelating agent (E), a solvent / process agent (F), a solubilizer (G), etc. as necessary. These components may be contained. Moreover, you may contain surfactant other than nonionic surfactant (A).
Examples of the polymeric 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 vinyl acetate copolymer, maleic anhydride acrylonitrile copolymer, maleic anhydride acrylic ester copolymer, maleic anhydride butadiene copolymer, maleic anhydride isoprene copolymer, maleic anhydride and Derived from carbon monoxide Poly-β-ketocarboxylic acid, itaconic acid, ethylene copolymer, itaconic acid aconitic acid copolymer, itaconic acid maleic acid copolymer, itaconic acid acrylic acid copolymer, malonic acid methylene copolymer, itaconic acid fumaric acid Examples thereof include copolymers, ethylene glycol ethylene terephthalate copolymers, vinyl pyrrolidone vinyl acetate copolymers, 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.
As the chelating agent (E), 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 (9), iminodisuccinic acid compounds represented by the following formula (10), iminodiacetic acid represented by the following formula (11) System compounds.

［式（９）中、Ｍは同一又は異なって−Ｈ、−Ｎａ、−Ｋ又は−ＮＨ_４である。ｓ、ｔは整数である。］

［式（１０）中、Ｍは同一又は異なって−Ｈ、−Ｎａ、−Ｋ又は−ＮＨ_４である。］

［式（１１）中、Ｍは同一又は異なって−Ｈ、−Ｎａ、−Ｋ又は−ＮＨ_４である。］

[In formula (9), M is the same or different and is —H, —Na, —K or —NH ₄ . s and t are integers. ]

[In formula (10), M is the same or different and is —H, —Na, —K or —NH ₄ . ]

[In formula (11), 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 in the case where the dosage form is solid, and preferably has a neutral pH, and examples thereof include sodium sulfate and powdered silica.
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). It is defined as the pH measured by weight%).

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

Example 1
As a nonionic surfactant as a raw material, a surfactant (Aoki Yushi Kogyo Co., Ltd.) having a hydrocarbon group R ¹ having 18 carbon atoms and an average added mole number x of oxyethylene groups of 15 in the general formula (1) (Brownon SR715) (90 g) was prepared, 50 g of propylene oxide and 10 mol% of potassium tert-butoxide as a catalyst were added to the nonionic surfactant, and the mixture was stirred at room temperature for 5 days. Sulfuric acid was added to terminate the reaction, and unreacted propylene oxide was distilled off to obtain an oxypropylene group adduct. From the weight difference between the added propylene oxide and the distilled propylene oxide, it was confirmed that the average added mole number y of oxypropylene groups was 3. 10 g of dihydropyran (DHP) and 1 mol% of p-toluenesulfonic acid as a catalyst were added to a methylene chloride solution (50 ml) of the above oxypropylene group adduct (30 g) and stirred overnight (10 hours) at room temperature. did. Sodium hydrogencarbonate was added to terminate the reaction, and after filtration, the solvent was distilled off to obtain the desired product.
The obtained product is a nonionic surfactant having an acetal structure at the end, which is obtained by reacting a hydroxyl group at the end of a nonionic surfactant which is an oxypropylene group adduct of BROWNON SR715 with DHP. .

(Examples 2-7, Comparative Examples 1-3)
In Example 1, the weight of propylene oxide to be added and the reaction time with propylene oxide were changed, and the nonionic surfactant as a raw material was changed to the one shown below. A nonionic surfactant having a structure was obtained. However, about Example 6, Example 7, and Comparative Example 3, reaction with a propylene oxide was not performed but only addition of DHP was performed.
Note that Blaunon SA30 / 70 2000R used in Example 7 is a random adduct of an oxyethylene group and an oxypropylene group.
Moreover, about Example 5, the oxybutylene group adduct was obtained using butylene oxide instead of propylene oxide.
Carbon number of hydrocarbon group R ¹ in general formula (1), average addition mole number x of oxyethylene group (EO), average addition mole number y of oxypropylene group (PO), average addition of oxybutylene group (BO) The number of moles z is shown in Table 1.
Example 2: Aoki Yushi Kogyo Co., Ltd., BROWNON EN1507
Example 3: Aoki Yushi Kogyo Co., Ltd., BROWNON CH308
Example 4: New Nippon Rika Co., Ltd., Conion B65-250
Example 5: Aoki Yushi Kogyo Co., Ltd., BROWNON SR715 (same as Example 1)
Example 6: Aoki Yushi Kogyo Co., Ltd., BROWNON EN1507
Example 7: Aoki Yushi Kogyo Co., Ltd., BROWNON SA30 / 70 2000R
Comparative example 1: Sanyo Chemical Industries, Emarumin NL100
Comparative example 2: Aoki Yushi Kogyo Co., Ltd., Finesurf 320
Comparative Example 3: Emarumin NL110, manufactured by Sanyo Chemical Industries
As a substance to be added to the terminal hydroxyl group of the nonionic surfactant, DHP, 1,4-dioxene or 2,3-dihydrofuran was used as shown in Table 1.

(Comparative Examples 4 to 13)
As nonionic surfactants used in the evaluation tests described later, the nonionic surfactants having a hydroxyl group at the terminal used in Examples 1 to 7 and Comparative Examples 1 to 3, and Comparative Examples 4 to 13, respectively. did.

(Chlorine stability test)
In the chlorine stability test, a cleaning composition containing any of the nonionic surfactants of the examples and comparative examples was prepared, and the chlorine stability of each cleaning composition was evaluated.
The composition of the cleaning composition was as follows: nonionic surfactant 1.3% by weight, sodium hypochlorite aqueous solution (effective chlorine concentration 12%) 44.2% by weight, sodium hydroxide aqueous solution (concentration 48% by weight) ) Was 10.0% by weight, the solubilizer (xylene sulfonate aqueous solution (concentration 40% by weight)) was 30.0% by weight, and water was 14.5% by weight.

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) and 10 mL of acetic acid were added and mixed thoroughly to prepare a mixed solution. 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 measurement of the effective chlorine concentration by the above method was performed immediately after the preparation of the cleaning composition (0 day), 3 days, 7 days, and 10 days later.
The cleaning composition was stored in a 45 ° C. incubator for a predetermined number of days.
The effective chlorine concentration immediately after preparation of the cleaning composition is defined as 100 (%), and the ratio (%) of effective chlorine concentration after 3 days, 7 days, and 10 days to the effective chlorine concentration immediately after preparation of the cleaning composition. The effective chlorine residual rate (%) was obtained and shown in Table 1.
In FIG. 1, the graph which shows a time-dependent change of the effective chlorine residual rate in a chlorine stability test was shown.

Comparing the results of Examples 1 to 7 and Comparative Examples 4 to 10, it can be seen that the chlorine stability is increased by changing the terminal of the nonionic surfactant from a hydroxyl group to an acetal structure.
Further, comparing the results of Examples 1 to 7 and Comparative Examples 1 to 3, the chlorine stability of the surfactant having an acetal structure at the end is that Example 1 in which the hydrocarbon group R ¹ has 16 or more carbon atoms. It can be seen that it is higher at ˜7.

(Foamability test)
The foamability test was performed by evaluating the foamability after 0 minutes at 25 ° C. for each nonionic surfactant using the Ross Miles method (based on JIS K3362).
It can be said that the lower the foam height, the less foaming occurs.
The results of the Ross Miles test are shown in Table 2.

As shown in Table 2, it can be seen that when the terminal of the nonionic surfactant has an acetal structure and the hydrocarbon group R ¹ has 16 or more carbon atoms, the foaming suppression effect is suitably exhibited.

Claims (5)

The nonionic surfactant characterized by being shown by following General formula (1).

(In the general formula (1), R ¹ is a hydrocarbon group having 16 or more carbon atoms which may have a substituent, R ² is a hydrogen atom or an alkyl group, and R ³ is a hydrocarbon group which may contain an ether bond. And a carbon atom and an oxygen atom form a ring structure, and a substituent other than a hydrogen atom may be bonded to the carbon atom forming the ring structure, and AO may be the same or different An alkylene group, and n represents the average number of moles added of the oxyalkylene group, and is a number from 1 to 400.) The nonionic surfactant according to claim 1, wherein R ¹ is an optionally substituted hydrocarbon group having 16 to 22 carbon atoms. The nonionic surfactant of Claim 1 or 2 shown by following General formula (2).

(R ⁴ is a hydrogen atom or substituent bonded to any of the carbon atoms forming the ring structure, and a plurality of R ⁴ may be present.) Synthesis of the nonionic surfactant represented by the general formula (1) by carrying out an addition reaction to the hydroxyl group at the end of the alkylene oxide of the nonionic surfactant represented by the following general formula (4) The method for producing a nonionic surfactant according to any one of claims 1 to 3, wherein:

(In General Formula (4), R ¹ is a hydrocarbon group having 16 or more carbon atoms which may have a substituent, AO is an oxyalkylene group which may be the same or different, and n is an oxyalkylene group. This represents the average number of moles added and is a number from 1 to 400.) The method for producing a nonionic surfactant according to claim 4, wherein the addition reaction is a reaction in which dihydropyran is added to a hydroxyl group under an acid catalyst.

Images