JPWO2014073644A1 - Cleaning composition - Google Patents

Abstract

An object of the present invention is to provide a highly alkaline detergent composition and a low foaming detergent composition. The detergent composition of the present invention comprises the following (A) to (A) to It contains component (B) and has a pH of greater than 12. (A) Nonionic surfactant having a structure represented by the general formula (1) at the terminal (B) Alkaline agent [Chemical formula 1] (wherein R1 is a hydrogen atom or an alkyl group, R2 and R3 are ether bonds) A hydrocarbon group which may be contained, R2 and R3 may form a ring, AO is an oxyalkylene group which may be the same or different, and n is an integer of 1 to 400.)

Description

The present invention relates to a cleaning composition.

As a detergent composition for an automatic dishwasher, a composition containing a surfactant is often used, but if a large amount of foam is generated during washing using an automatic dishwasher, the foam overflows and It may cause failure. Also, the cleaning power may be reduced due to the generation of bubbles.
Therefore, low foaming property is calculated | required by the cleaning composition for automatic dishwashers.

In order to suppress generation | occurrence | production of foam, the method of mix | blending a silicone type antifoamer as described in patent document 1 is known.
It is also known that a pluronic surfactant, which is a kind of nonionic surfactant, has a low foaming property and functions as an antifoaming agent.

In addition, as a detergent composition, a composition having a high pH by adding a large amount of an alkaline agent has an advantage of having a strong detergency against food-derived dirt (oil dirt, complex dirt containing oils, fats, starches, proteins, etc.). Have In particular, a composition having a pH exceeding 12 has a strong detergency.

JP 2007-161854 A

However, when the above-described silicone-based antifoaming agent is blended in a highly alkaline detergent composition, the silicone-based antifoaming agent is weak against alkali and thus has a problem that the function as the antifoaming agent is lowered.
In addition, when a pluronic surfactant is used in a highly alkaline environment, the hydroxyl group at the end is oxidized and anionized, resulting in a structure similar to that of an anionic surfactant, which increases foaming properties. It turns out that there is a problem that.
In particular, this tendency is remarkable under a high alkaline environment where the pH exceeds 12 and a detergent composition having low foaming properties under a high alkaline environment where the pH exceeds 12 has not been obtained so far.

The present invention has been made in order to solve the above-described problems, and an object thereof is to provide a highly alkaline detergent composition that has a low foaming property. To do.

The present inventors have recognized that it is a problem that a nonionic surfactant, such as a pluronic-type surfactant, has a hydroxyl group at its end, and paid attention to the structure of the end. investigated. As a result, the non-ionic surfactant having an acetal structure containing an oxygen atom at the end of the alkylene oxide at the terminal does not anionize the terminal acetal structure even in a highly alkaline environment. It has been discovered that the low foaming properties inherent in active agents are retained.
Based on the above findings, a detergent composition is prepared by blending a nonionic surfactant having an acetal structure containing an oxygen atom at the end of an alkylene oxide and an alkali agent, and adjusting the pH to a high range. Thus, the present invention has been conceived.

（式中、Ｒ^１は水素原子またはアルキル基、Ｒ^２及びＲ^３はエーテル結合を含んでもよい炭化水素基であり、Ｒ^２とＲ^３は環を形成していてもよく、ＡＯは、同一又は異なっていてもよいオキシアルキレン基であり、ｎは１〜４００の整数である。）That is, the cleaning composition of the present invention contains the following components (A) to (B) and has a pH of greater than 12.
(A) Nonionic surfactant having a structure represented by the general formula (1) at the terminal (B) Alkali agent

(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 is an integer of 1 to 400.)

A nonionic surfactant (A) has an acetal structure (AO-C (R < ¹ >) (R < ² >)-O-R < ³ >) containing the oxygen atom of the alkylene oxide terminal at the terminal.
The acetal structure is unstable under acidic conditions and generates a hydroxyl group, but is stable under neutral and alkaline conditions. In particular, the nonionic surfactant (A) can act as an antifoaming agent under high alkalinity because it is stable even under high alkalinity where the pH exceeds 12.
Under alkaline conditions where the pH is greater than 12 and there is a hydroxyl group at the end of the nonionic surfactant, the tendency of the hydroxyl group to be oxidized and anionized to increase the foaming property is remarkable. The acetal structure possessed by the nonionic surfactant (A) is stable even under high alkalinity having a pH of more than 12, and since it is anionized and does not increase foaming properties, the cleaning composition of the present invention Has an advantageous effect that the foaming property can be kept low even when the pH exceeds 12 and is highly alkaline.
In addition, since the cleaning composition of the present invention has a pH exceeding 12 and has an effect of high cleaning power against oil stains.
That is, the cleaning composition of the present invention is a highly alkaline cleaning composition that is resistant to oil stains and has a low foaming property, so that it is suitable as a cleaning composition for automatic dishwashers. It becomes a thing.

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.

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.
When these alkaline agents are used, it is easy to make the pH higher than 12, and therefore, it is suitable for a cleaning composition suitable for cleaning oil stains.

（式中、ｍは３以上の整数である。）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.

(In the formula, 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.

（式中、Ｘはアルコールの残基又はアルキルフェノールの残基である。）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.)

It is desirable that the cleaning composition of the present invention further contains (C) a chlorine agent.
When a chlorine agent is blended in the cleaning composition, both bleaching and bactericidal effects can be exhibited.
Moreover, since the nonionic surfactant (A) mix | blended with the cleaning composition of this invention does not react with a chlorine agent, it does not deactivate a chlorine agent and has a high chlorine stability. It becomes a thing.

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.

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 low foaming property can be reliably ensured.

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

The cleaning composition of the present invention has the effect that the foamability can be kept low even under a high alkaline pH exceeding 12 and the cleaning power is high.

（式中、Ｒ^１は水素原子またはアルキル基、Ｒ^２及びＲ^３はエーテル結合を含んでもよい炭化水素基であり、Ｒ^２とＲ^３は環を形成していてもよく、ＡＯは、同一又は異なっていてもよいオキシアルキレン基であり、ｎは１〜４００の整数である。）The cleaning composition of the present invention contains the following components (A) to (B) and has a pH of greater than 12.
(A) Nonionic surfactant having a structure represented by the general formula (1) at the terminal (B) Alkali agent

(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 is an integer of 1 to 400.)

The structure represented by the general formula (1) is an acetal structure.
An acetal structure is a structure used as a protecting group for a hydroxyl group. By making the hydroxyl group terminal an acetal structure, the terminal structure is not anionized even in a highly alkaline environment.
Therefore, low foaming property is maintained even in a high alkaline environment.

Since the acetal structure is a stable structure under alkalinity, the nonionic surfactant (A) is suitable for use in an alkaline detergent composition.
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 an alkaline environment” and “the hydroxyl group does not remain because it is formed by an 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 has either a feature of “high stability in an alkaline environment” that is a feature of the acetal structure or a feature that “the hydroxyl group does not remain because it is formed by an addition reaction”. Therefore, it is not suitable as a structure for blocking the hydroxyl group end. That is, the nonionic surfactant (A) having a hydroxyl group end blocked with an acetal structure is less “low-induced in a high alkaline environment than a surfactant having a hydroxyl group end blocked with another protecting group. It can be said that it is advantageous in order to exhibit the effect of “foaming”.

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.

（式中、ｍは３以上の整数である。）
上記一般式（２）で示される構造は、一般式（１）においてＲ^２とＲ^３が環を形成した構造である。A desirable structure as an acetal structure contained in the general formula (1) is a structure represented by the following general formula (2).

(In the formula, 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).

上記一般式（３）で示される構造は、一般式（２）においてｍが４である構造である。
また、一般式（３）で表される構造のうち、さらに望ましい構造は、Ｒ^１がＨである構造（テトラヒドロピラニルエーテル）である。
テトラヒドロピラニルエーテルは、アルカリに対する安定性が高く、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、下記式（６）で表される３，４−ジヒドロ−２Ｈ−ピラン（ＤＨＰ）を意味する。

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 preferred because it has high alkali stability and dihydropyran, which is a raw material for the acetal structure, is inexpensive and readily available.
As will be described later, this structure can be obtained by adding dihydropyran to a hydroxyl group under an acid catalyst.
In addition, dihydropyran in this specification 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 structure having a ring represented by the general formulas (2) and (3), the structure having a ring includes the following formulas (7), (8), ( The structure represented by 9) is also included.

The structure represented by the formula (7) is 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) is 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 is 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.

上記一般式（１３）で示される構造は、一般式（１）においてＲ^１とＲ^２が共にメチル基であり、Ｒ^３がエチル基である構造である。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 is obtained by adding 2-ethoxypropene to a hydroxyl group under an acid catalyst.

上記一般式（１４）で示される構造は、一般式（１）においてＲ^１がメチル基、Ｒ^２がエチル基、Ｒ^３がメチル基である構造である。
上記構造は、酸触媒下でヒドロキシル基に２−メトキシ−１−ブテンを付加させることにより得られる。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.

上記一般式（１５）で示される構造は、一般式（１）においてＲ^１がメチル基、Ｒ^２がペンチル基、Ｒ^３がメチル基である構造である。
上記構造は、酸触媒下でヒドロキシル基に２−メトキシ−１−ヘプテンを付加させることにより得られる。

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.

上記一般式（１６）で示される構造は、一般式（１）においてＲ^１がメチル基、Ｒ^２がメチル基、Ｒ^３がシクロヘキシル基である構造である。
上記構造は、酸触媒下でヒドロキシル基に２−シクロヘキシルオキシ−１−プロペンを付加させることにより得られる。

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 is obtained by adding 2-cyclohexyloxy-1-propene to a hydroxyl group under an acid catalyst.

上記一般式（１７）で示される構造は、一般式（１）においてＲ^１がメチル基、Ｒ^２がメチル基、Ｒ^３がフェニル基である構造である。
上記構造は、酸触媒下でヒドロキシル基に２−フェノキシ−１−プロペンを付加させることにより得られる。

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.

上記一般式（１８）で示される構造は、一般式（１）においてＲ^１、Ｒ^２、Ｒ^３がいずれもメチル基である構造である。
上記構造は、酸触媒下でヒドロキシル基に２−メトキシプロペンを付加させることにより得られる。

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.

上記一般式（１９）で示される構造は、一般式（１）においてＲ^１、Ｒ^２がいずれもメチル基、Ｒ^３がベンジル基である構造である。
上記構造は、酸触媒下でヒドロキシル基にベンジルイソプロぺニルエーテルを付加させることにより得られる。

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.

上記一般式（２０）で示される構造は、一般式（１）においてＲ^１が水素原子、Ｒ^２がメチル基であり、Ｒ^３がエチル基である構造である。Moreover, among the structures included in the general formula (1), it is also desirable to have a structure represented by the following general formula (20) at the terminal.

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 an oxyethylene group, an oxypropylene group, and an 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 addition number n of AO in the nonionic surfactant (A) is 1 to 400, and a preferable range of n is 3 to 30, and a more preferable range is 5 to 15.
In addition, n shows the average added mole number of AO.
Usually, the nonionic surfactant (A) is a mixture of a plurality of compounds having different addition mole numbers n of AO. The added mole number of AO contained in each nonionic surfactant molecule is an integer value, but the measured value when the added mole number of AO is measured is contained in each nonionic surfactant molecule. It is measured as an average value of the added mole number of AO (average added mole number). If the average added mole number of AO of the nonionic surfactant which is the object of the present invention is measured and it can be confirmed that the measured value is between 1 and 400, the added mole number n of AO is 1. It can be judged that the nonionic surfactant of this invention which is an integer of -400 is contained.
Further, the nonionic surfactant (A) may be a mixture of a plurality of compounds having different types of AO.

（Ｘはアルコールの残基又はアルキルフェノールの残基である。）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, decyl alcohol residue, lauryl alcohol residue, myristyl alcohol residue, and cetyl alcohol residue. Groups, stearyl alcohol residues, oleyl alcohol residues, octyldodecyl alcohol, 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.

（式中、Ｒ^１及びＲ^４は水素原子またはアルキル基、Ｒ^２、Ｒ^３、Ｒ^５及びＲ^６はエーテル結合を含んでもよい炭化水素基であり、Ｒ^２とＲ^３、Ｒ^５とＲ^６はそれぞれ環を形成していてもよく、ＡＯは、同一又は異なっていてもよいオキシアルキレン基であり、ｎは１〜４００の整数である。）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 ⁶ may each form a ring, AO is an oxyalkylene group which may be the same or different, and n is an integer of 1 to 400.)

この構造は、ポリエチレングリコール等の両末端にヒドロキシル基を有する界面活性剤１モルに対してジヒドロピランを２モル付加させることによって得られる。
また、上記一般式（２１）で示される構造の界面活性剤の他の具体例としては、両末端がジオキサニル基（式（７）参照）である構造、両末端がテトラヒドロフラニルエーテル（式（８）参照）である構造、両末端が２-エトキシエチル基（一般式（２０）参照）である構造、両末端が２-エトキシプロピル基（一般式（１３）参照）である構造等が挙げられる。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 formula (7)), and both ends are in tetrahydrofuranyl ether (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)), and the like. .

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, Ltd.), the product name “Brownon” (manufactured by Aoki Yushi Kogyo Co., Ltd.), the product name “Adekanol” (manufactured by ADEKA), and the product names “Pulla fuck” and “Pluronic”. (BASF Japan Co., Ltd.), trade name “Neugen” (Daiichi Kogyo Seiyaku Co., Ltd.), trade name “Peletex” (Miyoshi Oil & Fats 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, 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 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 aqueous solution etc. can be used.

The reaction conditions can be appropriately determined depending on the kind 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, After adding 10 to 15 g of dihydropyran and 1 to 10 mol% of p-toluenesulfonic acid as an acid catalyst with respect to ethylene lauryl ether, the mixture is stirred for 0.5 hours to overnight (10 hours) at room temperature, and then sodium bicarbonate. Is added to terminate the reaction, and after filtration, the solvent is distilled off.

Although the density | concentration of the nonionic surfactant (A) in the cleaning composition of this invention is not specifically limited, It is desirable that it is 0.1-30 weight%, 0.5-25 weight % Is more desirable, and 0.5 to 20% by weight is further desirable.

As the alkali agent (B), 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 (B) 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.

In the cleaning composition of the present invention, the pH is higher than 12 by adding an alkaline agent.
The terminal acetal structure of the nonionic surfactant (A) contained in the cleaning composition of the present invention is stable even under such a high pH, and the nonionic surfactant is under a high pH. Therefore, it is possible to exhibit both a cleaning effect against oil stains due to alkali, a cleaning effect due to a nonionic surfactant, and a function as an antifoaming agent.
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 cleaning composition of the present invention may further contain a chlorinating agent (C). Examples of the chlorinating agent (C) include chlorinated isocyanurate (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 (C). Inactivation of the chlorine agent (C) in the cleaning composition is prevented.
Although the density | concentration of the chlorine agent in a cleaning composition is not specifically limited, It is desirable to mix | blend so that it may become 0 to 45 weight% as an effective chlorine density | concentration. The concentration of the chlorinating agent is preferably 0 to 50% by weight, and more preferably 2 to 50% by weight.

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 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 (23), iminodisuccinic acid compounds represented by the following formula (24), iminodiacetic acid represented by the following formula (25) System compounds.

［式（２３）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（２４）中、Ｍは同一又は異なって−Ｈ、−Ｎａ、−Ｋ又は−ＮＨ_４である。］

［式（２５）中、Ｍは同一又は異なって−Ｈ、−Ｎａ、−Ｋ又は−ＮＨ_４である。］

[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 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.

(Production Example 1) Production of (A-1) As a nonionic surfactant, a polyoxyalkylene alkyl ether having an oxyalkylene group in the range of 1 to 400 and having a hydroxyl group at the alkylene oxide terminal (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 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 (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, polyoxyalkylene alkyl ether having an oxyalkylene group in the range of 1 to 400 and having a hydroxyl group at the end of alkylene oxide (Co., Ltd.) 18 g of ethyl vinyl ether and 1 mol% of p-toluenesulfonic acid as a catalyst were added to a solution of ADEKA, Adecanol BO-922 (110 g) in methylene chloride (50 ml), and the mixture was stirred overnight (10 hours) at room temperature. 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 (A-2) having an acetal structure at the terminal, which is formed by the reaction of 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 a oxyalkylene group in the range of 1 to 400 and having a hydroxyl group at the end of the 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 was distilled off to obtain the desired product.
The obtained product is a nonionic surfactant (A-3) having an acetal structure at the end, which is formed 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, polyoxyalkylene alkyl ether having an oxyalkylene group in the range of 1 to 400 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 hydrogencarbonate was added to terminate the reaction, and after filtration, the solvent was distilled off to obtain the desired product.
The resulting product is a nonionic surfactant having an acetal structure at the end, which is obtained by reacting the terminal hydroxyl group 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 alkylene oxide terminal (first 20 g of dihydropyran (DHP) and 1 mol% of paratoluenesulfonic 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 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 (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 (24 mmol) of a polyalkylene glycol having a hydroxyl group at both ends of the molecule (trade name: Pluronic RPE 3110) was prepared. 6 g (71 mmol) of dihydropyran (DHP) and 1 mol% of p-toluenesulfonic acid as a catalyst were added to a methylene chloride solution (50 ml) of glycol, 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.
Pluronic RPE 3110 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 = 1: 9.

(Production Example 7) In Production Example 6 of (A-7), instead of polyalkylene glycol (trade name: Pluronic RPE 3110), another polyalkylene glycol (trade name: Blaunon P 174) was used. The desired product was obtained in the same manner.
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 1-6)
The following surfactants were prepared as surfactants used in the evaluation test described below.
(Comparative Production Example 1) Surfactant (A′-1)
Polyoxyalkylene alkyl ether having an oxyalkylene group in the range of 1 to 400 and having a hydroxyl group at the end of alkylene oxide (manufactured by ADEKA Corporation, Adecanol B722).
(Comparative Production Example 2) Surfactant (A'-2)
Polyoxyalkylene alkyl ether having an oxyalkylene group in the range of 1 to 400 and having a hydroxyl group at the end of alkylene oxide (manufactured by ADEKA Corporation, Adecanol BO-922).
(Comparative Production Example 3) Surfactant (A'-3)
A polyoxyalkylene alkyl ether having an oxyalkylene group in the range of 1 to 400 and having a hydroxyl group at the alkylene oxide terminal (manufactured by ADEKA Corporation, Adecanol B-2020).
(Comparative Production Example 4) Surfactant (A'-5)
A 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) (100 g).
(Comparative Production Example 5) Surfactant (A'-6)
AO has a structure of HO- (PO) _o3- (EO) _p3- (PO) _q3- H (o3, p3 and q3 are integers of 1 or more), and the molar ratio of EO and PO is EO: Polyalkylene glycol with PO = 1: 9 (trade name: Pluronic RPE 3110).
(Comparative Production Example 6) Surfactant (A'-7)
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), the molar ratio of EO and PO is EO: Polyalkylene glycol with PO = 4: 6 (trade name: Blaunon P 174).
Surfactants (A′-1) to (A′-3) and (A′-5) to (A′-7) are surfactants (A-1) to (A) produced in Production Examples, respectively. -3) and (A-5) to (A-7).

(Preparation of cleaning composition)
The detergent compositions of Examples 1 to 25 and Comparative Examples 1 to 10 were prepared using the surfactants prepared in the above Production Examples and Comparative Production Examples.
Table 1 shows the formulations of the cleaning compositions of Examples 1 to 25, and Table 2 shows the formulations of the cleaning compositions of Comparative Examples 1 to 10, respectively.

(Measurement of pH)
About the detergent composition of Examples 1-7, 12-17, 19-23 and Comparative Examples 1-4, 7, it mixed with water so that the density | concentration of a detergent composition might be 10 weight%, pH meter The pH was measured using (H-21, Ltd., D-21 type).
About the detergent composition of Examples 8-11, 18, 24, 25 and Comparative Examples 5, 6, 8-10, a pH meter (D- 21) was used to measure the pH.
The evaluation results are shown in Tables 1 and 2.

(Observation of appearance (presence of discoloration))
Regarding the cleaning composition of each example and comparative example, the color change of the cleaning composition was visually observed immediately after preparation of the cleaning composition and after the cleaning composition was stored at 45 ° C. for 30 days or 15 days. Confirmed with. The evaluation results are shown in Tables 1 and 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 preparing the cleaning composition or the cleaning composition after storage at 45 ° C. for 30 days or 15 days is transferred to an automatic dishwasher of Hobart one-tank conveyor type. Each of the compositions was added to a concentration of 0.05% by weight and operated at 60 ° C. for 2 minutes, and the foam height immediately after the operation was measured. The evaluation results are shown in Tables 1 and 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 manufactured by Hoshizaki Electric Co., Ltd. was used, and the 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 Tables 1 and 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 performed on the cleaning compositions prepared in Examples 1, 3, 9, 11, 18, 19 to 25 and Comparative Examples 1, 2, 5, 6, and 8 to 10.
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 an aqueous glacial acetic acid solution were added and mixed well 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 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 storage at 45 ° C / 15 days, after storage at 45 ° C / 8 days, or at 25 ° C / 4. Each day was carried out after storage.
Tables 1 and 2 show the amount of available chlorine immediately after preparation and after storage at 45 ° C / 30 days, after storage at 45 ° C / 15 days, after storage at 45 ° C / 8 days or after storage at 25 ° C / 4 days, and preparation. The decrease rate of available chlorine between immediately after storage was shown.

From these evaluation results, the detergent compositions of Examples 1 to 25 containing a surfactant having an acetal structure at the end and having a pH of 12 or more have no discoloration, less foaming, and high detergency. Recognize.
On the other hand, the detergent compositions of Comparative Examples 1 to 6 and 8 to 10 contained a surfactant having a hydroxyl group at the end, and thus foamed greatly and were not suitable for use in an automatic dishwasher.
Further, the detergent compositions of Comparative Examples 3 and 4 containing a surfactant having a hydroxyl group at the end and having a large pH showed discoloration.
Moreover, since the pH of the cleaning composition of Comparative Example 7 was less than 12, the cleaning power was insufficient. Moreover, although the detergent composition of Comparative Example 7 contained a surfactant having a hydroxyl group at the end, foaming was small because the pH was less than 12. From this, it can be seen that when the pH of the detergent composition containing a surfactant having a hydroxyl group at the end is higher than 12 and the foaming property tends to be high.

For the chlorine stability test, Example 1 and Comparative Example 1, Example 3 and Comparative Example 2, Example 9 and Comparative Example 5, Example 11 and Comparative Example 6, and Example 18 differing only in the type of surfactant. And Comparative Example 8, Example 24 and Comparative Example 9, and Example 25 and Comparative Example 10 are respectively compared and evaluated.
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 (9)

A cleaning composition containing the following components (A) to (B) and having a pH greater than 12.
(A) Nonionic surfactant having a structure represented by the general formula (1) at the terminal (B) Alkali agent

(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 is an integer of 1 to 400.) The alkali 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 said nonionic surfactant is a cleaning composition of Claim 1 or 2 which has a structure shown by General formula (2) at the terminal.

(In the formula, m is an integer of 3 or more.) The said nonionic surfactant is a cleaning composition of Claim 3 which has a structure shown by General formula (3) at the terminal.

The said nonionic surfactant is a cleaning composition in any one of Claims 1-4 which has a structure shown by General formula (4) at the terminal.

(In the formula, X is an alcohol residue or an alkylphenol residue.) (C) The cleaning composition according to any one of claims 1 to 5, further comprising a chlorine agent. 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 claim 6, which is a seed. 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 in any one of Claims 1-7 manufactured by providing the acetal structure shown by this.

The cleaning composition according to claim 8, wherein the addition reaction is a reaction of adding dihydropyran to a hydroxyl group under an acid catalyst.