WO2014203643A1 - Solid cleaning agent composition - Google Patents

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) one or more types of alkali agent selected from a group consisting of an alkali metal hydroxide, an alkali metal salt of a metasilicic acid, an alkali metal salt of a sesquisilicic acid, an alkali metal salt of an orthosilicic acid, an alkali metal salt of an orthophosphoric acid, an alkali metal salt of a pyrophosphoric acid, an alkali metal salt of a tetraphosphoric acid, an alkali metal salt of a pentaphosphoric acid, an alkali metal salt of a hexaphosphoric acid, and an alkali metal salt of a carboxylic acid. (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

Solid detergent composition

The present invention relates to a solid detergent 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 the generation of bubbles, a method using a nonionic surfactant as described in Patent Document 1 is known.

The detergent composition described in Patent Document 1 includes a nonionic surfactant having a detergency such as permeation, emulsification, and dispersion with respect to dirt and low foaming properties, saponification of fats and oils, and chelating action of metal ions And an alkaline agent.

Furthermore, it is known that when an automatic dishwasher is continuously used, poorly water-soluble substances such as calcium carbonate and magnesium carbonate are deposited on piping inside the automatic dishwasher, a heating part of the cleaning liquid, and the like. These deposits are called scales, and are known to cause problems such as reducing the cross-sectional area of the piping to lower the cleaning efficiency and, if deposited on the heating part of the cleaning liquid, significantly reducing the thermal efficiency. ing.

Among alkaline agents, sodium carbonate is widely used in cleaning compositions because it is inexpensive. In particular, in the detergent composition for automatic dishwashers, the effects of enzymes, chelating agents, and bleaching agents are expressed in alkaline washing with sodium carbonate to improve washing power.
For example, Patent Document 2 discloses that 35a to 80% by weight of sodium carbonate as the component (a), 1 to 10% by weight of sodium bicarbonate as the component (b), 0.5 to 0.5% of the surfactant as the component (c). A composition comprising 10% by weight, wherein the content ratio of component (a) and component (b) is in the range of 8: 1 to 20: 1 by weight, for an automatic dishwasher Detergents are described.

JP 2005-112890 A JP 2001-107092 A

However, it has been found that the cleaning composition as described above is inferior in cleaning power. Furthermore, when a carbonate such as sodium carbonate is used as an alkaline agent, the concentration of carbonate ions in the cleaning liquid increases, so that there is a problem that scale is likely to precipitate.

Thus, the inventors have changed the composition of the above-described cleaning composition and investigated the cause of poor cleaning power. As a result, it has been found that the cleaning power is improved by changing the alkaline agent.

Therefore, when the detergent composition was prepared by changing the alkali agent of the detergent composition described in Patent Document 1 to sodium hydroxide, potassium hydroxide, sodium metasilicate, sodium orthosilicate, etc., the detergency improved. There was a problem that a large amount of foam was generated.

The present invention has been made in order to solve the above-described problems, and is a solid detergent composition having a high detergency and low foaming property, and a solid detergent in which scale does not easily precipitate. An object is to provide a composition.

The present inventors have recognized that it is a problem that a nonionic surfactant such as the surfactant described in Patent Document 1 has a hydroxyl group at the terminal, and pay attention to the structure of the terminal. And studied diligently. As a result, the hydroxyl group terminal is oxidized by an alkali agent and bubbles are generated by anionization. As a result of further investigation, the nonionic surfactant having an acetal structure containing an oxygen atom at the alkylene oxide terminal is It has been discovered that the low aeration property inherent to nonionic surfactants is maintained because the terminal acetal structure is not anionized by the alkali agent.
Furthermore, in the case of using a detergent composition using an alkali metal hydroxide, an alkali metal salt of silicic acid, an alkali metal salt of phosphoric acid, an alkali metal salt of carboxylic acid or the like as an alkali agent instead of sodium carbonate. Even if it exists, it discovered that low foaming property was hold | maintained.
It was also found that the precipitation of scale can be suppressed by using an alkali agent that does not contain carbonate ions such as carbonate.
In light of the above findings, the present invention has been conceived by blending a nonionic surfactant having an acetal structure containing an oxygen atom at the end of alkylene oxide with a predetermined alkali agent.

That is, the solid detergent composition of the present invention is characterized by containing the following components (A) and (B).
(A) Nonionic surfactant having the structure represented by the general formula (1) at the terminal (B) Alkali metal hydroxide, alkali metal salt of metasilicic acid, alkali metal salt of sesquisilicate, alkali of orthosilicate Selected from the group consisting of metal salts, alkali metal salts of orthophosphoric acid, alkali metal salts of pyrophosphoric acid, alkali metal salts of tetraphosphoric acid, alkali metal salts of pentaphosphoric acid, alkali metal salts of hexaphosphoric acid and alkali metal salts of carboxylic acid And at least one alkaline 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 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.
In the presence of an alkaline agent, when a hydroxyl group is present at the end of a nonionic surfactant, the hydroxyl group is oxidized, so that it exhibits properties similar to an anionic surfactant and has high foaming properties. The tendency to become is remarkable. Since the acetal structure possessed by the nonionic surfactant (A) is stable even in the presence of an alkaline agent and is not anionized to increase foaming properties, the solid detergent composition of the present invention is an alkaline agent. This has the advantageous effect that the foamability can be kept low even in the presence of.
That is, the solid detergent composition of the present invention is a detergent composition that is stable even in the presence of an alkaline agent, is resistant to oil stains, and has low foaming properties, so that it is a detergent for an automatic dishwasher. It becomes a suitable detergent 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.

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 by reaction with an alkaline agent to become a carboxyl group, resulting in discoloration. Since this reaction does not occur when is an acetal structure, discoloration is suppressed.

In the solid detergent composition of the present invention, the alkali agent is an alkali metal hydroxide, an alkali metal salt of metasilicic acid, an alkali metal salt of sesquisilicic acid, an alkali metal salt of orthosilicate, an alkali metal salt of orthophosphoric acid, pyrroline It is desirable to be at least one selected from the group consisting of alkali metal salts of acids, alkali metal salts of tetraphosphoric acid, alkali metal salts of pentaphosphoric acid, alkali metal salts of hexaphosphoric acid, and alkali metal salts of carboxylic acid.
When these alkaline agents are used, a higher cleaning power can be obtained than when sodium carbonate is used, and a low foaming property is maintained, so that the cleaning composition is suitable for cleaning oil stains. Suitable for that. In addition, since no carbonate is used, the carbonate ion concentration in the cleaning liquid does not increase, and scale does not easily precipitate.

In the solid detergent 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 solid detergent 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 solid detergent 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 solid detergent 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) blended in the solid detergent composition of the present invention does not react with the chlorine agent, it does not deactivate the chlorine agent and has a high chlorine stability. It becomes a composition.

In the solid detergent 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 acid.

In the solid detergent composition of the present invention, the nonionic surfactant is added 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 end. It is desirable that the acetal structure represented by the general formula (1) is provided at the terminal by performing the above.

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 solid detergent 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 dosage form of the solid detergent composition of the present invention is desirably a powder, granule, tablet, tablet, flake or block.

The solid detergent composition of the present invention has an effect that the foamability can be kept low, the detergency is high, and scale does not easily precipitate.

The solid detergent composition of the present invention is characterized by containing the following components (A) and (B).
(A) Nonionic surfactant having the structure represented by the general formula (1) at the terminal (B) Alkali metal hydroxide, alkali metal salt of metasilicic acid, alkali metal salt of sesquisilicate, alkali of orthosilicate Selected from the group consisting of metal salts, alkali metal salts of orthophosphoric acid, alkali metal salts of pyrophosphoric acid, alkali metal salts of tetraphosphoric acid, alkali metal salts of pentaphosphoric acid, alkali metal salts of hexaphosphoric acid and alkali metal salts of carboxylic acid And at least one alkaline 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 represents the average number of added moles of the oxyalkylene group and is a number of 1 to 400.)

The structure represented by the general formula (1) is an acetal structure.
The 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 does not react with an alkali agent to be anionized.
Therefore, low foamability is maintained even in the presence of an alkaline agent.

Since the acetal structure is a stable structure in the presence of an alkali agent, the nonionic surfactant (A) is suitable for use in a detergent composition containing an alkali agent.
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 the presence of an alkaline agent” 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 has a feature of “high stability in the presence of an alkali agent” which is a characteristic of the acetal structure, or “a hydroxyl group does not remain because it is formed by an addition reaction”. Since either of these is not satisfied, it is not suitable as a structure for blocking the hydroxyl group terminal. That is, the nonionic surfactant (A) having the hydroxyl group end blocked with an acetal structure is less “low in the presence of an alkali agent” than the surfactant having the hydroxyl group end blocked with another protecting group. It can be said that it is advantageous in order to exhibit the effect of “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).

(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).

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 addition 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 Yushi Kogyo Co., Ltd.), trade name "Adekanol" (Adeka Co., Ltd.), trade name "Plurafuck" "Pluronic" (BASF Japan Ltd.), 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 solid detergent composition of the present invention is not particularly limited, but is preferably 0.1 to 60% by weight, and preferably 0.5 to 40 More preferably, it is 0.5% by weight, and more preferably 0.5-30% by weight.

Examples of the alkali agent (B) include alkali metal hydroxide, alkali metal salt of metasilicic acid, alkali metal salt of sesquisilicic acid, alkali metal salt of orthosilicate, alkali metal salt of orthophosphoric acid, alkali metal salt of pyrophosphoric acid, tetralin At least one selected from the group consisting of an alkali metal salt of acid, an alkali metal salt of pentaphosphoric acid, an alkali metal salt of hexaphosphoric acid, and an alkali metal salt of carboxylic acid is used.
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 solid detergent composition of the present invention is not particularly limited, but is preferably 2 to 95% by weight, more preferably 30 to 95% by weight. 45 to 95% by weight is more desirable.
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.

When the alkali agent (B) is an alkali metal hydroxide, it is preferably 2 to 95% by weight, more preferably 5 to 80% by weight, and preferably 10 to 80% by weight. More desirable.
When the alkali agent (B) is an alkali metal salt of metasilicic acid, an alkali metal salt of sesquisilicic acid or an alkali metal salt of orthosilicic acid, it is preferably 2 to 95% by weight, and 10 to 95% by weight. More preferably, the content is 10 to 60% by weight.
When the alkaline agent (B) is an alkali metal salt of orthophosphoric acid, pyrophosphoric acid, tetraphosphoric acid, pentaphosphoric acid and hexaphosphoric acid, it is preferably 2 to 95% by weight, and preferably 10 to 95% by weight. More desirably, the amount is 10 to 60% by weight.
When the alkali agent (B) is an alkali metal salt of a carboxylic acid, it is preferably 2 to 95% by weight, more preferably 15 to 95% by weight, and 15 to 70% by weight. More desirable.

The alkaline agent in the present invention is not limited to those that exhibit alkalinity when dissolved in water, but includes compounds that exhibit acidity and neutrality to such an extent that the terminal acetal structure of the nonionic surfactant (A) does not decompose. Therefore, when the cleaning composition of the present invention is dissolved in water, the pH of the aqueous solution may be 7.0 or less.

The alkali agent (B) may be an anhydride or a hydrate.

As an alkali metal which comprises an alkaline agent (B), lithium, sodium, and potassium are preferable, and sodium and potassium are more preferable.

Among the alkali agents (B), the alkali metal hydroxide is preferably sodium hydroxide or potassium hydroxide.

Among the alkali agents (B), the alkali metal salt of silicic acid is represented by the following formula (23), and a / b = 1.0 to 2.0, sodium metasilicate (a / b = 1.0), potassium metasilicate (a / b = 1.0), sodium sesquisilicate (a / b = 1.5), potassium sesquisilicate (a / b = 1.5), sodium orthosilicate ( a / b = 2.0) and potassium orthosilicate (a / b = 2.0).
When a / b is less than 1.0, since the silica component in the compound increases, silica scale which is a hardly soluble precipitate derived from silica is likely to be generated.

[In the formula (23), M represents —Li, —Na or —K. a and b are integers of 1 or more, and c is an integer of 0 or more. ]

Among the alkali agents (B), the alkali metal salts of phosphoric acid include sodium orthophosphate, potassium orthophosphate, sodium pyrophosphate, potassium pyrophosphate, sodium tetraphosphate, potassium tetraphosphate, sodium pentaphosphate, potassium pentaphosphate, hexalin And sodium acid phosphate and potassium hexaphosphate.

In the present specification, unless otherwise specified, the alkali metal salt of phosphoric acid refers to a compound in which hydrogens of all hydroxyl groups are substituted with alkali metals. For example, sodium orthophosphate indicates trisodium orthophosphate and sodium pyrophosphate indicates tetrasodium pyrophosphate.

Among the alkaline agents (B), the carboxylate is not particularly limited in the number of carboxyl groups, and examples thereof include monovalent to pentavalent carboxylates. Examples of the monovalent carboxylate include acetate, propionate, and gluconate.
Examples of the divalent carboxylate include malate, tartrate and hydroxyethyliminodiacetate.
Examples of the trivalent carboxylate include citrate, hydroxyethylethylenediamine triacetate, nitrilotriacetate, methylglycine diacetate and 2-phosphonobutane-1,2,4-tricarboxylate.
Examples of the tetravalent carboxylate include ethylenediamine tetraacetate, ethylenediamine disuccinate, glutamate diacetate, and aspartate diacetate.
Examples of the pentavalent carboxylic acid include ethylene triamine pentaacetate.

As the alkaline agent (B), a polyaspartic acid compound represented by the following formula (24), an iminodisuccinic acid compound represented by the following formula (25), and an iminodiacetic acid represented by the following formula (26) Also included are system compounds.

[In the formula (24), M is the same or different and is —H, —Li, —Na or —K, and at least one M is —Li, —Na or —K. s and t are integers. ]

[In the formula (25), M is the same or different and is —H, —Li, —Na or —K, and at least one M is —Li, —Na or —K. ]

[In Formula (26), M is the same or different and is —H, —Li, —Na or —K, and at least one M is —Li, —Na or —K. ]

For divalent or higher carboxylates, all carboxyl group hydrogens may be replaced with alkali metal ions, or some of the carboxyl group hydrogens may be replaced with alkali metal ions, From the viewpoint of force, it is preferable that all carboxyl group hydrogens are replaced with alkali metal ions.
That is, as the divalent carboxylate, disodium malate, dipotassium malate, disodium tartrate, dipotassium tartrate, disodium hydroxyethyliminodiacetic acid, dipotassium hydroxyethyliminodiacetic acid,
Trivalent carboxylates include trisodium citrate, tripotassium citrate, trisodium hydroxyethylethylenediamine triacetate, tripotassium hydroxyethylethylenediamine triacetate, trisodium nitrilotriacetate, tripotassium nitrilotriacetate, methylglycine Trisodium acetate, tripotassium methylglycine diacetate, trisodium 2-phosphonobutane-1,2,4-tricarboxylate, tripotassium 2-phosphonobutane-1,2,4-tricarboxylate are preferred,
Tetravalent carboxylates include ethylenediaminetetraacetic acid tetrasodium, ethylenediaminetetraacetic acid tetrapotassium, ethylenediamine disuccinic acid tetrasodium, ethylenediamine disuccinic acid tetrapotassium, glutamic acid diacetic acid tetrasodium, glutamic acid diacetic acid tetrapotassium, aspartic acid Tetrasodium acetate, tetrapotassium aspartate diacetate are preferred,
As the pentavalent carboxylate, ethylenetriaminepentaacetic acid pentasodium and ethylenetriaminepentaacetic acid pentapotassium are preferable.

In addition, the divalent or higher carboxylic acid salt may contain a plurality of types of alkali metal ions. For example, as the tetravalent carboxylic acid salt, disodium ethylenediaminetetraacetate or the like can be suitably used.

Among the above alkali metal salts of carboxylic acids, from the viewpoint of detergency, ethylenediaminetetraacetic acid tetrasodium, ethylenediaminetetraacetic acid tetrapotassium, methylglycine diacetic acid trisodium, methylglycine diacetic acid tripotassium, nitrilotriacetic acid trisodium and nitrilotrimethyl Tripotassium acetate is particularly preferred.

The terminal acetal structure of the nonionic surfactant (A) contained in the solid detergent composition of the present invention is stable even in the presence of the alkali agent, and the nonionic surfactant is stably present. Therefore, it is possible to exhibit both the cleaning effect against oil stains due to alkali, the cleaning effect due to the nonionic surfactant, and the function as an antifoaming agent.

The pH when the solid detergent composition of the present invention is dissolved in water is not particularly limited, but from the viewpoint of the stability of the acetal structure at the end of the nonionic surfactant (A), it is neutral. It is desirable to be in an alkaline region.
The pH when the solid detergent composition is dissolved in water is a neutral detergent as the pH measured in a state where 10 g of the detergent composition is mixed with 90 g of water (the concentration of the detergent composition is 10% by weight). In the case of a 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 the strongly alkaline detergent composition In this case, the pH is desirably 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.

The solid detergent composition of the present invention may further contain a chlorinating agent (C). Examples of the chlorinating agent (C) include chlorinated isocyanurates (chlorinated isocyanurate sodium, chlorinated isocyanuric acid). Potassium), 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 (A) contained in the solid detergent composition of the present invention does not have a hydroxyl group at the terminal and has an acetal structure, and the acetal structure does not react with the chlorine agent (C). Therefore, deactivation of the chlorine agent (C) in the cleaning composition is prevented.
The concentration of the chlorine agent (C) in the cleaning composition is not particularly limited, but it is desirable that the concentration be 0 to 45% by weight as the effective chlorine concentration. The concentration of the chlorinating agent is more preferably 0 to 50% by weight, and further preferably 2 to 50% 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.

The solid detergent composition of the present invention may contain other components blended in the detergent composition such as a polymer dispersant (D) and a process agent (E) as necessary. 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, malonic acid derived from rain acid and carbon monoxide Examples include methylene copolymers, itaconic acid fumaric acid 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.

The process agent (E) is a thickener or extender added to control the dosage form of the detergent composition, and preferably has a neutral pH, such as water, sodium sulfate, powdered silica, 12- Examples thereof include hydroxystearic acid.
As other components, oxygen-based bleaching agents such as sodium perborate may be included.

The dosage form of the solid detergent composition of the present invention is preferably a powder, granule, tablet, tablet, flake or block, etc., even if some of the components constituting the detergent composition are liquid. The cleaning composition as a whole may be solid, such as impregnated in the components, and does not indicate that all the components are solid.

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, 80 g of polyalkylene glycol having a hydroxyl group at both molecular ends (trade name: Pluronic RPE 2520) was prepared, and methylene chloride of the above polyalkylene glycol. 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-5) 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 6) (A-6)
In Production Example 5, 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-6) 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 3)
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'-3)
A polyoxyalkylene alkyl ether having 1 to 400 oxyalkylene groups and having a hydroxyl group at the end of the alkylene oxide (manufactured by ADEKA Corporation, Adecanol B-2020).
Surfactants (A′-1) to (A′-3) are raw materials for surfactants (A-1) to (A-3) produced in Production Examples, respectively.

(Preparation of cleaning composition)
The detergent compositions of Examples 1 to 30 and Comparative Examples 1 to 10 were prepared using the surfactants prepared in the above Production Examples and Comparative Production Examples.
The formulations of the detergent compositions of Examples 1 to 30 are shown in Table 1-1 and Table 1-2, and the formulations of the detergent compositions of Comparative Examples 1 to 10 are shown in Table 2, respectively.

(Measurement of pH)
About the cleaning composition of each Example and the comparative example, it mixed with water so that the density | concentration of cleaning composition might be 10 weight%, and measured pH using a pH meter (Horiba, D-21 type). did.
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 performed on the cleaning compositions prepared in Examples 1 to 3, 7, 14 to 29 and Comparative Examples 1, 2, and 7 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 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 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 25 ° C / 45 days, or at 25 ° C / 4. Each day was carried out after storage.
Table 1-1, Table 1-2 and Table 2 show that immediately after preparation and after storage at 45 ° C / 30 days, after storage at 45 ° C / 15 days, after storage at 25 ° C / 45 days or after storage at 25 ° C / 4 days. The amount of effective chlorine and the decrease rate of effective chlorine immediately after preparation and after storage were shown.

(Scale deposition test)
For the cleaning compositions of Examples 14 to 24 and Comparative Examples 5 and 6, a scale deposition test was performed according to the following procedure.
A solution prepared by dissolving 4.41 g of calcium chloride dihydrate in purified water to give a 2000 ml solution was prepared as artificial hard water.
In a 200 ml stainless beaker, put 21 g of artificial hard water, 10 g of a detergent composition (aqueous solution diluted to 2% by weight with water) and 169 g of tap water, cover with a wrap and heat in a 90 ° C. constant temperature bath for 27 hours. Allowed to cool overnight.
Thereafter, the solution in the stainless beaker was slowly transferred to a 200 ml glass beaker, and the empty stainless beaker was dried.
The bottom surface of the dried stainless beaker was observed to visually check whether there was a white deposit (scale) and evaluated according to the following criteria.
○: No scale adhesion.
X: There is scale adhesion.

From these evaluation results, the detergent compositions of Examples 1 to 30 containing a nonionic surfactant having an acetal structure at the end and containing an alkali metal hydroxide or the like as an alkali agent have no discoloration and foaming. There is little and it turns out that detergency is high.
On the other hand, since the detergent compositions of Comparative Examples 1 to 4 and 7 to 10 contained a surfactant having a hydroxyl group at the end, foaming was large and it was not suitable for use in an automatic dishwasher.
From this, it can be seen that a detergent composition containing a nonionic surfactant having a hydroxyl group at the end tends to have high foamability.
Further, discoloration was observed in the cleaning compositions of Comparative Examples 3 and 4 containing a surfactant having a hydroxyl group at the end.
Moreover, since the cleaning composition of Comparative Examples 5 and 6 contained sodium carbonate as an alkaline agent, in addition to lack of cleaning power, a large amount of scale deposition was observed.

For the chlorine stability test, Example 1 and Comparative Example 1, which differ only in the type of surfactant, and Example 3 and Comparative Example 2 are compared and evaluated. Further, Examples 22 to 24 and Comparative Examples 7 to 10 have similar compositions except that the types of the surfactants are different, and in contrast, are combinations capable of evaluating chlorine stability.
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)

1. A solid detergent composition comprising the following components (A) and (B):
   (A) Nonionic surfactant having the structure represented by the general formula (1) at the terminal (B) Alkali metal hydroxide, alkali metal salt of metasilicic acid, alkali metal salt of sesquisilicate, alkali of orthosilicate Selected from the group consisting of metal salts, alkali metal salts of orthophosphoric acid, alkali metal salts of pyrophosphoric acid, alkali metal salts of tetraphosphoric acid, alkali metal salts of pentaphosphoric acid, alkali metal salts of hexaphosphoric acid and alkali metal salts of carboxylic acid And at least one alkaline 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 represents the average number of added moles of the oxyalkylene group and is a number of 1 to 400.)
2. The said nonionic surfactant is a solid cleaning composition of Claim 1 which has a structure shown by General formula (2) at the terminal.
   

   

   (In the formula, m is an integer of 3 or more.)
3. The said nonionic surfactant is a solid cleaning composition of Claim 1 or 2 which has a structure shown by General formula (3) at the terminal.
   

   
4. The solid detergent composition according to any one of claims 1 to 3, wherein the nonionic surfactant has a structure represented by the general formula (4) at a terminal.
   

   

   (In the formula, X is an alcohol residue or an alkylphenol residue.)
5. 5. The solid detergent composition according to claim 1, further comprising (C) a chlorine agent.
6. 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 solid detergent composition according to claim 5, which is a seed.
7. 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 solid detergent composition according to any one of claims 1 to 6, which is produced by providing an acetal structure represented by
   

   
8. The solid detergent composition according to claim 7, wherein the addition reaction is a reaction in which dihydropyran is added to a hydroxyl group under an acid catalyst.
9. The solid detergent composition according to any one of claims 1 to 8, wherein the dosage form is a powder, granule, tablet, tablet, flake or block.