JP2008297332A - Defoaming agent for alkali detergent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonionic surfactant soluble in a high concentration alkali aqueous solution and having high defoaming effect in an alkali detergent. <P>SOLUTION: The defoaming agent for the alkali detergent comprises a compound (A) obtained by adding ethylene oxide to a 8-22C bivalent aliphatic alcohol and a compound (B) obtained by adding ethylene oxide to an amine having 1-5 activated hydrogen atoms and having HLB of 10.0-16.0, wherein the weight ratio of the compound (B) to the compound (A) is 0.5-4.0. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an antifoaming agent for an alkaline cleaner. Specifically, the present invention relates to an antifoaming agent that uniformly dissolves in a high-concentration alkaline agent aqueous solution and maintains transparency.

For cleaning hard surfaces such as metal, glass, ceramics, plastics, etc., generally washing with an alkali agent such as sodium hydroxide is performed, and it is industrially easy to measure, transport, store, etc. High-concentration alkaline detergents that are diluted with water are used.
Foam derived from dirt (oil, fat, mineral oil, protein, etc.) at the time of washing inhibits the circulation of the washing liquid. Therefore, in order to suppress foaming, an anti-foaming agent should be uniformly applied to the high-concentration alkaline detergent using an activator, etc. It is proposed to blend (Patent Documents 1 to 3).
JP-A-6-240480 JP-A-6-346259 Japanese translation of National Publication No. 11-503784

  However, the above-described cleaning agent has a problem that the antifoaming effect is not sufficient because foaming of the active agent used in combination and the amount of antifoaming agent that can be blended are limited. Therefore, an antifoaming agent having a high defoaming effect that dissolves in a high concentration aqueous alkali solution has been desired.

The inventor of the present invention has arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention comprises a compound (A) represented by the following general chemical formula (1) and a compound (B) having an HLB represented by the following general chemical formula (2) of 10.0 to 16.0. An antifoaming agent for an alkaline cleaner, wherein the weight ratio of (B) / compound (A) is 0.5 to 4.0.

[Wherein Y represents a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms, or R ¹ —OCH ₂ — group, and this R ¹ is a linear or branched chain having 6 to 20 carbon atoms. K and m are average numbers of added moles of oxyethylene groups, respectively, and are positive numbers satisfying k + m = 0.4 to 6.0. ]

[In the formula, Z is an amine having p active hydrogens or a residue obtained by removing active hydrogen from ammonia, n is an average number of moles of oxyethylene group added and is a number of 0.5 to 1.5, p is It is an integer of 1-5. ]

  The nonionic surfactant of the present invention is dissolved in a high-concentration alkaline aqueous solution, and is excellent in foam suppression, foam breaking and sustainability.

  The antifoaming agent for an alkaline detergent of the present invention has two components, a compound (A) represented by the following general chemical formula (1) and a compound (B) represented by the following general chemical formula (2) as essential components. The HLB of the compound (B) is 10.0 to 16.0. As will be described later, when the compound (B) is a combination of two or more compounds, the weighted average of individual HLBs should satisfy 10.0 to 16.0 based on the weight ratio thereof. However, a single HLB is not necessarily limited to this range.

[Wherein Y represents a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms, or R ¹ —OCH ₂ — group, and this R ¹ is a linear or branched chain having 6 to 20 carbon atoms. K and m are average numbers of added moles of oxyethylene groups, respectively, and are positive numbers satisfying k + m = 0.4 to 6.0. ]

[In the formula, Z is an amine having p active hydrogens or a residue obtained by removing active hydrogen from ammonia, n is an average number of moles of oxyethylene group added and is a number of 0.5 to 1.5, p is It is an integer of 1-5. ]

  In the antifoaming agent for an alkaline detergent of the present invention, the compound (A) which is one of the essential components is represented by the following general chemical formula (1).

Y in the general chemical formula (1) represents a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms, or an R ¹ —OCH ₂ — group, and this R ¹ is a straight chain having 6 to 20 carbon atoms. Represents a chain or branched chain alkyl group.
The compound (A) of the present invention comprises a divalent aliphatic alcohol (A ′) having 8 to 22 carbon atoms represented by Y—CH (OH) CH ₂ —OH, or an alkyl group having 6 to 20 carbon atoms. It is obtained by adding an average of k + mmol of ethylene oxide to the two hydroxyl groups of the glyceryl ether compound (A ″).

Specific examples of the divalent aliphatic alcohol (A ′) used as the raw material for the compound (A) include 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, and 1,2-undecane. Diol, 1,2-dodecanediol, 1,2-tridecanediol, 1,2-tetradecanediol, 1,2-pentadecanediol, 1,2-hexadecanediol, 1,2-octadecanediol, 1,2-nona Examples thereof include divalent straight chain or branched chain saturated or unsaturated aliphatic alcohols such as decanediol, 1,2-eicosanediol; 7-octene-1,2-diol. Two or more of these may be combined.
Of these divalent aliphatic alcohols, preferred are divalent saturated aliphatic alcohols having 8 to 18 carbon atoms, and more preferred are divalent saturated aliphatic alcohols having 10 to 14 carbon atoms. If the number of carbon atoms exceeds 22, the solubility of the defoamer for alkaline detergents of the present invention in a high-concentration aqueous alkali solution decreases, and if the number of carbon atoms is less than 8, the defoaming property deteriorates.

Specific examples of the glyceryl ether compound (A ″) used as the raw material for the compound (A) include hexyl glyceryl ether, n-octyl glyceryl ether, 2-ethylhexyl glyceryl ether, decyl glyceryl ether, undecyl glyceryl ether, dodecyl glyceryl ether. Glyceryl ethers having a linear or branched alkyl group such as tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, pentadecyl glyceryl ether, octadecyl glyceryl ether, nonadecyl glyceryl ether It is done. Two or more of these may be combined.
Among these glyceryl ether compounds, preferred are glyceryl ether compounds having an alkyl group having 8 to 18 carbon atoms, and more preferred are glyceryl ether compounds having an alkyl group having 10 to 14 carbon atoms. If the number of carbon atoms exceeds 20, the solubility of the defoamer for alkaline detergents of the present invention in a high-concentration aqueous alkali solution will decrease, and if the number of carbon atoms is less than 8, the defoaming properties will deteriorate.

  As a raw material of the compound (A) of the present invention, among the above-mentioned divalent aliphatic alcohol (A ′) and glyceryl ether compound (A ″), the high-concentration alkali of the antifoaming agent for the alkaline detergent of the present invention From the viewpoint of solubility in an aqueous solution, a divalent aliphatic alcohol (A ′) is preferable.

  In the above general chemical formula (1), k and m are the average added mole numbers of oxyethylene groups, and the total k + m is a positive number satisfying 0.4 to 6.0. k + m is preferably 0.4 to 4.0, and more preferably 0.5 to 3.0. When k + m is less than 0.4, the water solubility is insufficient, and when k + m exceeds 6.0, the defoaming effect is reduced, and the high-concentration aqueous alkaline solution of the antifoaming agent for an alkaline detergent of the present invention is used. This is not preferable because the solubility in selenium decreases.

Examples of adducts of divalent aliphatic alcohols that can be used as the compound (A) of the present invention (hereinafter, ethylene oxide is abbreviated as EO) include 1,2-octanediol EO 0.5 mol adduct, 1 , 2-nonanediol EO 1.0 mol adduct, 1,2-decanediol EO 1.0 mol adduct, 1,2-undecandiol EO 1.0 mol adduct, 1,2-dodecandiol EO 1.0 mol adduct 1,2-tridecanediol EO 1.5 mol adduct, 1,2-tetradecanediol EO 1.5 mol adduct, 1,2-pentadecanediol EO 2.0 mol adduct, 1,2-hexadecanediol EO2.0 Mole adduct, 1,2-octadecanediol EO 3.0 mol adduct, 1,2-nonadecanediol EO 4.0 mol adduct, 1 EO adduct of divalent aliphatic alcohols such as 2-eicosanediol Sanji ol EO5.0 mole adduct, such as 7-octene-1,2-diol EO1.0 mol adduct.
Examples of ethylene oxide adducts of glyceryl ether compounds include hexyl glyceryl ether EO 0.5 mol adduct, n-octyl glyceryl ether EO 0.5 mol adduct, 2-ethylhexyl glyceryl ether EO 0.5 mol adduct, decyl glyceryl ether. EO 0.5 mol adduct, undecyl glyceryl ether EO 1.0 mol adduct, dodecyl glyceryl ether EO 1.0 mol adduct, tridecyl glycidyl ether EO 1.5 mol adduct, tetradecyl glycidyl ether EO 2.0 mol adduct, Pentadecyl glycidyl ether EO 2.0 mol adduct, hexadecyl glycidyl ether EO 2.0 mol adduct, pentadecyl glyceryl ether EO 2.0 mol adduct, octadecyl glyceryl ether EO 3.0 Le adduct, EO adducts of alkyl glyceryl ether such nonadecyl glyceryl ether EO4.0 mol adduct.

Among these ethylene oxide adducts, in the compound (A) of the present invention, an EO adduct of a divalent aliphatic alcohol is used from the viewpoint of the solubility of the defoamer for alkaline detergent of the present invention in a high concentration aqueous alkali solution. From the viewpoint of antifoaming property, a divalent aliphatic alcohol EO 0.5 to 3.0 mol adduct having 10 to 14 carbon atoms is more preferable.
In addition, as a compound (A), even if it uses 2 or more types together, it does not interfere.

  The compound (A) of the present invention is produced by addition reaction of ethylene oxide with a divalent aliphatic alcohol (A ′) or glyceryl ether compound (A ″) as a raw material. The manufacturing method and conditions are as follows.

  The reaction temperature when the ring-opening addition reaction of ethylene oxide with the divalent aliphatic alcohol (A ′) and glyceryl ether compound (A ″) as raw materials is preferably 70 to 200 ° C. More preferably, it is 90 degreeC-180 degreeC. The reaction pressure is preferably −0.1 to 0.5 MPa. The reaction time is preferably 2 to 24 hours, more preferably 5 to 15 hours.

This addition reaction is carried out in the presence of a catalyst, and the catalyst may be a commonly used known catalyst, such as an alkali catalyst such as sodium hydroxide, potassium hydroxide, metallic sodium, metallic potassium, boron trifluoride, tin tetrachloride. Lewis acid catalysts such as Lewis acid catalyst are preferable. The usage-amount of a catalyst is 0.01-5 mass% with respect to the finishing amount of the ethylene oxide adduct (A) of monohydric aliphatic alcohol, Preferably it is 0.1-0.5 mass%.
These catalysts may be left in the antifoaming agent, or the catalyst may be treated by adsorption, filtration and removal using an adsorbent, or neutralization to deactivate the catalyst. Also good.

  In the antifoaming agent for an alkaline cleaner of the present invention, the compound (B), which is another essential component, is represented by the following general chemical formula (2), and its HLB is 10.0 to 16.0.

The HLB of the present invention employs the Griffin method. Further, when a plurality of compounds are mixed, additivity is established in the HLB value.
As described above, when the compound (B) represented by the general formula (2) is used in combination as two or more components, the weighted average value of each HLB satisfies this range based on the weight ratio thereof. Well, the HLB of the compound (B) used alone is not necessarily limited to this range.

Z in the general chemical formula (2) represents an amine (B ′) having p active hydrogens or a residue obtained by removing active hydrogens from ammonia, where p is an integer of 1 to 5.
The compound (B) of the present invention can be obtained by adding (n × p) mol of ethylene oxide to amine or ammonia having p active hydrogens.
Specific examples of amines (B ′) having p active materials, that is, 1 to 5 active hydrogens, are methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, 2-aminopropanol, 4 -Monoamines having 1 to 6 carbon atoms such as aminobutanol and 3-methoxypropylamine; ethylenediamine, 1,2-diaminopropane, diaminobutane, diaminopentane, trimethylenediamine, hexamethylenediamine, N-cyclohexyl-1,3 -Aliphatic diamines such as propanediamine, dimethylaminoethylamine, ethylaminoethylamine, methylaminopromylamine, 1,2-bis (3-aminopropoxy) ethane; bis (3-aminopropyl) amine, diethylenetriamine, bis (hexamethyle) N) Aliphatic polyamines such as triamine and methyliminobispropylamine; Cycloaliphatic diamines such as dicyclohexylmethanediamine and isohorndiamine; phenylenediamine, tolylenediamine, diethyltolylenediamine, xylylenediamine, diphenylmethanediamine, diphenyletherdiamine, etc. 2 or more types may be combined.
Of these amines (B ′) and ammonia, monoamines having 1 to 6 carbon atoms, aliphatic and aromatic diamines are preferable.

  In the compound (B) of the present invention, p in the general chemical formula (2) represents the number of active hydrogens and is an integer of 1 to 5. If it is 6 or more, it is not preferable because the foam is stabilized. Two or more are preferable from the viewpoint of solubility in the high-concentration aqueous alkali solution, and more preferably 2 to 4 from the viewpoint of handling properties.

  In the said General formula (2), n represents the average addition mole number of an oxyethylene group, is a number of 0.5-1.5, Preferably it is 1-1.2, More preferably, it is 1. If n is less than 0.5 or exceeds 1.5, the solubility in a high concentration aqueous alkali solution is lowered, which is not preferable.

  The HLB of the compound (B) of the present invention (when two or more kinds are used in combination, the weighted average value is 10 to 16. The antifoaming agent for an alkaline detergent of the present invention comprising the compound (A) and the compound (B)). Is required to be 10 or more in order to be blended into a highly concentrated aqueous alkali solution in a transparent liquid state, on the other hand, when the HLB value of the compound (B) exceeds 16, the compound (B) itself Although it dissolves in a high-concentration alkaline aqueous solution, the compound (A) cannot be blended in a high-concentration alkaline aqueous solution into a transparent liquid.

  Among the compounds (B) of the present invention, the compound (B1) that can be added to 5% by weight in a 30% by weight aqueous sodium hydroxide solution and can maintain a transparent liquid state at 20 ° C. has an HLB value of Usually, it is 1.01-16.0, Preferably it is 11.5-15.0, More preferably, it is 11.5-13.0.

In addition, among the compounds (B) of the present invention, the compound (B2) that can be added to 5% by weight in a 20% by weight sodium hydroxide aqueous solution and can maintain a transparent liquid state at 20 ° C. includes HL
B value is 10.0-12.0 normally, Preferably it is 10.5-12.0.

  Specific examples of the ethylene oxide adducts of amines and ammonia having 1 to 5 active hydrogens as the compound (B) of the present invention include methylamine EO2 molar adduct, ethylamine EO2 molar adduct, propylamine EO2 Mole adduct, Butylamine EO 2 mol adduct, Pentylamine EO 2 mol adduct, Hexylamine EO 3 mol adduct, 2-Aminopropanol EO 2 mol adduct, 4-Aminobutanol EO 2 mol adduct, 3-Methoxypropylamine EO 2 mol adduct EO adducts of monoamines having 1 to 6 carbon atoms such as products; ethylenediamine EO 3 mol adduct, 1,2-diaminopropane EO 4 mol adduct, diaminobutane EO 4 mol adduct, diaminopentane EO 4 mol adduct, trimethylenediamine EO 5 mol adduct, hexamethylene Diamine EO 4 mol adduct, N-cyclohexyl-1,3-propanediamine EO 5 mol adduct, ethylaminoethylamine EO 3 mol adduct, methylaminopromylamine EO 3 mol adduct, 1,2-bis (3-aminopropoxy) ethane EO adducts of aliphatic diamines such as EO4 mol adduct, dimethylaminoethylamine EO2 mol adduct; diethylenetriamine EO5 mol adduct, bis (hexamethylene) triamine EO6 mol adduct, bis (3-aminopropyl) amine EO5 mol addition , EO adduct of aliphatic polyamine such as methyliminobispropylamine EO4 mol adduct; EO adduct of alicyclic polyamine such as cyclohexylamine EO3 mol adduct, dicyclohexylmethanediamine EO6 mol adduct; phenylenediamine EO4 EO addition of aromatic diamines, such as thiol adduct, tolylenediamine EO4 mol adduct, diethyltolylenediamine EO4 mol adduct, xylylenediamine EO4 mol adduct, diphenylmethanediamine EO4 mol adduct, diphenyl ether diamine EO5 mol adduct, etc. A triethanolamine; an ethylene oxide adduct of ammonia, and the like.

Among these ethylene oxide adducts, those which do not contain primary and secondary amine compounds from the viewpoint of handling properties and odor, that is, the average addition mole number n of EO is 1 to 1.5 per one active hydrogen. Some are preferred. From the viewpoint of blending the compound (A) in a high-concentration alkaline aqueous solution in a transparent liquid state, more preferably, monoamines having 1 to 6 carbon atoms in which the average added mole number n of EO is 1 per active hydrogen, EO adducts of aliphatic and aromatic diamines.
The compound (B) of the present invention is produced by addition reaction of ethylene oxide with amine (B ′) which is a raw material of the compound (B) which is the raw material. The general production method and conditions are the same as those described for compound (a), but the production can be carried out without using a catalyst.

  In the antifoaming agent for an alkaline detergent of the present invention, the weight ratio of compound (B) / compound (A) is usually 0.5 to 4.0, preferably 0.8 to 2.0, more preferably 1. 0.0 to 1.5. Since the compound (B) enhances the compatibility with the aqueous alkali solution, if it is less than the lower limit, the solubility in the high-concentration aqueous alkali solution deteriorates. On the other hand, since only the compound (A) exhibits the defoaming effect, the defoaming effect becomes worse when the upper limit is exceeded.

  In order to further improve the antifoaming effect, the antifoaming agent for alkaline cleaner of the present invention is a compound represented by the following general chemical formula (3) in addition to the essential components (A) and (B). (C1), at least one compound (C) selected from the group consisting of compound (C2) represented by the following general chemical formula (4) and compound (C3) represented by the following general chemical formula (5) is added be able to.

[Wherein, at least one of R ^{2 to} R ⁴ is independently a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, and the remainder is a hydrogen atom. ]

[Wherein, R ⁵ and R ⁶ are each independently a linear or branched alkyl group or alkenyl group having 8 to 28 carbon atoms; q is the average number of added moles of oxyethylene group and is 0.5 to 2. The number is 5. ]

[Wherein, R ⁷ is a linear or branched alkyl group or alkenyl group having 8 to 34 carbon atoms, and r is an average added mole number of oxyethylene group, and is a number of 0 to 5.0. ]

  In the antifoaming agent for an alkaline cleaner of the present invention, the compound (C1) among the compounds (C) to be further contained is an aliphatic amine represented by the following general chemical formula (3).

At least one of R ^{2 to} R ^{4 in} the general chemical formula (3) is independently a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, and the rest represents a hydrogen atom.
Specific examples of the aliphatic amines as the compound (C1) of the present invention include octylamine, 2-ethylhexylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecyl. Primary amines such as amine, heptadecylamine, octadecylamine, nonadecylamine, oleylamine and mixtures thereof such as coconut amine, palm oil amine, beef tallow amine, soybean amine; dibutylamine, dipentylamine, dioctylamine, didodecylamine Secondary amines such as dicocoalkylamine; dimethylbutylamine, dimethylhexylamine, dimethyloctylamine, dimethyllarlylamine, dimethylcoconutamine, dimethylmyristylamine, dimethylpalmi Triethanolamine, dimethyl stearyl amine, dimethyl oleyl amine, dioctyl monomethylamine, didecyl monomethylamine, didodecyl monomethylamine, tertiary amines such as dioleyl monomethyl amine.
Of these aliphatic amines, the compound (C1) of the present invention is preferably a tertiary amine from the viewpoint of handling, and more preferably has 2 alkyl groups having 8 to 20 carbon atoms from the viewpoint of antifoaming properties. Secondary amines.
In addition, as a compound (C1), these 2 or more types may be used together.

  In the antifoaming agent for an alkaline cleaner of the present invention, the compound (C2) is an ethylene oxide adduct of a secondary aliphatic amine represented by the following general chemical formula (4).

R ⁵ and R ^{6 in the} general chemical formula (4) each independently represent a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms.
The compound (C2) of the present invention can be obtained by adding an average q mol of ethylene oxide to secondary aliphatic amines composed of an alkyl group having 8 to 22 carbon atoms.
Specific examples of the secondary aliphatic amines (C2 ′) as the raw material include dioctylamine, di (2-ethylhexyl) amine, didecylamine, diundecylamine, didodecylamine, ditridecylamine, ditetradecylamine, Secondary aliphatic amines having 8 to 22 carbon atoms such as dipentadecylamine, dihexadecylamine, diheptadecylamine, dioctadecylamine, dinonadecylamine, dioleylamine, dicocoalkylamine, ditallow alkylamine and the like. Is mentioned. Two or more of these may be combined.
Among these secondary aliphatic amines, preferred are secondary aliphatic amines having an alkyl group having 8 to 18 carbon atoms, and more preferred are secondary fats having an alkyl group having 12 to 18 carbon atoms. It is a group amine.
If the number of carbon atoms exceeds 22, the solubility of the defoamer for alkaline detergents of the present invention in a high-concentration aqueous alkali solution decreases, and if the number of carbon atoms is less than 8, the defoaming property deteriorates.

  In the general chemical formula (4), q is the average number of moles added of the oxyethylene group and is a number of 0.5 to 2.5, preferably 1.0 to 2.0, more preferably 2.0. is there. When q exceeds 2.5, the defoaming effect is lowered, and the solubility of the defoamer for alkaline detergents of the present invention in a high-concentration aqueous alkali solution is not preferred.

Examples of the ethylene oxide adduct of the secondary aliphatic amines which are the compound (C2) of the present invention include dioctylamine EO 1 mol adduct, di (2-ethylhexyl) amine EO 1 mol adduct, didecylamine EO 1 mol adduct, diundecyl. Amine EO 1 mol adduct, didodecylamine EO 1.5 mol adduct, ditridecylamine EO 1 mol adduct, ditetradecylamine EO 1.5 mol adduct, dipentadecylamine EO 1.5 mol adduct, dihexadecylamine EO2 mol adduct, diheptadecylamine EO2 mol adduct, dioctadecylamine EO2 mol adduct, dinonadecylamine EO 2.5 mol adduct, dioleylamine EO1 mol adduct, dicocoalkylamine EO1 mol adduct, di Beef tallow alkylamine EO 1.5 mol adduct That. Two or more of these may be combined.
Among these ethylene oxide adducts, in the compound (C2) of the present invention, EO1-2 of secondary aliphatic amines is used from the viewpoint of solubility of the antifoaming agent for alkaline detergent of the present invention in a high concentration aqueous alkali solution. Mole adducts are preferred, and more preferably EO 1-2 mol adducts of secondary aliphatic amines having a cocoalkyl group, an oleyl group, and a branched alkyl group from the viewpoint of handling properties (freezing point).

  The compound (C2) of the present invention is produced by subjecting a secondary aliphatic amine (C2 ′), which is a raw material thereof, to an addition reaction of ethylene oxide. The general production method and conditions are the same as those described for the compound (a) except that an acid catalyst such as p-toluenesulfonic acid, boron trifluoride, tin tetrachloride or the like is used as a catalyst. is there.

  In the antifoaming agent for an alkaline detergent of the present invention, the compound (C3) is a monovalent aliphatic alcohol represented by the following general chemical formula (5) or an ethylene oxide adduct of this aliphatic alcohol.

R ^{7 in the} general chemical formula (5) represents a linear or branched alkyl group or alkenyl group having 8 to 34 carbon atoms.
The compound (C3) of the present invention is an addition obtained by adding an average r mole of ethylene oxide to a monovalent aliphatic alcohol having 8 to 34 carbon atoms or a monovalent aliphatic alcohol having 8 to 34 carbon atoms. It is a thing.

Specific examples of the monovalent aliphatic alcohol (C3 ′) used in the present invention include octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, Straight chain or branched chain aliphatic alcohols such as diol, nonadecanol, eicosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, heptacosanol, octacosanol, triacontanol, dotriacontanol, tetratriacontanol, etc. Can be mentioned. Two or more of these may be combined.
Among these monovalent aliphatic alcohols, preferred are monovalent aliphatic alcohols having 12 to 28 carbon atoms from the viewpoint of solubility of the antifoaming agent for alkaline detergents of the present invention in a high-concentration aqueous alkali solution. From the viewpoint of defoaming property, monovalent aliphatic alcohols having a branched chain having 12 to 28 carbon atoms are more preferable.

  In the above general chemical formula (5), r is the average number of added moles of oxyethylene groups, and is a number of 0 to 5.0, preferably 0 to 3.0. When r exceeds 5.0, the defoaming effect is reduced because the compound (C3) itself has foaming properties, and the solubility of the defoamer for alkaline detergents of the present invention in a high-concentration alkaline aqueous solution is lowered. Therefore, it is not preferable.

Examples of the ethylene oxide adduct (C3 ″) of a monovalent aliphatic alcohol having 8 to 34 carbon atoms that can be used as the compound (C3) of the present invention include octanol EO 1 mol adduct, nonanol EO 1 mol adduct, decanol EO 1 mol. Adduct, undecanol EO 1 mol adduct, dodecanol EO 2 mol adduct, tridecanol EO 2 mol adduct, tetradecanol EO 3 mol adduct, pentadecanol EO 3 mol adduct, hexadecanol EO 3 mol adduct, heptadecanol EO 3 mol adduct Adduct, Octadecanol EO4 mol adduct, Nonadecanol EO3 mol adduct, Eicosanol EO3 mol adduct, Docosanol EO2 mol adduct, Tricosanol EO3 mol adduct, Tetracosanol EO3 mol adduct, Pentacosanol EO4 mol adduct , Monovalent oxacosanol EO4 mol adduct, heptacosanol EO4 mol adduct, octacosanol EO4 mol adduct, triacontanol EO4 mol adduct, dotriacontanol EO4 mol adduct, tetratriacontanol EO 4.5 mol adduct, etc. EO adducts of linear or branched aliphatic alcohols. Two or more of these may be combined.
Of these monovalent aliphatic alcohol ethylene oxide adducts, from the viewpoint of the solubility of the antifoaming agent for alkaline detergents of the present invention in a high-concentration aqueous alkaline solution, monovalents having 12 to 28 carbon atoms are preferred. A monohydric aliphatic alcohol EO addition having a branched chain of 12 to 28 carbon atoms, in which an average addition mole number r of EO is 3 or less, is an aliphatic alcohol EO adduct, and from the viewpoint of defoaming properties It is a thing.

  In the compound (C3) of the present invention, among these monovalent aliphatic alcohols and ethylene oxide adducts of monovalent aliphatic alcohols, 1 having a branched chain having 12 to 28 carbon atoms from the defoaming viewpoint. A monovalent aliphatic alcohol and a monovalent aliphatic alcohol EO adduct having a branched chain having 12 to 28 carbon atoms and having an average addition mole number r of EO of 3 or less are preferred.

  Among the compounds (C3) of the present invention, the monovalent aliphatic alcohol ethylene oxide adduct (C3 ″) is obtained by addition reaction of ethylene oxide with the monovalent aliphatic alcohol (C3 ′) as a raw material. The general production method and conditions are the same as those described for compound (a).

The antifoaming agent for an alkaline detergent of the present invention can contain at least one compound (C) in addition to the essential components (A) and (B), and the total content thereof is the present invention. 1 to 15% by weight of the total amount of the antifoaming agent for alkaline detergent.
If it is less than 1% by weight, the effect of enhancing the defoaming effect is not expressed, and if it exceeds 15% by weight, the solubility of the defoamer for alkaline detergents of the present invention in a high-concentration alkaline aqueous solution decreases. Therefore, it is not preferable.
In addition, the weight ratio of the compound (B) / compound (A) at this time is also usually 0.5 to 4.0.

The antifoaming agent of the present invention is used by blending with an alkaline detergent. Here, the alkaline detergent is a liquid or powdery detergent containing 10 to 40% by weight of an alkali agent, and its use is particularly Although it does not limit, it is suitable for the washing | cleaning process of a metal material, and washing | cleaning of the glass container for drinks.
The blending amount of the antifoaming agent of the present invention with respect to the alkaline detergent is 0.1 to 20% by weight, and may be appropriately set according to the foamed state, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, particularly preferably 1 to 5% by weight. If it is less than 0.1% by weight, the defoaming performance is insufficient.

  Examples of the alkali agent include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, silicates such as sodium orthosilicate and sodium metasilicate, disodium carbonate, sodium bicarbonate, dipotassium carbonate and potassium bicarbonate. And borate salts such as sodium borate, and two or more alkali agents may be combined. Of these, a hydroxide is preferred as the liquid alkaline detergent, and sodium hydroxide is particularly preferred. Preferred as the powder alkaline detergent are silicates and carbonates, and particularly preferred is sodium metasilicate.

  The antifoaming agent for an alkaline cleaner of the present invention is usually liquid or solid at room temperature, and is preferably liquid from the viewpoint of handling.

The defoamer for alkaline detergents of the present invention has high defoaming properties, and specifically means that the following relational expression (1) is satisfied.
F _X / F ₀ ≦ 0.5 (1)

In the above relational formula (1), F ₀ is a mixture of 1.5 g of sodium hydroxide, 0.15 g of ethylenediaminetetraacetic acid-4 sodium salt and 0.015 g of sodium oleate to make a 50 ml aqueous solution, and a 100 ml female with a stopper The amount of foaming (ml) after placing in a cylinder and adjusting the temperature to 80 ° C., shaking 10 times in 3 seconds in the vertical direction at a width of 10 cm and allowing to stand for 1 minute is shown.
F _X represents the foaming amount (ml) when 50 ml of the above aqueous solution further mixed with 0.05 g of the antifoaming agent of the present invention is subjected to the same operation.
F _X / F ₀ is usually 0.5 or less, preferably 0.3 or less.

The antifoaming agent for alkaline detergents of the present invention has high solubility in a high concentration aqueous alkali solution, and is added to a 10 to 40% by weight aqueous alkaline agent solution to maintain a transparent liquid state. In particular, the compound (B), which is an essential component, is selected and combined with (A), so that a transparent liquid can be maintained even when 5% by weight is added to a 30% by weight sodium hydroxide aqueous solution (B1). And (B2) can provide a defoaming agent having high solubility even when added to a 20 wt% sodium hydroxide aqueous solution in an amount of 5 wt%.
The solubility is visually determined as to whether or not an aqueous solution in which 5% by weight is added to a 30% by weight or 20% by weight sodium hydroxide aqueous solution is a transparent liquid at 20 ° C.

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to this. Below, a part shows a weight part.

[Example 1]
Into a 1 liter stainless steel autoclave equipped with stirring and temperature control, 174 parts (1 mol) of 1,2-decanediol and 0.5 part of aluminum perchlorate 9 hydrate were added, and the mixture system was filled with nitrogen. After substitution, dehydration was performed at 90 ° C. for 1 hour under reduced pressure (1 to 5 mmHg). Subsequently, 22 parts (0.5 mol) of EO were sequentially introduced at a temperature of 95 ° C. over 20 hours with stirring. Five parts of Kyoward 500 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the reaction product, and after the catalyst was adsorbed at 70 ° C., (A-1) was obtained by filtration. The k + m of (A-1) was 0.5.
In a 1 liter stainless steel autoclave equipped with stirring and temperature control, 116 parts (1 mole) of hexamethylenediamine was added, and after nitrogen substitution, 176 parts (4 moles) of EO was stirred at a temperature of 120 ° C. for 3 hours. Introduced sequentially. The reaction was further completed at 140 ° C. over 2 hours to obtain (B-1). The HLB of (B-1) was 12.1, and n was 1.0.
40 parts of the obtained (A-1) and 60 parts of the obtained (B-1) were put into a beaker and mixed in a 50 ° C. hot water bath to obtain an antifoaming agent (X1) of the present invention. The weight ratio of compound (B) / compound (A) in (X1) was 1.50.

[Example 2]
Into an autoclave similar to that in Example 1, 174 parts (1, mol) of 1,2-decanediol and 0.6 part of aluminum perchlorate 9 hydrate were substituted, and the inside of the mixed system was replaced with nitrogen. 1 to 5 mmHg), and dehydration was performed at 90 ° C. for 1 hour. Next, 88 parts (2.0 mol) of EO were sequentially introduced at a temperature of 95 ° C. over 20 hours with stirring. 6 parts of Kyoward 500 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the reaction product, and after the catalyst was adsorbed at 70 ° C., (A-2) was obtained by filtration. The k + m of (A-2) was 2.0.
In an autoclave similar to that in Example 1, 122 parts (1 mole part) of diaminotoluene (trade name: TDA-80, manufactured by Nippon Polyurethane Industry Co., Ltd.) was substituted with nitrogen, and then 176 parts (4 mole parts) of EO was stirred. However, it was successively introduced at a temperature of 120 ° C. over 5 hours. Further, the reaction was completed at 140 ° C. over 2 hours to obtain (B-2). The HLB of (B-2) was 11.8, and n was 1.0.
45 parts of the obtained (A-2) and 55 parts of the obtained (B-2) were put into a beaker and mixed in a 50 ° C. hot water bath to obtain the antifoaming agent (X2) of the present invention. The weight ratio of compound (B) / compound (A) in (X2) was 1.22.

[Example 3]
Into the same autoclave as in Example 1, 202 parts (1, 1 mol) of 1,2-dodecanediol and 0.5 part of aluminum perchlorate 9 hydrate were added, and the inside of the mixed system was replaced with nitrogen. 1 to 5 mmHg), and dehydration was performed at 90 ° C. for 1 hour. Subsequently, 44 parts (1.0 mol) of EO were sequentially introduced at a temperature of 95 ° C. over 20 hours with stirring. Five parts of Kyoward 500 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the reaction product, and after the catalyst was adsorbed at 70 ° C., (A-3) was obtained by filtration. The k + m of (A-3) was 1.0.
In an autoclave similar to that in Example 1, 73 parts (1 mol) of t-butylamine was substituted with nitrogen, and then 88 parts (2 mol) of EO was sequentially introduced at 120 ° C. over 5 hours with stirring. Further, the reaction was completed at 140 ° C. for 2 hours to obtain (B-3). The HLB of (B-3) was 10.9, and n was 1.0.
40 parts of the obtained (A-3) and 60 parts of the obtained B3 were put in a beaker and mixed to obtain an antifoaming agent (X3) of the present invention. The weight ratio of compound (B) / compound (A) in (X3) was 1.50.

[Example 4]
Into the same autoclave as in Example 1, 202 parts (1, 1 mol) of 1,2-dodecanediol and 0.5 part of aluminum perchlorate 9 hydrate were added, and the inside of the mixed system was replaced with nitrogen. 1 to 5 mmHg), and dehydration was performed at 90 ° C. for 1 hour. Next, 66 parts (1.5 mol) of EO were sequentially introduced at a temperature of 95 ° C. over 20 hours with stirring. Five parts of Kyoward 500 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the reaction product, and after the catalyst was adsorbed at 70 ° C., (A-4) was obtained by filtration. The k + m of (A-4) was 1.5.
40 parts of the obtained (A-4) and 60 parts of the above (B-1) were put in a beaker and mixed in a 50 ° C. hot water bath to obtain an antifoaming agent (X4) of the present invention. The weight ratio of compound (B) / compound (A) in (X4) was 1.50.

[Example 5]
Into the same autoclave as in Example 1, 202 parts (1, 1 mol) of 1,2-dodecanediol and 0.5 part of aluminum perchlorate 9 hydrate were added, and the inside of the mixed system was replaced with nitrogen. 1 to 5 mmHg), and dehydration was performed at 90 ° C. for 1 hour. Next, 88 parts (2 mol) of EO were sequentially introduced at a temperature of 95 ° C. with stirring for 20 hours. Five parts of Kyoward 500 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the reaction product, and the catalyst was adsorbed at 70 ° C., and (A-5) was obtained by filtration. The k + m of (A-5) was 2.0.
In an autoclave similar to Example 1, 116 parts (1 mol) of hexamethylenediamine and 0.5 part of potassium hydroxide were added, and the atmosphere was purged with nitrogen, followed by dehydration at 90 ° C. for 1 hour under reduced pressure (1-5 mmHg). It was. Subsequently, 194 parts (4.4 mol) of EO were sequentially introduced at a temperature of 120 ° C. with stirring for 3 hours. The reaction was further completed at 160 ° C. over 3 hours to obtain (B-4). The HLB of (B-4) was 12.5, and n was 1.1.
40 parts of the obtained (A-5) and 60 parts of the obtained (B-4) were put into a beaker and mixed in a 50 ° C. hot water bath to obtain an antifoaming agent (X5) of the present invention. The weight ratio of compound (B) / compound (A) in (X5) was 1.50.

[Example 6]
Into the same autoclave as in Example 1, 202 parts (1, 1 mol) of 1,2-dodecanediol and 0.5 part of aluminum perchlorate 9 hydrate were added, and the inside of the mixed system was replaced with nitrogen. 1 to 5 mmHg), and dehydration was performed at 90 ° C. for 1 hour. Subsequently, 132 parts (3 mol) of EO were sequentially introduced at a temperature of 95 ° C. over 20 hours with stirring. Five parts of Kyoward 500 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the reaction product, and after the catalyst was adsorbed at 70 ° C., (A-6) was obtained by filtration. The k + m of (A-6) was 3.0.
40 parts of the obtained (A-6), 40 parts of the above (B-1), and 20 parts of N-methyldiethanolamine as a component (B) to be used together are mixed in a 50 ° C. hot water bath. The antifoaming agent (X6) of the present invention was obtained. The weighted average values of HLB of the above (B-1) having an HLB of 12.1 and N-methyldiethanolamine having an HLB of 14.8 were 13.0 and n was 1.0. The weight ratio of compound (B) / compound (A) in (X6) was 1.50.

[Example 7]
Into the same autoclave as in Example 1, 230 parts (1, 1 mole) of 1,2-tetradecanediol and 0.6 part of aluminum perchlorate 9-hydrate were substituted with nitrogen, and then reduced pressure ( 1 to 5 mmHg), and dehydration was performed at 90 ° C. for 1 hour. Subsequently, 132 parts (3 mol) of EO were sequentially introduced at a temperature of 95 ° C. over 20 hours with stirring. 6 parts of Kyoward 500 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the reaction product, and after the catalyst was adsorbed at 70 ° C., (A-7) was obtained by filtration. The k + m of (A-7) was 3.0.
25 parts of the obtained (A-7), 30 parts of the above (B-1), and 45 parts of triethanolamine as a component (B) to be used together are mixed in a 50 ° C. hot water bath, An antifoaming agent (X7) of the present invention was obtained. The weighted average value of HLB of the above (B-1) having an HLB of 12.1 and triethanolamine having an HLB of 17.7 was 15.5, and n was 1.0. The weight ratio of compound (B) / compound (A) in (X7) was 3.00.

[Example 8]
Into the same autoclave as in Example 1, 230 parts (1, 1 mole) of 1,2-tetradecanediol and 0.6 part of aluminum perchlorate 9-hydrate were substituted with nitrogen, and then reduced pressure ( 1 to 5 mmHg), and dehydration was performed at 90 ° C. for 1 hour. Next, 88 parts (2 mol) of EO were sequentially introduced at a temperature of 95 ° C. with stirring for 20 hours. 6 parts of Kyoward 500 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the reaction product, and after the catalyst was adsorbed at 70 ° C., (A-8) was obtained by filtration. The k + m of (A-8) was 2.0.
60 parts of the obtained (A-8) and 40 parts of the above (B-2) were put into a beaker and mixed in a 50 ° C. hot water bath to obtain an antifoaming agent (X8) of the present invention. The weight ratio of compound (B) / compound (A) in (X8) was 0.67.

[Example 9]
26.7 parts of the above (A-3), 66.6 parts of the above (B-2), and 6.7 parts of dimethyldodecylamine (trade name: Armin DM12D, manufactured by Lion Akzo Co., Ltd.) are placed in a beaker and heated to 50 ° C. It mixed in the hot water bath and the antifoamer (X9) of this invention was obtained. The weight ratio of compound (B) / compound (A) in (X9) was 2.50, and the content of compound (C) was 6.7%.

[Example 10]
48 parts of the above (A-3), 44 parts of the above (B-2), and 8 parts of didecylmethylamine (trade name: Armin M210D, manufactured by Lion Akzo Co.) are placed in a beaker and mixed in a 50 ° C. hot water bath. And the antifoamer (X10) of this invention was obtained. The weight ratio of compound (B) / compound (A) in (X10) was 0.92, and the content of compound (C) was 8.0%.

[Example 11]
25.0 parts of the above (A-3), 72.5 parts of the above (B-2), and 2.5 parts of coconut amine (trade name: Farmin CS, manufactured by Kao Corporation) are placed in a beaker, and a 50 ° C. hot water bath. To obtain an antifoaming agent (X11) of the present invention. The weight ratio of compound (B) / compound (A) in (X11) was 2.90, and the content of compound (C) was 2.5%.

[Example 12]
In an autoclave similar to that in Example 1, 375 parts (1 mol) of dicocoalkylamine (trade name: Armin 2C, manufactured by Lion Akzo) and 4 parts of p-toluenesulfonic acid monohydrate were substituted with nitrogen. Under reduced pressure (1 to 5 mmHg), dehydration was performed at 100 ° C. for 1 hour. Subsequently, 66 parts (1.5 mol) of EO were successively introduced at a temperature of 100 ° C. over 8 hours with stirring. The reaction was further completed at 100 ° C. for 5 hours to obtain (C2-1). The q of (C2-1) was 1.5.
28.6 parts of the above (A-3), 64.3 parts of the above (B-2), and 7.1 parts of the obtained (C2-1) were put in a beaker and mixed in a 50 ° C. hot water bath, An antifoaming agent (X12) of the present invention was obtained. The weight ratio of compound (B) / compound (A) in (X12) was 2.25, and the content of compound (C) was 7.1.

[Example 13]
In an autoclave similar to that in Example 1, 375 parts (1 mol) of dicocoalkylamine (trade name: Armin 2C, manufactured by Lion Akzo) and 4 parts of p-toluenesulfonic acid monohydrate were substituted with nitrogen. Under reduced pressure (1 to 5 mmHg), dehydration was performed at 100 ° C. for 1 hour. Subsequently, 88 parts (2.0 mol) of EO were sequentially introduced at a temperature of 100 ° C. over 10 hours with stirring. The reaction was further completed at 100 ° C. for 5 hours to obtain (C2-2). Q of (C2-2) was 2.0.
23.3 parts of the above (A-3), 70.0 parts of the above (B-2), and 6.7 parts of the obtained (C2-2) were put into a beaker and mixed in a 50 ° C. hot water bath, An antifoaming agent (X13) of the present invention was obtained. The weight ratio of compound (B) / compound (A) in (X13) was 3.00, and the content of compound (C) was 6.7%.

[Example 14]
38.0 parts of the above (A-3), 58.0 parts of the above (B-2), 4.0 parts of C12-13 branched alcohol (trade name: Neodol 23, manufactured by Shell) were placed in a beaker, and 50 ° C. It mixed in the hot water bath and the antifoamer (X14) of this invention was obtained. The weight ratio of compound (B) / compound (A) in (X14) was 1.53, and the content of compound (C) was 4.0%.

[Example 15]
38.0 parts of the above (A-4), 58.0 parts of the above (B-2), and 4.0 parts of 2-decyltetradecanol (trade name: Isofol24, manufactured by Sasol Corporation) are placed in a beaker at 50 ° C. To obtain an antifoaming agent (X15) of the present invention. The weight ratio of compound (B) / compound (A) in (X15) was 1.53, and the content of compound (C) was 4.0%.

[Example 16]
35.3 parts of the above (A-4), 58.8 parts of the above (B-2), 5.9 parts of 2-hexyl decanol (trade name: Isofol 18T, manufactured by Sasol) were put in a beaker, It mixed in the hot water bath and the antifoamer (X16) of this invention was obtained. The weight ratio of compound (B) / compound (A) in (X16) was 1.67, and the content of compound (C) was 5.9%.

[Example 17]
20.2 parts of the above (A-5), 65.2 parts of the above (B-2), and a C13 secondary alcohol EO3 molar adduct having 3 as the (C) component (trade name: Softanol 30, manufactured by Kao Corporation) 14.6 parts was put into a beaker and mixed in a 50 ° C. hot water bath to obtain an antifoaming agent (X17) of the present invention. The weight ratio of compound (B) / compound (A) in (X17) was 3.22, and the content of compound (C) was 14.6%.

[Example 18]
Into the same autoclave as in Example 1, 220 parts (1 mol) of C14-15 branched alcohol (trade name: Neodol 45, manufactured by Shell) and 0.06 part of aluminum perchlorate 9 hydrate were added, and the inside of the mixed system was filled. After substituting with nitrogen, dehydration was performed at 90 ° C. for 1 hour under reduced pressure (1 to 5 mmHg). Next, 88 parts (2.0 mol) of EO were sequentially introduced at a temperature of 95 ° C. over 18 hours with stirring. Three parts of Kyoward 500 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the reaction product, and the catalyst was adsorbed at 70 ° C., and (C3-1) was obtained by filtration. R of (C3-1) was 2.0.
20.5 parts of the above (A-5), 65.9 parts of the above (B-2), and 13.6 parts of the obtained (C3-1) were put in a beaker and mixed in a 50 ° C. hot water bath, An antifoaming agent (X18) of the present invention was obtained. The weight ratio of compound (B) / compound (A) in (X18) was 3.22, and the content of compound (C) was 13.6%.

[Comparative Example 1]
Into the same autoclave as in Example 1, 202 parts (1, 1 mol) of 1,2-dodecanediol and 0.5 part of aluminum perchlorate 9 hydrate were added, and the inside of the mixed system was replaced with nitrogen. 1 to 5 mmHg), and dehydration was performed at 90 ° C. for 1 hour. Next, 440 parts (10 moles) of EO were sequentially introduced at a temperature of 95 ° C. over 20 hours with stirring. Five parts of Kyoward 500 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the reaction product, and the catalyst was adsorbed at 70 ° C., followed by filtration to obtain (A-9). The k + m of (A-9) was 10.0.
40 parts of the obtained (A-9) and 60 parts of the above (B-1) were put into a beaker and mixed in a 50 ° C. hot water bath to obtain a defoaming agent (Q1) for comparison. The weight ratio of compound (B) / compound (A) in (Q1) was 1.50.

[Comparative Example 2]
95 parts of (A-5) and 5 parts of (B-1) were placed in a beaker and mixed in a 60 ° C. hot water bath to obtain a defoaming agent (Q2) for comparison. The weight ratio of compound (B) / compound (A) in (Q2) was 0.05.

[Comparative Example 3]
15 parts of the above (A-5) and 85 parts of (B-1) were put in a beaker and mixed in a 60 ° C. hot water bath to obtain a defoaming agent (Q3) for comparison. The weight ratio of compound (B) / compound (A) in (Q3) was 5.70.

[Comparative Example 4]
40 parts of the above (A-5) and 60 parts of triethanolamine were put into a beaker and mixed in a 40 ° C. hot water bath to obtain a comparative antifoaming agent (Q4). The weight ratio of compound (B) / compound (A) in (Q4) was 1.50.

Table 1 shows the composition, chemical structure, HLB, and the like of the antifoaming agents obtained in Examples 1 to 18 and Comparative Examples 1 to 4.

The antifoaming properties of the antifoaming agents obtained in Examples 1 to 18 and Comparative Examples 1 to 4 were evaluated as follows. Table 2 shows the results of the foaming amounts Fx and F _x / F ₀ .
[Defoaming test]
Add 50g of defoaming agent, 1.5g of sodium hydroxide, 0.15g of ethylenediaminetetraacetic acid-4sodium salt and 0.015g of sodium oleate to make 50ml sample aqueous solution, put into 100ml graduated cylinder with stopper. After adjusting the temperature to 80 ° C., shake 10 times in the vertical direction at 10 cm width for 3 seconds, and measure the amount of foaming (ml) after standing for 1 minute. In the sample aqueous solution, a blank containing no antifoaming agent is used.

The alkali-soluble evaluation with respect to 30 weight% and 20 weight% sodium hydroxide aqueous solution of the antifoamer obtained in Examples 1-18 and Comparative Examples 1-4 was performed as follows. The result is not shown in Table 2 ← <Table 3 for some reason. However, this time, Table 2 and Table 3 of you are merged into New Table 2>.
[Alkali solubility test]
An antifoaming agent was added to a 20 or 30% by weight aqueous sodium hydroxide solution by 5% by weight, and the liquid state at 20 ° C. was visually observed and judged according to the following criteria.
○: Whole is transparent ×: Precipitation or separation is observed in part

Since the antifoaming composition of the present invention has good solubility in an aqueous alkali solution, it is suitable as an antifoaming agent in a cleaning process using a high-concentration alkaline cleaning agent, particularly in alkaline degreasing cleaning when cleaning a solid surface. is there. Moreover, the use of the antifoamer of this invention is not specifically limited, It is suitable also as a defoamer for wastewater treatment, such as a bioprocess, a foodstuff manufacturing process, a pulp manufacturing process, a papermaking process, fiber processing, metal processing. For example, foaming obstacles are all problems in manufacturing and processing processes that generate a large amount of wastewater, such as the pulp and paper industry, the paint industry, the textile industry, the synthetic resin industry, the resin emulsion industry, the food industry, the mechanical metal industry, and the electronic parts industry. It can be used for manufacturing and processing processes.

Claims (6)

The compound (A) represented by the following general chemical formula (1) and the compound (B) having an HLB represented by the following general chemical formula (2) of 10.0 to 16.0 are composed of compound (B) / compound ( An antifoaming agent for an alkaline detergent, wherein the weight ratio of A) is 0.5 to 4.0.

[Wherein Y represents a linear or branched alkyl group or alkenyl group having 6 to 20 carbon atoms, or R ¹ —OCH 2 — group, and this R ¹ represents a linear or branched chain group having 6 to 20 carbon atoms. An alkyl group; k and m each represent an average addition mole number of an oxyethylene group, and are positive numbers satisfying k + m = 0.4 to 6.0. ]

[In the formula, Z is an amine having p active hydrogens or a residue obtained by removing active hydrogen from ammonia, n is an average number of moles of oxyethylene group added and is a number of 0.5 to 1.5, p is It is an integer of 1-5. ] Furthermore, from the group consisting of the compound (C1) represented by the following general chemical formula (3), the compound (C2) represented by the following general chemical formula (4), and the compound (C3) represented by the following general chemical formula (5). The antifoaming agent for alkaline detergents according to claim 1, comprising at least one compound (C) selected.

[Wherein, at least one of R ^{2 to} R ⁴ is independently a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms, and the remainder is a hydrogen atom. ]

[Wherein, R ⁵ and R ⁶ are each independently a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms; q is the average number of added moles of oxyethylene group; The number is 5. ]

[Wherein, R ⁷ is a linear or branched alkyl group or alkenyl group having 8 to 34 carbon atoms, and r is an average added mole number of oxyethylene group, and is a number of 0 to 5.0. ]   The antifoaming agent for an alkaline detergent according to claim 1 or 2, wherein the content of the compound (C) is 1 to 15% by weight. The defoamer for alkaline detergents in any one of Claims 1-3 which shows the defoaming property which satisfy | fills the following relational expression (1).
F _X / F ₀ ≦ 0.5 (1)
[In the formula, F ₀ is a mixture of 1.5 g of sodium hydroxide, 0.15 g of ethylenediaminetetraacetic acid-4 sodium salt and 0.015 g of sodium oleate to make a 50 ml aqueous solution, and put it in a 100 ml graduated cylinder with a stopper. Represents the amount of foaming (ml) after temperature control at 80 ° C., 10 times in 3 seconds, 10 cm width in the vertical direction, and standing for 1 minute. F _X is foamed when the same operation is performed with a 50 ml aqueous solution containing 0.05 g of the defoaming agent, 1.5 g of sodium hydroxide, 0.15 g of ethylenediaminetetraacetic acid-4 sodium salt and 0.015 g of sodium oleate. Represents volume (ml). ]   The compound (B) is a compound (B1) having an HLB (weighted average value in the case of a mixture) of 11.0 to 16.0, and 5% by weight in a 30% by weight sodium hydroxide aqueous solution. The antifoaming agent for an alkali cleaner according to any one of claims 1 to 4, which is added to keep a transparent liquid at 20 ° C. The compound (B) is a compound (B2) having an HLB (weighted average value in the case of a mixture) of 10.0 to 12.0, and 5% by weight in a 20% by weight sodium hydroxide aqueous solution. The antifoaming agent for an alkali cleaner according to any one of claims 1 to 4, which is added to keep a transparent liquid at 20 ° C.