JP2009227664A - Low foamability cationic surfactant composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cationic surfactant composition having low foamability, causing neither separation nor precipitation even when preserving for a long time, and excellent in defoaming property. <P>SOLUTION: The low foamability cationic surfactant composition comprises a specific cationic surfactant (A), a polyether (B) represented by general formula (2) and having &le;1 g solubility to 100 g water at 30&deg;C and a 3-14C water-soluble alkylene glycol alkyl ether (C), or the (A), the (B), a 2-6 valent polyhydric alcohol (D) and a 1-5C univalent alcohol (E). R<SP>5</SP>O-(R<SP>6</SP>O)<SB>p</SB>-H (2). (Wherein, R<SP>5</SP>is an aliphatic hydrocarbon group; R<SP>6</SP>is a 2-4C alkylene group; and p is an average value and represents a number of 5-57). <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a low foaming cationic surfactant composition. More specifically, the present invention relates to a low foaming cationic surfactant composition containing a quaternary ammonium salt.

Conventionally, cationic surfactants are used in various applications, but basically they are easily foamed. Depending on the application, the cationic surfactant overflows from the inside of the container due to intense foaming, and the cationic surfactant is caused by the foam. Various troubles such as a decrease in fluidity of the added solution may occur. More specific examples include power plants, refineries and steelworks that use seawater as cooling water to prevent marine organisms such as mussels and barnacles from adhering to the cooling water piping. A small amount of cationic surfactant is added to the seawater cooling water. However, since the cationic surfactant has severe foaming, bubbles are generated in the cooling water piping to reduce the flow of cooling water, cause pump cavitation to reduce the pumping efficiency of seawater, and cool water to the seawater. There is a problem that bubbles are generated when flowing into the sea and remain on the sea surface for a long time.
In order to suppress foaming of the cationic surfactant, a method of adding a higher aliphatic amine salt to the cationic surfactant (Patent Document 1) and a method of adding a silicon-based antifoaming agent (Patent Document 2) have been proposed. Yes. However, the addition of higher aliphatic amines does not have sufficient antifoaming properties, and the addition of silicon-based antifoaming agents causes the antifoaming agent component to settle immediately, resulting in a decrease in antifoaming properties. There is a problem.

JP-A-4-334508 Japanese Patent Publication No.52-39895

  An object of the present invention is to provide a cationic surfactant composition that has low foaming properties and does not separate and settle even after long-term storage and has excellent antifoaming properties.

［式中、Ｒ¹、Ｒ²及びＲ³はそれぞれ同一若しくは異なる炭素数１〜２４の直鎖若しくは分岐のアルキル基又は炭素数３〜２４の直鎖若しくは分岐のアルケニル基；Ｒ⁴は炭素数６〜２４の直鎖若しくは分岐のアルキル基若しくはアルケニル基又は炭素数７〜２４のアリールアルキル基若しくはアリールアルケニル基；ｆは１〜１０の整数、Ｘ^f-はｆ価の対イオンであり、ハロゲンイオン、ヒドロキシイオン、硫酸イオン、リン酸イオン、硝酸イオン、カルボン酸イオン、スルホン酸イオン、硫酸エステルイオン、リン酸エステルイオン及び超強酸イオンからなる群から選ばれる１種以上のイオンである。］
Ｒ⁵Ｏ−（Ｒ⁶Ｏ）_p−Ｈ （２）
［式中、Ｒ⁵は炭素数１〜２４の脂肪族炭化水素基、Ｒ⁶は炭素数２〜４のアルキレン基、ｐは平均値であって５〜５７の数、ｐ個のＲ⁶の内の５〜５０個はプロピレン基であり、０〜２個はエチレン基であり、０〜５個はブチレン基であり、ｐ個のＲ⁶が２種以上のアルキレン基から構成される場合は、ｐ個のＲ⁶Ｏの結合形式はブロックでもランダムでもこれらの併用でもよい。］ As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention. That is, the present invention relates to a cationic surfactant (A) represented by the general formula (1), a polyether (B) represented by the general formula (2) and having a solubility in 100 g of water at 30 ° C. of 1 g or less. And water-soluble alkylene glycol alkyl ether (C) having 3 to 14 carbon atoms, or (A), (B), 2 to 6-valent polyhydric alcohol (D), and 1 to 5 carbon monovalent alcohol. It is a low foaming cationic surfactant composition comprising (E).

[Wherein, R ^1, R ² and R ³ are alkenyl group linear or branched in each the same or different 3-24 alkyl group carbon atoms or a linear or branched carbon atoms 1 to 24; R ⁴ is the number of carbon atoms A linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, or an arylalkyl group or arylalkenyl group having 7 to 24 carbon atoms; f is an integer of 1 to 10, X ^f− is an f-valent counter ion, One or more ions selected from the group consisting of ions, hydroxy ions, sulfate ions, phosphate ions, nitrate ions, carboxylate ions, sulfonate ions, sulfate ester ions, phosphate ester ions, and super strong acid ions. ]
^{R 5 O- (R 6 O)} p -H (2)
[Wherein, R ⁵ is an aliphatic hydrocarbon group having 1 to 24 carbon atoms, R ⁶ is an alkylene group having 2 to 4 carbon atoms, p is an average value of 5 to 57, and p R ⁶ 5 to 50 of them are propylene groups, 0 to 2 are ethylene groups, 0 to 5 are butylene groups, and p R ⁶ is composed of two or more alkylene groups The bonding form of p R ⁶ Os may be block, random, or a combination thereof. ]

The low-foaming cationic surfactant composition of the present invention has little foaming and is excellent in storage stability without separation and sedimentation even when stored for a long period of time.
In addition, the low foaming cationic surfactant composition of the present invention is used in facilities that use seawater (for example, when seawater is used as cooling water) and the like (for example, seawater cooling water piping) while suppressing foaming. Excellent effect in preventing marine organisms from adhering to the seawater contact surface.

The cationic surfactant (A) in the present invention [hereinafter sometimes simply referred to as (A)] is represented by the general formula (1).
In the general formula (1), R ¹ , R ² and R ³ are linear or branched alkyl groups having 1 to 24 carbon atoms, preferably 1 to 18 carbon atoms, or 3 to 24 carbon atoms, preferably 3 to 3 carbon atoms. 18 straight-chain or branched alkenyl groups.

  Examples of the linear or branched alkyl group having 1 to 24 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, and n-hexyl. Group, n-heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, isodecyl group, n-dodecyl group, isododecyl group, n-myristyl group, isomyristyl group, n-cetyl Group, isocetyl group, n-octadecyl group, isooctadecyl group, n-nonadecyl group, isononadecyl group, n-icosyl group, isoicosyl group, n-henicosyl group, isohenicosyl group, n-docosyl group, isodocosyl group, n-tricosyl group , Isotricosyl group, n-tetracosyl group, isotetracosyl group and the like.

  Examples of the linear or branched alkenyl group having 3 to 24 carbon atoms include allyl group, methallyl group, propenyl group, butenyl group, n-pentenyl group, isopentenyl group, n-hexenyl group, isohexenyl group, n-heptenyl group, Isoheptenyl group, n-octenyl group, isooctenyl group, n-nonenyl group, isononenyl group, n-decenyl group, isodecenyl group, n-undecenyl group, isoundecenyl group, n-dodecenyl group, isododecenyl group, n-tridecenyl group, isotridecenyl group N-tetradecenyl group, isotetradecenyl group, n-pentadecenyl group, isopentadecenyl group, n-hexadecenyl group, isohexadecenyl group, n-heptadecenyl group, n-oleyl group, isooleyl group, n-nonadecenyl group, isononadecenyl group, n-icosenyl , Isoikoseniru group, n- henicosenyl group, N'ikoseniru group isohexyl, n- docosenyl, n- tricosenyl group and n- tetracosenyl group.

R ¹ , R ² and R ³ may be the same or different.
Among R ¹ , R ² and R ³ , preferred combinations are all those having 1 or 2 carbon atoms, particularly a methyl group, and R ¹ and R ² are 1 or 2 carbon atoms, particularly a methyl group, and R ³ is The combination is an alkyl group having 8 to 18 carbon atoms, particularly 12 to 16 carbon atoms.

R ⁴ is a linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, or an arylalkyl group or arylalkenyl group having 7 to 24 carbon atoms.
Examples of the linear or branched alkyl group and alkenyl group having 6 to 24 carbon atoms include those having 6 to 24 carbon atoms among the aforementioned alkyl groups and alkenyl groups.
Examples of the arylalkyl group having 7 to 24 carbon atoms include phenylalkyl groups having an alkyl group having 1 to 18 carbon atoms such as a benzyl group, a phenylethyl group, and a phenylbutyl group.
Examples of the arylalkenyl group having 7 to 24 carbon atoms include a phenylethenyl group and a phenylpropenyl group.
Among preferred for R ⁴ is a linear or branched alkyl group or an arylalkyl group having 7 to 24 carbon atoms of 6 to 24 carbon atoms, in the case of R ¹ to R ³ are all carbon atoms 1 or 2 R ⁴ Is more preferably an alkyl group having 10 to 24 carbon atoms, and when R ¹ and R ² are 1 or 2 carbon atoms and R ³ is an alkyl group having 8 to 18 carbon atoms, R ⁴ is an alkyl group having 8 to 18 carbon atoms. And arylalkyl groups are preferred.

Specific examples of preferable quaternary ammonium cations constituting (A) include:
(1) R ^{1 to} R ³ are all having 1 or 2 carbon atoms and R ⁴ is an alkyl group having 10 to 24 carbon atoms;
Dodecyltrimethylammonium, tetradecyltrimethylammonium, hexadecyltrimethylammonium, trimethyloctadecylammonium, trimethylcoconut oil alkylammonium (coconut oil alkyl means an alkyl group obtained by removing a hydroxyl group from alcohol derived from coconut oil, the same applies hereinafter) , Ethyl dodecyl dimethyl ammonium, ethyl dimethyl tetradecyl ammonium, ethyl hexadecyl dimethyl ammonium, ethyl dimethyl octadecyl ammonium, ethyl dimethyl coconut oil alkyl ammonium, diethyl dodecyl methyl ammonium, diethyl methyl tetradecyl ammonium, diethyl hexadecyl methyl ammonium, diethyl octadecyl methyl Ammonium and diethyl methyl coconut oil alkylammoni Mukachion;
(2) R ¹ and R ² are alkyl groups having 1 or 2 carbon atoms, R ³ is an alkyl group having 8 to 18 carbon atoms, and R ⁴ is a benzyl group;
Benzyldecyldimethylammonium, benzyldodecyldimethylammonium, benzyldimethyltetradecylammonium, benzylhexadecyldimethylammonium and benzyldimethylcoconut oil alkylammonium cations;
(3) R ¹ and R ² are alkyl groups having 1 or 2 carbon atoms, and R ³ and R ⁴ are alkyl groups having 8 to 14 carbon atoms;
Dimethyldioctylammonium, decyldimethyloctylammonium, didecyldimethylammonium, decyldodecyldimethylammonium, didodecyldimethylammonium, dimethylditetradecylammonium, ethyldidecylmethylammonium and didecyldiethylammonium cations;
Etc.

  Of these, hexadecyltrimethylammonium, didecyldimethylammonium, benzyldodecyldimethylammonium and benzyldimethyltetradecylammonium cations are more preferable from the viewpoint of the marine organism adhesion preventing effect.

In the general formula (1), f is an integer of 1 to 10, preferably 1 to 3, and X ^f− is an f-valent counter ion.
X ^f− includes halogen ion (fluorine ion, chlorine ion, bromine ion and iodine ion), hydroxy ion, sulfate ion, phosphate ion, nitrate ion, carboxylate ion, sulfonate ion, sulfate ester ion, phosphate ester One or more kinds of ions selected from the group consisting of ions and super strong acid ions can be mentioned.
In the present invention, hydrogen sulfate ions (HSO ₄ ⁻ ) are included as sulfate ions, and HPO ₄ ²⁻ and H ₂ PO ₄ ⁻ are also included as phosphate ions.

  Examples of the carboxylic acid that forms the carboxylate ion include monovalent or divalent to 10-valent carboxylic acids.

  Examples of monovalent carboxylic acids include aliphatic acids having 1 to 18 carbon atoms such as formic acid, acetic acid, propionic acid, butyric acid, caprylic acid, 2-ethylhexanoic acid, nonanoic acid, dodecanoic acid, tetradecanoic acid, stearic acid and oleic acid. And aromatic monovalent carboxylic acids having 7 to 18 carbon atoms such as carboxylic acid and benzoic acid, ethylbenzoic acid, cinnamic acid and t-butylbenzoic acid.

  Examples of the divalent carboxylic acid include aliphatic divalent saturated carboxylic acids having 2 to 8 carbon atoms such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, and azelaic acid, and 4 carbon atoms such as maleic acid and itaconic acid. -18 aliphatic divalent unsaturated carboxylic acids and aromatic divalent carboxylic acids having 8 to 20 carbon atoms such as phthalic acid, isophthalic acid and terephthalic acid.

  Examples of the trivalent to 10-valent carboxylic acids include aliphatic tetravalent carboxylic acids such as butanetetracarboxylic acid, and aromatic trivalent or tetravalent carboxylic acids such as trimellitic acid and pyromellitic acid.

  Examples of the sulfonic acid that forms the sulfonate ion include aromatic monovalent sulfonic acids such as p-toluenesulfonic acid, benzenesulfonic acid, alkylbenzenesulfonic acid, naphthalenesulfonic acid, and p-phenolsulfonic acid.

Sulfate esters that form sulfate ion include methyl sulfate, ethyl sulfate, propyl sulfate, octyl sulfate, 2-ethylhexyl sulfate, decyl sulfate, dodecyl sulfate, tetradecyl sulfate, octadecyl sulfate, and oleyl. Examples thereof include monoalkyl or monoalkenyl sulfates having 1 to 24 carbon atoms such as sulfate esters and dimethyl sulfate. When dimethyl sulfate is used, any ^one of R ^{1 to} R ³ in general formula (1) is methyl, and the counter ion is monomethyl sulfate ion.

  Examples of the phosphoric acid ester that forms a phosphoric acid ester ion include monooctyl esters having 1 to 24 carbon atoms such as octyl phosphoric acid ester, 2-ethylhexyl phosphoric acid ester, decyl phosphoric acid ester, dodecyl phosphoric acid ester, octadecyl phosphoric acid ester and oleyl phosphoric acid ester Or a dialkyl or mono- or dialkenyl phosphate ester.

A super strong acid that forms a super strong acid ion has a Hammett acidity function (H ₀ ) of less than −11.93 (value of 100% sulfuric acid), and is composed of a proton acid and a combination of a proton acid and a Lewis acid. Is mentioned.
Specific examples of the protonic acid include trifluoromethanesulfonic acid (H ₀ = -14.10) and pentafluoroethanesulfonic acid (H ₀ = -14.00).
Examples of the protonic acid used in the combination of the protonic acid and the Lewis acid include hydrogen halides (hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, etc.), and examples of the Lewis acid include boron trifluoride and pentafluoride. And phosphorus arsenide, antimony pentafluoride, and arsenic pentafluoride.
The combination of the protonic acid and the Lewis acid is arbitrary, but specific examples include boron tetrafluoride acid, hexafluorophosphoric acid, chlorofluoroboronic acid, hexafluoroantimonic acid, and hexafluoroarsenic acid. It is done.

  The f-valent counter ion includes the f-valent ion of the f-valent acid and the f-valent counter ion (partial salt) of the [(f + α) -valent] acid higher than the f valence. For example, when the acid is a polybasic acid (a dibasic acid having 2 to 18 carbon atoms such as oxalic acid, maleic acid, succinic acid and adipic acid), (A) includes a mono salt and a polyvalent salt. .

  Of the f-valent counter ions, halogen ions, carboxylate ions, sulfate ions and superacid ions are preferred from the viewpoint of the effect of preventing marine organism adhesion, and halogen ions, carboxylate ions and sulfates are more preferred. Ester ions, particularly preferred are halogen ions and sulfate ester ions, particularly preferred are chloride ions, bromine ions and sulfate ester ions, and most preferred are sulfate ester ions.

The production method of the cationic surfactant (A) in the present invention is not particularly limited, and examples thereof include the following known methods (1) to (4).
(1) A reaction temperature of 85 ° C. to 95 ° C. in the presence of a solvent [for example, a water-soluble alkylene glycol alkyl ether (C) and water described below] in a tertiary amine obtained by removing one alkyl cation from the quaternary ammonium cation. A method of obtaining (A) in which the counter ion is a methylsulfate ion by adding dimethylsulfate dropwise and quaternizing with stirring.
(2) To a tertiary amine obtained by removing one alkyl cation from the quaternary ammonium cation, a solvent [for example, a divalent to hexavalent polyhydric alcohol (D) described later; the amount of the solvent is based on the weight of the tertiary amine. 10 to 1,000% by weight] in the presence of a reaction temperature of 80 to 120 ° C. and a pressure of 0.1 to 0.5 Mpa for 0.5 to 5 hours (equivalent of tertiary amine / alkyl halide). The ratio is 1/1 to 1 / 1.3), stirred at a temperature of 80 to 120 ° C. and a pressure of 0.1 to 0.5 MPa for 1 to 5 hours, cooled to 50 to 80 ° C., and nitrogen is introduced into the liquid. A method of obtaining (A) in which the counter ion is a halogen ion by removing unreacted alkyl halide by flowing at a flow rate of 0.1 to 0.5 L / min for 1 to 3 hours.
(3) Tertiary amine obtained by removing one alkyl cation from the quaternary ammonium cation and a dialkyl carbonate (the alkyl group has 1 to 5 carbon atoms, and the equivalent ratio of tertiary amine / dialkyl carbonate is 1/1 to 1). /1.3) in the presence of a solvent [eg 2 to 6 valent polyhydric alcohol (D) described below; the amount of the solvent is 10 to 1,000% by weight based on the weight of the tertiary amine]. A quaternary ammonium salt is produced by reacting at 80 to 120 ° C. and a pressure of 0.1 to 0.5 Mpa for 0.5 to 5 hours, and further 1.0 to 1.2 equivalents based on the equivalent of the quaternary ammonium. To obtain (A) in which the counter ion is a proton acid ion by adding salt of the proton acid and stirring for 1 hour at 10 to 50 ° C. for salt exchange.
(4) Alkaline (for example, sodium hydroxide and potassium hydroxide; quaternary ammonium salt / alkali equivalent ratio is usually 1/1 to 1 / 1.1) in (A) obtained in (1) to (3). ) And stirring for 1 hour at 10 to 50 ° C. for salt exchange to obtain (A) the counter ion is a hydroxy ion.

  The polyether (B) in the present invention [hereinafter sometimes simply abbreviated as (B)] has a function of suppressing the foaming property of the cationic surfactant.

In the general formula (2) representing (B), R ⁵ is an aliphatic hydrocarbon group having 1 to 24 carbon atoms.
Examples of the aliphatic hydrocarbon group having 1 to 24 carbon atoms include linear or branched alkyl groups having 1 to 24 carbon atoms, linear or branched alkenyl groups having 3 to 24 carbon atoms, and alicyclic rings having 4 to 15 carbon atoms. Groups and the like.
Specific examples of the linear or branched alkyl group having 1 to 24 carbon atoms and the linear or branched alkenyl group having 3 to 24 carbon atoms include the same groups as those exemplified for the aforementioned R ^{1 to} R ^3. It is done. Examples of the alicyclic group having 4 to 15 carbon atoms include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, an ethylcyclohexyl group, a propylcyclohexyl group, an octylcyclohexyl group, and a nonylcyclohexyl group.
From the viewpoint of the internal antifoaming property of R ⁵ , a linear or branched alkyl group having 1 to 24 carbon atoms is preferable, a linear alkyl group is more preferable, and particularly preferable is a linear alkyl group having 1 to 2 carbon atoms. 12 straight chain alkyl groups.

R ⁶ in the general formula (2) is an alkylene group having 2 to 4 carbon atoms, such as an ethylene group, a propylene group (1,2-propylene group and a 1,3-propylene group) and a butylene group (1,2-butylene). Group, 1,3-butylene group, 1,4-butylene group and the like).

In the general formula (2), p is usually 5 to 57, and preferably 10 to 40 from the viewpoint of foam suppression. (B) is usually produced by an addition reaction of alkylene oxide, and usually has a distribution in the number of moles of alkylene oxide added, so p represents an average value of the number of moles of alkylene oxide added and is an integer. Not necessarily.
In addition, 5 to 50 of p R ⁶ is usually a propylene group, and if it exceeds 50, it is not preferable from the viewpoint of compatibility with (A), and if it is less than 5, it is preferable because it does not become low foaming property. Absent. The number of propylene groups in R ⁶ is preferably 10 to 40 from the viewpoint of foam suppression.
Usually, 0 to 2 of p R ⁶ are ethylene groups, and if it exceeds 2, R 2 is not preferred because it does not have low foaming properties.
Usually, 0 to 5 of p R ⁶ are butylene groups, and if it exceeds 5, the compatibility with (A) decreases, which is not preferable. The number of propylene groups, ethylene groups, and butylene groups among the p R ⁶ is an average value and is not necessarily an integer.
The bonding form of p R ⁶ Os may be block, random, or a combination thereof, but from the viewpoint of foam suppression, a block is preferred.
(B) may be used independently and may use 2 or more types together.

(B) is usually in the presence or absence of a catalyst, a monohydric alcohol to the alkylene oxide having 2 to 4 carbon atoms represented by R ⁵ -OH [such as ethylene oxide (hereinafter, abbreviated as EO), propylene oxide ( 1,2-propylene oxide and 1,3-propylene oxide, hereinafter abbreviated as PO), butylene oxide (1,2-butylene oxide, 1,3-butylene oxide and 1,4-butylene oxide, , And abbreviated as BO)]. As the catalyst, a known alkaline catalyst (such as potassium hydroxide or sodium hydroxide) and an acid catalyst (such as BF ₃ ) can be used, and the reaction temperature is usually 50 to 180 ° C. although it varies depending on the kind of alkylene oxide to be added.

R ⁵ —OH used in the production of (B) may be a natural alcohol or a synthetic alcohol (Ziegler alcohol, oxo alcohol, etc.), and specifically, an alcohol in which a hydroxyl group is bonded to the hydrocarbon group mentioned as R ^5. Is mentioned.

  The solubility of (B) in 100 g of water at 30 ° C. is usually 1 g or less, preferably 0.8 g or less, more preferably 0.3 g or less, particularly 0.01 g or less from the viewpoint of foam suppression. In the present invention, the solubility in water at 30 ° C. is the maximum number of grams of a sample that completely dissolves in 100 g of ion-exchanged water at 30 ° C.

  Specific examples of preferred polyethers (B) in the present invention include adducts of 19 mol PO of n-butanol (solubility in 100 g of water at 30 ° C. = 0.01 g or less), 1 mol PO of n-dodecyl alcohol and 5 mol PO. Random adduct (solubility in 100 g of water at 30 ° C. = 0.01 g or less), random adduct of EO 2 mol and PO 5 mol of ethanol (solubility in 100 g of water at 30 ° C. = 1.0 g), EO 1 of methanol Molar PO 10 mol BO 5 mol random adduct (solubility in water 100 g at 30 ° C. = 0.3 g) and octadecyl alcohol PO 30 mol BO 5 mol random adduct (solubility in water 100 g at 30 ° C. = 0.01 g or less) Etc.

The water-soluble alkylene glycol alkyl ether (C) having 3 to 14 carbon atoms in the present invention (hereinafter sometimes abbreviated as (C) in some cases) is stable when the cationic surfactant composition is stored for a long period of time. And a function of reducing the viscosity of the cationic surfactant composition. In addition, (C) can be used as a reaction solvent for producing (A).
In the present invention, water-soluble means that 100 g or more is dissolved in 100 g of water at 30 ° C.

Examples of the water-soluble alkylene glycol alkyl ether (C) having 3 to 14 carbon atoms include ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether. , Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether and triethylene glycol dibutyl ether.
Among these, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, triethylene glycol monobutyl ether and triethylene glycol dibutyl ether are preferable from the viewpoint of stability and low viscosity when the cationic surfactant composition is stored for a long period of time. is there.
(C) may be used alone or in combination of two or more.

  The divalent to hexavalent polyhydric alcohol (D) in the present invention (hereinafter sometimes simply referred to as (D)) has a function of enhancing stability when the cationic surfactant composition is stored for a long period of time. Have. Moreover, (D) can be used as a reaction solvent when producing (A).

(D) includes ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 1,4-butanediol, glycerin, trimethylolethane, trimethylolpropane, Examples include 2-methylglycerin, diglycerin, triglycerin, tetraglycerin, pentaerythritol, dipentaerythritol, and sorbitol. Among these, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol are preferable from the viewpoint of stability when the cationic surfactant composition is stored for a long period of time. Butanediol, 2,3-butanediol and 1,4-butanediol, more preferably ethylene glycol and propylene glycol.
(D) may be used alone or in combination of two or more.

  The monohydric alcohol (E) having 1 to 5 carbon atoms in the present invention [hereinafter sometimes simply referred to as (E)] has a function of reducing the viscosity of the cationic surfactant composition.

(E) includes methanol, ethanol, n-propanol, isopropanol, 1,2-dimethylpropanol, 1,1-dimethylpropanol, 2,2-dimethylpropanol, n-butanol, sec-butanol, isobutanol, tert- Examples include butanol, 2-methyl-1-butanol, n-pentyl alcohol, sec-pentyl alcohol, isopentyl alcohol, and 3-pentyl alcohol.
(E) may be used alone or in combination of two or more.

  As described above, a water-soluble alkylene glycol alkyl ether (C) having 3 to 14 carbon atoms is used, or a 2 to 6-valent polyhydric alcohol (D) and a monovalent alcohol (E) having 1 to 5 carbon atoms are used in combination. Accordingly, the storage stability of the cationic surfactant composition is improved and the viscosity can be lowered. Therefore, the constitution of the present invention includes the cationic surfactant (A), the polyether (B) and (C). There are two forms: those containing as essential components and those containing (A), (B), (D) and (E) as essential components.

  The low foaming cationic surfactant composition of the present invention can contain water. The kind of water is not particularly limited, and industrial water, tap water, well water, ion exchange water, distilled water, and the like can be used.

  If necessary, other additives may be added to the low foaming cationic surfactant composition of the present invention as long as the effects of the present invention are not impaired. Examples of the additive include an antifoaming agent, a pH adjuster, an antioxidant, an ultraviolet absorber, an algaeproofing agent, and a corrosion inhibitor. Examples of the antifoaming agent include silicone (dimethylpolysiloxane, etc.), mineral oil, Metal soap, etc .; caustic alkali (caustic soda, etc.) as pH adjuster, amine (mono-, di- or triethanolamine etc.), phenolic [2,6-di-t-butyl-p as antioxidant -Cresol (BHT) and 2,2'-methylenebis (4-methyl-6-t-butylphenol), etc.], sulfur-based [dilauryl 3,3'-thiodipropionate (DLTDP) and dioctadecyl 3,3'- Thiodipropionate (DSTDP) etc.], phosphorus [triphenyl phosphite (TPP) and triisodecyl phosphite (TDP) etc.], amine [octylated di Phenylamine, Nn-butyl-p-aminophenol, N, N-diisopropyl-p-phenylenediamine, etc.]; UV absorbers such as benzophenones (2-hydroxybenzophenone and 2,4-dihydroxybenzophenone), Salicylates (such as phenyl salicylate and 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate), benzotriazoles [(2′-hydroxyphenyl) benzotriazole and (2′-hydroxy-5′-methylphenyl) benzotriazole etc.], acrylic [ethyl-2-cyano-3,3-diphenyl acrylate and methyl-2-carbomethoxy-3- (paramethoxybenzyl) acrylate etc.] Etc .; As antibacterial agents, isothiazolone compounds Halogenated aliphatic nitro compounds (such as 2-bromo-2-nitro-1,3-propanediol and 2,2-dibromo-2-nitroethanol) and esters thereof, dibromonitrile propionamide, alkylene bis thiocyanate (methylene) Bisthiocyanate, etc.), 1,4-bisbromoacetoxy-2-butene, hexabromodimethylsulfone, isophthalonitrile compounds (5-chloro-2,4,6-trifluoroisophthalonitrile, tetrachloroisophthalonitrile, etc.) , Dimethyldithiocarbamate, 4,5-dichloro-1,2-diol-3-one, 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide, triiodoallyl alcohol, bromonitrostyrene, aldehyde Compound (glutar aldehyde , Phthalaldehyde, isophthalaldehyde and terephthalaldehyde), dichloroglyoxime, benzaldoxime compounds (such as α-chlorobenzaldoxime and α-chlorobenzaldoxime acetate) and halogenated hydantoin compounds (1,3-dichloro- 5,5-dimethylhydantoin and 1,3-dibromo-5,5-dimethylhydantoin, etc.), etc. As an algae, Amerington, etc .; As a corrosion inhibitor, triazole compounds (tolyltriazole, benzotriazole, methylbenzotriazole, etc.) ), Molybdic acid, tungstic acid, silicic acid, nitrous acid and their salts, zinc chloride, acidic zinc chloride hydrochloride, zinc sulfate, zinc lignin sulfonate and hydrazine.

  The viscosity at 25 ° C. of the low-foaming cationic surfactant composition of the present invention is preferably 10 to 500 mPa · s, more preferably 10 to 300 mPa · s, and particularly preferably 10 to 200 mPa from the viewpoint of ease of handling. -S.

The content of (A) in the low-foaming cationic surfactant composition of the present invention is based on the weight of the low-foaming cationic surfactant composition, from the viewpoint of low foaming properties and marine organism adhesion prevention properties. 3 to 40% by weight, more preferably 5 to 30% by weight, and particularly preferably 7 to 25% by weight.
The content of (B) is preferably 2 to 50% by weight, more preferably 4 to 45% from the viewpoint of low foaming property and product stability, based on the weight of the low foaming cationic surfactant composition. %, Particularly preferably 6 to 40% by weight.
The content of (C) is preferably 5 to 60% by weight, more preferably 10 based on the weight of the low foaming cationic surfactant composition, from the viewpoint of low foaming property, product stability and viscosity reduction. It is -55 weight%, Most preferably, it is 20-50 weight%.
The content of (D) is preferably 20 to 60% by weight, more preferably 25 to 55% by weight based on the weight of the low foaming cationic surfactant composition, from the viewpoint of low foaming and product stability. %, Particularly preferably 30 to 50% by weight.
The content of (E) is preferably 3 to 20% by weight, more preferably 5 to 18% by weight based on the weight of the low foaming cationic surfactant composition, from the viewpoint of viscosity reduction and low foaming property. Particularly preferably, it is 7 to 15% by weight.
When the low-foaming cationic surfactant composition contains water, the water content is based on the weight of the low-foaming cationic surfactant composition, when the cationic surfactant composition is stored for a long period of time. From the viewpoint of stability, the content is preferably 1 to 70% by weight, more preferably 5 to 65% by weight, and particularly preferably 10 to 60% by weight.

  When using other additives, the amount used is based on the weight of the low-foaming cationic surfactant composition of the present invention, and the antifoaming agent is usually 0.01 to 1% by weight, preferably 0.01. -0.1 wt%, pH adjuster is usually 0.1-5 wt%, preferably 0.2-2.5 wt%, antioxidant and UV absorber are usually 0.01-2 wt%, Preferably 0.02-1% by weight, antibacterial agent, anti-algae agent and corrosion inhibitor are usually 0.2-2% by weight, preferably 0.5-1% by weight, respectively.

  When the low-foaming cationic surfactant composition of the present invention is used by adding it to seawater, it is preferably diluted with seawater so that the concentration becomes 0.05 to 1 ppm, and more preferably 0. 0.07 to 0.5 ppm, particularly preferably 0.1 to 0.3 ppm. If the concentration is within this range, the foaming property is low and the effect of preventing marine organism adhesion is good, and there is little effect on marine organisms other than those targeted for adhesion prevention such as mussels and barnacles.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Below, a part shows a weight part.

Production Example 1
A pressure-resistant SUS autoclave equipped with a heating / cooling device, a stirrer, and a pressure-resistant cylinder was charged with 44.0 parts of n-butanol and 0.4 parts of potassium hydroxide, and the inside of the autoclave was purged with nitrogen at 0.2 MPa three times. The temperature was raised to ˜130 ° C., 655.6 parts of 1,2-propylene oxide placed in a pressure cylinder was injected over about 3 hours, and the reaction was continued for 2 hours at the same temperature. Obtained 700 parts of propylene oxide 19 mol adduct (B-1).

Production Example 2
A pressure-resistant SUS autoclave equipped with a heating / cooling device, a stirrer, and a pressure-resistant cylinder was charged with 250.1 parts of n-dodecyl alcohol and 0.8 parts of potassium hydroxide, and the inside of the autoclave was purged with nitrogen at 0.2 MPa three times. The temperature was raised to 100 to 130 ° C., a mixture of 59.2 parts of ethylene oxide and 389.9 parts of 1,2-propylene oxide placed in a pressure cylinder was injected over about 2 hours, and the reaction was continued for 2 hours at the same temperature. Then, 700 parts of 1 mol of ethylene oxide of n-dodecyl alcohol and 5 parts of random adduct of 1,2-propylene oxide (B-2) were obtained.

Production Example 3
A pressure-resistant SUS autoclave equipped with a heating / cooling device, a stirrer, and a pressure-resistant cylinder was charged with 22.0 parts of methanol and 0.4 part of potassium hydroxide, and the inside of the autoclave was purged with nitrogen at 0.2 MPa three times. The temperature was raised to 0 ° C., and a mixture of 30.3 parts of ethylene oxide, 399.4 parts of 1,2-propylene oxide and 247.9 parts of 1,2-butylene oxide placed in a pressure cylinder was injected over about 4 hours, The reaction was continued at the same temperature for 2 hours to obtain 700 parts of 1 mol of ethylene oxide, 1 mol of 1,2-propylene oxide, 1 mol of 1,2-butylene oxide and 5 mol of random adduct (B-3).

Production Example 4
A glass reaction vessel equipped with a heating / cooling device, a stirrer and a dropping funnel was charged with 295.0 parts of dimethyl oleylamine and 263.7 parts of water, temperature-controlled at 20 to 40 ° C., and placed in the dropping funnel under stirring. 104.3 parts of% hydrochloric acid was added dropwise over 1 hour and the mixture was further stirred for 30 minutes to obtain 663 parts of a 50% aqueous solution of dimethyloleylamine hydrochloride.

Example 1
A pressure-resistant glass autoclave equipped with a heating / cooling device, a stirrer and a pressure cylinder was charged with 121.5 parts of hexadecyldimethylamine and 309.6 parts of propylene glycol, and the inside of the autoclave was purged with nitrogen at 0.2 MPa three times. After raising the temperature to ˜95 ° C., 23.6 parts of methyl chloride was dropped from the pressure cylinder over 30 minutes, and the mixture was further stirred at the same temperature for 2 hours, then cooled to 70 to 75 ° C., and nitrogen was 0.5 L / min. The unreacted methyl chloride was removed by flowing in the liquid at a flow rate of 1 hour for 1 hour. Further, after cooling to 30 ° C., 85.0 parts of (B-1) obtained in Production Example 1, 49.0 parts of n-butanol and 112.5 parts of water were added and stirred for 30 minutes, and the viscosity at 25 ° C. Obtained 700 parts of a cationic surfactant composition having a viscosity of 90 mPa · s.

Example 2
Into a pressure-resistant glass autoclave equipped with a heating / cooling device, a stirrer and a pressure-resistant cylinder, 60.8 parts of hexadecyldimethylamine and 179.6 parts of propylene glycol were charged, and the inside of the autoclave was replaced with nitrogen three times with 0.2 MPa of nitrogen. After raising the temperature to ˜95 ° C., 11.8 parts of methyl chloride was dropped from the pressure cylinder over 30 minutes, and further stirred at the same temperature for 2 hours, then cooled to 70 to 75 ° C., and nitrogen was 0.5 L / min. The unreacted methyl chloride was removed by flowing in the liquid at a flow rate of 1 hour for 1 hour. Further, after cooling to 30 ° C., 288.4 parts of (B-1) obtained in Production Example 1, 49.0 parts of n-butanol and 111.0 parts of water were added and stirred for 30 minutes, and the viscosity at 25 ° C. Of 700 mPa · s of a cationic surfactant composition was obtained.

Example 3
A pressure-resistant glass autoclave equipped with a heating / cooling device, a stirrer and a pressure cylinder was charged with 207.6 parts of didecylmethylamine and 182.8 parts of ethylene glycol, and the inside of the autoclave was purged with nitrogen at 0.2 MPa three times. After raising the temperature to ˜95 ° C., 35.4 parts of methyl chloride was dropped from the pressure cylinder over 30 minutes, and the mixture was further stirred at the same temperature for 2 hours, then cooled to 70 to 75 ° C., and nitrogen was 0.5 L / min. The unreacted methyl chloride was removed by flowing in the liquid at a flow rate of 1 hour for 1 hour. Further, after cooling to 30 ° C., 221.5 parts of (B-2) obtained in Production Example 2, 50.0 parts of methanol and 4.5 parts of water were added and stirred for 30 minutes, and the viscosity at 25 ° C. was 120 mPa -Obtained 700 parts of s cationic surfactant composition.

Example 4
Cationic surfactant having a viscosity of 100 mPa · s at 25 ° C. in the same manner as in Example 3 except that (B-2) obtained in Production Example 2 was replaced with (B-3) obtained in Production Example 3. 700 parts of a composition were obtained.

Example 5
A pressure-resistant glass autoclave equipped with a heating / cooling device, a stirrer, and a pressure-resistant cylinder was charged with 128.5 parts of benzyldodecylmethylamine and 184.3 parts of diethylene glycol, and the inside of the autoclave was purged with nitrogen at 0.2 MPa three times. After the temperature was raised to 95 ° C., 23.6 parts of methyl chloride was added dropwise from the pressure cylinder over 30 minutes, and the mixture was further stirred at the same temperature for 2 hours, and then cooled to 70 to 75 ° C. The unreacted methyl chloride was removed by flowing in the liquid at a flow rate for 1 hour. Further, after cooling to 30 ° C., 144.2 parts of (B-1) obtained in Production Example 1, 60.0 parts of n-pentyl alcohol and 160.6 parts of water were added and stirred for 30 minutes. 700 parts of a cationic surfactant composition having a viscosity of 110 mPa · s were obtained.

Example 6
A cationic surfactant having a viscosity at 25 ° C. of 80 mPa · s in the same manner as in Example 5 except that (B-1) obtained in Production Example 1 was replaced with (B-2) obtained in Production Example 2. 700 parts of a composition were obtained.

Example 7
A pressure-resistant glass autoclave equipped with a heating / cooling device, a stirrer and a pressure cylinder was charged with 132.1 parts of dimethyloctadecylamine and 233.5 parts of dipropylene glycol, and the inside of the autoclave was purged with nitrogen at 0.2 MPa three times. After raising the temperature to ˜95 ° C., 23.6 parts of methyl chloride was dropped from the pressure cylinder over 30 minutes, and the mixture was further stirred at the same temperature for 2 hours, then cooled to 70 to 75 ° C., and nitrogen was 0.5 L / min. The unreacted methyl chloride was removed by flowing in the liquid at a flow rate of 1 hour for 1 hour. After further cooling to 30 ° C., 94.0 parts of (B-3) obtained in Production Example 3, 55.0 parts of isopropyl alcohol and 163.0 parts of water were added and stirred for 30 minutes, and the viscosity at 25 ° C. 700 parts of 60 mPa · s cationic surfactant composition was obtained.

Example 8
A pressure-resistant glass autoclave equipped with a heating / cooling device, a stirrer and a pressure cylinder was charged with 66.1 parts of dimethyloctadecylamine and 190.5 parts of propylene glycol, and the inside of the autoclave was purged with nitrogen at 0.2 MPa three times. After raising the temperature to 95 ° C., 11.8 parts of methyl chloride was dropped from the pressure cylinder over 30 minutes, and the mixture was further stirred at the same temperature for 2 hours, then cooled to 70 to 75 ° C., and nitrogen was reduced to 0.5 L / min. The unreacted methyl chloride was removed by flowing in the liquid at a flow rate for 1 hour. Further, after cooling to 30 ° C., 288.4 parts of (B-3) obtained in Production Example 3, 40.0 parts of isopropyl alcohol and 103.8 parts of water were added and stirred for 30 minutes, and the viscosity at 25 ° C. 700 parts of a cationic surfactant composition having 140 mPa · s was obtained.

Example 9
A glass reaction vessel equipped with a heating / cooling device, a stirrer and a dropping funnel was charged with 36.5 parts of hexadecyldimethylamine, 190 parts of triethylene glycol monobutyl ether and 386.6 parts of water, and the temperature was adjusted to 60 to 80 ° C. While stirring, 16.9 parts of dimethyl sulfuric acid placed in the dropping funnel was added dropwise over 1 hour, followed by further stirring for 30 minutes. Further, after cooling to 30 ° C., 70 parts of (B-1) obtained in Production Example 1 was added and stirred for 30 minutes to obtain 700 parts of a cationic surfactant composition having a viscosity at 25 ° C. of 50 mPa · s. .

Comparative Example 1
A pressure-resistant glass autoclave equipped with a heating / cooling device, a stirrer, and a pressure cylinder was charged with 121.5 parts of hexadecyldimethylamine and 460.0 parts of water, and the inside of the autoclave was purged with nitrogen at 0.2 MPa three times. After raising the temperature to 95 ° C., 23.6 parts of methyl chloride was dropped from the pressure cylinder over 30 minutes, and further stirred at the same temperature for 2 hours, then cooled to 70 to 75 ° C., and nitrogen was reduced to 0.5 L / min. The unreacted methyl chloride was removed by flowing in the liquid at a flow rate for 1 hour. Further, after cooling to 30 ° C., 96.1 parts of a 50% aqueous solution of oleyldimethylamine hydrochloride obtained in Production Example 1 was added and stirred for 30 minutes to obtain 700 parts of a cationic surfactant composition.

Comparative Example 2
A pressure-resistant glass autoclave equipped with a heating / cooling device, a stirrer, and a pressure cylinder was charged with 121.5 parts of hexadecyldimethylamine and 555.4 parts of water, and the inside of the autoclave was purged with nitrogen at 0.2 MPa three times. After raising the temperature to 95 ° C., 23.6 parts of methyl chloride was dropped from the pressure cylinder over 30 minutes, and further stirred at the same temperature for 2 hours, then cooled to 70 to 75 ° C., and nitrogen was reduced to 0.5 L / min. The unreacted methyl chloride was removed by flowing in the liquid at a flow rate for 1 hour. Further, after cooling to 30 ° C., 0.7 part of a silicon-based antifoaming agent SN-500E [manufactured by San Nopco Co., Ltd.] was added and stirred for 30 minutes to obtain 700 parts of a cationic surfactant composition.

  Using the cationic surfactant compositions of Examples 1 to 9 and Comparative Examples 1 and 2, the results of evaluation of product stability, foaming property and marine organism adhesion prevention property are shown in Table 1 by the following methods. .

<Product stability evaluation method>
50 g of the cationic surfactant composition was put in a glass bottle, covered, and allowed to stand at −5 ° C., 25 ° C. and 50 ° C. for 6 months, and the change in appearance was observed. The product stability was evaluated according to the following criteria.
○: Uniform and transparent with no separation / precipitation ×: Separation / precipitation has occurred

<Foamability evaluation method>
30 ml of a test solution obtained by diluting a cationic surfactant composition that was allowed to stand at 25 ° C. for 6 months with seawater so that the concentration of the cationic surfactant composition was 0.09% was placed in a 100 ml stoppered measuring cylinder and stoppered. After shaking the graduated cylinder 10 times by hand, the foam volume after 1 minute and 5 minutes was measured. The smaller the foam volume, the lower the foaming property.

<Evaluation method for marine organism adhesion prevention>
Seawater was pumped from the beach, and the cationic surfactant compositions of Examples 1 to 9 and Comparative Examples 1 and 2 were added so that the concentration of the cationic surfactant composition was 0.1 ppm, and the inner diameter was 74 mm and the length was 2 m. Water was passed through the PVC pipe at a flow rate of 3 tons / hour for 40 days, and the number of mussels and barnacles adhering to the PVC pipe was measured.

The low-foaming cationic surfactant composition of the present invention has less foaming and is excellent in storage stability without separation and sedimentation even after long-term storage. In addition, the range of use can be expanded to applications where the foamability has been problematic so far.
Further, by adding the low-foaming cationic surfactant composition of the present invention to seawater cooling water, adhesion of marine organisms such as blue mussels and barnacles to the cooling water piping can be prevented, and low Problems with conventional surfactants, such as foaming, decrease in fluidity of cooling water due to foaming in pipes and pumps, and bubbles remain on the sea surface for a long time due to foaming when flowing cooling water into the sea It is possible to solve the point.

Claims (5)

Cationic surfactant (A) represented by general formula (1), polyether (B) represented by general formula (2) and having a solubility in 100 g of water at 30 ° C. of 1 g or less, and 3 to 14 carbon atoms Water-soluble alkylene glycol alkyl ether (C) or (A), (B), a bivalent to hexavalent polyhydric alcohol (D), and a monohydric alcohol (E) having 1 to 5 carbon atoms. A low-foaming cationic surfactant composition.

[Wherein, R ^1, R ² and R ³ are alkenyl group linear or branched in each the same or different 3-24 alkyl group carbon atoms or a linear or branched carbon atoms 1 to 24; R ⁴ is the number of carbon atoms A linear or branched alkyl group or alkenyl group having 6 to 24 carbon atoms, or an arylalkyl group or arylalkenyl group having 7 to 24 carbon atoms; f is an integer of 1 to 10, X ^f− is an f-valent counter ion, One or more ions selected from the group consisting of ions, hydroxy ions, sulfate ions, phosphate ions, nitrate ions, carboxylate ions, sulfonate ions, sulfate ester ions, phosphate ester ions, and super strong acid ions. ]
^{R 5 O- (R 6 O)} p -H (2)
[Wherein, R ⁵ is an aliphatic hydrocarbon group having 1 to 24 carbon atoms, R ⁶ is an alkylene group having 2 to 4 carbon atoms, p is an average value of 5 to 57, and p R ⁶ 5 to 50 of them are propylene groups, 0 to 2 are ethylene groups, 0 to 5 are butylene groups, and p R ⁶ is composed of two or more alkylene groups The bonding form of p R ⁶ Os may be block, random, or a combination thereof. ]   Based on the weight of the low foaming cationic surfactant composition, the content of (A) is 3 to 40% by weight, the content of (B) is 2 to 50% by weight, and the content of (C) The low-foaming cationic surfactant composition according to claim 1, wherein 5 to 60% by weight, the content of (D) is 20 to 60% by weight, and the content of (E) is 3 to 20% by weight. object.   3. The (C) is one or more water-soluble alkylene glycol alkyl ethers selected from the group consisting of diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, triethylene glycol monobutyl ether and triethylene glycol dibutyl ether. Low foaming cationic surfactant composition.   (D) is selected from the group consisting of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, and 1,4-butanediol. The low-foaming cationic surfactant composition according to claim 1, which is one or more dihydric alcohols.   The low-foaming cationic surfactant composition according to any one of claims 1 to 4, which is used for preventing marine organism adhesion.