JP2008188480A - Defoamer composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a wax emulsion type defoamer which does not easily cause solidification due to drying on a liquid surface, eliminates a solidified object by dissolution by adding a new defoamer in a service tank or the like even when it is caused, and is excellent in emulsion stability and a defoaming effect. <P>SOLUTION: In the defoamer composition based on oil-in-water emulsion for which an oil phase occupies 5 to 60 mass% of emulsion components, one or two or more kinds of compounds expressed by a formula; R-O-(C<SB>3</SB>H<SB>7</SB>O)<SB>m</SB>/(C<SB>2</SB>H<SB>5</SB>O)<SB>n</SB>-H are used as an emulsifier. In the formula, R represents a saturated or unsaturated C8-24 alkyl group, an acyl group, a substituted or unsubstituted aryl group or rosin residues, m is the integer of 1-10, and n is the integer of 20-80. A symbol "/" indicates that an addition form can be in a random shape or a block shape. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an oil-in-water emulsion antifoaming agent composition, and more particularly, to an antifoaming agent composition that makes it difficult to cause solidification by drying on the liquid surface and is excellent in emulsion stability and antifoaming effect.

  Conventional oil-in-water emulsion defoamers typically include wax emulsion defoamers mainly composed of higher alcohols (see Patent Documents 1 to 3). The wax emulsion type antifoaming agent has a good defoaming effect on fine bubbles intervening in the pulp slurry and has excellent effects such as little influence on the size effect. Yes. However, when a conventional wax emulsion type antifoaming agent is used, it tends to be difficult to use because the solidified product resulting from drying on the product surface clogs the metering pump, etc. when the service tank is used in an open system. It was. Patent Documents 4 and 5 can be cited as examples of solutions to such problems, but there is room for improvement in the defoaming effect and emulsion stability. That is, because emphasis is placed on the suppression of solidification, the defoaming effect and the emulsion stability may be impaired, and a balanced antifoam composition has been demanded.

JP-A-60-156516 Special table 2002-522657 JP 2001-62204 A JP-A-11-76703 JP 2003-164707 A

  The present invention has been made in consideration of such a situation, and solves various problems of conventional wax emulsion antifoaming agents. That is, the object of the present invention is that it is difficult to cause solidification by drying on the liquid surface, and even if it occurs, the solidified product disappears due to dissolution by addition of a new antifoaming agent in a service tank or the like, and the emulsion stability Another object of the present invention is to provide a wax emulsion type antifoaming agent having an excellent antifoaming effect.

As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that by using a specific nonionic surfactant as an emulsifier for an oil-in-water emulsion, suppression of solidification, emulsion stability and antifoaming effect The present invention was completed by finding that a defoamer composition balanced in all of the above can be obtained.
That is, the present invention relates to an antifoaming agent composition based on an oil-in-water emulsion in which the oil phase accounts for 5 to 60% by mass of the emulsion constituents, and as an emulsifier, one of the compounds represented by the following general formula (1): It is an antifoamer composition characterized by using 2 or more types.

R—O— (C ₃ H ₇ O) _m / (C ₂ H ₅ O) _n —H (1)

In the formula, R represents a saturated or unsaturated alkyl group having 8 to 24 carbon atoms, an acyl group, a substituted or unsubstituted aryl group, or a rosin residue. m represents an integer of 1 to 10, and n represents an integer of 20 to 80. “/” Indicates that the additional form may be random or block.

  The antifoam composition of the present invention has a controlled dispersion state of emulsion particles on the product surface, hardly causes solidification due to drying on the liquid surface. It has the effect that the solidified product disappears by dissolution by adding. In addition, it is practically very useful in that the emulsion stability and the defoaming effect are not impaired.

  The present invention will be described in detail below.

The emulsifier used in the present invention is represented by the following general formula (1).

R—O— (C ₃ H ₇ O) _m / (C ₂ H ₅ O) _n —H (1)

In the formula, R represents a saturated or unsaturated alkyl group having 8 to 24 carbon atoms, an acyl group, a substituted or unsubstituted aryl group, or a rosin residue. m represents an integer of 1 to 10, and n represents an integer of 20 to 80. “/” Indicates that the additional form may be random or block.
In the general formula (1), m represents the number of added moles of propylene oxide, and is an integer of 1 to 10, preferably an integer of 2 to 4. n represents the number of added moles of ethylene oxide and is an integer of 20 to 80, preferably an integer of 40 to 60. 25-75 are preferable and, as for the total (m + n) of the addition mole number of ethylene oxide and propylene oxide, 40-60 are more preferable. The ratio of the number of moles of ethylene oxide and propylene oxide added is preferably n: m = 20: 1 to 8: 1, more preferably 20: 1 to 15: 1. The addition form of ethylene oxide and propylene oxide may be random or block.

Among the emulsifiers according to the present invention, it is particularly preferable to use a compound represented by the following general formula (2) from the viewpoints of suppression of solidification and defoaming effect.

_{R-O- (C 2 H 5} O) p (C 3 H 7 O) m (C 2 H 5 O) q -H (2)

In the formula, R and m are the same as those in the general formula (1). p and q are in the range of 1 to 30, 20 to 60, respectively, and are positive integers satisfying the relationship of p + q = n (n is the same as that in the general formula (1)). Among these, those in which p is an integer of 2 to 5 and q is an integer of 40 to 55 are particularly preferable.

  Specific examples when R in the general formulas (1) and (2) is a saturated or unsaturated alkyl group having 8 to 24 carbon atoms include 1-octyl group, 1-decyl group, 1-undecyl group, 1 -Dodecyl group, 1-tridecyl group, 1-tetradecyl group, 1-pentadecyl group, 1-hexadecyl group, 1-heptadecyl group, 1-octadecyl group, 1-nonadecyl group, 1-eicosyl group, 1-heneicosyl group, 1 -Primary alkyl group such as docosyl group, 1-tricosyl group, 1-tetracosyl group, oleyl group, elaidyl group, linoleyl group, linolenyl group, 2-octyl group, 2-decyl group, 2-undecyl group, 2-dodecyl group Group, 2-tridecyl group, 2-tetradecyl group, 2-pentadecyl group, C12-14 secondary alcohol “Softanol” (registered trademark) manufactured by Nippon Shokubai Co., Ltd. Although the secondary alkyl group can be mentioned, the secondary alkyl group is preferred in that there is no thickening of the emulsion over time after emulsification.

  Specific examples when R in the general formulas (1) and (2) is a saturated or unsaturated acyl group having 8 to 24 carbon atoms include 1-octanoyl group, 1-decanoyl group, 1-dodecanoyl group, 1 -Tetradecanoyl group, 1-pentadecanoyl group, 1-hexadecanoyl group, 1-heptadecanoyl group, 1-octadecanoyl group, 1-nonadecanoyl group, 1-eicosanoyl group, 1-heneicosanoyl group, In addition to 1-docosanoyl group, 1-tricosanoyl group, 1-tetracosanoyl group, oleoyl group, straight chain such as elaidic acid residue, linoleic acid residue, linolenic acid residue, stearolic acid residue, ricinoleic acid residue Examples include fatty acids having branches such as fatty acid residues, isooctadecanoic acid residues, isoeicosanoic acid residues, isodocosanoic acid residues, and isotetracosanoic acid residues. But not particularly limited thereto.

但し、Ｒ^２は水素原子またはフェニル基またはベンジル基またはスチリル基または炭素数１〜１２のアルキル基またはモノベンジルフェニル基またはジベンジルフェニル基またはモノスチリルフェニル基またはジスチリルフェニル基またはクミル基またはモノベンジルクミル基またはジベンジルクミル基またはモノスチリルクミル基またはジスチリルクミル基を示す。ｎは１〜３の整数であり、ｎが２または３の場合はＲ^２の種類は上記のものからそれぞれ独立に選ばれる。 Examples of the substituted or unsubstituted aryl group include a group represented by the following general formula (3) or a substituted or unsubstituted naphthyl group.

R ² represents a hydrogen atom, a phenyl group, a benzyl group, a styryl group, an alkyl group having 1 to 12 carbon atoms, a monobenzylphenyl group, a dibenzylphenyl group, a monostyrylphenyl group, a distyrylphenyl group, a cumyl group, or a monovalent group. A benzyl cumyl group, a dibenzyl cumyl group, a monostyryl cumyl group or a distyryl cumyl group is shown. n is an integer of 1 to 3, and when n is 2 or 3, the type of R ² is independently selected from the above.

  The rosins include rosin obtained from a resin contained in pine itself and derivatives thereof. The rosin itself can be broadly classified into gum rosin, wood rosin, tall oil rosin, and the main components thereof are abietic acid, neoabietic acid, levopimaric acid, hydroabietic acid, pimaric acid, dextropimalic acid and the like. Derivatives of rosin include disproportionated rosin, hydrogenated rosin, dehydrogenated rosin, and polymerized rosin.

  The compounds represented by the general formulas (1) and (2) can be obtained by a known method. For example, a saturated or unsaturated alcohol having 8 to 24 carbon atoms or a saturated or unsaturated fatty acid may be basic. It can be obtained by adding ethylene oxide and propylene oxide in the presence of a catalyst.

  Although the usage-amount of an emulsifier is not specifically limited, 0.1-5 mass% is preferable in an oil-in-water emulsion.

  Specifically, as the oil phase component of the oil-in-water emulsion according to the present invention, (a) an α-olefin having 26 or more carbon atoms, (b) a higher alcohol having 12 to 32 carbon atoms, and (c) 12 to 12 carbon atoms. The higher fatty acid ester which consists of 32 higher alcohol and a C12-C32 higher fatty acid etc. is mentioned, The total amount contains 5-60 mass% in water, Preferably it contains 15-35 mass%. If it is less than 5% by mass, it is not economical, and if it exceeds 60% by mass, the emulsion tends to solidify, which is not preferable.

  In the present invention, a known water-soluble polymer can be used as an emulsion separation inhibitor. Examples of water-soluble polymers include starch, mannagalactan, sodium alginate, xanthan gum, gum tragacanth, arabic gum, dextran, gelatin, casein, methylcellulose, ethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, carboxymethyl starch, polyvinyl alcohol, sodium polyacrylate, polyethylene oxide And the like.

  In the oil-in-water emulsion of the present invention, known preservatives can be used for the purpose of preserving storage, but there is no limitation on the use of these preservatives.

  The method for producing an oil-in-water emulsion according to the present invention is not particularly limited, and is a method commonly used in the production of conventional oil-in-water emulsions (for example, the method described in JP-A-2001-113104). Can be used.

  EXAMPLES Next, although an Example is given and this invention is further demonstrated, this invention is not limited to these Examples.

The emulsifiers shown in the table below were synthesized by a conventional method and subjected to the evaluation described below.

(Example 1)
60 g of α-olefin (Dialene 30 manufactured by Mitsubishi Chemical Corporation) containing 95% or more of carbon atoms in a container (150 g), 150 g of higher alcohol (NAFOL1822 manufactured by CONDEA) containing 92 or more carbon atoms, stearyl alcohol and stearic acid 8 g of the ester and 9 g of the above emulsifier 1 were added, heated to 85 ° C., 700 g of hot water having the same temperature was added, stirred and mixed, and then stirred at 8000 rpm for 1 minute using a homomixer (manufactured by Nippon Seiki). An oil-type emulsion was prepared, and then cooled to 30 ° C. to prepare an antifoam composition according to the present invention.

(Examples 2-6, Comparative Examples 1-3)
The formulation and manufacturing method are the same as in Example 1 except that emulsifiers 2 to 9 were used.

Performance evaluation (1)
Confirmation of generation state of solidified product by drying of liquid surface Each 20 g of the antifoam composition was placed in a 100 cc beaker and left in an open state to visually observe the generation state of solidified product by drying (implemented for 5 days). Next, 20 g of each antifoaming agent was further added to the beaker subjected to the 5-day test, and after 6 hours, filtration was performed with a 100 mesh wire, and the residue (%) on the wire was measured as an undissolved solidified product ( Assuming additional antifoam in service tank). The results are shown in the table below.

Performance evaluation (2)
Defoaming performance, emulsion stability test [foaming liquid production method]
Corrugated used paper was disaggregated with a desktop disintegrator to obtain a pulp slurry having a concentration of 5%. Dilute to 1% with tap water and warm to 65 ° C, size agent (Perosa WS Modern Chemical Co., Ltd.) 5% (as pulp and solids), paper strength enhancer (PS-117 Arakawa Chemical Co., Ltd.) ) 0.4% (vs. pulp, as solid content) was added and stirred well, and then adjusted to pH 5.0 with the addition of sulfuric acid sulfate. The filtrate obtained by filtering the pulp using a 40-mesh wire mesh was used for the test.

[Defoaming power test method]
Method a (confirmation of liquid level foam)
1000 ml of the filtrate prepared by the above method is placed in a glass cylinder having an inner diameter of 80 mm and a height of 600 mm and maintained at 40 ° C. Next, the liquid is circulated from the bottom of the cylinder to the top using a water flow pump at a flow rate of 10 L / min and foamed. After 5 seconds from the start of pump circulation, 2 μl of antifoaming agent is added, and the height of the foam on the liquid surface as the circulation time elapses is measured. After 7 minutes, the pump is stopped and the height of the foam with the passage of time is measured in the same manner. An antifoaming agent was added and the foam height (mm) was measured after 3 minutes, 5 minutes and 1 minute after the circulation was stopped. The results are shown in Table 3.

Method b (confirmation of bubbles in liquid)
Place 200 ml of the filtrate prepared in the above manner into a 500 ml glass graduated cylinder, add 2 μl of antifoaming agent and then hold at 40 ° C. Next, the time required for settling of the fine fiber was measured by shaking for 3 minutes with a shaker. The results are shown in Table 3.

[Test method for emulsion stability]
The antifoaming agent (100 ml) diluted 100-fold with the filtrate prepared by the above method adjusted to 40 ° C. was shaken for 2 minutes with a shaker, and the stable state of the emulsion particles was observed by the following method. The results are shown in Table 3.
a) Measurement of particle diameter (measured with SALD-2100 manufactured by Shimadzu)
b) The shaking tow liquid was filtered with a 40 mesh wire, and the state of attachment of the antifoaming agent was confirmed.

The antifoam composition of the present invention hardly causes solidification by drying on the liquid surface of the product, and even if it occurs, the solidified product disappears due to the addition of a new antifoam in a service tank or the like. It is very useful in practical use. Moreover, it is also excellent in emulsion stability and antifoaming effect.

Claims (4)

In an antifoaming composition comprising an oil-in-water emulsion in which the oil phase accounts for 5 to 60% by mass of the emulsion constituents, one or more of the compounds represented by the following general formula (1) are used as an emulsifier. An antifoam composition characterized by the above.

R—O— (C ₃ H ₇ O) _m / (C ₂ H ₅ O) _n —H (1)

In the formula, R represents a saturated or unsaturated alkyl group having 8 to 24 carbon atoms, an acyl group, a substituted or unsubstituted aryl group, or a rosin residue. m is an integer of 1 to 10, and n is an integer of 20 to 80. “/” Indicates that the additional form may be random or block. The antifoaming composition according to claim 1, wherein the emulsifier is one or more of the following general formula (2).

_{R-O- (C 2 H 5} O) p (C 3 H 7 O) m (C 2 H 5 O) q -H (2)

In the formula, R and m are the same as those in the general formula (1). p and q are in the range of 1 to 30, 20 to 60, respectively, and are positive integers satisfying the relationship of p + q = n (n is the same as that in the general formula (1)). The antifoaming composition according to claim 1 or 2, wherein, in the general formula (1) or (2), R is a secondary alkyl group having 8 to 24 carbon atoms. The antifoaming composition according to claim 1 or 2, wherein, in the general formula (1) or (2), R is a group represented by the following general formula (3) or a substituted or unsubstituted naphthyl group.

R ² represents a hydrogen atom, a phenyl group, a benzyl group, a styryl group, an alkyl group having 1 to 12 carbon atoms, a monobenzylphenyl group, a dibenzylphenyl group, a monostyrylphenyl group, a distyrylphenyl group, a cumyl group, or a monovalent group. A benzyl cumyl group, a dibenzyl cumyl group, a monostyryl cumyl group or a distyryl cumyl group is shown. n is an integer of 1 to 3, and when n is 2 or 3, the type of R ² is independently selected from the above.