JP4595492B2 - Oil-in-water emulsion defoamer composition - Google Patents

Description

  The present invention relates to an oil-in-water emulsion antifoam composition. More specifically, the present invention relates to an oil-in-water emulsion defoamer composition that has an excellent defoaming effect and hardly thickens during storage.

  Conventionally, an oil-in-water emulsion antifoaming agent has been widely used as a foaming inhibitor in various manufacturing processes including a papermaking process and a wastewater treatment process. Among oil-in-water emulsion antifoaming agents, a composition containing a higher alcohol component is known as an excellent effect (Patent Document 1). However, this antifoaming agent has a problem that handling property becomes extremely poor because it thickens vigorously during the storage period and solidifies into a cream. As a method for solving such problems, the present inventors have developed an antifoaming composition using an ethylene oxide adduct of a secondary alcohol as an emulsifier (Patent Document 2). However, it has been clarified that even this antifoaming agent composition has an insufficient viscosity stability with time.

  In an oil-in-water emulsion containing a higher aliphatic alcohol, it is known that a liquid crystal or gel is formed in an aqueous phase that is a continuous phase, and the viscosity is increased to stabilize the system (Non-Patent Document 1). It is surmised that the oil-in-water emulsion antifoaming agent containing a higher aliphatic alcohol thickens during storage due to the formation of such a liquid crystal or gel. By using an ethylene oxide adduct of a secondary alcohol as an emulsifier, the formation of this liquid crystal or gel can be avoided with a considerable probability, but cannot be completely avoided.

In general, in liquid products, physical properties such as viscosity are stable even after storage for a long period of time, and can be quickly taken out from a storage container, and a simple dispensing pump can provide a stable discharge amount. Handling is required. Therefore, the development of an oil-in-water emulsion defoamer with a blending composition that cannot sufficiently suppress the thickening over time with an ethylene oxide adduct of a secondary alcohol and that does not thicken even after long-term storage is desired. It was.
JP 48-62683 A (first page) JP 2001-62204 A (second page) Emulsification / Dispersion Technology Application Handbook, Science Forum (1987), p. 131

  The present invention has an excellent antifoaming effect, and has an excellent storage stability with respect to a formulation in which sufficient storage stability cannot be secured even when an ethylene oxide adduct of a secondary alcohol is used as an emulsifier. The object of the present invention is to provide an oil-in-water emulsion antifoaming agent composition that hardly thickens inside.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that a branched alkyl group can be used for a formulation in which sufficient storage stability cannot be secured even when an ethylene oxide adduct of a secondary alcohol is used as an emulsifier. It has been found that the use of an ethylene oxide adduct of a primary alcohol having a viscosity as an emulsifier can prevent thickening over time, and the present invention has been completed based on this finding.

That is, the present invention
(1) (A) an oil phase component containing a higher aliphatic alcohol having 12 to 30 carbon atoms and (B) a primary alcohol having a branched alkyl group having 6 to 15 carbon atoms having 2 to 4 carbon atoms adducts a defoamer composition (HLB of the adduct in a 13 to 19) containing the papermaking white water 500mL newsprint addition of the antifoam composition 4 mg / L, inner diameter 70 mm, placed in a graduated glass cylinder vessel 1 in capacity 1L, circulated by a pump 2 through a flow meter 3 is circulated in the 1, 000ML / min flow rate, the cylindrical container from the water surface in the cylindrical container from a height of 50cm carried out at a temperature of 30 ° C. the test of dropping in, when reading the foam volume in the graduated glass cylinder container of 5 minutes after the start circulating, oil foaming amount is equal to or less than 17mL Type emulsion antifoam composition, as well as,
(2) the content of the higher aliphatic alcohols having a carbon number of 12 to 30 in the oil phase component is 40 to 85 by weight% (1) oil-in-water emulsion defoamer composition according,
Is to provide.

  The oil-in-water emulsion defoamer composition of the present invention has an excellent defoaming effect, hardly thickens during product storage, and is excellent in stability over time.

  The oil-in-water emulsion antifoam composition of the present invention comprises (A) an oil phase component containing a higher aliphatic alcohol having 12 to 30 carbon atoms, and (B) a primary alcohol having a branched alkyl group having 2 to 2 carbon atoms. 4 alkylene oxide adducts. In the composition of the present invention, (A) an oil phase component containing a higher aliphatic alcohol having 12 to 30 carbon atoms is (B) an alkylene oxide adduct having 2 to 4 carbon atoms of a primary alcohol having a branched alkyl group. Is emulsified as an emulsifier.

  In the composition of the present invention, (A) the content of the oil phase component containing a higher aliphatic alcohol having 12 to 30 carbon atoms is preferably 5 to 50% by weight, more preferably 15 to 40% by weight. preferable. If the content of the oil phase component containing a higher aliphatic alcohol having 12 to 30 carbon atoms is less than 5% by weight, the defoaming effect may not be sufficiently exhibited. When the content of the oil phase component containing a higher aliphatic alcohol having 12 to 30 carbon atoms exceeds 50% by weight, the viscosity of the resulting oil-in-water emulsion antifoaming agent composition is increased and handling properties are reduced. There is also a possibility that the stability over time may be lowered.

  In the composition of the present invention, the content of the higher aliphatic alcohol having 12 to 30 carbon atoms in the oil phase component is preferably 40 to 85% by weight, and more preferably 45 to 70% by weight. If the content of the higher aliphatic alcohol having 12 to 30 carbon atoms in the oil phase component is less than 40% by weight, the defoaming effect may be reduced. If the content of the higher aliphatic alcohol having 12 to 30 carbon atoms in the oil phase component exceeds 85% by weight, the oil-in-water emulsion antifoaming composition may tend to thicken over time.

  Examples of the higher aliphatic alcohol having 12 to 30 carbon atoms used in the composition of the present invention include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, eicosyl alcohol, behenyl alcohol, tetracosyl alcohol, ceryl alcohol, Mericil alcohol can be mentioned. These higher aliphatic alcohols can be used alone or in combination of two or more. Moreover, as higher aliphatic alcohols, alcohols derived from natural animal and vegetable oils and fats can be used, synthetic alcohols can be used, and crude synthetic products of synthetic alcohols can also be used. Among these, a higher aliphatic alcohol having 16 to 24 carbon atoms can be particularly preferably used. Even if the aliphatic alcohol has less than 12 carbon atoms or more than 30 carbon atoms, the antifoaming property of the antifoaming composition may be deteriorated.

  In the composition of the present invention, examples of the components other than the higher aliphatic alcohol in the oil phase component include, for example, esters of 1 to 22 carbon atoms with 1 to 3 alcohols and fatty acids with 12 to 22 carbon atoms, mineral oils and paraffins. There may be mentioned hydrocarbons such as wax. The content of components other than the higher aliphatic alcohol in the oil phase component is preferably 15 to 60% by weight, and more preferably 30 to 55% by weight.

  In the composition of the present invention, the content of the alkylene oxide adduct having 2 to 4 carbon atoms of the primary alcohol (B) having a branched alkyl group is preferably 0.3 to 5% by weight, and 0.6. More preferably, it is ˜2% by weight. When the content of the alkylene oxide adduct of the primary alcohol having a branched alkyl group is less than 0.3% by weight, emulsification and dispersion in the antifoaming agent composition becomes insufficient, resulting in an increase in particle diameter and particle aggregation. May cause it. When the content of the alkylene oxide adduct of the primary alcohol having a branched alkyl group is 5% by weight or less, sufficient emulsification stability of the antifoaming composition is obtained. Viscosity is likely to increase because of finer and more free emulsifiers.

  The primary alcohol having a branched alkyl group used in the composition of the present invention is synthesized from, for example, a trimer of isohexyl alcohol, isoheptyl alcohol, isooctyl alcohol, 2-ethylhexyl alcohol, isononyl alcohol, and propylene. Branched nonyl alcohol, isodecyl alcohol, isoundecyl alcohol, isododecyl alcohol, 2-butyloctyl alcohol obtained by gel reaction of hexyl alcohol, branched dodecyl alcohol synthesized from tetramer of propylene, isotridecyl alcohol, butene Examples thereof include branched tridecyl alcohol, isotetradecyl alcohol, and isopentadecyl alcohol obtained by hydroformylation and hydrogenation of the above trimer. These primary alcohols can be used alone or in combination of two or more. Many of the primary alcohols having a branched alkyl group produced industrially are mixtures of isomers and the like, and these mixtures can add alkylene oxides as they are without separation. An alkylene oxide adduct of a primary alcohol having a branched alkyl group has a stronger emulsifying power than an alkylene oxide adduct of a primary alcohol having a linear alkyl group, and has an excellent stability. An agent composition can be obtained.

  In the composition of the present invention, examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, 1,2-propylene oxide, 1,3-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, and the like. Can be mentioned. Among these, ethylene oxide can be particularly preferably used. When adding a C3-C4 alkylene oxide to the primary alcohol which has a branched alkyl group, it is preferable to add so that it may become a copolymer chain with ethylene oxide. The copolymer chain of ethylene oxide and a C3-C4 alkylene oxide can be made into a random form, or can also be made into a block form. In the composition of the present invention, the number of moles of ethylene oxide added to the primary alcohol having a branched alkyl group is not particularly limited, but is preferably 5 to 100 moles of ethylene oxide with respect to 1 mole of the primary alcohol. It is more preferable that it is 10-50 mol of ethylene oxide with respect to 1 mol of primary alcohols.

In the composition of the present invention, (B) the HLB of the alkylene oxide adduct having 2 to 4 carbon atoms of the primary alcohol having a branched alkyl group is preferably 13 to 19 and is 15 to 18.5. It is more preferable. If the HLB of the alkylene oxide adduct is less than 13 or more than 19, the emulsion phase inversion of the oil phase component becomes difficult and the stability of the resulting oil-in-water emulsion antifoaming agent composition decreases. There is a fear. The value of HLB can be obtained by the Griffin equation, and when the hydrophilic group is only polyethylene oxide,
HLB = (% by weight of ethylene oxide unit) / 5
It can be calculated according to

  From the viewpoint of keeping the emulsifying power and emulsification stability of the resulting alkylene oxide adduct high, in the composition of the present invention, the branched alkyl group of the primary alcohol preferably has 6 to 15 carbon atoms, More preferably, it is 13.

  There is no restriction | limiting in particular in the manufacturing method of the oil-in-water-type emulsion antifoamer composition of this invention, The well-known method conventionally used in manufacture of an oil-in-water type emulsion can be used. For example, (A) an oil phase component containing a higher aliphatic alcohol having 12 to 30 carbon atoms and (B) an alkylene oxide adduct having 2 to 4 carbon atoms of a primary alcohol having a branched alkyl group are mixed and heated and melted. In addition, an oil-in-water emulsion defoamer composition can be obtained by emulsion phase inversion by adding hot water while stirring. In the composition of the present invention, the average particle size of the oil phase component fine particles in the oil-in-water emulsion is preferably 2 to 15 μm, more preferably 4 to 10 μm. If the average particle size of the fine particles of the oil phase component is less than 2 μm, the viscosity tends to increase during storage. If the average particle size of the fine particles in the oil phase exceeds 15 μm, phase separation may occur during storage.

  The composition of the present invention may contain a polymeric polysaccharide as necessary. Examples of the polymeric polysaccharide include welan gum, lanthanum gum, xanthan gum, succinoglycan, xanthan gum, guar gum, carrageenan and the like. By containing the polymer polysaccharide, aggregation of fine particles of the oil phase component can be suppressed, and the antifoaming composition can be stabilized.

  The composition of the present invention can be applied to all processes in which foaming is a problem, such as various production processes including papermaking processes such as papermaking and coating, and various wastewater treatment processes such as activated sludge and discharge. It can be suitably used as a foaming inhibitor in papermaking processes and wastewater treatment processes such as activated sludge. Although there is no restriction | limiting in particular in the addition amount of the antifoamer composition of this invention, Usually, it is preferable to add 0.1-1,000 mg / L with respect to a process liquid, and adding 1-100 mg / L. More preferred. The oil-in-water emulsion defoamer composition of the present invention has an excellent defoaming effect and hardly thickens during product storage, so there is no special consideration for quality deterioration over time. It can be used stably.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In Examples and Comparative Examples, the antifoaming effect and the change in viscosity with time of the antifoaming composition were measured by the following methods.
(1) Defoaming effect FIG. 1 is a schematic view of an apparatus used for evaluating the defoaming effect. 500 mL of newsprint paper white water added with 4 mg / L of antifoam composition is placed in a graduated glass cylindrical container 1 having an inner diameter of 70 mm and a capacity of 1 L, and 1,000 mL / L via a flow meter 3 by a circulation pump 2. It is circulated at a flow rate of minutes and dropped into the cylindrical container from a height of 50 cm from the water surface in the cylindrical container. The test is performed at 30 ° C., and the amount of foam in the graduated glass cylindrical container is read after 1 minute, 2 minutes, 3 minutes, 4 minutes and 5 minutes after the start of circulation.
(2) Viscosity change with time The antifoam composition (immediately after production, stored at 10 ° C., 20 ° C., 30 ° C., 40 ° C. for 30 days) is allowed to stand in a constant temperature water bath at 25 ° C. Using a viscometer and a No. 2 spindle, the viscosity is measured at 30 ° C. with a spindle speed of 30 rpm.

Example 1
Mixture of aliphatic alcohols having 18 to 22 carbon atoms [SASOL, Stenol 1822] 20 parts by weight, solid paraffin [Kanto Chemical Co., Ltd., melting point 68 to 70 ° C.] 4 parts by weight, oleic acid triglyceride [Fuji Oil Co., Ltd. ), Hyol] 6 parts by weight and an aqueous solution of 35 mol adduct of primary alcohol having a branched alkyl group having an average carbon number of about 11 as an emulsifier [Kao Co., Ltd., Emulgen 1135S-70, HLB 17.9, concentration 70 wt. %] 1.5 parts by weight of the mixture was mixed and melted, and then 68.5 parts by weight of hot water at 73 ° C. was added while stirring the melt with a turbine blade at a peripheral speed of 5.2 m / s at 73 ° C. And emulsified phase inversion. Next, 0.1 part by weight of Welan gum [Co., Ltd., K1C376] was added, and then cooled from 73 ° C to 30 ° C over 18 hours to obtain an oil-in-water emulsion antifoaming agent composition.
In the defoaming test, the foaming amount was 10 mL after 1 minute, 11 mL after 2 minutes, 14 mL after 3 minutes, 16 mL after 4 minutes, 17 mL after 5 minutes. In the viscosity increase test over time, the viscosity was 220 mPa · s immediately after production, 10 ° C., 20 ° C., 30 ° C., and 40 ° C. for 30 days, respectively, 218 mPa · s, 223 mPa · s, 220 mPa · s, 228 mPa · s. Met.

Comparative Example 1
As an emulsifier, instead of 1.1 parts by weight of an adduct of 35 moles of ethylene oxide of a primary alcohol having a branched alkyl group having an average carbon number of about 11 [Kao Corporation, Emulgen 1135S-70, HLB17.9] A mixture of 30 to 14 parts of ethylene oxide 30 mol adduct of a secondary alcohol having a hydroxyl group on the 3-7 position carbon in 12 to 14 [Japan Catalyst, Softanol 300, HLB17.4] was mixed at 73 ° C. An oil-in-water emulsion antifoam composition was prepared in the same manner as in Example 1 except that 69.2 parts by weight of hot water was added.
In the defoaming test, the foaming amount was 10 mL after 1 minute, 11 mL after 2 minutes, 13 mL after 3 minutes, 16 mL after 4 minutes, and 18 mL after 5 minutes. In the thickening test with time, the viscosity was 228 mPa · s immediately after production, 10 ° C., 20 ° C., 30 ° C., and 40 ° C. for 30 days, 226 mPa · s, 1,160 mPa · s, and 1,060 mPa · s, respectively. It was 1,140 mPa · s.

Comparative Example 2
As an emulsifier, instead of 1.1 parts by weight of an adduct of 35 moles of ethylene oxide of a primary alcohol having a branched alkyl group having an average carbon number of about 11 [Kao Corporation, Emulgen 1135S-70, HLB17.9] A mixture of 20 to 14 moles of an ethylene oxide 20 mol adduct of a secondary alcohol having a hydroxyl group on the 3-7 position carbon at 12 to 14 [Nippon Catalysts, Softanol 200, HLB16.3] was mixed at 73 ° C. An oil-in-water emulsion antifoam composition was prepared in the same manner as in Example 1 except that 69.2 parts by weight of hot water was added.
In the defoaming test, the foaming amount was 10 mL after 1 minute, 12 mL after 2 minutes, 14 mL after 3 minutes, 17 mL after 4 minutes, 19 mL after 5 minutes. In the thickening test with time, the viscosity was 245 mPa · s immediately after production, 10 ° C., 20 ° C., 30 ° C., 40 ° C. for 30 days, 2,208 mPa · s, 278 mPa · s, 253 mPa · s, 251 mPa, respectively.・ It was s.
Table 1 shows the composition of the oil-in-water emulsion antifoaming compositions of Example 1 and Comparative Examples 1 and 2, Table 2 shows the results of the defoaming test, and Table 3 shows the results of the thickening test over time. Show.

As seen in Table 2, the oil-in-water emulsion defoamer composition of Example 1 and Comparative Examples 1 and 2 emulsified with an oil phase component containing an aliphatic alcohol having 18 to 22 carbon atoms was added to 4 mg of papermaking white water. When / L is added, the amount of foaming is small in the defoaming effect test, and all of these antifoaming compositions have an excellent defoaming effect.
As seen in Table 3, the oil-in-water emulsion defoamer composition of Example 1 using a 35 mol adduct of a primary alcohol having a branched alkyl group as an emulsifier is 10 to 40 ° C. for 30 days. Even after storage, there is almost no change in viscosity, indicating excellent storage stability. On the other hand, even if it is the same oil phase component as Example 1, the oil-in-water type emulsion antifoamer composition of the comparative example 1 which uses the 30 mol addition product of ethylene oxide of secondary alcohol as an emulsifier is 20-40. The viscosity increases when stored at 30 ° C. for 30 days, and the oil-in-water emulsion defoamer composition of Comparative Example 2 using a 20-mole ethylene oxide adduct of a secondary alcohol as an emulsifier increases in viscosity when stored at 10 ° C. for 30 days. To do.

  The oil-in-water emulsion defoamer composition of the present invention not only has an excellent defoaming effect, but also has almost no change in viscosity after being stored at 10 to 40 ° C. for 30 days, and can be handled in the same manner as immediately after production. it can.

It is the schematic of the apparatus used for evaluation of a defoaming effect.

1 Glass cylinder with scale 2 Circulation pump 3 Flow meter

Claims (2)

(A) Oil phase component containing a higher aliphatic alcohol having 12 to 30 carbon atoms and (B) an alkylene oxide adduct having 2 to 4 carbon atoms of a primary alcohol having a branched alkyl group having 6 to 15 carbon atoms ( The adduct has an HLB of 13 to 19), and is made up of 500 mL of newsprint paper white water to which 4 mg / L of the antifoam composition is added, with an inner diameter of 70 mm and a capacity of 1 L. Test in glass cylinder 1 with scale, circulate by flow pump 3 at a flow rate of 1,000 mL / min with circulation pump 2 , and drop into cylinder from 50 cm height from water surface in cylinder The oil-in-water emulsion antifoaming agent is characterized in that the foaming amount is 17 mL or less when the foaming amount in a glass cylindrical container with a scale 5 minutes after the start of circulation is read. Composition. The oil- in-water emulsion antifoaming composition according to claim 1 , wherein the content of the higher aliphatic alcohol having 12 to 30 carbon atoms in the oil phase component is 40 to 85% by weight .

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