CN101053797A - Foam suppressing composition - Google Patents

Foam suppressing composition Download PDF

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Publication number
CN101053797A
CN101053797A CNA2007100058604A CN200710005860A CN101053797A CN 101053797 A CN101053797 A CN 101053797A CN A2007100058604 A CNA2007100058604 A CN A2007100058604A CN 200710005860 A CN200710005860 A CN 200710005860A CN 101053797 A CN101053797 A CN 101053797A
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竹脇一幸
池田辉喜
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Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical Co Ltd
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    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47K—SANITARY EQUIPMENT NOT OTHERWISE PROVIDED FOR; TOILET ACCESSORIES
    • A47K7/00—Body washing or cleaning implements
    • A47K7/02—Bathing sponges, brushes, gloves, or similar cleaning or rubbing implements
    • A47K7/03—Bathing sponges, brushes, gloves, or similar cleaning or rubbing implements containing soap or other cleaning ingredients, e.g. impregnated
    • A—HUMAN NECESSITIES
    • A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
    • A47K—SANITARY EQUIPMENT NOT OTHERWISE PROVIDED FOR; TOILET ACCESSORIES
    • A47K10/00—Body-drying implements; Toilet paper; Holders therefor
    • A47K10/24—Towel dispensers, e.g. for piled-up or folded textile towels; Toilet-paper dispensers; Dispensers for piled-up or folded textile towels provided or not with devices for taking-up soiled towels as far as not mechanically driven
    • A47K10/32—Dispensers for paper towels or toilet-paper
    • A47K10/42—Dispensers for paper towels or toilet-paper dispensing from a store of single sheets, e.g. stacked
    • A47K10/421—Dispensers for paper towels or toilet-paper dispensing from a store of single sheets, e.g. stacked dispensing from the top of the dispenser
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D83/00—Containers or packages with special means for dispensing contents
    • B65D83/08—Containers or packages with special means for dispensing contents for dispensing thin flat articles in succession

Abstract

A foam suppressing composition contains: (A) 1-40 percent of silicon oil mixture using mixed treatment to the following formula (i)-(iii), wherein (i) is hydrophobic organopolysiloxane, (ii) is micro powder silicon dioxide whose surface is treated by using organopolysiloxane and (iii) is basic catalyst; 1-40 percent of polyoxyethylene modified organopolysiloxane showed in formula (III): R<SUP>6</SUP><SUB>2</SUB>R<SUP>8</SUP>SiO-(R<SUP>6</SUP><SUB>2</SUB>SiO)<SUB>m</SUB>-(R<SUP>6</SUP>R<SUP>7</SUP>SiO)<SUB>n</SUB>-SiR<SUP>6</SUP><SUB>2</SUB>R<SUP>8</SUP> (III). [R<SUP>6</SUP> is monovalent hydrocarbon radical, R<SUP>7</SUP> is showed as formula (IV), R<SUP>8</SUP> is R<SUP>6</SUP>, R<SUP>7</SUP>, hydroxide radical or alkoxy, m is 5-200, n is 1-30, -R<SUP>9</SUP>-O(CH<SUB>2</SUB>CH<SUB>2</SUB>O)<SUB>c</SUB>-R<SUP>10</SUP> (IV). R<SUP>9</SUP> is bivalent hydrocanbon radical, R<SUP>10</SUP> is hydrogen atom, alkyl, acetyl or isocyano group, c is 3-50; (D) polyoxyalkylene polymer; (E) nonionic surfactant; (F) water: the rest. The foam suppressing composition in this invention has excellent foam suppressing persistence and deterioration with time is small even if long-stem storage if foamed liquid is added to the foam suppressing composition.

Description

Defoaming agent composition
Technical field
After adding in the present invention relates in the expanding foam solution of expanding foam solution, particularly alkalescence, though the long preservation performance through the time deterioration also little silicon-type defoaming agent composition.
Background technology
The silicon-type defoamer is compared the character with various excellences with other defoamers, therefore chemical industry, food industry, petroleum industry, textile industry, paper industry, pulp industry or medical industry etc. with the operation of foaming in be extensive use of, for example, the oily blend type defoamer that silicone oil such as dimethyl polysiloxane, methyl phenyl silicone, methylvinyl-polysiloxane are mixed with micropowder silica, that these oily blends and surfactant are scattered in the emulsion type defoaming agent that forms in the water is widely-used.But, this emulsion type defoaming agent is under the such rigor condition of high temperature, high alkalinity, high shear force, exist emulsion particle destroyed, the problem of froth breaking ability drop, therefore as its substitute, having proposed will be with the organopolysiloxane of polyoxyalkylenes modification and the self-emulsifying type defoamer of oily blend and usefulness [special public clear 51-71886 number, special public clear 54-43015 number, special public clear 52-19836 number, special public clear 52-22638 number, spy's public clear 55-23084 communique (patent documentation 1～5)].
But these silicon-type defoamers produce sometimes by with the expanding foam solution Long contact time antifoam performance being descended, and perhaps produce problems such as separation, sediment, and this point is remarkable especially when expanding foam solution is alkalescence.
In addition, when going through when long-time,, therefore need append the interpolation defoamer, produce the various rough sledding that yield reduces, a large amount of interpolations of defoamer produce sometimes owing to pass antifoam performance and preliminary phase in time than reducing with the operation of foaming.
In order to improve these problems, antifoam performance is further improved, various schemes have been proposed, patent documentation 6), method (the special public clear 51-35556 communique: patent documentation 7) etc., but need its characteristic further to improve silica handled with the organo-silicon compound that contain nitrogen for example can enumerate in advance method (the special public clear 52-31836 communique: that makes the silicon dioxide drainageization of using in the oily blend with chlorosilane etc.
Patent documentation 1: special public clear 51-71886 communique
Patent documentation 2: special public clear 54-43015 communique
Patent documentation 3: special public clear 52-19836 communique
Patent documentation 4: special public clear 52-22638 communique
Patent documentation 5: special public clear 55-23084 communique
Patent documentation 6: special public clear 52-31836 communique
Patent documentation 7: special public clear 51-35556 communique
Summary of the invention
The present invention In view of the foregoing proposes, after adding in its purpose is to provide in the expanding foam solution of expanding foam solution, particularly alkalescence, even long preservation, separation, sedimentary generation, antifoam performance through the time deterioration also few, and the defoaming agent composition of froth breaking continuation excellence.
The present inventor has carried out conscientiously research to achieve these goals repeatedly, found that and contain by in the presence of base catalyst, handling the silicone oil blend (silicone oil compound) that obtains with mixture with organopolysiloxane of specific rerum natura to carried out surface-treated micropowder silica with organopolysiloxane, polyoxyethylene modification organopolysiloxane and water with ad hoc structure and rerum natura, also contain polyoxyalkylene modification organopolysiloxane as required with ad hoc structure and rerum natura, polyoxyalkylene polymers, the defoaming agent composition of nonionic surfactant, it is for expanding foam solution, particularly alkaline expanding foam solution in add stability and froth breaking continuation excellence, thereby finished the present invention.
Therefore, the invention provides defoaming agent composition, it is characterized in that containing:
(A), neutralize as required and/or the removal of low boiler cut and the silicone oil blend that obtains: 1～40 quality % by under room temperature～200 ℃, following (i)～(iii) composition being carried out mixed processing
(i) viscosity under 25 ℃ is 10～100000mm 2/ s is essentially hydrophobic organopolysiloxane: 100 mass parts
(ii) carried out surface-treated micropowder silica: 1～20 mass parts with organopolysiloxane
(iii) base catalyst: 0.01～5 mass parts;
(B) viscosity under 25 ℃ shown in the following general formula (I) is 10～10000mm 2The mixture more than a kind or 2 kinds of the polyoxyalkylene modification organopolysiloxane of/s: 0～30 quality %
R 1 2R 3SiO-(R 1 2SiO) x-(R 1R 2SiO) y-SiR 1 2R 3 (I)
[in the formula, R 1Be the replacement that is same to each other or different to each other or the monovalence alkyl of unsubstituted carbon number 1～18, R 2Be any monovalent organic radical group shown in the following general formula (II), R 3Be R 1, R 2, hydroxyl or carbon number 1～6 alkoxyl, x is 5～200 integer, y is 1～30 integer,
-R 4-O(CH 2CH 2O) a-(CH 2(CH 3)CHO) b-R 5 (II)
(in the formula, R 4Be the bivalent hydrocarbon radical of carbon number 2～6, R 5For hydrogen atom or be selected from any monovalent organic radical group of alkyl, acetyl group and the isocyano group of carbon number 1～6, a and b are for satisfying the positive number of 3≤a+b≤80 and a/b=2/8～8/2)];
(C) mixture more than a kind or 2 kinds of the polyoxyethylene modification organopolysiloxane shown in the following general formula (III): 1～40 quality %
R 6 2R 8SiO-(R 6 2SiO) m-(R 6R 7SiO) n-SiR 6 2R 8 (III)
[in the formula, R 6Be the replacement that is same to each other or different to each other or the monovalence alkyl of unsubstituted carbon number 1～18, R 7Be the polyoxyethylene groups shown in the following general formula (IV), R 8Be R 6, R 7, hydroxyl or carbon number 1～6 alkoxyl, m is 5～200 integer, n is 1～30 integer,
-R 9-O(CH 2CH 2O) c-R 10 (IV)
(in the formula, R 9Be the bivalent hydrocarbon radical of carbon number 2～6, R 10For hydrogen atom or be selected from any monovalent organic radical group of alkyl, acetyl group and the isocyano group of carbon number 1～6, c is 3～50 positive number)];
(D) 1 of polyoxyalkylene polymers kind or the mixture more than 2 kinds: 0～40 quality %;
(E) 1 of nonionic surfactant kind or the mixture more than 2 kinds: 0～20 quality %;
(F) water: remainder.
Add behind expanding foam solution in the defoaming agent composition of the present invention, though long preservation, performance through the time deterioration little, froth breaking continuation excellence.
The specific embodiment
Constitute (A) composition silicone oil blend of defoaming agent composition of the present invention, become the principal component that is used to give the said composition defoaming, by (ii) being principal component, they are handled and obtaining in base catalyst existence (iii) to be essentially hydrophobic organopolysiloxane (i) and to have carried out surface-treated micropowder silica with organopolysiloxane.
(A) organopolysiloxane that uses in the composition (i) is essentially hydrophobicity.Wherein, what is called is essentially hydrophobicity, even be meant in a part of functional group and contain hydrophilic radical, but shows hydrophobicity as organopolysiloxane integral body.
Being essentially hydrophobic organopolysiloxane (i) can be the straight chain shape, also can be branch-like, the organopolysiloxane shown in the preferred especially following average group accepted way of doing sth (V).
R 11 pSiO (4-p)/2 (V)
In the above-mentioned formula (V), R 11Be the monovalence alkyl of replacement or unsubstituted carbon number 1～18, they can be the same or different.As R 11The monovalence alkyl, specifically can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, tridecyl, myristyl, cetyl, alkyl such as octadecyl, cycloalkyl such as cyclohexyl, vinyl, thiazolinyls such as pi-allyl, phenyl, aryl such as tolyl, styryl, aralkyl such as AMS base etc., or part or all of the hydrogen atom that combines with carbon atom of these groups is by halogen atom, cyano group, amino, the chloromethyl that hydroxyl etc. replace, the 3-chloropropyl, 3,3, the 3-trifluoro propyl, cyanoethyl, the 3-aminopropyl, N-(beta-aminoethyl)-gamma-amino propyl group etc., from defoaming and economy aspect, preferred all R 1180 moles of % above, preferred especially 90 moles of % are above is methyl.In addition, p is the positive number of 1.9≤p≤2.2, preferred 1.95≤p≤2.15.Moreover the end of organopolysiloxane can be used R 11 3The three Organosilyl end-blockings that Si-represents also can be used HOR 11 2Two organic hydroxyl silicyl end-blockings shown in the Si-.
This is essentially hydrophobic organopolysiloxane (i) and adopts viscosity under 25 ℃ that Ostwald viscosimeter measures, from defoaming, operability aspect, is 10～100000mm 2/ s is preferably 50～10000mm 2/ s.If not enough 10mm 2/ s, antifoam performance is poor, if surpass 100000mm 2/ s, the viscosity of silicone oil blend increases, the operability variation.
On the other hand, carried out surface-treated micropowder silica (ii) with organopolysiloxane, for example, can make by the former powder of micropowder silica being carried out surface treatment, but also can use the commercially available prod with the organopolysiloxane shown in the following composition formula (VI).
R 12 2R 13SiO-(R 12 2SiO) w-SiR 12 2R 13 (VI)
In the above-mentioned formula (VI), R 12Monovalence alkyl for the carbon number 1～18 that is same to each other or different to each other, specifically can enumerate alkyl such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, tridecyl, myristyl, cetyl, octadecyl, cycloalkyl such as cyclohexyl, aryl such as phenyl, tolyl etc., from defoaming and economy aspect, preferred all R 1280 moles of % above, preferred especially 90 moles of % are above is methyl.R 13Be R 12, carbon number 1～6 such as hydroxyl or methoxyl group, ethyoxyl, propoxyl group, butoxy alkoxyl.In addition, w makes this organopolysiloxane adopt viscosity under 25 ℃ that Ostwald viscosimeter measures from the preferred 10～1000mm in operability aspect 2/ s, 20～100mm more preferably 2The number of/s.
The former powder of micropowder silica can be known product, can be any of wet method silica, dry method silica.As the former powder of these micropowder silica, can the illustration precipitated silica, silica xerogel, fumed silica etc., specifically can enumerate commercially available products such as Nipsil (eastern Cao シ リ カ society system), Silysia (Silysia of Fuji chemistry society system), AEROSIL (Japanese AEROSIL society system).In addition, the specific area that adopts the BET method to measure is preferably 100m 2/ g～700m 2/ g is preferably 150m especially 2/ g～500m 2/ g.
The surface treatment of micropowder silica can be adopted known method, for example use mixing, dispersal devices such as Henschel mixer, Loedige mixer, high-speed mixer to carry out, can be by in the said apparatus that the former powder of micropowder silica is packed into, thus before stirring or while stirring, the organopolysiloxane spraying is made.Also can heat, add base catalysts such as ammoniacal liquor as required.In this case, preferably under room temperature～100 ℃, preferred especially 50～80 ℃, carry out handling in 10 minutes～2 hours, preferred especially 15 minutes～1 hour.
Moreover surface conditioning agent (organopolysiloxane) is different because of the specific area of micropowder silica with respect to the amount of micropowder silica, if the BET specific area is 100～700m 2/ g is 1～50 mass parts with respect to micropowder silica 1 00 mass parts then, is preferably 5～30 mass parts.
Having carried out surface-treated micropowder silica addition (ii) with organopolysiloxane, is 1～20 mass parts with respect to organopolysiloxane (i) 100 mass parts, is preferably 5～15 mass parts.If addition less than 1 mass parts, then antifoam performance is poor, if more than 20 mass parts, then the viscosity of silicone oil blend increases, the operability variation.
In addition, the base catalyst that uses in (A) of the present invention composition (iii), can use the known base catalyst that uses in the transfer reaction of polysiloxanes, the for example oxide of alkali metal or alkaline-earth metal, hydroxide, alkoxide or organosilicate (siliconate) etc., but preferred organic potassium silicate and potassium hydroxide.
Base catalyst use amount (iii) is 0.01～5 mass parts with respect to organopolysiloxane (i) 100 mass parts, is preferably 0.1～3 mass parts.If less than 0.01 mass parts, a little less than the effect as catalyst, even surpass 5 mass parts, the effect of catalyst does not improve yet, and becomes unfavorable aspect cost.
In addition, the silicone oil blend of the present invention (A) composition can followingly be made: use set amount be essentially hydrophobic organopolysiloxane (i) and with above-mentioned organopolysiloxane carried out surface-treated micropowder silica (ii) with base catalyst (iii), room temperature～200 ℃, preferred 100～200 ℃, more preferably carry out mixed processing under 150～200 ℃ the temperature, neutralize as required then and/or the removal of low boiler cut.
Moreover the mixed processing time is preferably 10 minutes～5 hours, be preferably 1～3 hour especially.In addition, mixed processing is preferably carried out under inert atmospheres such as nitrogen.
Neutralization can be used organic acids such as ethylene chlorhydrin, formic acid, acetate, and inorganic acids such as watery hydrochloric acid, dilute sulfuric acid etc. carry out.In addition, the removal of low boiler cut can adopt methods such as decompression distillation to carry out.
In defoaming agent composition of the present invention, the content of above-mentioned silicone oil blend (A) is 1～40 quality % of defoaming agent composition integral body, is preferably 5～30 quality %.If content lacks than 1 quality %, it is not enough that antifoam performance becomes, if many than 40 quality %, the stability of product with in add bad stability.
(B) the polyoxyalkylene modification organopolysiloxane of composition is used to make above-mentioned silicone oil blend emulsification to disperse, and is represented by following general formula (I).
R 1 2R 3SiO-(R 1 2SiO) x-(R 1R 2SiO) y-SiR 1 2R 3 (I)
In the above-mentioned formula (I), R 1Be the replacement that is same to each other or different to each other or the monovalence alkyl of unsubstituted carbon number 1～18, specifically can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, tridecyl, myristyl, cetyl, alkyl such as octadecyl, cycloalkyl such as cyclohexyl, vinyl, thiazolinyls such as pi-allyl, phenyl, aryl such as tolyl, styryl, aralkyl such as AMS base etc., or part or all of the hydrogen atom that combines with carbon atom of these groups is by halogen atom, cyano group, the chloromethyl that amino etc. replace, the 3-chloropropyl, 3,3, the 3-trifluoro propyl, cyanoethyl, the 3-aminopropyl, N-(beta-aminoethyl)-monovalence alkyl such as gamma-amino propyl group.
In addition, R 2Be the polyoxyalkylenes shown in the following general formula (II).
-R 4-O(CH 2CH 2O) a-(CH 2(CH 3)CHO) b-R 5 (II)
In the above-mentioned formula (II), R 4Be the bivalent hydrocarbon radical of carbon number 2～6, can enumerate alkylidene, alkenylene etc., can enumerate for example ethylidene, propylidene, butylidene, pentylidene, hexylidene etc.In addition, R 5For alkyl, acetyl group or the isocyano group of hydrogen atom, carbon number 1～6,, can enumerate methyl, ethyl, propyl group, butyl, amyl group etc. as alkyl.A and b be for satisfying 3≤a+b≤80, preferred 5≤a+b≤60, and the positive number of a/b=2/8～8/2, preferred a/b=2.5/7.5～7.5/2.5.
On the other hand, R 3For with R 1Or R 2The alkoxyl of identical group, hydroxyl or carbon number 1～6 specifically can be enumerated as above-mentioned R 1And R 2Illustrated group as alkoxyl, can be enumerated methoxyl group, ethyoxyl, propoxyl group, butoxy etc.
Moreover the x in the above-mentioned formula (I) is 5～200, preferred 20～150 integer, and y is 1～30, preferred 1～20 integer.
This polyoxyalkylene modification organopolysiloxane can use a kind separately, also can use the mixture more than 2 kinds, and using the viscosity under 25 ℃ that adopt Ostwald viscosimeter mensuration is 10～10000mm 2/ s, preferred 50～8000mm 2/ s, more preferably 500～5000mm 2The polyoxyalkylene modification organopolysiloxane of/s.
In defoaming agent composition of the present invention, the content of above-mentioned polyoxyalkylene modification organopolysiloxane (B) is 0～30 quality % of defoaming agent composition integral body, is preferably 1～30 quality %, is preferably 1～20 quality % especially.If content surpasses 30 quality %, the froth breaking characteristic variation of composition.
(C) composition polyoxyethylene modification organopolysiloxane be used to make defoaming agent composition in add stability, storage stability, dilution stability, high-temperature stability, defoaming and improve, shown in following general formula (III).
R 6 2R 8SiO-(R 6 2SiO) m-(R 6R 7SiO) n-SiR 6 2R 8 (III)
In the above-mentioned formula (III), R 6For the replacement that is same to each other or different to each other or the monovalence alkyl of unsubstituted carbon number 1～18, specifically can enumerate as above-mentioned R 1Illustrated group, but from defoaming and economy aspect, preferred all R 680 moles of % above, preferred especially 90 moles of % are above is methyl.
In addition, R 7Be the polyoxyethylene groups shown in the following general formula (IV).
-R 9-O(CH 2CH 2O) c-R 10 (IV)
In the above-mentioned formula (IV), R 9Be the bivalent hydrocarbon radical of carbon number 2～6, can enumerate alkylidene, alkenylene etc., can enumerate for example ethylidene, propylidene, butylidene, pentylidene, hexylidene etc.In addition, R 10For alkyl, acetyl group or the isocyano group of hydrogen atom, carbon number 1～6,, can enumerate methyl, ethyl, propyl group, butyl, amyl group etc. as alkyl.C satisfies 3～50, preferred 4～30 positive number.If c is littler than 3, then internally add stability, storage stability, dilution stability, high-temperature stability, defoaming generation harmful effect.In addition, if greater than 50, then fusing point and melt viscosity raise, and operability, defoaming reduce.
On the other hand, R 8For with R 6Or R 7The alkoxyl of identical group, hydroxyl or carbon number 1～6 specifically can be enumerated as above-mentioned R 6And R 7Illustrated group as alkoxyl, can be enumerated methoxyl group, ethyoxyl, propoxyl group, butoxy etc.
Moreover the m in the above-mentioned formula (III) is 5～200, preferred 10～150 integer.If m is greater than 200, emulsifying dispersivity descends, and internally adds stability, storage stability, dilution stability, high-temperature stability, defoaming generation harmful effect.N is 1～30, preferred 1～20 integer.
This polyoxyethylene modification organopolysiloxane can use a kind separately, also can use the mixture more than 2 kinds.
In defoaming agent composition of the present invention, the content of above-mentioned polyoxyethylene modification organopolysiloxane (C) is 1～40 quality % of defoaming agent composition integral body, is preferably 5～20 quality %.If content is less than 1 mass parts, then the effect to stability, defoaming is little, if surpass 40 quality %, then the viscosity of defoaming agent composition raises, the water dispersible variation.
Moreover, (B) the polyoxyalkylene modification organopolysiloxane of composition and (C) the polyoxyethylene modification organopolysiloxane of composition, for example, make by in the presence of catalyst such as platinum, making polyoxyalkylene that the organic hydrogen polysiloxanes that contains the Si-H base and molecule chain end have unsaturated group of aliphatic series such as pi-allyl or polyoxyethylene compound carry out addition reaction.
(D) polyoxyalkylene polymers of composition becomes emulsion adjuvant in defoaming agent composition of the present invention, therefore the polymer shown in the preferred following general formula of use (VII).
R 14O-(R 15O) z-R 14 (VII)
In the above-mentioned formula (VII), R 14Can enumerate hydrogen atom, or alkyl such as methyl, ethyl, propyl group, butyl, thiazolinyls such as vinyl, pi-allyl, carbon numbers such as acetyl group or stearyl 1～20, particularly 1～18 any monovalent organic radical group, they can be the same or different.R 15Bivalent hydrocarbon radical for carbon numbers such as alkylidene 2～6 such as ethylidene, propylidene.In this case, R 15It can be the group more than 2 kinds that differs from one another.
In addition, z is that the polystyrene conversion weight average molecular weight that makes this polyoxyalkylene polymers adopt GPC to measure is preferably 500～5000, more preferably 1000～4000 number.Wherein, if weight average molecular weight less than 500, the possible variation of the emulsion stability of the defoaming agent composition that obtains if surpass 5000, might viscosity raise the operability variation.Moreover polyoxyalkylene polymers can be used a kind separately, also can use the mixture more than 2 kinds.
In defoaming agent composition of the present invention, the content of above-mentioned polyoxyalkylene polymers (D) is 0～40 quality % of defoaming agent composition integral body, is preferably 0～20 quality %.If surpass 40 quality %, the emulsification property variation of defoaming agent composition.Moreover, can be effective dose during cooperation, preferably cooperate more than the 5 quality %.
(E) nonionic surfactant of composition is used to make antifoam composition [i.e. (A)～(D) composition] to be scattered in water, usually can be known nonionic surfactant, can enumerate for example sorbitan fatty acid esters, fatty acid glyceride, polyglyceryl fatty acid ester, methyl glycol fatty acid ester, sucrose fatty ester, cithrol, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid esters, the polyoxyethylene fatty acid glyceride, the polyoxyethylene polyoxypropylene diol fatty acid ester, Emulsifier EL-60, polyoxyethylene hardened castor oil etc.
Moreover in defoaming agent composition of the present invention, this nonionic surfactant can use a kind separately, also can use the mixture more than 2 kinds, and its content is 0～20 quality %, is preferably 1～20 quality %, is preferably 1～10 quality % especially.If surpass 20 quality %, the viscosity of defoaming agent composition raises, the operability variation.
In defoaming agent composition of the present invention, need to add as (F) composition with the necessary water of above-mentioned (A)～(E) composition emulsification, its amount is the remainder that contains proportional total with respect to (A)～(E) each composition, preferably add 50～2000 mass parts, more preferably 80～400 mass parts with respect to total 100 mass parts of (A)～(E) composition.
In addition, defoaming agent composition of the present invention can mix by above-mentioned (A)～(F) composition with set amount, the limit heating edge adopts known method as required, for example adopt that mixing such as homomixer, homogenizer, colloid mill, dispersion machine stir equably, emulsification and preparing, be preferably as follows method especially: after (A)～(E) composition of set amount is evenly mixed, disperses, add the part of (F) composition of set amount, stir, add remaining (F) composition again after the emulsification, stir equably, mix, the preparation defoaming agent composition.
In addition, in defoaming agent composition of the present invention, can add a spot of preservation material, sterilization material arbitrarily for anticorrosion.As this concrete example of preserving material, sterilization material, can enumerate clorox, sorbic acid, potassium sorbate, salicylic acid, sodium salicylate, benzoic acid, Sodium Benzoate, parabens, iso thiazolinium compound etc.Its addition is 0～0.5 mass parts with respect to defoaming agent composition 100 mass parts of the present invention, preferred especially 0.005～0.5 mass parts.
The defoaming agent composition of the present invention that obtains like this by add to expanding foam solution, particularly alkalescence expanding foam solution in, even long preservation, performance through the time deterioration little, in add stability and froth breaking continuation excellence.Moreover there is no particular restriction for the addition of defoaming agent composition, preferably adds 0.001～3 quality % with respect to expanding foam solution, especially preferably adds 0.01～1 quality %.In addition, as the expanding foam solution of alkalescence, can enumerate water-based cutting oil, black liquor etc.
Embodiment
Embodiment and comparative example below are shown, the present invention is specifically described, but the present invention is not limited to following embodiment.Moreover in following example, % represents quality %, and viscosity is the value that adopts under 25 ℃ that Ostwald viscosimeter measures.
[embodiment 1～6, comparative example 1～4]
Use following (A)～(E) composition with the amount shown in the table 1, be heated to 70 ℃, after the use homomixer evenly mixes, slowly add the water of (F) composition, the preparation defoaming agent composition.For said composition, adopt the method shown in following to defoaming, in add stability, product stability is estimated.Show the result in table 1.
(A) silicone oil blend
[silicone oil blend (a-1)]
Use viscosity to be 8000mm 2/ s, contain the CH of 0.01 mole fraction 3SiO 3/2Dimethyl polysiloxane 100 mass parts of the branch-like of unit are as being essentially hydrophobic organopolysiloxane, following (1) of using 5 mass parts is as micropowder silica, use contains organic silicic acid potassium 3.3 mass parts of 3% potassium hydroxide as base catalyst, under nitrogen atmosphere, 150 ℃ mix down after 3 hours, neutralize with ethylene chlorhydrin, then low boiler cut is removed and obtained.
[silicone oil blend (a-2)]
Use viscosity to be 10000mm 2Dimethyl polysiloxane 100 mass parts of/s are as being essentially hydrophobic organopolysiloxane, following (2) of using 10 mass parts are as micropowder silica, use contains organic silicic acid potassium 5 mass parts of 3% potassium hydroxide as base catalyst, under nitrogen atmosphere, 150 ℃ mix down after 3 hours, neutralize with ethylene chlorhydrin, then low boiler cut is removed and obtained.
[silicone oil blend (a-3)]
Use viscosity to be 8000mm 2/ s, contain the CH of 0.01 mole fraction 3SiO 3/2Dimethyl polysiloxane 100 mass parts of the branch-like of unit are as being essentially hydrophobic organopolysiloxane, and following (1) of using 5 mass parts as micropowder silica, under nitrogen atmosphere, 150 ℃ mixed 3 hours down and obtain.
[silicone oil blend (a-4)]
Use viscosity to be 8000mm 2/ s, contain the CH of 0.01 mole fraction 3SiO 3/2Dimethyl polysiloxane 100 mass parts of the branch-like of unit are as being essentially hydrophobic organopolysiloxane, the AEROSIL 200 that uses 5 mass parts is as micropowder silica, use contains organic silicic acid potassium 3.3 mass parts of 3% potassium hydroxide as base catalyst, under nitrogen atmosphere, 150 ℃ mix down after 3 hours, neutralize with ethylene chlorhydrin, then low boiler cut is removed and obtained.
[micropowder silica]
(1) with the AEROSIL 300[of 100g Japan AEROSIL society system, specific area 300m 2/ g] in the Loedige mixer of packing into, while stirring with vaporific interpolation two terminal hydroxyl dimethyl polysiloxane (viscosity 50mm 2/ s) 20g stirred 30 minutes down and obtains at 70 ℃.
(2) with the Nipsil HD-2[of 100g east Cao シ リ カ society system, specific area 300m 2/ g] in the Loedige mixer of packing into, while stirring with vaporific interpolation two terminal hydroxyl dimethyl polysiloxane (viscosity 50mm 2/ s) 20g stirred 30 minutes down and obtains at 70 ℃.
(B) polyoxyalkylene modification organopolysiloxane
[polyoxyalkylene modification organopolysiloxane (b-1)]
Represented by following formula average the composition, and viscosity is 1000mm 2/ s.
R 1 2R 3SiO-(R 1 2SiO) x-(R 1R 2SiO) y-SiR 1 2R 3
(in the formula, R 1And R 3For-CH 3, R 2For-C 3H 6O (C 2H 4O) 25.5(C 3H 6O) 8.5C 4H 9, x is 30, y is 5)
[polyoxyalkylene modification organopolysiloxane (b-2)]
Represented by following formula average the composition, and viscosity is 2500mm 2/ s.
R 1 2R 3SiO-(R 1 2SiO) x-(R 1R 2SiO) y-SiR 1 2R 3
(in the formula, R 1And R 3For-CH 3, R 2For-C 3H 6O (C 2H 4O) 21(C 3H 6O) 21CH 3, x is 135, y is 15)
[polyoxyalkylene modification organopolysiloxane (b-3)]
Represented by following formula average the composition, and viscosity is 800mm 2/ s.
R 1 2R 3SiO-(R 1 2SiO) x-(R 1R 2SiO) y-SiR 1 2R 3
(in the formula, R 1And R 3For-CH 3, R 2For-C 3H 6O (C 2H 4O) 8(C 3H 6O) 24H, x are 70, and y is 3)
[polyoxyalkylene modification organopolysiloxane (b-4)]
Represented by following formula average the composition, and viscosity is 1500mm 2/ s.
R 1 2R 3SiO-(R 1 2SiO) x-(R 1R 2SiO) y-SiR 1 2R 3
(in the formula, R 1And R 3For-CH 3, R 2For-C 3H 6O (C 2H 4O) 24(C 3H 6O) 16H, x are 30, and y is 5)
(C) polyoxyethylene modification organopolysiloxane
[polyoxyethylene modification organopolysiloxane (c-1)]
Represented by following formula average the composition, and viscosity is 450mm 2/ s.
R 1 2R 3SiO-(R 1 2SiO) x-(R 1R 2SiO) y-SiR 1 2R 3
(in the formula, R 1And R 3For-CH 3, R 2For-C 3H 6O (C 2H 4O) 9.4H, x are 24, and y is 4)
[polyoxyethylene modification organopolysiloxane (c-2)]
Represented by following formula average the composition, and fusing point is 40 ℃.
R 1 2R 3SiO-(R 1 2SiO) x-SiR 1 2R 3
(in the formula, R 1For-CH 3, R 3For-C 3H 6O (C 2H 4O) 32CH 3, x is 60)
(D) polyoxyalkylene polymers
[polyoxyalkylene polymers (d-1)]
On average form by HO-(C 3H 6O) 35-H represents.
[polyoxyalkylene polymers (d-2)]
On average form by CH 2=CHCH 2O-(C 2H 4O) 21(C 3H 6O) 21-CH 3Expression.
(E) nonionic surfactant
(e-1) sorbitan monostearate
(e-2) Vinlub 73 (EO addition molal quantity 12)
(e-3) polyoxyl 40 stearate (EO addition molal quantity 200)
(e-4) polyoxyethylene cetyl ether (EO addition molal quantity 20)
" evaluation method "
Defoaming (just having added the back):
Add each sample of counting 0.2 quality % with the active ingredient amount in commercially available water-based machining fluid, water is diluted to 30 times with it, stirs 2 minutes with 6000rpm with homomixer, measures to stop to the time that finishes full disappearance from stirring.
Defoaming (after 50 ℃ * 7 days):
In commercially available water-based machining fluid, add each sample of counting 0.2 quality % with the active ingredient amount, preserved 7 days down at 50 ℃, water is diluted to 30 times with it then, stirs 2 minutes with 6000rpm with homomixer, measures to stop to the time that finishes full disappearance from stirring.
In add stability:
In commercially available water-based machining fluid, add each sample of 0.2 quality %, visual and observe outward appearance when under 50 ℃, having preserved 7 days according to following standard.
Zero: do not have swim, sediment, △: slightly swim, sediment, *: swim, sediment is many
Product stability:
Visual and observe state after under 45 ℃ each sample having been preserved 7 days according to following standard.
Zero: do not have and separate △: deep or light separation is arranged, *: separate
Table 1
Embodiment Comparative example
1 2 3 4 5 6 1 2 3 4
Composition (quality %) (A) (a-1) 12 15 15 15 20 12
(a-2) 25 10
(a-3) 12 10
(a-4) 12 10
(B) (b-1) 5 3 3 2 5 5 5 5
(b-2) 5
(b-3) 2 1 2 2
(b-4) 3 2 5 3
(C) (c-1) 5 3 3 1
(c-2) 3 2 2 2 3 3 3 3
(D) (d-1) 12 5 5 10 12 12 10 15
(d-2) 2 10 5
(E) (e-1) 3 3 2 2 3 3 3 3 3
(e-2) 1 1 1 1 1 1
(e-3) 2 1 1 2 2 2 2 2
(e-4) 1 2
(F) Water 62 50 54 63 70 55 62 62 55 62
Cut bubble After just having added 0’45” 1’30” 0’30” 0’45” 1’00” 0’30” 1’00” 1’30” 0’45” 1’00”
After 50 ℃ * 7 days 1’15” 3’00” 1’30” 1’30” 2’00” 2’15” More than 10 minutes 7’45” 9’00” 3’30”
In add stability ○ ○ ○ ○ ○ ○ × △ × ×
Product stability ○ ○ ○ ○ ○ ○ ○ × ○ ○

Claims (4)

1. defoaming agent composition is characterized in that containing:
(A), neutralize as required and/or the removal of low boiler cut and the silicone oil blend that obtains: 1～40 weight % by under room temperature～200 ℃, following (i)～(iii) composition being mixed
(i) viscosity under 25 ℃ is 10～100000mm 2/ s is essentially hydrophobic organopolysiloxane: 100 weight portions
(ii) carried out surface-treated micropowder silica: 1～20 weight portion with organopolysiloxane
(iii) base catalyst: 0.01～5 weight portion;
(B) viscosity under 25 ℃ shown in the following general formula (I) is 10～10000mm 2The polyoxyalkylene modification organopolysiloxane of/s or its mixture: 0～30 weight %
R 1 2R 3SiO-(R 1 2SiO) x-(R 1R 2SiO) y-SiR 1 2R 3 (I)
In the formula, R 1Be the replacement that is same to each other or different to each other or the monovalence alkyl of unsubstituted carbon number 1～18, R 2Be any monovalent organic radical group shown in the following general formula (II), R 3Be R 1, R 2, hydroxyl or carbon number 1～6 alkoxyl, x is 5～200 integer, y is 1～30 integer,
-R 4-O(CH 2CH 2O) a-(CH 2(CH 3)CHO) b-R 5 (II)
In the formula, R 4Be the bivalent hydrocarbon radical of carbon number 2～6, R 5For hydrogen atom or be selected from any monovalent organic radical group of alkyl, acetyl group and the isocyano group of carbon number 1～6, a and b are for satisfying the positive number of 3≤a+b≤80 and a/b=2/8～8/2;
(C) the polyoxyethylene modification organopolysiloxane shown in the following general formula (III) or its mixture: 1～40 weight %
R 6 2R 8SiO-(R 6 2SiO) m-(R 6R 7SiO) n-SiR 6 2R 8 (III)
In the formula, R 6Be the replacement that is same to each other or different to each other or the monovalence alkyl of unsubstituted carbon number 1～18, R 7Be the polyoxyethylene groups shown in the following general formula (IV), R 8Be R 6, R 7, hydroxyl or carbon number 1～6 alkoxyl, m is 5～200 integer, n is 1～30 integer,
-R 9-O(CH 2CH 2O) c-R 10 (IV)
In the formula, R 9Be the bivalent hydrocarbon radical of carbon number 2～6, R 10For hydrogen atom or be selected from any monovalent organic radical group of alkyl, acetyl group and the isocyano group of carbon number 1～6, c is 3～50 positive number;
(D) polyoxyalkylene polymers or its mixture: 0～40 weight %;
(E) nonionic surfactant or its mixture: 0～20 weight %;
(F) water: it is 100 weight % that its content makes the total content of component (A)～(F).
2. the described defoaming agent composition of claim 1, wherein the content of component (B) is 1～30 weight %.
3. the described defoaming agent composition of claim 1, wherein component (D) polyoxyalkylene polymers is by shown in the following general formula (VI I), and its content is 5～40 weight %,
R 14O-(R 15O) z-R 14 (VII)
Wherein, R 14Be any monovalent organic radical group of hydrogen atom or carbon number 1～20, R 15Be the bivalent hydrocarbon radical of carbon number 2～6, z is that the polystyrene conversion weight average molecular weight that makes this polyoxyalkylene polymers adopt GPC to measure is 500～5000 number.
4. the described defoaming agent composition of claim 1, wherein the content of component (E) is 1～20 weight %.
CNA2007100058604A 2006-02-24 2007-02-25 Foam suppressing composition Pending CN101053797A (en)

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