CN1689692A - Surfactant - Google Patents

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Publication number
CN1689692A
CN1689692A CN200510059477.8A CN200510059477A CN1689692A CN 1689692 A CN1689692 A CN 1689692A CN 200510059477 A CN200510059477 A CN 200510059477A CN 1689692 A CN1689692 A CN 1689692A
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parts
surfactant
silica
water
oil
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CN200510059477.8A
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CN100518918C (en
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八木胜幸
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NIPPON NOPCO ASSISTANT CO Ltd
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NIPPON NOPCO ASSISTANT CO Ltd
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Abstract

The invention provides a surfactant with a reduced variation in surface activity. The surfactant comprises (A) a hydrophilic silica of a specific surface area of 100-450 m<SP>2</SP>/g, measured by the BET method (JIS R1626-1996), (D) a polyoxyalkylene compound and (C) a hydrophobic silica. (D) preferably contains one or more of compounds of formulae (1) and (2) (wherein R is a 1-6C linear alkyl or alkenyl group or a hydrogen atom; OA is each a 3-4C oxyalkylene group; n is a 10-100 integer; and m is 0 or 1). More preferably, the surfactant contains (B) water in a B/A weight ratio of 0.1-20.

Description

Surfactant
Technical field
The present invention relates to surfactant.In more detail, relate to a kind of pulp industry, food industry, fiber industry, building materials be suitable as in fields such as sheet material manufacturing, coatings industry or chemical industry manufacturing procedure with and the surfactant used of drainage position science and engineering preface.
Background technology
A known class contains the surfactant (spy opens clear 56-147858 communique, the spy opens the 2001-212403 communique) of hydrophobic silica and polyethers at present.
The surfactant that contains hydrophobic silica and polyethers in the past, owing to long-term storage makes hydrophobic silica generation sedimentation, surface active energy (antifoam performance etc.) is often different in use,, exists the problem that deviation can take place surface active easily that is.
Summary of the invention
The objective of the invention is to, provide a kind of surface active can be difficult to take place the surfactant of deviation.
The inventor has carried out meticulous research repeatedly in order to solve above-mentioned problem, found that, uses specific hydrophily silica to achieve the above object, thereby has finished the present invention.That is, the feature of surfactant of the present invention is that wherein containing the specific area that records by BET method (JIS R1626-1996) is 100～450m 2The hydrophily silica (A) of/g, polyoxyalkylene compounds (D) and hydrophobic silica (C).
Surfactant of the present invention is because the goods excellent in stability often can have been given play to identical surface active energy (antifoam performance etc.).That is, surface active can be difficult to take place deviation.Therefore, can be used as pulp industry, food industry, fiber industry, building materials with the manufacturing procedure of sheet material manufacturing, coatings industry or chemical industry etc. with and the surfactant used of wastewater treatment operation.Particularly can be used as defoamer.
The specific embodiment
As hydrophily silica (A), comprise (1) damp process silica: by with the inorganic silicon dioxide aeroge (with the moisture in the silica hydrogel with a kind of boiling point after below 70 ℃ and with glassware for drinking water solvent (methyl alcohol, acetone, methyl formate, the methyl acetate etc.) displacement of compatibility being arranged, remove the cataloid that this solvent obtains by heating); (2) thermal decomposition method silica: fumed silica (cataloid that the silica carbon black that is generated by the roasting silicon tetrachloride constitutes); And (3) molten solids method silica: settleability silica (condensing the silicon dioxide granule that obtains) etc. by in sodium silicate aqueous solution, splashing into sodium ions such as sodium chloride, sodium sulphate; The silica that adopts any method to make can.Wherein, the considerations such as viewpoint from the goods stability of surfactant are preferably fumed silica and settleability silica, more preferably settleability silica.
Should illustrate that hydrophily silica is to be used for being different from following hydrophobic silica, be meant the silicon oxide particle of not handling through hydrophobization.On the other hand, hydrophobic silica is meant the silicon oxide particle of handling through hydrophobization.
Specific area (the m of the hydrophily silica (A) that employing BET method records 2/ g) be preferably 100～450, more preferably 150～400, be preferably 250～350 especially.If be in this scope, then the goods of surfactant stability further improves.
Should illustrate that specific area is that the value measured according to JIS R1626-1996 (one point method) { is measured sample: 50mg (sample that formed in 15 minutes 200 ℃ of following heat treated), the assay method of adsorbance: fixed molten method, adsorbent: gaseous mixture (N 270 volume %, He 30 volume %), measure the balance relative pressure: 0.3, device: for example big storehouse reason is ground the system automatic powder surface measurements device AMS-8000} of society.
The particle diameter of hydrophily silica (A) (μ m) is preferably 1～50, and more preferably 1.5～40, be preferably 2～30 especially.Should illustrate that particle diameter is to measure according to the 5.7.2.1 resistance-type granulometry of JIS K1150-1994.As determinator, can use for example コ one Le one マ Le チ サ イ ザ one (ベ Star Network マ Application コ one Le カ ウ Application one (strain)) { electrolyte: ISOTONII (ベ Star Network マ Application コ one Le one (strain)), sample solution concentration: 1.0 weight %, capillary ア パ one チ ヤ チ ュ one ズ aperture: 30 μ m} etc.
Hydrophily silica (A) can easily be buied from market, can list for example commodity of table 1.
[table 1]
The name of an article Specific area m 2/g Particle diameter μ m Producer
NIPGEL?AY-200 ?300 ?2.0 Japan silica Industrial Co., Ltd
NIPGEL?BY-200 ?450 ?1.7
Nipsil?L-250 ?170 ?2.0
Nipsil?E-220 ?110 ?1.5
FINESIL?E70 ?155 ?1.9 The ト of Co., Ltd. Network ヤ マ
FINESIL?T32 ?202 ?1.5
SYLYSIA?250N ?300 ?2.7 シ リ シ ア KCC of Fuji
SYLYSIA?350 ?300 ?1.8
SYLYSIA?430 ?300 ?2.5
AEROSIL?130 ?130 ?16 Japan ア エ ロ ジ Le Co., Ltd.
AEROSIL?300 ?300 ?12
AEROSIL?380 ?380 ?7
The amount (weight %) of hydrophily silica (A) is a benchmark with the weight of surfactant, is preferably 0.01～10, more preferably 0.1～6, be preferably 0.2～5 especially.If be in this scope, then the goods of surfactant stability further improves.
As polyoxyalkylene compounds (D),, just can use ad lib so long as contain the compound of polyoxyalkylenes.
As polyoxyalkylenes, comprise the group that a plurality of oxyalkylene groups (oxidation ethylidene, propylene oxide and oxybutylene) chemical bonding of carbon number 2～4 forms.
Polyoxyalkylenes can be made of a kind in the oxyalkylene group, also can be by constituting more than 2 kinds.By the occasion that constitutes more than 2 kinds, combining form can be block, random and mixed form any.
As polyoxyalkylene compounds (D), comprise compound with general formula (1) or (2) expression; Special public clear 50-5157 number, special public clear 49-38923 number, special public clear 50-1475 number, special public clear 45-7973 communique, the spy opens clear 50-4282 number or the special polyoxyalkylene compounds of putting down in writing in flat 2-289526 number each communique of opening; PAG (carbon number 2～8, the degree of polymerization 1～100) higher fatty acids (carbon number 8～24) ester { single octadecane acid esters of polyethylene glycol (degree of polymerization 20) and polyethylene glycol (degree of polymerization 30) octadecanoid acid diester etc. }, polyoxyalkylene (carbon number 2～8, the degree of polymerization 1～100) polynary (3～10 yuan) pure higher fatty acids (carbon number 8～24) ester { polyoxyethylene (degree of polymerization 10) sorbitan dodecylic acid list or diester etc. }, oxyalkylene (carbon number 2～8) addition product (adduct number 1～100) of alkylamine (carbon number 8～24) { lauryl amine ethylene oxide adduct (adduct number 20) etc. }, and condensation alkylphenol (carbon number 8～24) polyoxyalkylene (carbon number 2～8) addition product (adduct number 1～100) { condensation nonyl phenol ethylene oxide adduct (adduct number 20) etc. }; And their mixture etc.
Wherein, preferably, preferably contain this compound at least with the compound of general formula (1) or (2) expression.
R-(OA)n-OH????????????????????(1)
CH 2-(OA)n-OH
|
{CH-(OA)n-OH}m????????????????(2)
|
CH 2-(OA)n-OH
In the general formula (1), R represents straight chained alkyl or the straight alkenyl or the hydrogen atom of carbon number 1～6.
As straight chained alkyl, can list ethyl, n-pro-pyl, normal-butyl, n-pentyl and n-hexyl.
As straight alkenyl, can list vinyl, 1-acrylic, 2-acrylic, 3-cyclobutenyl, 2-cyclobutenyl, 4-pentenyl, 5-hexenyl and 1-hexenyl etc.
Wherein, from the considerations such as viewpoint of defoaming, preferred straight chained alkyl, more preferably n-pro-pyl, normal-butyl, n-pentyl and n-hexyl, especially preferably normal-butyl, n-pentyl and n-hexyl.
In general formula (1) and (2), OA represents the oxyalkylene group of carbon number 3～4, comprises propylene oxide, butylene oxide and their mixture.Wherein, preferred propylene oxide.
Should illustrate,,, also can contain the oxidation ethylidene of some so long as be that main body gets final product with the oxyalkylene group of carbon number 3～4 as oxyalkylene group.So-called main body is meant that the total mole number with oxyalkylene group formation unit is a benchmark, contains 70 moles of % at least, preferably contains 75 moles more than the %, more preferably contains 80 moles more than the %, especially preferably contains 85 moles more than the %, most preferably contains 90 moles more than the %.
Under the occasion that contains multiple class oxyalkylene group, can be block-wise, random shape and mixed form thereof any, preferred random shape.
In general formula (1) and (2), n represents 10～100 integer, is preferably 20～50 integer, more preferably 25～45 integer.If be in this scope, then can further suppress the generation of pearl etc. of contracting.
In the general formula (2), m represents 0 or 1.
As the polyoxyalkylene compounds of general formula (1) expression, can list with the compound of following chemical formulation etc.Should illustrate that eo represents the oxidation ethylidene, po represents oxypropylene, and bo represents oxybutylene, the expression block-wise ,/represent random shape (following same).
C 2H 5-(po) 25-OH??????????????????????????????????????(3)
C 2H 5-(po) 45-OH??????????????????????????????????????(4)
C 2H 5-(po) 30·(bo) 2-OH??????????????????????????????(5)
C 3H 7-(po) 25-OH??????????????????????????????????????(6)
C 3H 7-(po) 45-OH??????????????????????????????????????(7)
C 3H 7-(po) 30·(bo) 2-OH??????????????????????????????(8)
C 4H 9-(po) 25-OH??????????????????????????????????????(9)
C 4H 9-(po) 45-OH??????????????????????????????????????(10)
C 4H 9-(po) 30·(bo) 2-OH??????????????????????????????(11)
C 4H 9-(po) 30/(bo) 5-OH???????????????????????????????(12)
C 5H 11-(po) 25-OH???????????????????????????????????????(13)
C 5H 11-(po) 45-OH???????????????????????????????????????(14)
C 5H 11-(po) 30·(bo) 2-OH???????????????????????????????(15)
C 6H 13-(po) 25-OH???????????????????????????????????????(16)
C 6H 13-(po) 45-OH???????????????????????????????????????(17)
C 6H 13-(po) 30·(bo) 2-OH???????????????????????????????(18)
H-(po) 20-OH??????????????????????????????????????????????(19)
H-(po) 40-OH??????????????????????????????????????????????(20)
H-(po) 60-OH??????????????????????????????????????????????(21)
H-(po) 80-OH??????????????????????????????????????????????(22)
H-(po) 100-OH??????????????????????????????????????????????(23)
As the polyoxyalkylene compounds of general formula (2) expression, can list with the compound of following chemical formulation etc.
CH 2-(po)n 1-OH
|???????????????????????????????????????????????????????????(24)
CH 2-(po)n 2-OH????n 1n 26(n 1+n 2＝12)
CH 2-(po)n 1-OH
|
CH-(po)n 2-OH??????????????????????????????????????????????(25)
|
CH 2-(po)n 3-OH????n 1n 2n 313(n 1+n 2+n 3＝40)
CH 2-(po)n 1-OH
|
CH-(po)n 2-OH??????????????????????????????????(26)
|
CH 2-(po)n 3-OH??????n 1n 2n 320(n 1+n 2+n 3＝60)
CH 2-(po)n 1-(eo)n 4-OH
|
CH-(po)n 2-(eo)n 5-OH?????????????????????????(27)
|
CH 2-(po)n 3-(eo)n 6-OH
n 1n 2n 313(n 1+n 2+n 3＝40)
n 4n 5n 65(n 4+n 5+n 6＝15)
CH 2-(po)n 1-(eo)n 4-OH
|
CH-(po)n 2-(eo)n 5-OH??????????????????????????(28)
|
CH 2-(po)n 3-(eo)n 6-OH
n 1n 2n 320(n 1+n 2+n 3＝60)
n 4n 5n 65(n 4+n 5+n 6＝15)
In these polyoxyalkylene compounds, preferably with the compound of general formula (1) or (2) expression, more preferably with the polyoxyalkylene compounds of formula (7), (10), (14), (15), (21), (27) or (16) expression, especially preferably with the polyoxyalkylene compounds of formula (7), (10) or (15), (21), (27) expression.
With the polyoxyalkylene compounds of general formula (1) or (2) expression, the method that can adopt the oxyalkylene of the straight chain alkanol that makes carbon number 2～6 or straight chain enol or polyalcohol and carbon number 3～4 to react waits and obtains.
As polyoxyalkylene compounds with general formula (1) or (2) expression, can easily buy from market, as trade name, can list ニ ュ one Port, one Le series (LB-65, LB-385, LB-625, LB-1145, LB-1715, LB-1800X, PP-950, PP-1000, PP-2000, PP-3000, PP-4000, PP-5000 etc.), サ Application ニ Star Network ス ト リ オ one Le series (GP-3000, GP-4000, GP-5000, GL-3000 and GL-5000 etc.) { Sanyo changes into industry (strain) product }; And ュ ニ Le one Block series (MB-19, MB-38 and MB-370 etc.) { Japanese grease (strain) product } etc.
The amount (weight %) of polyoxyalkylene compounds (D) is a benchmark with the weight of surfactant, is preferably 0.1～90, more preferably 20～80, be preferably 40～75 especially.If be in this scope, then the goods stability of surfactant becomes better.
As hydrophobic silica (C), comprise by above-mentioned hydrophily silica (A) being carried out hydrophobization and handle the silica make (special public clear 42-26179 communique) etc. with hydrophobizers.
As hydrophobizers, comprise silicone oil and modified silicon oil etc.
As silicone oil, can list kinematic viscosity 10～3000 (mm 2/ s, 25 ℃) dimethyl siloxane etc., also comprise ring four (dimethyl) siloxanes etc.
As modified siloxane, comprise that a part of methyl of above-mentioned dimethyl siloxane replaces with the aminoalkyl of the alkoxyl of the alkyl of carbon number 2～6, carbon number 2～4, phenyl, hydrogen atom, halogen (chlorine and bromine etc.) atom and/or carbon number 2～6 etc. and the siloxanes that forms etc.
As the use amount (weight %) of hydrophobizers, be benchmark with the weight of the hydrophily silica (A) handled by hydrophobization, be preferably 5～70, more preferably 7～50, be preferably 10～30 especially.If be in this scope, then defoaming is better.
The temperature of handling as hydrophobization (℃), be preferably 100～400, more preferably 150～350, be preferably 200～300 especially.
When hydrophobization is handled, can use solvent { hydrocarbon ils, kinematic viscosity (mm 2/ s, 40 ℃) be 5～30 paraffin oils and operation wet goods and catalysts (sulfuric acid, nitric acid, hydrochloric acid, glycolic acid, trifluoroacetic acid, paranitrobenzoic acid, potassium hydroxide, lithium hydroxide etc.).
As hydrophobic silica (C), can buy from market, can list Nipsil series (SS-10, SS-40, SS-50 and SS-115 etc.) as trade name (Japanese silica Co., Ltd.); AEROSIL series (R972, RX200 and RY200 etc.) (Japanese ア エ ロ ヅ Le Co., Ltd.); (キ ヤ ボ Star ト カ one ボ Application societies) such as TS-530, TS-610, TS-720; AEROSIL series (R202, R805 and R812 etc.) (デ ゲ サ ヅ ヤ パ Application Co., Ltd.); REOLOSIL series (MT-10, DM-10 and DM-20S etc.) (ト of Co., Ltd. Network ヤ マ); And SYLOPHOBIC series (100,702,505 and 603 etc.) (シ リ シ ア KCC of Fuji) etc.
In the occasion that contains hydrophobic silica (C), its amount (weight %) is a benchmark with the weight of surfactant, is preferably 0.1～20, more preferably 0.5～15, be preferably 1～10 especially.If be in this scope, then surface active can (antifoam performance etc.) etc. becomes better.
In the surfactant of the present invention, preferably further contain water (B).
There is no particular limitation as water (B), can use distilled water, ion exchange water, running water, water for industrial use, well water, spring, river water and rainwater etc.Consider from the viewpoint of the goods stability of surfactant, preferably use soft water such as ion exchange water, running water and water for industrial use.
In the occasion that contains water (B), its amount (weight %) is a benchmark with the weight of surfactant, is preferably 0.001～40, more preferably 0.1～30, be preferably 0.3～20 especially.If be in this scope, then surface active can (antifoam performance etc.) etc. becomes better.In addition, in this occasion, the weight ratio (B/A) of hydrophily silica (A) and water (B) is preferably 0.1～20, and more preferably 1～15, be preferably 3～7 especially.If be in this scope, then the goods of surfactant stability further improves.
In the surfactant of the present invention, preferably also contain hydrocarbon ils (E).
Aromatic hydrocarbon composition (fragrance ingredient in the hydrocarbon ils (E); CA) amount (weight %) is a benchmark with the weight of (E), is preferably 1～30, more preferably 2～20, be preferably 4～15 especially, and most preferably be 6～12.If be in this scope, then defoaming and goods stability (surfactant separate etc.) become better.
Should illustrate that each amount of fragrance ingredient, cycloalkane composition and alkane composition is that the employing ring analysis (come quantitative by (n-d-M) method (ASTM D 3238-74).
Kinematic viscosity (mm as hydrocarbon ils (E) 2/ s; 40 ℃), be preferably 2～150, more preferably 2.5～30, be preferably 3～28 especially, most preferably be 4～25.
Hydrocarbon ils (E) can easily be buied from market, can list commodity of table 2 for example etc.
[table 2]
Trade name Amount (weight %) Kinematic viscosity mm 2/ s Producer's name
Fragrance ingredient The cycloalkane composition The alkane composition
コスモピュアスピンG 9.7 ?30.6 ?59.7 21.0 コ ス モ oil Le Block リ カ Application Star Co., Ltd.
コスモピュアスピンE 9.7 ?23.0 ?67.3 4.7
コスモ?SP10 2.5 ?30.8 ?66.7 9.5
コ ス モ ニ ュ one ト ラ Le 150 6.9 ?26.6 ?66.5 31.7
コスモ?SC?22 2.5 ?30 ?67.5 21.1
コ ス モ RC bobbin oil 2.5 ?30.8 ?66.7 9.5
コ ス モ RB bobbin oil 3.1 ?26.7 ?70.2 15.4
Day stone ス one パ one オ イ Le B 7.0 ?28.0 ?65.0 51.6 Nippon Petrochemicals Company, Limited
Day stone ス one パ one オ イ Le C 5.5 ?29 ?65.5 97.5
Day stone ス one パ one オ イ Le D 6 ?27.5 ?66.5 147
ス ノ one Le 35 7 ?27 ?66 9.3 エ Star ソ oil Co., Ltd.
ス ノ one Le 43N 4 ?28 ?68 28.9
ス ノ one Le 52 4 ?27 ?69 56.3
ス ノ one Le 69 5 ?27 ?68 127
ス ノ one Le LP35 7 ?30 ?65 11.5
Off Star コ one Le SH ス ピ Application 4 ?27 ?69 9.1 Emerging product Co., Ltd. of Fuji
Off Star コ one Le ST マ Star Application 6 ?31 ?63 9.5
Off Star コ one Le NT60 ?5.5 ?28.5 ?66 9.6
Off Star コ one Le NT100 ?4.5 ?25.5 ?70 21.6
Off Star コ one Le NT100S ?4 ?27 ?69 21.4
Off Star コ one Le NT150 ?4.5 ?26 ?69.5 27.5
Off Star コ one Le NT200 ?4.5 ?26 ?69.5 39.4
Should illustrate,, also can use vegetable and animals oils and above-mentioned mineral wet goods and mixture of vegetable and animals oils etc. as hydrocarbon ils (E).
As vegetable and animals oils, can use crude vegetal, natural animal oil and modification wet goods thereof, can list tallow, lard, whale oil, fish oil, rapeseed oil, soybean oil, sunflower oil, cottonseed oil, peanut oil, rice bran oil, corn oil, safranine caul-fat, olive oil, sesame oil, evening primrose oil, palm oil, cherish Ah fat, spread road fat, cocoa butter, coconut oil, palm kernel wet goods and hydrogenation wet goods thereof.
In the occasion that contains hydrocarbon ils (E), its amount (weight %) is a benchmark with the weight of surfactant, is preferably 0.1～50, more preferably 10～40, be preferably 20～30 especially.If be in this scope, then goods stability (separation of surfactant etc.) and defoaming become better.
Hydrophily silica (A), water (B), hydrophobic silica (C), polyoxyalkylene compounds (D) or hydrocarbon ils (E) also can be used in combination of two or more respectively.
The occasion that in surfactant of the present invention, contains hydrophily silica (A), water (B), hydrophobic silica (C), polyoxyalkylene compounds (D) and hydrocarbon ils (E), they contain weight ratio (A: B: C: D: E) be preferably (0.01～10): (0.001～40): (0.1～20): (0.1～90): (0.1～50), more preferably (0.1～6): (0.1～30): (0.5～15): (20～80): (10～40) are preferably (0.2～5) especially: (0.3～20): (1～10): (40～75): (20～30).If be in this scope, then goods stability (separation of surfactant etc.) and defoaming become better.
In the surfactant of the present invention, except containing hydrophily silica (A), water (B), hydrophobic silica (C), polyoxyalkylene compounds (D) and hydrocarbon ils (E), can also contain other constituent (fatty acid amide of the alcohol of water soluble polymer, native paraffin, synthetic wax, carbon number 12～30, the carboxylate of carbon number 12～30, carbon number 8～30 and/or silicone oil etc.).And then, also can contain additive (known surfactant, tackifier, anticorrisive agent and/or solvent etc.).Other constituent and additive also can be used in combination more than 2 kinds separately.
In the occasion of constituent that contains other and/or additive, their total amount (weight %) is a benchmark with the weight of surfactant of the present invention, is preferably 0.01～30, more preferably 0.1～20, be preferably 1～10 especially.If be in this scope, then goods stability (separation of surfactant etc.) and defoaming become better.
As the water soluble polymer that other constituents contain, can use water soluble anion macromolecule, water-soluble nonionic macromolecule, water-soluble cationic macromolecule and soluble amphoteric macromolecule.
As the water soluble anion macromolecule, can list water soluble anion macromolecule [polyacrylic acid (the salt) (weight average molecular weight 2 that adopts radical polymerization to obtain, 000～100,000), polystyrolsulfon acid (salt) (weight average molecular weight 1,000～100,000), polyacrylic acid ethoxy phosphate monoester (weight average molecular weight 2,000～50,000) etc.], water soluble anion macromolecule [naphthalene sulfonic acids (salt) formaldehyde condensation products (condensation degree 2～10) etc.] that employing non-free radical polymerization (condensation etc.) obtains and the water soluble anion macromolecule [lignosulfonic acid (weight average molecular weight 10 that obtains by natural goods, 000～1,000,000), alginic acid (salt) (weight average molecular weight 10,000～1,000,000) etc.] etc.
The water-soluble nonionic macromolecule, can list the water-soluble nonionic macromolecule [polyvinyl alcohol (weight average molecular weight 5 that adopts radical polymerization to obtain, 000～100,000), polyacrylamide (weight average molecular weight 1,000～100,000) etc.], water-soluble nonionic macromolecule [polyethylene glycol (the weight average molecular weight 2 that adopts non-free radical polymerization (addition etc.) to obtain, 000～1,000,000) etc.] and the water-soluble nonionic macromolecule [methylcellulose (weight average molecular weight 1 that obtains by natural goods, 000～1,000,000), hydroxyethylcellulose (weight average molecular weight 1,000～1,000,000) etc.] etc.
As the water-soluble cationic macromolecule, can list water-soluble cationic macromolecule [the poly-aminoethyl methacrylate (weight average molecular weight 1 that adopts radical polymerization to obtain, 000～50,000) etc.], water-soluble cationic macromolecule [the poly-ethylidene polyamines (weight average molecular weight 1 that adopts the non-free radical polymerization to obtain, 000～100,000) etc.] and the water-soluble cationic macromolecule [cationic starch (weight average molecular weight 5,000～1 that obtains by natural goods, 000,000) etc.] etc.
As the soluble amphoteric macromolecule, can list acrylic acid/aminoethyl methacrylate copolymer (weight average molecular weight 1,000～100,000) etc.
Should illustrate, as salt, the carbon number that can list ammonium salt, alkyl is that the carbon number of 1～4 alkylamine (mono aminoethane, dibutyl amine and triethylamine etc.) salt, alkanol is 1～4 alkanolamine (MEA, diethanol amine and triethanolamine etc.) salt, alkali metal (lithium, sodium and potassium etc.) salt and alkaline-earth metal (magnesium, calcium and zinc etc.) salt etc., can be fully or partly form salt.Herein, in the present invention, what is called is water-soluble to be meant that the solubility in water 100g is down more than the 20g (preferred 30g) at 25 ℃.
As native paraffin, can list candelila wax, Brazil wax, rice wax, haze tallow, jojoba oil, honeybee and lanolin etc.
As synthetic wax, can list microwax, vaseline, Tissuemat E and Fischer-Tropsch synthetic wax etc.
As alcohol, can use natural alcohol (laruyl alcohol, myristyl alcohol, cetanol, stearyl alcohol, eicosanol, docosanol, tetracosanol, hexacosyl alcohol, octacosanol, beacon are spent alcohol and oleyl alcohol etc.) and synthol (adopt synthetic non-the chain of straight chain of ziegler process saturated alcohols, adopt the synthetic straight chain primary alcohol of carbonyl process or branched-chain primary alcohol, linear secondary that the alkane air oxidation is synthetic etc.) etc.
As the carboxylate of carbon number 12～30, can use fatty acid ester (stearic acid palm ester, stearic acid stearyl ester, oleic acid stearyl ester, oleic acid oil base ester and stearic acid oil base ester etc.) that the carboxylic acid of 1～6 yuan of alcohol of carbon number 1～30 and carbon number 12～30 generates etc.
As the fatty acid amide of carbon number 8～30, can list the two palmitamides of ethylenebisstearamide, ethylenebis palmitamide, ethylenebis lauramide, butylidene bis-stearamides and butylidene etc.
As silicone oil, can use dimethyl polysiloxane, polyether modified silicone, alkyl-modified silicone etc.
As can using nonionic surface active agent, anionic surfactant, cationic surface active agent and amphoteric surfactant as the known surfactant of additive.
As nonionic surface active agent, can list polynary (2～10 yuan) polyol fatty acids (carbon number 8～24) ester [glycerine list octadecane acid esters, single octadecanoid acid glycol ester and sorbitan octadecenic acid list or diester etc.], aliphatic alkane alcohol amide [coconut oil fatty acid monoethanolamide, dodecylic acid diglycollic amide etc.] and alkyl (carbon number 8～24) dialkyl group (carbon number 1～6) amine oxide [oxidizing dodecyl dimethyl amine etc.] etc.
As anionic surfactant, can list alkyl (carbon number 8～24) polyoxyalkylene (carbon number 2～3; the degree of polymerization 1～100) carboxylic acid or its salt (alkali metal salt and ammonium salt etc.) [dodecyl polyoxyethylene (degree of polymerization 20) sodium acetate etc.]; the sulfuric acid of carbon number 8～24 [laurilsulfate sodium; dodecyl polyoxyethylene (degree of polymerization 30) sodium sulfovinate etc.]; sulfonate [the neopelex of carbon number 8～24; sulfosuccinic acid two-2-Octyl Nitrite sodium etc.]; the phosphate ester salt of carbon number 8～24 [dodecylphosphoric acid sodium; dodecyl polyoxyethylene (degree of polymerization 30) sodium phosphate etc.]; carboxy acid alkali's slaine; ammonium salt or amine salt [dodecylic acid sodium; dodecylic acid triethanolamine and hendecanoic acid ammonium etc.]; acylated amino acid coco-nut oil fatty acid N-methyltaurine sodium [coconut oil fatty acyl group-L-glutamic acid triethanolamine etc.].
As cationic surfactant, can list quaternary [chlorination octadecyl trimethylammonium, chlorination two (octadecyl) dimethylammonium etc.], amine salt type [octadecanoid acid lignocaine acetamide lactate etc.] etc.
As amphoteric surfactant, can list betaine type amphoteric surfac-tant's [coconut oil fatty amide propyl dimethylamino acetate betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazole betaine salt etc.], amino acid type amphoteric surfactant [β-dodecane alanine sodium etc.].
As tackifier, can list organically modified montmorillonite clay, organically-modified saponite, organically-modified hectorite, organically-modified sodium silicon mica sodium, organically-modified lithium taincolite [taeniolite], organic modified bentonite, hydroxy stearic acid, polyisobutene, polyalkyl methacrylate and metallic soap etc.
As anticorrisive agent, can list 2-bromo-2-nitro-1, ammediol (BNP), 5-chloro-2-methyl-4-isothiazoline-3-ketone (MIT), 1,2-[4-morpholinodithio quinoline-3-ketone, 2-methyl-4-isothiazoline-3-ketone, six hydrogen-1,3,5-three (2-ethoxy)-s-triazine, six hydrogen-1,3,5-three (2-ethyl)-s-triazine, adjacent phenyl-phenol, 3-methyl-4-chloro-phenol, pyridine mercaptan oxidation sodium, dithiocarbamate, 4-(2-nitro butyl) morpholine and 1-(3-chloro pi-allyl)-3,5,7-three azepines-1-azo group two adamantane chlorides etc.
As solvent, can use ester (acetic acid esters and butyl acetate etc.), aklylene glycol monoether (ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether etc.) etc.
Surfactant of the present invention can adopt the mixed uniformly manufacture method of constituent waited to obtain, and can adopt known method manufacturing.As known method, can list hydrophily silica (A), water (B), hydrophobic silica (C), polyoxyalkylene compounds (D) and hydrocarbon ils constituents such as (E) joined and carry out even stirring method etc. in the agitating device.
Evenly there is no particular limitation for the temperature that stirs, but for easy mixing, can be heated to about 50 ℃.
Hydrophobic silica (C) is preferably used hydrocarbon ils (E) dilution in advance, more preferably will (C) and (E) evenly stir after, carry out the diffusing processing of differential with ball mill, dispersion mill, homogenizer or high woods homogenizer etc.
As even mixing arrangement, so long as can mixed uniformly device just without limits, can use propeller-type mixer, dissolving machine, homomixer, ball mill, sand mill, ultrasonic dispersing machine, kneading machine and flow mixer etc.Should illustrate that these devices can be used in combination.
The viscosity of surfactant of the present invention (mpas/25 ℃) is preferably 200～4000, and more preferably 300～3000, be preferably 400～3500 especially, most preferably be 500～2000.If be in this scope, then operability and the defoaming when goods stability (separation of surfactant etc.), operation becomes better.Should illustrate that viscosity is to measure according to the method for the 4.2 single cylinder rotation viscometer methods (corresponding with ISO2555) of JIS K7233-1986.
Surfactant of the present invention can adopt continuous additive process, interrupted additive process or make the bubble analyzer and the method for defoamer adding set interlock etc., adds in being added liquid.And, also can be to add at 1 position and multiple spot adds any in adding.In addition, during interpolation, also can dilute with suitable dilution solvent or water etc.
Surfactant of the present invention also can and be used with following known defoamer: for example, and polyether antifoam agent (special public clear 50-5157 number, special public clear 49-38923 number, special public clear 50-1475 number, special public clear 45-7973 communique, the spy opens clear 50-4282 number and the spy opens flat 2-289526 number each communique etc.), silicone antifoam agent (special public clear 51-35556 number, the spy opens clear 57-48307 number, the spy opens clear 52-2887 number, special public clear 52-19836 number, special public clear 52-22638 number, special public clear 55-23084 number, Te Kaiping 6-142410 number and spy open flat 6-142411 number each communique etc.), mineral oil antifoam agent (special public clear 49-109276 number, the spy opens clear 51-80692 number, the spy opens clear 52-22356 number, the spy opens clear 54-32187 number, the spy opens clear 55-70308 number and spy and opens clear 56-136610 number each communique etc.) and the wax emulsion defoamer (spy opens clear 47-114336 number, special public clear 56-17124 number, the spy opens clear 60-156516 number, the spy opens clear 62-171715 number, the spy opens clear 64-68595 number, Te Kaiping 1-210005 number and spy open flat 4-349904 number each communique etc.) etc.
The addition of surfactant of the present invention (weight %), can wait aptly according to the foamed state that is added liquid and set, but, with the weight that is added liquid is benchmark, be preferably 0.0001～10, more preferably 0.0005～8, be preferably 0.001～5 especially, most preferably be 0.005～3.
[embodiment]
Below, further describe the present invention with embodiment, but the present invention is not subjected to the qualification of following examples.Should illustrate, unless otherwise specified, " part " expression weight portion, " % " expression weight %.
＜embodiment 1 〉
With (E1) 230 parts in E bobbin oil { コ ス モ oil Le Block リ カ Application Star (strain) system }, NipsilSS-10{ Japan's silica (strain) system } (C1) 30 parts and ニ ュ one Port one Le LB-625{ Sanyo change into industry (strain) system } (D1) 700 parts, ア エ ロ ヅ Le 300{ Japan's ア エ ロ ヅ Le (strain) system; Specific area 300m 3After 20 parts of 5 parts of/g} (A1), ion exchange water (B1) put in the reaction vessel that can heat, stir and cool off, be warming up to 50 ℃, under this temperature, continued to add thermal agitation 3 hours while stir.Stirred 15 minutes with the rotating speed of the homogenizer that the impeller type blade is installed (Ha イ Off レ Star Network ス デ イ ス パ one サ one HG-92G イ テ Star Network (strain) system, following same) again, obtain defoamer of the present invention (S1) with 4000rpm.In addition, in decentralization test { JIS K5600-2-5:1999 (corresponding with ISO 1524:1983) }, affirmation does not have the particle more than 5 microns.
＜embodiment 2 〉
20 parts of 30 parts of Nipsil SS-10 (C1), ニ ュ one Port one 700 parts of Le LB-625 (D1), 5 parts of ア エ ロ ヅ Le 300 (A1) and ion exchange waters (B1) are changed to (C1) 35 parts, (D1) 600 parts, (A1) 15 parts and (B1) 70 parts, in addition, obtain defoamer of the present invention (S2) similarly to Example 1.In addition, confirm not have particle more than 5 microns similarly to Example 1.
＜embodiment 3 〉
30 parts of Nipsil SS-10 (C1), 5 parts of ア エ ロ ヅ Le 300 (A1) and ion exchange water (B1) are changed to (C1) 35 parts, ア エ ロ ヅ Le 130{ Japan's ア エ ロ ヅ Le (strain) system for 20 parts; Specific area 130m 3In addition 15 parts of/g} (A2) and (B1) 70 parts, obtain defoamer of the present invention (S3) similarly to Example 1.In addition, confirm not have particle more than 5 microns similarly to Example 1.
＜embodiment 4 〉
30 parts of Nipsil SS-10 (C1), ニ ュ one Port one 700 parts of Le LB-625 (D1), 5 parts of ア エ ロ ジ Le 300 (A1) and ion exchange water (B1) are changed to (C1) 35 parts, (D1) 600 parts, ア エ ロ ヅ Le 380{ Japan ア エ ロ ヅ Le (strain), specific area 380m for 20 parts 3In addition 15 parts of/g} (A2) and (B1) 70 parts, obtain defoamer of the present invention (S4) similarly to Example 1.In addition, confirm not have particle more than 5 microns similarly to Example 1.
＜embodiment 5 〉
20 parts of (E1) 230 parts in E bobbin oil { コ ス モ oil Le Block リ カ Application Star (strain) system }, 30 parts of NipsilSS-10 (C1), ニ ュ one Port one 700 parts of Le LB-625 (D1), 5 parts of ア エ ロ ヅ Le 300 (A1) and ion exchange waters (B1) are changed to (E1) 0 part, (C1) 35 parts, (D1) 600 parts, (A1) 15 parts and (B1) 70 parts, in addition, obtain defoamer of the present invention (S5) similarly to Example 1.In addition, confirm not have particle more than 5 microns similarly to Example 1.
＜embodiment 6 〉
20 parts of 30 parts of Nipsil SS-10 (C1), ニ ュ one Port one 700 parts of Le LB-625 (D1), 5 parts of ア エ ロ ジ Le 300 (A1) and ion exchange waters (B1) are changed to (C1) 35 parts, ニ ュ one Port one 600 parts of Le PP-3000 (D2), (A1) 15 parts and (B1) 5 parts, in addition, obtain defoamer of the present invention (S6) similarly to Example 1.In addition, confirm not have particle more than 5 microns similarly to Example 1.
＜embodiment 7 〉
20 parts of 30 parts of Nipsil SS-10 (C1), ニ ュ one Port one 700 parts of Le LB-625 (D1), 5 parts of ア エ ロ ヅ Le 300 (A1) and ion exchange waters (B1) are changed to (C1) 35 parts, ニ ュ one Port one 600 parts of Le PP-3000 (D2), (A1) 4 parts and (B1) 70 parts, in addition, obtain defoamer of the present invention (S7) similarly to Example 1.In addition, confirm not have particle more than 5 microns similarly to Example 1.
＜embodiment 8 〉
20 parts of (E1) 230 parts in E bobbin oil { コ ス モ oil Le Block リ カ Application Star (strain) system }, 30 parts of NipsilSS-10 (C1), ニ ュ one Port one 700 parts of Le LB-625 (D1), 5 parts of ア エ ロ ジ Le 300 (A1) and ion exchange waters (B1) are changed to (E2) 230 parts in G bobbin oil { コ ス モ oil Le Block リ カ Application Star (strain) system }, (C1) 1 part, (D1) 600 parts, (A1) 15 parts and (B1) 70 parts, in addition, obtain defoamer of the present invention (S8) similarly to Example 1.In addition, confirm not have particle more than 5 microns similarly to Example 1.
＜embodiment 9 〉
20 parts of (E1) 230 parts in E bobbin oil { コ ス モ oil Le Block リ カ Application Star (strain) system }, 30 parts of NipsilSS-10 (C1), ニ ュ one Port one 700 parts of Le LB-625 (D1), 5 parts of ア エ ロ ヅ Le 300 (A1) and ion exchange waters (B1) are changed to (E2) 230 parts in G bobbin oil { コ ス モ oil Le Block リ カ Application Star (strain) system }, (C1) 50 parts, (D1) 100 parts, (A1) 15 parts and (B1) 70 parts, in addition, obtain defoamer of the present invention (S9) similarly to Example 1.In addition, confirm not have particle more than 5 microns similarly to Example 1.
＜embodiment 10 〉
20 parts of 30 parts of Nipsil SS-10 (C1), ニ ュ one Port one 700 parts of Le LB-625 (D1), 5 parts of ア エ ロ ジ Le 300 (A1) and ion exchange waters (B1) are changed to 35 parts of NipsilSS-50 (C2), ニ ュ one Port one 600 parts of Le GL-3000 (D2), (A1) 15 parts and (B1) 70 parts, append SILWET L-7001{ Japan ュ ニ カ one (strain) system again } (F1) 50 parts, in addition, obtain defoamer of the present invention (S10) similarly to Example 1.In addition, confirm not have particle more than 5 microns similarly to Example 1.
＜embodiment 11 〉
20 parts of 30 parts of Nipsil SS-10 (C1), ニ ュ one Port one 700 parts of Le LB-625 (D1), 5 parts of ア エ ロ ヅ Le 300 (A1) and ion exchange waters (B1) are changed to 35 parts of NipsilSS-50 (C2), ニ ュ one Port one 600 parts of Le GL-3000 (D2), (A1) 15 parts and (B1) 70 parts, append ア Le Off ロ one H-50S{ Japan's grease (strain) system again } (F2) 50 parts, in addition, obtain defoamer of the present invention (S10) similarly to Example 1.In addition, confirm not have particle more than 5 microns similarly to Example 1.
＜comparative example 1 〉
20 parts of 30 parts of Nipsil SS-10 (C1), ニ ュ one Port one 700 parts of Le LB-625 (D1), 5 parts of ア エ ロ ヅ Le 300 (A1) and ion exchange waters (B1) are changed to (C1) 35 parts, (D1) 600 parts, (A1) 0 part and (B1) 70 parts, in addition, obtain the relatively defoamer of usefulness (HS1) similarly to Example 1.In addition, confirm not have particle more than 5 microns similarly to Example 1.
＜comparative example 2 〉
Do not use ニ ュ one Port one Le LB-625 (D1), in addition, obtain the relatively defoamer of usefulness (HS2) similarly to Example 1.In addition, confirm not have particle more than 5 microns similarly to Example 1.
＜comparative example 3 〉
5 parts of ア エ ロ ヅ Le 300 (A1) and ion exchange water (B1) are changed to NipsilE one 75{ Japan's silica (strain) system, specific area 40m for 20 parts 2In addition 3 parts of/g} (A4) and (B1) 70 parts, obtain the relatively defoamer of usefulness (HS3) similarly to Example 1.In addition, confirm not have particle more than 5 microns similarly to Example 1.
＜comparative example 4 〉
5 parts of ア エ ロ ヅ Le 300 (A1) and ion exchange water (B1) are changed to NipgelCX-200{ Japan's silica (strain) system specific area 750m for 20 parts 2In addition 150 parts of/g} (A5) and (B1) 10 parts, obtain the relatively defoamer of usefulness (HS4) similarly to Example 1.In addition, confirm not have particle more than 5 microns similarly to Example 1.
Defoamer S1～S11 and HS1～HS4 for obtaining in embodiment 1～11 and the comparative example 1～4 are shown in its composition in table 3 and the table 4.In addition, goods stability is shown in Table 5.
Should illustrate that the evaluation method of goods stability is, about 110ml defoamer that will place 140ml glass system closed container 40 ℃ place 30 days down after, visualization is estimated according to following metewand.
Well: do not have and separate and gelation
Gelation: do not have flowability, even and then vigorous stirring do not have flowability yet
Separate: liquid-liquid is separated into 2 layers
[table 31]
Trade name Embodiment
??1 ??2 ??3 ??4 ??5 ??6 ??7 ??8 ??9 ??10 ??11
? ??A ??アエロヅル?300 ??アエロヅル?130 ??アエロヅル?380 ??5 ??15 ? ??15 ? ? ??15 ??15 ??15 ??4 ??15 ??15 ??15 ??15
??B Ion exchange water ??20 ??70 ??70 ??70 ??70 ??5 ??70 ??70 ??70 ??70 ??70
??C ? ??Nipsil?SS-10 ??Nipsil?SS-50 ??30 ? ??35 ? ??35 ? ??35 ? ??35 ? ??35 ? ??35 ? ??1 ? ??50 ? ? ??35 ? ??35
? ??D ニ ュ one Port one Le LB-625 ニ ュ one Port one Le PP-3000 ニ ュ one Port one Le GL-3000 ??700 ? ? ? ??600 ? ? ? ??600 ? ? ? ??600 ? ? ? ??600 ? ? ? ? ??600 ? ? ? ??600 ? ? ??600 ? ? ? ??100 ? ? ? ? ? ??600 ? ??600 ? ? ?
??E ? ? E bobbin oil G bobbin oil ??230 ? ? ??230 ? ? ??230 ? ? ??230 ? ? ??0 ? ? ??230 ? ? ??230 ? ? ? ???230 ? ? ??230 ? ??230 ? ? ??230 ? ?
Other compositions SIL WET L-7001 ア Le Off ロ one H-50S ??50 ? ? ? ??50 ? ?
??B/A ??4.0 ??4.7 ??4.7 ??4.7 ??4.7 ??0.3 ??17. ??4.7 ??4.7 ??4.7 ??4.7
[table 4]
Trade name Comparative example
??1 ?2 ?3 ?4
?A アエロヅル?300 Nipsil??E-75 Nipgel?CX-200 ?150 ?3 ?150
?B Ion exchange water ??70 ?70 ?70 ?10
?C Nipsil??SS-10 ??35 ?35 ?30 ?30
?D ニ ュ one Port one Le LB-625 ??600 ?0 ?700 ?700
?E E bobbin oil ??230 ?230 ?230 ?230
?B/A ??- ?0.5 ?23 ?0.07
[table 5]
Goods stability
Embodiment ????1 Well
????2 Well
????3 Well
????4 Well
????5 Well
????6 Well
????7 Well
????8 Well
????9 Well
????10 Well
????11 Well
Comparative example ????1 Separate
????2 Gelation
????3 Separate
????4 Separate
＜evaluation Example 1 〉
Use the defoamer S1～HS4 that obtains in embodiment 1～11 and the comparative example 1～4, as following, prepare emulsion coatings.According to following method, estimate the defoaming of these emulsion coatings and the pearl that contracts, it the results are shown in the table 6.
(1) preparation of emulsion-based coating
Form according to following raw material, use excellent homogenizer automatically that the impeller type blade is installed (Japanese smart device commercial firm system, Model ED), grind and sedimentation, make coating.Detect the decentralization of the coating that obtains similarly to Example 1, affirmation does not have the particle more than 5 microns.
Then, with this aqueous coating dilution,, obtain emulsion-based coating so that the viscosity that stormer viscosity meter (JISK5400-1990) is measured is 77KU (25 ℃).
＜grinding step 〉
8.2 parts in water
SN デ イ ス パ one サ Application 5027; 1.2 parts of サ Application ノ プ コ (strain) system dispersants
SN シ Star Network Na 1; 0.5 part of サ Application ノ プ コ (strain) system tackifier
(25%) 0.2 part of ammonia spirit
3.4 parts of ethylene glycol
イ one ペ one Network R930; 27.8 parts of the former industry of stone (strain) system titanium dioxide
＜sedimentation operation 〉
ボ Application コ one ト EC819; 55.5 parts of big Japanese ink chemical industry (strain) system acrylic emulsions
ノ プ コ サ イ De SN215; 1.0 parts of サ Application ノ プ コ (strain) system anticorrisive agents
テ キ サ ノ one Le; Eastman Chemical makes film and adjusts 2.0 parts of agent
One 636 0.2 parts of SN シ Star Network Na
Add up to 100.0 parts
(2) preparation of emulsion coatings
In emulsion-based coating, add defoamer S1～HS4, so that its concentration becomes 1 weight % (with respect to emulsion-based coating), with the excellent homogenizer automatically that the impeller type blade is installed, under 15～25 ℃, rotating speed with 2000rpm mixed 3 minutes, obtained emulsion coatings 1～17.
In addition, make the coating that does not add defoamer, as emulsion coatings 16.
(3) evaluation of the defoaming and the pearl that contracts
With galvanized iron sheet { thick 0.5mm, be cut into 20 * 30cm size } carry out degreasing with acetone/cloth after, with roll coating emulsion coatings 1～9, so that wet coating thickness becomes 250 μ m, then, in being adjusted to 25 ℃, the operating room of 60% relative humidity, make its dry 1 day, observe film coated surface, according to the following benchmark evaluation defoaming and the pearl that contracts.
In addition, emulsion coatings 1～9 is being left standstill keeping after 1 month (aging back) under 40 ℃, use the excellent homogenizer automatically that the impeller type blade is installed once more under 15～25 ℃, rotating speed with 2000rpm mixed 3 minutes, obtain the aging emulsion coatings of estimating usefulness, similarly estimate defoaming and the pearl that contracts.
＜defoaming 〉
5: have below 2 and steep trace
4: 2～5 bubble traces are arranged
3: 5～10 bubble traces are arranged
2: 10～20 bubble traces are arranged
1: have more than 20 and steep trace
＜pearl contracts 〉
5: contract below 2 pearl or indenture [cratering trace] are arranged
4: 2～5 contract pearl or indentures are arranged
3: 5～10 contract pearl or indentures are arranged
2: 10～20 contract pearl or indentures are arranged
1: contract more than 20 pearl or indenture are arranged
＜evaluation Example 2 〉
Use the defoamer S1～HS6 that obtains in embodiment 1～11 and the comparative example 1～6, as following, prepare the colouring agent for paint that coated paper is used.According to following method, estimate the defoaming of these colouring agent for paint, it the results are shown in the table 6.
(1) preparation of colouring agent for paint base-material
Form according to following raw material, use excellent homogenizer automatically that the impeller type blade is installed (Japanese smart device commercial firm system, Model ED), make the colouring agent for paint base-material.
＜colorant formulations 〉
29.4 parts in water
SN デ イ ス パ one サ Application ト 5040; 0.35 part of サ Application ノ プ コ (strain) system dispersant
(50%) 0.22 part of sodium hydrate aqueous solution
FMT-90; 53.3 parts of (strain) Off ア イ マ テ Star Network system powdered whitings
HT clay: 60.0 parts of secondary clays
20.0 parts of SBR2803F:JSR (strain) system SBR ラ テ Star Network ス
MS4600: 8.6 parts of japanese food processing (strain) oxygenerating starch
Add up to 172.0 parts
(2) evaluation of the defoaming and the pearl that contracts
In the colouring agent for paint base-material, add defoamer so that its concentration becomes 1%, under 15～25 ℃, mixed 10 minutes, obtain colouring agent for paint with the rotating speed of 2000rpm with the excellent homogenizer automatically that the impeller type blade is installed.In addition, except not adding defoamer, similarly obtain blank colouring agent for paint (not adding defoamer) with said method.Then, (metal system specific gravity bottle: method hydrometer jar) is measured the proportion of the colouring agent for paint of these colouring agent for paint after stirring 10 minutes according to JIS K5600-2-4:1999.Proportion is big more, and the bubble that then enters in the coating is few more, and the expression defoaming is good more.
In addition, glass plate { thick 5mm is cut into 20 * 30cm size } carried out degreasing with acetone/cloth after, with spreader coating composition colouring agent,, then, observe film coated surface, according to the following benchmark evaluation pearl that contracts so that wet coating thickness becomes 250 μ m.
＜pearl contracts 〉
5: the pearl that contracts below 2 is arranged
4: 2～5 pearls that contract are arranged
3: 5～10 pearls that contract are arranged
2: 10～20 pearls that contract are arranged
1: the pearl that contracts more than 20 is arranged
[table 6]
Evaluation Example 1 Evaluation Example 2
Defoamer After the preparation After aging Defoaming proportion Pearl contracts
Defoaming Pearl contracts Defoaming Pearl contracts
Embodiment ?1 ????S1 ????5 ???5 ????5 ??5 ?1.332 ??5
?2 ????S2 ????5 ???5 ????5 ??5 ?1.335 ??5
?3 ????S3 ????5 ???5 ????5 ??5 ?1.325 ??5
?4 ????S4 ????5 ???5 ????5 ??5 ?1.343 ??5
?5 ????S5 ????5 ???5 ????5 ??5 ?1.314 ??5
?6 ????S6 ????5 ???5 ????5 ??5 ?1.325 ??5
?7 ????S7 ????5 ???5 ????5 ??5 ?1.337 ??5
?8 ????S8 ????5 ???5 ????5 ??5 ?1.352 ??5
?9 ????S9 ????5 ???5 ????5 ??5 ?1.323 ??5
?10 ????S10 ????5 ???5 ????5 ??5 ?1.368 ??5
?11 ????S11 ????5 ???5 ????5 ??5 ?1.311 ??5
Comparative example ?1 ????HS12 ????5 ???3 ????5 ??2 ?1.261 ??3
?2 ????HS13 ????3 ???4 ????2 ??4 ?1.246 ??4
?3 ????HS14 ????2 ???4 ????1 ??4 ?1.332 ??4
?4 ????HS15 ????3 ???4 ????2 ??4 ?1.203 ??4
Do not add ????2 ???5 ????1 ??5 ?1.135 ??5
Surfactant of the present invention can be used for making whole manufacturing treatment process that the manufacturing treatment process that makes water in a large number of pulp industry, food industry, fiber industry, synthetic resin industry, China Synthetic Rubber Industry, resin emulsion industry, concrete industry, coatings industry, night soil processing, draining processing etc. etc., foaming throw into question.
Need to prove that " above, following " in this specification includes end points.

Claims (4)

1. surfactant, wherein containing the specific area that adopts BET method (JIS R1626-1996) to record is 100～450m 2The hydrophily silica (A) of/g, polyoxyalkylene compounds (D) and hydrophobic silica (C).
2. surfactant according to claim 1, wherein polyoxyalkylene compounds (D) comprises the compound with general formula (1) or (2) expression,
R-(OA)n-OH???????????????????(1)
In the formula, R represents straight chained alkyl or the straight alkenyl or the hydrogen atom of carbon number 1～6, and OA represents the oxyalkylene group of carbon number 3～4, and n represents 10～100 integer, and m represents 0 or 1.
3. surfactant according to claim 1 and 2 wherein also contains water (B), and hydrophily silica (A) is 0.1～20 with the weight ratio (B/A) of water (B).
4. a defoamer wherein contains each described surfactant in the claim 1～3.
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