CN1751768A - Defoamer - Google Patents

Abstract

To provide a defoaming agent causing less cissing. The defoaming agent contains an aluminum carboxylate (A) and hydrocarbon oil (B), but contains no alkaline earth metals, wherein (A) is an aluminum di-carboxylate (A2) or a mixture of an aluminum mono-carboxylate (A1) and an aluminum di-carboxylate (A2), the content, by weight, of (A) is 0.1-60% and the content of (B) is 40-99.9% based on the weight of (A) and (B), and the content of A(1) is <=40% based on the total weight of (A1) and (A2). In addition, the defoaming agent contains free fatty acid (FA) and the content of (FA) is preferably 1-30% based on the weight of (A1) and (A2). In addition, the defoaming agent contains hydrocarbon oil (B) containing aromatic carbon (BA), and the content of (BA) is preferably 1-30% by number based on the total number of carbons of (B).

Description

Defoamer

Technical field

The present invention relates to a kind of defoamer.In more detail, relate to a kind of applicable to pulp industry, food industry, fiber industry, building materials with the manufacturing procedure of plate manufacturing, coatings industry or chemical industry etc. and the defoamer of draining treatment process.

Background technology

As known defoamer, the defoamer (patent documentation 1) that contains polysiloxane one polyether block polymer, water unmixability oil, polypropylene glycol-polyethylene glycol block polymer, emulsifying agent and metallic soap (fatty acid alkali and/or fatty acid aluminium) is arranged.

The defoamer that contains metallic soap in the past is when being used for low viscous coating, and existing films goes up the problem that a lot of depressions occur.

Patent documentation 1: special public clear 63-52927 communique (corresponding to USP4384976)

Summary of the invention

The objective of the invention is to, a kind of less defoamer of appearance of depression is provided.

The inventor concentrates on studies in order to address the above problem, and found that by using specific aluminum carboxylate can reach above-mentioned purpose, thereby has finished the present invention.That is, defoamer of the present invention is characterised in that, is the defoamer that contains aluminum carboxylate (A) and hydrocarbon ils (B) and do not contain carboxy acid alkali's earth metal,

(A) be the mixture of two (carboxylic acid) aluminium (A2) or one (carboxylic acid) aluminium (A1) and two (carboxylic acid) aluminium (A2),

With respect to (A) and weight (B), content (A) is 0.1～60 weight %, and content (B) is 40～99.9 weight %,

(A1) content is below the 40 weight % with respect to (A1) and gross weight (A2).

Depression seldom appears in defoamer of the present invention.And then, have supereminent antifoam performance.Thus, be suitable as pulp industry, food industry, fiber industry, building materials with the defoamer that uses in the manufacturing procedure of plate manufacturing, coatings industry or chemical industry etc. and the draining treatment process.

The specific embodiment

Aluminum carboxylate (A) is made of two (carboxylic acid) aluminium (A2), and perhaps the mixture by one (carboxylic acid) aluminium (A1) and two (carboxylic acid) aluminium (A2) constitutes.

The carbon number that constitutes the carboxylic acid of one (carboxylic acid) aluminium (A1) and two (carboxylic acid) aluminium (A2) is preferably 4～30, and more preferably 8～24, be preferably 14～22 especially.When carbon number during, can further improve antifoam performance in this scope.

As this carboxylic acid, can use in aliphatic carboxylic acid and the ester ring type carboxylic acid etc. any, wait the preferred aliphat carboxylic acid from the viewpoint of defoaming.

As one (carboxylic acid) aluminium (A1), can enumerate one (butyric acid) aluminium, one (sad) aluminium, one (tetradecanoic acid) aluminium, one (pentadecanoic acid) aluminium, one (hexadecanoic acid) aluminium, one (Heptadecanoic acide) aluminium, one (octadecanoid acid) aluminium, one (nonadecylic acid) aluminium, one (arachic acid) aluminium, one (behenic acid) aluminium, one (melissic acid) aluminium, one (tetradecenoic acid) aluminium, one (gaidic acid) aluminium, one (octadecenoic acid) aluminium, one (eicosenoic acid) aluminium, (docosenoic acid) aluminium and one (leukotrienes) aluminium etc.Wherein, wait from the viewpoint of defoaming, preferred one (sad) aluminium, one (tetradecanoic acid) aluminium, one (pentadecanoic acid) aluminium, one (hexadecanoic acid) aluminium, one (Heptadecanoic acide) aluminium, one (octadecanoid acid) aluminium, (nonadecylic acid) aluminium and one (behenic acid) aluminium, further preferred one (sad) aluminium, one (hexadecanoic acid) aluminium, (octadecanoid acid) aluminium and one (behenic acid) aluminium.

As two (carboxylic acid) aluminium (A2), can enumerate two (butyric acid) aluminium, two (sad) aluminium, two (tetradecanoic acid) aluminium, two (pentadecanoic acid) aluminium, two (hexadecanoic acid) aluminium, two (Heptadecanoic acide) aluminium, two (octadecanoid acid) aluminium, two (nonadecylic acid) aluminium, two (arachic acid) aluminium, two (behenic acid) aluminium, two (melissic acid) aluminium, two (gaidic acid) aluminium, two (octadecenoic acid) aluminium and two (linoleic acid) aluminium etc.

Wherein, viewpoint from defoaming, preferred two (sad) aluminium, two (tetradecanoic acid) aluminium, two (pentadecanoic acid) aluminium, two (hexadecanoic acid) aluminium, two (Heptadecanoic acide) aluminium, two (octadecanoid acid) aluminium, two (nonadecylic acid) aluminium and two (behenic acid) aluminium, further preferred two (sad) aluminium, two (hexadecanoic acid) aluminium, two (octadecanoid acid) aluminium and two (behenic acid) aluminium.

These (carboxylic acid) aluminium and/or two (carboxylic acid) aluminium can be two or more mixtures, when it is under the situation of mixture, preferably contain above-mentioned preferred compound as principal component.Wherein, principal component among the present invention is meant the composition that contains 40 weight % with respect to the weight of all the components at least, preferably contains more than the 50 weight %, further preferably contains more than the 60 weight %, especially preferably contain more than the 70 weight %, most preferably contain more than the 80 weight %.

One (carboxylic acid) aluminium (A1) content (weight %) is preferably below 40 with respect to the gross weight of (A1) and two (carboxylic acid) aluminium (A2), and more preferably 0 or 0.1～30, be preferably 0 or 0.1～22 especially, most preferably be 0.If in this scope, can further reduce the generation of depression.

The content (weight %) of aluminum carboxylate (A) is preferably 0.1～60 with respect to the weight of (A) and hydrocarbon ils (B), and more preferably 2～33, be preferably 3～17 especially, most preferably be 4～16.If in this scope, can further improve antifoam performance.

Aluminum carboxylate (A) can pass through known method (for example double decomposition or direct method etc.) and make { fatty acid chemistry＜revised and enlarged edition 〉, in clear and on August 10th, 45, Co., Ltd. issues in the good fortune study }.

Double decomposition is meant with alkali (NaOH) and carboxylic acid is converted to the method that this neutralized salt and aluminium inorganic compound (for example aluminium hydroxide) is reacted after the neutralized salt and make aluminum carboxylate.In addition, direct method is meant the method that carboxylic acid and aluminium inorganic compound are reacted.

In defoamer of the present invention, can further contain free fatty (FA).

As free fatty (FA), can use the compound identical etc. with the carboxylic acid that constitutes aluminum carboxylate (A), preferred compound is also identical.

When containing free fatty (FA), (FA) preferably constitute the carboxylic acid of aluminum carboxylate (A).

Free fatty can be the mixture more than 2 kinds, when it is mixture, preferably contains above-mentioned preferred compound as principal component.

When containing free fatty (FA), with respect to the gross weight of one (carboxylic acid) aluminium (A1) and two (carboxylic acid) aluminium (A2), content (FA) (weight %) is preferably 1～30, and more preferably 2～27, be preferably 3～25 especially.When in this scope, can further improve antifoam performance.

In aluminum carboxylate (A), contain free fatty (FA) usually.Therefore, can from aluminum carboxylate (A), remove free fatty (FA) (cleaning, distillation etc.), to reach above-mentioned content.On the other hand, also can append free fatty (FA), to reach above-mentioned preferable range.

The aluminum carboxylate that contains free fatty (FA) obtains easily from the market, can enumerate the commodity of following table etc.In addition, also can easily obtain aluminum carboxylate from reagent manufacturer etc.

Table 1

Trade name	Content (weight %)			Manufacturer's title
					(A1)	(A2)	(FA)
	SA-1000	20	75					5	Sakai chemical industry (strain)
SA-1500				0	85	15
	SA-2000	0	80				20
Aluminum stearate #300				19	75	6		Japan's grease (strain)
	Aluminum stearate #600	9	81				10
Aluminum stearate				8	72	20			Light southern chemical industry (strain)

Defoamer of the present invention does not contain carboxy acid alkali's earth metal.As carboxy acid alkali's earth metal, be the material that constitutes by carboxylic acid and alkaline-earth metal.This carboxylic acid is identical with the carboxylic acid that constitutes aluminum carboxylate (A).As carboxy acid alkali's earth metal, can enumerate two (octadecanoid acid) magnesium and one (octadecanoid acid) calcium etc.When containing carboxy acid alkali's earth metal, depression appears easily.

As hydrocarbon ils (B), can use 250～415 ℃ cut in the crude oil is carried out hydrogenation and the mineral wet goods that obtains.

In hydrocarbon ils (B), preferably contain aromatic series carbon (aromatic carbon) (BA).When containing aromatic series carbon (BA), with respect to the total carbon atom number of hydrocarbon ils (B), content (BA) (number %) is preferably 1～30, and more preferably 2～20, be preferably 4～15 especially, most preferably be 6～12.If in this scope, antifoam performance and product stability (gelation, separate etc.) are better.

When in hydrocarbon ils (B), containing naphthenic carbon (naphthenic carbon) (BB) time, with respect to the total carbon atom number of hydrocarbon ils (B), content (BB) (number %) is preferably 15～40, and more preferably 18～36, be preferably 20～34 especially, most preferably be 22～32.If in this scope, defoaming is better.

When in hydrocarbon ils (B), containing paraffinic carbon (paraffinic carbon) (BC) time, with respect to the total carbon atom number of hydrocarbon ils (B), content (BC) (number %) is preferably 50～80, and more preferably 54～74, be preferably 56～72 especially, most preferably be 58～70.If in this scope, defoaming is better.

Wherein, the content of aromatic series carbon (BA), naphthenic carbon (BB) and paraffinic carbon (BC) is that benchmark is measured with ring analysis (n-d-M) method { ASTM D3238-74 (Reapproved 1979) }.

Kinematic viscosity (the mm of hydrocarbon ils (B) ²/ s; 40 ℃), be preferably 4～146, further preferred 4～30, be preferably 10～28 especially, most preferably be 15～25.If in this scope, antifoam performance and product stability are better.

As hydrocarbon ils (B), obtain from market easily, can enumerate the commodity represented by following table etc.In the middle of them, wait from the viewpoint of antifoam performance and product stability, preferred COSMOPURESPIN (コ ス モ ピ ュ ア ス ピ Application) G, COSMO PURESPIN E, COSMOSP10, Stanol (ス ノ one Le) 35, Stanol LP35, Off Star コ one Le ST マ シ Application, COSMO NEUTRAL (コ ス モ ニ ュ one ト ラ Le) 150, day stone Super Oil (ス one パ one オ イ Le) D and day stone Super Oil B, further preferred COSMO PURESPIN G and COSMO PURESPIN E.These hydrocarbon ils (B) can be the mixtures more than 2 kinds.

Table 2

The trade name of hydrocarbon ils	Content (eight number %)			Kinematic viscosity (mm 2/g) 40℃	Manufacturer's title
						(BA)	(BB)	(BC)
	COSMO SC22	2.5	30						67.5	21	コ ス モ oil Le ヅ リ カ Application Star (strain)
COSMO SP10				2.5	30.8	66.7	10
	COSMO RC bobbin oil	2.5	30.8					66.7	10
COSMO RB bobbin oil				3.1	26.7	70.2	15
	COSMO NEUTRAL 150	6.9	26.6					66.5	32
COSMO PURESPIN G				9.7	30.6	59.7	21
	COSMO PURESPIN E	9.7	23.0					67.3	5
Day stone Super Oil C				5.5	29	65.5	93			Japan petroleum chemistry (strain)
	Day stone Super Oil D	6	27.5					66.5	141
Day stone Super Oil B				7.0	28.0	65.0	54
	Stanol 43N	4	28					68	27		エ Star ソ oil (strain)
Stanol 52				4	27	69	56
	Stanol 69	5	27					68	145
Stanol 35				7	27	66	9
	Stanol LP35	7	30					65	11
Off Star コ one Le SH SPIN				4	27	69	9			The emerging product of Fuji (strain)
	Off Star コ one Le NT100S	4	27					69	2
Off ッ コ one Le NT100				4.5	25.5	70	21
	Off Star コ one Le NT150	4.5	26					69.5	28
Off Star コ one Le NT200				4.5	26	69.5	39
	Off Star コ one Le NT60	5.5	28.5					66	10
Off Star コ one Le ST マ シ Application				6	31	63	9
	J.S.Oアロマ790	37	28					35	16		Japan's サ Application oil (strain)

Wherein, as hydrocarbon ils (B), also can use vegetable and animals oils and above-mentioned hydrocarbon ils and mixture of vegetable and animals oils etc.

As vegetable and animals oils, crude vegetal, natural animal oil and their modification wet goods can be used, butter, lard, whale oil, fish oil, rapeseed oil, soybean oil, sunflower seeds oil, cottonseed oil, peanut oil, rice bran oil, corn oil, safflower oil, olive oil, sesame oil, evening primrose oil, palm oil, coconut oil, palm kernel oil etc. and their hydrogenation wet goods can be enumerated.

With respect to the weight of aluminum carboxylate (A) and hydrocarbon ils (B), the content (weight %) of hydrocarbon ils (B) is preferably 40～99.8, and more preferably 67～98, be preferably 83～97 especially, most preferably be 84～96.If in this scope, defoaming is better.

The polyoxyalkylene compounds (C) that in defoamer of the present invention, preferably further contains useful general formula (1) expression.

As polyoxyalkylene compounds (C),, then can use ad lib so long as contain the compound of polyoxyalkylenes.

As polyoxyalkylenes, comprising by a plurality of carbon numbers is the group that 3～4 alkylene oxide group (inferior ethoxyl, inferior propoxyl group and inferior butoxy) has formed chemical bond.In polyoxyalkylenes, can constitute by a kind of alkylene oxide group, can also be by constituting more than 2 kinds.When constituting more than 2 kinds, combining form can be block, random and mix in any.

Also can replace polyoxyalkylene compounds (C) with general formula (1) expression, perhaps on this basis, use the public clear 50-5157 communique of spy, special public clear 49-38923 communique, special public clear 50-1475 communique, special public clear 45-7973 communique, spy and open clear 50-4282 communique or specially open the polyoxyalkylene compounds described in each communique such as flat 2-289526 communique; And their mixture etc.

But, the polyoxyalkylene compounds (C) that preferably contains useful general formula (1) expression at least.

[changing 1]

R ¹{-(OA) ⁿ-OR ²} _m (1)

Wherein, in general formula (1), R ¹Expression hydrogen atom or carbon number are 2～22 organic group, R ²Expression hydrogen atom or carbon number are 8～31 acyl group, and OA represents that carbon number is 3～4 alkylene oxide group, and m represents 1～3 integer, and n represents 10～60 integer.

As carbon number is 2～22 organic group, comprises straight chained alkyl, straight-chain alkenyl and acyl group etc.

As straight chained alkyl, can enumerate ethyl, n-pro-pyl, normal-butyl, n-pentyl and base, octyl group, lauryl, myristyl, stearyl (stearyl) and Shan Yu base etc. just.

As straight-chain alkenyl, can enumerate vinyl, 1-acrylic, 2-acrylic, 3-cyclobutenyl, 2-cyclobutenyl, 4-pentenyl, 5-hexenyl, 1-hexenyl, octenyl, decene base, oleyl, vaccenic acid base and eicosylene base etc.

As acyl group, can enumerate caproyl, lauroyl, myristoyl, stearyl (stearoyl), Shan Yu acyl group, tetracosa carbon acyl group, 26 carbonic acyl radicals and oleoyl etc.

At these R ¹In the middle of, wait preferred hydrogen atom, straight chained alkyl and straight-chain alkenyl, further preferred hydrogen atom and straight chained alkyl from the viewpoint of defoaming and depression, preferred especially n-pro-pyl, normal-butyl, n-pentyl and n-hexyl, most preferably normal-butyl, n-pentyl and n-hexyl.

As carbon number is 8～31 acyl group, can enumerate caproyl, lauroyl, myristoyl, stearyl, Shan Yu acyl group, tetracosa carbon acyl group, 26 carbonic acyl radicals and oleoyl.

At these R ²In the middle of, wait preferred hydrogen atom, lauroyl, myristoyl, oleoyl and stearyl, further preferred hydrogen atom, lauroyl, oleoyl and stearyl, preferred especially hydrogen atom from the viewpoint of defoaming and depression.

As carbon number is 3～4 alkylene oxide group, comprises inferior propoxyl group, inferior butoxy and their mixture.Wherein, preferred inferior propoxyl group.

Also have, as alkylene oxide group, wherein containing carbon number as main body is that 3～4 alkylene oxide group gets final product, and also can contain inferior ethoxyl in the part.Main body is meant that the molal quantity with respect to the component unit of alkylene oxide group contains at least 70 moles of %, preferably contains 75 moles more than the %, further preferably contains 80 moles more than the %, especially preferably contains 85 moles more than the %, most preferably contains 90 moles more than the %.

When containing multiple alkylene oxide group, can be in the middle of block-wise, random shape and their mixing any, preferred random shape.

As n, be preferably 10～60 integer, more preferably 20～50 integer is preferably 25～45 integer especially.If in this scope, can further suppress the generation of caving in.

As polyoxyalkylene compounds, can enumerate with the compound of following chemical formulation etc. with general formula (1) expression.Wherein, po represents inferior propoxyl group, and bo represents inferior butoxy, the expression block-wise ,/represent random shape.

[changing 2]

C ₂H ₅-(po) ₂₅-OH (2)

C ₂H ₅-(po) ₄₅-OH (3)

C ₂H ₅-(po) ₃₀·(bo) ₂-OH (4)

C ₃H ₇-(po) ₂₅-OH (5)

C ₃H ₇-(po) ₄₅-OH (6)

C ₃H ₇-(po) ₃₀·(bo) ₂-OH (7)

C ₄H ₉-(po) ₂₅-OH (8)

C ₄H ₉-(po) ₄₅-OH (9)

C ₄H ₉-(po) ₃₀·(bo) ₂-OH (10)

C ₄H ₉-(po) ₃₀/bo ₅)-OH (11)

C ₅H ₁₁-(po) ₂₅-OH (12)

C ₅H ₁₁-(po) ₄₅-OH (13)

C ₅H ₁₁-(po) ₃₀·(bo) ₂-OH (14)

C ₆H ₁₃-(po) ₂₅-OH (15)

C ₆H ₁₃-(po) ₄₅-OH (16)

C ₆H ₁₃-(po) ₃₀·(bo) ₂-OH (17)

C ₃H ₇-(po) ₁₀-OCO-C ₁₂H ₂₃ (18)

C ₃H ₇-(po) ₁₅-OCO-C ₁₂H ₂₃ (19)

C ₃H ₇-(po) ₁₅-OCO-C ₁₇H ₃₃ (20)

C ₄H ₉-(po) ₃₀/eo ₅)-OH (21)

C ₆H ₁₃-(po) ₃₀/eo ₂)-OH (22)

Wherein, preferably use the polyoxyalkylene compounds of formula (6), (9), (13), (14), (15), (19) or (20) expression, further preferred polyoxyalkylene compounds with formula (6), (9), (14) or (20) expression.These polyoxyalkylene compounds (C) can be the mixtures more than 2 kinds, when it is mixture, preferably contain above-mentioned preferred compound as principal component.

Polyoxyalkylene compounds (C) can obtain by known method, for example, making carbon number is that 2～22 straight chain alkanol or straight chain enol and carbon number are the method that 3～4 alkylene oxide reacts, in addition, making carbon number is that 2～22 straight chain alkanol or straight chain enol and carbon number are after 3～4 alkylene oxide reacts, make this product and carbon number be 2～22 or carbon number be method of reacting of 8～31 aliphatic acid etc.

Polyoxyalkylene compounds (C) with general formula (1) expression, obtain from market easily, the commodity in use name can be exemplified as ニ ュ one Port one Le LB-385, LB-625, LB-1145, LB-1715 and LB-1800X{ Sanyo and change into industry (strain) system }, and ュ ニ Le one Block MB-19, MB-38 and MB-370{ Japan's grease (strain) system etc.

When containing polyoxyalkylene compounds (C), with respect to the weight of aluminum carboxylate (A), its content (weight %) is preferably 3～70000, and more preferably 20～400, be preferably 90～300 especially.If in this scope, can further reduce depression.

In defoamer of the present invention, can further contain silica (D).

Silica (D) can use known inorganic powder silica and inorganic powder silica has been implemented hydrophobic silica that hydrophobization handles etc.

Wherein, from the viewpoint of defoaming etc., preferred hydrophobic silica.

As inorganic powder silica, contain following severally, can be the silica made from any method.(1) damp process silica: the inorganic silicon dioxide aeroge is (with having the boiling point below 70 ℃ and with glassware for drinking water blended solvent (methyl alcohol being arranged, acetone, methyl formate, methyl acetate etc.) moisture in the silica hydrogel is replaced after, heating is removed this solvent and the colloidal silica that obtains), (2) thermal decomposition method silica: fumed silica (by through the calcining of silicon tetrachloride and the colloidal silica that the silica coal that generates constitutes), (3) molten solids method silica: settleability silica is (by dripping sodium chloride in sodium silicate aqueous solution, sodium ions such as sodium sulphate carry out aggegation and the silicon dioxide granule that obtains) etc.Wherein, the viewpoint from defoaming waits preferred fumed silica and settleability silica, further preferred settleability silica.

Trade name as inorganic powder silica can be enumerated NIPGEL AY-200, AY-401, AY-601, AZ-200, AZ-400, BY-200, BZ-200, CX-200, Nipsil L-250, E-200A, E-220, G-300, N-300A (Japanese シ リ カ Co., Ltd.); FINESIL E70, T32, K41, F80 (ト of Co., Ltd. Network セ マ); SYLYSIA 250N, 310P, 350,420 (シ リ シ ア KCCs of Fuji); AEROSIL 130,200,300,380, OX50 (Japanese ア エ ロ ジ Le Co., Ltd.); L-90, LM-150, MS-55, EH-5, M-7D (キ ヤ ボ Star ト カ one ボ Application company); And AEROSIL OX50, MOX80 (デ ゲ サ ジ セ パ Application Co., Ltd.) etc.These inorganic powder silica can be the mixtures more than 2 kinds.

Also have, hydrophobic silica can easily obtain by with hydrophobizers above-mentioned inorganic powder silica being carried out heat treated.

As hydrophobizers, can contain silicone oil and modified silicon oil etc.As silicone oil, can enumerate kinematic viscosity is 10～3000 (mm ²/ s, 25 ℃) dimethyl siloxane etc., also contain ring four dimethyl siloxanes etc.

As modified silicon oil, can contain useful carbon number and be 2～6 alkyl, carbon number and be 2～4 alkoxyl, phenyl, hydrogen atom, halogen (chlorine and bromine etc.) atom and/or carbon number and be 2～6 aminoalkyl etc. and the part of the methyl of above-mentioned dimethyl siloxane carried out the material that replaces etc.

Content (weight %) as hydrophobizers with respect to the weight of hydrophobic silica, is preferably 5～70, and more preferably 7～50, be preferably 10～30 especially.If in this scope, then defoaming is outstanding.

Heating-up temperature in handling as hydrophobization (℃), be preferably 100～400, more preferably 150～350, be preferably 200～300 especially.

In hydrophobization is handled, can use solvent { hydrocarbon ils (B), kinematic viscosity (mm ²/ s, 40 ℃) be the paraffin oil of 5-30 and processing oil (process oil) etc. and catalysts (sulfuric acid, nitric acid, hydrochloric acid, hydroxacetic acid, trifluoracetic acid, paranitrobenzoic acid, potassium hydroxide, lithium hydroxide etc.) etc.

Trade name as hydrophobic silica can be enumerated Nipsil SS-10, SS-40, SS-50 and SS-115 (Japanese シ リ カ Co., Ltd.); AEROSIL R972, RX200 and RY200 (Japanese ア エ ロ ジ Le Co., Ltd.); TS-530, TS-610, TS-720 (キ セ ボ Star ト カ one ボ Application company); AEROSIL R202, R805, R812 (デ ゲ サ ジ セ パ Application Co., Ltd.); REOLOSIL MT-10, DM-10 and DM-20S (ト of Co., Ltd. Network セ マ); And SYLOPHOBIC 100,702,505 and 603 (シ リ シ ア KCC of Fuji) etc.These hydrophobic silicas can be the mixtures more than 2 kinds.

When containing silica (D), with respect to the weight of aluminum carboxylate, its content (weight %) is preferably 0.1～100, and more preferably 1～50, be preferably 2～30 especially.If in this scope, defoaming is better.

In this defoamer, except containing aluminum carboxylate (A), hydrocarbon ils (B), polyoxyalkylene compounds (C) and silica (D), can also contain other compositions { native paraffin, carbon number are that 12～30 alcohol, carbon number are that 12～30 carboxylate, carbon number are 8～30 fatty acid amide and/or silicone oil etc. }.And then, (new surface active agents is crossed the threshold, Sanyo changes into clear and the 2nd printing of distribution in 60 years of industry (strain) can also to contain known surfactant, 63～81 pages etc.), thickener, anticorrisive agent (fungi-proofing mould inhibitor dictionary, clear and the 1st edition distribution in 61 years of the fungi-proofing mildew-resistant association of Japan, 1～32 page etc.) and/or solvent (solvent handbook, clear and the distribution in 51 years of talk society, 143-881 page or leaf etc.).

As native paraffin, can enumerate candelila wax, Brazil wax, rice wax, haze tallow, ホ ホ バ oil, montan wax, beeswax and lanolin (lanolin) etc.These native paraffins can be the mixtures more than 2 kinds, when it is mixture, as principal component preferably contain Brazil wax, montan wax and/lanolin.

When containing native paraffin, with respect to the weight of aluminum carboxylate (A), its content (weight %) is preferably 0.1～30, and is further preferred 0.3～20, is preferably 0.5～10 especially.If in this scope, defoaming is better.

As synthetic wax, can enumerate microwax, vaseline (petrolatum), Tissuemat E and f-t synthetic wax etc.These synthetic waxs can be the mixtures more than 2 kinds, when it is mixture, preferably contain microwax as principal component to examine/or Tissuemat E.

When containing synthetic wax, with respect to the weight of aluminum carboxylate (A), its content (weight %) is preferably 0.01～300, and is further preferred 0.3～250, is preferably 5～200 especially.If in this scope, defoaming is better.

As alcohol, can use natural alcohol (laruyl alcohol, myristyl alcohol, cetanol, stearyl alcohol, eicosanol, tadenan, tetracosanol, hexacosanol, n-octacosanol, triacontanol and oleyl alcohol etc.) and synthol (saturated alcohols by the synthetic non-branch-like of straight chain of ziegler process, by the synthetic straight chain primary alcohol of oxidizing process or branched-chain primary alcohol, alkane is carried out air oxidation and synthetic linear secondary etc.).These alcohol can be the mixtures more than 2 kinds, when it is mixture, preferably contain laruyl alcohol, stearyl alcohol nuclear/or oleyl alcohol as principal component.

When containing alcohol, with respect to the weight of aluminum carboxylate (A), its content (weight %) is preferably 0.1～300, and is further preferred 0.3～200, is preferably 5～180 especially.If in this scope, defoaming is better.

It as carbon number 12～30 carboxylate, can use carbon number is that 1～30 the pure and mild carbon number of 1～6 valency is the fatty acid ester of 12～30 carboxylic acid, can enumerate stearic acid palm ester, stearic acid stearyl ester, oleic acid stearyl ester, oleyl oleate and stearic acid grease etc.These carboxylates of 12～30 can be the mixtures more than 2 kinds, when it is mixture, preferably contain stearic acid palm ester, stearic acid stearyl ester, oleic acid stearyl ester, oleyl oleate and/or stearic acid grease as principal component.

When to contain carbon number be 12～30 carboxylate, with respect to the weight of aluminum carboxylate (A), its content (weight %) was preferably 0.1～300, and is further preferred 0.3～200, is preferably 0.5～160 especially.If in this scope, defoaming is better.

As carbon number is 8～30 fatty acid amide, can enumerate ethene for bis-stearamides, ethene for two palmitamides, ethene for bimonthly osmanthus acid amides, butylene for bis-stearamides and butylene for two palmitamides etc.These fatty acid amides can be the mixtures more than 2 kinds, when it is mixture, preferably contains ethene and replace bis-stearamides as principal component.

When to contain carbon number be 8～30 fatty acid amide, with respect to the weight of aluminum carboxylate (A), its content (weight %) was preferably 0.1～400, and is further preferred 0.3～200, is preferably 5～160 especially.If in this scope, defoaming is better.

As silicone oil, can use dimethyl polysiloxane, polyether modified silicone, alkyl-modified silicone and above-mentioned silicone oil (hydrophobizers) etc.These silicone oil can be the mixtures more than 2 kinds, when it is mixture, preferably contain dimethyl polysiloxane and/or polyether modified silicone as principal component.

When containing silicone oil, with respect to the weight of aluminum carboxylate (A), its content (weight %) is preferably 0.1～300, and is further preferred 0.3～200, is preferably 5～100 especially.If in this scope, defoaming is better.

As known surfactant, can use nonionic surfactant, anionic surfactant, cationic surfactant and amphoteric surfactant.

When containing known surfactant, with respect to the weight of aluminum carboxylate (A), its content (weight %) is preferably 0.01～200, and is further preferred 0.1～100, is preferably 0.3～50 especially.If in this scope, product stability (separation) is better.

As thickener, can enumerate organically-modified montmorillenite, organically-modified saponite, organically-modified hectorite, organically-modified sodium silicon mica sodium, organically-modified lithium taincolite, rock, hydroxy stearic acid, polyisobutene, polyalkyl methacrylate and ethylene-propylene copolymer etc. take off in organically-modified class.These thickeners can be the mixtures more than 2 kinds, when it is mixture, preferably contain polyalkyl methacrylate, ethylene-propylene copolymer as principal component.

When containing thickener, with respect to the weight of aluminum carboxylate (A), its content (weight %) is preferably 0.01～200, and is further preferred 0.1～100, is preferably 0.3～50 especially.If in this scope, product stability (separation) is better.

As anticorrisive agent, can enumerate 2-bromo-2-nitro-1, ammediol (BNP), 5-chloro-2-methyl-4-isothiazoline-3-ketone (MIT), 1,2-[4-morpholinodithio quinoline-3-ketone and 2-methyl-4-isothiazoline-3-ketone etc.

When containing anticorrisive agent, with respect to the weight of aluminum carboxylate (A), its content (weight %) is preferably 0.001～5, and is further preferred 0.01～3, is preferably 0.1～2 especially.If in this scope, product stability is better.

As solvent, can use ethylene glycol monobutyl ether, propylene glycol monobutyl ether and water.

When containing solvent, with respect to the weight of aluminum carboxylate (A), its content (weight %) is preferably 0.1～300, and is further preferred 0.3～200, is preferably 0.5～100 especially.If in this scope, product stability and defoaming are better.

Defoamer of the present invention can pass through aluminum carboxylate (A), hydrocarbon ils (B) and the polyoxyalkylene compounds (C) with general formula (1) expression that adds as required, silica (D), other compositions, known surfactant, thickener, anticorrisive agent and/or solvent are heated and the acquisition of mixed uniformly method.

As the heating mixing temperature (℃), preferably make the temperature of aluminum carboxylate fusion or dissolving, for example preferred 80～190, further preferred 100～180, preferred especially 130～170, most preferably 140～160.

As heating and mixing device, so long as can be heated to above-mentioned temperature and can mixed uniformlyly install, just be not particularly limited, can enumerate propeller-type mixer, dissolvers, homo-mixer, ball mill, sand mill, ultrasonic dispersing machine, kneader and line mixer etc.Wherein, these devices can be used in combination.

After heating mixes, preferably adjust the particle diameter of aluminum carboxylate (A).As the method for adjustment of particle diameter, can be applied in and carry out stirring method etc. under 5～40 ℃, in the device that heating mixes, can directly be cooled to 5～40 ℃.

The viscosity of defoamer of the present invention (mPas/25) is preferably 30～2000, and more preferably 50～1000, be preferably 70～500 especially.If in this scope, defoaming is better.Wherein, viscosity is that 4.2 single cylinder rotation viscometer methods (corresponding with ISO2555) with JIS K7233-1986 are that benchmark is measured.

Defoamer of the present invention can be by disposable additive process, continuously adding method, interrupted adding method or the method etc. that connects bubble measuring appliance and defoamer adding set are added to and be added liquid second month in a season.In addition, can adopt a place to add and the many places interpolation in any.In addition, can dilute with suitable dilution solvent or water etc. during interpolation.

Defoamer of the present invention can with known defoamer { for example, polyether antifoam agent, silicone defoamer (special public clear 51-35556 number, the spy opens clear 52-2887 number, special public clear 52-19836 number, special public clear 55-23084 number, Te Kaiping 6-142410 number, and the spy opens flat 6-142411 number each communique etc.), mineral oil antifoam agent (special public clear 49-109276 number, the spy opens clear 52-22356 number, the spy opens clear 54-32187 number, the spy opens clear 55-70308 number and the spy opens clear 56-136610 number each communique etc.) and the wax emulsion defoamer (spy opens clear 47-114336 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. and use.

The addition of defoamer of the present invention (weight %) can suitably be set according to the foamed state that is added liquid, temperature, viscosity etc., with respect to the weight that is added liquid, preferred 0.0001～10, further preferred 0.0005～8, preferred especially 0.001～5, most preferably 0.005～3.Add temperature and be preferably about 0～100 ℃, further preferred 10～60 ℃, preferred especially 20～50 ℃.

[embodiment]

Below, describing the present invention in detail by embodiment, the present invention is not limited to following embodiment.Wherein, short of special record, part is meant that weight portion, % are meant weight %.

＜Production Example 1 〉

In possessing the stainless steel reaction container of thermometer, mixer and reflux, put into 100 parts of ion exchange waters, 50% 50 parts of sodium hydrate aqueous solutions and surfactant { Na ロ ア Network テ イ HN-80, Sanyo changes into industry (strain) } 10 parts, under agitation be heated to 70 ℃.Then, put into sad 90 parts, stirred 1 hour down at 70 ℃ while stir.Then, put into 57.1 parts in aluminium hydroxide with 1 hour time down, and then stirred 1 hour down at 70 ℃ at 70 ℃.Then, the mixture that obtains is cooled to 30 ℃ with 1 hour time, filters, wash, obtain aluminium octoate (a4).

The content of one (sad) aluminium (a41) is 39% with respect to the gross weight of (a41) and two (sad) aluminium (a42).In addition, the content of free sad (fal) is 5% with respect to (a41) and gross weight (a42).About aluminium octoate (a4), carried out near DSC (differential scanning formula calorimeter: Differential Scanning Calorimetry) analyze, confirm that not observing endothermic peak 85 ℃ (fusing points of three (sad) aluminium) { does not contain three (sad) aluminium } (a4).

In addition, the content (weight %) of one (carboxylic acid) aluminium (A1) { one (sad) aluminium (a41) }, two (carboxylic acid) aluminium (A2) { two (sad) aluminium (a42) } and free fatty (FA) { free sad (fa1) } can obtain by method as follows.

(1) free fatty (FA) is quantitative

In the conical flask of 100cc, accurately take by weighing 1g and measure sample, put into the isopropyl alcohol 50g of the superfine level of reagent, after fully stirring 10 minutes under 70 ℃, use the acetone of superfine grade of reagent accurately to be adjusted to 100cc with volumetric flask.Subsequently, filter with No.5C filter paper (ADVANTEC corporate system), its filtrate is for analyzing in gas chromatography (GC).

(2) fatty acid total amount is quantitative

In the conical flask of 100cc, accurately take by weighing 5g and measure sample, put into ion exchange water 1ml and concentrated hydrochloric acid 1ml, under 90 ℃, make its reaction 10 minutes.Subsequently, use the acetone of the superfine level of reagent accurately to be adjusted to 100cc with volumetric flask.After leaving standstill 2 hours, supernatant is supplied to analyze in gas chromatography (GC).

＜GC measuring condition 〉

Device: GC-14B (Shimadzu Seisakusho Ltd.'s system)

Post: DB-FFAP capillary column (Agilent Technologies 30m)

Injection temperature: 250 ℃

Detector temperature: 250 ℃

Column temperature: 100 ℃ of initial stages, 10 ℃/minute of temperature rising speed,

Final 250 ℃ (30 minutes retention times)

Carrier flow velocity: helium 1.0ml/ minute, separate (split) than 1/20

Make-up gas: nitrogen 40ml/ minute

Injection rate: 1ml

(3) the aluminium atom is quantitative

In the conical flask of 100ml, accurately take by weighing 2.000g and measure sample, add nitric acid 15ml, ether 10ml, water 30ml, after fully stirring, use separatory funnel to carry out the ether extraction.Separate ether layer and water layer, add nitric acid 20ml once more in the ether layer, water layer (so repeatable operation is 3 times) is collected in fully vibration.Boil the water layer 10 minutes of collection, put into after the cooling in the 250ml volumetric flask, add water and make it become 250ml, do not have measuring pipette with 50ml and take out 50ml, be put in the 200ml beaker, with the ammonium acetate aqueous solution of 20 weight % neutralize (using indicator B.P.B Huang → indigo plant).And then making its pH with acetic acid (with the pure pharmaceutical worker's industry of light (strain) superfine) is 3～3.5 (Huang → indigo plants), adds Cu-PAN indicator 1ml then, is heated to 100 ℃, at once with the titration of 1/100mol/1-EDTA solution.If color becomes orange colour, be heated to 100 ℃ once more, titration continues 1 minute up to orange colour repeatedly under 100 ℃, calculates aluminium atom content (weight %) by following formula.

The use amount (ml) * 0.02698 * 5/2.000 of X (weight %)=EDTA solution

(4) calculate

From the total content of aliphatic acid, deduct the content of free fatty (FA), obtain the content (GCC) of the carboxylic acid that contains in the aluminum carboxylate (A), then, use and be somebody's turn to do (GCC), aluminium atom content (GA), the atomic weight 27 of aluminium atom and the molecular weight (M) of carboxylic acid, calculate the content (GA1) of one (carboxylic acid) aluminium (A1) and the content (GA2) of two (carboxylic acid) aluminium (A2) by following formula.

Several 1

(GA2)＝{2×(M)+27-2+17}×{(GCC)/(M)-(GA)/27}

(GA1)＝{(M)+27-1+17×2}×{2×(GA)/27-(GCC)/(M)}

About Production Example 1, concrete computational methods are as follows.

Because the content of free fatty (fa1) is 5g, sad total content is 81.6g, and the aluminium atom content is 9.6g, so

The content of two (sad) aluminium (a42) is 330 * (76.6/144-9.6/27)=58.2g,

The content of one (sad) aluminium (a41) is 204 * (2 * 9.6/27-76.6/144)=36.6g.

Content with respect to (a41) of (a41) and gross weight (a42) is 39%, in addition, is 5% with respect to the content of the free fatty (fa1) of (a41) and gross weight (a42).

The measuring condition of dsc analysis is as follows.

Device name: DSC 6200 (セ イ コ one イ Application ス Star Le メ Application Star corporate system)

Beginning temperature: 20 ℃

Limit temperature: 200 ℃

Programming rate: 5 ℃/minute

Retention time under 200 ℃: 10 minutes

Sample size: 10mg

Sample container: simple and easy sealed aluminum container made

Environment: air

＜Production Example 2 〉

In possessing the stainless steel reaction container of thermometer, mixer and reflux, put into 100 parts of ion exchange waters, 50% 25 parts of sodium hydrate aqueous solutions and surfactant { Na ロ ア Network テ イ HN-80, Sanyo changes into industry (strain) } 10 parts, under agitation be heated to 70 ℃.Then, put into 90 parts of behenic acids, stirred 1 hour down at 70 ℃ while stir.Then, put into 39.4 parts in aluminium hydroxide with 1 hour time down, and then stirred 1 hour down at 70 ℃ at 70 ℃.Then, the mixture that obtains is cooled to 30 ℃ with 1 hour time, filters, wash, obtain behenic acid aluminium (a5).

Wherein, the content of one (behenic acid) aluminium (a5) is 11% with respect to the gross weight of (a51) and two (behenic acid) aluminium (a42).In addition, the content of free behenic acid (fa2) is 11% with respect to (a51) and gross weight (a52).

In addition, (a5) carried out dsc analysis for behenic acid aluminium, confirms that not observing endothermic peak near 110 ℃ (fusing points of three (behenic acid) aluminium) { does not contain three (behenic acid) aluminium } (a5).

＜embodiment 1 〉

In possessing the stainless steel reaction container of thermometer, mixer, put into 786 parts of hydrocarbon ils (b1) { by COSMO PURESPIN G＜COSMO oil (strain)〉715 parts and JSO ア ロ マ 790＜Japanese サ Application oil (strain)〉the mixing hydrocarbon ils of 71 parts of formations }, then, put into 44 parts of aluminum carboxylates (a1) { SA-1000, Sakai chemical industry (strain) } while stirring.The mixture that obtains is heated to 135 ℃, put into 70 parts of 100 parts of polyoxyalkylene compounds { ニ ュ one Port one Le LB-385 (c1), Sanyo change into industry (strain) } and native paraffins { Licowax S (e1), Network ラ リ ア Application ト (strain) montan wax } then, stirred 1 hour down at 135 ℃.Then, the mixture that obtains is cooled to 20 ℃ with 1 hour time, obtains defoamer of the present invention (S1).Then, by decentralization test { JISK5600-2-5:1999 (corresponding with ISO 1524:1983): following identical }, affirmation does not have the particle more than the 5 μ m in this (S1).

＜embodiment 2 〉

With 786 parts of hydrocarbon ils (b1), 44 parts of aluminum carboxylates (a1), 100 parts of polyoxyalkylene compounds (c1), 70 parts of native paraffins { Licowax S (e1) }, be modified to 786 parts of hydrocarbon ils (b2) { by COSMOSP10＜COSMO oil (strain)〉511 parts and COSMO PURESPIN G＜COSMO oil (strain)〉the mixing hydrocarbon ils of 275 parts of formations }, aluminum carboxylate (a2) { SA-1500, Sakai chemical industry (strain) } 44 parts, 100 parts of polyoxyalkylene compounds (c1), synthetic wax { FT-100 (e2), Japan's smart wax (strain) synthetic wax } 7 parts, in addition, obtain defoamer of the present invention (S2) in the same manner with embodiment 1.Also have, confirmed not have particle more than 5 microns by the decentralization test in the same manner with embodiment 1.

＜embodiment 3 〉

With 786 parts of hydrocarbon ils (b1), 44 parts of aluminum carboxylates (a1), 100 parts of polyoxyalkylene compounds (c1), 70 parts of native paraffins { Licowax S (e1) }, be modified to 786 parts of hydrocarbon ils (b3) { by 259 parts of COSMOPURESPIN G and 527 parts of mixing hydrocarbon ils that JSO ア ロ マ 790 constitutes }, aluminum carboxylate (a3) { SA-2000, Sakai chemical industry (strain) } 44 parts, 0 part of polyoxyalkylene compounds (c1), 70 parts of alcohol { カ Le コ one Le 18, flower king's (strain) stearyl alcohol (e3) }, in addition, obtain defoamer of the present invention (S3) in the same manner with embodiment 1.Also have with embodiment 1 and confirmed not have particle more than 5 microns by the decentralization test in the same manner.

＜embodiment 4 〉

With 44 parts of aluminum carboxylates (a1), 100 parts of polyoxyalkylene compounds (c1), 70 parts of native paraffins { LicowaxS (e1) }, be modified to 44 parts of aluminium octoates (a4) in Production Example 1, obtaining, 70 parts of polyoxyalkylene compounds (c1), (e4) 70 parts of synthetic waxs { エ キ セ パ one Le OL-OL, flower king (strain) system oleyl oleate }, in addition, obtain defoamer of the present invention (S4) in the same manner with embodiment 1.Also have, confirmed not have particle more than 5 microns by the decentralization test in the same manner with embodiment 1.

＜embodiment 5 〉

With 44 parts of aluminum carboxylates (a1), 70 parts of native paraffins { Licowax S (e1) }, be modified to 44 parts in the behenic acid aluminium (a5), 70 parts of the silicone { SILWET L-720 Japan ユ ニ カ one (strain) silicone oil (e5) } that in Production Example 2, obtain, in addition, obtain defoamer of the present invention (S5) in the same manner with embodiment 1.Also have, confirmed not have particle more than 5 microns by the decentralization test in the same manner with embodiment 1.

＜embodiment 6 〉

With 100 parts of polyoxyalkylene compounds (c1), 70 parts of native paraffins { Licowax S (e1) }, be modified to 100 parts of polyoxyalkylene compounds { ニ ュ one Port one Le LB-3000, Sanyo change into industry (strain) (c2) }, 0 part of native paraffin (e1), and use 5 parts of silica (d1) { the シ リ カ industry (strain) of NIPSIL SS-10 Japan }, in addition, obtain defoamer of the present invention (S6) in the same manner with embodiment 1.Also have, confirmed not have particle more than 5 microns by the decentralization test in the same manner with embodiment 1.

＜embodiment 7 〉

With 44 parts of aluminum carboxylates (a1), 786 parts of hydrocarbon ils (b1), be modified to 1 part of aluminum carboxylate (a2), 999 parts of hydrocarbon ils (b1), in addition, obtain defoamer of the present invention (S7) in the same manner with embodiment 1.Also have, confirmed not have particle more than 5 microns by the decentralization test in the same manner with embodiment 1.

＜embodiment 8 〉

With 44 parts of aluminum carboxylates (a1), 786 parts of hydrocarbon ils (b1), 100 parts of polyoxyalkylene compounds (c1), be modified to 60 parts of aluminum carboxylates (a2), 40 parts of hydrocarbon ils (b1), 785 parts of polyoxyalkylene compounds (c2), in addition, obtain defoamer of the present invention (S8) in the same manner with embodiment 1.Also have, confirmed not have particle more than 5 microns by the decentralization test in the same manner with embodiment 1.

＜comparative example 1 〉

Except not containing aluminum carboxylate (a1), obtain being used for the defoamer (HS1) of comparison in the same manner with embodiment 1.Also have, confirm not have particle more than 5 microns by the decentralization test in the same manner with embodiment 1.

＜comparative example 2 〉

Except 44 parts of aluminum carboxylates (a1) being modified to 22 parts in 22 parts of aluminum carboxylates (a2) and one (stearic acid) aluminium { with the pure medicine of light (strain) (stearic acid) aluminium (purity 85%) }, obtain being used for the defoamer (HS2) of comparison in the same manner with embodiment 1.Also have, confirm not have particle more than 5 microns by the decentralization test in the same manner with embodiment 1.

＜comparative example 3 〉

Except 44 parts of aluminum carboxylates (a1) are modified to 22 parts of aluminum carboxylates (a2) and dolomol SM-1000, Sakai chemical industry (strain) two (stearic acid) magnesium (purity 90%)) 22 parts, obtain being used for the defoamer (HS3) of comparison in the same manner with embodiment 1.Wherein, confirm not have particle more than 5 microns by decentralization test in the same manner with embodiment 1.

＜comparative example 4 〉

Except 44 parts of aluminum carboxylates (a1) being modified to 22 parts in 22 parts of aluminum carboxylates (a2) and three (stearic acid) aluminium { clear and chemical (strain) three (stearic acid) aluminium (purity 95%) }, obtain being used for the defoamer (HS4) of comparison in the same manner with embodiment 1.Wherein, confirm not have particle more than 5 microns by decentralization test in the same manner with embodiment 1.

The product stability of defoamer S1～S8 that obtains in embodiment 1～8 and comparative example 1～4 and the composition of HS1～HS4 and their defoamer is as shown in table 3.

Wherein, the defoamer of putting into the about 110ml in the 140ml glass system closed container is carried out visualization after placing 30 days under 40 ℃, and estimate by following metewand.

Well: do not separate and gelation

Gelation: do not have flowability, even high degree of agitation does not have flowability yet

Separate: be separated into two-layer

Table 3

Trade name			Embodiment								Comparative example
															1	2	3	4	5	6	7	8	1	2	3	4
			A	SA-1000(a1)		44					44																22	22	22
SA-1500(a2)															44					1	60
				SA-2000(a3)				44
Aluminium octoate (a4)																	44
				Behenic acid aluminium (a5)						44
Content (%) is annotated)	(A1)	21													0	0	39	11	21	21	21		58	21	21
				(A2)	79	100	100	61	89	79	79	79		42												79	79
	(FA)	5													18	25	5	11	5	5	5		3	5	5
				B	PURESPIN G		715	275	259	715	715	715	909	36												715	715	715	715
PURESPIN E
					JSOアロマ790		71		527	71	71	71	90	4											71	71	71	71
COSMO SP10			511
					(BA) content (number %)		12	5	28	12	12	12	12	12											12	12	12	12
C	ニ ュ one Port one Le LB385 (c1)		100												100		70	100		100		100	100	100					100
				ニ ュ one Port one Le LB3000 (c2)							100		785
	D	Nipsil SS-10(d1)																		5
E				Licowax S(e1)		70						70	70	70											70	70	70
	FT-100(e2)														7
				カ Le コ one Le 18 (e3)				70
	ェ キ セ パ one Le OL-OL (e4)																70
				SILWET L-720(e5)						70
	One (stearic acid) aluminium																							22
SM-1000														22
			Three (stearic acid) aluminium																								22
Product stability						Well	Well	Well	Well	Well	Well	Well	Well	Well											Separate			Separate	Gelation

A: aluminum carboxylate { one (carboxylic acid) aluminium (A1), two (carboxylic acid) aluminium (A2), free fatty (FA) }

B: hydrocarbon ils { aromatic series hydrocarbon ils (BA) }

C: polyoxyalkylene compounds

D: silica

E: other compositions

Annotate) with respect to (A1) and (A2) content of gross weight (%)

＜evaluation Example 1 〉

Defoamer S1～HS4 that use obtains in embodiment 1～8 and comparative example 1～4 is by method modulation emulsion coating as follows.About these emulsion coating, estimate defoaming and depression by following method, their result is as shown in table 4.

(1) modulation of emulsion coating

Form with following raw material, use super automatic homogenizer that the turbine type blade is installed (Japanese smart device commercial firm system, model ED), grind (grinding) and, thereby finish coatingization its discharging (let down).Detect the decentralization of the coating that obtains in the same manner with embodiment, confirm not have the particle more than 5 microns.

Then, make it to reach 77KU (25 ℃), obtain emulsion coating with this coating of Si Tuomu viscosimeter (JIS K5400-1990) dilute with water.

＜grind operation 〉

8.2 parts in water

SN デ ィ ス パ one サ シ ト 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 thickener

(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

＜discharging operation 〉

ボ Application コ one ト EC819; 55.5 parts of big Japanese ink chemical industry (strain) system acrylic acid emulsus

Liquid

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; イ one ス ト マ Application ケ ミ カ Le corporate system film is adjusted 2.0 parts of agent

One 636 0.2 parts of SN シ Network Na

Add up to 100.0 parts

(2) modulation of emulsion coating

In emulsion coating, add defoamer S1～HS4 and make its amount reach 1 weight % (for the emulsion basic coating), the super automatic homogenizer that use is equipped with the turbine type blade carries out 3 minutes mixing with 2000rpm under 15～25 ℃, obtain emulsion coating 1～12.

In addition, make the coating that does not add defoamer, as emulsion coating 13.

(3) evaluation of defoaming and depression

With acetone/cloth to tin-coated steel dermatotome { thick 0.5mm, be cut into 20 * 30cm} and carry out degreasing, cylinder is coated with emulsion coating 1～13 and makes wet-film thickness reach 250 μ m then, be dried 1 day in the control room that is adjusted to 25 ℃ and relative humidity 60% then, observe film coated surface, according to following benchmark evaluation defoaming and depression.

In addition, under 40 ℃ emulsion coating 1～13 is being left standstill keeping after 1 month (after the ageing), again under 15～25 ℃, carry out 3 minutes mixing with the super automatic homogenizer that the turbine type blade is installed with 2000rpm, obtain being used to estimate the emulsion coating of ageing (aging), estimate defoaming and depression equally.

＜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

＜depression 〉

5: have 2 with lower recess or cratering (cratering) trace

4: 2～5 depressions or cratering trace are arranged

3: 5～10 depressions or cratering trace are arranged

2: 10～20 depressions or cratering trace are arranged

1: depression or cratering trace more than 20 are arranged

＜evaluation Example 2 〉

Defoamer S1～HS4 that use obtains in embodiment 1～8 and comparative example 1～4 modulates the coating (coating color) that is used on the coating paper by method as follows.Estimated defoaming and depression for these coating by following method, its result is as shown in table 4.

(1) modulation of base coat

Form with following raw material, use super automatic homogenizer that the turbine type blade is installed (Japanese smart device commercial firm system, model ED), make base coat.

The prescription of＜base coat 〉

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 ァ ィ マ テ Star Network system powdered whitings

HT clay: 60.0 parts of secondary clays

20.0 parts in SBR2803F:JSR (strain) system SBR latex

MS4600: 8.6 parts of japanese food processing (strain) oxygenerating starch

Add up to 172.0 parts

(2) evaluation of defoaming and depression

In base coat, add defoamer and make its amount reach 1%, use the super automatic homogenizer that the turbine type blade is installed under 15～25 ℃, to carry out 10 minutes mixing, obtain coating with 2000rpm.In addition, except not adding defoamer, adopt method same as described above to obtain blank coating (not adding defoamer).Then, for these coating with JIS K5600-2-4:1999 (metal system specific gravity bottle: the proportion of the coating after the stirring of firm end after 10 minutes that be reference measurement hydrometer jar).Proportion is big more, shows that the intervention of bubble is few more, and defoaming is good.

In addition, { thick 0.5mm is cut into 20 * 30cm} and carries out degreasing, uses the applicator coating composition then, makes its wet-film thickness reach 250 μ m, observes film coated surface then, by following benchmark evaluation depression to glass plate with acetone/cloth.

＜depression 〉

5: have 2 with lower recess

4: 2～5 depressions are arranged

3: 5～10 depressions are arranged

2: 10～20 depressions are arranged

1: depression more than 20 is arranged

Table 4

			Evaluation Example 1				Evaluation Example 2
											Defoamer	After just having modulated		After the ageing		Defoaming proportion	Depression
Defoaming	Depression	Defoaming	Depression
				Embodiment	1	S1	5	5				5	5	1.335	5
2	S2	5	5						5	5	1.332					5
					3	S3	5	5				5	5	1.321	5
4	S4	5	5						4	5	1.345					5
					5	S5	5	4				5	5	1.325	5
6	S6	5	5						5	5	1.333					5
					7	S7	5	5				5	5	1.325	5
8	S8	5	5						5	5	1.346					5
					Comparative example	1	HS1	1				3	1	3	1.221		1
2	HS2	4	1	3					2	1.236	2
						3	HS3	2				2	2	3	1.245	4
4	HS4	3	4	2					4	1.321	3
						Do not add defoamer						2	5	1	5	1.135	5

Industrial utilizability

The present invention's defoamer can be in paper pulp industry processed, food industry, fiber industry, synthetic resin industry, synthetic rubber industry, resin emulsion is industrial, concrete is industrial, coatings industry, the processing of dung urine, draining processing etc. make in a large number the foaming such as manufacturing treatment process of water become in all manufacturings, treatment process of problem and use.

Claims (4)

1, a kind of defoamer is the defoamer that contains aluminum carboxylate (A) and hydrocarbon ils (B) and do not contain carboxy acid alkali's earth metal, it is characterized in that,

(A) be the mixture of two (carboxylic acid) aluminium (A2) or one (carboxylic acid) aluminium (A1) and two (carboxylic acid) aluminium (A2),

With respect to (A) and weight (B), content (A) is 0.1～60 weight %, and content (B) is 40～99.9 weight %,

(A1) content is below the 40 weight % with respect to (A1) and gross weight (A2).

2, defoamer as claimed in claim 1 is characterized in that,

Also contain free fatty (FA), content (FA) is 1～30 weight % with respect to the weight of one (carboxylic acid) aluminium (A1) and two (carboxylic acid) aluminium (A2).

3, as claim 1 or 2 described defoamers, it is characterized in that,

The hydrocarbon ils (B) that also contains aromatic series carbon (BA), the content of aromatic series carbon (BA) is 1～30 number % with respect to the total carbon atom number of hydrocarbon ils (B).

4, as any described defoamer in the claim 1～3, it is characterized in that,

The polyoxyalkylene compounds (C) that also contains useful general formula (1) expression,

R ¹{-(OA) _n-OR ²} _m (1)

Wherein, in general formula (1), R ¹Expression hydrogen atom or carbon number are 2～22 organic group, R ²Expression hydrogen atom or carbon number are 8～31 acyl group, and OA represents that carbon number is 3～4 alkylene oxide group, and m represents 1～3 integer, and n represents 10～60 integer.