JP6197768B2 - Oil compound for defoamer, method for producing the same, and defoamer composition - Google Patents

Description

  The present invention relates to an oil compound for an antifoaming agent containing a specific organopolysiloxane as a silica surface treating agent, and is excellent in the initial antifoaming property and antifoaming sustainability in a foaming liquid, particularly an alkaline foaming liquid. The present invention relates to an oil compound, a production method thereof, and an antifoaming composition containing the same.

  Silicone antifoaming agents are widely used in processes involving foaming in the chemical industry, food industry, petroleum industry, paper industry, textile industry, pharmaceutical industry, etc., and include dimethylpolysiloxane, methylphenylpolysiloxane, and methylvinylpolysiloxane. An oil compound type antifoaming agent in which a silicone oil such as the above is mixed with fine powder silica has been widely used.

  In actual use, an emulsion type antifoaming agent in which the oil compound type antifoaming agent is dispersed in water together with a surfactant, or an organopolysiloxane modified with a polyoxyalkylene group and an oil compound are used in combination. Self-emulsifying antifoaming agents and the like have been proposed (Patent Document 1: Japanese Patent Laid-Open No. 51-71886, Patent Document 2: Japanese Patent Publication No. 54-43015, Patent Document 3: Japanese Patent Publication No. 52-19836). Gazette, patent document 4: Japanese Patent Publication No. 52-22638, patent document 5: Japanese Patent Publication No. 55-23084), and the defoaming performance of the oil compound-type antifoaming agent as a raw material is large. Defoaming performance may be insufficient. As an example, problems such as insufficient initial defoaming performance and deterioration of the defoaming performance over time due to prolonged contact with the foaming liquid may occur, which is particularly noticeable when the foaming liquid is alkaline. there were.

  Various proposals have been made to improve these problems and to further improve the defoaming performance. For example, a method of hydrophobizing silica used in an oil compound with chlorosilane or the like in advance (Patent Document 6: JP-B 52-52). No. 31836), a method of treating silica with a nitrogen-containing organosilicon compound (Patent Document 7: Japanese Patent Publication No. 51-35556) and the like. There has been a demand for further improvement in performance.

  In response to these problems, a self-emulsifying antifoaming composition with improved alkali resistance by mixing hydrophobic organopolysiloxane and finely divided silica surface-treated with organopolysiloxane in the presence of an alkaline catalyst (patented) Document 8: Japanese Patent No. 4232031), emulsion type antifoaming composition (Patent Document 9: Japanese Patent Application Laid-Open No. 2007-222812) and the like have been proposed. However, in the neutralization process of oil compound production, there is a problem that the viscosity of the oil compound changes over time due to lack of neutralization, or organic acids and inorganic acids used as a neutralizing agent are not easily removed. is there.

  Recently, to solve these problems, a mixture of a hydrophobic organopolysiloxane and finely divided silica is mixed in the presence of an alkaline catalyst, and then neutralized with a solid acid such as succinic acid, whereby the viscosity of the oil compound is increased. Has been proposed (Patent Document 10: Japanese Patent Application Laid-Open No. 2011-104525), and the like, which has little change over time and can easily remove the residue of the neutralizing agent from the oil compound.

JP-A-51-71886 Japanese Patent Publication No.54-43015 Japanese Patent Publication No.52-19836 Japanese Patent Publication No. 52-22638 Japanese Patent Publication No. 55-23084 Japanese Patent Publication No.52-31836 Japanese Patent Publication No. 51-35556 Japanese Patent No. 4232031 JP 2007-222812 A JP 2011-104525 A

  The present invention has been made in view of the above circumstances, and an oil compound having good initial defoaming property and less deterioration over time even in a foaming liquid, particularly an alkaline foaming liquid, and an excellent defoaming performance, and a production method thereof, and its An object of the present invention is to provide an antifoaming composition containing an oil compound.

［式中、Ｒ¹は独立に炭素数１〜２０の一価の有機基であり、Ｘ¹、Ｘ²はそれぞれ独立にＲ¹又は下記式（ｉ）

（式中、Ｒ¹は上記と同じであり、Ｒ²は同一でも異なっていてもよく、水素原子、又は非置換もしくは置換の、飽和もしくは不飽和の、炭素数１〜２０の一価炭化水素基である。ａは２以上の整数であり、ｂは１〜３の整数である。）
で示される基であり、Ｙは独立に下記式（ｉｉ）

（式中、Ｒ¹、Ｘ²は上記と同じであり、Ｘ³はＸ¹と同じであり、ｆは０以上の整数である。）
で示される基であり、ｃ、ｄ、ｅは０以上の整数である。但し、Ｘ¹〜Ｘ³のうち少なくとも１個は式（ｉ）で示される基である。］
を含有してなり、（Ｂ）成分の表面処理剤として（Ｃ）成分を用いる消泡剤用オイルコンパウンドを使用することで、アルカリ性の発泡液中でも初期消泡性及び特に消泡持続性が優れるシリコーン系の消泡剤組成物を得ることができることを見出し、本発明をなすに至った。 As a result of intensive studies to achieve the above object, the present inventors
(A) Essentially hydrophobic organopolysiloxane having a viscosity at 25 ° C. of 10 to 100,000 mm ² / s: 100 parts by mass
(B) Fine powder silica having a specific surface area of 50 m ² / g or more: 1 to 30 parts by mass,
(C) Organopolysiloxane represented by the following general formula (I): 0.001 to 5 parts by mass

[Wherein, R ¹ is independently a monovalent organic group having 1 to 20 carbon atoms, and X ¹ and X ² are each independently R ¹ or the following formula (i):

(In the formula, R ¹ is the same as above, and R ² may be the same or different, and is a hydrogen atom, or an unsubstituted or substituted, saturated or unsaturated, monovalent hydrocarbon having 1 to 20 carbon atoms. A is an integer of 2 or more, and b is an integer of 1 to 3.)
Y is independently represented by the following formula (ii)

(In the formula, R ¹ and X ² are the same as above, X ³ is the same as X ¹ , and f is an integer of 0 or more.)
And c, d, and e are integers of 0 or more. However, at least one of X ^{1 to} X ³ is a group represented by the formula (i). ]
By using an antifoaming agent oil compound that uses the component (C) as a surface treating agent for the component (B), the initial defoaming property and particularly the defoaming sustainability are excellent even in an alkaline foaming liquid. The inventors have found that a silicone-based antifoaming agent composition can be obtained, and have reached the present invention.

［式中、Ｒ¹はメチル基であり、Ｘ¹、Ｘ²はそれぞれ独立にＲ¹又は下記式（ｉ）

（式中、Ｒ¹は上記と同じであり、Ｒ²は同一でも異なっていてもよく、水素原子、又は非置換もしくは置換の、飽和もしくは不飽和の、炭素数１〜２０の一価炭化水素基である。ａは２以上の整数であり、ｂは１〜３の整数である。）
で示される基であり、Ｙは独立に下記式（ｉｉ）

（式中、Ｒ¹、Ｘ²は上記と同じであり、Ｘ³はＸ¹と同じであり、ｆは０以上の整数である。）
で示される基であり、ｃ、ｄ、ｅは０以上の整数である。但し、Ｘ¹〜Ｘ³のうち少なくとも１個は式（ｉ）で示される基であり、上記式（Ｉ）で表されるオルガノポリシロキサンは、式（ｉ）で示される基を少なくとも１個有する。］
を含有してなり、（Ｂ）成分の表面処理剤として（Ｃ）成分を用いることを特徴とする消泡剤用オイルコンパウンド。
〔２〕
（１）（Ａ）２５℃における粘度が１０〜１００，０００ｍｍ²／ｓである本質的に疎水性のオルガノポリシロキサン：１００質量部、
（Ｂ）比表面積が５０ｍ²／ｇ以上の微粉末シリカ：１〜３０質量部、
（Ｃ）下記一般式（Ｉ）で表されるオルガノポリシロキサン：０．００１〜５質量部、

［式中、Ｒ¹はメチル基であり、Ｘ¹、Ｘ²はそれぞれ独立にＲ¹又は下記式（ｉ）

（式中、Ｒ¹は上記と同じであり、Ｒ²は同一でも異なっていてもよく、水素原子、又は非置換もしくは置換の、飽和もしくは不飽和の、炭素数１〜２０の一価炭化水素基である。ａは２以上の整数であり、ｂは１〜３の整数である。）
で示される基であり、Ｙは独立に下記式（ｉｉ）

（式中、Ｒ¹、Ｘ²は上記と同じであり、Ｘ³はＸ¹と同じであり、ｆは０以上の整数である。）
で示される基であり、ｃ、ｄ、ｅは０以上の整数である。但し、Ｘ¹〜Ｘ³のうち少なくとも１個は式（ｉ）で示される基であり、上記式（Ｉ）で表されるオルガノポリシロキサンは、式（ｉ）で示される基を少なくとも１個有する。］
（Ｄ）水：０〜５質量部
を混練する第一の工程、
（２）この第一の工程で得られた混練物を熱処理する第二の工程からなる第一コンパウンディングと、
（３）この第二の工程で得られた混練物に、
（Ｅ）アルカリ触媒又は酸触媒：０．００１〜５質量部
を混練する第三の工程、
（４）この第三の工程で得られた混練物を熱処理する第四の工程からなる第二コンパウンディングと、
（５）この第四の工程で得られた混練物に、中和剤として酸又はアルカリを混練する第五の工程
とを含むことを特徴とする消泡剤用オイルコンパウンドの製造方法。
〔３〕
〔１〕記載のオイルコンパウンドを含むことを特徴とする消泡剤組成物。
この場合、消泡剤組成物は、溶液型、自己乳化型、エマルション型として調製し得、アルカリ性の発泡液用として好適である。
Accordingly, the present invention provides an oil compound for an antifoaming agent, a method for producing the same, and an antifoaming agent composition comprising the same.
[1]
(A) Essentially hydrophobic organopolysiloxane having a viscosity at 25 ° C. of 10 to 100,000 mm ² / s: 100 parts by mass
(B) Fine powder silica having a specific surface area of 50 m ² / g or more: 1 to 30 parts by mass,
(C) Organopolysiloxane represented by the following general formula (I): 0.001 to 5 parts by mass

[Wherein, R ¹ is a methyl group , and X ¹ and X ² are each independently R ¹ or the following formula (i):

(In the formula, R ¹ is the same as above, and R ² may be the same or different, and is a hydrogen atom, or an unsubstituted or substituted, saturated or unsaturated, monovalent hydrocarbon having 1 to 20 carbon atoms. A is an integer of 2 or more, and b is an integer of 1 to 3.)
Y is independently represented by the following formula (ii)

(In the formula, R ¹ and X ² are the same as above, X ³ is the same as X ¹ , and f is an integer of 0 or more.)
And c, d, and e are integers of 0 or more. Provided that at least one of X ¹ to X ³ is Ri Oh a group of the formula (i), organopolysiloxane represented by the formula (I), at least a group represented by the formula (i) 1 Have one. ]
And (C) component is used as a surface treating agent of (B) component, and the oil compound for antifoamers characterized by the above-mentioned.
[2]
(1) (A) Essentially hydrophobic organopolysiloxane having a viscosity at 25 ° C. of 10 to 100,000 mm ² / s: 100 parts by mass
(B) Fine powder silica having a specific surface area of 50 m ² / g or more: 1 to 30 parts by mass,
(C) Organopolysiloxane represented by the following general formula (I): 0.001 to 5 parts by mass,

[Wherein, R ¹ is a methyl group , and X ¹ and X ² are each independently R ¹ or the following formula (i):

(In the formula, R ¹ is the same as above, and R ² may be the same or different, and is a hydrogen atom, or an unsubstituted or substituted, saturated or unsaturated, monovalent hydrocarbon having 1 to 20 carbon atoms. A is an integer of 2 or more, and b is an integer of 1 to 3.)
Y is independently represented by the following formula (ii)

(In the formula, R ¹ and X ² are the same as above, X ³ is the same as X ¹ , and f is an integer of 0 or more.)
And c, d, and e are integers of 0 or more. Provided that at least one of X ¹ to X ³ is Ri Oh a group of the formula (i), organopolysiloxane represented by the formula (I), at least a group represented by the formula (i) 1 Have one. ]
(D) Water: first step of kneading 0 to 5 parts by mass,
(2) a first compound comprising a second step of heat-treating the kneaded product obtained in the first step;
(3) In the kneaded material obtained in this second step,
(E) Alkali catalyst or acid catalyst: third step of kneading 0.001 to 5 parts by mass;
(4) a second compounding comprising a fourth step of heat treating the kneaded product obtained in the third step;
(5) A method for producing an oil compound for an antifoaming agent, comprising the fifth step of kneading an acid or an alkali as a neutralizing agent in the kneaded product obtained in the fourth step.
[3]
[1] An antifoam composition comprising the oil compound according to [1].
In this case, the antifoaming agent composition can be prepared as a solution type, a self-emulsifying type, or an emulsion type, and is suitable for an alkaline foaming liquid.

  According to the present invention, it is possible to obtain a silicone-based antifoaming agent composition that imparts good initial antifoaming property even in an alkaline foaming liquid, in particular, has little performance deterioration with time and is excellent in defoaming performance.

Hereinafter, the present invention will be described in more detail.
The oil compound for an antifoaming agent of the present invention is
(A) an essentially hydrophobic organopolysiloxane having a viscosity at 25 ° C. of 10 to 100,000 mm ² / s,
(B) fine powder silica having a specific surface area of 50 m ² / g or more,
(C) An organopolysiloxane represented by the general formula (I) is contained, and the component (C) is used as a surface treatment agent for the component (B).

Component (A) The organopolysiloxane of component (A) is essentially hydrophobic. Here, “essentially hydrophobic” means that even if some functional groups contain hydrophilic groups, the organopolysiloxane as a whole exhibits hydrophobicity.

The essentially hydrophobic organopolysiloxane (A) may be linear or branched, and those represented by the following average composition formula (II) are particularly preferred.
R ³ _g SiO _{(4-g) / 2} (II)

In the above formula (II), R ³ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, particularly 1 to 15 carbon atoms, which may be the same or different. Specific examples of the monovalent hydrocarbon group for R ³ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group. Alkyl groups such as dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, cycloalkyl group such as cyclohexyl group, alkenyl group such as vinyl group, allyl group, aryl group such as phenyl group, tolyl group, styryl group An aralkyl group such as an α-methylstyryl group or the like, or a chloromethyl group in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom, a cyano group, an amino group or a hydroxyl group, 3-chloro Propyl group, 3,3,3-trifluoropropyl group, cyanoethyl group, 3-aminopropyl group, N- (β-amino Although chill)-.gamma.-aminopropyl group and the like, 80 mol% of the total R ³ in terms of defoaming and economy more, and particularly preferably more than 90 mol% are methyl groups.
Moreover, g is a positive number satisfying 1.9 ≦ g ≦ 2.2, preferably 1.95 ≦ g ≦ 2.15.

The end of the organopolysiloxane may be blocked with a triorganosilyl group represented by R ³ ₃ Si— or a diorganohydroxysilyl group represented by (HO) R ³ ₂ Si—. Good.

The viscosity at 25 ° C. of this essentially hydrophobic organopolysiloxane (A) measured by an Ostwald viscometer is 10 to 100,000 mm ² / s from the viewpoint of defoaming and workability, preferably 50 to 30,000 mm ² / s. 10mm inferior antifoaming performance is less than ² / s, ^{100,000mm 2} / s more than a defoaming agent for oil compound workability viscosity is increased (hereinafter, sometimes referred to as a silicone oil compound) is poor .

  The component (A) of the present invention is usually produced by ring-opening polymerization of a cyclic low molecular siloxane such as octamethylcyclotetrasiloxane using a catalyst, but after the polymerization, the cyclic low molecular siloxane as a raw material is contained. Therefore, it is preferable to use what was distilled off while heating and reducing pressure while allowing an inert gas to pass through during reaction generation.

（式中、ｈ≧１０であり、ｉ≧１である。） Examples of the specific structure of the component (A) of the present invention include, but are not limited to, those shown below. In the following formulae, Me, Vi, Ph, and OH represent a methyl group, a vinyl group, a phenyl group, and a hydroxyl group, respectively.

(Where h ≧ 10 and i ≧ 1)

Component (B) The finely divided silica of component (B) is preferably fumed silica or hydrophilic silica such as precipitated silica, and these can be used alone or in combination of two or more. The specific surface area of the finely divided silica (BET method) is at 50 m ² / g or higher, preferably 100~700m ² / g, more preferably 150~500m ² / g. When the specific surface area is less than 50 m ² / g, preferable defoaming performance cannot be obtained.

As an example of a commercially available (B) component that can be used in the present invention, AEROSIL (registered trademark) 300 (hydrophilic fumed silica having a BET specific surface area of 300 m ² / g) that can be purchased from Nippon Aerosil Co., Ltd. AEROSIL (registered trademark) 200 (hydrophilic fumed silica having a BET specific surface area of 200 m ² / g) and NIPSIL (registered trademark) L-250 (170 m ² / g which can be purchased from Tosoh Silica Co., Ltd.) And hydrophilic precipitated silica having a BET specific surface area of

  The ratio of (B) component is 1-30 mass parts with respect to 100 mass parts of (A) component, Preferably it is the range of 5-15 mass parts. If it is less than 1 part by mass, sufficient defoaming performance cannot be obtained, and if it exceeds 30 parts by mass, the viscosity of the resulting silicone oil compound increases and the workability deteriorates.

［式中、Ｒ¹は独立に炭素数１〜２０の一価の有機基であり、Ｘ¹、Ｘ²はそれぞれ独立にＲ¹又は下記式（ｉ）

（式中、Ｒ¹は上記と同じであり、Ｒ²は同一でも異なっていてもよく、水素原子、又は非置換もしくは置換の、飽和もしくは不飽和の、炭素数１〜２０の一価炭化水素基である。ａは２以上の整数であり、ｂは１〜３の整数である。）
で示される基であり、Ｙは独立に下記式（ｉｉ）

（式中、Ｒ¹、Ｘ²は上記と同じであり、Ｘ³はＸ¹と同じであり、ｆは０以上の整数である。）
で示される基であり、ｃ、ｄ、ｅは０以上の整数である。但し、Ｘ¹〜Ｘ³のうち少なくとも１個は式（ｉ）で示される基である。］ (C) Component The organopolysiloxane represented by the following general formula (I) of the component (C) performs surface hydrophobization treatment of the component (B) and wettability of the component (B) to the component (A). These improve the dispersibility, and these can be used alone or in combination of two or more. The component (C) is different from the component (A) in that it includes an alkylene structure [Si—C _a H _2a —Si (a is an integer of 2 or more)].

[Wherein, R ¹ is independently a monovalent organic group having 1 to 20 carbon atoms, and X ¹ and X ² are each independently R ¹ or the following formula (i):

(In the formula, R ¹ is the same as above, and R ² may be the same or different, and is a hydrogen atom, or an unsubstituted or substituted, saturated or unsaturated, monovalent hydrocarbon having 1 to 20 carbon atoms. A is an integer of 2 or more, and b is an integer of 1 to 3.)
Y is independently represented by the following formula (ii)

(In the formula, R ¹ and X ² are the same as above, X ³ is the same as X ¹ , and f is an integer of 0 or more.)
And c, d, and e are integers of 0 or more. However, at least one of X ^{1 to} X ³ is a group represented by the formula (i). ]

In the above formula (I), R ¹ is a monovalent organic group having 1 to 20 carbon atoms, and these may be the same or different. R ¹ includes methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, Hexadecyl, octadecyl and other alkyl groups, cyclohexyl and other cycloalkyl groups, vinyl and allyl groups and other alkenyl groups, phenyl and tolyl groups and other aryl groups, styryl groups and α-methylstyryl groups and other aralkyl groups It is preferable that it is a C1-C20, especially 1-15 monovalent hydrocarbon group, such as an alkyl group or an aryl group, More preferably, it is a C1-C10 alkyl group or a phenyl group. It is.

R ² is a hydrogen atom or an unsubstituted or substituted, saturated or unsaturated, monovalent hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 15 carbon atoms, and they are the same or different. May be. Specific examples of the monovalent hydrocarbon group for R ² include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group. Alkyl groups such as dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, cycloalkyl group such as cyclohexyl group, alkenyl group such as vinyl group, allyl group, aryl group such as phenyl group, tolyl group, styryl group , An aralkyl group such as an α-methylstyryl group, etc., or a chloromethyl group, a 3-chloropropyl group, 3 or a part of the hydrogen atoms bonded to carbon atoms of these groups substituted with a halogen atom, a cyano group, , 3,3-trifluoropropyl group, cyanoethyl group and the like. R ² is preferably an alkyl group.

a is an integer greater than or equal to 2, the integer of 2-30 is preferable, More preferably, it is an integer of 2-20, More preferably, it is an integer of 2-10. b is an integer of 1 to 3, preferably 2 or 3, more preferably 3.
c and f are integers of 0 or more, preferably an integer of 0 to 100, more preferably an integer of 2 to 80, and still more preferably an integer of 2 to 50. d and e are integers of 0 or more, preferably an integer of 0 to 100, more preferably an integer of 0 to 80, and still more preferably an integer of 0 to 50. Note that c + d + e + (d × f) is preferably an integer of 0 to 300, and more preferably an integer of 0 to 150.

The organopolysiloxane represented by the above formula (I) has at least 1, preferably 1 to 50, more preferably 1 to 25 groups represented by the above formula (i).
The organopolysiloxane represented by the above formula (I) preferably has 1 to 150, particularly 1 to 75, organoxy groups or hydroxyl groups represented by OR ² in the molecule.

  The organopolysiloxane represented by the general formula (I) may be either terminal, side chain or both terminal side chain organoxy or hydroxy-modified organopolysiloxane, but both terminal, side chain or both terminal side chain di or tri Alkoxy-modified organopolysiloxanes are preferred, more preferably both end, side chain or both end side chain trialkoxy-modified organopolysiloxanes.

Examples of the specific structure of the component (C) of the present invention include, but are not limited to, those shown below. In the following formulae, Me, OH and OMe represent a methyl group, a hydroxyl group and a methoxy group, respectively.

（式中、ｊ≧２であり、ｋ≧０であり、ｌ≧１であり、ｍ≧１であり、ｎ≧１である。）

(Where j ≧ 2, k ≧ 0, l ≧ 1, m ≧ 1, and n ≧ 1)

  (C) The usage-amount of a component is 0.001-5 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.01-3 mass parts. If it is less than 0.001 part by mass, sufficient antifoaming performance cannot be obtained, and if it exceeds 5 parts by mass, the defoaming performance of the silicone oil compound obtained is deteriorated.

  The feature of the method for producing a silicone oil compound in the present invention is that the compounding is performed in two stages of a first compounding and a second compounding. The main purpose of the first compounding is to adsorb or immobilize the organopolysiloxane (C) component on the surface of the fine powdered silica (B) component, and the second compounding is the component (A). The main object is to fix the polymer component such as organopolysiloxane and the reactive group derived from the component (C) on the fine powder silica surface as the component (B).

［式中、Ｒ¹は独立に炭素数１〜２０の一価の有機基であり、Ｘ¹、Ｘ²はそれぞれ独立にＲ¹又は下記式（ｉ）

（式中、Ｒ¹は上記と同じであり、Ｒ²は同一でも異なっていてもよく、水素原子、又は非置換もしくは置換の、飽和もしくは不飽和の、炭素数１〜２０の一価炭化水素基である。ａは２以上の整数であり、ｂは１〜３の整数である。）
で示される基であり、Ｙは独立に下記式（ｉｉ）

（式中、Ｒ¹、Ｘ²は上記と同じであり、Ｘ³はＸ¹と同じであり、ｆは０以上の整数である。）
で示される基であり、ｃ、ｄ、ｅは０以上の整数である。但し、Ｘ¹〜Ｘ³のうち少なくとも１個は式（ｉ）で示される基である。］
（Ｄ）水：０〜５質量部
を混練する第一の工程、
（２）この第一の工程で得られた混練物を熱処理する第二の工程からなる第一コンパウンディングと、
（３）この第二の工程で得られた混練物に、
（Ｅ）アルカリ触媒又は酸触媒：（上記（Ａ）成分１００質量部に対し）０．００１〜５質量部
を混練する第三の工程、
（４）この第三の工程で得られた混練物を熱処理する第四の工程からなる第二コンパウンディングと、
（５）この第四の工程で得られた混練物に、中和剤として酸又はアルカリを混練する第五の工程
とを含み、これによって消泡剤用オイルコンパウンドを製造するものである。 That is, in the present invention,
(1) (A) Essentially hydrophobic organopolysiloxane having a viscosity at 25 ° C. of 10 to 100,000 mm ² / s: 100 parts by mass
(B) Fine powder silica having a specific surface area of 50 m ² / g or more: 1 to 30 parts by mass,
(C) Organopolysiloxane represented by the following general formula (I): 0.001 to 5 parts by mass,

[Wherein, R ¹ is independently a monovalent organic group having 1 to 20 carbon atoms, and X ¹ and X ² are each independently R ¹ or the following formula (i):

(In the formula, R ¹ is the same as above, and R ² may be the same or different, and is a hydrogen atom, or an unsubstituted or substituted, saturated or unsaturated, monovalent hydrocarbon having 1 to 20 carbon atoms. A is an integer of 2 or more, and b is an integer of 1 to 3.)
Y is independently represented by the following formula (ii)

(In the formula, R ¹ and X ² are the same as above, X ³ is the same as X ¹ , and f is an integer of 0 or more.)
And c, d, and e are integers of 0 or more. However, at least one of X ^{1 to} X ³ is a group represented by the formula (i). ]
(D) Water: first step of kneading 0 to 5 parts by mass,
(2) a first compound comprising a second step of heat-treating the kneaded product obtained in the first step;
(3) In the kneaded material obtained in this second step,
(E) Alkali catalyst or acid catalyst: a third step of kneading 0.001 to 5 parts by mass (with respect to 100 parts by mass of component (A) above),
(4) a second compounding comprising a fourth step of heat treating the kneaded product obtained in the third step;
(5) The kneaded product obtained in the fourth step includes a fifth step of kneading acid or alkali as a neutralizing agent, thereby producing an antifoaming oil compound.

  By using the silicone oil compound produced through the first to fifth steps, it is possible to obtain a defoaming agent composition having excellent initial defoaming property and defoaming durability even in a foaming liquid, particularly an alkaline foaming liquid. it can.

  The components (A) to (C) are as described above.

(D) Component Water of component (D) promotes hydrolysis of component (C) and plays a role of increasing the surface treatment rate of component (B). Since component (B) may contain water such as adsorbed water, component (D) may not be essential.

  (D) The usage-amount of a component is 0-5 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.01-5 mass parts, More preferably, it is 0.01-3 mass parts. is there.

(E) component (E) A component is an alkali catalyst or an acid catalyst. As the alkali catalyst, an alkali metal or alkaline earth metal oxide, hydroxide, alkoxide or siliconate, which is a known alkali catalyst used for an equilibrium reaction of polysiloxane, can be used, preferably potassium siliconate and Potassium hydroxide. Examples of the acid catalyst include organic acids such as acetic acid, butyric acid, maleic acid, and citric acid, and inorganic acids such as hydrochloric acid, nitric acid, phosphoric acid, and sulfuric acid. As the component (E), an alkali catalyst is preferable to an acid catalyst.

  (E) The usage-amount of a component is 0.001-5 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.01-5 mass parts, More preferably, it is 0.01-3 mass. Part, more preferably 0.05 to 3 parts by mass. If it is less than 0.001 part by mass, a sufficient catalytic effect cannot be obtained, and if it exceeds 5 parts by mass, the effect of the catalyst is not greatly improved, which is disadvantageous in terms of cost.

As the neutralizing agent for the alkali catalyst, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and carboxylic acid that is solid at room temperature can be used, and preferably solid carboxylic acid at room temperature. is there. Carboxylic acids that are solid at room temperature include monocarboxylic acids such as benzoic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and other dicarboxylic acids, citric acid, isocitrate. Tricarboxylic acids such as acids, oxalosuccinic acid and aconitic acid are used. Of these, succinic acid is preferable because it has a small acid dissociation constant and is strong as an acid, and is easily available. Further, as a neutralizing agent for the acid catalyst, an alkali metal or alkaline earth metal oxide, hydroxide, alkoxide or siliconate can be used, and potassium siliconate and potassium hydroxide are preferred.
In addition, the usage-amount of a neutralizing agent should just be the quantity which can neutralize the said (E) component.

  In this case, in the first step, the components (A) to (C) or the components (A) to (D) are preferably kneaded at a temperature of 100 ° C. or lower, more preferably 80 ° C. or lower. It is not particularly necessary to heat from the outside, and can be kneaded at room temperature (for example, 10 to 30 ° C.), and the temperature raised by heat generation in the system due to frictional resistance generated during kneading is adjusted to 100 ° C. or less, particularly 80 ° C. or less It is good to do. When kneading is performed at a temperature exceeding 100 ° C., the component (C) may volatilize and may not function effectively. The treatment time of the first step largely depends on the kneading apparatus and the scale and cannot be defined unconditionally, but is usually 0.1 to 3 hours, particularly about 0.5 to 2 hours.

  The second step is a heat treatment step for immobilizing (C) component hydrolyzed by at least one of adsorbed water in component (B) or component (D) on the surface of component (B), It heat-processes at 120-200 degreeC, Preferably it is 140-180 degreeC, Preferably kneading | mixing. When the heat treatment temperature is less than 120 ° C, the defoaming performance is inferior, and when the heat treatment temperature exceeds 200 ° C, the component (A) may be deteriorated (decomposed). The processing time of the second step largely depends on the kneading apparatus and the scale and cannot be specified unconditionally, but is usually 0.1 to 4 hours, particularly about 0.5 to 2 hours.

  In the third step, the component (E) is added to the kneaded product obtained in the second step to make the oil compound system alkaline or acidic. For the same reason as in the first step, the third step is preferably kneaded at a temperature of 100 ° C. or lower. In this case as well, kneading can be performed at room temperature (for example, 10 to 30 ° C.). The processing time of the third step is also largely dependent on the kneading apparatus and scale and cannot be defined unconditionally, but it is usually 0.05 to 3 hours, particularly about 0.1 to 2 hours.

  The fourth step is a heat treatment step for immobilizing a polymer component such as organopolysiloxane of component (A) and a reactive group derived from component (C) on the surface of fine powder silica of component (B), 120 It heat-processes at -200 degreeC, Preferably it is 140-180 degreeC, Preferably kneading | mixing. When the heat treatment temperature is less than 120 ° C, the defoaming performance is inferior, and when the heat treatment temperature exceeds 200 ° C, the component (A) may be deteriorated (decomposed). The processing time of the fourth step largely depends on the kneading apparatus and the scale and cannot be defined unconditionally, but is usually 0.1 to 6 hours, particularly about 2 to 4 hours.

  The fifth step is a step of neutralizing the alkali catalyst or acid catalyst used in the second compounding. For the same reason as in the first and third steps, the fifth step is preferably kneaded at a temperature of 100 ° C. or lower. In this case as well, kneading can be performed at room temperature (for example, 10 to 30 ° C.). The processing time of the fifth step is also largely dependent on the kneading apparatus and scale and cannot be defined unconditionally, but is usually 0.1 to 4 hours, particularly about 0.5 to 3 hours.

  Examples of the kneader used for kneading in the production method of the present invention include a planetary mixer, a kneader, a pressure kneader, a twin-screw kneader, an intensive mixer, an azimuth mixer, a disper, a planetary disper, and the like. However, it is not particularly limited. These kneaders can be used in any of the first step to the neutralization step.

  The silicone oil compound obtained by kneading and heat-treating the above components is used as it is, or an antifoam composition containing the silicone oil compound, specifically, a solution type antifoam dispersed in an appropriate solvent. It can be used as an agent composition, a self-emulsifying antifoaming composition in combination with an organopolysiloxane modified with a polyoxyalkylene group, or an emulsion defoaming composition obtained by a known emulsifying technique. .

  Here, in the case of a solution-type antifoaming agent composition dispersed in a suitable solvent, as the solvent, a solvent in which the essentially hydrophobic organopolysiloxane as component (A) is dissolved, for example, toluene, xylene, Examples include hexane, chloroform, 2-butanone and 4-methyl-2-pentanone.

  When setting it as a solution type antifoamer composition, it is preferable that content of a silicone oil compound is 5-80 mass% of the whole antifoamer composition, More preferably, it is 30-70 mass%. If the silicone oil compound content is too low, the defoaming performance of the antifoaming composition may be inferior. If it is too high, the main purpose of the solution type antifoaming composition is to improve the dispersibility of the silicone oil compound. There are cases where it is not possible.

In addition, when a self-emulsifying antifoam composition is used in combination with an organopolysiloxane modified with a polyoxyalkylene group, the organopolysiloxane modified with a polyoxyalkylene group is represented by the following general formula (III): What is shown.
R ⁴ ₂ R ⁶ SiO— (R ⁴ ₂ SiO) _o — (R ⁴ R ⁵ SiO) _p —SiR ⁴ ₂ R ⁶ (III)

In the above formula (III), R ⁴ is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, particularly 1 to 15 carbon atoms, specifically, a methyl group, an ethyl group, Propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group and other alkyl groups, cyclohexyl Bonded to a cycloalkyl group such as a group, an alkenyl group such as a vinyl group or an allyl group, an aryl group such as a phenyl group or a tolyl group, an aralkyl group such as a styryl group or an α-methylstyryl group, or a carbon atom of these groups Chloromethyl group, 3-chloropropyl group, 3, 3 in which some or all of the hydrogen atoms are substituted with halogen atoms, cyano groups, amino groups, etc. , 3-trifluoropropyl group, cyanoethyl group, 3-aminopropyl group, monovalent hydrocarbon group such as N- (β-aminoethyl) -γ-aminopropyl group.

R ⁵ is a polyoxyalkylene group represented by the following general formula (IV).
_{^{-R 7 -O (CH 2 CH 2}} O) q - (CH 2 (CH 3) CHO) r -R 8 (IV)
In the above formula (IV), R ⁷ is a divalent hydrocarbon group having 2 to 6 carbon atoms, and examples thereof include an alkylene group and an alkenylene group, such as an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group. Etc. R ⁸ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acetyl group or an isocyan group, and examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. q and r may be polymerized in block or random form, and the degree of polymerization (q + r) is 3 ≦ q + r ≦ 80, preferably 5 ≦ q + r ≦ 60, and q / r = 2/8 to 8/2, preferably Is a positive number satisfying q / r = 2.5 / 7.5 to 7.5 / 2.5.

On the other hand, R ⁶ is the same group as R ⁴ or R ⁵ , a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms. Specifically, the groups exemplified as the above R ⁴ and R ⁵ and the alkoxy group include methoxy Group, ethoxy group, propoxy group, butoxy group and the like.
In the above formula (III), o is an integer of 5 to 200, preferably 20 to 150, and p is an integer of 1 to 30, preferably 1 to 20.

The organopolysiloxane modified with the polyoxyalkylene group may be used singly or as a mixture of two or more, but the viscosity at 25 ° C. measured by Ostwald viscometer is 10 to 10, 000 mm ² / s, preferably 50~8,000mm ² / s, more preferably it is possible to use those which are 500~5,000mm ² / s.

Specific examples of the organopolysiloxane modified with a polyoxyalkylene group include, but are not limited to, the following.
(CH ₃ ) ₃ SiO — [(CH ₃ ) ₂ SiO] ₃₀ — [(CH ₃ ) R′SiO] ₅ —Si (CH ₃ ) ₃
R ′: —C ₃ H ₆ O— (C ₂ H ₄ O) ₃₀ — (C ₃ H ₆ O) ₁₀ —C ₄ H ₉ ,
(CH ₃ ) ₃ SiO — [(CH ₃ ) ₂ SiO] ₃₀ — [(CH ₃ ) R′SiO] ₃ —Si (CH ₃ ) ₃
R ′: —C ₃ H ₆ O— (C ₂ H ₄ O) ₂₀ — (C ₃ H ₆ O) ₂₀ —C ₄ H ₉ ,
(CH ₃ ) ₃ SiO — [(CH ₃ ) ₂ SiO] ₄₀ — [(CH ₃ ) R′SiO] ₄ —Si (CH ₃ ) ₃
R ′: —C ₃ H ₆ O— (C ₂ H ₄ O) ₂₁ — (C ₃ H ₆ O) ₇ —COCH ₃ ,
_{(CH 3) 3 SiO - [} (CH 3) 2 SiO] 50 - [(CH 3) R''SiO] 6 - [(CH 3) R '''SiO] 1 -Si (CH 3) 3
R ″: —C ₃ H ₆ O— (C ₂ H ₄ O) ₃₂ — (C ₃ H ₆ O) ₈ —C ₄ H ₉
R ′ ″: —C ₁₂ H ₂₅ ,
(CH ₃ ) ₃ SiO — [(CH ₃ ) ₂ SiO] ₁₃₅ — [(CH ₃ ) R′SiO] ₁₅ —Si (CH ₃ ) ₃
R ′: —C ₃ H ₆ O— (C ₂ H ₄ O) ₂₁ — (C ₃ H ₆ O) ₂₁ —CH ₃ ,
(CH ₃ ) ₃ SiO — [(CH ₃ ) ₂ SiO] ₃₀ — [(CH ₃ ) R′SiO] ₅ —Si (CH ₃ ) ₃
R ′: —C ₃ H ₆ O— (C ₂ H ₄ O) _25.5 — (C ₃ H ₆ O) _8.5 —C ₄ H ₉ ,
(CH ₃ ) ₃ SiO — [(CH ₃ ) ₂ SiO] ₂₇ — [(CH ₃ ) R′SiO] ₃ —Si (CH ₃ ) ₃
R ′: —C ₃ H ₆ O— (C ₂ H ₄ O) ₂₃ — (C ₃ H ₆ O) ₂₃ —C ₄ H ₉

  In the self-emulsifying antifoaming agent composition, the organopolysiloxane modified with the polyoxyalkylene group may be used alone or in a mixture of two or more, but the content thereof is self-emulsifying. It is preferable that it is 0-95 mass% of the whole type | mold antifoamer composition, More preferably, it is 0-70 mass%. If the content is too small, the main purpose of the self-emulsifying antifoam composition to increase the dispersibility of the silicone oil compound may not be satisfied. If the content is too large, the defoaming performance as an antifoam composition may be inferior. is there. In addition, although it can be set as an effective amount when mix | blending, it is preferable to mix | blend 20 mass% or more.

In addition, in the self-emulsifying antifoaming agent composition in combination with an organopolysiloxane modified with a polyoxyalkylene group,
HO— [CH ₂ (CH ₃ ) CHO] ₃₅ —H,
HO— [CH ₂ (CH ₃ ) CHO] ₇₀ —H,
HO— (CH ₂ CH ₂ O) ₄ — [CH ₂ (CH ₃ ) CHO] ₃₀ —H,
_{HO- (C 2 H 4 O)} 25 - (C 3 H 6 O) 35 -H,
HO— (C ₃ H ₆ O) ₃₀ —H,
_{CH 2 = CHCH 2 O- (CH} 2 CH 2 O) 32 - [CH 2 (CH 3) CHO] 8 -H,
_{CH 2 = CHCH 2 O- (CH} 2 CH 2 O) 22 - [CH 2 (CH 3) CHO] 22 -C 4 H 9,
_{CH 2 = CHCH 2 O- (CH} 2 CH 2 O) 10 -CH 3
A polyoxyalkylene polymer such as exemplified by sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene oxypropylene alkyl ether, Non-ionic surfactants such as polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil Good.
In addition, the compositional formula illustrated above is an example, and does not restrict | limit this invention.

  In the self-emulsifying antifoaming agent composition, the polyoxyalkylene polymer is blended in order to increase the dispersibility of the silicone oil compound, and even if it is used alone or in combination of two or more. However, the content is preferably 0 to 95% by mass, more preferably 0 to 70% by mass, based on the entire self-emulsifying antifoam composition. When there is too much content, the defoaming performance as an antifoamer composition may be inferior. In addition, although it can be set as an effective amount when mix | blending, it is preferable to mix | blend 20 mass% or more.

  Moreover, in the self-emulsifying antifoaming agent composition, the nonionic surfactant is blended in order to improve the dispersibility of the silicone oil compound, and even if it is used alone, it is a mixture of two or more. However, the content is preferably 0 to 95% by mass, more preferably 0 to 70% by mass, based on the entire self-emulsifying antifoam composition. When there is too much content, the defoaming performance as an antifoamer composition may be inferior. In addition, although it can be set as an effective amount when mix | blending, it is preferable to mix | blend 20 mass% or more.

  Moreover, when setting it as a self-emulsification type antifoamer composition, it is preferable that content of a silicone oil compound is 5-80 mass% of the whole self-emulsification type antifoamer composition, More preferably, it is 10-70 mass. %, And more preferably 20 to 60% by mass. If the content of the silicone oil compound is too small, the defoaming performance as an antifoaming composition may be inferior. If the content is too large, the main purpose of the self-emulsifying antifoaming composition is to increase the dispersibility of the silicone oil compound. You may not be satisfied.

  Further, when an emulsion type antifoaming agent composition is used, a known method can be used. As an emulsifier for emulsifying a silicone oil compound, the above-mentioned organopolysiloxane modified with a polyoxyalkylene group or polyoxyalkylene can be used. An alkylene polymer, a nonionic surfactant, etc. can be used.

  In the emulsion type antifoaming agent composition, the organopolysiloxane modified with the polyoxyalkylene group may be used singly or in a mixture of two or more, but the content thereof is an emulsion type antifoaming agent. It is preferable that it is 0-30 mass% of the whole foaming agent composition, More preferably, it is 1-20 mass%. When content exceeds 30 mass%, the defoaming performance of a composition may worsen.

  Further, in the emulsion type antifoaming agent composition, the polyoxyalkylene polymer serves as an emulsification aid, and may be used alone or in a mixture of two or more. Is preferably 0 to 40% by mass, more preferably 0 to 20% by mass, based on the whole emulsion antifoam composition. When content exceeds 40 mass%, the emulsification characteristic of a composition may worsen. In addition, although it can be set as an effective amount when mix | blending, it is preferable to mix | blend 5 mass% or more.

  Furthermore, in the emulsion-type antifoaming agent composition, the nonionic surfactant is for dispersing the silicone oil compound in water, and even if it is used alone or in a mixture of two or more. However, the content is preferably 0 to 20% by mass, more preferably 1 to 12% by mass, based on the whole emulsion antifoam composition. When it exceeds 20 mass%, the viscosity of an antifoamer composition may become high and workability | operativity may worsen.

  Moreover, when setting it as an emulsion type antifoamer composition, it is preferable that content of a silicone oil compound is 5-50 mass% of the whole emulsion type antifoamer composition, More preferably, it is 10-40 mass%. is there. If the content of the silicone oil compound is too small, the defoaming performance as the antifoaming composition may be inferior, and if it is too large, the viscosity of the antifoaming composition may be increased and workability may be deteriorated.

  In the emulsion type antifoaming agent composition, water necessary for emulsifying each component such as silicone oil compound, organopolysiloxane modified with polyoxyalkylene group, polyoxyalkylene polymer, nonionic surfactant and the like. The amount is the balance with respect to the total content of each component, preferably 50 to 2,000 parts by mass, more preferably 80 to 400 parts by mass with respect to 100 parts by mass of each component in total. Add to be.

  The emulsion-type antifoaming agent composition is a known method, for example, a mixer / disperser such as a homomixer, homogenizer, colloid mill or the like, while mixing a predetermined amount of each component other than water and heating as necessary. It can be prepared by stirring and emulsifying, but in particular, after a predetermined amount of each component other than water is uniformly mixed and dispersed, a part of water is added, and the remaining after stirring and emulsification A method of adding water and stirring and mixing uniformly is preferable.

  In addition, a small amount of preservatives and bactericides may optionally be added to the emulsion antifoam composition for the purpose of preserving. Specific examples of the preservative / disinfectant include sodium hypochlorite, sorbic acid, potassium sorbate, salicylic acid, sodium salicylate, benzoic acid, sodium benzoate, parabens, isothiazoline compounds and the like. This addition amount is preferably 0 to 0.5% by mass, particularly preferably 0.005 to 0.5% by mass, based on the total emulsion antifoam composition.

  In addition, a small amount of a thickener may be optionally added to the emulsion antifoam composition for the purpose of thickening. Specific examples of the thickener include polyacrylic acid, sodium polyacrylate, acrylic acid / methacrylic acid copolymer, sodium carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, xanthan gum, and guar gum. This addition amount is preferably 0 to 1.0% by mass, and particularly preferably 0.01 to 0.5% by mass, based on the whole emulsion antifoam composition.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, the viscosity is a value at 25 ° C. measured with an Ostwald viscometer, and the average degree of polymerization is a value obtained as a number average degree of polymerization in terms of polystyrene in GPC (gel permeation chromatography) analysis. In the following formulae, Me is a methyl group, and OMe is a methoxy group.

で表される両末端トリメトキシ変性ジメチルポリシロキサン０．３質量部、水０．３質量部をプラネタリーミキサーを使用して１時間混練した。その後、温度を１５０℃に昇温し、引き続き２時間混練した。１００℃以下に冷却後、アルカリ触媒として、水酸化カリウムを３質量％含有するカリウムシリコネート２質量部を添加して１００℃以下で０．１時間混練した後、混練したまま温度を１５０℃に昇温、保持し、昇温してから合計で４時間混練した。１００℃以下に冷却後、コハク酸０．１質量部を添加して３時間混練することで中和し、シリコーンオイルコンパウンド（ａ−１）を得た。
このシリコーンオイルコンパウンド（ａ−１）３０質量部に、平均組成が下記式

で表され、且つ粘度が２，５００ｍｍ²／ｓであるポリオキシアルキレン変性メチルポリシロキサン（ａ−２）７０質量部を室温で混合して自己乳化型消泡剤組成物（Ａ）を調製した。 [Example 1]
As an essentially hydrophobic organopolysiloxane, 100 parts by mass of dimethylpolysiloxane having a viscosity of 10,000 mm ² / s and both ends of the molecular chain blocked with trimethylsilyl groups, as fine powder silica, AEROSIL 300 [Japan Aerosil Co., Ltd., BET specific surface area of 300 m ² / g] as 5 parts by mass, silica surface treatment agent,

The mixture was mixed with 0.3 parts by mass of trimethoxy-modified dimethylpolysiloxane at both ends and 0.3 parts by mass of water using a planetary mixer for 1 hour. Thereafter, the temperature was raised to 150 ° C. and kneading was continued for 2 hours. After cooling to 100 ° C. or lower, 2 parts by weight of potassium siliconate containing 3% by weight of potassium hydroxide as an alkali catalyst was added and kneaded at 100 ° C. or lower for 0.1 hour. The temperature was raised and maintained, and the temperature was raised and kneaded for a total of 4 hours. After cooling to 100 ° C. or lower, 0.1 part by mass of succinic acid was added and neutralized by kneading for 3 hours to obtain a silicone oil compound (a-1).
30 parts by mass of this silicone oil compound (a-1) has an average composition of the following formula

A self-emulsifying antifoam composition (A) was prepared by mixing 70 parts by mass of polyoxyalkylene-modified methyl polysiloxane (a-2) having a viscosity of 2,500 mm ² / s at room temperature. .

[Example 2]
After heating and dissolving a mixture of 20 parts by mass of the silicone oil compound (a-1), 4 parts by mass of sorbitan monostearate and 6 parts by mass of polyoxyethylene (55) monostearate of Example 1, 70 parts by mass of water was added. In addition, the mixture was stirred and emulsified with a homomixer to prepare an emulsion antifoam composition (B).

で表される両末端トリメトキシ変性ジメチルポリシロキサン０．７２質量部をプラネタリーミキサーを使用して１時間混練した。その後、温度を１５０℃に昇温し、引き続き２時間混練した。１００℃以下に冷却後、アルカリ触媒として、水酸化カリウムを３質量％含有するカリウムシリコネート３質量部を添加して１００℃以下で０．１時間混練した後、混練したまま温度を１５０℃に昇温し、１５０℃にて２時間混練した。１００℃以下に冷却後、コハク酸０．１５質量部を添加して３時間混練することで中和し、シリコーンオイルコンパウンド（ｃ−１）を得た。
このシリコーンオイルコンパウンド（ｃ−１）３０質量部に、平均組成が下記式

で表され、且つ粘度が１，０００ｍｍ²／ｓであるポリオキシアルキレン変性メチルポリシロキサン（ｃ−２）５０質量部と、平均組成が下記式
ＨＯ−（Ｃ₂Ｈ₄Ｏ）₂₅−（Ｃ₃Ｈ₆Ｏ）₃₅−Ｈ
で表されるポリオキシアルキレン重合体（ｃ−３）２０質量部を室温で混合して自己乳化型消泡剤組成物（Ｃ）を調製した。 [Example 3]
As an essentially hydrophobic organopolysiloxane, 100 parts by mass of dimethylpolysiloxane having a viscosity of 8,000 mm ² / s and both ends of the molecular chain blocked with trimethylsilyl groups, and as fine powder silica, AEROSIL 200 [Japan Aerosil Co., Ltd., BET specific surface area of 200 m ² / g] as 12 parts by mass, silica surface treatment agent,

0.72 parts by mass of trimethoxy-modified dimethylpolysiloxane represented by the formula was kneaded for 1 hour using a planetary mixer. Thereafter, the temperature was raised to 150 ° C. and kneading was continued for 2 hours. After cooling to 100 ° C. or lower, 3 parts by weight of potassium siliconate containing 3% by weight of potassium hydroxide as an alkali catalyst was added and kneaded for 0.1 hour at 100 ° C. or lower. The temperature was raised and kneaded at 150 ° C. for 2 hours. After cooling to 100 ° C. or less, 0.15 parts by mass of succinic acid was added and neutralized by kneading for 3 hours to obtain a silicone oil compound (c-1).
30 parts by mass of this silicone oil compound (c-1) has an average composition of the following formula

And 50 parts by mass of polyoxyalkylene-modified methyl polysiloxane (c-2) having a viscosity of 1,000 mm ² / s and an average composition of the following formula: HO— (C ₂ H ₄ O) ₂₅ — (C ₃ H ₆ O) ₃₅ -H
A self-emulsifying antifoam composition (C) was prepared by mixing 20 parts by mass of a polyoxyalkylene polymer (c-3) represented by

[Example 4]
After heating and dissolving a mixture of 20 parts by mass of the silicone oil compound (c-1), 6 parts by mass of sorbitan monostearate and 6 parts by mass of polyoxyethylene (55) monostearate of Example 3, 68 parts by mass of water was added. In addition, the mixture was stirred and emulsified with a homomixer to prepare an emulsion antifoam composition (D).

で表される側鎖トリメトキシ変性メチルポリシロキサン０．３質量部、水０．３質量部をプラネタリーミキサーを使用して１時間混練した。その後、温度を１５０℃に昇温し、引き続き２時間混練した。１００℃以下に冷却後、アルカリ触媒として、水酸化カリウムを３質量％含有するカリウムシリコネート３質量部を添加して１００℃以下で０．１時間混練した後、混練したまま温度を１５０℃に昇温し、１５０℃にて２時間混練した。１００℃以下に冷却後、コハク酸０．１５質量部を添加して３時間混練することで中和し、シリコーンオイルコンパウンド（ｅ−１）を得た。
このシリコーンオイルコンパウンド（ｅ−１）３０質量部に、平均組成が下記式

で表され、且つ粘度が２，５００ｍｍ²／ｓであるポリオキシアルキレン変性メチルポリシロキサン（ｅ−２）７０質量部を室温で混合して自己乳化型消泡剤組成物（Ｅ）を調製した。 [Example 5]
As an essentially hydrophobic organopolysiloxane, 100 parts by mass of dimethylpolysiloxane having a viscosity of 10,000 mm ² / s and both ends of the molecular chain blocked with trimethylsilyl groups, as fine powder silica, AEROSIL 300 [Japan Aerosil Co., Ltd., BET specific surface area of 300 m ² / g] as 5 parts by mass, silica surface treatment agent,

Then, 0.3 part by mass of a side chain trimethoxy-modified methylpolysiloxane represented by the formula (1) and 0.3 part by mass of water were kneaded for 1 hour using a planetary mixer. Thereafter, the temperature was raised to 150 ° C. and kneading was continued for 2 hours. After cooling to 100 ° C. or lower, 3 parts by weight of potassium siliconate containing 3% by weight of potassium hydroxide as an alkali catalyst was added and kneaded for 0.1 hour at 100 ° C. or lower. The temperature was raised and kneaded at 150 ° C. for 2 hours. After cooling to 100 ° C. or lower, 0.15 parts by mass of succinic acid was added and neutralized by kneading for 3 hours to obtain a silicone oil compound (e-1).
30 parts by mass of this silicone oil compound (e-1) has an average composition of the following formula

A self-emulsifying antifoam composition (E) was prepared by mixing 70 parts by mass of polyoxyalkylene-modified methylpolysiloxane (e-2) having a viscosity of 2,500 mm ² / s at room temperature. .

[Example 6]
After heating and dissolving a mixture of 20 parts by mass of the silicone oil compound (e-1), 4 parts by mass of sorbitan monostearate and 6 parts by mass of polyoxyethylene (55) monostearate of Example 5, 70 parts by mass of water was added. In addition, the mixture was stirred and emulsified with a homomixer to prepare an emulsion antifoam composition (F).

で表され、且つ粘度が２，５００ｍｍ²／ｓであるポリオキシアルキレン変性メチルポリシロキサン（ｇ−２）７０質量部を室温で混合して自己乳化型消泡剤組成物（Ｇ）を調製した。 [Comparative Example 1]
As an essentially hydrophobic organopolysiloxane, 100 parts by mass of dimethylpolysiloxane having a viscosity of 10,000 mm ² / s and both ends of the molecular chain blocked with trimethylsilyl groups, as fine powder silica, AEROSIL 300 [Japan Aerosil Co., Ltd., BET specific surface area 300 m ² / g] 5 parts by mass, alkali catalyst, 2 parts by mass of potassium siliconate containing 3% by mass of potassium hydroxide, and a planetary mixer in a nitrogen gas atmosphere It was used and kneaded at 150 ° C. for 3 hours. After cooling to 100 ° C. or less, the mixture was neutralized with 0.1 part by mass of succinic acid to obtain a silicone oil compound (g-1).
30 parts by mass of this silicone oil compound (g-1) has an average composition of the following formula

A self-emulsifying antifoam composition (G) was prepared by mixing 70 parts by mass of polyoxyalkylene-modified methylpolysiloxane (g-2) having a viscosity of 2,500 mm ² / s at room temperature. .

[Comparative Example 2]
After heating and dissolving a mixture of 20 parts by mass of the silicone oil compound (g-1), 4 parts by mass of sorbitan monostearate and 6 parts by mass of polyoxyethylene (55) monostearate of Comparative Example 1, 68 parts by mass of water was added. In addition, the emulsion type antifoaming agent composition (H) was prepared by stirring and emulsifying with a homomixer.

  The antifoam compositions (A) to (H) obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were evaluated by the following methods. The results are shown in Table 1.

[Evaluation method]
A 100 mL glass bottle was filled with 50 g of a sulphite pulp waste liquid derived from conifers whose nonvolatile content was adjusted to 8% by mass, and this was preheated at 80 ° C.
Defoaming property (initial):
After adding 0.1% by mass of an antifoaming agent composition as an active ingredient (silicone oil compound) to a test solution preheated at 80 ° C., the mixture was bubbled by shaking for 30 seconds with a shaker. The defoaming property was evaluated by measuring the time until the (liquid level + bubble) and defoaming.
Defoaming property (persistence):
After adding 0.1% by mass of each antifoam composition as an active ingredient (silicone oil compound) to the above sulfite pulp waste liquor at 80 ° C., every predetermined time (after 30 minutes and 120 minutes) The defoaming property was evaluated by measuring the foam height (liquid level + foam) and the time until defoaming by shaking with a shaker for 30 seconds.

Claims (7)

(A) Essentially hydrophobic organopolysiloxane having a viscosity at 25 ° C. of 10 to 100,000 mm ² / s: 100 parts by mass
(B) Fine powder silica having a specific surface area of 50 m ² / g or more: 1 to 30 parts by mass,
(C) Organopolysiloxane represented by the following general formula (I): 0.001 to 5 parts by mass

[Wherein, R ¹ is a methyl group , and X ¹ and X ² are each independently R ¹ or the following formula (i):

(In the formula, R ¹ is the same as above, and R ² may be the same or different, and is a hydrogen atom, or an unsubstituted or substituted, saturated or unsaturated, monovalent hydrocarbon having 1 to 20 carbon atoms. A is an integer of 2 or more, and b is an integer of 1 to 3.)
Y is independently represented by the following formula (ii)

(In the formula, R ¹ and X ² are the same as above, X ³ is the same as X ¹ , and f is an integer of 0 or more.)
And c, d, and e are integers of 0 or more. Provided that at least one of X ¹ to X ³ is Ri Oh a group of the formula (i), organopolysiloxane represented by the formula (I), at least a group represented by the formula (i) 1 Have one. ]
And (C) component is used as a surface treating agent of (B) component, and the oil compound for antifoamers characterized by the above-mentioned. (1) (A) Essentially hydrophobic organopolysiloxane having a viscosity at 25 ° C. of 10 to 100,000 mm ² / s: 100 parts by mass
(B) Fine powder silica having a specific surface area of 50 m ² / g or more: 1 to 30 parts by mass,
(C) Organopolysiloxane represented by the following general formula (I): 0.001 to 5 parts by mass,

[Wherein, R ¹ is a methyl group , and X ¹ and X ² are each independently R ¹ or the following formula (i):

(In the formula, R ¹ is the same as above, and R ² may be the same or different, and is a hydrogen atom, or an unsubstituted or substituted, saturated or unsaturated, monovalent hydrocarbon having 1 to 20 carbon atoms. A is an integer of 2 or more, and b is an integer of 1 to 3.)
Y is independently represented by the following formula (ii)

(In the formula, R ¹ and X ² are the same as above, X ³ is the same as X ¹ , and f is an integer of 0 or more.)
And c, d, and e are integers of 0 or more. Provided that at least one of X ¹ to X ³ is Ri Oh a group of the formula (i), organopolysiloxane represented by the formula (I), at least a group represented by the formula (i) 1 Have one. ]
(D) Water: first step of kneading 0 to 5 parts by mass,
(2) a first compound comprising a second step of heat-treating the kneaded product obtained in the first step;
(3) In the kneaded material obtained in this second step,
(E) Alkali catalyst or acid catalyst: third step of kneading 0.001 to 5 parts by mass;
(4) a second compounding comprising a fourth step of heat treating the kneaded product obtained in the third step;
(5) A method for producing an oil compound for an antifoaming agent, comprising the fifth step of kneading an acid or an alkali as a neutralizing agent in the kneaded product obtained in the fourth step.   An antifoaming composition comprising the oil compound according to claim 1.   The antifoam composition according to claim 3, which is a solution type.   The antifoaming composition according to claim 3, wherein the composition is a self-emulsifying type in combination with an organopolysiloxane modified with a polyoxyalkylene group.   The antifoam composition according to claim 3, which is an emulsion type.   The antifoaming composition according to any one of claims 3 to 6, which is used for an alkaline foaming liquid.