JP2021030222A - Defoaming agent composition - Google Patents

Abstract

To provide a silicone-based defoaming agent having excellent defoaming property and finish appearance when being obliquely viewed.SOLUTION: A defoaming agent composition includes polyoxyalkylene modified silicone A, a nonionic surfactant except the compound A and a silicone oil having a viscosity of 10-100,000 mm2/s at 25°C. The compound A consists of a reactant of a silicone modifier X having formula (1) and hydrogen organopolysiloxane having a specific formula. MH and ML calculated from a chromatogram obtained by the gel permeation chromatography measurement of the silicone modifier X having the formula (1) are satisfied with formula (2). R1O-(AO1)a-[(AO2)b/(EO)c]-R2...(1) 0.20≤ML/MH≤0.60...(2)SELECTED DRAWING: Figure 1

Description

The present invention relates to a defoaming composition containing a polyoxyalkylene modified silicone, a silicone oil and a nonionic surfactant.

Silicone-based defoaming agents have excellent defoaming properties, and are therefore used in a wide range of fields such as fermentation in food production, pulp / paper making, paints, ink / printing, and wastewater. Generally, a silicone-based defoaming agent is a composition obtained by emulsifying and dispersing silicone oil with a surfactant, but from the viewpoint of high emulsifying and dispersing ability and no effect on defoaming property, it can be used as a surfactant. , Polyoxyalkylene-modified silicone is used.

Polyoxyalkylene-modified silicone is a silicone that uses dimethylpolysiloxane as its basic skeleton and has a polyoxyalkylene structure introduced into a part of its methyl group. Since it is easy to control the compatibility of the above, it is preferably used.
For example, as a composition having enhanced defoaming performance, a defoaming agent composition containing a polyether-modified silicone and a silicone oil (Patent Document 1) has been proposed.

However, since the defoaming agent has high hydrophobicity, if the blending amount is increased in water-based applications, repellents and oil spots may occur in the blended system containing an aqueous component such as a dye. For this repellent, a defoaming agent containing a polyoxyalkylene-modified silicone having a polyoxyalkylene chain having a specific structure and a silicone oil has been proposed (Patent Document 2).

Japanese Unexamined Patent Publication No. 5-117352 Japanese Unexamined Patent Publication No. 2004-181415

However, in water-based paints such as acrylic emulsions, many surfactants are blended in order to stably emulsify the resin component for a long period of time, and there are cases where sufficient defoaming properties cannot be obtained. In addition, from the viewpoint of designability, the requirements for the appearance of the coating film are becoming stricter, and the appearance is good at a level that does not cause color unevenness even when viewed from an angle, especially in a thin coating film formed on a smooth surface. Is required.
Therefore, there is a demand for a silicone defoaming agent having excellent defoaming properties and excellent finished appearance when viewed from an angle.

An object of the present invention is to make it possible to provide a silicone-based defoaming agent having excellent defoaming properties and a good finished appearance when viewed from an angle.

As a result of diligent studies in view of the above problems, the present inventor has solved the above problems with hydrogen polysiloxane and polyoxyalkylene derivative-modified silicone having a polyoxyalkylene chain having a specific bias in the molecular weight distribution and an alkenyl group. We have found that it can be solved and arrived at the present invention.

（式（３）中、
ｄは１〜２００、ｅは０〜１００であり、ｅ／ｄは０〜１であり、
Ｒ^３は、炭素数１〜８の炭化水素基であり、
Ｒ^４およびＲ^５は、それぞれ独立して、水素原子または炭素数１〜８の炭化水素基であり、ｅ＝０のときにはＲ^４とＲ^５との少なくとも一つは水素原子である。）

（２） （Ｂ）前記非イオン界面活性剤が、式（４）で表されるシリコーン変性剤Ｙと式（３）で表されるハイドロジェンオルガノポリシロキサンの反応物からなり、式（４）で表されるシリコーン変性剤Ｙのゲル浸透クロマトグラフィー測定により求められるクロマトグラムから算出されるＭ_ＨとＭ_Ｌとが式（５）の関係を満足することを特徴とする、（１）の消泡剤組成物

Ｒ^６Ｏ−（ＡＯ^３）_ｆ−Ｒ^７ ・・・（４）

（式（４）中、
Ｒ^６は炭素数２〜８のアルケニル基を示し、
ＡＯ^３は炭素数２〜４のオキシアルキレン基を示し、
ＡＯ^３の平均付加モル数ｆは１０〜１００であり、
Ｒ^７は水素原子または炭素数１〜４のアルキル基である。）

０．８０≦ Ｍ_Ｌ／Ｍ_Ｈ ≦１．２０ ・・・（５）

（式（４）で表されるシリコーン変性剤Ｙのゲル浸透クロマトグラフィー測定により求められる前記クロマトグラム上の屈折率強度が最大となる極大点ＫからベースラインＢへの垂線の長さをＬとし、屈折率強度がＬ／２０となるクロマトグラム上の２点のうち溶出時間が早いほうを点Ｏとし、溶出時間が遅いほうを点Ｑとし、点Ｏと点Ｑを結ぶ直線Ｇと前記極大点Ｋから前記ベースラインＢへ引いた垂線との交点をＰとしたとき、点Ｏと交点Ｐの距離をＭ_Ｈとし、点Ｑと交点Ｐの距離をＭ_Ｌとする。） The present invention is as follows.
(1) (A) Polyoxyalkylene-modified silicone, (B) (A) Nonionic surfactant other than polyoxyalkylene-modified silicone, and (C) ^{Silicone having a viscosity of 10 to 100,000 mm 2} / s at 25 ° C. An antifoaming composition comprising an oil.

(A) Gel permeation of the silicone denaturant X represented by the formula (1) and the reaction product of the hydrogen organopolysiloxane represented by the formula (3). satisfy the relation of M _H and M _L Togashiki calculated from the chromatogram obtained by chromatography measurement (2), polyoxyalkylene-modified silicone

R ¹ O- (AO ¹ ) _a -[(AO ² ) _b / (EO) _c ] -R ² ... (1)

(In equation (1),
R ¹ represents an alkenyl group having 2 to 8 carbon atoms.
AO ¹ and AO ² each exhibit an oxyalkylene group having 3 to 4 carbon atoms.
EO indicates an oxyethylene group,
The average number of moles a added to AO ^{1 is greater than 0,}
The average number of moles b of AO ^{2 and} the average number of moles c of EO are 0 or more.
The sum of a, b and c is 10 to 100,
When ^{the average number of moles of AO 2} b and the average number of moles of EO c are greater than 0, (AO ² ) _b / (EO) _c ^{is the oxyalkylene group AO 2} having 3 to 4 carbon atoms and the oxy. Indicates that ethylene group EO is randomly added,
R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )

_{0.20 ≦ M L / M H ≦} 0.60 ··· (2)

(The elution time of the two points on the chromatogram where the length of the perpendicular line from the maximum point K where the refractive index intensity on the chromatogram is maximum to the baseline B is L and the refractive index intensity is L / 20. When the earlier point is the point O, the slower dissolution time is the point Q, and the intersection of the straight line G connecting the point O and the point Q and the perpendicular line drawn from the maximum point K to the baseline B is P, the point. the distance between the O and the intersection P and _{M H,} the distance between the point Q and the point of intersection P and _{M L.)}

(In equation (3),
d is 1 to 200, e is 0 to 100, and e / d is 0 to 1.
R ³ is a hydrocarbon group having 1 to 8 carbon atoms.
R ⁴ and R ⁵ are independently hydrogen atoms or hydrocarbon groups having 1 to 8 carbon atoms, and when e = 0, at least one of ^{R 4} and R ^{5 is a hydrogen atom.} )

(2) (B) The nonionic surfactant comprises a reaction product of a silicone modifier Y represented by the formula (4) and a hydrogen organopolysiloxane represented by the formula (3), and the formula (4). and satisfies the relation in M _H calculated from the chromatogram obtained by gel permeation chromatography measurement of the silicone modifier Y represented with M _L Togashiki (5), consumption of (1) Foaming composition

R ⁶ O- (AO ³ ) _f- R ⁷ ... (4)

(In equation (4),
R ⁶ represents an alkenyl group having 2 to 8 carbon atoms.
AO ³ represents an oxyalkylene group having 2 to 4 carbon atoms.
The average number of moles of AO ³ added is 10 to 100, and the average number of moles added is 10 to 100.
R ⁷ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )

_{0.80 ≦ M L / M H ≦} 1.20 ··· (5)

Let L be the length of the perpendicular line from the maximum point K to the baseline B where the refractive index intensity on the chromatogram is maximized, which is obtained by gel permeation chromatography measurement of the silicone modifier Y represented by the formula (4). Of the two points on the chromatogram having a refractive index intensity of L / 20, the one with the earliest dissolution time is designated as the point O, the one with the slowest melting time is designated as the point Q, and the straight line G connecting the points O and the point Q and the maximum when the intersection of the perpendicular drawn to the base line B from point K and is P, a distance between the point O and the intersection P and M _H, the distance between the point Q and the point of intersection P and M _L.)

According to the defoaming agent composition of the present invention, the water-based paint also has excellent defoaming properties, and further, it is possible to impart an excellent finished appearance even when viewed from an angle.

FIG. 1 is a model chromatogram diagram for explaining _ML and _MH defined in the present invention.

(Silicone denaturant X)
The silicone modifier X according to the present invention is composed of a polyoxyalkylene compound represented by the following formula (1).

R ¹ O- (AO ¹ ) _a -[(AO ² ) _b / (EO) _c ] -R ² ... (1)

In the formula (1), a (> 0) ^{indicates the average number of moles of the oxyalkylene group AO 1} having 3 to 4 carbon atoms, and b (≧ 0) indicates the oxyalkylene group AO ^{2 having 3 to 4 carbon atoms.} Indicates the average number of added moles of oxyethylene group EO, and c (≧ 0) indicates the average number of added moles of the oxyethylene group EO. When the sum of a, b and c is less than 10, it is 10 or more because it causes defoaming property and deterioration of the finished appearance when viewed from an angle, but 15 or more is more preferable. Further, when the sum of a, b, and c exceeds 100, the viscosity increases, which adversely affects the production of polyoxyalkylene-modified silicone, which is not preferable. Therefore, the value is 100 or less, preferably 80 or less, and more preferably 60 or less. ..

Further, a is not particularly limited as long as it satisfies a + b + c = 10 to 100, but is preferably 1 or more, and more preferably 3 or more. Further, a is preferably 80 or less, and more preferably 60 or less.
Further, b + c is not particularly limited as long as it satisfies a + b + c = 10 to 100, but is preferably 5 or more, more preferably 10 or more, and most preferably 30 or more. b + c is preferably 80 or less, more preferably 60 or less, and most preferably 40 or less. The ratio of b to c is not particularly limited, but b / c = 1/9 to 9/1 is preferable, 2/8 to 7/3 is more preferable, and 6/4 to 4/6 is even more preferable.

In the formula (1), R ¹ is an alkenyl group having 2 to 8 carbon atoms, and ^{the carbon number of R 1} is more preferably 3 or more, and more preferably 5 or less. From the viewpoint of productivity of the silicone modifier, allyl groups and metharyl groups are more preferable.

In the formula (1), R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and from the viewpoint of productivity of the silicone modifier, a hydrogen atom and a methyl group are preferable, and a hydrogen atom is more preferable.

The silicone modifier X of the present invention is defined by a chromatogram obtained using a differential refractometer in gel permeation chromatography (GPC). This chromatogram is a graph showing the relationship between the refractive index intensity and the elution time. In the silicone modifier X of the present invention, the chromatogram is asymmetrical and satisfies the relationship of the formula (2). In _{addition, M} L / _M
The closer H is to 1, the more symmetrical the shape of the chromatogram.

_{0.20 ≦ M L / M H ≦} 0.60 ···· (2)

Here, FIG. 1 is a model diagram of a chromatogram obtained by gel permeation chromatography of silicone modifier X, where the horizontal axis represents the elution time and the vertical axis represents the refractive index intensity obtained by using a differential refractometer. Is shown.

When the sample solution is injected into the gel permeation chromatograph and developed, elution starts from the molecule with the highest molecular weight, and the elution curve increases as the refractive index intensity increases. After that, when the maximum point K at which the refractive index intensity becomes maximum is passed, the elution curve descends.

Further, in the gel permeation chromatography of the silicone modifier X of the present invention, when there are a plurality of maximum points of the refractive index intensity of the chromatogram, the point having the highest refractive index intensity is defined as the maximum point K. Further, when there are a plurality of maximum points having the same refractive index intensity, the one with the slower elution time is defined as the maximum point K of the refractive index intensity. At this time, peaks caused by the developing solvent used for gel permeation chromatography and pseudo peaks caused by baseline fluctuations caused by the columns and devices used are excluded.

M _L / _{M H,} respectively, calculated from the chromatogram in the following manner.
(1) A perpendicular line is drawn from the maximum point K of the refractive index intensity on the chromatogram to the baseline B, and the length of the perpendicular line is L.
(2) Of the two points on the chromatogram having a refractive index intensity of L / 20, the one with the earlier elution time is designated as point O, and the one with the slower elution time is designated as point Q.
(3) Let P be the intersection of the straight line G connecting the points O and Q and the perpendicular line drawn from the maximum point K of the refractive index intensity to the baseline B.
(4) point O and the intersection point P distance _{M H} of the distance of an intersection P and the point Q and _{M L.}

Silicone modifier X of the present invention _is M L / _{M H} satisfies _{0.20 ≦ M L / M H ≦} 0.60. When M L _/ M _H is greater than 0.60, the distribution of the polyoxyalkylene chain of the structure of the polyoxyalkylene-modified silicone is reduced, it is not a good finished appearance when viewed from the defoaming property and the oblique. In this _respect, the M L / _{M H} is 0.60 or less, more preferably be 0.50 or less.

Also, as M L _/ M _H is reduced, the bias of the high molecular weight side is increased in the molecular weight distribution, and increase in viscosity derived therefrom seen. When M L _/ M _H is less than 0.20, too high viscosity, undesirably a negative effect on the production of the polyoxyalkylene-modified silicone. From this point of _view, but 0.20 or more M L / _{M H,} more preferably it is 0.30 or more.

In the present invention, _{gel permeation chromatography (GPC) for determining ML} and _MH is a system dedicated to SHODEX® GPC101 GPC, a differential refractometer of SHODEX RI-71s, and a guard column of SHODEX.
Three KF-G and HODEX KF804L were continuously mounted as a column, and tetrahydrofuran was flown as a developing solvent at a flow rate of 1 ml / min at a column temperature of 40 ° C., and 0.1 ml of a 0.1 wt% tetrahydrofuran solution of the obtained reaction product was added. Inject and use a BORWIN GPC calculation program to obtain a chromatogram represented by refractive index intensity and elution time.

The silicone modifier X of the present invention is ring-opened and added with an alkylene oxide having 3 to 4 carbon atoms in the presence of a composite metal cyanide catalyst (hereinafter abbreviated as DMC catalyst), or subsequently has 3 to 4 carbon atoms. It is produced by further ring-opening addition of alkylene oxide and ethylene oxide.

In the production of the silicone modifier X, preferably, an initiator having 2 to 8 carbon atoms and one hydroxyl group in the molecule and a DMC catalyst are added to the reaction vessel, and the mixture is stirred in an inert gas atmosphere. Addition polymerization is carried out by continuously or intermittently adding an alkylene oxide having 3 to 4 carbon atoms. The alkylene oxide having 3 to 4 carbon atoms may be added under pressure, or may be added under atmospheric pressure.

At this time, the average supply rate of alkylene oxide is not limited, but it is desirable to change it depending on the amount of alkylene oxide charged. Specifically, the speed (supply amount per unit time) while _{supplying 5 to 20 wt% of the total supply amount of alkylene oxide is V 1} , and the speed while supplying 20 to 50 wt% of the total supply amount of alkylene oxide is V 1. When V ₂ and 50 to 100 wt% of the total supply of alkylene oxide are supplied as V ₃ , V ₁ / V ₂ = 1.1 to 2.0, V ₂ / V ₃ = 1. It is preferable to control the average supply rate of the alkylene oxide so as to be 1 to 1.5.

The reaction temperature is preferably 50 ° C. to 150 ° C., more preferably 80 ° C. to 120 ° C. If the reaction temperature is higher than 150 ° C., the catalyst may be deactivated. When the reaction temperature is lower than 50 ° C., the reaction rate is slow and the productivity is poor.

The amount of water contained in the initiator and the alkylene oxide is not particularly limited, but it is desirable that the amount of water contained in the initiator is 0.5 wt% or less and that of the alkylene oxide is 0.01 wt% or less. ..

The amount of the DMC catalyst used is not particularly limited, but is preferably 0.0001 to 0.1 wt%, more preferably 0.001 to 0.05 wt% with respect to the silicone modifier to be produced. The DMC catalyst may be introduced into the reaction system all at once at the beginning, or may be introduced in a sequential manner. After completion of the polymerization reaction, the composite metal complex catalyst is removed. The catalyst can be removed by a known method such as filtration, centrifugation, or treatment with a synthetic adsorbent.

A known DMC catalyst can be used in the present invention, and can be represented by, for example, the formula (6).

Mg [M'x (CN) y] h (H ₂ O) i · (R ⁸ ) j
... (6)

In formula (6), M and M'are metals, R ⁸ is an organic ligand, g, h, x and y are positive integers that vary depending on the valence and coordination number of the metal, and i and j are. It is a positive integer that changes depending on the coordination number of the metal.

Examples of the metal M include Zn (II), Fe (II), Fe (III), Co (II), Ni (II), Al (III), Sr (II), Mn (II), Cr (III), Examples thereof include Cu (II), Sn (II), Pb (II), Mo (IV), Mo (VI), W (IV), W (VI), and Zn (II) is preferably used.

Examples of the metal M'are Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn (III), Ni (II). , V (IV), V (V) and the like, and among them, Fe (II), Fe (III), Co (II) and Co (III) are preferably used.

As the organic ligand R ⁸ , alcohol, ether, ketone, ester or the like can be used, and alcohol is more preferable. Preferred organic ligands are water-soluble, and specific examples thereof include tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, N, N-dimethylacetamide, ethylene glycol dimethyl ether (glyme), and diethylene glycol dimethyl ether (). Jiglime) and the like. Particularly preferably, it is Zn ₃ [Co (CN) ₆ ] ₂ coordinated with tert-butyl alcohol.

A silicone modifier produced using a DMC catalyst is a silicone modifier having an alkyl group having 1 to 4 carbon atoms at the terminal represented by the formula (1) by a Williamson etherification reaction with an organic halide in the presence of a base. Can be used in the manufacture of. Specific examples of the base used in the etherification reaction include sodium hydroxide, potassium hydroxide, sodium hydride, potassium carbonate and the like. The organic halide is a compound in which an alkyl group having 1 to 4 carbon atoms and a halogen atom are bonded. Specific examples include methyl chloride and butyl chloride.

Further, in the production of a silicone modifier, an initiator having an alkyl group having 1 to 4 carbon atoms and one hydroxyl group in the molecule and a DMC catalyst may be used for addition polymerization of alkylene oxide. In that case, after addition polymerization of the alkylene oxide, in the presence of a base, a Williamson etherification reaction of a compound in which an alkenyl group having 3 to 5 carbon atoms and a halogen atom are bonded is carried out by a Williamson etherification reaction, and the terminal having 1 to 1 carbon atoms represented by the formula (1). A silicone modifier having an alkyl group of 4 can be produced. Specific examples of the organic halide include allyl chloride, allyl iodide, metallyl chloride, allyl bromide and the like.

(Polyoxyalkylene modified silicone)
The polyoxyalkylene-modified silicone of the present invention comprises a reaction product of a silicone modifier X represented by the formula (1) and a hydrogen organopolysiloxane represented by the formula (3).

(Hydrogen Organopolysiloxane)
In the formula (3), d is 1 to 200 and e is 0 to 100. From the viewpoint of defoaming property and the appearance of the finished product when viewed from an angle, d is 200 or less, preferably 150 or less, and more preferably 100 or less. Further, d is 1 or more, but 2 or more is more preferable. Further, e is 100 or less, preferably 50 or less, and more preferably 20 or less, from the viewpoint of defoaming property and the finished appearance when viewed from an angle. The e / d is 1 or less, preferably 0.4 or less, and more preferably 0.2 or less, from the viewpoint of defoaming property and the appearance of the finished product when viewed from an angle.

R ³ represents a hydrocarbon group having 1 to 8 carbon atoms. Examples of such a hydrocarbon group include an alkyl group, a cycloalkyl group and an alkenyl group, and an alkyl group is preferable. Specific compound names include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group and the like, and a methyl group is particularly preferable.

R ⁴ and R ⁵ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and are preferably a hydrocarbon group having 1 to 8 carbon atoms. Examples of such a hydrocarbon group include an alkyl group, a cycloalkyl group and an alkenyl group, and an alkyl group is preferable. Specific examples of the compound name include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group and the like, and a methyl group is preferable. When c = 0, ^{at least one of R 4} or R ⁵ is a hydrogen atom.

((B) Nonionic surfactant)
The (B) nonionic surfactant of the present invention is a nonionic surfactant other than (A). The nonionic surfactant (B) may be any of polyoxyalkylene-modified silicone, sorbitan fatty acid ester, polyoxyethylene cured castor oil and the like, and polyoxyalkylene-modified silicone is preferable. Further, two or more kinds can be mixed and used.

In a preferred embodiment, the polyoxyalkylene modified silicone comprises a reactant of the silicone modifier Y represented by the following formula (4) and the hydrogen organopolysiloxane represented by the formula (3). ..

R ⁶ O- (AO ³ ) _f- R ⁷ ... (4)

In the formula (4), f represents the average number of moles of the ^{oxyalkylene group AO 3 having 2 to 4 carbon atoms.} When f is less than 10, it is set to 10 or more because the defoaming property and the finished appearance when viewed from an angle are deteriorated, but 15 or more is more preferable. Further, when d exceeds 100, the viscosity increases, which adversely affects the production of polyoxyalkylene-modified silicone, which is not preferable. Therefore, the viscosity is preferably 100 or less, more preferably 80 or less, and even more preferably 60 or less.

In the formula (4), R ⁶ is an alkenyl group having 2 to 8 carbon atoms, and ^{the carbon number of R 6} is more preferably 3 or more, and more preferably 5 or less. From the viewpoint of productivity of the silicone modifier, allyl groups and metharyl groups are more preferable.

In the formula (4), R ⁷ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and from the viewpoint of productivity of the silicone modifier, a hydrogen atom and a methyl group are preferable, and a hydrogen atom is more preferable.

Silicone modifier Y of the present _invention has M L / _{M H} satisfies _{0.80 ≦ M L / M H ≦} 1.20, preferably _{0.85 ≦ M L / M H ≦} 1.15, more preferably _{0.90 ≦ M L / M H ≦} 1.15, particularly preferably _{0.90 ≦ M L / M H ≦} 1.10.

((C) Silicone oil)
Silicone oil of the present invention may be any of linear and branched, a viscosity of 10~100,000mm ² / s at 25 ℃, 50~50,000mm ² from the viewpoint of antifoaming property and workability / It is preferably s. Further, two or more kinds can be mixed and used.

(Defoamer composition)
The content of each component of the defoaming agent composition of the present invention is not particularly limited as long as each component is contained as an essential component, but the component (A) is preferably 10 to 98% by mass. It is more preferably 20 to 90% by mass, still more preferably 30 to 80% by mass.
The component (B) is preferably 1 to 89% by mass, more preferably 10 to 80% by mass, and further preferably 20 to 70% by mass.
The component (C) is preferably 1 to 20% by mass, more preferably 2 to 15% by mass, and further preferably 3 to 10% by mass.
The defoaming agent composition of the present invention has a mass ratio ((A) / (B)) of (A) polyoxyalkylene-modified silicone and a nonionic surfactant other than (B) and (A), preferably 10 /. It is 90 to 99/1, more preferably 20/80 to 90/10, and even more preferably 30/70 to 80/20.

In the defoaming agent composition of the present invention, the mass ratio of the sum of (A) and (B) and (C) ^{a silicone oil having a viscosity of 10 to 100,000 mm 2} / s at 25 ° C. ([(A) + (B) )] / (C)) is 80/20 to 99/1, preferably 85/15 to 98/2, and even more preferably 90/10 to 97/3.

The antifoaming agent composition of the present invention may be diluted with a solvent such as water or acetone before use in order to make it easy to handle and add.

The defoaming agent composition of the present invention may further contain other components such as powders such as silica as long as the effects of the present invention are not impaired.

Among these, it is preferable to blend powder from the viewpoint of defoaming property. The powder may be either organic or inorganic powder, and for example, hydrophilic silica, hydrophobic silica, natural wax, synthetic wax, fatty acid amide, metal soap, titanium dioxide, aluminum oxide, quartz powder, resin powder and the like. is there. Preferred are natural silica waxes, synthetic waxes, fatty acid amides and metal soaps, more preferably hydrophilic silicas and hydrophobic silicas.

The hydrophilic silica may be either wet silica or dry silica, and precipitated silica, silica xerogel, and fumed silica can be used untreated. As the hydrophobic silica, one obtained by hydrophobizing the hydrophilic silica with an organosilicon compound such as organopolysiloxane can be used by a conventionally known method. Further, it is preferable that the specific surface area by the BET method is 100 m ^{2 / g or more.}
These powders may be used in the form of oil compounds pretreated with silicone oil.

Hereinafter, the present invention will be described in detail with reference to examples, but the technical scope of the present invention is not limited thereto. The synthetic product was analyzed by the method shown below.

(Analysis method)
Degree of unsaturation: Analysis was performed by a method conforming to JIS K 1557-3.
Kinematic viscosity: Analysis was performed by a method conforming to JIS K 2283.
Gel permeation chromatography:
SHODEX GPC101 GPC dedicated system as a system, SHODEX as a differential refractometer
RI-71S, SHODEX KF-GS as a guard column, and HODEX KF804L as a column were continuously mounted, and the column temperature was 40 ° C., and tetrahydrofuran was flown as a developing solvent at a flow rate of 1 ml / min, and the resulting reaction product was 0.1. Analysis was performed by injecting 0.1 ml of a weight% tetrahydrofuran solution and using a BORWIN GPC calculation program to obtain chromatograms represented by refractive index intensity and elution time.

(Synthesis Example 1: Synthesis of Composite Metal Cyanide Complex (DMC) Catalyst)
In an aqueous solution of 2.0ml containing zinc chloride 2.1 g, an aqueous solution of potassium hexacyanocobaltate _K 3 Co _{(CN) 6} and comprises 0.84 g 15 ml, was added dropwise over 15 minutes with agitation at 40 ° C.. After completion of the dropping, 16 ml of water and 16 g of tert-butyl alcohol were added, the temperature was raised to 70 ° C., and the mixture was stirred for 1 hour. After cooling to room temperature, a filtration operation (first filtration) was performed to obtain a solid. To this solid, 14 ml of water and 8.0 g of tert-butyl alcohol were added, and the mixture was stirred for 30 minutes and then filtered (second filtration) to obtain a solid.

Further, once again, 18.6 g of tert-butyl alcohol and 1.2 g of methanol were added to this solid, and after stirring for 30 minutes, a filtration operation (third filtration) was performed, and the obtained solid was dried at 40 ° C. under reduced pressure for 3 hours. Then, 0.7 g of DMC catalyst was obtained.

(Synthesis Example 2: Synthesis of Silicone Denaturer X-1)
700 g of allyl alcohol (manufactured by Showa Denko) and 7 g of sodium methylate (manufactured by Nippon Soda) were charged into a 5-liter autoclave equipped with a stirrer, a nitrogen introduction pipe, and a thermocouple. After nitrogen substitution, the temperature was raised to 100 ° C., and 2,150 g of propylene oxide (manufactured by Sumitomo Chemical Co., Ltd.) was charged over 20 hours under the condition of 0.5 MPa or less. The residual propylene oxide was removed by performing a reduced pressure treatment at 75 to 85 ° C. and −0.097 MPa (gauge pressure) for 1 hour. After neutralization with hydrochloric acid, water is removed by nitrogen bubbling at 80 ° C., and 14 g each of Kyoward # 300 and # 700 (manufactured by Kyowa Chemical Industry Co., Ltd.) is added, and then 80 ° C., -0.097 MPa (gauge). Pressure) Below, adsorption treatment was carried out in nitrogen bubbling for 1 hour, and 2,360 g of tripropylene glycol allyl ether (unsaturation: 4.11 meq / g, Mn: 240) was obtained by filtration.

Subsequently, 400 g of tripropylene glycol allyl ether and 0.05 g of the DMC catalyst obtained in Synthesis Example 1 were charged into an autoclave having a capacity of 5 liters equipped with a stirrer, a nitrogen introduction tube, and a thermocouple. After nitrogen substitution, the temperature was raised to 120 ° C., and 50 g of propylene oxide was charged over 1 hour under the conditions of 0.3 MPa or less. At this time, the changes over time in the pressure and temperature in the reaction vessel were measured. After 5 hours, the pressure in the reaction vessel decreased sharply. Then, while keeping the inside of the reaction vessel at 120 ° C., propylene oxide was gradually added under the condition of 0.6 MPa or less, and a total of 2,050 g of propylene oxide was continuously pressurized and added under stirring. At this time, the time required to introduce 2,050 g of propylene oxide was 10 hours. After decompression treatment at 75 to 85 ° C. and −0.097 MPa (gauge pressure) for 1 hour, filtration was performed to obtain 2,400 g of silicone denaturant X-1. The degree of unsaturation of the obtained denaturant was 0.65 meq / g and Mn: 1,440. _{Further, when ML} / _MH was determined from the chromatogram obtained by the measurement of gel permeation chromatography, it was 0.42.

(Synthesis Example 3: Synthesis of Silicone Denaturer X'-1)
An autoclave having a capacity of 5 liters equipped with a stirrer, a nitrogen introduction tube, and a thermocouple was charged with 100 g of allyl alcohol and 5 g of sodium methylate. After nitrogen substitution, the temperature was raised to 100 ° C., and 3,300 g of propylene oxide was charged over 50 hours under the condition of 0.5 MPa or less. The residual propylene oxide was removed by performing a reduced pressure treatment at 75 to 85 ° C. and −0.097 MPa (gauge pressure) for 1 hour. After neutralization with hydrochloric acid, remove water at 80 ° C. in nitrogen bubbling, add 3.3 g each of Kyoward # 300 and # 700, and then add 3.3 g each at 80 ° C., -0.097 MPa (gauge pressure) or less. The adsorption treatment was carried out in nitrogen bubbling for 1 hour, and the silicone modifier X'-1 (unsaturation: 0.64 meq / g, Mn: 1,460) was obtained in an amount of 3,150 g by filtration. _{Further, when ML} / _MH was obtained from the chromatogram obtained by the measurement of gel permeation chromatography, it was 1.15.

(Synthesis Example 4: Synthesis of Silicone Denaturer Y-1)
80 g of allyl alcohol and 4 g of sodium methylate were charged into a 5 liter capacity autoclave equipped with a stirrer, a nitrogen introduction tube, and a thermocouple. After nitrogen substitution, the temperature was raised to 100 ° C., and 2,050 g of propylene oxide and 1,500 g of ethylene oxide were charged over 50 hours under the conditions of 0.5 MPa or less. The pressure was reduced at 75 to 85 ° C. and −0.097 MPa (gauge pressure) for 1 hour to remove residual propylene oxide and ethylene oxide. After neutralization with hydrochloric acid, water is removed by nitrogen bubbling at 80 ° C., and after adding 3.6 g each of Kyoward # 300 and # 700, 80 ° C., −0.097 MPa (gauge pressure) or less, The adsorption treatment was carried out in nitrogen bubbling for 2 hours, and the silicone modifier Y-1 (unsaturation: 0.44 meq / g, Mn: 2,100) was obtained in an amount of 3,450 g by filtration. _{Further, when ML} / _MH was obtained from the chromatogram obtained by the measurement of gel permeation chromatography, it was 1.06.

(Synthesis Example 5: Synthesis of Polyoxyalkylene Modified Silicone A-1)
Hydrogendimethylpolysiloxane (HMS-082 (manufactured by Gelest), SiH equivalent per gram = 1.08 meq / g in a 300 ml four-necked flask equipped with a stirrer, nitrogen blowing tube, thermocouple and cooling tube. , E = 75, f = 6.5) 65 parts by mass and the silicone modifier X-1 (151 parts by mass, unsaturated equivalent; 0.65 meq / g) synthesized in Synthesis Example 2 were charged, and platinum chloride was used as a catalyst. An isopropyl alcohol solution (1 × 10 ^-3 mol / liter) of acid hexahydrate was prepared so as to have a platinum equivalent of 50 ppm, and the reaction was carried out at 90 ° C. with stirring under a nitrogen atmosphere. Sampling was performed, an isopropyl alcohol solution of N / 10 potassium hydroxide was added, and the reaction was continued until hydrogen gas was no longer generated. By FT-IR measurement, the absorption of ^{2100 to 2300 cm -1 derived from the SiH group disappeared.} After confirming that, a polyoxyalkylene-modified silicone A-1 having a kinematic viscosity of 105 Pa · s at 100 ° C. was obtained.

(Synthesis Example 6: Synthesis of Polyoxyalkylene Modified Silicone A'-1)
Similar to Synthesis Example 5 except that the silicone modifier X'-1 (154 parts by mass, unsaturated equivalent; 0.64 meq / g) synthesized in Synthesis Example 3 was used instead of the silicone modifier X-1. The operation was carried out to obtain a polyoxyalkylene-modified silicone A'-1 having a kinematic viscosity of 100 ° C. and a kinematic viscosity of 102 Pa · s.

(Synthesis Example 7: Synthesis of Nonionic Surfactant B-1)
The operation was the same as in Synthesis Example 5 except that the silicone modifier Y-1 (223 parts by mass, unsaturated equivalent; 0.44 meq / g) synthesized in Synthesis Example 4 was used instead of the silicone modifier X-1. To obtain a nonionic surfactant B-1 having a kinematic viscosity of 100 ° C. and a kinematic viscosity of 295 Pa · s.

(Synthesis Example 8: Synthesis of Silicone Denaturer X-2)
400 g of tripropylene glycol allyl ether and 0.05 g of the composite metal cyanide complex catalyst obtained in Synthesis Example 1 were charged into a 5 liter capacity autoclave equipped with a stirrer, a nitrogen introduction tube, and a thermocouple. After nitrogen substitution, the temperature was raised to 120 ° C., and 50 g of propylene oxide was charged over 1 hour under the conditions of 0.3 MPa or less. At this time, the changes over time in the pressure and temperature in the reaction vessel were measured. After 5 hours, the pressure in the reaction vessel decreased sharply. Then, while keeping the inside of the reaction vessel at 120 ° C., 1,650 g of propylene oxide and 1,500 g of ethylene oxide were gradually added under the condition of 0.6 MPa or less, and continuously pressurized and added over 13 hours under stirring. did. After decompression treatment at 75 to 85 ° C. and −0.097 MPa (gauge pressure) for 1 hour, filtration was performed to obtain 3,480 g of silicone denaturant X-2. The degree of unsaturation of the obtained denaturant was 0.44 meq / g and Mn: 2,080.
_{Further, when ML} / _MH was determined from the chromatogram obtained by the measurement of gel permeation chromatography, it was 0.38.

(Synthesis Example 9: Synthesis of Polyoxyalkylene Modified Silicone A-2)
The operation was the same as in Synthesis Example 5 except that the silicone modifier X-2 (224 parts by mass, unsaturated equivalent; 0.44 meq / g) synthesized in Synthesis Example 8 was used instead of the silicone modifier X-1. To obtain a polyoxyalkylene-modified silicone A-2 having a kinematic viscosity of 310 Pa · s at 100 ° C.

(Preparation of antifoaming agent composition: Examples 1 to 4, Comparative Examples 1 to 3)
The antifoaming agent composition shown in Table 3 was prepared by the following preparation method. Specifically, under room temperature conditions, the A, B, and C components of Examples and Comparative Examples were stirred until they became uniform.

-Component A or component A': Polyoxyalkylene-modified silicone (A-1, A-2, A'-1)
-Component B: Nonionic surfactant (B-1) other than component A
-C component: Silicone oil with a viscosity of 1,000 mm ² / s (KF-96-1000cs, manufactured by Shin-Etsu Chemical Co., Ltd.)

(Evaluation of defoaming property of defoaming agent composition)
100 parts by weight of 60 mass% acrylic resin emulsion (Aron AN1417, manufactured by Toa Synthetic) is placed in a 300 mL glass transparent container, and 0.1 parts by weight of a 10 wt% acetone solution of each defoaming agent composition is added dropwise thereto, and then 10 parts are added. Stirring (3000 rpm) was continued with a homomixer for 1 minute. The defoaming property was evaluated by comparing the liquid levels before stirring, immediately after stirring, and after 1 hour.

Evaluation criteria immediately after the end of stirring "◎": Difference in liquid level from before stirring is less than 2 cm "○": Difference in liquid level from before stirring is 2 cm or more and less than 2.5 cm "△": Liquid before stirring Surface difference is 2.5 cm or more and less than 4 cm

Evaluation criteria 1 hour after the end of stirring "◎": Difference in liquid level from before stirring is less than 1 cm "○": Difference in liquid level from before stirring is 1 cm or more and less than 1.5 cm "△": Before stirring Liquid level difference of 1.5 cm or more and less than 2 cm

(Evaluation of the finished appearance of the coating film)
The sample used in the defoaming property evaluation was used to evaluate the finished appearance. Using a brush, the sample was thinly applied onto a glass plate washed and dried with a solvent, and after drying, the presence or absence of unevenness in the coating film was visually confirmed from angles of 90 ° and 45 ° with respect to the glass plate.

"○": Visually from 90 ° and 45 °, there is no unevenness.
"△": There is no unevenness when viewed from 90 °, but there is unevenness when viewed from 45 °.

In Examples 1 to 4, the difference in liquid level between before stirring, immediately after stirring, and after 1 hour is small, the defoaming property is excellent, unevenness is not observed visually from 45 °, and the finished appearance is excellent. It was. In the control example to which no antifoaming agent was added, the difference in liquid level before and after stirring was 4 cm.

In Comparative Example 1, a component A'-1 having a large _ML / _{MH is used instead of the component (A).} As a result, the defoaming property is excellent, but unevenness is observed visually from 45 °, and the finished appearance is inferior.
In Comparative Example 2, although the component (C) was not contained, the defoaming property was inferior.
In Comparative Example 3, although the component (A) is not contained, the defoaming property immediately after the completion of stirring is inferior, and unevenness is observed visually from 45 °, and the finished appearance is inferior.

Claims (2)

Contains (A) polyoxyalkylene-modified silicone, (B) (A) nonionic surfactant other than polyoxyalkylene-modified silicone, and (C) silicone oil having a ^{viscosity of 10 to 100,000 mm 2 / s at 25 ° C.} A defoaming agent composition, characterized in that it does.

(A) Gel permeation of the silicone denaturant X represented by the formula (1) and the reaction product of the hydrogen organopolysiloxane represented by the formula (3). satisfy the relation of M _H and M _L Togashiki calculated from the chromatogram obtained by chromatography measurement (2), polyoxyalkylene-modified silicone

R ¹ O- (AO ¹ ) _a -[(AO ² ) _b / (EO) _c ] -R ² ... (1)

(In equation (1),
R ¹ represents an alkenyl group having 2 to 8 carbon atoms.
AO ¹ and AO ² each exhibit an oxyalkylene group having 3 to 4 carbon atoms.
EO indicates an oxyethylene group,
The average number of moles a added to AO ^{1 is greater than 0,}
The average number of moles b of AO ^{2 and} the average number of moles c of EO are 0 or more.
The sum of a, b and c is 10 to 100,
When ^{the average number of moles of AO 2} b and the average number of moles of EO c are greater than 0, (AO ² ) _b / (EO) _c ^{is the oxyalkylene group AO 2} having 3 to 4 carbon atoms and the oxy. Indicates that ethylene group EO is randomly added,
R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )

_{0.20 ≦ M L / M H ≦} 0.60 ··· (2)

(The elution time of the two points on the chromatogram where the length of the perpendicular line from the maximum point K where the refractive index intensity on the chromatogram is maximum to the baseline B is L and the refractive index intensity is L / 20. When the earlier point is the point O, the slower dissolution time is the point Q, and the intersection of the straight line G connecting the point O and the point Q and the perpendicular line drawn from the maximum point K to the baseline B is P, the point. the distance between the O and the intersection P and _{M H,} the distance between the point Q and the point of intersection P and _{M L.)}

(In equation (3),
d is 1 to 200, e is 0 to 100, and e / d is 0 to 1.
R ³ is a hydrocarbon group having 1 to 8 carbon atoms.
R ⁴ and R ⁵ are independently hydrogen atoms or hydrocarbon groups having 1 to 8 carbon atoms, and when e = 0, at least one of ^{R 4} and R ^{5 is a hydrogen atom.} )
(B) The nonionic surfactant comprises a reaction product of a silicone modifier Y represented by the formula (4) and a hydrogen organopolysiloxane represented by the formula (3), and is represented by the formula (4). and satisfies the relation of M _H and M _L Togashiki calculated from the chromatogram obtained by gel permeation chromatography measurement of the silicone modifier Y (5) that, according to claim 1, wherein the defoaming agent Composition

R ⁶ O- (AO ³ ) _f- R ⁷ ... (4)

(In equation (4),
R ⁶ represents an alkenyl group having 2 to 8 carbon atoms.
AO ³ represents an oxyalkylene group having 2 to 4 carbon atoms.
The average number of moles of AO ³ added is 10 to 100, and the average number of moles added is 10 to 100.
R ⁷ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )

_{0.80 ≦ M L / M H ≦} 1.20 ··· (5)

Let L be the length of the perpendicular line from the maximum point K to the baseline B where the refractive index intensity on the chromatogram is maximized, which is obtained by gel permeation chromatography measurement of the silicone modifier Y represented by the formula (4). Of the two points on the chromatogram having a refractive index intensity of L / 20, the one with the earliest dissolution time is designated as the point O, the one with the slowest melting time is designated as the point Q, and the straight line G connecting the points O and the point Q and the maximum when the intersection of the perpendicular drawn to the base line B from point K and is P, a distance between the point O and the intersection P and M _H, the distance between the point Q and the point of intersection P and M _L.)

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