JP2002066205A - Foam inhibitor composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a foam inhibitor composition that is excellent in foam inhibition, water dispersability and stability. SOLUTION: This foam inhibitor composition comprises the following (A) and (B) components as main components: (A) 30-90 wt.% of an oil compound comprising following (i) and (ii) components as main components; (i) 80-99.9 wt.% of an organopolysiloxane comprising R13SiO1/2 unit, R12SiO2/2 unit and R1SiO3/2 unit (provided that R1s denote each a same or different mono-valent organic group having a carbon number of 1-20), having a structure with a constitutional ratio; R13SiO1/2 unit, R12SiO2/2 unit, R1SiO3/2 unit = 0.1-5/90-99.8/0.1-5 (mole %), and having a viscosity at 25 deg.C of 1,000-1,000,000 mPa.S and (ii) 0.1-20 wt.% of silica fine powder; and (B) 10-70 wt.% of one or more dialkylpolysiloxanes each having a viscosity at 25 deg.C of 2-500 mPa.S and capable of having the viscosity of a mixture when mixed with (A) of 5,000 mPa.S or less.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foam inhibitor composition having excellent foam suppressing properties, workability and stability.

[0002]

2. Description of the Related Art Silicone-based antifoaming agents are superior in defoaming properties to other types, and are therefore used for synthetic resins, synthetic rubbers, oils and fats, fermentation, food, fiber, and petroleum. Used in a wide range of industrial fields such as pharmaceuticals. Among them, foam suppressant compositions suitable under severe conditions such as high temperature, high pH and high shear force have been proposed (JP-B-52-19836, JP-B-52-22638, JP-B-52-22638, Publication No. 55-23084). However, in these, further improvement of the foam suppressing property has been desired. In response to this requirement, compositions comprising an organopolysiloxane into which a crosslinking unit has been introduced as a main component have been proposed (JP-B-3-14481, JP-B-3-14482).
JP-A-63-147507, JP-A-1-3175
No. 05, JP-A-3-188905), all of which have poor stability.

More recently, it has been proposed that an organopolysiloxane having a branched unit introduced into its structure is used as a main component of an oil compound (Japanese Patent Laid-Open No. Hei 5-27).
1689, JP-A-8-196811, JP-A-8-3
09104 publications). As a result, a considerable improvement in foam suppressing properties was recognized, but it was not yet satisfactory.

[0004] Accordingly, an object of the present invention is to provide a foam inhibitor composition having excellent foam suppressing properties, workability and stability.

[0005]

Means for Solving the Problems and Embodiments of the Invention In order to achieve the above object, the present invention provides a foam inhibitor composition comprising the following components (A) and (B) as main components. (A) below (i) and (ii) component oil compound 30-90 wt% of a main _{^{component, (i) R 1 3 SiO}} 1/2 units, R ¹ ₂ SiO _2/2 units, R ¹ SiO _{3 / 2} unit (and however, R ¹ is the same or different monovalent organic group having 1 to 20 carbon atoms with each other), R ¹ ₃ SiO _1/2 units / R ¹ ₂ SiO _2/2 units / R ¹ SiO _3/2 unit = 0.1-5 / 90-99.8 / 0.1-5 (mol%) It has a structure and the viscosity at 25 ° C is 1,000-1,000,000 mPa · S. 80 to 99.9% by weight of an organopolysiloxane, (ii) 0.1 to 20% by weight of finely divided silica, (B) a viscosity at 25 ° C. of 2 to 500 mPa · S, and a mixture with the component (A). One or more dialkyl polysiloxanes, which, when combined, can result in a mixture of 5,000 mPa · S or less 0 to 70% by weight.

In this case, the viscosity at 25 ° C. represented by the following structural formula (1) is from 500 to 100,000 mPa · S with respect to 100 parts by weight of the total amount of the components (A) and (B). Polyoxyalkylene-modified silicone oil 0.1 to
It is preferable to add 50 parts by weight.

[0007]

Embedded image

Wherein R ² represents the same or different monovalent organic group having 1 to 20 carbon atoms, and A represents —R ³ —O (CH ₂ CH ₂ O) _p (CH ₂ CH (CH ₃ ) O)
_q- R ⁴ (where R ³ represents a divalent hydrocarbon group having 1 to 4 carbon atoms, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group or an isocyanic acid group, and p and q represent 3 ≦ p + q ≦ 100, 30
It is a number that satisfies / 70 ≦ p / q ≦ 100/0. ) Is a polyoxyalkylene-containing group. a and b are 10 ≦ a + b ≦ 1,000, 50/50 ≦ a / b ≦ 99
It is a number that satisfies / 1. The foam inhibitor composition of the present invention exhibits excellent foam suppressing properties, and is excellent in workability and stability.

Hereinafter, the present invention will be described in more detail.

[0010] The oil compound as the component (A) of the foam inhibitor composition of the present invention is a main component for imparting the foam inhibitory property to this composition. A) organopolysiloxane and (ii) finely divided silica.

The organopolysiloxane (i) used herein comprises the following structural units.

[0012] ^{_{[R 1 3 SiO 1/2] [}} R 1 2 SiO 2/2] [R 1 SiO 3/2] This R ¹ is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group , Heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, alkyl group such as octadecyl group, cycloalkyl group such as cyclohexyl group, alkenyl group such as vinyl group, allyl group, phenyl group, Aryl groups such as a tolyl group or a chloromethyl group in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups have been substituted with halogen atoms, cyano groups, etc., 3-chloropropyl group, 3,3,3 One or two or more carbon atoms having a carbon number of 1 or more selected from a trifluoropropyl group and a cyanoethyl group;
Although there are 20 unsubstituted or substituted monovalent hydrocarbon groups (organic groups), it is preferable that 90 mol% or more of the whole is a methyl group.

[0013] The a structural unit of the organopolysiloxane [R ¹ ₃ SiO _1/2] units becomes too high viscosity is less than 0.1 mol%, to the handling becomes difficult, more than 5 mol% And the viscosity becomes too low, resulting in poor foam control. Furthermore, [R ¹ ₂ SiO _2/2] units is too low viscosity when is 90 mol% MatsuMitsuru, to suppress foaming is poor, 9
If it exceeds 9.8 mol%, the viscosity becomes too high and handling becomes difficult. Further, if the [R ¹ SiO _3/2 ] unit is less than 0.1 mol%, the foam-suppressing property becomes poor, and if it exceeds 5 mol%, the viscosity becomes too high and handling becomes difficult. _{^{Therefore, [R 1 3 SiO 1/2]}} / [R 1 2 SiO 2/2] /
_{^{[R 1 SiO 3/2] = 0.1~5}} / 90~99.8 / 0.
1 to 5 (mol%), preferably 1 to 3/94
９８98/1 to 3 (mol%).

It is preferable that the viscosity is as low as possible from the viewpoint of easy dispersibility and workability, and the higher the viscosity, the better from the viewpoint of foam suppression. When the viscosity is less than 1,000 mPa · S, the obtained composition has poor defoaming property, and when the viscosity is more than 100,000 mPa · S, there is a problem in workability at the time of finishing the emulsion. Although it is set to 10,000 mPa · S, it is more preferably 2,000 to 20,000 mPa · S.

The (ii) fine powdered silica used here may be a known one, which may be either wet silica or dry silica, including precipitated silica, silica xerogel, fumed silica or Further, those whose surfaces have been subjected to a hydrophobic treatment are exemplified. Specifically, Aerosil [trade name of Nippon Aerosil Co., Ltd.], Nipsil [trade name of Nippon Silica Co., Ltd.], CABOSIL [trade name of CABONET, USA] No.] and Santocell [trade name manufactured by Monsanto Co., USA], which have a specific surface area of 100 m ² / g or more because the larger the value of the specific surface area by the BET method, the better the defoaming property. And more preferably 200 m ² / g or more.

If the amount of component (A) of the finely divided silica in the oil compound is less than 0.1% by weight, the foaming resistance is poor, and if it exceeds 20% by weight, the oil compound is inferior. Is too high and handling becomes difficult, so it is 0.1 to 20% by weight, preferably 1 to 10% by weight.

The oil compound as the component (A) is heat-treated at 60 to 200 ° C. while mixing a predetermined amount of the above-mentioned organopolysiloxane and fine powdered silica in a mixer having an appropriate stirring mechanism. It can be produced by removing low-boiling fractions by adding inorganic ammonium salts, organosilicon compounds, siloxane resins, etc. to improve the defoaming ability, high temperature properties, dilution stability, etc. (Refer to Japanese Patent Publication No. 4-42043, JP-A-5-261206, and JP-A-5-261207) is optional.

The dialkylpolysiloxane as the component (B) of the foam inhibitor composition of the present invention has a role as a solvent for facilitating the dispersion of the main antifoaming component (A). The viscosity is preferably as low as possible from the viewpoint of easy dispersibility and workability. However, considering the possibility of ignition during normal handling, danger arises if the viscosity is too low. Therefore, the viscosity should be 2-5
00 mPa · S, preferably 2 to 100 mPa · S, and when mixed with (A), the mixture is 5,000
It is preferably at most mPa · S. If it is less than 2 mPa · S, the flash point becomes 70 ° C. or less, which is dangerous.
If the mixture exceeds mPa · S or is mixed with (A), if the mixture exceeds 5,000 mPa · S, not only the dispersibility deteriorates, but also the workability in the final step such as pumpability deteriorates. As the dialkyl polysiloxane, dimethyl polysiloxane (dimethyl silicone oil) is preferable.

Specific examples of commercially available dialkylpolysiloxanes include KF96A-10 mPa · S and KF96A-
100 mPa · S, KF96A-350 mPa · S (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

In the present invention, (A)
In order to improve water dispersibility in addition to the component (B),
It is preferable to blend one or more water-insoluble surfactants (polyoxyalkylene-modified silicone oil) represented by the following general formula (1) as the component (C).

[0021]

Embedded image

Here, R ² is a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group Such as an alkyl group, a cycloalkyl group such as a cyclohexyl group, a vinyl group, an alkenyl group such as an allyl group, a phenyl group, an aryl group such as a tolyl group, or a part of a hydrogen atom bonded to a carbon atom of these groups, or A chloromethyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, all of which are substituted with a halogen atom, a cyano group, and the like;
One or more unsubstituted or substituted monovalent hydrocarbon groups having 1 to 20 carbon atoms (organic groups) selected from a cyanoethyl group or the like, and 90 mol% or more of them are methyl groups. Is desirable.

A is a general formula -R ³ -O (CH ₂ CH ₂ O) _p (CH ₂ CH (CH ₃ ) O)
_q is a group represented by R ⁴ . In this case, R ³ is a divalent hydrocarbon group having 1 to 4 carbon atoms such as an alkylene group such as a methylene group, an ethylene group, a propylene group, and a butylene group, and R ⁴ is a hydrogen atom, or a methyl group, an ethyl group, a propyl group, 1 carbon atom selected from an alkyl group such as a butyl group, a pentyl group and a hexyl group, an acyl group such as an acetyl group, a propionyl group, a butyryl group and a hexanoyl group, and an isocyanic acid group
~ 6 monovalent organic groups. When the value of p + q is less than 10, it becomes difficult to emulsify and disperse the obtained foam inhibitor composition. When the value of p + q is more than 100, the viscosity increases and the workability deteriorates. And preferably 20 ≦ p + q ≦ 70.

Further, if the value of p / q is less than 30/70, it becomes difficult to emulsify and disperse the oil compound of the component (A), so that 30/70 ≦ p / q ≦ 100/0. . Preferably it is 50 / 50-80 / 20.

The polyoxyalkylene-modified silicone oil is preferably liquid at room temperature.
When the viscosity at 50 ° C. is lower than 50 mPa · S, the effect of improving the dispersibility is low, and when the viscosity is higher than 100,000 mPa · S,
Since the obtained foam inhibitor composition becomes difficult to disperse when dispersing it in water, and the workability is deteriorated, the viscosity is reduced to 500,000 to 100,000 mP.
a · S, preferably in the range of 100 to 10,000 mPa
-It is S.

When a + b is less than 10, the viscosity becomes too low, and the obtained foam inhibitor composition is easily separated and has low stability. When it is more than 1,000, the viscosity becomes too high, and the obtained foam suppressing composition becomes too high. It becomes difficult to disperse the agent composition when dispersing it in water, and the workability deteriorates.
+ B ≦ 1,000, preferably 50 ≦ a + b ≦ 500.

Further, if the value of a / b is smaller than 50/50 or larger than 99/1, it becomes difficult to emulsify and disperse the foam inhibitor composition, so that 50/50 ≦ a / b ≦ 99/1. However, preferably, 80/20 ≦ a / b ≦ 95/5.

The component (C) can be prepared by a conventional method, for example, by adding a polyoxyalkylene compound having an unsaturated group such as a vinyl group or an allyl group at the terminal of a molecular chain to an organopolysiloxane having a −Si—H group. It can be easily obtained by performing an addition reaction in the presence of a catalyst.

(A) in the foam inhibitor composition of the present invention
The content of the component is 30% of the total amount of the components (A) and (B).
When the amount is less than 90% by weight, the foam-suppressing effect of the composition becomes insufficient, and when the amount is more than 90% by weight, dispersibility in water is poor,
Since it becomes difficult to handle, it is necessary to be 30 to 90% by weight, preferably 40 to 80% by weight.

(B) in the foam inhibitor composition of the present invention
The content of the component is 10% of the total amount of the components (A) and (B).
When the amount is less than 10% by weight, the dispersibility of the composition in water is poor, and when the amount is more than 70% by weight, the foam suppressing effect of the composition becomes insufficient. Preferably, it is 20 to 60% by weight.

If the amount of component (C) is less than 0.1 part by weight based on 100 parts by weight of the total of components (A) and (B), the effect of improving water dispersibility is not sufficient, 50
If the amount is more than 10 parts by weight, the foam suppressing property is reduced.
The amount is preferably 1 part by weight, more preferably 1 to 10 parts by weight.

In order to further improve the water dispersibility of the foam inhibitor composition comprising the above components (A) and (B), (D)
It is preferable to add one or more surfactants as components. As the component (D), generally known components can be used, and examples thereof include sorbitan fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkyl ether, and polyoxyethylene. Propylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene propylene glycol fatty acid ester, polyoxyethylene castor oil , Polyoxyethylene hydrogenated castor oil, polyoxyethylene phytostanol ether, polyoxyethylene Phytosterols ether, polyoxyethylene cholesterol ether,
Examples include polyoxyethylene cholesteryl ether, alkanolamide, sugar ether, sugar amide and the like.

If the amount of the component (D) is less than 0.1 part by weight, based on 100 parts by weight of the total of the components (A) and (B), the effect of improving the water dispersibility is not sufficient.
If the amount is more than 10 parts by weight, the foam suppressing property is reduced.
Parts by weight. More preferably, it is 1 to 10 parts by weight.

The foam inhibitor composition of the present invention can be obtained by mixing the above components (A) and (B), and in some cases, further mixing a predetermined amount of the components (C) and / or (D). These components are uniformly mixed using a mixer such as a homomixer, a universal mixer (trade name), an ultra mixer (trade name), a planetary mixer (trade name), a combimix (trade name), or the like. The mixing method is not particularly limited, but heating and mixing may be performed in the range of 40 to 150 ° C.

The composition of the present invention may be added as it is to a material which is easily foamed as a foam inhibitor, or may be added by emulsification by adding water using the above mixer.

[0036]

The following are examples of the synthesis of silicone oil used in the examples and comparative examples of the present invention, examples of the production of oil compounds, and examples and comparative examples. It shows a measured value, and% indicates% by weight.

[Synthesis Example] 1,1,1,3,5,7,7,
4.5 g of 7-octamethyl-3,5-dihydroxytetrasiloxane, octamethylcyclotetrasiloxane 1
95 g and tetrabutylphosphonium hydroxide silanolate (tetrabutylphosphonium hydroxide 10
%) And mixed under a nitrogen stream,
Stir at 0 ° C for 2 hours, add 0.2 g of calcium hydroxide silanolate (containing 10% potassium hydroxide),
It heated and stirred at 150-160 degreeC for 4 hours. Then 80
At ~ 90 ° C, 0.2 g of ethylene chlorohydrin is added, and 8
The mixture was stirred for 2 hours at 0 to 90 ° C. The resulting reactant is
Heating at 150 to 160 ° C. under reduced pressure of 0 mmHg for 2 hours,
The low molecular siloxane was removed to obtain 8,000 mPa · S “Silicone Oil A”. ^{When the} structure was analyzed by ²⁹ Si NMR, [(CH ₃ ) ₃ SiO _1/2 ] / [(C
_{H 3) 2 SiO 2/2] /} [CH 3 SiO 3/2] = 1.0 / 9
The composition was 8.0 / 1.0 (mol%).

[Oil Compound Production Example 1] 276 g of “Silicone Oil A” obtained in Synthesis Example 1 as a silicone oil, and Nipsil HD-2 as fine powder silica
[Product name, manufactured by Nippon Silica Co., Ltd., specific surface area 300 m ² /
g] into a 500 ml planetary mixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 150 ° C. under a nitrogen gas stream.
And mix for 2 hours with oil compound "(A)-
1 "was prepared.

[Oil Compound Production Example 2] “285 g” of “silicone oil A” obtained in Synthesis Example 1 as a silicone oil, and Aerosil 200 as fine powder silica
[Nippon Aerosil Co., Ltd. product name, specific surface area 200m ²
/ G] using 15 g of silica whose surface was hydrophobized with (CH ₃ ) ₃ SiNHSi (CH ₃ ) ₃ , further adding 0.9 g of ammonium carbonate (trade name, manufactured by Kanto Chemical Co., Ltd.) and adding nitrogen gas The mixture was mixed at 150 ° C. for 3 hours under an air stream to prepare an oil compound “(A) -2”.

[Synthesis Example 1 of Component (C)] A stirrer equipped with an anchor type stirring blade, a Dimroth reflux cooler, and a thermometer 1
"Organopolysiloxane-1" 9
0 g, 332 g of "allylated polyether-1", 103 g of isopropyl alcohol, 1.5 g of a 10% ethanol solution of potassium acetate, and 0.1 g of a 5% n-butanol solution of chloroplatinic acid were added at 100 ° C. for 6 hours. After stirring, stripping was performed at 140 to 150 ° C. under reduced pressure of 2 mmHg, and the viscosity was 1,000 mPa · S.
As a result, a light yellow uniform "(C) -1" component was obtained.

[0041]

Embedded image “Organopolysiloxane-1” CH ₂ ＣＨCHCH ₂ O (CH ₂ CH ₂ O) ₃₃ (CH ₂ CH
(CH ₃ ) O) ₁₁ H “Allylated polyether-1”

[0042]

Embedded image (A ₁ : —CH ₂ CH ₂ CH ₂ O (CH ₂ CH ₂ O) ₃₃ (CH
_{2 CH (CH 3) O)} 11 H) "(C) -1" [(C) component Synthesis Example 2] "allylated polyether -1]
Was synthesized in the same manner as in Component Synthesis Example 1 except that “(C) -2” was changed to “allylated polyether-2”. As a result, light yellow uniform “(C) -2” having a viscosity of 900 mPa · S was obtained. Was done. CH ₂ ＣＨCHCH ₂ O (CH ₂ CH ₂ O) ₂₂ (CH ₂ CH
(CH ₃ ) O) ₂₂ H “Allylated polyether-2”

[0043]

Embedded image (A ₂ : —CH ₂ CH ₂ CH ₂ O (CH ₂ CH ₂ O) ₂₂ (CH
₂ CH (CH ₃ ) O) ₂₂ H) “(C) -2” [Example 1] 200 g of “(A) -1” obtained above,
Dimethyl polysiloxane KF96A-10mPa · S
[Shin-Etsu Chemical Co., Ltd. product name] 180 g and “(C) -1” 20 g were put into a 500 ml planetary mixer, stirred at room temperature for 1 hour, and turned grayish white and having a viscosity of 1,
000 mPa · S of “Composition-1” was obtained. Using this "Composition-1", a defoaming test was carried out as shown below. The foaming amount after the test was 120 ml. In addition, a pump circulation test was performed using “Composition-1” as shown below, and “Composition-1” circulated.

[Defoaming test] Emulgen 9 which is a polyoxyethylene nonylphenyl ether was added to a household mixer.
09 [trade name of Kao Corporation] 0.1% aqueous solution 500m
1 and 50 ppm of “Composition-1” was added, and the mixture was stirred at a high speed for 30 seconds.
The foam volume after seconds was measured.

[Pump circulation (workability) test] 1 L of "Composition-1" was added to the circulation tester shown in FIG.
Minutes confirmed circulation. In FIG. 1, 1 is a cylinder, 2 is a gear-type circulation pump, and 3 is a vinyl hose.

[Examples 2 to 9, Comparative Examples 1 and 2] A foam inhibitor composition was prepared in the same amount as in [Example 1] at the compounding amounts shown in Table 1, and subjected to the above-described defoaming test and pump circulation. A sex test was performed. Table 1 shows the results.

[0047]

[Table 1]

[0048]

The foam inhibitor composition of the present invention has excellent foam suppressing properties, water dispersibility and stability.

[Brief description of the drawings]

FIG. 1 is a schematic diagram illustrating a pump circulation test method.

[Explanation of symbols]

 1 cylinder 2 pump 3 hose

Claims (3)

[Claims] 1. A foam inhibitor composition comprising the following components (A) and (B) as main components. (A) below (i) and (ii) component oil compound 30-90 wt% of a main _{^{component, (i) R 1 3 SiO}} 1/2 units, R ¹ ₂ SiO _2/2 units, R ¹ SiO _{3 / 2} unit (and however, R ¹ is the same or different monovalent organic group having 1 to 20 carbon atoms with each other), R ¹ ₃ SiO _1/2 units / R ¹ ₂ SiO _2/2 units / R ¹ SiO _3/2 unit = 0.1-5 / 90-99.8 / 0.1-5 (mol%) It has a structure and the viscosity at 25 ° C is 1,000-1,000,000 mPa · S. 80 to 99.9% by weight of an organopolysiloxane, (ii) 0.1 to 20% by weight of finely divided silica, (B) a viscosity at 25 ° C. of 2 to 500 mPa · S, and a mixture with the component (A). One or more dialkyl polysiloxanes, which, when combined, can result in a mixture of 5,000 mPa · S or less 0 to 70% by weight. 2. (C) 25 represented by the following structural formula (1) based on 100 parts by weight of the total amount of the components (A) and (B).
The foam inhibitor composition according to claim 1, wherein 0.1 to 50 parts by weight of a polyoxyalkylene-modified silicone oil having a viscosity at 50 ° C of 500 to 100,000 mPa · S is blended. Embedded image [Wherein, R ² represents the same or different monovalent organic group having 1 to 20 carbon atoms, and A represents —R ³ —O (CH ₂ CH ₂ O) _p (CH ₂ CH (CH ₃ ) O)
_q- R ⁴ (where R ³ represents a divalent hydrocarbon group having 1 to 4 carbon atoms, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an acyl group or an isocyanic acid group, and p and q represent 3 ≦ p + q ≦ 100, 30
It is a number that satisfies / 70 ≦ p / q ≦ 100/0. ) Is a polyoxyalkylene-containing group. a and b are 10 ≦ a + b ≦ 1,000, 50/50 ≦ a / b ≦ 99
It is a number that satisfies / 1. ] 3. The foam control according to claim 1, wherein 0.1 to 50 parts by weight of the surfactant (D) is blended with respect to 100 parts by weight of the total amount of the components (A) and (B). Composition.