JPH0433481B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for producing a silicone antifoam composition. [Prior Art] In general, in various industrial methods that include a liquid treatment process or a liquid treatment process, foaming in the liquid often poses a serious problem. That is, foaming of the liquid can cause a decrease in the efficiency of necessary processing steps and a decrease in the quality of the manufactured product. In order to solve the foaming problem of liquids, it is known to apply antifoaming agents that have a foam-breaking effect of extinguishing liquid bubbles or a foaming suppressing effect of suppressing and reducing the foaming property of liquids. Silicone antifoaming agents are preferable because they are chemically stable, have little effect on the objects to which they are applied, and can provide a relatively large antifoaming effect with a small amount. Hitherto, various silicone antifoaming agents have been proposed and known; for example,
Publication No. 23613 describes an antifoaming agent consisting of dimethylpolysiloxane oil, a specific siloxane resin, and silica aerogel. Further, Japanese Patent Publication No. 1602/1983 describes an antifoaming agent obtained by heating polyorganosiloxane with a fine powder additive such as silica in the presence of an alkaline substance. [Problems to be Solved by the Invention] However, these conventional silicone antifoaming agents have a problem in that their antifoaming effect, especially the foaming suppressing effect, is not long-lasting, and foaming cannot be suppressed for a long period of time. There is a problem that the required steps cannot be fully satisfied. [Means for Solving the Problems] The present invention has been made based on the above-mentioned circumstances, and its object is to develop a silicone antifoaming material that can exhibit an excellent foaming suppressing effect over a long period of time. An object of the present invention is to provide a method for producing a pharmaceutical composition. The features of the present invention are (1) General formula

[Formula] (In the formula, R ¹ represents a monovalent hydrocarbon group or halogenated hydrocarbon group having 1 to 10 carbon atoms, and the average value of a is
1.9 to 2.2. ) and having a viscosity of 20 cs to 100000 cs at 25°C, 0 to 100 parts by weight of a polyorganosiloxane, (2) General formula

[Formula] (In the formula, R ² represents a monovalent hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group, and R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. represents a hydrocarbon group, and the average value of b+c is
1.9 to 2.2, and c is one or more - in one molecule.
This value is sufficient to provide an OR ³ group, and at least one of the -OR ³ groups is present at the end of the molecular chain. ), and the viscosity at 25℃ ranges from 200 cs to several million cs
It is. (3) polyorganosiloxane in an amount within the range of 0 to 100 parts by weight such that the total with component (1) is 100 parts by weight, and (3) a total of 100 parts by weight of components (1) and (2) above. for,
0.2 to 20 parts by weight of one or more compounds selected from the following a) to d), and a) general formula R ⁴ _d SiX _4-d (wherein R ⁴ : has 1 to 5 carbon atoms) A saturated or unsaturated monovalent hydrocarbon group X: a hydrolyzable group The average value of d is 1 or less) Organosilicon compound represented by b) Partial hydrolysis condensate of the above compound a) c (CH ₃ ) ₃ A siloxane resin consisting essentially of SiO _1/2 units and SiO ₂ units, in which the ratio of (CH ₃ ) ₃ SiO _1/2 units to SiO ₂ units is in the range of 0.4/1 to 1.2/1. ) and compound a) or b) (4) 0.2 to 30 parts by weight of a fine powder filler, based on a total of 100 parts by weight of the above components (1) and (2), and (5) a catalyst. (6) for a total of 100 parts by weight of the above components (1) and (2), at least one ≡COR ⁵ , -COOR ⁶ or -(OR ⁷ ) _o - in one molecule; (In the formula, R ⁵ and R ⁶ are hydrogen atoms or monovalent saturated or unsaturated hydrocarbon groups, and R ⁷ is 2 having 2 to 6 carbon atoms.
represents a valent hydrocarbon group, and n is an average value of 1 or more. ) at least 0.2 parts by weight of one or more compounds selected from the following (i) to (viii), (i) alkylene glycols (ii) polyhydric alcohols (iii) carvone; Acids or their esters (iv) Nonionic surfactants (v) Polyoxyethylene-type anionic surfactants (vi) Polyether-modified silicones (vii) Nonionic fluorine-based surfactants (viii) Containing OH groups (7) For a total of 100 parts by weight of the above components (1) and (2),
general formula

[Formula] (In the formula, R ⁸ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group, and R ⁹ represents a hydrogen atom or a halogenated hydrocarbon group having 1 to 10 carbon atoms.
represents a valent hydrocarbon group, and the average value of e+f is
1.9 to 2.2, and f is 2 or more − in one molecule.
This value is sufficient to provide an OR ⁹ group, and at least one of the -OR ⁹ groups is present at the end of the molecular chain. ) and having a viscosity of 5 cs to 200 cs at 25° C. are reacted at 50° C. to 300° C. To explain specifically below, in the present invention,
At least one of the following ingredients (1) and (2) and ingredients (3) to
A mixture with component (6) or a mixture further containing component (7) is heated and reacted to obtain a silicone antifoam composition. Component (1): General formula

A polyorganosiloxane represented by the formula and having a viscosity of 20 cs to 100000 cs at 25°C. The organo groups R ¹ of this polyorganosiloxane may all be the same or different and are monovalent hydrocarbon groups or halogenated hydrocarbon groups having 1 to 10 carbon atoms. Specific examples thereof are well known in the silicone industry and include methyl, ethyl, propyl, butyl, octyl, trifluoropropyl, phenyl, 2-phenylethyl, vinyl, etc., especially methyl. is preferred. In the above general formula, a has a value in the range of 1.9 to 2.2. This polyorganosiloxane essentially consists of R ¹ ₂ SiO units and R ¹ ₃ SiO _1/2 units, and as long as the value of a representing the R ¹ /Si molar ratio is within the above range, other constituent siloxanes may be used. It may contain R ¹ SiO _3/2 and SiO _4/2 units. Further, the OH group and the hydrolyzable group may be present in a residual amount included in the manufacturing process, but it is preferable that they are essentially not included. A particularly preferred polyorganopolysiloxane is a trimethylsilyl end-capped polydimethylsiloxane having a viscosity of 100 cs to 15,000 cs at 25°C. Component (2): General formula

A polyorganosiloxane represented by the formula and having a viscosity of 200 cs to several million cs at 25°C. R ² is a monovalent hydrocarbon group or halogenated hydrocarbon group having 1 to 10 carbon atoms, and specific examples thereof are the same as those for R ¹ above.
R ³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms similar to R ² , and -OR ³
At least one of the groups is present at the end of the polyorganosiloxane molecular chain. b+c is a value in the range of 1.9 to 2.2, and c is one or more - in one molecule.
This value is sufficient to provide ^three OR groups. The polyorganosiloxane is particularly preferably a hydroxyl end-capped polydimethylsiloxane having a viscosity of 500 cs to 50,000 cs at 25°C. Component (3): Any one or more of the following compounds a) to d). (a) An organic silicon compound represented by the general formula R ⁴ _d SiX _4-d . R ⁴ represents a saturated or unsaturated monovalent hydrocarbon group, and X is -OR', -OYOR', -NR'R'', -ON=CR'R'', -OOCR', OCR'=CR'R ", -ONR'R", -NR'-CO-R", and R' and R" represent hydrogen or monovalent hydrocarbon groups (-ON=CR'R", R 'and
R″ is the terminus connected to each other.

(which may have the structure of the formula), and Y represents a divalent hydrocarbon group having 1 to 5 carbon atoms. The average value of d is less than 1, so R ⁴ SiX ₃ or
It means SiX ₄ alone or a mixture thereof. These organosilicon compounds are well known in the silicone industry and include, for example, CH ₃ Si(OCH ₃ ) ₃ , CH ₃ Si(OC ₂ H ₅ ) ₃ , CH ₂ =CHSi(OCH ₃ ) ₃ , C ₆ H ₅ Si _{( OC2H5 ) 3} , Si( _{OC2H5 ) 4 ,} Si _{( OC3H7 ) 4} , _CH2 =CHSi( _{OC2H5 ) 3} , Si( _OC2H4OC2H5 ) ₄ , _CH3Si [N( _C4H9 ) ₂ ] ₃ , _{CH3Si [} ON=C( _CH3 ) ₂ ] ₃ , _CH3Si ( _OOCCH3 ) ₃ , _CH3Si [OC( _CH3 )= Examples include CH ₂ ] ₃ , CH ₃ Si[ON(C ₂ H ₅ ) ₂ ] ₃ , and the like. (b) A partially hydrolyzed condensate of the above compound (a). The method for producing this condensate is known. (c) Siloxane consisting essentially of (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units, and in which the ratio of (CH ₃ ) ₃ SiO _1/2 units to SiO ² units is in the range of 0.4/1 to 1.2/1. resin. This siloxane resin is commercially available and is prepared by cohydrolysis/condensation of (CH ₃ ) ₃ SiCl and SiCl ₄ or by reaction of (CH ₃ ) ₃ SiCl with a silicate solution. Typically produced siloxane resins have residual hydroxyl groups (approximately 2-5% by weight). This residual hydroxyl group can be reduced to virtually nothing by known methods. All of these siloxane resins are useful in this invention regardless of the amount of residual hydroxyl groups. D. A condensate of the siloxane resin of the above compound c) and the above compound a) or b). Component (4): Silica and fumes of TiO ₂ , Al ₂ O ₃ and
Finely powdered fillers such as Al ₂ O ₃ /SiO ₂ . Particularly preferred are finely powdered silica, including dry method silica produced by thermal decomposition of silicon halide, heating reaction of silicic acid-containing materials, decomposition reaction of sodium silicate metal salt with acid, aerogen method, etc. There is a wet process silica produced. Particle size is from several millimeters to several microns, specific surface area is 500
Various types of silica are commercially available, ranging from about m ² /g to 50 m ² /g. Fumes of TiO ₂ , Al ₂ O ₃ and Al ₂ O ₃ /SiO ₂ are obtained by calcining TiCl ₄ , AlCl ₃ and SiCl ₄ according to known methods. Component (5): A compound as a catalyst to promote the reaction between each component. The compound is preferably a catalyst for siloxane equilibrium reactions or silanol condensation, for example alkali metal hydroxides, alkali metal silanolates,
Selected from alkali metal alkoxides, quaternary ammonium hydroxides/silanolates, quaternary phosphonium hydroxides/silanolates, and organic acid metal salts. These compounds are also well known in silicone chemistry and need not be explained much. Examples of alkali metal hydroxides include KOH,
There are CsOH etc. Alkali metal silanolates are obtained by reacting any one of these with low molecular weight silicones, silicates, or partially hydrolyzed products thereof. When the low molecular weight silicone or silicate used here falls under any of the components (3), the alkali metal silanolate also qualifies as the component (3), and therefore the amount of the alkali metal silanolate is equal to the component (3). When satisfying 3), it is not necessarily necessary to blend component (3) consisting of an independent compound. Alkali metal alkoxides are reaction products of the above-mentioned alkali metal hydroxides and alcohols having 1 to 5 carbon atoms. Examples of the quaternary ammonium hydroxide include β-hydroxyethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, and tetramethylammonium hydroxide. Examples of the quaternary phosphonium hydroxide include tetraphosphonium hydroxide and tetraethylphosphonium hydroxide. Examples of organic acid metal salts include dibutyltin dilaurate, stannous acetate, stannous octoate, lead naphthenate, zinc octoate, iron 2-ethylhexanoate,
Cobalt naphthenate, etc. Component (6): At least one ≡COR ⁵ , − in one molecule
One or more compounds selected from the following (i) to (viii) having a group represented by COOP ⁶ or -(OR ⁷ ) _o -. Here R ⁵ and R ⁶ are hydrogen atoms or 1
R ⁷ represents a divalent hydrocarbon group having 2 to 6 carbon atoms, and n is an average value of 1 or more. Examples of this include the following compounds. (i) Alkylene glycols (R′ and R″ are hydrogen atoms or monovalent hydrocarbon groups, and p+d is an average value of 1 or more), specifically, There are polyoxyethylene-polyoxypropylene copolymers and the like. (ii) Polyhydric alcohols such as glycerin and sorbitol, or condensates thereof. (iii) Carboxylic acids or esters thereof Propionic acid, caprylic acid, lauric acid, phthalic acid, acrylic acid, etc., and esters thereof may also be exemplified. Castor oil is also included in this class and may be used. (iv) Nonionic surfactants For example, sorbitan fatty acid ester, sucrose fatty acid ester, (poly)glycerin fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester enyl formaldehyde and its condensates, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene castor oil, polyoxyethylene maleate, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, condensate of alkylene diamine and polyoxyalkylene, Others (v) Polyoxyethylene type anionic surfactants, such as polyoxyethylene alkyl ether sulfates, alkyl sulfate alkanolamines, polyoxyethylene alkyl ether phosphates, and others (vi) Polyether-modified silicones, which are linear It is a copolymer of siloxane or resin-like siloxane and polyoxyalkylene, and there are various types, but those represented by the following formula are particularly preferred. R ₃ SiO (R ₂ SiO) _r (RGSiO) _s SiR ₃ (In the formula, R represents the same or different monovalent hydrocarbon group, and a methyl group is particularly preferred. G represents a polyoxyalkylene group, and r and s are (Represents an integer.) (vii) Nonionic fluorine-based surfactants such as CF ₃ (CF ₂ ) ₆ (OCH ₂ CH ₂ ) ₅ OH, CF ₃ (CF ₂ ) ₆ (OCH ₂ CH ₂ ) ₅ OCH ₃ etc. (viii) OH group-containing polymer compounds Examples include hydroxyethyl cellulose, hydroxymethyl cellulose, carboxymethyl cellulose, arabic gum, xanthan gum, and others. These compounds are publicly known and commercially available, and one or more of them can be used in combination. Component (7): General formula

[Test method for defoaming properties]

Each of the compositions produced as described above was milked according to the following recipe to prepare a 10% emulsion solution.

[Shaking conditions]

Test container: Glass bottle with a capacity of 200ml Foaming liquid: 100ml aqueous solution of sodium dodecylbenzenesulfonate with a concentration of 0.25% by weight in distilled water Amount of antifoaming agent added: Amount to bring the composition to 200ppm or silicone content to 200ppm Number of shakes: 350 Cycles/min Test temperature: 25°C From the results in Tables 1 to 6, according to the method of the present invention,
It is clear that silicone antifoam compositions with excellent antifoam effects are obtained.

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Claims (1)

[Claims] 1 (1) General formula [Formula] (wherein R ¹ represents a monovalent hydrocarbon group or a halogenated hydrocarbon group having 1 to 10 carbon atoms, and the average value of a is 1.9 to 2.2) and has a viscosity of 20 cs to 100,000 cs at 25°C, 0 to 100 parts by weight of polyorganosiloxane, (2) general formula [formula] (wherein R ² is carbon Represents a monovalent hydrocarbon group or halogenated hydrocarbon group having 1 to 10 atoms, R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and the average of b+c value is
1.9 to 2.2, and c is one or more - in one molecule.
This value is sufficient to provide an OR ³ group, and at least one of the -OR ³ groups is present at the end of the molecular chain. ), and the viscosity at 25℃ ranges from 200 cs to several million cs
(3) polyorganosiloxane in an amount within the range of 0 to 100 parts by weight such that the total with component (1) is 100 parts by weight, and (3) the total of components (1) and (2) is 100 parts by weight. For parts by weight,
0.2 to 20 parts by weight of one or more compounds selected from the following a) to d), and a) general formula R ⁴ _d SiX _4-d (wherein R ⁴ : has 1 to 5 carbon atoms) A saturated or unsaturated monovalent hydrocarbon group X: a hydrolyzable group The average value of d is 1 or less) Organosilicon compound represented by b) Partial hydrolysis condensate of the above compound a) c (CH ₃ ) ₃ A siloxane resin consisting essentially of SiO _1/2 units and SiO ₂ units, in which the ratio of (CH ₃ ) ₃ SiO _1/2 units to SiO ₂ units is in the range of 0.4/1 to 1.2/1. ) and compound a) or b) (4) 0.2 to 30 parts by weight of a fine powder filler, based on a total of 100 parts by weight of the above components (1) and (2), and (5) a catalyst. (6) for a total of 100 parts by weight of the above components (1) and (2), at least one ≡COR ⁵ , -COOR ⁶ or -(OR ⁷ ) _o - in one molecule; (In the formula, R ⁵ and R ⁶ are hydrogen atoms or monovalent saturated or unsaturated hydrocarbon groups, and R ⁷ is 2 having 2 to 6 carbon atoms.
represents a valent hydrocarbon group, and n is an average value of 1 or more. ) at least 0.2 parts by weight of one or more compounds selected from the following (i) to (viii), and (i) alkylene glycols (ii) polyhydric alcohols (iii) Carboxylic acids or their esters (iv) Nonionic surfactants (v) Polyoxyethylene type anionic surfactants (vi) Polyether-modified silicones (vii) Nonionic fluorine surfactants (viii) OH group 1. A method for producing a silicone antifoam composition, which comprises reacting a contained polymer compound at 50°C to 300°C. 2 (1) General formula R ¹ _a SiO _4-a2 (wherein R ¹ represents a monovalent hydrocarbon group or halogenated hydrocarbon group having 1 to 10 carbon atoms, and the average value of a is
1.9 to 2.2. ), and the viscosity at 25°C is 20 cs to 100000 cs. 0 to 100 parts by weight of ^{polyorganosiloxane} ; ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and the average value of b + c is
1.9 to 2.2, and c is one or more - in one molecule.
This value is sufficient to provide an OR ³ group, and at least one of the -OR ³ groups is present at the end of the molecular chain. ), and the viscosity at 25℃ ranges from 200 cs to several million cs
It is. (3) polyorganosiloxane in an amount within the range of 0 to 100 parts by weight such that the total with component (1) is 100 parts by weight, and (3) a total of 100 parts by weight of components (1) and (2) above. for,
0.2 to 20 parts by weight of one or more compounds selected from the following a) to d), and a) general formula R ⁴ _d SiX _4-d (wherein R ⁴ : has 1 to 5 carbon atoms) A saturated or unsaturated monovalent hydrocarbon group X: a hydrolyzable group The average value of d is 1 or less) Organosilicon compound represented by b) Partial hydrolysis condensate of the above compound a) c (CH ₃ ) ₃ A siloxane resin consisting essentially of SiO _1/2 units and SiO ₂ units, in which the ratio of (CH ₃ ) ₃ SiO _1/2 units to SiO ₂ units is in the range of 0.4/1 to 1.2/1. ) and compound a) or b) (4) 0.2 to 30 parts by weight of a fine powder filler, based on a total of 100 parts by weight of the above components (1) and (2), and (5) a catalyst. (6) for a total of 100 parts by weight of the above components (1) and (2), at least one ≡COR ⁵ , -COOR ⁶ or -(OR ⁷ ) _o - in one molecule; (In the formula, R ⁵ and R ⁶ are hydrogen atoms or monovalent saturated or unsaturated hydrocarbon groups, and R ⁷ is 2 having 2 to 6 carbon atoms.
represents a valent hydrocarbon group, and n is an average value of 1 or more. ) at least 0.2 parts by weight of one or more compounds selected from the following (i) to (viii), and (i) alkylene glycols (ii) polyhydric alcohols (iii) Carboxylic acids or their esters (iv) Nonionic surfactants (v) Polyoxyethylene type anionic surfactants (vi) Polyether modified silicones (vii) Nonionic fluorine surfactants (viii) OH group Containing polymer compound (7) For a total of 100 parts by weight of the above components (1) and (2),
General formula [Formula] (In the formula, R ⁸ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms or a halogenated hydrocarbon group, and R ⁹ represents a hydrogen atom or a halogenated hydrocarbon group having 1 to 10 carbon atoms. 1
represents a valent hydrocarbon group, and the average value of e+f is
1.9 to 2.2, and f is 2 or more − in one molecule.
This value is sufficient to provide an OR ⁹ group, and at least one of the -OR ⁹ groups is present at the end of the molecular chain. ) with 0.5 to 100 parts by weight of a polyorganosiloxane having a viscosity of 5 cs to 200 cs at 25°C, and reacting at 50°C to 300°C. Method.