WO2021090803A1 - 水可溶性シリコーン消泡剤組成物およびそれを含む水系塗料 - Google Patents
水可溶性シリコーン消泡剤組成物およびそれを含む水系塗料 Download PDFInfo
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- WO2021090803A1 WO2021090803A1 PCT/JP2020/041053 JP2020041053W WO2021090803A1 WO 2021090803 A1 WO2021090803 A1 WO 2021090803A1 JP 2020041053 W JP2020041053 W JP 2020041053W WO 2021090803 A1 WO2021090803 A1 WO 2021090803A1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
- B01D19/0409—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance compounds containing Si-atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
- C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
- C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
Definitions
- the present invention relates to a water-soluble silicone defoaming agent composition and a water-based paint containing the same.
- the present invention also relates to a defoaming method and a quality maintaining method for water-based paints, which are characterized by the addition of the water-soluble silicone defoaming agent composition.
- silicone-based defoamers exhibit a defoaming effect with a small amount of addition compared to non-silicone-based defoamers such as alcohol-based, ester-based, mineral oil / vegetable oil, and synthetic oil, and are used in the chemical industry, food industry, and petroleum. It is widely used as a defoaming agent and a defoaming agent in fields such as industry, textile industry, plastic industry, cement industry, paint / adhesive industry, and various compositions have been proposed.
- polyether-modified silicones such as polyoxyalkylene modifying groups and silicone-based defoamers to which polypropylene glycol or the like is optionally added are liquid and have excellent dispersibility in water, so that the undiluted solution can be used as it is or in water.
- dispersing (diluting) and adding / blending to a liquid having foaming property the foaming can be effectively suppressed, so that it is excellent in handling workability and initial defoaming effect, and is widely used industrially. .. (For example, Patent Documents 1 to 5)
- silicone-based defoamers are water-dispersible, they are not uniformly solubilized in the aqueous phase, and the aqueous phase is suspended or the transparency is lowered. Be restricted.
- Patent Document 6 it is proposed to add a water-soluble polymer such as a polyether-modified silicone, a polyhydric alcohol alkyl ether, and optionally polyvinyl alcohol to the silicone-based defoaming agent.
- a water-soluble silicone defoaming agent composition that can be uniformly solubilized in the aqueous phase and has excellent defoaming property and storage stability is strongly desired.
- IPA is a volatile organic compound (VOC, boiling point 50-260 ° C) defined by WHO, and is also a highly volatile organic compound Very Volatile Organic Compounds (VVOC, boiling point 100 ° C or less), so it has an environmental load. Its use is not preferred from a reduced / eco-friendly standpoint.
- alcohols that can be used as a dispersion medium for silicone-based defoamers are VOCs or VVOCs, including IPA, and it is not necessary to substantially use these dispersion media, and they are excellent in solubilization in water.
- Silicone-based defoaming agents have not been known so far, and it has not been possible to provide silicone-based defoaming agents with less environmental impact.
- silicone-based defoamers suppress the generation of viable bacteria when blended in industrial products such as water-based paints, foods, cosmetics, etc., and maintain product quality control and safety. From the standpoint, it is common to add preservatives, bactericides, and antibacterial agents to commercialize the product. However, some preservatives and fungicides are highly toxic components, and there is a demand for industrial products that are used in small amounts or are free of preservatives / fungicides.
- silicone-based defoamers that do not require the use of preservatives / bactericides and have excellent solubilization properties in water have not been known so far, and are preservative / bactericide-free as described above. It was not possible to provide a silicone-based defoaming agent product.
- the object of the present invention is to achieve uniform solubilization with respect to the aqueous phase and to achieve volatile organic compound (VOC) free as defined by WHO, and to achieve its defoaming properties and storage stability. It is to provide an excellent water-soluble silicone defoaming agent composition. Further, an object of the present invention is, if necessary, water-soluble, which does not impair storage stability and quality even if it is preservative / fungicide-free, and does not easily cause a problem of viable bacteria even when blended in a water-based paint or the like. The purpose is to provide a silicone antiseptic composition.
- an object of the present invention is to provide a water-based paint additive and a water-based paint using the water-soluble silicone defoaming agent composition, and is characterized by the addition of the water-soluble silicone defoaming agent composition.
- the purpose is to provide a defoaming method and a quality maintaining method for water-based paints.
- the present inventions are selected from triethylene glycol mono-n-butyl ether and triethylene glycol butyl methyl ether, such as polyether-modified silicones in which the average value of HLB is in a specific range1.
- polyether-modified silicones in which the average value of HLB is in a specific range1.
- the water-soluble silicone defoaming agent composition of the present invention is (A) one or more types of polyether-modified silicone, polyglycerin having an average value of HLB in the range of 0.5 to 5.0. It contains modified silicone or a mixture thereof, one or more selected from (B) triethylene glycol mono-n-butyl ether and triethylene glycol butyl methyl ether, and (C) water.
- the above-mentioned component (B), particularly preferably triethylene glycol mono-n-butyl ether is a component capable of specifically achieving water solubility when used in combination with the component (A) and the component (C). And since the boiling point is 260 ° C.
- VOC-free composition can be designed as needed.
- component (B) the growth of viable bacteria in the composition is strongly suppressed, and if necessary, a preservative / fungicide-free silicone defoamer composition and a water-based paint containing the same can be obtained. It can be designed. The technical effect cannot be achieved with other triethylene glycol alkyl ethers having a similar structure.
- the water-soluble silicone defoaming agent composition of the present invention has sufficient defoaming properties and storage stability in practical use, can be uniformly solubilized in the aqueous phase, and has problems of turbidity and phase separation. Does not occur. Further, the water-soluble silicone defoamer composition of the present invention can achieve WHO definition of volatile organic compound (VOC) -free and, if necessary, preservative / bactericide-free water-soluble. It is possible to provide a silicone defoaming agent composition, a water-based paint, and the like.
- VOC volatile organic compound
- the water-soluble silicone defoaming agent composition of the present invention can provide a water-based paint additive and a water-based paint. Further, it is possible to provide a defoaming method and a quality maintaining method of a water-based paint, which are characterized by the addition of the water-soluble silicone defoaming agent composition.
- the water-soluble silicone defoaming agent composition of the present invention will be described.
- the composition comprises (A) one or more types of polyether-modified silicones, polyglycerin-modified silicones or mixtures thereof, in which the average value of HLB is in the range of 0.5 to 5.0, and (B) triethylene.
- glycol mono-n-butyl ether and triethylene glycol butyl methyl ether and (C) water, optionally, (D) having an average HLB of 2.0 to 12.0 1
- nonionic surfactants excluding component (A)
- E Hydrophobic silica
- F Organopolysiloxane having a silanol group at the end of the molecular chain
- G Polypropylene glycol, etc. May be further included.
- the "HLB value" in the water-soluble silicone defoaming agent composition of the present invention is a calculated value given by Griffin's formula based on the target molecular structure.
- the component (A) of the present invention is one kind or two or more kinds of polyether-modified silicone, polyglycerin-modified silicone, or a mixture thereof, in which the average value of HLB is in the range of 0.5 to 5.0.
- a defoaming component such as a defoaming compound containing hydrophobic silica and / or an organopolysiloxane having a silanol group at the end of the molecular chain, which will be described later, is solubilized in water. It is an essential ingredient for
- the component (A) is a silicone compound having a polyether-modifying group represented by at least one polyoxyalkylene group or a polyglycerin-modifying group having two or more glycerol units in the molecule, and the polyether-modified silicone and polyglycerin.
- An example is one or more selected from modified silicones, co-modified silicones with polyether polyglycerin and mixtures thereof.
- the structure of the silicone compound is not particularly limited, and may be a linear, branched, resinous or cyclic polysiloxane structure, and two or more polysiloxane structures are polyoxyalkylene structures or alkylenes.
- the component (A) is preferably a linear or branched polydimethylsiloxane having a polyether-modifying group or a polyglycerin-modifying group at the side chain or the terminal, and optionally, decyl.
- a long-chain alkyl group such as a group or an alkyl halide group such as a fluoroalkyl group may be contained in the molecule.
- the component (A) is preferably a polyether-modified silicone having a polyoxyalkylene group in the molecule, and is -R 1- O (C 2 H 4 O) p (C 3 H 6 O) q- R 2 (here).
- R 1 is a divalent hydrocarbon group having 1 to 4 carbon atoms
- R 2 is a hydrogen atom and an alkyl group having 1 to 6 carbon atoms
- p and q are 10 ⁇ p + q ⁇ 100, 10: 90 ⁇ p.
- the C 2 H 4 O unit may be referred to as “EO”, and the C 3 H 6 O unit may be referred to as “PO”.
- the divalent hydrocarbon group having 1 to 4 carbon atoms of R 1 include a methylene group, an ethylene group, a propylene group and a butylene group
- examples of the alkyl group having 1 to 6 carbon atoms of R 2 include a methylene group, an ethylene group, a propylene group and a butylene group. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and a hexyl group.
- the component (A) needs to have an average HLB value in the range of 0.5 to 5.0 from the viewpoint of water solubilization.
- the average value of HLB means that if the component (A) is one kind of polyether-modified silicone or the like, the HLB value is in the range of 0.5 to 5.0, but the component ( If A) is a mixture of two or more types of polyether-modified silicone, the average HLB value of each polyether-modified silicone or the like according to its mass ratio is in the range of 0.5 to 5.0.
- each of the polyether-modified silicones and the like may have an HLB value of less than 0.5 or more than 5.0. ..
- the component (A) is a polyether-modified silicone or a mixture thereof having an average value of (A1) HLB in the range of 1.0 to 4.0, and an average value of HLB of 1.0 to 3. It is particularly preferably in the range of 0.0, 1.1 to 2.5, 1.2 to 2.0.
- the component (A) is not particularly limited in terms of its molecular weight and viscosity (25 ° C.) as long as the above-mentioned condition of the average value of HLB is satisfied, but the handling workability and handling workability in the water-soluble silicone defoaming agent composition and From the viewpoint of compounding stability, the kinematic viscosity at 25 ° C. is preferably in the range of 5 to 10,000 mPa ⁇ s, and particularly preferably in the range of 100 to 5000 mPa ⁇ s.
- the component (B) of the present invention is one or more selected from triethylene glycol mono-n-butyl ether and triethylene glycol butyl methyl ether, and preferably triethylene glycol mono-n-butyl ether (as a trade name, " Butoxytriglycol "or” butyltriglycol ").
- the component (B) is a component capable of achieving solubilization of the silicone defoaming agent composition of the present invention in water by being used in combination with the above-mentioned component (A) and the component (C) which is water. Since its boiling point is 260 ° C.
- VOC-free composition can be designed for the composition according to the present invention, if necessary. Since the technical effect cannot be achieved with other triethylene glycol alkyl ethers having a similar structure, it is necessary to preferably use triethylene glycol mono-n-butyl ether at least one of the above two types. ..
- the applicant can use one or more selected from triethylene glycol mono-n-butyl ether and triethylene glycol butyl methyl ether to obtain the silicone defoaming agent composition itself and the water-based paint containing the composition. It was also found that the growth of viable bacteria is strongly suppressed and that a preservative / fungicide-free composition can be designed. Similar effects, especially those comparable to commonly used preservatives, have not been identified with other dispersion media.
- the component (C) of the present invention is water, and a defoaming component such as a defoaming compound composed of an organopolysiloxane of the composition, an arbitrary nonionic surfactant, and a water-soluble optional component such as polypropylene glycol are contained.
- a defoaming component such as a defoaming compound composed of an organopolysiloxane of the composition, an arbitrary nonionic surfactant, and a water-soluble optional component such as polypropylene glycol are contained.
- water may contain other water-soluble optional components described later in advance.
- the water is preferably clean and does not contain a component that impairs the storage stability of the silicone defoaming agent composition of the present invention, and ion-exchanged water, distilled water, well water, and tap water are exemplified. From the viewpoint of designing a preservative / fungicide-free composition, it is practically preferable that the water is clean water in which the growth of various germs is suppressed by ozone water, heating, filtration treatment, or the like.
- the silicone antifoaming agent composition of the present invention requires the above components (A) to (C), and when the total composition is 100% by mass,
- the content of the component (A) is preferably in the range of 1 to 70% by mass, more preferably in the range of 5 to 50% by mass, and particularly preferably in the range of 5 to 30% by mass.
- the content of the component (B) is preferably in the range of 1 to 50% by mass, more preferably in the range of 5 to 50% by mass, and particularly preferably in the range of 5 to 30% by mass.
- the content of the component (C) is preferably in the range of 1 to 70% by mass, more preferably in the range of 5 to 60% by mass, and particularly preferably in the range of 5 to 50% by mass.
- the silicone antifoaming agent composition of the present invention preferably contains arbitrary components other than the components (A) to (C).
- the component (D) of the present invention is one or more nonionic surfactants having an average HLB value of 2.0 to 12.0, and the component (A) is excluded from the range.
- the component (D) is used in combination with the component (A)
- the average value of HLB of the nonionic surfactant is less than the above lower limit, the solubilization property in water may not be sufficiently improved.
- the component (D) has a silicone-based nonionic surfactant such as polyoxyalkylene-modified silicone, polyglyceryl-modified silicone, glyceryl-modified silicone, and sugar-modified silicone as long as it has an average value of HLB different from that of the component (A).
- An agent may be contained, but from the viewpoint of improving water solubilization, a nonionic surfactant composed of an organic compound containing no siloxane bond in the molecule is particularly preferable.
- the average HLB value of the component (D) is preferably 11 or less, and more preferably in the range of 5 to 11, 6 to 10.
- nonionic surfactant which is the component (D), polyoxyalkylene ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters (for example, polyethylene glycol (or ethylene oxide)) and higher fatty acids (for example, carbon) Consists of linear or branched fatty acids (numbers 12 to 18)), polyoxyalkylene fatty acid diesters, polyoxyalkylene resin acid esters, polyoxyalkylene (hardened) castor oils, polyoxyalkylene alkylphenols, Polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene phenyl phenyl ethers, polyoxyalkylene alkyl esters, polyoxyalkylene alkyl esters, sorbitan fatty acid esters, polyoxyalkylene sorbitan alkyl esters (eg, sorbitan, polyethylene glycol and higher grades) Consists of fatty acids (eg, linear or branched fatty acids with
- the component (D) is preferably a polyoxyalkylene monoalkyl ether having an average value of (D1) HLB of 11 or less or a mixture thereof, and the average value of the HLB is It may be in the range of 5 to 11, 6 to 10.
- the component (E) is hydrophobic silica, and both the component (F) is a component that imparts defoaming property and defoaming durability.
- examples thereof include powder, precipitated silica fine powder, silica aerogel, quartz fine powder, and molten silica fine powder.
- these hydrophobic silicas preferably have a BET specific surface area of 50 m2 / g or more, and particularly preferably 100 m2 / g or more.
- the hydrophobizing treatment of the component (E) is not particularly limited, but it is common to hydrophobize the surface of the component (F) by kneading it with a hydrophobizing agent typified by the component (F), an organosilane and an organosiloxane oligomer. is there.
- a hydrophobizing agent typified by the component (F)
- an organosilane and an organosiloxane oligomer there.
- Well-known compounds can be used as the organosilane or the organosiloxane oligomer, and examples of the organosilane include dimethyldichlorosilane, methyltrichlorosilane, hexamethyldisilazane, and dimethyldialkoxysilane.
- organosiloxane oligomer examples include both-terminal silanol group-blocking dimethylsiloxane oligomer, both-terminal trimethylsiloxy group-blocking methylhydrogensiloxane oligomer, 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-. Examples thereof include tetramethylcyclotetrasiloxane.
- hydrophobizing agents include stearic acid, sodium stearate, vinyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and 3- (N-2-aminoethyl). Aminopropyltrimethoxysilane and the like are exemplified.
- the component (F) is an organopolysiloxane having a silanol group at the end of the molecular chain, and is a silicone compound that imparts defoaming property and defoaming durability to the composition by mixing with itself or with the component (E). Can be formed.
- the component (F) is preferably dimethylpolysiloxane having silanol groups at both ends of the molecular chain, and optionally has a hydrophobic functional group such as fluoroalkyl. May be further included.
- the kinematic viscosity of the component (F) at 25 ° C. is not particularly limited, but may be in the range of 1.5 to 100,000 mPa ⁇ s, and is in the range of 5.0 to 10,000 mPa ⁇ s. It is preferably in the range of 5.0 to 5,000 mPa ⁇ s, and more preferably in the range of 5.0 to 5,000 mPa ⁇ s.
- the component (F) of the present invention is (F1) a dimethylpolysiloxane having silanol groups at both ends of the molecular chain, the viscosity of which is in the range of 5.0 to 1,000 mPa ⁇ s at 25 ° C. Is preferably exemplified.
- the mass ratio of the component (F) to the component (E) is in the range of 100: 1 to 50. It is preferable to have. This is because if the mass ratio of the component (F), which is hydrophobic silica, is less than 1, the expected defoaming property and defoaming durability may not be realized, while the mass ratio of the component (F) is 50. If it exceeds, it may be difficult to prepare a uniform defoaming agent composition. From the viewpoint of defoaming property, it goes without saying that the component (E) or the component (F) may be used alone.
- the component (G) is polypropylene glycol, and preferably, when used in combination with the above components (A) to (E), the defoaming property and defoaming property of the entire silicone defoaming agent composition according to the present invention. It is an ingredient that improves sustainability.
- the component (A) is triethylene glycol mono-n-butyl ether, and by using polypropylene glycol as the component (G), the uniformity and solubilization in water are excellent, and the defoaming property and defoaming property are achieved.
- a silicone defoaming composition with further improved durability can be provided.
- the above components (D) to (G) are arbitrary configurations of the present invention, and when the total composition is 100% by mass,
- the content of the component (D) is preferably in the range of 0 to 40% by mass, more preferably in the range of 5 to 40% by mass, and particularly preferably in the range of 5 to 35% by mass.
- the content of the component (E) is preferably in the range of 0 to 5% by mass, more preferably in the range of 0.1 to 3% by mass, and particularly preferably in the range of 0.2 to 2% by mass.
- the content of the component (F) is preferably in the range of 0 to 10% by mass, more preferably in the range of 0.2 to 8% by mass, and particularly preferably in the range of 0.5 to 6% by mass.
- the content of the component (G) is preferably in the range of 0 to 50% by mass, more preferably in the range of 0 to 30% by mass, and particularly preferably in the range of 5 to 25% by mass.
- the silicone antifoaming agent composition of the present invention may contain other emulsifiers, alcohols, solvents, stabilizers, thickeners, preservatives, pH adjusters and the like as long as the object of the present invention is not impaired. Good.
- the amount added to the target object in the use of the defoaming agent composition of the present invention is determined by various conditions such as the target process, the properties of the defoaming target object, and the influence on the physical properties of the final product, but is generally used.
- 1 to 500 ppm is desirable for a high-concentration defoaming agent composition containing a small amount of water, and 100 to 10.000 ppm is desirable for a low-concentration defoaming agent composition containing a large amount of water.
- VOC-free defined by WHO can be achieved and preservative / bactericide-free can be achieved by selecting the component (B). Therefore, when having these technical intentions, it is particularly preferable not to use alcohols or solvents having a low boiling point and not to use preservatives or the like.
- the content of the preservative or disinfectant component is such that it is 0.05% by mass or less of the total water-based paint containing the silicone defoamer composition, and is substantially. It is particularly preferred that it does not contain preservatives and fungicides.
- the silicone defoaming agent composition of the present invention can be produced by uniformly stirring the above components (A) to (C) and other components using mechanical force of a mixer or the like.
- the stirring / mixing device is not particularly limited as long as it is a device capable of charging raw materials and uniformly stirring, and the temperature conditions during stirring are not particularly limited as long as uniform stirring is possible, and the purpose is to reduce the viscosity. It may be heated up to about 50 ° C. with the like.
- the above-mentioned component (E) and component (F) may be mixed in advance and blended in the form of a silicone compound, and the water-soluble component is mixed in advance in water which is the component (C). The whole may be stirred uniformly.
- a high-pressure emulsifying device or the like capable of applying a high shearing force such as a colloid mill, a ball mill, a disper mill, a homogenizer or a golin homogenizer.
- the water-soluble silicone defoaming agent composition of the present invention is effective against an aqueous foaming liquid, and is an antifoaming agent for paints (water-based paints, paper coating paints, etc.) and various manufacturing processes (paper making process, fermentation process, etc.). It can be particularly preferably used as a defoaming agent for wastewater treatment steps, monomer stripping steps, polymer polymerization steps, etc., and by solubilizing it in the aqueous phase, it has a transparent to translucent and uniform appearance. It is possible to achieve an excellent defoaming or defoaming effect while maintaining it.
- the water-soluble silicone defoaming agent composition of the present invention is suitable as an additive for water-based paints, and further suitable as a defoaming agent for water-based paints.
- water-based paints water-based building exterior paints, building interior paints, water-based inks, paper coating paints, etc.
- it is particularly suitable as a defoaming agent for emulsion-containing water-based paints and paper coating paints.
- the emulsion used for the emulsion coating material include emulsions of vinyl acetate resin, acrylic resin, styrene resin, halogenated olefin resin, urethane resin, silicone resin, fluorine atom-containing silicone resin, and the like.
- the water-soluble silicone defoamer composition of the present invention is effective for all water-based paints including alcohol-based or emulsion-type paints because it is otherwise uniform solubilized in the aqueous phase, and is a conventional emulsion-type silicone defoamer. And unlike the suspension type silicone defoaming agent, it is uniformly solubilized in the aqueous phase of the paint, so it does not easily affect the stability of the dosage form and emulsion, and achieves high defoaming and defoaming performance. can do.
- the method for adding the water-soluble silicone defoaming agent composition of the present invention may be added at the time of pigment dispersion or after the paint is prepared, but in particular, the aqueous phase may be continuously added. It is preferable to add it after preparing the coating material as a layer.
- any of (1) raw material supply, (2) before heating and / or depressurization treatment, and / or (3) addition to the final finishing step or the like may be used.
- the amount of the water-soluble silicone defoaming agent composition of the present invention added is in the range of 0.01 to 2.0% by mass with respect to the solid content of the water-based paint in terms of solid content, and is 0.05 to 1
- the range of 0.0% by mass is more preferable, and the range of 0.05 to 0.5% by mass is particularly preferable.
- the water-soluble silicone defoaming agent composition of the present invention can preferably achieve a defoaming or defoaming effect by blending it with a water-based paint in the above-mentioned addition amount. Furthermore, as described above, by using the component (B), the water-soluble silicone defoaming agent composition of the present invention strongly suppresses the growth of viable bacteria by itself, and preserves the quality of water-based paints (antibacterial and antiseptic effects). It is possible to realize a composition that is substantially free of preservatives / disinfectants for the water-based paint.
- the water-soluble silicone defoaming agent composition of the present invention and the water-based paint containing the same will be described in detail with reference to Examples.
- the viscosity is a value measured using a rotational viscometer at 25 ° C.
- the same sample was coated on a 200 mm x 300 mm tin-plated steel plate (tin plate) with a medium-hair roller (reciprocating 20 times), and after 30 seconds, the number of bubbles (1.0 mm or more in diameter) within the 10 cm x 15 cm area of the central part was determined. , Defoaming property (number of bubbles after 30 seconds) was evaluated.
- the test sample was inoculated with the test bacterial solution prepared after pre-culture, and after a certain period of time, the viable cell count was measured to evaluate the storage efficacy.
- the bacterial species are Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, Candida albicans, Aspergillus brushliensis and Pseudomonas fluorescence.
- a viable cell test has not been conducted on the test specimens for which a uniform sample cannot be obtained.
- A-1) Polyether-modified silicone having a polyether structure containing EO units and PO units in the molecule (HLB 1.6, molecular weight 10000, viscosity 650 mPa ⁇ s)
- A-2) Polyether-modified silicone having a polyether structure containing only EO units in the molecule (HLB 1.8, molecular weight 5000, viscosity 150 mPa ⁇ s)
- B-1) to B-14 only B-1) and B-14) are the components (B) of the present invention used in the examples, and the others are similar compounds for comparative experiments and Alcohols.
- B-1) Triethylene glycol mono-n-butyl ether, purity> 98%, manufactured by Tokyo Kasei Kogyo Co., Ltd.
- B-2) Diethylene glycol mono-n-butyl ether, purity> 98%, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., etc.
- B-4) Dipropylene glycol monomethyl ether, purity> 95%, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
- B-5) Tripropylene glycol Monobutyl ether, purity> 95%, Kanto Chemical Co., Ltd.
- B-6) Triethylene glycol, purity> 98%, Alpha Acer B-7) Tetraethylene glycol, purity> 95%, manufactured by Tokyo Kasei Kogyo Co., Ltd. B-8) Tetraethylene glycol dimethyl ether, purity> 98%, manufactured by Tokyo Kasei Kogyo Co., Ltd. B-9) Triethylene glycol dimethyl ether, purity> 97%, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. B-10) 2-Butoxyethanol / Ethylene glycol mono-n-butyl ether, purity> 99%, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. B-11) Triethylene glycol dimethyl ether purity> 97%, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
- Examples 1 to 4 and Comparative Examples 1 to 2 The above components are uniformly stirred and mixed by mechanical force (mixer) so as to have the concentration (mass%) shown in Table 1, a water-solubilized silicone defoamer is adjusted, and the mixture is allowed to stand for 24 hours and 1 week. Then, the appearance and the presence or absence of phase separation were judged by the above method and recorded in Table 1. In addition, 0.4 parts by mass (%) is added to acrylic emulsion paint (Udable (registered trademark) E-135 based on Nippon Catalyst Co., Ltd.), and the mixture is uniformly stirred and mixed by mechanical force (mixer) to eliminate its defoaming performance. Was evaluated by the above method and shown in the table below.
- Example 5 The B-1) component of "Example 1" described in the above table is replaced with the component B-14) which is the component (B) of the present invention, and the same as in Example 1, the mechanical force (mixer) is uniform.
- the water-solubilized silicone defoaming agent was prepared and allowed to stand for 24 hours, and the presence or absence of phase separation was determined by the above method and recorded.
- B-14) triethylene glycol butyl methyl ether was used, it was uniformly dispersed and the composition could be solubilized in water.
- the water-soluble silicone defoamer according to the examples is water-soluble, it has excellent handling workability and uniform dispersibility, and when simply blended with a water-based paint by stirring with a mixer, it becomes a uniform and transparent silicone composition, and even after one week, the phase is maintained. There was no separation. Furthermore, the composition has excellent defoaming properties, and not only can a uniform coating film be obtained, but also suppresses the growth of viable bacteria for a long period of time without using preservatives, antibacterial agents, or bactericidal agents. It was antibacterial-free and had excellent storage stability. Further, the component (B) used in the example does not correspond to any volatile organic compound, has the above-mentioned advantages, and is a volatile component (VOC) -free water-solubilized silicone defoamer. Is to be realized.
- VOC volatile component
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Abstract
Description
本発明の成分(A)は、HLBの平均値が0.5~5.0の範囲にある1種類または2種類以上のポリエーテル変性シリコーン、ポリグリセリン変性シリコーンまたはこれらの混合物であり、成分(B)および成分(C)と併用することで、後述する疎水性シリカおよび/または分子鎖末端にシラノール基を有するオルガノポリシロキサンを含む消泡性コンパウンド等の消泡性成分を、水中に可溶化するための必須成分である。
本発明の成分(B)はトリエチレングリコールモノ―n-ブチルエーテルおよびトリエチレングリコールブチルメチルエーテルから選ばれる1種類以上であり、好適には、トリエチレングリコールモノ―n-ブチルエーテル(商品名として、「ブトキシトリグリコール」または「ブチルトリグリコール」と呼ばれることがある)である。成分(B)は、上記の成分(A)および水である成分(C)と併用することで、本発明のシリコーン消泡剤組成物の水に対する可溶化を達成可能な成分であり、かつ、その沸点が260℃以上であるので、WHOの定義するVOCには該当せず、必要に応じて、本発明に係る組成物について、VOCフリーの組成が設計可能である。なお、類似構造の他のトリエチレングリコールアルキルエーテルでは当該技術的効果は達成できないため、上記の2種類の少なくとも一方、好適には、トリエチレングリコールモノ―n-ブチルエーテルを使用することが必要である。
本発明の成分(C)は水であり、組成物のオルガノポリシロキサンからなる消泡性コンパウンド等の消泡性成分、任意の非イオン性界面活性剤、およびポリプロピレングリコール等の水溶性任意成分が分散した水相を形成する成分であり、かつ、上記の成分(A)および成分(B)と併用することで、本発明のシリコーン消泡剤組成物全体の水に対する可溶化を達成可能な成分である。なお、水は、予め、後述するその他の水溶性の任意成分を含んでもよい。
上記成分(A)の含有量が1~70質量%の範囲であることが好ましく、5~50質量%の範囲がより好ましく、5~30質量%が特に好ましい。
上記成分(B)の含有量が1~50質量%の範囲であることが好ましく、5~50質量%の範囲がより好ましく、5~30質量%が特に好ましい。
上記成分(C)の含有量が1~70質量%の範囲であることが好ましく、5~60質量%の範囲がより好ましく、5~50質量%が特に好ましい。
なお、本発明のシリコーン消泡剤組成物は、成分(A)~(C)以外の任意成分を含むことが好ましい。
本発明の成分(D)はHLBの平均値が2.0~12.0である1種類または2種類以上の非イオン性界面活性剤であり、その範囲から成分(A)は除外される。成分(D)を成分(A)と併用することで、組成物全体の均一性、保存安定性がさらに改善され、水への可溶化性および分散性がさらに向上する利点がある。一方、非イオン性界面活性剤のHLBの平均値が前記下限未満では、特に水への可溶化性が十分に改善できない場合がある。また、HLBの平均値が前記上限を超えると、後述するシリカ成分およびオルガノポリシロキサン成分の組み合わせによっては、水への可溶化性および組成物全体の均一性が損なわれる場合がある。なお、成分(D)は、成分(A)と異なるHLBの平均値を有する限りにおいて、ポリオキシアルキレン変性シリコーン,ポリグリセリル変性シリコーン,グリセリル変性シリコーン,糖変性シリコーン等のシリコーン系の非イオン性界面活性剤を含んでもよいが、水可溶化性の改善の見地からは、シロキサン結合を分子内に含まない有機化合物からなる非イオン性界面活性剤であることが特に好ましい。また、成分(D)のHLBの平均値は、11以下であることが好ましく、5~11、6~10の範囲であることがより好ましい。
成分(E)は疎水性シリカであり、成分(F)共に、消泡性および消泡持続性を付与する成分であり、具体的には、疎水化処理を施したヒュ-ムドシリカ,焼成シリカ微粉末,沈澱シリカ微粉末,シリカアエロゲル,石英微粉末,溶融シリカ微粉末が例示される。これらの疎水性シリカは、消泡効果上、そのBET比表面積が50m2/g以上であることが好ましく、特に100m2/g以上であることが特に好ましい。
成分(F)は、分子鎖末端にシラノール基を有するオルガノポリシロキサンであり、それ自身、または成分(E)と共に混合することにより、組成物に消泡性および消泡持続性を付与するシリコーンコンパウンドを形成することができる。
成分(G)はポリプロピレングリコールであり、好適には、上記の成分(A)~(E)と組み合わせて使用することで、本発明に係るシリコーン消泡剤組成物全体の消泡性および消泡持続性を改善する成分である。特に、成分(A)がトリエチレングリコールモノ―n-ブチルエーテルであり、成分(G)としてポリプロピレングリコールを併用することで、均一性および水に対する可溶化性に優れ、かつ、消泡性および消泡持続性がさらに改善されたシリコーン消泡剤組成物を与えることができる。
上記成分(D)の含有量が0~40質量%の範囲であることが好ましく、5~40質量%の範囲がより好ましく、5~35質量%が特に好ましい。
上記成分(E)の含有量が0~5質量%の範囲であることが好ましく、0.1~3質量%の範囲がより好ましく、0.2~2質量%が特に好ましい。
上記成分(F)の含有量が0~10質量%の範囲であることが好ましく、0.2~8質量%の範囲がより好ましく、0.5~6質量%が特に好ましい。
上記成分(G)の含有量が0~50質量%の範囲であることが好ましく、0~30質量%の範囲がより好ましく、5~25質量%が特に好ましい。
本発明のシリコーン消泡剤組成物には、本発明の目的を損なわない範囲で、他の乳化剤、アルコール類、溶剤、安定剤、増粘剤、防腐剤、pH調整剤等を配合してもよい。本発明の消泡剤組成物の使用における対象物への添加量は、対象とする工程、消泡対象物の性質、最終製品の物性への影響等の諸条件によって決定されるが、一般的な目安としては、水の配合量の少ない高濃度消泡剤組成物の場合は、1~500ppm、水の配合量の多い低濃度消泡剤組成物の場合は100~10.000ppmが望ましい。
本発明のシリコーン消泡剤組成物は、上記の成分(A)~(C)およびその他の成分を、ミキサー等の機械力を用いて均一に攪拌することで製造することができる。原料の仕込みおよび均一な攪拌が可能な装置であれば特に攪拌/混合装置は制限されるものではなく、攪拌時の温度条件も、均一攪拌できれば特に制限されるものではなく、粘度を低下させる目的等で50℃程度まで加熱してもよい。なお、前記の成分(E)および成分(F)は事前に混合して、シリコーンコンパウンドの形態で配合してもよく、成分(C)である水中に、水溶性の成分を事前に混合してから全体を均一に攪拌してもよい。さらに、必要に応じて、各成分を均一に攪拌した後、コロイドミル、ボールミル、ディスパーミル、ホモジナイザー又はゴーリンホモジナイザー等の高い剪断力を加えることができる高圧乳化装置等でさらに処理してもよい。
本発明の水可溶性シリコーン消泡剤組成物は、水性発泡液に対して効果的であり、塗料(水性塗料、紙塗工塗料等)用消泡剤及び各種製造工程(抄紙工程、発酵工程、排水処理工程、モノマーストリッピング工程及びポリマー重合工程等)用消泡剤等として、特に好適に使用することができ、水相に対して可溶化することで、透明~半透明かつ均一な外観を維持したまま優れた消泡乃至抑泡効果を実現しうる。
本発明の水可溶性シリコーン消泡剤組成物は、好適には、上記の添加量で水系塗料に配合することにより、消泡乃至抑泡効果を実現することができる。さらに、上記の通り、成分(B)の使用により、本発明の水可溶性シリコーン消泡剤組成物は、それ自体が生菌の繁殖を強く抑制し、水系塗料の品質保存(抗菌および腐敗防止効果を含む)に用いることができ、当該水系塗料について、実質的に防腐剤/殺菌剤フリーの組成を実現可能である。
外観および相分離の有無を目視により評価し、「透明」または「濁りあり」と評価した。
なお、わずかでも分離が見られた場合は「分離あり」と評価し、全体が均一な場合には、「均一(相分離なし)」と評価した。
直径55mmのガラス瓶に下記の組成を有するコーティング剤を50g 入れ、本発明のシリコーン消泡剤またはそれ以外のシリコーンオイルを0.4質量% 添加し、試料とした。これについて、エッジドタービン型攪拌羽根を用いて5,000rpm の回転速度で1分間攪拌し、攪拌停止直後の液面の高さを測定し消泡性(攪拌後の液面高さ (mm))を評価した。
さらに同試料を200mmx300mmのスズめっき鋼板(ブリキ板)に中毛ローラーで塗装(往復20回)し、30秒後の中央部分の10cm×15cm面積内の泡(直径1.0mm以上)の数により、消泡性(30秒後の泡数)を評価した。
上記の試料を150mmx50mmのガラス板にバーコーター#16で塗布し、塗装面10cmx10cm面積内のハジキの発生数を目視で評価した。
ハジキの発生件数が5個以下の場合は「良好」とし、6個以上の場合には「不良」と評価し、ハジキ数を記録した。
試験試料へ前培養後作製した試験菌液をそれぞれ接種し、一定時間経過後、生菌数測定を行い,保存効力を評価した。 菌種は大腸菌、緑膿菌、黄色ブドウ球菌、カンジダ・アルビカンス、アスペルギルス・ブラシリエンシスおよびシュードモナス・フルオレッセンスである。
なお、均一な試料が得られない試験体については、生菌試験は実施していない。
A-1)分子内にEO単位およびPO単位を含むポリエーテル構造を有するポリエーテル変性シリコーン(HLB 1.6、分子量 10000、粘度650 mPa・s)
A-2) 分子内にEO単位のみを含むポリエーテル構造を有するポリエーテル変性シリコーン(HLB 1.8、分子量 5000、粘度150 mPa・s)
以下のB-1)~B-14)のうち、B-1)およびB-14)のみが、実施例に使用する本発明の成分(B)であり、他は比較実験用の類似化合物およびアルコール類である。
B-1) トリエチレングリコールモノ-n-ブチルエーテル、純度>98%、東京化成工業株式会社製
B-2) ジエチレングリコールモノ-n-ブチルエーテル、純度>98%、富士フイルム和光純薬株式会社製
ほか
B-3) 2-プロパノール、純度>99.7%、富士フイルム和光純株式会社製
B-4) ジプロピレングリコールモノメチルエーテル、純度>95%、富士フイルム和光純株式会社製
B-5) トリプロピレングリコールモノブチルエーテル、純度>95%、関東化学株式会社製
B-6) トリエチレングリコール、純度>98%、アルファ・エイサー社製
B-7) テトラエチレングリコール、純度>95%、東京化成工業株式会社製
B-8) テトラエチレングリコールジメチルエーテル、純度>98%、東京化成工業株式会社製
B-9) トリエチレングリコールジメチルエーテル、純度>97%、富士フイルム和光純薬株式会社製
B-10) 2-ブトキシエタノール/エチレングリコールモノ-n-ブチルエーテル、純度>99%、富士フイルム和光純薬株式会社製
B-11) トリエチレングリコールジメチルエーテル純度>97%、富士フイルム和光純薬株式会社製
B-12) トリエチレングリコールモノメチルエーテル、純度>98%、東京化成工業株式会社製
B-13) 酢酸2-エトキシエチル、純度>98%、関東化学株式会社製
B-14) トリエチレングリコールブチルメチルエーテル、純度>97%、富士フイルム和光純薬株式会社製
C) 水 イオン交換水
D-1) 非イオン系界面活性剤 商品名サンノニック SS-30 (三洋化成工業株式会社製)HLB=8
D-2) 非イオン系界面活性剤 商品名サンノニック SS-50 (三洋化成工業株式会社製)HLB=10.5
E) 疎水性シリカ 商品名アエロジルR-972(日本アエロジル株式会社製)
F) 分子鎖両末端にシラノール基を有するジメチルポリシロキサン (分子量 900、粘度40 mPa・s)
G) ポリプロピレングリコール 商品名サンニックス PP-2000 (三洋化成工業株式会社製)
上記の成分を、表1に記載の濃度(質量%)となるように、機械力(ミキサー)で均一に攪拌混合し、水可溶化シリコーン消泡剤を調整し、24時間および1週間静置して、その外観および相分離の有無を上記の方法で判断し、表1に記録した。
また、アクリルエマルション塗料(ユーダブル(登録商標)E-135 株式会社日本触媒製ベース)に0.4質量部(%)添加して、機械力(ミキサー)で均一に攪拌混合しその消泡性能等を上記の方法で評価し、下表に示した。
上の表に記載の「実施例1」のB-1)成分を、本発明の成分(B)に該当しない、成分B-4)~B-13)で置き換えて、実施例1同様に、機械力(ミキサー)で均一に攪拌混合し、水可溶化シリコーン消泡剤を調整し、24時間静置して、その相分離の有無を上記の方法で判断し、記録した。結果、本発明の成分(B)に該当しない、B-4)~B-13)を使用した比較例においては、すべて、相分離が発生し、均一な消泡剤組成物を得ることができなかった。
上の表に記載の「実施例1」のB-1)成分を、本発明の成分(B)である成分B-14)で置き換えて、実施例1同様に、機械力(ミキサー)で均一に攪拌混合し、水可溶化シリコーン消泡剤を調整し、24時間静置して、その相分離の有無を上記の方法で判断し、記録した。結果、B-14)トリエチレングリコールブチルメチルエーテルを使用した場合、均一に分散し、かつ、当該組成物は水に対して可溶化することができた。
実施例にかかる水可溶化シリコーン消泡剤は、水可溶性なので、取り扱い作業性と均一分散性に優れ、単にミキサー攪拌による水系塗料に配合すると均一で透明なシリコーン組成物となり、1週間後も相分離等を起こすことがなかった。さらに、同組成物は優れた消泡性を有し、均一な塗膜を得られるだけでなく、防腐剤・抗菌剤・殺菌剤を使用しなくても、長期にわたり生菌の繁殖を抑制し、抗菌剤フリーで保存安定性に優れるものであった。さらに、当該実施例において使用した成分(B)は、すべて揮発性有機化合物に該当せず、上記のような利点を有し、かつ、揮発性成分(VOC)フリーな水可溶化シリコーン消泡剤を実現するものである。
Claims (13)
- (A)HLBの平均値が0.5~5.0の範囲にある1種類または2種類以上のポリエーテル変性シリコーン、ポリグリセリン変性シリコーンまたはこれらの混合物、
(B)トリエチレングリコールモノ―n-ブチルエーテルおよびトリエチレングリコールブチルメチルエーテルから選ばれる1種類以上、並びに
(C)水を含有する、水可溶性シリコーン消泡剤組成物。 - さらに、(D)HLBの平均値が2.0~12.0である1種類または2種類以上の非イオン性界面活性剤(ただし、成分(A)を除く)を含有する、請求項1に記載の水可溶性シリコーン消泡剤組成物。
- さらに、(E)疎水性シリカを含有する、請求項1または請求項2に記載の水可溶性シリコーン消泡剤組成物。
- さらに、(F)分子鎖末端にシラノール基を有するオルガノポリシロキサンを含有する、請求項1~請求項3のいずれか1項に記載の水可溶性シリコーン消泡剤組成物。
- さらに、(G)ポリプロピレングリコールを含有する、請求項1~請求項4のいずれか1項に記載の水可溶性シリコーン消泡剤組成物。
- 組成物全体を100質量%としたとき、
上記成分(A)の含有量が1~70質量%の範囲であり、
上記成分(B)の含有量が1~50質量%の範囲であり、
上記成分(C)の含有量が1~70質量%の範囲であり、
上記成分(D)の含有量が0~40質量%の範囲であり、
上記成分(E)の含有量が0~5質量%の範囲であり、
上記成分(F)の含有量が0~10質量%の範囲であり、かつ、
上記成分(G)の含有量が0~50質量%の範囲である、
請求項1~請求項5のいずれか1項に記載の水可溶性シリコーン消泡剤組成物。 - 上記成分(A)が、(A1)HLBの平均値が1.0~4.0の範囲にあるポリエーテル変性シリコーンまたはその混合物であり、
上記成分(A)100質量部に対して、上記成分(B)の含有量が10~150質量部の範囲であり、上記成分(A)100質量部に対して、上記成分(C)の含有量が1~200質量部の範囲である、請求項1~請求項6のいずれか1項に記載の水可溶性シリコーン消泡剤組成物。 - 請求項1~請求項7のいずれか1項に記載の水可溶性シリコーン消泡剤組成物であって、さらに、(D1)HLBの平均値が11以下であるポリオキシアルキレンモノアルキルエーテルまたはその混合物を含む、水可溶性シリコーン消泡剤組成物。
- 水系塗料添加剤である、請求項1~請求項8のいずれか1項に記載の水可溶性シリコーン消泡剤組成物。
- 請求項1~請求項8のいずれか1項に記載の水可溶性シリコーン消泡剤組成物を含む、水系塗料。
- さらに、防腐剤または殺菌剤成分の含有量が、水系塗料全体の0.05質量%以下である、請求項10に記載の水系塗料。
- 1種類以上の水系塗料の固形分に対し、固形分に換算して0.01~2.0質量%の請求項1~請求項8のいずれか1項に記載の水可溶性シリコーン消泡剤組成物を添加することを特徴とする、水系塗料の消泡方法。
- 1種類以上の水系塗料の固形分に対し、固形分に換算して0.01~2.0質量%の請求項1~請求項8のいずれか1項に記載の水可溶性シリコーン消泡剤組成物を添加することを特徴とする、水系塗料の品質保存方法。
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