WO2002098983A1 - Silicone composition for water-repellent coating - Google Patents

Silicone composition for water-repellent coating Download PDF

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Publication number
WO2002098983A1
WO2002098983A1 PCT/JP2002/005130 JP0205130W WO02098983A1 WO 2002098983 A1 WO2002098983 A1 WO 2002098983A1 JP 0205130 W JP0205130 W JP 0205130W WO 02098983 A1 WO02098983 A1 WO 02098983A1
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WIPO (PCT)
Prior art keywords
weight parts
silicone composition
component
parts
water
Prior art date
Application number
PCT/JP2002/005130
Other languages
French (fr)
Inventor
Hideki Kobayashi
Motoshi Sasaki
Original Assignee
Dow Corning Toray Silicone Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Corning Toray Silicone Co., Ltd. filed Critical Dow Corning Toray Silicone Co., Ltd.
Priority to KR10-2003-7015533A priority Critical patent/KR20040030640A/en
Priority to EP02728164A priority patent/EP1392772B1/en
Priority to CA002448750A priority patent/CA2448750A1/en
Priority to DE60221383T priority patent/DE60221383T2/en
Priority to US10/478,158 priority patent/US20060281889A1/en
Publication of WO2002098983A1 publication Critical patent/WO2002098983A1/en

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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
    • C08L83/14—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • 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
    • 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
    • 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
    • C09D183/14—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • 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
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • 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
    • C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • C08G77/50—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages

Definitions

  • the present invention relates to a silicone composition for a water-repellent coating, and more particularly to a silicone composition for a water-repellent coating capable of forming a soft water-repellent film when cured for a short time at a low temperature.
  • silicone compositions are used as treatment agents that give the surfaces of various substrates water repellency or water resistance.
  • Known examples include silicone resin compositions and compositions primarily containing alkylalkoxysilanes.
  • Japanese Patent Application Publication(Kokai) No.Hei 9-255941 discloses a water repellency treatment agent containing a fluoroalkylsilane.
  • Japanese Patent Application Publication(Kokai) No.Hei 9-255941 discloses a water repellency treatment agent containing a fluoroalkylsilane.
  • Japanese Patent Application Publication(Kokai) No.Hei 9-255941 discloses a water repellency treatment agent containing a fluoroalkylsilane.
  • Japanese Patent Application Publication(Kokai) No.Hei 9-255941 discloses a water repellency treatment agent containing a fluoroalkylsilane.
  • Japanese Patent Application Publication(Kokai) No.Hei 9-255941 disclose
  • Application Publication(Kokai) No.Hei 11-21508 discloses a coating agent composed of a hydrolyzable silicone resin, a phenylsilane, a partial hydrolysate of alkoxysilane, and a tin catalyst.
  • surface treatment agents are disadvantageous in that they have inadequate water repellency and take long to cure, and thus need additional improvement.
  • Rl x Si(OR2) 4 _ x where * is a C ⁇ to Cg monovalent hydrocarbon group, R ⁇ is a C ⁇ to Cg alkyl group, and x is an integer from 0 to 3 ;
  • R is a Ci to Cio monovalent hydrocarbon group such as methyl, ethyl, propyl, or other alkyl. Of these, methyl and ethyl are preferred.
  • Q is an oxygen atom or a C to C o alkylene group. Examples of alkylene groups include ethylene, propylene, butylene, and hexylene.
  • n is an integer from 10 to 1000, preferably 100 to 800, and ideally 300 to 700.
  • Component (A) can be readily produced by a conventionally known method.
  • the component may, for example, be synthesized by condensing a tetraalkoxysilane and a silanol-blocked polydimethylsiloxane in the presence or absence of a catalyst.
  • the reaction ratio thereof expressed as the tetraalkoxysilane/silanol group molar ratio, should preferably be 5 to 15.
  • a trialkoxychlorosilane and a silanol-blocked polydimethylsiloxane are condensed in the presence of a pyridine or other hydrogen halide receptor.
  • the component may be produced by a method in which a trialkoxysilane and an alkenyl-blocked polydimethylsiloxane are hydrosilated in the presence of a platinum catalyst, or a method in which an alkenyltrialkoxysilane and an SiH-blocked polydimethylsiloxane are hydrosilated in the presence of a platinum catalyst.
  • Component (B) is a partial hydrolysate/condensate of alkoxysilane, wherein the alkoxysilane has a general formula R* x Si(OR2) _ x .
  • R! is a C ⁇ to C monovalent hydrocarbon group such as methyl, ethyl, propyl, or other alkyl group; vinyl, allyl, 5-hexenyl, or other alkenyl group; or phenyl or other aryl group, of which methyl is preferred.
  • R2 is a C] to C alkyl group such as methyl, ethyl, or propyl, of which methyl and ethyl are preferred.
  • x is an integer from 0 to 3, and preferably 1 or 0.
  • alkoxysilanes suitable for component (B) include dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane.
  • Component (B) may be prepared by adding water to such an alkoxysilane to achieve partial hydrolysis/condensation, and the resulting partial hydrolysate/condensate should preferably contain alkoxy groups in an amount at which the
  • OR ⁇ /Si ratio falls within a range of 0.8 to 2.6. This is because a ratio greater than 2.6 increases volatility and makes it more likely that the degree of crosslinking will vary, whereas a ratio less than 0.8 reduces compatibility with component (A).
  • the viscosity of component (B) at 25°C should preferably be 1 to 100 mm ⁇ /s.
  • Component (B) should be added in an amount of 5 to 100 weight parts, preferably 5 to 20 weight parts because of considerations related to curability, in each case per 100 weight parts of component (A).
  • the organotitanium-based catalyst facilitates the hydrolysis and condensation of alkoxy groups.
  • specific examples of such catalysts include tetramethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetra(2-ethylhexyl) titanate, titanium tetraacetyl acetonate, and bis(isopropoxy)titanium bis(acetyl acetonate).
  • Component (C) should be added in an amount of 0.1 to 10 weight parts, preferably 0.5 to 5 weight parts because of considerations related to curability, in each case per 100 weight parts of component (A).
  • the aliphatic hydrocarbon solvent or ester-based solvent is a component that dissolves component (A) or (B) and improves the applicability of the present composition.
  • suitable aliphatic hydrocarbon solvents include hexane, octane, heptane, n-paraffins (such as Normal Paraffin SL, L, and M® from Nippon Petrochemicals), and other linear aliphatic hydrocarbons, and isohexane, isoparaffins (such as Isosol 200 and 300® from Nippon Petrochemicals), and other branched aliphatic hydrocarbons.
  • ester-based solvents include ethyl acetate, butyl acetate, and isobutyl acetate.
  • Component (D) should be added in an amount of 50 to 900 weight parts, preferably 100 to 500 weight parts because of considerations related to the ease of application, in each case per 100 weight parts of component (A).
  • the alcohol-based solvent (component (E)) is a diluting component designed to improve the dispersibility of component (C) and storage stability of the present composition. Specific examples include methanol, ethanol, isopropanol, butanol, and isobutanol. These alcohol-based solvents may also contain small amounts of moisture.
  • Component (E) should be added in an amount of 0.1 to 100 weight parts, and preferably 0.5 to 50 weight parts, in each case per 100 weight parts of component (A). This is because adding less than 0.1 weight part has an adverse effect on the dispersion stability of component (C), whereas adding more than 100 weight parts has an adverse effect on applicability.
  • composition of the present invention comprises the above-described components (A) to (E), it is also possible to optionally add coloring pigments, anticorrosive pigments, and other pigments; antimicrobials agents; polyether-modified silicones and other leveling agents; antifouling agents; and the like in an appropriate manner.
  • the following components may also be added in an appropriate manner in order to improve the adhesion of the resulting coating film: 3-aminopro ⁇ yltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldiethoxysilane, and other aminosilane coupling agents; and 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and other epoxysilane coupling agents; as well as 3-mercaptopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and the like. It should be noted
  • the present composition may, for example, be applied by dipping, spraying, or brushing.
  • the coating film may have any thickness, but a thickness of 1 to 500 ⁇ m is preferred.
  • a film with excellent water repellency can be formed by applying a material and heating it
  • the composition of the present invention is characterized in that fast curing can be achieved even at comparatively low heating temperatures (50 to 100°C).
  • a cured film can be formed in 0.5 to 20 minutes when the material is heated to 100°C, and in 1 to 30 minutes when the material is heated to 80°C. Additional benefits include the fact that the present composition has excellent storage stability and can form a film that exhibits excellent water repellency at a low temperature in a short time even after prolonged standing.
  • the composition is therefore suitable as a water-repellent coating for acrylic resins, ABS resins, polyester nonwovens, leather, synthetic imitation leather, and other organic materials. Glass, iron, aluminum, and stainless steel plates can also be cited as examples of substrates to which the present composition can be applied. Since a cured film commonly has a pencil hardness of 6B or less, the composition of the present invention can be used as a water-repellent agent for forming coatings on materials for which such soft films are required, such as wallpaper, ceiling finishes, flooring materials, cloth, curtains, and other materials for interior use; doors, roofs, seats, and other interior materials of automobile or vehicle; and films, sheets, and other packaging materials.
  • part refers to weight parts
  • viscosity denotes values measured at 25°C
  • Me refers to methyl group.
  • contact angle of the film with water was measured using a contact angle meter (CA-Z® from Kyowa Interface Science), and the pencil hardness was measured by the method defined in JIS K5400.
  • the resulting silicone composition was applied to a polyester nonwoven for wallpaper and heat-treated for 5 minutes in a 100°C oven, yielding a cured film.
  • the contact angle of the film with water was 106° and the pencil hardness thereof was 6B or less.
  • the silicone composition was stored for 3 months at room temperature, and a cured film was formed on the surface of a polyester nonwoven for wallpaper in the same manner.
  • the contact angle of the film with water was measured and it was found that the result was the same as that obtained immediately after preparation. In addition, no change was detected in product appearance.
  • Working Example 2
  • the resulting silicone composition was applied to a polyester nonwoven for wallpaper and heat-treated for 5minutes in a 100°C oven, yielding a cured film.
  • the contact angle of the film with water was 105° and the pencil hardness thereof was 6B or less.
  • Comparative Example 1 A silicone composition for coating was prepared in the same manner as in Working Example 2 except that the bis(isopropoxy)titanium bis(acetyl acetonate) (3 parts) used in Working Example 2 was dispensed with.
  • the resulting silicone composition was applied to a polyester nonwoven for wallpaper and heat-treated for 5 minutes in a 100°C oven, yielding a film.
  • the contact angle of the film with water was measured and it was found that water had penetrated into the polyester nonwoven and that the film had failed to become water repellent.
  • silicone composition for coating.
  • the resulting silicone composition was applied to a polyester nonwoven for wallpaper and heat-treated for 5minutes in a 100°C oven, yielding a cured film.
  • the contact angle of the film with water was 106° and the pencil hardness thereof was 6B or less.
  • the resulting silicone composition was applied to a polyester nonwoven for wallpaper and heat-treated for 10 minutes in a 80°C oven, yielding a cured film.
  • the contact angle of the film with water was 105° and the pencil hardness thereof was 6B or less.
  • Comparative Example 2 The following components were added to 100 parts of a polydimethylsiloxane fluid that had a viscosity of about 3000 mPa-s and was described by the average molecular formula (MeO)3SiO(Me2SiO)30()Si(OMe)3: 20 parts of the partial hydrolysate/condensate of methyltrimethoxysilane(Bl) obtained as the synthetic example, 400 parts of isopropyl alcohol, and 3 parts of bis(isopropoxy)titanium bis(acetyl acetonate), yielding a silicone composition for coating.
  • the resulting silicone composition was applied to a polyester nonwoven for wallpaper and heat-treated for 5 minutes in a 100°C oven, yielding a cured film.
  • the contact angle of the film with water was 106°.
  • the silicone composition was stored for 3 months at room temperature, a cured film was formed on the surface of a polyester nonwoven for wallpaper in the same manner and the contact angle of the film with water was measured and found to have decreased to 100°. It was thus demonstrated that the silicone composition had inadequate storage stability.
  • Comparative Example 3 The following components were added to 100 parts of a polydimethylsiloxane fluid that had a viscosity of about 3000 mPa-s and was described by the average molecular formula (MeO)3SiO(Me2SiO)30()Si(OMe)3: 20 parts of the partial hydrolysate/condensate of methyl trimethoxysilane(Bl) obtained as the synthetic example, 400 parts of an isoparaffin solvent (Isosol 300® from Nippon Petrochemicals), and 3 parts of bis(isopropoxy)titanium bis(acetyl acetonate), yielding a light-yellow transparent silicone composition for coating.
  • an isoparaffin solvent Isosol 300® from Nippon Petrochemicals
  • the silicone composition was stored at room temperature, and cloudiness was observed in two months. It was thus demonstrated that the silicone composition had inadequate storage stability.
  • Comparative Example 4 The following components were added to 100 parts of a polydimethylsiloxane fluid that had a viscosity of about 3000 mPa-s and was described by the average molecular formula (MeO)3SiO(Me2SiO)30()Si(OMe)3: 20 parts of the partial hydrolysate/condensate of methyltrimethoxysilane(Bl) obtained as the synthetic example, 390 parts of an isoparaffin solvent (Isosol 300® from Nippon Petrochemicals), 10 parts of isopropyl alcohol, and 3 parts of dibutyltin dilaurate, yielding a silicone composition for coating.
  • an isoparaffin solvent Isosol 300® from Nippon Petrochemicals
  • the resulting silicone composition was applied to a polyester nonwoven for wallpaper and heat-treated for 5 minutes in a 100°C oven, yielding a cured film.
  • the contact angle of the film with water was measured and found to be 100°, indicating that the film had inadequate water repellency.
  • the present silicone composition as described above is capable of forming a soft water-repellent film when cured for a short time at a low temperature, it is suitable as a water- repellent coating for acrylic resins, ABS resins, polyester nonwovens, leather, synthetic imitation leather, and other organic materials; and it can be used as a water-repellent agent for forming coatings on materials such as wallpaper, ceiling finishes, flooring materials, cloth, curtains, and other materials for interior use; doors, roofs, seats, and other interior materials of automobile or vehicle; and films, sheets, and other packaging materials.

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Abstract

A silicone composition for a water-repellent coating comprising (A) a polydimethylsiloxane expressed by the general formula: (RO)3Si-Q-{(CH3)2SiO}n-(CH3)2Si-Q-Si(OR)3, where R is a C1 to C10 monovalent hydrocarbon group, Q is an oxygen atom or a C2 to C10 alkylene group, and n is an integer from 10 to 1000; (B) an alkoxysilane partial hydrolysate/condensate, where the alkoxysilane is described by general formula: R1xSi(OR2)4-x, where R1 is a C¿1? to C6 monovalent hydrocarbon group, R2 is a C1 to C6 alkyl group, and x is an integer from 0 to 3; (C) an organotitanium-based catalyst; (D) an aliphatic hydrocarbon solvent or ester-based solvent; and (E) an alcohol-based solvent.

Description

DESCRIPTION
SILICONE COMPOSITION FOR WATER-REPELLENT COATING
Technical Field
The present invention relates to a silicone composition for a water-repellent coating, and more particularly to a silicone composition for a water-repellent coating capable of forming a soft water-repellent film when cured for a short time at a low temperature.
Background Art
In conventional practice, silicone compositions are used as treatment agents that give the surfaces of various substrates water repellency or water resistance. Known examples include silicone resin compositions and compositions primarily containing alkylalkoxysilanes. For example, Japanese Patent Application Publication(Kokai) No.Hei 9-255941 discloses a water repellency treatment agent containing a fluoroalkylsilane. In addition, Japanese Patent
Application Publication(Kokai) No.Hei 11-21508 discloses a coating agent composed of a hydrolyzable silicone resin, a phenylsilane, a partial hydrolysate of alkoxysilane, and a tin catalyst. However, such surface treatment agents are disadvantageous in that they have inadequate water repellency and take long to cure, and thus need additional improvement. Specifically, it is an object of the present invention to provide a silicone composition for a water-repellent coating capable of forming a soft water-repellent film when cured for a short time at a low temperature.
Disclosure of Invention A silicone composition for a water-repellent coating comprising
(A) 100 weight parts of a polydimethylsiloxane described by general formula
(RO)3Si-Q-{(CH3)2SiO}n-(CH3)2Si-Q-Si(OR)3 , where R is a Ci to Ci o monovalent hydrocarbon group, Q is an oxygen atom or a C2 to C\Q alkylene group, and n is an integer from 10 to 1000; (B) 5 to 100 weight parts of a partial hydrolysate/condensate of alkoxysilane, wherein the alkoxysilane has a general formula
RlxSi(OR2)4_x , where * is a C\ to Cg monovalent hydrocarbon group, R^ is a C\ to Cg alkyl group, and x is an integer from 0 to 3 ;
(C) 0.1 to 10 weight parts of an organotitanium-based catalyst;
(D) 50 to 900 weight parts of an aliphatic hydrocarbon solvent or ester-based solvent; and
(E) 0.1 to 100 weight parts of an alcohol-based solvent.
The present invention will now be described in detail. The polydimethylsiloxane of component (A) is described by general formula
(RO)3Si-Q-{(CH3)2SiO}n-(CH3)2Si-Q-Si(OR)3. hi this formula, R is a Ci to Cio monovalent hydrocarbon group such as methyl, ethyl, propyl, or other alkyl. Of these, methyl and ethyl are preferred. Q is an oxygen atom or a C to C o alkylene group. Examples of alkylene groups include ethylene, propylene, butylene, and hexylene. In the formula, n is an integer from 10 to 1000, preferably 100 to 800, and ideally 300 to 700. Component (A) can be readily produced by a conventionally known method. When Q in the above general formula is an oxygen atom, the component may, for example, be synthesized by condensing a tetraalkoxysilane and a silanol-blocked polydimethylsiloxane in the presence or absence of a catalyst. The reaction ratio thereof, expressed as the tetraalkoxysilane/silanol group molar ratio, should preferably be 5 to 15. According to another possible method, a trialkoxychlorosilane and a silanol-blocked polydimethylsiloxane are condensed in the presence of a pyridine or other hydrogen halide receptor. When the Q in the above general formula is an alkylene group, the component may be produced by a method in which a trialkoxysilane and an alkenyl-blocked polydimethylsiloxane are hydrosilated in the presence of a platinum catalyst, or a method in which an alkenyltrialkoxysilane and an SiH-blocked polydimethylsiloxane are hydrosilated in the presence of a platinum catalyst.
Component (B) is a partial hydrolysate/condensate of alkoxysilane, wherein the alkoxysilane has a general formula R*xSi(OR2) _x. In this formula, R! is a C\ to C monovalent hydrocarbon group such as methyl, ethyl, propyl, or other alkyl group; vinyl, allyl, 5-hexenyl, or other alkenyl group; or phenyl or other aryl group, of which methyl is preferred.
R2 is a C] to C alkyl group such as methyl, ethyl, or propyl, of which methyl and ethyl are preferred. In the formula, x is an integer from 0 to 3, and preferably 1 or 0. Examples of alkoxysilanes suitable for component (B) include dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane. These compounds can be used singly or as mixtures of two or more components. Component (B) may be prepared by adding water to such an alkoxysilane to achieve partial hydrolysis/condensation, and the resulting partial hydrolysate/condensate should preferably contain alkoxy groups in an amount at which the
OR^/Si ratio falls within a range of 0.8 to 2.6. This is because a ratio greater than 2.6 increases volatility and makes it more likely that the degree of crosslinking will vary, whereas a ratio less than 0.8 reduces compatibility with component (A). The viscosity of component (B) at 25°C should preferably be 1 to 100 mm^/s. Component (B) should be added in an amount of 5 to 100 weight parts, preferably 5 to 20 weight parts because of considerations related to curability, in each case per 100 weight parts of component (A).
The organotitanium-based catalyst (component (C)) facilitates the hydrolysis and condensation of alkoxy groups. Specific examples of such catalysts include tetramethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetra(2-ethylhexyl) titanate, titanium tetraacetyl acetonate, and bis(isopropoxy)titanium bis(acetyl acetonate). Component (C) should be added in an amount of 0.1 to 10 weight parts, preferably 0.5 to 5 weight parts because of considerations related to curability, in each case per 100 weight parts of component (A).
The aliphatic hydrocarbon solvent or ester-based solvent (component (D)) is a component that dissolves component (A) or (B) and improves the applicability of the present composition. Specific examples of suitable aliphatic hydrocarbon solvents include hexane, octane, heptane, n-paraffins (such as Normal Paraffin SL, L, and M® from Nippon Petrochemicals), and other linear aliphatic hydrocarbons, and isohexane, isoparaffins (such as Isosol 200 and 300® from Nippon Petrochemicals), and other branched aliphatic hydrocarbons. Specific examples of suitable ester-based solvents include ethyl acetate, butyl acetate, and isobutyl acetate. Component (D) should be added in an amount of 50 to 900 weight parts, preferably 100 to 500 weight parts because of considerations related to the ease of application, in each case per 100 weight parts of component (A).
The alcohol-based solvent (component (E)) is a diluting component designed to improve the dispersibility of component (C) and storage stability of the present composition. Specific examples include methanol, ethanol, isopropanol, butanol, and isobutanol. These alcohol-based solvents may also contain small amounts of moisture. Component (E) should be added in an amount of 0.1 to 100 weight parts, and preferably 0.5 to 50 weight parts, in each case per 100 weight parts of component (A). This is because adding less than 0.1 weight part has an adverse effect on the dispersion stability of component (C), whereas adding more than 100 weight parts has an adverse effect on applicability.
Although the composition of the present invention comprises the above-described components (A) to (E), it is also possible to optionally add coloring pigments, anticorrosive pigments, and other pigments; antimicrobials agents; polyether-modified silicones and other leveling agents; antifouling agents; and the like in an appropriate manner. The following components may also be added in an appropriate manner in order to improve the adhesion of the resulting coating film: 3-aminoproρyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-aminoethyl)aminopropyltriethoxysilane, 3-(2-aminoethyl)aminopropylmethyldimethoxysilane, 3-(2-aminoethyl)aminopropylmethyldiethoxysilane, and other aminosilane coupling agents; and 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and other epoxysilane coupling agents; as well as 3-mercaptopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and the like. It should be noted, however, that the present composition does not contain any alkoxysilanes that have phenyl groups.
The present composition may, for example, be applied by dipping, spraying, or brushing. The coating film may have any thickness, but a thickness of 1 to 500 μm is preferred. Although it is common knowledge that a film with excellent water repellency can be formed by applying a material and heating it, the composition of the present invention is characterized in that fast curing can be achieved even at comparatively low heating temperatures (50 to 100°C). For example, a cured film can be formed in 0.5 to 20 minutes when the material is heated to 100°C, and in 1 to 30 minutes when the material is heated to 80°C. Additional benefits include the fact that the present composition has excellent storage stability and can form a film that exhibits excellent water repellency at a low temperature in a short time even after prolonged standing.
The composition is therefore suitable as a water-repellent coating for acrylic resins, ABS resins, polyester nonwovens, leather, synthetic imitation leather, and other organic materials. Glass, iron, aluminum, and stainless steel plates can also be cited as examples of substrates to which the present composition can be applied. Since a cured film commonly has a pencil hardness of 6B or less, the composition of the present invention can be used as a water-repellent agent for forming coatings on materials for which such soft films are required, such as wallpaper, ceiling finishes, flooring materials, cloth, curtains, and other materials for interior use; doors, roofs, seats, and other interior materials of automobile or vehicle; and films, sheets, and other packaging materials.
Best Mode for Carrying Out the Invention
The present invention will now be described through working and comparative examples. In the working examples, "parts" refers to weight parts, "viscosity" denotes values measured at 25°C, and "Me" refers to methyl group. In addition, the contact angle of the film with water was measured using a contact angle meter (CA-Z® from Kyowa Interface Science), and the pencil hardness was measured by the method defined in JIS K5400.
Synthesis Example. Hydrochloric acid (1/100 N, 115 g) was added in drops while methyltrimethoxysilane (775 g) and methanol (110 g) were stirred. Following the dropwise addition, the system was heated and stirred under reflux for 7 hours. Stripping was then performed at a reduced pressure and the product was cooled and filtered, yielding 490 g of a partial hydrolysate/condensate of methyltrimethoxysilane(Bl) with a viscosity of 25 mm^/s. It was determined by l^C-NMR analysis that the resulting partial hydrolysate/condensate had a methoxy residue/Si ratio of 0.9. Working Example 1. The following components were added to 100 parts of a polydimethylsiloxane fluid that had a viscosity of about 3000 mPa-s and was described by the average molecular formula (MeO)3SiO(Me2SiO)3ooSi(OMe)3: 20 parts of the partial hydrolysate/condensate of methyltrimethoxysilane(Bl) obtained as the synthetic example, 390 parts of an isoparaffin solvent (Isosol 300® from Nippon Petrochemicals), 10 parts of isopropyl alcohol, and 3 parts of bis(isopropoxy)titaniurn bis(acetyl acetonate), yielding a light-yellow transparent silicone composition for coating.
The resulting silicone composition was applied to a polyester nonwoven for wallpaper and heat-treated for 5 minutes in a 100°C oven, yielding a cured film. The contact angle of the film with water was 106° and the pencil hardness thereof was 6B or less. The silicone composition was stored for 3 months at room temperature, and a cured film was formed on the surface of a polyester nonwoven for wallpaper in the same manner. The contact angle of the film with water was measured and it was found that the result was the same as that obtained immediately after preparation. In addition, no change was detected in product appearance. Working Example 2. The following components were added to 100 parts of a polydimethylsiloxane fluid that had a viscosity of about 3000 mPa-s and was described by the average molecular formula (MeO)3SiO(Me2SiO)3ooSi(OMe)3: 20 parts of a partial hydrolysate/condensate of tetraethoxysilane(Ethyl Silicate 40® from Tama Chemicals) with a viscosity of 5 mm^/s and an ethoxy residue/Si ratio of 2.2, 390 parts of an isoparaffin solvent (Isosol 300® from Nippon Petrochemicals), 10 parts of isopropyl alcohol, and 3 parts of bis(isopropoxy)titanium bis(acetyl acetonate), yielding a silicone composition for coating.
The resulting silicone composition was applied to a polyester nonwoven for wallpaper and heat-treated for 5minutes in a 100°C oven, yielding a cured film. The contact angle of the film with water was 105° and the pencil hardness thereof was 6B or less. Comparative Example 1. A silicone composition for coating was prepared in the same manner as in Working Example 2 except that the bis(isopropoxy)titanium bis(acetyl acetonate) (3 parts) used in Working Example 2 was dispensed with.
The resulting silicone composition was applied to a polyester nonwoven for wallpaper and heat-treated for 5 minutes in a 100°C oven, yielding a film. The contact angle of the film with water was measured and it was found that water had penetrated into the polyester nonwoven and that the film had failed to become water repellent.
Working Example 3. The following components were added to 100 parts of a polydimethylsiloxane fluid that had a viscosity of about 3000 mPa-s and was described by the average molecular formula (MeO)3SiO(Me2SiO)30()Si(OMe)3: 20 parts of a partial hydrolysate/condensate of methyltrimethoxysilane(MS51® from Mitsubishi Chemical) with a viscosity of 5mm2/s and an methoxy residue/Si ratio of 2.5, 390 parts of an isoparaffin solvent
(Isosol 300® from Nippon Petrochemicals), 10 parts of isopropyl alcohol, and 3 parts of bis(isopropoxy)titanium bis(acetyl acetonate), yielding a silicone composition for coating. The resulting silicone composition was applied to a polyester nonwoven for wallpaper and heat-treated for 5minutes in a 100°C oven, yielding a cured film. The contact angle of the film with water was 106° and the pencil hardness thereof was 6B or less.
Working Example 4. The following components were added to 100 parts of a polydimethylsiloxane fluid that had a viscosity of about 3000 mPa-s and was described by the average molecular formula (MeO)3Si-C2H4-(Me2SiO)30()Me2Si-C2H4-Si(OMe)3: 20 parts of the partial hydrolysate/condensate of methyltrimethoxysilane(Bl) obtained as the synthetic example, 390 parts of an isoparaffin solvent (Isosol 200® from Nippon Petrochemicals), 10 parts of isopropyl alcohol, and 3 parts of bis(isopropoxy)titanium bis(acetyl acetonate), yielding a silicone composition for coating. The resulting silicone composition was applied to a polyester nonwoven for wallpaper and heat-treated for 5 minutes in a 100°C oven, yielding a cured film. The contact angle of the film with water was 106° and the pencil hardness thereof was 6B or less.
Working Example 5. The following components were added to 100 parts of a polydimethylsiloxane fluid that had a viscosity of about 3000 mPa-s and was described by the average molecular formula (MeO)3SiO(Me2SiO)3θθSi(OMe)3 : 20 parts of the partial hydrolysate/condensate of methyltrimethoxysilane(Bl) obtained as the synthetic example, 390 parts of ethyl acetate, 10 parts of isopropyl alcohol, and 3 parts of bis(isopropoxy)titanium bis(acetyl acetonate), yielding a silicone composition for coating.
The resulting silicone composition was applied to a polyester nonwoven for wallpaper and heat-treated for 10 minutes in a 80°C oven, yielding a cured film. The contact angle of the film with water was 105° and the pencil hardness thereof was 6B or less.
Comparative Example 2. The following components were added to 100 parts of a polydimethylsiloxane fluid that had a viscosity of about 3000 mPa-s and was described by the average molecular formula (MeO)3SiO(Me2SiO)30()Si(OMe)3: 20 parts of the partial hydrolysate/condensate of methyltrimethoxysilane(Bl) obtained as the synthetic example, 400 parts of isopropyl alcohol, and 3 parts of bis(isopropoxy)titanium bis(acetyl acetonate), yielding a silicone composition for coating.
The resulting silicone composition was applied to a polyester nonwoven for wallpaper and heat-treated for 5 minutes in a 100°C oven, yielding a cured film. The contact angle of the film with water was 106°. The silicone composition was stored for 3 months at room temperature, a cured film was formed on the surface of a polyester nonwoven for wallpaper in the same manner and the contact angle of the film with water was measured and found to have decreased to 100°. It was thus demonstrated that the silicone composition had inadequate storage stability.
Comparative Example 3. The following components were added to 100 parts of a polydimethylsiloxane fluid that had a viscosity of about 3000 mPa-s and was described by the average molecular formula (MeO)3SiO(Me2SiO)30()Si(OMe)3: 20 parts of the partial hydrolysate/condensate of methyl trimethoxysilane(Bl) obtained as the synthetic example, 400 parts of an isoparaffin solvent (Isosol 300® from Nippon Petrochemicals), and 3 parts of bis(isopropoxy)titanium bis(acetyl acetonate), yielding a light-yellow transparent silicone composition for coating.
The silicone composition was stored at room temperature, and cloudiness was observed in two months. It was thus demonstrated that the silicone composition had inadequate storage stability.
Comparative Example 4. The following components were added to 100 parts of a polydimethylsiloxane fluid that had a viscosity of about 3000 mPa-s and was described by the average molecular formula (MeO)3SiO(Me2SiO)30()Si(OMe)3: 20 parts of the partial hydrolysate/condensate of methyltrimethoxysilane(Bl) obtained as the synthetic example, 390 parts of an isoparaffin solvent (Isosol 300® from Nippon Petrochemicals), 10 parts of isopropyl alcohol, and 3 parts of dibutyltin dilaurate, yielding a silicone composition for coating.
The resulting silicone composition was applied to a polyester nonwoven for wallpaper and heat-treated for 5 minutes in a 100°C oven, yielding a cured film. The contact angle of the film with water was measured and found to be 100°, indicating that the film had inadequate water repellency.
Industrial Applicability Because the present silicone composition as described above is capable of forming a soft water-repellent film when cured for a short time at a low temperature, it is suitable as a water- repellent coating for acrylic resins, ABS resins, polyester nonwovens, leather, synthetic imitation leather, and other organic materials; and it can be used as a water-repellent agent for forming coatings on materials such as wallpaper, ceiling finishes, flooring materials, cloth, curtains, and other materials for interior use; doors, roofs, seats, and other interior materials of automobile or vehicle; and films, sheets, and other packaging materials.

Claims

1. A silicone composition for a water-repellent coating comprising (A) 100 weight parts of a polydimethylsiloxane described by general formula
(RO)3Si-Q-{(CH3)2SiO}n-(CH3)2Si-Q-Si(OR)3 , where R is a Ci to Cio monovalent hydrocarbon group, Q is an oxygen atom or a C2 to Cio alkylene group, and n is an integer from 10 to 1000;
(B) 5 to 100 weight parts of a partial hydrolysate/condensate of alkoxysilane, wherein the alkoxysilane has a general formula
RlxSi(OR2)4_x , where R is a C to C monovalent hydrocarbon group, R^ is a Ci to Cg alkyl group, and x is an integer from 0 to 3;
(C) 0.1 to 10 weight parts of an organotitanium-based catalyst; (D) 50 to 900 weight parts of an aliphatic hydrocarbon solvent or ester-based solvent; and (E) 0.1 to 100 weight parts of an alcohol-based solvent.
2. The silicone composition according to Claim 1, where the content of alkoxy groups in component (B), expressed as the OR^/Si ratio, is 0.8 to 2.6.
3. The silicone composition according to either Claim 1 or 2, where R! is methyl, R^ is selected from methyl and ethyl, and x is 1 or 0.
4. The silicone composition according to either Claim 1 or 2, where n is an integer from 100 to 800.
5. The silicone composition according to either Claim 1 or 2, where component (B) has a viscosity at 25°C of 1 to 100mm /s.
6. The silicone composition according to either Claim 1 or 2, comprising 5 to 20 weight parts of component (B) per 100 weight parts of component (A).
7. The silicone composition according to either Claim 1 or 2, comprising 100 to 500 weight parts of component (D) per 100 weight parts of component (A).
8. The silicone composition according to either Claim 1 or 2, comprising 0.5 to 50 weight parts of component (E) per 100 weight parts of component (A).
9. A silicone composition for a water-repellant coating comprising
(A) 100 weight parts of a polydimethylsiloxane described by general formula (RO)3Si-Q-{(CH3)2SiO}n-(CH3)2Si-Q-Si(OR)3 , where R is a Ci to C o monovalent hydrocarbon group, Q is an oxygen atom or a C2 to Cio alkylene group, and n is an integer from 100 to 800; (B) 5 to 20 weight parts of a partial hydrolysate/condensate of alkoxysilane, wherein the alkoxysilane has a general formula
RlxSi(OR2)4_x , where R^ is methyl, R2 is selected from the group consisting of methyl and ethyl, x is 1 or 0, and the ratio of OR2/Si is 0.8 to 2.6; (C) 0.1 to 10 weight parts of an organotitanium-based catalyst;
(D) 100 to 500 weight parts of an aliphatic hydrocarbon solvent or ester-based solvent; and
(E) 0.5 to 50 weight parts of an alcohol-based solvent.
10. An organic material coated with the composition of any of Claims 1, 2 or 9.
PCT/JP2002/005130 2001-05-30 2002-05-27 Silicone composition for water-repellent coating WO2002098983A1 (en)

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