WO2007116988A1 - Agent d'enrobage durcissable a la silicone - Google Patents

Agent d'enrobage durcissable a la silicone Download PDF

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Publication number
WO2007116988A1
WO2007116988A1 PCT/JP2007/057799 JP2007057799W WO2007116988A1 WO 2007116988 A1 WO2007116988 A1 WO 2007116988A1 JP 2007057799 W JP2007057799 W JP 2007057799W WO 2007116988 A1 WO2007116988 A1 WO 2007116988A1
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Prior art keywords
coating agent
curable silicone
silicone coating
groups
wet
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PCT/JP2007/057799
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English (en)
Inventor
Hideyuki Mori
Junya Yokoi
Yuya Yamano
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Dow Corning Toray Co., Ltd.
Tokuyama Corporation
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Publication of WO2007116988A1 publication Critical patent/WO2007116988A1/fr

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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
    • 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
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • 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
    • 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
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • 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

Definitions

  • the present invention relates to a curable silicone coating agent that contains a wet-process silica. More specifically, the present invention relates to a curable silicone coating agent which is characterized by a relatively low viscosity for a given content of the wet-process silica and high uniformity, and is capable of forming a cured coating with excellent surface smoothness and high mechanical strength.
  • Curable silicone coating agents that contain dry-process silica, that is, fumed silica, especially hydrophobicallytreated fumed silica as a filler, are well known in the art and commercially produced ⁇ see Patent Reference 1 (Japanese Unexamined Patent Application Publication [hereinafter referred to as "JP Kokai”] H10-316933) and Patent Reference 2 (JP Kokai 2001-139816 ⁇ .
  • wet-process silica is merely exemplified as one of fillers which can be contained in curable silicone coating agents, and there is no practical example concerning curable silicone coating agents containing the wet-process silica in these patent references.
  • wet-process silicas were not be uniformly dispersed into cross-linkable diorganopolysiloxanes which constitute the main component of curable silicone coating agents, furthermore, an increase in the amount of the wet-process silica considerably increased viscosity, compositions containing such wet-process silica lacked uniformity, and surface smoothness and mechanical strength of a cured coating or cured film formed from the compositions were not enough.
  • a curable silicone coating agent that contains a wet-process silica which is characterized by a relatively low viscosity for a given content of the wet-process silica, and which makes it possible to prepare a uniform composition and to form a smooth and strong cured coating or cured film.
  • the present invention specifically relates to the following •" [l] A curable silicone coating agent that contains a wet-process silica which satisfies the requirements (l) to (3) given below :
  • the curable silicone coating agent of item [5], wherein the condensation-curable silicone coating agent comprises: (A) a diorganopolysiloxane which is liquid at room temperature and is capped at molecular terminals with silanol groups or silicon-bonded hydrolyzable groups;
  • component (B) an organosilane-type or an organosiloxane-type cross-linking agent having an amount of silicon-bonded hydrolyzable groups sufficient for cross-linking with component (A);
  • component (C) a wet-process silica as claimed in Claims 1 or % and
  • component (D) a condensation re action -accelerating catalyst in an amount required for curing component (A).
  • component (A) is a dimethylpolysiloxane capped at molecular terminals with silanol groups, silicon-bonded ketoximo groups, or silicon-bonded alkoxy groups which has a viscosity of 20 to 20,000 mPa-s at 25°C;
  • component (B) is an organosilane of the following general formula '• (where R is a univalent hydrocarbon group with 1 to 10 carbon atoms; X is a ketoximo group or an alkoxy group, and "a" is 0 or l); and component (D) is an organic tin compound or an organic titanium compound.
  • component (A) is a mixture of constituents (Al) and (A2) described below and combined in a weight ratio which is in a range of 1/99 to 10/90:
  • (A2) a dimethylpolysiloxane capped at both molecular terminals with silanol groups which has a viscosity of 1000 to 5000 mPa-s at 25°C.
  • the curable silicone coating agent of the present invention contains the wet-process silica satisfying the following three requirements : (l) average diameter of agglomerated particles measured by a laser diffraction scattering method: not exceeding 5 ⁇ m, (2) percentage of silica particles with a size of not greater than 1 ⁇ m, as measured by the laser diffraction scattering method, per all silica particles: not less than 10%; and (3) boiled linseed oil absorption: not less than 200c/100 g, and preferably further additional requirement: (4) BET specific surface area in the range of 100 to 300 m 2 /g, it becomes possible to provide a curable silicone coating agent that is characterized by a relatively low viscosity for a given content of the wet-process silica, an excellent uniformity as the composition, and a smooth and strong cured coating or cured film.
  • a curable silicone coating agent of the present invention is characterized by containing a wet-process silica which satisfies the requirements (l) to (3) given below: (1) average diameter of agglomerated particles measured by a laser diffraction scattering method: not exceeding 5 ⁇ m
  • the aforementioned wet-process silica preferably satisfies the requirement: (4) BET specific surface area in the range of 100 to 300 m 2 /g.
  • the curable silicone coating agent has a viscosity which is relatively low for a given content of the wet-process silica. In other words, even though the content of the wet-process silica in the curable silicone coating agent is high, this does not significantly increase the viscosity of the curable silicone coating agent.
  • wet-process silica used in the present invention can be dispersed into a cross -linkable organopolysiloxane (which is the main component of the curable silicone coating agent) and a cross-linking agent much easier and uniformly than a conventional wet-process silica by kneading with a small share force.
  • the resultant curable silicone coating agent acquires excellent . uniformity and storage stability as a composition, and a cured coating therefrom acquires excellent surface smoothness and high mechanical strength.
  • the wet-process silica used in the present invention can be contained in the curable silicone coating agent in a larger amount. But if the content of the wet-process silica is too high, this increases viscosity and decreases coatability. Therefore it is recommended that the maximum content of the aforementioned wet-process silica does not exceed 40 wt.%, preferably 30 wt.%.
  • the content of the wet-process silica in the coating agent should be preferably 1 wt.% or more, and should be more preferably 4 wt.% or more.
  • the first feature of the aforementioned wet-process silica is that the average diameter of agglomerated particles measured by a laser diffraction scattering method (hereinafter referred to as "LS method") does not exceed 5 ⁇ m. More specifically, the wet-process silica should have an average size of agglomerated particles not exceeding 5 ⁇ m when measured by the LS method with the use of a commercial grain size distribution measurement instrument (such as an instrument of Beckman Coulterjnc.; COULTER® LS230).
  • LS method laser diffraction scattering method
  • the average diameter of agglomerated particles exceeds 5 ⁇ m, it will not be possible to uniformly disperse the wet-process silica in the cross-linkable organopolysiloxane (which is the main component of the curable silicone coating agent) and to obtain a smooth and mechanically strong cured coating.
  • the minimal limit of the average diameter of agglomerated particles but if this diameter is too small, a thickening property and mechanical strength of the cured coating will become insufficient.
  • the minimum size of the aforementioned particles should be 0.5 ⁇ m.
  • the average size of agglomerated particles measured by the LS method be in the range of 0.5 ⁇ m to 5.0 ⁇ m.
  • the second distinguishing feature of the wet-process silica used in the present invention is that the percentage of silica particles with a size of not greater than 1 ⁇ m, as measured by the LS method, per all silica particles is not less than 10%. If the percentage of silica particles with a size of not greater than 1 ⁇ m is less than 10%, then, even with the average diameter of agglomerated particles not exceeding 5 ⁇ m, it will be difficult to provide sufficient dispersion of the wet-process silica in a cross-linkable organopolysiloxane, which is the main component of the curable silicone coating agent, and so forth. This, in turn, will impair uniformity of the coating agent, and surface smoothness and mechanical strength of the cured coating.
  • the content of silica particles with the size of not greater than 1 ⁇ m is not less than 10%, preferably not lower than 20%, more preferably not less than 30%, and most preferably not less than 50%.
  • the upper limit of the content of particles not greater than I ⁇ m may be as high as 100%. In reality, however, the upper limit of the content of the aforementioned particles is 90% due to manufacturing techniques therefore.
  • the wet-process silica in which the percentage of silica particles with the size of not greater than 1 ⁇ m is not less than 10% and in which an average diameter of an agglomerated particle measured by the LS method does not exceed 5 ⁇ m, can be much easier dispersed in a cross-linkable organopolysiloxane, which is the main component of the curable silicone coating agent, and a cross-linking agent than a conventionally used dry-process silica. Moreover, mutual aggregation of secondary aggregation particles is relatively weak. Therefore, it becomes possible to restrict the viscosity increase during kneading, even if it is compounded at high concentrations.
  • the third distinguishing feature of the wet-process silica used in the present invention is that boiled linseed oil absorption measured in accordance with JIS K5101 is not less than 200 cc/100 g. With a boiled linseed oil absorption less than 200 cc/100g, the cured coating formed from the curable silicone coating agent will lose its mechanical strength and become brittle, even though the wet-process silica satisfies both requirements mentioned above. Therefore, it is recommended that the boiled linseed oil absorption be in the range of 230 cc/100 g to 320 cc/100 g.
  • the fourth distinguishing feature of the wet-process silica used in the present invention is that it preferably has a BET specific surface area in the range of 100 to 300 m 2 /g.
  • the BET specific surface area is the specific surface area measured by the application of the polymolecular layer adsorption theory described by S. Brunauer, P.H. Emmett, and E. Teller in: "J. Am. Chem. Soc, 60, 309 (1938). Concretely speaking, it is the specific surface area measured by the nitrogen -adsorption method (one-point method).
  • BET specific surface area is less than 100 m 2 /g, then interaction with the cross-linkable organopolysiloxane, and hence the mechanical strength of the cured coating, will be insufficient. If, on the contrary, the BET specific area exceeds 300 m 2 /g, this will strengthen mutual coagulation of wet-process silica particles in a dried state, hamper crushing of the silica particles to a fine state, increase viscosity of the curable silicone coating agent, impair dispersion of the silica particles in a cross-linkable organopolysiloxane that constitutes the main component of the curable silicone coating agent and a cross-linking agent, and thus will impair coatability of the curable silicone coating agent.
  • BET specific surface area should be preferably in the range of 150 m 2 /g to 250 m 2 /g.
  • the aforementioned wet-process silica satisfying the aforementioned requirements (l) to (3), or (l) to (4) is not restricted by any other properties , and it may have any appropriate content of water, pH value, bulk specific gravity, pore volume, electrical conductivity, etc. It may be recommended, however, to have a water content not exceeding 8 wt.%, pH value in the range of 4.0 to 7.0, bulk specific gravity in the range of 15 to 50 g/L, and pore volume in the range of 2.0 to 5.0 cm 3 /g.
  • finely crushed wet-process silica can be easily produced by coarsely crushing with the use of an impact crusher normally used for conventional wet-process silica (such as TOKUSIL USA, a product of Tokuyama Corporation) with subsequent fine crushing in a jet-type crusher.
  • an impact crusher normally used for conventional wet-process silica (such as TOKUSIL USA, a product of Tokuyama Corporation)
  • Typical examples of coarse crushers are a pin-type mill, a hammer mill (a product of SEISHIN ENTERPRISES CO., LTD.), NARA MiU (a product of NARA MACHINERY CO., LTD.).
  • Typical examples of fine crushers are a single-track jet mill, JETO-MILL (a product of SEISHIN ENTERPRISES CO., LTD.), cross-jet mill (a product of KURIMOTO, LTD.), and counter-jet mill (a product of HOSOKAWA MICRON CORPORATION).
  • a method for manufacturing the wet-process silica subjected to finely crushing is not limited. It consists of causing precipitation of a hydrous silicic acid by neutralizing sodium silicate, which is dissolved in water, with the use of sulfuric acid. For example, sulfuric acid is continuously added dropwise to the aqueous solution of sodium silicate adjusted to a predetermined concentration; a sodium silicate and sulfuric acid are added to an aqueous solution of sodium silicate dropwise and simultaneously, while stirring the solution at the predetermined temperature; or a method intermediate between both aforementioned methods can be used.
  • the boiled linseed oil absorption can be adjusted by controlling various conditions in the neutralization reaction and by controlling drying method and conditions. For example, for constant specific surface area, the higher is the neutralization reaction temperature, the greater is the boiled linseed oil absorption.
  • drying There are no special restrictions with regard to the method of drying, and steam drying, stationary drying, flash drying, etc. can be applied without limitation, of which the flash drying is most preferable for obtaining a wet-process silica with larger boiled linseed oil absorption.
  • a wet-process silica manufactured by the above-described methods is compounded with a cross-linkable organopolysiloxane, which is the main component of the curable silicone coating agent, and a cross-linking agent.
  • a cross-linkable organopolysiloxane which is the main component of the curable silicone coating agent, and a cross-linking agent.
  • Curing of the curable silicone coating agent of the present invention may be carried out with the use of any curing mechanism suitable for that purpose.
  • this can be condensation-reaction curing, hydrosilylation-reaction curing, curing by UV radiation, curing with organic peroxide, etc.
  • a cross-linkable organopolysiloxane especially a cross-linkable diorganopolysiloxane, is an indispensable component of the curable silicone coating agent of the present invention.
  • the curable silicone coating agent In order to impart to the uncured composition good flowability and coatability, and in order to impart to a cured body good physical properties, it is recommended for the curable silicone coating agent to contain the wet-process silica in the range of 1 to 40 wt.%, and to provide a viscosity of the composition at 25°C. (as measures by the method specified in below-given paragraph [0045]) preferably in the range of 0.01 to 50.0 Pa-s, that is, 10 to 50,000 mPa-s, and, more preferably, 100 to 25,000 mPa-s.
  • a condensation-curable silicone coating agent is a one-part RTV type
  • it can be stored over a long period of time under moisture-isolated conditions and can be cured at room temperature when exposed to wet air. Therefore, the one-part RTV type is preferred.
  • a typical condensation-curable silicone coating agent consists of the following components ⁇ ' (A) a diorganopolysiloxane which is liquid at room temperature and is capped at molecular terminals with silanol groups or silicon-bonded hydrolysable groups; (B) a curing agent of an organosilane or organosiloxane type that contains silicon-bonded hydrolysable groups in an amount sufficient for cross-linking with component (A); (C) a wet-process silica as claimed in Claim 1 or Claim 2; and (D) a condensation re action- accelerating catalyst in a required quantity.
  • Component (A) is a main component of the curable silicone coating agent. It is cross-linked with component (B) by a condensation reaction and is cured. Depending on the type of silicon-bonded hydrolysable groups, component (A) can be cured without component (D). However, presence of component (D) is desirable for acceleration of curing. There are no special restrictions with regard to the viscosity of component (A), provided that it is liquid at room temperature. However, the viscosity of component (A) is preferably in the range of 20 to 20,000 mPa-s at 25 0 C.
  • Silicon-bonded organic groups of the aforementioned diorganopolysiloxane may be exemplified by methyl groups, ethyl groups, propyl groups, or similar alkyl groups; vinyl groups, allyl groups, or similar alkenyl groups,' phenyl groups, or similar unsubstituted univalent hydrocarbon groups; and 3,3,3-trifluoropropyl groups, nanofluorohexyl groups, or similar perfluoroalkyl groups, of which preferable are methyl, vinyl, phenyl, and 3,3,3-trifluoropropyl groups, and most preferable are methyl groups.
  • Aforementioned component (A) can be exemplified by a dimethylpolysiloxane, a dimethylsiloxane • methylphenylsiloxane copolymer, a methylalkylpolysiloxane, and a methyl (3,3,3-trifluoropropyl) polysiloxane, which are capped at both molecular terminals with silanol groups, silicon-bonded methoxy groups, or ethoxy groups. From the viewpoint of low cost and improved properties of a cured product, the use of dimethylpolysiloxane is most preferable.
  • Terminal groups of the dimethylpolysiloxane capped with silicon-bonded methoxy groups or ethoxy groups can be represented by methyldimethoxysiloxy groups, methyldiethoxysiloxy groups, trimethoxysiloxy groups, triethoxysiloxy groups, methyldimethoxysilylethyl (dimethyl) siloxy groups, and trimethoxysilylethyl (dimethyl) siloxy groups.
  • Component (A) may be composed of two or more jointly used diorganopolysiloxanes of different viscosities.
  • component (A) may comprise a mixture of (Al) a dimethylpolysiloxane which is capped at both molecular terminals with silanol groups and has a viscosity of 20 to 100 mPa-s at 25°C. and (A2) a dimethylpolysiloxane which is capped at both molecular terminals with silanol groups and has a viscosity of 1000 to 5000 mPa-s at 25 0 C.
  • Constituents (Al) and (A2) can be mixed in a weight ratio of 1/99 to 10/90.
  • Component (B) which is a cross-slinking agent for component (A), contains at least two, and preferably three or four, silicon-bonded hydrolysable groups.
  • this component is an organosilane represented by the general formula: R a SiX4- a (where R is a univalent hydrocarbon group with 1 to 10 carbon atoms, X is a hydrolysable group, and "a" is 0 or l) or an organosiloxane oligomer which is a product of partial hydrolysis and condensation of the aforementioned organosilane.
  • R a SiX4-a represents an organosilane represented by the general formula: R a SiX4- a (where R is a univalent hydrocarbon group with 1 to 10 carbon atoms, X is a hydrolysable group, and "a" is 0 or l) or an organosiloxane oligomer which is a product of partial hydrolysis and condensation of the aforementioned organosilane.
  • R a SiX4-a also may be used as a cross-linking agent.
  • R is a univalent hydrocarbon with 1 to 10 carbon atoms, such as a methyl group, propyl group, tert-butyl group, 2-ethylhexyl group, or a similar alkyl group; a vinyl group, allyl group, or a similar alkenyl group; or a phenyl group, or a similar aryl group.
  • a methyl group, propyl group, tert-butyl group, 2-ethylhexyl group, or a similar alkyl group such as a methyl group, propyl group, tert-butyl group, 2-ethylhexyl group, or a similar alkyl group; a vinyl group, allyl group, or a similar alkenyl group; or a phenyl group, or a similar aryl group.
  • preferable are an alkyl group, alkenyl group, and phenyl group, and most preferable is a methyl group.
  • X designates a silicon-bonded hydrolysable group, examples of which are given above in paragraph [0024].
  • component (B) tetramethoxysilane, tetraethoxysilane, n-propylorthosilicate, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, vinyltrimethoxysilane, vinyHris (2-methoxyethoxy) silane, 3-aminopropyl trimethoxysilane, 3-glycidoxy propylmethyl dimethoxy silane, bis-[3-(triethoxysilyl)-propyl] tetrasulfide, bis-3-(triethoxysilyl)-propyl] disulfide, triethoxysilylpropyl-methacrylate monosulfide, tetrakis (methylethylketoximo) silane, methyl-tris (methylethylketoximo) silane, vinyl-
  • tetraethoxysilane methyltriethoxysilane, vinyltrimethoxysilane, vinyl-tris (2-methoxyethoxy) silane, or a similar alkoxysilane,' [0028] methyl-tris (inethylethylketoximo) silane of the following structural formula (l) :
  • ketoximosilane also known as a "ketoximinosilane”
  • component (B) When terminals of component (A) are capped with silanol groups, component (B) may be used with any hydrolyzable groups, but when terminals of component (A) are capped with hydrolysable groups, component (B) should be selected with the hydrolysable groups which are the same kind of hydrolysable groups on the terminals of the component (A). For example, when molecular terminals of component (A) are capped with alkoxy groups, X in the above formula of component (B) also should be an alkoxy group, and when molecular terminals of component (A) are capped with ketoximo groups, X in the above formula of component (B) also should be a ketoximo group.
  • Component (B) should be contained in an amount sufficient for curing component (A). This amount is defined as one that allows prolonged storage of the curable silicone coating agent which is one-part RTV type under moisture isolated conditions and that allows curing at room temperature in moisture -containing air. It is impossible to give a common recommendation for the content of component (B) since the specific amount will depend on the amount of silanol groups or hydrolysable groups present in component (A), as well as on the amount of hydrolysable groups in component (B), but in general component (B) can be contained in an amount of 2 to 30 wt %. For example, it can be contained in an amount of 5 to 100 parts by weight per 100 parts by weight component (A), but the range of 8 to 40 part by weight per 100 parts by weight component (A) is preferable from the viewpoint of improved curability.
  • Component (C) is a reinforcing filler, which is another indispensable component of the curable silicone coating agent. Its properties, characteristics, methods of production, etc. were described above.
  • component (C) can be contained in the curable silicone coating agent of the present invention, but if the amount of component (C) is too small, the curable silicone coating agent will be too thin and it will become difficult to coat it. Furthermore, the cured coating therefrom will have low mechanical strength. If, on the other hand, component (C) is contained in an excessive amount, the curable silicone coating agent will become too sticky and it will become difficult to coat it. Therefore, it is recommended to contain component (C) in an amount of 1 to 40 wt.%, preferably 4 to 30 wt.%.
  • component (C) can be contained, e.g., in an amount of 1 to 60 parts by weight per 100 parts by weight of component (A). From the viewpoint of improved coatability and water repellency, component (C) should be contained in an amount of preferably 5 to 40 parts by weight, more preferably 8 to 35 parts by weight.
  • the curable silicone coating agent of the present invention may be composed only of the aforementioned components from (A) to (C). However, depending on the kind of component (B), it is preferable to contain a condensation reaction-accelerating catalyst in order to improve curing properties.
  • Such a catalyst may be conventional one used for the same purpose and may be represented by the following compounds: dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate, tin octylated, or a similar organic tin compound; tetra (i-propyl) titanate, tetra (n-butyl) titanate, dibutoxy bis (acetylacetonate) titanium, isopropyl triisostearoyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, bis (pyrophosphate) oxyacetate titanate, or a similar organic titanium compound!
  • tetrabutyl zirconate tetrakis (acetylacetonate) dizirconium, tetraisobutyl zirconate, tetraisobutyl zirconate, butoxytris (acetylacetonate) zirconium, zirconium naphthenate, or a similar organic zirconium compound; tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, or a similar organic aluminum compound; zinc naphthenate, cobalt naphthenate, or a similar metal salt of organic- acid; and diethanolamine, triethanolamine, or a similar amine -type catalyst.
  • Organic tin compounds and organic titanate compounds are most suitable for an alcohol-liberating condensation-reaction curable silicone coating agents, and organic titanate compounds are most suitable for oxime-liberating condensation-reaction curable silicone coating agents.
  • the condensation-reaction accelerating catalyst (D) contained in the curable silicone coating agent should be contained in an amount sufficient for accelerating condensation reaction in which components (A) and (B) participate.
  • This component is contained in an amount of, for example, 0 to 15 wt.%, preferably 0.1 to 8 wt.%.
  • component (D) can be contained, e.g., in an amount of 0 to 20 parts by weight, and for better curability, in an amount of 0.1 to 12 parts by weight, per 100 parts by weight of component (A).
  • the curable silicone coating agent of the present invention may be combined with various organic functional silane coupling agents and organosiloxane oligomers that contain organic functional groups and silicon-bonded alkoxy groups.
  • organic functional silane coupling agents and organosiloxane oligomers that contain organic functional groups and silicon-bonded alkoxy groups.
  • adhesion promoters are the following: 3-aminopropyl trimethoxy silane, 3-aminopropyl trimethoxy silane, 3-(2-aminoethyl) aminopropyl trimethoxy silane,
  • adhesion promoters should be contained in amounts sufficient for improving adhesion when cured, e.g., in an amount of 0 to 15 wt.%.
  • the aforementioned adhesion promoters should be contained, e.g., in an amount of 1 to 10 parts by weight, preferably 1.5 to 8 parts by weight per 100 parts by weight of component (A).
  • the curable silicone coating agent is too thick, its viscosity can be reduced by containing an organic solvent.
  • the organic solvent can reduce the viscosity and improve coatability of the curable silicone coating agent.
  • the appropriate organic solvent should have a boiling point preferably in the range of 100°C to 200 0 C and should be able to dissolve components (A) and (B).
  • iso-paraffin normal paraffin ("Isosol® 200", “Isosol® 300”, and “Normal Paraffin SL", the products of Nippon Petrochemical Co., Ltd.), or similar aliphatic hydrocarbons; butyl acetate, isobutyl acetate, or similar carboxylic-acid esters; hexamethyldisiloxane; octamethyltrisiloxane, or similar cyclic dimethylsiloxane oligomers; or a mixture of two of more compounds listed above.
  • the aforementioned organic solvent should be contained in an amount sufficient for reducing the viscosity of the curable silicone coating agent, e.g., in an amount of 4 to 100 wt.%, preferably 10 to 50 wt.% per total content of components (A) to (C). It goes without saying that the curable silicone coating of the present invention can be used as a non-solvent type.
  • the curable silicone coating of the present invention may be further combined with non- re active and hydrophobic silicone fluids.
  • Such fluids are liquid diorganosiloxanes the molecules of which are free of condensation-reactive groups such as silanol groups and hydrolysable groups.
  • the aforementioned fluids should have a viscosity in the range of 10 to 10,000 mPa- s at 25°C.
  • the silicon-bonded organic groups can be exemplified by methyl groups, ethyl groups, propyl groups, or similar alkyl groups! vinyl groups, allyl groups, or similar alkenyl groups! and phenyl groups, or similar aryl groups.
  • a trimethylsiloxycapped dimethylpolysiloxane fluid a dimethylsiloxane • methylphenylsiloxane copolymer fluid, dimethylsiloxane • methylvinylsiloxane copolymer fluid, and a dimethylsiloxane -dip henylsiloxane copolymer fluid.
  • Such non-reactive silicone fluids can be contained in an amount of 1 to 50 wt.%, preferably 5 to 40 wt.% per total content of components (A) to (C).
  • the curable silicone coating agent of the present invention may also contain optionally other additives and fillers, such as titanium oxide, Navy blue, Berlin blue, zinc oxide, red iron oxide, carbon black, transparent iron oxide, aluminum powder, or a similar inorganic pigment; azo-type pigment, triphenylmethane-type pigment, quinoline-type pigment, antraquinone-type pigment, phthalocyanine-type pigment, or similar organic pigments; finely powdered quartz, powdered calcium carbonate, powdered diatomaceous earth, powdered aluminum hydroxide, finely powdered alumina, powdered magnesia, as well as the aforementioned powders surface-treated with silanes, silazanes, low-degree-polymerization siloxanes, or organic compounds; glass baloons, hollow thermoplastic resin powders, or similar hollow fillers)" a powdered cerium oxide, powdered cerium hydroxide, powdered iron oxide, or similar heat-resistant agents; a platinum-type catalyst
  • the curable silicone coating agent of the present invention is easily prepared by kneading aforementioned components (A) to (C), if necessary with some of the aforementioned arbitrary components, in a conventional kneading machine, such as a planetary mixer, Hobart mixer, Torero mixer, roll mill, Henschel mixer, Banbury mixer, kneader mixer, flowjet mixer, ball mill, vibration mill, extruder, paddle mixer, ribbon mixer, etc. Mixing must be carried out under conditions that do not cause a condensation reaction. Components can be mixed in an arbitrary sequence.
  • components (A) to (C) and, if needed, arbitrary components, can be mixed simultaneously; components (A) and (C) can be first kneaded to uniformity at room temperature or with heating, then cooled, and combined with other components; or components (A) and (B) can be first kneaded to uniformity and then combined and kneaded with other components.
  • the curable silicone coating agent of the present invention may also be of a type curable with a hydrosilylation reaction.
  • a hydrosilylation-curable silicone coating agent may consists, e.g., of an diorganopolysiloxane having in one molecule at least two silicon-bonded alkenyl groups (e.g., a dimethylpolysiloxane capped at both molecular terminals with dimethylvinylsiloxy groups), an organopolysiloxane having in one molecular at least two, and preferably three or more, silicon-bonded hydrogen atoms (e.g., a methylhydrogenpolysiloxane capped at both molecular terminals with trimethylsiloxy groups), a hydrosilylation catalyst (e.g., a chloroplatinic acid), and the aforementioned wet-process silica.
  • the above-described composition may further include a hydrosilylation-reaction inhibitor.
  • the wet-process silica may
  • hydrosilylation-curable silicone coating agent that contains a hydrosilylation-reaction inhibitor is coated onto a substrate and cured at 50 to 200°C, it quickly forms on the substrate surface a rubber-like cured coating.
  • the curable silicone coating agent of the present invention may also be of a type curable with the use of an organic peroxide.
  • An organic-peroxide-curable silicone coating agent comprises the following components : a diorganopolysiloxane having in one molecule at least two alkenyl groups; component (C); and an organic peroxide.
  • the organic peroxide can be exemplified by a dibenzoyl peroxide, 2,4-dimethylbenzoyl peroxide, 4-methylbenzoyl peroxide, dicumyl peroxide, tert-butyl perbenzoate, tert-butyl peroxide, 2,5-dimethyl-2,5"bis(tert-butylperoxy) hexane, and cumyHert-butyl peroxide.
  • the aforementioned wet-process silica can be contained in an amount of preferably 1 to 40 wt.%, more preferably 4 to 30 wt.%.
  • the organic-peroxide -curable silicone coating agent When the organic-peroxide -curable silicone coating agent is coated onto the . surface of a substrate and the applied coating is heated, e.g., to a temperature in the range of 100°C to 240°C, the coating is turned into a thin rubber-like cured coating on the substrate surface.
  • the curable silicone coating agent can be of a UV-curable type.
  • a UV-curable coating agent may consist of (l) a hydrosilylation-reaction-curable organopolysiloxane composition and a photo-polymerization initiator; (2) an acryHunctional polysiloxane and a polymerization initiator," or (3) an epoxyfunctional organopolysiloxane and a cation- generation type catalyst.
  • the photo-polymerization initiator may be selected from known compounds that generate radicals under the effect of UV radiation, which are exemplified by an organic peroxide, carbonyl compound, azo compound, or the like.
  • the cation-generating type catalyst used for a silicone coating agent composed of an epoxyfunctional organopolysiloxane and a cation- generating type catalyst is exemplified by known onium salt, such as a triaryl sulfonium salt, triaryl iodonium salt, or bis (dodecylphenyl)hexafluoro antimonite.
  • the aforementioned UV-curable silicone coating agent contains the wet-process silica in an amount of preferably 1 to 40 wt.%, and more preferably 4 to 30 wt.%.
  • the UV-curable silicone coating agent is coated onto a substrate, and then the coating is irradiated with UV rays in the wavelength range of 200 to 400 nm.
  • the wavelength range of 200 to 300 nm is preferable for UV-curable silicone coating agents that contain a cation- generating catalyst, and the wavelength of 300 to 400 nm is preferable for UV-curable silicone coating agents of a hydrosilylation-curable type. Radiation is carried out at a temperature of 0 to 80 0 C. As a result, a cured coating is formed.
  • the curable silicone coating agent of the present invention may have a viscosity arbitrarily selected to match the coating conditions.
  • a viscosity measured by the method described in paragraph [0045] below in the range of preferably 0.01 to 50.0 Pa-s, i.e., 10 to 50,000 mPa-s at 25°C, and more preferably 100 to 25,000 mPa-s at 25 0 C.
  • the curable silicone coating agent of the present invention may be coated onto a substrate by brushing, blade coating, spin coating, dipping, spraying, or by any convenient known method.
  • the coating may be applied not only as a single layer but in form of several layers. Since the curable silicone coating agent of the present invention has a viscosity which is rather low relative to the content of the wet-process silica, it is suitable for spray coating.
  • the coating layer is cured either by leaving it intact at room temperature or by heating.
  • the coating layer may have an arbitrary thickness which can be selected, e.g., in the range of 1 to 500 ⁇ m. An appropriate thickness is selected, depending on the purpose of the coating and smoothness of the substrate.
  • a substrate suitable for application of the curable silicone coating agent of the present invention may be arbitrary and can be made from a metal, mortar, slate, concrete, wood, plastic, film, rubber, synthetic leather, cloth, glass cloth, glass, ceramic, etc.
  • the silicone coating agent forms a cured coating with excellent surface smoothness and mechanical properties.
  • This characteristic was measured by a BET one-point method based on simplified nitrogen absorption method.
  • Diameters of agglomerated particles and percentage of particles with a size of not greater than 1 ⁇ m among all agglomerated particles were measured by means of a laser diffraction scattering instrument for measuring grain size distribution (instrument of Beckman Coulter,Inc.; model COULTER® LS230).
  • This measurement was carried out in accordance with the following sequence.
  • a test tube was filled with 0.1 g of the wet-process silica and 30 ml of methanol, and then dispersion was carried out with the use of an ultrasonic washer filled with water for three minutes at a power of 40W.
  • the dispersion was transferred to the laser diffraction scattering instrument for measuring grain size distribution (instrument of Beckman CoulterJncJ model COULTER® LS230), and then grain size distribution was measured by the method specified for the used equipment. In this case, purified water was used as a solvent for the instrument for measuring grain size distribution.
  • Viscosity Viscosity was measured by means of a VDA-type viscosimeter (the product of
  • the coating agent was visually observed prior to curing, and the appearance thereof was evaluated in accordance with the following criteria : ® - distribution is uniform
  • a mold form having a depth of 2 mm, a width of 50 mm, and a length of 250 mm was placed onto a polytetrafluoroethylene sheet, the mold form was filled with a curable silicone coating agent, and the surface of the filled coating agent was slowly spread with a spatula, whereby a 2 mnrdeep, 50 mm-wide, and 250 mnvlong sheet-like layer was formed. This layer was cured by retaining it indoors in a horizontal position for seven days. As a result, a silicone rubber sheet was produced.
  • a separate silicone rubber sheet was made from the silicone coating agent only of Application Example 10 by press vulcanization for 15 min. at 150 0 C.
  • Example 1 to Example 6 A mixer was filled with the following components ⁇ 100 parts by weight of a dimethylpolysiloxane capped at both molecular terminals with silanol groups having a viscosity of 2,200 mPa-s! 3.75 parts by weight of a dimethylpolysiloxane capped at both molecular terminals with silanol groups having a viscosity of 40 mPa-s; and 20 parts by weight of each of the wet-process silicas A to F.
  • a mixer was filled with the following components' 100 parts by weight of a dimethylpolysiloxane capped at both molecular terminals with silanol groups having a viscosity of 2,200 mPa-s; 3.75 parts by weight of a dimethylpolysiloxane capped at both molecular terminals with silanol groups having a viscosity of 40 mPa-sJ and 10 parts by weight of wet-process silica A.
  • the components were uniformly mixed at 120 0 C, cooled, and then uniformly mixed under moisture -isolated conditions with 8.0 parts by weight of a methyl-tris (methylethylketoximo) silane of structural formula (l) shown in paragraph [0028] and 8.0 parts by weight of a vinyl-tris (methylethylketoximo) silane of structural formula (2) shown in paragraph [0028].
  • a pasty oxime -liberating condensation-reaction curable silicone coating agent was prepared.
  • the prepared silicone coating agent was visually observed, and its viscosity and surface smoothness were measured. The results of measurement are shown in Table 2. Physical properties of the silicone rubber sheet prepared by curing the aforementioned coating agent are also shown in Table 2.
  • Example 8 A mixer was filled with the following components : 100 parts by weight of a dimethylpolysiloxane capped at both molecular terminals with silanol groups having viscosity of 2,200 mPa-s ⁇ 3.75 parts by weight of a dimethylpolysiloxane capped at both molecular terminals with silanol groups having a viscosity of 40 mPa-s; and 30 parts by weight of wet-process silica A.
  • the components were uniformly mixed at 12O 0 C, cooled, and then uniformly mixed under moisture-isolated conditions with 8.0 parts by weight of a methyl-tris (methylethylketoximo) silane of structural formula (l) shown in paragraph [0028] and 8.0 parts by weight of a vinyHris (methylethylketoximo) silane of structural formula (2) shown in paragraph [0028].
  • a pasty oxime-liberating condensation-reaction curable silicone coating agent was prepared.
  • the prepared silicone coating agent was visually observed, and its viscosity and surface smoothness were measured. The results of measurement are shown in Table 2. Physical properties of the silicone rubber sheet prepared by curing the aforementioned coating agent are also shown in Table 2.
  • Example 9 A mixer was filled with the following components ⁇ 100 parts by weight of a dimethylpolysiloxane capped at both molecular terminals with silanol groups having a viscosity of 2,000 mPa-sJ and 20 parts by weight of wet-process silica A. The components were uniformly mixed at 12O 0 C, cooled, and then uniformly mixed under moisture-isolated conditions with 7.5 parts by weight of a methyltrimethoxysilane and 2.0 parts by weight of a diisopropoxy-bis (ethylacetoacetate) titanium. As a result, a pasty methanoHiberating condensation-reaction curable silicone coating agent was prepared. The prepared silicone coating agent was visually observed, and its viscosity and surface smoothness were measured. The results of measurement are shown in Table 2. Physical properties of the silicone rubber sheet prepared by curing the aforementioned coating agent are also shown in Table 2.
  • a mixer was filled with the following components-" 100 parts by weight of a dimethylpolysiloxane capped at both molecular terminals with silanol groups having a viscosity of 2,200 mPa-sJ 3.75 parts by weight of a dimethylpolysiloxane having a viscosity of 40 mPa-s and capped at both molecular terminals with silanol groups having a viscosity of 40 mPa-s! and 20 parts by weight of wet-process silica G.
  • the components were uniformly mixed at 120 0 C, cooled, and then uniformly mixed under moisture -isolated conditions with 8.0 parts by weight of a methyl-tris (methylethylketoximo) silane of structural formula (l) shown in paragraph [0028] and 8.0 parts by weight of a vinyHris (methylethylketoximo) silane of structural formula (2) shown in paragraph [0028].
  • a pasty oxime -liberating condensation-reaction curable silicone coating agent was prepared.
  • the prepared silicone coating agent was visually observed, and its viscosity and surface smoothness were measured. The results of measurement are shown in Table 3. Physical properties of the silicone rubber sheet prepared by curing the aforementioned coating agent are also shown in Table 3.
  • [0055] A pasty oxime -liberating condensation-reaction curable silicone coating agent was prepared in the same manner as in Comparative Example 1, with the exception that 10 parts by weight of a hydrophilic dry-process silica H (the product of a Japanese silica manufacturer) having a BET specific surface area of 200 m 2 /g, an average agglomerated particles size of 0.2 ⁇ m, a 100% content of agglomerated particles with a size of not exceeding 1 ⁇ m, and an oil absorption of 200 cc/100 g were used instead of 20 parts by weight of the wet-process silica G of Comparative Example 1.
  • the prepared silicone coating agent was visually observed, and its viscosity and surface smoothness were measured. The results of measurement are shown in Table 3. Physical properties of the silicone rubber sheet prepared by curing the aforementioned coating agent are also shown in Table 3.
  • An oxime -liberating condensation-reaction curable silicone coating agent was prepared in the same manner as in Comparative Example 1, with the exception that 20 parts by weight of the hydrophilic dry-process silica H used in Comparative Example 2 were added instead of 20 parts by weight of the wet-process silica G of Comparative Example 1.
  • the prepared silicone coating agent was visually observed, and its surface smoothness was measured. However, viscosity of the obtained agent could not be measured since the product was too viscous.
  • the results are shown in Table 3. Physical properties of the silicone rubber sheet prepared by curing the aforementioned coating agent are also shown in Table 3.
  • a condensation-reaction curable silicone coating agent was prepared in the same manner as in Comparative Example 1, with the exception that 20 parts by weight of the hydrophobic dry-process silica I used in Comparative Example 4 were added instead of 20 parts by weight of the wet-process silica G of Comparative Example 1.
  • the prepared silicone coating agent was visually observed, and its surface smoothness was measured. However, viscosity of the . obtained agent could not be measured since the composition was too viscous.
  • the results are shown in Table 3. Physical properties of the silicone rubber sheet prepared by curing the aforementioned coating agent are also shown in Table 3. 059]
  • a flowable liquid silicone rubber base was prepared by loading 100 parts of a dimethylpolysiloxane capped at both molecular terminals with dimethylvinylsiloxy groups having a viscosity of 1,000 mPa-s and 20 parts by weight of aforementioned wet-process silica A into a mixer, mixing the components to homogeneity, and then uniformly mixing with heating. Following this, 100 parts of the prepared liquid silicone rubber base cooled to room temperature were combined with 5.0 parts of a methylhydrogensiloxane • dimethylsiloxane copolymer of the following average structural formula- Me 3 SiO (MeHSiO) 6 (Me 2 SiO) 4 SiMe 3
  • the components were uniformly mixed, whereby a silicone rubber-type coating agent was produced. Viscosity of the coating agent could not be measured, but the wet-process silica A was uniformly dispersed.
  • the prepared silicone rubber-type coating agent was formed into a silicone rubber sheet which had a hardness of 50, a tensile strength of 1.5 mPa, and an elongation of 80%.
  • the curable silicone coating agent of the present invention is useful as coating agents for architectural structures, civil engineering structures, vehicles, ships and vessels, industrial materials, industrial products, living wares, etc. comprising various substrates such as metals, mortar, slates, concrete, wood, plastics, films, rubber, synthetic leather, cloth, glass cloth, glass, ceramics, and other materials.

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Abstract

L'invention concerne un agent d'enrobage durcissable à la silicone, en particulier du type durcissable par réaction de condensation et contenant de la silice traitée par voie humide satisfaisant aux exigences (1) à (3) suivantes : (1) le diamètre moyen d'une particule agglomérée, mesuré par diffusion/diffraction laser, ne dépasse pas 5 micromètres ; (2) le pourcentage de particules de silice dont la taille, mesurée par diffusion/diffraction laser, ne dépasse pas 1 micromètre, n'est pas inférieur à 10 % de la quantité totale de particules de silice ; enfin (3) le taux d'absorption d'huile de graines de lin bouillies n'est pas inférieur à 200 cc/100 g.
PCT/JP2007/057799 2006-03-31 2007-04-02 Agent d'enrobage durcissable a la silicone WO2007116988A1 (fr)

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WO2013118483A1 (fr) * 2012-02-09 2013-08-15 パナソニック株式会社 Composition de matériau de revêtement et article revêtu avec cette composition de revêtement
CN103360820B (zh) * 2012-03-31 2015-11-25 攀钢集团攀枝花钢铁研究院有限公司 一种金属防护涂料及其用途和热镀金属材料
WO2016006591A1 (fr) * 2014-07-10 2016-01-14 Nok株式会社 Agent de traitement pour modification de surface, élément pour dispositif de formation d'image, et mécanisme de fixation de toner

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EP1167455A2 (fr) * 2000-06-30 2002-01-02 Shin-Etsu Chemical Co., Ltd. Composition de silicone à durcissement rapide à température ambiante
EP1557446A1 (fr) * 2004-01-22 2005-07-27 Shin-Etsu Chemical Co., Ltd. Compositions d'élastomère à silicone, leur production et utilisation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1167455A2 (fr) * 2000-06-30 2002-01-02 Shin-Etsu Chemical Co., Ltd. Composition de silicone à durcissement rapide à température ambiante
EP1557446A1 (fr) * 2004-01-22 2005-07-27 Shin-Etsu Chemical Co., Ltd. Compositions d'élastomère à silicone, leur production et utilisation

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