Classifications

• • 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
  • C08G77/06—Preparatory processes
  • C08G77/08—Preparatory processes characterised by the catalysts used
• • 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 hydroxy 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
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences

Definitions

• the present invention relates to a curable coating composition containing an organopolysiloxane.
• Silicone resin is currently widely used in various fields because it has excellent properties such as water repellency, heat resistance, weather resistance, cold resistance, electrical insulation, chemical resistance, and safety to the body. ..
• organopolysiloxane having a three-dimensional crosslinked structure containing SiO 4/2 unit (Q unit) or RSiO 3/2 unit (T unit) (R is an organic group such as an alkyl group or a phenyl group) as a main component is used.
• Silicone resin and silicone alkoxy oligomer which are widely used in paints, coating agents, binders, etc. due to their curability.
• the liquid silicone alkoxy oligomer having an alkoxysilyl group as a cross-linking group is used as the main agent of a solvent-free paint that is flammable and does not contain an organic solvent harmful to the human body (Non-Patent Document 1).
• the silicone alkoxy oligomer containing an alkoxysilyl group can be mixed with a curing catalyst to cause the alkoxysilyl group at room temperature.
• the groups can react to form a siloxane network. Since such a polysiloxane cured film is excellent in heat resistance and weather resistance, it is used in a wide range of fields from outdoor buildings to electronic parts.
• the silicone alkoxy oligomer undergoes a curing reaction even at room temperature, but the reaction can be promoted by heating, and a heat curing step is appropriately introduced depending on the application, and it can be said that the technique has excellent coating adaptability. ..
• silicone resins and silicone alkoxy oligomers have the advantages of good curability and high surface hardness due to their three-dimensional crosslinked structure, while their flexibility and bending resistance are high due to their high crosslink density. There is a problem that the coating film is insufficient and cracks occur over time after film formation or when external stress is applied.
• a method of incorporating a diorganosiloxane (R 2 SiO 2/2 ) unit (D unit) is generally adopted when synthesizing a silicone resin or a silicone alkoxy oligomer.
• D unit diorganosiloxane (R 2 SiO 2/2 ) unit
• Non-Patent Document 1 a method of adding silicone oil whose molecular end is sealed with TEOS (Si (OCH 2 CH 3 ) 4 ) has also been proposed (Non-Patent Document 1), but its compatibility with silicone resin and silicone alkoxy oligomer is poor, and it is poor. It caused cloudiness and repelling of the coating film.
• Patent Documents 1 and 2 The technique of introducing an alkoxysilyl group into linear silicone by a sill ethylene structure is possible and known by using a hydrosilylation reaction (Patent Documents 1 and 2).
• Patent Document 1 a side chain methyl / phenyl type silicone oil compound containing a hydrosilyl group and having a chain structure of D units and a silicone alkoxy oligomer compound having both an olefin and an alkoxysilyl group in the side chain are hydrosilyled.
• organopolysiloxane compounds containing both a silicone alkoxy oligomer structure having an alkoxysilyl group in one molecule and a structure derived from a side chain methyl / phenyl type silicone oil structure obtained by the chemical reaction.
• Patent Document 1 Since the organopolysiloxane compound of Patent Document 1 has a relatively long chain and a high molecular weight side chain methyl / phenyl type silicone oil structure, it is effective when added as a crack resistance imparting agent. However, even in this case, the hardness was insufficient when it was cured by itself, and it was difficult to use it alone for paints and coating agents.
• Patent Document 2 is a technique that emphasizes the aim of improving the feel of linear silicone such as a hair treatment agent, and does not mention its application as a flexible coating material.
• Patent Document 3 discloses that a silicone in which a long-chain alkyl group, an oxyalkylene group, a trialkoxysilyl group and the like are modified on the side chain of a branched organopolysiloxane is used as a powder surface treatment agent for cosmetics. .. However, its use as a coating component has not been described or suggested.
• the present invention has been made in view of the above circumstances, and contains an organopolysiloxane that provides a cured product having both hardness and bending resistance, an appearance with less friction on the coated surface, and a good feel and safety. It is an object of the present invention to provide a composition for coating.
• R 1 has an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 14 carbon atoms, and an aralkyl group having 3 to 10 carbon atoms. It is an organic group selected from the group consisting of a fluorine-substituted alkyl group and an organic group represented by the following general formula (2).
• R 4 is an alkyl group having 1 to 30 carbon atoms or an acyl group having 1 to 30 carbon atoms
• d is 0 ⁇ d ⁇ 15
• e is 0 ⁇ e ⁇ 50
• f is 0 ⁇ f ⁇ 50.
• R2 is a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or a group selected from the following general formula (3).
• R 5 is a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, or a phenyl group
• R 6 is an alkoxy group having 1 to 6 carbon atoms.
• Z is an integer of 2 to 8 and p is an integer of 1 to 3.
• R 3 is a silicone compound residue represented by the following general formula (4).
• R 7 independently has an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 14 carbon atoms, and a carbon number of carbon atoms.
• R 1 to R 7 are contained in the molecule, they may be the same or different from each other, where a is 1.0 ⁇ a ⁇ 2.5 and b is 0.001 ⁇ b ⁇ 1.5. And c are numbers 0 ⁇ c ⁇ 1.5.
• R 8 may have an independently substituent and has an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 to 7 carbon atoms. It is a group selected from the group consisting of 14 aralkyl groups and a fluorine-substituted alkyl group having 3 to 10 carbon atoms, R 9 is independently a hydrogen atom, a methyl group or an ethyl group, and m is 4 ⁇ m ⁇ . It is an integer of 50.
• C A curable coating composition containing a condensation curing catalyst is provided.
• a coating composition containing an organopolysiloxane that achieves both hardness and bending resistance, and further provides a cured product having an appearance with less friction on the coated surface and an excellent safety to the touch. Can be.
• the weight average molecular weight of the component (A) measured by gel permeation chromatography is 300 to 100,000 in terms of polystyrene.
• the composition is not sticky, and the coating film formed from the composition has sufficient surface slipperiness and water slipperiness.
• component (C) is one or more selected from the group consisting of an acid catalyst, an amine compound and a salt thereof, an aminoalkyl group-substituted alkoxysilane, and an aluminum-based, titanium-based and tin-based organometallic catalyst. It is preferable to have.
• Such a condensation curing catalyst can be used in the curable coating composition of the present invention.
• the curable coating composition of the present invention further contains (D) an organic solvent.
• the present invention provides an article having a cured film of the above-mentioned curable coating composition.
• the curable coating composition of the present invention can be suitably used for coating articles.
• the curable coating composition containing the organopolysiloxane of the present invention has a linear silicone as an essential structure as a film constituent, and further contains an alkoxysilyl group or a silanol group having hydrolytic condensability, so that it is cured by siloxane condensation cross-linking. Has the ability to form a film. Further, since the organopolysiloxane used in the present invention has excellent compatibility with other silicone components due to the silicone branched chain contained in the structure, both end functional silicones are optional for the curable coating composition of the present invention. It can be introduced into the film, which makes it easy to adjust the balance between film hardness and flexibility.
• the linear silicone structure contributes to the improvement of the touch, the water repellency, and the water slip property due to the low surface tension. Therefore, the present invention provides a coating composition containing an organopolysiloxane that achieves both hardness and bending resistance, and further provides a cured product having an appearance with less friction on the coated surface and an excellent feel and safety. be able to.
• the curable coating composition of the present invention having such characteristics gives durability and a certain hardness to a base material that is bent multiple times, and requires water repellency and a feel of the coating film surface. It can be suitably used for the intended use.
• the present inventors have introduced alkoxysilyl groups into the linear silicone main chain via a sylethylene structural group, and both ends of the organopolysiloxane and the linear silicone are dimethyl. It has been found that a hydrolyzed condensation-cured coating containing an organopolysiloxane as an essential component of a silanol group or a dimethylalkoxy group imparts desired properties, and the present invention has been made.
• the present invention comprises the following components (A) to (C); (A) Organopolysiloxane represented by the following general formula (1)
• R 1 has an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 14 carbon atoms, and an aralkyl group having 3 to 10 carbon atoms. It is an organic group selected from the group consisting of a fluorine-substituted alkyl group and an organic group represented by the following general formula (2).
• R 4 is an alkyl group having 1 to 30 carbon atoms or an acyl group having 1 to 30 carbon atoms
• d is 0 ⁇ d ⁇ 15
• e is 0 ⁇ e ⁇ 50
• f is 0 ⁇ f ⁇ 50.
• R2 is a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or a group selected from the following general formula (3).
• R 5 is a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, or a phenyl group
• R 6 is an alkoxy group having 1 to 6 carbon atoms.
• Z is an integer of 2 to 8 and p is an integer of 1 to 3.
• R 3 is a silicone compound residue represented by the following general formula (4).
• R 7 independently has an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 14 carbon atoms, and a carbon number of carbon atoms.
• R 1 to R 7 are contained in the molecule, they may be the same or different from each other, where a is 1.0 ⁇ a ⁇ 2.5 and b is 0.001 ⁇ b ⁇ 1.5. And c are numbers 0 ⁇ c ⁇ 1.5.
• R 8 may have an independently substituent and has an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 to 7 carbon atoms. It is a group selected from the group consisting of 14 aralkyl groups and a fluorine-substituted alkyl group having 3 to 10 carbon atoms, R 9 is independently a hydrogen atom, a methyl group or an ethyl group, and m is 4 ⁇ m ⁇ . It is an integer of 50.
• C A curable coating composition containing a condensation curing catalyst.
• organopolysiloxane [(A) Organopolysiloxane]
• the organopolysiloxane of the component (A) according to the present invention is represented by the following general formula (1).
• R 1 is an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 14 carbon atoms, and the like. It is an organic group selected from the group consisting of a fluorine-substituted alkyl group having 3 to 10 carbon atoms and an organic group represented by the following general formula (2), and has an alkyl group having 1 to 6 carbon atoms and an organic group having 3 to 6 carbon atoms. A fluorine-substituted alkyl group or an organic group represented by the following general formula (2) is preferable.
• R 4 is an alkyl group having 1 to 30 carbon atoms or an acyl group having 1 to 30 carbon atoms, preferably an alkyl group having 7 to 30 carbon atoms, and d is 0 ⁇ d ⁇ . It is 15, 2 ⁇ d ⁇ 10 is preferable, e is an integer of 0 ⁇ e ⁇ 50, f is an integer of 0 ⁇ f ⁇ 50, but it is preferable that d, e, and f do not become 0 at the same time.
• R 1 examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group and tetradecyl group.
• Alkyl group such as pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, cycloalkyl group such as cyclopentyl group and cyclohexyl group, aryl group such as phenyl group and trill group, benzyl group, phenethyl group and the like.
• Examples thereof include an organic group represented by a fluorine-substituted alkyl group such as an aralkyl group, a trifluoropropyl group and a heptadecafluorodecyl group.
• Preferred are a methyl group, an octyl group, a decyl group, a dodecyl group, a phenyl group, and a trifluoropropyl group.
• the above-mentioned alkyl group may be used alone or in combination of two or more, and when two or more are used in combination, a short-chain alkyl group having 1 to 4 carbon atoms and a long-chain alkyl group having 8 or more carbon atoms are used. It is preferable to use them together.
• an organic group represented by the general formula (2) as R 1 is also preferable, and examples thereof include higher alcohol residues such as alkylene alkyl ether groups, oleoyl alcohols, cetyl alcohols, oleyl alcohols, and stearyl alcohols, and their polys.
• Polyoxyalkylene adducts can be mentioned.
• R 4 is an alkyl group having 1 to 10 carbon atoms, an alkylene alkyl ether group is included.
• the general formula (2) is ⁇ OR 4 .
• R 4 is an alkyl group having 7 to 30 carbon atoms
• higher alcohol residues such as cetyl alcohol, oleyl alcohol, and stearyl alcohol are included, or if R 4 is an acyl group having 1 to 30 carbon atoms. , Fatty residues are included.
• d When d is 3 or more, it is -C d H 2d -O- (C 2 H 4 O) e (C 3 H 6 O) f R 4 (d ⁇ 3), and the above higher alcohol or fatty acid alkenyl ether or Includes alkenyl ester residues and their alkylene oxide adduct residues.
• These groups can be introduced into the organopolysiloxane, for example, by a dehydrogenation reaction between the hydrosilyl group of the organohydrogenpolysiloxane and a higher alcohol, or by an addition reaction between the hydrosilyl group and the alkenyl ether or ester.
• R2 is a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or a group selected from the following general formula (3).
• R 5 is a group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, or a phenyl group, and R 6 has a carbon number of carbon atoms. It is an alkoxy group of 1 to 6, z is an integer of 2 to 8 and p is an integer of 1 to 3, preferably 2 or 3.
• Specific examples of the portion of ⁇ SiR 5 3-p R 6 p in the general formula (3) include a dimethylmethoxysilyl group, a dimethoxymethylsilyl group, a trimethoxysilyl group, a dimethylethoxysilyl group, and a diethoxymethylsilyl group. , Triethoxysilyl group, more preferably trimethoxysilyl group, triethoxysilyl group.
• the group represented by the general formula (3) can be introduced into the organohydropolysiloxane skeleton by, for example, adding vinylsilane having a vinyl group bonded to the silyl group to the hydrosilyl group.
• R 3 is a silicone compound residue represented by the following general formula (4).
• R 7 independently has an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 to 14 carbon atoms.
• It is a group selected from the group consisting of an aralkyl group and a fluorine-substituted alkyl group having 3 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, and x is an integer of 1 ⁇ x ⁇ 5 and 2 or 3 is preferable, and y is an integer of 0 ⁇ y ⁇ 500, 3 ⁇ y ⁇ 100 is preferable, and 1 ⁇ y ⁇ 15 is more preferable. If y is larger than 500, problems such as poor reactivity with the hydrogen siloxane portion of the main chain may occur.
• R 7 examples include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group, cyclopentyl group and cycloalkyl group such as cyclohexyl group.
• Examples thereof include an aryl group such as a group, a phenyl group and a trill group, an aralkyl group such as a benzyl group and a phenethyl group, and a fluorine-substituted alkyl group such as a trifluoropropyl group and a heptadecafluorodecyl group.
• aryl group such as a group, a phenyl group and a trill group
• an aralkyl group such as a benzyl group and a phenethyl group
• a fluorine-substituted alkyl group such as a trifluoropropyl group and a heptadecafluorodecyl group.
• Preferred are a methyl group, an ethyl group, a phenyl group and a trifluoropropyl group.
• R 1 to R 7 When a plurality of R 1 to R 7 are contained in the molecule, they may be the same or different from each other, and a in the general formula (1) is 1.0 ⁇ a ⁇ 2.5 and 1.2 ⁇ . a ⁇ 2.3 is preferable, b is 0.001 ⁇ b ⁇ 1.5, 0.05 ⁇ b ⁇ 1.0 is preferable, and c is a number of 0 ⁇ c ⁇ 1.5, which is 0. .001 ⁇ c ⁇ 1.5 is preferable, and 0.05 ⁇ c ⁇ 1.0 is more preferable.
• the cross-linking reaction point with (B) polysiloxane diol and / or its alkoxy equivalent, which will be described later, is insufficient, and the ability to form a cured film is insufficient. If b is larger than 1.5, the cross-linking reaction point with the component (B) becomes excessive, and the cured film becomes hard and brittle. Further, if c is larger than 1.5, the component (A) may become too bulky and the reaction with the component (B) may not proceed sufficiently.
• the organopolysiloxane compound represented by the general formula (1) is, for example, an organopolysiloxane containing a hydrosilyl group, an alkenyl ether of a higher alcohol or a fatty acid, an alkenyl ester or an alkylene oxide addition thereof, or a higher alcohol and an alkenyl.
• the organopolysiloxane compound represented by the general formula (1) preferably has a kinematic viscosity of 10 to 1,000 mm 2 / s, and particularly preferably 30 to 300 mm 2 / s.
• the weight average molecular weight thereof is preferably 300 to 100,000, particularly preferably 1,000 to 10,000.
• the viscosity of the organopolysiloxane compound becomes appropriate and the texture such as stickiness disappears.
• it is at least the above lower limit the surface slipperiness and water-sliding characteristic of the organopolysiloxane compound can be sufficiently obtained.
• the kinematic viscosity is a value measured at 25 ° C. by a Canon-Fenceke viscometer measured by the method described in JIS Z 8803: 2011, and the weight average molecular weight is a gel permeation chromatograph measured under the conditions shown below. It is a value obtained by converting polystyrene having a known molecular weight as a standard substance by chromatography (GPC).
• the organopolysiloxane of the component (A) may be synthesized by a known method or a commercially available product may be used. Specific examples of commercially available products include KF-9908 and KF-9909 of Shin-Etsu Chemical Co., Ltd.
• (B) Polysiloxane diol and / or its alkoxy equivalent The (B) polysiloxane diol and / or its alkoxy equivalent according to the present invention is represented by the following general formula (5).
• R 8 may have the same or different substituents, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, and an aryl group having 6 to 10 carbon atoms.
• Preferred examples include a methyl group, an ethyl group and a phenyl group.
• the substituent is not particularly limited, and examples thereof include an amino group, an amide group, an ether group, an ester group, a carbonyl group, a carboxyl group, a hydroxyl group, an alkoxy group, an epoxy group, and a nitrile group.
• R 9 is a hydrogen atom, a methyl group or an ethyl group which may be the same or different, and in the case of a hydrogen atom, it is silanol (silaneol).
• silanol silanol
• R 9 is a methyl group and an ethyl group, it is an alkoxy group equivalent.
• M is an integer of 4 ⁇ m ⁇ 50.
• m is less than 4, the silicone chain length is too short, and the characteristics of silicone required in the present application are not sufficiently exhibited.
• it is larger than 50, there arises a problem that the silicone has insufficient compatibility with the above-mentioned (A) polysiloxane, and as a result, a cured film giving a uniform surface state cannot be obtained.
• the polysiloxane diol and / or its alkoxy equivalent as the component (B) may be synthesized by a known method or a commercially available product may be used. Specific examples of commercially available products include KF-9701, X-21-3153, X-21-5841 and KF-857 of Shin-Etsu Chemical Co., Ltd.
• the (C) condensation curing catalyst according to the present invention contains (A) an organopolysiloxane, (B) a polysiloxane diol and / or a hydrolyzable silyl group such as a silanol group contained in an alkoxy equivalent thereof. It is a component that promotes the reaction of being hydrolyzed and condensed by water in the air, promotes the subsequent dehydration condensation reaction between silanols, and as a result promotes the curing of the composition, and is added for efficient curing.
• the amount of the component (C) added is not particularly limited, but the curing rate is adjusted to an appropriate range to produce a cured film having desired physical properties, and the workability at the time of coating is improved. Considering the economic efficiency associated with the addition, 0.01 to 50 parts by mass is preferable, 0.05 to 10 parts by mass is more preferable, and 0. 1 to 5 parts by mass is even more preferable.
• the condensation curing catalyst is not particularly limited as long as it is a curing catalyst used for curing a general moisture condensation curing composition, and specific examples thereof include acids such as carboxylic acid, hydrochloric acid, sulfuric acid, and phosphoric acid.
• acids such as carboxylic acid, hydrochloric acid, sulfuric acid, and phosphoric acid.
• Compounds; Alkyl tin compounds such as dibutyl tin oxide and dioctyl tin oxide; Alkyl tin ester compounds such as dibutyl tin diacetate, dibutyl tin dilaurate, dioctyl tin dilaurate, dibutyl tin dioctate, dioctyl tin dioctate, and dioctyl tin diversatetate; tetraisopropoxytitanium.
• Chelate compounds and their partial hydrolysates zinc naphthenate, zinc stearate, zinc-2-ethyloctate, iron-2-ethylhexoate, cobalt-2-ethylhexoate, manganese-2-ethylhe Organic metal compounds such as xoate, cobalt naphthenate, aluminum trihydroxide, aluminum alcoholate, aluminum acylate, salts of aluminum acylate, aluminosyroxy compounds, aluminum chelate compounds; 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) - ⁇ -amino Propyltriethoxysilane, N- ⁇ - (
• Tertiary ammonium salts lower fatty acid salts of alkali metals such as potassium acetate, sodium acetate, lithium oxalate; dialkyl hydroxylamines such as dimethyl hydroxylamine and diethyl hydroxylamine; tetramethylguanidylpropyltrimethoxysilane, tetramethyl Silanes containing guanidyl groups such as guanidylpropylmethyldimethoxysilane, tetramethylguanidylpropyltriethoxysilane, tetramethylguanidylpropylmethyldiethoxysilane, tetramethylguanidylpropyltris (trimethylsiloxy) silane and Siloxane; silanes containing phosphazene bases such as N, N, N', N', N ", N" -hexamethyl-N'''- [3- (trimethoxysilyl) propyl]
• phosphoric acid, tetra n-butoxytitanium, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- ⁇ - (aminoethyl) have a balance of reactivity and little impact on the environment.
• - ⁇ -Aminopropyltrimethoxysilane, bis [3- (trimethoxysilyl) propyl] amine, N, N'-bis [3- (trimethoxysilyl) propyl] ethane-1,2-diamine are preferred.
• the curable coating composition of the present invention can be used by appropriately adding an organic solvent (organic solvent) for the purpose of adjusting the viscosity to improve workability and ensuring the storage stability of the composition. From the viewpoint of viscosity adjustment, emulsification is also one method.
• solvents that can be used include hydrocarbon solvents such as hexane, heptane, decane, and isododecane, ester solvents such as ethyl acetate and butyl acetate, and non-reactive volatile silicone solvents such as decamethylcyclopentasiloxane and permethylpentasiloxane.
• hydrocarbon solvents such as hexane, heptane, decane, and isododecane
• ester solvents such as ethyl acetate and butyl acetate
• non-reactive volatile silicone solvents such as decamethylcyclopentasiloxane and permethylpentasiloxane.
• any of the curable coating compositions of the present invention can be used as long as it does not participate in the hydrolysis and condensation reaction of the silyl group and dissolves the components (A) to (C). More preferably, a solvent having less burden on the operator and the environment is preferable
• a silane compound optionally containing an alkoxysilyl group, a silicone alkoxy oligomer having an alkoxysilyl group and / or a silanol group in one molecule, and one or more compounds selected from silicone resins (A). It may be mixed separately from the component organopolysiloxane.
• the silicone alkoxy oligomer having an alkoxysilyl group and / or a silanol group in one molecule is not particularly limited, and may be a commercially available product. Specific examples thereof include X-40-9250, X-40-9246, X-40-9225, KR-500, KR-515, KC-89S, KR-401N, X-40 manufactured by Shin-Etsu Chemical Co., Ltd. -9227, KR-510, KR-9218, KR-400, X-40-2327, KR-401 and the like can be mentioned.
• the silicone resin is not particularly limited, and may be a commercially available product. Specific examples thereof include KR-220L, KR-251, KR-112, KR-300, KR-311, KR-480, and KR-216 manufactured by Shin-Etsu Chemical Co., Ltd.
• the curable coating composition of the present invention includes an adhesive improver, an inorganic and organic ultraviolet absorber, a light stabilizer, a storage stability improver, a plasticizer, a filler, a pigment, etc., depending on the purpose of use.
• an adhesive improver an inorganic and organic ultraviolet absorber
• a light stabilizer a storage stability improver
• a plasticizer a filler, a pigment, etc., depending on the purpose of use.
• a filler a pigment, etc.
• ⁇ Cureable coating composition When the curable coating composition of the present invention comes into contact with moisture in the atmosphere, the hydrolysis reaction of the alkoxysilyl group contained in (A) organopolysiloxane proceeds, and the silanol group contained in the silicone of (B) proceeds. , The cross-linking condensation reaction with the alkoxysilyl group is started. Any humidity of 10 to 100% RH may be sufficient as an index of moisture in the atmosphere, and humidity in the air is sufficient. However, in general, the higher the humidity, the faster the hydrolysis proceeds, so that the moisture in the atmosphere is desired. May be added.
• the curing reaction temperature and time can be appropriately changed depending on factors such as the substrate used, the water concentration, the catalyst concentration, and the type of hydrolyzable group. Usually, it is about 1 minute to 1 week within a range that does not exceed the heat resistant temperature of the base material to be used.
• the curable coating composition of the present invention cures well even at room temperature, the stickiness (tack) on the coating film surface disappears in a few minutes to a few hours, especially when room temperature curing is essential for on-site construction.
• the heat treatment may be performed within a range not exceeding the heat resistant temperature of the base material.
• the present invention provides an article having a cured film of the above-mentioned curable coating composition.
• the article of the present invention is, for example, a coated solid substrate which is a cured article by applying the curable coating composition of the present invention to the surface of a solid substrate and curing it to form a coating layer (cured coating). Is obtained.
• the coating method is not particularly limited, and specific examples thereof can be appropriately selected from known methods such as spray coating, spin coating, dip coating, roller coating, brush coating, bar coating, and flow coating.
• the solid substrate is not particularly limited, and specific examples thereof include epoxy resins, phenol resins, polycarbonates and polycarbonate blends, acrylic resins such as poly (methyl methacrylate), poly (ethylene terephthalate), and poly (butylene terephthalate).
• Polyester resin such as unsaturated polyester resin, polyamide resin, polyimide resin, acrylonitrile-styrene copolymer, styrene-acrylonitrile-butadiene copolymer, polyvinyl chloride resin, polystyrene resin, blend of polystyrene and polyphenylene ether, cellulose Organic polymer base material such as acetate butyrate, polyethylene resin, metal base material such as steel plate, paint coated surface, glass, ceramic, concrete, slate plate, textile, wood, stone, tile, (hollow) silica, titania, zirconia, Examples thereof include inorganic fillers such as alumina, glass fibers, glass cloths, glass tapes, glass mats, and glass papers.
• the material and shape of the base material are not particularly limited, but the curable coating composition of the present invention can be particularly preferably used for coating a steel plate, a urethane acrylate resin base material, and glass.
• the curable coating composition of the present invention can also be used as a cosmetic.
• it can be suitably used for cosmetics for treating human hair.
• the kinematic viscosity of each product is a value measured at 25 ° C. by a Canon-Fenceke viscometer measured by the method described in JIS Z 8803: 2011, and the molecular weight is a GPC (gel permeation chromatograph) manufactured by Toso Co., Ltd. Graph) Viscosity-equivalent weight average molecular weight determined by GPC measurement using tetrahydrofuran (THF) as a solvent and RI as a detector using an apparatus.
• THF tetrahydrofuran
• the average silicone composition was calculated from the integrated values of the detection spectra in 1 H-NMR and 29 Si-NMR using a 300 MHz-NMR measuring device manufactured by JEOL Ltd.
• silanol amount The content of silanolic hydroxyl groups (mass%, hereinafter referred to as silanol amount) contained in each product was quantified from the amount of methane gas generated when the Grignard reagent (methylmagnesium iodide) was allowed to act on each product.
• the component (A) is silicone A-1 manufactured by Shin-Etsu Chemical Industry Co., Ltd .: in the general formula (1), R 1 is a methyl group, R 2 is a triethoxysilylethyl group, and R 3 is dimethyl.
• Polysiloxysilylethyl group (y 8 [average value] in general formula (4)), a is 1.82, b is 0.06, c is 0.24, and the kinematic viscosity at 25 ° C.
• the kinematic viscosity is 48 mm 2 / s, the weight average molecular weight is 2,900 and silicone A-3:
• R 1 is a methyl group and an organic group represented by the general formula (2) (general formula (general formula (1)).
• d is 3
• e is 0,
• f is 3
• R 2 is triethoxysilyl.
• a 1.88
• b 0.06
• c 0.18 at 25 ° C.
• the kinematic viscosity of 61 mm 2 / s and the weight average molecular weight of 4,080 were used.
• Silicone B-1 manufactured by Shin-Etsu Chemical Industry Co., Ltd .:
• R8 is a methyl group
• R9 is a hydrogen atom
• m is 40 at 25 ° C.
• the kinematic viscosity is 60 mm 2 / s
• the amount of silanol is 1,500 g / mol
• silicone B-2 In the general formula (5), R 8 is a methyl group, R 9 is a hydrogen atom, and m is 13, at 25 ° C.
• a kinematic viscosity of 30 mm 2 / s and an amount of silanol of 500 g / mol were used.
• tetrabutoxytitanate as a component (C)
• a 2-propanol solution of phosphoric acid solid content 24.9%
• 3-aminopropyltriethoxysilane KBE-manufactured by Shin-Etsu Chemical Co., Ltd.
• isododecane was used as the component (D).
• TBT Tetrabutyl titanate
• PA / IPA 2-propanol solution of phosphoric acid (solid content 24.9%)
• KBE-903 3-aminopropyltriethoxysilane
• Comparative Example 3 the one using the room temperature curable coating agent KR-400 (methyl silicone alkoxy oligomer) of Shin-Etsu Chemical Co., Ltd. was designated as Comparative Example 3.
• Comparative Example 4 was prepared by blending 2% of tetrabutoxytitanate as a curing catalyst with X-40-9246 (methyl silicone alkoxy oligomer), which is the company's flexibility-imparting grade.
• the coating compositions obtained in Examples and Comparative Examples were subjected to Bar Coater No. 1 at 25 ° C. and 50% RH in air. 14 is applied to a glass plate having a thickness of 2 mm or a polished steel plate having a thickness of 0.5 mm, and dried and cured in air at 25 ° C. and 50% RH for 1 day to prepare a cured film. An evaluation was carried out. The results are shown in Tables 2 and 3.
• slipperiness to the touch The slipperiness of the surface was judged according to the following criteria by touching the test piece having the cured film formed on the polished steel sheet with a non-woven fabric. Slippery A Slightly slippery B No slipperiness C
• the cured film obtained in the examples can have both hardness, bending resistance and surface slipperiness as compared with the cured film obtained in the comparative example.
• the cured film produced in Comparative Example 1 did not sufficiently cure, and a film sufficient for practical use could not be obtained.
• Comparative Example 2 since the component (B) was not added, good bending resistance could not be obtained.
• Comparative Examples 3 and 4 since the silicone alkoxy oligomer having an alkoxysilyl group and / or a silanol group in one molecule used as another component in the present invention was used, it also has sufficient bending resistance and slipping to the touch. I could't get sex.
• Examples 1, 4, 5, 7 and Comparative Examples 1 to 4 were diluted with decamethylcyclopentasiloxane so that the film-forming component was 10 wt%, and the test hair was bleached with a bleaching agent.
• the hair bundle (length 6 cm) was coated with 1 g of the liquid so as to be applied to 1 g of the hair bundle.
• the hair bundle was dried with a hair dryer while combing, and the curability of the film was evaluated.
• the hair bundle was repeatedly treated for 20 consecutive cycles with shampooing and washing with water as one cycle. The properties such as combability, flexibility, and luster of each hair immediately after the treatment and after the continuous 20-cycle treatment were observed and evaluated as compared with the untreated normal hair.
• each characteristic was observed by 5 specialized panelists, and the scores were scored according to the criteria shown in Table 4, and the arithmetic mean score was used as the evaluation score.
• the obtained average score was judged by A to E according to the following criteria. Judgment of average score: The average score obtained is 4.5 points or more A The average score obtained is 3.5 points or more and less than 4.5 points B The average score obtained is 2.5 points or more and less than 3.5 points C The average score obtained is 1.5 points or more and less than 2.5 points D The average score obtained is less than 1.5 points E
• Table 5 shows the determination results of curability, combability, flexibility, and gloss.
• the present invention is not limited to the above embodiment.
• the above-described embodiment is an example, and any one having substantially the same structure as the technical idea described in the claims of the present invention and having the same effect and effect is the present invention. Is included in the technical scope of.

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