Classifications

• • 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
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
• • 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
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
• • 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
  • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
  • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
  • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • 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
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/65—Additives macromolecular
• • 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
• • 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
  • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/08—Stabilised against heat, light or radiation or oxydation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/10—Transparent films; Clear coatings; Transparent materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets
  • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

• the present invention relates to a room-temperature-curable silicone coating agent composition that provides a cured product or coating film having a hardness of 50 or more as measured by a type A durometer specified in JIS K 6249 (duro A hardness).
• a dealcoholization type room-temperature-curable silicone coating composition characterized by being easy to produce and inexpensive, capable of forming a coating film of high hardness, and having a cured coating film of high transparency and excellent heat resistance. It is about.
• Room temperature vulcanizable (RTV) silicone rubber compositions which can be crosslinked and cured at room temperature (23°C ⁇ 15°C) by atmospheric humidity to give a silicone elastomer (cured silicone rubber), are easy to handle and Due to its excellent weather resistance and electrical properties, it is used in various fields such as sealing materials for building materials and adhesives in the electrical and electronic fields. Especially in the electrical and electronic fields, dealcoholization type RTV silicone rubber compositions tend to be used because of their suitability for adhesion and coating to adherends (resin systems). Dealcoholization type RTV silicone rubber compositions are also used as coating agents around liquid crystals and power supply circuit boards, for which demand has been rapidly increasing in recent years.
• this coating agent satisfies its main purpose of insulating and moisture-proofing electric and electronic circuits, it has a hardness as a conformal coating agent for the purpose of protecting wiring, etc. as circuit patterns become finer. Improvement was insufficient.
• the following techniques have been disclosed for silicone rubber intended to protect circuit patterns and the like and to prevent moisture.
• Patent Document 2 discloses a room temperature curable organopolysiloxane composition having excellent moisture resistance.
• (CH 3 ) 3 SiO 1/2 units and SiO 4/2 units, (CH 3 ) 3 SiO 1/2 units/SiO 4/2 units (molar ratio) 0.74, and both ends of the molecular chain are
• Organopolysiloxane having silanol groups is dissolved in toluene to form a resinous copolymer, and a room-temperature curable organopolysiloxane composition is prepared by heating.
• the problem is that the production is not convenient due to the heating process.
• Patent Document 3 also discloses a method for producing a room-temperature-curable organopolysiloxane composition that provides a cured product or coating film with high strength.
• (CH 3 ) 3 SiO 1/2 units and SiO 4/2 units, (CH 3 ) 3 SiO 1/2 units/SiO 4/2 units (molar ratio) 0.75;
• An organopolysiloxane having a group content of 1.1% by mass and a dimethylpolysiloxane having both ends blocked with silanol groups are subjected to a condensation reaction with tetramethylguanidine at room temperature for 1 hour.
• Patent Document 2 Japanese Patent Application Laid-Open No. 2002-327115
• Patent Document 4 discloses a method for producing a room temperature curable organosiloxane composition characterized by simple production and a short tact time, wherein R 3 SiO 1/2 units and an organopolysiloxane resin having a three-dimensional network structure composed of SiO 4/2 units and an organosilane compound having an average of two or more hydrolyzable groups bonded to silicon atoms per molecule, using an amino group-containing organosilane as a catalyst.
• the organopolysiloxane resin After introducing hydrolyzable groups into an organopolysiloxane resin having a three-dimensional network structure in advance by condensation reaction, the organopolysiloxane resin is combined with a linear diorganopolysiloxane having both molecular chain ends blocked with silanol groups and a catalyst.
• this composition is easily hydrolyzed by the moisture in the air. Since alkoxytitanium (single substance) is contained as a condensation catalyst, the composition itself may whiten.
• a composition containing a general condensation catalyst such as alkoxytitanium (simple substance) has problems such as yellowing during long-term storage. Japanese Patent No.
• Patent Document 4 discloses a deacetone type room temperature curable composition containing vinyltriisopropenoxysilane as a cross-linking agent and tetramethylguanidylpropyltrimethoxysilane as a condensation catalyst.
• the silane is expensive and the condensation catalyst such as tetramethylguanidylpropyltrimethoxysilane exhibits strong basicity, so it is not used for electric/electronic parts and their substrates. It reacts with the flux component and forms a conductive salt, which may lead to a decrease in electrical performance.
• these compositions have problems such as low transparency and low heat resistance of the resulting cured products.
• the present invention has been made in view of the above circumstances, and is an organopolysiloxane resin with a three-dimensional network structure that is easy to manufacture and inexpensive as a coating agent in the electrical and electronic fields (especially around liquid crystals and power supply circuit boards).
• a dealcoholized room-temperature-curable silicone coating composition containing excellent long-term storage stability, transparency and heat resistance, and providing a cured product (coating film) of high hardness, and coating with the cured product of the composition The purpose is to provide the goods that have been
• an organopolysiloxane resin having a three-dimensional network structure with a specific molecular weight and a specific molecular structure having a specific amount of silanol groups as a main agent, and as a cross-linking agent (B) a hydrolyzable (organo)silane compound having 3 or more hydrolyzable groups in one molecule and/or a partial hydrolyzed condensate thereof, and (C) a silanol at both ends of the molecular chain as a flexibility imparting agent
• a room-temperature-curable silicone coating composition containing a specific amount of a linear diorganopolysiloxane blocked with groups and (D) a moisture-curing initiator consisting of an oligomer of an organotitanium compound as a curing catalyst is easy to produce.
• the cost is low, and furthermore, it gives a hardened product (coating film) with a hardness of 50 or more as measured by a type A durometer specified in JIS K 6249, and the cured coating film has transparency and heat resistance.
• the present inventors have found that a room-temperature-curable silicone coating agent composition that can be suitably applied as a conformal coating material that has excellent long-term storage stability without discoloration even when stored for a long period of time. I came to the eggplant.
• the present invention provides the following room-temperature-curable silicone coating composition and an article coated with a cured product of the composition.
• Components (A) to (D) below (A) R 3 SiO 1/2 units (wherein R independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms or a hydroxy group) and SiO 4/2 units, wherein the molar ratio of R 3 SiO 1/2 units to SiO 4/2 units is 0.5 to 1.5, and further R 2 SiO 2/2 units and RSiO 3/2 units.
• R in each of the above formulas, R is as defined above, may be contained in a molar ratio of 0 to 1 with respect to SiO 4/2 units, respectively, and a hydroxy group (silanol group) bonded to a silicon atom 100 parts by mass of an organopolysiloxane resin with a three-dimensional network structure having a molecular weight of 2,000 to 10,000 and having a molecular weight of 0.005 to 0.15 mol/100 g;
• B Hydrolyzable (organo)silane compound having 3 or more hydrolyzable groups in one molecule and/or partial hydrolytic condensate thereof: moles of component (B) to silanol groups in component (A) an amount that gives a ratio of 0.2 to 2,
• C a linear diorganopolysiloxane having both molecular chain ends blocked with silanol groups: 10 to 100 parts by mass
• D Moisture curing initiator consisting of an oligomer of an organotitanium
• a room temperature vulcanizable silicone coating composition which provides: [2] The room-temperature-curable silicone coating composition according to [1], wherein component (D) is an oligomer of a titanate compound and/or an oligomer of a titanium chelate compound. [3] The room-temperature-curable silicone coating composition according to [1] or [2], which gives a cured product that does not generate air bubbles when left in an environment of 250° C. for 5 minutes. [4] The room-temperature-curable silicone coating composition according to any one of [1] to [3], which gives a cured product having a thickness of 1 mm and a light transmittance of 70% or more in the wavelength range of 450 to 800 nm. thing.
• the hardened product It is possible to provide a room-temperature-curable silicone coating composition that provides a cured film having both transparency and heat resistance.
• the room-temperature-curable silicone coating composition of the present invention comprises the following components (A) (main agent), (B) (crosslinking agent), (C) (flexibility imparting agent) and (D) (curing catalyst). ) and gives a cured product having a hardness of 50 or more as measured with a type A durometer specified in JIS K 6249 (hereinafter sometimes referred to as duro A hardness).
• component (A) used as the main agent (base polymer) consists of R 3 SiO 1/2 units (wherein R is independently an unsubstituted or substituted carbon (representing a monovalent hydrocarbon group having 1 to 6 atoms or a hydroxy group) and SiO 4/2 units, wherein the molar ratio of R 3 SiO 1/2 units to SiO 4/2 units is 0.5 to 1.5 and further contains R 2 SiO 2/2 units and RSiO 3/2 units (where R is as defined above) in a molar ratio of 0 to 1 relative to SiO 4/2 units, respectively.
• R 3 SiO 1/2 units wherein R is independently an unsubstituted or substituted carbon (representing a monovalent hydrocarbon group having 1 to 6 atoms or a hydroxy group) and SiO 4/2 units, wherein the molar ratio of R 3 SiO 1/2 units to SiO 4/2 units is 0.5 to 1.5 and further contains R 2 SiO 2/2 units and RSiO 3/2 units (where R is as defined above) in a
• organopolysiloxane resin with a three-dimensional network structure having a molecular weight of 2,000 to 10,000 and having 0.005 to 0.15 mol/100 g of hydroxy groups (silanol groups) bonded to silicon atoms. be.
• the R represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms or a hydroxy group
• examples of the monovalent hydrocarbon group for R include a methyl group, an ethyl group, a propyl group and an isopropyl group.
• a methyl group, an ethyl group, a propyl group and a phenyl group are preferable, and a methyl group and a phenyl group are particularly preferable.
• the molar ratio of R 3 SiO 1/2 units to SiO 4/2 units is in the range of 0.5 to 1.5, preferably 0.6 to 1.3, particularly preferably 0.5. 65 to 1.2. If this molar ratio is less than 0.5, the reinforcing properties of the cured product will be insufficient, and if it exceeds 1.5, the hardness of the cured product will be insufficient.
• the three-dimensional network structure organopolysiloxane resin of component (A) preferably consists of only R 3 SiO 1/2 units and SiO 4/2 units. Both the molar ratio of the units and the molar ratio of the RSiO 3/2 units to the SiO 4/2 units may be in the range of 0 to 1, and more preferably the molar ratio is 0.8 or less (0 to 0 .8).
• the silanol groups contained in the three-dimensional network structure organopolysiloxane resin of component (A) should be 0.005 to 0.15 mol/100 g (that is, 0.00 in terms of the amount of OH of hydroxyl groups bonded to silicon atoms). 085 to 2.5% by mass), preferably 0.01 to 0.13 mol/100g (0.17 to 2.2% by mass), more preferably 0.02 to 0.02% by mass. 12 mol/100 g (0.3 to 2.0% by mass). If more than 0.15 mol/100 g of silanol groups are present, the physical properties (especially hardness) of the rubber become high, and cracks may occur in the composition. On the other hand, if the silanol group content is less than 0.005 mol/100 g, the condensation reaction between the components (A) and (C) may not proceed sufficiently, and the intended properties may not be obtained.
• the organopolysiloxane resin having a three-dimensional network structure as component (A) has a molecular weight of about 2,000 to 10,000, preferably about 2,500 to 8,000.
• the cured product (cured silicone rubber product) obtained by curing the composition has poor rubber elasticity and is easily cracked.
• This molecular weight (or degree of polymerization) is usually determined as the polystyrene-equivalent number average molecular weight (or number average degree of polymerization) in gel permeation chromatography (GPC) analysis using toluene, tetrahydrofuran (THF), etc. as a developing solvent. can.
• GPC gel permeation chromatography
• the three-dimensional network structure organopolysiloxane resin of component (A) comprises a monofunctional triorganosilane having one hydrolyzable group, together with a tetrafunctional silane having four hydrolyzable groups, or obtained by cohydrolyzing and condensing in an organic solvent together with a trifunctional silane having three hydrolyzable groups and/or a bifunctional silane having two hydrolyzable groups, substantially It is a known material that does not contain volatile components (copolymer).
• the organic solvent used in the co-hydrolysis reaction is required to dissolve the organopolysiloxane resin as the component (A).
• Solvents include halogen-based solvents such as chloroform and dichloromethane, and hydrocarbon-based solvents such as cyclohexane, ethylcyclohexane, and isoparaffin.
• Component (B) is a hydrolyzable (organo ) A silane compound and/or a partial hydrolysis condensate thereof (a siloxane oligomer having 3 or more remaining hydrolyzable groups in the molecule formed by partially hydrolyzing/condensing the silane compound), and the (organo )
• the silane compound include monosilane compounds and disilane compounds and trisilane compounds in which monosilanes are linked by an alkylene group or an alkenylene group, preferably represented by the following general formulas (1) to (6).
• R 1 is an alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, hexyl group, decyl group; vinyl group (ethenyl); , allyl group, propenyl group, isopropenyl group, butenyl group, pentenyl group, alkenyl group such as hexenyl group; phenyl group, tolyl group, xylyl group, aryl group such as ⁇ -, ⁇ -naphthyl group; aralkyl groups such as phenylethyl group and 3-phenylpropyl group; groups in which some or all of the hydrogen atoms in these groups are substituted with halogen atoms such as F, Cl and Br, cyano groups and the like; 3-chloropropyl group, 3,3,3
• the hydrolyzable group (OR 2 ) includes, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy and tert-butoxy groups having 1 to 4 carbon atoms, particularly 1 or 4 carbon atoms.
• alkoxy group of 2 alkoxyalkoxy group having 2 to 4 carbon atoms such as methoxyethoxy group, ethoxyethoxy group and methoxypropoxy group; 3 carbon atoms such as dimethylketoxime group, ethylmethylketoxime group and diethylketoxime group ⁇ 7 ketooxime group; vinyloxy group, propenyloxy group, isopropenyloxy group, alkenyloxy group having 2 to 6 carbon atoms such as 1-ethyl-2-methylvinyloxy group; acetoxy group, octanoyloxy group, benzoyl acyloxy groups having 2 to 8 carbon atoms such as an oxy group; is particularly preferred.
• X is ethylene group, propylene group (trimethylene group, methylethylene group), butylene group (tetramethylene group, methylpropylene group), alkylene group having 2 to 6 carbon atoms such as hexamethylene group; vinylene group, propenylene group, 1 alkenylene groups having 2 to 4 carbon atoms such as -butenylene group and 2-butenylene group;
• component (B) include methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, trialkoxy such as n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, isobutyltrimethoxysilane, n-hexyltrimethoxysilane, n-decyltrimethoxysilane; Tetraalkoxysilanes such as silane, tetramethoxysilane, tetraethoxysilane, bis[2-(dimethoxy(methyl)silyl)etheny
• an organooxy group for example, a hydrolyzable organosilane compound having a methylene group (for example, an organooxymethyl group such as an alkoxymethyl group) having an alkoxy group or the like can also be used.
• R 3 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms
• R 4 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms
• Y is a hydrolyzable group
• m is 0 or 1.
• Hydrogen groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, Alkyl groups such as nonyl group, decyl group and dodecyl group; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, pentenyl group and hexenyl group; Aryl groups such as
• Hydrogen groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, Alkyl groups such as nonyl group, decyl group and dodecyl group; Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; Alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, pentenyl group and hexenyl group; Aryl groups such as
• Y is a hydrolyzable group, for example, a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, tert-butoxy group, etc.
• alkoxy group of 4 alkoxyalkoxy group having 2 to 4 carbon atoms such as methoxyethoxy group, ethoxyethoxy group and methoxypropoxy group; acyloxy group having 2 to 8 carbon atoms such as acetoxy group, octanoyloxy group and benzoyloxy group Group; vinyloxy group, propenyloxy group, isopropenyloxy group, alkenyloxy group having 2 to 6 carbon atoms such as 1-ethyl-2-methylvinyloxy group; dimethylketoxime group, methylethylketoxime group, diethylketoxime group ketooxime group having 3 to 7 carbon atoms such as; amino group having 2 to 6 carbon atoms such as dimethylamino group, diethylamino group, butylamino group and cyclohexylamino group; aminoxy groups of 2 to 6; amide groups of 3 to 8 carbon atoms such as N-methylacetamide group, N
• hydrolyzable organosilane compounds containing an organooxymethyl group such as an alkoxymethyl group bonded to a silicon atom in the molecule represented by the above formula (7) and partial hydrolysis condensates thereof include: Methoxymethyltrimethoxysilane, ethoxymethyltriethoxysilane, methoxymethyl(methyl)dimethoxysilane, ethoxymethyl(methyl)diethoxysilane, methoxymethyl(ethyl)dimethoxysilane, ethoxymethyl(ethyl)diethoxysilane, methoxymethyl(hexyl) ) dimethoxysilane, ethoxymethyl(hexyl)diethoxysilane, methoxymethyl(octyl)dimethoxysilane, ethoxymethyl(octyl)diethoxysilane, methoxymethyl(phenyl)dimethoxysilane, ethoxymethyl(phenyl)diethoxys
• the hydrolyzable (organo)silane compound having 3 or more hydrolyzable groups in one molecule of component (B) and/or its partial hydrolytic condensate is , and acts as a cross-linking agent (curing agent) that bonds component (A) and component (C), which will be described later. ) is such that the molar ratio of the components is 0.2 to 2, particularly preferably 0.4 to 2. If the amount of component (B) is too small, sufficient rubber physical properties may not be obtained even if the composition is cured, or the storage stability may be deteriorated. is.
• the amount of component (B) to be blended is preferably such that the molar ratio of component (B) to the sum of the amounts of silanol groups in components (A) and (C) is 0.3 to 1. , 0.4 to 1.0 is more preferred. If the molar ratio of component (B) to the sum of silanol groups in components (A) and (C) is less than 0.3, good storage stability cannot be obtained. In addition to being long, it is disadvantageous in terms of cost.
• the hydrolyzable (organo)silane compound of component (B) is a monovalent carbonized silane compound substituted with a functional group (excluding an organooxy group) having a heteroatom such as nitrogen, oxygen or sulfur in the molecule. In that it does not have a hydrogen group, it is clearly distinguished from the silane coupling agent as an optional component described later.
• Component (C) is a necessary component for connecting organopolysiloxane resins having a three-dimensional network structure by mixing with components (A) and (B) and condensing with these components. Addition of component (C) makes it possible to impart flexibility to the cured product (cured film) of the room-temperature-curable silicone coating composition of the present invention.
• component (C) is a linear diorganopolysiloxane having both ends of the molecular chain blocked with silanol groups (or hydroxydiorganosiloxy groups), represented by the following general formula (8): preferable.
• R 5 is independently an unsubstituted or alkoxy-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 10 or more.
• examples of the unsubstituted or alkoxy-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms for R 5 include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, Alkyl groups such as sec-butyl group, tert-butyl group, pentyl group and hexyl group; cycloalkyl groups such as cyclohexyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group and naphthyl group; Some or all of the hydrogen atoms of are substituted with alkoxy groups, for example, alkoxy-substituted monovalent hydrocarbon groups such as alkoxy-substituted alkyl groups such as methoxymethyl group, methoxyethyl group, ethoxymethyl group, and ethoxyethyl group can be done.
• the viscosity of component (C) is 10,000 mPa s or less at 23° C. (usually 30 to 10,000 mPa s), preferably 50 to 8,000 mPa s, particularly preferably about 100 to 6,000 mPa s. is preferably a fluid (liquid substance) exhibiting a viscosity of , and usually the number of repeating units n (degree of polymerization) in the above formula (8) is about 10 to 1,000, preferably 30 to 500, more preferably It corresponds to about 50 to 400.
• the viscosity can usually be measured by a rotational viscometer (eg, BL type, BH type, BS type, cone plate type, etc.) (same below).
• the blending amount of component (C) is 10 to 100 parts by mass, preferably 10 to 80 parts by mass, per 100 parts by mass of component (A). If the amount of component (C) is too small, the composition will cure, but the hardness will be too high, and good rubber properties will not be obtained. If it is too large, it may not mix uniformly with the component (A).
• Component (D) is a moisture-curing initiator composed of an oligomer of an organotitanium compound (poly(condensation) compound of an organotitanium compound with a low degree of polymerization). 23 ° C ⁇ 15 ° C), it is a component that functions as a catalyst that accelerates moisture curing by atmospheric moisture (moisture), and even if one type is used alone as an organotitanium compound oligomer, it can be used as a mixture of two or more types. may be used.
• component (D) is preferably an oligomer of a titanate ester compound and/or an oligomer of a titanium chelate compound.
• component (D) include oligomers of tetra-n-propoxy titanium, oligomers of tetraisopropoxy titanium, oligomers of tetra-n-butoxy titanium (also known as tetra-n-butyl titanate), and tetraisobutoxy titanium.
• Titanate compound oligomers such as oligomers, tetra-sec-butoxy titanium oligomers, tetra-tert-butoxy titanium oligomers, tetrakis(2-ethylhexoxy) titanium oligomers, titanium isopropoxy octylene glycol oligomers, diisopropoxy Oligomers of organotitanium compounds, such as oligomers of titanium chelates such as oligomers of bis(acetylacetonato)titanium, oligomers of diisopropoxybis(ethylacetoacetonato)titanium.
• tetra-n-butoxytitanium oligomers and tetra-tert-butoxytitanium are preferred from the standpoints of environmental and human toxicity and long-term color resistance of the room-temperature-curable silicone coating composition of the present invention.
• Oligomers of butyl titanate compounds such as oligomers of are particularly preferred.
• Tyzor BTP manufactured by Dorf Ketal
• the oligomer of the organotitanium compound has a structure in which the titanate ester or titanium chelate compound is condensed, and is preferably a 2-50 mer of these organotitanium compounds, preferably a 2-20 mer. is more preferred.
• Such an oligomer of an organotitanium compound is obtained by reacting the organotitanium compound with water in an alcohol solution to condense it.
• Component (D) is 0.1 to 5 parts by mass, preferably 0.1 to 4 parts by mass, particularly preferably 0.5 to 3 parts by mass, per 100 parts by mass of component (A). If it is less than 0.1 parts by mass, sufficient crosslinkability cannot be obtained, and the desired cured product cannot be obtained. If the amount exceeds 5 parts by mass, there are disadvantages such as being disadvantageous in terms of cost and decreasing the curing speed.
• the room-temperature-curable silicone coating composition of the present invention may optionally contain fillers and various additives as long as the objects of the present invention are not compromised.
• Fillers include ground silica, fumed silica, calcium carbonate, zinc carbonate, aluminum hydroxide, aluminum hydroxide oxide, alumina, magnesium oxide, wet-process silica, and the like.
• Additives include known additives such as polyethers as wetters and thixotropy improvers, plasticizers, non-reactive dimethylsilicone oils, and the like.
• colorants such as pigments and dyes, fluorescent brighteners, antifungal agents, antibacterial agents, non-reactive phenylsilicone oils as bleeding oils, fluorosilicone oils, and organic liquids incompatible with silicone.
• a surface modifier such as may also be added.
• a silane coupling agent for imparting adhesiveness other than component (B), a functional group having a monovalent hydrocarbon group substituted with a functional group having a heteroatom such as nitrogen, oxygen, sulfur, etc. in the molecule
• a group-containing hydrolyzable organosilane compound (so-called carbon functional silane compound) may be blended.
• silane compounds having an alkoxysilyl group or alkenoxysilyl group as a hydrolyzable group such as ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, , ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, N- ⁇ -(aminoethyl) ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, 3-(N -aminomethylbenzylamino)propyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N,N-bis[3-(trimethoxysilyl)propyl]amine, ⁇ -mercaptopropyl Trimeth
• the blending amount is 0.1 to 20 parts by mass, preferably 0.1 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass per 100 parts by mass of component (A). is. If the amount is less than 0.1 part by mass, sufficient adhesiveness cannot be obtained, and if the amount exceeds 20 parts by mass, not only is the cost disadvantageous, but also good curability may not be exhibited.
• the room-temperature-curable silicone coating composition of the present invention can be prepared by mixing the above ingredients in a conventional manner, stored in a moisture-free atmosphere, and placed at room temperature (23°C ⁇ 15°C). When left to stand at room temperature, it usually cures in the presence of moisture in the air in 5 minutes to 1 week.
• a predetermined organic solvent for example, aromatic solvents such as toluene and xylene, halogen solvents such as chloroform and dichloromethane, cyclohexane and ethylcyclohexane.
• a hydrocarbon solvent such as isoparaffin
• the viscosity of the room-temperature-curable silicone coating composition of the present invention is preferably 10 to 5,000 mPa ⁇ s, more preferably 20 to 3,000 mPa ⁇ s at 23°C.
• the room-temperature-curable silicone coating composition of the present invention is particularly easy to produce and inexpensive, can form a coating film with high hardness, and the cured coating film is highly transparent, excellent in heat resistance, and long-lasting. It is characterized by no discoloration.
• the room-temperature-curable silicone coating composition of the present invention contains the components (A) to (D) defined above, and has a hardness of 50 as measured with a type A durometer defined in JIS K 6249. As described above, it is characterized in that a cured product having a hardness of preferably 50 to 90 is obtained. If the Duro A hardness of the obtained cured product is less than 50, it is unsuitable as a conformal coating agent for the purpose of protecting wiring and the like associated with miniaturization of circuit patterns.
• the above-described components (A) to (D) are blended in the above-described specific blending ratios.
• the composition is condensed and cured at room temperature with moisture in the air, etc., according to a conventional method (for example, an operation such as standing for 7 days so that the thickness becomes 3 mm in an environment of 23 ° C./50% RH. ) can be achieved.
• the cured product of the room-temperature-curable silicone coating composition of the present invention preferably does not generate air bubbles when left in an environment of 250° C. for 5 minutes. It is preferably 70% or more in the wavelength region of 450 to 800 nm.
• a composition obtained by blending the above-described components (A) to (D) in the above-described specific blending ratio is condensed with moisture in the air at room temperature in accordance with a conventional method. It can be achieved by curing (for example, by leaving for 7 days in an environment of 23° C./50% RH so that the thickness becomes 3 mm).
• the light transmittance in the above-mentioned specific wavelength range can usually be measured with a spectrophotometer.
• the room-temperature-curable silicone coating composition of the present invention can be stored at room temperature (23°C ⁇ 15°C) for a long period of time (for example, about 4 months) in a sealed state without moisture, and the color of the composition does not change. It is preferable that the storage stability is excellent for a long period of time.
• Such a room-temperature-curable silicone coating composition of the present invention is suitable as a conformal coating material, and is particularly suitable as a coating agent for electric/electronic parts and/or their substrates, a sealing agent for liquid crystal display elements, and the like. Further, according to the present invention, it is possible to provide an article coated with a cured product of the room-temperature-curable silicone coating composition of the present invention.
• Articles to which the present invention is applied include, for example, liquid crystal peripherals, power supply circuit boards, water-repellent coated base materials for vehicles, and the like.
• Me is a methyl group
• the viscosity is a value measured by a rotational viscometer at 23° C.
• the molecular weight is the polystyrene-equivalent number-average molecular weight in GPC analysis using toluene as a developing solvent.
• Example 1 [Example 1] (A) consists of Me 3 SiO 1/2 units and SiO 4/2 units, the molar ratio of Me 3 SiO 1/2 units to SiO 4/2 units is 0.68, and the molecular weight is about 3. 500, the silanol group content is 0.11 mol/100 g (1.87% by mass), and the solid content is 60% by mass. ), and 10 parts by mass of tetraethoxysilane as component (B) (molar ratio of component (B) to silanol groups in component (A) is 0.79 35 parts by mass of dimethylpolysiloxane having a viscosity of 5,000 mPa s at 23° C.
• component (C) both molecular chain ends of which are blocked with hydroxydimethylsilyl groups
• component (D) 1 part by mass of tetra-n-butoxytitanium oligomer Tyzor BTP (manufactured by Dorf Ketal) and 1.6 parts by mass of ⁇ -aminopropyltriethoxysilane were mixed at room temperature (23°C) for 30 minutes. Composition 1 was obtained.
• (A) consists of Me 3 SiO 1/2 units and SiO 4/2 units, the molar ratio of Me 3 SiO 1/2 units to SiO 4/2 units is 0.68, and the molecular weight is about 3. 500, a silanol group content of 0.11 mol/100 g (1.87% by mass), and 92 parts by mass of a three-dimensional network methylpolysiloxane resin dissolved with Isopar E to a solid content of 60% by mass.
• component (B) 10 parts by mass of tetraethoxysilane as component (B) (an amount that provides a molar ratio of component (B) to silanol groups in component (A) of 0.79); 35 parts by mass of dimethylpolysiloxane blocked with hydroxydimethylsilyl groups, having a viscosity of 5,000 mPa s at 23° C.
• composition 2 a tetra-n-butoxytitanium oligomer Tyzor BTP as the component (D) (manufactured by Dorf Ketal) and 0.8 parts by mass of ⁇ -aminopropyltriethoxysilane were mixed at room temperature (23° C.) for 30 minutes to obtain composition 2.
• Example 3 (A) consists of Me 3 SiO 1/2 units and SiO 4/2 units, the molar ratio of Me 3 SiO 1/2 units to SiO 4/2 units is 0.68, and the molecular weight is about 3. 500, a silanol group content of 0.11 mol/100 g (1.87% by mass), and 92 parts by mass of a three-dimensional network methylpolysiloxane resin dissolved with Isopar E to a solid content of 60% by mass.
• component (B) 10 parts by mass of methyltrimethoxysilane as component (B) (an amount that makes the molar ratio of component (B) to silanol groups in component (A) 1.21), and both molecular chain ends as component (C) is blocked with hydroxydimethylsilyl groups, and has a viscosity at 23° C. of 700 mPa s and a degree of polymerization of about 270, and 40 parts by mass of dimethylpolysiloxane, and a tetra-n-butoxytitanium oligomer Tyzor BTP as component (D). (manufactured by Dorf Ketal) was mixed at room temperature (23° C.) for 30 minutes to obtain composition 3.
• (A) consists of Me 3 SiO 1/2 units and SiO 4/2 units, the molar ratio of Me 3 SiO 1/2 units to SiO 4/2 units is 0.68, and the molecular weight is about 3. 500, a silanol group content of 0.11 mol/100 g (1.87% by mass), and 92 parts by mass of a three-dimensional network methylpolysiloxane resin dissolved with Isopar E to a solid content of 60% by mass.
• component (B) 10 parts by mass of (ethoxymethyl)triethoxysilane as component (B) (an amount that gives a molar ratio of component (B) to silanol groups in component (A) of 0.74), and a molecule as component (C) 35 parts by mass of dimethylpolysiloxane having both chain ends blocked with hydroxydimethylsilyl groups, having a viscosity of 5,000 mPa s at 23°C and a degree of polymerization of about 389, and tetra-n-butoxytitanium as component (D).
• Tyzor BTP manufactured by Dorf Ketal
• ⁇ -aminopropyltriethoxysilane 1 part by mass of ⁇ -aminopropyltriethoxysilane were mixed at room temperature (23° C.) for 30 minutes to obtain composition 4.
• (A) consists of Me 3 SiO 1/2 units and SiO 4/2 units, the molar ratio of Me 3 SiO 1/2 units to SiO 4/2 units is 0.68, and the molecular weight is about 3. 500, a silanol group content of 0.11 mol/100 g (1.87% by mass), and 92 parts by mass of a three-dimensional network methylpolysiloxane resin dissolved with Isopar E to a solid content of 60% by mass.
• tetraethoxysilane as component (B) (an amount that provides a molar ratio of component (B) to silanol groups in component (A) of 0.79); 35 parts by mass of dimethylpolysiloxane blocked with hydroxydimethylsilyl groups, having a viscosity of 5,000 mPa s at 23° C. and a degree of polymerization of about 389, 1 part by mass of tetra-n-butyl titanate (single substance), and ⁇ A composition 5 was obtained by mixing 1.6 parts by mass of -aminopropyltriethoxysilane at room temperature (23° C.) for 30 minutes.
• (A) consists of Me 3 SiO 1/2 units and SiO 4/2 units, the molar ratio of Me 3 SiO 1/2 units to SiO 4/2 units is 0.68, and the molecular weight is about 3. 500, a silanol group content of 0.11 mol/100 g (1.87% by mass), and 92 parts by mass of a three-dimensional network methylpolysiloxane resin dissolved with Isopar E to a solid content of 60% by mass.
• tetraethoxysilane as component (B) (an amount that provides a molar ratio of component (B) to silanol groups in component (A) of 0.79); 35 parts by mass of dimethylpolysiloxane blocked with hydroxydimethylsilyl groups, having a viscosity of 5,000 mPa s at 23° C. and a degree of polymerization of about 389, 1 part by mass of tetra-n-octyl titanate (single substance), and ⁇ A composition 6 was obtained by mixing 1.6 parts by mass of -aminopropyltriethoxysilane at room temperature (23° C.) for 30 minutes.
• (A) consists of Me 3 SiO 1/2 units and SiO 4/2 units, the molar ratio of Me 3 SiO 1/2 units to SiO 4/2 units is 0.68, and the molecular weight is about 3. 500, a silanol group content of 0.11 mol/100 g (1.87% by mass), and 92 parts by mass of a three-dimensional network methylpolysiloxane resin dissolved with Isopar E to a solid content of 60% by mass.
• composition 7 10 parts by mass of tetraethoxysilane as component (B) (an amount that provides a molar ratio of component (B) to silanol groups in component (A) of 0.79); 35 parts by mass of dimethylpolysiloxane blocked with hydroxydimethylsilyl groups, having a viscosity of 5,000 mPa s at 23° C. and a degree of polymerization of about 389, and 1.6 parts by mass of ⁇ -aminopropyltriethoxysilane at room temperature.
• Composition 7 was obtained by mixing at (23° C.) for 30 minutes.
• (A) consists of Me 3 SiO 1/2 units and SiO 4/2 units, the molar ratio of Me 3 SiO 1/2 units to SiO 4/2 units is 0.68, and the molecular weight is about 3. 500, a silanol group content of 0.11 mol/100 g (1.87% by mass), and 92 parts by mass of a three-dimensional network methylpolysiloxane resin dissolved with Isopar E to a solid content of 60% by mass.
• component (B) 8 parts by mass of (ethoxymethyl)triethoxysilane as component (B) (an amount that gives a molar ratio of component (B) to silanol groups in component (A) of 0.74), and a molecule as component (C) 30 parts by mass of dimethylpolysiloxane having both chain ends blocked with hydroxydimethylsilyl groups, a viscosity of 5,000 mPa s at 23°C and a degree of polymerization of about 389, and 0.8 mass of ⁇ -aminopropyltriethoxysilane and 0.1 part by mass of ⁇ -(N,N'-dimethylguanidyl)propyltrimethoxysilane were mixed at room temperature (23° C.) for 30 minutes to obtain composition 8.
• compositions 1 to 8 are left on an aluminum plate of 50 mm ⁇ 50 mm ⁇ 5 mm in thickness in an environment of 23 ° C./50% RH for 7 days so that the thickness becomes 5 mm and cured. rice field.
• the cured specimens of Compositions 1 to 8 were left in an oven at 250° C. for 5 minutes, and the presence or absence of air bubbles in the cured rubber was checked.
• Judgment shall be as follows. (criterion) ⁇ : No air bubbles are observed in the test piece (good heat resistance) ⁇ : Bubbles were generated in the test body (poor heat resistance)
• compositions 1 to 4 As a result, in Examples 1 to 4 (compositions 1 to 4), a good cured product having a Duro A hardness of 50 or more was obtained, the heat resistance was good, and the light transmittance at wavelengths of 450 nm, 600 nm, and 800 nm was also good. All of them were 70% or more, and they were stable with no change in color even after long-term storage. On the other hand, in Comparative Examples 1 and 2 (compositions 5 and 6), good cured products were obtained and had good heat resistance, but yellowing was confirmed during long-term storage. Further, in Comparative Example 3 (composition 7), no cured product was obtained even when left in an environment of 23° C./50% RH, and hardness, heat resistance and light transmittance could not be measured.
• composition 8 by blending (ethoxymethyl)triethoxysilane, which is excellent in rapid curing, as component (B), component (D) was not blended, or component (D) Even if a basic condensation catalyst was blended instead, a cured product was obtained, but in the heat resistance evaluation, a large number of air bubbles were generated in the cured product, resulting in poor heat resistance.

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