Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/068—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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/04—Polysiloxanes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • 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
• • 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
• • 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
  • 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
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/10—Block or graft copolymers containing polysiloxane sequences
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2203/00—Other substrates
  • B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
  • B05D2203/35—Glass
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2518/00—Other type of polymers
  • B05D2518/10—Silicon-containing polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
  • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
  • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules

Definitions

• the present invention relates to a resin composition, a cured product and a method for producing the same, and a laminate.
• This application is based on Japanese Patent Application No. 2020-15163 filed in Japan on September 11, 2020, and Japanese Patent Application Nos. 2020-198572 and 2020-199028 filed in Japan on November 30, 2020. And the priority is claimed based on Japanese Patent Application No. 2020-199037, and the contents thereof are incorporated herein by reference.
• Polymethylmethacrylate resin, polymethacrylicimide resin, polycarbonate resin, polystyrene resin, acrylonitrile styrene resin and the like are used for members such as various lamp lenses for automobiles, glazing, exteriors, and covers of instruments. Resin molded products made from these resins are lightweight, have excellent impact resistance, and have good transparency. Further, in recent years, with the miniaturization of various parts, transparent glass having excellent durability has been increasingly used for the cover member.
• ADAS advanced driver assistance system
• a sensor device sometimes called a millimeter-wave radar
• radio waves millimeter waves
• LiDAR sensor device
• Patent Document 1 describes a silicone composition containing a tetrafunctional alkoxysilane and a trifunctional alkoxysilane or a partially hydrolyzed condensate thereof, a reactive silicone having a specific structure containing a polydimethylsiloxane structure, an acid or a base catalyst, and the like. Coating compositions containing water have been proposed.
• the coating composition described in Patent Document 1 has a high curing temperature, so that it is not suitable for a resin base material, for example.
• the compatibility between the component contributing to water permeability and other components is poor, and the appearance of the formed coating layer is easily spoiled.
• the durability of the coating layer is insufficient, and the appearance and water-sliding property may be deteriorated by the moisture resistance test.
• the present invention relates to a resin composition capable of forming a cured product having excellent appearance, water-sliding and durability, a cured product having excellent appearance, water-sliding, weather resistance and durability and a method for producing the same, and appearance, water-sliding and weather resistance. It is an object of the present invention to provide a laminate having a cured product layer having excellent durability.
• the total of the ratio of the structural unit based on the silicone macromonomer (X) and the ratio of the structural unit based on the monomer (Y) to the total mass of all the structural units constituting the copolymer (A) is 55.
• M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta
• R 1 represents a hydrocarbon group having 1 to 5 carbon atoms
• R 2 represents a hydrocarbon group having 1 to 5 carbon atoms.
• R3 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an aryl group, or an acyl group.
• m represents an integer of 3 to 4 according to M
• r represents an integer of 0 to 3
• r R 2s may be different from each other
• mr is In the case of 2 or more, the (mr) OR 3s may be different from each other.
• R 4 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group
• R 5 represents an alkyl group or a phenyl group
• n represents an integer of 2 to 4
• n OR 5s are different from each other.
• n represents an integer of 2 to 4
• n represents an integer of 2 to 4
• n OR 5s are different from each other.
• n represents an integer of 2 to 4
• R4s may be different from each other.
• the proportion of the structural unit based on the silicone macromonomer (X) is 15 to 60% by mass with respect to the total mass of all the structural units constituting the copolymer (A), and the monomer (Y).
• a partially hydrolyzed condensate in which the component (B) is at least one kind of the silane compound and has a weight average molecular weight of 300 to 3000 is further hydrolyzed in the presence of a catalyst.
• a component (B) composed of a silane compound or a partially hydrolyzed condensate thereof.
• M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta
• R 1 represents a hydrocarbon group having 1 to 5 carbon atoms
• R 2 represents a hydrocarbon group having 1 to 5 carbon atoms.
• R3 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an aryl group, or an acyl group.
• m represents an integer of 3 to 4 according to M
• r represents an integer of 0 to 3
• r R 2s may be different from each other
• mr is In the case of 2 or more, the (mr) OR 3s may be different from each other.
• a resin composition comprising, a component (B) composed of a silane compound or a partial hydrolysis condensate thereof, and a photopolymerization initiator. -R 1 -M (R 2 ) r (OR 3 ) m-r ...
• M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta
• R 1 represents a hydrocarbon group having 1 to 5 carbon atoms
• R 2 represents a hydrocarbon group having 1 to 5 carbon atoms.
• R3 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an aryl group, or an acyl group.
• M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta
• R 1 represents a hydrocarbon group having 1 to 5 carbon atoms
• R 2 represents a hydrocarbon group having 1 to 5 carbon atoms.
• R3 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an aryl group, or an acyl group.
• a method for producing a cured product wherein a resin composition containing a silane compound or a component (B) containing a partially hydrolyzed condensate thereof is cured by heat treatment or irradiation with active energy rays.
• a resin composition containing a silane compound or a component (B) containing a partially hydrolyzed condensate thereof is cured by heat treatment or irradiation with active energy rays.
• M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta
• R 1 represents a hydrocarbon group having 1 to 5 carbon atoms
• R 2 represents a hydrocarbon group having 1 to 5 carbon atoms.
• R3 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an aryl group, or an acyl group.
• m represents an integer of 3 to 4 according to M
• r represents an integer of 0 to 3
• r R 2s may be different from each other
• mr is In the case of 2 or more, the (mr) OR 3s may be different from each other.
• a resin composition capable of forming a cured product having excellent curability and excellent appearance, water-sliding, weathering resistance and durability, a cured product having excellent appearance, water-sliding, weathering resistance and durability, and a method for producing the same.
• a laminate having a cured product layer excellent in appearance, water slipperiness, weather resistance and durability can be provided.
• the resin composition according to one aspect of the present invention is a copolymer (A) containing a polydimethylsiloxane unit and at least one specific silane compound or a portion thereof. It contains a component (B) composed of a hydrolysis condensate.
• the present resin composition may further contain an initiator (C) and a diluent, if necessary.
• the present resin composition may further contain components other than the above, if necessary.
• the copolymer (A) contains a polyalkylsiloxane unit.
• the polyalkylsiloxane unit contains two or more alkylsiloxane units. Examples of the polyalkylsiloxane unit include a linear type, a branched type, and a dendrimer type, and among them, a linear type polyalkylsiloxane unit represented by- ( Si (R18) 2O ) n- may be contained. preferable.
• R 18 represents a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms, and more preferably a methyl group.
• n indicates the average degree of polymerization of the polyalkylsiloxane unit.
• the average degree of polymerization of the polyalkylsiloxane unit is preferably 5 to 1000, more preferably 10 to 500, still more preferably 30 to 300, and particularly preferably 50 to 200.
• the average degree of polymerization is at least the above lower limit value, the water-sliding property of the cured product of the present resin composition is more excellent, and when it is at least the above upper limit value, a monomer having a polyalkylsiloxane unit (a silicone macromonomer described later).
• X)) is easily compatible with other monomers, and the copolymer (A) tends to be easily produced.
• the copolymer (A) may contain a polyalkylsiloxane unit in the main chain, in the side chain, or in both the main chain and the side chain. From the viewpoint of water permeability and ease of production of the copolymer (A), it is preferable to include a polydimethylsiloxane unit in at least the side chain.
• the copolymer (A) containing at least the polyalkylsiloxane unit in the side chain is used in consideration of the ease of introducing the polyalkylsiloxane unit and the ease of controlling the performance such as slipperiness.
• a copolymer containing a structural unit based on the silicone macromonomer (X) hereinafter, also referred to as “macromonomer (X)”) (hereinafter, also referred to as “constituent unit (X)”) is preferable.
• the copolymer (A) is a structural unit based on the monomer (Y) having a group represented by the specific formula (1) from the viewpoint of improving the performance such as water-sliding property (hereinafter, “constituent unit (hereinafter,“ structural unit (hereinafter, “constituent unit”). It is also preferable to further include Y) ”.
• the copolymer (A) is a structural unit based on a monomer (Z) other than the macromonomer (X) and the monomer (Y), if necessary, as long as the performance is not impaired (hereinafter, “constituent unit”). (Z) ”) may be further included.
• silicone macromonomer (X) examples include compounds containing a polyalkylsiloxane unit and a polymerizable functional group.
• the polymerizable functional group may be any group containing a polymerizable unsaturated bond such as a polymerizable carbon-carbon double bond, and examples thereof include a (meth) acryloyl group, a vinyl group, and a (meth) acrylamide group. .. Among these, the (meth) acryloyl group is preferable from the viewpoint of easiness of copolymerization with other monomers.
• the polyalkylsiloxane unit and the polymerizable functional group may be bonded via a linking group. Examples of the linking group include a hydrocarbon group such as an alkylene group having 1 to 6 carbon atoms.
• silicone macromonomer (X) having a (meth) acryloyl group examples include a compound represented by the following formula (2).
• CH 2 CR 19 -CO-O-R 20- (Si (R 18 ) 2 O) n -R 21 ...
• R 18 represents a hydrocarbon group having 1 to 10 carbon atoms
• n represents an average degree of polymerization
• R 19 represents a hydrogen atom or a methyl group
• R 20 represents a hydrocarbon group having 1 to 10 carbon atoms.
• R 21 represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an aryl group.
• n is the same as the preferable range of the average degree of polymerization of the polyalkylsiloxane unit described above.
• R 18 represents a hydrocarbon group having 1 to 10 carbon atoms, a hydrocarbon group having 1 to 5 carbon atoms is preferable, a methyl group is more preferable, R 19 is preferably a methyl group, and R 20 is carbon.
• a hydrocarbon group having 1 to 6 carbon atoms is preferable, a hydrocarbon group having 2 to 4 carbon atoms is more preferable, a hydrocarbon group having 1 to 6 carbon atoms is preferable, and a hydrocarbon group having 1 to 4 carbon atoms is more preferable. preferable.
• the weight average molecular weight of the silicone macromonomer (X) (hereinafter, also referred to as “Mw”) is preferably 500 to 40,000, more preferably 700 to 30,000, further preferably 800 to 20,000, particularly preferably 1,000 to 18,000, and 2000. ⁇ 15000 is the most preferable.
• Mw of the silicone macromonomer (X) is at least the above lower limit value, the smoothness of the cured product of the present resin composition is more excellent, and when it is at least the above upper limit value, the silicone macromonomer (X) is a monomer ( It tends to be easily compatible with Y) and the monomer (Z), and it tends to be easy to produce the copolymer (A).
• Mw of the silicone macromonomer (X) is a standard polystyrene-equivalent value measured by gel permeation chromatography (GPC).
• silicone macromonomer (X) a commercially available product can be used.
• linear silicone macromonomers (X) include JNC's Cyraplane (registered trademark) FM-0711 (number average molecular weight catalog publication value: 1000) and Cyraplane FM-0721 (number average).
• Silaplane FM-0725 number average molecular weight catalog publication value: 10000
• X-22-174ASX number average molecular weight catalog publication value: 900
• -174BX number average molecular weight catalog publication value: 2300
• KF-2012 number average molecular weight catalog publication value: 4600
• X-22-2426 number average molecular weight catalog publication value: 12000
• examples of the dendrimer type silicone macromonomer (X) include HGO-3002 manufactured by Silicon Material Development. As the silicone macromonomer (X), one type may be used alone, or two or more types may be used in combination.
• the monomer (Y) has a group represented by the following formula (1) (hereinafter, also referred to as “group (1)”).
• group (1) When the group (1) is introduced into the copolymer (A) by the monomer (Y), the group (1) in the copolymer (A) and the component (B) react with each other to form a polydimethylsiloxane unit. Can be prevented from bleeding out to the surface of the cured product of the present resin composition, and the durability is improved.
• M represents Al, Fe, In, Ge, Hf, Si, Ti, Sn, Zr, or Ta
• R 1 represents a hydrocarbon group having 1 to 5 carbon atoms
• R 2 represents a hydrocarbon group having 1 to 5 carbon atoms.
• R 3 represents a hydrogen atom , an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an aryl group, or an acyl group.
• M represents an integer of 3 to 4 according to M
• r represents an integer of 0 to 3
• r R2s may be different from each other
• mr is 2.
• the (mr) R3s may be different from each other.
• M is Al (aluminum), Fe (iron), In (indium), Ge (germanium), Hf (hafnium), Si (silicon), Ti (titanium), Sn (tin), Either Zr (zirconium) or Ta (tantal) may be used, but Al, Si, Ti, or Zr is preferable from the viewpoint of reactivity and availability, and Si is particularly preferable because it is inexpensive and easy to use. ..
• Examples of the aryl group of R 2 and R 3 include a phenyl group, a toluyl group, a naphthyl group and the like.
• the alkyl group, alkenyl group, and aryl group of R 2 and R 3 may each have a substituent.
• Examples of the substituent include a halogen atom such as a chlorine atom, a methoxy group, an alkoxy group of an ethoxy group, and the like.
• acyl group of R 3 examples include a (meth) acrylic group, an acetyl group, an acetimideyl group, an aldehyde group, a thioacetyl group, a propionyl group, a benzenesulfonyl group and a benzoyl group.
• OR 3 can be subdivided into an alkoxy group, an alkenyloxy group, an aryloxy group, an acyloxy group, a ketoximate group, and a hydroxy group.
• an alkoxy group, an alkenyloxy group, an acyloxy group, and a hydroxy group are preferable because of their high reactivity, and an alkoxy group such as a methoxy group and an ethoxy group or a hydroxy group is preferable because the hydrolyzability is easy to control and handle. Groups are particularly preferred.
• Examples of the group (1) (also referred to as a hydrolyzable silyl group) when M in the formula (1) is Si include a trimethoxysilyl group, a triethoxysilyl group, a triisopropoxysilyl group and a dimethoxymethylsilyl.
• Group, diethoxymethylsilyl group, diisopropoxymethylsilyl group, tris (2-propenyloxy) silyl group, (chloromethyl) dimethoxysilyl group, (methoxymethyl) dimethoxysilyl group, (methoxymethyl) diethoxysilyl group, (Ethoxymethyl) dimethoxysilyl group is mentioned.
• a trimethoxysilyl group, a triethoxysilyl group, and a dimethoxymethylsilyl group are preferable, and a dimethoxymethylsilyl group is more preferable, from the viewpoint of general purpose, high activity, and good curability.
• a dimethoxymethylsilyl group and a triethoxysilyl group are preferable.
• a (chloromethyl) dimethoxysilyl group and a (methoxymethyl) dimethoxysilyl group are preferable from the viewpoint of exhibiting particularly high curability.
• a trifunctional silyl group such as a trimethoxysilyl group or a triethoxysilyl group is preferable in that the recoverability of the cured product tends to be high.
• Examples of the monomer (Y) include a compound having the above-mentioned group (1) and a polymerizable functional group or a reactive group capable of being added (polymer reaction) to the polymer.
• Examples of the polymerizable functional group include the same as described above, and the same applies to preferred embodiments.
• Examples of the reactive group include a vinyl group, a (meth) acryloyl group, a (meth) acrylamide group, an epoxy group, a cyclic epoxy group, a mercapto group, an amino group, a diamino group, an acid anhydride group, an isocyanate group and the like. ..
• the group (1) and the polymerizable functional group or the reactive group may be bonded via a linking group.
• Examples of the linking group include a hydrocarbon group such as an alkylene group having 1 to 6 carbon atoms.
• Examples of the monomer (Y) include vinyltrimethoxysilane, vinyltriethoxylan, vinyltris ( ⁇ -methoxyethoxy) silane, (meth) acrylic acid (3-trimethoxysilyl) propyl, and (meth) acrylic.
• Vinyl-based silane compounds such as acrylic acid (dimethoxymethylsilyl) methyl, ⁇ -aminopropyltrimethoxylane, N- ⁇ - (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- ⁇ - (aminoethyl) ⁇ - Amino-based silane compounds such as aminopropylmethyldimethoxysilane and ⁇ -ureidopropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxylane, ⁇
• the monomer (Y) is not limited to these.
• a titanate-based, aluminate-based, or zirconate-based coupling agent having a polymerizable functional group that can be copolymerized with another monomer or a reactive group other than the group (1) that can be added to the polymer may be used. good.
• the monomer (Y) one type may be used alone, or two or more types may be used in combination.
• the silicone macromonomer (X) and the monomer (Y) are copolymerized, the better the copolymerizability of the silicone macromonomer (X) and the monomer (Y), the more the unreacted monomer is reduced. This can be done, and the durability of the cured product of the present resin composition tends to be improved.
• the polymerizable functional group of the silicone macromonomer (X) is a (meth) acryloyl group
• the monomer (Y) is particularly preferably a vinyl-based silane compound having a (meth) acryloyl group.
• the monomer (Z) may be copolymerizable with the silicone macromonomer (X), and for example, the above-mentioned compound having a polymerizable functional group (however, the silicone macromonomer (X) and the monomer (Y)) may be used. ) Is excluded.)
• the monomer (Z) include the following. Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, (meth) acrylic Acid tert-butyl, (meth) acrylate n-pentyl, (meth) acrylate n-hexyl, (meth) acrylate cyclohexyl, (meth) acrylate n-heptyl, (meth) acrylate n-octyl, (meth) ) 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (
• Styrene-based monomers such as styrene, vinyltoluene, ⁇ -methylstyrene, chlorstyrene, styrenesulfonic acid and salts thereof.
• Maleic anhydride maleic acid, monoalkyl esters and dialkyl esters of maleic acid; monoalkyl esters and dialkyl esters of fumaric acid, fumaric acid.
• Maleimide-based monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, and cyclohexylmaleimide.
• Nitrile group-containing vinyl-based monomers such as acrylonitrile and methacrylonitrile.
• Amide group-containing vinyl-based monomers such as acrylamide and methacrylamide.
• Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamic acid.
• Alkenes such as ethylene and propylene. Conjugated diene such as butadiene and isoprene. Vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, etc.
• the monomer (Z) one type may be used alone, or two or more types may be used in combination.
• the silicone macromonomer (X) and the monomer (Z) are copolymerized, the better the copolymerizability of the silicone macromonomer (X) and the monomer (Z), the more the unreacted monomer is reduced. This can be done, and the durability of the cured product of the present resin composition tends to be improved.
• the polymerizable functional group of the silicone macromonomer (X) is a (meth) acryloyl group
• the monomer (Z) is derived from the styrene-based monomer and the (meth) acrylic acid-based monomer. At least one of them is preferable, and a (meth) acrylic acid-based monomer is particularly preferable.
• the ratio of the structural unit (X) to the total mass of all the structural units constituting the copolymer (A) is preferably 15 to 60% by mass, more preferably 15 to 50% by mass, still more preferably 20 to 50% by mass. ..
• the ratio of the structural unit (X) is at least the above lower limit value, the smoothness of the cured product becomes better, and when it is at least the above upper limit value, the amount of unpolymerized silicone macromonomer (X) can be reduced. Therefore, the transparency of the cured product tends to be good.
• the ratio of the structural unit (Y) to the total mass of all the structural units constituting the copolymer (A) is preferably 40 to 85% by mass, more preferably 40 to 80% by mass, still more preferably 40 to 75% by mass. ..
• the ratio of the constituent unit (Y) is at least the above lower limit value, the durability of the cured product is better, and when it is at least the above upper limit value, the proportion of the constituent unit (X) can be sufficiently increased, so that the cured product is cured.
• the water-sliding property of an object tends to be good.
• the total of the ratio of the structural unit based on the silicone macromonomer (X) and the ratio of the structural unit based on the monomer (Y) to the total mass of all the structural units constituting the copolymer (A) is 55% by mass.
• the above is preferable, 70% by mass or more is more preferable, 80% by mass or more is further preferable, 90% by mass or more is particularly preferable, and 100% by mass is most preferable.
• the total of the ratios of the structural unit (X) and the structural unit (Y) is at least the above lower limit value, the durability of the cured product and the water-sliding property of the cured product tend to be better.
• the ratio of the structural unit (Z) to the total mass of all the structural units constituting the copolymer (A) is preferably 0 to 45% by mass, more preferably 0 to 40% by mass, still more preferably 0 to 30% by mass. , 0 to 20% by mass is particularly preferable, and 0 to 10% by mass is most preferable.
• the higher the proportion of the structural unit (Z) the better the copolymerizability when producing the copolymer (A) tends to be.
• the ratio of each structural unit is obtained by an analysis method such as infrared spectroscopic analysis by a nuclear magnetic resonance method or a total internal reflection measurement method.
• the Mw of the copolymer (A) is preferably 3000 to 40000, more preferably 5000 to 100,000, and particularly preferably 7000 to 80000. Further, 8000 to 40,000 is more preferable.
• the Mw of the copolymer (A) is equal to or higher than the above lower limit value, the copolymer (A) is firmly immobilized in the cured product, so that the water smoothness and durability tend to be improved, and the above upper limit value. If the following, the compatibility with other components in the present resin composition is improved, so that the appearance of the cured product tends to be improved.
• the Mw of the copolymer (A) is a standard polystyrene-equivalent value measured by gel permeation chromatography (GPC).
• the method for producing the copolymer (A) is not particularly limited, and a known method can be appropriately adopted.
• a copolymer having a structural unit (X) and a structural unit (Y) can be produced by the following method (i) or (ii).
• a monomer mixture containing a silicone macromonomer (X) and, if necessary, a monomer (Z) is polymerized, and the obtained polymer contains a reactive group that can be added to the polymer.
• the ratio of the silicone macromonomer (X) to the total mass of the silicone macromonomer (X), the monomer (Y) and the monomer (Z) is 15 to 60% by mass. Is preferable, 15 to 50% by mass is more preferable, and 20 to 50% by mass is further preferable.
• the ratio of the silicone macromonomer (X) is not less than the above lower limit value, the smoothness of the cured product becomes better, and when it is not more than the above upper limit value, the amount of unpolymerized silicone macromonomer (X) can be reduced. As a result, the transparency of the cured product tends to be good.
• the ratio of the monomer (Y) to the total mass of the silicone macromonomer (X), the monomer (Y), and the monomer (Z) is preferably 40 to 85% by mass, more preferably 40 to 80% by mass. It is preferable, and more preferably 40 to 75% by mass.
• the proportion of the monomer (Y) is at least the above lower limit value, the durability of the cured product becomes better, and when it is at least the above upper limit value, the proportion of the silicone macromonomer (X) can be sufficiently increased. , The water-sliding property of the cured product tends to be good.
• the ratio of the monomer (Z) to the total mass of the silicone macromonomer (X), the monomer (Y), and the monomer (Z) is preferably 0 to 45% by mass, more preferably 0 to 40% by mass. It is preferable, 0 to 30% by mass is more preferable, 0 to 20% by mass is particularly preferable, and 0 to 10% by mass is most preferable.
• the higher the proportion of the monomer (Z) the better the copolymerizability of the monomer mixture tends to be.
• the polymerization method of the monomer mixture is not particularly limited, and known polymerization methods such as solution polymerization method, suspension polymerization, bulk polymerization and emulsion polymerization can be used.
• the polymerization conditions are not particularly limited, but can be, for example, 0.5 to 24 hours at 30 to 180 ° C.
• the monomer mixture is preferably polymerized in the presence of a polymerization initiator.
• a polymerization initiator various known polymerization initiators can be used.
• V-70 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile)
• V-65 2,2'-azobis (2,4-dimethylvaleronitrile)
• Nichiyu Nichiyu
• Succinic Acid Peroxide Paroyl SA, Nichiyu
• Benzoyl Peroxide Nyper® BW, Nichiyu
• Isobutylyl Peroxide Paroyl IB, Nichiyu
• 2 4-Dichlorobenzoyl peroxide (Nyper CS, manufactured by Nissui), 3,5,5-trimethylhexanoyl peroxide (Paroyl355, manufactured by Nissui), etc.
• Dialkyl peroxides such as 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (Perhexa® 25B, manufactured by Nichiyu); ⁇ , ⁇ '-bis (manufactured by Nichiyu).
• Neodecanoylperoxy Diisopropylbenzene (Diper (registered trademark) ND, manufactured by Nichiyu), Kumilperoxy Neodecanoate (Parkmill (registered)) Trademarks) ND, manufactured by NOF Corporation), 1,1,3,3-tetramethylbutylperoxyneodecanoate (PeroctaND, manufactured by NOF CORPORATION), 1-cyclohexyl-1-methylethylperoxyneodecanoate (trademark) Percyclo (registered trademark) ND, manufactured by NOF Corporation, t-hexyl peroxyneodecanoate (Perhexyl (registered trademark) ND, manufactured by NOF Corporation), t-butyl peroxyneodecanoate (perbutyl ND, manufactured by NOF) ), T-hexyl peroxypivalate (Perhexyl PV, NOF), t-butyl peroxypivalate (Per
• the polymerization initiator is not particularly limited to these.
• the polymerization initiator one type may be used alone, or two or more types may be used in combination.
• the amount of the polymerization initiator used is, for example, 0.01 to 10 parts by mass with respect to 100 parts by mass of the monomer mixture.
• a silicone macromonomer (X) and a monomer (Z) containing a hydroxyl group are copolymerized, and then an isocyanate group is used.
• examples thereof include a method of addition-reacting a compound containing a compound (1) with a group (1), but the present invention is not particularly limited.
• the component (B) is composed of at least one silane compound represented by the following formula (b) (hereinafter, also referred to as “silane compound (b)”) or a partially hydrolyzed condensate thereof.
• silane compound (b) represented by the following formula (b) (hereinafter, also referred to as “silane compound (b)”) or a partially hydrolyzed condensate thereof.
• R 4 4-n Si (OR 5 ) n ...
• R 4 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group
• R 5 represents an alkyl group or a phenyl group
• n represents an integer of 2 to 4
• n OR 5s are different from each other.
• n is 2, ( 4 -n) R4s may be different from each other.
• the alkyl group of R4 may be linear or branched.
• the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 4.
• the aryl group include a phenyl group, a toluyl group, a naphthyl group and the like.
• the aralkyl group include a benzyl group and a phenethyl group.
• the alkyl group of R5 may be linear or branched, and is preferably linear from the viewpoint of hydrolysis rate.
• the number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 or 2, and even more preferably 1 from the viewpoint of the rate of hydrolysis.
• silane compound (b1) The silane compound when n in the formula (b) is 4 (hereinafter, also referred to as “silane compound (b1)”) is represented by the following formula (b1).
• R 6 , R 7 , R 8 and R 9 independently represent an alkyl group or a phenyl group, respectively.
• R6, R7 , R8 and R9 are the same as R5 above.
• silane compound (b2) The silane compound when n in the formula (b) is 3 (hereinafter, also referred to as “silane compound (b2)”) is represented by the following formula (b2).
• R 10 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.
• R 11 , R 12 and R 13 independently represent an alkyl group or a phenyl group, respectively.
• R 10 is the same as R 4 above.
• R 11 , R 12 and R 13 are the same as R 5 above.
• silane compound (b3) The silane compound when n in the formula (b) is 2 (hereinafter, also referred to as “silane compound (b3)”) is represented by the following formula (b3).
• R 14 and R 15 independently represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, respectively.
• R 16 and R 17 independently represent an alkyl group or a phenyl group, respectively.
• R 14 and R 15 are the same as R 4 above.
• R 16 and R 17 are the same as R 5 above.
• silane compound (b1) examples include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrapentyloxysilane, tetraphenyloxysilane, trimethoxymonoethoxysilane, dimethoxydiethoxysilane, and triethoxy.
• silane compound (b2) examples include trimethoxysilane, triethoxysilane, tripropoxysilane, trypentyloxysilane, triphenyloxysilane, dimethoxymonoethoxysilane, diethoxymonomethoxysilane, and dipropoxymonomethoxysilane.
• Dipropoxymonoethoxysilane dipentyloxylmonomethoxysilane, dipentyloxymonoethoxysilane, dipentyloxymonopropoxysilane, diphenyloxylmonomethoxysilane, diphenyloxymonoethoxysilane, diphenyloxymonopropoxysilane, methoxyethoxypropoxysilane, monopropoxydimethoxy Hydrosilane compounds such as silane, monopropoxydiethoxysilane, monobutoxydimethoxysilane, monopentyloxydiethoxysilane, and monophenyloxydiethoxysilane;
• Naftilt Remethoxysilane Naftilt Riethoxysilane, Naftilt Repropoxysilane, Naftilt Lipentyloxysilane, Naftilt Riphenyloxysilane, Naftilmonomethoxydiethoxysilane, Naftylmonomethoxydipropoxysilane, Naftylmonomethoxydipentyloxysilane, Naftilmono Naftylsilane compounds such as methoxydiphenyloxysilane, naphthylmethoxyethoxypropoxysilane, and naphthylmonomethoxymonoethoxymonobutoxysilane;
• silane compound (b3) examples include dimethoxysilane, diethoxysilane, dipropoxysilane, dipentyloxysilane, diphenyloxysilane, methoxyethoxysilane, methoxypropoxysilane, methoxypentyloxysilane, methoxyphenyloxysilane, and ethoxypropoxy.
• Hydrosilane compounds such as silane, ethoxypentyloxysilane, and ethoxyphenyloxysilane;
• Methyldimethoxysilane Methylmethoxyethoxysilane, Methyldiethoxysilane, Methylmethoxypropoxysilane, Methylmethoxypentyloxysilane, Methylethoxypropoxysilane, Methyldipropoxysilane, Methyldipentyloxysilane, Methyldiphenyloxysilane, Methylmethoxyphenyloxysilane Methylhydrosilane compounds such as;
• Hydroxyphenyldimethoxysilane hydroxyphenylmethoxyethoxysilane, hydroxyphenyldiethoxysilane, hydroxyphenylmethoxypropoxysilane, hydroxyphenylmethoxypentyloxysilane, hydroxyphenylethoxypropoxysilane, hydroxyphenyldipropoxysilane, hydroxyphenyldipentyloxysilane, hydroxyphenyl Hydroxyphenylhydrosilane compounds such as diphenyloxysilane and hydroxyphenylmethoxyphenyloxysilane;
• Hydroxybenzyldimethoxysilane hydroxybenzylmethoxyethoxysilane, hydroxybenzyldiethoxysilane, hydroxybenzylmethoxypropoxysilane, hydroxybenzylmethoxypentyloxysilane, hydroxybenzylethoxypropoxysilane, hydroxybenzyldipropoxysilane, hydroxybenzyldipentyloxysilane, hydroxybenzyl Hydroxybenzylhydrosilane compounds such as diphenyloxysilane and hydroxybenzylmethoxyphenyloxysilane;
• Dimethylsilane compounds such as dimethyldimethoxysilane, dimethylmethoxyethoxysilane, dimethylmethoxypropoxysilane, dimethyldiethoxysilane, dimethyldipentyloxysilane, dimethyldiphenyloxysilane, dimethylethoxypropoxysilane, dimethyldipropoxysilane;
• Diethylsilane compounds such as diethyldimethoxysilane, diethylmethoxyethoxysilane, diethylmethoxypropoxysilane, diethyldiethoxysilane, diethyldipentyloxysilane, diethyldiphenyloxysilane, diethylethoxypropoxysilane, diethyldipropoxysilane;
• Dipropoxy such as dipropyldimethoxysilane, dipropylmethoxyethoxysilane, dipropylmethoxypropoxysilane, dipropyldiethoxysilane, dipropyldipentyloxysilane, dipropyldiphenyloxysilane, dipropylethoxypropoxysilane, dipropyldipropoxysilane Silane compound;
• Dibutylsilane compounds such as dibutyldimethoxysilane, dibutylmethoxyethoxysilane, dibutylmethoxypropoxysilane, dibutyldiethoxysilane, dibutyldipentyloxysilane, dibutyldiphenyloxysilane, dibutylethoxypropoxysilane, dibutyldipropoxysilane;
• Diphenylsilane compounds such as diphenyldimethoxysilane, diphenylmethoxyethoxysilane, diphenylmethoxypropoxysilane, diphenyldiethoxysilane, diphenyldipentyloxysilane, diphenyldiphenyloxysilane, diphenylethoxypropoxysilane, diphenyldipropoxysilane; Di (Hydroxyphenyl) Dimethoxysilane, Di (Hydroxyphenyl) methoxyethoxysilane, Di (Hydroxyphenyl) methoxypropoxysilane, Di (Hydroxyphenyl) Diethoxysilane, Di (Hydroxyphenyl) Dipentyloxysilane, Di (Hydroxyphenyl) Diphenyl Di (hydroxyphenyl) silane compounds such as oxysilane, di (hydroxyphenyl) ethoxypropoxy
• Dinaphthyl such as dinaphthyldimethoxysilane, dinaphthylmethoxyethoxysilane, dinaphthylmethoxypropoxysilane, dinaphthyldiethoxysilane, dinaphthyldipentyloxysilane, dinaphthyldiphenyloxysilane, dinaphthylethoxypropoxysilane, dinaphthyldipropoxysilane Silane compound;
• Dibenzyl such as dibenzyldimethoxysilane, dibenzylmethoxyethoxysilane, dibenzylmethoxypropoxysilane, dibenzyldiethoxysilane, dibenzyldipentyloxysilane, dibenzyldiphenyloxysilane, dibenzylethoxypropoxysilane, dibenzyldipropoxysilane Silane compound;
• Methylethyl such as methylethyldimethoxysilane, methylethylmethoxyethoxysilane, methylethylmethoxypropoxysilane, methylethyldiethoxysilane, methylethyldipentyloxysilane, methylethyldiphenyloxysilane, methylethylethoxypropoxysilane, methylethyldipropoxysilane Silane compound;
• Methylpropyl such as Methylpropyldimethoxysilane, Methylpropylmethoxyethoxysilane, Methylpropylmethoxypropoxysilane, Methylpropyldiethoxysilane, Methylpropyldipentyloxysilane, Methylpropyldiphenyloxysilane, Methylpropylethoxypropoxysilane, Methylpropyldipropoxysilane Silane compound;
• Methylbutyl such as methylbutyldimethoxysilane, methylbutylmethoxyethoxysilane, methylbutylmethoxypropoxysilane, methylbutyldiethoxysilane, methylbutyldipentyloxysilane, methylbutyldiphenyloxysilane, methylbutylethoxypropoxysilane, methylbutyldipropoxysilane, etc.
• Silane compound Silane compound
• Methyl (phenyl) dimethoxysilane Methyl (phenyl) methoxyethoxysilane, Methyl (phenyl) methoxypropoxysilane, Methyl (phenyl) diethoxysilane, Methyl (phenyl) dipentyloxysilane, Methyl (phenyl) diphenyloxysilane, Methyl (phenyl) ) Methyl (phenyl) silane compounds such as ethoxypropoxysilane and methyl (phenyl) dipropoxysilane;
• Methyl (hydroxyphenyl) silane compounds such as oxysilane, methyl (hydroxyphenyl) ethoxypropoxysilane, methyl (hydroxyphenyl) dipropoxysilane;
• Methyl (naphthyl) dimethoxysilane Methyl (naphthyl) methoxyethoxysilane, Methyl (naphthyl) methoxypropoxysilane, Methyl (naphthyl) diethoxysilane, Methyl (naphthyl) dipentyloxysilane, Methyl (naphthyl) diphenyloxysilane, Methyl (naphthyl) ) Methyl (naphthyl) silane compounds such as ethoxypropoxysilane, methyl (naphthyl) dipropoxysilane;
• Methyl (benzyl) dimethoxysilane methyl (benzyl) methoxyethoxysilane, methyl (benzyl) methoxypropoxysilane, methyl (benzyl) diethoxysilane, methyl (benzyl) dipentyloxysilane, methyl (benzyl) diphenyloxysilane, methyl (benzyl) ) Methyl (benzyl) silane compounds such as ethoxypropoxysilane, methyl (benzyl) dipropoxysilane;
• Methyl (hydroxybenzyl) silane compounds such as oxysilane, methyl (hydroxybenzyl) ethoxypropoxysilane, methyl (hydroxybenzyl) dipropoxysilane;
• Ethylpropyl such as ethylpropyldimethoxysilane, ethylpropylmethoxyethoxysilane, ethylpropylmethoxypropoxysilane, ethylpropyldiethoxysilane, ethylpropyldipentyloxysilane, ethylpropyldiphenyloxysilane, ethylpropylethoxypropoxysilane, ethylpropyldipropoxysilane Silane compound;
• Ethylbutyl such as ethylbutyldimethoxysilane, ethylbutylmethoxyethoxysilane, ethylbutylmethoxypropoxysilane, ethylbutyldiethoxysilane, ethylbutyldipentyloxysilane, ethylbutyldiphenyloxysilane, ethylbutylethoxypropoxysilane, ethylbutyldipropoxysilane Silane compound;
• Ethyl (hydroxyphenyl) silane compounds such as oxysilane, ethyl (hydroxyphenyl) ethoxypropoxysilane, ethyl (hydroxyphenyl) dipropoxysilane;
• Ethyl (hydroxybenzyl) silane compounds such as oxysilane, ethyl (hydroxybenzyl) ethoxypropoxysilane, ethyl (hydroxybenzyl) dipropoxysilane;
• Propylbutyl such as propylbutyldimethoxysilane, propylbutylmethoxyethoxysilane, propylbutylmethoxypropoxysilane, propylbutyldiethoxysilane, propylbutyldipentyloxysilane, propylbutyldiphenyloxysilane, propylbutylethoxypropoxysilane, propylbutyldipropoxysilane Silane compound;
• a propyl (hydroxyphenyl) silane compound such as oxysilane, propyl (hydroxyphenyl) ethoxypropoxysilane, propyl (hydroxyphenyl) dipropoxysilane;
• propyl (hydroxybenzyl) silane compounds such as oxysilane, propyl (hydroxybenzyl) ethoxypropoxysilane, and propyl (hydroxybenzyl) dipropoxysilane.
• silane compound (b) one type may be used alone or two or more types may be used in combination.
• the partially hydrolyzed condensate of at least one silane compound (b) is obtained by hydrolyzing and condensing the silane compound (b) or a mixture of two or more thereof by a known method.
• a predetermined amount of water and, if necessary, an organic solvent are added to the monomer of tetramethoxysilane, and the reaction is usually carried out at about room temperature to 100 ° C. while distilling off by-produced alcohol in the presence of a catalyst.
• hydrolysis and condensation of tetramethoxysilane proceed to produce a liquid tetramethoxysilane partial hydrolysis condensate (average degree of polymerization is usually about 2 to 8, most of which is 3 to 7).
• the liquid tetramethoxysilane partial hydrolysis condensate is represented by, for example, CH 3 O- (Si (OCH 3 ) 2 -O) s -CH 3 .
• s is a number of 2 to 8 representing the average degree of polymerization.
• the degree of hydrolysis can be appropriately adjusted depending on the amount of water used.
• the liquid tetramethoxysilane partial hydrolysis condensate obtained as described above may be further hydrolyzed and condensed.
• the method of further hydrolyzing and condensing the liquid tetramethoxysilane partial hydrolysis condensate is the same as the method of using the primary reaction product described later as the secondary reaction product.
• a partially hydrolyzed condensate can be obtained in the same manner.
• a mixture of two or more kinds of silane compounds (b) may be used as a partially hydrolyzed condensate.
• the catalyst examples include inorganic acids such as hydrochloric acid, acetic acid, nitrate, formic acid, sulfuric acid and phosphoric acid, and organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, paratoluenesulfonic acid, benzoic acid, phthalic acid and maleic acid.
• Alkaline catalysts such as potassium hydroxide, sodium hydroxide, calcium hydroxide, ammonia, organic metals, metal alkoxides, eg organic tin compounds such as dibutyltin dilaurylate, dibutyltin dioctate, dibutyltin diacetate, aluminum tris (acetylacetate).
• metal chelate compounds such as (acetylacetonate) and zirconium bis (isopropoxy) bis (acetylacetonate), and boron compounds such as borate butoxide and borate.
• an organic acid or a metal chelate compound is particularly preferable, and maleic acid or a metal acetylacetonate is particularly preferable for the production of a secondary reaction product.
• the amount of the acid catalyst used is not particularly limited as long as it can exhibit the function as a catalyst, but is usually about 0.001 to 10 parts by mass with respect to 100 parts by mass of the silane compound (b). It is selected from the range, preferably 0.003 to 5 parts by mass.
• the component (B) is a silane compound (b1) in which R 6 , R 7 , R 8 and R 9 in the formula (b1) are alkyl groups, that is, tetraalkoxysilane or a partial hydrolysis condensation thereof. It is preferably contained, more preferably it contains a partially hydrolyzed condensate of tetraalkoxysilane, and particularly preferably it contains a partially hydrolyzed condensate of tetramethoxysilane.
• the Mw of the component (B) is preferably 500 or more, more preferably 600 or more, from the viewpoint of the appearance of the cured product.
• the upper limit of Mw of the component (B) is, for example, 10,000.
• the Mw of the component (B) is a standard polystyrene-equivalent value measured by gel permeation chromatography (GPC).
• the component (B) is a partially hydrolyzed condensate of at least one silane compound (b) from the viewpoint of reactivity, and is a partially hydrolyzed condensate having an Mw of 300 to 3000 (hereinafter, “primary reactant”). (Also also referred to as)) is preferably hydrolyzed and condensed in the presence of a catalyst (hereinafter, also referred to as “secondary reactant”).
• a catalyst hereinafter, also referred to as “secondary reactant”.
• silanol groups Si—OH
• the silanol group has higher reactivity than Si-OR 5 , the curability is improved.
• the condensation reaction is promoted, the molecular weight becomes large and cracks are suppressed, so that the appearance can be improved.
• the Mw of the primary reaction product is 300 or more, the appearance of the cured product tends to be good, and when it is 3000 or less, the reactivity tends to be good.
• the Mw of the primary reaction product is preferably 400 to 2000, more preferably 500 to 1000.
• the silane compound (b) forming the primary reaction product the silane compound (b1) is preferable, the tetraalkoxysilane is more preferable, and the tetramethoxysilane is further preferable, from the viewpoint of the hardness of the cured product.
• the primary reaction product is obtained by subjecting the silane compound (b) or a mixture of two or more thereof to a hydrolysis condensation reaction.
• primary reactants can also be used, for example, MS51, MS53, MS57, MS56S manufactured by Mitsubishi Chemical, ethyl silicate 40 manufactured by Corcote, ethyl silicate 48, methyl silicate 51, methyl silicate 53A, EMS-. 485 and the like can be mentioned.
• a method of further hydrolyzing and condensing the primary reaction product in the presence of a catalyst to obtain a secondary reaction product there is a method of adding water, a catalyst and a solvent to the primary reaction product and stirring at 25 ° C. for 1 day or more. .. Further, the progress of the reaction can be promoted by heating the primary reaction product, and in that case, for example, a method of stirring at 30 ° C. to 100 ° C. for 1 hour or more can be used.
• the Mw of the secondary reaction product is preferably 400 to 50,000, more preferably 600 to 30,000, further preferably 800 to 10,000, and even more preferably 900 to 5,000, based on the empirical temperature and reaction time in the study by the present inventors. Is particularly preferable, and 1000 to 2000 is most preferable.
• the reaction of the secondary reaction product proceeds over time, it is difficult to specify its structure and characteristics (for example, size such as radius, hydroxyl value, etc.) in addition to Mw by a general analytical method. ..
• Mw can be measured, the reactivity of the present resin composition and the appearance of the cured product are different between the case where the primary reaction product is used as the component (B) and the case where the secondary reaction product is used. That is, there are circumstances (impossible / impractical circumstances) in which it is impossible or approximately impractical to directly identify the secondary reactant by its structure or properties.
• the secondary reaction product is "a partially hydrolyzed condensate of at least one silane compound (b) having a Mw of 300 to 3000, which is further hydrolyzed and condensed in the presence of a catalyst. It is more appropriate to specify.
• ⁇ Initiator (C)> When the present resin composition contains the initiator (C), the hydrolysis-condensation reaction of the component (B) and the group (1) is facilitated, and the curability of the present resin composition is improved.
• the initiator (C) include a photopolymerization initiator, a thermal polymerization initiator, a metal catalyst, an acid catalyst and the like.
• Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photoacid generator, and a photobase generator.
• Examples of the thermal polymerization initiator include a thermal radical polymerization initiator, a thermal acid generator, and a thermal base generator.
• Examples of the metal catalyst or acid catalyst include catalysts similar to those used for obtaining a partially hydrolyzed condensate of the silane compound (b). Any one of these may be used alone or two or more thereof may be used in combination.
• the photopolymerization initiator is preferable as the initiator (C).
• the present resin composition contains a photopolymerization initiator
• curing of the present resin composition can be promoted by irradiation with active energy rays such as ultraviolet rays. If the resin composition is applied to a resin base material and then cured by heat, the resin base material may be deformed by heat, but if it is cured by active energy rays, the resin base material is deformed by heat. It can be applied to a resin base material having low heat resistance. Further, in general, curing by active energy rays is expected to improve productivity because the curing time is shorter than other curing methods such as thermal curing and moisture curing.
• the photopolymerization initiator As the photopolymerization initiator, the hydrolysis-condensation reaction of the component (B) and the group (1) can be started, and the present resin composition can be efficiently cured. Therefore, the photoradical polymerization initiator and the photoacid generation At least one selected from the group consisting of agents and photobase generators is preferred, at least one selected from the group consisting of photoacid generators and photobase generators is more preferred, and photoacid generators are even more preferred.
• photoradical polymerization initiator Typical examples of the photoradical polymerization initiator (hereinafter, also simply referred to as “photoinitiator”) are diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and benzyldimethylketal.
• Typical examples of photoacid generators include sulfonium salts such as triarylsulfonium hexafluorophosphate (eg, p-phenylthiophenyldiphenylsulfonium hexafluorophosphate) and triarylsulfonium hexafluoroantimonate (particularly triaryl).
• sulfonium salts such as triarylsulfonium hexafluorophosphate (eg, p-phenylthiophenyldiphenylsulfonium hexafluorophosphate) and triarylsulfonium hexafluoroantimonate (particularly triaryl).
• Sulfonium salt diaryliodonium hexafluorophosphate, diaryliodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, iodonium [4- (4-methylphenyl-2-methylpropyl) phenyl] hexafluoro Examples thereof include iodonium salts such as sulfonate.
• the photoacid generator is not limited to the exemplified compounds. One type of photoacid generator may be used alone, or two or more types may be used in combination.
• Typical examples of photobase generators are N-cyclohexylcarbamate 1- (anthraquinone-2-yl) ethyl, N, N-diethylcarbamate 9-anthrylmethyl, piperidine-1-carboxylic acid 9-an.
• the present resin composition contains a diluent
• the coating workability when the present resin composition is applied to the substrate the smoothness and uniformity of the formed coating film and its cured film, and the basis of the cured film. Adhesion to the material is improved.
• the diluent include water, an organic solvent and the like, and an organic solvent is preferable.
• the component (B) is a hydrolyzed condensate of the silane compound (b)
• the diluent may contain water compounded for hydrolyzing and condensing the silane compound (b).
• organic solvent examples include alcohol-based solvents, glycol-based solvents, hydrocarbon-based solvents, ester-based solvents, ketone-based solvents, ether-based solvents and the like.
• Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, nbutanol, isobutanol, octanol, n-propyl alcohol, acetylacetone alcohol and the like.
• Glycol-based solvents include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol mono n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene.
• glycol monoethyl ether examples thereof include glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate.
• hydrocarbon solvent examples include benzene, kerosene, toluene, xylene and the like.
• ester solvent examples include methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate and the like.
• ketone solvent examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone and the like.
• ether solvent examples include ethyl ether, butyl ether, methyl cellosolve, ethyl cellosolve, dioxane, furan, tetrahydrofuran and the like.
• the organic solvent may be used alone or in combination of two or more.
• an alcohol solvent is preferable, and methanol, ethanol, isopropanol, or n-propanol is preferable because it is easy to handle, has good storage stability in a liquid, and has excellent characteristics of the obtained cured product. More preferred.
• ⁇ Other ingredients examples include polymers other than the copolymer (A), ultraviolet absorbers, light stabilizers, silane coupling agents, inorganic fine particles, antioxidants, anti-yellowing agents, brewing agents, pigments, and the like. Examples thereof include leveling agents, antifoaming agents, thickening agents, antisettling agents, antistatic agents and antifogging agents.
• the content of the copolymer (A) is preferably 1 to 95% by mass, more preferably 10 to 90% by mass, and further 20 to 85% by mass, based on 100% by mass of the total non-volatile components in the resin composition. Preferably, 25 to 85% by mass is particularly preferable, and 30 to 70% by mass is most preferable.
• the non-volatile component represents a component excluding the organic solvent.
• the content of the component (B) is preferably 1 to 90% by mass, more preferably 5 to 80% by mass, still more preferably 10 to 75% by mass, based on 100% by mass of the total non-volatile components in the resin composition. 20 to 70% by mass is particularly preferable, and 30 to 65% by mass is most preferable.
• the content of the component (B) is at least the above lower limit value, the strength of the cured product is more excellent, and when it is at least the above upper limit value, the appearance of the cured product is more excellent.
• the content of the initiator (C) is preferably 0.01 to 10% by mass, more preferably 0.05 to 9% by mass, and 0.1 to 0.1 to 100% by mass, based on 100% by mass of the total non-volatile components in the resin composition. 8% by mass is more preferable, 0.2 to 5% by mass is particularly preferable, and 0.2 to 3% by mass is most preferable.
• the content of the initiator (C) is at least the above lower limit value, the curability (reactivity) of the present resin composition and the productivity of the cured product are more excellent, and when it is at least the above upper limit value, the cured product is slippery. It is more water-based.
• the concentration of the non-volatile component in the present resin composition may be any concentration suitable for the coating method and is not particularly limited.
• the lower the concentration of the non-volatile component the better the smoothness and uniformity of the formed coating film and its cured film (cured product layer), and the better the adhesion between the substrate and the cured film, and the concentration of the non-volatile component.
• the higher the value the better the sagging suppressing effect when the present resin composition is applied to the substrate.
• the concentration of the non-volatile component with respect to the entire resin composition is not particularly limited, but is preferably 80% by mass or less, more preferably 0.1 to 60% by mass, still more preferably 1 to 40% by mass, and particularly preferably 1 to 30% by mass. %, Most preferably in the range of 1 to 20% by mass. By using it in the above range, a resin composition having excellent coatability can be obtained.
• the sliding angle of 20 ⁇ L of water at 23 ° C. on the surface of a cured film (initial cured film) formed by spray-coating the resin composition on a substrate and curing it is preferably 60 ° or less, preferably 50. ° or less is more preferable, 40 ° or less is further preferable, 30 ° or less is particularly preferable, and 20 ° or less is most preferable.
• the sliding angle is measured while changing the tilt angle by 1 °. Details are as described in Examples described later. Conventionally, the sliding angle is often measured while continuously changing the inclination angle. The sliding angle measured while changing the tilt angle by 1 ° tends to be larger than the sliding angle measured while continuously changing the tilt angle.
• the sliding angle can be adjusted by adjusting the content and type of the polyalkylsiloxane unit in the resin composition. Specifically, the content of the copolymer (A) is increased, the proportion of the silicone macromonomer (X) to be copolymerized in the copolymer (A) is increased, or the silicone macromonomer (X) is longer. Choosing one containing a chain polyalkylsiloxane unit tends to reduce the water sliding angle of the initial cured film.
• the sliding angle after the durability test is particularly important in a wide range of application development, and a lower one is preferable, and a smaller change from the initial stage is preferable.
• the surface of the cured film is 23 ° C.
• the sliding angle of 20 ⁇ L of water is preferably 60 ° or less, more preferably 50 ° or less, further preferably 40 ° or less, particularly preferably 30 ° or less, and most preferably 20 ° or less.
• the amount of change in the water sliding angle of the cured film after the durability test from the initial water sliding angle is as follows. 40 ° or less is preferable, 30 ° or less is more preferable, 20 ° or less is further preferable, and 15 ° or less is most preferable. There is no particular lower limit, but it is preferably 0 °. Within this range, the same level of performance as in the initial stage can be exhibited over a long period of time, and product design becomes easier.
• the sliding angle after the weather resistance test is particularly important in a wide range of application development, and a lower one is preferable, and a smaller change from the initial stage is preferable.
• a cured film is formed as described above, and the conditions are 12 minutes of rainfall in 60 minutes, irradiation intensity 180 W / m 2 (300 to 400 nm), black panel temperature 63 ° C, tank temperature 50 ° C, and tank humidity 50%.
• the sliding angle of 20 ⁇ L of water at 23 ° C. on the surface of the cured film (cured film after the durability test) after the weather resistance test for 500 hours is preferably 60 ° or less, more preferably 50 ° or less. It is preferable, more preferably 40 ° or less, particularly preferably 30 ° or less, and most preferably 20 ° or less.
• There is no particular limitation on the lower limit of the sliding angle of water for example, 1 ° or more.
• the amount of change in the water sliding angle of the cured film after the weather resistance test from the initial water sliding angle is as follows. 40 ° or less is preferable, 30 ° or less is more preferable, 20 ° or less is further preferable, and 15 ° or less is most preferable. There is no particular lower limit, but it is preferably 0 °. Within this range, the same level of performance as in the initial stage can be exhibited over a long period of time, and product design becomes easier.
• the present resin composition can be produced by mixing a copolymer (A), a component (B), an initiator (C) if necessary, a diluent, and other components.
• the diluent contains water
• the water may be added at the time of preparing the hydrolyzed condensate of the silane compound (b), may be added at the time of producing the present resin composition, and the water of the silane compound (b) may be added. It may be blended both at the time of preparing the decomposition condensate and at the time of producing the present resin composition.
• the present resin composition described above contains the copolymer (A), the component (B), and the initiator (C), a cured product having excellent appearance, water slipperiness, weather resistance, and durability is formed. can.
• This resin composition is used for sensing members such as surface materials of members through which electromagnetic waves of sensing members (millimeter wave radar, LiDAR, etc.) pass; various lamp lenses for automobiles (lighting equipment for vehicles) and hard coating agents for resin glazing. It can be used for road signs, traffic signals, camera lenses, 5G-related members, antennas, solar panels, window glass, resin glass, automobile glass, and the like.
• the use of the present resin composition is preferably a sensing member.
• the surface material of the emblem or front grill located on the front side of the millimeter wave radar or LiDAR in a vehicle is composed of a cured product of this resin composition, even if raindrops or snow adhere to the outermost surface of the emblem or the like, it is easy. It can prevent the electromagnetic waves of millimeter-wave radar and LiDAR from being attenuated or scattered by raindrops or snow.
• the cured product according to one aspect of the present invention (hereinafter, also referred to as “this cured product”) is a cured product of the present resin composition.
• the present cured product is obtained by curing the present resin composition.
• the curing method include a method of irradiating the resin composition with active energy rays, a method of curing by heating, a method of curing by utilizing the moisture in the air, and the like, from the viewpoint of the temperature applied to the substrate and productivity. Therefore, a method of irradiating the present resin composition with active energy rays is preferable.
• Examples of the active energy ray include ultraviolet rays and electron beams.
• Ultraviolet rays are preferable because they can be easily used and have excellent polymerizable properties.
• a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a UV-LED, a low-pressure mercury lamp, a xenon excimer lamp, or the like can be used as a light source. From the viewpoint of productivity, it is preferable to use a light source that exhibits maximum irradiation intensity at a wavelength of 150 to 420 nm.
• the integrated irradiation amount of ultraviolet rays is preferably 50 to 3000 mJ / cm 2 , more preferably 100 to 2000 mJ / cm 2 .
• the active energy ray may be irradiated in an air atmosphere or in an inert gas atmosphere such as nitrogen or argon.
• the time for irradiating the active energy rays is preferably in the range of 1 minute or less, more preferably 30 seconds or less, and further preferably 15 seconds or less in relation to the appearance and intensity of the cured product. There is no particular lower limit, but it is, for example, 0.1 seconds.
• the method of curing by irradiating with active energy rays can be cured in a shorter time than the method of thermosetting, and is therefore a preferable form in consideration of productivity and cost.
• the present resin composition may be heat-treated in order to remove the diluent before irradiating the present resin composition with active energy rays.
• This heat treatment can be performed by irradiation with a near-infrared lamp, circulation of warm air, or the like.
• the resin composition may be heat-treated after being irradiated with active energy rays.
• This heat treatment can be performed by irradiation with a near-infrared lamp, circulation of warm air, or the like.
• the cured product obtained by heat treatment after curing by irradiation with active energy rays tends to have excellent hardness and durability because the condensation reaction rate is higher than that without heat treatment.
• the sliding angle of water at 23 ° C. and 20 ⁇ L on the surface of the cured product (initial cured product) formed as described above is preferably as low as possible, preferably 60 ° or less, more preferably 50 ° or less, and more preferably 40 °. The following is more preferable, 30 ° or less is particularly preferable, and 20 ° or less is most preferable. There is no particular limitation on the lower limit of the sliding angle of water, and it is 0 ° or more. If the sliding angle of water is not more than the above upper limit, raindrops and snow adhering to the surface can easily slide down.
• the sliding angle of water after the durability test is particularly important in a wide range of application development, and a lower one is preferable, and a smaller change from the initial stage is preferable.
• the surface of the cured product (cured product after the durability test) is 23 ° C.
• the sliding angle of 20 ⁇ L of water is preferably 60 ° or less, more preferably 50 ° or less, further preferably 40 ° or less, particularly preferably 30 ° or less, and most preferably 20 ° or less.
• the amount of change in the water slide angle of the cured product after the durability test from the initial water slide angle is as follows. 40 ° or less is preferable, 30 ° or less is more preferable, 20 ° or less is further preferable, and 15 ° or less is most preferable. There is no particular lower limit, but it is preferably ⁇ 40 °. Within this range, the same level of performance as in the initial stage can be exhibited over a long period of time, and product design becomes easier.
• the cured product described above is a cured product of a resin composition containing the copolymer (A) and the component (B), and is therefore excellent in productivity, appearance, water permeability and durability.
• This cured product is used for sensing members such as the surface material of members through which electromagnetic waves of sensing members (millimeter wave radar, LiDAR, etc.) pass; various automobile lamp lenses (vehicle lamps), hard coats for resin glazing, road signs, etc. , Traffic traffic lights, camera lenses, 5G-related members, antennas, solar panels, window glass, resin glass, automobile glass, and the like.
• sensing members such as the surface material of members through which electromagnetic waves of sensing members (millimeter wave radar, LiDAR, etc.) pass; various automobile lamp lenses (vehicle lamps), hard coats for resin glazing, road signs, etc. , Traffic traffic lights, camera lenses, 5G-related members, antennas, solar panels, window glass, resin glass, automobile glass, and the like.
• the sensing member is the most suitable application for the cured product.
• a curable composition containing a copolymer (A) and a component (B) composed of at least one silane compound (b) or a partially hydrolyzed condensate thereof is coated on a substrate. It can be manufactured by working and curing (cured product forming step). After the cured product forming step, the formed cured product and the substrate may be peeled off, if necessary.
• the curable composition contains the copolymer (A) and the component (B).
• the curable composition typically comprises a diluent.
• the curable composition preferably contains the initiator (C).
• the curable composition may contain other components other than the above, if necessary.
• the copolymer (A), initiator (C), and other components are as described above.
• the component (B) comprises at least one silane compound (b) or a partially hydrolyzed condensate thereof.
• the silane compound (b) is as described above.
• the partially hydrolyzed condensate of at least one silane compound (b) is obtained by hydrolyzing and condensing the silane compound (b) or a mixture of two or more thereof by a known method.
• a predetermined amount of water and, if necessary, an organic solvent are added to the monomer of tetramethoxysilane, and the reaction is usually carried out at about room temperature to 100 ° C. while distilling off by-produced alcohol in the presence of a catalyst.
• hydrolysis and condensation of tetramethoxysilane proceed to produce a liquid tetramethoxysilane partial hydrolysis condensate (average degree of polymerization is usually about 2 to 8, most of which is 3 to 7).
• the liquid tetramethoxysilane partial hydrolysis condensate is represented by, for example, CH 3 O- (Si (OCH 3 ) 2 -O) s -CH 3 .
• s is a number of 2 to 8 representing the average degree of polymerization.
• the degree of hydrolysis can be appropriately adjusted depending on the amount of water used.
• the liquid tetramethoxysilane partial hydrolysis condensate obtained as described above may be further hydrolyzed and condensed.
• the method of further hydrolyzing and condensing the liquid tetramethoxysilane partial hydrolysis condensate is the same as the method of using the primary reaction product described later as the secondary reaction product.
• a partially hydrolyzed condensate can be obtained in the same manner.
• a mixture of two or more kinds of silane compounds (b) may be used as a partially hydrolyzed condensate.
• the catalyst examples include inorganic acids such as hydrochloric acid, acetic acid, nitrate, formic acid, sulfuric acid and phosphoric acid, and organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, paratoluenesulfonic acid, benzoic acid, phthalic acid and maleic acid.
• Alkaline catalysts such as potassium hydroxide, sodium hydroxide, calcium hydroxide, ammonia, organic metals, metal alkoxides, eg organic tin compounds such as dibutyltin dilaurylate, dibutyltin dioctate, dibutyltin diacetate, aluminum tris (acetylacetate).
• metal chelate compounds such as (acetylacetonate) and zirconium bis (isopropoxy) bis (acetylacetonate)
• boron compounds such as borate butoxide and borate.
• the amount of the acid catalyst used is not particularly limited as long as it can exhibit the function as a catalyst, but is usually about 0.001 to 10 parts by mass with respect to 100 parts by mass of the silane compound (b). It is selected from the range, preferably 0.003 to 5 parts by mass.
• the component (B) is a silane compound (b1) in which R 6 , R 7 , R 8 and R 9 in the formula (b1) are alkyl groups, that is, tetraalkoxysilane or a partial hydrolysis thereof, from the viewpoint of the hardness of the cured product. It is preferably a decomposition condensate, more preferably a partial hydrolysis condensate of tetraalkoxysilane, and particularly preferably a partial hydrolysis condensate of tetramethoxysilane, from the viewpoint of the sliding angle of water.
• the Mw of the component (B) is preferably 500 or more, more preferably 600 or more, from the viewpoint of appearance.
• the upper limit of Mw of the component (B) is, for example, 10,000.
• the Mw of the component (B) is a standard polystyrene-equivalent value measured by gel permeation chromatography (GPC).
• the component (B) is a partially hydrolyzed condensate of at least one silane compound (b) and has a Mw of 300 to 3000 (hereinafter, "primary reactant”). (Also referred to as)) is preferably hydrolyzed and condensed in the presence of a catalyst (hereinafter, also referred to as “secondary reactant”).
• a catalyst hereinafter, also referred to as “secondary reactant”.
• silanol group Si—OH
• Si-OR 5 Since the silanol group has higher reactivity than Si-OR 5 , the curability is improved. In addition, since the condensation reaction is promoted, the molecular weight becomes large and cracks are suppressed, so that the appearance can be improved.
• the Mw of the primary reaction product is 300 or more, the appearance of the cured product tends to be good, and when it is 3000 or less, the reactivity tends to be good.
• the Mw of the primary reaction product is preferably 400 to 2000, more preferably 500 to 1000.
• the silane compound (b) forming the primary reaction product the silane compound (b1) is preferable, tetraalkoxysilane is more preferable, and tetramethoxysilane is further preferable, from the viewpoint of the hardness of the cured layer.
• the primary reaction product is obtained by subjecting the silane compound (b) or a mixture of two or more thereof to a hydrolysis condensation reaction.
• primary reactants can also be used, for example, MS51, MS53, MS57, MS56S manufactured by Mitsubishi Chemical, ethyl silicate 40 manufactured by Corcote, ethyl silicate 48, methyl silicate 51, methyl silicate 53A, EMS-. 485 and the like can be mentioned.
• Examples of the method for hydrolyzing and condensing the primary reaction product in the presence of a catalyst include a method in which water, a catalyst and a solvent are added to the primary reaction product and the mixture is stirred at 25 ° C. for 1 day or longer. Further, the progress of the reaction can be promoted by heating the primary reaction product, and in that case, for example, a method of stirring at 30 ° C. to 100 ° C.
• the Mw of the secondary reaction product is preferably 400 to 50,000, more preferably 600 to 30,000, further preferably 800 to 10,000, and even more preferably 900 to 5,000, based on the empirical temperature and reaction time in the study by the present inventors. Is particularly preferable, and 1000 to 2000 is most preferable.
• the reaction of the secondary reaction product proceeds over time, it is difficult to specify its structure and characteristics (for example, size such as radius, hydroxyl value, etc.) in addition to Mw by a general analytical method. ..
• Mw can be measured, the reactivity of the curable composition and the appearance of the cured product differ between the case where the primary reaction product is used as the component (B) and the case where the secondary reaction product is used. That is, there are circumstances (impossible / impractical circumstances) in which it is impossible or approximately impractical to directly identify the secondary reactant by its structure or properties.
• the secondary reaction product is "a partially hydrolyzed condensate of at least one silane compound (b) having a Mw of 300 to 3000, which was hydrolyzed and condensed in the presence of a catalyst. It is more appropriate to specify.
• the coating workability when applying the curable composition, the smoothness and uniformity of the cured product formed, and the adhesion between the substrate and the cured product are improved. improves.
• the diluent include water, an organic solvent and the like, and an organic solvent is preferable.
• the organic solvent include alcohol-based solvents, glycol-based solvents, hydrocarbon-based solvents, ester-based solvents, ketone-based solvents, ether-based solvents and the like.
• Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, nbutanol, isobutanol, octanol, n-propyl alcohol, acetylacetone alcohol and the like.
• Glycol-based solvents include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol mono n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene.
• glycol monoethyl ether examples thereof include glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate.
• hydrocarbon solvent examples include benzene, kerosene, toluene, xylene and the like.
• ester solvent examples include methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate and the like.
• ketone solvent examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone and the like.
• ether solvent examples include ethyl ether, butyl ether, methyl cellosolve, ethyl cellosolve, dioxane, furan, tetrahydrofuran and the like.
• the organic solvent may be used alone or in combination of two or more.
• the diluent an alcohol solvent is preferable, and methanol, ethanol, isopropanol or n-propanol is more preferable because it is easy to handle, has good storage stability in a liquid, and has excellent characteristics of the obtained cured product. preferable.
• the diluent may contain water compounded for hydrolyzing and condensing the silane compound (b).
• the content of the copolymer (A) is preferably 1 to 95% by mass, more preferably 10 to 90% by mass, and 20 to 20 to 100% by mass with respect to 100% by mass of the non-volatile component in the curable composition. 85% by mass is more preferable, 25 to 85% by mass is particularly preferable, and 30 to 65% by mass is most preferable.
• the content of the copolymer (A) is at least the above lower limit value, the water-sliding property and appearance of the cured product are more excellent, and when it is at least the above upper limit value, the appearance and strength of the cured product are more excellent.
• the content of the component (B) is preferably 1 to 90% by mass, more preferably 5 to 80% by mass, still more preferably 10 to 75% by mass, and 18% by mass with respect to 100% by mass of the non-volatile component in the curable composition. ⁇ 70% by mass is particularly preferable, and 30 to 65% by mass is most preferable.
• the content of the component (B) is at least the above lower limit value, the durability and strength of the cured product are more excellent, and when it is at least the above upper limit value, the appearance of the cured product is more excellent.
• the content of the initiator (C) is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, based on 100% by mass of the non-volatile component in the curable composition.
• the lower limit is not particularly limited, but in the case of a cured product cured by irradiation with active energy rays, 0.01% by mass or more is preferable, 0.05% by mass or more is more preferable, and 0.2% by mass or more is further preferable. preferable.
• the concentration of the non-volatile component with respect to the entire curable composition is not particularly limited, but is preferably 80% by mass or less, more preferably 0.1 to 60% by mass, still more preferably 1 to 40% by mass, and particularly preferably 1 to 30%. It is in the range of% by mass, most preferably 1 to 20% by mass. By using it in the above range, a composition having excellent coatability can be obtained.
• the non-volatile component represents a component excluding the diluent.
• the content of other components is not particularly limited, but can be, for example, about 0 to 30% by mass with respect to 100% by mass of the non-volatile component in the curable composition.
• the curable composition can be prepared by mixing the copolymer (A), the component (B), and if necessary, the diluent, the initiator (C), and other components.
• the diluent contains water
• the water may be added during the preparation of the hydrolyzed condensate of the silane compound (b), may be added during the production of the curable composition, and the water of the silane compound (b) may be added. It may be blended both at the time of preparing the decomposition condensate and at the time of producing the present composition.
• ⁇ Curing product formation process> Known methods such as brush coating, gravure coater method, die coater method, bar coater method, spray coating method, flow coating method, dip coating method, spin coating method and curtain coating method are used as coating methods for the curable composition. Can be used.
• Examples of the curing method include a method of irradiating the curable composition with active energy rays, a method of curing by heating, a method of curing by utilizing the humidity in the air, and the like.
• a method of irradiating the curable composition with active energy rays may be preferable.
• the heating method When the curable composition is cured by heating, examples of the heating method include irradiation with a near-infrared lamp, circulation of warm air, and the like. As the heating conditions, heating at 60 ° C. to 200 ° C. for 10 minutes to 3 hours is preferable, and heating at 80 ° C. to 150 ° C. for 30 minutes to 2 hours is more preferable.
• the curable composition may be heated in an air atmosphere or in an atmosphere of an inert gas such as nitrogen or argon.
• the active energy rays include ultraviolet rays and electron beams.
• Ultraviolet rays are preferable from the viewpoint of ease of introduction of equipment and cost.
• a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a UV-LED, a low-pressure mercury lamp, a xenon excimer lamp, or the like can be used as a light source. From the viewpoint of productivity, it is preferable to use a light source that exhibits maximum irradiation intensity at a wavelength of 150 to 420 nm.
• the integrated irradiation amount of ultraviolet rays is preferably 50 to 3000 mJ / cm 2 , more preferably 100 to 2000 mJ / cm 2 .
• the active energy rays may be irradiated in an air atmosphere or in an atmosphere of an inert gas such as nitrogen or argon.
• the curable composition contains a diluent
• the curable composition is used to remove the diluent after coating the curable composition and before irradiating the curable composition with active energy rays for drying.
• the object may be heat-treated. This heat treatment can be performed by irradiation with a near-infrared lamp, circulation of warm air, or the like.
• the cured product obtained by irradiating the cured product with active energy rays after the heat treatment does not easily leave a diluent inside the cured product, so that the long-term adhesion outdoors is improved as compared with the product without the heat treatment. Tend to do.
• the surface temperature of the substrate (hereinafter referred to as heating temperature) is preferably 40 to 90 ° C, more preferably 50 to 70 ° C, and dried.
• the time is preferably 60 to 180 seconds, more preferably 90 to 150 seconds.
• the curable composition may be heat-treated after being irradiated with active energy rays.
• This heat treatment can be performed by irradiation with a near-infrared lamp, circulation of warm air, or the like.
• the cured product obtained by heat treatment after curing by irradiation with active energy rays tends to have excellent hardness and durability because the condensation reaction rate is higher than that without heat treatment.
• the contact angle of 1 ⁇ L distilled water at 23 ° C. (hereinafter, also referred to as “water contact angle”) on the surface of the initial cured layer is preferably 70 ° or higher, more preferably 80 ° or higher, and further preferably 90 ° or higher. It is preferable, 95 ° or more is particularly preferable, and 100 ° or more is most preferable. When the contact angle is at least the above lower limit value, the antifouling property is more excellent.
• the upper limit is not particularly limited, but is preferably 150 °.
• the contact angle of water can be adjusted by the content of the copolymer (A), the content of the silicone macromonomer (X) in the copolymer (A), and the like. Specifically, when the content of the copolymer (A) is increased or the content of the silicone macromonomer (X) in the copolymer (A) is increased, the contact angle tends to increase.
• the thickness of the cured product formed on the substrate is preferably 10 nm to 4 ⁇ m, more preferably 20 nm to 3 ⁇ m.
• the thickness of the cured product is at least the above lower limit value, the water-sliding property and scratch resistance of the cured product are more excellent, and when it is at least the above upper limit value, cracks are less likely to occur in the cured product.
• the cured product described above contains the copolymer (A) and the component (B), it is excellent in water-sliding property, appearance and durability.
• the cured product is used for sensing members such as members through which electromagnetic waves of sensing members (millimeter wave radar, LiDAR, etc.) pass; various automobile lamp lenses (vehicle lamps), resin glazing, road signs, traffic signals, camera lenses, etc. It can be used for 5G-related members, antennas, solar panels, window glass, resin glass, automobile glass and the like.
• sensing member application is preferable as the application of the cured product.
• the laminate according to one aspect of the present invention (hereinafter, also referred to as “the present laminate”) has a base material and a layer made of a cured product (hereinafter, also referred to as a “cured product layer”).
• the cured product layer is preferably located on the outermost surface layer of the present laminated body.
• a primer layer may be provided between the base material and the cured product layer.
• the laminate When a resin base material is used as the base material, the laminate preferably contains at least one selected from the group consisting of an ultraviolet absorber and a light stabilizer.
• the laminate contains an ultraviolet absorber and a light stabilizer, deterioration of the laminate itself and the member underlying the laminate due to ultraviolet rays and the like is suppressed, and weather resistance and durability are improved.
• the UV absorber and the light stabilizer will be described in detail later.
• the ultraviolet absorber and the light stabilizer may be contained in any layer of the laminate.
• the ultraviolet absorber and the light stabilizer are contained in the base material or the primer layer, and the laminated body. Considering the ease of designing the whole, it is more preferable to be contained in the primer layer.
• the base material or the primer layer contains a light stabilizer
• the primer layer contains a light stabilizer. Since the light stabilizer can capture radicals generated by light, it can improve resistance to light (particularly ultraviolet rays). In particular, it is preferable that an ultraviolet absorber is contained together with the light stabilizer.
• the content of the ultraviolet absorber or light stabilizer cannot be unequivocally determined because it depends on the layer used in the laminate and the film thickness of the layer.
• the content of each of the ultraviolet absorber and the light stabilizer is usually 10% by mass or less, preferably 0.01, based on the total mass of the base material. It is in the range of ⁇ 5% by mass, more preferably 0.1 to 3% by mass.
• the content of each of the UV absorber and the light stabilizer is preferably 30% by mass or less, more preferably 0.01 with respect to the total mass of the primer layer.
• It is in the range of about 20% by mass, more preferably 0.1 to 15% by mass, and particularly preferably 0.3 to 15% by mass. By using it in the above range, it is possible to improve the weather resistance of the base material and the member while maintaining other characteristics, and it is possible to prevent deterioration.
• base material glass base material; metal base material such as zinc-plated steel plate, zinc alloy-plated steel plate, stainless steel plate, tin-plated steel plate; polymethyl methacrylate resin, polycarbonate resin, polyester resin, polystyrene resin, ABS resin, AS resin Examples thereof include resin base materials such as polyamide resin, polyarylate resin, polyurethane resin, polyvinyl resin, triacetyl cellulose, polymethacrylicimide resin and polyallyl diglycol carbonate resin.
• the resin constituting the resin base material is glass, polycarbonate resin, polyester resin, triacetyl cellulose, polyurethane resin or polyvinyl resin from the viewpoint of transparency and mechanical strength.
• the resin substrate is added with an ultraviolet absorber, a light stabilizer, a plasticizer, an antistatic agent, a flame retardant, a reinforcing material, a filler, a colorant, a lubricant, a foaming agent, an easy lubricant, a curing catalyst, etc. It may contain an agent. If necessary, a primer layer may be present on the substrate for improving adhesion, etc., and an adhesive layer, an antifogging layer, etc. may be present on the side opposite to the side where the cured product layer of the substrate is present. It is also possible to have a functional layer such as an antireflection layer. Further, the heater may be mounted on the side opposite to the outermost surface of the laminated body or inside.
• the primer layer contributes to the adhesion between the base material and the cured layer and the improvement of the coatability when laminating the cured layer.
• the primer layer typically contains a resin component.
• the primer layer preferably contains at least one selected from the group consisting of an ultraviolet absorber and a light stabilizer. If necessary, the primer layer may contain additives other than the ultraviolet absorber and the light stabilizer as long as the effects of the present invention are not impaired.
• the resin component examples include acrylic resin, polyester resin, urethane resin, vinyl resin and the like. Among these, acrylic resin or urethane resin is particularly preferable from the viewpoint of improving adhesion. These resin components may be used alone or in combination of two or more. Further, the resin component may be a non-curable resin or a compound derived from a curable compound (monomer, oligomer, etc.). Examples of the compound derived from the curable compound include a cured product of the curable compound. The compound derived from the curable compound is preferable from the viewpoint of further improving the adhesion to the cured layer and improving the durability of the cured layer.
• a primer layer containing a compound derived from a curable compound is formed by containing a curable compound in the primer forming the primer layer, applying the primer on the substrate, and curing the curable compound on the substrate. ..
• the primer layer has excellent adhesion to the substrate and improves the adhesion between the substrate and the cured layer, as compared with the case where the resin component is only a non-curable resin.
• the durability of the cured layer is compared with the case where a non-curable compound is used. Tends to be excellent.
• the curable compound examples include an active energy ray-curable compound and a thermosetting compound, and an active energy ray-curable compound is preferable. If the primer is applied to the resin base material and then cured by heat, the resin base material may be deformed by heat, but if it is cured by active energy rays, the deformation of the resin base material by heat can be suppressed. It can also be applied to resin substrates with low heat resistance. Further, in general, curing by active energy rays is expected to improve productivity because the curing time is shorter than other curing methods such as heat curing and moisture curing.
• the active energy ray-curable compound a conventionally known active energy ray-curable compound can be used, and examples thereof include compounds having a radically polymerizable group such as a (meth) acryloyl group.
• the compound having a radically polymerizable group various conventionally known compounds can be used, and examples thereof include (meth) acrylate and other monomers copolymerizable with (meth) acrylate.
• the compounds having a radically polymerizable group include a monofunctional compound having one radically polymerizable group, a bifunctional compound having two radically polymerizable groups, and a trifunctional or more polyfunctional compound having three or more radically polymerizable groups. Examples include functional compounds. Among these, it is preferable to contain a polyfunctional compound in order to form a primer layer having an increased degree of curing in order to improve the adhesion to the cured layer.
• polyfunctional compound examples include polyfunctional (meth) acrylates.
• the polyfunctional (meth) acrylate is not particularly limited, but for example, pentaerythritol triacrylate, dipentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and trimethylolpropane.
• Polyester (meth) acrylates such as polyester oligomers having an acryloyl group (specifically, M8030, M7100, etc. manufactured by Toa Synthetic); isocyanurates of isophorone diisocyanate (IPDI), polytetramethylene glycol (PTMG) and hydroxyethyl.
• Polyfunctional urethane (meth) acrylates such as acrylate (HEA) reactants, pentaerythritol triacrylate reactants to hexamethylene diisocyanate (HDI) and PTMG reactants; oligoesters and pentaerythritol triacrylates using polycarbonate diols.
• Polyester (meth) acrylate having a carbonate bond such as a reactant
• Polyurethane (meth) acrylate such as a reactant of diisocyanate and a trifunctional or higher polyol and a reaction product of a hydroxyl group-containing (meth) acrylate
• Examples thereof include triethoxy (meth) acrylates having an isocyanurate ring; these alkylene oxide modified products; and these polycaprolactone modified products.
• pentaerythritol triacrylate pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, and trimethylolpropane tetraacrylate.
• Acrylate, dipentaerythritol triacrylate; these alkylene oxide modified products; these caprolactone modified products are preferably contained.
• the (meth) acrylate may be used alone or in combination of two or more.
• Examples of the monofunctional compound include monofunctional (meth) acrylate and (meth) acrylic acid.
• the monofunctional (meth) acrylate is not particularly limited, but is, for example, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth).
• Alkyl (meth) acrylates such as acrylates, cyclohexyl (meth) acrylates and isobornyl (meth) acrylates, hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylates, hydroxypropyl (meth) acrylates and hydroxybutyl (meth) acrylates.
• Amino group-containing (meth) acrylates such as aromatic (meth) acrylates, diaminoethyl (meth) acrylates, diethylaminoethyl (meth) acrylates, methoxyethylene glycol (meth) acrylates, phenoxypolyethylene grease (meth) acrylates, and phenylphenols.
• ethylene oxide-modified (meth) acrylate such as ethylene oxide-modified (meth) acrylate, glycidyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate.
• the bifunctional polyfunctional (meth) acrylate is not particularly limited, but for example, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di.
• Modified products; Examples thereof include these polycaprolactone modified products.
• thermosetting compound a conventionally known thermosetting compound can be used.
• various polyols and various polyisocyanates are used in combination.
• polystyrene resin examples include conventionally known ones, and examples thereof include polymers such as polycarbonate polyol, polyester polyol, acrylic polyol, polyurethane polyol, polyolefin polyol, polyether polyol, and polyvinyl alcohol, and terminals such as dendrimer and hyperbranched polymer.
• Polymers with a dendritic branched structure that are hydroxyl groups ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol , 1,5-Pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol , 1,10-decanediol, neopentaneglycol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptan, trimethylolethane, trimethylolpropane, glycerol, polycaprolactone triol, erythritol, pentaerythr
• a polymer type or a polyol having a branched structure is preferable because the cross-linking density is high and the curability and durability are excellent. Among them, a highly branched structure is formed and the cross-linking density is effectively high. Dendrimers and hyperbranched polymers are more preferred from the standpoint of being able to be made and improving durability. These polyols may be used alone or in combination of two or more.
• polyisocyanate examples include those conventionally known, and examples thereof include aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylenedi isocyanate, naphthalenedi isocyanate, and trizine diisocyanate, ⁇ , ⁇ , ⁇ ', and ⁇ .
• aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, methylene diphenyl diisocyanate, phenylenedi isocyanate, naphthalenedi isocyanate, and trizine diisocyanate, ⁇ , ⁇ , ⁇ ', and ⁇ .
• '-Aliphatic diisocyanate having an aromatic ring such as tetramethylxylylene diisocyanate, methylene diisocyanate, propylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, aliphatic diisocyanate such as hexamethylene diisocyanate, cyclohexanediisocyanate, methylcyclohexanediisocyanate, isophorone diisocyanate, Examples thereof include alicyclic diisocyanates such as dicyclohexammethane diisocyanate and isopropyridene dicyclohexyldiisocyanate.
• trifunctional or higher polyisocyanates such as a burette body, a trimethylolpropane adduct body, an isocyanurate body, and an allophanate body synthesized using these bifunctional polyisocyanates as starting materials can also be mentioned. These may be used alone or in combination of two or more.
• a trifunctional or higher functional polyisocyanate it is preferable to contain a trifunctional or higher functional polyisocyanate, and it is more preferable to contain an isocyanurate form, because the crosslink density is high and the curability and durability are excellent.
• an aromatic ring structure or an alicyclic structure are preferable, and from the viewpoint of being less likely to turn yellow, those having an aliphatic structure or an alicyclic structure are preferable.
• the content of the resin component is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, and may be 100% by mass with respect to the total mass of the primer layer. ..
• UV absorber examples include an organic ultraviolet absorber and an inorganic ultraviolet absorber. From the viewpoint of transparency, an organic ultraviolet absorber is preferable.
• the organic ultraviolet absorber is not particularly limited, and is, for example, a hydroxyphenyltriazine ultraviolet absorber, a benzotriazole ultraviolet absorber, a cyclic imino ester ultraviolet absorber, a benzophenone ultraviolet absorber, and a salicylate ester ultraviolet absorber. , Cyanoacrylate-based ultraviolet absorbers and the like.
• hydroxyphenyltriazine-based UV absorbers are more preferable, and hydroxyphenyltriazine-based UV absorbers are even more preferable, from the viewpoint of weather resistance and durability.
• These ultraviolet absorbers may be used alone or in combination of two or more. Furthermore, it is also possible to use those in which these compounds are incorporated into a polymer.
• the hydroxyphenyltriazine-based ultraviolet absorber is not limited to the following, but is, for example, 2- [4-([2-hydroxy-3-dodecyloxypropyl] oxy) -2-hydroxyphenyl] -4, 6-bis (2,4-dimethylphenyl) -1,3,5-triazine and 2- [4-([2-hydroxy-3-tridecyloxypropyl] oxy) -2-hydroxyphenyl] -4,6 -Bis (2,4-dimethylphenyl) -1,3,5-triazine (Tinuvin (registered trademark) (registered trademark) 400 manufactured by BASF), 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol), 2- (2,4-dihydroxyphenyl) -4,6-bis- ( Reaction product of 2,4-
• the benzotriazole-based ultraviolet absorber is not limited to the following, but is, for example, 2- [2'-hydroxy-5'-(methacryloxymethyl) phenyl] -2H-benzotriazole, 2- [2'. -Hydroxy-5'-(methacryloyloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(methacryloyloxypropyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy -5'-(methacryloyloxyhexyl) phenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5'-(methacryloxyethyl) phenyl] -2H-benzotriazole, 2- [2'-Hydroxy-5'-tert-butyl-3'-(methacryloyloxyethyl) phenyl
• the cyclic iminoester-based ultraviolet absorber is not limited to the following, but is, for example, 2-methyl-3,1-benzoxazine-4-one, 2-butyl-3,1-benzoxazine-4-one.
• benzophenone-based ultraviolet absorber (benzophenone-based compound) and oxybenzophenone-based ultraviolet absorber (oxybenzophenone-based compound) include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-.
• Methoxybenzophenone-5-sulfonic acid anhydrous and trihydrate
• 2-hydroxy-4-octyloxybenzophenone 4-dodecyloxy-2-hydroxybenzophenone
• 4-benzyloxy-2-hydroxybenzophenone 2,2'- Dihydroxy-4-methoxybenzophenone (trade name "KEMISORB111”, manufactured by Chemipro Kasei Co., Ltd.), 2,2', 4,4'-tetrahydroxybenzophenone (trade name "SEESORB106", manufactured by Cipro Kasei Co., Ltd.), 2,2 '-Dihydroxy-4,4-dimethoxybenzophenone and the like can be mentioned.
• salicylic acid ester-based ultraviolet absorber examples include phenyl-2-acryloyloxybenzoate, phenyl-2-acryloxy-3-methylbenzoate, and phenyl-2-acryloyloxy-4.
• cyanoacrylate-based ultraviolet absorber examples include alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, alkoxyalkyl-2-cyanoacrylate, alkenyl-2-cyanoacrylate, and alkynyl-2. -Cyanoacrylate and the like can be mentioned.
• the light stabilizer is not particularly limited, and examples thereof include an amine-based light stabilizer, a phenol-based light stabilizer, a phosphorus-based light stabilizer, and a thioether-based light stabilizer.
• an amine-based light stabilizer, Phenolic light stabilizers and phosphorus light stabilizers are preferable, and amine light stabilizers are more preferable in consideration of less yellowing and the like.
• These light stabilizers may be used alone or in combination of two or more. It is also possible to use a polymer incorporating these compounds.
• amine-based light stabilizer examples include a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol (Tinuvin (registered trademark) 622, manufactured by BASF), Kohaku. Polymers of dimethyl acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and N, N', N'', N''-tetrakis- (4,6-bis- (4,6-bis-) One-to-one with butyl- (N-methyl-2,2,6,6-tetramethylpiperidine-4-yl) amino) -triazine-2-yl) -4,7-diazadecan-1,10-diamine Reaction product (Tinuvin® 119, manufactured by BASF), dibutylamine 1,3-triazine N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6) -Hexamethylenediamine and N- (2,2,6,6-
• phenolic photostabilizer examples include 2,6-di-tertiary butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tertiary butylphenol, and 2,6-di-third.
• Grade Butyl-4-ethylphenol Butylated hydroxyanisole, n-octadecyl-3- (4-hydroxy-3,5-di-tertiary butylphenyl) propionate, distearyl- (4-hydroxy-3-methyl-) 5-Primary Butyl) benzylmalonate, tocopherol, 2,2'-methylenebis (4-methyl-6-tertiary butylphenol), 2,2'-methylenebis (4-ethyl-6-tertiary butylphenol) , 4,4'-methylenebis (2,6-di-tertiary butylphenol), 4,4'-butylidenebis (6-tertiary butyl-m-cresol), 4,4'-thiobis (6-third)
• Examples of the phosphorus-based photostabilizer include trisnonylphenyl phosphite, tris (2,4-di-tertiary butylphenyl) phosphite, and tris [2-tertiary butyl-4- (3-third).
• Phenylphosphite Tridecylphosphite, Octyldiphenylphosphite, Di (decyl) monophenylphosphite, Di (tridecyl) pentaerythritol diphosphite, Distealyl pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tertiary butylphenyl) pentaerythritol diphosphite, bis (2,6-di-third) Butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tri-tertiary butylphenyl) pentaerythritol diphosphite, tetra
• thioether-based light stabilizer examples include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl, and distearyl; ⁇ -alkyl mercaptopropionic acid of a polyol such as tetrakis [methylene (3-dodecylthio) propionate] methane. Examples include ester compounds.
• additives include, for example, leveling agents, silane coupling agents, defoaming agents, thickeners, antistatic agents, infrared absorbers, foaming agents, inorganic fine particles, organic fine particles, dyes, pigments, antioxidants, etc. Examples thereof include anti-yellowing agents, brewing agents, anti-foaming agents, anti-settling agents, and adhesion-imparting agents.
• the Martens hardness of the primer layer at 23 ° C. is preferably 50 to 300 N / mm 2 , more preferably 100 to 250 N / mm 2, and even more preferably 150 to 200 N / mm 2 .
• the Martens hardness is at least the above lower limit value, the adhesion with the upper layer is improved, and when it is at least the above upper limit value, the adhesion with the lower layer tends to be improved.
• the method for measuring the Martens hardness is as described in Examples described later.
• the Martens hardness of the primer layer can be adjusted by the type of resin component constituting the primer layer, the crosslink density, and the like.
• the contact angle of 1 ⁇ L of distilled water at 23 ° C. on the surface of the primer layer is preferably 100 ° or less, more preferably 95 ° or less, still more preferably 90 ° or less.
• the lower limit of the contact angle of water is not particularly limited, but is preferably 1 ° or more. The method for measuring the contact angle of water is as described in Examples described later.
• the contact angle of water can be adjusted by the amount of the leveling agent added, the content of the raw material having a hydrophilic group (hydroxyl group, amino group, sulfonyl group, carboxyl group, salts thereof, etc.) and the like. Specifically, if the amount of the leveling agent added is reduced, the leveling agent is changed to a leveling agent having a low surface tension lowering ability, or the content of the raw material having a hydrophilic group is increased, the contact angle of water tends to be reduced.
• the thickness of the primer layer is preferably 0.01 to 30 ⁇ m, more preferably 0.5 to 20 ⁇ m, still more preferably 1 to 20 ⁇ m.
• the thickness of the primer layer is at least the above lower limit value, the adhesion between the substrate and the cured layer is more excellent, and when it is at least the above upper limit value, the appearance tends to be better.
• a primer layer is formed on a substrate (primer layer forming step), and a copolymer (A) and at least one silane compound (b) or a portion thereof are formed on the primer layer. It can be produced by applying a curable composition containing a component (B) composed of a hydrolyzed condensate and curing the composition to form a cured layer (cured layer forming step).
• Primer layer forming process examples include a method in which a primer containing a resin component and a diluent is applied onto a substrate and the diluent is removed by drying.
• the primer preferably contains at least one selected from the group consisting of UV absorbers and light stabilizers. If necessary, the primer may contain additives other than the ultraviolet absorber and the light stabilizer as long as the effects of the present invention are not impaired.
• the resin component, ultraviolet absorber, light stabilizer, and other additives are as described above.
• Examples of the diluent include water, an organic solvent and the like.
• Examples of the organic solvent include alcohol-based solvents, glycol-based solvents, hydrocarbon-based solvents, ester-based solvents, ketone-based solvents, ether-based solvents and the like.
• Examples of the alcohol solvent include methanol, ethanol, isopropyl alcohol, nbutanol, isobutanol, octanol, n-propyl alcohol, acetylacetone alcohol and the like.
• Glycol-based solvents include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol mono n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene.
• examples thereof include glycol monoethyl ether, propylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate.
• hydrocarbon solvent examples include benzene, kerosene, toluene, xylene and the like.
• ester solvent examples include methyl acetate, ethyl acetate, butyl acetate, methyl acetoacetate, ethyl acetoacetate and the like.
• ketone solvent examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone and the like.
• ether solvent examples include ethyl ether, butyl ether, methyl cellosolve, ethyl cellosolve, dioxane, furan, tetrahydrofuran and the like.
• the organic solvent may be used alone or in combination of two or more.
• the content of the resin component is preferably 30% by mass or more, more preferably 50% by mass or more, further preferably 70% by mass or more, even if it is 100% by mass, based on 100% by mass of the non-volatile component of the primer. good.
• the content of the ultraviolet absorber varies depending on the type of the ultraviolet absorber, but is preferably 30% by mass or less, more preferably 0.01 to 20% by mass, and further preferably 0 with respect to 100% by mass of the non-volatile component of the primer. It is in the range of 1 to 15% by mass, particularly preferably 0.3 to 15% by mass.
• the content of the light stabilizer varies depending on the type of the light stabilizer, but is preferably 30% by mass or less, more preferably 0.01 to 20% by mass, and further preferably 0 with respect to 100% by mass of the non-volatile component of the primer. It is in the range of 1 to 15% by mass, particularly preferably 0.3 to 15% by mass.
• the concentration of the non-volatile component with respect to the entire primer is not particularly limited, but is preferably in the range of 80% by mass or less, more preferably 0.1 to 70% by mass, still more preferably 10 to 70%, and particularly preferably 20 to 60%. be. By using it in the above range, a curable composition having excellent coatability can be obtained.
• Primers can be prepared by mixing resin components, diluents, UV absorbers, light stabilizers, and other additives as needed.
• the coating method known methods such as brush coating, gravure coater method, die coater method, bar coater method, spray coating method, flow coating method, dip coating method, spin coating method and curtain coating method can be used. ..
• the curing method include the same methods as described above, and a method of irradiating the curable composition with active energy rays is preferable.
• the curable composition contains a diluent
• for drying to remove the diluent after coating the substrate with the curable composition and before irradiating the curable composition with active energy rays. It may be heat-treated.
• the heat treatment for drying can be performed by irradiation with a near-infrared lamp, circulation of warm air, or the like.
• the cured product layer obtained by irradiating the cured product layer with active energy rays after the heat treatment has a long-term outdoor adhesion as compared with the one without the heat treatment because the diluent is less likely to remain inside the cured product layer.
• the drying conditions are preferably 40 to 90 ° C., more preferably 50 to 70 ° C., and preferably 60 to 180 seconds, preferably 90 to 150 seconds as the drying time from the viewpoint of the appearance and adhesion of the cured product layer. Is more preferable.
• the curable composition may be heat-treated after being irradiated with active energy rays.
• This heat treatment can be performed by irradiation with a near-infrared lamp, circulation of warm air, or the like.
• the cured product layer obtained by heat treatment after curing by irradiation with active energy rays tends to have excellent hardness and durability because the condensation reaction rate is higher than that without heat treatment.
• the sliding angle of water at 23 ° C. and 20 ⁇ L on the surface of the cured product layer (initial cured product layer) formed as described above is preferably as low as possible, preferably 60 ° or less, more preferably 50 ° or less. 40 ° or less is more preferable, 30 ° or less is particularly preferable, and 20 ° or less is most preferable.
• the lower limit of the sliding angle of water There is no particular limitation on the lower limit of the sliding angle of water, and it is 0 ° or more. If the sliding angle of water is not more than the above upper limit, raindrops and snow adhering to the surface can easily slide down.
• the sliding angle of water after the durability test is particularly important in a wide range of application development, and a lower one is preferable, and a smaller change from the initial stage is preferable.
• the surface of the cured product layer (cured product layer after the durability test) after the cured product layer is formed as described above and a durability test is performed at 50 ° C. and 99% RH or higher for 96 hours.
• the sliding angle of 20 ⁇ L of water at 23 ° C. is preferably 60 ° or less, more preferably 50 ° or less, further preferably 40 ° or less, particularly preferably 30 ° or less, and most preferably 20 ° or less.
• There is no particular limitation on the lower limit of the sliding angle of water for example, 1 ° or more.
• the amount of change in the water slide angle of the cured product layer after the durability test from the water slide angle of the initial cured product layer is preferably 40 ° or less, more preferably 30 ° or less, further preferably 20 ° or less, and most preferably 15 ° or less. There is no particular lower limit, but it is preferably 0 °. Within this range, the same level of performance as in the initial stage can be exhibited over a long period of time, and product design becomes easier.
• the cured product layer is composed of a cured product of the resin composition containing the copolymer (A) and the component (B), it is excellent in appearance, water permeability and durability.
• This laminated body is used for sensing members such as members through which electromagnetic waves of sensing members (millimeter wave radar, LiDAR, etc.) pass; various automobile lamp lenses (vehicle lamps), resin glazing, road signs, traffic signals, camera lenses, etc. It can be used for 5G-related members, antennas, solar panels, window glass, resin glass, automobile glass and the like. Among the above, the sensing member is most suitable for the use of the laminated body.
• ⁇ Appearance> The appearance of the evaluation sample was visually evaluated.
• the judgment criteria are as follows. (criterion) A: A transparent and smooth coating film is formed without any abnormalities such as whitening, cracks and blisters. B: There are slight abnormalities such as whitening, cracks, and blisters. C: Abnormalities such as whitening, cracks, and blisters are observed.
• ⁇ Water smoothness> With respect to the cured film surface of the evaluation sample, the sliding angle of water at 23 ° C. and 20 ⁇ L was measured by tilting the substrate by the intermittent tilting method, and the slipperiness was evaluated. Specifically, a contact angle meter (DM-500, manufactured by Kyowa Interface Science) was used on the cured film surface of the evaluation sample horizontally placed on the sample fixing table in an environment of 23 ° C. and 50% RH. After dropping a droplet of 20 ⁇ L of distilled water, the evaluation sample was intermittently tilted by 1 °, and the tilt angle when the droplet started to slide was taken as the slide angle.
• the criteria for determining water smoothness are as follows.
• the primer layer to be used for measuring the Martens hardness was prepared under the following conditions. (Method of making test pieces) Base material: Polycarbonate plate (PC, 3 mm thick), Coating: Spray coating, Dry film thickness: 13 ⁇ m, Curing conditions: High-pressure mercury lamp 2000 mJ / cm 2 when the primer is active energy ray curable, 120 ° C x 30 minutes when the primer is thermosetting. The Martens hardness value changes depending on the type and film thickness of the base material.
• ⁇ Contact angle> The contact angle of water was measured by the sessile drop method. Specifically, in an environment of 23 ° C. and 50% RH, a contact angle meter (DM-500, Kyowa) was placed on the surface of the cured layer (or the surface of the primer layer before forming the cured layer) of the evaluation sample placed horizontally. 1 ⁇ L of distilled water was added dropwise using (manufactured by Kyowa Interface Science), and the contact angle (static contact angle) was measured 5 seconds after the addition.
• DM-500 DM-500, Kyowa
• the adhesiveness of the cured layer was evaluated by peeling the cellophane tape. Specifically, in an environment of 23 ° C. and 50% RH, cellophane tape was crimped to the surface of the cured layer of the evaluation sample with a finger, quickly peeled off in the direction of 45 ° diagonally toward you, and the area of the cured layer that was visually peeled off (the area of the cured layer was visually removed. The peeling area) was confirmed, and the adhesiveness was evaluated.
• the evaluation criteria for adhesion are as follows. A: No peeling. B: Peeling is observed, but the peeling area is less than 50% of the crimping area of the cellophane tape. C: The peeled area is 50% or more of the crimping area of the cellophane tape.
• ⁇ Durability> For the cured film of the evaluation sample, a wetness tester (device name: wetness tester, model CT-3H, manufactured by Suga Test Instruments Co., Ltd.) was used, and the temperature inside the tank was 50 ° C. and the humidity inside the tank was 99% RH or more. A 96-hour durability test was carried out under the conditions. After the durability test, the above-mentioned appearance and water-sliding property were evaluated.
• ⁇ Weather resistance> For the weather resistance test, a weather resistance tester (device name: Super Xenon Weather Meter, model SX75, manufactured by Suga Test Instruments Co., Ltd.) was used for 12 minutes of rainfall in 60 minutes and an irradiation intensity of 180 W / m 2 (300). A weather resistance test was carried out for 500 hours under the conditions of ( ⁇ 400 nm), a black panel temperature of 63 ° C., a tank temperature of 50 ° C., and a tank humidity of 50%. The evaluation sample was arranged so that the laminated cured film surface and the light source side of the weathering resistance tester were perpendicular to each other.
• KBM-5103 "KBM-5103" manufactured by Shin-Etsu Chemical Co., Ltd. (3-acryloxypropyltrimethoxysilane, 100% non-volatile component).
• FM-0721 "Silaplane FM-0721” manufactured by JNC Corporation (polydimethylsiloxane having a methacryloyl group at one end, Mw4200, 100% non-volatile component).
• FM-0711 "Silaplane FM-0711” manufactured by JNC Corporation (polydimethylsiloxane having a methacryloyl group at one end, Mw900, 100% non-volatile component).
• the structures of FM-0721 and FM-0711 are as follows.
• CH 2 C (CH 3 ) -COO-C 3 H 6- (Si (CH 3 ) 2 O) n- (CH 2 ) 3 CH 3
• Copolymer (E-2): The copolymer (FM-0721: KBM-5) obtained in Synthesis Example 6 described later. 103 20:30 (mass ratio), Mw53300).
• Component (B-1) Alkoxysilane hydrolyzed condensate (Mw1000) obtained in Synthesis Example 7 described later.
• Component (B-2) Alkoxysilane hydrolyzed condensate (Mw1600) obtained in Synthesis Example 8 described later.
• MS51 "MS51” manufactured by Mitsubishi Chemical Corporation (tetramethoxysilane partial hydrolysis condensate, Mw 800 to 1100, 100% non-volatile component).
• Photoacid generator "CPI-200K” manufactured by San-Apro (p-phenylthiophenyldiphenylsulfonium hexafluorophosphate, 50% non-volatile component).
• IPA 2-propanol.
• PGM Propylene glucol monomethyl ether.
• Perocta O “Perocta O” manufactured by NOF CORPORATION (2-ethylhexaneperoxyate 1,1,3,3-tetramethylbutyl).
• copolymers (A-1) to (A-4) correspond to the copolymer (A), and the copolymers (E-1) and (E-2) are copolymers. This is a comparative product that does not fall under (A).
• the product obtained was a polymer having a non-volatile component of 30% and a weight average molecular weight (Mw) of 16200.
• the product obtained was a polymer having a non-volatile component of 30% and a weight average molecular weight (Mw) of 19,800.
• the flask was set in an oil bath, stirring was started under a nitrogen atmosphere, and the temperature was raised until the internal temperature reached 85 ° C. Thirty minutes after the internal temperature reached 85 ° C., the monomer mixture was added dropwise from the dropping funnel over 2 hours and held for 1 hour, then 0.21 g of Perocta O was added, and 1 hour later, further Per Octa O was added. 0.21 g was added, the reaction was carried out for 5 hours, and then the mixture was cooled.
• the product obtained was a polymer having a non-volatile component of 30% and a weight average molecular weight (Mw) of 15500.
• the monomer mixture was added dropwise from the dropping funnel over 2 hours and held for 1 hour, then 0.20 g of Perocta O was added, and 1 hour later, the Per Octa O was further added. 0.20 g was added, the reaction was carried out for 5 hours, and then the mixture was cooled.
• the product obtained was a polymer having a non-volatile content of 30% and a weight average molecular weight (Mw) of 23400.
• Example 1 ⁇ Preparation of resin composition> 3.5 parts of the copolymer (A-1), 4.2 parts of the component (B-1), 10 parts of the IPA, 10 parts of the PGM, and the photoacid generator CPI-200K (Sun Appro). A resin composition was prepared by mixing with 0.04 part of (manufactured by).
• the obtained resin composition was applied to the surface of a polycarbonate resin plate (PC plate) having a thickness of 3 mm (manufactured by Mitsubishi Engineering Plastics Co., Ltd., trade name: "IUPILON ML-300"), and the thickness after drying was 0.7 ⁇ m.
• the coating film was dried (solvent volatilized) by heating for 120 seconds in a hot air dryer preheated to 60 ° C.
• the dried coating film was subjected to 1000 mJ / cm 2 (integrated irradiation amount at a wavelength of 340 to 380 nm) using a high-pressure mercury lamp (USX5-0902, manufactured by Igraphic) in an air atmosphere.
• the coating film was cured by irradiating with ultraviolet rays (measured using (manufactured by ORC Manufacturing Co., Ltd.)) to obtain an evaluation sample in which a cured film of a resin composition was laminated on a PC plate.
• Examples 2 to 7, Comparative Examples 1 to 5, Reference Example 1 The composition was prepared in the same manner as in Example 1 except that the types and amounts (parts) of the components to be blended in the composition were as shown in Tables 1 and 2, and evaluation samples were prepared. The evaluation results of the composition and the evaluation sample are shown in Tables 1 and 2. However, in Comparative Example 5, the compatibility of the composition in the liquid state was low and it could not be molded as a cured film, so that the evaluation sample was not prepared and evaluated.
• Example 8 to 10 The composition was prepared in the same manner as in Example 1 except that the types and amounts (parts) of the components to be blended in the composition were as shown in Table 1. Using this composition, an evaluation sample was prepared in the same manner as in Example 1 except that the base material was changed from a PC plate to a glass plate having a thickness of 5 mm. The evaluation results of the composition and the evaluation sample are shown in Table 1.
• ⁇ Preparation of primer> In a resin obtained by mixing 22 parts of a caprolactone modified product of dipentaerythritol hexaacrylate (DPHA) (“DPCA-20” manufactured by Nippon Kayaku Co., Ltd.) and 16 parts of urethane acrylate, 0.9 part of benzophenone as a photopolymerization initiator was added. After adding 3 parts of tinubin 400 (manufactured by BASF) as an ultraviolet absorber and 0.15 parts of tinubin 123 (manufactured by BASF) as a light stabilizer, propylene glycol monomethyl ether is used to make the non-volatile component 32% by mass.
• DPHA dipentaerythritol hexaacrylate
• an active energy ray-curable primer (1) Diluted to prepare an active energy ray-curable primer (1).
• the urethane acrylate was prepared as follows. In a flask equipped with a dropping funnel with a heat retaining function, a reflux condenser, a stirring blade and a temperature sensor, 530 g (2 mol) of dicyclohexylmethane diisocyanate and 300 ppm of din-butyl tin dilaurate were charged and heated to 40 ° C. Then, 800 g (weight average molecular weight 800) of polycarbonate diol (trade name: Kuraray polyol C-770, manufactured by Kuraray Co., Ltd.) as a polyol compound was added dropwise over 4 hours. After stirring at 40 ° C.
• polycarbonate diol trade name: Kuraray polyol C-770, manufactured by Kuraray Co., Ltd.
• the product obtained was a polymer having a non-volatile component of 75% and a molecular weight of 1500.
• the above primer (1) was spray-coated on a 3 mm-thick polycarbonate resin plate (PC plate) (manufactured by Mitsubishi Engineering Plastics, trade name: "IUPILON ML-300") and then preheated to 70 ° C.
• the coating film was dried (solvent volatilized) by heating in a hot air dryer for 90 seconds.
• the dried coating film was measured in an air atmosphere using a high-pressure mercury lamp at 2000 mJ / cm 2 (integrated irradiation dose at a wavelength of 340 to 380 nm was measured using an ultraviolet photometer UV-351 (manufactured by ORC Manufacturing Co., Ltd.).
• the curable composition is spray-coated on the primer layer so that the thickness after drying is 700 nm, and then heated in a hot air dryer preheated to 60 ° C. for 120 seconds to form a coating film. It was dried (the solvent was volatilized).
• the dried coating film was subjected to 1000 mJ / cm 2 (integrated irradiation amount at a wavelength of 340 to 380 nm) using a high-pressure mercury lamp (USX5-0902, manufactured by Igraphic) in an air atmosphere, with an ultraviolet photometer UV-351.
• the coating film was cured by irradiating with ultraviolet rays (measured using (manufactured by ORC Manufacturing Co., Ltd.)). As a result, a laminated body in which a primer layer and a cured layer were sequentially laminated on a PC plate was obtained.
• Examples 12, 13, 16 and Comparative Examples 6 to 9 The composition was prepared in the same manner as in Example 11 except that the types and amounts (parts) of the components to be blended in the composition were as shown in Tables 3 and 4, and evaluation samples were prepared. The evaluation results of the composition and the evaluation sample are shown in Tables 3 and 4.
• Example 14 100 parts of Basonol (registered trademark) HPE1170B (manufactured by BASF) as a polyol, 30 parts of Kuraray polyol C-1090 (manufactured by Kuraray), 159 parts of Duranate MHG-80B as an isocyanate (manufactured by Asahi Kasei Co., Ltd.), MEK as inorganic fine particles.
• Basonol registered trademark
• HPE1170B manufactured by BASF
• Kuraray polyol C-1090 manufactured by Kuraray
• Duranate MHG-80B as an isocyanate
• MEK as inorganic fine particles.
• thermosetting primer (2) (manufactured by Nissan Chemical Co., Ltd.) 70 parts, Chinubin 405 (manufactured by BASF) as an ultraviolet absorber 30 parts, Chinubin 152 (manufactured by BASF) as a light stabilizer 0.5 parts, as a curing acceleration catalyst 0.05 parts of dibutyltin dilaurate (DBTDL) was uniformly mixed, and further diluted with cyclohexanone and MIBK so that the concentration of the non-volatile component was about 32% to prepare a thermosetting primer (2). ..
• DBTDL dibutyltin dilaurate
• the primer (2) When forming the primer layer, the primer (2) was spray-coated so that the thickness of the coating film after curing was 10 ⁇ m, and the cured film (primer layer) was formed by heat-treating at 120 ° C. for 30 minutes. Prepared an evaluation sample in the same manner as in Example 11. The evaluation results are shown in Table 3.
• Example 15 16 parts of BR-83 (manufactured by Mitsubishi Chemical Co., Ltd.) as a non-curable acrylic resin, 2.2 parts of tinubin PS (manufactured by BASF) as an ultraviolet absorber, and 1 part of tinubin 123 (manufactured by BASF) as a light stabilizer. .8 parts were diluted with PGM and methyl ethyl ketone (MEK) so that the concentration of the non-volatile component was 16%, and mixed uniformly to prepare the primer (3). When forming the primer layer, the primer (3) is spray-coated so that the thickness of the coating film after drying becomes 10 ⁇ m, and heat-treated at 90 ° C. for 30 minutes to form a non-curable coating film (primer layer). An evaluation sample was prepared in the same manner as in Example 11 except that the above was formed. The evaluation results are shown in Table 3.
• Example 17 When a 100 ⁇ m-thick polycarbonate film (PC film, FE-2000 manufactured by Mitsubishi Engineering Plastics) was used instead of the PC plate to form the primer layer and the cured layer, the primer (1) and the above-mentioned primer (1) were applied on the above-mentioned PC film.
• An evaluation sample was prepared in the same manner as in Example 11 except that the resin composition described in Example 12 was coated with a bar coater so that the thickness after drying was 10 ⁇ m and 700 nm, respectively. The evaluation results are shown in Table 3.
• Example 18 When a polyethylene terephthalate film (PET film, Mitsubishi Chemical Diafoil T600E50 W07) having a thickness of 50 ⁇ m was used instead of the PC plate to form the primer layer and the cured layer, the primer (1) and the above-mentioned primer (1) were applied on the PET film.
• An evaluation sample was prepared in the same manner as in Example 11 except that the resin composition described in Example 12 was coated with a bar coater so that the thickness after drying was 10 ⁇ m and 700 nm, respectively. The evaluation results are shown in Table 3.
• a curable composition was prepared by mixing 3.5 parts of the copolymer (A-1), 4.2 parts of the component (B-1), 10 parts of IPA, and 10 parts of PGM. ..
• a curable composition is spray-coated on a glass plate having a thickness of 5 mm so that the thickness after curing is 0.7 ⁇ m, and the glass plate is cured by heating in a hot air dryer at 150 ° C. for 1 hour. An evaluation sample in which a cured film was laminated was obtained.
• Example 20 and 21 Comparative Examples 10 to 13
• a curable composition was prepared and an evaluation sample was prepared in the same manner as in Example 19 except that the types and amounts (parts) of the components to be blended in the curable composition were as shown in Table 5.
• the evaluation results of the evaluation sample are shown in Table 5.
• Comparative Example 13 a cured film could not be formed, so evaluation was not performed.
• Example 22 A curable composition was prepared in the same manner as in Example 1 except that the types and amounts (parts) of the components to be blended in the curable composition were as shown in Table 5.
• the obtained curable composition was spray-coated on a glass plate having a thickness of 5 mm so as to have a thickness of 0.7 ⁇ m after curing, and then 120 in a hot air dryer preheated to 60 ° C.
• the coating film was dried (solvent volatilized) by heating for seconds.
• the dried coating film was subjected to 1000 mJ / cm 2 (integrated irradiation amount at a wavelength of 340 to 380 nm) using a high-pressure mercury lamp (USX5-0902, manufactured by Igraphic) in an air atmosphere, with an ultraviolet photometer UV-351.
• the coating film was cured by irradiating with ultraviolet rays (measured using (manufactured by ORC Manufacturing Co., Ltd.)) to obtain a laminated body in which a cured film was laminated on a glass plate.
• the evaluation results of the evaluation sample are shown in Table 5.
• each component is the amount including volatile matter.
• An “x” in the evaluation of "water-sliding” means that the droplets did not move on the surface of the cured film even when the inclination angle was changed to 90 °, and the sliding angle could not be measured.
• “-” Means that the surface of the cured film was hydrophilic, so that droplets were not formed and the sliding angle could not be measured.
• N / A means that the measurement could not be performed due to the influence of the surface condition of the coating film and the like.
• the cured products of the compositions of Examples 1 to 10 were excellent in appearance and water smoothness both in the initial stage and after the durability test.
• the composition of Comparative Example 1 did not contain a copolymer that imparts water-sliding property, and the surface of the cured film was hydrophilic, so that it was impossible to determine the water-sliding property as shown in Table 2.
• the composition of Comparative Example 2 did not contain the component (B), the appearance of the cured film was low as shown in Table 2. In addition, the hardness of the cured film was low.
• Comparative Example 3 used a copolymer containing no polydimethylsiloxane unit, which is a component that imparts water smoothness, the water smoothness was low as shown in Table 2.
• Comparative Example 4 used a copolymer having a low content of polydimethylsiloxane unit, which is a component that imparts water smoothness, the water smoothness was low as shown in Table 2.
• Comparative Example 5 was added as a monomer without copolymerizing the constituent components of the copolymer (A-1), the compatibility in the liquid state was low, and as shown in Table 2, it was cured. It could not be molded as a film.
• the laminates of Examples 11 to 18 were excellent in adhesion between the base material and the cured layer, appearance of the cured layer, water slipperiness, hardness and hardness. Further, in Examples 11 to 14 and 16 to 18, the appearance and water permeability of the cured layer after the durability test were also good, and the durability was excellent. On the other hand, since the laminated body of Comparative Example 6 did not have the component (B), the appearance was low as shown in Table 4. In addition, the curability was also poor, the strength of the coating film was poor, and the film did not function as a cured film. Since the laminate of Comparative Example 7 did not have the copolymer (A), it was inferior in water-sliding property as shown in Table 4.
• the cured films of Examples 19 to 22 were excellent in appearance and water smoothness at the initial stage and after the weather resistance test.
• the cured film of Comparative Example 10 did not contain a copolymer that imparts water-sliding property, and the surface of the cured film was hydrophilic, so that it was impossible to determine the water-sliding property as shown in Table 5.
• the cured film of Comparative Example 11 did not contain the component (B), the appearance was low as shown in Table 5.
• the curability was also poor, the strength of the coating film was poor, and the film did not function as a cured film.
• Comparative Example 12 As the cured film of Comparative Example 12 used a copolymer containing no polyalkylsiloxane unit which is a component for imparting water smoothness, the water smoothness was low as shown in Table 5. In Comparative Example 13, since the constituent components of the copolymer (A-1) were added to the curable composition as a monomer without copolymerization, the compatibility in the liquid state was low as shown in Table 5. , Can not be molded as a cured film.

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