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
• • 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
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
  • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
  • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
  • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/81—Unsaturated isocyanates or isothiocyanates
  • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
  • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
  • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
  • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
  • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
  • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
• • 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
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
• • 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
  • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D171/02—Polyalkylene oxides
• • 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
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
• • 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
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • 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
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/106—Esters of polycondensation macromers
  • C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
• • 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
  • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica

Definitions

• the present invention provides an active energy ray-curable composition capable of imparting high pencil hardness to the surface of various articles, and further imparting excellent scratch resistance, antifouling property, and slipperiness, a cured product thereof, and a cured coating film thereof. It relates to an article having.
• the active energy ray-curable composition has a low heat history to the substrate to be applied, and is excellent in coating film hardness and scratch resistance. For example, it is soft and has a defect that the surface is easily damaged. It is used as a hard coat agent that imparts scratch resistance to the surface.
• a fluorine compound having a perfluoropolyether group and a polymerizable group is proposed as a material to be added to the active energy ray curable composition. (For example, refer to Patent Document 1).
• the cured coating film of the active energy ray-curable composition to which the fluorine compound described in Patent Document 1 is added has a problem that it is inferior in scratch resistance, pencil hardness and slipperiness although it has excellent antifouling properties. Accordingly, there has been a demand for an active energy ray-curable composition that can provide a cured coating film that has excellent antifouling properties and is excellent in scratch resistance, pencil hardness, and slipperiness.
• the problem to be solved by the present invention is an active energy ray-curable composition that has a high pencil hardness, and further provides a cured coating film having excellent scratch resistance, antifouling properties, and slipperiness, a cured product thereof, and It is to provide an article having the cured coating.
• the present inventors have made active energy ray curing in which a fluorine compound having a specific structure, reactive silica and non-reactive silica are added to the active energy ray curable compound.
• the surface of the cured coating film of the adhesive composition has high pencil hardness, and further has excellent scratch resistance, antifouling property, and slipperiness, and the present invention has been completed.
• a cyclopolysiloxane structure is bonded to both ends of the active energy ray-curable compound (A) and the poly (perfluoroalkylene ether) chain via a divalent linking group, and the cyclopolysiloxane structure is bonded to the cyclopolysiloxane structure.
• Active energy comprising a fluorine compound (B) having a structure in which a (meth) acryloyl group is bonded via a divalent linking group, reactive silica (C1), and non-reactive silica (C2)
• the present invention relates to a linear curable composition, a cured product thereof, and an article having the cured coating film. Furthermore, this invention relates to the protective film which provided the hard-coat film which used the hardened
• the active energy ray-curable composition of the present invention has a surface of various articles because the surface of the cured coating film has high pencil hardness and excellent scratch resistance, antifouling property, and slipperiness. It is extremely useful as a hard coat agent for protection.
• a cyclopolysiloxane structure is bonded to both ends of the active energy ray-curable compound (A) and the poly (perfluoroalkylene ether) chain via a divalent linking group
• a fluorine compound (B) having a structure in which a (meth) acryloyl group is bonded to the cyclopolysiloxane structure through a divalent linking group
• (meth) acrylate refers to one or both of acrylate and methacrylate
• (meth) acryloyl group refers to one or both of acryloyl group and methacryloyl group.
• Examples of the active energy ray-curable compound (A) include urethane (meth) acrylate and polyfunctional acrylate.
• (A1) is composed of four or more (meta) in one molecule obtained by reacting an aliphatic polyisocyanate (a1) with a (meth) acrylate (a2) having a hydroxyl group. ) It has an acryloyl group.
• the aliphatic polyisocyanate (a1) is a compound in which a portion excluding an isocyanate group is composed of an aliphatic hydrocarbon.
• Specific examples of the aliphatic polyisocyanate (a1) include aliphatic polyisocyanates (a1-1) such as hexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate; norbornane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), Alicyclic polyisocyanates (a1-2) such as 1,3-bis (isocyanatomethyl) cyclohexane, 2-methyl-1,3-diisocyanatocyclohexane, 2-methyl-1,5-diisocyanatocyclohexane, etc.
• a trimerization product obtained by trimming the aliphatic polyisocyanate (a1-1) or the alicyclic polyisocyanate (a1-2) can also be used as the aliphatic polyisocyanate (a1).
• aliphatic polyisocyanates (a1) hexamethylene diisocyanate, which is a diisocyanate of linear aliphatic hydrocarbons, norbornane diisocyanate, which is an alicyclic diisocyanate, and isophorone diisocyanate are those of the active energy ray-curable composition of the present invention. It is preferable because the pencil hardness and scratch resistance on the surface of the cured coating film can be further improved.
• the (meth) acrylate (a2) is a compound having a hydroxyl group and a (meth) acryloyl group, but the urethane (meth) acrylate (A1) has four or more (meth) acryloyl groups in one molecule. Therefore, it is preferable to have two or more (meth) acryloyl groups.
• (meth) acrylate (a2) for example, trimethylolpropane di (meth) acrylate, ethylene oxide modified trimethylolpropane di (meth) acrylate, propylene oxide modified trimethylolpropane di (meth) acrylate, glycerin di (Meth) acrylate, bis (2- (meth) acryloyloxyethyl) hydroxyethyl isocyanurate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc. .
• (meth) acrylates (a2) can be used alone or in combination of two or more with respect to one of the aliphatic polyisocyanates (a1).
• pentaerythritol tri (meth) acrylate and dipentaerythritol penta (meth) acrylate are pencil hardnesses on the surface of the cured coating film of the active energy ray-curable composition of the present invention. And scratch resistance can be further improved.
• the reaction between the aliphatic polyisocyanate (a1) and the (meth) acrylate (a2) can be carried out by a conventional urethanization reaction. Moreover, in order to accelerate
• urethanization catalyst examples include amine compounds such as pyridine, pyrrole, triethylamine, diethylamine and dibutylamine; phosphorus compounds such as triphenylphosphine and triethylphosphine; dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin Examples thereof include organic tin compounds such as diacetate and tin octylate, and organic zinc compounds such as zinc octylate.
• the urethane (meth) acrylate (A1) obtained by the above urethanization reaction can be used alone or in combination of two or more. Moreover, when using 2 or more types, the urethane acrylate obtained using hexamethylene diisocyanate as said aliphatic polyisocyanate (a1) and the trimer of hexamethylene diisocyanate as said aliphatic polyisocyanate (a1) are used.
• the combined use with the obtained urethane acrylate is preferable because the pencil hardness and scratch resistance of the cured coating film surface of the active energy ray-curable composition of the present invention can be further improved.
• the polyfunctional (meth) acrylate (A2) is a compound having three or more (meth) acryloyl groups in one molecule.
• Specific examples of the polyfunctional (meth) acrylate (A2) include trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, ditrile.
• polyfunctional (meth) acrylates (A2) can be used alone or in combination of two or more.
• the (meth) acryloyl group The equivalent weight is 50 to 200 g / eq. In the range of 70 to 150 g / eq. In the range of 80 to 120 g / eq. The thing of the range is more preferable.
• the (meth) acryloyl group equivalent is 80 to 200 g / eq.
• polyfunctional (meth) acrylate (A2) in the range of 5 are pentaerythritol tetraacrylate (acryloyl group equivalent: 88 g / eq.), Dipentaerythritol hexaacrylate (acryloyl group equivalent: 118 g / eq.), And the like. Is mentioned.
• the mass ratio [(A1) / (A2)] of the urethane (meth) acrylate (A1) and the polyfunctional (meth) acrylate (A2) can improve the scratch resistance, 90/10 to 10/90
• the range of 80/20 to 20/80 is more preferable, and the range of 75/25 to 25/75 is more preferable.
• the active energy ray-curable composition of the present invention includes one molecule within a range not impairing the effects of the present invention, in addition to the urethane (meth) acrylate (A1) and the polyfunctional (meth) acrylate (A2).
• Other (meth) acrylates such as mono (meth) acrylate having one (meth) acryloyl group in it and di (meth) acrylate having two (meth) acryloyl groups in one molecule may be blended.
• the blending amounts thereof are the urethane (meth) acrylate (A1) and the polyfunctional (meth) acrylate (A2). 40 parts by mass or less is preferable with respect to a total of 100 parts by mass, and 20 parts by mass or less is more preferable.
• the fluorine compound (B) has a cyclopolysiloxane structure bonded to both ends of the poly (perfluoroalkylene ether) chain via a divalent linking group, and the cyclopolysiloxane structure via a divalent linking group. It is a compound having a structure in which a (meth) acryloyl group is bonded.
• poly (perfluoroalkylene ether) is sometimes referred to as “perfluoropolyether”.
• Examples of the poly (perfluoroalkylene ether) chain of the fluorine compound (B) include those having a structure in which a divalent fluorocarbon group having 1 to 3 carbon atoms and oxygen atoms are alternately connected.
• the divalent fluorinated carbon group having 1 to 3 carbon atoms may be one kind or a combination of two or more kinds. Specific examples include those represented by the following structural formula (1). It is done.
• X is the following formulas (1-1) to (1-5), and X is one of the following formulas (1-1) to (1-5)
• two or more of the following formulas (1-1) to (1-5) may be present in a random or block form, and n represents a repeating unit. Represents an integer of 2 to 200.
• the perfluoromethylene represented by the formula (1-1) is used.
• a poly (perfluoroalkylene ether) chain in which a group and a perfluoroethylene group represented by the formula (1-2) are combined is preferable.
• the molar ratio of the perfluoromethylene group represented by the formula (1-1) to the perfluoroethylene group represented by the formula (1-2) [(1-1) / (1-2 )] Is preferably in the range of 1/10 to 10/1.
• the value of n in the general formula (1) is preferably in the range of 2 to 200, more preferably in the range of 10 to 100, and further preferably in the range of 20 to 80.
• Examples of the cyclopolysiloxane structure possessed by the fluorine compound (B) include a structure represented by the following general formula (2).
• R 1 is a methyl group
• R 3 is a divalent organic group bonded to a poly (perfluoroalkylene ether) chain
• R 4 is a 1 having a (meth) acryloyl group.
• m is an integer of 2 to 5.
• cyclopolysiloxane structures a cyclotetrasiloxane structure in which m in the general formula (2) is 3 is preferable.
• the divalent linking group that connects the poly (perfluoroalkylene ether) chain and the cyclopolysiloxane structure is not particularly limited as long as it is a divalent organic group.
• the divalent linking group is represented by the following general formula (3). Can be mentioned.
• Y is an alkylene group having 1 to 6 carbon atoms.
• the divalent linking group that bonds the cyclopolysiloxane structure and the (meth) acryloyl group is not particularly limited as long as it is a divalent organic group.
• it is represented by the following general formula (4). Things.
• Z 1 , Z 2 and Z 3 are each independently an alkylene group having 1 to 6 carbon atoms.
• Examples of the method for producing the fluorine compound (B) include a method for producing the fluorine compound (B) through the following steps (1) to (3).
• a compound having an allyl group at both ends of a poly (perfluoroalkylene ether) chain and a cyclopolysiloxane compound having a hydrosilyl group are reacted in the presence of a platinum-based catalyst to form both poly (perfluoroalkylene ether) chains.
• the blending amount of the fluorine compound (B) in the active energy ray-curable composition of the present invention can impart higher pencil hardness to the cured coating film surface of the active energy ray-curable composition of the present invention, and scratch resistance.
• the urethane (meth) acrylate (A1), the polyfunctional (meth) acrylate (A2), and other (meth) acrylates optionally blended in a total of 100 parts by mass
• the range of 0.05 to 5 parts by mass is preferable, and the range of 0.1 to 2 parts by mass is more preferable.
• the reactive silica (C1) is obtained by introducing a reactive group such as a (meth) acryloyl group on the surface of silica particles by surface modification.
• the reactive silica (C1) is preferably nanometer-sized, since it can further improve the transparency of the cured coating film of the active energy ray-curable composition of the present invention and the pencil hardness of the surface.
• Silica is preferred.
• the specific average particle size is preferably in the range of 5 to 200 nm, more preferably in the range of 5 to 100 nm.
• the non-reactive silica (C2) does not have a reactive group on the surface of the silica particles, but may be surface-modified with a non-reactive organic group. Further, the non-reactive silica (C2) can further improve the transparency of the cured coating film and the pencil hardness of the surface of the active energy ray-curable composition of the present invention, and can further improve the curl resistance.
• An order size is preferable, and colloidal silica is preferable.
• the specific average particle size is preferably in the range of 5 to 200 nm, more preferably in the range of 5 to 100 nm.
• the use ratio [(C1) / (C2)] of the reactive silica (C1) and the non-reactive silica (C2) is the pencil hardness of the cured coating film surface of the active energy ray-curable composition of the present invention.
• the range of 0.5 to 1.5 is preferable, and the range of 0.6 to 1 is more preferable.
• the total amount of the reactive silica (C1) and the non-reactive silica (C2) in the active energy ray-curable composition of the present invention is the amount of the cured coating film surface of the active energy ray-curable composition of the present invention. Since the pencil hardness, scratch resistance, antifouling property and slipperiness can be further improved, the urethane (meth) acrylate (A1), the polyfunctional (meth) acrylate (A2), and other (meth) acrylates optionally blended Is preferably in the range of 100 to 300 parts by mass, more preferably in the range of 150 to 280 parts by mass.
• the active energy ray-curable composition of the present invention can be formed into a cured coating film by irradiating active energy rays after being applied to a substrate.
• the active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
• a photopolymerization initiator (D) is added to the active energy ray curable composition of the present invention to improve curability.
• a photosensitizer can be further added to improve curability.
• Examples of the photopolymerization initiator (D) include intramolecular cleavage type photopolymerization initiators and hydrogen abstraction type photopolymerization initiators.
• Examples of the intramolecular cleavage type photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo [2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propanone], benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy -2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Acetophenone compounds such as
• the hydrogen abstraction type photopolymerization initiator includes, for example, benzophenone, methyl 4-phenylbenzophenone o-benzoylbenzoate, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide.
• the photosensitizer examples include tertiary amine compounds such as diethanolamine, N-methyldiethanolamine and tributylamine, urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothuronium-p. -Sulfur compounds such as toluene sulfonate.
• tertiary amine compounds such as diethanolamine, N-methyldiethanolamine and tributylamine
• urea compounds such as o-tolylthiourea, sodium diethyldithiophosphate, s-benzylisothuronium-p.
• -Sulfur compounds such as toluene sulfonate.
• the amount of these photopolymerization initiator and photosensitizer used is preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of the non-volatile component in the active energy ray-curable composition of the present invention. More preferred is 15% by mass.
• the active energy ray-curable composition of the present invention includes a polymerization inhibitor, a surface conditioner, an antistatic agent, an antifoaming agent, a viscosity as necessary.
• Additives such as regulators, light stabilizers, weather stabilizers, heat stabilizers, UV absorbers, antioxidants, leveling agents, organic pigments, inorganic pigments, pigment dispersants, silica beads, organic beads; silicon oxide, oxidation Inorganic fillers such as aluminum, titanium oxide, zirconia, and antimony pentoxide can be blended. These other blends can be used alone or in combination of two or more.
• the method for applying the active energy ray-curable composition of the present invention to the substrate varies depending on the application, but includes, for example, die coating, microgravure coating, gravure coating, roll coating, comma coating, air knife coating, kiss coating, spray coating, Examples include dip coating, spinner coating, wheeler coating, brush coating, full surface coating with silk screen, wire bar coating, and flow coating.
• the active energy rays for curing the active energy ray-curable composition of the present invention are ionizing radiations such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
• the sources of ultraviolet rays are low pressure mercury lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, electrodeless lamps, chemical lamps, black light lamps, mercury-xenon. Examples include lamps, short arc lamps, helium / cadmium lasers, argon lasers, sunlight, and LEDs.
• the substrate to which the active energy ray-curable composition of the present invention is applied is a film substrate
• the influence of heat on the film substrate can be reduced by using a flashing xenon-flash lamp. Therefore, it is preferable.
• the generation source of the electron beam include a scanning electron beam accelerator and a curtain type electron beam accelerator.
• the active energy ray-curable composition of the present invention when the active energy ray-curable composition of the present invention is irradiated with ultraviolet rays to form a cured coating film, it may be performed in an air atmosphere, but a cured coating film having higher pencil hardness is obtained, Furthermore, it is preferable to carry out in an atmosphere having an oxygen concentration of 5,000 ppm or less because a cured coating film having excellent scratch resistance and slipperiness can be obtained.
• the active energy ray-curable composition of the present invention Since the cured coating film of the active energy ray-curable composition of the present invention has excellent antifouling properties and is excellent in scratch resistance and slipperiness, the active energy ray-curable composition of the present invention is variously used. By applying and curing on the surface of an article, high pencil hardness can be imparted to the surface of various articles, and excellent antifouling properties, scratch resistance and slipperiness can also be imparted. Therefore, the active energy ray-curable composition of the present invention is very useful as a hard coating agent capable of imparting high scratch resistance, antifouling property and the like to the surface of various articles.
• Articles to which the active energy ray-curable composition of the present invention can be applied include housings for home appliances such as televisions, refrigerators, washing machines, and air conditioners; electronic devices such as personal computers, smartphones, mobile phones, digital cameras, and game machines. Enclosures; Interior materials for various vehicles such as automobiles and railway vehicles; Various building materials such as decorative panels; Woodwork materials such as furniture; Artificial and synthetic leather; FRP bathtubs; Liquid crystal displays (LCD) such as triacetylcellulose (TAC) films Optical film; Prism sheet or diffusion sheet as backlight member of LCD; Various display screens (hard coat layer, antireflection layer) such as plasma display (PDP) and organic EL display; Touch panel; Electronics such as mobile phones and smartphones Terminal screen: Color filter for liquid crystal display (hereinafter referred to as “CF”) ) Transparent protective film; Optical recording media such as CD, DVD, Blu-ray Disc; Transfer film for insert mold (IMD, IMF); Rubber roller for OA equipment such as copiers and printers
• the hard coat film of the present invention has a hard coat layer obtained by curing the active energy ray-curable composition of the present invention on at least one surface of a film substrate.
• a film substrate various commonly used resin film substrates can be used, for example, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, cellophane, diacetylcellulose, triacetylcellulose, acetylcellulose butyrate.
• the film substrate may be a substrate composed only of the resin film mentioned above, but in order to improve the adhesion with the active energy ray-curable composition of the present invention, the resin film It may be a film substrate provided with a primer layer.
• the primer layer include those made of polyester resin, urethane resin, acrylic resin, and the like.
• the surface of the resin film is subjected to surface concavo-convex treatment by sandblasting method, solvent treatment method, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone
• the treatment can also be performed by ultraviolet irradiation treatment, oxidation treatment or the like.
• the thickness of the film substrate is preferably in the range of 50 to 200 ⁇ m, more preferably in the range of 80 to 150 ⁇ m, and still more preferably in the range of 90 to 130 ⁇ m.
• curling can be easily suppressed even when a hard coat layer is provided on one side of the film substrate.
• a film substrate having an elastic modulus in the range of 3 to 7 GPa is preferably used, and a film substrate in the range of 3 to 5 GPa is particularly preferable.
• the elastic modulus is within this range, deformation of the film substrate is less likely to occur when a protective film is formed, and cracking of the hard coat layer can be suppressed, and a decrease in hardness of the hard coat film surface can be easily suppressed.
• the flexibility of the film base material can be ensured, it is easy to follow a gentle curved surface when a protective film described later is attached.
• the protective film of the present invention has an adhesive layer on one side of the hard coat film.
• the pressure-sensitive adhesive layer can be provided by attaching a pressure-sensitive adhesive tape to the film base material, or by directly applying a pressure-sensitive adhesive layer to the surface opposite to the hard coat surface of the film base material.
• the thickness of the pressure-sensitive adhesive layer of the protective film of the present invention is preferably in the range of 5 to 50 ⁇ m, more preferably in the range of 8 to 30 ⁇ m, and even more preferably in the range of 10 to 25 ⁇ m.
• this invention by making the thickness of an adhesive layer into the said range, it is excellent in adhesive reliability, and can maintain the surface hardness of a hard coat film not remarkably impaired.
• the pressure-sensitive adhesive used in the pressure-sensitive adhesive layer used in the present invention known acrylic, rubber-based, silicone-based pressure-sensitive resins can be used.
• an acrylic copolymer obtained by polymerizing a (meth) acrylate monomer having an alkyl group having 2 to 14 carbon atoms as a repeating unit as a main component has excellent adhesion to a film substrate, transparency, It is preferable from the point of weather resistance.
• Examples of the (meth) acrylate monomer having 2 to 14 carbon atoms include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, and n-hexyl acrylate.
• an alkyl (meth) acrylate having an alkyl group having 4 to 9 carbon atoms is preferable, and an alkyl acrylate having an alkyl group having 4 to 9 carbon atoms is more preferable.
• an alkyl acrylate having an alkyl group having 4 to 9 carbon atoms is more preferable.
• the alkyl acrylates n-butyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate, isononyl acrylate, and ethyl acrylate are particularly preferable.
• the content of the (meth) acrylate having 2 to 14 carbon atoms in the monomer constituting the acrylic copolymer used in the pressure-sensitive adhesive layer of the present invention is preferably 90 to 99% by mass, More preferably, it is made -96 mass%. By setting the content of the (meth) acrylate in this range, it is easy to ensure a suitable adhesive force.
• (meth) acrylate monomers having polar groups such as hydroxyl, carboxyl and amide groups and vinyl monomers having other polar groups should be used as monomer components. Is preferred.
• Examples of the (meth) acrylate monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, hydroxypropyl (meth) acrylate, Examples include caprolactone-modified (meth) acrylate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate. Of these, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth) acrylate are preferably used.
• Examples of the (meth) acrylate monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, acrylic acid or methacrylic acid dimer, ethylene oxide-modified succinic acid acrylate, and the like. Can be mentioned. Among these, it is preferable to use acrylic acid.
• Examples of the (meth) acrylate monomer having an amide group include N-vinyl-2-pyrrolidone, N-vinylcaprolactam, acryloylmorpholine, acrylamide, N, N-dimethylacrylamide, N-acryloyloxyethyl-3, 4,5,6-tetrahydrophthalimide and the like. Of these, N-vinyl-2-pyrrolidone, N-vinylcaprolactam, and acryloylmorpholine are preferably used.
• Examples of the other vinyl monomers having a polar group include vinyl acetate, acrylonitrile, maleic anhydride, itaconic anhydride and the like.
• the content of the monomer having a polar group is preferably 0.1 to 20% by mass, more preferably 1 to 13% by mass, based on the monomer component constituting the acrylic copolymer. More preferably, it is 1.5 to 8% by weight.
• the weight average molecular weight Mw of the acrylic copolymer used for the pressure-sensitive adhesive layer is preferably 400,000 to 1,400,000, and more preferably 600,000 to 1,200,000. When the weight average molecular weight Mw of the acrylic copolymer is within the range, it is easy to adjust the adhesive force to a specific range.
• the weight average molecular weight Mw can be measured by gel permeation chromatography (GPC). More specifically, as a GPC measurement device, “SC8020” manufactured by Tosoh Corporation can be used to measure and obtain the following GPC measurement conditions based on polystyrene conversion values. (GPC measurement conditions) Sample concentration: 0.5% by weight (tetrahydrofuran solution) Sample injection volume: 100 ⁇ L ⁇ Eluent: Tetrahydrofuran (THF) ⁇ Flow rate: 1.0 mL / min Column temperature (measurement temperature): 40 ° C ⁇ Column: “TSKgel GMHHR-H” manufactured by Tosoh Corporation ⁇ Detector: Differential refraction
• a crosslinking agent to the pressure-sensitive adhesive.
• a crosslinking agent an isocyanate type crosslinking agent, an epoxy type crosslinking agent, a chelate type crosslinking agent etc. are mentioned, for example.
• the addition amount of the crosslinking agent is preferably adjusted so that the gel fraction of the pressure-sensitive adhesive layer is 25 to 80% by mass, more preferably adjusted to be 40 to 75% by mass, and 50 to 70% by mass. It is most preferable to adjust so that.
• the gel fraction in the present invention is expressed as a percentage of the original mass by immersing the cured pressure-sensitive adhesive layer in toluene, measuring the mass after drying of the insoluble matter remaining after standing for 24 hours, and the original mass. Is.
• a tackifier resin may be added to improve the adhesive strength of the adhesive layer.
• the addition amount of the tackifier resin is preferably in the range of 10 to 60 parts by mass with respect to 100 parts by mass of the acrylic copolymer when the adhesive resin is an acrylic copolymer. Further, when importance is attached to adhesion, it is preferably added in the range of 20 to 50 parts by mass.
• additives can be added to the adhesive.
• the silane coupling agent in the range of 0.001 to 0.005 parts by mass with respect to 100 parts by mass of the pressure-sensitive adhesive.
• a plasticizer, a softening agent, a filler, a pigment, a flame retardant, etc. can also be added as other additives as needed.
• the protective film of the present invention can be applied to various uses because it has suitable scratch resistance and slipperiness, and is particularly suitable for an image display unit of an image display device such as a liquid crystal display (LCD) or an organic EL display. Applicable.
• an image display unit of an image display device such as a liquid crystal display (LCD) or an organic EL display.
• LCD liquid crystal display
• organic EL display an organic EL display.
• portable electronic devices that are highly demanded for miniaturization and thinning of electronic notebooks, mobile phones, smartphones, portable audio players, mobile personal computers, tablet terminals, etc. It is suitable as a protective film for the image display unit of the terminal image display device.
• an image display device for example, a configuration in which an image display module such as an LCD module or an organic EL module is included in the configuration, and a transparent panel for protecting the image display module is provided above the image display module.
• an image display module such as an LCD module or an organic EL module
• a transparent panel for protecting the image display module is provided above the image display module.
• it is effective to prevent scratches and to prevent scattering when the transparent panel is damaged by being attached to the front or back surface of the transparent panel.
• urethane acrylate (A1-2) having 6 acryloyl groups in one molecule A non-volatile content 80% by mass solution was obtained. This solution contains 19.5% by mass of PE4A in addition to urethane acrylate (A1-2) in the nonvolatile content.
• trimerized hexamethylene diisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd.) Module N3390BA ”, 90% by mass of non-volatile content, NCO%: 19.6, NCO equivalent: 214 g / eq.) 107 parts by mass and 50 parts by mass of methyl ethyl ketone were added dropwise over 2 hours. After completion of the dropwise addition, the mixture was reacted at 75 ° C.
• a perfluoropolyether compound (2) which is a pale yellow transparent liquid represented by
• an active energy ray-curable composition was prepared as follows.
• the active energy ray-curable composition (1) obtained above is coated with a wire bar (# 40) on the easy-adhesion treated surface of a polyethylene terephthalate film (“Cosmo Shine A4100” manufactured by Toyobo Co., Ltd., thickness 100 ⁇ m).
• a polyethylene terephthalate film (“Cosmo Shine A4100” manufactured by Toyobo Co., Ltd., thickness 100 ⁇ m).
• an ultraviolet irradiation device (“MIDN-042-C1” manufactured by Eye Graphics Co., Ltd., lamp: 120 W / cm, high pressure mercury lamp in an atmosphere having an oxygen concentration of 5,000 ppm or less. )
• MIDN-042-C1 manufactured by Eye Graphics Co., Ltd., lamp: 120 W / cm, high pressure mercury lamp in an atmosphere having an oxygen concentration of 5,000 ppm or less.
• MIDN-042-C1 manufactured by Eye Graphics Co., Ltd., lamp: 120 W / cm, high pressure mercury
• test piece film obtained above was evaluated or measured for the following curls, pencil hardness, scratch resistance, water contact angle, antifouling property, and slipperiness.
• the test piece film obtained above is cut into a 30 cm ⁇ 2 cm rectangle, fixed to a flat friction tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) with a jig, a load of 1 kg / cm 2 using steel wool # 0000, a stroke
• the scratched state of the test piece after 10 cm, speed 20 cm / sec, and reciprocating 200 times was visually observed, and scratch resistance was evaluated according to the following criteria.
• ⁇ 5 or more scratches are attached, but the entire test piece film is not damaged.
• X The test piece film is scratched.
• test piece film obtained above was cut into a 1 ⁇ 5 cm rectangle, and the cured film of the test piece film was fixed to the glass plate with a double-sided tape, and an automatic contact angle meter “DROMPAMSTER500” manufactured by Kyowa Interface Science Co., Ltd. was used. The contact angle of 4 to 4.5 ⁇ L of purified water was measured.
• Example 2 The non-volatile content was 40 as in Example 1 except that the 20% by mass solution of the fluorine compound (B-1) used in Example 1 was changed to 5 parts by mass (1 part by mass as the fluorine compound (B-1)).
• a mass% active energy ray-curable composition (2) was prepared. Using the obtained active energy ray-curable composition (2), in the same manner as in Example 1, evaluation or measurement was performed after preparing a test piece film.
• Example 4 The compounding amount of the methyl ethyl ketone dispersion having a nonvolatile content of 40% by mass of the reactive silica (C1-1) used in Example 1 was 287.5 parts by mass to 187.5 parts by mass (75 as reactive silica (C1-1)).
• An active energy ray-curable composition (4) having a nonvolatile content of 40% by mass was prepared in the same manner as in Example 1 except that the content was changed to (parts by mass). Using the obtained active energy ray-curable composition (4), in the same manner as in Example 1, evaluation or measurement was performed after preparing a test piece film.
• Composition (R1) Active energy ray curable having a nonvolatile content of 40% by mass, as in Example 1, except that the reactive silica (C1-1) and non-reactive silica (C2-1) used in Example 1 were not blended.
• Composition (R1) was prepared. Using the obtained active energy ray-curable composition (R1), in the same manner as in Example 1, evaluation or measurement was performed after producing a test piece film.
• Example 3 The compounding amount of the methyl ethyl ketone dispersion having a nonvolatile content of 40% by mass of the reactive silica (C1-1) used in Example 1 is 287.5 parts by mass to 200 parts by mass (200 parts by mass as reactive silica (C1-1)).
• the active energy ray-curable composition (R3) having a nonvolatile content of 40% by mass was prepared in the same manner as in Example 1 except that the non-reactive silica (C2-1) was not added. Using the obtained active energy ray-curable composition (R3), in the same manner as in Example 1, evaluation or measurement was performed after preparing a test piece film.
• Example 4 The blending amount of the non-reactive silica (C2-1) methyl ethyl ketone dispersion having a nonvolatile content of 40% by mass used in Example 1 is 312.5 parts by mass to 500 parts by mass (200 as non-reactive silica (C2-1)).
• the active energy ray-curable composition (R4) having a nonvolatile content of 40% by mass was prepared in the same manner as in Example 1 except that the reactive silica (C1-1) was not blended. Using the obtained active energy ray-curable composition (R4), in the same manner as in Example 1, evaluation or measurement was performed after producing a test piece film.
• Table 1 shows the compositions and evaluation results of the active energy ray-curable compositions obtained in Examples 1 to 4 and Comparative Examples 1 to 4 described above.
• the compositions in Table 1 are all described in terms of non-volatile content, and for urethane acrylates (A1-1) to (A1-3), the blending amounts including PE4A are described.
• the active energy ray-curable compositions of Examples 1 to 4 of the present invention have no problem in appearance as a coating agent, and there is no problem in the appearance of the cured coating film. I was able to confirm. It was also confirmed that the active energy ray-curable composition of the present invention has low curl after curing and high curl resistance. Furthermore, it was confirmed that the cured coating film surface of the active energy ray-curable composition of the present invention has high pencil hardness and excellent scratch resistance, pencil hardness, antifouling property and slipperiness.
• Comparative Example 1 is an example of an active energy ray-curable composition that does not use both the reactive silica (C1) and the non-reactive silica (C2) used in the present invention, but the pencil hardness is not sufficient. Was confirmed.
• Comparative Example 2 is an example of an active energy ray-curable composition using a fluorine compound other than the fluorine compound (B) used in the present invention, but it can be confirmed that pencil hardness, scratch resistance, and slipperiness are not sufficient. It was.
• Comparative Example 3 is an example of an active energy ray-curable composition that does not use the non-reactive silica (C2) used in the present invention, but the pencil hardness is insufficient, the curl after curing is large, and the curl resistance It was confirmed that it was not enough.
• Comparative Example 4 is an example of an active energy ray-curable composition that did not use the reactive silica (C1) used in the present invention, but it was confirmed that pencil hardness and scratch resistance were not sufficient.

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