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
  • C08F290/062—Polyethers
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
  • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
• • 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
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
• • 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
• • 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
  • C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
• • 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
  • 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
• • 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

Definitions

• the present invention relates to a curable composition useful as a material for forming a hard coat layer applied to a surface of a flexible display or the like. Specifically, the present invention relates to a curable composition having extremely high scratch resistance, flex resistance, and stretchability, and capable of forming a hard coat layer capable of further providing abrasion resistance.
• a cover glass is used on the surface of the smartphone to prevent the display from being damaged.
• glass cannot be bent back and cannot be applied to flexible displays. Therefore, application of a plastic film provided with a hard coat layer having scratch resistance has been attempted.
• a plastic film having such a hard coat layer is bent with the hard coat layer facing outside, a stress in a tensile direction is generated in the hard coat layer. Therefore, the hard coat layer is required to have a certain stretchability.
• a highly crosslinked structure is formed, that is, a surface structure is increased by forming a crosslinked structure having low molecular mobility, and resistance to external force is given.
• a technique is adopted.
• these hard coat layer forming materials polyfunctional acrylate materials which are three-dimensionally cross-linked by radicals are currently most used.
• polyfunctional acrylate materials generally do not have stretchability due to their high crosslink density. As described above, there is a trade-off relationship between the stretchability of the hard coat layer and the scratch resistance, and it has been an issue to achieve both properties.
• Patent Document 1 a technique using a combination of a polyfunctional urethane acrylate oligomer and a polyfunctional acrylate modified with ethylene oxide having high molecular mobility is disclosed.
• a touch panel is also mounted on the flexible display, and an operation is performed by touching the touch panel with a finger. For this reason, there is a problem that a fingerprint is attached to the touch panel every time the finger is touched, and the appearance is impaired.
• the fingerprint contains moisture derived from sweat and oil derived from sebum, and it is strongly desired that the hard coat layer be provided with water repellency and oil repellency in order to make it difficult for both the moisture and oil to adhere. ing. From such a viewpoint, it is desired that the surface of the hard coat layer has antifouling property against fingerprints and the like.
• a method for imparting antifouling property to the surface of the hard coat layer a method of adding a small amount of a fluorine-based surface modifier to a coating solution for forming the hard coat layer is used.
• the added fluorine-based surface modifier segregates on the surface of the hard coat layer due to its low surface energy, and imparts water repellency and oil repellency.
• the fluorine-based surface modifier has a number average molecular weight of about 1,000 to 5,000 having a poly (oxyperfluoroalkylene) chain, which is called perfluoropolyether. Is used.
• the perfluoropolyether has a high fluorine concentration, it is generally difficult to dissolve in an organic solvent used for a coating solution for forming a hard coat layer. In addition, aggregation occurs in the formed hard coat layer.
• an object of the present invention is to provide a curable composition having extremely high abrasion resistance, bending resistance, and stretchability, and capable of forming a hard coat layer that can also have abrasion resistance.
• the present inventors have conducted intensive studies to achieve the above object, and as a result, via a urethane bond at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group, not via a poly (oxyalkylene) group.
• a curable composition containing less than 3 mol of an oxyethylene-modified polyfunctional monomer can form a hard coat layer having extremely high scratch resistance, bending resistance, and stretchability, and further having wear resistance. The inventors have found that the present invention has been completed.
• the present invention as a first aspect, (A) 100 parts by mass of an oxyethylene-modified polyfunctional monomer having at least three active energy ray polymerizable groups, wherein the average oxyethylene-modified amount is less than 3 mol per 1 mol of the polymerizable group , (B) A perfluoropolyether having an active energy ray-polymerizable group at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via a urethane bond (however, the poly (oxyperfluoroalkylene) group Excluding a perfluoropolyether having a poly (oxyalkylene) group between the and the urethane bond.) 0.1 to 10 parts by mass, and (c) 1 mass of a polymerization initiator which generates a radical by an active energy ray To 20 parts by weight of the curable composition.
• the present invention relates to the curable composition according to the first aspect, wherein the (b) perfluoropolyether has at least two active energy ray-polymerizable groups at both ends.
• the present invention relates to the curable composition according to the second aspect, wherein the (b) perfluoropolyether has at least three active energy ray-polymerizable groups at both ends.
• the poly (oxyperfluoroalkylene) group is a group having — [OCF 2 ] — and — [OCF 2 CF 2 ] — as a repeating unit.
• the present invention relates to the curable composition according to any one of the above.
• the present invention relates to the curable composition according to the fourth aspect, wherein the (b) perfluoropolyether has a partial structure represented by the following formula [1].
• n represents the total number of repeating units — [OCF 2 CF 2 ] — and the number of repeating units — [OCF 2 ] —.
• the (a) oxyethylene-modified polyfunctional monomer contains at least one selected from the group consisting of an oxyethylene-modified polyfunctional (meth) acrylate compound and an oxyethylene-modified polyfunctional urethane (meth) acrylate compound.
• a curable composition according to any one of the first to fifth aspects.
• the average oxyethylene-modified amount of the (a) oxyethylene-modified polyfunctional monomer is 2 mol or less per 1 mol of the polymerizable group, according to any one of the first to sixth aspects.
• the curable composition of an eighth aspect the present invention relates to the curable composition according to any one of the first to seventh aspects, further including (d) a solvent.
• the present invention relates to a cured film obtained from the curable composition according to any one of the first to eighth aspects.
• the present invention relates to a hard coat film provided with a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer comprises the cured film according to the ninth aspect.
• the present invention relates to a hard coat film including a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer has a curability according to any one of the first to eighth aspects.
• the present invention relates to a hard coat film formed by a method including a step of applying a composition onto a film substrate to form a coating film, and a step of irradiating the coating film with an active energy ray and curing.
• the present invention relates to the hard coat film according to the tenth or eleventh aspect, wherein the hard coat layer has a thickness of 1 ⁇ m to 10 ⁇ m.
• a step of applying the curable composition according to any one of the first to eighth aspects on a film substrate to form a coating film, and irradiating the coating film with active energy rays The present invention relates to a method for producing a laminate including a step of curing.
• curable composition having extremely high scratch resistance, bending resistance, and stretchability, and capable of forming a hard coat layer capable of having abrasion resistance.
• the curable composition of the present invention in detail, (A) 100 parts by mass of an oxyethylene-modified polyfunctional monomer having at least three active energy ray polymerizable groups, wherein the average oxyethylene-modified amount is less than 3 mol per 1 mol of the polymerizable group , (B) A perfluoropolyether having an active energy ray-polymerizable group at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group via a urethane bond (however, the poly (oxyperfluoroalkylene) group Excluding a perfluoropolyether having a poly (oxyalkylene) group between the and the urethane bond.) 0.1 to 10 parts by mass, and (c) 1 mass of a polymerization initiator which generates a radical by an active energy ray To 20 parts by weight of the curable composition.
• each of the components (a) to (c) will be any of the components (a) to (c
• the oxyethylene-modified polyfunctional monomer having at least three active energy ray-polymerizable groups is an oxyethylene-modified polyfunctional monomer having at least three active energy ray-polymerizable groups, and has an average oxyethylene modification amount.
• the preferred (a) oxyethylene-modified polyfunctional monomer having at least three active energy ray-polymerizable groups in the curable composition of the present invention includes at least three active energy ray-polymerizable groups and an average oxyethylene-modified amount.
• the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound.
• (meth) acrylic acid refers to acrylic acid and methacrylic acid.
• the average amount of oxyethylene modification in the oxyethylene-modified polyfunctional monomer having at least three active energy ray-polymerizable groups is less than 3 mol per 1 mol of the active energy ray-polymerizable group of the monomer, and It is 2 mol or less per 1 mol of the active energy ray polymerizable group of the monomer. Further, (a) the average oxyethylene-modified amount of the oxyethylene-modified polyfunctional monomer having at least three active energy ray-polymerizable groups is larger than 0 mol, preferably 1 mol, per 1 mol of the active energy ray-polymerizable group of the monomer. The amount is 0.1 mol or more, more preferably 0.5 mol or more, based on 1 mol of the active energy ray polymerizable group of the monomer.
• Examples of the oxyethylene-modified polyfunctional (meth) acrylate compound include a (meth) acrylate compound of a polyol modified with oxyethylene.
• Examples of the polyol include glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, decaglycerin, polyglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.
• Examples of the active energy ray polymerizable group in the oxyethylene-modified polyfunctional monomer having at least three active energy ray polymerizable groups include a (meth) acryloyl group, a vinyl group, and an epoxy group.
• the number of oxyethylene added to one molecule of the oxyethylene-modified polyfunctional monomer having at least three active energy ray polymerizable groups is 1 to 30, preferably 1 to 12.
• the oxyethylene-modified polyfunctional monomer (a) having at least three active energy ray-polymerizable groups can be used alone or in combination of two or more.
• the component (b) plays a role as a surface modifier in a hard coat layer to which the curable composition of the present invention is applied.
• the component (b) has excellent compatibility with the component (a), thereby suppressing the hard coat layer from becoming cloudy and enabling formation of a hard coat layer having a transparent appearance.
• the above-mentioned poly (oxyalkylene) group means a group in which the number of repeating units of the oxyalkylene group is 2 or more, and the alkylene group in the oxyalkylene group is an unsubstituted alkylene group.
• the number of carbon atoms of the alkylene group in the poly (oxyperfluoroalkylene) group is not particularly limited, but is preferably 1 to 4 carbon atoms. That is, the poly (oxyperfluoroalkylene) group refers to a group having a structure in which a divalent fluorocarbon group having 1 to 4 carbon atoms and an oxygen atom are alternately connected, and the oxyperfluoroalkylene group is a carbon atom. It refers to a group having a structure in which a divalent fluorocarbon group of Formulas 1 to 4 and an oxygen atom are connected.
• oxyperfluoroalkylene group may be used alone or in a combination of two or more.
• bonds of the plural kinds of oxyperfluoroalkylene groups are block bonds and random bonds. Any of these may be used.
• -[OCF 2 ]-(oxyperfluoromethylene group) and-[OCF 2 CF 2 ] are used as poly (oxyperfluoroalkylene) groups from the viewpoint of obtaining a cured film having good scratch resistance. It is preferable to use a group having both-(oxyperfluoroethylene group) as a repeating unit.
• the bond of these repeating units may be any of a block bond and a random bond.
• the total number of repeating units of the oxyperfluoroalkylene group is preferably in the range of 5 to 30, and more preferably in the range of 7 to 21.
• the weight average molecular weight (Mw) of the poly (oxyperfluoroalkylene) group measured by gel permeation chromatography (GPC) in terms of polystyrene is 1,000 to 5,000, preferably 1,500 to 3, 000, or 1,500 to 2,000.
• Examples of the active energy ray polymerizable group bonded via the urethane bond include a (meth) acryloyl group and a vinyl group.
• the perfluoropolyether having a polymerizable group at both ends is not limited to one having an active energy ray polymerizable group such as a (meth) acryloyl group at each end, but two or more active energy rays. It may have a polymerizable group at both ends.
• an active energy ray polymerizable group such as a (meth) acryloyl group at each end, but two or more active energy rays. It may have a polymerizable group at both ends.
• the terminal structure containing an active energy ray polymerizable group the following structures [A1] to [A5], and acryloyl in these structures And a structure in which the group is substituted with a methacryloyl group.
• Examples of the perfluoropolyether having a polymerizable group at both ends include, for example, a perfluoropolyether having at least two active energy ray-polymerizable groups at both ends, and an active energy ray-polymerizable group at each end. Perfluoropolyethers having at least three are preferred. As such (b) perfluoropolyether having a polymerizable group at both ends, for example, a compound represented by the following formula [2] can be mentioned.
• A represents one of the structures represented by the formulas [A1] to [A5] and a structure in which an acryloyl group is substituted with a methacryloyl group in these structures
• PFPE is the poly (oxy) A perfluoroalkylene) group (provided that the side bonded to L 1 is an oxy terminal and the side bonded to L 2 is a perfluoroalkylene terminal), and L 1 and L 2 each have 1 to 3 fluorine atoms.
• A represents one of the structures represented by the formulas [A1] to [A5] and a structure in which an acryloyl group in these structures is substituted with a methacryloyl group.
• a structure represented by the formula [B3] is preferable, and a combination of the formula [B3] and the formula [A3] is particularly preferable.
• Preferred examples of (b) the perfluoropolyether having a polymerizable group at both terminals include a compound having a partial structure represented by the following formula [1].
• N in the formula [1] represents the total number of the number of repeating units-[OCF 2 CF 2 ]-and the number of repeating units-[OCF 2 ]-, and is preferably in the range of 5 to 30, more preferably 7 to A range of 21 is more preferred.
• the ratio of the number of repeating units — [OCF 2 CF 2 ] — to the number of repeating units — [OCF 2 ] — is preferably in the range of 2: 1 to 1: 2, and is approximately 1: 1. It is more preferable to be within the range.
• the bond of these repeating units may be any of a block bond and a random bond.
• a perfluoropolyether having a polymerizable group at both ends is defined as 0 to 100 parts by mass of the (a) oxyethylene-modified polyfunctional monomer having at least three active energy ray polymerizable groups. It is desirable to use it at a ratio of 1 to 10 parts by mass, preferably 0.2 to 5 parts by mass.
• the (b) perfluoropolyether having a polymerizable group at both ends is, for example, represented by the following formula [3] (Wherein, PFPE, L 1 , L 2 , L 3 and n have the same meanings as described above.)
• An isocyanate compound having a polymerizable group with respect to the hydroxy groups present at both ends of the compound That is, a compound in which an isocyanato group is bonded to a bond in the structures represented by the formulas [A1] to [A5] and a structure in which an acryloyl group is substituted by a methacryloyl group in these structures (for example, 2- (meth) ) Acryloyloxyethyl isocyanate, 1,1-bis ((meth) acryloyloxymethyl) ethyl isocyanate) to form a urethane bond.
• the curable composition of the present invention includes (b) a perfluoropolyether having an active energy ray-polymerizable group via a urethane bond at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group ( However, in addition to the poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond, urethane is added to one end of the molecular chain containing the poly (oxyperfluoroalkylene) group.
• a perfluoropolyether having an active energy ray-polymerizable group through a bond and having a hydroxy group at the other end of the molecular chain (provided that the poly (oxyperfluoroalkylene) group and the urethane bond have No poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the hydroxy group), and A perfluoropolyether having a hydroxy group at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group as represented by the above formula [3] (provided that the poly (oxyperfluoroalkylene) group and the (No poly (oxyalkylene) group is present between the hydroxy groups.) [Compound having no active energy ray-polymerizable group] may be included.
• the present invention also relates to a perfluoropolyether compound having at least three active energy ray-polymerizable groups via a urethane bond at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group (provided that Excluding a perfluoropolyether having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond).
• a perfluoropolyether compound having a polymerizable group at both ends a compound having a partial structure represented by the above formula [1] is preferable.
• the perfluoropolyether compound of the present invention has excellent compatibility with the component (a), whereby the hard coat layer is prevented from becoming cloudy and has a transparent appearance. It has an excellent effect of enabling formation.
• the present invention also relates to a surface modifier comprising the above perfluoropolyether compound, and to the use of the perfluoropolyether compound for surface modification.
• a polymerization initiator which generates a radical by a preferred active energy ray is, for example, an active energy such as an electron beam, an ultraviolet ray, and an X-ray. It is a polymerization initiator that generates radicals by radiation, especially by ultraviolet irradiation.
• Examples of the polymerization initiator (c) include benzoins, alkylphenones, thioxanthones, azos, azides, diazos, o-quinonediazides, acylphosphine oxides, oxime esters, organic peroxides, Examples include benzophenones, biscoumarins, bisimidazoles, titanocenes, thiols, halogenated hydrocarbons, trichloromethyltriazines, and onium salts such as iodonium salts and sulfonium salts. These may be used alone or in combination of two or more.
• alkylphenones As the polymerization initiator (c), it is preferable to use alkylphenones as the polymerization initiator (c) from the viewpoints of transparency, surface curability, and thin film curability.
• alkylphenones By using the alkylphenones, a cured film having more improved scratch resistance can be obtained.
• alkylphenones examples include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) ⁇ -hydroxy such as 2-methylpropan-1-one, 2-hydroxy-1- (4- (4- (2-hydroxy-2-methylpropionyl) benzyl) phenyl) -2-methylpropan-1-one Alkylphenones; 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one ⁇ -aminoalkylphenones such as 2,2-dimethoxy-1,2-diphenylethan-1-one; phenylglio Methyl xylate is mentioned.
• the polymerization initiator (c) is used in an amount of 1 to 20 parts by mass, preferably 1 to 20 parts by mass, based on 100 parts by mass of the (a) oxyethylene-modified polyfunctional monomer having at least three active energy ray-polymerizable groups. It is desirable to use 2 to 10 parts by mass.
• the curable composition of the present invention may further contain (d) a solvent, that is, it may be in the form of a varnish (film-forming material).
• the solvent is appropriately selected by dissolving the components (a) to (c) and taking into consideration the workability at the time of coating for forming a cured film (hard coat layer) to be described later, the drying property before and after curing, and the like. do it.
• the solvent examples include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, and cyclohexane; methyl chloride; Halides such as methyl bromide, methyl iodide, dichloromethane, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate; Esters or ester ethers such as propylene glycol monomethyl ether acetate; diethyl ether, tetrahydrofuran, 1,4-dioxane, methyl cellosolve
• the amount of the solvent used is not particularly limited, but is used, for example, at a concentration at which the solid content in the curable composition of the present invention is 1% by mass to 70% by mass, preferably 5% by mass to 50% by mass.
• the solid content concentration also referred to as non-volatile content concentration refers to the solid content based on the total mass (total mass) of the components (a) to (d) (and other additives as required) of the curable composition of the present invention. (Content of all components excluding solvent components).
• the curable composition of the present invention includes additives generally added as necessary, as long as the effects of the present invention are not impaired, such as a polymerization inhibitor, a photosensitizer, a leveling agent, and a surfactant.
• additives generally added as necessary, as long as the effects of the present invention are not impaired, such as a polymerization inhibitor, a photosensitizer, a leveling agent, and a surfactant.
• Agents, adhesion promoters, plasticizers, ultraviolet absorbers, antioxidants, storage stabilizers, antistatic agents, inorganic fillers, pigments, and dyes may be appropriately blended.
• the curable composition of the present invention can form a cured film by applying (coating) on a substrate to form a coating film, and irradiating the coating film with active energy rays to polymerize (cur).
• the cured film is also an object of the present invention.
• a hard coat layer in a hard coat film to be described later can be made of the cured film.
• the base material in this case include various resins (polycarbonate, polymethacrylate, polystyrene, polyester such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN)), polyolefin, polyamide, polyimide, epoxy resin, melamine resin, triamine, and the like.
• ABS acrylonitrile-butadiene-styrene copolymer
• AS acrylonitrile-styrene copolymer
• TPU thermoplastic polyurethane
• metal wood, paper, glass, and slate.
• the shape of these substrates may be plate-like, film-like or three-dimensionally formed.
• the coating method on the substrate is, for example, a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a spray coating method, a bar coating method, a die coating method, an inkjet method, a printing method (for example, , Letterpress printing method, intaglio printing method, lithographic printing method, screen printing method).
• a printing method for example, , Letterpress printing method, intaglio printing method, lithographic printing method, screen printing method.
• the method can be used for a roll-to-roll method, and a thin film coating property can be used.
• the curable composition is filtered using a filter having a pore size of about 0.2 ⁇ m or the like in advance, and then subjected to coating.
• a solvent may be added to the curable composition, if necessary, to form a varnish.
• examples of the solvent include various solvents described in the above [(d) solvent].
• the coating film is pre-dried by a heating means such as a hot plate or an oven, if necessary, to remove the solvent (solvent removing step).
• the heating and drying conditions at this time are preferably, for example, at 40 ° C. to 120 ° C. for about 30 seconds to 10 minutes.
• the coating film is cured by irradiation with active energy rays such as ultraviolet rays.
• active energy rays such as ultraviolet rays.
• the active energy ray include an ultraviolet ray, an electron beam, and an X-ray, and an ultraviolet ray is particularly preferable.
• a light source used for ultraviolet irradiation for example, a solar ray, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, and a UV-LED can be used.
• the polymerization may be completed by performing post-baking, specifically, by heating using a heating means such as a hot plate or an oven.
• the thickness of the formed cured film after drying and curing is usually 0.01 ⁇ m to 50 ⁇ m, preferably 0.05 ⁇ m to 20 ⁇ m.
• a hard coat film having a hard coat layer on at least one surface (surface) of a film substrate can be produced.
• the hard coat film is also an object of the present invention, and the hard coat film is suitably used for protecting the surface of various display elements such as a flexible display.
• the hard coat layer in the hard coat film of the present invention is a step of applying the curable composition of the present invention on a film substrate to form a coating film, and irradiating the coating film with active energy rays such as ultraviolet rays. And a step of curing the coating film.
• Preferred resin films include, for example, polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polycarbonate, polymethacrylate, polystyrene, polyolefin, polyamide, polyimide, triacetyl cellulose, and thermoplastic.
• PET polyethylene terephthalate
• PBT polybutylene terephthalate
• PEN polyethylene naphthalate
• polycarbonate polymethacrylate
• polystyrene polyolefin
• polyamide polyamide
• polyimide polyimide
• TPU Polyurethane
• the method for applying the curable composition on the film substrate (coating film forming step) and the method for irradiating the coating film with active energy rays (curing step) may be the same as those described in the above ⁇ Curing film>.
• a solvent is contained in the curable composition of the present invention (varnish form)
• a step of drying the coating film and removing the solvent may be included as necessary.
• the method for drying a coating film (solvent removal step) described in the above ⁇ Curing film> can be used.
• the thickness of the hard coat layer thus obtained is preferably 1 ⁇ m to 20 ⁇ m, more preferably 1 ⁇ m to 10 ⁇ m.
• the present invention also relates to a method for producing a laminate, comprising the steps of applying the curable composition described above on a film substrate to form a coating film, and irradiating the coating film with an active energy ray to cure the coating film.
• a method for producing a laminate comprising the steps of applying the curable composition described above on a film substrate to form a coating film, and irradiating the coating film with an active energy ray to cure the coating film.
• the step of applying a film on a film substrate to form a coating film and the step of irradiating the coating film with active energy rays and curing the same can be performed under the same operation and conditions as described above.
• Coating device using a bar coater PM-9050MC manufactured by SMT Co., Ltd.
• Bar OSG System Products Co., Ltd.
• Coating speed 4 m / min
• Oven Equipment Advantech Toyo Co., Ltd. dust-free dryer DRC433FA
• UV curing device Heraeus Co., Ltd.
• CV-110QC-G Lamp High pressure mercury lamp H-bulb manufactured by Heraeus Corporation (4) Gel permeation chromatography (GPC) Apparatus: Tosoh Corporation HLC-8220GPC Column: Shodex (registered trademark) GPC K-804L, GPC K-805L manufactured by Showa Denko KK Column temperature: 40 ° C Eluent: tetrahydrofuran Detector: RI (5) Scratch resistance test device: Shinto Kagaku Co., Ltd. reciprocating wear tester TRIBOGEAR TYPE: 30S Scanning speed: 3,000 mm / min Scanning distance: 50 mm (6) Contact angle device: DropMaster DM-501 manufactured by Kyowa Interface Science Co., Ltd.
• Bending test device Cylindrical mandrel bending tester manufactured by Allgood Co., Ltd.
• Tensile testing device Tabletop precision universal testing machine Autograph AGS-10kNX manufactured by Shimadzu Corporation Gripping tool: 1 kN manual screw type flat gripping tool Gripping tooth: High-strength rubber-coated gripping tooth Peeling speed: 50 mm / min Measurement temperature: 23 ° C (9)
• Abrasion resistance test device Reciprocating wear tester manufactured by Shinto Kagaku Co., Ltd. TRIBOGEAR TYPE: 30S Scanning speed: 4,500mm / min Scanning distance: 50mm
• a-1 Ethylene oxide-modified trimethylolpropane triacrylate [Aronix (registered trademark) M-350, manufactured by Toagosei Co., Ltd., 3 mol of oxyethylene groups]
• a-2 Ethylene oxide modified pentaerythritol tetraacrylate [KAYALAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., 4 mol of oxyethylene groups]
• a-3 Ethylene oxide-modified diglycerin tetraacrylate [Aronix (registered trademark) M-460, manufactured by Toagosei Co., Ltd., 4 mol of oxyethylene groups]
• a-4 Ethylene oxide-modified tetraglycerin polyacrylate [SA-TE6 manufactured by Sakamoto Pharmaceutical Co., Ltd., number of functional groups 6, oxyethylene group 6 mol] a-5: Ethylene oxide-modified decaglycerin
• the weight average molecular weight: Mw of the obtained SM3 measured by GPC in terms of polystyrene was 2,900, and the degree of dispersion: Mw (weight average molecular weight) / Mn (number average molecular weight) was 1.2.
• the obtained hard coat film was evaluated for scratch resistance (appearance, stain resistance), bending resistance, and stretchability. The procedure of each evaluation is shown below. The results are shown in Table 2.
• A The contact angle value before the test is 90 degrees or more and the difference between the contact angle values before and after the test is less than 10 degrees
• C The contact angle value before the test is 90 degrees or more and the difference between the contact angle values before and after the test is 10 degrees or more Or the contact angle value before the test is less than 90 degrees
• the hard coat film was cut into a rectangle having a length of 80 mm and a width of 20 mm to prepare a test piece.
• the short side of the test piece was fixed to a tester in which a mandrel was set, and the test piece was bent by 180 degrees over 1 to 2 seconds such that the hard coat layer was on the outside.
• the bent hard coat layer was visually observed to confirm the presence or absence of cracks.
• the test was performed with a mandrel having a radius of curvature of 1 mmR, 2 mmR, 3 mmR, 5 mmR, and 10 mmR, and the minimum radius of curvature in which no crack occurred was evaluated as bending resistance according to the following criteria A, B, and C.
• A less than 3 mmR B: 3 mmR or more and less than 10 mmR C: 10 mmR or more
• the hard coat film was cut into a rectangle having a length of 60 mm and a width of 10 mm to prepare a test piece.
• the hard coat layer of the test piece was visually observed, and the maximum stretch ratio at which no crack occurred was evaluated as stretchability according to the following criteria A, B and C. In addition, assuming actual use as the hard coat layer, at least B is required, and A is desirable.
• an oxyethylene-modified acrylate having 3 or more functional groups and 1 to 2 mol of oxyethylene groups per 1 mol of the functional group was used as a polyfunctional monomer.
• the hard coat films (Examples 1 to 7) produced using the curable compositions in which the perfluoropolyether SM1 having four acryloyl groups were respectively blended through the film had excellent scratch resistance and bending resistance. It was found that the film had good stretchability and moderate stretchability. Further, a hard coat film (Examples 8 and 9) produced using a curable composition containing perfluoropolyether SM2 or SM3 instead of SM1 as a surface modifier has excellent scratch resistance. In addition, it became clear that it had bending resistance and moderate stretchability.
• the hard coat films (Comparative Examples 1 to 4) using trifunctional to hexafunctional acrylates not modified with oxyethylene as the polyfunctional monomers resulted in extremely inferior bending resistance and stretchability.
• the hard coat films using the oxy (methylethylene) -modified trifunctional acrylate (Comparative Examples 5 and 6) resulted in inferior abrasion resistance even when the oxyalkylene group was 1 mol per 1 mol of the functional group. .
• a hard coat film using an acrylate having 3 mol of oxyethylene groups per 1 mol of functional group (Comparative Example 7) resulted in poor antifouling properties.
• the hard coat film containing no perfluoropolyether as a surface modifier resulted in inferior scratch resistance and stain resistance.
• Examples 10 to 12 Comparative Example 9
• the following components (1) to (4) were mixed to prepare a curable composition having a solid content concentration shown in Table 3.
• the solid content refers to components other than the solvent.
• [parts] represents [parts by mass]
• EO represents an oxyethylene group.
• the obtained hard coat film was evaluated for abrasion resistance in addition to the evaluation of [scratch resistance], [flexibility] and [stretchability] described above.
• the procedure of the wear resistance evaluation is shown below. Table 4 shows the results.
• oxyethylene-modified acrylate in which the number of functional groups is 3 or more and oxyethylene group is 1 mol per 1 mol of functional group is used as a polyfunctional monomer, and perfluoropolyether SM1, SM2 or
• the hard coat films (Examples 10 to 12) produced using the curable compositions in which SM3 was respectively blended exhibited excellent abrasion resistance in addition to excellent abrasion resistance, bending resistance and stretchability. It became clear to have.

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