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
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
• • 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
  • C08G18/80—Masked polyisocyanates
  • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
  • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
  • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
  • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
  • C08G18/8025—Masked aliphatic or cycloaliphatic polyisocyanates
• • 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
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
• • 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
  • C08F290/067—Polyurethanes; Polyureas
• • 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
  • C08F290/08—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 side groups
  • C08F290/14—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
  • C08F290/08—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 side groups
  • C08F290/14—Polymers provided for in subclass C08G
  • C08F290/147—Polyurethanes; Polyureas
• • 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
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/2815—Monohydroxy compounds
  • C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
  • C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
• • 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
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/2815—Monohydroxy compounds
  • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
• • 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
  • C08G18/6725—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing ester groups other than 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
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/7806—Nitrogen containing -N-C=0 groups
  • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
  • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret 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
  • C08G18/77—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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/28—Treatment by wave energy or particle radiation
• • 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
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • 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
  • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
• • G02B1/105—
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
  • G02B1/14—Protective coatings, e.g. hard coatings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

• the present invention relates to an actinic energy ray-curable composition useful as paints or coating agents for products where scratch resistance is required.
• an ultraviolet curable composition containing an ultraviolet curable urethane (meth)acrylate oligomer and a photoinitiator.
• the oligomer is obtained by reacting an isocyanate prepolymer compound having three or more isocyanate groups in one molecule with a polycaprolactone-modified hydroxyethyl(meth)acrylate.
• the ultraviolet curable composition In a cured product of the ultraviolet curable composition, scratches generated on the surface of the product can be repaired by self-repairing ability. Therefore, the cured product has scratch resistance. Accordingly, the ultraviolet curable composition is useful as paints or coating agents for products where scratch resistance is required.
• the scratch resistance of the cured product is not necessarily satisfied in some applications. This limits the applications for the ultraviolet curable composition.
• An object of the present invention is to provide an actinic energy ray-curable composition capable of forming a cured product having excellent scratch resistance.
• the following actinic energy ray-curable composition is provided.
• a scratch mark is made at a vertical load of 235 mN using a diamond indenter with a tip diameter of 15 ⁇ m
• the scratch mark is repaired by self-repairing ability under an atmosphere at 25° C. and at a relative humidity of 50%.
• the following actinic energy ray-curable composition contains a urethane(meth)acrylate obtained by reacting an organic isocyanate having a plurality of isocyanate groups in one molecule with a polycaprolactone-modified alkyl(meth)acrylate.
• the urethane(meth)acrylate contains two or more kinds of urethane(meth)acrylates different from one another in a number of repetitions of a caprolactone unit per one residue of the polycaprolactone-modified alkyl(meth)acrylate.
• the following actinic energy ray-curable composition contains a urethane(meth)acrylate obtained by reacting an organic isocyanate having a plurality of isocyanate groups in one molecule with two or more kinds of polycaprolactone-modified alkyl(meth)acrylates different from one another in a number of repetitions of a caprolactone unit per one molecule.
• the following actinic energy ray-curable composition contains a urethane(meth)acrylate obtained by reacting an organic isocyanate having a plurality of isocyanate groups in one molecule with a polycaprolactone-modified alkyl(meth)acrylate, and a urethane(meth)acrylate obtained by reacting an organic isocyanate having a plurality of isocyanate groups in one molecule with a hydroxyalkyl(meth)acrylate.
• the following actinic energy ray-curable composition contains a urethane(meth)acrylate obtained by reacting an organic isocyanate having a plurality of isocyanate groups in one molecule with a polycaprolactone-modified alkyl(meth)acrylate and a hydroxyalkyl(meth)acrylate.
• the actinic energy ray-curable composition according to the first embodiment contains two or more kinds of urethane(meth)acrylates different from one another in the number of repetitions of a caprolactone unit per one residue of a polycaprolactone-modified alkyl(meth)acrylate.
• the average number of repetitions per one molecule of the urethane(meth)acrylate relative to the number of repetitions of the caprolactone unit per one residue of the polycaprolactone-modified alkyl(meth)acrylate is preferably in the range of from 1 to 5, more preferably in the range of from 1 to 2.5.
• the maximum difference in the number of repetitions of the caprolactone unit per one residue of the polycaprolactone-modified alkyl(meth)acrylate between two kinds of the urethane(meth)acrylates is preferably 9 or less, more preferably in the range of from 4 to 9.
• Each of the urethane(meth)acrylates is synthesized by reacting an organic isocyanate with a polycaprolactone-modified alkyl(meth)acrylate. By mixing these urethane (meth)acrylates, the actinic energy ray-curable composition is prepared.
• the reaction temperature is preferably from an ordinary temperature to 100° C. and the reaction time is preferably from 1 to 10 hours.
• the organic isocyanate is an organic compound having a plurality of isocyanate groups in one molecule.
• the number of isocyanate groups contained in one molecule of the organic isocyanate is preferably 3 or more.
• organic isocyanate having two isocyanate groups in one molecule include diisocyanate monomers such as tolylene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, methyl-2,6-diisocyanato hexanoate and norbornane diisocyanate.
• diisocyanate monomers such as tolylene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethylhe
• organic isocyanate having three or more isocyanate groups in one molecule include isocyanate prepolymers such as a compound represented by the following general formula (1) obtained by subjecting a diisocyanate monomer to isocyanurate modification, a compound represented by the following general formula (2) obtained by subjecting a diisocyanate monomer to adduct modification, a compound represented by the following general formula (3) obtained by subjecting a diisocyanate monomer to biuret modification, 2-isocyanatoethyl-2,6-diisocyanatocaproate, and triaminononane triisocyanate.
• isocyanate prepolymers such as a compound represented by the following general formula (1) obtained by subjecting a diisocyanate monomer to isocyanurate modification, a compound represented by the following general formula (2) obtained by subjecting a diisocyanate monomer to adduct modification, a compound represented by the following general formula (3) obtained by subjecting a diisocyanate monomer
• R represents
• R has the same meaning as defined in the above general formula (1).
• the polycaprolactone-modified alkyl(meth)acrylate is a compound represented by the following general formula (4) and has an actinic energy ray-curable functional group such as a terminal methylene group (CH 2 ⁇ )
• Specific examples of the polycaprolactone-modified alkyl(meth)acrylate include a polycaprolactone-modified hydroxyethyl(meth)acrylate, a polycaprolactone-modified hydroxypropyl(meth)acrylate, and a polycaprolactone-modified hydroxybutyl(meth)acrylate.
• R represents H or CH 3 , n is an integer of 1 to 10, and m is an integer of 1 to 25.
• the actinic energy ray-curable composition can be used as paints and coating agents for products where scratch resistance is required. More specifically, the actinic energy ray-curable composition is applied (painted or coated) onto electrical or electronic apparatus such as cell phones, watches, compact disks, optical disks, audio equipment, and office automation equipment; electronic material parts such as touch panels, and antireflection board for cathode ray tubes; household electrical appliances such as refrigerators, vacuum cleaners, and microwave ovens; interior of automobiles such as meter panels and dashboards; pre-coated metal steel plates; vehicular parts such as automobile bodies, bumpers, spoilers, door knobs, steering wheels, head lamps, fuel tanks of motorcycles, plated, vapor-deposited, or sputtered aluminum wheels, and door mirrors; roofs of carports and roofs for natural lighting; molded products of plastics such as polyvinyl chloride, acrylic resin, polyethylene terephthalate, polycarbonate, and ABS resin; wood products such as stairs, floors, tables, chairs, chests, and other furniture
• the actinic energy ray-curable composition is applied according to known methods such as air spraying, airless spraying, electrostatic coating, roll coater, flow coater, and spin coating.
• the thickness of the coated film is preferably from about 1 to 100 ⁇ m.
• the actinic energy ray-curable composition is cured by irradiation with an actinic energy ray such as an ultraviolet ray and an electron beam.
• the irradiation with an ultraviolet ray is preferably conducted using a UV light source such as a mercury lamp and a metal halide lamp so that the curing energy (integral light intensity) becomes from 100 to 1000 mJ/cm 2 .
• the irradiation with an electron beam is preferably conducted at an accelerating voltage of 150 to 250 keV so that the dose becomes from 1 to 5 Mrad.
• the cured product of the actinic energy ray-curable composition according to the first embodiment is molded into a predetermined shape or a cured layer made of the actinic energy ray-curable composition is provided on the surface of a substrate, the functional member and the optical member according to the first embodiment are formed.
• the cured layer itself may function as a functional member or an optical member or may be one for protecting a substrate functioning as a functional member or an optical member.
• the functional member is a member having some kind of useful characteristic.
• Specific examples of the functional member include light reflective film, antireflection film, polarizing film, light diffusing film, phase contrast film, film for adjusting angle of visibility, heat reflective film, ultraviolet ray shielding film, electromagnetic wave shielding film, and film for touch sensors.
• the optical member is a member having a useful optical characteristic. Specific examples of the optical member include light reflective film, antireflection film, polarizing film, light diffusing film, phase contrast film, and film for adjusting angles of visibility.
• the actinic energy ray-curable composition is cured by irradiation with an actinic energy ray such as an ultraviolet ray and an electron beam.
• an actinic energy ray such as an ultraviolet ray and an electron beam.
• Preferable irradiation conditions for an actinic energy ray at this time are as described above.
• the first embodiment has the following advantages.
• a maximum scratch load is defined as a critical load where when a scratch mark is made on a test specimen using a diamond indenter having a tip diameter of 15 ⁇ m, the scratch mark can be repaired by a self-repairing ability of the test specimen under an atmosphere at 25° C. and at a relative humidity of 50%.
• the value of the critical load is larger than that in a cured product of a conventional ultraviolet-curable composition.
• the value of the critical load measured using the cured product (cured film) having a thickness of 60 ⁇ m formed from the actinic energy ray-curable composition according to the first embodiment is at least 235 mN (24 gf) or more, and optionally 390 mN (40 gf) or more. Since the cured product has excellent scratch resistance as described above, the actinic energy ray-curable composition according to the first embodiment is useful as paints or coating agents for products where scratch resistance is particularly strongly required.
• an actinic energy ray-curable composition according to a second embodiment is described mainly with respect to points differing from the actinic energy ray-curable composition according to the first embodiment.
• the actinic energy ray-curable composition according to the second embodiment contains a urethane(meth)acrylate obtained by reacting an organic isocyanate with two or more kinds of polycaprolactone-modified alkyl(meth)acrylates different from each other in the number of repetitions of a caprolactone unit per one molecule.
• the average of the number of repetitions of the caprolactone unit per one molecule of the polycaprolactone-modified alkyl(meth)acrylate is preferably in a range of from 1 to 5, more preferably in a range of from 1 to 2.5.
• the maximum difference in the number of repetitions of the caprolactone unit between two kinds of the polycaprolactone-modified alkyl(meth)acrylates is preferably 9 or less, more preferably in a range of from 4 to 9.
• a functional member and an optical member according to the second embodiment are described mainly with respect to points differing from the functional member and the optical member according to the first embodiment.
• a cured product of the actinic energy ray-curable composition according to the second embodiment is molded into a predetermined shape or a cured layer made of the actinic energy ray-curable composition is provided on the surface of a substrate, a functional member and optical member according to the second embodiment are formed.
• the second embodiment has the following advantages.
• the actinic energy ray-curable composition according to the second embodiment has the same advantages as in (a) and (b) described in the description of the first embodiment.
• an actinic energy ray-curable composition according to a third embodiment is described mainly with respect to points differing from the actinic energy ray-curable compositions according to the first and second embodiments.
• the actinic energy ray-curable composition according to the third embodiment contains a urethane(meth)acrylate obtained by reacting an organic isocyanate with a polycaprolactone-modified alkyl(meth)acrylate, and a urethane (meth)acrylate obtained by reacting an organic isocyanate with a hydroxyalkyl(meth)acrylate.
• hydroxyalkyl(meth)acrylate examples include a compound represented by the following general formula (5) such as hydroxyethyl(meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl(meth)acrylate.
• R represents H or CH 3 and 1 is an integer of 1 to 10.
• the hydroxyalkyl(meth)acrylate can be considered as a (meth)acrylate monomer where the number of repetitions of the caprolactone unit is zero.
• the average number of repetitions per one molecule of the urethane(meth)acrylate relative to the number of repetitions of the caprolactone unit per one residue of the (meth)acrylate monomer is preferably in a range of from 1 to 5, more preferably in a range of from 1 to 2.5.
• the maximum difference in the number of repetitions of the caprolactone unit per one residue of the (meth)acrylate monomer between two kinds of the urethane(meth)acrylates is preferably 9 or less, more preferably in the range of from 4 to 9.
• a functional member and an optical member according to the third embodiment are described mainly with respect to points differing from the functional member and the optical member according to the first embodiment.
• a cured product of the actinic energy ray-curable composition according to the third embodiment is molded into a predetermined shape or a cured layer made of the actinic energy ray-curable composition is provided on the surface of a substrate, the functional member and the optical member according to the third embodiment are formed.
• the third embodiment has the following advantages.
• the actinic energy ray-curable composition according to the third embodiment has the same advantages as in (a), described above in the description of the first embodiment.
• an actinic energy ray-curable composition according to a fourth embodiment is described mainly with respect to points differing from the actinic energy ray-curable compositions according to the first to third embodiments.
• An actinic energy ray-curable composition according to the fourth embodiment contains a urethane(meth)acrylate obtained by reacting an organic isocyanate with a polycaprolactone-modified alkyl(meth)acrylate and a hydroxyalkyl(meth)acrylate.
• the actinic energy ray-curable composition according to the fourth embodiment contains a urethane(meth)acrylate obtained by reacting an organic isocyanate with two or more kinds of (meth)acrylate monomers different from each other in the number of repetitions of a caprolactone unit per one molecule.
• the average of the number of repetitions of the caprolactone unit per one molecule of the (meth)acrylate monomer is preferably in a range of from 1 to 5, more preferably in a range of from 1 to 2.5.
• the maximum difference in the number of repetitions of the caprolactone unit between two kinds of the (meth)acrylate monomers is preferably 9 or less, more preferably in a range of from 4 to 9.
• a functional member and an optical member according to the fourth embodiment are described mainly with respect to points differing from the functional member and the optical member according to the first embodiment.
• a cured product of the actinic energy ray-curable composition according to the fourth embodiment is molded into a predetermined shape or a cured layer made of the actinic energy ray-curable composition is provided on the surface of a substrate, a functional member and an optical member according to the fourth embodiment are formed.
• the fourth embodiment has the following advantages.
• the actinic energy ray-curable composition according to the fourth embodiment has the same advantages as in (a), described above in the description of the first embodiment.
• a synthesis reaction of the urethane(meth)acrylate may be performed in a solvent.
• the solvent include aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and ester solvents such as ethyl acetate, propyl acetate, isobutyl acetate, and butyl acetate.
• a catalyst or a polymerization inhibitor may be used.
• the catalyst include dibutyltin laurate, dibutyltin diethylhexoate, and dibutyltin sulfite.
• the polymerization inhibitor include hydroquinone monomethyl ether.
• a long-chain alcohol may be added.
• the addition of the long-chain alcohol improves surface smoothness of the cured product of the actinic energy ray-curable composition, and as a result, it improves scratch resistance of the cured product.
• long-chain alcohol examples include tridecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, polyoxyethylene monostearate, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and glycerol monostearate.
• Preferable long-chain alcohol is a long-chain alcohol subjected to polyether modification, such as a polyether-modified cetyl alcohol. The addition of the long-chain alcohol subjected to polyether modification imparts an antistatic effect to the cured product made of the actinic energy ray-curable composition.
• Each actinic energy ray-curable composition according to the embodiments described above may further contain any one of a long-chain alkyl group-containing compound, a silicone compound, and a fluorine compound.
• the long-chain alkyl group-containing compound, the silicone compound, and the fluorine compound improve surface smoothness of the cured product of the actinic energy ray-curable composition, and as a result, they improve scratch resistance of the cured product.
• the long-chain alkyl group-containing compound, the silicone compound, and the fluorine compound each preferably have an actinic energy ray-curable functional group.
• the long-chain alkyl group-containing compound, the silicone compound, and the fluorine compound each having the actinic energy ray-curable functional group reduce the viscosity of the actinic energy ray-curable composition and make the composition highly solid. They further improve adhesion to a substrate and solvent resistance, in the cured product of the actinic energy ray-curable composition.
• the number of carbon atoms of the long-chain alkyl group contained in the long-chain alkyl group-containing compound is preferably from 13 to 25. This is because the scratch resistance of the cured product made of the actinic energy ray-curable composition is further improved.
• the long-chain alkyl group-containing compound having 13 to 25 carbon atoms include a long-chain alcohol such as tridecanol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, polyoxyethylene cetyl alcohol, polyoxyethylene stearyl alcohol, and glycerol monostearate; and an actinic energy ray-curable compound such as tridecyl (meth)acrylate, myristyl(meth)acrylate, cetyl(meth)acrylate, stearyl(meth)acrylate, behenyl(meth)acrylate, and stearoxypolyethylene glycol mono(meth)acrylate.
• the actinic energy ray-curable compound has an actinic energy ray-curable functional group.
• silicone compound examples include polydimethylsiloxane, alkyl-modified polydimethylsiloxane, carboxyl-modified polydimethylsiloxane, amino-modified polydimethylsiloxane, epoxy-modified polydimethylsiloxane, fluorine-modified polydimethylsiloxane, and (meth)acrylate-modified polydimethylsiloxane (e.g., “GUV-235”, trade name, produced by Toagosei Co., Ltd.).
• the fluorine compound include compounds having a fluoroalkyl group such as fluoroalkyl carboxylate, fluoroalkyl quaternary ammonium salt, and fluoroalkyl ethylene oxide adduct; compounds having a perfluoroalkyl group such as perfluoroalkyl carboxylate, perfluoroalkyl quaternary ammonium salt, and perfluoroalkyl ethylene oxide adduct; compounds having a fluorocarbon group; tetrafluoroethylene polymers; copolymers of vinylidene fluoride with tetrafluoroethylene; copolymers of vinylidene fluoride with hexafluoropropylene; fluorine-containing (meth)acrylic acid ester; polymers of fluorine-containing (meth)acrylic acid ester; polymers of fluorine-containing alkyl(meth)acrylate; and copolymers of fluorine-containing (meth)acrylic acid
• Each actinic energy ray-curable composition according to the embodiments described above may further contain an actinic energy ray-curable functional group-containing compound.
• the actinic energy ray-curable functional group-containing compound reduces the viscosity of the actinic energy ray-curable composition and makes the composition highly solid.
• the compound further improves adhesion to a substrate and solvent resistance, in the cured product made of the actinic energy ray-curable composition.
• actinic energy ray-curable functional group-containing compound examples include monofunctional and polyfunctional monomers each having a (meth)acryloyl group, and monofunctional and polyfunctional oligomers each having a (meth)acryloyl group.
• examples thereof include monofunctional monomers such as phthalic acid monohydroxyethyl(meth)acrylate, 2-ethoxyhexyl(meth)acrylate, phenoxyethyl(meth)acrylate, 2-ethoxyethyl(meth)acrylate, 2-ethoxyethoxyethyl(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate, polycaprolactone-modified hydroxyethyl(meth)acrylate, dicyclopentenyloxyethyl(meth)acrylate, N-vinylpyrrolidone, acryloylmorpholine, isobornyl(meth)acrylate, vinyl acetate, and styrene; difunctional monomers such as neopentyl glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,6-hexanediol di(
• actinic energy ray-curable functional group-containing compound further include phenylphenolethoxy(meth)acrylate, phenylphenoldiethoxy (meth)acrylate, phenylphenolpentaethoxy(meth)acrylate, 1,3-bis[2-methacryloyloxy-3-(2,4,6-tribromophenoxy)propoxy]benzene, bisphenoxyethanolfluorene di(meth)acrylate, urethane (meth)acrylate having fluorene skeleton and (meth)acrylate of ⁇ -caprolactone adduct having fluorene skeleton; and sulfur-containing (meth)acrylate such as 4,4′-bis(4-hydroxyphenyl)sulfone di(meth)acrylate, 4,4′-bis(4-hydroxyethoxyphenyl)sulfone di(meth)acrylate, 2,5-diacryloyloxy-1,4-dithiane, bis-2-(meth)
• Each actinic energy ray-curable composition according to the embodiments described above may further contain a photoinitiator.
• the photoinitiator improves curing characteristics of the actinic energy ray-curable composition such as acceleration of cure rate.
• Specific examples of the photoinitiator include isopropylbenzoin ether, isobutylbenzoin ether, benzophenone, Michler's ketone, o-benzoylmethyl benzoate, acetophenone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, ethylanthraquinone, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, 1-hydroxycyclohexyl phenyl ketone (for example, “Irgacure 184” produced by Ciba Specialty Chemicals Inc.), 2-hydroxy-2-methyl-1-
• Each actinic energy ray-curable composition according to the embodiments described above may further contain beads.
• the beads impart an antireflection effect to the cured product of the actinic energy ray-curable composition.
• Specific examples of the beads include beads each made of a synthetic resin such as polymethyl methacrylate, nylon, polyurethane, silicone, or polycarbonate, or a rubber; beads each made of a metal such as titanium oxide, titanium dioxide, aluminum oxide, tin oxide, indium oxide, zinc oxide, antimony oxide, antimony-containing tin oxide, or tin-containing indium oxide; and beads each made of silicon dioxide or glass.
• Each actinic energy ray-curable composition according to the embodiments described above may further contain an antistatic agent.
• the antistatic agent imparts an antistatic effect to the cured product of the actinic energy ray-curable composition.
• Specific examples of the antistatic agent include anionic antistatic agents such as alkyl phosphates, cationic antistatic agents such as quaternary ammonium salts, nonionic antistatic agents such as polyoxyethylene alkyl ethers, and antistatic agents containing salts of an alkali metal such as lithium, sodium, or potassium.
• a preferable antistatic agent is one containing a lithium salt.
• Each actinic energy ray-curable composition according to the embodiments described above may further contain a solvent, a leveling agent, or an ultraviolet absorber.
• the solvent include aromatic hydrocarbon solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, isopropyl alcohol, n-butanol, and isobutanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as ethyl acetate, propyl acetate, butyl acetate, and isobutyl acetate.
• leveling agent examples include acrylic copolymers and silicone leveling agents and fluorine leveling agents.
• ultraviolet absorber examples include benzophenone-based, benzotriazole-based, oxalic anilide-based, triazine-based, and hindered amine-based ultraviolet absorbers.
• Part(s) means “part(s) by weight”.
• urethane acrylate having a solid content of 50% by weight.
• the number of repetitions of a caprolactone unit per one residue of the acrylate monomer in the obtained urethane acrylate is 2.
• urethane acrylate having a solid content of 50% by weight.
• the number of repetitions of a caprolactone unit per one residue of the acrylate monomer in the obtained urethane acrylate is 3.
• toluene 50 parts of toluene, 50 parts of hexamethylene diisocyanate subjected to isocyanurate modification (“TAKENATE D-170N”), 179 parts of polycaprolactone-modified hydroxyethyl acrylate (“PLACCEL FA5”, trade name, produced by Daicel Chemical Industries, Ltd.), 0.02 parts of dibutyltin laurate, and 0.02 parts of hydroquinone monomethyl ether were mixed and the mixture was maintained at 70° C. for 5 hours. Thereafter, 179 parts of toluene was added to obtain a urethane acrylate having a solid content of 50% by weight. The number of repetitions of a caprolactone unit per one residue of the acrylate monomer in the obtained urethane acrylate is 5.
• toluene 50 parts of toluene, 25 parts of hexamethylene diisocyanate subjected to isocyanurate modification (“TAKENATE D-170N”), 162.8 parts of polycaprolactone-modified hydroxyethyl acrylate (“PLACCEL FA10”, trade name, produced by Daicel Chemical Industries, Ltd.), 0.02 parts of dibutyltin laurate, and 0.02 parts of hydroquinone monomethyl ether were mixed and the mixture was maintained at 70° C. for 5 hours. Thereafter, 137.8 parts of toluene was added to obtain a urethane acrylate having a solid content of 50% by weight. The number of repetitions of a caprolactone unit per one residue of the acrylate monomer in the obtained urethane acrylate is 10.
• toluene 25 parts of toluene, 25 parts of hexamethylene diisocyanate subjected to isocyanurate modification (“TAKENATE D-170N”), 32 parts of 2-hydroxyethyl acrylate (“LIGHT ESTER HOA”, trade name, produced by KYOEISHA CHEMICAL Co., LTD), 0.02 parts of dibutyltin laurate, and 0.02 parts of hydroquinone monomethyl ether were mixed and the mixture was maintained at 70° C. for 5 hours. Thereafter, 32 parts of toluene was added to obtain a urethane acrylate having a solid content of 50% by weight. The number of repetitions of a caprolactone unit per one residue of the acrylate monomer in the obtained urethane acrylate is 0.
• PLACCEL FA1 polycaprolactone-modified hydroxyethyl acrylate
• 0.02 parts of dibutyltin laurate and 0.02 parts of hydroquinone monomethyl ether were added and the mixture was maintained at 70° C. for 3 hours. Thereafter, 56.2 parts of toluene was added to obtain a urethane acrylate having a solid content of 50% by weight.
• the number of repetitions of a caprolactone unit per one residue of the acrylate monomer in the obtained urethane acrylate is 1.
• the average number of repetitions per one molecule of the urethane acrylate relative to the number of repetitions of a caprolactone unit per one residue of an acrylate monomer is 1.5. Further, the maximum difference in the number of repetitions between two kinds of the urethane acrylates is 2.
• the average number of repetitions per one molecule of the urethane acrylate relative to the number of repetitions of a caprolactone unit per one residue of an acrylate monomer is 1.5. Further, the maximum difference in the number of repetitions between two kinds of the urethane acrylates is 4.
• urethane acrylate having a solid content of 50% by weight.
• the average number of repetitions per one molecule of the urethane acrylate relative to the number of repetitions of a caprolactone unit per one residue of an acrylate monomer is 2. Further, the maximum difference in the number of repetitions between two kinds of the urethane acrylates is 10.
• the average number of repetitions per one molecule of the urethane acrylate relative to the number of repetitions of a caprolactone unit per one residue of an acrylate monomer is 2. Further, the maximum difference in the number of repetitions between two kinds of the urethane acrylates is 5.
• urethane acrylate having a solid content of 50% by weight.
• the average number of repetitions per one molecule of the urethane acrylate relative to the number of repetitions of a caprolactone unit per one residue of an acrylate monomer is 2. Further, the maximum difference in the number of repetitions between two kinds of the urethane acrylates is 19.
• the average number of repetitions per one molecule of the urethane acrylate contained in the actinic energy ray-curable composition, relative to the number of repetitions of a caprolactone unit per one residue of an acrylate monomer is 1.5. Further, the difference in the number of repetitions between two kinds of the urethane acrylates contained in this actinic energy ray-curable composition is 2.
• an actinic energy ray-curable composition having a solid content of 50% by weight.
• the average number of repetitions per one molecule of the urethane acrylate contained in the actinic energy ray-curable composition, relative to the number of repetitions of a caprolactone unit per one residue of an acrylate monomer is 2. Further, the difference in the number of repetitions between two kinds of the urethane acrylates contained in this actinic energy ray-curable composition is 9.
• the average number of repetitions per one molecule of the urethane acrylate contained in the actinic energy ray-curable composition, relative to the number of repetitions of a caprolactone unit per one residue of an acrylate monomer is 1.5. Further, the difference in the number of repetitions between two kinds of the urethane acrylates contained in the actinic energy ray-curable composition is 5.
• an actinic energy ray-curable composition having a solid content of 50% by weight.
• the average number of repetitions per one molecule of the urethane acrylate contained in the actinic energy ray-curable composition, relative to the number of repetitions of a caprolactone unit per one residue of an acrylate monomer is 1.5. Further, the maximum difference in the number of repetitions between urethane acrylates contained in the actinic energy ray-curable composition is 2.
• the average number of repetitions per one molecule of the urethane acrylate contained in the actinic energy ray-curable composition, relative to the number of repetitions of a caprolactone unit per one residue of an acrylate monomer is 1.5. Further, the maximum difference in the number of repetitions between urethane acrylates contained in this actinic energy ray-curable composition is 4.
• an actinic energy ray-curable composition having a solid content of 50% by weight.
• the average number of repetitions per one molecule of the urethane acrylate contained in the actinic energy ray-curable composition, relative to the number of repetitions of a caprolactone unit per one residue of an acrylate monomer is 2.0. Further, the maximum difference in the number of repetitions between urethane acrylates contained in this actinic energy ray-curable composition is 5.
• an actinic energy ray-curable composition having a solid content of 50% by weight.
• the average number of repetitions per one molecule of the urethane acrylate contained in the actinic energy ray-curable composition, relative to the number of repetitions of a caprolactone unit per one residue of an acrylate monomer is 2. Further, the maximum difference in the number of repetitions between urethane acrylates contained in this actinic energy ray-curable composition is 19.
• the average number of repetitions per one molecule of the urethane acrylate contained in the actinic energy ray-curable composition, relative to the number of repetitions of a caprolactone unit per one residue of an acrylate monomer is 4.5. Further, the maximum difference in the number of repetitions between urethane acrylates contained in this actinic energy ray-curable composition is 4.
• an actinic energy ray-curable composition having a solid content of 50% by weight.
• the average number of repetitions per one molecule of the urethane acrylate contained in the actinic energy ray-curable composition, relative to the number of repetitions of a caprolactone unit per one residue of an acrylate monomer is zero.
• urethane acrylate (“M-1100”, trade name, produced by Toagosei Co., Ltd.), 65 parts of polycaprolactone-modified hydroxyethyl acrylate (“PLACCEL FA2D”), 100 parts of toluene, and 6 parts of a photoinitiator (“IRGACURE 184”) were mixed to prepare an actinic energy ray-curable composition having a solid content of 50% by weight.
• the average number of repetitions per one molecule of the urethane acrylate contained in the actinic energy ray-curable composition, relative to the number of repetitions of a caprolactone unit per one residue of an acrylate monomer is zero.
• urethane acrylate (“M-1200”, trade name, produced by Toagosei Co., Ltd.), 32 parts of polycaprolactone-modified hydroxyethyl acrylate (“PLACCEL FA5”), 100 parts of toluene, and 6 parts of a photoinitiator (“IRGACURE 184”) were mixed to prepare an actinic energy ray-curable composition having a solid content of 50% by weight.
• the average number of repetitions per one molecule of the urethane acrylate contained in the actinic energy ray-curable composition, relative to the number of repetitions of a caprolactone unit per one residue of an acrylate monomer is zero.
• compositions prepared in Examples 1 to 10 and Comparative Examples 1 to 6 were subjected to evaluation and measurement on each of the following items (1) to (14). The results thereof are shown in the following table 2.
• a cured layer having a thickness of 10 ⁇ m made of each composition was provided to prepare a test plate.
• TC-H3DPK trade name, produced by Tokyo Denshoku K.K.
• test plate where a measured value was 0/100 was evaluated as ⁇
• test plate where the measured value was from 1/100 to less than 5/100 was evaluated as ⁇
• test plate where the measured value was from 5/100 to less than 10/100 was evaluated as ⁇
• test plate where the measured value was from 10/100 to less than 20/200 was evaluated as ⁇
• test plate where the measured value was 20/100 or more was evaluated as x.
• a haze value of each test plate was measured before and after treatment where the above-described test plate was left under an atmosphere at 50° C. and at a relative humidity of 98% for 50 hours.
• a test plate where a value obtained by subtracting a haze value measured before the treatment from a haze value measured after the treatment was less than 5% was evaluated as ⁇
• a test plate where the value was from 5 to 10% was evaluated as ⁇
• a test plate where the value was from 10 to 20% was evaluated as ⁇
• a test plate where the value was from 20 to 30% was evaluated as ⁇
• a test plate where the value was 30% or more was evaluated as x.
• Solvent resistance was evaluated by rubbing each of the test plates back and forth 10 times with a wiper (“KIMWIPE”, trade name, produced by Crecia Corporation) soaked with toluene.
• a test plate where no scratch or adhesion of fiber of the wiper was found was evaluated as ⁇
• a test plate where scratch or adhesion of fiber of the wiper was slightly found was evaluated as ⁇
• a test plate where scratch or adhesion of fiber of the wiper was remarkably found was evaluated as x.
• Scratch resistance was evaluated by measuring a haze value (%) of each test plate rubbed back and forth 30 times at a load of 500 g using #0000 steel wool.
• Self-repairing ability was evaluated by allowing test plates scratched with a nail to stand at room temperature for 30 minutes. A test plate where the scratch was repaired was evaluated as ⁇ , and a test plate where the scratch was not repaired was evaluated as x.
• test plate having a cut face where no burr was generated was evaluated as ⁇
• test plate having a cut face where a burr was generated was evaluated as x.
• Curling depth (mm) was measured by making a cross cut with a 2 cm square size in the center of a test plate cut into a size of 10 cm square.
• Flexure resistance was evaluated by bending each of the test plates at 180 degrees by a vice such that one sheet of material with the same thickness as the test plate was caught in the test plate.
• a test plate having a cured layer where no damage such as crack or fracture was generated was evaluated as ⁇ , and a test plate having a cured layer where damage such as crack or fracture was generated was evaluated as x.
• a haze value of each test plate was measured before and after the treatment where cotton wool impregnated with 0.1 N sulfuric acid was left on each of the test plates under an atmosphere at 25° C. for 24 hours.
• the test plate where a value obtained by subtracting a haze value measured before the treatment from a haze value measured after the treatment was less than 5% was evaluated as ⁇ , a test plate where the value was from 5 to 10% was evaluated as ⁇ , a test plate where the value was from 10 to 20% was evaluated as ⁇ , a test plate where the value was from 20 to 30% was evaluated as ⁇ , and a test plate where the value was 30% or more was evaluated as x.
• a haze value of each test plate was measured before and after the treatment where cotton wool impregnated with 0.1 N sodium hydroxide was left on each of the test plates under an atmosphere at 25° C. for 24 hours.
• a test plate where a value obtained by subtracting a haze value measured before the treatment from a haze value measured after the treatment was less than 5% was evaluated as ⁇ , a test plate where the value was from 5 to 10% was evaluated as ⁇ , a test plate where the value was from 10 to 20% was evaluated as ⁇ , a test plate where the value was from 20 to 30% was evaluated as ⁇ , and a test plate where the value was 30% or more was evaluated as x.
• Productivity was evaluated by time required to cure each composition coated on an easily-adhesive polyethylene terephthalate film during preparing each of the test plates. A test plate where the time required was less than 1 minute was evaluated as 0, and a test plate where the time required was 1 minute or more was evaluated as x.
• a cured layer made of each of the compositions prepared in Examples 1 to 10 and Comparative Examples 1 to 6 was provided on the surface of an easily-adhered polyethylene terephthalate film having a thickness of 100 ⁇ m to prepare a test plate.
• the thickness of a cured layer made of the composition prepared in Comparative Example 5 was 20 ⁇ m, and the thickness of a cured layer other than this layer was 50 ⁇ m (this is because when the thickness of the cured layer made of the composition prepared in Comparative Example 5 exceeds 20 ⁇ m, the test plate was curled to generate fractures).
• the maximum scratch load (vertical load [mN]) where when a scratch mark was made on the cured layer of the test plate using a diamond indenter with a tip diameter of 15 ⁇ m, the scratch mark was capable of being repaired by self-repairing ability of the cured layer under an atmosphere at 25° C. and at a relative humidity of 50% was measured by means of a scratch tester produced by HEIDON Co.
• the unit of the measured value in parenthesis shown in Table 2 is gf. TABLE 2 2. 1. Coated 3. 4. 5. 6. 7. 9. 10. 11. 12. 13. Paint film Adhe- Moisture Solvent Scratch Self- 8. Curling Flexure Acid Alkali Pro- 14.
• Examples 1 to 10 were excellent in view of scratch resistance as compared with Comparative Examples 1 to 4 and Comparative Example 6, and had scratch resistance at the same level as Comparative Example 5 as a general hard coating agent. Further, with respect to the value of the critical load measured by the scratch test, all of Examples 1 to 10 were larger than Comparative Examples 1 to 4 and Comparative Example 6, and were the same level as Comparative Example 5. Further, there was such a tendency that Examples 1, 5, 7, 9 and 10 in which the maximum difference in the number of repetitions of the caprolactone unit per one residue of the acrylate monomer between two kinds of the urethane acrylates contained in the actinic energy ray-curable composition was out of the range of from 4 to 9 were slightly inferior to the other Examples in scratch resistance.
• Example 2 Onto one side of a polyethylene terephthalate film (“LUMIRROR T-60”, trade name, produced by Toray Industries, Inc.) having a thickness of 50 ⁇ m, the actinic energy ray-curable composition in Example 1 was coated to have a dry film thickness of 50 ⁇ m and cured to form a reflective resin layer. Next, 7 parts of barium sulfate and 3 parts of titanium dioxide were dispersed in 60 parts of a urethane polyester polyol resin (“BURNOCK D6-439”) to prepare a coating liquid. Onto the reflective resin layer, the coating liquid was coated to have a dry film thickness of 100 ⁇ m and cured to form a white resin layer.
• a polyethylene terephthalate film (“LUMIRROR T-60”, trade name, produced by Toray Industries, Inc.
• the actinic energy ray-curable composition in Example 2 was coated to have a dry film thickness of 100 ⁇ m and cured to form a lower resin layer.
• a photoinitiator (“IRGACURE 184”) was blended in 100 parts of “OPSTAR JM5010” (trade name, produced by JSR Co., Ltd.) to prepare a coating liquid.
• the coating liquid was coated by spin coating to have a dry film thickness of 0.1 ⁇ m and cured to form a layer having a low refractive index.
• the actinic energy ray-curable composition in Example 1 was coated to have a dry film thickness of 100 ⁇ m and cured to form a lower resin layer.
• a coating liquid comprising 10 parts of dipentaerythritol hexaacrylate (“M-400”), 200 parts of a titanium dioxide-dispersed liquid (200 parts of a 15% toluene solution) and 0.3 parts of a photoinitiator (“IRGACURE 184”) was prepared. Further, onto the lower resin layer, the coating liquid was coated by spin coating to have a dry film thickness of 0.1 ⁇ m and cured to form a layer having a high refractive index.
• a photoinitiator (“IRGACURE 184”) was blended in 100 parts of OPSTAR JM5010 to prepare a coating liquid.
• the coating liquid was coated by spin coating and cured to form a layer having a low refractive index.
• Example 3 Onto a triacetyl cellulose film (“FUJI TACK F-T-UV80”, trade name, produced by Fuji Photo Film Co., Ltd.) having a thickness of 80 ⁇ m, the actinic energy ray-curable composition in Example 3 was coated to have a dry film thickness of 60 ⁇ m and cured.
• FUJI TACK F-T-UV80 trade name, produced by Fuji Photo Film Co., Ltd.
• Example 3 10 parts of ultrafine particles ZnO was dispersed in 90 parts of the actinic energy ray-curable composition in Example 3 to prepare a coating liquid.
• a coating liquid Onto an existing polarizing plate consisting of a three-layered structure of a triacetyl cellulose film, polarizing element and a triacetyl cellulose film, the coating liquid was coated and cured.
• Example 4 35 parts of beads (“GM-0630H”, trade name, produced by Ganz Chemical Co., Ltd.) made of polymethyl methacrylate was dispersed in 100 parts of the actinic energy ray-curable composition in Example 4 to prepare a coating liquid. Onto a polyethylene terephthalate film (“Lumirror T-60”) having a thickness of 50 ⁇ m, the coating liquid was coated to have a dry film thickness of 15 ⁇ m and cured.
• beads GM-0630H”, trade name, produced by Ganz Chemical Co., Ltd.
• Example 4 Onto an existing light-diffusing film, the actinic energy ray-curable composition in Example 4 was coated and cured.
• Example 6 Onto a film prepared by uni-axially stretching a polycarbonate film having a thickness of 100 ⁇ m up to from 1.15 to 1.25 times, the actinic energy ray-curable composition in Example 6 was coated and cured.
• Example 7 Onto a polyethylene terephthalate film having a thickness of 188 ⁇ m (“A4100”, trade name, produced by Toyobo Co., Ltd.), the actinic energy ray-curable composition in Example 7 was coated to have a dry film thickness of 60 ⁇ m and cured.
• A4100 trade name, produced by Toyobo Co., Ltd.
• the actinic energy ray-curable composition of the present invention is useful as paints or coating agents for products where scratch resistance is required.

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