CN113423749A - Curable composition for antiglare hardcoat - Google Patents

Curable composition for antiglare hardcoat Download PDF

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Publication number
CN113423749A
CN113423749A CN202080013197.6A CN202080013197A CN113423749A CN 113423749 A CN113423749 A CN 113423749A CN 202080013197 A CN202080013197 A CN 202080013197A CN 113423749 A CN113423749 A CN 113423749A
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hard coat
group
curable composition
mass
meth
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鹿内康史
原口将幸
松山元信
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Nissan Chemical Corp
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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
    • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
    • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements

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  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • Optics & Photonics (AREA)
  • Theoretical Computer Science (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides a material for forming a hard coat layer, which has excellent anti-glare property and scratch resistance and shows high initial hydrophobicity. A curable composition and a hard coat film provided with a hard coat layer formed from the composition, the curable composition comprising: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer; (b) a perfluoropolyether containing a poly (oxyperfluoroalkylene) group, the perfluoropolyether having an active energy ray-polymerizable group at both ends of the molecular chain thereof via a urethane bond being 0.05 to 10 parts by mass (with the exception of the perfluoropolyether having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond); (c) 5 to 40 parts by mass of fine particles having an average particle diameter of 0.2 to 15 μm; and (d) 1 to 20 parts by mass of a polymerization initiator that generates radicals using active energy rays.

Description

Curable composition for antiglare hardcoat
Technical Field
The present invention relates to a curable composition useful as a material for forming a hard coat layer applied to the surface of various display elements such as touch panel displays and liquid crystal displays, and more particularly to a curable composition capable of forming a hard coat layer excellent in abrasion resistance and anti-glare properties (anti-glare function) and also excellent in initial hydrophobicity.
Background
Products such as personal computers, mobile phones, portable game devices, and ATMs having touch panel displays mounted thereon are widely commercialized. In particular, with the advent of smart phones and tablet PCs, the number of capacitive touch panels having a multi-touch (multi-touch) function has increased.
In order to prevent a reduction in visibility due to reflection of external light on the screen, a method of bonding an antiglare hard coat film having a hard coat layer of about several μm with irregularities formed on the surface thereof to the surface of these touch panel displays has been used. As a method for forming irregularities on the surface, a method is generally used in which fine particles having a particle diameter of about several μm are contained in the hard coat layer.
However, the capacitive touch panel is operated by touching with a human finger. Therefore, there is a fear that the following problems occur: each time an operation is performed, a fingerprint is attached to the surface of the touch panel, which significantly impairs the visibility of an image of the display or impairs the appearance of the display. The fingerprint contains moisture derived from sweat and oil derived from sebum, and in order to make both of them difficult to adhere, it is strongly desired to impart hydrophobicity and oleophobicity to the hard coating layer of the display surface.
However, since a person touches the capacitive touch panel with a finger every day, even if the initial antifouling property reaches a high level, the display often suffers from scratches during use, which degrades the visibility of the image on the display and the antifouling property. In particular, since the hard-coated antiglare layer has irregularities on the surface thereof, the hard-coated antiglare layer is likely to be caught and easily scratched. Therefore, durability of antifouling property during use becomes a problem.
Heretofore, the following techniques have been disclosed: in a hard coat layer having antiglare properties and scratch resistance, a surface modifier having a poly (perfluoroalkylene oxide) structure and a (meth) acryloyl group in the molecule is used as a component for imparting antifouling properties and scratch resistance to the surface of the hard coat layer, and methyl methacrylate-styrene copolymer (MS) resin fine particles are used as a component for imparting antiglare properties to the hard coat layer (patent document 1). On the other hand, the following techniques are disclosed: as a component for imparting antiglare property to the hard coat layer, polymethyl methacrylate particles were used, using perfluoropolyether having active energy ray-polymerizable groups via urethane bonds at both ends of a molecular chain containing a poly (oxyperfluoroalkylene) group as a surface modifier (patent document 2).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2013-257359
Patent document 2: international publication No. 2016/163478
Disclosure of Invention
Problems to be solved by the invention
The method specifically described in patent document 1 has the following problems: the surface modifier having a poly (perfluoroalkylene oxide) structure and a (meth) acryloyl group in the molecule has a low fluorine content, and thus sufficient antifouling properties and scratch resistance cannot be obtained. Further, there are problems as follows: when the amount of MS resin particles added is reduced in order to obtain scratch resistance, sufficient antiglare properties cannot be obtained, and when MS resin particles are added to such an extent that sufficient antiglare properties can be obtained, scratch resistance is significantly reduced. Further, the dispersibility of the resin particles in the hard coat layer is poor, and the resin particles become aggregates to impair the appearance of the coating film. Further, the method specifically described in patent document 2 has the following problems: although scratch resistance and sufficient antiglare properties can be obtained, the initial water contact angle is insufficient and hydrophobicity is low. That is, a hard coat layer having excellent antiglare properties and scratch resistance and exhibiting high initial hydrophobicity has been desired.
Means for solving the problems
The present inventors have conducted extensive studies to achieve the above object, and as a result, have found that a hard coat layer having excellent antiglare properties and high scratch resistance and exhibiting high initial hydrophobicity can be formed by using a curable composition containing a perfluoropolyether as a fluorine-based surface modifier and fine particles added thereto, and have completed the present invention by finding that the perfluoropolyether contains a poly (oxyperfluoroalkylene) group, and the perfluoropolyether has an active energy ray-polymerizable group at both ends of the molecular chain thereof via a urethane bond without via the poly (oxyalkylene) group.
That is, the present invention relates to, as a first aspect, a curable composition comprising: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer; (b) a perfluoropolyether containing a poly (oxyperfluoroalkylene) group, the perfluoropolyether having an active energy ray-polymerizable group at both ends of the molecular chain thereof via a urethane bond being 0.05 to 10 parts by mass (with the exception of the perfluoropolyether having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond); (c) 5 to 40 parts by mass of fine particles having an average particle diameter of 0.2 to 15 μm; and (d) 1 to 20 parts by mass of a polymerization initiator that generates radicals using active energy rays.
A second aspect relates to the curable composition according to the first aspect, wherein the perfluoropolyether (b) has at least two active energy ray-polymerizable groups at each end of the molecular chain thereof via a urethane bond.
A third aspect relates to the curable composition according to the second aspect, wherein the perfluoropolyether (b) has at least three active energy ray-polymerizable groups at each end of the molecular chain thereof via a urethane bond.
A fourth aspect of the present invention relates to the curable composition according to any one of the first to third aspects, wherein the poly (oxyperfluoroalkylene) group has a repeating unit- [ OCF ]2]-and a repeating unit- [ OCF2CF2]Both of them are groups in which these repeating units are bonded in a block bonding, a random bonding, or a block bonding and a random bonding.
A fifth aspect relates to the curable composition according to the fourth aspect, wherein the perfluoropolyether (b) has a partial structure represented by the following formula [1 ].
Figure BDA0003200610890000031
(the above formula [1]]In which n represents a repeating unit- [ OCF ]2CF2]Number and repeating Unit- [ OCF ]2]-is an integer from 5 to 30, said repeating unit- [ OCF2CF2]-and said recurring unit- [ OCF2]The bonding is performed by block bonding, random bonding, or any of block bonding and random bonding. )
A sixth aspect relates to the curable composition of any one of the first to fifth aspects, wherein the fine particles of the component (c) are organic fine particles.
A seventh aspect of the present invention relates to the curable composition according to the sixth aspect, wherein the organic fine particles of the component (c) are polymethyl methacrylate fine particles.
An eighth aspect relates to the curable composition according to any one of the first to seventh aspects, further comprising (e) a solvent.
A ninth aspect relates to a cured film obtained from the curable composition according to any one of the first to eighth aspects.
A tenth aspect relates to a hard coat film comprising a hard coat layer formed from the cured film according to the ninth aspect on at least one side of a film base.
An eleventh aspect relates to the hard coat film according to the tenth aspect, wherein the hard coat layer has a layer thickness of 1 μm to 20 μm.
A twelfth aspect relates to the hard coat film according to the eleventh aspect, wherein the hard coat layer has a layer thickness of 3 μm to 15 μm.
A thirteenth aspect of the present invention relates to a method for producing a hard coat film, including a hard coat layer provided on at least one surface of a film base, the hard coat layer including: a step of applying the curable composition according to any one of the first to eighth aspects to a film substrate to form a coating film; and a step of irradiating the coating film with an active energy ray to cure the coating film.
A fourteenth aspect relates to a display comprising the hard coat film according to any one of the tenth to twelfth aspects.
A fifteenth aspect relates to a polarizing plate comprising the hard coat film according to any one of the tenth to twelfth aspects.
Effects of the invention
According to the present invention, it is possible to provide a curable composition which is useful for forming a cured film and a hard coat layer which have excellent scratch resistance and high antiglare properties even in a thin film having a thickness of about 1 μm to 20 μm, and which have excellent appearance and exhibit high initial hydrophobicity.
Further, the present invention can provide a hard coat film having a cured film obtained from the curable composition or a hard coat layer formed therefrom on the surface, and can provide a hard coat film having excellent antiglare properties, scratch resistance, and appearance, and excellent initial hydrophobicity.
Detailed Description
< curable composition >
More specifically, the curable composition of the present invention relates to a curable composition comprising: (a) 100 parts by mass of an active energy ray-curable polyfunctional monomer; (b) a perfluoropolyether containing a poly (oxyperfluoroalkylene) group, the perfluoropolyether having an active energy ray-polymerizable group at both ends of the molecular chain thereof via a urethane bond being 0.05 to 10 parts by mass (with the exception of the perfluoropolyether having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond); (c) 5 to 40 parts by mass of fine particles having an average particle diameter of 0.2 to 15 μm; and (d) 1 to 20 parts by mass of a polymerization initiator that generates radicals using active energy rays.
Hereinafter, the respective components (a) to (e) will be described first.
[ (a) active energy ray-curable polyfunctional monomer ]
The active energy ray-curable polyfunctional monomer is a monomer that is cured by a polymerization reaction by irradiation with an active energy ray such as ultraviolet ray.
In the curable composition of the present invention, the active energy ray-curable polyfunctional monomer (a) is preferably a monomer selected from the group consisting of polyfunctional (meth) acrylate compounds.
In the present invention, the (meth) acrylate compound means both of an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.
Examples of the polyfunctional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylateAlkenoic acid esters, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, ethoxylated glycerol tri (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, 1, 3-propanediol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 2-methyl-1, 8-octanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, 1, 10-decanediol di (meth) acrylate, mixtures thereof, Neopentyl glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tricyclo [5.2.1.02，6]Decane dimethanol di (meth) acrylate, dioxane diol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1, 3-di (meth) acryloyloxypropane, 9-bis [ 4- (2- (meth) acryloyloxyethoxy) phenyl]Fluorene, bis [ 4- (meth) acryloyl-thiophenyl]Thioether, bis [ 2- (meth) acryloylthioethyl]Thioether, 1, 3-adamantanediol di (meth) acrylate, 1, 3-adamantanedimethanol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate.
Among them, preferable polyfunctional (meth) acrylate compounds include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
In addition, examples of the polyfunctional (meth) acrylate compound include polyfunctional urethane (meth) acrylate compounds. The polyfunctional urethane (meth) acrylate compound has a plurality of acryloyl groups or methacryloyl groups in 1 molecule and has one or more urethane bonds (-NHCOO-).
Examples of the polyfunctional urethane (meth) acrylate compound include: a compound obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group, and a compound obtained by reacting a polyfunctional isocyanate with a (meth) acrylate having a hydroxyl group and a polyol, but the polyfunctional urethane (meth) acrylate compound that can be used in the present invention is not limited to these examples.
Examples of the polyfunctional isocyanate include tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, and hexamethylene diisocyanate.
Examples of the (meth) acrylate having a hydroxyl group include: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol hepta (meth) acrylate, and the like.
Examples of the polyol include: glycols such as ethylene glycol, propylene glycol, neopentyl glycol, 1, 4-butanediol, 1, 6-hexanediol, diethylene glycol, and dipropylene glycol; polyester polyols which are reaction products of these diols with aliphatic dicarboxylic acids such as succinic acid, maleic acid and adipic acid, or dicarboxylic anhydrides; a polyether polyol; a polycarbonate diol.
In the present invention, the active energy ray-curable polyfunctional monomer (a) may be used alone or in combination of two or more selected from the group consisting of the polyfunctional (meth) acrylate compound (compound containing no urethane bond) and the polyfunctional urethane (meth) acrylate compound. From the viewpoint of scratch resistance of the resulting cured product, it is preferable to use a polyfunctional (meth) acrylate compound (compound containing no urethane bond) and a polyfunctional urethane (meth) acrylate compound in combination.
Further, as the above-mentioned polyfunctional (meth) acrylate compound, it is preferable to use a polyfunctional (meth) acrylate compound having 5 or more functions and a polyfunctional (meth) acrylate compound having 4 or less functions in combination (in this case, the same applies hereinafter regardless of whether or not a urethane bond is contained).
Further, in the case where the above-mentioned polyfunctional (meth) acrylate compound (compound not containing a urethane bond) and the above-mentioned polyfunctional urethane (meth) acrylate compound are used in combination, the polyfunctional urethane (meth) acrylate compound is preferably used in an amount of 20 to 100 parts by mass, more preferably 30 to 70 parts by mass, relative to 100 parts by mass of the polyfunctional (meth) acrylate compound (compound not containing a urethane bond).
Further, in the case where the 5 or more functional polyfunctional (meth) acrylate compound and the 4 or less functional polyfunctional (meth) acrylate compound are used in combination in the above polyfunctional (meth) acrylate compound, it is preferable to use 10 to 100 parts by mass, more preferably 20 to 60 parts by mass of the 4 or less functional (meth) acrylate compound per 100 parts by mass of the 5 or more functional polyfunctional (meth) acrylate compound.
Further, it is preferable that: 20 to 100 parts by mass of a polyfunctional urethane (meth) acrylate compound per 100 parts by mass of a polyfunctional (meth) acrylate compound (a compound not containing a urethane bond), and 10 to 100 parts by mass of a 4-or-less polyfunctional (meth) acrylate compound per 100 parts by mass of a 5-or-more polyfunctional (meth) acrylate compound; 20 to 100 parts by mass of a polyfunctional urethane (meth) acrylate compound per 100 parts by mass of a polyfunctional (meth) acrylate compound (a compound not containing a urethane bond), and 20 to 60 parts by mass of a 4-or-less polyfunctional (meth) acrylate compound per 100 parts by mass of a 5-or-more polyfunctional (meth) acrylate compound; 30 to 70 parts by mass of a polyfunctional urethane (meth) acrylate compound per 100 parts by mass of a polyfunctional (meth) acrylate compound (a compound not containing a urethane bond), and 10 to 100 parts by mass of a 4-or-less polyfunctional (meth) acrylate compound per 100 parts by mass of a 5-or-more polyfunctional (meth) acrylate compound; the polyfunctional urethane (meth) acrylate compound is used in an amount of 30 to 70 parts by mass per 100 parts by mass of the polyfunctional (meth) acrylate compound (compound not containing a urethane bond), and the polyfunctional (meth) acrylate compound having 4 or less functions is used in an amount of 20 to 60 parts by mass per 100 parts by mass of the polyfunctional (meth) acrylate compound having 5 or more functions.
[ (b) a perfluoropolyether having a poly (oxyperfluoroalkylene) group having an active energy ray-polymerizable group at both ends of the molecular chain via a urethane bond (except for the perfluoropolyether having a poly (oxyperfluoroalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond) ]
In the present invention, as the component (b), a perfluoropolyether containing a poly (oxyperfluoroalkylene) group having an active energy ray-polymerizable group via a urethane bond without via the poly (oxyalkylene) group at both ends of the molecular chain thereof (hereinafter, simply referred to as "(b) a perfluoropolyether having a polymerizable group at both ends of the molecular chain) is used. (b) The component (a) functions as a surface modifier in a hard coat layer to which the curable composition of the present invention is applied.
Further, the hard coat layer having a transparent appearance can be formed by suppressing the generation of white turbidity by the excellent compatibility of the component (b) and the component (a).
The poly (oxyalkylene) group is a group in which the number of repeating units of an oxyalkylene group is 2 or more and an 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 limitedThe number of carbon atoms is preferably 1 to 4. That is, the poly (oxyperfluoroalkylene) group means a group having a structure in which a divalent fluorocarbon group having 1 to 4 carbon atoms and an oxygen atom are alternately bonded, and the oxyperfluoroalkylene group means a group having a structure in which a divalent fluorocarbon group having 1 to 4 carbon atoms and an oxygen atom are bonded. Specifically, it includes- [ OCF ]2]- (perfluoromethylene oxide), - [ OCF2CF2]- (perfluoroethylene oxide), - [ OCF2CF2CF2]- (Oxoperfluoropropane-1, 3-diyl), [ OCF2C(CF3)F]- (perfluoropropane oxide-1, 2-diyl), and the like.
The above-mentioned oxyperfluoroalkylene group may be used singly or in combination of two or more, and in this case, the bonding of the multiple oxyperfluoroalkylene groups may be either of a block bonding and a random bonding.
Among them, it is preferable to use a poly (oxyperfluoroalkylene) group having- [ OCF ] as a poly (oxyperfluoroalkylene) group from the viewpoint of obtaining a cured film having good scratch resistance2]- (perfluoromethylene oxide) and- [ OCF2CF2]Both of (perfluoroethylene oxide) and (perfluoroethylene oxide) are groups of the repeating unit.
Among them, as the poly (oxyperfluoroalkylene) group, preferred is a poly (oxyperfluoroalkylene) group in which: - [ OCF2]And- [ OCF2CF2]-as [ repeating units: - [ OCF2]－]: [ repeating unit: - [ OCF2CF2]－]2: 1 to 1: 2, more preferably, in a ratio of about 1: the ratio of 1 comprises the groups of the above repeating units. The bonding of these repeating units may be either block bonding or random bonding.
The number of repeating units of the above-mentioned oxyperfluoroalkylene group is preferably in the range of 5 to 30, more preferably in the range of 7 to 21, in terms of the total number of repeating units thereof.
Further, the weight average molecular weight (Mw) of the above poly (oxyperfluoroalkylene) group as determined in terms of polystyrene by gel permeation chromatography is 1000 to 5000, preferably 1500 to 3000.
Examples of the active energy ray-polymerizable group include a (meth) acryloyl group and a vinyl group.
(b) The perfluoropolyether having polymerizable groups at both ends of the molecular chain is not limited to those having active energy ray-polymerizable groups such as one (meth) acryloyl group at both ends of the molecular chain, and may have two or more active energy ray-polymerizable groups at both ends of the molecular chain, and examples of the terminal structure containing an active energy ray-polymerizable group include structures represented by the following formulas [ a1] to [ a5], and structures in which acryloyl groups in these structures are substituted with methacryloyl groups.
Figure BDA0003200610890000091
Figure BDA0003200610890000101
Examples of the perfluoropolyether having a polymerizable group at both ends of the molecular chain (b) include compounds represented by the following formula [2 ].
Figure BDA0003200610890000102
(formula [2]]Wherein A represents the formula [ A1]]To the formula [ A5]PFPE represents one of the structures shown and structures in which an acryloyl group in their structures is substituted with a methacryloyl group, and the poly (oxyperfluoroalkylene) group (wherein, with L, a group represented by formula1The side directly bonded is an oxy terminal, and the side bonded to an oxygen atom is a perfluoroalkylene terminal. ) L is1Represents an alkylene group having 2 or 3 carbon atoms substituted with 1 to 3 fluorine atoms, m independently represents an integer of 1 to 5, L2Represents a residue of valence m +1 with OH removed from m +1 polyol. )
As the above alkylene group having 2 or 3 carbon atoms substituted with 1 to 3 fluorine atoms, for example, there may be mentionedList of-CH2CHF－、－CH2CF2－、－CHFCF2－、－CH2CH2CHF－、－CH2CH2CF2－、－CH2CHFCF2-, preferably-CH2CF2－。
As the above formula [2]Partial structure of the shown compound (A-NHC (═ O)mL2Examples of the "A", "B", and "B1" include]To the formula [ B12]The structure shown.
Figure BDA0003200610890000111
Figure BDA0003200610890000121
(in the formulae [ B1] to [ B12], A represents one of the structures represented by the formulae [ A1] to [ A5] and a structure in which an acryloyl group in the structures is substituted with a methacryloyl group.)
In the structures represented by formulae [ B1] to [ B12], formulae [ B1] and [ B2] correspond to the case where m is 1, formulae [ B3] to [ B6] correspond to the case where m is 2, formulae [ B7] to [ B9] correspond to the case where m is 3, and formulae [ B10] to [ B12] correspond to the case where m is 5.
Among them, the structure represented by the formula [ B3] is preferable, and the combination of the formula [ B3] and the formula [ A3] is particularly preferable.
As a particularly preferable structure of (b) the perfluoropolyether having a polymerizable group at both ends of the molecular chain, a compound having a partial structure represented by the following formula [1] can be exemplified.
Figure BDA0003200610890000122
The partial structure represented by the formula [1] corresponds to a portion where a — NHC (═ O) is removed from the compound represented by the formula [2 ].
Formula [1]Wherein n represents a repeating unit- [ OCF ]2CF2]Number and repeating Unit- [ OCF ]2]-preferably an integer ranging from 5 to 30, more preferably an integer ranging from 7 to 21. Furthermore, the repeating unit- [ OCF ]2CF2]The number and repeating units of- [ OCF ]2]The ratio of the quantities of-is preferably 2: 1 to 1: 2, more preferably about 1: 1, in the above range. The bonding of these repeating units may be either block bonding or random bonding.
In the present invention, (b) perfluoropolyether having polymerizable groups at both ends of the molecular chain is used in a proportion of 0.05 to 10 parts by mass, for example, in a proportion of 0.1 to 10 parts by mass, preferably in a proportion of 0.1 to 5 parts by mass, relative to 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer.
By using (b) the perfluoropolyether having polymerizable groups at both ends of the molecular chain in a proportion of 0.05 part by mass or more, sufficient scratch resistance can be imparted to the hard coat layer. Further, by using (b) perfluoropolyether having polymerizable groups at both ends of the molecular chain in a proportion of 10 parts by mass or less, the (a) active energy ray-curable polyfunctional monomer can be sufficiently compatible, and a hard coat layer with less white turbidity can be obtained.
The perfluoropolyether (b) having polymerizable groups at both ends of the molecular chain can be obtained, for example, by reacting hydroxyl groups present at both ends of the compound represented by the following formula [3] with an isocyanate compound having polymerizable groups, that is, a compound having isocyanate groups bonded to bonding bonds in the structures represented by the formulae [ a1] to [ a5] and in the structures in which the acryloyl groups in these structures are replaced with methacryloyl groups (for example, 2- (meth) acryloyloxyethyl isocyanate, 1-bis ((meth) acryloyloxymethyl) ethyl isocyanate) to form urethane bonds.
(HO)mL2-O-L1-PFPE-O-L1-O-L2(OH)m [3]
(formula [3]]Middle, PFPE, L1、L2And m represents a group represented by the formula [, ]2]The same meaning is used. )
The curable composition of the present invention may contain: (b) a perfluoropolyether containing a poly (oxyperfluoroalkylene) group, the perfluoropolyether having an active energy ray-polymerizable group at both ends of a molecular chain thereof via a urethane bond (wherein no poly (oxyalkylene) group is present between the poly (oxyperfluoroalkylene) group and the urethane bond), and in addition, the perfluoropolyether may contain: a perfluoropolyether that contains a poly (oxyperfluoroalkylene) group, the perfluoropolyether having an active energy ray-polymerizable group at one end (one end terminal) of its molecular chain via a urethane bond and a hydroxyl group at the other end (the other end terminal) of its molecular chain (wherein there is no poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond and between the poly (oxyperfluoroalkylene) group and the hydroxyl group.); a perfluoropolyether containing a poly (oxyperfluoroalkylene) group as represented by the above formula [3], the perfluoropolyether having hydroxyl groups at both ends of the molecular chain thereof (wherein no poly (oxyperfluoroalkylene) group is present between the poly (oxyperfluoroalkylene) group and the hydroxyl group) [ a compound having no active energy ray-polymerizable group ].
[ (c) microparticles having an average particle diameter of 0.2 μm to 15 μm ]
In the curable composition of the present invention, the fine particles having an average particle diameter of 0.2 to 15 μm (hereinafter, also simply referred to as "(c) fine particles") form the surface of the hard coat layer formed from the curable composition into an uneven shape to impart antiglare properties.
In the present invention, as the fine particles (c), organic fine particles, inorganic fine particles, and organic-inorganic composite fine particles can be used. Among these fine particles, organic fine particles are preferably used from the viewpoint of transparency. The organic fine particles can also play a role in controlling the haze value of the hard coat layer by controlling the difference between the refractive index thereof and the refractive index of the curable composition as a hard coat layer-forming material.
The shape of the fine particles (c) is not particularly limited, and may be, for example, substantially spherical in the form of beads or amorphous particles such as powder, but substantially spherical particles are preferable, substantially spherical particles having an aspect ratio of 1.5 or less are more preferable, and spherical particles are most preferable.
Examples of the organic fine particles include: polymethyl methacrylate microparticles (PMMA microparticles), silicone microparticles, polystyrene microparticles, polycarbonate microparticles, acrylic styrene microparticles, benzoguanamine microparticles, melamine microparticles, polyolefin microparticles, polyester microparticles, polyamide microparticles, polyimide microparticles, and polyvinyl fluoride microparticles. These organic fine particles may be used alone or in combination of two or more.
Of these organic fine particles, polymethyl methacrylate fine particles can be preferably used.
The average particle diameter of the (c) fine particles used in the present invention is in the range of 0.2 μm to 15 μm, for example, preferably in the range of 1 μm to 10 μm. Here, the average particle diameter (μm) means a 50% volume diameter (median diameter) measured by a laser diffraction/scattering method based on Mie theory. If the average particle diameter of the fine particles (c) is larger than the above numerical range, the image clarity of the display is lowered, and if the average particle diameter of the fine particles (c) is smaller than the above numerical range, sufficient antiglare properties are not obtained, and the problem of increased glare tends to occur. The particle size distribution of the fine particles (c) is not particularly limited, but monodisperse fine particles having uniform particle diameters are preferable.
The (c) fine particles preferably have a refractive index difference of 0 to 0.20 from a cured product of the (a) active energy ray-curable polyfunctional monomer, and the refractive index difference is more preferably 0 to 0.10.
The fine particles (c) are preferably selected so that the average particle diameter thereof satisfies the range of 0.1 to 1.0 of the average particle diameter b/film thickness a of the fine particles with respect to the film thickness of a cured film obtained from the curable composition of the present invention described later.
The organic fine particles may be those commercially available, and for example, the following may be used: TECHNLYMER (registered trademark) MBX series, TECHNLYMER SBX series, TECHNLYMER MSX series, TECHNLYMER SMX series, TECHNLYMER SSX series, TECHNLYMER BMX series, TECHNLYMER ABX series, TECHNLYMER ARX series, TECHNLYMER AFX series, TECHNLYMER MB series, TECHNLYMER MBP series, TECHNLYMER MB-C series, TECHNLYMER ACX series, TECHNLYMER ACP series [ made by hydropyrolysis product industry (strain) above ]; TOSPEARL (registered trademark) series [ manufactured by Momentive Performance Materials Japan (accumulated chemical industry Co., Ltd.) ]; EPOSTER (registered trademark) series, EPOSTER MA series, EPOSTER ST series, EPOSTER MX series [ manufactured by japan catalyst, ltd. ]; OPTBEADS (registered trademark) series [ manufactured by Nissan chemical industry Co., Ltd ]; flow beads series [ manufactured by Sumitomo Seiko Co., Ltd ]; toraypearl (registered trademark) PPS, Toraypearl PAI, Toraypearl PES, and Toraypearl EP [ all of the above products, manufactured by Toray corporation ]; 3M (registered trademark) Dyneon TF micropoders series [ manufactured by 3M Co. ]; chemisnow (registered trademark) MX series, Chemisnow MZ series, Chemisnow MR series, Chemisnow KMR series, Chemisnow KSR series, Chemisnow MP series, Chemisnow SX series, and Chemisnow SGP series [ manufactured by general research chemical Co., Ltd ]; TAFTIC (registered trademark) AR650 series, TAFTIC AR-750 series, TAFTIC FH-S series, TAFTIC A-20 series, TAFTIC YK series, TAFTIC ASF series, TAFTIC HU series, TAFTIC F series, TAFTIC C series, and TAFTIC WS series [ manufactured by Toyo Boseki Kabushiki Kaisha ]; ART PEARL (registered trademark) GR series, ART PEARL SE series, ART PEARL G series, ART PEARL GS series, ART PEARL J series, ART PEARL MF series, ART PEARL BE series [ all of which are manufactured by Tokyo industries (Ltd.) ]; shin-Etsu silicone (registered trademark) KMP series (manufactured by shin-Etsu chemical industry Co., Ltd.).
In the present invention, the (c) fine particles are used in a proportion of 5 to 40 parts by mass, for example, 5 to 30 parts by mass, preferably 8 to 25 parts by mass, relative to 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer.
[ (d) polymerization initiator generating free radical by active energy ray ]
In the curable composition of the present invention, the polymerization initiator which generates radicals by irradiation with an active energy ray such as an electron ray, an ultraviolet ray, or an X-ray (hereinafter, also simply referred to as "(d) polymerization initiator") is preferably a polymerization initiator which generates radicals by irradiation with an active energy ray.
Examples of the polymerization initiator (d) include: benzoins, alkylbenzones, thioxanthones, azos, azines, diazos, o-quinonediazines, acylphosphine oxides, oxime esters, organic peroxides, 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.
Among them, in the present invention, alkylbenzophenones are preferably used as the polymerization initiator (d) from the viewpoint of transparency, surface curability, and film curability. By using the alkylphenones, a cured film having further improved scratch resistance can be obtained.
Examples of the above-mentioned alkylphenones include: α -hydroxyalkylbenzones such as 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one, and 2-hydroxy-1- (4- (2-hydroxy-2-methylpropanoyl) benzyl) phenyl) -2-methylpropan-1-one; α -aminoalkylbenzones such as 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one; 2, 2-dimethoxy-1, 2-diphenylethan-1-one; methyl phenylglyoxylate.
In the present invention, the (d) polymerization initiator is used in a proportion of 1 to 20 parts by mass, preferably 2 to 10 parts by mass, relative to 100 parts by mass of the above-mentioned (a) active energy ray-curable polyfunctional monomer.
[ (e) solvent ]
The curable composition of the present invention may further contain (e) a solvent, and may be in the form of a varnish (film-forming material).
The solvent may be appropriately selected in consideration of workability in coating for forming a cured film (hard coat layer) described later, drying properties before and after curing, and the like, as long as the components (a) to (d) are dissolved/dispersed. Examples thereof include: aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetrahydronaphthalene; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirits, and cyclohexane; halogenated substances such as methyl chloride, methyl bromide, methyl iodide, methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, o-dichlorobenzene and the like; esters or ester ethers such as ethyl acetate, propyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, and Propylene Glycol Monomethyl Ether Acetate (PGMEA); ethers such as diethyl ether, Tetrahydrofuran (THF), 1, 4-dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, Propylene Glycol Monomethyl Ether (PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-isopropyl ether, and propylene glycol mono-n-butyl ether; ketones such as acetone, Methyl Ethyl Ketone (MEK), methyl isobutyl ketone (MIBK), di-n-butyl ketone, and cyclohexanone; alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexanol, benzyl alcohol and ethylene glycol; amides such as N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), and N-methyl-2-pyrrolidone (NMP); sulfoxides such as dimethyl sulfoxide (DMSO); and mixing two or more of these solvents.
Further, a solvent having a high boiling point may be used for the purpose of controlling the dispersibility of the fine particles at the time of drying after coating.
Examples of such solvents include: cyclohexyl acetate, propylene glycol diacetate, 1, 3-butanediol diacetate, 1, 4-butanediol diacetate, 1, 6-hexanediol diacetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, 3-methoxybutyl acetate, ethylene glycol, diethylene glycol, propylene glycol, 1, 3-butanediol, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, 3-methoxybutanol, dipropylene glycol dimethyl ether, dipropylene glycol methyl-propyl-ether.
(e) The amount of the solvent used is not particularly limited, but is used, for example, at a concentration of 1 to 70 mass%, preferably 5 to 50 mass%, of the solid content in the curable composition of the present invention. The solid content concentration (also referred to as nonvolatile content concentration) herein means the content of a solid content (a portion where a solvent component is removed from all components) with respect to the total mass (total mass) of the components (a) to (d) (and other additives as needed) in the curable composition of the present invention.
[ other additives ]
In the curable composition of the present invention, if necessary, additives usually added, for example, a polymerization accelerator, a polymerization inhibitor, a photosensitizer, a leveling agent, a surfactant, an adhesion imparting agent, a plasticizer, an ultraviolet absorber, a light stabilizer, an antioxidant, a storage stabilizer, an antistatic agent, an inorganic filler, a pigment, and a dye may be appropriately blended as long as the effects of the present invention are not impaired.
Further, inorganic fine particles such as titanium oxide may be blended for the purpose of controlling the haze value of the cured film.
For the purpose of improving the hardness and scratch resistance of the cured film, for example, inorganic fine particles such as silica (silica) and silica (silica) having a reactive group such as an active energy ray-curable group may be blended. As the inorganic fine particles of the other additives, nanoparticles having an average particle diameter of less than 0.2 μm can be used.
< cured film >
The curable composition of the present invention is applied (coating) to a substrate to form a coating film, and the coating film is irradiated with active energy rays to polymerize (cure) the coating film, whereby a cured film can be formed. The cured film is also an object of the present invention. In addition, a hard coat layer in a hard coat film described later may be a layer formed of the cured film.
Examples of the base material in this case include: various resins (polyesters such AS polycarbonate, polymethacrylate, polystyrene, polyethylene terephthalate (PET), and polyethylene naphthalate (PEN), polyurethane, Thermoplastic Polyurethane (TPU), polyolefin, polyamide, polyimide, epoxy resin, melamine resin, triacetyl cellulose (TAC), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene copolymer (AS), norbornene-based resin, and the like), metal, wood, paper, glass, and slate. The shape of these substrates may be a plate, a film or a three-dimensional molded body.
As a coating method on the substrate, 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 ink jet method, a printing method (a relief printing method, a gravure printing method, a planographic printing method, a screen printing method, and the like) can be appropriately selected, and among these methods, a relief printing method is preferably used from the viewpoint of applicability to a roll-to-roll method and also from the viewpoint of film coatability, and particularly, a gravure coating method is preferably used. It is preferable that the curable composition is filtered in advance using a filter having a pore size of about 0.2 μm or the like and then applied. In the case of coating, a solvent may be further added to the curable composition as needed. As the solvent in this case, various solvents listed in the above-mentioned [ (e) solvent ] can be used.
After a curable composition is applied to a substrate to form a coating film, the coating film is pre-dried by a heating means such as a hot plate or an oven as necessary to remove a solvent (solvent removal step). The conditions for the heat drying at this time are, for example, preferably about 30 seconds to 10 minutes at 40 ℃ to 120 ℃.
After drying, the coating film is cured by irradiation with active energy rays such as ultraviolet rays. Examples of the active energy ray include ultraviolet rays, electron beams, and X-rays, and ultraviolet rays are particularly preferable. Examples of the light source for ultraviolet irradiation include 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.
Then, the polymerization can be completed by baking, specifically, heating using a heating means such as a hot plate or an oven.
After drying and curing, the thickness of the cured film formed is usually 0.01 μm to 50 μm, for example, 0.05 μm to 20 μm, preferably 1 μm to 20 μm, and more preferably 3 μm to 15 μm.
< hard coating film >
A hard coat film having a hard coat layer on at least one surface (surface) of a film substrate can be produced using the curable composition of the present invention. The hard coat film is also an object of the present invention, and is preferably used for protecting the surface of various display elements such as a touch panel and a liquid crystal display.
The hard coat layer in the hard coat film of the present invention can be formed by a method comprising the steps of: a step of applying the curable composition of the present invention to a film substrate to form a coating film; and a step of curing the coating film by irradiating the coating film with active energy rays such as ultraviolet rays. A method for producing a hard coat film comprising these steps and having a hard coat layer on at least one surface of a film substrate is also an object of the present invention.
As the film substrate, various transparent resin films that can be used for optical applications among the substrates listed as < cured film > above can be used. Preferred resin films include, for example: films of polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN), polyurethanes, Thermoplastic Polyurethanes (TPU), polycarbonates, polymethacrylates, polystyrene, polyolefins, polyamides, polyimides, and triacetyl cellulose (TAC).
In addition, as the method of applying the curable composition to the film base material (coating film forming step) and the method of irradiating the coating film with active energy rays (curing step), the methods listed under the above-mentioned < cured film > can be used. In the case where the curable composition of the present invention contains a solvent (in the form of a varnish), the coating film forming step may be followed by a step of drying the coating film to remove the solvent, if necessary. In this case, the coating film drying method (solvent removal step) listed as the above-mentioned < cured film > can be used.
The thickness (film thickness) of the hard coat layer thus obtained is preferably set to a thickness 1 to 10 times larger than the average particle diameter of the fine particles (c). For example, the thickness of the hard coat layer is preferably 1 μm to 20 μm, more preferably 3 μm to 15 μm.
The hard coat film of the present invention can be used as a hard coat film for a display or a polarizing plate, and a display or a polarizing plate having the hard coat film is also an object of the present invention.
[ examples ]
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the following examples.
In the examples, the apparatus and conditions for sample preparation and physical property analysis were as follows.
(1) Coating with a rod coater
The device comprises the following steps: TQC SHEEN, Automatic Filmapplector AB 3125.
Rod 1: A-Bar OSP-42 manufactured by OSG SYSTEM PRODUCTS, Inc., and having a maximum wet film thickness of 42 μm (equivalent to WIRE BAR # 16).
And (2) a rod: A-Bar OSP-22 manufactured by OSG SYSTEM PRODUCTS, Inc., and having a maximum wet film thickness of 22 μm (equivalent to WIRE BAR # 9).
And (3) a rod: A-Bar OSP-52 manufactured by OSG SYSTEM PRODUCTS, Inc., and having a maximum wet film thickness of 52 μm (equivalent to WIRE BAR # 20).
Coating speed: 4 m/min.
(2) Baking oven
The device comprises the following steps: three base counter (Kabushiki Kaisha) 2-layer clean oven (formula above) PO-250-45-D.
(3) UV curing
The device comprises the following steps: CV-110 QC-G was manufactured by Heraeus.
Lamp: high pressure mercury lamp H-bulb manufactured by Heraeus.
(4) Film thickness (layer thickness)
The device comprises the following steps: nikon digital length measuring machine Digimicro MH-15M + COUNTER TC-101.
(5) Measurement of gloss
The device comprises the following steps: GM-268 Plus glossmeter manufactured by Konica Minolta corporation.
Measuring an angle: 60 degrees.
(6) Scratch resistance test
The device comprises the following steps: the reciprocating abrasion tester TRIBOGEAR TYPE manufactured by Xindong science (strain): 30H.
Scanning speed: 4500 mm/min.
Scanning distance: 50 mm.
(7) Total light transmittance and haze
The device comprises the following steps: NDH5000 haze Meter manufactured by Nippon Denshoku industries Ltd.
(8) Contact Angle determination
The device comprises the following steps: DropMaster DM-501, manufactured by Kyowa interface science (Inc.).
Measuring temperature: at 20 ℃.
In addition, the abbreviation indicates the following meaning.
PFPE 1: perfluoropolyethers having two hydroxyl groups at both ends of the molecular chain without a poly (oxyalkylene) group [ Fomblin (registered trademark) T4, product of Solvay Specialty Polymers ].
PFPE 2: perfluoropolyether having hydroxyl groups at both ends of the molecular chain via poly (oxyalkylene) groups (repeating number of units: 8 or 9) [ Fluorolink 5147X manufactured by Solvay Specialty Polymers ].
BEI: 1, 1-bis (acryloyloxymethyl) ethyl isocyanate [ Karenz (registered trademark) BEI, manufactured by Showa Denko K.K. ].
DOTDD: dioctyltin dineodecanoate [ NEOSTAN (registered trademark) U-830, available from NIDDM CHEMICAL CRYSTAL CO., LTD.).
DBTDL: dibutyl tin dilaurate (manufactured by Tokyo chemical industry Co., Ltd.).
DPHA: dipentaerythritol pentaacrylate/dipentaerythritol hexaacrylate mixture [ KAYALAD (registered trademark) DN-0075, manufactured by NIPPON CHEMICAL MEDICINE, Inc. ].
PETA: pentaerythritol triacrylate/pentaerythritol tetraacrylate mixture [ NK ESTER A-TMM-3 LM-N, manufactured by Newzhongcun chemical industry Co., Ltd ].
UA: a 6-functional aliphatic urethane acrylate oligomer [ EBECRYL (registered trademark) 5129 manufactured by Daicel Allnex, Ltd ].
FP 1: crosslinked polymethyl methacrylate spherical particles [ TECHNOLYMER (registered trademark) SSX-105 manufactured by HYPERMERIZATION PRODUCTS INDUSTRY, Inc.; average particle diameter 5 μm ].
FP 2: crosslinked polymethyl methacrylate spherical particles [ TECHNOLYMER (registered trademark) SSX-108 manufactured by HYPERMERIZATION PRODUCTS INDUSTRY, Inc.; average particle diameter 8 μm ].
FP 3: crosslinked polymethyl methacrylate spherical particles [ TECHNOLYMER SSX-110 (registered trademark) manufactured by HYPERMERIZATION PRODUCTS INDUSTRY, Inc.; average particle diameter: 10 μm ].
FP 4: crosslinked polymethyl methacrylate spherical particles [ TECHNOLYMER (registered trademark) SSX-103 manufactured by HYPERMERIZATION PRODUCTS INDUSTRY, Inc.; average particle diameter 3 μm ].
O2959: 2-hydroxy-1- (4- (2-hydroxyethoxy) phenyl) -2-methylpropan-1-one [ OMNIRAD (registered trademark) 2959, manufactured by IGM Resins Co., Ltd ].
EPA: ethyl p-dimethylaminobenzoate [ KAYACURE (registered trademark) EPA manufactured by Nippon Kagaku Co., Ltd ].
PET: a double-sided easy-adhesion treated polyethylene terephthalate (PET) film [ Lumiror (registered trademark) U403, manufactured by Toray corporation, thickness 100 μm ].
TAC: a double-sided easy-adhesion treated cellulose Triacetate (TAC) film [ FUJITAC (registered trademark) TD80ULP, manufactured by Fuji film, Ltd., thickness 80 μm ].
MEK: methyl ethyl ketone.
MIBK: methyl isobutyl ketone.
PGME: propylene glycol monomethyl ether.
Production example 1 production of perfluoropolyether (SM1) having four acryloyl groups at each end of the molecular chain via a urethane bond (not via a poly (oxyalkylene) group)
Into the spiral tube were charged 1.19g (0.5mmol) of PFPE1, 0.52g (2.0mmol) of BEI, 0.017g (an amount of 0.01 times the total mass of PFPE1 and BEI) of DOTDD, and 1.67g of MEK. The mixture was stirred at room temperature (about 23 ℃) for 24 hours using a stirrer Chip (starter Chip), to obtain a 50 mass% MEK solution of SM1 as a target compound.
Weight average molecular weight of the obtained SM1 in terms of polystyrene based on GPC: mw of 3000, dispersity: mw (weight average molecular weight)/Mn (number average molecular weight) was 1.2.
Production example 2 production of perfluoropolyether (SM2) having acryloyl groups at both ends of the molecular chain via poly (oxyalkylene) groups
A spiral tube was charged with 1.05g (0.5mmol) of PFPE2, 0.26g (1.0mmol) of BEI, 0.01g (0.02mmol) of DBTDL and 1.30g of MEK. The mixture was stirred using a stirrer chip at room temperature (about 23 ℃) for 24 hours. The reaction mixture was diluted with 3.93g of MEK to give a 20 mass% MEK solution of SM2 as a target compound.
Examples 1 to 9 and comparative examples 1 to 4
The following components were mixed as described in table 1 to prepare a curable composition having a solid content of 40 mass%. Here, the solid component means a component other than the solvent. In table 1, [ parts ] and [% ] represent [ parts by mass ].
(1) A polyfunctional monomer: 50 parts by mass of DPHA, 30 parts by mass of UA and 20 parts by mass of PETA.
(2) Surface modifier: the surface modifier (in terms of solid content or active ingredient) shown in Table 1 in the amounts shown in Table 1.
(3) Organic microparticles: the amount of the organic fine particles shown in Table 1 is shown in Table 1.
(4) Polymerization initiator: 5 parts by mass of O2959.
(5) Polymerization accelerator: EPA in the amounts shown in Table 1.
(6) Solvent: the amount of the solvent described in Table 1 is as described in Table 1.
The curable composition was applied to a film having a size of a4 shown in table 2 by a bar coater using a bar shown in table 2 to obtain a coating film. The coating film was dried in an oven under the conditions described in table 2, and the solvent was removed. The obtained film was exposed to UV light at the exposure amount shown in table 2 in a nitrogen atmosphere, thereby producing a hard coat film having a hard coat layer (cured film) having a thickness shown in table 2.
The hard coat film obtained was evaluated for anti-glare property, scratch resistance, water contact angle, haze and total light transmittance. Evaluation methods of antiglare properties, scratch resistance and water contact angle are shown below. The results are also shown in table 3.
[ anti-dazzle Property ]
The hard coat film thus obtained was placed on a black stage having a gloss Gs (60 °) of 11.8, and the gloss Gs (60 °) of the hard coat layer surface of the hard coat film was measured and evaluated according to the following criteria A, B and C. When it is assumed that the hard coat layer is actually used, at least B, preferably a is required.
A：Gs(60°)≤120。
B：120＜Gs(60°)≤125。
C：Gs(60°)＞125。
[ scratch resistance ]
The hard coat surface of the hard coat film was treated with steel wool (Liberon #0000 from Liberon corporation) attached to the reciprocating abrasion tester]Application of 500g/cm2The load of (2) was repeated 2000 times. The degree of the scratch was visually confirmed under a three-color light source, and evaluated according to the following criteria A, B and C. When it is assumed that the hard coat layer is actually used, at least B, preferably a is required.
A: has no scar.
B: several fine scars were produced.
C: the whole surface was scratched.
[ contact Angle ]
The contact angle θ after 5 seconds of the hard coat film surface was measured at 5 points by attaching 1 μ L of water to the hard coat layer surface, and the average value thereof was set as the water contact angle value, and evaluated according to the following criteria a and C. When the hard coat layer is actually used, the water contact angle (initial hydrophobicity) is required to be a (108 ° or more).
A: the value of the water contact angle is more than or equal to 108 degrees.
C: the water contact angle value is < 108 deg.
[ Table 1]
Figure BDA0003200610890000251
[ Table 2]
Figure BDA0003200610890000252
[ Table 3]
Figure BDA0003200610890000261
As shown in tables 1 to 3, in each of the hardcoats having hardcoats produced using the curable compositions of examples 1 to 9, a hardcoat having a hardcoat excellent in scratch resistance and antiglare property can be obtained at a layer thickness of 10 μm to 14 μm of the layer, and in the curable composition, perfluoropolyether SM1 having four acryloyl groups at both ends of the molecular chain via urethane bonds (without poly (oxyalkylene) groups) is used as a surface modifier in the hardcoat, and organic fine particles are blended. The initial hydrophobicity was 108 ° or more, and all satisfied the criteria in consideration of the actual use as compared with the comparative examples described later.
On the other hand, the hard coating film of comparative example 1 having a hard coating layer produced using perfluoropolyether SM2 having acryloyl groups at both ends of the molecular chain via poly (oxyalkylene) groups as a surface modifier could not obtain desired initial hydrophobicity.
In addition, the desired antiglare properties were not obtained in comparative examples 2 and 3 which did not contain organic fine particles. In comparative example 4 containing 50 parts by mass of the organic fine particles, high antiglare properties were obtained, but the scratch resistance was poor.

Claims (15)

1. A curable composition comprising:
(a) 100 parts by mass of an active energy ray-curable polyfunctional monomer;
(b) a perfluoropolyether containing a poly (oxyperfluoroalkylene) group, the perfluoropolyether having an active energy ray-polymerizable group at both ends of the molecular chain thereof via a urethane bond being 0.05 to 10 parts by mass, excluding the perfluoropolyether having a poly (oxyalkylene) group between the poly (oxyperfluoroalkylene) group and the urethane bond;
(c) 5 to 40 parts by mass of fine particles having an average particle diameter of 0.2 to 15 μm; and
(d) 1 to 20 parts by mass of a polymerization initiator that generates radicals using active energy rays.
2. The curable composition according to claim 1,
the perfluoropolyether (b) has at least two active energy ray-polymerizable groups at both ends of the molecular chain thereof via urethane bonds.
3. The curable composition according to claim 2,
the perfluoropolyether (b) has at least three active energy ray-polymerizable groups at each end of the molecular chain thereof via a urethane bond.
4. The curable composition according to any one of claims 1 to 3,
the poly (oxyperfluoroalkylene) group is a poly (oxyalkylene) group having a repeating unit- [ OCF ]2]-and a repeating unit- [ OCF2CF2]Both of them are groups in which these repeating units are bonded in a block bonding, a random bonding, or a block bonding and a random bonding.
5. The curable composition according to claim 4,
the perfluoropolyether (b) has a partial structure represented by the following formula [1],
Figure FDA0003200610880000011
the above formula [1]In which n represents a repeating unit- [ OCF ]2CF2]Number and repeating Unit- [ OCF ]2]-the total number of numbers is an integer from 5 to 30,
said repeating unit- [ OCF ]2CF2]-and said recurring unit- [ OCF2]The bonding is performed by block bonding, random bonding, or any of block bonding and random bonding.
6. The curable composition according to any one of claims 1 to 5,
the fine particles of the component (c) are organic fine particles.
7. The curable composition according to claim 6,
the organic fine particles of the component (c) are polymethyl methacrylate fine particles.
8. The curable composition according to any one of claims 1 to 7,
further comprising (e) a solvent.
9. A cured film obtained from the curable composition according to any one of claims 1 to 8.
10. A hard coat film comprising a hard coat layer formed from the cured film according to claim 9 on at least one surface of a film substrate.
11. The hard coating film according to claim 10, wherein,
the hard coat layer has a layer thickness of 1 μm to 20 μm.
12. The hard coating film according to claim 11, wherein,
the hard coat layer has a layer thickness of 3 μm to 15 μm.
13. A method for producing a hard coat film, which comprises a hard coat layer on at least one surface of a film substrate, wherein the hard coat layer comprises:
a step of applying the curable composition according to any one of claims 1 to 8 to a film substrate to form a coating film; and
and a step of irradiating the coating film with an active energy ray to cure the coating film.
14. A display provided with the hard coat film according to any one of claims 10 to 12.
15. A polarizing plate provided with the hard coat film according to any one of claims 10 to 12.
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