JP2014008607A - Hard coat film and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film having a hard coat layer with high lipophilicity, which allows visibility of adhesion traces of a sebum component such as a finger print to be reduced, and having excellent smoothness or uniformity of the surface.SOLUTION: A hard coat film includes a transparent base film and a hard coat layer formed on at least one face of the base film. The hard coat layer is formed of a hardened layer of a curable composition including a (meth)acrylic monomer or oligomer (A), a lipophilic resin (B) having a polymerizable group and a water-repellent and lipophilic region, and a resin (C) having a polymerizable group and a branched fluoro aliphatic hydrocarbon group. The pencil hardness of the hard coat layer is 1H or more.

Description

  The present invention relates to a hard coat film having an anti-scratch function (abrasion resistance) and a method for producing the same. In more detail, touch panel, liquid crystal display (LCD), plasma display panel (PDP), electroluminescence (EL) display (organic EL display, etc.), field emission display (FED), and other display-type display devices. Hard coat film disposed on the surface and having the function of protecting the surface and preventing scratches (abrasion resistance), in particular, a hard coat film with reduced fingerprint visibility (or improved fingerprinting property) and its production Regarding the method.

  In a display device such as a liquid crystal display (LCD) or an organic EL display, a hard coat film having a hard coat layer is disposed on the display surface in order to protect the surface. However, human fingerprints (sebum), sweat, cosmetics, dust, etc., adhere to the surface of the hard coat layer and are easily soiled, which hinders aesthetics, display quality, visibility and operability. In particular, dirt due to lipid components such as fingerprints cannot be easily wiped off.

  It is also known to reduce the contact angle by increasing the affinity with the attached fingerprint by forming an oleophilic film in order to prevent soiling due to lipid components (fingerprint adhesion, etc.). Japanese Patent Application Laid-Open No. 2001-353808 (Patent Document 1) discloses that a lipophilic film (with a surface energy of 30 to 70 mN / m) is formed on a biological lipid component to prevent the stain from being noticeable. ing. Specifically, a collection of molecules treated with 2-trichlorosilane ethyl stearate or the like, orienting lipophilic groups such as fatty acid ester groups outward of the substrate, and chemically bonding a part of the molecules to the substrate It is described that imparting lipophilicity to the group, making the film lipophilic by dispersing and adding the constituent components of the film and the lipophilic substance. When such a lipophilic film is formed, stains due to sebum (such as fingerprints) can be made difficult to see, and fingerprint stain resistance (or sebum stain resistance) can be improved. However, it is difficult to increase the hardness of the coating, and the scratch resistance is reduced.

  It is also known that a lipophilic compound is added to a hard coat agent that forms a hard coat layer having a high film hardness to make the surface of the hard coat layer oleophilic. Japanese Patent Application Laid-Open No. 2004-359834 (Patent Document 2) does not include any of an organo (poly) siloxane group and an organic fluorine compound group, and has a (meth) acrylate having a water repellent group such as an alkyl group having 12 or more carbon atoms. (Meth) acrylic copolymer (A) or a complex of this and an inorganic oxide fine particle (such as colloidal silica), and the pencil hardness of the coating film is 5B or more (particularly 2H). A contamination resistance imparting agent having a contact angle with water of 80 ° or more and a contact angle with oleic acid, triolein or squalene of 10 ° or less is disclosed. This document may further contain a (meth) acrylate having a hydrophilic group (polyalkylene glycol group, hydroxyl group, etc.) as a copolymerization component, a polyfunctional (meth) acrylate compound (B), and photopolymerization initiation. It also describes that it may contain an agent (C) and may be active energy ray curable. Furthermore, a stain resistant article having a coating film formed with the above stain resistance imparting agent on its surface is also disclosed. When such a lipophilic coating film is formed, dirt due to sebum (fingerprints, etc.) can be hardly seen, and fingerprint stain resistance (or sebum stain resistance) can be improved. However, the stain resistance imparting agent alone cannot form a coating film having a high hardness, and in order to form a coating film having a high hardness, a polyfunctional (meta) having three or more (meth) acryloyl groups in the molecule. ) Requires acrylate. Further, the removability cannot be maintained for a long period of time, and the soil removability is reduced by repeated use.

  In JP 2009-249484 A (Patent Document 3), in order to prevent contamination of the coating surface, (I) (A) a polymer of a linear aliphatic alkyl group having 10 or more carbon atoms (containing a functional group). Monomer 1 in which a radical polymerizable double bond is introduced into a terminal functional group of a monomer (A-2) polymerized with a monomer having an alkyl group having 10 or more carbon atoms in the presence of a chain transfer agent (A-1) ~ 50% by weight, (B) a monomer having a curable functional group (ultraviolet cationic curable functional group such as glycidyl group, alkoxysilyl group) 5 to 50% by weight, and (C) the monomer (A) as required And a graft copolymer obtained by reacting 0 to 94% by weight of a monomer not belonging to the monomer (B), and (II) a curing agent (ultraviolet cationic curing agent) that crosslinks the curable functional group of the monomer (B) Such) To form a coating film is disclosed by painting the coating composition containing. Even this lipophilic coating film can make it difficult to see dirt due to sebum (such as fingerprints), and can improve fingerprint resistance (or resistance to sebum resistance). However, since cationic polymerization is used, the curing rate is low, and the curing reaction proceeds even when irradiated with ultraviolet rays.

  Further, in Patent Documents 2 and 3, the visibility of dirt due to lipid components (such as fingerprints) such as sebum cannot be reduced, and the dirt is easily noticeable. Furthermore, the surface smoothness and uniformity of the lipophilic coating film may be impaired.

  In order to improve the surface smoothness of the hard coat layer, the addition of a leveling agent is effective. As typical leveling agents, oil-repellent leveling agents such as silicone-based and fluorine-based leveling agents are used. Are known. However, when such a leveling agent is added to a coating agent that forms an oleophilic film, the leveling agent is oleophobic, so the surface properties of the film are reduced, and the anti-fingerprint stain resistance based on oleophilicity is improved. Be inhibited.

JP 2001-353808 A (Claims and Examples) JP 2004-359834 A (Claims and Examples) JP 2009-249484 A (Claims, paragraph [0016])

  Accordingly, an object of the present invention is to provide a film provided with a hard coat layer having high lipophilicity and excellent surface smoothness or uniformity, and a method for producing the film.

  Another object of the present invention is to provide a film provided with a hard coat layer capable of reducing the visibility of dirt (for example, fingerprint visibility) due to lipid components such as sebum and a method for producing the same.

  Still another object of the present invention is to improve the leveling property even if the amount of the leveling agent used is small, without impairing the lipophilicity of the coating, and to prevent contamination by sebum and the like, especially by contamination with lipid components such as sebum. It is providing the film provided with the hard-coat layer which can reduce the visibility (conspicuousness degree of dirt) largely, and its manufacturing method.

  Another object of the present invention is that a film having a hard coat layer having the above characteristics is disposed on the surface, and the visibility of dirt due to lipid components such as sebum (for example, fingerprint visibility) is remarkably reduced, so that it can be used repeatedly. However, there is a need to provide a display device that does not deteriorate the display quality.

  As a result of intensive investigations to achieve the above-mentioned problems, the inventors of the present invention added leveling without impairing the lipophilicity of the coating when a fluorinated resin (including oligomers) having a branched structure was added to the lipophilic hardcoat agent. In addition to improving the properties, the inventors have found that the visibility of dirt due to lipid components (for example, fingerprint visibility) can be greatly improved, and the present invention has been completed.

  That is, the hard coat film of the present invention includes a transparent base film and a hard coat layer formed on at least one surface of the base film, and the hard coat layer is a (meth) acrylic single layer. A polymer or oligomer (A), a lipophilic resin (B) having a radical polymerizable group and a water-repellent lipophilic site, and a resin (C) having a radical polymerizable group and a branched fluoroaliphatic hydrocarbon group. It is formed of a cured layer of a radically curable composition that contains it, and has a pencil hardness of 1H or more. In addition, the radical curable composition may further contain a radical polymerization initiator (D).

In such a curable composition, the component (A) usually contains at least a polyfunctional (meth) acrylate having a plurality of (meth) acryloyl groups. The component (B) has a radically polymerizable group and a (meth) acrylic polymer having a non-aromatic hydrocarbon group having 10 or more carbon atoms in the side chain, for example, a long chain alkyl group (meta ) It may be a polymer of a monomer component containing 10 to 70% by weight of acrylate. The component (B) is often a (meth) acrylic polymer containing at least a C _10-24 alkyl (meth) acrylate as a monomer component. The amount of component (B) used may be about 0.025 to 5 parts by weight with respect to 100 parts by weight of the total amount of component (A).

  Furthermore, the component (C) has a radically polymerizable group and has a branched fluoroalkyl group or a branched fluoroalkenyl group (for example, a perfluoroisopropyl group and / or a perfluoroisopropylidene group) in the side chain (meth). It may be a (meth) acrylic polymer containing an acrylic monomer as a monomer component. Furthermore, the component (C) includes a (meth) acrylic monomer having a branched fluoroalkyl group or a branched fluoroalkenyl group, a (meth) acrylic monomer having a hydroxyl group, and, if necessary, these (meth) It may be a polymer of a monomer component containing an acrylic monomer and a copolymerizable monomer that can be copolymerized, and an isocyanate having a (meth) acryloyl group in the hydroxyl group of the side chain of this polymer The compound may be urethane-bonded. Furthermore, the component (C) is a single amount containing a (meth) acrylic monomer having a branched fluoroalkyl group or a branched fluoroalkenyl group in a proportion of about 5 to 75% by weight (for example, 10 to 50% by weight). It may be a body component polymer (such as a (meth) acrylic polymer). The proportion of component (C) may be about 0.01 to 0.1 parts by weight with respect to 100 parts by weight of the total amount of component (A).

  The pencil hardness of the hard coat layer may be 2H or higher (for example, 3H or higher). Further, the haze value of the hard coat film may be 1.8% or less.

  The hard coat layer may be formed on at least one surface of the base film, or may be formed on both surfaces of the base film. In this case, the surface of the hard coat layer on both sides may be smooth, the surface of the hard coat layer on one side is smooth, and the surface of the hard coat layer on the other side is formed to be rough or uneven. It may be. Unrenewton ring properties may be imparted by a rough or uneven hard coat layer.

  The present invention also discloses a radical curable composition containing the component (A), the component (B), and the component (C). Such a composition can be applied to a substrate film and cured to form a hard coat layer, or can be applied to a display surface and cured to form a hard coat layer.

  The hard coat film is a pencil in which a radical curable composition containing the component (A), the component (B), and the component (C) is applied to at least one surface of the transparent substrate film, and the coating film is cured. It can be manufactured by forming a hard coat layer having a hardness of 1H or more. The transparent substrate film may be a polyester resin, an acrylic resin, a polyolefin resin film, a cellulose resin film, or the like.

  The hard coat film is useful for protecting the display surface (or touch panel surface) and the like. Moreover, even if lipid components, such as sebum, adhere, the visibility (fingerprint visibility) of a deposit can be reduced. Therefore, in addition to protecting the display surface, it is also useful for improving the visibility of display display. Therefore, the present invention also includes a display device having the hard coat film on the surface.

  In this specification, an acrylic monomer or an acrylic resin and a methacrylic monomer or a methacrylic resin are collectively referred to as a (meth) acrylic monomer or a (meth) acrylic resin (or polymer). To do. In addition, “resin” and “polymer” are not limited to high molecular weight polymers, but also include dimers, trimers and the like, and oligomers having a weight average molecular weight of about 300 to 15000 (for example, 500 to 10,000). Used to mean including Further, the radical polymerizable group may be simply referred to as a polymerizable group.

  In the present invention, since the lipophilic hard coat layer contains a predetermined fluorine-containing resin, a hard coat layer excellent in surface smoothness or uniformity can be formed while maintaining high lipophilicity. Therefore, the visibility of dirt due to lipid components such as sebum (for example, fingerprint visibility) can be greatly reduced. In addition, the leveling property can be improved even if the amount of the leveling agent used is small, without impairing the lipophilicity of the hard coat layer (coating film). The property (conspicuousness of dirt) can be greatly reduced. Therefore, if a hard coat film is provided on the display surface (display surface) of the display device, the visibility of dirt due to lipid components such as sebum (for example, fingerprint visibility) can be significantly reduced, and high display quality even after repeated use Can be maintained.

[Transparent substrate film]
The transparent substrate film only needs to have transparency that does not impair the display quality of the display device and have an appropriate mechanical strength. Examples of the resin for the substrate film include polyester resins (polyethylene terephthalate) And poly C _2-4 alkylene C _6-10 arylate resins, polyarylate resins, etc. containing 50 to 100 mol% of C _2-4 alkylene C _6-10 arylate units such as polyethylene naphthalate); acrylic Resins (polymethyl methacrylate, etc.); Olefin resins (chain olefin resins such as polyethylene and polypropylene, cyclic olefin resins, etc.); Polycarbonate resins; Cellulose resins, for example, cellulose acylate resins (cellulose triacetate, cellulose) Diacetate, cellulose Acetate propionate, cellulose acetate butyrate, etc.); polyamide resin; styrene resin (polystyrene, styrene-methyl methacrylate copolymer, acrylonitrile-styrene resin (AS resin), etc.); polysulfone resin; polyethersulfone resin ; Polyetherketone resin; Polyetherketoneimide resin; Polyimide resin; Chlorine-containing resin (vinyl chloride resin, vinylidene chloride resin, etc.); Vinyl alcohol resin (polyvinyl alcohol, ethylene-vinyl alcohol copolymer resin, etc.) And the like. These films may be single layer films or laminated films.

  A preferable transparent substrate film is a film excellent in transparency, mechanical strength, and flexibility, for example, a polyester resin film, an acrylic resin film, a polyolefin resin film, or a cellulose resin film.

  The thickness of the transparent substrate film can be selected from a range of about 10 to 300 μm, for example, and is usually about 20 to 250, preferably about 35 to 190 μm (for example, 75 to 200 μm). The visible light transmittance of the base film may be, for example, 80% or more, preferably 85% or more, and more preferably 90% or more.

  In addition, an anchor layer may be formed on the surface (surface on which the hard coat layer is formed) of the base film, or an easy adhesion treatment such as a corona discharge treatment may be performed.

[Hard coat layer]
The hard coat layer comprises a (meth) acrylic monomer or oligomer (A), a lipophilic resin (B) having a radical polymerizable group and a water-repellent lipophilic portion, a radical polymerizable group and a branched fluoroaliphatic group. It is formed with the hardened | cured material of the composition containing resin (C) which has a hydrocarbon group.

Component (A): The (meth) acrylic monomer or oligomer component (A) is a monofunctional (meth) acrylate having one (meth) acryloyl group in the molecule as long as a hard cured film can be formed. However, in order to impart hard coat properties and improve film strength, usually, a polyfunctional (meth) acrylate having a plurality of (for example, about 2 to 8) (meth) acryloyl groups and / or two or more functional groups. Oligomers or resins are widely used.

Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and hexanediol. Alkanediol di (meth) acrylate such as di (meth) acrylate; Alkane polyol di (meth) acrylate such as glycerin di (meth) acrylate; Polyalkylene glycol di (meth) acrylate such as diethylene glycol di (meth) acrylate; Bisphenols di (meth) acrylates of _{C 2-4} alkylene oxide adduct of; tricyclo [5.2.1.0 ^2,6] decanedimethanol di (meth) acrylate, adamantane di (meth) acrylate , And others bridged cyclic di (meth) acrylate and the like.

Examples of trifunctional or higher (about 3 to 8 functional) (meth) acrylates include, for example, esterified products of polyhydric alcohol and (meth) acrylic acid, such as glycerin tri (meth) acrylate, trimethylolethane tri (meth). Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate; ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate; dipentaerythritol penta (meth) acrylate; dipentaerythritol hexa ( And (meth) acrylate. Further, in these polyfunctional (meth) acrylates, the polyhydric alcohol may be an adduct of alkylene oxide (for example, C _2-4 alkylene oxide such as ethylene oxide). These polyfunctional (meth) acrylates can be used alone or in combination of two or more.

  In the polyfunctional (meth) acrylate, the number of (meth) acryloyl groups in one molecule is, for example, 2 to 8, preferably 3 to 8 (for example, 3 to 7), and more preferably 4 to 7 (for example, 5). About 7).

  Examples of the bifunctional or higher oligomer or resin include epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, melamine (meth) acrylate, and silicone (meth) acrylate. The number average molecular weight of the oligomer may be about 500 to 10000 (for example, 750 to 5000). Bifunctional or higher oligomers or resins may be used in combination with polyfunctional (meth) acrylates.

  The monomer of component (A) usually does not contain a monomer having an organopolysiloxane unit and a monomer having a fluorinated alkyl group. In addition, the component (A) may contain a monofunctional monomer.

The monofunctional monomer includes a (meth) acrylic monomer and a vinyl monomer. Examples of (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, t-butyl (meth) acrylate, Pentyl (meth) acrylate, t-amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) Acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, hex _{C 5-10} cycloalkyl (meth) acrylates such as cyclohexyl (meth) acrylate; decyl (meth) acrylate, octadecyl (meth) _{C 1-20} alkyl (meth) acrylates such as acrylate adamantyl (meth) acrylate, isobornyl (meth ) (Meth) acrylate having a bridged cyclic hydrocarbon group such as acrylate; aryl (meth) acrylate such as phenyl (meth) acrylate; aralkyl such as benzyl (meth) acrylate and 2-phenylethyl (meth) acrylate (meta) ) Acrylate; hydroxyalkyl (meth) acrylate such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and ethylene Polyoxy C _2-4 alkylene glycol mono (meth) acrylate such as polyglycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate; Alkoxyalkyl (meth) acrylate; (meth) acrylic acid; glycidyl (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide, amide group-containing (meth) acrylic monomers such as (meth) acryloylmorpholine Dimer aminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate. Examples of vinyl monomers include fatty acid vinyl esters such as vinyl acetate, N-vinyl pyrrolidone, and the like. These monofunctional monomers can be used alone or in combination of two or more. Preferred monofunctional monomers are alkyl (meth) acrylate, (meth) acrylate having a bridged cyclic hydrocarbon group, monomer having a reactive functional group (hydroxyalkyl (meth) acrylate, glycidyl (meth)) Acrylate) and N-vinylpyrrolidone.

  The proportion of polyfunctional (meth) acrylate [for example, bifunctional or higher, preferably tetrafunctional or higher (meth) acrylate] is 50% by weight or more, preferably 70% by weight or more, more preferably 85% by weight of the total component (A). % By weight or more (for example, 90 to 100% by weight).

Component (B): The lipophilic resin component (B) having a radically polymerizable group and a water-repellent / lipophilic part is composed of a (meth) acrylic polymer having a radically polymerizable group and a water-repellent / lipophilic part. it can.

  Examples of the radical polymerizable group include a (meth) acryloyloxy group and a vinyl group, and a (meth) acryloyloxy group is preferable. The radical polymerizable group may be located in the side chain of the polymer or may be located at the end of the main chain.

The water-repellent / lipophilic portion is often located in the side chain of the polymer and can be formed of a non-aromatic hydrocarbon group having 10 or more carbon atoms. Non-aromatic hydrocarbon groups include, for example, linear or branched alkyl groups such as decyl, isodecyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, heicosyl, docosyl group, etc. An alicyclic hydrocarbon group such as cyclodecyl, cyclododecyl, adamantyl or isobornyl group; Carbon number of a non-aromatic hydrocarbon group is 10-24, for example, Preferably it is 12-20, More preferably, it is about 14-18. Preferred non-aromatic hydrocarbon groups are long chain alkyl groups such as linear or branched C _10-24 alkyl groups, preferably C _12-20 alkyl groups, more preferably C _14-18 alkyl groups. , A C _10-16 alkyl group.

Examples of such a monomer having a non-aromatic hydrocarbon group (hereinafter sometimes simply referred to as a lipophilic monomer) include, for example, decyl (meth) acrylate, dodecyl (meth) acrylate, and tridecyl (meth) acrylate. , Tetradecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate and other long chain alkyl (meth) acrylates, adamantyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^{2 , 6} ] (Meth) acrylate having an alicyclic hydrocarbon group such as decane monomethanol (meth) acrylate. These monomers can be used alone or in combination of two or more.

The lipophilic resin may be a copolymer of a monomer (lipophilic monomer) having a water-repellent / lipophilic portion and a copolymerizable monomer. Examples of the copolymerizable monomer include a monomer similar to the monofunctional monomer described in the above-mentioned component (A), and a polymerizable monomer having an alkoxysilyl group (for example, 2-methacrylic monomer). Polymerizable monomer having a _C1-2 alkoxysilyl group and a polymerizable group such as loxypropyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, vinyltrimethoxysilane), polymerizable having an isocyanate group Monomer (for example, isocyanate alkyl (meth) acrylate such as 2-isocyanatoethyl (meth) acrylate, isocyanate C _2-4 alkyloxy C _2-4 alkyl- (meth) acrylate, isocyanate alkanedi-yl- (meth) Acrylate, isocyanate alkanetri-yl- (meth) acrylate, etc.), acid anhydride groups Examples thereof include polymerizable monomers (such as maleic anhydride). Preferred monofunctional monomers are monomers having non-reactive groups (alkyl (meth) acrylates such as C _1-8 alkyl- (meth) acrylate, C _5-8 cycloalkyl- (meth) acrylates, etc.) Aryl (meth) acrylates such as cycloalkyl- (meth) acrylate, phenyl (meth) acrylate, aralkyl (meth) acrylates such as benzyl (meth) acrylate, (meth) acrylates having a bridged cyclic hydrocarbon group), Monomers (for example, hydroxyalkyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate) having the reactive functional group (hydroxyl group, carboxyl group, epoxy group, alkoxysilyl group, isocyanate group, etc.) A polymerizable monomer having an alkoxysilyl group, iso A polymerizable monomer having a Aneto group, or the like). As the monomer having a non-reactive group, at least C _1-6 alkyl- (meth) acrylate is often used. Moreover, the monomer which has a reactive functional group can be used individually or in combination of 2 or more types of different reactive functional groups.

  Furthermore, if necessary, you may use together the polyfunctional (meth) acrylate as described in the term of the said component (A), and / or the oligomer or resin more than bifunctional.

  Component (B) may be prepared by copolymerizing a lipophilic monomer and a polyfunctional (meth) acrylate to leave an unreacted (meth) acryloyl group in the resin. Reactive functional group of copolymer produced by copolymerizing monomer component of oily monomer, monomer having reactive functional group, and monomer having non-reactive group if necessary On the other hand, it can be prepared by reacting a polymerizable monomer having a reactive group. In such lipophilic resin (B), a polymerizable group (such as a (meth) acryloyl group) can be introduced into the side chain.

  Specifically, when the reactive functional group of the copolymer is a hydroxyl group, a polymerizable monomer reactive with the hydroxyl group (for example, a polymerizable monomer having an alkoxysilyl group, a polymerizable having an isocyanate group). Monomer, a polymerizable monomer having an acid anhydride group such as maleic anhydride, etc.), when the reactive functional group of the copolymer is a carboxyl group, Reaction with a monomer (polymerizable monomer having a hydroxyl group, polymerizable monomer having an epoxy group, polymerizable monomer having an alkoxysilyl group, etc.), the reactive functional group of the copolymer is an epoxy group In this case, the lipophilic resin (B) can be prepared by reacting an epoxy group with a reactive polymerizable monomer (such as a polymerizable monomer having a carboxyl group).

  The ratio of the lipophilic monomer (such as (meth) acrylate having a long chain alkyl group) is 10 to 95% by weight (for example, 10 to 70% by weight), preferably 20 to 20% with respect to the whole monomer component. It may be about 90% by weight (for example, 25 to 60% by weight), more preferably about 30 to 80% by weight (for example, 30 to 50% by weight). When the ratio of the lipophilic monomer is too small, the stain resistance and fingerprint resistance are liable to be lowered, and when too large, the hardness of the coating film is liable to be lowered. In addition, the ratio of the polymerizable monomer having a reactive functional group can be selected according to the double bond equivalent or double bond concentration (for example, molecular weight per acryloyloxy) of the lipophilic resin. 5 to 50% by weight (for example, 7 to 40% by weight), preferably 10 to 40% by weight (for example, 15 to 35% by weight), more preferably 15 to 30% by weight (for example, 20 to 30%). % By weight). The total amount of monomer components is 100% by weight. In the polymer, at least a part of the reactive functional group may react with the reactive group of the polymerizable monomer, and 10 to 100 mol% (preferably 20 to 95%) of the reactive functional group introduced into the polymer. Mol%), preferably 30 to 95 mol% (for example, 40 to 90 mol%), more preferably 50 to 90 mol% (for example, 60 to 85 mol%) reacts with the reactive group of the polymerizable monomer. You may do it.

  Such a lipophilic resin (B) can be prepared by polymerizing a monomer component by a conventional method and reacting the reactive functional group of the produced copolymer with a monomer having a reactive group. . Polymerization is performed using, for example, a radical polymerization initiator (an azo polymerization initiator such as azobisisobutyronitrile, a peroxide polymerization initiator such as peroxide) in an organic solvent under an inert atmosphere. It can be performed at a temperature of about ~ 120 ° C. Examples of the organic solvent include aromatic hydrocarbons such as toluene; aliphatic hydrocarbons such as hexane; alicyclic hydrocarbons such as cyclohexane; esters such as ethyl acetate; alcohols such as ethanol and isopropyl alcohol; acetone, Ketones such as methyl ethyl ketone and methyl isobutyl ketone; and mixed solvents thereof. For the reaction between the reactive functional group of the copolymer and the monomer having a reactive group, a catalyst (for example, tertiary amine, esterification catalyst, etc.) corresponding to the reaction is used in the presence of a solvent. , At a temperature of about 60 to 120 ° C.

  The number average molecular weight (polystyrene conversion) of the lipophilic resin (B) may be, for example, 500 to 50000, preferably 1000 to 30000, and more preferably 2500 to 20000 in gel permeation chromatography. When the molecular weight is too small, the coating film properties are liable to be lowered, and when it is too large, the solubility with the component (A) is liable to be lowered.

  In addition, a lipophilic resin (B) may introduce | transduce a polymeric group not only into a side chain but at the terminal (terminal part of a polymerization chain). Such a lipophilic resin (B) is obtained by polymerizing a monomer component containing at least a lipophilic monomer in the presence of the chain transfer agent having the reactive functional group, and reacting at the terminal of the produced polymer. It can be prepared by reacting a functional group with a monomer having a reactive group. The chain transfer agent having a reactive functional group may have a mercapto group involved in chain transfer and a reactive functional group. For example, thioglycolic acid, mercaptoacetic acid, mercaptopropionic acid, mercaptosuccinic acid Chain transfer agents having a carboxyl group such as thiomalic acid and thiosalicylic acid; having a hydroxyl group such as 2-mercaptoethanol, 1-mercapto-1-propanol, 3-mercapto-2-butanol, 1-thioglycerol and mercaptophenol Chain transfer agents; chain transfer agents having an alkoxysilyl group such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropylmethyldimethoxysilane. These chain transfer agents can be used alone or in combination of two or more.

  The ratio of the lipophilic monomer to the whole monomer component is the same as described above. The monomer component may contain a lipophilic monomer and a monomer having an unreactive group (such as an alkyl (meth) acrylate). The ratio of the chain transfer agent may be about 0.5 to 10 mol%, preferably 1 to 8 mol%, more preferably about 2 to 7 mol%, based on the entire monomer component.

  Polymerization of the monomer component, reaction between the reactive functional group of the polymer and the reactive group of the polymerizable monomer can be performed in the same manner as described above. Since a chain transfer agent is used, the molecular weight of the polymer tends to decrease. For example, the number average molecular weight (polystyrene conversion) by gel permeation chromatography is 500 to 50000, preferably 800 to 30000, more preferably 1000 to It may be about 20000.

  In addition, in the polymerization using the chain transfer agent, when a polymerizable monomer having a reactive functional group is used in combination, a reactive functional group can be introduced into both the side chain and the terminal of the copolymer, A polymerizable group can be introduced into both the side chain and the terminal by reaction with the polymerizable monomer.

  Further, if necessary, the polymer having a polymerizable group introduced into the side chain and / or terminal thereof may be a polymerizable monomer having a reactive functional group and / or a polymerizable monomer having a non-reactive group. When the monomer is graft polymerized and, if necessary, a polymerizable monomer having a reactive functional group is used, the reactivity of the polymerizable monomer with respect to the reactive functional group introduced into the graft polymer It may be a graft copolymer in which a polymerizable group is introduced by reacting a group. As the solvent for graft polymerization, the same solvents as described above can be used. The number average molecular weight (polystyrene conversion) of the graft copolymer by gel permeation chromatography may be, for example, about 1,000 to 200,000, preferably about 5,000 to 100,000.

The component (B) is often a (meth) acrylic polymer containing at least C _10-24 alkyl- (meth) acrylate as a monomer component, and the polymerizable group is a side chain and / or terminal of the polymer. It is often introduced into (especially at least the side chain).

  The double bond equivalent (for example, molecular weight per acryloyloxy) of the lipophilic resin (B) is, for example, about 100 to 3000 g / eq, preferably 200 to 2000 g / eq, and more preferably about 300 to 1000 g / eq.

  In addition, about the lipophilic resin of a component (B), the said patent document 3 etc. can be referred, for example. Moreover, the lipophilic resin of a component (B) can be obtained as a brand name "ZX-214-A" from T & K TOKA, for example.

Component (C): When forming a resin hard coat layer having a radically polymerizable group and a branched fluoroaliphatic hydrocarbon group , due to surface surface defects occurring when the coating film is dried, for example, due to the convection phenomenon of the coating liquid Defects are generated on the surface due to the appearance of geometric patterns, surface roughness such as small holes and “pear texture” due to solvent volatilization, surface roughness due to condensation, and repellency of the coating liquid due to abnormal parts of the substrate, forming a smooth surface There are cases where it is not possible. In order to suppress the generation of these defects, the type of solvent, the component ratio, and the solid content concentration are adjusted, but there are cases where sufficient countermeasures cannot be taken due to manufacturing restrictions. In such a case, it is effective to control the surface tension of the coat layer surface in a wet state from immediately after coating to drying, and a leveling agent is added for such adjustment.

  Common leveling agents are roughly classified into acrylic compounds, silicone compounds, and fluorine compounds. Among these leveling agents, the silicone leveling agent and the fluorine leveling agent exhibit leveling properties with a relatively small addition amount of 1% by weight or less with respect to the solid content of the coat layer, and more than the silicone leveling agent. Fluorine leveling agents generally tend to exhibit leveling effects with less addition. Since such a leveling agent easily aggregates on the surface of the coating film, a smoothing effect is expected when added in a small amount. For example, as a fluorine leveling agent, a chemical structure that easily aggregates is formed by a linear fluorinated hydrocarbon group (or a flexible hydrocarbon chain), and high water and oil repellency is exhibited. Specific products include the product name Novec (Sumitomo 3M Co., Ltd.), the product name MegaFac (DIC Co., Ltd.), the product name Surflon (AGC Seimi Chemical Co., Ltd.), and the product name Polyfox (Kitamura Chemical Industry Co., Ltd.). Can be illustrated.

  In addition, as countermeasures against lipid components (sebum such as fingerprints) adhering to the hard coat surface, there are two contradicting directions, namely, a direction that makes it easy to wipe fingerprints by imparting water and oil repellency, and lipophilicity. There is a direction to improve the wettability with the applied and attached fingerprint and make the fingerprint inconspicuous. However, adding a fluorine-based leveling agent with water and oil repellency to the coating film that forms the surface of the oleophilic hard coat will cause oleophobic properties contrary to the intended oleophilic design, resulting in impaired fingerprint visibility. There is. For this reason, the fluorine leveling agent is not compatible with the lipophilic hard coat layer.

  Therefore, as a result of examining various fluorine-based leveling agents, when a leveling agent having a branched fluorinated aliphatic hydrocarbon group (particularly a highly branched fluorinated aliphatic hydrocarbon group) is used, a lipophilic resin (long chain) It has been found that a lipophilic hard coat layer containing an alkyl group exhibits a high leveling effect while maintaining lipophilicity.

  That is, the component (C) of the present invention can be composed of a polymer having a radically polymerizable group and a branched-structured fluoroaliphatic hydrocarbon group. The radical polymerizable group may be a (meth) acryloyloxy group and / or a vinyl group as in the component (B), and is usually a (meth) acryloyloxy group. The radical polymerizable group may be located at the end of the main chain of the polymer, but is usually located in the side chain in many cases.

The branched fluoroaliphatic hydrocarbon group is composed of an alkyl group and / or alkenyl group having a branched structure, and at least a part of the aliphatic hydrocarbon group is fluorinated. That is, the component (C) is composed of a (meth) acrylic polymer having a branched fluoroalkyl group and / or fluoroalkenyl group in the side chain. Examples of the fluoroaliphatic hydrocarbon group include fluoroisopropyl, fluoroisobutyl, fluoro s-butyl, fluoro t-butyl, fluoroisopentyl, fluoroneopentyl, fluoro t-pentyl, fluoroisohexyl, fluoro-2-ethylhexyl group and the like. fluoroalkyl _{C 3-16} alkyl group, or these fluoro _{C 3-16} alkenyl groups corresponding to the alkyl group (such as fluoro neo-1-yl group, fluoro neo-2-yl group, fluoro t- pentane - 1-yl group, fluoro t-pentan-2-yl group, etc.). The aliphatic hydrocarbon group preferably has a highly branched structure, and 2 to 6 (preferably 2 to 4) alkyl groups may be branched based on the longest carbon chain. The alkyl chain may be a methyl group, and the alkyl chain having 2 or more carbon atoms (for example, a C _2-4 alkyl group) may be linear or branched like an isopropyl group. Such highly branched hydrocarbon groups include, for example, dimers (dimers) and trimers of alkenes (C _3-6 alkenes such as propylene, butene, isobutene, pentene, isopentene, in particular branched alkenes). In many cases, it corresponds to a hydrocarbon group of a multimer (preferably dimer to tetramer, particularly trimer) such as (trimer) and tetramer (tetramer).

Examples of the alkyl group and / or alkenyl group corresponding to the fluoroalkyl group and / or fluoroalkenyl group having such a branched structure include a 1,3-dimethylbutyl group and a 1,3-dimethyl-2-isopropylbutyl group. Branched C _6-18 alkyl groups such as 2-ethyl-2-butyl-hexyl group, 2,2,4-trimethylpentyl group, 2,2,4-trimethyl-2-isobutylpentyl group; Corresponding groups (1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-buten-1-yl group), groups corresponding to propylene trimer (1,3-dimethyl-2-isopropylidenebutenyl Group, 1,3-dimethyl-2-isopropyl-1-butenyl group), a group corresponding to butene trimer (2-ethyl-2-butyl-1-hexene) -1-yl group, 2-ethyl-2-butyl-2-hexene-1- group), groups corresponding to isobutene dimer (2,2,4-trimethyl-1-penten-1-yl group, 2, 2,4-trimethyl-2-penten-1-yl group), groups corresponding to isobutene trimer (2,2,4-trimethyl-2-isobutyl-1-penten-1-yl group, 2,2,4 _-Branched C _6-18 alkenyl groups such as -trimethyl-2-isobutyl-2-penten-1-yl group).

  Further, the aliphatic hydrocarbon group having a branched structure may be a perfluoroaliphatic hydrocarbon group in which at least a part of hydrogen atoms are substituted with fluorine atoms, and all the hydrogen atoms are substituted with fluorine atoms. Also good.

The branched fluoroalkyl group and / or branched fluoroalkenyl group often contains at least one fluoro-branched alkyl group and / or fluoro-branched alkenyl group as the minimum branched chain unit. Examples thereof include perfluoro C _4-6 alkyl groups such as perfluoroisopropyl group, perfluoroisobutyl group and perfluoroisopentyl group. Examples of the fluoro-branched alkenyl group include perfluoroisopropylidene group, perfluoro Examples thereof include perfluoro C _4-6 alkenyl groups such as a -1-isobutenyl group and a perfluoro-1-isopentenyl group. In particular, the smallest branched chain unit often contains at least one or both of a perfluoro C _4-6 alkyl group and a perfluoro C _4-6 alkenyl group.

Examples of such a fluoroaliphatic hydrocarbon group containing the smallest branched chain unit include a group represented by R ₃ in the following formula (1), such as perfluoro (1,3-dimethyl-2-isopropylidene). Denbutenyl) group (= 2-perfluoroisopropylidene-2-perfluoroisopropyl-1- (trifluoromethyl) ethyl group), (perfluoro 1,3-dimethyl-2-isopropyl-1-butenyl) group (= 2,2-di (perfluoroisopropyl) -1- (trifluoromethyl) vinyl group) and the like.

  The polymerizable monomer having such a branched structure (or) fluoroaliphatic hydrocarbon group may contain, for example, a polymerizable monomer represented by the following formula (1).

(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group or an alkyleneoxyalkylene group, and R ₃ represents the following formula (2a) or (2b)

Represents a branched fluoroalkenyl group represented by
The alkylene group and alkyleneoxyalkylene group represented by R ₂ are groups corresponding to the polymerizable monomer ((meth) acrylate) having the hydroxyl group.

  The component (C) is a polymerizable monomer having at least a branched-chain fluoroaliphatic hydrocarbon group (for example, a (meth) acrylic monomer having a branched fluoroalkyl group and / or a branched fluoroalkenyl group). It is a polymer (for example, a (meth) acrylic polymer) contained as a monomer component, and the side chain of the polymer has a branched-structured fluoroaliphatic hydrocarbon group.

Component (C) may be a homopolymer of a polymerizable monomer having a branched structure fluoroaliphatic hydrocarbon group as long as it has a polymerizable group, but at least a polymerizable monomer having a reactive functional group. In many cases, it is a copolymer with a copolymerizable monomer containing a monomer. As the copolymerizable monomer, the same (meth) acrylic monomer and vinyl monomer as the monofunctional monomer described in the above-mentioned component (A) can be used. These monofunctional monomers can be used alone or in combination of two or more. The monofunctional monomer includes at least a polymerizable monomer having a reactive functional group and includes a polymerizable monomer having a non-reactive group, as in the above-described component (B). May be. Examples of the polymerizable monomer having a reactive functional group include a polymerizable monomer having a hydroxyl group [2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) ) Hydroxy C _2-10 alkyl (meth) acrylate such as acrylate, etc. Hydroxyalkyl (meth) acrylate such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate etc. C _2-4, such as alkylene glycol mono (meth) acrylate], a polymerizable monomer having a carboxyl group [(meth) acrylic acid, a polymerizable monomer having an epoxy group [such as glycidyl (meth) acrylate, alkoxy Having polymerizable monomer [2-methacryloxy propyl trimethoxy silane, 3- (meth) acryloxy propyl trimethoxy silane, C _1-2 alkoxysilyl group and a polymerizable group such as vinyltrimethoxysilane having a silyl group Polymerizable monomer], polymerizable monomer having an isocyanate group [isocyanate alkyl (meth) acrylate such as 2-isocyanatoethyl (meth) acrylate)] and the like. These polymerizable monomers having a reactive functional group can be used alone or in combination of two or more. As the polymerizable monomer having a reactive functional group, a polymerizable monomer having a hydroxyl group, (meth) acrylic acid, or glycidyl (meth) acrylate is often used.

Examples of the polymerizable monomer having a non-reactive group include C _1-20 alkyl (meth) acrylate; C _5-10 cycloalkyl (meth) acrylate; adamantyl (meth) acrylate, and isobornyl (meth) acrylate. (Meth) acrylate having a bridged cyclic hydrocarbon group; aryl (meth) acrylate such as phenyl (meth) acrylate; aralkyl (meth) acrylate such as benzyl (meth) acrylate and 2-phenylethyl (meth) acrylate, polyoxy Examples thereof include C _2-4 alkylene glycol mono C _1-4 alkyl ether mono (meth) acrylate. As the polymerizable monomer having a non-reactive group, at least C _1-6 alkyl- (meth) acrylate is often used.

  The content of the polymerizable monomer having a branched-structured fluoroaliphatic hydrocarbon group is 5 to 75% by weight, preferably 10 to 60% by weight, more preferably 15 to 50%, based on the entire monomer component. The weight% (for example, about 20 to 40% by weight) or about 10 to 50% by weight (for example, 25 to 35% by weight) may be used. The ratio of the polymerizable monomer having a reactive functional group (such as a hydroxyl group) is 5 to 50% by weight (for example, 7.5 to 40% by weight), preferably 10 to 10% by weight based on the whole monomer component. The ratio of the polymerizable monomer having a non-reactive group (alkyl group, aralkyl group, etc.) may be 0 to 70% by weight (for example, 5 to 60% by weight), preferably 10 to 55% by weight, and more preferably about 20 to 50% by weight. The total of the monomer components is 100% by weight.

  The polymerizable group produced a polymer of a monomer component containing a polymerizable monomer having a reactive functional group, and the reactive functional group of this polymer was explained in the section of the component (B). Similarly to the above, it can be introduced by reacting a polymerizable monomer having a reactive group. For example, when a polymerizable monomer having a hydroxyl group (such as hydroxyalkyl (meth) acrylate) is used as the polymerizable monomer having a reactive functional group, alkoxysilyl is used with respect to the hydroxyl group of the produced polymer. A polymerizable group can be introduced by reacting with a polymerizable monomer having a group, a polymerizable monomer having an isocyanate group, or a polymerizable monomer having an acid anhydride group such as maleic anhydride. When a carboxyl group-containing polymerizable monomer such as acrylic acid is used, a polymerizable monomer having a hydroxyl group, a polymerizable monomer having an epoxy group, and an alkoxysilyl group are added to the carboxyl group of the copolymer. A polymerizable group can be introduced by reacting with a polymerizable monomer or the like. When using a polymerizable monomer having an epoxy group such as glycidyl (meth) acrylate, the polymerizable group is reacted by reacting a polymerizable monomer having a carboxyl group with the epoxy group of the copolymer. Can be introduced.

  Component (C) includes a (meth) acrylic monomer having a branched fluoroalkyl group or a branched fluoroalkenyl group, a (meth) acrylic monomer having a hydroxyl group, and, if necessary, these (meth) acrylic monomers A monomer component polymer containing a monomer and a copolymerizable monomer, and an isocyanate compound having a (meth) acryloyl group in the hydroxyl group of the side chain of this polymer is bonded to a urethane. It may be a polymer. JP, 2010-47680, A, etc. can be referred to for such a component (C) (leveling agent).

  Component (C) is prepared by a method similar to that of the lipophilic resin (B), for example, by reacting a monomer component with a reactive functional group of the produced copolymer and a monomer having a reactive group. It can be prepared by reacting.

  The number average molecular weight (in terms of polystyrene) of the component (C) may be, for example, 500 to 50000, preferably 1000 to 30000, and more preferably about 2000 to 20000 in gel permeation chromatography. Moreover, the double bond equivalent (for example, molecular weight per acryloyloxy) of a component (C) is 100-3000 g / eq, for example, Preferably it is 200-2000 g / eq, More preferably, it may be about 300-1000 g / eq. Good.

  Such a component (C) has low volatility and high thermal stability, and is suitable for imparting surface smoothness.

  Regarding the polymer having a branched structure aliphatic aliphatic hydrocarbon group (component (C)), JP 2010-047680 A, JP 2010-241879 A, JP 2011-057589 A, Reference can be made to Japanese Unexamined Patent Publication No. 2011-074129. The polymer (component (C)) having a branched-chain fluoroaliphatic hydrocarbon group can be obtained, for example, from Neos Co., Ltd. as “Factent” such as “Factent 602A”.

[Radical polymerization initiator (D)]
The radical curable composition may contain a radical polymerization initiator (D). In order to cure the component (A), the component (B) and the component (C) with heat energy (heat rays) or light energy (light rays), a radical polymerization initiator (D) is often included. The radical polymerization initiator (D) may be a thermal polymerization initiator (thermal radical generator such as a peroxide such as benzoyl peroxide) or a photopolymerization initiator (photo radical generator). . A preferred polymerization initiator is a photopolymerization initiator. Examples of the photopolymerization initiator include acetophenones or propiophenones, benzyls, benzoins, benzophenones, thioxanthones, and acylphosphine oxides. A conventional photosensitizer or photopolymerization accelerator (for example, tertiary amines) may be used in combination with the photopolymerization initiator.

  The polymerizable composition containing the polymerization initiator may be a thermosetting composition, but is a photocurable composition that can be cured in a short time, for example, an ultraviolet curable composition or an electron beam curable composition. Also good. In particular, a practically advantageous composition is an ultraviolet curable composition. In addition, when hardening a coating film with high energy rays, such as an electron beam, a polymerization initiator is not necessarily required.

Use amount of each component The use amount of component (B) is 0.025 to 5 parts by weight (for example, 0.05 to 4 parts by weight), preferably 0.1 to 100 parts by weight of the total amount of component (A). May be about 3 to 3 parts by weight (for example, 0.2 to 2.5 parts by weight), more preferably about 0.3 to 2 parts by weight (for example, 0.5 to 1.5 parts by weight). Even in the range of about 0.3 to 1.5 parts by weight (for example, 0.5 to 1 part by weight), a high lipophilic coating film can be obtained.

  The proportion of component (C) is 0.01 to 0.1 parts by weight (for example, 0.02 to 0.1 parts by weight), preferably 0.03 to 0 parts per 100 parts by weight of the total amount of component (A). 0.8 parts by weight (for example, 0.04 to 0.7 parts by weight), and more preferably 0.05 to 0.6 parts by weight (for example, 0.06 to 0.5 parts by weight).

  The proportion of the polymerization initiator is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 100 parts by weight of the total amount of component (A), component (B) and component (C). It may be about 1 to 8 parts by weight (particularly 1 to 5 parts by weight).

  If necessary, the polymerizable composition may further contain conventional additives, such as other thermoplastic polymers, stabilizers (antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, etc.), blocking. Inhibitors, pigments, dyes, flame retardants, flame retardant aids, fillers, organic particles (resin fine particles) or inorganic particles (inorganic fine particles), plasticizers, impact modifiers, reinforcing agents, dispersants, antistatic agents, It may contain an antibacterial agent. These additives can be used alone or in combination of two or more.

  The polymerizable composition may further contain a solvent. Examples of the solvent include hydrocarbons (toluene, hexane, etc.), alcohols (ethanol, isopropyl alcohol, methoxypropanol, ethoxyethanol, etc.), esters (ethyl acetate, butyl acetate, etc.), ketones (acetone, methyl ethyl ketone, Examples include methyl isobutyl ketone), ethers (diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, etc.), cellosolves (methyl cellosolve, etc.), cellosolve acetates (ethylene glycol monomethyl ether acetate, etc.), sulfoxides, amides, and the like. These solvents can be used alone or in combination of two or more, and may be a mixed solvent. The usage-amount of a solvent can be selected according to coating property etc., for example, 5-500 weight part (for example, 10-300 weight) with respect to 100 weight part of total amounts of component (A) (B) and (C). Part) degree.

[Method for producing hard coat film]
The hard coat film of the present invention can be obtained by applying a polymerizable composition to at least one surface of a substrate film, and then drying and curing the solvent when a solvent is used.

  As a coating method of the polymerizable composition, conventional methods such as roll coater, air knife coater, blade coater, rod coater, reverse coater, bar coater, comma coater, dip squeeze coater, die coater, gravure coater, microgravure coater Examples include coater, silk screen coater method, dip method, spray method, spinner method and the like. If necessary, the polymerizable composition may be applied multiple times. Drying may be performed, for example, at a temperature of about 40 to 150 ° C., preferably 50 to 120 ° C., and more preferably about 60 to 100 ° C.

The coating film may be cured using heat rays, but is preferably cured by irradiation with active energy rays. As active energy rays to be irradiated, radiation (gamma rays, X-rays, etc.), ultraviolet rays, visible rays, electron beams (EB), etc. can be used. As the light source, for example, in the case of ultraviolet rays, a Deep UV lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a halogen lamp, a laser light source (light source such as a helium-cadmium laser or an excimer laser) may be used. it can. The amount of irradiation light (irradiation energy) varies depending on the thickness of the coating film, but may be, for example, about 50 to 10,000 mJ / cm ² , preferably 70 to 7000 mJ / cm ² , and more preferably about 100 to 5000 mJ / cm ² . The irradiation with active energy rays can be performed in air, and if necessary, may be performed in an inert gas (for example, nitrogen gas, argon gas, helium gas, etc.) atmosphere.

  Furthermore, if necessary, after light irradiation, depending on the type of the base film, heat treatment (for example, heat treatment at a temperature of about 50 to 150 ° C.) may be performed to advance the curing.

  In addition, a hard coat layer may be formed on at least one surface of the base film, and the other surface of the base film is, for example, a transparent conductive layer, an anti-Newton ring layer, an antiglare layer, a light scattering layer, or a reflection. Functional layers such as a prevention layer, a polarizing layer, and a retardation layer may be formed. Moreover, you may form a hard-coat layer on both surfaces of a base film. In such a hard coat film, the surface of the hard coat layer (surface layer) on at least one surface may be smooth, and the surface of the hard coat layer on the other surface may be smooth, rough, or uneven. You may form in. When a rough surface or an uneven surface is formed, anti-Newton ring properties (light scattering properties, antireflection properties, etc.) can be imparted. The rough or uneven surface can be formed by applying a polymerizable composition containing organic or inorganic fine particles and curing the coating film, and applying a polymerizable composition containing a plurality of phase-separable components. Then, after the phase separation is generated, the coating film may be cured.

  By such a curing treatment, a hard coat layer can be formed on the surface of the transparent substrate film. The thickness of the hard coat layer can be selected from the range of, for example, about 1 to 100 μm, and may be usually 2 to 50 μm, preferably 3 to 25 μm (for example, 5 to 15 μm), and more preferably about 5 to 10 μm. 5 to 50 μm (especially 10 to 30 μm).

  The pencil hardness (load 750 gf) of the hard coat layer is, for example, HB or more (for example, F or more), preferably 1H or more (for example, 1H to 5H), more preferably 2H or more (for example, 2H to 4H), particularly 3H. That's it. If the pencil hardness of the hard coat layer is too low, the protective effect of the display surface is lowered, and if it is too high, cracks are likely to occur during punching.

  The hard coat layer of the hard coat film has high scratch resistance. For example, when a test is performed in which a weight of 1 kgf is placed on steel wool (# 0000) and the surface of the hard coat layer is rubbed 20 times, the flaw is not damaged.

  The transparent laminated film of the present invention has a total light transmittance of 80% or more (for example, 85 to 99.9%), preferably 88 to 99%, more preferably 90 to 98% (for example, 92) in accordance with JIS K7136. (About 96%). Moreover, transparency is high, for example, the haze value based on JISK7136 is 1.8% or less (for example, 0.2 to 1.5%), preferably 0.3 to 1.2%, more preferably About 0.5 to 1% may be sufficient.

  The contact angle of the hard coat layer with respect to water is, for example, about 90 ° or more (for example, 90 to 98 °), preferably about 92 to 97 °, and more preferably about 93 to 96 ° (for example, 94 to 96 °). If the contact angle with water is too large, repellency may occur and the smoothness of the coating surface may be reduced. If the contact angle with water is too low, the lipophilicity will decrease and the adhesion of lipid components such as sebum will be noticeable. easy. The contact angle of the hard coat layer with respect to n-hexadecane (nHD) is, for example, about 10 ° or less (for example, 3 to 10 °), preferably about 5 to 8 ° (for example, 5 to 7.5 °). . If the contact angle with respect to nHD is too large, fingerprints and sebum are easily noticeable.

  The hard coat layer of the present invention has lipophilicity, and even if a lipid component derived from a living body (such as fingerprint sebum) adheres to the lipid component, the adhesion of the lipid component is difficult to visually identify, Fingerprint visibility can be greatly reduced. In addition, it has excellent anti-fingerprint and pollutant removal properties, and even if lipid components (fingerprints) adhere to the hard coat layer surface, it can be easily done with tissue paper (for example, within 5 times, especially within 3 times). Can be removed by wiping operation).

  The hard coat film of the present invention not only has high hardness and is effective for protecting the display surface, but also can greatly reduce the visibility even when a lipid component adheres. Therefore, it is useful as a film for protecting the surface by being disposed on a display surface (for example, a touch panel surface), and reducing the visibility of lipid component adhesion traces on the display surface and / or the operation surface.

  The present invention also includes a display device provided on the surface with the hard coat film (hard coat film disposed with the hard coat layer positioned on the surface side). Examples of such a display device include a touch panel, a liquid crystal display (LCD), an organic EL display, a PDP, an FED, a CRT, and the like. It is suitable for protecting the surface by disposing a hard coat film on the operation surface.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
(A) Dipentaerythritol hexaacrylate (trade name “DPHA” manufactured by Daicel Cytec Co., Ltd.) as an acrylic monomer [polyfunctional (meth) acrylate] is added to 100 parts by weight of (B) radical polymerizable group and water repellent. Lipophilic resin having a lipophilic part [trade name “ZX-214-A” manufactured by T & K TOKA Co., Ltd .; butyl acetate / isopropyl alcohol solution of an acrylic oligomer having a radical polymerizable group and a water-repellent / lipophilic group Double bond equivalent 560 g / eq (nonvolatile content)] 1.25 parts by weight (resin content 0.5 parts by weight), (C) a resin having a radical polymerizable group and a branched fluoroaliphatic hydrocarbon group [( Made by Neos Co., Ltd., trade name “Futagent 602A”; double bond concentration 8.2 × 10 ⁻⁴ mol / g (non-volatile content); oligomer ethyl acetate solution] 0.06 Parts by weight (0.03 parts by weight as a resin component), and (D) a radical polymerization initiator (manufactured by BASF, trade name “Irgacure 184”; radical photopolymerization initiator), 3.0 parts by weight, Dilution with methyl ethyl ketone / butyl acetate = 8/2; weight ratio)) gave a coating composition having a nonvolatile content of 50% by weight.

  On one surface of a base film (polyethylene terephthalate film (PET film) having a film thickness of 188 μm (trade name “O321E188WE98” manufactured by Mitsubishi Plastics, Inc.)), the coating composition was applied at a coating speed of 3 m / min using a micro gravure coater. After being dried at 80 ° C. for about 30 seconds with a dryer, the coating film is cured by irradiating with a high-pressure mercury lamp in a nitrogen atmosphere to form a coating film (hard coat layer) having a thickness of about 7 μm. A PET film was obtained.

Example 2
Component (B) lipophilic resin [trade name “ZX-214-A” manufactured by T & K TOKA Co., Ltd.] is used in an amount of 1 part by weight, and component (C) [manufactured by Neos Co., Ltd., trade name “Furgent” 602A "] was used in the same manner as in Example 1 except that the amount used was 0.13 parts by weight (resin content was 0.05 parts by weight) to obtain a PET film having a hard coat layer.

Comparative Example 1
A PET film having a hard coat layer was obtained in the same manner as in Example 1 without adding the component (C) [trade name “Factent 602A” manufactured by Neos Co., Ltd.].

Comparative Example 2
Component (C) [made by Neos Co., Ltd., trade name “Factent 602A”, oil repellent fluorine compound having radical polymerizable group [Kitamura Chemical Industry Co., Ltd., trade name “Polyfox 3320” as a resin component] A PET film having a hard coat layer was obtained in the same manner as in Example 1 except that 0.03 part by weight was added.

  After leaving the obtained PET film having a hard coat layer at room temperature for 24 hours, the following evaluation methods were used to evaluate the pencil hardness, steel wool resistance, fingerprint resistance, and contamination of the surface coating film (hard coat layer). Substance removability, water / n-hexadecane (nHD) contact angle were measured. Moreover, while measuring the haze value and total light transmittance of the whole PET film which has a hard-coat layer, the presence or absence of an interference fringe and a repellency was evaluated. The results are shown in Table 1.

(1) Pencil Hardness Pencil hardness was evaluated according to JIS K 5600 using a scratch hardness (pencil method) testing device (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) at a load of 750 g, a 45 degree method, and a measurement distance of 30 mm. . The measurement was made 5 times with 3H and 2H pencils, and “◯” was given when the scratch was not made 3 times or more, and “X” was given when the scratch was made 3 times or more.

(2) Steel wool (SW) resistance (scratch resistance)
# 000 steel wool with a load of 1 kg and rubbed for 20 reciprocating rubs was marked with “◯”, and those with scratches were marked with “X”.

(3) Fingerprint visibility The fingerprint was adhered to the coating film, and the visibility of the fingerprint was visually observed against a black background. “◯” indicates that the fingerprint is inconspicuous, “Δ” indicates that the fingerprint is slightly conspicuous, and “x” indicates that the fingerprint is conspicuous.

(4) Contaminant removability The fingerprint was adhered to the coating film and wiped with a tissue paper to evaluate the removability of the fingerprint. The number of wipes of tissue paper until the fingerprint was removed is shown. If the number of times of wiping is up to 4, it is usually within the allowable range, but it is preferably 3 times or less.

(5) Water / n-hexadecane (nHD) contact angle Using an automatic / dynamic contact angle meter (model KDC-UZ, manufactured by Kyowa Interface Science Co., Ltd.) Five points were measured and averaged.

(6) Haze value / total light transmittance The haze value / total light transmittance was measured according to JISK 7136 using a haze meter (trade name “NDH5000W” manufactured by JASCO Corporation).

(7) Interference fringes A PET film having a hard coat layer is placed on a black background, and a three-wavelength fluorescent tube is used as a light source. The interference pattern was observed. The rainbow-colored interference pattern that was difficult to see was judged as “◯”, the thin-looking one as “△”, and the one that looked strong as “x”.

(8) Repelling The coated portion was visually observed for the presence or absence of a transparent portion having a diameter of about 0.5 mm or more in a range of 20 cm in width. Observation was performed using transmission and reflection of a fluorescent lamp. About 3 m in length was observed and the number was counted.

  As is apparent from Table 1, in Comparative Example 1 in which the component (C) is not added, “repellency” occurs on the coating surface. Further, in Comparative Example 2 in which the same amount of an oil-repellent fluorine compound that is not a fluorinated hydrocarbon group having a branched structure was added as in Example 1, “repellency” can be suppressed, but the fingerprint visibility is reduced due to the repelling of the fingerprint. To do. On the other hand, in each of the embodiments, not only can the leveling property be improved while maintaining a high hardness, but the attached fingerprint is not noticeable, and the fingerprint resistance visibility can be greatly improved. If the amount of component (C) added is too large, the contact angle with respect to nHD tends to increase. The fingerprint is not repelled on the surface of the coating and is repelled, making the fingerprint more noticeable and lowering the fingerprint visibility. It seems to do.

  The hard coat film of the present invention has high hardness and excellent transparency, and can greatly reduce the visibility of adhesion marks even when a lipid component adheres. Therefore, the hard coat film can be applied to various display devices such as a touch panel, a liquid crystal display device (LCD), and an organic EL display with the hard coat layer positioned on the surface side. In particular, it is suitable for application to a touch panel type display surface or operation surface in which an input / output operation is performed with a fingertip and lipid components are easily attached.

Claims (19)

  A hard coat film having a hard coat layer formed on at least one surface of a transparent substrate film, wherein the hard coat layer comprises a (meth) acrylic monomer or oligomer (A), a radical polymerizable group, Formed of a cured layer of a radically curable composition comprising a lipophilic resin (B) having a water-repellent lipophilic part and a resin (C) having a radically polymerizable group and a branched fluoroaliphatic hydrocarbon group, and A hard coat film having a pencil hardness of 1H or more.   The hard coat film according to claim 1, wherein the component (A) contains at least a polyfunctional (meth) acrylate having a plurality of (meth) acryloyl groups.   The hard coat film according to claim 1 or 2, wherein the component (B) is a (meth) acrylic polymer having a radical polymerizable group and a non-aromatic hydrocarbon group having 10 or more carbon atoms in the side chain.   The hard coat film according to any one of claims 1 to 3, wherein the component (B) is a polymer of a monomer component containing (meth) acrylate having a long-chain alkyl group in a proportion of 10 to 70% by weight. Component (B) is a (meth) acrylic polymer containing at least C _10-24 alkyl (meth) acrylate as a monomer component, and component (B) is added to 100 parts by weight of the total amount of component (A). The hard coat film according to claim 1, which is contained at a ratio of 0.025 to 5 parts by weight.   Component (C) has a radically polymerizable group and a (meth) acrylic polymer containing a (meth) acrylic monomer having a branched fluoroalkyl group or branched fluoroalkenyl group in the side chain as a monomer component The hard coat film according to claim 1.   The component (C) is a (meth) acrylic polymer containing a (meth) acrylic monomer having a perfluoroisopropyl group and / or a perfluoroisopropylidene group as a monomer component. The hard coat film according to any one of the above.   Component (C) is a (meth) acrylic monomer having a branched fluoroalkyl group or branched fluoroalkenyl group, a (meth) acrylic monomer having a hydroxyl group, and if necessary, these (meth) acrylic monomers A monomer component polymer containing a monomer and a copolymerizable monomer, and an isocyanate compound having a (meth) acryloyl group in the hydroxyl group of the side chain of this polymer is bonded to a urethane. The hard coat film according to claim 1, wherein the hard coat film is a polymer.   The component (C) is a polymer of a monomer component containing a (meth) acrylic monomer having a branched fluoroalkyl group or a branched fluoroalkenyl group in a proportion of 5 to 75% by weight. The hard coat film according to any one of the above.   The ratio of a component (C) is 0.01-0.1 weight part with respect to 100 weight part of total amounts of a component (A), The hard coat film in any one of Claims 1-9.   The hard coat film according to any one of claims 1 to 10, wherein the radical curable composition further contains a radical polymerization initiator (D).   The hard coat film according to claim 1, wherein the hard coat layer has a pencil hardness of 2H or more.   The hard coat film according to claim 1, having a haze value of 1.8% or less.   A hard coat layer is formed on both sides of the base film, the surface of the hard coat layer on one side is smooth, and the surface of the hard coat layer on the other side is formed smooth or rough or uneven Item 14. The hard coat film according to any one of Items 1 to 13.   The hard coat film according to claim 1, which is a film for protecting a display surface or a touch panel surface.   The hard coat film according to claim 1, wherein the transparent substrate film is a polyester resin, an acrylic resin, a polyolefin resin film, or a cellulose resin film.   (Meth) acrylic monomer or oligomer (A), a lipophilic resin (B) having a radical polymerizable group and a water-repellent lipophilic portion, a radical polymerizable group and a branched fluoroaliphatic hydrocarbon group A radical curable composition comprising a resin (C) and forming a hard coat layer having a pencil hardness of 1H or more by curing.   On at least one surface of the transparent substrate film, a (meth) acrylic monomer or oligomer (A), a lipophilic resin (B) having a radical polymerizable group and a water-repellent lipophilic portion, and radical polymerizable Of a hard coat film in which a radical curable composition containing a group and a resin (C) having a branched fluoroaliphatic hydrocarbon group is applied and the coating film is cured to form a hard coat layer having a pencil hardness of 1H or more. Method.   The display apparatus which equips the surface with the hard coat film in any one of Claims 1-16.