Fingerprint-resistant composition, cured product layer, fingerprint-resistant article, and hard coating film

Abstract

The invention provides a fingerprint-resistant composition for a hard coating film. The fingerprint-resistant composition comprises: at least one selected from the group consisting of polyfunctional (meth) acrylate monomers, (meth) acrylate prepolymers, and urethane polymers; the present invention relates to a fingerprint-resistant composition comprising a polyethylene terephthalate film having a thickness of 125 [mu] m, a cured product layer having a thickness of 10 [mu] m and formed by curing the fingerprint-resistant composition, and a plasticizer, the number of scratches occurring when the surface of the cured product layer is wiped five times at a load of 125 g / cm2 and 10 cm back and forth using # 0000 steel wool. According to the cured product layer based on the fingerprint-resistant composition, the scratch resistance is excellent, fingerprint marks caused by sebum do not need to be wiped off, and the fingerprint marks cannot be seen.

Description

Technical Field

[0001] The present invention relates to an anti-fingerprint composition, a cured product and a cured product layer of the anti-fingerprint composition, an anti-fingerprint article, and an anti-fingerprint hard coating film. Background Art

[0002] In recent years, various electronic devices have been using touch panels that are both display devices and input means. Since the touch panels are often operated with fingers, fingerprints are usually attached to the surface of the touch panels due to the sebum of the fingers. If fingerprints are attached to the surface of the touch panel, the appearance will be deteriorated and the displayed image will be difficult to see.

[0003] In order to prevent scratches, a hard coating film having a hard coating layer is often provided on the surface of the touch panel as described above. Therefore, Patent Document 1 proposes a hard coating film that can easily wipe off attached fingerprints.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2014-232277 Summary of the invention

[0007] 1. Technical issues to be resolved

[0008] The hard coating film described in Patent Document 1 can easily wipe off attached fingerprints, but requires an operation of wiping off sebum.

[0009] The present invention has been made in view of such actual situation, and an object of the present invention is to provide a fingerprint-resistant composition, a cured product, a cured product layer, a fingerprint-resistant article, and a hard coating film which can achieve excellent scratch resistance, eliminate the need to wipe off fingerprints caused by sebum, and make fingerprints invisible.

[0010] (II) Technical solution

[0011] In order to achieve the above object, first, the present invention provides an anti-fingerprint composition, which contains: at least one selected from a multifunctional (meth)acrylate monomer, a (meth)acrylate prepolymer and a urethane polymer; and a plasticizer, wherein the anti-fingerprint composition is characterized in that a cured product layer with a thickness of 10 μm formed by curing the anti-fingerprint composition is formed on a polyethylene terephthalate film with a thickness of 125 μm, and a #0000 steel wool is used on the surface of the cured product layer at a temperature of 125 g / cm 2 When the load was applied 5 times with a reciprocating motion of 10 cm, the number of scratches generated was 10 or less (Invention 1).

[0012] The cured product formed by curing the anti-fingerprint composition of the above invention (Invention 1) has the above-mentioned physical properties, thereby exhibiting excellent scratch resistance. In addition, even if the cured product (layer) formed by curing the anti-fingerprint composition containing the above-mentioned components has fingerprints caused by sebum attached to the surface of the cured product (layer), the sebum will be absorbed by the cured product (layer) over time. Therefore, it is not necessary to wipe off the fingerprints caused by sebum, and the fingerprints can be made invisible.

[0013] The above invention (Invention 1) preferably contains a cross-linking agent (Invention 2).

[0014] Second, the present invention provides a cured product obtained by curing the anti-fingerprint composition (Inventions 1 and 2) (Invention 3).

[0015] Thirdly, the present invention provides a cured product layer obtained by curing the anti-fingerprint composition (Inventions 1 and 2) into a layer (Invention 4).

[0016] Fourthly, the present invention provides a fingerprint-resistant article having the above-mentioned cured product layer on the surface (Invention 4) (Invention 5).

[0017] Fifth, the present invention provides a hard coating film, comprising: a substrate film, and a hard coating layer provided on at least one side of the substrate film, wherein the hard coating layer is formed by curing an anti-fingerprint composition, wherein the anti-fingerprint composition contains: at least one selected from a multifunctional (meth)acrylate monomer, a (meth)acrylate prepolymer, and a urethane polymer; and a plasticizer, wherein the hard coating film is characterized in that a #0000 steel wool is used on the surface of the hard coating layer at a temperature of 125 g / cm 2 When the load was applied 5 times with a reciprocating motion of 10 cm, the number of scratches generated was 10 or less (Invention 6).

[0018] In the above invention (Invention 6), it is preferred that the anti-fingerprint composition contains a crosslinking agent (Invention 7).

[0019] In the above inventions (Inventions 6 and 7), it is preferred that the thickness of the hard coat layer is 0.5 μm or more and 50 μm or less (Invention 8).

[0020] The hard coat film of the above inventions (Inventions 6 to 8) is preferably for optical use (Invention 9).

[0021] (III) Beneficial effects

[0022] The anti-fingerprint composition, cured product, cured product layer, anti-fingerprint article, and hard coating film of the present invention can achieve excellent scratch resistance without wiping off fingerprints caused by sebum, and the fingerprints are invisible. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a cross-sectional view of a hard coating film according to one embodiment of the present invention. DETAILED DESCRIPTION

[0024] Hereinafter, embodiments of the present invention will be described.

[0025] [Anti-fingerprint composition]

[0026] Preferably, the anti-fingerprint composition of one embodiment of the present invention (hereinafter sometimes referred to as "anti-fingerprint composition F") contains: at least one selected from a multifunctional (meth)acrylate monomer, a (meth)acrylate prepolymer and a urethane polymer (hereinafter sometimes referred to as "curable component (A)"); and a plasticizer (B). In addition, a cured product layer having a thickness of 10 μm formed by curing the anti-fingerprint composition F is formed on a polyethylene terephthalate film having a thickness of 125 μm, and the surface of the cured product layer is subjected to a 125 g / cm2 curing process using #0000 steel wool. 2 When the load is applied 5 times with a 10 cm reciprocating motion, the number of scratches produced is less than 10.

[0027] The solidified material cured by the anti-fingerprint composition F of the present embodiment has the above-mentioned physical properties, thereby exhibiting excellent scratch resistance, and when the solidified material is in a layered state, it becomes a hard coating. In addition, in the solidified material (layer) cured by the anti-fingerprint composition F containing the curable component (A) and the plasticizer (B), even if fingerprints caused by sebum are attached to the surface of the solidified material (layer), the sebum will be absorbed by the solidified material (layer) over time. Therefore, there is no need to wipe off the fingerprints caused by sebum, and the fingerprints can be made invisible. This effect is sometimes called "anti-fingerprint property".

[0028] In addition, in this specification, "(meth)acrylate" refers to both acrylate and methacrylate. The same applies to other similar terms.

[0029] 1. Each ingredient

[0030] (1) Curable component (A)

[0031] In this embodiment, the multifunctional (meth)acrylate monomer, (meth)acrylate prepolymer and urethane polymer as the curable component (A) are curable materials, which may be thermosetting or active energy ray curable. The multifunctional (meth)acrylate monomer, (meth)acrylate prepolymer and urethane polymer may be used alone or in combination of any two or three.

[0032] Examples of the polyfunctional (meth)acrylate monomer include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, dicyclopentyl di(meth)acrylate, caprolactone-modified dipentenyl di(meth)acrylate, ethylene oxide-modified phosphoric acid di(meth)acrylate, allylated cyclohexyl di(meth)acrylate, isocyanurate di(meth)acrylate, tris(meth)acrylate, and tert-butyl esters. Multifunctional (meth)acrylates such as methylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate, tri(acryloyloxyethyl)isocyanurate, propionic acid-modified dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate. These may be used alone or in combination of two or more.

[0033] Examples of the (meth)acrylate prepolymer include polyester acrylate-based, epoxy acrylate-based, urethane acrylate-based, and polyol acrylate-based prepolymers.

[0034] The polyester acrylate prepolymer can be obtained, for example, by esterifying the hydroxyl groups of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of a polycarboxylic acid and a polyol with (meth)acrylic acid, or by esterifying the terminal hydroxyl groups of an oligomer obtained by adding an alkylene oxide to a polycarboxylic acid with (meth)acrylic acid.

[0035] The epoxy acrylate prepolymer can be obtained by, for example, reacting and esterifying an oxirane ring of a relatively low molecular weight bisphenol epoxy resin or a novolac epoxy resin with (meth)acrylic acid.

[0036] The urethane acrylate prepolymer can be obtained by esterifying a polyurethane oligomer obtained by a reaction of a polyether polyol or a polyester polyol with a polyisocyanate with (meth)acrylic acid, for example.

[0037] The polyol acrylate-based prepolymer can be obtained, for example, by esterifying a hydroxyl group of a polyether polyol with (meth)acrylic acid.

[0038] The (meth)acrylate prepolymer may have a reactive functional group that reacts with the crosslinking agent (C) described below. Examples of the reactive functional group include a hydroxyl group, a carboxyl group, and an amino group.

[0039] The weight average molecular weight of the (meth)acrylate prepolymer is preferably 1,000 to 60,000, more preferably 3,000 to 40,000, and particularly preferably 5,000 to 30,000. The “weight average molecular weight” in this specification is a value measured by gel permeation chromatography (GPC) in terms of standard polystyrene.

[0040] The above prepolymers may be used alone or in combination of two or more.

[0041] Urethane polymers are generally obtained by reacting a polyol compound with a polyisocyanate compound. Examples of polyol compounds include polyester polyols, polyether polyols, polyether ester polyols, polyester amide polyols, acrylic polyols, polycarbonate polyols, polyhydroxyalkanes, polyurethane polyols, etc. These can be used alone or in combination of two or more.

[0042] Examples of the polyisocyanate compound include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, aromatic aliphatic diisocyanates, triisocyanates, etc. These may be used alone or in combination of two or more.

[0043] The urethane polymer may have a reactive functional group that reacts with the crosslinking agent (C) described below. Examples of the reactive functional group include hydroxyl group, carboxyl group, and amino group. Among them, hydroxyl group is preferred because it is likely to remain in the production process of the urethane polymer.

[0044] The weight average molecular weight of the urethane polymer is preferably 1,000 to 300,000, more preferably 5,000 to 200,000, particularly preferably 10,000 to 100,000, and further preferably 20,000 to 60,000.

[0045] Among the above-mentioned curable components (A), carbamate polymers are preferred from the viewpoint that the scratch resistance is excellent even when a plasticizer (B) is added and the sebum absorption brought by the plasticizer (B) is easily exerted. Among them, when an isocyanate crosslinking agent is used as the crosslinking agent (C) described later, a carbamate polymer having a hydroxyl group is particularly preferred. By combining them, the hardness of the obtained cured product can be effectively improved, making the scratch resistance more excellent.

[0046] (2) Plasticizer (B)

[0047] The plasticizer (B) is generally a material that softens a resin, but in the present embodiment, the plasticizer (B) is present in a cured product having hard-coat properties, thereby absorbing sebum attached to the surface of the cured product.

[0048] Examples of the plasticizer (B) include citric acid plasticizers such as acetyl tributyl citrate and acetyl triethyl citrate; phthalate plasticizers such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, di-n-octyl phthalate, and dicyclohexyl phthalate; trimellitic acid ester plasticizers such as trioctyl trimellitic acid, triisononyl trimellitic acid, and triisodecyl trimellitic acid; dioctyl adipate , diisononyl adipate, diisodecyl adipate and other adipic acid plasticizers; phthalic acid polyester and other polyester plasticizers; tricresyl phosphate, trioctyl phosphate, triphenyl phosphate and other phosphate ester plasticizers; epoxidized linseed oil, epoxidized butyl stearate and other epoxy plasticizers; liquid polybutene, mineral oil, lanolin, wax, liquid polyisoprene, liquid polyacrylate, triethanolamine, alkylamine, amine-alkylene oxide adduct, glycerol, diglycerol, silicone oil, etc. These can be used alone or in combination of two or more.

[0049] Among them, from the viewpoint of maintaining scratch resistance while exhibiting sebum absorption, citric acid-based plasticizers are preferred, and acetyl tributyl citrate is more preferred.

[0050] The content of the plasticizer (B) in the anti-fingerprint composition F of the present embodiment is preferably 0.1 to 100 parts by mass, more preferably 1.0 to 75 parts by mass, particularly preferably 3.0 to 50 parts by mass, further preferably 6.0 to 25 parts by mass, and particularly preferably 9.0 to 15 parts by mass, relative to 100 parts by mass of the curable component (A). This allows effective sebum absorption while maintaining scratch resistance.

[0051] (3) Cross-linking agent (C)

[0052] The anti-fingerprint composition F of this embodiment also preferably contains a crosslinking agent (C). By containing a crosslinking agent (C), crosslinking with the curable component (A) can further increase the hardness of the obtained cured product and make the scratch resistance (hard coating property) more excellent.

[0053] The crosslinking agent (C) may be any agent as long as it can react with the curable component (A) and crosslink with the curable component (A). Examples of the crosslinking agent (C) include isocyanate crosslinking agents, epoxy crosslinking agents, amine crosslinking agents, melamine crosslinking agents, aziridine crosslinking agents, hydrazine crosslinking agents, aldehyde crosslinking agents, oxazoline crosslinking agents, metal alkoxide crosslinking agents, metal chelate crosslinking agents, metal salt crosslinking agents, and ammonium salt crosslinking agents.

[0054] When the curable component (A) is a urethane polymer (particularly a urethane polymer having a hydroxyl group), it is preferred to use an isocyanate crosslinking agent that easily crosslinks the urethane polymer. In addition, the crosslinking agent (C) can be used alone or in combination of two or more.

[0055] The isocyanate crosslinking agent contains at least a polyisocyanate compound. Examples of the polyisocyanate compound include aromatic polyisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate; and biuret and isocyanurate forms thereof; and adducts thereof as reaction products with low molecular weight active hydrogen-containing compounds such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, and castor oil. Among them, isocyanurate forms of aliphatic polyisocyanates are preferred from the perspective of maintaining scratch resistance while exerting sebum absorption.

[0056] The content of the crosslinking agent (C) in the anti-fingerprint composition F of the present embodiment is preferably 1 to 100 parts by mass, more preferably 5 to 75 parts by mass, particularly preferably 10 to 50 parts by mass, and further preferably 15 to 25 parts by mass, relative to 100 parts by mass of the curable component (A). Thus, while maintaining the sebum absorbency brought about by the plasticizer (B), the scratch resistance (hard coating property) can be made more excellent.

[0057] (4) Leveling agent (D)

[0058] The anti-fingerprint composition F of this embodiment also preferably contains a leveling agent (D). This allows the formed cured layer to have a uniform film thickness without streaky defects or unevenness, and to exhibit excellent optical properties and appearance.

[0059] As the leveling agent (D), for example, silicone leveling agents, fluorine leveling agents, acrylic leveling agents, vinyl leveling agents, etc. can be mentioned, among which silicone leveling agents are preferred from the perspective of leveling properties or compatibility with other components. In addition, the leveling agent (D) can be used alone or in combination of two or more.

[0060] The leveling agent (D) may be a modified leveling agent or an unmodified leveling agent. Furthermore, the leveling agent (D) may have a reactive group or may not have a reactive group, but from the perspective of effectively exerting leveling properties while maintaining scratch resistance (hard coating properties) and sebum absorption properties, it is preferred to have a reactive group, and particularly preferably a hydroxyl group.

[0061] The content of the leveling agent (D) in the anti-fingerprint composition F of the present embodiment is preferably 0.01 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass, and further preferably 0.3 to 2 parts by mass, relative to 100 parts by mass of the curable component (A). Thus, the leveling property can be effectively exhibited while maintaining the scratch resistance (hard coating property) and the sebum absorption property.

[0062] (5) Other ingredients

[0063] In addition to the above components, the anti-fingerprint composition F of this embodiment may contain various additives. Examples of the various additives include photopolymerization initiators, fillers, dispersants, antifouling agents, ultraviolet absorbers, infrared absorbers, antioxidants, light stabilizers, antistatic agents, silane coupling agents, anti-aging agents, polymerization inhibitors, colorants, surfactants, storage stabilizers, lubricants, defoaming agents, and the like.

[0064] 2. Preparation of Anti-Fingerprint Composition

[0065] The anti-fingerprint composition F of the present embodiment is prepared by mixing the curable component (A), the plasticizer (B), and, if necessary, the crosslinking agent (C), the leveling agent (D), additives, and the like, preferably in a solvent.

[0066] [cured material]

[0067] The cured product according to one embodiment of the present invention is obtained by curing the anti-fingerprint composition F according to the above embodiment. The cured product according to this embodiment can exhibit excellent scratch resistance and anti-fingerprint properties.

[0068] When the anti-fingerprint composition F of the above embodiment is cured, it is preferred to perform thermal curing or active energy ray curing depending on the type of the anti-fingerprint composition F.

[0069] The heating temperature during heat curing is preferably 15 to 100° C., particularly preferably 18 to 60° C., and further preferably 22 to 40° C. The heating time is preferably 1 to 14 days, particularly preferably 2 to 10 days, and further preferably 3 to 7 days.

[0070] Examples of active energy rays include ultraviolet rays and electron beams. Ultraviolet irradiation can be performed using, for example, a high-pressure mercury lamp, an H lamp manufactured by Heraeus, a xenon lamp, etc. The ultraviolet irradiation amount is preferably an illuminance of 50 to 1000 mW / cm 2 , Light intensity 50~1000mJ / cm 2 On the other hand, electron beam irradiation can be performed using an electron beam accelerator or the like, and the irradiation amount of the electron beam is preferably about 10 to 1000 krad.

[0071] [Cured layer]

[0072] The cured layer of one embodiment of the present invention is formed by curing the anti-fingerprint composition F of the above embodiment into a layer, and is a so-called hard coat layer. The cured layer of this embodiment exhibits excellent scratch resistance and anti-fingerprint properties.

[0073] The thickness of the cured product layer in this embodiment is preferably 0.5 to 50 μm, more preferably 1.0 to 30 μm, particularly preferably 2.0 to 20 μm, further preferably 3.0 to 15 μm, and particularly preferably 5.0 to 12 μm. This can exhibit excellent scratch resistance and sebum absorption.

[0074] When forming the cured product layer of the present embodiment, the coating liquid of the anti-fingerprint composition F of the above embodiment is applied to a desired object and dried to cure the formed coating layer.

[0075] The coating liquid of the fingerprint-resistant composition F may be the fingerprint-resistant composition F itself, or may contain a solvent as required. The solvent may be used to improve coating properties, adjust viscosity, adjust solid content concentration, etc., and may be used without particular limitation as long as the components are dissolved or dispersed. Specific examples of solvents include: alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, ethyl lactate, and γ-butyrolactone; ethers such as ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), diethylene glycol monobutyl ether (butyl cellosolve), and propylene glycol monomethyl ether; aromatic hydrocarbons such as benzene, toluene, and xylene; amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, etc.

[0076] The concentration and viscosity of the coating liquid of the anti-fingerprint composition F are not particularly limited as long as they are within the coating range and can be appropriately selected according to the situation. For example, the anti-fingerprint composition F is diluted to a concentration of 10 to 60% by mass.

[0077] The coating liquid of the anti-fingerprint composition F can be applied by a common method, for example, by bar coating, knife coating, roll coating, blade coating, die coating, or gravure coating.

[0078] The coating liquid is preferably dried after application by heat treatment. The heating temperature of the heat treatment is preferably 50 to 150° C., particularly preferably 70 to 120° C. The heating time is preferably 10 seconds to 10 minutes, particularly preferably 50 seconds to 2 minutes.

[0079] The curing method and curing conditions of the coating layer of the anti-fingerprint composition F are as described above.

[0080] [Anti-fingerprint items]

[0081] The anti-fingerprint article according to one embodiment of the present invention is an article having the above-mentioned cured product layer on the surface. The anti-fingerprint article according to this embodiment exhibits excellent scratch resistance and anti-fingerprint properties on the surface of the cured product layer.

[0082] The type of article is not particularly limited, as long as it is an article requiring scratch resistance and fingerprint resistance, and generally an article having a certain degree of hardness and smoothness is selected. Examples of such articles include resin products (including molded products, films, etc.), glass products, metal products, ceramic products, etc.

[0083] [Hard Coat]

[0084] Preferably, a hard coating film of one embodiment of the present invention comprises: a substrate film and a hard coating layer provided on at least one side of the substrate film. The hard coating layer is formed by curing an anti-fingerprint composition (hereinafter sometimes referred to as "anti-fingerprint composition F'"), wherein the anti-fingerprint composition contains: at least one selected from a multifunctional (meth)acrylate monomer, a (meth)acrylate prepolymer and a urethane polymer (curable component (A)); and a plasticizer (B). In addition, a #0000 steel wool is used on the surface of the hard coating layer at a temperature of 125 g / cm 2 When the load is applied 5 times with a 10 cm reciprocating motion, the number of scratches produced is less than 10.

[0085] The hard coating film of the present embodiment has the above-mentioned physical properties, thereby exerting excellent scratch resistance. In addition, in the hard coating layer formed by curing the fingerprint-resistant composition F' containing a curable component (A) and a plasticizer (B), even if the fingerprint marks caused by sebum are attached to the surface of the hard coating layer, the sebum will be absorbed by the hard coating layer over time. Therefore, it is not necessary to wipe off the fingerprint marks caused by sebum, so that the fingerprint marks cannot be seen, and the fingerprint resistance is excellent. In addition, because the finger sliding property of the surface of the above-mentioned hard coating layer is excellent, the hard coating film of the present embodiment is suitable as a surface layer of a touch panel, etc.

[0086] The anti-fingerprint composition F' of this embodiment has the same composition as the anti-fingerprint composition F of the above embodiment except that the physical properties based on the scratch resistance test are not required.

[0087] Hereinafter, the hard coating film according to the present embodiment will be described with reference to the drawings. Figure 1 This is a cross-sectional view of a hard coating film according to one embodiment of the present invention. A hard coating film 1 according to this embodiment includes a base film 11 and a hard coating layer 12 provided on one surface side of the base film 11 .

[0088] 1. Requirements

[0089] (1) Hard coating

[0090] The hard coating layer 12 of the hard coating film 1 of the present embodiment is formed by curing the anti-fingerprint composition F', wherein the anti-fingerprint composition F' contains: at least one selected from a multifunctional (meth)acrylate monomer, a (meth)acrylate prepolymer and a urethane polymer (curable component (A)); and a plasticizer (B).

[0091] The details of the curable component (A), plasticizer (B) and other components, and the curing method of the anti-fingerprint composition F' are the same as those of the previous embodiment. The thickness of the hard coating layer 12 is the same as that of the cured product layer of the previous embodiment.

[0092] (2) Base film

[0093] The base film 11 is not particularly limited, but a resin film is preferably used. In particular, in the case of optical applications, a resin film having a predetermined transparency is preferably used.

[0094] Examples of such resin films include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyolefin films such as polyethylene film and polypropylene film; resin films such as cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, fluororesin film, polyamide film, acrylic resin film, polyurethane resin film, norbornene polymer film, cyclic olefin polymer film, cyclic conjugated diene polymer film, vinyl alicyclic hydrocarbon polymer film, and laminated films thereof. Among them, polyethylene terephthalate films, polycarbonate films, triacetyl cellulose films, norbornene-based polymer films, and the like are preferred from the viewpoint of mechanical strength and the like.

[0095] In order to improve the adhesion between the layers provided on the surface of the substrate film 11, the surface treatment may be applied to one or both sides by primer treatment, oxidation method, convexoconcave method, etc. as required. The surface treatment may be applied to one or both sides by primer treatment, oxidation method, convexoconcave method, etc. These surface treatment methods may be appropriately selected according to the type of the substrate film 11, but generally, the corona discharge treatment method is preferably adopted from the perspectives of improving the adhesion effect and operability.

[0096] The thickness of the base film 11 varies depending on its type, purpose, etc., but is usually preferably 25 to 5000 μm, more preferably 50 to 2000 μm, particularly preferably 75 to 1000 μm, further preferably 90 to 500 μm, and particularly preferably 110 to 300 μm.

[0097] (3)Adhesive layer

[0098] The hard coat film 1 of this embodiment may also include an adhesive layer on the surface side of the substrate film 11 opposite to the hard coat layer 12. The adhesive constituting the adhesive layer is not particularly limited, and for example, known adhesives such as acrylic adhesives, rubber adhesives, silicone adhesives, and urethane adhesives can be used, and an adhesive having a predetermined transparency is preferably used.

[0099] In addition, when the hard coat film 1 of the present embodiment has the above-mentioned adhesive layer, the hard coat film 1 of the present embodiment may also be laminated with a release film on the surface of the adhesive layer opposite to the base film 11. The release film is not particularly limited as long as it has the desired release properties on its release surface (the surface in contact with the adhesive layer), and a known release film such as a release film obtained by performing a release treatment on one side of a resin film with a release agent can be used.

[0100] 2. Method for manufacturing hard coating film

[0101] The hard coating film 1 of this embodiment can be produced by coating the anti-fingerprint composition F' onto the substrate film 11 and curing the coating layer. The coating method and curing method of the anti-fingerprint composition F' are the same as those of the cured product and cured product layer of the previous embodiment.

[0102] 3. Physical properties of hard coating

[0103] (1) Haze value

[0104] The haze value of the hard coating film 1 is preferably 0 to 10%, more preferably 0.1 to 6.0%, particularly preferably 0.8 to 3.0%, and further preferably 1.5 to 2.0%. Therefore, it is particularly suitable for optical applications. In addition, the "haze value" in this specification is a value measured according to JIS K7136:2000.

[0105] (2) Change in haze value

[0106] When a 0.2 mass % ethanol solution of oleic acid (simulated sebum liquid) is applied to the surface of the hard coating film 1 of the present embodiment using a wire bar #2 and allowed to dry naturally, the upper limit of the haze value change (points) obtained by subtracting the haze value (%) before the application from the haze value (%) after the application of the simulated sebum liquid for 25 hours is preferably 2.0 points or less, more preferably 1.5 points or less, particularly preferably 1.0 points or less, further preferably 0.5 points or less, and preferably 0.1 points or less, and the lower limit is most preferably 0.0 points. Since the haze value change is small as described above, the simulated sebum liquid can be absorbed by the hard coating film 12 over time, so even if fingerprints are attached to the surface of the hard coating film 1 (hard coating film 12), the fingerprints will not be visible over time.

[0107] (3) Contact angle

[0108] The oleic acid contact angle of the hard coating layer 12 of the hard coating film 1 of the present embodiment is preferably 30° to 130°, more preferably 40° to 110°, particularly preferably 50° to 90°, and further preferably 60° to 70°. In addition, the so-called "oleic acid contact angle" refers to the angle on the side containing the droplet among the angles formed by the droplet tangent line of the grounding part of the hard coating surface of the droplet and the hard coating surface when the oleic acid droplet is left stationary on the surface of the hard coating.

[0109] The water contact angle of the surface of the hard coating layer 12 of the hard coating film 1 of this embodiment is preferably 50° to 160°, more preferably 70° to 140°, particularly preferably 90° to 120°, and further preferably 100° to 110°. The detailed method for measuring the contact angle is shown in the test examples described below.

[0110] (4) Surface free energy

[0111] The surface free energy of the hard coating layer 12 of the hard coating film 1 of the present embodiment is preferably 1 to 40 mJ / m 2 , more preferably 5 to 35 mJ / m 2 , particularly preferably 10 to 30 mJ / m 2 , more preferably 15~25mJ / m 2 The method for measuring the surface free energy is shown in the test examples described later.

[0112] In addition, it is preferred that the cured product, cured product layer, and anti-fingerprint article of the aforementioned embodiment also have the same physical properties as described above.

[0113] 4. Application of hard coating

[0114] The hard coating film 1 of this embodiment can be used without any particular limitation as long as it is used for applications requiring scratch resistance and fingerprint resistance, and is particularly suitable for optical applications. Specifically, the hard coating film 1 of this embodiment can be used as a surface layer of various displays (display bodies) such as liquid crystal displays, organic EL displays, and touch panels. More specifically, it is preferably stacked on a covering material in a display having a display body module such as a liquid crystal (LCD) module, a light emitting diode (LED) module, an organic electroluminescent (organic EL) module, etc. The stacking of the hard coating film 1 on the covering material is preferably attached via the aforementioned adhesive layer.

[0115] By laminating the hard coating film 1 of this embodiment on a display body, a display with a hard coating film can be obtained. Specifically, the display with a hard coating film comprises a hard coating film and a display body, and is formed by laminating the substrate film side of the hard coating film on the display surface side of the display body. The hard coating film may be directly laminated on the display surface of the display body, or may be laminated on the display surface side of the display body via other members, layers, etc.

[0116] The embodiments described above are described to facilitate understanding of the present invention, and are not described to limit the present invention. Therefore, each element disclosed in the above embodiments also includes all design changes or equivalents within the technical scope of the present invention.

[0117] For example, another layer may be interposed between the base film 11 and the hard coating layer 12 of the hard coating film 1. In addition, the hard coating layer 12 may be provided on both surfaces of the base film 11.

[0118] In addition, unless otherwise specified, in this specification, when "X to Y" (X, Y are arbitrary numbers) is recorded, it means "X or more and Y or less", and also includes the meaning of "preferably greater than X" or "preferably less than Y". In addition, unless otherwise specified, in this specification, when "X or more" (X is an arbitrary number) is recorded, it includes the meaning of "preferably greater than X", and unless otherwise specified, when "Y or less" (Y is an arbitrary number) is recorded, it includes the meaning of "preferably less than Y".

[0119] Example

[0120] Hereinafter, the present invention will be described in more detail using examples and the like, but the scope of the present invention is not limited to these examples and the like.

[0121] [Example 1]

[0122] 100 parts by mass (solid content conversion value, the same below) of a urethane polymer (weight average molecular weight: 32000, containing hydroxyl groups) as a thermosetting resin, 11.8 parts by mass of acetyl tributyl citrate as a plasticizer, 18 parts by mass of an isocyanurate of hexamethylene diisocyanate (manufactured by Mitsui Chemicals, Inc., product name “TAKENATE D-170HN”) as a crosslinking agent, and 0.75 parts by mass of a silicone leveling agent (manufactured by BYK-Chemie, product name “BYK-SILCLEAN 3700”, containing hydroxyl groups) were mixed with toluene to obtain a coating liquid of an anti-fingerprint composition having a solid content concentration of 25% by mass.

[0123] The coating liquid of the anti-fingerprint composition obtained above was applied on one side of a polyethylene terephthalate film (manufactured by TORAY INDUSTRIES, INC., product name "LUMIRROR U48", thickness: 125 μm) as a substrate film using a wire bar #30, and heated and dried at 120°C for 1 minute to form a coating layer. Then, the coating layer was left at room temperature for 4 days to thermally cure. In this way, a coating layer with a thickness of 10 μm was formed on the substrate film to obtain a coating film.

[0124] The thickness of the coating layer is a value measured using a constant pressure thickness tester (manufactured by TECLOCK CORPORATION, product name "PG-02") in accordance with JIS K7130 (the same shall apply hereinafter).

[0125] [Comparative Example 1]

[0126] Propylene glycol monomethyl ether was used to mix 100 parts by mass of a polyfunctional urethane acrylate (manufactured by Arakawa Chemical Industries, Ltd., product name “BEAMSET 577”) as a UV-curable resin, 25 parts by mass of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate as a plasticizer, 0.05 parts by mass of a silicone leveling agent (manufactured by BYK-Chemie, product name “BYK-3550”), and 5 parts by mass of α-hydroxyphenyl ketone as a photopolymerization initiator to obtain a coating liquid of an anti-fingerprint composition having a solid content concentration of 40% by mass.

[0127] The anti-fingerprint composition coating liquid obtained above was applied onto one surface of a polyethylene terephthalate film (manufactured by TORAY INDUSTRIES, INC., product name "LUMIRROR U48", thickness: 125 μm) as a substrate film using a wire bar #12 and dried at 70°C for 1 minute to form a coating layer.

[0128] Next, the coating layer was irradiated with ultraviolet rays under nitrogen atmosphere using an ultraviolet irradiation device (manufactured by EYE GRAPHICS CO., LTD., product name “EYE GRANTAGE ECS-401GX”) under the following conditions to form a coating layer with a thickness of 5 μm on the substrate film to obtain a coating film.

[0129] [Ultraviolet irradiation conditions]

[0130] Light source: high pressure mercury lamp

[0131] Lamp power: 2kW

[0132] Conveyor speed: 4.23m / min

[0133] Illuminance: 200mW / cm 2

[0134] Light intensity: 200mJ / cm 2

[0135] [Comparative Example 2]

[0136] A coating film was produced in the same manner as in Comparative Example 1 except that no plasticizer was blended.

[0137] [Test Example 1] (Quantitative evaluation of anti-fingerprint properties)

[0138] A 0.2 mass % ethanol solution of oleic acid as a simulated sebum liquid was applied to the coating surface of the coating film produced in the examples and comparative examples using a wire bar #2 and then naturally dried. Oleic acid manufactured by Tokyo Chemical Industry Co., Ltd. was used.

[0139] The above-mentioned coating film was measured for the haze value (%) before, immediately after, and 25 hours after the application of the simulated sebum liquid using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JIS K7136:2000. In addition, the haze value change (points) obtained by subtracting the haze value (%) before the application from the haze value (%) of the simulated sebum liquid just after the application, and the haze value change (points, quantitative evaluation of fingerprint resistance) obtained by subtracting the haze value (%) before the application from the haze value (%) of the simulated sebum liquid 25 hours after the application were calculated. The respective results are shown in Table 1.

[0140] [Test Example 2] (Sensory evaluation of anti-fingerprint properties)

[0141] Fingerprints were left on the coating surfaces of the coating films produced in the Examples and Comparative Examples using finger sebum. After 25 hours, the surfaces of the coating films were visually observed under a three-wavelength fluorescent lamp, and sensory evaluation of fingerprint resistance was performed according to the following criteria. The results are shown in Table 1.

[0142] ◎…There are almost no fingerprints.

[0143] 〇…Fingerprints are not obvious.

[0144] △…Fingerprints are slightly obvious.

[0145] ×…Fingerprints are clearly visible.

[0146] [Test Example 3] (Evaluation of scratch resistance)

[0147] The coating surfaces of the coating films produced in the examples and comparative examples were stained with #0000 steel wool at a temperature of 125 g / cm 2 The surface of the coating film was visually observed under a three-wavelength fluorescent lamp, and the scratch resistance was evaluated according to the following criteria. The results are shown in Table 1.

[0148] ◎…The number of scratches is 0.

[0149] 〇…The number of scratches is 1 or more and 10 or less.

[0150] △…The number of scratches is 11 or more and 50 or less.

[0151] ×…The number of scratches is 51 or more.

[0152] [Test Example 4] (Evaluation of finger sliding properties)

[0153] The finger was slid on the coating surface of the coating film produced in the Examples and Comparative Examples, and the finger slidability was evaluated according to the following criteria. The results are shown in Table 1.

[0154] ◎…Fingers are very smooth.

[0155] 〇…My fingers are smooth.

[0156] △…Fingers don’t easily slide.

[0157] ×…Fingers cannot slide.

[0158] [Test Example 5] (Measurement of contact angle)

[0159] The oleic acid contact angle of the coating surface of the coating film produced in the Examples and Comparative Examples was measured under the following conditions using a contact angle meter (manufactured by Kyowa Interface Science, Inc., product name "DM-701" manufactured by Kyowa Interface Science, Inc.). In addition, as oleic acid, oleic acid manufactured by Tokyo Chemical Industry Co., Ltd. was used. The results are shown in Table 1.

[0160] Oleic acid drop volume: 2 μl

[0161] ·Measurement time: 3 seconds after dripping

[0162] Image analysis method: θ / 2 method

[0163] The water contact angles on the coating surfaces of the coating films produced in Examples and Comparative Examples were measured in the same manner as above. The conditions were as follows. The results are shown in Table 1.

[0164] ·Water drop volume: 2μl

[0165] ·Measurement time: 3 seconds after dripping

[0166] Image analysis method: θ / 2 method

[0167] [Test Example 6] (Measurement of surface free energy)

[0168] The contact angles of various liquid droplets on the coating surface of the coating films produced in the examples and comparative examples were measured, and the surface free energy (mJ / m 2 The contact angle was measured using a contact angle meter (manufactured by Kyowa Interface Science, Inc., product name "DM-701") according to the static drop method in accordance with JIS R3257. As for the droplets, diiodomethane was used as the "dispersing component", 1-bromonaphthalene was used as the "dipole component", and distilled water was used as the "hydrogen bonding component". The results are shown in Table 1.

[0169] [Table 1]

[0170]

[0171] As apparent from Table 1, the coating films (hard coating films) produced in Examples exhibited excellent scratch resistance and fingerprint resistance, and were also excellent in finger sliding properties.

[0172] Industrial Applicability

[0173] The anti-fingerprint composition, cured product, cured product layer, anti-fingerprint article, and hard coating film of the present invention are suitable for use as a surface layer of a touch panel that requires scratch resistance and fingerprint resistance.

[0174] Description of Reference Numerals

[0175] 1: hard coating film; 11: substrate film; 12: hard coating layer.

Claims

1. A fingerprint-resistant composition comprising: At least one selected from the group consisting of a multifunctional (meth)acrylate monomer, a (meth)acrylate prepolymer, and a urethane polymer; and Plasticizers, The anti-fingerprint composition is characterized in that a cured product layer having a thickness of 10 μm is formed on a polyethylene terephthalate film having a thickness of 125 μm, and a #0000 steel wool is used to coat the surface of the cured product layer at a temperature of 125 g / cm 2 When the load is applied 5 times with a 10 cm reciprocating motion, the number of scratches produced is less than 10.

2. The anti-fingerprint composition according to claim 1, characterized in that It contains a cross-linking agent.

3. A solidified product, characterized in that: The fingerprint-resistant composition is cured by curing the fingerprint-resistant composition according to claim 1.

4. A cured product layer, characterized in that: The anti-fingerprint composition according to claim 1 is cured into a layer.

5. A fingerprint-resistant article, characterized in that: It has the cured product layer according to claim 4 on its surface.

6. A hard coating film comprising a substrate film and a hard coating layer provided on at least one surface side of the substrate film, The hard coating film is characterized in that the hard coating layer is formed by curing the anti-fingerprint composition, and the anti-fingerprint composition contains: at least one selected from a multifunctional (meth)acrylate monomer, a (meth)acrylate prepolymer, and a urethane polymer; and a plasticizer. For the hard coating surface, use #0000 steel wool at 125g / cm 2 When the load is applied 5 times with a 10 cm reciprocating motion, the number of scratches produced is less than 10.

7. The hard coating film according to claim 6, characterized in that The anti-fingerprint composition contains a cross-linking agent.

8. The hard coating film according to claim 6, characterized in that The hard coating layer has a thickness of 0.5 μm or more and 50 μm or less.

9. The hard coating film according to claim 6, characterized in that: It is for optical use.

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