WO2003026881A1 - Film de revetement dur, base sur laquelle ce film est forme, et affichage d'image comportant ceux-ci - Google Patents

Film de revetement dur, base sur laquelle ce film est forme, et affichage d'image comportant ceux-ci Download PDF

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Publication number
WO2003026881A1
WO2003026881A1 PCT/JP2002/004364 JP0204364W WO03026881A1 WO 2003026881 A1 WO2003026881 A1 WO 2003026881A1 JP 0204364 W JP0204364 W JP 0204364W WO 03026881 A1 WO03026881 A1 WO 03026881A1
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WO
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Prior art keywords
hard coat
film
layer
coat film
coat layer
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PCT/JP2002/004364
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English (en)
Japanese (ja)
Inventor
Akihiro Matsufuji
Yuuzou Muramatsu
Seiya Sakurai
Kenichiro Hatayama
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Fuji Photo Film Co., Ltd.
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Application filed by Fuji Photo Film Co., Ltd. filed Critical Fuji Photo Film Co., Ltd.
Priority to JP2003530497A priority Critical patent/JPWO2003026881A1/ja
Priority to KR1020047003621A priority patent/KR100905683B1/ko
Publication of WO2003026881A1 publication Critical patent/WO2003026881A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/416—Reflective
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/51—Elastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

Definitions

  • Hard coat film base material laminated with hard coat film, and image display device provided with these
  • the present invention provides a hard coat film having excellent scratch resistance and surface hardness, an anti-reflection layer, an ultraviolet / infrared absorption layer, a selective wavelength absorption layer, an antistatic layer, an electromagnetic wave shielding layer, and a hard coat film.
  • the present invention relates to a hard coat film with a functional thin film provided with a functional thin film such as an antiglare layer and an antifouling layer. Further, the present invention relates to a base material on which a hard coat film is laminated. Further, the present invention relates to an image display device provided with a hard coat film or a substrate on which the hard coat film is laminated.
  • Conventional hard coat films are usually prepared by coating an active energy ray-polymerizable resin such as a thermosetting resin or an ultraviolet-curing resin directly on a plastic substrate film or through a primer layer of about 1 zm or less. It is manufactured by forming a thin coating of about 15 1m.
  • an active energy ray-polymerizable resin such as a thermosetting resin or an ultraviolet-curing resin directly on a plastic substrate film or through a primer layer of about 1 zm or less. It is manufactured by forming a thin coating of about 15 1m.
  • the resin-forming component of the layer is a polyfunctional acrylate monomer, which contains a powdery inorganic filler such as alumina, silica, titanium oxide, and a polymerization initiator.
  • a coating composition is disclosed in Patent No. 1,815,116.
  • a photopolymerizable composition containing an inorganic filler made of silica or alumina surface-treated with an alkoxysilane or the like is disclosed in Japanese Patent No. 1416240.
  • filling with crosslinked organic fine particles has recently been studied.
  • Japanese Patent Application Laid-Open No. 2000-520472 proposes a method of satisfying curl and scratch resistance by forming a two-layer hard coat layer and adding fine particle silica to the first layer. ing.
  • Japanese Patent Application Laid-Open No. 2000-71392 discloses a hard coat layer having a two-layer structure, a lower layer using a cured resin layer composed of a blend of a radical-curable resin and a cation-curable resin, and an upper layer. Describes a hard coat film using a cured resin layer composed of only a radical curable resin. However, these were also not sufficiently hard.
  • Japanese Patent Laid-Open Publication No. 2000-15734 discloses that the cured resin film layer has a specific elastic modulus to achieve pencil hardness. It was difficult to do this. Disclosure of the invention
  • the first problem to be solved by the present invention is to provide a hard coat film using a base film such as a PET film, having a pencil hardness of 4 H or more and having a large surface hardness and improved curl and brittleness.
  • Another object of the present invention is to provide a hard coat film with a functional thin film having functions such as antireflection, antiglare, and antifouling.
  • a second problem to be solved by the present invention is to provide a substrate on which a hard coat film is laminated.
  • a third problem to be solved by the present invention is to provide an image display device provided with a hard coat film or a base material on which a hard coat film is laminated.
  • a substrate on which the hard coat film is laminated A substrate on which the hard coat film is laminated.
  • the surface elastic modulus in the present invention is a value obtained by using a micro surface hardness tester (Fisher's Instruments, Inc .: Fisher scope H100VP-HCU). Specifically, use a diamond pyramid indenter (tip-to-face angle: 1 36 °) and adjust the indentation depth under an appropriate test load within the indentation depth not exceeding 1 im. It is an elastic modulus that is measured and obtained from changes in load and displacement when the load is removed. BEST MODE FOR CARRYING OUT THE INVENTION
  • a plastic film is preferable, and polyester such as polyethylene terephthalate and polyethylene naphthate, and cellulose such as poly-carbonate, carbonate, triacetyl cellulose and diacetyl cellulose.
  • polystyrene such as polypropylene, polyethylene, polymethylpentene, and syndiotactic polystyrene, norbornene-based resins such as cyclic olefins (eg, Zeonor, Zeonex, and Oneton manufactured by Zeon Corporation, JSR Corporation) Etc.)
  • films of polysulfone, polyether sulfone, polyarylate, polyether imide, polymethyl methacrylate and polyether ketone are preferred.
  • the thickness of the film is preferably from 20 to 500 / m.
  • the substrate film is preferably transparent, and the light transmittance of the transparent substrate film is 400 ⁇ ! It is preferably at least 80%, more preferably at least 90%, in the wavelength range of up to 780 nm. It is of course possible to apply the hard coat layer of the present invention to a sheet-like or panel-like substrate other than a film, preferably to a transparent substrate.
  • the rigidity of the hard coat layer is proportional to the flexural rigidity, which is related to the elastic modulus and film thickness.
  • the bending stiffness of the hard coat layer is low, the node coat layer itself is easily deformed, and the load of the pencil test is applied to the base film, and the base film is deformed.
  • the bending stiffness of the hard coat layer By increasing the bending stiffness of the hard coat layer, deformation due to the load in the pencil test is reduced, and deformation of the base film can be suppressed. It is preferable to increase the bending stiffness, but it is necessary that the substrate film has a certain bending stiffness or less for handling by rolls.
  • Cube of the product of the surface elastic modulus and the hard coat layer thickness of the hard coat layer is preferably from 3 0 KP a 'mm 3 ⁇ 7 0 0 KP a ⁇ mm 3, 1 0 OKP a ⁇ mm 3 ⁇ 4 0 OKP a • mm 3 is particularly preferred.
  • the hard coat layer The surface elastic modulus of the hard coat layer is preferably at least 4. OGPa, and more preferably at least 4.5 GPa. With a hard coat layer having a surface elastic modulus of less than 4. OGPa, sufficient pencil hardness and scratch resistance may not be obtained.
  • the surface elastic modulus is preferably 9. OGPa or less, more preferably 7. OGPa or less.
  • the surface elastic modulus of the hard coat layer is preferably from 4. OGPa to 9. OGPa, and more preferably from 4.5 GPa to 7.0 GPa.
  • the surface elastic modulus of the hard coat layer is adjusted by changing the cross-linking density by selecting a polyfunctional monomer used for the curable composition that is cured by heat or active energy rays, or by adding a polymer containing a polymerizable group. can do. It can also be adjusted by adding inorganic fine particles of a metal oxide such as silica, alumina or titania or organic fine particles such as a crosslinked polymer to the hard coat layer.
  • the thickness of the hard coat layer of the present invention is preferably at least 10 / m, more preferably at least 20 m. When the thickness is increased, the pencil hardness is improved, but it is difficult to bend the film, and cracking due to bending is more likely to occur. Therefore, the thickness is preferably 60 m or less, more preferably 5 Ozm or less. It is more preferably from 10 to 6 Om, particularly preferably from 20 to 60 m, most preferably from 20 to 50 zm.
  • the hard coat layer is composed of at least one layer, and may be in a form of two or more layers.
  • the hard coat layer be rounded with the outer side being rounded, so as to reduce the crackability of the hard coat represented by the diameter of the winding when cracks occur in the hard coat layer.
  • the crackability of the hard coat layer of the present invention is preferably 150 mm or less, and more preferably 8 Omm or less.
  • C Curable compositions include thermosetting compositions and active energy ray polymerizable compositions. It is possible to use a cross-linking reaction of prepolymers such as melamine resin, urethane resin, epoxy resin, etc., which is based on the sol-gel reaction of silicate, but the active energy ray is difficult to control the reaction. Polymerizable resin is preferred Commonly used.
  • the hard coat layer in the present invention is preferably a layer mainly composed of a curable composition hardened by irradiation with active energy rays.
  • a layer mainly composed of a curable composition cured by irradiation with active energy rays means, in addition to the curable composition by active energy rays, inorganic or organic fine particles described later, It means that an initiator and other additives may be contained.
  • curable compositions containing compounds having a polyfunctional polymerizable group or a bridging group that react by irradiation with active energy rays are subject to volume shrinkage during curing, and the curl increases as the film thickness increases. have.
  • the shrinkage at the time of hardening is small.
  • the volume shrinkage before and after curing at 25 ° C. is 0 to 15%, preferably 0 to 13%, and more preferably 0 to 11%.
  • the volume shrinkage due to curing can be determined from the change in density of the curable composition before and after curing.
  • MULTI VOLUME PYC manufactured by Micrometrics Inc.
  • the value of the curl value with respect to the thickness of the hard coat that is,
  • the value (absolute value) divided by the film thickness (jm) of the substrate be smaller, and the value be 0.45 (1 / (m ⁇ ⁇ -)) or less, more preferably 0 ⁇ 35 (1 / (m -jum)) It is preferred that:
  • the force value is a value obtained by the following formula B.
  • the volume of the hard coat layer may expand and contract depending on the amount of moisture absorption. twenty five
  • the absolute value of the difference between the curl value at 10% RH at 25 ° C and 80% RH at 25 ° C is 24 or less.
  • the curability of the curable composition after curing by irradiation with active energy rays is small, and the I / O value of the curable composition after curing related to hydrophilicity is 0. It is preferably from 1 to 0.85. More preferably, it is 0.25 to 0.8, most preferably 0.35 to 0.75.
  • the I / O value exceeds 0.85, the polymer produced by curing becomes more hydrophilic, and the volume expansion and hardness of the hard coat layer are greatly affected by humidity, and the high surface hardness is maintained. However, it tends to be difficult to obtain a hard coat film having good curl characteristics. If the I / O value is too small, the moisture expansion may be small and the curl at normal humidity may be large.
  • I / O values are described in Atsushi Fujita, "Systematic Organic Qualitative Analysis, Pure Products” (Kazama Publishing, 1970), Yoshio Koda, “Organic Conceptual Diagram” (Sankyo Publishing, 1984), etc. It is the “inorganic (I) / organic (0)” value obtained by the method. I / O values are used as a means to predict various physicochemical properties of organic compounds. Organic can be compared by comparing the number of carbon atoms, and inorganic can be compared by comparing the boiling points of hydrocarbons with the same number of carbons.
  • one (one CH 2 —) (actually C) is determined to have an organic value of 20, and the inorganic value is determined to be 100 due to the effect of the hydroxyl group (-OH) on the boiling point. is there.
  • the values of other substituents (inorganic groups) obtained based on the inorganic value of (-OH) of 100 are shown in the “Inorganic Group Table”.
  • the ratio of the above-mentioned inorganic value and organic value in the composition after irradiating the curable composition forming the hard coat layer with active energy rays and curing was used as the I / O value.
  • the I / O value of the curable composition cured by irradiation with active energy rays is calculated as the I / O value of each repeating unit of the polymer formed by irradiation with active energy rays, and the mass fraction of each repeating unit. Multiplied by the rate, the total value.
  • the I / O value of the curable composition hardened by irradiation with active energy rays can be adjusted to 0.1 to 0.85 by appropriately setting the composition of the curable composition before curing. is there.
  • the I / O value can be controlled to 0.1 to 0.85 by reducing the groups such as —OH, —COOR, —NH 2 , and —CO— in the cured composition.
  • the amount of moisture absorption can be reduced.
  • Moisture absorption of the hard coat layer of the present invention at 25 ° C and 60% RH The amount is preferably 3% by mass or less, more preferably 2.5% by mass or less, most preferably 2% by mass or less based on the hard coat layer at the time of drying.
  • the active energy ray polymerizable resin layer preferably used as the hard coat layer of the present invention contains a polyfunctional monomer and / or an oligomer, a polymer having a polymerizable functional group or a crosslinkable reactive group in a side chain, and a polymerization initiator. It can be formed by applying a coating liquid on the above-mentioned base film and polymerizing a polyfunctional monomer, oligomer or polymer.
  • a radical polymerizable unsaturated double bond group / open-opening polymerizable cyclic ether group is preferable.
  • Examples of the polymerizable unsaturated double bond group include an acryloyl group, a methyl acryloyl group, a vinyl group and an aryl group. From the viewpoint of reactivity, an acryloyl group and a methyl acryloyl group are preferably used.
  • a monomer having a polyfunctional polymerizable unsaturated double bond group examples include glycol-based (meth) acrylates such as ethylene glycol di (meth) acrylate and ethylene glycol di (meth) acrylate, and n— Hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropanetri (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pen Erythritol tetra (meth) acrylate, dipentyl erythritol pentyl (meth) acrylate, dipentyl erythritol hexyl (meth) acrylate, 1,4-cyclohexanedioldi (meth) acrylate, 1,3 , 5 —cyclohexanetrio
  • a polyisocyanate polyurethane oligomer composed of a condensation product of polyepoxyacrylates and polyisocyanate with a polyol and a hydroxyl group-containing acrylate such as hydroxyethyl (meth) acrylate. Obtained urethane evening Nakuri Rates and the like can be mentioned.
  • Examples of the ring-opening polymerizable cyclic ether compound include epoxy derivatives, oxetane derivatives, tetrahydrofuran derivatives, and cyclic imino ethers such as oxazoline derivatives.Epoxy derivatives, oxetane derivatives, and oxazoline derivatives are particularly preferable. .
  • ring-opening polymerizable cyclic ether compounds are preferably compounds having two or more, preferably three or more, of the above-mentioned cyclic structures in the same molecule.
  • trifunctional glycidyl ethers such as trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trishydroxyethyl isocyanurate, etc.
  • Epoxides with three or more functionalities are epoxy resin GT-301, such as sorbitol tetraglycidyl ether, pen erythritol tetraglycyl ether, polyglycidyl ether of cresol novolak resin, and polyglycidyl ether of phenol novolak resin.
  • a monofunctional monomer can be added to the polyfunctional monomer to adjust the surface elasticity, reduce curing shrinkage, and improve adhesion.
  • Monofunctional monomers alkyl esters of acrylic acid such as methyl (meth) acrylate and butyl (meth) acrylate; hydroxyethyl (meth) acrylate; dimethylaminoethyl (meth) acrylate; glycidyl (meth) acrylate
  • Acrylic esters containing polar groups such as acrylamides such as (meth) acrylamide, N-methylol (meth) acrylamide, and existing monomers such as N-vinylpyrrolidone, styrene, vinyl acetate, and maleic anhydride.
  • compounds having one or two ring-polymerizable groups in the same molecule can be used in combination, if necessary.
  • Preferred compounds are monofunctional or bifunctional glycidyl ethers, monofunctional or bifunctional glycidyl ethers.
  • Functional epoxies, monofunctional or two-functional Oxetanes, and various commercially available or known compounds can be used.
  • an oligomer or polymer containing at least two or more radically polymerizable groups to a polyfunctional monomer.
  • the oligomer or polymer containing a radical polymerizable group include oligomers and polymers having a polymerizable group such as a (meth) acryloyl group or an aryl group in a pendant group. Examples thereof include an oligomer having a hydroxyl group and a polymer having a hydroxyl group.
  • examples include epoxy ring polymer such as glycidyl (meth) acrylate, a polymer, an oligomer having a quenched acetyl group, and a polymer into which an acryloyl group is introduced by a dehydrochlorination reaction of a polymer.
  • the compound having three or more ring-opening polymerizable groups in the same molecule contains a crosslinkable polymer containing a repeating unit represented by the formula (1).
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or a methyl group.
  • L 1 is a single bond or a divalent linking group, preferably a single bond, a 10—, an alkylene group, an arylene group, and a * 0-CO *, * _CONH—, * — linked to the main chain on the * side. OCO— ⁇ * —NHCO—.
  • P 1 is a monovalent group containing a ⁇ polymerizable group, preferred P 1, epoxy ⁇ , Okisetan ring, a tetrahydrofuran ring, a lactone ring, the force - Boneto ring one, including Iminoeteru rings such Okisazorin ⁇ And a monovalent group containing an epoxy ring, an oxetane ring, or an oxazoline group.
  • the crosslinkable polymer of the present invention containing a repeating unit represented by the formula (1) is preferably synthesized simply by polymerizing a corresponding monomer.
  • radical polymerization is the simplest and preferable. Specific examples include polyglycidyl methacrylate, polymethyl glycidyl methacrylate, polyepoxycyclohexylmethyl methacrylate, and poly (3-ethyl) -3-oxenyl dimethylmethyl methacrylate. Rates and the like.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • P 1 is a monovalent group containing a cyclic polymerizable group
  • L 1 is a single bond or a divalent linking group. is there.
  • the polyfunctional polymerizable unsaturated double bond group-containing monomer or polymer or polymer and the polyfunctional cyclic structure-containing compound may be used in combination.
  • a polyfunctional polymerizable unsaturated double bond When adding a monofunctional monomer, an oligomer containing at least two or more polymerizable unsaturated double bond groups or a polymer or a ring-opening polymerizable cyclic ether compound, a polyfunctional polymerizable unsaturated double bond
  • the amount added to the bond-containing monomer is preferably 50% by mass or less, more preferably 35% by mass or less. If the proportion of monofunctional monomers, oligomers or polymers containing at least two or more polymerizable unsaturated double bond groups or ring-opening polymerizable cyclic ether compounds becomes too large, the desired hardness cannot be obtained. .
  • Inorganic or organic fine particles are added to these active energy ray polymerizable resin layers to adjust the surface elastic modulus of the hard coat layer or reduce the curing shrinkage to reduce the force of the hard coat film. can do.
  • the fine particles include inorganic oxides and internally crosslinked polymer resin particles.
  • the inorganic oxide particles those having a high hardness are preferable, and inorganic oxide particles having a Mohs hardness of 6 or more are preferable.
  • Examples include silicon dioxide particles, titanium dioxide particles, zirconium oxide particles, aluminum oxide particles, and the like.
  • organic fine particles examples include resin particles such as acrylic resin, polystyrene, polysiloxane, melamine resin, benzoguanamine resin, polytetrafluoroethylene, cellulose acetate, polycarbonate, nylon, and the like. Particles composed of methyl acrylate (divinylbenzene copolymer), polysiloxane, polystyrene, melamine resin, benzoguanamine resin, and a complex thereof are preferred. Further, internally crosslinked polymer resin fine particles obtained by copolymerization with a monomer having a bifunctional or higher functional group are preferred.
  • the volume average particle diameter of these fine particles is 1 nm or more and 400 nm or less, more preferably 5 nm or more and 200 nm or less, and still more preferably 10 nm or more and 100 nm or less. At lnm or less, dispersion is difficult and aggregated particles are formed. At more than 400nm, the haze increases, and both are unfavorable because transparency is reduced.
  • the addition amount of these fine particles is more preferably from 5 to 80% by mass, and even more preferably from 10 to 50% by mass, based on the total amount of the active energy ray-polymerizable resin layer.
  • inorganic fine particles have a poor affinity for the active energy ray-polymerizable resin, so that the interface is easily broken by simply mixing the two, the film is easily broken, and it is difficult to improve the scratch resistance.
  • the surface of the inorganic fine particles can be treated with a surface modifier containing an organic segment.
  • the surface modifier preferably forms a bond with the inorganic fine particles on the one hand, and has a high affinity with the active energy linear polymerizable resin on the other hand.
  • Examples of the compound capable of forming a bond with the surface of the inorganic fine particles include metal alkoxide compounds such as silicon, aluminum, titanium, and zirconium, phosphate esters, phosphonate groups, sulfate esters, sulfonic acid groups, and carboxylic acid groups.
  • An anionic compound having the same is preferred.
  • a polymerizable unsaturated double bond group or a ring-opening polymerizable compound may be added to the terminal of the metal alkoxide compound or anionic compound. It preferably has a cyclic ether group.
  • the heat resistance of the plastic film itself is low. Therefore, when the curable resin is hardened by heating, it is preferable to cure at a temperature as low as possible.
  • the heating temperature in that case is 140. C or lower, more preferably 100 ° C. or lower.
  • hardening by the action of light is often used because the crosslinking reaction often proceeds at a low temperature.
  • examples of the active energy ray include radiation, gamma ray, alpha ray, electron beam, and ultraviolet ray. Particularly preferred is a method of adding a polymerization initiator for generating the above, followed by curing with ultraviolet rays. In addition, by heating after irradiating with ultraviolet rays, it may be possible to further promote the stiffening.
  • the preferable heating temperature in this case is 140 ° C. or less.
  • Examples of the photoradical polymerization initiator include acetophenones, benzophenones, Michler's ketone, benzoylbenzoate, benzoins, hyacyloxime ester, tetramethylthiuram monosulfide, and thioxanthone.
  • a photosensitizer may be used in addition to the photopolymerization initiator. Examples of photosensitizers include n-butylamine, triethylamine, triethanolamine, tri-n-butylphosphine, thioxanthone, and the like.
  • photoacid generators that generate cations include compounds such as triarylsulfonium salts, diaryliodonium salts, and nitrobenzyl esters of sulfonic acids.
  • Various known photoacid generators such as the compounds described in "Materials" published by Bunshin Publishing Co., Ltd. (1997) can be used.
  • a sulfonium salt such as diphenyl 4-thiophenoxyphenylsulfonium hexafluoroantimonate or diphenyldonium salt, and a counter ion As PF 6- , S b F 6 _, A s F 6 —, B (C 6 F 5 ) 4 — and the like are preferred.
  • polymerization initiator is preferably used in the range of 0.1 to 15 parts by mass, more preferably in the range of 1 to 10 parts by mass, based on 100 parts by mass of the polyfunctional monomer. preferable.
  • the coating solution of the active energy ray polymerizable resin may be mixed with an organic solvent such as ketones such as methyl ethyl ketone and methyl isobutyl ketone, alcohols such as ethyl alcohol and isopropyl alcohol, esters such as ethyl acetate, and the above polyfunctional monomer. It is prepared by dissolving a nomer and a polymerization initiator mainly. In order to omit the drying step, it is possible to use a non-solvent.
  • an organic solvent such as ketones such as methyl ethyl ketone and methyl isobutyl ketone, alcohols such as ethyl alcohol and isopropyl alcohol, esters such as ethyl acetate, and the above polyfunctional monomer. It is prepared by dissolving a nomer and a polymerization initiator mainly. In order to omit the drying step, it is possible to use a non-solvent.
  • the hard coat film of the present invention is obtained by coating an active energy ray polymerizable resin paint on a base film by a dipping method, a spinner method, a spray method, a roll coat method, a gravure method, a wire bar method, or an extruder method. It can be formed by a known thin film forming method such as a blade method, a die coating method, and the like, dried, and irradiated with active energy rays.
  • one or both surfaces can be subjected to a surface treatment by an oxidation method, a roughening method, or the like, if desired.
  • the oxidation method include a corona discharge treatment, a glow discharge treatment, a plasma treatment, a chromic acid treatment (wet method), a flame treatment, a hot air treatment, and an ozone irradiation with ultraviolet rays.
  • one or more undercoat layers can be provided.
  • Examples of the material for the undercoat layer include copolymers or latexes such as vinyl chloride vinyl chloride, vinylidene chloride, butadiene, (meth) acrylate and vinyl ester, and water-soluble polymers such as low molecular weight polyester and gelatin.
  • copolymers or latexes such as vinyl chloride vinyl chloride, vinylidene chloride, butadiene, (meth) acrylate and vinyl ester
  • water-soluble polymers such as low molecular weight polyester and gelatin.
  • Metal oxides such as tin oxide, ITO and zinc oxide and ionic organic compounds can be added to the undercoat layer as a conductive substance.
  • the hard coat layer may be a single layer, but may be composed of two or more layers. Many The layered structure may be formed by sequentially laminating layers having different surface elastic moduli. In the case of a multi-layer structure, the elastic modulus, cure shrinkage, IZO value, and moisture absorption of each layer can be obtained as values obtained by correcting the characteristics of each layer with the thickness.
  • a functional thin film such as an antireflection layer, an antiglare layer, and an antifouling layer can be provided on the hard coat layer. Furthermore, it is also possible to laminate and combine an ultraviolet or infrared absorption layer, a selective wavelength absorption layer, an antistatic layer, and an electromagnetic wave shielding layer, and it is provided as a hard coat film with a highly functional thin film.
  • These functional thin films can be formed by a wet method of applying a solution of a known functional material, or a dry method of forming a vacuum film such as a sputter or vapor deposition.
  • FIG. 1 is a schematic diagram showing the layer structure of a hard coat film as one embodiment of the present invention
  • FIG. 2 is a layer structure of a hard coat film with a functional thin film as one embodiment of the present invention.
  • 1 is a substrate film
  • 2 is a hard coat layer
  • 3a is a high refractive index layer
  • 3b is a low refractive index layer
  • 4 is an antistatic undercoat layer.
  • a substrate on which these hard coat films are laminated is preferably used as a substrate having excellent scratch resistance and surface hardness.
  • a base material include a plastic sheet to which a hard coat film is attached to prevent surface damage, and a show window or window glass to which a hard coat film is attached to prevent scattering. And the like.
  • the hard coat film can be laminated with an adhesive and attached to a substrate.
  • the hard coat film may be attached to only one side of the substrate, or may be attached to both sides of the substrate.
  • Glass or plastic can be used as a substrate on which the hard coat film is laminated.
  • the plastic include cellulose esters, polyamides, polycarbonates, polyesters, polystyrenes, polyolefins, polysulfones, polyestersulfones, polyarylates, polyetherimides, polymethylmethacrylates and polyetherketones.
  • the substrate is preferably transparent, and the light transmittance of the substrate is 400 ⁇ ! It is preferably at least 80%, more preferably at least 90% in a wavelength range of up to 780 m. New
  • the thickness of the substrate is preferably 1 to 30 mm, and the substrate may be in any shape such as a sheet shape, a panel shape, and a plate shape.
  • the image display device provided with the hard coat film of the present invention or the substrate on which the laminated film is provided has excellent abrasion resistance, and is preferably used as an image display device having surface hardness.
  • the image display devices provided include flat panel displays (FPDs) such as liquid crystal displays (LCDs), plasma display panels (PDPs), field emission displays (FEDs), electroluminescence displays (ELDs), and cathode ray tube displays. (CRT), touch panels, and the like.
  • FPDs flat panel displays
  • LCDs liquid crystal displays
  • PDPs plasma display panels
  • FEDs field emission displays
  • ELDs electroluminescence displays
  • CTR cathode ray tube displays.
  • FIG. 3 is a schematic view showing a cross section of an image display device provided with a hard coat film as one embodiment of the present invention
  • FIG. 4 is a hard disk as one embodiment of the present invention
  • FIG. 3 is a schematic view showing a cross section of an image display device provided with a base material on which a tofilm is laminated. 3 or 4,
  • A indicates an image display device
  • B indicates a substrate
  • C indicates a hard coat film or a hard coat film with a functional thin film.
  • the product of the surface elastic modulus of the hard coat layer and the cube of the thickness is 3 OKP a-mm 3 or more 70
  • FIG. 1 is a schematic view showing the layer constitution of one embodiment of the hard coat film of the present invention.
  • FIG. 2 is a schematic diagram showing a layer configuration of one embodiment of the hard coat film with a functional thin film of the present invention.
  • FIG. 3 is a schematic view showing a cross section of an image display device provided with a hard coat film or a hard coat film with a functional thin film of the present invention.
  • FIG. 4 is a schematic view showing a cross section of an image display device provided with a substrate on which a hard coat film or a hard coat film with a functional thin film of the present invention is laminated.
  • the curable resin described in Table 1 was dissolved in methyl ethyl ketone (MEK), a polymerization initiator was added, and the mixture was filtered through a polypropylene filter having a pore size of 1 zm to prepare a curable yarn.
  • MEK methyl ethyl ketone
  • Latex made of styrene butadiene copolymer having a glass transition temperature of 37 ° C (LX407C5; manufactured by Nippon Zeon Co., Ltd.) previously treated with corona and a tin oxide-acid-antimony complex oxide (FS-10D; Ishihara (Manufactured by Co., Ltd.) in a ratio of 5: 5 by mass, and applied so that the film thickness after drying becomes 0.2 m, so that the antistatic undercoat layer is formed to a thickness of 175 mm.
  • a PET film (biaxially stretched polyester terephthalate film) and an 80 zm triacetyl cellulose film were separately manufactured.
  • the dangling composition was applied on the two antistatic films by an extrusion method so as to have a predetermined thickness (the thickness was determined by the dissolution concentration of the curable composition and the coating amount). Adjusted with.) After drying the curable composition at 100 ° C, irradiate ultraviolet rays with illuminance of 75 OmJ / cm 2 to form a hard coat film with a hard coat layer (samples with t added to triacetyl cellulose) was created.
  • irgacure 184 manufactured by Ciba Geigy Co., Ltd.
  • liposome dosyl 2074 manufactured by Rhodia
  • the calorie content was 4% by mass based on the curable resin.
  • the alumina dispersion ** is 234 parts of methyl isobutyl ketone, A mixture of 36 parts of M-530 (methacrylate containing a carboxylic acid group; manufactured by Toagosei Co., Ltd.) and 180 parts of fine-particle alumina (AKP-GO15; manufactured by Sumitomo Chemical Co., Ltd.)
  • M-530 methacrylate containing a carboxylic acid group
  • a mixture of fine-particle alumina (AKP-GO15; manufactured by Sumitomo Chemical Co., Ltd.)
  • This is a dispersion of alumina fine particles that has been surface-treated by dispersing with a ceramic-coated sand mill using zirconium aviation of 1 ⁇ as the medium.
  • the mass in the table is the mass of the solid component.
  • Table 1 shows the pencil hardness, curl value, cracking property, etc. of the hard coat film.
  • a hard coat material having a small curl can be obtained by using a hard coat material having a volume shrinkage of 15% or less after curing.
  • the surface elastic modulus of the hard coat layer is 9 GPa or more, the brittleness is remarkably deteriorated even if the curing shrinkage is small, and the hard coat layer may be easily broken.
  • the product of the cube of the surface elastic modulus and the thickness of the prepared hard coat layer, the surface elastic modulus, the thickness, the cure shrinkage of the cured composition, the I / O value, and the hard coat film when PET is used as the base film Table 2 shows the pencil hardness, curl value, cracking property, and the like.
  • the product of the surface elastic modulus and the cube of the film thickness is large, and the volume shrinkage of the curable composition after curing is 15% by volume or less and the I / O value is 0.85 or less.
  • Titanium dioxide fine particles (TTO-55B, manufactured by Ishihara Sangyo Co., Ltd.) 30.0 parts by mass, anionic monomer (M-5300, manufactured by Toagosei Co., Ltd.) 4.5 parts by mass and cyclohexanone 65.2 mass
  • the parts were dispersed by a sand grinder mill to prepare a titanium dioxide dispersion having a mass average diameter of 55 nm.
  • the titanium dioxide dispersion and dipentyl erythritol hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.), a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy Co., Ltd.), a photosensitizer (Kayacure-DETX, Nippon Kagaku)
  • the total volume of monomers (total amount of dipentyl erythritol hexylacrylate and anionic monomer) and titanium dioxide is 60/40
  • the photopolymerization initiator and photosensitizer To the methyl ethyl ketone so that the mass ratio with the sensitizer is 3/1, and the mass ratio of the total amount of the photopolymerization initiator and the photosensitizer to the total amount of the monomers is 6/100
  • the mixture was mixed to prepare a high refractive index layer coating solution.
  • the refractive index was 1.80.
  • the coating liquid of the high refractive index layer (a-1) was applied to the hard coat film of Example 43 using a bar so as to have a dry film thickness of 9 Onm, dried, and irradiated with ultraviolet rays.
  • the low-refractive-index layer coating solution of (a-2) is dried on the high-refractive-index layer to a thickness of 85 nm.
  • a hard coat film with an antifouling antireflection layer having an antireflection layer formed by applying, drying, and irradiating ultraviolet rays was obtained.
  • Table 4 shows that the image display device provided with the hard coat film of the present invention has a large surface hardness, is hardly damaged, and has excellent image visibility.
  • Hardening shrinkage rate of hardening composition According to the method already described.
  • Pencil hardness test The hardness of the pencil pull test is 25 for the prepared hard coat film. After conditioning for 5 hours under the condition of 60% relative humidity, using a test pencil specified by JIS S 6006, in accordance with the pencil hardness evaluation method specified by JISK 5400, the scratches and dents were formed under a load of 9.8 N. This is a pencil hardness value that is not recognized.
  • Mechanical pencil drawing After conditioning the film for 5 hours at a temperature of 25 ° C and a relative humidity of 60%, use a HE I DON surface tester N-14 (manufactured by Shinto Kagaku Co., Ltd.). The tip of a metal tip of a mechanical pencil (PD 355, manufactured by Bentel) was rubbed while varying the load, and the load when scratches were generated was examined.
  • Curl value It is a value measured using the curl measurement template of method A of "Method for measuring curl of photographic film" in JIS K7619-1988.
  • the test condition for 60% curl is 25 ° relative humidity 60%.
  • curl is positive,
  • the curl where the coated side of the hard coat layer of LUM is inside the curve is defined as negative, and the curl where the coated side is outside the curve is defined as negative.
  • the larger the value the more the curl is significant.
  • Curl humidity difference The curl values were read at 80% and 10% relative humidity at 25 ° C and expressed as the absolute value of the difference between the two values.
  • Moisture absorption After drying for 2 hours in a dry atmosphere at a dew point of 40 ° C, the sample was left at 60 ° C at 25 ° C for 3 hours, and the moisture absorption was determined from the weight change before and after the storage.
  • Eraser rubbing The surface was reciprocated 50 times with a load of lkg using an eraser No. 50 manufactured by Lion Corporation, and the surface damage was visually evaluated. If no scratching or change was observed, it was marked as ⁇ .
  • a quick-drying oil-based ink (Zebra, “Maduki” (registered trademark)) written on the film surface was rubbed several times with “Toray Shi” (registered trademark) manufactured by Toray Industries, Inc. ( ⁇ indicates a state where the written mark has been completely wiped off, ⁇ indicates a state where a part has not been wiped off, and X indicates a state where most of the trace has been wiped off).
  • Fingerprint wiping property Evaluated the ease with which fingerprints on the surface could be wiped off using Toray Co., Ltd.'s "Treshi-1" (registered trademark). X is the one that can be rubbed with force, ⁇ is the middle one).
  • Scratch resistance The number of times a slight visual scratch occurs when the surface of a hard-coated film is rubbed with a load of 1.96 N / cm 2 using # 1000 steel wool. was observed.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

L'invention a trait à un film de revêtement dur présentant d'excellentes propriétés de résistance à l'abrasion et de dureté superficielle, ainsi que des caractéristiques améliorées de frisage et de tendance à l'écaillage ; à une base sur laquelle ce film est formé ; et à un affichage d'image comportant ceux-ci. Ce film, qui présente une couche de revêtement dur sur au moins une face du film de base, est caractérisé en ce que le produit du module d'élasticité de surface de la couche de revêtement dur et du cube de l'épaisseur de ladite couche est compris entre 30 Kpa x mm3 et 700 Kpa x mm3. Le module d'élasticité de surface de la couche de revêtement dur est de préférence compris entre 4,0 et 9,0 Gpa. La couche de revêtement dur est de préférence constituée principalement d'une composition traitée par rayonnement à l'aide d'un faisceau d'énergie active ; et le facteur de retrait volumique de cette composition, après traitement, est de préférence compris entre 10 et 15 %.
PCT/JP2002/004364 2001-09-25 2002-05-01 Film de revetement dur, base sur laquelle ce film est forme, et affichage d'image comportant ceux-ci WO2003026881A1 (fr)

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JP2003530497A JPWO2003026881A1 (ja) 2001-09-25 2002-05-01 ハードコートフィルム、ハードコートフィルムを積層した基材、及びこれらを設けた画像表示装置
KR1020047003621A KR100905683B1 (ko) 2001-09-25 2002-05-01 하드 코팅 필름, 하드 코팅 필름을 적층한 기재 및 이들을형성한 화상표시장치

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JP2005292203A (ja) * 2004-03-31 2005-10-20 Konica Minolta Opto Inc 反射防止積層体、偏光板及び表示装置
JP2005288921A (ja) * 2004-03-31 2005-10-20 Nippon Paper Industries Co Ltd ハードコートフィルム
JP2006142493A (ja) * 2004-11-16 2006-06-08 Toppan Printing Co Ltd ハードコートフィルム
JP4563145B2 (ja) * 2004-11-16 2010-10-13 凸版印刷株式会社 ハードコートフィルム
JP2012166140A (ja) * 2011-02-14 2012-09-06 Nippon Zeon Co Ltd ハードコートフィルム及びハードコートフィルムの製造方法
JP2013045044A (ja) * 2011-08-26 2013-03-04 Konica Minolta Advanced Layers Inc ハードコートフィルム
JP2014148151A (ja) * 2013-02-01 2014-08-21 Art & Tech Kk 複合着色シート
US20160099403A1 (en) * 2013-04-10 2016-04-07 Mitsui Chemicals, Inc. Layered body
JPWO2014184983A1 (ja) * 2013-05-16 2017-02-23 三菱レイヨン株式会社 樹脂積層体及びその製造方法並びにディスプレー前面板
WO2014184983A1 (fr) * 2013-05-16 2014-11-20 三菱レイヨン株式会社 Stratifié à base de résine, son procédé de fabrication et panneau d'affichage frontal
KR101858328B1 (ko) 2013-05-16 2018-05-15 미쯔비시 케미컬 주식회사 수지 적층체 및 그의 제조 방법, 및 디스플레이 전면판
WO2014199990A1 (fr) * 2013-06-14 2014-12-18 コニカミノルタ株式会社 Film multicouche dérivatif
WO2015098495A1 (fr) * 2013-12-24 2015-07-02 Dic株式会社 Film de revêtement dur et dispositif d'affichage d'information
JP5939449B2 (ja) * 2013-12-24 2016-06-22 Dic株式会社 ハードコートフィルム及び情報表示装置
JPWO2015098495A1 (ja) * 2013-12-24 2017-03-23 Dic株式会社 ハードコートフィルム及び情報表示装置
JP2019111527A (ja) * 2017-12-20 2019-07-11 ローム アンド ハース エレクトロニック マテリアルズ エルエルシーＲｏｈｍ ａｎｄ Ｈａａｓ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＬＬＣ ハードコート
JP2021070183A (ja) * 2019-10-30 2021-05-06 株式会社ダイセル ハードコートフィルム

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CN1286640C (zh) 2006-11-29
JPWO2003026881A1 (ja) 2005-01-06
KR100905683B1 (ko) 2009-07-03
CN1558824A (zh) 2004-12-29
TWI225159B (en) 2004-12-11
KR20040037081A (ko) 2004-05-04

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