WO2015087827A1 - Film à haute dureté - Google Patents

Film à haute dureté Download PDF

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Publication number
WO2015087827A1
WO2015087827A1 PCT/JP2014/082396 JP2014082396W WO2015087827A1 WO 2015087827 A1 WO2015087827 A1 WO 2015087827A1 JP 2014082396 W JP2014082396 W JP 2014082396W WO 2015087827 A1 WO2015087827 A1 WO 2015087827A1
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WIPO (PCT)
Prior art keywords
film
meth
acrylate
hard coat
base material
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PCT/JP2014/082396
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English (en)
Japanese (ja)
Inventor
昇平 福田
誠司 瀬口
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王子ホールディングス株式会社
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Priority to JP2015552435A priority Critical patent/JP6350546B2/ja
Publication of WO2015087827A1 publication Critical patent/WO2015087827A1/fr

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    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • 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
    • B32B2307/542—Shear strength
    • 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
    • B32B2307/70—Other properties
    • B32B2307/718—Weight, e.g. weight per square meter

Definitions

  • the present invention relates to a high hardness film having a hard coat layer.
  • a thin glass substrate may be used on the surface of the flat panel display, and a protective sheet is affixed to the front or back surface of the glass substrate in order to prevent the glass substrate from scattering.
  • the protective sheet attached to the glass substrate include a front adhesive sheet imparted with an antiglare property and a fingerprint adhesion preventive property, and a back adhesive sheet for decoration.
  • Patent Document 1 discloses a hard coat film that attempts to achieve both high hardness and improved curl by providing two hard coat layers on one side of a substrate.
  • Patent Document 2 discloses a touch panel protective sheet having a front film and a back film bonded together and having two layers of base materials and three hard coat layers.
  • Patent Document 1 is inferior in the balance of the layer structure, and time may elapse, or curling or delamination may occur during heating or processing.
  • Patent Document 2 cannot be said to have a well-balanced layer structure, and still has room for improvement in curling prevention and delamination prevention performance.
  • An object of the present invention is to provide a high-hardness film that can reduce the occurrence of curling and delamination while maintaining high surface hardness as an alternative to a glass substrate.
  • the present inventors have made various studies in order to solve the above problems. Curling and delamination become a problem not only when used as a final product, but also when a laminated film composed of multiple layers is sequentially laminated at the time of manufacture. When curling or delamination occurs, manufacturing becomes difficult and the product life is shortened. Analysis of the delaminated laminated films revealed that in many cases peeling occurred at the interface of the adhesive layer. Furthermore, the relationship between the thermal and dynamic behavior of the adhesive layer and delamination was examined.
  • the dynamic viscoelastic behavior at room temperature is related to the peeling performance at the interface between the adhesive layer and the substrate during use
  • the dynamic viscoelastic behavior during heating is It was found to be related to the peeling performance at the interface between the layer and the substrate. And in order to prevent delamination, it became clear that it was important to control the dynamic shear storage elastic modulus at the time of room temperature and at the time of heating to a specific range, respectively.
  • the surface hardness of the laminated film is not simply determined by the surface hardness or thickness of only the hard coat layer formed on the outermost surface, but the entire layer structure of the laminated film is involved. Furthermore, it has also been found that it is effective in preventing the occurrence of curling and delamination that the layers constituting the high-hardness film are as symmetrical as possible on both sides of the adhesive layer.
  • the present invention has been completed based on many findings as described above. That is, the present invention has the following configuration.
  • the thickness t 2 of the base material has a relationship of t 1 ⁇ t 2 ⁇ 1.1 ⁇ t 1
  • the dynamic shear storage elastic modulus G ′ (20 ° C.) of the adhesive layer at 20 ° C. and a frequency of 1 Hz is A high-hardness film characterized in that the dynamic shear storage modulus G ′ (80 ° C.) of the adhesive layer at 80 ° C.
  • the thickness of the first substrate and the second substrate is 50 to 250 ⁇ m, the total thickness of the hard coat layer is 15 to 80 ⁇ m, and the thickness of the adhesive layer is 5 to 25 ⁇ m.
  • the high-hardness film according to any one of (1) to (6), wherein:
  • the high hardness film of the present invention is thin and lightweight, and can reduce the occurrence of curling and delamination while maintaining high surface hardness.
  • the high hardness film of the present invention can be used as a surface protective film for protecting an image display device or the like.
  • the image display device means a flat panel display such as a liquid crystal system or an organic EL system. These are used for various applications such as personal computers, mobile phones, portable game machines, flat-screen TVs, various displays for advertising and information display. In recent years, flat panel displays having not only flat surfaces but also curved surfaces have been developed.
  • FIG. 3 is a schematic cross-sectional view showing the configuration of the first embodiment of the present invention.
  • the high hardness film 1 of FIG. 3 is configured by attaching a front film 20 a and a back film 21 a with an adhesive layer 13 interposed therebetween.
  • the surface film 20a has the 1st base material 12a and the 1st hard-coat layer 11a laminated
  • the back film 21a has the 2nd base material 12b and the 2nd hard-coat layer 11b laminated
  • first base material 12a and the second base material 12b may be collectively referred to as the base material 12.
  • first hard coat layer 11a, the second hard coat layer 11b, and the third hard coat layer 11c described later may be collectively referred to as the hard coat layer 11.
  • each layer constituting the high hardness film 1 has a substantially symmetrical layer configuration on both sides of the adhesive layer 13.
  • the first base material 12a and the second base material 12b are present on both sides of the adhesive layer 13 at substantially the same thickness and in symmetrical positions.
  • the first hard coat layer 11a and the second hard coat layer 11b are present at symmetrical positions on both ends with the adhesive layer 13 in between.
  • each layer on both sides of the adhesive layer 13 is balanced in thickness.
  • the first substrate 12a and the second substrate 12b which are substrates, have the same thickness. That is, it is necessary that the thickness t 1 of the first base material 12 a and the thickness t 2 of the second base material 12 b have a relationship of t 1 ⁇ t 2 ⁇ 1.1 ⁇ t 1 . Since the 3rd hard coat layer 11c may be formed in the back of the 1st substrate 12a, the 2nd substrate layer 12b is more than the 1st substrate layer 12a from the balance with the 3rd hard coat layer 11c. Can be a little thicker.
  • the layers constituting the high-hardness film have a symmetrical layer structure as much as possible on both sides of the adhesive layer 13.
  • the first base material 12a and the second base material 12b, and the first hard coat layer 11a and the second hard coat layer 11b are symmetrical with respect to the adhesive layer 13, respectively. Therefore, it has a preferable layer structure.
  • the material forming the first base material 12a and the second base material 12b is a transparent material that transmits 80% or more of visible light, and is a film-like material.
  • polyester films such as polyethylene terephthalate film, polyethylene naphthalate film, polypropylene terephthalate film, polypropylene naphthalate film, polytrimethylene terephthalate film, polybutylene terephthalate film are preferable.
  • first substrate 12a and the second substrate 12b may be the same material or different materials. From the viewpoint of curling and delamination prevention, the same material is preferable.
  • Each of the first base material 12a and the second base material 12b may contain various additives.
  • the additive include antioxidants, heat stabilizers, ultraviolet absorbers, organic particles, inorganic particles, pigments, dyes, antistatic agents, nucleating agents, and coupling agents.
  • the first substrate 12a and the second substrate 12b may be subjected to a surface treatment in order to improve adhesion with the hard coat layer 11 and the adhesive layer 13.
  • a surface treatment include surface roughening treatment such as sandblast treatment and solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and the like.
  • FIG. 4 is a schematic cross-sectional view showing a configuration of a modified example of the first embodiment of the present invention.
  • the high-hardness film 2 shown in FIG. 4 in addition to the layer configuration of the first embodiment, it easily adheres to both surfaces of the first substrate 12a of the front film 20b and both surfaces of the second substrate 12b of the back film 21b.
  • Layer 15 is provided.
  • the easy-adhesion layer 15 contains an acrylic resin or a polyester resin, and may contain a urethane resin or the like as necessary.
  • the acrylic resin used for the easy adhesion layer 15 include those polymerized from an acrylic monomer as shown below.
  • alkyl acrylate or alkyl methacrylate having a linear, branched or cyclic alkyl group, a hydroxy-containing monomer, an epoxy group-containing monomer, a monomer containing an amide group, etc. are not limited thereto. Absent. These monomer components may be copolymerized using two or more kinds.
  • polyester resins include those that are polycondensed from a polybasic acid component and a polyol component.
  • the polybasic acid used include terephthalic acid, isophthalic acid, and diphenylcarboxylic acid.
  • the polyol component include ethylene glycol and diethylene glycol, but are not limited thereto. These monomer components may be copolymerized using two or more kinds.
  • Examples of the urethane resin include those obtained as a reaction product of a polyol compound and an isocyanate compound.
  • Examples of the polyol compound used include polyester polyol, polyether diol, and polyacetal diol.
  • Examples of the isocyanate compound include, but are not limited to, tolylene diisocyanate and phenylene diisocyanate. Moreover, these components can also be reacted using 2 or more types. Further, if necessary, a chain extender, a crosslinking agent and the like may be used.
  • Particles can be added to the easy-adhesion layer 15 for the purpose of imparting slipperiness and adjusting the refractive index.
  • the particles include inorganic pigments and organic fillers, but it is preferable to use silica because the refractive index is relatively close to the resin of the easy-adhesion layer 15 and high transparency is obtained.
  • the particles used for the purpose of adjusting the refractive index of the easy-adhesion layer 15 include alumina-silica composite, titanium oxide, zirconium oxide, zinc oxide and the like, but are not limited to these. Two or more types may be used. Moreover, you may add various additives, such as an antistatic agent and a plasticizer, to the easily bonding layer 15 as needed. A surfactant and a pH adjuster may be added for the purpose of improving coating suitability and reactivity.
  • the thickness of the easy-adhesion layer 15 is not particularly limited, but can be, for example, 0.1 nm or more, and can be selected within a range of 1 nm or more and 5 nm or more. Although an upper limit changes with uses, it is also possible to select within the range of 1 micrometer or less, 100 nm or less, and 50 nm or less, for example.
  • the method for forming the easy adhesion layer 15 is not particularly limited, but when the polyester film is used for the first base material 12a and the second base material 12b, the easy adhesion layer 15 is formed on the polyester film after the polyester film is melt-extruded. It is preferable to do.
  • the polyester film may be a uniaxially stretched polyester film or a biaxially stretched polyester film. In the case of a uniaxially stretched polyester film, the polyester film is melted and extruded, and then stretched 3 to 10 times in the longitudinal or transverse direction to form a uniaxially stretched polyester film, and if necessary, corona discharge treatment Apply.
  • the easy-adhesion layer resin is applied to at least one surface and dried to form the easy-adhesion layer 15.
  • the polyester film is melted and extruded, then stretched 3 to 10 times in the longitudinal direction to form a longitudinally stretched polyester film, and subjected to corona discharge treatment as necessary.
  • the easy-adhesion layer resin is applied to at least one surface and dried to form the easy-adhesion layer 15.
  • the biaxially stretched polyester film is formed by further stretching the film having the easy adhesion layer 15 3 to 10 times in the transverse direction.
  • the polyester film and the resin for the easy adhesion layer are extruded simultaneously to form a laminated film, and the laminated film is stretched monoaxially or biaxially by a known method 9 to 100 times to form the easy adhesion layer 15. You may do it.
  • the film produced as described above may be further subjected to surface treatment by a known method such as corona discharge treatment or flame treatment so that the haze value does not increase as necessary.
  • the thickness of the first base material 12a and the second base material 12b is 50 to 250 ⁇ m including the easy-adhesion layer 15 from the viewpoint of securing mechanical strength as the high-hardness film 1 and preventing curling. preferable. More preferably, it is 100 to 200 ⁇ m.
  • the dimensional change rate before and after heating the first base material 12a and the second base material 12b is small.
  • the difference in the dimensional change rate between the first base material 12a and the second base material 12b is preferably 0.5% or less in both the vertical direction and the horizontal direction. More preferably, it is 0.3% or less.
  • the dimensional change rate (%) is obtained from the difference in dimensions before and after the heat treatment at 150 ° C. for 30 minutes in accordance with JIS C2151 in each of the vertical direction and the horizontal direction.
  • the vertical direction is the length direction of the base material
  • the horizontal direction is a direction perpendicular to the length direction of the base material.
  • the hard coat layer 11 of the present embodiment is a layer containing a hard component for imparting surface hardness to the high hardness film 1. In the present embodiment, it is preferable to use a curable resin as the hard coat layer 11.
  • Examples of the curable resin used for the hard coat layer 11 include a thermosetting resin and an active energy ray curable resin.
  • the thermosetting resin include phenol resin, urea resin, diallyl phthalate resin, melamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, amino alkyd resin, silicon resin, polysiloxane resin, and the like.
  • the active energy ray curable resin include acrylic curable resins and urethane curable resins.
  • the acrylic curable resin is a polymer of a curable composition composed of a monomer or oligomer having an acrylic polymerizable unsaturated group.
  • Monomers and oligomers having an acrylic polymerizable unsaturated group include monofunctional and polyfunctional ones.
  • the monofunctional monomer having an acrylic polymerizable unsaturated group examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth ) N-butyl acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, N-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, (meta ) N-undecyl
  • the monofunctional oligomer having an acrylic polymerizable unsaturated group include ethoxylated o-phenylphenol acrylate, methoxy polyethylene glycol (mass average molecular weight 400) acrylate, phenoxy polyethylene glycol acrylate, and the like.
  • a polyfunctional (meth) acrylic ester is used as the monomer or oligomer having an acrylic polymerizable unsaturated group. It is preferable to have.
  • the polyfunctional (meth) acrylic acid ester include dipropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and polyethylene glycol (mass average molecular weight 600).
  • Bifunctional (meth) acrylates such as acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth)
  • Trifunctional (meth) acrylates such as acrylate, polyether tri (meth) acrylate, glycerin propoxytri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, ditrimethylolpropane tetra (meth)
  • Urethane curable resin is a polymer of urethane acrylate monomer or oligomer.
  • examples of the urethane acrylate oligomer include those having a polyoxyalkylene segment and / or a saturated polyester segment linked via a urethane bond and having acryloyl groups at both ends.
  • the curable resin may be a thermosetting type or an active energy ray curable type.
  • the active energy ray curable type is preferable.
  • Active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, visible rays, and ⁇ rays.
  • thermosetting or active energy ray-curable acrylic curable resin In order to obtain a thermosetting or active energy ray-curable acrylic curable resin, a thermal polymerization initiator or an active energy ray polymerization initiator is added to the monomer or oligomer having the polymerizable unsaturated group, It is necessary to make it a thermosetting or active energy ray-curable composition.
  • thermal polymerization initiator known ones can be used. Examples thereof include peroxide compounds such as benzoyl peroxide and di-t-butyl peroxide.
  • the addition amount of the thermal polymerization initiator is preferably 1 to 10% by mass with respect to the monomer or oligomer having a polymerizable unsaturated group.
  • active energy ray polymerization initiator known ones can be used.
  • benzoin benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1 -One, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, propi Phenone, dich
  • One of these active energy ray polymerization initiators may be used alone, or two or more thereof may be used in combination.
  • the addition amount of the active energy ray polymerization initiator is preferably 1 to 10% by mass relative to the monomer or oligomer having a polymerizable unsaturated group.
  • a photosensitizer can be further contained.
  • the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine and the like.
  • the hard coat layer 11 may contain a flexible component as necessary. When the flexible component is contained, it is possible to prevent the occurrence of cracks when punched with a high gel fraction.
  • a flexible component (meth) acrylates having one or more polymerizable unsaturated groups in the molecule are preferable. Examples of (meth) acrylates include tricyclodecanemethylol di (meth) acrylate, ethylene oxide modified di (meth) acrylate of bisphenol F, ethylene oxide modified di (meth) acrylate of bisphenol A, and ethylene oxide modified of isocyanuric acid.
  • Bifunctional (meth) acrylates such as di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, propylene oxide modified tri (meth) acrylate of trimethylpropane , Trifunctional (meth) acrylates such as ethylene oxide modified tri (meth) acrylate of trimethylpropane, urethane (meth) acrylate, polyester (meth ) Acrylates, polyether (meth) acrylate.
  • trifunctional (meth) acrylate and urethane (meth) acrylate are more preferable.
  • These (meth) acrylates can be used singly or in combination of two or more.
  • the hard coat layer 11 may contain reactive inorganic oxide particles or reactive organic particles.
  • the first hard coat layer 11 contains reactive inorganic oxide particles or reactive organic particles because the surface hardness of the high hardness film can be improved.
  • the reactive inorganic oxide particles are inorganic oxide particles treated with a coupling agent, and the reactive organic particles are organic particles treated with a coupling agent.
  • the bonding strength with the polymer can be increased. As a result, surface hardness and scratch resistance can be improved.
  • the inorganic oxide particles preferably have high hardness.
  • silicon dioxide particles, titanium dioxide particles, zirconium oxide particles, aluminum oxide particles and the like can be used.
  • organic particles that can be used include resin particles such as acrylic resin, polystyrene, polysiloxane, melamine resin, benzoguanamine resin, polytetrafluoroethylene, cellulose acetate, polycarbonate, and polyamide.
  • Examples of coupling agents include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ -mercaptopropyltrimethoxy.
  • Examples thereof include silane, ⁇ -aminopropyltriethoxysilane, and ⁇ -aminopropyltriethoxyaluminum. These may be used individually by 1 type and may use 2 or more types together.
  • the treatment amount of the coupling agent is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the inorganic oxide particles or organic particles.
  • the hard coat layer 11 may contain components other than those described above as long as the effects of the present invention are not impaired.
  • inorganic fine particles for imparting anti-blocking properties for imparting antibacterial properties; fluorine-based antifouling agents for imparting antifouling properties; fluorine-based lubricants or silicon for imparting slipperiness Leveling agent for improving coating suitability; Metal oxide fine particles for imparting antistatic performance, antistatic resin, conductive polymer; Metal oxide fine particles for providing UV shielding, UV absorption Agents; light stabilizers and the like.
  • the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer 13 for example, a natural rubber-based pressure-sensitive adhesive, a synthetic rubber-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, or the like is used. Moreover, any of solvent system, emulsion system, and water system may be sufficient. Among these, solvent-type acrylic pressure-sensitive adhesives are particularly preferred from the viewpoints of transparency, weather resistance, durability, cost and the like when used for optical system applications.
  • the acrylic pressure-sensitive adhesive is obtained by crosslinking an acrylic polymer with a crosslinking agent.
  • the acrylic polymer is a polymer having a non-crosslinkable acrylic monomer unit and a crosslinkable monomer unit.
  • the “monomer unit” is a repeating unit constituting the polymer.
  • An “acrylic monomer” is a compound having a (meth) acryloyl group.
  • (Meth) acryloyl group” means an acryloyl group or a methacryloyl group.
  • the non-crosslinkable acrylic monomer is an acrylic monomer that does not have crosslinkability, and the crosslinkable monomer is a monomer having a crosslinkable group.
  • the crosslinkable monomer may be an acrylic monomer or a non-acrylic monomer as long as it can be polymerized with the non-crosslinkable acrylic monomer.
  • the crosslinkable group include a carboxyl group, a hydroxy group, an amino group, an epoxy group, and a glycidyl group.
  • non-crosslinkable acrylic monomer unit examples include a (meth) acrylic acid ester unit in which the hydrogen atom of the carboxyl group of (meth) acrylic acid is substituted with a hydrocarbon group.
  • the hydrocarbon group preferably has 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms.
  • the hydrocarbon group may have a substituent.
  • the substituent is not particularly limited as long as it does not contain a crosslinkable group, and examples thereof include alkoxy groups such as methoxy group and ethoxy group.
  • the (meth) acrylic acid ester examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n- (meth) acrylate Octyl, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-undecyl (meth) acrylate, N-do
  • (meth) acrylic acid means containing both “acrylic acid” and “methacrylic acid”.
  • the crosslinkable monomer unit includes a carboxyl group-containing copolymerizable monomer unit, a hydroxy group-containing copolymerizable monomer unit, an amino group-containing copolymerizable monomer unit, and a glycidyl group-containing copolymerizable monomer.
  • Examples include body units.
  • Examples of the carboxyl group-containing copolymerizable monomer include ⁇ , ⁇ -unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and grataconic acid, and anhydrides thereof. Such as things.
  • hydroxy group-containing copolymerizable monomer examples include (meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate.
  • (Meth) acrylic acid lactones such as hydroxyalkyl, (meth) acrylic acid (meth) acrylic acid mono (diethylene glycol) [(mono, di or poly) alkylene glycol], (meth) acrylic acid monocaprolactone and the like.
  • Examples of the amino group-containing copolymerizable monomer include (meth) acrylamide and allylamide.
  • Examples of the glycidyl group-containing copolymerizable monomer include glycidyl (meth) acrylate.
  • a carboxyl group-containing copolymerizable monomer is preferable from the viewpoints of adhesiveness, crosslinkability, polymerizability, and the like.
  • auxiliaries include antioxidants, tackifiers, silane coupling agents, ultraviolet absorbers, light stabilizers such as hindered amine compounds, and fillers.
  • antioxidants examples include phenolic antioxidants, amine antioxidants, lactone antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. These antioxidants may be used alone or in combination of two or more.
  • tackifier examples include rosin resin, terpene resin, terpene phenol resin, coumarone indene resin, styrene resin, xylene resin, phenol resin, petroleum resin, and the like.
  • silane coupling agent examples include mercaptoalkoxysilane compounds (for example, mercapto group-substituted alkoxy oligomers).
  • ultraviolet absorber examples include benzotriazole compounds and benzophenone compounds.
  • the thickness of the adhesive layer 13 is preferably 25 ⁇ m or less. Further, it is more preferably 5 to 25 ⁇ m, further preferably 5 to 20 ⁇ m, and further preferably 10 to 15 ⁇ m. When the thickness of the pressure-sensitive adhesive layer 13 is within the above range, it becomes easy to ensure high hardness without causing delamination.
  • G ′ (20 ° C.) When G ′ (20 ° C.) is within the above range, the adhesive layer 13 can follow the deformation of the base film 12 due to curling or the like, and the shape of the final product is hardly impaired. Further, when G ′ (20 ° C.) is 1 ⁇ 10 5 Pa or more, the protrusion of the adhesive layer 13 and the surface hardness of the film are hardly lowered. When G ′ (20 ° C.) is 1 ⁇ 10 7 Pa or less, delamination hardly occurs.
  • the hard coat layer 11 and the adhesive layer 13 are formed by applying a hard coat composition or an adhesive composition using a solvent to the substrate 12, heating and drying, and then curing. The It is necessary to prevent curling and peeling even during such heating or after a long time has passed since the final product was manufactured.
  • the viscosity of the adhesive layer 13 is required to have a value in a specific range at a high temperature. That is, the dynamic shear storage elastic modulus G ′ (80 ° C.) (Pa) of the adhesive layer 13 at 80 ° C. and a frequency of 1 Hz needs to satisfy the following formula (2). 1 ⁇ 10 4 Pa ⁇ G ′ (80 ° C.) ⁇ 1 ⁇ 10 6 Pa (2) Preferably, 5 ⁇ 10 4 Pa ⁇ G ′ (80 ° C.) ⁇ 5 ⁇ 10 5 Pa.
  • G ′ (80 ° C.) is within the above range, the adhesive layer 13 can follow the deformation of the base film 12 such as curl that occurs during heating or at room temperature for a long time, and the final product There is little damage to the shape. Further, when G ′ (80 ° C.) is 1 ⁇ 10 4 Pa or more, the adhesive layer 13 is difficult to flow, and a layer having a uniform thickness is easily formed. When G ′ (80 ° C.) is 1 ⁇ 10 6 Pa or less, curling and delamination hardly occur.
  • the dynamic shear storage elastic modulus G ′ of the pressure-sensitive adhesive layer 13 in the present invention is obtained by taking a test piece having a thickness of 100 to 150 ⁇ m and using a viscoelasticity tester, the frequency is 1 Hz, the strain is 0.1%, and the heating rate is It can be obtained by measuring the storage elastic modulus (G ′) (Pa) at a temperature of 20 ° C. and 80 ° C. at 3 ° C./min. The test piece can be measured after laminating thin sheets of adhesive to obtain a predetermined thickness.
  • the laminated film of the base material and the pressure-sensitive adhesive may be overlapped and measured. In the latter case, the total thickness of only the adhesive layer 13 is adjusted to a predetermined thickness.
  • the value of the dynamic shear storage modulus G ′ of the adhesive layer 13 can be adjusted by the weight average molecular weight of the polymer, the composition of the monomer, the blending amount of the crosslinking agent (crosslinking density), and the like. For example, in order to bring G ′ (20 ° C.) within the above range, it can be adjusted by increasing the number of monomers having a high glass transition temperature or by increasing the crosslinking density. Similarly, when adjusting the inclination from G ′ (20 ° C.) to G ′ (80 ° C.), G ′ (80 ° C.) can be set within the above range by adjusting the crosslinking density.
  • Monomers having a high glass transition temperature include isobornyl acrylate, t-butyl acrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, lauryl acrylate, stearyl acrylate, cyclohexyl acrylate, 3-methyl-1, 5- Examples include pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and t-butyl methacrylate. In order to increase the crosslinking density, it is effective to use a tetrafunctional or higher functional (meth) acrylate.
  • the adhesive strength of the adhesive layer 13 is preferably 5 N / 25 mm or more. More preferably, it is 10 N / 25 mm or more. When it is 5 N / 25 mm or more, curling and delamination are unlikely to occur during manufacture or use.
  • FIG. 5 is a schematic cross-sectional view showing the configuration of the second embodiment of the present invention.
  • the high-hardness film 3 in FIG. 5 is configured by attaching a front film 20 c and a back film 21 c via an adhesive layer 13.
  • the surface film 20c includes a first substrate 12a, a first hard coat layer 11a laminated on the surface of the first substrate 12a, and a third hard coat layer 11c laminated on the back surface of the first substrate 12a.
  • the back film 21c has the 2nd base material 12b and the 2nd hard-coat layer 11b laminated
  • FIG. 6 is a schematic cross-sectional view showing the configuration of the third embodiment of the present invention.
  • the high hardness film 4 of FIG. 6 is configured by attaching a front film 20d and a back film 21d with an adhesive layer 13 interposed therebetween.
  • the surface film 20d has the 1st base material 12a and the 1st hard-coat layer 11a laminated
  • the back film 21d includes a second base 12b and a second hard coat layer 11b laminated on the back of the second base 12b. Further, a printed layer 14 is formed on the back surface of the second hard coat layer 11b for the purpose of decoration or the like.
  • the reason why the printing layer 14 is disposed on the back surface of the second hard coat layer 11b is that, in an image display device or the like, the printing layer 14 is enclosed inside, and there is no physical contact from the outside, and the printing surface is This is because it is protected.
  • each layer constituting the second embodiment and the third embodiment is the same as that of the first embodiment, the description thereof is omitted. Further, in the following description, except for the description relating to the print layer, the embodiment is common to each embodiment when the embodiment is not specified.
  • the surface films 20a, 20b, 20c, and 20d may be collectively referred to as the surface film 20.
  • back film 21a, 21b, 21c, 21d may be collectively described as back film 21.
  • the printing layer 14 of the third embodiment is a layer formed by printing colored ink containing a colorant and a binder.
  • a pigment or a dye is used as the colorant.
  • the binder resins such as polyvinyl resins, polyamide resins, polyacrylic resins, polyurethane resins, polyvinyl acetal resins, polyester urethane resins, cellulose ester resins, and alkyd resins can be used.
  • a metal particle such as aluminum, titanium, bronze, or a pearl pigment obtained by coating titanium oxide on mica can be used as a colorant.
  • the high hardness film of this embodiment can have a pencil hardness measured based on JIS K5600-5-4 of 5H or more, and can be used as a substitute for a glass plate.
  • the surface hardness (pencil hardness) of the high-hardness film is not determined only by the material forming the outermost first hard coat layer 11a, but the first hard coat layer 11a from the back.
  • the composition and materials of all other layers that support it are involved.
  • the hard coat layer 11 needs to be provided on the outermost surface of the high hardness film 1.
  • the 3rd hard-coat layer 11c can further be provided in the back surface of the surface film 20 for the purpose of pencil hardness improvement (refer FIG. 5).
  • a fourth hard coat layer can be provided on the surface of the back film 21 (not shown).
  • the third hard coat layer 11c is preferably provided not on the surface of the back film 21 but on the back surface of the front film 20.
  • the pencil hardness of the single hard coat layer is preferably such that the first hard coat layer 11a> the second hard coat layer 11b ⁇ the third hard coat layer 11c.
  • the plurality of hard coat layers 11 may be made of the same material or different materials.
  • the hard coat layer 11 is a layer that affects the surface hardness. Therefore, it is effective to make the hard coat layer 11 thicker.
  • the total thickness of the plurality of hard coat layers 11 is related to the surface hardness. On the other hand, if the total thickness of the hard coat layer 11 is too large, drying and curing may be insufficient in production. Therefore, the total thickness of the hard coat layer 11 is preferably 15 to 80 ⁇ m, more preferably 25 to 60 ⁇ m, and still more preferably 35 to 55 ⁇ m.
  • a conductive layer, a low reflection layer, an anti-fingerprint layer, and the like can be given.
  • the high hardness film of this embodiment can be manufactured as follows, for example.
  • the following manufacturing process can also be performed continuously in a roll-to-roll manner.
  • (1) 1st base material formation process The 1st hard-coat layer 11a is formed in the single side
  • (2) 2nd base material formation process The 2nd hard-coat layer 11b is formed in the single side
  • the hard coat layer can be formed as follows. First, an uncured coating film is formed by coating a hard coat layer forming coating solution containing a curable resin on each substrate.
  • Examples of the solvent for the hard coat layer forming coating solution include methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, toluene, n-hexane, n-butyl alcohol, methyl isobutyl ketone, methyl butyl ketone, ethyl butyl ketone, cyclohexanone, Ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, N-methyl-2-pyrrolidone and the like are used. These may be used alone or in combination of two or more.
  • solvents having different evaporation rates For example, it is preferable to use a mixture of methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, and propylene glycol monomethyl ether.
  • the coating liquid for hard-coat layer formation contains a well-known photoinitiator in order to accelerate hardening.
  • crosslinking agents such as an isocyanate compound and an epoxy compound.
  • Examples of the coating method of the hard coat layer forming coating solution include a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a micro gravure coater, a rod blade coater, a lip coater, a die coater, a curtain coater, and printing. The method using a machine etc. is mentioned.
  • the coating film is dried by heating the substrate having the coating film.
  • the heating is performed at a temperature of 60 to 100 ° C. and a heating time of 1 to 5 minutes.
  • the uncured coating film is cured.
  • the uncured coating film contains a thermosetting resin, it is cured by heating using a heating furnace or an infrared lamp.
  • the uncured coating film contains an active energy ray-curable resin, it is cured by irradiation with active energy rays.
  • the active energy rays include ultraviolet rays and electron beams. Among them, ultraviolet rays are preferable from the viewpoint of versatility.
  • the ultraviolet light source for example, a high pressure mercury lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, a xenon arc, an electrodeless ultraviolet lamp, or the like can be used.
  • Curing by irradiation with active energy rays is preferably performed in the presence of an inert gas such as nitrogen.
  • the curing process may be performed in two stages, a preliminary curing process and a main curing process.
  • the front film 20 and the back film 21 can be stuck by any of the following methods.
  • the pressure-sensitive adhesive coating liquid in the above (a) and (b) contains a pressure-sensitive adhesive, a solvent, and an auxiliary as necessary.
  • the solvent include alcohol (eg, methanol, ethanol, propanol, etc.), ketone (eg, acetone, methyl ethyl ketone, etc.), ether (eg, diethyl ether, methyl cellosolve, ethyl cellosolve, etc.) and the like.
  • Examples of the coater for applying the adhesive coating solution include a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a rod blade coater, a lip coater, a die coater, a curtain coater, and a printing machine. Drying is performed by a heat dryer or a vacuum dryer.
  • the double-sided PSA sheet in the above (c) and (d) is one in which an adhesive layer is provided between a pair of release sheets.
  • the material for the release sheet include paper and film.
  • the release sheet is preferably a single-sided release sheet having a release layer on one side. Moreover, it is preferable that the peeling force with respect to the adhesion layer of one peeling sheet differs from the peeling force with respect to the adhesion layer of the other peeling sheet. Thereby, it becomes easy to peel only one release sheet first.
  • an offset printing method, a gravure printing method, a screen printing method, or the like is applied as a forming method (printing method) of the printing layer 14, and multi-color printing or gradation expression is performed.
  • a screen printing method is preferred.
  • Printing may be performed before “(3) sticking step”. That is, you may print on the back surface film 21 before sticking with the surface film 20.
  • the printing may be performed after “(4) Punching process”.
  • the punching is performed by inserting a punching blade into the laminated film in which the front film 20 and the back film 21 are bonded.
  • the punching blade may be rotated or reciprocated with respect to the laminated film.
  • PET film a trade name Cosmo Shine A4300, manufactured by Toyobo Co., Ltd., 210 mm ⁇ 297 mm, thickness 125 ⁇ m
  • Ii PET film b
  • Lumirror U34 manufactured by Toray Industries, Inc., 210 mm ⁇ 297 mm, thickness 125 ⁇ m
  • IIii PET film c
  • KEL86W manufactured by Teijin DuPont Co., Ltd., 210 mm ⁇ 297 mm, thickness 125 ⁇ m
  • PET film d trade name Cosmo Shine A4300, manufactured by Toyobo Co., Ltd., 210 mm ⁇ 297 mm, thickness 250 ⁇ m
  • ⁇ Preparation of film A> As an active energy ray-curable resin composition, 49 parts by mass of dipentaerythritol hexaacrylate (trade name: A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.), leveling agent (trade name BYK-310, Big Chemie Japan Co., Ltd.) 0.1 parts by mass, 1.5 parts by mass of a photopolymerization initiator (trade name IRGACURE184, manufactured by BASF Corporation) and 49.4 parts by mass of methyl ethyl ketone were mixed to prepare a composition for forming a film A.
  • dipentaerythritol hexaacrylate trade name: A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • leveling agent trade name BYK-310, Big Chemie Japan Co., Ltd.
  • a photopolymerization initiator trade name IRGACURE184, manufactured by BASF Corporation
  • a PET film a was used as a substrate, and the film A-forming composition was bar-coated on the PET film a. Then, it dried for 120 second with a 80 degreeC hot-air dryer. Furthermore, using a high-pressure mercury lamp ultraviolet ray irradiator (made by Eye Graphics Co., Ltd.), ultraviolet rays were irradiated under the conditions of an irradiation intensity of 200 mW / cm 2 , an integrated light amount of 300 mJ / cm 2 , and an oxygen concentration of 10,000 ppm or less. Through the above steps, a hard coat layer having a film thickness of 25 ⁇ m was formed on the base material to obtain a film A.
  • a high-pressure mercury lamp ultraviolet ray irradiator made by Eye Graphics Co., Ltd.
  • ⁇ Preparation of film B> As an active energy ray curable resin composition, 49 parts by mass of trimethylolpropane triacrylate (trade name A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.), leveling agent (trade name BYK-310, manufactured by Big Chemie Japan Co., Ltd.) ) 0.1 parts by mass, 1.5 parts by mass of a photopolymerization initiator (trade name IRGACURE 184, manufactured by BASF Corp.) and 49.4 parts by mass of methyl ethyl ketone were mixed to prepare a composition for forming film B.
  • A-TMPT trimethylolpropane triacrylate
  • leveling agent trade name BYK-310, manufactured by Big Chemie Japan Co., Ltd.
  • a photopolymerization initiator trade name IRGACURE 184, manufactured by BASF Corp.
  • a PET film a was used as a substrate, and a film B forming composition was bar-coated on the PET film a. Then, it dried for 60 second with a 80 degreeC hot-air dryer. Furthermore, using a high-pressure mercury lamp ultraviolet ray irradiator (made by Eye Graphics Co., Ltd.), ultraviolet rays were irradiated under the conditions of an irradiation intensity of 200 mW / cm 2 , an integrated light amount of 300 mJ / cm 2 , and an oxygen concentration of 10,000 ppm or less. Through the above steps, a hard coat layer having a film thickness of 25 ⁇ m was formed on the base material to obtain a film B.
  • a high-pressure mercury lamp ultraviolet ray irradiator made by Eye Graphics Co., Ltd.
  • ethoxylated isocyanuric acid triacrylate (trade name A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.), leveling agent (trade name BYK-310, Big Chemie Japan Co., Ltd.) 0.1 parts by mass, 1.5 parts by mass of a photopolymerization initiator (trade name IRGACURE184, manufactured by BASF Corp.) and 49.4 parts by mass of methyl ethyl ketone were mixed to prepare a composition for forming film C.
  • the film C-forming composition was bar coated on the surface of the film A on which the hard coat layer was not formed. Then, it dried for 60 second with a 80 degreeC hot-air dryer. Furthermore, using a high-pressure mercury lamp ultraviolet ray irradiator (made by Eye Graphics Co., Ltd.), ultraviolet rays were irradiated under the conditions of an irradiation intensity of 200 mW / cm 2 , an integrated light amount of 300 mJ / cm 2 , and an oxygen concentration of 10,000 ppm or less. Through the above steps, a hard coat layer having a thickness of 3 ⁇ m was formed on the base material, and a film C was obtained.
  • a high-pressure mercury lamp ultraviolet ray irradiator made by Eye Graphics Co., Ltd.
  • tolylene diisocyanate (trade name Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.), which is a cross-linking agent, is mixed with 100 parts by mass of the acrylic polymer solid content to obtain a weight average molecular weight of 80.
  • Ten thousand adhesive solution 1 was obtained.
  • the weight average molecular weight is calculated based on a calibration curve prepared using a polystyrene standard material by gel permeation chromatography (GPC) measurement.
  • a pressure-sensitive adhesive solution 2 was prepared. That is, in the reactor, 65 parts by mass of 2-ethylhexyl acrylate which is an acrylic monomer, 10 parts by mass of methyl methacrylate, 15 parts by mass of ethyl methacrylate, 10 parts by mass of hydroxyethyl acrylate, and 2,2 ′ which is a polymerization initiator. -0.1 part by weight of azoisobutyronitrile was added. Then, it superposed
  • tolylene diisocyanate (trade name Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.), which is a crosslinking agent, is mixed with 100 parts by mass of the acrylic polymer solid content, and the weight average molecular weight is 1,500,000.
  • An adhesive solution 2 was prepared.
  • tolylene diisocyanate (trade name Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.), which is a cross-linking agent, is mixed with 100 parts by mass of the acrylic polymer solid content to obtain a weight average molecular weight of 50.
  • Ten thousand adhesive solution 3 was prepared.
  • Example 1 The pressure-sensitive adhesive solution 1 obtained above was applied to the surface of the film B, which is the back film, on which the hard coat layer was not formed, using a knife coater so that the coating thickness after drying was 10 ⁇ m, and 100 It was dried at 0 ° C. for 2 minutes to form an adhesive layer. Next, the pressure-sensitive adhesive layer and the surface of the film A, which is a surface film, were bonded together to form a laminated film 1.
  • Example 2 A laminated film 2 was produced in the same manner as in Example 1 except that the thickness of the adhesive layer was changed to 15 ⁇ m.
  • Example 3 A laminated film 3 is formed in the same manner as in Example 1 except that the film C is used instead of the film A which is a surface film and the film C is bonded to the surface on which the hard coat layer having a film thickness of 3 ⁇ m is formed. Produced.
  • Example 4 A laminated film 4 was produced in the same manner as in Example 1 except that the film A was used instead of the film B as the back film, and an adhesive layer was formed on the surface where the hard coat layer was not formed.
  • Example 5 A laminated film 5 was produced in the same manner as in Example 1 except that the first substrate was changed to the PET film b.
  • Example 6 A laminated film 6 was produced in the same manner as in Example 1 except that the second substrate was changed to the PET film b.
  • Example 7 A laminated film 7 was produced in the same manner as in Example 1 except that the first substrate and the second substrate were changed to the PET film c.
  • Example 8 A laminated film 8 was produced in the same manner as in Example 1 except that the first substrate was changed to the PET film c.
  • Example 9 A laminated film 9 was produced in the same manner as in Example 1 except that the second substrate was changed to the PET film c.
  • Example 10 A laminated film 10 was produced in the same manner as in Example 1 except that the thickness of the adhesive layer was changed to 25 ⁇ m.
  • Example 2 A laminated film 12 was produced in the same manner as in Example 1 except that the adhesive solution 3 was used.
  • Example 3 A laminated film 13 was produced in the same manner as in Example 1 except that the pressure-sensitive adhesive was applied to the surface of the film A, which is a surface film, on which the hard coat layer was formed.
  • Example 4 A laminated film 14 was produced in the same manner as in Example 1 except that a pressure-sensitive adhesive was applied to the surface of the film B that is the back film on which the hard coat layer was formed.
  • Example 5 A laminated film 15 was produced in the same manner as in Example 1 except that the PET film a was used instead of the film B as the back film.
  • Example 6 The composition for forming film A was applied to the surface of PET film d under the same conditions as in Example 1 without using an adhesive layer, thereby forming a hard coat layer having a thickness of 25 ⁇ m.
  • a film B forming composition was applied under the same conditions as in Example 1 under the same conditions as in Example 1 to form a hard coat layer with a film thickness of 25 ⁇ m. 16 was produced.
  • the laminated films obtained in the above examples and comparative examples were evaluated for various properties and performances by the methods described below.
  • the produced laminated film was cut into a size of 200 mm ⁇ 200 mm and allowed to stand in an environment of 23 ° C. and 50% RH for 24 hours. After that, place the test piece on a horizontal plate so that the test piece is concave (the concave part is on the upper side), and lift the four corners (distance from the plate surface to each corner) with a ruler. The average value (mm) at the four corners was obtained. A sample having an average value at four corners of less than 10 mm was evaluated as ⁇ , a sample having a mean value of 10 mm or more and less than 15 mm was evaluated as ⁇ , and a sample having a mean value of 15 mm or more was evaluated as ⁇ . Further, the curl after the heat treatment was measured after the sample cut in the same manner was placed in a drier at 150 ° C. for 1 hour for heat treatment, and then allowed to stand in the same manner as described above.
  • the thickness of the pressure-sensitive adhesive layer of the laminated film after drying is measured with a knife coater on one side of a PET film (trade name Cosmo Shine A4300, manufactured by Toyobo Co., Ltd., thickness 100 ⁇ m) as a base material. The coating was made to be the same as the thickness. Next, the film was dried at 100 ° C. for 2 minutes, and bonded to a silicone PET release film (trade name: 75RL-07 (L), manufactured by Oji F-Tex Co., Ltd., 75 ⁇ m thickness). Then, after aging for 7 days in an environment of a temperature of 23 ° C.
  • a test piece having a width of 25 mm ⁇ a length of 100 mm was sampled from the film.
  • an alkali glass plate was prepared by washing the surface with ethanol and leaving it for 3 hours or more in an environment of a temperature of 23 ° C. and a humidity of 50% RH. What peeled off the peeling film from the test piece was bonded together by making it reciprocate on the surface of an alkali glass plate with the pressurization roller of mass 2kg. After 30 minutes from the pasting, the adhesive strength (N / 25 mm) was measured by peeling at a tensile rate of 300 mm / min by the 180-degree peeling method defined in JIS Z0237.
  • the PET film substrate was cut into a size of 100 mm long ⁇ 100 mm wide, and the dimensional change rate (%) in the vertical direction and the horizontal direction after heat treatment at 150 ° C. for 30 minutes was calculated in accordance with JIS C2151.
  • Comparative Example 1 did not satisfy both of the formulas (1) and (2) of the dynamic shear storage modulus of the adhesive layer, but the adhesive layer had weak adhesive force and delamination occurred. Therefore, it was difficult to evaluate.
  • the value of the dynamic shear storage elastic modulus of the adhesive layer was less than the lower limit of the formula (1), and the pencil hardness and the surface hardness were inferior.
  • Comparative Example 3 was inferior in pencil hardness, surface hardness and curl because the position of the hard coat layer of the surface film was reversed.
  • Comparative Example 4 was inferior in curl because the position of the hard coat layer on the back film was reversed.
  • Comparative Example 5 a PET film was used as the back film, but the pencil hardness, surface hardness and curl were inferior. Comparative Example 6 did not have an adhesive layer, but was inferior in curling.
  • the high hardness film of the present invention can be used as a surface protective film for protecting an image display device or the like. Moreover, since it is thin and transparent, it can be used as a base material for various display plates as an alternative to a thin glass plate. Moreover, by sticking on the surface of various plastic molded products, it is possible to increase the surface hardness to protect the inside, improve the scratch resistance, and prevent debris from scattering at the time of destruction.

Abstract

La présente invention concerne un film à haute dureté fin et léger et pouvant être réduit par tuilage ou délaminage, tout en maintenant une dureté de surface élevée. Ce film à haute dureté est caractérisé en ce qu'il comprend : un film de surface avant (20a) ayant une première base (12a) et une couche de revêtement dur (11a) laminée au moins sur la surface avant de la première base (12a) ; un film de surface arrière (21a) qui a une seconde base (12b) et une couche de revêtement dur (11b) laminée au moins sur la surface arrière de la seconde base (12b) ; et une couche adhésive (13) agencée entre la surface arrière du film de surface avant (20a) et la surface avant du film de surface arrière (21a) et qui relie les films entre eux. Ce film à haute dureté est également caractérisé en ce que : l'épaisseur t1 de la première base (12a) et l'épaisseur t2 de la seconde base (12b) ont une relation représentée par t1 ≤ t2 ≤ 1,1 × t1 ; et les modules de conservation de cisaillement dynamique G'(20 °C) et G'(80 °C) de la couche adhésive (13) remplissent les formules ci-dessous. 1 × 105 Pa ≤ G'(20 °C) ≤ 1 × 107 Pa 1 × 104 Pa ≤ G'(80 °C) ≤ 1 × 106 Pa
PCT/JP2014/082396 2013-12-09 2014-12-08 Film à haute dureté WO2015087827A1 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017065169A (ja) * 2015-09-30 2017-04-06 大日本印刷株式会社 筐体用積層板及び筐体
JP2017065170A (ja) * 2015-09-30 2017-04-06 大日本印刷株式会社 筐体用積層板及び筐体
JP2017200739A (ja) * 2016-05-06 2017-11-09 ホシデン株式会社 樹脂積層体及びこれを備えたタッチ入力装置
CN111164174A (zh) * 2017-10-02 2020-05-15 日东电工株式会社 粘合带
CN113088211A (zh) * 2021-04-29 2021-07-09 江西昊泽光学膜科技有限公司 一种无极度可热弯聚酯保护膜、制备方法及其应用
CN113444485A (zh) * 2020-03-27 2021-09-28 荒川化学工业株式会社 活性能量射线固化型粘合剂组合物、粘合剂层、层叠体
JP7416152B2 (ja) 2016-05-20 2024-01-17 大日本印刷株式会社 光学積層体、及び、画像表示装置

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08148036A (ja) * 1994-11-18 1996-06-07 Nitto Denko Corp 透明導電性フィルム
JP2006056117A (ja) * 2004-08-19 2006-03-02 Sony Corp 透明導電性積層体及びこれを用いたタッチパネル
WO2011007861A1 (fr) * 2009-07-16 2011-01-20 積水化学工業株式会社 Ruban adhésif sensible à la pression, stratifié et dispositif d'affichage d'image
JP2013035210A (ja) * 2011-08-08 2013-02-21 Oike Ind Co Ltd 積層体
WO2014088058A1 (fr) * 2012-12-06 2014-06-12 日東電工株式会社 Corps stratifié et film conducteur transparent utilisant ledit corps stratifié

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000263702A (ja) * 1999-03-18 2000-09-26 Dainippon Printing Co Ltd ハードコートフィルム、その製造方法及びハードコートフィルム貼付陰極線管
JP5304339B2 (ja) * 2009-03-11 2013-10-02 東洋インキＳｃホールディングス株式会社 粘着剤組成物及びそれを用いてなる粘着積層体
JP2011039823A (ja) * 2009-08-12 2011-02-24 Oji Paper Co Ltd タッチパネル用保護シート及びタッチパネル用導電性積層体
JP6225025B2 (ja) * 2011-08-03 2017-11-01 リンテック株式会社 ガスバリア性粘着シート、その製造方法、並びに電子部材及び光学部材
JP5845765B2 (ja) * 2011-09-21 2016-01-20 凸版印刷株式会社 透明導電性積層体及びその製造方法
JP5885021B2 (ja) * 2011-12-26 2016-03-15 Dic株式会社 ハードコートフィルム

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08148036A (ja) * 1994-11-18 1996-06-07 Nitto Denko Corp 透明導電性フィルム
JP2006056117A (ja) * 2004-08-19 2006-03-02 Sony Corp 透明導電性積層体及びこれを用いたタッチパネル
WO2011007861A1 (fr) * 2009-07-16 2011-01-20 積水化学工業株式会社 Ruban adhésif sensible à la pression, stratifié et dispositif d'affichage d'image
JP2013035210A (ja) * 2011-08-08 2013-02-21 Oike Ind Co Ltd 積層体
WO2014088058A1 (fr) * 2012-12-06 2014-06-12 日東電工株式会社 Corps stratifié et film conducteur transparent utilisant ledit corps stratifié

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017065169A (ja) * 2015-09-30 2017-04-06 大日本印刷株式会社 筐体用積層板及び筐体
JP2017065170A (ja) * 2015-09-30 2017-04-06 大日本印刷株式会社 筐体用積層板及び筐体
JP2017200739A (ja) * 2016-05-06 2017-11-09 ホシデン株式会社 樹脂積層体及びこれを備えたタッチ入力装置
KR20170125703A (ko) * 2016-05-06 2017-11-15 호시덴 가부시기가이샤 수지적층체 및 이것을 구비한 터치 입력 장치
US10556399B2 (en) 2016-05-06 2020-02-11 Hosiden Corporation Plastic laminate structure and touch sensing device having the same
KR102367188B1 (ko) 2016-05-06 2022-02-23 호시덴 가부시기가이샤 수지적층체 및 이것을 구비한 터치 입력 장치
JP7416152B2 (ja) 2016-05-20 2024-01-17 大日本印刷株式会社 光学積層体、及び、画像表示装置
CN111164174A (zh) * 2017-10-02 2020-05-15 日东电工株式会社 粘合带
US11186750B2 (en) 2017-10-02 2021-11-30 Nitto Denko Corporation Pressure-sensitive adhesive tape
CN113444485A (zh) * 2020-03-27 2021-09-28 荒川化学工业株式会社 活性能量射线固化型粘合剂组合物、粘合剂层、层叠体
JP7405110B2 (ja) 2020-03-27 2023-12-26 荒川化学工業株式会社 活性エネルギー線硬化型粘着剤組成物、粘着剤層、積層体
CN113088211A (zh) * 2021-04-29 2021-07-09 江西昊泽光学膜科技有限公司 一种无极度可热弯聚酯保护膜、制备方法及其应用

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