WO2015087827A1 - High hardness film - Google Patents
High hardness film Download PDFInfo
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- 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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- 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
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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
- B32B7/06—Interconnection of layers permitting easy separation
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/542—Shear strength
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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
- 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.
Landscapes
- Laminated Bodies (AREA)
Abstract
Provided is a high hardness film which is thin and lightweight and is able to be reduced in the occurrence of curling or delamination, while maintaining high surface hardness. This high hardness film is characterized by comprising: a front surface film (20a) which has a first base (12a) and a hard coat layer (11a) that is laminated at least on the front surface of the first base (12a); a back surface film (21a) which has a second base (12b) and a hard coat layer (11b) that is laminated at least on the back surface of the second base (12b); and an adhesive layer (13) which is arranged between the back surface of the front surface film (20a) and the front surface of the back surface film (21a), and which bonds the films with each other. This high hardness film is also characterized in that: the thickness t1 of the first base (12a) and the thickness t2 of the second base (12b) have a relationship represented by t1 ≤ t2 ≤ 1.1 × t1; and the dynamic shear storage moduli G'(20°C) and G'(80°C) of the adhesive layer (13) satisfy the formulae below.
1 × 105 Pa ≤ G'(20°C) ≤ 1 × 107 Pa
1 × 104 Pa ≤ G'(80°C) ≤ 1 × 106 Pa
Description
本発明は、ハードコート層を有する高硬度フィルムに関するものである。
The present invention relates to a high hardness film having a hard coat layer.
近年、液晶方式や有機EL方式などのフラットパネルディスプレイや、看板、道路標識等の案内表示ディスプレイ等の様々な画像表示装置がある。さらに、パーソナルコンピューター、携帯電話、携帯ゲーム機器等のフラットパネルディスプレイには、タッチパネルが付与された製品が数多く商品化されている。このような画像表示装置を保護するために表面に保護シートが貼付される。
In recent years, there are various image display devices such as a flat panel display such as a liquid crystal system and an organic EL system, and a guide display such as a signboard and a road sign. In addition, many flat panel displays such as personal computers, mobile phones, and portable game machines have been commercialized with touch panels. In order to protect such an image display device, a protective sheet is attached to the surface.
特に、フラットパネルディスプレイの表面には薄いガラス基材が用いられることがあり、このガラス基材が飛散するのを防止するためにガラス基材表面または裏面に保護シートが貼付される。このガラス基材に貼付される保護シートには、防眩性や指紋付着防止性を付与した表貼りシートや、加飾のための裏貼りシートがある。
In particular, 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. Examples of 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.
しかし、軽量化、薄肉化の流れやフラットではない画像表示装置が現れ始めている中にあって、ガラス基材をプラスチック素材で置き換えようとする試みが数多くなされてきている。
However, while the trend toward lightening and thinning and image display devices that are not flat are beginning to appear, many attempts have been made to replace glass substrates with plastic materials.
特許文献1には、ハードコート層を基材の片側に2層設けることによって、高硬度とカールの改善の両立を図ろうとするハードコートフィルムが開示されている。
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.
特許文献2には、表面フィルムと裏面フィルムとを貼り合せたものであって、2層の基材と3つのハードコート層とを有するタッチパネル用保護シートが開示されている。
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.
しかしながら、特許文献1に記載の発明は、層構成のバランスに劣り、時間が経過したり、加熱時や加工時に、カールや層間剥離が生じる場合があった。また、特許文献2に記載の発明も、十分にバランスが取れた層構成であるとは言えず、カール防止や層間剥離防止の性能として、まだ改善する余地を有するものであった。
However, the invention described in 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. In addition, the invention described in 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.
本発明は、ガラス基材に代わるものとして、薄く軽量で、高い表面硬度を維持しながら、カールや層間剥離の発生を低減し得る高硬度フィルムを提供することを課題としている。
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.
本発明者らは、上記課題を解消するために、種々の検討を重ねた。
カールや層間剥離は、最終製品として使用されているときに問題となるのみならず、製造時において、多層からなる積層フィルムを高速で順次積層していくときにも問題となる。カールや層間剥離が発生すると、製造が困難となったり、商品寿命を短縮することにつながる。層間剥離した積層フィルムを分析したところ、多くの場合、粘着層の界面で剥離が生じるとの知見を得た。さらに、粘着層の熱的・動的挙動と層間剥離との関係について検討を加えた。その結果、室温時における動的粘弾性の挙動が使用時の粘着層と基材との界面での剥離性能に係り、加熱時における動的粘弾性の挙動が加工時や長時間経過時の粘着層と基材との界面での剥離性能に係っていることが判明した。そして、層間剥離を防止するためには、室温時と加熱時の動的せん断貯蔵弾性率をそれぞれ特定の範囲に制御することが肝要であることが判明した。 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. As a result, 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, and 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.
カールや層間剥離は、最終製品として使用されているときに問題となるのみならず、製造時において、多層からなる積層フィルムを高速で順次積層していくときにも問題となる。カールや層間剥離が発生すると、製造が困難となったり、商品寿命を短縮することにつながる。層間剥離した積層フィルムを分析したところ、多くの場合、粘着層の界面で剥離が生じるとの知見を得た。さらに、粘着層の熱的・動的挙動と層間剥離との関係について検討を加えた。その結果、室温時における動的粘弾性の挙動が使用時の粘着層と基材との界面での剥離性能に係り、加熱時における動的粘弾性の挙動が加工時や長時間経過時の粘着層と基材との界面での剥離性能に係っていることが判明した。そして、層間剥離を防止するためには、室温時と加熱時の動的せん断貯蔵弾性率をそれぞれ特定の範囲に制御することが肝要であることが判明した。 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. As a result, 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, and 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.
また、積層フィルムの表面硬度は、単純に、最表面に形成したハードコート層のみの表面硬度や厚さで決定される訳ではなく、積層フィルムの層構造全体が関わっていることを見出した。さらに、高硬度フィルムを構成する各層が、粘着層の両側において互いにできるだけ対称的な層構成となっていることがカールや層間剥離の発生防止に有効であることも見出した。
Also, it was found that 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.
本発明は、上記のような多くの知見を基に、完成するに至ったものである。即ち、本発明は以下のような構成を有している。
The present invention has been completed based on many findings as described above. That is, the present invention has the following configuration.
(1)第1基材と該第1基材の少なくとも表面に積層されたハードコート層とを有する表面フィルムと、第2基材と該第2基材の少なくとも裏面に積層されたハードコート層とを有する裏面フィルムと、前記表面フィルムの裏面と前記裏面フィルムの表面との間に設けられ、両フィルムを貼着する粘着層を備え、前記第1基材の厚さt1と前記第2基材の厚さt2とが、t1≦t2≦1.1×t1の関係にあり、前記粘着層の20℃、周波数1Hzにおける動的せん断貯蔵弾性率G´(20℃)および前記粘着層の80℃、周波数1Hzにおける動的せん断貯蔵弾性率G´(80℃)が下記式(1)および式(2)を満足することを特徴とする高硬度フィルム。
1×105Pa≦G´(20℃)≦1×107Pa ・・・(1)
1×104Pa≦G´(80℃)≦1×106Pa ・・・(2) (1) A surface film having a first substrate and a hard coat layer laminated on at least the surface of the first substrate, and a hard coat layer laminated on at least the back surface of the second substrate and the second substrate. A back film having a thickness t 1 of the first base material and a second thickness of the first base material. The thickness t 2 of the base material has a relationship of t 1 ≦ t 2 ≦ 1.1 × t 1 , and 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. and a frequency of 1 Hz satisfies the following formulas (1) and (2).
1 × 10 5 Pa ≦ G ′ (20 ° C.) ≦ 1 × 10 7 Pa (1)
1 × 10 4 Pa ≦ G ′ (80 ° C.) ≦ 1 × 10 6 Pa (2)
1×105Pa≦G´(20℃)≦1×107Pa ・・・(1)
1×104Pa≦G´(80℃)≦1×106Pa ・・・(2) (1) A surface film having a first substrate and a hard coat layer laminated on at least the surface of the first substrate, and a hard coat layer laminated on at least the back surface of the second substrate and the second substrate. A back film having a thickness t 1 of the first base material and a second thickness of the first base material. The thickness t 2 of the base material has a relationship of t 1 ≦ t 2 ≦ 1.1 × t 1 , and 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. and a frequency of 1 Hz satisfies the following formulas (1) and (2).
1 × 10 5 Pa ≦ G ′ (20 ° C.) ≦ 1 × 10 7 Pa (1)
1 × 10 4 Pa ≦ G ′ (80 ° C.) ≦ 1 × 10 6 Pa (2)
(2)前記粘着層の厚さが25μm以下である前記(1)に記載の高硬度フィルム。
(2) The high hardness film according to (1), wherein the adhesive layer has a thickness of 25 μm or less.
(3)前記粘着層の粘着力が5N/25mm以上である前記(1)または(2)に記載の高硬度フィルム。
(3) The high hardness film according to (1) or (2), wherein the adhesive strength of the adhesive layer is 5 N / 25 mm or more.
(4)前記第1基材と前記第2基材の寸法変化率の差が、縦方向と横方向のいずれも0.5%以下である前記(1)~(3)のいずれか1項に記載の高硬度フィルム。
(4) Any one of (1) to (3), wherein a difference in dimensional change between the first base material and the second base material is 0.5% or less in both the vertical direction and the horizontal direction. The high hardness film described in 1.
(5)JIS K5600-5-4に基づいて測定される鉛筆硬度が5H以上である前記(1)~(4)のいずれか1項に記載の高硬度フィルム。
(5) The high-hardness film according to any one of (1) to (4), wherein the pencil hardness measured based on JIS K5600-5-4 is 5H or more.
(6)前記第1基材と前記第2基材が、ポリエステルフィルムであり、前記ハードコート層が、アクリル系またはウレタン系硬化性樹脂であることを特徴とする前記(1)~(5)のいずれか1項に記載の高硬度フィルム。
(6) The above (1) to (5), wherein the first substrate and the second substrate are polyester films, and the hard coat layer is an acrylic or urethane curable resin. The high hardness film of any one of these.
(7)前記第1基材と前記第2基材の厚さがそれぞれ50~250μm、前記ハードコート層の厚さの合計が15~80μm、前記粘着層の厚さが5~25μmであることを特徴とする前記(1)~(6)のいずれか1項に記載の高硬度フィルム。
(7) The thickness of the first substrate and the second substrate is 50 to 250 μm, the total thickness of the hard coat layer is 15 to 80 μm, and the thickness of the adhesive layer is 5 to 25 μm. The high-hardness film according to any one of (1) to (6), wherein:
本発明の高硬度フィルムは、薄く軽量で、高い表面硬度を維持しながら、カールや層間剥離の発生を低減することができる。
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.
以下に、本発明の実施形態について、具体的な実施形態例を挙げつつ説明する。但し、本発明の実施形態は、以下の実施形態のみに限定されるものではない。
Hereinafter, embodiments of the present invention will be described with reference to specific embodiments. However, embodiments of the present invention are not limited to the following embodiments.
本発明の高硬度フィルムは、画像表示装置等を保護するための表面保護フィルムとして使用することができる。ここで、画像表示装置とは、液晶方式や有機EL方式などのフラットパネルディスプレイのことを意味している。これらは、パーソナルコンピューター、携帯電話、携帯ゲーム機器、薄型テレビ、広告用や情報表示用等の各種ディスプレイ等の各種用途に用いられている。また近年は、フラットパネルディスプレイとして、平面だけではなく、曲面となったものも開発されてきている。
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. Here, 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.
[高硬度フィルムの構成]
〔第1実施形態〕
本発明の第1実施形態の高硬度フィルムの構成例を図3を用いて説明する。
図3は、本発明の第1実施形態の構成を示す模式的断面図である。図3の高硬度フィルム1は、表面フィルム20aと裏面フィルム21aが、粘着層13を介して貼着されて構成されている。
表面フィルム20aは、第1基材12aと、第1基材12aの表面に積層された第1ハードコート層11aとを有している。
裏面フィルム21aは、第2基材12bと、第2基材12bの裏面に積層された第2ハードコート層11bとを有している。 [Configuration of high hardness film]
[First Embodiment]
The structural example of the high hardness film of 1st Embodiment of this invention is demonstrated using FIG.
FIG. 3 is a schematic cross-sectional view showing the configuration of the first embodiment of the present invention. Thehigh 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.
Thesurface film 20a has the 1st base material 12a and the 1st hard-coat layer 11a laminated | stacked on the surface of the 1st base material 12a.
Theback film 21a has the 2nd base material 12b and the 2nd hard-coat layer 11b laminated | stacked on the back surface of the 2nd base material 12b.
〔第1実施形態〕
本発明の第1実施形態の高硬度フィルムの構成例を図3を用いて説明する。
図3は、本発明の第1実施形態の構成を示す模式的断面図である。図3の高硬度フィルム1は、表面フィルム20aと裏面フィルム21aが、粘着層13を介して貼着されて構成されている。
表面フィルム20aは、第1基材12aと、第1基材12aの表面に積層された第1ハードコート層11aとを有している。
裏面フィルム21aは、第2基材12bと、第2基材12bの裏面に積層された第2ハードコート層11bとを有している。 [Configuration of high hardness film]
[First Embodiment]
The structural example of the high hardness film of 1st Embodiment of this invention is demonstrated using FIG.
FIG. 3 is a schematic cross-sectional view showing the configuration of the first embodiment of the present invention. The
The
The
以下、第1基材12aと第2基材12bとをまとめて、基材12と記載することがある。また、第1ハードコート層11aと第2ハードコート層11bと後記する第3ハードコート層11cをまとめて、ハードコート層11と記載することがある。
Hereinafter, the first base material 12a and the second base material 12b may be collectively referred to as the base material 12. In addition, the 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.
第1実施形態では、高硬度フィルム1を構成する各層が、粘着層13の両側において互いにほぼ対称的な層構成となっている。すなわち、第1基材12aと第2基材12bは、粘着層13の両側に、ほぼ同等の厚さで、かつ対称的な位置に存在している。また、第1ハードコート層11aと第2ハードコート層11bは、粘着層13を挟んで、両端の対称的な位置に存在している。
In the first embodiment, each layer constituting the high hardness film 1 has a substantially symmetrical layer configuration on both sides of the adhesive layer 13. In other words, 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. Further, 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.
カールや層間剥離の発生防止のためには、粘着層13を挟んで両側の各層が、厚さにおいて、バランスが取れたものとすることが有効である。特に、基材である第1基材12aと第2基材12bとは相互に厚さが同等であることが好ましい。即ち、第1基材12aの厚さt1と第2基材12bの厚さt2とが、t1≦t2≦1.1×t1の関係にあることが必要である。第1基材12aの裏面には、第3ハードコート層11cを形成することがあるため、第3ハードコート層11cとのバランスから、第2基材層12bを第1基材層12aよりも少し厚くすることができる。
In order to prevent the occurrence of curling and delamination, it is effective that each layer on both sides of the adhesive layer 13 is balanced in thickness. In particular, it is preferable that 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.
また、カールや層間剥離の発生防止のためには、高硬度フィルムを構成する各層が、粘着層13の両側において互いにできるだけ対称的な層構成となっていることが有効である。第1実施形態においては(図3参照)、粘着層13を挟んで、第1基材12aと第2基材12b、第1ハードコート層11aと第2ハードコート層11bとがそれぞれ互いに対称的な位置関係にあるため、好ましい層構成を有している。
Also, in order to prevent the occurrence of curling and delamination, it is effective that the layers constituting the high-hardness film have a symmetrical layer structure as much as possible on both sides of the adhesive layer 13. In the first embodiment (see FIG. 3), 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.
第1実施形態の高硬度フィルム1を構成する各層を形成する材料について以下、詳細に説明する。
Hereinafter, materials for forming each layer constituting the high hardness film 1 of the first embodiment will be described in detail.
(基材)
第1基材12aおよび第2基材12bを形成する材料としては、可視光線を80%以上透過する透明な材料であって、フィルム状の材料である。具体的には、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリプロピレンテレフタレートフィルム、ポリプロピレンナフタレートフィルム、ポリトリメチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム等のポリエステルフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、セロファン、ジアセチルセルロースフィルム、トリアセチルセルロースフィルム、アセチルセルロースブチレートフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム、ポリビニルアルコールフィルム、エチレン-酢酸ビニル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリメチルペンテンフィルム、ポリスルホンフィルム、ポリエーテルエーテルケトンフィルム、ポリエーテルスルホンフィルム、ポリエーテルイミドフィルム、ポリイミドフィルム、フッ素樹脂フィルム、ポリアミドフィルム、アクリル樹脂フィルム等が挙げられる。中でも、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリプロピレンテレフタレートフィルム、ポリプロピレンナフタレートフィルム、ポリトリメチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム等のポリエステルフィルムが好ましい。 (Base material)
The material forming thefirst 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. Specifically, polyethylene terephthalate film, polyethylene naphthalate film, polypropylene terephthalate film, polypropylene naphthalate film, polytrimethylene terephthalate film, polyester film such as polybutylene terephthalate film, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, Triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether Ether ketone film Polyether sulfone film, polyether imide film, a polyimide film, a fluororesin film, a polyamide film, and acrylic resin film. Among them, polyester films such as polyethylene terephthalate film, polyethylene naphthalate film, polypropylene terephthalate film, polypropylene naphthalate film, polytrimethylene terephthalate film, polybutylene terephthalate film are preferable.
第1基材12aおよび第2基材12bを形成する材料としては、可視光線を80%以上透過する透明な材料であって、フィルム状の材料である。具体的には、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリプロピレンテレフタレートフィルム、ポリプロピレンナフタレートフィルム、ポリトリメチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム等のポリエステルフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、セロファン、ジアセチルセルロースフィルム、トリアセチルセルロースフィルム、アセチルセルロースブチレートフィルム、ポリ塩化ビニルフィルム、ポリ塩化ビニリデンフィルム、ポリビニルアルコールフィルム、エチレン-酢酸ビニル共重合体フィルム、ポリスチレンフィルム、ポリカーボネートフィルム、ポリメチルペンテンフィルム、ポリスルホンフィルム、ポリエーテルエーテルケトンフィルム、ポリエーテルスルホンフィルム、ポリエーテルイミドフィルム、ポリイミドフィルム、フッ素樹脂フィルム、ポリアミドフィルム、アクリル樹脂フィルム等が挙げられる。中でも、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルム、ポリプロピレンテレフタレートフィルム、ポリプロピレンナフタレートフィルム、ポリトリメチレンテレフタレートフィルム、ポリブチレンテレフタレートフィルム等のポリエステルフィルムが好ましい。 (Base material)
The material forming the
特に、透明性、耐候性、耐溶剤性、剛性、コストの観点から、ポリエチレンテレフタレートフィルムを用いることがより好ましい。また、第1基材12aと第2基材12bは、同一の材料であっても、異なる材料であってもよい。カールや層間剥離の防止の観点からは、同一の材料であることが好ましい。
In particular, it is more preferable to use a polyethylene terephthalate film from the viewpoints of transparency, weather resistance, solvent resistance, rigidity, and cost. Further, the 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.
第1基材12aおよび第2基材12bには、各々、各種添加剤が含まれていてもよい。添加剤としては、例えば、酸化防止剤、耐熱安定剤、紫外線吸収剤、有機粒子、無機粒子、顔料、染料、帯電防止剤、核剤、カップリング剤等が挙げられる。
Each of the first base material 12a and the second base material 12b may contain various additives. Examples of the additive include antioxidants, heat stabilizers, ultraviolet absorbers, organic particles, inorganic particles, pigments, dyes, antistatic agents, nucleating agents, and coupling agents.
第1基材12aおよび第2基材12bには、ハードコート層11や粘着層13との密着性を向上させるために、表面処理が施されていてもよい。表面処理としては、例えば、サンドブラスト処理や溶剤処理等の凹凸化処理、コロナ放電処理、クロム酸処理、火炎処理、熱風処理、オゾン・紫外線照射処理等の表面酸化処理などが挙げられる。
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. Examples of the 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.
第1基材12aと第2基材12bの表面にはそれぞれ、易接着層が設けられていてもよい。易接着層は、各基材12の片面あるいは両面に設けることができる。易接着層を設けることによって、各基材12とハードコート層11または各基材12と粘着層13との接着強度を増大させて、当該界面での層間剥離の防止に寄与することができる。図4は、本発明の第1実施形態の変形例の構成を示す模式的断面図である。図4に示された高硬度フィルム2においては、第1実施形態の層構成に加えて、表面フィルム20bの第1基材12aの両面と裏面フィルム21bの第2基材12bの両面に易接着層15が設けられている。
An easy-adhesion layer may be provided on each of the surfaces of the first base material 12a and the second base material 12b. The easy adhesion layer can be provided on one side or both sides of each substrate 12. By providing the easy-adhesion layer, the adhesive strength between each substrate 12 and the hard coat layer 11 or each substrate 12 and the adhesive layer 13 can be increased, which can contribute to prevention of delamination at the interface. FIG. 4 is a schematic cross-sectional view showing a configuration of a modified example of the first embodiment of the present invention. In 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.
易接着層15はアクリル系樹脂又はポリエステル系樹脂を含有し、必要に応じてウレタン系樹脂等を含有していてもよい。
易接着層15に使用されるアクリル系樹脂としては、以下に示すようなアクリルモノマーから重合されるものが例示される。例えば、直鎖状、分岐状、環状のアルキル基を有したアルキルアクリレートやアルキルメタクリレート、ヒドロキシ含有モノマー、エポキシ基含有モノマー、アミド基を含有するモノマー等が挙げられるが、これらに限定されるものではない。また、これらのモノマー成分は、2種以上を用いて共重合しても良い。 The easy-adhesion layer 15 contains an acrylic resin or a polyester resin, and may contain a urethane resin or the like as necessary.
Examples of the acrylic resin used for theeasy adhesion layer 15 include those polymerized from an acrylic monomer as shown below. For example, 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.
易接着層15に使用されるアクリル系樹脂としては、以下に示すようなアクリルモノマーから重合されるものが例示される。例えば、直鎖状、分岐状、環状のアルキル基を有したアルキルアクリレートやアルキルメタクリレート、ヒドロキシ含有モノマー、エポキシ基含有モノマー、アミド基を含有するモノマー等が挙げられるが、これらに限定されるものではない。また、これらのモノマー成分は、2種以上を用いて共重合しても良い。 The easy-
Examples of the acrylic resin used for the
また、ポリエステル系樹脂としては、多塩基酸成分とポリオール成分とから重縮合されるものが例示される。用いられる多塩基酸としてはテレフタル酸、イソフタル酸、ジフェニルカルボン酸等が挙げられる。ポリオール成分としては、エチレングリコール、ジエチレングリコール等が挙げられるが、これらに限定されるものではない。また、これらのモノマー成分は、2種類以上を用いて共重合しても良い。
Also, examples of polyester resins include those that are polycondensed from a polybasic acid component and a polyol component. Examples of the polybasic acid used include terephthalic acid, isophthalic acid, and diphenylcarboxylic acid. Examples of 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.
ウレタン系樹脂としては、ポリオール化合物とイソシアネート化合物の反応生成物として得られるものが例示される。用いられるポリオール化合物としては、ポリエステルポリオール、ポリエーテルジオール、ポリアセタールジオール等が挙げられる。イソシアネート化合物としては、トリレンジイソシアネート、フェニレンジイソシアネート等が挙げられるが、これらに限定されるものではない。また、これらの成分は、2種類以上を用いて反応させることもできる。更に、必要であればこの他に鎖長延長剤、架橋剤などを使用しても良い。
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.
易接着層15には、易滑性の付与や屈折率の調整を目的として粒子を添加させることができる。粒子としては、無機顔料や有機フィラー等が挙げられるが、易接着層15の樹脂と屈折率が比較的近く、高い透明性が得られるため、シリカを使用することが好ましい。易接着層15の屈折率を調整する目的で使用される粒子としてはアルミナ-シリカ複合体や酸化チタン、酸化ジルコニウム、酸化亜鉛等が挙げられるが、これらに限定されるものではなく、これらの粒子は2種類以上を使用しても良い。
また、易接着層15には必要に応じて帯電防止剤、可塑剤等の種々の添加剤を添加しても良い。塗工適性や反応性向上を目的として界面活性剤やpH調整剤を添加しても良い。 Particles can be added to the easy-adhesion layer 15 for the purpose of imparting slipperiness and adjusting the refractive index. Examples of 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 bondinglayer 15 as needed. A surfactant and a pH adjuster may be added for the purpose of improving coating suitability and reactivity.
また、易接着層15には必要に応じて帯電防止剤、可塑剤等の種々の添加剤を添加しても良い。塗工適性や反応性向上を目的として界面活性剤やpH調整剤を添加しても良い。 Particles can be added to the easy-
Moreover, you may add various additives, such as an antistatic agent and a plasticizer, to the easily bonding
易接着層15の厚みは特に制限されないが、例えば、0.1nm以上にすることができ、1nm以上、5nm以上の範囲内で選択することも可能である。上限は用途によって異なるが、例えば1μm以下、100nm以下、50nm以下の範囲内で選択することも可能である。
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.
易接着層15の形成方法は特に制限されないが、第1基材12aおよび第2基材12bにポリエステルフィルムを用いる場合、ポリエステルフィルムを溶融押出しした後に、ポリエステルフィルムの上に易接着層15を形成することが好ましい。ポリエステルフィルムは1軸延伸ポリエステルフィルムであってもよく、2軸延伸ポリエステルフィルムであってもよい。1軸延伸ポリエステルフィルムの場合、ポリエステルフィルムは、溶融し、押し出された後、縦方向または横方向に3~10倍延伸して、1軸延伸ポリエステルフィルムを形成し、必要に応じてコロナ放電処理を施す。その少なくとも一面に易接着層用樹脂を塗布し、乾燥して易接着層15を形成する。2軸延伸ポリエステルフィルムの場合、ポリエステルフィルムは、溶融し、押し出された後、縦方向に3~10倍延伸して、縦延伸ポリエステルフィルムを形成し、必要に応じてコロナ放電処理を施す。その少なくとも一面に易接着層用樹脂を塗布し、乾燥して易接着層15を形成する。その後、易接着層15を有するフィルムをさらに横方向に3~10倍延伸することによって2軸延伸ポリエステルフィルムを形成する。当該方法によって、同時に横方向に延伸された易接着層15を形成することができる。
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. In the case of a biaxially stretched polyester film, 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. Thereafter, 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. By this method, the easy adhesion layer 15 stretched in the transverse direction at the same time can be formed.
また、別法として、ポリエステルフィルムと易接着層用樹脂を同時に押し出し、積層フィルムとし、積層したフィルムを9~100倍に公知の方法にて1軸または2軸延伸して易接着層15を形成しても良い。
上記のようにして製造されたフィルムに、必要に応じてヘイズ値が大きくならないように、さらにコロナ放電処理、火炎処理等の公知の方法により表面処理を施しても良い。 Alternatively, 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 knownmethod 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.
上記のようにして製造されたフィルムに、必要に応じてヘイズ値が大きくならないように、さらにコロナ放電処理、火炎処理等の公知の方法により表面処理を施しても良い。 Alternatively, 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
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.
第1基材12aと第2基材12bの厚さは、高硬度フィルム1としての機械的強度の確保やカール防止の観点から、易接着層15も含めて、それぞれ50~250μmであることが好ましい。より好ましくは、100~200μmである。
The thickness of the first base material 12a and the second base material 12b is 50 to 250 μm 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 μm.
カールや層間剥離の発生防止のためには、第1基材12aと第2基材12bの加熱前後の寸法変化率は、小さい方が好ましい。具体的には、第1基材12aと第2基材12bの寸法変化率の差が、縦方向と横方向のいずれも0.5%以下であることが好ましい。より好ましくは、0.3%以下である。寸法変化率(%)は、縦方向および横方向のそれぞれについて、JIS C2151に準拠して150℃、30分間の加熱処理前後の寸法の差から求められる。ここで、縦方向とは、基材の長さ方向のことであり、横方向とは基材の長さ方向と直角の方向のことをいう。
In order to prevent the occurrence of curling and delamination, it is preferable that the dimensional change rate before and after heating the first base material 12a and the second base material 12b is small. Specifically, 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. Here, the vertical direction is the length direction of the base material, and the horizontal direction is a direction perpendicular to the length direction of the base material.
(ハードコート層)
本実施形態のハードコート層11とは、高硬度フィルム1に表面硬度を付与するための硬質成分を含有する層である。本実施形態において、ハードコート層11として、硬化性樹脂を用いることが好ましい。 (Hard coat layer)
Thehard 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.
本実施形態のハードコート層11とは、高硬度フィルム1に表面硬度を付与するための硬質成分を含有する層である。本実施形態において、ハードコート層11として、硬化性樹脂を用いることが好ましい。 (Hard coat layer)
The
ハードコート層11に用いられる硬化性樹脂としては、熱硬化型樹脂、活性エネルギー線硬化型樹脂等が挙げられる。熱硬化型樹脂としては、例えば、フェノール樹脂、尿素樹脂、ジアリルフタレート樹脂、メラミン樹脂、不飽和ポリエステル樹脂、ポリウレタン樹脂、エポキシ樹脂、アミノアルキッド樹脂、珪素樹脂、ポリシロキサン樹脂等が挙げられる。活性エネルギー線硬化型樹脂としては、アクリル系硬化性樹脂やウレタン系硬化性樹脂が挙げられる。
Examples of the curable resin used for the hard coat layer 11 include a thermosetting resin and an active energy ray curable resin. Examples of 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. Examples of the active energy ray curable resin include acrylic curable resins and urethane curable resins.
アクリル系硬化性樹脂とは、アクリル系の重合性不飽和基を有するモノマーまたはオリゴマーからなる硬化性組成物の重合体である。アクリル系の重合性不飽和基を有するモノマーまたはオリゴマーとしては、単官能のものと多官能のものがある。
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.
アクリル系の重合性不飽和基を有する単官能のモノマーの具体例としては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸n-ペンチル、(メタ)アクリル酸n-ヘキシル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸n-オクチル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸n-ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸n-デシル、(メタ)アクリル酸イソデシル、(メタ)アクリル酸n-ウンデシル、(メタ)アクリル酸n-ドデシル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸エトキシエチル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸ベンジル等の(メタ)アクリル酸エステルが挙げられる。これらは1種を単独で使用してもよいし、2種以上を併用してもよい。また、アクリル系の重合性不飽和基を有する単官能のオリゴマーの具体例としては、エトキシ化o-フェニルフェノールアクリレート、メトキシポリエチレングリコール(質量平均分子量400)アクリレート、フェノキシポリエチレングリコールアクリレート等が挙げられる。
Specific examples of the monofunctional monomer having an acrylic polymerizable unsaturated group 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 acrylate, n-dodecyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylate Le methoxyethyl acrylate, ethoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, and (meth) (meth) acrylic acid esters of benzyl acrylate and the like. These may be used individually by 1 type and may use 2 or more types together. Specific examples of 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.
アクリル系の重合性不飽和基を有するモノマーまたはオリゴマーからなる組成物が硬化性となるためには、アクリル系の重合性不飽和基を有するモノマーまたはオリゴマーとして、多官能(メタ)アクリル酸エステルを有していることが好ましい。多官能(メタ)アクリル酸エステルとしては、例えば、ジプロピレングリコールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート、ポリエチレングリコール(質量平均分子量600)ジ(メタ)アクリレート、プロピレンオキサイド変性ネオペンチルグリコールジ(メタ)アクリレート、変性ビスフェノールAジ(メタ)アクリレート、トリシクロデカンジメタノールジ(メタ)アクリレート、ポリエチレングリコール(質量平均分子量400)ジ(メタ)アクリレート等の2官能の(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、トリメチロールプロパンエトキシトリ(メタ)アクリレート、ポリエーテルトリ(メタ)アクリレート、グリセリンプロポキシトリ(メタ)アクリレート等の3官能の(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ペンタエリスリトールエトキシテトラ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、プロピオン酸変性ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールモノヒドロキシペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート等の4官能以上の(メタ)アクリレートが挙げられる。これらの多官能アクリレートは、1種を単独で使用してもよいし、2種以上を組み合わせて使用してもよい。
ハードコート層11としての硬度を確保するためには、4官能以上の(メタ)アクリル酸エステルを使用することが好ましい。 In order for a composition comprising a monomer or oligomer having an acrylic polymerizable unsaturated group to be curable, a polyfunctional (meth) acrylic ester is used as the monomer or oligomer having an acrylic polymerizable unsaturated group. It is preferable to have. Examples of 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). ) Di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, modified bisphenol A di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, polyethylene glycol (mass average molecular weight 400) di (meth) ) 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) ) Acrylate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These polyfunctional acrylates may be used individually by 1 type, and may be used in combination of 2 or more type.
In order to ensure the hardness of thehard coat layer 11, it is preferable to use a tetrafunctional or higher (meth) acrylic ester.
ハードコート層11としての硬度を確保するためには、4官能以上の(メタ)アクリル酸エステルを使用することが好ましい。 In order for a composition comprising a monomer or oligomer having an acrylic polymerizable unsaturated group to be curable, a polyfunctional (meth) acrylic ester is used as the monomer or oligomer having an acrylic polymerizable unsaturated group. It is preferable to have. Examples of 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). ) Di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, modified bisphenol A di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, polyethylene glycol (mass average molecular weight 400) di (meth) ) 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) ) Acrylate, propionic acid-modified dipentaerythritol penta (meth) acrylate, dipentaerythritol monohydroxypenta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. These polyfunctional acrylates may be used individually by 1 type, and may be used in combination of 2 or more type.
In order to ensure the hardness of the
ウレタン系硬化性樹脂とは、ウレタンアクリレートモノマーまたはオリゴマーの重合体である。ウレタンアクリレートオリゴマーとしては、ウレタン結合を介してポリオキシアルキレンセグメント又は飽和ポリエステルセグメントあるいはその両方が連結し、両末端にアクリロイル基を有するものが挙げられる。
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.
硬化性樹脂は、熱硬化型であってもよいし、活性エネルギー線硬化型であってもよい。製造時におけるカールの発生を極力抑制するためには、活性エネルギー線硬化型であることが好ましい。活性エネルギー線とは、紫外線、電子線、可視光線、γ線等の電離性放射線のことをいう。
The curable resin may be a thermosetting type or an active energy ray curable type. In order to suppress the occurrence of curling during production as much as possible, the active energy ray curable type is preferable. Active energy rays refer to ionizing radiation such as ultraviolet rays, electron beams, visible rays, and γ rays.
熱硬化型または活性エネルギー線硬化型のアクリル系硬化性樹脂とするためには、上記の重合性不飽和基を有するモノマーまたはオリゴマーに、熱重合開始剤または活性エネルギー線重合開始剤を加えて、熱硬化性または活性エネルギー線硬化性の組成物とすることが必要である。
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.
熱重合開始剤としては、公知のものを使用することができる。例えば、ベンゾイルパーオキサイド、ジ-t-ブチルパーオキサイドなどのパーオキサイド化合物などを挙げることができる。熱重合開始剤の添加量は、重合性不飽和基を有するモノマーまたはオリゴマーに対して、1~10質量%であることが好ましい。
As the 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.
また、活性エネルギー線重合開始剤としては、公知のものを使用することができる。例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾイン-n-ブチルエーテル、ベンゾインイソブチルエーテル、アセトフェノン、ジメチルアミノアセトフェノン、2,2-ジメトキシ-2-フェニルアセトフェノン、2,2-ジエトキシ-2-フェニルアセトフェノン、2-ヒドロキシ-2-メチル-1-フェニルプロパン-1-オン、1-ヒドロキシシクロヘキシルフェニルケトン、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノ-プロパン-1-オン、4-(2-ヒドロキシエトキシ)フェニル-2(ヒドロキシ-2-プロプル)ケトン、ベンゾフェノン、p-フェニルベンゾフェノン、4,4’-ジエチルアミノベンゾフェノン、プロピオフェノン、ジクロロベンゾフェノン、2-メチルアントラキノン、2-エチルアントラキノン、2-ターシャリーブチルアントラキノン、2-アミノアントラキノン、2-メチルチオキサントン、2-エチルチオキサントン、2-クロロチオキサントン、2,4-ジメチルチオキサントン、2,4-ジエチルチオキサントン、ベンジルジメチルケタール、アセトフェノンジメチルケタール、p-ジメチルアミン安息香酸エステルなどを挙げることができる。これら活性エネルギー線重合開始剤は1種を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。活性エネルギー線重合開始剤の添加量は、重合性不飽和基を有するモノマーまたはオリゴマーに対して、1~10質量%であることが好ましい。
In addition, as the active energy ray polymerization initiator, known ones can be used. For example, 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, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 , 4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylamine benzoate, and the like. 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.
また、光重合開始剤に加えて、光増感剤をさらに含有することもできる。光増感剤としては、たとえば、n-ブチルアミン、トリエチルアミン、トリ-n-ブチルホスフィン等が挙げられる。
In addition to the photopolymerization initiator, a photosensitizer can be further contained. Examples of the photosensitizer include n-butylamine, triethylamine, tri-n-butylphosphine and the like.
ハードコート層11には、必要に応じて、柔軟性成分が含まれてもよい。柔軟性成分が含まれていると、ゲル分率が高い状態で打ち抜いた際のクラックの発生を防止することができる。柔軟性成分としては、分子内に1個以上の重合性不飽和基を有する(メタ)アクリレート類が好ましい。(メタ)アクリレート類としては、例えば、トリシクロデカンメチロールジ(メタ)アクリレート、ビスフェノールFのエチレンオキサイド変性ジ(メタ)アクリレート、ビスフェノールAのエチレンオキサイド変性ジ(メタ)アクリレート、イソシアヌル酸のエチレンオキサイド変性ジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート等の2官能(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、トリメチルプロパンのプロピレンオキサイド変性トリ(メタ)アクリレート、トリメチルプロパンのエチレンオキサイド変性トリ(メタ)アクリレート等の3官能(メタ)アクリレート、ウレタン(メタ)アクリレート、ポリエステル(メタ)アクリレート、ポリエーテル(メタ)アクリレート等が挙げられる。特に、3官能(メタ)アクリレート、ウレタン(メタ)アクリレートがより好ましい。
これらの(メタ)アクリレート類は、1種を単独で使用することも、2種以上を組み合わせて使用することもできる。 Thehard 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. As the 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. In particular, trifunctional (meth) acrylate and urethane (meth) acrylate are more preferable.
These (meth) acrylates can be used singly or in combination of two or more.
これらの(メタ)アクリレート類は、1種を単独で使用することも、2種以上を組み合わせて使用することもできる。 The
These (meth) acrylates can be used singly or in combination of two or more.
また、ハードコート層11には、反応性無機酸化物粒子または反応性有機粒子を含有してもよい。特に第1ハードコート層11に反応性無機酸化物粒子または反応性有機粒子を含有させると、高硬度フィルムの表面硬度を向上させることができるので好ましい。
Further, the hard coat layer 11 may contain reactive inorganic oxide particles or reactive organic particles. In particular, it is preferable that 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.
反応性無機酸化物粒子は、カップリング剤によって処理した無機酸化物粒子であり、反応性有機粒子は、カップリング剤によって処理した有機粒子である。無機酸化物粒子または有機粒子をカップリング剤によって処理することにより、重合体との間の結合力を高めることができる。その結果、表面硬度や耐擦傷性を向上させることができる。
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. By treating the inorganic oxide particles or the organic particles with a coupling agent, the bonding strength with the polymer can be increased. As a result, surface hardness and scratch resistance can be improved.
ここで、無機酸化物粒子としては、硬度が高いものが好ましく、例えば、二酸化ケイ素粒子、二酸チタン粒子、酸化ジルコニウム粒子、酸化アルミニウム粒子などを用いることができる。
有機粒子としては、例えば、アクリル樹脂、ポリスチレン、ポリシロキサン、メラミン樹脂、ベンゾグアナミン樹脂、ポリテトラフルオロエチレン、セルロースアセテート、ポリカーボネート、ポリアミドなどの樹脂粒子などを用いることができる。 Here, the inorganic oxide particles preferably have high hardness. For example, silicon dioxide particles, titanium dioxide particles, zirconium oxide particles, aluminum oxide particles and the like can be used.
Examples of 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.
有機粒子としては、例えば、アクリル樹脂、ポリスチレン、ポリシロキサン、メラミン樹脂、ベンゾグアナミン樹脂、ポリテトラフルオロエチレン、セルロースアセテート、ポリカーボネート、ポリアミドなどの樹脂粒子などを用いることができる。 Here, the inorganic oxide particles preferably have high hardness. For example, silicon dioxide particles, titanium dioxide particles, zirconium oxide particles, aluminum oxide particles and the like can be used.
Examples of 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.
カップリング剤としては、例えば、γ-アミノプロピルトリエトキシシラン、γ-アミノプロピルトリメトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-メルカプトプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、γ-アミノプロピルトリエトキシアルミニウム等が挙げられる。これらは1種を単独で使用してもよいし、2種以上を併用してもよい。
カップリング剤の処理量は、無機酸化物粒子または有機粒子100質量部に対して、0.1~20質量部であることが好ましく、1~10質量部であることがより好ましい。 Examples of coupling agents include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-mercaptopropyltrimethoxy. Examples thereof include silane, γ-aminopropyltriethoxysilane, and γ-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.
カップリング剤の処理量は、無機酸化物粒子または有機粒子100質量部に対して、0.1~20質量部であることが好ましく、1~10質量部であることがより好ましい。 Examples of coupling agents include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-mercaptopropyltrimethoxy. Examples thereof include silane, γ-aminopropyltriethoxysilane, and γ-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.
ハードコート層11には、必要に応じて、本発明の効果を損なわない範囲で、上記以外の成分を含有しても良い。例えば、アンチブロッキング性を付与するための無機微粒子;抗菌性を付与するための抗菌剤;防汚性を付与するためのフッ素系防汚剤;指すべり性を付与するためのフッ素系滑剤またはシリコン系滑剤;塗工適性を向上させるためのレベリング剤;帯電防止性能を付与するための金属酸化物微粒子、帯電防止樹脂、導電性高分子;紫外線遮蔽性をするための金属酸化物微粒子、紫外線吸収剤;光安定化剤等が挙げられる。
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. For example, inorganic fine particles for imparting anti-blocking properties; antibacterial agents 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.
(粘着層)
粘着層13を形成する粘着剤としては、例えば、天然ゴム系粘着剤、合成ゴム系粘着剤、アクリル系粘着剤、ウレタン系粘着剤、シリコーン系粘着剤などが使用される。また、溶剤系、エマルジョン系、水系のいずれであってもよい。なかでも光学系用途に使用する場合は透明度、耐候性、耐久性、コスト等の観点から溶剤型アクリル系粘着剤が特に好ましい。 (Adhesive layer)
As 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.
粘着層13を形成する粘着剤としては、例えば、天然ゴム系粘着剤、合成ゴム系粘着剤、アクリル系粘着剤、ウレタン系粘着剤、シリコーン系粘着剤などが使用される。また、溶剤系、エマルジョン系、水系のいずれであってもよい。なかでも光学系用途に使用する場合は透明度、耐候性、耐久性、コスト等の観点から溶剤型アクリル系粘着剤が特に好ましい。 (Adhesive layer)
As the pressure-sensitive adhesive forming the pressure-
アクリル系粘着剤は、アクリル系重合体が架橋剤によって架橋されたものである。アクリル系重合体は、非架橋性アクリル単量体単位と架橋性単量体単位とを有する重合体である。ここで、「単量体単位」は重合体を構成する繰り返し単位である。「アクリル単量体」は、(メタ)アクリロイル基を有する化合物である。「(メタ)アクリロイル基」は、アクリロイル基またはメタクリロイル基であることを示す。また、非架橋性アクリル単量体は架橋性を有さないアクリル単量体であり、架橋性単量体は架橋性基を有する単量体である。架橋性単量体は、非架橋性アクリル単量体と重合可能なものであればアクリル単量体であっても非アクリル単量体であってもよいが、アクリル単量体であることが好ましい。架橋性基としては、カルボキシル基、ヒドロキシ基、アミノ基、エポキシ基、グリシジル基等が挙げられる。
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. Here, 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. preferable. Examples of the crosslinkable group include a carboxyl group, a hydroxy group, an amino group, an epoxy group, and a glycidyl group.
非架橋性アクリル単量体単位としては、たとえば、(メタ)アクリル酸のカルボキシル基の水素原子を炭化水素基で置換した(メタ)アクリル酸エステル単位が挙げられる。該炭化水素基の炭素数は1~18が好ましく、1~8がより好ましい。該炭化水素基は置換基を有していてもよい。該置換基としては、架橋性基を含まないものであれば特に限定されず、たとえばメトキシ基、エトキシ基等のアルコキシ基が挙げられる。
Examples of the non-crosslinkable acrylic monomer unit 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.
該(メタ)アクリル酸エステルとして具体的には、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸t-ブチル、(メタ)アクリル酸n-ペンチル、(メタ)アクリル酸n-ヘキシル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸n-オクチル、(メタ)アクリル酸イソオクチル、(メタ)アクリル酸n-ノニル、(メタ)アクリル酸イソノニル、(メタ)アクリル酸n-デシル、(メタ)アクリル酸イソデシル、(メタ)アクリル酸n-ウンデシル、(メタ)アクリル酸n-ドデシル、(メタ)アクリル酸ステアリル、(メタ)アクリル酸メトキシエチル、(メタ)アクリル酸エトキシエチル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸ベンジル等が挙げられる。これらは1種を単独で使用してもよいし、2種以上を併用してもよい。これらの中でも、接着性の観点からは、アクリル酸n-ブチル、アクリル酸2-エチルヘキシル、アクリル酸メチルが好ましい。なお、本発明において、「(メタ)アクリル酸」とは、「アクリル酸」及び「メタクリル酸」の両方を含むことを意味する。
Specific examples of the (meth) acrylic acid ester 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-dodecyl (meth) acrylate, stearyl (meth) acrylate, methoxyethyl (meth) acrylate, Meth) ethoxyethyl acrylate, cyclohexyl (meth) acrylate include benzyl (meth) acrylate and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, n-butyl acrylate, 2-ethylhexyl acrylate, and methyl acrylate are preferable from the viewpoint of adhesiveness. In the present invention, “(meth) acrylic acid” means containing both “acrylic acid” and “methacrylic acid”.
架橋性単量体単位としては、カルボキシル基含有共重合性単量体単位、ヒドロキシ基含有共重合性単量体単位、アミノ基含有共重合性単量体単位、グリシジル基含有共重合性単量体単位が挙げられる。カルボキシル基含有共重合性単量体としては、例えば、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸、グラタコン酸などのα,β-不飽和カルボン酸やその無水物などが挙げられる。
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 α, β-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.
ヒドロキシ基含有共重合性単量体としては、例えば、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸4-ヒドロキシブチル、(メタ)アクリル酸2-ヒドロキシプロピルなどの(メタ)アクリル酸ヒドロキシアルキル、(メタ)アクリル酸モノ(ジエチレングリコール)などの(メタ)アクリル酸[(モノ、ジ又はポリ)アルキレングリコール]、(メタ)アクリル酸モノカプロラクトンなどの(メタ)アクリル酸ラクトンが挙げられる。
Examples of the hydroxy group-containing copolymerizable monomer 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.
アミノ基含有共重合性単量体としては、例えば、(メタ)アクリルアミド、アリルアミドなどが挙げられる。グリシジル基含有共重合性単量体としては、例えば、(メタ)アクリル酸グリシジルなどが挙げられる。
これらの中でも、粘着性、架橋性および重合性等の観点から、カルボキシル基含有共重合性単量体が好ましい。 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.
Among these, a carboxyl group-containing copolymerizable monomer is preferable from the viewpoints of adhesiveness, crosslinkability, polymerizability, and the like.
これらの中でも、粘着性、架橋性および重合性等の観点から、カルボキシル基含有共重合性単量体が好ましい。 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.
Among these, a carboxyl group-containing copolymerizable monomer is preferable from the viewpoints of adhesiveness, crosslinkability, polymerizability, and the like.
粘着剤には、必要に応じて他の助剤が添加されてもよい。他の助剤としては、酸化防止剤、粘着付与剤、シランカップリング剤、紫外線吸収剤、ヒンダードアミン系化合物等の光安定剤、充填剤などが挙げられる。
Other adhesives may be added to the adhesive as necessary. Examples of other auxiliaries include antioxidants, tackifiers, silane coupling agents, ultraviolet absorbers, light stabilizers such as hindered amine compounds, and fillers.
酸化防止剤としては、フェノール系酸化防止剤、アミン系酸化防止剤、ラクトン系酸化防止剤、リン系酸化防止剤、イオウ系酸化防止剤等が挙げられる。これら酸化防止剤は1種を単独で使用してもよいし、2種以上を併用してもよい。
Examples of the antioxidant 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.
粘着付与剤として、例えば、ロジン系樹脂、テルペン系樹脂、テルペンフェノール系樹脂、クマロンインデン系樹脂、スチレン系樹脂、キシレン系樹脂、フェノール系樹脂、石油樹脂などが挙げられる。
Examples of the tackifier include rosin resin, terpene resin, terpene phenol resin, coumarone indene resin, styrene resin, xylene resin, phenol resin, petroleum resin, and the like.
シランカップリング剤としては、例えば、メルカプトアルコキシシラン化合物(例えば、メルカプト基置換アルコキシオリゴマー等)などが挙げられる。
紫外線吸収剤としては、例えば、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物などが挙げられる。 Examples of the silane coupling agent include mercaptoalkoxysilane compounds (for example, mercapto group-substituted alkoxy oligomers).
Examples of the ultraviolet absorber include benzotriazole compounds and benzophenone compounds.
紫外線吸収剤としては、例えば、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物などが挙げられる。 Examples of the silane coupling agent include mercaptoalkoxysilane compounds (for example, mercapto group-substituted alkoxy oligomers).
Examples of the ultraviolet absorber include benzotriazole compounds and benzophenone compounds.
粘着層13の厚さは、25μm以下であることが好ましい。また、5~25μmであることがより好ましく、5~20μmであることがさらに好ましく、10~15μmであることが一層好ましい。粘着層13の厚さが前記範囲内であると、層間剥離が発生することなく高硬度を確保し易くなる。
The thickness of the adhesive layer 13 is preferably 25 μm or less. Further, it is more preferably 5 to 25 μm, further preferably 5 to 20 μm, and further preferably 10 to 15 μm. 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.
(動的せん断貯蔵弾性率)
本発明者らの検討によると、層間剥離は、粘着層13と他の層との界面で生じる。そして、カールや層間剥離は、加工時や使用時において発生する。室温付近における加工時や使用時において、粘着層13のはみ出しや、カールや層間剥離の発生がなく、フィルムの表面硬度を低下させないことが必要とされる。そのためには、粘着層13の20℃、周波数1Hzにおける動的せん断貯蔵弾性率G´(20℃)(Pa)が下記式(1)を満足することが必要である。
1×105Pa≦G´(20℃)≦1×107Pa ・・・(1)
好ましくは、5×105Pa≦G´(20℃)≦5×106Paである。 (Dynamic shear storage modulus)
According to the study by the present inventors, delamination occurs at the interface between the pressure-sensitive adhesive layer 13 and other layers. Curling and delamination occur during processing and use. During processing and use near room temperature, the adhesive layer 13 does not protrude, curl or delaminate, and the surface hardness of the film must not be reduced. For this purpose, it is necessary that the dynamic shear storage elastic modulus G ′ (20 ° C.) (Pa) of the adhesive layer 13 at 20 ° C. and a frequency of 1 Hz satisfies the following formula (1).
1 × 10 5 Pa ≦ G ′ (20 ° C.) ≦ 1 × 10 7 Pa (1)
Preferably, 5 × 10 5 Pa ≦ G ′ (20 ° C.) ≦ 5 × 10 6 Pa.
本発明者らの検討によると、層間剥離は、粘着層13と他の層との界面で生じる。そして、カールや層間剥離は、加工時や使用時において発生する。室温付近における加工時や使用時において、粘着層13のはみ出しや、カールや層間剥離の発生がなく、フィルムの表面硬度を低下させないことが必要とされる。そのためには、粘着層13の20℃、周波数1Hzにおける動的せん断貯蔵弾性率G´(20℃)(Pa)が下記式(1)を満足することが必要である。
1×105Pa≦G´(20℃)≦1×107Pa ・・・(1)
好ましくは、5×105Pa≦G´(20℃)≦5×106Paである。 (Dynamic shear storage modulus)
According to the study by the present inventors, delamination occurs at the interface between the pressure-
1 × 10 5 Pa ≦ G ′ (20 ° C.) ≦ 1 × 10 7 Pa (1)
Preferably, 5 × 10 5 Pa ≦ G ′ (20 ° C.) ≦ 5 × 10 6 Pa.
G´(20℃)が前記範囲内であると、カール等による基材フィルム12の変形に粘着層13が追従することができ、最終製品としての形状を損なうことが少ない。また、G´(20℃)が1×105Pa以上であると粘着層13のはみ出しやフィルムの表面硬度が低下しにくい。G´(20℃)が1×107Pa以下であると、層間剥離が発生しにくい。
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.
カールや層間剥離は、高硬度フィルムの加熱時や、最終製品として使用されているときの、室温での経時変化においても問題となる。
ハードコート層11や粘着層13は、後記するように、基材12に溶剤を用いたハードコート組成物や粘着剤組成物を塗布した後に、加熱・乾燥し、その後、硬化させることによって形成される。かかる加熱時や、最終製品製造時から長時間経過後であってもカールや剥離が生じないようにすることが必要となる。 Curling and delamination also pose a problem even when the high-hardness film is heated or when it is used as a final product over time at room temperature.
As will be described later, thehard 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.
ハードコート層11や粘着層13は、後記するように、基材12に溶剤を用いたハードコート組成物や粘着剤組成物を塗布した後に、加熱・乾燥し、その後、硬化させることによって形成される。かかる加熱時や、最終製品製造時から長時間経過後であってもカールや剥離が生じないようにすることが必要となる。 Curling and delamination also pose a problem even when the high-hardness film is heated or when it is used as a final product over time at room temperature.
As will be described later, the
そのためには、粘着層13の粘度として高温時に特定の範囲の値を有していることが求められる。すなわち、粘着層13の80℃、周波数1Hzにおける動的せん断貯蔵弾性率G´(80℃)(Pa)が下記式(2)を満足することが必要である。
1×104Pa≦G´(80℃)≦1×106Pa ・・・(2)
好ましくは、5×104Pa≦G´(80℃)≦5×105Paである。 For this purpose, the viscosity of theadhesive 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.
1×104Pa≦G´(80℃)≦1×106Pa ・・・(2)
好ましくは、5×104Pa≦G´(80℃)≦5×105Paである。 For this purpose, the viscosity of the
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℃)が前記範囲内であると、加熱時や室温での長時間経過時において発生する、カール等の基材フィルム12の変形に粘着層13が追従することができ、最終製品としての形状を損なうことが少ない。また、G´(80℃)が1×104Pa以上であると、粘着層13が流動しにくく、均一な厚さの層を形成しやすい。G´(80℃)が1×106Pa以下であると、カールや層間剥離が発生しにくい。
If 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.
本発明における粘着層13の動的せん断貯蔵弾性率G´は、厚さ100~150μmの試験片を採取して、粘弾性試験機を用いて、周波数1Hz、歪0.1%、昇温速度3℃/分で、温度20℃および80℃での貯蔵弾性率(G’)(Pa)を測定することによって得ることができる。試験片は薄い粘着剤のシートを積層して、所定の厚さとしてから測定することができる。また、基材と粘着剤の積層フィルムを幾重にも重ねて測定してもよい。後者の場合には粘着層13のみの厚さの合計が、所定の厚さとなるように調整する。
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 μm 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. In addition, 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.
粘着層13の動的せん断貯蔵弾性率G´の値は、重合体の重量平均分子量、単量体の組成、架橋剤の配合量(架橋密度)等により調節することができる。例えば、G´(20℃)を上記の範囲内にするには、ガラス転移温度が高い単量体を多くしたり、架橋密度を高くすることで調節できる。G´(20℃)からG´(80℃)への傾きを調整する際も、同様に架橋密度を調整することでG´(80℃)を上記範囲内とすることができる。
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.
ガラス転移温度が高い単量体としては、イソボルニルアクリレート、t-ブチルアクリレート、ポリエチレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、ラウリルアクリレート、ステアリルアクリレート、シクロヘキルシルアクリレート、3-メチル-1、5-ペンタンジオールジアクリレート、1、6-ヘキサンジオールジアクリレート、1、9-ノナンジオールジアクリレート、t-ブチルメタクリレート等が挙げられる。架橋密度を高めるためには、4官能以上の(メタ)アクリレートを使用することが有効である。
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.
粘着層13の粘着力は、5N/25mm以上であることが好ましい。より好ましくは、10N/25mm以上である。5N/25mm以上であると、製造時あるいは使用時において、カールや層間剥離が発生しにくいものとなる。
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.
〔第2実施形態〕
図5は、本発明の第2実施形態の構成を示す模式的断面図である。図5の高硬度フィルム3は、表面フィルム20cと裏面フィルム21cが、粘着層13を介して貼着されて構成されている。
表面フィルム20cは、第1基材12aと、第1基材12aの表面に積層された第1ハードコート層11aと、第1基材12aの裏面に積層された第3ハードコート層11cとを有している。
裏面フィルム21cは、第2基材12bと、第2基材12bの裏面に積層された第2ハードコート層11bとを有している。 [Second Embodiment]
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.
Thesurface 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. Have.
Theback film 21c has the 2nd base material 12b and the 2nd hard-coat layer 11b laminated | stacked on the back surface of the 2nd base material 12b.
図5は、本発明の第2実施形態の構成を示す模式的断面図である。図5の高硬度フィルム3は、表面フィルム20cと裏面フィルム21cが、粘着層13を介して貼着されて構成されている。
表面フィルム20cは、第1基材12aと、第1基材12aの表面に積層された第1ハードコート層11aと、第1基材12aの裏面に積層された第3ハードコート層11cとを有している。
裏面フィルム21cは、第2基材12bと、第2基材12bの裏面に積層された第2ハードコート層11bとを有している。 [Second Embodiment]
FIG. 5 is a schematic cross-sectional view showing the configuration of the second embodiment of the present invention. The high-
The
The
〔第3実施形態〕
図6は、本発明の第3実施形態の構成を示す模式的断面図である。図6の高硬度フィルム4は、表面フィルム20dと裏面フィルム21dが、粘着層13を介して貼着されて構成されている。
表面フィルム20dは、第1基材12aと、第1基材12aの表面に積層された第1ハードコート層11aとを有している。
裏面フィルム21dは、第2基材12bと、第2基材12bの裏面に積層された第2ハードコート層11bとを有している。さらに、第2ハードコート層11bの裏面には、加飾等の目的で印刷層14が形成されている。印刷層14を第2ハードコート層11bの裏面に設置する理由は、画像表示装置等においては、印刷層14が内部に封入されることとなり、外部からの物理的な接触がなくなり、印刷面が保護されるからである。 [Third Embodiment]
FIG. 6 is a schematic cross-sectional view showing the configuration of the third embodiment of the present invention. Thehigh 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.
Thesurface film 20d has the 1st base material 12a and the 1st hard-coat layer 11a laminated | stacked on the surface of the 1st base material 12a.
Theback 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.
図6は、本発明の第3実施形態の構成を示す模式的断面図である。図6の高硬度フィルム4は、表面フィルム20dと裏面フィルム21dが、粘着層13を介して貼着されて構成されている。
表面フィルム20dは、第1基材12aと、第1基材12aの表面に積層された第1ハードコート層11aとを有している。
裏面フィルム21dは、第2基材12bと、第2基材12bの裏面に積層された第2ハードコート層11bとを有している。さらに、第2ハードコート層11bの裏面には、加飾等の目的で印刷層14が形成されている。印刷層14を第2ハードコート層11bの裏面に設置する理由は、画像表示装置等においては、印刷層14が内部に封入されることとなり、外部からの物理的な接触がなくなり、印刷面が保護されるからである。 [Third Embodiment]
FIG. 6 is a schematic cross-sectional view showing the configuration of the third embodiment of the present invention. The
The
The
上記の第2実施形態および第3実施形態を構成する各層を形成する材料については、第1実施形態と同等であるので、その説明を省略する。また、以下の説明において、印刷層に係る説明以外は、特に実施形態の指定をしていないときは、各実施形態に共通するものである。なお、以下の説明において、表面フィルム20a、20b、20c、20dをまとめて、表面フィルム20と記載することがある。同様に、裏面フィルム21a、21b、21c、21dをまとめて、裏面フィルム21と記載することがある。
Since the material forming 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. In the following description, the surface films 20a, 20b, 20c, and 20d may be collectively referred to as the surface film 20. Similarly, back film 21a, 21b, 21c, 21d may be collectively described as back film 21.
(印刷層14)
第3実施形態の印刷層14は、着色剤とバインダとを含む着色インキを印刷することによって形成される層である。着色剤としては、顔料または染料が使用される。バインダとしては、ポリビニル系樹脂、ポリアミド系樹脂、ポリアクリル系樹脂、ポリウレタン系樹脂、ポリビニルアセタール系樹脂、ポリエステルウレタン系樹脂、セルロースエステル系樹脂、アルキッド樹脂などの樹脂が使用できる。金属発色をさせる場合には、着色剤として、アルミニウム、チタン、ブロンズ等の金属の粒子やマイカに酸化チタンをコーティングしたパール顔料等を用いることができる。 (Print layer 14)
Theprinting 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. As 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. In the case of producing a metal color, 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.
第3実施形態の印刷層14は、着色剤とバインダとを含む着色インキを印刷することによって形成される層である。着色剤としては、顔料または染料が使用される。バインダとしては、ポリビニル系樹脂、ポリアミド系樹脂、ポリアクリル系樹脂、ポリウレタン系樹脂、ポリビニルアセタール系樹脂、ポリエステルウレタン系樹脂、セルロースエステル系樹脂、アルキッド樹脂などの樹脂が使用できる。金属発色をさせる場合には、着色剤として、アルミニウム、チタン、ブロンズ等の金属の粒子やマイカに酸化チタンをコーティングしたパール顔料等を用いることができる。 (Print layer 14)
The
(表面硬度)
本実施形態の高硬度フィルムは、JIS K5600-5-4に基づいて測定される鉛筆硬度を5H以上とすることが可能であり、ガラス板の代替となり得るものである。 (surface hardness)
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.
本実施形態の高硬度フィルムは、JIS K5600-5-4に基づいて測定される鉛筆硬度を5H以上とすることが可能であり、ガラス板の代替となり得るものである。 (surface hardness)
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.
本発明者らの検討によると、高硬度フィルムの表面硬度(鉛筆硬度)は、最表面の第1ハードコート層11aを形成する材料のみで決まるわけではなく、第1ハードコート層11aを裏から支える他のすべての層の構成や材料が関わっている。
According to the study by the present inventors, 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.
フィルムの高硬度化のためにハードコート層11は、高硬度フィルム1の最表面に設けることが必要である。また、鉛筆硬度向上の目的で表面フィルム20の裏面に第3ハードコート層11cをさらに設けることができる(図5参照)。さらに、裏面フィルム21の表面に第4ハードコート層を設けることができる(不図示)。3つのハードコート層を設けるときは、第3ハードコート層11cは、裏面フィルム21の表面ではなく、表面フィルム20の裏面に設ける方が好ましい。さらに、ハードコート層単体の鉛筆硬度は第1ハードコート層11a>第2ハードコート層11b≧第3ハードコート層11cであることが好ましい。複数あるハードコート層11は、同一の材料であっても、異なる材料であってもよい。
In order to increase the hardness of the film, the hard coat layer 11 needs to be provided on the outermost surface of the high hardness film 1. Moreover, 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). Furthermore, a fourth hard coat layer can be provided on the surface of the back film 21 (not shown). When three hard coat layers are provided, 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. Furthermore, 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.
ハードコート層11は、表面硬度に影響を及ぼす層である。そのため、ハードコート層11をより厚くすることが有効である。そして、複数あるハードコート層11の厚さの合計が、表面硬度に関わっている。一方、ハードコート層11の厚さの合計が大き過ぎると、製造上、乾燥・硬化が不十分となるおそれがある。そのため、ハードコート層11の厚さの合計は、15~80μmであることが好ましく、25~60μmであることがより好ましく、35~55μmであることがさらに好ましい。
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 μm, more preferably 25 to 60 μm, and still more preferably 35 to 55 μm.
本実施形態の高硬度フィルムでは、必要に応じて、本発明の効果を阻害しない範囲において、他の機能性の層をさらに設けることが可能である。例えば、導電層、低反射層、防指紋層などが挙げられる。
In the high hardness film of this embodiment, it is possible to further provide other functional layers as long as they do not impair the effects of the present invention. For example, a conductive layer, a low reflection layer, an anti-fingerprint layer, and the like can be given.
[高硬度フィルムの製造方法]
本実施形態の高硬度フィルムは、例えば、以下のようにして製造することができる。下記製造工程は、ロールツーロール方式で連続的に行うことも可能である。
(1)第1基材形成工程
第1基材12aの片面に第1ハードコート層11aを形成して表面フィルム20を形成する。
(2)第2基材形成工程
第2基材12bの片面に第2ハードコート層11bを形成して裏面フィルム21を形成する。
(3)貼着工程
表面フィルム20と裏面フィルム21を、粘着層13を介して貼着する。
(4)打ち抜き工程
所望の形状に打ち抜く。 [Method for producing high hardness film]
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 | surface of the 1st base material 12a, and the surface film 20 is formed.
(2) 2nd base material formation process The 2nd hard-coat layer 11b is formed in the single side | surface of the 2nd base material 12b, and the back surface film 21 is formed.
(3) Adhesion process The front film 20 and theback film 21 are adhered via the adhesive layer 13.
(4) Punching process Punching into a desired shape.
本実施形態の高硬度フィルムは、例えば、以下のようにして製造することができる。下記製造工程は、ロールツーロール方式で連続的に行うことも可能である。
(1)第1基材形成工程
第1基材12aの片面に第1ハードコート層11aを形成して表面フィルム20を形成する。
(2)第2基材形成工程
第2基材12bの片面に第2ハードコート層11bを形成して裏面フィルム21を形成する。
(3)貼着工程
表面フィルム20と裏面フィルム21を、粘着層13を介して貼着する。
(4)打ち抜き工程
所望の形状に打ち抜く。 [Method for producing high hardness film]
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-
(2) 2nd base material formation process The 2nd hard-
(3) Adhesion process The front film 20 and the
(4) Punching process Punching into a desired shape.
上記「(1)第1基材形成工程」、「(2)第2基材形成工程」において、ハードコート層の形成は、以下のようにして行うことができる。
まず、硬化性樹脂を含むハードコート層形成用塗工液を各基材に塗工して未硬化塗膜を形成する。 In the above “(1) first base material forming step” and “(2) second base material forming step”, 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.
まず、硬化性樹脂を含むハードコート層形成用塗工液を各基材に塗工して未硬化塗膜を形成する。 In the above “(1) first base material forming step” and “(2) second base material forming step”, 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.
ハードコート層形成用塗工液の溶剤としては、例えば、メタノール、エタノール、イソプロパノール、アセトン、メチルエチルケトン、トルエン、n-ヘキサン、n-ブチルアルコール、メチルイソブチルケトン、メチルブチルケトン、エチルブチルケトン、シクロヘキサノン、酢酸エチル、酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、N-メチル-2-ピロリドンなどが使用される。これらは1種以上を単独で使用してもよいし、2種以上を混合して使用してもよい。塗工ムラを軽減するためには、蒸発速度の異なる溶剤を使用することが好ましい。例えば、メチルエチルケトン、メチルイソブチルケトン、酢酸エチル、酢酸ブチル、プロピレングリコールモノメチルエーテルを混合して使用することが好ましい。
また、ハードコート層形成用塗工液は、硬化を促進させるために、公知の光重合開始剤を含有することが好ましい。また、熱硬化性の硬質成分を用いる場合には、イソシアネート化合物やエポキシ化合物等の架橋剤を含有することが好ましい。 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. In order to reduce coating unevenness, it is preferable to use 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.
Moreover, it is preferable that the coating liquid for hard-coat layer formation contains a well-known photoinitiator in order to accelerate hardening. Moreover, when using a thermosetting hard component, it is preferable to contain crosslinking agents, such as an isocyanate compound and an epoxy compound.
また、ハードコート層形成用塗工液は、硬化を促進させるために、公知の光重合開始剤を含有することが好ましい。また、熱硬化性の硬質成分を用いる場合には、イソシアネート化合物やエポキシ化合物等の架橋剤を含有することが好ましい。 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. In order to reduce coating unevenness, it is preferable to use 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.
Moreover, it is preferable that the coating liquid for hard-coat layer formation contains a well-known photoinitiator in order to accelerate hardening. Moreover, when using a thermosetting hard component, it is preferable to contain crosslinking agents, such as an isocyanate compound and an epoxy compound.
ハードコート層形成用塗工液の塗工方法としては、例えば、ブレードコーター、エアナイフコーター、ロールコーター、バーコーター、グラビアコーター、マイクログラビアコーター、ロッドブレードコーター、リップコーター、ダイコーター、カーテンコーター、印刷機等を用いた方法が挙げられる。
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.
次いで、塗膜を有した基材を加熱することによって、塗膜を乾燥させる。通常は、加熱温度60~100℃で、加熱時間1~5分の条件で行う。
Next, the coating film is dried by heating the substrate having the coating film. Usually, the heating is performed at a temperature of 60 to 100 ° C. and a heating time of 1 to 5 minutes.
次いで、未硬化塗膜を硬化させる。未硬化塗膜が、熱硬化型の樹脂を含有する場合には、加熱炉や赤外線ランプ等を用いた加熱より硬化させる。未硬化塗膜が、活性エネルギー線硬化型の樹脂を含有する場合には、活性エネルギー線の照射によって硬化させる。
活性エネルギー線としては、紫外線、電子線が挙げられ、中でも、汎用性の点から、紫外線が好ましい。紫外線の光源としては、例えば、高圧水銀灯、低圧水銀灯、超高圧水銀灯、メタルハライドランプ、カーボンアーク、キセノンアーク、無電極紫外線ランプ等を使用できる。
活性エネルギー線の照射による硬化は、窒素等の不活性ガス存在下で行うことが好ましい。硬化させる工程は、予備硬化工程と本硬化工程の2段階に分けて行ってもよい。 Next, the uncured coating film is cured. When the uncured coating film contains a thermosetting resin, it is cured by heating using a heating furnace or an infrared lamp. When the uncured coating film contains an active energy ray-curable resin, it is cured by irradiation with active energy rays.
Examples of the active energy rays include ultraviolet rays and electron beams. Among them, ultraviolet rays are preferable from the viewpoint of versatility. As 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.
活性エネルギー線としては、紫外線、電子線が挙げられ、中でも、汎用性の点から、紫外線が好ましい。紫外線の光源としては、例えば、高圧水銀灯、低圧水銀灯、超高圧水銀灯、メタルハライドランプ、カーボンアーク、キセノンアーク、無電極紫外線ランプ等を使用できる。
活性エネルギー線の照射による硬化は、窒素等の不活性ガス存在下で行うことが好ましい。硬化させる工程は、予備硬化工程と本硬化工程の2段階に分けて行ってもよい。 Next, the uncured coating film is cured. When the uncured coating film contains a thermosetting resin, it is cured by heating using a heating furnace or an infrared lamp. When the uncured coating film contains an active energy ray-curable resin, it is cured by irradiation with active energy rays.
Examples of the active energy rays include ultraviolet rays and electron beams. Among them, ultraviolet rays are preferable from the viewpoint of versatility. As 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.
上記「(3)貼着工程」において、表面フィルム20と裏面フィルム21の貼着は、以下の何れかの方法によって行うことができる。
(a)表面フィルム20における第1基材12aの裏側に、粘着剤塗工液を塗布・乾燥して粘着層13を形成し、その後裏面フィルム21を貼着する。
(b)裏面フィルム21における第2基材12bの表側に、粘着剤塗工液を塗布・乾燥して粘着層13を形成し、その後表面フィルム20を貼着する。
(c)表面フィルム20における第1基材12aの裏側に、両面粘着シートを用いて粘着層13を形成し、その後裏面フィルム21を貼着する。
(d)裏面フィルム21における第2基材12bの表側に、両面粘着シートを用いて粘着層13を形成し、その後表面フィルム20を貼着する。 In the “(3) sticking step”, the front film 20 and theback film 21 can be stuck by any of the following methods.
(A) On the back side of thefirst substrate 12a in the front film 20, the pressure-sensitive adhesive coating solution is applied and dried to form the pressure-sensitive adhesive layer 13, and then the back film 21 is adhered.
(B) On the front side of thesecond substrate 12b in the back film 21, an adhesive coating solution is applied and dried to form the adhesive layer 13, and then the surface film 20 is adhered.
(C) Theadhesive layer 13 is formed on the back side of the first substrate 12a in the surface film 20 using a double-sided adhesive sheet, and then the back film 21 is adhered.
(D) On the front side of thesecond substrate 12b in the back film 21, the adhesive layer 13 is formed using a double-sided adhesive sheet, and then the surface film 20 is adhered.
(a)表面フィルム20における第1基材12aの裏側に、粘着剤塗工液を塗布・乾燥して粘着層13を形成し、その後裏面フィルム21を貼着する。
(b)裏面フィルム21における第2基材12bの表側に、粘着剤塗工液を塗布・乾燥して粘着層13を形成し、その後表面フィルム20を貼着する。
(c)表面フィルム20における第1基材12aの裏側に、両面粘着シートを用いて粘着層13を形成し、その後裏面フィルム21を貼着する。
(d)裏面フィルム21における第2基材12bの表側に、両面粘着シートを用いて粘着層13を形成し、その後表面フィルム20を貼着する。 In the “(3) sticking step”, the front film 20 and the
(A) On the back side of the
(B) On the front side of the
(C) The
(D) On the front side of the
上記(a)、(b)における粘着剤塗工液は、粘着剤と溶剤及び必要に応じて助剤を含むものである。溶剤としては、アルコール(例えば、メタノール、エタノール、プロパノール等)、ケトン(例えば、アセトン、メチルエチルケトン等)、エーテル(例えば、ジエチルエーテル、メチルセロソルブ、エチルセロソルブ等)などが挙げられる。
粘着剤塗工液を塗工するコーターとしては、例えば、ブレードコーター、エアナイフコーター、ロールコーター、バーコーター、グラビアコーター、ロッドブレードコーター、リップコーター、ダイコーター、カーテンコーター、印刷機等が挙げられる。
乾燥は、加熱乾燥機や真空乾燥機などによって行う。 The pressure-sensitive adhesive coating liquid in the above (a) and (b) contains a pressure-sensitive adhesive, a solvent, and an auxiliary as necessary. Examples of 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.
粘着剤塗工液を塗工するコーターとしては、例えば、ブレードコーター、エアナイフコーター、ロールコーター、バーコーター、グラビアコーター、ロッドブレードコーター、リップコーター、ダイコーター、カーテンコーター、印刷機等が挙げられる。
乾燥は、加熱乾燥機や真空乾燥機などによって行う。 The pressure-sensitive adhesive coating liquid in the above (a) and (b) contains a pressure-sensitive adhesive, a solvent, and an auxiliary as necessary. Examples of 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.
上記(c)、(d)における両面粘着シートは、一対の剥離シートの間に粘着層が設けられたものである。剥離シートとしては公知のものが採用できる。剥離シートの材質としては、紙、フィルムなどが挙げられる。剥離シートは、片面に剥離層を有する片面剥離シートであることが好ましい。
また、一方の剥離シートの粘着層に対する剥離力と他方の剥離シートの粘着層に対する剥離力とは、異なることが好ましい。これにより、一方の剥離シートだけを先に剥離することが容易となる。
両面粘着シートを用いる場合、一方の剥離シートだけを先に剥離して粘着層を露出させ、表面フィルム20又は裏面フィルム21の一方に貼着する。次いで、他方の剥離シートを剥離して、裏面フィルム21又は表面フィルム20の他方と貼り合わせる。 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. A well-known thing can be employ | adopted as a peeling sheet. Examples of 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.
When using a double-sided pressure-sensitive adhesive sheet, only one release sheet is peeled first to expose the pressure-sensitive adhesive layer, and is adhered to one of the surface film 20 or theback film 21. Next, the other release sheet is peeled off and bonded to the other of the back film 21 or the front film 20.
また、一方の剥離シートの粘着層に対する剥離力と他方の剥離シートの粘着層に対する剥離力とは、異なることが好ましい。これにより、一方の剥離シートだけを先に剥離することが容易となる。
両面粘着シートを用いる場合、一方の剥離シートだけを先に剥離して粘着層を露出させ、表面フィルム20又は裏面フィルム21の一方に貼着する。次いで、他方の剥離シートを剥離して、裏面フィルム21又は表面フィルム20の他方と貼り合わせる。 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. A well-known thing can be employ | adopted as a peeling sheet. Examples of 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.
When using a double-sided pressure-sensitive adhesive sheet, only one release sheet is peeled first to expose the pressure-sensitive adhesive layer, and is adhered to one of the surface film 20 or the
第3実施形態において、印刷を行う場合、印刷層14の形成方法(印刷方法)としては、オフセット印刷法、グラビア印刷法、スクリーン印刷法などが適用され、多色刷りや階調表現を行うには、スクリーン印刷法が好ましい。
印刷は、「(3)貼着工程」前に行ってもよい。すなわち、表面フィルム20と貼着する前の裏面フィルム21に印刷してもよい。また、印刷は、「(4)打ち抜き工程」後に行ってもよい。 In the third embodiment, when printing is performed, an offset printing method, a gravure printing method, a screen printing method, or the like is applied as a forming method (printing method) of theprinting 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 theback surface film 21 before sticking with the surface film 20. The printing may be performed after “(4) Punching process”.
印刷は、「(3)貼着工程」前に行ってもよい。すなわち、表面フィルム20と貼着する前の裏面フィルム21に印刷してもよい。また、印刷は、「(4)打ち抜き工程」後に行ってもよい。 In the third embodiment, when printing is performed, 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 may be performed before “(3) sticking step”. That is, you may print on the
上記「(4)打ち抜き工程」において、打ち抜きは、表面フィルム20と裏面フィルム21を貼り合わせた積層フィルムに、打ち抜き刃を差し込むことによって行う。打ち抜き刃は、回転するものであってもよいし、積層フィルムに対して往復運動するものであってもよい。
In the “(4) punching step”, 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.
本実施形態を下記の実施例によって、さらに具体的に説明する。
ここで、基材としてのポリエチレンテレフタレート(PET)フィルムは以下のものを用いた。これらのフィルムは、すべて両面に易接着層を有している。
(i)PETフィルムa;商品名コスモシャインA4300、東洋紡績(株)製、210mm×297mm、厚さ125μm
(ii)PETフィルムb;商品名ルミラーU34、東レ(株)製、210mm×297mm、厚さ125μm
(iii)PETフィルムc;商品名KEL86W、帝人デュポン(株)製、210mm×297mm、厚さ125μm
(iv)PETフィルムd;商品名コスモシャインA4300、東洋紡績(株)製、210mm×297mm、厚さ250μm This embodiment will be described more specifically with reference to the following examples.
Here, the following were used for the polyethylene terephthalate (PET) film as a base material. These films all have an easy-adhesion layer on both sides.
(I) PET film a; trade name Cosmo Shine A4300, manufactured by Toyobo Co., Ltd., 210 mm × 297 mm, thickness 125 μm
(Ii) PET film b; trade name Lumirror U34, manufactured by Toray Industries, Inc., 210 mm × 297 mm, thickness 125 μm
(Iii) PET film c; trade name KEL86W, manufactured by Teijin DuPont Co., Ltd., 210 mm × 297 mm, thickness 125 μm
(Iv) PET film d; trade name Cosmo Shine A4300, manufactured by Toyobo Co., Ltd., 210 mm × 297 mm, thickness 250 μm
ここで、基材としてのポリエチレンテレフタレート(PET)フィルムは以下のものを用いた。これらのフィルムは、すべて両面に易接着層を有している。
(i)PETフィルムa;商品名コスモシャインA4300、東洋紡績(株)製、210mm×297mm、厚さ125μm
(ii)PETフィルムb;商品名ルミラーU34、東レ(株)製、210mm×297mm、厚さ125μm
(iii)PETフィルムc;商品名KEL86W、帝人デュポン(株)製、210mm×297mm、厚さ125μm
(iv)PETフィルムd;商品名コスモシャインA4300、東洋紡績(株)製、210mm×297mm、厚さ250μm This embodiment will be described more specifically with reference to the following examples.
Here, the following were used for the polyethylene terephthalate (PET) film as a base material. These films all have an easy-adhesion layer on both sides.
(I) PET film a; trade name Cosmo Shine A4300, manufactured by Toyobo Co., Ltd., 210 mm × 297 mm, thickness 125 μm
(Ii) PET film b; trade name Lumirror U34, manufactured by Toray Industries, Inc., 210 mm × 297 mm, thickness 125 μm
(Iii) PET film c; trade name KEL86W, manufactured by Teijin DuPont Co., Ltd., 210 mm × 297 mm, thickness 125 μm
(Iv) PET film d; trade name Cosmo Shine A4300, manufactured by Toyobo Co., Ltd., 210 mm × 297 mm, thickness 250 μm
<フィルムAの作製>
活性エネルギー線硬化型樹脂組成物として、ジペンタエリスリトールヘキサアクリレート(商品名:A-DPH、新中村化学(株)製)49質量部、レベリング剤(商品名BYK-310、ビッグケミージャパン(株)製)0.1質量部、光重合開始剤(商品名IRGACURE184、BASF(株)製)1.5質量部、メチルエチルケトン49.4質量部を混合して、フィルムA形成用組成物を調製した。 <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.
活性エネルギー線硬化型樹脂組成物として、ジペンタエリスリトールヘキサアクリレート(商品名:A-DPH、新中村化学(株)製)49質量部、レベリング剤(商品名BYK-310、ビッグケミージャパン(株)製)0.1質量部、光重合開始剤(商品名IRGACURE184、BASF(株)製)1.5質量部、メチルエチルケトン49.4質量部を混合して、フィルムA形成用組成物を調製した。 <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.
基材として、PETフィルムaを用い、該PETフィルムa上にフィルムA形成用組成物をバー塗工した。その後、80℃の熱風乾燥機にて120秒間乾燥した。さらに高圧水銀ランプ紫外線照射機(アイグラフィックス(株)製)を用いて、照射強度200mW/cm2、積算光量300mJ/cm2、酸素濃度10000ppm以下の条件で、紫外線を照射した。以上の工程を経て、膜厚25μmのハードコート層を基材上に形成して、フィルムAを得た。
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 μm was formed on the base material to obtain a film A.
<フィルムBの作製>
活性エネルギー線硬化型樹脂組成物として、トリメチロールプロパントリアクリレート(商品名A-TMPT、新中村化学(株)製)49質量部、レベリング剤(商品名BYK-310、ビッグケミージャパン(株)製)0.1質量部、光重合開始剤(商品名IRGACURE184、BASF(株)製)1.5質量部、メチルエチルケトン49.4質量部を混合して、フィルムB形成用組成物を調製した。 <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.
活性エネルギー線硬化型樹脂組成物として、トリメチロールプロパントリアクリレート(商品名A-TMPT、新中村化学(株)製)49質量部、レベリング剤(商品名BYK-310、ビッグケミージャパン(株)製)0.1質量部、光重合開始剤(商品名IRGACURE184、BASF(株)製)1.5質量部、メチルエチルケトン49.4質量部を混合して、フィルムB形成用組成物を調製した。 <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.
基材として、PETフィルムaを用い、該PETフィルムa上にフィルムB形成用組成物をバー塗工した。その後、80℃の熱風乾燥機にて60秒間乾燥した。さらに高圧水銀ランプ紫外線照射機(アイグラフィックス(株)製)を用いて、照射強度200mW/cm2、積算光量300mJ/cm2、酸素濃度10000ppm以下の条件で、紫外線を照射した。以上の工程を経て、膜厚25μmのハードコート層を基材上に形成して、フィルムBを得た。
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 μm was formed on the base material to obtain a film B.
<フィルムCの作製>
活性エネルギー線硬化型樹脂組成物として、エトキシ化イソシアヌル酸トリアクリレート(商品名A-9300、新中村化学(株)製)49質量部、レベリング剤(商品名BYK-310、ビッグケミージャパン(株)製)0.1質量部、光重合開始剤(商品名IRGACURE184、BASF(株)製)1.5質量部、メチルエチルケトン49.4質量部を混合して、フィルムC形成用組成物を調製した。 <Preparation of film C>
As an active energy ray-curable resin composition, 49 parts by mass of 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.
活性エネルギー線硬化型樹脂組成物として、エトキシ化イソシアヌル酸トリアクリレート(商品名A-9300、新中村化学(株)製)49質量部、レベリング剤(商品名BYK-310、ビッグケミージャパン(株)製)0.1質量部、光重合開始剤(商品名IRGACURE184、BASF(株)製)1.5質量部、メチルエチルケトン49.4質量部を混合して、フィルムC形成用組成物を調製した。 <Preparation of film C>
As an active energy ray-curable resin composition, 49 parts by mass of 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.
上記フィルムAのハードコート層を形成していない面に、フィルムC形成用組成物をバー塗工した。その後、80℃の熱風乾燥機にて60秒間乾燥した。さらに高圧水銀ランプ紫外線照射機(アイグラフィックス(株)製)を用いて、照射強度200mW/cm2、積算光量300mJ/cm2、酸素濃度10000ppm以下の条件で、紫外線を照射した。以上の工程を経て、膜厚3μmのハードコート層を基材上に形成して、フィルムCを得た。
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 μm was formed on the base material, and a film C was obtained.
<粘着剤溶液1の調製>
攪拌機、温度計、還流冷却機、滴下装置、窒素導入管を備えた反応装置に、窒素ガスを封入後、溶媒である酢酸エチルを添加した。次いで、反応装置内に、アクリル単量体であるブチルアクリレート65質量部、メチルアクリレート35質量部、アクリル酸2質量部と、重合開始剤である2,2´-アゾイソブチロニトリル0.1質量部を添加した。その後、攪拌しながら窒素ガス気流中、溶媒の還流温度で8時間重合した。反応終了後、トルエンを添加してアクリル重合体溶液を得た。次いで、該アクリル重合体固形分100質量部に対して、架橋剤であるトリレンジイソシアネート(商品名コロネートL、日本ポリウレタン工業(株)製)0.1質量部を混合して、重量平均分子量80万の粘着剤溶液1を得た。なお、重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)測定によりポリスチレン標準物質を用いて作成した検量線をもとに計算されたものである。 <Preparation ofadhesive solution 1>
Nitrogen gas was sealed in a reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, and then ethyl acetate as a solvent was added. Next, in the reactor, 65 parts by mass of butyl acrylate as an acrylic monomer, 35 parts by mass of methyl acrylate, 2 parts by mass of acrylic acid, and 2,2′-azoisobutyronitrile as a polymerization initiator 0.1 Part by weight was added. Then, it superposed | polymerized at the reflux temperature of the solvent for 8 hours in nitrogen gas stream, stirring. After completion of the reaction, toluene was added to obtain an acrylic polymer solution. Next, 0.1 parts by mass of 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 thousandadhesive 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.
攪拌機、温度計、還流冷却機、滴下装置、窒素導入管を備えた反応装置に、窒素ガスを封入後、溶媒である酢酸エチルを添加した。次いで、反応装置内に、アクリル単量体であるブチルアクリレート65質量部、メチルアクリレート35質量部、アクリル酸2質量部と、重合開始剤である2,2´-アゾイソブチロニトリル0.1質量部を添加した。その後、攪拌しながら窒素ガス気流中、溶媒の還流温度で8時間重合した。反応終了後、トルエンを添加してアクリル重合体溶液を得た。次いで、該アクリル重合体固形分100質量部に対して、架橋剤であるトリレンジイソシアネート(商品名コロネートL、日本ポリウレタン工業(株)製)0.1質量部を混合して、重量平均分子量80万の粘着剤溶液1を得た。なお、重量平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)測定によりポリスチレン標準物質を用いて作成した検量線をもとに計算されたものである。 <Preparation of
Nitrogen gas was sealed in a reactor equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube, and then ethyl acetate as a solvent was added. Next, in the reactor, 65 parts by mass of butyl acrylate as an acrylic monomer, 35 parts by mass of methyl acrylate, 2 parts by mass of acrylic acid, and 2,2′-azoisobutyronitrile as a polymerization initiator 0.1 Part by weight was added. Then, it superposed | polymerized at the reflux temperature of the solvent for 8 hours in nitrogen gas stream, stirring. After completion of the reaction, toluene was added to obtain an acrylic polymer solution. Next, 0.1 parts by mass of 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
<粘着剤溶液2の調製>
粘着剤溶液1の調製のときと同様にして粘着剤溶液2を調整した。すなわち、反応装置内に、アクリル単量体である2-エチルヘキシルアクリレート65質量部、メチルメタクリレート10質量部、エチルメタクリレート15質量部、ヒドロキシエチルアクリレート10質量部と、重合開始剤である2,2´-アゾイソブチロニトリル0.1質量部を添加した。その後、攪拌しながら窒素ガス気流中、溶媒の還流温度で8時間重合した。反応終了後、トルエンを添加してアクリル重合体溶液を得た。次いで、該アクリル重合体固形分100質量部に対して、架橋剤であるトリレンジイソシアネート(商品名コロネートL、日本ポリウレタン工業(株)製)2質量部を混合して、重量平均分子量150万の粘着剤溶液2を調製した。 <Preparation ofadhesive solution 2>
In the same manner as in the preparation of the pressure-sensitive adhesive solution 1, 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 | polymerized at the reflux temperature of the solvent for 8 hours in nitrogen gas stream, stirring. After completion of the reaction, toluene was added to obtain an acrylic polymer solution. Next, 2 parts by mass of 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.
粘着剤溶液1の調製のときと同様にして粘着剤溶液2を調整した。すなわち、反応装置内に、アクリル単量体である2-エチルヘキシルアクリレート65質量部、メチルメタクリレート10質量部、エチルメタクリレート15質量部、ヒドロキシエチルアクリレート10質量部と、重合開始剤である2,2´-アゾイソブチロニトリル0.1質量部を添加した。その後、攪拌しながら窒素ガス気流中、溶媒の還流温度で8時間重合した。反応終了後、トルエンを添加してアクリル重合体溶液を得た。次いで、該アクリル重合体固形分100質量部に対して、架橋剤であるトリレンジイソシアネート(商品名コロネートL、日本ポリウレタン工業(株)製)2質量部を混合して、重量平均分子量150万の粘着剤溶液2を調製した。 <Preparation of
In the same manner as in the preparation of the pressure-
<粘着剤溶液3の調製>
粘着剤溶液1の調製のときと同様にして、反応装置内に、アクリル単量体であるブチルアクリレート90質量部、エチルメタクリレート5質量部、アクリル酸2質量部、ヒドロキシエチルアクリレート3質量部と、重合開始剤である2,2´-アゾイソブチロニトリル0.1質量部を添加した。その後、攪拌しながら窒素ガス気流中、溶媒の還流温度で8時間重合した。反応終了後、トルエンを添加してアクリル重合体溶液を得た。次いで、該アクリル重合体固形分100質量部に対して、架橋剤であるトリレンジイソシアネート(商品名コロネートL、日本ポリウレタン工業(株)製)0.1質量部を混合して、重量平均分子量50万の粘着剤溶液3を調製した。 <Preparation ofadhesive solution 3>
In the same manner as in the preparation of the pressure-sensitive adhesive solution 1, 90 parts by mass of butyl acrylate as an acrylic monomer, 5 parts by mass of ethyl methacrylate, 2 parts by mass of acrylic acid, 3 parts by mass of hydroxyethyl acrylate, 0.12 parts by mass of 2,2′-azoisobutyronitrile as a polymerization initiator was added. Then, it superposed | polymerized at the reflux temperature of the solvent for 8 hours in nitrogen gas stream, stirring. After completion of the reaction, toluene was added to obtain an acrylic polymer solution. Next, 0.1 parts by mass of 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.
粘着剤溶液1の調製のときと同様にして、反応装置内に、アクリル単量体であるブチルアクリレート90質量部、エチルメタクリレート5質量部、アクリル酸2質量部、ヒドロキシエチルアクリレート3質量部と、重合開始剤である2,2´-アゾイソブチロニトリル0.1質量部を添加した。その後、攪拌しながら窒素ガス気流中、溶媒の還流温度で8時間重合した。反応終了後、トルエンを添加してアクリル重合体溶液を得た。次いで、該アクリル重合体固形分100質量部に対して、架橋剤であるトリレンジイソシアネート(商品名コロネートL、日本ポリウレタン工業(株)製)0.1質量部を混合して、重量平均分子量50万の粘着剤溶液3を調製した。 <Preparation of
In the same manner as in the preparation of the pressure-
(実施例1)
上記で得られた粘着剤溶液1を、裏面フィルムであるフィルムBのハードコート層を形成していない面にナイフコーターにより、乾燥後の塗工厚さが10μmになるように塗工し、100℃で2分間乾燥させて、粘着層を形成した。次いで、該粘着層と表面フィルムであるフィルムAのハードコート層が形成されていない面と貼り合わせて、積層フィルム1を作製した。 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 μm, 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.
上記で得られた粘着剤溶液1を、裏面フィルムであるフィルムBのハードコート層を形成していない面にナイフコーターにより、乾燥後の塗工厚さが10μmになるように塗工し、100℃で2分間乾燥させて、粘着層を形成した。次いで、該粘着層と表面フィルムであるフィルムAのハードコート層が形成されていない面と貼り合わせて、積層フィルム1を作製した。 Example 1
The pressure-
(実施例2)
粘着層の厚さを、15μmへ変更した以外は、実施例1と同様にして、積層フィルム2を作製した。 (Example 2)
Alaminated film 2 was produced in the same manner as in Example 1 except that the thickness of the adhesive layer was changed to 15 μm.
粘着層の厚さを、15μmへ変更した以外は、実施例1と同様にして、積層フィルム2を作製した。 (Example 2)
A
(実施例3)
表面フィルムであるフィルムAの代わりにフィルムCを使用し、フィルムCの膜厚3μmのハードコート層が形成されている面と貼り合わせた以外は、実施例1と同様にして、積層フィルム3を作製した。 Example 3
Alaminated 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 μm is formed. Produced.
表面フィルムであるフィルムAの代わりにフィルムCを使用し、フィルムCの膜厚3μmのハードコート層が形成されている面と貼り合わせた以外は、実施例1と同様にして、積層フィルム3を作製した。 Example 3
A
(実施例4)
裏面フィルムであるフィルムBの代わりにフィルムAを使用し、ハードコート層を形成していない面に粘着層を形成した以外は、実施例1と同様にして、積層フィルム4を作製した。 Example 4
Alaminated 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.
裏面フィルムであるフィルムBの代わりにフィルムAを使用し、ハードコート層を形成していない面に粘着層を形成した以外は、実施例1と同様にして、積層フィルム4を作製した。 Example 4
A
(実施例5)
第1基材をPETフィルムbへ変更した以外は実施例1と同様にして、積層フィルム5を作製した。 (Example 5)
Alaminated film 5 was produced in the same manner as in Example 1 except that the first substrate was changed to the PET film b.
第1基材をPETフィルムbへ変更した以外は実施例1と同様にして、積層フィルム5を作製した。 (Example 5)
A
(実施例6)
第2基材をPETフィルムbへ変更した以外は実施例1と同様にして、積層フィルム6を作製した。 (Example 6)
Alaminated film 6 was produced in the same manner as in Example 1 except that the second substrate was changed to the PET film b.
第2基材をPETフィルムbへ変更した以外は実施例1と同様にして、積層フィルム6を作製した。 (Example 6)
A
(実施例7)
第1基材をおよび第2基材をPETフィルムcへ変更した以外は実施例1と同様にして、積層フィルム7を作製した。 (Example 7)
Alaminated 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.
第1基材をおよび第2基材をPETフィルムcへ変更した以外は実施例1と同様にして、積層フィルム7を作製した。 (Example 7)
A
(実施例8)
第1基材をPETフィルムcへ変更した以外は実施例1と同様にして、積層フィルム8を作製した。 (Example 8)
Alaminated film 8 was produced in the same manner as in Example 1 except that the first substrate was changed to the PET film c.
第1基材をPETフィルムcへ変更した以外は実施例1と同様にして、積層フィルム8を作製した。 (Example 8)
A
(実施例9)
第2基材をPETフィルムcへ変更した以外は実施例1と同様にして、積層フィルム9を作製した。 Example 9
Alaminated film 9 was produced in the same manner as in Example 1 except that the second substrate was changed to the PET film c.
第2基材をPETフィルムcへ変更した以外は実施例1と同様にして、積層フィルム9を作製した。 Example 9
A
(実施例10)
粘着層の厚さを25μmへ変更した以外は、実施例1と同様にして、積層フィルム10を作製した。 (Example 10)
Alaminated film 10 was produced in the same manner as in Example 1 except that the thickness of the adhesive layer was changed to 25 μm.
粘着層の厚さを25μmへ変更した以外は、実施例1と同様にして、積層フィルム10を作製した。 (Example 10)
A
表1と表2において、フィルムAの基材のPETフィルムをPETフィルムaからPETフィルムbに変えたものをフィルムA1と表示した。同様に、フィルムAの基材のPETフィルムをPETフィルムaからPETフィルムcに変えたものをフィルムA2と表示した。フィルムBの基材のPETフィルムをPETフィルムaからPETフィルムbに変えたものをフィルムB1と表示した。同様に、フィルムBの基材のPETフィルムをPETフィルムaからPETフィルムcに変えたものをフィルムB2と表示した。
In Tables 1 and 2, a film A1 obtained by changing the PET film as the base material of the film A from the PET film a to the PET film b was displayed. Similarly, what changed the PET film of the base material of the film A from PET film a to PET film c was displayed as film A2. What changed the PET film of the base material of the film B from PET film a to PET film b was displayed as film B1. Similarly, what changed the PET film of the base material of the film B from PET film a to PET film c was displayed as film B2.
(比較例1)
粘着剤溶液2を使用した以外は、実施例1と同様にして、積層フィルム11を作製した。 (Comparative Example 1)
Alaminated film 11 was produced in the same manner as in Example 1 except that the adhesive solution 2 was used.
粘着剤溶液2を使用した以外は、実施例1と同様にして、積層フィルム11を作製した。 (Comparative Example 1)
A
(比較例2)
粘着剤溶液3を使用した以外は、実施例1と同様にして、積層フィルム12を作製した。 (Comparative Example 2)
Alaminated film 12 was produced in the same manner as in Example 1 except that the adhesive solution 3 was used.
粘着剤溶液3を使用した以外は、実施例1と同様にして、積層フィルム12を作製した。 (Comparative Example 2)
A
(比較例3)
表面フィルムであるフィルムAのハードコート層を形成している面に粘着剤を塗工した以外は、実施例1と同様にして、積層フィルム13を作製した。 (Comparative Example 3)
Alaminated 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.
表面フィルムであるフィルムAのハードコート層を形成している面に粘着剤を塗工した以外は、実施例1と同様にして、積層フィルム13を作製した。 (Comparative Example 3)
A
(比較例4)
裏面フィルムであるフィルムBのハードコート層を形成している面に粘着剤を塗工した以外は、実施例1と同様にして、積層フィルム14を作製した。 (Comparative Example 4)
Alaminated 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.
裏面フィルムであるフィルムBのハードコート層を形成している面に粘着剤を塗工した以外は、実施例1と同様にして、積層フィルム14を作製した。 (Comparative Example 4)
A
(比較例5)
裏面フィルムであるフィルムBの代わりにPETフィルムaを使用した以外は、実施例1と同様にして、積層フィルム15を作製した。 (Comparative Example 5)
Alaminated 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.
裏面フィルムであるフィルムBの代わりにPETフィルムaを使用した以外は、実施例1と同様にして、積層フィルム15を作製した。 (Comparative Example 5)
A
(比較例6)
粘着層を介さずに、PETフィルムdの表面に、実施例1と同条件でフィルムA形成用組成物を塗工し、膜厚25μmのハードコート層を形成した。そのPETフィルムdの反対側の裏面に、実施例1と同条件でフィルムB形成用組成物を実施例1と同条件で塗工し、膜厚25μmのハードコート層を形成して、積層フィルム16を作製した。 (Comparative 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 μm. On the reverse side of the PET film d, 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 μm. 16 was produced.
粘着層を介さずに、PETフィルムdの表面に、実施例1と同条件でフィルムA形成用組成物を塗工し、膜厚25μmのハードコート層を形成した。そのPETフィルムdの反対側の裏面に、実施例1と同条件でフィルムB形成用組成物を実施例1と同条件で塗工し、膜厚25μmのハードコート層を形成して、積層フィルム16を作製した。 (Comparative 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 μm. On the reverse side of the PET film d, 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 μm. 16 was produced.
上記の実施例、比較例で得られた積層フィルムは、以下に記載する方法で、各種特性や性能の評価を行った。
The laminated films obtained in the above examples and comparative examples were evaluated for various properties and performances by the methods described below.
<粘着層の貯蔵弾性率G´の評価用試料の調製>
評価用試料としては、各積層フィルムの作成に使用した粘着剤のみのシートを積層して、100~150μm厚のシートを作成して、測定に供した。 <Preparation of sample for evaluation of storage elastic modulus G 'of adhesive layer>
As a sample for evaluation, a sheet of only the pressure-sensitive adhesive used for preparation of each laminated film was laminated to prepare a sheet having a thickness of 100 to 150 μm, which was used for measurement.
評価用試料としては、各積層フィルムの作成に使用した粘着剤のみのシートを積層して、100~150μm厚のシートを作成して、測定に供した。 <Preparation of sample for evaluation of storage elastic modulus G 'of adhesive layer>
As a sample for evaluation, a sheet of only the pressure-sensitive adhesive used for preparation of each laminated film was laminated to prepare a sheet having a thickness of 100 to 150 μm, which was used for measurement.
<粘着層の貯蔵弾性率G´の評価>
レオメーター(Reologica社製、型式DYNALYSER DAR-200)を用いて、周波数1Hz、歪0.1%、昇温速度3℃/分の条件で、-100~100℃の範囲で測定した。温度20℃および80℃での数値をもって、動的せん断貯蔵弾性率G´(20℃)およびG´(80℃)とした。 <Evaluation of storage elastic modulus G ′ of adhesive layer>
Using a rheometer (Model DYNALYSER DAR-200, manufactured by Reologica), the measurement was performed in the range of −100 to 100 ° C. under the conditions of a frequency of 1 Hz, a strain of 0.1%, and a heating rate of 3 ° C./min. The numerical values at temperatures of 20 ° C. and 80 ° C. were used as dynamic shear storage moduli G ′ (20 ° C.) and G ′ (80 ° C.).
レオメーター(Reologica社製、型式DYNALYSER DAR-200)を用いて、周波数1Hz、歪0.1%、昇温速度3℃/分の条件で、-100~100℃の範囲で測定した。温度20℃および80℃での数値をもって、動的せん断貯蔵弾性率G´(20℃)およびG´(80℃)とした。 <Evaluation of storage elastic modulus G ′ of adhesive layer>
Using a rheometer (Model DYNALYSER DAR-200, manufactured by Reologica), the measurement was performed in the range of −100 to 100 ° C. under the conditions of a frequency of 1 Hz, a strain of 0.1%, and a heating rate of 3 ° C./min. The numerical values at temperatures of 20 ° C. and 80 ° C. were used as dynamic shear storage moduli G ′ (20 ° C.) and G ′ (80 ° C.).
<鉛筆硬度の評価>
作製した積層フィルムの表面を、鉛筆引掻塗膜硬さ試験機((株)コーティングスター工業製)を用いて、JIS K5600-5-4に準拠して測定した。荷重は750gである。引掻いた鉛筆の中で表面に傷が入らなかった最も硬い鉛筆の硬度をそのフィルムの鉛筆硬度とした。 <Evaluation of pencil hardness>
The surface of the produced laminated film was measured according to JIS K5600-5-4 using a pencil scratch coating film hardness tester (manufactured by Coating Star Industry Co., Ltd.). The load is 750 g. Among the scratched pencils, the hardness of the hardest pencil with no scratch on the surface was taken as the pencil hardness of the film.
作製した積層フィルムの表面を、鉛筆引掻塗膜硬さ試験機((株)コーティングスター工業製)を用いて、JIS K5600-5-4に準拠して測定した。荷重は750gである。引掻いた鉛筆の中で表面に傷が入らなかった最も硬い鉛筆の硬度をそのフィルムの鉛筆硬度とした。 <Evaluation of pencil hardness>
The surface of the produced laminated film was measured according to JIS K5600-5-4 using a pencil scratch coating film hardness tester (manufactured by Coating Star Industry Co., Ltd.). The load is 750 g. Among the scratched pencils, the hardness of the hardest pencil with no scratch on the surface was taken as the pencil hardness of the film.
<表面硬度の評価>
鉛筆硬度の評価と同様に作製した積層フィルムの表面を、鉛筆引掻塗膜硬さ試験機((株)コーティングスター工業製)を用いて、JIS K5600-5-4に準拠して測定した。荷重は750gである。硬度5Hの鉛筆で引掻いたときに表面に傷が入らず、打痕もないものを○、傷は入らなかったが打痕がややあるものを△、打痕の有無に関わらず傷が入ったものを×とした。 <Evaluation of surface hardness>
The surface of the laminated film produced in the same manner as in the pencil hardness evaluation was measured using a pencil scratch coating film hardness tester (manufactured by Coating Star Industry Co., Ltd.) according to JIS K5600-5-4. The load is 750 g. When scratched with a pencil with a hardness of 5H, the surface does not have scratches and there are no dents, ○, there is no scratches but there are some dents, and there is scratches regardless of the presence or absence of dents. Was marked with x.
鉛筆硬度の評価と同様に作製した積層フィルムの表面を、鉛筆引掻塗膜硬さ試験機((株)コーティングスター工業製)を用いて、JIS K5600-5-4に準拠して測定した。荷重は750gである。硬度5Hの鉛筆で引掻いたときに表面に傷が入らず、打痕もないものを○、傷は入らなかったが打痕がややあるものを△、打痕の有無に関わらず傷が入ったものを×とした。 <Evaluation of surface hardness>
The surface of the laminated film produced in the same manner as in the pencil hardness evaluation was measured using a pencil scratch coating film hardness tester (manufactured by Coating Star Industry Co., Ltd.) according to JIS K5600-5-4. The load is 750 g. When scratched with a pencil with a hardness of 5H, the surface does not have scratches and there are no dents, ○, there is no scratches but there are some dents, and there is scratches regardless of the presence or absence of dents. Was marked with x.
<カールの評価>
作製した積層フィルムを、200mm×200mmの大きさに断裁し、23℃50%RH環境下に24時間静置した。その後、試験片を水平な板上に試験片を凹となるように(凹んだ部分が上側となるように)置き、4つの角の浮き上がり(板面から各々の角までの距離)を定規にて測定し、その4隅の平均値(mm)を求めた。4隅の平均値が10mm未満のものを○、10mm以上15mm未満のものを△、15mm以上のものを×とした。
また、熱処理後のカールは、同様に裁断した試料を150℃の乾燥機に1時間入れて熱処理を施した後に、上記と同様に静置してから測定した。 <Evaluation of curls>
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 Δ, 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.
作製した積層フィルムを、200mm×200mmの大きさに断裁し、23℃50%RH環境下に24時間静置した。その後、試験片を水平な板上に試験片を凹となるように(凹んだ部分が上側となるように)置き、4つの角の浮き上がり(板面から各々の角までの距離)を定規にて測定し、その4隅の平均値(mm)を求めた。4隅の平均値が10mm未満のものを○、10mm以上15mm未満のものを△、15mm以上のものを×とした。
また、熱処理後のカールは、同様に裁断した試料を150℃の乾燥機に1時間入れて熱処理を施した後に、上記と同様に静置してから測定した。 <Evaluation of curls>
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 Δ, 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.
<粘着力の評価>
作製した粘着剤溶液を基材であるPETフィルム(商品名コスモシャインA4300、東洋紡績(株)製、厚さ100μm)の片面に、ナイフコーターにより、乾燥後の厚さが積層フィルムの粘着層の厚さと同じになるように塗工した。次いで、100℃で2分間乾燥させ、シリコーンPET剥離フィルム(商品名;75RL-07(L)、王子エフテックス社製、75μm厚)へ貼り合わせた。その後、温度23℃、湿度50%の環境下で7日間エージングさせた後、このフィルムから、幅25mm×長さ100mmの試験片をサンプリングした。一方、表面をエタノールで洗浄し、温度23℃、湿度50%RHの環境下にて3時間以上放置したアルカリガラス板を用意した。試験片から剥離フィルムを剥離したものを、アルカリガラス板の表面に質量2kgの圧着ローラーで一往復させることによって貼り合せた。貼り合せてから30分経過した後、JIS Z0237に規定された180度引きはがし法によって、引張速度300mm/分で引きはがして、粘着力(N/25mm)を測定した。 <Evaluation of adhesive strength>
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 μm) 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 μm thickness). Then, after aging for 7 days in an environment of a temperature of 23 ° C. and a humidity of 50%, a test piece having a width of 25 mm × a length of 100 mm was sampled from the film. On the other hand, 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.
作製した粘着剤溶液を基材であるPETフィルム(商品名コスモシャインA4300、東洋紡績(株)製、厚さ100μm)の片面に、ナイフコーターにより、乾燥後の厚さが積層フィルムの粘着層の厚さと同じになるように塗工した。次いで、100℃で2分間乾燥させ、シリコーンPET剥離フィルム(商品名;75RL-07(L)、王子エフテックス社製、75μm厚)へ貼り合わせた。その後、温度23℃、湿度50%の環境下で7日間エージングさせた後、このフィルムから、幅25mm×長さ100mmの試験片をサンプリングした。一方、表面をエタノールで洗浄し、温度23℃、湿度50%RHの環境下にて3時間以上放置したアルカリガラス板を用意した。試験片から剥離フィルムを剥離したものを、アルカリガラス板の表面に質量2kgの圧着ローラーで一往復させることによって貼り合せた。貼り合せてから30分経過した後、JIS Z0237に規定された180度引きはがし法によって、引張速度300mm/分で引きはがして、粘着力(N/25mm)を測定した。 <Evaluation of adhesive strength>
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 μm) 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 μm thickness). Then, after aging for 7 days in an environment of a temperature of 23 ° C. and a humidity of 50%, a test piece having a width of 25 mm × a length of 100 mm was sampled from the film. On the other hand, 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.
<寸法変化率の評価>
PETフィルム基材を縦100mm×横100mmの大きさに断裁し、JIS C2151に準拠して150℃、30分間加熱処理後の縦方向および横方向の寸法変化率(%)をそれぞれ算出した。 <Evaluation of dimensional change rate>
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.
PETフィルム基材を縦100mm×横100mmの大きさに断裁し、JIS C2151に準拠して150℃、30分間加熱処理後の縦方向および横方向の寸法変化率(%)をそれぞれ算出した。 <Evaluation of dimensional change rate>
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.
評価結果を図1と図2に示した。図1、図2において、実施例1~10は、いずれも粘着層の動的せん断貯蔵弾性率の式(1)および式(2)の規定を満足し、本発明の要件を満足するものである。カール、鉛筆硬度および表面硬度において、実用的に優れた性能を有するものであった。
The evaluation results are shown in FIG. 1 and FIG. 1 and 2, each of Examples 1 to 10 satisfies the requirements of the dynamic shear storage elastic modulus (1) and (2) of the adhesive layer and satisfies the requirements of the present invention. is there. The curl, pencil hardness and surface hardness had practically excellent performance.
比較例1は、粘着層の動的せん断貯蔵弾性率の式(1)および式(2)の規定をいずれも満足していないものであったが、粘着層の粘着力も弱く、層間剥離が発生して、評価することが困難であった。比較例2は、粘着層の動的せん断貯蔵弾性率の数値が式(1)の下限未満のものであり、鉛筆硬度および表面硬度に劣るものであった。比較例3は、表面フィルムのハードコート層の位置が逆となっているために、鉛筆硬度、表面硬度およびカールにおいて劣るものであった。比較例4は、裏面フィルムのハードコート層の位置が逆となっているために、カールにおいて劣るものであった。比較例5は、裏面フィルムにPETフィルムを用いたものであるが、鉛筆硬度、表面硬度およびカールにおいて劣るものであった。比較例6は、粘着層を有しないものであるが、カールにおいて劣るものであった。
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. In Comparative Example 2, 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. In 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.
本発明の高硬度フィルムは、画像表示装置等を保護するための表面保護フィルムとして使用することができる。また、薄く透明であるため、薄いガラス板の代替として各種表示板の基材として使用することができる。また、各種プラスチック成形品の表面に貼付することによって、表面硬度を上げて内部を保護したり、耐擦傷性を向上させたり、破壊時に破片が飛び散るのを防止することができる。
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.
1、2、3、4 高硬度フィルム
11a 第1ハードコート層
11b 第2ハードコート層
11c 第3ハードコート層
12a 第1基材
12b 第2基材
13 粘着層
14 印刷層
15 易接着層
20a、20b、20c、20d 表面フィルム
21a、21b、21c、21d 裏面フィルム 1, 2, 3, 4High hardness film 11a 1st hard coat layer 11b 2nd hard coat layer 11c 3rd hard coat layer 12a 1st base material 12b 2nd base material 13 Adhesive layer 14 Print layer 15 Easy adhesion layer 20a, 20b, 20c, 20d Surface film 21a, 21b, 21c, 21d Back film
11a 第1ハードコート層
11b 第2ハードコート層
11c 第3ハードコート層
12a 第1基材
12b 第2基材
13 粘着層
14 印刷層
15 易接着層
20a、20b、20c、20d 表面フィルム
21a、21b、21c、21d 裏面フィルム 1, 2, 3, 4
Claims (7)
- 第1基材と該第1基材の少なくとも表面に積層されたハードコート層とを有する表面フィルムと、
第2基材と該第2基材の少なくとも裏面に積層されたハードコート層とを有する裏面フィルムと、
前記表面フィルムの裏面と前記裏面フィルムの表面との間に設けられ、両フィルムを貼着する粘着層を備え、
前記第1基材の厚さt1と前記第2基材の厚さt2とが、t1≦t2≦1.1×t1の関係にあり、
前記粘着層の20℃、周波数1Hzにおける動的せん断貯蔵弾性率G´(20℃)および前記粘着層の80℃、周波数1Hzにおける動的せん断貯蔵弾性率G´(80℃)が下記式(1)および式(2)を満足することを特徴とする高硬度フィルム。
1×105Pa≦G´(20℃)≦1×107Pa ・・・(1)
1×104Pa≦G´(80℃)≦1×106Pa ・・・(2) A surface film having a first substrate and a hard coat layer laminated on at least the surface of the first substrate;
A back film having a second substrate and a hard coat layer laminated on at least the back surface of the second substrate;
Provided between the back surface of the front film and the surface of the back film, comprising an adhesive layer for adhering both films,
The thickness t 2 of the thickness t 1 of the first substrate the second substrate is in the relationship of t 1 ≦ t 2 ≦ 1.1 × t 1,
The dynamic shear storage elastic modulus G ′ (20 ° C.) at 20 ° C. and a frequency of 1 Hz of the adhesive layer and the dynamic shear storage elastic modulus G ′ (80 ° C.) of the adhesive layer at 80 ° C. and a frequency of 1 Hz are represented by the following formula (1 ) And formula (2).
1 × 10 5 Pa ≦ G ′ (20 ° C.) ≦ 1 × 10 7 Pa (1)
1 × 10 4 Pa ≦ G ′ (80 ° C.) ≦ 1 × 10 6 Pa (2) - 前記粘着層の厚さが25μm以下である請求項1に記載の高硬度フィルム。 The high hardness film according to claim 1, wherein the adhesive layer has a thickness of 25 μm or less.
- 前記粘着層の粘着力が5N/25mm以上である請求項1または請求項2に記載の高硬度フィルム。 The high hardness film according to claim 1 or 2, wherein the adhesive strength of the adhesive layer is 5 N / 25 mm or more.
- 前記第1基材と前記第2基材の寸法変化率の差が、縦方向と横方向のいずれも0.5%以下である請求項1~3のいずれか1項に記載の高硬度フィルム。 The high hardness film according to any one of claims 1 to 3, wherein a difference in dimensional change between the first base material and the second base material is 0.5% or less in both the vertical direction and the horizontal direction. .
- JIS K5600-5-4に基づいて測定される鉛筆硬度が5H以上である請求項1~4のいずれか1項に記載の高硬度フィルム。 The high hardness film according to any one of claims 1 to 4, wherein the pencil hardness measured based on JIS K5600-5-4 is 5H or more.
- 前記第1基材および前記第2基材が、ポリエステルフィルムであり、前記ハードコート層が、アクリル系またはウレタン系硬化性樹脂であることを特徴とする請求項1~5のいずれか1項に記載の高硬度フィルム。 6. The method according to claim 1, wherein the first base material and the second base material are polyester films, and the hard coat layer is an acrylic or urethane curable resin. High hardness film as described.
- 前記第1基材と前記第2基材の厚さがそれぞれ50~250μm、前記ハードコート層の厚さの合計が15~80μm、前記粘着層の厚さが5~25μmであることを特徴とする請求項1~6のいずれか1項に記載の高硬度フィルム。 The thickness of the first base material and the second base material is 50 to 250 μm, the total thickness of the hard coat layer is 15 to 80 μm, and the thickness of the adhesive layer is 5 to 25 μm, The high hardness film according to any one of claims 1 to 6.
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