WO2015079866A1 - ハードコートフィルムおよび透明導電性フィルム - Google Patents
ハードコートフィルムおよび透明導電性フィルム Download PDFInfo
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- WO2015079866A1 WO2015079866A1 PCT/JP2014/079063 JP2014079063W WO2015079866A1 WO 2015079866 A1 WO2015079866 A1 WO 2015079866A1 JP 2014079063 W JP2014079063 W JP 2014079063W WO 2015079866 A1 WO2015079866 A1 WO 2015079866A1
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- AOLMPVPUFVWGPN-UHFFFAOYSA-N diazanium;1-dodecoxydodecane;sulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=O.CCCCCCCCCCCCOCCCCCCCCCCCC AOLMPVPUFVWGPN-UHFFFAOYSA-N 0.000 description 1
- XDSGMUJLZDSCPA-UHFFFAOYSA-N diazanium;phenoxybenzene;sulfate Polymers [NH4+].[NH4+].[O-]S([O-])(=O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 XDSGMUJLZDSCPA-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- KQPPJWHBSYEOKV-UHFFFAOYSA-M dodecyl-ethyl-dimethylazanium;ethyl sulfate Chemical compound CCOS([O-])(=O)=O.CCCCCCCCCCCC[N+](C)(C)CC KQPPJWHBSYEOKV-UHFFFAOYSA-M 0.000 description 1
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- RHZNQEWFWUODFC-UHFFFAOYSA-N ethyl(dimethyl)azanium;ethyl sulfate Chemical compound CC[NH+](C)C.CCOS([O-])(=O)=O RHZNQEWFWUODFC-UHFFFAOYSA-N 0.000 description 1
- XUQIHIHYTRZORE-UHFFFAOYSA-M ethyl-dimethyl-octylazanium;ethyl sulfate Chemical compound CCOS([O-])(=O)=O.CCCCCCCC[N+](C)(C)CC XUQIHIHYTRZORE-UHFFFAOYSA-M 0.000 description 1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
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- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
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- 238000000691 measurement method Methods 0.000 description 1
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- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
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- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
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- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
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- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- RCMHUQGSSVZPDG-UHFFFAOYSA-N phenoxybenzene;phosphoric acid Chemical class OP(O)(O)=O.C=1C=CC=CC=1OC1=CC=CC=C1 RCMHUQGSSVZPDG-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
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- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
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- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
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- SOLUNJPVPZJLOM-UHFFFAOYSA-N trizinc;distiborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-][Sb]([O-])([O-])=O.[O-][Sb]([O-])([O-])=O SOLUNJPVPZJLOM-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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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
- B32B2255/00—Coating on the layer surface
-
- 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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
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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
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/418—Refractive
Definitions
- the present invention relates to a hard coat film and a transparent conductive film having high transparency and good blocking resistance, and in particular, a hard coat film suitable for a transparent conductive film and a transparent conductive film using the hard coat film. It relates to a property film.
- a hard coat film in which a hard coat layer is laminated on a base film is used as a surface film for a display or a touch panel, or as a base film for an electrode film for a touch panel (transparent conductive film for a touch panel).
- Hard coat films used for these applications are required to have high transparency and good blocking resistance.
- Patent Documents 1 to 3 In order to improve the blocking resistance of the hard coat film, it has been proposed to provide protrusions with particles on the surface (Patent Documents 1 to 3).
- an antiglare film on the display surface to prevent reflection of external light and reflection of an image. It is generally known that an antiglare film forms irregularities on the surface of an antiglare layer by containing relatively large particles in the antiglare layer (for example, Patent Document 4).
- the techniques disclosed in Patent Documents 1 to 3 have not yet fully satisfied transparency and blocking resistance.
- the antiglare film has relatively good blocking resistance because it forms irregularities on the surface using relatively large particles (for example, particles having an average particle diameter of 1 ⁇ m or more). can get.
- relatively large particles for example, particles having an average particle diameter of 1 ⁇ m or more.
- it is not suitable as a base film for a transparent conductive film.
- an object of the present invention is to provide a hard coat film having high transparency and good blocking resistance in view of the above-mentioned problems of the prior art.
- Another object of the present invention is to provide a hard coat film suitable for a transparent conductive film.
- 1 includes a particle aggregate in which a plurality of particles having a size of 0.5 times or less of the thickness (d: ⁇ m) of the hard coat layer is aggregated, and a protrusion by the particle aggregate is formed on the surface of the first hard coat layer.
- the base film is a polyethylene terephthalate film having a refractive index of 1.62 to 1.70, and a resin having a refractive index of 1.55 to 1.61 on one side or both sides of the polyethylene terephthalate film.
- the hard coat film according to any one of [1] to [10], wherein a first hard coat layer having a refractive index of 1.48 to 1.54 is laminated via the layer.
- the base film is a polyethylene terephthalate film having a refractive index of 1.62 to 1.70, and a resin layer having a refractive index of 1.55 to 1.61 on one surface of the polyethylene terephthalate film.
- a resin layer having a refractive index of 1.55 to 1.61 is laminated on the other surface of the polyethylene terephthalate film.
- a hard coat film having high transparency and good blocking resistance can be provided.
- the hard coat film of the present invention is suitable for a base film of a transparent conductive film.
- FIG. 1 is a schematic cross-sectional view of the hard coat film of the present invention.
- FIG. 2 is a schematic plan view (overhead view) of the surface of the first hard coat layer in the hard coat film of the present invention.
- FIG. 3 is an example of a surface photograph taken by a scanning electron microscope on the surface of the first hard coat layer in the hard coat film of the present invention.
- FIG. 4 is a diagram schematically showing individual particles forming the particle aggregate.
- the hard coat film of the present invention includes a first hard coat layer on at least one surface of the base film.
- the first hard coat layer has a plurality of particles having an average particle size (r: ⁇ m) of less than 0.5 ⁇ m and 0.5 times or less the thickness (d: ⁇ m) of the first hard coat layer.
- r: ⁇ m average particle size
- d thickness
- the first hard coat layer surface there are 1 protrusion per 4 ⁇ m square (4 ⁇ m ⁇ 4 ⁇ m) on the surface of the first hard coat layer. Exists at a density of more than one.
- the particle aggregate in which a plurality of particles are aggregated refers to a particle aggregated or bonded (connected).
- the existence density of protrusions (the number of protrusions per 4 ⁇ m square on the surface of the first hard coat layer) can be measured by observing the surface of the hard coat layer with a scanning electron microscope (SEM).
- SEM scanning electron microscope
- the density of protrusions in the present invention is obtained by measuring and averaging the number of protrusions at five arbitrarily selected locations.
- the density of protrusions is preferably 2 or more per 4 ⁇ m square on the surface of the first hard coat layer, more preferably 3 or more, and particularly preferably 4 or more from the viewpoint of improving blocking resistance.
- the upper limit is not particularly limited, but about 100 is appropriate. If the density of protrusions exceeds 100, the haze value tends to increase, and the transparency of the hard coat film may decrease. In this respect, the upper limit of the density of protrusions is preferably 80 or less, more preferably 70 or less, and particularly preferably 50 or less.
- FIG. 1 is a schematic cross-sectional view showing an example of the hard coat film of the present invention.
- a first hard coat layer 3 is laminated on a base film 2.
- a particle aggregate 10 in which a plurality of particles 1 are aggregated, and on the surface of the first hard coat layer, protrusions 11 formed by the particle aggregate 10 are formed.
- FIG. 2 is a schematic plan view showing two examples of the surface of the first hard coat layer of the hard coat film of the present invention.
- protrusions 11 made of a particle aggregate in which a plurality of particles 1 are aggregated.
- the protrusion is preferably formed of a plurality of particles, and the protrusion has a plurality of particles in the surface direction (planar) of the surface of the first hard coat layer. It is preferably formed in an aggregated state.
- a particle aggregate in which many particles are aggregated in the plane direction of the surface of the first hard coat layer is formed in the vicinity of the surface of the first hard coat layer. Preferably it is present.
- This particle aggregate preferably has a relatively small number of particles (particle stacking) in the direction perpendicular to the surface of the first hard coat layer (the thickness direction of the first hard coat layer).
- the ratio of the number of particles forming the protrusion to the total number of particles forming the particle aggregate is large. Become. That is, a protrusion having a relatively large area can be formed with a relatively small number of particles. As a result, good transparency and good blocking resistance can be satisfied at the same time.
- a mode in which a part of secondary aggregated particles formed by simply aggregating primary particles is projected on the surface of the hard coat layer is generally like the iceberg described above. Since it is close to the form, good transparency and good blocking resistance may not be stably obtained.
- the protrusion is preferably formed in a state where a plurality of particles are gathered in the surface direction of the surface of the first hard coat layer.
- the protruding portion is preferably formed in a state where 10 or more particles are gathered in the surface direction of the surface of the first hard coat layer.
- the protrusion is formed in a state in which 20 or more particles are gathered in the surface direction of the surface of the first hard coat layer.
- the upper limit of the number of particles forming the protrusion is not particularly limited, but about 1000 is appropriate.
- the protrusion is formed in a state where 10 or more particles (more preferably 20 or more particles) are gathered in the surface direction of the surface of the first hard coat layer, and the protrusion is the first. It is preferable to exist at a density of 1 or more per 4 ⁇ m square on the surface of one hard coat layer. According to this aspect, it is possible to achieve good transparency and further improved blocking resistance.
- FIG. 3 is a surface photograph of the surface of the first hard coat layer in the hard coat film of the present invention by a scanning electron microscope (SEM).
- SEM scanning electron microscope
- the length (L) of the protrusion is preferably 0.4 ⁇ m or more.
- the length (L) of the protruding portion is the maximum linear length of the protruding portion.
- the symbol L in FIG. 2 is the length (L) of the protrusion.
- the length (L) of the protruding portion is preferably 0.5 ⁇ m or more, more preferably 0.7 ⁇ m or more, and particularly preferably 1.0 ⁇ m or more.
- the upper limit of the length (L) of the protrusion is not particularly limited, but about 10 ⁇ m is appropriate.
- the protrusion having a length (L) of 0.4 ⁇ m or more (preferably 0.5 ⁇ m or more, more preferably 0.7 ⁇ m or more, particularly preferably 1.0 ⁇ m or more) It is preferable to exist at a density of 1 or more per 4 ⁇ m square on the surface of one hard coat layer. According to this aspect, it is possible to achieve good transparency and further improved blocking resistance.
- the height (T) of the protruding portion is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and particularly preferably 0.03 ⁇ m or more from the viewpoint of improving the blocking resistance.
- the upper limit of the height (T) of the protrusion is preferably 0.3 ⁇ m or less, more preferably 0.2 ⁇ m or less, and particularly preferably 0.1 ⁇ m or less from the viewpoint of suppressing an increase in haze value.
- the height (T) of the protruding portion is a vertical distance from the surface of the first hard coat layer to the highest portion of the protruding portion (reference numeral T in FIG. 1).
- the height (T) of the protrusion can be measured from a cross-sectional photograph taken with a transmission electron microscope (TEM) or a scanning electron microscope (SEM) of the first hard coat layer.
- the first hard coat layer a plurality of particles having an average particle diameter (r: ⁇ m) of less than 0.5 ⁇ m and 0.5 times or less with respect to the thickness (d: ⁇ m) of the first hard coat layer are gathered.
- the average particle diameter (r: ⁇ m) of the particles forming the particle aggregate is less than 0.5 ⁇ m
- the average particle diameter (r: ⁇ m) of the particles and the first hard coat layer It is important to satisfy two conditions that the ratio (r / d) of the thickness (d: ⁇ m) is 0.5 or less.
- the haze value increases even when the ratio (r / d) is 0.5 or less, and the average particle size of the particles is less than 0.5 ⁇ m.
- the ratio (r / d) exceeds 0.5, the haze value increases, and the transparency of the hard coat film decreases.
- Such particles having a small average particle diameter and aggregates of these particles are likely to float near the surface of the first hard coat layer by surface treatment described later, and the particle aggregates are unevenly distributed near the surface of the first hard coat layer. It becomes easy to let you. As a result, the blocking resistance is improved. Further, by using such particles having a small average particle diameter, an increase in the haze value of the hard coat layer is suppressed, and a hard coat film having good transparency can be obtained.
- the individual particles for forming the particle aggregate are observed by a scanning electron microscope (SEM) on the surface of the first hard coat layer, or a scanning electron microscope (SEM) of the first hard coat layer cross section.
- SEM scanning electron microscope
- SEM scanning electron microscope
- TEM transmission electron microscope
- the individual particles for forming the particle aggregate are in the form of primary particles or secondary particles in which a plurality of primary particles are closely aggregated (a form in which the primary particles cannot be discriminated so densely). ) Can be taken.
- FIG. 4 is a diagram schematically showing individual particles forming the particle aggregate.
- the particle aggregate 10 is formed of secondary particles 1a and primary particles 1b in which a plurality of primary particles are densely aggregated into one lump.
- the individual particles forming the particle aggregate 10 are secondary particles 1a and primary particles 1b.
- the secondary particles 1a are agglomerated so densely that the primary particles cannot be discriminated into one lump.
- the chain colloidal silica which will be described later, has a substantially spherical primary particle combined (connected) to form a chain-like particle aggregate, and the individual primary particles can be distinguished almost clearly.
- the individual particles in are primary particles.
- the average particle diameter (r: ⁇ m) of the particles is measured from a cross-sectional photograph taken with a transmission electron microscope (TEM) or a scanning electron microscope (SEM) of the first hard coat layer. .
- TEM transmission electron microscope
- SEM scanning electron microscope
- the ratio (r / d) of the average particle diameter (r: ⁇ m) of the particles to the thickness (d: ⁇ m) of the first hard coat layer is preferably from the above viewpoint (improvement of good transparency and blocking resistance). Is 0.4 or less, more preferably 0.3 or less, and particularly preferably 0.2 or less.
- the lower limit ratio (r / d) is preferably 0.005 or more, more preferably 0.01 or more, and particularly preferably 0.02 or more, since blocking resistance decreases when it is too small.
- the average particle diameter (r: ⁇ m) of the particles is preferably less than 0.4 ⁇ m, more preferably less than 0.3 ⁇ m, and particularly preferably less than 0.2 ⁇ m.
- the lower limit is preferably 0.005 ⁇ m or more, and particularly preferably 0.01 ⁇ m or more.
- the average particle diameter (r: ⁇ m) of the particles is preferably 0.01 ⁇ m or more and less than 0.4 ⁇ m.
- the thickness (d: ⁇ m) of the first hard coat layer is preferably 0.5 ⁇ m or more, more preferably 0.8 ⁇ m or more, and particularly preferably 0.9 ⁇ m or more from the viewpoint of ensuring high hardness.
- the pencil hardness (JIS K5600-5-4 (1999)) of the first hard coat layer is preferably F or higher, more preferably H or higher.
- the upper limit is about 9H.
- the upper limit thickness of the first hard coat layer is preferably less than 4.0 ⁇ m from the viewpoint that the particle aggregate is unevenly distributed in the vicinity of the surface of the first hard coat layer and the protruding portion is efficiently formed. Is preferably less than 2.0 ⁇ m, particularly preferably less than 2.0 ⁇ m, and most preferably less than 1.7 ⁇ m.
- the thickness (d: ⁇ m) of the first hard coat layer is preferably 0.5 ⁇ m or more and less than 4 ⁇ m.
- the first hard coat layer contains a particle aggregate.
- the particles for forming such a particle aggregate include organic particles and inorganic particles.
- an acrylic resin As the resin constituting the organic particles, an acrylic resin, a styrene resin, a polyester resin, a polyurethane resin, a polycarbonate resin, a polyamide resin, a silicone resin, a fluorine resin, or 2 used for the synthesis of the above resin.
- examples thereof include copolymer resins of more than one type of monomer.
- acrylic resin particles are preferably used.
- acrylic resin particles acrylic resin particles, methacrylic resin particles, acrylic monomers or methacrylic monomers and other monomers (for example, styrene, urethane acrylate, urethane methacrylate, polyester acrylate, polyester) And copolymer resin particles such as methacrylate, silicone acrylate, and silicone methacrylate).
- organic particles are preferably synthesized by an emulsion polymerization method, and organic particles having an average particle diameter of less than 0.5 ⁇ m can be obtained by synthesis by an emulsion polymerization method.
- the inorganic particles include inorganic particles such as silica, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, and zeolite. Among these, silica particles are preferable.
- the content of the particles to be contained in the first hard coat layer is preferably 3% by mass or more with respect to 100% by mass of the total solid content of the first hard coat layer from the viewpoint of forming a protrusion effective for blocking resistance. 5 mass% or more is more preferable, and 7 mass% or more is especially preferable.
- the upper limit content is preferably less than 30% by mass, more preferably less than 25% by mass, and particularly preferably less than 20% by mass from the viewpoint of suppressing an increase in the haze value of the hard coat layer.
- a plurality of particles having an average particle diameter (r: ⁇ m) of less than 0.5 ⁇ m and not more than 0.5 times the thickness (d: ⁇ m) of the first hard coat layer are collected on the surface of the first hard coat layer.
- a relatively large amount of the particle aggregate is present near the surface of the first hard coat layer (ie, uneven distribution).
- the method (1) As a method for causing a relatively large amount of particle aggregates to be present in the vicinity of the surface of the first hard coat layer, in the formation process (application process, drying process, curing process) of the first hard coat layer, (1) Method of moving (floating) near the surface of the hard coat layer, or (2) Method of moving particles (floating) near the surface of the first hard coat layer or forming a particle aggregate after moving (floating) Is mentioned.
- the method (1) is preferable because the particle aggregate can be efficiently moved (floated) near the surface of the first hard coat layer.
- particles or particle aggregates subjected to surface treatment for reducing surface free energy or surface treatment with a surfactant are used. It is preferable to use a body.
- the first hard coat layer comprises (i) a particle aggregate comprising particles subjected to surface treatment for reducing surface free energy or surface treatment with a surfactant and / or (ii) It contains a particle aggregate that has been subjected to a surface treatment for reducing the surface free energy or a surface treatment with a surfactant.
- surface treatment means a surface treatment for reducing the above-mentioned surface free energy or a surface treatment with a surfactant unless otherwise specified. Further, this surface treatment is sometimes referred to as “surface treatment of the present invention”.
- inorganic particles and inorganic particle aggregates are preferable, and silica particles and silica particle aggregates are particularly preferable.
- Silica particles and silica particle aggregates are preferable because they usually have a silanol group on the surface and are easily surface treated. Details of the surface treatment will be described later.
- the particles are preferably silica particles, and the silica particles or the silica particle aggregate is preferably subjected to a surface treatment for reducing the surface free energy or a surface treatment with a surfactant.
- Silica particles are roughly classified into wet method silica and gas phase method silica.
- silica particles often refer to wet-process silica.
- Wet process silica includes silica sol obtained through metathesis by sodium silicate acid and ion exchange resin layer, colloidal silica obtained by heating and aging this silica sol, silica gel obtained by gelling this silica sol (change the production conditions)
- silica gel obtained by gelling this silica sol (change the production conditions)
- three-dimensional secondary particles in which primary particles of several ⁇ m to 10 ⁇ m have siloxane bonds are known.
- Vapor phase silica is also called a dry method with respect to the above wet method, and is generally made by a flame hydrolysis method.
- a method of making silicon tetrachloride by burning with hydrogen and oxygen is generally known, but silanes such as methyltrichlorosilane and trichlorosilane can be used alone or silicon tetrachloride instead of silicon tetrachloride. Can be used in a mixed state.
- silica particles preferably used in the present invention include colloidal silica.
- the average primary particle size of the colloidal silica is preferably less than 100 nm, more preferably less than 80 nm, and particularly preferably less than 70 nm.
- the lower limit of the average primary particle diameter is preferably 5 nm or more, and more preferably 10 nm or more.
- Colloidal silica is generally commercially available and can be obtained.
- Examples of commercially available products include the “organosilica sol” series manufactured by Nissan Chemical Industries, Ltd., the “Adelite AT” series manufactured by Asahi Denka Kogyo Co., Ltd., the “Crebosol” series manufactured by Clariant Japan Co., Ltd., and DuPont Co., Ltd. ) “Ludox” series manufactured by Fuso, and “Quartron PL” series manufactured by Fuso Chemical Industry Co., Ltd.
- colloidal silica tends to aggregate or aggregate in a hard coat layer coating solution to form a particle aggregate.
- colloidal silica particle aggregate that has not been surface-treated does not move (float) in the vicinity of the surface of the hard coat layer, it is impossible to efficiently form protrusions due to the particle aggregate on the surface of the hard coat layer.
- colloidal silica when colloidal silica is used as the silica particles, it is preferable to prepare a particle aggregate of colloidal silica and subject the particle aggregate to a surface treatment in advance before adding the colloidal silica to the hard coat layer coating solution. . Colloidal silica that has been subjected to surface treatment is less likely to agglomerate or bond, making it difficult to form a particle aggregate.
- Methods for preparing particle aggregates by aggregating or bonding colloidal silica include electrolytes (eg, citrate, tartrate, sulfate, acetate, chloride, bromide, nitrate, iodide, sodium carboxymethylcellulose, alginic acid Sodium, etc.), nonionic polymers (eg, polyvinyl alcohol, methylcellulose, etc.), polymer flocculants (eg, acrylic acid, acrylamide, sodium acrylate, dimethylaminoethyl methacrylate) A polymer flocculant composed of a polymer of a monomer, etc.), a method of adjusting pH by adding an acid or a base, a dehydrating agent (for example, alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol). Of adding quaternary ammonium salt , Or addition of a thione surfactants.
- electrolytes eg, citrate, tartrate, sulfate,
- a colloidal silica aggregate in which colloidal silica is secondarily bonded in a chain shape can be used.
- the average primary particle diameter of colloidal silica for forming this chain colloidal silica aggregate is preferably less than 100 nm, more preferably less than 80 nm, and particularly preferably less than 70 nm.
- the lower limit of the average primary particle diameter is preferably 5 nm or more, and more preferably 10 nm or more.
- the chain colloidal silica aggregate is preferably subjected to a surface treatment.
- Chain colloidal silica aggregates are commercially available from Nissan Chemical Industries, Ltd. as organosilica sols IPA-ST-UP, MEK-ST-UP, MA-ST-UP, etc., and these chain colloidal silicas are available. It is preferable to use the aggregate after subjecting it to a surface treatment.
- the average primary particle size of the vapor phase silica is preferably less than 100 nm, more preferably less than 80 nm, and particularly preferably less than 70 nm.
- the lower limit of the average primary particle diameter is preferably 5 nm or more, and more preferably 10 nm or more.
- Vapor phase silica is also called dry silica or fumed silica, and is commercially available, for example, as “Aerosil” from Nippon Aerosil Co., Ltd. and as “Leoseal” from Tokuyama Co., Ltd.
- Vapor phase silica is less susceptible to loose agglomeration due to the lower density of silanol groups on the particle surface than wet method silica, and the primary or secondary particles are linked in a network structure or chain. It is characterized by being easily present in an agglomerated state. Therefore, a moderately sized particle aggregate can be obtained by appropriately pulverizing or dispersing the vapor phase silica in a solvent. Then, by subjecting this gas phase method silica particle aggregate to surface treatment, it can be moved (floated) to the vicinity of the surface of the first hard coat layer to be unevenly distributed.
- a bead mill As a device for pulverizing or dispersing vapor phase silica in a solvent, a bead mill, a paint shaker, a roll mill, a ball mill, an attritor, a sand mill, a jet mill, a hammer mill, a turbo mill, an ultrasonic disperser, an optimizer, a nanomizer, a disper,
- a disperser having a stirring blade such as a turbine blade
- a pressure disperser such as a high-pressure homogenizer, and an ultrahigh-pressure homogenizer
- a thin film-circulating disperser As a device for pulverizing or dispersing vapor phase silica in a solvent, a bead mill, a paint shaker, a roll mill, a ball mill, an attritor, a sand mill, a jet mill, a hammer mill, a turbo mill, an ultrasonic disperser, an optimizer, a
- an organosilane compound having a fluorine atom represented by the following general formula (1), a hydrolyzate of the organosilane, and the organo As the surface treatment for reducing the surface free energy of the particles or the particle aggregate, an organosilane compound having a fluorine atom represented by the following general formula (1), a hydrolyzate of the organosilane, and the organo
- the method of surface-treating with the at least 1 compound chosen from the group which consists of the partial condensate of the hydrolyzate of silane is mentioned.
- n represents an integer of 1 to 10
- m represents an integer of 1 to 5.
- Q represents an alkoxy group having 1 to 5 carbon atoms or a halogen atom).
- the surface is treated with a compound represented by the following general formula (2) and further a fluorine compound represented by the following general formula (3).
- the method of processing is mentioned.
- B and D each independently represent a reactive site
- R 4 and R 7 are each independently derived from an alkylene group having 1 to 3 carbon atoms, or the alkylene group.
- R 5 and R 6 each independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms
- Rf 2 represents a fluoroalkyl group
- n represents an integer of 0 to 2.
- Examples of the reactive site represented by B and D include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an epoxy group, a carboxyl group, and a hydroxyl group.
- Specific examples of the general formula (2) include acryloxyethyltrialkoxysilane, acryloxypropyltrialkoxysilane, Acryloxybutyltrialkoxysilane, acryloxypentyltrialkoxysilane, acryloxyhexyltrialkoxysilane, acryloxyheptyltrialkoxysilane, methacryloxyethyltrialkoxysilane, methacryloxypropyltrialkoxysilane, methacryloxybutyltrialkoxysilane, methacryloxybutyl Examples thereof include loxyhexyltrialkoxysilane, methacryloxyheptyltrialkoxysilane, methacryloxypropylmethyl dialkoxysilane, methacryloxypropylmethyl dialkoxysilane, and compounds containing a compound in which an alkoxy group in these compounds is substituted with a hydroxyl group.
- examples of the alkoxy group include a me
- Specific examples of the general formula (3) include 2,2,2-trifluoroethyl acrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2-perfluorobutylethyl acrylate, 3-perfluoro Butyl-2-hydroxypropyl acrylate, 2-perfluorohexylethyl acrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, perfluorooctylmethyl acrylate, 2-perfluorooctylethyl acrylate, 3-perfluorooctyl-2- Hydroxypropyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluoro-3-methylbutylethyl acrylate, 3-perfluoro-3-methoxybutyl-2-hydroxypropyl acrylate, 2-perf Oro-5-methylhexyl ethyl acrylate, 3-perfluoro-5-methylhexyl-2-
- a surfactant having an ethyleneoxy group in the molecule is preferably used.
- examples of such surfactants include the following compounds.
- Cationic surfactants for example, octyl dimethyl ethyl ammonium ethyl sulfate, lauryl dimethyl ethyl ammonium ethyl sulfate, valmityl dimethyl ethyl ammonium ethyl sulfate, stearyl dimethyl hydroxyethyl ammonium paratoluene sulfonate, etc.
- Anionic surfactants for example, polyoxyethylene alkyl ether phosphates, polyoxyalkylene alkyl ether phosphates, polyoxyalkylene alkyl phenyl ether phosphates, polyoxyethylene tridecyl ether phosphates, polyoxyethylene Alkyl ether phosphate ester, polyoxyethylene alkyl ether phosphate monoethanolamine salt, polyoxyethylene lauryl ether phosphate ester, polyoxyethylene trilauryl ether phosphate monoethanolamine salt, polyoxyethylene styrenated phenyl ether phosphate Acid ester, sodium polyoxyethylene lauryl ether acetate, polyoxyethylene sulfosuccinate lauryl disodium, polyoxyethylene Alkylsulfosuccinate disodium, polyoxystyrenated phenyl ether ammonium sulfate, polyoxyalkylene branched sodium decyl ether sulfate, polyoxyethylene isodecyl
- the first hard coat layer preferably contains a thermosetting resin or an active energy ray curable resin as a resin, and particularly preferably contains an active energy ray curable resin.
- the active energy ray-curable resin means a resin that is polymerized and cured by active energy rays such as ultraviolet rays and electron beams.
- a compound (monomer or oligomer) having a polymerizable functional group such as acryloyl group, methacryloyl group, acryloyloxy group, methacryloyloxy group, vinyl group, and allyl group.
- the first hard coat layer is coated with the active energy ray-curable composition containing the polymerizable compound and the above-described particles or particle aggregate by a wet coating method, dried as necessary, and then irradiated with active energy rays. Then, it is preferably formed by curing.
- a coating method such as a reverse coating method, a spray coating method, a bar coating method, a gravure coating method, a rod coating method, a die coating method, a spin coating method or an extrusion coating method can be used.
- Active energy rays include ultraviolet rays, visible rays, infrared rays, electron beams, rays, ⁇ rays, ⁇ rays and the like. Among these active energy rays, ultraviolet rays and electron beams are preferable, and ultraviolet rays are particularly preferably used.
- an ultraviolet fluorescent lamp for irradiating an ultraviolet-ray
- a low pressure mercury lamp for example, an ultraviolet fluorescent lamp, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp etc.
- An ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation, or the like can also be used.
- an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp are preferably used.
- an atmosphere having a low oxygen concentration for example, an atmosphere having an oxygen concentration of 500 ppm or less because it can be cured efficiently.
- Irradiation light amount of the ultraviolet rays is preferably from 50 mJ / cm 2 or more, 100 mJ / cm 2 or more, and particularly 150 mJ / cm 2 or more.
- the upper limit is preferably 2000 mJ / cm 2 or less, and more preferably 1000 mJ / cm 2 or less.
- ... (Meth) acrylate includes two compounds “... acrylate” and “... methacrylate”.
- Examples of the monomer include methyl (meth) acrylate, lauryl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl ( Monofunctional acrylates such as (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythrito Rutetra (meth) acrylate, dipentaerythritol tri
- polyfunctional monomers having 3 or more polymerizable functional groups in one molecule are preferably used.
- oligomer examples include polyester (meth) acrylate, polyurethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, alkit (meth) acrylate, melamine (meth) acrylate, and silicone (meth) acrylate. be able to.
- polyfunctional urethane (meth) acrylate oligomers having 3 or more polymerizable functional groups in one molecule are preferably used.
- a polyfunctional urethane (meth) acrylate oligomer a commercially available product can be used.
- the content of the polymerizable compound in the active energy ray-curable composition is preferably 50% by mass or more and 55% by mass or more with respect to 100% by mass of the total solid content of the active energy ray-curable composition. More preferably, it is more preferably 60% by mass or more, and particularly preferably 70% by mass or more.
- the upper limit is preferably 97% by mass or less, more preferably 95% by mass or less, and particularly preferably 90% by mass or less.
- the active energy ray curable composition preferably contains a photopolymerization initiator.
- the photopolymerization initiator include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4′-dichlorobenzophenone, 4,4′-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methyl benzoylformate, p-isopropyl- ⁇ -hydroxyisobutylphenone, ⁇ -hydroxyisobutylphenone, 2, Carbonyl compounds such as 2-dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexyl phenyl ket
- photopolymerization initiators are generally commercially available and can be used.
- Irgacure registered trademark
- Irgacure 907 Irgacure 379
- Irgacure 819 Irgacure 127
- Irgacure 500 Irgacure 754
- Irgacure 250 Irgacure 1800
- Irgacure 1870 Irgacure OXEDA
- ROCIA OXEDA manufactured by Ciba Specialty Chemicals Co., Ltd.
- the range of the content of the photopolymerization initiator is suitably in the range of 0.1 to 10% by mass with respect to 100% by mass of the total solid content of the active energy ray-curable composition, and 0.5 to 8% by mass.
- the range of is preferable.
- the active energy ray-curable composition can further contain various additives such as an antioxidant, an ultraviolet absorber, a leveling agent, an organic antistatic agent, a colorant, and a pigment.
- the surface of the first hard coat layer has a protruding portion.
- the surface of the first hard coat layer is preferably relatively smooth from the viewpoint of reducing the haze value of the hard coat film. That is, the center line average roughness (Ra1) on the surface of the first hard coat layer is preferably 25 nm or less.
- the center line average roughness (Ra1) on the surface of the coat layer can be controlled to 25 nm or less.
- the center line average roughness (Ra1) of the first hard coat layer surface is further preferably 20 nm or less, more preferably 18 nm or less, particularly preferably 15 nm or less, and most preferably 13 nm or less.
- the lower limit center line average roughness (Ra1) is preferably 3 nm or more, preferably 5 nm. The above is more preferable.
- the refractive index range of the first hard coat layer is preferably from 1.48 to 1.54, more preferably from 1.50 to 1.54.
- the active energy ray-curable composition described above is applied by a wet coating method, dried as necessary, and then irradiated with active energy rays to form a first hard coat layer, whereby the refractive index is reduced.
- a first hard coat layer in the range of 1.48 to 1.54 can be obtained.
- the refractive index of the first hard coat layer and the refractive indexes of the base film, resin layer, second hard coat layer, and refractive index adjustment layer described below are wavelengths 589 nm unless otherwise specified.
- the base film of the present invention is preferably a plastic film.
- the material constituting the base film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyimide, polyphenylene sulfide, aramid, polypropylene, polyethylene, polylactic acid, polyvinyl chloride, polycarbonate, and polymethacrylic.
- polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyimide, polyphenylene sulfide, aramid, polypropylene, polyethylene, polylactic acid, polyvinyl chloride, polycarbonate, and polymethacrylic.
- Examples include methyl acid, alicyclic acrylic resin, cycloolefin resin, triacetyl cellulose, and those obtained by mixing and / or copolymerizing these resins.
- a film obtained by unstretching, uniaxially stretching, or biaxially stretching these resins can be used as
- polyester films are preferred because of their excellent transparency, dimensional stability, mechanical properties, heat resistance, electrical properties, chemical resistance, etc., and particularly polyethylene terephthalate films (PET films).
- PET films polyethylene terephthalate films
- a biaxially stretched PET film is preferably used.
- the thickness of the substrate film is suitably in the range of 20 to 300 ⁇ m, preferably in the range of 30 to 200 ⁇ m, and more preferably in the range of 50 to 150 ⁇ m.
- the base film preferably has at least a resin layer as shown below on the surface on which the first hard coat layer is laminated. That is, it is preferable that the hard coat film of this invention has the resin layer shown below between a base film and a 1st hard coat layer.
- the base film is preferably provided with a resin layer on at least the surface on which the first hard coat layer is laminated.
- the resin layer is a layer containing a resin as a main component. Specifically, the resin layer contains 50% by mass or more of resin with respect to 100% by mass of the total solid content of the resin layer.
- the resin forming the resin layer include polyester resin, acrylic resin, urethane resin, polycarbonate resin, epoxy resin, alkyd resin, urea resin, and the like. These resins can be used alone or in combination.
- the resin layer is interposed between the base film and the first hard coat layer, and from the viewpoint of improving the adhesion between the base film and the first hard coat layer, the resin is a polyester resin, an acrylic resin, and a polyurethane resin. It is preferable to contain at least one selected from the group consisting of In particular, the resin layer preferably contains at least a polyester resin as a resin.
- the resin content in the resin layer is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more with respect to 100% by mass of the total solid content of the resin layer.
- the resin content in the resin layer is preferably 95% by mass or less, and more preferably 90% by mass or less.
- the resin layer may be formed in a two-layer configuration.
- a first resin layer mainly composed of a polyester resin and a second resin layer mainly composed of an acrylic resin are sequentially formed from the base film side. Details of the two-layer configuration will be described later.
- the resin layer preferably contains particles from the viewpoint of ensuring appropriate slipping and winding properties in the manufacturing process of the hard coat film.
- the particles contained in the resin layer are not particularly limited, but inorganic particles such as silica particles, titanium oxide, aluminum oxide, zirconium oxide, calcium carbonate, zeolite particles, acrylic particles, silicone particles, polyimide particles, Teflon (registered trademark) ) Organic particles such as particles, crosslinked polyester particles, crosslinked polystyrene particles, crosslinked polymer particles, and core-shell particles.
- silica particles are preferable, and colloidal silica is particularly preferable.
- the particles contained in the resin layer preferably have an average particle size larger than the thickness of the resin layer.
- the average particle diameter is preferably 1.3 times or more of the thickness of the resin layer, more preferably 1.5 times or more, and particularly preferably 2.0 times or more.
- the upper limit is preferably 20 times or less, more preferably 15 times or less, and particularly preferably 10 times or less.
- the average particle size of the particles contained in the resin layer is appropriately selected according to the thickness design of the resin layer. Specifically, the average particle size is preferably in the range of 0.02 to 1 ⁇ m, 0.05 The range of -0.7 ⁇ m is more preferable, and the range of 0.1-0.5 ⁇ m is particularly preferable. If the average particle size is less than 0.02 ⁇ m, the slipperiness may be lowered. If the average particle diameter exceeds 1 ⁇ m, the particles may fall off, the transparency may be lowered, or the appearance may be deteriorated.
- the thickness range of the resin layer is preferably in the range of 0.005 to 0.3 ⁇ m.
- the thickness of the resin layer is less than 0.005 ⁇ m, the adhesion between the base film and the first hard coat layer is lowered.
- the thickness of the resin layer is larger than 0.3 ⁇ m, the blocking resistance after the first hard coat layer is laminated may be lowered.
- the resin layer is comprised by multiple layers, let the total thickness of multiple layers be the thickness of a resin layer.
- the thickness of the resin layer is further preferably 0.01 ⁇ m or more, more preferably 0.015 ⁇ m or more, and particularly preferably 0.02 ⁇ m or more. Regarding the upper limit, the thickness of the resin layer is preferably 0.25 ⁇ m or less, preferably 0.2 ⁇ m or less, particularly preferably 0.15 ⁇ m or less.
- the range of the content of the particles in the resin layer is preferably in the range of 0.05 to 10% by mass, more preferably in the range of 0.1 to 8% by mass, particularly 0% to 100% by mass of the total solid content of the resin layer.
- the range of 5 to 5% by mass is preferable.
- the content of the particles in the resin layer is less than 0.05% by mass, good slipperiness may not be obtained.
- the content of the particles exceeds 10% by mass, the transparency may be lowered, The applicability of the 1 hard coat layer may deteriorate, or the adhesion between the base film and the first hard coat layer may deteriorate.
- the resin layer preferably further contains a crosslinking agent.
- the resin layer is preferably a thermosetting layer containing the above-described resin and a crosslinking agent.
- the conditions (heating temperature, time) for thermosetting the resin layer are not particularly limited, but the heating temperature is preferably 70 ° C or higher, more preferably 100 ° C or higher, particularly preferably 150 ° C or higher, and most preferably 200 ° C or higher. .
- the heating temperature is preferably 300 ° C. or lower.
- the range of the heating time is preferably 5 to 300 seconds, and more preferably 10 to 200 seconds.
- crosslinking agent examples include melamine crosslinking agent, oxazoline crosslinking agent, carbodiimide crosslinking agent, isocyanate crosslinking agent, aziridine crosslinking agent, epoxy crosslinking agent, methylolated or alkylolized urea crosslinking agent, acrylamide
- examples thereof include system crosslinking agents, polyamide resins, amide epoxy compounds, various silane coupling agents, and various titanate coupling agents.
- laminic crosslinking agents, oxazoline crosslinking agents, carbodiimide crosslinking agents, isocyanate crosslinking agents, and aziridine crosslinking agents are preferable, and melamine crosslinking agents are particularly preferable.
- Examples of the melamine-based crosslinking agent include imino group type methylated melamine resin, methylol group type melamine resin, methylol group type methylated melamine resin, and fully alkyl type methylated melamine resin. Among these, imino group type melamine resins and methylolated melamine resins are preferably used.
- the range of the content of the crosslinking agent in the resin layer is preferably in the range of 0.5 to 40% by mass, more preferably in the range of 1 to 30% by mass, especially 2 to 2% with respect to 100% by mass of the solid content of the resin layer. A range of 20% by weight is preferred.
- the reflection color of the hard coat film obtained by laminating the first hard coat layer on the base film via the resin layer is preferably a neutral colorless hue.
- the range of the refractive index of the resin layer is preferably 1.55 to 1.61, and more preferably 1.56 to 1.60. A range of 1.57 to 1.59 is more preferable.
- the refractive index of a polyethylene terephthalate film is generally about 1.62 to 1.70, and by adjusting the refractive index of the resin layer to the above range (1.55 to 1.61), The reflected color can be close to neutral and colorless.
- the base film is a polyethylene terephthalate film having a refractive index of 1.62 to 1.70, and the refractive index is on at least one surface of the polyethylene terephthalate film (that is, on one surface or both surfaces).
- the first hard coat layer having a refractive index of 1.48 to 1.54 is preferably laminated through a resin layer having a thickness of 1.55 to 1.61.
- a polyester resin containing a naphthalene ring in the molecule is preferable to use as the resin.
- a polyester resin containing a naphthalene ring can be synthesized, for example, by using a polyvalent carboxylic acid such as 1,4-naphthalenedicarboxylic acid or 2,6-naphthalenedicarboxylic acid as a copolymerization component.
- the range of the content of the polyester resin containing a naphthalene ring in the molecule in the resin layer is preferably 5 to 70% by mass, more preferably 10 to 60% by mass with respect to 100% by mass of the total resin.
- the resin layer is applied on the base film by a wet coating method, and is thermoset and laminated. Furthermore, it is preferable that the resin layer is applied by a wet coating method in the manufacturing process of the base film, which is applied by a so-called in-line coating method, and is thermally cured and laminated. Examples of the wet coating method include a reverse coating method, a spray coating method, a bar coating method, a gravure coating method, a rod coating method, and a die coating method.
- a resin layer having a two-layer structure can be adopted.
- Such a two-layered resin layer is preferably formed by applying one coating solution once and causing self-phase separation in the drying process. That is, a coating liquid containing the main component (polyester resin) of the first resin layer and the main component (acrylic resin) of the second resin layer is applied, and self-phase separation of each component is utilized in the drying process. It is preferable to employ a method of forming the first resin layer and the second resin layer.
- the surface energy difference between the main component (polyester resin) of the first resin layer and the main component (acrylic resin) of the second resin layer it is preferable to increase the surface energy difference between the main component (polyester resin) of the first resin layer and the main component (acrylic resin) of the second resin layer. That is, it is preferable to use a polyester resin having a high surface energy and an acrylic resin having a low surface energy. In particular, it is preferable to use a polyester resin having a sulfonic acid group in order to increase the surface energy of the polyester resin.
- the thickness of the first resin layer is set from the viewpoint of enhancing the adhesion between the base film and the first hard coat layer and making the reflected color of the hard coat film close to neutral and colorless. It is preferable to be larger than the thickness of the two resin layers.
- the thickness of the first resin layer is preferably 1.5 times or more, more preferably 2.0 times or more, and particularly preferably 3.0 times or more the thickness of the second resin layer.
- the thickness range of the first resin layer is preferably 0.02 to 0.2 ⁇ m, more preferably 0.03 to 0.15 ⁇ m, and particularly preferably 0.05 to 0.12 ⁇ m. preferable.
- the thickness of the second resin layer is preferably in the range of 0.005 to 0.1 ⁇ m, more preferably in the range of 0.01 to 0.07 ⁇ m, and particularly preferably in the range of 0.01 to 0.05 ⁇ m.
- the hard coat film of the present invention has a first hard coat layer on at least one surface of the base film.
- the hard coat film may have a first hard coat layer only on one side of the base film, or may have a first hard coat layer on both sides of the base film.
- the hard coat film of the present invention preferably has a first hard coat layer on both sides of the base film. With this configuration, it is possible to further improve the blocking resistance while maintaining high transparency (small haze value). When providing a 1st hard-coat layer on both surfaces of a base film, it is preferable to provide a 1st hard-coat layer on both surfaces of a base film through the above-mentioned resin layer, respectively.
- the first hard coat layer is provided on one side of the base film, and the first hard of the base film (that is, the first hard of the base film).
- the first hard of the base film that is, the first hard of the base film.
- examples thereof include a hard coat film having a second hard coat layer (on the side opposite to the side on which the coat layer is provided).
- the hard coat film of the present invention is suitable as a base film of a transparent conductive film as will be described later. Since the transparent conductive film is required to have high transparency, the base film (hard coat film) preferably has a small haze value.
- the hard coat film of the present invention preferably has a haze value of 0.7% or less, more preferably 0.5% or less, and particularly preferably 0.3% or less.
- the lower haze value is preferably as small as possible, and is not particularly limited.
- the thickness of the second hard coat layer is preferably 0.5 ⁇ m or more, more preferably 0.8 ⁇ m or more, and particularly preferably 0.9 ⁇ m or more from the viewpoint of ensuring high hardness.
- the pencil hardness (JIS K5600-5-4 (1999)) of the second hard coat layer is preferably F or higher, more preferably H or higher.
- the upper limit is about 9H.
- the upper limit thickness of the second hard coat layer is preferably less than 4.0 ⁇ m, more preferably less than 3.0 ⁇ m, and particularly preferably less than 2.0 ⁇ m from the viewpoint of suppressing curling of the hard coat film.
- the surface of the second hard coat layer is preferably smooth and clear from the viewpoint of reducing the haze value of the hard coat film. That is, the center line average roughness (Ra2) of the surface of the second hard coat layer is preferably 20 nm or less, more preferably 15 nm or less, and particularly preferably 13 nm or less. The lower limit is not particularly limited, but is practically about 0.1 nm.
- the second hard coat layer has a center line average roughness (Ra2) of 20 nm or less on the surface of the second hard coat layer
- the second hard coat layer substantially contains particles having an average particle diameter of 0.5 ⁇ m or more. It is preferable not to contain.
- the fact that the second hard coat layer does not substantially contain particles having an average particle diameter of 0.5 ⁇ m or more means that the coating liquid for forming the second hard coat layer (for example, active energy ray curable) is used. It means that particles having an average particle size of 0.5 ⁇ m or more are not intentionally added to the composition.
- grains contained in a 2nd hard-coat layer is calculated
- the second hard coat layer preferably has no protrusions due to particles or particle aggregates on the surface thereof.
- the second hard coat layer can contain particles having an average particle size of less than 0.5 ⁇ m, but it is preferable to adjust the average particle size of the particles contained in the second hard coat layer from the above viewpoint.
- the average particle diameter of the particles is preferably 0.2 ⁇ m or less, and more preferably 0.1 ⁇ m or less.
- the content of such particles is suitably in the range of 0.1 to 15% by mass, more preferably in the range of 0.5 to 10% by mass with respect to 100% by mass of the total solid content of the second hard coat layer. In particular, the range of 1 to 8% by mass is preferable.
- the second hard coat layer does not contain any particles.
- the second hard coat layer preferably contains a thermosetting resin or an active energy ray curable resin as the resin, and particularly preferably contains an active energy ray curable resin.
- the active energy ray-curable resin means a resin that is polymerized and cured by active energy rays such as ultraviolet rays and electron beams.
- the same compounds as those described in the first hard coat layer can be used. Further, the content of the active energy ray-curable resin is the same as the content in the first hard coat layer.
- the second hard coat layer is coated with an active energy ray-curable composition containing a polymerizable compound by a wet coating method, dried as necessary, and then irradiated with active energy rays. It is preferably formed by curing.
- the active energy ray-curable composition for forming the second hard coat layer preferably contains a photopolymerization initiator.
- a photopolymerization initiator the same photopolymerization initiator as that contained in the active energy ray-curable composition for forming the first hard coat layer described above can be used.
- the content of the photopolymerization initiator is the same as the content in the active energy ray-curable composition for forming the first hard coat layer.
- the refractive index range of the second hard coat layer is preferably in the range of 1.48 to 1.54, more preferably in the range of 1.50 to 1.54.
- the second hard coat layer is formed by applying the active energy ray-curable composition described above by a wet coating method, drying it as necessary, and then irradiating and curing with an active energy ray, whereby the refractive index. Can be obtained in the range of 1.48 to 1.54.
- the range of the refractive index of the resin layer provided between the base film and the second hard coat layer is preferably in the range of 1.55 to 1.61, more preferably in the range of 1.56 to 1.60.
- the range of .57 to 1.59 is particularly preferred. This makes it possible to bring the reflected color of the hard coat film closer to neutral colorlessness.
- a refractive index is provided on one surface of a polyethylene terephthalate film having a refractive index of 1.62 to 1.70 via a resin layer having a refractive index of 1.55 to 1.61.
- the first hard coat layer having a refractive index of 1.48 to 1.54 is laminated, and the refractive index is 1.5 through the resin layer having a refractive index of 1.55 to 1.61 on the other surface of the polyethylene terephthalate film.
- An embodiment in which a second hard coat layer of 48 to 1.54 is laminated is mentioned.
- the transparent conductive film in which the transparent conductive film patterned through the refractive index adjustment layer described later is formed on at least one hard coat layer of the preferable hard coat film is a patterned transparent conductive film.
- the so-called “bone appearance” in which the pattern portion of the film is visually recognized is effectively suppressed.
- the hard coat film of the present invention is suitable as a base film for a transparent conductive film. That is, the transparent conductive film using the hard coat film of the present invention as a base film is obtained by laminating a transparent conductive film on at least one surface of the hard coat film of the present invention.
- the transparent conductive film may be laminated on only one side of the hard coat film of the present invention, or may be laminated on both sides.
- i) or iii) is preferable. That is, from the viewpoint of ensuring the blocking resistance of the hard coat film in the transparent conductive film laminating step and processing step, it is preferable to expose the first hard coat layer without laminating the transparent conductive film.
- the hard coat layer on the surface on which the transparent conductive film is laminated is relatively smooth and clear. Therefore, in the configuration example i) or iii), the center line average roughness Ra1 of the surface of the first hard coat layer or the center line average roughness Ra2 of the surface of the second hard coat layer is preferably 20 nm or less, more preferably 15 nm or less. Particularly preferred is 13 nm or less.
- Transparent conductive film examples of the material for forming the transparent conductive film include tin oxide, indium oxide, antimony oxide, zinc oxide, ITO (indium tin oxide), ATO (antimony tin oxide), and other metal oxides, metal nanowires (for example, silver nanowires). Wire) and carbon nanotubes.
- ITO is preferably used.
- the thickness of the transparent conductive film is preferably 8 nm or more, and more preferably 10 nm or more, from the viewpoint of ensuring good conductivity with a surface resistance value of 10 3 ⁇ / ⁇ or less.
- the upper limit of the thickness of the transparent conductive film is preferably 60 nm or less. 50 nm or less is more preferable, and 40 nm or less is particularly preferable.
- the method for forming the transparent conductive film is not particularly limited, and a conventionally known method can be used. Specifically, a dry film forming method (vapor phase film forming method) such as a vacuum vapor deposition method, a sputtering method, an ion plating method, or a wet coating method can be used.
- the transparent conductive film formed as described above may be patterned.
- the patterning can form various patterns depending on the application to which the transparent conductive film is applied.
- the pattern portion the portion where the transparent conductive film is laminated on the surface of the hard coat film
- the non-pattern portion the portion where the transparent conductive film is not laminated on the surface of the hard coat film
- examples of the shape of the pattern portion include a stripe shape and a lattice shape.
- the patterning of the transparent conductive film is generally performed by etching.
- a transparent conductive film is patterned by forming a patterned etching resist film on the transparent conductive film by a photolithography method, a laser exposure method, or a printing method and then performing an etching process. After the transparent conductive film is patterned, the etching resist film is peeled off with an alkaline aqueous solution.
- etching liquid A conventionally well-known thing is used as an etching liquid.
- inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, nitric acid and phosphoric acid, organic acids such as acetic acid, and mixtures thereof, and aqueous solutions thereof are used.
- Examples of the alkaline aqueous solution used for stripping and removing the etching resist film include 1 to 5% by mass of a sodium hydroxide aqueous solution and a potassium hydroxide aqueous solution.
- the transparent conductive film may be directly laminated on the first hard coat layer or the second hard coat layer.
- the transparent conductive film and the first hard coat layer or the second hard coat layer may be laminated. It is preferable to interpose a refractive index adjusting layer between the coat layer.
- the refractive index adjustment layer will be described.
- the refractive index adjusting layer may be composed of only one layer or may be a laminated structure of two or more layers.
- the refractive index adjustment layer has a function for adjusting the reflection color and transmission color of the transparent conductive film laminated thereon, or a so-called “bone appearance” in which the patterned portion of the patterned transparent conductive film is visually recognized. It is a layer having a function to suppress.
- the refractive index adjusting layer for example, one layer configuration of a high refractive index layer having a refractive index of 1.60 to 1.80, and one layer configuration of a low refractive index layer having a refractive index of 1.30 to 1.55 Or the laminated structure of the said high refractive index layer and a low refractive index layer (low refractive index layer arrange
- the refractive index of the high refractive index layer is preferably in the range of 1.63 to 1.78, more preferably in the range of 1.65 to 1.75.
- the refractive index of the low refractive index layer is further preferably in the range of 1.35 to 1.53, and more preferably in the range of 1.40 to 1.51.
- the thickness of the refractive index adjusting layer (referring to the total thickness in the case of a multilayer structure) is preferably 0.2 ⁇ m or less, more preferably 0.15 ⁇ m or less, particularly preferably 0.12 ⁇ m or less, and 0.1 ⁇ m or less. Most preferred.
- the lower limit thickness is preferably 0.03 ⁇ m or more, more preferably 0.04 ⁇ m or more, particularly preferably 0.05 ⁇ m or more, and most preferably 0.06 ⁇ m or more.
- an active energy ray-curable composition containing metal oxide fine particles having a refractive index of 1.65 or more is applied by a wet coating method, dried as necessary, and then irradiated with active energy rays. Then, it can be formed by curing.
- the active energy ray-curable composition is a composition containing at least the active energy ray-curable resin described in the first hard coat layer and a photopolymerization initiator.
- the metal oxide fine particles include metal oxide particles such as titanium, zirconium, zinc, tin, antimony, cerium, iron, and indium.
- Specific examples of the metal oxide fine particles include, for example, titanium oxide, zirconium oxide, zinc oxide, tin oxide, antimony oxide, cerium oxide, iron oxide, zinc antimonate, tin oxide-doped indium oxide (ITO), and antimony-doped tin oxide. (ATO), phosphorus-doped tin oxide, aluminum-doped zinc oxide, gallium-doped zinc oxide, fluorine-doped tin oxide, and the like. These metal oxide fine particles may be used alone or in combination.
- titanium oxide and zirconium oxide are particularly preferable because they can increase the refractive index without reducing transparency.
- the content of the metal oxide fine particles in the active energy ray-curable composition is preferably 30% by mass or more, more preferably 40% by mass or more, with respect to 100% by mass of the total solid content of the active energy ray-curable composition.
- a mass% or more is particularly preferred.
- the upper limit is preferably 70% by mass or less, and preferably 60% by mass or less.
- the low refractive index layer is, for example, coated with an active energy ray-curable composition containing low refractive index inorganic particles and / or a fluorine-containing compound as a low refractive index material by a wet coating method and, if necessary, dried. It can be formed by irradiating with active energy rays and curing.
- the active energy ray-curable composition is a composition containing the active energy ray-curable resin and the photopolymerization initiator described in the first hard coat layer.
- inorganic particles such as silica and magnesium fluoride are preferable. Further, these inorganic particles are preferably hollow or porous.
- the content of such low refractive index inorganic particles is preferably in the range of 1 to 50% by mass, more preferably in the range of 3 to 40% by mass with respect to 100% by mass of the total solid content of the active energy ray-curable composition. In particular, the range of 5 to 35% by mass is preferable.
- the fluorine-containing compound examples include fluorine-containing monomers, fluorine-containing oligomers, and fluorine-containing polymer compounds.
- the fluorine-containing monomer or fluorine-containing oligomer is a monomer or oligomer having the above-mentioned ethylenically unsaturated group and fluorine atom in the molecule.
- fluorine-containing monomers and fluorine-containing oligomers examples include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, and 2- (perfluorobutyl).
- fluorine-containing polymer compound examples include a fluorine-containing copolymer having a fluorine-containing monomer and a monomer for imparting a crosslinkable group as structural units.
- fluorine-containing monomer unit examples include, for example, fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene, hexafluoropropylene, perfluoro-2,2-dimethyl-1,3-dioxole, etc.
- (Meth) acrylic acid partial or fully fluorinated alkyl ester derivatives for example, Biscoat 6FM (manufactured by Osaka Organic Chemical), M-2020 (manufactured by Daikin), etc.), fully or partially fluorinated vinyl ethers, and the like.
- a monomer for imparting a crosslinkable group in addition to a (meth) acrylate monomer having a crosslinkable functional group in the molecule like glycidyl methacrylate, it has a carboxyl group, a hydroxyl group, an amino group, a sulfonic acid group, etc.
- Acrylate monomers for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, etc.).
- the content of the fluorine-containing compound is preferably in the range of 5 to 50% by mass, more preferably in the range of 10 to 45% by mass, particularly preferably 15 to 40% with respect to 100% by mass of the total solid content of the active energy ray-curable composition. A range of mass% is preferred.
- the transparent conductive film having the hard coat film of the present invention as a base fill is preferably used as one of constituent members of the touch panel.
- a resistive touch panel usually has a configuration in which an upper electrode and a lower electrode are arranged via a spacer.
- a transparent conductive film using the hard coat film of the present invention as a base fill has an upper electrode and a lower electrode. Can be used for either or both.
- Capacitive touch panels are usually composed of patterned X and Y electrodes, but the transparent conductive film using the hard coat film of the present invention as a base fill is either an X electrode or a Y electrode. It can be used for either or both.
- the hard coat film of the present invention is suitable as a base film for a transparent conductive film of a capacitive touch panel.
- the transparent conductive film used for the touch panel is required to have good transparency and workability (blocking resistance), but the transparent conductive film based on the hard coat film of the present invention has the above-mentioned characteristics. Can be fully satisfied.
- the refractive index of the substrate film was measured at 589 nm using an Abbe refractometer according to JIS K7105 (1981).
- the cross section of the first hard coat layer was observed with a TEM (transmission electron microscope) (approximately 10,000 to 100,000 times), and the cross-sectional photograph thereof From 30 randomly selected particles (wherein the particles (in the case where the particles form a particle aggregate, the individual particles forming the particle aggregate) are: This means a single mass that cannot be further subdivided visually, in which case the particles are in the form of primary particles or secondary particles in which multiple primary particles are closely aggregated (so that the primary particles cannot be discriminated. The maximum lengths of each of the agglomerated dense forms) were measured, and the average of them was taken as the average particle diameter of the particles.
- the hard coat film in which the 1st hard coat layer was provided in both surfaces it arrange
- a black adhesive tape (Nitto Denko “Vinyl Tape No. 21 Tokuhaba Black”) is applied to the surface of the first hard coat layer of the hard coat film, and the reflection color of the second hard coat layer surface is set to three wavelengths in the dark room. It observed visually under the fluorescent lamp and performed on the following references
- Resin layer forming coating solution a In terms of solid content, Tg (glass transition temperature) of 120 ° C. is 26% by mass of polyester resin a, Tg is 80 ° C. of polyester resin b is 54% by mass, melamine-based crosslinking agent is 18% by mass, and particles are 2% by mass. % Was mixed to prepare an aqueous dispersion coating solution.
- Polyester resin a polyester resin obtained by copolymerizing 43 mol% of 2,6-naphthalenedicarboxylic acid, 7 mol% of 5-sodium sulfoisophthalic acid, and 50 mol% of a diol component containing ethylene glycol; polyester resin b; Polyester resin and melamine-based crosslinking agent obtained by copolymerization of 38 mol% terephthalic acid, 12 mol% trimellitic acid, and 50 mol% diol component containing ethylene glycol; "Nikarac MW12LF" manufactured by Sanwa Chemical Co., Ltd. ) Particles: colloidal silica having an average particle size of 0.19 ⁇ m.
- aqueous dispersion coating solution was prepared by mixing 80% by mass of the following acrylic resin, 18% by mass of the melamine-based crosslinking agent, and 2% by mass of the particles in a solid content mass ratio.
- Acrylic resin (acrylic resin consisting of the following copolymer composition) Methyl methacrylate 63% by weight Ethyl acrylate 35% by weight Acrylic acid 1% by weight N-methylolacrylamide 1% by weight
- Melamine-based cross-linking agent “Nicarac MW12LF” manufactured by Sanwa Chemical Co., Ltd.)
- Particles colloidal silica having an average particle size of 0.19 ⁇ m.
- particle dispersion A Vapor phase silica (“Aerosil OX50” from Nippon Aerosil Co., Ltd., average primary particle size of 40 nm) was dispersed in an organic solvent (methyl isobutyl ketone) to obtain a dispersion having a silica concentration of 15 mass%. A bead mill was used as a dispersing device.
- Pore dispersion B Vapor phase silica (“Aerosil OX50” from Nippon Aerosil Co., Ltd., average primary particle size of 40 nm) was dispersed in an organic solvent (methyl isobutyl ketone) to obtain a dispersion having a silica concentration of 15 mass%. A bead mill was used as a dispersing device.
- KBM7103 manufactured by Shin-Etsu Chemical Co., Ltd., fluoroalkylalkoxysilane
- a particle dispersion B surface-treated.
- a dispersion of silica particles was obtained.
- Particle dispersion C Gas phase method silica (“Aerosil OX50” from Nippon Aerosil Co., Ltd., average primary particle size 40 nm), 100 parts by mass of organic solvent (methyl isobutyl ketone), Fluoroalkylalkoxysilane (Shin-Etsu Chemical Co., Ltd.) 17 parts by mass of “KBM7103” manufactured by the manufacturer was mixed and dispersed for 3 hours using a paint shaker. Subsequently, the dispersion was heated and stirred at 50 ° C. for 1 hour to obtain a particle dispersion C (a dispersion of surface-treated silica particles).
- organic solvent methyl isobutyl ketone
- Fluoroalkylalkoxysilane Shin-Etsu Chemical Co., Ltd. 17 parts by mass of “KBM7103” manufactured by the manufacturer was mixed and dispersed for 3 hours using a paint shaker. Subsequently, the dispersion was heated and stirred at 50
- Pore dispersion D Vapor phase silica (“Aerosil OX50” from Nippon Aerosil Co., Ltd., average primary particle size of 40 nm) was dispersed in an organic solvent (methyl isobutyl ketone) to obtain a dispersion having a silica concentration of 15 mass%. A bead mill was used as a dispersing device.
- a particle dispersion D surface-treated silica particle dispersion treated with a surfactant was obtained.
- Particle dispersion E 13.7 parts by mass and 10% by mass of methacryloxypropyltrimethoxysilane are added to 150 parts by mass of chain colloidal silica (“organosilica sol MEK-ST-UP”, Nissan Chemical Industries, Ltd., average primary particle size 10 to 20 nm).
- chain colloidal silica (“organosilica sol MEK-ST-UP”, Nissan Chemical Industries, Ltd., average primary particle size 10 to 20 nm).
- formic acid aqueous solution was mixed and stirred at 70 ° C. for 1 hour, and then 13.8 parts by mass of fluorine compound (H 2 C ⁇ CH—COO—CH 2 — (CF 2 ) 8 F) and 2 Then, 0.57 parts by mass of 2-azobisisobutyronitrile was added, followed by heating and stirring at 90 ° C. for 60 minutes to obtain particle dispersion E (dispersion of surface-treated silica particles).
- Particle dispersion F Anionic surfactant having an ethyleneoxy group in the molecule (No. 1) on 150 parts by mass of chain colloidal silica (“organosilica sol MEK-ST-UP”, Nissan Chemical Industries, Ltd., average primary particle size 10-20 nm) 3 parts by mass of Ichi Kogyo Seiyaku Co., Ltd .: Prisurf A212E) were mixed and stirred for 20 hours to obtain a particle dispersion F (surface-treated silica particle dispersion) treated with a surfactant.
- organosilica sol MEK-ST-UP Nissan Chemical Industries, Ltd., average primary particle size 10-20 nm
- Prisurf A212E Prisurf A212E
- particle dispersion G 5 parts by weight of 3-methacryloxypropylmethyldimethoxysilane was added to 100 parts by weight of colloidal silica (“organosilica sol MIBK-ST-L”, Nissan Chemical Industries, Ltd., average primary particle size 40 nm), and 1 at 50 ° C.
- colloidal silica organic silica
- Patent dispersion H Colloidal silica (“organosilica sol MEK-ST-2040” manufactured by Nissan Chemical Industries, Ltd., average primary particle size: 170 to 230 nm) was used as it was.
- PMMA particles “MP series” from Soken Chemical Co., Ltd., average primary particle size 700 nm are dispersed as organic particles in an organic solvent (methyl isobutyl ketone), and the particle concentration is 15% by mass. A liquid was obtained. A bead mill was used as a dispersing device.
- Example 1 A hard coat film was prepared in the following manner.
- PET pellets (intrinsic viscosity 0.63 dl / g) substantially free of externally added particles are sufficiently vacuum-dried, then supplied to an extruder, melted at 285 ° C., extruded from a T-shaped die into a sheet shape, It was wound around a mirror-casting drum having a surface temperature of 25 ° C. using an electric application casting method and cooled and solidified. This unstretched film was heated to 90 ° C. and stretched 3.4 times in the longitudinal direction to obtain a uniaxially stretched film. After performing corona discharge treatment in air on both surfaces of the uniaxially stretched film, the resin layer coating solution a was applied to both surfaces of the uniaxially stretched film.
- the uniaxially stretched film coated with the resin layer coating solution a on both sides is held by clips and guided to a preheating zone, dried at an ambient temperature of 75 ° C., raised to 110 ° C. using a radiation heater, and again at 90 ° C. And then continuously stretched 3.5 times in the width direction in a heating zone at 120 ° C., followed by heat treatment for 20 seconds in a heating zone at 220 ° C. Produced.
- the thickness of the resin layer laminated PET film thus obtained was 100 ⁇ m, and the thickness of the resin layer laminated on both sides was 0.09 ⁇ m. Moreover, the refractive index of the PET film was 1.65, and the refractive index of the resin layer laminated on both surfaces was 1.59.
- the refractive index of the PET film was measured under the same conditions as described above except that the resin layer was not laminated on both sides, and the value was taken as the refractive index of the PET film.
- the active energy ray-curable composition a for forming the following first hard coat layer was applied by the gravure coating method on the resin layer on one side of the resin layer-laminated PET film obtained above, at 90 ° C. After drying, ultraviolet rays 400 mJ / cm 2 were irradiated and cured to form a first hard coat layer.
- This first hard coat layer had a thickness of 1.0 ⁇ m and a refractive index of 1.51.
- a composition was prepared.
- an organic solvent methyl ethyl ketone
- Example 2 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first hard coat layer was changed to the following composition.
- This first hard coat layer had a thickness of 1.0 ⁇ m and a refractive index of 1.51.
- Example 3 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first hard coat layer was changed to the following composition.
- This first hard coat layer had a thickness of 1.0 ⁇ m and a refractive index of 1.51.
- Example 4 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first hard coat layer was changed to the following composition.
- This first hard coat layer had a thickness of 1.0 ⁇ m and a refractive index of 1.51.
- Example 5 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first hard coat layer was changed to the following composition.
- This first hard coat layer had a thickness of 1.0 ⁇ m and a refractive index of 1.51.
- Example 6 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first hard coat layer was changed to the following composition.
- This first hard coat layer had a thickness of 1.0 ⁇ m and a refractive index of 1.51.
- Example 1 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first hard coat layer was changed to the following composition.
- This first hard coat layer had a thickness of 1.0 ⁇ m and a refractive index of 1.51.
- Example 2 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first hard coat layer was changed to the following composition.
- This first hard coat layer had a thickness of 1.0 ⁇ m and a refractive index of 1.51.
- Example 3 A hard coat film was produced in the same manner as in Example 1 except that the active energy ray-curable composition for forming the first hard coat layer was changed to the following composition.
- This first hard coat layer had a thickness of 1.0 ⁇ m and a refractive index of 1.52.
- Comparative Example 4 In Comparative Example 3, a hard coat film was prepared in the same manner as in Comparative Example 3 except that the thickness of the first hard coat layer was changed to 2.0 ⁇ m.
- the first hard coat layer is laminated on one surface of the above resin layer laminated PET film in the same manner as in Comparative Example 1, and the second hard coat layer is laminated on the other surface in the same manner as in Example 1 to form a hard coat.
- a film was prepared.
- the thickness of the first hard coat layer was 1.0 ⁇ m and the refractive index was 1.51, and the thickness of the second hard coat layer was 1.5 ⁇ m and the refractive index was 1.52.
- the center line average roughness (Ra2) on the surface of the second hard coat layer was 5 nm.
- composition refers to “active energy ray-curable composition”.
- number of protrusions of “0.1 or less” means that protrusions are not confirmed in all five randomly shot areas, but a very small number of protrusions are confirmed when observed widely with a scanning electron microscope. Means when In addition, about such a sample, the measurement of the length (L) of a protrusion part, height (T), and protrusion part formation particle
- the haze value is small, and there are one or more protrusions per 4 ⁇ m square on the surface of the first hard coat layer. It turns out that blocking property is favorable.
- Examples 1 to 4 of the present invention there are one or more protrusions per 4 ⁇ m square having a protrusion length (L) of 0.7 ⁇ m or more. As a result, Examples 1 to 4 have very good blocking resistance.
- Examples 1 to 4 of the present invention it is confirmed that there are one or more protrusions per 4 ⁇ m square in which the number of particles forming the protrusions is 20 or more. As a result, Examples 1 to 4 have very good blocking resistance.
- Comparative Examples 1, 2, and 5 have 0.1 or less protruding portions, and sufficient blocking resistance is not obtained. This is because the silica particles or the silica particle aggregate is not subjected to the surface treatment of the present invention, so that the silica particle aggregate does not sufficiently move (float) near the surface of the first hard coat layer. Guessed.
- the first hard coat layer had an average particle size (r: ⁇ m) of 0.5 ⁇ m or more, and the average particle size (r: ⁇ m) and the thickness of the first hard coat layer (d: ⁇ m) It contains particles with a ratio (r / d) exceeding 0.5.
- this hard coat film has good blocking resistance, the average particle diameter (r: ⁇ m) and ratio (r / d) of the particles are beyond the range of the present invention, and the haze value of the hard coat film is greatly increased. Is rising.
- Comparative Example 4 the thickness (d: ⁇ m) of the first hard coat layer in Comparative Example 3 was increased to 2.0 ⁇ m, the average particle diameter (r: ⁇ m) and the thickness of the first hard coat layer (d: ⁇ m) The ratio (r / d) is 0.5 or less, but the haze value of the hard coat film is still large.
- the average particle size (r: ⁇ m) is less than 0.5 ⁇ m, and the average particle size (r: ⁇ m) and the thickness of the first hard coat layer (d: ⁇ m) It can be seen that it is important to satisfy the two conditions that the ratio (r / d) is 0.5 or less.
- the hard coat film having a high haze value as in Comparative Examples 3 and 4 is unsuitable for application to a base film of a transparent conductive film requiring high transparency.
- Example 11 to 16 The following high refractive index layer and low refractive index layer were laminated in this order on the surface of the second hard coat layer of each of the hard coat films obtained in Examples 1 to 6, and then on the low refractive index layer, the following The transparent conductive film was formed to produce a transparent conductive film for a capacitive touch panel.
- active energy ray-curable composition for forming a high refractive index layer As an active energy ray-curable resin, 47 parts by mass of dipentaerythritol hexaacrylate, 50 parts by mass of zirconium oxide, and 3 parts by mass of a polymerization initiator (“Irgacure (registered trademark) 184” manufactured by Ciba Specialty Chemicals Co., Ltd.) are organic. It was prepared by dispersing and dissolving in a solvent (propylene glycol monoethyl ether).
- solvent propylene glycol monoethyl ether
- ⁇ Lamination of low refractive index layer> The following active energy ray-curable composition for forming a low refractive index layer is applied by a gravure coating method, dried at 90 ° C., and cured by irradiation with ultraviolet rays of 400 mJ / cm 2 to have a thickness of 0.04 ⁇ m. A rate layer was formed. The refractive index of this low refractive index layer was 1.46.
- (Active energy ray-curable composition for forming a low refractive index layer) 84 parts by mass of dipentaerythritol hexaacrylate, 14 parts by mass of hollow silica as an active energy ray curable resin, 2 parts by mass of a monomer polymerization initiator (“Irgacure (registered trademark) 184” manufactured by Ciba Specialty Chemicals) A part was prepared by dispersing and dissolving in an organic solvent (a mixed solvent of methyl isobutyl ketone and propylene glycol monoethyl ether having a mass ratio of 1: 1).
- an organic solvent a mixed solvent of methyl isobutyl ketone and propylene glycol monoethyl ether having a mass ratio of 1: 1).
- An ITO film was laminated by a sputtering method so as to have a thickness of 22 nm, and a transparent conductive film was formed by pattern processing (etching process) into a lattice pattern.
- evaluation of blocking resistance of the transparent conductive film was changed so that the surface of the first hard coat layer and the surface of the transparent conductive film face each other in the above-mentioned “(10) Evaluation of blocking resistance”. Evaluation was performed in the same manner except that.
- Example 21 In Example 1, a hard coat film was produced in the same manner as in Example 1 except that the first hard coat layer was laminated on both sides of the resin layer laminated PET film. The thickness of the 1st hard-coat layer provided in both surfaces of the resin layer laminated PET film was 1.0 micrometer, respectively.
- Example 22 In Example 2, a hard coat film was produced in the same manner as in Example 2 except that the first hard coat layer was laminated on both sides of the resin layer laminated PET film. The thickness of the 1st hard-coat layer provided in both surfaces of the resin layer laminated PET film was 1.0 micrometer, respectively.
- Example 23 In Example 3, a hard coat film was produced in the same manner as in Example 3 except that the first hard coat layer was laminated on both sides of the resin layer laminated PET film. The thickness of the 1st hard-coat layer provided in both surfaces of the resin layer laminated PET film was 1.0 micrometer, respectively.
- Example 24 In Example 4, a hard coat film was produced in the same manner as in Example 4 except that the first hard coat layer was laminated on both sides of the resin layer laminated PET film. The thickness of the 1st hard-coat layer provided in both surfaces of the resin layer laminated PET film was 1.0 micrometer, respectively.
- Example 25 a hard coat film was produced in the same manner as in Example 5 except that the first hard coat layer was laminated on both sides of the resin layer laminated PET film.
- the thickness of the 1st hard-coat layer provided in both surfaces of the resin layer laminated PET film was 1.0 micrometer, respectively.
- Example 26 In Example 6, a hard coat film was produced in the same manner as in Example 6 except that the first hard coat layer was laminated on both sides of the resin layer laminated PET film. The thickness of the 1st hard-coat layer provided in both surfaces of the resin layer laminated PET film was 1.0 micrometer, respectively.
- Examples 21 to 26 regarding the number of protrusions, the length (L), the height (T), and the number of particles forming the protrusions on the surface of the first hard coat layer provided on both surfaces, The results on both surfaces were almost the same as those of Examples 1 to 6 corresponding to Examples 21 to 26 (the results were the same as those of Examples 1 to 6 in Table 2).
- Examples 21 to 26 all have a small haze value and good blocking resistance.
- Examples 31 to 36 The following high refractive index layer and low refractive index layer were laminated in this order on the surface of the first hard coat layer on one side of each of the hard coat films obtained in Examples 21 to 26, and then the low refractive index layer A transparent conductive film for a capacitive touch panel was produced by forming the following transparent conductive film on the substrate.
- ⁇ Lamination of high refractive index layer> The following active energy ray-curable composition for forming a high refractive index layer is applied by a gravure coating method, dried at 90 ° C., cured by irradiation with ultraviolet rays of 400 mJ / cm 2 , and a thickness of 0.03 ⁇ m. A rate layer was formed. The refractive index of this high refractive index layer was 1.70.
- active energy ray-curable composition for forming a high refractive index layer As active energy ray-curable resin, 37 parts by mass of dipentaerythritol hexaacrylate, 60 parts by mass of zirconium oxide, and 3 parts by mass of a photopolymerization initiator (“Irgacure (registered trademark) 184” manufactured by Ciba Specialty Chemicals Co., Ltd.) It was prepared by dispersing and dissolving in an organic solvent (propylene glycol monoethyl ether).
- an organic solvent propylene glycol monoethyl ether
- ⁇ Lamination of low refractive index layer> The following active energy ray-curable composition for forming a low refractive index layer is applied by a gravure coating method, dried at 90 ° C., and cured by irradiation with ultraviolet rays of 400 mJ / cm 2 to have a thickness of 0.04 ⁇ m. A rate layer was formed. The refractive index of this low refractive index layer was 1.51.
- a solvent a mixed solvent of methyl isobutyl ketone and propylene glycol monoethyl ether having a mass ratio of 1: 1).
- An ITO film was laminated by a sputtering method so as to have a thickness of 20 nm, and a transparent conductive film was formed by pattern processing (etching process) into a lattice pattern.
- the evaluation of the blocking resistance of the transparent conductive film is such that the surface of the first hard coat layer on the other side faces the surface of the transparent conductive film in the above-mentioned “(10) Evaluation of blocking resistance”. Evaluations were made in the same manner except that they were changed to overlap.
- the transparent conductive films of Examples 31 to 36 all had good blocking resistance and visibility of the transparent conductive film pattern.
Landscapes
- Laminated Bodies (AREA)
- Non-Insulated Conductors (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Abstract
Description
[1] 基材フィルムの少なくとも一方の面に第1ハードコート層を備えたハードコートフィルムであって、第1ハードコート層は、平均粒子径(r:μm)が0.5μm未満でかつ第1ハードコート層の厚み(d:μm)に対して0.5倍以下である粒子が複数個集合した粒子集合体を含有し、第1ハードコート層表面に前記粒子集合体による突出部が第1ハードコート層表面の4μm平方当たり1個以上の密度で存在することを特徴とするハードコートフィルム。
[2] 前記突出部は、第1ハードコート層表面の面方向(平面的)に10個以上の粒子が集合した状態で形成されている、前記[1]に記載のハードコートフィルム。
[3]前記突出部の長さ(L)が0.4μm以上である、前記[1]または[2]に記載のハードコートフィルム。
[4]前記粒子がシリカ粒子であり、シリカ粒子またはシリカ粒子集合体が、表面自由エネルギーを小さくするための表面処理もしくは界面活性剤による表面処理が施されている、前記[1]~[3]のいずれかに記載のハードコートフィルム。
[5]前記シリカ粒子が気相法シリカである、前記[4]に記載のハードコートフィルム。
[6]ハードコートフィルムのヘイズ値が0.7%以下である、前記[1]~[5]のいずれかに記載のハードコートフィルム。
[7]前記第1ハードコート層表面の中心線平均粗さ(Ra1)が25nm以下である、前記[1]~[6]のいずれかに記載のハードコートフィルム。
[8]前記粒子の平均粒子径(r:μm)が0.01μm以上0.4μm未満である、前記[1]~[7]のいずれかに記載のハードコートフィルム。
[9]前記第1ハードコート層の厚み(d:μm)が0.5μm以上4μm未満である、前記[1]~[8]のいずれかに記載のハードコートフィルム。
[10]前記基材フィルムの両面に第1ハードコート層を備えた、前記[1]~[9]のいずれかに記載のハードコートフィルム。
[11]前記基材フィルムが、屈折率が1.62~1.70であるポリエチレンテレフタレートフィルムであり、該ポリエチレンテレフタレートフィルムの片面もしくは両面に、屈折率が1.55~1.61である樹脂層を介して屈折率が1.48~1.54である第1ハードコート層が積層されている、前記[1]~[10]のいずれかに記載のハードコートフィルム。
[12]前記基材フィルムが、屈折率が1.62~1.70であるポリエチレンテレフタレートフィルムであり、該ポリエチレンテレフタレートフィルムの一方の面に屈折率が1.55~1.61である樹脂層を介して屈折率が1.48~1.54である第1ハードコート層が積層されており、かつ前記ポリエチレンテレフタレートフィルムの他方の面に屈折率が1.55~1.61である樹脂層を介して屈折率が1.48~1.54である第2ハードコート層が積層されている、前記[1]~[9]のいずれかに記載のハードコートフィルム。
[13]前記[1]~[12]のいずれかに記載のハードコートフィルムの少なくとも一方の面に透明導電膜を有する、透明導電性フィルム。
第1ハードコート層は、高い硬度を確保するという観点から、その厚み(d:μm)は0.5μm以上が好ましく、0.8μm以上がより好ましく、0.9μm以上が特に好ましい。第1ハードコート層の鉛筆硬度(JIS K5600-5-4(1999年))は、F以上が好ましく、H以上がより好ましい。上限は9H程度である。
アクリル系樹脂粒子としては、アクリル樹脂粒子、メタクリル樹脂粒子、アクリルモノマーあるいはメタクリルモノマーと他のモノマー(例えば、スチレン、ウレタンアクリレート、ウレタンメタクリレート、ポリエステルアクリレート、ポリエステルメタクリレート、シリコーンアクリレート、シリコーンメタクリレート等)との共重合樹脂粒子が挙げられる。
・・・・一般式(1)
(一般式(1)において、nは1~10の整数、mは1~5の整数を表す。Qは炭素数1~5のアルコキシ基またはハロゲン原子を表す。)。
C6F13CH2CH2Si(OCH3)3
C8F17CH2CH2Si(OCH3)3
C6F13CH2CH2CH2Si(OCH3)3
C6F13CH2CH2CH2CH2Si(OCH3)3
C6F13CH2CH2Si(OC2H5)3
C8F17CH2CH2CH2Si(OC2H5)3
C6F13CH2CH2CH2CH2Si(OC2H5)3
C6F13CH2CH2SiCl3
C6F13CH2CH2SiBr3
C6F13CH2CH2CH2SiCl3
C6F13CH2CH2Si(OCH3)Cl2。
・・・・一般式(2)。
・・・・一般式(3)。
アクリロキシブチルトリアルコキシシラン、アクリロキシペンチルトリアルコキシシラン、アクリロキシヘキシルトリアルコキシシラン、アクリロキシヘプチルトリアルコキシシラン、メタクリロキシエチルトリアルコキシシラン、メタクリロキシプロピルトリアルコキシシラン、メタクリロキシブチルトリアルコキシシラン、メタクリロキシヘキシルトリアルコキシシラン、メタクリロキシヘプチルトリアルコキシシラン、メタクリロキシプロピルメチルジアルコキシシラン、メタクリロキシプロピルメチルジアルコキシシラン及びこれら化合物中のアルコキシ基が水酸基に置換された化合物を含むものなどが挙げられる。ここで、アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基が挙げられる。
陰イオン性界面活性剤;例えば、ポリオキシエチレンアルキルエーテルリン酸塩、ポリオキシアルキレンアルキルエーテルリン酸エステル、ポリオキシアルキレンアルキルフェニルエーテルリン酸エステル、ポリオキシエチレントリデシルエーテルリン酸エステル、ポリオキシエチレンアルキルエーテルリン酸エステル、ポリオキシエチレンアルキルエーテルリン酸エステルモノエタノールアミン塩、ポリオキシエチレンラウリルエーテルリン酸エステル、ポリオキシエチレントリラウリルエーテルリン酸エステルモノエタノールアミン塩、ポリオキシエチレンスチレン化フェニルエーテルリン酸エステル、ポリオキシエチレンラウリルエーテル酢酸ナトリウム、ポリオキシエチレンスルホコハク酸ラウリルニナトリウム、ポリオキシエチレンアルキルスルホコハク酸ニナトリウム、ポリオキシスチレン化フェニルエーテル硫酸アンモニウム、ポリエキシアルキレン分岐デシルエーテル硫酸ナトリウム、ポリオキシエチレンイソデシルエーテル硫酸アンモニウム、ポリオキシエチレントリデシルエーテル硫酸ナトリウム、ポリオキシエチレンラウリルエーテル硫酸ナトリウム、ポリオキシエチレンラウリルエーテル硫酸アンモニウム、ポリオキシエチレンアルキルエーテル硫酸ナトリウム、ポリオキシエチレンオレイルセチルエーテル硫酸アンモニウム、ポリオキシエチレンオレイルセチルエーテル硫酸ナトリウム等、
非イオン性界面活性剤;例えば、ポリオキシアルキレンデシルエーテル、ポリオキシエチレントリデシルエーテル、ポリオキシアルキレントリデシルエーテル、ポリオキシアルキレンアルキルエーテル、ポリオキシエチレンイソデシルエーテル、ポリオキシアルキレンラウリルエーテル、ポリオキシエチレンスチレン化フェニルエーテル、ポリオキシエチレンナフチルエーテル、ポリオキシエチレンフェニルエーテル、ポリオキシエチレンポリエキシプロピレングリコール、ポリオキシエチレンラウルルエーテル、ポリオキシエチレンオレイルセチルエーテル、ポリオキシエチレンオレイン酸エステル、ポリエキシエチレンステアリン酸エステル、ポリエキシエチレンソルビタンモノココエート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタンモノオレート、イソステアリン酸ポリオキシエチレングリセリル、ポリオキシエチレンアルキルアミン等、
が挙げられる。
本発明の基材フィルムは、プラスチックフィルムが好ましく用いられる。基材フィルムを構成する材質としては、例えば、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート(PEN)などのポリエステル、ポリイミド、ポリフェニレンスルフィド、アラミド、ポリプロピレン、ポリエチレン、ポリ乳酸、ポリ塩化ビニル、ポリカーボネート、ポリメタクリル酸メチル、脂環式アクリル樹脂、シクロオレフィン樹脂、トリアセチルセルロース、およびこれら樹脂を混合および/または共重合したものが挙げられる。これらの樹脂を未延伸、一軸延伸、二軸延伸してフィルムとしたものを基材フィルムとして適用することができる。
基材フィルムと第1ハードコート層の密着性を強化するために、基材フィルムは少なくとも第1ハードコート層が積層される面に樹脂層が設けられていることが好ましい。
本発明のハードコートフィルムは、基材フィルムの少なくとも一方の面に第1ハードコート層を有する。ハードコートフィルムは、基材フィルムの片面のみに第1ハードコート層を有していてもよいし、基材フィルムの両面に第1ハードコート層を有していてもよい。
以下、基材フィルムの他方の面に設けられる第2ハードコート層について説明する。
本発明のハードコートフィルムは、透明導電性フィルムのベースフィルムとして好適である。つまり、本発明のハードコートフィルムをベースフィルムとして用いた透明導電性フィルムは、本発明のハードコートフィルムの少なくとも一方の面に透明導電膜が積層されたものである。
ii)透明導電膜/第1ハードコート層/樹脂層/基材フィルム/樹脂層/第1ハードコート層/透明導電膜
iii)第1ハードコート層/樹脂層/基材フィルム/樹脂層/第2ハードコート層/透明導電膜
iv)透明導電膜/第1ハードコート層/樹脂層/基材フィルム/樹脂層/第2ハードコート層
v)透明導電膜/第1ハードコート層/樹脂層/基材フィルム/樹脂層/第2ハードコート層/透明導電膜。
透明導電膜を形成する材料としては、例えば、酸化錫、酸化インジウム、酸化アンチモン、酸化亜鉛、ITO(酸化インジウム錫)、ATO(酸化アンチモン錫)等の金属酸化物、金属ナノワイヤー(例えば銀ナノワイヤー)、カーボンナノチューブが挙げられる。これらの中でも、ITOが好ましく用いられる。
上記透明導電性フィルムの構成例において、透明導電膜は第1ハードコート層あるいは第2ハードコート層の上に直接に積層されてもよいが、透明導電膜と第1ハードコート層あるいは第2ハードコート層との間に屈折率調整層を介在させることが好ましい。以下、屈折率調整層について説明する。
本発明のハードコートフィルムをベースフィルとする透明導電性フィルムは、タッチパネルの構成部材の1つとして好ましく用いられる。
それぞれの塗布液をシリコンウエハー上にスピンコーターにて塗工形成した塗膜(乾燥厚み約2μm)について、25℃の温度条件下で位相差測定装置(ニコン(株)製:NPDM-1000)で589nmの屈折率を測定した。
樹脂層が積層された基材フィルムの断面を超薄切片に切り出し、RuO4染色、OsO4 染色、あるいは両者の二重染色による染色超薄切片法により、TEM(透過型電子顕微鏡)で断面構造が目視可能な以下の条件にて観察し、その断面写真から樹脂層の厚みを測定する。尚、測定個所は粒子が存在しない部分である。なお、5箇所を測定して、その平均値を樹脂層の厚みとした。
・測定装置:透過型電子顕微鏡(日立(株)製 H-7100FA型)
・測定条件:加速電圧 100kV
・試料調整:凍結超薄切片法
・倍率:30万倍。
ハードコートフィルムの断面を超薄切片に切り出し、TEM(透過型電子顕微鏡)で加速電圧100kVにて観察(1~30万倍の倍率で観察)し、その断面写真から厚みを測定する。尚、第1ハードコート層のように表面に突出部を有する層については、突出部が存在しない部分における厚みである。厚みの測定は5箇所で行い、その平均値を厚みとした。
第1ハードコート層の断面をTEM(透過型電子顕微鏡)で観察(約1万~10万倍)し、その断面写真から、無作為に選択した30個の粒子(ここで、粒子(粒子が粒子集合体を形成している場合は、粒子集合体を形成している個々の粒子)とは、TEMによる観察において、視覚的にこれ以上細分化できない1つの塊を意味する。この意味において、粒子は、一次粒子の形態あるいは複数個の一次粒子が密に凝集した二次粒子の形態(一次粒子が判別できないほどに密に凝集した形態)を取り得る。)のそれぞれの最大長さを計測し、それらを平均した値を粒子の平均粒子径とした。
基材フィルムに積層された樹脂層(易接着層)表面を、SEM(走査型電子顕微鏡)を用いて倍率一万倍で観察し、粒子の画像(粒子によってできる光の濃淡)をイメージアナライザー(たとえばケンブリッジインストルメント製QTM900)に結び付け、観察箇所を変えてデータを取り込み、合計粒子数5000個以上となったところで次の数値処理を行ない、それによって求めた数平均径dを平均粒径(直径)とした。
・d=Σdi /N
ここでdi は粒子の等価円直径(粒子の断面積と同じ面積を持つ円の直径)、Nは個数である。
JIS B0601(1982)に基づき、触針式表面粗さ測定器SE-3400((株)小坂研究所製)を用いて測定した。
送り速さ;0.5mm/s
評価長さ;8mm
カットオフ値λc;0.08mm。
ハードコートフィルムのカットサンプル(20cm×15cm)を用意し、このカットサンプルの第1ハードコート層の表面をSEM(走査型電子顕微鏡)にてランダムに5箇所撮影(約1万~10万倍)し、5つの画像(表面写真)を作製する。次に、5つの画像それぞれについて、画像の4μm平方(面積16μm2)の範囲に存在する突出部の個数を計測し、平均した。
上記(7)で撮影した画像(表面写真)の中から無作為に選択した10個の突出部の長さ(L)を測定し、平均した。
ハードコートフィルムのカットサンプル(20cm×15cm)を用意し、このカットサンプルの第1ハードコート層の断面をTEM(透過型電子顕微鏡)にて5箇所撮影(約1万~10万倍)し、5つの断面写真を作製する。次に、5つの断面写真に存在する全ての突出部の高さを測定し、平均した。
JIS K 7136(2000)に基づき、日本電色工業(株)製の濁度計「NDH-2000」を用いて測定した。測定に際し、ハードコートフィルムの第1ハードコート層が設けられている側の表面に光が入射するように配置する。
ハードコートフィルムの一方の表面を第1面とし、他方の表面を第2面とする。
ハードコートフィルムを切断して2枚のシート片(20cm×15cm)を作製する。この2枚のシートの第1面と第2面とが向き合うようにして重ね合わせる。次に、2枚のシート片を重ね合わせた試料をガラス板で挟み込み、約3kgの重りを載せて、50℃、90%(RH)の雰囲気下に48時間放置する。次に、重ね合わせ面を目視により観察しニュートンリングの発生状況を確認した後、両者を剥離し、以下の基準で評価した。
○(極めて良好):剥離前はニュートンリングが発生しておらず、剥離時には剥離音を立てずに軽く剥離される。
△(良好):剥離前は一部ニュートンリングが発生しており、剥離時には小さな剥離音を立てながら剥離される。
×(不良):剥離前は全面にニュートンリングが発生しており、剥離時には大きな剥離音を立てて剥離される。
ハードコートフィルムの第2ハードコート層の面に黒粘着テープ(日東電工製“ビニルテープNo.21 トクハバ 黒”)を貼り付け、第1ハードコート層の面の反射色を暗室三波長蛍光灯下にて目視にて観察し、以下の基準で行った。
○:反射色がニュートラルでほぼ無色である。
×:反射色が着色を呈している。
黒い板の上に透明導電性フィルムを置き、目視により透明導電膜のパターン部が視認できるかどうか以下の基準で評価した。
○:パターン部が視認できない。
×:パターン部が視認できる。
(樹脂層形成用塗布液a)
固形分質量比で、Tg(ガラス転移温度)が120℃のポリエステル樹脂aを26質量%、Tgが80℃のポリエステル樹脂bを54質量%、メラミン系架橋剤を18質量%、粒子を2質量%混合して水分散塗布液を調製した。
・ポリエステル樹脂a;2,6-ナフタレンジカルボン酸43モル%、5-ナトリウムスルホイソフタル酸7モル%、エチレングリコールを含むジオール成分50モル%を共重合して得られたポリエステル樹脂
・ポリエステル樹脂b;テレフタル酸38モル%、トリメリット酸12モル%、エチレングリコールを含むジオール成分50モル%を共重合して得られたポリエステル樹脂
・メラミン系架橋剤;三和ケミカル(株)製の「ニカラック MW12LF」)
・粒子;平均粒子径0.19μmのコロイダルシリカ。
固形分質量比で、下記のアクリル樹脂を80質量%、メラミン系架橋剤を18質量%、粒子を2質量%混合して水分散塗布液を調製した。
・アクリル樹脂(下記の共重合組成からなるアクリル樹脂)
メチルメタクリレート 63重量%
エチルアクリレート 35重量%
アクリル酸 1重量%
N-メチロールアクリルアミド 1重量%
・メラミン系架橋剤;三和ケミカル(株)製の「ニカラック MW12LF」)
・粒子;平均粒子径0.19μmのコロイダルシリカ。
(粒子分散液A)
気相法シリカ(日本アエロジル(株)の「アエロジルOX50」、平均一次粒子径が40nm)を有機溶剤(メチルイソブチルケトン)中で分散してシリカ濃度が15質量%の分散液を得た。分散装置としてビーズミルを用いた。
気相法シリカ(日本アエロジル(株)の「アエロジルOX50」、平均一次粒子径が40nm)を有機溶剤(メチルイソブチルケトン)中で分散してシリカ濃度が15質量%の分散液を得た。分散装置としてビーズミルを用いた。
気相法シリカ(日本アエロジル(株)の「アエロジルOX50」、平均一次粒子径が40nm)100質量部に、有機溶剤(メチルイソブチルケトン)を570質量部、フルオロアルキルアルコキシシラン(信越化学(株)製の「KBM7103」)を17質量部混合し、ペイントシェーカーを用いて3時間分散した。次いで、分散液を50℃で1時間加熱撹拌して粒子分散液C(表面処理されたシリカ粒子の分散液)を得た。
気相法シリカ(日本アエロジル(株)の「アエロジルOX50」、平均一次粒子径が40nm)を有機溶剤(メチルイソブチルケトン)中で分散してシリカ濃度が15質量%の分散液を得た。分散装置としてビーズミルを用いた。
鎖状コロイダルシリカ(日産化学工業(株)の「オルガノシリカゾルMEK-ST-UP」、平均一次粒子径10~20nm)150質量部に、メタクリロキシプロピルトリメトキシシラン13.7質量部と10質量%蟻酸水溶液1.7質量部を混合し、70℃にて1時間撹拌し、次いで、フッ素化合物(H2C=CH-COO-CH2-(CF2)8F)13.8質量部および2,2-アゾビスイソブチロニトリル0.57質量部を加えた後、60分間90℃にて加熱撹拌して、粒子分散液E(表面処理されたシリカ粒子の分散液)を得た。
鎖状コロイダルシリカ(日産化学工業(株)の「オルガノシリカゾルMEK-ST-UP」、平均一次粒子径10~20nm)150質量部に、分子中にエチレンオキシ基を有する陰イオン界面活性剤(第一工業製薬(株)製:プライサーフA212E)3質量部を混合し20時間撹拌して、界面活性剤で処理した粒子分散液F(表面処理されたシリカ粒子の分散液)を得た。
コロイダルシリカ(日産化学工業(株)の「オルガノシリカゾルMIBK-ST-L」、平均一次粒子径が40nm)100重量部に3-メタクリロキシプロピルメチルジメトキシシランを5重量部添加し、50℃で1時間加熱処理することにより、3-メタクリロキシプロピルメチルジメトキシシランで処理された粒子分散液G(反応性シリカの分散液)を得た。但し、この処理は、先に定義した本発明の表面処理には含まれない。
コロイダルシリカ(日産化学工業(株)の「オルガノシリカゾルMEK-ST-2040」、平均一次粒子径170~230nm)をそのまま用いた。
有機粒子としてポリメタクリル酸メチル粒子(綜研化学(株)のPMMA粒子「MPシリーズ」、平均一次粒子径が700nm)を有機溶剤(メチルイソブチルケトン)中で分散して粒子濃度が15質量%の分散液を得た。分散装置としてビーズミルを用いた。
下記の要領でハードコートフィルムを作製した。
実質的に外部添加粒子を含有しないPETペレット(極限粘度0.63dl/g)を充分に真空乾燥した後、押し出し機に供給し285℃で溶融し、T字型口金よりシート状に押し出し、静電印加キャスト法を用いて表面温度25℃の鏡面キャスティングドラムに巻き付けて冷却固化せしめた。この未延伸フィルムを90℃に加熱して長手方向に3.4倍延伸し、一軸延伸フィルムとした。この一軸延伸フィルムの両面に空気中でコロナ放電処理を施した後、一軸延伸フィルムの両面にそれぞれ樹脂層塗布液aを塗布した。
上記で得られた樹脂層積層PETフィルムの一方の面の樹脂層上に下記の第1ハードコート層を形成するための活性エネルギー線硬化性組成物aをグラビアコート法で塗布し、90℃で乾燥後、紫外線400mJ/cm2を照射し硬化させて、第1ハードコート層を形成した。この第1ハードコート層は、厚みが1.0μmm、屈折率が1.51であった。
ジペンタエリスリトールヘキサアクリレート40質量部、ウレタンアクリレートオリゴマー(根上工業(株)の「UN-901T」;分子中に重合性官能基を9個含む)40質量部、粒子分散液Aを固形分換算で15質量部、光重合開始剤(チバ・スペシャリティ・ケミカルズ(株)製「イルガキュア(登録商標)184」)5質量部を有機溶剤(メチルイソブチルケトン)に混合して、固形分濃度が30質量%の組成物を調製した。
次いで、樹脂層積層PETフィルムの他方の面(第1ハードコート層が積層された面とは反対面)の樹脂層上に、下記の第2ハードコート層を形成するための活性エネルギー線硬化性組成物Zをグラビアコート法で塗布し、90℃で乾燥後、紫外線400mJ/cm2を照射し硬化させて、第2ハードコート層を形成した。この第2ハードコート層は、厚みが1.5μmm、屈折率が1.52であった。
ジペンタエリスリトールヘキサアクリレート48質量部、ウレタンアクリレートオリゴマー(根上工業(株)の「UN-901T」;分子中に重合性官能基を9個含む)47質量部、光重合開始剤(チバ・スペシャリティ・ケミカルズ(株)製「イルガキュア(登録商標)184」)5質量部を有機溶剤(メチルエチルケトン)に混合して、固形分濃度が30質量%の組成物を調製した。
第1ハードコート層を形成するための活性エネルギー線硬化性組成物を下記の組成物に変更する以外は、実施例1と同様にしてハードコートフィルムを作製した。この第1ハードコート層は、厚みが1.0μmm、屈折率が1.51であった。
ジペンタエリスリトールヘキサアクリレート40質量部、ウレタンアクリレートオリゴマー(根上工業(株)の「UN-901T」;分子中に重合性官能基を9個含む)40質量部、粒子分散液Bを固形分換算で15質量部、光重合開始剤(チバ・スペシャリティ・ケミカルズ(株)製「イルガキュア(登録商標)184」)5質量部を有機溶剤(メチルイソブチルケトン)に混合して、固形分濃度が30質量%の組成物を調製した。
第1ハードコート層を形成するための活性エネルギー線硬化性組成物を下記の組成物に変更する以外は、実施例1と同様にしてハードコートフィルムを作製した。この第1ハードコート層は、厚みが1.0μmm、屈折率が1.51であった。
ジペンタエリスリトールヘキサアクリレート40質量部、ウレタンアクリレートオリゴマー(根上工業(株)の「UN-901T」;分子中に重合性官能基を9個含む)40質量部、粒子分散液Cを固形分換算で15質量部、光重合開始剤(チバ・スペシャリティ・ケミカルズ(株)製「イルガキュア(登録商標)184」)5質量部を有機溶剤(メチルイソブチルケトン)に混合して、固形分濃度が30質量%の組成物を調製した。
第1ハードコート層を形成するための活性エネルギー線硬化性組成物を下記の組成物に変更する以外は、実施例1と同様にしてハードコートフィルムを作製した。この第1ハードコート層は、厚みが1.0μmm、屈折率が1.51であった。
ジペンタエリスリトールヘキサアクリレート40質量部、ウレタンアクリレートオリゴマー(根上工業(株)の「UN-901T」;分子中に重合性官能基を9個含む)40質量部、粒子分散液Dを固形分換算で15質量部、光重合開始剤(チバ・スペシャリティ・ケミカルズ(株)製「イルガキュア(登録商標)184」)5質量部を有機溶剤(メチルイソブチルケトン)に混合して、固形分濃度が30質量%の組成物を調製した。
第1ハードコート層を形成するための活性エネルギー線硬化性組成物を下記の組成物に変更する以外は、実施例1と同様にしてハードコートフィルムを作製した。この第1ハードコート層は、厚みが1.0μmm、屈折率が1.51であった。
ジペンタエリスリトールヘキサアクリレート40質量部、ウレタンアクリレートオリゴマー(根上工業(株)の「UN-901T」;分子中に重合性官能基を9個含む)40質量部、粒子分散液Eを固形分換算で15質量部、光重合開始剤(チバ・スペシャリティ・ケミカルズ(株)製「イルガキュア(登録商標)184」)5質量部を有機溶剤(メチルイソブチルケトン)に混合して、固形分濃度が30質量%の組成物を調製した。
第1ハードコート層を形成するための活性エネルギー線硬化性組成物を下記の組成物に変更する以外は、実施例1と同様にしてハードコートフィルムを作製した。この第1ハードコート層は、厚みが1.0μmm、屈折率が1.51であった。
ジペンタエリスリトールヘキサアクリレート40質量部、ウレタンアクリレートオリゴマー(根上工業(株)の「UN-901T」;分子中に重合性官能基を9個含む)40質量部、粒子分散液Fを固形分換算で15質量部、光重合開始剤(チバ・スペシャリティ・ケミカルズ(株)製「イルガキュア(登録商標)184」)5質量部を有機溶剤(メチルイソブチルケトン)に混合して、固形分濃度が30質量%の組成物を調製した。
第1ハードコート層を形成するための活性エネルギー線硬化性組成物を下記の組成物に変更する以外は、実施例1と同様にしてハードコートフィルムを作製した。この第1ハードコート層は、厚みが1.0μmm、屈折率が1.51であった。
ジペンタエリスリトールヘキサアクリレート35質量部、ウレタンアクリレートオリゴマー(根上工業(株)の「UN-901T」;分子中に重合性官能基を9個含む)30質量部、粒子分散液Gを固形分換算で30質量部、光重合開始剤(チバ・スペシャリティ・ケミカルズ(株)製「イルガキュア(登録商標)184」)5質量部を有機溶剤(メチルイソブチルケトン)に混合して、固形分濃度が30質量%の組成物を調製した。
第1ハードコート層を形成するための活性エネルギー線硬化性組成物を下記の組成物に変更する以外は、実施例1と同様にしてハードコートフィルムを作製した。この第1ハードコート層は、厚みが1.0μmm、屈折率が1.51であった。
ジペンタエリスリトールヘキサアクリレート40質量部、ウレタンアクリレートオリゴマー(根上工業(株)の「UN-901T」;分子中に重合性官能基を9個含む)40質量部、粒子分散液Hを固形分換算で15質量部、光重合開始剤(チバ・スペシャリティ・ケミカルズ(株)製「イルガキュア(登録商標)184」)5質量部を有機溶剤(メチルイソブチルケトン)に混合して、固形分濃度が30質量%の組成物を調製した。
第1ハードコート層を形成するための活性エネルギー線硬化性組成物を下記の組成物に変更する以外は、実施例1と同様にしてハードコートフィルムを作製した。この第1ハードコート層は、厚みが1.0μmm、屈折率が1.52であった。
ジペンタエリスリトールヘキサアクリレート40質量部、ウレタンアクリレートオリゴマー(根上工業(株)の「UN-901T」;分子中に重合性官能基を9個含む)40質量部、粒子分散液Iを固形分換算で15質量部、光重合開始剤(チバ・スペシャリティ・ケミカルズ(株)製「イルガキュア(登録商標)184」)5質量部を有機溶剤(メチルイソブチルケトン)に混合して、固形分濃度が30質量%の組成物を調製した。
比較例3において、第1ハードコート層の厚みを2.0μmに変更する以外は比較例3と同様にしてハードコートフィルムを作成した。
実施例1の樹脂層積層PETフィルムの作製において、樹脂層形成用塗布液を樹脂層形成用塗布液bに変更する以外は、実施例1と同様にして両面に樹脂層が積層されたPETフィルムを作製した。PETフィルムの両面に積層された樹脂層はそれぞれ、屈折率が1.52で、厚みが0.09μmであった。
上記の樹脂層積層PETフィルムの一方の面に第1ハードコート層を比較例1と同様にして積層し、他方の面に第2ハードコート層を実施例1と同様にして積層してハードコートフィルムを作製した。第1ハードコート層の厚みは1.0μm、屈折率は1.51であり、第2ハードコート層の厚みは1.5μm、屈折率は1.52であった。
上記の実施例および比較例で得られたハードコートフィルムについて、前述の測定方法および評価方法に従って、各項目の測定および評価を行った。その結果を表1および表2に示す。
実施例1~6で得られたそれぞれのハードコートフィルムの第2ハードコート層の面に、下記の高屈折率層と低屈折率層をこの順に積層し、次いで低屈折率層の上に下記の透明導電膜を形成して、静電容量式タッチパネル用の透明導電性フィルムを作製した。
下記の高屈折率層形成用の活性エネルギー線硬化性組成物をグラビアコート法により塗布し、90℃で乾燥後、紫外線400mJ/cm2を照射して硬化させて厚みが0.04μmの高屈折率層を形成した。この高屈折率層の屈折率は1.65であった。
活性エネルギー線硬化性樹脂としてジペンタエリスリトールヘキサアクリレート47質量部、酸化ジルコニウム50質量部、および重合開始剤(チバ・スペシャリティ・ケミカルズ(株)製「イルガキュア(登録商標)184」)3質量部を有機溶媒(プロピレングリコールモノエチルエーテル)に分散・溶解して調製した。
下記の低屈折率層形成用の活性エネルギー線硬化性組成物をグラビアコート法により塗布し、90℃で乾燥後、紫外線400mJ/cm2を照射して硬化させて厚みが0.04μmの低屈折率層を形成した。この低屈折率層の屈折率は1.46であった。
活性エネルギー線硬化性樹脂としてジペンタエリスリトールヘキサアクリレート84質量部、中空シリカ14質量部、単量体の重合開始剤(チバ・スペシャリティ・ケミカルズ(株)製「イルガキュア(登録商標)184」)2質量部を有機溶媒(メチルイソブチルケトンとプロピレングリコールモノエチルエーテルとの質量比1:1の混合溶媒)に分散・溶解して調製した。
ITO膜を厚みが22nmとなるようにスパッタリング法で積層し、格子状パターンにパターン加工(エッチング処理)して透明導電膜を形成した。
実施例11~16の透明導電性フィルムについて、耐ブロッキング性および透明導電膜パターンの視認性を評価した。その結果を表3に示す。
実施例1において、樹脂層積層PETフィルムの両面にそれぞれ第1ハードコート層を積層する以外は、実施例1と同様にしてハードコートフィルムを作製した。樹脂層積層PETフィルムの両面に設けられた第1ハードコート層の厚みは、それぞれ1.0μmであった。
実施例2において、樹脂層積層PETフィルムの両面にそれぞれ第1ハードコート層を積層する以外は、実施例2と同様にしてハードコートフィルムを作製した。樹脂層積層PETフィルムの両面に設けられた第1ハードコート層の厚みは、それぞれ1.0μmであった。
実施例3において、樹脂層積層PETフィルムの両面にそれぞれ第1ハードコート層を積層する以外は、実施例3と同様にしてハードコートフィルムを作製した。樹脂層積層PETフィルムの両面に設けられた第1ハードコート層の厚みは、それぞれ1.0μmであった。
実施例4において、樹脂層積層PETフィルムの両面にそれぞれ第1ハードコート層を積層する以外は、実施例4と同様にしてハードコートフィルムを作製した。樹脂層積層PETフィルムの両面に設けられた第1ハードコート層の厚みは、それぞれ1.0μmであった。
実施例5において、樹脂層積層PETフィルムの両面にそれぞれ第1ハードコート層を積層する以外は、実施例5と同様にしてハードコートフィルムを作製した。樹脂層積層PETフィルムの両面に設けられた第1ハードコート層の厚みは、それぞれ1.0μmであった。
実施例6において、樹脂層積層PETフィルムの両面にそれぞれ第1ハードコート層を積層する以外は、実施例6と同様にしてハードコートフィルムを作製した。樹脂層積層PETフィルムの両面に設けられた第1ハードコート層の厚みは、それぞれ1.0μmであった。
上記の実施例21~26で得られたハードコートフィルムについて、前述の測定方法および評価方法に従って、各項目の測定および評価を行った。その結果を表4に示す。
実施例21~26で得られたそれぞれのハードコートフィルムの一方の面の第1ハードコート層の面に、下記の高屈折率層と低屈折率層をこの順に積層し、次いで低屈折率層の上に下記の透明導電膜を形成して、静電容量式タッチパネル用の透明導電性フィルムを作製した。
下記の高屈折率層形成用の活性エネルギー線硬化性組成物をグラビアコート法により塗布し、90℃で乾燥後、紫外線400mJ/cm2を照射して硬化させて厚みが0.03μmの高屈折率層を形成した。この高屈折率層の屈折率は1.70であった。
活性エネルギー線硬化性樹脂としてジペンタエリスリトールヘキサアクリレート37質量部、酸化ジルコニウム60質量部、および光重合開始剤(チバ・スペシャリティ・ケミカルズ(株)製「イルガキュア(登録商標)184」)3質量部を有機溶媒(プロピレングリコールモノエチルエーテル)に分散・溶解して調製した。
下記の低屈折率層形成用の活性エネルギー線硬化性組成物をグラビアコート法により塗布し、90℃で乾燥後、紫外線400mJ/cm2を照射して硬化させて厚みが0.04μmの低屈折率層を形成した。この低屈折率層の屈折率は1.51であった。
活性エネルギー線硬化性樹脂としてジペンタエリスリトールヘキサアクリレートを88質量部、コロイダルシリカ(日産化学工業(株)のオルガノシリカゾル「MIBK-SD-L」、平均粒子径45nm)を固形分換算で10質量部、重合開始剤としてオリゴマー型光重合開始剤(ランベルティ社製のエザキュアワン;ポリ[2-ヒドロキシ-2-メチル-1-〔4-(1-メチルビニル)フェニル〕プロパノン])2質量部を有機溶媒(メチルイソブチルケトンとプロピレングリコールモノエチルエーテルとの質量比1:1の混合溶媒)に分散・溶解して調製した。
ITO膜を厚みが20nmとなるようにスパッタリング法で積層し、格子状パターンにパターン加工(エッチング処理)して透明導電膜を形成した。
実施例31~36の透明導電性フィルムについて、耐ブロッキング性および透明導電膜パターンの視認性を評価した。その結果を表5に示す。
2 基材フィルム
3 第1ハードコート層
10 粒子集合体
11 突出部
1a 二次粒子
1b 一次粒子
T 突出部の高さ
L 突出部の長さ
Claims (13)
- 基材フィルムの少なくとも一方の面に第1ハードコート層を備えたハードコートフィルムであって、第1ハードコート層は、平均粒子径(r:μm)が0.5μm未満でかつ第1ハードコート層の厚み(d:μm)に対して0.5倍以下である粒子が複数個集合した粒子集合体を含有し、第1ハードコート層表面に前記粒子集合体による突出部が第1ハードコート層表面の4μm平方当たり1個以上の密度で存在することを特徴とするハードコートフィルム。
- 前記突出部は、第1ハードコート層表面の面方向(平面的)に10個以上の粒子が集合した状態で形成されている、請求項1に記載のハードコートフィルム。
- 前記突出部の長さ(L)が0.4μm以上である、請求項1または2に記載のハードコートフィルム。
- 前記粒子がシリカ粒子であり、シリカ粒子またはシリカ粒子集合体が、表面自由エネルギーを小さくするための表面処理もしくは界面活性剤による表面処理が施されている、請求項1~3のいずれかに記載のハードコートフィルム。
- 前記シリカ粒子が気相法シリカである、請求項4に記載のハードコートフィルム。
- ハードコートフィルムのヘイズ値が0.7%以下である、請求項1~5のいずれかに記載のハードコートフィルム。
- 前記第1ハードコート層表面の中心線平均粗さ(Ra1)が25nm以下である、請求項1~6のいずれかに記載のハードコートフィルム。
- 前記粒子の平均粒子径(r:μm)が0.01μm以上0.4μm未満である、請求項1~7のいずれかに記載のハードコートフィルム。
- 前記第1ハードコート層の厚み(d:μm)が0.5μm以上4μm未満である、請求項1~8のいずれかに記載のハードコートフィルム。
- 前記基材フィルムの両面に第1ハードコート層を備えた、請求項1~9のいずれかに記載のハードコートフィルム。
- 前記基材フィルムが、屈折率が1.62~1.70であるポリエチレンテレフタレートフィルムであり、該ポリエチレンテレフタレートフィルムの片面もしくは両面に、屈折率が1.55~1.61である樹脂層を介して屈折率が1.48~1.54である第1ハードコート層が積層されている、請求項1~10のいずれかに記載のハードコートフィルム。
- 前記基材フィルムが、屈折率が1.62~1.70であるポリエチレンテレフタレートフィルムであり、該ポリエチレンテレフタレートフィルムの一方の面に屈折率が1.55~1.61である樹脂層を介して屈折率が1.48~1.54である第1ハードコート層が積層されており、かつ前記ポリエチレンテレフタレートフィルムの他方の面に屈折率が1.55~1.61である樹脂層を介して屈折率が1.48~1.54である第2ハードコート層が積層されている、請求項1~9のいずれかに記載のハードコートフィルム。
- 請求項1~12のいずれかに記載のハードコートフィルムの少なくとも一方の面に透明導電膜を有する、透明導電性フィルム。
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WO2013147151A1 (ja) * | 2012-03-30 | 2013-10-03 | 三菱化学株式会社 | 活性エネルギー線硬化性樹脂組成物、積層体およびロール状積層体 |
JP2014141075A (ja) * | 2012-12-27 | 2014-08-07 | Jgc Catalysts & Chemicals Ltd | ハードコート膜付基材およびハードコート膜形成用塗布液 |
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JP2018044151A (ja) * | 2016-09-07 | 2018-03-22 | 東山フイルム株式会社 | 透明導電性フィルム用のハードコートフィルム |
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JP5835517B1 (ja) | 2015-12-24 |
CN105764690B (zh) | 2018-05-18 |
JP2016027404A (ja) | 2016-02-18 |
KR20160090799A (ko) | 2016-08-01 |
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CN105764690A (zh) | 2016-07-13 |
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