JP6575191B2 - Finger sliding layer forming resin composition, finger sliding film and image display device using the same - Google Patents

Description

  The present invention relates to a finger-slip film, which is a finger-slip film having good finger slipperiness when a display is flicked. The present invention also relates to a resin composition for forming a finger sliding layer used for the finger sliding film and an image display device using the finger sliding film.

  Touch panel displays such as car navigation systems and smartphones, in addition to tapping (flicking with a finger), flicking (flicking with a finger), swiping (flicking with a finger), drag (moving with a finger placed), pinch-in ( Although it supports various gestures such as pinching out (operation to reduce the interval between two fingers) and pinch out (operation to increase the interval between two fingers), it is convenient in that information can be input by intuitive operation. For comfortable operation, it is necessary to slide a finger smoothly on the display, and excellent tactile sensation is required. In order to enhance the operability, it is required that the finger slippery during flicking is high.

  Therefore, Patent Document 1 discloses a surface film for the purpose of improving the touch of the surface without impairing the visibility of the display. In patent document 1, it is the surface film for multi-touch displays in which the unevenness | corrugation by the phase-separation structure of the some polymer was formed in the surface, Comprising: Haze is 15 to 50% and mapping using 0.5 mm width optical comb A surface film having a map definition of 5 to 50% measured by a property measuring instrument and a surface three-dimensional arithmetic average roughness Sa of 0.15 to 1 μm is disclosed. According to Patent Document 1, it is said that this surface film can improve tactile sensation while suppressing an increase in haze by forming irregularities by a phase separation structure of a plurality of polymers.

JP 2014-92657 A

  However, since the film disclosed in Patent Document 1 has a large average surface roughness Sa of 0.15 μm or more, the clear feeling is impaired. In addition, the touch panel display is operated by touching the surface with a finger, so there is a problem that the visibility is lowered due to the adhesion of the fingerprint. However, Patent Document 1 describes nothing about the wiping property of the fingerprint adhering to the surface. No.

  Accordingly, an object of the present invention is to provide a finger sliding film having a high clear feeling, good finger slipperiness during flicking, and good fingerprint wiping properties. Moreover, it is providing the image display apparatus using the resin composition for finger slip layer formation used for the finger slip film, and the finger slip film.

  The resin composition for forming a finger slip layer of the present invention comprises (a) 8.0 to 74.0% by mass of silica fine particles having an average particle size of 0.01 to 0.10 μm, and (b) an average particle size (Pdia). 1.0 to 9.0% by mass of translucent organic fine particles having an A of 0.5 to 1.3 μm, (c) 8.0 to 74.0% by mass of an ultraviolet curable resin, and (d) a fluorine-containing ultraviolet curable type 1.5 to 15.0 mass% of resin, (e) 0.8 to 11.0 mass% of polydimethylsiloxane having an acrylic group, (f) 0.1 to 12.0 mass% of photopolymerization initiator (provided that (A) (b) (c) (d) (e) (f) total is 100% by mass), and the finger slip is less than (%) by mass% in (e) It is a resin composition for layer formation.

  The finger slip film of the present invention has a hard base layer and a finger slip layer laminated in this order on a transparent substrate film, and the finger slip layer is formed by curing the resin composition for finger slip layer formation, The ratio t / Pdia of the film thickness t of the finger sliding layer and the average particle diameter Pdia of the translucent organic fine particles is 0.1 ≦ t / Pdia ≦ 0.9.

The finger-slip film of the present invention preferably has an arithmetic average roughness Ra and an average interval Sm of irregularities defined by JIS B0601-1994 in the surface shape satisfying the following formulas (I) and (II).
0.06 ≦ Ra ≦ 0.13 Formula (I)
0.02 ≦ Sm ≦ 0.05 Formula (II)

  The slip film referred to in the present invention is provided on the surface of an image display device.

  In this specification, “XX to XX” indicating a numerical range means “XX or more and XX or less” unless otherwise specified.

  According to the present invention, it is possible to provide a finger sliding film having high clearness, good finger slipperiness during flicking, and good fingerprint wiping property. Moreover, the resin composition for finger slip layer formation used for the finger slip film and the image display apparatus using the finger slip film can be provided.

≪Resin composition for finger sliding layer formation≫
The resin composition for forming a finger slip layer is a resin composition for forming a finger slip layer formed on the surface of a finger slip film provided on the surface of an image display device such as a touch panel, (a) silica fine particles, (B) translucent organic fine particles, (c) an ultraviolet curable resin, (d) a fluorine-containing ultraviolet curable resin, (e) an acrylic group-containing polydimethylsiloxane, and (f) a photopolymerization initiator.

<(A) Silica fine particles>
(A) The silica fine particles have an average particle diameter of 0.01 μm or more and 0.10 μm or less. Silica fine particles are typically spherical. When the average particle size of the silica fine particles is less than 0.01 μm, the particles are likely to aggregate and it may be difficult to achieve uniform finger slipping. On the other hand, if the average particle diameter exceeds 0.10 μm, visible light is likely to be scattered, and thus haze may increase.

  As long as the particle diameter of the silica fine particles is a method for measuring the average particle diameter of the particles, any measuring method can be applied. Preferably, the particles are observed with a transmission electron microscope (magnification of 20,000 to 2,000,000 times). And 100 particles are observed, and the average value is defined as the (average) particle diameter.

  In the resin composition for forming a finger slip layer, the ratio of (a) silica fine particles in the total 100 mass% of (a) to (f) is 8.0 to 74.0 mass%. When the ratio of the mass of the silica fine particles having an average particle diameter of 0.01 μm or more and 0.10 μm or less is less than 8.0% by mass, the surface irregularity interval (≈Sm) becomes large, and the finger slipperiness is deteriorated. (Friction coefficient increases). On the other hand, when the ratio of the mass of silica fine particles having an average particle diameter of 0.01 μm or more and 0.10 μm or less exceeds 74.0% by mass, the content of (c) ultraviolet curable resin as a binder is relatively small. Therefore, the surface hardness of the finger sliding film tends to decrease.

<(B) Translucent organic fine particles>
(B) The translucent organic fine particles have an average particle size of 0.5 μm or more and 1.3 μm or less. The light-transmitting organic fine particles are spherical and have an average particle size of 0.01 μm or more and 0.10 μm or less. An uneven shape is formed on the surface of the finger-slip film by the translucent organic fine particles having an average particle diameter of 0.5 μm or more and 1.3 μm or less. When the average particle diameter Pdia is less than 0.5 μm, the surface unevenness (≈Ra) becomes too small, and the finger slipping property is deteriorated. On the other hand, when the average particle size Pdia exceeds 1.3 μm, the surface unevenness interval (≈Sm) increases, and the contact area with the finger increases, so the finger slipping property decreases. By controlling to 0.5 μm ≦ Pdia ≦ 1.3 μm, the size of the surface unevenness (≈Ra) and the surface unevenness interval (≈Sm) can be adjusted appropriately.

  The average particle diameter Pdia of the light-transmitting organic fine particles may be any measuring method as long as it is a method for measuring the average particle diameter of the particles, but is preferably a transmission electron microscope (magnification of 20,000 to 2,000,000 times). The particles are observed, and 100 particles are observed, and the average value is defined as the (average) particle diameter.

  If the specific gravity of the light-transmitting organic fine particles is smaller than that of the silica fine particles, the light-transmitting organic fine particles are easily segregated on the upper layer portion of the finger sliding layer to form irregularities. As a guideline, the specific gravity Pden is Pden ≦ Those that are 1.6 can be selected. Examples of such materials include acrylic resins, polystyrene, polymethacrylstyrene, cross-linked acrylic-styrene copolymer resins, benzoguanamine formaldehyde condensates, benzoguanamine / melamine / formaldehyde condensates, melamine / formaldehyde condensates, polyethylene resins, epoxy resins, and silicone resins. , Polyvinylidene fluoride, and polyfluorinated ethylene resin. Of these, acrylic, polystyrene, and a cross-linked acrylic-styrene copolymer resin are preferable because they have a low specific gravity and easily develop finger slipping properties. The light-transmitting organic fine particles may be used alone or in combination of two or more. If the specific gravity of the translucent organic fine particles is smaller than the specific gravity of the finer particles (silica fine particles) and the specific gravity of the silica fine particles exceeds 3 times the specific gravity of the translucent organic fine particles, The balance between the antiglare property and the clear feeling, which are in a trade-off relationship with each other, is lost, and the antiglare property tends to be exhibited and the clear feeling tends to be impaired. When the anti-glare property is exhibited in the finger sliding film, it is not preferable because glare is easily generated when the finger sliding film is provided on the surface of the image display device.

  In the resin composition for forming a finger slip layer, the ratio of (b) the light-transmitting organic fine particles in the total of 100% by mass of (a) to (f) is 1.0 to 9.0% by mass. When the ratio of the mass of the light-transmitting organic fine particles is less than 1.0% by mass, the interval between the concaves and convexes (≈Sm) is increased, and the finger slipping property is degraded. On the other hand, when the ratio of the mass of the light-transmitting organic fine particles exceeds 9.0% by mass, the unevenness (≈Ra) on the surface becomes too large, and the clear feeling is impaired.

<(C) UV curable resin>
(C) As an ultraviolet curable resin, a monomer having a radical polymerizable functional group such as an acryloyl group, a methacryloyl group, an acryloyloxy group or a methacryloyloxy group, or a cationic polymerizable functional group such as an epoxy group, a vinyl ether group or an oxetane group , Oligomers, and prepolymers are used alone or mixed appropriately. Examples of monomers include methyl acrylate, methyl methacrylate, methoxy polyethylene methacrylate, cyclohexyl methacrylate, phenoxyethyl methacrylate, ethylene glycol dimethacrylate, dipentaerythritol hexaacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, and the like. it can. As oligomers and prepolymers, polyester acrylate, polyurethane acrylate, polyfunctional urethane acrylate, epoxy acrylate, polyether acrylate, acrylate compounds such as alkit acrylate, melamine acrylate, silicone acrylate, unsaturated polyester, tetramethylene glycol diglycidyl ether, Epoxy compounds such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A diglycidyl ether and various alicyclic epoxies, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3- Examples include oxetane compounds such as ethyl-3-oxetanyl) methoxy] methyl} benzene and di [1-ethyl (3-oxetanyl)] methyl ether. Door can be. These can be used alone or in combination.

  In the resin composition for forming a finger slip layer, the proportion of the mass of the (c) ultraviolet curable resin in the total 100 mass% of (a) to (f) is 8.0 to 74.0 mass%. When it exceeds 74.0% by mass, the average particle size is 0.5 μm or more and 1.3 μm or less. (B) Translucent organic fine particles and the average particle size is 0.01 μm or more and 0.10 μm or less (a) Silica Since the content of the fine particles is reduced, the unevenness interval (≈Sm) is increased, and the finger slipping property is deteriorated. On the other hand, when the ratio of (c) the ultraviolet curable resin is less than 8.0% by mass, voids are generated in the film and the strength is lowered.

<(D) Fluorine-containing UV curable resin>
(D) The fluorine-containing ultraviolet curable resin is for exhibiting an antifouling function, and can weaken the adhesion of fingerprints that adhere when the finger sliding layer surface is touched. Specific examples of (d) fluorine-containing ultraviolet curable resins include those represented by the following chemical formula (1) and those represented by the following chemical formula (2).

（ 式中、ｎ は０ 〜 １ ０ ０ の整数である。また、Ｘ はＨまたはCH₃である。）

(In the formula, n is an integer of 0 to 1 0 0. X is H or CH _3. )

（ 式中、Ｘ はパーフルオロアルキル基又はパーフルオロポリエーテルを表す。）

(Wherein X represents a perfluoroalkyl group or a perfluoropolyether)

  In the resin composition for forming a finger slip layer, the ratio of (d) the fluorine-containing ultraviolet curable resin in the total 100 mass% of (a) to (f) is 1.5 to 15.0 mass%. If the content is less than 1.5% by mass, the adhesion of the fingerprint when the surface of the finger sliding layer is touched cannot be effectively reduced. On the other hand, when it exceeds 15.0 mass%, the wiping property of fingerprints deteriorates.

<(E) Polydimethylsiloxane having an acrylic group>
(E) The polydimethylsiloxane having an acrylic group is for improving the wiping property of fingerprints attached to the surface of the finger sliding layer.

(E) The basic skeleton (polydiorganosiloxane) of polydimethylsiloxane having an acrylic group is represented by the following general formula (3), and has at least two polymerizable reactive groups in one molecule, preferably 2 to 8 Compound.

  A and B in the general formula (3) are linear or branched organic groups, an alkyl chain (C1-30), a perfluoroalkyl chain (C1-10), an arylalkyl chain, Aliphatic to aromatic (poly) ester chains (partial molecular weight of the organic chain 100 to 3000), aliphatic to aromatic (poly) ether chains (partial molecular weight of the organic chain 100 to 3000) and aliphatic Or at least one skeleton selected from the group consisting of aromatic (poly) urethane chains (partial molecular weight of the organic chain 100 to 3000), and a polymerizable reactive group is introduced into the organic group In the molecule, A and B may be the same or different, and A or B may be the same or different. However, the number of polymerizable reactive groups introduced into A and B is a compound having two, preferably 2 to 8, per molecule. Furthermore, it is more preferable that the polymerizable reactive group is introduced into B for the convenience of synthesis. C in the general formula (3) represents the length of the polysiloxane skeleton in the form of c + 1, and is preferably an integer of 3 to 250, more preferably 6 to 100.

  As the polymerizable reactive group, at least an acrylic group is introduced. The acryl group to be introduced is preferably an acryloyloxy group in terms of excellent reactivity. In addition to the acryloyloxy group, a (meth) acryloyloxy group, an α-fluoroacryloyloxy group, and the like can also be introduced. As a bonding method between the polymerizable reactive group and the polysiloxane skeleton, a conventionally known bonding method, for example, (poly) ether type, (poly) ester type, (poly) ester type and (poly) urethane type are combined. All of the bonding methods such as a bonding method combining a (poly) ether type and a (poly) urethane type, a bonding method combining a (poly) ester type and a (poly) ether type, and the like can be employed.

  For example, in the case of a bonding method combining a polyester type and a polyurethane type, the structure of the polydiorganosiloxane molecule has a basic skeleton as shown in the following general formula (4) and extends from the polysiloxane site. A polymerizable reactive group is bonded to the ends of three or more side chains of the chain.

  X in the general formula (4) is an integer of 3 to 250, preferably an integer of 6 to 100, and Y and Z are integers satisfying that Y + Z is 3 or more, preferably 4 to 20, m and n are both integers of 1-10. m and n may be the same or different, but the same is preferable in that a polydimethylsiloxane having an acrylic group can be easily prepared.

  R1 in the general formula (4) is a linear alkyl group (1 to 30 carbon atoms), a perfluoroalkyl group (1 to 10 carbon atoms), an arylalkyl group, a polyester group (partial molecular weight of the side chain) 200 to 2000, and bonded to the Si atom via an alkyl chain), a polyether group (partial molecular weight of the side chain is 200 to 2000, and bonded to the Si atom via an alkyl chain) One of them). R1 may be the same or different in the molecule, but it is more preferable that they are the same because the preparation of polydimethylsiloxane having an acrylic group is simple. Further, from the viewpoint of compatibility with the resin at the time of use, it is most general and preferable that R1 is a methyl group.

  R2 in the general formula (4) is a linear or branched chain having 3 to 30 carbon atoms, preferably 3 to 15 carbon atoms, and has at least two urethane bonds on the chain. It is bonded to the siloxane skeleton and R3 (provided that R3 is bonded so that three or more are contained in one molecule of polydiorganosiloxane). R2 may be the same or different in the molecule, but it is more preferable that they are the same because preparation of polydimethylsiloxane having an acrylic group is simple.

  R3 in the general formula (4) is a portion having a polyester skeleton, preferably a polyester skeleton containing three or more ester bonds, and has a polymerizable reactive group as described above, preferably a (meth) acryloyl group at the terminal. Are combined. In the molecule, R3 may be the same or different, but the same is more preferable because preparation of polydimethylsiloxane having an acrylic group is simple. Further, from the viewpoint of compatibility with the resin at the time of use, it is most general and preferable that R3 has a polycaprolactone skeleton composed of 3 or more caprolactones.

  R4 in the general formula (4) is any one of hydrogen, fluorine and methyl groups, and R4 may be the same or different in the molecule, but the preparation of polydimethylsiloxane having an acrylic group is simple. Are more preferable.

  Next, some more specific examples in the case of using the bonding method combining the polyester type and the polyurethane type as described above will be described together with an example of the manufacturing method. However, the example about the following manufacturing method does not mean that polydimethylsiloxane which has an acrylic group is limited to the following example.

  For example, by ring-opening polymerization of ε-caprolactone using polydimethylsiloxane represented by average formula (5) obtained by a conventionally known method, triisocyanate represented by general formula (6), and ethylene glycol monomethacrylate. Using the prepared polymerizable reactive group-containing polyester represented by the general formula (7) in a molar ratio of 1: 2: 4, a polycrystal represented by the average formula (8) is obtained by a conventionally known urethane bond forming reaction. A dimethylsiloxane compound is obtained. At this time, after adding polydimethylsiloxane (5) to triisocyanate (6) and forming urethane bonds at both ends of polydimethylsiloxane (5), urethane with polymerizable reactive group-containing polyester (7) By forming a bond, a by-product [for example, a by-product composed only of polydimethylsiloxane (5) and triisocyanate (6), or a polymerizable reactive group-containing polyester (7) and triisocyanate (6) only. The desired polydimethylsiloxane (8) can be obtained in a high yield by suppressing the production of by-products and the like].

  Here, d in the average formulas (5) and (8) is an integer of 15 to 20, e is an integer of 1 to 5, f in the general formula (6) is an integer of 4 to 8, and the general formula (7) And g in average formula (8) is an integer of 3-5. In the average formulas (5) and (8), Me represents a methyl group.

  In addition, for example, polydimethylsiloxane represented by the average formula (9) obtained by a conventionally known method, diisocyanate represented by the general formula (10), and ε-caprolactone using pentaerythritol triacrylate By using a polymerizable reactive group-containing polyester represented by the general formula (11) prepared by ring-opening polymerization in a molar ratio of 1: 2: 2, an average formula (12) is obtained by a conventionally known urethane bond forming reaction. The polydimethylsiloxane compound represented by these is obtained. At this time, after adding polydimethylsiloxane (9) to diisocyanate (10) and forming urethane bonds at both ends of polydimethylsiloxane (9), urethane bonds with polymerizable reactive group-containing polyester (11) By forming a by-product [for example, a by-product consisting of only polydimethylsiloxane (9) and diisocyanate (10), or a by-product consisting only of polymerizable reactive group-containing polyester (11) and diisocyanate (10) Etc.] and the desired polydimethylsiloxane (12) can be obtained in high yield.

  Here, h in the average formula (9) is an integer of 25 to 35, i is an integer of 1 to 5, j in the general formula (10) is an integer of 5 to 10, and k in the general formula (11). Is an integer of 3-5. In the average formula (12), h is 29, i is 5, j is 6, and k is 5.

  Further, for example, the above two examples are combined to react polydimethylsiloxane represented by the average formula (9), triisocyanate (6), and polymerizable reactive group-containing polyester (11) at a molar ratio of 1: 2: 4. (12) polydimethylsiloxane having an acryloyloxy group can also be obtained.

  In addition to this, polydimethylsiloxane is synthesized by a method in which a polyester portion having a polymerizable reactive group and a polyurethane portion are bonded and then introduced into a siloxane skeleton, or a method in which a polymerizable reactive group is finally introduced. It is also possible. Usually, the compound represented by General formula (3) can be used individually or in combination of 2 or more types.

  In addition, organopolysiloxane having one polymerizable reactive group in one molecule, for example, one-terminal (meth) acryloyloxy-modified polydimethylsiloxane, polydiorganosiloxane having the above specific structure (polydimethylsiloxane having an acrylic group), and Can also be used in combination.

  In the resin composition for forming a finger sliding layer, (e) polydimethylsiloxane having an acrylic group is contained in an amount of 0.8 to 11.0% by mass in a total of 100% by mass of (a) to (f). When the content is less than 0.8% by mass, the wiping property of the fingerprint attached to the surface of the finger sliding layer is not improved. On the other hand, if it exceeds 11.0% by mass, the adhesion of the fingerprint when the surface of the finger sliding layer is touched cannot be weakened.

<(F) Photopolymerization initiator>
(F) The photopolymerization initiator is used as a polymerization initiator when the finger slip layer forming resin composition is cured by an active energy ray such as ultraviolet (UV) to form a coating film. (F) As a photoinitiator, if a polymerization is started by irradiation with active energy ray, it will not specifically limit, A well-known compound can be used. For example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -One, acetophenone polymerization initiators such as 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzoin, 2,2-dimethoxy 1,2 -Benzoin polymerization initiators such as diphenylethane-1-one, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ', 4,4' -Benzophenone polymerization initiators such as tetra (t-butylperoxycarbonyl) benzophenone, 2-chlorothio Sandton, such thioxanthone type polymerization initiators such as 2,4-diethyl thioxanthone, and the like.

  In the resin composition for forming a finger sliding layer, the ratio of the photopolymerization initiator (f) in the total 100% by mass of (a) to (f) is 0.1 to 12.0% by mass. When the photopolymerization initiator is less than the above range, the polymerization becomes insufficient and the adhesion cannot be exhibited. On the other hand, when the amount is larger than the above range, the cross-linking density of the film is lowered, and the strength is weakened.

  If necessary, the resin composition for forming a finger sliding layer may be prepared by adding conventionally known additives such as a surface preparation agent, an ultraviolet absorber, an ultraviolet stabilizer, an antioxidant, an antistatic agent, and an antifoaming agent. You may contain in the range which does not impair an effect.

≪Finger slip film≫
The finger sliding film is based on a transparent substrate film, and a hard coat layer and a finger sliding layer are laminated in this order on at least one surface thereof.

<Transparent substrate film>
The transparent substrate film is not particularly limited as long as it is colorless and transparent. Examples of the material for forming such a transparent substrate film include polyesters such as triacetyl cellulose and polyethylene terephthalate, cycloolefin polymers, polycarbonate resins, or polymethyl methacrylate resins, polyarylate, and polyether sulfone. Of these, triacetyl cellulose and polyethylene terephthalate are preferable in terms of high versatility. These transparent base films have a refractive index of about 1.47 to 1.70 for light of 589 nm.

  The thickness of the transparent substrate film is preferably about 25 to 400 μm, more preferably about 50 to 200 μm. When the thickness of the transparent substrate film is thinner than 25 μm or thicker than 400 μm, the handleability during the production and use of the finger sliding film is lowered.

<Hard coat layer>
A hard coat layer is provided between the transparent substrate film and the finger slip layer in order to increase the surface hardness of the sliding film.

  The film thickness of the hard coat layer is preferably 1 μm or more. A film thickness of less than 1 μm is not preferable because the surface hardness cannot be increased effectively. Further, the film thickness of the hard coat layer is preferably 3 μm or more. When the thickness exceeds 20 μm, problems such as a decrease in flex resistance occur, which is not preferable.

  The material for the hard coat layer is not particularly limited as long as it is a known material conventionally used for a film provided on the surface of a display. For example, a reactive silicon compound such as tetraethoxysilane or an active energy ray curable resin can be used, and these may be mixed. And the hard-coat layer can be formed by irradiating and hardening | curing active energy rays, such as an ultraviolet-ray and an electron beam, to the coating liquid for hard-coat layers prepared by adding a photoinitiator to these.

  Examples of the active energy ray-curable resin include monofunctional (meth) acrylate and polyfunctional (meth) acrylate. Specifically as monofunctional (meth) acrylate, (meth) acrylic acid alkyl ester, (meth) acrylic acid (poly) ethylene glycol group-containing (meth) acrylic acid ester and the like are preferable. Examples of the polyfunctional (meth) acrylate include ester compounds of polyhydric alcohol and (meth) acrylic acid, polyfunctional polymerizable compounds containing two or more (meth) acryloyl groups such as urethane-modified acrylate, and the like.

  Among these, from the viewpoint of achieving both productivity and hardness, a cured product of a composition containing an active energy ray-curable resin having a pencil hardness (evaluation method: JIS-K5600-5-4) of H or higher is preferable. . The composition containing such an active energy ray curable resin is not particularly limited. For example, a known active energy ray curable resin or a mixture of two or more known active energy ray curable resins may be mixed. And those commercially available as ultraviolet curable hard coat materials.

  The photopolymerization initiator is used as a polymerization initiator when a coating film is formed by curing the hard coat layer coating liquid with an active energy ray such as ultraviolet (UV). The photopolymerization initiator is not particularly limited as long as it initiates polymerization upon irradiation with active energy rays, and known compounds can be used. For example, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 -One, acetophenone polymerization initiators such as 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzoin, 2,2-dimethoxy 1,2 -Benzoin polymerization initiators such as diphenylethane-1-one, benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 3,3 ', 4,4' -Benzophenone polymerization initiators such as tetra (t-butylperoxycarbonyl) benzophenone, 2-chlorothio Xanthone, such thioxanthone type polymerization initiators such as 2,4-diethyl thioxanthone, and the like.

  The solvent of the coating solution is not particularly limited as long as it is a known one that has been conventionally used for the coating solution for forming each layer in this type of antireflection film, and examples thereof include alcohol-based, ketone-based, and ester-based solvents. Can be selected in a timely manner.

  Furthermore, the hard coat layer may contain other additives. Examples of other additives include inorganic particles for adjusting the refractive index, antistatic agents, ultraviolet absorbers, ultraviolet stabilizers, antioxidants, and surface modifiers. As the antistatic agent, conductive metal oxide fine particles such as ATO fine particles and ITO fine particles, conductive polymers such as PEDOT, and surfactants such as quaternary ammonium salts can be used. As the surface conditioner, a silicon leveling agent such as polydimethylsiloxane or an acrylic leveling agent can be used.

≪Finger sliding layer≫
The finger sliding layer is formed by curing the finger sliding layer forming resin composition with ultraviolet rays. The sliding layer has fine unevenness on the surface, and the unevenness reduces the contact area of the finger to reduce the frictional force and enhance the finger slipping property. In addition, the finger slipping layer is designed to have a low surface free energy, and thus has a function that the attached fingerprint can be easily wiped off.

  The film thickness t of the finger sliding layer has an average particle diameter of 0.5 μm or more and 1.3 μm or less. (B) The ratio t / Pdia of the light-transmitting organic fine particles to the average particle diameter Pdia is 0.1 ≦ t / It is formed so as to satisfy Pdia ≦ 0.9. Here, the film thickness t of the finger sliding layer is the thickness of the portion without protrusion (convex) due to particles in the finger sliding layer. As long as the film thickness t of the finger sliding layer is a method for measuring the film thickness, any measurement method can be applied, but preferably, a reflection spectrum of a portion without protrusion (convex) due to particles is measured by a spectral film thickness meter. Then, it is calculated from the obtained reflection spectrum by the peak valley method. When t / Pdia> 0.9, the average particle diameter Pdia of the light-transmitting organic fine particles is small with respect to the film thickness t, and the surface unevenness (≈Ra) is small. Decreases. When 0.1 ≦ t / Pdia ≦ 0.9, the finger slipping property is good. If the thickness is 0.1 μm> t, the strength of the finger sliding layer tends to be reduced. When t> 1.3 μm, the surface unevenness interval (≈Sm) tends to increase, and the finger slipping property tends to deteriorate.

The finger sliding layer has an arithmetic average roughness Ra (average value of absolute value deviation from the average line) defined by JIS B 0601-1994 and an average interval Sm of unevenness (roughness curve intersects the average line) in the surface shape. By satisfying the following formulas (I) and (II), the average value of the valleys and the intervals obtained from the intersection points is easy to achieve both good finger slipping and clearness.
0.06 ≦ Ra ≦ 0.13 Formula (I)
0.02 ≦ Sm ≦ 0.05 Formula (II)
In the case of Ra <0.06, the finger contact area is increased, and thus the finger slipping property is deteriorated. When Ra> 0.13, there is a tendency for clearness to disappear. In the case of Sm <0.02, the haze increases, and thus there is a tendency that the clear feeling is lost. In the case of Sm> 0.05, the finger contact area is increased, and thus the finger slipping property is deteriorated.

  The finger slipping layer is, as necessary, a conventionally known additive such as a surface preparation agent, an ultraviolet absorber, an ultraviolet stabilizer, an antioxidant, an antistatic agent, and an antifoaming agent, in a range that does not impair the effects of the present invention. It may contain.

≪Formation of each layer≫
The method for forming the finger slip layer and the hard coat layer is not particularly limited. For example, each coating liquid prepared by appropriately diluting each layer forming resin composition with a solvent by a coating method of a wet coating method is applied to the transparent base film. The method of apply | coating and hardening can be employ | adopted. As the coating method, the wet coating method is particularly preferable in terms of productivity and production cost. The wet coating method may be a known method, and typical examples include a roll coating method, a die coating method, a spin coating method, and a dip coating method. In these, the method which can form a coating film continuously, such as a roll coat method, is preferable from the point of productivity. The formed coating film can form a cured film by performing a curing reaction by heating, irradiation with active energy rays such as ultraviolet rays and electron beams.

<Image display device with finger slip film on surface>
The image display device provided with the above-mentioned finger slip film on the surface of the screen can improve the slipperiness of the finger when flicking while maintaining a clear feeling on the screen, and can easily wipe off the attached fingerprint. Can do. Examples of the image display device include a car navigation system, a smartphone, a mobile PC, and an electronic blackboard display. The finger sliding film is attached to the observation side surface of the image display device via an OCA (optical clear adhesive), or attached to the observation side surface as a polarizing film. In the case of using a finger sliding film as a polarizing film, the polarizing film is generally a protective film laminated on at least one surface of a polarizer composed of a polyvinyl alcohol-based resin film adsorbed and oriented with iodine or a dichroic dye. Although many of the shapes are made, if the finger slip film is bonded to one surface of such a polarizing film, a polarizing film having a finger slip effect is obtained. Further, the above-mentioned finger sliding film is also used as a protective film, and a polarizing film having a finger sliding effect can also be obtained by pasting on one side of a polarizer so that one surface on which the finger sliding layer is laminated is outside. be able to.

(Example 1-1 to Example 1-13, Comparative Example 1-1 to 1-11)
[Finger sliding layer forming resin composition]
The following raw materials are used as the resin composition for forming the finger slip layer, and each raw material has the composition described in Table 1 and Table 2 below, (a) silica fine particles, (b) translucent organic fine particles, (c) Ultraviolet curable resin, (d) fluorine-containing ultraviolet curable resin, (e) polydimethylsiloxane having an acrylic group, and (f) photopolymerization initiator are mixed to form finger slipping layers of Examples and Comparative Examples A resin composition was prepared. In addition, the compounding quantity of each material has described the mass% of solid content.

The raw materials for the finger slip layer forming resin composition are as follows.
(A) Silica fine particles Silica ultra fine particles (particle size: 100 nm) “SIMIBK15WT% -H58” manufactured by CIK Nanotech Co., Ltd.
Silica ultrafine particles (particle size 15nm) "MIBK-ST" manufactured by Nissan Chemical Industries, Ltd.
In Comparative Example 1-1, instead of silica fine particles, zirconia fine particles (particle diameter: 15 nm) “ZRMEK 25 wt% -F47” manufactured by CIK Nanotech Co., Ltd.
(B) Translucent organic fine particles Cross-linked acrylic polymer resin fine particles (manufactured by Soken Chemical Co., Ltd., MX80H3wT, monodisperse fine particles with uniform particle diameter, average particle size is 0.8 μm)
Fine particles of acrylic polymer resin (manufactured by Nippon Paint Co., Ltd., FS-501, average particle size is 0.5 μm)
Fine particles of crosslinked acrylic polymer resin (manufactured by Sekisui Chemical Co., Ltd., SSX-101, monodisperse fine particles with uniform particle size, average particle size is 1.0 μm)
Polystyrene fine particles [manufactured by Soken Chemical Co., Ltd., SX-130H, monodispersed fine particles with uniform particle size, average particle size is 1.3 μm]
Fine particles of cross-linked acrylic polymer resin (manufactured by Soken Chemical Co., Ltd., MX-150, monodisperse fine particles with uniform particle size, average particle size is 1.5 μm)
(C) UV curable resin dipentaerythritol hexaacrylate, “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.
Multifunctional urethane acrylate "Shikou UV-7600B" manufactured by Nippon Synthetic Chemical Industry Co., Ltd.
(D) Fluorine-containing UV curable resin “OPTOOL DAC-HP” manufactured by Daikin Industries, Ltd.
"Megafuck RS-75" manufactured by DIC Corporation
(E) Polydimethylsiloxane having an acrylic group "BYK-UV 3570" manufactured by Big Chemie Japan Co., Ltd. Polyester-modified polydimethylsiloxane having an acrylic group "BYK-UV 3500" poly having an acrylic group manufactured by Big Chemie Japan Co., Ltd. Ether-modified polydimethylsiloxane (f) photopolymerization initiator
“IRGACURE907 (I-907)” manufactured by Ciba Specialty Chemicals Co., Ltd.
“IRGACURE2959 (I-2959)” manufactured by Ciba Specialty Chemicals Co., Ltd.
“IRGACURE 184 (I-184)” manufactured by Ciba Specialty Chemicals Co., Ltd.

[Production of finger sliding film]
[Transparent substrate film]
In each Example and Comparative Example, the following were used as the transparent substrate film.
Polyethylene terephthalate film (PET):
“U403” manufactured by Toray Industries, Inc. Thickness 100 μm

[Hardcoat layer forming resin composition]
HC-1: UV curing type hard coating agent having an acrylic group “Aika Itron Z735HSL” (manufactured by Aika Industry Co., Ltd.)
HC-2: UV curable hard coat agent having an acrylic group "OPSTAR Z7503" (manufactured by JSR Corporation)
HC-3: UV curable hard coating agent having a quaternary ammonium salt and an acrylic group “Rioduras LAS1303NL” (manufactured by Toyo Ink Co., Ltd.)

(Example 2-1)
On one side of a polyethylene terephthalate film “U403, 100 μm” manufactured by Toray Industries, Inc., a hard coat agent “Aika Itron Z735HSL” (HC-1) having an acrylic group is applied with a bar coater and dried. Cured and coated so that the film thickness after curing (film thickness measured avoiding particles) is 4 μm, cured by irradiating with 400 mJ ultraviolet light with a 120 W high-pressure mercury lamp, and having a surface resistivity of 1E + 9Ω. A hard coat layer was formed on a polyethylene terephthalate film.

  Further, a coating solution prepared by mixing the resin composition for forming the finger slip layer of Example 1-1 and the solvent (methyl isobutyl ketone) at a ratio of 1: 1 on the hard coat layer was applied with a bar coater, dried and cured. The film was coated so that the film thickness after curing (the film thickness measured avoiding particles) was 0.4 μm, and a finger sliding layer was formed by irradiating with a 120 W high-pressure mercury lamp by irradiating with 400 mJ ultraviolet rays. A sliding film was prepared.

(Example 2-2 to Example 2-17, Comparative Example 2-1 to Comparative Example 2-13)
As a resin composition for forming a finger slip layer, a hard coat layer and a finger slip layer were formed in the same manner as in Example 2-1 with the compositions and configurations described in Table 3 and Table 4 to prepare a finger slip film.

  Various characteristics of the obtained finger sliding films of Examples and Comparative Examples were measured and evaluated by the following methods.

<Film thickness of finger sliding layer (t)>
(1) A reflection spectral film thickness meter [FE3000, manufactured by Otsuka Electronics Co., Ltd.] was used to measure a reflection spectrum of a portion without protrusion (convex) due to particles, and described in the following <refractive index of each layer composition after curing>. Based on the refractive index of the film after curing of the hard coat layer obtained in the procedure, the total film thickness (ii) of the hard coat layer and the finger slip layer is calculated from the obtained reflection spectrum by the peak valley method. The film thickness of the finger sliding layer was calculated in (A).
Film thickness of finger sliding layer (iii) = (total film thickness of hard coat layer and finger sliding layer (ii) −film thickness of hard coat layer (i)) × refractive index of hard coat layer / refractive index of finger sliding layer (Formula A)

<The refractive index of each layer composition after curing>
(1) The coating liquid for each layer is 100 to 1000 nm in thickness after drying and curing with a bar coater on the surface of the PET film [trade name “A4100”, manufactured by Toyobo Co., Ltd.] without the easy adhesion layer. Thus, the thickness of the layer was adjusted and applied. After drying, the film was cured by irradiating with 400 mJ of ultraviolet light using a 120 W high-pressure mercury lamp in a nitrogen atmosphere with an ultraviolet irradiation device (manufactured by Iwasaki Electric Co., Ltd.) to prepare a film for refractive index measurement.
(2) The reflection spectrum was measured with a reflection spectral film thickness meter (FE3000, manufactured by Otsuka Electronics Co., Ltd.) after the back surface of the produced film was roughened with sandpaper and painted with black paint.
(3) From the reflectance read from the reflection spectrum, the constant of the wavelength dispersion formula (Formula 1) of n-Cauchy shown below was obtained, and the refractive index at the wavelength of 589 nm was obtained.
N (λ) = a / λ4 + b / λ2 + c (Formula 1)
The refractive index of the finger sliding layer is calculated by curing a composition excluding large-diameter particles among the compositions constituting the finger sliding layer to form a cured film, and measuring the reflection spectrum of the cured film. did.

<Film thickness of hard coat layer (i)>
The reflection spectrum film thickness meter (FE3000, manufactured by Otsuka Electronics Co., Ltd.) measured the reflection spectrum of the part without protrusion (convex) due to the particles, and determined by the procedure described in <Refraction index of each layer composition after curing> Based on the refractive index of the film after curing of the layer, it was calculated from the obtained reflection spectrum by the peak valley method.

<Surface roughness>
Arithmetic average roughness in accordance with the provisions of JIS B 0601-1994, using a surface roughness measuring machine manufactured by Kosaka Laboratory Co., Ltd., Surfcorder SE500, under conditions of a scanning range of 4 mm and a scanning speed of 0.2 mm / s. Ra (μm) and the average interval Sm (mm) of the irregularities were measured.

<Finger slipperiness>
The coefficient of dynamic friction with respect to an artificial skin model of urethane elastomer material (trade name: Bio Skin Plate Plate #BS Color 1, manufactured by Beaulux Co., Ltd.) was measured by a measurement method based on JIS K 7125-1999.

  The friction coefficient evaluated by this evaluation method correlates with the slipperiness when flicking with a human finger. The smaller the friction coefficient, the easier the finger slips, and the higher the friction coefficient, the more sensitive the finger is, It was evaluated. In addition, when the friction coefficient is such that the friction coefficient ≦ 0.5, 90% or more of the evaluators (N = 30) determined that the finger is easy to slip when flicking.

<Clear>
(1) <Transparent image definition, 45 ° reflection image definition>
An image definition value (transmission image definition) through an optical comb having a width of 1 mm using an image definition measuring device (image clarity measuring device manufactured by Suga Test Instruments Co., Ltd., ICM-1T) based on JIS K 7105-1981. (Degree) (%) and image sharpness value (45 ° reflected image sharpness) (%) measured at 45 ° reflection. As the transmitted image definition and the 45 ° reflected image definition are larger, the clearer the better.

(2) <Haze>
A haze meter (Nippon Denshoku Industries Co., Ltd., NDH2000) was used, and the haze value (%) as an optical characteristic was measured.

<Fingerprint wiping>
The attached fingerprint was wiped with Toray-made Toraysee under a load of 200 gf / cm ² , and the number of times of wiping necessary to make the fingerprint invisible was counted.
○: 20 round trips or less, x: 21 round trips or more

<Surface hardness>
The load was set to 750 g and evaluated according to JIS K 5600.

  From the results of each Example, (a) 8.0 to 74.0% by mass of silica fine particles having an average particle diameter of 0.01 to 0.10 μm, and (b) an average particle diameter (Pdia) of 0.5 to 1 1.0 μm to 9.0% by mass of translucent organic fine particles of 3 μm, (c) 8.0 to 74.0% by mass of ultraviolet curable resin, and (d) 1.5 to 15 fluorine-containing ultraviolet curable resin. 0.0% by mass, (e) 0.8-15.0% by mass of polydimethylsiloxane having an acrylic group, (f) 0.1-12.0% by mass of photopolymerization initiator (provided that (a) (b) (The sum of (c), (d), (e), and (f) is 100% by mass), and the resin composition for forming a finger sliding layer is less than (%) by mass% of (e). A finger slip film in which the ratio t / Pdia between the thickness t of the finger slip layer and the average particle diameter Pdia of the light-transmitting organic fine particles is 0.10 ≦ t / Pdia ≦ 0.90 According to a high clearness, a good slipperiness of the finger at the time of the flick, and wiping of the fingerprint is found to be good.

  On the other hand, from Comparative Example 2-1, it can be seen that when (a) zirconia fine particles are used instead of silica fine particles, the transmitted image line brightness and the 45 ° reflected image sharpness are reduced, and the clearness is lowered. In Comparative Example 2-2, (a) too few silica fine particles and (c) too much ultraviolet curable resin, the surface irregularity interval (≈Sm) becomes large and the finger slipping property is inferior. In Comparative Example 2-3, (a) Too much silica fine particles (c) Too little ultraviolet curable resin, fingerprint wiping properties are poor. In Comparative Example 2-4, since (b) the light-transmitting organic fine particles are too small, the surface unevenness interval (≈Sm) is increased and the finger slipping property is inferior. In Comparative Example 2-5, (b) since there are too many translucent organic fine particles, the transmitted image line brightness and the 45 ° reflected image sharpness are small, and the haze is high, so the clearness is low. In Comparative Example 2-6, (b) the average particle diameter of the light-transmitting organic fine particles was too large, so that the transmitted image line brightness and the 45 ° reflected image sharpness were small and the clearness was low, and the unevenness of the surface (≈Sm) The finger slipperiness becomes slightly inferior. In Comparative Example 2-7, since the ratio t / Pdia between the film thickness t of the finger sliding layer and the average particle diameter Pdia of (b) the translucent organic fine particles is too small, the surface hardness is low. In Comparative Example 2-8, t / Pdia is too large, the surface unevenness (≈Ra) is small, and the surface unevenness interval (≈Sm) is large. In Comparative Example 2-9 and Comparative Example 2-10, since (d) the fluorine-containing ultraviolet curable resin is too little or too much, the fingerprint wiping property is poor. In Comparative Example 2-11, since there is too little (e) polydimethylsiloxane having an acrylic group, the fingerprint wiping property is poor. In Comparative Example 2-12 and Comparative Example 2-13, the fingerprint wiping property is poor because (e) the mass% of the polydimethylsiloxane having an acrylic group is larger than (d) the mass% of the fluorine-containing ultraviolet curable resin.

Claims (4)

(A) 8.0 to 74.0% by mass of silica fine particles having an average particle size of 0.01 to 0.10 μm,
(B) 1.0 to 9.0% by mass of translucent organic fine particles having an average particle diameter (Pdia) of 0.5 to 1.3 μm,
(C) UV curable resin 8.0 to 74.0% by mass,
(D) 1.5 to 15.0% by mass of a fluorine-containing ultraviolet curable resin,
(E) 0.8-11.0% by mass of polydimethylsiloxane having an acrylic group,
(F) Photoinitiator 0.1-12.0 mass%
(However, the total of (a) (b) (c) (d) (e) (f) is 100% by mass.)
Including
A resin composition for forming a finger sliding layer, wherein the mass% of (e) is less than the mass% of (d).   A hard coat layer and a finger slip layer are laminated in this order on a transparent base film, and the finger slip layer is formed by curing the resin composition for forming a finger slip layer according to claim 1. A finger sliding film, wherein a ratio t / Pdia of a layer thickness t and an average particle diameter Pdia of the translucent organic fine particles is 0.1 ≦ t / Pdia ≦ 0.9. The finger sliding film according to claim 2, wherein in the surface shape, the arithmetic average roughness Ra and the average interval Sm of irregularities defined in JIS B0601-1994 satisfy the following formulas (I) and (II): .
0.06 ≦ Ra ≦ 0.13 Formula (I)
0.02 ≦ Sm ≦ 0.05 Formula (II)   The image display apparatus provided with the finger-slip film of Claim 2 or Claim 3 on the surface.