JP2016099827A - Touch panel, laminate, and production method of laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a touch panel using a laminate having high hardness and excellent flexibility.SOLUTION: The touch panel includes a hard coat layer on one surface of a base film and a laminate having a resin cured layer on the other surface of the base film. The base film has a thickness of 40 to 125 μm; the hard coat layer has a thickness of 10 to 25 μm; and the total thickness of the laminate is 100 to 220 μm.SELECTED DRAWING: None

Description

The present invention relates to a touch panel, a laminate used for the touch panel, and a method for manufacturing the laminate.

Although glass products have high pencil hardness, they have a problem in workability that they are easy to break when they are difficult to bend, and they are also heavier than plastic products. For this reason, in recent years, plastic products have been replaced with glass products in terms of processability and weight reduction. However, since the surfaces of these plastic products are easily scratched, a base material that is a resin film for the purpose of imparting scratch resistance. In many cases, a hard coat film in which a hard coat layer is formed is bonded to the film.

Such a conventional hard coat film is usually prepared by applying an ionizing radiation curable resin such as a thermosetting resin or an ultraviolet curable resin directly on the base film or through a primer layer of about 1 μm. It is manufactured by forming a thin coating film of about 15 μm.
However, even if the hardness of the hard coat layer is sufficient, the conventional hard coat film has a hard film corresponding to the deformation of the underlying substrate film due to the thin coating film thickness. The coat layer was also deformed and the hardness of the hard coat film as a whole was lowered, which was not satisfactory.
For example, in a hard coat film in which an ultraviolet curable coating is applied in the above thickness on a polyethylene terephthalate (PET) film widely used as a base film, a pencil hardness of 3H is generally used, and glass The pencil hardness was not much higher than 9H.

On the other hand, for example, if the thickness of the hard coat layer is simply made thicker than the usual 3 to 15 μm, the hardness of the obtained hard coat film is improved, but cracking and peeling of the hard coat layer are likely to occur and at the same time due to curing shrinkage. There was a problem that the curl of the hard coat film was increased. For this reason, it has been difficult to obtain a hard coat film having good characteristics that can be used practically by the conventional technique.
As such a hard coat film, for example, in Patent Document 1, a hard coat layer having a thickness of 3 to 15 μm is formed on at least one surface of a plastic substrate film via a buffer layer having a thickness of 3 to 15 μm. A hard coat film having a hardness of 4H to 8H is disclosed.
Furthermore, as glass substitute materials, for example, Nippon Steel & Sumikin Chemical Co., Ltd., Sylplus (registered trademark), Showa Denko Co., Ltd., Shoreiaru (registered trademark), Nippon Gosei Chemical Co., Ltd., Olga (registered trademark), Nasaka Regalia and the like are commercially available from Vacuum Industries.

By the way, recently, there is an increasing demand for glass substitute products that are flexible in design, such as displays that can handle curved surfaces for digital signage applications and curved OLEDs, and hard coat films used for such applications. In addition, sufficient flexibility as well as excellent flexibility are required.
In particular, thin and flexible flexible organic EL displays have been developed in recent years, and attention has also been focused on portable panels such as smartphones and wristwatch-type terminals, display devices inside automobiles, and flexible panels used for watches and the like. It is coming.
However, the conventional hard coat film described in Patent Document 1 and Sylplus (registered trademark) of Nippon Steel & Sumikin Chemical Co., Ltd. are mainly focused on the hardness as the hard coat performance. However, no consideration was given to curved surfaces.

As a conventional laminate having hardness and flexibility, for example, in Patent Document 2, a hard coat layer is provided on one surface of a first plastic film that is an acrylic resin film, and an adhesive is provided on the other surface. There is described a laminate comprising a second plastic film laminated via layers, wherein the hard coat layer is a layer made of a resin containing an organic-inorganic hybrid type resin and a fluorine compound additive.
However, the laminate described in Patent Document 2 has a pencil hardness of about 5H and is not sufficient as a glass substitute material. Also, when it is wound around a cylinder having a diameter of 80 mm, cracks and peeling occur. However, it was not sufficient and could not be processed in a roll state and could not be wound.

JP-A-11-300873 JP2013-35210A

In view of the above-mentioned present situation, the present invention aims to provide a touch panel using a laminate having high hardness and excellent flexibility, a laminate useful as a glass substitute material for the touch panel, and a method for producing the laminate. To do.

The present invention is a touch panel including a laminate having a hard coat layer on one surface of a substrate film and a resin cured layer on the other surface of the substrate film, The touch panel is characterized in that the thickness is 40 to 125 μm, the thickness of the hard coat layer is 10 to 25 μm, and the total thickness of the laminate is 100 to 220 μm.

In the touch panel of the present invention, the laminate does not cause cracks when wound around a cylinder having a diameter of 20 mm. In the pencil hardness test (load 750 g) according to JIS K5600-5-4 (1999), the laminate is 6H or more. Preferably there is.
The hard coat layer preferably contains an antifouling agent having a reactive functional group.
It is preferable that the contact angle with respect to the water of the surface of the said hard-coat layer is 100-120 degrees.
Moreover, it is preferable that the said resin cured layer side surface of the said laminated body is stuck on a polarizer or a polarizing plate through an adhesive layer or an adhesive bond layer.
Moreover, it is preferable that the said resin cured layer is a cured layer of a monofunctional monomer.
The monofunctional monomer is preferably a monofunctional acrylic monomer.
The monofunctional acrylic monomer is at least one selected from the group consisting of acryloylmorpholine, N-acryloyloxyethylhexahydrophthalimide, cyclohexyl acrylate, tetrahydrofuryl acrylate, isobornyl acrylate, phenoxyethyl acrylate, and adamantyl acrylate. Preferably it is a seed.
Moreover, it is preferable that the laminated body has another base film on the surface opposite to the base film of the resin cured layer, and is provided on the surface opposite to the resin hardened layer of the other base film. It is preferable to have a hard coat layer.

Moreover, this invention is also a laminated body characterized by being used for the touchscreen of this invention.
The present invention also includes a step of forming a hard coat layer on one surface of the base film using the hard coat layer composition, and a cured layer composition on the other surface of the base film. It is also a method for producing a laminate having a step of forming a cured resin layer using a roll-to-roll method.
The present invention is described in detail below.

As a result of intensive studies on a laminate having a structure in which a hard coat layer is formed on a base film that is a resin film, the inventors have found that a cured resin layer is formed on the side surface opposite to the hard coat layer of the base film. The laminate formed and having the base film and the hard coat layer within the predetermined range has extremely excellent hardness and flexibility, and is extremely suitable as a glass substitute material used for a touch panel. As a result, the present invention has been completed.

This invention has a laminated body which has a hard-coat layer on one surface of a base film, and has a resin cured layer on the other surface of the said base film. The laminate having such a configuration is extremely excellent in hardness and flexibility as compared with a laminate used as a conventional glass substitute material.

In the touch panel of the present invention, the laminate does not cause cracks when wound around a cylinder having a diameter of 20 mm. In the pencil hardness test (load 750 g) according to JIS K5600-5-4 (1999), the laminate is 6H or more. Preferably there is.
When cracks occur when the laminate is wound around a cylinder with a diameter of 20 mm, the flexibility becomes insufficient, and the laminate can be made to correspond to a curved surface such as a flexible panel or manufactured by a roll-to-roll method. There are times when you can't. The winding around the cylinder is performed such that the hard coat layer side of the laminate of the present invention is on the outside.
Moreover, when the pencil hardness is less than 6H, the laminate may not be used as a glass substitute material.
The laminate is more preferably one that does not crack when wound on a cylinder having a diameter of 16 mm, and the pencil hardness is more preferably 8H or more.

The base film is not particularly limited. For example, polyester resin, acetate resin, polyethersulfone resin, polycarbonate resin, polyamide resin, polyimide resin, polyolefin resin, (meth) acrylic resin, Examples thereof include polyvinyl chloride resins, polyvinylidene chloride resins, polystyrene resins, polyvinyl alcohol resins, polyarylate resins, polyphenylene sulfide resins, and the like. Of these, polyester resins, polycarbonate resins, and polyolefin resins are preferably used.

In addition, as said base film, the amorphous olefin polymer (Cyclo-Olefin-Polymer: COP) film which has alicyclic structure is mentioned. This is a base material in which a norbornene polymer, a monocyclic olefin polymer, a cyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer, and the like are used. Zeonoa (norbornene-based resin), Sumitrite FS-1700 manufactured by Sumitomo Bakelite, Arton (modified norbornene-based resin) manufactured by JSR, Appel (cyclic olefin copolymer) manufactured by Mitsui Chemicals, Topas (cyclic) manufactured by Ticona Olefin copolymer), Optretz OZ-1000 series (alicyclic acrylic resin) manufactured by Hitachi Chemical Co., Ltd., and the like.
Further, the FV series (low birefringence, low photoelastic modulus film) manufactured by Asahi Kasei Chemicals is also preferable as an alternative base material for triacetylcellulose.

In the present invention, the base film has a thickness of 40 to 125 μm. If the thickness is less than 40 μm, the mechanical strength of the laminate is insufficient, and the laminate cannot be used as a glass replacement application. If the thickness exceeds 125 μm, the flexibility of the laminate is insufficient. The minimum with the preferable thickness of the said base film is 50 micrometers, a preferable upper limit is 115 micrometers, a more preferable minimum is 60 micrometers, and a more preferable upper limit is 100 micrometers.

The substrate film may have been subjected to etching treatment or undercoating treatment such as sputtering, corona discharge, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, etc. on the surface in advance. By performing these treatments in advance, it is possible to improve the adhesion with the hard coat layer formed on the base film and the cured layer of the monofunctional monomer. Moreover, before forming a hard-coat layer or a hardened layer, the base film surface may be dust-removed and cleaned by solvent cleaning, ultrasonic cleaning, or the like as necessary.

The hard coat layer preferably contains fine particles and a binder resin.
When the hard coat layer contains fine particles, the pencil hardness defined in JIS K 5400 of the hard coat layer can be improved. As a result, the laminate has excellent hardness, and is used as a glass substitute material. It can be suitably used.
Examples of the fine particles include inorganic fine particles and organic fine particles.
Examples of the inorganic fine particles include metal oxides such as silica (SiO ₂ ), alumina, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide. Examples thereof include fine particles, fine metal fluoride particles such as magnesium fluoride and sodium fluoride. Further, as the fine particles, metal fine particles, metal sulfide fine particles, metal nitride fine particles and the like may be used.
In particular, in order to improve the pencil hardness of the laminate, the fine particles are preferably silica or alumina.

The organic fine particles are not particularly limited, and examples thereof include high-density polyethylene, ultrahigh molecular weight polyethylene having a molecular weight of 300,000 or more, polypropylene, polycarbonate, polyamide, polyester, melamine resin, diallyl phthalate resin, acrylic resin, and silicone resin. Fine particles

The fine particles preferably have an average particle diameter of 5 to 100 nm. If it is less than 5 nm, it is difficult to produce the fine particles themselves, and the hardness of the hard coat layer may not be sufficiently improved. Furthermore, the fine particles themselves may cause aggregation in the composition when forming the hard coat layer. If it exceeds 100 nm, the transparency of the hard coat layer may deteriorate and haze may also deteriorate. The more preferable lower limit of the average particle diameter of the fine particles is 10 nm, and the more preferable upper limit is 50 nm.

The hard coat layer preferably contains 30 to 300 parts by mass of the fine particles with respect to 100 parts by mass of the binder resin. If the amount is less than 30 parts by mass, the hardness of the hard coat layer may not be sufficiently improved. If the amount exceeds 300 parts by mass, the flexibility of the laminate may be insufficient. The transparency of the hard coat layer may be lowered. Furthermore, since the adhesiveness of a base film and a hard-coat layer also worsens, it is not preferable. The minimum with more preferable content of the said fine particle is 40 mass parts, and a more preferable upper limit is 200 mass parts.
The fine particles preferably have an ultraviolet (UV) curable reactive group on the surface, and specifically, reactive silica is preferable. As said UV curable reactive group, a methacrylate group or an acrylate group is mentioned suitably, for example.
Further, the shape of the fine particles is preferably atypical in terms of the hardness of the hard coat layer. For example, atypical silica is suitably used as such fine particles.

As said binder resin, a transparent thing is preferable, for example, it is preferable that the ionizing radiation hardening type resin which is resin hardened | cured by an ultraviolet-ray or an electron beam hardens | cures by irradiation of an ultraviolet-ray or an electron beam.
In the present specification, “resin” is a concept including monomers, oligomers, polymers and the like unless otherwise specified.

Examples of the ionizing radiation curable resin include compounds having one or more unsaturated bonds such as compounds having functional groups such as acrylates. Examples of the compound having one unsaturated bond include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone and the like. Examples of the compound having two or more unsaturated bonds include trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and pentaerythritol. Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) ) Acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol octa (meth) acrylate Rate, tetrapentaerythritol deca (meth) acrylate, isocyanuric acid tri (meth) acrylate, isocyanuric acid di (meth) acrylate, polyester tri (meth) acrylate, polyester di (meth) acrylate, bisphenol di (meth) acrylate, diglycerin Polyfunctional compounds such as tetra (meth) acrylate, adamantyl di (meth) acrylate, isoboronyl di (meth) acrylate, dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate Etc. Of these, pentaerythritol tetraacrylate (PETTA) is preferably used. In the present specification, “(meth) acrylate” refers to methacrylate and acrylate. In the present invention, as the ionizing radiation curable resin, a compound obtained by modifying the above-described compound with PO, EO or the like can also be used.
Among these, the ionizing radiation curable resins include dipentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tripentaerythritol. Octa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetrapentaerythritol (meth) decaacrylate, tetrapentaerythritol (meth) octaacrylate , Tetrapentaerythritol (meth) nonaacrylate, trimethylolpropane trimethacrylate, or ditrimethylo Propane hexa methacrylate are most preferred.
Furthermore, as the ionizing radiation curable resin, urethane acrylate can be used, and tetrafunctional or higher urethane (meth) acrylate is preferable, and hexafunctional or higher urethane (meth) acrylate is particularly preferable.
The urethane (meth) acrylate is suitable in terms of hardness, but is more tough, and is therefore suitable when the laminate is made to correspond to a curved surface such as a flexible panel. Furthermore, by having the urethane (meth) acrylate, not only is the curling and cracking prevention properties of the laminated body excellent, but in the post-process (bonding and punching) after the production of the laminated body, Cracks and the like hardly occur in the coat layer.

In addition to the above compounds, relatively low molecular weight polyester resins having unsaturated double bonds, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, etc. It can be used as an ionizing radiation curable resin.

The ionizing radiation curable resin is used in combination with a solvent-drying resin (a thermoplastic resin or the like, which is a resin that forms a film only by drying the solvent added to adjust the solid content during coating). You can also. By using the solvent-drying resin in combination, film defects on the coating surface of the coating liquid can be effectively prevented when forming the hard coat layer.
The solvent-drying resin that can be used in combination with the ionizing radiation curable resin is not particularly limited, and a thermoplastic resin can be generally used.
The thermoplastic resin is not particularly limited. For example, a styrene resin, a (meth) acrylic resin, a vinyl acetate resin, a vinyl ether resin, a halogen-containing resin, an alicyclic olefin resin, a polycarbonate resin, or a polyester resin. Examples thereof include resins, polyamide-based resins, cellulose derivatives, silicone-based resins, rubbers, and elastomers. The thermoplastic resin is preferably amorphous and soluble in an organic solvent (particularly a common solvent capable of dissolving a plurality of polymers and curable compounds). In particular, from the viewpoint of transparency and weather resistance, styrene resins, (meth) acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives (cellulose esters, etc.) and the like are preferable.

The hard coat layer may contain a thermosetting resin.
The thermosetting resin is not particularly limited. For example, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation Examples thereof include resins, silicon resins, polysiloxane resins, and the like.

In the present invention, the hard coat layer preferably has a surface contact angle with water of 100 to 120 °. If it is less than 100 °, the antifouling performance of the surface of the hard coat layer will be insufficient, and the laminate may not be suitable for touch panel applications, and the contact angle of water on the surface of the hard coat layer exceeds 120 ° It is difficult to do.

The hard coat layer having such a contact angle preferably contains an antifouling agent having a reactive functional group. By including the antifouling agent having the reactive functional group, the contact angle with respect to the water on the surface of the hard coat layer can be controlled within the above range for the following reasons. This is preferable because it can be larger than the contact angle with respect to.
That is, when the antifouling agent has a reactive functional group, the binder resin contained in the hard coat layer reacts with the antifouling agent when the hard coat layer is formed. And after manufacturing the said laminated body, although a saponification process is normally given to a hard-coat layer, the antifouling agent of the said hard-coat layer is contained in the state which reacted with binder resin, As a result of the saponification treatment, the antifouling agent hardly falls off, and as a result, it is possible to maintain a large contact angle with water on the surface of the hard coat layer.
In addition, since the antifouling agent has a reactive functional group, the antifouling agent has durability (durability against a heat test, a wet heat test, a light resistance test, a low temperature test, a heat cycle test, etc.), and the touch panel of the present invention is repeatedly used ( The performance is maintained even if it is touched). Furthermore, when the antifouling agent has a reactive functional group, the performance is maintained even when the surface of the hard coat layer is wiped with a chemical.
As a result, the contact angle of water on the surface of the hard coat layer of the laminate may be larger than the contact angle of water on the surface of the lower hard coat layer.
On the other hand, in the lower hard coat layer described later, a leveling agent is added to the composition in order to improve applicability of the composition when the lower hard coat layer is formed, but the leveling agent is non-reactive. Are preferably used. For this reason, when a saponification process is performed on the lower hard coat layer, the non-reactive leveling agent falls off, and as a result, the contact angle of the surface of the lower hard coat layer with water becomes small. In addition, even if the lower hard-coat layer mentioned later is a case where saponification is not performed, it is preferable that the contact angle with respect to water is small. This is because the lower hard coat layer is directly attached to the polarizing plate, or an adhesive film is attached to the polarizing plate or OLET, so that a smaller contact angle with water is more effective in terms of adhesion. . Furthermore, the lower hard coat layer may be subjected to decorative printing (black, white, other colors, etc.). If the contact angle with water on the surface of the lower hard coat layer is large, the decorative printing ink is repelling. In some cases, the appearance may not be clean.

Examples of the antifouling agent having a reactive functional group include, for example, OPTOOL DAC manufactured by Daikin Industries, MegaFac RS71, RS74 manufactured by DIC, TU2224, TU2225 manufactured by JSR, and X71-1203M manufactured by Shin-Etsu Chemical. , X22-164E, X22-164C, Neogene's TF 601AD, 602A, 650A, BYK UV3500, BYK UV3505, BYK UV3510, BYK UV3570, BYK UV3575, BYK UV3576, and the like.

The content of the antifouling agent having a reactive functional group in the hard coat layer is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the binder resin. If it is less than 0.05 parts by mass, the contact angle of water on the surface of the hard coat layer becomes small, and the antifouling performance may be insufficient. On the other hand, even if it exceeds 5 parts by mass, the antifouling performance does not change, resulting in high production costs, white turbidity in the hard coat layer, or sea islands, and poor hardness. Sometimes. Furthermore, if the amount of the unreacted antifouling agent in the hard coat layer is increased, it is not preferable because it is set off by roll-to-roll processing. Furthermore, when a saponification process is performed, a saponification bath may be contaminated.
The minimum with more preferable content of the antifouling agent which has the said reactive functional group is 0.1 mass part, and a more preferable upper limit is 3 mass parts.

The hard coat layer containing the fine particles, the binder resin and the antifouling agent having a reactive functional group is, for example, the hard containing the fine particles, the monomer component of the binder resin, the antifouling agent having a reactive functional group, and a solvent. The coating layer composition can be formed by applying a coating film on the substrate film and drying it to cure it by irradiation with ionizing radiation.

Examples of the solvent contained in the hard coat layer composition include alcohols (eg, methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol), ketones, and the like. (Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons ( Toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfo Sid compound (dimethylsulfoxide), amides (dimethylformamide, dimethylacetamide, etc.) and the like can be exemplified, or a mixture thereof.

The hard coat layer composition preferably further contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited, and known ones can be used. Specific examples include, for example, acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, thioxanthones, propio Examples include phenones, benzyls, benzoins, and acylphosphine oxides. In addition, it is preferable to use a mixture of photosensitizers, and specific examples thereof include n-butylamine, triethylamine, poly-n-butylphosphine, and the like.

As the photopolymerization initiator, when the binder resin is a resin system having a radically polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether or the like may be used alone or in combination. preferable. When the binder resin is a resin system having a cationic polymerizable functional group, examples of the photopolymerization initiator include aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metallocene compounds, benzoin sulfonate esters, and the like. Are preferably used alone or as a mixture.

The content of the photopolymerization initiator in the hard coat layer composition is preferably 0.5 to 10.0 parts by mass with respect to 100 parts by mass of the binder resin. If it is less than 0.5 parts by mass, the hardness of the hard coat layer to be formed may be insufficient, and if it exceeds 10.0 parts by mass, there is a possibility that the curing may be hindered. Absent.

Although it does not specifically limit as a content rate (solid content) of the raw material in the said composition for hard-coat layers, Usually, it is preferable to set it as 5-70 mass%, especially 25-60 mass%.

In the hard coat layer composition, according to the purpose of increasing the hardness of the hard coat layer, suppressing curing shrinkage, controlling the refractive index, etc., conventionally known dispersants, surfactants, antistatic agents, Silane coupling agent, thickener, anti-coloring agent, coloring agent (pigment, dye), antifoaming agent, leveling agent, flame retardant, UV absorber, adhesion-imparting agent, polymerization inhibitor, antioxidant, surface modification An agent or the like may be added as long as the effects of the present invention described above are not impaired.
As the leveling agent, for example, silicone oil, fluorine-based surfactant and the like are preferable because the hard coat layer is prevented from having a Benard cell structure. When a resin composition containing a solvent is applied and dried, a surface tension difference or the like is generated between the coating film surface and the inner surface in the coating film, thereby causing many convections in the coating film. The structure generated by this convection is called a Benard cell structure, and causes a problem such as the skin and coating defects in the hard coat layer to be formed.

The method for preparing the hard coat layer composition is not particularly limited as long as each component can be uniformly mixed. For example, the composition can be performed using a known apparatus such as a paint shaker, a bead mill, a kneader, or a mixer.

The method for applying the hard coat layer composition onto the light-transmitting substrate is not particularly limited. For example, spin coating, dipping, spraying, die coating, bar coating, roll coater, meniscus coater And publicly known methods such as a method, a flexographic printing method, a screen printing method, and a pea coater method.

In addition, as a method of irradiating ionizing radiation when curing the coating film after drying, for example, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp is used. A method is mentioned.
Moreover, as a wavelength of an ultraviolet-ray, the wavelength range of 190-380 nm can be used. Specific examples of the electron beam source include various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type.

In the laminate, the hard coat layer has a thickness of 10 to 25 μm. If it is less than 10 μm, the surface of the hard coat layer is likely to be damaged, and if it exceeds 25 μm, not only can the hard coat layer be thinned, but the hard coat layer is liable to break, curl also increases, The flexibility (bending) is not sufficient. The preferable lower limit of the thickness of the hard coat layer is 12 μm, the preferable upper limit is 22.5 μm, the more preferable lower limit is 14 μm, and the more preferable upper limit is 20 μm.
In addition, the thickness of the said hard-coat layer can be measured by cross-sectional microscope observation.

The laminate has a cured resin layer on the other surface of the base film.
In the present invention, the cured resin layer is preferably a cured layer of a monofunctional monomer (hereinafter also simply referred to as a cured layer), and a laminate having such a cured layer has extremely excellent hardness as a glass substitute material. In addition to being able to make it easy, it can be made excellent in flexibility.
The thickness of the cured resin layer is preferably 1 to 25 μm. If the thickness is less than 1 μm, the hardness of the laminate and the adhesion to the base film may be insufficient. If the thickness exceeds 25 μm, the cured resin layer cannot be thinned and the curl is large. Sometimes. It becomes easy to break. The more preferable range of the thickness of the said resin cured layer is 3-20 micrometers, More preferably, it is 4-15 micrometers.
In addition, the thickness of the said resin cured layer can be measured by cross-sectional microscope observation.

The monofunctional monomer is preferably a monofunctional acrylic monomer.
The monofunctional acrylic monomer is at least one selected from the group consisting of acryloylmorpholine, N-acryloyloxyethylhexahydrophthalimide, cyclohexyl acrylate, tetrahydrofuryl acrylate, isobornyl acrylate, phenoxyethyl acrylate, and adamantyl acrylate. Of these, acryloylmorpholine is more preferable. By having such a hardened layer, it is possible to sufficiently improve the hardness and flexibility of the laminate.

The cured layer is formed by, for example, applying the cured layer composition containing the above-described monofunctional monomer and solvent to the side surface opposite to the hard coat layer of the base film, and curing the formed coating film after drying. Can be formed. In addition, what is necessary is just to adjust the degree of drying of the said coating film suitably, However, In this invention, what is necessary is just to dry the said coating film until it becomes 100% of solid content. If the solvent remains in the cured layer after pasting to the base film, the adhesion with the base film deteriorates, the adhesiveness deteriorates after the durability test, or the whitening and transparency deteriorates. There is a risk of doing.
As a solvent in the said composition for hardened layers, the thing similar to what was illustrated with the composition for hard-coat layers mentioned above is mentioned.
In addition, the hardened layer composition, like the hard coat layer composition, is a photopolymerization initiator, a dispersant, a surfactant, an antistatic agent, a silane coupling agent, a thickener, a coloring inhibitor, Colorants (pigments, dyes), antifoaming agents, leveling agents, flame retardants, ultraviolet absorbers, adhesion-imparting agents, polymerization inhibitors, antioxidants, surface modifiers, and the like may be added.

The preparation method of the said composition for hardening layers, the coating method, the drying and hardening method of a coating film, etc. are not specifically limited, The method similar to the composition for hard-coat layers mentioned above is mentioned.

It is preferable that the said laminated body has another base film on the opposite surface to the base film of the said resin cured layer. By having said another base film, the hardness of the said laminated body can be made more excellent and it becomes possible to use more suitably as a glass substitute material.
As said another base film, the thing similar to the base film mentioned above is mentioned.
In addition, when it has said another base film, the base film mentioned above and another base film may consist of the same material, and may consist of a different material. Furthermore, the another base film and the base film described above may have the same or different thickness.

In the case of having the other base film, the laminate, for example, forms a hard coat layer on one surface of the base film described above and applies the above-described composition for a hardened layer on the other surface. After forming a coating film, it can manufacture by sticking said another base film to the said coating film, and hardening the said coating film after that.
In addition, the laminated body has an optical function layer (a low refractive index layer, a high refractive index layer, an antifouling layer, an antistatic layer, an antiglare layer) on the side opposite to the base film of the hard coat layer. Layer, etc.) may be formed. These optical functional layers may be organic materials, inorganic materials, or a mixture of organic materials and inorganic materials, and can be formed by a conventionally known configuration and method. For example, the composition can be reduced by applying and curing a composition in which hollow silica or the like is mixed in an organic binder, laminating a low refractive index layer, or sputtering an inorganic thin film such as SiOx (x = 1 to 2). When one or more functional layers are provided on the hard coat layer, such as by laminating a refractive index layer, the indentation hardness due to nanoindentation of the laminate of the present invention is twice that of the hard coat layer alone. It can be improved up to 3 times higher hardness (upper limit is about 4 GPa). This is a state in which the hardness of the outermost surface is improved, so that the scratch resistance is very good.

The laminate preferably has a lower hard coat layer on the other surface of the another base film. By having the said lower hard-coat layer, the hardness of the said laminated body can be made more excellent.
Examples of the thickness, material, and forming method of the lower hard coat layer include the same methods as those for the hard coat layer described above.

In the present invention, the lower hard coat layer preferably has a surface contact angle with water of 30 to 90 °. If it is less than 30 °, the coated surface often deteriorates and the visibility may deteriorate, and if it exceeds 90 °, the printing performance on the surface of the lower hard coat layer may be insufficient. The adhesive strength between the lower hard coat layer and the layer provided on the side opposite to the other substrate film side may deteriorate. The contact angle is more preferably a lower limit of 35 ° and a more preferable upper limit of 70 °.
From the viewpoint of adhesion with the layer provided on the side opposite to the other base film side of the lower hard coat layer, the contact angle of water is also important, but the contact angle of hexadecane is also important. The contact angle of hexadecane on the surface of the lower hard coat layer is preferably 1 to 30 °. In addition, the contact angle of hexadecane on the surface of the hard coat layer described above (or the outermost surface of the laminate) is preferably 40 ° or more.
Further, the lower hard coat layer side may be subjected to saponification treatment or treatment such as corona treatment, in which case, the contact angle with respect to the water of the surface of the lower hard coat layer after treatment is It is preferable that it is 30-90 degrees.
However, when saponification treatment is performed, when the saponification conditions are severe (high alkaline aqueous solution concentration, saponification treatment time is long), the contact angle with water can be lowered, but to the base film or the surface layer Damage may become stronger, and the target hardness may deteriorate.

The lower hard coat layer having such a contact angle preferably contains a non-reactive leveling agent. By containing the non-reactive leveling agent, the contact angle with respect to water on the surface of the lower hard coat layer can be controlled within the above range, and the contact angle with respect to water on the surface of the hard coat layer described above is smaller. It can be. The reason is as described above.
The surface of the lower hard coat layer may be printed depending on the design of the touch panel of the present invention, but the contact angle of the surface of the lower hard coat layer with water is smaller. Thereby, the printability of the surface of the lower hard coat layer can be further improved.

Examples of the non-reactive leveling agent include silicone, fluorine, and non-fluorine non-silicone.
In the case of the above silicone-based or fluorine-based leveling agent, hydrophilic chemical bonds (hydroxyl group, carboxyl group, amino group, PO-modified site, EO-modified site, caprolactone-modified site, isocyanuric acid are used to reduce the contact angle with water. Those having a denatured site) are preferred. Those having a small content of fluorine atoms and silicone atoms are preferred.
Among these, BYK 350, BYK 354, BYK 381, BYK 392, BYK 394, BYK 3441, manufactured by BYK Chemie, OD002, OD007, OD012, etc. manufactured by Nissan Chemical are suitably used for non-fluorine non-silicone (acrylic). It is done.
In the silicone system, polyether modified BYK 300, BYK 302, BYK 306, BYK 307, BYK 310, BYK 320, BYK 325, BYK 330, BYK 333, BYK 342 BYK 347, BYK 349, BYK 349, BYK 348, BYK 348, BYK 349, BYK , BYK 378, BYK 3455, BYK 370, BYK 377 and the like containing BYK Chemie's hydroxyl group are preferably used.
In addition, in the fluorine system, polyether modified footage 251, 212M, 215M, 250F, 209F, 222F, 245F, 208G, 240G, 212P, 220P, 228P, FTX218, DFX18, manufactured by DIC, F477, F445, manufactured by Neos. Etc. are preferably used.
The content of the non-reactive leveling agent is preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the binder resin in the lower hard coat layer. If it is less than 0.01 parts by weight, the composition for forming the lower hard coat layer may not be uniformly applied, and the contact angle with respect to the water of the surface of the formed lower hard coat layer is increased. Printability may be reduced. If it exceeds 5 parts by mass, settling may occur. The minimum with more preferable content of the said non-reactive leveling agent is 0.05 mass part, and a more preferable upper limit is 3 mass parts.

Since the touch panel of the present invention has the above-described laminated body excellent in hardness and flexibility as a glass substitute material, it can be made suitable for curved surfaces, and in addition, a roll-to-roll system can be used during the production of the laminated body. Can be manufactured.
Such a laminate used for the touch panel of the present invention and a method for producing the same are also one aspect of the present invention.
That is, the method for producing a laminate of the present invention includes a step of forming a hard coat layer on one surface of a base film using a composition for a hard coat layer, and the other surface of the base film. And a step of forming a cured resin layer by a roll-to-roll method using the composition for a cured layer.

In the touch panel of the present invention, the laminate preferably contains an antifouling agent having a hard coat layer having a reactive functional group, and the lower hard coat layer preferably contains a non-reactive leveling agent. By having a hard coat layer and a lower hard coat layer, the laminate is excellent in the stain resistance of the hard coat layer, while being excellent in the printability of the surface of the lower hard coat layer.
In addition, as a manufacturing method of the laminated body of this invention which has such a hard-coat layer and a lower hard-coat layer, a hard-coat layer is used for example on one surface of a base film using the composition for hard-coat layers. And forming the lower hard coat layer on the other surface of the base film using the lower hard coat layer composition in a roll-to-roll manner. The layer composition contains an antifouling agent having a reactive functional group, and the lower hard coat layer contains a non-reactive leveling agent.

The laminate in the touch panel of the present invention preferably has another base film on the surface of the lower hard coat layer opposite to the cured resin layer. By having said another base film, the hardness of the said laminated body can be made more excellent and it becomes possible to use more suitably as a glass substitute material.
As said another base film, the thing similar to the base film mentioned above is mentioned.
In addition, when it has said another base film, the base film mentioned above and another base film may consist of the same material, and may consist of a different material. Furthermore, the another base film and the base film described above may have the same or different thickness.

In the case of having the another base film, the laminate is formed, for example, by applying the above-described cured layer composition on one surface of the above-described base film to form a coating film, and then via the coating film. A second base film is applied, the coating film is cured to form a resin cured layer, a hard coat layer is formed on the side opposite to the resin cured layer side of the base film, and It can manufacture by forming a lower hard-coat layer on the opposite side to the said resin cured layer side of another base film.
In addition, the laminated body has an optical function layer (a low refractive index layer, a high refractive index layer, an antifouling layer, an antistatic layer, an antiglare layer) on the side opposite to the base film of the hard coat layer. Layer, etc.) may be formed. These optical functional layers may be organic materials, inorganic materials, or a mixture of organic materials and inorganic materials, and can be formed by a conventionally known configuration and method. For example, the composition can be reduced by applying and curing a composition in which hollow silica or the like is mixed in an organic binder, laminating a low refractive index layer, or sputtering an inorganic thin film such as SiOx (x = 1 to 2). When one or more functional layers are provided on the hard coat layer, such as by laminating a refractive index layer, the pencil hardness of the laminate is 2 to 3 times higher than that of the hard coat layer alone (upper limit) Can be improved to 9H). This is a state in which the hardness of the outermost surface is improved, so that the scratch resistance is very good.

By having the above-described configuration, the laminate has extremely excellent hardness and can be suitably used as a glass substitute material.
Specifically, by adopting the above-described configuration, the laminate can achieve a pencil hardness of 6H or more at a load of 750 g while having flexibility that can be wound around a 20 mm cylinder.
Although it does not specifically limit as a touchscreen of this invention which has such a laminated body, For example, it is preferable that it is a conventionally well-known in-cell type touchscreen.
Moreover, it is preferable that the said resin cured layer side surface of the said laminated body is stuck on a polarizer or a polarizing plate through an adhesive layer or an adhesive bond layer. The polarizer or polarizing plate is not particularly limited, and examples thereof include conventionally known ones. The pressure-sensitive adhesive and adhesive are not particularly limited, and those made of conventionally known materials can be used.

In addition, since the laminate has extremely excellent flexibility, as a display that can cope with a curved surface, for example, a thin and bent flexible organic EL display, or a mobile terminal such as a smartphone or a wristwatch type terminal. It can be suitably used for a display panel inside a car, a flexible panel used for a wristwatch, and the like. The laminate can also be applied to an image display device such as a liquid crystal display device.
In addition, it has the hard coat layer on one surface of the base film described above and the resin cured layer on the other surface of the base film, and is disposed on the opposite side of the base film of the resin cured layer. The laminate having another base film through the hard coat layer has extremely excellent hardness as described above, but the hardness of each layer preferably has a relationship satisfying the following inequality.
Hard coat layer and lower hard coat layer> resin cured layer> base film and another base film Here, the hardness of each layer is a cross section of each layer that appears by cutting the laminate of the above configuration in the thickness direction. Is the hardness measured by indenting the indenter by the nanoindentation method in the cross-sectional direction.
The hardness measurement by the nanoindentation method was performed using “TI950 TriboIndenter” manufactured by HYSITRON (Heiditron). That is, a Berkovich indenter (triangular pyramid) was pushed in by 500 nm from the surface of the hard coat layer or the like of the above laminate, and after holding the residual stress to relieve the residual stress, unload it and measure the max load after relaxation. The indentation hardness is calculated from P _max / A using the max load (P _max (μN)) and the indentation area (A (nm ² )) having a depth of 500 nm.

Furthermore, the laminate having the above-described structure is formed by forming a hard coat layer or a lower hard coat layer on a base film or another base film, and measuring the pencil hardness (1) measured on the surface of the hard coat layer. A resin cured layer is formed on the film or another substrate film, and the pencil hardness (2) measured on the surface of the resin cured layer side and the pencil hardness measured on the surface of the substrate film and another substrate film ( 3) preferably have a relationship of pencil hardness (1)> pencil hardness (2)> pencil hardness (3).
That is, specifically, using each layer of the laminate according to Example 1 described later, when the hard coat layer according to Example 1 having a thickness of 15 μm is formed on a triacetyl cellulose substrate having a thickness of 80 μm, The pencil hardness (1) on the surface of the coating layer is 7H, and when the cured resin layer according to Example 1 having a thickness of 10 μm using acryloylmorpholine is formed on a triacetyl cellulose substrate having a thickness of 80 μm, The pencil hardness (2) is B, and the pencil hardness (3) on the surface of the triacetylcellulose substrate having a thickness of 80 μm is 3B. These preferable hardness relationships are equal to the hardness of the cross section by the nanoindentation method.

In addition, as described above, in the laminate having the structure having the another base film, after the hard coat layer is formed on one surface of the base film, the coating film is formed on the other surface of the base film. Although another base film may be attached via the above-mentioned base film, after the base film and another base film are pasted together via the above-mentioned coating film, on one surface of the base film After forming the hard coat layer, it is preferable to form the lower hard coat layer on the surface of the other base film. As described above, the hard coat layer preferably contains an antifouling agent having a reactive functional group, but when such a hard coat layer is formed first, the reactive functional group in the hard coat layer is reduced. The antifouling agent to be contained hardly falls off due to being contained in a sufficiently reacted state with the binder resin. On the other hand, the lower hard coat layer preferably contains a non-reactive leveling agent. However, since the non-reactive leveling agent easily falls off, if the lower hard coat layer is formed first, the non-reactive leveling agent is not reacted. Due to the removal of the property leveling agent, it may be difficult to produce the laminate, and it may be difficult to control the contact angle of the upper and lower hard coat layers with water.
In addition, if the non-reactive leveling agent in the lower hard coat layer does not transfer to another base film surface on the hard coat layer side, the base film and another base film pass through the resin cured layer. After being affixed, the lower hard coat layer may be formed, and then the hard coat layer may be formed.

In addition, even if it is a case where it manufactures by any said method, the said coating film may be hardened by irradiating light from any surface side of a base film direction and another base film direction. .
Further, the base film and / or another base film often contains a UV absorber. In the laminate, the base film and / or another base film is the resin. As long as the cured layer is sufficiently adhered, a UV absorber may or may not be contained. In addition, when the said base film and another base film contain UV absorber, when hardening the said coating film, it is necessary to irradiate an ultraviolet-ray firmly.
When the adhesion between the base film and another base film and the cured resin layer is insufficient, the laminate may be peeled off, which is not preferable because of poor pencil hardness.
The adhesive strength between the base film and another base film and the cured resin layer is 10 N / when the width is 25 mm, the peel rate is 300 mm / min, and the 180 ° peel strength is measured at room temperature (23 ° C.). It is preferable that it is 25 mm or more. When it is less than 10 N / 25 mm, the above-mentioned base film and another base film can be easily peeled off from the cured resin layer, and it has high hardness and excellent flexibility, and is useful as a glass substitute material. In some cases, the excellent effect of the present invention can not be sufficiently obtained. The adhesive strength between the base film and another base film and the cured resin layer is 15 N / 25 mm or more when the 180 ° peel strength is measured at a width of 25 mm, a peel rate of 300 mm / min, and room temperature (23 ° C.). It is more preferable that it is 25N / 25mm.

Here, regarding a conventional hard coat film having a hard coat layer on a base film, it is known that black frame printing or white frame printing is applied to the side surface opposite to the hard coat layer of the base film to enhance design properties. It has been. As a method for mounting such a hard coat film with improved design on a liquid crystal display device or the like, for example, the surface subjected to the black frame printing or the like is filled with an adhesive, and the surface filled with the adhesive is displayed as an image. Examples thereof include a method of pasting on a polarizing plate on the display screen side of the apparatus or a glass plate provided on the polarizing plate.
However, in the case where the designability is enhanced by the black frame printing or the like, light transmission occurs unless the black frame printing or white frame printing is considerably thick, for example, about 5 to 20 μm, and the designability is impaired. was there. For this reason, for example, when black frame printing is performed on a conventional hard coat film to enhance the design, a difference in level is likely to occur between the filled adhesive and the black frame printing portion, and it is affixed to a polarizing plate or a glass plate. There was a problem that became difficult.
For such a problem, for example, another base film is further provided on the surface of the conventional hard coat film filled with the pressure-sensitive adhesive, and the another base film is attached to a polarizing plate or a glass plate. Thus, the problem of the step can be solved, and the problem of sticking to a polarizing plate or a glass plate can be solved.
However, since the pressure-sensitive adhesive has a high viscosity, air may be mixed in when filled on the surface of the base film on which the black frame printing has been performed. The hard coat film that has been attached to another base film also has a problem of insufficient hardness.

On the other hand, when the design of the laminate is enhanced by the method described above, that is, the laminate is printed on the outer peripheral portion of the cured resin layer between the base film and another base film. In the case of a configuration in which white frame printing or the like is performed, such a problem that air is mixed in or a problem that the hardness becomes insufficient does not occur.
The laminated body of the present invention having such a structure is, for example, the above-described cured layer on the surface subjected to the black frame printing or the like on the side opposite to the side on which the hard coat layer of the base film is provided. After the coating film formed by applying the composition for drying is dried, it can be produced by pasting and curing the other base film. In addition, the above-mentioned black frame printing etc. are given on one side of another substrate film, and the coating film formed by applying the above-mentioned composition for hardened layers on the side which gave the black frame printing etc. of this other substrate film It can also be produced by drying and attaching to a base film having a hard coat layer formed through the coating film.
Even if it is a case where it manufactures by any method, since the viscosity of the said composition for hardening layers is sufficiently low compared with the conventional adhesive mentioned above, on the surface which carried out the said black frame printing etc., without mixing air It is easy to apply to.
And since the said laminated body is a structure which has a hard-coat layer on one side of a base film as mentioned above and a predetermined | prescribed resin hardened layer on the other side, high hardness and the outstanding flexibility It will be something that combines.
As described above, in the present invention, when the laminate has a lower hard coat layer, and the contact angle of water on the surface of the lower hard coat layer is controlled, the surface of the lower hard coat layer is printed. The design property of the laminate is enhanced.

Since the touch panel of the present invention has the above-described configuration, it has a laminate having extremely excellent hardness and flexibility.
The laminate is suitably used as a glass substitute material for touch panel applications.
In addition, the laminate is a thin and bendable flexible organic EL display, a mobile terminal such as a smartphone or a wristwatch type terminal, a display device inside an automobile, a flexible panel used for a wristwatch, or the like, and a liquid crystal display. It can also be suitably used for an image display device such as a device.

The contents of the present invention will be described with reference to the following examples, but the contents of the present invention should not be construed as being limited to these embodiments.

Example 1
As a base film, a triacetyl cellulose base material (manufactured by Fuji Film Co., Ltd., TD80ULN) having a thickness of 80 μm is prepared, and a hard coat layer composition (1) having the following composition is formed on one surface of the base film. It was applied to form a coating film. Next, the solvent in the coating film is evaporated by circulating dry air at 70 ° C. for 45 seconds with respect to the formed coating film, and using an ultraviolet irradiation device (Fusion UV System Japan, light source H bulb), A hard coat layer having a thickness of 15 μm (at the time of curing) was formed by irradiating ultraviolet rays under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) so that the integrated light amount was 200 mJ / cm ² to cure the coating film.

(Composition for hard coat layer (1))
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku DPHA) 50 parts by mass Reactive deformed silica (manufactured by JGC Catalysts & Chemicals, ELCOM V8803) 50 parts by mass Irgacure 184 (manufactured by BASF Japan) 4 parts by mass MIBK 60 parts by mass MEK 60 parts by mass Part antifouling agent (X71-1203M, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass

Next, on the side opposite to the side on which the hard coat layer of the base film was formed, the cured layer composition (1) having the following composition was applied, and a coating film was formed so that the film thickness after curing was 10 μm. The solvent in the coating film was evaporated by passing dry air of 70 ° C. for 45 seconds.
Thereafter, using an ultraviolet irradiation device (Fusion UV System Japan, light source H bulb), the ultraviolet ray is irradiated in a nitrogen atmosphere (oxygen concentration of 200 ppm or less) so that the integrated light quantity becomes 600 mJ / cm ^2. Was cured to form a cured resin layer having a thickness of 10 μm (during curing) to produce a laminate having a total thickness of 105 μm.

(Curing layer composition (1))
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku DPHA) 50 parts by mass Reactive deformed silica (manufactured by JGC Catalysts & Chemicals, ELCOM V8803) 50 parts by mass Irgacure 184 (manufactured by BASF Japan) 4 parts by mass MIBK 60 parts by mass MEK 60 parts by mass Part leveling agent (DIC Corporation, F477) 0.1 parts by mass

(Example 2)
A laminate having a total thickness of 102 μm was produced in the same manner as in Example 1 except that the thickness of the hard coat layer was 12 μm.

(Example 3)
A laminate having a total thickness of 110 μm was manufactured in the same manner as in Example 1 except that the thickness of the hard coat layer was 20 μm.

Example 4
A laminate having a total thickness of 115 μm was produced in the same manner as in Example 1 except that the thickness of the hard coat layer was 25 μm.

(Example 5)
A laminate having a total thickness of 110 μm was manufactured in the same manner as in Example 1 except that the thickness of the cured resin layer was 15 μm.

(Example 6)
As in Example 1, except that a triacetyl cellulose base material (manufactured by Fuji Film Co., Ltd., TD60ULP) having a thickness of 60 μm was used as the base film, and the thickness of the hard coat layer and the cured resin layer was 22 μm. Thus, a laminate having a total thickness of 104 μm was manufactured.

(Example 7)
A laminate having a total thickness of 105 μm was produced in the same manner as in Example 1 except that the hard coat layer composition (2) having the following composition was used instead of the hard coat layer composition (1).

(Composition for hard coat layer (2))
Urethane acrylate (DPHA40H manufactured by Nippon Kayaku Co., Ltd.) 50 parts by mass Reactive deformed silica (manufactured by JGC Catalysts & Chemicals, ELCOM V8803) 50 parts by mass Irgacure 184 (manufactured by BASF Japan) 4 parts by mass MIBK 60 parts by mass MEK 60 parts by mass Stain (X71-1203M, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass

(Example 8)
A laminate having a total thickness of 105 μm was produced in the same manner as in Example 1 except that the hard coat layer composition (3) having the following composition was used instead of the hard coat layer composition (1).

(Composition for hard coat layer (3))
Dipentaerythritol hexaacrylate (Nippon Kayaku DPHA) 50 parts by mass Urethane acrylate (Nippon Kayaku DPHA 40H) 50 parts by mass Irgacure 184 (manufactured by BASF Japan) 4 parts by mass MIBK 60 parts by mass MEK 60 parts by mass antifouling agent (X71-1203M, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass

Example 9
A laminate having a total thickness of 105 μm was produced in the same manner as in Example 1 except that the hard coat layer composition (4) having the following composition was used instead of the hard coat layer composition (1).

(Composition for hard coat layer (4))
Dipentaerythritol hexaacrylate (Nippon Kayaku DPHA) 50 parts by mass Solid silica (Nissan Chemical Co., MIBKDL) 50 parts by mass Irgacure 184 (BASF Japan) 4 parts by mass MIBK 60 parts by mass MEK 60 parts by mass antifouling Agent (X71-1203M, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass

(Example 10)
A laminated body having a total thickness of 105 μm was produced in the same manner as in Example 1 except that instead of the composition for cured layer (1), the composition for cured layer (2) having the following composition was used.

(Curing layer composition (2))
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku DPHA) 50 parts by mass Reactive deformed silica (manufactured by JGC Catalysts & Chemicals, ELCOM V8803) 50 parts by mass Irgacure 184 (manufactured by BASF Japan) 4 parts by mass MIBK 60 parts by mass MEK 60 parts by mass Part leveling agent (BYK302, manufactured by Big Chemie) 0.1 parts by mass

(Example 11)
A laminated body having a total thickness of 105 μm was produced in the same manner as in Example 1, except that the composition for cured layer (3) having the following composition was used instead of the composition for cured layer (1).

(Curing layer composition (3))
Urethane Acrylate (Nippon Kayaku Co., Ltd. DPHA40H) 100 parts by mass Irgacure 184 (manufactured by BASF Japan) 4 parts by mass MIBK 60 parts by mass MEK 60 parts by mass Leveling agent (manufactured by DIC, F477) 0.1 parts by mass

(Example 12)
A laminate having a total thickness of 105 μm was produced in the same manner as in Example 1 except that the composition for cured layer (4) having the following composition was used instead of the composition for cured layer (1).

(Composition for cured layer (4))
Pentaerythritol triacrylate (manufactured by Nippon Kayaku Co., Ltd., PET30) 50 parts by mass PMMA (manufactured by DNP Fine Chemical Co., Ltd., HRAG acrylic) 50 parts by mass Irgacure 184 (manufactured by BASF Japan) 4 parts by mass MIBK 60 parts by mass MEK 60 parts by mass leveling agent (DIC Corporation, F477) 0.05 parts by mass

(Example 13)
In the same manner as in Example 1, a hard coat layer was formed on one side of the base film, and on the side opposite to the side on which the hard coat layer was formed, the cured layer composition (1) was applied. Instead, a coating film was formed using the cured layer composition (5) having the following composition, and the solvent in the coating film was evaporated.

(Composition for cured layer (5))
Acrylyl morpholine (manufactured by Kojin Film Chemicals Co., Ltd., ACMO) 100 parts by mass MIBK 10 parts by mass Leveling agent (manufactured by DIC, F477) 0.1 parts by mass

As another base film, a triacetyl cellulose base material (manufactured by Fuji Film Co., Ltd., TD80ULN) having a thickness of 80 μm was prepared and attached to the another base film through the coating film.
Thereafter, from another base film side, using an ultraviolet irradiation device (light source H bulb, manufactured by Fusion UV System Japan Co., Ltd.), the integrated light quantity is 600 mJ / cm ² under a nitrogen atmosphere (oxygen concentration of 200 ppm or less). The cured resin film was irradiated to form a cured resin layer having a thickness of 10 μm (during curing), and a laminate having a total thickness of 185 μm was produced.

(Example 14)
A laminate having a total thickness of 105 μm was obtained in the same manner as in Example 13 except that a 40 μm-thick triacetyl cellulose base material (Konica Minolta, KC4UA) was used as the base film and another base film. Manufactured.

(Example 15)
A laminate having a total thickness of 105 μm was produced in the same manner as in Example 1 except that the hard coat layer composition (5) having the following composition was used instead of the hard coat layer composition (1).

(Composition for hard coat layer (5))
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku DPHA) 50 parts by mass Reactive deformed silica (manufactured by JGC Catalysts & Chemicals, ELCOM V8803) 50 parts by mass Irgacure 184 (manufactured by BASF Japan) 4 parts by mass MIBK 60 parts by mass MEK 60 parts by mass Part antifouling agent (BYK-UV3500, manufactured by Big Chemie) 0.5 parts by mass

(Example 16)
A laminate having a total thickness of 105 μm was produced in the same manner as in Example 1 except that the hard coat layer composition (6) having the following composition was used instead of the hard coat layer composition (1).

(Composition for hard coat layer (6))
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku DPHA) 50 parts by mass Reactive deformed silica (manufactured by JGC Catalysts & Chemicals, ELCOM V8803) 50 parts by mass Irgacure 184 (manufactured by BASF Japan) 4 parts by mass MIBK 60 parts by mass MEK 60 parts by mass Part antifouling agent (X71-1203M, manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts by mass

(Example 17)
A laminate having a total thickness of 105 μm was produced in the same manner as in Example 1 except that the hard coat layer composition (7) having the following composition was used instead of the hard coat layer composition (1).

(Composition for hard coat layer (7))
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku DPHA) 50 parts by mass Reactive deformed silica (manufactured by JGC Catalysts & Chemicals, ELCOM V8803) 50 parts by mass Irgacure 184 (manufactured by BASF Japan) 4 parts by mass MIBK 60 parts by mass MEK 60 parts by mass Part antifouling agent (X71-1203M, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1 parts by mass

(Example 18)
A laminate having a total thickness of 105 μm was produced in the same manner as in Example 1 except that the hard coat layer composition (8) having the following composition was used instead of the hard coat layer composition (1).

(Composition for hard coat layer (8))
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku DPHA) 50 parts by mass Reactive deformed silica (manufactured by JGC Catalysts & Chemicals, ELCOM V8803) 50 parts by mass Irgacure 184 (manufactured by BASF Japan) 4 parts by mass MIBK 60 parts by mass MEK 60 parts by mass Part antifouling agent (manufactured by DIC, MegaFac RS74) 0.1 parts by mass

(Example 19)
A laminate having a total thickness of 125 μm was produced in the same manner as in Example 1 except that a polyethylene terephthalate (PET) base material (Toray Industries, Inc., Toray U48) having a thickness of 100 μm was used as the base film.

(Example 20)
A laminate having a total thickness of 213 μm was produced in the same manner as in Example 1 except that a 188 μm thick polyethylene terephthalate (PET) substrate (Toray Industries, Inc., Toray U48) was used as the substrate film.

(Comparative Example 1)
A laminate having a total thickness of 95 μm was produced in the same manner as in Example 1 except that the thickness of the hard coat layer was 5 μm.

(Comparative Example 2)
A laminate having a total thickness of 120 μm was produced in the same manner as in Example 1 except that the thickness of the hard coat layer was 30 μm.

(Comparative Example 3)
A laminate having a total thickness of 96 μm was produced in the same manner as in Example 1 except that the thickness of the cured resin layer was 1 μm.

(Comparative Example 4)
A laminate having a total thickness of 65 μm was produced in the same manner as in Example 1 except that a 40 μm-thick triacetylcellulose substrate (manufactured by Konica Minolta, KC4UA) was used as the base film.

(Comparative Example 5)
A laminate having a total thickness of 105 μm was produced in the same manner as in Example 1 except that the hard coat layer composition (1) was used instead of the cured layer composition (1).

(Comparative Example 6)
The thickness of the hard coat layer and the cured resin layer was set to 22 μm, and the same procedure as in Example 1 was used except that a 25 μm-thick triacetyl cellulose base material (Konica Minolta, KC2UA) was used as the base film. Thus, a laminate having a total thickness of 69 μm was manufactured.

(Reference Example 1)
A laminate having a total thickness of 105 μm was produced in the same manner as in Example 1 except that the hard coat layer composition (9) having the following composition was used instead of the hard coat layer composition (1).

(Composition for hard coat layer (9))
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku DPHA) 50 parts by mass Reactive deformed silica (manufactured by JGC Catalysts & Chemicals, ELCOM V8803) 50 parts by mass Irgacure 184 (manufactured by BASF Japan) 4 parts by mass MIBK 60 parts by mass MEK 60 parts by mass Part leveling agent (manufactured by DIC, F477) 0.6 parts by mass

(Reference Example 2)
A laminate having a total thickness of 105 μm was produced in the same manner as in Example 1 except that the hard coat layer composition (10) having the following composition was used instead of the hard coat layer composition (1).

(Composition for hard coat layer (10))
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku DPHA) 50 parts by mass Reactive deformed silica (manufactured by JGC Catalysts & Chemicals, ELCOM V8803) 50 parts by mass Irgacure 184 (manufactured by BASF Japan) 4 parts by mass MIBK 60 parts by mass MEK 60 parts by mass Part antifouling agent (X71-1203M, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.01 parts by mass

The following evaluation was performed about each laminated body obtained by the Example, the comparative example, and the reference example. The evaluation results are shown in Table 1, respectively.

(Surface contact angle, water)
The surface contact angle with respect to the water of the laminates obtained in Examples, Comparative Examples, and Reference Examples is the outermost surface of the laminate using a contact angle measuring device (Kyowa Interface Chemical Co., Ltd., model number: CA-X). A predetermined amount of pure water was dropped on the surface of the hard coat layer, and after 10 seconds, the shape of the water droplet was observed with an optical microscope or a CCD camera.

(Back contact angle, water)
The contact angle measuring device (Kyowa Interface Chemical Co., Ltd., model number: CA-X) is used for the back surface contact angle with respect to water of the laminates obtained in Examples, Comparative Examples, and Reference Examples. A certain amount of pure water was dropped, and after 10 seconds, the shape of the water droplet was observed and measured with an optical microscope or a CCD camera.

(Pencil hardness)
In the production process of the laminates obtained in Examples, Comparative Examples and Reference Examples, a sample in which an upper hard coat layer was formed on a base film was separately prepared as a sample, and the pencil hardness (1) of the sample was carried out. The pencil hardness (2) of the laminates according to Examples, Comparative Examples, and Reference Examples was measured based on JIS K5600-5-4 (1999), respectively.

(Flexibility)
The laminates according to Examples, Comparative Examples, and Reference Examples were used as 100 mm × 150 mm samples, wound around a cylinder with the hard coat layer side facing outside, and the diameter of the limit cylinder without cracks was determined. As a result, when the diameter of the cylinder was 20 mm or less, it was evaluated that it was excellent in flexibility.

(Anti-fouling performance)
Fingerprints were attached to the surfaces of the laminates according to Examples, Comparative Examples, and Reference Examples, and then wiped off with a tissue. The state of the surface after wiping off was visually observed and evaluated according to the following criteria.
○: Completely wiped off ×: Completely wiped off, leaving fingerprint marks

As shown in Table 1, the laminates according to the examples had high hardness and excellent flexibility, and were excellent in antifouling performance.
On the other hand, the laminates according to Comparative Examples 1, 3, 4 and 6 are inferior in hardness, the laminate according to Comparative Example 2 is inferior in flexibility, and the laminate according to Comparative Example 5 is in contact with water on the back surface. The corner was big. The laminates according to Reference Examples 1 and 2 were excellent in hardness and flexibility, but the antifouling performance was inferior because the antifouling agent was not contained in the hard coat layer or the content was small.

The touch panel of the present invention has a laminated body having extremely excellent hardness and flexibility, and the laminated body is suitably used as a touch panel application as a glass substitute material, and is a flexible and flexible organic type. It can also be used for EL displays, portable terminals such as smartphones and wristwatch-type terminals, display devices inside automobiles, flexible panels used for wristwatches, and the like, and also for image display devices such as liquid crystal display devices.

Claims (12)

A touch panel comprising a laminate having a hard coat layer on one surface of a base film and a resin cured layer on the other surface of the base film,
The base film has a thickness of 40 to 125 μm,
The hard coat layer has a thickness of 10 to 25 μm,
The total thickness of the said laminated body is 100-220 micrometers, The touch panel characterized by the above-mentioned. The touch panel according to claim 1, wherein the laminate does not cause cracks when wound on a cylinder having a diameter of 20 mm and is 6H or more in a pencil hardness test (load 750 g) according to JIS K5600-5-4 (1999). . The touch panel according to claim 1, wherein the hard coat layer contains an antifouling agent having a reactive functional group. The touch panel according to claim 3, wherein a contact angle of water on the surface of the hard coat layer with respect to water is 100 to 120 °. The touch panel according to claim 1, 2, 3, or 4, wherein the laminate has a resin-cured layer side surface attached to a polarizer or a polarizing plate via an adhesive layer or an adhesive layer. The touch panel according to claim 1, wherein the resin cured layer is a cured layer of a monofunctional monomer. The touch panel according to claim 6, wherein the monofunctional monomer is a monofunctional acrylic monomer. The monofunctional acrylic monomer is at least one selected from the group consisting of acryloylmorpholine, N-acryloyloxyethylhexahydrophthalimide, cyclohexyl acrylate, tetrahydrofuryl acrylate, isobornyl acrylate, phenoxyethyl acrylate, and adamantyl acrylate. The touch panel according to claim 7. The touch panel according to claim 1, 2, 3, 4, 5, 6, 7 or 8, further comprising another base film on a surface opposite to the base film of the resin cured layer. The touch panel according to claim 9, further comprising a lower hard coat layer on a surface opposite to the resin cured layer of another base film. A laminated body used for the touch panel according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. Forming a hard coat layer on one surface of the base film using the hard coat layer composition; and
The manufacturing method of the laminated body which has the process of forming a resin hardened layer by the roll-to-roll system using the composition for hardened layers on the other surface of the said base film.