JP7102727B2 - Active energy ray-curable composition and index matching layer and laminate using it - Google Patents

Description

The present invention relates to an active energy ray-curable composition. Further, the present invention relates to an index matching layer and a laminate using the same.

Conventionally, a laminate in which a transparent conductive layer is provided on a base material such as polyester has been used for touch panel applications and the like. As the transparent conductive layer, a thin film of a metal oxide such as indium tin oxide (ITO) is generally used, and the transparent conductive layer is laminated on the base material by a sputtering method or a vacuum vapor deposition method.
The resistance film type is the mainstream as the operation method of the touch panel, but the capacitance type has been rapidly expanding in recent years. The transparent conductive laminate used in a resistive touch panel is usually composed of an unpatterned transparent conductive layer. On the other hand, in the laminated body used for the capacitive touch panel, the transparent conductive layer is patterned by photolithography etching or the like, and the patterned portion and the non-patterned portion of the transparent conductive layer are present on the laminated body.

Capacitive touch panels using a laminate having such a patterned transparent conductive layer have a problem of so-called "bone visibility" in which the patterned portion and the non-patterned portion of the transparent conductive layer are visually visually recognized. There is a problem that the appearance as a display device is finally deteriorated. On the other hand, for example, in Patent Document 1, an attempt is made to solve the visibility by providing a refractive index adjusting layer (referred to as an index matching layer) between the base material and a transparent conductive layer such as ITO. The index matching layer suppresses "bone visibility" by reducing the difference in reflectance between the portion having the transparent conductive layer and the portion not having the transparent conductive layer.

In recent years, a laminate having an index matching layer has one or both sides of the laminate being multi-layered depending on the application, and ultraviolet rays and other active energy rays are excessive during the process of multi-layering or the subsequent patterning of the transparent conductive layer. May be irradiated. In that case, there is a problem that the adhesiveness between the index matching layer and the base material or between the index matching layer and the transparent conductive layer is lowered.
Further, when the active energy ray-curable composition is stored for a long period of time, the composition having poor storage stability causes thickening or the like, and when an index matching layer is formed using the composition, the transparency is lowered and the transparency is lowered. The refractive index of the index matching layer may be affected, or defects may occur during coating. Therefore, the active energy ray-curable composition has durability against active energy rays as well as stability of the composition. Coating suitability is also required.

For example, Patent Documents 2 and 3 have proposed an index matching layer that solves the problems of visual recognition of a transparent conductive layer pattern and UV durability. Patent Document 2 proposes an index matching layer using a cardo resin, and although the adhesion to glass and ITO is shown, the adhesion to a plastic base material is not shown. Further, Patent Document 3 proposes an index matching layer in which the zeta potential is defined, and although the adhesion between the plastic base material and the index matching layer is mentioned, the adhesion with the ITO electrode layer is also mentioned. However, the stability and coating suitability of the active energy ray composition itself have not been clarified.

Japanese Unexamined Patent Publication No. 2014-209333 Japanese Unexamined Patent Publication No. 2014-152197 JP-A-2017-002112

INDUSTRIAL APPLICABILITY The present invention is active for forming an index matching layer which can maintain adhesiveness to a base material and a transparent conductive layer regardless of excessive activation energy ray irradiation, has excellent coating suitability, and has a good appearance. An object of the present invention is to provide an energy ray-curable composition.

As a result of diligent research on the above problems, the present inventor has found that the problem can be solved by using the active energy ray-curable composition described below, and has reached the present invention.

The present invention is an active energy ray-curable composition containing a metal oxide having an average particle diameter of 4 to 200 nm, which may be surface-treated, for forming an index matching layer on a substrate. The present invention relates to an active energy ray-curable composition characterized by satisfying (1) to (3).
(1) The metal oxide contains zirconium oxide and titanium oxide and / or zinc oxide in a mass ratio of 99/1 to 65/35.
(2) The ratio of the average particle size of the metal oxide (zirconium oxide / titanium oxide or zirconium oxide / zinc oxide) is 1.0 / 0.3 to 1.0 / 1.8.
(3) Contains a pentaerythritol acrylate compound.

The present invention relates to the active energy ray-curable composition, wherein at least one selected from zirconium oxide, titanium oxide and zinc oxide is surface-treated with a silane compound.

The present invention further contains at least one resin selected from the group consisting of urethane acrylate, polyester acrylate, epoxy acrylate and acrylic resin (excluding the above pentaerythritol acrylate-based compound) having a weight average molecular weight of 1000 to 30,000. The present invention relates to the above-mentioned active energy ray-curable composition.

The present invention relates to the active energy ray-curable composition, characterized in that the wettability index of the surface of the substrate in contact with the index matching layer is 35 to 65 dyne / cm.

The present invention relates to the active energy ray-curable composition, which is characterized by being used for gravure printing.

The present invention relates to a laminate having a base material, an index matching layer made of the active energy ray-curable composition, and a transparent electrode layer in this order.

According to the present invention, the activity for forming an index matching layer which can maintain the adhesiveness to the base material and the transparent conductive layer, has excellent coating suitability, and has a good appearance regardless of excessive activation energy ray irradiation. An energy ray-curable composition could be provided.

The embodiments of the present invention will be described in detail below, but the description of the requirements described below is an example (representative example) of the embodiments of the present invention, and the present invention has the contents as long as the gist of the present invention is not exceeded. Not limited to.

The present invention is an active energy ray-curable composition containing a metal oxide having an average particle diameter of 4 to 200 nm, which may be surface-treated, for forming an index matching layer on a substrate. It is an active energy ray-curable composition characterized by satisfying 1) to (3).
(1) The metal oxide contains zirconium oxide and titanium oxide and / or zinc oxide in a mass ratio of 99/1 to 65/35.
(2) The ratio of the average particle size of the metal oxide (zirconium oxide / titanium oxide or zirconium oxide / zinc oxide) is 1.0 / 0.3 to 1.0 / 1.8.
(3) Contains a pentaerythritol acrylate compound.
When the metal oxide contains zirconium oxide and titanium oxide and / or zinc oxide in the corresponding ratio, the adhesion between the base material and the transparent conductive layer is improved, and the average particle size of the metal oxide is within the corresponding range. The transparency of the laminate having the index matching layer is good. Further, by containing a pentaerythritol acrylate compound, it is possible to improve the scratch resistance of the laminate.

<Index matching layer>
In the present invention, the "index matching layer" refers to an active energy ray-curable resin layer provided between a base material and a transparent conductive layer. The film thickness of the index matching layer is preferably 0.02 to 30 μm, and the refractive index of the index matching layer is preferably 1.4 to 2.0.

<Active energy ray-curable composition>
The active energy ray-curable composition refers to a composition containing a resin component that is cured through a cross-linking reaction or the like by irradiation with active energy rays such as ultraviolet rays or electron beams. In the following description, the active energy ray-curable composition may be simply abbreviated as "composition", but it has the same meaning.
After coating the active energy ray-curable composition, it is cured by irradiating it with active energy rays such as ultraviolet rays and electron beams to form an index matching layer.

<Metal oxide>
The surface-treated metal oxide having an average particle size of 4 to 200 nm contains zirconium oxide and titanium oxide and / or zinc oxide, and the ratio of their contents (zirconium oxide / titanium oxide and zinc oxide). ) Is 99/1 to 65/35. It is preferably 95/5 to 70/30 because it contributes to blocking active energy rays such as ultraviolet rays. Zirconium oxide and titanium oxide and / or zinc oxide are preferably contained in a total of 80% or more in the total mass of the metal oxide. The average particle size is preferably 10 to 100 nm. The average particle size is the average particle size in the dispersed state, and refers to the measured value of D50 by the dynamic light scattering method. The dynamic light scattering measurement can be performed using, for example, "Nanotrack UPA" manufactured by Nikkiso Co., Ltd.

The average particle size ratio of the metal oxide (zirconium oxide / titanium oxide or zirconium oxide / zinc oxide) is 1.0 / 0.3 to 1.0 / 1.8. The ratio of the average particle size of zirconium oxide to titanium oxide and / or zinc oxide in a dispersed state is more preferably 1.0 / 0.5 to 1.0 / 1.7.
The total amount of zirconium oxide, titanium oxide and / or zinc oxide is preferably contained in the total solid content of the composition in an amount of 10 to 80% by mass. The solid content refers to the total mass of the non-volatile components in the composition.

The specific surface area of titanium oxide and zinc oxide is preferably 20 to 160 m ² / g, and more preferably 30 to 150 m ² / g. The specific surface area means a value measured by the measuring method described in JIS Z 8830: 2001. When the specific surface area is within this range, the transparency of the index matching layer becomes good, and even when the active energy rays are excessively irradiated as the integrated light amount, the adhesiveness to the substrate can be maintained well.

In the present invention, the metal oxide is preferably a combination of zirconium oxide and titanium oxide. The surface of the metal oxide may be treated with an organic substance or an inorganic substance. The titanium oxide is preferably a rutile-type crystal.

<Surface treatment with silane compound>
At least one metal oxide selected from zirconium oxide, titanium oxide and zinc oxide is preferably surface-treated with a silane compound. A known silane compound can be used for the surface treatment. Such a silane compound preferably has a kind of group selected from the group such as an alkoxyl group, a hydroxyl group, a vinyl group, a styryl group, a (meth) acryloyl group, and an epoxy group, and in particular, a styryl group and a vinyl group. Alternatively, those having a (meth) acryloyl group are more preferable. This is because the compatibility with the resin and the like described later is good.

The surface treatment refers to a state in which the metal oxide particles are coated by the reaction of the silane compound. For the treatment with the silane compound, for example, the silane compound and the treatment method described in JP-A-2010-195967 can be used.

The silane compound is not limited to the following, but a silane compound having a styryl group, a vinyl group or a (meth) acryloyl group is preferable, and for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltricrolsilane, vinyltriphenoxysilane, p. -Styryltrimethoxysilane, p-styryltriethoxysilane, p-styryltrichlorosilislane, p-styryltriphenoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-acryloyloxypropyl Trichlorosilane, 3-acryloyloxypropyltriphenyloxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltrichlorosilane, 3-methacryloyloxypropyltriphenoxysilane, allyltrimethoxy Examples thereof include silane, allyltriethoxysilane, allyltrichlorosisilane, and allyltriphenoxysilane.

In addition to the above, the silane compound may be used in combination with a silane compound having an alkyl group, a silane compound having a phenyl group, a silane compound having an amino group, or another silane compound having a non-polymerizable group.

The amount of the silane compound used is preferably in the range of 0.1 to 40% by mass with respect to the metal oxide. More preferably, it is 5 to 30% by mass. This is because the dispersion stability is good. The treatment with the silane compound is preferably performed by at least one selected from zirconium oxide, titanium oxide and zinc oxide. It is more preferable that at least zirconium oxide is surface-treated.

In the following description, (meth) acrylate means methacrylate and acrylate, and (meth) acrylic means both methacrylic and acrylic.

<Pentaerythritol acrylate compound>
Pentaerythritol acrylate compounds include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tripenta acrylate octa (meth) acrylate. Further, those having a polyether structure such as a polyethylene oxide structure and a polypropylene oxide structure between the pentaerythritol structure and the (meth) acrylate group structure of these compounds can be mentioned, and are selected from the group consisting of these. At least one type of acrylic, which has a molecular weight of less than 700. These pentaerythritol (meth) acrylate compounds may be used alone or in combination of two or more. The pentaerythritol acrylate-based compound is preferably contained in an amount of 10 to 80% by mass in the total solid content of the composition. Further, it is more preferably contained in an amount of 10 to 70% by mass. Further, the mass ratio of the total of the above metal oxides to the pentaerythritol acrylate-based compound (metal oxide meter / pentaerythritol acrylate-based compound) is preferably 90/10 to 20/80, preferably 90/10 to 30. It is more preferable to contain it at / 70.

<Resin>
In the present invention, it is preferable that the composition further contains at least one resin selected from the group consisting of urethane acrylate, polyester acrylate, epoxy acrylate and acrylic resin having a weight average molecular weight of 1000 to 30,000.
The content of the resin is preferably 5 to 45% by mass, more preferably 10 to 40% by mass, based on the total solid content of the composition. Further, from the viewpoint of gravure coatability, the weight average molecular weight is more preferably 1000 to 20000. Further, it has a polymerizable functional group such as an acryloyl group, and the number of polymerizable functional groups (number of functional groups) in one molecule is preferably 4 to 15.
As the resin, a polyfunctional resin such as urethane acrylate, polyepoxy acrylate, or polyester acrylate can be preferably used from the viewpoint of coating strength and abrasion resistance (scratch resistance). Of these, polyester acrylate and / or urethane acrylate are preferable.

When the above resin is contained, the mass ratio (resin / pentaerythritol acrylate compound) with the pentaerythritol acrylate compound is preferably 90/10 to 10/90, and is preferably 80/20 to 50/50. Is more preferable.

<Epoxy acrylate>
Examples of the polyepoxy acrylate include those in which the glycidyl group of the epoxy resin is esterified with (meth) acrylic acid and the functional group is used as the (meth) acrylate group. Addition of (meth) acrylic acid to the bisphenol A type epoxy resin. There are (meth) acrylic acid additions to novolak type epoxy resins.

<Urethane acrylate>
The polyurethane acrylate is, for example, one obtained by reacting diisocyanate with (meth) acrylates having a hydroxyl group, or an isocyanate group-containing urethane prepolymer obtained by reacting a polyol and polyisocyanate under a condition of excess isocyanate group. Some are obtained by reacting with (meth) acrylates having a hydroxyl group. Alternatively, a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate under a condition of excess hydroxyl group can be obtained by reacting with (meth) acrylates having an isocyanate group.

For example, urethane acrylate can be obtained by reacting polyisocyanate with a hydroxyl group-containing (meth) acrylate. It can also be obtained by reacting a urethane prepolymer having an isocyanate group at the terminal with a hydroxyl group-containing (meth) acrylate. However, the method for synthesizing urethane acrylate is not limited to these.

Known polyisocyanates can be used, and examples thereof include aromatic diisocyanates, aliphatic diisocyanates, and alicyclic diisocyanates.
Examples of the aromatic diisocyanate include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzylisocyanate, and 1,3-phenylene. Examples thereof include diisocyanate, 1,4-phenylenediocyanate, tolylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, and 2,6-diisocyanate-benzyl chloride.
Examples of the aliphatic diisocyanate include butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.
Examples of the alicyclic diisocyanate include cyclohexane-1,4-diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, dimeryl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, and 1,3-bis (isocyanatemethyl) cyclohexane. Examples thereof include methylcyclohexanediisocyanate, norbornandiisocyanate, and diisocyanate obtained by converting the carboxy group of dimer acid into an isocyanate group.
These may be trimers and have an isocyanurate ring structure. These polyisocyanates can be used alone or in combination of two or more.
Of these, isocyanurates of tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hexamethylene diisocyanate, and hexamethylene diisocyanate are preferable.

Examples of the hydroxyl group-containing (meth) acrylate include trimethylolpropandi (meth) acrylate, trimethylol ethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate (meth) acrylic acid 2-. Hydroxyethyl, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate Hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) Acrylic acid ester, (meth) acrylic acid 10-hydroxydecyl, (meth) acrylic acid 12-hydroxylauryl, (meth) acrylic acid ethyl-α- (hydroxymethyl), monofunctional (meth) acrylic acid glycerol, or these. (Meta) acrylate and (meth) acrylic acid ester having a hydroxyl group at the terminal due to ring-open addition of ε-caprolactone lactone, and alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide with respect to the hydroxyl group-containing (meth) acrylate. Examples thereof include hydroxyl group-containing (meth) acrylic acid esters such as alkylene oxide-added (meth) acrylic acid ester to which the above is repeatedly added. Among them, those containing at least one selected from trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.

<Polyester acrylate>
The polyester acrylate can be obtained, for example, by reacting a polyester polycarboxylic acid obtained by polycondensing a polybasic acid and a polyhydric alcohol with a hydroxyl group-containing (meth) acrylate or the like.
Examples of the above-mentioned polybasic acid include aliphatic type, alicyclic group type, and aromatic type, and each of them can be used without particular limitation. For example, aliphatic polybasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebatic acid, azelaic acid, suberic acid, maleic acid, fumaric acid, dodecanedioic acid, pimeric acid, citraconic acid, and glutaric acid. Examples thereof include itaconic acid, succinic anhydride, maleic anhydride and the like, and these aliphatic dicarboxylic acids and anhydrides thereof can be used. Derivatives of acid anhydride can also be used.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol, triethylene glycol, butylene glycol, 3-methyl-1,5-pentanediol, and 2,4-diethyl-1,5. -Pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptan, 2-butyl-2-ethyl-1,3-propanediol, polyoxyethylene glycol (additional moles: 10 or less) , Polyoxypropylene glycol (additional number of moles 10 or less), propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol , Neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, cyclopentadienedimethanol, dimerdiol and other aliphatic or fats. Cyclic diols can be mentioned.

In addition, some polyols containing three or more hydroxyl groups, such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol, may be used.

Among the above polyhydric alcohols, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3 Branched alkanes such as'-dimethylol heptane, 2-butyl-2-ethyl-1,3-propanediol, butylethylpentanediol, 2-ethyl-1,3-hexanediol, trimethylolpropane, etc. have hydroxyl groups. It is preferable that two or more of them are introduced in terms of adhesiveness, heat resistance and the like of the oligomer.

Examples of the hydroxyl group-containing (meth) acrylate include the same as above, among which trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (dipentaerythritol penta). Those containing at least one selected from meta) acrylates are preferred.

<Acrylic resin>
Acrylic resin is a copolymer obtained by using an acrylic monomer. The acrylic monomers constituting the acrylic resin are listed below. The acrylic monomer may be used alone or in combination of two or more. Among the acrylic monomers listed below, the acrylic monomer preferably contains an alkyl methacrylate and / or an alkyl acrylate, and the alkyl group of the acrylic monomer preferably has 1 to 6 carbon atoms. The weight average molecular weight is preferably 1000 to 30,000. Further, it may or may not have a polymerizable functional group such as an acryloyl group. When having the functional group, the double bond equivalent is preferably 200 to 2000 g / mol. The double bond equivalent means the weight average molecular weight per 1 mol of the double bond.

As the acrylic monomer, alkyl (meth) acrylate is preferable, and methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, ( Hexyl acrylate, Cyclopentyl (meth) acrylate, Cyclopentyl (meth) acrylate, Methylcyclohexyl (meth) acrylate, Bornyl (meth) acrylate, Isobornyl (meth) acrylate, Dicyclopentenyl (meth) acrylate , (Meta) dicyclopentanyl acrylate, (meth) 2-ethylhexyl acrylate, (meth) isooctyl acrylate, (meth) decyl acrylate, (meth) dodecyl acrylate, (meth) tetradecyl acrylate, (meth) ) Hexadecyl acrylate, octadecyl (meth) acrylate and the like. Among these, methyl (meth) acrylate is preferable because it is easy to obtain good adhesion to the substrate.

Further, as the acrylic monomer, a hydroxyl group-containing alkyl (meth) acrylate is also suitable, and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth). ) 2-Hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, etc. Glycol mono (meth) acrylates such as meta) acrylic acid hydroxyalkyl esters, polyethylene glycol mono (meth) acrylates, polypropylene glycol mono (meth) acrylates, 1,4-cyclohexanedimethanol mono (meth) acrylates, and caprolactone-modified (meth) acrylates. ) Acrylate, hydroxyethyl acrylamide and the like can be mentioned. Among these, 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are preferable.

Examples of other acrylic monomers include those having a carboxyl group, those having an amide bond, those having an amino group, those having an alkylene oxide group, those having an epoxy group, and the like.

Further, a monomer other than the acrylic monomer may be included as a constituent unit of the acrylic resin. Examples thereof include acidic monomers such as maleic acid, maleic anhydride, monoethyl maleic acid, itaconic acid, citraconic acid, and fumaric acid, and styrene-based monomers such as styrene and α-methylstyrene. These monomers can be contained within a range that does not impair the effects of the present invention.

The pentaerythritol-based compound and resin constituting the active energy ray-curable composition of the present invention preferably contain a polymerization inhibitor from the viewpoint of stability. Examples of the polymerization inhibitor include hydroquinone compounds, and hydroquinone, methylhydroquinone, and paramethoxyphenol are preferable. The content is preferably 100 to 500 ppm with respect to the resin.

Examples of the above-mentioned commercially available resin products include the following.
Toa Synthetic Co., Ltd .: Aronix M-7100, Aronix M-8030, Aronix M-8060, Chemical Industry Co., Ltd .: CN986NS, CN9010NS, Daicel Ornex Co., Ltd .: Ebecryl 220, Ebecryl 1290, Ebecryl 1830 , Shin Nakamura Chemical Industry Co., Ltd .: NK Oligo U6LPA, NK Oligo U10PA, NK Oligo U10HA, NK Oligo UA-33H, NK Oligo UA-53H, Arakawa Chemical Industry Co., Ltd .: Beam set 371, Beam set 575, Beam set 577, manufactured by Negami Kogyo Co., Ltd .: Art Resin UN-3320HA, Art Resin UN-3320HB, Art Resin UN-3320HC, Art Resin UN-3320HS, Art Resin UN-9000H, Art Resin UN-901T, Art Resin UN -904, Art Resin UN-905, Art Resin UN-952, Art Resin HDP, Art Resin HDP-3, Art Resin H61, manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: Purple Light UV-7600B, Purple Light UV-7610B, Purple Light UV -7620EA, Purple Light UV-7630B, Purple Light UV-1700B, Purple Light UV-6300B, Purple Light UV-7640B
Made by Kyoeisha Chemical Co., Ltd .: UA-306H, UA-306T, UA-306I.

<Other monomers>
The active energy ray-curable composition of the present invention may contain a (meth) acrylate monomer having a pentafunctionality or less (however, the pentaerythritol-based compound is not included). For example, examples of the 3-4 functional (meth) acrylate monomer include trimethylolpropane tetraacrylate, trimethylolpropane tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, and ethoxylated trimethylolpropane tri. Examples thereof include acrylate and propoxylated trimethylolpropane triacrylate. Further, various bifunctional and monofunctional monomers can be appropriately used.

Examples of the bifunctional (meth) acrylate monomer include trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpoly acrylate, and PO-modified trimethylolpoly (meth) acrylate. These (meth) acrylates may be used alone or in combination of two or more.

Examples of the monofunctional (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate.

<Organic solvent>
The active energy ray-curable composition of the present invention may contain an organic solvent as a liquid medium. The organic solvent used is preferably used as a mixed solvent, such as aromatic organic solvents such as toluene and xylene, ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, n-propyl acetate, isopropyl acetate and isobutyl acetate. , Ester-based organic solvents, alcohol-based organic solvents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and glycoether-based organic solvents such as propylene glycol monomethyl ether can be used. In particular, it is preferable to contain a glycol ether-based organic solvent.

Examples of the glycol ether-based organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, and ethylene glycol dipropyl. Ethylene glycol such as ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol dibutyl ether, ethylene glycol isoamyl ether, ethylene glycol monohexyl ether, ethylene glycol mono2-ethylhexyl ether, methoxyethoxyethanol, ethylene glycol monoallyl ether, etc. Ethers;
Propylene glycol ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, butoxypropanol;
Of these, methylpropylene glycol, 3-methoxy-1-butanol is preferable.

<Photopolymerization initiator>
The active energy ray-curable composition can further contain a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has a function of initiating vinyl polymerization of a (meth) acryloyl group for forming an active energy ray-cured film by photoexcitation. For example, a monocarbonyl compound or a dicarbonyl compound. , Acetophenone compound, benzoin ether compound, acylphosphine oxide compound, aminocarbonyl compound and the like can be preferably used.

Examples of the monocarbonyl compound include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 4- (4-methylphenylthio) phenyl-etanone, 3 , 3'-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,3,3'-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,4,7,10) , 13-Pentaoxotridecyl) benzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N, N-trimethyl-1-propaneamine hydrochloride, 4 -Benzophenone-N, N-dimethyl-N-2- (1-oxo-2-propenyloxyethyl) metaammonium oxalate, 2- / 4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4 -Dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroki-3- (3,4-dimethyl-9-oxo-9H thioxanthone-2-iroxy-N, N, N-trimethyl-1-propaneamine hydrochloride Examples thereof include salts, benzoylmethylene-3-methylnaphtho (1,2-d) thiazolin and the like.

Examples of the dicarbonyl compound include 1,2,2-trimethyl-bicyclo [2.1.1] heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxo. Examples thereof include benzene acetate and 4-phenylbenzyl.
Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-. (4-Isopropylphenyl) -2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxy-cyclohexylphenylketone, 2-hydroxy-2-methyl-1-styrylpropane-1-one Polymers, diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2-methyl-1 -[4- (Methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, 1-phenyl-1,2- Propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2-morpholino-propanonyl) -9-butylcarbazole and the like can be mentioned.

Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin normal butyl ether and the like.
Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide and the like.

Examples of the aminocarbonyl compound include methyl-4- (dimethoxyamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-n-butoxyethyl-4- (dimethylamino) benzoate, and isoamyl-4- (dimethylamino). Benzoate, 2- (dimethylamino) ethylbenzoate, 4,4'-bis-4-dimethylaminobenzophenone, 4,4'-bis-4-diethylaminobenzophenone, 2,5'-bis (4-diethylaminobenzal) cyclo Pentanone and the like can be mentioned.

Commercially available products of the above photopolymerization initiator include Omnirad73, 481, 659, 248, 264, 4817, BDK, TPO, TPO-L, 380, Omnipol910, BP, 2702, Esasure One, 1001M, A198, KIP150, manufactured by IGM Resins. And so on.

The photopolymerization initiator is not limited to the above compounds, and may be used alone or in combination of two or more. Regarding the amount of the photopolymerization initiator used, in the active energy ray-curable composition forming the index matching layer in the present invention, it is used within the range of 1 to 20% by mass with respect to the total mass of the solid content excluding the metal oxide. It is preferable to do so. As a sensitizer, a known organic amine or the like can be added. Further, in addition to the above-mentioned initiator for radical polymerization, an initiator for cationic polymerization can also be used in combination.

<Other combined resins>
The active energy ray-curable composition may contain other polymer materials as long as its properties are not impaired, and is not limited to the following, but is photocurable other than the pentaerythritol acrylate-based compound and the resin. Resin, chlorinated polypropylene resin, polyolefin resin, ethylene-vinyl acetate copolymer resin, vinyl acetate resin, alkyd resin, polyvinyl chloride resin, rosin resin, rosin-modified maleic acid resin, terpene resin, phenol-modified terpene resin, ketone Examples thereof include resins, cyclized rubbers, rubber chlorides, butyral, petroleum resins, and modified resins thereof. These resins can be used alone or in combination of two or more, and the content thereof is preferably 1 to 20% by mass based on the total mass of the resin solids in the active energy ray-curable composition.

<Additives>
The active energy ray-curable composition of the present invention may further contain various additives as long as the object and effect of the present invention are not impaired. Specifically, polymerization inhibitors, photosensitizers, leveling agents, surfactants, antibacterial agents, antiblocking agents, plasticizers, UV absorbers, infrared absorbers, antioxidants, conductive polymers, conductive interfaces. Activators, inorganic fillers, pigments, dyes and the like can be mentioned.

<Manufacturing of active energy ray-curable composition>
The active energy ray-curable composition of the present invention does not have any problem as long as it can be uniformly stirred and mixed. It can be produced by uniformly stirring with a stirrer, a disper, a homogenizer, or the like. In the present invention, metal oxides such as zirconium oxide, titanium oxide and zinc oxide are dispersed together with pentaerythritol acrylate-based compounds, resins such as urethane acrylate and polyester acrylate and an organic solvent using a three-roll, sand mill, gamma mill or the like. Acrylate may be blended, or a commercially available dispersion of an organic solvent or the like may be blended and used.

<Base material>
The base material of the present invention is not limited to the following, but is preferably a polyester film, a triacetyl cellulose film, a polyolefin film, a cycloolefin film, an acrylic film, a polycarbonate film or other plastic base material. In particular, a polyester film such as polyethylene terephthalate (PET) film is suitable. The film thickness of the base material may be appropriately selected according to the desired application, but is preferably in the range of 20 μm to 300 μm, preferably in the range of 50 μm to 250 μm, and more preferably in the range of 50 μm to 200 μm. The refractive index of the base material is preferably 1.45 to 1.75, more preferably 1.75 to 1.75, from the viewpoint of greatly contributing to the visibility of the entire laminate having the base material, the index matching layer, and the transparent conductive layer in this order. , 1.45 to 1.70.

The wettability index of the surface of the base material in contact with the index matching layer is preferably 35 to 65 dyne / cm, more preferably 38 to 60 dyn / cm. A layer made of an organic substance and / or an inorganic substance may be further provided on the surface in contact with the index matching layer, and specific examples thereof include an easy-adhesion layer for improving the adhesiveness with other layers. Examples of the easy-adhesion layer include various types such as corona discharge treatment, UV-ozone treatment, plasma treatment, and primer treatment, which may be treated in combination. Among them, a substrate which has been subjected to primer treatment or corona discharge treatment is particularly suitable. It is preferable that the substrate is primed. The wettability index means a value measured by JISK6768.

<Manufacturing of index matching layer>
The method for producing the index matching layer includes, for example, a step of applying the active energy ray-curable composition to the substrate and a step of irradiating the substrate with active energy rays to cure the active energy ray-curable composition on the substrate. include. More specifically, this active energy ray-curable composition is applied to a base material so that the film thickness after drying is preferably 0.02 to 30 μm, more preferably 0.02 to 20 μm, and then activated. It can be formed by curing treatment with energy rays.

As a coating method of the active energy ray-curable composition, a known method can be used, for example, a method using a lot or a wire bar, a microgravure coating method, a gravure coating method, a die coating method. , Curtain coating method, lip coating method, slot coating method or spin coating method and various other coating methods can be used. In the present invention, a microgravure coating method or a gravure coating method, which is a gravure printing method, is particularly preferable. This is because the smoothness of the coated surface is excellent.

As a curing method after coating, a known technique can be used. For example, it can be cured by irradiating it with active energy rays such as ultraviolet rays, electron beams, and visible rays having a wavelength of 400 to 500 nm. For the source (light source) of ultraviolet rays and visible light having a wavelength of 400 to 500 nm, for example, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used. A thermoelectron radiation gun, an electrolytic radiation gun, or the like can be used as the electron radiation source. The integrated light amount of the active energy rays to be irradiated is preferably in the range of 50 to 1000 mJ / cm ² from the viewpoint of easy control in the process. Heat treatment by infrared rays, far infrared rays, hot air, high frequency heating or the like can be used in combination with these activation energy ray irradiations.

The index matching layer may be formed by applying an active energy ray-curable composition to a base material and naturally or forcibly drying it and then performing a curing treatment, or after applying and curing the index matching layer. It may be naturally or forcibly dried, but it is more preferable to perform the curing treatment after the natural or forcibly dried. In particular, when curing with an electron beam, it is more preferable to perform the curing treatment after natural or forced drying in order to prevent the coating film from being hardened by water or the strength of the coating film from being lowered due to the residual organic solvent. The timing of the curing treatment may be at the same time as the coating or after the coating.

Since the obtained cured film is excellent in transparency and adhesiveness, it can be suitably used as an optical material. The thickness of the cured film is preferably 0.02 to 30 μm. Further, the refractive index of the cured film is preferably in the range of 1.4 to 2.0, more preferably in the range of 1.5 to 1.9.

<Transparent conductive layer>
As the material of the transparent conductive layer, a known material used for the electrode of the touch panel can be used. Examples thereof include metal oxides such as tin oxide, indium oxide, antimony oxide, zinc oxide, ITO (indium tin oxide) and ATO (antimony oxide). Of these, ITO is preferably used. The method for forming the transparent conductive layer is not particularly limited, and a conventionally known method can be used. Specifically, a dry process such as a vacuum deposition method, a sputtering method, or an ion plating method can be used.

The thickness of the transparent conductive layer is preferably 10 to 60 nm, more preferably 15 to 50 nm, and particularly preferably 20 to 40 nm, for example, from the viewpoint of ensuring good conductivity having a surface resistance value of ¹⁰³ Ω / □ or less. The refractive index of the transparent conductive layer is 1.8 or more. Further, the refractive index of the transparent conductive layer is preferably 1.8 to 2.2. Further, it is more preferably 1.9 to 2.1. The transparent conductive layer of the present invention is patterned. For example, a striped shape, a grid shape, or the like can be mentioned, and it is generally performed by etching. Examples of the etching include a photolithography method and a laser exposure method. Examples of the etching solution include inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, nitrate and phosphoric acid, organic acids such as acetic acid, and these. Mixtures and aqueous solutions thereof are used.

<Laminated body>
The laminate of the present invention refers to one having a base material, an index matching layer, and a transparent conductive layer in this order. The base material and the index matching layer are in contact with each other, and the other layer configurations are arbitrary, and a base material layer, a layer having a different refractive index, an adhesive layer and other layers (M) can be provided as needed. An example is shown below.
(I) Base material / index matching layer / transparent conductive layer
(II) Base material / Index matching layer / (M) / Transparent conductive layer (III) (M) / Base material / Index matching layer / Transparent conductive layer (IV) (M) / Base material / Index matching layer / (M) ) / Transparent conductive layer (V) (M) / Index matching layer / Base material / Index matching layer / Transparent conductive layer (VI) Index matching layer / Base material / Index matching layer / Transparent conductive layer

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, parts and% in the present invention represent parts by weight or% by weight.

(Average particle size)
The measurement was performed using a dynamic light scattering method (Nanotrack UPA manufactured by Nikkiso Co., Ltd.) in an environment of 25 ° C. The dispersion liquid concentration was adjusted in the range of 0.7 or more and 1.3 or less of the loading index value, and the value of D50 measured by detecting the scattered light of the laser light was taken as the average particle size.
(Specific surface area)
Measured by the method described in JISZ8830: 2001.
(viscosity)
Measured by the method described in JISZ8803: 2011.
(Acid value)
The acid value of the solid content was measured by the method described in JIS K0070.
(Wetness index)
It was determined according to the method described in JIS K6768.
(Weight average molecular weight)
The weight average molecular weight was determined by measuring the molecular weight distribution using a GPC (gel permeation chromatography) apparatus (HLC-8220 manufactured by Tosoh Corporation) and using polystyrene as a standard substance as a converted molecular weight. The measurement conditions are shown below.
Column: The following columns were connected in series and used.
TSKgel SuperAW2500 manufactured by Tosoh Corporation
TSKgel SuperAW3000 manufactured by Tosoh Corporation
TSKgel SuperAW4000 manufactured by Tosoh Corporation
TSKgel guardcolum SuperAWH manufactured by Tosoh Corporation
Detector: RI (Differential Refractometer)
Measurement conditions: Column temperature 40 ° C
Eluent: Tetrahydrofuran Flow rate: 1.0 mL / min

(Synthesis Example 1) <Urethane Acrylate PU1>
In a flask equipped with a stirring blade, a thermometer, a reflux condenser, and a gas introduction tube, 150 parts of propyl acetate, 17 parts of hexamethylene diisocyanate, a temperature of 90 ° C., and dipentaerythritol pentaacrylate of about 60% by weight while blowing air. 182 parts of a mixture with about 40% by weight of pentaerythritol hexaacrylate (product name: "Aronix M403" manufactured by Toa Synthetic Co., Ltd.) and 49 parts of propyl acetate were mixed well and then added dropwise, and stirring was maintained for 10 hours after the completion of the addition. The molar ratio of the isocyanate group derived from hexamethylene diisocyanate to the hydroxyl group derived from dipentaerythritol pentaacrylate is isocyanate group: hydroxyl group (derived from dipentaerythritol pentaacrylate) = 1: 1. After confirming the disappearance of the peak derived from the isocyanate group in the IR spectrum, the mixture was cooled to room temperature to obtain PU1 as a mixture of urethane acrylate and dipentaerythritol hexaacrylate. PU1 has the following properties.
<Characteristics of PU1>
-The solid content mass ratio of urethane acrylate and dipentaerythritol hexaacrylate in PU1 is 61:39.
-The urethane acrylate in PU1 has 10 acrylate groups (acryloyl groups).
The weight average molecular weight of PU1 is 1900.

(Synthesis Example 2) <Urethane Acrylate PU2>
The same operation as in Synthesis Example 3 was carried out except that 22 parts of isophorone diisocyanate was used instead of 17 parts of hexamethylene diisocyanate used in Synthesis Example 3 to obtain PU2, a mixture of urethane acrylate and dipentaerythritol hexaacrylate. PU2 has the following properties.
<Characteristics of PU2>
-The solid content mass ratio of urethane acrylate and dipentaerythritol hexaacrylate in PU2 is 63:37.
-The urethane acrylate in PU2 has 10 acrylate groups (acryloyl groups).
-The weight average molecular weight of PU2 is 2100.

(Synthesis Example 3) <Urethane Acrylate PU3>
Instead of 17 parts of hexamethylene diisocyanate used in Synthesis Example 1, 22 parts of isophorone diisocyanate (NCO group: 2) was used, and instead of 182 parts of "Aronix M403", pentaerythritol triacrylate and pentaerythritol tetraacrylate were weighted. The same operation as in Synthesis Example 1 was carried out except that 90 parts by weight of a mixture having a ratio of 70:30 (product name: "Aronix M306" manufactured by Toagosei Co., Ltd.) was used to obtain a mixture PU3 of urethane acrylate and pentaerythritol triacrylate. .. PU3 has the following properties.
<Characteristics of PU3>
-The solid content mass ratio of urethane acrylate and pentaerythritol triacrylate in PU3 is 73:27.
-The urethane acrylate in PU3 has 6 acrylate groups (acryloyl groups).
-The weight average molecular weight of PU2 is 1500.

(Synthesis Example 4) <Polyester Acrylate PE1>
A four-necked flask equipped with a stirrer, a reflux condenser, a dry air introduction tube, and a thermometer contains 80.0 parts of 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, and a penta with a hydroxyl value of 122 mgKOH / g. Erislitol triacrylate (Product name: KAYARAD PET-30, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate) 250.0 parts, 0.24 parts of methylhydroquinone, 217.8 parts of cyclohexanone, and 60 ° C. The temperature was raised to. Next, 1.65 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and the mixture was stirred at 90 ° C. for 8 hours. When the acid value of the reaction product was measured at this point, it was 94 mgKOH / g.
Then, 78.3 parts of methacrylglycidyl ether and 54.0 parts of cyclohexanone were added, then 2.65 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C. for 6 hours, and the reaction was periodically carried out while continuing the reaction. When the acid value became 5.0 mgKOH / g or less, the reaction was stopped by cooling to room temperature to obtain PE1 which is a mixture of polyester acrylate and pentaerythritol tetraacrylate. PE1 was pale yellow and transparent, had a solid content of 60%, and had an acid value of 3.0 mgKOH / g.
<Characteristics of PE1>
-The solid content mass ratio of polyester acrylate and pentaerythritol tetraacrylate in PE1 is 76:24.
-The polyester acrylate in PE1 has eight acrylate groups (acryloyl groups).
-The weight average molecular weight of PE1 is 3500.

(Synthesis Example 5) <Polyester Acrylate PE2>
Same as Synthesis Example 4 except that pentaerythritol triacrylate was changed to dipentaerythritol pentaacrylate (product name: A-9570W dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) manufactured by Shin-Nakamura Chemical Industry Co., Ltd. By the method, a mixture PE2 of polyester acrylate and dipentaerythritol hexaacrylate was obtained.
<Characteristics of PE2>
-The solid content mass ratio of polyester acrylate and dipentaerythritol hexaacrylate in PE2 is 69:31.
-The polyester acrylate in PE2 has 12 acrylate groups (acryloyl groups).
-The weight average molecular weight of PE2 is 4000.

(Synthesis Example 6) <Acrylic Resin Ac1>
As an acrylic monomer, 29 parts of methyl methacrylate, 71 parts of butyl methacrylate, 125 parts of n-propyl acetate, and 2.5 parts of 2,2′-azobisisobutyronitrile were mixed under a nitrogen stream. After reacting at a temperature of 85 ° C. for 6 hours, an additional 1.5 parts of 2,2'-azobisisobutyronitrile was added and the reaction was carried out for another 1 hour. After completion of the reaction, 125 parts of n-propyl acetate was added to bring the solid content to 40%.
The obtained acrylic resin Ac1 had a weight average molecular weight (Mw) of 30,000, a molecular weight distribution (Mw / Mn) of 4.5, and a glass transition temperature of 40 ° C.

(Adjustment Example 1) <Surface Treatment of Zirconium Oxide Particles (ZrO ₂ Dispersion (1))>
200.0 g of a zirconium oxide particle dispersion (particle concentration 30% by weight, average particle diameter 22 nm (product name: "Zirconeo-Ck" manufactured by Aitec Inc.)) was placed in a separable flask, and 3-acryloyloxypropyltrimethoxysilane (3-acryloyloxypropyltrimethoxysilane) was added. Product name KBM-5103; manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 18.0 g was added and mixed by stirring to obtain a uniform solution. Further, 3.1 g of a 0.18 mass% HCl aqueous solution was added as a reaction catalyst to this mixed solution. In addition, the mixture was heated and stirred under the condition of an internal temperature of 40 ° C. for 6 hours to obtain zirconium oxide particles (ZrO ₂ dispersion (1)) surface-treated with a silane compound. The average particle size was 25 nm.

(Adjustment Example 2) <Surface Treatment of Titanium Oxide Particles (TiO ₂ Dispersion (1))>
The surface was treated with a silane compound by the same method as in Production Example 1 except that a titanium oxide dispersion (particle concentration 20% by weight, average particle diameter 10 nm, specific surface area 120 m ² / g, manufactured by JGC Catalysts and Chemicals, Inc.) was used. Titanium oxide fine particles (TiO ₂ dispersion (1)) were obtained. The average particle size was 11 nm.

(Example 1) <Preparation of active energy ray-curable composition S1>
As the metal oxide, 47 parts of the ZrO ₂ dispersion (1) obtained in Adjustment Example 1 was used as the particle solid content, and 5 parts of the TiO ₂ dispersion (1) obtained in Adjustment Example 2 was used as the particle solid content. As an erythritol acrylate-based compound, pentaerythritol tetraacrylate (product name: "Aronix M450" manufactured by Toa Synthetic Co., Ltd.) is used as ZrO ₂ particle mass: TiO ₂ particle mass: pentaerythritol acrylate compound mass = 47 parts: 5 parts: 44. Mix to form parts, and further use 5 parts of ESACURE ONE (oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone] manufactured by IGM Resins) as a photopolymerization initiator, and an organic solvent. The propylene glycol monomethyl ether was adjusted so that the solid content of the composition was 40%, to obtain an active energy ray-curable composition S1.
However, Example 1 is a reference example.

(Examples 2 to 20) <Preparation of active energy ray-curable compositions S2 to S20>
Active energy ray-curable compositions S2 to S20 were prepared in the same procedure as in Example 1 except that the raw materials and composition ratios shown in Table 1 were used. In Table 1, only the solid content component is shown. The abbreviations in the table are as follows.
However, Examples 2 to 4, 11, 16 to 20 are reference examples.
<Inorganic oxide particles>
ZrO ₂ dispersion (2): No silane compound treatment, particle solid content 30% by weight, average particle diameter 22 nm (Product name manufactured by Aitec Co., Ltd .: "Zirconeo-Ck")
TiO ₂ dispersion (2): No silane compound treatment, particle solid content 15% by weight, average particle diameter 36 nm, specific surface area 45 m ² / g Anatase-type titanium oxide spherical particles (Product name manufactured by CIK Nanotech Co., Ltd .: "NanoTeck TiO ₂ " )
ZnO dispersion: No silane compound treatment, particle solid content 15% by weight, average particle diameter 34 nm, specific surface area 30 m ² / g (Product name manufactured by CIK Nanotech Co., Ltd .: "NanoTeck ZnO")
<Pentaerythritol compound>
PET4A: Pentaerythritol tetraacrylate (manufactured by Toagosei Co., Ltd., product name: "Aronix M450")
DPHA: Dipentaerythritol hexaacrylate (manufactured by Sartmer, product name: "DPHA")
PET3A / PET4A = 70/30: Pentaerythritol triacrylate / pentaerythritol tetraacrylate = 70/30 (mass ratio) mixture (manufactured by Toagosei Co., Ltd., product name: "Aronix M306")
DPPA / DPHA = 60/40: Mixture of dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate = 60/40 (mass ratio) (manufactured by Toagosei Co., Ltd., product name: "Aronix M403")
<Epoxy acrylate>
EP1: Epoxy acrylate Diesel Ornex Co., Ltd. Product name EBECRYL860 Number of functional groups 4 Weight average molecular weight 1200

(Comparative Examples 1 to 10) <Preparation of active energy ray-curable compositions SS1 to SS10>
The active energy ray-curable compositions SS1 to SS8 were prepared in the same procedure as in Examples 1 to 20 except that the raw materials and composition ratios shown in Table 2 were used. Examples 9 and 10 were prepared by mixing in the same procedure as in Example 1 and then performing a dispersion treatment with a bead mill for 10 minutes.
The abbreviations in the table are as follows.
TiO ₂ pigment: Titanium oxide manufactured by TAYCA JR-403 Average particle size 250 nm
Al ₂ O ₃ dispersion: particle concentration 15% by weight, average particle diameter 31 nm, specific surface area 55 m ² / g (product name: "NanoCheck Al ₂ O ₃ ", manufactured by CIK Nanotech Co., Ltd.)
SiO ₂ dispersion: particle concentration 15% by weight, average particle diameter 25 nm, specific surface area 110 m ² / g (product name: "NanoCheck SiO2", manufactured by CIK Nanotech Co., Ltd.)
TMPTA: Trimethylolpropane triacrylate DTMPTA: Ditrimethylolpropane tetraacrylate <Urethane acrylate resin> manufactured by Shin-Nakamura Chemical Co., Ltd.
PU4: Urethane acrylate Kyoeisha Chemical Co., Ltd. Product name UF8001-G Number of functional groups 2 Weight average molecular weight 4500

(Example 21) <Preparation of laminated body R1>
The active energy ray-curable composition S1 is applied to a 125 μm-thick easy-adhesive polyester (PET) film (“Lumira UH13” manufactured by Toray Industries, Inc .: wettability index 44 dyn / cm) (hereinafter abbreviated as “base material 1”). , Using a microgravure coater (manufactured by Yasui Seiki Co., Ltd.), the film was coated so that the film thickness after drying was 1.5 μm, and then irradiated with ultraviolet rays of 500 mJ / cm ² with a high-pressure mercury lamp. An index matching layer was formed. Further, on the obtained index matching layer, a transparent conductive layer is laminated by a sputtering method so that the thickness of the ITO film is 30 nm, and then only the transparent conductive layer is etched (patterned) into stripes to form a laminated body. Obtained R1.
However, Example 21 is a reference example.

(Examples 22 to 40) <Preparation of laminated bodies R2 to R20>
Laminates R2 to R20 were prepared in the same procedure as in Example 21 except that the active energy ray-curable compositions S2 to S20 shown in Table 1 were used.
However, Examples 22 to 24, 31, and 36 to 40 are reference examples.

(Examples 41 to 47) <Preparation of laminated bodies R21 to R27>
Laminates R2 to R20 were obtained by applying S8 in the same procedure as in Example 21 except that a base material having the following wetting index was used. The base materials 2 to 8 are shown below.
Base material 2: Easy-adhesion-treated polyester (PET) film: Lumirror U34, manufactured by Toray Industries, Inc. (wetting index 38 dyn / cm)
Base material 3: Easy-adhesion-treated polyester (PET) film: Cosmo Shine A4300, manufactured by Toyobo Co., Ltd. (wetting index 58 dyn / cm)
Base material 4: Triacetyl cellulose film: Fujitac TD80UF, manufactured by FUJIFILM Corporation (wetting index 44dyn / cm)
Base material 5: Polycarbonate film: Pure Ace, manufactured by Teijin Limited, wettability index 44 dyn / cm by corona treatment)
Base material 6: Cycloolefin film: Zeonoa ZF16 (manufactured by Zeon Corporation: Wetting index 34 dyn / cm)
Base material 7: Cycloolefin film: Zeonoa ZF16 (manufactured by Zeon Corporation: Wetting index 55 dyn / cm)
Base material 8: Cycloolefin film: Zeonoa ZF16 (manufactured by Zeon Corporation: Wetting index 62din / cm)
The wetting index of the base material was adjusted by corona discharge treatment.

(Example 48) <Preparation of laminated body R28>
The active energy ray-curable composition S1 is dried on an easily adhesive-treated polyester (PET) film having a film thickness of 125 μm (“Lumilar UH13” manufactured by Toray Industries, Inc .: wettability index 44 dyn / cm) using a bar coater # 4. After coating so that the film thickness was 1.5 μm, an index matching layer was formed by irradiating with an ultraviolet ray of 500 mJ / cm ² with a high-pressure mercury lamp. Further, on the obtained index matching layer, the transparent conductive layer is laminated as a transparent conductive layer by a sputtering method so that the thickness of the ITO film is 30 nm, and then only the transparent conductive layer is patterned (etched) in a stripe shape to obtain the present invention. R28 was obtained.

In Table 3, "MG" indicates coating with a microgravure coater, and "B" indicates coating with a bar coater.

(Comparative Examples 11 to 20) <Preparation of laminated bodies RR1 to RR10>
Laminates RR1 to RR10 were prepared in the same procedure as in Example 21 except that the active energy ray-curable compositions S1 and SS1 to SS10 shown in Table 2 were used.

[Characteristic evaluation]
Using the active energy curable compositions S1 to S20 (Example) and SS1 to SS10 (Comparative Example), laminates R1 to R28 (Example), and RR1 to RR10 (Comparative Example) obtained above, the following Was evaluated. The evaluation results are shown in Tables 3 and 4.

<Stability of composition over time>
Compositions S1 to S20 (Examples) and SS1 to SS10 (Comparative Examples) were compared at 40 ° C. for 10 days before and after standing, and the rate of change in viscosity (thickening rate) and appearance of the composition were compared. The evaluation was made on the following five stages.
A: The rate of change in viscosity is less than 10%, and no precipitation is observed. (excellence)
B: The rate of change in viscosity is 10% or more and less than 20%, and no precipitation is observed. (Good)
C: The rate of change in viscosity is 20% or more and less than 50%, and some precipitation is observed. (Slightly bad)
D: Precipitation is observed in which the rate of change in viscosity is 50% or more and less than 100%. (Defective)
E: The composition is extremely thickened or has a large amount of precipitate. (Extremely bad)
Note that A and B are levels at which there is no problem in practical use.

<Appearance>
Each of the laminates R1 to R28 (Example) and RR1 to RR10 (Comparative Example) was cut into test pieces having a size of 100 mm × 100 mm, and the appearance was visually evaluated in the following five stages.
(Evaluation criteria)
A: Unevenness or defects cannot be visually confirmed in the laminated body. (excellence)
B: One or two irregularities or defects can be confirmed in the laminated body. (Good)
C: 3 to 10 irregularities or defects can be confirmed in the laminated body. (Slightly bad)
D: 11 or more irregularities or defects can be confirmed in the laminated body. (Defective)
E: There are many irregularities or defects in the laminated body, and the base material is exposed. (Extremely bad)
Note that A and B are levels at which there is no problem in practical use.

<Adhesiveness> (Base material / Index matching layer)
In the laminated bodies R1 to R28 (Example) and RR1 to RR10 (Comparative Example), after irradiating the laminated body with ultraviolet rays of 10500 mJ / cm ² and 14500 mJ / cm ² in an integrated light amount with a high-pressure mercury lamp, the ITO layer of the laminated body is formed. For the non-laminated portion, the adhesiveness between the substrate / index matching layers was evaluated by the adhesive cross-cut method in accordance with JIS K5600-5-6. The evaluations of 0 to 5 in the JIS standard are described by replacing each with A to F.
(Evaluation criteria)
A: The edges of the cut are completely smooth, and there is no peeling in the eyes of any grid. (excellence)
B: Small peeling of the laminate at the intersection of the cuts. Peeling less than 5% per unit area. (Good)
C: The laminate is peeled off along the edges of the cut and / or at the intersection.
Peeling of 5% or more and less than 15% per unit area. (Slightly bad)
D: The laminate has a large peeling partially or wholly along the edge of the cut.
And / or various parts of the eye are partially or wholly peeled off.
Peeling of 15% or more and less than 35% per unit area. (Defective)
E: The laminate has a large peeling along the edge of the cut, partially or entirely.
And / or some eyes are partially or completely peeled off.
Peeling less than 35% per unit area. (Badness between D and F)
F: Peeling of 35% or more per unit area. (Extremely bad)
Note that A and B are levels at which there is no problem in practical use.

<Adhesiveness> (between index matching layer / transparent electrode)
In the laminated bodies R1 to R28 (Example) and RR1 to RR10 (Comparative Example), the adhesiveness between the index matching layer / transparent electrode was evaluated by the same method as described above. The evaluation criteria were the same as above. Evaluations A and B are at a level where there is no problem in practical use.

<Transparency>
In the laminated bodies R1 to R28 (Example) and RR1 to RR10 (Comparative Example), after irradiating ultraviolet rays under the same conditions as above (10500 mJ / cm ² ), the portion of the laminated body in which the ITO layer is not laminated is transparent. The property was evaluated by its turbidity value (Haze value) using a Haze meter (manufactured by Suga Test Instruments Co., Ltd.).
(Evaluation criteria)
A: The Haze value is less than 1.0%. (excellence)
B: The Haze value is 1.0% or more and less than 1.5%. (Good)
C: Haze value is 1.5% or more and less than 2.0%. (Slightly bad)
D: The Haze value is 2.0% or more and less than 3.0%. (Defective)
E: The Haze value is 3.0% or more. (Extremely bad)
It should be noted that A and B are at a level where there is no problem in practical use.

<Scratch resistance>
After irradiating each of the laminates R1 to R28 (Example) and RR1 to RR10 (Comparative Example) with ultraviolet rays under the same conditions as above (10500 mJ / cm ² ), they were set in a Gakushin tester and made of steel wool (No. Using 0000), they were rubbed 10 times with a load of 250 g. The degree of scratches on the taken-out laminate was judged according to the following five-step visual evaluation.
(Evaluation criteria)
A: There are no scratches. (excellence)
B: Slightly scratched. (Good)
C: There are scratches, but the base material is not visible. (Slightly bad)
D: The cured film is partially peeled off due to scratches. (Defective)
E: The cured film is peeled off and the base material is exposed. (Extremely bad)
Note that A and B are levels at which there is no problem in practical use.

From the results of Tables 3 and 4, the compositions S1 to S20 (Examples) are excellent in coating suitability and storage stability, and the laminates R1 to R28 (Examples) are transparent, scratch resistant and adhesive. It was excellent because it was compatible with all of the above. On the other hand, the compositions SS1 to SS10 (Comparative Example) have poor storage stability, and the laminates RR1 to RR10 (Comparative Example) have adhesiveness between the base material and the index matching layer or transparent conductivity between the index matching layer and the index matching layer. The adhesiveness between the layers (ITO) was insufficient. Even when the adhesiveness was good, the transparency or scratch resistance was deteriorated.
However, S1 to S4, S11, S16 to S20, and R1 to R4, R11, and R16 to R20 are reference examples.

According to the present invention, the activity for forming an index matching layer which can maintain adhesiveness to a base material and a transparent conductive layer regardless of irradiation with a large amount of active energy rays, has excellent coating suitability, and has a good appearance. An energy ray-curable composition could be provided.

Claims (5)

An active energy ray-curable composition containing a metal oxide having an average particle diameter of 4 to 200 nm for forming an index matching layer on a substrate, which satisfies the following (1) to (4). A characteristic active energy ray-curable composition.
(1) The metal oxide contains zirconium oxide and titanium oxide and / or zinc oxide in a mass ratio of 99/1 to 65/35.
(2) The ratio of the average particle size of the metal oxide (zirconium oxide / titanium oxide or zirconium oxide / zinc oxide) is 1.0 / 0.3 to 1.0 / 1.8.
(3) Contains a pentaerythritol acrylate compound.
(4) At least one resin selected from the group consisting of urethane acrylate, polyester acrylate (excluding cardo resin), and epoxy acrylate having a weight average molecular weight of 1000 to 30,000 (however, the above pentaerythritol acrylate type). Contains compounds). The active energy ray-curable composition according to claim 1, wherein at least one selected from zirconium oxide, titanium oxide and zinc oxide is surface-treated with a silane compound. The active energy ray-curable composition according to claim 1 or 2, wherein the wettability index of the surface of the base material in contact with the index matching layer is 35 to 65 dyne / cm. The active energy ray-curable composition according to any one of claims 1 to 3, which is for gravure printing. A laminate having a base material, an index matching layer composed of the active energy ray-curable composition according to any one of claims 1 to 4, and a transparent electrode layer in this order.