TWI672338B - Active energy ray-curable composition and laminate using the same - Google Patents

Abstract

The present invention provides an active energy ray-curable composition for forming a refractive index matching layer. Even if the refractive index matching layer is excessively irradiated with active energy rays, the transparency and scratch resistance are good, and it can be maintained relative to the substrate. And the adhesion of the transparent conductive layer. An active energy ray hardening composition comprising a metal oxide and used to form a refractive index matching layer in a laminate having a refractive index matching layer and a transparent conductive layer on a substrate, the active energy ray hardening composition Objects are characterized by satisfying the following (1) to (4).

Description

Active energy ray curable composition and laminate using the same

The present invention relates to an active energy ray-curable composition and a laminate using the same.

Conventionally, a transparent conductive laminate in which a transparent conductive layer is provided on a substrate such as polyester is used for touch panel applications and the like. The transparent conductive layer is generally a thin film of a metal oxide such as indium tin oxide (ITO), and is laminated on a substrate by a sputtering method or a vacuum evaporation method. As the operation method of the touch screen, the resistance film type is the mainstream, but in recent years, the capacitance type has been rapidly expanded. A transparent conductive laminate used in a resistive film touch screen usually includes an unpatterned transparent conductive layer. On the other hand, in a capacitive touch screen, a transparent conductive laminate in which a patterned transparent conductive layer is laminated is generally used.

A transparent conductive laminate used in an electrostatic capacitance type touch screen is usually patterned by photolithoetching or the like. There are patterned portions and non-patterned portions of the transparent conductive layer in a plan view. In a capacitive touch screen using a transparent conductive layered patterned transparent conductive layered body as described above, the phenomenon of so-called "see-through" in which the pattern portion of the transparent conductive layer is visible becomes a problem, making it a display device. The quality is degraded. For example, Patent Literature 1, Patent Literature 2, and the like propose to suppress the see-through of the transparent conductive layer pattern. In addition, Patent Document 3 proposes a laminated body that has transparency and adhesiveness that is resistant to a large amount of active energy ray irradiation and transparent conductivity when a large number of laminated bodies having transparent conductivity are produced. Furthermore, Patent Document 4 proposes an index matching laminated body having improved internal stress and hardening shrinkage.

In recent years, depending on the application of the laminate, multilayering may be performed on one or both sides of the substrate, and a large amount of active energy rays may be irradiated during the formation of the respective layers or the patterning of the transparent conductive layer. In this case, although the technology of Patent Document 1 or Patent Document 2 exhibits the effect of suppressing the see-through of the transparent conductive layer pattern, when the refractive index matching layer receives a large amount of active energy rays, there is a problem with the base. The problem of lowering the adhesiveness of wood. In addition, if the layer structure is designed so that the accumulated light amount of the active energy rays does not become large in order to ensure the adhesion between the substrate and the refractive index matching layer, a problem arises that the layer structure of the laminate is limited. In addition, the technology of Patent Document 3 discloses a transparent conductive material and a transparent conductive material which has transparency and resistance to a large amount of active energy ray irradiation when it is produced, Laminated body. However, further improvement in adhesion is required. [Prior Art Literature]

[Patent Literature] [Patent Literature 1] Japanese Patent Laid-Open No. 2011-084075 [Patent Literature 2]: International Publication WO2012 / 176481 [Patent Literature 3]: Japanese Patent Laid-Open Publication No. 2017-35816 [Patent Literature 4] ]: Japanese Patent Laid-Open No. 2014-209333

[Problems to be Solved by the Invention] The present invention provides an active energy ray-curable composition for forming a refractive index matching layer. Regardless of the amount of active energy ray exposure, the transparency and scratch resistance of the refractive index matching layer are both. Good, and can maintain the adhesion to the substrate and the transparent conductive layer. [Technical means to solve the problem]

The present inventors have intensively studied the above problems, and as a result, have found that the problems are solved by using an active energy ray-curable composition described below, and the present invention has been completed.

That is, one embodiment of the present invention relates to an active energy ray-curable composition that includes a metal oxide and is used to form a laminate having a refractive index matching layer and a transparent conductive layer in this order on a substrate. The refractive index matching layer is characterized in that the active energy ray-curable composition satisfies the following (1) to (4). (1) The average particle diameter of the metal oxide is 4 nm to 200 nm, and zirconium oxide and titanium oxide and / or zinc oxide are contained in a mass ratio of 95/5 to 40/60. (2) 100% by mass of the solid content of the active energy ray-curable composition contains 10 to 80% by mass of a pentaerythritol acrylate-based compound having a molecular weight of less than 700. (3) an acrylate resin containing 6 or more (meth) acryl fluorene groups and a mass average molecular weight of 700 to 10,000, and the acrylate resin is a polyester acrylate and / or a urethane acrylate (4) A mass ratio of the acrylate resin to the pentaerythritol acrylate compound is 80/20 to 50/50.

Moreover, in one embodiment of the present invention, the specific surface area of the titanium oxide and / or zinc oxide may be 20 m ² / g to 160 m ² / g.

In addition, in an embodiment of the present invention, the use of the laminated body after irradiating an active energy ray of 6500 mJ / cm ² is used in accordance with an adhesion test according to Japanese Industrial Standards (JIS) K5600-5-6. The measured adhesion of the refractive index matching layer to the substrate may be less than 15% of a peeling area.

An embodiment of the present invention may further include an acrylate resin (excluding the pentaerythritol acrylate-based compound) having 6 or more (meth) acrylfluorenyl groups and having a mass average molecular weight of 700 to 10,000.

Moreover, another embodiment of this invention is related with the laminated body which has a refractive index matching layer as a hardened | cured material of the said active-energy-ray-curable composition, and a transparent conductive layer in order on a base material. [Effect of the invention]

According to the present invention, there can be provided an active energy ray-curable composition for forming a refractive index matching layer. Regardless of the amount of active energy ray exposure, the refractive index matching layer has good transparency and scratch resistance, and can Maintains adhesion to the substrate and transparent conductive layer.

Hereinafter, the embodiment of the present invention will be described in detail. However, the description of the constituent elements described below is an example (representative example) of the embodiment of the present invention, and the present invention is not limited to these contents as long as it does not exceed the gist thereof.

Hereinafter, each element which comprises this invention is demonstrated in detail.

An embodiment of the present invention is an active energy ray-curable composition that includes a metal oxide and is used to form a refractive index matching layer in a laminate having a refractive index matching layer and a transparent conductive layer in this order on a substrate. The active energy ray-curable composition is characterized by satisfying the following (1) and (2). (1) The average particle diameter of the metal oxide is 4 nm to 200 nm, and zirconium oxide and titanium oxide and / or zinc oxide are contained in a mass ratio of 99/1 to 30/70. (2) A pentaerythritol acrylate-based compound is contained in 100% by mass of the solid content of the active energy ray-curable composition, in an amount of 10% by mass to 80% by mass.

<Substrate> Examples of the substrate of the present invention include, but are not limited to, polyester films, triethylfluorene-based cellulose films, polyolefin films, cycloolefin-based films, acrylic films, polycarbonate-based films, and the like. . It is particularly preferable to use a polyester film and a polyethylene terephthalate (PET) film among them. The thickness of the substrate may be appropriately selected according to the intended use, and is suitably in a range of 20 μm to 300 μm, preferably in a range of 50 μm to 250 μm, and more preferably in a range of 50 μm to 200 μm.

The refractive index of the base material is preferably from 1.45 to 1.75, and more preferably from the viewpoint of greatly contributing to the visibility of the entire laminated body having the base material, the refractive index matching layer, and the transparent conductive layer in this order. 1.45 to 1.70.

The substrate may further include a layer including an organic substance and / or an inorganic substance on a surface thereof. As a specific example thereof, an easily-adhesive layer for improving adhesion with other layers may be mentioned, but is not limited thereto. Examples of the easily-adhesive layer include various layers formed by a corona discharge treatment, an ultraviolet (UV) -ozone treatment, a plasma treatment, a primer treatment, or the like, or a combination treatment. Among them, a substrate treated with a primer or a corona discharge is particularly preferred, and a substrate treated with a primer is more preferred.

<Refractive index matching layer> In the present invention, the "refractive index matching layer" refers to a layer that forms a laminate used in a display device such as a touch screen, and is intended to reduce a portion having a transparent conductive layer on a substrate. A layer provided between a base material such as a PET film and the transparent conductive layer with a difference in optical characteristics from a portion having no transparent conductive layer. Although not limited to the following, the film thickness of the refractive index matching layer is preferably 0.02 μm to 30 μm, and the refractive index is preferably 1.4 to 2.0.

<Active-energy-ray-curable composition> Hereinafter, the active-energy-ray-curable composition of the present invention for forming a refractive index matching layer will be described.

The active energy ray-curable composition refers to a composition containing a resin component that is hardened by irradiation of an active energy ray such as ultraviolet rays or electron beams through a crosslinking reaction or the like. After the application of the active energy ray-curable composition, the active energy ray is irradiated to harden to form a refractive index matching layer. Examples of the resin include ultraviolet curable resins and electron beam curable resins. Representative resins are preferable in terms of excellent mechanical film strength (scratch resistance, pencil hardness), and are cured by ultraviolet radiation. Examples include compounds having an acrylate group, such as pentaerythritol acrylate-based compounds, but are not limited thereto.

<Metal Oxide> The average particle diameter of the metal oxide contained in the active energy ray-curable composition of the present invention is 4 nm to 200 nm, and if it is within the above range, the transparency of the refractive index matching layer is excellent. It is more preferably 10 nm to 100 nm. In this specification, the average particle diameter of a metal oxide means the average particle diameter in the state dispersed in a composition, and is a D50 value in the particle size distribution measured by the dynamic light scattering method. The dynamic light scattering measurement can be performed using, for example, "Nanotrac UPA" manufactured by Nikkiso Co., Ltd. and the like.

The ratio of the average particle diameter of zirconia to titanium oxide and / or zinc oxide is preferably 1.0: 0.3 to 1.0: 1.8, and more preferably 1.0: 0.5 to 1.0: 1.5. When both titanium oxide and zinc oxide are used, it is preferable that the ratio of each average particle diameter to the average particle diameter of a zirconia is in the said range.

Regarding the mass ratio of zirconia to titanium oxide and / or zinc oxide, in order to effectively block active energy rays such as ultraviolet rays, it is preferable to contain zirconia / titanium oxide / zinc oxide at a mass ratio of 99/1 to 30/70. . It is more preferably 95/5 to 40/60. In addition, the solid content of the active energy ray-curable composition is preferably 100% by mass, and preferably contains zirconia, titanium oxide, and / or zinc oxide in a total amount of 10% to 80% by mass.

The primary particle diameter of the metal oxide is preferably 4 nm to 200 nm. Within this range, active energy rays such as ultraviolet rays can be blocked more effectively. The ratio of the primary particle diameter of zirconia to titanium oxide and / or zinc oxide is preferably 1.0: 10 to 1.0: 0.3, and more preferably 1.0: 5 to 1.0: 0.4. When both titanium oxide and zinc oxide are used, it is preferable that the ratio of each primary particle diameter to the primary particle diameter of a zirconia is in the said range.

In the present specification, the primary particle diameter of the metal oxide refers to a value obtained by measurement using a transmission electron microscope, and it is preferable to take an average of the measured values of 5 points or more.

The surface of the metal oxide may be treated with an organic substance or an inorganic substance. Titanium oxide is preferably a rutile crystal, and zinc oxide is preferably a hexagonal crystal. The particle shape of the metal oxide is not particularly limited, and is, for example, spherical, hollow, porous, rod-like, plate-like, fibrous, or random, and preferably spherical.

The specific surface area of the titanium oxide and zinc oxide is preferably 20 m ² / g to 160 m ² / g, and more preferably 30 m ² / g to 150 m ² / g. The specific surface area can be measured by a measurement method described in JIS Z 8830: 2001. When the specific surface area is within the above range, the transparency of the refractive index matching layer becomes good, and even when the active energy ray is irradiated in a large amount as a cumulative light amount, the adhesion to the substrate can be maintained well. .

In the present invention, the metal oxide is preferably a combination of zirconia and titanium oxide.

The true density of the titanium oxide and zinc oxide is preferably 3 to 6.5. The bulk density is preferably 0.20 g / cm ³ to 0.40 g / cm ³ .

In the following description, (meth) acrylate refers to a collective name of methacrylate and acrylate, and (meth) acrylic acid refers to a collective name of methacrylic acid and acrylic acid.

<Pentaerythritol acrylate compound> The active-energy-ray-curable composition of this invention contains 10 mass%-80 mass% of pentaerythritol acrylate compounds in 100 mass% of solid content. It is preferably 20% by mass to 70% by mass. The mass ratio of the total of the metal oxides to the pentaerythritol acrylate-based compound (metal oxide / pentaerythritol acrylate-based compound) is preferably contained at 90/10 to 15/85.

In this specification, the pentaerythritol acrylate compound refers to pentaerythritol triacrylate (molecular weight 298), pentaerythritol trimethacrylate (molecular weight 340), pentaerythritol tetraacrylate (molecular weight 352), pentaerythritol tetramethacrylate (molecular weight) 408), dipentaerythritol pentaacrylate (molecular weight 524), dipentaerythritol pentamethacrylate (molecular weight 594), dipentaerythritol hexaacrylate (molecular weight 578), dipentaerythritol hexamethacrylate (molecular weight 662), etc. have pentaerythritol structure Compounds having a (meth) acrylate structure and compounds having a polyether structure such as polyethylene oxide and polypropylene oxide between the pentaerythritol structure and the (meth) acrylate structure of these compounds, and having a molecular weight Less than 700 compounds. These pentaerythritol (meth) acrylate compounds may be used alone or in combination of two or more. Among the above, pentaerythritol triacrylate (molecular weight 298), pentaerythritol tetraacrylate (molecular weight 352), dipentaerythritol pentaacrylate (molecular weight 524), and dipentaerythritol hexaacrylate (molecular weight 578) are preferred.

In addition, pentaerythritol acrylate compounds having no hydroxyl group, such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate, are contained in pentaerythritol triacrylate, dipentaerythritol, diamine, and other raw materials that are used to obtain acrylic resin. In products such as pentaerythritol pentaacrylate. Therefore, the obtained resin composition becomes a mixture of an acrylate resin and a pentaerythritol acrylate-based compound.

<Acrylic Resin> The active energy ray-curable composition may further contain an acrylate resin (where the pentaerythritol (the pentaerythritol ( Except for meth) acrylates). The content of the acrylate resin is preferably 5 to 45% by mass, and more preferably 10 to 40% by mass, based on 100% by mass of the solid content of the composition. From the viewpoint of coating properties, the mass average molecular weight is more preferably 1,000 to 8,000. In addition, as the viscosity, a B-type viscometer is used, and preferably 500 mPa ･ s to 30,000 mPa ･ s at 60 ° C. As the resin, a polyfunctional (formaldehyde) such as a urethane acrylate, a polyepoxy acrylate, and a polyester acrylate can be preferably used from the viewpoints of coating film strength and abrasion (scratch) resistance. Based) acrylic resin. Among these, polyester acrylate and / or urethane acrylate is preferable.

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

<Polyepoxy Acrylate> Examples of the polyepoxy acrylate include (meth) acrylic acid esterifying a glycidyl group of an epoxy resin and having a functional group as a (meth) acrylate group. (Meth) acrylic acid adduct to bisphenol A epoxy resin, (meth) acrylic acid adduct to novolac epoxy resin, and the like.

<Urethane acrylate> Examples of the urethane acrylate include those obtained by reacting a polyisocyanate with a (meth) acrylate having a hydroxyl group; and a condition in which a polyol and a polyisocyanate have an excess of isocyanate groups. An isocyanate group-containing urethane prepolymer obtained by the following reaction, a product obtained by reacting with a (meth) acrylate having a hydroxyl group, and the like. Alternatively, it may be obtained by reacting a polyol with a polyisocyanate under conditions in which a hydroxyl group is excessive, and a urethane-containing urethane prepolymer that reacts with a (meth) acrylate having an isocyanate group.

A method for producing a urethane acrylate is shown below, but this is an example and is not limited to these methods. For example, urethane acrylates can be used to oxidize polyisocyanates and hydroxyl groups in the presence of a suitable urethanization catalyst and in an oxygen environment at 60 ° C to 100 ° C for 4 to 8 hours. (Meth) acrylate was obtained by stirring. Specific examples of the urethane catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, dibutyltin dilaurate, triethylamine, and 1,4-diazabicyclo [2.2.2] octane, 2,6,7-trimethyl-1,4-diazabicyclo [2.2.2] octane, etc. Among these specific examples, dibutyltin dilaurate and the like are particularly preferable.

Examples of the polyisocyanate include aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate, but are not limited to these polyisocyanates. Examples include 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate , Dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene diisocyanate, butane-1, 4-diisocyanate, hexamethylene diisocyanate, isopropylidene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane -1,4-diisocyanate, xylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, methyl ring Hexane diisocyanate, norbornane diisocyanate, m-tetramethylxylene diisocyanate, 4,4-diphenylmethane diisocyanate, bis-chloromethyl-diphenylmethane-diisocyanate, 2,6-di Isocyanate-benzyl chloride or dimeric diisocyanate obtained by converting the carboxyl group of a dimer acid into an isocyanate group, etc., but not It is limited to these polyisocyanates. These polyisocyanates may also form a trimer to form an isocyanurate ring structure. These polyisocyanates can be used alone or in combination of two or more. Among these, isocyanurate of toluene diisocyanate, isophorone diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, hexamethylene diisocyanate, and hexamethylene diisocyanate is preferred.

Examples of the hydroxyl-containing (meth) acrylate include trimethylolpropane di (meth) acrylate, trimethylolethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, Polyfunctional (meth) acrylates such as dipentaerythritol penta (meth) acrylate; 2-hydroxyethyl (meth) acrylate, -1-hydroxypropyl (meth) acrylate, -2 -Hydroxypropyl ester, 3-hydroxypropyl (meth) acrylate, -1-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxy (meth) acrylate Butyl ester, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylic acid Esters, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, ethyl-α- (hydroxymethyl) (meth) acrylate, monofunctional (meth) acrylic acid (Meth) acrylates such as glycerides; or (meth) acrylates containing the hydroxyl group, ε-caprolactone is subjected to ring-opening addition to obtain (meth) acrylates having a hydroxyl group at the terminal, Or for the hydroxyl-containing (methyl) Hydroxyl-containing (meth) acrylates such as alkylene oxide (meth) acrylates obtained by repeating addition of acrylates to alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, but not It is not limited to these (meth) acrylates. Among them, it is preferably selected from the group consisting of trimethylolpropane di (meth) acrylate, trimethylolethane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (methyl) At least one of acrylates.

<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 (meth) acrylate containing a carboxyl group or a hydroxyl group. Examples of the polybasic acid include aliphatic systems, alicyclic systems, and aromatic systems, and each of them can be used without particular limitation. For example, examples of the aliphatic polybasic acid include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, suberic acid, maleic acid, and chloromaleic acid. Acids, fumaric acid, dodecanedioic acid, pimelic acid, citraconic acid, glutaric acid, itaconic acid, succinic anhydride, maleic anhydride, etc. These aliphatic dicarboxylic acids and Its anhydrous. In addition, derivatives of succinic anhydride (methylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, butylsuccinic anhydride, isobutylsuccinic anhydride, hexylsuccinic anhydride, octylbutanedioic acid) Dianhydride, dodecenyl succinic anhydride, phenylsuccinic anhydride, etc.), derivatives of glutaric anhydride (glutaric anhydride, 3-allyl glutaric anhydride, 2,4-dimethylglutaric anhydride, 2,4-diethylglutaric anhydride, butylglutaric anhydride, hexylglutaric anhydride, etc.), maleic anhydride derivatives (2-methylmaleic anhydride, 2,3-dimethyl Maleic anhydride, butyl maleic anhydride, pentyl maleic anhydride, hexyl maleic anhydride, octyl maleic anhydride, decyl maleic anhydride, dodecyl maleic anhydride , 2,3-dichloromaleic anhydride, phenylmaleic anhydride, 2,3-diphenylmaleic anhydride, etc.) and other anhydrous derivatives.

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'-dimethylolheptane, 2-butyl-2-ethyl-1 , 3-propanediol, polyoxyethylene glycol (additional mole number is less than 10), polyoxypropylene glycol (additional mole number is less than 10), propylene glycol, 1,3-butanediol, 1,4-butanediol Glycol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, octanediol, butylethylpentanediol, 2-ethyl-1 , Aliphatic or alicyclic diols such as 3-hexanediol, cyclohexanediol, cyclohexanedimethanol, tricyclodecanedimethanol, cyclopentadienedimethanol, dimer diol;

1,3-bis (2-hydroxyethoxy) benzene, 1,2-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4'- Methylene diphenol, 4,4 '-(2-norbornene) diphenol, 4,4'-dihydroxybiphenol, o-dihydroxybenzene, m-dihydroxybenzene and p-dihydroxybenzene, 4,4 Aromatic diols such as' -isopropylidenephenol and addition bisphenols in which alkylene oxide is added to bisphenols are not limited to these polyols.

Examples of the bisphenol as a raw material of the addition-molded bisphenol include bisphenol A, bisphenol F, and the like, and examples of the raw material alkylene oxide include ethylene oxide and propylene oxide, but are not limited to these compounds.

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

Among the polyols, neopentyl glycol, 3-methyl-1,5-pentanediol, and 2,4-diethyl are preferred in terms of adhesion and heat resistance of the oligomer. -1,5-pentanediol, 2-methyl-1,8-octanediol, 3,3'-dimethylolheptane, 2-butyl-2-ethyl-1,3-propanediol, Polyols having two or more hydroxyl groups introduced into a branched alkane, such as butylethylpentanediol, 2-ethyl-1,3-hexanediol, and trimethylolpropane.

The polyester acrylate first obtains a polyester by polycondensing a polybasic acid and a polyhydric alcohol by a known method. At this time, the molecular weight, the terminal functional group, and the like are adjusted using the balance between the amount of carboxyl groups and the amount of hydroxyl groups.

In the case of "the amount of carboxyl groups contained in the polybasic acid> the amount of hydroxyl groups contained in the polyhydric alcohol", the terminal functional group is a carboxyl group, and the hydroxyl groups of the hydroxyl-containing (meth) acrylate and the terminal functional groups The group undergoes a condensation reaction to obtain a target polyester acrylate.

Examples of the hydroxy-containing (meth) acrylate include the same hydroxy-containing (meth) acrylate as described above. Among them, it is preferable to include a group selected from the group consisting of trimethylolpropane di (meth) acrylate and trimethylol. At least one of ethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate.

The polyester acrylate can also be obtained by reacting a polybasic acid anhydride with a hydroxyl group-containing (meth) acrylate, and further reacting the generated carboxyl group with an epoxy compound. Examples of the polybasic acid anhydride include 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 1,2,4,5 -Tetracarboxylic dianhydride such as pyromellitic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride and the like, and a polybasic acid anhydride having a fluorene structure or a biphenyl structure is preferred. Examples of the epoxy compound include biphenyl glycidyl ether, glycidyl methacrylate, and glycidyl ether of 4-hydroxybutyl acrylate. However, the epoxy compound is not limited to these epoxy compounds.

<Polymerization inhibitor> The acrylate resin having a mass average molecular weight of 700 to 10,000 may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone-based compounds, and hydroquinone and methylhydroquinone are preferred. The content is preferably 100 ppm to 500 ppm based on the acrylate resin.

As a commercial item of the said acrylate resin which has 6 or more (meth) acryl fluorenyl groups, and whose mass average molecular weight is 700-10000, the following commercial item can be illustrated. Made by East Asia Synthetic (Aronix): Aronix M-7100, Aronix M-8030, Aronix M-8060, chemical drug Sartomer (stock) : CN986NS, CN9010NS, made by Daicel Allnex (shares): Ebecryl 220, Ebecryl 1290, Ebecryl 1830, Shin Nakamura Chemical Industrial (stock) manufacturing: NK oligo (NK OLIGO) U6LPA, NK oligo (NK OLIGO) U10PA, NK oligo (NK OLIGO) U10HA, NK oligo (NK OLIGO) UA-33H, NK oligo (NK OLIGO) OLIGO) UA-53H, manufactured by Arakawa Chemical Industry Co., Ltd .: Beamset 371, Beamset 575, Beamset 577, manufactured by Genjo Industry: Art resin UN-3320HA, Art resin UN-3320HB, Art resin UN-3320HC, Art resin UN-3320HS, Art Art resin UN-9000H, Art resin UN-901T, Art resin UN-904, Art resin Art resin UN-905, Art resin UN-952, Art resin HDP, Art resin HDP-3, Art resin ) H61, manufactured by Japan Synthetic Chemical Industry Co., Ltd .: Violet UV-7600B, Violet UV-7610B, Violet UV-7620EA, Violet UV-7630B, Violet UV-1700B, Violet UV-6300B, Violet UV-7640B, Gongrong Made by social chemical (stock): UA-306H, UA-306T, UA-306I.

<Other monomers> The active energy ray-curable composition of the present invention may contain a (meth) acrylic acid ester monomer having 5 or less functions. For example, examples of the trifunctional to tetrafunctional (meth) acrylate monomers include di-trimethylolpropane tetraacrylate, trimethylolpropane tri (meth) acrylate, and tri (2-hydroxyethyl). Group) isocyanurate triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane triacrylate, but are not limited to these monomers.

Examples of the bifunctional (meth) acrylate monomer include trimethylolpropane di (meth) acrylate, dicyclopentyl dimethylene di (meth) acrylate, and 5-ethyl- 2- (2-hydroxy-1,1-dimethylethyl) -5- (hydroxymethyl) -1,3-dioxadi (meth) acrylate, neopentyl glycol di (methyl) Acrylate, 1,6-hexanediol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1, 9-nonanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene Glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, glycerol dimethacrylate, Hexanediol di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, and the like are not limited to these monomers. As preferred specific examples, trimethylolpropane tri (meth) acrylate, ethylene oxide (EO) modified trimethylol triacrylate, and propylene oxide can be listed. , PO) modified trimethylol tris (meth) acrylate and the like. These (meth) acrylic acid esters 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, isobutyl (meth) acrylate, N-stearyl (meth) acrylate, n-butoxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and the like are not limited to these monomers.

The blending amount of the metal oxide, pentaerythritol acrylate-based compound, and (meth) acrylic acid ester resin having 6 (meth) acrylfluorenyl groups and a mass average molecular weight of 700 to 10,000 is preferably 70. It is contained at a ratio of / 10/20 to 10/50/40, and is preferably contained at 70% by mass to 100% by mass of 100% by mass of the solid content of the composition. When the blending amount is within the above range, a refractive index matching layer excellent in abrasion resistance can be obtained.

<Organic solvent> The active-energy-ray-curable composition of this invention may contain an organic solvent as a liquid medium. As the organic solvent to be used, it is preferable to use it as a mixed solvent. Aromatic organic solvents such as toluene and xylene can be used; ketone organic solvents such as methyl ethyl ketone and methyl isobutyl ketone; ethyl acetate Esters, n-propyl acetate, isopropyl acetate, isobutyl acetate and other ester-based organic solvents; methanol, ethanol, n-propanol, isopropanol, n-butanol and other alcohol-based organic solvents; propylene glycol monomethyl ether and other glycols Known organic solvents such as ether-based organic solvents. It is particularly preferable to include 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, and ethylene glycol. Alcohol monoisopropyl ether, ethylene glycol dipropyl ether, ethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol dibutyl ether, ethylene glycol isoamyl ether, ethylene glycol monohexyl ether, ethyl alcohol Glycol mono 2-ethylhexyl ether, methoxyethoxy ethanol, ethylene glycol monoallyl ether, and other glycol ethers; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether Propylene glycol ethers such as ether and butoxypropanol; but not limited to these organic solvents. Among the organic solvents used in the active energy ray-curable composition of the present invention, methyl propylene glycol and 3-methoxy-1-butanol are preferred.

<Photopolymerization initiator> The active energy ray-curable composition may further include a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it has a function of initiating photopolymerization of a (meth) acrylfluorene-based vinyl group to form an active energy ray-cured film by photoexcitation. A monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, a fluorenylphosphine oxide compound, an aminocarbonyl compound, or the like is used.

Specifically, examples of the monocarbonyl compound include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4- (4-methylphenylthio) phenyl-ethanone, 3,3'-dimethyl-4-methoxybenzophenone, 4- (1, 3-propenyl-1,3-dimethyl-4-methoxy) benzophenone, 4- (1,3-propenyl-1,4,7,10,13-pentaoxo (Trialkyl) benzophenone, 3,3 ', 4,4'-tetrakis (third butylperoxycarbonyl) benzophenone, 4-benzylidene-N, N, N-trimethyl 1-propylamine hydrochloride, 4-benzylamino-N, N-dimethyl-N-2- (1-oxo-2-propenyloxyethyl) ammonium metaoxalate, 2- / 4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- Hydroxy-3- (3,4-dimethyl-9-oxo-9H-thiaxanthone-2-yloxy) -N, N, N-trimethyl-1-propylamine hydrochloride, benzene Formamidine methylene-3-methylnaphtho (1,2-d) thiazoline and the like are not limited to these compounds.

Examples of the dicarbonyl compound include 1,2,2-trimethyl-bicyclo [2.1.1] heptane-2,3-dione, benzamidine, 2-ethylanthraquinone, and 9,10-phenanthrenequinone. , Methyl α-oxophenylacetate, 4-phenylbenzidine, and the like, but are not limited to these compounds. Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropane-1-one and 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-1- Phenylpropane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-di-2-methyl-1-phenylpropane-1-one, 1-hydroxy-cyclohexylphenyl ketone , 2-hydroxy-2-methyl-1-styrylpropane-1-one polymer, 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-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) butane-1-one, 1-phenyl -1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2-morpholinyl-propionyl) -9-butyloxazole, etc., It is not limited to these compounds.

Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin n-butyl ether, but are not limited to these compounds. Examples of the fluorenylphosphine oxide compounds include 2,4,6-trimethylbenzylidenediphenylphosphine oxide and 4-n-propylphenyl-bis (2,6-dichlorobenzyl) oxide Phosphine and the like are not limited to these compounds.

Examples of the aminocarbonyl compound include methyl 4- (dimethoxyamino) benzoate, ethyl 4- (dimethylamino) benzoate, and 4- (dimethylamino) benzoate-2 -N-butoxyethyl ester, 4- (dimethylamino) isoamyl benzoate, 2- (dimethylamino) ethyl benzoate, 4,4'-bis-4-dimethyl Aminobenzophenone, 4,4'-bis-4-diethylaminobenzophenone, 2,5'-bis (4-diethylaminobenzylidene) cyclopentanone, etc., but It is not limited to these compounds. Examples of commercially available photopolymerization initiators include Omnirad 73 manufactured by IGM Resins, Omnirad 481, Omnirad 659, and Auman Omnirad 248, Omnirad 264, Omnirad 4817, Omnirad BDK, Omnirad TPO, Omnirad TPO-L, Omnirad 380, Omnipol 910, Omnipol BP, Omnipol 2702, Esacure One, Esacure Esacure 1001M, Esacure A198, Esacure KIP150 and so on.

The photopolymerization initiator is not limited to the compound, and may be any compound as long as it has the ability to initiate polymerization by photoexcitation. These photopolymerization initiators may be used singly or in combination of two or more kinds. The use amount of the photopolymerization initiator is not particularly limited, but is preferably 100% by mass relative to the solid content other than the metal oxide in the active energy ray-curable composition forming the refractive index matching layer in the present invention. , And used within the range of 1% to 20% by mass. In addition, as the sensitizer, a known organic amine or the like may be added. Furthermore, in addition to the initiator for radical polymerization, an initiator for cationic polymerization may be used in combination.

<Other combined resins> The active energy ray-curable composition in the present invention may also contain other polymer materials, and examples include but are not limited to chlorinated polypropylene resins, polyolefin resins, and ethylene-vinyl acetate copolymers. Resin, vinyl acetate resin, alkyd resin, polyvinyl chloride resin, rosin-based resin, rosin modified maleic acid resin, terpene resin, phenol modified terpene resin, ketone resin, cyclized rubber, chlorinated Rubber, butyral, petroleum resin, and modified resins of these resins. These resins can be used singly or in combination of two or more, and the content thereof is preferably 1 to 20% by mass based on 100% by mass of the resin solid content in the active energy ray-curable composition.

<Additives> The active energy ray-curable composition of the present invention may further include various additives within a range that does not impair the object or effect of the present invention. Specific examples include photocurable compounds other than pentaerythritol (meth) acrylate-based compounds and acrylic resins having 6 or more (meth) acrylfluorene groups and a mass average molecular weight of 700 to 10,000, and polymerization inhibition. Agents, photosensitizers, levelling agents, surfactants, antibacterial agents, anticaking agents, plasticizers, ultraviolet absorbers, infrared absorbers, antioxidants, silane coupling agents, conductive polymers, conductivity Surfactants, inorganic fillers, pigments, dyes, etc. are not limited to these additives.

<Production of active energy ray-curable composition> The active energy ray-curable composition of the present invention is not a problem as long as it can be uniformly stirred and mixed. For example, a predetermined blender, disperser, or homogenizer can be used to activate the composition. A metal oxide, a pentaerythritol-based compound, an acrylate resin, an organic solvent, and the like of the energy ray-curable composition are produced by uniformly stirring. For metal oxides such as zirconia, titanium oxide, and zinc oxide, three rollers and sanding can be used together with pentaerythritol acrylates, urethane acrylates, polyester acrylates and other acrylate resins, and organic solvents. A metal oxide that has been dispersed, such as a mill, a hammer mill, or the like, may be used by dispersing a commercially available organic solvent.

<Manufacture of a refractive index matching layer> Next, the manufacturing method of the refractive index matching layer which hardened the active-energy-ray-curable composition is demonstrated. A method for manufacturing the refractive index matching layer includes, for example, applying an active energy ray-curable composition to a substrate; and irradiating the active energy ray to harden the active energy ray-curable composition on the substrate. More specifically, it can be formed by coating the active energy ray-curable composition so that the film thickness after drying becomes preferably 0.02 μm to 30 μm, and more preferably 0.02 μm to 20 μm. After being applied to a substrate, a hardening treatment is performed.

As the coating method, a known method can be used, for example, a method using a rod or a wire bar, or a micro-gravure, a gravure, a mold, a curtain, a lip, a slit, or the like can be used. Various coating methods such as slot or rotation.

The hardening method can be performed by using a known technique such as irradiation of active energy rays such as ultraviolet rays, electron beams, and visible rays having a wavelength of 400 to 500 nm. As the line source (light source) of ultraviolet rays and visible rays with a wavelength of 400 nm 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, or a carbon arc lamp can be used. As the electron beam source, a thermionic radiation gun, an electrolytic radiation gun, or the like can be used. In terms of easy management in terms of steps, the cumulative light amount of the amount of active energy rays irradiated is preferably within a range of 50 mJ / cm ² to 1000 mJ / cm ² . When these active energy rays are irradiated, heat treatment using infrared rays, far infrared rays, hot air, and high-frequency heating can be used in combination.

The refractive index matching layer can be formed by coating an active energy ray-curable composition on a substrate, and then subjecting it to natural drying or forced drying, followed by hardening treatment. Alternatively, it can be naturally dried or forced dried after being coated and hardened. However, it is more preferable to perform the hardening treatment after natural drying or forced drying. In particular, in the case of hardening by an electron beam, in order to prevent a reduction in the strength of the coating film due to the hindrance of hardening caused by water or the residue of an organic solvent, it is more preferable to perform the hardening treatment after natural drying or forced drying. The timing of the hardening treatment may be simultaneous with or after the application.

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

<Transparent conductive layer> As a material of the transparent conductive layer, a known material used for electrodes of a touch screen can be used. Examples include, but are not limited to, metal oxides such as tin oxide, indium oxide, antimony oxide, zinc oxide, indium tin oxide (ITO), and antimony tin oxide (Antimony Tin Oxide (ATO)). Among these metal oxides, ITO is preferably used.

For example, from the viewpoint of ensuring good conductivity with a surface resistance value of 10 ³ Ω / □ or less, the thickness of the transparent conductive layer is preferably 10 nm or more, more preferably 15 nm or more, and particularly preferably 20 nm or more. On the other hand, if the thickness of the transparent conductive layer becomes too large, there may be a problem that the transparency decreases. Therefore, the upper limit of the thickness of the transparent conductive layer is preferably 60 nm or less, more preferably 50 nm or less. It is preferably 40 nm or less. The refractive index of the transparent conductive layer is preferably 1.81 or more, more preferably 1.85 or more, and even more preferably 1.90 or more. The upper limit of the refractive index of the transparent conductive layer is preferably 2.20 or less, and more preferably 2.10 or less.

The method for forming the transparent conductive layer is not particularly limited, and a conventionally known method can be used. Specifically, for example, a dry process such as a vacuum evaporation method, a sputtering method, or an ion plating method can be used. For the transparent conductive layer formed in the above manner, various patterns can be formed according to the application to which the transparent conductive film is applied. Furthermore, the patterned portion and the non-patterned portion are formed by patterning the transparent conductive layer. Examples of the shape of the pattern portion include a stripe shape and a lattice shape, but are not limited to these shapes. The patterning of the transparent conductive layer is usually performed by etching. For example, a photoresist method, a laser exposure method, or a printing method is used to form a patterned anti-etching film on the transparent conductive layer and then perform an etching process to pattern the transparent conductive layer. As the etching solution, conventionally known etching solutions can be used. For example, inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid, nitric acid, and phosphoric acid; organic acids such as acetic acid; a mixture of these acids;

The laminate of the present invention is only required to have a substrate, a refractive index matching layer as an active energy ray cured film, and a transparent conductive layer, and the substrate and the refractive index matching layer may be adjacent to each other. The structure of the other layers is arbitrary, and if necessary, a film or an adhesive layer having a different refractive index is provided on one side of the base material or the refractive index matching layer.

Some preferred examples of the laminate of the present invention are listed below, but the present invention is not limited to these examples. In the following configuration examples, the transparent conductive layer is a patterned transparent conductive layer. The layers other than the transparent conductive layer are not patterned. (I) substrate / index matching layer / transparent conductive layer (II) substrate / index matching layer / (M) / transparent conductive layer (III) (M) / substrate / index matching layer / transparent conductive layer (IV) (M) / Substrate / Refractive index matching layer / (M) / Transparent conductive layer (V) (M) / Refractive index matching layer / Substrate / Refractive index matching layer / Transparent conductive layer (VI) Refractive index In the matching layer / base material / refractive index matching layer / transparent conductive layer, (M) represents any of films or adhesive layers having different refractive indexes.

The films having different refractive indexes are films having functions other than those of the refractive index matching layer of the present invention. The formation method is not particularly limited, and it can be formed by a known method. For example, a dry coating method such as vapor deposition or sputtering, a method using a rod or a wire rod, or a wet coating method such as a micro gravure, a gravure, a mold, a curtain, a die lip, a slit, or a spin can be used. The materials to be used are not limited, and if necessary, one or more functions capable of imparting an information recording function, an anti-glare function, a Newton's rings prevention function, a sticking function, blocking at a specific wavelength, and hue correction to the laminated body can be used. Any material.

The laminated body of the present invention is irradiated with active energy rays during the manufacture of the refractive index matching layer or any layer during hardening or the patterning of the transparent conductive layer. In the manufacturing process of the laminate of the present invention, even if the total amount of active energy rays irradiated to the refractive index matching layer is 6500 mJ / cm ² or more in cumulative light amount, the substrate and the refractive index matching layer as an active energy ray hardened film It is also excellent in adhesion. It should be noted that the cumulative light amount refers to a total value of the light amount of the active energy ray, and may be a total amount of light irradiated at one time or a total amount of light irradiated in fractions. It should be noted that the present invention also includes an integrated light amount during hardening for forming a refractive index matching layer. The durability of the refractive index matching layer with respect to the accumulated light amount is preferably 6500 mJ / cm ² or more, and more preferably 8000 mJ / cm ² or more. It is more preferably 10,000 mJ / cm ² or more.

The adhesiveness of the laminate having the substrate, the refractive index matching layer, and the transparent conductive layer of the present invention is, as far as the adhesiveness is evaluated by the adhesive cross-cut method according to JIS K5600-5-6, The peeling area per unit area is less than 15%, and the transparency and scratch resistance are also excellent. The peeling area is preferably less than 10%, and more preferably less than 5%. Examples

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited to these examples. In addition, the part and% in this invention show a mass part and a mass% without a special note.

(Average particle diameter) The "Nanoc UPA" manufactured by Nikkiso Co., Ltd. was used to measure the dynamic light scattering method, and the value of D50 was used.

(Specific surface area) It calculated | required according to the method described in JIS Z 8830: 2001.

(Measurement Method of Acid Value) The measured acid value (mgKOH / g) was converted into a solid content in accordance with the potentiometric titration method of JIS K 0070.

(Mass average molecular weight) The mass average molecular weight is measured using a gel permeation chromatography (GPC) device (HLC-8220 manufactured by Tosoh Co., Ltd.), and is used for polystyrene. Calculate the molecular weight as a reference material. The measurement conditions are shown below. Tubing: Use the following tubing in series. TSKgel SuperAW2500 manufactured by Tosoh Co., Ltd. TSKgel SuperAW3000 manufactured by Tosoh Co., Ltd. TSKgel SuperAW4000 manufactured by Tosoh Co., Ltd. TSKgel guardcolumn SuperAWH detector manufactured by Tosoh Co., Ltd .: RI ( Differential refractive index meter) Measurement conditions: column temperature 40 ° C eluent: tetrahydrofuran flow rate: 1.0 mL / min

(Synthesis example 1) <urethane acrylate PU1> 150 parts of propyl acetate and 17 parts of hexamethylene diisocyanate were put into a flask equipped with a stirring blade, a thermometer, a reflux cooler, and a gas introduction tube, While blowing in air at a temperature of 90 ° C, a mixture of 60% by mass of dipentaerythritol pentaacrylate and 40% by mass of dipentaerythritol hexaacrylate (product name: "Aronix M403") (Production) 182 parts and 49 parts of propyl acetate were thoroughly mixed and added dropwise, and the stirring was maintained for 10 hours after the completion of the dropwise 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 = 1: 1. After confirming that the peak derived from the isocyanate group disappeared by IR spectrum, it was cooled to room temperature to obtain PU1, a mixture of urethane acrylate and dipentaerythritol hexaacrylate. Furthermore, PU1 has the following properties. <Properties of PU1>-The solid content mass ratio of the urethane acrylate and dipentaerythritol hexaacrylate in PU1 was 61:39. -The urethane acrylate in PU1 has 10 acryl groups.・ The mass average molecular weight of PU1 is 1900.

(Synthesis Example 2) <Carbamate Acrylate PU2> In addition to 22 parts of isophorone diisocyanate, 17 parts of hexamethylene diisocyanate used in Synthesis Example 1 were replaced and synthesized. In the same manner as in Example 1, a mixture PU2 of a urethane acrylate and dipentaerythritol hexaacrylate was obtained. Furthermore, PU2 has the following properties. <Properties of PU2>-The solid content mass ratio of the urethane acrylate and dipentaerythritol hexaacrylate in PU2 was 63:37. -The urethane acrylate in PU2 has 10 acryl groups.・ The mass average molecular weight of PU2 is 2100.

(Synthesis Example 3) <Urethane acrylate PU3> 22 parts of isophorone diisocyanate were used instead of 17 parts of hexamethylene diisocyanate used in Synthesis Example 1, and pentaerythritol triacrylate and 90 parts by weight of a mixture of pentaerythritol tetraacrylate with a mass ratio of 70:30 (product name: "Aronix M306" manufactured by Toa Kosei Co., Ltd.) was used in place of "Aronix (Aronix ) M403 "(mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate in a mass ratio of 60:40) 182 parts, except that the same operation as in Synthesis Example 1 was performed to obtain a urethane acrylate and A mixture of pentaerythritol triacrylate PU3. Furthermore, PU3 has the following properties. <Properties of PU3>-The solid content mass ratio of urethane acrylate and pentaerythritol triacrylate in PU3 was 73:27. -The urethane acrylate in PU3 has 6 acryl groups.・ The mass average molecular weight of PU3 is 1500.

(Synthesis Example 4) <Polyester Acrylate PE1> 80.0 parts of 3,3 ', 4,4'-biphenyltetracarboxylic acid was put into a four-necked flask equipped with a stirrer, a reflux cooler, a dry air introduction tube, and a thermometer. Dianhydride, 250.0 parts of pentaerythritol triacrylate with a hydroxyl value of 122 mgKOH / g (Pentaerythritol triacrylate manufactured by Nippon Kayaku Co., Ltd. Product name: KAYARAD PET-30, containing pentaerythritol tetraacrylic acid as a by-product Ester), 0.24 parts of methyl hydroquinone, and 217.8 parts of cyclohexanone, and the temperature was raised to 60 ° C. Then, 1.65 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and it stirred at 90 degreeC for 8 hours. It was confirmed by IR measurement of the reactant that the peak of the acid anhydride group, that is, peaks around 1780 cm ^-1 and 1850 cm ^-1 disappeared, and then the reaction was cooled to stop the reaction. The acid value of the reactant was measured at this time point, and it was 94 mgKOH / g. Thereafter, 78.3 parts of glycidyl methacrylate and 54.0 parts of cyclohexanone were added, and then 2.65 parts of dimethylbenzylamine was added as a catalyst, and the mixture was stirred at 100 ° C for 6 hours. The reaction was periodically measured while continuing the reaction. When the acid value of the product becomes 5.0 mgKOH / g or less, it is cooled to room temperature and the reaction is stopped. The obtained resin varnish was light yellow and transparent, had a solid content of 60%, and the final acid value was 3.0 mgKOH / g. Conversion from the acid value yielded a mixture PE1 of polyester acrylate and pentaerythritol tetraacrylate. <Properties of PE1>-The solid content mass ratio of polyester acrylate and pentaerythritol tetraacrylate in PE1 was 76:24.・ The polyester acrylate in PE1 has 8 acryl groups.・ The mass average molecular weight of PE1 is 3500.

(Synthesis Example 5) <Polyester Acrylate PE2> 80.0 parts of 3,3 ', 4,4'-biphenyltetracarboxylic acid was put into a four-necked flask equipped with a stirrer, a reflux cooler, a dry air introduction tube, and a thermometer. Dianhydride, 359.0 parts of dipentaerythritol pentaacrylate with a hydroxyl value of 85 mgKOH / g (manufactured by Shin Nakamura Chemical Industry Co., Ltd., dipentaerythritol pentaacrylate product name: A-9570W, as a by-product also includes dipentaerythritol hexaacrylic acid Ester), 0.29 parts of methyl hydroquinone, and 290.1 parts of cyclohexanone, and the temperature was raised to 60 ° C. Then, 2.19 parts of 1,8-diazabicyclo [5.4.0] -7-undecene was added as a catalyst, and it stirred at 90 degreeC for 8 hours. It was confirmed by IR measurement of the reactant that the peak of the acid anhydride group, that is, peaks around 1780 cm ^-1 and 1850 cm ^-1 disappeared, and then the reaction was cooled to stop the reaction. The acid value of the reactant was measured at this time point, and it was 74 mgKOH / g. Thereafter, 78.3 parts of glycidyl methacrylate and 48.7 parts of cyclohexanone were added, followed by 3.53 parts of dimethylbenzylamine as a catalyst, and the mixture was stirred at 100 ° C for 6 hours. The reaction was periodically measured while continuing the reaction. When the acid value of the product becomes 5.0 mgKOH / g or less, it is cooled to room temperature and the reaction is stopped. The obtained resin varnish was light yellow and transparent, had a solid content of 60%, and the final acid value was 3.0 mgKOH / g. Converted from the acid value, a mixture PE2 of polyester acrylate and dipentaerythritol hexaacrylate was obtained. <Properties of PE2>-The solid content mass ratio of polyester acrylate and dipentaerythritol hexaacrylate in PE2 was 69:31.・ The polyester acrylate in PE2 has 12 acryl groups.・ The mass average molecular weight of PE2 is 4000.

(Comparative Synthesis Example 1) <Urethane acrylate PU4> 67 parts of isophorone diisocyanate (NOC group: 2) were used instead of 17 parts of hexamethylene diisocyanate used in Synthesis Example 1 139 parts by weight of 2-hydroxyethyl acrylate was used instead of 182 parts of "Aronix M403" (a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate) used in Synthesis Example 1, except that Other than that, the same operation as in Synthesis Example 3 was performed to obtain a urethane acrylate PU4. Moreover, the molar ratio of the isocyanate group derived from isophorone diisocyanate to the hydroxyl group derived from 2-hydroxyethyl acrylate is isocyanate group: hydroxyl group (derived from 2-hydroxyethyl acrylate) = 1: 1 . The properties of PU4 are shown below. <Properties of PU4>-PU4 does not contain pentaerythritol acrylate compounds.・ PU4 has 2 acryl groups.・ The mass average molecular weight of PU4 is 1,000.

In this specification, Examples 5 to 9 and Examples 15 to 16 are reference examples (Example 1) <Production of active energy ray-curable composition S1> As the metal oxide, 47 based on the solid content of ZrO _{2 was} used. Parts of ZrO ₂ dispersion (1): a particle concentration of 30% by mass, an average particle size of 4 nm (product name manufactured by Sakai Chemical Co., Ltd .: "SZR-K"), and 5 parts of TiO as a solid content of TiO _{2 2} Dispersion (1): The particle concentration is 15% by mass, the average particle size is 36 nm, and the specific surface area is 45 m ² / g. Rutile titanium oxide spherical particles (CIK NanoTeck) Product name: "NanoTeck TiO ₂ "), and 44 parts of pentaerythritol tetraacrylate as a pentaerythritol acrylate-based compound (product name of Toa Sangyo Co., Ltd .: "Aronix M450") were mixed, and further added as light Oligomeric [2-hydroxy-2-methyl-1- [4- (1-methylvinyl)] made of 4 parts of ESACURE ONE (IGM Resins) as a polymerization initiator Phenyl] acetone]), and added as organic by adjusting the solid content to 40% Agent is propylene glycol monomethyl ether, to obtain an active energy ray curable composition S1.

(Examples 2 to 20) <Production of active energy ray-curable composition S2 to active energy ray-curable composition S20> The same materials as in Example 1 were used except that the raw materials and composition ratios described in Table 1 were used. The active-energy-ray-curable composition S2 to the active-energy-ray-curable composition S20 are sequentially prepared. The abbreviations in Table 1 are shown below. ZrO ₂ dispersion (2): particle concentration is 30% by mass, average particle size is 19 nm, and primary particle size is 10 nm or less (Product name of "ITEC" company: "Zirconeo-Ck") TiO ₂ dispersion (2): particle concentration of 20% by mass, average particle size of 13 nm, specific surface area of 120 m ² / g, rutile titanium oxide (product name manufactured by Niwa Catalyst Co., Ltd .: "Optolake ) 6320Z ") ZnO dispersion: particle concentration is 15% by mass, average particle size is 34 nm, bulk density is 0.36 g / cm ^3, specific surface area is 30 m ² / g (CIK NanoTeck) product name:" NanoTeck ZnO ") PET4A: Pentaerythritol tetraacrylate (manufactured by Toa Kosei Co., Ltd., product name:" Aronix M450 ") DPHA: dipentaerythritol hexaacrylate (Sartomer) Manufactured, product name: "DPHA") PET3A / PET4A = 70/30: Pentaerythritol triacrylate / Pentaerythritol tetraacrylate = 70/30 mixture (manufactured by East Asia Synthesis Co., Ltd., product name: "Aronix" M306 ") DPPA / DPHA = 60/4 0: A mixture of dipentaerythritol pentaacrylate / dipentaerythritol hexaacrylate = 60/40 (manufactured by Toa Kosei Co., Ltd., product name: "Aronix M403")

(Example 21) <Preparation of laminated body R1> An active energy ray-curable composition S1 was applied to a 125 μm-thick, easily-adhesive polymer using a bar coater so that the film thickness after drying became 1.5 μm. After the polyester (PET) film ("Lumirror UH13" manufactured by Toray Co., Ltd.) was applied, 500 mJ / cm ² of ultraviolet light was irradiated with a high-pressure mercury lamp to form a refractive index matching layer. Furthermore, on the obtained refractive index matching layer, after laminating by a sputtering method so that the thickness of the ITO film as a transparent conductive layer became 30 nm, only the transparent conductive layer was patterned (etched) to form Stripe shape, to obtain the laminate R1 of the present invention.

(Examples 22 to 40) <Preparation of Laminated Body R2 to Laminated Body R20> Except that the active energy ray curable composition S2 to the active energy ray curable composition S20 described in Table 1 were used, the same procedures as in the examples were used. In the same order as 21, a laminated body R2 to a laminated body R20 were produced.

(Comparative example 1 to comparative example 10) <Production of active energy ray curable composition SS1 to active energy ray curable composition SS10> The same materials as in Example 1 were used except that the raw materials and composition ratios shown in Table 2 were used. The active energy ray-curable composition SS1 to the active energy ray-curable composition SS10 were sequentially prepared. The abbreviations in Table 2 are shown below. Al ₂ O ₃ dispersion: particle concentration is 15% by mass, average particle size is 31 nm, specific surface area is 55 m ² / g (product name: "NanoTeck" Al ₂ O ₃ ", CIK NanoTeck (Manufactured by the company) SiO ₂ dispersion: particle concentration is 15% by mass, average particle size is 25 nm, specific surface area is 110 m ² / g (product name: "NanoTeck SiO ₂ ", CIK Nateck (Manufactured by CIK NanoTeck) TMPTA: trimethylolpropane triacrylate manufactured by Shin Nakamura Chemical Co., Ltd. DTMPTA: di-trimethylolpropane tetraacrylate manufactured by Shin Nakamura Chemical Co., Ltd.

(Comparative Example 11 to Comparative Example 20) <Preparation of Laminate RR1 to Laminate RR10> Except that the active energy ray-curable composition SS1 to the active energy ray-curable composition SS10 described in Table 2 were used, the examples were the same as the examples. In the same order as 21, a laminated body RR1 to a laminated body RR10 were produced.

[Evaluation] The active energy ray curable composition S1 to the active energy ray curable composition S20 (Example) and the active energy ray curable composition SS1 to the active energy ray curable composition SS10 (Comparative) Example), laminated body R1 to laminated body R20 (example), laminated body RR1 to laminated body RR10 (comparative example), and the following evaluations were performed. The evaluation results are shown in Tables 3 and 4.

<Adhesiveness> (Substrate / Refractive Index Matching Layer) In the laminated body R1 to laminated body R20 (Example), laminated body RR1 to laminated body RR10 (comparative example), a high-pressure mercury lamp was irradiated with a cumulative light amount of 6,500. After ultraviolet rays of mJ / cm ² , 10500 mJ / cm ² , 14500 mJ / cm ² , the substrate / refraction is determined by the adhesive cross-cut method according to JIS K5600-5-6 for the non-laminated ITO layer of the laminate. The adhesion between layers was evaluated by rate matching. In addition, the evaluation of 0 to 5 in the JIS standard is replaced by A to F, respectively. <Evaluation Criteria> A: The edge of the cut was completely smooth, and no peeling occurred in any of the grid holes. B: The laminate at the intersection of the cuts has small peeling. Exfoliation is less than 5% per unit area. C: The laminate is peeled off along the edge of the cut and / or at the intersection. Exfoliation per unit area is 5% or more and less than 15%. D: The laminated body locally or comprehensively exfoliates along the edges of the cuts, and / or many parts of the holes exfoliate locally or comprehensively. The peeling per unit area is 15% or more and less than 35%. E: The laminated body is locally or comprehensively exfoliated along the edge of the incision, and / or the holes in several locations are locally or fully exfoliated. Exfoliation is less than 35% per unit area. F: Peeling per unit area is 35% or more. Furthermore, A and B are practically problem-free levels.

<Adhesiveness> (between refractive index matching layer / transparent electrode) In the laminated body R1 to laminated body R20 (Example), laminated body RR1 to laminated body RR10 (comparative example), a high-pressure mercury lamp was irradiated with the cumulative light amount as: After 6500 mJ / cm ² , 10500 mJ / cm ² , and 14500 mJ / cm ² ultraviolet rays, the refractive index of the part of the laminated body without the ITO layer was matched according to JIS K5600-5-6 by the adhesive cross cutting method. The adhesion between the layers / transparent electrodes was evaluated. The evaluation criteria are as described above.

<Transparency (haze value)> In the laminated body R1 to laminated body R20 (Example), the laminated body RR1 to laminated body RR10 (comparative example), regarding the part of the laminated body where the ITO layer is not laminated, the transparency ( Haze value), and the haze was measured using a haze meter (manufactured by Suga Test Machine Co., Ltd.). A: The haze value is less than 1.0%. B: The haze value is 1.0% or more and less than 1.5%. C: The haze value is 1.5% or more and less than 2.0%. D: The haze value is 2.0% or more and less than 3.0%. E: The haze value is 3.0% or more. Furthermore, A and B are practically problem-free levels.

<Scratch resistance> Laminates R1 to R20 (Examples) and Laminates RR1 to RR10 (Comparative Examples) were respectively set on a school vibration test machine, and steel wool No. 0000 was used to load 250 g of scrape Rub 10 times. About the removed laminated body, the damage was judged according to the following 5 stages of visual evaluation. A: No scratch at all. B: Slight scratches. C: Although scratched, the substrate was not seen. D: There are scratches, and part of the cured film is peeled off. E: The cured film is peeled and the base material is exposed. Furthermore, A and B are practically problem-free levels.

From the results of Tables 3 and 4, it was found that the laminates R1 to R20 (Examples) are excellent in balance in transparency, abrasion resistance, and adhesion, and are excellent. Moreover, even if a metal oxide is contained in the refractive index matching layer as an active energy ray hardened film, transparency and adhesiveness are well balanced and excellent.

In contrast, the adhesion between the polyester substrate of the laminate RR1 to the laminate RR10 (comparative example) and the refractive index matching layer as the active energy ray cured film, and the refractive index matching layer as the active energy ray cured film is transparent. The adhesiveness of the conductive layer is generally insufficient. In addition, it was found that when the adhesiveness was good, the transparency or scratch resistance deteriorated.

According to the present invention, it is possible to provide an active energy ray-curable composition for forming a refractive index matching layer. Even if the refractive index matching layer is excessively irradiated with active energy rays, the transparency and scratch resistance are good, and the relative resistance Adhesion to substrate and transparent conductive layer.

[Table 1] [Table 2] [table 3] [Table 4]

no.

no

Claims (4)

An active energy ray-curable composition, which comprises a metal oxide and is used to form a refractive index matching layer in a laminate having a refractive index matching layer and a transparent conductive layer in this order on the substrate. The energy ray hardening composition is characterized by satisfying the following (1) to (4): (1) The average particle diameter of the metal oxide is 4 nm to 200 nm, and it contains oxidation at a mass ratio of 95/5 to 40/60 Zirconium and titanium oxide and / or zinc oxide; (2) 100% by mass of the solid content of the active energy ray-curable composition, containing 10% to 80% by mass of a pentaerythritol acrylate compound having a molecular weight of less than 700; ( 3) containing an acrylate resin having 6 or more (meth) acrylfluorene groups and a mass average molecular weight of 700 to 10,000, and the acrylate resin is a polyester acrylate and / or a urethane acrylate; (4) The mass ratio of the acrylate resin and the pentaerythritol acrylate compound is 80/20 to 50/50. The active energy ray-curable composition according to item 1 of the scope of application, wherein the specific surface area of the titanium oxide and / or the zinc oxide is 20 m ² / g to 160 m ² / g. The active energy ray-curable composition according to claim 1 or claim 2, wherein the use of the laminate after irradiation with an active energy ray of 6500 mJ / cm ² is in accordance with Japanese Industrial Standard K5600-5- The adhesion of the refractive index matching layer to the substrate measured in the adhesion test of 6 is less than 15% of the peeling area. A laminated body having a refractive index matching layer as a cured product of the active energy ray-curable composition according to any one of claims 1 to 3 on a substrate, and a transparent conductive material in this order. Floor.