JP2017211512A - Laminate including high refractive index pattern, optical element using the same, and method for forming high refractive index pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate including a high refractive index pattern that is inexpensive and excellent in reproducibility obtained through a simple process, an optical element using the laminate, and a method for forming a high refractive index pattern.SOLUTION: The laminate comprises: a substrate; a laser light absorbing layer formed on the substrate and formed of a composition comprising a compound having absorption in an emission wavelength region of laser light; and a high refractive index pattern formation layer formed on the laser light absorbing layer, which comprises a cured film of a coating liquid of a composition for forming a high refractive index pattern, the composition containing metal oxide nanoparticles surface-modified with a compound having at least a photopolymerizable reactive group. The composition for forming a high refractive index pattern contains the metal oxide nanoparticles by 25 wt.% or more in a solid content. The laser light absorbing layer has a film thickness of 500 nm or more and 50 μm or less. The high refractive index pattern formation layer has a film thickness of 50 nm or more and 5 μm or less.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a laminate including a high refractive index pattern, an optical element using the same, and a high refractive index pattern forming method.

  The high refractive index pattern provided on the substrate is used for optical members such as light diffusing members, optical wiring members, and diffraction gratings, holograms, and the like.

  For example, holograms are used for covers such as books and magazines, displays such as POPs, and gifts because of their excellent design and decoration effects. Further, since it can be said that the hologram is equivalent to the recording of information in submicron units, it is also used for forgery prevention marks such as securities and credit cards.

  In particular, volume phase holograms can modulate the phase without absorbing the light beam passing through the image by forming spatial interference fringes with different refractive indexes in the hologram recording medium instead of optical absorption. Therefore, in recent years, in addition to display applications, they are also used in hologram optical elements (HOE) represented by head-up displays (HUD) mounted on automobiles.

  When producing these volume phase holograms, the coating film in which two or more types of photosensitive resins having different refractive indexes are mixed is irradiated with laser, and the refractive index varies within the coating film due to the intensity of the laser interference light. Stripes are formed to obtain a hologram structure (Patent Document 1).

  However, there are many cases where a process such as development or heat treatment is necessary, and there are many manufacturing processes, so that there is a problem that the reproducibility of the pattern is lacking.

JP 2000-47552 A

  An object of the present invention is to provide a laminate including a high refractive index pattern with low cost and excellent reproducibility, an optical element using the same, and a method for forming a high refractive index pattern by a simple process.

  The present invention comprises a substrate and a composition comprising a compound having absorption in the laser light emission wavelength region, and comprises a laser light absorption layer formed on the substrate and a compound having at least a photopolymerizable reactive group. It consists of a cured film of a coating solution of a composition for forming a high refractive index pattern containing surface-modified metal oxide nanoparticles, and is provided with a high refractive index pattern forming layer formed on a laser light absorbing layer, and has high refraction The composition for forming a refractive index pattern contains metal oxide nanoparticles in a solid content of 25 wt% or more, the thickness of the laser light absorption layer is from 500 nm to 50 μm, and the thickness of the high refractive index pattern forming layer is 50 nm. The laminate is characterized by having a thickness of 5 μm or less.

  The metal oxide constituting the metal oxide nanoparticles may be any of titanium oxide, zirconium oxide, zinc oxide, and tin oxide.

  Moreover, the particle size of the metal oxide nanoparticles may be 1 nm or more and 100 nm or less.

  According to the present invention, a first photosensitive layer made of a composition containing a compound having an absorption in the emission wavelength region of laser light is formed on a substrate, and the first photosensitive layer is irradiated with ultraviolet rays to emit laser light. A step of forming an absorption layer and a second photosensitive layer comprising a composition for forming a high refractive index pattern comprising metal oxide nanoparticles surface-modified with a compound having at least a photopolymerizable reactive group. And forming a high refractive index pattern forming layer by irradiating the second photosensitive layer with ultraviolet rays, irradiating the high refractive index pattern forming layer with laser light according to a predetermined pattern, And a step of forming a high refractive index pattern, wherein the composition for forming a high refractive index pattern contains metal oxide nanoparticles in a solid content of 25 wt% or more, and the thickness of the laser light absorption layer is from 500 nm to 50 μm. , One, wherein the thickness of the high refractive index pattern forming layer is 50nm or more 5μm or less, a high refractive index pattern forming method.

  Moreover, this invention is an optical element provided with the laminated body containing said high refractive index pattern.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body containing the high refractive index pattern excellent in reproducibility, the optical element using the same, and the high refractive index pattern formation method are realizable by a simple process.

It is a figure which shows the model of the cross section of the state before forming the high refractive index pattern in the laminated body which concerns on one Example of this invention. It is a schematic diagram of the laminated body which concerns on one Example of this invention.

  The present inventor has formed a high refractive index pattern including a laser light absorption layer containing a compound having absorption in the emission wavelength region of laser light and metal oxide nanoparticles surface-modified with a compound having a photopolymerizable reactive group A method of forming a high refractive index pattern in a simple process without using a mold or the like by laminating a high refractive index pattern forming layer containing a composition for irradiation and irradiating an arbitrary pattern using a laser beam And found the present invention.

  By the laser irradiation, the compound having absorption in the emission wavelength region of the laser light of the laser light absorption layer absorbs the laser light, whereby the metal oxide nanoparticles of the high refractive index pattern forming layer are heated. Moreover, the metal oxide nanoparticles of the high refractive index pattern forming layer are heated by laser irradiation. As a result, the first region irradiated with the laser of the high refractive index pattern forming layer becomes dense, and only the first region has a high refractive index. As a result, a refractive index difference is generated between the first region irradiated with the laser and the second region not irradiated with the laser, so that a high refractive index pattern is formed.

  Hereinafter, a laminate including a high refractive index pattern according to this embodiment will be described with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view showing an example of a laminated body before a high refractive index pattern according to this embodiment is formed. As shown in FIG. 1, the laminate 10 includes a base material layer 11, a laser light absorption layer 12 formed on one surface of the base material layer 11, and a high refractive index pattern forming layer 13. The laser light absorption layer 12 is formed by irradiating a coating film containing a compound having absorption in the emission wavelength region of laser light with ultraviolet rays. The high refractive index pattern forming layer 13 is formed by irradiating the coating film of the composition for forming a high refractive index pattern containing metal oxide nanoparticles surface-modified with a compound having a photopolymerizable reactive group with ultraviolet rays. It is formed.

  FIG. 2 is a schematic cross-sectional view showing a state in which a high refractive index pattern is formed on the laminate shown in FIG. As shown in FIG. 2, the first region 14 irradiated with the laser and the second region 15 not irradiated with the laser are formed in the high refractive index pattern forming layer 13 of the stacked body 10.

  That is, by irradiating the laser beam to the high refractive index pattern forming layer 13 laminated on the laser light absorption layer 12, only the laser irradiated portion is heated, and as a result, the first region 14 irradiated with the laser is heated. And a second region 15 which is not irradiated with a laser, a refractive index difference is generated, and a high refractive index pattern is formed.

  Hereinafter, the composition for forming a laser light absorption layer and the composition for forming a high refractive index pattern according to this embodiment will be described.

  First, the composition for forming a laser light absorption layer will be described. The composition for forming a laser light absorption layer contains at least a compound having absorption in the emission wavelength region of laser light, a photopolymerizable compound, and a photopolymerization initiator. Moreover, you may contain a solvent etc. as needed.

[Compound having absorption in the emission wavelength region of laser light]
The composition for forming a laser light absorption layer contains a compound having absorption in the emission wavelength region of laser light. Examples of the compound having absorption in the laser light emission wavelength region include metal nanoparticles, pigments, and dyes. These compounds can be used alone or in combination of two or more.

  Although it does not specifically limit as a metal nanoparticle, A metal oxide, boride, etc. are mentioned. Moreover, in order to improve the dispersibility of the nanoparticle in a solvent, what carried out the appropriate surface treatment on the nanoparticle surface can also be used.

  The metal constituting the metal nanoparticles is not particularly limited as long as it has absorption in the emission wavelength region of the laser beam, and examples thereof include gold, silver, tin, and lanthanum.

Commercially available metal nanoparticles include: Ishihara Sangyo: SN-100P (ATO), FS-10P (ATO), SN-102P (ATO), FS-12P (ATO), Mitsubishi Materials: T-1 ( ATO), S-1200 (tin oxide), Mitsui Mining & Smelting manufactured: Pastran (ATO), manufactured by CI Kasei Co.: Nanotech SnO _2, NANOTEC SiO _2, catalysts & Chemicals Ltd.: TL-20 (ATO), TL-30 (ATO), Sumitomo Metal Mining: KHF-7AH (lanthanum hexaboride), Sigma-Aldrich: Silver nanoparticle dispersion, gold nanoparticles, Shikoku Keiki Kogyo: silver nanoparticles, gold nanoparticles, etc.

  Commercially available pigments and dyes are manufactured by Orient Chemical Industries: BONASORB UA-3701, BONASORB UA-3911, VALIFAST BLUE 1603, VALIFAST GREEN 1501, manufactured by Dainichi Seika: Chromofine PB-15, PB-15: 2, PB-15: 3, PB-15: 4, Sanyo Dye: SF GREEN GC6036, SF BLUE GB1377, Sumitomo Chemtex: SUMIPLAST BLUE OR, SUMIPLAST Yellow FL7G, and the like.

[Photopolymerizable compound]
The composition for forming a laser light absorption layer according to this embodiment contains a photopolymerizable compound. The photopolymerizable compound will be described later.

(Photopolymerization initiator)
The composition for forming a laser light absorption layer according to this embodiment includes a photopolymerization initiator. The photopolymerization initiator will be described later.

〔solvent〕
The composition for forming a laser light absorption layer according to this embodiment may further contain a solvent. The solvent will be described later.

[Optional substances]
The composition for forming a laser light absorption layer according to this embodiment may contain a conventional additive as long as it does not inhibit the curing of the present invention, if desired. The additive will be described later.

  The composition for forming a laser light absorption layer can be obtained by preparing the above materials at an arbitrary ratio.

  Next, the composition for forming a high refractive index pattern will be described. The composition for forming a high refractive index pattern includes at least metal oxide nanoparticles surface-modified with a compound having a photopolymerizable reactive group and a photopolymerization initiator. Moreover, you may contain a photopolymerizable compound, a solvent, etc. as needed.

[Metal oxide nanoparticles]
The metal oxide nanoparticles are surface-modified by a compound having at least one photopolymerizable reactive group in one molecule and at least one reactive group that forms a bond with the metal oxide described later. Yes.

  Examples of the photopolymerizable reactive group include a radical polymerization type reactive group, a cationic polymerization type reactive group, a thiol / ene addition type reactive group, and the like, and a radical polymerization type reactive group is particularly preferable. Examples of the radical polymerization type reactive group include reactive groups having an ethylenically unsaturated double bond group such as acryloyl group, methacryloyl group, vinyl group, and allyl group. In particular, an acryloyl group or a methacryloyl group is preferable.

  Examples of the reactive group that forms a bond with the metal oxide include an alkoxysilyl group, a hydroxyl group, an amino group, a phosphate group, and a silicate group. A phosphate group is particularly preferable. Metal oxide nanoparticles having a photopolymerizable reactive group on the surface by a hydrolysis reaction between a compound having a reactive group that forms a bond with the photopolymerizable reactive group and the metal oxide and a metal oxide described later Is obtained.

(Metal oxide)
The metal oxide is a compound mainly composed of a metal atom and an oxygen atom, and fine particles of the metal oxide may be used as they are, or a metal oxide sol may be produced by a known method and used.

  Although it does not specifically limit as a metal in a metal oxide, For example, titanium, a zirconium, hafnium, aluminum, zinc, tin etc. are mentioned. Of these, titanium, zirconium, zinc, and tin are preferable because of their high refractive index. Accordingly, titanium oxide, zirconium oxide, zinc oxide, and tin oxide are preferable as the metal oxide nanoparticles constituting the metal oxide nanoparticles surface-modified with the compound having a photopolymerizable reactive group. These metal oxides can be used alone or in combination of two or more.

Commercially available metal oxide nanoparticles include Ishihara Sangyo: TTO-55 (titanium oxide), TTO-51 (titanium oxide), TTO-S-1 (titanium oxide), TTO-S-2 (titanium oxide). ), TTO-S-3 (titanium oxide), TTO-S-4 (titanium oxide), ST-01 (titanium oxide), ST-21 (titanium oxide), ST-31 (titanium oxide), manufactured by Sumitomo Osaka Cement : OZC-3YC (zirconium oxide), OZC-3YD (zirconium oxide), OZC-3YFA (zirconium oxide), OZC-8YC (zirconium oxide), OZC-0S100 (zirconium oxide), manufactured by Nippon Electric Works: PCS (zirconium oxide) , T-01 (zirconium oxide), first rare element: UEP (zirconium oxide), UEP-100 (zirconium oxide), Mitsubishi Teriaru made: T-1 (ITO), Mitsui Mining & Smelting manufactured: Pastran (ITO), manufactured by CI Kasei Co.: Nanotech ITO, NANOTEC TiO _2, Nanotech _Al 2 _{O 3,} NANOTEC ZnO, Hakusui Tech Ltd. PazetCK (aluminum-doped zinc oxide), PazetGK (gallium-doped zinc oxide), manufactured by Sakai Chemical: SC-18 (aluminum-doped zinc oxide), FINEX-25 (zinc oxide), FINEX-25LP (zinc oxide), FINEX-50 (zinc oxide), FINEX-50LP2 ( Zinc oxide), FINEX-75 (zinc oxide) STR-60C (titanium oxide), STR-60C-LP (titanium oxide), STR-100C (titanium oxide), manufactured by Nippon Aerosil Co., Ltd .: Aluminum Oxide C (aluminum oxide), etc. is there.

  The metal oxide sol can be produced, for example, by a method of adding a solvent to a metal alkoxide or metal halide, followed by hydrolysis and condensation. As the solvent used for the production of the metal oxide sol, any of an inorganic solvent such as water, an organic solvent described later, or a mixture thereof may be used. Although it does not specifically limit as an organic solvent, For example, alcohol (For example, alkyl alcohols, such as ethanol, propanol, isopropanol, glycols, such as ethylene glycol, propylene glycol, etc.), hydrocarbons (for example, fats, such as hexane) Aromatic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene), halogenated hydrocarbons (eg methylene chloride, chloroform etc.), ethers (eg dimethyl ether, Chain ethers such as diethyl ether, cyclic ethers such as dioxane, tetrahydrofuran, etc.), esters (eg, methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, ethyl butyrate), ketones (eg, acetone, ethyl) Methyl ketone, methyl isobuty Ketones, cyclohexanone, N-methyl-2-pyrrolidone, etc.), cellosolves (eg, methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.), carbitols (eg, methyl carbitol, ethyl carbitol, butyl carbitol, etc.), propylene Glycol monoalkyl ethers (eg, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-butyl ether), glycol ether esters (eg, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, etc.), amides (For example, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), sulfoxides (for example, dimethylsulfamide) Kishido etc.), nitriles (e.g., acetonitrile, benzonitrile, etc.) and the like. Specifically as a solvent which is a mixture, the mixture etc. which combined toluene, isopropyl alcohol, and water are mentioned, for example.

  Examples of the metal alkoxide include titanium alkoxide, zirconium alkoxide, hafnium alkoxide, aluminum alkoxide, zinc alkoxide, and tin alkoxide.

  Although it does not specifically limit as titanium alkoxide, For example, dialkoxy titanium, such as dialkyl dialkoxy titanium (for example, dimethyl dimethoxy titanium, diethyl diethoxy titanium, etc.); Trialkoxy titanium (for example, trimethoxy titanium, triethoxy titanium, etc.) Trialkoxy titanium such as alkyltrialkoxytitanium (eg, ethyltrimethoxytitanium), aryltrialkoxytitanium (eg, phenyltrimethoxytitanium); tetraalkoxytitanium (eg, tetramethoxytitanium, tetraethoxytitanium, tetrapropoxy) Titanium, tetraisopropoxy titanium, tetraisobutoxy titanium, tetra n-butoxy titanium, tetra t-butoxy titanium, tetranonyloxy titanium, tetrakis (2-ethylhex From the viewpoints of tetraalkoxytitanium having 1 to 18 carbon atoms such as (ruoxy) titanium, tetrakis (methoxypropoxy) titanium, tetrastearyloxytitanium, tetraisostearyloxytitanium, etc. Alkoxy titanium, more preferably tetraalkoxy titanium having 1 to 6 carbon atoms, and the like.

  Although it does not specifically limit as a zirconium alkoxide, For example, tetraalkoxy zirconium (For example, tetramethoxy zirconium, tetraethoxy zirconium, tetraisopropoxy zirconium, tetraisobutoxy zirconium, tetra n-butoxy zirconium, tetra t-butoxy zirconium, tetrakis ( 2-ethylhexyloxy) zirconium, tetrakis (2-methyl-2-butoxy) zirconium such as tetraalkoxyzirconium having 1 to 18 carbon atoms, from the viewpoint of hydrolyzability, preferably tetraalkoxyzirconium having 1 to 10 carbon atoms, More preferable examples include tetraalkoxy zirconium having 1 to 6 carbon atoms.

  The hafnium alkoxide is not particularly limited, and examples thereof include tetramethoxyhafnium, tetraethoxyhafnium, tetraisopropoxyhafnium, tetrat-butoxyhafnium, and the like.

  The aluminum alkoxide is not particularly limited, and examples thereof include trialkoxyaluminum (trimethoxyaluminum, triethoxyaluminum, tripropoxyaluminum, tri-n-butoxyaluminum, tris-butoxyaluminum, tri-t-butoxyaluminum, etc.) and the like. It is done.

  Although it does not specifically limit as a zinc alkoxide, For example, diethoxy zinc, bismethoxyethoxy zinc, etc. are mentioned.

  Although it does not specifically limit as a tin alkoxide, For example, tetraethoxy tin, tetraisopropoxy tin, tetra n-butoxy tin etc. are mentioned.

  Of the above metal alkoxides, titanium alkoxides or zirconium alkoxides are preferable from the viewpoint of increasing the refractive index. Further, among titanium alkoxides, tetraethoxy titanium, tetra n-propoxy titanium, tetraisopropoxy titanium, tetra n-butoxy titanium, tetraisobutoxy titanium, tetra s-butoxy titanium, tetra t-butoxy titanium are among the zirconium alkoxides. Tetraethoxyzirconium, tetran-propoxyzirconium, tetraisopropoxyzirconium, tetran-butoxyzirconium, tetraisobutoxyzirconium, tetras-butoxyzirconium, and tetrat-butoxyzirconium are more preferred. Of these, tetra n-butoxy titanium, tetraisobutoxy titanium, tetra s-butoxy titanium, and tetra t-butoxy titanium are particularly preferable.

  The metal halide is not particularly limited, but titanium halides such as titanium tetrachloride and titanium tetrabromide; zirconium halides such as zirconium tetrachloride, zirconium tetrabromide and zirconium iodide; zirconium oxychloride and zirconium oxyiodide Zirconium oxyhalides such as hafnium tetrachloride; hafnium oxyhalides such as hafnium oxychloride; aluminum halides such as aluminum bromide, aluminum chloride and aluminum iodide; zinc chloride, zinc bromide and iodine Zinc halides such as zinc halide; tin halides such as tin chloride, tin bromide, tin iodide, and the like.

  Among the above metal halides, titanium tetrachloride, titanium tetrabromide, zirconium tetrachloride, zirconium tetrabromide, and zirconium oxychloride are preferable from the viewpoint of increasing the refractive index of the thin film, and titanium tetrachloride, tetrachloride. Zirconium and zirconium oxychloride are particularly preferred.

  As a metal oxide nanoparticle surface-modified with a compound having at least one photopolymerizable reactive group in one molecule and at least one reactive group that forms a bond with the metal oxide, And methacryloyl group-modified titanium oxide nanoparticles manufactured by Daihachi Chemical Industry Co., Ltd .: SR-0820.

  In the composition for forming a high refractive index pattern, it is preferable that the metal oxide nanoparticles surface-modified with a compound having a photopolymerizable reactive group contain 25 wt% or more in the solid content. In particular, it is preferably 50 wt% or more. When the content of the metal oxide nanoparticles is less than 25 wt% in the solid content, the energy that can be absorbed out of the irradiated laser light is small, so the metal oxide nanoparticles are not sufficiently heated and increased in refractive index, This is because there is no difference in refractive index sufficient to form a high refractive index pattern between the first region 14 irradiated with the laser and the second region 15 not irradiated with the laser.

  Moreover, it is desirable that the particle diameter of the metal oxide nanoparticles surface-modified with a compound having a photopolymerizable reactive group is 1 nm or more and 100 nm or less. In particular, the thickness is preferably 2 nm or more and 30 nm or less. When the particle diameter is smaller than 1 nm, the particles are aggregated, so that a uniform coating film is not formed and a high refractive index pattern cannot be produced uniformly. On the other hand, when the particle size is 100 nm or more, light is scattered and the transparency of the coating film may be lost.

[Photopolymerizable compound]
As a photopolymerizable compound contained in the composition for forming a laser light absorption layer and the composition for forming a high refractive index pattern according to this embodiment, for example, an acrylate or a methacrylate compound can be used.

  In the present specification, “(meth) acrylate” indicates both “acrylate” and “methacrylate”.

  Examples of the monofunctional (meth) acrylate compound include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl ( (Meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) Acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene oxide modified phosphoric acid (meth) acrylate, phenoxy (meth) acrylate , Ethylene oxide modified phenoxy (meth) acrylate, propylene oxide modified phenoxy (meth) acrylate, nonylphenol (meth) acrylate, ethylene oxide modified nonylphenol (meth) acrylate, propylene oxide modified nonylphenol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, Methoxypolyethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hydrogen phthalate, 2- (meth) acryloyloxypropylhexahydrohydrogenphthalate, 2- (meth) acryloyloxypropyltetrahydrophthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexa Fluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, 2-a And adamantyl acrylate having a monovalent mono (meth) acrylate derived from damantane and adamantanediol.

  Examples of the bifunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and nonanediol di (meth). Acrylate, ethoxylated hexanediol di (meth) acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, tripropylene glycol Di (meth) acrylate and di (meth) acrylate.

  Examples of the trifunctional or higher functional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and tris 2-hydroxyethyl. Trifunctional (meth) acrylate compounds such as isocyanurate tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate Pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipen Trifunctional or more polyfunctional (meth) acrylate compounds such as erythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylolpropane hexa (meth) acrylate, and the like ( Examples thereof include polyfunctional (meth) acrylate compounds in which a part of (meth) acrylate is substituted with an alkyl group or ε-caprolactone.

  These photopolymerizable compounds can be used alone or in combination of two or more.

(Photopolymerization initiator)
The photopolymerization initiator contained in the composition for forming a laser light absorption layer and the composition for forming a high refractive index pattern according to the present embodiment may be any one that generates radicals when irradiated with ultraviolet rays. Benzoins (for example, benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether); acetophenones (for example, acetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2) -Methyl-1-phenylpropan-1-one, 2,2-diethoxy-2-phenylacetophenone, 2-phenyl-2-hydroxy-acetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc. Propiophenones (eg, p-dimethylaminopropiophenone, 2-hydroxy-2-methyl-propiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc.); butyrylphenones ( For example, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propan-1-one, etc.); aminoacetophenones (for example, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one 2-methyl-2-morpholino-1-phenylpropan-1-one, 2-dimethylamino-2-methyl-1- (4-methylphenyl) propan-1-one, 1- (4-butylphenyl)- 2-dimethylamino-2-methylpropan-1-one, 2-dimethylamino-1- (4-methoxyphenyl) -2-methylpropan-1-one, 2-dimethylamino-2-methyl-1- (4 -Methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-dimethylaminophenyl) -butan-1-one, etc.); benzophenones (Eg, benzophenone, benzyl, 4,4′-bis (dimethylamino) benzophenone (Michler's ketone), N, N′-dialkylaminobenzophenone, etc.); ketals (eg, acetophenone dimethyl ketal, benzyldimethyl ketal, etc.); thioxanthene (Eg, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, etc.); anthraquinones (eg, 2-ethylanthraquinone, 1-chloroanthraquinone, 1,2-benzanthraquinone, 2,3-diphenyl) Anthraquinone); (thio) xanthones (eg, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc.); (Eg, 1,3-bis- (9-acridinyl) propane, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, etc.); triazines {eg, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine, etc.); sulfides (eg, benzyldiphenyl sulfide, etc.); acylphosphine oxides (eg, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc.) A titanocene photopolymerization initiator; oxime esters and the like. These photopolymerization initiators can be used alone or in combination of two or more.

〔solvent〕
As the solvent contained in the composition for forming a laser light absorption layer and the composition for forming a high refractive index pattern according to this embodiment, either an organic solvent or an inorganic solvent can be used.

  Although it does not specifically limit as an organic solvent, For example, alcohols (For example, alkyl alcohols, such as ethanol, propanol, isopropanol, glycols, such as ethylene glycol, propylene glycol, etc.), hydrocarbons (for example, fats, such as hexane) Aromatic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as toluene and xylene), halogenated hydrocarbons (eg methylene chloride, chloroform etc.), ethers (eg dimethyl ether, Chain ethers such as diethyl ether, cyclic ethers such as dioxane, tetrahydrofuran, etc.), esters (eg, methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, ethyl butyrate), ketones (eg, acetone, ethyl) Methyl ketone, methyl isobutyl , Cyclohexanone, N-methyl-2-pyrrolidone, etc.), cellosolves (eg, methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.), carbitols (eg, methyl carbitol, ethyl carbitol, butyl carbitol, etc.), propylene Glycol monoalkyl ethers (eg, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-butyl ether), glycol ether esters (eg, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, etc.), amides (For example, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), sulfoxides (for example, dimethylsulfo Side), nitriles (for example, acetonitrile, benzonitrile, etc.) can be used, and from the viewpoint of dispersibility of nanoparticles, aromatic hydrocarbons and glycol ether esters are preferable, and toluene is particularly preferable. And propylene glycol monomethyl ether acetate.

  The inorganic solvent is not particularly limited, and examples thereof include acidic aqueous solutions such as hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, and phosphoric acid; and salts such as sodium hydroxide, magnesium hydroxide, calcium hydroxide, potassium hydroxide, and sodium hydrogen carbonate. Basic aqueous solution to be contained; neutral aqueous solution such as pure water and saline.

  These organic solvents may be used alone or in combination of two or more. Moreover, only one of an organic solvent or an inorganic solvent may be used as the solvent, or a mixture of both may be used.

[Optional substances]
The composition for forming a laser light absorption layer and the composition for forming a high refractive index pattern according to this embodiment may contain a conventional additive to the extent that the effects of the present invention are not impaired as desired. Examples of additives include thickeners, sensitizers, antifoaming agents, leveling agents, coatability improvers, lubricants, stabilizers (antioxidants, heat stabilizers, light stabilizers, etc.), plasticizers, and interfaces. Activators, dissolution accelerators, fillers, antistatic agents, curing agents, flame retardants and the like can be mentioned. These additives may be used alone or in combination of two or more.

  Next, a method for forming a high refractive index pattern according to this embodiment will be described. The method for forming a high refractive index pattern according to this embodiment includes three steps: a laser light absorption layer forming step, a high refractive index pattern layer forming step, and a pattern drawing step.

  First, the laser light absorption layer forming step will be described.

  A coating liquid made of a composition for forming a laser light absorption layer is applied on the base material layer 11 to form a first photosensitive layer, and the first photosensitive layer is irradiated with ultraviolet rays to form the first photosensitive layer. It hardens | cures and the laser beam absorption layer 12 is formed.

  The film thickness of the laser light absorbing layer 12 is preferably in the range of 500 nm to 50 μm. When the film thickness is less than 500 nm, the compound having absorption in the emission wavelength region of the laser beam is not heated when irradiated with the laser, and the metal oxide nanoparticles in the high refractive index pattern forming layer are not heated by the compound. It becomes difficult to heat. As a result, since it is difficult for a difference in refractive index to occur in the high refractive index pattern forming layer, a high refractive index pattern may not be formed. When the film thickness is thicker than 50 μm, the curability is lowered and there is a possibility that a coating film cannot be produced.

  As the base material layer 11, a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, a glass plate, etc. can be used.

  As the film forming method, a wet coating method using a roll coater, reverse roll coater, gravure coater, micro gravure coater, knife coater, bar coater, wire bar coater, die coater, dip coater, spin coater can be used. .

  You may provide a drying process, after apply | coating a coating liquid on the base material layer 11. FIG. In particular, when the coating liquid contains a solvent, it is necessary to provide a drying step in order to remove the solvent of the formed coating film. Examples of the drying means include heating using a heat source such as an oven, a hot plate, and an IR heater, blowing, and hot air.

  For irradiating the first photosensitive layer with ultraviolet rays, ultraviolet irradiation lamps such as a high pressure mercury lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, and a xenon arc can be used. Moreover, nitrogen can be used as an inert gas introduced in order to reduce oxygen concentration at the time of ultraviolet irradiation. In addition to ultraviolet irradiation lamps, flash xenon lamps can also be used.

  Next, the high refractive index pattern layer forming step will be described.

  First, a coating liquid made of a composition for forming a high refractive index pattern is applied on the laser light absorption layer 12 to form a second photosensitive layer, and the second photosensitive layer is irradiated with ultraviolet rays to thereby form a second photosensitive layer. The photosensitive layer is cured, and the high refractive index pattern forming layer 13 is formed.

  The film thickness of the high refractive index pattern forming layer 13 is preferably in the range of 50 nm to 5 μm. When the film thickness is less than 50 nm, sufficient heating is not performed by laser irradiation, and a difference in refractive index does not occur. When the film thickness is thicker than 5 μm, the film-forming property is lowered and a cured coating film may not be obtained.

  As the film forming method, a wet coating method using a roll coater, reverse roll coater, gravure coater, micro gravure coater, knife coater, bar coater, wire bar coater, die coater, dip coater, spin coater can be used. .

  You may provide a drying process, after apply | coating a coating liquid on the laser beam absorption layer 12. FIG. In particular, when the coating liquid contains a solvent, it is necessary to provide a drying step in order to remove the solvent of the formed coating film. Examples of the drying means include heating using a heat source such as an oven, a hot plate, and an IR heater, blowing, and hot air.

  For irradiating the photosensitive layer with ultraviolet rays, ultraviolet irradiation lamps such as a high pressure mercury lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc, and a xenon arc can be used. Moreover, nitrogen can be used as an inert gas introduced in order to reduce oxygen concentration at the time of ultraviolet irradiation. In addition to ultraviolet irradiation lamps, flash xenon lamps can also be used.

  Next, in the pattern drawing process, an arbitrary pattern is created in advance by CAD or the like, and a first position of the high refractive index pattern forming layer 13 is irradiated by irradiating a desired position of the high refractive index pattern forming layer 13 according to the created pattern. The region 14 is heated to form a high refractive index pattern. As the laser used, the laser emission wavelength is included in the absorption wavelength range of the compound of the laser light absorption layer 12 and the absorption wavelength range of the metal oxide nanoparticles of the high refractive index pattern formation layer 13. I just need it. The compound having absorption in the laser light emission wavelength region of the laser light absorption layer irradiated with the laser absorbs the laser light, whereby the metal oxide nanoparticles of the high refractive index pattern forming layer are heated. Moreover, the metal oxide nanoparticles of the high refractive index pattern forming layer are heated by laser irradiation. Thereby, the 1st area | region 14 irradiated with the laser of the high refractive index pattern formation layer becomes dense, and only the 1st area | region 14 raises a refractive index. As a result, only the first region 14 irradiated with the laser has a high refractive index, and a difference in refractive index occurs between the first region 14 irradiated with the laser and the second region 15 not irradiated with the laser.

  Depending on the type of metal oxide to be used and the modification group of the metal oxide, for example, 0.05 to 0 in the first region 14 irradiated with laser and the second region 15 not irradiated with laser. It is desirable that a difference in refractive index of 2 or less occurs. In particular, a difference in refractive index of 0.1 or more and 0.2 or less is more preferable. When the refractive index difference is smaller than 0.05, sufficient diffracted light cannot be obtained.

Examples of the laser include gas lasers such as CO ₂ laser, He—Ne laser, Ar laser, and excimer laser, solid lasers such as YAG laser and YVO 4 laser, and semiconductor lasers.

  As described above, the high refractive index pattern according to the present embodiment is formed.

  According to the laminate including the high refractive index pattern and the method for forming the high refractive index pattern according to the present embodiment, the first region irradiated with the laser beam and the second laser beam not irradiated by the heating by the laser irradiation. Therefore, a high refractive index pattern can be formed by a simple method. In addition, since there are few steps, reproduction can be performed with good reproducibility, and a mold is unnecessary, so that patterns of various shapes can be manufactured at low cost. Further, by providing the laser light absorbing layer, it becomes easier to heat the metal oxide nanoparticles of the high refractive index pattern forming layer than in the case of only the high refractive index pattern forming layer. Therefore, the output of the laser beam can be kept low, and the pattern can be formed even when the film thickness of the high refractive index pattern forming layer is reduced, and the cost can be reduced.

  Examples of the present invention are shown below.

[Preparation of coating solution for laser light absorption layer formation]
(Preparation of laser light absorption layer forming coating solution 1)
Trimethylolpropane triacrylate (TMPTA, Biscoat # 295, manufactured by Osaka Organic Chemical Industry Co., Ltd.) with a solid content of 97 wt% and lanthanum hexaboride nanoparticles (KHF-7AH, particle size 20 nm, toluene dispersion, Sumitomo Metals) Mine Co., Ltd.) is mixed at 3 wt% in the solid content, and Irgacure 184 (BASF Japan Co., Ltd.) is added as a photopolymerization initiator at 10 wt% with respect to TMPTA so that the total solid content becomes 30 wt%. And diluted with methyl ethyl ketone.

(Preparation of coating solution 2 for forming a laser light absorbing layer)
Trimethylolpropane triacrylate (TMPTA, Biscoat # 295, manufactured by Osaka Organic Chemical Industry Co., Ltd.) with a solid content of 98 wt%, lanthanum hexaboride nanoparticles (KHF-7AH, particle size 20 nm, toluene dispersion, Sumitomo Metals) Mine Co., Ltd.) is mixed at 2 wt% in the solid content, and Irgacure 184 (BASF Japan Co., Ltd.) as a photopolymerization initiator is added at 10 wt% with respect to TMPTA so that the total solid content becomes 30 wt%. And diluted with methyl ethyl ketone.

(Preparation of laser light absorption layer forming coating solution 3)
Trimethylolpropane triacrylate (TMPTA, Biscoat # 295, manufactured by Osaka Organic Chemical Industry Co., Ltd.) in a solid content of 99 wt%, lanthanum hexaboride nanoparticles (KHF-7AH, particle size 20 nm, toluene dispersion, Sumitomo Metals) Mine Co., Ltd.) is mixed at 1 wt% in the solid content, and Irgacure 184 (BASF Japan Co., Ltd.) as a photopolymerization initiator is added at 10 wt% to TMPTA so that the total solid content becomes 30 wt%. And diluted with methyl ethyl ketone.

(Preparation of laser light absorption layer forming coating solution 4)
Trimethylolpropane triacrylate (TMPTA, Biscoat # 295, manufactured by Osaka Organic Chemical Industry Co., Ltd.) is added at 100 wt% in the solid content, and Irgacure 184 (manufactured by BASF Japan Co., Ltd.) as a photopolymerization initiator is added at 10 wt% relative to TMPTA. And diluted with methyl ethyl ketone so that the total solid content was 30 wt%.

(Preparation of laser light absorption layer forming coating solution 5)
Trimethylolpropane triacrylate (TMPTA, Biscoat # 295, manufactured by Osaka Organic Chemical Industry Co., Ltd.) with a solid content of 80 wt% and ATO particles (ELCOM V-3508, particle size 8 nm, 1-methoxy-2-propanol (hereinafter referred to as “Methoxy”) , PGME) dispersion, manufactured by JGC Catalysts & Chemicals Co., Ltd.) at a solid content of 20 wt%, and Irgacure 184 (manufactured by BASF Japan Co., Ltd.) as a photopolymerization initiator was added at 10 wt% with respect to TMPTA. Dilution with methyl ethyl ketone was performed so that the solid content was 30 wt%.

[Preparation of coating solution for forming high refractive index pattern forming layer]
(Preparation of coating liquid 1 for forming a high refractive index pattern forming layer)
Methacryloyl group-modified titanium oxide nanoparticles (SR-0820, particle size 2 to 5 nm, toluene dispersion, manufactured by Daihachi Chemical Industry Co., Ltd.) 100 wt% in the solid content, Irgacure 907 (BASF Japan Co., Ltd.) as a photopolymerization initiator ) Was added at a solid content ratio of 5 wt%, and diluted with toluene so that the total solid content was 10 wt%.

(Preparation of coating liquid 2 for forming a high refractive index pattern forming layer)
Methacryloyl group-modified titanium oxide nanoparticles (SR-0820, particle size 2 to 5 nm, toluene dispersion, manufactured by Daihachi Chemical Industry Co., Ltd.) 60 wt% in solid content, pentaerythritol triacrylate (PE-3A, Kyoeisha Chemical Co., Ltd.) )) In a solid content of 40 wt%, and Irgacure 907 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator is added at a solid content ratio of 5 wt%, so that the total solid content is 10 wt%. Diluted with

(Preparation of coating solution 3 for forming a high refractive index pattern forming layer)
Methacryloyl group-modified titanium oxide nanoparticles (SR-0820, particle size 2 to 5 nm, toluene dispersion, manufactured by Daihachi Chemical Industry Co., Ltd.) in a solid content of 20 wt%, pentaerythritol triacrylate (PE-3A, Kyoeisha Chemical Co., Ltd.) )) Is mixed at 80 wt% in the solid content, and Irgacure 907 (BASF Japan Co., Ltd.) is added as a photopolymerization initiator at a solid content ratio of 5 wt%, so that the total solid content is 10 wt%. Diluted with

(Preparation of coating solution 4 for forming a high refractive index pattern forming layer)
Titanium oxide nanoparticles (NSU-399JPF-7, particle size 10 nm, PGME dispersion, manufactured by Nagase ChemteX Corporation) surface-modified with a non-photopolymerizable compound were 80 wt% in solid content, pentaerythritol triacrylate (PE 3A, manufactured by Kyoeisha Chemical Co., Ltd.) at a solid content of 20 wt%, Irgacure 907 (BASF Japan Co., Ltd.) as a photopolymerization initiator was added at a solid content ratio of 5 wt%, and the total solid content was 10 wt%. It diluted with PGME so that it might become%.

(Preparation of coating liquid 5 for forming a high refractive index pattern forming layer)
Titanium oxide nanoparticles (NSU-399JPF-7, particle size 10 nm, PGME dispersion, manufactured by Nagase ChemteX Corp.) surface-modified with a non-photopolymerizable compound, 60 wt% in solid content, pentaerythritol triacrylate (PE -3A, manufactured by Kyoeisha Chemical Co., Ltd.) at a solid content of 40 wt%, Irgacure 907 (manufactured by BASF Japan Co., Ltd.) as a photopolymerization initiator was added at a solid content ratio of 5 wt%, and the total solid content was 10 wt%. It diluted with PGME so that it might become%.

(Preparation of coating liquid 6 for forming a high refractive index pattern forming layer)
Zirconium oxide nanoparticles modified with a compound having a photopolymerizable reactive group (NSU-357FPG-1, average particle size 26 nm, propylene glycol-1-monomethyl ether-2-acetate (hereinafter, PGMEA) dispersion, Nagase Chem Tex Co., Ltd.) was added at 100 wt% in the solid content, and Irgacure 907 (manufactured by BASF Japan Co., Ltd.) as a photopolymerization initiator was added at a solid content ratio of 5 wt%, so that the total solid content was 10 wt%. Diluted with

(Preparation of coating liquid 7 for forming a high refractive index pattern forming layer)
Zirconium oxide nanoparticles modified with a compound having a photopolymerizable reactive group (NSU-357FPG-1, average particle size 26 nm, PGMEA dispersion, manufactured by Nagase ChemteX Corp.) in solid content of 60 wt%, pentaerythritol Triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) was mixed at 40 wt% in the solid content, and Irgacure 907 (manufactured by BASF Japan) was added as a photopolymerization initiator at a solid content ratio of 5 wt%. It diluted with PGMEA so that solid content might be 10 wt%.

(Preparation of coating liquid 8 for forming a high refractive index pattern forming layer)
Zirconium oxide nanoparticles modified with a compound having a photopolymerizable reactive group (NSU-357FPG-1, average particle size 26 nm, PGMEA dispersion, manufactured by Nagase ChemteX Corp.) in a solid content of 20 wt%, pentaerythritol Triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) was mixed at 80 wt% in the solid content, and Irgacure 907 (manufactured by BASF Japan) was added as a photopolymerization initiator at a solid content ratio of 5 wt%. It diluted with PGMEA so that solid content might be 10 wt%.

(Preparation of coating solution 9 for forming a high refractive index pattern forming layer)
Zirconium oxide particles (NAU-476LZK, average particle size 30 nm, PGME dispersion, manufactured by Nagase Chemtex Co., Ltd.) having a surface modification with a non-photopolymerizable compound were 100 wt% in the solid content, and Irgacure 907 (photopolymerization initiator) BASF Japan Co., Ltd.) was added at a solid content ratio of 5 wt%, and diluted with PGME so that the total solid content was 10 wt%.

(Preparation of coating solution 10 for forming a high refractive index pattern forming layer)
Zirconium oxide particles (NAU-476LZK, average particle size 30 nm, PGME dispersion, manufactured by Nagase ChemteX Corporation) surface-modified with a non-photopolymerizable compound, 60 wt% in solid content, pentaerythritol triacrylate (PE- 3A, manufactured by Kyoeisha Chemical Co., Ltd.) at a solid content of 40 wt%, and Irgacure 907 (BASF Japan Co., Ltd.) as a photopolymerization initiator was added at a solid content ratio of 5 wt%, so that the total solid content was 10 wt%. So that it was diluted with PGME.

[Pattern creation]
Pattern data having a line width of 1 μm and a space width of 1 μm and a range of 10 mm × 10 mm was created, and this image data was taken into a laser drawing apparatus (DWL66fs, manufactured by Heidelberg).

[Example 1]
On the transparent glass substrate, the coating solution 1 for forming a laser light absorbing layer is applied using a doctor blade so that the film thickness after curing is 4 μm, dried in an oven at 60 ° C. for 1 minute, and then subjected to ultraviolet light under a nitrogen purge. Was irradiated at an exposure amount of 400 mJ / cm ² to prepare a laser light absorption layer. Next, coating solution 1 for forming a high refractive index pattern forming layer is applied on the laser light absorption layer using a doctor blade so that the film thickness after curing is 200 nm, and dried in an oven at 60 ° C. for 1 minute. Thereafter, ultraviolet rays were irradiated at an exposure amount of 400 mJ / cm ² under a nitrogen purge to produce a high refractive index pattern forming layer. Next, the high refractive index pattern forming layer is irradiated with the above-described pattern at a laser output of 1.0 W using a laser drawing apparatus (DWL66fs, manufactured by Heidelberg), and the high refractive index pattern forming layer is irradiated with the high refractive index pattern. Was made.

[Example 2]
A high refractive index pattern was prepared in the same manner as in Example 1 except that the laser light absorbing layer forming coating solution 2 was used instead of the laser light absorbing layer forming coating solution 1.

[Example 3]
A high refractive index pattern was prepared in the same manner as in Example 1 except that the laser light absorbing layer forming coating solution 3 was used instead of the laser light absorbing layer forming coating solution 1.

[Example 4]
A high refractive index pattern was prepared in the same manner as in Example 1 except that the film thickness after curing of the high refractive index pattern forming layer was 100 nm.

[Example 5]
A high refractive index pattern was produced in the same manner as in Example 3 except that the thickness of the laser light absorption layer after curing was changed to 10 μm.

[Example 6]
A high refractive index pattern was produced in the same manner as in Example 1 except that the film thickness after curing of the laser light absorbing layer was changed to 0.7 μm.

[Example 7]
Example 1 except that the high refractive index pattern forming layer forming coating liquid 2 is used instead of the high refractive index pattern forming layer forming coating liquid 1 and the film thickness of the high refractive index pattern forming layer is 0.4 μm. Similarly, a high refractive index pattern was produced.

[Example 8]
A high refractive index pattern was prepared in the same manner as in Example 1 except that the laser light absorbing layer forming coating solution 5 was used instead of the laser light absorbing layer forming coating solution 1.

[Comparative Example 1]
A high refractive index pattern was prepared in the same manner as in Example 1 except that the laser light absorbing layer forming coating solution 4 was used instead of the laser light absorbing layer forming coating solution 1.

[Comparative Example 2]
A high refractive index pattern was prepared in the same manner as in Example 1 except that the thickness of the laser light absorption layer after curing was 0.2 μm.

[Comparative Example 3]
A high refractive index pattern was produced in the same manner as in Example 7 except that the film thickness after curing of the high refractive index pattern forming layer was 6 μm.

[Comparative Example 4]
Example except that the coating liquid 3 for forming a high refractive index pattern forming layer is used instead of the coating liquid 1 for forming a high refractive index pattern forming layer, and the film thickness after curing of the high refractive index pattern forming layer is 1.5 μm. 1 was used to produce a high refractive index pattern.

[Comparative Example 5]
A high refractive index pattern was prepared in the same manner as in Example 1 except that the high refractive index pattern forming layer forming coating solution 4 was applied instead of the high refractive index pattern forming layer forming coating solution 1.

[Comparative Example 6]
Except for applying the high refractive index pattern forming layer forming coating liquid 5 instead of the high refractive index pattern forming layer forming coating liquid 1 and setting the film thickness after curing of the high refractive index pattern forming layer to 0.4 μm, A high refractive index pattern was prepared in the same manner as in Example 1.

[Examples 9 to 13]
A high refractive index pattern was prepared in the same manner as in Examples 1 to 5 except that the high refractive index pattern forming layer forming coating solution 6 was used instead of the high refractive index pattern forming layer forming coating solution 1.

[Example 14]
A high refractive index pattern was prepared in the same manner as in Example 7 except that the high refractive index pattern forming layer forming coating solution 7 was used instead of the high refractive index pattern forming layer forming coating solution 2.

[Example 15]
A high refractive index pattern was prepared in the same manner as in Example 8 except that the high refractive index pattern forming layer forming coating solution 6 was used instead of the high refractive index pattern forming layer forming coating solution 1.

[Comparative Example 7]
A high refractive index pattern was prepared in the same manner as in Comparative Example 1 except that the high refractive index pattern forming layer forming coating solution 6 was used instead of the high refractive index pattern forming layer forming coating solution 1.

[Comparative Example 8]
A high refractive index pattern was prepared in the same manner as in Comparative Example 2 except that the high refractive index pattern forming layer forming coating solution 6 was used instead of the high refractive index pattern forming layer forming coating solution 1.

[Comparative Example 9]
A high refractive index pattern was prepared in the same manner as in Comparative Example 4 except that the high refractive index pattern forming layer forming coating solution 8 was used instead of the high refractive index pattern forming layer forming coating solution 3.

[Comparative Example 10]
A high refractive index pattern was prepared in the same manner as in Comparative Example 5 except that the high refractive index pattern forming layer forming coating solution 9 was used instead of the high refractive index pattern forming layer forming coating solution 4.

[Comparative Example 11]
A high refractive index pattern was prepared in the same manner as in Comparative Example 6 except that the high refractive index pattern forming layer forming coating solution 10 was used instead of the high refractive index pattern forming layer forming coating solution 5.

The diffracted light of the produced high refractive index pattern was visually evaluated.
◎: Diffracted light can be confirmed very clearly ○: Diffracted light can be confirmed Δ: Diffracted light cannot be confirmed unless the back of the substrate is black ×: Diffracted light is not visible

  The evaluation results are shown in Tables 1 and 2.

  In Examples 1-8 and Examples 9-15, a high refractive index pattern was formed, and diffracted light was confirmed.

  In particular, in Examples 1-2 and Examples 4-5, diffracted light was confirmed very clearly.

  When Comparative Example 1 and Comparative Example 7 did not contain a compound having a laser light absorption component, no diffracted light was observed. From this, when the laser light absorption layer does not contain a compound having absorption in the emission wavelength region of the laser light, the metal oxide nanoparticles are not heated by the compound. It was found that the refractive index was not increased, and a difference in refractive index sufficient for confirming diffracted light between the laser irradiated portion and the unirradiated portion was not generated.

  In Comparative Example 2 and Comparative Example 8, when the thickness of the laser light absorption layer was thin, diffracted light could not be observed. Therefore, when the laser light absorption layer is thin, the compound having a laser light absorption component has a low effect of laser light absorption, and the metal oxide nanoparticles are not heated by the compound. It was found that the particles were not sufficiently heated and increased in refractive index, and a refractive index difference sufficient for confirming diffracted light between the laser irradiated portion and the unirradiated portion was not generated.

  It was found that when the film thickness of the high refractive index pattern forming layer in Comparative Example 3 is large, the film forming property is lowered, and thus a cured coating film cannot be obtained.

  In Comparative Example 4 and Comparative Example 9, when the content of the metal oxide nanoparticles in the high refractive index pattern forming layer was small, no diffracted light was observed. From this, when the content of metal oxide nanoparticles in the high refractive index pattern forming layer is small, the energy that can be absorbed in the irradiated laser light is small, so the metal oxide nanoparticles are sufficiently heated and highly refracted. It was found that the refractive index difference was not sufficient to confirm the diffracted light between the laser irradiated portion and the laser non-irradiated portion.

  When the metal oxide nanoparticles without photopolymerization in Comparative Example 5 and Comparative Example 10 are used and the content of the particles is large, the coating film has low curability so that a cured coating film can be obtained. I knew it was n’t there.

  In the case of using the metal oxide nanoparticles having no photopolymerization in Comparative Example 6 and Comparative Example 11, there is no difference in refractive index between the laser irradiated part and the laser non-irradiated part, and diffracted light is not observed. all right.

  The composition for forming a high refractive index pattern according to the present invention can be used for light diffusing members, optical wiring members, optical member applications such as diffraction gratings, decorations such as holograms, and security applications.

DESCRIPTION OF SYMBOLS 10 Laminated body 11 Base material layer 12 Laser light absorption layer 13 High refractive index pattern formation layer 14 1st area | region 15 2nd area | region

Claims (5)

A substrate;
A composition comprising a compound having absorption in the emission wavelength region of laser light, a laser light absorption layer formed on the substrate,
A cured film of a coating solution of a composition for forming a high refractive index pattern containing metal oxide nanoparticles surface-modified with a compound having at least a photopolymerizable reactive group, and formed on the laser light absorbing layer A high refractive index pattern forming layer,
The composition for forming a high refractive index pattern includes the metal oxide nanoparticles in a solid content of 25 wt% or more,
A layered product, wherein the laser light absorbing layer has a thickness of 500 nm to 50 μm, and the high refractive index pattern forming layer has a thickness of 50 nm to 5 μm.   The laminate according to claim 1, wherein the metal oxide constituting the metal oxide nanoparticles is any one of titanium oxide, zirconium oxide, zinc oxide, and tin oxide.   The laminate according to claim 1 or 2, wherein the metal oxide nanoparticles have a particle size of 1 nm or more and 100 nm or less. A first photosensitive layer made of a composition containing a compound having absorption in the emission wavelength region of laser light is formed on a substrate, and the first photosensitive layer is irradiated with ultraviolet rays to form a laser light absorbing layer. Process,
Forming a second photosensitive layer comprising a composition for forming a high refractive index pattern comprising metal oxide nanoparticles surface-modified with a compound having at least a photopolymerizable reactive group on the laser light absorbing layer, Irradiating the second photosensitive layer with ultraviolet rays to form a high refractive index pattern forming layer;
Irradiating the high refractive index pattern forming layer with laser light in accordance with a predetermined pattern to form a high refractive index pattern,
The composition for forming a high refractive index pattern includes the metal oxide nanoparticles in a solid content of 25 wt% or more,
A method for forming a high refractive index pattern, wherein the laser light absorbing layer has a thickness of 500 nm to 50 μm, and the high refractive index pattern formation layer has a thickness of 50 nm to 5 μm.   An optical element provided with the laminated body containing the high refractive index pattern of Claims 1 thru | or 3.