JP2016218226A - Composition for forming high refractive index pattern, and laminate, optical element and method for forming high refractive index pattern using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for forming a high refractive index pattern, a laminate, an optical element and a method for forming a high refractive index pattern, for inexpensively forming a pattern excellent in reproducibility through a simple process.SOLUTION: The composition for forming a high refractive index pattern comprises: metal oxide nanoparticles (A) having surfaces modified with a compound having at least a photopolymerizable reactive group; a compound (B) having absorption in an emission wavelength region of laser light; and a photopolymerization initiator (C). The total content of the metal oxide nanoparticles (A) and the compound (B) is 25 wt.% or more in the solid content; and a weight ratio of the metal oxide nanoparticles (A) to the compound (B) ranges from 99:1 to 80:20.SELECTED DRAWING: Figure 2

Description

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

  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 composition for forming a high refractive index pattern, a laminate, an optical element, and a method for forming a high refractive index pattern that are low cost and excellent in reproducibility by a simple process.

  The present invention comprises a metal oxide nanoparticle (A) surface-modified with a compound having at least a photopolymerizable reactive group, a compound (B) having absorption in the emission wavelength region of laser light, a photopolymerization initiator ( C) and a composition for forming a high refractive index pattern. Furthermore, the total content of the metal oxide nanoparticles (A) and the compound (B) is 25 wt% or more in the solid content, and the weight ratio between the metal oxide nanoparticles (A) and the compound (B) is 99: 1 to 80:20.

  Moreover, the composition for high refractive index pattern formation may further contain a photopolymerizable compound (D).

  In addition, the metal oxide constituting the metal oxide nanoparticles (A) may be any of titanium oxide, zirconium oxide, zinc oxide, and tin oxide.

  Moreover, 1 nm or more and 100 nm or less may be sufficient as the particle size of a metal oxide nanoparticle (A).

  The present invention also includes a step of laminating a composition for forming a high refractive index pattern on a substrate to form a photosensitive layer, and irradiating the photosensitive layer with laser light in accordance with a predetermined pattern to form a high refractive index pattern. And a step of irradiating the photosensitive layer with ultraviolet rays and curing a region not irradiated with laser light.

  Moreover, it is equipped with the base material and the photosensitive layer laminated | stacked on the base material using the composition for high refractive index pattern formation, and the photosensitive layer is irradiated with the laser beam and the first region irradiated with the laser beam. A laminated body in which a refractive index pattern is formed by including a second region that is not provided and the first region and the second region having different refractive indexes may be used.

  Moreover, an optical element provided with the laminated body in which the high refractive index pattern was formed may be sufficient.

  According to the present invention, a composition for forming a high refractive index pattern, a laminate, an optical element, and a method for forming a high refractive index pattern that are low in cost and excellent in reproducibility can be realized by a simple process.

Sectional schematic diagram which shows an example of the laminated body which concerns on embodiment of this invention Schematic cross section showing a state in which a high refractive index pattern is formed on the laminate shown in FIG.

  The present inventor forms a high refractive index pattern comprising metal oxide nanoparticles (A) surface-modified with a compound having a photopolymerizable reactive group and a compound (B) having absorption in the emission wavelength region of laser light. After applying the composition for a base material layer, by irradiating an arbitrary pattern using a laser beam, a method for forming a high refractive index pattern in a simple process without using a mold or the like is found, The present invention has been reached.

  Specifically, the composition for forming a high refractive index pattern comprises a metal oxide nanoparticle (A) surface-modified with a compound having a photopolymerizable reactive group, and a compound having absorption in the emission wavelength region of laser light. (B) and a photoinitiator (C) are included. By irradiating the composition for forming a high refractive index pattern with a laser, a polymerization reaction occurs, and the metal oxide nanoparticles (A) and the compound (B) absorb the laser beam and are heated, thereby irradiating the laser. Only the formed first region has a high refractive index. A refractive index difference is formed between the first region irradiated with the laser and the second region not irradiated with the laser, and a high refractive index pattern is formed by the first region.

  Hereinafter, a composition for forming a high refractive index pattern, a laminate using the same, an optical element and a method for forming a high refractive index pattern according to an embodiment of the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view showing an example of a laminate according to this embodiment. As shown in FIG. 1, the laminate 10 includes a base material layer 11 and a photosensitive layer 12 formed on one surface of the base material layer 11. The photosensitive layer 12 includes a metal oxide nanoparticle (A) surface-modified with a compound having a photopolymerizable reactive group, a compound (B) having absorption in the emission wavelength region of laser light, a photopolymerization initiator ( C) and a composition for forming a high refractive index pattern.

  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, a first region 13 irradiated with a laser and a second region 14 not irradiated with a laser are formed in the photosensitive layer 12 of the stacked body 10.

  That is, by irradiating the photosensitive layer 12 laminated with the high refractive index pattern forming composition on the base layer 11 with laser light, polymerization and heating occur, and as a result, the first region 13 irradiated with the laser and A difference in refractive index occurs between the second region 14 not irradiated with laser and a high refractive index pattern is formed on the base material layer 11. Thereafter, in order to cure the second region not irradiated with the laser, the entire coating film is irradiated with ultraviolet rays to form a cured coating film having a high refractive index pattern. The high refractive index pattern forming method will be described later.

  Hereinafter, the composition for forming a high refractive index pattern according to this embodiment will be described.

[Metal oxide nanoparticles (A)]
The metal oxide nanoparticles (A) have a surface formed by a compound having at least one photopolymerizable reactive group in one molecule and at least one reactive group that forms a bond with a metal oxide described later. It is qualified.

  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. Therefore, titanium oxide, zirconium oxide, zinc oxide, and tin oxide are preferable as the metal oxide nanoparticles constituting the metal oxide nanoparticles (A) whose surface is modified by 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: SN-100P (ATO), FS-10P (ATO), SN-102P (ATO), FS-12P (ATO), 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 (oxidation) Zirconium), OZC-8YC (zirconium oxide), OZC-0S100 (zirconium oxide), manufactured by Nippon Electric Works: PCS (zirconium oxide), T-01 (acid) Zirconium), first rare element: UEP (zirconium oxide), UEP-100 (zirconium oxide), Mitsubishi Materials: T-1 (ITO), S-1200 (tin oxide), Mitsui Metals: Pastoran (ITO, ATO), manufactured by CI Kasei Co.: Nanotech ITO, NANOTEC SnO _2, NANOTEC TiO _2, NANOTEC SiO _2, Nanotech _Al 2 _{O 3,} NANOTEC ZnO, catalysts & Chemicals Ltd.: TL-20 (ATO), TL-30 (ATO), TL -30S (PTO), TL-120 (ITO), TL130 (ITO), manufactured by HakuSitec: PazetCK (aluminum doped zinc oxide), PazetGK (gallium doped zinc oxide), Sakai Chemical: SC-18 (aluminum doped zinc oxide) , FINEX-25 (zinc oxide), FINEX-2 LP (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) and the like.

  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.

[Compound (B) having absorption in the emission wavelength region of laser light]
Examples of the compound (B) having absorption in the emission wavelength region of laser light contained in the high refractive index pattern forming composition include metal nanoparticles, pigments, dyes and the like. 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 titanium, zirconium, zinc, silver, tin, and lanthanum.

Commercially available metal nanoparticles include: Ishihara Sangyo: SN-100P (ATO), FS-10P (ATO), SN-102P (ATO), FS-12P (ATO), 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) Ni), first rare element: UEP (zirconium oxide), UEP-100 (zirconium oxide), Mitsubishi Materials: T-1 (ITO), S-1200 (tin oxide), Mitsui Metals: Pastoran (ITO, ATO), CI Kasei: Nanotech ITO, Nanotech SnO ₂ , Nanotech TiO ₂ , Nanotech SiO ₂ , Nanotech ZnO, JGC Catalysts & Chemicals: ELCOM V-3560 (zirconium oxide), ELCOM V-3508 (zirconium oxide), Sakai Chemical Manufactured: 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 Sumitomo Metal Mining Co., Ltd .: KHF-7AH (lanthanum hexaboride), manufactured by Shikoku Keisoku Kogyo Co., Ltd .: silver nanoparticles, and the like.

  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, manufactured by Sanyo Dye: SF GREEN GC6036, SF BLUE GB1377, manufactured by Sumitomo Chemtex: SUMIPLAST BLUE OR, SUMIPLAST Yellow FL7G, and the like.

[Photopolymerization initiator (C)]
The photopolymerization initiator (C) contained in the composition for forming a high refractive index pattern may be any one that generates radicals when irradiated with ultraviolet rays. For example, benzoins (for example, benzoin, benzoin methyl ether) Benzoin alkyl ethers such as benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether); acetophenones (eg, acetophenone, p-dimethylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-phenyl-2-hydroxy-acetophenone, 1,1-dichloroacetophenone, 1-hydroxy Cyclohexyl phenyl ketone, etc.]; propiophenones (for example, p-dimethylaminopropiophenone, 2-hydroxy-2-methyl-propiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, etc.) Butyrylphenones (eg, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propane) -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, -(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) -butane -1-one etc.); benzophenones (eg benzophenone, benzyl, 4,4′-bis (dimethylamino) benzophenone (Michler's ketone), N, N′-dialkylaminobenzophenone etc.); ketals (eg acetophenone dimethyl ketal) Thioxanthenes (eg, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene); anthraquinones (eg, 2-ethylanthraquinone, 1-chloroanthraquinone, 1,2) -Benzanthraquinone, 2,3-diphenylanthraquinone, etc.); (thio) xanthones (for example, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopro Luthioxanthone, etc.); acridines (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-trimethyl) Benzoyldiphenylphosphine oxide, etc.); titanocene photopolymerization initiators; oxime esters. These photopolymerization initiators can be used alone or in combination of two or more.

[Photopolymerizable compound (D)]
The composition for forming a high refractive index pattern according to this embodiment may further contain a photopolymerizable compound (D). By including the photopolymerizable compound (D) in the composition for forming a high refractive index pattern, the curability of the coating film can be improved. As the photopolymerizable compound (D) contained in the composition for forming a high refractive index pattern, for example, an acrylate or 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, acryloylmorpholine, tetrahydrofurfryl 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, -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) a Liloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxypropyl hydrogen phthalate, 2- (meth ) Acryloyloxypropylhexahydrohydrogen phthalate, 2- (meth) acryloyloxypropyltetrahydrophthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) ) Acrylate, octafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, 2-adamantane and And adamantyl acrylate having a monovalent mono (meth) acrylate derived from 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.

〔solvent〕
The composition for forming a high refractive index pattern according to this embodiment may contain a solvent. As the solvent, 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 high refractive index pattern according to this embodiment may contain a conventional additive to the extent that the effect of the present invention is not inhibited 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.

  The coating liquid obtained by preparing the above materials is applied onto a substrate such as a polyethylene terephthalate (PET) film, a triacetyl cellulose (TAC) film, or a glass plate to form a photosensitive layer 12 for forming a high refractive index pattern. Is done.

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

  The composition for forming a high refractive index pattern comprises a metal oxide nanoparticle (A) surface-modified with a compound having a photopolymerizable reactive group and a compound (B) having absorption in the emission wavelength region of laser light. It is preferable that the total amount contains 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 (A) and the compound (B) is less than 25 wt% in the solid content, there is little energy that can be absorbed in the irradiated laser light, and the metal oxide nanoparticles (A) This is because the refractive index difference is not sufficient to form a high refractive index pattern between the first region 13 irradiated with the laser and the second region 14 not irradiated with the laser because of insufficient heating.

  The weight ratio of the metal oxide nanoparticles (A) surface-modified with a compound having a photopolymerizable reactive group to the compound (B) having absorption in the emission wavelength region of laser light is 99: 1 to 80: 20 is preferable. In particular, the ratio is preferably 98: 2 to 80:20. When the compound (B) having an absorption in the emission wavelength region of the laser beam is less than 1 wt%, the energy absorbed by the laser irradiation is small, and the metal oxide nanoparticles (A) are not heated sufficiently. In addition, there is a possibility that a refractive index difference sufficient for forming a high refractive index pattern between the first region 13 and the second region 14 not irradiated with the laser does not occur. On the other hand, when there is more compound (B) than 20 wt%, the sclerosis | hardenability of a coating film falls and a cured coating film may not be obtained.

  Moreover, it is desirable that the particle diameter of the metal oxide nanoparticles (A) 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 size is smaller than 1 nm, the particles are aggregated, so that a uniform coating film is not formed and a high refractive index pattern may not be produced uniformly. On the other hand, if the particle size is 100 nm or more, light may be scattered and the transparency of the coating film may be lost.

  Next, a method for forming a high refractive index pattern according to this embodiment will be described.

  The high refractive index pattern forming method has three steps of a high refractive index pattern forming composition forming step, a pattern drawing step, and a cured coating film forming step. Since the high refractive index pattern forming composition forming step is as described above, it is omitted here.

  First, the pattern drawing process will be described.

  As the pattern drawing process, an arbitrary pattern is created in advance by CAD or the like, and the first region 13 of the photosensitive layer 12 is exposed by laser irradiation to a desired position of the photosensitive layer 12 in accordance with the created pattern, so that high refraction is achieved. Rate pattern formation can be performed. Any laser may be used as long as the emission wavelength of the laser is within the absorption wavelength range of the photopolymerization initiator and metal oxide nanoparticles in the coating film. Thereby, the polymerization reaction of the laser irradiation part occurs, the metal oxide is heated, and the refractive index increases. As a result, only the first region 13 irradiated with the laser has a high refractive index, and a difference in refractive index occurs between the first region 13 irradiated with the laser and the second region 14 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 13 subjected to laser exposure and the second region 14 not subjected to laser exposure. 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. A semiconductor laser is particularly preferably used for reasons such as versatility of the apparatus.

  Next, the cured coating film forming step will be described.

  By irradiating ultraviolet rays to the photosensitive layer 12 on which the high refractive index pattern is drawn, the second region 14 not irradiated with laser is cured, and a cured coating film having a high refractive index pattern is formed. For irradiation 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.

  In addition, you may provide a heating process after forming a cured coating film. Examples of the heating means include heating using a heat source such as an oven, a hot plate, and an IR heater, blowing, and hot air.

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

  According to the composition for forming a high refractive index pattern and the method for forming a high refractive index pattern according to this embodiment, the first region irradiated with the laser beam and the laser beam are not irradiated by the polymerization and heating by laser irradiation. Since a refractive index difference is generated between the second region and the second region, 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.

  Examples of the present invention are shown below.

[Preparation of coating liquid]
(Preparation of photosensitive layer forming coating solution 1)
Methacryloyl group-modified titanium oxide nanoparticles (SR-0820, particle size 2 nm to 5 nm, toluene dispersion, manufactured by Daihachi Chemical Industry Co., Ltd.) with a solid content of 100 wt%, Irgacur 907 (BASF Japan ( Co., Ltd.) 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 photosensitive layer forming coating solution 2)
Methacryloyl group-modified titanium oxide nanoparticles (SR-0820, particle size 2 nm to 5 nm, toluene dispersion, manufactured by Daihachi Chemical Industry Co., Ltd.) in a solid content of 98 wt%, lanthanum hexaboride nanoparticles (KHF-7AH, Irgacure 907 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator is added at a solid content ratio of 5 wt% with respect to 2 wt% in the solid content of a particle size of 20 nm, toluene dispersion, manufactured by Sumitomo Metal Mining Co., Ltd. Dilution with toluene was performed so that the total solid content was 10 wt%.

(Preparation of photosensitive layer forming coating solution 3)
Methacryloyl group-modified titanium oxide nanoparticles (SR-0820, particle size 2 nm to 5 nm, toluene dispersion, manufactured by Daihachi Chemical Industry Co., Ltd.) in a solid content of 95 wt%, lanthanum hexaboride nanoparticles (KHF-7AH, Irgacure 907 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator is added at a solid content ratio of 5 wt% with respect to 5 wt% in the solid content of a particle size of 20 nm, toluene dispersion, manufactured by Sumitomo Metal Mining Co., Ltd. Dilution with toluene was performed so that the total solid content was 10 wt%.

(Preparation of photosensitive layer forming coating solution 4)
Methacryloyl group-modified titanium oxide nanoparticles (SR-0820, particle size 2 nm to 5 nm, toluene dispersion, manufactured by Daihachi Chemical Industry Co., Ltd.) in a solid content of 90 wt%, lanthanum hexaboride nanoparticles (KHF-7AH, Irgacure 907 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator is added at a solid content ratio of 5 wt% with respect to 10 wt% in the solid content of a particle size of 20 nm, toluene dispersion, manufactured by Sumitomo Metal Mining Co., Ltd. Dilution with toluene was performed so that the total solid content was 10 wt%.

(Preparation of photosensitive layer forming coating solution 5)
Methacryloyl group-modified titanium oxide nanoparticles (SR-0820, particle size 2 nm to 5 nm, toluene dispersion, manufactured by Daihachi Chemical Industry Co., Ltd.) in a solid content of 70 wt%, lanthanum hexaboride nanoparticles (KHF-7AH, Irgacure 907 (manufactured by BASF Japan Ltd.) as a photopolymerization initiator is added at a solid content ratio of 5 wt% with respect to 30 wt% in the solid content of a particle size of 20 nm, toluene dispersion, manufactured by Sumitomo Metal Mining Co., Ltd. Dilution with toluene was performed so that the total solid content was 10 wt%.

(Preparation of photosensitive layer forming coating solution 6)
Methacryloyl group-modified titanium oxide nanoparticles (SR-0820, particle size 2 nm to 5 nm, toluene dispersion, manufactured by Daihachi Chemical Industry Co., Ltd.) in a solid content of 95 wt%, ATO nanoparticles (ELCOM V-3508, particle size) 8 nm, PGME dispersion, manufactured by JGC Catalysts & Chemicals Co., Ltd.) with 5 wt% in solid content, Irgacure 907 (manufactured by BASF Japan Co., Ltd.) as a photopolymerization initiator is added at a solid content ratio of 5 wt%, and the whole The solution was diluted with toluene so that the solid content was 10 wt%.

(Preparation of photosensitive layer forming coating solution 7)
Methacryloyl group-modified titanium oxide nanoparticles (SR-0820, particle size 2 nm or more and 5 nm or less, toluene dispersion, manufactured by Daihachi Chemical Industry Co., Ltd.) in a solid content of 90 wt%, ATO nanoparticles (ELCOM V-3508, particle size) 8 nm, PGME dispersion, manufactured by JGC Catalysts & Chemicals Co., Ltd.) is 10 wt% in the solid content, and Irgacure 907 (manufactured by BASF Japan Co., Ltd.) is added as a photopolymerization initiator in a solid content ratio of 5 wt%. The solution was diluted with toluene so that the solid content was 10 wt%.

(Preparation of photosensitive layer forming coating solution 8)
Methacryloyl group-modified titanium oxide nanoparticles (SR-0820, particle size 2 nm or more and 5 nm or less, toluene dispersion, manufactured by Daihachi Chemical Industry Co., Ltd.) in solid content of 80 wt%, ATO nanoparticles (ELCOM V-3508, particle size) 8 nm, PGME dispersion, manufactured by JGC Catalysts & Chemicals Co., Ltd.) with a solid content of 20 wt%, Irgacur 907 (manufactured by BASF Japan Co., Ltd.) as a photopolymerization initiator was added at a solid content ratio of 5 wt%. The solution was diluted with toluene so that the solid content was 10 wt%.

(Preparation of photosensitive layer forming coating solution 9)
A methacryloyl group-modified titanium oxide nanoparticle (SR-0820, particle size 2 nm to 5 nm, toluene dispersion, manufactured by Daihachi Chemical Industry Co., Ltd.) in a solid content of 70 wt%, ATO nanoparticle (ELCOM V-3508, particle size) 8 nm, PGME dispersion, manufactured by JGC Catalysts & Chemicals Co., Ltd.) and 30 wt% in solid content, Irgacure 907 (manufactured by BASF Japan Co., Ltd.) as a photopolymerization initiator is added at a solid content ratio of 5 wt%. The solution was diluted with toluene so that the solid content was 10 wt%.

(Preparation of photosensitive layer forming coating solution 10)
Solid titanium oxide nanoparticles (NSU-399JPF-7, particle size 10 nm, 1-methoxy-2-propanol (hereinafter referred to as PGME) dispersion, manufactured by Nagase ChemteX Corporation) surface-modified with non-photopolymerizable compound The solid content ratio of Irgacure 907 (manufactured by BASF Japan Co., Ltd.) as a photopolymerization initiator with respect to 80 wt% in the content and 20 wt% in the solid content of pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) 5 wt%, and diluted with PGME so that the total solid content was 10 wt%.

(Preparation of photosensitive layer forming coating solution 11)
Titanium oxide nanoparticles (NSU-399JPF-7, particle size 10 nm, PGME dispersion, manufactured by Nagase ChemteX Co., Ltd.) surface-modified with a compound having no photopolymerizability, 60 wt% in solid content, pentaerythritol triacrylate ( PE-3A (manufactured by Kyoeisha Chemical Co., Ltd.) is 40 wt% in the solid content, and Irgacure 907 (manufactured by BASF Japan Ltd.) is added as a photopolymerization initiator in a solid content ratio of 5 wt%. It diluted with PGME so that it might become 10 wt%.

(Preparation of photosensitive layer forming coating solution 12)
Methacryloyl group-modified titanium oxide nanoparticles (SR-0820, particle size 2 nm to 5 nm, toluene dispersion, manufactured by Daihachi Chemical Industry Co., Ltd.) in a solid content of 72 wt%, lanthanum hexaboride nanoparticles (KHF-7AH, Particle size 20 nm, toluene dispersion, manufactured by Sumitomo Metal Mining Co., Ltd.) in solid content 8 wt% and pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) in solid content 20 wt%, Irgacure 907 (manufactured by BASF Japan Ltd.) was added as a photopolymerization initiator in a solid content ratio of 5 wt%, and diluted with toluene so that the total solid content was 10 wt%.

(Preparation of photosensitive layer forming coating solution 13)
Methacryloyl group-modified titanium oxide nanoparticles (SR-0820, particle size 2 nm to 5 nm, toluene dispersion, manufactured by Daihachi Chemical Industry Co., Ltd.) in a solid content of 54 wt%, lanthanum hexaboride nanoparticles (KHF-7AH, The particle size is 20 m, toluene dispersion, manufactured by Sumitomo Metal Mining Co., Ltd.) in solid content of 6 wt%, and pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) in solid content of 40 wt%. Irgacure 907 (manufactured by BASF Japan Ltd.) was added as a photopolymerization initiator in a solid content ratio of 5 wt%, and diluted with toluene so that the total solid content was 10 wt%.

(Preparation of photosensitive layer forming coating solution 14)
Methacryloyl group-modified titanium oxide nanoparticles (SR-0820, particle size of 2 nm to 5 nm, toluene dispersion, manufactured by Daihachi Chemical Industry Co., Ltd.) in a solid content of 36 wt%, lanthanum hexaboride nanoparticles (KHF-7AH, Particle size 20 nm, toluene dispersion, manufactured by Sumitomo Metal Mining Co., Ltd.) 4 wt% in solid content, and pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) in 60 wt% in solid content, Irgacure 907 (manufactured by BASF Japan Ltd.) was added as a photopolymerization initiator in a solid content ratio of 5 wt%, and diluted with toluene so that the total solid content was 10 wt%.

(Preparation of photosensitive layer forming coating solution 15)
Methacryloyl group-modified titanium oxide nanoparticles (SR-0820, particle size 2 nm to 5 nm, toluene dispersion, manufactured by Daihachi Chemical Industry Co., Ltd.) in a solid content of 18 wt%, lanthanum hexaboride nanoparticles (KHF-7AH, The particle size is 20 nm, the toluene dispersion, manufactured by Sumitomo Metal Mining Co., Ltd.) is 2 wt% in the solid content, and the pentaerythritol triacrylate (PE-3A, manufactured by Kyoeisha Chemical Co., Ltd.) is 80 wt% in the solid content. Irgacure 907 (manufactured by BASF Japan Ltd.) was added as a photopolymerization initiator in a solid content ratio of 5 wt%, and diluted with toluene so that the total solid content was 10 wt%.

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

[Example 1]
A laser drawing apparatus in which a coating solution 2 for forming a photosensitive layer is applied on a transparent glass substrate using a doctor blade so that the film thickness after curing is 600 nm, and dried in an oven at 60 ° C. for 1 minute, and a pattern is taken in. Was used to irradiate with a laser output of 0.3 W to form a pattern on the coating film. Thereafter, ultraviolet rays were irradiated at an exposure amount of 400 mJ / cm ² under a nitrogen purge to cure the uncured portion and produce a cured coating film.

[Example 2]
A cured coating film was prepared in the same manner as in Example 1 except that the photosensitive layer forming coating solution 3 was used instead of the photosensitive layer forming coating solution 2 and the laser output was changed to 0.1 W.

[Example 3]
A cured coating film was produced in the same manner as in Example 2 except that the laser output was 0.2 W.

[Example 4]
A cured coating film was produced in the same manner as in Example 2 except that the laser output was 0.3 W.

[Examples 5 to 7]
A cured coating film was prepared in the same manner as in Examples 2 to 4 except that the photosensitive layer forming coating solution 4 was used instead of the photosensitive layer forming coating solution 3.

[Example 8]
A cured coating film was prepared in the same manner as in Example 1 except that the photosensitive layer forming coating solution 6 was used instead of the photosensitive layer forming coating solution 2.

[Example 9]
A cured coating film was prepared in the same manner as in Example 1 except that the photosensitive layer forming coating solution 7 was used instead of the photosensitive layer forming coating solution 2 and the laser output was 0.2 W.

[Example 10]
A cured coating film was prepared in the same manner as in Example 1 except that the photosensitive layer forming coating solution 7 was used instead of the photosensitive layer forming coating solution 2.

[Examples 11 to 13]
A cured coating film was prepared in the same manner as in Examples 2 to 4 except that the photosensitive layer forming coating solution 8 was used instead of the photosensitive layer forming coating solution 2.

[Comparative Example 1]
A cured coating film was prepared in the same manner as in Example 1 except that the photosensitive layer forming coating solution 1 was used instead of the photosensitive layer forming coating solution 2.

[Comparative Example 2]
A cured coating film was produced in the same manner as in Comparative Example 1 except that the laser output was 0.5 W.

[Comparative Example 3]
A cured coating film was produced in the same manner as in Comparative Example 1 except that the laser output was 1.0 W.

[Comparative Example 4]
A cured coating film was prepared in the same manner as in Example 1 except that the photosensitive layer forming coating solution 5 was used instead of the photosensitive layer forming coating solution 2.

[Comparative Example 5]
A cured coating film was prepared in the same manner as in Example 1 except that the photosensitive layer forming coating solution 9 was used instead of the photosensitive layer forming coating solution 2.

[Comparative Example 6]
A cured coating film was prepared in the same manner as in Example 1 except that the photosensitive layer forming coating solution 10 was used instead of the photosensitive layer forming coating solution 2.

[Comparative Example 7]
A cured coating film was prepared in the same manner as in Example 1 except that the photosensitive layer forming coating solution 11 was used instead of the photosensitive layer forming coating solution 2 and the laser output was 1.0 W.

[Example 14]
A cured coating film was prepared in the same manner as in Example 1 except that the photosensitive layer forming coating solution 12 was used instead of the photosensitive layer forming coating solution 2 and the laser output was 0.1 W.

[Example 15]
A cured coating film was prepared in the same manner as in Example 1 except that the photosensitive layer forming coating solution 13 was used instead of the photosensitive layer forming coating solution 2 and the laser output was 0.2 W.

[Example 16]
A cured coating film was prepared in the same manner as in Example 1 except that the photosensitive layer forming coating solution 14 was used instead of the photosensitive layer forming coating solution 2 and the laser output was 1.0 W.

[Comparative Example 8]
A cured coating film was prepared in the same manner as in Example 1 except that the photosensitive layer forming coating solution 15 was used instead of the photosensitive layer forming coating solution 2 and the laser output was changed to 1.0 W.

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 of Examples 1 to 13 and Comparative Examples 1 to 7 are shown in Table 1.

  In Examples 1 to 13, a high refractive index pattern was formed, and diffracted light was confirmed.

  In Comparative Examples 1 and 2, only the metal oxide nanoparticles (A) surface-modified with a compound having a photopolymerizable reactive group are used, and the compound (B) having absorption in the emission wavelength region of the laser beam is not used. Therefore, the diffracted light could not be confirmed unless the surface of the substrate was blackened. In Comparative Example 3, diffracted light was clearly confirmed, but the output of the laser light had to be increased as compared with the Example. From this, when the compound (B) is not added, the energy absorbed by laser irradiation is small, and the metal oxide nanoparticles (A) are not sufficiently heated, so that the efficiency of polymerization and heating by laser irradiation is reduced. It was found that a difference in refractive index sufficient to form a high refractive index pattern hardly occurs between the first region 13 irradiated with the laser and the second region 14 not irradiated with the laser.

  When the content of the metal oxide nanoparticles (A) surface-modified with the compound having a photopolymerizable reactive group in Comparative Examples 4 to 5 is small, the cured coating film has low curability. I can't get it.

  In Comparative Example 6, when the non-photopolymerizable metal oxide nanoparticles and the photopolymerizable compound (D) are used and the compound (B) having absorption in the emission wavelength region of the laser beam is not used, It was found that a cured coating film could not be obtained because the content was large and the curability of the coating film was low.

  In Comparative Example 7, when the non-photopolymerizable metal oxide nanoparticles and the photopolymerizable compound (D) are used and the compound (B) having absorption in the emission wavelength region of the laser beam is not used, the laser beam It was found that even if the output of is increased, there is no difference in refractive index between the first region 13 irradiated with the laser and the second region 14 not irradiated with the laser, and no diffracted light is observed.

  Table 2 shows the evaluation results of Examples 14 to 16 and Comparative Example 8.

  In Examples 14 to 16, a high refractive index pattern was formed, and diffracted light was confirmed.

  In Comparative Example 8, when the total content of the metal oxide nanoparticles (A) surface-modified with the compound having a photopolymerizable reactive group and the compound (B) having absorption in the emission wavelength region of laser light is small In this case, diffracted light could not be confirmed. Therefore, when the total content of the metal oxide nanoparticles (A) and the compound (B) is small, the energy that can be absorbed in the irradiated laser light is small, and the metal oxide nanoparticles (A) are sufficient. Thus, it was found that there was no difference in refractive index between the first region 13 irradiated with the laser and the second region 14 not irradiated with the laser so that diffracted light was confirmed.

  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 Photosensitive layer 13 1st area | region 14 2nd area | region

Claims (7)

Metal oxide nanoparticles (A) surface-modified with a compound having at least a photopolymerizable reactive group;
Compound (B) having absorption in the emission wavelength region of laser light,
A photopolymerization initiator (C),
The total content of the metal oxide nanoparticles (A) and the compound (B) is 25 wt% or more in solid content,
A composition for forming a high refractive index pattern, wherein the weight ratio of the metal oxide nanoparticles (A) to the compound (B) is 99: 1 to 80:20.   The composition for forming a high refractive index pattern according to claim 1, further comprising a photopolymerizable compound (D).   3. The high refractive index according to claim 1, wherein the metal oxide constituting the metal oxide nanoparticles (A) is any one of titanium oxide, zirconium oxide, zinc oxide, and tin oxide. Pattern forming composition.   The composition for forming a high refractive index pattern according to any one of claims 1 to 3, wherein the metal oxide nanoparticles (A) have a particle size of 1 nm or more and 100 nm or less. A step of forming a photosensitive layer by laminating the composition for forming a high refractive index pattern according to claim 1 on a substrate;
Irradiating the photosensitive layer with laser light according to a predetermined pattern to form a high refractive index pattern;
A method of forming a high refractive index pattern, comprising: irradiating the photosensitive layer with ultraviolet rays to cure a region not irradiated with the laser beam. A laminate in which a high refractive index pattern is formed,
A substrate;
A photosensitive layer laminated on the substrate using the composition for forming a high refractive index according to any one of claims 1 to 4,
The photosensitive layer includes a first region irradiated with laser light and a second region not irradiated with laser light,
A laminate in which the first region and the second region have different refractive indexes to form the high refractive index pattern.   An optical element comprising the laminate according to claim 6.