Radiation sensitive refractive index changing composition, pattern forming method and optical material

Composition that is sensitive to radiation and changes in refractive index, method for forming pattern, and optical material

The present invention relates to a composition that is sensitive to radiation and changes in refractive index, a method of forming a refractive index pattern, a refractive index pattern, and an optical material. More specifically, it relates to a method of forming a refractive index pattern, which provides a novel refractive index pattern. And optical materials used in the fields of optoelectronics and display, and compositions suitable for use in this method that are sensitive to radiation and change in refractive index.

In the modern society called the "multimedia society", there is a great demand for refractive index profiled optical molded products each composed of different refractive index regions. This product includes not only optical fibers for transmitting information, but also In optical diffraction gratings and optical memories with periodic changes in refractive index, the information is written in parts with different refractive indexes, optical coupling elements such as optical ICs with fine refractive index patterns, optical control elements, optical modulation elements, and optical Transfer components.

Refractive index distribution type optical molded products can be divided into two types: one has a continuous refractive index distribution in the product, such as GI-type optical fiber (hereinafter referred to as "GRIN optical molded product") and the other has a discontinuous refractive index distribution, For example, optical diffraction gratings and SI-type optical waveguides.

GRIN optical molding products attract a lot of attention as the next generation of optical molding products. For example, a GI-type optical fiber whose refractive index decreases from the center axis of the fiber core in a parabolic form can transmit a lot of information. The refractive index Among them, the continuously changing GRIN lens is used as a reading lens in a photocopier. It is a spherical lens or microscope lens used to connect fibers. It uses its characteristics to have refractive power even on a flat surface, and it has no spherical aberration.

Many methods have been proposed so far for the production of the above-mentioned GRIN optical molded products, such as JP-A 9-133813, JP-A 8-336911, JP-A 8-337609, JP-A 3-192310, JP-A 5-60931 (The term "JP-A" as used herein refers to "Unchecked Publication of Japanese Patent Application"), WO93/19505 and WO94/04949 disclose that low molecular weight compounds or monomers are dispersed into polymers and their concentrations are continuously distributed. For the method of obtaining GI optical fiber, JP-A 62-25705 discloses that rod-shaped GI optical molded products or optical fibers are obtained by photo-copolymerization of two or more vinyl monomers with different refractive indexes and reactivity ratios. In addition, JP-A 7-56026 discloses a method of obtaining a refractive index distribution by forming a polymer A containing a photo-reactive functional group, and dispersing a compound B having a lower refractive index than polymer A into polymer A to form a compound The concentration of B is distributed, and the polymer A and compound B are photo-reacted.

Some methods of producing GRIN optical molded products of inorganic materials have also been proposed. For example, one of them is the method of producing GI-shaped rods, which is achieved by adding high refractive index thallium to rod-shaped glass consisting essentially of silicon or lead. The glass is immersed in a molten solution containing potassium with a low refractive index, and the potassium concentration distribution is formed through ion exchange.

The GRIN lens can similarly be obtained by applying the above method to a short rod, that is, an optically molded product similar to the lens, or alternatively, the GI type rod manufactured by the above method can be sliced.

In one of the methods for manufacturing optical molded products with fine refractive index patterns, such as the above-mentioned optical diffraction gratings or optical ICs, a technique is known to obtain changes in refractive index through the photochemical reaction of the molded products caused by exposure to light. For example, in the case of inorganic materials, germanium-doped glass changes its refractive index after exposure to light to produce optical diffraction gratings. In the case of organic materials, the above technique is called photochromium reaction or photobleaching, JP-A 7-92313 discloses a technique to disperse a photochemical reaction in a polymer by exposure to laser light, causing the refractive index of a material containing low molecular weight compounds to change, thereby obtaining an optical diffraction grating. In addition, JP-A 9-178901 recently proposed This technology is applied for the manufacture of GRIN optical molded products. This method uses the phenomenon that light is applied to the molded product to be absorbed and the strength is weakened to provide a continuous refractive index distribution in the deep direction after radiation.

However, in the refractive index distribution obtained by using the above-mentioned materials, the maximum refractive index difference is only about 0.001 to 0.02, and it is difficult to provide a wider refractive index distribution for preventing optical loss and suppressing circuit failure.

Moreover, when the above-mentioned conventional materials are used in a situation where the wavelength of the light is close to the refractive index wavelength after the refractive index distribution is formed, it is impossible to prevent the phenomenon that the refractive index gradually changes, thereby causing deterioration.

The purpose of the present invention is to provide a refractive index pattern and a method for obtaining an optical material by changing the refractive index of the material by a simple method, the refractive index difference of which is large enough and stable regardless of the use situation, and a novel method for its formation.

The other objects and advantages of the present invention can be better understood from the following description.

According to the present invention, first of all, the above-mentioned objects and advantages of the present invention are achieved through a combination of (A) inorganic oxide particles, (B) polymerizable compounds, (C) radiation-sensitive decomposers, and (D) escapeable compounds. Achieved by a composition that is sensitive to radiation and changes in refractive index.

Secondly, the above-mentioned objects and advantages of the present invention are achieved through a method of forming a refractive index pattern, including applying radiation to the above-mentioned composition part that is sensitive to radiation and changes in refractive index.

Third, the above-mentioned objects and advantages of the present invention are achieved by forming a refractive index pattern through the above-mentioned method of forming a refractive index pattern.

In the fourth aspect, the above-mentioned objects and advantages of the present invention are achieved by forming a refractive index pattern on an optical material through the above-mentioned method of forming a refractive index pattern.

In the present invention, "refractive index pattern" refers to a refractive index distribution type material containing regions with different refractive indexes.

Detailed description of preferred embodiments

The components of the refractive index-changing composition used in the present invention will be described in detail as follows.

(A) Inorganic oxide particles

Almost all kinds of inorganic oxide particles can be used as component (A). Preferably, the inorganic oxide particles are stable against acids, alkalis, or radicals formed from the radiation-sensitive decomposer (C) described below. It absorbs light passing through it and has a specific wavelength range, and has high optical transparency. According to the application purpose, a better value can be selected as the refractive index of the oxide particles.

Preferred examples of oxide particles include atoms containing such as Me, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W Oxides of Zn, B, Al, Si, Ge, Sn, Pb, Bi or Te. More preferable examples of oxide particles include oxides such as BeO, MgO, CaO, SrO, BaO, Sc₂O₃, Y₂O₃, La₂O₃, Ce₂O₃, Gd₂O₃, Tb₂O₃, Dy₂O₃, Yb₂O₃, Lu₂O₃, TiO₂, ZrO₂, HfO₂, Nb₂O₃, MoO₃, WO₃, ZnO, B₂O₃, Al₂O₃, SiO₂, GeO₂, SnO₂, PbO, Bi₂O₃TeO₂, And composite oxides containing these such as Al₂O₃-MgO, Al₂O₃-SiO₂, ZnO-Y₂O₃, ZrO₂-Ce₂O₃, ZrO₂-TiO₂-SnO₂, TeO₂-BaO-ZnO, TeO₂-WO₃-Ta₂O₅, TeO₂-WO₃-Bi₂O₃, TeO₂-BaO-PbO, CaO-Al₂O₃, CaO-Al₂O₃-BaO, CaO-Al₂O₃-Na₂O, CaO-Al₂O₃-K₂O, CaO-Al₂O₃-SiO₂, PbO-Bi₂O₃-BaO, PbO-Bi₂O₃-ZnO, PbO-Bi₂O₃, PbO-Bi₂O₃-BaO-ZnO, PbO-Bi₂O₃-CdO-Al₂O₃, PbO-Bi₂O₃-GeO₂, PbO-Bi₂O₃-GeO₂-Tl₂O, BaO-PbO-Bi₂O₃, BaO-PbO-Bi₂O₃-ZnO, Bi₂O₃-Ga₂O₃-PbO, Bi₂O₃-Ga₂O₃-CdO and Bi₂O₃-Ga₂O₃-(Pb,Cd)O.

The particle diameter of the oxide particles is preferably smaller than the wavelength of the light used to change the refractive index of the composition of the present invention, and may be, for example, 2 microns or less, more preferably 0.2 microns or less, and particularly preferably 0.1 microns or more. Small, when the particle diameter is greater than 2 microns, the transparency of the resulting refractive index changed composition may decrease or the surface state of the film obtained therefrom may be problematic.

The shape of the oxide particles is not particularly limited, but it is more preferable to be substantially spherical because the scattering of incident light is small.

The above-mentioned oxide particles can be contacted with a silane coupling agent, a surfactant, or a coordination compound capable of coordinating metal atoms to form an oxide, so as to modify the surface of the particle before use.

(B) Polymerizable compound

Polymers whose crosslinking density is increased by acids, bases, or radicals formed from decomposing agents (C) sensitive to radiation can be used as polymerizable compounds (B). Component (B) is, for example, containing ethylenic unsaturated bonds, ring Oxy group, sulfide group,<img file="TWI289727B_D0001.tif" />Oxetanyl,<img file="TWI289727B_D0002.tif" />Azole,<img file="TWI289727B_D0003.tif" />Or maleimide-based polymers, or alkoxy-containing polysiloxanes.

Contains ethylenically unsaturated bonds, epoxy groups, sulfide groups,<img file="TWI289727B_D0004.tif" />Tanky,<img file="TWI289727B_D0005.tif" />Azole,<img file="TWI289727B_D0006.tif" />The polymer containing epoxy group or maleimide group can contain epoxy group, cyclic sulfide group,<img file="TWI289727B_D0007.tif" />Tanky,<img file="TWI289727B_D0008.tif" />Azole,<img file="TWI289727B_D0009.tif" />Homopolymers of monomers based on the base or maleimide group, or copolymers of the above-mentioned monomers and other base-based polymerizable monomers. Examples of other base-based polymerizable monomers include monocarboxylic acids such as acrylic acid, Methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; anhydrides of these dicarboxylic acids; alkyl methacrylates such as methyl methacrylate , Ethyl methacrylate, n-butyl methacrylate, second butyl methacrylate and tertiary butyl methacrylate; alkyl acrylates such as methyl acrylate and isopropyl acrylate; cyclic alkyl methacrylate For example, cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclic methacrylate [5.2.1.0^2,6] Deca-8-ester (commonly known as dicyclopentyl methacrylate in this technical field), dicyclopentyloxyethyl methacrylate and isobornyl methacrylate; alkyl cyclic acrylates such as cyclohexyl acrylate , 2-methylcyclohexyl acrylate and tricyclic acrylate [5.2.1.0^2,6] Deca-8-ester (commonly known as dicyclopentyl acrylate in this technical field), dicyclopentyloxyethyl acrylate and isobornyl acrylate; aryl methacrylates such as phenyl methacrylate and benzyl methacrylate Esters; aryl acrylates such as phenyl acrylate and benzyl acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; hydroxyalkyl esters such as methacrylic acid 2- Hydroxyethyl and 2-hydroxypropyl methacrylate; and styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, Acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene and 2,3-dimethyl -1,3-butadiene, these base-based polymerizable monomers can be used alone or in combination of two or more.

Examples of monomers containing ethylenically unsaturated bonds include allyl acrylate, allyl methacrylate, allyl acrylate α-ethyl, allyl acrylate α-n-propyl, allyl acrylate α-n-butyl Ester, 1-butenyl acrylate, 1-butenyl methacrylate, 2-(2'-vinyloxyethoxy) ethyl acrylate, 2-(2'-vinyloxyethoxy methacrylate) ) Ethyl acrylate, 2-(2'-aryloxyethoxy) ethyl acrylate, 2-(2'-aryloxyethoxy) ethyl methacrylate, tetrahydrophthalate propylene oxy-normal Propyl ester and methacryloxy-n-propyl tetrahydrophthalate.

Examples of epoxy-containing monomers include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl acrylate α-n-propyl, glycidyl acrylate α-n-butyl, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, glycidyl methyl acrylate , Methyl methacrylate glycidyl ester, ethyl acrylate glycidyl ester, ethyl methacrylate glycidyl ester, n-propyl acrylate glycidyl ester, n-propyl methacrylate glycidyl ester, n-butyl acrylate glycidyl ester Ester, n-butyl methacrylate glycidyl ester, hydroxymethyl acrylate glycidyl ether, hydroxymethyl methacrylate glycidyl ether, 2-hydroxyethyl acrylate glycidyl ether, 2-hydroxyethyl methacrylate glycidyl ether Ether, 3-hydroxy n-propyl acrylate glycidyl ether, 3-hydroxy n-propyl methacrylate glycidyl ether, 4-hydroxy n-butyl acrylate glycidyl ether, 4-hydroxy n-butyl methacrylate glycidyl ether, 2,3-epoxycyclohexyl methyl acrylate, 2,3-epoxycyclohexyl methyl methacrylate, 3,4-epoxycyclohexyl methyl acrylate, 3,4-epoxycyclohexyl methyl methacrylate Esters, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 1,2-epoxy-3-vinylcyclohexane And 1,2-epoxy-4-vinylcyclohexane.

The cyclic sulfide group-containing monomer may be a monomer obtained by substituting the epoxy group of the above-mentioned epoxy group-containing monomer with a vinyl sulfide group, as shown in J. Org. Chem., 28, 229 (1963), for example.

Contain<img file="TWI289727B_D0010.tif" />Examples of monomers of tanky include 2-propenyloxy<img file="TWI289727B_D0011.tif" />Tan, 3-methacryloyloxy<img file="TWI289727B_D0012.tif" />Tan, 2-propenyloxymethyl<img file="TWI289727B_D0013.tif" />Tan, 2-methacryloxymethyl<img file="TWI289727B_D0014.tif" />Tan, 3-propenyloxymethyl<img file="TWI289727B_D0015.tif" />Tan, 3-methacryloxymethyl<img file="TWI289727B_D0016.tif" />Tan, 3-methyl-3-methacryloxymethyl<img file="TWI289727B_D0017.tif" />Tan, 3-methyl-3-propenyloxymethyl<img file="TWI289727B_D0018.tif" />Tan, 3-ethyl-3-propenyloxymethyl<img file="TWI289727B_D0019.tif" />Tan, 3-ethyl-3-methacryloxymethyl<img file="TWI289727B_D0020.tif" />Tan, 3-n-propyl-3-propenyloxymethyl<img file="TWI289727B_D0021.tif" />Tan, 3-n-propyl-3-methacryloxymethyl<img file="TWI289727B_D0022.tif" />Tan, 3-n-butyl-3-propenyloxymethyl<img file="TWI289727B_D0023.tif" />Tan, 3-n-butyl-3-methacryloxymethyl<img file="TWI289727B_D0024.tif" />Tan, acrylic 3-(2'-<img file="TWI289727B_D0025.tif" />Tanmethoxy) adamantyl ester, 3-(2'-methacrylic acid)<img file="TWI289727B_D0026.tif" />Tanmethoxy) adamantyl ester, acrylic acid 3-(2'-<img file="TWI289727B_D0027.tif" />Tanethoxy) adamantyl ester, 3-(2'-methacrylic acid)<img file="TWI289727B_D0028.tif" />Tanethoxy) adamantyl ester, acrylic acid 3-(2'-<img file="TWI289727B_D0029.tif" />Tan-n-propoxy)adamantyl ester, 3-(2'-methacrylic acid)<img file="TWI289727B_D0030.tif" />Tan-n-propoxy) adamantyl ester, 2-<img file="TWI289727B_D0031.tif" />Tanmethoxy proponene, 2-<img file="TWI289727B_D0032.tif" />Tanethoxy Probornene, 2-<img file="TWI289727B_D0033.tif" />Tan-n-propoxy proponyl, o-vinylbenzyl-2-<img file="TWI289727B_D0034.tif" />Methyl ether, m-vinylbenzyl-2-<img file="TWI289727B_D0035.tif" />Methyl ether and p-vinylbenzyl-2-<img file="TWI289727B_D0036.tif" />Tan methyl ether.

Contain<img file="TWI289727B_D0037.tif" />Examples of azole monomers include 2-propenyloxy<img file="TWI289727B_D0038.tif" />Oxazoline, 2-methacryloyloxy<img file="TWI289727B_D0039.tif" />Oxazoline, 2-propenyloxymethyl<img file="TWI289727B_D0040.tif" />Oxazoline, 2-methacryloyl methoxy<img file="TWI289727B_D0041.tif" />Oxazoline, 2-propenylmethoxy<img file="TWI289727B_D0042.tif" />Oxazoline, 2-methacryloyl ethoxy<img file="TWI289727B_D0043.tif" />Oxazoline, 2-propenyl ethoxy<img file="TWI289727B_D0044.tif" />Oxazoline, 2-allyl<img file="TWI289727B_D0045.tif" />Oxazoline, 2-isopropenyl-2-<img file="TWI289727B_D0046.tif" />Oxazoline, 2-(3-methyl-1-propenyl)<img file="TWI289727B_D0047.tif" />Oxazoline, 2-(4-butenyl)<img file="TWI289727B_D0048.tif" />Oxazoline and 2-n-Hanyl-2-<img file="TWI289727B_D0049.tif" />Oxazoline.

Contain<img file="TWI289727B_D0050.tif" />Examples of monomers include 2-propenyloxy<img file="TWI289727B_D0051.tif" />, 2-methacryloyloxy<img file="TWI289727B_D0052.tif" />, 2-propenyloxymethyl<img file="TWI289727B_D0053.tif" />, 2-methacryloyl methoxy<img file="TWI289727B_D0054.tif" />, 2-propenyl methoxy<img file="TWI289727B_D0055.tif" />, 2-Methylpropenylethoxy<img file="TWI289727B_D0056.tif" />, 2-propenylethoxy<img file="TWI289727B_D0057.tif" />, 2-allyl<img file="TWI289727B_D0058.tif" /><img file="TWI289727B_D0059.tif" />, 2-isopropenyl-2-<img file="TWI289727B_D0060.tif" />, 2-(3-methyl-1-propenyl)<img file="TWI289727B_D0061.tif" />, 2-(4-butenyl)<img file="TWI289727B_D0062.tif" />And 2-Non-Kanyl-2-<img file="TWI289727B_D0063.tif" />。

Examples of monomers containing maleimide groups include acrylic acid (3,4,5,6-tetrahydrophthalimino) methyl ester, methacrylic acid (3,4,5,6-tetrahydrophthalimide) Amino) methyl ester, (3,4,5,6-tetrahydrophthalimino) ethyl acrylate, (3,4,5,6-tetrahydrophthalimino) ethyl methacrylate, 3-(3,4,5,6-tetrahydrophthalimino) n-propyl acrylate, 3-(3,4,5,6-tetrahydrophthalimino) n-propyl methacrylate, N-vinylmaleimide, N-allylmaleimide, N-(2-isopropenyl)maleimide and N-(4-butenyl)maleimide .

Examples of polymerization solvents used to polymerize these monomers include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol alkyl groups Ether acetates such as methyl cellulose acetate and ethyl cellulose acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether And diethylene glycol ethyl methyl ether; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Propylene glycol propyl ether acetate and propylene glycol butyl ether acetate; propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; aromatic Group hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone; and esters such as methyl acetate, ethyl acetate, propyl acetate Ester, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, Butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3-hydroxypropionic acid Butyl ester, methyl 2-hydroxy-3-methylbutyrate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate , Ethoxy ethyl acetate, ethoxy propyl acetate, ethoxy butyl acetate, propoxy methyl acetate, propoxy ethyl acetate, propoxy propyl acetate, propoxy butyl acetate, Methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2- Propyl methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, 2- Butyl ethoxy propionate, methyl 2-butoxy propionate, ethyl 2-butoxy propionate, propyl 2-butoxy propionate, butyl 2-butoxy propionate, 3- Methyl methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxy propionate, 3-ethoxy propyl propionate, 3-ethoxy butyl propionate, 3-propoxy methyl propionate, 3-propoxy ethyl propionate, 3- Propoxy propionate, 3-propoxy butyl propionate, 3-butoxy methyl propionate, 3-butoxy ethyl propionate, 3-butoxy propyl propionate and 3-butoxy propionate DingButyloxypropionate.

Generally known free radical polymerization initiators can be used as polymerization initiators for the production of ethylenically unsaturated bonds, epoxy groups, sulfide groups,<img file="TWI289727B_D0064.tif" />Tanky,<img file="TWI289727B_D0065.tif" />Azole,<img file="TWI289727B_D0066.tif" />The polymer containing epoxy group or maleimide group can contain epoxy group, cyclic sulfide group,<img file="TWI289727B_D0067.tif" />Tanky,<img file="TWI289727B_D0068.tif" />Azole,<img file="TWI289727B_D0069.tif" />Examples of free radical polymerization initiators include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-(2,4 -Dimethylvaleronitrile); organic peroxides such as phenylperoxide, laurel peroxide, t-butyl peroxypivalate and 1,1-bis-(tert-butylperoxy)cyclohexane Alkane; and hydrogen peroxide. When peroxide is used as a radical polymerization initiator, it can be used in combination with a reducing agent as a redox initiator.

Contains ethylenically unsaturated bonds, epoxy groups, sulfide groups,<img file="TWI289727B_D0070.tif" />Tanky,<img file="TWI289727B_D0071.tif" />Azole,<img file="TWI289727B_D0072.tif" />The weight average molecular weight (hereinafter referred to as "Mw") of the polymer based on polystyrene or maleimide group is preferably 1x10³To 1x10⁵, More preferably 5x10³Up to 5x10⁴, When Mw is lower than 1x10³, The resulting coating film is not fully cured and it is difficult to obtain mechanical strength, when Mw is higher than 1x10⁵, It is difficult to obtain a high cross-linking contrast between the exposed part and the unexposed part, resulting in a small difference in refractive index between the exposed part and the unexposed part.

Polysiloxane is a hydrolysate of the compound represented by the following formula (1) or its condensate: R¹_nSi(OR²)_4-n (1) where R¹And R²It may be the same or different and each is a monovalent organic group, and n is an integer from 0 to 2.

In the above formula (1), the monovalent organic group is, for example, an alkyl group, an aryl group, an allyl group or a glyceryl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Up to 5 carbon atoms, these alkyl groups can be linear or branched and can also replace hydrogen atoms with halogen atoms such as fluorine atoms. In the above formula (1), the aryl group is, for example, phenyl or naphthyl, in the above formula ( In 1), n is preferably 1 or 2.

Examples of alkyl alkoxysilanes represented by the above formula (1) include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltriisopropoxysilane, methyl Tri-n-butoxysilane, methyl tri-second butoxy silane, methyl tri-tertiary butoxy silane, methyl triphenoxy silane, ethyl trimethoxy silane, ethyl triethoxy silane, Ethyl tri-n-propoxy silane, ethyl tri-isopropoxy silane, ethyl tri-n-butoxy silane, ethyl three second butoxy silane, ethyl three third butoxy silane, ethyl three Phenoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltri-n-propoxysilane, n-propyltriisopropoxysilane, n-propyltri-n-butoxy Silane, n-propyl three second butoxy silane, n-propyl three third butoxy silane, n-propyl triphenoxy silane, isopropyl trimethoxy silane, isopropyl triethoxy silane, Isopropyl tri-n-propoxy silane, isopropyl tri-isopropoxy silane, isopropyl tri-n-butoxy silane, isopropyl tri-n-butoxy silane, isopropyl tri-terti-butoxy silane Silane, isopropyltriphenoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-butyltri-n-propoxysilane, n-butyltriisopropoxysilane, n-butyl Tri-n-butoxy silane, n-butyl tri-second butoxy silane, n-butyl tri-tertiary butoxy silane, n-butyl triphenoxy silane, second butyl trimethoxy silane, second Butyl triethoxy silane, second butyl tri-n-propoxy silane, second butyl tri-isopropoxy silane, second butyl tri-n-butoxy silane, second butyl tri-second butoxy Base silane, second butyl tritertiary butoxy silane, second butyl triphenoxy silane, tertiary butyl trimethoxy silane, tertiary butyl triethoxy silane, tertiary butyl tri-n Propoxysilane, tertiary butyl triisopropoxy silane, tertiary butyl tri-n-butoxy silane, tertiary butyl tri-second butoxy silane, tertiary butyl tri-tertiary butoxy silane , Tertiary butyl triphenoxy silane, cyclohexyl trimethoxy silane, cyclohexyl triethoxy silane, cyclohexyl tri-n-propoxy silane, cyclohexyl tri-isopropoxy silane, cyclohexyl tri-n-butoxy Cyclohexyl tri-second butoxy silane, cyclohexyl tri-tertiary butoxy silane, cyclohexyl triphenoxy silane, n-Han group trimethoxy silane, n-Han group triethoxy silane, n-Han group Tri-n-propoxysilane, n-kanyl tri-isopropoxysilane, n-kanyl tri-n-butoxysilane, n-kanyl tri-second butoxy silane, n-kanyl tri-tertiary butoxy silane, N-Hanyl Triphenoxy Silane, Phenyl Trimethoxy Silane, Phenyl Triethoxy Silane, Phenyl Tri-n-Propoxy Silane, Phenyl Triisopropoxy Silane, Phenyl Tri-n-Butoxy Silane , Phenyl Tri-Second Butoxy SilicaAlkyl, phenyl tritertiary butoxy silane, phenyl triphenoxy silane, dimethyl dimethoxy silane, dimethyl diethoxy silane, dimethyl di-n-propoxy silane, dimethyl Diisopropoxy silane, dimethyl di-n-butoxy silane, dimethyl two second butoxy silane, dimethyl two third butoxy silane, dimethyl diphenoxy silane, two Ethyl dimethoxysilane, diethyldiethoxysilane, diethyldi-n-propoxysilane, diethyldiisopropoxysilane, diethyldi-n-butoxysilane, diethyl Di second butoxy silane, diethyl di tertiary butoxy silane, diethyl diphenoxy silane, di-n-propyl dimethoxy silane, di-n-propyl diethoxy silane, di-n Propyl di-n-propoxy silane, di-n-propyl diisopropoxy silane, di-n-propyl di-n-butoxy silane, di-n-propyl di-butoxy silane, di-n-propyl di-third Butoxysilane, di-n-propyl diphenoxy silane, diisopropyl dimethoxy silane, diisopropyl diethoxy silane, diisopropyl di-n-propoxy silane, diisopropyl Diisopropoxysilane, diisopropyl di-n-butoxy silane, diisopropyl di-n-butoxy silane, diisopropyl di-tertiary butoxy silane, diisopropyl diphenoxy Silane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-butyldi-n-propoxysilane, di-n-butyldiisopropoxysilane, di-n-butyldi-n- Butoxysilane, di-n-butyl di second butoxy silane, di-n-butyl di-tertiary butoxy silane, di-n-butyl diphenoxy silane, di-n-butyl dimethoxy silane, Di-second butyl diethoxy silane, di-second butyl di-n-propoxy silane, di-second butyl di-isopropoxy silane, di-second butyl di-n-butoxy silane, di-second butyl di-n-butoxy silane Butyl di 2 butoxy silane, di 2 butyl di 3 butoxy silane, di 2 butyl diphenoxy silane, di 3 butyl dimethoxy silane, di ter butyl Diethoxysilane, di-tertiary butyl di-n-propoxy silane, di-tertiary butyl diisopropoxy silane, di-tertiary butyl di-n-butoxy silane, di-tertiary butyl di-second Butoxysilane, di-tertiary butyl di-tertiary butoxy silane, di-tertiary butyl diphenoxy silane, dicyclohexyl dimethoxy silane, dicyclohexyl diethoxy silane, dicyclohexyl Di-n-propoxy silane, dicyclohexyl diisopropoxy silane, dicyclohexyl di-n-butoxy silane, dicyclohexyl two second butoxy silane, dicyclohexyl two third butoxy silane, two Cyclohexyl diphenoxysilane, di-n-hanyl dimethoxysilane, di-n-hanyl diethoxysilane, di-n-hanyl di-n-propoxy silane, di-n-hanyl diisopropoxy silane, Two-n-Hanyl Di-n-Butoxy Silane, Two-n-Hanyl Two Second Butoxy Silane, Two-n-Hanyl Two ThirdButoxysilane, Di-n-Hanyl Diphenoxy Silane, Diphenyl Dimethoxy Silane, Diphenyl Diethoxy Silane, Diphenyl Di-n-Propoxy Silane, Diphenyl Diisopropyl Oxide Diphenyl di-n-butoxy silane, diphenyl di-n-butoxy silane, diphenyl di-n-butoxy silane, diphenyl di-tertiary butoxy silane, diphenyl diphenoxy silane, divinyl dimethoxy silane Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glyceryloxypropyltrimethoxysilane, γ-glyceryloxypropyltriethoxy Cyclosilane, γ-trifluoropropyltrimethoxysilane and γ-trifluoropropyltriethoxysilane, also including those obtained by extracting part or all of the hydrogen atoms of the above-mentioned alkyl alkoxysilanes with fluorine atoms Compounds, these alkyl alkoxysilanes can be used alone or in combination of two or more.

Among the compounds represented by the above formula (1), alkyltrialkoxysilanes are preferred, where n is 1, and methyltrimethoxysilane and methyltriethoxysilane are particularly preferred. When methyltrimethoxysilane is used Silane and/or methyltriethoxysilane is used in 70 mol% or more based on the total amount of all alkyl alkoxysilanes , which is beneficial to obtain a good balance between heat resistance and refractive index. A balanced cured product. The hydrolyzed product of the compound represented by the above formula (1) and its condensate is better than this compound. When the component (B) is the condensate of the compound represented by the above formula (1), under polystyrene The weight average molecular weight is preferably 500 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight under polystyrene is less than 500, the resulting coating film is not fully cured and it is difficult to obtain mechanical strength. The weight average molecular weight under styrene is higher than 100,000. It is difficult to obtain a high crosslinking contrast between the exposed part and the unexposed part, resulting in a small difference in refractive index between the exposed part and the unexposed part.

The hydrolysis reaction and/or condensation reaction of the hydrolyzed product of the compound represented by formula (1) and/or its condensate above component (B) is carried out in the presence of water and a suitable catalyst and will be described below.

To be more certain, the compound represented by the above formula (1) is dissolved in a suitable organic solvent, and water is added intermittently or continuously to the resulting solution. The catalyst can be dissolved or dispersed in the organic solvent, or dissolved or dispersed in the added solution. In the water.

The temperature of the current hydrolysis and/or condensation reaction is preferably 0 to 100°C, more preferably 15 to 80°C.

The water used for the hydrolysis and/or condensation reaction of the compound represented by the above formula (1) is not particularly limited, but ion exchange water is preferred.

The amount of water is 0.25 to 3 mol, preferably 0.3 to 2.5 mol, and R of the compound represented by formula (1) above 1 mol²The total number of bases represented by O- is the benchmark.

The catalyst used for the hydrolysis and/or condensation reaction of the compound represented by the above formula (1) is, for example, a metal chelate compound, an organic acid, an inorganic acid, an organic base, or an inorganic base.

Examples of metal chelating compounds used as catalysts include titanium chelating compounds such as triethoxy. Single (acetylacetonyl) titanium, tri-n-propoxy. Single (acetylacetonyl) titanium, triisopropoxy. Single (acetylacetonyl) titanium, tri-n-butoxy. Single (acetylacetonyl) titanium, three second butoxy. Single (acetylacetonyl) titanium, three third butoxy. Single (acetylacetonyl) titanium, diethoxy. Bis (acetylacetonyl) titanium, di-n-propoxy. Bis (acetylacetonyl) titanium, diisopropoxy. Bis (acetylacetonyl) titanium, di-n-butoxy. Bis (acetylacetonyl) titanium, two second butoxy. Bis (acetylacetonyl) titanium, two third butoxy. Bis (acetylacetonyl) titanium, monoethoxy. Participation (acetylacetonyl) titanium, mono-n-propoxy. Participation (acetylacetonyl) titanium, monoisopropoxy. Participation (acetylacetonyl) titanium, mono-n-butoxy. Participation (acetylacetonyl) titanium, single second butoxy. Participation (acetylacetonyl) titanium, single third butoxy. Participants (acetylacetonyl) titanium, Si (acetylacetonyl) titanium, triethoxy. Single (acetyl ethyl acetate) titanium, tri-n-propoxy. Single (acetyl ethyl acetate) titanium, triisopropoxy. Single (acetyl ethyl acetate) titanium, tri-n-butoxy. Single (acetyl ethyl acetate) titanium, three second butoxy. Single (acetyl ethyl acetate) titanium, three third butoxy. Single (acetyl ethyl acetate) titanium, diethoxy. Bis (acetyl ethyl acetate) titanium, di-n-propoxy. Bis (acetyl ethyl acetate) titanium, diisopropoxy. Bis (acetyl ethyl acetate) titanium, di-n-butoxy. Bis (acetyl ethyl acetate) titanium, two second butoxy. Bis (acetyl ethyl acetate) titanium, two third butoxy. Double (acetyl ethyl acetate) titanium, monoethyl. Ginseng (acetyl ethyl acetate) titanium, single n-propoxy. Ginseng (acetyl ethyl acetate) titanium, monoisopropoxy. Ginseng (acetyl ethyl acetate) titanium, single n-butoxy. Ginseng (acetyl ethyl acetate) titanium, single second butoxy. Ginseng (acetyl ethyl acetate) titanium, single third butoxy. Ginseng (acetyl ethyl acetate) titanium, Si (acetyl ethyl acetate) titanium, mono (acetyl acetonyl) ginseng (acetyl acetate) titanium, bis (acetyl acetonyl) bis (acetate) Ethyl acetate) titanium and ginseng (acetylacetonyl) single (acetate ethyl acetate) titanium; zirconium chelating compounds such as triethoxy. Single (acetylacetonyl) zirconium, tri-n-propoxy. Single (acetylacetonyl) zirconium, triisopropoxy. Single (acetylacetonyl) zirconium, tri-n-butoxy. Single (acetylacetonyl) zirconium, three second butoxy. Single (acetylacetonyl) zirconium, three third butoxy. Single (acetylacetonyl) zirconium, diethoxy. Bis (acetylacetonyl) zirconium, di-n-propoxy. Bis (acetylacetonyl) zirconium, diisopropoxy. Bis (acetylacetonyl) zirconium, di-n-butoxy. Bis (acetylacetonyl) zirconium, two second butoxy. Bis (acetylacetonyl) zirconium, two third butoxy. Bis (acetylacetonyl) zirconium, monoethoxy. Participation (acetylacetonyl) zirconium, single n-propoxy. Participation (acetylacetonyl) zirconium, monoisopropoxy. Participation (acetylacetonyl) zirconium, single n-butoxy. Participation (acetylacetonyl) zirconium, single second butoxy. Participation (acetylacetonyl) zirconium, single third butoxy. Participation (acetylacetonyl) zirconium, four (acetylacetonyl) zirconium, triethoxy. Single (acetyl ethyl acetate) zirconium, tri-n-propoxy. Single (acetyl ethyl acetate) zirconium, triisopropoxy. Single (acetyl ethyl acetate) zirconium, tri-n-butoxy. Single (acetyl ethyl acetate) zirconium, three second butoxy. Single (acetyl ethyl acetate) zirconium, three third butoxy. Single (acetyl ethyl acetate) zirconium, diethoxy. Bis (acetyl ethyl acetate) zirconium, di-n-propoxy. Bis (acetyl ethyl acetate) zirconium, diisopropoxy. Bis (acetyl ethyl acetate) zirconium, di-n-butoxy. Bis (acetyl ethyl acetate) zirconium, two second butoxy. Bis (acetyl ethyl acetate) zirconium, two third butoxy. Bis (acetyl ethyl acetate) zirconium, single ethoxy. Ginseng (acetyl ethyl acetate) zirconium, single n-propoxy. Ginseng (acetyl ethyl acetate) zirconium, monoisopropoxy. Ginseng (acetyl ethyl acetate) zirconium, single n-butoxy. Ginseng (acetyl ethyl acetate) zirconium, single second butoxy. Ginseng (acetyl ethyl acetate) zirconium, single third butoxy. Ginseng (acetyl ethyl acetate) zirconium, Si (acetyl ethyl acetate) zirconium, mono (acetylacetonyl) ginseng (acetyl acetate) zirconium, bis (acetyl acetonyl) bis (acetate) Ethyl acetate) zirconium, ginseng (acetylacetonyl) mono(acetate ethyl acetate) zirconium; and aluminum chelating compounds such as ginseng (acetylacetonyl) aluminum and ginseng (ethyl acetate) aluminum. (Ethyl acetate) zirconium, three second butoxy. Single (acetyl ethyl acetate) zirconium, three third butoxy. Single (acetyl ethyl acetate) zirconium, diethoxy. Bis (acetyl ethyl acetate) zirconium, di-n-propoxy. Bis (acetyl ethyl acetate) zirconium, diisopropoxy. Bis (acetyl ethyl acetate) zirconium, di-n-butoxy. Bis (acetyl ethyl acetate) zirconium, two second butoxy. Bis (acetyl ethyl acetate) zirconium, two third butoxy. Bis (acetyl ethyl acetate) zirconium, single ethoxy. Ginseng (acetyl ethyl acetate) zirconium, single n-propoxy. Ginseng (acetyl ethyl acetate) zirconium, monoisopropoxy. Ginseng (acetyl ethyl acetate) zirconium, single n-butoxy. Ginseng (acetyl ethyl acetate) zirconium, single second butoxy. Ginseng (acetyl ethyl acetate) zirconium, single third butoxy. Ginseng (acetyl ethyl acetate) zirconium, Si (acetyl ethyl acetate) zirconium, mono (acetyl acetonyl) ginseng (acetyl acetate) zirconium, bis (acetyl acetonyl) bis (acetate) Ethyl acetate) zirconium, ginseng (acetylacetonyl) mono(acetate ethyl acetate) zirconium; and aluminum chelating compounds such as ginseng (acetylacetonyl) aluminum and ginseng (ethyl acetate) aluminum. (Ethyl acetate) zirconium, three second butoxy. Single (acetyl ethyl acetate) zirconium, three third butoxy. Single (acetyl ethyl acetate) zirconium, diethoxy. Bis (acetyl ethyl acetate) zirconium, di-n-propoxy. Bis (acetyl ethyl acetate) zirconium, diisopropoxy. Bis (acetyl ethyl acetate) zirconium, di-n-butoxy. Bis (acetyl ethyl acetate) zirconium, two second butoxy. Bis (acetyl ethyl acetate) zirconium, two third butoxy. Bis (acetyl ethyl acetate) zirconium, single ethoxy. Ginseng (acetyl ethyl acetate) zirconium, single n-propoxy. Ginseng (acetyl ethyl acetate) zirconium, monoisopropoxy. Ginseng (acetyl ethyl acetate) zirconium, single n-butoxy. Ginseng (acetyl ethyl acetate) zirconium, single second butoxy. Ginseng (acetyl ethyl acetate) zirconium, single third butoxy. Ginseng (acetyl ethyl acetate) zirconium, Si (acetyl ethyl acetate) zirconium, mono (acetylacetonyl) ginseng (acetyl acetate) zirconium, bis (acetyl acetonyl) bis (acetate) Ethyl acetate) zirconium, ginseng (acetylacetonyl) mono(acetate ethyl acetate) zirconium; and aluminum chelating compounds such as ginseng (acetylacetonyl) aluminum and ginseng (ethyl acetate) aluminum.

Examples of organic acids used as catalysts include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, caprylic acid, pelargonic acid, capric acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, Sebacic acid, gallic acid, butyric acid, mellitic acid arachidonic acid, shikimic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, P-aminobenzoic acid, p-toluenesulfonic acid, phenylsulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid , Citric acid and tartaric acid.

Examples of inorganic acids used as catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

Examples of organic bases used as catalysts include pyridine, pyrrole, hexahydropyridine<img file="TWI289727B_D0073.tif" />, Pyrrolidine, hexahydropyridine, picolin, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonomethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, two Azabicyclononane, diazabicycloundecene and tetramethylammonium hydroxide.

Examples of inorganic bases used as catalysts include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide.

Among these catalysts, metal chelate compounds, organic acids and inorganic acids are more preferred, and titanium chelate compounds and organic acids are more preferred.

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

The amount of the catalyst is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 10 parts by weight, and 100 parts by weight are used in SiO₂The compound represented by the above formula (1) under the name is a reference.

After the compound represented by the above formula (1) is hydrolyzed and/or condensed, it is preferable to remove the remaining water and the alcohol produced as a by-product of the reaction.

The above-mentioned known compounds can be used as the polymerizable compound (B) in the present invention without limitation, but when the compound contains an aromatic ring, it is advantageous to use a halogen atom or a sulfur atom to increase the refractive index.

The hydrogen atoms contained in all the compounds listed in the above compound (B) can be through chlorine atoms, bromine atoms, hydroxyl groups, mercapto groups, alkoxy groups, alkylthio groups, haloalkyl groups, haloalkoxy groups, and haloalkylthio groups. , Thioester, mercaptoalkyl, aryl, aralkyl, or cyano substitution.

Examples of the above-mentioned alkoxy groups which may be linear or branched include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, first Tributoxy, n-pentyloxy, neopentyloxy and n-hexyloxy.

Examples of the aforementioned alkylthio groups that may be straight or branched include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, second butylthio, first Tributylthio, n-pentylthio, neopentylthio and n-hexylthio.

Examples of the above-mentioned haloalkyl which may be linear or branched include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, chloromethyl, 2-chloroethyl, 3-chloropropyl, 1-chloromethyl Base ethyl, 4-chlorobutyl, 2-chloromethylpropyl, 5-chloropentyl, 3-chloromethylbutyl, 2-chloroethylpropyl, 6-chlorohexyl, 3-chloromethyl Pentyl, 4-chloromethylpentyl, 2-chloroethylbutyl, bromomethyl, 2-bromoethyl, 3-bromopropyl, 1-bromomethylethyl, 4-bromobutyl, 2 -Bromomethylpropyl, 5-bromopentyl, 3-bromomethylbutyl, 2-bromoethylpropyl, 6-bromohexyl, 3-bromomethylpentyl, 4-bromomethylpentyl and 2-Bromoethylbutyl.

Examples of the above-mentioned haloalkoxy include trifluoromethoxy, pentafluoroethoxy, heptafluoropropoxy, chloromethoxy, 2-chloroethoxy, 3-chloropropoxy, 1-chloromethyl Ethoxy, 4-chlorobutoxy, 2-chloromethylpropoxy, 5-chloropentoxy, 3-chloromethylbutoxy, 2-chloroethylpropoxy, 6-chlorohexoxy Group, 3-chloromethylpentoxy, 4-chloromethylpentoxy, 2-chloroethylbutoxy, bromomethoxy, 2-bromoethoxy, 3-bromopropoxy, 1- Bromomethylethoxy, 4-bromobutoxy, 2-bromomethylpropoxy, 5-bromopentoxy, 3-bromomethylbutoxy, 2-bromoethylpropoxy, 6- Bromohexyloxy, 3-bromomethylpentyloxy, 4-bromomethylpentyloxy and 2-bromoethylbutoxy.

Examples of the above-mentioned haloalkylthio include trifluoromethylthio, pentafluoroethylthio, heptafluoropropylthio, chloromethylthio, 2-chloroethylthio, 3-chloropropylthio, 1-chloromethyl Ethylthio, 4-chlorobutylthio, 2-chloromethylpropylthio, 5-chloropentylthio, 3-chloromethylbutylthio, 2-chloroethylpropylthio, 6-chlorohexylthio Group, 3-chloromethylpentylthio, 4-chloromethylpentylthio, 2-chloroethylbutylthio, bromomethylthio, 2-bromoethylthio, 3-bromopropylthio, 1- Bromomethylethylthio, 4-bromobutylthio, 2-bromomethylpropylthio, 5-bromopentylthio, 3-bromomethylbutylthio, 2-bromoethylpropylthio, 6- Bromohexylthio, 3-bromomethylpentylthio, 4-bromomethylpentylthio and 2-bromoethylbutylthio.

Examples of the above-mentioned thioester group include acetyl-p-anisyl sulfonyl, propyl-p-anisyl sulfonyl, n-butyryl p-anisyl sulfonyl, isobutyryl p-anisyl sulfonyl, n-pentyl sulfonyl Aminobenzene sulfonyl, neopentyl p-aminobenzene sulfonyl and n-hexyl p-aminobenzene sulfonyl.

Examples of the above-mentioned mercaptoalkyl include mercaptomethyl, 2-mercaptoethyl, 3-mercaptopropyl, 1-mercaptomethylethyl, 4-mercaptobutyl, 2-mercaptomethylpropyl, 5-mercaptopentyl , 3-mercaptomethylbutyl, 2-mercaptoethylpropyl, 6-mercaptohexyl, 3-mercaptomethylpentyl, 4-mercaptomethylpentyl and 2-mercaptoethylbutyl.

Examples of the aforementioned aryl group include phenyl, tolyl, xylyl, cumenyl and 1-naphthyl.

Examples of the aforementioned aralkyl group include benzyl, α-methylbenzyl, phenethyl, and naphthylmethyl.

These compounds listed as component (B) can be used alone or in combination of two or more.

The amount of ingredient (B) is preferably 5 to 95 parts by weight, more preferably 10 to 90 parts by weight, based on the total of 100 parts by weight of ingredients (A) and (B), when ingredient (B) When the amount is less than 5 parts by weight, the material with changed refractive index is likely to become brittle, and when the equivalent is greater than 95 parts by weight, the difference in refractive index obtained is likely to become smaller.

(C) Decomposer sensitive to radiation

The radiation-sensitive decomposer (C) used in the present invention may be a radiation-sensitive acid generator, a radiation-sensitive base generator or a radiation-sensitive base generator. When the acid-reactive compound is used as a polymerizable When the compound (B) is used, it is better to use a radiation-sensitive acid generator as a radiation-sensitive decomposer (C). When the alkali-reactive compound is used as a polymerizable compound (B), it is better to use Radiation-sensitive base generators are used as radiation-sensitive decomposition agents (C), and when the base-reactive compound is used as polymerizable compound (B), it is more appropriate to use radiation-sensitive base generators as radiation-sensitive base generators. Sensitive decomposition agent (C) is used.

The above-mentioned radiation-sensitive acid generators are, for example, trichloromethyl-s-tris<img file="TWI289727B_D0074.tif" />, Diaryliodonium, triarylsulfonium, quaternary ammonium or sulfonate.

Trichloromethyl-s-tri<img file="TWI289727B_D0075.tif" />Examples include 2,4,6-ginseng (trichloromethyl)-s-tri<img file="TWI289727B_D0076.tif" />, 2-Phenyl-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0077.tif" />, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0078.tif" />, 2-(3-chlorophenyl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0079.tif" />, 2-(2-chlorophenyl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0080.tif" />, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0081.tif" />, 2-(3-Methoxyphenyl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0082.tif" />, 2-(2-Methoxyphenyl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0083.tif" />, 2-(4-Methylthiophenyl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0084.tif" />, 2-(3-Methylthiophenyl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0085.tif" />, 2-(2-Methylthiophenyl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0086.tif" />, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0087.tif" />, 2-(3-Methoxynaphthyl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0088.tif" />, 2-(2-Methoxynaphthyl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0089.tif" />, 2-(4-Methoxy-β-styryl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0090.tif" />, 2-(3-Methoxy-β-styryl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0091.tif" />, 2-(2-Methoxy-β-styryl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0092.tif" />, 2-(3,4,5-trimethoxy-β-styryl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0093.tif" />, 2-(4-Methylthio-β-styryl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0094.tif" />, 2-(3-Methylthio-β-styryl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0095.tif" />, 2-(3-Methylthio-β-styryl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0096.tif" />, 2-piperonyl-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0097.tif" />, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0098.tif" />, 2-[2-(5-Methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0099.tif" />And 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0100.tif" />。

Examples of the aforementioned diaryl iodonium salts include diphenyl iodonium tetrafluoroborate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroarsenate, diphenyl iodonium trifluoromethyl Sulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium butyl ginseng (2,6-difluorophenyl) borate, diphenyl Iodonium hexyl ginseng (p-fluorophenyl) borate, diphenyl iodonium hexyl ginseng (3-trifluoromethylphenyl) borate, 4-methoxyphenyl phenyl iodonium tetrafluoroborate , 4-Methoxyphenylphenyliodonium hexafluorophosphate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate Acid salt, 4-methoxyphenylphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodonium-p-toluenesulfonate, 4-methoxyphenylphenyliodonium butyl Ginseng (2,6-difluorophenyl) borate, 4-methoxyphenyl phenyl iodonium hexyl ginseng (p-fluorophenyl) borate, 4-methoxyphenyl phenyl iodonium ginseng (3-Trifluoromethylphenyl) borate, bis(4-tertiary butylphenyl) iodonium tetrafluoroborate, bis(4-tertiary butylphenyl) iodonium hexafluoroarsenate, Bis(4-tertiary butylphenyl) iodonium trifluoromethanesulfonate, bis(4-tertiary butylphenyl) iodonium trifluoroacetate, bis(4-tertiary butylphenyl) Iodonium-p-toluenesulfonate, bis(4-tertiary butylphenyl) iodonium butyl ginseng (2,6-difluorophenyl) borate, bis(4-tertiary butylphenyl) Iodonium hexyl ginseng (p-fluorophenyl) borate and bis(4-tertiary butylphenyl) iodonium hexyl ginseng (3-trifluoromethylphenyl) borate.

Examples of the above-mentioned triarylsulfonium salts include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate Acid salt, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, triphenylsulfonium butyl ginseng (2,6-difluorophenyl) borate, triphenyl Sulfonium hexyl ginseng (p-fluorophenyl) borate, triphenyl sulfonium hexyl ginseng (3-trifluoromethylphenyl) borate, 4-methoxyphenyl diphenyl sulfonium tetrafluoroborate , 4-methoxyphenyldiphenylsulfonium hexafluorophosphate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoro Methanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyl Diphenylsulfonium butyl ginseng (2,6-difluorophenyl) borate, 4-methoxyphenyl diphenylsulfonium hexyl ginseng (p-fluorophenyl) borate, 4-methoxy Phenyldiphenylsulfonium ginseng (3-trifluoromethylphenyl) borate, 4-phenylthiophenyldiphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenylsulfonium Hexafluorophosphate, 4-phenylthiophenyldiphenylsulfonium hexafluoroarsenate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate, 4-phenylthiophenyl Diphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenylsulfonium butyl ginseng (2,6- Difluorophenyl) borate, 4-phenylthiophenyl diphenyl sulfonium hexyl ginseng (p-fluorophenyl) borate, 4-phenylthio phenyl diphenyl sulfonium ginseng (3-trifluoro Methylphenyl) borate, 4-hydroxy-1-naphthyldimethylsulfonium tetrafluoroborate, 4-hydroxy-1-naphthyldimethylsulfonium hexafluorophosphate, 4-hydroxy-1- Naphthyldimethylsulfonium hexafluoroarsenate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoroacetic acid Salt, 4-hydroxy-1-naphthyldimethylsulfonium-p-toluenesulfonate, 4-hydroxy-1-naphthyldimethylsulfonium butyl ginseng (2,6-difluorophenyl) boric acid Salt, 4-hydroxy-1-naphthyldimethylsulfonium hexyl ginseng (p-fluorophenyl) borate and 4-hydroxy-1-naphthyl dimethylsulfonium ginseng (3-trifluoromethylphenyl) ) Borate.

Examples of the above-mentioned quaternary ammonium salts include tetramethylammonium tetrafluoroborate, tetramethylammonium hexafluorophosphate, tetramethylammonium hexafluoroarsenate, tetramethylammonium trifluoromethanesulfonate, tetramethylammonium trifluoroacetic acid Salt, tetramethylammonium-p-toluenesulfonate, tetramethylammonium butyl ginseng (2,6-difluorophenyl) borate, tetramethylammonium hexyl ginseng (p-fluorophenyl) borate, tetramethylammonium Ginseng (3-trifluoromethylphenyl) borate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium hexafluorophosphate, tetrabutylammonium hexafluoroarsenate, tetrabutylammonium trifluoromethanesulfonate, Tetrabutylammonium trifluoroacetate, tetrabutylammonium-p-toluenesulfonate, tetrabutylammonium butyl ginseng (2,6-difluorophenyl) borate, tetrabutylammonium hexyl ginseng (p-fluorophenyl) Borate, tetrabutylammonium ginseng (3-trifluoromethylphenyl) borate, benzyltrimethylammonium tetrafluoroborate, benzyltrimethylammonium hexafluorophosphate, benzyltrimethylammonium hexafluoroarsenate, benzyl Trimethylammonium trifluoromethanesulfonate, benzyltrimethylammonium trifluoroacetate, benzyltrimethylammonium-p-toluenesulfonate, benzyltrimethylammonium butyl ginseng (2,6-difluorophenyl) borate , Benzyl trimethyl ammonium hexyl ginseng (p-fluorophenyl) borate, benzyl trimethyl ammonium ginseng (3-trifluoromethyl phenyl) borate, benzyl dimethyl phenyl ammonium tetrafluoroborate, benzyl Dimethylphenylammonium hexafluorophosphate, benzyldimethylphenylammonium hexafluoroarsenate, benzyldimethylphenylammonium trifluoromethanesulfonate, benzyldimethylphenylammonium three Fluoroacetate, benzyl dimethyl phenyl ammonium-p-toluene sulfonate, benzyl dimethyl phenyl ammonium butyl ginseng (2,6-difluorophenyl) borate, benzyl dimethyl benzene Base ammonium hexyl ginseng (p-fluorophenyl) borate, benzyl dimethyl phenyl ammonium ginseng (3-trifluoromethyl phenyl) borate, N-cinnamylidene ethyl phenyl ammonium tetrafluoroborate , N-cinnamylidene ethyl phenyl ammonium hexafluorophosphate, N-cinnamylidene ethyl phenyl ammonium hexafluoroarsenate, N-cinnamylidene ethyl phenyl ammonium trifluoromethane sulfonate, N-cinnamylidene ethyl phenyl ammonium trifluoroacetate, N-cinnamylidene ethyl phenyl ammonium-p-toluene sulfonate, N-cinnamylidene ethyl phenyl ammonium butyl ginseng (2,6 -Difluorophenyl) borate, N-cinnamylidene ethyl phenyl ammonium hexyl ginseng (p-fluorophenyl) borate and N-cinnabinyl ethyl phenyl ammonium ginseng (3-trifluoromethyl benzene)base)Borate.

Examples of the above-mentioned sulfonic acid esters include α-hydroxymethylbenzoin-p-toluenesulfonate, α-hydroxymethylbenzoin-trifluoromethanesulfonate, α-hydroxymethylbenzoin-methane Sulfonate, pyrogallol-tris(p-toluenesulfonic acid) ester, pyrogallol-tris(trifluoromethanesulfonic acid) ester, pyrogallol-trimethylsulfonate, 2,4-dinitro Benzyl-p-toluenesulfonate, 2,4-dinitrobenzyl-trifluoromethanesulfonate, 2,4-dinitrobenzyl-methanesulfonate, 2,4-di Nitrobenzyl-1,2-naphthoquinone diazide-5-sulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-tri Fluoromethylsulfonate, 2,6-dinitrobenzyl-methanesulfonate, 2,6-dinitrobenzyl-1,2-naphthoquinonediazide-5-sulfonate, 2-nitrobenzyl-p-toluenesulfonate, 2-nitrobenzyl-trifluoromethanesulfonate, 2-nitrobenzyl-methanesulfonate, 2-nitrobenzyl-1 , 2-Naphthoquinone diazide-5-sulfonate, 4-nitrobenzyl-p-toluenesulfonate, 4-nitrobenzyl-trifluoromethanesulfonate, 4-nitrobenzyl -Methylsulfonate, 4-nitrobenzyl-1,2-naphthoquinonediazide-5-sulfonate, N-hydroxynaphthalimino-p-toluenesulfonate, N- Hydroxy naphthalene imino-trifluoromethane sulfonate, N-hydroxy naphthalene imino-methane sulfonate, N-hydroxy-5-proporbornene-2,3-dicarboxy imino -P-toluenesulfonate, N-hydroxy-5-orthobornene-2,3-dicarboxyamido-trifluoromethanesulfonate, N-hydroxy-5-orbornene-2,3 -Dicarboxyimino-methanesulfonate, 2,4,6,3',4',5,-hexahydroxybenzophenone-1,2-naphthoquinone diazide-4-sulfonate Ester and 1,1,1-tris(p-hydroxyphenyl)ethane-1,2-naphthoquinonediazido-4-sulfonate.

Among these compounds, 2-(3-chlorophenyl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0101.tif" />, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0102.tif" />, 2-(4-Methylthiophenyl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0103.tif" />, 2-(4-Methoxy-β-styryl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0104.tif" />, 2-piperonyl-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0105.tif" />, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0106.tif" />, 2-[2-(5-Methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0107.tif" />, 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0108.tif" />And 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-tri<img file="TWI289727B_D0109.tif" />Is the preferred trichloromethyl-s-tri<img file="TWI289727B_D0110.tif" />Class; diphenyl iodonium trifluoroacetate, diphenyl iodonium trifluoromethane sulfonate, 4-methoxyphenyl phenyl iodonium trifluoromethane sulfonate and 4-methoxybenzene Phenylphenyl iodonium trifluoroacetate is the preferred diaryliodonium salt; triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxybenzene Diphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluoromethanesulfonate And 4-phenylthiophenyldiphenylsulfonium trifluoroacetate are preferred triarylsulfonium salts; tetramethylammonium butyl ginseng (2,6-difluorophenyl) borate, tetramethylammonium hexyl Ginseng (p-fluorophenyl) borate, tetramethyl ammonium ginseng (3-trifluoromethyl phenyl) borate, benzyl dimethyl phenyl ammonium butyl ginseng (2,6-difluorophenyl) borate Salt, benzyl dimethyl phenyl ammonium hexyl ginseng (p-fluorophenyl) borate, and benzyl dimethyl phenyl ammonium ginseng (3-trifluoromethyl phenyl) borate are the preferred quaternary ammoniums Salt; and 2,6-dinitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-trifluoromethanesulfonate, N-hydroxynaphthalimino-p-toluene Sulfonic acid esters and N-hydroxynaphthalimino-trifluoromethanesulfonic acid esters are preferred sulfonic acid esters.

The compounds disclosed in JP-A 4-330444 and USP 5,627,010 are suitable as the above-mentioned radiation-sensitive base generators. However, any radiation-sensitive base generator is acceptable if its function is to form a base after exposure to radiation.

In the present invention, the radiation-sensitive base generator is preferably an optically active carbamate such as triphenylmethanol, benzyl carbamate or benzoin carbamate; an amide such as O-carbamate Hydroxy amide, O-amino methionyl oxime, aromatic sulfonamide, α-lactam or N-(2-allylethynyl) amide or other amides; oxime ester, α-amine Base Acetylbenzene or Cobalt Complex.

Examples of radiation-sensitive base generators include compounds represented by the following formulas (2) to (13):<chemistry general="n"><img file="TWI289727B_D0111.tif" /></chemistry>Where R³Is an alkyl group containing 1 to 6 carbon atoms, an alkoxy group containing 1 to 6 carbon atoms, an alkylthio group containing 1 to 6 carbon atoms, a dialkylamino group containing 1 to 6 carbon atoms, six Hydropyridyl, nitro, hydroxyl, mercapto, alkenyl with 2 to 6 carbon atoms, alkynyl with 2 to 6 carbon atoms, aryl with 6 to 20 carbon atoms, fluorine atom, chlorine atom or Bromine atom, k is an integer from 0 to 3, R⁴Is a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, an alkynyl group containing 2 to 6 carbon atoms or an aryl group containing 6 to 20 carbon atoms, and R⁵And R⁶Each independently is a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, an alkynyl group containing 2 to 6 carbon atoms, and an aryl group containing 6 to 20 carbon atoms Or benzyl, or R⁵And R⁶It bonds with the nitrogen to which it is bonded to form a ring structure containing 5 to 6 carbon atoms.

<chemistry general="n"><img file="TWI289727B_D0112.tif" /></chemistry>Where R⁷Is an alkyl group containing 1 to 6 carbon atoms, an alkoxy group containing 1 to 6 carbon atoms, an alkylthio group containing 1 to 6 carbon atoms, a dialkylamino group containing 1 to 6 carbon atoms, six Hydropyridyl, nitro, hydroxyl, mercapto, alkenyl with 2 to 6 carbon atoms, alkynyl with 2 to 6 carbon atoms or aryl with 6 to 20 carbon atoms, R⁸Is a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, an alkynyl group containing 2 to 6 carbon atoms or an aryl group containing 6 to 20 carbon atoms, and R⁹And R¹⁰Each independently is a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, an alkynyl group containing 2 to 6 carbon atoms, and an aryl group containing 6 to 20 carbon atoms Or benzyl, or R⁹And R¹⁰It bonds with the nitrogen to which it is bonded to form a ring structure containing 5 to 6 carbon atoms.

<chemistry general="n"><img file="TWI289727B_D0113.tif" /></chemistry>Where R¹¹Is an alkyl group containing 1 to 6 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, an alkynyl group containing 2 to 6 carbon atoms or an aryl group containing 6 to 20 carbon atoms, and R¹²And R¹³Each independently is a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, an alkynyl group containing 2 to 6 carbon atoms, and an aryl group containing 6 to 20 carbon atoms Or benzyl, or R¹²And R¹³It bonds with the nitrogen to which it is bonded to form a ring structure containing 5 to 6 carbon atoms.

<chemistry general="n"><img file="TWI289727B_D0114.tif" /></chemistry>Where R¹⁴And R¹⁵Each is independently an alkyl group containing 1 to 6 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, an alkynyl group containing 2 to 6 carbon atoms, or an aryl group containing 6 to 20 carbon atoms.

<chemistry general="n"><img file="TWI289727B_D0115.tif" /></chemistry>Where R¹⁶, R¹⁷And R¹⁸Each is independently an alkyl group containing 1 to 6 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, an alkynyl group containing 2 to 6 carbon atoms, or an aryl group containing 6 to 20 carbon atoms.

<chemistry general="n"><img file="TWI289727B_D0116.tif" /></chemistry>Where R¹⁹Is an alkyl group containing 1 to 6 carbon atoms, an alkoxy group containing 1 to 6 carbon atoms, an alkylthio group containing 1 to 6 carbon atoms, a dialkylamino group containing 1 to 6 carbon atoms, six Hydropyridyl, nitro, hydroxyl, mercapto, alkenyl with 2 to 6 carbon atoms, alkynyl with 2 to 6 carbon atoms or aryl with 6 to 20 carbon atoms, R²⁰Is a hydrogen atom, an alkenyl group containing 2 to 6 carbon atoms, an alkynyl group containing 2 to 6 carbon atoms, or an aryl group containing 6 to 20 carbon atoms, and R²¹, R²²And R²³Each independently is a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, an alkynyl group containing 2 to 6 carbon atoms, and an aryl group containing 6 to 20 carbon atoms Or benzyl.

<chemistry general="n"><img file="TWI289727B_D0117.tif" /></chemistry>Where R²⁴Is an alkyl group containing 1 to 6 carbon atoms, an alkoxy group containing 1 to 6 carbon atoms, an alkylthio group containing 1 to 6 carbon atoms, a dialkylamino group containing 1 to 6 carbon atoms, six Hydropyridyl, nitro, hydroxyl, mercapto, alkenyl with 2 to 6 carbon atoms, alkynyl with 2 to 6 carbon atoms or aryl with 6 to 20 carbon atoms, R²⁵And R²⁶Each independently is a hydrogen atom, a hydroxyl group, a mercapto group, a cyano group, a phenoxy group, an alkyl group containing 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom or an aryl group, and R²⁷And R²⁸Each independently is a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, an alkynyl group containing 2 to 6 carbon atoms, and an aryl group containing 6 to 20 carbon atoms Or benzyl, or R²⁷And R²⁸It bonds with the nitrogen to which it is bonded to form a ring structure containing 5 to 6 carbon atoms.

<chemistry general="n"><img file="TWI289727B_D0118.tif" /></chemistry>Where R²⁹And R³⁰Each is independently an alkyl group containing 1 to 6 carbon atoms, an alkoxy group containing 1 to 6 carbon atoms, an alkylthio group containing 1 to 6 carbon atoms, and a dialkylamine containing 1 to 6 carbon atoms R³¹To R³⁴Each independently is a hydrogen atom, a hydroxyl group, a mercapto group, a cyano group, a phenoxy group, an alkyl group containing 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an alkenyl group containing 2 to 6 carbon atoms, a An alkynyl group of 2 to 6 carbon atoms or an aryl group of 6 to 20 carbon atoms, and A¹Is the hydroxyl group bonded to monoalkylamine, hexahydropyridine by excluding two hydrogen atoms<img file="TWI289727B_D0119.tif" />, Aromatic diamine or aliphatic diamine one or two nitrogen atoms to form a divalent group.

<chemistry general="n"><img file="TWI289727B_D0120.tif" /></chemistry>Where R³⁵And R³⁶Each is independently an alkyl group containing 1 to 6 carbon atoms, an alkoxy group containing 1 to 6 carbon atoms, an alkylthio group containing 1 to 6 carbon atoms, and a dialkylamine containing 1 to 6 carbon atoms R³⁷And R³⁸Each independently is a hydrogen atom, a hydroxyl group, a mercapto group, a cyano group, a phenoxy group, an alkyl group containing 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an alkenyl group containing 2 to 6 carbon atoms, Alkynyl group with 2 to 6 carbon atoms or aryl group with 6 to 20 carbon atoms, R³⁹To R⁴²Each independently is a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, an alkynyl group containing 2 to 6 carbon atoms, and an aryl group containing 6 to 20 carbon atoms Or benzyl, or R³⁹And R⁴⁰, And R⁴¹And R⁴²Bond with the nitrogen to which it is bonded to form a ring structure containing 5 to 6 carbon atoms, and A²It is an alkylene, cyclohexylene, phenylene or single bond containing 1 to 6 carbon atoms.

<chemistry general="n"><img file="TWI289727B_D0121.tif" /></chemistry>Where R⁴³To R⁴⁵Each independently is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group containing 1 to 6 carbon atoms, an alkoxy group containing 1 to 6 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, An alkynyl group containing 2 to 6 carbon atoms or an aryl group containing 6 to 20 carbon atoms.

L_mCO³⁺. 3[(R⁴⁶)₃R⁴⁷(12) Wherein L is at least one selected from the group consisting of ammonia, pyridine, imidazole, ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, propylenediamine, 1,2-cyclohexanediamine, N,N-Diethylethylenediamine and diethylenetriamine ligand, m is an integer from 2 to 6, R⁴⁶Is an alkenyl group containing 2 to 6 carbon atoms, an alkynyl group containing 2 to 6 carbon atoms or an aryl group containing 6 to 20 carbon atoms, and R⁴⁷Is an alkyl group containing 1 to 18 carbon atoms.

<chemistry general="n"><img file="TWI289727B_D0122.tif" /></chemistry>Where R⁴⁸To R⁵¹Each independently is a hydrogen atom, a nitro group, a fluorine atom, a chlorine atom, a bromine atom, an alkyl group containing 1 to 6 carbon atoms, an alkenyl group containing 2 to 6 carbon atoms, an alkyne containing 2 to 6 carbon atoms Group, alkoxy group or aryl group containing 1 to 6 carbon atoms, R⁵²And R⁵³Each is independently acetoxy, acetoxy or cyano, and R⁵⁴Is a hydrogen atom, an alkyl group containing 1 to 6 carbon atoms, an aryl group or a benzyl group.

In all of the above formulas (2) to (13), the alkyl group may be linear, branched or cyclic. Examples of the aryl group include phenyl, naphthyl, anthracenyl, and fluorine, chlorine, bromine, Haloalkyl, hydroxyl, carboxyl, mercapto, cyano, nitro, azide, dialkylamino, alkoxy or alkylthio group substituted for the hydrogen atoms of these groups.

Among these radiation-sensitive alkali generators, 2-nitrobenzylcyclohexyl carbamate, triphenylmethanol, O-aminomethanyl hydroxyamide, O-aminomethanyl Oxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[[(2,6-dinitrobenzyl)oxy]carbonyl]hexane 1,6-di Amine, 4-(methylthiobenzyl)-1-methyl-1-morpholinylethane, (4-morpholinylbenzyl)-1-benzyl-1-dimethyl Aminopropane, N-(2-nitrobenzyl ester) pyrrolidine, hexaamine cobalt(III) ginseng (triphenylmethyl borate), 2-benzyl-2-dimethylamino-1-( 4-morpholinylbenzyl)-butanone, 2,6-dimethyl-3,5-diacetyl-4-(2'-nitrophenyl)-1,4-dihydro Pyridine and 2,6-Dimethyl-3,5-diacetyl-4-(2',4'-dinitrophenyl)-1,4-dihydropyridine.

Examples of the above-mentioned radiation-sensitive radical generators include α-diketones such as benzyl and diacetyl; acylins such as benzoin; azoin ethers such as benzoin methyl ether and benzoin ethyl ether And benzoin isopropyl ether; benzophenones such as thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (Dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone; Acetylbenzenes such as acetylbenzene, p-dimethylaminoacetylbenzene, α,α '-Dimethoxy acetoxy acet benzene, 2,2'-dimethoxy-2-phenyl acet benzene, p-methoxy acet benzene, 2-methyl-[4-( (Methylthio)phenyl]-2-morpholinyl-1-propanone and 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one; Quinones such as anthraquinone and 1,4-naphthoquinone; halogen-based compounds such as phenacyl chloride, tribromomethyl phenyl sulfide and ginseng (trichloromethyl)-s-tri<img file="TWI289727B_D0123.tif" />; Phosphine oxides such as 2,4,6-trimethylbenzyl diphenyl phosphine oxide, bis (2,6-dimethoxybenzyl)-2,4,4-three Methyl-pentylphosphine oxide and bis(2,4,6-trimethylbenzyl)phenylphosphine oxide; and peroxides such as di-tert-butyl peroxide.

The commercial supply products of these radiation-sensitive base generators include IRGACURE-184, 369, 500, 651, 907, 1700, 819, 1000, 2959, 149, 1800 and 1850, and Darocur-1173, 1116, 2959, 1664 And 4043 (Ciba Speciality Chemicals Co., Ltd.), KAYACURE-DETX, -MBP, -DMBI, -EPA and -OA (Nippon Kayaku Co., Ltd.), VICURE-10 and 55 (STAUFFER Co., Ltd.) ), TRIGONALP1 (AKZO Co., Ltd.), SANDORAY 1000 (SANDOZ Co., Ltd.), DEAP (APJOHN Co., Ltd.) and QUANTACURE-PDO, -ITX and -EPD (WARD BLEKINSOP Co., Ltd.) ).

Radiation-sensitive base generators can be used in combination with a radiation-sensitive sensitizer to obtain a resin composition that is highly sensitive to radiation.

When the above-mentioned radiation-sensitive decomposer (C) is a radiation-sensitive acid generator or alkali generator, its amount is preferably 0.01 parts by weight or more, and more preferably 0.05 parts by weight or more. The total number of inorganic oxide particles (A) and polymerizable compounds (B) of 100 weight components is based on the basis. When the amount of acid generators or alkali generators sensitive to radiation is less than 0.01 weight components, it is The sensitivity will decrease, and the upper limit is preferably 30 weight components, more preferably 20 weight components.

The dosage of the radiation-sensitive base generator is preferably 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, based on 100 parts by weight of inorganic oxide particles (A) and polymerizable compounds (B) Based on the total number, when the amount of the radiation-sensitive base generator is less than 1 weight component, its sensitivity to radiation will decrease.

The above-listed compounds as component (C) can be used alone or in combination of two or more.

(D) Compounds that can escape

The escapeable compound (D) used in the present invention is a known compound. When heated, it decomposes, sublimates or evaporates and escapes through volatilization. The heating temperature is preferably 70 to 400°C, more preferably 150 to 350°C, the refractive index of component (D) is preferably 1.3 to 1.9, more preferably 1.4 to 1.9. The molecular weight of the escapeable compound used as component (D) is not particularly limited and can be as low as monomer or oligomer. Things.

The escapeable compounds are, for example, polyethers, fatty acids, fatty acid esters, hydrazine compounds, hydrazone compounds, azo compounds, or amine-based compounds. Typical examples of escapeable compounds are as follows.

Examples of polyethers include polyethylene glycol, polypropylene glycol, intercalated copolymers of polyethylene glycol and polypropylene glycol, random copolymers of polyethylene glycol and polypropylene glycol, and modified polyethylene glycol terminal hydroxyl groups. Fatty acid esters or alkyl ethers, fatty acid esters or alkyl ethers obtained by modifying the terminal hydroxyl groups of polypropylene glycol, fatty acid esters or alkyl ethers obtained by modifying the terminal hydroxyl groups of polyethylene glycol-polypropylene glycol copolymers, Polyethylene glycol sorbitan fatty acid ester obtained by modifying sorbitol anhydride with ethylene glycol, polypropylene glycol sorbitan fatty acid ester obtained by modifying sorbitan with propylene glycol, and polyethylene glycol- The polyethylene glycol-polypropylene glycol sorbitan fatty acid ester obtained by the modification of sorbitol by polypropylene glycol copolymer is added to type A bisphenol by adding polyethylene glycol, polypropylene glycol or polyethylene glycol-polypropylene glycol copolymer The obtained polyether glycol, the polyether triol obtained by adding polyethylene glycol, polypropylene glycol or polyethylene glycol-polypropylene glycol copolymer to glycerin, and the polyether triol obtained by adding polyethylene glycol, polypropylene glycol or polyethylene glycol -Polyether tetraol obtained from polypropylene glycol copolymer to ethylene diamine.

Examples of fatty acids include butyric acid, valeric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid, as well as substituting double bonds for part or all of the single bonds of the above fatty acids The resulting unsaturated fatty acid.

Examples of fatty acid esters include ethyl caprylate, ethyl pelargonate, methyl myristate, ethyl myristate, methyl palmitate, methyl stearate and methyl arachidonic acid, as well as the use of double bonds An unsaturated fatty acid ester obtained by substituting part or all of the single bonds of the above fatty acid ester.

Examples of hydrazine compounds include hydrazine salicylate, hydrazine maleate, p-toluenesulfonyl hydrazine, p, p'-oxy bisphenylsulfonyl hydrazine, thiocarbonate hydrazine, 3- Hydroxy-2-naphthoate hydrazine, carbodihydrazine, adipate dihydrazine, sebacate dihydrazine, dodecane dihydrazine, isophthalate dihydrazine, dihydrazine propionate, bis( Cyclohexylidene) acid oxalyl dihydrazide and aminopolyacrylamide.

Examples of hydrazone compounds include benzophenone hydrazone, p-toluenesulfonylacetone hydrazone, carbonyl cyanide meta-chlorophenyl hydrazone, and carbonyl cyanide 3-chlorophenyl hydrazone.

Examples of azo compounds include azodicarbamide, diphenylcarbazone, diphenylthiocarbazone, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4 -Dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylbutyronitrile), 1,1'-azobis(1-acetoxy-1-phenylethane) ) And 2,2'-azobis(2-methylbutane amidoxime).

Examples of amine compounds include octylamine, laurylamine, stearylamine, oleylamine, myristamine, cetylammonium, triethanolamine, and dinitrosopentamethylenetetramine.

Component (D) can be used as a dispersant for inorganic oxide particles (A).

The hydrogen atoms contained in the molecules of the above compounds can be through ethylenically unsaturated bonds, epoxy groups, sulfide groups,<img file="TWI289727B_D0124.tif" />Tankyl, isocyanate group, cyanate group,<img file="TWI289727B_D0125.tif" />Azole,<img file="TWI289727B_D0126.tif" />Substitution of groups or silyl groups, which can be polymerized via acids, bases, or groups formed from the radiation-sensitive decomposer (C). The above-listed known compounds can be used as the escapeable compound (D) in the present invention without limitation, but compounds containing aromatic rings, halogen atoms or sulfur atoms are useful for increasing the refractive index.

The hydrogen atoms of all compounds listed as component (D) can be through chlorine atom, bromine atom, hydroxyl group, mercapto group, alkoxy group, alkylthio group, haloalkyl group, haloalkoxy group, haloalkylthio group, thioester group , Mercaptoalkyl, aryl, aralkyl or cyano substituted.

Examples of the above-mentioned alkoxy groups which may be straight or branched include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, first Tributoxy, n-pentyloxy, neopentyloxy and n-hexyloxy.

Examples of the aforementioned alkylthio groups that may be straight or branched include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, second butylthio, first Tributylthio, n-pentylthio, neopentylthio and n-hexylthio.

Examples of the above-mentioned haloalkyl groups include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, chloromethyl, 2-chloroethyl, 3-chloropropyl, 1-chloromethylethyl, 4-chlorobutane Group, 2-chloromethylpropyl, 5-chloropentyl, 3-chloromethylbutyl, 2-chloroethylpropyl, 6-chlorohexyl, 3-chloromethylpentyl, 4-chloromethyl Pentyl, 2-chloroethylbutyl, bromomethyl, 2-bromoethyl, 3-bromopropyl, 1-bromomethylethyl, 4-bromobutyl, 2-bromomethylpropyl, 5 -Bromopentyl, 3-bromomethylbutyl, 2-bromoethylpropyl, 6-bromohexyl, 3-bromomethylpentyl, 4-bromomethylpentyl and 2-bromoethylbutyl.

Examples of the above-mentioned haloalkoxy include trifluoromethoxy, pentafluoroethoxy, heptafluoropropoxy, chloromethoxy, 2-chloroethoxy, 3-chloropropoxy, 1-chloromethyl Ethoxy, 4-chlorobutoxy, 2-chloromethylpropoxy, 5-chloropentoxy, 3-chloromethylbutoxy, 2-chloroethylpropoxy, 6-chlorohexoxy Group, 3-chloromethylpentoxy, 4-chloromethylpentoxy, 2-chloroethylbutoxy, bromomethoxy, 2-bromoethoxy, 3-bromopropoxy, 1- Bromomethylethoxy, 4-bromobutoxy, 2-bromomethylpropoxy, 5-bromopentoxy, 3-bromomethylbutoxy, 2-bromoethylpropoxy, 6- Bromohexyloxy, 3-bromomethylpentyloxy, 4-bromomethylpentyloxy and 2-bromoethylbutoxy.

Examples of the above-mentioned haloalkylthio include trifluoromethylthio, pentafluoroethylthio, heptafluoropropylthio, chloromethylthio, 2-chloroethylthio, 3-chloropropylthio, 1-chloromethyl Ethylthio, 4-chlorobutylthio, 2-chloromethylpropylthio, 5-chloropentylthio, 3-chloromethylbutylthio, 2-chloroethylpropylthio, 6-chlorohexylthio Group, 3-chloromethylpentylthio, 4-chloromethylpentylthio, 2-chloroethylbutylthio, bromomethylthio, 2-bromoethylthio, 3-bromopropylthio, 1- Bromomethylethylthio, 4-bromobutylthio, 2-bromomethylpropylthio, 5-bromopentylthio, 3-bromomethylbutylthio, 2-bromoethylpropylthio, 6- Bromohexylthio, 3-bromomethylpentylthio, 4-bromomethylpentylthio and 2-bromoethylbutylthio.

Examples of the above-mentioned thioester group include acetylsulfonamide, isobutyrylsulfonamide, n-pentylsulfonamide, neopentylsulfonamide, and n-hexylsulfonamide.

Examples of the above-mentioned mercaptoalkyl include mercaptomethyl, 2-mercaptoethyl, 3-mercaptopropyl, 1-mercaptomethylethyl, 4-mercaptobutyl, 2-mercaptomethylpropyl, 5-mercaptopentyl , 3-mercaptomethylbutyl, 2-mercaptoethylpropyl, 6-mercaptohexyl, 3-mercaptomethylpentyl, 4-mercaptomethylpentyl and 2-mercaptoethylbutyl.

Examples of the aforementioned aryl group include phenyl, tolyl, xylyl, cumenyl and 1-naphthyl.

Examples of the aforementioned aralkyl group include benzyl, α-methylbenzyl, phenethyl, and naphthylmethyl.

These compounds as component (D) can be used alone or in combination of two or more.

The amount of ingredient (D) is preferably 1 to 99 parts by weight, more preferably 5 to 90 parts by weight, based on the total of 100 parts by weight of ingredients (A) and (B), when ingredient (D) When the amount is less than 1 weight component, the resulting difference in refractive index is likely to become smaller, and when the equivalent weight is greater than 99 weight components, the material with changed refractive index is likely to become brittle.

&lt;Other ingredients&gt;

The composition with changing refractive index of the present invention may contain other ingredients, the limitation of which is not to undermine the purpose of the present invention. The additives include ultraviolet light absorbers, sensitizers, surfactants, heat-resistant modifiers and adhesion promoters.

The aforementioned ultraviolet light absorber is, for example, benzotriazole, salicylate, benzophenone, whale-substituted acrylonitrile, xanthene, coumarin, flavone or chalcone. Specific examples of the ultraviolet light absorber include Tinubin 234 (2-(2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl)-2H-benzotriazole), Tinubin 571 (hydroxyphenyl benzotriazole two derived ) And Tinubin 1130 (methyl-3-(3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxypropyl) propionate and polyethylene glycol (molecular weight 300)) (Ciba Specialty Chemicals Co., Ltd.), 1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione and benzylidene Base acetone.

By adding an ultraviolet light absorber, the acid or base formed from component (C) can gradually decrease as the refractive index change material of the present invention increases from the surface depth of the exposed part, and it can be used to form GRIN, ultraviolet light absorber The amount is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on the total number of components (A) and (B) in 100 parts by weight.

The above-mentioned sensitizers are, for example, coumarin, flavonoids, dibenzylidene acetone, dibenzylidene cyclohexane, chalcone, xanthene, thioxanthene containing substituents at the 3- and/or 7-position , Poline, Phthalocyanine, Acridine or Anthracene.

The amount of the sensitizer is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, based on the total number of components (A) and (B) in 100 parts by weight.

The above-mentioned surfactants may be added to improve coating properties such as prevention of flare and improvement of color rendering power.

Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers including polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene aryl ether Classes include polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; and polyethylene glycol dialkyl esters include polyethylene glycol dilaurate and polyethylene glycol distearate; Fluorine-based surfactants, which are in F Top EF301, EF303 and EF352 (Shin Akita Kasei Co., Ltd.), Megafac F171, F172 and F173 (Dainippon Ink and Chemicals, Inc.), Florade FC430 and FC431 (Sumitomo 3M Limited) and Asahi Guard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105 and SC-106 (Asahi Glass Co., Ltd.) under the trade name Chemical supply; and other surfactants which are in o KP341 organosiloxane polymer (Shin-Etsu Chemical Co., Ltd.) and Polyflow No.57 and No.95 acrylic acid or methacrylic acid matrix (co) polymer (Kyoeisha Kagaku Co., Ltd.) commercialized supply under the brand name.

The amount of the surfactant is preferably 2 parts by weight or less, more preferably 1 part by weight or less, based on the total number of components (A) and (B) in 100 parts by weight.

The aforementioned adhesion promoter can be added to improve the adhesion to the substrate and is preferably a silane coupling agent.

The above heat-resistant modifier is an unsaturated compound such as polyacrylate.

If necessary, an antistatic agent, a stabilizer, a halo inhibitor, an anti-foaming agent, a pigment, and an acid heat generator can be added to the composition with a refractive index change of the present invention.

&lt;Forming a refractive index pattern&gt;

In the present invention, for example, a refractive index pattern can be formed from the above-mentioned refractive index changed composition below.

First, dissolve or disperse the composition with changed refractive index in a solvent to prepare a composition solution with a solid content of 5 to 70% by weight, and filter the composition solution through a filter paper with an opening diameter of about 0.1 to 10 microns before use.

Subsequently, the composition solution is applied to the surface of a substrate such as a silicon wafer and pre-baked to remove the solvent so as to form a coating film of a composition with a refractive index change, and then part of the formed coating film is exposed to radiation through a patterned mask , And carry out post-exposure bake (PEB) to make the refractive index difference between the exposed and unexposed parts of the composition whose refractive index is changed.

The acid, base or base formed from the radiation-sensitive decomposition agent (C) through the above exposure will act on the polymerizable compound as the component (B) to polymerize and crosslink the component (B), thereby limiting the escapeable compounds (D) and prevent component (D) from escaping, because the above-mentioned polymerization and cross-linking will not occur in the unexposed parts, component (D) escapes, due to the presence and absence of component (D), resulting in exposed and unexposed parts The difference in refractive index of parts.

The solvent used to prepare the solution containing the refractive index-changing compound used in the present invention can uniformly dissolve or disperse the above-mentioned components (A), (B), (C) and (D) and other additives, and will not interact with these components. reaction.

Examples of solvents include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, and propylene glycol; ethers such as tetrahydrofuran; cellulose such as methyl cellulose, ethyl cellulose, propyl cellulose, and Butyl cellulose; ethylene glycol alkyl ether acetate such as methyl cellulose acetate and ethyl cellulose acetate; diethylene glycol such as diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol mono Ethyl methyl ether and diethylene glycol diethyl ether; propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol ethyl ether acetate , Propylene glycol propyl ether acetate and propylene glycol butyl ether acetate; propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate; aromatic Hydrocarbons such as toluene and xylene; ketones such as methyl ethyl ketone, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone; esters such as methyl acetate, ethyl acetate, propyl acetate, Butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, hydroxyacetic acid Butyl ester, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate , 2-hydroxy-3-methylbutyrate methyl ester, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl Ethoxy acetate, ethoxy propyl acetate, ethoxy butyl acetate, propoxy methyl acetate, propoxy ethyl acetate, propoxy propyl acetate, propoxy butyl acetate, butoxy Methyl acetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy Propyl propionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, butyl 2-ethoxypropionate, 2-ethoxy Methyl propionate, butyl 2-ethoxy propionate, methyl 2-butoxy propionate, ethyl 2-butoxy propionate, propyl 2-butoxy propionate, 2-butoxy Butyl 3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxy propionate, propyl 3-ethoxy propionate, butyl 3-ethoxy propionate, methyl 3-propoxy propionate, 3-propoxy Ethyl propionate, propyl 3-propoxy propionate, butyl 3-propoxy propionate, methyl 3-butoxy propionate, ethyl 3-butoxy propionate, 3-Propyl butoxypropionate, butyl 3-butoxypropionate; and solvents containing fluorine atoms such as trifluoromethylbenzene, 1,3-bis(trifluoromethyl)benzene, thiofluorobenzene, hexafluoro Cyclohexane, perfluorodimethylcyclohexane, perfluoromethylcyclohexane, octafluorodecalin and 1,1,2-trichloro-1,2,2-trifluoroethane.

Among these solvents, alcohols, glycol ethers, glycol alkyl ether acetates, propylene glycol alkyl ether acetates, Ketones, esters and diethylene glycols are preferred.

In addition, a high-boiling point solvent can be used in combination with the above-mentioned solvents. Examples of the high-boiling point solvent include N-methylformamide, N,N-dimethylformamide, N-methylformaniline, and N-methylformamide. Acetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, Caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate Ester, phenyl cellulose acetate and diethylene glycol monobenzyl ether.

The refractive index-changing composition used in the present invention is molded into various shapes before exposure to radiation in consideration of the application purpose, for example, molded into rods, fibers, long plates, balls, films, or lenses. The present invention There is no limitation to this, and conventional methods can be used to mold the refractive index change composition of the present invention. For example, injection molding, compression molding, blow molding, extrusion, in-mold polymerization, leveling, and extraction can be used. Drawing, heating/cooling, VCD deposition, sintering or scanning methods, according to the application purpose of the optical molded product, can also use spin coating, slitting, strip coating, solvent casting, LB, spray, roll coating, relief plate Printing and screen printing.

In this molding method before exposure to radiation, heating is more suitable (hereinafter referred to as "pre-baking"). The heating conditions are changed according to the materials of the composition of the present invention and the types of additives, and it is more preferable to 30 to 200°C, more preferably 40 to 150°C, a hot plate or oven, or infrared radiation can be used for heating. The radiation used for exposure is i-rays with a wavelength of 365 nanometers, h-rays with a wavelength of 404 nanometers, g-rays with a wavelength of 436 nanometers, ultraviolet radiation from a wide-wavelength light source such as xenon lamps, extreme ultraviolet radiation such as KrF excitation laser light with a wavelength of 248 nanometers or ArF excitation laser light with a wavelength of 193 nanometers, X-radiation such as synchrotron radiation, charged particle beams such as electron beams, visible light radiation or mixtures thereof, of which far ultraviolet rays are more preferred For radiation and visible light radiation, the illuminance determined by the radiation wavelength is preferably 1 to 1,000 watts/square meter, because the highest response efficiency can be obtained. The composition that is sensitive to radiation and changes in refractive index can be patterned by exposing to the above-mentioned radiation through a patterned mask. As for the accuracy of the pattern affected by the use of the light source, an optical part with a refractive index change distribution with a resolution of about 0.2 microns can be generated.

In the present invention, it is better to heat after exposure (referred to as "post-exposure bake (PEB)"). Similar devices to the above-mentioned pre-bake device can be used for PEB, and the PEB situation can be arbitrary, and the heating temperature is preferably 30 to 150°C, more preferably 30 to 130°C.

In addition, re-exposure can be carried out to decompose the residual component (C) existing in the unexposed part and further improve the stability of the material.

Re-exposure can be based on the way of changing the refractive index, applying the same wavelength of radiation to the entire surface of the pattern at the same amount.

If necessary, further heating can be carried out to completely remove the component (D) existing in the unexposed part, and to further improve the stability of the material. The pre-baking device used in molding can be used for heating and the heating situation can be arbitrary. .

In the above-mentioned refractive index pattern formed according to the present invention, the refractive index of the exposed part is higher than that of the unexposed part. This difference can be controlled by controlling the components (A) and ( The type and content of B) can be adjusted to the desired value. For example, the maximum value of the refractive index difference can be adjusted to a value greater than 0.02.

Because the refractive index pattern of the present invention does not deteriorate without changing the refractive index, even when it is used when the light wavelength is close to the above-mentioned wavelength through which it is used to change the refractive index, it is very suitable for use as an optical material in the field of optoelectronics and display. .

Instance

The following examples are provided to further illustrate the purpose of the present invention and should not be regarded as a limitation.

The weight average molecular weight of each compound under polystyrene is measured using GPC CHROMATOGRAPH SYSTEM-21 of Showa Denko KK.

Synthesis example of component (B)

Synthesis Example 1

Feed 7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethyl methyl ether into a flask equipped with a cooling tube and a stirrer , Subsequently, 10 parts by weight of styrene, 20 parts by weight of methacrylic acid, 40 parts by weight of 2-(2'-vinyloxyethoxy) ethyl methacrylate and 25 parts by weight of methacrylic acid Dicyclopentyl methacrylate was fed into the flask, the inside of the flask was replaced with nitrogen, and 5 parts by weight of 1,3-butadiene was fed into the flask and stirred gently. It would be easy to heat to 70°C and maintain it at The polymer solution containing the copolymer (B-1) was obtained at this temperature for 5 hours. The solid content of the obtained polymer solution was 33.5% and the weight average molecular weight of the polymer (B-1) was 29,000.

Synthesis Example 2

After the inside of a 500 ml three-necked flask equipped with a stirrer and a thermometer was completely replaced with nitrogen, 140 g of toluene, 24 g of styrene and 4.9 g of 2-isopropenyl-2-<img file="TWI289727B_D0127.tif" />The oxazoline was added to the flask. After the internal temperature of the flask rose to 100°C, 2.3 g of 2,2'-azobis-2,4-dimethylvaleronitrile was added as an initiator to start the reaction. Subsequently, 61.5 Grams of styrene, 4.9 grams of initiator and 61.5 grams of toluene were added dropwise to the reaction solution at the same time, and then the reaction product was aged for 15 hours to obtain a light yellow polymer solution.

The resulting polymer solution was diluted with 400 g of toluene and injected into 2 liters of methanol for precipitation, and the precipitate was dissolved in 400 g of toluene and injected again into 2 liters of methanol to be purified by reprecipitation, and dried at 120°C under vacuum , 62 g of polymer (B-2) was obtained, and the weight average molecular weight of the obtained polymer (B-2) was 160,000.

Synthesis Example 3

Charge 71 grams of phenyltrimethoxysilane and 10 grams of methyltrimethoxysilane into a 500 ml three-necked flask equipped with a stirrer and a thermometer. Add 90 grams of n-butanol and dissolve in the mixture. The resulting mixture The solution was heated at 60°C and stirred with a magnetic stirrer, and a solution prepared by adding 1.2 g of 1N hydrochloric acid to a 1:1 mixed solution of 40 g of ion exchange water and n-butanol was added to the resulting solution for 10 minutes After reacting at 60°C for 4 hours, the resulting reaction solution was cooled to room temperature.

Subsequently, the reaction by-product methanol was distilled off from the reaction solution under reduced pressure, and the reaction solution was concentrated to a solid content of 30% by weight to obtain a solution containing polymer (B-3). This polymer (B-3) The weight average molecular weight of) is 5,000.

Synthesis Example 4

50 g of methyl trimethoxysilane, 90 g of propylene glycol methyl ether and 0.25 g of Si (vinylacetone) titanium were fed into a 500 ml three-necked flask equipped with a stirrer and a thermometer to dissolve them, and the resulting mixture was mixed The solution was heated at 60°C and stirred with a magnetic stirrer. A 40g 1:1 mixed solution of ion-exchanged water and propylene glycol methyl ether was continuously added to the resulting solution. After 1 hour, the solution was reacted at 60°C for 4 hours. The reaction solution was cooled to room temperature.

Subsequently, the reaction by-product methanol was distilled off from the reaction solution under reduced pressure, and the reaction solution was concentrated to a solid content of 30% by weight to obtain a solution containing polymer (B-4). This polymer (B-4) The weight average molecular weight of) is 10,000.

Example 1

90 weight component ZrO which will be used as component (A)₂The particles are dispersed in Homogenol L-18 (Kao Corporation), which is a special polycarboxylic acid polymer surfactant of 3 parts by weight as a dispersant, and 4,4'-bis(two) as a 10 parts by weight of component (C). Ethylamino) benzophenone and 12 parts by weight of stearic acid as component (D) are dissolved in diethylene glycol ethyl methyl ether so that the total solid content is 20%, and the opening diameter of the resulting solution is 0.2 Filter with micron membrane filter paper to prepare a composition with changing refractive index.

(1) Forming a coating film

The above composition is applied to the silicon substrate with a spinner and pre-baked on a hot plate at 100° C. for 1 minute to form a coating film with a thickness of 1.0 μm.

(2) Form a refractive index pattern

The NSR150516A reduction projection exposure device (Nikon Corporation, NA=0.45, λ=365nm) was used to expose the above-obtained coating film to 4,000 joules/m² and 8,000 joules/m² through a patterned mask at an optimal depth of focus. The coating film is then baked at 220°C for 30 minutes to form a refractive index pattern with a refractive index difference between the exposed and unexposed parts.

(3) Measuring refractive index

The refractive index of the exposed part and the unexposed part of the above-formed refractive index pattern is at 633 nanometers using MODEL2010 Mirror mirror Coupler (METRICON Co., Ltd.) and #200-P-1 or #200-P- 2 Measure the measurement, the results are listed in Table 1.

(4) Measure porosity with mercury porosimeter

The porosity of the low refractive index part and the high refractive index part of the refractive index pattern formed above is measured with a mercury porosimeter (Autopore 9200, Shimadzu Corporation, the smallest measurable hole diameter is 34<img file="TWI289727B_D0128.tif" />)Measurement.

(5) Transparency assessment

Except that Corning 1737 glass substrate (Corning Co., Ltd.) is used instead of the silicon substrate, the same method as (1) and (2) is used to form a refractive index pattern on the glass substrate.

The transparency of the exposed and unexposed parts of the refractive index pattern formed on the glass substrate is measured with a 150-20 dual-beam photometer (Hitachi, Ltd.) at a wavelength of 400 to 800 nanometers, at 400 nanometers The measured transparency results are listed in Table 1.

Example 2

Except that 10 weight component polymer (B-1) is used as component (B) and 12 weight component dinitrosopentamethylenetetramine is used as component (D), the evaluation is performed in the same manner as in Example 1, and the results are listed In Table 1.

Example 3

In addition to using 10 weight component polymer (B-3) as component (B), 1 weight component 4-hydroxy-1-naphthyldimethylsulfonium trifluoroacetate as component (C) and 12 weight component Azocarbamide was used as component (D), and it was subjected to post-exposure baking at 80°C for 5 minutes. The evaluation was carried out in the same manner as in Example 1. The results are listed in Table 1.

Example 4

In addition to using 85 weight component TiO₂Particles as component (A) and 15 weight component polymer (B-2) as component (B) are dispersed in 12 weight component PE-62 polyethylene glycol-polypropylene glycol intercalated copolymer (Sanyo Chemical Industries, Ltd) Except for the dispersion of component (D), the evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.

Example 5

In addition to using 15 weight component polymer (B-4) as component (B) and 7 weight component 2,6-dimethyl-3,5-diacetyl-4-(2',4'-two Nitrophenyl)-1,4-dihydropyridine was used as component (C), and it was subjected to post-exposure baking at 110°C for 1 minute. The evaluation was carried out in the same manner as in Example 4, and the results are listed in Table 1.

Example 6

Except that 15 weight component polymer (B-1) is used as component (B) and 5 weight component 4-trimethyl-pentylphosphine oxide is used as component (C), the evaluation is performed in the same manner as in Example 4. The results are listed in Table 1.

Example 7

In addition to the use of 85 weight component Al₂O₃Particles as component (A) and 15 weight component polymer (B-1) as component (B) dispersed in 8 weight component PEG-200 polyethylene glycol (Sanyo Chemical Industries, Ltd) as component (D) dispersion Except for the liquid, the evaluation was carried out in the same way as in Example 1, and the results are listed in Table 1.

Example 8

In addition to using 15 weight component polymer (B-3) as component (B) and 5 weight component 6-diamine-4-(methylthiobenzyl)-1-methyl-1-morpholine Ethane was used as the component (C) and was subjected to post-exposure baking at 80°C for 3 minutes. The evaluation was carried out in the same manner as in Example 7. The results are listed in Table 1.

Example 9

Except for using 15 weight component polymer (B-4) as component (B) and 5 weight component of triphenylsulfonium tetrafluoroborate as component (C), and baking at 110°C for 2 minutes Otherwise, the same method as in Example 7 was used for evaluation, and the results are listed in Table 1.

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Because the refractive index pattern formed by the method of the present invention has a sufficiently large refractive index difference and the obtained refractive index difference is stable to light and heat, it is very suitable for use as an optical material in the field of optoelectronics and display. The refractive index pattern of the present invention can also Used as optical materials for optical arrays, lenses, optical couplers, optical repeaters, polarized light splitters, holograms, single-mode and multi-mode optical fibers, bundled fibers, light guides, single-core, multi-core and Photoelectric coupling optical connectors, optical separators, optical sensors such as photodiodes, optical penetrators, optical-ICs, CCD image sensors, CMOS image sensors, optical fiber sensors, and optical fiber gyros , Optical discs such as CD, LD, PD and DVD, optical converters, waveguides, optical touch panels, diffraction gratings, optical guides, optical diffusers, anti-reflectors and optical seals.