Emission-sensitive composition with variable refractory index and a method for varying refractory index

FIELD: special-destination substances.

SUBSTANCE: invention provides emission-sensitive composition containing polymerizable compound A, non-polymerizable compound B having lower refractory index than polymer of polymerizable compound A, and emission-sensitive polymerization initiator C. Invention also provides method for varying refractory index, structure formation method, and optical material preparation method.

EFFECT: stabilized structure and optical material independent of application conditions.

6 cl, 1 tbl, 12 ex

 

The scope of the invention

This invention relates to sensitive to radiation composition with changing refractive index, to a method of forming a formed by the refractive index structure, formed by the refractive index structure and to the optical material. More specifically, it relates to a new sensitive to radiation composition with varying refractive index, which is used in the fields of Photonics and display devices, to a method of forming a formed by the refractive index structure, formed by the refractive index structure and to the optical material.

Description of the prior art,

In modern society, called "media society", optically molded products with the distribution of the refractive index, each of which consists of areas with different refractive indices, are in great demand. The products contain not only the optical fiber to transmit information, but also the optical diffraction grating having a periodic variation in refractive index, optical storage device, in which information is recorded at positions having different refractive indices, associated optical elements such as optical integrated circuits (IC), having the e thin (i.e. fine or precision) structure formed by refractive index, optical control elements, the elements of the optical modulation and optical transmitting elements.

Optically molded products with the distribution of the refractive index are divided into two types: one having a continuous distribution of refractive index, for example, gradient-index optical fiber GI type in molded products (from the English. Gradient Index fiber, hereafter denoted as "optically molded products GRIN type"), and another with intermittent distribution of refractive index, such as an optical diffraction grating and an optical waveguide-type SI, i.e. graded fibers (from the English. Step Index fiber).

Optically molded products GRIN type attracted much attention as an optically molded products of the next generation. For example, optical fiber GI type refractive index which decreases from the Central axis of the core of the optical fiber to the periphery of a parabola, can transfer a large amount of information. The GRIN lens type, the refractive index continuously changes, are used as reading lenses for use in copying machines, spherical lenses for connecting fibers or lenses, allowing the use of their characteristic features is, namely, that they have a refractive ability even on a flat surface and that they are free from spherical aberration.

By now there have been proposed a large number of methods of production of these optically molded products GRIN type. For example, JP-A 9-133813, JP-A 8-336911, JP-A 8-337609, JP-A 3-192310, JP-A 5-60931 (used herein, the term "JP-A" means "not passed examination published patent application of Japan"). WO93/19505 and WO94/04949 disclose a method of obtaining an optical fiber GI-type dispersing a low-molecular compound or monomer in the polymer and the continuous distribution of its concentration. JP-A 62-25705 reveals starinavity optically molded product GI type optical fiber, which is obtained by photodepolymerization two or more vinyl monomers having different refractive indices and reactivity (copolymerization constants). Further, JP-A 7-56026 discloses a method of obtaining a distribution of refractive index forming polymer And having photoreaction-capable functional group, the dispersion connection having a lower refractive index than the polymer A, the polymer And to create a distribution concentration of the compound In, and photosimulation polymer And compound Century

Were also suggested some of the ways gender is implemented optically molded products GRIN type of inorganic material. One of them is, for example, a method of producing rod GI type addition of thallium with a high refractive index to sergevideo glass consisting essentially of silicon or lead, by immersing the glass in a molten solution containing potassium with low refractive index, and create a distribution of the concentration of potassium by ion exchange.

The GRIN lens type can be obtained similarly by applying the above method to short rod, that is, the lens-like optical molded product. Alternatively, the rod GI type, obtained by the above method, can be cut into layers.

As one of the above methods for obtaining optically molded product having a fine structure formed by the refractive index, such as an optical diffraction grating and optical IP-known technology achieve changes in refractive index cause a photochemical reaction in the molded product by the influence of light. For example, in the case of inorganic material is glass with an additive Germany is exposed to light to change its refractive index so as to obtain an optical diffraction grating. In the case of organic material such technology is known as photochromic reaction or photooverlay. JP-A 7-92313 races is rivet technology for the production of diffraction gratings produce changes in the refractive index of the material, containing dispersed polymer in the low-molecular compound having a photochemical reactivity by laser beam. Further, in JP-A 9-178901 recently proposed the application of this technology to obtain optically molded product GRIN type. This method provides a continuous distribution of refractive index in the direction of depth in relation to the radiation, using the fact that the light projected onto the molded product is absorbed and weakened in intensity.

However, the distribution of refractive index is achieved with the above conventional materials, the maximum difference of the refractive indices is only from about 0,001 to 0.02, and thus it is difficult to achieve a wider distribution of the refractive index to prevent optical loss and suppression of the improper functioning of the circuit.

In addition, when the above conventional materials used in those conditions after the formation of a distribution of refractive index through them passes light having a wavelength close to the wavelength used to change the refractive index, it is impossible to prevent the phenomenon of the gradual change of the refractive index, thereby destroying the materials.

The invention

D. the TES invention was made, considering the above situation and problems of the prior art.

Thus, the purpose of this invention is to provide sensitive to radiation with variable refractive index, the refractive index of which is changed by a simple method, the difference of the modified refractive index which is sufficiently large and which can provide a stable structure of the distribution of the refractive index and stable optical material, regardless of the conditions of their application.

Another purpose of this invention is to provide a method of forming patterns with the distribution of the refractive index of the composition according to the invention.

Another objective of this invention is to provide structre with the distribution of the refractive index or optical material obtained according to the method according to the invention.

Other objectives and advantages of this invention will become apparent from the following description.

First, the objectives and advantages of the invention are achieved through sensitive to radiation with variable refractive index, containing curable compound (A), polimerizuet compound (B)having a lower refractive index than the polymer of the curable compound (A), and is sensitive to the radiation initiator (C) the floor is merisalo.

Second, the objectives and advantages of the invention are achieved by using a method of changing the refractive index, is the impact of radiation on sensitive radiation composition with variable refractive index according to the invention.

Thirdly, the objectives and advantages of the invention are achieved with a method of forming patterns with the distribution of the refractive index, is the impact of radiation through the template structure sensitive to radiation, the composition of the variable refractive index according to the invention, which has been previously subjected to heat treatment and which has been pre-attached to the required form.

Fourth, objectives and advantages of the invention are achieved with a method of obtaining optical material, is the impact of radiation on the form for an optical material sensitive to radiation with variable refractive index according to the invention through the template for the formation of optical material having a structure with a distribution of refractive index.

In this invention, the term "structure, distribution of refractive index" means a material with a distribution of refractive index is formed in the form of areas having different refractive indices. A comparison of values show the lei of refraction is performed on the basis of the refractive indices, measured at room temperature and at a wavelength of 633 nm.

Preferred variants of the embodiment of the invention

Next, the detailed description of each component material with variable refractive index used in the method of forming patterns formed by the refractive index according to this invention.

Curable compound (A)

Any known compound which polymerizes or interacts with acid, base or radical, can be used as the curable compound (A)used in this invention. The refractive index of its polymer preferably from equal to 1.45 to 1.9, more preferably from 1.5 to 1.9. Although curable compound used as component (A)is typically a monomer, its molecular weight is not specifically limited, and it may have a molecular weight, such as oligomer. The compound, which has in the molecule two or more curable functional groups such as double bonds, can also be preferably used.

Compound that polymerizes or interacts with acid, base or radical derived from sensitive to radiation present and degrades substance is a compound having in a molecule capable of polymerization options the regional group, such as vinylgroover, group etilenimina, epoxypropan, apicultura group, hydroxyl group or oceanodroma.

Examples of the above compounds include vinylaromatic connection, the connection is simple vinyl ether, acrylic acid and methacrylic acid monomers, polymerized with ring opening with apachegroup, connection oxetane and maleimide. Typical examples of these compounds are given below.

Typical examples vinylaromatic compounds include styrene and derivatives of styrene such substituents as alkyl, alkoxyl, halogen, halogenated, nitro, cyano, amide groups, ether complex and/or halogen in α-, o-, m - and/or p-position; monovinyl aromatic compounds, such as styrelseledamot acid, 2,4-dimethylstyrene, para-dimethylaminostyryl, vinylbenzoate, vinylbenzene, inden, 1-methylindene, acenaphthalene, vinylnaphthalene, vinylanthracene, vinylcarbazole and 2-viniflora; polyfunctional vinylaromatic compounds such as o-, m - and p-divinylbenzene, o-, m - and p-diisopropenylbenzene, 1,2,4-trivinylbenzene, 1,2-vinyl-3,4-xylene, 1,3-Divinington, 1,3,5-trigeneration, 2,4-diphenylmethane, 3,5,4'-triphenylmethane, 1,2-divinyl-3,4-xylene and 1,5,6-trivinyl-3,7-deethylation. The divinylbenzene and diisopropenylbenzene can be in the form of the-, m - and p-isomers or in the form of mixtures of these isomers.

Typical examples of compounds with simple vinyl ether include monoalkylamines ethers, such as metilidinovy simple ether, ethylenically simple ether, n-propylvinyl simple ether, n-butylvinyl simple ether, tert-butylaniline simple ether, isobutylphenyl simple ether, tert-millinery simple ether, dodecylphenol simple ether, octadecylsilyl simple ether, butylvinyl simple ether of ethylene glycol, ethylenically simple ether of triethylene glycol, 2-khlorehtilaminami simple ether, 2-ethylhexylacrylate simple ether, cyclohexylaniline simple ether, aminopropylsilyl simple ester and 2-(diethylamino)ethylenically simple ether; monoarylamino simple esters, such as benzylaniline simple ether, phenyleneoxy simple ether, para-toolwindows simple ether and nativeenergy simple ether; divinelvie ethers, such as divinely simple ether of butane-1,4-diol, divinely simple ether hexane-1,6-diol, divinely simple ether of 1,4-cyclohexanedimethanol, di(4-vinyloxy)butyl-isophthalate, di(4-vinyloxy)butyl terephthalate, di(4-vinyloxy)butyl-glutarate, di(4-vinyloxy)butyl succinate, divinely simple ether of ethylene glycol, divinely simple ether of diethylene glycol and divinely simple EPE is triethylene glycol; criminologie ethers, such as criminology simple ether of trimethylolpropane; Terminologie ethers, such as terminology simple ester of pentaerythritol, and containing a hydroxyl group, vinyl ethers, such as monomineralic simple ether of butanediol, monomineralic simple ether of ethylene glycol, monomineralic simple ether of diethylene glycol, monomineralic simple ether cyclohexanedimethanol and monomineralic simple ether hexandiol.

Typical examples of compounds of methacrylic acid and acrylic acids include methacrylic acid, acrylic acid and esters, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentalogy, neopentylene, isoenergetically, cyclohexyloxy, adamantly, allyl, propargilovyh, phenyl, nattily, antrectomy, antrachinonnoy, peperonity, salicylic, cyclohexyloxy, benzyl, finitely, crazily, glycidyloxy, 1,1,1-cryptonemiales, perforations, PERFLUORO-n-propyl, PERFLUORO-isopropyl, triphenylmethane, tricyclo[5.2.1.02,6]decane-8-silt (called "dicyclopentadienyl" in this technical field), tomilovy, 3-(N,N-dimethylamino)propyl, 3-(N,N-dimethylamino)ethyl, furrowy and furfuryl ester of methacrylic acid and acrylic key is lots; anilide and amides of methacrylic or acrylic acid, such as amide, N,N-dimethyl, N,N-diethyl, N,N-dipropyl, N,N-aminobutiramida and antranig-methacrylic acid and acrylic acid; polyfunctional (meth)acrylates such as di(meth)acrylate of ethylene glycol, di(meth)acrylate of diethylene glycol, di(meth)acrylate of propane diol, di(meth)acrylate butanediol di(meth)acrylate of hexanediol, di(meth)acrylate of trimethylolpropane, three(meth)acrylate of trimethylolpropane three(meth)acrylate of pentaerythritol, Tetra(meth)acrylate of pentaerythritol, (meth)acryloyloxyhexyloxy, 1,4-bis[(meth)acryloyldimethyltaurate]benzene, di(meth)acrylate compounds obtained by the accession of propylene oxide ethylene oxide to both ends of hydroquinone or bisphenol a, 2,2-bis(4-(methacryloyloxy)phenyl)propane, 2-acryloyloxy-2-hydroxypropionate, bis(4-Methacrylonitrile)sulfide, n-bis(2-methacryloyloxyethyl)xylylene and p-bis(2-methacryloyloxyethyl)xylylene.

Typical examples of polymerized with ring opening monomers having apachegroup include diglycidyl simple ether of bisphenol A, diglycidyl simple ether of bisphenol F, diglycidyl simple ether of bisphenol S, diglycerol simple ether of brominated bisphenol A, diglycidyl simple ether of brominated bisphenol F, diglycidyl simple ether of brominated bisphenol S, diglycidyl the first simple ether of hydrogenated bisphenol A, diglycidyl simple ether of hydrogenated bisphenol F, diglycidyl simple ether of hydrogenated bisphenol S, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-Spiro-3,4-epoxy)cyclohexanediamine, bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexane, 4-venereologica, bis(3,4-epoxy-6-methylcyclohexyl-methyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylic, Methylenebis(3,4-epoxycyclohexane), Dicyclopentadiene-diepoxide, ethylene glycol di(3,4-epoxycyclohexane carboxylate), dioctyl epoxyacrylate, di-2-ethylhexyl epoxyacrylate, diglycerol simple ether of 1,4-butanediol, diglycidyl simple ether of 1,6-hexandiol, triglycerol simple ether of glycerol, triglycerol simple ether of trimethylolpropane, diglycidyl simple ether of polyethylene glycol, diglycidyl simple ether polypropylenglycol, polyglycidyl ethers of polyetherpolyols obtained by adding one or more alkalisation to aliphatic polyhydric alcohol such as ethylene glycol, propylene glycol or glycerol, diglycidyl esters of aliphatic dibasic acids with long-chain, monoglycidyl ethers of aliphatic higher alcohol and monoglycidyl ethers Hairdryer is La, cresol, butylphenol or politisite obtained by attaching accelerated to these alcohols. In addition, can also be used diepoxybutane obtained by substitution of the oxygen atom apostolica each of these compounds by sulfur atom.

Typical examples of compounds of oxetane include:

3-ethyl-3-methoxyethoxide,

3-ethyl-3-ethoxyethylacetate,

3-ethyl-3-butoxyethoxy,

3-ethyl-3-hexyloxyethoxy,

3-methyl-3-hydroxyethyloxy,

3-ethyl-3-hydroxyethyloxy,

3-ethyl-3-allyloxymethyl,

3-ethyl-3-(2'-hydroxyethyl)oxytetracyclin,

3-ethyl-3-(2'-hydroxy-3'-phenoxypropan)oxytetracyclin,

3-ethyl-3-(2'-hydroxy-3'-butoxypropyl)oxytetracyclin,

3-ethyl-3-[2'-(2"-ethoxyethyl)oxymethyl]oxetan,

3-ethyl-3-(2'-butoxyethyl)oxytetracyclin,

3-ethyl-3-benzyloxypyridine and

3-ethyl-3-(p-tert-butylbenzylamine)oxetan.

Also preferably can be used in connection with and oxetanyl, and the polymerized vinylgroover in the molecule, such as:

3-((meth)acryloyloxy)oxetan,

3-((meth)acryloyloxy)-2-triftormetilfosfinov,

3-((meth)acryloyloxy)-2-phenyloxirane,

2-((meth)acryloyloxy)oxetan and

2-((meth)acryloyloxy)oxetan and

2-((meth)acryloyloxy)-4-trifloromethyl Satan.

Typical examples of monomers based maleimide include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, benzoate N-Succinimidyl-3-maleimide, butyrate N-Succinimidyl-4-maleimide, caproate N-Succinimidyl-6-maleimide, propionate, N-Succinimidyl-3-maleimide and N-(9-acridine)maleimide.

Can also be used Acrylonitrile, acrolein, Methacrylonitrile, vinyl chloride, vinylidenechloride, viniferin, vinylidenefluoride, N-vinyl pyrrolidone, vinylpyridine and vinyl acetate.

The hydrogen atom contained in these compounds, designated as component (a)may be substituted by a chlorine atom, a bromine atom, a hydroxyl group, mercaptopropyl, alkoxygroup, tiukinhoy, halogenlampe, halogenlampe, halogenoalkanes, the group of complex alkylthiophene, mercaptoethanol, allgroups, arlbergpass or cyano.

This alkoxygroup may be linear or branched. Examples of alkoxygroup include a methoxy group, ethoxypropan, n-propoxylate, isopropoxy, n-butoxypropyl, isobutoxy, sec-butoxypropyl, tert-butoxypropyl, n-pentyloxy, neopentadactyla and n-hexyloxy.

This allylthiourea may be linear or branched. Examples of ancilliary include metalcorp, atilt the group, n-PropertyGroup, isopropylthio, n-butylthiourea, isobutylthiazole, sec-butylthiourea, tert-butylthiourea, n-intelligroup, pointertype and n-vexillographer.

Examples of the specified halogenlampe include triptoreline, pentaceratops, heptafluoropropyl, chlorotalpa, 2-chlorotalpa, 3-chloropropyl, 1-chloromethylating, 4-chlorobutyrate,

2-chloromethylpyridine, 5-Charpentier,

3-chloromethylstyrene, 2-chloroethylamino,

6-chlorhexiderm, 3-chlorotitanium,

4-chlorotitanium, 2-chlorideviagra, bromyalgia, 2-bramaterra, 3-bromopropyl, 1-bromoethylamine, 4-brombutylruber, 2-bromomethylpropane, 5-bramantesque, 3-brombutylruber, 2-prematilleke,

6-bromhexinum, 3-bromomethylphenyl,

4-bromomethylphenyl and 2-promativatj.

Examples of the specified halogenlampe include cryptometer, pentafluoropropyl,

heptafluoropropoxy, chlorotoxin, 2-chlorethoxyfos, 3-chloropropoxy, 1-chloromethyloxirane,

4-chlorotoxin, 2-chloromethyloxirane,

5-Globetrotter, 3-chloromethyloxirane,

2-chlorotyrosine, 6-chlorhexiderm,

3-chloromethylmethylether is the SCP, 4-chloromethyloxirane,

2-chloroethylnitrosourea, bromoethoxy, 2-pomatocalpa, 3-bromoprop, 1-Bromeliaceae,

4-bromoethoxy, 2-bromomethylpropanes,

5-Bromeliaceae, 3-bromomethylphenyl,

2-prematilleke, 6-Bromhexine,

3-bromodiphenylmethane, 4-bromodiphenylmethane and 2-prematilleke.

Examples of the specified halogenation include triptoreline, pentafluoropropyl,

heptafluorobutyrate, chloromethylthiazole, 2-chloroethylthio, 3-chloropropionate, 1-chlortetracycline, 4-chloroethylthio, 2-chloromethylpyridine, 5-chlorphentermine, 3-chloromethylpyridine, 2-chloroethylnitrosourea, 6-chlorhexidine, 3-chloromethylpyridine, 4-chloromethylpyridine, 2-chloroethylnitrosourea, bromatology, 2-bromatology, 3-bromopropionate, 1-promediacorp, 4-bromatologia, 2-bromomethylphenyl, 5-bcompetitio, 3-bromocinnamaldehyde, 2-brometalia, 6-bromhexinum, 3-bromomethylphenyl, 4-bromomethylphenyl and 2 bromocinnamaldehyde.

Examples of the specified mercaptoacetate include mercaptomethyl, 2-mercaptoethyl,

3-marketpro is idgruppo, 1-mercaptopyridine, 4-mercaptopurine, 2-mercaptoethylamine, 5-mercaptophenyl, 3-mercaptoethylamine, 2-mercaptoethylamine, 6-mercaptohexyl, 3-mercaptopyridine, 4-mercaptopyridine and 2-mercaptoethylamine.

Examples of the specified airgroup include panelgroup, tailgroup, cellgroup, Kolenergo and 1-aftercrop.

Examples of the specified Uralkaliy include benzerrou, α-methylbenzyl, panelgroup and naphthylmethyl.

Known compounds listed above can be used as the curable compound (A) in this invention without limitation. The compound having an aromatic ring, a halogen atom or a sulfur atom, can be advantageously used to increase the difference between the refractive index and the refractive index of the component (B).

The polymerized oligomeric compound can also be used as the curable compound (A) in this invention.

Specified reactive oligomeric compound selected from such compounds as polymerized oligomeric compound having unsaturated type ethylene bond, oligomeric epoxysilane, oligomeric tieran connection, the oligomeric compound of oxetane, connect the tion of alkoxysilanes, alkoxymethyl-glycoluril connection, connection alkoxymethyl-benzoguanamine, the connection alkoxylation, the connection isocyanate compound cyanate, connection oxazoline, the connection of oxazine and siliconindia (halogenated siliconindia or other siliconindia).

Specified curable oligomeric compound having unsaturated type ethylene bond, is preferably monofunctional or bifunctional (meth)acrylate or (meth)acrylate having a functionality of 3 or more, especially preferred from the point of view of polimerizuet and strength obtained utverzhdenii film bifunctional (meth)acrylate or (meth)acrylate having a functionality of 3 or more.

The examples of the mentioned monofunctional (meth)acrylate include 2-hydroxyethyl-(meth)acrylate, carbitol-(meth)acrylate, isobornyl-(meth)acrylate, 3-methoxybutyl-(meth)acrylate and 2-(meth)acryloyloxy-2-hydroxypropionate. Commercially available products of the specified monofunctional (meth)acrylate include Aronix M-101, M-111 and M-114 (Toagosei Chemical Industry Co., Ltd.), KAYARAD TC-110S and TS-120S (Nippon Kayaku Co., Ltd.) and Biscoat 158 and 2311 (Osaka Yuki Called Kogyo Co., Ltd.).

Examples of the specified bifunctional (meth)acrylate include (meth)acrylate of ethylene glycol, di(meth)acrylate 1,6-hexanediol, di(meth)acrylate 1,9-nonanediol, di(meth)acrylate, polypropylene bags, is angelicola, di(meth)acrylate of tetraethyleneglycol, diacrylate bifunctionality, 2,2-bis(4-((meth)acroloxidae)phenyl)propane, 2-(meth)acryloyloxy-2-hydroxypropionate, bis(4-(meth)acryloyldimethyl)sulfide, n-bis(2-(meth)acryloyloxy)xylylene and

p-bis(2(meth)acryloyloxy)xylylene. Commercial

available products specified bifunctional (meth)acrylate include Aronix M-210, M-240 and M-6200 (Toagosei Chemical Industry Co., Ltd.), KAYARAD HDDA, HX-220 and R-604 (Nippon Kayaku Co., Ltd.) and Biscoat 260, 312 and 335HP (Osaka Yuki Called Kogyo Co., Ltd.).

Examples specified (meth)acrylate having a functionality of 3 or more, include three(meth)acrylate of trimethylolpropane, three(meth)acrylate of pentaerythritol, three((meth)acryloyloxy)phosphate, Tetra(meth)acrylate of pentaerythritol, Penta(meth)acrylate of dipentaerythritol and hexa(meth)acrylate of dipentaerythritol. Commercially available products of the specified (meth)acrylate having a functionality of 3 or more include Aronix M-309, M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M-1310, M-1600, M-1960, M-8100, M-8530, M-8560 and M-9050 (Toagosei Chemical Industry Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60 and DPCA-120 (Nippon Kayaku Co., Ltd.) and Biscoat 295, 300, 360, GPT, 3PA and 400 (Osaka Yuki Called Kogyo Co., Ltd.).

In addition to these compounds (meth)acrylate, as polymerized compounds having unsaturated type ethylene bond, in this invention an advantageous manner can be further used in the urethane acrylates, and the products of urethane and acrylate polyesters. Commercially available products of these curable compounds having unsaturated type ethylene communication include Aronix M-7100, M-8030, M-8060, M-1310, M-1600, M-1960, M-8100, M-8530, M-8560 and M-9050 (Toagosei Chemical Industry Co., Ltd.).

These monofunctional and bifunctional (meth)acrylates, (meth)acrylates having a functionality of 3 or more, urethane acrylates, urethane adducts and acrylate polyesters can be used separately or in combination.

Examples of the specified OPC epoxysilane include epoxy resin based on bisphenol A, epoxy resin based on bisphenol F, phenol Novolac epoxy resin, kretlow Novolac epoxy resin, cyclic aliphatic epoxy resin, epoxysilane bisphenol A and an aliphatic polyglycidyl simple ether.

Examples of commercially available products of these compounds are given below. Commercially available products of epoxy resins based on bisphenol A include Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010 and 828 (Yuka Shell Epoxy Co., Ltd.), the products of epoxy resins based on bisphenol F include Epicoat 807 (Yuka Shell Epoxy Co., Ltd.), the products of phenolic Novolac epoxy resin include Epicoat 152 and 154 (Yuka Shell Epoxy Co., Ltd.) and EPPN201 and 202 (Nippon Kayaku Co., Ltd.), products krasilnoj Novolac epoxy resins include EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 (Nippon Kyaku Co., Ltd.) and Epicoat 180S75 (Yuka Shell Epoxy Co., Ltd.), the products of cyclic aliphatic epoxy resin include CY175, CY177 and CY179 (CIBA-GEIGY A.G.), ERL-4234, ERL-4299, ERL-4221 and ERL-4206 (U.C.C. Co., Ltd.), Showdyne 509 (Showa Denko K.K.), Araldyte CY-182, CY-192 and CY-184 (CIBA-GEIGY A.G.), Epichlon 200 and 400 (Dainippon Ink and Chemicals, Inc.), Epicoat 871 and 872 (Yuka Shell Epoxy Co., Ltd.) and ED-5661 and ED-5662 (Celanees Coating Co., Ltd.) and products of aliphatic polyglycidyl simple ether include Epolite 100MF (Kyoeisha Depending Co., Ltd.) and Epiol TMP (NOF Corporation).

In addition to these compounds, preferably can be used containing sulphur epoxysilane, such as:

bis(β-epoxypropyl)sulfide,

bis(β-epoxypropyl)methane,

1,2-bis(β-epoxypropyl)ethane,

1,3-bis(β-epoxypropyl)propane,

1,2-bis(β-epoxypropyl)propane,

1-(β-epoxypropyl)-2-(β-epoxypropoxyphenyl)propane,

1,4-bis(β-epoxypropoxy)butane,

1,3-bis(β-epoxypropoxy)butane,

1-(β-epoxypropyl)-3-(β-epoxypropoxyphenyl)butane,

1,5-bis(β-epoxypropyl)pentane,

1-(β-epoxypropyl)-4-(β-epoxypropoxyphenyl)pentane,

1,6-bis(β-epoxypropyl)hexane,

1-(β-epoxypropyl)-5-(β-epoxypropoxyphenyl)hexane,

1-(β-epoxypropyl)-2-[(2-β-epoxypropyl)thio]ethane,

1-(β-epoxypropyl)-2-[(2-(2-β-epoxypropyl)thioethyl)thio]ethane,

tetrakis(β-epoxypropoxyphenyl)methane,

1,1,1-Tris(β-epoxypropoxyphenyl)propane,

1,5-bis(β-epoxypropyl)-2-(β-epoxypropoxyphenyl)-thiopental,

1,5-bis(β-epoxypropyl)-2,4-bis(β-epoxypropoxyphenyl)-3-thiopental,

1-(β-epoxypropoxy)-2,2-bis(β-epoxypropoxyphenyl)-4-tuexen,

1,5,6-Tris(β-epoxypropyl)-4-(β-epoxypropoxyphenyl)-3-tuexen,

1,3 - and 1,4-bis(β-epoxypropyl)cyclohexane,

1,3 - and 1,4-bis(β-epoxypropoxyphenyl)cyclohexane,

bis[4-(β-epoxypropyl)cyclohexyl]methane,

2,2-bis[4-(β-epoxypropyl)cyclohexyl]propane,

bis[4-(β-epoxypropyl)cyclohexyl]sulfide,

2,5-bis(β-epoxypropoxyphenyl)-1,4-dition,

2,5-bis(β-epoxypropyltrimethylammonium)-1,4-dition,

1,3 - and 1,4-bis(β-epoxypropyl)benzenes,

1,3 - and 1,4-bis(β-epoxypropoxyphenyl)benzenes,

bis[4-(β-epoxypropyl)phenyl]methane,

2,2-bis[4-(β-epoxypropyl)phenyl]propane,

bis[4-(β-epoxypropyl)phenyl]sulfide,

bis[4-(β-epoxypropyl)phenyl]sulfon and

4,4'-bis(β-epoxypropyl)biphenyl;

and oligomeric epoxysilane, such as phenylglycidyl simple ether, butespecially simple ether, 3,3,3-triftormetilfullerenov, stimulated, geksaftorpropilenom, cyclohexanone, N-gilderfluke, (nonfor-N-butyl)epoxide, perforat glycidyloxy simple ether, the epichlorohydrin, epibromohydrin, N,N-diglycidyl-aniline and 3-[2-(perferences)ethoxy]-1,2-epoxypropane.

Examples of the specified tieran-compounds include compounds obtained by substitution of apachegroup these oligomeric epoxy compounds group tylenchida, as shown, for example, in J. Org. Chem., 28, 229 (1963).

Examples of the specified oligomeric compounds oxetane include:

bis[(3-ethyl-3-oxetanemethanol)methyl]benzene (trade

name: XDO, produced by Toagosei Chemical Industry Co., Ltd.),

bis[(3-ethyl-3-oxetanemethanol)were]methane,

bis[(3-ethyl-3-oxetanemethanol)were]a simple ether

bis[(3-ethyl-3-oxetanemethanol)were]propane,

bis[(3-ethyl-3-oxetanemethanol)were]sulfon,

bis[(3-ethyl-3-oxetanemethanol)were]ketone,

bis[(3-ethyl-3-oxetanemethanol)were]hexaferrite,

three[(3-ethyl-3-oxetanemethanol)methyl]benzene and

Tetra[(3-ethyl-3-oxetanemethanol)methyl]benzene.

These connection alkoxysilanes, the connection of alkoxybenzenes, the connection of alkoxyglycerols and connection alkoxylation get a replacement Mediagroup connection methylaniline, connection methylolmethacrylamide, connection Meterological and connection metrologiya alkoxygroup, respectively. Type alkoxygroup Conques is to maintain not limited to, examples can be methoxymethyl, ethoxymethylene, propoxymethyl and butoxymethyl.

Commercially available products of these compounds include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170 and 1174 and UFR65 and 300 (of Mitsui Cyanamid Co., Ltd.) and Nikalac Mx-750, Mx-032, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11 and Mw-30 (Sanwa Chemical Co., Ltd.).

Examples of the compounds of the isocyanate include:

phenylene-1,3-diisocyanate,

phenylene-1,4-diisocyanate,

1-methoxyphenyl-2,4-diisocyanate,

1-methylphenylene-2,4-diisocyanate,

2,4-tolylenediisocyanate,

2,6-tolylenediisocyanate,

1,3-xylylenediisocyanate,

1,4-xylylenediisocyanate,

biphenylene-4,4'-diisocyanate,

3,3'-dimethoxybiphenyl-4,4'-diisocyanate,

3,3'-dimethylbiphenyl-4,4'-diisocyanate,

the difenilmetana-2,4'-diisocyanate,

the difenilmetana-4,4'-diisocyanate,

3,3'-dimethoxybiphenyl-4,4'-diisocyanate,

3,3'-dimethyldiphenyl-4,4'-diisocyanate,

naftilan-1,5-diisocyanate,

CYCLOBUTANE-1,3-diisocyanate,

cyclopentene-1,3-diisocyanate,

cyclohexyl-1,3-diisocyanate,

cyclohexyl-1,4-diisocyanate,

1-methylcyclohexane-2,4-diisocyanate,

1-methylcyclohexane-2,6-diisocyanate,

1-isocyanate-3,3,5-trimethyl-5-isocyanate

methylcyclohexane,

cyclohexane-1,3-bis(methyl isocyanate),

cyclohexane-1,4-bis(methyl isocyanate),

isophorondiisocyanate,

D. cyclohexylmethyl-2,4'-diisocyanate,

dicyclohexylmethane-4,4'-diisocyanate,

atlantaatlanta,

tetramethylene 1,4-diisocyanate,

hexamethylen-1,6-diisocyanate,

dodecamethyl-1,12-diisocyanate,

methyl ester of lysine diisocyanate, and prepolymers having an isocyanate group at both ends, obtained by the reaction of a stoichiometric excess of one of these organic diisocyanates and containing bifunctional active hydrogen compound.

The specified diisocyanate may be used in combination with an organic polyisocyanate having 3 or more isocyanate groups, such as:

phenyl-1,3,5-triisocyanate,

the difenilmetana-2,4,4'-triisocyanate,

the difenilmetana-2,5,4'-triisocyanate,

triphenylmethane-2,4',4"-triisocyanate,

triphenylmethane-4,4',4"-triisocyanate,

the difenilmetana-2,4,2',4'-tetrazocine,

the difenilmetana-2,5,2',5'-tetrazocine,

cyclohexane-1,3,5-triisocyanate,

cyclohexane-1,3,5-Tris(methyl isocyanate),

3,5-dimethylcyclohexane-1,3,5-Tris(methyl isocyanate),

1,3,5-trimethylcyclohexane-1,3,5-Tris(methyl isocyanate),

dicyclohexylmethane-2,4,2'-triisocyanate or

dicyclohexylmethane-2,4,4'-triisocyanate, or

a prepolymer having an isocyanate group at the end, obtained by the reaction of a stoichiometric excess of one of these organic polyisocyanates, having the x 3 or more isocyanate groups, and containing polyfunctional active hydrogen compounds having 2 or more hydrogen atoms.

Examples of the compounds of oxazoline include:

2,2'-bis(2-oxazoline),

4-furan-2-ylmethylene-2-phenyl-4H-oxazol-5-he,

1,4-bis(4,5-dihydro-2-oxazolyl)benzene,

1,3-bis(4,5-dihydro-2-oxazolyl)benzene,

2,3-bis(4-Isopropenyl-2-oxazoline-2-yl)butane,

2,2'-bis-4-benzyl-2-oxazoline,

2,6-bis(isopropyl-2-oxazoline-2-yl)pyridine,

2,2'-isopropylidene-bis(4-tert-butyl-2-oxazoline),

2,2'-isopropylidene-bis(4-phenyl-2-oxazoline),

2,2'-methylene-bis(4-tert-butyl-2-oxazoline), and

2,2'-methylene-bis(4-phenyl-2-oxazoline).

Examples of the compounds of oxazine include:

2,2'-bis(2-oxazin),

4-furan-2-ylmethylene-2-phenyl-4H-oksazil-5-he,

1,4-bis(4,5-dihydro-2-oksazil)benzene,

1,3-bis(4,5-dihydro-2-oksazil)benzene,

2,3-bis(4-Isopropenyl-2-oxazin-2-yl)butane,

2,2'-bis-4-benzyl-2-oxazin,

2,6-bis(isopropyl-2-oxazin-2-yl)pyridine,

2,2'-isopropylidene-bis(4-tert-butyl-2-oxazin),

2,2'-isopropylidene-bis(4-phenyl-2-oxazin),

2,2'-methylene-bis(4-tert-butyl-2-oxazin) and

2,2'-Methylenebis(4-phenyl-2-oxazin).

Examples of the specified halogenated siliconindia include tetrachlorosilane, such as tetrachlorosilane, tetrabromide, tetraiodide, trichlorosilane and dichloropropylene;

monoalkyl halogenosilanes, such as methyltrichlorosilane, methyldichlorosilane and cyclohexyltrichlorosilane;

monoacrylated, such as phenyltrichlorosilane, naphthylthiourea, 4-chlorophenyltrichlorosilane and phenyldichloroarsine;

monohalomethanes, such as panaxytriol and PEROXYDICARBONATE;

monoalkylation, such as metaxytherium and amoxicillan;

dialkyldiphenyl, such as a clear, methyl(ethyl)DICHLOROSILANE and methyl(cyclohexyl)dichlorsilane;

monoalkylammonium, such as methyl(phenyl)DICHLOROSILANE;

diarylethylenes, such as diphenyldichlorosilane;

dialogtitleversion, such as Diphenoxylate;

monoaminooxidase, such as methyl(phenoxy)dichlorsilane;

monoaminooxidase, such as phenyl(phenoxy)dichlorsilane;

dialkoxybenzene, such as diethoxymethylsilane;

monoaminooxidase, such as methyl(ethoxy)dichlorsilane;

monoaminooxidase, such as phenyl(ethoxy)dichlorsilane;

trialkylaluminium, such as trimethylchlorosilane, dimethyl(ethyl)chlorosilane and dimethyl(cyclohexyl)chlorosilane;

dialkylaminoalkyl, such as dimethyl(phenyl)chlorosilane;

was monoalkylammonium enseleni, such as methyl(diphenyl)chlorosilane;

triaminotrinitrobenzene, such as trigonometrician;

monoalkylammonium, such as methyl(diphenoxy)chlorosilane;

monocrystallization, such as phenyl(diphenoxy)chlorosilane;

dialkylmonothiophosphinate, such as dimethyl(phenoxy)chlorosilane;

diarylaminochloroquinones, such as diphenyl(phenoxy)chlorosilane;

monoaminodinitrotoluenes, such as methyl(phenyl)(phenoxy)chlorosilane;

triethoxyoctylsilane, such as triethoxysilane; and their oligomers, such as dimer, trimer, tetramer and pentamer of tetrachlorosilane.

Examples of other specified siliconindia include:

hexamethyldisilazane, tert-butyldimethylchlorosilane,

bis(trimethylsilyl)triptorelin,

diethylaminocoumarin, trimethylsilanol,

hexamethyldisiloxane, chlorotrimethylsilane,

acetyltryptamine, ethoxytrimethylsilane,

triphenylsilanol, triethylsilanol, Tripropylamine,

tributyltin, hexaethyldisiloxane,

trimethyloxonium, trimethylaluminium,

triethylammonium, triethylaluminium,

acetoxyisobutyryl,

1,3-bis(hydroxybutyl)tetramethyldisiloxane,

1,3-bis(hydroxypropyl)tetramethyldisiloxane is,

γ-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane,

N-β(aminoethyl)-γ-aminopropyltrimethoxysilane,

N-β(aminoethyl)-γ-aminopropyltrimethoxysilane,

N-phenyl-γ-aminopropyltrimethoxysilane,

γ-anilinopyrimidines,

γ-dibutylaminoethanol,

γ-ureidopropionic,

hydrochloric N-β(N-vinylbenzoate)-γ-aminopropyltrimethoxysilane,

γ-methacryloxypropyltrimethoxysilane,

γ-methacryloxypropyltrimethoxysilane,

VINYLTRIMETHOXYSILANE, vinyltriethoxysilane,

vinyltrichlorosilane, vinyl-Tris(β-methoxyethoxy)silane,

γ-glycidoxypropyltrimethoxysilane,

γ-glycidoxypropyltrimethoxysilane,

γ-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,

γ-glycidoxypropyltrimethoxysilane,

γ-mercaptopropionylglycine,

γ-chloropropionitrile, trimethylchlorosilane,

hexamethyldisilazane, N-trimethylsilylimidazole,

bis(trimethylsilyl)urea, trimethylsilylacetamide,

bestemmelsessted, trimethylsilyltriflate,

trimethyloxonium, trimethylaluminium,

methyltrimethoxysilane, methyltriethoxysilane,

dimethyldiethoxysilane, dimethyldiethoxysilane,

tert-butyldimethylchlorosilane, tert-butyldiphenylchlorosilane

triisopropylchlorosilane, n-propyltrimethoxysilane,

isobutyltrimethoxysilane, n-hexyltrimethoxysilane,

n-decyltrimethoxysilane, n-hexadecyltrimethylammonium,

1,6-bis(trimethoxysilyl)hexane, dimethylimidazolidin, methicillinresistant, phenyltrimethoxysilane,

diphenylimidazole and penicillinresistant.

These known compounds can be used without limitation as reactive oligomeric compounds. Although any reactive oligomeric compound with a preferred refractive index can be selected in accordance with the refractive index of the component (B), a compound containing an aromatic ring and the sulfur atom may be preferably used to increase the difference of refractive indices between him and the component (B).

Preferably, the compound having a boiling point at 1 Torr (133,3 PA) is preferably 160°C or lower, more preferably 130°With or below, is contained in the amount of at least 20 wt.% as the curable compound (A) in this invention. When the number of connections is less than 20 wt.%, the composition, which provides a large difference between the refractive indices cannot be obtained.

From compounds other than reactive about egomania connection listed above and contained in the curable compound (A), vinylaromatic connections, connections simple vinyl ether and (meth)acrylic acid mainly provide a curable compound having a boiling point at 1 Torr 160°With or below.

When reactive oligomeric compound is used as the curable compound (A), the strength of the structure formed by the refractive index and formed by the method according to this invention, is improved. These compounds are listed as component (A)may be used singularly or in combination of two or more compounds.

Polimerizuet connection (In)

Component (C)used in this invention is a material which is resistant to acid, base or radical and preferably has a high optical transparency. The refractive index of the component (C) can be set and communicated to the preferred values, respectively purpose. The refractive index of nBcompound (B) is less than the refractive index of nApolymer polymerized compounds (A) and, particularly preferably satisfies the following expression (1):

Polimerizuet compound (B) may be a binder polymer, i.e. a polymer that can serve as a binder for compound (A).

Examples of the binder polymer (B) include acrylic resin, urethane resin, resin-based complex polyester, polycarbonate resin, norbornene resin, styrene resin, resin-based polyether sulfone, silicone resin, polyamide resin, polyimide resin, polysiloxane resin, fluorocarbon resin, polybutadiene resin, a resin based on a simple vinyl ether resin based on vinyl ether complex. The preferred binder polymer (B) can be selected in accordance with the refractive index of the used polymer compound (A). To increase the difference of refractive indices between him and the polymer compound (A) and to reduce the transmission loss for the long optical path in it, may be advantageously used binder polymer (B)obtained by substitution of hydrogen atoms of the specified resin fluorine atom.

Illustrative examples of the binder polymer (B) include the following polymers (numbers inside the parentheses are values of the refractive index, measured using a d-ray): polyvinylidene fluoride (1,42), polydimethylsiloxane (1,43), politicomilitary (1,44), polyoxypropylene (1,45), polivinilbutilovy Rostow ether (1,45), polyvinylether (1,45), polyoxyethylene (1,46), polyvinylbutyral simple ether (1,46), polivinilbutilovy simple ether (1,46), polyvinilcelates simple ether (1,46), poly(4-methyl-1-penten) (of 1.46 to 1.47), acetate-butyrate cellulose (1,46-1,49), poly(4-fluoro-2-trifloromethyl) (1,46), polivinilbutilovy simple ether (1,46), poly(vinyl-2-ethylhexyloxy simple ether) (1,46), polivinilbutilovy simple ether (1,46), poly(2-methoxyethylamine) (1,46), polymethylacrylate (1,46), poly(tert-butyl methacrylate) (1,46), polivinilbutilovy simple ether (1,46), poly(3-ethoxypropylamine) (1,47), polioksidony-tetramethylene (1,47), polyvinylpyridine (1,47),polyvinyl acetate (1,47), polivinilbutilovy simple ether (1,47), politicalit (1,47), copolymer of ethylene-vinyl acetate (1,47-1,50), cellulose propionate (80%-20% vinyl acetate) (1,47-1,49), acetate-propionate cellulose (1,47), benzyltoluene (1,47-1,58), phenol-formaldehyde resin (1,47 is 1.70), triacetate cellulose (about 1.47 to 1.48), polivinilbutilovy simple ether (isotactic) (1,47), poly(3-methoxypropylacetate) (1,47), poly(2-ethoxyethylacetate) (1,47), polymethylacrylate (about 1.47 to 1.48), polyisopropylene (1,47), poly(1-mission) (1,47), polypropylene (atactic, density 0,8575 g/cm3) (1,47), poly(vinyl sec-butyl simple ether) (isotactic) (1,47), politicallegal (1,47), polyoxyethylene-oxycontino (1,47), (poliatilenaksida) polytetramethylene (1,47), copolyme the ethylene-propylene (EPR rubber) (about 1.47 to 1.48), polyhexamethylenediamine (1,48), polyvinylformal (1,48), poly(2-foraminotomies) (1,48), polyisobutylcyanoacrylate (1,48), ethylcellulose (1,48), polyvinylacetal (1,48-1,50), cellulose acetate (1,48-1,50), tripropionin cellulose (1,48-1,49), Polyoxymethylene (1,48), polyvinyl butyral (1,48-1,49), poly(n-hexyllithium) (1,48), poly(n-butylmethacrylate) (1,48), polietilentireftalat (1,48), poly(2-ethoxyethylacetate) (1,48), polyoxyethylene-oximeter (1,48), (polietilensorbit) poly(n-propylbetaine) (1,48), poly(3,3,5-trimethylcyclohexylidene) (1,49), polimetilmetakrilat (1,49), poly(2-nitro-2-methylpropionitrile) (1,49), politicalinstability (1,49), poly(1,1-diarylpropionitrile) (1,49), polymethylmethacrylate (1,49), poly(2-decyl-1,3-butadiene) (1,49), polyvinyl alcohol (1,49-1,53), polyethylene-glycolate-methacrylate (1,49), poly(3-methylcyclohexylamine) (1,49), poly(cyclohexyl-α-ethoxyacrylate) (1,50), methyl cellulose (low viscosity) (1,50), poly(4-methylcyclohexylamine) (1,50), dimethacrylate of politicalideological (1,50), polyurethane (1,50-1,60), poly(1,2-butadiene) (1,50), polyvinylformal (1,50), poly(2-bromo-4-trifloromethyl) (1,50), cellulose nitrate (1,50-1,51), poly(sec-butylα-chloroacrylate) (1,50), poly(2-heptyl-1,3-butadiene) (1,50), poly(ethyl-α-chloroacrylate) (1,50), poly(2-isopropyl-1,3-butadiene) (1,50), poly(2-methylcyclohexylamine) (1,50), polypropylene (density 0,9075 g/cm3) (1,50),polyisobutene (1,51), polybutylmethacrylate (1,51), poly(2-tert-butyl-1,3-butadiene) (1,51), dimethacrylate of polyethylene glycol (1,51), polycyclohexylene (1,51), poly(cyclohexanediol-1,4-dimethacrylate) (1,51), butyl rubber (unvulcanized) (1,51), polytetrahydrofuran (1,51), gutta-percha (β) (1,51), ion meter polyethylene (1,51), polyoxyethylene (molecular) (1,51-1,54), polyethylene (density 0,914 g/cm3) (1,51), (density of 0.94-0,945 g/cm3) (1,52-1,53), (density 0,965 g/cm3) (1,55), poly(1-methylcyclohexylamine) (1,51), poly(2-hydroxyethylmethacrylate) (1,51), polivinilacetat (1,51), polybutene (isotactic) (1,51), polivinilatsetat (1,51), poly(N-butyl-methacrylamide) (1,51), gutta-percha (α) (1,51), terpene resin (1,52), poly(1,3-butadiene) (1,52), shellac (1,51-1,53), poly(methyl-α-chloroacrylate) (1.52m), poly(2-claritromicina) (1,52), poly(2-diethylaminoethylmethacrylate) (1,52), poly(2-chlorocyclohexanone) (1,52), poly(1,3-butadiene) (35% CIS-form; 56% TRANS-form 1,5180; 7% 1,2-addition), natural rubber (1,52), polyalkylacrylate (1,52), polyvinyl chloride + 40% dioctylphthalate (1,52), polyacrylonitrile (1,52), polymethacrylamide (1,52), poly(1,3-butadiene) (enriched CIS-form) (1,52), copolymer of butadiene-Acrylonitrile (1,52), polyethylenepropylene (1,52), polyisoprene (1,52), hard polyester resin (50% styrene) (1,52-1,54), poly(N-(2-methoxyethyl)methacrylamide) (1,52), poly(2,3-dimethylbutan the yen) (metilius) (1,53), the copolymer is a vinyl chloride-vinyl acetate (95/5-90/10) (1,53-1,54), polyacrylic acid (1,53), poly(1,3-dichloropropionitrile) (1,53), poly(2-chloro-1-(chloromethyl)ethyl methacrylate) (1,53), polyacrolein (1,53), poly(1-vinyl-2-pyrrolidone) (1,53), rubber hydrochloride (1,53-1.55V), nylon 6; nylon 6,6; nylon 6,10 (molded product) (1,53), copolymer of butadiene-styrene (about 30% styrene) (1,53), block copolymers of poly(cyclohexyl-α-chloroacrylate) (1,53), poly(2-chloroethyl-α-chloroacrylate) (1,53), copolymer of butadiene-styrene (about 75/25) (1,54), poly(2-aminoheterocycles) (1,54), polyfurfuryl (1,54), polimetilmetakrilat (1,54), poly(1-phenyl-N-amylmetacresol) (1,54), poly(N-methyl-methacrylamide) (1,54), cellulose (1,54), polyvinyl chloride (1,54-1.55V), urea resin (1,54-1,56), poly(sec-butyl-α-bromacil) (1,54), poly(cyclohexyl-α-bromacil) (1,54), poly(2-bromatological) (1,54), policyidreference acid (1,54), Polubarinova acid (1,546), polyethylenepolyamines (1,55), poly(N-allylmethylamine) (1,55), poly(1-fenilatilmalonamid) (1,55), polyvinylformal (1,55), poly(2-vinyltetrahydrofuran) (1,55), poly(vinyl chloride) + 40% tricresylphosphate (1,55), poly(p-methoxybenzylthio) (1,55), polyisopropylene) (1,55), poly(p-isopropylthio) (1,55), polychloroprene (1,55-1,56), poly(oksietilenom-α-benzoate-methacrylate) (1,56), poly(p,p'-xylylenediamine) (1,6), poly(1-federalmileagerate) (1,56), poly(p-cyclohexenylmethyl) (1,56), poly(2-fenilatilmalonamid) (1,56), poly(oxycarbonyl-1,4-phenylene-1-propyl) (1,56), poly(1-(o-chlorophenyl)ethyl methacrylate) (1,56), a styrene-malinowy anhydride (1,56), poly(1-phenylcyclohexylamine) (1,56), poly(oxycarbonyl-1,4-phenylene-1,3-dimethylbutylamine-1,4-phenylene) (1,57), poly(methyl-α-bromacil) (1,57), polybenzimidazole (1,57), poly(2-(phenylsulfonyl)ethyl methacrylate) (1,57), poly(m-kizilmescit) (1,57), a styrene-Acrylonitrile (about 75/25) (1,57), poly(oxycarbonyl-1,4-phenylene-isobutylidene-1,4-phenylene) (1,57), poly(o-methoxyphenylacetyl) (1,57),

polyphenylmethyl (1,57), poly(o-kizilmescit) (1,57), polivalente (1,57), poly(2,3-dibromopropylether) (1,57), poly(oxycarbonyl-1,4-phenylene-1-methylethylidene-1,4-phenylene) (1,57), poly(oxy-2,6-dimethylphenyl) (1,58), polyoxyethylene oxetanemethanol (amorphous) (1,58), polyethylene terephthalate (1,51-1,64), polyvinylether (1,58), poly(oxycarbonyl-1,4-familienbetrieben-1,4-phenylene) (1,58), poly(1,2-diphenylethylenediamine) (1,58), poly(o-chlorobenzonitrile) (1,58), poly(oxycarbonyl-1,4-phenylene-second-butylidene-1,4-phenylene) (1,58),

polyoxyethyleneglycol (1,58), poly(m-nitrobenzonitrile) (1,58), poly(oxycarbonyl-1,4-phenyleneisopropylidene-1,4-phenylene) (1,59), poly(N-(2-phenylethyl)methacrylamide) (1,59), poly(4-what ethoxy-2-methylsterol) (1,59), poly(o-methylsterol) (1,59), polystyrene (1,59), poly(oxycarbonyl-1,4-phenyltrichlorosilane-1,4-phenylene) (1,59), poly(o-mitoxantron) (1,59), polydiphenylsiloxane (1,59), poly(oxycarbonyl-1,4-phenylaniline-1,4-phenylene) (1,59), poly(p-bromophenylacetate) (1,60), poly(N-benzylacrylamide) (1,60), poly(p-mitoxantron) (1,60), grades (1,60-1,63), polysulfide ("Thiokol") (1,6-1,7), poly(o-chlorodiphenylmethane) (1,60), poly(oxycarbonyl-1,4-(2,6-dichloro)phenylene-isopropylidene-1,4-(2,6-dichloro)phenylene) (1,61), poly(oxycarbonyl-bis(1,4-(3,5-dichloraniline))) polymethacrylates (1,61), poly(o-chloresterol) (1,61), poly(phenyl-α-bromacil) (1,61), poly(p-divinylbenzene) (1,62), poly(N-vinylphthalimide) (1,62), poly(2,6-dichlorostyrene) (1,62), poly(β-naphthylmethyl) (1,63), poly(α-nattermannallee) (1,63), polysulfone (1,63), poly(2-venitien) (1,64), poly(α-naphthylmethyl) (1,64), poly(oxycarbonyl-1,4-phenylenevinylene-1,4-phenylene) (1,65), polyphenylenesulfide (1,66), butylphenol-formaldehyde resin (1,66), urea-tiomochevina-formaldehyde resin (1,66), polivinildeftorid (1,68), polyvinylcarbazole (1,68), naftalin-formaldehyde resin (1,70), phenol-formaldehyde resin (1,70) and polypentaerythritols (1,71).

Of these preferred polymers having a refractive index of 1.6 or less, and the polymers having the indicator rotten is possible d-ray 1.5 or less.

Srednevekovaja molecular weight depolymerizing connection (In), especially a binder polymer, preferably equal to from 100 to 500,000, more preferably from 100 to 200,000.

Hydrolyzed compounds represented by the following formula (1), or the condensation product used as depolymerizing compounds (B):

nA-nB≥0,05(1)
R1nSi(OR2)4-n(1)

where R1and R2may be the same or different and each means a monovalent organic group, and n means an integer from 0 to 2.

Examples of the monovalent organic group in the formula (1) include accelgroup, alicyclic group, airgroup, allgraph and goldengrape. Examples of altergroup include methylgroup, telgraph, profilgruppen and bodygraph. The number of carbon atoms of altergroup is preferably from 1 to 5. Altergroup may be linear or branched and may contain a halogen atom such as a fluorine atom, a replacement of its hydrogen atom. Examples of the alicyclic group include cyclohexylprop and norbornyl. Examples of airgroup include panelgroup and aftercrop, n in the formula (1) preferably is 0 or 1.

Illustrative examples connections PR is stavlennika specified by formula (1), include:

methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-proposition, methyltriethoxysilane, methyltri-n-butoxysilane, methyltri-second-butoxysilane, methyltri-tert-butoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Atilla-n-proposition,

ethyltriethoxysilane, Atilla-n-butoxysilane, Atilla-second-butoxysilane, Atilla-tert-butoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-properti-n-proposition, n-propyltriethoxysilane, n-properti-n-butoxysilane, n-properti-second-butoxysilane, n-properti-tert-butoxysilane, n-propyltrimethoxysilane, isopropylimidazole, isopropylthioxanthone, isopropylthio-n-proposition, isopropylthiazole, isopropylthio-n-butoxysilane, isopropylthio-second-butoxysilane, isopropylthio-tert-butoxysilane, isopropylideneglycerol, n-butyltrichlorosilane,

n-butyltrichlorosilane, n-builti-n-proposition,

n-butyldiethanolamine, n-builti-n-butoxysilane,

n-builti-second-butoxysilane, n-builti-tert-butoxysilane, n-butyltrichlorosilane, second-butyldimethylsilyl, second-butylisothiazolinon, second-builti-n-proposition, second-butylisoxazole, second-builti-n-butoxysilane, second-builti-second-butoxysilane, sec-butyl is ri-tert-butoxysilane, second-butyldiphenylsilyl, tert-butyldimethylsilyl, tert-butyltrichlorosilane, tert-builti-n-proposition, tert-butylisoxazole, tert-builti-n-butoxysilane, tert-builti-second-butoxysilane, tert-builti-tert-butoxysilane, tert-butyldiphenylsilyl, cyclohexyltrichlorosilane,

cyclohexyltrichlorosilane, cyclohexyl-n-proposition, cyclohexyltrichlorosilane, cyclohexyl-n-butoxysilane, cyclohexylthio-second-butoxysilane, cyclohexylthio-tertbutoxide, cyclohexyltrichlorosilane,

norbornenedicarboxylic, norbornenedicarboxylic, norbornylene-n-proposition, norbornenedicarboxylic, norbornylene-n-butoxysilane, norbornylene-second-butoxysilane, norbornylene-tert-butoxysilane, norbornenedicarboxylic, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-proposition,

phenyltriethoxysilane, phenyltri-n-butoxysilane, phenyltri-second-butoxysilane, phenyltri-tert-butoxysilane,

phenyltrimethoxysilane, dimethyldiethoxysilane,

dimethyldiethoxysilane, dimethyldi-n-proposition,

dimethyldiethoxysilane, dimethyldi-n-butoxysilane, dimethyldi-second-butoxysilane, dimethyldi-tert-butoxysilane,

dimethyldiethoxysilane, diethylammonium,

diethyldichlorosilane, diatide-n-proposition,

diethylaminopropyl the LAN, diatide-n-butoxysilane, diatide-second-butoxysilane, diatide-tert-butoxysilane,

diethyldichlorosilane, di-n-propyltrimethoxysilane, di-n-propyltriethoxysilane, di-n-property-n-proposition, di-n-propertiesproperties, di-n-property-n-butoxysilane, di-n-property-second-butoxysilane, di-n-property-tert-butoxysilane, di-n-providefinancial, diisobutyldimethoxysilane,

diisobutyldimethoxysilane, diisopropyl-n-proposition,

diisobutyldimethoxysilane, diisopropyl-n-butoxysilane, diisopropyl-second-butoxysilane, diisopropyl-tertbutoxide, diisobutyldimethoxysilane,

di-n-butyldimethylsilyl, di-n-butyldichlorosilane, di-n-buildi-n-proposition, di-n-butyldiethanolamine, di-n-buildi-n-butoxysilane, di-n-buildi-second-butoxysilane, di-n-buildi-tert-butoxysilane, di-n-butyldiphenoquinone,

di-sec-butyldimethylsilyl, di-sec-butyldichlorosilane, di-sec-buildi-n-proposition, di-sec-butyldimethylsilyl, di-sec-buildi-n-butoxysilane, di-sec-buildi-second-butoxysilane, di-sec-buildi-tert-butoxysilane, di-sec-butyldiphenoquinone, di-tert-butyldimethylsilyl, di-tert-butyldichlorosilane, di-tert-buildi-n-proposition, di-tert-butyldiethanolamine, di-tert-buildi-n-butoxysilane, di-tert-buildi-second-butoxysilane, di-tert-buildi-tert-BU is oxsilan, di-tert-butyldiphenoquinone, dicyclohexylammonium, dicyclohexylmethane, DICYCLOHEXYL-n-proposition, dicyclohexylcarbodiimide, DICYCLOHEXYL-n-butoxysilane, DICYCLOHEXYL-second-butoxysilane, DICYCLOHEXYL-tert-butoxysilane, dicyclohexylcarbodiimide,

deerbenevskaya, derbandikhan,

donorbridge-n-proposition, dinornithiformes, donorbridge-n-butoxysilane, donorbridge-second-butoxysilane, donorbridge-tert-butoxysilane, dinornithiformes, diphenylmethylsilane, diphenyldichlorosilane, definilty-n-proposition, diphenyldichlorosilane, definilty-n-butoxysilane, definilty-second-butoxysilane, definilty-tert-butoxysilane, divinerdiagnostician, diphenylchlorosilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidylmethacrylate,

γ-glycidylmethacrylate,

γ-cryptosporidiosis and γ-cryptosporidiosis.

Compounds obtained by substituting fluorine atoms for some or all of hydrogen atoms of these compounds may also be used. These alkylalkoxysilane can be used as one by one or in combination of two or more compounds.

Compounds predstavleniya formula (1), particularly preferred allyltriethoxysilane formula (1), where R1and R2both mean accelgroup, and n is 1. Of them preferred methyltrimethoxysilane and methyltriethoxysilane. When methyltrimethoxysilane and/or methyltriethoxysilane used in the amount of 70 mol.% on the basis of the sum of all alkylalkoxysilane, you get cured product having a good balance between heat resistance and refractive index. Preferably the hydrolysate of the compound represented by the specified formula (1), and the condensation product have srednevekovoy molecular weight based on polystyrene from 500 to 100000.

Hydrolytic reaction and condensation reaction of the hydrolysate of the compound represented by the specified formula (1), and condensation products of component (C) is carried out in the presence of water and a suitable catalyst, as will be described further here.

More specifically found that the compound represented by the specified formula (1), is dissolved in a suitable organic solvent and this solution continuously or in portions add water. The catalyst may preferably be dissolved or dispersed in an organic solvent, or dissolved or dispersed in water, which you want to add.

Temperature holding hydrolytic reaction and the condensation reaction of prepact the tion is from 0 to 100° S, more preferably from 15 to 80°C.

Water to conduct hydrolysis and condensation of the compound represented by the specified formula (1)preferably represents water purified by ion exchange.

The amount of water is preferably from 0.25 to 3 mol, particularly preferably from 0.3 to 2.5 mol per 1 mol of all groups, represented as R2O - compound represented by the specified formula (1).

A catalyst for hydrolysis and condensation of the compound represented by the specified formula (1), is a chelate compound of the metal, organic acids, inorganic acids, organic bases or inorganic bases.

Examples of the chelate compound of the metal used as the catalyst include chelate compounds of titanium, such as:

triethoxy·mono(acetylacetonato)titanium,

tri-n-propoxy·mono(acetylacetonato)titanium,

three-isopropoxy·mono(acetylacetonato)titanium,

tri-n-butoxy·mono(acetylacetonato)titanium,

three-Deut-butoxy·mono(acetylacetonato)titanium,

three-tert-butoxy·mono(acetylacetonato)titanium,

diethoxy·bis(acetylacetonato)titanium,

di-n-propoxy·bis(acetylacetonato)titanium,

di isopropoxy·bis(acetylacetonato)titanium,

di-n-butoxy·bis(acetylacetonato)titanium,

di-tert-butoxy·bis(acetylacetonato)titanium,

monoatomic·Tris(acetylacetonato)titanium,

mono-n-propoxy·Tris(acetylacetonato)titanium,

mono-isopropoxy·Tris(acetylacetonato)titanium,

mono-n-butoxy·Tris(acetylacetonato)titanium,

mono-Deut-butoxy·Tris(acetylacetonato)titanium,

mono-tert-butoxy·Tris(acetylacetonato)titanium,

tetrakis(acetylacetonato)titanium,

triethoxy·mono(ethylacetoacetate)titanium,

tri-n-propoxy·mono(ethylacetoacetate)titanium,

three-isopropoxy·mono(ethylacetoacetate)titanium,

tri-n-butoxy·mono(ethylacetoacetate)titanium,

three-Deut-butoxy·mono(ethylacetoacetate)titanium,

three-tert-butoxy·mono(ethylacetoacetate)titanium,

diethoxy·bis(ethylacetoacetate)titanium,

di-n-propoxy·bis(ethylacetoacetate)titanium,

di isopropoxy·bis(ethylacetoacetate)titanium,

di-n-butoxy·bis(ethylacetoacetate)titanium,

di-sec-butoxy·bis(ethylacetoacetate)titanium,

di-tert-butoxy·bis(ethylacetoacetate)titanium,

monoatomic·Tris(ethylacetoacetate)titanium,

mono-n-propoxy·Tris(ethylacetoacetate)titanium,

mono-isopropoxy·Tris(ethylacetoacetate)titanium,

mono-n-butoxy·Tris(ethylacetoacetate)titanium,

mono-Deut-butoxy·Tris(ethylacetoacetate)titanium,

p> mono-tert-butoxy·Tris(ethylacetoacetate)titanium,

tetrakis(ethylacetoacetate)titanium,

mono(acetylacetonato)Tris(ethylacetoacetate)titanium,

bis(acetylacetonato)bis(ethylacetoacetate)titanium and

Tris(acetylacetonato)mono(ethylacetoacetate)titanium;

chelate compounds of zirconium, such as:

triethoxy·mono(acetylacetonato)zirconium,

tri-n-propoxy·mono(acetylacetonato)zirconium,

three-isopropoxy·mono(acetylacetonato)zirconium,

tri-n-butoxy·mono(acetylacetonato)zirconium,

three-Deut-butoxy·mono(acetylacetonato)zirconium,

three-tert-butoxy·mono(acetylacetonato)zirconium,

diethoxy·bis(acetylacetonato)zirconium,

di-n-propoxy·bis(acetylacetonato)zirconium,

di isopropoxy·bis(acetylacetonato)zirconium,

di-n-butoxy·bis(acetylacetonato)zirconium,

di-sec-butoxy·bis(acetylacetonato)zirconium,

di-tert-butoxy·bis(acetylacetonato)zirconium,

monoatomic·Tris(acetylacetonato)zirconium,

mono-n-propoxy·Tris(acetylacetonato)zirconium,

mono-isopropoxy·Tris(acetylacetonato)zirconium,

mono-n-butoxy·Tris(acetylacetonato)zirconium,

mono-Deut-butoxy·Tris(acetylacetonato)zirconium,

mono-tert-butoxy·Tris(acetylacetonato)zirconium,

tetrakis(acetylacetone is)zirconium,

triethoxy·mono(ethylacetoacetate)zirconium,

tri-n-propoxy·mono(ethylacetoacetate)zirconium,

three-isopropoxy·mono(ethylacetoacetate)zirconium,

tri-n-butoxy·mono(ethylacetoacetate)zirconium,

three-Deut-butoxy·mono(ethylacetoacetate)zirconium,

three-tert-butoxy·mono(ethylacetoacetate)zirconium,

diethoxy·bis(ethylacetoacetate)zirconium,

di-n-propoxy·bis(ethylacetoacetate)zirconium,

di isopropoxy·bis(ethylacetoacetate)zirconium,

di-n-butoxy·bis(ethylacetoacetate)zirconium,

di-sec-butoxy·bis(ethylacetoacetate)zirconium,

di-tert-butoxy·bis(ethylacetoacetate)zirconium,

monoatomic·Tris(ethylacetoacetate)zirconium,

mono-n-propoxy·Tris(ethylacetoacetate)zirconium,

mono-isopropoxy·Tris(ethylacetoacetate)zirconium,

mono-n-butoxy·Tris(ethylacetoacetate)zirconium,

mono-Deut-butoxy·Tris(ethylacetoacetate)zirconium,

mono-tert-butoxy·Tris(ethylacetoacetate)zirconium,

tetrakis(ethylacetoacetate)zirconium,

mono(acetylacetonato)Tris(ethylacetoacetate)zirconium,

bis(acetylacetonato)bis(ethylacetoacetate)zirconium and

Tris(acetylacetonato)mono(ethylacetoacetate)zirconium;

and chelate compounds of aluminum, such as:

Tris(acetylacetonato)aluminum and

Tris(ethylacetoacetate)and uminia.

Examples of the organic acid used as the catalyst, includes such as acetic acid, propionic acid, butane acid, pentane acid, Capraia acid, heptane acid, octanoic acid, novanova acid, cekanova acid, oxalic acid, maleic acid, methylmalonate acid, adipic acid, sabotinova acid, Gallic acid, butyric acid, malletova acid, arachidonic acid, shikimic acid, 2-ethylhexanoate acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluensulfonate acid, benzolsulfonat acid, monochloracetic acid, dichloracetic acid, trichloroacetic acid, triperoxonane acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid and tartaric acid.

Examples of the inorganic acid used as the catalyst include chloroethanol acid, nitric acid, sulfuric acid, hydrofluoric acid and phosphoric acid.

Examples of the organic base used as the catalyst include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, treat the Lamin, monoethanolamine, diethanolamine, dimethylaminoethanol, monomethylethanolamine, triethanolamine, diazabicyclo, diazabicyclo, disalicylidene and hydroxide of Tetramethylammonium.

Examples of the inorganic base used as the catalyst include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide and calcium hydroxide.

One of them is preferably used as the catalyst chelate compound of the metal, organic acid or inorganic acid, and more preferably use a chelate compound of the metal or organic acid.

These compounds can be used as a catalyst in one or in combination of two or more.

The amount of catalyst is preferably from 0.001 to 10 parts by weight, more preferably from 0.01 to 10 parts by weight based on 100 parts by weight of the compound represented by above formula (1) per SiO2.

In addition, it is preferable to remove residual water and alcohol formed as a by-product of the reaction after hydrolysis and condensation of the compound represented by above formula (1).

Polysilsesquioxane ladder type, represented by the following formula (2), its hydrolysis or condensation product of the hydrolysate is preferably used as naprimer is used for the connection (In):

where R3means a monovalent organic group, R4means a hydrogen atom or monovalent organic group, R3and R4may be the same or different, and n indicates a positive integer, corresponding to the molecular mass.

Examples of the monovalent organic group in the formula (2) include accelgroup, alicyclic group, airgroup, allgraph and goldengrape. Examples of altergroup include methylgroup, telgraph and profilgruppen. The number of carbon atoms of altergroup preferably from 1 to 5. Altergroup may be linear or branched. Examples of the alicyclic group include cyclohexylprop and norbornyl. Examples of airgroup include panelgroup, aftercrop and tailgroup. In addition, the hydrogen atoms of accelgroup, airgroup, allergry and goldengrape can be substituted by a halogen atom such as fluorine atom.

The method of obtaining compounds having a structure represented by the specified formula (2), disclosed, for example, in JP-A 56-157885, JP-A 57-40562 and JP-A 58-69217. Commercially available products of the compounds include GR-100, GR-650, GR-908 and GR-950 (Showa Denko KK).

Hydrolytic reaction and the condensation reaction of the compound represented by the specified formula (2)can be carried out in the us is the conditions (catalyst, water, reaction temperature), such conditions Ricci hydrolysis/condensation of the compound represented by formula (1). Srednevekovaja molecular weight based on polystyrene compounds represented by the specified formula (2), its hydrolysis or condensation product of the hydrolysate equal preferably from 500 to 500,000, more preferably from 500 to 300,000.

The amount of component (b) is preferably from 10 to 95 parts by weight, more preferably from 10 to 90 parts by weight, even more preferably from 20 to 90 parts by weight, particularly preferably from 20 to 70 parts by weight based on 100 parts by weight of the sum of components (a) and (B). When the amount of component (b) is less than 10 parts by weight, the resulting material that changes refractive index, has a tendency to become brittle, and when its amount is more than 90 parts by weight, the resulting difference of the refractive index tends to decrease.

Sensitive to radiation initiator (C) polymerization

Sensitive to radiation initiator (C) polymerization used in the present invention, can be sensitive to radiation generator acid, sensitive to the radiation generator or base sensitive to the radiation generator of free radicals. In this case, preferably used is sensitive to the radiation generator acid as sensitive to radiation initiator (C) polymerization when the curable compound (A) is used as a compound capable of interacting with the acid; sensitive to radiation generator base used as sensitive to radiation initiator (C) polymerization, when the curable compound (A) is used as a compound capable of interacting with the base, and sensitive to the radiation generator radicals are used as sensitive to radiation initiator (C) polymerization, when the curable compound (A) is used as a compound capable of interacting with the radical.

Specified sensitive to radiation generator acid selected from trichloromethyl-s-triazine, salt diarylethene, salt triarylsulfonium, salts of Quaternary ammonium and complex ether sulfonic acid.

Examples of trichloromethyl-s-triazine include:

2,4,6-Tris(trichloromethyl)-s-triazine,

2-phenyl-4,6-bis(trichloromethyl)-s-triazine,

2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine,

2-(3-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine,

2-(2-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine,

2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,

2-(3-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,

2-(2-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,

2-(4-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine,

2-(3-methylthiophenyl)-,6-bis(trichloromethyl)-s-triazine,

2-(2-methylthiophenyl)- 4,6-bis(trichloromethyl)-s-triazine,

2-(4-methoxyethyl)-4,6-bis(trichloromethyl)-s-triazine,

2-(3-methoxyethyl)-4,6-bis(trichloromethyl)-s-triazine,

2-(2-methoxyethyl)-4,6-bis(trichloromethyl)-s-triazine,

2-(4-methoxy-β-styryl)-4,6-bis(trichloromethyl)-s-triazine,

2-(3-methoxy-β-styryl)-4,6-bis(trichloromethyl)-s-triazine,

2-(2-methoxy-β-styryl)-4,6-bis(trichloromethyl)-s-triazine,

2-(3,4,5-trimetoksi-β-styryl)-4,6-bis(trichloromethyl)-s-triazine,

2-(4-methylthio-β-styryl)-4,6-bis(trichloromethyl)-s-triazine,

2-(3-methylthio-β-styryl)-4,6-bis(trichloromethyl)-s-triazine,

2-(3-methylthio-β-styryl)-4,6-bis(trichloromethyl)-s-triazine,

2 piperonyl-4,6-bis(trichloromethyl)-s-triazine,

2-[2-(furan-2-yl)ethynyl]-4,6-bis(trichloromethyl)-s-triazine,

2-[2-(5-methylfuran-2-yl)ethynyl]-4,6-bis(trichloromethyl)-s-triazine and

2-[2-(4-diethylamino-2-were)ethynyl]-4,6-bis(trichloromethyl)-s-triazine.

Examples of the specified salt diarylethene include:

diphenyliodonium tetrafluoroborate,

diphenyliodonium hexaflurophosphate,

diphenyliodonium hexafluoroarsenate,

diphenyliodonium triftorbyenzola,

diphenyliodonium triptorelin,

diphenyliodonium-p-toluene sulfonate,

diphenyliodonium butyltin(2,6-differenl)borate,

diphenyliodonium exillis(p-chlorophenyl)borate,

diphenyliodonium exillis(3-triptoreline)boron is t,

4-methoxyphenylacetone tetrafluoroborate,

4-methoxyphenylacetone hexaflurophosphate,

4-methoxyphenylacetone hexafluoroarsenate,

4-methoxyphenylacetone triptorelin sulfonate,

4-methoxyphenylacetone triptorelin,

4-methoxybenzylidene-p-toluene sulfonate,

4-methoxyphenylacetone butyltin(2,6-differenl)borate,

4-methoxyphenylacetone exillis(p-chlorophenyl)borate,

4-methoxyphenylacetone exillis(3-triptoreline)borate,

bis(4-tert-butylphenyl)iodone tetrafluoroborate,

bis(4-tert-butylphenyl)iodone hexafluoroarsenate,

bis(4-tert-butylphenyl)iodone triptorelin sulfonate,

bis(4-tert-butylphenyl)iodone triptorelin,

bis(4-tert-butylphenyl)iodone-p-toluene sulfonate,

bis(4-tert-butylphenyl)iodone butyltin(2,differenl)borate,

bis(4-tert-butylphenyl)iodone exillis(p-chlorophenyl)borate and bis(4-tert-butylphenyl)iodone exillis(3-triptoreline)borate.

Examples of the specified salt triarylsulfonium include:

triphenylsulfonium tetrafluoroborate,

triphenylsulfonium hexaflurophosphate,

triphenylsulfonium hexafluoroarsenate,

triphenylsulfonium triptorelin sulfonate,

triphenylsulfonium triptorelin,

triphenylsulfonium-p-toluene sulfonate,

triphenylsulfonium built the IP(2,6-differenl)borate,

triphenylsulfonium exillis(p-chlorophenyl)borate,

triphenylsulfonium exillis(3-triptoreline)borate,

4-methoxybenzenesulfonyl tetrafluoroborate,

4-methoxybenzenesulfonyl hexaflurophosphate,

4-methoxybenzenesulfonyl hexafluoroarsenate,

4-methoxybenzenesulfonyl triptorelin sulfonate,

4-methoxybenzenesulfonyl triptorelin,

4-methoxybenzenesulfonyl-p-toluene sulfonate,

4-methoxybenzenesulfonyl butyltin(2,6-differenl)borate,

4-methoxybenzenesulfonyl exillis(p-chlorophenyl)

Borat,

4-methoxybenzenesulfonyl exillis(3-triptoreline)borate,

4-phenyldiethanolamine tetrafluoroborate,

4-phenyldiethanolamine hexaflurophosphate,

4-phenyldiethanolamine hexafluoroarsenate,

4-phenyldiethanolamine triptorelin sulfonate,

4-phenyldiethanolamine triptorelin,

4-phenyldiethanolamine-p-toluene sulfonate,

4-phenyldiethanolamine butyltin(2,6-differenl)borate,

4-phenyldiethanolamine exillis(p-chlorophenyl)borate,

4-phenyldiethanolamine exillis(3-triptoreline)borate,

4-hydroxy-1-naphthalenedisulfonic tetrafluoroborate,

4-hydroxy-1-naphthalenediol Alfani hexaflurophosphate,

4-hydroxy-1-naphthalenedisulfonic hexafluoroarsenate,

4-hydroxy-1-naphthalenedisulfonic triptorelin

sulfonate,

4-hydroxy-1-naphthalenedisulfonic triptorelin,

4-hydroxy-1-naphthalenedisulfonic-p-toluene sulfonate,

4-hydroxy-1-naphthalenedisulfonic butyltin(2,6-differenl)borate,

4-hydroxy-1-naphthalenedisulfonic exillis(p-chlorophenyl)borate and

4-hydroxy-1-naphthalenedisulfonic exillis(3-triptoreline)borate.

Examples of the specified Quaternary ammonium salt include:

Tetramethylammonium tetrafluoroborate,

Tetramethylammonium hexaflurophosphate,

Tetramethylammonium hexafluoroarsenate,

Tetramethylammonium triptorelin sulfonate,

Tetramethylammonium triptorelin,

Tetramethylammonium-p-toluene sulfonate,

Tetramethylammonium butyltin(2,6-differenl)borate,

Tetramethylammonium exillis(p-chlorophenyl)borate,

Tetramethylammonium exillis(3-triptoreline)borate,

tetrabutylammonium tetrafluoroborate,

tetrabutylammonium hexaflurophosphate,

tetrabutylammonium hexafluoroarsenate,

tetrabutylammonium triptorelin sulfonate,

tetrabutylammonium triptorelin,

tetrabutylammonium-p-toluene sulfonate,

tetrabutylammonium butyltin(2,6-differenl)borate,

Tetrao ilmoni exillis(p-chlorophenyl)borate,

tetrabutylammonium exillis(3-triptoreline)borate,

the designed tetrafluoroborate,

the designed hexaflurophosphate,

the designed hexafluoroarsenate,

the designed triptorelin sulfonate,

the designed triptorelin,

the designed-p-toluene sulfonate,

the designed butyltin(2,6-differenl)borate,

the designed exillis(p-chlorophenyl)borate,

the designed exillis(3-triptoreline)borate,

benzyldimethylammonium tetrafluoroborate,

benzyldimethylammonium hexaflurophosphate,

benzyldimethylammonium hexafluoroarsenate,

benzyldimethylammonium triptorelin sulfonate,

benzyldimethylammonium triptorelin,

benzyldimethylammonium-p-toluene sulfonate,

benzyldimethylammonium butyltin(2,6-differenl)borate,

benzyldimethylammonium exillis(p-chlorophenyl)borate,

benzyldimethylammonium exillis(3-triptoreline)borate,

N-cinnamylpiperazine tetrafluoroborate,

N-cinnamylpiperazine hexaflurophosphate,

N-cinnamylpiperazine hexafluoroarsenate,

N-cinnamylpiperazine triptorelin sulfonate,

N-cinnamylpiperazine triptorelin,

-cinnamylpiperazine-p-toluene sulfonate,

N-cinnamylpiperazine-butyltin(2,6-differenl)borate,

N-cinnamylpiperazine exillis(p-chlorophenyl)borate and

N-cinnamylpiperazine exillis(3-triptoreline)borate.

Examples of specified complex ether sulfonic acids include:

ester α-hydroxymethylbenzene-p-toluensulfonate acid,

ester α-hydroxymethylbenzene-triftormetilfullerenov acid,

ester α-hydroxymethylbenzene-methanesulfonic acid,

ester the pyragollole-three(p-toluensulfonate acid),

ester the pyragollole three(triftormetilfullerenov acid),

ester the pyragollole-trimethylsulfonium acid,

ester 2,4-dinitrobenzyl-p-toluensulfonate acid,

ester 2,4-dinitrobenzyl-triftormetilfullerenov acid,

ester 2,4-dinitrobenzyl-methanesulfonic acid,

ester 2,4-dinitrobenzyl-1,2-nattokinase-5-sulfonic acid,

ester 2,6-dinitrobenzyl-p-toluensulfonate acid,

ester 2,6-dinitrobenzyl-triftormetilfullerenov acid,

ester 2,6-dinitrobenzyl-methanesulfonic acid,

ester 2,6-dinitrobenzyl-1,2-nattokinase-5-sulfonic acid,

ester 2-nitrobenzyl-p-toluensulfonate acid,

the false ester 2-nitrobenzyl-triftormetilfullerenov acid,

ester 2-nitrobenzyl-methanesulfonic acid,

ester 2-nitrobenzyl-1,2-nattokinase-5-sulfonic acid,

ester 4-nitrobenzyl-p-toluensulfonate acid,

ester 4-nitrobenzyl-triftormetilfullerenov acid,

ester 4-nitrobenzyl-methanesulfonic acid,

ester 4-nitrobenzyl-1,2-nattokinase-5-sulfonic acid,

ester N-hydroxyphthalimide-p-toluensulfonate acid, an ester of N-hydroxyphthalimide-triftormetilfullerenov acid,

ester N-hydroxyphthalimide-methanesulfonic acid, an ester of N-hydroxy-5-norbornene-2,3-dicarboximido-p-toluensulfonate acid,

ester of N-hydroxy-5-norbornene-2,3-dicarboximido-triftormetilfullerenov acid,

ester of N-hydroxy-5-norbornene-2,3-dicarboximido-methanesulfonic acid,

ester 2,4,6,3',4',5'-hexahydroxybenzene-1,2-nattokinase-4-sulfonic acid and

ester 1,1,1-three(p-hydroxyphenyl)ethane-1,nattokinase-4-sulfonic acid.

Of these compounds preferred as trichloromethyl-s-triazines:

2-(3-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine,

2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine,

2-(4-methylthiophenyl)-4,6-bis(trichloromethyl)-s-triazine,

2-(4-methoxy-β-styryl)-4,6-bistriflate)-s-triazine,

2 piperonyl-4,6-bis(trichloromethyl)-s-triazine,

2-[2-(furan-2-yl)ethynyl]-4,6-bis(trichloromethyl)-s-triazine,

2-[2-(5-methylfuran-2-yl)ethynyl]-4,6-bis(trichloromethyl)-s-triazine,

2-[2-(4-diethylamino-2-were)ethynyl]-4,6-bis(trichloromethyl)-s-triazine and

2-(4-methoxyethyl)-4,6-bis(trichloromethyl)-s-triazine diphenyliodonium triptorelin,

diphenyliodonium triptorelin sulfonate,

4-methoxyphenylacetone triptorelin sulfonate and

4-methoxyphenylacetone triptorelin preferred as salts diarylethene;

triphenylsulfonium triptorelin sulfonate,

triphenylsulfonium triptorelin,

4-methoxybenzenesulfonyl triptorelin sulfonate,

4-methoxybenzenesulfonyl triptorelin,

4-phenyldiethanolamine triptorelin sulfonate and

4-phenyldiethanolamine triptorelin

preferred as salts triarylsulfonium;

Tetramethylammonium butyltin(2,6-differenl)borate,

Tetramethylammonium exillis(p-chlorophenyl)borate,

Tetramethylammonium exillis(3-triptoreline)borate,

benzyldimethylammonium butyltin(2,6-differenl)borate,

benzyldimethylammonium exillis(p-chlorophenyl)borate and benzyldimethylammonium exillis(3-triptoreline)borate are preferred as Quaternary ammonium salts; and

ester 2,6-dinitrobenzyl-p-toluensulfonate acid, an ester of 2,6-dinitrobenzyl-triftormetilfullerenov acid,

ester N-hydroxyphthalimide-p-toluensulfonate acid and an ester of N-hydroxyphthalimide-triftormetilfullerenov acid is preferred as esters sulfonic acid.

As specified sensitive to radiation generator Foundation upon use, which are disclosed in the following sources: JP-A 4-330444, "Polymer", pages 242-248, volume 46, No. 6 (1997) and USP 5627010. However, sensitive to the radiation generator base is not limited to the above compounds, if it forms the base under the influence of radiation.

Preferred are sensitive to the radiation generator base in this invention is selected from a photoactive carbamates, such as triphenylmethanol, benzylcarbamoyl or antinormal; amides such as O-carbarnoyl hydroxylamin, carbamoyloximes, aromatic sulfonamide, alpha-lactam or N-(2-allylamine)amide, and other amides; esters of oxime, α-aminoacetophenone and complex cobalt.

Illustrative examples are sensitive to the radiation generator base include compounds represented by the following formula(3)-(13):

where R5means alking the PPU, having from 1 to 6 carbon atoms, alkoxygroup having from 1 to 6 carbon atoms, toolkitpro having from 1 to 6 carbon atoms, dialkylamino having from 1 to 6 carbon atoms in each accelgroup, piperidino, the nitro-group, a hydroxy-group, mercaptopropyl, altergroup or Altenilpe having from 2 to 6 carbon atoms, airgroup having from 6 to 20 carbon atoms, a fluorine atom, a chlorine atom or a bromine atom, k is an integer from 0 to 3, R6means a hydrogen atom, accelgroup having from 1 to 6 carbon atoms, altergroup or quinil group having from 2 to 6 carbon atoms, or airgroup having from 6 to 20 carbon atoms, and R7and R8each independently represent a hydrogen atom, accelgroup having from 1 to 6 carbon atoms, altergroup or Altenilpe having from 2 to 6 carbon atoms, airgroup having from 6 to 20 carbon atoms, or benzerrou, or R7and R8can be linked together with the formation of a cyclic structure having 5 to 6 carbon atoms together with the nitrogen atom associated with them;

where R9means altergroup having from 1 to 6 carbon atoms, alkoxygroup having from 1 to 6 carbon atoms, toolkitpro having from 1 to 6 carbon atoms, dialkylamino having from 1 to 6 carbon atoms in each is skillgroup, piperidino, the nitro-group, a hydroxy-group, mercaptopropyl, altergroup or quinil group having from 2 to 6 carbon atoms, or aryl group having from 6 to 20 carbon atoms, R10means a hydrogen atom, accelgroup having from 1 to 6 carbon atoms, altergroup or quinil group having from 2 to 6 carbon atoms, or aryl group having from 6 to 20 carbon atoms, and R11and R12each independently represent a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, altergroup or Altenilpe having from 2 to 6 carbon atoms, airgroup having from 6 to 20 carbon atoms, or benzyl group, or R11and R12can be linked together with the formation of a cyclic structure having 5 to 6 carbon atoms together with the nitrogen atom associated with them;

where R13means altergroup having from 1 to 6 carbon atoms, altergroup or quinil group having from 2 to 6 carbon atoms, or airgroup having from 6 to 20 carbon atoms, and R14and R15each independently represent a hydrogen atom, accelgroup having from 1 to 6 carbon atoms, altergroup or Altenilpe having from 2 to 6 carbon atoms, airgroup having from 6 to 20 carbon atoms, or benzerrou, or R14and R15can be linked together with obrazovatelnoi patterns, having from 5 to 6 carbon atoms together with the nitrogen atom associated with them;

where R16and R17each independently represent altergroup having from 1 to 6 carbon atoms, altergroup or quinil group having from 2 to 6 carbon atoms, or airgroup having from 6 to 20 carbon atoms;

where R18, R19and R20each independently represent altergroup having from 1 to 6 carbon atoms, altergroup or Altenilpe having from 2 to 6 carbon atoms, or aryl group having from 6 to 20 carbon atoms;

where R21means altergroup having from 1 to 6 carbon atoms, alkoxygroup having from 1 to 6 carbon atoms, toolkitpro having from 1 to 6 carbon atoms, dialkylamino having from 1 to 6 carbon atoms in each accelgroup, piperidino, the nitro-group, a hydroxy-group, mercaptopropyl, altergroup or Altenilpe having from 2 to 6 carbon atoms, or airgroup having from 6 to 20 carbon atoms, R22means a hydrogen atom, accelgroup having from 1 to 6 carbon atoms, altergroup or quinil group having from 2 to 6 carbon atoms, or airgroup having from 6 to 20 carbon atoms, and R23, R24and R25each independently represent the atoms is hydrogen, altergroup having from 1 to 6 carbon atoms, altergroup or Altenilpe having from 2 to 6 carbon atoms, airgroup having from 6 to 20 carbon atoms, or benzerrou;

where R26means altergroup having from 1 to 6 carbon atoms, alkoxygroup having from 1 to 6 carbon atoms, toolkitpro having from 1 to 6 carbon atoms, dialkylamino having from 1 to 6 carbon atoms in each accelgroup, piperidino, the nitro-group, a hydroxy-group, mercaptopropyl, altergroup or Altenilpe having from 2 to 6 carbon atoms, or airgroup having from 6 to 20 carbon atoms, R27and R28each independently represent a hydrogen atom, a hydroxy-group, mercaptopropyl, cyano, fenoxaprop, accelgroup having from 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, altergroup or Altenilpe having from 2 to 6 carbon atoms, or airgroup having from 6 to 20 carbon atoms, and R29and R30each independently represent a hydrogen atom, accelgroup having from 1 to 6 carbon atoms, altergroup or Altenilpe having from 2 to 6 carbon atoms, airgroup having from 6 to 20 carbon atoms, or benzerrou, or R29and R30can be linked together with the formation of a cyclic structure having 5 to 6 atoms in the of Lerida together with the nitrogen atom, associated with them;

where R31and R32each independently represent altergroup having from 1 to 6 carbon atoms, alkoxygroup having from 1 to 6 carbon atoms, toolkitpro having from 1 to 6 carbon atoms, dialkylamino having from 1 to 6 carbon atoms in each accelgroup, piperidino, the nitro-group, a hydroxy-group, mercaptopropyl, altergroup or Altenilpe having from 2 to 6 carbon atoms, or airgroup having from 6 to 20 carbon atoms, R33-R36each independently represent a hydrogen atom, a hydroxy-group, mercaptopropyl, cyano, fenoxaprop, accelgroup having from 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, altergroup or Altenilpe having 2 to 6 carbon atoms, or airgroup having from 6 to 20 carbon atoms, and A1means a divalent atomic group formed by excluding two hydrogen atoms associated with one or two nitrogen atoms of monoalkylamines, piperazine, aromatic diamine or aliphatic diamine;

where R37and R38each independently represent altergroup having 1 to 6 carbon atoms, alkoxygroup having from 1 to 6 carbon atoms, toolkitpro having from 1 to 6 carbon atoms, dialkylamino with to 6 carbon atoms in each accelgroup, piperidino, the nitro-group, a hydroxy-group, mercaptopropyl, altergroup or Altenilpe having from 2 to 6 carbon atoms, or airgroup having from 6 to 20 carbon atoms, R39and R40each independently represent a hydrogen atom, a hydroxyl group, mercaptopropyl, cyano, fenoxaprop, accelgroup having from 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, altergroup or Altenilpe having from 2 to 6 carbon atoms, or airgroup having from 6 to 20 carbon atoms, R41-R44each independently represent a hydrogen atom, accelgroup having from 1 to 6 carbon atoms, altergroup or Altenilpe having from 2 to 6 carbon atoms, airgroup having from 6 to 20 carbon atoms, or benzerrou, or R41and R42and R43and R44can be linked together with the formation of a cyclic structure having 5 to 6 carbon atoms together with the nitrogen atoms bound to them, and A2means akilagpa having from 1 to 6 carbon atoms, cyclohexylprop, familiegroep or single bond;

where R45-R47each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, accelgroup having from 1 to 6 carbon atoms, alkoxygroup having from 1 to 6 carbon atoms, altergroup is whether Altenilpe, having from 2 to 6 carbon atoms, or airgroup having from 6 to 20 carbon atoms;

LmCO3+·3[(R48)3R49]-(13)

where L denotes at least one ligand selected from the group consisting of such members as ammonia, pyridine, imidazole, Ethylenediamine, trimethylenediamine, tetramethylaniline, hexamethylenediamine were, Propylenediamine, 1,2-cyclohexanediamine, N,N-diethylethylenediamine and Diethylenetriamine, m means an integer from 2 to 6, R48means altergroup or Altenilpe having from 2 to 6 carbon atoms, or airgroup having from 6 to 20 carbon atoms, and R49means altergroup having 1 to 18 carbon atoms.

In all the above formulas (3)-(13) altergroup can be linear, branched or cyclic. Examples of altergroup include vinylgroover and PropertyGroup, examples of altenergy include acetylenyl, and examples of airgroup include panelgroup, aftercrop and anthranilate. Also included are those containing a fluorine atom, a chlorine atom, a bromine atom, halogenating, hydroxyl group, carboxyl group, mercaptopropyl, a cyano, a nitro-group, asiagraph, dialkylamino, alkoxygroup or toolkitpro, replacement and the ohms of the hydrogen of the above groups.

From the above sensitive to radiation generators reason preferred 2-nitrobenzenesulfonate, triphenylmethanol, o-carbamoyltransferase, carbamoyloximes, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine,

bis[[(2-nitrobenzyl)oxy]carbonyl]hexane-1,6-diamine,

4-(methylthiomethyl)-1-methyl-1-morpholinoethyl,

(4-morpholinomethyl)-1-benzyl-1-dimethylaminopropane,

N-(2-nitrobenzenesulfonyl)pyrrolidin,

hexaamminecobalt(III)-Tris(triphenylmethyl) and

2-benzyl-2-dimethylamino-1-(4-morpholinomethyl)-butanone.

Examples of specified sensitive to radiation generator radicals include αdiketones such as benzil and diacetyl; acyloin, such as benzoin; ethers of allenov, such as benzoin methyl simple ether, benzoin ethyl simple ether and benzoin-isopropyl simple ether; benzophenone, such as thioxanthone, 2,4-dietitican, thioxanthone-4-sulfonic acid, benzophenone,

4,4'-bis(dimethylamino)benzophenone and

4,4'-bis(diethylamino)benzophenone; acetophenone, such as

the acetophenone, p-dimethylaminoazobenzene, α,α'-dimethoxybenzophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl[4-(methylthio)phenyl]-2-morpholino-1-propanone and 2-benzyl-2-dimethylamino-1-(4-morpholinomethyl)-butane-1-he; quinones such as anthraquinone and 1,4-on thenon; compounds of halogen, such as penicillanic, tribromoanisole and Tris(trichloromethyl)-s-triazine; acylphosphatase, such as 2,4,6-trimethylbenzenesulfonamide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-interference and bis(2,4,6-trimethylbenzoyl)phenylphosphine, and peroxides, such as

di-tert-butylperoxide.

Commercially available products of these is sensitive to radiation of the radical polymerization initiators include IRGACURE-184, 369, 500, 651, 907, 1700, 819, 1000, 2959, 149, 1800 and 1850, Darocur-1173, 1116, 2959, 1664 and 4043 (Ciba Specialty Chemicals Co., Ltd.), KAYACURE-DETX, MBP, DMBI, EPA and OA (Nippon Kayaku Co., Ltd.), VICURE-10 and 55 (STAUFFER Co., Ltd.), TRIGONALPI (AKZO Co., Ltd.), SANDORAY 1000 (SANDOZ Co., Ltd.), DEAP (APJOHN Co., Ltd.) and QUANTACURE-PDO, ITX and EPD (WARD BLEKINSOP Co., Ltd.).

Sensitive to radiation, the resin composition having high sensitivity can be obtained using one of the specified sensitive to radiation radical polymerization initiators in combination with sensitive radiation sensitizer.

Specified sensitive to radiation initiator (C) polymerization is used in amounts of preferably 0.01 part or more by mass, more preferably 0.05 part or more by mass for 100 parts by weight of the amount of the polymerized compounds (A) and depolymerizing compounds (B), when sensitive to radiation initiator (C) polymerization is sensitive to what zlucenie the acid generator or the generator base. When the amount of component (C) is less than 0.01 part by weight, sensitivity to radiation tends to decrease. The value of the upper limit is preferably 30 parts by mass, more preferably 20 parts by mass.

Sensitive to the radiation generator of radicals contained in an amount of preferably from 1 to 50 parts by weight, more preferably from 5 to 30 parts by weight per 100 parts by weight of the amount of the polymerized compounds (A) and depolymerizing compounds (B). When the number is sensitive to the radiation generator (S) radicals is less than 1 part by weight, sensitivity to radiation tends to decrease.

Other components

Composition with changing refractive index used in this invention may contain other additives within limits not harmful to the object of the present invention. Additives include UV absorbers, a sensitizer, a surfactant that improves thermal or heat resistant agent and adhesive excipient.

The specified UV absorbers are selected from benzotriazole, salicylate, benzophenone, substituted Acrylonitrile, xanthene, coumarin, flavone and chalcone. Specific examples of the ultraviolet absorber of radiation include Tinubn 234 (2-(2-hydroxy-3,5-bis(α thatα-dimethylbenzyl)phenyl)-2H-benzotriazole), Tinubin 571 (derived hydroxyphenylacetate) and Tinubin 1130 (the condensation product of methyl-3-(3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl)propionate and polyethylene glycol (molecular weight 300)) (Ciba Specialty Chemicals Co., Ltd.), 1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadien-3,5-dione and dibenzylidene-acetone.

Adding absorber of ultraviolet radiation, which is useful as a means of forming structures GRIN type, amount of acid, base or radical generated from the component (C)may gradually become smaller with increasing depth from the surface of the exposed part of the composition of the variable refractive index according to this invention. The number of the absorber of ultraviolet radiation is preferably 30 parts by mass or less, more preferably 20 parts by weight per 100 parts by weight of the sum of components (A) and (B).

The specified sensitizer selected from coumarin derivatives having a substituent in position 3 and/or 7, flavone, dibenzalacetone, dibenzalacetone, chalcone, Xanten, thioxanthene, porphyrin, phthalocyanine derivatives, acridine and anthracene.

The amount of the sensitizer is preferably 30 parts by mass or less, more preferably 20 parts by weight per 100 parts by weight of the sum of components (A) and (B).

the shown surface-active agent may be added to improve opacity, for example, to prevent broadcasti (banding), and improve the ability to manifest.

Examples of surfactants include nonionic surfactants, such as alkalemia ethers of polyoxyethylene, including larrouy simple polyoxyethylene ether, stearyl simple ether and polyoxyethylene alerby simple ester of polyoxyethylene, arrowie ethers of polyoxyethylene, including octylphenoxy simple ether and polyoxyethylene nonylphenols simple ester of polyoxyethylene, and dialkylamino esters of polyethylene glycol, including dilaurate of polyethylene glycol and distearate of polyethylene glycol; a surfactant-based fluoride, commercially available under the trade names F Top EF301, EF303 and EF352 (of 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 (of Asahi Glass Co., Ltd.); other surfactants, commercially available under the trade names organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.) and (co)polymer based on acrylic or methacrylic acid Polyflow No. 57 and No. 95 (Kyoeisha Depending Co., Ltd.).

The amount of surfactant is preferably 2 parts by mass or less, more preferably 1 part by weight or less to 100 parts by weight of the amounts of the components (A) and (B).

Specified adhesive excipient may be added to improve adhesion to the substrate (the substrate), and is preferably silane binding agent.

The above enhancement of the heat resistance agent is an unsaturated compound, such as polyvalent acrylate.

The antistatic agent, an agent that improves stability during curing, the fogging inhibitor, prepodavatel, a pigment and a thermal acid generator may be added to modify the refractive index of the material used in this invention, if necessary.

The formation of the structure formed by the refractive index of

In this invention, the structure formed by the refractive index can be formed from the above composition with changing refractive index, for example, as follows.

First, the composition of the variable refractive index is dissolved or dispersed in the solvent, to obtain a composition having a solids content from 5 to 70 wt.%. The composition, if necessary, can be filtered through a filter having a pore diameter of from about 0.1 to 10 μm before use.

Then this composition is applied to the surface of the substrate (substrate)such as a silicon plate, and subjected to preliminary heat treatment that is advised to remove the solvent and form a film coating of the composition with changing refractive index. The part formed of the coating film is then exposed to radiation through a pattern and heated to create a difference in refractive index between the exposed and unexposed parts of the composition with changing refractive index.

Under the radiation exposure of sensitive radiation polymerization initiator formed by acid, base or radicals to initiate the polymerization or reaction of the component (A). This component (A) unexposed part is dissipated during heating after exposure. As a result, there is a difference of refractive index between the exposed and unexposed parts.

The solvent used to obtain the solution containing the composition with changing refractive index used in this invention, uniformly dissolves the components (A), (B) and (C) and other optional additives and does not interact with these components.

Illustrative examples of the solvent include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol and propylene glycol; ethers such as tetrahydrofuran; ethers of glycol, such as onomatology simple ether of ethylene glycol and monotropy simple ether of ethylene glycol; acetates Olkiluoto simple ether ethylenglycol what I such as methyl-cellosolve-acetate and ethyl cellosolve-acetate; diethylenglycol, such as onomatology simple ether of diethylene glycol, monotropy simple ether of diethylene glycol, dimethyl simple ether of diethylene glycol and utilmately simple ether of diethylene glycol; monoalkyl ethers of propylene glycol, such as methyl simple ether of propylene glycol, ethyl simple ether of propylene glycol, propyl simple ether of propylene glycol and butyl simple ether of propylene glycol; acetates Olkiluoto simple ether of propylene glycol, such as methyl acetate simple ether of propylene glycol, ethyl acetate simple ether of propylene glycol, propyl acetate simple ester of propylene glycol and butyl acetate simple ether of propylene glycol; propionate Olkiluoto simple ether of propylene glycol, such as methyl propionate simple ether of propylene glycol, ethyl propionate simple ether of propylene glycol, propyl propionate simple ester of propylene glycol and butyl propionate simple ether of propylene glycol; 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, butyl acetate, ethyl-2-hydroxypropionate, methyl-2-hydroxy-2-methylpropionate ethyl-2-hydroxy-2-methylpropionate, methyl-hydroxyacetate, ethyl hydroxyacetate, butyl-hydroxyacetate, mutilated, ethyllactate, prophylactic, butylacetate, methyl-3-hydroxypropionate, ethyl-3-hydroxypropionate, propyl-3-hydroxypropionate, butyl-3-hydroxypropionate, methyl-2-hydroxy-3-methylbutanoate, methyl-methoxyacetate, ethyl methoxyacetate, propyl-methoxyacetate, butyl-methoxyacetate, methyl-ethoxyacetic, ethyl ethoxyacetic, propyl-ethoxyacetic, butyl-ethoxyacetic, methyl-propoxylated, ethyl propoxylated, propyl-propoxylated, butyl propoxylated, methyl-butoxylated, ethyl butoxylated, propyl-butoxylated, butyl-butoxylated, methyl-2-methoxypropionate, ethyl-2-methoxypropionate, propyl-2-methoxypropionate, butyl-2-methoxypropionate, methyl-2-ethoxypropionate, ethyl-2-ethoxypropionate, propyl-2-ethoxypropionate, butyl-2-ethoxypropionate, methyl-2-butoxypropyl, ethyl-2-butoxypropyl, propyl-2-butoxypropyl, butyl-2-butoxypropyl, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, propyl-3-ethoxypropionate, butyl-3-methoxypropionate, methyl-3-ethoxypropionate, ethyl-3-ethoxypropionate, propyl-3-ethoxypropionate, butyl-3-ethoxypropionate, methyl-3-propoxyphenol, ethyl-3-propoxyphenol, propyl-3-propoxyphenol, butyl-3-propoxyphenol, methyl-3-butoxypropan, ethyl-3-butoxypropan, propyl-3-butoxypropan and butyl-3-butoxypropyl is at; and containing a fluorine atom solvents, such as triptoreline, 1,3-bis(trifluoromethyl)benzene, phenyl, hexaferrites, performatilicious, performatilicious, acceptancein and 1,1,2-trichloro-1,2,2-trifluoroethane.

Of these solvents, alcohols, ethers, glycol acetates Olkiluoto simple ether of ethylene glycol, acetates Olkiluoto simple ether of propylene glycol, ketones, esters and dietilen glycols are preferred from the viewpoint of solubility, reactivity with each component and ease of formation of the coating film.

In addition, the high-boiling solvent may be used in combination with the above solvent. Examples of high-boiling solvent include N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-dimethylacetamide, N-organic, dimethylsulfoxide, benzylation simple ether, directroy simple ether, acetonylacetone, isophorone, Caproic acid, Caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzoylacetate, ethylbenzoic, diethyloxalate, diethylmaleate, γ-butyrolactone, ethylene carbonate resulting, propylene carbonate and phenyl-cellosolve-acetate.

Composition with changing refractive index used in this invention, before pododvigat influence is the influence of radiation (exposure), attach different forms depending on the purpose of its application. For example, it is formed into the form of a rod, fiber, long panel, spheres, films or lenses, and the invention is not limited with this. Can be applied to a conventional technology of forming, represented, for example, injection molding, direct pressing, pneumoperitoneum, extrusion molding, polymerization in the form, application by brush, extractor fan, heating/cooling, CDV deposition (chemical vapor deposition, CVD), sintering and scanning. Floor rotation, longitudinal cutting, floor plate, formed by dipping in a solution, LB, sputtering, high printing or screen printing can also be used in accordance with the purpose of the optically molded product.

In the specified molding process is preferably conducted heat (referred to hereafter as "pre-cooking"). Conditions of heat, which vary in accordance with the material composition according to this invention and the type of each additive are preferably from 30 to 200°S, more preferably from 40 to 150°C. heating can be used hot plate, oven or infrared radiation.

The radiation used for exposure or exposure, represents an i-line having a wavelength of 365 nm, h-line, and euwww wavelength of 404 nm, g-line having a wavelength of 436 nm, ultraviolet radiation from the light source with a broad wavelength range, such as a xenon lamp, the radiation in the far ultraviolet region, such as the beam from the excimer KrF laser having a wavelength of 248 nm, or the beam from the excimer ArF laser having a wavelength of 193 nm, x-rays such as synchrotron radiation, charged particle beam, such as electron beam, visible light, or their mixture. Which one is preferable ultraviolet radiation and visible radiation. Illumination, which depends on the wavelength of the radiation is preferably from 0.1 to 100 mW/cm2as this is achieved the highest efficiency of the reaction. The projection of the radiation through the template allows you to copy his picture on sensitive to radiation from the material with variable refractive index. With regard to the accuracy of the copy, which are affected by the light source used, there can be obtained an optical part having the distribution of changes of the refractive index with a resolution of about 0.2 μm.

The present invention after exposure is preferably conducted heat (the heat treatment after exposure, TPE). A device similar to the above device for pre-heat, can be used for TPE, and the conditions TPE can be arbitrary. The temperature of the heating is preferably from 30 to 150°S, more preferably from 30 to 130°C. If the component (A) unexposed part is not dissipated completely by heating at normal pressure can be carried out by heating under reduced pressure. Thus, the structure formed by the refractive index can be formed efficiently.

Can be optionally repeated exposure to decompose the residual component (S)present in the unexposed part, and further improve the stability of the material.

Repeated exposure can be conducted, for example, the projection of the radiation having the same wavelength as the radiation used to change the refractive index, on the entire surface of the structure in the same amount.

Optionally, the stability of the material can be further improved by heating. A device similar to the device for preliminary heat treatment used during molding material, can be used for heating, and the heating conditions can be arbitrary.

According to this invention, a method of forming patterns formed by the refractive index, in the present invention can also be carried out by exposing the composition to change the available refractive index, containing the above components (A), (b) and (C)radiation through the template and process developer.

With regard to the type of the specified developer, the preferred developer which dissolves the component (A) and need not be added to the catalyst, but does not dissolve the polymer formed from the component (A)and component (B). When you choose (remove) the developer, the surface of the resulting structure formed by the refractive index, does not become uneven.

The developer is an alkaline aqueous solution containing an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, metasilicate sodium or ammonia water; primary amines, such as ethylamine or n-Propylamine; a secondary amine such as diethylamine or di-n-Propylamine; tertiary amines, such as triethylamine, methyldiethylamine or N-organic; Amin alcohol, such as dimethylethanolamine or triethanolamine; a Quaternary ammonium salt, such as a hydroxide of Tetramethylammonium, the hydroxide of tetraethylammonium or choline; or a cyclic amine such as pyrrole, piperidine, 1,8-divisibile[5.4.0]-7-undecene or 1,5-diazabicyclo[4.3.0]-5-nonen. An organic solvent selected from alcohols, such as methanol, ethanol, isopropanol, n-propanol, n-butanol, Isobutanol, tert-butanol, cyclohexanol, ethylene glycol, propylenglycol the ü or diethylene glycol; ethers, such as diethyl simple ether or tetrahydrofuran; ethers of glycol, such as onomatology simple ether of ethylene glycol or monotropy simple ether of ethylene glycol; acetates Olkiluoto simple ether of ethylene glycol, such as methyl-cellosolve-acetate or ethyl cellosolve-acetate; diethylenglycol, such as onomatology simple ether of diethylene glycol, monotropy simple ether of diethylene glycol or dimethyl simple ether of diethylene glycol; monoalkyl simple glycol esters, such as methyl simple ether of propylene glycol or ethyl simple ether of propylene glycol; acetates Olkiluoto simple ether of propylene glycol, such as methyl acetate simple ether of propylene glycol or ethyl acetate simple ether of propylene glycol; propionato Olkiluoto simple ether of propylene glycol, such as methyl propionate simple ether of propylene glycol, ethyl propionate simple ether of propylene glycol, propyl propionate simple ether of propylene glycol or butyl propionate simple ether of propylene glycol; aromatic hydrocarbons such as toluene or xylene; aliphatic hydrocarbons such as n-hexane, n-heptane or n-octane; ketones such as methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, methylmercaptan or 4-hydroxy-4-methyl-2-PE is the Thanon; or esters, such as ethyl acetate, propyl, butyl acetate, ethyl-2-hydroxypropionate, methyl-2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, butyl-hydroxyacetate, ethyllactate, prophylactic, butylacetate, methyl 3-hydroxypropionate, methyl-2-hydroxy-3-methylbutanoate, utilitarianist, butylmethacrylate, ethyl-2-methoxypropionate, butyl-2-methoxypropionate, butyl-2-ethoxypropionate, butyl-2-butoxypropyl, butyl-3-ethoxypropionate, butyl-3-ethoxypropionate, butyl-3-propoxyphene or butyl-3-butoxypropan, can also be used as a developer.

One of them is preferably used water, alcohols, ethers, glycol and acetates Olkiluoto simple ether of ethylene glycol.

The developing time is usually from 30 to 180 seconds, and can be a manifestation of the coating or the manifestation of dipping. After developing, the film coating is washed with running water for 30-180 seconds and dried with compressed air or compressed nitrogen to remove water from the substrate, thus obtaining the structure formed by the refractive index.

Can be optionally repeated exposure to decompose the residual component (S)present in the unexposed part, and further improve the stability of the material.

As for what is not described method f is Mirovaya patterns, formed by refractive index, which includes the specified stabilization, it should be understood that the above description of the method of forming patterns formed by the refractive index is applied here directly or with modifications obvious to people having ordinary skill in the technical field.

Residual curable compound (A), present in the unexposed part, remove specified by heating, preferably to form pores.

According to this invention, in the structure formed by the refractive index and formed by any of the above various methods, the refractive index of the exposed portion (the first section) is preferably greater than the rate in the unexposed part (second plot). This difference can be brought to the desired value of the control (control) types and content of components (a) and (b) in the composition with changing refractive index used in this invention. For example, the highest value of the difference in refractive index can be increased to a value of more than 0.02.

The structure formed by refractive index, in the present invention has pores or has no pores in the unexposed part.

When the unexposed portion has a u the market, its porosity is preferably from 10 to 99.9%, more preferably from 15 to 99.9%, particularly preferably from 20 to 99.9%.

Since the structure formed by the refractive index, in the present invention is not impaired, while maintaining without change of the refractive index, even when it is used in conditions when passed through the light having a wavelength close to the wavelength used to change the refractive index, as described above, it is extremely useful as an optical material for use in opto-electronic and display devices (displays).

Since the structure formed by the refractive index, according to this invention has a sufficiently large difference between the refractive indices, and achieved the difference between the refractive resistant to light and heat, it is extremely useful as an optical material for use in opto-electronic field and displays. The structure formed by refractive index, in the present invention can also be used in optical parts such as fototapete (sets), lenses, photon-coupled pair, photointerrupters, the polarization separator of the light beam, the hologram, single-mode and multimode optical fibers, fiber bundles, fiber optic cables, single core, stranded and photos kricheskii optical link connectors, optical isolators, polarizers, optical sensors such as photodiodes, photointerrupter, photo-IP, CCD image sensors based on charge-coupled devices). charge-coupled device), CMOS image sensors (based on complementary metal-oxide-semiconductor structures, CMOS), optical fiber sensors and optical fiber gyroscopes, optical discs such as CDS (compact discs), LD (laser disk) and DVD (digital versatile disks), optical switches, waveguides, optical contact panel, diffraction gratings, optical control panel, optical diffusers, antitreaty and optical seals.

The method of obtaining optical parts

Composition with changing refractive index used in this invention, before exposing it to radiation, give different forms depending on the purpose of its application.

For example, it is formed into the form of a rod, fiber, long panel, spheres, films or lenses, and the invention is not limited with this. Can be applied to a conventional technology of forming, for example, injection molding, direct pressing, pneumotropica, extrusion, polymerization in the form, application by brush, extractor fan, heating/cooling, CDV deposition, sintering and scan. Floor rotation, longitudinal cutting, etc is their bar, forming dipping in the solution, LB, floor cushion, high printing or screen printing can also be used in accordance with the purpose of the optically molded product.

The radiation used for exposure, represents an i-line having a wavelength of 365 nm, h-line having a wavelength of 404 nm, g-line having a wavelength of 436 nm, ultraviolet radiation from the light source a wide range of wavelengths, such as a xenon lamp, the radiation in the far ultraviolet region, such as the beam from the excimer KrF laser having a wavelength of 248 nm, or the beam from the excimer ArF laser having a wavelength of 193 nm, x-rays such as synchrotron radiation, charged particle beam, such as electron beam, visible light, or their mixture. Which one is preferable ultraviolet radiation and visible radiation. Illumination, which depends on the wavelength of the radiation is preferably from 0.1 to 100 mW/cm2as this is achieved the highest efficiency of the reaction. The projection of the radiation through the template allows you to copy his picture on sensitive to radiation from the material with variable refractive index. With regard to the accuracy of the copy, which are affected by the light source used can be obtained an optical part having the distribution is giving variations of the refractive index with a resolution of about 0.2 μm.

The present invention is preferably carried out heat treatment after exposure (TPE). Conditions of heat, which vary in accordance with the material composition according to this invention and the type of each additive, preferably range from 30 to 200°S, more preferably from 40 to 150°C. heating can be used hot plate, oven or infrared radiation. Component (A) in the unexposed part can be removed by heating under reduced pressure or by using the developer, as described above.

The difference between the maximum refractive index and the minimum refractive index distribution of the refractive optical part according to this invention can be brought to a desired value in accordance with the intended application, as described above. For example it can be set at the level of 0.02 or more if necessary 0.03 or more, 0.05 or more or 0.08 or more.

Examples

The following examples are presented to further illustrate this invention, but should not be interpreted as restrictive.

Srednevekovoy molecular weight of the polymer based on polystyrene measured by GPC chromatographically system-21 from Showa Denko K.K.

Examples of the synthesis of the component In the

Example of synthesis 1

15,22 g tetramethoxysilane and 27,24 g methyltris is doxycyline dissolved in 100 g of simple mutilative ether of ethylene glycol in a 1-liter three-neck flask, and the obtained mixed solution is heated at 60°under stirring with a magnetic stirrer. 5.20 g purified with ion exchange water is continuously added to the mixed solution for 1 hour. After 4 hours of reaction at 60°With the resulting reaction solution was cooled to room temperature. After that, 9,20 g of methanol, which is a side product of the reaction is distilled off from the reaction solution under reduced pressure. The solids content in the solution of the obtained polymer (B-1) 33.2%, and srednevekovaja molecular weight of the polymer is equal to 2200.

Example of synthesis 2

After substitution of nitrogen gas of the internal volume of 1.5 liter stainless steel autoclave equipped with an electromagnetic stirrer, autoclave serves 500 g of ethyl acetate, to 57.2 g of etilenovogo simple ether (EVE), 10.2 g hydroxyethylcellulose simple ether (HEVE) and 3 g of eurailpasses and cooled to -50°With dry ice and methanol, and then remove oxygen from the system with gaseous nitrogen. Then served 146 g hexaferrite (HFP), and the temperature begins to rise. When the temperature inside the autoclave reaches 60°C, the pressure is equal to 5.3 kgf/cm2. After that, the reaction continued at 60°C for 20 hours with stirring, after which the autoclave is cooled with water, when the pressure drops to 1.5 kgf/ cm2to stop the reaction. After reaching room temperature, unreacted monomers discharged and the autoclave was opened to obtain a polymer solution having a solids content of 28.1%. The obtained polymer solution injected into methanol to precipitate the polymer, which is then washed with methanol and dried in vacuum at 50°to get 193 g of fluorine-containing copolymer. Srednevekovaja molecular weight of the obtained polymer (b-2) is equal to 17000.

Example of synthesis 3

8 g of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 g of simple dimethyl ether of diethylene glycol is served in a 500-ml three-neck flask. Then the flask serves 20 g of methacrylic acid, 30 g glycidylmethacrylate and 50 g of pentabromoethylbenzene, the internal volume of the flask filled with nitrogen and begin moderate stirring. The temperature of the solution was raised to 70°and maintain at this temperature for 3 hours to obtain a polymer solution (b-3). The solids content in the resulting polymer solution is 31,0%, and srednevekovaja molecular weight of the polymer is equal to 12000.

Example of synthesis 4

50 g of methyltrimethoxysilane served in 1-liter three-neck flask, add 100 g 1 ethoxy-2-propanol and dissolved in methyltrimethoxysilane, and then the obtained mixed solution is heated at 60°With stirring with a magnetic stirrer. 19,85 g of purified ion is m water is continuously added thereto over 1 hour. After 4 hours of reaction at 60°With the resulting reaction solution was cooled to room temperature.

After that, methanol, which is a side product of the reaction is distilled off from the reaction solution under reduced pressure, and then the reaction solution is concentrated until solids content of 20 wt.%, to obtain a solution containing the compound (b-4). Srednevekovaja molecular weight compounds (b-4) is equal to 8000.

Obtaining composition

Example 1

40 parts by weight of divinylbenzene as a component (A), 60 parts by weight of the condensation product of a joint (molecular weight 2000) a mixture of methyltrimethoxysilane and tetramethoxysilane (mass ratio of 55:5) as the component (b) and 3 parts by weight of 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine as a component (C) is dissolved in utilityroom simple ether of diethylene glycol to the total solids content of 20 wt.% and the resulting solution is filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a solution containing sensitive to radiation composition with changing refractive index.

The formation of the coating film

This solution is applied onto a substrate made of silicon by means of a centrifuge and subjected to preliminary heat treatment on a hot plate at 90°C for 2 minutes, that is to form a coating film of a thickness of 1.0 μm.

The formation of the structure formed by the refractive index of

The resulting film coating is exposed to radiation of 70 MJ/cm2at the optimum depth of focus using transformative projection exposure device NSR1505i6A (Nikon Corporation, NA = 0.45, and λ = 365 nm)to obtain the difference of refractive index between the exposed and unexposed parts of the composition with changing refractive index. The film coating is then subjected to heat treatment after exposure on a hot plate at 100°and a reduced pressure of 0.5 Torr for 2 minutes and additionally heated in an oven at 200°at normal pressure for 10 minutes.

Measurement of refractive index of

The indices of refraction of the exposed and unexposed parts on a substrate of silicon at room temperature is measured at 633 nm by using ellipsometry Auto EL IV NIR III (Rudolf Research Co., Ltd.). The results are shown in table 1.

Assessment of transparency

The glass substrate coated with sensitive radiation composition with changing refractive index, receive the same manner as described above, with the difference that instead of the substrate of silicon using a glass substrate of Corning 1737 (Corning Co., Ltd.).

After that, the transmittance of the obtained glass substrate measured length of the e wave from 400 to 800 nm two-150-20 spectrophotometer (Hitachi, Ltd.). Usually it is said that when the minimum transmittance greater than 95%, the transparency is satisfactory, and when the minimum transmittance equal to 95% or less, the transparency is poor. The results are shown in table 1.

Example 2

The procedure of example 1 is repeated, except that the quantitative exposure index change up to 250 MJ/cm2to evaluate the refractive index and transparency. The results are shown in table 1.

Example 3

Assessment is conducted in the same manner as in example 1, except that as component (B) used 60 parts by weight polysilsesquioxane ladder GR-650 (Showa Denko K.K.). The results are shown in table 1.

Example 4

Assessment is conducted in the same manner as in example 1, except that as component (A) using 65 parts by weight of divinylbenzene and as component (B) 35 parts by weight of the condensation product of methyltrimethoxysilane (molecular weight 2000). The results are shown in table 1.

Example 5

50 parts by weight of benzylmethylamine and 40 parts by weight of bis(4-acryloyldimethyl)sulfide as a component (A), the solution containing the polymer (b-3) (equivalent to 50 parts by weight (solids content) of the polymer (b-3), as component (b) and 25 parts by weight of the 2-benzyl-2-dimethylamino-1-(4-morpholinomethyl)butane-1-it (IRGACURE-369; Ciba Specialty Chemicals Co., Ltd.) as component (C) is dissolved in utilityroom simple ether of diethylene glycol to the total solids content of 20 wt.%, and the resulting solution is filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a solution containing sensitive to radiation composition with changing refractive index. The formation of the coating film, the measurement of refractive index and transparency are conducted in the same manner as in example 1. The formation of the structure formed by the refractive index, carried out as follows. The results are shown in table 1.

The formation of the structure formed by the refractive index of

The resulting film coating is exposed to radiation of 100 MJ/cm2at the optimum depth of focus using transformative projection exposure device NSR1505i6A (Nikon Corporation, NA = 0.45, and λ = 365 nm)to obtain the difference of refractive index between the exposed and unexposed parts of the composition with changing refractive index. The film coating is then subjected to heat treatment after exposure on a hot plate at 100°With under reduced pressure of 0.5 Torr for 2 minutes, show isopropanol at 25°C for 60 seconds and washed with a jet of clean water for 1 minute. And the finally, heat it in the oven at 200°at normal pressure for 10 minutes.

Example 6

Assessment is conducted in the same manner as in example 5 except that as component (B) use the solution containing the polymer (B-1) (equivalent to 50 parts by weight (solids content) of the polymer (B-1). The results are shown in table 1.

Example 7

Assessment is conducted in the same manner as in example 5 except that as component (A) used 40 parts by weight of benzylmethylamine, 20 parts by weight of vinylnaphthalene and 40 parts by weight of bis(4-acryloyldimethyl)sulfide, and as component (B) use the solution containing the polymer (b-3) (equivalent to 40 parts by weight (solids content) of the polymer (b-3). The results are shown in table 1.

Example 8

Assessment is conducted in the same manner as in example 5 except that as component (C) used 30 parts by weight of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-it (IRGACURE-907; Ciba Specialty Chemicals Co., Ltd.) and 3 parts by weight of 2,4-dietitican, and quantitative exposure index for the formation of patterns formed by the refractive index change, as shown in table 1. The results are shown in table 1.

Example 9

60 parts by weight of di(4-vinyloxy)BUTYLCARBAMATE and 30 parts by weight of tetrakis(β-EPoX propylthiouracil)methane as components (A), the solution containing the polymer (b-4) (equivalent to 40 parts by weight (solids content) of the polymer (b-4)as the component (b) and 3 parts by weight of sulfonate 4-phenyldiethanolamine-triptorelin as component (C) is dissolved in utilityroom simple ether of diethylene glycol to the total solids content of 20 wt.%, and the resulting solution is filtered through a membrane filter having a pore diameter of 0.2 μm to obtain a solution containing sensitive to radiation composition with changing refractive index. The formation of the coating film, the measurement of refractive index and transparency are conducted in the same manner as in example 1, and the quantitative measure of exposure and temperature of heat treatment after exposure for forming a pattern of refractive index change, as shown in table 1. The products of example 5, except as specified, repeat. The results are shown in table 1.

Example 10

Assessment is conducted in the same manner as in example 9 except that as component (B) use the solution containing the polymer (b-2) (equivalent to 40 parts by weight (solids content) of the polymer (b-2). The results are shown in table 1.

Example 11

Assessment is conducted in the same manner as in example 9, except that com is Ananta (C) using 1 part by weight of triptoreline diphenylethane, and that the quantitative measure of exposure for forming a pattern of refractive index is changed as shown in table 1. The results are shown in table 1.

Example 12

Assessment is conducted in the same manner as in example 9 except that as component (A) used 60 parts by weight of di(4-vinyloxy)butyl-terephthalate and 30 parts by weight of bis[(3-ethyl-3-oxetanemethanol)were]sulfone. The results are shown in table 1.

98,7%
Table 1
The conditions of forming the patterns formed by the refractive indexOptical properties
A quantitative measure of exposure (MJ/cm2)The temperature of the TPE (°)Refractive indextransparency
The exposed partUnexposed partThe exposed partUnexposed part
App.1701001,511,4298,6%98,7%
PR2501001,511,4298,5%
PR701001,511,4298,8%99,1%
PR701001,541,4298,5%99,0%
PR1001001,531,4298,6%98,7%
PR1001001,531,4298,6%99,0%
PR1001001,551,4298,4%99,1%
PR1401001,531,42of 98.2%98,6%
PR901301,501,4298,5%the 98.9%
PR901301,461,3898,5%99,0%
Proverbs 111201301,501,4298,5%the 98.9%
PR901301,481,42the 98.9%the 98.9%
PR.: Example

1. Sensitive to radiation the structure composition with changing refractive index, containing curable compound (A), polimerizuet compound (B)having a lower refractive index than the polymer of the curable compound (A), and is sensitive to the radiation initiator (C) polymerization.

2. The composition according to claim 1, in which the maximum difference in refractive index between the exposed and neprodvinutymi radiation parts of the composition is 0.02 or more.

3. The composition according to claim 1 or 2, wherein a ratio between a refractive index of nBdepolymerizing compounds (B) and the refractive index nApolymer polymerized compounds (A) satisfy the following expression (1):

4. How to change the refractive index, is the impact of radiation on sensitive to radiation with variable refractive index according to claim 1.

5. The method of forming patterns with the distribution of the refractive index, is the impact of radiation through the template structure sensitive to radiation, the composition of the variable refractive index according to claim 1, which has been previously subjected to heat treatment and which has been pre-attached to the required form.

6. The method of obtaining optical material, is the impact of radiation on the form for an optical material of the sensitivity is high to radiation with variable refractive index according to claim 1 through a template for the formation of the optical material, having a structure with a distribution of refractive index.



 

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