TW200936660A - Highly refractive resin composition, film optical member using the composition and manufacturing method of the highly refractive resin composition - Google Patents

Abstract

A highly refractive resin composition used for forming a film optical member which is transparent and has high refractivity, a film optical member using the composition and manufacturing method of the highly refractive resin composition are provided. The highly refractive resin composition includes a highly refractive intermediate containing metal. The highly refractive intermediate containing metal is obtained by mixing and heating the titanalkoxide, diethanolamine and water, and then distilling the alcohol of by-product formed by hydrolysis; the highly refractive resin composition is characterized in that the diethanolamine and water are further added after the alcohol is removed by distillation.

Description

200936660

3U3UUpii.dOC VI. [Technical Field] The present invention relates to a south refractive resin composition, a film-shaped optical member using the composition, and a method for producing a high refractive resin composition. More specifically, the present invention relates to a plastic lens, a prism, an optical fiber, an information recording substrate (disc), a filter, a member for a liquid crystal display, and a plasma. a film-shaped optical member represented by a member for a display, a prism sheet, a diffuser, a light-scattering film, a viewing angle-enlarging film, a brightness enhancement film, a polarizing element, a light-trapping film for a solar cell, and the like The resin material of the optical member is particularly related to a film-like optical member having a high refractive index and a high refractive resin composition for providing a film-like optical member, and a method for producing a fat composition. [Prior Art] In recent years, it is required to have a high refractive index transparent material of about h6 to 2 2 for a resin material which is light in weight and rich in I, and is suitable as various members. Refractive resin material). 'The high-refractive-index resin material in human sputum can be exemplified by polysulfide _ , thiline formic acid obtained from polyisocyanate compound = ^ gossip) (for example, 'refer to Japanese patent special fair _ _ Wei Li Qian Lun (episulflde (4) = poly", (for example, 'refer to Japanese Patent Laid-Open No. _132. No. ❹ ❹ 200936660 ju^uupn.aoc In addition, there are commercially available benzene rings on the benzene ring. The concentration rate is about 1.6. fold

Moreover, since bromine-containing compounds may be produced, they have been restricted in recent years. In addition, a technique of dispersing titanium oxide and oxygen metal oxide fine particles in a resin has been proposed (for example, see Japanese Patent Publication No. 2002-277609). However, it is extremely difficult to cause light scattering without causing light scattering. In addition, a large number of organic-inorganic hybrids (four) reports on the sol-gel reaction (s〇1_GelReacti〇n) of titanium alkoxide (Alkoxuie) in a resin matrix have been proposed (for example, refer to Japanese Although it is caused by light scattering, it has not been actually applied to optical applications because it causes light scattering. In addition, the invention described in the Japanese Patent Publication No. Hei 07-014834, or the Japanese Patent Application Publication No. Hei. No. Hei. Too low to form a thicker film of i division ~ 1 〇. In addition, when using a highly reactive metal oxide, the organic polymer-inorganic polymer composite and the J method of the Japanese Patent Laid-Open No. 322136 are difficult to control the reactivity, and it is difficult to achieve uniform dispersion. For example, since the reactivity of the titanium alcohol (tetra) sol-gel reaction is extremely high, the titanium oxide particles are likely to become particles having a light scattering degree or more (greater than 100 nm). 5 200936660 3U3UUpit.doc And titanium oxide has a polymer of photocatalytic active medium. Therefore, % will be invaded as a dispersion. [Invention] The object of the present invention is to provide an optical member which can be a film-like optical member, which is entangled into a moon, a refractive index, and a composition, _ the composition #膜a (1)-high refractive resin composition of a pre-formed member and a high-refractive resin composition, which comprises an intermediate, which contains a high-refraction medium-cut-salt amine and is heated after water age. The highly refractive resin composition obtained by removing the alcohol produced by the hydrolysis is characterized in that ', after the above alcohol is distilled off, diethanolamine and water are further added. (2) The high-refractive-resin composition according to the above (1), which is obtained by adding the above-mentioned diethanolamine, and then adding K to (3) the high refractive resin composition according to the above (1), the alcohol After the steamed mash is removed, 'addition of water mixed in advance to form a mixture invites ethanolamine. (4) The high-fat composition of any one of the above (1) to (3), wherein the mixed molar ratio of the titanium alkoxide, the diol amine, and the water before the alcohol is distilled off When n:m:l is set, it satisfies the meaning of B (5) as described in any of the above items (1) to (4): 6 200936660 ju^wpii.aoc a fat composition in which the above alcohol is removed before being removed. Contains solvent. The film-shaped optical member' is characterized in that it is a difficult optical lens of 0 (4) formed by using a high refractive resin composition as described in the second article, and has a thickness of 1 (8) - a high refractive resin. The method for producing a composition is characterized in that ❹ ❹ w\ ζ£*· and the _salt, diethanolamine and water are mixed and heated, and the by-product alcohol vapor is removed from the shot to obtain a metal-containing high-fold addition. After the high-refraction intermediate containing metal is described, in the first step, in the step of producing the medium-high refractive resin composition, diethanolamine is added first, followed by adding water. The method, jitb is as described in the above (8). The water of the production of the high-refractive-resin composition is pre-mixed with the mixture of diethyl ether and the mixture of the two of the above-mentioned (8) to (1), and the high refractive index as described in any one of the above (8) to (1). In the above first step, when the steam is set to a mixed molar ratio of nm 'diethanolamine and water, the above mixing ratio is used to mix the above alcohol (12) as described above (8) to (11). High-refraction 7 200936660 iu^uupit.aoc A method for producing a resin composition, wherein The solvent is further contained before the alcohol distillation in the first step is removed. According to the configuration described above, the present invention can be applied to plastic lenses, iridium, optical fibers, information recording substrates, filters, components for liquid crystal displays, Membrane-shaped optical member represented by a member for a plasma display, a sheet, a diffuser, a light-scattering film, a viewing angle-enlarging film, a brightness enhancement film, a polarizing element, a light-trapping film for a solar cell, and the like, and a resin of the film-shaped optical member The material is particularly applicable to a film-like optical member having a high refractive index and a high-refractive resin composition. [Effect of the Invention] According to the present invention, it is possible to provide a more transparent, higher refractive index and obtainable than before. A high refractive resin composition of the thick optical member, and a method for producing a high refractive resin composition of the high refractive resin composition. Further, according to the present invention, it is possible to provide a more transparent and refractive index than before. And a film-like optical member having a desired film thickness can be obtained. In order to make the above-mentioned features and gamma energy of the present invention more important, the embodiment will be described in detail with reference to the drawings. [Embodiment] From: L First, the embodiment of the high-refractive-resin composition of the present invention is formed: === The method of manufacturing the refractive resin composition is the same as the method 8 200936660 ^ujuupn.aoc The by-product alcohol is distilled to obtain the component, and the refractive resin composition is characterized by two:: after the removal, water and diethanolamine are further added. The upper handle is distilled. The high refractive resin composition machine of the present invention includes: In the first step, the titanium alkoxide and the diethyl ester are heated and the by-product formed by the hydrolysis is heated to emit an intermediate; and the second step is obtained as a high refractive index of the metal-containing metal.

After the addition, water and diethanolamine were added. [Metal-containing high-refraction intermediate] As described above, the "metal-containing high-refraction intermediate" is obtained by heating a titanium alkoxide and heating after diethylation, and removing by-product alcohol produced by hydrolysis. Further, the step of obtaining the metal-containing high refractive intermediate is the first step of the production method of the present invention. The diethanolamine functions to be coordinated to the titanium alkoxide to control the progress of the hydrolysis reaction, thereby suppressing the growth of the titanium oxide particles. As described above, the birefringent resin composition of the present invention can obtain a metal-containing high refractive intermediate by actively distilling off the by-product alcohol produced by the hydrolysis, thereby suppressing the growth of the titanium oxide particles, and thus does not form a desired Larger particles above the size can avoid light scattering of the hardened material. (Titanium alkoxide) The above titanium alkoxide may also partially use other metal alkoxides depending on the purpose. The metal of the other metal-fired oxide is not particularly limited, and examples thereof include zinc (Zn), zirconium (Zr), lanthanum (La), yttrium (Th), yttrium (Ta), yttrium (Si), yttrium (Ge), and the like. . 9 200936660 3U3U0pit.doc For the above high refractive resin composition, there is no special structure for the base group, for example, the Kina carbon number is a 6-membered group, an isomer, a decyloxy group, a hexyloxy group and the like. When the calcination number is 2: the sol-gel reaction can be sufficiently carried out, and therefore g 3 , isopropoxy group or butoxy group is preferable, and isopropoxy group is particularly preferable. The types of the alkoxy groups may be all the same or different. The titanium alkoxide used in the above high refractive resin composition is: tetramethoxytitanium, tetraethoxyphosphonium, tetra-n-propoxytitanium, tetra-::oxytitanium, tetra-n-butoxytitanium, Tetra-t-butoxide, titanium-tetra-butadiene-based titanium, tetraphenoxytitanium, etc.; trimethoxytitanium, titanium, tripropoxytitanium, fluorotrimethoxytitanium, fluorine tri Ethoxy ruthenium, ruthenium oxyhydroxide, titanium triethoxytitanium, decyl tri-n-propoxy titanium, methyl = -isopropyl, titanium, ruthenium tri-n-butoxy titanium, methyl Tri-isobutoxytitanium, methyltri-t-butoxytitanium, methyltriphenoxytitanium, ethyltrimethoxy-f, ethyltriethoxytitanium, ethyltri-n-propoxy Titanium, ethyl tri-iso-, titanium, ethyl tri-n-butoxy titanium, ethyl tri-isobutoxy fluorene, ethyl di-t-butoxy titanium, ethyl triphenyloxy titanium , n-propyltrimethoxytitanium, propyl-ethyl-lactyl, n-propyltri-n-propoxy, n-propyl: ^_isopropoxy titanium, n-propyl tri-n-butoxy titanium , n-propyl tri-isobutoxy titanium, n-propyl tri-t-butoxy titanium, n-propyl triphenoxy titanium, Isopropyltrimethoxytitanium, isopropyltriethoxytitanium, isopropyltris-n-propoxytitanium, isopropyltris-isopropoxytitanium, isopropyltri-n-butoxytitanium, Isopropyl tri-isobutoxytitanium, isopropyl tri-t-butoxytitanium, isopropyl tri-alkoxy, zheng 200936660 ^υ^υυριι.αοο butyl tridecyloxy titanium, positive Butyl triethoxy titanium, n-butyl tri-n-propoxy titanium, n-butyl tri-isopropoxy titanium, n-butyl tri-n-butoxy titanium, n-butyl tri-isobutoxy Titanium, n-butyltri-t-butoxytitanium, n-butyltriphenoxide titanium, second butyltrimethoxytitanium, second butyltriethoxytitanium, second butyltri-n-propyl Titanium oxide, titanium dibutyl tris-isopropoxide, titanium dibutyl tri-n-butoxide, titanium dibutyl tri-isobutoxide, second butyl tri-tertiary butoxide Titanium, second butyltriphenyloxytitanium, tert-butyltrimethoxytitanium, tert-butyltriethoxytitanium, tert-butyltri-n-propoxytitanium, tert-butyltri-- Titanium isopropoxide, titanium tributyltri-n-butoxide, titanium tributyltris-isobutoxide, tert-butyl - titanium titanate, titanium tributyltriphenyloxide, titanium phenyltrimethoxytitanium, phenyltriethoxytitanium, phenyltri-n-propoxytitanium, phenyltri-isopropoxy Titanium, phenyltri-n-butoxytitanium, phenyltri-isobutoxytitanium, phenyltri-tert-butoxytitanium, phenyltriphenyloxytitanium, trifluoromethyltrimethoxytitanium , pentafluoroethyltrimethoxytitanium, 3,3,3-trifluoropropyltrimethoxytitanium, 3,3,3-trifluoropropyltriethoxytitanium, etc.; Tertyldimethoxytitanium, dimercaptodiethoxytitanium, dimercapto-di-n--n-propoxytitanium, di-decyldi-isopropoxytitanium, dimercapto-di-n-butoxytitanium , dimercapto-di-t-butoxide titanium, di-decyl bis-t-butoxytitanium, dinonyldiphenoxytitanium, diethyldimethoxytitanium, diethyldiethoxy Chin, diethyldi-n-propyl lactyl, diethyldi-isopropoxy, diethyldi-n-butoxytitanium, diethyldi-t-butoxytitanium, diethyl Di-t-butoxytitanium, diethyldiphenoxytitanium, di-n-propyldimethoxytitanium, -mono-n-propyl-monoethoxy-di-n-propyl-propyl - n-propyl lactyl, di-n-propyl di-isopropoxy titanium, di-n-propyl di-n-butoxy titanium, di-n-propyl 2 11 200936660 3〇3DOpif_doc • second butoxy Titanium, di-n-propyldi-t-butoxytitanium, di-n-propyldiphenoxytitanium, di-isopropyldimethoxytitanium, di-isopropyldiethoxytitanium, two - isopropyl di-n-propoxy titanium, di-isopropyl bis-isopropoxy titanium, di- isopropyl di-n-butoxy titanium, di-isopropyl bis-butoxy Titanium di-isopropyl-t-butoxy-, mono-isopropyldiphenoxy, di-n-butyldimethoxytitanium, di-n-butyldiethoxytitanium, di- n-Butyl-n-propoxytitanium, mono-yt-butylbis-isopropoxytitanium, di-n-butyldi-n-butoxy

Titanium, di-n-butyldi-t-butoxytitanium, one-stop Φ-le-g-titanium, di-n-butyldiphenoxide titanium, di-t-butyldimethoxytitanium, Di-t-butyldiethoxytitanium, di-t-butyldi-n-propoxytitanium, di-t-butyldi-isopropoxytitanium, di-t-butyldi-n-butoxy Titanium, bis. second butyl di-second butoxide titanium, bis-t-butyl bis-butadiene titanate, mono-t-butyldiphenoxide titanium, di-t-butyl bis Alkoxy phthalate, di-tert-butyldiethoxytitanium, di-t-butyldi-n-propoxy phthalate, monopropoxytitanium, di-t-butyldi-n-butoxytitanium ,: - first one base two - first butoxy titanium, two - third butyl two - third

Q Titanium, dibutyldiphenoxy phthalate, diphenyldimethoxytitanium, two ethoxytitanium, diphenyldi-n-propoxytitanium, diphenyldi-^ =-ben Basic di-n-butoxytitanium, diphenyldi-second-butoxy uranium gas: titanium butoxide, diphenyldiphenoxytitanium, bis(,, disubstituted dimethoxyl, The towel, the oxime and the like, the butanyl salt of the butoxy group, the special H is preferably contained with a *propoxy group, and the gas is different. For the present; the titanium alkoxide containing the isopropoxy group In the case of the resin composition, when the mixing molar ratio of titanium alkoxide, diethanolamine, and water before alcohol removal is set to n: m : 1 , it is preferable to make 1 < nsm. When the amount of water is large or when the amount of diethanolamine is small, the titanium particles are decomposed, so that the above inequality can be satisfied: a transparent and homogeneous composition can be formed. More specifically, a preferred one is preferable. It is 1 = 2 to 6, m = 5 to 9, and n = 3 to 7. (Polymer, oligomer, reactive monomer) The high refractive resin composition of the present invention may contain a polymer or oligomer and / or anti-numeral monomer, for polymer or low (4) There is no particular limitation, and those having high light transmittance or folding material, and having excellent miscibility and weather resistance are preferable, and examples thereof include epoxy resin, pGlyamide, and polyurethane. 'Polyurea (poly-), polyimine, P〇lyimide, polyamide irnide, polyethylene, polypropylene, polyether (P〇1yether), Polysulfide, polyester, polycarbonate, polyketon, etc. Adding the above polymer filaments into

== The weight of the fat component is 1 〇 by weight, and the amount of the polymer or the amount of 77 added is preferably 1 part by weight to 1 part by weight. A polymerized form of, for example, an ionic polymerizable component is known to be obtained by using a f-conjugated, hardened, high-refraction tree test (methane acid i::; body f epoxy derivative, isocyanate, alkene, butadiene) , propylene oxime, "steep diamine, styrene, isoprene, isocyanide, ^ A) H ethylene, of which epoxy epoxide from divalent acrylate, dicarboxylic acid, diol is preferred. , diamine, 13 200936660 3U300pit.doc styrene. When the above reactive monomer is added, 100 parts by weight of the component is obtained, and 1 part by weight is added to the high refractive resin group. The amount of the body to be added is preferably (solvent), preferably the alcohol in the r step of the above-described method for producing an alcohol oxime; that is, the solvent of the present invention preferably has a polarity and has a solvent. Two or more kinds are used, and among them, N-methylpyrrolidone using the same as the original two can be cited. 15 When the amount is preferably measured, the amount of the agent added to the high refractive resin composition is preferably 岐i. Parts by weight ~〗 _ _ Solvents are methanol, ethanol, propanol, isopropanol, butanol, butanol: 1 - pentanol: 2-pentyl , 3_pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2: heptanol, 3-heptanol, 4-heptanol, octanol, 2-octanol, 3 Dit-octanol, ethylene glycol monomethyl _ many kinds of alcohols are not particularly limited. Among them, 1-pentanol, ethylene glycol monoterpene ether, and heptanol are particularly preferable. (Additive) Further 'The present invention★ The refractive resin composition may contain an additive force. The above-mentioned additive may be a polymerization initiator such as a photoradical polymerization initiator or a ruthenium radical polymerization initiator, if necessary, and may be exemplified by ^200936660 ^ujuupxi. Aoc external absorbent, light stabilizer, stabilizer such as antioxidant, coupling flame retardant, etc. The radical polymerization initiation is relative to 100 parts by weight of the polymer or oligomer component and the reactive monomer component. The amount of the agent added is in the range of 0.01 parts by weight to 10 parts by weight, more preferably in the range of 1 part by weight of the hydrazine. & total relative to the polymer or oligomer component and the reactive monomer component. ❹ 100 parts by weight of the above-mentioned ultraviolet absorber or light-stabilized in a range of 0.05 parts by weight to 20 parts by weight. The antioxidants are changed according to the compatibility with the filler or the conditions such as the formation and the stability of the tree. In general, the phase polymer or oligomer component and The total amount of the reactive component is 100 parts by weight, and the antioxidant is added in an amount of ～10,000 ppm. The total amount of the I-copolymer as a component of the bifurcated slag component is 100 wt% of the coupling agent is usually added by adding G GG1 parts by weight. The total amount of the above-mentioned flame retardant is preferably in the range of 10 parts by weight to 300 parts by weight, based on the total amount of the monomer component of the polymer or the oligomer. 1 knife "heating ~ hydrolysis" and human = hair: Π containing metal high refractive index intermediate is by the following means. In addition, the above-mentioned titanium-diethanolamine solvent and additives are mixed, and *'舳&a Hanyou is used for hydrolysis by using the mouth and heating. Although an alcohol which is a by-product of hydrolysis of 15 200936660 ^wuupii.aoc is produced, the above alcohol batch is distilled off. The μ alcohol is volatilized by heating, and the temperature of the acid which is preferably heated at this step is preferably 6 (rc~1〇(rc) when the shoe is near the 15th product. In addition, if the by-product is isopropyl, the distillation of the alcohol calculated from the second or tenth == is good, the addition of the Cl compound (the second step) is refracted by heat and hydrolysis. The resin composition 'adds diethanolamine and water to the second step of the manufacturing process of the present invention after removing the second substance in the addition method, and the addition of diethanolamine and water. The purpose of the call is '10'. After it is processed into a film, L is hardened by heat treatment. At this time, ::: The diethanolamine on the two of the two is volatilized outside the system or is present at the right. Can make the TM structure grow further, from

Sts refractive index. That is, the final cured product can be obtained with a higher refractive index by adding water. This is because, by the addition of water, the structure in which the diethanolamine coordinated to the B atom is volatilized or freed by heating is entangled to cause a condensation reaction, and the Ti〇 structure is grown. In addition, the addition of diethyl _ at the same time helps stabilize the system and controls the rapid formation of titanium oxide particles. Further, when water is added first, when the amount of addition is large, the reaction proceeds rapidly, and gelation or precipitation of particles may occur. Therefore, the order of addition of water and diethanolamine is preferably followed by the addition of diethanolamine. Add water. Alternatively, water may be preliminarily mixed with diethanolamine to be added in the form of a mixture of 16 ❹ ❹ 200936660. When the water is pre-mixed with diethanolamine, the amount of water added is better than that of diethanolamine. The water is 2 moles to 18 moles: 疋帛: for the alkoxide 3 moles ~ 7 mo water (1) 6 molars with diethanolamine ~ ^ Mo Er. 'Yes 2: 2~18: 2, more preferably 6: 2~&amp; ratio = (X ·· y) better where 'water (X) and diethanolamine (), ^ ·· y) are better The mixing ratio is 2: 2~14 · 2. j alkoxide is 3 moles, the better mixing ratio is 2:2 ' when 4 moles, the better mixing ratio is 2:2~14:2 := When the salt is 5 moles, the preferred mixing ratio is 2:2~18; when 2::== ears, the preferred mixing ratio is 2: 2~20: 2. Titanium alcohol:, the upper limit of the upper limit of the water in the mixing ratio which is considered to be better. <Film-like optical member> The film-shaped optical member of the present invention is the above-described sorghum-in-the-month composition of the present invention. The formed, for example, can be obtained by applying the high refractive visceral group of the present invention to a substrate and drying it as needed. The method of applying the high refractive tree test composition to the substrate is not particularly limited, and examples thereof include a brush coating method, a spin coating method, a spray method, a slit coating method, and gravure printing. Gravureprinting, screen printing, and the like. Further, the above-mentioned substrate may be exemplified by a glass plate, a plastic plate, a plastic film, and the like, and a solar cell tank of 17200936660 3U3UUpit.d〇c. &gt; Drying is performed after the resin composition is refracted, and e' is to be volatilized. The drying conditions of the drying method are not particularly limited. For example, a heating plate (5), a fine electric furnace, or the like can be used. Preferably, it is 50 ° C ~ 1 耽, more preferably 6 (TC ~ 12crc 3 = 3 dry t if the drying temperature is less than 5 ° ° C 'can not fully dry the agent into a knife, right drying temperature If it exceeds 15 〇t:, the monomer will volatilize, and it will be difficult to obtain a good cured film. The knives are equal to 〇 = hardening after drying, and the high refractive resin composition is allowed to stand at a suitable temperature to determine the hardening temperature. 2 minutes ~ 3. minutes into the second:: The heat is less than 100.% may not be fully hardened. Right to the servant tit when the high refractive resin composition is photohardenable composition, the use of high pressure mercury lamps for the hard raft The hardening of the m cm is carried out. The high refractive resin composition is finally shot, and the film thickness of the optical member can be easily formed by adjusting the high-folding member. For example, if you reduce the eight* high refraction tree as the above solvent The viscosity of the composition is increased = 22 to 2, and 1 is added to the member; if the addition of the above-mentioned solvent component is relatively thick, the addition of a light-receiving knife is high, and the high refractive resin group 18 200936660 ^u^uupn.aoc When the viscosity of the product is lowered, it is easy to form an optical member having a relatively thin film thickness. Further, when a spin coating method is used as a coating method for a high refractive resin composition, a film can be formed by reducing the number of rotations or increasing the number of coatings. Thicker thick optical members, and by increasing the number of rotations or reducing the number of coatings, it is possible to open optical components with a relatively thick film thickness. The specific preferred thickness depends on the use of the optical member, but in the range of 1 μm [Examples] Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to the following examples. [Example 1] Separate flask (separabie fjask) in four mouths (1〇四个mi) four ports, respectively connected to the stirring wing, so as to supply nitrogen and distillation to remove volatile components of the connecting tube, and the Liebig condenser (Uebig condenser). Add to the separable flask Ethanolamine i4 72 g, water 1.44 g, and 1-pentanol 17.94 g' were stirred under a nitrogen stream. After a few minutes, it was confirmed that the mixture was sufficiently stirred to carefully add 28.42 g of tetraisopropoxide as far as possible without contact with air. After the addition of titanium tetraisopropoxide, the temperature of the flask rises, and the flask is cooled to about room temperature (25 ° C), and then the volatile component is removed by distillation using an oil bath. The distillation removal at this time is tetraisopropoxide. The by-product isopropanol produced by the hydrolysis reaction was carried out. Using a separately prepared sample tube, 4.90 g of water and 4.2 g of diethanolamine were sufficiently mixed to obtain a mixture. Next, after performing the above-described distillation removal for 6 hours, the separable flask was cooled to room temperature (25 ° C), and the 19 200936660 3U3 UUpit.d〇c mixture was added. The obtained liquid is referred to as liquid A (high refractive resin composition). To a separable flask, a solution obtained by adding 4,965 g of a polyester diol (manufactured by Kuraray Co., Ltd., trade name: Ajiaki 1 P1010) was added to 1494 g of N-methylpyrrolidone, and the mixture was thoroughly stirred. To the solution, 4,4-cyclohexylsulfonium diisocyanate (manufactured by sumika Bayer Urethane (trade name: Desmodur-W) 1009 g was added dropwise for 2 hours to obtain a B1 liquid (polymer or oligomer relative to A) 1 part by weight of the liquid, 1 part by weight of the B1 solution was added, and the mixture was sufficiently stirred. The resin composition thus obtained was spin-coated on a semiconductor wafer and a glass slide, and heated by a heating plate of 100 c for 5 minutes to remove The solvent obtained a film having a unit thickness of light having an absorbance (OD#m) for light having a wavelength of 450 nm of 〇._780' and a refractive index of the film for light having a wavelength of 632 8 nm of 1.68. In the film thickness, the film thickness of the film for measuring the refractive index was 〇·5 μm, and the film thickness for measuring the absorbance was 11 μm. Further, the measurement of the refractive index and the measurement of the absorbance were carried out as follows. Measurement> The obtained high refractive resin composition was diluted about 5 times with ΝΜΡ (Ν-methylpyrrolidone), and then coated on a semiconductor wafer for rpm at 1000 rpm using a spin coater. Leap second, to 2〇 The rotation speed of 〇 rpm was applied for 30 seconds. Thereafter, the film was obtained by heating to 15 (heated plate of rc for 15 minutes). The film was measured at the He_Ne laser wavelength using an ellipsometer MARY-102 manufactured by Five Lab. 632.8 nm) 200936660 refractive index at ju^uupn.aoc. &lt;Measurement of Absorbance&gt; The obtained high refractive resin composition was directly coated on a glass slide using a spin coater. Heating with 15 ° C The glass plate coated with the resin composition was heated for 15 minutes to obtain a film. At this time, the rotation speed of the spin coater was adjusted so that the film thickness became about 1 μμη!. Using a UV_VIS spectrophotometer (Japan Distribution Co., Ltd.) The manufactured JASCOV-540) measures the absorbance spectrum of the film on the obtained ruthenium glass substrate and divides it by the measured value of the film thickness to obtain the spectrum of the OD/μη unit. Here, the value is specifically 45 〇 nm. [Example 2] An ultraviolet ray ultraviolet (UV) hardening resin (manufactured by 曰立化成工业) was added as a B2 liquid to 1 part by weight of the liquid A obtained in Example 1. Hi Taloid7981) 10 parts by weight and fully disturbed' The resin composition liquid thus obtained was spin-coated on a semiconductor wafer and a glass slide, and heated by a heating plate at 100 ° C for 5 minutes to remove the agent. The film was cured by irradiation with ultraviolet rays, and the film thickness per unit film thickness of the film having a wavelength of 450 nm was 0.000842, and the refractive index of light having a wavelength of 632.8 nm was 1.70. In the film thickness of the formed film, the film thickness for measuring the refractive index is about 0.5 μΠ1. The film thickness for measuring the absorbance is about 10 μm. Further, the measurement methods of these measurements are the same as in the first embodiment. [Example 3] An epoxy resin (manufactured by Otsuka Ink Co., Ltd., trade name EXA-4850-1000) as a 21 200936660 3U3 UUpii.doc B3 liquid was added to 100 parts by weight of the mash obtained in Example 1. 10 parts by weight and stirring well, and the resin composition liquid thus obtained was spin-coated on a semiconductor wafer and a glass slide, and heated by a heating plate of 8 ° C for 5 minutes to remove the solvent, further using i5 〇 °c The hot plate was heat-hardened for 15 minutes to obtain a film. The unit film thickness of the film has an absorbance (0.D /) xm) for light having a wavelength of 450 nm of 〇 564, and a refractive index of 173 for light having a wavelength of 632.8 nm. In the film thickness of the formed film, the film thickness for measuring the refractive index was about 0.5 μm, and the film thickness for measuring the absorbance was about 10 μm. Further, the measurement methods of these measurements were the same as in the first embodiment. [Comparative Example 1] A stirring blade was attached to each of four ports of a four-neck separable flask (l〇〇ml) to facilitate supply of nitrogen gas and distillation to remove volatile components, and a Liebig condenser. To the separable flask were placed 14.72 g of diethanolamine, 1.44 g of water and 17.94 g of 1-pentanol, and the mixture was stirred under a nitrogen stream. After a few minutes, confirm that the mixture has been thoroughly stirred to carefully add 28.42 g of titanium tetraisopropoxide as far as possible without contact with air. After the addition of tetraisopropoxide, the temperature of the separable flask was raised, and the flask was cooled to room temperature (25. (:)) and then used 80. (: The oil bath removed the volatile components. The removal product is a by-product isopropanol formed by hydrolysis of tetraisopropoxide titanium oxide. This liquid is referred to as liquid C. In a separable flask, 'addition of N-methylpyrrolidone 1494 g to 4965 g of Kuraray was added. The solution obtained by the trade name Kuraray Polyol P1010 was fully scrambled, and 1〇〇9 g of 200936660 ^υ^υυριι.αοο was added dropwise thereto.

The product name Desm〇dur_w, manufactured by Sumika Bayer Urethane (share), was obtained in 2 hours to obtain B1. liquid (polymer or oligomer). Compared with the weight fraction of the C liquid, the liquid is mixed with a weight of 1 ,, and the thus obtained resin composition droplet is added to the current glass slide of the semi-sickle blade, but the surface of the composition liquid is in contact with air. A coating film capable of measuring optical properties is obtained by the method. The results of the above examples and comparative examples are shown in the table ❹ 2009 23 200936660 ※铒驷卡-一冷絮雀雀迪3»崁玦3:徊谇-Θ?*» Minced M ^ Di net bran smashed. Film thickness (μη〇 refractive index absorbance (〇.D./pm) Solvent polymer or oligomer 1 addition | Synthetic material Diethylamine water (1) Diethanolamine (m) Titanium yeast (η) 1 0.5 2 10.0 1.68 0.000780 1-pentanyl N-methylpyrrolidone Di Ο &amp;&quot;Fog® -3⁄4 撖 Bu 0.27 mol 0.4 mol Water 0.08 mol Diethylamine 0.138 mol Tetraisopropanol hydrazine ·1 〇〇mol Example 1 ©0.5 ©10.0 1.70 0.000842 1-pentyl N-methylpyrrolidone acrylic polyurethane 0.27 mol 0.4 mol Water 0.08 mol Diethylamine 0.138 mol Tetraisopropoxide 0.100 mol Example 2 1 0.5 2 10.0 1.73 0.000564 1-pentanyl N-methylpyrrolidone epoxy resin 0.27 mol 0,4 mol water 0.08 mol diethylamine 0.138 mol tetraisopropyl oxide 0.100 mol Example 3 failure to film formation can not be assessed 1-pentyl N-methylpyrrolidone oxime &amp; O to fis 撖 Bu water 0.08 mol Diethylamine 0.052 mol Tetraisopropoxide 0.100 mol Comparative Example 1 30300pif.doc 200936660 ovi^uupu.uoc As can be seen from Table 1 Examples 1 to 3 can form a transparent, high-emission rate and a desired film thickness. In contrast, in Comparative Example 1 in which the alcohol was distilled off and the mixture of water and diethanolamine which were previously mixed was not further added, it was not possible to obtain a coating film capable of measuring optical characteristics. The following Example 4 to implementation Example 25 and Reference Example 1 to Reference Example 3' are examples in which a high refractive resin composition containing only a metal-containing refractive index intermediate is cured without using a polymer or the like. Win [Example 4] Four-port separable type On the four ports of the flask (2000 ml), the stirring wings were respectively fastened to facilitate the supply of nitrogen and the connection tube for removing the volatile components, and the Liebig condenser. The diethanolamine 262.9 g, the water i8.〇g and 1- 325.2 g of pentanol was added to a separable flask and stirred under a nitrogen stream. After a few minutes, it was confirmed that the mixture was sufficiently stirred to carefully add 426.3 g of tetraisopropoxide as much as possible in contact with air. After the titanium oxide, the temperature of the flask was raised, and the flask was cooled to room temperature (25 C), and then the volatile component was removed by steaming using an 80 ° C oil bath. The distilled residue at this time was tetraisopropyl. For titanium byproducts generated by the hydrolysis reaction of isopropanol. 105.1 g of diethanolamine mixture was obtained using another sample tube to prepare, mix 18 〇g water. Next, after the above-described distillation and removal for 6 hours, the separable flask was cooled to room temperature (25 Å), and the mixture was added (hereinafter referred to as "subsequent addition" in Table 2) to obtain a high refractive resin composition. The solution state, color, viscosity, and absorbance of the high refractive resin composition were evaluated and measured, and the results shown in Table 2 were obtained. In addition, each evaluation 25 200936660 JUiuupit.aoc price item evaluation method is as follows. &lt;Solution state&gt; The high refractive resin composition prepared by visual observation was evaluated as "good" when no turbidity was observed at all. When the turbidity was observed, it was evaluated as "micro turbidity", and turbidity evaluation was observed at a glance. It is "turbid". &lt;Color&gt;

The prepared high refractive resin composition was visually observed, and the color of the solution was observed. When it was transparent, it was evaluated as "transparent", when it was pale yellow, it was evaluated as "light color", and when it was yellow, it was evaluated as "yellow", and when it was yellow, it was evaluated as orange. It is orange." &lt;Viscosity&gt; The viscosity of the prepared high refractive resin composition was measured using an E-type viscometer. &lt;NV (nonvolatile content ratio)&gt;. The prepared high refractive resin composition 丨g was added dropwise to the pure one, and heat treatment was carried out for 2 hours under a thief, and the change in weight before and after the heat treatment was measured to calculate N V . 〇NV—(weight after heat treatment)/(weight before heat treatment) <Measurement of absorbance (solution)&gt; In disposable battery (disp〇sable _) (optical path length: ^ light/spectrum, material is the wavelength of the representative value In addition, the length of the pool is called lem, and the position is (10) / curry. Next, the results of the measurement are shown in Table 2 by the method of T, which is prepared by the above (4), 2009 26660 ^u^uupir.aoc. Measurement of refractive index and absorbance &lt;Measurement of refractive index&gt; H Ϊ high refractive resin composition and U pentanol in a weight ratio of 2: K) You add to the dream wafer '3G second rotation at 5 rpm After 1 G minutes of heat treatment under the coated boots, the measurement was carried out using an ellipsometer MARy_1〇2 manufactured by FiveLab. &lt;Measurement of absorbance (film)&gt; 0 The obtained ruthenium refractive resin composition was dropped on a glass slide, spin-coated at 500 rpm for 30 seconds, and heat-treated with 15 Torr of the hot plate for 1 m after heat treatment. The light was incident from the glass side of the substrate, and the absorbance spectrum was measured by a spectrophotometer (manufactured by JASCO Corporation, JASCO V-540). The value of the absorbance at a wavelength of 450 nm was divided by the thickness of the coating film, and the absorbance at a unit thickness of O.D./μιη was obtained for evaluation. Table 2

Material Example 4 Example 5 Example 6 Example 7 Reference Example 1 Mo Erbi Titanium Salt 〇) 3 3 3 3 3 Synthesis of Diethylamine (m) 5 5 5 5 5 Water (1) 2 2 2 2 2 1 - Fermentation is adjusted to NV = ( »•6 Subsequent addition of diethanolamine 2 2 2 2 2 Water 2 6 10 14 18 Solution state Good 妤 Good good turbid color Light light pale light pale pale liquid "1 Viscosity (mPa-s) 169.1 112,2 91.3 78.9 - NV 0,55 0.54 0.51 0.50 - Absorbance (〇D/cm) 0.009180 0.008000 0.008100^ 0.141900 Male Μ Refractive index 1.66 1.68 1.71 1.72 --- Absorbance (OD/μιη) 0.000815 0.000799 0.000770 0.000744 - 27 200936660 ^u^uupii.aoc [Example 5 to Example 7 and Reference Example η High-fold (four) fat in the middle ^ (4) The amount of water added was added in the manner shown in Table 2 to prepare a high-fat composition. The evaluation results are shown in Table 2. [Example 8 to Example u and Reference Example 2] The amount of tetraisopropoxide was changed to 8 g, 2, 252.3 g, and water to 21.6 g. And the conversion of u-pentanol to 3〇9 5^ is carried out in the same manner as in the case of real_4 to real_7. (4) The high refractive resin compositions of Example 11 and Reference Example 2 were evaluated in the same manner as in Example 4. The evaluation results are shown in Table 3. Table 3 Materials [i Example 9 X Court Example 10 |锏n 来者锏2 ------ Mo Erbi Titanium Fermentation a (η) 4 4 4 4 4 Synthesis of Diethylamine (m) F 6 6 6 6 6 Water (1) 3 3 3 3 3 1-E Yeast. «秣NV=i K6 Subsequent Diethylamine 2 2 2 2 2 Add water 1 1 H 'aeaB=aaa-aBB^=^Bj 2 6 10 14 18 Good in good condition Good good turbid color Light color light color Light pastel liquid 艟 viscosity (mPa*s) 240.3 124.2 115.4 93.3 84.0 NV 0.56 0.56 0.53 0.52 0,49 Absorbance (〇D/cm) 0.025360 0.020380 0.019660 0.020640 0.029380 Refractive index 1.66 1.68 1.70 ] 1.71 1.73 Absorbance (OD/μηΟ 0.000946 0.000849 0.000796 0.000762 0.000859 [Example 12 to Example I5 and Reference Example 3] The amount of the titanium tetraisopropoxide was changed to 497.4 g, the diethanolamine was changed to 257.6 g, the water was changed to 25.2 g, and the 1-pentanol was changed to 314.0 g. , 28 200936660 ^υ^υυριι,αος and Example 4 to Example 7 The refracting resin compositions of Examples 12 to 15 and Reference Example 3 were prepared in the same manner, and evaluated in the same manner as in Example 4. The evaluation results are shown in Table 4. Table 4 Materials Example 12 丨 4 application wi 丨霣 Example 14 丨 f Example 15 | Reference Example 3 - Synthesis of titanium yeast salt (η) 5 5 5 5 5 Diethylamine (m) 7 7 7 7 7 Water (1) 4 4 4 4 4 1-pentaldehyde is adjusted to NV=0.6 Subsequent addition of diethylamine 2 2 2 2 2 Water 2 6 10 14 18 Liquid 溶液 Good condition Good good Good turbid color light light pale light pale light viscosity ( mPa*s) 403.8 268.1 196.0 146.8 119.5 NV 0.57 0.55 0.52 0.50 0.48 Absorbance (〇D/cm) 0.026480 0.019000 0.023280 0.019740 0*019310 Boqi Refractive Index 1.66 1.68 1.69 1.70 1.73 Absorbance (OD/μηι) 0.000981 0.001153 0.000797 0.000752 0.000809 [ Example 16 to Example 20] Example 4 was carried out except that the titanium tetraisopropoxide was changed to 511.6 g, the diethanolamine was changed to 252.3 g, the water was changed to 27.0 g, and the 1-pentanol was changed to 306.1 g. The high refractive resin compositions of Examples 16 to 20 were prepared in the same manner as in Example 7 and evaluated in the same manner as in Example 4. The evaluation results are shown in Table 5. 29 200936660 jujuupn.aoc Table 5 Materials Example 16 Example Π Example 18 Example 19 Travel Example 20 Moerby Synthetic Titanium Fermentation only (η) 6 6 6 6 6 Diethylamine (m) 8 $ 8 8 8 Water (1) 5 5 5 5 5 1-pentaldehyde is NV=0.6 Subsequent addition of diethylamine 2 2 2 2 2 Water 2 6 10 14 18 Liquid "1 Good solution in good condition Good good color ● Light color light pastel color Light color viscosity (mPa's) 437.2 293.6 Γ 213.9 169.1 136.0 NV 0*58 0.56 0.55 0.54 0.53 Absorbance (〇D/cm) 0.041130 0.036370 0.033420 0.032290 0.032430 Film refractive index 1.66 1.66 1.69 1.70 1.69 Absorbance (OD/μιη) 0.001183 0.001041 0.000870 0.000806 0.000830

[Examples 21 to 25] Except that the titanium tetraisopropoxide was changed to 537 2 g, the diethanolamine was changed to 255.5 g, the water was changed to 29.2 g, and the pentanol was changed to 3〇8 8 g, The high refractive tree enthalpy of Example 25 was prepared in the same manner as in Example 4 to Example 7, and was the same as Example 4. The evaluation results are shown in Table 6.订汗30 200936660^υ^υυριι.αοο Material Example 21 Example 22 Example 23 IT Example 24 丨 Example 25 _ Mo Erbi Titanium S (η) 7 7 7 7 7 Synthesis of Diethanolamine (m) 9 9 9 9 9 Water (1) 6 6 6 6 6 1-pentaldehyde adjusted to NV=fl •6 Subsequent diethylamine 2 2 2 2 2 Add water 2 6 10 14 18 The solution is in good condition *Good, good good liquid醴Color light color light color light color light color viscosity (mPa's) 498.1 321.7 240,3 199.5 165.3 NV 0.61 0.59 0.56 0.55 0.53 Absorbance (OD/cm) 0.025900 0.024640 0.022990 0.026030 0.016170 Film refractive index 1.67 1.67 1·69 1.69 1.69 Absorbance (OD /μπι) 0.001190 0.001075 0.000922 0.000851 0.000861 It can be seen from Table 2 to Table 6 that if the amount of water added later is increased, turbidity can be seen, but if the amount of titanium tetraisopropoxide is increased at this time, the turbidity disappears. If the amount of water added later is increased, the viscosity and ^^¥ become smaller. Regarding the absorbance of the liquid, if the amount of water to be subsequently added is increased, the absorbance is lowered, but when it exceeds a certain amount, turbidity is generated and the absorbance is increased. Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and those skilled in the art can make some modifications and refinements without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims. [Simple description of the schema] &quot; None. [Main component symbol description] 〇 31

Claims (1)

200936660 30300pit.doc VII. Patent application scope: 1. A high refractive resin composition comprising a metal-containing high refractive intermediate. The metal-containing refractive intermediate is heated by mixing titanium alkoxide, diethanolamine and water. The high refractive resin composition obtained by distilling off the by-product alcohol produced by the hydrolysis is characterized in that after the above alcohol is distilled off, diethanolamine and water are further added. 2. The high refractive resin composition as described in claim i, wherein the above alcohol is distilled off, the above-mentioned diethanolamine is added first, and then water is added. 3. For the application of the high-refractive resin composition in the first item of the special rhyme, in which the water is mixed with the diethanolamine in the form of a pre-aged mixture. 4. If you apply for a patent scope! Item to item 3, wherein: the test of the tree shooter, wherein the mixed molar ratio of the above alcohol alkoxide, diethanolamine and water is set to n:m:= 5. The material (4) 丨 述 之 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高 高The patented optical member ' is characterized in that it is formed using the high refractive index composition (4) as described in the first item of the application (4). I, if you look at the 6th grain thickness, the thickness is 1 to 1000 μπι. Sleeping: 8. A method for producing a high refractive resin composition, characterized in that it comprises a package 32 200936660 jujuupn.aoc, a first step, which comprises mixing titanium alkoxide, diethanolamine and water, and heating and generating the auxiliary The product alcohol vapor is removed to obtain a metal-containing high refractive intermediate; and the second step 'after obtaining the metal-containing high refractive intermediate, more diethanolamine and water are added. The refractory resin composition of the high-refractive-refining resin composition described in the eighth aspect of the invention is in which the diethanolamine is added first in the second step, and then water is added. In the high refractive resin composition t described in the eighth aspect of the patent, in the second step, water and diethanolamine which are previously mixed into a mixed form are added. 11. The method for producing a refractive resin composition according to the eighth aspect of the patent application, wherein: the above-mentioned, y molar ratio U η : m and water mixed titanium alkoxide, the above diethanolamine are distilled off The high refractive resin composition described in the above-mentioned compounding ratio is further mixed with the solvent material 1 before the spicy cutting material is removed. 33 200936660 ^ujuupn.aoc IV. Designated representative figure: (1) The case Designated representative map: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: