TW201020581A - Heat-resistant composite lens - Google Patents

Abstract

To provide a heat-resistant composite lens durable against a solder reflow process. The composite lens includes a lens base to which a resin layer is joined, wherein each of the lens base and the resin layer is made of a curable resin. At least the lens base includes a cured silicone resin containing polyorganosilsesquioxane expressed by general formula (1):(RSiO<SB>1.5</SB>)m(RSiO<SB>0.5</SB>)n and having a cage structure in the structural unit. In formula (1), R represents an unsaturated group expressed by (a) -R1-OCO-CR2=CH2, (b) -R1-CR2=CH2 or (c) -CH=CH2, an alkyl group, a cycloalkyl group, a cycloalkenyl group, a phenyl group, a hydrogen atom, an alkoxyl group or an alkylsiloxy group, and a plurality of R in formula (1) may be mutually different but at least one of them includes (a), (b) or (c); R1 represents an alkylene group, an alkylidene group or a phenylene group; R2 represents a hydrogen atom or an alkyl group; m represents a number from 8 to 16; and n represents a number from 0 to 4.

Description

201020581 IX. INSTRUCTIONS OF THE INVENTION [Technical Field of the Invention] The present invention relates to a heat-resistant composite lens characterized in that a composite lens formed by bonding a resin layer to a lens substrate is, for example, carried in action. A CCD (Charge Coupled Device) with a lens or a CMOS (Complementary Metal Oxide Semiconductor) sensor with a lens, such as a telephone or a digital camera, and is suitable for a semiconductor camera and a lens. Wait for users. [Prior Art] Conventionally, a lens for a camera module uses a lens made of plastic based on the purpose of lowering the price. A lens made of a plastic can be obtained by injection molding or the like of a transparent resin such as a polycarbonate resin, a acryl resin or an alicyclic hydrocarbon-containing polymer to obtain a convex lens or a concave lens. In recent years, based on the purpose of reducing the cost of mounting electronic components, it has been possible to reflow soldering the camera module in the same manner as other electronic components, so that it can be refilled at one time. Furnace heat (26 (TC). However, the current plastic lens cannot pass the reflow oven because its heat resistance temperature is only below 180 ° C. One of the means to solve this problem, such as special opening 2004- 1 3 3 Japanese Patent Publication No. 3 (Patent Document 1) discloses that a heat-resistant or photocurable resin capable of withstanding a reflow temperature is used as a post-replenishment material. However, in general, a curable resin is likely to be generated by a reaction. In the case of the hardening and shrinkage, the molding is broken during the forming process, and it is difficult to ensure the stability of the mold reproducibility of the molded article, etc., in the case of the Japanese Patent Publication No. 2005-60657 (Patent Document 2). A composite lens in which a glass lens is used as a base material to form a film of heat or light hardening resin on the surface thereof. However, the conventional composite lens has a difference in linear expansion coefficient between glass and resin. In particular, in the hot and humid environment, the adhesion to the interface between the glass and the resin is easily lowered, which is not complete at the point of durability. Further, in the composite lens, the glass lens of the base material is compared with the plastic lens. However, due to the long forming time and the high production cost, the manufacturing cost is high, and it is not suitable for a camera module for a mobile phone or a digital camera that can be produced inexpensively and mass-produced. Patent Document 1: Special Opening 2004 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION In order to solve the above problems, an object of the present invention is to provide a heat-resistant composite lens. The present invention is suitable for use as a lens for a camera module capable of withstanding a reflow soldering step, etc. Solution to Problem The inventors of the present invention have conducted intensive review to solve the problem of the conventional plastic lens or composite lens. , found that at least the clustered structure of polyorganic sand silsesquioxane as the main component of -6 - 201020581 The hardened resin made of the ketone resin is applied to the lens substrate, and the resin layer formed of the hardened resin is bonded to the lens substrate to provide an inexpensive heat supply which can be supplied to the reflow soldering step. The present invention has been completed. That is, the present invention is a heat-resistant composite lens characterized by a composite lens in which a resin layer is bonded to a lens substrate, and a lens base. Each of the material and the resin layer is made of a hardened resin, and at least the lens substrate is represented by the following general formula (1): (RSi〇15)m (RsiO〇.5) „ (1) (only, R system (a) -R^OCO-CR^CHi ' (b) -R1-CR2 = CH2 or (c) -CH = an unsaturated group represented by CH2, an alkyl group, a cycloalkyl group, a cycloalkenyl group, a phenyl group, a hydrogen atom, an alkoxy group, or an alkylcarbomethoxy group, wherein a plurality of R in the formula (1) may be different, but at least one system contains the above (O, (b) or (c) In one case, R1 is an alkyl group, an alkylidene or a phenyl group, R2 is a hydrogen or an alkyl group, m = 8 to 16, and n = 0 to 4), and is a cluster having a cage structure in a structural unit. Organic Poly siloxane silicone-resin main component of the semi-hardening the winner. Further, in a preferred aspect of the invention, the resin layer is represented by the general formula (1), and in the structural unit, a polyfluorene ketone having a polyorgano sesquioxanes having a cage structure as a main component The resin is hardened. In the present invention, a hardening resin may be obtained, wherein the polyfluorene ketone resin is compounded with a compound having at least one hydrogenated methyl sulfonium-7-201020581 group in the molecule and/or having ethyl acrylate unsaturated Further, the compound of the base is further blended with a curable resin composition obtained by hydrogenating a formazan alkylation catalyst and/or a radical initiator, and then the curable resin composition is thermally cured or photocured. Hereinafter, the present invention will be specifically described. Each of the resin substrate and the resin layer in the present invention is made of a cured resin, and at least the resin substrate is cured by a polyketone resin which will be specifically described below. That is, the polyfluorene ketone resin used in the present invention is a polyorgano sesquioxanes having a cage structure as shown in the above formula (n, that is, a cage structure in a structural unit (hereinafter, also referred to as " Here, the structural unit, specifically, the repeating unit represented by m or η in the general formula (1), is called in the structural unit. In the case of a cage structure, it means that one of the repeating units indicated by m or η or both has a cage structure. Further, a polyorgano sesquioxanes having a cage structure are as described below. It consists of a three-dimensional polyhedron structure skeleton and R, but one of the three-dimensional polyhedral structural skeletons is also included in the open loop (that is, the incomplete cage structure). Here, the general formula ( In the case of 1), it is necessary that at least one of R is an unsaturated group represented by the above (a), (b) or (c), and a specific example of such an unsaturated group is 3-methylpropenyloxy. a propyl group, a 3-propenyloxypropyl group, an aryl group, a vinyl group, a styryl group, etc. The polyfluorene ketone of the present invention Among the fats, in addition to the polyorganobexesquioxane having a cage structure, the ruthenium contains a polyfluorene ketone resin having the following structure or no cage structure, and the proportion thereof is preferably less than 30% by weight. 201020581 【化1】

O' ? •^i~0~ R R&quot;0_

• RR~0* K ν (In the above formula, at least one of R is based on the general formula (1), and y ® is the number of repetitions 1 to 1 000.) The general formula (1) is expressed by three times. The polyhedral structural skeleton and the cage polyoxyalkylene formed by R, each of which is an example of the following formula (3) when m in the general formula (1) is 8 and η is 0: when m When 10 is 10 and η is 0, it is the following structural formula (4); when m is 12 and η is 〇, it is the following structural formula (5): and, when m is 8 and η is 2, It is the following structural formula (6). However, the polyketone resin represented by the general formula (1) is not limited to those represented by the structural formulae (3), (4), (5 ® ), and (6). -9- 201020581 【化2 RSi-Ο-SiR/ /1 RSi^—?·〇-SiR ? (3)

RSi-0-SiR R

(4)

R R —〇一Si,

RSi^° 〇 0 \jR Hirose, I R.〇ri

1 Less Bu (RSi^ 〇 〇 u R R

〇 RSi —!〇—Si I I — SiR 9

〇J (5)

&gt;SiR

The cage type polysiloxanes represented by the above structural formulas (3), (4), and (5) may be used singly or in combination with the oxime compound represented by the following general formula (7), -10- 201020581

RSiX3 (R, R system (a) - R1-OCO-CR2 = CH2 ' ( b ) -R1-CR2 = CH2 or (c) -CH = unsaturated group represented by CH2, alkyl group, cycloalkyl group, ring Alkenyl, phenyl, hydrogen, alkoxy, or alkylformyloxy, R1 is alkyl, alkyl or phenyl, R2 is hydrogen or alkyl, and X is selected from alkoxy a hydrolyzable group of one of a group of a halogen group and a hydroxyl group), and a solvent which is used in one or both of a nonpolar solvent and a polar solvent under a basic catalyst, and simultaneously Made by condensation. Further, the cage type polyoxyalkylene shown by the above structural formula (6) can further form a cage type polyoxane represented by the structural formula (3), (4), or (5). The re-condensation product obtained by re-condensation in the presence of a polar solvent and a basic catalyst is obtained by subjecting a dioxane compound to an equilibrium reaction. ® For the polar solvent in the case of obtaining the cage-type siloxane of the structural formulae (3) to (6), for example, an alcohol such as methanol, ethanol or 2-propanol may be mentioned. Further, as the nonpolar solvent, for example, toluene, xylene, benzene or the like is mentioned. Further, examples of the basic catalyst include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, benzyltriethylammonium hydroxide, and the like. Ammonium hydroxide salt. Among them, tetramethylammonium hydroxide is preferred from the viewpoint of high catalyst activity. Further, in the case of an alkaline catalyst, an aqueous solution is generally used. Further, in the present invention, for the polyfluorene ketone resin, a compound having at least one ethylenically unsaturated double bond in the molecule -11 - 201020581 or a compound having at least a hydrogenated methyl hydrazine group in the molecule may be blended. Alternatively, a curable resin composition may be used; or both of them may be blended to form a curable resin composition. Then, the curable resin composition may be thermally cured or photocured to obtain either or both of a lens substrate or a resin layer. Here, if a compound having at least one ethylenically unsaturated double bond in the molecule is blended, it may contain a radical initiator in the curable resin composition; and if it is a compound, it has at least hydrogenation in the molecule. In the case of a carbaryl alkylate compound, a hydroformylation catalyst can be contained in the curable resin composition. The compound having at least one ethylenically unsaturated double bond in the above molecule may be an unsaturated compound which can be copolymerized with a polyfluorene ketone resin and a radical, but is compounded on the above polyfluorene ketone resin. Suitable polymers are reactive oligomers of polymers having a repeat number of from 2 to 20, and low molecular weight and low viscosity reactive monomers. Further, it may be a monofunctional unsaturated compound having one unsaturated group and a polyfunctional unsaturated compound having two or more. For the purpose of obtaining a good 3D crosslinked body, a very small amount (about 1% or less) of a polyfunctional unsaturated compound may be contained, and when the heat resistance and strength of the copolymer are expected, the average molecular weight per molecule is 1.1. More than one is preferred, and 1.5 or more is better '1.6 to 5 is the best. Therefore, a monofunctional unsaturated compound and a polyfunctional unsaturated compound having 2 to 5 unsaturated groups may be used in combination, and the average number of functional groups may be adjusted. Specifically, reactive oligomers, for example, epoxy acrylate, -12-201020581 epoxidized oil acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate , vinyl acrylate, polyolefin / thiol, poly fluorenone ~ acrylate, polybutadiene, polystyrene ethyl methacrylate and the like. These are monofunctional unsaturated compounds and polyfunctional unsaturated compounds, reactive monofunctional monomers such as styrene, vinyl acetate, N-vinyl pyrrolidone, butyl acrylate, 2-ethylhexyl acrylate , η-hexyl acrylate, cyclohexyl acrylate, η-mercapto acrylate φ, isobornyl acrylate, dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl Acrylate and the like. Further, a reactive polyfunctional monomer such as tripropylene glycol diacrylate having an unsaturated compound other than the general formula (2), 1,6-hexanediol diacrylate, bisphenol quinone diepoxypropyl ether II Acrylate, tetraethylene glycol diacrylate, hydroxytrimethylacetic acid neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate Wait. ® A compound having at least one ethylenically unsaturated double bond in the molecule which can be used in the present invention, and various reactive oligomers or monomers can be used in addition to those exemplified above. Further, these reactive oligomers or monomers may be used singly or in combination of two or more kinds. By radical copolymerizing these, it is also possible to obtain a radical initiator which is used in combination with a compound having at least one ethylenically unsaturated double bond in the molecule. As long as it can be used as a photopolymerization initiator or a thermal polymerization initiator. Here, the photopolymerization initiator is suitable for a compound such as an acetophenone system, a benzoin system, a benzophenone system, a thioxanthone system or a mercaptophosphine oxide system. Specifically, for example, trichlorophenylacetamidine, monoethoxyphenidinium, 1-phenyl&quot;yl-2-carbazino-2-methylpropan-1-pyrene, 1-hydroxy-cyclohexylphenyl Ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, benzoin methyl ether, thioxanthone, 2,4,6-trimethyl Benzamidine diphenylphosphine oxide, methylphenylglyoxylate, camphorquinone, benzoin, oxime, rice ketone, and the like. Further, it is also possible to combine a photopolymerization initiator with a light-starting aid or a sensitizer φ which can exert an effect. These photopolymerization initiators may be used singly or in combination of two or more types. Further, a thermal polymerization initiator used for the above purpose is suitable for a user having a ketone peroxide system, a peroxyketal system, a hydroperoxide system, a dialkyl peroxide system, and a dithiol peroxidation. Various organic peroxides such as a system, a peroxydicarbonate system, and a peroxy ester system. Specifically, for example, cyclohexanone peroxide, 1,1-bis(t-hexaperoxy)cyclohexanone, cumene hydroperoxide, dicumyl peroxide, benzamidine peroxide And diisopropyl hydrazine peroxide, t-butylperoxy-2-ethylhexanoate, etc., but are not limited to these ranges. Further, these thermal polymerization initiators may be used singly or in combination of two or more types. When a radical initiator, such as a photopolymerization initiator or a thermal polymerization initiator, is added, the amount thereof is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the polyfluorenone resin, and is 0.1 to 0.1. The range of 3 parts by weight is optimal. If the amount is less than 0.1 part by weight, the hardening may be incomplete, and the strength or rigidity of the obtained lens may be lowered. On the other hand, if it exceeds 5 parts -14 - 201020581 parts, problems such as the color of the lens may occur. In another aspect, the compound having at least a hydrogenated methylation group in the above molecule is preferably an oligomer and a monomer, and the oligomer and the monomer are characterized by at least a ruthenium atom in the molecule. A hydrogen atom having one or more hydrogenated methyl hydrazides. An oligomer having a hydrogen atom on a ruthenium atom, for example, a polyhydrogenadiene oxyalkylene, a polydimethylhydroformaloxy alkoxy olefin, a copolymer thereof, and a terminal dimethyl hydroformane A methoxy group modified with an oxy group. Further, as the monomer having a hydrogen atom on the ruthenium atom, for example, a cyclic siloxane such as tetramethylcyclotetraoxane or pentamethylcyclopentane, dihydrodioxane or trihydrogen is used. Monodecanes, dihydromonodecanes, monohydromonodecanes, dimethylformamoxyoxyalkylenes, and the like. These can also be used in combination of 2 or more types. a hydroformamidine catalyst used in combination with a compound having at least a hydroformyloxy group in the molecule, for example, a chlorine (IV), a chloroplatinic acid, a chlorolead acid, and a complex of an alcohol, an aldehyde, a ketone, A complex of chloroplatinic acid and an olefin, a complex of a pin and a vinyl siloxane, a dicarbonyl chloroplatinum, a palladium catalyst, and a platinum group metal catalyst such as a ruthenium catalyst. Among these, from the viewpoint of catalyst activity, a complex selected from the group consisting of chloroplatinic acid, chloroplatinic acid, and an olefin, and a complex of lead and vinyl alumoxane are preferred. Further, these may be used alone or in combination of two or more types. When the above-mentioned hydroformylation catalyst is blended, the amount of addition is preferably 1 to 1 〇〇〇 ppm based on the weight of the polyfluorene ketone resin, and is preferably in the range of 20 to 500 ppm. . The hydroformyl alkyl catalyst can be used singly or in combination with the radical initiator described above, and two types of -15-201020581 or more can be used. In the present invention, when the curable resin composition containing the above polyfluorene-copper resin is obtained, the composite lens is obtained by curing the polyfluorene-containing resin, or the physical properties of the composite lens are improved. It is suitably selected: a compound having at least one ethylenically unsaturated double bond in the molecule, a compound having at least one hydroformyl group in the molecule, and a radical initiator "hydroformamidine alkylation catalyst" It is better to cooperate with it. That is, if a compound having an ethylenically unsaturated double bond or a compound having a hydroformyl group is added, it can be combined with a hydroformylation catalyst as an additive for promoting the reaction to obtain a radical. The agent (thermal polymerization initiator or photopolymerization initiator) may further contain a thermal polymerization accelerator, a photo-starting aid, a sharpener, and the like. In addition, organic/inorganic chelating agents, plasticizers, flame retardants, thermal stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents may be added as long as they do not deviate from the object of the present invention. Various additives such as a agent, a release agent, a foaming agent, a nucleating agent, a coloring agent, a crosslinking agent, a dispersing aid, and a resin component. Further, in the present invention, the resin layer may be used other than those hardened by using the above polyketone resin. In this case, it is also possible to use a compound having at least one ethylenically unsaturated double bond in the molecule to be hardened. The composite lens of the present invention can be obtained by curing the above polyfluorene ketone resin by heating or light irradiation to form a lens substrate, and forming a resin layer on the lens substrate. When the lens substrate is produced by heating, the molding temperature can be selected from a wide range of from room temperature to 200 ° C -16 to 201020581 by selection of a heat polymerization initiator or accelerator. In this case, for example, a polyketone resin (or a curable resin composition) may be cast on a metal plate or a glass plate, and hardened by heating to obtain a sheet-like lens substrate. Further, when a lens substrate is produced by light irradiation, an ultraviolet ray having a wavelength of 100 to 400 nm or a visible ray having a wavelength of 400 to 700 nm can be irradiated to obtain a molded body (lens substrate). The wavelength of the light to be used is not particularly limited, but it is suitable for near ultraviolet rays having a wavelength of 200 to 400 nm. As the light source of the ultraviolet light, for example, a low-pressure mercury lamp (output: 0_4 to 4 W/cm), a high-pressure mercury lamp (40 to 160 W/cm), an ultra-high pressure mercury lamp (1 73 to 43 5 W/cm), a metal halide lamp (80 to 1 60 W/cm), pulsed xenon lamp (80 to 120 W/cm), electrodeless discharge lamp (80 to 1 20 W/cm), and the like. These ultraviolet lamps are characterized by their respective spectral distributions and can be selected depending on the type of photopolymerization initiator to be used. Further, in the same manner as the above-described method of producing by heating, for example, a polyfluorenone resin (or a curable resin composition) ® can be cast on a glass plate, and a lens substrate having a sheet shape can be obtained by photocuring. Further, the resin layer constituting the composite lens of the present invention may be provided on the lens substrate by a resin having a curing property such as a polyfluorene ketone resin or a compound having an ethylenically unsaturated double bond. In the case of a liquid, it also contains casting, etc., and it is hardened by heat or light irradiation. Further, in order to make the lens substrate or the resin layer into a predetermined shape or thickness, a conventionally known method can be used. For example, in a mold that is processed into a predetermined shape (for example, a mold having a spherical recessed shape, etc.), a resin or a compound having a curing property as a resin layer may be quantitatively charged at -17 to 201020581. Further, in a state where the lens substrate which has been previously hardened is provided on the upper side thereof, it is hardened by heating or light irradiation to obtain a molded article of a lens shape. It is also possible to use the molded product as a late composite lens, but a resin layer of a predetermined shape may be similarly disposed on the other side of the lens substrate, and then two resins on both sides of the lens substrate may be used. The layers are joined to form a composite lens. Further, a mold having a predetermined shape may be provided on the resin layer which has been previously hardened, and a polyketone resin (or a curable resin composition) may be filled therein to form a lens substrate. @ Furthermore, when making a composite lens, if necessary, it is also possible to apply surface honing and anti-reflection based on anti-reflection, high hardness, improved wear resistance, and anti-fogging property. Physical or chemical treatments such as electrostatic treatment, hard coating treatment, non-reflective coating treatment, and dimming treatment. The composite lens of the present invention is excellent in heat resistance because at least the lens substrate is hardened by a polyketone resin containing a polyorganosilsesquioxane having a cage structure as a main component. Therefore, it can be supplied to a reflow soldering step, and is suitable for use in, for example, a mobile phone, a lens-attached CCD mounted on a digital camera, or a CMOS sensor with a lens, etc., and an integrated camera lens for a semiconductor and a lens. Group of lenses and other users. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be specifically described by way of examples. However, the invention is not limited by the scope of the examples. -18- 201020581 Embodiment Hereinafter, an embodiment of the present invention will be described. Further, the polyfluorene ketone resins used in the following examples were obtained by the methods shown in the following synthesis examples. Synthesis Example 1 In a reaction vessel having a stirrer, a dropping funnel, and a thermometer, 40 ml of 2-propanol (IPA) as a solvent and 5% aqueous solution of tetramethylammonium hydroxide (TMAH aqueous solution) as a basic catalyst were charged. ). In addition, IP A 15 ml and 3-methylpropoxypropyltrimethoxydecane (MTMS: SZ-6 300 manufactured by Toray Dow Corning Copolysinone Co., Ltd.) 12·69 g were placed in the dropping funnel. The reaction container was stirred while one side of the MTMS was dropped into it for 30 minutes. After the end of the dropping of MTMS, the mixture was stirred for 2 hours without heating. The solvent which was stirred for 2 hours was removed under reduced pressure, and dissolved in 50 ml of toluene. The reaction solution was washed with a saturated saline solution to neutrality, and then dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off to concentrate to obtain 8.6 g of a hydrolyzed product (hydrazine sesquioxane). The sesquioxanes are colorless viscous liquids which are soluble in various organic solvents. Next, in the reaction vessel having a stirrer, a "Dust Stark" polycondensation unit, and a cooling tube, 1.2 g of the obtained sesquisesquioxane 8.0 g, toluene 32 ml, and 10% TMAH aqueous solution were added, and the mixture was slowly heated. The water was distilled off and heated to 13 (TC), and the toluene was subjected to recondensation reaction at a reflux temperature. The temperature of the reaction solution at this time was 108 ° C. After the toluene was still flowed and stirred for 2 hours, the reaction was terminated. The reaction solution was washed with water to neutrality after -19-201020581, and then dehydrated with anhydrous magnesium sulfate. The anhydrous magnesium sulfate was filtered off to concentrate to obtain a polyfluorene ketone resin having the following average composition (yield 7.5 g). , yield 87%). The obtained polyfluorenone resin is a colorless viscous liquid which is soluble in various organic solvents. [CH2=CH (CH3) OCO (CH2) 3SiO, 5] m [CH2=CH (CH3) 0C0 (CH2) 3Si00.5] n ( 8 ) In Table 1, the obtained polyfluorene ketone resin (8 ) was analyzed by liquid chromatography analysis atmospheric pressure ionization analyzer (LC/APC1-MS)@ The main peak measured by the quantitative analysis, and the number of m and η of the polyfluorene ketone resin (8) corresponding thereto The measured peak portion m/z is a molecular weight of the polyfluorene ketone resin shown by the polyfluorene resin (8) (only m is 8 to 16 and η is 0 to 4). Table 1] Reward touch m η 14 5 1 8 0 18 0 9 10 0 2 18 9 12 .0 Synthesis Example 2 In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 150 ml of toluene as a solvent was charged. 2-propanol (ΙΡΑ) 85 ml and a 5 % tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) as a basic catalyst 37_2 g. Into the dropping funnel, 25 ml of toluene and trimethoxyvinyl decane were placed. 50.3 g of KBM1003) manufactured by Shin-Etsu Chemical Co., Ltd., and the reaction vessel was stirred while stirring, and a toluene solution of trimethoxyvinylnonane-20-201020581 was dropped into it for 3 hours. After the end of the dropwise drop of trimethoxyvinyl decane The mixture was stirred at room temperature for 2 hours. After stirring for 1 hour, the stirring was stopped and allowed to stand for 1 day. The reaction solution was neutralized with 1 〇% citric acid aqueous solution 2 3.0 g, and then washed with saturated brine, and It was dehydrated with anhydrous magnesium sulfate, filtered off with anhydrous magnesium sulfate, and concentrated to give 20.6 g (yield 77%) a polycondensate which is a poorly soluble white solid which is insoluble in various organic solvents. Next, it is added to a reaction vessel having a stirrer, a "Dust Stark" polycondensation unit, a cold φ tube, and a thermometer. 15.0 g of the polycondensate obtained above, 380 ml of toluene and 1.72 g of a 5% TMAH aqueous solution were distilled off at 120 ° C, and the toluene was further heated to carry out a polycondensation reaction. After the toluene was still allowed to flow and stirred for 3 hours, the room temperature was returned and the reaction was terminated. The reaction solution was neutralized with 23.0 g of 10% citric acid, and then washed with saturated brine and then dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off to concentrate to give a recondensate of 14.5 g. The resulting recondensate is a white solid and is poorly soluble in various solvents. # Finally, in the reaction vessel with a stirrer, a "Dust Stark" polycondensation unit, and a cooling tube, 14.5 g of the obtained recondensate, 300 ml of toluene, 3.0 g of a 5% TMAH aqueous solution, and 1,3 were added. -Divinyl-1,1,3,3-tetramethyldioxane (Ding\10¥0 8: LS-7250, manufactured by Shin-Etsu Chemical Co., Ltd.) 9.76 g, distilling water at 120 ° C Then, the toluene is further heated to carry out a polycondensation reaction. After the toluene was still flowed and stirred for 3 hours, the room temperature was returned and the reaction was terminated. The reaction solution was neutralized with 3.24 g of 10% citric acid, and then washed with a saturated aqueous solution of sodium chloride and then evaporated. Anhydrous magnesium sulfate was filtered off to concentrate to obtain a polyfluorene ketone resin (yield: 16.9 g, yield: 88%) having the following average composition formula -21 - 201020581. The obtained polyketone resin is a colorless viscous liquid which is soluble in various organic solvents. [CH2=CHSi015]m[CH2=CH(CH3)2Si00.5]n (9) In Table 2, the above obtained polyfluorene ketone resin was analyzed by liquid chromatography to analyze the atmospheric pressure ionization analyzer (LC/APC1- MS) The main peak measured by the mass analysis, and the number η of m and η corresponding to the polyfluorene ketone resin (9) φ. The measured peak portion m/z is a polyfluorene ketone resin (9) (only m is 8 to 16, η is 〇~4), and the molecular weight of the polyfluorene ketone resin (9) is added with ammonium ions. . [Table 2] The detected peaks m η 8 2 2. 1 9 1 8 3 6. 2 8 2 9 8 0.1 11 1 9 9 4. 1 10 2 115 2. 1 12 2 116 6. 2 11 3 1 3 2 4. 1 13 3 1 4 8 2. 1 15 3

Example 1 The cage type polyfluorene ketone resin having a methacryl fluorenyl group on a ruthenium atom obtained in the above Synthesis Example 1 : 25 parts by weight, dicyclopentyl diacrylate: 75 parts by weight, as a photopolymerization initiator Then, hydroxycyclohexyl phenyl ketone: -22-201020581 2.5 parts by weight, and mixed to obtain a transparent curable resin composition (polyfluorenone resin composition). In Table 3, the composition of the polyketone resin composition used in the present Example 1 is shown. Further, the numbers in Table 3 are expressed in parts by weight. [Table 3] ABGDE Example 1 25 75 2. 5 Example 2 50 50 2. 5 Example 3 50 10 40 2. 5 Example 4 20 50 30 2. 5 Example 5 25 65 10 2. 5 Comparative Example 1 25 60 15 2.5 Comparative Example 2 50 30 20 2.5 The symbols A to E used in Table 3 are as follows. ❹ A : Polyfluorene ketone resin B obtained in Synthesis Example 1: dimethyl methoxy propyl polydimethyl decane ("DMS-R11" manufactured by Azmak Co., Ltd.) C: dipentaerythritol Acrylate ("Excellent" acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.) D: Dicyclopentyl diacrylate (Kyoto Chemical Co., Ltd.) "Lite" acrylate vinegar DCP-A In the general formula, n = 0, R = H) E : 1 -hydroxycyclohexyl phenyl ketone (polymerization initiator) One part of the above-mentioned curable resin composition is poured into a glass plate -23- 201020581 The model 'make a thickness of 2 mm' using a high-pressure mercury lamp of 30 W/cm, and hardening it by an integrated amount of 2000 mJ/cm 2 to obtain a sheet-like polyketone resin molded body having a predetermined thickness (lens substrate i) Then, as shown in Fig. 1, the curable resin composition 2 is filled in a glass mold 3 having a processed concave portion in a predetermined spherical shape, and is composed of a curable resin which is filled with When the surface (liquid level) of the object 2 can be contacted, 30 W/c is used in a state in which the lens substrate 1 is provided. The high-pressure mercury lamp is further hardened by an integrated exposure of 1 000 mJ/cm 2 to form a resin layer having a thickness of 〇 2 mm on the lens substrate. Further, on the remaining surface of the lens substrate 1, the curable resin composition 2 is cured in the same manner to obtain a composite lens 5 having a resin layer 4 joined on both surfaces of the lens substrate 1. . The physical properties of the obtained composite lens 5 are shown in Table 4. The physical property evaluation of the composite lens 5 is as follows. 1) Total light transmittance (reference specification JISK 7361-1): Measurement was carried out using a violet visible infrared spectrophotometer (V-63 0M Japan Spectrophotometer). 2) Refractive index: Measurement was carried out using an Abbe refractometer (DR-M4, manufactured by Yada Co., Ltd.). 3) Suction ratio: After the sample was dried at 50 ° C, the weight was measured and immersed in 25 C of warm water for 24 hours. The weight after 24 hours was measured, and the water absorption rate was determined according to the following formula. Water absorption rate (%) = [(water absorption weight - dry weight) / dry weight] χ 1〇〇 201020581 4) Linear expansion coefficient: using a thermomechanical analysis device (manufactured by TMA) at a heating rate of 5 ° C / min, a compression load of 0.1 The linear expansion coefficient is measured in the range of 30 ° C to 200 ° C under the conditions of hydrazine. 5) Heat-resistant discoloration: The peak penetration temperature is set at a reflow furnace maintained at 260 °C -1 5 seconds, and the light transmittance of the sample is measured after passing through the reflow furnace twice in succession (400 nm). And the light transmittance before passing through, and the change in transmittance (%) before and after passing through was evaluated as heat discoloration resistance.

[Table 4] Total light transmittance (%) Refractive index (nd) Water absorption (%) Linear expansion (ppm/k) Heat discoloration (%) Example 1 88 1. 531 0. 5 75 0.4 Implementation Example 2 90 1. 525 0· 8 71 0· 3 Example 3 90 1. 527 1. 5 62 0.4 Example 4 87 1. 532 2. 1 54 0, 6 Example 5 88 1. 530 2. 7 37 0.6 Example 6 91 1. 458 0. 02 90 0. 1 Example 7 90 1. 518 0· 3 95 0. 2 Example 8 90 1. 516 0· 2 89 0. 2 Example 9 90 1. 517 0. 2 80 0. 2 Comparative Example 1 88 1. 508 2. 8 110 0.4 Comparative Example 2 89 1. 497 2. 2 150 0. 3 Comparative Example 3 90 1. 432 0. 02 220 0.2 Comparative Example 4 90 1 491 0. 3 ----- 180 ------- 〇. 3 (Examples 2 to 5 and Comparative Examples 1 and 2) The composition of the composition of the curable resin is as shown in Table 3. Further, -25-201020581 The rest was operated in the same manner as in Example 1 to produce a composite lens 5. Further, the physical properties of the obtained composite lens 5 were evaluated in the same manner as in Example 1. The results are shown in Table 4. (Example 6) 60 parts by weight of a vinyl group-containing resin obtained by the above Synthesis Example 2, and a terminal hydrogen-modified methylhydroquinone-phenylmethyl decane copolymer ("Azmak" 40 parts by weight of HPM-502, manufactured by Co., Ltd., and 0.5 parts by weight of lead-vinyl oxime complex ("SIP 6830.3" manufactured by Azmak Co., Ltd.), mixed until uniform, and made sclerosing Resin composition. In Table 5, the composition of the curable resin composition of the present Example 6 was used. Further, the numbers in Table 5 are expressed in parts by weight. [Table 5] FG Η ICJ Example 6 60 40 0. 5 Example 7 35 15 0. 5 50 2. 5 Example 8 40 10 0. 5 50 2. 5 Example 9 53 7 0. 5 40 2. 5 Comparative Example 3 60 40 0. 5 Comparative Example 4 40 10 0_ 5 50 2. 5

The symbols F~J used in Table 5 are as follows. F: Polyfluorene ketone resin obtained in Synthesis Example 2-26-201020581 G: Divinylpolydimethylpolyfluorene ketone ("DMS-V05" manufactured by Azmak Co., Ltd.) H: terminal hydrogen-modified methyl group Hydroquinoxane-phenylmethyl decane copolymer' (HPM-5 02, manufactured by Azmaks Co., Ltd.) 1: Platinum-vinyl oxirane complex ("Azmak" SIP6830.3) manufactured by Co., Ltd. J: Dicumyl peroxide ("Pakumur D" manufactured by Nippon Oil & Fat Co., Ltd.) The composition of the curable resin obtained above is converted into a model composed of a glass plate. The thickness is 2 mm, and then heated at 1 °C for 1 hour, 120 °C for 1 hour, 140 °C for 1 hour, 160 °C for 1 hour, and 180 °C for 2 hours to obtain a sheet of a predetermined thickness. The polyketone resin molded body (lens substrate 1). Next, as shown in FIG. 1, the curable resin composition 2 is entangled in a glass mold 3 having a processed concave portion in a predetermined spherical shape, and the curable resin composition is filled. In the case where the surface (liquid level) of 2 can be contacted, and in the state in which the lens substrate formed in advance is provided, another 1 hour, 1 hour at 120 ° C, 1 hour at 140 ° C, 1 hour, 160 °C 1 hour, 18 (TC 2 hours heating to harden, and a resin layer 4 having a thickness of 0.02 mm is formed on the lens substrate. Further, on the remaining surface of the lens substrate 1, the above-mentioned curable resin is composed The material 2 is cured in the same manner to obtain a composite lens 5 in which the resin layer 4 is bonded to both surfaces of the lens substrate 1. The physical properties of the obtained composite lens 5 are the same as in the first embodiment. Evaluation, -27-201020581 The results are shown in Table 4. (Examples 7 to 9 and Comparative Examples 3 and 4) The composition of the curable resin composition was as shown in Table 5, and the others were carried out as described above. Example 6 was operated in the same manner to produce a composite lens 5. The physical properties of the composite lens 5 are evaluated in the same manner. The results are shown in Table 4. Industrial Applicability The heat-resistant composite lens of the present invention is applied to, for example, a mobile phone or a digital camera. A CCD with a lens, a CMOS sensor with a lens, etc., and a semiconductor lens and a lens are integrated into a lens of a camera module, etc. Further, it can be used for a camera module or the like that requires heat resistance. Fig. 1 is a flow chart showing a method of manufacturing the heat-resistant composite lens of the present invention. [Explanation of main component symbols] 1: Lens base material 2: Curable resin composition 3 : Glass mold 4 : Resin layer -28- 201020581 5 : Composite lens

-29

Claims (1)

201020581 X. Patent Application Area 1. A heat-resistant composite lens characterized in that it is a composite lens in which a resin layer is bonded to a lens substrate, and the lens substrate and the resin layer are each formed of a hardened resin. , at least the lens substrate is represented by the following general formula (i), (RSi015)m(Rsi〇〇.5)n ( 1 ) Θ (only, R system (a) - R1-OCO-CR2 = CH2 &gt; (b) -R^CR^CHj or (c) -CH = an unsaturated group represented by CH2, an alkyl group, a cycloalkyl 'cycloalkenyl group, a phenyl group, a hydrogen atom, an alkoxy group, or an alkyl formane The oxy group, a plurality of R in the formula (1) may be the same or different, but at least one of the above includes (a), (b) or (c), and the R1 is an alkyl group or an alkylidene group. Or a phenyl group, R2 is hydrogen or a hospital base, m = 8~16, n = 0~4), in the structural unit is a polyorgano-sesity sesquioxane with a cage structure as the main component The ketone resin is hardened. G 2. The heat-resistant composite lens according to claim 1, wherein the resin layer is represented by the general formula (1), and in the structural unit, the polyorgano sesquioxanes having a cage structure are used. The main component of the polyketone resin is hardened. 3. The heat-resistant composite lens according to claim 1 or 2, wherein the lens substrate and/or the resin layer, for the polyfluorene ketone resin, is compounded with at least one ethyl group in the molecule. a compound having a saturated double bond and/or a compound having at least a hydroformylalkyl group in the molecule, and further comprising a sclerosing resin composition obtained by using a -30-201020581 free radical initiator and/or a hydrogenated methylation catalyst; Further, the curable resin composition is cured. -31 -