TWI459020B - A method for manufacturing a heat resistant composite lens - Google Patents

Description

Heat-resistant composite lens manufacturing method

The present invention relates to a heat-resistant composite lens characterized by a composite lens in which a resin layer is bonded to a lens substrate, for example, a lens-attached CCD (Charge Coupled) mounted on a mobile phone or a digital camera. Device) or a CMOS (complementary metal oxide film semiconductor) sensor with a lens, etc., and is suitable for a user such as a lens of a camera module in which a semiconductor and a lens are integrated.

Conventionally, a lens for a camera module uses a lens made of plastic based on the purpose of lowering the price. A plastic lens can be obtained by injection molding a transparent resin such as a polycarbonate resin, a methacrylic resin or an alicyclic olefin 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, there is a proposal to reflow soldering the camera module in the same manner as other electronic components, so that it can be mounted in one time. (260 ° C). However, the current plastic lens cannot pass the reflow furnace because its heat resistance temperature is only below 180 °C.

For example, the heat or photocurable resin which can withstand the reflow temperature is used as a post-repair material as described in JP-A-2004-133328 (Patent Document 1). However, in general, the curable resin is liable to cause molding cracking in the forming process due to hardening shrinkage generated during the reaction, and it is difficult to ensure the stability of mold reproducibility of the molded product.

In addition, as described in JP-A-2005-60657 (Patent Document 2), a composite lens in which a glass lens is used as a base material and a heat or photocurable resin is formed on the surface thereof is used. However, in the conventional composite lens described above, the adhesion between the glass and the resin is particularly likely to be lowered in the wet heat environment due to the difference in linear expansion coefficient between the glass and the resin, and the durability is not complete. Further, in the composite lens, the glass lens of the base material is more expensive to manufacture due to the long forming time and the mass production than the plastic lens, and the action is required to be suitable and mass-produced. It is not suitable for camera modules for telephones or digital cameras.

Patent Document 1: JP-A-2004-133328

Patent Document 2: JP-A-2005-60657 Gazette

In view of the above problems, an object of the present invention is to provide a heat-resistant composite lens which is suitable for use as a lens for a camera module capable of withstanding a reflow soldering step.

As a result of intensive review to solve the problem of the conventional plastic lens or composite lens, the inventors have found that at least a polyorgano-silsesquioxane having a cage structure is mainly composed. The hardened resin formed by the polyketone resin is applied to the lens substrate, and the resin layer formed of the cured resin is bonded to the lens substrate to provide an inexpensive heat supply which can be supplied to the reflow soldering step. A composite lens has been completed, thereby completing the present invention.

That is, the present invention is a heat-resistant composite lens characterized by being 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 (1),

(RSiO _1.5 ) _m (RsiO _0.5 ) _n (1)

(R), R system (a)-R ¹ -OCO-CR ² =CH ₂ , (b)-R ¹ -CR ² =CH ₂ or (c)-CH=CH ₂ unsaturated group, 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 of the above contains (a) Or (b) or (c), R ¹ is an alkyl group, an alkylidene or a phenyl group, R ² is a hydrogen or an alkyl group, m = 8 to 16, and n = 0 to 4) In the structural unit, the polyfluorene ketone resin having a polyorgano sesquioxane having a cage structure as a main component is hardened.

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 hydrazine group in the molecule and/or a compound having an ethylenically unsaturated group. Further, after the curable resin composition obtained by hydrogenating a formazan-catalyzed catalyst and/or a radical initiator is further added, the curable resin composition is thermally cured or photocured.

Hereinafter, the present invention will be specifically described.

Each of the resin base material and the resin layer in the present invention is made of a cured resin, and at least the resin base material 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 general formula (1), that is, a cage structure in a structural unit (hereinafter, also referred to as "cage" The structure of polyorganophosphoric acid sesquioxane" is the main component. Here, the structural unit specifically refers to a repeating unit represented by m or n in the general formula (1), and the so-called cage type construct in the structural unit means one of the repeating units indicated by m or n. The two or both have the meaning of a cage structure. Further, the polyorganopurine sesquioxane having a cage structure is composed of a ternary polyhedral structural skeleton and R as described below, but one of the three-dimensional polyhedral structural skeletons is an open loop (also That is, the incomplete cage structure is also included.

Here, in the general formula (1), it is necessary that at least one of R is an unsaturated group represented by the above (a), (b) or (c), and specific examples of such unsaturated groups are 3-methacryloxypropyl, 3-propenyloxypropyl, aryl, vinyl, and styryl groups. In the polyfluorene ketone resin of the present invention, in addition to the polyorganosilsesquioxane having a cage structure, a polyfluorene ketone resin having the following structure or no cage structure is included, and the ratio is less than 30% by weight. Preferably.

(In the above formula, at least one of R is a base represented by the general formula (1), and y is a repeat number of 1 to 1000)

The general formula (1) is a cage-type polyoxane composed of a ternary polyhedral structure skeleton and R, and each of them is an example. When m in the general formula (1) is 8 and n is 0, it is The following structural formula (3); when m is 10 and n is 0, it is the following structural formula (4); when m is 12 and n is 0, it is the following structural formula (5); When m is 8 and n 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).

The cage polyoxyalkylene 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).

RSiX ₃ (7)

(R), R system (a)-R ¹ -OCO-CR ² =CH ₂ , (b)-R ¹ -CR ² =CH ₂ or (c)-CH=CH ₂ unsaturated group, alkyl group , cycloalkyl, cycloalkenyl, phenyl, hydrogen, alkoxy, or alkylcarboxykoxy, R ¹ is alkyl, alkyl or phenyl, R ² is hydrogen or alkyl, X is a hydrolyzable group selected from the group consisting of an alkoxy group, a halogen atom, and a hydroxyl group, and is used as a one or both of a nonpolar solvent and a polar solvent under an alkaline catalyst. The solvent is hydrolyzed while being condensed in one part.

Further, in the case of the cage type polyoxane represented by the above structural formula (6), the cage type polyoxane represented by the structural formula (3), (4), or (5) can be further 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.

Examples of the polar solvent in the case of obtaining the cage-type siloxane of the structural formulae (3) to (6) include alcohols such as methanol, ethanol, and 2-propanol. 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, as the polyfluorenone resin, any one of a compound having at least one ethylenically unsaturated double bond in the molecule or a compound having at least a hydrogenated methyl group in the molecule may be blended. Further, a curable resin composition is prepared; and these two may be blended to form a curable resin composition. Next, 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 compound of a germyl group, 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, 1.5 or more is better, and 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 such as epoxy acrylate, epoxidized acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl acrylic Ester, polyene/thiol, polyketone 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 , n-hexyl acrylate, cyclohexyl acrylate, n-mercapto acrylate, isobornyl acrylate, dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methyl Acrylate and the like. Further, a reactive polyfunctional monomer such as tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, bisphenol A diepoxypropyl ether, which is an unsaturated compound other than the general formula (2) 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 can be used, 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. The polyfluorenone resin copolymer can also be obtained in the same manner by radical copolymerization of these.

The radical initiator which is used in combination with a compound having at least one ethylenically unsaturated double bond in the molecule may be used as a photopolymerization initiator or a thermal polymerization initiator. Here, the photopolymerization initiator is suitable for a compound such as an acetophenone-based, a benzoin-based, a benzophenone-based, a thioxanthone-based or a mercaptophosphine-based oxide. Specifically, for example, trichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxy-cyclohexyl phenyl ketone, 2- Methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, benzoin methyl ether, thioxanthone, 2,4,6-trimethylbenzhydryl Phenylphosphine oxide, methylphenylglyoxylate, camphorquinone, benzoin, anthracene, rice ketone, and the like. Further, it is also possible to use a photopolymerization initiator in combination with a photoinitiator or a sensitizer 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 , diisopropyl 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 kinds.

The radical initiator, when a photopolymerization initiator or a thermal polymerization initiator is blended, is preferably added in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polyfluorenone resin, and is 0.1 to 0.1% by weight. 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, when it exceeds 5 parts by weight, problems such as coloring of the lens may occur.

On the other hand, as the compound having at least a hydrogenated methylation group in the above molecule, it is preferably an oligomer and a monomer, and the oligomer and the monomer are characterized by having at least a ruthenium atom in the molecule. More than one hydrogen atom which can be hydrogenated to formylated. 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 may also be used in combination of two or more types.

a hydroformamidine catalyst used in combination with a compound having at least a hydroformyloxy group in the molecule, for example, a chloroplatinum (IV), a chloroplatinic acid, a chloroplatinic acid, and a complex of an alcohol, an aldehyde, a ketone, A complex of chloroplatinic acid and an olefin, a complex of platinum and a vinyl siloxane, a platinum group metal catalyst such as dicarbonyl chloroplatinum, a palladium catalyst or 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 platinum and vinyl decane are preferred. Further, these may be used alone or in combination of two or more types.

When the hydroformylation catalyst is blended, the amount thereof is preferably from 1 to 1,000 ppm, more preferably from 20 to 500 ppm, based on the weight of the polyfluorene ketone resin. The hydroformylalkyl catalyst may be used singly or in combination with the radical initiator described above, and two or more types may be used in combination.

In the present invention, when the curable resin composition containing the above polyfluorene copper resin is obtained, the purpose of obtaining a composite lens by curing the polyfluorene-containing resin or improving the physical properties of the composite lens is 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, a radical initiator, a hydroformylation catalyst, and the like. It is better to cooperate. That is, if a compound having an ethylenically unsaturated double bond or a compound having a hydroformyl group is blended, a hydroformylation catalyst as a promoter for promoting the reaction can be used as a radical initiator ( A thermal polymerization initiator or a photopolymerization initiator) may further contain a thermal polymerization accelerator, a photo-starting aid, a sharpening agent, and the like. In addition, organic/inorganic fillers, plasticizers, flame retardants, thermal stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, slip agents, antistatic agents may be added as long as they do not deviate from the object of the present invention. Various additives such as 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 from room temperature to 200 ° C by selection of a thermal polymerization initiator or an accelerator. At this time, for example, a polyfluorene ketone resin (or a curable resin composition) may be cast on a metal plate or a glass plate, and cured by heat to obtain a flaky 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 a near-ultraviolet light 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 water lamp (40 to 160 W/cm), an ultra-high pressure mercury lamp (173 to 435 W/cm), and a metal halide lamp (80~) 160W/cm), pulsed xenon lamp (80~120W/cm), electrodeless discharge lamp (80~120W/cm), etc. 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 polyfluorene ketone resin (or a curable resin composition) may be cast on a glass plate, and photo-cured to obtain a flaky lens substrate.

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 hardening property as a resin layer may be filled in a quantitative manner and on the upper side thereof. In the state in which the lens substrate which has been previously hardened is provided, it is hardened by heating or light irradiation to obtain a molded article of a lens shape. A composite lens can also be formed by the molded article, but a resin layer of a predetermined shape can be similarly disposed on the remaining surface of the lens substrate, and then two resin layers on both sides of the lens substrate can be applied. Join to make 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.

Further, when a composite lens is produced, if necessary, surface grinding and antistatic treatment may be applied for the purpose of improving antireflection, imparting high hardness, improving wear resistance, and imparting antifogging properties. Conventional physical or chemical treatments such as hard coating treatment, non-reflective coating treatment, and dimming treatment.

In the composite lens of the present invention, at least the lens substrate is cured by a polyketone resin having a polyorgano sesquioxane having a cage structure as a main component, and the heat resistance is excellent. 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 a semiconductor camera and a lens integrated camera module. Users such as lenses.

The best form of implementing the invention

The invention is further illustrated by the following examples. However, the invention is not limited by the scope of the examples.

Example

Hereinafter, embodiments of the 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

Into a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 40 ml of 2-propanol (IPA) as a solvent and a 5% aqueous solution of tetramethylammonium hydroxide (aqueous solution of TMAH) as a basic catalyst were charged. In addition, 12.69 g of IPA 15 ml and 3-methylpropoxypropyltrimethoxydecane (MTMS: SZ-6300, manufactured by Toray Dow Corning Co., Ltd.) were placed in a dropping funnel, and the reaction vessel was stirred on one side. The IPMS of MTMS was dropped into it for 30 minutes. After the end of the dropping of MTMS, the mixture was stirred without heating for 2 hours. 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 water to a neutral state with saturated brine, and then dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to give 8.6 g of a hydrolyzed product. The sesquioxanes are colorless viscous liquids which are soluble in various organic solvents.

Next, in a reaction vessel equipped with a stirrer, a "Dust Stark" polycondensation unit, and a cooling tube, 8.0 g of the above-obtained sesquioxanes, 32 ml of toluene, and 1.2 g of a 10% TMAH aqueous solution were added, and the mixture was heated slowly. The water was distilled and heated again to 130 ° C, and toluene was subjected to recondensation 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. Further, the reaction solution was washed with a saturated saline solution until it was neutralized, and then dehydrated with anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off to concentrate to obtain a polyfluorene ketone resin (yield: 7.5 g, yield: 87%) having the following average composition. The obtained polyfluorenone resin is a colorless viscous liquid which is soluble in various organic solvents.

[CH ₂ =CH(CH ₃ )OCO(CH ₂ ) ₃ SiO _1.5 ] _m [CH ₂ =CH(CH ₃ )OCO(CH ₂ ) ₃ SiO _0.5 ] _n (8)

In Table 1, the main peaks obtained by mass analysis of the obtained polyfluorene ketone resin (8) by liquid chromatography analysis atmospheric pressure ionization analyzer (LC/APC1-MS), and the equivalent The values of m and n of the polyketone resin (8). The measured peak portion m/z is a value of ammonium ion added to the molecular weight of the polyfluorene ketone resin represented by the polyfluorene ketone resin (8) (m is 8 to 16, n is 0 to 4).

Synthesis Example 2

In a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 150 ml of toluene as a solvent, 85 ml of 2-propanol (IPA), and 5% aqueous solution of tetramethylammonium hydroxide (aqueous solution of TMAH) as a basic catalyst were charged 37.2. g. In addition, 25 ml of toluene and 50.3 g of trimethoxyvinyl decane (KBM1003 manufactured by Shin-Etsu Chemical Co., Ltd.) were placed in a dropping funnel, and the toluene solution of trimethoxyvinyl decane was dropped over 3 hours while stirring the reaction vessel. among them. After completion of the dropwise addition of trimethoxyvinyl decane, it 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 23.0 g of a 10% aqueous citric acid solution, and then washed with saturated brine and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to give 20.6 g (yield: 77%) of a poly condensate. The polycondensate is a poorly soluble white solid which is insoluble in various organic solvents.

Next, 15.0 g of the polycondensate obtained above, 380 ml of toluene, and 1.72 g of a 5% TMAH aqueous solution were placed in a reaction vessel equipped with a stirrer, a "Dust Stark" polycondensation unit, a cooling tube, and a thermometer at 120 ° C. The water was distilled off, and the toluene was further heated to carry out a polycondensation reaction. After the toluene was still flowed and stirred for 3 hours, 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 and concentrated to give 14.5 g of a recondensate. The resulting recondensate is a white solid and is poorly soluble for various solvents.

Finally, 14.5 g of the obtained recondensate, 300 ml of toluene, 3.0 g of a 5% TMAH aqueous solution, and 1,3-two were placed in a reaction vessel equipped with a stirrer, a "Dust Stark" polycondensation unit, and a cooling tube. 9.76 g of vinyl-1,1,3,3-tetramethyldioxane (TMDVDS: LS-7250, manufactured by Shin-Etsu Chemical Co., Ltd.), water was distilled off at 120 ° C, and toluene was further heated to carry out heat treatment. Polycondensation reaction. After the toluene was still flowed and stirred for 3 hours, 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 saturated brine and then dried over anhydrous magnesium sulfate. 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. The obtained polyfluorene ketone resin is a colorless viscous liquid which is soluble in various organic solvents.

[CH ₂ =CHSiO _1.5 ] _m [CH ₂ =CH(CH ₃ ) ₂ SiO _0.5 ] _n (9)

In Table 2, the main peaks measured by the mass analysis of the polyfluorenone resin obtained above by a liquid chromatography analysis atmospheric pressure ionization analyzer (LC/APC1-MS), and the aggregation corresponding thereto are collected. The value of m and n of the ketone resin (9). The measured peak portion m/z is the value of the ammonium ion added to the molecular weight of the polyfluorene ketone resin (9) represented by the polyfluorene ketone resin (9) (only m is 8 to 16, n is 0 to 4). .

Example 1

The cage type polyfluorene ketone resin having a methacryl fluorenyl group on the ruthenium atom obtained in the above Synthesis Example 1 : 25 parts by weight, dicyclopentyl diacrylate: 75 parts by weight, as a photopolymerization initiator 1- Hydroxycyclohexyl phenyl ketone: 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 numerical values in Table 3 are expressed in parts by weight.

The symbols A to E used in Table 3 are as follows.

A: Polyacrylone resin obtained in Synthesis Example 1

B: dimethyl methoxy propyl polydimethyl decane ("DMS-R11" manufactured by Azmaks Co., Ltd.)

C: dipentaerythritol hexaacrylate ("Excellent" acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.)

D: Dicyclopentyl diacrylate (Kelly acrylate DCP-A manufactured by Kyoeisha Chemical Co., Ltd.: in the general formula, n = 0, R = H)

E: 1-hydroxycyclohexyl phenyl ketone (polymerization initiator)

One part of the above-mentioned curable resin composition was poured into a model composed of a glass plate to have a thickness of 2 mm, and a high-pressure mercury lamp of 30 W/cm was used, and the exposure amount was 2000 mJ/cm ² to harden it to obtain a predetermined thickness. A flaky polyketone resin molded body (lens substrate 1).

Next, 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 formed on the surface of the filled curable resin composition 2. When the liquid level is in contact with each other, a 30 W/cm high-pressure mercury lamp is used in a state where the lens substrate 1 is provided, and an exposure amount of 1000 mJ/cm ² is used to harden it, and a thickness of 0.02 is formed on the lens substrate. Mm resin layer.

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 property values 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 JIS K 7361-1): Measurement was carried out using an ultraviolet-visible infrared spectrophotometer (V-630M manufactured by JASCO Corporation).

2) Refractive index: Measurement was carried out using an Abbe refractometer (DR-M4 manufactured by Yada Co., Ltd.).

3) Water absorption rate: After the sample was dried at 50 ° C, the weight was measured, and further immersed in warm water of 25 ° C 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] × 100

4) Linear expansion coefficient: The linear expansion coefficient was measured in the range of 30 ° C to 200 ° C using a thermomechanical analyzer (manufactured by TMA) at a temperature increase rate of 5 ° C / min and a compression load of 0.1 N.

5) Heat-resistant discoloration: After the peak temperature was set at a reflow furnace maintained at 260 ° C for 15 seconds, the sample was passed through the reflow furnace twice, and the light transmittance (400 nm) of the sample was measured and passed. The light transmittance was evaluated by the change in transmittance (%) before and after the heat resistance.

(Examples 2 to 5 and Comparative Examples 1 and 2)

The composite lens 5 was obtained in the same manner as in Example 1 except that the composition of the curable resin composition was as shown in Table 3. 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 in the above Synthesis Example 2, and a terminal hydrogen-modified methylhydroquinone-phenylmethyl decane copolymer ("HPZ manufactured by Azmak" Co., Ltd. - 502) 0.5 parts by weight of a platinum-vinyl oxime complex ("SIP 3030.3" manufactured by Azmak Co., Ltd.) was mixed and homogenized to form a curable resin composition. In Table 5, the composition of the curable resin composition of the present Example 6 was used. Further, the numerical values in Table 5 are expressed in parts by weight.

The symbols F~J used in Table 5 are as follows.

F: Polyfluorene ketone resin obtained in Synthesis Example 2

G: Divinylpolydimethylpolyfluorene ("Daz-V05" manufactured by Azmaks Co., Ltd.)

H: terminal hydrogen-modified methylhydroquinone-phenyl methoxy alkane copolymer-("Azmax" Co., Ltd. HPM-502)

I: Platinum-vinyl oxirane complex ("SIPZ 0.30.3 by Azmak" Co., Ltd.)

J: dicumyl peroxide ("Pakumur D" manufactured by Nippon Oil & Fat Co., Ltd.)

The curable resin composition obtained above was introduced into a model of a glass plate to have a thickness of 2 mm, and further at 100 ° 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. The film was heated to obtain a sheet-like polyketone resin molded body (lens substrate 1) having a predetermined thickness.

Next, 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 formed on the surface of the filled curable resin composition 2. (liquid level) can be contacted, and in a state in which a lens substrate formed in advance is provided, another one at 100 ° 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. The resin layer 4 having a thickness of 0.02 mm was formed on the lens substrate by heating to harden it.

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 were evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Examples 7 to 9 and Comparative Examples 3 and 4)

The composite lens 5 was produced in the same manner as in the above-described Example 6, except that the composition of the curable resin composition was as shown in Table 5. Moreover, the physical property values of the obtained composite lens 5 were similarly evaluated. The results are shown in Table 4.

Industrial availability

The heat-resistant composite lens of the present invention is applied to, for example, a lens-equipped CCD, a lens-equipped CMOS sensor, or the like, which is mounted on a mobile phone or a digital camera, and a semiconductor camera and a lens integrated camera module. A user such as a lens. In addition, it can also be used for a lens or the like of a camera module for a vehicle that requires heat resistance.

1. . . Lens substrate

2. . . Curable resin composition

3. . . Glass mold

4. . . Resin layer

5‧‧‧Composite lens

Fig. 1 is a flow chart showing a method of producing a heat resistant composite lens of the present invention.

Claims (3)

A method for producing a heat-resistant composite lens, which is a method for producing a composite lens in which a resin layer is bonded to a lens substrate, wherein the lens substrate and the resin layer are each formed of a hardened resin, at least a lens The substrate is represented by the following general formula (1), (RSiO _1.5 ) _m (RsiO _0.5 ) _n (1) (except that R is (a)-R ¹ -OCO-CR ² =CH ₂ , (b)- R ¹ -CR ² =CH ₂ or (c)-CH=CH ₂ unsaturated group, alkyl group, cycloalkyl group, cycloalkenyl group, phenyl group, hydrogen atom, alkoxy group or 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 R ¹ is an alkyl group or an alkyl group. Fork or phenyl, R ² is hydrogen or alkyl, m = 8 to 16, n = 1 to 4), in the structural unit is a polyorgano sesquioxane with a cage structure as the main component The polyketone resin is a hardened resin composition containing a compound having at least a hydrogenated methyl hydrazine group in the molecule and a hydroformylation catalyst, and is filled into a resin in a specific amount in a mold having a concave shape. a layer of a hardening resin composition, and Its upper side is provided with a previously curable resin composition forming state of the lens substrate of a sheet, heating or light irradiation to the resin layer is hardened, whereby the lens to the substrate and the resin layer are integrated. The method for producing a heat-resistant composite lens according to the first aspect of the invention, wherein the lens substrate and the resin layer are integrated on both the inner and outer sides of the lens substrate. The method for producing a heat-resistant composite lens according to the first aspect of the invention, wherein the resin layer is represented by the general formula (1), and is a polyorgano-indene which has a cage structure in a structural unit. A curable resin composition of a polyfluorene ketone resin containing a semi-oxygen as a main component is cured.