JP5336399B2 - Heat-resistant compound lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat-resistant compound lens which is durable against a solder reflow process and applied as a lens for camera module. <P>SOLUTION: The heat-resistant compound lens is obtained by joining a resin layer to a lens base material, wherein at least the resin layer is formed by curing a silicone resin represented by formula: [[(R<SP>1</SP>SiO<SB>3/2</SB>)<SB>n</SB>](R<SP>2</SP><SB>2</SB>SiO<SB>2/2</SB>)]<SB>m</SB>[[XO<SB>2/2</SB>](R<SP>2</SP><SB>2</SB>SiO<SB>2/2</SB>)]<SB>l</SB>, having a weight-average molecular weight Mw of 5,000 to 1,000,000, and containing two or more groups of at least one kind of reactive functional group selected from the group comprising vinyl group, allyl group and (meth)acryloyl group having an unsaturated double bond. In the formula, R<SP>1</SP>and R<SP>2</SP>are each vinyl group, allyl group, alkyl group, aryl group, (meth)acryloyl group or a group having an oxirane ring; X is a 5-50C aliphatic structure, alicyclic structure, aromatic structure or a structure having one or more -OCOO-bonds; n, m and l are each represent an average value, and n is a number of 6-14, m and l are each 1 or more, and m+l is 2 to 2,000. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a compound lens in which a resin layer is bonded to a lens substrate, for example, a CCD with a lens (Charge Coupled Device) or a CMOS with a lens (complementary metal oxide film) mounted on a mobile phone, a digital camera or the like. The present invention relates to a heat-resistant compound lens that is preferably used as a lens of a camera module in which a semiconductor and a lens are integrated, such as a semiconductor sensor.

  Conventionally, as a lens for a camera module, a plastic lens has been used for the purpose of reducing the price. A plastic lens has a convex lens and a concave lens obtained by injection molding a transparent resin such as a polycarbonate resin, a methacrylic resin, and an alicyclic olefin polymer.

  In recent years, for the purpose of reducing the mounting cost of electronic components, a method of batch mounting a camera module by solder reflow like other electronic components has been proposed, and it is necessary to withstand the heat (260 ° C.) of a reflow furnace. However, since the current plastic lens has a heat resistant temperature of 180 ° C. or lower, it cannot be passed through a reflow furnace.

  As means for solving this problem, for example, as described in Japanese Patent Application Laid-Open No. 2004-133328 (Patent Document 1), a heat or photo-curable resin that can withstand the reflow temperature is considered as a candidate material. However, in general, the curable resin tends to cause molding cracks in the molding process due to curing shrinkage that occurs during the reaction, and in addition, there is a problem that it is difficult to stably secure the mold transferability of the molded product.

  For example, as described in JP-A-2005-60657 (Patent Document 2), it is conceivable to apply 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. The compound lens does not require a molding machine, and since the amount of resin used is small, the effect of curing shrinkage on the optical characteristics is small.

  However, in the conventional composite lens as described above, due to the difference in linear expansion coefficient between glass and resin, the adhesion at the glass-resin interface is likely to be lowered, particularly in a humid heat environment, and the durability is high. Inadequate from the aspect.

Japanese Patent Laid-Open No. 2004-133328 JP2005-60657

  Accordingly, the present invention has been made to solve the above-described problems, and an object thereof is to provide a heat-resistant composite lens that can be applied as a lens for a camera module, for example, capable of withstanding a solder reflow process. To do.

  As a result of intensive investigations to solve the problems of conventional plastic lenses and compound lenses, the present inventors have found that a cured resin comprising a silicone resin mainly composed of polyorganosilsesquioxane having a cage structure. It was found that a heat-resistant composite lens that can be used in a solder reflow process can be obtained by applying the resin layer to at least a resin layer and then bonding the resin layer to a lens base material, thereby completing the present invention. .

That is, the present invention is a composite lens in which a resin layer is bonded to a lens substrate, wherein the lens substrate and the resin layer are each made of a cured resin, and at least the resin layer is represented by the following general formula (1).
[[(R ¹ SiO _3/2 ) _n ] (R ² ₂ SiO _2/2 )] _m [[XO _2/2 ] (R ² ₂ SiO _2/2 )] _l (1)
(However, R ¹ and R ² are vinyl groups, allyl groups, alkyl groups, aryl groups, (meth) acryloyl groups, or groups having an oxirane ring, and may be the same or different from each other, The structure includes one or more of an aliphatic structure having 5 to 50 carbon atoms, an alicyclic structure, an aromatic structure, and an —OCOO— bond, and n, m, and l each represent an average value, and n is 6 to 14 M and l are 1 or more, and m + 1 is 2 to 2,000). The weight average molecular weight is Mw = 5,000 to 1,000,000 and unsaturated Curing a silicone resin having at least two reactive functional groups in one molecule selected from the group consisting of a vinyl group having a double bond, an allyl group, and a (meth) acryloyl group; Heat-resistant composite type It is a diagram.

  Moreover, the preferable aspect in this invention is a heat resistant compound type lens in which the said lens base material hardens the silicone resin represented by General formula (1) further.

  In the present invention, a compound having at least one ethylenically unsaturated group and / or a compound having a hydrosilyl group in the molecule is blended with the silicone resin, and a radical initiator and / or a hydrosilylation catalyst is blended. Then, after obtaining a curable resin composition, the curable resin composition may be thermally cured or photocured to obtain a cured resin.

Hereinafter, the present invention will be specifically described.
The lens substrate and the resin layer in the present invention are each made of a cured resin, and at least the resin layer is made of a cured silicone resin as will be described in detail below. That is, the silicone resin used in the present invention is a polyorganosilsesquioxane represented by the above general formula (1) and having a cage structure in the structural unit (hereinafter referred to as “cocoon-type polyorganosilsesquioxane”). (Also called) as the main component. Here, the structural unit specifically means a repeating unit represented by m in the general formula (1), and having a cage structure in the structural unit means that m and n are 1 or more. means. The polyorganosilsesquioxane having a cage structure is composed of a three-dimensional polyhedral structure skeleton and R ¹ and R ² , as described below. Among these, a part of the three-dimensional polyhedral structure skeleton is formed. It shall also include those that have opened (ie, incomplete cage structures).

Here, R ¹ and R ² in the general formula (1) are groups having a vinyl group, an allyl group, an alkyl group, an aryl group, a (meth) acryloyl group or an oxirane ring, and are the same or different from each other. There may be, but it is necessary that at least one of R ¹ or R ² is an unsaturated group. Specific examples of these unsaturated groups include (meth) acryloyl groups such as 3-methacryloxypropyl group and 3-acryloxypropyl group, as well as aryl groups, vinyl groups, allyl groups, and styryl groups. And those having an unsaturated double bond.

  In the present invention, at least the silicone resin forming the resin layer is mainly composed of polyorganosilsesquioxane having a cage structure. However, if the amount is small, a secondary resin is produced in the production of the silicone resin of the general formula (1). The resulting polyorganosilsesquioxane containing no cocoon structure may be included. However, the ratio is desirably less than 30 wt% in the silicone resin forming the resin layer.

In the present invention, the following formula (1)
[[(R ¹ SiO _3/2 ) _n ] (R ² ₂ SiO _2/2 )] _m [[XO _2/2 ] (R ² ₂ SiO _2/2 )] _l (1)
(However, R ¹ and R ² are vinyl groups, allyl groups, alkyl groups, aryl groups, (meth) acryloyl groups, or groups having an oxirane ring, and may be the same or different from each other, The structure includes one or more of an aliphatic structure having 5 to 50 carbon atoms, an alicyclic structure, an aromatic structure, and an —OCOO— bond, and n, m, and l each represent an average value, and n is 6 to 14 M and l are 1 or more, and m + 1 is 2 to 2,000.), And the weight average molecular weight Mw is 5,000 to 1,000,000. And an organic-inorganic composite having at least one reactive functional group selected from the group consisting of a vinyl group having an unsaturated double bond, an allyl group, and a (meth) acryloyl group. As used in the resin layer that forms the compound lens Preferably, it is used for both the resin layer and the lens substrate.

（但し、Ｒ²は水素原子、ビニル基、アリル基、アルキル基、アリール基、（メタ）アクリロイル基又はオキシラン環を有する基であって互いに同じか異なるものであってもよい。）で表されるジクロロシランをシラノール基含有籠型シロキサン及び有機ジオールの合計モルに対して０．５〜５倍モル、好ましくは０．５〜３．０倍モルの範囲で添加して脱塩酸縮合させて、式（１）で表される有機−無機複合体とすることができる。なお、一般式（２）又は（４）におけるＲ¹とＲ²のいずれかに不飽和基が含まれ、式（１）で表される有機−無機複合体1分子中にすくなくとも不飽和基を２以上含むようにしておく必要がある。 As a preferable method for obtaining the organic-inorganic composite represented by the above formula (1), the following formula (2):
(R ¹ SiO _3/2 ) _n (HO _2/2 ) _k (2)
(However, R ¹ may be a vinyl group, an allyl group, an alkyl group, an aryl group, a (meth) acryloyl group or a group having an oxirane ring, and may be the same or different from each other, and n and k are average values. And n represents a number of 6 to 14, and k represents a number of 1 to 4.) and a silanol group-containing cage-type siloxane represented by the following formula (3):
HO-X-OH (3)
(Wherein X is an aliphatic structure having 5 to 50 carbon atoms, an alicyclic structure, an aromatic structure and a structure containing one or more of —OCOO— bonds), and an organic diol compound represented by Following formula (4)

(However, R ² is a hydrogen atom, a vinyl group, an allyl group, an alkyl group, an aryl group, a (meth) acryloyl group, or a group having an oxirane ring and may be the same or different from each other). Dichlorosilane is added in a range of 0.5 to 5 times mol, preferably 0.5 to 3.0 times mol to the total mol of silanol group-containing cage-type siloxane and organic diol, and dehydrochlorinated, It can be set as the organic-inorganic composite represented by Formula (1). In addition, an unsaturated group is included in either R ¹ or R ² in the general formula (2) or (4), and at least an unsaturated group is contained in one molecule of the organic-inorganic complex represented by the formula (1). It is necessary to include two or more.

  Regarding specific reaction conditions for copolymerizing silanol group-containing cage-type siloxane of formula (2) and organic diol compound of formula (3) by dehydrochlorination using dichlorosilane of formula (4), Should be carried out under basic conditions. For example, a solution obtained by dissolving a silanol group-containing cage-type siloxane and an organic diol compound as a solvent and base in a mixed solution of pyridine or tetrahydrofuran and triethylamine, and dissolving dichlorosilane in pyridine at room temperature under an inert gas atmosphere such as nitrogen It is good to carry out stirring at room temperature for 2 hours or more after that. At this time, if the reaction time is short, the reaction is not completed. After completion of the reaction, toluene and water are added, and the organic-inorganic complex represented by the formula (1) is dissolved in toluene, and by-product hydrochloric acid and hydrochloride are dissolved and removed in the aqueous layer. Further, the organic layer is dried using a desiccant such as magnesium sulfate, and the used base and solvent are removed by concentration under reduced pressure.

Following formula (2)
(R ¹ SiO _3/2 ) _n (HO _2/2 ) _k (2)
(However, R ¹ may be a vinyl group, an allyl group, an alkyl group, an aryl group, a (meth) acryloyl group or a group having an oxirane ring, and may be the same or different from each other, and n and k are average values. Yes, n represents a number of 6 to 14, and k represents a number of 1 to 4. For a preferable means for obtaining a silanol group-containing cage-type siloxane represented by the following formula (5):
R ¹ SiY ₃ (5)
(Wherein R ¹ is a vinyl group, an allyl group, an alkyl group, an aryl group, a (meth) acryloyl group or a group having an oxirane ring, and Y is selected from the group consisting of an alkoxy group, a halogen atom and a hydroxyl group. ¹ or 2 is used, and the basic catalyst is R ¹ SiY ₃ : basic catalyst = 3 to 7 mol: 1 mol of basic catalyst is present. In the process of hydrolysis (condensation of silanol groups) and cleavage (equilibrium), hydrolysis is performed in a polar solvent or nonpolar solvent or a mixed solvent thereof and the hydrolyzate is subjected to a condensation reaction. After the counter cation derived from the sex catalyst is bonded to the cleavage portion, it can be obtained by treating with an acid and converting the cleavage portion to a hydroxyl group. At this time, if the basic catalyst used is less than the above range, the condensation of the silanol group is prioritized and the silanol group is reduced. On the other hand, when the amount is larger than the above range, cleavage of the siloxane bond is given priority, and excess silanol groups are increased. From these facts, when the amount of the basic catalyst is out of the above range, the condensation reaction using the dehydrochlorination reaction of dichlorosilane with the organic compound in the next step causes insufficient reaction or gelation.

  The solvent used for obtaining the silanol group-containing cage-type siloxane represented by the above formula (2) is a solvent obtained by combining one or both of a nonpolar solvent and a polar solvent. Among these, examples of the nonpolar solvent include hydrocarbon solvents such as hexane, toluene, xylene, and benzene. Examples of the polar solvent include ether solvents such as diethyl ether and tetrahydrofuran, ester solvents such as ethyl acetate, alcohol solvents such as methanol, ethanol and 2-propanol, and ketone solvents such as acetone and methyl ethyl ketone. Among these, a two-phase system of 2-propanol and toluene is preferable from the viewpoint of reaction rate control. The volume ratio of 2-propanol / toluene is preferably 1/2. The preferred amount of these organic solvents used is such that the molar concentration (mol / liter: M) relative to the silicon compound of formula (5) is in the range of 0.01 to 10M, more preferably 0.01 to 1M. There should be.

About the reaction conditions at the time of synthesize | combining the silanol group containing cage-type siloxane of said Formula (2), 0-60 degreeC is preferable and 20-40 degreeC is more preferable. When the reaction temperature is lower than 0 ° C., the reaction rate becomes slow, resulting in a large amount of unreacted hydrolyzable groups and silanol groups remaining. On the other hand, when the temperature is higher than 60 ° C., the reaction rate is too high, so that a complicated condensation reaction proceeds, and as a result, high molecular weight is promoted. Although the reaction time varies depending on R ¹ a structure represented by the above formula (5), typically a few minutes to several hours, preferably good is 1-3 hours.

Specific examples of the silanol group-containing cage-type siloxane compound represented by the formula (2) are shown in the following structural formulas (6) to (12), respectively. Structural formula (6) is n = 6, k = 2, (7) is n = 7, k = 3, (8) -1 and (8) -2 are n = 8, k = 2, (9) is n = 9, k = 1, (10) is n = 10, k = 2, (11) is n = 12, k = 2, (12) is n = 14, k = 2. However, the structural unit represented by the formula (2) is not limited to those shown in the structural formulas (6) to (12). In Structural Formulas (6) to (12), R ¹ is the same as Formula (5).

  Examples of the silicon compound represented by the above formula (5) include phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, and n-propyltrimethoxysilane. Ethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, methacryloxymethyltrimethoxy Silane, methacryloxymethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyl Reethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexylethyl) trimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, Examples include p-styryltrimethoxysilane, p-styryltriethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. Of these, phenyltrimethoxysilane, methyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane and vinyltrimethoxysilane, which are easily available, are preferred.

  Examples of the basic catalyst used in the hydrolysis and condensation reaction of the above formula (5) include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide. And ammonium hydroxide salts such as tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide. Among these, tetramethylammonium hydroxide is preferably used because of its high catalytic activity.

  After completion of the reaction for obtaining the silanol group-containing cage-type siloxane represented by the above formula (2), the reaction solution is neutralized with a weakly acidic solution. After neutralization or acidification, water or water-containing reaction solvent is separated. Thereafter, the organic layer is sufficiently washed with water or saturated saline. Then, it dries with drying agents, such as anhydrous magnesium sulfate. After removing the desiccant by filtration, the reaction product (silanol group-containing cage siloxane) can be recovered by concentration under reduced pressure. Concentration under reduced pressure is performed at 40 ° C or lower. If the temperature exceeds 40 ° C., the silanol groups produced by the reaction are condensed, resulting in a problem that the high molecular weight and gelation and the subsequent reaction do not proceed. Examples of the weakly acidic solution include sulfuric acid diluted solution, hydrochloric acid diluted solution, citric acid diluted solution, acetic acid, ammonium chloride aqueous solution, malic acid solution, oxalic acid solution and the like.

  Next, the siloxane siloxane and the organic component are obtained by copolymerizing the silanol group-containing cage siloxane obtained above and the organic diol compound of the formula (3) using dichlorosilane of the formula (4). An organic-inorganic composite consisting of

（但し、上記式（２０）のＲ³は炭素数５〜１０の脂肪族炭化水素及び／又は脂環式炭化水素であり、Ｍｗ＝５００〜２,０００である。）等を例示することができるが、これらに何ら制限されるものではない。またこれらを単独で使用してもよく、２種以上併用してもよい。 Here, as the organic diol compound represented by the formula (3), pentanediol, hexanediol, 1,9-nonanediol, the following formulas (13) to (20),

(However, R ³ in the above formula (20) is an aliphatic hydrocarbon and / or alicyclic hydrocarbon having 5 to 10 carbon atoms, and Mw = 500 to 2,000). Yes, but you are not limited to these. Moreover, these may be used independently and may be used together 2 or more types.

  Examples of the dichlorosilane compound represented by the formula (4) include allyldichlorosilane, allylhexyldichlorosilane, allylmethyldichlorosilane, allylphenyldichlorosilane, methyldichlorosilane, dimethyldichlorosilane, divinyldichlorosilane, diethyldichlorosilane, Methylpropyldichlorosilane, diethoxydichlorosilane, butylmethyldichlorosilane, phenyldichlorosilane, diallyldichlorosilane, methylpentyldichlorosilane, methylphenyldichlorosilane, cyclohexylmethyldichlorosilane, hexylmethyldichlorosilane, phenylvinyldichlorosilane, 6-methyldichlorosilyl-2-norbornene, 2-methyldichlorosilylnorbornene, 3-methacryloxypropyldichloromethylsilane , Heptylmethylsilane, dibutyldichlorosilane, methyl-β-phenethyldichlorosilane, methyloctyldichlorosilane, t-butylphenyldichlorosilane, decylmethyldichlorosilane, diphenyldichlorosilane, dihexyldichlorosilane, dodecylmethyldichlorosilane, methyl Although octadecyl dichlorosilane etc. can be illustrated, it is not restrict | limited at all to these. Moreover, these may be used independently and may use 2 or more types together.

  Moreover, in this invention, when obtaining the cured resin which forms both a resin layer or a resin layer, and a lens base material, with respect to the silicone resin represented by the said General formula (1), at least 1 in a molecule | numerator Either a compound having an ethylenically unsaturated double bond or a compound having at least a hydrosilyl group in the molecule may be blended to form a curable resin composition, or both may be blended to form a curable resin composition. Also good. Then, such a curable resin composition may be heat-cured or photocured to obtain either one or both of the lens substrate and the resin layer. Here, when a compound having at least one ethylenically unsaturated double bond is included in the molecule, it is preferable to include a radical initiator in the curable resin composition, and at least hydrosilylation in the molecule. When a compound having a group is blended, a hydrosilylation catalyst is preferably included in the curable resin composition.

  The compound having at least one ethylenically unsaturated double bond in the molecule may be any unsaturated compound that can be radically copolymerized with the silicone resin of the general formula (1), but is added to the silicone resin. Suitable for the above are roughly classified into a reactive oligomer which is a polymer having about 2 to 20 repeating structural units, and a low molecular weight and low viscosity reactive monomer. Further, it can be broadly classified into a monofunctional unsaturated compound having one unsaturated group and a polyfunctional unsaturated compound having two or more. In order to obtain a good three-dimensional crosslinked product, it is preferable to contain a very small amount of polyfunctional unsaturated compound (about 1% or less). However, when the heat resistance, strength, etc. of the copolymer are expected, a general formula ( The average of 1.1 or more, preferably 1.5 or more, more preferably 1.6 to 5 per molecule of 1) silicone resin. For this purpose, it is preferable to adjust the average number of functional groups using a mixture of a monofunctional unsaturated compound and a polyfunctional unsaturated compound having 2 to 5 unsaturated groups.

  Specifically, as reactive oligomers, for example, epoxy acrylate, epoxidized oil acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl acrylate, polyene / thiol, silicone acrylate, polybutadiene, polystyrylethyl methacrylate, etc. Can be illustrated. These include monofunctional unsaturated compounds and polyfunctional unsaturated compounds, and reactive monofunctional monomers include styrene, vinyl acetate, N-vinylpyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, Examples include cyclohexyl acrylate, n-decyl acrylate, isobornyl acrylate, dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate, trifluoroethyl methacrylate, and the like. In addition, reactive polyfunctional monomers include unsaturated compounds other than the general formula (2) such as tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, bisphenol A diglycidyl ether diacrylate, and tetraethylene glycol diacrylate. Examples thereof include acrylate, hydroxypivalate neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and the like.

  In addition, the compound having at least one ethylenically unsaturated double bond in the molecule that can be used in obtaining the curable resin composition in the present invention includes various reactivity in addition to those exemplified above. Oligomers or monomers can be used. These reactive oligomers and monomers may be used alone or in combination of two or more. Similarly, a silicone resin copolymer can be obtained by radical copolymerization thereof.

  As a radical initiator to be blended with a compound having at least one ethylenically unsaturated double bond in the molecule, a photopolymerization initiator or a thermal polymerization initiator may be used. Here, as the photopolymerization initiator, compounds such as acetophenone-based, benzoin-based, benzophenone-based, thioxanthone-based, and acylphosphine oxide-based compounds can be suitably used. Specifically, trichloroacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2 -Morpholinopropan-1-one, benzoin methyl ether, benzyldimethyl ketal, benzophenone, thioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, camphorquinone, benzyl, anthraquinone, Michler's ketone, etc. can do. Moreover, the photoinitiator adjuvant and the sharpening agent which show an effect in combination with a photoinitiator can also be used together. These photopolymerization initiators may be used alone or in combination of two or more.

  In addition, as the thermal polymerization initiator used for the above purpose, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxydicarbonate, peroxyester Various organic peroxides can be suitably used. Specifically, cyclohexanone peroxide, 1,1-bis (t-hexaperoxy) cyclohexanone, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, diisopropyl peroxide, t-butyl peroxide-2-ethyl Although hexanoate etc. can be illustrated, it is not restrict | limited at all to this. These thermal polymerization initiators may be used alone or in combination of two or more.

  When a photopolymerization initiator or a thermal polymerization initiator is blended as the radical initiator, the addition amount is preferably in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight of the curable resin composition. A range of 1 to 3 parts by weight is more preferable. If this addition amount is less than 0.1 parts by weight, curing will be insufficient and the strength and rigidity of the resulting lens will be reduced. On the other hand, when the amount exceeds 5 parts by weight, there is a possibility that problems such as coloring of the lens may occur.

  On the other hand, the compound having at least a hydrosilyl group in the molecule is preferably an oligomer or monomer having at least one hydrosilylatable hydrogen atom on the silicon atom in the molecule. Examples of the oligomer having a hydrogen atom on a silicon atom include polyhydrogensiloxanes, polydimethylhydroxysiloxanes and copolymers thereof, and siloxanes whose ends are modified with dimethylhydrosiloxy. Examples of the monomer having a hydrogen atom on a silicon atom include cyclic siloxanes such as tetramethylcyclotetrasiloxane and pentamethylcyclopenta, dihydrodisiloxanes, trihydromonosilanes, dihydromonosilanes, and monohydromonosilanes. And dimethylsiloxysiloxanes. Two or more of these may be mixed.

  For hydrosilylation catalysts formulated with compounds having at least a hydrosilyl group in the molecule, platinum chloride, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, ketone complex, chloroplatinic acid and olefin complex And platinum group metal catalysts such as platinum and vinylsiloxane complexes, dicarbonyldichloroplatinum and palladium catalysts, rhodium catalysts, and the like. Among these, those selected from chloroplatinic acid, complexes of chloroplatinic acid and olefins, and complexes of platinum and vinylsiloxane are preferable from the viewpoint of catalytic activity. Moreover, these may be used independently and may be used together 2 or more types.

  When the hydrosilylation catalyst is blended, the amount added is preferably 1 to 1000 ppm, more preferably 20 to 500 ppm as a metal atom with respect to the weight of the curable resin composition. Further, the hydrosilylation catalyst may be used alone or in combination with two or more of the radical initiators described above.

  As described above, in the present invention, when the curable resin composition containing the silicone resin is obtained, the silicone resin is cured to form a resin layer or both a resin layer and a lens base material, thereby forming a composite lens. Compounds having at least one ethylenically unsaturated double bond in the molecule, compounds having at least a hydrosilyl group in the molecule, radical initiator, hydrosilylation catalyst Etc. may be appropriately selected and blended. That is, when a compound having an ethylenically unsaturated double bond or a compound having a hydrosilyl group is blended, a hydrosilylation catalyst or radical initiator (thermal polymerization initiator or photopolymerization initiator) is used as an additive for promoting the reaction. In addition, a thermal polymerization accelerator, a photoinitiator assistant, a sharpener, and the like may be added. In addition, organic / inorganic fillers, plasticizers, flame retardants, thermal stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents, mold release agents are within the scope of the present invention. Various additives such as a foaming agent, a nucleating agent, a colorant, a crosslinking agent, a dispersion aid, and a resin component can also be added.

  Moreover, in this invention, you may form using things other than what hardened the silicone resin represented by General formula (1) mentioned above as a lens base material. In this case, for example, a compound obtained by curing a compound having at least one ethylenically unsaturated double bond in the molecule as described above may be used.

  The resin layer forming the composite lens of the present invention has a function of forming a curved lens surface, and its shape, thickness, and the like vary depending on the application, and are not particularly limited. For example, a spherical lens or an aspheric lens Any of these can be formed. On the other hand, the lens base material functions to adjust the lens thickness, and the shape and thickness thereof are not particularly limited because they vary depending on the application. There may be. In addition, the resin layer may be provided on both surfaces of the lens base material, or may be formed only on one side of the lens base material.

  The composite lens of the present invention can be obtained by forming the resin layer on the lens substrate by curing the silicone resin on the lens substrate by heating or light irradiation. In the case of manufacturing, the molding temperature can be selected from a wide range from room temperature to around 200 ° C. by selection of a thermal polymerization initiator, an accelerator and the like. In this case, for example, a sheet-shaped lens base material can be obtained by casting the silicone resin of the general formula (1) (or a curable resin composition containing the same) on a metal plate or a glass plate, followed by heat curing. it can.

  Moreover, when manufacturing a lens base material by light irradiation, a molded object (lens base material) can be obtained by irradiating the ultraviolet rays with a wavelength of 100-400 nm and the visible light with a wavelength of 400-700 nm. The wavelength of light to be used is not particularly limited, but near ultraviolet light having a wavelength of 200 to 400 nm is preferably used. The lamps used as ultraviolet light sources include low-pressure mercury lamps (output: 0.4 to 4 W / cm), high-pressure mercury lamps (40 to 160 W / cm), ultra-high pressure mercury lamps (173 to 435 W / cm), metal halide lamps (80 ˜160 W / cm), pulse xenon lamp (80 to 120 W / cm), electrodeless discharge lamp (80 to 120 W / cm), and the like. Each of these ultraviolet lamps is characterized by its spectral distribution, and is therefore selected according to the type of photopolymerization initiator used. Moreover, similarly to the method of manufacturing by heating, for example, a silicone resin of the general formula (1) (or a curable resin composition containing the same) is cast on a glass plate and photocured to form a sheet. A lens substrate can be obtained.

  As described above, the resin layer constituting the composite lens of the present invention is obtained by placing the silicone resin of the general formula (1) (or a curable resin composition containing the same) on the lens substrate (liquid state). In the case of an object, including the case of casting or the like), it can be formed by curing by heating or light irradiation.

  Moreover, in order to make a lens base material and a resin layer into a predetermined shape and thickness, a conventionally well-known method can also be used. For example, a silicone resin of the general formula (1) (or a curable resin composition containing the same) serving as a resin layer on a mold (for example, a mold having a spherical recess) processed into a predetermined shape. A lens-shaped molded product can be obtained by curing with heating or light irradiation in a state where a predetermined amount is filled and a preliminarily cured lens base material is placed on the upper side. Although it is possible to form a compound lens by this molding, a resin layer having a predetermined shape is similarly provided on the remaining surface of the lens substrate, and two resin layers are formed on both surfaces of the lens substrate. A composite lens formed by bonding may be used. A pre-cured resin layer is provided with a mold having a predetermined shape and filled with a silicone resin of general formula (1) (or a curable resin composition containing the same) to form a lens substrate. You may make it do.

  In addition, when obtaining a compound lens, surface polishing, antistatic treatment, hard coat treatment, no coating, etc. are performed for the purpose of improving antireflection, imparting high hardness, improving abrasion resistance, imparting antifogging, etc. as necessary. You may make it perform well-known physical or chemical processes, such as a reflective coating process and a light control process.

  The composite lens of the present invention is excellent in heat resistance because at least the resin layer is made of a silicone resin mainly composed of polyorganosilsesquioxane having a cage structure represented by the general formula (1). Further, by forming the resin layer from the silicone resin in the same manner as the lens substrate, the adhesion at the lens substrate-resin interface can be improved. Therefore, it can be used in the solder reflow process. For example, a lens of a camera module in which a semiconductor and a lens are integrated, such as a CCD with a lens and a CMOS sensor with a lens mounted on a mobile phone, a digital camera, etc. Etc. are suitably used.

FIG. 1 is a flowchart showing a method for producing a heat-resistant composite lens of the present invention.

  Hereinafter, the present invention will be specifically described based on examples and the like. The scope of the present invention is not limited by these examples.

  Examples of the present invention will be described below. In addition, the silicone resin used in the following Example was obtained by the method shown in the following synthesis examples.

[Synthesis Example 1]
To a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 14.3 g of tetramethylammonium hydroxide pentahydrate as a basic catalyst is added and dissolved in 17 g of water, followed by 189 mL of toluene and 95 mL of 2-propanol. Put. To the dropping funnel, 23.4 g of vinyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd .; KBM1003) and 23.7 g of ethyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd .; LS-890) are added, and the reaction vessel is stirred. Then, a mixed solution of vinyltrimethoxysilane and ethyltrimethoxysilane was added dropwise at room temperature over 3 hours. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After completion of the stirring, the stirring was stopped and the mixture was left for one day. Next, the reaction vessel was equipped with a Din Stark and a cooling tube, 95 mL of toluene was added, and 2-propanol and methanol generated during hydrolysis were removed at 90 ° C. using an oil bath. Thereafter, the temperature of the oil bath was set to 120 ° C., and toluene was heated to reflux while removing water to perform a recondensation reaction. After refluxing toluene, the mixture was stirred for 3 hours and then returned to room temperature to complete the reaction. The reaction solution was neutralized with 82.9 g of 10% aqueous citric acid solution. The aqueous layer was extracted with toluene, and the organic layer was washed 3 times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 25.5 g (98%) of a colorless and transparent viscous liquid silanol group-containing cage-type siloxane (23).

From the result of measuring GPC of the colorless and transparent viscous liquid silanol group-containing cage-type siloxane (23) obtained above, it was confirmed that Mw = 1136 and Mw / Mn = 1.390. Among them, the peaks on the low molecular side occupying 70% of the area ratio were Mw = 659 and Mw / Mn = 1.084. Next, as a result of measuring ¹ H-NMR, a multiplet peak due to a vinyl group of 5.8 to 6.2 ppm, a multiplet peak due to an ethyl group of 0.4 to 1.2 ppm, and a silanol group of 1.6 ppm The peak integration ratio was 1 for ethyl group and 0.189 for silanol group relative to 1 vinyl group. Therefore, the compound estimated from the low molecular side Mw which is the main peak and the integration ratio is represented by the following formula (2).
[R ¹ SiO _3/2 ] _n [HO _1/2 ] _k (2)
It was suggested that n is 8 and k is 2 (R ¹ is vinyl group: ethyl group = 1: 1).

  In a reaction vessel equipped with a stirrer and a dropping funnel, 20.0 g of the silanol group-containing cage-type silsesquioxane compound (23) obtained above and 4.4 g of cyclohexanedimethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) are weighed. The solution was purged with nitrogen and dissolved in 61 mL of pyridine. To the dropping funnel, 19.2 g of dimethyldichlorosilane and 76 mL of pyridine were added dropwise at room temperature over 2 hours. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After stirring for 2 hours, 140 mL of toluene and 70 mL of distilled water were added. The aqueous layer was extracted with toluene, and the organic layer was washed 3 times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated to obtain 35.3 g (recovery rate: 92%) of an organic-inorganic composite (24) as a colorless transparent viscous liquid.

From the result of measuring GPC of the organic-inorganic composite (24) obtained above, it was Mw = 6671 and Mw / Mn = 2.095. Therefore, the obtained organic-inorganic composite (24) has the following formula (1):
[[(R ¹ SiO _3/2 ) _n ] (R ² ₂ SiO _2/2 )] _m [[XO _2/2 ] (R ² ₂ SiO _2/2 )] _l (1)
(R ¹ is a vinyl resin: ethyl group = 1: 1, R ² is a methyl group, and X is composed of cyclohexanedimethanol (CHDM)), n is a silicone resin of 6 to 14, m + 1 = 13 It was confirmed.

[Synthesis Example 2]
Synthesis was performed in the same manner as in Synthesis Example 1 except that diphenyldichlorosilane was used instead of dimethyldichlorosilane as dichlorosilane, and 35.3 g of a colorless and transparent viscous liquid organic-inorganic composite (25) (recovery rate: 92%) )Obtained.

From the results of measuring GPC of the organic-inorganic composite (25) obtained above, Mw = 6263 and Mw / Mn = 1.849. Therefore, the obtained organic-inorganic composite (25) has the following formula (1)
[[(R ¹ SiO _3/2 ) _n ] (R ² ₂ SiO _2/2 )] _m [[XO _2/2 ] (R ² ₂ SiO _2/2 )] _l (1)
(R ¹ is vinyl group: ethyl group = 1: 1, R ² is phenyl group, and X is made of cyclohexanedimethanol (CHDM)), n is a silicone resin of 6-14, m + 1 = 10 It was confirmed.

[Synthesis Example 3]
To a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 14.3 g of tetramethylammonium hydroxide pentahydrate as a basic catalyst is added and dissolved in 17 g of water, followed by 189 mL of toluene and 95 mL of 2-propanol. Put. To the dropping funnel, 78.4 g of 3-methacryloxypropyltrimethoxyxysilane (manufactured by Shin-Etsu Chemical Co., Ltd .; KBM503) was added, and 3-methacryloxypropyltrimethoxysilane was added at room temperature for 3 hours while stirring the reaction vessel. And dripped. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After completion of the stirring, the stirring was stopped and the mixture was left for one day. Next, the reaction vessel was equipped with a Din Stark and a cooling tube, 95 mL of toluene was added, and 2-propanol and methanol generated during hydrolysis were removed at 90 ° C. using an oil bath. Thereafter, the temperature of the oil bath was set to 120 ° C., and toluene was heated to reflux while removing water to perform a recondensation reaction. After refluxing toluene, the mixture was stirred for 3 hours and then returned to room temperature to complete the reaction. The reaction solution was neutralized with 82.9 g of 10% aqueous citric acid solution. The aqueous layer was extracted with toluene, and the organic layer was washed 3 times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 47.4 g (98%) of a colorless transparent viscous liquid silanol group-containing cage-type siloxane (26).

From the result of measuring GPC of the colorless and transparent viscous liquid silanol group-containing cage-type siloxane (26) obtained above, it was confirmed that Mw = 1575 and Mw / Mn = 1.222. Among them, the peaks on the low molecular side occupying 70% of the area ratio were Mw = 1198 and Mw / Mn = 1.082. Next, as a result of measuring ¹ H-NMR, the peak integration ratio of 5.4 to 6.2 ppm methacryl group and 1.6 ppm silanol group was 0.189 with respect to methacryl group 1. there were. Therefore, the compound estimated from the low molecular side Mw which is the main peak and the integration ratio is represented by the following formula (2).
[R ¹ SiO _3/2 ] _n [HO _1/2 ] _k (2)
It was suggested that n is 8, and k is 2 (R ¹ is a 3-methacryloxypropyl group).

  In a reaction vessel equipped with a stirrer and a dropping funnel, 20.0 g of the silanol group-containing cage silsesquioxane compound (26) obtained above and 4.4 g of cyclohexanedimethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) are weighed. The solution was purged with nitrogen and dissolved in 61 mL of pyridine. To the dropping funnel, 19.2 g of dimethyldichlorosilane and 76 mL of pyridine were added dropwise at room temperature over 2 hours. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After stirring for 2 hours, 140 mL of toluene and 70 mL of distilled water were added. The aqueous layer was extracted with toluene, and the organic layer was washed 3 times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 35.3 g (recovery rate: 92%) of an organic-inorganic composite (27) as a colorless transparent viscous liquid.

From the result of measuring GPC of the organic-inorganic composite (27) obtained above, Mw = 88013 and Mw / Mn = 8.536. Therefore, the obtained organic-inorganic composite (27) has the following formula (1):
[[(R ¹ SiO _3/2 ) _n ] (R ² ₂ SiO _2/2 )] _m [[XO _2/2 ] (R ² ₂ SiO _2/2 )] _l (1)
(R ¹ is a 3-methacryloxypropyl group, R ² is a methyl group, and X is composed of cyclohexanedimethanol (CHDM)), and n is a silicone resin of 6 to 14 and m + 1 = 88 did.

[Synthesis Example 4]
Synthesis was performed in the same manner as in Synthesis Example 3 except that diphenyldichlorosilane was used instead of dimethyldichlorosilane as dichlorosilane, and 35.3 g of a colorless and transparent viscous liquid organic-inorganic composite (28) (recovery rate: 92%) )Obtained.

From the result of measuring GPC of the organic-inorganic composite (28) obtained above, Mw = 40025 and Mw / Mn = 4.769. Therefore, the obtained organic-inorganic composite (28) has the following formula (1):
[[(R ¹ SiO _3/2 ) _n ] (R ² ₂ SiO _2/2 )] _m [[XO _2/2 ] (R ² ₂ SiO _2/2 )] _l (1)
(R ¹ is a 3-methacryloxypropyl group, R ² is a phenyl group, and X is cyclohexanedimethanol (CHDM)), and n is a silicone resin of 6 to 14 and m + 1 = 36 did.

[Synthesis Example 5]
In a reaction vessel equipped with a stirrer and a dropping funnel, 20.0 g of the silanol group-containing cage-type silsesquioxane compound (23) obtained above and 4.4 g of cyclohexanedimethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) are weighed. The solution was purged with nitrogen and dissolved in 61 mL of pyridine. To the dropping funnel, 15.3 g of dimethyldichlorosilane, 3.9 g of diphenyldichlorosilane, and 76 mL of pyridine were added dropwise at room temperature over 2 hours. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After stirring for 2 hours, 140 mL of toluene and 70 mL of distilled water were added. The aqueous layer was extracted with toluene, and the organic layer was washed 3 times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated to obtain 35.3 g (recovery rate 92%) of an organic-inorganic composite (29) as a colorless transparent viscous liquid.

From the result of measuring GPC of the organic-inorganic composite (29) obtained above, Mw = 6467 and Mw / Mn = 1.972. Therefore, the obtained organic-inorganic composite (29) has the following formula (1):
[[(R ¹ SiO _3/2 ) _n ] (R ² ₂ SiO _2/2 )] _m [[XO _2/2 ] (R ² ₂ SiO _2/2 )] _l (1)
(R ¹ is represented by vinyl group: ethyl group = 1: 1, R ² is methyl group: phenyl group = 8: 2, and X is composed of cyclohexanedimethanol (CHDM)), n is 6 to 14, m + 1 = 12 silicone resin was confirmed.

[Synthesis Example 6]
In a reaction vessel equipped with a stirrer and a dropping funnel, 20.0 g of the silanol group-containing cage silsesquioxane compound (26) obtained above and 4.4 g of cyclohexanedimethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) are weighed. The solution was purged with nitrogen and dissolved in 61 mL of pyridine. To the dropping funnel, 15.3 g of dimethyldichlorosilane, 3.9 g of diphenyldichlorosilane, and 76 mL of pyridine were added dropwise at room temperature over 2 hours. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After stirring for 2 hours, 140 mL of toluene and 70 mL of distilled water were added. The aqueous layer was extracted with toluene, and the organic layer was washed 3 times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 35.3 g (recovery rate: 92%) of an organic-inorganic composite (30) as a colorless transparent viscous liquid.

From the result of measuring GPC of the organic-inorganic composite (30) obtained above, Mw = 64019 and Mw / Mn = 6.653. Therefore, the obtained organic-inorganic composite (30) has the following formula (1):
[[(R ¹ SiO _3/2 ) _n ] (R ² ₂ SiO _2/2 )] _m [[XO _2/2 ] (R ² ₂ SiO _2/2 )] _l (1)
(R ¹ is 3-methacryloxypropyl group, R ² is methyl group: phenyl group = 7: 3, and X is composed of cyclohexanedimethanol (CHDM)), n is 6 to 14, and m + 1 = 64 It was confirmed that it was a silicone resin.

[Synthesis Example 7]
To a reaction vessel equipped with a stirrer, a dropping funnel and a thermometer, 14.3 g of tetramethylammonium hydroxide pentahydrate as a basic catalyst is added and dissolved in 17 g of water, followed by 189 mL of toluene and 95 mL of 2-propanol. Put. To the dropping funnel, 23.4 g of vinyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd .; KBM1003) and 39.2 g of 3-methacryloxypropyltrimethoxyxysilane (Shin-Etsu Chemical Co., Ltd .; KBM503) were added and the reaction vessel was added. While stirring, a mixed liquid of vinyltrimethoxysilane and 3-methacryloxypropyltrimethoxyxysilane was added dropwise at room temperature over 3 hours. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After completion of the stirring, the stirring was stopped and the mixture was left for one day. Next, the reaction vessel was equipped with a Din Stark and a cooling tube, 95 mL of toluene was added, and 2-propanol and methanol generated during hydrolysis were removed at 90 ° C. using an oil bath. Thereafter, the temperature of the oil bath was set to 120 ° C., and toluene was heated to reflux while removing water to perform a recondensation reaction. After refluxing toluene, the mixture was stirred for 3 hours and then returned to room temperature to complete the reaction. The reaction solution was neutralized with 82.9 g of 10% aqueous citric acid solution. The aqueous layer was extracted with toluene, and the organic layer was washed 3 times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 25.5 g (98%) of a colorless and transparent viscous liquid silanol group-containing cage-type siloxane (31).

From the result of measuring GPC of the colorless and transparent viscous liquid silanol group-containing cage-type siloxane (31) obtained above, it was confirmed that Mw = 1707 and Mw / Mn = 1.369. Among them, the peaks on the low molecular side occupying 70% of the area ratio were Mw = 1021 and Mw / Mn = 1.097. Next, as a result of measuring ¹ H-NMR, a peak of a multiplet peak due to a vinyl group of 5.8 to 6.2 ppm, a peak due to a methacryl group of 5.4 to 6.2 ppm, and a peak integration of a silanol group of 1.6 ppm The ratio of vinyl group 1 to methacryl group 1 and silanol group 0.189. Therefore, the compound estimated from the low molecular side Mw which is the main peak and the integration ratio is represented by the following formula (2).
[R ¹ SiO _3/2 ] _n [HO _1/2 ] _k (2)
It was suggested that n is 8 and k is 2 (R ¹ is vinyl group: 3-methacryloxypropyl group = 1: 1).

  In a reaction vessel equipped with a stirrer and a dropping funnel, 20.0 g of the silanol group-containing cage silsesquioxane compound (31) obtained above and 4.4 g of cyclohexanedimethanol (manufactured by Tokyo Chemical Industry Co., Ltd.) are weighed. The solution was purged with nitrogen and dissolved in 61 mL of pyridine. To the dropping funnel, 15.3 g of dimethyldichlorosilane, 3.9 g of diphenyldichlorosilane, and 76 mL of pyridine were added dropwise at room temperature over 2 hours. After completion of dropping, the mixture was stirred at room temperature for 2 hours. After stirring for 2 hours, 140 mL of toluene and 70 mL of distilled water were added. The aqueous layer was extracted with toluene, and the organic layer was washed 3 times with distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and concentrated to obtain 35.3 g (recovery rate 92%) of an organic-inorganic composite (32) as a colorless transparent viscous liquid.

From the result of measuring the GPC of the organic-inorganic composite (32) obtained above, Mw = 36793 and Mw / Mn = 4.386. Therefore, the obtained organic-inorganic composite (32) has the following formula (1):
[[(R ¹ SiO _3/2 ) _n ] (R ² ₂ SiO _2/2 )] _m [[XO _2/2 ] (R ² ₂ SiO _2/2 )] _l (1)
(R ¹ is represented by vinyl group: 3-methacryloxypropyl group = 1: 1, R ² is methyl group: phenyl group = 7: 3, and X is composed of cyclohexanedimethanol (CHDM)), and n is 6 It was confirmed that the silicone resin was ˜14, m + 1 = 47.

  Table 1 summarizes the raw materials used in Synthesis Examples 1-7.

[Example 1]
90 parts by weight of the organic-inorganic composite (24) obtained in Synthesis Example 1 and 10 parts by weight of the compound dicyclopentanyl diacrylate (Kyoeisha Chemical Co., Ltd .; DCP-A) represented by the following formula (33) 1 part by weight of a curing catalyst dicumyl peroxide (Nippon Yushi Co., Ltd .; Park Mill D) represented by the following formula (34) is mixed and stirred well, and the curable resin composition of Example 1 is mixed. Was prepared.

  The curable resin composition obtained above was poured into a mold made of glass plates to a thickness of 2 mm, 1 hour at 100 ° C, 1 hour at 120 ° C, 1 hour at 140 ° C, 1 hour at 160 ° C, and A sheet-shaped silicone resin molded body (lens substrate 1) having a predetermined thickness was obtained by heating at 180 ° C. for 2 hours.

  Next, as shown in FIG. 1, the curable resin composition 2 is filled into a metal mold 3 having a concave portion processed into a predetermined spherical shape, and the filled curable resin composition 2 With the previously formed lens base material placed in contact with the surface (liquid surface), 100 ° C. for 1 hour, 120 ° C. for 1 hour, 140 ° C. for 1 hour, 160 ° C. for 1 hour, and 180 ° C. The resin layer 4 having a thickness of 0.02 mm was bonded to the lens substrate 1 at the thickest part by heating and curing for 2 hours.

  Further, the curable resin composition 2 was cured on the remaining upper surface of the lens substrate 1 by the same method, and a composite lens 5 in which the resin layers 4 were bonded to both surfaces of the lens substrate 1 was obtained.

[Examples 2 and 7]
Instead of the organic-inorganic composite (24), 70 parts by weight of the organic-inorganic composite (25) and (32) obtained in Synthesis Examples 2 and 7, respectively, and the above formula (33) are used. Compound dicyclopentanyl diacrylate (manufactured by Kyoeisha Chemical Co., Ltd .; DCP-A) 30 parts by weight is mixed, and the curing catalyst dicumyl peroxide represented by the above formula (34) (manufactured by NOF Corporation; Park Mill D) 1 part by weight was mixed and stirred well to prepare curable resin compositions of Examples 2 and 7. Otherwise, the composite lens 5 was obtained in the same manner as in Example 1.

[Example 5]
The curable resin composition of Example 5 was the same as Example 1 except that the organic-inorganic composite (29) obtained in Synthesis Example 5 was used instead of the organic-inorganic composite (24). Was prepared. Otherwise, the composite lens 5 was obtained in the same manner as in Example 1.

[Example 3]
70 parts by weight of the organic-inorganic composite (27) obtained in Synthesis Example 3 and 30 parts by weight of the above formula (33) are mixed, and the curing catalyst 1-hydroxycyclohexyl phenyl ketone represented by the following formula (35) 1 part by weight (manufactured by Ciba Japan Co., Ltd .; Irgacure184) was mixed and stirred well to prepare the curable resin composition of Example 3.

The curable resin composition obtained above is poured into a mold made of glass plates so as to have a thickness of 2 mm, and cured with an accumulated exposure amount of 2000 mJ / cm ² using a 30 W / cm high-pressure mercury lamp, to a predetermined thickness. A sheet-shaped silicone resin molded body (lens substrate 1) was obtained.

Next, as shown in FIG. 1, the curable resin composition 2 filled with the above-described curable resin composition 2 is filled in a glass mold 3 having a concave portion processed into a predetermined spherical shape. By using a 30 W / cm high-pressure mercury lamp with the lens substrate 1 placed so as to touch the surface (liquid level) of the film, it is cured at an accumulated exposure amount of 1000 mJ / cm ² , so that the thickness is the thickest part. A 0.02 mm resin layer 4 was bonded to the lens substrate 1.

  Further, the curable resin composition 2 was cured on the remaining upper surface of the lens substrate 1 by the same method, and a composite lens 5 in which the resin layers 4 were bonded to both surfaces of the lens substrate 1 was obtained.

[Examples 4 and 6]
In the same manner as in Example 3, except that the organic-inorganic composites (28) and (30) obtained in Synthesis Examples 4 and 6 were used instead of the organic-inorganic composite (27), respectively. 4 and 6 curable resin compositions were prepared. Otherwise, the composite lens 5 was obtained in the same manner as in Example 3.

[Comparative Example 1]
50 parts by weight of dimethacryloxypropyl polydimethylsiloxane (DMS-R11 manufactured by AMAX Co., Ltd.), 30 parts by weight of dipentaerythritol hexaacrylate (light acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.), and dicyclopentanyl diacrylate ( 20 parts by weight of Kyoeisha Chemical Co., Ltd. light acrylate DCP-A) is mixed, and the curing catalyst 1-hydroxycyclohexyl phenyl ketone represented by the above formula (35) (Ciba Japan Co., Ltd .; Irgacure184) is added to the resin. 1 part by weight was mixed with respect to 100 parts by weight and stirred well to prepare a curable resin composition of Comparative Example 1. Otherwise, the composite lens 5 was obtained in the same manner as in Example 3.

[Comparative Example 2]
70 parts by weight of dimethacryloxypropyl polydimethylsiloxane (DMS-R11 manufactured by Amax Co., Ltd.), 20 parts by weight of dipentaerythritol hexaacrylate (light acrylate DPE-6A manufactured by Kyoeisha Chemical Co., Ltd.), and dicyclopentanyl diacrylate ( 10 parts by weight of Kyoeisha Chemical Co., Ltd. light acrylate DCP-A) is mixed, and the curing catalyst 1-hydroxycyclohexyl phenyl ketone represented by the above formula (35) (Ciba Japan Co., Ltd .; Irgacure184) is added to the resin. 1 part by weight was mixed with respect to 100 parts by weight and stirred well to prepare a curable resin composition of Comparative Example 2. Otherwise, the composite lens 5 was obtained in the same manner as in Example 3.

Table 2 summarizes the compositions of the curable resin compositions obtained in the above Examples and Comparative Examples. In addition, the numerical value in a table | surface represents a weight part. The meanings of symbols A to F used in Table 2 are as follows, and the parentheses () after the numerical value of item A are specific silicone resins (organic-inorganic composites) obtained in the synthesis examples. ).
A: Silicone resin B obtained in the synthesis example B: Dimethacryloxypropyl polydimethylsiloxane (DMS-R11 manufactured by Amax Co., Ltd.)
C: Dipentaerythritol hexaacrylate (Kyoeisha Chemical Co., Ltd. light acrylate DPE-6A)
D: Dicyclopentanyl diacrylate (Kyoeisha Chemical Co., Ltd. light acrylate DCP-A)
E: Dicumyl peroxide (Nippon Yushi Co., Ltd .; Park Mill D)
F: 1-hydroxycyclohexyl phenyl ketone (Ciba Japan Co., Ltd .; Irgacure184)

  The physical properties of the composite lens 5 obtained in the above examples and comparative examples were evaluated as follows. The results are shown in Table 3.

1) Total light transmittance (JIS K 7361-1): Measured using an ultraviolet-visible light infrared spectrophotometer (V-630M manufactured by JASCO Corporation).
2) Refractive index: Measured using an Abbe refractometer (DR-M4 Atago Co., Ltd.).
3) Water absorption: The sample was dried at 50 ° C., weighed, and then immersed in warm water at 25 ° C. for 24 hours. The weight after 24 hours was measured, and the water absorption was determined by the following formula.
Water absorption rate (%) = [(water absorption weight−dry weight) / dry weight] × 100
4) Linear expansion coefficient: Using a thermomechanical analyzer (manufactured by TMA), the linear expansion coefficient in the range of 30 ° C. to 200 ° C. was measured under conditions of a heating rate of 5 ° C./min and a compression load of 0.1 N .
5) Curing shrinkage: The specific gravity before and after curing was measured to calculate the volume shrinkage. The specific gravity of the curable resin composition was determined by a pycnometer method (JIS K 7112), and the cured product was determined by an underwater substitution method (JIS K 7112).
Curing shrinkage = (1-specific gravity of resin before curing / specific gravity of resin after curing) × 100

  The compound lens according to the present invention is suitably used as a lens for a camera module in which a semiconductor and a lens are integrated, such as a CCD with a lens and a CMOS sensor with a lens mounted on a mobile phone or a digital camera. Is done. In addition, it can also be used for lenses such as in-vehicle camera modules that require heat resistance.

1: Lens substrate 2: Curable resin composition 3: Glass mold 4: Resin layer 5: Composite lens

Claims (3)

A compound lens in which a resin layer is bonded to a lens substrate, wherein the lens substrate and the resin layer are each made of a cured resin, and at least the resin layer has the following general formula (1)
[[(R ¹ SiO _3/2 ) _n ] (R ² ₂ SiO _2/2 )] _m [[XO _2/2 ] (R ² ₂ SiO _2/2 )] _l (1)
(However, R ¹ and R ² are vinyl groups, allyl groups, alkyl groups, aryl groups, (meth) acryloyl groups, or groups having an oxirane ring, and may be the same or different from each other, The structure includes one or more of an aliphatic structure having 5 to 50 carbon atoms, an alicyclic structure, an aromatic structure, and an —OCOO— bond, and n, m, and l each represent an average value, and n is 6 to 14 M and l are 1 or more, and m + 1 is 2 to 2,000). The weight average molecular weight is Mw = 5,000 to 1,000,000 and unsaturated Curing a silicone resin having at least two reactive functional groups in one molecule selected from the group consisting of a vinyl group having a double bond, an allyl group, and a (meth) acryloyl group; Heat-resistant composite type 'S.   2. The heat resistant composite lens according to claim 1, wherein the lens substrate is formed by curing a silicone resin represented by the general formula (1).   The lens base material and / or the resin layer is compounded with a compound having at least one ethylenically unsaturated double bond in the molecule and / or a compound having at least a hydrosilyl group in the molecule with respect to the silicone resin. 3. The heat resistant composite lens according to claim 1, wherein a curable resin composition obtained by blending an initiator and / or a hydrosilylation catalyst is cured.

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