JP2009155442A - Lens resin composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for lens which has heat resistance durable for reflow soldering and is excellent in low water absorption, transparency and low heat expansion property. <P>SOLUTION: The resin composition for lens essentially comprises: cage silsesquioxane (A) having at least two aliphatic unsaturated bonds in one molecule; organohydrogenpolysiloxane (B) having at least two SiH groups in one molecule; ethylenic unsaturated compound (C) having at least two (meth)acrylic groups in one molecule; and curing catalyst (D), wherein the ratio of the number of aliphatic unsaturated bond groups of the component (A) to the number of SiH groups of the component (B) is 1/(0.1 to 2.0), and the mol number of (meth)acrylic groups per resin component 100g consisting of the component (A), component (B) and component (C) becomes more than 0.2. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a lens resin composition and a cured product thereof, and in particular, to obtain a lens having heat resistance capable of withstanding solder reflow and having excellent low water absorption, high transparency, and low thermal expansion. It is related with the resin composition for lenses which can be manufactured.

  In recent years, along with the miniaturization of various electronic devices, the electronic components to be mounted have also been miniaturized and chipped. Conventionally, in mounting these electronic components on a circuit board, a surface mounting method in which soldering is performed using a reflow furnace (solder reflow) is generally used. Among these electronic components, for example, electronic components that integrate a semiconductor and a lens, such as a CCD (Charge Coupled Device) with a lens and a CMOS (Complementary Metal Oxide Semiconductor) sensor with a lens, are for industrial use. Widely used for commercial, medical and consumer use.

  However, it is necessary to withstand the heat (260 ° C.) of a reflow furnace adapted for mounting as a lens used for the electronic component. If it is a glass lens, it can usually withstand the reflow temperature. Conventionally, the alicyclic olefin polymer (COP) described in Patent Document 1 that has been mainly used, and the polycarbonate (PC) described in Patent Document 2 are used. ) And the like have the advantage of being inexpensive, but are thermoplastic, so that the heat resistance in the reflow process is insufficient, causing problems such as deformation and yellowing.

High heat-resistant silicone resins are expected as heat-resistant materials that can withstand the reflow temperature. However, the silicone materials described in Patent Documents 3 and 4 are high heat resistance and low water absorption by addition-curing a specific organopolysiloxane (such as a cage silsesquioxane) and a specific organohydrogenpolysiloxane. In fact, the above-mentioned silicone materials have a high coefficient of thermal expansion. Furthermore, after leaving them in a high-temperature and high-humidity state, which is an object of lens material evaluation, the temperature is returned to room temperature. Another problem arises that the resin becomes cloudy.
JP 2005-139370 A Japanese Patent Laid-Open No. 2002-129027 JP 2002-265787 A WO2007 / 119477 pamphlet

  Accordingly, an object of the present invention is to provide a lens resin composition that eliminates the drawbacks of the prior art described above, has performance equivalent to that of a thermoplastic resin, and has reflow heat resistance.

  As a result of intensive studies to solve the above problems, the present inventors have (A) a cage silsesquioxane having two or more aliphatic unsaturated bonds in one molecule, and (B) in one molecule. For lenses having an organohydrogenpolysiloxane having two or more SiH groups, (C) an ethylenically unsaturated compound having two or more (meth) acrylic groups in one molecule, and (D) a curing catalyst. It has been found that the above problems can be solved by using a resin composition, and the present invention has been completed.

  That is, the present invention includes (A) a cage silsesquioxane having two or more aliphatic unsaturated bonds in one molecule, (B) an organohydrogenpolysiloxane having two or more SiH groups in one molecule, (C) An ethylenically unsaturated compound having two or more (meth) acrylic groups in one molecule, and (D) a curing catalyst as essential components, and (A) the number of aliphatic unsaturated bonding groups in component ( B) The ratio of SiH groups in the component is 1: 0.1 to 2.0, and the number of moles of (meth) acrylic per 100 g of the resin component consisting of the components (A), (B) and (C) is 0. A resin composition for molding a lens characterized by exceeding .2.

  Moreover, this invention is a hardened | cured material which consists of the said resin composition for lenses. Furthermore, this invention is a lens obtained by shape | molding the said resin composition for lenses. The “resin component comprising the (A) component, the (B) component, and the (C) component” refers to a component that combines the (A) component, the (B) component, and the (C) component.

  According to the lens resin composition of the present invention, a lens having heat resistance capable of withstanding solder reflow and excellent in low water absorption, transparency, and low thermal expansion can be formed. And the obtained lens can be utilized suitably for various electronic components.

The (A) component cage silsesquioxane has two or more aliphatic unsaturated bonds in one molecule. As a particularly preferred example of such a cage silsesquioxane, the following average composition formula (1)
[R ¹ SiO _3/2 ] _n [R ¹ R ² ₂ SiO _1/2 ] _m (1)
(However, R ¹ is a group having a vinyl group, an allyl group, an alkyl group, an aryl group, a (meth) acryloyl group or an oxirane ring, and at least two of the (m + n) R ¹ groups are unsaturated divalent groups. 1 or 2 or more reactive functional groups selected from the group consisting of a vinyl group having a heavy bond, an allyl group, and a group having a (meth) acryloyl group, and R ² represents a methyl group. M is a number from 1 to 4, n is a number from 8 to 16, the sum of m and n is a number from 10 to 20, and the number average molecular weight (Mn) is from 500 to 5,000. This is a cage-type siloxane having a molecular weight dispersity (Mw / Mn) of 1.0 to 3.5. Mw represents a weight average molecular weight.

(A) About the preferable means to obtain the cage silsesquioxane of a component, following General formula (3)
R ¹ SiX ₃ (3)
(Where 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 X is selected from the group consisting of an alkoxy group, a halogen atom and a hydroxyl group. Using a single or a plurality of silicon compounds represented by a hydrolyzable group), a basic catalyst is used to hydrolyze with one or both of a nonpolar solvent and a polar solvent and to condense one part. The polycondensate obtained was further recondensed in the presence of a nonpolar solvent and a basic catalyst, and the resulting recondensation product was further added to the following general formula (4).
[R ¹ R ² ₂ Si] ₂ O (4)
(However, R ¹ is a group having a vinyl group, an allyl group, an alkyl group, an aryl group, a (meth) acryloyl group, or an oxirane ring, and R ² represents a methyl group.) It is good to obtain by reaction.

Examples of structural formulas of the cage silsesquioxane (A) are shown in the following formulas (5) to (11), respectively. Structural formula (5) is m = 2, n = 8, (6) is m = 3, n = 9, (7) is m = 2, n = 10, (8) is m = 3, n = 11, (9) is m = 2, n = 12, (10) is m = 3, n = 13, and (11) is m = 2, n = 14. In addition, the cage silsesquioxane of the component (A) is not limited to the following formulas (5) to (11). In the structural formulas (5) to (11), R ¹ and R ² are the same as the average composition formula (1).

Regarding a preferable means for obtaining the cage silsesquioxane of component (A), first, the silicon compound represented by the general formula (3) is converted into one of a nonpolar solvent and a polar solvent in the presence of a basic catalyst. Alternatively, the hydrolysis reaction is performed in a solvent in which both are combined. In general formula (3), R ¹ is an organic group selected from a vinyl group, a phenyl group, an alkyl group, a (meth) acryloyl group, an allyl group, or a group having an oxirane ring.

  Preferred compounds among the silicon compounds represented by the general formula (3) include phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, methacryloxymethyltrimethoxysilane , Methacryloxymethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acrylo Xylpropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexylethyl) trimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane , P-styryltriethoxysilane, p-styryltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane. Of these, phenyltrimethoxysilane, methyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and vinyltrimethoxysilane, which are easily available, are more preferable.

  Examples of the basic catalyst used in the hydrolysis reaction include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, cesium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, Examples thereof include ammonium hydroxide salts such as benzyltrimethylammonium hydroxide and benzyltriethylammonium hydroxide. Among these, tetramethylammonium hydroxide is preferably used because of its high catalytic activity. The basic catalyst is usually used as an aqueous solution.

  Regarding the hydrolysis reaction conditions, the reaction temperature is preferably 0 to 60 ° C, more preferably 20 to 40 ° C. When the reaction temperature is lower than 0 ° C., the reaction rate becomes slow and the hydrolyzable group remains in an unreacted state, resulting in a long reaction time. 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, the hydrolysis product is increased in molecular weight. The reaction time is preferably 2 hours or more. If the reaction time is less than 2 hours, the hydrolysis reaction does not proceed sufficiently and the hydrolyzable group remains in an unreacted state.

  In the hydrolysis reaction, the presence of water is essential, but this can be supplied from an aqueous solution of a basic catalyst or may be added as water separately. The amount of water is not less than an amount sufficient to hydrolyze the hydrolyzable group, preferably 1.0 to 1.5 times the theoretical amount. In addition, one or both of a nonpolar solvent and a polar solvent are used during hydrolysis. Preferably both are used or only polar solvents are used. As the polar solvent, alcohols such as methanol, ethanol, 2-propanol, or other polar solvents can be used. Preferred are lower alcohols having 1 to 6 carbon atoms that are soluble in water, and 2-propanol is more preferred. When only a nonpolar solvent is used, the reaction system is not uniform and the polymer is likely to precipitate during the reaction.

  After completion of the hydrolysis reaction, the reaction solution is neutralized with a weakly acidic solution to make it neutral or acidic, and then water or a water-containing reaction solvent is separated. Separation of the water or the water-containing reaction solvent can employ means such as washing the solution with a saline solution to sufficiently remove moisture and other impurities, and then drying with a drying agent such as anhydrous magnesium sulfate. When a polar solvent is used, means such as evaporation under reduced pressure can be employed. After removing the polar solvent, a nonpolar solvent is added to dissolve the polycondensate, and washing and drying are performed in the same manner as described above. For weakly acidic solutions, sulfuric acid diluted solution, hydrochloric acid diluted solution, citric acid solution, acetic acid, ammonium chloride aqueous solution, malic acid solution, phosphoric acid solution, oxalic acid solution and the like are used. If the nonpolar solvent is separated by means such as evaporation, the hydrolysis reaction product can be recovered. If the nonpolar solvent can be used as the nonpolar solvent used in the next reaction, it is separated. do not have to.

  In the hydrolysis reaction to obtain the (A) component cage silsesquioxane, a condensation reaction of the hydrolyzate occurs together with the hydrolysis. The polycondensate accompanied by the condensation reaction of the hydrolyzate usually becomes a colorless viscous liquid having a number average molecular weight of 500 to 7000. Although the polycondensate varies depending on the reaction conditions, it becomes a resin (or oligomer) having a number average molecular weight of 500 to 3000, and most, preferably almost all, of the hydrolyzable group X represented by the general formula (3) is an OH group. And most of the OH group, preferably 95% or more, is condensed.

  Regarding the structure of the polycondensate, there are several types of cage-type, ladder-type, and random-type siloxanes, and even for compounds that have a cage-type structure, the percentage of the complete cage-type structure is small, and part of the cage is opened. The incomplete cage type structure is mainly. The polycondensate is further heated in the presence of a nonpolar solvent and a basic catalyst to condense the siloxane bond (referred to as recondensation) to selectively produce a recondensate (a siloxane having a cage structure). That is, after separating water or a water-containing reaction solvent from the polycondensate, a recondensation reaction is performed in the presence of a nonpolar solvent and a basic catalyst. Regarding the reaction conditions for the recondensation reaction, the reaction temperature is preferably in the range of 90 to 200 ° C, more preferably 100 to 140 ° C. If the reaction temperature is too low, a sufficient driving force is not obtained for the recondensation reaction, and the reaction does not proceed. If the reaction temperature is too high, the reactive organic functional group may cause a self-polymerization reaction. Therefore, it is necessary to suppress the reaction temperature or add a polymerization inhibitor or the like. The reaction time is preferably 2 to 12 hours. The amount of the nonpolar solvent used is preferably an amount sufficient to dissolve the hydrolysis reaction product, and the amount of the basic catalyst used is in the range of 0.1 to 5 wt% with respect to the recondensate. More preferably, it is in the range of 0.5 to 2.0 wt%.

  Any nonpolar solvent may be used as long as it is insoluble or hardly soluble in water, but a hydrocarbon solvent is preferred. Examples of the hydrocarbon solvent include nonpolar solvents having a low boiling point such as toluene, benzene, and xylene. Among them, toluene is preferably used. On the other hand, as the basic catalyst, a basic catalyst used in the hydrolysis reaction can be used. Alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and cesium hydroxide, tetramer ammonium ammonium hydroxide, tetraethyl Examples thereof include ammonium hydroxide salts such as ammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and benzyltriethylammonium hydroxide, but a catalyst that is soluble in a nonpolar solvent such as tetraalkylammonium is preferable.

  The hydrolysis product used for recondensation is preferably washed, dehydrated and concentrated, but can be used without washing and dehydration. In this reaction, water may be present, but it is not necessary to add it positively, and it is preferable that the water is brought to the extent of water brought from the basic catalyst solution. In addition, when hydrolysis of the polycondensate is not sufficiently performed, water of a theoretical amount or more necessary for hydrolyzing the remaining hydrolyzable group is necessary. After the recondensation reaction, the catalyst is washed away with water and concentrated to obtain a recondensate.

Next, by adding a disiloxane compound to the recondensate obtained above, the cage silsesquioxane of component (A) can be obtained. Specifically, the disiloxane compound can be represented by the following general formula (4). In addition, for the reaction when adding the disiloxane compound to the recondensate, nonpolar solvents such as toluene, benzene and xylene, and basic such as tetramerammonium hyhydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, etc. It is good to carry out in presence of a catalyst.
(R ¹ R ² ₂ Si) ₂ O (4)
(However, R ¹ is one or two groups selected from a vinyl group, an allyl group, an alkyl group, an aryl group, a (meth) acryloyl group, or a group having an oxirane ring, and R ² is a methyl group. Show.)

  The addition reaction under the base catalyst between the recondensate and the disiloxane compound represented by the general formula (4) is an equilibration reaction, and a silicon atom unit (T It is necessary to preferentially carry out the former (cleavage of the recondensate) as much as possible because it is a competitive reaction of increasing the molecular weight of the recondensate composed of units) or by using the recondensate alone. In addition, since this reaction is basically an equilibrium reaction, the number average molecular weight Mn, yield, and production rate of the vertical silsesquioxane (A) component having a reactive functional group at the end of the target product are The reaction temperature, the reaction time, the ratio of both raw materials added, the amount of alkali catalyst, etc. are naturally determined, and therefore, the reaction is preferably carried out under the conditions described below.

  That is, the recondensate obtained above is added with a disiloxane compound represented by the general formula (4) in the presence of a nonpolar solvent and a basic catalyst. Regarding the reaction conditions, the reaction temperature is preferably in the range of 90 to 200 ° C, more preferably 100 to 140 ° C. However, for those having a low boiling point of the disiloxane compound represented by the general formula (4), the reaction temperature may exceed the boiling point and evaporate out of the reaction system. . Under basic conditions, the siloxane bond that forms the recondensed cage is in equilibrium between the cleavage and the bond, but in the presence of the disiloxane compound, the cleaved portion reacts with the disiloxane compound so that a portion of the cage is A cage-cleavable siloxane resin is obtained which is stable in the cleaved state. The cage-cleavage-type siloxane here refers to a siloxane molecular structure in which an incomplete cage structure is formed by breaking at least one of the siloxane bonds forming the cage structure. The reaction time is preferably 1 to 5 hours.

The amount of the nonpolar solvent used is preferably an amount sufficient to dissolve the recondensate. On the other hand, the reaction ratio between the recondensate and the disiloxane compound is 0 for the disiloxane compound per 1 mol of the structural unit represented by [R ¹ SiO _1.5 ] ₁₀ corresponding to 10 T units of the recondensate. It is good to carry out hydrolysis addition so that it may become 0.5-4.0 mol, Preferably it is 1.0-2.0 mol. If the disiloxane compound is less than this range, the reaction does not proceed. If the disiloxane compound is more than this range, the unreacted product may adversely affect the physical properties of the product. For example, when a highly volatile disiloxane compound such as hexamethyldisiloxane or 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is used, the amount volatilized during the reaction. Considering the above, it may be possible to set a larger amount.

As for the amount of basic catalyst used in which addition of disiloxane compound Saichijimigo was to structural units to 1 mol of the re-condensation product represented by [R ¹ SiO _{1.5] 10,} a basic catalyst In an amount of 0.05 to 0.15 mol, preferably 0.06 to 0.1 mol.

  Among the disiloxane compounds represented by the general formula (4), 1,3-diphenyl-1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, hexaethyldisiloxane, Hexaphenyldisiloxane, pentamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,3,3-tetravinyldimethyldisiloxane, 1,3-diethyl-1,1,3,3 -Tetramethyldisiloxane, 1,3-di-n-propyl-1,1,3,3-tetramethyldisiloxane, 1,3-dibutyl-1,1,3,3-tetramethyldisiloxane, 1,3 -Dipentyl-1,1,3,3-tetramethyldisiloxane, 1,3-dioctyl-1,1,3,3-tetramethyldisiloxane, 1,3-dimethacryloxymethyl-1,1,3, 3-tetramethyldisiloxane, 1,3-di (3-methacryloxypropyl) -1,1,3,3-tetramethyldisiloxane, 1,3-diacryloxymethyl-1,1,3,3- Tetra Tildisiloxane, 1,3-di (3-acryloxypropyl) -1,1,3,3-tetramethyldisiloxane, 1,3-di (3-glycidoxypropyl) -1,1,3, 3-tetramethyldisiloxane, bis- [2- (3,4-epoxycyclohexyl) ethyl] -tetramethyldisiloxane, 1,3-diallyl-1,1,3,3-tetramethyldisiloxane, 1,2- Examples include di-p-styryl-1,1,3,3-tetramethyldisiloxane and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane.

  As described above, the vertical silsesquioxane of the component (A) has the general formula (1) in which m is a number from 1 to 4, n is a number from 8 to 16, and m and n In many cases, the sum is obtained as a mixture of compounds represented by structural formulas (5) to (11) represented by a number of 10 to 20.

  Next, the organohydrogenpolysiloxane of component (B) has two or more SiH groups in one molecule. The (B) component organohydrogenpolysiloxane acts as a cross-linking agent, and the cured product is formed by an addition reaction between the SiH group in the component and the unsaturated bond in the component (A) and component (C). To form. Since this addition reaction proceeds from a low temperature when the resin composition is thermally cured, the rapid radical polymerization reaction of (meth) acrylate due to the decomposition of the organic peroxide can be suppressed, and the entire curing reaction is moderated. Can be advanced.

The organohydrogenpolysiloxane as component (B) is particularly preferably the following average composition formula (2)
[H _a (R ³ ) _b SiO _{(4-ab) / 2} ] _l (2)
Wherein R ³ is one or more substituted or unsubstituted monovalent hydrocarbon groups not containing an aliphatic unsaturated bond, and a and b are 0.001 ≦ a <2, 0.7 ≦ b ≦ 2 and 0.8 ≦ a + b ≦ 3), and the repeating unit 1 is 3 to 300, and 2 hydrogen atoms bonded to silicon atoms (SiH groups) are included in one molecule. An organohydrogensilicone oligomer having at least one is preferable. The position of the hydrogen atom bonded to the silicon atom is not particularly limited, and may be at the end of the molecule or in the middle.

Here, the monovalent hydrocarbon group represented by R ³ in the above formula (2) is preferably a group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, or an isopropyl group. Butyl group, isobutyl group, t-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group and other alkyl groups, phenyl group, tolyl group, xylyl group, naphthyl group, etc. Aralkyl groups such as an aryl group, benzyl group, phenylethyl group, phenylpropyl group, etc., and a part or all of the hydrogen atoms in these monovalent hydrocarbon groups may be halogens such as fluorine, bromine and chlorine. Substituted with an atom, a cyano group, etc., for example, a halogen-substituted alkyl group such as a chloromethyl group, a chloropropyl group, a bromoethyl group, a trifluoropropyl group, Anoechiru group, and the like.

Specific examples of the organohydrogenpolysiloxane include trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both ends, trimethylsiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer at both ends, and dimethylhydrogensiloxy group-blocked dimethyl at both ends. Polysiloxane, both ends dimethylhydrogensiloxy group-blocked methylhydrogensiloxane / methylphenylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy group-blocked methylhydro Gensiloxane / diphenylsiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane Methylsiloxane copolymer, (CH _{3) 2} HSiO copolymers consisting of _1/2 units and SiO _4/2 units, and, (CH ₃₎ and ₂ HSiO _1/2 units and SiO _4/2 units (C ₆ H ₅ ) Copolymers composed of SiO _3/2 units. The molecular structure of the organohydrogenpolysiloxane may be any of linear, cyclic, branched, and three-dimensional network structures.

Such organohydrogenpolysiloxanes are usually R ³ SiHCl ₃ , (R ³ ) ₃ SiCl, (R ³ ) ₂ SiCl ₂ , or (R ³ ) ₃ SiHCl (R ³ is as described above). It can be obtained by hydrolyzing or by equilibrating the siloxane obtained by hydrolysis.

  The compounding amount of the organohydrogenpolysiloxane in the lens molding resin composition needs to be an effective amount necessary for curing the component (A), specifically, the unsaturated bond of the component (A). The ratio of the number of bases (for example, vinyl group) and the number of SiH groups in the component (B) is 1: 0.1 to 2.0, preferably 1: 0.1 to 1.5, more preferably 1: 0.1 to 1. Use at a ratio of zero. When the number of SiH groups in component (B) is less than 0.1 relative to the number of unsaturated bond groups in component (A), curing by addition reaction does not proceed, and (meth) acrylic groups react rapidly due to decomposition of the peroxide. However, it is difficult to obtain a cured product. On the other hand, if it exceeds 2.0, a large amount of unreacted SiH groups are present in the cured product, which causes the physical properties to change over time.

  The (C) component ethylenically unsaturated compound is an ethylenically unsaturated compound having two or more (meth) acryloyl groups in one molecule. Specific examples of the component (C) include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dimethylol-tricyclodecane di (meth) acrylate, di (meth) acrylate ester of bisphenol A type epoxy compound, trimethylolpropane tri Although (meth) acrylate etc. are mentioned, the ethylenically unsaturated compound which has one (meth) acryloyl group in 1 molecule can also be used together.

  About the compounding quantity of the ethylenically unsaturated compound of (C) component, the (meth) acryl mole number per 100g of resin components consisting of (A) component, (B) component, and (C) component seems to exceed 0.2. Blend in. Below this range, a phenomenon that the molded product becomes clouded under high temperature and high humidity conditions is observed. However, if it exceeds 0.8, the water absorption rate increases and the reliability decreases, which is not preferable. In this case, the preferable water absorption range is less than 1%. The number of moles of (meth) acrylic per 100 g of resin component consisting of (A) component, (B) component and (C) component is (weight of (A) component per 100 g of resin component / (meta) of (A) component ) Acrylic equivalent) + (weight of component (C) per 100 g of resin component / (meth) acrylic equivalent of component (C)).

  As the curing catalyst for the component (D), the addition reaction between the aliphatic unsaturated bond of the components (A) and (C) and the SiH group of the component (B) can proceed, and (A) What is necessary is just to be able to advance the unsaturated bond of a component and (C) component by radical polymerization reaction. Preferably, a platinum group metal catalyst that allows the former addition reaction to proceed and an organic peroxide that can cause the latter radical polymerization reaction to proceed. That is, it is preferable to use two types of curing catalysts having different catalytic actions in combination.

Of these, platinum group metal catalysts include platinum chloride, chloroplatinic acid, chloroplatinic acid and alcohol complexes, chloroplatinic acid and aldehyde complexes, chloroplatinic acid and ketone complexes, chloroplatinic acid and Examples include complexes with olefins, complexes of platinum and vinyl siloxane, and dicarbonyldichloroplatinum. Among these, chloroplatinic acid, a complex of chloroplatinic acid and an olefin, and a complex of platinum and vinylsiloxane are preferable from the viewpoint of catalytic activity. Specifically, Pt ⁰ · CO · (CH ₂ = CH (CH ₃ ) SiO) ₄ , Pt ⁰ · 1.5 [(CH ₂ = CH (CH ₃ ) ₂ Si) ₂ O], Pt ⁰ · (CH ₂ = CH (CH ₃ ) SiO) ₄ , Pt ⁰ · (HC (O) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ), etc. is not. Moreover, these may be used independently and may use 2 or more types together.

  Examples of the organic peroxide include ketone peroxides, diacylalkyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, and carbonates. Among these, dialkyl peroxide is preferable from the viewpoint of catalytic activity. Specifically, cyclohexanone peroxide, 1,1-bis (t-hexaperoxy) cyclohexanone, cumene hydroperoxide, dicumyl peroxide, benzoyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t -Hexylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexanoate and the like can be exemplified, but are not limited thereto. These may be used alone or in combination of two or more.

  About the addition amount of a platinum group-type metal catalyst, 0.001-0.1 weight part as a metal atom with respect to a total of 100 weight part of (A) component, (B) component, and (C) component, More preferably It is preferable to add in the range of 0.002 to 0.05 parts by weight. If this addition amount is less than 0.001 part by weight, the progress of the addition reaction between the SiH group in the component (B) and the unsaturated bond in the component (A) and the component (C) is slow and the organic peroxide is decomposed. The rapid radical polymerization reaction of (meth) acrylate due to the above cannot be suppressed. On the other hand, when the amount exceeds 0.1 parts by weight, there is a problem that the addition reaction proceeds rapidly and the pot life is short. The amount of the organic peroxide added is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight in total of the components (A), (B) and (C). More preferably, it is 01-5 weight part. If the amount of the organic peroxide added is less than 0.01 parts by weight, curing will be insufficient, and the strength and rigidity of the molded product will be lowered. On the other hand, if it exceeds 5 parts by weight, problems such as coloring of the molded product will occur. There is a fear.

  The lens resin composition of the present invention is prepared by uniformly blending the above-mentioned components, but is stored in two liquids so that curing does not proceed, and the two liquids are mixed and cured at the time of use. You may do it. Of course, a small amount of a curing inhibitor such as acetylene alcohol can be added and used as one liquid.

  Further, in the lens resin composition of the present invention, as long as the transparency is not hindered, a conventionally known antioxidant, ultrafine silica such as Aerosil, an inorganic filler matched to a resin whose refractive index is cured May be appropriately blended from the viewpoint of improving the mechanical strength and adjusting the thermal expansion coefficient.

  The resin composition for lenses of the present invention can obtain a cured product by thermosetting. In addition, a lens having a predetermined shape can be obtained by injection molding or compression molding. When molding a lens by injection molding, etc., it is possible to use a one-component type, but the two-component type has a longer pot life and is easier to handle. What is necessary is just to inject | pour the mixed thing into an injection molding apparatus, and to shape | mold. The molding apparatus used at this time is not particularly limited. Moreover, about the conditions which harden | cure a resin composition, although it depends also on sclerosis | hardenability of a resin composition, it can be normally hardened in about 30-180 second in the range of 120-200 degreeC. In this case, you may make it perform post-cure (additional heating) on the conditions of 100-200 degreeC and 5 minutes-4 hours as needed.

  The lens resin composition of the present invention can produce various lenses, and is excellent in heat resistance, low water absorption, transparency, and low thermal expansion. It is also possible to replace the lens with a resin composition. In addition, the cured product made of the resin composition of the present invention also has heat resistance that can withstand solder reflow, and therefore, for example, a CCD with a lens mounted on a mobile phone, a digital camera, an in-vehicle camera, a CMOS sensor with a lens, etc. As described above, the present invention can be applied to electronic parts such as a camera module in which a semiconductor and a lens are integrated, and can also be used for glass substitute materials such as a diffraction grating, a polarizing part, and a reflecting mirror.

  Hereinafter, preferred embodiments of the present invention will be described based on synthesis examples, examples and comparative examples, but the present invention is not limited to the following contents.

[Synthesis Example 1]
In a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer, 150 mL of toluene and 85 mL of 2-propanol are placed as a solvent, and 37.2 g of a 5 wt% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) is added as a basic catalyst. I put it in. To the dropping funnel, 25 mL of toluene and 50.3 g of trimethoxyvinylsilane (KBM1003 manufactured by Shin-Etsu Chemical Co., Ltd.) were added, and a toluene solution of trimethoxyvinylsilane was added dropwise at room temperature over 3 hours while stirring the reaction vessel. 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. The reaction solution was neutralized with 23.0 g of 10 wt% aqueous citric acid solution, washed with saturated brine, and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 20.6 g of a polycondensate.

Next, 15.0 g of the polycondensate obtained above, 380 mL of toluene, and 1.72 g of 5 wt% TMAH aqueous solution were placed in a reaction vessel equipped with a stirrer, a Dinsterk, a condenser, and a thermometer, and the temperature was 120 ° C. While removing water, toluene was heated to reflux to carry out a recondensation reaction. After stirring for 3 hours after refluxing toluene, the reaction was terminated by returning to room temperature. The reaction solution was neutralized with 23.0 g of 10 wt% citric acid, washed with saturated brine, and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain a recondensate. Finally, 14.5 g of the recondensate obtained above in a reaction vessel equipped with a stirrer, a Din Stark and a cooling tube, 300 mL of toluene, 3.0 g of 5 wt% TMAH aqueous solution and 1,3-divinyl-1,1 , 3,3-Tetramethyldisiloxane (TMDVDS: LS7250 manufactured by Shin-Etsu Chemical Co., Ltd.) 9.76 g was added, and toluene was refluxed and heated for equilibration at 120 ° C. to perform an equilibration reaction. After stirring for 3 hours after refluxing toluene, the reaction was terminated by returning to room temperature. The reaction solution was neutralized with 3.24 g of a 10 wt% citric acid aqueous solution and then concentrated to obtain a cage silsesquioxane having the following average composition formula (12). The obtained cage-type siloxane was a colorless viscous liquid soluble in various organic solvents.
[CH ₂ = CHSiO _3/2 ] _n [CH ₂ = CH (CH ₃ ) ₂ SiO _1/2 ] _m (12)

When ¹ H-NMR of the above cage silsesquioxane (12) was measured, the peak integration ratio of 5.8 to 6.2 ppm multiples by vinyl group and 0.17 ppm by methyl group was 30. 8 was methyl group 6.

  Moreover, the result of having measured GPC of the said cage silsesquioxane (12) is shown in FIG. The cage silsesquioxane (12) had Mn = 1049 and Mw / Mn = 1.17.

  FIG. 2 shows the results of mass spectrometry of the cage siloxane (12) by liquid chromatography atmospheric pressure ionization analyzer (LC / APCl-MS). Table 3 summarizes the main peaks detected by mass spectrometry and the numerical values applicable to n and m of the corresponding cage silsesquioxane (12). The detected peak m / z is the addition of ammonium ions to the molecular weight of the cage silsesquioxane (12) (where m is 1 to 4 and n is 8 to 16). It is the value.

  As a result of measuring the vinyl equivalent of the above cage-type siloxane (12) by the iodine value method, 82 g / eq. Met.

[Synthesis Example 2]
In a reaction vessel equipped with a stirrer, a dropping funnel, and a thermometer, 150 mL of toluene and 85 mL of 2-propanol are placed as a solvent, and 37.2 g of a 5 wt% tetramethylammonium hydroxide aqueous solution (TMAH aqueous solution) is added as a basic catalyst. I put it in. In a dropping funnel, 25 mL of toluene, 25.2 g of trimethoxyvinylsilane (KBM1003 manufactured by Shin-Etsu Chemical Co., Ltd.), and 23.1 g of trimethoxymethylsilane (SZ-6070 manufactured by Toray Dow Corning Silicone Co., Ltd.) were added, and the reaction vessel was stirred. Then, a toluene solution of trimethoxyvinylsilane and trimethoxymethylsilane 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. The reaction solution was neutralized with 23.0 g of 10 wt% aqueous citric acid solution, washed with saturated brine, and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain 20.6 g of a polycondensate.

Next, 15.0 g of the polycondensate obtained above, 380 mL of toluene, and 1.72 g of 5 wt% TMAH aqueous solution were placed in a reaction vessel equipped with a stirrer, a Dinsterk, a condenser, and a thermometer, and the temperature was 120 ° C. While removing water, toluene was heated to reflux to carry out a recondensation reaction. After stirring for 3 hours after refluxing toluene, the reaction was terminated by returning to room temperature. The reaction solution was neutralized with 23.0 g of 10 wt% citric acid, washed with saturated brine, and dried over anhydrous magnesium sulfate. Anhydrous magnesium sulfate was filtered off and concentrated to obtain a recondensate. Finally, 14.5 g of the recondensate obtained above in a reaction vessel equipped with a stirrer, a Din Stark and a cooling tube, 300 mL of toluene, 3.0 g of 5 wt% TMAH aqueous solution and 1,3-divinyl-1,1 , 3,3-Tetramethyldisiloxane (TMDVDS: LS7250 manufactured by Shin-Etsu Chemical Co., Ltd.) 9.76 g was added, and toluene was refluxed and heated for equilibration at 120 ° C. to perform an equilibration reaction. After stirring for 3 hours after refluxing toluene, the reaction was terminated by returning to room temperature. The reaction solution was neutralized with 3.24 g of a 10 wt% citric acid aqueous solution and then concentrated to obtain a cage silsesquioxane having the following average composition formula (13). The obtained cage-type siloxane was a colorless viscous liquid soluble in various organic solvents.
[CH ₂ = CHSiO _3/2 ] _n [CH ₃ SiO _3/2 ] _k [CH ₂ = CH (CH ₃ ) ₂ SiO _1/2 ] _m (13)

When the ¹ H-NMR of the above cage silsesquioxane (13) was measured, the peak integration ratio of 5.8 to 6.2 ppm multiples by vinyl group and 0.17 ppm by methyl group was 21. The methyl group was 27.3 with respect to 5.

  The result of measuring the GPC of the cage silsesquioxane (13) is shown in FIG. The cage silsesquioxane (13) had Mn = 876 and Mw / Mn = 1.19.

  As a result of measuring the vinyl equivalent of the cage-type siloxane (13) by the iodine value method, 131 g / eq. Met.

で示される両末端ジメチルハイドロジェンシロキシ基封鎖メチルハイドロジェンシロキサン・メチルフェニルシロキサン共重合体（ＨＰＭ−５０２：Ｍｎ＝１６３８、ｊ：ｉ＝１：１、ＳｉＨ当量＝２０８ｇ／ｅｑ．：アズマックス株式会社）を３８重量部、（Ｃ）成分である下記式（１５）

で示されるジメチロール-トリシクロデカンジアクリレート（ＤＣＰＡ：共栄社化学）を３３重量部、（Ｄ）成分である２．３ｗｔ％白金・シクロビニルメチルシロキサン錯体を０．４重量部及び（Ｄ）成分であるジ−ｔ−ブチルパーオキサイド（パーブチルＤ：日本油脂）を０．１重量部加え、よく撹拌し、実施例１のレンズ用樹脂組成物として調製した。この樹脂成分の「（Ａ）成分の不飽和結合基数」：「（Ｂ）成分のＳｉＨ基数」は１：０．５であり、（Ａ）成分、（Ｂ）成分及び（Ｃ）成分よりなる樹脂成分１００ｇあたりの（メタ）アクリルモル数は、（樹脂成分１００ｇあたりの（Ａ）成分の重量／（Ａ）成分の（メタ）アクリル当量）＋（樹脂成分１００ｇあたりの（Ｃ）成分の重量／（Ｃ）成分の（メタ）アクリル当量）＝２９／０＋３３／１５２＝０．２２である。 29 parts by weight of the cage silsesquioxane (12) obtained in Synthesis Example 1 as the component (A) and the following formula (14) as the component (B)

Dimethylhydrogensiloxy group-blocked methylhydrogensiloxane / methylphenylsiloxane copolymer (HPM-502: Mn = 1638, j: i = 1: 1, SiH equivalent = 208 g / eq .: Asmax Co., Ltd.) ) Is 38 parts by weight, and component (C) is the following formula (15)

33 parts by weight of dimethylol-tricyclodecane diacrylate (DCPA: Kyoeisha Chemical Co., Ltd.) represented by the following formula: 0.4 parts by weight of component (D) 2.3 wt% platinum-cyclovinylmethylsiloxane complex and component (D) 0.1 parts by weight of a certain di-t-butyl peroxide (perbutyl D: Japanese fats and oils) was added and stirred well to prepare a lens resin composition of Example 1. This resin component has “the number of unsaturated bonds in component (A)”: “the number of SiH groups in component (B)” is 1: 0.5, and consists of component (A), component (B), and component (C). The number of moles of (meth) acrylic per 100 g of resin component is (weight of component (A) per 100 g of resin component / (meth) acrylic equivalent of component (A)) + (weight of component (C) per 100 g of resin component) / (C) component (meth) acryl equivalent) = 29/0 + 33/152 = 0.22.

22 parts by weight of the cage silsesquioxane (12) obtained in Synthesis Example 1 as the component (A), 28 parts by weight of HPM-502 as the component (B), and 50% of DCPA as the component (C) Example 2 0.4 parts by weight of 2.3 wt% platinum / cyclovinylmethylsiloxane complex as component (D) and 0.1 part by weight of perbutyl D as component (D) were added and stirred well. The lens resin composition was prepared. This resin component has “the number of unsaturated bonds in component (A)”: “the number of SiH groups in component (B)” is 1: 0.5, and consists of component (A), component (B), and component (C). The number of moles of (meth) acrylic per 100 g of resin component is 22/0 + 50/152 = 0.33.

  22 parts by weight of the cage silsesquioxane (12) obtained in Synthesis Example 1 as the component (A), 28 parts by weight of HPM-502 as the component (B), and 50% of DCPA as the component (C) Example 2 0.4 parts by weight of 2.3 wt% platinum / cyclovinylmethylsiloxane complex as component (D) and 0.5 parts by weight of perbutyl D as component (D) were added and stirred well. The lens resin composition was prepared. This resin component has “the number of unsaturated bonds in component (A)”: “the number of SiH groups in component (B)” is 1: 0.5, and consists of component (A), component (B), and component (C). The number of moles of (meth) acrylic per 100 g of resin component is 22/0 + 50/152 = 0.33.

  40 parts by weight of the cage silsesquioxane (12) obtained in Synthesis Example 1 as the component (A), 10 parts by weight of HPM-502 as the component (B), and 50% of DCPA as the component (C) Example 4 0.4 parts by weight of 2.3 wt% platinum / cyclovinylmethylsiloxane complex as component (D) and 1.0 part by weight of perbutyl D as component (D) were added and stirred well. The lens resin composition was prepared. This resin component has “the number of unsaturated bonds in component (A)”: “the number of SiH groups in component (B)” is 1: 0.1, and consists of component (A), component (B) and component (C). The number of moles of (meth) acrylic per 100 g of the resin component is 40/0 + 50/152 = 0.33.

で示される両末端トリメチルシロキシ基封鎖メチルハイドロジェンシロキサン・ジメチルシロキサン共重合体（ＨＭＳ−５０１：Ｍｎ＝９００−１２００、ｈ：ｇ＝１：０．７５：ＳｉＨ当量＝１３５ｇ／ｅｑ．：アズマックス株式会社）を２３重量部、（Ｃ）成分であるＤＣＰＡを５０重量部、（Ｄ）成分である２．３ｗｔ％白金・シクロビニルメチルシロキサン錯体を０．４重量部及び（Ｄ）成分であるパーブチルＤを１．０重量部加え、よく撹拌し、実施例５のレンズ用樹脂組成物として調製した。この樹脂成分の「（Ａ）成分の不飽和結合基数」：「（Ｂ）成分のＳｉＨ基数」は１：０．５であり、（Ａ）成分、（Ｂ）成分及び（Ｃ）成分よりなる樹脂成分１００ｇあたりの（メタ）アクリルモル数は、２７／０＋５０／１５２＝０．３３である。 27 parts by weight of the cage silsesquioxane (12) obtained in Synthesis Example 1 as the component (A) and the following formula (16) as the component (B)

A methylhydrogensiloxane / dimethylsiloxane copolymer blocked with trimethylsiloxy groups at both ends (HMS-501: Mn = 900-1200, h: g = 1: 0.75: SiH equivalent = 135 g / eq .: ASMAX stock Company) 23 parts by weight, component (C) DCPA 50 parts by weight, component (D) 2.3 wt% platinum-cyclovinylmethylsiloxane complex 0.4 parts by weight and component (D) perbutyl 1.0 part by weight of D was added and stirred well to prepare a lens resin composition of Example 5. This resin component has “the number of unsaturated bonds in component (A)”: “the number of SiH groups in component (B)” is 1: 0.5, and consists of component (A), component (B), and component (C). The number of moles of (meth) acrylic per 100 g of the resin component is 27/0 + 50/152 = 0.33.

  19 parts by weight of the cage silsesquioxane (13) obtained in Synthesis Example 2 as the component (A), 31 parts by weight of HPM-502 as the component (B), and 50 DCPA as the component (C) Example 6 0.4 parts by weight of 2.3 wt% platinum / cyclovinylmethylsiloxane complex as component (D) and 1.0 part by weight of perbutyl D as component (D) were added and stirred well. The lens resin composition was prepared. The resin component “(A) component unsaturated bond group number”: “(B) component SiH group number” is 1: 1, and the resin component is composed of (A) component, (B) component and (C) component. The number of moles of (meth) acrylic per 100 g is 19/0 + 50/152 = 0.33.

で示されるトリメチロールプロパントリ（メタ）アクリレート（ＴＭＰＴＡ：共栄社株式会社）を２５重量部、（Ｄ）成分である２．３ｗｔ％白金・シクロビニルメチルシロキサン錯体を０．４重量部及び（Ｄ）成分であるパーブチルＤを１．０重量部加え、よく撹拌し、実施例７のレンズ用樹脂組成物として調製した。この樹脂成分の「（Ａ）成分の不飽和結合基数」：「（Ｂ）成分のＳｉＨ基数」は１：０．５であり、（Ａ）成分、（Ｂ）成分及び（Ｃ）成分よりなる樹脂成分１００ｇあたりの（メタ）アクリルモル数は、２２／０＋２５／１５２＋２５／９９＝０．４２である。 22 parts by weight of the cage silsesquioxane (12) obtained in Synthesis Example 1 as the component (A), 28 parts by weight of HPM-502 as the component (B), and 25 DCPA as the component (C) The following formula (17) which is part by weight and component (C)

25 parts by weight of trimethylolpropane tri (meth) acrylate (TMPTA: Kyoeisha Co., Ltd.) represented by the formula: 0.4 parts by weight of component (D) 2.3 wt% platinum-cyclovinylmethylsiloxane complex and (D) The component perbutyl D, 1.0 part by weight, was added and stirred well to prepare a lens resin composition of Example 7. This resin component has “the number of unsaturated bonds in component (A)”: “the number of SiH groups in component (B)” is 1: 0.5, and consists of component (A), component (B), and component (C). The number of moles of (meth) acrylic per 100 g of the resin component is 22/0 + 25/152 + 25/99 = 0.42.

[Comparative Examples 1 and 2]
In Example 1, except that the ethylenically unsaturated compound as component (C) was not blended, the same as in Example 1 was used as Comparative Example 1, and 11 parts by weight of DCPA as component (C) was blended (The number of moles of (meth) acrylic per 100 g of the resin component comprising the (A) component, the (B) component, and the (C) component is 29/0 + 11/152 = 0.07). Each of the same samples was prepared as Comparative Example 2.

[Comparative Example 3]
67 parts by weight of the cage silsesquioxane (12) obtained in Synthesis Example 1 as the component (A), 33 parts by weight of DCPA as the component (C), and 2.3 wt% platinum as the component (D) The lens of Comparative Example 3 was added 0.4 parts by weight of cyclovinylmethylsiloxane complex and 0.1 part by weight of component (D) di-t-butyl peroxide (perbutyl D: Nippon Oil & Fats) and stirred well. It was prepared as a resin composition. The number of moles of (meth) acrylic per 100 g of resin component consisting of component (A) and component (C) of this resin component is (weight of (A) component per 100 g of resin component / (meth) acrylic of (A) component. Equivalent) + (weight of component (C) per 100 g of resin component / (meth) acryl equivalent of component (C)) = 67/0 + 33/152 = 0.22.

  Using the compositions prepared in the above examples and comparative examples, it was poured into a mold incorporated in a glass plate to a thickness of 2 mm and heated at 120 ° C. for 1 hour, 150 ° C. for 1 hour, and 180 ° C. for 2 hours. Molding was performed to obtain a molded product for testing of 50 mm × 25 mm × thickness 2 mm. About the obtained molding, the water absorption, the thermal expansion coefficient, the heat resistance after the reflow test, and the transparency were evaluated by the following methods. The results are shown in Tables 1 and 2.

Water absorption: After the molded product was completely dried, it was immersed in water for 24 hours and obtained from the change in weight.
Coefficient of thermal expansion: The coefficient of thermal expansion was determined under the conditions of a heating rate of 5 ° C./min and a compression load of 0.1 N based on a thermomechanical analysis method.
Heat resistance: The thermal deformation after the molding was passed twice continuously through an IR reflow furnace set so that the peak temperature was maintained at 260 ° C. for 15 min was visually observed, and the refractive index (Abago Abbe refractometer) ) And light transmittance (400 nm, 2 mmt). Similarly, the color difference (ΔE) was also measured.
Constant humidity test: The molded product was immersed in warm water at 80 ° C., returned to room temperature after 1 hour, and the state was observed.

1 shows a GPC chart of a cage silsesquioxane obtained in Synthesis Example 1. FIG. FIG. 2 shows the mass spectrometry result of the cage silsesquioxane obtained in Synthesis Example 1. FIG. 3 shows a GPC chart of the cage silsesquioxane obtained in Synthesis Example 2.

Claims (6)

(A) a cage silsesquioxane having two or more aliphatic unsaturated bonds in one molecule;
(B) an organohydrogenpolysiloxane having two or more SiH groups in one molecule;
(C) an ethylenically unsaturated compound having two or more (meth) acrylic groups in one molecule, and (D) a curing catalyst,
Is an essential component, and the ratio of the number of aliphatic unsaturated bond groups in the component (A) to the SiH group in the component (B) is 1: 0.1 to 2.0, and the components (A) and (B) And a resin composition for molding a lens, wherein the number of moles of (meth) acrylic per 100 g of the resin component comprising the component (C) exceeds 0.2. The (A) component siliceous silsesquioxane has the following average composition formula (1)
[R ¹ SiO _3/2 ] _n [R ¹ R ² ₂ SiO _1/2 ] _m (1)
(However, R ¹ is a group having a vinyl group, an allyl group, an alkyl group, an aryl group, a (meth) acryloyl group or an oxirane ring, and at least two of the (m + n) R ¹ groups are unsaturated divalent. 1 or 2 or more types of reactive functional groups selected from the group consisting of a vinyl group having a heavy bond, an allyl group and a group having a (meth) acryloyl group, and R ² represents a methyl group. M is a number from 1 to 4, n is a number from 8 to 16, the sum of m and n is a number from 10 to 20, and the number average molecular weight (Mn) ranges from 500 to 5,000. The resin composition for a lens according to claim 1, wherein the molecular weight dispersity (Mw / Mn) is 1.0 to 3.5. Component (B) is an organohydrogenpolysiloxane having the following average composition formula (2)
[H _a (R ³ ) _b SiO _{(4-ab) / 2} ] _l (2)
(However, R ³ is one or two or more substituted or unsubstituted monovalent hydrocarbon groups not containing an aliphatic unsaturated bond, and a and b are 0.001 ≦ a <2, 0.7 The resin composition for a lens according to claim 1, wherein the resin unit is a repeating unit represented by: ≦ b ≦ 2 and 0.8 ≦ a + b ≦ 3.   The lens resin composition according to claim 1, wherein the curing catalyst comprises two types of platinum group metal catalyst and organic peroxide.   Hardened | cured material which consists of the resin composition for lenses of any one of Claims 1-4.   The lens obtained by shape | molding the resin composition for lenses of any one of Claims 1-4.

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