JP2009258385A - Curable silicone composition for optical lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable silicone composition excellent in resistance against thermal deformation and resistance against thermal discoloration, having sufficient optical characteristics and physical characteristics as a lens material, and useful as a material of an optical lens for a cellular phone with a camera, or the like. <P>SOLUTION: The curable silicone composition for an optical lens contains: (A) an addition reaction product of (a) a specific di(hydrosilyl)benzene compound and (b) a polycyclic hydrocarbon having a carbon-carbon double bond, the addition reaction product having at least two addition-reactive carbon-carbon double bonds; (B) an organic silicon compound having at least three hydrosilyl groups; and (C) a hydrosilylation reaction catalyst. A cured product of the composition has a refractive index of 1.50 or more, Abbe's number of 40 or more and a glass transition temperature of 70°C or higher. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a curable silicone composition for an optical lens containing a polycyclic hydrocarbon skeleton-containing component, which is useful as a plastic lens material, particularly as an optical lens material for a camera-equipped mobile phone.

  In recent years, plastic lenses are suitably used for compact cameras, camera-equipped mobile phones, and the like that are excellent in low cost and portability. As such plastic lens materials, thermoplastic resins such as polymethyl acrylate, polycarbonate, and cyclic olefin polymers are used.

  On the other hand, as a general method of mounting a camera module equipped with such a plastic lens on a camera-equipped mobile phone or the like, a heat-resistant connector is installed on a wiring board, and after heating and reflow wiring at 250 ° C. or higher, the camera There is a way to install modules. However, as a disadvantage of such a camera module mounting method, there are problems such as an increase in thickness due to the mounting of the connector parts, and a cost due to the increased cost and process of the connector parts.

  As a method for solving such a problem, there has been proposed a method in which a camera module is arranged directly on a wiring board and mounted by reflow processing without using a connector component. In this method, connector parts are not required, so that the thickness can be reduced, and the cost can be reduced by shortening the process.

  However, when the above-mentioned thermoplastic plastic material is used in the proposed mounting method, the thermoplastic plastic lens material is melted by the heat of the reflow process, so that there is a drawback that it is deformed or colored.

As a material that compensates for such drawbacks, there is a thermosetting silicone material that is excellent in heat distortion resistance and heat discoloration (for example, Patent Document 1). However, a high refractive index and a high Abbe that are necessary optical characteristics of a lens material. No material has been found that simultaneously satisfies the above numbers and has both high hardness and high glass transition point, which are necessary physical characteristics of a lens.
Electronic materials (September 2005, pages 90-93)

  In view of the above-mentioned problems of the prior art, the present invention can withstand the reflow process, has excellent heat distortion resistance (shape retention), heat resistance discoloration, and sufficient optical characteristics as a lens material (high refractive index, high Abbe Number) and physical properties (high hardness, high glass transition point), curable silicone compositions for optical lenses containing a polycyclic hydrocarbon skeleton-containing component, useful as materials for plastic lenses, especially optical lenses for camera-equipped mobile phones The purpose is to provide goods.

  As a result of intensive studies to achieve the above object, the present inventors have completed the present invention.

That is, the present invention
(A) (a) The following general formula (1):

[Wherein A represents the following general formula (2):

A divalent group selected from the group consisting of groups represented by:
R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
A compound having two hydrogen atoms bonded to a silicon atom represented by
(b) an addition reaction product with a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and the addition-reactive carbon-carbon double bond in one molecule An addition reaction product having at least two
(B) an organosilicon compound having three or more hydrogen atoms bonded to a silicon atom in one molecule, and
(C) A composition containing a hydrosilylation reaction catalyst, wherein the cured product has a refractive index of 1.50 or higher, an Abbe number of 40 or higher, and a glass transition temperature of 80 ° C. or higher. It is to provide.

  The present invention also provides an optical lens made of a cured silicone resin having a refractive index of 1.50 or higher, an Abbe number of 40 or higher, and a glass transition temperature of 70 ° C. or higher, obtained by molding and curing the above composition. It is to provide.

  The curable silicone composition for an optical lens of the present invention is a plastic lens, particularly a camera, in order to give a cured product having a high refractive index and a high Abbe number without causing deterioration of transparency due to thermal deformation or thermal discoloration due to reflow treatment. It is useful as a material for an optical lens for a cellular phone.

  The present invention will be described in detail below.

[Component (A)]
The component (A) of the composition of the present invention is:
(a) The following general formula (1):

[Wherein A represents the following general formula (2):

A divalent group selected from the group consisting of groups represented by:
R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
A compound having two hydrogen atoms bonded to a silicon atom represented by
(b) an addition reaction product with a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and the addition-reactive carbon-carbon double bond in one molecule Is an addition reaction product having at least two. Hereinafter, the component (a) and the component (b) will be described.

<(A) component>
The reaction raw material of the component (A) has (a) two hydrogen atoms bonded to the silicon atom represented by the general formula (1) (hereinafter sometimes referred to as “SiH”) in one molecule. In the compound, when A in the general formula (1) is a divalent group represented by the general formula (2), the compound includes the following general formula (3):

(R is independently an unsubstituted or substituted C1-C12, preferably C1-C6 monovalent hydrocarbon group or C1-C6, preferably C1-C4 alkoxy group. )
The compound represented by these is mentioned.

  In the above formula (3), when R is the above monovalent hydrocarbon group, for example, methyl group, ethyl, propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group Alkyl groups such as sec-hexyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, o-, m-, and p-tolyl; aralkyl groups such as benzyl group and 2-phenylethyl group An alkenyl group such as a vinyl group, an allyl group, a 1-butenyl group, or a 1-hexenyl group; an alkenyl aryl group such as a p-vinylphenyl group; and one or more hydrogen atoms bonded to carbon atoms in these groups; Substituted with a halogen atom, a cyano group, an epoxy ring-containing group, etc., for example, a halogenated alkyl such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, etc. Group; 2-cyanoethyl group; 3-glycidoxypropyl group and the like.

  Examples of the case where R is an alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and a tert-butoxy group.

  Among the above, as R, those other than alkenyl group and alkenylaryl group are preferable, and those in which all of them are methyl groups are preferable because they are easy to produce industrially and are easily available. .

As the compound represented by the general formula (3), for example,
Structural formula: HMe ₂ Si-p-C ₆ H ₄ -SiMe ₂ H
1,4-bis (dimethylsilyl) benzene represented by
Structural _{formula: HMe 2 Si-m-C} 6 H 4 -SiMe 2 H
1,3-bis (dimethylsilyl) benzene represented by
Structural formula: HMe ₂ Si—o—C ₆ H ₄ —SiMe ₂ H
And a silphenylene compound such as 1,2-bis (dimethylsilyl) benzene represented by the formula:

  In addition, the compound represented by the general formula (3) can be used alone or in combination of two or more.

  Furthermore, the component (a), which is a reaction raw material for the component (A), can be used alone or in combination of two or more.

<(B) component>
In (b) a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, which is a reaction raw material of component (A), the above-mentioned “addition reactivity” means bonding to a silicon atom. Means the property of being able to undergo the addition of hydrogen atoms (known as hydrosilylation reactions).

  In addition, the component (b) includes (i) an addition reactive carbon-carbon double bond formed between two adjacent carbon atoms among the carbon atoms forming the polycyclic skeleton of the polycyclic hydrocarbon. (Ii) a hydrogen atom bonded to a carbon atom forming the polycyclic skeleton of a polycyclic hydrocarbon is replaced by an addition-reactive carbon-carbon double bond-containing group, or (Iii) an addition reactive carbon-carbon double bond is formed between two adjacent carbon atoms among the carbon atoms forming the polycyclic skeleton of the polycyclic hydrocarbon, and the polycyclic The hydrogen atom bonded to the carbon atom forming the polycyclic skeleton of the formula hydrocarbon may be any substituted with an addition-reactive carbon-carbon double bond-containing group. Here, examples of the addition-reactive carbon-carbon double bond-containing group include alkenyl groups such as vinyl group, allyl group, propenyl group, butenyl group, hexenyl group, norbornyl group, particularly those having 2 to 12 carbon atoms. Etc.

  As the component (b), for example, the following general formula (4):

（式中、Ｒ’は非置換または置換の炭素原子数２〜１２のアルケニル基である。）
で表されるアルケニルノルボルネン化合物が挙げられる。さらに、該一般式（４）で表される化合物の具体例として、下記構造式（５）：

(In the formula, R ′ is an unsubstituted or substituted alkenyl group having 2 to 12 carbon atoms.)
The alkenyl norbornene compound represented by these is mentioned. Furthermore, as a specific example of the compound represented by the general formula (4), the following structural formula (5):

（５）

(5)

5-vinylbicyclo [2.2.1] hept-2-ene represented by
The following structural formula (6):

（６）

(6)

6-vinylbicyclo [2.2.1] hept-2-ene, and a combination of both. (Hereinafter, when it is not necessary to distinguish these three, they may be collectively referred to as “vinyl norbornene”).

  Incidentally, the substitution position of the vinyl group of the vinyl norbornene may be either a cis configuration (exo type) or a trans configuration (end type). Since there is no difference in the above, it is possible to use a combination of both isomers.

<Preparation of component (A)>
The component (A) of the composition of the present invention has two addition-reactive carbon-carbon double bonds in one molecule with respect to 1 mole of the component (a) having two SiH in one molecule. An addition reaction product containing no SiH is obtained by subjecting an excess of more than 1 mole to 10 moles or less, preferably more than 1 mole and less than 5 moles of the component (b) in the presence of a hydrosilylation reaction catalyst. Can be obtained as

  The component (A) thus obtained is derived from the component (a) in addition to the addition-reactive carbon-carbon double bond derived from the component (b) (specifically, R in the general formula (1) (From) an addition-reactive carbon-carbon double bond, so that it contains at least two addition-reactive carbon-carbon double bonds in one molecule, but this number is preferably 2-6, more preferably Two. When there are too many this addition reactive carbon-carbon double bonds, it will become easy to produce a crack in the hardened | cured material obtained by hardening the composition of this invention.

  Any conventionally known hydrosilylation reaction catalyst can be used. For example, carbon powder carrying platinum metal, platinum black, secondary platinum chloride, chloroplatinic acid, reaction product of chloroplatinic acid and monohydric alcohol, complex of chloroplatinic acid and olefins, platinum bisacetoacetate, etc. And platinum group metal catalysts such as palladium catalysts and rhodium catalysts. Moreover, about addition reaction conditions, use of a solvent, etc., it will not be specifically limited, What is necessary is just to be normal.

  As mentioned above, when preparing the component (A), the component (b) is used in an excess molar amount with respect to the component (a). Therefore, the component (A) is derived from the structure of the component (b). It has two addition-reactive carbon-carbon double bonds in one molecule. Furthermore, the component (A) has a residue derived from the component (a), and the residue is derived from the structure of the component (b) but does not have an addition-reactive carbon-carbon double bond. It may contain a structure linked by a divalent residue of a polycyclic hydrocarbon.

That is, as the component (A), for example, the following general formula (7):
Y-X- (Y'-X) p-Y (7)
Wherein X is a divalent residue of the compound of the component (a), Y is a monovalent residue of the polycyclic hydrocarbon of the component (b), and Y ′ is the above (b ) Component divalent residue, p is an integer of 0 to 10, preferably 0 to 5)
The compound represented by these is mentioned.

  In addition, about the value of p which is the number of the repeating units represented by said (Y'-X), adjusting the excess molar amount of said (b) component made to react with respect to 1 mol of said (a) component. It is possible to set by.

  As Y in the general formula (7), specifically, for example, the following structural formula:

(Hereinafter, when it is not necessary to distinguish these six members, they are collectively referred to as “NB group”, and “NB” without distinguishing the structure of the six members) May be abbreviated.).

  As Y ′ in the general formula (7), specifically, for example, the following structural formula:

The bivalent residue represented by these is mentioned.

  However, the asymmetrical divalent residue represented by the above structural formula is not limited in the left-right direction as described above. It also shows the structure rotated 180 degrees.

  Preferred specific examples of the component (A) represented by the general formula (7) are shown below, but are not limited thereto. (The meaning of “NB” is as described above.)

（８）

(8)

(In the formula, p is an integer of 0 to 10).

  Furthermore, the component (A) of the present invention can be used singly or in combination of two or more.

[Component (B)]
The component (B) of the present invention is a compound having 3 or more SiH molecules in one molecule. SiH in the component (B) is added by an addition reactive carbon-carbon double bond and at least two of the component (A) in one molecule and a hydrosilylation reaction to form a cured product having a three-dimensional network structure. give.

  Examples of the component (B) include the following general formula (9):

(In the formula, R ¹ is independently a monovalent hydrocarbon group having 1 to 12, preferably 1 to 6 carbon atoms that are unsubstituted or substituted other than a hydrogen atom or an alkenyl group, and q is 3 to 10, preferably An integer of 3 to 8, r is an integer of 0 to 7, preferably 0 to 2. The sum of q + r is preferably an integer of 3 to 10, more preferably an integer of 3 to 6. A siloxane unit to which q is attached And the siloxane units to which r is attached are randomly arranged.)
The cyclic siloxane type compound represented by these is mentioned.

Examples of the case where R ¹ in the general formula (9) is an unsubstituted or substituted monovalent hydrocarbon group other than an alkenyl group include, for example, methyl group, ethyl, propyl group, isopropyl group, butyl group, tert-butyl Group, alkyl group such as pentyl group, isopentyl group, hexyl group, sec-hexyl group; cycloalkyl group such as cyclopentyl group, cyclohexyl group; aryl group such as phenyl group, o-, m-, p-tolyl; benzyl group An aralkyl group such as 2-phenylethyl group; an alkenylaryl group such as p-vinylphenyl group; and one or more hydrogen atoms bonded to carbon atoms in these groups contain a halogen atom, a cyano group or an epoxy ring Substituted with a group or the like, for example, a halogenated alkyl group such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group; 2-cyanoethyl group; 3 -A glycidoxypropyl group etc. are mentioned.

Among the above, as R ¹ , those in which all are methyl groups are particularly preferable because they are easy to produce industrially and are easily available.

  In addition, as the component (B), for example, the general formula (10):

（１０）

（式中、Ｒ^１、ｑ及びｒは一般式（９）で定義の通りであり、Ｒ”は炭素原子数２〜１２の２価のアルキレン基であり、ｎは１〜１００の整数である。ｑ１およびｑ２はおのおの０〜８の整数であり、但しｑ１＋ｑ２は１〜８の整数である。ｒ１およびｒ２はおのおの０〜７の整数であり、但しｒ１＋ｒ２は０〜７の整数である。）
で表されるノルボルナン環含有環状シロキサン化合物を好ましく挙げることができる。

(10)

Wherein R ¹ , q and r are as defined in the general formula (9), R ″ is a divalent alkylene group having 2 to 12 carbon atoms, and n is an integer of 1 to 100. Q1 and q2 are each an integer of 0 to 8, provided that q1 + q2 is an integer of 1 to 8. r1 and r2 are each an integer of 0 to 7, provided that r1 + r2 is an integer of 0 to 7)
The norbornane ring containing cyclic siloxane compound represented by these can be mentioned preferably.

  The norbornane ring-containing cyclic siloxane compound represented by the general formula (10) is a hydrosilylation reaction between the alkenyl norbornene compound represented by the general formula (4) and the cyclic siloxane compound represented by the general formula (9). Can be manufactured. The alkylene group R ″ in the general formula (10) is generated by the addition reaction of the SiH group present in the general formula (9) with the alkenyl group R ′ in the general formula (4).

  Specific examples of the norbornane ring-containing cyclic siloxane compound of the general formula (10) include SiH obtained by hydrosilylation reaction of one or two kinds of vinyl norbornene with 1,3,5,7-tetramethylcyclotetrasiloxane. Addition reaction product having 3 or more per molecule, for example, the following general formula (11):

(Wherein x is 1 or 2, s is an integer of 1 to 100, preferably 1 to 10)
3 or more of SiH obtained by hydrosilylation reaction of one or two of the above-mentioned vinyl norbornene and 1,3,5,7,9-pentamethylcyclopentasiloxane. Addition reaction product having, for example, the following general formula (12):

(Wherein y is 1, 2 or 3 and t is an integer of 1-100, preferably 1-10)
The compound represented by these is mentioned.

Although the preferable example of the said (B) component is shown below, it is not limited to this.
(HMeSiO) ₄
(HMeSiO) ₅
(HMeSiO) ₃ (Me ₂ SiO)
(HMeSiO) ₄ (Me ₂ SiO)

(Wherein x is 1 or 2)

(Wherein y is 1, 2 or 3)

  The component (B) of the present invention can be used singly or in combination of two or more.

  The blending amount of component (B) is preferably set as follows. As will be described later, the composition of the present invention comprises a component having a hydrogen atom bonded to a silicon atom other than the component (B) and / or an addition-reactive carbon-carbon bond bonded to a silicon atom other than the component (A). A component having a heavy bond can be contained. Therefore, the amount of hydrogen atoms bonded to silicon atoms in the composition relative to 1 mol of addition-reactive carbon-carbon double bonds bonded to silicon atoms in the composition is usually 0.5 to 3.0 mol, preferably 0.8 to 2.0 mol. When the blending amount of the component (B) satisfies such conditions, the composition of the present invention can provide a cured product having sufficient hardness when used as a lens material.

  When the above-mentioned optional components are not included, the blending amount of the component (B) in the composition of the present invention is based on 1 mol of the addition reactive carbon-carbon double bond in the component (A). The amount of SiH in the component (B) is usually 0.5 to 3.0 mol, preferably 0.8 to 2.0 mol.

[Component (C)]
The hydrosilylation reaction catalyst which is the component (C) of the present invention is the same as that described in the above “Preparation of the component (A)”.

  The compounding amount of the component (C) in the composition of the present invention is not particularly limited as long as it is an effective amount as a catalyst, but platinum is added to the total mass of the component (A) and the component (B). As a group metal atom, it is preferable to mix | blend normally the quantity used as about 1-500 ppm, especially about 2-100 ppm. By setting the blending amount within the above range, the time required for the curing reaction becomes appropriate, and problems such as coloring of the cured product do not occur.

[Other ingredients]
In addition to the above-mentioned components (A) to (C), it is optional to add other components to the composition of the present invention within a range that does not impair the objects and effects of the present invention.

<Antioxidant>
In the cured product of the curable resin composition of the present invention, the addition reactive carbon-carbon double bond in the component (A) may remain unreacted,
The following structural formula (13):

（１３）

(13)

2- (bicyclo [2.2.1] hept-2-en-5-yl) ethyl group and / or the following structural formula (14):

（１４）

(14)

In some cases, a carbon-carbon double bond of 2- (bicyclo [2.2.1] hept-2-en-6-yl) ethyl group represented by the formula: And when the said carbon-carbon double bond is contained, it will be oxidized by oxygen in air | atmosphere and will cause the said hardened | cured material to color.

  Then, the said coloring can be prevented beforehand by mix | blending antioxidant with the composition of this invention as needed.

  As the antioxidant, all conventionally known antioxidants can be used. For example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-amylhydroquinone, 2, 5-di-t-butylhydroquinone, 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'- And methylenebis (4-ethyl-6-t-butylphenol). These can be used singly or in combination of two or more.

  In addition, when using this antioxidant, the blending amount thereof is not particularly limited as long as it is an effective amount as an antioxidant, but with respect to the total mass of the component (A) and the component (B). Usually, it is preferably 10 to 10,000 ppm, particularly preferably about 100 to 1,000 ppm. By setting the blending amount within the above range, the antioxidant ability is sufficiently exhibited, and a cured product having excellent optical characteristics without coloration, white turbidity, oxidative deterioration and the like is obtained.

<Viscosity / Hardness modifier>
In order to adjust the viscosity of the composition of the present invention or the hardness of the cured product obtained from the composition of the present invention, a linear diorganopolysiloxane or reticulated organopolysiloxane having an alkenyl group or SiH bonded to a silicon atom A non-reactive (that is, having no alkenyl group and SiH bonded to a silicon atom) linear or cyclic diorganopolysiloxane, silphenylene compound, etc. may be blended.

  When (D1) organopolysiloxane having various structures having an alkenyl group bonded to a silicon atom is blended in the composition of the present invention, the blending amount is the addition reactivity of the alkenyl group and the component (A). The amount of SiH in the component (B) is usually 0.5 to 3.0 mol, preferably 0.8 to 2.0 mol, per 1 mol of the total amount with the carbon-carbon double bond. In addition, when (D2) SiH-containing organopolysiloxanes with various structures are blended, the blending amount is the total amount of the SiH and the SiH that the (B) component has, and the addition that the (A) component has The amount is usually 0.5 to 3.0 mol, preferably 0.8 to 2.0 mol, per 1 mol of the reactive carbon-carbon double bond.

<Others>
Moreover, in order to ensure pot life, an addition reaction control agent such as 1-ethynylcyclohexanol and 3,5-dimethyl-1-hexyn-3-ol can be blended. Furthermore, an inorganic filler such as fumed silica may be blended in order to improve the strength within a range that does not affect transparency, and if necessary, a dye, pigment, flame retardant, etc. may be blended. Also good.

  Furthermore, it is also possible to use a light stabilizer in order to impart resistance to light degradation caused by light energy such as sunlight. As this light stabilizer, a hindered amine stabilizer that captures radicals generated by photooxidation degradation is suitable, and the antioxidant effect is further improved by using it together with the antioxidant. Specific examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyl-2,2,6,6-tetramethylpiperidine and the like.

    In addition, about the curing conditions of the composition of this invention, it changes with the quantity, Although it does not restrict | limit in particular, Usually, it is preferable to set it as 60-180 degreeC and the conditions for 10 to 300 minutes.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

Synthesis Example 1 Preparation of Component (A) Into a 500 mL four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, vinyl norbornene (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd .; 5-vinylbicyclo 60 g (0.5 mol) of [2.2.1] hept-2-ene and 6-vinylbicyclo [2.2.1] hept-2-ene in an approximately equimolar amount of isomer mixture) was added, and the oil bath was used to add 85 Heated to ° C. To this, 0.02 g of carbon powder supporting 5% by mass of platinum metal was added, and 38.8 g (0.2 mol) of 1,4-bis (dimethylsilyl) benzene was added dropwise over 25 minutes while stirring. After completion of the dropwise addition, the mixture was further stirred at 90 ° C. for 24 hours, and then cooled to room temperature. Thereafter, platinum metal-supported carbon was removed by filtration, and excess vinylnorbornene was distilled off under reduced pressure to obtain 79 g of a colorless and transparent oily reaction product (viscosity at 25 ° C .: 1220 mm ² / s).

As a result of analyzing the reaction product by FT-IR, NMR, GPC, etc.,
(1) Compound having one p-phenylene group: NBMe ₂ Si—p—C ₆ H ₄ —SiMe ₂ NB about 72 mol%,
(2) Compound having two p-phenylene groups: about 24 mol% (an example of a typical structural formula is shown below),

And (3) a compound having three p-phenylene groups: about 4 mol% (an example of a typical structural formula is shown below)

It was found to be a mixture of Moreover, the content rate of the addition reactive carbon-carbon double bond as the whole mixture was 0.40 mol / 100 g.

[Synthesis Example 2] Preparation of Component (B) To a 500 mL four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, 80 g of toluene and 1,3,5,7-tetramethylcyclotetrasiloxane 115.2 g (0.48 mol) was added and heated to 117 ° C. using an oil bath. To this, 0.05 g of carbon powder supporting 5% by mass of platinum metal was added and stirred with vinyl norbornene (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd .; 5-vinylbicyclo [2.2.1] hept-2-ene and 48 g (0.4 mol) of an approximately equimolar amount of isomer mixture with 6-vinylbicyclo [2.2.1] hept-2-ene was added dropwise over 16 minutes. After completion of the dropwise addition, the mixture was further heated and stirred at 125 ° C. for 16 hours, and then cooled to room temperature. Thereafter, platinum metal-supported carbon was removed by filtration, and toluene was distilled off under reduced pressure to obtain 152 g of a colorless and transparent oily reaction product (viscosity at 25 ° C .: 2,500 mm ² / s).

As a result of analyzing the reaction product by FT-IR, NMR, GPC, etc.,
(1) Compound having one tetramethylcyclotetrasiloxane ring: about 6 mol% (an example of a typical structural formula is shown below),

(2) Compound having two tetramethylcyclotetrasiloxane rings: about 25 mol% (an example of a typical structural formula is shown below),

(3) Compound having three tetramethylcyclotetrasiloxane rings: about 16 mol% (an example of a typical structural formula is shown below)

(Wherein x is 1 or 2)

(4) having four tetramethylcyclotetrasiloxane rings: about 11 mol% (an example of a typical structural formula is shown below),

(Wherein x is 1 or 2)

And (5) a compound having 5 to 12 tetramethylcyclotetrasiloxane rings: the remainder (an example of a typical structural formula is shown below)

(In the formula, x is 1 or 2, and n is an integer of 4 to 11.)
It was found to be a mixture of In addition, the content rate of SiH as the said mixture whole was 0.63 mol / 100g.

Synthesis Example 3 Preparation of Component (B) Into a 500 mL four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a thermometer, 80 g of toluene and 1,3,5,7,9-pentamethylcyclopenta 144.0 g (0.48 mol) of siloxane was added and heated to 117 ° C. using an oil bath. To this, 0.05 g of carbon powder supporting 5% by mass of platinum metal was added and stirred with vinyl norbornene (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd .; 5-vinylbicyclo [2.2.1] hept-2-ene and 48 g (0.4 mol) of an approximately equimolar amount of isomer mixture with 6-vinylbicyclo [2.2.1] hept-2-ene was added dropwise over 16 minutes. After completion of the dropwise addition, the mixture was further heated and stirred at 125 ° C. for 16 hours, and then cooled to room temperature. Thereafter, platinum metal-supported carbon was removed by filtration, and toluene was distilled off under reduced pressure to obtain 172 g of a colorless and transparent oily reaction product (viscosity at 25 ° C .: 3,500 mm ² / s).

As a result of analyzing the reaction product by FT-IR, NMR, GPC, etc.,
(1) Compound having one pentamethylcyclopentasiloxane ring: about 5 mol% (an example of a typical structural formula is shown below),

(2) Compound having two tetramethylcyclotetrasiloxane rings: about 28 mol% (an example of a typical structural formula is shown below),

(3) Compound having three tetramethylcyclotetrasiloxane rings: about 14 mol% (an example of a typical structural formula is shown below)

(Wherein y is 1, 2 or 3)

(4) having four tetramethylcyclotetrasiloxane rings: about 10 mol% (an example of a typical structural formula is shown below),

(Wherein y is 1, 2 or 3)

And (5) a compound having 5 to 12 tetramethylcyclotetrasiloxane rings: the remainder (an example of a typical structural formula is shown below)

(In the formula, y is 1, 2 or 3, and n is an integer of 4 to 11.)
It was found to be a mixture of In addition, the content rate of SiH as the whole mixture was 0.78 mol / 100g.

[Example 1]
(A) Reaction product obtained in Synthesis Example 1: 75 parts by mass
(B) (MeHSIO) ₅ : 25 parts by mass (total SiH in component (B) / total carbon-carbon double bond (molar ratio) in component (A)) (SiH / C = C ( In the same manner, the molar ratio of SiH / carbon-carbon double bond is described as “SiH / C = C (molar ratio)”)),
(C) platinum-vinylsiloxane complex: an amount of 20 ppm relative to the total mass of (A) and (B) as platinum metal atoms, and
1-Ethynylcyclohexanol: 0.03 part by mass was uniformly mixed to obtain a composition. This composition was poured into a mold made of glass plates to a thickness of 2 mm and heated at 150 ° C. for 2 hours to obtain a cured product.

[Example 2]
(A) Reaction product obtained in Synthesis Example 1: 60 parts by mass
(B1) (MeHSIO) ₄ : 10 parts by mass, (B2) Reaction product obtained in Synthesis Example 2: 30 parts by mass (SiH / C = C (molar ratio) = 1.48)
(C) platinum-vinylsiloxane complex: an amount of 20 ppm relative to the total mass of (A), (B1) and (B2) as platinum metal atoms, and
1-Ethynylcyclohexanol: 0.03 part by mass was uniformly mixed to obtain a composition. This composition was poured into a mold made of glass plates to a thickness of 2 mm and heated at 150 ° C. for 2 hours to obtain a cured product.

[Example 3]
(A) Reaction product obtained in Synthesis Example 1: 58 parts by mass
(B) Reaction product obtained in Synthesis Example 3: 42 parts by mass (SiH / C = C (molar ratio) = 1.41)
(C) platinum-vinylsiloxane complex: an amount of 20 ppm relative to the total mass of (A1) and (B2) as platinum metal atoms, and
1-Ethynylcyclohexanol: 0.03 part by mass was uniformly mixed to obtain a composition. This composition was poured into a mold made of glass plates to a thickness of 2 mm and heated at 150 ° C. for 2 hours to obtain a cured product.

[Comparative Example 1]
A methyl silicone resin-based curable composition (trade name: X-32-2480-4, manufactured by Shin-Etsu Chemical Co., Ltd.) was poured into a mold made of glass plates in the same manner as in Example 1 so as to have a thickness of 2 mm. And heated at 150 ° C. for 2 hours to obtain a cured product.

[Comparative Example 2]
A phenyl silicone resin-based curable composition (trade name: X-32-2712, manufactured by Shin-Etsu Chemical Co., Ltd.) was poured into a mold made of glass plates in the same manner as in Example 1 to a thickness of 2 mm, and 150 Heated at 2 ° C. for 2 hours to obtain a cured product.

<Performance evaluation method>
About the hardened | cured material obtained by each said Example and comparative example, performance was evaluated in accordance with the following method.

-Transparency evaluation-
The light transmittance of 400 nm, 450 nm, and 600 nm was measured for each cured product having a thickness of 2 mm using a spectrophotometer. (The measurement blank was air.) The measurement results are shown in Table 1.

-Hardness-
The hardness (ShoreD) of each cured product was measured according to ASTMD2240. The measurement results are shown in Table 1.

-Glass transition point-
About each hardened | cured material, Tg was observed using the TMA measuring apparatus.

-Refractive index and Abbe number-
Using each cured product, the refractive index at 25 ° C. with respect to wavelengths of 486 nm, 589 nm, and 656 nm was measured, and the Abbe number was calculated. The measurement results are shown in Table 1.

-Heat discoloration evaluation-
Using the 2 mm-thick cured product obtained above, after leaving it in a 260 ° C. environment for 3 minutes and then leaving it at room temperature for 10 minutes, the light transmittance at 400 nm was measured, The difference with the transmittance was compared. The measurement results are shown in Table 1.

-Thermal deformation resistance evaluation-
The cured product having a thickness of 2 mm obtained above was allowed to stand for 3 minutes in a 260 ° C. environment and then for 10 minutes at room temperature, and then the appearance was observed and compared with the initial one. The observation results are shown in Table 1.

[Evaluation]
In contrast to the comparative examples, the cured products of the examples all have high hardness and glass transition point, high refractive index and Abbe number of 40 or more, and are excellent in heat discoloration resistance and heat distortion resistance. On the other hand, it can be seen that methyl silicone resin and phenyl silicone resin do not satisfy both high refractive index and high Abbe number at the same time.

Claims (9)

(A) (a) The following general formula (1):

[In the formula, A represents the following general formula (2):

A divalent group selected from the group consisting of groups represented by:
R is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms or an alkoxy group having 1 to 6 carbon atoms.
A compound having two hydrogen atoms bonded to a silicon atom represented by
(b) an addition reaction product with a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and the addition-reactive carbon-carbon double bond in one molecule An addition reaction product having at least two
(B) an organosilicon compound having three or more hydrogen atoms bonded to a silicon atom in one molecule, and
(C) A curable silicone composition for optical lenses, comprising a hydrosilylation reaction catalyst, wherein the cured product has a refractive index of 1.50 or more, an Abbe number of 40 or more, and a glass transition temperature of 70 ° C. or more. The curable silicone composition for an optical lens according to claim 1, wherein the component (b) is an alkenyl norbornene compound represented by the following general formula (4).

(In the formula, R ′ is an unsubstituted or substituted alkenyl group having 2 to 12 carbon atoms.)   The curable silicone composition according to claim 2, wherein the component (b) is 5-vinylbicyclo [2.2.1] hept-2-ene, 6-vinylbicyclo [2.2.1] hept-2-ene. Or the curable silicone composition for optical lenses which is a combination of both. It is a curable silicone composition which concerns on Claims 1-3, Comprising: This (B) component is General formula (9):

(Wherein R ¹ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than a hydrogen atom or an alkenyl group, q is an integer of 3 to 10, and r is 0 to 7) (The siloxane unit with q and the siloxane unit with r are randomly arranged with respect to each other.)
A curable silicone composition for optical lenses, which is a cyclic siloxane compound represented by the formula:   The curable silicone resin composition according to claim 4, wherein the component (B) is 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopenta A curable silicone composition for optical lenses, which is siloxane or a combination of both. It is a curable silicone resin composition which concerns on any one of Claims 1-3, Comprising: The said (B) component is General formula (10):

(10)
Wherein R ¹ , q and r are as defined in the general formula (9), R ″ is a divalent alkylene group having 2 to 12 carbon atoms, and n is an integer of 1 to 100. Q1 and q2 are each an integer of 0 to 8, provided that q1 + q2 is an integer of 1 to 8. r1 and r2 are each an integer of 0 to 7, provided that r1 + r2 is an integer of 0 to 7)
The curable silicone composition for optical lenses which is a norbornane ring containing cyclic siloxane compound represented by these.   The curable silicone resin composition according to claim 6, wherein the component (B) is 5-vinylbicyclo [2.2.1] hept-2-ene, 6-vinylbicyclo [2.2.1] hept-2-ene. Ene or a combination of the two and 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, or a combination of the two A curable silicone composition for optical lenses.   A cured silicone resin having a refractive index of 1.50 or more, an Abbe number of 40 or more, and a glass transition temperature of 70 ° C. or more, obtained by molding and curing the composition according to claim 1. An optical lens consisting of   The optical lens according to claim 8, which is for a mobile phone with a camera.