TWI515263B - A hardened silicone oxygen composition for optical lenses - Google Patents

Description

Curable polyfluorene composition for optical lenses

The present invention relates to a plastic lens material, and more particularly to a curable polyoxyxene composition for an optical lens which can be used as an optical lens material for a mobile phone with a camera and which contains a polycyclic hydrocarbon skeleton component.

In recent years, the plastic lens system can be suitably used for a compact camera or a camera-equipped mobile phone which is excellent in low price and portability. The plastic lens material thus used may be a polymethacrylate of a thermoplastic resin, a polycarbonate, a cyclic olefin polymer or the like.

In addition, a general method of mounting a camera module having such a plastic lens on a mobile phone with a camera is such that a connector having heat resistance is provided on the wiring substrate, and a camera is mounted after heating and reflowing at 250 ° C or higher. The method of the module. However, such a disadvantage of the camera module mounting method has the following problems: the thickness of the connector component is loaded, or the cost of the connector component is increased, so that the cost is high.

In order to solve such a problem, a method of directly arranging a camera module on a wiring substrate without using a connector component and performing packaging by reflow processing has been proposed. In this method, there is an advantage that since the connector parts are not required, the thickness can be reduced, and the steps can be shortened to reduce the cost.

However, in the proposed packaging method, when the above thermoplastic plastic material is used, the thermoplastic plastic lens material is completely melted by the heat of the reflow step, so that it has the disadvantage of deformation or coloration.

A material which compensates for such a shortcoming is a thermosetting polysulfonated material which is excellent in heat deformation resistance and heat discoloration resistance (for example, Patent Document 1), but it is a necessary optical material for a lens material, that is, a high refractive index is simultaneously satisfied. The Abbe number, further, the material of high hardness and high glass transition point which has the necessary physical properties as a lens has not been found.

[Patent Document 1] Electronic Materials (September 2005, pp. 90-93)

(disclosure of the invention)

In view of the above problems of the prior art, an object of the present invention is to provide a heat-resistant deformability (shape retention) which can withstand a reflow step, is excellent in further heat discoloration resistance, and has a sufficient optical material (high refractive index) as a lens material. Plastic lenses with high physical properties (high hardness, high glass transition point), especially for optical lenses containing optical lenses for camera-equipped mobile phones and containing polycyclic hydrocarbon skeleton components A sclerosing polyoxyl composition is used.

The inventors of the present invention have completed the present invention in order to achieve the above object and carry out intensive studies.

That is, the present invention provides a curable polyfluorene oxygen composition for an optical lens, which comprises:

(A) (a) is given by the following general formula (1): Wherein A is selected from the group consisting of the following formula (2): a divalent group of the group consisting of the groups shown, wherein R is 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 deuterium atom;

(b) an addition reaction product of a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and having at least two addition-reactive carbon-carbon double bonds in one molecule Addition reaction product;

(B) an organic ruthenium compound having three or more hydrogen atoms bonded to a ruthenium atom in one molecule;

(C) A composition of a hydroformylation reaction catalyst having a cured product having a refractive index of 1.50 or more, an Abbe number of 40 or more, and a glass transition temperature of 80 ° C or more.

Moreover, the present invention provides an optical lens obtained by molding and curing the above composition, that is, 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. It is composed of hardened polyoxyn resin.

The curable polyfluorene oxide composition for an optical lens of the present invention is excellent in transparency due to thermal deformation or thermal discoloration caused by no reflow treatment, and has a high refractive index and a cured product having a high Abbe number. It can be used as a plastic lens, especially a material for an optical lens for a mobile phone of a camera.

(to implement the best form of invention)

Hereinafter, the present invention will be described in detail.

[(A) ingredient]

The component (A) of the composition of the present invention is (a) is represented by the following formula (1): Wherein A is selected from the group consisting of the following formula (2): a divalent group of the group consisting of the groups shown, wherein R is an independently 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 deuterium atom;

(b) an addition reaction product of a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and having at least two addition-reactive carbon-carbon double bonds in one molecule Addition reaction product. Hereinafter, the components (a) and (b) related to these will be described.

<(a) component>

(a) is a compound which has two hydrogen atoms (hereinafter, referred to as "SiH") bonded to the ruthenium atom represented by the above formula (1) in one molecule. In the case where A in the above formula (1) is a divalent group represented by the above formula (2), the compound may, for example, be represented by the following formula (3):

(R is independently substituted or substituted with 1 to 12 carbon atoms, and preferably 1 to 6 monovalent hydrocarbon groups or 1 to 6 carbon atoms, and preferably 1 to 4 alkoxy groups) Compound.

In the above formula (3), when R is the above monovalent hydrocarbon group, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a hexyl group or a second hexyl group may be mentioned. Or an alkyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; an aryl group such as a phenyl group, an o-, m- or p-xylyl group; an aralkyl group such as a benzyl group or a 2-phenylethyl group; Or an alkenyl group such as a vinyl group, an allyl group, a 1-butenyl group or a 1-hexenyl group; an alkenylaryl group such as a p-vinylphenyl group; and a carbon atom in the group bonded thereto One or more hydrogen atoms, a halogenated alkyl group such as a chloromethyl group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group or the like substituted with a halogen atom, a cyano group, an epoxy group or the like; Cyanoethyl; 3-epoxypropanepropyl.

Further, when R is the above alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a second butoxy group, a third butoxy group or the like can be mentioned.

Among the above, the above R is preferably an alkenyl group or an alkenylaryl group. In particular, all of them are methyl groups, and are industrially easy to manufacture and easy to obtain.

The compound represented by the above formula (3) may, for example, be 1,4-bis(dimethylformamido)benzene represented by the structural formula: HMe ₂ Si-pC ₆ H ₄ -SiMe ₂ H. In the formula: 1,3-bis(dimethylformamido)benzene represented by HMe ₂ Si-mC ₆ H ₄ -SiMe ₂ H, in the formula: HMe ₂ Si-oC ₆ H ₄ -SiMe ₂ H An fluorene-based compound such as 1,2-bis(dimethylformamido)benzene shown.

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

Further, the component (a) of the reaction raw material of the component (A) may be used alone or in combination of two or more.

<(b) component>

In the polycyclic hydrocarbon having two addition reactive carbon-carbon double bonds in one molecule of the reaction raw material of the component (A), the above-mentioned "addition reactivity" means that it can be bonded to The addition of a hydrogen atom of a halogen atom (known as a hydroformylation reaction).

Further, the component (b) is (i) a carbon atom of a polycyclic skeleton in which a polycyclic hydrocarbon is formed, and an addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms, and (ii) is bonded to a hydrogen atom forming a carbon atom of a polycyclic skeleton of a polycyclic hydrocarbon, which is substituted by a group containing an addition-reactive carbon-carbon double bond; or (iii) a carbon atom of a polycyclic skeleton forming a polycyclic hydrocarbon Forming a reactive carbon-carbon double bond between two adjacent carbon atoms and binding to a hydrogen atom of a carbon atom forming a polycyclic skeleton of a polycyclic hydrocarbon, by adding an addition-reactive carbon-carbon double It is also possible to replace any of the key bases. Here, the group containing an addition-reactive carbon-carbon double bond may, for example, be an alkenyl group such as a vinyl group, an allyl group, a propenyl group, a butenyl group, a pentenyl group or a norbornene group, and especially a carbon atom. 2~12.

The component (b) may, for example, be represented by the following formula (4):

(wherein R' is an unsubstituted or substituted alkenyl group having 2 to 12 carbon atoms) represented by an alkenyl norbornene compound. Further, specific examples of the compound represented by the formula (4) are represented by the following structural formula (5):

The 5-vinylbicyclo[2.2.1]hept-2-ene shown has the following structural formula (6):

6-vinylbicyclo[2.2.1]hept-2-ene as shown, and combinations of the two. (In the following, when it is not necessary to distinguish between these three, it is sometimes referred to as "vinyl norbornene").

Further, the substitution position of the vinyl group of the vinyl norbornene may be either a cis-type (Exo-shape) or a trans-configuration (Endo-shape), and the arrangement may be different. There is no particular difference in the reactivity of the components, and the like, and therefore, the combination of the two phases of the heterogeneous body may be used.

<Modulation of (A) component>

The component (A) of the composition of the present invention has 1 addition of two kinds of addition-reactive carbon-carbon double bonds in one molecule to 1 mol of the above-mentioned (a) component having SiH in one molecule ( b) the composition is more than 1 mole, less than 10 moles, preferably more than 1 mole, less than 5 moles of excess, addition reaction in the presence of a hydroformylation reaction catalyst, bismuth formation does not have SiH It is obtained by adding an addition reaction product.

The component (A) obtained in this manner may contain, in addition to the addition-reactive carbon-carbon double bond derived from the component (b), derived from the component (a) (specifically, derived from the formula (1) R) addition of a reactive carbon-carbon double bond, so that at least two addition-reactive carbon-carbon double bonds are contained in one molecule, but the number is preferably from 2 to 6, more preferably two. If the addition of reactive carbon-carbon double bonds is too large, the cured product obtained by hardening the composition of the present invention is liable to be cracked.

The hydroformylation reaction catalyst system can be used from the conventional to the public. For example, a carbon powder containing platinum metal, platinum black, chlorinated second platinum, chloroplatinic acid, a reaction product of chloroplatinic acid and a monovalent alcohol, and a chloroplatinic acid and an olefin may be mixed. A platinum-based catalyst such as platinum or bis-acetoxyacetone; a platinum group-based catalyst such as a palladium-based catalyst or a ruthenium-based catalyst. In addition, the conditions of the addition reaction, the use of the solvent, and the like are not particularly limited and may be as usual.

As described above, when the component (A) is prepared, the excess amount of the component (b) is used in excess of the component (a). Therefore, the component (A) has two derived from the above (b). The addition of a reactive carbon-carbon double bond to the structure of the component. Further, the component (A) has a residue derived from the component (a), and the residue is derived from the structure of the component (b), but may also contain an addition-reactive carbon-carbon double bond. The constructor of the combination of the divalent residues of the polycyclic hydrocarbon.

That is, the component (A) may, for example, be represented by the following formula (7): Y-X-(Y'-X)p-Y (7)

(wherein X is a divalent residue of the compound of the above component (a), Y is a monovalent residue of the polycyclic hydrocarbon of the above component (b), and Y' is a divalent component of the component (b) The compound represented by the residue, p is 0 to 10, preferably an integer of 0 to 5.

Further, the p value of the number of repeating units represented by the above (Y'-X) can be set by adjusting the excess amount of the molar amount of the above component (b) which is the molar reaction of the component (a).

The Y in the above formula (7) is specifically exemplified by the following structural formula:

The residue of one of the valences shown (these are generally referred to as "NB-based" when it is not necessary to distinguish between these six, and the structure of the above-mentioned six is sometimes referred to as "NB").

Specifically, Y' in the above formula (7) may be, for example, the following structural formula:

The divalent residue shown.

However, the asymmetric divalent residue represented by the above structural formula is not limited to the left-right direction as described above, and the structural formula is substantially represented by a structure in which the respective structures are rotated by 180 degrees on the paper surface. .

A suitable specific example of the component (A) represented by the above formula (7) is shown below, but is not limited thereto. (Also, the meaning of "NB" is as above)

(where p is an integer from 0 to 10).

Further, the component (A) of the present invention may be used alone or in combination of two or more.

[(B) ingredients]

The component (B) of the present invention is a compound having three or more SiHs in one molecule. The SiH in the component (B) is added by alkylation reaction of an addition-reactive carbon-carbon double bond having at least two of the above components (A) with hydroformylation to impart a hardening of a three-dimensional network structure. Things.

The component (B) is of the formula (9):

(wherein R ¹ is an unsubstituted or substituted carbon atom having 1 to 12, preferably 1 to 6 carbon atoms, other than an independent hydrogen atom or an alkenyl group, and q is 3 to 10, preferably 3 to 8 The integer, r is 0~7, preferably an integer of 0~2; the sum of q+r is preferably 3~10, more preferably an integer of 3~6. The unit of oxane with q is attached A cyclic oxoxane compound represented by a random arrangement of r oxoxane units.

When R ¹ in the above formula (9) is an unsubstituted or substituted monovalent hydrocarbon group other than an alkenyl group, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group or a pentyl group may be mentioned. An alkyl group such as a cyclopentyl group, a cyclohexyl group or the like; an aryl group such as a phenyl group, an o-, m- or p-xylyl group; a benzyl group; An aralkyl group such as 2-phenylethyl; an alkenylaryl group such as p-vinylphenyl; and one or more hydrogen atoms bonded to a carbon atom in the group, a halogenated alkyl group such as chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl or the like substituted by a cyano group, an epoxy group or the like; 2-cyanoethyl; 3-epoxypropanepropyl Wait.

Among the above, R ^{1 is} particularly preferably a methyl group, but it is industrially easy to manufacture and easy to obtain.

Further, the component (B) is preferably, for example, in the formula (10):

(wherein R ¹ , q and r are as defined in the formula (9), R" is a divalent alkyl group having 2 to 12 carbon atoms, n is an integer of 1 to 100, and q1 and q2 are respectively An integer from 0 to 8, except that q1+q2 is an integer from 1 to 8, and r1 and r2 are integers from 0 to 7, respectively, but r1+r2 is an integer from 0 to 7) ring containing a norbornane ring. A siloxane compound.

The cyclic oxane compound containing a norbornane ring represented by the formula (10) can be represented by the alkenyl norbornene compound represented by the formula (4) and the formula (9). The cyclic siloxane-based compound is produced by a hydroformylation reaction. The alkylene group R" in the formula (10) is produced by the addition of the alkenyl group R' in the formula (4) to the SiH group of the formula (9).

Specific examples of the cyclic oxonane compound containing a norbornane ring of the formula (10) include, for example, one or two of the above vinyl norbornenes and 1,3,5,7-tetramethyl. The SiH obtained by the hydroformylation reaction of the cyclotetramethylene oxide has three or more addition reaction products in one molecule, for example, the following formula (11):

(wherein, x is 1 or 2, s is 1 to 100, preferably an integer of 1 to 10), and one or both of the above vinyl norbornenes are 1, 3, 5, The SiH obtained by the hydroformylation reaction of 7,9-pentamethylcyclopentaoxane has three or more addition reaction products in one molecule, for example, the following formula (12):

(wherein, y is 1, 2 or 3, and t is 1 to 100, preferably an integer of 1 to 10).

A specific specific example of the component (B) is shown below, but is not limited thereto.

(HMeSiO) ₄

(HMeSiO) ₅

(HMeSiO) ₃ (Me ₂ SiO)

(HMeSiO) ₄ (Me ₂ SiO)

(where x is 1 or 2).

(where y is 1, 2 or 3)

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

The amount of the component (B) to be formulated is preferably set as follows. As described later, the composition of the present invention contains a component having a hydrogen atom bonded to a halogen atom other than the component (B), and/or an addition-reactive carbon having a halogen atom bonded to the component (A). The composition of the carbon double bond. Therefore, the amount of the hydrogen atom of the ruthenium atom bonded to the present composition is generally 0.5 to 3.0 m, relative to the addition-reactive carbon-carbon double bond 1 mol of the ruthenium atom bonded to the composition. It is 0.8~2.0 m. When the blending amount of the component (B) satisfies such conditions, the composition of the present invention can be used as a material of a lens to obtain a cured product having sufficient hardness.

In the case where the above-mentioned optional component is not contained, the amount of the component (B) in the composition of the present invention is 1 mol with respect to the addition-reactive carbon-carbon double bond in the component (A). The SiH in the composition is generally 0.5 to 3.0 m, and preferably 0.8 to 2.0 m.

[(C) ingredient]

The hydroformamidine alkylation reaction catalyst system of the component (C) of the present invention is the same as those described in the above "Preparation of the component (A)".

The amount of the component (C) of the composition of the present invention is not particularly limited as long as it is an effective amount as a catalyst, but the platinum group is based on the total mass of the components (A) and (B). For metal atoms, it is generally suitable to mix 1~500 ppm, especially about 2~100 ppm. In the above range, the amount of time required for the hardening reaction is moderate, and there is no problem such as coloring of the cured product.

[Other compounding ingredients]

In the composition of the present invention, in addition to the above components (A) to (C), other components may be arbitrarily formulated without departing from the object and effect of the present invention.

<antioxidant>

In the cured product of the curable resin composition of the present invention, when the addition-reactive carbon-carbon double bond in the component (A) is not directly reacted, the following structural formula (13) may be included:

2-(Bicyclo[2.2.1]hept-2-en-5-yl)ethyl shown and/or in the following formula (14):

The carbon-carbon double bond of 2-(bicyclo[2.2.1]hept-2-en-6-yl)ethyl is shown. Then, when the carbon-carbon double bond is contained, it is caused by oxidation of oxygen in the atmosphere and coloring of the cured product.

Therefore, in the composition of the present invention, the above-mentioned coloring can be prevented by the formulation of an antioxidant as needed.

The antioxidant may be used in all of the conventionally known ones, and examples thereof include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-amylhydroquinone, and 2,5-di Tributylhydroquinone, 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-third Phenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), and the like. These may be used alone or in combination of two or more.

In addition, when the antioxidant is used, the amount of the antioxidant is particularly limited as long as it is an effective amount of the antioxidant. However, it is generally preferable to mix 10 to 10,000 ppm with respect to the total mass of the component (A) and the component (B). Especially, it is about 100~1000ppm. By the amount of the above-mentioned range, the oxidation resistance can be sufficiently exhibited, and no coloring, white turbidity, oxidative degradation, or the like can be generated, and a cured product excellent in optical characteristics can be 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, it is also possible to formulate an alkenyl group bonded to a ruthenium atom or a linear diorganopolyoxane or network having SiH. Organopolyoxymethane; non-reactive (ie, alkenyl and SiH not bonded to a ruthenium atom) linear or cyclic diorganopolyoxyalkylene, silphenylene compound, etc. .

In the composition of the present invention, when the organopolysiloxane having various structures bonded to the alkenyl group of the (D1) fluorene atom is formulated, the amount thereof is added to the above-mentioned alkenyl group and the above component (A). The total amount of reactive carbon-carbon double bonds is 1 mole, and the SiH in the above component (B) is generally 0.5 to 3.0 moles, preferably 0.8 to 2.0 moles. Further, (D2), when the organopolysiloxane having various structures of SiH is blended, the blending amount is the total amount of SiH of the SiH and the component (B), and the addition reaction with respect to the component (A). The carbon-carbon double bond is 1 mol, generally 0.5 to 3.0 m, preferably 0.8 to 2.0 m.

<Other>

Further, in order to secure the operation time, an addition reaction controlling agent such as 1-ethynylcyclohexanol or 3,5-dimethyl-1-hexyn-3-ol may be blended. Further, in order to improve the strength, the inorganic filler such as gas phase cerium oxide may be blended, and a dye, a pigment, a flame retardant, or the like may be blended as needed.

Further, in order to impart resistance to photodegradation caused by light energy such as solar rays, a light stabilizer may be used. The light stabilizer is preferably an amine-blocking stabilizer which compensates for radicals generated by photooxidative degradation, and is used in combination with an antioxidant to improve the antioxidant effect. Specific examples of the photosensitizer include, for example, bis(2,2,6,6-tetramethyl-4-hexahydropyridine) sebacate, 4-benzylidene-2,2,6,6-tetra Methyl hexahydropyridine and the like.

Further, the curing conditions of the composition of the present invention vary depending on the amount thereof, and are not particularly limited, but are generally 60 to 180 ° C for 10 to 300 minutes.

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the examples described below.

[Examples]

[Synthesis Example 1] Modulation of component (A)

Vinyl norbornene (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd.; 5-vinyl bicyclo [2.2.1] G-2) was added to four flasks of 500 ml equipped with a stirring device, a cooling tube, a dropping funnel, and a thermometer. - 60 g (0.5 mol) of an alkene and a mixture of 6-vinylbicyclo[2.2.1]hept-2-ene, a slight molar amount of isomers, heated to 85 ° C using an oil bath. Further, 0.02 g of carbon powder containing 5% by mass of platinum metal was added, and while stirring, the 1,4-bis(dimethylformamido)benzene 38.8 g (0.2 mol) was dropped for 25 minutes. After the completion of the dropwise addition, the mixture was further heated and stirred at 90 ° C for 24 hours, and then cooled to room temperature. Thereafter, the carbon of the platinum metal was removed by filtration, and the excess vinyl norbornene was distilled off under reduced pressure to obtain a reaction product of a colorless transparent oil (viscosity at 25 ° C: 1220 mm ² /s), 79 g. .

The result of analyzing the reaction product by FT-IR, NMR, GPC, etc.

(1) a compound having one p-phenylene group: NBMe ₂ Si-pC ₆ H ₄ -SiMe ₂ NB is about 72 mol%,

(2) A compound having two p-phenylene groups: about 24 mol% (an example of a representative structural formula is shown below)

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

mixture. Further, the content ratio of the addition-reactive carbon-carbon double bond as the entire mixture was 0.40 mol/100 g.

[Synthesis Example 2] Modulation of component (B)

Into four flasks of 500 ml equipped with a stirring device, a cooling tube, a dropping funnel and a thermometer, 80 g of toluene and 115.2 g (0.48 mol) of 1,3,5,7-tetramethylcyclotetraoxane were added, and oil was used. Heat to 117 ° C in the bath. Further, 0.05 g of carbon powder containing 5% by mass of platinum metal was added, and vinyl norbornene was dropped for 16 minutes while stirring (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd.; 5-vinyl bicyclo [2.2 .1] a mixture of hept-2-ene and 6-vinylbicyclo[2.2.1]hept-2-ene in a slight molar amount of isomer) 48 g (0.4 mol). After the completion of the dropwise addition, the mixture was further heated and stirred at 125 ° C for 16 hours, and then cooled to room temperature. Then, the carbon of the platinum metal was removed by filtration, and the toluene was distilled off under reduced pressure to obtain 152 g of a reaction product (viscosity at 25 ° C: 2500 mm ² /s) in the form of a colorless transparent oil.

The result of analyzing the reaction product by FT-IR, NMR, GPC, etc.

(1) A compound having one tetramethylcyclotetraoxane ring: about 6 mol% (an example of a representative structural formula is shown below),

(2) a compound having two tetramethylcyclotetraoxane rings: about 25 mol% (an example of a representative structural formula is shown below),

(3) a compound having three tetramethylcyclotetraoxane rings: about 16 mol% (an example of a representative structural formula is shown below),

(where x is 1 or 2)

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

(where x is 1 or 2)

And (5) a compound having 5 to 12 tetramethylcyclotetraoxane rings: residual (an example of a representative structural formula shown below),

(where x is 1 or 2 and n is 4 to 11)

mixture. Further, the content ratio of SiH as the entire mixture was 0.63 mol/100 g.

[Synthesis Example 3] Modulation of component (B)

To 400 ml of four flasks equipped with a stirring device, a cooling tube, a dropping funnel and a thermometer, 80 g of toluene and 144.0 g (0.48 mol) of 1,3,5,7,9-pentamethylcyclopentaoxane were added. Heat to 117 ° C using an oil bath. Further, 0.05 g of carbon powder containing 5% by mass of platinum metal was added, and vinyl norbornene was dropped for 16 minutes while stirring (trade name: V0062, manufactured by Tokyo Chemical Industry Co., Ltd.; 5-vinyl bicyclo [2.2 .1] a mixture of hept-2-ene and 6-vinylbicyclo[2.2.1]hept-2-ene in a slight molar amount of isomer) 48 g (0.4 mol). After the completion of the dropwise addition, the mixture was further heated and stirred at 125 ° C for 16 hours, and then cooled to room temperature. Then, the carbon of the platinum metal was removed by filtration, and the toluene was distilled off under reduced pressure to obtain 172 g of a reaction product (viscosity at 25 ° C: 3500 mm ² /s) in the form of a colorless transparent oil.

The result of analyzing the reaction product by FT-IR, NMR, GPC, etc.

(1) A compound having one pentamethylcyclopentaoxane ring: about 5 mol% (an example of a representative structural formula is shown below),

(2) a compound having two tetramethylcyclotetraoxane rings: about 28 mol% (an example of a representative structural formula is shown below),

(3) A compound having three tetramethylcyclotetraoxane rings: about 14 mol% (an example of a representative structural formula is shown below),

(where y means 1, 2 or 3)

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

(where y means 1, 2 or 3)

And (5) a compound having 5 to 12 tetramethylcyclotetraoxane rings: residual (an example of a representative structural formula shown below),

(where y is 1, 2 or 3, and n is an integer from 4 to 11)

mixture. Further, the content ratio of SiH as the entire mixture was 0.78 mol/100 g.

[Example 1]

(A) The reaction product obtained in Synthesis Example 1 : 75 parts by mass,

(B) (MeHSiO) ₅ : 25 parts by mass (again, the total SiH in the component (B) / the total carbon-carbon double bond (mol ratio) in the above (A) component (SiH/C=C ( Mohr ratio = 1.39 or less, and the molar ratio of the SiH/carbon-carbon double bond is described as "SiH/C=C (Mohr ratio)"),

(C) a platinum-vinyl oxime complex: an amount of 20 ppm with respect to the total mass of the platinum metal atom with respect to the total mass of (A) and (B), and

1-ethynylcyclohexanol: 0.03 parts by mass

The mixture was uniformly mixed to obtain a composition. This composition was poured into a glass plate composite mold to a thickness of 2 mm, and heated at 150 ° C for 2 hours to obtain a cured product.

[Embodiment 2]

(A) The reaction product obtained in Synthesis Example 1 : 60 parts by mass, (B1) (MeHSiO) ₄ : 10 parts by mass, (B2) The reaction product obtained in Synthesis Example 2: 30 parts by mass (SiH/ C=C (Morby) = 1.48)

(C) a platinum-vinyl oxime complex: an amount of 20 ppm with respect to the total mass of the platinum metal atom with respect to the total mass of (A), (B1), and (B2), and

1-ethynylcyclohexanol: 0.03 parts by mass

The mixture was uniformly mixed to obtain a composition. This composition was poured into a glass plate composite mold to a thickness of 2 mm, and heated at 150 ° C for 2 hours to obtain a cured product.

[Example 3]

(A) The 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 (Mohr ratio) = 1.41)

(C) a platinum-vinyl oxime complex: an amount of 20 ppm with respect to the total mass of the platinum metal atom with respect to the total mass of (A1) and (B2), and

1-ethynylcyclohexanol: 0.03 parts by mass

The mixture was uniformly mixed to obtain a composition. This composition was poured into a glass plate composite mold to a thickness of 2 mm, and heated at 150 ° C for 2 hours to obtain a cured product.

[Comparative Example 1]

In the same manner as in Example 1, the methyl polyoxynene resin-based curable composition (product name: X-32-2480-4, manufactured by Shin-Etsu Chemical Co., Ltd.) was poured into a glass plate mold to a thickness of 2 mm, and was 150. The mixture was heated at ° C for 2 hours to obtain a cured product.

[Comparative Example 2]

In the same manner as in Example 1, a phenyl fluorinated resin-based curable composition (trade name: X-32-2712, manufactured by Shin-Etsu Chemical Co., Ltd.) was poured into a glass plate mold to a thickness of 2 mm, and heated at 150 ° C. Hardened material was obtained in 2 hours.

<Performance evaluation method>

With respect to the compositions obtained in the above respective Examples and Comparative Examples, the properties were evaluated by the following methods.

-Transparency assessment -

The light transmittances at 400 nm, 450 nm, and 600 nm were measured using a spectrophotometer for each of the 2 mm thick hardened materials. (Measurement of blank group is air) The measurement results are shown in Table 1.

-hardness-

The hardness (Shore D) of each hardened material was measured in accordance with ASTM D 2240. The measurement results are shown in Table 1.

- glass transfer point -

For each cured product, Tg was observed using a TMA measuring device.

- refractive index and Abbe number -

Using each of the cured materials, the refractive index at 25 ° C for 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 resistance discoloration evaluation -

Using the 2 mm thick cured product obtained above, it was allowed to stand at 260 ° C for 3 minutes, and then left at room temperature for 10 minutes. After repeating this three times, the light transmittance at 400 nm was measured, and the initial transmittance was compared. difference. The measurement results are shown in Table 1.

- Heat deformation resistance evaluation -

The cured product having a thickness of 2 mm obtained as described above was allowed to stand in an environment of 260 ° C for 3 minutes, and then left at room temperature for 10 minutes. After the above three times, the appearance was observed and compared with the initial stage. The observation results are shown in Table 1.

[assessment]

In comparison with the comparative example, it was found that any of the cured products of the examples had high hardness and glass transition point, and had a high refractive index, and had an Abbe number of 40 or more, and was excellent in heat discoloration resistance and heat deformation resistance. Further, it is understood that the methyl polyoxyn resin or the phenyl polyoxy resin does not satisfy both the high refractive index and the high Abbe number.

Claims (7)

A curable polyfluorene oxygen composition for an optical lens, comprising: (A) (a) having the following general formula (1): Wherein A is selected from the group consisting of the following formula (2): a divalent group of the group consisting of the groups shown, wherein R is an independently 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 deuterium atom; and (b) an addition reaction product of a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and An addition reaction product having at least two addition-reactive carbon-carbon double bonds in one molecule; (B) an organic ruthenium compound having three or more hydrogen atoms bonded to a ruthenium atom in one molecule; and (C) A composition of a hydroformylation reaction catalyst having a cured product having a refractive index of 1.50 or more, an Abbe number of 40 or more, a glass transition temperature of 70 ° C or more, and the component (B) having the following formula (10): (wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms other than an independent hydrogen atom or an alkenyl group, q is an integer of 3 to 10, and r is an integer of 0 to 7; The oxoxane unit and the arsonane unit with r are randomly arranged, R" is a two-valent alkyl group having 2 to 12 carbon atoms, n is an integer of 1 to 100, and q1 and q2 are 0~ respectively. An integer of 8, but q1+q2 is an integer from 1 to 8, and r1 and r2 are integers of 0 to 7, respectively, but r1+r2 is an integer of 0 to 7) Oxyalkane compound. The curable polyfluorene oxide composition for an optical lens according to the first aspect of the invention, wherein the component (b) is an alkenyl norbornene compound represented by the following formula (4). (wherein R' is an unsubstituted or substituted alkenyl group having 2 to 12 carbon atoms). The curable polyfluorene oxide composition for an optical lens according to claim 2, wherein the component (b) is 5-vinylbicyclo[2.2.1]hept-2-ene and 6-vinylbicyclo[2.2. 1] Hept-2-ene or a combination of the two. Such as the patented scope of the first item of the optical lens for the use of hardening polyoxyl a composition wherein the component (B) is 1,3,5,7-tetramethylcyclotetraoxane, or 1,3,5,7,9-pentamethylcyclopentaoxane or both The combination. The hardenable polyfluorene composition for an optical lens according to claim 1, wherein the component (B) is 5-vinylbicyclo[2.2.1]hept-2-ene and 6-vinylbicyclo[2.2. 1] hept-2-ene or a combination of the two, and 1,3,5,7-tetramethylcyclotetraoxane, 1,3,5,7,9-pentamethylcyclopentaoxane Or an addition reaction product of a combination of the two. An optical lens obtained by molding and hardening a composition according to any one of claims 1 to 5, and having a refractive index of 1.50 or more, an Abbe number of 40 or more, and a glass transition temperature. It is composed of a hardened polyoxyl resin of 70 ° C or more. An optical lens as claimed in claim 6 is a mobile phone with a camera attached thereto.