TW201120145A - Curable composition for optical material - Google Patents

Abstract

Disclosed is a curable composition for optical materials which comprises (A) an organic compound having a number-average molecular weight of 10,000 or lower and having, per molecule, at least two carbon-carbon double bonds reactive with an SiH group, (B) a polysiloxane compound which is obtained by reacting a di- or polyfunctional organic compound with a polysiloxane compound and which contains at least two SiH groups per molecule, (C) a hydrosilylation catalyst, and (D) a silicone compound which has a structure represented by the general formula R1 nSiO(4-n)/2 (wherein R1s may be the same or different and each represents a hydrogen atom or a C1-50 monovalent organic group optionally substituted by an oxygen, nitrogen, sulfur, or halogen atom, and n is an integer of 1-3) and which has, per molecule, at least two SiH groups and/or carbon-carbon double bonds reactive with an SiH group, the amount of the ingredient (D) being 0.005-10 parts by weight per 100 parts by weight of the sum of the ingredients (A) and (B).

Description

[Technical Field] The present invention relates to a curable composition for an optical material which can provide a cured product excellent in mold release property to a substrate, a cured product thereof, and a cured product. Optical components, optical components, and optical semiconductor modules. [Prior Art] In general, optical materials such as lenses or optical fibers, or other adhesives or coating agents, LEDs, or light-receiving elements, etc., are called optical semiconductors, and optical materials for optical materials. A high transparency and hardness are required, and an epoxy resin, an acrylic resin, a polycarbonate resin, a cycloolefin resin, etc. are currently used. However, due to the increased emphasis on environmental protection, the use of low-melting-point solders containing ships (Pb) used up to now has been limited, and the temperature applied during welding of Annon has become high. In fact, sometimes it is subjected to a temperature history of more than 25 (rc, even if the resin which has been used up to now causes discoloration or deformation. Therefore, it is proposed to use a polyoxyl resin excellent in heat resistance and transparency. Document 1 or Patent Document 2 discloses that an optical lens or composition containing polyoxin or yt-[the oxalate is proposed to have an optical lens for ensuring heat resistance, transparency, and hardness. In general, in the case of using a polysulfide resin, the linear expansion coefficient is increased with respect to the resin, so that there is a problem that the refractive index dependence with respect to temperature becomes large or that a crack occurs when a thermal shock is applied. CITATION LIST OF THE INVENTION PROBLEM TO BE SOLVED BY THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION It is to provide a curable composition which can provide high transparency and hardness, and has excellent heat discoloration resistance and small birefringence. The present invention relates to a curable composition for an optical material comprising: ^ (A) l having at least two carbon-carbon double bonds reactive with a siH group in the molecule An organic compound having a number average molecular weight of 10,000 or less, (B) a polyoxyalkylene compound having at least two SiH groups in one molecule obtained by reacting a difunctional or higher organic compound with a polyoxyalkylene compound, (C) a hydrogen catalyzed catalyst, and (D) having the structure represented by the following formula: R nSiO(4-n)/2 (R1 is hydrogen or a valence organic group having a carbon number of 1 to 5 Å, which can be oxygenated, The substitution of nitrogen, sulfur or a halogen atom for 'each R' may be the same or different; η is an integer of 1 to 3), and at least 2 SiH groups in one molecule and/or carbon-1⁄4 double reactive with SiH groups a polyoxo compound having a bond; wherein the component is contained in an amount of from 0 to 005 to 10 parts by weight based on 100 parts by weight of the total of the components (A) and (B). { S1 149086.doc 201120145 Preferred component (D) The viscosity at 23 ° C is 〇.001~5. 〇Pa · s. Preferably, the component (D) is by gel permeation chromatography. The number average molecular weight measured in terms of polystyrene is 300 to 30000. It is preferred that the component (D) is less than 1% by weight in a thermogravimetric measuring apparatus after heating at 10 rc! minutes. The component (B) is obtained from a bifunctional or higher organic compound represented by the following formula (I): [Chemical Formula 1]

0,, N \〇 (wherein R2 is an organic group having a carbon number of 1 to 50, which may be substituted by oxygen, nitrogen, sulfur, or a halogen atom; each R2 may be the same or different). It is preferred that the component (B) is obtained from a bifunctional or higher organic compound represented by the following formula (II): [Chemical 2]

(wherein R 3 is an organic group having a carbon number of 1 to 5 Å, and may be substituted by oxygen, nitrogen, sulfur, or a halogen atom; and each R 3 may be the same or different). Preferably, the component (B) is obtained from a difunctional or higher aliphatic compound having a cyclic structure, 149086.doc 201120145. The component (4) is a monthly aliphatic hydrocarbon compound having a cyclic structure. The component (4) is selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the formula (II).

Ub3] ^ species.

(I) (wherein R2 is a carbon number of W0, which is organic*, and may be substituted by oxygen, nitrogen, sulfur or a halogen atom; each ruler 2 may be the same or different. [Chemical 4]

R3 (wherein R3 is an organic group having a carbon number of 丨~ curse, and may be substituted by oxygen, nitrogen, sulfur, or a halogen atom; each R3 may be the same or different). Preferably, the component (A) is selected from the group consisting of triallyl isocyanurate, diallyl monoglycidyl dimethacrylate, divinylbenzene, bisphenol A diallyl ether, bisphenol S diallyl At least one of the group consisting of ether, polybutadiene, vinyl norbornene, vinylcyclohexene, and M,6-trivinylcyclohexane. Preferably, the component (A) contains 0.4 mmol or more per 1 g of the component (A) [S1: 149086.doc 201120145

The SiH group has a reactive carbon-carbon double bond. It is preferred to provide a cured product having a cured product (thickness of 3 mm) having a light transmittance of 60% or more at a wavelength of 4 〇〇 nm. It is preferable to provide a cured product having a light transmittance of 60% or more at a wavelength of 4 〇〇 nm after heat treatment for 3 minutes by heat-treating the cured product (3 claws thickened in the atmosphere) for 3 minutes. It is preferred to provide a hardener having a Shore D hardness of 30 or more at 25 °C. It is preferred to provide a cured product having a linear expansion coefficient of 150 ppm/K or less at 30 °C. Further, the present invention relates to a transparent cured product obtained by curing the above-mentioned optical material with a curable composition. Further, the present invention relates to an optical member, an optical component, and an optical semiconductor module using the above transparent cured product. Advantageous Effects of Invention The curable resin for optical materials of the present invention has a polyfluorene compound having a specific structure and having at least two SiH groups in one molecule and/or a carbon-carbon double bond reactive with SiH groups. Therefore, it is possible to obtain a suitable optical material for which the mold release property is excellent, the birefringence is small (the hardening unevenness is small), the transparency, the thermal discoloration property and the hardness are high, and the linear expansion coefficient at a high temperature is small. Hardened matter. [Embodiment] Hereinafter, preferred embodiments for carrying out the invention will be described. ((A) component) 149086.doc 201120145 (A) The component is one molecule and Y has at least two reactive carbon-carbon double bonds with SiH groups. The average number of octagonal λ λ is 10,000 or less. Organic compound. The above organic compounds are divided into six elements, early. The structure is not particularly limited, and as the above-mentioned compound, it is not a polysulfonate-containing organic gas-polymerization copolymer graft copolymer containing an oxime-containing oxime-alkane-alkaline (hO-Si) Preferably, 90% by weight or more of the constituent elements are 遝6 and are selected from the group consisting of 6, "! At least one of ^, 〇, 8 and a group of halogens. & For the case of (4) oxonium, there is a problem of gas permeability or elasticity. Further, if the number average molecular weight is used, it is a coffee. The above is based on the organic compound T test #. The wood of the material, Tg (glass transition temperature) is lowered to cause problems in heat resistance of the cured product. The number average molecular weight is preferably 5,000 or less. In the present invention, the number average molecular weight means the number average molecular weight in terms of polystyrene as measured by gel permeation chromatography (Gpc). The organic compound having at least two carbon-carbon double bonds reactive with the SiH group in the (A) molecule preferably contains an organic f-frame moiety, and is covalently bonded to the organic skeleton moiety and has SiH A group having a reactive carbon-carbon double bond. The above-mentioned group having a carbon-carbon double bond reactive with the SiH group may be covalently bonded to any portion of the organic skeleton. First, a carbon-carbon double bond reactive with a SiH group will be described. The organic compound having the component (A) has a carbon-carbon double bond group, and is not particularly limited as long as it has reactivity with the SiH group. The group having a carbon-carbon double bond having reactivity with the μη group is preferably a group having a structure represented by the following formula (III) in terms of high reactivity: 149086.doc 201120145 [ 5] R4 H2C=C—(丨丨丨) (wherein R4 is a hydrogen atom or a methyl group). In the case where the raw material is easily obtained, it is particularly preferable that R4 is a hydrogen atom. In view of the fact that the heat resistance of the cured product is high, the base having the carbon-carbon double bond is preferably a group having a structure represented by the following formula (IV): [Chemical Formula 6] (IV) ( Wherein R5 represents an argon atom or a fluorenyl group; each ruler 5 may be the same or different). Further, in terms of easily obtaining a raw material, it is particularly preferable that R5 is a hydrogen atom. The group having a carbon-carbon double bond reactive with the SiH group may be covalently bonded to the organic skeleton portion via a functional group having a valence of two or more. The functional group having two or more valences is preferably a functional group having a carbon number of 〇~2〇, more preferably a functional group having a carbon number of 〇~1 〇. There is no particular limitation, and examples of such a functional group include compounds having the following general formula. [化7] 0

« 149086.doc 201120145 ο I! —ο—c 一〇 II Η '―0*^— 0 CH3 ch3 —s — —S′ — —c— —P— II H ch3

Xn (n represents an integer from 1 to 10), (n represents an integer from 0 to 4), ~0^CH2)n [化8]

(η represents an integer of 0 to 4) Further, in the above, two or more functional groups may be bonded by a covalent bond to form one divalent or higher functional group in a larger unit. Specific examples of the group having a carbon-carbon double bond include a vinyl group, an allyl group, a decyl allyl group, an acrylonitrile group, a decyl acryl fluorenyl group, and 2-. [S1 149086.doc -10 - 201120145 Allyl phenyl, 3-allylphenyl, 4-allylphenyl, 2-(allyloxy)phenyl, 3-(allyloxy)phenyl, 4-(allyl Oxy)phenyl, 2-(allyloxy)ethyl, 3-(allyloxy)propyl, 2,2-bis(allyloxymethyl)butyl, 3-dipropyloxy_ 2,2-bis(allyloxymethyl)propyl group, a group represented by the following formula. [11] (11 represents an integer satisfying 521122) Η2 H2C^ ~CH2_ (R represents a divalent group selected from the group)

〆 Η (η represents an integer of 0 to 4) Next, the organic skeleton portion will be described. The carbonate-based or aryl ester mainly contains an element selected from the group consisting of carbon, hydrogen, a nitrogen atom, a two-framework '----------- limited. For example, it can be as long as it is a saturated hydrocarbon system, a squamous system, a sulphuric acid system, or an H 2 acrylic acid: ethylene system, 149086.doc •11. 201120145 is a urethane type, a quinone imine type, a benzoic acid type ( An organic poly-moon frame such as a resin, or an aromatic flue system such as a phthalate, a bismuth, a benzene or a naphthalene, an aliphatic smog, an aliphatic alcohol, a cyclic hydrocarbon, etc. More than one type of organic monomer skeleton. The molecular weight of the machine frame portion is not particularly limited, and from the viewpoint of workability, 5 is preferably 10,000 or less, more preferably 5,000 or less. The so-called "molecular weight" in the present month indicates the number average molecular weight of the polystyrene exchanged by GPC. Specific examples of the "polymeric skeleton" include polyether polystyrenes such as polyoxyethylene, polyoxypropylene, polytetrahydrofuran, and polyoxyethylene-polyoxypropylene copolymer, and polybutadiene. For example, it can be cited: [Chemical 10] C-X'

0—R74~~(-0—R8- q

Ό-Υ-C=CI (wherein R6 represents a carbon number of 〇~50 one-valent organic group, r, r8 represents = divalent organic group, the same or different and directly ^^ number is 1~Μ The divalent organic group, P, and Γ are respectively represented by 1 to 6 〇山再再, R6 is preferably a divalent hydrocarbon group having a carbon number of 〇~6, a divalent hydrocarbon group of r7 and r preferably = 1 to 1〇0, Preferably, the carbonization number is from 1 to 1 〇0, and the carbonization number is a stretching base of carbon number 50, preferably the same or different non-direct bonding or carbon number W0 bivalent cigarette base, ρ, 咖佳149086.doc -12- m. 201120145 respectively represents an integer from 1 to 50. Further, the organic group herein is not particularly limited, and is preferably a rolling bond, a shrink key, a quinone bond, or a amide bond car. The official website is the same as the "organic group" listed below. As the other organic polymer used as the skeleton of the organic polymer, it is taken as "1". "Do not mention, for example: - acid, neighbor two Dibasic acids such as formic acid, isophthalic acid, p-benzoic acid phthalic acid and - , hexa- 4,-r. Benzene-poly, propylene glycol, 'monool, neopentyl glycol, etc. Condensation or lactone s 3 cheek opening Agglomerated polymer obtained by polymerization; ethylene-propylene copolymer; copolymer of polyisobutylene, isobutylene and isoprene; gas butadiene; polyisoprene: isoprene and butyl a copolymer of H dilonitrile and benzene, a copolymer of butadiene, butadiene, stupid ethylene, acrylonitrile, etc., a polyolefin (saturated hydrocarbon) polymer obtained by hydrogenating polyisoprene, a polyolefin-based polymer obtained by hydrogenating polybutadiene, a polyolefin-based polymer obtained by hydrogenating a copolymer of isoprene and acrylonitrile, styrene or the like, butadiene with acrylonitrile, styrene a polyolefin-based Z compound obtained by hydrogenating a copolymer; a polyacrylate obtained by radically polymerizing a monomer such as ethyl acrylate or butyl acrylate; a propyl ester such as ethyl acrylate or butyl acrylate; An acrylate-based copolymer with vinyl acetate, acrylonitrile, decyl methacrylate, styrene or the like; a graft polymer obtained by polymerizing an ethylene monomer in the above organic polymer; a polysulfide-based polymer; By the ring-opening polymerization of ε-caprolactam 6. Nylon 66 obtained by polycondensation of 1,6-hexanediamine with adipic acid, nylon 610 obtained by polycondensation of 1,6-hexanediamine and sebacic acid, by 11- Alkyl-acid polycondensation to obtain Nikon 149086.doc 201120145 'Long 11, nylon 12 obtained by ring-opening polymerization of dodecylamine, copolymerized nylon having two or more of the above nylons Polyurethane-based polymer produced by polycondensation of aramid-based polymer, poly-A and stone ruthenium gas; o-phenyl-I-allyl-acrylic acid-based polymer; varnish-type resin, soluble An antimony resin such as a resin, an amino acid-type resin, or a light-weight antimony resin, etc. Further, an organic compound of the component (A) having an alkenyl group introduced into a side chain or a terminal end of the organic polymer skeleton Specific examples include: [Chem. 11] H2C=:c—X-

•R 10

• R 11 Ύ a C—CH 2 r —R 9 (wherein R represents a hydrogen atom or a base group, and R 10 and R 11 are the same or different and represent a divalent organic group numbered from 1 to 100, and X and Y are the same or different A direct bond, or a divalent organic group having a carbon number of 1 to 48, and p, q, and r represent an integer of 00, respectively.) [12] H2C=c-xi-〇J^.Ri3 .{{_〇_ R14

R 12 Ο—Y-C~CH2

Wherein R is a hydrogen atom or a methyl group, and R13 and R14 are the same or different and represent a divalent organic group having a number of 1 to 1 Å, and X and Y are the same or different and represent a direct bond or a carbon number. It is a divalent organic group of 1 to 48, and n represents an integer of 1 to 50. ) ill 149086.doc 201120145 [Chem. 13]

(wherein Rl5 represents a hydrogen atom or a fluorenyl group, and R16 and R17 are the same or different and represent a divalent organic group of 1 to 1 〇〇, and X and Y are the same or different and represent a direct bond or a carbon number of 1 to 48 of the divalent organic group, p and q respectively represent an integer of 1 to 50' r represents an integer of 1 to 2 。.) [Chem. 14]

(wherein Rl8 represents a hydrogen atom or a fluorenyl group, and R19, R20 and R21 are the same or different and represent a divalent organic group having a carbon number of 1 to 6, and X and γ are the same or different and represent a direct bond or a carbon number of 丨The divalent organic group of -48, p, q&r represents an integer of 1 to 50, s represents an integer of 1 to 20, and the like. Further, R10, R", ruler 13 and ruler 14 are divalent organic groups of diterpenoids (8), preferably a hydrocarbon group, more preferably an alkylene group. Further, the carbon number of the organic group is preferably from 1 to 60 Å. R16 and R17 are a divalent organic group having a carbon number of from 1 to 1 Torr, preferably a hydrocarbon group, and 149086.doc 15 201120145 is more preferably an alkylene group. Further, the carbon number of the organic group is preferably 丨. R19, R2Q and R21 are a divalent organic group having 1 to 6 carbon atoms, preferably a divalent hydrocarbon group having 1 to 6 carbon atoms, more preferably an alkyl group having a carbon number. X and Y are directly bonded or a divalent organic group having a carbon number of ruthenium, preferably a direct bond or a divalent hydrocarbon group having a carbon number of 1 to 48, more preferably a direct bond or a carbon number of 1 to 48. Alkyl. The carbon number of the organic group is preferably 12. P and q are each preferably an integer of 1 to 20, r is preferably an integer of 丨 to 汕, s is preferably an integer of 1 to 1 ,, and η is preferably an integer of i to 1 〇. As an example of the organic monomer, it is an aliphatic bond-like compound of Ethylene, Acrylic or Isobutyl, or an aliphatic cyclic compound of cyclopentane, dicyclopentane or norbornane, or an epoxy or oxygen. Heterocyclic butane, furan, thiophene, pyrrole oxazole, isoxazole, thiazole, imidazole, pyrazole, furazolium, diazole, tetrazole, pyran, sulfur A heterocyclic hexene system, a pyridine system, a chewing system, a sulphate system, a sulphate system, a bismuth system, a pyrazine compound, and a heterocyclic compound. Here, the heterocyclic ring is not particularly limited as long as it is a cyclic compound having a hetero element in the cyclic skeleton. It does not include those containing Si in the ring-forming atom. In other words, the number of atoms forming the ring is not particularly limited to '3 or more. It is preferably 1 or less in terms of availability. Specific examples of the (Α) component containing an organic monomer include an aliphatic bond-like polyphosphorus compound such as dibutyl sulphate, isoprene-supplied _ ^ ^ olefin oxime, and a ring. An aliphatic cyclic polyene compound cyclopentene such as hexadiene, cyclooctadiene, dicyclopentadiene, tricyclo: ene, norbornadiene, r, ruthenium ρ β ^ dilute, vinyl norbornene Alkene, etc., substituted aliphatic ring [si i49086.doc • 16 - 201120145, a dilute & compound system, o-dicarboxylic acid diene ester, trimellitic acid triallyl s-ethylidene diacetate, three Mercaptopropene-diallyl dialone, quaternary tetraol triallyl ether, 1,1,2,2-tetraallyloxyethane, diisopropylidene pentaerythritol, triallyl cyanurate , Isopropyl cyanurate, vinegar, diallyl monoglycidyl isocyanurate, tris(2-propene oxyethyl) isocyanurate, 1,2,4-trivinylcyclohexane , divinylbenzene (purity of 50 to 100%, preferably 80 to 100% purity), divinylbiphenyl, 1,3-diisopropene stupid, anthracene, 4_diisopropene benzene, Having a base of the following formula Compounds, etc. [化15]

(n^l) 149086.doc 17 201120145 [Chemical 16] One (where n is an integer from 4 to 9), shouting GH=CH2 (where η is 2~18). δ——,( Where „为为~17的字符), CHa 0 CH3 CH2-CH=CH2 , A C—CJFCHz , C—0—CH2-CH=CH2 ^Q,~

OH I - CH2~CH-CH2**0-CH2-CH-CH2 , 0 y-NH-CHjtCH=GH2

OH

—CH2-CH 0—CH2~CH=CH2 —CH2-CH_GH2-〇—ch2-gh=ch2 , a CH-CH2 ^CH2yOH-CH2 (where n is a number from 2 to 18)

The component (A) preferably has a reaction with SiH groups of 0.4 mmol or more per 1 g of the component (A) from the viewpoint of further improving heat resistance.

E SI 149086.doc •18- 201120145 The carbon and carbon double bond of the sex is more preferably 1·0 mmol or more per 1 g. The number of carbon-carbon double bonds reactive with the siH group of the component (A) is usually at least 2 per molecule, in order to further improve the mechanical strength.

The shape is preferably more than two, more preferably three or more. When the number of carbon-carbon double bonds reactive with the SiH group in the component (a) is one or less per molecule, even if it reacts with the component (B), only a graft structure is formed without forming a cross. Joint structure. The component (A) preferably has one or more vinyl groups in the molecule, and more preferably has two or more vinyl groups in the oxime molecule. Further, from the viewpoint of facilitating the storage stability, it is preferred to have 6 or less vinyl groups per molecule, and more preferably 4 or less vinyl groups per molecule. The component (A) preferably has a fluidity at a temperature lower than HHTC from the viewpoint of high mechanical heat resistance and a low drawability of the raw material liquid, and good moldability, workability, and coatability. The shape may be linear or branched. Preferably, the lower limit of the molecular weight is 5 Å and the upper limit is 5 Å. The lower molecular weight is more volatile, and if the molecular weight is too large, there is a tendency that the raw material becomes highly viscous, the workability is deteriorated, and it is difficult to express. The crosslinking effect by the reaction of an alkenyl group and a sulfhydryl group is exhibited. • As a component of (4)' In order to achieve a uniform mixing with other ingredients and good workability, the viscosity is less than 3〇〇〇pa under 2yc. $ is better than 2000 Pa. s. It is not more than 1〇〇〇pa·$. The viscosity can be measured by the E-type viscometer. As the component (8), it is important to suppress the coloration and the yellowing is yellow. 149086.doc •19- 201120145 The compound having a phenolic hydroxyl group and/or a phenolic θ.1 group of bamboo organisms is less contained, and more preferably a compound containing no derivative having a right hydroxy group and/or a phenolic hydroxyl group. In the present invention, the phenolic hydroxyl group of hydrazine refers to a hydroxyl group directly bonded to the nucleophilic nucleus of the sulphuric hydrocarbon nucleus of the sulphur, which is exemplified by the present, naphthalene ring, anthracene ring, etc., and is derived from a phenolic base. The system refers to the hydrogen atom of the (4) (4) group via a methyl group, an ethyl group, etc., an ethylene group, an allyl group, etc. a group obtained by substituting a fluorenyl group such as an alkenyl group or an ethenyloxy group, etc. The (4) component is preferably a 4-alkenylcyclohexene or a dicyclopentane from the viewpoint that the obtained cured product has less coloration and higher light resistance. Dilute, heterogeneous uric acid: Rare propyl cool 'isocyanuric acid dil propyl mono-glycid vinegar, three (2 _ gynecoxy oxyethyl) isocyanuric acid vinegar, 2, 2 _ double (4_ via base ring Diethyl propyl dipropyl ether, 1'2,4-divinylcyclohexane; particularly preferred: isocyanuric acid triallylpyridinium 2,2-bis(4-hydroxycyclohexyl)propane Diallyl ether, i, 2,4-trivinylcyclohexane. As the component (A), it may have another reactive group. As a reaction in this case, an epoxy group or an amine may be mentioned. a radical, a polymerizable unsaturated group, a carboxyl group, an isocyanate group, a hydroxyl group, an alkoxyalkylene group, etc. In the case of having such a reactive group, the adhesion of the obtained curable composition is easily ruthenium and the resulting hardening The strength of the substance tends to be high. In terms of further improving the adhesion, the epoxy group is preferably an epoxy group. Further, the resulting cured product is easily obtained. In terms of heat resistance, it is preferable to have one or more reactive groups per molecule. In particular, as the component (A), from the viewpoint of heat resistance and light resistance, a general formula (preferably) I) Compound represented by: m 149086.doc -20- 201120145 [Chem. 17] Ο

(wherein R2 is a one-valent organic group having a carbon number of 1 to 50, and may be substituted by oxygen, nitrogen, sulfur, or a halogen atom; and each R2 may be the same or different). As R2 of the above formula (1), from the viewpoint of further increasing the heat resistance of the obtained cured product, it is preferred that the carbon number is one of the organic groups, and more preferably the carbon number is from 1 to 10. The valence organic group is more preferably a valence organic group having a carbon number of 1 to 4. Examples of such preferred R2 include a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a benzyl group, a stupid ethyl group, a vinyl group, an allyl group, a glycidyl group, and the following groups. [Chem. 18]

149086.doc -21. 201120145

H 1 H ^fO4^0

Preferable specific examples of the organic compound represented by the above formula (I) include triallyl isocyanurate and the following compounds.

化 °γ% 〇丫 丫Ο 丫Ο ^γΝγΝτ^

0 0 0

m. 149086.doc -22- 201120145

9 ΟγΝγ, Ο ΟγΝγ.0 Ο , 〇 In order to simultaneously achieve the improvement of the resin strength and light resistance of the cured product, it is preferred to use a mixture of triisopropyl uric acid and diisopropyl propyl monoglycidyl urethane. Since the mixture has an isocyanuric acid ring skeleton, it is also effective in terms of heat. The mixing ratio can be arbitrarily set, and in order to achieve the above object, it is preferred that triallyl isocyanurate/diallyl monoglycidyl isocyanurate (mole ratio) = 99/1 to 1/99, more preferably 95/5~5/95, especially good for 90/10~10/90. Further, from the viewpoint of increasing the Abbe number of the obtained cured product, the component (A) is preferably an aliphatic hydrocarbon compound having a cyclic structure. For example, vinyl norbornene, vinylcyclohexene, diallyl ether of 2,2-bis(4-hydroxycyclohexyl)propylamine, 1,2,4-trivinylcyclohexane Wait. From the viewpoint of lowering the Abbe number of the obtained cured product, a compound having the skeleton of the above formula (II) is preferred. Further, from the viewpoint of increasing the number of shells of the obtained cured product, it is preferably a compound having a skeleton of the above formula (1) or an aliphatic hydrocarbon compound having a cyclic structure. Further, from the viewpoint of high heat resistance and high refractive index of the obtained cured product, a compound represented by the general formula (II) is preferred: [Chem. 20]

Wherein R is a one-valent organic group having a carbon number of (10), which may be substituted by an oxygen, a nitrogen sulfur, a 3 or a γ atom; each R3 may be the same or different). R3 is a valence organic group having a carbon number of (d), preferably a hydrocarbon group, more preferably a * group. Further, the carbon number of the organic group is preferably 丨~;^. Specifically, it is preferably divinylbenzene, divinylbiphenyl, A isopropene benzene, ruthenium di(tetra)benzene, and a material (four), or a two-year dilute propyl test, or a double [4- (2. Dilute propoxy) phenyl w (bis(tetra) dilute w =), stupid (four) paint resin, etc., containing epoxy resin on the ring, . One or all of the glycidyl group is replaced by a propyl group. /乍: R3 of the formula (11) can further improve the resistance of the obtained cured product, and is preferably a compound having a plurality of aromatic rings. As such a square ring, it is preferably the structure shown below. [Chem. 21]

i490S6.doc •24- 201120145 -I- Further, in terms of further improving heat resistance, the component (A) is preferably selected from diallyl isocyanurate or diallyl monoglycidyl isocyanurate.稀 稀 丨, 丨, 4/-trivinylcyclohexane, vinyl cyclohexene, vinyl norbornene, bisphenol A diallyl ether and bisphenol S diallyl ether Bisphenol A diallyl ether and bisphenol s diallyl ether maintain a low Abbe number and improve heat resistance. The component (A) may be used singly or in combination of two or more. (Component (B)) (R represents a divalent group selected from the group consisting of 卜~~ch2-) CM3 OH〇9^3ί: Next, the (Β) component is described. β (Β) component of the present invention is double A polyoxo compound having at least two SiH groups in one molecule obtained by reacting an organic compound having a functional group or more with a polyoxyalkylene compound. The molecular structure of the above organic compound is not particularly limited, and it is preferably not a polyoxane-organo block copolymer or a polyoxyalkylene-organic graft copolymer containing a siloxane unit (Si-0-Si). 90% by weight or more of the constituent elements are at least one selected from the group consisting of c, H, N, oxime, s, and halogen. This means that the component (B) is not a compound containing only a siloxane skeleton. Here, the so-called siloxane skeleton is, for example, (R223 Si〇)/2)P(R222Si〇2/2)q(R22Si03/2)r(Si04/2)t (R22 represents the same or different Substituted or substituted one-valent hydrocarbon 149086.doc -25- 201120145 base, P, q, r and t represent the molar number of each oxane unit, p, qr and 1 are 〇 or positive number, leaf 廿: +1 =1) As usual, the main chain only contains the skeleton of the continuous si〇 bond. A compound containing only the Shihe oxygen 6 skeleton, when the value is large, the linear expansion coefficient becomes large, and it is difficult to use it as an optical component. When the value of the coffee is large, it may become easily broken when a thermal shock is applied. The tendency. p is 〇~300, preferably 〇~1〇〇; £] is 〇~5〇〇, preferably 〇~3〇〇; 犷 is 〇~500, preferably 〇~30〇; t4〇~ 5〇〇, preferably 〇~3〇〇. The viewpoint of having good compatibility with the component (A) and the fact that the volatility of the component (b) is low and it is difficult to generate gas from the resulting composition, the component of the component (B) is preferably An organic compound (α) having two or more carbon-carbon double bonds reactive with an SiH group in one molecule of a difunctional or higher organic compound, and at least three SiHs as a polyoxymethane compound A compound obtained by conducting a cerium nitridation reaction on a polyorgano oxy-oxygen (p). The molecular weight of the component (B) is not particularly limited, and any of them can be preferably used. From the viewpoint of more easily controlling the fluidity of the curable composition, it is preferred to use a low molecular weight. In this case, the lower limit of the preferred molecular weight is 50, and the upper limit of the preferred molecular weight is 1 Torr, more preferably 1 Torr, more preferably 2,000 Å ((〇〇)) The component of the ") component preferably has a number average molecular weight of at least two carbon-carbon double bonds reactive with the SiH group in one molecule from the viewpoint of compatibility with the component (A) or the component (D). It is an organic compound of 3 Å or less. It is also possible to use (αΐ), which has at least 2 and SiH groups in the molecule i as the component (A) above, 149086.doc -26· m 201120145 The reactive carbon-carbon double bond has the same number average organic molecular weight of 1 〇〇〇〇 or less. When the (αΐ) component is used, the crosslinking density of the obtained cured product is improved, and it is easy to obtain hardening with high mechanical strength. As the (α) component, (α2) may be used, which is an organic compound having two carbon-carbon double bonds having a reactivity of a carbon-carbon double bond and having a molecular weight of more than 〇. Among them, the (α1) component is more preferably used from the viewpoint of heat-resistant discoloration of the obtained cured product or transparency at a high temperature. The component (8) is preferably a compound having a skeleton of the above formula (I) or formula (II) in view of high calorific value. The component (4) is preferably a compound having a cyclic structure from the viewpoint of a high refractive index, for example, an aliphatic tobacco compound such as a dilute norbornene or a compound having a skeleton of the above formula (11). Examples of the compound having a skeleton of the formula (II) include divinylbenzene-based divinylbiphenyl, 1,3-diisopropenebenzene, M-diisopropylbenzene, and the like. , or double-folded A di-propyl propyl group, or double [4_(2_-dipropoxy)phenyl] stone wind, benzene anti-clear varnish resin and other glycidyl groups bonded on an epoxy resin containing an aromatic ring Some or all of them are replaced by a weak propyl group. • As a result of (4)' reducing the Abbe number of the obtained cured product, it is a compound having a skeleton of the above formula (9). Further, from the viewpoint of increasing the Abbe number of the obtained cured product, a compound having the skeleton of the above formula (1) or an aliphatic hydrocarbon compound having a cyclic structure or the like is preferable. ((β) component) It can be used as a polyorganismite having at least 3 SiH groups in one molecule of (8) 149086.doc -27· 201120145 Burning is not particularly limited, and Tongru can use International Publication No. 96/15 The compound disclosed in the manual No. 194 has at least three SiH bases in the knives. In the polyorgano enthalpy having at least three SiH groups in one molecule, as a chain compound, the organopolyoxane is a compound of the above formula (V).

(V) (wherein R23 and R24 represent hydrogen or a carbon number is a one-valent organic group of (9), and each of R and β may be the same or different and at least (10) is hydrogen; η represents (i) an integer of 嶋). From the viewpoint that R and R ' can improve the heat resistance of the obtained cured product, it is preferably a valence organic group having a carbon number of 1 to 2 Å, more preferably an organic group having a carbon number of i 15 15 or more. The carbon number is one of the organic groups. As an example of such a comparison, a methyl group, an ethyl group, a propyl group, a butyl tertyl group, a phenethyl group, a methoxy group, an ethoxy group, an ethyl bake group, and an allyl glycidyl group are mentioned. Wait. η is preferably an integer of 1 to 3 Å. In the polyorganosiloxane having at least three SiH groups in the knives, examples of the cyclic polyorganooxanes include those represented by the following formula (VI): at least three of the molecules in the molecule. Cyclic polyorganosiloxanes, etc.: Knife 149086.doc •28· (VI) 201120145 [Chem. 23]

= Ί25 represents hydrogen or a carbon number of the organic group of carbon 6, each R25 can be the same as =, at least 3 are hydrogen; η represents an integer of 2 to 10, and R25 of the above two groups is preferably c, H, 〇 constitutes a carbon number of 1 to 6 'better' is more preferably a hydrocarbon number of carbon number 6, more preferably a carbon number of the burnt soil of the 6 and η is preferably an integer of 3 to 1 〇 . Preferred examples of the cyclic polyorgano oxy-oxygenation represented by the general formula (VI) are as follows: (8) trimethylcyclotrisocene, tetramethylcyclotetraoxane, 1,3 , 5,7,9-pentamethylcyclopentaoxane, and the like. Among these, in terms of availability, a chain-like and/or cyclic and/or branched polyorganosiloxane having a number of > 3 SiH groups in the oxime molecule is preferred. Further, in terms of compatibility with the component (A), a cyclic polyorganosiloxane or a linear polyorganosiloxane having a molecular weight of 10,000 or less is preferred. From the viewpoint of the glass transition temperature, a cyclic and branched polyorganosiloxane is preferred. From the viewpoint of higher strength, a cyclic polyorganosiloxane is preferred. Further, the '(β) component may be used singly or in combination of two or more. (Pre-Reaction) Next, the reaction for obtaining the (Β) component will be described. 149086.doc -29· 201120145 When the bifunctional or higher organic compound and the (iv) oxygen (tetra) compound are subjected to a chlorination reaction, if the mixing ratio of the two is in the range of two or more SiH groups remaining in the molecule, There is no special limit. In the case where the above component (4) is reacted with the component (8), the molar number (χ) of the carbon-carbon double bond having an anti-acute property with the sinyl group in the (4) component is from the viewpoint of the (4) of the obtained cured product. (8) The molar number of the centiole (7) in the composition is preferably Y/, more preferably Y/Xg. Further, from the viewpoint of heat resistance of the cured product, it is preferably UY/X of .7, more preferably 2&Y/X2 0.8. In the case of the hydrogenation of the stone, a suitable catalyst can be used. As the catalyst, for example, a component (c) described later can be used. The amount of the catalyst to be added is not particularly limited, and in order to have sufficient hardenability and to suppress the cost of the curable composition to be low, the lower limit of the amount of addition is preferable for the polyorgano-zepaic gas having eight SiH groups ( p) The essence of the ingredient is 丨 quot quot 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 莫 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; &1 is the ear ^, Moer, better is 1 〇 · 3 Mo. In the above catalyst, a co-catalyst may be used in combination, and examples thereof include a phosphorus compound such as trisylphosphine, a dimethyl maleate or the like, a diester compound, and a 2-trans-base 2_methyl group. An ethyl thiosulfate compound such as a butane alcohol compound such as butane or an amine compound such as triethylamine. The amount of the catalyst added is particularly limited, and the limit of the preferred addition amount of the hydrogen peroxide catalyst is 10. 5 moles, more preferably 1 {rl mole, and the upper limit of the preferred addition amount. It is better to be 10 moles. [S1. 149086.doc •30· 201120145 As a catalyst mixing method in the reaction, various methods may be employed, preferably by mixing the (α) component with the ruthenium hydrogenation catalyst (c) to (β) ) Ingredients. When the method of mixing the hydrogenation catalyst (C) in a mixture of the (α) component and the (β) component is used, it is difficult to control the reaction. Further, when a method of mixing the (α) component with the (β) component and the ruthenium hydrogenation catalyst (c) is used, the (β) component may be present in the presence of the ruthenium hydrogenation catalyst (C). The moisture incorporated is reactive and causes deterioration. The reaction temperature can be set to various temperatures, and the lower limit of the preferred temperature range is 30 ° C, more preferably 50 ° C, and the upper limit of the preferred temperature range is 2 °t, more preferably 150 °C. If the reaction temperature is low, there is a tendency that the reaction time required for sufficient reaction is prolonged; if the reaction temperature is high, it is industrially disadvantageous. The reaction can be carried out at a fixed temperature, and the temperature can be changed in multiple stages or continuously as needed. The reaction time and the pressure during the reaction can also be variously set as needed. There is no special appointment for the response time. For example, (10) sexual considerations, preferably within 2 hours, more preferably within 1G hours. There is no particular limitation on the pressure, and it is preferable to use a special device or an operation to be mixed. It is preferably atmospheric pressure ~ 5 MPa ‘more preferably atmospheric dust ~ 2 Mpa. A solvent can be used in the hydrogenation reaction of Shixi. The solvent which can be used is not particularly limited as long as it does not interfere with the hydrogenation reaction of the genus, and, as a specific example, a hydrocarbon solvent such as benzene, toluene, hexane or heptane, tetrahydrofuran, Μ·-noise, or the like can be preferably used. 1,3· Dioxolane, Diethylene (4), Solvent, Propionium, Methyl Ethyl and other oxime solvents such as chloroform, dichloromethyl chloroform, U-dialdehyde and other functional solvents. Solvents can also be made into two or more mixed solvents for use in 149086.doc •31- 201120145. The solvent 'preferably, yttrium benzene, quaternary ... is a small dioxolane, anthracene, 4-dioxane, chloroform. The amount of the solvent to be used can also be appropriately set. The amount of the solvent to be used is not particularly limited, and it is preferred to completely dissolve the component (4) in order to make the reaction uniform and to promote the reverse f'. The amount of the component (α) is 2 parts by weight or more and 5 parts by weight or less, more preferably 50 parts by weight or more and 3 parts by weight or less with respect to the (α) component of the ι 〇〇. Further, various additives can be used based on the purpose of controlling the reactivity and the like. After the hydrogenation reaction, the organic compound component having one carbon-carbon double bond reactive with the SiH group in the solvent or the unreacted ruthenium molecule, and the polyorganoindene having at least three SiH groups in one molecule may be removed. Oxytomane (ρ) component. By removing these volatile components, the problem of voids and cracks caused by volatilization of volatile components during hardening is less likely to occur. As the removal method, for example, in addition to the devolatilization under reduced pressure, the treatment with activated carbon 'aluminum silicate, tannin or the like can be mentioned. In the case of devolatilization under reduced pressure, it is preferred to carry out the treatment at a low temperature. In this case, the upper limit of the preferred temperature is 12 〇 ° c ', more preferably i 〇〇 ° c. If it is treated at a high temperature, it is likely to be accompanied by deterioration such as thickening. As an example of the component (B) obtained by the above method, a reaction product of triallyl isocyanurate tetradecylcyclotetraoxane, diallyl monoglycidyl isocyanurate and four are more preferable. Reaction of methylcyclotetracycline, reaction of monoallyl diglycidyl isocyanurate with hydrazine, 3,5,7-tetradecylcyclotetraoxane, divinylbenzene and 13,5 , 7·Tetramethylcyclotetraoxane reactant, bisphenol A diallyl ether and i,3,5,7-tetramethyl 149086.doc •32· [S1 201120145 , Si Shi Xi a reactant, a reaction of a vinyl norbornene with u, 5,7-tetramethyl-tetraoxane, or a bis[4·(2·allyloxy)phenyl]sulfone oxime 1,3, 5,7_tetradecyl ring tetradecane reactant. In the present invention, the component (8) may be used singly or in combination of two or more. (Component (C)) Next, a hydrogenation catalyst which is a component (C) will be described. The rhodium hydrogenation catalyst is not particularly limited as long as it has a catalytic activity for the hydrogenation reaction, and examples thereof include a simple substance of platinum; and a solid platinum supported on a carrier such as alumina, ceria or carbon black; Acid; a complex of chloroplatinic acid with an alcohol, an aldehyde 'ketone, etc.; a platinum-olefin complex (eg, Pt(CH2=CH2)2(PPh3)2, Pt(CH2=CH2)2Cl2); Alkoxy oxane complex (eg Pt(ViMe2SiOSiMe2Vi)a, Pt[(MeViSiO)4]b); platinum-phosphine complex (eg Pt(PPh3)4, Pt(PBii3)4); platinum-phosphorous acid a salt complex (for example, Pt[p(〇Ph)3]4, Pt[P(OBu)3]4) (wherein Me represents a methyl group, 'Bu represents a butyl group, and Vi represents a vinyl group'. , a, b denotes an integer), a dicarbonyl dimethyl gas; a Karstedt catalyst; a platinum-hydrocarbon complex (expressed in the white-smoke complex disclosed in the specification of the American Patent Nos. 3,159,601 and 3, 596, 962) Catalyst (e.g., an alkanol platinum catalyst disclosed in the specification of U.S. Patent No. 3,220,972 to Lamoreaux). Further, a vaporized platinum-olefin composite (for example, a platinum chloride-olefin complex disclosed in the specification of Modic, U.S. Patent No. 3,516,946) can also be used in the present invention. Further, examples of the catalyst other than the platinum compound include RhCl(PPh)3, 149086.doc-33-201120145

RhCl3, RhAl2〇3, RuCl3, IrCi3, Feci 2H2〇, NiCl2, TiCl4, and the like. 3, A1C13

PdCl2 In the above, in terms of catalyst activity, a gas (tetra), a surface olefin, a platinum, a vinyl fluorene complex, or the like is preferable. Further, these catalysts may be used singly or in combination of two or more. The catalyst can be used in combination with the above catalyst. Examples of the catalyst include a phosphorus compound such as triphenylphosphine, a dimethyl maleate or the like, a >2-di:: compound, and a 2-amino-2-methylbutyne. An acetylene alcohol-based compound, a sulfur-based compound such as elemental sulfur, or an amine-based compound such as triethylamine or the like. The addition of the auxiliary catalyst is not particularly limited, and is preferably a lower limit of 1 〇·5 mol with respect to the above-mentioned chlorinated catalyst i mole, and the upper limit is a range of 1 〇 2 mol, more preferably a lower limit. It is 10-1 moles and the upper limit is 1 〇 mole range. (Component (D)) Next, a polyfluorene having at least two SiH groups and/or a carbon-carbon double bond reactive with the SiH group in the structural molecule represented by the following formula as the component (D) The oxygen compound is described as R nSiO(4_n)/2 (R1 is hydrogen or a monovalent organic group having a carbon number of 1 to 50, which may be substituted by an oxygen, nitrogen, sulfur or an atom of the im group. 'R may be the same or different; An integer of 1 to 3) The component (D) is a chain-like and/or cyclic polyoxo compound having at least two SiH groups and/or a carbon-carbon double bond reactive with an SiH group in one molecule. Further, there is no particular limitation. For example, the conformity of the compounds disclosed in the International Publication No. WO 96/1551 can be used. Here, the carbon-carbon double bond reactive with the SiH substrate i S3 149086.doc -34· 201120145 is preferably described in the content related to the component (A). R1' is preferably hydrogen or a monovalent organic group having 1 to 6 carbon atoms, more preferably hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. In the component (D), the carbon molecule has at least two SiH groups and/or a carbon-carbon double bond reactive with the siH group, and thus has the following advantages: easy entry into the repetition of the (A) component and the (B) component In the unit, the surface of the obtained hardened material is transferred! • It is difficult to seep out. Further, the number of the carbon-carbon double bonds reactive with the SiH group and/or the SiH group is preferably 5 Å or less in one molecule from the viewpoint of ensuring availability, workability, and responsiveness. Specific examples of the above-mentioned bond-like polyoxo compound are shown by the following formula (V): [Chemical 24] >24 >24 R24Si-R23 n J>24 丨23~ R24 \ j)24 /

(V) (wherein R24 main 丄 丄 r23^r24 and 11 are not 虱 or carbon number is 1~50 one-valent organic group, and each R and R may be the same or different,

SiHA ^ is a carbon-carbon double bond having at least 2 hydrogens in the knife or having reactivity with the μ group; η represents an integer of the coffee. The above carbon number is 1 to 5 彳 - 彳 f right & Further, the center/preferably is a hydrocarbon group, more preferably a number. The inverse of the earth stone is preferably from 1 to 6. η is preferably υοο. As the above-mentioned cyclic 14 oxy compound, for example, a cyclic polyorgano-crushed alkane represented by the following formula (5) J 49086.doc • 35· 201120145 [Chem. 25] ^ R25

(VI) (wherein R 5 represents hydrogen or a carbon number of one of the organic groups, and each π may be the same or different 'is at least 2 hydrogens in one molecule or reacts with SiH groups - Stone is double-keyed; n means an integer from 2 to 1). Further, in the above formula (10), "the preferred gas or the organic group having the carbon number of C, H, (10) is "," and the organic group is more preferably a hydrocarbon group having a carbon number of 6 or more, more preferably a carbon number. Further, η is preferably an integer of from 3 to 10. Further preferred examples of the R23, R24 and R25 include a methyl group, an ethyl group, a propyl group, a butyl group and a phenyl group. , a benzyl group, a methoxy group: an ethoxy group, a vinyl group, an allyl group, a glycidyl group, an acrylonitrile group, etc. As the above polyfluorene oxide compound, if a compound having an alkoxy group or a hydroxyl group is used, When the cured product is exposed to high humidity conditions, there is a tendency for white turbidity to occur or the adhesion to the substrate tends to be high. Further, it is compatible with other components contained in the curable composition. From a sexual point of view, the component (D) is at 23. (The viscosity below is preferably 〇.001~5 〇pa. s, more preferably 0,003 to 4.00 Pa · s. And the '(D) component by GPC The number average molecular weight measured in terms of polystyrene is preferably from 300 to 30,000, more preferably from 300 to 2 Torr, most preferably I49086.doc -36-E S1 20112 0145 300 to 15000. In order to obtain the appearance of the cured product, in particular, the foaming of the component (D) caused by the volatile component or the like is controlled in a thermogravimetric measuring device at a temperature of 1 Torr. Preferably, the amount is less than 1%. More preferably, it is less than 5%. Further, in order to suppress volatilization of the component (D) at the time of hardening, from the viewpoint of transparency or refractive index of the obtained cured product, it is preferred to use the above. The material in the range. As the component (D), from the viewpoint of the mold release property of the cured product, a linear polycene oxygen is preferable, for example, a linear dimethyl polysulfide ((5) is manufactured by a company. DMS-V00, DMS_v〇3, DMS V〇5, dms v2i, DMs_H03, DMS-H21, etc.), methylhydrogen oxyhydrogen_dimethyl oxalate copolymer (HMS-03 manufactured by Gelest) 1. HMS-1 5 1 , HMS-301, etc.), diphenyl siloxane oxide, dinonyl fluorene copolymer (1 manufactured by Gelest); ;) ¥ _ 1625, PmM 631, _ _ 233 1, pDV 2335, etc., vinyl end% monomethyl phthalocyanine (LS-8670 manufactured by Shin-Etsu Chemical Co., Ltd.). From the viewpoint of heat resistance or low-line expansion In other words, it is preferably a linear polyfluorene or a cyclic siloxane having a plurality of SiH groups in the ruthenium molecule, for example, as a linear polycyanium, which is a ruthenium, and a methyl hydride. Methyl oxime & copolymer (HMS-〇31, HMS-151, HMS-301, etc., manufactured by GeleSt Co., Ltd.), as a cyclic oxirane, LS_8600, LS-8670 manufactured by Shin-Etsu Chemical Co., Ltd. , LS-8990, etc. The amount of the component (D) added is preferably 〇.005 to 10 parts by weight, preferably 0.03 to 5 parts by weight, based on the total weight of the components (A) and (B). 0.1 to 3.5 parts by weight. In the case of less than 0.005 parts by weight, there are 149086.doc •37-201120145 in the following problems: it is impossible to ensure sufficient mold release property with the substrate, or hardening unevenness due to hardening hardening reaction is more than 1 In the case of 〇 by weight, there is a problem of oozing or a decrease in surface hardness. Further, in either case, there is a problem that the birefringence of the cured product is improved. Further, in terms of the coefficient of linear expansion, it is preferably 0.005 to 2.5 parts by weight. In the invention of the present invention, the use of the component (D) has a tendency to increase the coefficient of linear expansion. However, by using a specific amount of the component (D), it is possible to suppress the coefficient of linear expansion within a practically acceptable range. And a composition of a hardened material having a low birefringence. Moreover, the mold release property of the cured product can also be improved. (Curable composition) The ratio of the component (A) to the component (B) in the curable composition is preferably: [the carbon of the component (A) having reactivity with the SiH group in the curable composition - carbon The molar value of the double bond/the number of moles of the wh group of the component (B) in the curable composition is a ratio of a lower limit of 〇.〇5 and an upper limit of 1〇, and more preferably a lower limit of 0.1. The upper limit is the ratio of the range of 5. More preferably, it is a ratio in which the lower limit is 0 · 3 and the upper limit is 2.5. When it is less than 〇〇5, there is a tendency that the crosslinking effect by the reaction of the carbon-carbon double bond and the SiH group is insufficient; in the case of more than 10, there is an unreacted (A) component self-hardening substance. The tendency to ooze out. From the viewpoint of heat resistance and photochromic resistance of the cured product, the above ratio is preferably 1.5 or less. If it is larger than 丨.5, there is a case where the coloration after the environmental test becomes large. The amount of the hydrogenation catalyst added to the component (C) in the curable composition is not limited to 149086.doc -38- m 201120145 In order to impart sufficient hardenability, the lower limit is 10-1 moles, more preferably 10-8 moles, relative to the base of the (A) component, in order to suppress hardening: the cost of the composition is suppressed to be low. The upper limit is 1 〇·2 mol, and more preferably the range of 1 〇·3 mol, relative to the 8 卍 i-mole of the component (A). In addition, when the catalyst exhibits sufficient hardenability in the amount remaining in the case of synthesizing the component (B), it is not necessary to add it, and the touch may be newly added in the above range in order to adjust the hardenability. Media. (Other Additives) In order to improve the storage stability of the composition of the present invention or to adjust the reactivity of the hydration reaction in the production process, the retarder may be hardened. The hardening retarder may, for example, be a compound containing a simple non-fresh bond, an organic filler compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound or an organic peroxide. These may be used singly or in combination of two or more. The compound containing an aliphatic unsaturated bond may, for example, be a propanol = 'm compound or a maleic acid s. The organic squaring can be exemplified by a triorganophosphine, a diorgano scaly, an organic arsenic, a triorganomide or the like. Examples of the organic sulfur compound include organic: alcohols, diorganosulfides, hydrogen sulfide, benzo(tetra), (iv), and thiazole disulfides. j is a nitrogen-containing compound, and examples thereof include ammonia, primary to tertiary alkylamines, amines, urea, and cultivating. The tin-based compound may, for example, be stannized dihydrate, stannous acid or the like. The organic peroxide may, for example, be dibutyl butyl peroxide, dicumyl peroxide, benzammonium peroxide, or 149086.doc • 39- 201120145 tert-butyl benzoate. Among these hardening retarders, benzothiazepine, thiostilbene, maleic acid dimethyl vinegar, and 3-hydroxyl methyl butyl butyl acrylate are preferred from the viewpoints of good delayed activity and good raw material availability. Ethyl bromide 1-cyclohexanol. The amount of the hardening retarder added is preferably 1 mol relative to the amount of the catalytic catalyst used, the lower limit is ... the molar limit, the upper limit is 1 〇 3 moles, more preferably the lower limit is 1 mol, and the upper limit is 5 〇 Mo range. The various resins which can be added to modify the properties of the curable composition of the present invention will be described. The resin may, for example, be a polycarbonate resin, a polyacetal resin, a polyaryl vinegar resin, an epoxy resin, a sulphuric acid vinegar resin, or a (four) (four) resin' polystyrene resin, a polyethylene shrink resin, an amine group. Ethyl formate resin, polyester resin, etc., but it is not limited to these. / It may be desirable to add an inorganic filler to the curable composition of the present invention. When an inorganic filler is added, it is possible to effectively increase the strength of the material or improve the flame retardancy and the like. As the inorganic filler, preferably in the form of fine particles, examples include: oxidized sulphur, sulphuric acid, molten sulphur dioxide, crystalline sulphur dioxide, ultrafine powder, amorphous silica dioxide, hydrophobic ultrafine powder dioxide Shi Xi, talc, barium sulfate, phosphor, etc. Examples of the method of adding the filler include a hydrolyzable sulphuric acid monomer or a condensed polymer such as an alkoxy group, an alkoxy sulphide or a catalyzed sinter, or a metal such as titanium or a metal. A method of adding an oxide, cerium oxide or a dentate or the like to the curable composition of the present invention, reacting in a composition or a part of the reactants of the composition, thereby producing an inorganic filler in the composition 149086.doc • 40· i S1 201120145 and so on. An anti-aging agent may also be added to the curable composition obtained in the present invention. As the anti-aging agent, in addition to the commonly used anti-aging agent such as a hindered phenol system, gluconic acid or phosphoric acid, a sulfur-based anti-aging agent and the like can be cited. As a hindered anti-aging agent, it can be used to refine it from Ciba (Ciba

Chemicals) obtained various hindered phenolic anti-aging agents led by Irgan〇x 1〇1〇. Examples of the sulfur-based anti-aging agent include sulfur compounds such as mercaptans and sulfurs, sulfides of sulfurized carboxylic acid esters or hindered phenol-based sulfides, polysulfides, and dithio(tetra) salts. , thioureas, thiophosphoric acid vinegars, sulphur compounds, thioaldehydes, thiones, thiones, thiols, monothio acids, polythio acids, thioguanides, sulfoxides Wait. Further, these anti-aging agents may be used singly or in combination of two or more. A radical inhibitor may also be added to the curable composition obtained in the present invention. As the radical inhibitor, for example, 2,6-di-t-butyl-3-methyl phenol (ΒΗΤ), 2,2|·methylene bis (4-methyl-tert-butyl benzene) ) tetrakis (methylene-3(3,5-di-t-butyl-4-yl-phenyl)-propionic acid vinegar), such as a free radical inhibitor, or phenyl I naphthylamine, α-naphthylamine 'Ν, Ν, _ two second butyl p-phenylenediamine, (tetra) azine, hydrazine, hydrazine, diphenyl p-phenylenediamine and other amine-based free radical inhibitors. It is also possible to use two kinds in combination, and the radical inhibitors can be used alone.

First, ultraviolet absorbing can be added to the curable composition towel obtained by the present invention. Examples of the ultraviolet absorber include 2—(2,-trans-p-, di-dibutylphenyl)benzotrienyl, bis(2,2,6,6-tetramethyl-4(4)).癸二149086.doc 201120145 acid ester and so on. Further, the ultraviolet absorbers may be used singly or in combination of two or more kinds, and other flame retardants, surfactants, and the like may be added to the curable composition of the present invention within the range not detracting from the object and effect of the present invention. Antifoaming agent, emulsification known] leveling agent, anti-shrinking agent, recording agent for recording and ionic ions, thixotropic imparting agent, tackifier, anti-odor oxidizing agent, light stabilizer, thickener, plasticizer, antioxidant , heat stabilizer, processing stabilizer, reactive diluent, antistatic agent, radiation blocker, nucleating agent, phosphorus peroxide decomposer, lubricant, pigment, metal passivator, adhesion imparting agent, physical property Adjusting agent, etc. The curable composition of the present invention is obtained by mixing the above components and the like. Further, the method for curing the curable composition of the present invention is not particularly limited, and the respective components may be mixed and the reaction may be carried out, and the reaction may be carried out by heating. From the viewpoint of quick reaction and easy availability of a material having high heat resistance, a method of reacting by heating is preferred. As the reaction temperature, various settings can be made, and the lower limit is 25 t, the upper limit is 300 T: the temperature range, and the lower limit is 5 (TC, the upper limit is 280 ° C, and the lower limit is l〇〇 °c). The upper limit is 260 ° C. If it is less than 25 ° C, the reaction time for sufficient reaction tends to be long; if it is higher than 300 ° C, the product tends to be prone to thermal deterioration. It can be carried out at a fixed temperature, and the temperature can be changed in multiple stages or continuously as needed. Compared with the reaction at a fixed temperature, the reaction is easily carried out in a multi-stage or 149086.doc •42·201120145 continuously increasing the temperature. The deformed uniform hardened material is preferred, and the pressure during the reaction can be variously set as needed, and can be reacted under constant pressure, high pressure, or reduced pressure. (Cured product) The hardenable composition of the present invention is hardened. The hardened material obtained is transparent, and the transmittance is maintained well in the ultraviolet region. Specifically, a cured product having a light transmittance of 60% or more at a wavelength of 400 nm at a thickness of 3 mm can be obtained. Better More than 70%, more preferably 80% or more. Further, even if the cured product is heat-treated, the change in transmittance at a wavelength of 4 〇〇 nm is extremely small. Specifically, it is performed at 280 ° C for 3 minutes in the atmosphere. After the heat treatment, the light transmittance at a wavelength of 400 nm is 6% or more, and the light transmittance can be maintained at 10% or less. The light transmittance after heating is preferably 7% or more, more preferably 80% or more. The light transmittance change is preferably 5% or less. Thus, the cured product of the present invention has reflow resistance, and the design freedom of the optical semiconductor or the module and the optical component can be increased by such high heat resistance. Or use. The birefringence of the cured product obtained by hardening the curable composition of the present invention is small. The amount of birefringence is preferably less than 2 〇〇 mn, more preferably less than 10 〇 nm, so that the present invention The cured product obtained by curing the curable composition has a small coefficient of linear expansion. For example, the linear expansion coefficient at 3 〇t is 15 〇 ppm/κ or less, and at 150 C is 2 〇〇 ppm/K or less. Preferably 185

Hardened material below Ppm/K. In this way, it is possible to obtain a cured product having a linear expansion coefficient which is practically not problematic and has a small birefringence, so that the deviation of the focus or aberration caused by the temperature of the optical component of 149086.doc -43· 201120145 can be made small. Moreover, the thermal shock during the thermal history when the part is applied is small, and the optical component has excellent characteristics when used for optical parts. Further, depending on the part, various types of coatings such as anti-reflective coating (AR Coatmg) are necessary. At this time, if the coefficient of linear expansion at a high temperature is lower than =, there is a case where the heat process is limited in the coating step, the step is complicated or the coating treatment cannot be performed, but the cured product having the composition of the present invention can be used. Improve these issues. The cured product obtained by curing the composition of the present invention may have a hardness (Shore D) measured by a D-type hardness tester of JIS K6253 of 3 Å or more, preferably 50 or more at 25 ° C. More preferably 55 or more, more preferably 6 or more. Since the Shore D hardness is high, it has the following advantages: it has mechanical strength, the surface is less likely to form scratches, and it is less likely to adhere to dust. Further, since the machining of cutting or drilling can be performed, a complicated shape or a modified shape can be imparted after the optical component is formed. The glass transition temperature of the cured product obtained by hardening the composition of the present invention is preferably 6 Å or more, more preferably 8 〇 ° C or more, still more preferably 12 (TC or more. When the glass transition point is changed, the optical characteristics or dimensional accuracy may vary greatly. Therefore, if it is less than 6 (rc, the usable temperature range of the obtained molded body tends to be narrowed. The hardening obtained by hardening the composition of the present invention is obtained. The material exhibits excellent mold release property to the substrate. The substrate is not particularly limited, and examples thereof include metal steel materials or glass used in plastic molding, and such materials may be made of Cr or Νι. For the treatment of plating or fluorine-containing special plating, etc. [S1 149086.doc -44- 201120145 is used as a mold. The optical material according to the present invention means visible light, infrared light, ultraviolet light, X-ray, All the materials used for the light such as laser light to pass through the use of the material. The above-mentioned optical (4) can be made into various shapes such as a film-like body of a job film or a block of a lens or a prism. Light guide or An optical component such as a reflective film, an optical component such as a lens or a prism, an optical semiconductor module, etc. More specifically, for example, a camera (a still camera, a digital camera, a surveillance camera, a mobile phone camera, a vehicle-mounted camera, etc.) Or various kinds of lenses or cymbals used in optical measuring instruments, optical memory devices, etc., optical semiconductor sealing agents, light guide plates, anti-reflective cymbals, cymbals, deflecting plates, various transparent films or sheets, or light The receiving component is a photo-semiconductor module, etc. The hardened material obtained by the composition of the material of the first element of the field can be combined with the two types of materials, especially for the use of the color difference. Abbe number material and low Abbe number

The material 'the curable composition of the present invention can be made into these two materials, and can be preferably used in such applications. As an A lens unit, etc. The above-mentioned use is exemplified, for example, by the use of such components, and the number of methods applicable to the right ten is increased. Therefore, the assembly module 9 can be economically advantageous by studying the method. [Examples] However, the present invention is not limited to the following, and examples and comparative examples of the invention are disclosed below. 149086.doc •45· 201120145 (NMR) A 300 MHz NMR apparatus manufactured by Varian Technologies Japan Ltd. was used. (B) The reaction rate of the allyl group in the synthesis of the component is determined by diluting the reaction solution to about 1% with deuterated chloroform, and adding it to the tube for NMR, and measuring from the unreacted allyl group. The peak of the base is obtained from the peak derived from the methylene group of the reactive propyl group. The reaction rate of the vinyl group is determined by diluting the reaction liquid to about 1% by using chloroform in an atmosphere, and adding it to the tube for NMR measurement, and the peak derived from the CH group derived from the unreacted carbon-carbon double bond, and the source thereof. It is obtained by reacting the peak of the CNN group of the Si-C bond. As the g-valent valence of the S i thiol-containing compound as a reaction product, the SiH base price (mmol/g) which was changed by 1,2 _ _ _. (Viscosity) An e-type viscometer manufactured by Tokyo Keiki (TOKYO-KEIKI) Co., Ltd. was used. The measurement was carried out using an EHD type 48 multi-cone at a measurement temperature of 23 °C. (weight reduction rate) using DTG5〇H » sample amount 11±1 mg manufactured by Shimadzu Corporation, under nitrogen flow (50 ml/min), and raising the temperature from room temperature to 100 °C at a temperature rise of 20 t/min. The weight reduction rate after holding at 100 ° C for 1 minute. (Synthesis Example 1) To a 2 L autoclave, 696 g of toluene, 556 g of 1 ς 1,1,j,5,7-tetramethylcyclotetraoxane was added, and the internal temperature was changed to 104 t. 80 g of isocyanuric acid dipropyl vinegar and 0.05 g of platinum-vinyl oxime oxime solution were added dropwise (149086.doc -46- [S, manufactured by Umicore Preci〇us Metals Co., Ltd.) ] 201120145 PTVTS-C-3.0X 'Plasma content of 3 wt0 / 〇), 60 g of toluene mixture, heated and stirred for 7 hours. Unreacted i,3,5,7-tetradecylcyclotetraoxane and terpene were distilled off under reduced pressure at 80 ° C and 4 4 kPa. It was found by 1H-NMR that one part of the SiH group of tetramethylcyclotetraoxane was reacted with triallyl isocyanurate (referred to as Bl, SiH valence: 9·4 mmol/g). The product is a mixture containing the following component (B) of the present invention as a main component. Further, it contains a platinum-vinyl anthracene compound as a component of the present invention. [Chem. 26]

(Synthesis Example 2)

Add 52 § bis[4-(2-dipropoxy)phenyl] fluorene and g-face vinyl vinyl fluorene 15 g benzene mixed

A solution of the alkane complex in xylene (platinum content: 3 wt〇/〇) was stirred and heated for 8 hours. At 110 ° C. Reduce unreacted 1,3,5,7-toluene at 80 ° C, 0.4 kPa! 149086.doc •47· 201120145 The structure of the SiH-based part of the 5,7·Tetramethylcyclotetracycline and the bis (2-dipropyl-based) phenyl] stone wind reaction (called μ, the price of u mmol / g). The product is a mixture, and 3 has the following components as the component (B) of the present invention as a main component. Further, there is a platinum-vinyl oxirane complex containing 3 as a component (c) of the present invention. [化27]

(Synthesis Example 3) Into 2 [four-neck eggplant-shaped flask, 600 g of toluene and 6 〇〇 tetramethylcyclotetrahydroborate were added], and the internal temperature was 9 Gt. A mixture of 73.5 g of divinylbenzene, ruthenium 3 § platinum-vinyl oxirane complex in a xylene solution (platinum content of 3 wt%), and 73.2 g of benzene was added dropwise. Unreacted 1,3,5,7-tetramethylcyclotetraoxane and toluene were distilled off under reduced pressure. It is known by ^-NMR that it is 丨, ^'tetramethylcyclotetraoxane

One part of the SiH group is reacted with divinylbenzene (referred to as B3, § bid: 9.0 mmol/g). The product is a mixture containing as the main component of the following component (B) of the present invention. Further, it contains the I-ethylene sulfonium complex as a component of the present invention.

[SI 149086.doc -48- 201120145 [Chem. 28]

(Synthesis Example 4) 600 g of toluene and 36 g of tetramethylcyclotetraoxane were added to 2 L of high pressure dad, and the internal temperature was 丨08t. 35 g of 5-vinylnorbornene and 〇.〇1 § platinum-vinyl oxirane complex in a xylene solution (platinum content of 3 wt%), 3 〇〇 曱 benzene Mix the mixture and heat and stir for 4 hours. During the addition, the internal temperature was raised to 110 C. The unreacted 1,3,5,7-tetramethylcyclotetrazepine was burned off under reduced pressure at 80 C and 0.1 kPa. It was found by iH_NMR that one part of the SiH group of 1,3,5,7-tetramethylcyclotetraoxane reacted with vinyl norbornene (called B4, SiH price: 8.0 mmol/g). The product is a mixture containing the following components as the component (B) of the present invention as a main component. Further, it contains a platinum-vinyloxirane complex as a component (c) of the present invention. [化29]

149086.doc -49- 201120145 (Examples 1 to 11 and Comparative Examples 1 to 4) The preparation was carried out in accordance with the following Table 1. Using triallyl isocyanurate, divinylbenzene, vinyl norbornene, polybutadiene (RICON-130 manufactured by SART0MER Co., Ltd., molecular weight in terms of polystyrene is 46〇〇~1〇〇〇〇) as A) The composition was synthesized using the composition of Synthesis Examples 1 to 4 as the component (B), and a solution of platinum-divinyltetramethyldioxane complex in diphenylbenzene (platinum content: 3 wt/〇) was used. (C) component, using DMS V〇5 manufactured by Gelest Corporation (vinyl end linear dimethyl polyfluorene, viscosity at 2; rc is 6 mPa · s, molecular weight in terms of polystyrene is 2200, weight The reduction rate is 4%) ' DMS_ H03 (SiH-based terminal linear dimethyl polyfluorene, at 23β (the viscosity is 4 mPa·s, the molecular weight in polystyrene is 21 〇〇, the weight reduction rate is 5%), PDV-2331 (vinyl end linear dimethyl diphenyl polyfluorene, viscosity at 23 C is 1 pa. s, molecular weight in polystyrene is 12,000, weight reduction is 1% ), 8670 manufactured by Shin-Etsu Chemical Co., Ltd. (vinyl-terminated cyclic dimethyl polyfluorene, at 23. The viscosity of the underarm is 3 mPa. s, polystyrene The molecular weight was 35 〇, and the weight reduction rate was 7%. As the component (D), χ22-22475 manufactured by Shin-Etsu Chemical Co., Ltd. was used as the monofunctional polyorganosiloxane to replace the component (D). Others, Irganox 1〇1〇 was used. An anti-aging agent, using a solution of a platinum-vinyl oxane complex of diphenylbenzene as a Lithium hydrogenation catalyst, using 1-ethylidene small cyclohexanol as a hardening retarder, and the formulation ratio shown in Table 1 The curable composition is produced by weighting and defoaming the composition as a curable composition. The curable composition is poured into a poly-stone rubber sheet having a thickness of 3 mm as a cross [S] 149086.doc •50. 201120145 The unit produced by sandwiching the separator into two glass plates is heated to a maximum of 18 〇<>c to obtain a cured product. For each of the obtained cured materials, the following test method is used. The transparency and heat resistance of the cured product 'glass transition temperature' linear expansion coefficient, hardness test, mold release property, and birefringence were measured. (Transparency of cured product) The measurement was performed by a spectrophotometer (Hitachi spectrophotometer U-3300). Hardened material (thickness 3 Mm) Transmittance at 400 nm (as "initial transmittance") (Heat resistance test) The heat resistance test was carried out by sandwiching the cured product in a glass heated to 28 Torr for 3 minutes. Using a spectrophotometer (Hitachi spectrophotometer U 33〇〇) The light transmittance of the cured product after the heat resistance test was measured at 4 〇〇 nm (as the "transmittance after the heat resistance test"), and the heat resistance test was conducted according to the following formula. Rate (transmission change) [Transmittance after heat resistance test] (%) = [initial transmittance] (% butyl) _ [transmittance after heat resistance test] (% τ) (glass transition temperature) Cut a test piece of 30 mmx5 mm><3 mm from the compound and use it

DVA_2〇〇 manufactured by Meter and Control Company measured dynamic viscoelasticity in tensile mode with a frequency of 10 Hz, strain 〇. 1 %, static/dynamic ratio 丨5, and heating rate of 5/min. The peak temperature of tanS is taken as the glass transition temperature of the carbide. When there is no clear peak, it is recorded as ND. 149086.doc -51- 201120145 (Linear expansion coefficient) A test piece of 5 mm×5 mm×3 mm was cut out from the hardened material, and ThermoPlus TMA83 10 manufactured by Rigaku Co., Ltd. was used, and the compression mode and the heating rate were I0°c/min. Thermomechanical analysis was performed under the conditions. The coefficient of linear expansion was obtained from the expansion ratio of 30-40 °C. (Hardness test) The cured product was placed on a blue glass, and the hardness at 25 ° C (Shore D) was measured in accordance with JIS K6253 using a D-type hardness meter. (Releasability test) The curable composition was placed in an iron ointment jar and a glass unit to which an external mold release agent was not applied, and hardened under the same curing conditions as in the above examples to check whether or not the cured product was taken out. The person who peeled off from the substrate after hardening was referred to as ◎, and the person who peeled off from the substrate after the application of the force was referred to as 〇, and the person who could not be peeled off from the substrate was referred to as X. (Birefringence judgment) A test piece of 50 x 50 x 3 mm was cut out, and measured by a KOBRA-CCD manufactured by Oji Scientific Instruments Co., Ltd., and the birefringence of the entire surface of 5 〇 x 5 〇 mm was measured. The amount of birefringence at 200 nmw was evaluated as X for hardening unevenness or streaking, and was evaluated as Δ for 1 〇〇 nm or more and less than 2 〇〇 nm, and 评价 for those less than 100 nm. . The data measured and evaluated under the above conditions are summarized in Table i. 149086.doc •52-

[SI 201120145 Comparative example inch (N ΓΟ 1 1 1 00 V〇1 〇1 1 1 mop 〇00 00 ο g (N 00 o 〇<1 (N ΓΟ 1 1 1 00 v〇1 0 1 oo CN 00 ss XXX Os m 1 1 1 宕1 o 〇\ 00 (Ν § 00 Ό 卜 ◎ ◎ <] Os 1 1 VO 1 1-^· 1 1 o as oo ο 1 in 00 CN 00 XX < Example»—寸 1 m (N ΓΛ VO 1 ooo 〇 \ oo § o <N 00 0 〇〇〇1 VO 1 1 s c> »· o 1—< o On OO <Ν ο § 00 o 〇〇〇 s VO 1 1 sopo ON oo (Ν o § ◎ ◎ 〇〇〇1 v〇ΓΟ I 1 s 0.05 1 mpo OS 00 g § 0 〇〇 1 1 00 ir> o 1 mpo 00 00 ο r-hgg ◎ ◎ 〇f〇1 1 00 VO 1 〇1 P oo r-" § ΚΓ) 00 o ο 〇Q\ 1 1 5 1 m 1 o ON oo ο § s cs 00 ◎ ο 〇 inch 〇 \ m 1 V〇 1 5 m 1 1 o ON 00 ND as On ◎ ◎ 〇m Os 1 S 1 r—^ 1 1 mo 1 o as oo ο § s VO 00 ◎ ◎ 〇 <N ON m 1 VO l fn d 1 to ON 00 D 2 g cs 00 ◎ ◎ 〇Os r-&g t; 1 1 »—H o ΓΛ 〇1 1 1 r—^ o 〇\ oo y-^ ND g (N 00 ◎ ◎ Triallyl isocyanurate divinylstyryl norbornene polybutadiene PQ (N m CQ inch CQ platinum-vinyl oxirane complex xylene solution DMS-V05 i DMS-H03 PDV-2331 LS-8670 ! X-22-2475 〇X 0 1 £f 1-ethynyl -1-cyclohexanol initial transmittance (%T) transmittance after heat resistance test (°/〇) glass transition temperature (°c) linear expansion coefficient (ppm/K) Xiao's D (25°c) Moulding test (glass) Release test (ointment tank) Determination of the amount of birefringence (parts by weight) Evaluation -53- 149086.doc 201120145 Using a cured product having the curable composition of the present invention, having optical transparency and heat resistance The discoloration property, the low linear expansion coefficient, the mold release property, and the low birefringence. [si 149086.doc 54-

Claims (1)

201120145 VII. Patent application scope: 1 · A curable composition for optical materials, comprising: (4) a number 1 average molecular weight of at least 2 carbon-carbon double bonds reactive with a siH group in 1 molecule is 1 () _ The following organic compound, (B) a polyoxyalkylene compound having at least two SiH groups in one molecule obtained by reacting a bifunctional or higher organic compound with a polyphenol compound, (C) a hydrogenation catalyst, And (D) having the structure represented by the following formula R nSi〇(4.n)/2 (R is hydrogen or a monovalent organic group having a carbon number of 1 to 50, which may be through an oxygen, nitrogen, sulfur or halogen atom Substituting, each R1 may be the same or different; η is an integer of U), and a polyoxo compound having at least 2 SiH groups and/or a slave-carbon double bond reactive with the SiH group in one molecule; The component (d) is contained in an amount of 〜1 〇 by weight based on the total amount of the component (A) and (B). 2. The curable composition for an optical material according to Item 1, wherein the viscosity of the component (D) at 2 3 C is 0.001 to 5.0 Pa·s. 3. The curable composition for optical materials according to claim 1 or 2, wherein the component (D) has an average molecular weight of 300 to 30,000 in terms of polystyrene as measured by gel permeation chromatography. 4. The curable composition for an optical material according to any one of claims 1 to 3, wherein the component (D) is heated in a thermogravimetric apparatus at i〇〇°c! After 1 minute, 149086.doc 201120145 The weight reduction was less than one. 5. The curable composition for an optical material according to any one of claims 1 to 4, wherein the (Β) component is obtained from a bifunctional or higher organic compound represented by the following formula (1). (wherein R is a monovalent organic group having a carbon number of (10) and may be substituted by oxygen, sulfur, or a halogen atom; each R2 may be the same or different). 6. The curable composition for an optical material according to any one of Items 1 to 4, wherein the (Β) component is obtained from a bifunctional or higher organic compound represented by the following formula (π) [Chemical 2 ] (In the formula, R3 is an organic group having a carbon number of 5% by weight, and may be substituted by oxygen, sulfonium or ii atom; each R3 may be the same or different). The curable composition for an optical material according to any one of claims 1 to 4, wherein the intermediate component is obtained from a difunctional or higher aliphatic compound having a cyclic structure. The invention relates to the hardening composition for optical materials of any one of claims 1 to 7, wherein the (A) component is an aliphatic hydrocarbon compound having a cyclic structure. . The curable composition for optical materials of any one of claims 1 to 7 wherein the component (A) is selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the formula (II). At least one of the group consisting of [3] 4 I (I) wherein R 2 is a one-valent organic group having a carbon number of 50 and may be substituted by oxygen, nitrogen, sulfur or a halogen atom; each R 2 may be the same or different). [Chemical 4] (wherein R3 is an organic group having a carbon number of 1 to 50, and may be substituted by oxygen, nitrogen, sulfur, or a halogen atom; and each R3 may be the same or different). The curable composition for optical materials according to any one of items 1 to 7, wherein the component (A) is selected from the group consisting of triallyl isocyanurate and dimercaptopropyl monoglycidyl isocyanurate. Divinylbenzene, bisphenol A dimercaptopropyl ether, bisphenol S diallyl ether, polybutadiene, vinyl norbornene, vinylcyclohexene, and 1,4,6-trivinyl ring At least one of the group consisting of hexane. The hardening composition for optical materials according to any one of claims 1 to 1, wherein the (Α) component is contained in the parent 1 g (A) component and contains 〇 4 mmol or more and the SiH group. Reactive carbon-carbon double bond. The curable composition for optical materials according to any one of claims 1 to 11, which provides a hardening (thickness of 3 mm) hardening at a wavelength of 4 〇〇 nm of 60% or more. Things. The hardenable composition for optical materials according to any one of claims 1 to 12, which provides a light transmittance of a cured product (thickness: 3 mm) in the atmosphere at 28 (TC for 3 minutes of heat treatment) A hardened composition for an optical material according to any one of claims 1 to 13, which can be provided at a Shore D at 25 ° C. A hardened composition for an optical material according to any one of claims 1 to 14, which can provide a hardening coefficient at a linear expansion coefficient of 15 〇ppm/K or less at 30 ° C. 16 _ a transparent cured product obtained by hardening an optical material according to any one of claims 1 to 5 with a hardenable composition. 1 7 · an optical component 'used as a request item A transparent hardened material of 18. 18. An optical component using a transparent cured material as claimed in claim 16. 19 An optical semiconductor module using a transparent hardened material as claimed in claim 6. [S] 149086.doc 201120145 4. Designated representative map: (1) The representative representative of the case is: (none) (2) FIG element symbol represents the brief description: Fifth, if the case of formula, please disclosed invention features most indicative of the formula: (None) m 149086.doc