TW201226476A - Curable silicone-based composition comprising polycyclic hydrocarbon skeleton containing component - Google Patents

Abstract

A curable silicone-based composition is provided by the present invention to have gas barrier ability, to prevent the bending of a substrate even in case of sealing the substrate, and to offer transparent hardened material with high hardness enough for dicing. The present invention relates to a curable silicone-based composition, which comprises (A) (a) a chemical compound containing two SiH bonds of formula (1) [wherein R is the monovalent hydrocarbon or alkoxyl group not substituted or substituted by halogen atom in formula (1)] and (b) an addition reactant of polycyclic hydrocarbon having two addition reactive carbon-carbon double bonds per molecule and an addition reactant product having two addition reactive carbon-carbon double bonds per molecule; (B) a linear siloxane containing three or more SiH bonds and the phenyl group per molecule; (C) a siloxane compound having an alkoxysilyl group and/or an epoxy group, and the SiH bond; and (D)a hydrosilylation catalyst.

Description

201226476 6. EMBODIMENT OF THE INVENTION: TECHNICAL FIELD The present invention relates to a curable polysulfonium system containing a polycyclic hydrocarbon skeleton component which is useful as an optical device member, an insulating material for an electronic device, or a coating material. Composition. [Prior Art] In recent years, the components for optical devices, particularly the sealing materials of blue light-emitting diodes (LEDs) or white light-emitting diodes (LEDs) with large light energy, have been used for LEDs related to polyoxyxylene resins. Various uses. In this case, various durability to the sealing material is required. Focusing on the gas permeability of the polyfluorene sealant material due to its excellent light resistance or heat discoloration resistance and having the characteristics of polyfluorene, the silver electrode is discolored due to the intrusion of uranium gas from the outside. As a result, there is The case where the brightness of the led is lowered. In addition, when focusing on the sealing step of LED, in addition to the method of suspending the sealing material in the cup device, it is also possible to apply a sealing resin to the substrate on which a plurality of LED chips are mounted and harden the resin. After the 'cutting process by pelletizing treatment. In the production method, when a high-density polyfluorene sealing material is used, the substrate is warped due to hardening shrinkage, and precise pelletizing treatment cannot be performed. First, the present inventors propose a compound containing a polycyclic hydrocarbon skeleton having two addition-reactive carbon-carbon double bonds in one molecule, and at least three or more bonding to a ruthenium atom in one molecule. The compound of a hydrogen atom and the hydrogen peroxide 201226476 catalyst are essential components of a curable composition (Patent Document 1). However, in the cured product obtained by heat-hardening the composition, the silver electrode may be discolored due to poor gas barrier properties. Further, when the resin is applied to the substrate and the resin is hardened, the substrate is warped, and the problem of precise pelletizing cannot be performed. [PRIOR ART DOCUMENT] [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 2 0 0 5 - 1 3 3 0 7 3 SUMMARY OF THE INVENTION In view of the above problems of the prior art, the present invention provides an When the sealing is performed on a substrate on which a plurality of LED chips are mounted, the substrate warpage does not occur, so that the cured product having a sufficient hardness at the time of pelletizing treatment can be obtained. Polyoxymethylene composition. In order to achieve the above object, the inventors of the present invention have completed the present invention by further reviewing the results of the research. In other words, the present invention provides a hardenable polyoxynene-based composition containing (A) (a) having two hydrogen atoms bonded to a halogen atom in one molecule as shown by the following general formula (1). compound of,

RISIR I ο

Η RIsi--R

\J/ Hi /V -6 - 201226476 [In the formula, R is a monovalent hydrocarbon group having 1 to 12 carbon atoms or a carbon number of 1 independently substituted or substituted with a halogen atom, a cyano group or a glycidoxy group. ～ alkoxy group], and (b) an addition reaction product of a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and having two additions in one molecule An addition reaction product of a reactive carbon-carbon double bond, (B) a linear linear oxirane having three or more hydrogen atoms bonded to a ruthenium atom and containing a phenyl group in one molecule, (C) having an optional A functional group in which at least one of a group of alkoxyalkylene group and an epoxy group is a group, a siloxane compound bonded to a hydrogen atom of a ruthenium atom, and (D) a hydrogenation reaction catalyst. [Effect of the Invention] The curable polyfluorene-based composition of the present invention can provide a gas barrier property for imparting discoloration to the electrode, and the substrate on which a plurality of LED chips are mounted can be produced even if the substrate is sealed. The warpage is a curable polyfluorene-based composition having sufficient hardness at the time of pelletizing treatment. Therefore, it can be used for the protection and sealing of the light-emitting diode elements corresponding to various manufacturing steps. In addition, the cured product is excellent in transparency, and is also useful as a lens material, an optical device sealing material, a display device material, various optical materials, an electronic device insulating material, and even a coating material. 201226476 [Formation for Carrying Out the Invention] The present invention will be described in detail below. Moreover, Me represents a methyl Ph which represents a phenyl group. - sclerosing polyoxo-based composition - [(A) component] The component (A) of the composition of the present invention is (a) having two bonds in one molecule as shown by the following general formula (1) a compound of a hydrogen atom of a ruthenium atom (hereinafter also referred to as "SiH"), [Chem. 2]

R (1) H-Si

I

R (wherein R is a monovalent hydrocarbon group having 1 to 12 (preferably 1 to 6) carbon atoms or 1 carbon atom which is independently unsubstituted or substituted with a halogen atom, a cyano group or a glycidoxy group. ～6 (preferably 1 to 4) alkoxy], 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 two addition-reactive carbon-carbon double bonds in one molecule. <(a) Component> The component (a) of the reaction raw material of the component (A) is a compound represented by the formula (1). -8 - 201226476 3 Η Η

-0- RISIR

H RIsi-IR

Tt / 1. /V wherein R is an independently unsubstituted or monovalent hydrocarbon group having 1 to 12 (preferably 1 to 6) carbon atoms substituted by a halogen atom, a cyano group or a glycidoxy group. Or an alkoxy group having 1 to 6 carbon atoms (preferably 1 to 4). R in the above general formula (1) is preferably a group other than an alkenyl group and an alkenyl group, and particularly preferably a methyl group. The compound represented by the above general formula (1), for example, a structural formula: 1,4-bis(dimethylformamido)benzene represented by HMe2Si-p-C6H4-SiMe2H: HMe2Si-m-C6H4- A benzene compound such as 1,3-bis(dimethylformamido)benzene represented by SiMe2H. In addition, the compound represented by the above formula (1) may be used alone or in combination of two or more. <(b) Component> In the (b) reaction raw material of the component (A), the above-mentioned "addition reactivity" in the polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule "" refers to a property obtained by addition reaction of a hydrogen atom bonded to a ruthenium atom by a known hydrazine hydrogenation reaction. Further, the component (b) is, for example, (i) forming an addition-reactive carbon-carbon double bond between two adjacent carbon atoms in a carbon atom forming a skeleton of a polycyclic hydrocarbon. Hydrogen of a carbon atom forming a skeleton of a polycyclic hydrocarbon s-9 - 201226476 Atom is substituted with a group containing an addition-reactive carbon-carbon double bond, and (iii) a carbon atom forming a skeleton of a polycyclic hydrocarbon An addition-reactive carbon-carbon double bond is formed between two adjacent carbon atoms, and a hydrogen atom bonded to a carbon atom forming a skeleton of the polycyclic hydrocarbon is subjected to addition-reactive carbon-carbon double bond The replacement of the base, all three can be. Here, the group containing an addition-reactive carbon-carbon double bond, for example, an alkenyl group such as a vinyl group, an allyl group, a propenyl group, a butenyl group, a hexenyl group, a raw spintenyl group or the like, particularly a carbon atom number 2 ~12 and so on. The component (b) is, for example, in the following structural formula (X):

5-vinylbicyclo[2.2.1]hept-2-ene represented by the following structural formula (y)

6-vinylbicyclo[2,2,1]hept-2-ene, or a combination of the two (in the following, when it is not necessary to distinguish between these three, it is collectively referred to as "vinyl raw spinel" ). Further, the substitution position of the vinyl group of the vinyl raw spinel may be any one of a cis position (outer shape) or a trans position (inner shape), and the reactivity of the component is different due to the aforementioned configuration. There is a particular difference, so that the isomers of the above two configurations can be combined. ^-10-201226476<Modulation of the component (A)> The component (A) of the composition of the present invention can be compared with In the case of the above-mentioned (a) component 1 mol of SiH having two SiH molecules, an excess amount of more than 1 mol, less than 1 mol, preferably less than 1 mol, and less than 5 mol is in the The above component (b) having two addition-reactive carbon-carbon double bonds in the molecule is subjected to an addition reaction in the presence of a sand hydrogenation catalyst to obtain an addition reaction product having no SiH. All of the conventional ones can be used for the above-mentioned hydrazine hydrogenation catalyst. For example, a platinum-bearing carbon powder, platinum black, platinum chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and an olefin, and a bis-indenyl group. A platinum-based catalyst such as platinum acetate; a lead-based metal catalyst such as a palladium-based catalyst or a ruthenium-based catalyst. Further, the conditions for the addition reaction, the use of the solvent, and the like are not particularly limited, and may be, for example, a general user. As described above, when the component (A) is prepared, the component (b) having an excess amount of mole relative to the component (a) is used, and the component (A) has two from one molecule. (b) The addition of a reactive carbon-carbon double bond to the structure of the component. Further, the residue derived from the above component (a) may be bonded by a divalent residue containing a polycyclic hydrocarbon having an addition reactive carbon-carbon double bond having no structure derived from the above component (b). Constructor. In other words, the component (A) is, for example, the following general formula (6): YX-(Y, -X) p-γ (6) [wherein X is a divalent residue of the compound of the above component (a) γ-system- 11 - 201226476 The valence residue of the polycyclic hydrocarbon of the component (b), γ, which is a divalent residue of the above component (b), p is 0 to 10, preferably an integer of 0 to 5; compound of. Further, the p値 of the number of repetition units indicated by the above (Υ'-Χ) can be set by adjusting the excess amount of the above-mentioned (b) component which is reacted with respect to the component (a). . γ in the above general formula (6), specifically, for example, the following structural formula

The monovalent residue (in the following description, when it is not necessary to distinguish the above six, these are collectively referred to as "NB-based"' and the other is not referred to as "NB". γ in the above general formula (6), specifically, for example, the following structural formula:

A divalent residue represented. However, the asymmetric bivalent residue represented by the above structural formula is not restricted by the above description in the left-right direction. The above structural formula substantially indicates a structure including the above-described structure rotated by 180 degrees on each of the paper sheets 12-201226476. Suitable specific examples of the component (A) represented by the above general formula (6) are as follows, but are not limited thereto. (Also, the meaning of "NB" is as described above) NB-Me2Si-p-C6H4-S iMe2-NB NB~Me2S i-m-C6H4~S ΐΜβ2~ΝΒ

[Component (B)] The component (B) of the present invention is a linear siloxane having three or more hydrogen atoms bonded to a ruthenium atom in one molecule and containing a phenyl group. The SiH in the component (B) is added to the above-mentioned (A) component by having two addition-reactive carbon-carbon double bonds in one molecule by hydrogenation reaction to form a three-dimensional network structure. Hardened material. The component (B) is, for example, the following general formula (2): R, 3SiO(R, 2SiO) nSiR' 3 (2) wherein R' represents an independent hydrogen atom, unsubstituted or a halogen atom, a cyano group or A monovalent hydrocarbon group having 1 to 12 carbon atoms substituted by a glycidoxy group, but 201226476 - at least 3 R's in the molecule are hydrogen atoms, and at least one R' in one molecule is a phenyl group, and η is a 0~ A linear siloxane compound represented by the number of 100]. R' in the above general formula (2) is a monovalent hydrocarbon group which is unsubstituted or substituted with a halogen atom, a cyano group or a glycidoxy group, such as a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group. An alkyl group such as a 3-butyl group, a pentyl group, an isopentyl group, a hexyl group, a 2-hexyl group or the like; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; a phenyl group, a fluorene-, an m-, a ρ-toluene group; An aryl group; an aralkyl group such as a benzyl group or a 2-phenylethyl group; an aryl group such as a P-vinylphenyl group; and a hydrogen atom having one or more carbon atoms bonded to the group Substituted with a halogen atom, a cyano group or a glycidoxy group, for example, a halogenated alkyl group such as a methyl chloride group, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group or the like; a 2-cyanoethyl group; ; 3 - glycidoxypropyl and the like. Further, in the case of being compatible with the component (A) and forming a transparent material, at least one R' in one molecule is a phenyl group in terms of gas barrier properties. The conditions satisfying the above conditions are industrially easy to manufacture and easy to obtain, and it is preferred that the residual R' is a methyl group and a phenyl group. Specific examples of suitable components of the above (B) are as follows, but are not limited thereto.

Me3SiO(MeHSiO)3(Ph2SiO)2SiMe3 Me3SiO(MeHSiO)4(Ph2SiO)2SiMe3HMe2SiO(MeHSiO) i (Ph2SiO) 2SiMe2H HMezSiO(MeHSiO) 2 (Ph2SiO) 2SiMe2H The component (B) of the present invention may be used alone or in combination (C) component is used in combination with the above-mentioned (C) component. The component (C) of the present invention has a functional group bonded to at least one selected from the group consisting of an alkoxymethylalkyl group and an epoxy group, and is bonded thereto. a oxoxane compound of a hydrogen atom of a halogen atom, and an addition-reactive carbon-carbon double bond of the component (A) is added by a hydrogenation reaction to form a cured product of a three-dimensional network structure, and is provided with a substrate material. Adhesive. The above-mentioned decyl oxalate group and epoxy group are usually bonded to a ruthenium atom via a divalent organic group, and the carbon atom of the divalent organic group such as an ethyl group, a trimethylene group or a tetramethylene group is 2~ The alkylene group of 6 and a plurality of methylene groups partially constituting the alkylene group are substituted with an alkylene group of an oxygen atom. The (〇) component such as 1-(.2-trimethoxyformamidoethyl)-1,3,5,7-tetramethylcyclotetraoxane, 1-(3-epoxypropoxypropane Base)-1,3,5,7-tetramethylcyclotetrazine, 1-(2-trimethoxycarbazideethyl)-3-(3-glycidoxypropyl)- 1,3,5,7-tetramethylcyclotetraoxane, and the like. These may be used alone or in combination of two or more. [Mixed amount of (A), (B), and (C) components] Generally, a cured product having sufficient hardness in the above-mentioned use such as a coating material or the like is used in the present composition. In the case where the total amount of the addition-reactive carbon-carbon double bonds is 1 mol, the total amount of SiH contained in the composition is usually in the range of 0.5 to 3.0 m, preferably 〇.8~ 1.5 range of moles. In other words, an anthraquinone compound having an addition-reactive carbon-carbon double bond other than the above component (A) and/or an anthraquinone compound having SiH other than the component (B) and the component (C) are blended as In the case of any of the following blending components, the addition reaction -15-201226476 carbon-carbon double bond and SiH group in any of the blending components must be considered. However, in addition to the (A) component, the (B) component, and the (C) component, when there are no oxime compounds having an addition-reactive carbon-carbon double bond and a ruthenium compound having a SiH group, (A), (B) And the blending amount of the component (C), the total amount of the addition-reactive carbon-carbon double bond in the component (A) is 1 mole, and the component (B) and the component (C) are SiH. The total amount is usually from 0.5 to 3.0 moles, preferably from 0.8 to 1.5 moles. Further, when an anthraquinone compound having an addition-reactive carbon-carbon double bond other than the component (A) is contained, the compound has an addition-reactive carbon-carbon double bond, and the addition reactivity in all the components The total amount of carbon-carbon double bonds is preferably 50 mol% or less, more preferably 〇30 mol%. Further, when the ruthenium compound having SiH other than the components (B) and (C) is contained, the SiH of the compound is preferably 50 mol% or less of the total amount of SiH in the total composition, more preferably It is 0~30% by mole. [Component (D)] The hydrogenation reaction catalyst of the component (D) of the present invention is the same as those described in the above "Preparation of the component (A)". The blending amount of the component (D) in the composition of the present invention is not particularly limited as an effective amount of the catalyst. In general, the platinum group metal atom is usually blended in an amount of about 1 to 500 ppm, particularly about 2 to 1 ppm, based on the total mass of the above components (A) and (B). . By the blending amount within the above range, the time required for the hardening reaction becomes moderate, and there is no problem such as coloring of the cured product. -16-201226476 [Other blending components] In the composition of the present invention, in addition to the above components (A) to (D), it may be arbitrarily blended within a range that does not impair the object and effect of the present invention. Other components exemplified. <Antioxidant> In the cured product of the curable resin composition of the present invention, an unreacted addition-reactive carbon-carbon double bond in the above-mentioned (A) component remains directly, and may be borrowed as needed. The aforementioned coloring is prevented in advance by the miscible antioxidant. The antioxidant may be used in all conventional sources, such as 2,6-di-tert-butyl-4-methylphenol, 2,5-di-3-pentylhydroquinone, 2,5-di- 3-butylhydroquinone, 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6- 3-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), and the like. These may be used alone or in combination of two or more. Further, when the antioxidant is used, the amount of the blending agent is not particularly limited as long as it has an effective amount as an antioxidant, and is usually blended with respect to the total mass of the components (A) and (B) described above. Mixing is preferably 10 to 10,000 ppm, particularly about 1 Torr to 1, and 00 00 ppm is preferred. By the blending amount in the above range, it is possible to obtain a cured product which exhibits excellent oxidation resistance without causing coloring, white turbidity, deterioration of oxidation, and the like. <Viscosity/hardness adjuster> -17-201226476 In order to adjust the viscosity of the composition of the present invention or the hardness of the cured product obtained by the composition of the present invention, it may be blended with a bond to a ruthenium atom group or SiH. Linear diorganopolyoxyalkylene or reticulated organopolyalkyl; non-reactive (ie, alkenyl and S iH not bonded to deuterium atoms) chain or cyclic diorganopolyoxyalkylene, anthracene A benzene-based compound or the like. <Other> Further, in order to secure the use period, an addition reaction controlling agent such as 1-ethynylcyclohexane 3,5-dimethyl-1-hexyne-3-ol may be blended. In addition, in the range which affects the transparency, in order to increase the strength, an inorganic sputum agent such as a fumed sputum may be blended, and a dye, a flame retardant or the like may be blended as needed. Further, in order to impart resistance to light deterioration by light energy such as sunlight or a fluorescent lamp, a light stabilizer may be used. The light stabilizer can complement the hindered amine stabilizer which is generated by the deterioration of photooxidation, and the antioxidation effect can be further enhanced by using the antioxidant. Specific examples of bromo, such as bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate 4-benzylidene-2,2,6,6-tetramethylpiperidine, etc. . Further, when the composition of the present invention is used as a sealing material, in order to adhere to a substrate, a decane coupling agent may be blended to prevent the addition of a plasticizer. Further, the curing conditions of the composition of the present invention are not particularly limited, and are usually preferably 60 to 180 ° C for 1 to 5 hours. The olefin of the material is chopped with oxygen, in the non-dioxide material, and the anti-acid can be used as an ester of an appropriate agent, and can be improved without the article 18-201226476 - a cured product of the composition - by making the above invention The cured product obtained by curing the composition is excellent in gas barrier properties, and the oxygen permeability at 23 ° C is 300 cm 3 /m 2 · day or less, preferably 0 to 200 cm 3 /m 2 * day, in terms of a sheet having a thickness of 1 mm. . However, when used as a sealing material in a semiconductor device such as a light-emitting diode, it is possible to prevent penetration of corrosive gas from the outside, and it is possible to prevent the silver electrode from being discolored or even the brightness of the LED being lowered. Further, in general, the hardness (Shore D) of the cured product is 50 or more, preferably 60 or more, and usually 60 to 70. Regardless of the high hardness, the cured product is less likely to cause deformation of the substrate when it is applied to the substrate and hardened. Therefore, the cured product can be applied to a substrate on which a plurality of LED chips are mounted, and then cured by applying a composition. The granules are made into a piece of manufacturing method. The above-mentioned cured product is colorless and transparent, and is suitable as a lens material, a sealing material for an optical device such as an LED or a light-receiving element, various optical materials such as a display device material, an insulating material for electronic equipment such as prepreg, and coating. material. [Embodiment] The present invention will be specifically described by way of Examples and Comparative Examples, and the present invention is not limited by the following examples. [Examples] [Synthesis Example 1] Preparation of component (A) -19-201226476 Into a four-neck flask equipped with a stirring device, a cooling tube, a dropping funnel and a thermometer, vinyl stearene was added (trade name: V〇〇62, manufactured by Tokyo Chemical Industry Co., Ltd.; about the same molar amount of 5-vinylbicyclo[2.2.1]hept-2-ene and 6-vinylbicyclo[2.2.1]hept-2-ene The mixture was 17858 (14.88 mol) and 455 g of toluene, and heated at 85 ° C using an oil bath. 3.6 g of a carbon powder carrying 5% by mass of platinum was added thereto, and stirring was carried out, and 1698 g (8.75 mol) of 1,4-bis(dimethylformamido)benzene was added dropwise thereto over 18 minutes. After the completion of the dropwise addition, the mixture was further stirred and stirred at ll 〇 ° C for 24 hours, and then cooled to room temperature. Then, the platinum-carrying carbon was removed by filtration, and toluene and excess vinylpyrene were distilled off under reduced pressure to obtain a colorless transparent oily reaction product (viscosity at 25 ° C: 1282 0 mPa·s) 3362 g. The product was analyzed by FT-IR, NMR, GPC, etc., and it was found that (1) a compound having two p-phenylene groups (hereinafter, a typical structural formula is shown): about 4 1 Moer% 【化1 0】

C2H4_Si

Me SiNB (2) A compound having three p-phenylene groups (hereinafter referred to as a typical structural example): about 32 mol% [Chemical 1 1]

And 20-201226476 (3) A compound having 4 or more p-phenylene groups, about 27 moles. /. a mixture. Further, the content ratio of the addition-reactive carbon-carbon double bond of the entire mixture was 0.36 mol/i〇〇g. [Example 1] (A) Reaction product obtained in Synthesis Example 1 : 40 parts by mass, (B) Me3SiO(MeHSiO) 3 (ph2SiO) 2SiMe3: 52 parts by mass > (C) 1-(2-trimethoxy) Methyl decylethyl)-3_(3_glycidoxypropyl)-1,3,5,7-tetramethylcyclotetraoxane: 8 parts by mass (and, SiH in the above composition) The molar ratio of the carbon-carbon double bond is 1〇3) (D) Platinum-vinyloxirane complex: the amount of platinum atom is 20 ppm with respect to the total mass of the above composition, and 1-ethynyl group Cyclohexanol: 0.03 parts by mass was uniformly mixed to obtain a composition [Example 2] (A) The reaction product obtained in Synthesis Example 1 : 56 parts by mass, (B) Me3SiO(MeHSiO) 4 ( Ph2SiO) 2SiMe3 : 36 parts by mass > (C) 1-(2-trimethoxymethyl decylethyl)-3 _(3_glycidoxypropyl)-1,3,5,7-tetramethylcyclotetra矽 oxygen institute: 8 parts by mass (and 'the molar ratio of SiH/carbon-carbon double bond in the above composition is 1〇4) -21 - 201226476 (D) Platinum-vinyl oxime complex: uranium The atom is in an amount of 20 ppm with respect to the total mass of the above composition, and 1-ethynylcyclohexanol 〇.〇3 parts by mass was uniformly mixed to obtain a composition [Example 3] (A) The reaction product obtained in Synthesis Example 1: 56 parts by mass, (B) HMe2SiO(MeHSiO) 1 (Ph2SiO) 2SiMe2H: 36 Parts by mass, (C) 1-(2-Trimethoxycarbamidoethyl)-3-(3-glycidoxypropyl)-1,3,5,7-tetramethylcyclotetrazepine Alkane: 8 parts by mass (however, the molar ratio of SiH/carbon-carbon double bond in the above composition is 1.05) (D) Platinum-vinyloxirane complex: mass of platinum atom relative to the above composition In the case of the amount of 20 ppm, and the amount of 1-ethynylcyclohexanol: 0.03 parts by mass, the composition was obtained. [Example 4] The reaction product obtained in Synthesis Example 1 (A): 59 parts by mass, ( B) HMe2SiO(MeHSiO) 2 ( Ph2SiO) 2SiMe2H : 33 parts by mass, (C) 1-(2-trimethoxycarbamidylethyl)-3-(3-epoxypropoxy-22- 201226476 propyl -1,3,5,7-tetramethylcyclotetraoxane: 8 parts by mass (and, the molar ratio of SiH/carbon/carbon double bonds in the above composition is 1〇9) (D) uranium -vinyl alkane complex: the total mass of the uranium atom relative to the above composition is 20 ppm by mass, and 1-ethynylcyclohexanol: 〇. 〇 3 parts by mass were uniformly mixed to obtain a composition [Comparative Example 1] In addition to the component (A) described in the above Example 1, 77 parts by mass was used, and A composition of the composition (B) was obtained in the same manner as in Example 1 except that 15 parts by mass of the component (B). (Also, SiH/carbon-carbon double bond (Mohr ratio) = 1.01) [Comparative Example 2] Except for the following 1,3,5,7-tetramethylcyclotetraoxane and vinylpyrene In the same manner as in Example 1, except that the component (B) described in the above Example 1 was used in an amount of 33 parts by mass of the addition reaction product, a composition was obtained. (Also, SiH/carbon-carbon double bond (Mohr ratio) = 1.11) [Chemical 1 2]

(wherein, η is an integer of 1 to 11) -23 - 201226476 <Performance evaluation method> The composition obtained by each of the examples and the comparative examples has the following properties as a cured product and performance. Evaluation. The hardening conditions were carried out by heating at 1 ° C for 1 hour, and then hardening at 15 (TC for 5 hours). The results are shown in Table 1 and Table 2. (1) Appearance exists in 2 mm thickness between 2 glasses The separator was placed in a space of 15 mm x 40 mm x 2 mm, and heat-hardened under the above conditions. The appearance of the obtained cured product was visually evaluated. (2) Hardness A hardened material of 6 mm thickness prepared in the same manner as (1) was used. (3) The hardness was measured (Shore D). (3) Evaluation of gas barrier property A cured product having an outer diameter of ΙΟΟηιιηφ and a thickness of 1 mm was prepared, and the measurement was carried out at 23 ° C using an oxygen permeability measuring apparatus (Model 8001) manufactured by Illinois Instruments. (4) Evaluation of the shape retainability of the substrate When the composition was hardened on the substrate and the cured product was formed, the substrate was evaluated for warpage. The composition was coated on a substrate (50 mm x 150 mm x 3 mm) and subjected to the above conditions. After hardening, a cured product having a thickness of 1 mm is formed on the substrate. After being placed at room temperature, the warpage of the aluminum substrate is measured. (5) Granulation test • 24-201226476 Laminate substrate for printed wiring board (Mitsubishi gas) The composition was coated on a HL820, 50 mm x 1 50 mm x 〇.2 mm), and cured under the above conditions, and a cured product having a thickness of 1 mm was formed on the substrate. After being left at room temperature, the adhesive film was attached thereto. After the substrate is cut into a size of 5 mm x 5 mm using a DISCO (grain) pelletizing device (DAD341 type). (6) Light transmittance. For the cured product prepared by (1), the measurement is performed using a spectrophotometer. : Light transmittance at 3 points such as 800 nm, 600 nm, and 400 nm. [Table 1], Example Comparative Example Item 1 2 3 4 1 2 (1) Appearance Colorless Transparent Colorless Transparent Colorless Transparent Colorless Transparent Colorless Transparent Colorless Transparent (2) Hardness (Shore D) 65 70 65 70 72 77 (3) Oxygen permeability (cm3/m2 · day) 180 160 170 150 320 350 (4) Shape retention without yfrTT Μ frn» fm*- warpage 15mm warp 10mm (5 granule test Good, good, good, good, not possible. Η Inability to perform η (Note) * The pelletizing test of Comparative Examples 1 and 2 caused a phenomenon in which the substrate could not be kept flat when attached to the adhesive film. [Table 2] Comparison of Examples Example wavelength (nm) 1 2 3 4 1 2 8 0 0 9 0 % 9 0% 9 0% 9 0% 9 0% 9 0% 6 0 0 9 0% 9 0% 9 0% 9 0% 9 0% 9 0% 4 0 0 8 9 % 8 9% 8 9% 8 9% 9 0% 8 9% -25- 201226476 [Evaluation] The cured product of the examples is excellent in transparency and gas barrier properties and does not cause hardening on a substrate even at high hardness. The warpage of the substrate. Therefore, it is suitable for pelletizing processing. Further, in the composition of the comparative example, the gas barrier property was poor, and when the cured product was formed on the substrate, since the warpage was large, the pelletizing process could not be performed. [Industrial Utilization Price] The composition of the present invention is extremely useful as a protection and sealing in the production steps of various light-emitting diode elements. Further, various optical materials such as a lens material, an optical device sealing material, and a display device material, and an insulating material for an electronic device and a coating material are also extremely useful. -26-

Claims (1)

201226476 VII. Patent application scope: 1. A sclerosing polyfluorene-based composition containing (A) (a) having two bonds to a ruthenium atom in one molecule as shown by the following general formula (1) Compound of hydrogen atom, [Chemical 1] Si-H (1) wherein R is independently a monovalent hydrocarbon group having 1 to 12 carbon atoms or a carbon number of 1 to 6 which is unsubstituted or substituted with a halogen atom, a cyano group or a glycidoxy group. An alkoxy group, and (b) an addition reaction product of a polycyclic hydrocarbon having two addition-reactive carbon-carbon double bonds in one molecule, and having two addition-reactive carbons in one molecule - an addition reaction product of a carbon double bond, (B) a linear linear oxirane having three or more hydrogen atoms bonded to a ruthenium atom in one molecule and containing a phenyl group, (C) having an alkyl group selected from the group consisting of A functional group having at least one of a group consisting of an oxymethane alkyl group and an epoxy group, a oxoxane compound bonded to a hydrogen atom of a ruthenium atom, and (D) a hydrogenation reaction catalyst. 2. The sclerosing polyoxo-based composition of claim 1, wherein the polycyclic hydrocarbon of the above (b) is 5-vinylbicyclo[2,2,1]hept-2-ene, 6- Vinyl bicyclo[2,2,1]hept-2-ene or a combination of the two. 3. The sclerosing polysiloxane composition of claim 1 or 2, wherein the component (B) is a linear siloxane having the following formula (2), ^ R' 3SiO (R, 2SiO) nSiR, 3 (2) [wherein R' represents an independent hydrogen atom, unsubstituted or substituted with a halogen atom, a cyano group or a glycidoxy group. A monovalent hydrocarbon group in which at least three R's in a single molecule are hydrogen atoms 'and at least one of the ones in one molecule is a phenyl group, and η means a number from 1 to 100]. 4. The hard north polyoxygen composition according to any one of claims 1 to 3, wherein the (Α) component is obtained by including the component (a) and the component (a). An addition reaction in which the above-mentioned component (b) has an excess amount of molybdenum in the presence of platinum-carrying carbon, and then the removal reaction of the uranium-bearing carbon is carried out by filtration. Things. The sclerosing polyoxygen-based composition according to any one of claims 1 to 4, wherein the cured product has gas barrier properties. 6. The sclerosing polysiloxane composition according to claim 5, wherein when the composition is formed into a sheet having a thickness of 1 mm, the sheet has an oxygen permeability at 23 ° C of 300 cm 3 /m 2 . day or less. . 7 - The sclerosing polysiloxane composition according to any one of claims 1 to 4, wherein after the composition is applied onto a substrate, the composition is hardened to cause deformation of the substrate, and the resulting composition can be obtained. The hardness of the cured product (ShoreD) is a pelletizing treatment of 50 or more. The sclerosing polysiloxane composition according to any one of claims 1 to 7 is used as an optical device or a material for an optical component. 9. A cured product characterized by being patented The composition of any of the above items 1 to 4-28 to 201226476 is obtained by hardening, and the oxygen permeability is 23 cm 3 or less at 23 ° C in terms of a thickness of 1 mm. -29 - 201226476 IV Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: none