TW201434976A - Curable transparent silicone composition for optical device - Google Patents

Abstract

Provided is a curable transparent silicone composition for optical devices, which comprises an organosilicon compound in a highly branched regular form as a main material, and a highly reactive terminal type cross linking agent capable of undergoing a cross linking reaction without directionality. Therefore, the curable transparent silicone composition for optical devices takes a short curing time; exhibits a high Shear modulus at a high temperature, a high degree of cross linking, high adhesive stress, a high degree of surface curing and a high degree of transparency; can maintain transparency without any risk of discoloration even after being exposed to ultraviolet radiation, moisture and heat for a long time; and is useful as an adhesive for photo semiconductor or as a transparent material.

Description

Curable transparent fluorenone composition for optical components

The present invention relates to a curable transparent fluorenone composition for an optical element.

For adhesives or sealants used to adhere or seal electronic instruments, office appliances, automobiles, precision instruments, building materials, and the like, a variety of resins, such as polyurethane resins, acrylics, are used. An acrylic resin, an epoxy resin, and a silicone resin. Due to the increasing demand for transparent organic resin materials having excellent heat resistance and light resistance, and the recent trend toward miniaturization of optical components or brightness enhancement of light sources, it is highly expected to use an anthrone-based resin as a material for optical components, particularly The adhesive of the photo-semiconductor member has excellent heat resistance and cold resistance, electrical insulating properties, weather resistance, water repellency (water resistance) compared to conventional adhesive or sealing resins. Repellency) and transparency, and the risk of discoloration and physical degradation is low.

Therefore, it has been studied and proposed to improve the properties of anthrone-based resins. A variety of methods of quality. In some specific examples, the Japanese Patent Application Laid-Open Publication No. 2004-186168 and the Japanese Patent Application Laid-Open Publication No. No. 2006-202952 disclose an addition-curable fluorenone resin composition which is bonded to a stilbene atom Curing with a hydrogenation reaction between a hydrogen atom bonded to a halogen atom; Japanese Patent Application Laid-Open No. 2006-342200 discloses an anthrone resin composition for die bonding, which has a high Hardness and excellent heat resistance, transparency, and light transmittance in a low wavelength range, as an organic polysiloxane when an addition-curable fluorenone resin composition is produced, the composition is used straight a chain organopolyoxane and a three-dimensional network of organopolyoxyalkylene resins having a fluorene-bonded alkenyl group and having 1000 mPa. Seconds (mPa.s) or less than 1000 mPas. The viscosity of the second, the three-dimensional network organopolysiloxane resin is a beeswax or a solid at 23 ° C; and Japanese Patent Application Laid-Open No. 2008-031190 discloses a method comprising an addition curing type fluorenone resin The method of using an inorganic ion exchange material in the curable fluorenone composition to suppress corrosion due to vulcanization of a metal member.

However, an organopolysiloxane having an alkenyl group bonded to a ruthenium atom is used as a base resin of an addition-curable fluorenone resin composition, undergoing primary curing, and the chain end is first at a low temperature of 70 ° C to 100 ° C. The ones react with each other to form one chain, and then undergo secondary curing, and the less reactive side chains are thereby reacted with each other at a high temperature of 150 ° C or higher to form crosslinks. Therefore, when cross-linking is formed in a form in which a heavier structure is suspended in a lighter structure during rapid high-temperature curing, residual internal stress is increased, and there is a problem that material properties are deteriorated.

In addition, Japanese Patent Application Laid-Open No. 2005-005614 discloses a thermosetting resin composition comprising an anthrone compound, an acid anhydride, and a catalyst, and having excellent adhesion, heat resistance, moisture resistance and low stress. The ketone compound has two or more than two epoxy groups in one molecule and has a molecular weight of from 500 to 2,100. Further, Japanese Patent Application Laid-Open No. 2006-077234 discloses a resin composition for LED component encapsulation which comprises an organic polyoxane and a condensation catalyst and has improved heat resistance, ultraviolet resistance, optical transparency, Toughness and adhesion, the organopolysiloxane has a specific structure and has a weight average of 5 x 10 ³ g/mole or more than 5 x 10 ³ g/mole relative to a polystyrene standard. Molecular weight.

In addition, U.S. Patent Application Publication No. 2007-0298223 discloses a curable composition comprising a radical polymerizable organic fluorene monomer, oligomer or polymer in a thermally activated organoborane-amine complex. Curing in the presence of (organoborane-amine complex) or by blending a free-radically polymerizable organogermanium monomer oligomer or polymer, an organoborane-amine complex, and an amine-reactive compound in an oxygen-containing environment Cured. WO 2007/100445 discloses a hydrazine hydride-curable composition comprising an alkenyl active phenyl group-containing polyorganosiloxane, a Si-H active (Si-H active) phenyl group-containing polyorganosiloxane or a combination thereof Hydrogendiorganosiloxy-terminated oligodiphenylsiloxane having a specific molecular weight, alkenyl active diorganooxyl-terminated oligo-diphenylfluorene having a specific molecular weight Alkenyl-active diorganosiloxy-terminated oligodiphenylsiloxane or a combination thereof; and a hydrazine hydrogenation catalyst, and forming an anthrone product having optical transparency, high refractive index, high temperature resistance, and high upon curing Mechanical strength, thereby improving the reliability when the fluorenone product is applied to a light-emitting element.

In addition, U.S. Patent No. 5,982,041 discloses a ketone ketone grain. a decane composition of an adhesive via a radical reaction of an acryl-based reactive organic polyoxyalkylene induced by exposure to high energy radiation and an organic activity of an alkenyl reactive organopolyoxyalkylene bonded to an oxime The hydrazine hydrogenation reaction between polyoxyalkylenes is carried out.

Korean Patent No. 377,590 discloses a curable anthrone composition comprising an air oxidatively curable unsaturated compound and (a) an alkoxy group having two or more than two bonded to a halogen atom and containing no linkage to An organopolyoxane having an alkenyl group of a ruthenium atom in each molecule, and an alkoxy group having two or more than two alkenyl groups bonded to a ruthenium atom and not containing a ruthenium atom bonded to each molecule; a mixture of organic polyoxyalkylenes, or (b) an organopolyoxane containing two or more alkoxy groups bonded to a ruthenium atom and two alkenyl groups bonded to a ruthenium atom in each molecule An organopolyoxane containing two or more hydrogen atoms bonded to a ruthenium atom in each molecule; a condensation reaction catalyst; and a platinum-based catalyst, which is cured during the hydrogenation reaction and the condensation reaction A cured product having an excellent matt characteristic is formed, and is further suitable for a light-emitting diode display element.

U.S. Patent Application Publication No. 2008-0185601 discloses an addition-curable organopolyoxane resin composition comprising an organopolysiloxane resin containing an alkenyl group and a phenyl group, and by gel chromatography Measured by using polystyrene as a reference material, the weight average molecular weight is 3000 or more; organic oligosiloxane, which contains an alkenyl group and a phenyl group; an organic hydrogen oligosiloxane or an organohydrogen polyoxyalkylene Which has a specific structure; an addition-reactive catalyst; and a mold releasing agent, and when cured, it can be formed to exhibit a degree of curing of 60 to 100 at 25 ° C and a degree of cure at 150 ° C of 40 Product to 100 (measured according to ASTM D2240-86).

Furthermore, WO 2006/077667 discloses an anthrone composition for a light-emitting member package comprising a vinyl-containing organopolyoxane having a three-dimensional network structure (having a specific structure) having at least two in one molecule An organohydrogen polyoxane of a hydrogen atom bonded to a ruthenium atom and a ruthenium hydrogenation catalyst, and a cured product having a linear expansion coefficient of from 10 × 10 ^-6 / ° C to 290 × 10 ^-6 / ° C can be formed.

Further, Korean Patent No. 704883 discloses an LED package composition comprising one or more polyorganosiloxanes and an addition-reactive catalyst, and becomes a resin material upon curing.

As such, in order to meet the required property requirements in accordance with the use of the optical component, it is important to develop an anthrone resin composition having a configuration optimized for the relevant use.

An object of the present invention is to provide a curable transparent fluorenone composition for an optical element which has a short curing time; exhibits a high shear modulus at a high temperature, a high degree of crosslinking, a high adhesion stress, High surface cure and high transparency; maintains transparency without any risk of discoloration even after exposure to UV radiation, moisture and heat for a long period of time; and is suitable as an adhesive for optical semiconductors or as a transparent material.

According to an aspect of the present invention, there is provided a curable transparent fluorenone composition for an optical element, the composition comprising an organic hydrazine compound, a crosslinking agent, and an addition-reactive catalyst, wherein the organic cerium compound comprises a branched or three-dimensional network of organooxane compounds, including in a unit molecule , as well as A bonding structure selected from the group consisting of three or more than three germanium atoms (Si) each having 2 to 10 carbon atoms bonded directly to the molecule or bonded via an oxygen atom (O) The alkenyl group to Si, and the vinyl content in the molecule of from 0.1 millimoles per gram to 20 millimoles per gram.

Regarding a curable transparent fluorenone composition for an optical element, the organogermanium compound may be composed of a group consisting of (a-1) a first organoantimony compound, (a-2) a second organodecane compound, and a mixture thereof Selected as: (a-1) a first organoantimony compound selected from the group consisting of compounds represented by the following formulas (1a) to (1c); and (a-2) by the following formula (4) A second organic oxoxane compound comprising a ruthenium atom in a unit molecule, including a Q unit (quadri-functional siloxane group) or a Q unit and a T unit (trifunctional oxirane) A mixed structure of a tri-functional siloxane group, and an alkenyl group comprising three or more than three Si having 2 to 10 carbon atoms bonded directly to the molecule:

Wherein in the formula (1a), a, b and c are each represented such that 0 a 3,0 b 3 and 0 c An integer of 3; T represents (wherein R' represents an alkenyl group having 2 to 10 carbon atoms, and z represents an integer of 0 or 1); X is selected from the group consisting of: , And a combination thereof, wherein each R is independently selected from the group consisting of: an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, an aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, An aromatic hydrocarbon group of 6 to 30 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an epoxy group, an amine group (-NR ^a R ^b , wherein R ^a and R ^b are each independently represented An alkyl group having 1 to 5 carbon atoms) and a combination thereof; and Y and Z each independently from an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, an aliphatic group having 2 to 20 carbon atoms An unsaturated hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms, a hydroxyl group, an epoxy group, an amine group (-NR ^a R ^b , wherein R ^a and R ^b each independently represent 1 to 5 carbon atoms The group consisting of the alkyl group and the group consisting of the functional groups represented by the following formula (2) are selected:

Wherein in the formula (2), b, c, T, X and Y have the same meanings as defined above;

Wherein in the formula (1b), e, f, and g are each represented such that 0 e 100,1 f 5 and 0 g An integer of 2, and when expressed in a dendrimer structure, a generation number of 2 or less; each R is independently selected from the group consisting of: 1 to 20 Aliphatic saturated hydrocarbon group of one carbon atom, aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, aromatic hydrocarbon group having 6 to 30 carbon atoms, hydroxyl group, alkoxy group having 1 to 20 carbon atoms a group, an epoxy group, an amine group (-NR ^a R ^b , wherein R ^a and R ^b each independently represent an alkyl group having 1 to 5 carbon atoms) and combinations thereof; and T represents (wherein R' represents an alkenyl group having 2 to 10 carbon atoms and z represents an integer of 0 or 1); and the limitation is that R and T are selected such that each of the molecules of the compound of the formula (1b) has 2 to The number of alkenyl groups of 10 carbon atoms will be 3 or greater;

Wherein in the formula (1c), h, i, and j are each represented such that 0 h 100,1 i 5 and 0 j An integer of 2; each R is independently selected from the group consisting of: an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, an aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, having 6 An aromatic hydrocarbon group of up to 30 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an epoxy group, an amine group (-NR ^a R ^b , wherein R ^a and R ^b are each independently represented as having An alkyl group of 1 to 5 carbon atoms) and combinations thereof; and T represents (wherein R' represents an alkenyl group having 2 to 10 carbon atoms; and z represents an integer of 0 or 1); and the restriction is that R and T are selected such that each of the molecules of the compound of the formula (1c) has 2 The number of alkenyl groups up to 10 carbon atoms is 3 or more; [Chemical Formula 4] (R ₃ Si) _a (SiO _4/2 ) _b (R ₂ SiO _1/2 ) _c (SiO _3/2 ) _d ( R ₃ Si) _e

Wherein in the formula (4), a, b, c, d, and e are each represented by 1 a 30,1 b 20,0 c 30,0 d 10 and 1 e An integer of 30; and each R is independently selected from the group consisting of an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, an aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, and An aromatic hydrocarbon group of 6 to 30 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an epoxy group, an amine group (-NR ^a R ^b , wherein R ^a and R ^b are each independently represented An alkyl group having 1 to 5 carbon atoms) and combinations thereof, with the proviso that at least three R each represents an alkenyl group having 2 to 10 carbon atoms.

Further, the first organic hydrazine compound may be selected from the group consisting of compounds represented by the following formulas (3a) to (3c):

In the above formulas, m and n each independently represent an integer of 0 to 100.

Regarding the curable transparent fluorenone composition for an optical element, the second organic siloxane compound may be an organic siloxane compound having a three-dimensional network structure including 3 to 30 each containing a Q unit (SiO _{4 / 2} ) or a branched repeating unit of a Q unit and a T unit (SiO _3/2 ), and includes a portion of -SiR ¹ R ² R ³ as a capping unit (wherein R ¹ and R ² each independently represent 1) An alkyl group of up to 10 carbon atoms; and R ³ represents an alkenyl group having 2 to 10 carbon atoms).

Further, the second organomethoxyl compound may be selected from the group consisting of compounds represented by the following formulas (6a) to (6c):

Wherein in the formula (6a), l represents an integer from 1 to 30;

Wherein in the formula (6c), m represents an integer of 1 to 10; and n represents an integer of 2 to 30.

Further, the second organooxane compound may have a viscosity of 100 mPa at 25 °C. Seconds or greater than 100 millipascals. Seconds of liquid, or solid.

Regarding the curable transparent fluorenone composition for an optical element, the crosslinking agent may be a third organic siloxane compound including two or more hydrogen atoms bonded to a ruthenium atom in one molecule, including The repeating unit represented by the following formula (7): [Chemical Formula 7]-(R1 _p H _q SiO _(4-pq)/2 )-

Wherein in the formula (7), p and q are represented such that 0 p 4 and 0 q 4, at the same time 0 p+q An integer of 4; and each R ^{1 is} independently selected from the group consisting of an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 30 carbon atoms, all of which may be Substituted or substituted by a substituent selected from the group consisting of: an alkyl group having 1 to 10 carbon atoms, a halogen group, a haloalkyl group having 1 to 10 carbon atoms, a hydroxyl group, and a cyano group And its combination.

Further, the crosslinking agent may be selected from the group consisting of compounds represented by the following formulas (8a) to (8d):

Wherein in the formulae (8a) to (8d), each R ^{1 is} independently a group consisting of an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms and an aromatic hydrocarbon group having 6 to 30 carbon atoms. Alternatively, it may be unsubstituted or substituted by a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a halogen group, a halane having 1 to 10 carbon atoms. a group, a hydroxyl group, and a cyano group, and combinations thereof; and v represents an integer from 1 to 20; w represents an integer from 1 to 100; x represents an integer from 0 to 100; and y represents an integer from 1 to 50.

In addition, the viscosity of the crosslinker at 25 ° C can be 1,000 mPa. Seconds or less than 1,000 millipascals. second.

Further, the crosslinking agent may be included in an amount such that the number of moles of hydrogen atoms bonded to the ruthenium atom in the molecule of the crosslinking agent is the number of alkenyl groups bonded to all of the ruthenium atoms in the organic ruthenium compound. 0.5 to 3 times the number of ears.

Further, the crosslinking agent may be included in an amount of from 1 part by weight to 15 parts by weight per 100 parts by weight of the organic hydrazine compound.

Regarding the curable transparent fluorenone composition for an optical element, the addition reaction type catalyst may be a platinum group metal catalyst.

Further, the addition reaction type catalyst may be included in an amount of from 10 parts per million (ppm) to 5,000 parts per million based on the total weight of the organic cerium compound and the mass of the platinum group metal element.

When applied to a glass plate to a thickness of 1 mm to 2 mm and cured, the curable clear fluorenone composition for optical elements exhibits 90% relative to glass transmittance at 450 nm and 600 nm. Or higher than 90% transmittance.

Further, when the curable clear fluorenone composition for an optical element is cured to a thickness of 2 mm, the shear modulus is 150 MPa (Mpa) or less than 150 MPa at 25 ° C, and at 100 ° C or It can be 20 MPa or more than 20 MPa at temperatures above 100 °C.

Specific details of other embodiments of the invention are included in the following detailed description of the invention.

The adhesive transparent composition for an optical element according to the present invention utilizes an organic cerium compound in a highly branched regular form as a main material, and performs a non-directional crosslinking reaction via a highly reactive blocked type crosslinking agent. Therefore, the adhesive transparent composition exhibits a short curing time, a high shear modulus at a high temperature, a high degree of crosslinking, a high adhesion stress, a high surface cure degree, and a high transparency, and even after long-term exposure to ultraviolet radiation. Transparency can be maintained after moisture and heat without any risk of discoloration. Thus, the adhesive transparent composition is suitable as an adhesive or transparent material for an optical semiconductor.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the results of Fourier transform infrared spectroscopy (FT-IR) observation of the compound of Synthesis Example 1.

Figure 2 is a graph showing the results of FT-IR observation of the compound of Synthesis Example 2.

Figure 3 is a graph showing the results of FT-IR observation of the compound of Synthesis Example 3.

4 is a graph showing the results of FT-IR observation of the compound of Synthesis Example 4.

Figure 5 is a graph showing the results of FT-IR observation of the compound of Synthesis Example 5.

6 is a graph showing observation results of the cured transparent fluorenone composition for optical elements of Examples 1 to 21 and Comparative Example 1 and Comparative Example 2 at a fixing temperature (150 ° C) at a curing completion point.

7 is a graph showing the results of measuring the light transmittance after the cured transparent ketone compositions for optical elements of Examples 1 to 21 and Comparative Example 1 and Comparative Example 2 Figure.

8 is a graph showing the results of measuring the shear modulus after the cured transparent ketone compositions for optical elements of Example 10, Example 13, Example 15, and Example 20 and Comparative Example 1 and Comparative Example 2.

In the following, examples of the invention will be described in detail so that those skilled in the art can readily carry out the invention. However, the invention is embodied in a number of different forms and is not intended to be limited to the examples described herein.

Unless otherwise specifically stated in the specification of the present invention, all compounds or substituents may be substituted or unsubstituted. As used herein, the term "substituted" means that a hydrogen atom is replaced by any one selected from the group consisting of: a halogen group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an amine group, a thio group, a methyl sulfide. Alkyl, alkoxy, aldehyde, epoxy, ether, ester, carbonyl, acetal, keto, alkyl, perfluoroalkyl, cycloalkyl, heterocycloalkyl, allyl, benzene Methyl, aryl, heteroaryl, derivatives thereof, and combinations thereof.

Unless specifically stated otherwise in the specification, the term "combination thereof" means that two or more functional groups are bonded by a bonding group such as a single bond, a double bond (extended ethyl group), a triple bond (acetylene group). a pendant alkyl group having 1 to 20 carbon atoms (for example, a methylene group (-CH ₂ -) or an ethylidene group (-CH ₂ CH ₂ -)) having a stretch of 1 to 20 carbon atoms Fluoroalkyl (for example, fluoromethyl (-CF ₂ -) or fluoroethyl (-CF ₂ CF ₂ -)), such as nitrogen (N), oxygen (O), phosphorus (P), sulfur (S Or a hetero atom of cerium (Si) or a functional group containing such a hetero atom (specifically, intramolecular carbonyl (-C=O-), ether (-O-), ester (-COO-), - S-, an amine group (-NH-) or a heteroalkyl group containing -N=N- or the like; or two or more functional groups are condensed and bonded.

The present invention is characterized in that it is highly branched when a curable transparent fluorenone composition for an optical element is prepared using (a) an organic hydrazine compound, (b) a crosslinking agent, and (c) an addition reaction type catalyst. The regular form of the organic fluorenone compound is as (a) an organic fluorenone compound containing a ruthenium atom in a unit molecule and having at least three or more than three crosslinking points. Further, unlike the conventional anthrone composition which forms a crosslinking reaction at the terminal sites of the anthrone compound and the side chain, the crosslinking reaction of the organic indolone compound proceeds non-directionally, and thus, curing The transparent fluorenone composition has a short curing time, exhibits high shear modulus at high temperatures, high degree of crosslinking, high adhesion stress, high surface cure, and high transparency, and is exposed to ultraviolet radiation and moisture even after prolonged exposure. Transparency can be maintained after gas and heat without any risk of discoloration. Thus, the anthrone composition is suitable as an adhesive or transparent material for optical semiconductors.

In the following, various components will be described in more detail.

Component (a)

The organic hydrazine compound of component (a) may be an organic oxoxane compound having a branched or three-dimensional network structure, including , , , , as well as The selected bonding structure contains three or more than three germanium atoms (Si) each having 2 to 10 carbon atoms bonded directly to the molecule or bonded to the Si atom via an oxygen atom (O) Alkenyl, and having a vinyl content in the molecule of from 0.1 millimole to gram to 20 millimoles per gram, and preferably from 0.5 millimoles per gram to 12 millimoles per gram.

If the vinyl content is less than 0.1 mmol/g, the degree of crosslinking in the composition is decreased, and the shear modulus and adhesion are deteriorated. If the vinyl content is greater than 20 millimoles per gram, the composition will become very brittle after curing or will be susceptible to heat yellowing.

Further, the organic cerium compound of the component (a) may have a dendritic polymer structure as an example of a branched or three-dimensional network structure, and in this case, an algebra of 3 or less may be preferable. If the algebra is greater than 3, it is difficult to control the crosslinking reaction and the curing rate, and the number of synthesis steps is increased, making commercialization difficult.

Specifically, the organogermanium compound of component (a) can be selected from the group consisting of (a-1) the first organoantimony compound described below, (a-2) the second described below. Organic oxoxane compounds and mixtures thereof.

(a-1) First organoantimony compound

The first organic cerium compound may be a polyoxy siloxane compound or a polycarbomethoxy hydride compound having a branched or three-dimensional network structure containing three or more than three alkenyl groups each having 2 to 10 carbon atoms More preferably, it contains three or more than three vinyl groups which are directly bonded to the Si atom in the molecule or bonded to the Si atom via the oxygen atom (O). More specifically, the first organic hydrazine compound can be selected from the group consisting of compounds represented by the following formulas (1a) to (1c):

Wherein in the formula (1a), a, b and c are each represented such that 0 a 3,0 b 3 and 0 c An integer of 3; T represents (wherein R' may be an alkenyl group having 2 to 10 carbon atoms, and is preferably a vinyl group; and z represents an integer of 0 or 1); X may be selected from the group consisting of: , , And a combination thereof, wherein each R can be independently selected from the group consisting of: an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, such as an alkyl group having 1 to 20 carbon atoms (for example, A) Base, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl) or a cycloalkyl group having from 3 to 20 carbon atoms (eg cyclopropyl, cyclobutyl or cyclohexyl) An aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, such as an alkenyl group having 2 to 10 carbon atoms (e.g., a vinyl group, a propenyl group or a butenyl group) having 2 to 10 carbon atoms An alkynyl group (for example, ethynyl, propynyl or butynyl) or a cycloalkenyl group having 3 to 20 carbon atoms; an aromatic hydrocarbon group having 6 to 30 carbon atoms, such as having 6 to 30 carbons An aryl group of an atom (e.g., phenyl); a hydroxyl group; an alkoxy group having from 1 to 20 carbon atoms (e.g., methoxy, ethoxy, propoxy or tert-butoxy); an epoxy group; an amine a group (-NR ^a R ^b , wherein R ^a and R ^b each independently represent an alkyl group having 1 to 5 carbon atoms, such as a methyl group or an ethyl group); and a combination thereof. Preferably, each R may be Narrator Among the selected groups, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a hydroxyl group, an epoxy group, and an amine group are selected. And combinations thereof; Y and Z may each independently be selected from the group consisting of aliphatic saturated hydrocarbon groups having 1 to 20 carbon atoms, such as alkyl groups having 1 to 20 carbon atoms ( For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl) or a cycloalkyl group having from 3 to 20 carbon atoms (eg cyclopropyl, cyclobutyl or ring) Hexyl); an aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, such as an alkenyl group having 2 to 10 carbon atoms (for example, a vinyl group, a propenyl group or a butenyl group) having 2 to 10 carbons An alkynyl group of an atom (for example, an ethynyl group, a propynyl group or a butynyl group) or a cycloalkenyl group having 3 to 20 carbon atoms; an aromatic hydrocarbon group having 6 to 30 carbon atoms, such as having 6 to 30 An aryl group of a carbon atom (for example, a phenyl group); a hydroxyl group; an alkoxy group having 1 to 20 carbon atoms (for example, a methoxy group, an ethoxy group, a propoxy group or a tert-butoxy group); an epoxy group; ; An amine group (-NR ^a R ^b , wherein R ^a and R ^b each independently represent an alkyl group having 1 to 5 carbon atoms, such as a methyl group or an ethyl group); and a functional group represented by the following formula (2) . Preferably, Y and Z are each independently selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and the following formula ( 2) The functional group indicated:

Wherein in the formula (2), b, c, T, X and Y have the same meanings as defined above, respectively.

Further, in the formula (1b), e, f, and g are each represented such that 0 e 100, 1 f 5 and 0 g An integer of 2; each R may be independently selected from the group consisting of aliphatic saturated hydrocarbon groups having 1 to 20 carbon atoms, such as an alkyl group having 1 to 20 carbon atoms (e.g., methyl group) , ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl) or a cycloalkyl group having from 3 to 20 carbon atoms (for example cyclopropyl, cyclobutyl or cyclohexyl); An aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, such as an alkenyl group having 2 to 10 carbon atoms (e.g., a vinyl group, a propenyl group or a butenyl group), an alkyne having 2 to 10 carbon atoms a group (for example, an ethynyl group, a propynyl group or a butynyl group) or a cycloalkenyl group having 3 to 20 carbon atoms; an aromatic hydrocarbon group having 6 to 30 carbon atoms, such as having 6 to 30 carbon atoms An aryl group (e.g., phenyl); a hydroxyl group; an alkoxy group having 1 to 20 carbon atoms (e.g., methoxy, ethoxy, propoxy or tert-butoxy); an epoxy group; an amine group (-NRR, wherein each R independently represents an alkyl group having 1 to 5 carbon atoms, such as methyl or ethyl); and combinations thereof, and may preferably be selected from the group consisting of: 1 To 10 carbon atoms in the alkyl group, having 6 to 18 carbon atoms an aryl group, a hydroxyl group, an epoxy group, an amino group, and combinations thereof; and T represents (wherein R' may be an alkenyl group having 2 to 10 carbon atoms, and particularly, a vinyl group is preferred; and z represents an integer of 0 or 1); and the limitation is that R and T may be selected such that the compound The number of alkenyl groups (preferably vinyl groups) each having 2 to 10 carbon atoms in the molecule of (1c) will be three or more than three.

Further, in the formula (1c), h, i, and j are each represented such that 0 h 100,1 i 5 and 0 j An integer of 2; and R and T have the same meaning as defined for formula (1b).

Further, the first organic hydrazine compound of the component (a-1) may be a compound having a dendritic polymer structure, and in this case, the algebra is preferably 2 or less. If the algebra is greater than 2, the viscosity is increased, so that it is difficult to control the composition, and the number of synthesis steps is increased, so that commercialization becomes difficult.

More specifically, the first organic hydrazine compound of the component (a-1) may be any one of the compounds represented by the following formulas (3a) to (3c):

In the formulae (3a) to (3c), the dotted line means each generation in the dendrimer structure; and m and n each independently represent an integer of 0 to 100.

(a-2) second organooxane compound

The second organic siloxane compound may be an organic siloxane compound containing a cerium (Si) atom in a unit molecule, which contains a Q unit (a tetrafunctional oxirane group: four -O- moieties bonded thereto) a Si atom) or a mixed structure of a Q unit and a T unit (a trifunctional oxirane group: a Si atom having three O-parts (a decane bond) bonded thereto), and containing three One or more than three Si atoms directly bonded to the molecule, each having 2 to 10 carbon atoms (preferably a vinyl group). Specifically, the second organic siloxane compound may be a compound having the structure of the following formula (4): [Chemical Formula 4] (R ₃ Si) _a (SiO _4/2 ) _b (R ₂ SiO _1/2 ) _c ( SiO _3/2 ) _d (R ₃ Si) _e

Wherein in the formula (4), a, b, c, d, and e are each represented by 1 a 30,1 b 20,0 c 30,0 d 10 and 1 e An integer of 30; each R is independently selected from the group consisting of: an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, such as an alkyl group having 1 to 20 carbon atoms (e.g., methyl group, Ethyl, propyl, isopropyl, butyl, isobutyl or tert-butyl) or a cycloalkyl group having from 3 to 20 carbon atoms (for example cyclopropyl, cyclobutyl or cyclohexyl); An aliphatic unsaturated hydrocarbon having 2 to 20 carbon atoms, such as an alkenyl group having 2 to 10 carbon atoms (e.g., a vinyl group, a propenyl group or a butenyl group), an alkynyl group having 2 to 10 carbon atoms (e.g., ethynyl, propynyl or butynyl) or a cycloalkenyl group having 3 to 20 carbon atoms; an aromatic hydrocarbon group having 6 to 30 carbon atoms, such as having 6 to 30 carbon atoms An aryl group (e.g., phenyl); a hydroxyl group; an alkoxy group having 1 to 20 carbon atoms (e.g., methoxy, ethoxy, propoxy or tert-butoxy); an epoxy group; an amine group ( -NRR, wherein each R independently represents an alkyl group having from 1 to 5 carbon atoms, such as methyl or ethyl); and combinations thereof, with the proviso that at least three R groups each have from 2 to 10 Carbon The alkenyl group of the atom, and preferably all of the R groups are vinyl groups.

Further, the second organic siloxane compound may be an organic siloxane compound having a three-dimensional network structure containing a total of 3 to 30, preferably 3 to 10 Q units (SiO _4/2 ) or Q units. And a T unit (SiO _3/2 ) as a branching repeating unit in the molecule, and containing a -SiR ¹ R ² R ³ moiety (wherein R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms) And R ³ represents an alkenyl group having 2 to 10 carbon atoms, and preferably a vinyl group, as a terminal unit, as shown in the following formula (5):

Wherein in the formula (5), the dotted line means a branching repeating unit which may further comprise a Q unit or a T unit.

Preferably, the second organooxane compound is selected from the group consisting of compounds represented by the following formulas (6a) to (6c):

Wherein in the formula (6a), l represents an integer of 1 to 30, and preferably an integer of 1 to 10;

Wherein in the formula (6c), m represents an integer of 1 to 10; and n represents an integer of 2 to 30.

The second organic siloxane compound having a structure such as described above preferably has a viscosity of 100 mPa at 25 °C. Seconds or greater than 100 millipascals. Second liquid Body, or solid. Since the organic siloxane compound has such a viscosity characteristic, the viscosity adjustment effect can be obtained according to the content of the second organic siloxane compound.

Since (a-1) the first organogermanium compound and (a-2) the second organooxane compound such as described above have three or more than three crosslinking points in the molecule and a highly branched regular structure Therefore, unlike the conventional oxane compounds which should be formed preferentially in the chain, the reaction can be via a highly reactive blocked crosslinker (ie, an organooxane compound terminated by a hydrogen atom (H-terminated organic hydrazine) The oxane) is carried out non-directionally, and thus the curing time is short, while at the same time obtaining a high degree of crosslinking. Therefore, when the compound is applied to the cured fluorenone composition, the shear modulus, adhesion stress, surface cure degree, and transparency at high temperatures are improved, and can be maintained even after long-term placement in ultraviolet radiation, moisture, and heat. Transparency without any risk of discoloration. Further, since the first organic germanium compound and the second organic germanium oxide compound which have formed the crosslinking point are bonded by the short crosslinking agent, shrinkage can be minimized even when cured at a high temperature.

The first organic hydrazine compound and the second organic siloxane compound such as described above may be incorporated into the curable transparent fluorenone composition for an optical element, either alone or as a mixture. When the compound is used in a mixture as compared with the case of using it alone, it is possible to simultaneously exhibit an increase in the reaction rate induced by the first organic sulfonium compound and a physics caused by the second organic siloxane compound. Enhanced in nature. Therefore, when the compound is incorporated as a mixture, the mixing ratio is not particularly limited, but from the viewpoint of the degree of improvement of the effect of the present invention, the first organic cerium compound and the second organic siloxane compound are preferably in the form of a mixture of 1 The weight ratio of 4:1 to 8 is incorporated, and more preferably, the compound may be incorporated as a mixture in a weight ratio of 1:4 to 1:5. If the mixing ratio is less than 1:4, the composition will be slightly yellowish and will heat up when heated. Easy to show yellowing. Further, when the mixing ratio is more than 1:8, the effect of the first organic cerium compound may be negligible.

Component (b)

The curable transparent fluorenone composition for an optical element according to the present invention comprises, as a component (b), a crosslinking agent which functions to hydrogenate with an alkenyl group in the organic hydrazine compound of the component (a). The reaction is induced to crosslink and cure the composition. As the crosslinking agent, a crosslinking agent used in a conventional curing type transparent fluorenone composition for an optical element can be used, but a third organic siloxane compound can be preferably used. The alkane compound contains two or more hydrogen atoms bonded to a ruthenium atom in one molecule, and thus can act as a crosslinking agent and a reactive diluent, and the reactive diluent is diluted with a transparent fluorenone. The material is obtained to obtain a viscosity suitable for the application.

In particular, the third organooxane compound may be an organic hydrogen comprising two or more than two, and preferably 2 to 50, hydrogen atoms (ie, SiH groups) bonded to a halogen atom in one molecule. a polyoxyalkylene which comprises the repeating unit of the following formula (7): [Chemical Formula 7]-(R1 _p H _q SiO _(4-pq)/2 )-

Wherein in the formula (7), each R ¹ may be independently selected from the group consisting of substituted or unsubstituted aliphatic saturated hydrocarbon groups having 1 to 20 carbon atoms, having 6 to A substituted or unsubstituted aromatic hydrocarbon group of 30 carbon atoms, and combinations thereof, and preferably selected from the group consisting of substituted or unsubstituted one to 20 carbon atoms. An alkyl group, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, and a combination thereof. When R is substituted, the group may be substituted with a functional group selected from the group consisting of: an alkyl group having 1 to 10 carbon atoms, a halogen group, having 1 to 10 carbon atoms Haloalkyl, hydroxy and cyano groups.

In particular, examples of R ¹ include an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, Octyl, fluorenyl or fluorenyl; cycloalkyl, such as cyclohexyl; aryl, such as phenyl, tolyl, xylyl or naphthyl; aralkyl, such as benzyl, phenethyl or phenylpropyl a halogenated alkyl group in which a part or all of a hydrogen atom of a group is substituted with a halogen atom such as a chlorine atom, a fluorine atom or a bromine atom, such as a chloromethyl group, a 3-chloropropyl group or a 3,3,3-trifluoropropyl group; And a cyanoethyl group substituted by a cyano group. Among them, an alkyl group having 1 to 10 carbon atoms may be preferred, and a methyl group may be more preferable because the methyl group has an excellent improvement effect in terms of light resistance and heat resistance of the cured product.

Further, the organohydrogen polyoxyalkylene of the formula (7) in which at least 0.01 mol% or more than 0.01 mol% of all the groups represented by R ¹ is a methyl group, because the compound and the component (a) are Component (c) has excellent compatibility and does not present a risk of turbidity or phase separation in the composition. More preferably, it is an organic hydrogen polyoxyalkylene having from 0.05 mol% to 10 mol% of a methyl group in the group represented by R ¹ .

In addition, p and q are such that 0 p 4 and 0 q 4, and preferably 0 p 3 and 1 q 4, at the same time 1 p+q An integer of 3.

In the third organooxane compound, a hydrogen atom (ie, a SiH group) bonded to two or more than one of the ruthenium atoms contained in one molecule may be located at a position at the end of the molecular chain and at a position in the middle of the molecular chain. One, or can be located at two locations.

Further, the molecular structure of the third organomethoxyl compound may be any one of a linear structure, a cyclic structure, a branched structure, and a three-dimensional network structure, however The number of germanium atoms (or degree of polymerization) in one molecule may be from 1 to 500, and preferably from 3 to 200. Further, the content of the hydrogen atom bonded to the halogen atom is preferably in the range of 0.1 mmol/g to 20 mmol/g, and more preferably 1 mg, relative to 1 g of the third organooxane compound. Moor / gram to 10 millimoles / gram range.

In addition, regarding the third organooxane compound, the viscosity at 1,000 ° C is 1,000 mPa. Seconds or less than 1,000 millipascals. Seconds, and better 10 millipascals. Seconds to 100 millipascals. The compound of the second is preferred because the effect of reducing the viscosity can be obtained. Specific examples of the third organooxane compound include 1,1,3,3-tetramethyldisiloxane; 1,3,5,7-tetramethylcyclo 1,3,5,7-tetramethylcyclotetrasiloxane; methylhydrogencyclopolysiloxane; methylhydrogensiloxane-dimethylsiloxane cyclic copolymer a methylhydrogenpolysiloxane having a trimethylsiloxy group block at both ends; a dimethyl methoxyoxane having a trimethyldecaneoxy block at both ends - dimethylsiloxane-methylhydrogensiloxane copolymer; dimethylpolysiloxane dimethyldihydrosiloxy group at both ends; at both ends a dimethylsiloxane-methylhydrogensiloxane copolymer of dimethylhydroquinoloxy block; methylhydroquinone oxide via a trimethyldecaneoxy block at both ends Alkyl-diphenylsiloxane (methylhydrogensiloxane-diphenylsiloxane) a polymer; a methylhydrogensiloxane-diphenylsiloxane-dimethylsiloxane copolymer having a trimethyldecaneoxy block at both ends; a methylhydrogensiloxane-methylphenylsiloxane-dimethylsiloxane copolymer having a terminal end via a trimethyldecaneoxy block; a dimethyl group at both ends a methylhydrogensiloxane-dimethylsiloxane-diphenylsiloxane copolymer comprising a (hydrogen siloxane) block comprising: (CH ₃ ) ₂ HSiO _1/2 unit and SiO _a copolymer of _4/2 units; a copolymer comprising (CH ₃ ) ₂ HSiO _1/2 units, (CH ₃ ) ₃ SiO _1/2 units, and SiO _4/2 units; and including (CH ₃ ) ₂ HSiO _1/ A copolymer of ₂ units, SiO _4/2 units, and (C ₆ H ₅ )SiO _3/2 units. Preferred examples include a compound represented by the following formula (8a) to formula (8d):

Wherein in the formulae (8a) to (8d), R ¹ has the same meaning as defined for the formula (7); v represents an integer of 1 to 20; w represents an integer of 1 to 100; and x represents 0 to 100. An integer; and y represents an integer from 1 to 50.

Such a third organooxane compound may be used singly or in the form of a mixture of two or more than two types.

Component (b) is preferably incorporated in an amount such that the amount of hydrogen atoms bonded to the ruthenium atom in component (b) is directly bonded to the ruthenium atom or via component (a) organic ruthenium The oxygen atom in the compound is bonded to the mole amount of the alkenyl group of the halogen atom by 0.5 to 3 times. When component (b) is incorporated at such a content, excellent improvement can be exhibited.

Further, the component (b) is preferably incorporated in an amount of from 1 part by weight to 15 parts by weight per 100 parts by weight of the component (a) of the organic hydrazine compound.

Component (c)

Further, the curable transparent fluorenone composition for an optical element according to the present invention may further comprise a hydrazine hydrogenation catalyst (i.e., an addition reaction type catalyst) as component (c) for carrying out and accelerating component (a) The hydrazine hydrogenation addition reaction between the alkenyl group and the SiH group in the crosslinking agent of component (b).

As the addition reaction type catalyst, a platinum group metal catalyst can be used, and specific examples thereof include a platinum group metal such as platinum, palladium, and rhodium; an alcohol modified chloroplatinic acid such as a reaction between chloroplatinic acid and a monohydric alcohol; a product; a platinum group metal-containing coordination compound between chloroplatinic acid and an olefin, a vinyl siloxane or an acetylene compound; and a platinum group metal compound such as tetrakis(triphenylphosphine)palladium (tetrakis) Triphenylphosphine) palladium) and chlorotris (triphenylphosphine) rhodium.

The addition reaction type catalyst described above may be used alone or in two or more A mixture of two types is used, and among them, an fluorenone-modified chloroplatinic acid which is modified with the component (a) and the component (b) Satisfactory compatibility and almost no chlorine impurities.

Further, the addition reaction type catalyst may be catalytically effective amount incorporated into the curable transparent fluorenone composition for an optical element, and preferably, the catalyst may be organic oxime relative to the component (a) The total weight of the compound, the platinum group metal element is incorporated in an amount from 10 parts per million to 5,000 parts per million. The catalyst is more preferably incorporated in an amount of from 50 parts per million to 2,000 parts per million because the rhodium hydrogenation reaction can be more efficiently accelerated.

(d) Other additives

Along with component (a), the curable transparent fluorenone composition for an optical element according to the present invention may contain a oxoxane compound for viscosity adjustment, which contains two or more bonds to a unit molecule The alkenyl group or the hydroxyl group of the atom, and having the effect of enhancing the adhesion to the material to be adhered via the hydrogen bond while reducing the viscosity, and reducing the stress after curing.

Specifically, the oxoxane compound for viscosity adjustment may be a diorganopolyoxy siloxane having a linear, branched or three-dimensional network structure, wherein the main chain contains a diorganooxy oxane represented by the following formula (9). a repeating unit in which the ends of the molecular chain are each blocked by a triorganosiloxy group (R ₃ Si _1/2 ) block and the unit molecule contains two or more than two alkenyl groups bonded to a ruthenium atom in one molecule Or hydroxyl group: [Chemical Formula 9]-[R ¹ R ² SiO _2/2 ]-

Wherein in the formula (9), R ¹ and R ² are each independently selected from the group consisting of an alkenyl group having 2 to 20 carbon atoms, a hydroxyl group, and having 1 to 20 carbon atoms. An alkyl group and an aryl group having 6 to 30 carbon atoms.

The oxoxane compound for viscosity adjustment may preferably contain 2 to 10, and more preferably 2 to 5, alkenyl groups or hydroxyl groups bonded to a ruthenium atom in the unit molecule. In this case, the alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms, and more preferably an alkenyl group having 2 to 6 carbon atoms. Specific examples thereof include a vinyl group, an allyl group, an isopropenyl group, a butenyl group, a pentenyl group, and a hexenyl group, and the alkenyl group is preferably a vinyl group.

The alkenyl group or the hydroxyl group may be present at any of the terminal of the molecular chain in the molecule and the non-terminal portion of the molecular chain (ie, the side chain of the molecular chain), or may exist in two positions. However, an alkenyl group or a hydroxyl group is preferably present at at least two ends of the molecular chain.

Further, at the total content of the organic group, the alkenyl group or the hydroxyl group may be contained in an amount of 0.01 mmol/g to 5.00 mmol/g, and preferably 0.10 mmol/g to 0.50 mmol/g. Inside. If the content of the alkenyl group or the hydroxyl group is less than 0.01 mmol/g, the degree of crosslinking is low and the adhesion is reduced, which is not preferable. When the content is 5.00 millimoles per gram, the material may become brittle or have a viscous surface, which is not preferred.

The oxoxane compound for viscosity adjustment is preferably selected from the group consisting of compounds represented by the following formulas (10a) to (10g): (R ⁴ ) ₂ (R ³ ) SiO [Si(R ³ ) ₂ O] _f Si(R ³ )(R ⁴ ) ₂ (10a)

(R ⁴ ) ₃ SiO[Si(R ³ ) ₂ O] _f Si(R ⁴ ) ₃ (10b)

(R ⁴ ) ₂ (R ³ )SiO[Si(R ³ )(R ⁴ )O] _g [Si(R ³ ) ₂ O] _h Si(R ³ )(R ⁴ ) ₂ (10c)

(R ⁴ ) ₃ SiO[Si(R ³ )(R ⁴ )O] _g [Si(R ³ ) ₂ O] _h Si(R ⁴ ) ₃ (10d)

(R ³ ) ₃ SiO[Si(R ³ )(R ⁴ )O] _g [Si(R ³ ) ₂ O] _h Si(R ³ ) ₃ (10e)

(R ⁴ )(R ³ ) ₂ SiO[Si(R ³ ) ₂ O] _f Si(R ³ ) ₂ (R ⁴ ) (10f)

(R ⁴ )(R ³ ) ₂ SiO[Si(R ³ )(R ⁴ )O] _g [Si(R ³ ) ₂ O] _h Si(R ³ ) ₂ (R ⁴ ) (10g)

In the formulae (10a) to (10g), R ³ and R ⁴ are each independently selected from the group consisting of an alkenyl group having 2 to 20 carbon atoms, a hydroxyl group, and having 1 to 20 An alkyl group of one carbon atom and an aryl group having 6 to 30 carbon atoms; f represents an integer of 0 to 200, and preferably 3 to 120; g represents an integer of 1 to 10, and preferably 1 to 5; h represents an integer from 0 to 200, and preferably from 3 to 110.

The siloxane compound for viscosity adjustment such as described above may be used singly or in the form of a mixture of two or more than two types.

The oxoxane compound for viscosity adjustment may be 1 part by weight to 30 parts by weight relative to 100 parts by weight of the component (a) organic cerium compound from the viewpoint of obtaining the desired viscosity reducing effect without any risk of deterioration of properties. The amount is incorporated, and preferably, the siloxane compound can be incorporated in an amount of from 10 parts by weight to 20 parts by weight.

Further, the curable transparent fluorenone composition for an optical element of the present invention may contain a decane compound containing one or more alkoxy groups having an effect of enhancing adhesion to a material to be adhered via hydrogen bonding.

The decane compound may be a compound represented by the following formula (11): [Chemical Formula 11] (R ⁶ O) _z (R ⁷ ) _z' Si-R ⁸ _(4-z-z')

Wherein in the formula (11), R ⁶ and R ⁷ each independently represent an aliphatic hydrocarbon group having 1 to 8 carbon atoms; and R ⁸ represents a group having 1 to 8 carbon atoms; Selected functional group-substituted hydrocarbyl group: vinyl group, glycidyl group, styryl group, methacryl fluorenyl group, acryl fluorenyl group, ureido group, chloroalkyl group, decyl group, isocyanate group, amine group, two a methylamino group, an imidazolyl group, an ethyl acetate group, and an epoxy group; z and z' are such that 1 z 4 and 0 z' 3, at the same time 1 z+z' An integer of 4.

Specific examples of decane compounds include triethyl citrate (triethyl) Silicate), vinyltriethoxysilane, vinyltrimethoxysilane, vinyltriacetoxysilane, vinyltris(2-methoxyethoxy)decane (viyltri(2-methoxyethoxy)silane), N-(3-propenyloxy-2-hydroxypropyl)-3-aminopropyltriethoxypropane (N-(3-acryloxy-2-hydroxypropyl) 3-aminopropyltriethoxysilane), 3-methacryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane (2-(3, 4-epoxycyclohexyl)ethyltrimethoxysilane), N-phenylaminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane (N-phenylaminopropyltrimethoxysilane) N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane), N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(N-(2-aminoethyl)-3-aminopropyltrimethoxysilane) (2-Aminoethyl)-3-aminoethyltris(2-ethylethoxy)silane, 3-amino group Propyl triethoxy 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl) 2-(3,4-epoxycyclohexylethyltrimethoxysilane), (3-glycidoxypropyl)methyldiethoxysilane, 3-glycidyloxy 3-glycidoxypropyltrimethoxysilane and bis[3-(trisethoxysilyl)propyl]tetrasulfide. Among them, one type may be used alone or in a mixture form Use two or more than two categories.

From the viewpoint of obtaining an adhesion-increasing effect without separating the decane compound from the main constituent component, the decane compound such as the above is preferably 0.1 weight based on 100 parts by weight of the component (a) of the organic cerium compound. The amount is incorporated in an amount of 5 parts by weight.

In addition to the components described above, the curable clear fluorenone composition for an optical element according to the present invention may optionally further contain an additive such as a thixotropy controlling agent such as smog-type cerium oxide. (fumed silica); light scattering agent, such as crystalline cerium oxide; reinforcing material, such as cerium oxide or smog-type cerium oxide; fluorescent material; petroleum-based solvent and viscosity modifier, such as non-reactive a functional group of non-reactive fluorenone oil; an adhesion enhancer such as a carbon functional decane, or an anthrone compound different from component (a) having an epoxy group, an alkoxy group, a bond to a ruthenium atom a hydrogen atom (ie, a SiH group) and one or more than one of a vinyl group such as a vinyl group bonded to a ruthenium atom; a conductivity imparting agent containing a powdery metal such as silver or gold; a pigment such as cobalt blue; a colorant such as an organic dye; a heat resistance and a flame retardant enhancer such as cerium oxide, zinc carbonate, manganese carbonate, red iron oxide, titanium oxide or carbon black; Inhibitors such as 3-methyl-1-butyn-3-ol and 3,5-dimethyl-1-hexyl-3-ol (3, 5-dimethyl-1-hexyl-3-ol), phenylbutynol, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetraoxane (1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane), 1,3-divinyltetramethyldisiloxane, tetramethyltetravinyl Tetramethyltetravinyltetracyclosiloxane, benzene And a benzotriazole, a phosphine compound or a mercapto compound; or a wavelength adjusting agent.

The additive may be used at an appropriate level depending on the use, within a range not inhibiting the effects of the present invention.

With respect to the curable transparent fluorenone composition for an optical element according to the present invention having a composition such as the above, 80 mol of all the monohydrocarbyl groups excluding the alkenyl group bonded to the ruthenium atom in the composition % or more than 80% by mole, and preferably 90% by mole to 100% by mole of the methyl ketone composition is more preferable because the composition has excellent heat resistance and light resistance (resistant Ultraviolet light) and excellent resistance to deterioration, including discoloration caused by stresses such as heat and ultraviolet radiation.

As such, the curable clear fluorenone composition for an optical element of the present invention can be prepared by mixing the components (a) to (c) with optionally other additives of component (d), or By separately preparing the fraction containing component (a) and component (b) and comprising component (a) and component (c) other than component (b) and optionally component (d) Part, and then mix the two parts to prepare.

The curable clear fluorenone composition for an optical element of the present invention contains a free fluorenone compound of the component (a) as a main material, and because the reaction of the composition is cross-linked by a highly reactive end-capping type of the component The agent is carried out non-directionally, so that long curing time as in the conventional case is not required, and exhibits strong mechanical properties, a low linear expansion coefficient, and high adhesion. Therefore, the anthrone composition has high adhesion stress and high surface curing degree, and thus is suitable as an adhesive for an optical semiconductor. Further, the anthrone composition also exhibits a function as a transparent material for increasing light extraction efficiency from an element, and has transparency and does not undergo discoloration even after long-term exposure to ultraviolet radiation, moisture, and heat. Characteristics.

In addition, the curing of the cured transparent fluorenone composition for the optical element can be It is carried out under conventional curing conditions and can be carried out by heating at, for example, 100 ° C to 180 ° C for 30 minutes to 3 hours. Specifically, the Shore D hardness of the cured product obtained by curing the composition is preferably 35 or higher, and particularly preferably 45 or higher, and about Shore. The D hardness is 45 or higher than 45, and the cured product can be obtained by curing the composition of the present invention by heating the composition at 100 ° C to 180 ° C for 30 minutes to 3 hours.

Instance

In the following, examples of the invention will be described in detail so that those skilled in the art to which the invention pertains can readily practice the invention. However, the invention may be embodied in many different forms and is not intended to be limited to the examples described herein.

[Synthesis Example 1] Synthesis of a compound of the formula (1a)

In a 500 ml four-neck reaction tank equipped with a reflux condenser, a stirrer, a thermometer, and an addition funnel containing a nitrogen sparge, 13.5 grams of methyltrisdimethylsiloxysilane and 0.02 grams of xylene were introduced. The zero-valent platinum catalyst was diluted at 50 parts by weight, and heated at 50 ° C and the resulting mixture was stirred. 48.4 g of vinyltris (trimethylsiloxysilane) was slowly added to the resulting reaction mixture by dropwise addition using an addition funnel, and the resulting mixture was reacted for 24 hours. Subsequently, the resulting reaction mixture was concentrated under reduced pressure. The thus obtained transparent light brown liquid was again introduced into the four-neck reaction tank, and 200 ml of anhydrous toluene and 0.01 g of a ruthenium hydroxide catalyst were introduced therein. The resulting mixture was heated and stirred at 80 °C. 29 g (0.5 mol (excess)) of allyl alcohol was introduced into the obtained reaction product over one hour using an addition funnel, and the moisture contained in the allyl alcohol had been removed from it in advance using a microsieve. The resulting mixture was allowed to react for another three hours. After the reaction is completed, The catalyst was removed using a paper filter. A mixed solution of 200 g of a 1:1 distilled water/toluene was added to the obtained reaction solution, and the resulting mixture was stirred for 10 minutes, and then the organic layer was separated. The organic layer thus separated was washed repeatedly with a large amount of distilled water, and the organic layer was distilled off under reduced pressure. Thus, the product (1a) was obtained. The obtained product was stored in a state of being dissolved in 30 g of xylene.

Wherein in the reaction scheme, R represents -CH ₃ .

[Synthesis Example 2] Synthesis of Compound of Formula (1b)

In a 500 ml four-neck reaction tank equipped with a reflux condenser, a stirrer, a thermometer, and an addition funnel containing a nitrogen sparger, 120 ml of anhydrous toluene and 20 g of polymethylhydroquinone (SiH 7.8 mmol) were introduced therein. Ear/gram, Gelest, Inc. and 0.01 gram of zero valent platinum catalyst, and the mixture was heated and stirred at 50 °C. Using an addition funnel by dropping 22.3 grams of ethylene The vinyltrimethoxysilane was slowly added to the resulting reaction mixture over two hours, and the resulting mixture was allowed to react for 24 hours. The resulting reaction product was washed several times with ethanol and then distilled off under reduced pressure. Thereby, a pale yellow liquid was obtained. The pale yellow liquid thus obtained was again introduced into a four-neck reaction tank, and 200 ml of anhydrous toluene and 0.01 g of a ruthenium hydroxide catalyst were added thereto. The resulting mixture was heated and stirred at 80 °C. 29 g (0.5 mol (excess)) of allyl alcohol was introduced into the resulting reaction product over one hour using an addition funnel, and the moisture contained in the allyl alcohol had been removed from it in advance using microsieve. The resulting mixture was allowed to react for another three hours. After the reaction was completed, the catalyst was removed using a paper filter. A mixed solution of 200 g of a 1:1 distilled water/toluene was added to the obtained reaction solution, and the resulting mixture was stirred for 10 minutes, and then the organic layer was separated. The organic layer thus separated was washed repeatedly with a large amount of distilled water, and the organic layer was distilled off under reduced pressure. Thus, the product (1b) was obtained. The obtained product was stored in a state of being dissolved in 30 g of xylene.

(average of n = 50)

[Synthesis Example 3] Synthesis of a compound of the formula (1c)

Equipped with a reflux condenser, a stirrer, a thermometer and a nitrogen spray In a 500 ml four-neck reaction tank of the addition funnel of the ejector, 120 ml of anhydrous toluene and 20 g of polydimethyldihydrogen siloxane (SiH 7.0 mmol/g, Brystel) were introduced therein. And 0.01 g of a zerovalent platinum catalyst, and the mixture was heated and stirred at 50 °C. 22.3 g of vinyltrimethoxysilane was slowly added to the resulting reaction mixture by dropwise addition using an addition funnel, and the resulting mixture was reacted for 24 hours. The resulting reaction product was washed several times with ethanol and then distilled off under reduced pressure. Thereby, a pale yellow liquid was obtained. The pale yellow liquid thus obtained was again introduced into a four-neck reaction tank, and 200 ml of anhydrous toluene and 0.01 g of a ruthenium hydroxide catalyst were added thereto. The resulting mixture was heated and stirred at 80 °C. 29 g (0.5 mol (excess)) of allyl alcohol was introduced into the resulting reaction product over one hour using an addition funnel, and the moisture contained in the allyl alcohol had been removed from it in advance using microsieve. The resulting mixture was allowed to react for another three hours. After the reaction was completed, the catalyst was removed using a paper filter. A mixed solution of 200 g of a 1:1 distilled water/toluene was added to the obtained reaction solution, and the resulting mixture was stirred for 10 minutes, and then the organic layer was separated. The organic layer thus separated was washed repeatedly with a large amount of distilled water, and the organic layer was distilled off under reduced pressure. Thus, the product (1c) was obtained. The obtained product was stored in a state of being dissolved in 30 g of xylene.

(average of n = 50)

[Synthesis Example 4] Synthesis of Compound of Formula (5)

In a 500 ml four-neck reaction tank, 20.8 g of tetraethoxysilane (0.1 mol, Sigma-Aldrich Co.) and 100 ml of ethanol were introduced and vigorously shaken at room temperature. The resulting mixture was stirred for two hours. The temperature of the reaction vessel was lowered to 0 ° C, and then 71 g of dimethylvinylchlorosilane (0.3 mol (excess), Dow Chemical Co.) was introduced thereto over one hour. The resulting mixture was allowed to react for two hours. After the completion of the reaction, 100 g of a mixed solution of 1:1 distilled water/diethyl ether and an aqueous sodium hydrogencarbonate solution were added to the obtained reaction product, and the resulting mixture was stirred for 10 minutes, and then the organic layer was separated. The separated organic layer was washed repeatedly with a large amount of distilled water and distilled under reduced pressure. Thus, 48 g of a product (5) having a three-dimensional network structure comprising a branching repeating unit of an average of 4.2 units in the molecule as a Q unit, and -SiR ¹ R ² R ³ (wherein R ¹ and R ^{2 ) were obtained} Each represents a methyl group; and R ³ represents a vinyl group) as a capping unit. The product thus obtained was stored in a state of being dissolved in 30 g of xylene.

The number of Q units (tetrafunctional units) in the compound (5) thus produced was 4.2 on average.

[Synthesis Example 5] Synthesis of a compound of the formula (6c)

In a 500 ml four-neck reaction tank, 20.8 g of tetraethoxydecane (0.1 mol, Sigma-Aldrich), 69.0 g of 1,3,5,7-tetravinyltetramethylcyclotetrazepine were introduced. Alkane (1,3,5,7-tetravinyltetramethylcyclotetrasiloxane) (0.2 mol, Gellert) and 200 ml of ethanol, to which 0.35 g of trifluoromethanesulfonic acid was introduced as a catalyst, and at room temperature The resulting mixture was stirred vigorously for two hours. To the obtained reaction product, a mixed solution of 4:1 distilled water/ethanol was added over 10 minutes, and then the resulting mixture was further reacted for one hour. Thereafter, 130.3 g of vinyldimethylethoxysilane (1.0 mol (excess), Dow Chemical Co., Ltd.) was introduced thereto over one hour, and the mixture was further reacted for two hours. To the reaction product thus obtained, 100 g of a mixed solution of 1:1 distilled water/diethyl ether and an aqueous sodium hydrogencarbonate solution were introduced, and the resulting mixture was stirred for 10 minutes, and then the organic layer was separated. The organic layer thus separated was repeatedly washed with a large amount of distilled water and distilled under reduced pressure, and thus 131 g of the final product (6c) was obtained.

The m and n in the compound (6c) produced as described above are 1 to 5, and 4 to 16, respectively, and the average values are 3.5 and 8.0, respectively.

Test case 1 1. Measurement of molecular weight

The weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (PDI) of the compounds produced in Synthesis Example 1 to Synthesis Example 5 were measured by GPC. These values, along with the yield, are presented in Table 1 below.

2. Vinyl content analysis

For the compounds produced in Synthesis Example 1 to Synthesis Example 5, FT-IR was used to measure the relative vinyl peak relative to the internal standard peak of the Si-O backbone of the molecule itself, and the compound was estimated from the relative vinyl peak. Vinyl content.

As in the following equation (1), the vinyl content is related to the main chain Relationship between the ratio of the characteristic peak height to the C=C characteristic peak height The calculation formula used above is derived from the FT-IR results of five standard samples having known vinyl contents.

[Equation 1] Y=0.5779X-0.1331

Where in Equation 1, Y = vinyl content (mole/g)

X=H _vinyl /H _{矽 alkane}

H _vinyl = the height of the vinyl absorption peak, at 1600 cm ^{-1 -} 1650 cm ^-1

H _oxane = height of the absorption peak of the Si-O main chain at 1940 cm ^-1

Correction constant (M) = 0.5779

Intercept (N) = -0.1331

The results are presented in Table 2 and Figures 1 to 5.

In Figure 4, the compound of Synthesis Example 4 exhibited a weak peak at 2140 nm. It is believed that the SiH bond remains in the molecule of the compound produced in Synthesis Example 4, and it is presumed that the reactivity is lowered due to the steric hindrance caused by such SiH bond.

[Synthesis Example 6] Synthesis of Compound of Formula (8a)

Equipped with a reflux condenser, a stirrer, a thermometer and a nitrogen spray In a 250 ml four-neck reaction tank of the addition funnel of the ejector, 13.2 g of tetramethyldioxane (0.1 mol, Wacker Chemie AG) and 37.1 g of methylcyclopentyl hydrazine were introduced. Decamethylcyclopentylsiloxane (0.1 mol, Sigma-Aldrich), and the resulting mixture was heated to 40 °C. 0.05 g of trifluoromethanesulfonic acid was introduced as a catalyst into the resulting reaction mixture, and then the resulting mixture was vigorously stirred at 40 ° C for two hours. A mixed solution of 4:1 distilled water/ethanol was added thereto over 10 minutes, and the resulting mixture was further reacted for one hour. After completion of the reaction, 100 g of a mixed solution of 1:1 distilled water/diethyl ether and an aqueous solution of sodium hydrogencarbonate were added to the reaction product thus obtained, and the resulting mixture was stirred for 10 minutes, and then the organic layer was separated. The organic layer thus separated was washed repeatedly with a large amount of distilled water, and then distilled under reduced pressure. Thus, 28 g of the final product (8a) was obtained.

Wherein each R ¹ represents a methyl group; and v represents 4.

[Synthesis Example 7] Synthesis of Compound of Formula (8b)

In a 250 ml four-neck reaction tank equipped with a reflux condenser, a stirrer, a thermometer, and an addition funnel containing a nitrogen sparge, 24.0 g of 1,3,5,7-tetramethylcyclotetraoxane (0.1 Mo was introduced). Ear, Gellert) and 13.2 grams of 1,1,3,3-tetramethyldioxane (0.1 mole, WACK), and the resulting mixture was heated to 40 °C. 0.05 g of trifluoromethanesulfonic acid was introduced as a catalyst into the resulting reaction mixture, and then the resulting mixture was vigorously stirred at 40 ° C for two hours. Subsequently, a mixed solution of 4:1 distilled water/ethanol was added thereto over 10 minutes, and the resulting mixture was further reacted for one hour. The reaction product thus obtained is treated by the method of Synthesis Example 1. The same method was carried out, and 24.5 g of the final product (8b) was obtained.

[Synthesis Example 8] Synthesis of a compound of the formula (8c)

In a 1000 ml four-neck reaction tank equipped with a reflux condenser, a stirrer, a thermometer, and an addition funnel containing a nitrogen sparge, 240.5 g of 1,3,5,7-tetramethylcyclotetraoxane was introduced (1, 3,5,7-tetramethylcyclotetrasiloxane) (1.0 mol, Gellert) and 3.3 g of hexamethyldioxane (0.02 mol, WACK), and the resulting mixture was heated to 40 °C. 0.35 g of trifluoromethanesulfonic acid was introduced as a catalyst into the resulting reaction mixture, and then the resulting mixture was vigorously stirred at 40 ° C for two hours. Subsequently, a mixed solution of 4:1 distilled water/ethanol was added thereto over 10 minutes, and the resulting mixture was further reacted for three hours. The treatment of the reaction product thus obtained was carried out by the same method as in the synthesis example 1, and 212.0 g of the final product (8c) was obtained.

Wherein each R ¹ represents a methyl group; and w represents 45.

[Synthesis Example 9] Synthesis of a compound of the formula (8d)

In a 500 ml four-neck reaction tank equipped with a reflux condenser, a stirrer, a thermometer, and an addition funnel containing a nitrogen sparge, 240 g of 1,3,5,7-tetramethylcyclotetraoxane (1.0 mol) was introduced. Ear, Gellert), 26.4 grams of 1,1,3,3-tetramethyldioxane (0.2 m, WACK) and 20.8 g of tetraethoxydecane (0.1 Mohr, Sigma-Aldrich), and the resulting mixture was heated to 40 °C. 0.35 g of trifluoromethanesulfonic acid was introduced as a catalyst into the resulting reaction mixture, and then the resulting mixture was vigorously stirred at 40 ° C for two hours. Subsequently, a mixed solution of 4:1 distilled water/ethanol was added thereto over 15 minutes, and the resulting mixture was further reacted for three hours. The treatment of the reaction product thus obtained was carried out by the same method as in the synthesis example 1, and the final product (8d) was obtained.

Wherein each R ¹ represents a methyl group; x represents 40; and y represents 1.

Test case 2

In order to demonstrate the synthesis results of Synthesis Example 7 to Synthesis Example 10, the viscosity and hardness of the corresponding synthetic product were measured. The results are presented in Table 3 below.

This time, the viscosity was measured using a Brookfield cone-and-plate type viscometer (HBDV-II Pro, CP51).

In addition, the hardness is measured using a standard resin. Specifically, 96 parts by weight of polydimethylsiloxane (PDMS, viscosity: 10,000 centipoise (cP), vinyl content: 0.3 mmol/g), 3 parts by weight of synthetic compound, 0.5 part by weight of apple The dimethyl acid ester and 0.5 part by weight of the addition reaction type platinum catalyst were mixed and degassed, and the resulting mixture was cured at 150 ° C for two hours, and then the hardness was measured.

[Example 1 to Example 21] Preparation of curable transparent fluorenone composition for optical components

First, each of the free fluorenone compounds containing xylene produced in Synthesis Example 1 to Synthesis Example 5 and vinyl siloxane resin (VS1000 ^TM , manufactured by Hanse Chemie GmbH); vinyl content: 0.12 mmol/g) were mixed at various mixing ratios specified in the following Table 4, and then the resulting mixture was distilled off under reduced pressure. Thereby, the resin mixture 1 to the resin mixture 21 are produced. At this time, the case of using 100 parts by weight of a vinyl fluorene oxide resin was designated as a comparative resin.

The resin mixture 1 to the resin mixture 21 specified in Table 4 were each used as a main resin, and the compound of Synthesis Example 9 which exhibited the highest hardness among the compounds synthesized in Synthesis Example 6 to Synthesis Example 9 was used as a main crosslinking agent. And the resin and the crosslinking agent are mixed with the components specified in the following Table 5 in the amounts specified in the same table. Thus, a curable clear fluorenone composition for an optical element was prepared.

The crosslinker factor was set to 1.5, and this is the amount of vinyl resin added in relation to the ratio of SiH content to vinyl content. The crosslinking agent is added in an amount calculated by measuring the required amount of the crosslinking agent and multiplying the amount by 1.5.

[Comparative Example 1] Preparation of curable transparent fluorenone composition for optical components

100 parts by weight of the main resin VS10000 ^TM: 9 Compound Synthesis Example crosslinker (Hans chemical, vinyl 0.05 mmol / g), corresponding to 1.5 parts by weight of the amount of a factor, 0.3 parts by weight Examples of the polymerization inhibitors are methylbutanol (Sigma - Aldrich), 0.5 parts by weight of an addition reaction type platinum catalyst (NC25 ^TM catalyst, Dow Corning - Toray Co., Ltd. (Dow Corning-Toray Co., Ltd )) And 0.5 part by weight of vinyltriethoxydecane was mixed and degassed, and thereby a curable clear fluorenone composition for an optical element was prepared.

[Comparative Example 2] Preparation of curable transparent fluorenone composition for optical components

100 parts by weight of the main resin VQM803 ^TM: 9 Compound Synthesis Example crosslinker (Hans chemical, vinyl 0.21 mmol / g), corresponding to 1.5 parts by weight of the amount of a factor, 0.3 parts by weight Examples of the polymerization inhibitors are methylbutanol (Sigma - Aldrich), 0.5 parts by weight of an addition reaction type platinum catalyst (NC25 ^TM catalyst, Dow Corning - Toray Co., Ltd.) and 0.5 parts by weight of vinyltriethoxysilane Silane It is mixed and degassed, and thereby a curable transparent fluorenone composition for an optical element is prepared.

Comparative Example 2 used the VQM803 ^TM (Hans chemical, vinyl: 0.21 mmol / g) as a silicone-resin comprising Q units (tetrafunctional), the selection and the resin as a comparative example, because it is a portion comprising The products of Synthesis Example 1 and Synthesis Example 2 of the Q unit were comparable.

[Test Example 3] Evaluation of Curable Transparent Anthrone Composition for Optical Elements

The curable clear fluorenone composition for optical elements prepared in Examples 1 to 21 and Comparative Example 1 and Comparative Example 2 was cured according to curing conditions, and then the curing rate, light transmittance, and characteristics were analyzed.

1) Curing rate

The formation of the reactants under heating conditions and the reaction rate at a fixed temperature were evaluated using a differential scanning calorimeter (DSC), and the curing rates of the various materials were compared by means of the reaction rate at a fixed temperature.

The fixed temperature was set at 150 ° C, which was a general curing condition, and the point in time at which no change in calories occurred was designated as the curing completion point. The results are presented in Figure 6.

As shown in Fig. 6, it was found that the cured transparent fluorenone composition for optical elements of Comparative Example 2 containing a polymer having a network structure had a curing rate faster than that of Comparative Example 1 containing only a linear polymer. A cured transparent ketone composition for an optical element. Similarly, the curable clear fluorenone composition for optical elements of Examples 1 to 21 containing the highly branched fluorenone compounds produced in Synthesis Examples 1 to 6 was exhibited as compared with Comparative Example 2 Significantly higher cure rates. It has been confirmed that as the content of the highly branched regular resin increases, the curing rate also increases.

2) Light transmittance

The cured clear fluorenone compositions for optical elements prepared in Examples 1 to 21 and Comparative Example 1 and Comparative Example 2 were each coated on a glass plate to a thickness of 1 mm or 2 mm, and then at 150 The fluorenone composition was cured at ° C for two hours. For the obtained cured film, the light transmittance with respect to the light transmittance of the glass at 450 nm and 600 nm was measured using a UV-VIS spectrometer. At this time, the light transmittance at 450 nm was used to study the transparency, and the light transmittance at 600 nm was used to study the degree of yellowing. The results are presented in Figure 7 below.

7 is a view showing curing obtained by coating the curable transparent fluorenone composition for an optical element of Examples 1 to 21 and Comparative Example 1 and Comparative Example 2 to a thickness of 1 mm and then curing the composition. A graph of the measurement results of the light transmittance (%) of the product.

As shown in Fig. 7, when a highly branched siloxane compound is added, the light transmittance is increased regardless of the content of the siloxane compound. In particular, in the case of Example 9 and Example 10, the composition exhibited the highest increase in light transmittance. On the other hand, in the case of Synthesis Example 5, even if the content was increased, the light transmittance did not reach the level of Synthesis Example 4; however, even in the case of the synthesis example 5 resin in the resin mixture used in Examples 13 to 21 In the meantime, when a small amount of the mixture of Synthesis Example 1 to Synthesis Example 4 was added thereto, the light transmittance increasing effect similar to the resin mixture using Synthesis Example 5 was also exhibited.

3) Shear modulus

The compositions were each coated on an aluminum cup instead of a glass plate to a thickness of 2 mm, and then the composition was cured at 150 ° C for two hours, and thereby a cured sample of the examples and comparative examples was produced. Subsequently, using a dynamic mechanical analyzer (DMA, Mettler Toledo, Inc.), the same method as that used in the partial "2) light transmittance was measured. The storage elastic modulus under shear stress. At this time, representative examples of various resin mixtures of Examples 1 to 21 were selected, and the results are presented in FIG.

As shown in FIG. 8, the compositions of Example 10, Example 13, Example 15, and Example 20 containing highly branched siloxane derivatives exhibited higher shear modulus than Comparative Example 1 and Comparative Example 2, and were clear. That is, in the case of Example 10, the composition exhibits a slight change from the glass transition temperature, and it can be confirmed The composition has an ideal elastic modulus characteristic. Further, in the case of Example 10 and Example 20 having a high content of highly branched aramidane compounds, the composition maintained a shear modulus of several tens of megapascals even at a high temperature.

The preferred embodiments of the present invention have been described in detail, but are not intended to limit the scope of the present invention, and various modifications and improvements may be made by those skilled in the art using the basic concepts of the invention as defined in the following claims. It is also included in the scope of the invention.

Claims (15)

A curable transparent fluorenone composition for an optical element, the composition comprising an organic hydrazine compound, a crosslinking agent, and an addition reaction type catalyst, wherein the organic cerium compound comprises an organic having a branched or three-dimensional network structure a oxoxane compound, which is included in a unit molecule , , , , as well as a bonded structure selected from the group consisting of three or more than three germanium atoms (Si) each having 2 to 10 carbon atoms bonded directly to the molecule or via an oxygen atom (O) The alkenyl group bonded to the Si atom and having a vinyl content of from 0.1 mmol/g to 20 mmol/g. The curable transparent fluorenone composition for an optical element according to claim 1, wherein the organic hydrazine compound is selected from the group consisting of: (a-1) a first organic hydrazine; a compound, (a-2) a second organic oxirane compound, and a mixture thereof: (a-1) a first organic oxime compound which is composed of a compound represented by the following formula (1a) to formula (1c) And (a-2) a second organooxane compound represented by the following formula (4), including a ruthenium atom in a unit molecule, including a Q unit (tetrafunctional oxirane group) or a Q unit and a mixed structure of T units (trifunctional oxoalkyl groups), and an alkenyl group comprising three or more than three Si atoms each having 2 to 10 carbon atoms bonded directly to the molecule: Wherein in the formula (1a), a, b and c each independently represent 0 a 3,0 b 3 and 0 c 3; T indicates Wherein R' represents an alkenyl group having 2 to 10 carbon atoms; and z represents an integer of 0 or 1; X is selected from the group consisting of: , And a combination thereof, wherein each R is independently selected from the group consisting of an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, an aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, and An aromatic hydrocarbon group of 6 to 30 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an epoxy group, an amine group -NR ^a R ^{b ,} and a combination thereof, wherein R ^a and R ^b are each independently The ground represents an alkyl group having 1 to 5 carbon atoms; and Y and Z are each independently selected from the group consisting of: an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, having 2 to An aliphatic unsaturated hydrocarbon group of 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, a hydroxyl group, an epoxy group, an amine group -NR ^a R ^{b ,} and a functional group represented by the following formula (2), wherein R ^a and R ^b each independently represent an alkyl group having 1 to 5 carbon atoms: Wherein in the formula (2), b, c, T, X and Y have the same meanings as defined above; Wherein in the formula (1b), e, f, and g are each represented such that 0 e 100,1 f 5 and 0 g An integer of 2, and when expressed in a dendrimer structure, algebra is 2 or less; each R is independently selected from the group consisting of: aliphatic saturation with 1 to 20 carbon atoms Hydrocarbyl group, aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, aromatic hydrocarbon group having 6 to 30 carbon atoms, hydroxyl group, alkoxy group having 1 to 20 carbon atoms, epoxy group, amine a group -NR ^a R ^b and combinations thereof, wherein R ^a and R ^b each independently represent an alkyl group having from 1 to 5 carbon atoms; and T represents Wherein R' represents an alkenyl group having 2 to 10 carbon atoms; and z represents an integer of 0 or 1; with the proviso that R and T are selected such that each of the molecules of the compound of the formula (1b) has The number of alkenyl groups of 2 to 10 carbon atoms will be 3 or greater; Wherein in the formula (1c), h, i, and j are each represented such that 0 h 100,1 i 5 and 0 j An integer of 2; each R is independently selected from the group consisting of: an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, an aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, having 6 An aromatic hydrocarbon group of up to 30 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an epoxy group, an amine group -NR ^a R ^b and combinations thereof, wherein R ^a and R ^b are each independently Represents an alkyl group having from 1 to 5 carbon atoms; and T represents Wherein R' represents an alkenyl group having 2 to 10 carbon atoms; and z represents an integer of 0 or 1; with the proviso that R and T are selected such that each of said molecules of said compound of formula (1c) The number of alkenyl groups having 2 to 10 carbon atoms is 3 or more; [Chemical Formula 4] (R ₃ Si) _a (SiO _4/2 ) _b (R ₂ SiO _1/2 ) _c (SiO _3/2 ) _d (R ₃ Si) _e wherein in the formula (4), a, b, c, d, and e are each represented by 1 a 30,1 b 20,0 c 30,0 d 10 and 1 e An integer of 30; and each R is independently selected from the group consisting of: an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms, an aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, An aromatic hydrocarbon group of 6 to 30 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an epoxy group, an amine group -NR ^a R ^{b ,} and a combination thereof, wherein R ^a and R ^b are each independently The ground represents an alkyl group having 1 to 5 carbon atoms, with the proviso that at least three R each represents an alkenyl group having 2 to 10 carbon atoms. The curable transparent ruthenium composition for an optical element according to claim 2, wherein the first organic ruthenium compound is composed of a compound represented by the following formula (3a) to formula (3c); Selected from the group: Wherein m and n each independently represent an integer from 0 to 100. The curable transparent ruthenium composition for an optical element according to claim 2, wherein the second organic siloxane compound is an organic siloxane compound having a three-dimensional network structure in which the molecule Including 3 to 30 branching repeating units each including a Q unit (SiO _4/2 ) or a Q unit and a T unit (SiO _3/2 ); and a SiR ¹ R ² R ³ portion as a capping unit, Wherein R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms; and R ³ represents an alkenyl group having 2 to 10 carbon atoms. The curable transparent fluorenone composition for an optical element according to the invention of claim 2, wherein the second organic oxoxane compound is a compound represented by the following formula (6a) to formula (6c) Among the ethnic groups selected: Wherein in the formula (6a), l represents an integer from 1 to 30; Wherein in the formula (6c), m represents an integer of 1 to 10; and n represents an integer of 2 to 30. The curable clear fluorenone composition for an optical element according to claim 2, wherein the second organic oxane compound has a viscosity of 100 mPa at 25 ° C. Second or higher than 100 mPa. Seconds of liquid or solid. The curable transparent fluorenone composition for an optical element according to claim 1, wherein the cross-linking agent is a hydrogen atom comprising two or more than two germanium atoms bonded to one molecule. a third organooxane compound comprising a repeating unit represented by the following formula (7): [Chemical Formula 7]-(R1 _p H _q SiO _(4-pq)/2 ) - wherein in the formula (7), p and q represent 0 p 4 and 0 q 4 simultaneous 0 p+q An integer of 4; and each R ^{1 is} independently selected from the group consisting of an aliphatic saturated hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 30 carbon atoms, all of which may be Substituted or substituted by a substituent selected from the group consisting of: an alkyl group having 1 to 10 carbon atoms, a halogen group, a haloalkyl group having 1 to 10 carbon atoms, a hydroxyl group, and a cyano group And its combination. The curable transparent fluorenone composition for an optical element according to the above aspect of the invention, wherein the cross-linking agent is a group consisting of a compound represented by the following formula (8a) to formula (8d) Selected from: Wherein in the formulae (8a) to (8d), each R ^{1 is} independently a group consisting of an aliphatic saturated hydrocarbon group having 1 to 10 carbon atoms and an aromatic hydrocarbon group having 6 to 30 carbon atoms. Alternatively, it may be unsubstituted or substituted by a substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a halogen group, a halane having 1 to 10 carbon atoms. a group, a hydroxyl group, and a cyano group, and combinations thereof; and v represents an integer from 1 to 20; w represents an integer from 1 to 100; x represents an integer from 0 to 100; and y represents an integer from 1 to 50. The curable clear fluorenone composition for an optical element according to claim 1, wherein the crosslinking agent has a viscosity of 1,000 mPa at 25 ° C. Seconds or less than 1,000 millipascals. second. The curable transparent fluorenone composition for an optical element according to claim 1, wherein a molar number of a hydrogen atom bonded to a ruthenium atom in a molecule of the crosslinking agent is bonded to the The number of moles of the alkenyl group of all the ruthenium atoms in the organic ruthenium compound is 0.5 to 3 times. The curable transparent fluorenone composition for an optical element according to claim 1, wherein the crosslinking agent is used in an amount of from 1 part by weight to 15 parts by weight per 100 parts by weight of the organic hydrazine compound. Included. Curing type for optical components as described in claim 1 The alumone composition, wherein the addition reaction type catalyst is a platinum group metal catalyst. The curable transparent fluorenone composition for an optical element according to claim 1, wherein the addition reaction type catalyst is the platinum group metal element with respect to the total weight of the organic hydrazine compound The amount from 10 parts per million to 5,000 parts per million is included. The curable transparent fluorenone composition for an optical element according to claim 1, wherein the curable transparent fluorenone composition for the optical element is applied to a glass plate to a thickness of 1 mm. When it is 2 mm and cured, it exhibits a light transmittance of 90% or more with respect to glass transmittance at 450 nm and 600 nm. The curable transparent fluorenone composition for an optical element according to claim 1, wherein when the curable transparent fluorenone composition for the optical element is cured to a thickness of 2 mm, at 25 The shear modulus at ° C is 150 MPa or less, and may be 20 MPa or more at 20 ° C or higher than 100 ° C.