TWI634160B - Organic-silicon metal composites, curable organopolysiloxane composition comprising thereof, and optical material comprising the composition - Google Patents

Abstract

The present invention provides an organic-inorganic metal composite, and a curable organopolyoxane composition comprising the same. The organic-ruthenium metal composite according to the present invention and the curable organopolyoxane composition comprising the same have good heat resistance and low adhesive properties, and can be suitably used in an optical element.

Description

Organic ruthenium metal complex, including curable organic poly Oxyaloxane composition and optical material comprising the same

This invention relates to an organic base metal composite and a curable organopolyoxyalkylene composition comprising the same.

A light-emitting diode (LED) is used as a solid-state light source with high efficiency and long life, and is a conventional incandescent lamp, fluorescent light, or high-intensity discharge lamp (HID lamp) that has not been resolved in comparison with the relationship between light emission and lifetime. ) or organic light-emitting diodes (OLEDs) are more widely used.

The size of the light emitting diode element is typically a few millimeters or less. Such devices are mounted on different substrates in single or multiple forms and sealed with a sealing resin for protecting and controlling light as a light source.

At the beginning of the development of light-emitting diodes, epoxy resin was used as the encapsulating resin. Recently, most of the high-output and reliability light-emitting diodes use a silicon resin as an encapsulating resin.

The lens of the light-emitting diode is generally formed by, for example, a potting process, and the package of the light-emitting diode is formed using a low-viscosity resin, and then in a separate process. The formed lens is attached to the light emitting diode. In this case, a primer and an adhesive may be used to improve the adhesion between the lens and the encapsulant of the light-emitting diode. However, in the light source of the output of the light-emitting diode, when light is released and the heat is increased, defects such as lens peeling and color change of the adhesive or the primer may occur.

In addition, after a long period of use under a high temperature state, the encapsulant of the light emitting diode may be prone to cracks. In order to reduce the generation of cracks, a cured product of a low hardness organopolysiloxane can be used. However, the use of low-hardness organopolyoxane may cause various defects including dust adhesion due to high adhesiveness during the manufacturing process of the light-emitting diode package.

The present invention provides an organogermanium metal composite and a curable organopolyoxane composition comprising the same that increases heat resistance and minimizes changes in physical properties.

An organic base metal composite according to an aspect of the invention includes one or more of the following Formula 1 or Formula 2.

[(Formula 1][(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d ] _X M _Y

In Formula 1, a, b, c, and d are each independently greater than or equal to 0 and less than 1, a+b+c+d=1, R ¹ , R ² , R ³ , R ⁴ , R ^{5 ,} and R ⁶ Each independently is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an epoxy group, a hydroxyl group, an alkoxy group, an oxetane group. (oxetanyl), acryloyloxy, methacryloyloxy, mercapto, amino or cyano, M is a metal atom in the periodic table, and 0< X/Y 4.

[Formula 2] [(R ⁷ R ⁸ R ⁹ Si-N-SiR ¹⁰ R ¹¹ R ¹² ) _e ] _x M _y

In Formula 2, e is more than 0 and less than 1, and R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aromatic group, or an epoxy group. a group, a hydroxyl group, an alkoxy group, an oxetanyl group, an acryloxy group, a methacryloxy group, a fluorenyl group, an amino group or a cyano group, M is a metal atom in the periodic table, and 0<X/Y 4.

Another aspect of the present invention provides a curable organopolyoxane composition comprising 0.5 to 10 parts by weight of an organoiridium metal complex, 30 to 95 parts by weight of an organopolyoxane, and 0.00005 To 0.003 parts by weight of a platinum group metal catalyst.

The organopolyoxane is represented by the following formula 3: [Formula 3] (R ¹³ R ¹⁴ R ¹⁵ SiO _1/2 ) _M (R ¹⁶ R ¹⁷ SiO _2/2 ) _D (R ¹⁸ SiO _3/2 ) _T ( SiO _4/2 ) _Q

In Formula 3, M, D, T, and Q are values greater than or equal to 0 and less than 1, M + D + T + Q = 1, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ^{17 ,} and R ¹⁸ Are each independently a hydrogen atom, or a monovalent or unsubstituted monovalent hydrocarbon group having the same or different aliphatic saturated groups, at least one of which is at the end or side chain of the molecule There are 1, 2 or more than 2 unsaturated groups, and the hydrocarbon group has a straight or branched main chain.

The organic hydrogen-containing polyoxyalkylene is represented by the following formula 4: [Formula 4] (R ¹⁹ R ²⁰ R ²¹ SiO _1/2 ) _m (R ²² R ²³ SiO _2/2 ) _d (R ²⁴ SiO _3/2 ) _t (SiO _4/2 ) _q

In Formula 4, m, d, t, and q are values greater than or equal to 0 and less than 1, m + d + t + q = 1, R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ^{23 ,} and R ²⁴ They are each independently a hydrogen atom, or a monovalent or unsubstituted monovalent hydrocarbon group which does not have the same or different aliphatic unsaturated bonds.

Beneficial effect

The organic base metal composite and the curable organopolyoxane composition according to the present invention have good heat resistance and low adhesive properties, and are preferably used in optical elements.

In order to solve the above problems, an aspect of the present invention provides an organic base metal composite which may include one or more of the following Formula 1 or Formula 2.

[(Formula 1] [(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _3/2 ) _c (SiO _4/2 ) _d ] _X M _Y

In Formula 1, a, b, c, and d are each independently greater than or equal to 0 and less than 1, a+b+c+d=1, R ¹ , R ² , R ³ , R ⁴ , R ^{5 ,} and R ⁶ Each independently is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an epoxy group, a hydroxyl group, an alkoxy group, an oxetane group. (oxetanyl), acryloyloxy, methacryloyloxy, mercapto, amino or cyano, M is a metal atom in the periodic table, and 0< X/Y 4.

[Formula 2] [(R ⁷ R ⁸ R ⁹ Si-N-SiR ¹⁰ R ¹¹ R ¹² ) _e ] _x M _y

In Formula 2, e is more than 0 and less than 1, and R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aromatic group, or an epoxy group. a group, a hydroxyl group, an alkoxy group, an oxetanyl group, an acryloxy group, a methacryloxy group, a fluorenyl group, an amino group or a cyano group, M is a metal atom in the periodic table, and 0<X/Y 4.

In the "organo ruthenium metal complex" according to an aspect of the invention, the "organo ruthenium metal complex" may be, for example, an organopolyoxane of the formula 1, or an organopolysilazane of the formula 2, for example. ).

The inclusion of the metal in the organic ruthenium complex should not be a simple addition of the metal to the organic ruthenium complex by physical or mechanical means, but rather by chemical bonding of the organic ruthenium complex (even if not exactly verified).

Conventionally, metal additions are sometimes added to stabilize the physical properties of the curable organopolyoxane composition at elevated temperatures. However, the metal composition is simple In the case of adding a composition, the transmittance (or haze) value of the final cured product may be significantly lowered.

The heat resistance and penetration of the cured product of the curable organopolyoxane composition including the organic ruthenium metal complex can be improved by including the metal in the organic ruthenium complex.

The metal may include a metal element in the periodic table to improve physical properties under high temperature, and may specifically include at least one selected from the group consisting of lanthanum (La), cerium (Ce), and praseodymium (Pr). , neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), Titanium (Homium, Ho), erbium (Er), thurium (Tm), ytterbium (Yb), lanthanum (Lu), zirconium (Zr) and titanium (Ti) Group of.

In Formula 1, d may be a range satisfying the relationship of 0 < d < 0.1. Since the reaction with the metal is preferably an organopolyoxane of the formula 1 which satisfies the above range, the product of the metal-containing composite may be increased, and at the same time, a heat-resistant curable organopolyoxane is required at a high temperature. The cured product provides high heat resistance.

The specific R ¹ to R ¹² in the formulae 1 and 2 may be an alkyl group and an alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group). Or may be an aryl group and an aromatic group having 6 to 18 carbon atoms (for example, phenyl, fluorophenyl, β-naphthyl, and β -fluorenyl) (β-anthranyl)).

The specific R ¹ to R ¹² in the formulae 1 and 2 is an alkenyl group, an alkenyl group having 2 to 6 carbon atoms, and may, for example, include a vinyl group, an allyl group, and a β -butenyl group. And γ -butenyl.

Further, the case of R ¹ to R ¹² specified in Formula 1 and Formula 2 can be applied to have an epoxy group, an oxetanyl group, a methacryloxy group, an acryloxy group, a decyl group, an amino group or a cyanide group. The substituent of the group, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms. In particular, an alkyl group having 1 to 3 carbon atoms including the above substituent may be suitable.

An epoxy group may include glycidyl (glycidyl), glycidoxy ethyl (glycidoxy ethyl), α - glycidoxy propyl (α-glycidoxy propyl), β - glycidoxypropyl ([beta] glycidoxy propyl), γ - glycidoxypropyltrimethoxysilane (γ-glycidoxy propyl), α - glycidoxybutyl (α-glycidoxy butyl), β - glycidoxybutyl (β-glycidoxy butyl), γ - γ-glycidoxy butyl, δ -glycidoxy butyl, α- (3,4-epoxycyclohexyl)methyl (α-(3,4- Epoxy cyclohexyl)methyl), β- (3,4-epoxycyclohexyl)ethyl, γ- (3,4-epoxycyclohexyl)propyl (γ) - (3,4-epoxy cyclohexyl) propyl ), δ - (3,4- epoxycyclohexyl) butyl (δ- (3,4-epoxy cyclohexyl) butyl) ... and so on.

The oxetane group may include (3-ethyloxetane-3-yl)propyl (3). The acryloxy group may include acryloyloxy methyl group, β -acryloyloxy ethyl group, β -acryloyloxy propyl group, γ -propylene group. Γ-acryloyloxy propyl... and so on.

Further, methyl group may include methyl Bingxi Xi Bing Xixi yloxymethyl (methacryloyloxymethyl), β - methyl Bing Xixi oxyethyl (β-methacryloyloxyethyl), β - methyl propyl Bingxi Xi (beta] -methacryloyloxypropyl), γ -methacryloyloxypropyl... and the like.

Mercapto may include mercaptomethyl (mercapto methyl), β - mercapto ethyl (β-mercapto ethyl), β - mercaptopropyl (β-mercapto propyl), γ - mercaptopropyl (γ-mercapto propyl) ... etc. Wait. Amino group may include aminomethyl (amino methyl), β - aminoethyl (β-amino ethyl), β - aminopropyl (β-amino propyl), γ - aminopropyl (γ-amino propyl), N- ( β - (aminoethyl) (N- (β- (amino ethyl )), γ -. aminopropyl (γ-amino propyl) ... etc. cyano may include cyanomethyl (cyanomethyl), β - Cyanoethyl (β-cyanoethyl) and β -cyanopropyl (β-cyanopropyl), γ -cyanopropyl (γ-cyanopropyl). Isocyano can include isocyanatomethyl , β - acyl isocyanate ethyl (β-isocyanoethyl), β - propyl isocyanate (β-isocyanopropyl), γ - isocyanato ester (γ-isocyanopropyl) ... and so on.

According to another aspect of the present invention, a curable organopolyoxane comprising one or more of the organic ruthenium metal complexes of Formula 1 or Formula 2 can be provided.

In particular, the curable organopolyoxane composition may comprise from 0.5 to 10 parts by weight of an organic base metal comprising one or more of Formula 1 or Formula 2 as a heat resistance additive. Complex. In the case where the organic base metal composite is less than 0.5 parts by weight, heat resistance may not be attained. In the case where the amount of the organic iridium metal complex is more than 10 parts by weight, the yellowing degree may increase, and the optical characteristics may be deteriorated.

The curable organopolyoxane composition according to an embodiment of the present invention plays a role in forming a backbone after curing the ruthenium composition, and may include 30 to 95 parts by weight of the following formula 3 Polyoxane. In the case where the amount of the organopolysiloxane is less than 30 parts by weight, the cured product of the curable composition becomes soft, and the cured product may be scratched or torn. In the case where the amount of the organopolysiloxane is more than 95 parts by weight, the liquid viscosity of the composition increases, and the workability thereof may deteriorate.

[Formula 3] (R ¹³ R ¹⁴ R ¹⁵ SiO _1/2 ) _M (R ¹⁶ R ¹⁷ SiO _2/2 ) _D (R ¹⁸ SiO _3/2 ) _T (SiO _4/2 ) _Q

In Formula 3, M, D, T, and Q are values greater than or equal to 0 and less than 1, M + D + T + Q = 1, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ^{17 ,} and R ¹⁸ They are each independently a hydrogen atom, or a monovalent or unsubstituted monovalent hydrocarbon group having the same or different aliphatic saturated groups, at least one of which has one or two at the end or side chain of the molecule. One or more than 2 unsaturated groups, and the hydrocarbon group has a straight or branched main chain.

In Formula 3, the value of M may be from 0.01 to 0.3. The value of D can be from 0.3 to 0.6. The value of T can be from 0 to 0.3. The value of Q can be from 0.4 to 0.8. Q and D can satisfy the relationship that Q/D is equal to 0.3 to 0.9. By controlling the value of the parameter of Equation 3 to the above In the circumference, the viscosity of the composition and the hardness of the cured product can be greatly controlled, and the cured product of the composition can obtain high transparency. In addition, the reliability of the adhesive can be obtained, and durability against light and heat can be ensured.

The curable organopolyoxane composition according to an embodiment of the present invention may include 1 to 30 parts by weight of an organohydro-polysiloxane of the formula 4 below, wherein the terminal or side of the molecule The chain includes a hydrogen atom, and after curing, the ruthenium composition forms a main chain, so that the cured product obtained by curing the finally obtained curable composition by using an organic hydrogen-containing polyoxyalkylene oxide and an organic polyoxyalkylene can be achieved. Good mechanical strength and hardness.

In the case where the amount of the organic hydrogen-containing polysiloxane is less than 1 part by weight, the cured product of the curable composition may become soft and may be easily torn. In the case where the amount of the organic hydrogen-containing polysiloxane is more than 30 parts by weight, the adhesion of the cured product of the composition may be deteriorated.

[Formula ^{4] (R 19 R 20 R} 21 SiO 1/2) m (R 22 R 23 SiO 2/2) d (R 24 SiO 3/2) t (SiO 4/2) q

In Formula 4, m, d, t, and q are values greater than or equal to 0 and less than 1, m + d + t + q = 1, R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ^{23 ,} and R ²⁴ They are each independently a hydrogen atom, or a monosubstituted or unsubstituted monovalent hydrocarbon group, and do not have the same or different aliphatic unsaturated bonds. In Formula 4, the value of m may be 0.01 to 0.2, the value of d may be 0.3 to 0.9, the value of t may be 0 to 0.3, and the value of q may be 0.1 to 0.8.

The hydrocarbon group of the R ¹³ to R ²⁴ functional group in the formula 3 or formula 4 may be an alkyl group and an alkyl group having 1 to 18 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group). Or it may be an aromatic group and an aromatic group having 6 to 18 carbon atoms (for example, a phenyl group, a fluorophenyl group, a naphthol ethyl group, and a β -fluorenyl group). The aromatic group may be included in a molar percentage of 45 moles or less than 45 moles based on the total number of moles of all the organic groups included in Formula 3 and/or Formula 4. In the case of an aromatic group comprising 45 mole percent or more than 45 mole percent, under the high temperature heat resistance test, yellowing due to thermal decomposition or oxidation of the aromatic group may become severe, and The penetration may be significantly deteriorated and thus may not be applied to an optical device.

In the case where the hydrocarbon group is an alkenyl group, an alkenyl group having 2 to 6 carbon atoms (for example, a vinyl group, an allyl group, a β -butenyl group, and a γ -butenyl group) can be used.

Further, in the case of the substituent of the epoxy group, the oxetanyl group, the methacryloxy group, the acryloxy group, the fluorenyl group, the amino group or the cyano group in the formula 3 and the formula 4, it has 1 to 6 A hydrocarbon group of one carbon atom, or a cycloalkyl group having 3 to 12 carbon atoms may be suitable. In particular, a hydrocarbon group having 1 to 3 carbon atoms including the above substituent may be highly suitable.

An epoxy group may include glycidyl (glycidyl), glycidoxy ethyl (glycidoxy ethyl), α - glycidoxy propyl (α-glycidoxy propyl), β - glycidoxypropyl ([beta] glycidoxy propyl), γ - glycidoxypropyltrimethoxysilane (γ-glycidoxy propyl), α - glycidoxybutyl (α-glycidoxy butyl), β - glycidoxybutyl (β-glycidoxy butyl), γ - γ-glycidoxy butyl, δ -glycidoxy butyl, α- (3,4-epoxycyclohexyl)methyl (α-(3,4- Epoxy cyclohexyl)methyl), β- (3,4-epoxycyclohexyl)ethyl, γ- (3,4-epoxycyclohexyl)propyl (γ) - (3,4-epoxy cyclohexyl) propyl ), δ - (3,4- epoxycyclohexyl) butyl (δ- (3,4-epoxy cyclohexyl) butyl) ... and so on.

The substituent having an oxetane group may include (3-ethyloxetane-3-yl)propyl (3). The substituent having an acryloxy group may include acryloyloxy methyl group, β -acryloyloxy ethyl group, β -acryloyloxy propyl group. , γ -acryloyloxypropyl (...), and the like.

Further, methyl group may include methyl Bingxi Xi Bing Xixi yloxymethyl (methacryloyloxymethyl), β - methyl Bing Xixi oxyethyl (β-methacryloyloxyethyl), β - methyl propyl Bingxi Xi (beta] -methacryloyloxypropyl), γ -methacryloyloxypropyl... and the like.

Having a mercapto group of the substituents may include a mercaptomethyl (mercapto methyl), β - mercapto ethyl (β-mercapto ethyl), β - mercaptopropyl (β-mercapto propyl), γ - mercaptopropyl (γ-mercapto propyl) ...and many more. Having an amino group (Amino) the substituent may include aminomethyl (amino methyl), β - aminoethyl (β-amino ethyl), β - aminopropyl (β-amino propyl), γ - aminopropyl ([gamma] Amino propyl), N-( β- (aminoethyl)(N-(β-(amino ethyl)), γ -aminopropyl (γ-amino propyl), etc., having a cyano The substituent may include cyanomethyl, β -cyanoethyl and β -cyanopropyl, γ -cyanopropyl... isocyano the like having a substituent may include methyl isocyanate (isocyanomethyl), β -. acyl isocyanate ethyl (β-isocyanoethyl), β - propyl isocyanate (β-isocyanopropyl), γ - iso Γ-isocyanopropyl... and so on.

The curable organopolyoxane composition may include 0.00005 to 0.003 parts by weight of a platinum group metal catalyst as a hydrosilylation catalyst for promoting solidification. In the case where the amount of the platinum group metal catalyst is less than 0.00005 parts by weight, the cross-linking reaction rate may be lowered, and curing may not be completed. In the case where the amount of the platinum group metal catalyst is more than 0.003 parts by weight, the curing rate may be too fast, workability may be poor, expensive platinum may be uneconomically used in large amounts, and coloring may occur, for example. The defect of coloring, which leads to functional limitation.

The platinum group metal catalyst may include at least one selected from the group consisting of platinum micropowder, platinum black, chloroplatinic acid, chloroplatinic acid, alcohol modifier, hydrogen. Chloroplatinic acid/diolefin complex, platinum/olefin complex, platinum carbonyl (platinum bis (acetoacetate)) Platinum bis (acetylacetonate), chloroplatinic acid/alkenyl siloxane complex (chloroplatinic acid/alkenyl siloxane complex) chloroplatinic acid/divinyltetramethyl bismuth oxychloride Chloroplatinic acid/divinyltetramethyldisiloxane complex and chloroplatinic acid/tetravinyl four Chloroplatinic acid/tetravinyltetramethylcyclotetrasiloxane complex, platinum/divinyltetramethyldisiloxane complex and platinum/tetravinyltetramethylcyclotetrazepine A platinum/alkenyl siloxane complex composed of a platinum/tetravinyltetramethylcyclotetrasiloxane complex, and a complex of chloroplatinic acid and acetylene alcohol.

The curable organopolyoxane composition may include a small amount of a reaction resist as needed, and the reaction resist may include, for example, 2-phenyl-3-butyn-2-ol (2-phenyl-3-butyn-2-ol) ). The amount of the resist may preferably be 0.0080 parts by weight based on the total weight of the composition. The lower limit of the resist may be, for example, 0.00010 parts by weight. In particular, in the case of including an excessive amount of the reaction resist, the curing rate may be lowered.

Further, the composition of the present invention may additionally include at least one selected from the group consisting of inorganic fillers (for example, silica, glass, alumina, zinc oxide, etc.), ruthenium rubber. Silicon rubber powder, resin powder (such as silicon resin, polymethacrylate resin, etc.), heat-resistant agent, antioxidant, radical scavenger (radical scavenger) An optional component of a light stabilizer, a dye, a pigment, or a flame retardant additive, as long as the object of the present invention is not impaired.

Further, the curable organopolyoxane composition according to the present invention can be prepared by using various methods known in the art. For example, the composition of the present invention in advance Liquid A and liquid B were separately prepared from the ingredients, and then the 2 liquids were mixed to obtain a final composition.

In the case where the cured product is formed by curing a curable organopolyoxane composition according to an embodiment of the present invention, the transmittance at a wavelength of 260 nm in the ultraviolet visible spectrum is 45% or less. %, the transmittance at a wavelength of 450 nm in the ultraviolet visible spectrum is 80% or more. Since the cured product of the curable organopolyoxane composition of one embodiment of the present invention has the above physical properties, high transparency and heat resistance can be achieved at high temperatures.

According to another aspect of the present invention, an optical material comprising a curable organopolyoxane composition may be provided, the optical material may include at least one selected from the group consisting of a light emitting diode, an optical semiconductor, an adhesive, and an optical coating. A group of materials, optical potting agents, optical encapsulants, optical cladding, and optical films.

Hereinafter, the present invention will be explained in more detail with reference to the following examples, but the present invention is not limited to the following examples.

Preparation of organic-inorganic metal composites

Synthesis example 1

120 g of mineral oil containing 22% cerium octoate was added to 50 g of xylene, followed by mixing. 120 g of hexamethyldisilazane was added, followed by stirring at 80 ° C for 12 hours. 20 g of a vinyl group-containing organic polyoxyalkylene (ViMe ₂ SiO(Me ₂ SiO) ₇₀ SiMe ₂ Vi) was added and stirred well.

Next, the low boiling point material was distilled and removed at 150 ° C under a reduced pressure of 5 torr. The resulting precipitate was filtered to obtain a fluid yellow solid polysiloxane metal composite (SYN-1).

Synthesis example 2

120 grams of mineral oil containing 22% bismuth octoate was added to 50 grams of xylene and mixed. 180 g of hexamethyldioxane was added, followed by stirring at 80 ° C for 12 hours. 20 g of a vinyl group-containing organic polyoxyalkylene (ViMe ₂ SiO(Me ₂ SiO) ₇₀ SiMe ₂ Vi) was added and stirred well.

Next, the low boiling point material was distilled and removed at 150 ° C under a reduced pressure of 5 torr. The resulting precipitate was filtered to obtain a flowing brown organopolyoxane metal complex (SYN-2).

Synthesis example 3

100 grams of mineral oil containing 22% bismuth octoate was added to 50 grams of xylene and mixed. 107 g of glycidoxypropyltrimethoxysilane was added, followed by stirring at 70 ° C for 9 hours. 40 g of a vinyl group-containing organic polyoxyalkylene (ViMe ₂ SiO(Me ₂ SiO) ₇₀ SiMe ₂ Vi) was added and stirred well.

Next, the low boiling point material was distilled and removed at 150 ° C under a reduced pressure of 5 torr. The resulting precipitate was filtered to obtain a flowing brown organopolyoxane metal complex (SYN-3).

Synthesis example 4

100 grams of mineral oil containing 22% bismuth octoate was added to 50 grams of xylene and mixed. 125 g of phenyltrimethoxysilane was added, followed by stirring at 105 ° C for 12 hours.

Next, the low boiling point material was distilled and removed at 150 ° C under a reduced pressure of 5 torr. The resulting precipitate was filtered to obtain a fluid dark yellow organopolyoxane metal complex (SYN-4).

Synthesis example 5

15 g of cerium butoxide was added to 50 g of xylene and mixed. 550 g of α,ω-hydroxypolysiloxane (HOMe ₂ SiO(Me ₂ SiO) ₄₀ SiMe ₂ OH) was added, followed by stirring at 80 ° C for 9 hours.

Next, the low boiling point material was distilled and removed at 150 ° C under a reduced pressure of 5 torr. The resulting precipitate was filtered to obtain a fluid yellowish organopolyoxane metal complex (SYN-5).

Synthesis example 6

18 g of cerium isopropoxide was added to 50 g of xylene and mixed. 550 g of a hydroxide polyoxydeoxyoxane (HOMe ₂ SiO(Me ₂ SiO) ₄₀ SiMe ₂ OH) was added, followed by stirring at 65 ° C for 12 hours.

Next, the low boiling point material was distilled and removed at 150 ° C under a reduced pressure of 5 torr. The resulting precipitate was filtered to obtain a fluid yellowish organopolyoxane metal complex (SYN-6).

Example 1-8 and Comparative Example 1-6

Example 1

100 g of vinyl-containing MQ resin (0.74 mmol/g vinyl content) and 100 g of linear dimethylpolyorganosiloxane substituted with vinyl at the end using a planetary mixer (ViMe ₂ SiO(Me ₂ SiO) ₁₃₀₀ SiMe ₂ Vi, hereinafter denoted by VP) to prepare a master batch (hereinafter referred to as MB1).

(1) Preparation of composition A

25 g of MB1, 28 g of VP, 0.03 g of platinum complex, and 1.2 g of "SYN-1" of Synthesis Example 1 prepared in advance were mixed at room temperature for 1 hour using an upright mixer to obtain a curable organopolyoxyalkylene. Composition A (hereinafter referred to as "PTA").

(2) Preparation of composition B

5.4 g of an organic hydrogen-containing polyoxyalkylene (hydrogen content: 7.3 mmol/g), 8.7 g of VP, 0.01 g of 1-ethynyl-1-cyclohexanol as a resist, and 0.7 Grafts of propylene glycol trimethoxy decane was placed in a glass vessel and mixed at room temperature for 1 hour using an upright mixer to obtain a curable organopolyoxane composition B (hereinafter referred to as "PTB").

(3) Mixed composition A and composition B

30 parts by weight of the composition A and 10 parts by weight of the composition B were weighed in a container, and pre-mixed using a spatula, and then a resonance-rotation mixer (ARE-310: THINKY corporation) (manufactured) was mixed under vacuum and defoamed for 1 minute to obtain a curable organopolyoxane composition. The composition is cured to produce a cured sheet.

Example 2

The curable organopolyoxane composition was obtained by performing the same process as described in Example 1, except that "SYN-1" of Synthesis Example 1 was changed to "SYN-2" of Synthesis Example 2. The composition is cured to produce a cured sheet.

Example 3

The curable organopolyoxane composition was obtained by the same process as described in Example 1, except that "SYN-1" of Synthesis Example 1 was changed to "SYN-3" of Synthesis Example 3. The composition is cured to produce a cured sheet.

Example 4

The curable organopolyoxane composition was obtained by the same process as described in Example 1, except that "SYN-1" of Synthesis Example 1 was changed to "SYN-4" of Synthesis Example 4. The composition is cured to produce a cured sheet.

Example 5

The curable organopolyoxane composition was obtained by performing the same process as described in Example 1, except that "SYN-1" of Synthesis Example 1 was changed to "SYN-5" of Synthesis Example 5. The composition is cured to produce a cured sheet.

Example 6

The curable organopolyoxane composition was obtained by the same process as described in Example 1, except that "SYN-1" of Synthesis Example 1 was changed to "SYN-6" of Synthesis Example 6. The composition is cured to produce a cured sheet.

Example 7

The curable organopolyoxane composition was obtained by the same procedure as described in Example 1, except that the addition amount of "SYN-1" of Synthesis Example 1 was changed to 3.0 g, and the composition was cured. A cured sheet is produced.

Example 8

The curable organopolyoxane composition was obtained by the same procedure as described in Example 1, except that the addition amount of "SYN-1" of Synthesis Example 1 was changed to 7.2 g, and the composition was cured. A cured sheet is produced.

Comparative example 1

The curable organopolyoxane composition was obtained by performing the same process as described in Example 1 except that "SYN-1" of Synthesis Example 1 was not added, and the composition was cured to produce a Cured sheet.

Comparative example 2

The curable organopolyoxane composition was described in Example 1 except that the "SYN-1" of Synthesis Example 1 was changed to a 0.5% mineral oil containing 22% cerium octoate. The same process is obtained and the composition is cured to produce a cured sheet.

Comparative example 3

The curable organopolyoxane composition was obtained by the same procedure as described in Example 1, except that "SYN-1" of Synthesis Example 1 was changed to 0.11% bismuth octoate (purity of 99.8%). And the composition is cured to make a cured sheet.

Comparative example 4

The curable organopolyoxane composition was obtained by the same procedure as described in Example 1, except that the "SYN-1" of Synthesis Example 1 was changed to 0.01% butoxyxime (purity of 99.8%). And the composition is cured to make a cured sheet.

Comparative Example 5

The curable organopolyoxane composition was obtained by the same procedure as described in Example 1, except that "SYN-1" of Synthesis Example 1 was changed to 0.07% isopropoxide (purity of 99.8%). And the composition is cured to make a cured sheet.

Comparative Example 6

The curable organopolyoxane composition was obtained by the same procedure as described in Example 1, except that "SYN-1" of Synthesis Example 1 was not added, and the composition was cured to produce a cured one. Sheet.

Experimental example

[experimental method]

Manufacture of cured sheets

The curable organopolyoxane composition is mainly cured at 120 ° C for 30 minutes in a mold for molding to a thickness of 2 mm, followed by post-curing in an oven for 2 hours at 150 ° C to form a cured Thin sheet.

1) Initial hardness

Three layers of cured sheets were overlapped and the hardness was measured using a Shore A-type or a Shore D durometer at 25 °C.

2) Hardness change

The sheet for measurement of the initial hardness was placed in an oven at 250 ° C, and the hardness was measured according to the elapsed time by the same method as the measurement of the initial hardness.

3) Penetration

The transmittance of the cured sheet (thickness 2 mm) of the organopolysiloxane according to the present invention was measured using ultraviolet visible spectrum (pattern name: Lambda 950, manufacturer: PERKIN ELMER).

4) Residual weight ratio

The cured product of the organopolyoxyalkylene was stood in an oven at 250 ° C for 168 hours, and its weight was measured before and after the storage to calculate the remaining weight ratio. The higher the residual weight ratio, the better the heat resistance.

5) Change ratio of coefficient of thermal expansion (CTE) (%)

The cured product of the organopolyoxyalkylene was stored in an oven at 250 ° C for 168 hours, and a dynamic thermal characteristics analyzer was used before and after storage (mode name: DMA8000, manufacturer: PERKIN ELMER) measures its coefficient of thermal expansion and calculates it according to the following formula. The lower the ratio of change in the coefficient of thermal expansion, the better the heat resistance.

The ratio of change in thermal expansion coefficient (%) = {(CTE before storage) - (CTE after storage) / (CTE before storage)} * 100 (%)

As shown in Tables 1 and 2, the highly reliable and curable organopolyoxane compositions (Examples 1 through 8) according to the present invention have 50% or less at 260 nm when measured by UV-visible spectroscopy. % penetration. However, when measured by the same method, the products having poor heat resistance according to Comparative Examples 1 to 6 had a transmittance of 60% or more.

After thoroughly examining Examples 1 to 8 and Comparative Examples 1 to 6, the initial penetration of the cured product of the organopolyoxane at 260 nm by UV-visible spectroscopy is generally ensured to be proportional to the heat resistance (remaining Weight ratio).

Further, the coefficient of thermal expansion generally differs depending on the hardness of the organopolyoxane of the cured product. The inventors of the present invention ensured that the coefficient of thermal expansion change before and after 168 hours of the heat resistance test at 250 ° C is similar The initial hardness (250 ° C, 0 hours) of the samples (Examples 1 to 6 and Comparative Examples 1 to 5) decreased with a decrease in the initial penetration.

For Examples 1 to 8 including sheets having low hardness (Examples 1 to 6) and high hardness sheets (Examples 7 and 8), the hardness did not increase at 250 ° C, 168 hours, and the penetration was lowered. Very small, the cured sheets have little thermal decomposition, the remaining weight ratio is high, and no cracks are formed in the sheets up to 2000 hours.

Even though it is not shown in the table, no cracks were formed in the composition of the hardness of Xiao's 50A (Examples 1 to 6) for 2000 hours.

In contrast, in Comparative Examples 1 to 6 excluding the organic-inorganic metal composite according to the embodiment of the present invention, the change in the transmittance was small, but the rate of increase in hardness and the rate of weight reduction were considerably large due to thermal decomposition.

Further, Comparative Examples 2 to 5 including a heat-resistant additive (a component different from the heat-resistant additive of the organic-inorganic metal composite) according to an embodiment of the present invention, when compared with Comparative Example 1 excluding a metal atom, Significantly poor penetration is shown, even showing a high hardness change and the remaining weight ratio. Further, when compared with the examples 1 to 8, all the physical properties of the above measurement were remarkably deteriorated, particularly, cracks were generated within 700 hours at 250 ° C, showing relatively low heat resistance.

Therefore, it can be ensured that the curable organopolyoxane including the heat-resistant additive (organic-inorganic metal composite) according to an embodiment of the present invention exhibits better physical properties than the other compositions.

The scope of protection of the present invention is defined by the scope of the appended patent application. The subject matter is defined by the above description and the exemplary embodiments described herein. This hair Various modifications within the meaning of the patent application scope and the scope of the patent application are considered to be within the scope of the invention.

Claims (12)

An organic ruthenium metal complex comprising one or more of the following formula 1: [(Formula 1][(R ¹ R ² R ³ SiO _1/2 ) _a (R ⁴ R ⁵ SiO _2/2 ) _b (R ⁶ SiO _{3 /2} ) _c (SiO _4/2 ) _d ] _X M _Y In Formula 1, a, b, c and d are each independently greater than or equal to 0 and less than 1, a+b+c+d=1, R ¹ And R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an epoxy group, or a hydroxyl group. ), alkoxy, oxetanyl, acryloyloxy, methacryloyloxy, mercapto, amino or cyano Cyano), and 0<X/Y 4; wherein M includes at least one selected from the group consisting of La, C, Pr, Nd, Pm, Sm, Eu, Gd ), 鋱 (Tb), 镝 (Dy), 鈥 (Ho), 铒 (Er), 銩 (Tm), 镱 (Yb), 镏 (Lu), zirconium (Zr) and titanium (Ti) group.醯醯 The organic base metal composite according to claim 1, further comprising one or more of the following formula 2: [Formula 2] [(R ⁷ R ⁸ R ⁹ Si-N-SiR ¹⁰ R ¹¹ R ¹² ) _e ] _x M _y In Formula 2, e is more than 0 and less than 1, and R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are each independently a hydrogen atom, an alkyl group, an alkenyl group, and an aromatic group. Base, epoxy group, hydroxyl group, alkoxy group, oxetanyl group, propylene methoxy group, methacryloxy group, fluorenyl group, amino group or cyano group, and 0<X/Y 4, wherein M comprises at least one selected from the group consisting of La, C, Pr, Nd, Pm, Sm, Eu, Gd ), 鋱 (Tb), 镝 (Dy), 鈥 (Ho), 铒 (Er), 銩 (Tm), 镱 (Yb), 镏 (Lu), zirconium (Zr) and titanium (Ti) group. The organic base metal composite according to claim 1, wherein in the formula 1, d satisfies the relationship of 0 < d < 0.1. A curable organopolyoxane composition comprising: 0.5 to 10 parts by weight of the organic ruthenium metal complex described in claim 1; 30 to 95 parts by weight of the organopolyoxygen represented by the following formula 3 Alkane: [Formula 3] (R ¹³ R ¹⁴ R ¹⁵ SiO _1/2 ) _M (R ¹⁶ R ¹⁷ SiO _2/2 ) _D (R ¹⁸ SiO _3/2 ) _T (SiO _4/2 ) _Q in Formula 3 , M, D, T and Q are values greater than or equal to 0 and less than 1, and R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, or have the same or different One or more of the substituted or unsubstituted monovalent hydrocarbon groups of the aliphatic saturated group, wherein at least one of the hydrocarbon groups has 1, 2 or more than 2 unsaturated groups at the terminal or side chain of the molecule, and the hydrocarbon group has a straight or Branched main chain); 1 to 30 parts by weight of an organohydro-polysiloxane represented by the following formula 4: [Formula 4] (R ¹⁹ R ²⁰ R ²¹ SiO _1/2 ) _m ( R ²² R ²³ SiO _2/2 ) _d (R ²⁴ SiO _3/2 ) _t (SiO _4/2 ) _q In Formula 4, m, d, t and q are values greater than or equal to 0 and less than 1, R ^{19, R 20, R 21,} R 22, R 23 and R ²⁴ are each independently a hydrogen atom, or Not have the same or different aliphatic unsaturated bonds of a substituted or unsubstituted monovalent hydrocarbon group; and .00005 to .003 parts by weight of platinum group metal catalyst (platinum group metal catalyst). The curable organopolyoxane composition according to claim 4, wherein in the formula 3, the value of M is 0.01 to 0.3, the value of D is 0.3 to 0.6, and the value of T is 0 to 0.3. The value of Q is 0.4 to 0.8, and Q and D satisfy the relationship that Q/D is equal to 0.3 to 0.9. The curable organopolyoxane composition according to claim 4, wherein in the formula 4, the value of m is 0.01 to 0.2, the value of d is 0.3 to 0.9, and the value of t is 0 to 0.3. And the value of q is 0.1 to 0.8. The curable organopolyoxane composition of claim 4, wherein the platinum group metal catalyst may comprise at least one selected from the group consisting of platinum micropowder, platinum black, and hydrochlorochloride. Chloroplatinic acid, alcohol modifier of chloroplatinic acid, hloroplatinic acid/diolefin complex, platinum/olefin complex, Platinum-carbonyl complex composed of platinum (bistoacetate) and platinum (acetylacetonate), hydrochloric acid a chloroplatinic acid/divinyltetramethyldisiloxane complex and a chloroplatinic acid/tetravinyltetramethylcyclotetrasiloxane complex Chloroplatinic acid/alkenyl siloxane complex, platinum/divinyltetramethyldisiloxane complex and platinum/tetravinyltetramethyl complex a platinum/alkenyl siloxane complex composed of a platinum/tetravinyltetramethylcyclotetrasiloxane complex and a complex of chloroplatinic acid and acetylene alcohol group. The curable organopolyoxane composition of claim 4, wherein the curable organopolyoxane composition comprises a plurality of organic polyoxyalkylene oxides and/or organic hydrogen-containing polyoxyalkylene oxides. An organic group, and wherein the organic groups comprise 45 mole percent or less than 45 mole percent of aromatic groups, based on the total moles of the organic groups. The curable organopolyoxane composition of claim 4, wherein the curable organopolyoxane composition has a transmittance of 45% or less in the ultraviolet visible spectrum at a wavelength of 260 nm. And wherein the curable organopolyoxane composition has a transmittance in the ultraviolet visible spectrum at a wavelength of 450 nm of 80% or more. The curable organopolyoxane composition of claim 4, wherein the curable organopolysiloxane composition has a weight loss of less than 8% after heating at 250 ° C for 168 hours. An optical material comprising a curable organopolyoxane composition as described in claim 4 of the patent application. The optical material according to claim 11, wherein the optical material comprises one less selected from the group consisting of a light emitting diode, an optical semiconductor, an adhesive, an optical coating material, an optical potting agent, an optical encapsulant, and an optical A group consisting of a cladding layer and an optical film.