KR20130035299A - Silicone-based resin composition and method of preparing the same - Google Patents
Silicone-based resin composition and method of preparing the same Download PDFInfo
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Abstract
The present invention relates to a silicone-based resin composition and a method for manufacturing the same, and in particular, it is easy to control the viscosity and reaction rate in the manufacturing process, has excellent transmittance, and is stable against ultraviolet rays or heat, thereby preventing yellowing. The present invention can be applied as a sealing material such as a light emitting element or a light receiving element in an optical semiconductor device (semiconductor light emitting device), particularly as a transparent sealing material for an optical semiconductor such as an LED.
Description
The present invention relates to a silicone-based resin composition and a method for producing the same.
An optical semiconductor device (semiconductor light emitting device) having a LED (light emitting diode) chip, which forms a pn bond in a semiconductor layer grown on a crystal substrate and uses the junction region as a light emitting layer, as a light emitting element is used for various display devices and display devices. It is widely used for such purposes.
Examples of the optical semiconductor device include visible light emitting devices and high temperature operating electronic devices using gallium nitride compound semiconductors such as GaN, GaAlN, InGaN, and InAlGaN, and recently developed in the fields of blue light emitting diodes and ultraviolet light emitting diodes. This is going on.
An optical semiconductor device including an LED chip as a light emitting element has a LED chip mounted on the light emitting surface side of a lead frame, electrically connects the LED chip and the lead frame by wire bonding, and serves as a protection and lens function of the light emitting element. It is sealed by resin.
Recently, white LEDs have attracted attention as a new light source, and it is said that the market will expand greatly in the future, mainly for lighting applications. White LED is applied to YN phosphor on a bare chip of GaN, mixed with blue light emission of GaN and yellow light emission of phosphor, and emits white light. . In addition, recently, a method of combining a plurality of phosphor materials by using an ultraviolet LED chip as a light source has been developed from the improvement of color tone. In addition, in order to use LED for a lighting use etc., the durability improvement is calculated | required.
On the other hand, an epoxy resin is often used as a sealing material used when sealing a light emitting element such as an LED (light emitting diode) chip. Epoxy resins are used for factors such as a transparent point and good workability. Generally, the epoxy resin for LED sealing consists of bisphenol A glycidyl ether, a hardening accelerator, such as methylhexahydro phthalic anhydride, an amine type, or phosphorus type.
However, since these components generate carbonyl groups by absorption of ultraviolet light, there is a drawback that they absorb visible light and yellow. In order to solve this problem, a method of using hydrogenated bisphenol A glycidyl ether has been proposed, but the performance is not sufficient.
Silicone resins are widely used to improve yellowing and lowering of luminance due to ultraviolet light. Silicone resin is excellent in transparency in an ultraviolet region, and there is very little fall of yellowing and transmittance by ultraviolet light. However, since the silicone resin has a low refractive index, light extraction efficiency is low. Accordingly, it is time to further develop a silicone-based resin having better refractive index and light transmittance.
The present invention is to provide a silicone-based resin composition that is easy to control the viscosity and reaction rate in the manufacturing process and excellent in transmittance, stable to ultraviolet rays or heat to prevent the occurrence of yellowing.
One embodiment of the present invention is a mixture of (a) alkoxysilane or chlorosilane containing a phenyl group, (b) alkoxysilane or chlorosilane containing a vinyl group and (c) alkoxysilane or chlorosilane containing a solvent and a solvent Then, adding a weak acid to polymerize to prepare an organopolysiloxane represented by the following formula (1) (S1); Preparing a organopolysiloxane represented by the following Chemical Formula 2 by adding a weak base to the organopolysiloxane represented by Chemical Formula 1 and polymerizing the same (S2); And adding an organohydrogenpolysiloxane and a platinum group metal catalyst represented by the following Formula 3 to the organopolysiloxane represented by the Formula 2, (S3).
≪ Formula 1 >
[R 1 a R 2 b Vi c SiO (4-abc) / 2 ] n
Wherein R 1 is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R 2 is hydroxyl At least one selected from period, methoxy and ethoxy, Vi is a vinyl group, a is a number from 1.00 to 1.80, b is a number from 0.09 to 0.5, c is a number from 0.01 to 0.2, n is 5 to 15.)
<Formula 2>
[R 1 a R 2 b Vi c SiO (4-abc) / 2 ] n
Wherein R 1 is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R 2 is hydroxyl At least one selected from period, methoxy and ethoxy, Vi is a vinyl group, a is a number from 1.00 to 1.90, b is a number from 0.001 to 0.2, c is a number from 0.01 to 0.2, n is Number from 10 to 100.)
<Formula 3>
[R 1 a R 2 b H c SiO (4-abc) / 2 ] n
Wherein R 1 is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R 2 is hydroxyl At least one selected from a period, methoxy and ethoxy, a is a number from 1.00 to 1.90, b is a number from 0.001 to 0.2, c is a number from 0.01 to 0.2, n is a number from 10 to 100 .)
Another embodiment of the present invention is the alkoxysilane or chlorosilane containing the (a) phenyl group, (b) alkoxysilane or chlorosilane containing a vinyl group in the step S1 and alkoxysilane or chloro containing (c) an alkyl group The silane is a method for producing a silicone-based resin composition, characterized in that the molar ratio of (a) :( b) :( c) is 0.2 to 0.8: 0.1 to 0.5: 0.01 to 0.2.
According to another embodiment of the present invention, in the step S1, the alkoxysilane or chlorosilane in (a) to (c) has a molar ratio of divalent alkoxysilane or chlorosilane and trivalent alkoxysilane or chlorosilane of 0.3 to 0.8: It is a manufacturing method of the silicone type resin composition characterized by mixing so that it may become 0.2-0.6.
Another embodiment of the present invention is a method of preparing a silicone-based resin composition in which the concentration of the weak acid in the step S1 is 0.0001 to 1M.
Another embodiment of the present invention is a weak acid in the step S1 is a method of producing a silicone-based resin composition of at least one selected from hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
Another embodiment of the present invention is a method for producing a silicone-based resin composition, characterized in that the weak acid is added in an amount of 1 to 3 equivalents based on 1 equivalent of the alkoxy group or the chloro group in the step S1.
Another embodiment of the present invention is a method for producing a silicone-based resin composition in which the concentration of the weak base in step S2 is 0.0001 to 1M.
Another embodiment of the present invention is a weak base in the step S2 is a method for producing a silicone-based resin composition of at least one selected from a metal hydrate and an amine organic salt.
Another embodiment of the present invention is a method for producing a silicone-based resin composition, characterized in that the weak base in step S2 is added in an amount of 0.5 to 1 equivalent based on 1 equivalent of weak acid.
Another embodiment of the present invention is a method for producing a silicone-based resin composition, characterized in that the organopolysiloxane represented by the formula (2) prepared in step S2 has a viscosity of 500 to 40000 cps.
Another embodiment of the present invention is based on 100 parts by weight of the organopolysiloxane represented by the formula (2) in step S3 10 to 80 parts by weight of the organohydrogenpolysiloxane represented by the formula (3) and 0.00001 to 1 weight of the platinum group metal catalyst It is a manufacturing method of the silicone type resin composition added by part.
Another embodiment of the present invention is the platinum group metal catalyst in the step S3 is platinum platinum vinyl siloxane complex, platinum 2,4-pentanedioate, platinum divinyl tetramethyl disiloxane complex and platinum carbonyl It is a manufacturing method of 1 or more types of silicone type resin composition chosen from cyclovinyl methylsiloxane complex.
Another embodiment of the present invention is a silicone-based resin composition comprising an organopolysiloxane represented by Formula 2, an organohydrogenpolysiloxane represented by Formula 3, and a platinum group metal catalyst.
<Formula 2>
[R 1 a R 2 b Vi c SiO (4-abc) / 2 ] n
Wherein R 1 is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R 2 is hydroxyl At least one selected from period, methoxy and ethoxy, Vi is a vinyl group, a is a number from 1.00 to 1.90, b is a number from 0.001 to 0.2, c is a number from 0.01 to 0.2, n is Number from 10 to 100.)
<Formula 3>
[R 1 a R 2 b H c SiO (4-abc) / 2 ] n
Wherein R 1 is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R 2 is hydroxyl At least one selected from a period, methoxy and ethoxy, a is a number from 1.00 to 1.90, b is a number from 0.001 to 0.2, c is a number from 0.01 to 0.2, n is a number from 10 to 100 .)
Another embodiment of the present invention is the silicone resin composition is a silicone resin composition prepared according to the manufacturing method.
The silicone resin composition according to the present invention is easy to control the viscosity and reaction rate in the manufacturing process, and excellent in transmittance (transmittance), stable to ultraviolet or heat to prevent the occurrence of yellowing, optical semiconductor device (semiconductor light emitting device) It is applicable as a sealing material, such as a light emitting element and a light receiving element in this invention, especially as a transparent sealing material for optical semiconductors, such as LED.
1 is a graph showing the transmittance of Example 1 according to the heat resistance change.
2 is a graph showing the transmittance of Example 2 according to the change in heat resistance.
3 is a graph showing the transmittance of Comparative Example 1 according to the heat resistance change.
According to one embodiment of the invention, (a) an alkoxysilane or chlorosilane comprising a phenyl group, (b) an alkoxysilane or chlorosilane comprising a vinyl group and (c) an alkoxysilane or chlorosilane comprising a solvent and a solvent After mixing, adding a weak acid to polymerize to prepare an organopolysiloxane represented by the following formula (S1); Preparing a organopolysiloxane represented by the following Chemical Formula 2 by adding a weak base to the organopolysiloxane represented by Chemical Formula 1 and polymerizing the same (S2); And adding a organohydrogenpolysiloxane and a platinum group metal catalyst represented by the following Formula 3 to the organopolysiloxane represented by the above Formula 2 (S3).
≪ Formula 1 >
[R 1 a R 2 b Vi c SiO (4-abc) / 2 ] n
Wherein R 1 is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R 2 is hydroxyl At least one selected from period, methoxy and ethoxy, Vi is a vinyl group, a is a number from 1.00 to 1.80, b is a number from 0.09 to 0.5, c is a number from 0.01 to 0.2, n is 5 to 15.)
<Formula 2>
[R 1 a R 2 b Vi c SiO (4-abc) / 2 ] n
Wherein R 1 is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R 2 is hydroxyl At least one selected from period, methoxy and ethoxy, Vi is a vinyl group, a is a number from 1.00 to 1.90, b is a number from 0.001 to 0.2, c is a number from 0.01 to 0.2, n is Number from 10 to 100.)
<Formula 3>
[R 1 a R 2 b H c SiO (4-abc) / 2 ] n
Wherein R 1 is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R 2 is hydroxyl At least one selected from a period, methoxy and ethoxy, a is a number from 1.00 to 1.90, b is a number from 0.001 to 0.2, c is a number from 0.01 to 0.2, n is a number from 10 to 100 .)
R 1 in
The alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, Cyclohexyl group, octyl group, nonyl group, decyl group, etc. are mentioned.
Examples of the aryl group having 2 to 12 carbon atoms, preferably 6 to 10 carbon atoms include a phenyl group, tolyl group, xylyl group, and naphthyl group.
Examples of the aralkyl group having 2 to 12 carbon atoms, preferably 6 to 10 carbon atoms, include a benzyl group, a phenylethyl group and a phenylpropyl group.
Examples of the alkenyl group having 2 to 12 carbon atoms, preferably 6 to 10 carbon atoms include vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, hexenyl group, cyclohexenyl group and octenyl group. .
In addition, some or all of the remaining hydrogen atoms except the hydrogen atom bonded to the silicon atom in the alkyl group, aryl group, aralkyl group and alkenyl group may be substituted with halogen atoms such as fluorine, bromine, chlorine and cyano groups.
First, a) an alkoxysilane or chlorosilane comprising a phenyl group, (b) an alkoxysilane or chlorosilane comprising a vinyl group and (c) an alkoxysilane or chlorosilane comprising an alkyl group are mixed with a weak acid, The polymerization is performed to prepare an organopolysiloxane represented by Formula 1 (S1).
The (a) alkoxysilane or chlorosilane containing a phenyl group, (b) the alkoxysilane or chlorosilane containing a vinyl group, and (c) the alkoxysilane or chlorosilane containing an alkyl group is (a) :( b) :( c It is preferable to mix so that molar ratio of) may be 0.2-0.8: 0.1-0.5: 0.01-0.2.
When the molar ratio of (a) is less than 0.2, it is difficult to achieve high refractive index, and when it exceeds 0.8, yellowing is caused. In addition, when the molar ratio of (b) is less than 0.1, curing is not performed. When the molar ratio is greater than 0.5, refractive index and overcuring phenomenon are caused. In addition, when the molar ratio of (c) is less than 0.01, it is difficult to obtain an effect of preventing yellowing, and when it exceeds 0.2, the effect is not increased any more and is meaningless.
Examples of the alkoxysilane or chlorosilane containing (a) phenyl group include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, and the like. It may include, but is not limited thereto.
Examples of the alkoxysilane or chlorosilane containing the (b) vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, divinyldimethoxysilane, divinyldiethoxysilane, divinyldichlorosilane, and the like. It may include, but is not limited thereto.
Examples of the alkoxysilane or chlorosilane containing the alkyl group (c) include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane and dimethyldichlorosilane. It is not limited thereto.
The alkoxysilane or chlorosilane in (a) alkoxysilane or chlorosilane containing a phenyl group, (b) alkoxysilane or chlorosilane containing a vinyl group and (c) an alkoxysilane or chlorosilane containing an alkyl group is a divalent alkoxy. Preference is given to using a mixture of silane or chlorosilane and trivalent alkoxysilane or chlorosilane. At this time, the molar ratio of the divalent alkoxysilane or chlorosilane and the trivalent alkoxysilane or chlorosilane is mixed so that the molar ratio of 0.3 to 0.8: 0.2 to 0.6. If the molar ratio of the divalent alkoxysilane or chlorosilane is less than 0.3, the molecular weight is small and low. Degrees and cracks may occur, and if it exceeds 0.8, the molecular weight increases when participating in the polymerization, the viscosity increases, and may be disadvantageous in hardness after curing. In addition, when the molar ratio of the trivalent alkoxysilane or chlorosilane is less than 0.2, the increase in molecular weight and hardness may be disadvantageous. When the molar ratio of trivalent alkoxysilane or chlorosilane is less than 0.2, the molecular weight is small so that the viscosity is low, and there is a problem of cracking after curing.
Examples of the solvent include methanol, ethanol, isopropyl alcohol, isobutyl alcohol, alkyl alcohols, alkyl esters, alkyl ketones, and the like, but is not limited thereto. The content of the solvent may be appropriately adjusted so as to dissolve the reactants of (a) to (c).
The weak acid is preferably in a concentration of 0.0001 to 1M in that it prevents yellowing due to the residual of the acid catalyst.
The weak acid may be at least one selected from hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, but is not limited thereto.
The weak acid is (a) an alkoxysilane or chlorosilane containing a phenyl group, (b) an alkoxysilane or chlorosilane containing a vinyl group and (c) an alkoxysilane or an alkoxy of chlorosilane, which is the raw material reacting material. It is added in an amount of 1 to 3 equivalents based on 1 equivalent of the group or chloro group, and when the weak acid is added in the above amount, there is an effect of condensing the silicon material with a minimum acid catalyst.
The organopolysiloxane represented by
In the present invention, by using the organopolysiloxane represented by the formula (1) to prepare the organopolysiloxane represented by the formula (2) by the production method according to the present invention, it is possible to improve the high refractive and high viscosity properties and stability by a stable synthesis method You can get the effect. In addition, in the present invention, by adding a weak base to the organopolysiloxane represented by
Subsequently, a weak base is added to the organopolysiloxane represented by
The weak base is preferable in that it can easily control the reaction rate having a concentration of 0.0001 to 1M.
The weak base may include at least one selected from general metal hydrates such as sodium hydroxide and potassium hydroxide, and amine organic salts, but is not limited thereto.
The weak base is added in an amount of 0.5 to 1 equivalent based on the acid, that is, the equivalent of 1 equivalent of the weak acid. When the weak base is added to the content, it is possible to control the rapid increase in molecular weight by alkali addition and decrease the catalytic effect due to neutralization. There is an effect that can suppress the back.
The organopolysiloxane represented by Formula 2 prepared above preferably has a viscosity of 500 to 40000 cps.
In the present invention, in order to obtain a high refractive index in the silicone resin, it is preferable to increase the a content in the organopolysiloxane represented by Formula 2 to contain a large amount of phenyl groups.
Organopolysiloxane represented by the formula (2) is n is 10 to 100, it is preferable to have a viscosity of 500 to 40000cps, if the number and viscosity of the n is less than the above range may cause heat shock due to shrinkage after curing If it exceeds the above range, turbidity may occur after blending.
The organopolysiloxane represented by Chemical Formula 2 satisfying the number and viscosity conditions of n may be prepared by adding a weak base to polymerize and then extracting using an organic solvent in a conventional manner.
The organic solvent is propylene glycol methyl ether acetate (PGMEA), propylene glycol ethyl ether acetate, propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl glycol methyl acetate, ethyl Oxypropionate, methylethoxypropionate, butyl acetate, ethyl acetate, cyclohexanone, acetone, methyl isobutyl ketone, dimethylformamide, dipropylene glycol methyl ether, toluene, methyl cellosolve and ethyl cellosolve Alkyl alcohols such as methanol, ethanol, isopropyl alcohol, alkyl esters, alkyl ketones, and the like, but are not limited thereto.
Subsequently, the organohydrogenpolysiloxane and the platinum group metal catalyst represented by Chemical Formula 3 are added to the organopolysiloxane represented by Chemical Formula 2 (S3).
That is, the silicone resin composition according to the present invention may be thermally cured by adding a platinum group metal catalyst to the organopolysiloxane represented by Formula 2 and the organohydrogenpolysiloxane represented by Formula 3.
The silicone resin composition may be added in an amount of 10 to 80 parts by weight of the organohydrogenpolysiloxane represented by Formula 3 and 0.00001 to 1 part by weight of a platinum group metal catalyst based on 100 parts by weight of the organopolysiloxane represented by Formula 2. do.
If the content of the organohydrogenpolysiloxane represented by the formula (3) is less than 10 parts by weight, there is a problem that hardening does not occur, and when it exceeds 80 parts by weight, problems such as refractive index, viscosity, and crack generation may occur.
In addition, when the content of the platinum group metal-based catalyst is out of the range there is a problem that white turbidity or curing does not proceed.
The platinum group metal-based catalyst may include a platinum microvinyl methyl siloxane complex, a platinum 2,4-pentanedioate, a platinum divinyl tetramethyl disiloxane complex, a platinum carbonylcyclovinyl methyl siloxane complex, and the like. It is not limited to this.
At this time, the organopolysiloxane represented by the formula (2) and the organohydrogenpolysiloxane represented by the formula (3) is the content of Si-Vi and Si-H of the organohydrogenpolysiloxane 100: 5 to 50 in the organopolysiloxane It is preferable that it mixes in the ratio of 100 to 10-40, and is contained in a silicone resin composition. When the molar ratio is within the above range, it is possible to obtain an effect of increasing hardness after curing.
The silicone resin composition prepared according to the present invention may optionally include additives in addition to the organopolysiloxane represented by Chemical Formula 2, the organohydrogenpolysiloxane represented by Chemical Formula 3, and the platinum group metal catalyst. The additive may be used without particular limitation as long as it is commonly used in the field to which the present invention belongs, and specifically, modifiers, inorganic fillers, antioxidants, and the like may be mentioned.
In the present invention, a high molecular weight organopolysiloxane represented by the general formula (2) having high viscosity may be prepared by adding a weak acid to polymerize the low molecular weight organopolysiloxane represented by the formula (1), and then adding the weak base to recondensation. have.
When the molecular weight, ie, the number of n, is low, the viscosity tends to be proportionally lowered, which is advantageous in terms of hardness, but yellowing or cracking occurs, and when mixed with the phosphor, the phosphor sinks downward, and thus the optical properties may be significantly decreased. have. In the case of condensation of organopolysiloxane with only weak acid, the reaction rate is slow and polymerization time is long to polymerize the polymer of the polymer.In the case of condensation using strong acid, the reaction takes place so fast that it is difficult to control the molecular weight, that is, the number of n. In addition, there is a relatively difficult problem in controlling the viscosity through the control of n number.
In order to solve this problem, silicone resin has excellent stability and optical properties through secondary condensation method by weak base after primary condensation with the weak acid, and is more mild than synthetic method by strong acid and strong alkali, so that the processability in the polymerization process is also increased. Can be obtained.
In addition, according to the preparation method of the present invention, by reducing the content of the alkoxy group defined by R 2 in
In addition, the present invention can obtain the effect of improving the permeability by minimizing the silanol group of the organopolysiloxane represented by the formula (2) prepared by the above-described manufacturing method.
According to another embodiment of the present invention, to provide a silicone-based resin composition comprising an organopolysiloxane represented by the formula (2), an organohydrogenpolysiloxane represented by the formula (3) and a platinum group metal catalyst.
<Formula 2>
[R 1 a R 2 b Vi c SiO (4-abc) / 2 ] n
Wherein R 1 is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R 2 is hydroxyl At least one selected from period, methoxy and ethoxy, Vi is a vinyl group, a is a number from 1.00 to 1.90, b is a number from 0.001 to 0.2, c is a number from 0.01 to 0.2, n is Number from 10 to 100.)
<Formula 3>
[R 1 a R 2 b H c SiO (4-abc) / 2 ] n
Wherein R 1 is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R 2 is hydroxyl At least one selected from a period, methoxy and ethoxy, a is a number from 1.00 to 1.90, b is a number from 0.001 to 0.2, c is a number from 0.01 to 0.2, n is a number from 10 to 100 .)
The silicone resin composition is prepared according to the above-described manufacturing method, and the content of the organopolysiloxane represented by Formula 2, the organohydrogenpolysiloxane represented by Formula 3, and the platinum group metal catalyst is the same as described above.
Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, the following embodiments are merely preferred embodiments of the present invention, and the present invention is not limited to the following embodiments.
Example One
0.25 mol of phenyltrimethoxysilane, 0.1 mol of vinyltrimethoxysilane, 0.05 mol of methyltrimethoxysilane, 0.35 mol of diphenyldimethoxysilane, 0.2 mol of methylvinyldimethoxysilane, 0.05 mol of dimethyldimethoxysilane and isobutyl Alcohol was added in an amount of 40% by weight of the total reactant, followed by mixing, followed by polymerization at 70 ° C. for 1 hour by adding 2.4 moles of 0.1M HCl to [R 1 a R 2 b Vi c SiO (4-abc) / 2 ] n (Wherein R 1 is a phenyl group and a methyl group, and R 2 is a methoxy and a hydroxy group.) A first compound was prepared. Where a is 1, b is 0.3, c is 0.1 and n is a number of 10. At this time, the molar content of the weak acid is alkoxy 1 of each of the reactants (phenyltrimethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane diphenyldimethoxysilane, methylvinyldimethoxysilane, dimethyldimethoxysilane) Total content calculated based on equivalents.
To the prepared first compound, 1.2 mol of 0.1 M NaOH, which is 0.5 equivalent based on 1 equivalent of the weak acid, was added to condense again to obtain [R 1 a R 2 b Vi c SiO (4-abc) / 2 ] n ( Wherein R 1 is a phenyl group and a methyl group, and R 2 is a methoxy and a hydroxy group.) A second compound (organopolysiloxane) was prepared. a is 1.20, b is 0.1, c is 0.1 and n is a number of 70.
Toluene was then added and extracted, and dehydration and solvent were removed. The prepared second compound and organohydrogenpolysiloxane, platinum-based catalyst and additives were formulated in a weight ratio content as shown in Table 1 below to obtain a silicone resin composition capable of thermosetting.
Example 2
0.25 mol of phenyltrimethoxysilane, 0.13 mol of vinyltrimethoxysilane, 0.02 mol of methyltrimethoxysilane, 0.4 mol of diphenyldimethoxysilane, 0.2 mol of methylvinyldimethoxysilane and 40% of the isobutyl alcohol. After adding by weight, the mixture was mixed with 2.4 mol of 0.1 M HCl, and then polymerized at 70 ° C. for 1 hour, where [R 1 a R 2 b Vi c SiO (4-abc) / 2 ] n (wherein R 1 is a phenyl group and A methyl group, R 2 is a methoxy and a hydroxy group.) A first compound was prepared. Where a is 1.2, b is 0.3, c is 0.1 and n is a number of 12. At this time, the molar content of the weak acid is alkoxy 1 of each of the reactants (phenyltrimethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane diphenyldimethoxysilane, methylvinyldimethoxysilane, dimethyldimethoxysilane) Total content calculated based on equivalents.
To the prepared first compound, 1.2 mol of 0.1 M NaOH, which is 0.5 equivalent based on 1 equivalent of the weak acid, was added to condense again to obtain [R 1 a R 2 b Vi c SiO (4-abc) / 2 ] n ( Wherein R 1 is a phenyl group and a methyl group, and R 2 is a methoxy and a hydroxy group.) A second compound (organopolysiloxane) was prepared. a is 1.4, b is 0.1, c is 0.1 and n is a number of 75.
Toluene was then added and extracted, and dehydration and solvent were removed. The prepared second compound and organohydrogenpolysiloxane, platinum-based catalyst and additives were formulated in a weight ratio content as shown in Table 1 below to obtain a silicone resin composition capable of thermosetting.
Comparative example One
0.3 mole of phenyltrimethoxysilane, 0.1 mole of vinyltrimethoxysilane, 0.37 mole of diphenyldimethoxysilane, 0.23 mole of methylvinyldimethoxysilane and 40% by weight of the entire isobutyl alcohol reactant were added together and 2.4 mole of 0.1 M HCl was added. It was added and polymerized at 70 ° C for 1 hour to give [R 1 a R 2 b Vi c SiO (4-abc) / 2 ] n (wherein R 1 is a phenyl group and a methyl group, and R 2 is a methoxy and a hydroxyl group). The first compound was prepared. Where a is 1, b is 0.3, c is 0.1 and n is a number of 10. Toluene was then added and extracted, and dehydration and solvent were removed. The first compound (organopolysiloxane), organohydrogenpolysiloxane, platinum catalyst, and additives prepared above were formulated in the same ratio as shown in Table 1 to obtain a silicone resin composition capable of thermosetting.
Comparative example 2
The same procedure as in Example 2 was carried out except that vinyltrimethoxysilane and methylvinyldimethoxysilane were not used.
(1) The platinum-based catalyst is Andisil series (Andisil).
(2) The silane coupling agent is KBM-403 brand name (Shin-Etsu).
(3) Polymerization inhibitors and fillers are Andisil sesies (Andisil).
The compositions according to Examples 1 and 2 and Comparative Examples 1 and 2 were cured at 150 ° C. for 60 minutes at high temperature to form a cured sheet having a thickness of 2 mm. The result after evaluation of the transmittance | permeability and heat resistance result of the obtained hardened | cured material using the method as described below is shown in Table 2 below.
(1) Transmittance: The transmittance at 400 nm was measured for the fabricated specimens of 2 mm using UV-VIS.
(2) Heat resistance: Permeability was measured in units of 10 hours after aging in a 150 ° C. oven, and the time when the transmittance was reduced by 5% was expressed as a heat resistance value.
(3) Refractive index: It measured at 588 nm using the Prism Coupler.
1 is a graph showing the transmittance of Example 1 according to the heat resistance change, Figure 2 is a graph showing the transmittance of Example 2 according to the heat resistance change, Figure 3 is a graph showing the transmittance of Comparative Example 1 according to the heat resistance change. .
As shown in Table 2 and FIGS. 1 to 3, in the case of Examples 1 and 2, it was found that the refractive index and the transmittance / thermal stability were superior to those of Comparative Example 1. In addition, Comparative Example 2 was not cured, and thus the transmittance, refractive index, and heat resistance could not be measured. From this, the silicone resin composition according to the present invention has excellent permeability and excellent heat resistance to heat, and thus sealing materials such as light emitting elements and light receiving elements in optical semiconductor devices (semiconductor light emitting devices), in particular for optical semiconductors such as LEDs, etc. It was found to be suitable for use as a transparent sealing material.
All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.
Claims (14)
Preparing a organopolysiloxane represented by the following Chemical Formula 2 by adding a weak base to the organopolysiloxane represented by Chemical Formula 1 and polymerizing the same (S2); And
Method of preparing a silicone-based resin composition comprising the step (S3) of adding the organohydrogenpolysiloxane represented by the following formula (3) and the platinum group metal catalyst to the organopolysiloxane represented by the formula (2).
[Formula 1]
[R 1 a R 2 b Vi c SiO (4-abc) / 2 ] n
Wherein R 1 is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R 2 is hydroxyl Period, methoxy and ethoxy, either a number from 1.00 to 1.80, b from 0.09 to 0.5, c from 0.01 to 0.2, and n from 5 to 15.)
(2)
[R 1 a R 2 b Vi c SiO (4-abc) / 2 ] n
Wherein R 1 is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R 2 is hydroxyl Any one selected from period, methoxy and ethoxy, Vi is a vinyl group, a is a number from 1.00 to 1.90, b is a number from 0.001 to 0.2, c is a number from 0.01 to 0.2, n is 10 To 100.)
(3)
[R 1 a R 2 b H c SiO (4-abc) / 2 ] n
Wherein R 1 is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R 2 is hydroxyl Period, methoxy and ethoxy, either a number from 1.00 to 1.90, b from 0.001 to 0.2, c from 0.01 to 0.2, n from 10 to 100.)
(2)
[R 1 a R 2 b Vi c SiO (4-abc) / 2 ] n
Wherein R 1 is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R 2 is hydroxyl Any one selected from period, methoxy and ethoxy, Vi is a vinyl group, a is a number from 1.00 to 1.90, b is a number from 0.001 to 0.2, c is a number from 0.01 to 0.2, n is 10 To 100.)
(3)
[R 1 a R 2 b H c SiO (4-abc) / 2 ] n
Wherein R 1 is at least one selected from an alkyl group having 1 to 12 carbon atoms, an aryl group having 2 to 12 carbon atoms, an aralkyl group having 2 to 12 carbon atoms, and an alkenyl group having 2 to 12 carbon atoms, and R 2 is hydroxyl Period, methoxy and ethoxy, either a number from 1.00 to 1.90, b from 0.001 to 0.2, c from 0.01 to 0.2, n from 10 to 100.)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20160079417A (en) | 2014-12-26 | 2016-07-06 | 코오롱인더스트리 주식회사 | Silicone Resin Hybrid Composition and Method of Preparing the Same |
| KR20160091600A (en) | 2015-01-26 | 2016-08-03 | 코오롱인더스트리 주식회사 | Silicone Resin Composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20160079417A (en) | 2014-12-26 | 2016-07-06 | 코오롱인더스트리 주식회사 | Silicone Resin Hybrid Composition and Method of Preparing the Same |
| KR20160091600A (en) | 2015-01-26 | 2016-08-03 | 코오롱인더스트리 주식회사 | Silicone Resin Composition |
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