KR101546299B1 - Composition for encapsulating light emitting device and light emitting device - Google Patents
Composition for encapsulating light emitting device and light emitting device Download PDFInfo
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Abstract
TECHNICAL FIELD The present invention relates to a composition for a light emitting device encapsulant and a light emitting device, and more particularly, to a composition for a light emitting device encapsulant and a light emitting device, which comprises a silicone resin containing an epoxy group, polysilazane and titanium dioxide surface- And a composition for a light-emitting element encapsulant having a high refractive index and a light-emitting element.
Description
The present invention relates to a composition for a light emitting device encapsulant and a light emitting device, and more specifically to a light emitting device comprising a silicone resin containing an epoxy group, polysilazane and titanium dioxide modified to include a hydrophobic functional group, , A composition for a light emitting material encapsulant excellent in heat resistance and refractive index, and a light emitting device.
The light emitting device has low power consumption and long life, can be installed in a narrow space, has a high response speed, and is resistant to vibration. Such a light emitting device is used as a backlight of a display device, and active research is currently underway to apply it to general lighting applications.
The light emitting device package is largely composed of a substrate, a light emitting element chip, an adhesive, an encapsulant, a phosphor, and a heat dissipation component. Among them, the light emitting device encapsulant must protect the light emitting device chip from external impact and environment, and therefore, it must have a surface hardness of a certain level or higher. Since the light emitted from the light emitting element passes through the light emitting element encapsulant in the light emitting element package, the encapsulant of the light emitting element must have optical transparency, that is, must have high light transmittance and have a high refractive index .
Korean Patent Laid-Open Publication No. 2009-0127885 (Patent Document 1) relates to a sealing material for a light-emitting device and a light-emitting device, in which silica having an average particle diameter of 1 to 30 nm is added to a silicone composition for sealing a light- And the refractive index can be improved.
In addition, an epoxy resin having a high refractive index and low cost has been widely used as a sealing material for a light emitting element in the past. For example, Korean Patent Registration No. 0559927 (Patent Document 2) discloses a light-emitting device employing the epoxy resin composition for encapsulation with improved light transmittance and hardness. However, since the epoxy resin has low heat resistance, it is deteriorated by heat in a high output light emitting device and yellowing occurs, which causes a problem of lowering brightness.
As a material having excellent light resistance in the ultraviolet ray region, a silicone resin has been used instead of an epoxy resin, but has a low refractive index and adhesive force, and thus has a problem in use as a sealing material for a light emitting device.
The present invention has been conceived to solve the conventional problems, and it is an object of the present invention to provide a silicone resin containing an epoxy group, a polysilazane, and a titanium dioxide surface-modified to include a hydrophobic functional group capable of reacting with an epoxy group, To improve the compatibility in the composition and to provide a composition for encapsulating a luminescent material excellent in light transmittance, surface hardness and heat resistance and having a high refractive index.
It is another object of the present invention to provide a light emitting device comprising a sealing material cured with the composition for a light emitting device encapsulant.
In order to accomplish the above object, the present invention provides a silicone resin composition comprising: a silicone resin containing an epoxy group; Polysilazane; And titanium dioxide whose surface is modified to include a hydrophobic functional group.
According to one embodiment of the present invention, 1 to 100 parts by weight of the polysilazane and 0.01 to 10 parts by weight of titanium dioxide surface-modified to include the hydrophobic functional group are added to 100 parts by weight of the silicone resin containing the epoxy group .
The epoxy resin-containing silicone resin according to an embodiment of the present invention may be selected from compounds represented by the following formulas (1) and (2).
[Chemical Formula 1]
(2)
(Wherein R4 to R11 each independently represent a hydrogen atom, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, A substituted or unsubstituted C1-C10 alkoxy group, or a substituted or unsubstituted C1-C10 alkylamino group, L1 is a substituted or unsubstituted C1-C10 alkylene group or a substituted or unsubstituted C1- E represents a substituted or unsubstituted C2-C10 alkenyl group having an epoxy group, a substituted or unsubstituted C3-C12 cycloalkyl group having an epoxy group, a substituted or unsubstituted C6-C20 cycloalkenyl group having an epoxy group, C20 aryloxy group, a substituted or unsubstituted C1-C10 alkoxy group having an epoxy group, or a substituted or unsubstituted C1-C10 alkylamino group having an epoxy group, and n is an integer of 4 to 15000.)
The silicone resin containing an epoxy group according to an embodiment of the present invention may be a compound represented by the following formula (3) or (4).
(3)
[Chemical Formula 4]
The polysilazane according to an embodiment of the present invention may be selected from perhydro polysilazane, polymethyl silazane, polydimethyl silazane, or one or more of them.
The titanium dioxide modified to include hydrophobic functional groups according to an embodiment of the present invention may be selected from the group consisting of butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, Heptyltrimethoxysilane, heptyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, octyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, Isopropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropylmethyldiethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropyltriethoxysilane, Aminopropyltrimethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltrimethoxysilane, and (3,4-epoxycyclohexyl (meth) acrylate, ) Ethyltrimethoxysilane. The sol-gel method can be used for surface modification.
In the titanium dioxide modified to include the hydrophobic functional group according to an embodiment of the present invention, the titanium dioxide and the silane coupling agent may be surface-modified in a weight ratio of 1: 0.01 to 1: 10.
The titanium dioxide surface-modified to include the hydrophobic functional group according to an embodiment of the present invention may be titanium dioxide surface-modified to include an epoxy group.
According to another aspect of the present invention, there is provided a light emitting device encapsulant comprising a cured product of the composition for a light emitting encapsulant, wherein the encapsulant has a transmittance of 500 to 80% 2.0.
According to another aspect of the present invention, there is provided a light emitting device comprising the composition for a light emitting device encapsulant encapsulated with a cured product.
According to the composition for a light emitting element encapsulant of the present invention and the light emitting element, a silicone resin containing an epoxy group, polysilazane, and titanium dioxide modified to include a hydrophobic functional group are contained so that a silicone resin, polysilazane, The light transmittance, the heat resistance and the surface hardness are remarkably improved and the refractive index is increased as the luminous efficiency is increased.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a reaction of surface-modified titanium dioxide to include a hydrophobic functional group according to an embodiment of the present invention; FIG.
2 is a graph showing the transmittance according to the wavelength of the encapsulant manufactured in Comparative Example 1 of the present invention.
3 is a graph showing the transmittance according to the wavelength of the encapsulant manufactured in Example 1 of the present invention.
4 is a graph showing the transmittance according to the wavelength of the encapsulant manufactured in Example 2 of the present invention.
Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments and methods for measuring properties of a composition for a light emitting element encapsulant and a light emitting device of the present invention will be described in detail. The present invention may be better understood by the following examples, which are for the purpose of illustrating the present invention and are not intended to limit the scope of protection defined by the appended claims.
The composition for encapsulating a light-emitting element of the present invention comprises a silicone resin containing an epoxy group; Polysilazane; And titanium dioxide whose surface has been modified to include a hydrophobic functional group.
The epoxy resin-containing silicone resin according to an embodiment of the present invention is not limited as long as it is a curable silicone resin that forms a three-dimensional curing structure by applying light or heat. For example, one or two or more selected from a phenyl-based silicone resin, a methyl-based silicone resin, and an epoxy-modified silicone resin is preferable.
In particular, the silicone resin containing an epoxy group is preferably a compound represented by the following formula (1) or (2).
[Chemical Formula 1]
(2)
R4 to R11 each independently represent a hydrogen atom, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, a substituted or unsubstituted C6- An aryl group, a substituted or unsubstituted C1-C10 alkoxy group, or a substituted or unsubstituted C1-C10 alkylamino group.
L1 may be either a substituted or unsubstituted C1-C10 alkylene group or a substituted or unsubstituted C6-C20 arylene group. For example, L1 may be a methylene group, an ethylene group, a propylene group or a phenylene group.
E represents a substituent having an epoxy group. For example, E is a substituted or unsubstituted C2-C10 alkenyl group having an epoxy group, a substituted or unsubstituted C3-C12 cycloalkyl group having an epoxy group, a substituted or unsubstituted C6-C20 aryl group having an epoxy group, Or a substituted or unsubstituted C1-C10 alkylamino group having an epoxy group. For example, E may be 1,2-epoxycyclohexane, 2-epoxycyclopentane or 1,2-epoxybutane.
and n is an integer selected from 4 to 15,000.
The weight average molecular weight of the epoxy resin-containing silicone resin according to an embodiment of the present invention may range from about 300 to 100,000 g / mol.
More specifically, the silicone resin containing the epoxy group may be, for example, a compound represented by the following formula (3) or (4).
(3)
[Chemical Formula 4]
The silicone resin containing an epoxy group can be produced by polymerization by a known method. For example, a silicone resin containing reactive hydrogen may be reacted with a compound containing an epoxy group and a double bond at the same time to replace the hydrogen group bonded to the silicone resin with a compound having an epoxy group, but the present invention is not limited thereto.
The polysilazane according to one embodiment of the present invention may be a compound represented by the following formula (5).
[Chemical Formula 5]
R1, R2 and R3 are each independently a hydrogen atom, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, a substituted or unsubstituted C6 A substituted or unsubstituted C1-C10 alkoxy group, or a substituted or unsubstituted C1-C10 alkylamino group.
The R1 to R3 may be the same or different among the basic constitutional units.
For example, in one basic building block, R1 may be methyl, and in other basic building blocks, R1 may be phenyl.
The term "substituted" in the present specification means that at least one hydrogen atom is replaced by a substituent selected from the group consisting of a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carboxyl group or a salt derivative thereof, a sulfonic acid group or a salt derivative thereof, C10 alkyl group, C2-C10 alkenyl group, C1-C10 alkoxy group, C3-C10 cycloalkyl group, C3-C10 cycloalkenyl group, C6-C20 aryl group, C6-C20 aryloxy group, An arylthio group, or a C3-C20 hetero aryl group.
The unsubstituted C1-C10 alkyl group in the present specification means a saturated hydrocarbon group having a linear and branched structure in which one hydrogen atom is absent from an alkane. Specific examples of the unsubstituted C1-C10 alkyl group include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl and hexyl.
In the present specification, an unsubstituted C2-C10 alkenyl group means a terminal group containing at least one carbon-carbon double bond at the middle or end of the unsubstituted C2-C10 alkyl group. Examples of unsubstituted C2-C10 alkenyl groups include ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, propadienyl, isoprenyl, allyl ) And the like.
In the present specification, the unsubstituted C3-C12 cycloalkyl group refers to a cyclic saturated hydrocarbon group, and specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like.
In the present specification, an unsubstituted C3-C10 cycloalkenyl group means a group containing at least one carbon-carbon double bond constituting a ring of a cyclic saturated hydrocarbon group. Examples of the unsubstituted C3-C10 cycloalkenyl group include cyclobutenyl, cyclopentenyl, cyclohexenyl, and the like.
In the present specification, an unsubstituted C6-C20 aryl group means a monovalent group having a carbocyclic aromatic system having 6 to 20 carbon atoms, which may be a monocyclic or polycyclic group, have. Examples of the unsubstituted C6-C20 aryl group include phenyl, naphtyl, and the like.
In the present specification, the unsubstituted C1-C10 alkoxy group has the formula -OY (wherein Y is the unsubstituted C1-C10 alkyl group), and specific examples thereof include methoxy, ethoxy, isopropyloxy, Pentoxy and the like.
In the present specification, the unsubstituted C1-C10 alkylamino group has the chemical formula -NQ1Q2 (wherein Q1 and Q2 are each hydrogen or a C1-C10 alkyl group, and Q1 and Q2 are not hydrogen at the same time) Amino, ethylamino, dimethylamino, diethylamino and the like.
In the present specification, the unsubstituted C6-C20 aryloxy group has the formula of -OAr (wherein Ar is the unsubstituted C6-C20 aryl group), and specific examples thereof include phenoxy, naphthalenoxy and the like .
In the present specification, the unsubstituted C6-C20 arylthio group has the formula of -OZ (wherein Z is the unsubstituted C6-C20 aryl group), and specific examples thereof include phenylthio, naphthalenylthio and the like .
The weight average molecular weight of the polysilazane may range from 100 to 100,000 g / mol, but is not limited thereto.
The polysilazane is particularly effective when it is a perhydro polysilazane, polymethylsilazane, or polydimethylsilazane.
Such a polysilazane may serve as a curing agent for a silicone resin containing an epoxy group, or may form a matrix of an encapsulating material together with a silicone resin containing an epoxy group, thereby enhancing the mechanical properties and enhancing the surface hardness.
The content of polysilazane is preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, per 100 parts by weight of the silicone resin containing an epoxy group.
When the polysilazane is contained in the above range, the sealing material formed from the composition can have a high refractive index without cracking, and can exhibit improved heat resistance.
The titanium dioxide surface-modified to include hydrophobic functional groups according to an embodiment of the present invention may be surface-modified with a silane coupling agent using a sol-gel method.
In the present invention, the term "hydrophobic" means a hydrophobic property which is not polarized and is not bonded to water. More specifically, in the present invention, an alkyl chain having 4 or more carbon atoms, A ring, an amino group, or an epoxy group.
Surface modification of titanium dioxide by the sol-gel method can improve compatibility with silicone resin or polysilazane containing an epoxy group rather than simply coating a material containing a hydrophobic functional group on the titanium dioxide surface. Therefore, the interface between titanium dioxide and the matrix does not occur, scattering of light generated at the interface can be reduced, and the transmittance and the refractive index can be improved, which is effective. In addition, there is an advantage that the compatibility can be improved in the composition and mechanical properties such as surface hardness can be improved.
That is, when a titanium dioxide and a silane coupling agent are reacted through a conventional sol-gel method, a hydrophobic functional group can be easily formed on the surface of titanium dioxide.
The silane coupling agent is not particularly limited as long as it is a silane coupling agent containing a hydrophobic group that is well known in the art. Examples of the silane coupling agent include butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxy Silane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropyltrimethoxysilane, Glycidoxypropylmethyldiethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropylmethyldiethoxysilane, methacryloxypropylmethyldiethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane, Can be selected.
More preferably, one or more of glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane and glycidoxypropylmethyldiethoxysilane can be selected.
When a sol-gel reaction is carried out with a silane coupling agent containing an epoxy group as described above, the compatibility with the silicone resin containing an epoxy group and the polysilazane is improved and not only mechanical properties such as surface hardness, but also heat resistance, And the refractive index is increased.
It is preferable that the titanium dioxide and the silane coupling agent are surface-modified in a weight ratio of 1: 0.01 to 1: 10, more preferably titanium dioxide and the silane coupling agent are 1: 0.1 To 1: 1 by weight.
When the silane coupling agent is less than 0.01 weight ratio, the surface of the titanium dioxide may not be sufficiently modified. If the silane coupling agent is more than 10 weight ratio, the surface modification effect may not be achieved. , It is most effective to perform the sol-gel reaction in the above-mentioned range.
The content of the titanium dioxide surface-modified to include the hydrophobic functional group is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the epoxy resin-containing silicone resin .
The light emitting device encapsulant according to an embodiment of the present invention can be manufactured by curing the epoxy resin-containing silicone resin together with the polysilazane and the surface-modified titanium dioxide to include the hydrophobic functional group.
Meanwhile, the composition for a light emitting device encapsulant of the present invention may further comprise a curing agent if necessary. The curing agent may be an acid anhydride and may include, but is not limited to, known acid anhydrides such as, for example, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride or methylhexahydrophthalic anhydride.
In addition, the composition for encapsulating a light-emitting element of the present invention may further contain additives if necessary. The additive may include, for example, a deterioration inhibitor, a softening agent, an antioxidant, a plasticizer, a lubricant, a flame retardant, an antistatic agent, a defoaming agent, an antioxidant, an ultraviolet absorber,
The light emitting device encapsulant thus manufactured may have a transmittance of 80% or more at a wavelength of 500 nm and a refractive index of 1.5 to 2.0.
The composition for a light emitting device encapsulant according to an embodiment of the present invention can be used for an encapsulant of blue, green, red, and white LEDs or OLEDs and can be used as a semiconductor laser, a photodiode, a solar cell, a phototransistor, Device.
EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Property measurement
1) Measurement of transmittance
The transmittance was measured using a UV-Vis spectrophotometer (ultraviolet-visible spectrophotometer) at a wavelength of 300 nm to 1000 nm with a resolution of 0.1 nm.
2) Heat resistance measurement
The heat resistance was measured by measuring the transmittance before and after the heat treatment at 200 ° C for 1 hour.
3) Measurement of refractive index
The refractive index of the film was measured using an Abbe refractometer.
4) Surface hardness measurement
The surface hardness was measured using a shore hardness tester.
[Production Example 1]
Preparation of Surface-Modified Titanium Dioxide Having Hydrophobic Function
50 mL of anhydrous MeOH is injected into 4 g of TiO 2 / MeOH (25% w / w) solution. Add 1 to 2 drops of HCl to act as a catalyst while stirring at 1000 rpm. octyltrimethoxysilane (0.3 mL) and anhydrous toluene (50 mL) were added. The reaction mixture was heated at 40 ° C. under reduced pressure to remove the methanol and reacted for 16 h to modify the surface of the titanium dioxide to include the hydrophobic functional group.
[Production Example 2]
Preparation of Surface-Modified Titanium Dioxide Having an Epoxy Group
50 mL of anhydrous MeOH is injected into 4 g of TiO 2 / MeOH (25% w / w) solution. Add 1 to 2 drops of HCl to act as a catalyst while stirring at 1000 rpm. (3-glydicyloxypropyl) trimethoxysilane (0.3 mL) and anhydrous toluene (50 mL) were added. The reaction mixture was heated at 40 ° C. under reduced pressure to remove methanol and reacted for 16 h to modify the surface of the titanium dioxide to include hydrophobic functional groups.
[Production Example 3]
Preparation of silicone resin containing epoxy group
As shown in Reaction Scheme 1, 0.001 mol (mol) of tetramethylcyclotetrasiloxane and 4-vinyl-1-cyclohexane 1,2-epoxy 0.042 The molar amount was dissolved in 20 ml of toluene. The mixed solvent was purged with nitrogen, refluxed at about 80 캜 for 1 hour, and then the temperature was lowered to room temperature. Then, 1 drop of Lamoreaux platinum catalyst was added to the mixed solvent, and the mixture was reacted at 70 ° C for 2 hours. After the completion of the reaction, the temperature of the mixed solvent was lowered to room temperature, 0.005 g of 2-mercaptobenzothiazole was added to the mixed solvent, and then the solvent was evaporated to obtain a solution of hydrogen in 1,2-epoxycyclohexylethyl Substituted tetramethyltetra (1,2-epoxycyclohexylethyl) cyclotetrasiloxane (Formula 3) was prepared.
[Reaction Scheme 1]
[Example 1]
1 g of the epoxy resin-containing silicone resin prepared in Preparation Example 3, 0.1 g of polymonomethylsilazane, and 0.01 g of titanium dioxide which had been surface-modified to contain the hydrophobic functional group prepared in Preparation Example 1 were mixed, The solvent is removed. The film was cured at 180 DEG C for 1 hour using a hot plate to obtain a sealing film having a thickness of 1 mm. Physical properties of the sealing film were shown in Table 1 below.
[Example 2]
1 g of the silicone resin containing the epoxy group prepared in Preparation Example 3, 0.1 g of polymonomethylsilazane, and 0.01 g of titanium dioxide surface-modified to have the epoxy group prepared in Preparation Example 2 were mixed and air bubbles and solvent Remove. The film was cured at 180 DEG C for 1 hour using a hot plate to obtain a sealing film having a thickness of 1 mm. Physical properties of the sealing film were shown in Table 1 below.
[Comparative Example 1]
A sealing film of 1 mm in thickness was obtained in the same manner as in Example 1, except that titanium dioxide which had been surface-modified to contain a hydrophobic functional group was not included. Physical properties of the sealing film were measured and are shown in Table 1 below.
[Comparative Example 2]
1 g of the silicone resin containing the epoxy group prepared in Preparation Example 3, 1.5 g of polymonomethylsilazane, and 0.01 g of titanium dioxide surface-modified to have the epoxy group prepared in Preparation Example 2 were mixed and air bubbles and solvent Remove. The film was cured at 180 ° C for 1 hour by using a hot plate, but the film was not formed and fractured, and the measurement of physical properties was impossible.
[Comparative Example 3]
1 g of the epoxy resin-containing silicone resin prepared in Preparation Example 3, 0.1 g of polymonomethylsilazane and 0.5 g of titanium dioxide whose surface was modified to have an epoxy group of Preparation Example 2 were mixed and the bubbles and the solvent were removed using a vacuum pump . The film was cured at 180 DEG C for 1 hour using a hot plate to obtain a sealing film having a thickness of 1 mm. Physical properties of the sealing film were shown in Table 1 below.
[Table 1]
FIG. 2 is a graph showing the transmittance of the encapsulant film prepared in Comparative Example 1 before and after the heat treatment (a) and after the heat treatment (b) FIG. 4 is a graph showing the transmittance according to the wavelengths (a) and (b) before and after the heat treatment of the encapsulant film prepared in Example 2. FIG.
As shown in Figs. 2 to 4, it can be seen that neither the comparative example nor the embodiment shows a large change in transmittance even after heat treatment at 200 DEG C for 1 hour. However, it was found that the transmittance of Examples 1 and 2 was generally improved over that of Comparative Example 1 based on the wavelength of 550 nm.
Further, it was found that Comparative Example 1 containing no surface-modified titanium dioxide having a hydrophobic group had a relatively low surface hardness and a low refractive index.
That is, in Example 1, it was found that the refractive index and the surface hardness were increased by containing the surface-modified titanium dioxide to include the hydrophobic functional group.
In addition, as shown in Example 2, when the surface-modified titanium dioxide containing an epoxy group was contained, the compatibility with the silicone resin containing an epoxy group and the polysilazane was improved and the surface hardness was remarkably improved .
In Comparative Example 2 in which polysilazane was added in an excess amount, phase separation and bubbles were generated and no film was formed. When an excess amount of surface-modified titanium dioxide was added as in Comparative Example 3, the refractive index and surface hardness were good, It was found that the transmittance and the heat resistance were sharply reduced and were not suitable for the encapsulating material.
While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention. Accordingly, the above description should not be construed as limiting the scope of the present invention defined by the limits of the following claims.
Claims (11)
With respect to 100 parts by weight of the silicone resin containing the epoxy group,
1 to 100 parts by weight of the polysilazane and 0.01 to 10 parts by weight of titanium dioxide surface-modified to include the hydrophobic functional group.
Wherein the silicone resin containing an epoxy group is a compound represented by the following formula (1) or (2).
[Chemical Formula 1]
(2)
In the formula, R4 to R11 each independently represent a hydrogen atom, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C3-C12 cycloalkyl group, A substituted or unsubstituted C1-C10 alkoxy group, or a substituted or unsubstituted C1-C10 alkylamino group, and L1 is a substituted or unsubstituted C1-C10 alkylene group or a substituted or unsubstituted C1- C6-C20 arylene group,
E is a substituted or unsubstituted C2-C10 alkenyl group having an epoxy group, a substituted or unsubstituted C3-C12 cycloalkyl group having an epoxy group, a substituted or unsubstituted C6-C20 aryl group having an epoxy group, A substituted or unsubstituted C1-C10 alkoxy group, or a substituted or unsubstituted C1-C10 alkylamino group having an epoxy group,
and n is an integer selected from 4 to 15,000.
The silicone resin containing the epoxy group is a compound represented by the general formula (3) or (4).
(3)
(In the above formula 3, n is an integer selected from 4 to 15000.)
[Chemical Formula 4]
Wherein the polysilazane is one or more selected from the group consisting of perhydro polysilazane, polymethyl silazane, and polydimethyl silazane.
The titanium dioxide surface-modified to include the hydrophobic functional group may be selected from the group consisting of butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, Hexadecyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, octadecyltriethoxysilane, octadecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, Silane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, aminopropyltrimethoxysilane, aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, Glycidoxypropylmethylethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropylmethyldimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, Aminopropyltrimethoxysilane, chloropropyltrimethoxysilane, mercaptopropyltrimethoxysilane, and (3,4-epoxycyclohexyl) ethyltrimethoxysilane < RTI ID = 0.0 & Wherein the titanium dioxide is titanium dioxide surface-modified with a sol-gel method using one or more silane coupling agents selected from the group consisting of titanium dioxide and titanium dioxide.
Wherein the titanium dioxide surface-modified to include the hydrophobic functional group is surface-modified with the titanium dioxide and the silane coupling agent in a weight ratio of 1: 0.01 to 1:10.
Wherein the titanium dioxide surface-modified to include the hydrophobic functional group is titanium dioxide surface-modified to include an epoxy group.
Wherein the light emitting element encapsulant has a transmittance of 80% or more at 500 nm and a refractive index of 1.5 to 2.0.
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