KR101375106B1 - Silicone Resin Composition - Google Patents

Abstract

The present invention relates to a silicone resin composition and an encapsulant for an electronic material including the same. The silicone resin composition of this invention has the effect which has more excellent heat resistance, hardness, and crack resistance, maintaining a high transmittance | permeability compared with the conventional silicone resin composition.

Description

Silicone resin composition {Silicone Resin Composition}

The present invention relates to a silicone resin composition and an encapsulant for an electronic material including the same.

Compared with conventional light sources, LEDs have a long service life, low operating voltage, easy light emission control, fast switching response, and small size, making them widely used as backlights for display devices such as LCD TVs and mobile phones. It is also being used for general lighting.

LEDs are encapsulated in a semiconductor chip with a transparent resin, and conventionally, an epoxy material has been mainly used as a material of the transparent resin. However, the epoxy resin has a high modulus of elasticity, so that a crack may occur between the wire, the chip, and the epoxy resin and the wire may break when the temperature changes. In addition, the low heat resistance has been a problem that the resin turns yellow when used for a long time to reduce the optical characteristics of the LED.

Accordingly, silicone resins having better transparency than epoxy resins and excellent heat resistance have been increasingly used mainly for blue and white LEDs. However, there remains a problem that silicone resins tend to be cracked because of poor mechanical properties such as bending strength.

Thus, Korean Patent No. 10-2005-0011195 has been studied for a curable silicone composition applied to an optical device or an optical component material having high hardness and strength and excellent light transmittance using a siloxane / polycyclic hydrocarbon system. However, a material composed of a composite material of silicon and polycyclic hydrocarbons has a disadvantage in that heat resistance is inferior as compared with pure silicon materials, and yellowing and cracking are more likely to occur.

In addition, Korean Patent No. 10-2010-0040615 has been conducted on a light emitting diode device encapsulant having no yellowing and cracks including a silicone resin containing a fluorenyl alkyl group. However, since the fluorenyl alkyl group induces a rapid increase in viscosity depending on the amount added, there is a disadvantage in that it is difficult to obtain a liquid high refractive index material.

In addition, Korean Patent No. 10-2009-0134327 has been studied for a light-transmissive resin composition for an encapsulant comprising a polymetallosiloxane obtained by copolymerizing a silicon compound containing a metal compound. The germanium-based compound used in the production of the polymetallosiloxane may be a rare earth metal, which may cause a cost increase in manufacturing the composite.

The present invention was derived to solve the above problems, the present invention is to provide a silicone resin composition having a high transmittance, and at the same time excellent in heat resistance, hardness and crack resistance.

The present invention relates to a silicone resin composition comprising at least one silicone resin represented by the following formula (1).

[Chemical Formula 1]

^{_{(R 1 SiO 3/2)}} a (R 2 R 3 SiO 2/2) b (R 4 R 5 R 6 SiO 1/2) c (SiO 4/2) d (BO (3-h) / 2) _e (R ⁷ BO _{(2-g) / 2} ) _f

In Chemical Formula 1, R ¹ to R ⁷ are each independently hydrogen, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 6 -30 Aryl group, substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted carbon atoms An alkenyl group of 2 to 30, a substituted or unsubstituted alkynyl group of 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group of 1 to 30 carbon atoms, a substituted or unsubstituted carbonyl group, a hydroxy group, or a combination thereof, 0 <a <1, 0≤b <1, 0≤c <1, 0≤d <1, 0≤e <1, 0≤f <1, 0≤h <1, 0≤g <1, and a + b + c + d + e + f = 1.

In the present invention, the boron unit structure of Chemical Formula 1 is any one selected from the group consisting of Chemical Formulas 2 to 4.

(2)

(3)

Formula 4

In the present invention, the silicone resin is not particularly limited in molecular weight, it may be preferably from 100 to 10,000 g / mol. In the present invention, unless otherwise specified, the term "molecular weight" means a weight average molecular weight (Weight Average Molecular Weight).

The viscosity of the silicone resin in the present invention is not particularly defined, but may be preferably 500 to 100,000 cps (centipoise) at 25 ℃.

The silicone resin composition according to the present invention may further include a hydrogen silicide catalyst, an adhesion promoter, a curing retardant, and the like in the silicone resin.

The hydrogen silicide catalyst may be a metal of Group 8 of the periodic table, a catalyst in which these metals are supported on a carrier of alumina or silica, or a salt or a complex of these metals, and the content of the hydrogen silicide catalyst is based on the total weight of the resin composition. It may be desirable to be from 0.1 to 100 ppm (parts per million).

Although the adhesion promoter is not particularly limited, it may be preferable to use a silane compound containing an alkoxy group.

Still another aspect of the present invention relates to an electronic material encapsulant comprising the silicone resin composition.

The silicone resin composition according to the present invention has an effect of having more excellent heat resistance, hardness and crack resistance while maintaining a high transmittance as compared with the conventional silicone resin composition.

Before describing the present invention in detail, it is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the invention, which is defined solely by the appended claims. shall. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art unless otherwise stated.

Throughout the description and claims, unless the context requires otherwise, the word "comprise" is intended to include the stated article, step or group of articles, and steps; It is not meant to exclude an object, step or group of objects or a group of steps.

On the contrary, the various embodiments of the present invention can be combined with any other embodiments as long as there is no clear counterpoint. In particular, any feature that is indicated to be advantageous or advantageous may be combined with any other feature or feature that is indicated to be advantageous or advantageous.

The present invention relates to a silicone resin composition comprising at least one silicone resin represented by the following formula (1).

[Chemical Formula 1]

^{_{(R 1 SiO 3/2)}} a (R 2 R 3 SiO 2/2) b (R 4 R 5 R 6 SiO 1/2) c (SiO 4/2) d (BO (3-h) / 2) _e (R ⁷ BO _{(2-g) / 2} ) _f

In Chemical Formula 1, R ¹ to R ⁷ are each independently hydrogen, a substituted or unsubstituted C 1 -C 30 alkyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 6 -30 Aryl group, substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted carbon atoms An alkenyl group of 2 to 30, a substituted or unsubstituted alkynyl group of 2 to 30 carbon atoms, a substituted or unsubstituted alkoxy group of 1 to 30 carbon atoms, a substituted or unsubstituted carbonyl group, a hydroxy group, or a combination thereof, 0 <a <1, 0≤b <1, 0≤c <1, 0≤d <1, 0≤e <1, 0≤f <1, 0≤h <1, 0≤g <1, and a + b + c + d + e + f = 1.

In the present invention, the boron unit structure of Chemical Formula 1 may be any one selected from the group consisting of Chemical Formulas 2 to 4.

(2)

(3)

Formula 4

Formula 2 may be expressed when h of (BO _{(3-h) / 2} ) in the boron unit structure of Formula 1 is 0.

Formula 3 may be expressed when g of (R ⁷ BO _{(2-g) / 2} ) in the boron unit structure of Formula 1 is 0.

Formula 4 may be expressed when g of (R ⁷ BO _{(2-g) / 2} ) in the boron unit structure of Formula 1 is 1.

The silicone resin according to the present invention is not particularly limited in molecular weight, but preferably may have a molecular weight of 100 to 10,000 g / mol. By adjusting the molecular weight of the silicone resin as described above, the encapsulant has excellent hardness, it can be maintained excellent processability.

In addition, the silicone resin of the present invention may be liquid or solid at 25 ℃. In particular, in order to be used as an encapsulant for an electronic material, it is preferable that the viscosity of the silicone resin is not too high, for example, it may be 500 to 100,000 cps (centipoise), more preferably 1,000 to 50,000 cps at 25 ° C. In this range, the silicone resin of the present invention can maintain excellent processability and hardness characteristics.

The silicone resin composition of the present invention may further include any one or more selected from the group consisting of a hydrogen silicide catalyst, an adhesion promoter, and a curing retardant in the silicone resin.

In the present invention, the hydrogen silicide catalyst acts as a catalyst in curing the silicone resin through a hydrogen silicide reaction, for example, a metal of Group 8 of the periodic table or the metal supported on a carrier such as alumina or silica. It may be a catalyst or a salt or a complex of the metal. Platinum, rhodium or ruthenium may be used as the metal of Group 8 of the periodic table, and platinum may be preferably used.

The hydrogen silicide catalyst is not particularly limited in content, but preferably may be 0.1 to 100 parts per million (ppm) based on the total weight of the resin composition. This is because when the hydrogenation siliconization catalyst is added less than 0.1 ppm to the total weight of the resin composition, the amount of the catalyst is too small, so that the hydrogen siliconization reaction does not proceed well. This is difficult, because yellowing (yellowing) is likely to occur during curing.

In the present invention, the adhesion improving agent is not particularly limited in kind, it may be preferable to use a silane compound containing an alkoxy group, for example vinyltriethoxysilane (vinyltriethoxysilane), γ- methacryloxypropyl Trimethoxysilane (γ-methacryloxypropyltrimethoxysilane), γ-glycidoxypropyltrimethoxysilane, and the like can be used.

The present invention relates to an encapsulant for an electronic material comprising the silicone resin composition.

Examples of the electronic material that can be encapsulated by the encapsulant including the silicone resin composition of the present invention include diodes, transistors, thyristors, integrated ICs, semiconductor devices used in hybrid ICs, and the like.

Hereinafter, the present invention will be described in detail through examples. However, the examples presented below are merely examples for describing the present invention, and the scope of the present invention is not limited thereto.

In the following examples, unless otherwise specified, Vi represents a vinyl group, Ph represents a phenyl group, and Me represents a methyl group.

<Examples>

Example  One

After dissolving 100 g of water and 1.5 g of boric acid in a three-necked flask, 100 g of toluene was added to the flask, and then maintained at 10 ° C., 65 g of phenyltrichlorosilane and diphenyldichlorosilane. ), A mixture of 5 g of trimethylchlorosilane, 5 g of trimethylchlorosilane, and 10 g of vinyldimethylchlorosilane was added dropwise over 1 hour. After the dropping was completed, the reaction was performed while refluxing at 80 ° C. for 4 hours. After the reaction was completed to remove the water layer to prepare a polymer solution dissolved in toluene. The obtained polymer solution was washed three times with water to remove hydrochloric acid, a reaction byproduct. Subsequently, the neutral polymer solution was distilled under reduced pressure to remove toluene to obtain a silicone resin (Formula 5) according to the present invention. The molecular weight of the obtained silicone resin (Formula 5) was measured by gel permeation chromatography, and the polystyrene reduced molecular weight was 2,700 g / mol, and the viscosity was measured by a Brookfield Viscometer. It was measured in cps.

[Chemical Formula 5]

_{(PhSiO 3/2) 0.64 (} Ph 2 SiO 2/2) 0.04 (Me 3 SiO 1/2) 0.1 (ViMe 2 SiO 1/2) 0.17 (BO 3/2) 0.05

Example  2

Except that the amount of boric acid is 0.6g was carried out in the same manner as in Example 1, to obtain a silicone resin of the formula (6). The molecular weight of the obtained silicone resin (Formula 6) was 2,500g / mol, the viscosity was measured to 25,000cps.

[Chemical Formula 6]

_{(PhSiO 3/2) 0.66 (} Ph 2 SiO 2/2) 0.04 (Me 3 SiO 1/2) 0.1 (ViMe 2 SiO 1/2) 0.18 (BO 3/2) 0.02

Example  3

Except that the amount of boric acid (0.3 g) was carried out in the same manner as in Example 1, to obtain a silicone resin of the formula (7). The molecular weight of the obtained silicone resin (Formula 7) was 2,400g / mol, the viscosity was measured to 18,000cps.

[Formula 7]

_{(PhSiO 3/2) 0.67 (} Ph 2 SiO 2/2) 0.04 (Me 3 SiO 1/2) 0.1 (ViMe 2 SiO 1/2) 0.18 (BO 3/2) 0.01

Example  4

After dissolving 100 g of water and 0.35 g of boric acid in a three-necked flask, 100 g of toluene was added to the flask and then maintained at 10 ° C., 65 g of phenyltrichlorosilane and diphenyldichlorosilane. A mixture of 5 g), 2 g of trimethylchlorosilane and 14 g of tetramethyldisiloxane was added dropwise over 1 hour. After the dropping was completed, the reaction was performed while refluxing at 80 ° C. for 4 hours. After the reaction was completed to remove the water layer to prepare a polymer solution dissolved in toluene. The obtained polymer solution was washed three times with water to remove hydrochloric acid, a reaction byproduct. Subsequently, the neutral polymer solution was distilled under reduced pressure to remove toluene to obtain a silicone resin as shown in the following formula (8). The molecular weight of the obtained silicone resin (Formula 8) was 1,800 g / mol, the viscosity was measured to 2,500 cps.

[Formula 8]

_{(PhSiO 3/2) 0.68 (} Ph 2 SiO 2/2) 0.04 (Me 3 SiO 1/2) 0.04 (HMe 2 SiO 1/2) 0.23 (BO 3/2) 0.01

Comparative Example  One : Phenyl vinyl silicone  Suzy

Into a three-necked flask, 100 g of water and 100 g of toluene were added to the flask, and then maintained at 10 ° C., 65 g of phenyltrichlorosilane, 5 g of diphenyldichlorosilane, 5 g of trimethylchlorosilane, and vinyl dimethylchlorosilane. The mixture which mixed 10 g of (vinyldimethylchlorosilane) was dripped over 1 hour. After the dropping was completed, the reaction was performed while refluxing at 80 ° C. for 4 hours. After the reaction was completed to remove the water layer to prepare a polymer solution dissolved in toluene. The obtained polymer solution was washed three times with water to remove hydrochloric acid and acetic acid as byproducts. Subsequently, the neutral polymer solution was distilled under reduced pressure to remove toluene, thereby obtaining a phenylvinylsilicone resin represented by the following formula (9). The molecular weight of the obtained phenyl vinyl silicone resin (Formula 9) was 2,300 g / mol, the viscosity was measured to 15,000 cps.

[Chemical Formula 9]

_{(PhSiO 3/2) 0.68 (} Ph 2 SiO 2/2) 0.04 (Me 3 SiO 1/2) 0.1 (ViMe 2 SiO 1/2) 0.18

Comparative Example  2 : Phenylhydrogensilicone  Suzy

Into a three-necked flask, 100 g of water and 100 g of toluene were added to the flask, and then maintained at 10 ° C., where 65 g of phenyltrichlorosilane, 5 g of diphenyldichlorosilane, and 14 g of tetramethyldisiloxane were mixed. Was added dropwise over 1 hour. After the dropping was completed, the reaction was performed while refluxing at 80 ° C. for 4 hours. After the reaction was completed to remove the water layer to prepare a polymer solution dissolved in toluene. The obtained polymer solution was washed three times with water to remove hydrochloric acid, a reaction byproduct. Subsequently, the neutral polymer solution was distilled under reduced pressure to remove toluene, thereby obtaining a phenylhydrogensilicone resin represented by the following Chemical Formula 10. The obtained phenylhydrogensilicone resin (Formula 10) had a molecular weight of 1,800 g / mol and a viscosity of 2,500 cps.

[Formula 10]

_{(PhSiO 3/2) 0.68 (} Ph 2 SiO 2/2) 0.04 (HMe 2 SiO 1/2) 0.24

Property evaluation experiment

Of the silicone resins according to the present invention of Examples 1 to 4 above, the silicone resins of Examples 1 and 4 were mixed with respect to the total weight of the composition, respectively 66.99% by weight and 43% by weight, and 0.01% by weight of a platinum catalyst (Aldrich). % Was added to prepare composition 1, and the silicone resins of Examples 2 and 4 were mixed with 66.99% by weight and 43% by weight, respectively, and 0.01% by weight of platinum catalyst (Aldrich) was added to composition 2. The silicone resins of Examples 3 and 4 were mixed with 66.99 wt% and 43 wt% of the total weight of the composition, and 0.01 wt% of a platinum catalyst (Aldrich) was added to prepare composition 3.

In addition, the silicone resin not according to the present invention of Comparative Example 1 and Comparative Example 2 was mixed 66.99% by weight, 43% by weight relative to the total weight of the composition, and 0.01% by weight of a platinum catalyst (Aldrich Co., Ltd.) was added to Comparative Composition 1 Prepared.

The compositions 1 to 3 and Comparative Composition 1 were compared by measuring the refractive index, transmittance, heat resistance, hardness and crack resistance, and the results are shown in the following [Table 1].

The refractive index was measured at 589 nm using an Abbe refractometer, and the transmittance was measured at 600 nm using a Shimadzu UV-spectrometer for 2 hours. In addition, the heat resistance measurement was measured for permeability after the cured specimens stay in the oven at 150 ℃ for 1000 hours, the crack resistance measurement was measured by dropping the specimen at a height of 1m, then measured the ratio of the cracked sample.

As shown in the following [Table 1], the compositions 1, 2 and 3 comprising the silicone resin according to the present invention can be seen that the excellent properties compared to the comparative composition 1 in heat resistance, hardness, crack resistance. Particularly, in Comparative Composition 1, yellowing occurred after 1000 hours in an oven at 150 ° C., resulting in a significantly lower heat resistance and a lower crack resistance.

division Composition 1 Composition 2 Composition 3 Comparative Composition 1 Silicone resin of Example 1 (% by weight) 66.99 Silicone resin of Example 2 (% by weight) 66.99 Silicone resin of Example 3 (% by weight) 66.99 Silicone resin of Example 4 (% by weight) 43 43 43 Silicone resin of Comparative Example 1 (% by weight) 66.99 Silicone resin of Comparative Example 2 (% by weight) 43 Platinum Catalyst (wt%) 0.01 0.01 0.01 0.01 Refractive index 1.528 1.529 1.532 1.528 Permeability (%) 98 99 99 97 Heat resistance 92 89 90 85 Hardness (shore D) 65 60 55 45 crack(%) 0 0 0 40

As described above, those skilled in the art will understand that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It will be understood by those skilled in the art that the present invention may be embodied in many other specific forms without departing from the spirit or scope of the invention as defined by the appended claims and their equivalents. .

Claims (11)

A silicone resin composition for encapsulating an electronic device comprising a silicone resin represented by Formula 1-1 and a silicone resin represented by Formula 1-2:
[Formula 1-1]
(R ¹ SiO _3/2 ) _a (R ² R ³ SiO _2/2 ) _b (R ⁴ R ⁵ R ⁶ SiO _1/2 ) _c (SiO _4/2 ) _d (BO _{(3-h) / 2} ) _e (R ⁷ BO _{(2-g) / 2} ) _f
(In Formula 1-1, R ¹ to R ⁷ are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon atom 6 to 30 aryl group, substituted or unsubstituted arylalkyl group having 7 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 30 carbon atoms, substituted or unsubstituted An alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms substituted or unsubstituted, a substituted or unsubstituted carbonyl group, a hydroxy group or a combination thereof, 0 < a <1, 0≤b <1, 0≤c <1, 0≤d <1, 0≤e <1, 0≤f <1, 0≤h <1, 0≤g <1, a + b + c + d + e + f = 1.)
[Formula 1-2]
(R ¹ SiO _3/2 ) _a (R ² R ³ SiO _2/2 ) _b (R ⁴ R ⁵ R ⁶ SiO _1/2 ) _c (SiO _4/2 ) _d (BO _{(3-h) / 2} ) _e (R ⁷ BO _{(2-g) / 2} ) _f
(In the above formula 1-2, R ¹ to R ⁷ are each independently hydrogen, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted carbon number 6 to 30 aryl groups, substituted or unsubstituted arylalkyl groups having 7 to 30 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 30 carbon atoms, substituted or unsubstituted heterocycloalkyl groups having 2 to 30 carbon atoms, substituted or unsubstituted A substituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted carbonyl group, a hydroxy group, or a combination thereof, At least one of R ⁴ to R ⁶ is hydrogen, 0 <a <1, 0≤b <1, 0≤c <1, 0≤d <1, 0≤e <1, 0≤f <1, 0 ≦ h <1, 0 ≦ g <1, and a + b + c + d + e + f = 1.) The method of claim 1,
The boron unit structures of Formula 1-1 and Formula 1-2 are any one selected from the group consisting of Formulas 2 to 4 below:
Formula 2

(3)

Formula 4

The method of claim 1,
The silicone resin has a molecular weight of 100 to 10,000 g / mol silicone resin composition.
The method of claim 1,
The silicone resin has a viscosity of 500 to 100,000 cps at 25 ° C.
The method of claim 1,
The silicone resin composition further comprises any one or more selected from the group consisting of a hydrogen silicide catalyst, an adhesion promoter and a curing retardant to the silicone resin.
6. The method of claim 5,
The hydrogen silicide catalyst is a metal of Group 8 of the periodic table, a catalyst having these metals supported on an alumina or silica carrier, or a salt or a complex of these metals.
The method according to claim 6,
The silicon resin composition of the periodic table group 8 metal is platinum.
6. The method of claim 5,
The hydrogen silicide catalyst is 0.1 to 100 ppm relative to the total weight of the resin composition.
6. The method of claim 5,
The adhesion promoter is a silicone resin composition which is a silane compound containing an alkoxy group.
6. The method of claim 5,
The adhesion improving agent is at least one of vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. Silicone resin composition.
An electronic material sealing material comprising the silicone resin composition of any one of claims 1 to 10.