Cured product

Abstract

The present application relates to a cured product and the use thereof. The cured product has excellent processability, workability, and adhesive properties or the like, and does not cause whitening and surface stickiness, etc. The cured product has excellent transparency, moisture resistance, mechanical properties, and cracking resistance, etc. The cured product, for example, may be applied as an encapsulant or an adhesive material of a semiconductor device to provide a device having high long-term reliability.

Claims

1. A cured product, which is a reaction product of a mixture comprising an aliphatic unsaturated bond functional polyorganosiloxane and a compound having hydrogen atoms bound to silicon atoms, and which comprises an alkenyl group bound to silicon atoms, wherein a ratio (Ak/Si) of the number of moles of the alkenyl group (Ak) to the total number of moles of silicon atoms (Si) is in a range of 0.001 to 0.15, wherein the aliphatic unsaturated bond functional polyorganosiloxane shows an average unit of Formula 4:
P.sub.aQ.sub.bSiO.sub.(4-a-b)/2  [Formula 4] where, in Formula 4, P is an alkenyl group, Q is an epoxy group, or an alkoxy group, a and b are numbers such that a+b is in a range of 1 to 2.2, and a/(a+b) is in a range of 0.001 to 0.15.

2. The cured product of claim 1, wherein the Ak/Si ratio is in a range of 0.001 to 0.1.

3. The cured product of claim 1, comprising a unit of the following Formula 1, wherein a ratio (C/Si) of the number of moles of carbon atoms (C) which are present in A of the following Formula 1 to the total number of moles of silicon atoms (Si) is in a range of 0.15 to 0.55:
(R.sub.2SiO.sub.1/2A.sub.1/2)  [Formula 1] where, in Formula 1, each R is independently hydrogen, an epoxy group, an alkoxy group, or a monovalent hydrocarbon group, and A is an alkylene group having 1 to 4 carbon atoms.

4. The cured product of claim 3, wherein the ratio (C/Si) of the number of moles of carbon atoms (C) which are present in A of Formula 1 to the total number of moles of silicon atoms (Si) is in a range of 0.15 to 0.5.

5. The cured product of claim 3, wherein the ratio (C/Si) of the number of moles of carbon atoms (C) which are present in A of Formula 1 to the total number of moles of silicon atoms (Si) is in a range of 0.15 to 0.45.

6. The cured product of claim 1, comprising an aryl group bound to the silicon atoms, wherein a ratio (Ar/Si) of the number of moles of the aryl group (Ar) to the total number of moles of silicon atoms (Si) is in a range of 0.2 to 1.2.

7. The cured product of claim 1, comprising a trifunctional siloxane unit bound to an aryl group, wherein a ratio (T/Si) of the number of moles of the trifunctional siloxane unit (T) to the total number of moles of silicon atoms (Si) is in a range of 0.19 to 0.6.

8. The cured product of claim 1, comprising a difunctional siloxane unit, wherein a ratio (D/Si) of the number of moles of the difunctional siloxane unit (D) to the total number of moles of silicon atoms (Si) is 0.6 or less.

9. The cured product of claim 1, wherein the compound having the hydrogen atoms bound to the silicon atoms shows an average unit of the following Formula 5:
H.sub.cQ.sub.dSiO.sub.(4-c-d)/2  [Formula 5] where, in Formula 5, Q is an epoxy group, or a monovalent hydrocarbon group, c and d are numbers such that c+d is in a range of 1 to 2.8, and c/(c+d) is in a range of 0.001 to 0. 34.

10. The cured product of claim 1, wherein the compound having the hydrogen atoms bound to the silicon atoms is a compound of the following Formula 6: ##STR00002## where, in Formula 6, each R is independently hydrogen, an epoxy group, or a monovalent hydrocarbon group, at least one R is an aryl group, and n is a number in a range of 1 to 2.

11. The cured product of claim 1, wherein a ratio (H/Ak) of the number of moles of the hydrogen atoms of the compound having the hydrogen atoms bound to the silicon atoms (H) to the number of moles of an aliphatic unsaturated bond of the aliphatic unsaturated bond functional polyorganosiloxane (Ak) is in a range of 1.05 to 1.3 in a mixture.

12. A semiconductor device encapsulated by an encapsulant comprising the cured product of claim 1.

13. An optical semiconductor device encapsulated by an encapsulant comprising the cured product of claim 1.

14. A liquid crystal display device comprising the optical semiconductor device of claim 13.

15. A lighting device comprising the optical semiconductor device of claim 13.

16. A light-emitting diode (LED) encapsulated by an encapsulant comprising the cured product of claim 1.

17. The light-emitting diode of claim 16, wherein after the light-emitting diode is operated for 1,000 hours with a current of 50 mA while being maintained at 85° C., a brightness decreasing rate is 7% or less.

Description

EMBODIMENTS

(1) Hereinafter, the mixture will be described in detail with reference to examples and comparative examples. However, the scope of the mixture is not limited by the following examples.

(2) Hereinafter, the abbreviation “Vi” refers to a vinyl group, the abbreviation “Ph” refers to a phenyl group, the abbreviation “Me” refers to a methyl group, and the abbreviation “Ep” refers to a 3-glycidoxypropyl group.

(3) Physical properties of cured products prepared in the examples and comparative examples were measured by the following methods.

(4) 1. Mole Fraction Evaluation Method

(5) Silicon atoms connected by an ethylene group which is present in a cured product, a ratio (C/Si) of the number of moles of carbon atoms (C) which are present in the ethylene group to the total number of moles of silicon atoms (Si), or the like were measured according to a well-known .sup.29Si NMR method. A reference compound used upon a measurement by .sup.29Si NMR was dilute tetramethylsilane (TMS) dissolved in CDCl.sub.3, and a chemical shift thereof was measured.

(6) 2. Long-term Reliability at High Temperature

(7) Properties of a device were evaluated using an LED package prepared by a poly phthal amide (PPA) or a polycyclohexyl phthal amide (PCT). Specifically, a surface-mount type LED was prepared by dispensing a mixture prepared in a PPA or PCT cup, and curing it under conditions represented in the examples or comparative examples. Subsequently, after the prepared LED operated for 1,000 hours with current of 50 mA while being maintained at 85° C., a brightness decreasing rate after operation with respect to initial brightness before the operation was measured, and thereby reliability was evaluated based on the following standard.

(8) [Evaluation Standard]

(9) O: brightness decreasing rate was 7% or less

(10) X: brightness decreasing rate was more than 7%

(11) 3. Heat and Shock Durability

(12) After 1 cycle was defined as maintaining the LED package at −40° C. for 15 minutes and then maintaining the LED package at 100° C. for 15 minutes again, and 200 cycles were repeated, the number of turned-off packages with respect to 20 of total evaluated packages was evaluated, and thereby heat and shock durability was evaluated.

Example 1

(13) 120.0 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the following Formula A, and having a weight-average molecular weight of about 2,300, and 36.6 g of a compound of the following Formula B were mixed, a catalyst of platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in which a content of Pt (0) was 2 ppm was also mixed therein, and thereby a mixture was prepared. Subsequently, the prepared mixture was maintained at 140° C. for 1 hour, and thereby a cured product was prepared. Curing of the cured product was performed after dispensing the mixture in the PPA cup. As the analysis result of the prepared cured product, it was determined that the cured product included a vinyl group bound to silicon atoms, and a ratio (V/Si) of the number of moles of the vinyl group (V) to the total number of moles of silicon atoms (Si) was about 0.01. Further, as the analysis result of the prepared cured product, the cured product was determined to include silicon atoms connected by an ethylene group, and a ratio (C/Si) of the number of moles of carbon atoms (C) which were present in the ethylene group to the total number of moles of silicon atoms (Si) was about 0.31. Further, a ratio (Ar/Si) of the total number of moles of aryl groups (Ar) which were present in the cured product to the total number of moles of silicon atoms (Si) was about 0.7, a ratio (T/Si) of the total number of moles of T units (T) in the cured product to the total number of moles of silicon atoms (Si) was about 0.42, and a ratio (D/Si) of the total number of moles of D units (D) in the cured product to the total number of moles of silicon atoms (Si) was about 0.24.
(ViMe.sub.2SiO.sub.1/2).sub.0.21(Me.sub.2SiO.sub.2/2).sub.0.14(Ph.sub.2SiO.sub.2/2).sub.0.08(PhSiO.sub.3/2).sub.0.58  [Formula A]
(HMe.sub.2SiO.sub.1/2).sub.2(Ph.sub.2SiO.sub.2/2)  [Formula B]

Example 2

(14) 108.2 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the following Formula C, and having a weight-average molecular weight of about 2,150, and 80.5 g of a compound of the following Formula B were mixed, a catalyst of platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in which a content of Pt (0) was 2 ppm was also mixed therein, and thereby a mixture was prepared. Subsequently, the prepared mixture was dispensed in a PCT cup, was maintained at 140° C. for 1 hour, and thereby a cured product was prepared. In the above description, a PCT cup prebaked at 160° C. for about 30 minutes before dispensing the mixture was used as the PCT cup in which the mixture was dispensed. As the analysis result of the prepared cured product, it was determined that the cured product included a vinyl group bound to silicon atoms, and a ratio (V/Si) of the number of moles of the vinyl group (V) to the total number of moles of silicon atoms (Si) was about 0.05. The cured product included silicon atoms connected by an ethylene group, and a ratio (C/Si) of the number of moles of carbon atoms (C) which were present in the ethylene group to the total number of moles of silicon atoms (Si) was about 0.54. Further, a ratio (Ar/Si) of the total number of moles of aryl groups (Ar) which were present in the cured product to the total number of moles of silicon atoms (Si) was about 0.50, a ratio (T/Si) of the total number of moles of T units (T) in the cured product to the total number of moles of silicon atoms (Si) was about 0.21, and a ratio (D/Si) of the total number of moles of D units (D) to the total number of moles of silicon atoms (Si) was about 0.19.
(ViMe.sub.2SiO.sub.1/2).sub.0.55(Me.sub.2SiO.sub.2/2).sub.0.06(Ph.sub.2SiO.sub.2/2).sub.0.03(PhSiO.sub.3/3).sub.0.36  [Formula C]

Example 3

(15) 104.0 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the following Formula D, and having a weight-average molecular weight of about 2,300, and 79.8 g of a compound of the following Formula B were mixed, a catalyst of platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in which a content of Pt (0) was 2 ppm was also mixed therein, and thereby a mixture was prepared. Subsequently, the prepared mixture was dispensed in a PCT cup, was maintained at 140° C. for 1 hour, and thereby a cured product was prepared. In the above description, a PCT cup prebaked at 160° C. for about 30 minutes before dispensing the mixture was used as the PCT cup in which the mixture was dispensed. As the analysis result of the prepared cured product, it was determined that the cured product included a vinyl group bound to silicon atoms, and a ratio (V/Si) of the number of moles of the vinyl group (V) to the total number of moles of silicon atoms (Si) was about 0.1. The cured product included silicon atoms connected by an ethylene group, and a ratio (C/Si) of the number of moles of carbon atoms (C) which were present in the ethylene group to the total number of moles of silicon atoms (Si) was about 0.52. Further, a ratio (Ar/Si) of the number of moles of total aryl groups (Ar) which were present in the cured product to the total number of moles of silicon atoms (Si) was about 0.45, a ratio (T/Si) of the total number of moles of T units (T) in the cured product to the total number of moles of silicon atoms (Si) was about 0.19, and a ratio (D/Si) of the total number of moles of D units (D) to the total number of moles of silicon atoms (Si) was about 0.17.
(ViMe.sub.2SiO.sub.1/2).sub.0.60(Me.sub.2SiO.sub.2/2).sub.0.04(Ph.sub.2SiO.sub.2/2).sub.0.01(PhSiO.sub.3/2).sub.0.32(SiO.sub.4/2).sub.0.03  [Formula D]

Comparative Example 1

(16) 108.2 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the following Formula F, and having a weight-average molecular weight of about 2,150, and 100.6 g of a compound of the following Formula B were mixed, a catalyst of platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in which a content of Pt (0) was 2 ppm was also mixed therein, and thereby a mixture was prepared. Subsequently, the prepared mixture was maintained at 140° C. for 1 hour, and thereby a cured product was prepared. As the analysis result of the prepared cured product, it was determined that the cured product included hydrogen atoms bound to silicon atoms without including a vinyl group bound to silicon atoms, and a ratio (H/Si) of the number of moles of the hydrogen atoms (H) to the total number of moles of silicon atoms (Si) was about 0.03. The cured product included silicon atoms connected by an ethylene group, and a ratio (C/Si) of the number of moles of carbon atoms (C) which were present in the ethylene group to the total number of moles of silicon atoms (Si) was about 0.57. Further, a ratio (Ar/Si) of the total number of moles of aryl groups (Ar) which were present in the cured product to the total number of moles of silicon atoms (Si) was about 0.54, a ratio (T/Si) of the total number of moles of T units (T) in the cured product to the total number of moles of silicon atoms (Si) was about 0.19, and a ratio (D/Si) of the total number of moles of D units (D) to the total number of moles of silicon atoms (Si) was about 0.21.
(ViMe.sub.2SiO.sub.1/2).sub.0.55(Me.sub.2SiO.sub.2/2).sub.0.06(Ph.sub.2SiO.sub.2/2).sub.0.03(PhSiO.sub.3/2).sub.0.36  [Formula F]

Comparative Example 2

(17) 104.0 g of an aliphatic unsaturated bond functional polyorganosiloxane having an average unit of the following Formula G, and having a weight-average molecular weight of about 2,400, and 109.8 g of a compound of the following Formula B were mixed, a catalyst of platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane in which a content of Pt (0) was 2 ppm was also mixed therein, and thereby a mixture was prepared. Subsequently, the prepared mixture was maintained at 140° C. for 1 hour, and thereby a cured product was prepared. As the analysis result of the prepared cured product, it was determined that the cured product included hydrogen atoms bound to silicon atoms without including a vinyl group bound to silicon atoms, and a ratio (H/Si) of the number of moles of the hydrogen atoms (H) to the total number of moles of silicon atoms (Si) was about 0.04. The cured product included silicon atoms connected by an ethylene group, and a ratio (C/Si) of the number of moles of carbon atoms (C) which were present in the ethylene group to the total number of moles of silicon atoms (Si) was about 0.60. Further, a ratio (Ar/Si) of the total number of moles of aryl groups (Ar) which were present in the cured product to the total number of moles of silicon atoms (Si) was about 0.5, a ratio (T/Si) of the total number of moles of T units (T) in the cured product to the total number of moles of silicon atoms (Si) was about 0.16, and a ratio (D/Si) of the total number of moles of D units (D) to the total number of moles of silicon atoms (Si) was about 0.19.
(ViMe.sub.2SiO.sub.1/2).sub.0.60(Me.sub.2SiO.sub.2/2).sub.0.04(Ph.sub.2SiO.sub.2/2).sub.0.01(PhSiO.sub.3/2).sub.0.32(SiO.sub.4/2).sub.0.03  [Formula G]

Comparative Example 3

(18) The cured product was prepared in the same manner as in Example 3 except that a PCT cup which was not prebaked was used as the PCT cup in which the mixture was dispensed. The prepared cured product included silicon atoms connected by an ethylene group, and a ratio (C/Si) of the number of moles of carbon atoms (C) which were present in the ethylene group to the total number of moles of silicon atoms (Si) was about 0.08. Further, a ratio (Ar/Si) of the total number of moles of aryl groups (Ar) which were present in the cured product to the total number of moles of silicon atoms (Si) was about 0.45, a ratio (T/Si) of the total number of moles of T units (T) in the cured product to the total number of moles of silicon atoms (Si) was about 0.19, a ratio (D/Si) of the total number of moles of D units (D) to the total number of moles of silicon atoms (Si) was about 0.17, and a ratio (V/Si) of the total number of moles of vinyl groups (V) in the cured product to the total number of moles of silicon atoms (Si) was about 0.

Comparative Example 4

(19) The cured product was prepared in the same manner as in Example 3 except that a mixture mixed with a catalyst (platinum (0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane) in which a content of Pt (0) was 0.2 ppm was used. The prepared cured product included silicon atoms connected by an ethylene group, and a ratio (C/Si) of the number of moles of carbon atoms (C) which were present in the ethylene group to the total number of moles of silicon atoms (Si) was about 0.13. Further, a ratio (Ar/Si) of the total number of moles of aryl groups (Ar) which were present in the cured product to the total number of moles of silicon atoms (Si) was about 0.45, a ratio (T/Si) of the total number of moles of T units (T) in the cured product to the total number of moles of silicon atoms (Si) was about 0.19, a ratio (D/Si) of the total number of moles of D units (D) to the total number of moles of silicon atoms (Si) was about 0.17, and a ratio (V/Si) of the total number of moles of vinyl groups (V) in the cured product to the total number of moles of silicon atoms (Si) was about 0.

(20) The measurement results of physical properties of the cured products in the examples and comparative examples were summarized and represented in the following Table 1.

(21) TABLE-US-00001 TABLE 1 Reliability at high temperature Heat and shock durability Example 1 ◯ 0/20 Example 2 ◯ 0/20 Example 3 ◯ 2/20 Comparative X 3/20 Example 1 Comparative X 5/20 Example 2 Comparative X 20/20  Example 3 Comparative X 20/20  Example 4