Silicone laminated substrate, method of producing same, silicone resin composition for producing silicone laminated substrate, and LED device

• US 8,765,264 B2
• Filed: 09/10/2009
• Issued: 07/01/2014
• Est. Priority Date: 09/11/2008
• Status: Active Grant

• Current Assignee: Shin-Etsu Chemical Company Limited
• Original Assignee: Shin-Etsu Chemical Company Limited
• Inventors: Kashiwagi, Tsutomu, Shiobara, Toshio
• Primary Examiner(s): Fink, Brieann R
• Application Number:
  US12/557,209
• Publication Number:
  US 20100065880A1
• Time in Patent Office: 1,755 Days
• Field of Search: 428/447, 428/429, 528/15, 528/31, 525/478
• US Class Current: 428/447
• CPC Class Codes: B32B 17/04 bonded with or embedded in a plastic substance
• CPC Class Codes: B32B 27/283 comprising polysiloxanes
• CPC Class Codes: C03C 25/1095 to obtain coated fabrics
• CPC Class Codes: C08G 77/12 containing silicon bound to hydrogen C08G77/045 takes precedence
• CPC Class Codes: C08G 77/16 to hydroxyl groups
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/70 Siloxanes defined by use of the MDTQ nomenclature
• CPC Class Codes: C08K 3/22 of metals
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: C08L 83/06 containing silicon bound to oxygen-containing groups C08L83/12 takes precedence
• CPC Class Codes: C09D 183/04 Polysiloxanes
• CPC Class Codes: H01L 2224/29339 Silver [Ag] as principal constituent
• CPC Class Codes: H01L 2224/32225 the item being non-metallic, e.g. insulating substrate with or without metallisation
• CPC Class Codes: H01L 2224/45144 Gold (Au) as principal constituent
• CPC Class Codes: H01L 2224/48091 Arched
• CPC Class Codes: H01L 2224/48227 connecting the wire to a bond pad of the item
• CPC Class Codes: H01L 2224/73265 Layer and wire connectors
• CPC Class Codes: H01L 24/29 of an individual layer connector
• CPC Class Codes: H01L 24/45 of an individual wire connector
• CPC Class Codes: H01L 2924/00 : Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/00012 : Relevant to the scope of the group, the symbol of which is combined with the symbol of this group
• CPC Class Codes: H01L 2924/00014 : the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
• CPC Class Codes: H01L 2924/12041 : LED
• CPC Class Codes: H01L 2924/12042 : LASER
• CPC Class Codes: H01L 2924/181 : Encapsulation
• CPC Class Codes: Y10T 428/249921 : Web or sheet containing structurally defined element or component
• CPC Class Codes: Y10T 428/31612 : As silicone, silane or siloxane
• CPC Class Codes: Y10T 428/31663 : As siloxane, silicone or silane

Abstract

Silicone-laminated substrate, including glass cloth, and cured product of silicone resin composition—with which the glass cloth is filled and a surface of the glass cloth is coated. The silicone resin composition includes: (A) an organopolysiloxane having a resin structure of specific siloxane units, (B) an organohydrogenpolysiloxane having a resin structure of specific siloxane units, (C) a platinum group metal-based catalyst, and (D) a filler. The silicone-laminated substrate exhibits excellent mechanical properties, flexibility and workability, has minimal surface tack, and is easy to handle. The silicone-laminated substrate is produced by impregnating a glass cloth with the silicone resin composition dissolved or dispersed in a solvent, subsequently evaporating the solvent from the glass cloth, and subjecting the composition impregnated into the glass cloth to heat-curing under compression-molding conditions. Also, an LED device which includes the silicone-laminated substrate and an LED chip mounted on top of the substrate.

Claims

1. A silicone laminated substrate, comprising:

a glass cloth, and

a cured product of a silicone resin composition with which the glass cloth is filled and a surface of the glass cloth is coated,

wherein the silicone resin composition is a solid or semisolid at room temperature and comprises;

(A) an organopolysiloxane having a resin structure, consisting of R¹SiO_1.5 units, R²₂SiO units and R³_aR⁴_bSiO_(4-a-b)/2 units, wherein, R¹, R² and R³ each independently represents a hydroxyl group, methyl group, ethyl group, propyl group, cyclohexyl group or phenyl group, each R⁴ independently represents a vinyl group or allyl group, a represents 0, 1 or 2, and b represents 1 or 2, provided that a+b is 2 or 3, and including a structure in which at least a portion of the R²₂SiO units are connected in a continuous repeating sequence, and a number of units in the repeating sequence is within a range from 5 to 50,

(B) an organohydrogenpolysiloxane having a resin structure, consisting of R¹SiO_1.5 units, R²₂SiO units and R³_cH_dSiO_(4-c-d)/2 units, wherein, R¹, R² and R³ are each independently as defined above, c represents 0, 1 or 2, and d represents 1 or 2, provided that c+d is 2 or 3, and including a structure in which at least a portion of the R²₂SiO units are connected in a continuous repeating sequence, and a number of units in the repeating sequence is within a range from 5 to 50;

in sufficient amount that a molar ratio of hydrogen atoms bonded to silicon atoms within component (B) relative to a combined total of vinyl groups and allyl groups within component (A) is within a range from 0.1 to 4.0,

(C) a platinum group metal-based catalyst;

in an effective amount, and

(D) a filler in an amount of not more than 900 parts by mass per 100 parts by mass of a combined total of components (A) and (B), wherein said filler component (D) comprises

(D1) a silica in an amount of from 10 to 600 parts by mass per 100 parts by mass of a combined total of components (A) and (B) and

(D2) a white pigment selected from titanium dioxide and alumina in an amount within a range from 1 to 300 parts by mass per 100 parts by mass of a combined total of components (A) and (B),

wherein light reflectance of the silicone-laminated substrate is not less than 80% across an entire visible light range.

2. The silicone laminated substrate according to claim 1, wherein either one or both of component (A) and component (B) comprises a silanol group.

3. The silicone laminated substrate according to claim 1, wherein a coefficient of linear expansion in a direction perpendicular to the silicone laminated substrate is not more than 50 ppm/°

C. across a temperature range from −

100 to 200°

C.

4. The silicone laminated substrate according to claim 1, wherein a coefficient of linear expansion in a direction parallel to the silicone laminated substrate is not more than 10 ppm/°

C. across a temperature range from −

100 to 200°

C.

5. The silicone laminated substrate according to claim 1, which is configured for use as an LED device.

6. The silicone laminated substrate according to claim 5, wherein either one or both of component (A) and component (B) comprises a silanol group.

7. The silicone laminated substrate according to claim 5, wherein a coefficient of linear expansion in a direction perpendicular to the silicone laminated substrate is not more than 50 ppm/°

C. across a temperature range from −

100 to 200°

C.

8. The silicone laminated substrate according to claim 5, wherein a coefficient of linear expansion in a direction parallel to the silicone laminated substrate is not more than 10 ppm/°

C. across a temperature range from −

100 to 200°

C.

9. The silicone laminated substrate according to claim 5, wherein light reflectance following an IR reflow treatment at a temperature of 260°

C. for 60 seconds is not less than 80% across an entire visible light range.

10. The silicone laminated substrate according to claim 5, wherein light reflectance following irradiation with ultraviolet light having a wavelength of 365 nm and an intensity of 30 mW/cm² for 24 hours at 120°

C. is not less than 80% across an entire visible light range.

15. The silicone-laminated substrate according to claim 1, wherein component (D2) is titanium dioxide.

18. The silicone laminated substrate according to claim 1, wherein

(D1) the silica is contained in an amount of from 50 to 500 parts by mass per 100 parts by mass of a combined total of components (A) and (B), and

(D2) the white pigment is contained in an amount of from 3 to 200 parts by mass per 100 parts by mass of a combined total of components (A) and (B).

11. A method of producing a silicone laminated substrate, wherein light reflectance of the silicone laminated substrate is not less than 80% across an entire visible light range, the method comprising:

impregnating a glass cloth with a silicone resin composition that is a solid or semisolid at room temperature and is dissolved or dispersed in a solvent,

subsequently removing the solvent from the glass cloth by evaporation, and

subsequently subjecting the silicone resin composition impregnated into the glass cloth to heat curing under compression molding conditions, wherein

the silicone laminated substrate comprises;

a glass cloth, and

a cured product of the silicone resin composition with which the glass cloth is filled and a surface of the glass cloth is coated, and

the silicone resin composition comprises;

(A) an organopolysiloxane having a resin structure, consisting of R¹SiO_1.5 units, R²₂SiO units and R³_aR⁴_bSiO_(4-a-b)/2 units, wherein, R¹, R² and R³ each independently represents a hydroxyl group, methyl group, ethyl group, propyl group, cyclohexyl group or phenyl group, each R⁴ independently represents a vinyl group or allyl group, a represents 0, 1 or 2, and b represents 1 or 2, provided that a+b is 2 or 3, and

including a structure in which at least a portion of the R²₂SiO units are connected in a continuous repeating sequence, and a number of units in the repeating sequence is within a range from 5 to 50,

(B) an organohydrogenpolysiloxane having a resin structure, consisting of R¹SiO_1.5 units, R²₂SiO units and R³_cH_dSiO_(4-c-d)/2 units, wherein, R¹, R² and R³ are each independently as defined above, c represents 0, 1 or 2, and d represents 1 or 2, provided that c+d is 2 or 3, and

including a structure in which at least a portion of the R²₂SiO units are connected in a continuous repeating sequence, and a number of units in the repeating sequence is within a range from 5 to 50;

in sufficient amount that a molar ratio of hydrogen atoms bonded to silicon atoms within component (B) relative to a combined total of vinyl groups and allyl groups within component (A) is within a range from 0.1 to 4.0,

(C) a platinum group metal-based catalyst;

in an effective amount, and

(D) a filler;

in an amount of not more than 900 parts by mass per 100 parts by mass of a combined total of components (A) and (B), wherein said filler of component (D) comprises;

(D1) a silica in an amount of from 10 to 600 parts by mass per 100 parts by mass of a combined total of components (A) and (B); and

(D2) a white pigment selected from titanium dioxide and alumina in an amount within a range from 1 to 300 parts by mass per 100 parts by mass of a combined total of components (A) and (B).

12. A silicone resin composition for producing a silicone laminated substrate, the composition comprising wherein the silicone resin composition is a solid or semisolid at room temperature and comprises:

(A) an organopolysiloxane having a resin structure, consisting of R¹SiO_1.5 units, R²₂SiO units and R³_aR⁴_bSiO_(4-a-b)/2 units, wherein, R¹, R² and R³ each independently represents a hydroxyl group, methyl group, ethyl group, propyl group, cyclohexyl group or phenyl group, each R⁴ independently represents a vinyl group or allyl group, a represents 0, 1 or 2, and b represents 1 or 2, provided that a+b is 2 or 3, and including a structure in which at least a portion of the R²₂SiO units are connected in a continuous repeating sequence, and a number of units in the repeating sequence is within a range from 5 to 50,

(B) an organohydrogenpolysiloxane having a resin structure, consisting of R¹SiO_1.5 units, R²₂SiO units and R³_cH_dSiO_(4-c-d)/2 units, wherein, R¹, R² and R³ are each independently as defined above, c represents 0, 1 or 2, and d represents 1 or 2, provided that c+d is 2 or 3, and including a structure in which at least a portion of the R²₂SiO units are connected in a continuous repeating sequence, and a number of units in the repeating sequence is within a range from 5 to 50;

in sufficient amount that a molar ratio of hydrogen atoms bonded to silicon atoms within component (B) relative to a combined total of vinyl groups and allyl groups within component (A) is within a range from 0.1 to 4.0,

(C) a platinum group metal-based catalyst;

in an effective amount, and

(D) a filler;

in an amount of not more than 900 parts by mass per 100 parts by mass of a combined total of components (A) and (B), wherein said filler component (D) comprises

(D1) a silica in an amount of from 10 to 600 parts by mass per 100 parts by mass of a combined total of components (A) and (B) and

(D2) a white pigment selected from titanium dioxide and alumina in an amount within a range from 1 to 300 parts by mass per 100 parts by mass of a combined total of components (A) and (B),

wherein light reflectance of the silicone-laminated substrate is not less than 80% across an entire visible light range.

16. The silicone composition according to claim 12, wherein the silicone-laminated substrate is configured for use as an LED device.

17. The silicone composition according to claim 16, wherein component (D2) is titanium dioxide.

19. The silicone resin composition according to claim 12, wherein

(D1) the silica is contained in an amount of from 50 to 500 parts by mass per 100 parts by mass of a combined total of components (A) and (B), and

(D2) the white pigment is contained in an amount of from 3 to 200 parts by mass per 100 parts by mass of a combined total of components (A) and (B).

13. An LED device, comprising:

a silicone laminated substrate, and

an LED chip mounted on top of the substrate, wherein

the silicone laminated substrate is used for an LED device and comprises;

a glass cloth, and

a cured product of a silicone resin composition with which the glass cloth is filled and a surface of the glass cloth is coated;

the silicone resin composition is a solid or semisolid at room temperature and comprises;

(A) an organopolysiloxane having a resin structure, consisting of R¹SiO_1.5 units, R²₂SiO units and R³_aR⁴_bSiO_(4-a-b)/2 units, wherein, R¹, R² and R³ each independently represents a hydroxyl group, methyl group, ethyl group, propyl group, cyclohexyl group or phenyl group, each R⁴ independently represents a vinyl group or allyl group, a represents 0, 1 or 2, and b represents 1 or 2, provided that a+b is 2 or 3, and

including a structure in which at least a portion of the R²₂SiO units are connected in a continuous repeating sequence, and a number of units in the repeating sequence is within a range from 5 to 50,

(B) an organohydrogenpolysiloxane having a resin structure, consisting of R¹SiO_1.5 units, R²₂SiO units and R³_cH_dSiO_(4-c-d)/2 units, wherein, R¹, R² and R³ are each independently as defined above, c represents 0, 1 or 2, and d represents 1 or 2, provided that c+d is 2 or 3, and

including a structure in which at least a portion of the R²₂SiO units are connected in a continuous repeating sequence, and a number of units in the repeating sequence is within a range from 5 to 50;

in sufficient amount that a molar ratio of hydrogen atoms bonded to silicon atoms within component (B) relative to a combined total of vinyl groups and allyl groups within component (A) is within a range from 0.1 to 4.0,

(C) a platinum group metal-based catalyst;

in an effective amount, and

(D) a filler;

in an amount of not more than 900 parts by mass per 100 parts by mass of a combined total of components (A) and (B); and

the filler of component (D) comprises;

(D1) a silica in an amount of from 10 to 600 parts by mass per 100 parts by mass of a combined total of components (A) and (B) and

(D2) a white pigment selected from titanium dioxide and alumina in an amount within a range from 1 to 300 parts by mass per 100 parts by mass of a combined total of components (A) and (B),

wherein light reflectance of the silicone laminated substrate is not less than 80% across an entire visible light range.

14. The LED device according to claim 13, wherein component (D2) is titanium dioxide.

20. The LED device according to claim 13, wherein

(D1) the silica is contained in an amount of from 50 to 500 parts by mass per 100 parts by mass of a combined total of components (A) and (B), and

(D2) the white pigment is contained in an amount of from 3 to 200 parts by mass per 100 parts by mass of a combined total of components (A) and (B).