Curable silicone composition, cured product of same, and laminate
Provided is a hot-melt curable silicone composition with excellent hot dispensing properties and storage stability, which can be cured by triggering an external energy stimulus, and which provides excellent adhesive and mechanical properties to the cured product, and applications thereof. A curable silicone composition, including in a specific mass % range, comprises: (A) a non-hot-melt solid organopolysiloxane resin mixture; (B) a linear organopolysiloxane that is liquid at 25° C. having the same curing reactive functional group; (C) an organohydrogen polysiloxane; and (D) a hydrosilylation reaction catalyst that is inert at room temperature but is activated by an external energy stimulus. The whole composition has hot-melt properties, and the melt viscosity (flow tester measurement) at 100° C. is 50 Pa·s or less. A cured product thereof, and use in semiconductor applications and the like, is also provided. The composition is particularly suitable for use as an adhesive or sealing agent in hot dispensing applications.
1 . A curable silicone composition, comprising:
(A) 100 parts by mass of organopolysiloxane resin containing the following components (A1) and (A2) at a mass ratio of from 20:80 to 90:10, where each of components (A1) and (A2) does not have hot-melt properties and is solid at 25° C.,
(A1) an organopolysiloxane resin having a curing reactive functional group with a carbon-carbon double bond included in a molecule, and containing siloxane units expressed by SiO 4/2 making up at least 20 mol % or more of all siloxane units, and
(A2) an organopolysiloxane resin not having a curing reactive functional group with a carbon-carbon double bond included in a molecule, and containing a siloxane unit expressed by SiO 4/2 making up at least 20 mol % or more of all siloxane units;
(B) 10 to 100 parts by mass of a linear organopolysiloxane in a liquid state at 25° C., having a curing reactive functional group containing at least two carbon-carbon double bonds in a molecule;
(C) an organohydrogen polysiloxane having at least two silicon atom-bonded hydrogen atoms in a molecule, at an amount where the number of hydrogen atoms bonded to a silicon atom per one alkenyl group bonded to a silicon atom included in the entire composition is 0.5 to 20.0; and
(D) a catalytic amount of a hydrosilylation reaction catalyst, which is inert at room temperature but activated in the composition after external energy stimulus;
wherein the composition as a whole has hot-melt properties, and the melt viscosity, measured using a flow tester: outlet nozzle diameter 1 mm, pressure 2.5 MPa, at 100° C. is 50 Pa·s or less; and
wherein component (A) has a mass loss ratio of 2.0 mass % or less when exposed to 200° C. for one hour.
2 . The curable silicone composition according to claim 1 , further comprising:
(E) 1 to 5000 ppm of a hydrosilylation reaction curing retarder having a boiling point of 200° C. or higher at atmospheric pressure, based on the total mass of the composition.
3 . The curable silicone composition according to claim 1 , wherein component (D) contains one or more hydrosilylation reaction catalyst selected from:
(D1) a hydrosilylation reaction catalyst that exhibits activity in the composition due to irradiated high energy beam; and
(D2) thermoplastic resin microparticles containing a hydrosilylation reaction catalyst.
4 . The curable silicone composition according to claim 1 , wherein component (A) has a mass loss ratio of 1.0 mass % or less when exposed to 200° C. for one hour.
5 . The curable silicone composition according to claim 1 , wherein:
component (A1) is (A1-1) an organopolysiloxane resin that does not have hot-melt properties alone, expressed by the following average unit formula:
(R 1 3 SiO 1/2 ) a (R 1 2 SiO 2/2 ) b (R 1 SiO 3/2 ) c (SiO 4/2 ) d (R 2 O 1/2 ) e
where each R 1 independently represents a monovalent hydrocarbon group with 1 to 10 carbon atoms, but 1 to 12 mol % of all R 1 in one molecule represents an alkenyl group; each R 2 represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms; and a, b, c, d, and e represent numbers that satisfy 0.10≤a≤0.60, 0≤b≤0.70, 0≤c≤0.80, 0.2≤d≤0.65, 0≤e≤0.05, but (c+d)>0.20 and (a+b+c+d)=1;
component (A2) is (A2-1) an organopolysiloxane resin that does not have hot-melt properties alone, expressed by the following average unit formula:
(R 3 3 SiO 1/2 ) f (R 3 2 SiO 2/2 ) g (R 3 SiO 3/2 ) h (SiO 4/2 ) i (R 2 O 1/2 ) j
where each R 3 independently represents a monovalent hydrocarbon group with 1 to 10 carbon atoms and that does not contain a carbon-carbon double bond; R 2 represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms; and f, g, h, i, and j represent numbers that satisfy 0.35≤f≤0.55, 0≤g≤0.20, 0≤h≤0.20, 0.45≤i≤0.65, 0≤j≤0.05, and (f+g+h+i)=1; and
component (B) is (B1) a linear diorganopolysiloxane expressed by the following structural formula:
R 4 3 SiO(SiR 4 2 O) k SiR 4 3
where each R 4 independently represents a monovalent hydrocarbon group with 1 to 10 carbon atoms, but at least two of the R 4 s in one molecule represent an alkenyl group, and k represents a number from 20 to 5,000.
6 . A hot-melt adhesive or hot-melt sealing agent, comprising the curable silicone composition according to claim 1 .
7 . A cartridge, comprising: the curable silicone composition according to claim 1 , in the form of a dispensing cartridge, pail, or drum filled with the curable silicone composition.
8 . A cured product, obtained by curing the curable silicone composition according to claim 1 .
9 . An electronic component, semiconductor device, or optical semiconductor device, comprising the cured product according to claim 8 .
10 . A laminate body, comprising: a substrate and an uncured location or layer containing the curable silicone composition according to claim 1 on a portion or all of the surface of the substrate.
11 . A laminate body, comprising: two or more substrates; and having a structure in which at least a portion of respective surfaces of the two substrates are bonded via the cured product according to claim 8 .
12 . The laminate body according to claim 11 , wherein the laminate body is one or more selected from electronic components, semiconductor devices, and optical semiconductor devices.
13 . A method of manufacturing the laminate body according to claim 11 , the method comprising:
process (I): heating the curable silicone composition to 50° C. or higher by a dispenser equipped with a heating part to make the curable silicone composition flowable, and dispensing the curable silicone composition onto a portion or all of the surface of at least one substrate;
process (II): irradiating the curable silicone composition dispensed from the dispenser with a high energy beam directly or through another substrate, either at the same time as process (I) or after process (I); and,
process (III): after process (I), but before or after process (II), adhering the curable silicone composition dispensed from the dispenser to another substrate.
14 . A method of manufacturing the laminate body according to claim 11 , the method comprising:
process (I): heating the curable silicone composition to 50° C. or higher by a dispenser equipped with a heating part to make the curable silicone composition flowable, and dispensing the curable silicone composition onto a portion or all of the surface of at least one substrate;
process (II): after process (I), adhering the curable silicone composition dispensed from the dispenser to another substrate; and
process (III): heating the resulting integrated substrate and curable silicone composition to a temperature of 130° C. or higher.
15 . The method of manufacturing a laminate body according to claim 14 , wherein in process (I), a heatable slot die is connected to an outlet of the dispenser, to dispense the curable silicone composition in the form of a film or sheet of desired thickness.
16 . The method of manufacturing a laminate body according to claim 13 , wherein in process (I), a heatable slot die is connected to an outlet of the dispenser, to dispense the curable silicone composition in the form of a film or sheet of desired thickness.