Curable hot-melt silicone composition, cured material thereof, and laminate containing curable hot-melt silicone composition or cured material thereof
A curable hot-melt silicone composition that is less susceptible to curing inhibition and with excellent storage stability, and a sheet or film containing the same, is provided. The composition comprises: (A) a solid organopolysiloxane resin containing a specific ratio of (A1) an organopolysiloxane resin having a curing reactive functional group that contains a carbon-carbon double bond and containing 20 mol % or more of a Q unit, and (A2) an organopolysiloxane resin not having a curing reactive functional group that contains a carbon-carbon double bond and containing 20 mol % or more of a Q unit; (B) a chain organopolysiloxane having a curing reactive functional group that contains at least two carbon-carbon double bonds; (C) an organohydrogenpolysiloxane resin having a mass loss ratio relative to pre-exposure of 10% or less after exposure to 100° C. for 1 hour under atmospheric pressure; and (D) a hydrosilylation reaction catalyst. The composition generally has hot-melt properties.
1. A curable silicone composition having hot-melt properties as a whole, comprising:
(A) 100 mass parts of an organopolysiloxane resin containing the following component (A1) and component (A2) at a mass ratio of 0:100 to 90:10;
(A1) an organopolysiloxane resin that is solid at 25° C., having a curing reactive functional group containing a carbon-carbon double bond in a molecule, containing a siloxane unit expressed by SiO 4/2 making up at least 20 mol % or more of all siloxane units, and not having hot-melt properties alone;
(A2) an organopolysiloxane resin that is solid at 25° C., not having a curing reactive functional group containing a carbon-carbon double bond in a molecule, containing a siloxane unit expressed by SiO 4/2 making up at least 20 mol % or more of all siloxane units, and not having hot-melt properties alone;
(B) 10 to 100 mass parts of a straight-chain or branched-chain organopolysiloxane that is liquid or has plasticity at 25° C., having a curing reactive functional group containing at least two carbon-carbon double bonds in a molecule;
(C) an organohydrogenpolysiloxane expressed by the following average compositional formula (1):
(R 4 3 SiO 1/2 ) a (R 5 2 SiO 2/2 ) b (R 5 SiO 3/2 ) c (SiO 4/2 ) d (1)
where R 4 independently represents a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having from 1 to 12 carbon atoms that does not contain an aliphatic unsaturated bond, R 5 independently represents an unsubstituted or substituted monovalent hydrocarbon group free from aliphatic unsaturated bonds and with 1 to 12 carbon atoms, at least two of all R 4 s represent hydrogen atoms, and a, b, c, and d represent numbers that satisfy conditions of 0.01≤a≤0.6, 0≤b, 0≤c≤0.9, 0≤d≤0.9, and (a+b+c+d)=1 and (c+d)≥0.2, and having a mass loss ratio relative to pre-exposure of 10% or less after exposure to 100° C. for 1 hour under atmospheric pressure, at an amount where the number of hydrogen atoms bonded to a silicon atom per alkenyl group bonded to a silicon atom included in the entire curable silicone composition is 0.5 to 20.0; and
(D) a sufficient amount of a hydrosilylation reaction catalyst to crosslink the curable silicone composition.
2. The curable silicone composition according to claim 1 , further comprising 1 to 5000 ppm of a curing retarder for a hydrosilylation reaction having a boiling point of 200° C. or higher under atmospheric pressure as component (E), based on the total mass of the composition.
3. The curable silicone composition according to claim 1 , wherein the component (C) is an organohydrogenpolysiloxane expressed by the following average compositional formula (2):
(HR 6 2 SiO 1/2 ) e (R 6 2 SiO 2/2 ) f (SiO 4/2 ) g (2)
where R 6 independently represents an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond with 1 to 12 carbon atoms, and e, f, and g represent numbers that satisfy conditions of 0.01≤e≤0.6, 0≤f≤0.9, 0.2≤g≤0.9, and e+f+g)=1.
4. The curable silicone composition according to claim 1 , wherein the component (C) is an organohydrogensiloxane as expressed by the following average compositional formula (3):
(HR 7 2 SiO 1/2 ) h (R 7 2 SiO 2/2 ) i (R 8 SiO 3/2 ) j (3)
where R 7 and R 8 each independently represent an unsubstituted or substituted monovalent hydrocarbon group that does not contain an aliphatic unsaturated bond with 1 to 12 carbon atoms, at least 10 mol % of all R 8 s represent aryl groups, and h, i, and j represent numbers that satisfy conditions of 0.01≤h≤0.6, 0≤i≤0.9, 0.2≤j≤0.9, and (h+i+j)=1.
5. The curable silicone composition according to claim 1 , wherein the 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′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 s in a 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 conditions of 0.10≤a≤0.60, 0≤b≤0.70, 0≤c≤0.80, 0≤d≤0.65, 0≤e≤0.05, and (c+d)>0.20 and (a+b+c+d)=1,
the 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 with an alkyl group with 1 to 10 carbon atoms; and f, g, h, i, and j represent numbers that satisfy conditions of 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
the component (B) is (B1) a straight-chain diorganopolysiloxane expressed by the following structural formula:
R 4 3 SiO(SiR 4 2 O) k SiR 4 3 4
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 represents an alkenyl group, and k represents a number from 20 to 5,000.
6. A sheet or film comprising the curable silicone composition according to claim 1 , which is melt-kneaded under vacuum within a temperature range of 50 to 150° C. and then molded into a sheet or film.
7. The curable silicone composition sheet or film according to claim 6 , wherein the thickness is between 10 and 1000 μm.
8. A sheet- or film-like adhesive, comprising the curable silicone composition sheet or film according to claim 6 .
9. A sheet- or film-like sealing agent, comprising the curable silicone composition sheet or film according to claim 6 .
10. A releasable laminate body, comprising:
the curable silicone composition sheet or film according to claim 6 ; and
a sheet- or film-like substrate adhered to one or two surfaces of the curable silicone composition sheet or film, and having a release surface facing the curable silicone composition sheet or film;
wherein the curable silicone composition sheet or film can be released from the sheet- or film-like substrate having the release surface.
11. A laminate body, comprising:
a substrate serving as an electronic component or a precursor thereof, and
a curable silicone composition layer formed with at least one surface of the curable silicone composition sheet or film according to claim 6 firmly adhered to a portion or all of a front surface of the substrate;
wherein the curable silicone composition is in an uncured state.
12. A cured product obtained by curing the curable silicone composition according to claim 1 .
13. The cured product according to claim 12 , as a member for a semiconductor device or a member for an optical semiconductor device.
14. A semiconductor device or an optical semiconductor device, comprising the cured product according to claim 12 .
15. A method of manufacturing the laminate body according to claim 11 , comprising a step of firmly adhering at least one surface of an uncured curable silicone composition sheet or film to a portion or all of a substrate serving as an electronic component or a precursor thereof, by one or more means selected from vacuum laminators, vacuum presses, and compression molding.