Curable silicone composition, cured product of same, and method for producing same
Provided is a curable silicone composition and uses thereof. The composition has hot-melt properties, strongly adheres to difficult-to-adhere to base materials, is particularly superior in flexibility and toughness at high temperatures from room temperature to about 150° C. in cured products such as overmolding, and provides a cured product that does not easily warp or become damaged even when integrally molded with a lead frame or the like. The composition comprises: (A1) an organopolysiloxane resin having no hot-melt properties as a whole molecule and contains 20 mol % or more of a siloxane unit represented by SiO 4/2 , (A2) a liquid chain organopolysiloxane having at least two curing-reactive functional groups in the molecule, (B) a silatrane derivative or carbasilatrane derivative, (C) a curing agent, and (D) a functional inorganic filler. The content of component (D) is at least 10% by volume. The composition has hot-melt properties at a temperature of 200° C. or lower.
1 . A curable silicone composition that is solid at 25° C. and has hot-melt properties at a temperature of 200° C. or lower, comprising:
(A1) an organopolysiloxane resin component having no hot-melt properties as a whole molecule and where 20 mol % or more of the total siloxane units of the organopolysiloxane resin component is siloxane units represented by SiO 4/2 , wherein “no hot-melt properties” means that component (A1), alone, does not exhibit heat melting behavior at a temperature of 200° C. or lower, and does not have a softening point and melt viscosity;
(A2) a straight- or branched-chain organopolysiloxane, liquid at 25° C., having at least two curing-reactive functional groups containing a carbon-carbon double bond in the molecule;
(B) one or more adhesion promoters selected from silatrane derivatives and carbasilatrane derivatives;
(C) a curing agent; and
(D) functional inorganic filler;
wherein the content of component (D) is 10% or more by volume relative to the entire composition; and
wherein “has hot-melt properties” means having a softening point of 50° C. or higher, and, at 150° C., having melt viscosity of less than 1,000 Pa·s, and having flowing properties; and
wherein “softening point” means the temperature at which the deformation amount in the height direction is 1 mm or more, and the melt viscosity is measured using a Koka-type flow tester.
2 . The curable silicone composition according to claim 1 , wherein the tensile elongation rate of a cured product formed from the curable silicone composition, as measured using the method specified in JIS K 6251-2010, is 50% or more.
3 . The curable silicone composition according to claim 2 , wherein at least part or all of component (A1) is an organopolysiloxane resin mixture comprising:
(A1-1) a first organopolysiloxane resin that does not have hot-melt properties as a whole molecule, does not have a curing reactive functional group containing a carbon-carbon double bond in the molecule, and where 20 mol % or more of the total siloxane units of the first organopolysiloxane resin is siloxane units represented by SiO 4/2 , and
(A1-2) a second organopolysiloxane resin that does not have hot-melt properties as a whole molecule, has at least one curing-reactive functional group containing a carbon-carbon double bond in the molecule, and where 20 mol % or more of the total siloxane units of the second organopolysiloxane resin is siloxane units represented by SiO 4/2 .
4 . The curable silicone composition according to claim 1 , wherein component (A2) is a straight-chain diorganopolysiloxane represented by the following structural formula:
where each R 4 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, except that at least two of the R 4 in one molecule are alkenyl groups, and k is a number from 20 to 5,000.
5 . The curable silicone composition according to claim 1 , comprising:
(A1) 100 mass parts of the organopolysiloxane resin component containing the following component (A1-1) and component (A1-2) in a mass ratio of 100:0 to 25:75;
(A1-1) a first organopolysiloxane resin that does not have hot-melt properties as a whole molecule, does not have a curing reactive functional group containing a carbon-carbon double bond in the molecule, and where 20 mol % or more of the total siloxane units of the first organopolysiloxane resin is siloxane units represented by SiO 4/2 ;
(A1-2) a second organopolysiloxane resin that does not have hot-melt properties as a whole molecule, has a curing reactive functional group containing a carbon-carbon double bond in the molecule, and where 20 mol % or more of the total siloxane units of the second organopolysiloxane resin is siloxane units represented by SiO 4/2 ; and
(A2-1) 10 to 200 mass parts of a straight-chain diorganopolysiloxane represented by the following structural formula:
where each R 4 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, except that at least two of the R 4 in one molecule are alkenyl groups, and k is a number from 20 to 5,000.
6 . The curable silicone composition according to claim 1 , wherein component (A1) is a spherical resin microparticle having an average primary particle diameter of 1 to 10 μm.
7 . The curable silicone composition according to claim 1 , wherein component (B) is:
(1) a silatrane derivative represented by the following structural formula (1):
where R 1 is the same or different hydrogen atom or alkyl group, R 2 is a hydrogen atom, an alkyl group, or the same or different groups selected from alkoxysilyl group-containing organic groups represented by the general formula: —R 4 —Si(OR 5 ) x R 6 (3-x) where R 4 is a divalent organic group, R 5 is an alkyl group having 1 to 10 carbon atoms, R 6 is a substituted or unsubstituted monovalent hydrocarbon group, and x is 1, 2, or 3; however, at least one of R 2 is this alkoxysilyl group-containing organic group, and R 3 is a group selected from a substituted or unsubstituted monovalent hydrocarbon group, an alkoxy group having 1 to 10 carbon atoms, a glycidoxyalkyl group, an oxiranylalkyl group, an acyloxyalkyl group, or an alkenyl group; or
(2) one or more carbasilatrane derivatives represented by the following structural formula (2):
where R 1 is an alkyl group, an alkenyl group, or an alkoxy group, and R 2 is the same or different group selected from the collection of groups represented by the general formulae:
where R 4 is an alkylene group or alkyleneoxyalkylene group, R 5 is a monovalent hydrocarbon group, R 6 is an alkyl group, R 7 is an alkylene group, R 8 is an alkyl group, alkenyl group, or acyl group, and a is 0, 1, or 2, and
R 3 is the same or different hydrogen atom or alkyl group.
8 . The curable silicone composition according to claim 1 , wherein component (C) is one or more curing agents selected from (c1) or (c2) below, in an amount necessary to cure the composition:
(c1) an organic peroxide;
(c2) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in the molecule and a hydrosilylation reaction catalyst.
9 . The curable silicone composition according to claim 1 , wherein component (D) is selected from the group consisting of a reinforcing filler, a white pigment, a thermally conductive filler, an electrically conductive filler, a phosphor, and a mixture of at least two of these.
10 . The curable silicone composition according to claim 1 , in a granular, pellet, or sheet form.
11 . A substantially flat, 10 to 1,000 μm thick, curable silicone composition sheet formed from the curable silicone composition according to claim 1 .
12 . A film-like adhesive, comprising the curable silicone composition sheet according to claim 11 .
13 . A releasable laminate, comprising:
the curable silicone composition sheet according to claim 11 , and
a sheet-like substrate with a release surface facing the curable silicone composition sheet on one or both surfaces of the curable silicone composition sheet.
14 . A cured product obtained by curing the curable silicone composition according to claim 1 .
15 . A semiconductor device or a member for a semiconductor device, the semiconductor device or member thereof comprising the cured product according to claim 14 .
16 . A method for manufacturing the curable silicone composition according to claim 1 , wherein each component that makes up the curable silicone composition is granulated by mixing under temperature conditions not exceeding 50° C.
17 . A method of molding a cured product, comprising the following steps:
(I) heating the curable silicone composition in the form of pellets or sheets according to claim 10 to a temperature of 100° C. or higher to melt;
(II) injecting the curable silicone composition in a liquid state obtained in step (I) into a mold or distributing the curable silicone composition obtained in step (I) to a mold by clamping; and
(III) curing the curable silicone composition injected or distributed in step (II).
18 . A method for molding a cured product, comprising a coating process for overmolding and underfilling a semiconductor device using a cured product formed from the curable silicone composition according to claim 1 ; optionally, the method comprising:
covering a surface of a semiconductor wafer substrate on which a single or plurality of semiconductor devices are mounted with a cured product produced by curing the curable silicone composition; and
overmolding so that a gap between the semiconductor devices is filled with the cured product.
19 . A method for manufacturing the curable silicone composition sheet according to claim 11 , comprising the following steps:
1) Mixing raw material components of the curable silicone composition at a temperature of 50° C. or higher;
2) kneading a mixture obtained in step 1) while heating and melting;
3) Laminating a heated and melted mixture obtained in step 2) between films provided with at least one release surface; and
4) Extending a laminate body obtained in step 3) between rollers to mold a curable silicone sheet having a specific film thickness.