CN121620566A - Curable silicone compositions, adhesives, and optoelectronic semiconductor devices - Google Patents

Curable silicone compositions, adhesives, and optoelectronic semiconductor devices

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Publication number
CN121620566A
CN121620566A CN202480050797.8A CN202480050797A CN121620566A CN 121620566 A CN121620566 A CN 121620566A CN 202480050797 A CN202480050797 A CN 202480050797A CN 121620566 A CN121620566 A CN 121620566A
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group
curable silicone
component
silicone composition
groups
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崔鑫楠
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Duropco Materials Co ltd
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Duropco Materials Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—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
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on 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; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

A curable silicone composition comprising (A) an alkenyl-containing organopolysiloxane having at least two alkenyl groups per molecule, (B) an organohydrogen polysiloxane having at least two hydrogen atoms bonded to silicon atoms per molecule, (C) a thermally conductive filler in an amount of 5 mass% or more relative to the total mass of the composition, (D) a cerium-containing organopolysiloxane, and (E) a curing catalyst.

Description

Curable silicone composition, adhesive, and optical semiconductor device
Technical Field
The present invention relates to a curable silicone composition, and more particularly, to a curable silicone composition suitable for an adhesive for optical semiconductors. The present invention also relates to an optical semiconductor device including an adhesive composed of a cured product of such a curable silicone composition.
The present application claims priority based on japanese patent application No. 2023-127893 filed in japan at 8/4 of 2023, and the contents thereof are incorporated herein.
Background
Curable silicone compositions are used in a wide variety of industrial fields because they cure to form cured products having excellent heat resistance, cold resistance, electrical insulation, weather resistance, water repellency, and transparency. In particular, the cured product is less likely to be discolored and less deteriorated in physical properties such as durability as compared with other organic materials, and therefore is widely used as an optical material, particularly as a silicone sealing material used in an optical semiconductor device such as a Light Emitting Diode (LED).
In order to improve the heat resistance and/or light resistance of the cured product of such a curable silicone composition, it is known to add a cerium-containing organopolysiloxane.
For example, patent document 1 discloses a curable silicone composition comprising at least (a) a linear organopolysiloxane having at least two alkenyl groups per molecule, (B) an average unit formula ：(R1SiO3/2)a(R1 2SiO2/2)b(R1 3SiO1/2)c(SiO4/2)d(XO1/2)e（ wherein R 1 is independently an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or a group in which part or all of hydrogen atoms of these groups are substituted with halogen atoms, wherein at least two R 1 are the alkenyl groups, X is a hydrogen atom or an alkyl group, a is a number of 0 to 0.3, B is 0 or a positive number, c is a positive number, e is a number of 0 to 0.4, a+b+c+d=1, c/d is a number of 0 to 10, and B/d is a number of 0 to 0.5. ) An organopolysiloxane { component A) and component (B) in an amount of 1/99 to 99/1 by mass, (C) an organopolysiloxane { 1 mole relative to the total amount of alkenyl groups in component (A) and component (B) having at least two silicon-bonded hydrogen atoms in one molecule, in an amount of 0.1 to 10 moles relative to the total amount of alkenyl groups in component (A), and (D) a cerium-containing organopolysiloxane { (D) in an amount of 20 to 2,000 ppm by mass relative to the total mass of the composition, and (E) a catalytic amount of a catalyst for hydrosilylation reaction.
Patent document 2 describes a curable white silicone composition containing (a) an organopolysiloxane having at least two alkenyl groups in one molecule, (B) a cerium-containing organopolysiloxane, (C) a white pigment, and (D) a curing catalyst.
However, when a large amount of a thermally conductive filler such as alumina is contained in the conventional curable silicone composition, there are problems that the thermal stability is lowered and the strength after aging at high temperature is lowered.
Prior art literature
Patent literature
Patent document 1 Japanese patent application laid-open No. 2016-513165
Patent document 2 Japanese patent laid-open No. 2021-88678
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a curable silicone composition that can form a cured product that exhibits excellent thermal stability even when a large amount of thermally conductive filler is contained.
Another object of the present invention is to provide a sealing material comprising the curable silicone composition of the present invention. Another object of the present invention is to provide an optical semiconductor device sealed with the sealing material of the present invention.
Means for solving the problems
As a result of intensive studies to solve the above-mentioned problems, the present inventors have unexpectedly found that a curable silicone composition comprising a cerium-containing organopolysiloxane can form a cured product exhibiting excellent thermal stability even in the case of containing a large amount of a thermally conductive filler, and have completed the present invention.
Thus, the present invention relates to a curable silicone composition comprising:
(A) An alkenyl-containing organopolysiloxane having at least two alkenyl groups per molecule;
(B) Organohydrogen polysiloxanes having at least two hydrogen atoms bonded to silicon atoms per molecule;
(C) A thermally conductive filler in an amount of 5 mass% or more relative to the total mass of the composition;
(D) Cerium-containing organopolysiloxane, and
(E) A curing catalyst.
The alkenyl-containing organopolysiloxane of (a) preferably comprises an MQ resin.
The thermally conductive filler (C) is preferably a metal oxide.
The (C) thermally conductive filler preferably contains two thermally conductive fillers having different average particle diameters.
The cerium atom of the (D) cerium-containing organopolysiloxane is preferably in an amount of 1 to 100 ppm relative to the total mass of all organopolysiloxane components of the present composition.
The present invention also relates to an adhesive comprising the curable silicone composition of the present invention.
The present invention also relates to an optical semiconductor device comprising the adhesive of the present invention.
Effects of the invention
According to the curable silicone composition of the present invention, a cured product that can exhibit excellent thermal stability can be formed even when a prescribed amount of thermally conductive filler is contained.
Detailed Description
[ Curable Silicone composition ]
The curable silicone composition of the present invention comprises at least:
(A) An alkenyl-containing organopolysiloxane having at least two alkenyl groups per molecule;
(B) Organohydrogen polysiloxanes having at least two hydrogen atoms bonded to silicon atoms per molecule;
(C) A thermally conductive filler in an amount of 5 mass% or more relative to the total mass of the composition;
(D) Cerium-containing organopolysiloxane, and
(E) A curing catalyst.
The components of the curable silicone composition of the present invention will be described in detail below.
(A) Alkenyl-containing organopolysiloxanes having at least two alkenyl groups per molecule
(A) The component (a) is a curable organopolysiloxane having at least two alkenyl groups in one molecule. The curable silicone composition of the present invention may contain one kind of (a) alkenyl group-containing organopolysiloxane or two or more kinds of (a) alkenyl group-containing organopolysiloxanes.
Examples of the molecular structure of the component (a) include linear, partially branched linear, branched, resinous, cyclic and three-dimensional network structures. (A) The component may be an organopolysiloxane having these molecular structures or a mixture of two or more organopolysiloxanes having these molecular structures. In the present specification, resin-like means having a branched or three-dimensional network structure in a molecular structure.
The curable silicone composition of the present invention preferably contains a resinous alkenyl group-containing organopolysiloxane as the component (a). The curable silicone composition of the present invention preferably contains an organopolysiloxane containing a linear alkenyl group as the component (a). The curable silicone composition of the present invention preferably contains both a resinous alkenyl group-containing organopolysiloxane and a linear alkenyl group-containing organopolysiloxane as component (a).
Examples of the alkenyl group contained in the component (a) include alkenyl groups having 2 to 12 carbon atoms such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, and the like, and vinyl groups are preferable.
Examples of the group bonded to a silicon atom other than an alkenyl group contained in the component (A) include a monovalent hydrocarbon group substituted or unsubstituted with a halogen atom other than an alkenyl group, for example, a group in which a part or all of hydrogen atoms of these groups are substituted with halogen atoms such as fluorine atoms, chlorine atoms and bromine atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl, an alkyl group having 1 to 12 carbon atoms, such as phenyl, tolyl, xylyl and naphthyl, an aryl group having 6 to 20 carbon atoms, such as benzyl, phenethyl and phenylpropyl, and an aralkyl group having 7 to 20 carbon atoms. Further, the silicon atom in the component (a) may have a small amount of an alkoxy group such as a hydroxyl group, a methoxy group, or an ethoxy group, as far as the object of the present invention is not impaired. (A) The group bonded to a silicon atom other than the alkenyl group of the component is preferably selected from alkyl groups having 1 to 6 carbon atoms, particularly methyl groups.
In one embodiment of the present invention, the component (A) may contain a resinous alkenyl-containing organopolysiloxane as the component (A-1). The resinous alkenyl-containing organopolysiloxane of (A-1) may preferably be represented by the following average unit formula (I-a):
Average unit type （I-a）：(R1 3SiO1/2)a(R1 2SiO2/2)b(R1SiO3/2)c(SiO4/2)d(XO1/2)e
(In the formula (I-a), R 1 is the same or different halogen-substituted or unsubstituted monovalent hydrocarbon groups, wherein, in one molecule, at least two R 1 are alkenyl groups, 0≤a <1, 0≤b <1, 0≤c < 0.9, 0≤d < 0.5, 0≤e < 0.4, a+b+c+d=1.0, and c+d > 0.e represents the number of (XO) groups when the total number of silicon atoms is set to 1 (ratio of the number of XO groups to the total number of silicon atoms)).
Examples of the monovalent halogen-substituted or unsubstituted hydrocarbon group represented by R 1 in the above formula (I-a) include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl, aryl groups having 6 to 20 carbon atoms such as phenyl, tolyl, xylyl, and naphthyl, aralkyl groups having 7 to 20 carbon atoms such as benzyl, phenethyl, and phenylpropyl, alkenyl groups having 2 to 12 carbon atoms such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and dodecenyl, and groups in which some or all of hydrogen atoms are substituted with halogen atoms such as fluorine atoms, chlorine atoms, and bromine atoms. R 1 may be a small amount of an alkoxy group such as a hydroxyl group, a methoxy group, or an ethoxy group, as long as the object of the present invention is not impaired. R 1 is preferably selected from alkyl groups having 1 to 6 carbon atoms, particularly methyl groups, alkenyl groups having 2 to 6 carbon atoms, particularly vinyl groups.
X in the above formula (I-a) is a hydrogen atom or an alkyl group. The alkyl group of X is preferably an alkyl group having 1 to 3 carbon atoms, and specifically, methyl, ethyl, and propyl are exemplified. X is preferably a hydrogen atom.
In the above formula (I-a), a is preferably in the range of 0.1≤a≤0.8, more preferably in the range of 0.2≤a≤0.7, and still more preferably in the range of 0.3≤a≤0.6. In the above formula (I-a), b is preferably in the range of 0≤b≤0.5, more preferably in the range of 0≤b≤0.3, and particularly in the range of 0≤b≤0.1. In the above formula (I-a), c is preferably in the range of 0≤c <05, more preferably in the range of 0≤c≤0.3, and particularly in the range of 0≤c≤0.1. In the above formula (I-a), d is preferably in the range of 0.1≤d≤0.8, more preferably in the range of 0.2≤d≤0.7, and still more preferably in the range of 0.3≤d≤0.6. In the above formula (I-a), e is preferably in the range of 0≤e≤0.15, more preferably in the range of 0≤e≤0.1, and particularly in the range of 0≤e≤0.05.
In a preferred embodiment of the present invention, the resinous alkenyl-containing organopolysiloxane of component (A-1) structurally comprises siloxane units (Q units) represented by SiO 4/2. The resinous alkenyl-containing organopolysiloxane of the component (a-1) may or may not contain in its structure a siloxane unit (D unit) represented by SiO 2/2, but preferably does not contain it. The resinous alkenyl-containing organopolysiloxane of component (a-1) may or may not contain in its structure a siloxane unit (T unit) represented by SiO 3/2, but preferably does not contain it.
In a preferred embodiment of the present invention, the resinous alkenyl-containing organopolysiloxane of component (A-1) contains alkenyl groups at the molecular terminals. The resinous organopolysiloxane of the component (a-1) preferably has an alkenyl group in the siloxane unit (M unit) represented by SiO 1/2, and may or may not contain an alkenyl group in the molecular chain side chains (i.e., the siloxane unit (D unit) represented by SiO 2/2 and the siloxane unit (T unit) represented by SiO 3/2, but preferably does not contain an alkenyl group.
In a preferred embodiment of the present invention, the resinous alkenyl-containing organopolysiloxane of component (A-1) comprises or consists solely of an MQ resin. The MQ resin is an organopolysiloxane containing only a siloxane unit (M unit) represented by SiO 1/2 and a siloxane unit (Q unit) represented by SiO 4/2. The MQ resin of the component (A-1) can be preferably represented by the following average unit formula (I-b).
Average unit formula (I-b) (R 1 3SiO1/2)s(SiO4/2)t(XO1/2)u
Wherein R 1 is the same or different halogen-substituted or unsubstituted monovalent hydrocarbon group, wherein, in one molecule, at least two R 1 are alkenyl groups, 0 < s < 1, 0 < t < 1, 0≤u < 0.4, and s+t=1.0, u represents the number of (XO) groups (ratio of the number of (XO) groups to the number of total silicon atoms) when the number of total silicon atoms is set to 1.
R 1 in formula (II-b) is as described in formula (II-a).
In the formula (II-b), s is preferably in the range of 0.2≤s≤0.8, more preferably in the range of 0.3≤s≤0.7, and still more preferably in the range of 0.4≤s≤0.6. In the above formula (II-b), t is preferably in the range of 0.2≤t≤0.8, more preferably in the range of 0.3≤t≤0.7, and particularly in the range of 0.3≤t≤0.7. In the above formula (II-b), u is preferably in the range of 0≤u≤0.3, more preferably in the range of 0≤u≤0.2, and particularly in the range of 0≤u≤0.1.
The content of alkenyl groups in the total of the organic groups bonded to silicon atoms of the resinous alkenyl-containing organopolysiloxane of the component (a-1) is not particularly limited, and may be, for example, 3 mol% or more, preferably 5 mol% or more, more preferably 10 mol% or more, and may be 40 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less of the total of the organic groups bonded to silicon atoms. The alkenyl group content can be determined by, for example, analysis methods such as Fourier transform infrared spectroscopy (FT-IR: fourier Transform Infrared Spectrometer) and nuclear magnetic resonance (NMR: nuclear Magnetic Resonance), or the following titration methods.
A method of quantifying the amount of alkenyl groups in each component by titration will be described. The alkenyl content of the organopolysiloxane component can be quantified with high accuracy by the generally known titration method known as the Welch method. The principle is as follows. First, as shown in formula (1), an alkenyl group in an organopolysiloxane raw material is subjected to an addition reaction with iodine monochloride. Then, by the reaction represented by the formula (2), an excessive amount of iodine monochloride is reacted with potassium iodide to free iodine. Then, the free iodine was titrated with a sodium thiosulfate solution.
Formula (1) CH 2 = CH- + 2ICl → CH2 I-CHCl- + ICl (excess)
ICl+KI→I 2 +KCl of formula (2)
The amount of alkenyl groups in the composition can be quantified based on the difference between the amount of sodium thiosulfate required for titration and the amount of the blank solution that is otherwise prepared.
The MQ resin of component (a-1) may be solid at ambient temperature (25 ℃).
When the component (a) contains one or more of the (a-1) resinous organopolysiloxanes, the content thereof is not particularly limited, but is preferably 1% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more, based on the total mass of the curable silicone composition of the present invention. The content of the component (a-1) is preferably 70 mass% or less, more preferably 60 mass% or less, and still more preferably 50 mass% or less, based on the total mass of the curable silicone composition. In this specification, the upper limit and the lower limit of the numerical range may be arbitrarily combined to set the numerical range.
(A) The component (A-2) may contain a linear alkenyl group-containing organopolysiloxane. The linear alkenyl group-containing organopolysiloxane of the component (A-2) may be preferably represented by the following average structural formula (I-c):
Average structural formula (I-c) R 1 3SiO(R1 2SiO2/2)mSiR2 3
(In the formula (I-c), R 1 is the same or different halogen substituted or unsubstituted monovalent hydrocarbon groups, wherein at least two R 1 are alkenyl groups in one molecule, and m is 1-500).
In the above formula (I-c), a halogen-substituted or unsubstituted monovalent hydrocarbon group of R 1 can be used as the same group as in the above formula (I-a).
In the above formula (I-c), m is preferably 2 to 300, more preferably 5 to 200, still more preferably 10 to 100, particularly preferably 15 to 50.
Examples of the component (A-2) include dimethylpolysiloxane having both molecular chain ends terminated with dimethylvinylsiloxy groups, dimethylpolysiloxane having both molecular chain ends terminated with diphenylvinylsiloxy groups, dimethylsiloxane-methylphenylsiloxane copolymer having both molecular chain ends terminated with dimethylvinylsiloxy groups, dimethylsiloxane-diphenylsiloxane copolymer having both molecular chain ends terminated with dimethylvinylsiloxy groups, dimethylsiloxane-methylphenylsiloxane copolymer having both molecular chain ends terminated with diphenylvinylsiloxy groups, dimethylsiloxane-methylvinylsiloxane copolymer having both molecular chain ends terminated with dimethylvinylsiloxy groups, dimethylsiloxane-methylvinylsiloxane copolymer having both molecular chain ends terminated with dimethylvinylsiloxy groups, dimethylsiloxane-diphenylsiloxane-methylvinylsiloxane copolymer having both molecular chain ends terminated with dimethylvinylsiloxy groups, methylvinylpolysiloxane having both molecular chain ends terminated with trimethylsiloxy groups, methylvinylsiloxane-methylsiloxane copolymer having both molecular chain ends terminated with trimethylsiloxy groups, and dimethylsiloxane-dimethylsiloxane copolymer having both molecular chain ends terminated with trimethylvinylsiloxy groups.
In a preferred embodiment of the present invention, the linear alkenyl group-containing organopolysiloxane of the component (a-2) may be a linear organopolysiloxane having alkenyl groups at both molecular chain ends and having alkenyl groups at both molecular chain ends. The linear organopolysiloxane of the component (a-2) may or may not contain alkenyl groups in the side chains of the molecular chain (i.e., D units), but is preferably free.
The content of the alkenyl groups contained in the linear organopolysiloxane of the component (a-2) (mole% of alkenyl groups in all the organic groups bonded to silicon atoms of the linear organopolysiloxane) may be designed as required, and may be generally 1 mole% or more, preferably 2 mole% or more, more preferably 3 mole% or more, and may be 20 mole% or less, preferably 15 mole% or less, more preferably 10 mole% or less. The alkenyl group content can be determined by analysis using, for example, fourier transform infrared spectroscopy (FT-IR), nuclear Magnetic Resonance (NMR), or the titration method described above.
When the component (a) contains the linear organopolysiloxane (a-2), the content thereof is not particularly limited, but is preferably 1 mass% or more, more preferably 2 mass% or more, and still more preferably 3 mass% or more based on the total mass of the curable silicone composition of the present invention. The content of the component (a-2) is preferably 50 mass% or less, more preferably 40 mass% or less, and still more preferably 30 mass% or less, based on the total mass of the curable silicone composition of the present invention.
In one embodiment, component (a) contains little or no aryl groups in the silicon atom-bonded organic group. Specifically, the amount of aryl groups in the entire silicon atom-bonded organic group may be 10 mol% or less, 5 mol% or less, 3 mol% or less, or 1 mol% or less.
(A) The viscosity of the alkenyl-containing organopolysiloxane is not particularly limited, and may be, for example, 5 mPa ·s to 5,000 mpa·s at 25 ℃, preferably 10 mPa ·s to 500 mPa ·s. In the present specification, the viscosity of the organopolysiloxane component can be measured by a rotational viscometer based on JISK 7117-1.
(A) The mass average molecular weight (Mw) of the alkenyl organopolysiloxane is not particularly limited, and is, for example, in the range of 1,000 to 100,000, preferably in the range of 1,500 to 15,000. In addition, in the present specification, the mass average molecular weight can be measured by GPC.
(A) The content of the entire component is not particularly limited, but may be 3 mass% or more, preferably 5 mass% or more, and more preferably 10 mass% or more based on the total mass of the curable silicone composition. The content of the component (a) may be 90% by weight or less, preferably 80% by weight or less, and more preferably 70% by weight or less, based on the total weight of the curable silicone composition.
(B) Organohydrogen polysiloxanes having at least two silicon atom-bonded hydrogen atoms per molecule
(B) The component functions as a crosslinking agent for the curable silicone composition by hydrosilylation curing reaction, and is an organohydrogen polysiloxane having at least two hydrogen atoms bonded to silicon atoms per molecule. The curable silicone composition of the present invention may contain one kind of (B) organohydrogen polysiloxane or two or more kinds of (B) organohydrogen polysiloxanes.
Examples of the molecular structure of the component (B) include linear, partially branched linear, branched, resinous, cyclic and three-dimensional network structures. (B) The component may be one kind of organohydrogen polysiloxane having these molecular structures or a mixture of two or more kinds of organohydrogen polysiloxanes having these molecular structures. The curable silicone composition of the present invention contains a linear organopolysiloxane as component (B).
Examples of the silicon atom-bonded group other than the silicon atom-bonded hydrogen atom contained in the component (B) include a monovalent hydrocarbon group substituted or unsubstituted with halogen other than an alkenyl group, for example, an alkyl group having 1 to 12 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, an aryl group having 6 to 20 carbon atoms such as phenyl, tolyl, xylyl, naphthyl, an aralkyl group having 7 to 20 carbon atoms such as benzyl, phenethyl, phenylpropyl, and a group in which part or all of hydrogen atoms of these groups are substituted with halogen atoms such as fluorine atom, chlorine atom, bromine atom. Further, the silicon atom in the component (B) may have a small amount of an alkoxy group such as a hydroxyl group, a methoxy group, or an ethoxy group, as long as the object of the present invention is not impaired. The group other than the silicon-bonded hydrogen atom bonded to the silicon atom of the component (B) is preferably selected from alkyl groups having 1 to 6 carbon atoms, particularly methyl groups.
In one embodiment of the present invention, the component (B) may contain a linear organohydrogen polysiloxane as the component (B-1). The linear organopolysiloxane of the component (B-1) can be preferably represented by the following average structural formula (II):
average structural formula (II) R 2 3SiO(R2 2SiO2/2)nSiR2 3
(In the formula (II), R 2 is a hydrogen atom or the same or different monovalent hydrocarbon groups which are substituted or unsubstituted by halogen and are other than alkenyl, wherein in one molecule, at least two R 2 are hydrogen atoms, and n is 1 to 200).
In the above formula (II), R 2 is a monovalent hydrocarbon group substituted or unsubstituted with halogen other than alkenyl, and examples thereof include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like, aryl groups having 6 to 20 carbon atoms such as phenyl, tolyl, xylyl, naphthyl and the like, aralkyl groups having 7 to 20 carbon atoms such as benzyl, phenethyl, phenylpropyl and the like, and groups in which part or all of hydrogen atoms of these groups are substituted with halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms and the like. R 2 may be a small amount of an alkoxy group such as a hydroxyl group, a methoxy group, or an ethoxy group, as long as the object of the present invention is not impaired. R 2 is preferably selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and particularly a methyl group.
In the above formula (II), n is preferably 2 to 150, more preferably 5 to 100.
In a preferred embodiment of the present invention, the linear organohydrogen polysiloxane of component (B-1) contains hydrogen atoms bonded to silicon atoms at both ends of the molecular chain. The linear organopolysiloxane of component (B-1) has a silicon atom-bonded hydrogen atom in the M unit and may or may not contain a silicon atom-bonded hydrogen atom in the D unit, but is preferably free of the silicon atom-bonded hydrogen atom.
In one embodiment, component (B) contains little or no aryl groups in the silicon atom-bonded organic group. Specifically, the amount of aryl groups in the entire silicon atom-bonded organic group may be 10 mol% or less, 5 mol% or less, 3 mol% or less, or 1 mol% or less.
(B) The content of the component is not particularly limited, and may be preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more, based on the total mass of the curable silicone composition. In a preferred embodiment, the content of the component (B) may be 30 mass% or less, preferably 20 mass% or less, more preferably 15 mass% or less, based on the total mass of the curable silicone composition.
In one embodiment of the present invention, the ratio (H/Ar) of the silicon atom-bonded alkenyl groups to the silicon atom-bonded hydrogen atoms contained in the organopolysiloxane component (B) may be 0.5 mol or more, preferably 0.7 mol or more, more preferably 1mol or more, particularly 1.2 mol or more, relative to 1mol of the silicon atom-bonded alkenyl groups in the curable silicone composition, and, for example, the silicon atom-bonded hydrogen atoms may be 5 mol or less, preferably 3 mol or less, more preferably 2.5 mol or less, more preferably 2 mol or less, relative to 1mol of the silicon atom-bonded alkenyl groups in the curable silicone composition.
(C) Thermally conductive filler
(C) The thermally conductive filler of the component is a component for imparting thermal conductivity required for the curable silicone composition of the present invention. The curable silicone composition of the present invention may contain one type of (C) thermally conductive filler, or may contain two or more types of (C) thermally conductive fillers.
(C) Examples of the composition may be selected from pure metals, alloys, metal oxides, metal hydroxides, metal nitrides, metal carbides, metal silicides, carbon, soft magnetic alloys and ferrites. Component (C) is preferably at least one powder and/or fiber, of which metal powder, metal oxide powder, metal nitride powder or carbon powder is preferred.
Examples of pure metals include bismuth, lead, tin, antimony, indium, cadmium, zinc, silver, copper, nickel, aluminum, iron, and metallic silicon. Examples of the alloy include alloys composed of two or more metals selected from bismuth, lead, tin, antimony, indium, cadmium, zinc, silver, aluminum, iron, and metallic silicon. Examples of the metal oxide include aluminum oxide (aluminum oxide), zinc oxide, silicon dioxide, magnesium oxide, beryllium oxide, chromium oxide, and titanium oxide. Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, barium hydroxide, and calcium hydroxide. Examples of the metal nitride include boron nitride, aluminum nitride, and silicon nitride. Examples of metal carbides include silicon carbide, boron carbide, and titanium carbide. Examples of the metal silicide include magnesium silicide, titanium silicide, zirconium silicide, tantalum silicide, niobium silicide, chromium silicide, tungsten silicide, and molybdenum silicide. Examples of carbon include diamond, graphite, fullerenes, carbon nanotubes, graphene, activated carbon, and amorphous carbon black. Examples of the soft magnetic alloy include Fe-Si alloy, fe-Al alloy, fe-Si-Cr alloy, fe-Ni-Co alloy, fe-Ni-Mo alloy, fe-Co alloy, fe-Si-Al-Cr alloy, fe-Si-B alloy, and Fe-Si-Co-B alloy. Examples of ferrites include Mn-Zn ferrites, mn-Mg-Zn ferrites, mg-Cu-Zn ferrites Ni-Zn ferrite, ni-Cu-Zn ferrite, and Cu-Zn ferrite.
(C) The component may preferably be selected from metal oxides, in particular from aluminium oxide (aluminium oxide), zinc oxide, silicon dioxide, magnesium oxide, beryllium oxide, chromium oxide and titanium oxide.
(C) The shape of the component is not particularly limited, and examples thereof include a sphere, a needle, a disk, a rod, and an indefinite shape, and a sphere is preferable.
(C) The average particle diameter of the 1 st order particles of the component is not particularly limited, but is preferably in the range of 0.01 to 50. Mu.m, more preferably in the range of 0.01 to 20. Mu.m, and still more preferably in the range of 0.1 to 5. Mu.m. In the present specification, the average particle diameter refers to a particle diameter (D50) at 50% of the cumulative value in the particle size distribution obtained by the laser diffraction-scattering method.
In a preferred embodiment of the present invention, component (C) comprises two thermally conductive fillers having different average particle sizes. In this embodiment, the component (C) preferably contains a combination of the component (C-1) having an average particle diameter of 2 μm or less and the component (C-2) having an average particle diameter exceeding 2 μm. The average particle diameter of the component (C-1) having a small average particle diameter is preferably in the range of 0.01 to 1.5. Mu.m, more preferably 0.1 to 1. Mu.m. The average particle diameter of the component (C-2) having a large average particle diameter is preferably in the range of 2.5 to 20. Mu.m, more preferably 3 to 5. Mu.m.
The content of the thermally conductive filler of the component (C) is 5 mass% or more based on the total mass of the curable silicone composition. The content of the thermally conductive filler of the component (C) may be preferably 7% by weight or more, more preferably 10% by weight or more, based on the total weight of the curable silicone composition. In a preferred embodiment, the content of the component (C) may be 90 wt% or less, preferably 80 wt% or less, based on the total weight of the curable silicone composition.
In another embodiment, the content of the thermally conductive filler of the component (C) may be 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, or 70% by mass or more, based on the total mass of the curable silicone composition. The content of the component (C) may be 90 wt% or less, preferably 80 wt% or less, based on the total weight of the curable silicone composition.
When the component (C) contains the component (C-1) and the component (C-2) having different particle diameters, the content ratio of the components is not particularly limited, but in general, the mass ratio of the component (C-2) to the component (C-1) is in the range of 1:10 to 10:1, preferably in the range of 1:5 to 5:1, more preferably in the range of 1: 3~3:1. In a preferred embodiment, the content of the component (C-2) is larger than that of the component (C-1), for example, the mass ratio of the component (C-1) is in the range of 1 to 10:1, preferably in the range of 1.25 to 5:1, more preferably in the range of 1.5 to 3:1.
(D) Cerium-containing organopolysiloxane
The curable silicone composition of the present invention contains a cerium-containing organopolysiloxane as the (D) component. (D) The cerium-containing organopolysiloxane can be prepared by, for example, reacting cerium chloride or a cerium salt of a carboxylic acid with an alkali metal salt of a silanol-containing organopolysiloxane. Thus, in the present specification, the term "cerium-containing organopolysiloxane" may refer to a cerium-containing organopolysiloxane obtained by reacting a silanol-group-containing organopolysiloxane with a cerium salt, the silanol group of the organopolysiloxane being chemically bonded to a cerium atom.
Examples of the cerium salt of the carboxylic acid include cerium 2-ethylhexanoate, cerium naphthenate, cerium oleate, cerium laurate, and cerium stearate. As the cerium chloride, cerium trichloride may be exemplified.
Further, as the alkali metal salt of the silanol-containing organopolysiloxane, there can be exemplified a potassium salt of a diorganopolysiloxane having both molecular chain ends blocked with silanol groups, a sodium salt of a diorganopolysiloxane having both molecular chain ends blocked with silanol groups, a potassium salt of a diorganopolysiloxane having one molecular chain end blocked with silanol groups and the other molecular chain end blocked with triorganosiloxy groups, and a sodium salt of a diorganopolysiloxane having one molecular chain end blocked with silanol groups and the other molecular chain end blocked with triorganosiloxy groups. Examples of the group bonded to the silicon atom in the organopolysiloxane include an alkyl group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group, an aryl group having 6 to 20 carbon atoms such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group, an aralkyl group having 7 to 20 carbon atoms such as a benzyl group, a phenethyl group, and a phenylpropyl group, and a group in which part or all of hydrogen atoms of these groups are substituted with halogen atoms such as a fluorine atom, a chlorine atom, and a bromine atom.
The reaction is carried out at room temperature or by heating in an organic solvent such as methanol, ethanol, isopropanol, butanol, aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, mineral spirits, light petroleum oils, and petroleum ethers. In addition, the reaction product obtained is preferably distilled off from the organic solvent, low-boiling components, or the precipitate is filtered as necessary. In order to promote the reaction, dialkylformamide, hexaalkylphosphamide, and the like may be added. The content of cerium atoms in the thus prepared cerium-containing organopolysiloxane is preferably in the range of 0.1 to 15 mass%.
(D) The component content is not particularly limited, but is preferably an amount in the range of 1 to 100 ppm, more preferably an amount in the range of 2 to 50 ppm, of the cerium atom content of the cerium-containing organopolysiloxane relative to the total mass of all organopolysiloxane components of the present composition.
(E) Curing catalyst
(E) The curing catalyst for the components is a hydrosilylation reaction curing catalyst, and is a catalyst for promoting the curing of the curable silicone composition of the present invention. Examples of the component (E) include a platinum-based catalyst such as chloroplatinic acid, an alcohol solution of chloroplatinic acid, a complex of platinum and an olefin, a complex of platinum and 1, 3-divinyl-1, 3-tetramethyldisiloxane, and a platinum-supported powder, a palladium-based catalyst such as tetrakis (triphenylphosphine) palladium, palladium black, and a mixture of tetrakis (triphenylphosphine), and a rhodium-based catalyst, and particularly preferably a platinum-based catalyst.
(E) The amount of the component (a) to be blended is a catalyst amount, more specifically, in the case of using a platinum-based catalyst as the component (E), the amount of platinum atoms is preferably 0.01 ppm or more, more preferably 0.1 ppm or more, still more preferably 1 ppm or more, relative to the total mass of the curable silicone composition of the present invention, and the amount of platinum atoms may be preferably 20 ppm or less, more preferably 15 ppm or less, still more preferably 10 ppm or less, and particularly preferably 5ppm or less, relative to the total mass of the curable silicone composition of the present invention.
(Other organopolysiloxane Components)
The curable silicone composition component of the present invention may contain an epoxy group-containing organopolysiloxane as an organopolysiloxane component other than the component (a) and the component (B). Preferably, the epoxy-containing organopolysiloxane is an organopolysiloxane containing at least one epoxy group and at least two alkenyl groups per molecule. The epoxy-containing organopolysiloxane may act as a tackifier.
Examples of the molecular structure of the epoxy-containing organopolysiloxane include linear, partially branched linear, branched, resinous, cyclic, and three-dimensional network structures, and the epoxy-containing organopolysiloxane is preferably a resinous one. The curable silicone composition of the present invention may contain one kind of epoxy-containing organopolysiloxane, or may contain two or more kinds of epoxy-containing organopolysiloxanes in combination.
The epoxy group-containing organopolysiloxane preferably contains, as alkenyl groups, alkenyl groups having 2 to 12 carbon atoms such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, etc., preferably vinyl groups, and examples of the epoxy group-containing organic groups include glycidoxyalkyl groups such as 2-glycidoxylethyl, 3-glycidoxypropyl, 4-glycidoxybutyl, etc., epoxycycloalkylalkyl groups such as 2- (3, 4-epoxycyclohexyl) -ethyl, 3- (3, 4-epoxycyclohexyl) -propyl, etc., epoxycycloalkyl groups such as 3, 4-epoxybutyl, 7, 8-epoxyoctyl, etc., preferably glycidoxyalkyl groups, particularly preferably 3-glycidoxypropyl groups.
Examples of the alkenyl group of the epoxy group-containing organopolysiloxane and the group bonded to a silicon atom other than the epoxy group-containing organic group include a monovalent hydrocarbon group substituted or unsubstituted with halogen other than the alkenyl group and the epoxy group-containing organic group, and examples thereof include alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, etc., aryl groups having 6 to 20 carbon atoms such as phenyl, tolyl, xylyl, naphthyl, etc., aralkyl groups having 7 to 20 carbon atoms such as benzyl, phenethyl, phenylpropyl, etc., and groups having some or all of hydrogen atoms substituted with halogen atoms such as fluorine atom, chlorine atom, bromine atom, etc., preferably 1 to 12 alkyl groups, particularly methyl groups.
The resinous epoxy-containing organopolysiloxane is preferably represented by the following average unit formula (III) .(R3 3SiO1/2)f(R3 2SiO2/2)g(R3SiO3/2)h(SiO4/2)i(XO1/2)j
{ Formula (III) wherein R 3 is independently a monovalent hydrocarbon group substituted or unsubstituted with halogen, wherein at least two R 3 are alkenyl groups, and further wherein at least one R 3 is an epoxy group-containing organic group, X is a hydrogen atom or an alkyl group, 0≤f < 1, 0≤g < 1, 0≤h < 0.9, 0≤i < 0.5, and 0≤j < 0.4, f+g+h+i=1.0, h+i > 0.j represents the number of (XO) groups (ratio of the number of (XO) groups to the total number of silicon atoms) when the total number of silicon atoms is 1.
In the above formula (III), examples of the monovalent hydrocarbon group substituted or unsubstituted with halogen of R 3 include the above alkenyl group, epoxy group-containing organic group, and monovalent hydrocarbon groups other than these. In the formula (III), X is a hydrogen atom or an alkyl group. The alkyl group of X is preferably an alkyl group having 1 to 3 carbon atoms, and specifically, methyl, ethyl, and propyl are exemplified.
In the above formula (III), f is preferably in the range of 0≤f≤0.5, more preferably in the range of 0≤f≤0.3, and still more preferably in the range of 0≤f≤0.1. In the above formula (III), g is preferably in the range of 0.1≤g≤0.7, more preferably in the range of 0.2≤g≤0.6, and particularly in the range of 0.3≤g≤0.5. In the above formula (III), h is preferably in the range of 0.2≤h≤0.8, more preferably in the range of 0.3≤h≤0.7, and particularly in the range of 0.4≤h≤0.65. In the above formula (III), i is preferably in the range of 0≤i≤0.4, more preferably in the range of 0≤i≤0.25, and particularly in the range of 0≤i≤0.1. In the above formula (III), j is preferably in the range of 0≤j≤0.3, more preferably in the range of 0≤j≤0.2, and particularly in the range of 0≤j≤0.1.
In a preferred embodiment of the present invention, the resinous epoxy-containing organopolysiloxane in formula (III) above, h is greater than 0, i.e., comprises siloxane units (T units) represented by SiO 3/2. The epoxy group-containing resinous organopolysiloxane may or may not contain a siloxane unit (Q unit) represented by SiO 4/2, but preferably does not contain it. The epoxy group-containing resinous organopolysiloxane may or may not contain a siloxane unit (M unit) represented by SiO 1/2, but preferably does not contain it.
In a preferred embodiment of the invention, the epoxy-containing organopolysiloxane has epoxy-containing organic groups as side groups of the molecular side chains. The epoxy-containing organopolysiloxane preferably has an epoxy-containing organic group in a siloxane unit (T unit) represented by SiO 3/2.
In a preferred embodiment, the amount of alkenyl groups in the entire organic groups bonded to silicon atoms in the epoxy group-containing organopolysiloxane is not particularly limited, and may be preferably 1 mol% or more, more preferably 3 mol% or more, further preferably 5 mol% or more, and may be, for example, 30 mol% or less, preferably 20 mol% or less, more preferably 15 mol% or less.
The amount of the epoxy group-containing organic group in the entire silicon atom-bonded organic group in the epoxy group-containing organopolysiloxane is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and further, for example, 60 mol% or less, preferably 50 mol% or less. The amount of the epoxy-containing organic group can be determined by, for example, analysis by fourier transform infrared spectroscopy (FT-IR), nuclear Magnetic Resonance (NMR), or the like.
The mass average molecular weight (Mw) of the epoxy group-containing organopolysiloxane is not particularly limited, and may be in the range of 1,000 to 10,000. In addition, in the present specification, the mass average molecular weight can be measured by GPC.
The content of the epoxy group-containing organopolysiloxane is not particularly limited, but is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and still more preferably 0.5 mass% or more, based on the total mass of the curable silicone composition of the present invention, and may be 20 mass% or less, more preferably 10 mass% or less, and still more preferably 5 mass% or less, based on the total mass of the curable silicone composition of the present invention.
As other organopolysiloxane components, the curable silicone composition may further include a cyclic organopolysiloxane having at least two alkenyl groups per molecule as a siloxane-reactive diluent. Such a cyclic organopolysiloxane may preferably be selected from the following
The average structural formula (IV) is (R) 4 2SiO)n
(In the formula (IV), R 4 is the same or different halogen substituted or unsubstituted monovalent hydrocarbon groups, wherein at least two R 4 are alkenyl groups in one molecule, n is 4 to 15, preferably 4 to 10, more preferably 4 to 8).
In the above formula (IV), the monovalent hydrocarbon group substituted or unsubstituted by halogen is preferably selected from the group consisting of alkyl groups having 1 to 12 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like, aryl groups having 6 to 20 carbon atoms such as phenyl, tolyl, xylyl, naphthyl and the like, alkenyl groups having 2 to 12 carbon atoms such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl and the like, and groups in which part or all of hydrogen atoms are substituted with halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms and the like. R 4 is preferably selected from an alkyl group having 1 to 6 carbon atoms, particularly a methyl group, or an alkenyl group having 2 to 6 carbon atoms, particularly a vinyl group.
The content of the cyclic organopolysiloxane is not particularly limited, but may be 0.01 mass% or more, more preferably 0.1 mass% or more, still more preferably 0.5 mass% or more, based on the total mass of the curable silicone composition of the present invention, and may be 20 mass% or less, more preferably 10 mass% or less, still more preferably 5 mass% or less, based on the total mass of the curable silicone composition of the present invention.
(Other Components)
The curable silicone composition of the present invention can contain any component within a range that does not interfere with the object of the present invention. Examples of the optional component include acetylene compounds, organic phosphorus compounds, vinyl-containing siloxane compounds, inorganic fillers other than the component (C), inorganic fillers such as ground quartz, silica, magnesium carbonate, diatomaceous earth, and the like, inorganic fillers obtained by hydrophobicizing the surface of such inorganic fillers with an organosilicon compound, surface treating agents, hydrosilylation reaction inhibitors, tackifiers, heat resistance imparting agents, cold resistance imparting agents, flame retardancy imparting agents, thixotropic imparting agents, phosphors, solvents, and the like. The amount of such optional components is usually 0.001 to 20% by mass based on the entire composition.
Examples of the silica in the inorganic filler include fumed silica, dry silica, wet silica, crystalline silica, and precipitated silica. The silica may be surface-hydrophobicized with an organosilicon compound such as an organoalkoxysilane compound, an organochlorosilane compound, an organosilane-nitrogen compound, or a low-molecular-weight siloxane compound, a silane coupling agent, or a titanate coupling agent.
The hydrosilylation reaction inhibitor is a component for inhibiting the hydrosilylation reaction of the curable silicone composition. Examples of such a curing reaction inhibitor include alkynols such as 2-methyl-3-butyn-2-ol, 3, 5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, 1-ethynyl-1-cyclohexanol, and 1-ethynyl-2-cyclohexanol, enyne compounds such as 3-methyl-3-penten-1-yne, 3, 5-dimethyl-3-hexen-1-yne, alkenyl-containing low molecular weight siloxanes such as tetramethyl tetravinyl cyclotetrasiloxane and tetramethyl tetrahexenyl cyclotetrasiloxane, and alkynyloxy silanes such as methyl-tris (1, 1-dimethylpropynyloxy) silane and vinyl-tris (1, 1-dimethylpropynyloxy) silane, methyl-tris- (3-methyl-1-butynyl-3-oxy) silane. Preferably, the hydrosilylation reaction inhibitor is selected from alkynols, particularly preferably 1-ethynyl-1-cyclohexanol. The amount of the reaction inhibitor to be added is usually 0.001 to 5% by mass based on the entire composition.
In one embodiment of the present invention, the curable silicone composition comprises two or more different curing reaction inhibitors. In a preferred embodiment, the curable silicone composition comprises a combination of at least one alkynol and at least one alkynyloxy silane as a curing reaction inhibitor.
The surface treatment agent is not particularly limited in the type of the surface treatment agent used for the filler, particularly the thermally conductive filler of the component (C), and examples thereof include organosilazanes, organocyclosiloxanes, organochlorosilanes, organoalkoxysilanes, alkoxysilylalkyl-containing organopolysiloxanes, low-molecular-weight linear siloxanes, organic compounds, and the like, and examples thereof include polyols, alkanolamines or derivatives thereof, organosilicon compounds such as organosiloxanes, higher fatty acids or metal salts thereof, organometallic compounds, organometallic complexes, fluorine-based organic compounds, anionic surfactants, cationic surfactants, nonionic surfactants, and the like.
The alkoxysilylalkyl-containing organopolysiloxane as a surface treatment agent can be represented by, for example, (R) aO)3Si-(CH2)p-(Rb 2SiO)q-Rc
(Wherein R a and R b are each independently an alkyl group of C 1~4, particularly methyl, R c is an alkyl group of C 1~10, preferably C 2~6, p is 3 to 12, preferably 4 to 10, q is 50 to 150, preferably 75 to 95).
The content of the surface treatment agent is not particularly limited, and is usually 0.01% by mass or more, more preferably 0.05% by mass or more based on the total weight of the curable silicone composition of the present invention, and may be 10% by weight or less, more preferably 5% by weight or less based on the total weight of the curable silicone composition of the present invention.
In a preferred embodiment of the present invention, the curable silicone composition can be cured to form a cured product having excellent thermal conductivity. For example, in a preferred embodiment, the thermal conductivity of the cured product of the curable silicone composition is 0.5 (W/(m·k)) or more, and more preferably 1.0 (W/(m·k)) or more. The upper limit of the thermal conductivity is not particularly limited, but is usually less than 3.0 (W/(m·k)). Thermal conductivity can be measured, for example, using a hotplate.
The curable silicone composition of the present invention can be prepared by mixing the components. The method of mixing the components may be a conventionally known method, and is not particularly limited, and may be prepared by mixing using a mixing device, for example. Such a mixing device is not particularly limited, and examples thereof include a single-or twin-shaft continuous mixer, a twin-roll kneader, a ross mixer, a jobert mixer, a dental mixer, a planetary mixer, a kneading mixer, a henschel mixer, and the like.
[ Adhesives ]
The present invention also relates to an adhesive comprising the curable silicone composition of the present invention. Preferably, the adhesive of the present invention may be used as a thermally conductive adhesive. Preferably, the adhesive of the present invention can be used as an adhesive for die bonding of optical semiconductor elements and the like. The shape of the adhesive of the present invention is not particularly limited, and is preferably a sheet shape. The semiconductor bonded by the adhesive of the present invention is not particularly limited, and examples thereof include a semiconductor such as SiC and GaN, and particularly an optical semiconductor such as a power semiconductor or a light emitting diode.
[ Optical semiconductor device ]
The present invention also relates to an optical semiconductor device comprising the adhesive of the present invention. Examples of the optical semiconductor element included in the optical semiconductor device include a Light Emitting Diode (LED), a semiconductor laser, a photodiode, a phototransistor, a solid-state imaging device, a light emitter for a photocoupler, and a photoconductor, and particularly, a Light Emitting Diode (LED) is preferable.
Since a Light Emitting Diode (LED) emits light from the upper, lower, left, and right sides of a semiconductor element, a material that absorbs light is not preferable as a member constituting the Light Emitting Diode (LED), and a material having high light transmittance or high reflectance is preferable. Therefore, a substrate on which the semiconductor element is mounted is also preferably made of a material having high light transmittance or high reflectance. Examples of the substrate on which such an optical semiconductor element is mounted include conductive metals such as silver, gold, and copper, nonconductive metals such as aluminum and nickel, thermoplastic resins in which white pigments such as PPA and LCP are mixed, thermosetting resins containing white pigments such as epoxy resins, BT resins, polyimide resins, and silicone resins, and ceramics such as alumina and aluminum nitride.
Specific embodiments of the invention are shown below.
Scheme 1 a curable silicone composition comprising (a) an alkenyl-containing organopolysiloxane having at least two alkenyl groups per molecule;
(B) Organohydrogen polysiloxanes having at least two hydrogen atoms bonded to silicon atoms per molecule;
(C) A thermally conductive filler in an amount of 5 mass% or more relative to the total mass of the composition;
(D) Cerium-containing organopolysiloxane, and
(E) A curing catalyst.
Scheme 2 the curable silicone composition according to scheme 1, wherein the (A) alkenyl-containing organopolysiloxane comprises an MQ resin.
Scheme 3 the curable silicone composition according to scheme 1 or 2, wherein the (C) thermally conductive filler is a metal oxide.
The curable silicone composition according to any one of items 1 to 3, wherein the (C) thermally conductive filler contains two thermally conductive fillers having different average particle diameters.
The curable silicone composition according to any one of the aspects 1 to 4, wherein the cerium atom of the (D) cerium-containing organopolysiloxane is in an amount of 1 to 100 ppm based on the total mass of all organopolysiloxane components of the present composition.
An adhesive according to claim 6, which comprises the curable silicone composition according to any one of claims 1 to 5.
Scheme 7 an optical semiconductor device comprising the adhesive of scheme 6.
Examples
The curable silicone composition of the present invention will be described in detail with reference to the following examples and comparative examples.
The components were mixed in accordance with the compositions (parts by mass) shown in the table to prepare curable silicone compositions. In the following, me represents a methyl group, vi represents a vinyl group, and Ep represents a 3-glycidoxypropyl group. In addition, the structure of the organopolysiloxane component is shown simplified in the table, and the parenthesis indicates M, D or an organic group other than Me on the T unit. In addition, H/Vi represents the molar ratio of the silicon-bonded hydrogen atom (H) to vinyl group (Vi) in the organopolysiloxane component. In the present specification, a chemical formula including a siloxane unit represented by (SiO x/2) (x is an integer of 1 to 4) is represented by a "unit formula", and a "structural formula" is represented by a chemical formula not including such a siloxane unit. In the table, the content of component d represents the content (ppm) of cerium atoms in the component d in the entire organopolysiloxane component.
Component a-1 resinous alkenyl group-containing organopolysiloxane (solid at 25 ℃ C., mass average molecular weight (Mw): 5,100) represented by average unit formula (Me3SiO1/2)40.9(ViMe2SiO1/2)7.1(SiO4/2)52(OH)4.9
Component a-2 Linear alkenyl-containing organopolysiloxane represented by the average structural formula ViMe 2SiO(M2SiO)46SiMe2 Vi
Component b Linear organohydrogen polysiloxane represented by average Structure Me 3SiO(MeHSiO)50SiMe3
Component c-1 alumina (average particle size: 3.4 μm)
Component c-2 alumina (average particle size: 0.5 μm)
Component d cerium-containing dimethylpolysiloxane having a cerium content of 1.4% by mass
Component e platinum complex with divinyl tetramethyl disiloxane having a platinum concentration of 3.0% by mass
Component f-1:1-ethynyl-2-cyclohexanol
Component f-2 methyl-tris- (3-methyl-1-butyn-3-yloxy) silane
Component g, a cyclic alkenyl-containing organopolysiloxane represented by the average structural formula (ViMeSiO) 4
Component h-condensation reaction product of a silanol-terminated methylvinylsiloxane oligomer at both molecular terminals with 3-glycidoxypropyl trimethoxysilane (mass average molecular weight (Mw): 1280, viscosity at 25 ℃ C.: 22.5 mm 2/s)
Component i fumed silica (surface treatment with hexamethyldisilazane and trimethylsilane)
Component j surface treatment agent containing alkoxysilylalkyl organopolysiloxane
[ Chip shear Strength ]
An alumina plate of 25 mm ×75× 75mm was used as a substrate, and 5 pieces of 5mm ×5× 5mm ×1× 1mm alumina chips were used as bonding chips. For each chip, a curable silicone composition of 0.0080 g ±0.0005 g was applied, and after the chips were placed thereon, each chip was bonded to a substrate by curing at 150 ℃ for 2 hours. The shear strength of the chips was measured using a push-pull force tester (model: SS-30WD, test mode: PH50 push, speed: 0.120 mm/sec). In addition, the test specimens were aged at 200℃for 1000 hours, and the chip shear strength was measured similarly. The results of the chip shear strength before and after aging are shown below.
TABLE 1
[ Thermal conductivity ]
The curable silicone composition was cured by holding at a temperature of 150 ℃, at a pressure of 20 MPa for 15 minutes and at atmospheric pressure for 105 minutes, obtaining a cylindrical cured sample having a height of 1 cm and a diameter of 2.1 cm. The thermal conductivity (W/(m.K)) of the sample was measured using a hot plate (model: TPS 500s, manufactured by Kyoto electronics Co., ltd.). The results are shown in the following table.
TABLE 2
[ Weight loss ]
The curable silicone composition was cured at a temperature of 150 ℃ for 15 minutes at a pressure of 20 MPa and at atmospheric pressure for 105 minutes, giving a plate-shaped cured product sample of 1 cm ×5 cm ×2 mm. The sample was aged at 200 ℃ and the weight after 500 hours and 1000 hours was measured, and the weight loss (%) was calculated by the following calculation formula.
(Initial weight-weight after aging)/initial weight×100
TABLE 3
As can be seen from the results of table 1, the curable silicone composition containing the thermally conductive filler of the present invention maintains excellent strength even after aging at high temperature, and exhibits excellent thermal stability. Further, as is clear from the results of table 2, the curable silicone composition of the present invention containing a high content of the thermally conductive filler can exhibit high thermal conductivity. Further, as is clear from the results of Table 3, the curable silicone composition of the present invention has a weight loss reduced by about 1% even after aging at high temperature for 1000 hours, and it has been found that the chemical structure thereof can be maintained even after aging.
Although the preferred embodiments of the present invention have been described above, the present invention is not limited to these embodiments. Additions, omissions, substitutions, and other modifications can be made to the structure without departing from the spirit of the present invention. The invention is not to be limited by the foregoing description but is only limited by the scope of the appended claims.

Claims (7)

1.一种固化性硅酮组合物，其包含：1. A curable silicone composition comprising: （A）每一分子具有至少两个烯基的含烯基有机聚硅氧烷；(A) Alkenyl-containing organopolysiloxanes having at least two alkenyl groups per molecule; （B）每一分子具有至少两个与硅原子键合的氢原子的有机氢聚硅氧烷；(B) Organohydrogen polysiloxanes, each molecule having at least two hydrogen atoms bonded to silicon atoms; （C）相对于组合物总质量为5质量%以上的导热性填料；(C) Thermally conductive fillers accounting for 5% or more of the total mass of the composition; （D）含铈有机聚硅氧烷；以及(D) Cerium-containing organopolysiloxanes; and （E）固化用催化剂。(E) Curing catalyst. 2.根据权利要求1所述的固化性硅酮组合物，其中，所述（A）含烯基有机聚硅氧烷含有MQ树脂。2. The curable silicone composition according to claim 1, wherein the (A) alkenyl organopolysiloxane contains MQ resin. 3.根据权利要求1或2所述的固化性硅酮组合物，其中，所述（C）导热性填料为金属氧化物。3. The curable silicone composition according to claim 1 or 2, wherein the thermally conductive filler (C) is a metal oxide. 4.根据权利要求1所述的固化性硅酮组合物，其中，所述（C）导热性填料含有平均粒径不同的两种导热性填料。4. The curable silicone composition according to claim 1, wherein the (C) thermally conductive filler contains two types of thermally conductive fillers with different average particle sizes. 5.根据权利要求1所述的固化性硅酮组合物，其中，所述（D）含铈有机聚硅氧烷的铈原子的含量相对于本组合物的全部有机聚硅氧烷成分的总质量为1~100 ppm的量。5. The curable silicone composition according to claim 1, wherein the content of cerium atoms in the (D) cerium-containing organopolysiloxane is 1 to 100 ppm relative to the total mass of all organopolysiloxane components of the composition. 6.一种粘合剂，其包含权利要求1至5中任一项所述的固化性硅酮组合物。6. An adhesive comprising the curable silicone composition according to any one of claims 1 to 5. 7.一种光半导体装置，其包括权利要求6所述的粘合剂。7. An optical semiconductor device comprising the adhesive of claim 6.
CN202480050797.8A 2023-08-04 2024-07-31 Curable silicone compositions, adhesives, and optoelectronic semiconductor devices Pending CN121620566A (en)

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