JP2016124967A - Curable silicone composition, semiconductor sealant comprising the same and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable silicone composition that gives a cured product having excellent initial physical strength, and maintains high physical strength even when exposed to a high temperature of 250°C or more, and a use thereof.SOLUTION: A curable silicone composition comprises (A) an organic silicon compound having an alkylene group with 2-20 carbon atoms and an alkenyl group with 2-20 carbon atoms bound to a silicon atom in a molecule and (B) a peroxide.SELECTED DRAWING: None

Description

  The present invention relates to a curable silicone composition, a semiconductor sealing agent comprising the curable silicone composition, and a semiconductor device sealed using the same.

  Since the curable silicone composition is cured to form a cured product having excellent heat resistance, cold resistance, electrical insulation, weather resistance, water repellency, and transparency, it is used in a wide range of industrial fields. In particular, the cured product is less likely to be discolored than other organic materials and has a small decrease in physical physical properties, and thus is suitable as an optical material. For example, Patent Document 1 proposes a liquid silicone resin composition for a light-emitting diode (LED) element, which comprises an alkenyl group-containing silicone resin, a silicon-bonded hydrogen atom-containing organopolysiloxane, and a hydrosilylation reaction catalyst. .

  On the other hand, due to the tendency of the junction temperature to increase in the semiconductor industry, there is an increasing demand for heat resistance during long-term high-temperature storage of the semiconductor sealing resin. However, a cured product of an epoxy resin composition that has been conventionally used as a sealing material for semiconductors has a drawback in that a dimensional change or a mass change occurs during long-term storage at a high temperature and cracks occur. Silicone resin compositions have better heat resistance than epoxy resin compositions, but phenyl resin-based silicone resin compositions have been proposed in terms of mechanical strength. On the other hand, since the phenyl resin-based silicone resin composition is inferior in heat resistance to the methyl-based silicone resin composition, it is an optimal silicone resin as a sealing resin used in power devices and the like that require super heat resistance. The present condition is that the composition is not found.

For example, Patent Document 2 contains phenyl group-containing organopolysiloxane containing an average of 3 or more alkenyl groups in one molecule and organic groups bonded to silicon atoms, and containing 2 or more alkenyl groups in the molecule. An alkenyl group-containing organopolysiloxane comprising a linear organopolysiloxane having 20 to 60% phenyl groups and the remainder being methyl groups, SiO _4/2 units and R ″ (CH ₃ ) ₂ SiO _1/2 Curability consisting of a unit (wherein R ″ is a hydrogen atom or a methyl group), an alkylhydrogenpolysiloxane containing 3 or more hydrogen atoms bonded to a silicon atom in the molecule, and a platinum group metal compound Although a silicone composition has been proposed, a cured product comprising this composition has excellent initial physical strength, but the strength is extremely reduced when exposed to a high temperature of 200 ° C. or higher. There is a problem in that.

Patent Document 3 discloses an organopolysiloxane having at least two alkenyl groups in one molecule, an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, a catalyst for hydrosilylation reaction, an average particle Proposed is a methyl curable silicone composition comprising at least spherical silica fine powder having a diameter of 50 μm or less and glass fibers having an average fiber length of 1,000 μm or less and an average fiber diameter of 30 μm or less. However, it is insufficient in physical strength and toughness as a sealing resin for semiconductors.

On the other hand, Patent Document 4 proposes to use a hydrosilylation catalyst and a peroxide curing reaction in a thermosetting composition containing an organopolysiloxane resin. There is no description or suggestion about pre-synthesis of a composition, especially an organopolysiloxane having an alkylene group and an alkenyl group in the molecule.

JP 2004-186168 A JP 2007-039483 A JP 2014-0665900 A JP 2007-246842 A

  An object of the present invention is to provide a curable silicone composition that is excellent in physical strength of an initial cured product and maintains high physical strength even when exposed to a high temperature of 250 ° C. or higher. Furthermore, the other object of this invention is to provide the sealing compound for semiconductors and a semiconductor device which consist of the said curable silicone composition.

  The curable silicone composition of the present invention comprises (A) an organosilicon compound having an alkylene group having 2 to 20 carbon atoms and an alkenyl group having 2 to 20 carbon atoms bonded to a silicon atom in the molecule; ) It contains a peroxide. Here, the content of the alkenyl group in the component (A) is preferably in the range of 0.20 to 5.00 mol%, and the [content of alkylene group (mol%)] in the component (A). The ratio of / [alkenyl group content (mol%)] is particularly preferably in the range of 0.20 to 5.00.

  The physical properties of the cured product are determined by the siloxane unit in component (A). Specifically, a resinous organopolysiloxane having many branched siloxane units imparts hardness and mechanical strength to the cured product, and the resulting organopolysiloxane having many chain siloxane units is tough to the cured product. Therefore, the component (A) is resin-like in the molecule because it can maintain high physical strength even when exposed to a high temperature of 250 ° C. or higher. It preferably has a siloxane structure and a chain siloxane structure. An organosilicon compound having such a structure is obtained by reacting a hydrosilylation-reactive resinous organopolysiloxane with a hydrosilylation-reactive chain organopolysiloxane in the presence of a hydrosilylation reaction catalyst. It can be obtained by a hydrosilylation reaction in a ratio designed so that the groups remain after the hydrosilylation reaction.

Therefore, the curable silicone composition of the present invention preferably has
(A) component is
(A1): at least two alkenyl groups having 2 to 20 carbon atoms in one molecule obtained by mixing the following components (a1-1) or (a1-2) at a mass ratio of 50:50 to 100: 0. One or more organopolysiloxanes (a1-1) having an alkenyl group-containing resinous organopolysiloxane represented by the following structural formula [R ^Vi R ² ₂ SiO _0.5 ] _p [R ² ₃ SiO _0.5 ] _q [R ² SiO _1.5 ] _r [SiO _2.0 ] _s (R ⁵ O _1/2 ) _e
In the formula, R ^Vi is an alkenyl group having 2 to 20 carbon atoms, R ² is an alkyl group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms. An aryl group and at least one group selected from a halogen-substituted aryl group having 6 to 20 carbon atoms, a hydroxyl group or an epoxy group-containing group, and R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. P + q + r + s = 1.0, (p + q) :( r + s) = 0.15-0.70: 0.85-0.30, p> 0, and e is in the range of 0-0.05. Is a number.
(A1-2) Alkenyl group-containing chain organopolysiloxane [R ^Vi R ² ₂ SiO _0.5 ] ₂ [R ² ₂ SiO _1.0 ] t represented by the following structural formula
In the formula, R ^Vi and R ² are the same groups as described above, and t is a number in the range of 1 to 1000.
And (a2): one or more organohydrogenpolysiloxanes in which the following components (a2-1) or (a2-2) are mixed at a mass ratio of 50:50 to 100: 0:
(A2-1) Resin-like or chain-like organohydrogenpolysiloxane having a silicon atom-bonded hydrogen atom at the end of the molecular structure represented by the following structural formula [HR ² ₂ SiO _0.5 ] _u [R ² ₂ SiO _{1 ^{.0] v [R 2 SiO 1.5}} ] w [SiO 2.0] x (R 5 O 1/2) e
In the formula, R ² and R ⁵ are the same groups as described above, u + v + w + x = 1.0, u: (v + w + x) = 0.01 to 0.75: 0.99 to 0.25, and e is It is a number in the range of 0 to 0.05.
(A2-2) Chain-like organohydrogenpolysiloxane having a silicon atom-bonded hydrogen atom in the side chain represented by the following structural formula [R ² ₃ SiO _0.5 ] ₂ [HR ² SiO _1.0 ] _y
Wherein R ² is the same group as described above, and y is a number in the range of 2 to 1000.
In the presence of (a3) hydrosilylation reaction catalyst, 1 mol of alkenyl group having 2 to 20 carbon atoms contained in component (a1) and silicon atom in organohydrogenpolysiloxane in component (a2) It is preferably an organosilicon compound obtained by hydrosilylation reaction in an amount such that the number of moles of bonded hydrogen atoms is 0.2 to 0.7 moles,
The component (B) is particularly preferably a peroxide having a 10-hour half-life temperature of 90 ° C. or higher. Furthermore, it is particularly preferable that the curable silicone composition contains (C) an inorganic filler in a range of 10 to 2000 parts by mass with respect to 100 parts by mass of the component (A).

  Moreover, the sealing agent for semiconductors of this invention consists of said curable silicone composition, and the semiconductor device of this invention has the hardened | cured material which hardens said curable silicone composition. is there.

  The curable silicone composition of the present invention has a high initial hardness and is characterized in that the physical strength is not greatly reduced even when exposed to a high temperature of 250 ° C. or higher. For this reason, when used as a sealant for various semiconductors, including light emitting diode (LED) elements and power semiconductors, the semiconductor is excellent in handling workability and even under conditions exposed to high output / high temperature. There is an advantage that the durability and reliability can be remarkably improved. Furthermore, the curable silicone composition of the present invention can optionally be imparted with a feature (= hot melt property) that is non-flowable at 25 ° C., has low surface tackiness, and is easily melted by heating. .

  The curable silicone composition of the present invention comprises (A) an organosilicon compound having an alkylene group having 2 to 20 carbon atoms and an alkenyl group having 2 to 20 carbon atoms bonded to a silicon atom in the molecule; ) It contains a peroxide. Further, the curable silicone composition particularly preferably contains (C) an inorganic filler in a range of 10 to 2000 parts by mass with respect to 100 parts by mass of the component (A). If desired, (D) a reaction inhibitor, You may contain 1 or more types chosen from an adhesion | attachment imparting agent and a heat resistance imparting agent, and another additive and fluorescent substance. Hereinafter, each component will be described.

[Organic silicon compound (component (A))]
The component (A) is an organosilicon compound having an alkylene group having 2 to 20 carbon atoms and an alkenyl group having 2 to 20 carbon atoms bonded to a silicon atom in the molecule. And (B) a component imparting curability and high-temperature durability due to peroxide. The component (A) may be prepared in advance, and each raw material component of the component (A) described later is mixed in a reaction ratio designed so that an alkylene group and an alkenyl group remain in the molecule, (B) You may make it react in advance at the temperature lower than the curing reaction temperature by a peroxide.

The component (A) is an organosilicon compound having an alkylene group having 2 to 20 carbon atoms and an alkenyl group having 2 to 20 carbon atoms bonded to a silicon atom in the molecule, and an alkylene bond between silicon and silicon. And a silalkylene-polysiloxane structure in which a chain or resin-like polysiloxane structure is bonded, and an alkenyl group capable of thermosetting reaction with a peroxide. By having such a structure, the (B) peroxide can be thermally cured by the remaining alkenyl group, so that the initial strength is high and the physical strength even when exposed to a high temperature of 250 ° C. or higher. Has the advantage that it does not drop significantly.

From the viewpoint of the thermosetting property due to the above (B) peroxide, the ratio of [alkylene group content (mol%)] / [alkenyl group content (mol%)] in component (A) is 0. It may be in the range of .20 to 5.00 and is preferably in the range of 0.20 to 4.00. If this ratio is less than the lower limit, the amount of alkenyl groups becomes excessive, and physical properties such as initial hardness and strength may be insufficient. On the other hand, if this ratio exceeds the upper limit, (B) thermosetting and high-temperature durability due to peroxide may be insufficient. The content of the alkenyl group in the component (A) (mol% of the alkenyl group in the entire silicon atom-bonded functional group in the component (A)) can be designed as desired. From the viewpoint of curability and high temperature durability, it may be 0.20 to 5.00 mol%, and is preferably in the range of 0.40 to 5.00 mol%. When the content of the alkenyl group is less than the lower limit, the thermosetting property by (B) peroxide may be insufficient, and when the content exceeds the upper limit, the content of the alkenyl group becomes excessive, and the initial cured product This is because physical properties such as hardness and strength may be impaired.

Component (A) comprises an organopolysiloxane having at least two alkenyl groups in one molecule and an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule [number of moles of alkenyl groups] / It can be obtained by a hydrosilylation reaction at a reaction ratio of [number of moles of silicon-bonded hydrogen atoms]> 1. The alkenyl group in the reaction raw material forms a silalkylene bond between polysiloxanes by a hydrosilylation reaction with a silicon atom-bonded hydrogen atom, while excess alkenyl groups are in the resulting hydrosilylation reaction product ( As the silicon-bonded alkenyl group in component A), it is used for (B) a thermosetting reaction with a peroxide.

(A) As an alkenyl group in a component, it is C2-C20, such as vinyl group, an allyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group These may be linear or branched, and are preferably a vinyl group or a hexenyl group. Similarly, examples of the alkylene group in component (A) include alkenyl groups having 2 to 20 carbon atoms such as ethylene group, propylene group, butylene group, pentylene group, and hexylene group, which may be linear or branched. However, it is preferably an ethylene group or a hexylene group.

（式中、ｋは１〜１０、特に２〜８の数である。） On the other hand, as the group bonded to the silicon atom other than the alkenyl group in the component (A), an alkyl group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms. Examples include aryl groups, and halogen-substituted aryl groups having 6 to 20 carbon atoms, hydroxyl groups, alkoxy groups, and epoxy group-containing groups. Particularly, methyl groups, ethyl groups, propyl groups, butyl groups, pentyl groups, hexyl groups, Alkyl group such as heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc .; C6-C20 such as phenyl group, tolyl group, xylyl group, naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group A group in which some or all of the aryl groups and hydrogen atoms bonded to these groups are substituted with halogen atoms such as chlorine atoms and bromine atoms; Epoxy group-containing group represented by the serial structure can be exemplified. Particularly preferred is a methyl group, a phenyl group, a glycidoxypropyl group or a hydroxyl group. An epoxy group-containing group such as a glycidoxypropyl group is a functional group used for an adhesion-imparting agent, and the cured product obtained when the component (A) after the semi-curing reaction has these epoxy group-containing groups. In some cases, the cured adhesiveness and adhesiveness of the product may be further improved.

(In the formula, k is a number of 1 to 10, particularly 2 to 8.)

The component (A) is non-flowable at 25 ° C. by making 10 mol% or more, preferably 20 mol% or more of the monovalent organic group bonded to the silicon atom an aryl group, preferably a phenyl group. Thus, it is possible to provide a curable composition containing a hot-melt organosilicon compound having low surface tackiness.

The siloxane unit or the silalkylene group-containing siloxane unit constituting the component (A) is not particularly limited, but in order to impart sufficient hardness and mechanical properties to the resulting cured product, a linear poly It is preferable that both the siloxane unit and the resin-like polysiloxane unit are in the same molecule. Such an organosilicon compound is preferably composed of the following siloxane units and silalkylene group-containing siloxane units.
M unit: siloxane unit represented by R ¹ R ² ₂ SiO _0.5 ,
D unit: siloxane unit represented by R ¹ R ² SiO _1.0 ,
R ³ M / R ³ D unit: Silalkylene group-containing siloxane unit represented by R ³ _0.5 R ² ₂ SiO _0.5 and a silalkylene group represented by R ³ _0.5 R ² SiO _1.0 At least one siloxane unit selected from contained siloxane units, and T / Q unit: at least one siloxane selected from siloxane units represented by R ² SiO _1.5 and siloxane units represented by SiO _2.0 unit

In the above formula, each R ¹ is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or 1 to 1 carbon atoms. 20 halogen-substituted alkyl groups, aryl groups having 6 to 20 carbon atoms, and halogen-substituted aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, alkoxy groups, hydroxyl groups, or the above structural formula Examples thereof include at least one group selected from epoxy group-containing groups. However, among all the siloxane units, at least one R ¹ is an alkenyl group having 2 to 20 carbon atoms, and examples thereof are the same groups as described above. Among all R ^1, the number of alkenyl groups in the component (A) in the range of 0.20 to 5.00 mol% is preferably an alkenyl group having 2 to 20 carbon atoms. R ¹ is preferably a methyl group, a vinyl group, a hexenyl group, a glycidoxypropyl group or a phenyl group.

In the above formula, each R ² independently represents an alkyl group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 6 to 20 carbon atoms. It is at least one group selected from a halogen-substituted aryl group and an epoxy group-containing group represented by the structural formula, and examples thereof are the same groups as described above. R ² is preferably a methyl group, a phenyl group, a glycidoxypropyl group or a hydroxyl group.

In the above formula, R ³ is a linear or branched alkylene group having 2 to 20 carbon atoms (= silalkylene group) bonded to a silicon atom in another siloxane unit. Examples of the alkylene group include the same groups as described above, and an ethylene group or a hexylene group is preferable. Here, the bonding form with other siloxane units via other silalkylene is mainly as follows. Each terminal O is bonded to a silicon atom in another siloxane unit.

The M unit is a siloxane unit that constitutes the end of the organosilicon compound that is the component (A), and the D unit is a siloxane unit that constitutes a linear polysiloxane structure. In addition, it is preferable that an alkenyl group or a silicon atom-bonded hydrogen atom is present on these M units or D units, particularly preferably M units. On the other hand, the R ³ M unit and the R ³ D unit are bonded to a silicon atom in another siloxane unit through a silalkylene bond and bonded to a silicon atom in another siloxane unit through an oxygen atom. It is. The T / Q unit is a branched siloxane unit that gives a resinous structure to polysiloxane. In the present invention, the (A) component is represented by a siloxane unit represented by R ² SiO _1.5 and a SiO _2.0 unit. It is preferable to contain at least one siloxane unit selected from siloxane units to be prepared. In particular, when it is desired to impart good hot melt properties to the composition, from the viewpoint of adjusting the content of aryl groups in the component (A), the component (A) is a siloxane unit represented by R ² SiO _1.5. In particular, R ² preferably contains a siloxane unit having a phenyl group.

The R ³ M / R ³ D unit is a characteristic structure of the component (A), and represents a structure in which silicon atoms are bridged via a silalkylene group as R ³ . Specifically, from a silalkylene group-containing siloxane unit represented by R ³ _0.5 R ² ₂ SiO _0.5 and a silalkylene group-containing siloxane unit represented by R ³ _0.5 R ² SiO _1.0 It is at least one siloxane unit selected, and at least two of the total siloxane units constituting the component (A) need to be these silalkylene group-containing siloxane units. The preferred bonding form between the siloxane units having a silalkylene group as R ³ is as described above, and the number of R ³ between the two silalkylene group-containing siloxane units is the same as that of oxygen in the M unit. It is expressed as “0.5”. Assuming that the number of R ³ is 1, [O _0.5 R ² ₂ SiR ³ SiR ² ₂ O _0.5 ], [O _0.5 R ² ₂ SiR ³ SiR ² O _1.0 ] and [O _1.0 R ² SiR ³ SiR ² O _1.0 ] is included in the component (A), and at least one selected from structural units of siloxane represented by _1.0 R ² SiR ³ SiR ² O _1.0 ]. Bonds to silicon atoms contained in D, T / Q units. By having such a structure, the component (A) can be designed relatively easily with a chain polysiloxane structure consisting of D units and a resin-like polysiloxane structure containing T / Q units in the molecule. , The physical properties are remarkably excellent.

Such component (A) comprises an organopolysiloxane having at least two alkenyl groups in one molecule and an organopolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule. Number] / [number of moles of silicon-bonded hydrogen atoms]> 1, which can be obtained by a hydrosilylation reaction at a reaction ratio, more preferably, the component (A) is a resin in the molecule. It has a chain siloxane structure and a chain siloxane structure, and at least part of the hydrosilylation-reactive organopolysiloxane is an organopolysiloxane having a resinous siloxane structure, and the other part has a chain siloxane structure. It is preferable that it is the organopolysiloxane which has.

For example, the component (A) is
(A ^R ) At least one siloxane unit selected from a siloxane unit represented by R ² SiO _1.5 and a siloxane unit represented by SiO _2.0 in the molecule (wherein R ² is the same as defined above) And at least one resinous organopolysiloxane having a hydrosilylation reactive functional group selected from an alkenyl group having 2 to 20 carbon atoms and a silicon-bonded hydrogen atom, and
^{(A L)} siloxane units (wherein, ^{R 2} is a is a similar group) represented by ^R ₂ 2 _{SiO 1.0} in the molecule contains, and said ^{(A R)} component hydrosilyl At least one chain organopolysiloxane having a reactive functional group selected from a C2-C20 alkenyl group and a silicon atom-bonded hydrogen atom,
It is an organosilicon compound obtained by reacting at a ratio designed so that an alkenyl group having 2 to 20 carbon atoms in the (A ^R ) component or the (A ^L ) component remains after the hydrosilylation reaction.

When at least a part of the (A ^R ) component is a resinous organopolysiloxane having an alkenyl group having 2 to 20 carbon atoms, at least a part of the (A ^L ) component has a silicon atom-bonded hydrogen atom. A chain organopolysiloxane is preferred.

Similarly, when at least a part of the (A ^R ) component is a resinous organopolysiloxane having a silicon atom-bonded hydrogen atom, at least a part of the (A ^L ) component is an alkenyl having 2 to 20 carbon atoms. A linear organopolysiloxane having a group is preferred.

Such a combination is not particularly limited, but preferably,
(A1): Organopolysiloxane having at least two alkenyl groups having 2 to 20 carbon atoms in the molecule, containing the following component (a1-1) or component (a1-2) (a1-1) Alkenyl group-containing resinous organopolysiloxane represented by the formula: [R ^Vi R ² ₂ SiO _0.5 ] _p [R ² ₃ SiO _0.5 ] _q [R ² SiO _1.5 ] _r [SiO _2.0 ] _s (R ⁵ O _1/2 ) _e
In the formula, R ^Vi is an alkenyl group having 2 to 20 carbon atoms, R ² is an alkyl group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 20 carbon atoms, or 6 to 20 carbon atoms. An aryl group and at least one group selected from a halogen-substituted aryl group having 6 to 20 carbon atoms, a hydroxyl group or an epoxy group, R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and p + q + r + s = 1.0, (p + q) :( r + s) = 0.15-0.70: 0.85-0.30, p> 0, and e is in the range of 0-0.05. Is a number.
(A1-2) Alkenyl group-containing chain organopolysiloxane [R ^Vi R ² ₂ SiO _0.5 ] ₂ [R ² ₂ SiO _1.0 ] t represented by the following structural formula
In the formula, R ^Vi and R ² are the same groups as described above, and t is a number in the range of 1 to 2000.
And (a2): organohydrogenpolysiloxane containing the following component (a2-1) or component (a2-2):
(A2-1) Resin-like or chain-like organohydrogenpolysiloxane having a silicon atom-bonded hydrogen atom at the end of the molecular structure represented by the following structural formula [HR ² ₂ SiO _0.5 ] _u [R ² ₂ SiO _{1 ^{.0] v [R 2 SiO 1.5}} ] w [SiO 2.0] x (R 5 O 1/2) e
In the formula, R ² and R ⁵ are the same groups as described above, u + v + w + x = 1.0, u: (v + w + x) = 0.01 to 0.75: 0.99 to 0.25, and e is It is a number in the range of 0 to 0.05.
(A2-2) Chain-like organohydrogenpolysiloxane having a silicon atom-bonded hydrogen atom in the side chain represented by the following structural formula [R ² ₃ SiO _0.5 ] ₂ [HR ² SiO _1.0 ] _y
Wherein R ² is the same group as described above, and y is a number in the range of 2 to 1000.
In the presence of (a3) hydrosilylation reaction catalyst, 1 mol of alkenyl group having 2 to 20 carbon atoms contained in component (a1) and silicon atom in organohydrogenpolysiloxane in component (a2) The hydrosilylation reaction is preferably carried out in such an amount that the number of moles of bonded hydrogen atoms is 0.2 to 0.7 mole.

The component (a1) may be a mixture having a mass ratio of the component (a1-1) and the component (a1-2) of 100: 0 to 0: 100, and in particular, the alkenyl that is the component (a1-1). It is preferable that the group-containing resinous organopolysiloxane is contained or is independent, and the mass ratio of the component (a1-1) to the component (a1-2) may be 50:50 to 100: 0. It is preferable that it is the range of 40-100: 0. In the case where the component (a1) is composed only of the alkenyl group-containing chain organopolysiloxane which is the component (a1-2), at least a part of the component (a2) is a resinous organoorganism which is the component (a2-1). A hydrogen polysiloxane is preferable.

The component (a2) may be a mixture having a mass ratio of the component (a2-1) and the component (a2-2) of 100: 0 to 0: 100, in particular, the resin that is the component (a2-1). It is preferable that it contains a chain-like or chain-like organohydrogenpolysiloxane or is independent, and the mass ratio of the component (a2-1) to the component (a2-2) may be 50:50 to 100: 0. 75:25 to 100: 0. In addition, when (a2) component consists only of chain | strand-shaped organohydrogenpolysiloxane which is (a2-2) component, at least one part of (a1) component is an alkenyl group containing resin which is (a1-1) component. It is preferable that it is an organopolysiloxane.

More preferably, the component (A) is obtained by reacting the following component (A1-1) or component (A1-2) with the component (A2) in the presence of a catalyst (A3) hydrosilylation reaction. it can.

The component (A1-1) is a polysiloxane containing an alkenyl group and having a relatively large amount of branch units.
Average unit formula:
(R ⁴ ₃ SiO _1/2 ) _a (R ⁴ ₂ SiO _2/2 ) _b (R ⁴ SiO _3/2 ) _c (SiO _4/2 ) _d (R ⁵ O _1/2 ) _e
An organopolysiloxane having at least two alkenyl groups in one molecule.

In the formula, R ⁴ is a halogen-substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and similarly to the above, an alkenyl group having 2 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms. An aryl group having 6 to 20 carbon atoms, a group in which some or all of the hydrogen atoms bonded to these groups are substituted with a halogen atom such as a chlorine atom or a bromine atom, or an epoxy such as a glycidoxypropyl group Examples are a group or a hydroxyl group. Preferably, they are a methyl group, a phenyl group, a vinyl group, a hydroxyl group or an epoxy group. However, at least two of R ⁴ are alkenyl groups having 2 to 20 carbon atoms. Moreover, hot-melt property can be provided to the composition obtained by making 10 mol% or more, preferably 20 mol% or more of all R ⁴ into phenyl groups. R ⁵ in the formula is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In the formula, a is a number in the range of 0 to 0.7, b is a number in the range of 0 to 0.7, c is a number in the range of 0 to 0.9, and d is 0 to 0.7. A number in the range, e is a number in the range of 0 to 0.1, c + d is a number in the range of 0.3 to 0.9, a + b + c + d is 1, and preferably a is 0 to 0.00. A number in the range of 6, b is a number in the range of 0 to 0.6, c is a number in the range of 0 to 0.9, d is a number in the range of 0 to 0.5, e is 0 to 0 A number in the range of 0.05, and c + d is a number in the range of 0.4 to 0.9. This is because the hardness and mechanical strength of the resulting cured product are excellent when a, b, and c + d are numbers within the above ranges.

Specific examples of such (A1-1) component include the following organopolysiloxanes. In the formula, Me, Ph, Vi, and Ep represent a methyl group, a phenyl group, a vinyl group, and a glycidoxypropyl group, respectively.
(ViMe ₂ SiO _1/2 ) _0.25 (PhSiO _3/2 ) _0.75 (HO _1/2 ) _0.02
(ViMe ₂ SiO _1/2 ) _0.25 (PhSiO _3/2 ) _0.75
(ViMe ₂ SiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80
(ViMe ₂ SiO _1/2 ) _0.15 (Me ₃ SiO _1/2 ) _0.38 (SiO _4/2 ) _0.47 (HO _1/2 ) _0.01
(ViMe ₂ SiO _1/2 ) _0.13 (Me ₃ SiO _1/2 ) _0.45 (SiO _4/2 ) _0.42 (HO _1/2 ) _0.01
(ViMe ₂ SiO _1/2 ) _0.15 (PhSiO _3/2 ) _0.85 (HO _1/2 ) _{0.01
(Me 2 SiO 2/2) 0.15 (} MeViSiO 2/2) 0.10 (PhSiO 3/2) 0.75 (HO 1/2) 0.04
(MeViPhSiO _1/2 ) _0.20 (PhSiO _3/2 ) _0.80 (HO _1/2 ) _0.05
(ViMe ₂ SiO _1/2 ) _0.15 (PhSiO _3/2 ) _0.75 (SiO _4/2 ) _0.10 (HO _1/2 ) _0.02
(Ph ₂ SiO _2/2 ) _0.25 (MeViSiO _2/2 ) _0.30 (PhSiO _3/2 ) _0.45 (HO _1/2 ) _0.04
(Me ₃ SiO _1/2 ) _0.20 (ViMePhSiO _1/2 ) _0.40 (SiO _4/2 ) _0.40 (HO _1/2 ) _0.08
(Me ₂ ViSiO _1/2 ) _0.2 (MeEpSiO _2/2 ) _0.25 (PhSiO _3/2 ) _0.55 (HO _1/2 ) _0.005

The component (A1-2) is a polysiloxane containing an alkenyl group having 2 to 20 carbon atoms and having a relatively large amount of chain siloxane units. And a chain polysiloxane having a structure containing disiloxane units in the range of 1 to 1998). Specifically, the component (A1-2) is an average unit formula:
(R ⁴ ₃ SiO _1/2 ) _f (R ⁴ ₂ SiO _2/2 ) _g (R ⁴ SiO _3/2 ) _h (SiO _4/2 ) _i (R ⁵ O _1/2 ) _j
An organopolysiloxane having at least two alkenyl groups in one molecule. In the formula, R ⁴ and R ⁵ are the same groups as described above.

In the formula, f is a number in the range of 0.001 to 0.7, g is a number in the range of 0.3 to 0.999, h is a number in the range of 0 to 0.2, and i is 0 to 0. A number in the range of 0.2, j is a number in the range of 0 to 0.1, h + i is a number in the range of 0 to 0.2, f + g + h + i is 1, and preferably f is 0. A number in the range of 002 to 0.70, g is a number in the range of 0.3 to 0.998, more preferably f is a number in the range of 0.01 to 0.70, g is A number in the range of 0.3 to 0.99, particularly preferably f is a number in the range of 0.01 to 0.30 and g is a number in the range of 0.4 to 0.99. is there. Preferably, h is a number in the range of 0 to 0.1, i is a number in the range of 0 to 0.1, j is a number in the range of 0 to 0.05, and h + i is 0. It is a number in the range of ~ 0.1. This is because toughness can be imparted to the resulting cured product when f, g, h, and i are numbers within the above ranges.

Specific examples of the component (A1-2) include the following organopolysiloxanes. In the formula, Me, Ph, and Vi represent a methyl group, a phenyl group, and a vinyl group, respectively.
ViMe ₂ SiO (SiMePhO) ₁₈ SiMe ₂ Vi, ie, (ViMe ₂ SiO _1/2 ) _0.10 (MePhSiO _2/2 ) _0.90
ViMe ₂ SiO (SiMePhO) ₃₀ SiMe ₂ Vi, ie, (ViMe ₂ SiO _1/2 ) _0.063 (MePhSiO _2/2 ) _0.937
ViMe ₂ SiO (SiMePhO) ₁₅₀ SiMe ₂ Vi, ie, (ViMe ₂ SiO _1/2 ) _0.013 (MePhSiO _2/2 ) _0.987
ViMe ₂ SiO (SiMe ₂ O) ₁₈ SiMe ₂ Vi, ie, (ViMe ₂ SiO _1/2 ) _0.10 (Me ₂ SiO _2/2 ) _0.90
ViMe ₂ SiO (SiMe ₂ O) ₃₀ SiMe ₂ Vi, ie, (ViMe ₂ SiO _1/2 ) _0.063 (Me ₂ SiO _2/2 ) _0.937
ViMe ₂ SiO (SiMe ₂ O) ₃₅ (SiMePhO) ₁₃ SiMe ₂ Vi, ie, (ViMe ₂ SiO _1/2 ) _0.04 (Me ₂ SiO _2/2 ) _0.70 (MePhSiO _2/2 ) _0.26
ViMe ₂ SiO (SiMe ₂ O) ₁₀ SiMe ₂ Vi, ie, (ViMe ₂ SiO _1/2 ) _0.17 (Me ₂ SiO _2/2 ) _0.83
(ViMe ₂ SiO _1/2 ) _0.10 (MePhSiO _2/2 ) _0.80 (PhSiO _3/2 ) _0.10 (HO _1/2 ) _0.02
(ViMe ₂ SiO _1/2 ) _0.20 (MePhSiO _2/2 ) _0.70 (SiO _4/2 ) _0.10 (HO _1/2 ) _0.01
HOMe ₂ SiO (MeViSiO) ₂₀ SiMe ₂ OH
Me ₂ ViSiO (MePhSiO) ₃₀ SiMe ₂ Vi
Me ₂ ViSiO (Me ₂ SiO) ₁₅₀ SiMe ₂ Vi

The component (A1-1) is essential from the viewpoint of imparting hardness and mechanical strength to the obtained cured product. The component (A1-2) can be added as an optional component from the viewpoint that toughness can be imparted to the resulting cured product, but when using a crosslinking agent having many chain siloxane units in the following component (A2) You may substitute. In any case, the mass ratio of the component having many branched siloxane units and the component having many chain siloxane units is preferably 50:50 to 100: 0, and more preferably 60: 40-100: 0. This is because the hardness and mechanical strength of the resulting cured product are improved when the mass ratio of the component having many branched siloxane units and the component having many chain siloxane units is within the above range. is there.

  The component (A2) is a component for crosslinking the component (A1-1) or the component (A1-2), and is an organopolysiloxane containing at least two silicon-bonded hydrogen atoms in one molecule. (A2) As a group couple | bonded with silicon atoms other than a hydrogen atom in a component, a C1-C20 alkyl group, a C1-C20 halogen substituted alkyl group, a C6-C20 aryl group And at least one group selected from a halogen-substituted aryl group having 6 to 20 carbon atoms or a hydroxyl group.

Such component (A2) is not limited, but preferably the average composition formula:
R ⁶ _k H _m SiO _{(4-km) / 2}
It is the organohydrogen polysiloxane represented by these.

In the formula, R ⁶ is a halogen-substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and the same alkyl group having 1 to 12 carbon atoms and aryl group having 6 to 20 carbon atoms as described above. , Aralkyl groups having 7 to 20 carbon atoms, and groups or hydroxyl groups in which some or all of the hydrogen atoms bonded to these groups are substituted with halogen atoms such as chlorine atoms and bromine atoms, preferably methyl. Group, phenyl group or hydroxyl group.

  In the formula, k is a number in the range of 1.0 to 2.5, preferably a number in the range of 1.2 to 2.3, and m is a number in the range of 0.01 to 0.9. Preferably, it is a number in the range of 0.05 to 0.8, and k + m is a number in the range of 1.5 to 3.0, preferably in the range of 2.0 to 2.7.

The component (A2) may be a resinous organohydrogenpolysiloxane having many branched siloxane units, or may be a chain organohydrogenpolysiloxane having many chain siloxane units. Specifically, the component (A2) is exemplified by organohydrogenpolysiloxane represented by the following (A2-1) or (A2-2) or a mixture thereof.

(A2-1) Resin-like organohydrogenpolysiloxane having a silicon atom-bonded hydrogen atom at the end of the molecular structure represented by the following structural formula [HR ² ₂ SiO _0.5 ] _u [R ² ₂ SiO _1.0 ] _v [R ² SiO _1.5 ] _w [SiO _2.0 ] _x (R ⁵ O _1/2 ) _e
In the formula, from an alkyl group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a halogen-substituted aryl group having 6 to 20 carbon atoms or a hydroxyl group At least one group selected, R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, u + v + w + x = 1.0, and u: (v + w + x) = 0.01 to 0.75: 0.99 to 0.25, and e is a number in the range of 0 to 0.05.

(A2-2) Chain organohydrogenpolysiloxane having a silicon atom-bonded hydrogen atom in the side chain represented by the following structural formula [R ² ₃ SiO _0.5 ] ₂ [HR ² SiO _1.0 ] _y
In the formula, R ² is the same group as described above, and y is a number in the range of 2 to 1,000.

As described above, in the composition of the present invention, the resinous organopolysiloxane having many branched siloxane units gives the cured product hardness and mechanical strength, and the resulting organopolysiloxane having many chain siloxane units is Since the toughness is imparted to the cured product, the (A2-1) component and the (A2-2) component are appropriately determined as the (A2) component according to the type of the (A) component. sell. Specifically, when there are few branched siloxane units in the component (A1), the crosslinking agent mainly comprises the resinous organohydrogenpolysiloxane as the component (A2-1) as the component (A2). In the case where there are few chain siloxane units in the component (A1), it is preferable to use a crosslinking agent mainly composed of the chain organohydrogenpolysiloxane as the component (A2-2). preferable. The component (A2) corresponding to the component (A1) is preferably the component (A2-1), the component (A2-2), or a mixture thereof, preferably the component (A2-1) And the mass ratio of the component (A2-2) is 50:50 to 100: 0, and more preferably 60:40 to 100: 0.

Specific examples of such component (A2) include the following organopolysiloxanes. In the formula, Me and Ph represent a methyl group and a phenyl group, respectively.
Ph ₂ Si (OSiMe ₂ H) ₂ , ie, Ph _0.67 Me _1.33 H _0.67 SiO _0.67
HMe ₂ SiO (Me ₂ SiO) ₂₀ SiMe ₂ H, ie, Me _2.00 H _0.09 SiO _0.95
HMe ₂ SiO (Me ₂ SiO) ₅₅ SiMe ₂ H,
PhSi (OSiMe ₂ H) ₃ , ie, Ph _0.25 Me _1.50 H _0.75 SiO _0.75
(HMe ₂ SiO _1/2 ) _0.6 (PhSiO _3/2 ) _0.4 , ie Ph _0.40 Me _1.20 H _0.60 SiO _0.90

  The amount of the component (A2) added is 1 mol of the alkenyl group having 2 to 20 carbon atoms in the components (A1-1) and (A1-2) (hereinafter referred to as “(A1) component”). (A2) The amount of silicon-bonded hydrogen atoms in the component is 0.2 to 0.7 mol, and preferably 0.3 to 0.6 mol. This is because the initial hardness and mechanical strength of the resulting cured product are good when the amount of component (A2) added is within the above range.

  The component (A3) is a hydrosilylation reaction catalyst for promoting the hydrosilylation reaction of the component (A1-1) or the components (A1-2) and (A2). Examples of such component (A3) include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts, and platinum-based catalysts are preferred because they can significantly accelerate the curing of the composition. Examples of the platinum-based catalyst include platinum fine powder, chloroplatinic acid, chloroplatinic acid alcohol solution, platinum-alkenylsiloxane complex, platinum-olefin complex, and platinum-carbonyl complex, and platinum-alkenylsiloxane complex is particularly preferable. . As this alkenylsiloxane, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, Examples thereof include alkenyl siloxanes in which part of the methyl groups of these alkenyl siloxanes are substituted with ethyl groups, phenyl groups, and the like, and alkenyl siloxanes in which the vinyl groups of these alkenyl siloxanes are substituted with allyl groups, hexenyl groups, and the like. In particular, since the stability of this platinum-alkenylsiloxane complex is good, 1,3-divinyl-1,1,3,3-teramethyldisiloxane is preferable.

  The addition amount of the component (A3) is an amount that promotes the hydrosilylation reaction of the component (A1-1) or the component (A1-2) and the component (A2), specifically, the component (A1-1) or ( It is preferable that the amount of metal atoms in this component is in the range of 0.01 to 500 ppm in terms of mass unit with respect to the total amount of component A1-2) and component (A2). The amount is preferably in the range of -100 ppm, and particularly preferably in the range of 0.01-50 ppm. This is because when the amount of the component (A3) is at least the lower limit of the above range, the hydrosilylation reaction of these components can be sufficiently promoted. This is because problems such as coloring are less likely to occur in objects.

  When mixing and reacting the above components (A1) to (A3), if the compound and the component A after the reaction can be handled as a liquid or paste, after mixing using a kneader such as a dental mixer or a loss mixer, The reaction may be carried out by applying heat, but when the blend itself or the component (A) after the reaction is solid, the blending and reaction may be carried out in the presence of an organic solvent. However, this solvent must not inhibit the hydrosilylation reaction. Alcohol solvents and solvents having a carbon-oxygen double bond may react with each other to produce by-products. Is preferred. Specific examples of the solvent include aliphatic hydrocarbons such as n-hexane, cyclohexane, and n-heptane; aromatic hydrocarbons such as toluene, xylene, and mesitylene; ethers such as tetrahydrofuran and dipropyl ether; hexamethyldisiloxane And silicones such as octamethyltrisiloxane and decamethyltetrasiloxane; esters such as ethyl acetate, butyl acetate and propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. This solvent can be removed by evaporation after the hydrosilylation reaction.

(A) component of this invention can be synthesize | combined by the said method, However, (B) In the presence of the peroxide mentioned later, hydrosilylation reaction is performed and (A) component is prepared in a system. Alternatively, after synthesizing the component (A) in advance, a peroxide (B) described later may be added. However, when synthesizing the component (A) in the presence of the component (B), the reaction temperature needs to be low enough not to activate the component (B). Examples of such reaction conditions include, for example, about 1 to 3 hours at 80 to 100 ° C.

[Peroxide (component (B))]
The curable silicone composition according to the present invention comprises the component (A) and a peroxide (B). The component (B) is a component that gives a cured product by cross-linking the alkenyl group in the liquid or hot melt component (A) at a high temperature, and the physical strength is greatly reduced even at a high temperature of 250 ° C. or higher. Gives the feature of not. Such a peroxide is not particularly limited, but an organic compound having a 10-hour half-life temperature of 90 ° C. or higher from the viewpoint of controlling the multistage curing reaction and improving durability at a high temperature of 250 ° C. or higher. A peroxide is particularly preferred. When the 10-hour half-life temperature is less than the lower limit, the thermosetting reaction by the peroxide proceeds during the hydrosilylation reaction or when the peroxide is kneaded into the component (A), and the curable silicone composition that can be handled. May not be obtained, or improvement in durability at a high temperature of 250 ° C. or higher may be insufficient.

Examples of the peroxide as component (B) include alkyl peroxides, diacyl peroxides, peroxide esters and peroxide carbonates.

Examples of alkyl peroxides include dicumyl peroxide, di-tert-butyl peroxide, di-tert-butylcumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane. 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, tert-butylcumyl, 1,3-bis (tert-butylperoxyisopropyl) benzene, 3,6,9-triethyl- 3,6,9-trimethyl-1,4,7-triperoxonane and the like can be mentioned.

Examples of the diacyl peroxides include benzoyl peroxide, lauroyl peroxide, decanoyl peroxide, and the like. Examples of peroxide esters include 1,1,3,3-tetramethylbutylperoxyneodecanoate, α-cumylperoxyneodecanoate, tert-butylperoxyneodecanoate, and tert-butyl. Peroxyneoheptanoate, tert-butyl peroxypivalate, tert-hexyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, tert-amyl peroxyl- 2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, di-tert-butylperoxyhexahydroterephthalate, tert-amylperoxy3,5,5 -Trimethylhexanoate, tert-butyl Oxy 3,5,5-trimethyl hexanoate, tert- butylperoxy acetate, tert- butyl peroxybenzoate, di - butylperoxy trimethyl Adi adipate, and the like.

Examples of the peroxide carbonates include di-3-methoxybutyl peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, diisopropyl peroxycarbonate, tert-butylperoxyisopropyl carbonate, and di (4-tert- Butylcyclohexyl) peroxydicarbonate, dicetylperoxydicarbonate, dimyristylperoxydicarbonate and the like.

Of these, alkyl peroxides are preferably used, and those having a half-life of 10 hours are preferably 90 ° C or higher, more preferably 95 ° C or higher. Such peroxides include dicumyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (tert -Butylperoxy) hexane, 1,3-bis (tert-butylperoxyisopropyl) benzene, di- (2-tert-butylperoxyisopropyl) benzene, 3,6,9-triethyl-3,6,9-trimethyl -1,4,7-triperoxonan.

The amount of the component (B) added is not particularly limited, but may be in the range of 0.05 to 10 parts by mass with respect to 100 parts by mass of the component (A). A range of parts by mass is preferred.

The component (B) may be added to the component (A) prepared in advance, and as described above, only the component (A) is synthesized by a hydrosilylation reaction in the state of coexisting with each raw material of the component (A). May be.

[Inorganic filler (component (C))]
The composition of the present invention preferably contains an inorganic filler from the viewpoint of mechanical strength, functionality and handling workability. The inorganic filler is preferably at least one selected from reinforcing fillers, white pigments, thermally conductive fillers, conductive fillers and phosphors. In particular, the composition of the present invention is used as a sealant, protective agent or adhesive. When used in applications, it is preferable to contain a reinforcing filler. Moreover, when using for the wavelength conversion material of LED, use of a fluorescent substance is preferable. Moreover, when using as a light reflection material for LED, use of a white pigment is preferable.

Although content in particular of an inorganic filler is not restrict | limited, It is preferable to contain in the range of 10-2000 mass parts with respect to 100 mass parts of (A) component, and it is the range of 100-1500 mass parts. Particularly preferred from the viewpoint of the hardness and mechanical strength of the cured product.

The reinforcing filler is a component for imparting mechanical strength to a cured product obtained by curing the present composition and improving the performance as a protective agent or an adhesive. Examples of such reinforcing fillers include fumed silica fine powder, precipitated silica fine powder, fused silica fine powder, calcined silica fine powder, fumed titanium dioxide fine powder, quartz fine powder, calcium carbonate fine powder. Examples include inorganic fillers such as powder, diatomaceous earth fine powder, aluminum oxide fine powder, aluminum hydroxide fine powder, zinc oxide fine powder, zinc carbonate fine powder, glass fiber, and carbon fiber. These inorganic fillers An organoalkoxysilane such as methyltrimethoxysilane, an organohalosilane such as trimethylchlorosilane, an organosilazane such as hexamethyldisilazane, an α, ω-silanol-blocked dimethylsiloxane oligomer, an α, ω-silanol-blocked methylphenylsiloxane oligomer , Α, ω-silanol group-blocked methylvinylsiloxa The inorganic filler surface treated by a treatment agent such as a siloxane oligomer such as an oligomer may contain. In particular, organopolysiloxane having a low polymerization degree having silanol groups at both ends of the molecular chain, preferably α, ω-silanol group-capped dimethylpolysiloxane having no reactive functional group other than the terminal silanol group in the molecule. The surface of the inorganic filler may be treated in advance.

The particle size of the fine powder of the reinforcing filler is not particularly limited, but may be, for example, in the range of 0.01 μm to 1000 μm in median diameter by laser diffraction scattering type particle size distribution measurement.

  The white pigment is a component that is added when the whiteness of the composition is increased and the cured product is used as a light reflecting material for an optical semiconductor device. Examples of such white pigments include metal oxides such as titanium oxide, alumina, zinc oxide, zircon oxide, and magnesium oxide, barium sulfate, zinc sulfate, barium titanate, aluminum nitride, boron nitride, and antimony oxide. Titanium oxide is preferable because of its high light reflectivity and concealability, and alumina, zinc oxide, and barium titanate are preferable because of its high light reflectivity in the UV region. The average particle diameter and shape of the white pigment are not limited, but the average particle diameter is preferably in the range of 0.05 to 10.0 μm, and particularly in the range of 0.1 to 5.0 μm. preferable. Further, this white pigment may be surface-treated with a silane coupling agent, silica, alumina or the like in the same manner as the reinforcing filler.

Thermally conductive filler or conductive filler is a component that imparts thermal conductivity or electrical conductivity to a cured silicone rubber obtained by curing the present composition, if desired, such as gold, silver, nickel, copper, etc. Metal fine powder: Fine powder obtained by depositing or plating a metal such as gold, silver, nickel, copper or the like on the surface of fine powder such as ceramic, glass, quartz, organic resin; metal compound such as aluminum oxide, aluminum nitride, zinc oxide, and the like A mixture of two or more of these is exemplified. Particularly preferred are silver powder, aluminum powder, aluminum oxide powder, zinc oxide powder, aluminum nitride powder or graphite. When the composition is required to have electrical insulation, it is preferably a metal oxide powder or a metal nitride powder, particularly an aluminum oxide powder, a zinc oxide powder, or an aluminum nitride powder. Preferably there is.

[Phosphor]
Furthermore, the present composition may contain a phosphor in order to convert the emission wavelength from the optical semiconductor element. Examples of the phosphor include oxide phosphors, oxynitride phosphors, nitride phosphors, sulfide phosphors, and oxysulfide phosphors that are widely used in light emitting diodes (LEDs). And yellow, red, green, and blue light emitting phosphors. Examples of oxide phosphors include yttrium, aluminum, and garnet-based YAG green to yellow light-emitting phosphors containing cerium ions, terbium, aluminum, garnet-based TAG yellow light-emitting phosphors including cerium ions, and Examples include silicate green to yellow light emitting phosphors containing cerium and europium ions. Examples of the oxynitride phosphor include silicon, aluminum, oxygen, and nitrogen-based sialon-based red to green light-emitting phosphors containing europium ions. Examples of nitride-based phosphors include calcium, strontium, aluminum, silicon, and nitrogen-based casoon-based red light-emitting phosphors containing europium ions. Examples of sulfide-based phosphors include ZnS-based green color phosphors including copper ions and aluminum ions. Examples of oxysulfide phosphors include Y ₂ O ₂ S red light-emitting phosphors containing europium ions. Two or more of these phosphors may be used in combination.

[One or more selected from a reaction inhibitor, an adhesion-imparting agent, and a heat-resistance imparting agent (component (D))]
In this composition, as other optional components, 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, etc. Alkyne alcohols; enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; 1,3,5,7-tetramethyl-1,3,5 , 7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, and a reaction inhibitor such as benzotriazole.

  The composition may contain an adhesion-imparting agent for improving its adhesiveness as other optional components. This adhesion-imparting agent may be an organosilicon compound having at least one alkoxy group bonded to a silicon atom in one molecule, and is a resinous organopolysiloxane exemplified as a raw material for the component (A). It may have an epoxy group or the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a methoxyethoxy group, and a methoxy group is particularly preferable. Examples of the group other than the alkoxy group bonded to the silicon atom of the organosilicon compound include halogen-substituted or unsubstituted monovalent hydrocarbon groups such as an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and a halogenated alkyl group; Glycidoxyalkyl groups such as 3-glycidoxypropyl group and 4-glycidoxybutyl group; 2- (3,4-epoxycyclohexyl) ethyl group, 3- (3,4-epoxycyclohexyl) propyl group and the like Examples include epoxycyclohexylalkyl groups; epoxyalkyl groups such as 3,4-epoxybutyl groups and 7,8-epoxyoctyl groups; acrylic group-containing monovalent organic groups such as 3-methacryloxypropyl groups; and hydrogen atoms. This organosilicon compound preferably has an alkenyl group or a group capable of reacting with a silicon atom-bonded hydrogen atom in the composition, and specifically, preferably has a silicon atom-bonded hydrogen atom or an alkenyl group. Moreover, since it can provide favorable adhesiveness to various types of substrates, the organosilicon compound preferably has at least one epoxy group-containing monovalent organic group in one molecule. Examples of such organosilicon compounds include organosilane compounds, organosiloxane oligomers, and alkyl silicates. Examples of the molecular structure of the organosiloxane oligomer or alkyl silicate include linear, partially branched linear, branched, cyclic, and network, particularly linear, branched, and network. Preferably there is. Examples of such organosilicon compounds include silane compounds such as 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane; A siloxane compound having at least one silicon atom-bonded alkenyl group or silicon atom-bonded hydrogen atom and silicon atom-bonded alkoxy group, and a silane compound or siloxane compound having at least one silicon atom-bonded alkoxy group and silicon in one molecule. Mixtures of siloxane compounds having at least one atom-bonded hydroxy group and at least one silicon-bonded alkenyl group, methyl polysilicate, ethyl polysilicate, epoxy group-containing ethyl polysilicate, JP-A-10-19508 The carbacyltolane derivative formed by cyclization by an alcohol exchange reaction when reacting an alkoxysilane having an amino group-containing organic group and an alkoxysilane having an epoxy group-containing organic group is exemplified by The The adhesion-imparting agent is preferably a low-viscosity liquid, and the viscosity is not limited, but is preferably in the range of 1 to 500 mPa · s at 25 ° C. Moreover, in this composition, although content of this adhesion | attachment imparting agent is not limited, It is preferable to exist in the range of 0.01-10 mass parts with respect to a total of 100 mass parts of this composition.

The composition may contain a heat resistance imparting agent such as iron oxide (Bengara), cerium oxide, cerium dimethylsilanolate, fatty acid cerium salt, cerium hydroxide, zirconium compound and the like.

In addition, as long as the object of the present invention is not impaired, the present composition includes, as other optional components, a silicone component having no silicon atom-bonded hydrogen atom; fine organic resin powder such as polymethacrylate resin; heat-resistant agent, dye, You may contain pigments other than white and a flame-retarding imparting agent.

In particular, the present composition may contain a release agent from the viewpoint of obtaining good releasability from the mold during molding. There is no restriction | limiting in particular as a mold release agent, A conventionally well-known thing can be used. Specific examples include higher fatty acids such as carnauba wax, montanic acid, stearic acid, higher fatty acid metal salts, fatty acid ester waxes, polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. These release agents may be used alone or in combination of two or more. Among these, higher fatty acid metal salts and fatty acid ester waxes are preferable. Examples of commercially available products include calcium salt, magnesium salt, zinc salt of stearic acid and montanic acid, and EW-440W manufactured by Riken Vitamin.

The curable silicone composition of the present invention can be produced by uniformly mixing the components (A), (B), (C), (D) and other optional components. It is also produced by uniformly mixing the raw materials of component A) and components (B) and (C), (D) and other optional components, and then synthesizing component (A) in the system by heating or the like. be able to. As described above, the reaction condition during the synthesis of the component (A) is preferably about 80 to 100 ° C. so that the component (B) is not activated. The mixing method of each component may be a conventionally known method and is not particularly limited, but usually a simple mixture is obtained by simple stirring. Moreover, when solid components, such as an inorganic filler, are included as arbitrary components, mixing using a mixing apparatus is more preferable. Such a mixing device is not particularly limited, and examples thereof include a single-screw or twin-screw continuous mixer, a two-roll, a loss mixer, a Hobart mixer, a dental mixer, a planetary mixer, a kneader mixer, and a Henschel mixer.

The curable silicone composition of the present invention may be either solid or liquid at 25 ° C., but when it is solid, it preferably has “hot melt property” that melts at a high temperature. A suitable hot-melt property is a solid that does not stick at room temperature, but more specifically, the curing reactive organopolysiloxane composition is non-flowable at 25 ° C. and has a melt viscosity of 8000 Pa at 100 ° C. -S or less.

Here, the non-fluidity means that it does not deform or flow in an unloaded state, and preferably, when it is molded into a tablet or the like, it does not deform or flow in an unloaded state at 25 ° C. . Such non-flowability can be evaluated by, for example, placing a curable silicone composition molded on a hot plate at 25 ° C. and substantially not deforming or flowing even when no load or a constant load is applied. is there. This is because if it is non-flowable at 25 ° C., a hot-melt curable silicone composition having good shape retention at the temperature and low surface tackiness can be obtained.

When the curable silicone composition of the present invention has hot melt properties, it preferably has a softening point in the range of 25 ° C. to 100 ° C. and deforms at 25 ° C. under no load or constant load. -Preferably it does not flow. Such a softening point is when the amount of deformation of the composition is measured after removing the load on a hot plate set in a range of 25 ° C. to 100 ° C. with a load of 100 grams for 10 seconds from the top. It means that the temperature at which the deformation in the height direction is 1 mm or more is in the range of 25 ° C. (however, not including 25 ° C.) to 100 ° C.

When the curable silicone composition of the present invention has hot melt properties, the melt viscosity at 100 ° C. is 8000 Pa · s or less, 5000 Pa · s or less, 4,000 Pa · s or less, more preferably 3,750 Pa · s. s or less, and most preferably in the range of 10 to 3,750 Pa · s. Within the above range, the fluidity at the time of hot melt is good and the mold flowability is improved. Furthermore, after hot-melting, a hot-melt curing-reactive organopolysiloxane composition having good adhesion to the substrate after cooling to 25 ° C. is obtained. Here, the melt viscosity can be measured with a rheometer AR2000EX (manufactured by TA Instruments Japan Co., Ltd.) or the like.

More preferably, the curable silicone composition preferably has a melt viscosity at 130 ° C. of 4000 Pa · s or less, particularly preferably 3000 Pa · s or less, 2000 Pa · s or less, or 1750 Pa · s or less. When the melt viscosity at 130 ° C. is in the above range in addition to the above melt characteristics at 100 ° C., the hot fluidity is excellent, and the hot adhesion is good after hot-melting and cooling to 25 ° C. This is because a meltable curable silicone composition is obtained.

Regarding the non-flowability and hot-melt property of the curable silicone composition of the present invention, for example, the ring-and-ball method of a hot-melt adhesive specified in JIS K 6863-1994 “Testing method for softening point of hot-melt adhesive” It is also preferred that the softening point needs to be higher than 25 ° C. in order to show a state below the softening point measured by the softening point test method according to, ie, to be non-flowable at 25 ° C. This is because if it is non-flowable at 25 ° C., a hot-melt curable silicone composition having good shape retention at the temperature and low surface tackiness can be obtained. The curable silicone composition of the present invention preferably has a melt viscosity of 3,000 Pa · s or higher at 50 ° C., and the melt viscosity at 50 ° C. is 20 times or more the melt viscosity at 100 ° C. It is preferable that it is 25 times or more. This is because the melt viscosity at 50 ° C. is not less than the above lower limit, or the melt viscosity at 50 ° C. is not less than the above lower limit with respect to the melt viscosity at 100 ° C. This is because the properties are low and good hot melt properties are exhibited.

The composition is preferably cured to form a cured product having a Type D durometer hardness of 60 or more at 25 ° C. This is because when the type D durometer hardness at 25 ° C. of the cured product is equal to or higher than the above lower limit, the cured product exhibits sufficient hardness as a sealing agent for semiconductors and the like. The type D durometer hardness is determined by a type D durometer according to JIS K 6253-1997 “Hardness test method for vulcanized rubber and thermoplastic rubber”.

[Semiconductor sealant]
The curable silicone composition of the present invention is useful as a sealing agent for semiconductors and can be used as a paste tablet or a semi-cured (B-stage) molding tablet. Common molding techniques include transfer molding, injection molding, and compression molding. For example, in transfer molding, the paste can be obtained by filling the paste or molding tablet into a plunger of a molding machine and performing automatic molding. As the molding machine, any of an auxiliary ram type molding machine, a slide type molding machine, a double ram type molding machine, and a low pressure sealing molding machine can be used.

In particular, the composition of the present invention can be suitably used for sealing semiconductor elements (including optical semiconductor elements). The semiconductor element can be sealed by applying the composition onto the semiconductor element and curing the composition or the tablet. Examples of the semiconductor element include elements for power semiconductors such as SiC and GaN. Examples of the optical semiconductor element include elements typified by light-emitting diodes, photodiodes, phototransistors, and laser diodes.

In addition, the curable silicone composition according to the present invention can be used as a light reflecting material for optical semiconductor devices, an electrical / electronic adhesive, a potting agent, a protective agent, a coating agent, and an underfill agent.

Next, the cured product of the present invention will be described in detail. The cured product of the present invention is obtained by curing the above curable silicone composition. The shape of the cured product of the present invention is not particularly limited, and can be various shapes depending on the molding machine used. The cured product of the present invention can be handled alone, but can also be handled in a state of covering or sealing a semiconductor element, an optical semiconductor element or the like.

  The curable silicone composition of this invention is demonstrated in detail by an Example and a comparative example. Whether or not the composition exhibits hot-melt properties is confirmed by whether it melts at 100 ° C. when it is solid after confirming whether it is solid or liquid at room temperature, and if possible, its viscosity Was measured. In the formula, Me, Ph, and Vi represent a methyl group, a phenyl group, and a vinyl group, respectively.

<Measurement method and evaluation criteria>
In each composition according to the following examples or comparative examples, the hardness, bending strength, and bending strength after the heat resistance test of the cured product were measured as follows, and the results are shown in Table 1 and Table 2. Indicated.

[Hardness of cured product]
The curable silicone composition was heated at 150 ° C. for 2 hours to prepare a cured product. The hardness of the cured product was measured with a type D durometer specified in JIS K 7215-1986 “Method for testing the durometer hardness of plastics”.

[Bending fracture strength of cured product]
The curable silicone composition was heated at 150 ° C. for 2 hours to prepare a cured product. The bending strength of the cured product was measured by the method specified in JIS K 6911-1995 “General Test Method for Thermosetting Plastics”.

[Bending fracture strength of cured product after heat test]
The curable silicone composition was heated at 150 ° C. for 2 hours to prepare a cured product. This cured product was put into an oven at 300 ° C. and aged for 1 week. Next, the bending strength of the cured product after aging was measured by the method specified in JIS K 6911-1995 “General Test Method for Thermosetting Plastics”.

[Softening point]
The composition was molded into a cylindrical tablet of φ13 mm × 18 mm. This tablet was placed on a hot plate set at 25 ° C. to 100 ° C., and continuously pressed for 10 seconds from the top with a load of 100 gram weight. After removing the load, the amount of deformation of the composition was measured. The temperature at which the amount of deformation in the height direction was 1 mm or more was taken as the softening point.

[Melt viscosity]
Regarding the composition having hot melt properties, the melt viscosity at 100 ° C. was measured at a shear rate of 1 (1 / s) using a rheometer AR2000EX (manufactured by TA Instruments Japan Co., Ltd.).

<Raw material components used in Examples / Comparative Examples>
In the following examples and comparative examples, the following raw material components were used.

[(A1 ^R ): Vinyl group-containing resinous siloxane]
(A1 ^R- 1) component: white solid at 25 ° C., toluene-soluble average unit formula:
(PhSiO _3/2 ) _0.75 (Me ₂ ViSiO _1/2 ) _0.25
An organopolysiloxane having two or more vinyl groups in one molecule (vinyl group content = 5.6% by mass)
(A1 ^R- 2) Component: Average unit formula that is white solid at 25 ° C. and is soluble in toluene:
(PhSiO _3/2 ) _0.80 (Me ₂ ViSiO _1/2 ) _0.20
An organopolysiloxane having two or more vinyl groups in one molecule (vinyl group content = 4.4% by mass)
(A1 ^R- 3) Component: A white solid at 25 ° C. and soluble in toluene. Average unit formula:
(Me ₂ ViSiO _1/2 ) _0.15 (Me ₃ SiO _1/2 ) _0.38 (SiO _4/2 ) _0.47 (HO _1/2 ) _0.01
An organopolysiloxane having two or more vinyl groups in one molecule (vinyl group content = 4.2 mass%)
(A1 ^R- 4) component: white solid at 25 ° C., toluene soluble, average unit formula:
(Me ₂ ViSiO _1/2 ) _0.13 (Me ₃ SiO _1/2 ) _0.45 (SiO _4/2 ) _0.42 (HO _1/2 ) _0.01
An organopolysiloxane resin having two or more vinyl groups in one molecule represented by (content of vinyl group = 3.4% by mass)

[(A1 ^L ): Vinyl group-containing linear siloxane]
(A1 ^L- 1) component:
The viscosity is 1,000 mPa · s,
Average formula Me ₂ ViSiO (MePhSiO) ₃₀ SiMe ₂ Vi
Dimethylvinylsiloxy group-blocked methylphenylpolysiloxane (both vinyl group content = 1.27% by mass)
(A1 ^L- 2) component:
The viscosity is 300 mPa · s,
Average formula Me ₂ ViSiO (Me ₂ SiO) ₁₅₀ SiMe ₂ Vi
Dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends of the molecular chain represented by the formula (vinyl group content = 0.48 mass%)

^[(A2 H): organo Jairo polysiloxane]
^(A2 H -1 ^L) component:
Average formula HMe ₂ SiO (Ph ₂ SiO) SiMe ₂ H
Dimethylhydrogensiloxy group-blocked diphenylpolysiloxane having a viscosity of 5 mPa · s and having a viscosity of 5 mPa · s (content of silicon-bonded hydrogen atoms = 0.6 wt%)
^(A2 H -2 ^R) component:
Average unit formula (PhSiO _3/2 ) _0.4 (HMe ₂ SiO1 / 2) _0.6
A branched organopolysiloxane having a viscosity of 25 mPa · s and having two or more silicon-bonded hydrogen atoms in one molecule (content of silicon-bonded hydrogen atoms = 0.65% by mass)
^(A2 H -3 ^L) component:
Average formula Me ₃ SiO (MeHSiO) ₅₅ SiMe ₃
Polymethylhydrogensiloxane blocked with trimethylsiloxy group-blocked polymethylhydrogensiloxane having a viscosity of 20 mPa · s and having a viscosity of 20 mPa · s (content of silicon-bonded hydrogen atoms = 1.6% by mass)
^(A2 H -4 ^L) component:
Average formula Me ₃ SiO (MeHSIO) ₁₅ SiMe ₃
A dimethylsiloxane-methylhydrogensiloxane copolymer blocked with a trimethylsiloxy group at both ends of a molecular chain having a viscosity of 5 mPa · s (content of silicon atom-bonded hydrogen atom = 1.42% by mass)

[(A3): Hydrosilylation reaction catalyst]
(A3) component: 1,3-divinyltetramethyldisiloxane solution of platinum, 1,3-divinyltetramethyldisiloxane complex (platinum metal content = about 4000 ppm)

[(B): Peroxide]
Component (B1): 2,5-dimethyl-2,5-di (t-butylperoxy) hexane * The temperature at which the half-life is 10 hours is 118 ° C.
Component (B2): 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane * The temperature at which the half-life is 10 hours is 125 ° C.

[(C): Inorganic filler]
Component (C1): spherical silica having an average particle diameter of 15 μm (HS-202 manufactured by Nippon Steel Materials Micron)
Component (C2): spherical silica having an average particle size of 50 μm (HS-104 manufactured by Nippon Steel Materials Micron)
Component (C3): Spherical silica (SP-60 manufactured by Nippon Steel Materials Micron) having an average particle size of 2.5 μm was used.
Component (C4): titanium oxide having an average particle size of 0.5 μm (SX-3103 manufactured by Sakai Chemical Co., Ltd.)

[Outline of Examples 1 to 8]
Examples 1, 2, 4, 6, and 8 are examples in which the composition of the present invention is obtained by pre-synthesizing the component (A) and then mixing with the component (B) and the component (C).
In Examples 3 and 5, the raw material of component (A) and component (C) are mixed, and component (A) is synthesized in the system by hydrosilylation reaction in the absence of component (B). This is an example of obtaining the composition of the present invention by adding the component B).
In Example 7, the raw material of the component (A), the component (B) and the component (C) are mixed, and the component (A) is added to the system by hydrosilylation reaction under a temperature condition in which the component (B) does not substantially react. This is an example in which the composition of the present invention is obtained.

[Example 1: Composition P1]
150 parts by mass of a toluene solution having a concentration of 50% by weight of the component (A1 ^R- 1),
(A1 ^L -1) component 10.0 parts by mass,
^(A2 H -1 ^L) component 15.0 parts by weight, and component (A3) were mixed (platinum metal relative to component A total amount corresponding to 1ppm in mass units), 2 hours at 100 ° C. while stirring After performing the reaction under the above conditions, stripping under reduced pressure was performed at 90 ° C. to remove toluene, and a component (A ^P1 ) having a solid phenyl group content of 45.5 mol% at room temperature was obtained. When the obtained (A ^P1 ) component was heated to 100 ° C., it liquefied.

100 parts by mass of the (A ^P1 ) component,
(B1) 0.5 parts by weight of an organic peroxide component
400 parts by mass of filler as component (C1) were mixed in a loss mixer heated to 100 ° C. to obtain a milky white solid composition P1 having low surface tackiness at room temperature.

[Example 2: Composition P2]
(A1 ^R -2) 155.4 parts by mass of a toluene solution having a concentration of 50% by mass,
(A1 ^L −1) component 10.4 parts by mass,
(A2 ^H −1 ^L ) Component 11.9 parts by mass and (A3) component (amount in which platinum metal is 2 ppm by mass with respect to the total component A) were mixed and then stirred at 100 ° C. for 2 hours. After performing the reaction under the above conditions, stripping under reduced pressure was performed at 90 ° C., and toluene was removed to obtain an ( ^{AP 2} ) component having a phenyl group content of 51.8 mol% solid at room temperature. When the obtained (A ^P2 ) component was heated to 100 ° C., it liquefied.

100 parts by mass of the (A ^P2 ) component,
(B1) 1.0 part by mass of organic peroxide as component
(C2) 262 parts by mass of filler as component,
(C4) 155 parts by mass of a filler as a component were mixed in a loss mixer heated to 100 ° C. to obtain a white solid composition P2 having low surface tackiness at room temperature.

[Example 3: Composition P3]
174.8 parts by weight of a toluene solution having a concentration of 50% by weight of the component (A1 ^R- 1),
^(A2 H -1 ^L) component 12.6 parts by mass were mixed and subjected to vacuum stripping at 90 ° C., to obtain a gum composition at room temperature to remove the toluene.

100 parts by weight of the above gum-like composition,
(A3) component (amount in which platinum metal is 1.5 ppm by mass with respect to the total of the above-mentioned gum-like composition),
226 parts by mass of the filler as component (C2) and 218 parts by mass of the filler as component (C3) are mixed in a loss mixer heated to 100 ° C., and reacted at 100 ° C. for 2 hours while stirring as it is. (A ^P3 ) component having a phenyl group content of 46.9 mol% in the presence of a filler was synthesized, and then the organic peroxide 1.6 (B2) component was allowed to cool while the mixer was naturally cooled. Mass was added and milky white solid composition P3 with low surface tackiness at room temperature was obtained.
Moreover, when this solid composition P3 was heated to 100 ° C., it melted and formed into a paste.

[Example 4: Composition P4]
(A1 ^R- 3) 134.7 parts by mass of a toluene solution having a component concentration of 50% by mass,
(A1 ^L -2) component 31.1 parts by mass,
^(A2 H -3 ^L) component 1.6 parts by weight, and (A3) after components were mixed (platinum metal relative to component A total amount corresponding to 1.0ppm in mass units), at 100 ° C. while stirring After performing the reaction under conditions of 2 hours, vacuum stripping was performed at 90 ° C. to remove toluene, and an (A ^P4 ) component having a phenyl group content of 0 mol% which was liquid at room temperature was obtained.

100 parts by mass of the (A ^P4 ) component,
0.8 parts by weight of organic peroxide as component (B1)
(C2) 417 parts by mass of a filler as a component was mixed in a loss mixer at room temperature to obtain a milky white paste-like composition P4.

[Example 5: Composition P5]
(A1 ^R- 4) 134.0 parts by mass of a toluene solution having a concentration of 50% by mass of the component,
(A1 ^L- 2) component 31.0 parts by mass and (A2 ^H -4 ^L ) component 2.1 parts by mass are mixed, vacuum stripping is performed at 90 ° C., toluene is removed, and the composition is liquid at room temperature. Got.

100 parts by weight of the liquid composition,
(A3) component (amount in which platinum metal is 3.0 ppm by mass with respect to the liquid composition),
(C1) 312 parts by weight of filler as component,
(C4) Component filler 103 parts by mass in a loss mixer heated to 100 ° C., and stirred for 2 hours at 100 ° C. with stirring, the phenyl group content in the presence of the filler After synthesizing the component (A ^P5 ) of 0 mol%, 0.6 parts by mass of the organic peroxide as component (B2) was added while allowing the mixer to cool naturally, and a milky white paste-like composition P5 was added at room temperature. was gotten.

[Example 6: Composition P6]
(A1 ^R- 3) 133.3 parts by mass of a toluene solution having a concentration of 50% by mass of the component,
(A1 ^L -2) component 30.8 parts by mass,
^(A2 H -3 ^L) component 2.6 parts by weight, and (A3) after components were mixed (platinum metal relative to component A total amount corresponding to 2.0ppm in mass units), at 100 ° C. while stirring After carrying out the reaction under the conditions for 2 hours, vacuum stripping was performed at 90 ° C. to remove toluene, and an (A ^P6 ) component having a phenyl group content of 0 mol% which was liquid at room temperature was obtained.

100 parts by mass of the (A ^P6 ) component,
(B1) component organic peroxide 0.6 parts by mass,
(C2) 207 parts by mass of filler as component,
205 parts by mass of a filler as component (C3) was mixed in a loss mixer at room temperature to obtain a milky white paste-like composition.

[Example 7: Composition P7]
(A1 ^R- 1) 150.0 parts by mass of a toluene solution having a concentration of 50% by mass of the component,
(A1 ^L -1) component 10.0 parts by mass,
After mixing 15.0 parts by mass of (A2 ^H -1 ^L ) component, vacuum stripping was performed at 90 ° C to remove toluene and obtain a gum-like composition at room temperature.

100 parts by weight of the above-mentioned gum-like composition, (A3) component (amount in which platinum metal is 1 ppm by mass with respect to the total gum-like composition),
(B1) 0.5 parts by weight of an organic peroxide component
(C1) Component filler 400 parts by weight are mixed in a loss mixer heated to 100 ° C. and reacted for 1 hour while stirring as it is, and the phenyl group content in the presence of the filler and peroxide is 45. After synthesizing the 5 mol% (A ^P7 ) component, a milky white solid composition P7 having low surface tack at room temperature was obtained.

[Example 8: Composition P8]
170.5 parts by mass of a toluene solution having a concentration of (A1 ^R- 2) component of 50% by mass,
(A1 ^L -1) component 11.4 parts by mass,
^(A2 H -1 ^L) component 3.41 parts by weight,
After mixing component (A3) (amount in which platinum metal is 3 ppm by mass with respect to the total amount of component A ′), the reaction was conducted at 100 ° C. for 2 hours with stirring, and then the vacuum was reduced at 90 ° C. Ripping was performed to remove toluene, and a solid ( ^{P 8} ) component having a sticky solid phenyl group content at room temperature was obtained.

100 parts by weight of solid (A ^P8 ) component obtained,
1.1 parts by mass of (B1) component organic peroxide,
(C1) 297 parts by mass of filler as component,
(C4) 171 parts by weight of filler as a component were mixed in a loss mixer heated to 100 ° C. to obtain a white solid composition P8 having low surface tackiness at room temperature.

[Outline of Comparative Examples 1 to 6]
Comparative Examples 1, 2 and 4: Hydrosilylation curable compositions not containing components (A) and (B).
Comparative Examples 3 and 5: A peroxide curable composition containing no component (A).
Comparative Example 6: A hydrosilylation / peroxide dual curable composition containing no component (A).

[Comparative Example 1: Composition C1]
134.5 parts by mass of a toluene solution having a concentration of the component (A1 ^R- 1) of 50% by mass,
9.0 parts by mass of (A1 ^L- 1) component,
After mixing 23.8 parts by mass of (A2 ^H −1 ^L ) component, vacuum stripping was performed at 90 ° C. to remove toluene and obtain a liquid composition at room temperature.

100 parts by mass of the obtained liquid composition,
Component (A3) (the amount by which platinum metal is 3 ppm by mass with respect to the liquid composition),
(C2) 348 parts by mass of the filler as the component was mixed in a loss mixer at room temperature to obtain a milky white paste-like composition C1.

[Comparative Example 2: Composition C2]
140.2 parts by mass of a toluene solution having a concentration of (A1 ^R- 2) component of 50% by mass,
(A1 ^L -1) component 9.3 parts by mass,
^(A2 H -1 ^L) component 10.3 parts by weight,
^(A2 H -2 ^R) after mixing the components 10.3 parts by mass, subjected to vacuum stripping at 90 ° C., to obtain a composition liquid at room temperature to remove the toluene.

100 parts by mass of the obtained liquid composition,
Component (A3) (the amount by which platinum metal is 3 ppm by mass with respect to the liquid composition),
(C1) 367 parts by mass of a filler as a component was mixed in a loss mixer at room temperature to obtain a milky white paste-like composition C2.

[Comparative Example 3: Composition C3]
(A1 ^R -2) 142.9 parts by mass of a toluene solution having a concentration of 50% by mass,
(A1 ^L -1) component 9.5 parts by mass,
After mixing 19.0 parts by mass of (A2 ^H −1 ^L ) component, vacuum stripping was performed at 90 ° C. to remove toluene and obtain a liquid composition at room temperature.

100 parts by mass of the obtained liquid composition,
0.95 parts by mass of the organic peroxide as component (B1)
(C1) 233 parts by mass of filler as component
(C4) 143 parts by mass of a filler as a component was mixed in a loss mixer at room temperature to obtain a milky white paste composition C3.

[Comparative Example 4: Composition C4]
(A1 ^R- 3) 125.6 parts by mass of a toluene solution having a component concentration of 50% by mass,
(A1 ^L -2) component 29.0 parts by mass,
After mixing 8.2 parts by mass of (A2 ^H -4 ^L ) component, vacuum stripping was performed at 90 ° C. to remove toluene and obtain a liquid composition at room temperature.

100 parts by mass of the obtained liquid composition,
(A3) component (amount in which platinum metal is 2 ppm by mass with respect to the liquid composition),
(C2) 383 parts by mass of a filler as a component was mixed in a loss mixer at room temperature to obtain a milky white paste composition C4.

[Comparative Example 5: Composition C5]
(A1 ^R -4) 125.6 parts by mass of a toluene solution having a concentration of 50% by mass,
(A1 ^L -2) component 29.0 parts by mass,
After mixing 8.2 parts by mass of (A2 ^H -4 ^L ) component, vacuum stripping was performed at 90 ° C. to remove toluene and obtain a liquid composition at room temperature.

100 parts by mass of the obtained liquid composition,
(B2) 1.0 part by weight of organic peroxide as component
(C1) 391 parts by mass of a filler as a component was mixed in a loss mixer at room temperature to obtain a milky white paste-like composition C5.

[Comparative Example 6: Composition C6]
(A1 ^R- 1) 150.0 parts by mass of a toluene solution having a concentration of 50% by mass of the component,
(A1 ^L -1) component 10.0 parts by mass,
After mixing 15.0 parts by mass of (A2 ^H -1 ^L ) component, vacuum stripping was performed at 90 ° C to remove toluene and obtain a gum-like composition at room temperature.

100 parts by mass of the obtained gum-like composition,
(A3) component (amount in which platinum metal is 1 ppm by mass with respect to the gum-like composition),
(B1) 0.5 parts by weight of an organic peroxide component
400 parts by mass of the filler as component (C1) were mixed in a loss mixer at room temperature to obtain a milky white paste-like composition C6.

Table 1 shows the results of evaluating the physical properties before and after curing of Examples 1 to 8 in Table 1 and Comparative Examples 1 to 6 in Table 2. As shown in Table 1, each of the compositions of Examples 1 to 8 is excellent in the physical strength of the initial cured product, and maintains high physical strength even when exposed to a high temperature of 250 ° C. or higher. there were. On the other hand, as shown in Table 2, the composition according to the comparative example was insufficient in toughness (breaking stress) such as bending fracture strength particularly when exposed to a high temperature of 250 ° C. or higher.

Claims (17)

(A) Curing comprising an organosilicon compound having an alkylene group having 2 to 20 carbon atoms and an alkenyl group having 2 to 20 carbon atoms bonded to a silicon atom in the molecule, and (B) a peroxide. Silicone composition. The ratio of [content of alkylene group (mol%)] / [content of alkenyl group (mol%)] in component (A) is in the range of 0.20 to 5.00. Curable silicone composition. The curable silicone composition according to claim 1 or 2, wherein the content of the alkenyl group in component (A) is in the range of 0.20 to 5.00 mol%. (A) component is
M unit: siloxane unit represented by R ¹ R ² ₂ SiO _0.5 ,
D unit: siloxane unit represented by R ¹ R ² SiO _1.0 ,
R ³ M / R ³ D unit: Silalkylene group-containing siloxane unit represented by R ³ _0.5 R ² ₂ SiO _0.5 and a silalkylene group represented by R ³ _0.5 R ² SiO _1.0 At least one siloxane unit selected from contained siloxane units, and T / Q unit: at least one siloxane selected from siloxane units represented by R ² SiO _1.5 and siloxane units represented by SiO _2.0 An organosilicon compound containing a unit,
In the formula, each R ¹ is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, and among all siloxane units, at least one R ¹ is an alkenyl group having 2 to 20 carbon atoms,
R ² represents an alkyl group having 1 to 20 carbon atoms, a halogen-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and a halogen-substituted aryl group having 6 to 20 carbon atoms, a hydroxyl group or Is at least one group selected from epoxy group-containing groups,
The curing according to any one of claims 1 to 3, wherein R ³ is a linear or branched silalkylene group having 2 to 20 carbon atoms bonded to a silicon atom in another siloxane unit. Silicone composition. (A) component is
(A1) At least one siloxane unit selected from a siloxane unit represented by R ² SiO _1.5 and a siloxane unit represented by SiO _2.0 in the molecule (wherein R ² represents the same group as described above) And at least one resinous organopolysiloxane having a hydrosilylation-reactive functional group selected from an alkenyl group having 2 to 20 carbon atoms and a silicon-bonded hydrogen atom, and (a2) ) Containing a siloxane unit represented by R ² ₂ SiO _1.0 in the molecule (wherein R ² is the same group as described above) and capable of hydrosilylation reaction with the component (a1) At least one linear organopolysiloxane having a functional group and a reactive functional group selected from an alkenyl group having 2 to 20 carbon atoms and a silicon-bonded hydrogen atom The
The organosilicon compound obtained by reacting the alkenyl group having 2 to 20 carbon atoms in the component (a1) or the component (a2) at a ratio designed to remain after the hydrosilylation reaction. Item 5. The curable silicone composition according to any one of Items 4 to 5. (A) component is
(A1): At least two alkenyl groups having 2 to 20 carbon atoms in one molecule obtained by mixing the following components (A1-1) or (A1-2) at a mass ratio of 50:50 to 100: 0. Organopolysiloxane (A1-1) Average unit formula:
(R ⁴ ₃ SiO _1/2 ) _a (R ⁴ ₂ SiO _2/2 ) _b (R ⁴ SiO _3/2 ) _c (SiO _4/2 ) _d (R ⁵ O _1/2 ) _e
Wherein R ⁴ is a halogen-substituted or unsubstituted monovalent hydrocarbon group or hydroxyl group having 1 to 20 carbon atoms, and at least two of R ⁴ are alkenyl groups having 2 to 20 carbon atoms; R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; a is a number in the range of 0 to 0.7, b is a number in the range of 0 to 0.7, and c is 0 to 0.9. D is a number in the range of 0 to 0.7, e is a number in the range of 0 to 0.1, and c + d is a number in the range of 0.3 to 0.9, a + b + c + d Is 1)
Organopolysiloxane (A1-2) average unit formula represented by:
(R ⁴ ₃ SiO _1/2 ) _f (R ⁴ ₂ SiO _2/2 ) _g (R ⁴ SiO _3/2 ) _h (SiO _4/2 ) _i (R ⁵ O _1/2 ) _j
Wherein R ⁴ and R ⁵ are the same groups as described above, and at least two of R ⁴ are alkenyl groups; f is a number within the range of 0.001 to 0.7, and g is 0.00. A number in the range of 3 to 0.999, h is a number in the range of 0 to 0.2, i is a number in the range of 0 to 0.2, j is a number in the range of 0 to 0.1, and H + i is a number in the range of 0 to 0.2, and f + g + h + i is 1.)
Organopolysiloxane (A2): Average composition formula:
R ⁶ _k H _m SiO _{(4-km) / 2}
Wherein R ⁶ is a halogen-substituted or unsubstituted monovalent hydrocarbon group or hydroxyl group having no aliphatic unsaturated bond, k is a number in the range of 1.0 to 2.5, and m is (The number is in the range of 0.01 to 0.9, and k + m is the number in the range of 1.5 to 3.0.)
In relation to 1 mol of an alkenyl group having 2 to 20 carbon atoms in the component (A1), 0.2 to 0.7 mol of silicon-bonded hydrogen atoms in this component Amount}
(A3) The curable silicone composition according to any one of claims 1 to 5, which is an organosilicon compound obtained by hydrosilylation reaction in the presence of a catalyst for hydrosilylation reaction. The curable silicone composition according to any one of claims 1 to 6, wherein in the component (A), the alkenyl group is a vinyl group and the alkylene group is an ethylene group. The curable silicone composition according to any one of claims 1 to 7, wherein in the component (A), 10 mol% or more of the monovalent organic group bonded to the silicon atom is an aryl group. The curable silicone composition according to any one of claims 1 to 8, wherein the component (B) is a peroxide having a 10-hour half-life temperature of 90 ° C or higher. Furthermore, the curable silicone composition in any one of Claims 1-9 which contains (C) inorganic filler in the range of 10-2000 mass parts with respect to 100 mass parts of (A) component. The curable silicone composition in any one of Claims 1-10 which has a softening point in the range of 25 to 100 degreeC, and has hot-melt property. The curable silicone composition in any one of Claims 1-11 whose type D durometer hardness in 25 degreeC of the hardened | cured material obtained by hardening | curing a curable silicone composition is 60 or more. The semiconductor sealing agent which consists of a curable silicone composition in any one of Claims 1-12. The light reflection material for optical semiconductors which consists of a curable silicone composition in any one of Claims 1-12. Hardened | cured material formed by hardening | curing the curable silicone composition in any one of Claims 1-12. A semiconductor having the cured product according to claim 15. A semiconductor sealing method using the curable silicone composition according to claim 1.