Curable organosilicon composition, cured product thereof, and method for producing the same

Abstract

The present invention provides a curable silicone composition and the like which have excellent workability such as hot melt properties and secondary molding and curing characteristics, and provide a cured product that does not become highly hardened or embrittled even when left at a temperature of 150 °C or higher for a long time. The curable silicone composition of the present invention and its uses, wherein the curable silicone composition contains: a polyorganosiloxane resin or a resin mixture which does not have hot melt properties as a whole molecule, contains at least 20 mol% or more of siloxane units represented by SiO4 / 2 among all siloxane units, and has a mass reduction rate of 2.0 mass% or less when exposed at 200 °C for 1 hour; a liquid linear or branched polyorganosiloxane; and a curing agent which has hot melt properties as a whole composition.

Description

Technical Field

[0001] The present invention relates to a curable silicone composition which can be obtained by a simple manufacturing method, has hot melt properties / formability, and whose cured product does not easily show a significant increase in hardness and embrittlement even when exposed to a temperature of 150 °C or higher for a long time, a molded product (particles, sheets, etc.) thereof, and a cured product thereof. Further, the present invention relates to a cured product of the composition and its uses (particularly including semiconductor components and semiconductors having the cured product), a manufacturing method of the composition, a molding method of the cured product, and the like. Background Art

[0002] Cured products formed by curing curable silicone compositions have excellent heat resistance, cold resistance, electrical insulation, weather resistance, hydrophobicity, and transparency, and are therefore used in a wide range of industrial fields. Such cured products of curable silicone compositions generally do not easily change color compared to other organic materials, and in addition, the reduction in physical properties is small, so they are also suitable as optical materials and encapsulants for semiconductor devices.

[0003] The present applicant has proposed a hot melt curable granular silicone composition for molding and a reactive silicone composition in Patent Document 1 and Patent Document 2. These silicone compositions are composed of so-called phenyl silicone resins, and have the advantages of excellent hot melt properties and excellent hardness and strength of the cured product compared to methyl silicone resins.

[0004] On the other hand, in recent years, the miniaturization and high output of optoelectronic devices and the like have been advanced. In the case of applying these hot melt curable granular silicone compositions, etc., particularly at a temperature of 200 °C or higher, coloring derived from phenyl silicone resin sometimes occurs, and particularly in the field of reflective materials, the light reflectance sometimes decreases. Therefore, there is a strong demand for a silicone composition that realizes hot melt properties and the mechanical strength of the cured product after molding, and satisfies higher heat resistance and color resistance requirements.

[0005] Here, in Patent Document 3, a transparent hot melt curable silicone sheet using a methyl silicone resin is disclosed. However, when the cured product formed from these compositions is exposed to a temperature of 150 °C or higher for a long time, there is a problem that the hardness extremely increases and embrittlement progresses, and it is difficult to use for applications such as encapsulating semiconductor elements.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Pamphlet of International Publication No. 2016 / 136243

[0009] Patent Document 2: Japanese Patent Application Laid-Open No. 2014-009322

[0010] Patent Document 3: Japanese Patent Application Laid-Open No. 2017-512224 Summary of the Invention

[0011] Problems to be Solved by the Invention

[0012] An object of the present invention is to provide a curable silicone composition having hot melt properties, less coloring at high temperatures, an increase in hardness when exposed to high temperatures of 150°C or higher for a long time, and a cured product that is not easily embrittled. Moreover, the present invention provides such a curable silicone composition in the form of granules, particles, flakes, etc., and in the form of a peelable laminate including a sheet of the curable silicone composition. In addition, an object of the present invention is to provide a member for a semiconductor device composed of a cured product of the curable silicone composition, a semiconductor device having the cured product, and a method for molding the cured product.

[0013] Technical Solution

[0014] The present inventors conducted in-depth research and found that by using the following curable silicone composition, the above technical problems can be solved, and thus the present invention was achieved. The curable silicone composition contains: a polyorganosiloxane resin that does not have hot melt properties as a whole molecule and contains 20 mol% or more of the siloxane units represented by SiO 4 / 2 shown siloxane units; a liquid linear or branched polyorganosiloxane; and a curing agent. The curable silicone composition has hot melt properties as a whole composition, and as the polyorganosiloxane resin, the mass reduction rate when exposed to 200°C for 1 hour is 2.0 mass% or less.

[0015] More specifically, the above technical problems can be solved by the following curable silicone composition,

[0016] The curable silicone composition is characterized by containing:

[0017] 100 parts by mass of a polyorganosiloxane resin (A) containing the following components (A1) and (A2) in a mass ratio of 0:100 to 90:10, and the mass reduction rate of the components (A1) and (A2) when exposed to 200°C for 1 hour is 2.0 mass% or less:

[0018] (A1) A polyorganosiloxane resin that does not have hot melt properties as a whole molecule, has a curing-reactive functional group containing a carbon-carbon double bond in the molecule, and contains 20 mol% or more of the siloxane units represented by SiO 4 / 2 shown siloxane units,

[0019] (A2) does not have hot melt properties as a whole molecule, does not have a functional group with a curing reactivity containing a carbon-carbon double bond in the molecule, and contains 20 mol% or more of SiO of all siloxane units 4 / 2 A polyorganosiloxane resin of the siloxane unit shown;

[0020] 10 to 100 parts by mass of (B) a linear or branched polyorganosiloxane that is liquid or plastic at 25°C and has at least two functional groups with a curing reactivity containing a carbon-carbon double bond in the molecule; and

[0021] An amount of (C) a curing agent required for curing of this curable organosilicon composition, which is one or more selected from the following (c1) or (c2):

[0022] (c1) An organic peroxide,

[0023] (c2) An organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms in the molecule and a hydrosilylation reaction catalyst,

[0024] This curable organosilicon composition has hot melt properties as a whole composition. Here, it may be that this curable organosilicon composition optionally contains (D) a functional filler, and it may be that (D) component is contained in a range of 10 to 2000 parts by mass based on 100 parts by mass of the sum of (A) component and (B) component. Moreover, it may be that this curable organosilicon composition is granular, particulate, or sheet-like.

[0025] It may be that the above curable organosilicon composition is in the form of a substantially flat curable organosilicon composition sheet having a thickness of 10 to 1000 μm.

[0026] Furthermore, it may be that the above curable organosilicon composition is used for a releasable laminate having the following constitution. That is, it may be in the form of such a releasable laminate that has: the above curable organosilicon composition sheet; and a sheet-like substrate, and on one side or both sides of this curable organosilicon composition sheet, there is provided a release surface facing the curable organosilicon composition sheet. Such a curable organosilicon composition sheet can also be used as a film-like or sheet-like silicone adhesive.

[0027] Moreover, the present inventors found that the above technical problem can be solved by the following content, and thus the present invention was achieved, that is, a cured product of the above curable organosilicon composition, in particular, the use of this cured product as a member for a semiconductor device and a semiconductor device having this cured product (including one or more selected from a power semiconductor device, an optical semiconductor device, and a semiconductor device mounted on a flexible circuit board).

[0028] Similarly, the inventors of the present invention have found that the above technical problems can be solved by the following methods, thereby realizing the present invention, that is, a manufacturing method characterized by granulating by mixing only the components constituting the curable organosilicon composition under a temperature condition of not exceeding 50°C; and a method for molding a cured product using the above curable granular organosilicon composition.

[0029] It should be noted that the above molding method includes transfer molding, compression molding or injection molding, and the curable organosilicon composition of the present invention is preferably used as these molding materials. Moreover, the curable organosilicon composition of the present invention can be used as a molding material for the process of covering a semiconductor element or a semiconductor circuit board by secondary molding through a cured product, that is, a molding material for a so-called secondary molding method.

[0030] Similarly, the inventors of the present invention provide a method for manufacturing a curable organosilicon composition sheet, which is characterized by the following steps.

[0031] Step 1: A step of mixing the raw material components of the above curable organosilicon composition at a temperature of 50°C or higher;

[0032] Step 2: A step of kneading the mixture obtained in Step 1 while heating and melting it;

[0033] Step 3: A step of laminating the heated and melted mixture obtained in Step 2 between films having at least one release surface; and

[0034] Step 4: A step of stretching the laminate obtained in Step 3 between rolls to form a curable organosilicon sheet having a specific film thickness.

[0035] Advantageous Effects

[0036] The curable silicone composition of the present invention has excellent operability such as hot melt properties and secondary molding, and excellent curing characteristics. Even when the cured product of the curable silicone composition is exposed at a temperature exceeding 150°C for a long time, it is not likely to cause an increase in hardness and embrittlement. Therefore, especially when used for encapsulation / protection of semiconductor devices used at high temperatures, etc., it can suppress the breakage or cracking of the cured product layer over time, and improve the durability and reliability of the semiconductor device. In addition, the curable silicone composition of the present invention can incorporate a relatively large amount of functional inorganic fillers without impairing the flexibility and stress relaxation properties of the cured product, and can impart desired functions such as heat dissipation to the cured product. Furthermore, such a curable silicone composition can be produced only through a simple mixing process, and can be manufactured efficiently. Moreover, through the present invention, such a curable silicone composition can be provided in the form of granules, particles, sheets, etc., and in the form of a peelable laminate including a sheet of the curable silicone composition. Therefore, in the manufacturing process of semiconductor devices, etc., it can also be cut into a desired size for use as needed, and has excellent application possibilities in industrial production processes. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 FIG. is a diagram showing the overall configuration (including the entire part of sheet formation) of a manufacturing apparatus for a curable hot-melt silicone composition sheet of a production example. DETAILED DESCRIPTION OF THE INVENTION

[0038] [Curable Silicone Composition]

[0039] The curable silicone composition of the present invention is characterized in that a polyorganosiloxane resin containing 20 mol% or more of the siloxane units shown in SiO 4 / 2 among all siloxane units is one of the main components, and the mass reduction rate of the polyorganosiloxane resin when exposed at 200°C for 1 hour is 2.0 mass% or less. In addition, the composition of the present invention is further characterized in that it has hot melt properties as a whole. It should be noted that in the present invention, unless otherwise specified, "having hot melt properties" means that the softening point is between 50 and 200°C, has a melt viscosity at 150°C (preferably a melt viscosity lower than 1000 Pa·s), and has a flowing property.

[0040] [Technical Significance of the Weight Reduction Rate of the Polyorganosiloxane Resin]

[0041] Here, the mass reduction rate of the polyorganosiloxane resin when exposed at 200°C for 1 hour being 2.0 mass% or less means that the amount of volatile components of the polyorganosiloxane resin is small. The first feature of the present invention is the use of a specific branched siloxane unit (SiO 4 / 2A polyorganosiloxane resin having a high content of ()) and a very small amount of volatile components in the resin. Specifically, when the polyorganosiloxane resin as the component (A) described later is exposed at 200 °C for 1 hour, the mass reduction rate needs to be 2.0% by mass or less, preferably 1.5% by mass or less, and more preferably 1.0% by mass or less.

[0042] Generally, in the production process of a polyorganosiloxane resin containing many branched siloxane units, volatile low-molecular-weight components are easily generated and mixed into the resin, and these volatile components have the effect of significantly reducing the hardness of the cured product obtained from the composition defined in the present invention. Therefore, if the cured product is exposed at a temperature exceeding 150 °C for a long time, the low-molecular-weight components will volatilize, and as a result, the hardness of the cured product will increase significantly. In addition, when a large amount of siloxane units shown by SiO 4 / 2 are contained in the network of the organosilicon cured product, the cured product with high hardness has a tendency to become extremely brittle, and as a result, embrittlement also occurs. By adopting the constitution defined in the present invention, a cured product that is not likely to have an increase in hardness and embrittlement even when exposed at a temperature exceeding 150 °C for a long time can be provided. Therefore, when the mass reduction rate when the polyorganosiloxane resin is exposed at 200 °C for 1 hour exceeds the above upper limit, the obtained cured product has a sharp increase in hardness especially at high temperatures and becomes prone to embrittlement. It should be noted that the lower limit of this mass reduction rate is 0.0% by mass, and it is particularly preferably free of volatile low-molecular-weight components. In the range of 0.1 to 2.0% by mass, in the range of 0.2 to 1.5% by mass, and in the range of 0.3 to 0.8% by mass, practically, the change in the hardness of the cured product can be sufficiently suppressed.

[0043] The type of the volatile low-molecular-weight component is not particularly limited. The polyorganosiloxane resin of the present invention contains many branched siloxane units (Q units) shown by SiO 4 / 2 , and therefore, it is easily by-produced with a volatile siloxane component represented by M4Q through the reaction with the siloxane unit (M unit) shown by R 3 SiO 1 / 2 . Particularly preferably in the present invention, by removing the volatile low-molecular-weight component mainly composed of the volatile siloxane component from the polyorganosiloxane resin, the above-mentioned mass reduction rate is achieved.

[0044] [Thermoplasticity and composition of the curable organosilicon composition]

[0045] The curable silicone composition of the present invention has hot melt properties as a whole composition, a softening point of 50 °C or higher, a melt viscosity at 150 °C (preferably a melt viscosity of less than 1000 Pa·s), and has a flowing property. It should be noted that the individual components constituting the composition may not have hot melt properties, especially in the case where the curable or non-reactive polyorganosiloxane resin is in a particulate form, and it is particularly preferred that it does not have hot melt properties at temperatures below 200 °C.

[0046] It should be noted that the curable silicone composition of the present invention may also be in a form molded into granules, particles or flakes according to its use, and this is preferred. Hereinafter, each component and optional component of the composition will be described. It should be noted that in the present invention, unless otherwise defined, "average particle diameter" refers to the primary average particle diameter of the particles.

[0047] More specifically, the curable silicone composition of the present invention contains the following substances:

[0048] 100 parts by mass of (A) a polyorganosiloxane resin containing the following components (A1) and (A2) in a mass ratio of 0:100 to 90:10, and the mass reduction rate when the components (A1) and (A2) are exposed at 200 °C for 1 hour is 2.0% by mass or less:

[0049] (A1) A polyorganosiloxane resin that does not have hot melt properties as a whole molecule, has a curable functional group containing a carbon-carbon double bond in the molecule, and contains 20 mol% or more of SiO 4 / 2 The polyorganosiloxane resin of the siloxane unit shown,

[0050] (A2) A polyorganosiloxane resin that does not have hot melt properties as a whole molecule, does not have a curable functional group containing a carbon-carbon double bond in the molecule, and contains 20 mol% or more of SiO 4 / 2 The polyorganosiloxane resin of the siloxane unit shown;

[0051] 10 to 100 parts by mass of (B) a linear or branched polyorganosiloxane that is liquid at 25 °C and has at least two curable functional groups containing a carbon-carbon double bond in the molecule; and

[0052] An amount of (C) a curing agent selected from one or more of the following (c1) or (c2) required for curing the present curable silicone composition:

[0053] (c1) An organic peroxide,

[0054] (c2) An organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms in the molecule and a hydrosilylation reaction catalyst,

[0055] It may also further optionally contain (D) functional inorganic fillers, and / or (E) hot-melt particles having a dropping point of 50 °C or higher and a melt viscosity of 10 Pas or less measured by a rotational viscometer at 150 °C, and / or other additives, etc.

[0056] The components and their contents will be described below.

[0057] [Component (A)]

[0058] The curable silicone composition of the present invention contains a polyorganosiloxane resin that does not have hot-melt properties as a whole molecule and contains 20 mol% or more of SiO 4 / 2 siloxane units shown. This polyorganosiloxane resin may further contain R 3 SiO 1 / 2 , R 2 SiO 2 / 2 , RSiO 3 / 2 (where R is a monovalent organic group) siloxane units, R 2 O 1 / 2 (where R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms) hydroxyl or alkoxy groups. Preferably, at least 40 mol% or more, especially in the range of 40 to 90 mol%, of all siloxane units contain SiO 4 / 2 siloxane units shown. When the content of SiO 4 / 2 shown siloxane units is less than the lower limit, even if a large amount of other branched siloxane units (such as RSiO 3 / 2 ) are contained, the technical effects of the present invention may sometimes not be achieved.

[0059] As described above, this polyorganosiloxane resin requires a low content of volatile low-molecular-weight components and needs to remove the volatile components generated in its production process. The degree of this removal is synonymous with the mass reduction rate when exposed at 200 °C for 1 hour as described above. In order to make this mass reduction rate 2.0 mass% or less, it is necessary to remove volatile low-molecular-weight components from the polyorganosiloxane resin.

[0060] Such an organopolysiloxane can be defined as the following polyorganosiloxane resin:

[0061] It contains the following (A1) and (A2) in a mass ratio of 0:100 to 90:10,

[0062] (A1) A polyorganosiloxane resin that does not have hot-melt properties as a whole molecule, has a curing-reactive functional group containing a carbon-carbon double bond in the molecule, and contains 20 mol% or more of SiO 4 / 2 siloxane units shown; and

[0063] (A2) does not have hot melt properties as a whole molecule and does not have a functional group with curing reactivity containing a carbon-carbon double bond in the molecule, and contains 20 mol% or more of SiO of all siloxane units 4 / 2 of the polysiloxane resin having the siloxane units shown

[0064] Moreover, the mass reduction rate when the component (A1) and the component (A2) are exposed at 200 °C for 1 hour is 2.0 mass% or less. It should be noted that the component (A1) is any constituent of the component (A), and only the component (A2) described below may be used.

[0065] The above-mentioned component (A) does not have hot melt properties as a whole molecule, and by using it in combination with the following component (B) within a specified amount range, the hot melt properties of the whole composition can be achieved. Such a component (A) can be used alone or together with other components in the form of fine particles. In this case, it is preferably spherical organosilicon fine particles with an average primary particle size of 1 to 20 μm.

[0066] [(A1) Polysiloxane resin having a curing reactive functional group]

[0067] The component (A1) is one of the main agents of this composition, contains 20 mol% or more of SiO of all siloxane units 4 / 2 of the siloxane units shown, does not have hot melt properties alone, and in addition, is a polysiloxane resin having a curing reactive functional group containing a carbon-carbon double bond in the molecule, and the weight reduction rate when exposed at 200 °C for 1 hour is 2.0 mass% or less.

[0068] The component (A1) needs to have a curing reactive group containing a carbon-carbon double bond in the molecule. Such a curing reactive group is a hydrosilylation reactive or organic peroxide curable functional group, and a cured product is formed through a crosslinking reaction with other components. Such a curing reactive group is an alkenyl or acryloyl group. For example, alkenyl groups having 2 to 10 carbon atoms such as vinyl, allyl, butenyl, pentenyl, hexenyl, and heptenyl; monovalent organic groups containing an acryloyl group such as 3-methacryloxypropyl and 3-acryloxypropyl can be cited. In particular, vinyl or hexenyl is preferably used.

[0069] (A1) component is a polyorganosiloxane resin that does not have hot melt properties as a whole molecule and is solid in a solvent-free state. Here, not having hot melt properties means that the resin as the (A1) component alone does not show a heat melting behavior below 200 °C. Specifically, it means that it does not have a softening point and a melt viscosity below 200 °C. In the (A1) component, there are no particular restrictions on such physical properties in terms of structure. Preferably, the functional group in the polyorganosiloxane resin is a monovalent hydrocarbon group having 1 to 10 carbon atoms, especially a functional group selected from alkyl groups having 1 to 10 carbon atoms such as methyl, and substantially does not contain aryl groups such as phenyl. In the case of containing a large amount of phenyl or the like, this component sometimes becomes hot melt, and sometimes the effect of enhancing the cured product specific to the SiO 4 / 2 group is reduced.

[0070] Preferably, the functional group bonded to the silicon atom in the (A1) component is a group selected from groups such as methyl and alkenyl groups such as vinyl. Preferably, 70 mol% to 99 mol% of the functional groups bonded to all silicon atoms are methyl, more preferably 80 to 99 mol% are methyl, and particularly preferably 88 to 99 mol% are methyl. The functional group bonded to other silicon atoms is an alkenyl group such as vinyl. Within this range, the (A1) component is not hot melt, and it can be designed as a component with particularly excellent heat resistance to coloring and the like of its cured product at high temperatures. It should be noted that in this (A1) component, a small amount of hydroxyl groups or alkoxy groups may also be contained.

[0071] (A1) component is characterized in that it is a polyorganosiloxane resin that is solid in a solvent-free state and contains 20 mol% or more of the siloxane units represented by SiO 4 / 2 in the molecule. Preferably, these branched siloxane units are at least 40 mol% or more, 50 mol% or more of all siloxane units, and in particular, are particularly preferably in the range of 50 to 90 mol%. In addition, R is a monovalent organic group, preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, especially a functional group selected from alkyl groups having 1 to 10 carbon atoms such as methyl and alkenyl groups, and from the viewpoint of technical effects, preferably substantially does not contain aryl groups such as phenyl in R.

[0072] Preferably, the (A1) component is a non-hot melt polyorganosiloxane resin represented by the following average unit formula (A1-1).

[0073] (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 )d (R 2 O 1 / 2 ) e

[0074] (In the formula, each R 1 are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, wherein all R 1 1-12 mol% are alkenyl groups; each R2 is a hydrogen atom or an alkyl group having 1-10 carbon atoms; a, b, c, d and e are numbers satisfying the following: 0.10≤a≤0.60, 0≤b≤0.70, 0≤c≤0.80, 0.2≤d≤0.65, 0≤e≤0.05, wherein c+d>0.20, and a+b+c+d=1)

[0075] In the above average unit formula, each R 1 are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or similar alkyl groups; vinyl, allyl, butenyl, pentenyl, hexenyl, or similar alkenyl groups; phenyl, tolyl, xylyl, or similar aryl groups; benzyl, phenethyl, or similar aralkyl groups; and chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, or similar halogenated alkyl groups. Moreover, all R in one molecule are 1 1 to 12 mol% are alkenyl groups, preferably all R 1 2 to 10 mol% of the alkenyl group is an alkenyl group. When the alkenyl group content is less than the lower limit of the range, the mechanical strength (hardness, etc.) of the obtained cured product may become insufficient. On the other hand, if the alkenyl group content is below the upper limit of the range, the composition containing this component can achieve good hot melt performance as a whole composition. It should be noted that each R 1 Preferably, R is a functional group selected from an alkyl group having 1 to 10 carbon atoms such as a methyl group, and an alkenyl group such as a vinyl group and a hexenyl group. 1 It is preferred that the phenyl group or other aryl group is not substantially contained. When a large amount of phenyl group or other aryl group is contained, the component (A) itself becomes hot-melt, and the technical effect of the present invention may not be achieved. In addition, in the cured product, SiO 4 / 2 The group-specific effect of reinforcing the cured product is reduced.

[0076] In the formula, R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 2 The alkyl group of R is exemplified by methyl, ethyl, propyl, butyl, pentyl or hexyl. 2 The functional group R 2 O 1 / 2 The same applies to the hydroxyl group or alkoxy group in the component (A).

[0077] In the formula, a is a number representing the proportion of siloxane units of the general formula R 1 3SiO 1 / 2 . This number satisfies 0.1 ≤ a ≤ 0.60, preferably 0.15 ≤ a ≤ 0.55. If a is above the lower limit of the said range, the composition containing this component can achieve good hot-melt properties as a whole composition. On the other hand, if a is below the upper limit of the said range, the mechanical strength (hardness, elongation rate, etc.) of the resulting cured product does not become too low.

[0078] In the formula, b is a number representing the proportion of siloxane units of the general formula R 1 2SiO 2 / 2 . This number satisfies 0 ≤ b ≤ 0.70, preferably 0 ≤ b ≤ 0.60. If b is below the upper limit of the range, the composition containing this component can achieve good hot-melt properties as a whole composition, and a composition with less stickiness at room temperature can be obtained.

[0079] In the formula, c is a number representing the proportion of siloxane units of the general formula R 3 SiO 3 / 2 . This number satisfies 0 ≤ c ≤ 0.80, preferably 0 ≤ c ≤ 0.75. If c is below the upper limit of the range, the composition containing this component can achieve good hot-melt properties as a whole composition, and a composition with less stickiness and no stickiness at room temperature can be obtained. In the present invention, c can be 0, and it is preferred.

[0080] In the formula, d is a number representing the proportion of siloxane units of SiO 4 / 2 , and 0.20 ≤ d ≤ 0.65 is required, particularly preferably 0.25 ≤ d ≤ 0.65. The reason is that within this numerical range, the composition containing this component can achieve good hot-melt properties as a whole composition, and the resulting cured product has sufficient softness.

[0081] In the present invention, c can be 0, but c + d > 0.20 is required. When the value of c + d is less than the said lower limit, good hot-melt properties cannot be achieved as a whole composition, and sometimes the technical effects of the present invention cannot be fully realized.

[0082] In the formula, e is a number representing the proportion of units of the general formula R 2 O 1 / 2 , and this unit refers to a hydroxyl group or an alkoxy group bonded to a silicon atom that may be contained in the polyorganosiloxane resin. This number satisfies 0 ≤ e ≤ 0.05, preferably 0 ≤ e ≤ 0.03. If e is below the upper limit of the range, a material with good hot-melt properties as a whole composition can be obtained. It should be noted that ultimately, the sum of a, b, c, and d as the total of each siloxane unit is equal to 1.

[0083] (A1) The component is a polyorganosiloxane resin having the above-mentioned characteristics. From the perspective of operability, it can also be used as spherical polyorganosiloxane resin particles with an average primary particle size of 1 to 20 μm measured by a laser diffraction / scattering method or the like. By using this particle component, the present composition can be prepared or produced into a curable granular composition with excellent operation workability and hot melt properties. Here, the method for manufacturing the (A1) component is not limited, and known methods can be used.

[0084] Examples of the method for manufacturing the particulate (A1) component include: a method of pulverizing the above-mentioned polyorganosiloxane resin using a pulverizer; a method of directly atomizing in the presence of a solvent. The pulverizer is not limited, and examples include: a roll mill, a ball mill, a jet pulverizer, a turbo mill, and a planetary pulverizer. In addition, as a method of directly atomizing the polyorganosiloxane resin in the presence of a solvent, examples include: spraying using a spray dryer; or atomization using a twin-screw kneader or a belt dryer. It should be noted that when obtaining the particulate (A1) component, a part of the following (C) component, for example, a hydrosilylation reaction catalyst, etc., can also be atomized together with the (A1) component. From the perspective of the storage stability of the obtained composition, it is not preferred to atomize a mixture having the property of curing by heating.

[0085] In particular, by using a spray dryer or the like, a spherical (A1) component with an average primary particle size of 1 to 500 μm, preferably 1 to 20 μm, can be manufactured. It should be noted that the heating / drying temperature of the spray dryer needs to be appropriately set based on the heat resistance of the polyorganosiloxane resin particles, etc. It should be noted that in order to prevent secondary aggregation of the obtained particles, it is preferred to control the temperature of the polyorganosiloxane resin particles below their glass transition temperature. The polyorganosiloxane resin particles obtained in this way can be recovered by a cyclone, a bag filter, etc.

[0086] In the above atomization, a solvent can also be used within a range that does not hinder the curing reaction. The solvent is not limited, and examples 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; organosilicons such as hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane; esters such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

[0087] [(A2) component]

[0088] (A2) component is one of the main agents of this composition. It is a polyorganosiloxane resin that does not have hot melt properties alone and contains curing-reactive functional groups. By being used in combination with the (A1) component and the (B) component within a specified amount range, it realizes the hot melt property of the whole composition and the excellent stress relaxation property of the cured product. Such an (A2) component can be used in the form of fine particles alone or together with other components (for example, the (A1) component as a non-reactive polyorganosiloxane resin, a part of the (C) component as a curing agent), or can be mixed with the (A1) component and the (B) component and processed into a hot melt solid.

[0089] (A2) component is a polyorganosiloxane resin that does not have hot melt properties as a whole molecule and is solid in a solvent-free state. Here, not having hot melt properties means that the resin of the (A2) component alone does not show a heat melting behavior. Specifically, it means not having a softening point and a melt viscosity. In the (A2) component, there are no particular structural limitations on such physical properties. Preferably, the functional group in the polyorganosiloxane resin is a monovalent hydrocarbon group having 1 to 10 carbon atoms, especially a functional group selected from alkyl groups having 1 to 10 carbon atoms such as methyl, and substantially does not contain aryl groups such as phenyl. In the case of a large amount of phenyl, etc., this component sometimes becomes hot melt, and sometimes the effect of enhancing the cured product unique to the SiO 4 / 2 group decreases.

[0090] (A2) component is characterized in that, like the (A1) component, it is solid, and is a polyorganosiloxane resin containing 20 mol% or more of the siloxane units shown by SiO 4 / 2 , and does not have a curing-reactive functional group containing at least one carbon-carbon double bond in the molecule. That is, the (A2) component is characterized in that it does not contain alkenyl groups such as vinyl as functional groups in the polyorganosiloxane resin. Examples of the functional group in this polyorganosiloxane include: a monovalent hydrocarbon group having 1 to 10 carbon atoms, especially an alkyl group having 1 to 10 carbon atoms such as methyl, and preferably substantially does not contain aryl groups such as phenyl.

[0091] Preferably, the functional group bonded to the silicon atom in the (A2) component is an alkyl group having 1 to 10 carbon atoms such as methyl. Preferably, 70 mol% to 100 mol% of the functional groups bonded to all silicon atoms are methyl, more preferably 80 to 100 mol% are methyl, and particularly preferably 88 to 100 mol% are methyl. Within this range, the (A2) component is not hot melt, and can be designed to be a component with particularly excellent enhanced effect of the cured product containing the siloxane units shown by SiO 4 / 2 . It should be noted that in this (A2) component, a small amount of hydroxyl groups or alkoxy groups can also be contained.

[0092] (A2) component does not have a curing reactive group containing a carbon-carbon double bond in the molecule, so it does not form a cured product by itself, but has the effects of improving the hot melt property of the whole composition and enhancing the cured product. In addition, as needed, it is a component required to achieve the technical effects of the present invention by being used in combination with the (A1) component having a curing reactive group.

[0093] The (A2) component is characterized in that it is a solid polyorganosiloxane resin in a solvent-free state, and contains more than 20 mol% of the siloxane units shown as branched-chain siloxane units in all the siloxane units. 4 / 2 The siloxane units shown. Preferably, the branched-chain siloxane units are at least 40 mol% or more, 50 mol% or more of all the siloxane units, and in particular, it is particularly preferably in the range of 50 to 65 mol%.

[0094] Preferably, the (A2) component is a non-hot-melt polyorganosiloxane resin represented by the following average unit formula (A2-1).

[0095] (R 3 3SiO 1 / 2 ) f (R 3 2SiO 2 / 2 ) g (R 3 SiO 3 / 2 ) h (SiO 4 / 2 ) i (R 2 O 1 / 2 ) j

[0096] (In the formula, each R 3 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms and not containing a carbon-carbon double bond; R2 is an alkyl group having a hydrogen atom or 1 to 10 carbon atoms; f, g, h, i, and j are numbers satisfying the following: 0.35 ≤ f ≤ 0.55, 0 ≤ g ≤ 0.20, 0 ≤ h ≤ 0.20, 0.45 ≤ i ≤ 0.65, 0 ≤ j ≤ 0.05, and f + g + h + i = 1)

[0097] In the above average unit formula, each R 3 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms and not containing a carbon-carbon double bond, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or a similar alkyl group; phenyl, tolyl, xylyl, or a similar aryl group; benzyl, phenethyl, or a similar aralkyl group; and chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, or a similar haloalkyl group, etc. Here, it is preferred that all R in one molecule 3More than 70 mol% thereof is an alkyl group having 1 to 10 carbon atoms such as methyl, and from the viewpoints of industrial production and the technical effects of the invention, more than 88 mol% being methyl is particularly preferred. On the other hand, R 3 Preferably, it substantially does not contain aryl groups such as phenyl. In the case of containing a large amount of aryl groups such as phenyl, the component (B) itself becomes hot-melt, and sometimes the technical effects of the present invention cannot be achieved. In addition, sometimes the color resistance of the cured product at high temperatures deteriorates.

[0098] In the formula, R 2 is the same group as described above.

[0099] In the formula, f is a number representing the proportion of the siloxane unit of the general formula R 3 3SiO 1 / 2 . This number satisfies 0.35 ≤ f ≤ 0.55, and preferably satisfies 0.40 ≤ a ≤ 0.50. If f is above the lower limit of the above range, the composition containing this component can achieve good hot-melt properties as a whole composition. On the other hand, if f is below the upper limit of the above range, the mechanical strength (such as hardness) of the obtained cured product does not become too low.

[0100] In the formula, g is a number representing the proportion of the siloxane unit of the general formula R 3 2SiO 2 / 2 . This number satisfies 0 ≤ g ≤ 0.20, and preferably satisfies 0 ≤ g ≤ 0.10. If g is below the upper limit of the range, the composition containing this component can achieve good hot-melt properties as a whole composition, and a composition with little tackiness at room temperature can be obtained. In the present invention, g can be 0, and it is preferred.

[0101] In the formula, h is a number representing the proportion of the siloxane unit of the general formula R 3 SiO 3 / 2 . This number satisfies 0 ≤ h ≤ 0.20, and preferably satisfies 0 ≤ h ≤ 0.10. If h is below the upper limit of the range, the composition containing this component can achieve good hot-melt properties as a whole composition, and a composition with little tackiness at room temperature can be obtained. In the present invention, h can be 0, and it is preferred.

[0102] In the formula, i is a number representing the proportion of the siloxane unit of SiO 4 / 2 , and it is required that 0.45 ≤ i ≤ 0.65, preferably 0.40 ≤ i ≤ 0.65, and particularly preferably 0.50 ≤ i ≤ 0.65. The reason is that within this numerical range, the composition containing this component can have good hot-melt properties as a whole composition, the mechanical strength of the obtained cured product is excellent, and a composition without tackiness and with good handling operability can be achieved as a whole composition.

[0103] In the formula, j is a number representing the general formula R 2 O1 / 2 The number of the proportion of units, where the units refer to the hydroxyl groups or alkoxy groups bonded to silicon atoms that may be contained in the polyorganosiloxane resin. This number satisfies 0 ≤ j ≤ 0.05, preferably 0 ≤ j ≤ 0.03. If j is below the upper limit of the range, a material with good hot-melt properties as a whole composition can be obtained. It should be noted that ultimately, the sum of f, g, h, and i as the total of each siloxane unit is equal to 1.

[0104] (A2) component is a polyorganosiloxane resin having the above characteristics. From the perspective of operability, it can be used as spherical polyorganosiloxane resin particles with an average primary particle size of 1 to 20 μm measured by methods such as laser diffraction / scattering method. By using this particulate component, the present composition can be prepared or produced into a curable granular composition with excellent operability and hot-melt properties. Here, the method for manufacturing the (A2) component can be exemplified by the same method as the method exemplified in the above (A1) component.

[0105] [Removal of volatile low-molecular-weight components in component (A)]

[0106] (A1) component and (A2) component generate volatile low-molecular-weight components in their production processes. Specifically, it is the M4Q structure, which appears as a by-product when polymerizing a polyorganosiloxane resin composed of M units (R 3 3SiO 1 / 2 ) and Q units (SiO 4 / 2 ). This structure has the effect of significantly reducing the hardness of the cured product formed from the composition of the present invention. The polyorganosiloxane resin is polymerized in the presence of a highly compatible organic solvent, and an individual polyorganosiloxane resin is obtained by removing the organic solvent by means of reduced-pressure drying, etc. The M4Q structure has a high mutual solubility with the polyorganosiloxane resin and cannot be removed under drying conditions such as removing the organic solvent. It is known that this structure can be removed by short-time exposure at a temperature of 200 °C or higher, but after being integrally formed with a substrate such as a semiconductor, if exposed at a high temperature for removal, the volume of the cured product decreases and a significant increase in hardness occurs, resulting in dimensional changes in the molded product and warping, etc. Therefore, for use in the applications of the present invention, it is necessary to remove the M4Q structure before the molding process with the substrate, that is, at the raw material stage in advance.

[0107] As methods for removing this structure, there can be exemplified: a method of removing it together with the above-mentioned organic solvent in a twin-screw kneader; a method of drying in an oven, etc. after forming the polyorganosiloxane resin into particles by the method described below.

[0108] More specifically, the components (A1) and (A2) are generated in the presence of an organic solvent, and volatile components appear as by-products during the synthesis. The volatile components can be removed by treating the polyorganosiloxane resin as the obtained crude raw material at a high temperature of about 200 degrees for a short time, so that the organic solvent and the volatile components can be removed from the components (A1) and (A2) at the same time in a twin-screw mixer set at about 200°C. In addition, when the components (A1) and (A2) are treated into spherical powders, the organic solvent can be removed in a spray dryer to form a powder, but in this treatment method, the volatile components cannot be removed. If the obtained powder is treated at a low temperature of about 120°C for 24 hours, the volatile components can be removed without agglomerating the powder.

[0109] [Mass Ratio of Component (A1) to Component (A2) in Component (A)]

[0110] In order to impart hot melt properties to the present composition as a whole, it is necessary to mix the component (A2) or a mixture of the component (A1) and the component (A2) with the component (B) described below at a predetermined ratio. The ratio of the component (A1) to the component (A2) may be in the range of 0:100 to 90:10, preferably in the range of 0:100 to 85:15, and more preferably 0:100 to 80:20. The component (A2) itself does not have curing properties, but by adding a small amount of the component (A1) to the present composition, the elastic modulus of the cured product formed by the present composition at high temperature can be controlled. When the functional inorganic filler described below is added to the present composition, the appropriate elastic modulus and softness can be achieved by appropriately adjusting the amount of the functional inorganic filler added and the amount of the component (A1) used. For example, when the amount of the functional inorganic filler added is large or when the elastic modulus of the cured product to be obtained is attempted to be reduced as much as possible, the composition may be prepared without adding the component (A1) and only the component (A2). On the other hand, when the functional inorganic filler described below is not added, the elastic modulus at room temperature and high temperature can be set to a desired value by increasing the amount of the component (A2) added.

[0111] [(B) ingredient]

[0112] The component (B) is one of the main ingredients of the present composition, and is a linear or branched polyorganosiloxane that is liquid or plastic at 25°C and has at least two curing-reactive functional groups containing carbon-carbon double bonds in the molecule. Such a curing-reactive linear polyorganosiloxane is mixed with the above-mentioned solid polyorganosiloxane resin, and the composition as a whole exhibits hot-melt properties.

[0113] (B) component needs to have a curing reactive group containing a carbon-carbon double bond within the molecule. Such a curing reactive group is a hydrosilylation reactive or organic peroxide curable functional group, and a cured product is formed through a crosslinking reaction with other components. Such a curing reactive group is an alkenyl group or an acryloyl group, and the same groups as those described above can be exemplified. In particular, a vinyl group or a hexenyl group is preferably used.

[0114] (B) component is a linear or branched polyorganosiloxane that is liquid or plastic at 25 °C (room temperature). By mixing with the solid (A) component at room temperature, the composition as a whole exhibits hot melt characteristics. Its structure can be a polyorganosiloxane with a branched structure having a small number of branches (for example, a T unit represented by the general formula R 4 SiO 3 / 2 (wherein R 4 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms) or a Q unit represented by SiO 4 / 2 ),

[0115] Preferably, it is a linear polydiorganosiloxane represented by the following structural formula.

[0116] R 4 3SiO(SiR 4 2O) k SiR 4 3

[0117] (In the formula, each R 4 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, and at least two of R4 in one molecule are alkenyl groups, and k is a number from 20 to 5000)

[0118] Preferably, it is a linear polydiorganosiloxane having an alkenyl group at each end of the molecular chain.

[0119] In the formula, each R 4 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or similar alkyl groups; vinyl, allyl, butenyl, pentenyl, hexenyl, or similar alkenyl groups; phenyl, tolyl, xylyl, or similar aryl groups; benzyl, phenethyl, or similar aralkyl groups; and chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl, or similar haloalkyl groups, etc. Moreover, at least two of R 4 in one molecule are alkenyl groups, preferably vinyl groups. In addition, each R 4 is preferably a functional group selected from alkyl groups having 1 to 10 carbon atoms such as methyl and alkenyl groups such as vinyl and hexenyl. Preferably, at least two of all R 4 are alkenyl groups, and the remaining R 4is methyl. It should be noted that, from the perspective of the technical effects of the invention, R 4 preferably substantially does not contain aryl groups such as phenyl. In the case of a large amount of aryl groups such as phenyl, the color resistance of the cured product at high temperatures sometimes deteriorates. Particularly preferably, it is preferred that each of the two ends of the molecular chain has an alkenyl group such as vinyl, and the other R 4 is methyl.

[0120] In the formula, k is a number from 20 to 5000, preferably from 30 to 3000, and particularly preferably from 45 to 800. If k is above the lower limit of the said range, a composition with less stickiness at room temperature can be obtained. On the other hand, if k is below the upper limit of the said range, good hot-melt properties can be achieved as a whole for the composition.

[0121] Here, in order to achieve hot-melt properties as a whole for the composition, the mass ratio of the (B) component, which is a linear or branched polyorganosiloxane, is in the range of 10 to 100 parts by mass, preferably in the range of 10 to 70 parts by mass, and more preferably in the range of 15 to 50 parts by mass, relative to 100 parts by mass of the (A) component, which is a polyorganosiloxane resin. If the content of the (B) component is within the said range, the composition can achieve good hot-melt properties, and moreover, the mechanical strength of the obtained cured product can be increased, and the stickiness of the obtained composition at room temperature can be reduced, improving its operability.

[0122] [(C) component]

[0123] (C) component is a curing agent for curing the above-mentioned (A) component and (B) component. Specifically, it is one or more curing agents selected from the following (c1) or (c2). It should be noted that two or more of these curing agents can be used in combination. For example, it can also be a curing system that simultaneously contains the (c1) component and the (c2) component.

[0124] (c1) Organic peroxide,

[0125] (c2) Organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms in the molecule and a hydrosilylation reaction catalyst.

[0126] (c1) Organic peroxide is a component that cures the above-mentioned (A) component and (B) component by heating, and examples thereof include: alkyl peroxides, diacyl peroxides, peresters, and percarbonates. It should be noted that the (c1) component can also react with a part of the (A2) component.

[0127] As the alkyl peroxides, examples thereof include: dicumyl peroxide, di-tert-butyl peroxide, di-tert-butyl cumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hex-3-yne, tert-butyl isopropylbenzene, 1,3-bis(tert-butylperoxyisopropyl)benzene, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane.

[0128] As the diacyl peroxides, examples thereof include: benzoyl peroxide, lauroyl peroxide, decanoyl peroxide, etc.

[0129] As the peresters, examples thereof include: 1,1,3,3-tetramethylbutyl peroxyneodecanoate, α-cumyl peroxyneodecanoate, tert-butyl peroxyneodecanoate, tert-butyl peroxyneoheptanoate, tert-butyl peroxypivalate, tert-hexyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, di-tert-butyl peroxyhexahydroterephthalate, tert-amyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, dibutyl peroxytrimethyladipate.

[0130] As the peroxydicarbonates, examples thereof include: bis(3-methoxybutyl) peroxydicarbonate, bis(2-ethylhexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, tert-butyl isopropyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate.

[0131] As such an organic peroxide, preferably an organic peroxide having a half-life of 10 hours at a temperature of 90 °C or higher or 95 °C or higher, examples thereof include: dicumyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, di-tert-butyl cumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,3-bis(tert-butylperoxyisopropyl)benzene, bis(2-tert-butylperoxyisopropyl)benzene, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxynonane.

[0132] (c1) The content of the organic peroxide is not limited, and is preferably in the range of 0.05 to 10 parts by mass, or in the range of 0.10 to 5.0 parts by mass, based on the total of components (A) and (B) (100 parts by mass).

[0133] (c2) The organohydrogenpolysiloxane having at least two silicon atoms bonded to hydrogen atoms in the molecule and the hydrosilylation reaction catalyst are components that cure the composition by the addition reaction (hydrosilylation reaction) of the organohydrogenpolysiloxane as a crosslinking agent with the carbon-carbon double bonds in the (A) component and the (C) component in the presence of the hydrosilylation reaction catalyst.

[0134] The structure of the organohydrogenpolysiloxane as a crosslinking agent is not particularly limited and can be linear, branched, cyclic or resinous. That is, the (c2) component can be the following organohydrogenpolysiloxane: with the organohydrogensiloxaneoxy unit (D 2 / 2 unit, R is independently a monovalent organic group) shown as the main structural unit and having the diorganohydrogensiloxaneoxy unit (M H unit, R is independently a monovalent organic group) shown at its end. In particular, in the case of uses other than the molding process described later, even if this curable organosilicon composition is a chain-like organohydrogenpolysiloxane composed of the above-mentioned D 1 / 2 units, etc., it can be cured sufficiently for practical use. H units, R is independently a monovalent organic group). In particular, in the case of uses other than the molding process described later, even if this curable organosilicon composition is a chain-like organohydrogenpolysiloxane composed of the above-mentioned D H units, etc., it can be cured sufficiently for practical use.

[0135] On the other hand, when this curable organosilicon composition is used in the molding process, the content of the curing-reactive functional groups containing carbon-carbon double bonds in this composition is small. Therefore, from the viewpoints of curing speed, its moldability, and curability, it is preferable that the organohydrogenpolysiloxane is: containing the monoorganosiloxaneoxy unit (T unit, R is a monovalent organic group or a silicon atom bonded to a hydrogen atom) shown as RSiO 3 / 2 or a branched unit of the siloxaneoxy unit (Q unit) shown as SiO 4 / 2 , and having at least two diorganohydrogensiloxaneoxy units (M 1 / 2 units, R is independently a monovalent organic group) in the molecule, and an organohydrogenpolysiloxane resin having an MH unit at the molecular end. H units, R is independently a monovalent organic group).

[0136] Particularly preferred organohydrogenpolysiloxane is the organohydrogenpolysiloxane resin shown by the following average unit formula.

[0137] (R 5 3SiO 1 / 2 ) l (R 6 2SiO 2 / 2 ) m (R 6 SiO 3 / 2 ) n (SiO 4 / 2 ) p (R 2 O1 / 2 ) q

[0138] In the formula, each R 5 is the same or different and is a monovalent hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom that does not have an aliphatic unsaturated carbon bond. Among them, at least two Rs in one molecule 5 are hydrogen atoms. As the monovalent hydrocarbon group of R 5 , for example, are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or similar alkyl groups; phenyl, tolyl, xylyl or similar aryl groups; benzyl, phenethyl or similar aralkyl groups; and chloromethyl, 3-chloropropyl, 3,3,3-trifluoropropyl or similar haloalkyl groups, etc. From an industrial perspective, methyl or phenyl is preferred.

[0139] In the formula, R 6 is a monovalent hydrocarbon group having 1 to 10 carbon atoms that does not have an aliphatic unsaturated carbon bond, and groups the same as the above monovalent hydrocarbon groups can be exemplified. On the other hand, R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and groups the same as R2 in the above component (A1) or component (A2) can be exemplified.

[0140] In the formula, l, m, n, and p are numbers that satisfy the following: 0.1 ≦ l ≦ 0.80, 0 ≦ m ≦ 0.5, 0 ≦ n ≦ 0.8, 0 ≦ p ≦ 0.6, 0 ≦ q ≦ 0.05, where n + p > 0.1 and l + m + n + p = 1. Here, when this composition is used in the molding process, specifically, the organohydrogenpolysiloxane resin as part of the (c2) component is preferably M H MT resin, M H MTT H resin, M H MTQ resin, M H MQ resin, M H MTT H Q, and M H Q resin.

[0141] Particularly preferably, the organohydrogenpolysiloxane as part of the (c2) component is the M H Q resin represented by the following formula.

[0142] (H(CH3)2SiO 1 / 2 ) l1 (SiO 4 / 2 ) p1

[0143] Here, l1 + p1 = 1, and preferably 0.1 ≦ l1 ≦ 0.80 and 0.20 ≦ p1 ≦ 0.90.

[0144] Similarly, the organohydrogenpolysiloxane as part of the component (c2) may contain linear polydiorganosiloxane, organohydrogenpolysiloxane or polydiorganosiloxane-organohydrogensiloxane copolymer whose molecular chain ends are capped with a silicon atom-bonded hydrogen atom or trimethylsiloxy group. The degree of siloxane polymerization of these linear organohydrogenpolysiloxanes is not particularly limited and is in the range of 2 to 200, preferably in the range of 5 to 100.

[0145] The content of the organohydrogenpolysiloxane as part of the component (c2) is an amount sufficient for curing the curable organosilicon composition of the present invention. The molar ratio of the silicon atom-bonded hydrogen atom in the organohydrogenpolysiloxane is 0.5 or more, preferably in the range of 0.5 to 20, relative to the curing-reactive functional groups containing carbon-carbon double bonds (such as alkenyl groups such as vinyl) in the components (A) and (B). In particular, when the component (c2) contains the above-mentioned organohydrogenpolysiloxane resin, the molar ratio of the silicon atom-bonded hydrogen atom in the organohydrogenpolysiloxane resin is preferably in the range of 0.5 to 20, or in the range of 1.0 to 10, relative to the curing-reactive functional groups containing carbon-carbon double bonds in the components (A) and (B).

[0146] Examples of the hydrosilylation reaction catalyst as part of the component (c2) include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts. From the aspect of significantly promoting the curing of this composition, platinum-based catalysts are preferred. Examples of this platinum-based catalyst include platinum micropowder, chloroplatinic acid, an alcoholic solution of chloroplatinic acid, a platinum-alkenylsiloxane complex, a platinum-olefin complex, a platinum-carbonyl complex, and a catalyst in which these platinum-based catalysts are dispersed or encapsulated by thermoplastic resins such as organosilicon resins, polycarbonate resins, and acrylic resins. A platinum-alkenylsiloxane complex is particularly preferred. Examples of this alkenylsiloxane include 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxanes in which a part of the methyl groups of these alkenylsiloxanes are replaced by ethyl, phenyl, etc., and alkenylsiloxanes in which the vinyl groups of these alkenylsiloxanes are replaced by allyl, hexenyl, etc. In particular, from the aspect of good stability of this platinum-alkenylsiloxane complex, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred, and it is preferably added in the form of an alkenylsiloxane solution of this complex. In addition, from the viewpoint of improving the operability and pot life of the composition, a particulate platinum-containing hydrosilylation reaction catalyst dispersed or encapsulated by a thermoplastic resin can also be used. It should be noted that as a catalyst for promoting the hydrosilylation reaction, non-platinum-based metal catalysts such as iron, ruthenium, and iron / cobalt can be used.

[0147] The addition amount of the hydrosilylation reaction catalyst as part of the component (c2) is preferably an amount in the range of 0.01 to 500 ppm, an amount in the range of 0.01 to 100 ppm, or an amount in the range of 0.01 to 50 ppm in terms of mass unit of the metal atom relative to the whole composition.

[0148] The particularly preferred component (c2) at least contains (c2-1) the organohydrogenpolysiloxane resin represented by the average unit formula and the hydrosilylation reaction catalyst.

[0149] When the above hydrosilylation reaction catalyst is used as part of the component (C), from the viewpoint of the storage stability of the present curable organosilicon composition, it is preferably contained in advance in the fine particles when producing polyorganosiloxane resin particles such as the component (A1) and the component (A2). Among them, it is preferable that the whole mixture constituting the fine particles does not become curable reactively alone.

[0150] When attempting to impart functionality to the obtained cured product with the curable organosilicon composition of the present invention, in addition to the above components (A) to (C), a component (D) functional filler may be further contained.

[0151] The functional filler as the component (D) is a component for imparting mechanical properties and other properties to the cured product, and examples thereof include: inorganic fillers, organic fillers, and mixtures thereof. Examples of the inorganic filler include: reinforcing fillers, white pigments, heat conductive fillers, conductive fillers, phosphors, and mixtures of at least two of them. Examples of the organic filler include: organosilicon resin-based fillers, fluororesin-based fillers, and polybutadiene resin-based fillers. It should be noted that the shape of these fillers is not particularly limited and may be spherical, spindle-shaped, flat-shaped, needle-shaped, irregular-shaped, etc.

[0152] When the present composition is used for applications such as encapsulants, protective agents, adhesives, etc., from the viewpoint of improving the mechanical strength, protectiveness, and adhesiveness of the cured product, it is preferable to contain a reinforcing filler in at least a part of the component (D).

[0153] In addition to improving the mechanical strength of the cured product, enhancing protection and adhesiveness, reinforcing fillers may also be added as binder fillers for curable silicone compositions prior to curing for the purpose of maintaining a solid particulate form. Examples of such reinforcing fillers include: fumed silica, precipitated silica, fused silica, calcined silica, fumed titanium dioxide, quartz, calcium carbonate, diatomaceous earth, alumina, aluminum hydroxide, zinc oxide, zinc carbonate. In addition, these reinforcing fillers may be surface-treated with substances such as: organoalkoxysilanes such as methyltrimethoxysilane; organohalosilanes such as trimethylchlorosilane; organosilazanes such as hexamethyldisilazane; siloxane oligomers such as α,ω-silanol-terminated dimethylsiloxane oligomers, α,ω-silanol-terminated methylphenylsiloxane oligomers, α,ω-silanol-terminated methylvinylsiloxane oligomers. The particle size of the reinforcing filler is not limited, and the median particle size based on laser diffraction scattering particle size distribution measurement is preferably in the range of 1 nm to 500 μm. Moreover, fibrous fillers such as calcium metasilicate, potassium titanate, magnesium sulfate, sepiolite, xonolite, aluminum borate, asbestos, and glass fiber can be used as the reinforcing filler.

[0154] Moreover, for the purpose of imparting other functions to the cured product obtained by using this composition, white pigments, heat-conductive fillers, electrically conductive fillers, or phosphors may also be incorporated. In addition, for the purpose of improving stress relaxation characteristics and the like of the cured product, organic fillers such as silicone elastomer fine particles may also be incorporated.

[0155] The white pigment is a component that imparts whiteness to the cured product and enhances light reflectivity, and the cured product obtained by curing this composition by incorporating this component can be used as a light-reflecting material for luminescent / optical devices. Examples of such white pigments include: metal oxides such as titanium oxide, alumina, zinc oxide, zirconia, and magnesia; hollow fillers such as glass spheres and glass beads; and barium sulfate, zinc sulfate, barium titanate, aluminum nitride, boron nitride, and antimony oxide. Titanium oxide is preferred in terms of high light reflectivity and hiding power. In addition, alumina, zinc oxide, and barium titanate are preferred in terms of high light reflectivity in the UV region. The average particle size and shape of the white pigment are not limited, and the average particle size is preferably in the range of 0.05 to 10.0 μm or in the range of 0.1 to 5.0 μm. In addition, the white pigment may be surface-treated with a silane coupling agent, silica, alumina, or the like.

[0156] Thermal conductive fillers or conductive fillers are added for the purpose of imparting thermal conductivity / electrical conduction to the cured product. Specifically, examples thereof include: metal fine powders such as gold, silver, nickel, copper, and aluminum; fine powders of ceramics, glass, quartz, organic resins, etc. with metals such as gold, silver, nickel, and copper vapor-deposited or plated on their surfaces; metal compounds such as alumina, magnesia, aluminum nitride, boron nitride, and zinc oxide; graphite; and mixtures of two or more of them. In the case where electrical insulation is required for this composition, metal oxide-based powders or metal nitride-based powders are preferred, and alumina powder, zinc oxide powder, or aluminum nitride powder is particularly preferred. These thermal conductive fillers or conductive fillers can also be used in combination in terms of the requirements for thermal conductivity / electrical conduction, such as type, particle size, and particle shape.

[0157] The phosphor is a component incorporated for the purpose of converting the emission wavelength from a light source (light semiconductor element) when the cured product is used as a wavelength conversion material. There is no particular limitation on the phosphor, and examples thereof include yellow, red, green, and blue light-emitting phosphors composed of oxide-based phosphors, oxynitride-based phosphors, nitride-based phosphors, sulfide-based phosphors, thioxide-based phosphors, etc., which are widely used in light-emitting diodes (LEDs).

[0158] Examples of the silicone fine particles include non-reactive silicone resin fine particles and silicone elastomer fine particles. From the viewpoint of improving the flexibility or stress relaxation characteristics of the cured product, silicone elastomer fine particles are preferably exemplified.

[0159] The silicone elastomer fine particles are crosslinked products of linear polydiorganosiloxanes mainly composed of diorganosiloxy units (D units). The silicone elastomer fine particles can be prepared by crosslinking reactions of polydiorganosiloxanes such as hydrosilylation reactions and condensation reactions of silanol groups. Among them, they can be preferably obtained by crosslinking an organohydrogenpolysiloxane having a silicon-bonded hydrogen atom in the side chain or at the end with a polydiorganosiloxane having an unsaturated hydrocarbon group such as an alkenyl group in the side chain or at the end under a hydrosilylation reaction catalyst. The silicone elastomer fine particles can have various shapes such as spherical, flat, and irregular shapes. From the aspect of dispersibility, spherical shapes are preferred, and regular spherical shapes are more preferred. Examples of commercially available products of such silicone elastomer fine particles include "TREFIL E series" and "EPPOWDER series" manufactured by DOW TORAY Co., Ltd., and "KMP series" manufactured by Shin-Etsu Chemical Co., Ltd.

[0160] For the purpose of stably incorporating the above-described functional fillers in the present composition, etc., a specific surface treatment agent can be used in an amount of 0.1 to 2.0% by mass, 0.1 to 1.0% by mass, or 0.2 to 0.8% by mass based on the total mass of the component (D) to perform surface treatment of the filler. Examples of these surface treatment agents can be, for example, fluorine compounds such as methylhydrogenpolysiloxane, silicone resin, metal soap, silane coupling agent, perfluoroalkylsilane, and perfluoroalkyl phosphate salt, etc.

[0161] In particular, when the component (D) is a heat-conductive filler and is incorporated in a large amount in the curable silicone composition of the present invention, as the heat-conductive filler, particularly preferred are plate-like boron nitride powder having an average particle size of 0.1 to 30 μm, granular boron nitride powder having an average particle size of 0.1 to 50 μm, spherical and / or crushed alumina powder having an average particle size of 0.01 to 50 μm, or spherical and / or crushed graphite having an average particle size of 0.01 to 50 μm, or a mixture of two or more of them. Most preferably, it is a mixture of two or more of spherical and crushed alumina powder having an average particle size of 0.01 to 50 μm. In particular, by combining alumina powder having a large particle size and alumina powder having a small particle size at a ratio in accordance with the maximum density packing theory distribution curve, the packing efficiency can be improved, and low viscosity and high heat conductivity can be achieved.

[0162] Moreover, the heat-conductive filler is particularly preferably treated on at least a part of its surface with one or more silicone compounds. The preferred range of the treatment amount is as described above. Here, examples of the silicone compound as the surface treatment agent are low molecular weight silicone compounds such as silanes, silazanes, siloxanes or the like; and silicone polymers or oligomers such as polysiloxanes, polycarbosiloxanes or the like. Examples of the preferred silanes are so-called silane coupling agents. Representative examples of such silane coupling agents are alkyltrialkoxysilanes (such as methyltrimethoxysilane, vinyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane or the like), trialkoxysilanes containing organic functional groups (such as glycidoxypropyltrimethoxysilane, epoxycyclohexylethyltrimethoxysilane, methacryloxypropyltrimethoxysilane, aminopropyltrimethoxysilane or the like). Examples of the preferred siloxanes and polysiloxanes include: hexamethyldisiloxane, 1,3-dihexyltetramethyldisiloxane, trialkoxysilyl single-terminated polydimethylsiloxane, trialkoxysilyl single-terminated dimethylvinyl single-terminated polydimethylsiloxane, trialkoxysilyl single-terminated organic functional group single-terminated polydimethylsiloxane, trialkoxysilyl doubly terminated polydimethylsiloxane, organic functional group doubly terminated polydimethylsiloxane or the like. When using siloxanes, the number n of siloxane bonds is preferably in the range of 2 to 150. Examples of the preferred silazanes are hexamethyldisilazane, 1,3-dihexyltetramethyldisilazane or the like. Examples of the preferred polycarbosiloxanes are polymers having Si-C-C-Si bonds in the polymer main chain.

[0163] (D) The content of the component is not limited. From the viewpoint of excellent hardness and mechanical strength of the obtained cured product, the content of the (D) component is preferably in the range of 10 to 2000 parts by mass, in the range of 10 to 1500 parts by mass, or in the range of 10 to 1000 parts by mass with respect to the sum (100 parts by mass) of the (A) component and the (B) component.

[0164] The curable silicone composition of the present invention contains the above-mentioned (A) to (C) components and an optional (D) component. From the viewpoint of further improving its melting characteristics, it is possible to add (E) hot-melt particles having a dropping point of 50 °C or higher and a melt viscosity measured by a rotational viscometer at 150 °C of 10 Pa·s or less, and it is preferred.

[0165] As long as the conditions of the dropping point and the kinematic viscosity during melting at 150°C described above are satisfied, there are no particular limitations on the type of component (E), and one or more selected from various hot-melt synthetic resins, waxes, fatty acid metal salts, etc. can be used. This component (E) exhibits a low kinematic viscosity at a high temperature (150°C) and forms a melt with excellent fluidity. Moreover, by using the above components (A) to (C) in combination, the component (E) in the melt formed from this composition rapidly diffuses throughout the composition at a high temperature, thereby presenting the following effects: reducing the viscosity of the substrate surface to which the molten composition is applied and the entire composition, and sharply reducing the surface friction between the substrate and the molten composition, and greatly increasing the fluidity of the entire composition. Therefore, by adding only a very small amount relative to the total amount of other components, the viscosity and fluidity of the molten composition can be greatly improved.

[0166] As long as component (E) satisfies the above conditions of the dropping point and the kinematic viscosity during melting, it can also be a petroleum-based wax such as paraffin wax. However, from the viewpoint of the technical effects of the present invention, a hot-melt component composed of a fatty acid metal salt and a fatty acid ester of an erythritol derivative is preferred, and a metal salt of a higher fatty acid such as stearic acid, palmitic acid, oleic acid, and isononanoic acid is particularly preferred; pentaerythritol tetrastearate, dipentaerythritol adipate stearate, glycerol tri-18-hydroxystearate, and pentaerythritol stearate. Here, there are no particular limitations on the type of the above fatty acid metal salt, and preferred examples include alkali metal salts such as lithium, sodium, and potassium; alkaline earth metal salts such as magnesium, calcium, and barium; or zinc salts.

[0167] As component (E), a fatty acid metal salt with a free fatty acid amount (E0) of 5.0% or less is particularly preferred, a fatty acid metal salt and an erythritol derivative of 4.0% or less, and 0.05 to 3.5%. As such components, for example, at least one or more metal stearates can be exemplified. Specifically, it is most preferable to use a hot-melt component having a melting point of 150°C or less selected from calcium stearate (melting point 150°C), zinc stearate (melting point 120°C); magnesium stearate (melting point 130°C), pentaerythritol tetrastearate (melting point 60 - 70°C), dipentaerythritol adipate stearate (melting point 55 - 61°C), pentaerythritol stearate (melting point 62 - 67°C), etc.

[0168] Regarding the usage amount of component (E), when the entire composition is set to 100 parts by mass, the content of component (E0) is in the range of 0.01 to 5.0 parts by mass, and can be 0.01 to 3.5 parts by mass, 0.01 to 3.0 parts by mass. If the usage amount of component (E) exceeds the above upper limit, the adhesiveness and mechanical strength of the cured product obtained from the curable silicone composition of the present invention may be insufficient. In addition, when the usage amount of component (E) is lower than the above lower limit, sufficient fluidity during heat melting may sometimes not be achieved.

[0169] In addition, in this composition, as long as the object of the present invention is not impaired, a curing retarder and a tackifier may be contained as any other components.

[0170] Examples of the curing retarder include: alkynols such as 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, 1-ethynyl-1-cyclohexanol; enyne compounds such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne; alkenyl-containing low molecular weight siloxanes such as tetramethyltetravinylcyclotetrasiloxane, tetramethyltetrahexenylcyclotetrasiloxane; alkynyloxy silanes such as methyl-tris(1,1-dimethylpropynyloxy)silane, vinyl-tris(1,1-dimethylpropynyloxy)silane. The content of this curing retarder is not limited, and is preferably in the range of 10 to 10,000 ppm in terms of mass unit relative to this composition.

[0171] As the tackifier, an organosilicon compound having at least one alkoxy group bonded to a silicon atom in one molecule is preferred. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and methoxyethoxy, and methoxy is particularly preferred. In addition, examples of the group bonded to the silicon atom other than the alkoxy group in the organosilicon compound include halogen-substituted or unsubstituted monovalent hydrocarbon groups such as alkyl, alkenyl, aryl, aralkyl, and haloalkyl; glycidoxyalkyl groups such as 3-glycidoxypropyl and 4-glycidoxybutyl; glycidoxycyclohexylalkyl groups such as 2-(3,4-epoxycyclohexyl)ethyl and 3-(3,4-epoxycyclohexyl)propyl; epoxyalkyl groups such as 3,4-epoxybutyl and 7,8-epoxyoctyl; acryloyl group-containing monovalent organic groups such as 3-methacryloxypropyl; and a hydrogen atom. The organosilicon compound preferably has a group capable of reacting with an alkenyl group or a hydrogen atom bonded to a silicon atom in the present composition. Specifically, it preferably has a hydrogen atom bonded to a silicon atom or an alkenyl group. In addition, from the aspect of being able to impart good adhesiveness to various substrates, the organosilicon compound preferably has at least one monovalent organic group containing an epoxy group in one molecule. Examples of such an organosilicon compound 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 structures, and linear, branched, and network structures are particularly preferred. Examples of the organosilicon compound include silane compounds such as 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane; a siloxane compound having at least one alkenyl group bonded to a silicon atom or a hydrogen atom bonded to a silicon atom and an alkoxy group bonded to a silicon atom in one molecule, a mixture of a silane compound or a siloxane compound having at least one alkoxy group bonded to a silicon atom and a siloxane compound having at least one hydroxyl group bonded to a silicon atom and an alkenyl group bonded to a silicon atom in one molecule, a reaction mixture of an amino-containing organoalkoxysilane and an epoxy-containing organoalkoxysilane, an organic compound having at least two alkoxysilyl groups in one molecule and containing a bond other than a silicon-oxygen bond between these silyl groups, a silane containing an epoxy group represented by the general formula R a n Si(OR b ) 4-n or a partial hydrolysis condensate thereof (wherein R a is a monovalent epoxy group-containing organic group, R b is an alkyl group having 1 to 6 carbon atoms or a hydrogen atom. n is a number in the range of 1 to 3)

[0172] A reaction mixture of a vinyl-containing siloxane oligomer (including a siloxane oligomer having a linear or cyclic structure) and an epoxy group-containing trialkoxysilane, polymethyl silicate, polyethyl silicate, and an epoxy group-containing polyethyl silicate. The tackifier is preferably a low-viscosity liquid, and its viscosity is not limited, preferably in the range of 1 to 500 mPa·s at 25°C. In addition, the content of the tackifier is not limited, and is preferably in the range of 0.01 to 10 parts by mass relative to 100 parts by mass in total of the present composition.

[0173] In the present invention, as a particularly preferred tackifier, a reaction mixture of an amino group-containing organoalkoxysilane and an epoxy group-containing organoalkoxysilane can be exemplified. Such a component is a component for improving the initial adhesiveness to various substrates in contact during curing, particularly the low-temperature adhesiveness to an uncleaned adherend. In addition, in the curing system of the curable silicone composition containing this adhesion promoter, it sometimes functions as a crosslinking agent. Such a reaction mixture is disclosed in Japanese Patent Publication No. 52-8854 and Japanese Unexamined Patent Publication No. 10-195085.

[0174] Examples of the alkoxysilane having an amino group-containing organic group constituting such a component include: aminomethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)aminomethyltributoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-anilinopropyltriethoxysilane.

[0175] In addition, examples of the epoxy group-containing organoalkoxysilane include: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane.

[0176] The ratio of these alkoxysilanes having an amino group-containing organic group to the alkoxysilanes having an epoxy group-containing organic group is preferably in the range of (1:1.5) to (1:5) in terms of molar ratio, and particularly preferably in the range of (1:2) to (1:4). The component (e1) can be easily synthesized by mixing the above-mentioned alkoxysilane having an amino group-containing organic group and the alkoxysilane having an epoxy group-containing organic group and reacting them at room temperature or by heating.

[0177] Particularly, in the present invention, when an alkoxysilane having an amino group-containing organic group is reacted with an alkoxysilane having an epoxy group-containing organic group by the method described in Japanese Patent Laid-Open No. 10-195085, it is particularly preferable to contain a cyclic carbazinosiloxane derivative represented by the following general formula, which is cyclized by transesterification.

[0178] [Chemical Formula 1]

[0179]

[0180] {In the formula, R 1 is an alkyl group, an alkenyl group or an alkoxy group, and R 2 are the same or different and are groups selected from the group consisting of groups represented by the following general formula:

[0181] [Chemical Formula 2]

[0182]

[0183] (In the formula, R 4 is an alkylene group or an alkyleneoxyalkylene group, R 5 is a monovalent hydrocarbon group, R 6 is an alkyl group, R 7 is an alkylene group, R 8 is an alkyl group, an alkenyl group or an acyl group, and a is 0, 1 or 2.)

[0184] R 3 are the same or different and are a hydrogen atom or an alkyl group.}

[0185] Examples of such a cyclic carbazinosiloxane derivative include a cyclic carbazinosiloxane derivative having a silicon atom-bonded alkoxy group or a silicon atom-bonded alkenyl group in one molecule represented by the following structure.

[0186] [Chemical Formula 3]

[0187]

[0188] (In the formula, Rc is a group selected from methoxy, ethoxy, vinyl, allyl and hexenyl)

[0189] In addition, in the present invention, a silazane derivative represented by the following structural formula can also be used as a tackifier.

[0190] [Chemical Formula 4]

[0191]

[0192] In the formula, R 1 are the same or different and are a hydrogen atom or an alkyl group, and particularly, as R 1, preferably a hydrogen atom or a methyl group. Further, R in the above formula 2 is selected from the group consisting of a hydrogen atom, an alkyl group, and a group of the general formula -R 4 -Si(OR 5 ) x R 6 (3-x) wherein the alkoxysilyl group-containing organic group shown, wherein at least one of R 2 is the alkoxysilyl group-containing organic group. As the alkyl group of R 2 , examples thereof include a methyl group and the like. Further, in the alkoxysilyl group-containing organic group of R 2 , R in the formula 4 is a divalent organic group, examples thereof include an alkylene group or an alkyleneoxyalkylene group, in particular, preferably an ethylene group, a propylene group, a butylene group, a methyleneoxypropylene group, a methyleneoxypentyl group. Further, R in the formula 5 is an alkyl group having 1 to 10 carbon atoms, preferably a methyl group or an ethyl group. Further, R in the formula 6 is a substituted or unsubstituted monovalent hydrocarbon group, preferably a methyl group. Further, x in the formula is 1, 2 or 3, preferably 3.

[0193] As such an alkoxysilyl group-containing organic group of R 2 , examples thereof include the groups described below.

[0194] -(CH2)2Si(OCH3)2-(CH2)2Si(OCH3)2CH3

[0195] -(CH2)3Si(OC2H5)2-(CH2)3Si(OC2H5)(CH3)2

[0196] -CH2O(CH2)3Si(OCH3)3

[0197] -CH2O(CH2)3Si(OC2H5)3

[0198] -CH2O(CH2)3Si(OCH3)2CH3

[0199] -CH2O(CH2)3Si(OC2H5)2CH3

[0200] -CH2OCH2Si(OCH3)2-CH2OCH2Si(OCH3)(CH3)2

[0201] R in the above formula 3 is at least one group selected from the group consisting of a substituted or unsubstituted monovalent hydrocarbon group, an alkoxy group having 1 to 10 carbon atoms, a glycidyloxyalkyl group, an epoxyethyloxyalkyl group, and an acyloxyalkyl group. As R3 The monovalent hydrocarbon group of R may, for example, be an alkyl group such as a methyl group. 3 The alkoxy group of R may, for example, be a methoxy group, an ethoxy group, or a propoxy group. 3 The glycidyloxyalkyl group of R may, for example, be 3-glycidyloxypropyl. 3 The ethyleneoxyalkyl group of R may, for example, be 4-ethyleneoxybutyl or 8-ethyleneoxyoctyl. 3 The acyloxyalkyl group of R may, for example, be acetoxypropyl or 3-methacryloxypropyl. In particular, as R 3 , it is preferably an alkyl group, an alkenyl group, or an alkoxy group, and further preferably an alkyl group or an alkenyl group. Particularly preferably, it is a group selected from a methyl group, a vinyl group, an allyl group, and a hexenyl group.

[0202] Moreover, in this composition, as long as the object of the present invention is not impaired, heat-resistant agents such as iron oxide (red iron oxide), cerium oxide, cerium dimethylsilicate, cerium fatty acid salt, cerium hydroxide, and zirconium compounds; and other dyes, pigments other than white, and flame retardant imparting agents may be contained as any other components.

[0203] This composition can be used in the form of granules, pellets, sheets, films, or the like. The pellets refer to the shape obtained by tableting this composition, and have excellent handling workability and curability. It should be noted that "pellets" are sometimes also referred to as "tablets". The shape of the pellets is not limited, and is usually spherical, ellipsoidal, or cylindrical. In addition, the size of the pellets is not limited. For example, it has an average particle diameter or equivalent circle diameter of 500 μm or more. In the case of producing such a granular composition, tableting the composition formed into granules is an efficient production method. In the case of attempting to granulate the composition of the present invention, when using components (A) to (C) and other additives constituting the curable silicone composition of the present invention, a granular composition can be produced by stirring them together using a powder kneader described later, and a pelletized composition can be produced by tableting the obtained granular composition.

[0204] This curable silicone composition is a solid that is non-fluid at 25°C. Here, non-fluid means that it does not deform and / or flow in the absence of external force. Preferably, when this curable silicone composition is formed into granules or ingots, etc., it does not deform and / or flow at 25°C in the absence of external force. Such non-fluidity can be evaluated, for example, as follows: The formed composition is placed on a heating plate at 25°C, and even when no external force is applied to the composition or a certain load is applied, the composition does not substantially deform and / or flow. When it is non-fluid at 25°C, the composition has good shape retention at this temperature and low surface adhesiveness, so the composition can be easily handled even in the uncured state.

[0205] In addition, the softening point of this composition is preferably 100°C or lower. Such a softening point means that, on a heating plate, when a load of 100 g is continuously pressed on the composition with a height of 2 cm from above for 10 seconds, and after removing the load, when measuring the deformation amount of the composition, the temperature at which the deformation amount in the height direction becomes 1 mm or more.

[0206] This composition has a tendency for the temperature to rise and the viscosity to decrease sharply under high temperature / high pressure (i.e., for example, in the manufacturing process of the above laminate). As a useful value of the melt viscosity for processing the composition, it is preferably a value measured under the same high temperature / high pressure conditions as those in actual use of this composition. Therefore, for the melt viscosity of this composition, compared with measurement using a rotational viscometer such as a rheometer, it is preferably measured under high pressure using a Koka-type flow tester (manufactured by Shimadzu Corporation). Specifically, preferably, the melt viscosity of this composition measured using a Koka-type flow tester at 150°C is 200 Pa·s or less, more preferably 150 or less. The reason is that after this composition is melted by heat (i.e., heated and melted), the composition has good adhesion to the substrate cooled to 25°C.

[0207] [Method for manufacturing curable silicone composition]

[0208] The present composition can be produced by the following method: components (A) to (C) and any other optional components are powder-mixed at a temperature below 50°C, and then heated and melted to uniformly mix the components. Then, cooling is performed as needed, but the method is not limited to this. The composition can be produced by any method. The powder mixer that can be used in this production method is not particularly limited. As examples, it can be a single-shaft or double-shaft continuous mixer, a two-roll mixer, a ROSS mixer, a HOBART mixer, a dental mixer, a planetary mixer, a kneading mixer, a small grinder (labomill ser), a small grinder, and a Henschel mixer. Preferably, it is a small grinder (labomill ser) and a Henschel mixer. [Method for producing a curable silicone sheet]

[0209] The curable silicone sheet having hot melt properties formed from the present composition is not limited to the following production methods. It can be produced using polyorganosiloxane resin fine particles as raw materials (Method A), or a solid polyorganosiloxane resin and any linear polydiorganosiloxane at room temperature can be dispersed in an organic solvent, and the hot melt solid component after removing the organic solvent can be used as raw materials (hot bulk method) (Method B).

[0210] Specifically, the former (Method A) is a production method including the following steps:

[0211] Step 1: A step of mixing polyorganosiloxane resin fine particles, a curing agent, and optionally selected functional fillers;

[0212] Step 2: A step of kneading the mixture obtained in Step 1 while heating and melting at a temperature of 120°C or lower;

[0213] Step 3: A step of forming a laminate by laminating the heated, melted, and kneaded mixture obtained in Step 2 between two films each having at least one release surface; and

[0214] Step 4: A step of stretching the mixture in the laminate obtained in Step 3 between rollers to form a curable hot melt silicone sheet having a specific film thickness.

[0215] On the other hand, the latter (Method B) is a production method including the following steps:

[0216] Step 1: A step of removing the organic solvent from a solution in which a solid polyorganosiloxane resin and any linear polydiorganosiloxane at room temperature are dispersed or dissolved in an organic solvent at a temperature of 150°C or higher to obtain a hot melt solid component;

[0217] Step 2: A step of adding all curing agents to the hot-melt solid component obtained in Step 1 and kneading the mixture while heating and melting it at a temperature of 120°C or lower;

[0218] Step 3, a step of forming a laminate by laminating the heated and melted mixture obtained in Step 2 between two films each having at least one release surface; and

[0219] Step 4, a step of stretching the mixture in the laminate obtained in Step 3 between rolls to form a curable hot-melt silicone sheet having a specific film thickness.

[0220] It should be noted that in any of the manufacturing methods (Method A or Method B), Step 3 and Step 4 can be continuous and integrated steps. For example, the heated and melted mixture obtained in Step 2 can be laminated by spraying or coating it directly below the rolls between the films each having at least one release surface. At the same time, by adjusting the gap between the rolls, it is stretched and formed into a specific film thickness. In this way, a manufacturing method having a step that substantially combines Step 3 and Step 4 is also included within the scope of the above-mentioned manufacturing methods.

[0221] That is, Step 3 and Step 4 can also be continuously and integrally performed as follows: spraying or coating the mixture obtained in Step 2 between two release films, and a step of sandwiching the mixture between two release films, for example, between two long-sized release films; and a step of continuously passing the two obtained release films and the laminate composed of the mixture sandwiched between them through the rolls, stretching and forming the mixture between the release films, adjusting it to a specified film thickness, and obtaining the target laminate. Such a method of integrally performing Step 3 and Step 4 is also included in the above-mentioned manufacturing methods.

[0222] In addition, in step 3 of the above Method A or Method B, the step of laminating the heat-melted mixture between the films is not particularly limited, and may be (i) spraying or coating the heat-melted mixture from step 2 onto the first release film having a release surface, and then bringing the second release film into contact with the surface of the mixture opposite to the surface in contact with the first release film, and sandwiching the heat-melted mixture between the first release film and the second release film, that is, the clamping step; or (ii) spraying or coating the heat-melted mixture from step 2 between the first release film and the second release film having a release surface, thereby sandwiching the heat-melted mixture between the two release films. (ii) The following method can be exemplified: making the first and second release films approach each other by an appropriate method, such as by two rollers, etc., spraying or coating the mixture from step 2 at the approaching part of the two release films, and clamping the mixture between the gaps of the two release films simultaneously or substantially simultaneously. The above steps 3 and 4 are particularly preferably continuous steps.

[0223] It should be noted that for these manufacturing methods, the applicant has proposed the overall process of the manufacturing method of the curable silicone sheet and the manufacturing apparatus for the manufacturing method, etc. in Japanese Patent Application No. 2019-167832, Japanese Patent Application No. 2019-167833 and their priority claim applications. In the present invention, this method and manufacturing apparatus can also be applied when forming the curable hot-melt silicone composition into a sheet or film.

[0224] The type of the film-like substrate for manufacturing the curable silicone sheet having hot-melt properties is not particularly limited, and polyester film, polyolefin film, polycarbonate film, acrylic film, etc. can be appropriately used. The sheet-like substrate is preferably non-porous.

[0225] The release layer is a necessary component for easily peeling the sheet-like member formed from the curable silicone composition from the film-like substrate, and is sometimes also referred to as a release liner, spacer, release layer or release coating. Preferably, the release layer is a release layer having release coating ability such as a silicone-based release agent, fluorine-based release agent, alkyd-based release agent, or fluorosilicone-based release agent, or it can also be a substrate itself that forms physically fine irregularities on the surface of the substrate or is not easily adhered to the curable reactive silicone composition of the present invention or the adhesive material layer composed of its cured product. In particular, in the laminate of the present invention, a release layer formed by curing a fluorosilicone-based release agent is preferably used as the release layer.

[0226] The above laminate can be used, for example, by applying the sheet-like member formed from the curable silicone composition to the adherend and then peeling the uncured sheet-like member from the film-like substrate.

[0227] Here, the sheet-like member formed from the curable silicone composition has a thickness of 1 mm or less and can be a film-like adhesive. That is, the laminate may include a peelable film-like adhesive held by a base film, and is preferred. Since the film-like adhesive has hot melt properties, it can be an adhesive for temporary fixation of semiconductor components, etc., and can also be used as a die attach film.

[0228] In addition, compression molding, press molding, etc. can be directly performed on the sheet-like member formed from the curable silicone composition to integrally mold it with the base material. At this time, molding is performed in a state where a film-like base material remains on one side, and it can also be used as a release film to prevent adhesion to the mold during molding.

[0229] [Curable silicone sheet]

[0230] The curable silicone sheet obtained by the above manufacturing method contains at least a polyorganosiloxane resin, an optional linear polyorganosiloxane, and a curing agent. Furthermore, it is a curable silicone composition optionally containing functional fillers and other components, has hot melt properties, can be used as a heat-melting adhesive material, and forms a silicone cured product with excellent heat resistance and stress relaxation through curing. In particular, the curable silicone sheet has excellent moldability, gap filling properties, and adhesive force / cohesive force, and can be used as a die attach film and a film adhesive. In addition, it can be preferably used as a curable silicone sheet for an encapsulation layer formed by compression molding, press molding, or vacuum lamination. Even when used for any purpose, the curable silicone sheet is a sheet-like product with hot melt properties, so it can be preferably used for large-area bonding and encapsulation.

[0231] Specifically, it can also be that after the curable silicone sheet obtained by the above manufacturing method is peeled off from the release film, it is disposed at a desired position such as a semiconductor, and a film adhesive layer that fills gaps and irregularities is formed on the adherend to temporarily fix, dispose, and bond the adherends. Then, the curable silicone sheet is heated to 150 °C or higher, and the adherends are bonded by the cured product of the curable silicone sheet. It should be noted that the release film can be peeled off after heating the curable silicone sheet to form a cured product, and this is preferably used when it is used as a layer for encapsulating a substrate such as a semiconductor. The peeling time can be selected according to the use and usage method of the curable silicone sheet.

[0232] The curable silicone sheet is hot-melt, so it can be softened or even fluidized by heating the sheet before final curing. For example, even if the adherend surface has unevenness, it can fill the unevenness and gaps without gaps to form an adhesive surface. As a heating method of the curable silicone sheet, for example, various constant temperature baths, heating plates, electromagnetic heating devices, heating rollers, etc. can be used. In order to perform lamination and heating more efficiently, for example, an electric hot press, a diaphragm type laminator, a roll laminator, etc. are preferably used.

[0233] As described above, the curable silicone sheet of the present invention has excellent gap filling property during melting and softness of the cured product at room temperature to high temperature. Therefore, through the cured product, it can be extremely preferably used in a molding method including the following processes: a covering process (so-called die bottom filling method) of performing secondary molding and under fill of a semiconductor element including an optoelectronic semiconductor at one time. Moreover, according to the above characteristics, this composition can be preferably used in a molding method including the following processes: covering the surface of a semiconductor wafer substrate on which a single or multiple semiconductor elements are mounted, and performing a secondary molding covering process (so-called wafer molding) in such a way that the gaps between the semiconductor elements are filled with the cured product.

[0234] In the above processes, a compression molding machine, an injection molding machine, an auxiliary ram type molding machine, a sliding type molding machine, a double piston type molding machine or a molding machine for low pressure encapsulation, hot pressing, a vacuum laminator, etc. can be used. In particular, the curable silicone sheet of the present invention can be preferably used for the purpose of obtaining a cured product by compression molding, compression molding and vacuum lamination.

[0235] As the conditions for thermally curing the curable silicone sheet, the optimal temperature can be selected according to its curing system. In the case of a hydrosilylation reaction, it is preferably 150 °C or higher, and in the case of organic peroxide curing, it is preferably 170 °C or higher.

[0236] From the viewpoint of preferably being a protective member such as a semiconductor, the D-type durometer hardness of the cured product obtained by curing the curable silicone sheet of the present invention at 25 °C is preferably 20 or higher. It should be noted that the D-type durometer hardness is obtained by a D-type durometer in accordance with JIS K 6253-1997 "Test Method for Hardness of Vulcanized Rubber and Thermoplastic Rubber".

[0237] Moreover, from the viewpoint of preferably being a packaging material for a semiconductor for a flexible application that requires softness, the flexural elongation of the cured product measured by the method specified in JIS K 6911-1995 "General Test Methods for Thermosetting Plastics" is preferably 2% or higher, or 4% or higher.

[0238] [Use of the curable silicone sheet of the present invention]

[0239] The curable silicone sheet of the present invention has hot melt properties, excellent gap filling properties, workability and curability during melting (hot melting), and is therefore preferably used as an encapsulant and underfill for semiconductors; an encapsulant and underfill for power semiconductors such as SiC and GaN; an encapsulant and light reflection material for optoelectronic semiconductors such as light emitting diodes, photodiodes, phototransistors, and laser diodes; an adhesive, potting agent, protective agent, and coating agent for electrical / electronic applications. In addition, since this composition has hot melt properties, it is also preferably used as a material for molding by compression molding, compression molding, or vacuum lamination. In particular, it is preferably used as an encapsulant for semiconductors using the mold underfill method or the wafer molding method during molding.

[0240] In particular, the curable silicone sheet of the present invention can be used for large-area encapsulation of semiconductor substrates (including wafers and optoelectronic semiconductor substrates). Moreover, the sheet formed by molding the curable silicone composition of the present invention can be used for chip mounting films, encapsulation of flexible devices, and stress relief layers between two different substrates, such as bonding large-area substrates and panels, and panels to each other.

[0241] [Use of the cured product of the curable silicone sheet of the present invention]

[0242] The use of the cured product of the present invention is not particularly limited. The composition of the present invention has hot melt properties, excellent moldability and gap filling characteristics, and the cured product has flexibility, high stress relaxation characteristics, and bending elongation rate at the above room temperature. Therefore, the cured product obtained by curing this composition can preferably be used as a component for semiconductor devices, and can preferably be used as an encapsulation material for semiconductor elements including optoelectronic semiconductors, IC chips, etc., a light reflection material for optoelectronic semiconductor devices, an adhesive / bonding component for semiconductor devices, and an adhesive / bonding component for display panels.

[0243] There is no particular limitation on the semiconductor device including the component composed of the above cured product. In particular, a power semiconductor device, an optoelectronic semiconductor device, and a semiconductor device mounted on a flexible circuit board are preferred.

[0244] [Method for molding the cured product]

[0245] This composition can be cured by a method including at least the following steps (I) to (III).

[0246] (I) A step of heating this composition to 100 °C or higher to perform melting;

[0247] (II) A step of injecting the curable silicone composition obtained in step (I) into a mold, or a step of spreading the curable silicone composition obtained in step (I) over the mold by closing the mold; and

[0248] (III) Step of curing the curable organosilicon composition injected in the step (II).

[0249] In the above steps, a transfer molding machine, a compression molding machine, an injection molding machine, an auxiliary piston molding machine, a sliding molding machine, a double piston molding machine, a molding machine for low-pressure encapsulation, a vacuum laminator, etc. can be used. In particular, the composition of the present invention can be preferably used for the purpose of obtaining a cured product by transfer molding, compression molding, press molding, or vacuum laminator.

[0250] Finally, in step (III), the curable organosilicon composition injected (applied) in step (II) is cured. It should be noted that when using (c1) organic peroxide as the component (C), the heating temperature is preferably 150 °C or higher or 170 °C or higher, and when using (c2) an organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms in the molecule and a hydrosilylation reaction catalyst, the heating temperature is preferably 100 °C or higher or 130 °C or higher.

[0251] Examples

[0252] The hot-melt curable organosilicon composition of the present invention and its manufacturing method will be described in detail through examples and comparative examples. It should be noted that in the formula, Me and Vi represent methyl and vinyl, respectively. In addition, for the curable organosilicon compositions of each example and comparative example, the softening point was measured by the following method. In addition, the curable organosilicon composition was heated at 150 °C for 2 hours to prepare a cured product, and the elastic modulus (initial and after being placed at 150 °C for 1000 hours) was measured by the following method. The results are shown in Table 1.

[0253] [Softening point]

[0254] The curable organosilicon composition was molded into cylindrical particles. The particles were placed on a hot plate set at 25 °C to 100 °C, continuously pressed from above with a load of 100 g for 10 seconds, and after removing the load, the deformation amount of the particles was measured. The temperature at which the deformation amount in the height direction was 1 mm or more was defined as the softening point.

[0255] [Storage modulus]

[0256] The curable organosilicon composition was heated at 150 °C for 2 hours to prepare a cured product (initial cured product). The cured product was placed in an oven set at 150 °C for 1000 hours to obtain a matured cured product. The storage modulus of the cured product from -50 °C to 250 °C was measured using a rheometer ARES (manufactured by TA Instruments Japan Co., Ltd.), and the value at 25 °C was read out. The measured values at 25 °C are shown in Table 1.

[0257] Hereinafter, using the methods shown in Reference Examples 1 and 2, a polyorganosiloxane resin containing a hydrosilylation reaction catalyst was prepared, and the presence or absence of hot melt properties was evaluated by the presence or absence of a softening point / melt viscosity. In addition, the polyorganosiloxane resin particles were prepared by the methods shown in Reference Examples 3 to 10, and their heating loss (= mass reduction rate) was evaluated. It should be noted that in the reference examples, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane used in the platinum complex as the hydrosilylation reaction catalyst is denoted as "1,3-divinyltetramethyldisiloxane".

[0258] [Reference Example 1]

[0259] Into a 1 L flask, 270.5 g of a 55 mass% xylene solution of a polyorganosiloxane resin represented by the average unit formula

[0260] (Me2ViSiO 1 / 2 ) 0.05 (Me3SiO 1 / 2 ) 0.39 (SiO 4 / 2 ) 0.56 (HO 1 / 2 ) 0.02

[0261] and 0.375 g of a 1,3-divinyltetramethyldisiloxane solution of a platinum 1,3-divinyltetramethyldisiloxane complex (platinum metal content = about 4000 ppm) were uniformly stirred at room temperature (25 °C) to prepare a xylene solution of a polyorganosiloxane resin (1) containing 10 ppm of platinum metal by mass. In addition, this polyorganosiloxane resin (1) does not soften / melt even when heated to 200 °C and does not have hot melt properties.

[0262] [Reference Example 2]

[0263] Into a 1 L flask, 270.5 g of a 55 mass% xylene solution of a polyorganosiloxane resin represented by the average unit formula

[0264] (Me3SiO 1 / 2 ) 0.44 (SiO 4 / 2 ) 0.56 (HO 1 / 2 ) 0.02

[0265] 270.5 g of a 55 mass% xylene solution of the polyorganosiloxane resin shown and 0.375 g of a 1,3-divinyltetramethyldisiloxane solution of a platinum 1,3-divinyltetramethyldisiloxane complex (platinum metal content = approximately 4000 ppm) were uniformly stirred at room temperature (25 °C) to prepare a xylene solution of the polyorganosiloxane resin (2) containing 10 ppm of platinum metal by mass. In addition, the polyorganosiloxane resin (2) does not soften / melt even when heated to 200 °C and does not have hot melt properties.

[0266] [Reference Example 3: Non-hot melt polyorganosiloxane resin particles (1)]

[0267] The xylene solution of the polyorganosiloxane resin (1) prepared in Reference Example 1 was atomized at 50 °C by a spraying method using a spray dryer while removing xylene to prepare spherical non-hot melt polyorganosiloxane resin particles (1). Observation of the particles using an optical microscope showed that the particle size was 5 - 10 μm and the average particle size was 6.9 μm. In addition, when the particles were exposed to 200 °C for 1 hour, the heat loss on heating was 4.7 wt%.

[0268] [Reference Example 4: Non-hot melt polyorganosiloxane resin particles (2)]

[0269] The polyorganosiloxane resin particles adjusted in Reference Example 3 were cured in an oven set at 120 °C for 4 hours to prepare spherical non-hot melt polyorganosiloxane resin particles (2). Observation of the particles using an optical microscope showed that the particle size was 5 - 10 μm and no aggregation due to curing was observed. In addition, when the particles were exposed to 200 °C for 1 hour, the heat loss on heating was 2.3 wt%.

[0270] [Reference Example 5: Non-hot melt polyorganosiloxane resin particles (3)]

[0271] The polyorganosiloxane resin particles adjusted in Reference Example 3 were cured in an oven set at 120 °C for 8 hours to prepare spherical non-hot melt polyorganosiloxane resin particles (3). Observation of the particles using an optical microscope showed that the particle size was 5 - 10 μm and no aggregation due to curing was observed. In addition, when the particles were exposed to 200 °C for 1 hour, the heat loss on heating was 1.3 wt%.

[0272] [Reference Example 6: Non-hot melt polyorganosiloxane resin particles (4)]

[0273] The polyorganosiloxane resin particles adjusted in Reference Example 3 were cured in an oven set at 120 °C for 24 hours to prepare spherical non-meltable polyorganosiloxane resin particles (4). When these particles were observed with an optical microscope, the particle size was found to be 5 to 10 μm, and no agglomeration due to curing was observed. In addition, when the particles were exposed at 200 °C for 1 hour, the loss on heating was 0.7 wt%.

[0274] [Reference Example 7: Non-meltable polyorganosiloxane resin particles (5)]

[0275] A xylene solution of the polyorganosiloxane resin (2) prepared in Reference Example 2 was atomized by a spray method using a spray dryer at 50 °C while removing xylene to prepare spherical non-meltable polyorganosiloxane resin particles (5). When these particles were observed with an optical microscope, the particle size was found to be 5 to 10 μm, and the average particle size was 7.4 μm. In addition, when the particles were exposed at 200 °C for 1 hour, the loss on heating was 4.8 wt%.

[0276] [Reference Example 8: Non-meltable polyorganosiloxane resin particles (6)]

[0277] The polyorganosiloxane resin particles adjusted in Reference Example 7 were cured in an oven set at 120 °C for 4 hours to prepare spherical non-meltable polyorganosiloxane resin particles (2). When these particles were observed with an optical microscope, the particle size was found to be 5 to 10 μm, and no agglomeration due to curing was observed. In addition, when the particles were exposed at 200 °C for 1 hour, the loss on heating was 2.1 wt%.

[0278] [Reference Example 9: Non-meltable polyorganosiloxane resin particles (7)]

[0279] The polyorganosiloxane resin particles adjusted in Reference Example 7 were cured in an oven set at 120 °C for 8 hours to prepare spherical non-meltable polyorganosiloxane resin particles (7). When these particles were observed with an optical microscope, the particle size was found to be 5 to 10 μm, and no agglomeration due to curing was observed. In addition, when the particles were exposed at 200 °C for 1 hour, the loss on heating was 1.2 wt%.

[0280] [Reference Example 10: Non-meltable polyorganosiloxane resin particles (8)]

[0281] The polyorganosiloxane resin particles adjusted in Reference Example 7 were cured in an oven set at 120 °C for 24 hours to prepare spherical non-melting polyorganosiloxane resin particles (8). Observation of the particles with an optical microscope revealed that the particle size was 5 to 10 μm and no aggregation due to curing was observed. In addition, when the particles were exposed at 200 °C for 1 hour, the weight loss on heating was 0.8 wt%.

[0282] [Example 1]

[0283] 67.0 g of non-melting polyorganosiloxane resin particles (7) (vinyl content = 0% by mass);

[0284] Formula

[0285] ViMe2SiO(Me2SiO) 800 SiViMe2

[0286] 33.0 g of dimethylpolysiloxane endblocked with dimethylvinylsilanyloxy groups at both ends of the molecular chain shown (vinyl content = 0.09% by mass);

[0287] Formula

[0288] Me3SiO(MeHSiO)7(Me2SiO) 6.5 SiMe3

[0289] 0.21 g of organohydrogenpolysiloxane shown;

[0290] {The amount such that the hydrogen atoms bonded to silicon atoms in the above organohydrogenpolysiloxane become 1.3 moles per mole of vinyl groups in the dimethylpolysiloxane endblocked with dimethylvinylsilanyloxy groups at both ends of the molecular chain},

[0291] 234.4 g of alumina with an average particle size of 0.44 μm (AES-12 manufactured by Sumitomo Chemical Co., Ltd.); and 1-ethynyl-1-cyclohexanol (in an amount of 1000 ppm by mass with respect to the present composition) were put into a small crusher and stirred at room temperature (25 °C) for 1 minute to prepare a uniform curable granular silicone composition. In addition, the measurement results of the softening point and the like of the composition are shown in Table 1.

[0292] [Example 2]

[0293] 63.3 g of non-melting polyorganosiloxane resin particles (7) (vinyl content = 0% by mass);

[0294] 3.5 g of non-melting polyorganosiloxane resin particles (3) (vinyl content = 1.91% by mass);

[0295] Formula

[0296] ViMe2SiO(Me2SiO) 800 SiViMe2

[0297] 33.2 g of dimethylpolysiloxane endblocked with dimethylvinylsilanyloxy at both ends of the molecular chain shown (vinyl content = 0.09% by mass);

[0298] Formula

[0299] Me3SiO(MeHSiO)7(Me2SiO) 6.5 SiMe3

[0300] 0.6 g of the organohydrogenpolysiloxane shown;

[0301] {The amount such that the hydrogen atoms bonded to silicon atoms in the above organohydrogenpolysiloxane become 1.2 moles relative to 1 mole of vinyl groups in the polyorganosiloxane resin particles (3) and dimethylpolysiloxane endblocked with dimethylvinylsilanyloxy at both ends of the molecular chain},

[0302] 218.4 g of alumina with an average particle size of 0.44 μm (AES-12 manufactured by Sumitomo Chemical Co., Ltd.); and 1-ethynyl-1-cyclohexanol (in an amount of 1000 ppm by mass relative to this composition) were put into a small grinder and stirred at room temperature (25 °C) for 1 minute to prepare a uniform curable granular organosilicon composition. In addition, the measurement results such as the softening point of this composition are shown in Table 1.

[0303] [Example 3]

[0304] 60.2 g of non-melting polyorganosiloxane resin particles (8) (vinyl content = 0% by mass);

[0305] 7.0 g of non-melting polyorganosiloxane resin particles (4) (vinyl content = 1.91% by mass);

[0306] Formula

[0307] ViMe2SiO(Me2SiO) 800 SiViMe2

[0308] 32.8 g of dimethylpolysiloxane endblocked with dimethylvinylsilanyloxy at both ends of the molecular chain shown (vinyl content = 0.09% by mass);

[0309] Formula

[0310] (HMe2SiO 1 / 2 ) 0.67 (SiO 4 / 2 ) 0.33

[0311] 0.65 g of the shown organohydrogenpolysiloxane resin (content of silicon atoms bonded to hydrogen atoms = 0.95% by mass);

[0312] {An amount such that the silicon atoms bonded to hydrogen atoms in the above organohydrogenpolysiloxane resin become 1.0 mole relative to 1 mole of vinyl groups in the polyorganosiloxane resin particles (4) and the dimethylvinylsilanyloxy-terminated dimethylpolysiloxane at both ends of the molecular chain},

[0313] 273.0 g of alumina with an average particle size of 0.44 μm (AES-12 manufactured by Sumitomo Chemical Co., Ltd.); and 1-ethynyl-1-cyclohexanol (in an amount of 1000 ppm by mass relative to this composition) were put into a small grinder and stirred at room temperature (25°C) for 1 minute to prepare a uniform curable granular organosilicon composition. In addition, the measurement results such as the softening point of this composition are shown in Table 1.

[0314] [Example 4]

[0315] 56.4 g of non-melting polyorganosiloxane resin particles (8) (vinyl group content = 0% by mass);

[0316] 10.3 g of non-melting polyorganosiloxane resin particles (4) (vinyl group content = 1.91% by mass);

[0317] Formula

[0318] ViMe2SiO(Me2SiO) 800 SiViMe2

[0319] 33.3 g of the dimethylvinylsilanyloxy-terminated dimethylpolysiloxane shown (vinyl group content = 0.09% by mass) at both ends of the molecular chain;

[0320] Formula

[0321] Me3SiO(MeHSiO)7(Me2SiO) 6.5 SiMe3

[0322] 1.57 g of the organohydrogenpolysiloxane shown;

[0323] {An amount such that the silicon atoms bonded to hydrogen atoms in the above organohydrogenpolysiloxane become 1.3 moles relative to 1 mole of vinyl groups in the polyorganosiloxane resin particles (4) and the dimethylvinylsilanyloxy-terminated dimethylpolysiloxane at both ends of the molecular chain},

[0324] 203.1 g of alumina with an average particle size of 0.44 μm (AES-12 manufactured by Sumitomo Chemical Co., Ltd.); and 1-ethynyl-1-cyclohexanol (in an amount of 1000 ppm by mass with respect to this composition) were put into a small grinder and stirred at room temperature (25 °C) for 1 minute to prepare a uniform curable granular silicone composition. In addition, the measurement results such as the softening point of this composition are shown in Table 1.

[0325] [Example 5]

[0326] 30.5 g of non-melting polyorganosiloxane resin fine particles (8) (vinyl content = 0% by mass);

[0327] 32.5 g of non-melting polyorganosiloxane resin fine particles (4) (vinyl content = 1.91% by mass);

[0328] Formula

[0329] ViMe2SiO(Me2SiO) 800 SiViMe2

[0330] 30.0 g of dimethylpolysiloxane endblocked with dimethylvinylsilanyloxy groups at both ends of the molecular chain shown (vinyl content = 0.09% by mass);

[0331] Formula

[0332] Me3SiO(MeHSiO)7(Me2SiO) 6.5 SiMe3

[0333] 2.0 g of organohydrogenpolysiloxane shown;

[0334] Formula

[0335] HMe2SiO(Me2SiO) 17 SiMe2H

[0336] 5.0 g of organohydrogenpolysiloxane shown;

[0337] {In an amount such that for 1 mole of vinyl in the polyorganosiloxane resin fine particles (4) and dimethylpolysiloxane endblocked with dimethylvinylsilanyloxy groups at both ends of the molecular chain, the silicon atom-bonded hydrogen atoms in the above two organohydrogenpolysiloxanes become 0.9 mole},

[0338] 1-ethynyl-1-cyclohexanol (in an amount of 1000 ppm by mass with respect to this composition) were put into a small grinder and stirred at room temperature (25 °C) for 1 minute to prepare a uniform curable granular silicone composition. In addition, the measurement results such as the softening point of this composition are shown in Table 1.

[0339] [Comparative Example 1]

[0340] 69.8 g of non - heat - fusible polyorganosiloxane resin particles (5) (vinyl content = 0% by mass);

[0341] Formula

[0342] ViMe2SiO(Me2SiO) 800 SiViMe2

[0343] 29.9 g of dimethylpolysiloxane endblocked with dimethylvinylsilanyloxy at both ends of the molecular chain (vinyl content = 0.09% by mass) shown by the formula;

[0344] Formula

[0345] Me3SiO(MeHSiO)7(Me2SiO) 6.5 SiMe3

[0346] 0.2 g of organohydrogenpolysiloxane shown by the formula;

[0347] {The amount of hydrogen atoms bonded to silicon atoms in the above organohydrogenpolysiloxane resin is 1.4 moles relative to 1 mole of vinyl in dimethylpolysiloxane endblocked with dimethylvinylsilanyloxy at both ends of the molecular chain},

[0348] 234.4 g of alumina with an average particle size of 0.44 μm (AES - 12 manufactured by Sumitomo Chemical Co., Ltd.) and 1 - ethynyl - 1 - cyclohexanol (in an amount of 1000 ppm by mass relative to the present composition) were put into a small grinder and stirred at room temperature (25°C) for 1 minute to prepare a uniform curable granular organosilicon composition. In addition, the measurement results such as the softening point of this composition are shown in Table 1.

[0349] [Comparative Example 2]

[0350] 66.0 g of non - heat - fusible polyorganosiloxane resin particles (5) (vinyl content = 0% by mass);

[0351] 3.0 g of non - heat - fusible polyorganosiloxane resin particles (1) (vinyl content = 1.91% by mass);

[0352] Formula

[0353] ViMe2SiO(Me2SiO) 800 SiViMe2

[0354] 29.8 g of dimethylpolysiloxane endblocked with dimethylvinylsilanyloxy at both ends of the molecular chain (vinyl content = 0.09% by mass) shown by the formula;

[0355] Formula

[0356] Me3SiO(MeHSiO)7(Me2SiO) 6.5 SiMe3

[0357] 0.6 g of the organohydrogenpolysiloxane shown;

[0358] {The amount of the silicon atom-bonded hydrogen atoms in the above organohydrogenpolysiloxane is 1.2 moles relative to 1 mole of the vinyl groups in the polyorganosiloxane resin particles (1) and the dimethylvinylsilanyloxy group-terminated dimethylpolysiloxane at both ends of the molecular chain},

[0359] 218.4 g of alumina with an average particle diameter of 0.44 μm (AES-12 manufactured by Sumitomo Chemical Co., Ltd.); and 1-ethynyl-1-cyclohexanol (in an amount of 1000 ppm by mass relative to this composition) were put into a small grinder and stirred at room temperature (25 °C) for 1 minute to prepare a uniform curable granular organosilicon composition. In addition, the measurement results such as the softening point of this composition are shown in Table 1.

[0360] [Comparative Example 3]

[0361] 62.5 g of non-melting polyorganosiloxane resin particles (6) (vinyl group content = 0% by mass);

[0362] 7.0 g of non-melting polyorganosiloxane resin particles (2) (vinyl group content = 1.91% by mass);

[0363] Formula

[0364] ViMe2SiO(Me2SiO) 800 SiViMe2

[0365] 29.8 g of the dimethylvinylsilanyloxy group-terminated dimethylpolysiloxane shown (vinyl group content = 0.44% by mass) at both ends of the molecular chain;

[0366] Formula

[0367] (HMe2SiO 1 / 2 ) 0.67 (SiO 4 / 2 ) 0.33

[0368] 0.65 g of the organohydrogenpolysiloxane resin shown (content of silicon atom-bonded hydrogen atoms = 0.95% by mass);

[0369] {The amount of the silicon atom-bonded hydrogen atoms in the above organohydrogenpolysiloxane is 1.0 mole relative to 1 mole of the vinyl groups in the polyorganosiloxane resin particles (2) and the dimethylvinylsilanyloxy group-terminated dimethylpolysiloxane at both ends of the molecular chain},

[0370] 273.0 g of alumina with an average particle size of 0.44 μm (AES-12 manufactured by Sumitomo Chemical Co., Ltd.); and 1-ethynyl-1-cyclohexanol (in an amount of 1000 ppm by mass relative to this composition) were put into a small crusher and stirred at room temperature (25 °C) for 1 minute to prepare a uniform curable granular silicone composition. In addition, the measurement results such as the softening point of this composition are shown in Table 1.

[0371] [Comparative Example 4]

[0372] 32.5 g of non-melting polyorganosiloxane resin fine particles (5) (vinyl content = 0% by mass);

[0373] 32.5 g of non-melting polyorganosiloxane resin fine particles (1) (vinyl content = 1.91% by mass);

[0374] Formula

[0375] ViMe2SiO(Me2SiO) 800 SiViMe2

[0376] 28.0 g of dimethylpolysiloxane endblocked with dimethylvinylsilanyloxy at both ends of the molecular chain shown (vinyl content = 0.09% by mass);

[0377] Formula

[0378] Me3SiO(MeHSiO)7(Me2SiO) 6.5 SiMe3

[0379] 2.0 g of the organohydrogenpolysiloxane shown;

[0380] Formula

[0381] HMe2SiO(Me2SiO) 17 SiMe2H

[0382] 5.0 g of the organohydrogenpolysiloxane shown;

[0383] {In an amount such that for 1 mole of vinyl in the polyorganosiloxane resin fine particles (1) and the dimethylpolysiloxane endblocked with dimethylvinylsilanyloxy at both ends of the molecular chain, the silicon-bonded hydrogen atoms in the above two organohydrogenpolysiloxanes are 0.9 mole}

[0384] 1-ethynyl-1-cyclohexanol (in an amount of 1000 ppm by mass relative to this composition) were put into a small crusher and stirred at room temperature (25 °C) for 1 minute to prepare a uniform curable granular silicone composition. In addition, the measurement results such as the softening point of this composition are shown in Table 1.

[0385] [Table 1]

[0386]

[0387] [Summary]

[0388] The curable silicone compositions of Examples 1 to 5 of the present invention are hot-melt compositions using a polyorganosiloxane resin with a weight loss rate of 2.0% by mass and having a softening point below 100°C. Even when the cured product is placed at 150°C for 1000 hours, no significant increase in the storage modulus is observed. Thus, it can be confirmed that the cured products obtained using the compositions of the respective examples can suppress hardening and maintain a tendency to be flexible through high-temperature storage. Therefore, it is considered that this composition is particularly preferably used for applications that are integrally molded with a substrate and used at high temperatures.

[0389] On the other hand, for Comparative Examples 1 to 4, the weight loss rates of the polyorganosiloxane resin components after being placed at 200°C for 1 hour are all 2% by mass or more. Although cured products having a softening point and an initial storage modulus similar to those of the respective examples are provided, when the obtained cured products are placed at 150°C for 1000 hours, a significant increase in the storage modulus is confirmed. Thus, it can be confirmed that the compositions of the comparative experiments tend to harden and become brittle through high-temperature storage.

[0390] [Production Example 1]

[0391] While heating the granular curable silicone composition of Example 1 etc. above to 80°C, heating and melt-kneading are carried out using a twin-screw extruder. In the form of a semi-solid softening material, it is supplied onto a release film (manufactured by TAKARA INCORPORATION, FL2-01) at a supply rate of 5 kg / hour and laminated between two release films. Next, by stretching this laminate between rolls, a hot-melt curable silicone sheet with a thickness of 500 μm is formed as a laminate between two release films, and the whole is cooled using a cooling roll set at -15°C. In this laminate, by separating the release films, a flat and homogeneous hot-melt curable silicone sheet can be obtained.

[0392] [Production Example 2]

[0393] While heating the curable silicone composition granulated in the above-mentioned Example 1 etc. to 80°C, heat-melting and kneading were carried out using a twin-screw extruder, and it was formed into a substantially sheet-like shape using a T-die (opening size: 800 μm × 100 mm, heated to 80°C), and it was supplied onto a release film (manufactured by TAKARAINCORPORATION Co., Ltd., FL2-01) at a supply rate of 5 kg / hour. After cooling the whole using a cooling roll set at -15°C, it was laminated between two release films. Next, by stretching this laminate between rolls, a hot-melt curable silicone sheet with a thickness of 500 μm was formed as a laminate laminated between two release films. In this laminate, by separating the release films, a flat and homogeneous hot-melt curable silicone sheet can be obtained.

[0394] <Production Example 3>

[0395] The polyorganosiloxane resin which is a white solid at 25°C and has an average unit formula

[0396] (Me2ViSiO 1 / 2 ) 0.05 (Me3SiO 1 / 2 ) 0.39 (SiO 4 / 2 ) 0.56 (HO 1 / 2 ) 0.02

[0397] as shown (vinyl content = 1.9% by mass) 3.76 kg;

[0398] The polyorganosiloxane resin which is a white solid at 25°C and has an average unit formula

[0399] (Me3SiO 1 / 2 ) 0.44 (SiO 4 / 2 ) 0.56 (HO 1 / 2 ) 0.02

[0400] as shown (vinyl content = 0% by mass) 3.08 kg; and the molecular chain two-terminal dimethylvinylsilanyloxy-terminated dimethylpolysiloxane shown by the formula ViMe2SiO(Me2SiO) 800 SiViMe2

[0401] as shown (vinyl content = 0.09% by mass) 2.56 kg

[0402] Dissolve a three-in-one motor in 4.00 kg of xylene in a barrel or tank. Feed the resulting solution into a twin-screw extruder with the maximum temperature set at 230°C, and remove xylene and low molecular weight polyorganosiloxane components under a vacuum of -0.08 MPa. As a result, a hot-melt transparent mixture 1 was obtained. Put mixture 1 into a cylindrical barrel or tank and cool it in this state to solidify. Measure the volatile component content of this mixture under the conditions of 200°C × 1 hour, and the result is 0.7% by mass.

[0403] Next, feed the obtained hot-melt mixture 1 into a twin-screw extruder at 170°C through a hot-melt machine for cylindrical barrels or tanks (VersaPail melter manufactured by Nordson Corporation) Figure 1 from the pipeline 1 shown at a rate of 9.67 kg / hr.

[0404] Next,

[0405] The

[0406] Me3SiO(Me2SiO) 37 (MeHSiO) 37 SiMe 23

[0407] shown organohydrogen polysiloxane of 0.500 kg / hr;

[0408] 1-Ethynyl-1-cyclohexanol in an amount of 500 ppm with respect to the whole composition

[0409] The mixture thus formed is fed from Figure 1 the pipeline 3-b shown. The set temperature of the input section is 150°C.

[0410] Next,

[0411] ViMe2SiO(Me2SiO) 800 SiViMe2

[0412] shown dimethylpolysiloxane endblocked with dimethylvinylsiloxy groups at both ends of the molecular chain (vinyl content = 0.09% by mass) of 0.15 kg / hr;

[0413] A mixture composed of a 1,3-divinyltetramethyldisiloxane solution of a platinum 1,3-divinyltetramethyldisiloxane complex (in an amount of 4.0 ppm by mass as platinum metal with respect to the whole composition) is fed from Figure 1 the pipeline 3-a (the set temperature of the input section is 80°C), and degassing and melt compounding are carried out under a vacuum of -0.08 MPa in the extruder.

[0414] The outlet temperature of the twin-screw extruder is set at 80 °C. As a semi-solid softened material, the mixture is fed at a rate of 1.0 m / minute onto a 330 mm-wide and 125 μm-thick release film (manufactured by TAKARA INCORPORATION, FL2-01), while the mixture is supplied onto the film at a rate of 5 kg / hr. The mixture is sandwiched between two release films to form a laminate. Then, the laminate is pressed and stretched between rollers with the temperature controlled at 90 °C, thereby forming a laminate with a cured hot-melt silicone composition sheet having a thickness of 300 μm sandwiched between two release films. Subsequently, the whole is cooled by air cooling. The Figure 1 shows the configuration of the manufacturing apparatus. By peeling off the release films from the obtained laminate, a bubble-free, flat, homogeneous, non-sticky, and transparent cured hot-melt silicone composition sheet with a softening temperature of 80 °C can be obtained.

[0415] Symbol Explanation

[0416] Figure 1

[0417] 1: Hot-melt machine

[0418] 2: Extruder

[0419] 3-a: Pump

[0420] 3-b: Pump

[0421] 3-c: Vacuum pump

[0422] 4-a: Release sheet

[0423] 4-b: Release sheet

[0424] 5-a: Tension roller (may optionally also have a temperature adjustment function)

[0425] 5-b: Tension roller (may optionally also have a temperature adjustment function)

[0426] 6: Cooling roller

[0427] 7: Film thickness gauge

[0428] 8: Slicing machine

[0429] 9: Foreign object inspection machine

Claims

1. A curable silicone composition having hot melt properties, characterized in that, The curable organosilicon composition contains: 100 parts by mass of (A) a polyorganosiloxane resin, the polyorganosiloxane resin containing the following components (A1) and (A2) in a mass ratio of 0:100 to 90:10, and the mass reduction rate when the components (A1) and (A2) are exposed at 200 °C for 1 hour being 2.0% by mass or less: (A1) As a whole molecule, it does not have thermoplasticity, has a functional group with curing reactivity containing a carbon-carbon double bond in the molecule, and contains 20 mol% or more of SiO of all siloxane units 4 / 2 a polyorganosiloxane resin of the siloxane unit shown, (A2) does not have thermoplasticity as a whole molecule, does not have a functional group with a curing reactivity containing a carbon-carbon double bond in the molecule, and contains 20 mol% or more of SiO of all siloxane units 4 / 2 a polyorganosiloxane resin of the siloxane unit shown; 10 to 100 parts by mass of (B) a linear or branched polyorganosiloxane that is liquid or plastic at 25 °C and has at least two curable reactive functional groups containing carbon-carbon double bonds in the molecule; and An amount of (C) a curing agent selected from the following (c1) or (c2) or more for curing the curable organosilicon composition: (c1) an organic peroxide, (c2) an organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms in the molecule and a hydrosilylation reaction catalyst; wherein, The component (A1) is a polyorganosiloxane resin represented by the following average unit formula: (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (R 2 O 1 / 2 ) e In the formula, each R 1 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, and 1 to 12 mol% of all Rs in one molecule 1 are alkenyl groups; each R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; a, b, c, d, and e are numbers satisfying the following: 0.10 ≤ a ≤ 0.60, 0 ≤ b ≤ 0.70, 0 ≤ c ≤ 0.80, 0.2 ≤ d ≤ 0.65, 0 ≤ e ≤ 0.05, where c + d > 0.20, and a + b + c + d = 1 The component (A2) is a polyorganosiloxane resin represented by the following average unit formula: (R 3 3SiO 1 / 2 ) f (R 3 2SiO 2 / 2 ) g (R 3 SiO 3 / 2 ) h (SiO 4 / 2 ) i (R 2 O 1 / 2 ) j In the formula, each R 3 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms and no carbon-carbon double bond; R2 is an alkyl group having a hydrogen atom or 1 to 10 carbon atoms; f, g, h, i, and j are numbers satisfying the following: 0.35 ≤ f ≤ 0.55, 0 ≤ g ≤ 0.20, 0 ≤ h ≤ 0.20, 0.45 ≤ i ≤ 0.65, 0 ≤ j ≤ 0.05, and f + g + h + i = 1; Among them, "having hot melt property" means that the softening point is between 50 and 200 °C, the melt viscosity at 150 °C is less than 1000 Pa·s, and it has a flowing property.

2. The curable organosilicon composition according to claim 1, wherein, The curable organosilicon composition further contains (D) a functional filler, and the amount of the component (D) is in the range of 10 to 2000 parts by mass with respect to 100 parts by mass of the sum of the components (A) and (B).

3. The curable organosilicon composition according to claim 1 or 2, wherein, The component (B) is a linear polydiorganosiloxane represented by the following structural formula: R 4 3SiO(SiR 4 2O) k SiR 4 3 In the formula, each R 4 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, and at least two of the Rs in one molecule 4 are alkenyl groups, and k is a number from 20 to 5000.

4. The curable organosilicon composition according to claim 1, wherein, The components (A1) and (A2) are spherical polyorganosiloxane resin fine particles with an average primary particle size of 1 to 20 μm.

5. The curable organosilicon composition according to claim 1, wherein, The component (C) at least contains (c2-1) an organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms in the molecule and (c2-2) a hydrosilylation reaction catalyst, The content of the organohydrogenpolysiloxane of (c2-1) is an amount such that the molar ratio of the silicon atom-bonded hydrogen atoms in the organohydrogenpolysiloxane resin to the curable reactive functional groups containing carbon-carbon double bonds in the components (A) and (B) becomes in the range of 0.5 to 20.

6. The curable organosilicon composition according to claim 1, wherein, The component (D) is a functional filler containing one or more selected from reinforcing fillers, white pigments, heat conductive fillers, conductive fillers, or organic fillers.

7. The curable organosilicon composition according to claim 1, wherein, The curable organosilicon composition is granular, particulate, or flaky.

8. A curable silicone composition sheet, which is formed from the curable silicone composition according to any one of claims 1 to 6, and the thickness of the curable silicone composition sheet is 10 to 1000 μm.

9. A film adhesive, which is the curable silicone composition sheet of claim 8.

10. A peelable laminate, which has: the curable silicone composition sheet of claim 8; and a sheet-like substrate, and on one or both sides of the curable silicone composition sheet, the sheet-like substrate has a peel surface facing the curable silicone composition sheet.

11. A cured product, which is obtained by curing the curable silicone composition according to any one of claims 1 to 6.

12. Use of the cured product according to claim 11 as a member for a semiconductor device or a member for an optoelectronic semiconductor device.

13. A semiconductor device or an optoelectronic semiconductor device, which has the cured product according to claim 11.

14. A method for manufacturing a silicone composition, which is a method for manufacturing the curable silicone composition according to any one of claims 1 to 6, and is characterized in that granulation is carried out by mixing only the components constituting the curable silicone composition under a temperature condition not exceeding 50 °C.

15. A method for molding a cured product, which at least includes the following steps (I) to (III): (I) A step of heating the curable silicone composition according to any one of claims 1 to 6 to 50 °C or higher and melting it; (II) A step of injecting the liquid curable silicone composition obtained in the step (I) into a mold, or a step of causing the curable silicone composition obtained in the step (I) to spread over the mold by closing the mold; and (III) A step of curing the curable silicone composition injected in the step (II).

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