Curable silicone composition having hot melt properties, cured product of same, and multilayer body comprising said composition

Abstract

[Problem] The present invention addresses the problem of providing: a curable silicone composition which has excellent curing characteristics and excellent fluidity during heating and melting, while enabling fine filling and exhibiting excellent storage stability as the whole composition, and which can be molded into a product having a thickness and forms a hard cured product that has little surface tackiness by means of curing; and a use of this curable silicone composition. [Solution] The present invention provides a curable silicone composition which contains: (A) a solid organopolysiloxane resin that contains (A1) an organopolysiloxane resin that has a curing-reactive functional group and contains 20% by mole or more of a Q unit, and (A2) an organopolysiloxane resin that does not have a curing-reactive functional group and contains 20% by mole or more of a Q unit; (B) 10 to 100 parts by mass of a linear or branched organopolysiloxane that has a curing-reactive functional group; (C) an organohydrogenpolysiloxane; and (D) a hydrosilylation catalyst-containing fine particles that use a thermoplastic resin which has a Tg within the range of 110°C to 200°C. This curable silicone composition as a whole has hot melt properties.

Description

Curable silicone composition having hot melt properties, cured product thereof, and laminate containing said composition

[0001] The present invention relates to a curable silicone composition that exhibits excellent curing properties and fluidity when heated and melted, allowing for fine filling, and that has excellent storage stability as a whole, allowing for molding to a relatively thick film, and that upon curing forms a relatively hard cured product with little surface tack, preferably a white or colored cured product.The present invention also relates to sheets / films formed from the curable silicone composition, laminates containing the same, methods for producing them, and uses for the cured products obtained by curing the composition.

[0002] Curable silicone compositions are used in a wide range of industrial fields because they can be cured to form cured products that have excellent heat resistance, cold resistance, electrical insulation, weather resistance, water repellency, and transparency. In particular, cured products of the curable silicone compositions of the present invention are generally less susceptible to discoloration than other organic materials and show little deterioration in their physical properties over time, making them suitable as sealants for semiconductor devices.

[0003] The applicant of the present invention has proposed a hot-melt curable granular silicone composition and a reactive silicone composition for molding in Patent Documents 1 and 2. These silicone compositions contain a large amount of inorganic filler to achieve their desired properties, and their melt viscosity is relatively high.

[0004] On the other hand, in recent years, miniaturization of semiconductor devices and the like has progressed, and the fineness of their substrate structures has become remarkable. When encapsulating substrates with such fine structures, low viscosity is required during encapsulation. Furthermore, with the recent increase in the area of ​​semiconductor devices, there is a tendency for film- or sheet-shaped encapsulants to be preferred.

[0005] Patent Document 3 discloses a transparent, hot-melt curable silicone sheet using a silicone resin. However, these compositions require the use of organic solvents due to their manufacturing process, making it difficult to incorporate inorganic fillers. Furthermore, due to their nature, all components are mixed and integrated, making it difficult to ensure storage stability. Furthermore, due to the disclosed manufacturing method, these curable silicone sheets have the problem of being difficult to produce with a film thickness of 100 μm or more.

[0006] To ensure the storage stability of curable silicone compositions, catalysts that are activated by irradiation with high-energy rays such as ultraviolet rays are sometimes used, and a curable silicone pressure-sensitive adhesive containing such a catalyst is proposed in Patent Document 4. However, these catalysts have the problem that, particularly in compositions that have strong absorption or reflection in the ultraviolet region, such as colored fillers or pigments, the high-energy rays are blocked, inhibiting the curing reaction, making them unsuitable for applications requiring coloration that include these pigments or fillers (for example, optical components such as reflectors and black sealants).

[0007] As described above, there is a need for a curable silicone composition that exhibits excellent fine sealing or filling properties when the composition is heated and melted, excellent storage stability, and excellent moldability, and that also exhibits sufficient curing properties even when a filler or pigment that blocks high-energy rays is used. The present applicants have proposed hot-melt silicone compositions (including film-form compositions) with excellent curing properties in Patent Documents 5 to 7, but there is still room for improvement, particularly in terms of fluidity and fine filling properties when heated and melted.

[0008] International Publication No. 2016 / 136243 Pamphlet International Publication No. 2019 / 078140 Pamphlet Special Publication No. 2017-512224 Patent Publication No. 2017-101137 International Publication No. 2021 / 200643 Pamphlet International Publication No. 2020 / 203304 Pamphlet International Publication No. 2021 / 132710 Pamphlet

[0009] An object of the present invention is to provide a hot-melt curable silicone composition that has low viscosity when heated and melted, excellent fluidity and fine filling properties, excellent curing characteristics and storage stability, and can maintain sufficient curability even when colored white, black, or other colors as needed, and to provide a cured product obtained by curing the composition that has little surface tack and is relatively hard. Furthermore, the present invention also provides a sheet or film made from such a curable silicone composition, particularly a void-free, substantially flat sheet or film with a film thickness of 10 to 1000 μm, and a peelable laminate comprising a sheet or film made from the curable silicone composition. A further object of the present invention is to provide a semiconductor device component made from a cured product of the curable silicone composition, a semiconductor device comprising the cured product, and a method for molding the cured product.

[0010] As a result of extensive investigations, the present inventors have discovered that: (A) an organopolysiloxane resin that is solid at 25°C and contains an organopolysiloxane resin that has a curing-reactive functional group and an organopolysiloxane resin that does not have a curing-reactive functional group in a specific ratio (20:80 to 90:10); (B) a linear or branched organopolysiloxane that has at least two curing-reactive functional groups in the molecule and is liquid or plastic at 25°C; (C) an organohydrogenpolysiloxane; We have discovered that the above problems can be solved by a curable silicone composition comprising (D) hydrosilylation catalyst-containing microparticles having a structure in which a hydrosilylation catalyst is encapsulated in a thermoplastic resin having a glass transition temperature (Tg) in the range of 110 to 200°C, (E) an inorganic filler in a specific quantitative range, and optionally (F) a hydrosilylation cure retarder having a boiling point of 200°C or higher, the composition as a whole having hot-melt properties, and have completed the present invention. In the present invention, it is preferred that at least a portion of component (E) is a white or colored inorganic filler.

[0011] The curable silicone composition may be formed into a sheet or film having a thickness of 10 to 2000 μm, and the curable silicone composition sheet or film may be a peelable laminate including a separator, or may be a laminate laminated with a portion of a substrate that is an electronic component or its precursor. Furthermore, the present invention can cure the curable silicone composition by heating it to a temperature equal to or higher than the glass transition point (Tg) of the thermoplastic resin in order to express the catalytic activity of component (D), thereby providing a cured product, its uses, and laminates containing the cured product.

[0012] The curable silicone composition of the present invention exhibits low viscosity and excellent heat-melting properties (i.e., hot-melt properties) with excellent fluidity and fine filling properties. At temperatures below the glass transition point (Tg) of the thermoplastic resin constituting component (D), the hydrosilylation reaction is suppressed, resulting in excellent storage stability. However, at temperatures above the melting point, instant curing is possible, resulting in excellent handling and workability (including control of the curing reaction) in overmolding and other processes. Furthermore, the curable silicone composition has the advantage of being highly thixotropic at temperatures above 100°C, meaning that it does not drip even when thermocompressed onto a substrate and then thermally cured in an oven or the like. Furthermore, because the curable silicone composition of the present invention is heat-curable, it is possible to compound large amounts of white or colored fillers or pigments without adversely affecting curing properties, thereby producing white or colored cured products and optical components and parts made therefrom.

[0013] Additionally, the curable silicone composition of the present invention forms a relatively hard cured product with little surface tack upon curing, making it suitable for use as a sealant to protect substrates, and also for double-sided adhesive applications where a relatively hard adhesive layer is required.

[0014] The curable silicone composition of the present invention can be produced using only a simple mixing step, and therefore can be produced efficiently. Furthermore, the present invention can provide such a curable silicone composition in the form of a void-free sheet or film having a thickness of 10 to 2000 μm, or in the form of a release laminate comprising the curable silicone composition sheet or film and a release sheet or film. Furthermore, a sheet or film made from the curable silicone composition of the present invention, or a release laminate comprising the same, can be cut to the desired size as needed in processes for producing electronic components, such as semiconductor devices, and can be used in industrial production processes such as bulk sealing or bulk bonding of large-area substrates.

[0015] FIG. 1 is a diagram showing the overall configuration of the curable silicone sheet manufacturing apparatus used in the examples (the entire section including the sheet forming section).

[0016] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to the preferred embodiments. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.

[0017] In the present invention, unless otherwise specified, "having hot-melt properties" means that the composition has a softening point between 50 and 200°C, a melt viscosity at 150°C (preferably a melt viscosity of less than 1000 Pa s), and flowable properties. Therefore, in this specification, the curable silicone composition of the present invention that has hot-melt properties is also referred to as a curable hot-melt silicone composition.

[0018] In the present invention, atmospheric pressure refers to the atmospheric pressure in the environment in which the curable silicone composition of the present invention is handled, such as in a laboratory or factory, and is not limited to a specific pressure. However, atmospheric pressure typically refers to a pressure in the range of 1 atmosphere (1013.25 hPa) to -100 hPa to +100 hPa, and particularly refers to 1 atmosphere (1013.25 hPa).

[0019] As used herein, room temperature refers to the temperature of the environment in which someone is handling the curable silicone composition of the present invention, and generally refers to a temperature of 0°C to 40°C, particularly 15°C to 30°C, and especially 18°C ​​to 25°C.

[0020] [Curable Hot-Melt Silicone Composition] The curable hot-melt silicone composition of the present invention is a composition (A1) of a silicone rubber composition having a mass loss of 2.0% by mass or less when exposed to 200°C for 1 hour, having a curable reactive functional group containing a carbon-carbon double bond in the molecule, and containing SiO ４／２ and (A2) an organopolysiloxane resin which is solid at 25°C and which does not have hot-melt properties by itself, and which has a mass loss of 2.0% or less when exposed to 200°C for 1 hour, does not have a curing-reactive functional group containing a carbon-carbon double bond in the molecule, and which contains 20% or more of Q units by mole of all siloxane units, and which does not have hot-melt properties by itself, in a mass ratio of (A1):(A2) = 20:80 to 90:10, 35:65 to 90:10, or 50:50 to 90:10. The silicone composition is heat-curable via a hydrosilylation reaction and comprises as its main components a combination of a 25°C (component (A)) and a linear or branched organopolysiloxane containing a secondary carbon-carbon bond (component (B)) that is liquid or plastic at 25°C, an organohydrogenpolysiloxane (component (C)) as a crosslinker, hydrosilylation catalyst-containing microparticles (component (D)) having a structure in which a hydrosilylation catalyst is encapsulated in a thermoplastic resin having a glass transition temperature (Tg) in the range of 110 to 200°C, and 0.01 to 100 parts by mass of an inorganic filler per 100 parts by mass of the total of components (A) to (D). The curable hot-melt silicone composition of the present invention may optionally contain a hydrosilylation reaction retarder, or so-called cure retarder. In this case, it is preferable to use a cure retarder with a boiling point of 200°C or higher, particularly a boiling point of 200°C or higher at 1 atmosphere (1013.25 hPa). Furthermore, other additives known in the art may be added to the curable hot-melt silicone composition of the present invention, as long as the desired properties of the present invention are maintained.

[0021] [Hot-melt properties and structure of curable silicone composition] The curable silicone composition of the present invention is characterized by having hot-melt properties as a whole composition and being flowable under heated conditions. In particular, it is preferable that the curable silicone composition of the present invention has a softening point of 50°C or higher and a melt viscosity at 150°C (preferably a melt viscosity of less than 200 Pa s as measured using a Koka type flow tester described below). Note that in the present invention, it is sufficient for the composition as a whole to have hot-melt properties, and the individual components that make up the composition (particularly component (A)) do not have hot-melt properties.

[0022] [Component (A)] In order to minimize the stickiness (surface tack) of the surface of the cured product obtained by curing the present composition and to suppress changes in the elastic modulus of the cured product at high temperatures, it is necessary that the mass loss of component (A) when exposed to 200°C for 1 hour be 2.0% by mass or less.

[0023] The curable silicone composition of the present invention comprises, as component (A), a combination of an organopolysiloxane resin that is solid at 25°C and does not exhibit hot melt properties by itself, and that has a curable functional group containing a carbon-carbon double bond and contains 20 mol% or more of Q units based on all siloxane units, and an organopolysiloxane resin that is solid at 25°C and does not exhibit hot melt properties by itself, and that does not have a curable functional group containing a carbon-carbon double bond and contains 20 mol% or more of Q units based on all siloxane units, in a mass ratio of 20:80 to 90:10, 35:65 to 90:10, or 50:50 to 90:10. ３ SiO １／２ , R ２ SiO ２／２ , RSiO ３／２ (R represents a monovalent organic group, particularly a monovalent hydrocarbon group having 1 to 10 carbon atoms), or a siloxane unit represented by R ２ O １／２ (R ２is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms), but suitably contains Q units in an amount of 20 mol % or more, preferably 40 mol % or more, and particularly 40 to 90 mol % of the total siloxane units. If the content of Q units is less than 20 mol %, even if the organopolysiloxane resin contains other branched siloxane units (for example, RSiO ３／２ Even if a large amount of ) is contained, the technical effect of the present invention may not be achieved.

[0024] The organopolysiloxane resin (A) is an organopolysiloxane resin mixture containing: (A1) an organopolysiloxane resin that has a curable functional group containing a carbon-carbon double bond in the molecule and contains Q units in an amount of 20 mol % or more of all siloxane units, and that does not have hot-melt properties by itself and is solid at 25°C; and (A2) an organopolysiloxane resin that does not have a curable functional group containing a carbon-carbon double bond in the molecule and contains Q units in an amount of 20 mol % or more of all siloxane units, and that does not have hot-melt properties by itself and is solid at 25°C, in a mass ratio of 20:80 to 90:10 (component (A1):component (A2)). Here, "cure-reactive" means that the component (C) can undergo a hydrosilylation reaction with the organohydrogensiloxane, thereby curing the entire composition, and refers to a curing-reactive functional group that contains a carbon-carbon double bond in the molecule, such as an alkenyl group or an acryloxy group.

[0025] The above-mentioned component (A) does not exhibit hot-melt properties by itself, but by using it in combination with the component (B) described below within a predetermined quantitative ratio, the composition of the present invention as a whole can be made to have hot-melt properties.

[0026] [Organopolysiloxane Resin (A1) Having a Curing-Reactive Functional Group] Component (A1) above is one of the main components of the composition, and is an organopolysiloxane resin that contains 20 mol % or more of Q units, does not have hot-melt properties on its own, and has a curing-reactive functional group containing a carbon-carbon double bond within the molecule.

[0027] Component (A1) must have a curing reactive group having a carbon-carbon double bond in the molecule. Such a curing reactive group is a hydrosilylation-reactive functional group that can form a cured product by a hydrosilylation crosslinking reaction with component (C). Such a curing reactive group may be, in particular, an alkenyl group, such as a vinyl group or a hexenyl group, having 2 to 10 carbon atoms.

[0028] Component (A1) is an organopolysiloxane resin that does not have hot-melt properties by itself and is solid in the absence of a solvent. "Not having hot-melt properties" here means that the organopolysiloxane resin (A1) by itself does not exhibit heat-melting behavior at or below 200°C. Specifically, it means that it has no softening point or melt viscosity at or below 200°C. For component (A1) to exhibit these physical properties, the functional groups in the organopolysiloxane resin are selected from monovalent hydrocarbon groups having 1 to 10 carbon atoms, particularly alkyl groups having 1 to 10 carbon atoms such as methyl, and are substantially free of aryl groups such as phenyl groups. For example, the proportion of aryl groups in all silicon-bonded organic groups may be 5 mol% or less, or even 2 mol% or less, and it is preferable that the resin contains no aryl groups at all. If component (A1) contains a large amount of aryl groups such as phenyl groups as organic groups, the component may exhibit hot-melt properties by itself, and the effect of reinforcing the cured product derived from the Q units may be reduced.

[0029] Preferably, the functional groups bonded to silicon atoms in the organopolysiloxane resin of component (A1) are selected from methyl groups and alkenyl groups such as vinyl groups, and 70 to 99 mol% of all silicon-bonded organic groups may be methyl groups, with the remaining silicon-bonded organic groups being alkenyl groups such as vinyl groups. Within this range, component (A1) does not by itself have hot-melt properties, but is useful as a component that is particularly excellent in terms of the discoloration resistance at high temperatures of the cured product obtained from the curable silicone composition of the present invention. The organopolysiloxane resin of component (A1) may also contain small amounts of hydroxyl groups or alkoxy groups.

[0030] Component (A1) is an organopolysiloxane resin that is solid in the absence of a solvent, and preferably component (A1) is: (A1-1) an organopolysiloxane resin represented by the following average unit formula: (R １ ３ SiO １／２ ) ａ (R １ ２ SiO 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 are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, provided that all R １ are alkenyl groups; and 1 to 12 mol % of each R ２ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; and a, b, c, d, and e are numbers that satisfy the following: 0.10≦a≦0.60, 0≦b≦0.70, 0≦c≦0.80, 0.20≦d≦0.65, 0≦e≦0.05, with the proviso that 0.20≦c+d and a+b+c+d=1), and is an organopolysiloxane resin that is solid at 25°C and does not possess hot-melt properties by itself.

[0031] In the above average unit formula, each R １ are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, for example, alkyl groups such as methyl groups; alkenyl groups such as vinyl groups; and aryl groups such as phenyl groups. １ 1 to 12 mol % of the total R １ Of these, 2 to 10 mol % are alkenyl groups, particularly preferably vinyl groups. If the alkenyl group content is below the lower limit of the above range, the mechanical strength (hardness, etc.) of the resulting cured product may be insufficient. On the other hand, if the alkenyl group content is equal to or less than the upper limit of the above range, a composition containing this component can achieve good hot-melt performance as a whole.

[0032] In the above formula, R ２ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.２ An example of the alkyl group of R is a methyl group. ２ Group R containing ２ O １／２ corresponds to the hydroxyl group or alkoxy group contained in the organopolysiloxane resin of component (A).

[0033] In the above formula, a represents the general formula: R １ ３ SiO １／２ a is a number indicating the proportion of siloxane units. a satisfies the conditions 0.1≦a≦0.60 and 0.15≦a≦0.55. When a is at or above the lower limit of the above range, a composition containing this component can achieve good hot melt performance as a whole. On the other hand, when a is at or below the upper limit of the above range, the mechanical strength (hardness, elongation, etc.) of the cured product obtained by curing the curable silicone composition of the present invention will not be too low.

[0034] In the above formula, b represents the general formula: R １ ２ SiO ２／２ b is a number indicating the proportion of siloxane units. b satisfies the conditions 0≦b≦0.70 and 0≦b≦0.60. When b is equal to or less than the upper limit of the aforementioned range, a composition containing this component can achieve good hot-melt performance as a whole and can also be obtained that is less sticky at room temperature.

[0035] In the above formula, c represents a group represented by the general formula: R ３ SiO ３／２ is a number indicating the proportion of siloxane units. c satisfies the conditions 0≦c≦0.80 and 0≦c≦0.75. When c is equal to or less than the upper limit of the above range, a composition containing this component can achieve good hot melt performance as a whole composition, and can obtain a low-tack or tack-free composition that is less sticky at room temperature. In the present invention, c may be, and preferably is, 0.

[0036] In the above formula, d is a number indicating the proportion of Q units and may be 0.20≦d≦0.65, or 0.25≦d≦0.65. When d is within this range, a composition containing this component can achieve good hot-melt performance as a whole, and the cured product obtained by curing the composition can be relatively hard and have sufficient flexibility for practical use.

[0037] In the above formula, e represents the general formula: R ２ O １／２ is a number indicating the proportion of units, and these units refer to hydroxyl or alkoxy groups bonded to silicon atoms that may be contained in the organopolysiloxane resin. e satisfies 0≦e≦0.05, and preferably 0≦e≦0.03. If e is equal to or less than the upper limit of the range, a material that achieves good hot melt performance as a whole composition can be obtained. Note that in the above formula, the sum of a, b, c, and d, which are the sums of the individual siloxane units, is equal to 1.

[0038] Component (A1) is an organopolysiloxane resin having the above characteristics, but because it is solid at room temperature, in order to physically mix it with component (B), which will be described later, it may be used in a dissolved state in a solvent or solvent mixture selected from the group consisting of aromatic hydrocarbons such as toluene, xylene, and mesitylene; ethers such as tetrahydrofuran and dipropyl ether; silicones 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. The solvent used here can be efficiently removed in the process described later.

[0039] [Component (A2)] Component (A2) is one of the main components of the composition, and is an organopolysiloxane resin that does not possess hot-melt properties on its own, does not contain any curing-reactive functional groups, and is solid at 25°C. When used in combination with the aforementioned components (A1) and (B) within a specified quantitative range, this component provides the curable silicone composition with hot-melt properties as a whole, and the cured product obtained by curing the curable silicone composition with excellent stress relaxation properties.

[0040] Component (A2) is an organopolysiloxane resin that does not have hot-melt properties by itself and is solid in the absence of a solvent. Similar to component (A1), the behavior of component (A2) when it does not have hot-melt properties and the fact that it is preferable that it does not contain aryl groups such as phenyl groups are the same as component (A1).

[0041] Component (A2), like component (A1), is a solid at 25°C and is an organopolysiloxane resin containing Q units at 20 mol% or more of all siloxane units, but is characterized by the absence of a curable functional group containing at least one carbon-carbon double bond within the molecule. That is, component (A2) is characterized by the absence of alkenyl groups such as vinyl groups as functional groups within the organopolysiloxane resin. The groups contained in the organopolysiloxane resin of component (A2) include monovalent hydrocarbon groups having 1 to 10 carbon atoms, particularly alkyl groups having 1 to 10 carbon atoms such as methyl. This organopolysiloxane resin is substantially free of aryl groups such as phenyl groups; for example, the proportion of aryl groups in all silicon-bonded organic groups may be 5 mol% or less, or even 2 mol% or less, and preferably contains no aryl groups at all.

[0042] Preferably, the functional groups bonded to silicon atoms in component (A2) are alkyl groups having 1 to 10 carbon atoms, such as methyl groups, and 70 to 100 mol % of all the organic groups bonded to silicon atoms may be methyl groups. Within this range, component (A2) does not exhibit hot-melt properties by itself, and SiO ４／２ It can be a component that has an especially excellent reinforcing effect on cured products containing siloxane units represented by the following formula: The organopolysiloxane resin of component (A2) may contain small amounts of hydroxyl groups or alkoxy groups.

[0043] Because component (A2) does not contain a curable reactive functional group containing a carbon-carbon double bond within the molecule, it does not itself form a cured product when combined with the organohydrogenpolysiloxane of component (C), but it does have the effect of improving the hot melt properties of the curable silicone composition of the present invention as a whole and reinforcing the cured product obtained by curing the curable silicone composition. Furthermore, by using component (A2) in combination with component (A1), which contains a curable reactive functional group, as necessary, it is possible to adjust the heat melting properties of the resulting curable silicone composition and the physical properties of the composition after curing.

[0044] Component (A2) is an organopolysiloxane resin that is solid at 25°C in the absence of a solvent and is characterized by containing Q units, which are branched siloxane units, in the molecule in an amount of 20 mol% or more of all siloxane units. Preferably, the organopolysiloxane of component (A2) contains Q units in an amount of 40 mol% or more, 50 mol% or more, and particularly 50 to 65 mol% of all siloxane units.

[0045] Preferably, component (A2) is (A2-1) an average unit formula: ３ ３ SiO １／２ ) ｆ (R ３ ２ SiO ２／２ ) ｇ (R ３ SiO ３／２ ) ｈ (SiO ４／２ ) ｉ (R ２ O １／２）ｊ (In the formula, each R ３ are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms and no carbon-carbon double bonds; R ２ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; and f, g, h, i, and j are numbers that satisfy 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), which does not have hot-melt properties by itself.

[0046] In the above average unit formula, each R ３ are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms and not containing a carbon-carbon double bond, for example, a group selected from the group consisting of alkyl groups such as methyl, aryl groups such as phenyl, and aralkyl groups such as benzyl. ３ It is particularly preferred from the viewpoint of industrial production and the technical effect of the invention that 70 mol % or more of R are alkyl groups having 1 to 10 carbon atoms, such as methyl groups, particularly methyl groups. ３Preferably, component (A2) is substantially free of aryl groups such as phenyl groups. If component (A2) contains a large amount of aryl groups such as phenyl groups, the component (A2) itself will have hot-melt properties, which may prevent the technical effects of the present invention from being achieved. In addition, the discoloration resistance at high temperatures of the cured product obtained by curing the curable silicone composition of the present invention may be impaired.

[0047] In the above formula, R ２ is as described above, but R ２ When is an alkyl group, an example is a methyl group.

[0048] In the above formula, f represents the general formula: R ３ ３ SiO １／２ is a number indicating the proportion of siloxane units. f satisfies the conditions 0.35≦f≦0.55 and 0.40≦f≦0.50. When f is at or above the lower limit of the above range, a curable silicone composition containing this component can achieve good hot-melt performance as a whole. On the other hand, when f is at or below the upper limit of the above range, the mechanical strength (hardness, etc.) of the resulting cured product will not be too low.

[0049] In the above formula, g represents a group represented by the general formula: R １ ２ SiO ２／２ g is a number indicating the proportion of siloxane units. g satisfies the conditions 0≦g≦0.20 and 0≦g≦0.10. When g is below the upper limit of the range, a curable silicone composition containing this component can achieve good hot-melt performance as a whole, and can also produce a composition that is less sticky at room temperature. In the present invention, g may be 0.

[0050] In the above formula, h represents the general formula: R １ SiO ３／２ h is a number indicating the proportion of siloxane units. h satisfies the conditions 0≦h≦0.20 and 0≦h≦0.10. When h is equal to or less than the upper limit of the range, a curable silicone composition containing this component can achieve good hot-melt performance as a whole, and can also produce a composition that is less sticky at room temperature. In the present invention, h may be 0.

[0051] In the above formula, i is a number indicating the proportion of Q units, and may be 0.45≦i≦0.65, or 0.50≦i≦0.65. When i is within this numerical range, a curable silicone composition containing this component can achieve good hot melt performance as a whole, and the cured product obtained by curing the curable silicone composition can have excellent mechanical strength, and the composition as a whole can be made to be non-sticky and easy to handle.

[0052] In the above formula, j represents the general formula: R ２ O １／２ is a number indicating the proportion of units, and these units represent hydroxyl or alkoxy groups bonded to silicon atoms that may be contained in the organopolysiloxane resin. j satisfies 0≦j≦0.05 and 0≦j≦0.03. When j is equal to or less than the upper limit of the above range, the curable silicone composition as a whole can achieve good hot melt performance. Note that in the above formula, the sum of f, g, h, and i, which are the sums of the individual siloxane units, is equal to 1.

[0053] Component (A2) is an organopolysiloxane resin having the above characteristics, and its handleability is similar to that of the aforementioned component (A1). That is, because component (A2) is a solid at room temperature (e.g., 25°C), like component (A1), it can be used in a dissolved state in the above-mentioned solvent or solvent mixture in order to mix with component (B), and the solvent can then be removed to prepare a curable silicone composition.

[0054] [Removal of Volatile Low-Molecular-Weight Components in Component (A)] Volatile low-molecular-weight components are generated in the production process of components (A1) and (A2). Specifically, the volatile low-molecular-weight components are M ４ Q structure, M unit (R ３ ３ SiO １／２ ) and Q unit (SiO ４／２This structure appears as a by-product during polymerization of an organopolysiloxane resin comprising M. This structure has the effect of significantly reducing the hardness of the cured product obtained from the curable silicone composition of the present invention. The organopolysiloxane resins of components (A1) and (A2) are produced by polymerization of raw material monomers in the presence of an organic solvent that is highly compatible with these components, and a solid organopolysiloxane resin can be obtained by removing the organic solvent by drying under reduced pressure or the like. ４ The structure of Q has high compatibility with organopolysiloxane resins and is difficult to remove under drying conditions such as those used to remove organic solvents. ４ It was known that the Q structure could be removed by briefly exposing the organopolysiloxane resin containing it to a temperature of 200°C or higher. ４ After the curable silicone composition containing the Q structure is integrally molded with a substrate such as a semiconductor, it is exposed to high temperatures to form an M ４ If the Q structure is removed, the volume of the cured product produced from the curable silicone composition will decrease and the hardness will increase significantly, which may result in changes in the dimensions of the molded product and lead to warping. ４ The Q structure also has the effect of imparting adhesiveness to the resulting cured product, and therefore essentially has the effect of increasing the surface tackiness of the cured product. When the cured product is used as a sealant to protect a substrate, particularly as a sealant for one-sided protection, it may be necessary to reduce the surface tackiness as much as possible, and ４ The existence of Q structure can be a problem. ４ If a large amount of Q structure remains in the composition or cured product, a significant increase in hardness occurs in the adhesive layer or sealing layer intended for double-sided adhesion, and the elastic modulus may change significantly. For this reason, in order to apply the curable silicone composition of the present invention to applications in which it is laminated with a substrate such as a semiconductor, it is necessary to remove M from the organopolysiloxane resin before the molding step in which the curable silicone composition is laminated with the substrate and cured, and if possible, at the raw material stage before preparing the curable silicone composition. ４ It is preferable to remove the Q structure.

[0055] M ４As a method for removing the Q structure from the organopolysiloxane resin, after obtaining particulate organopolysiloxane resin in the manufacturing process of the organopolysiloxane resin, the particulate organopolysiloxane resin is dried in an oven or the like to remove the M ４ Examples of the method include a method of removing the Q structure, and a method of removing it together with the organic solvent in a twin-screw kneader described later.

[0056] More specifically, component (A1) and component (A2) are produced in the presence of an organic solvent, and M ４ Volatile components such as Q structure appear as by-products. The obtained organopolysiloxane resin, which is the crude raw material, can be treated for a short period of time at a high temperature of about 200°C to remove the volatile components. Therefore, the organic solvent and M are removed from component (A1) and component (A2) using a twin-screw kneader set at a temperature of 200°C or higher. ４ From the perspective of efficiently producing the curable hot-melt silicone composition of the present invention, component (B), which will be described later, is added to component (A2) dissolved in an organic solvent or to a mixture of components (A1) and (A2), and the resulting mixture is mixed in a liquid state and fed into a twin-screw extruder set at 200°C or higher, where it is mixed with the organic solvent and the M ４ It is preferable to carry out a step of removing volatile components such as the Q structure. This method makes it possible to obtain a hot-melt mixture of components (A) and (B), which can be used in the step described below to knead with the remaining components that make up the curable silicone composition.

[0057] [Mass Ratio of Component (A1) to Component (A2) in Component (A)] In order to impart hot-melt properties to the present composition as a whole, component (A2), or a mixture of components (A1) and (A2), must be mixed with component (B), described below, in a predetermined ratio, and the ratio of components (A1) to (A2) may be in the range of 20:80 to 90:10, 35:65 to 90:10, or 50:50 to 90:10. Component (A2) itself does not have any curable functional groups and is therefore not curable. However, by using component (A2) in combination with component (A1) in the present composition, it is possible to adjust to some extent the storage modulus, loss modulus, and tan δ calculated from the ratio of these of the storage modulus and loss modulus of the cured product obtained by curing the present curable composition, thereby making it possible to achieve suitable elastic modulus, flexibility, and stress relaxation properties of the cured product. Alternatively, a curable hot-melt silicone composition having the desired properties of the present invention can be prepared by combining component (A2) with component (B) without component (A1).

[0058] [Component (B)] Component (B) is one of the main components of the present curable silicone composition, and is a linear or branched organopolysiloxane that is liquid or plastic at 25°C and has at least two curable functional groups containing carbon-carbon double bonds within the molecule. By mixing this type of curable linear organopolysiloxane with the solid organopolysiloxane resin of component (A) described above, the composition as a whole can exhibit hot melt properties.

[0059] Component (B) must have a curing reactive functional group with a carbon-carbon double bond in the molecule. Such a curing reactive functional group has hydrosilylation reactivity and forms a cured product by crosslinking with other components. Examples of such a curing reactive functional group include alkenyl groups similar to those in component (A1), and may particularly be vinyl or hexenyl groups.

[0060] Component (B) is a linear or branched organopolysiloxane that is liquid or plastic at 25°C (room temperature), and by mixing it with component (A), which is solid at room temperature, the composition as a whole can exhibit hot melt properties. The chemical structure of the organopolysiloxane of component (B) may be linear or may contain a small number of branched siloxane units (for example, a siloxane unit represented by the general formula: R ４ SiO ３／２ T units (R ４ are independently monovalent hydrocarbon radicals having 1 to 10 carbon atoms) or SiO ４／２ (B1) a branched-chain organopolysiloxane having a Q unit represented by the following structural formula: R ４ ３ SiO(SiR ４ ２ O) ｋ SiR ４ ３ (In the formula, each R ４ are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, provided that R ４ wherein at least two of the groups are alkenyl groups, and k is a number from 20 to 5,000. Linear diorganopolysiloxanes having one alkenyl group, particularly a vinyl group, at each end of the molecular chain are preferred.

[0061] In the above formula, each R ４ are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, for example, groups selected from the group consisting of alkyl groups such as methyl groups; alkenyl groups such as vinyl groups; aryl groups such as phenyl groups; and aralkyl groups such as benzyl groups. ４ At least two of the R groups may be alkenyl groups or vinyl groups. ４ may be a functional group selected from the group consisting of alkyl groups having 1 to 10 carbon atoms, such as a methyl group, and alkenyl groups, such as a vinyl group and a hexenyl group, and all R ４ At least two of the R ４ may be a methyl group. From the viewpoint of the technical effect of the invention, R ４Preferably, the curable silicone composition is substantially free of aryl groups such as phenyl groups. If the curable silicone composition contains a large amount of aryl groups such as phenyl groups, the cured product obtained from the curable silicone composition may have poor resistance to discoloration at high temperatures. Particularly preferably, the curable silicone composition has one alkenyl group such as a vinyl group at each end of the molecular chain, and other R ４ may be a methyl group.

[0062] In the above formula, k is a number between 20 and 5,000, between 30 and 3,000, or between 45 and 800. When k is at or above the lower limit of the above range, a curable silicone composition that is less sticky at room temperature can be obtained. On the other hand, when k is at or below the upper limit of the above range, the curable silicone composition as a whole can achieve good hot-melt performance.

[0063] In order for the composition as a whole to exhibit hot melt properties, the amount of component (B), which is a linear or branched organopolysiloxane, should be in the range of 10 to 100 parts by mass, 10 to 70 parts by mass, or 15 to 50 parts by mass per 100 parts by mass of component (A), which is an organopolysiloxane resin. If the content of component (B) is within the above range, the resulting curable silicone composition will exhibit good hot melt properties, and the mechanical strength of the cured product obtained by curing the curable silicone composition will be increased. Also, the stickiness of the resulting curable silicone composition at room temperature will be reduced, thereby improving the handling and workability of the composition.

[0064] [Component (C)] Component (C) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms per molecule that is crosslinkable with the carbon-carbon double bonds contained in components (A) and (B) above in the presence of a hydrosilylation catalyst, and is a component that cures the composition.

[0065] The structure of the organohydrogenpolysiloxane crosslinking agent is not particularly limited, and may be linear, branched, cyclic, or resinous. ２ SiO １／２ The hydrogen organosiloxy unit (M Ｈ units, R independently represents a monovalent organic group), or HRSiO２／２ The siloxy unit of hydrogen organic group (D Ｈ The organohydrogenpolysiloxane may be an organohydrogenpolysiloxane having units (R, R independently represents a monovalent organic group).

[0066] On the other hand, when the curable silicone composition is used in a molding process, the content of curable functional groups containing carbon-carbon double bonds in the composition is low, and therefore, from the standpoints of cure rate, moldability, and curability, the organohydrogenpolysiloxane is RSiO ３／２ Monoorganosiloxy units (T units, R is a monovalent organic group or a silicon-bonded hydrogen atom) represented by the formula: ４／２ and at least two HR ２ SiO １／２ Hydrogen diorganosiloxy units (M Ｈ units, and R are independently monovalent organic groups), and Ｈ The organohydrogenpolysiloxane resin may be an organohydrogenpolysiloxane resin having units.

[0067] Particularly suitable organohydrogenpolysiloxanes are those represented by the following average composition formula (1): ４ ３ SiO １／２ ) a (R ５ ２ SiO ２／２ ) b (R ５ SiO ３／２ ) c (SiO ４／２ ) d (R ２ O １／２）ｅ (1) (wherein, R ４ are each independently a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and not containing an aliphatic unsaturated bond, and R ５ are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and containing no aliphatic unsaturated bonds, and all R ４at least two of the groups are hydrogen atoms, and a, b, c, and d are numbers that satisfy the conditions 0.01≦a≦0.6, 0≦b, 0≦c≦0.9, 0≦d≦0.9, and a+b+c+d=1 and c+d≧0.2. Optionally, this organohydrogenpolysiloxane may be characterized in that after exposure to 100°C under atmospheric pressure for 1 hour, the mass loss rate compared to before exposure is 10% by mass or less.

[0068] In the above formula, each R ４ are the same or different monovalent hydrocarbon groups having 1 to 12 carbon atoms and no aliphatic unsaturated carbon bonds, or hydrogen atoms, provided that at least two, preferably at least three R ４ is a hydrogen atom. R other than a hydrogen atom ４ The monovalent hydrocarbon group represented by R is, for example, a group selected from the group consisting of alkyl groups such as methyl groups, aryl groups such as phenyl groups, and aralkyl groups such as benzyl groups. ４ The monovalent hydrocarbon groups represented by may independently be methyl or phenyl groups.

[0069] In the formula, R ５ is a monovalent hydrocarbon group having 1 to 12 carbon atoms and no aliphatic unsaturated carbon bond, and ４ Examples of the monovalent hydrocarbon groups include the same groups as those of R ５ may be a group selected from a methyl group and a phenyl group.

[0070] In the formula, a, b, c, and d are numbers that satisfy the following conditions: 0.01≦a≦0.6, 0≦b, 0≦c≦0.9, 0≦d≦0.9, and a+b+c+d=1 and c+d≧0.2. Ｈ MT resin, M Ｈ T resin, M Ｈ MTQ resin, M Ｈ MQ resin, M Ｈ DQ resin and M Ｈ In the above resin notation, M, D, T, and Q represent M units, D units, T units, and Q units, respectively; Ｈ represents an M unit having a hydrogen atom.

[0071] In the above formula (1), R ２ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. ２ Examples of the alkyl group of R include a methyl group. ２ Group R containing ２ O １／２ corresponds to the hydroxyl group or alkoxy group contained in the organohydrogenpolysiloxane of component (C).

[0072] In the above formula, e represents the general formula: R ２ O １／２ is a number indicating the proportion of units of the formula (1), and these units represent hydroxyl groups or alkoxy groups bonded to silicon atoms that may be contained in the organopolysiloxane resin. e satisfies 0≦e≦0.05 and 0≦e≦0.03. As mentioned above, in the formula (1), the sum of a, b, c, and d, which are the sums of the siloxane units, is equal to 1.

[0073] Component (C) is exemplified by organohydrogenpolysiloxanes represented by the following average composition formula (2): (HR ６ ２ SiO １／２ ) ｆ (R ６ ２ SiO ２／２ ) ｇ (SiO ４／２ ) ｈ (2) In formula (2), R ６ are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and containing no aliphatic unsaturated bonds, and f, g, and h are numbers that satisfy the conditions of 0.01≦f≦0.6, 0≦g≦0.9, 0.2≦h≦0.9, and f+g+h=1. Specific examples of this monovalent hydrocarbon group include those represented by R ４ are the same as the specific examples of the monovalent hydrocarbon group represented by R ６ may each independently be a group selected from a methyl group and a phenyl group.

[0074] Component (C) is exemplified by organohydrogenpolysiloxanes represented by the following average formula (3): (HR ７２ SiO １／２ ) ｉ (R ７ ２ SiO ２／２ ) ｊ (R ８ SiO ３／２ ) ｋ (3) In formula (3), R ７ and R ８ are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and containing no aliphatic unsaturated bonds, and all R ８ In the above average composition formula (1), 10 mol % or more of the groups are aryl groups, and i, j, and k are numbers that satisfy the conditions of 0.01≦i≦0.6, 0≦j≦0.9, 0.2≦k≦0.9, and i+j+k=1. Specific examples of the monovalent hydrocarbon group include the groups represented by R ４ are the same as the specific examples of the monovalent hydrocarbon group represented by R ８ is all R ８ may each independently be a group selected from a methyl group and a phenyl group, provided that 10 mol % or more of the groups are phenyl groups.

[0075] The organohydrogenpolysiloxane represented by the average composition formula (2) and the organohydrogenpolysiloxane represented by the average composition formula (3) may be used alone or in combination.

[0076] The content of the organohydrogenpolysiloxane of component (C) in the curable silicone composition of the present invention is an amount sufficient to cure the curable silicone composition, and may be such that the number of silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane of component (C) relative to the curable functional groups containing carbon-carbon double bonds (for example, alkenyl groups such as vinyl groups) in components (A) and (B) is such that the number of silicon-bonded hydrogen atoms per alkenyl group relative to the silicon-bonded alkenyl groups contained in the entire curable silicone composition (hereinafter referred to as the "SiH / Vi ratio") is 0.5 to 20.0, and particularly 1.0 to 10.

[0077] [Removal of Volatile Components] Regardless of the structure, these organohydrogenpolysiloxanes are preferably components that are not easily volatilized at atmospheric pressure, particularly at 1 atmosphere (1013.25 hPa) and around 100°C. This is because, in the production process of the curable hot-melt silicone sheet or film of the present invention described below, in order to obtain a sheet or film free of voids, etc., it is necessary to melt-knead the components of the curable silicone composition and the composition obtained therefrom at a temperature range of 50 to 150°C under reduced pressure. By using the components of the present invention, a sheet or film free of voids, etc., can be produced. Although the components are exposed to the specified temperature under reduced pressure for only a short time, if a large amount of the active ingredient volatilizes under these kneading conditions, the composition cannot be obtained with the designed properties. In particular, since the amount of organohydrogenpolysiloxane used as a crosslinking agent is small relative to the total mass of the curable silicone composition, the volatilization of these components can significantly alter the properties of the composition (e.g., curing characteristics and physical properties of the cured product) from their intended values. For this reason, it is necessary to use a component (C) that is not easily volatile. Specifically, the mass loss rate after exposure to 100°C under atmospheric pressure for 1 hour compared to before exposure may be 10% by mass or less, which is preferable depending on the application.

[0078] [Component (D)] Component (D) is one of the characteristic features of the curable silicone composition of the present invention. It is a hydrosilylation catalyst-containing microparticle having a structure in which a hydrosilylation catalyst is encapsulated in a thermoplastic resin having a glass transition temperature (Tg) in the range of 110 to 200°C. Such component (D) may be either (D-1) microparticles in which the hydrosilylation catalyst is dissolved or dispersed in the thermoplastic resin, or (D-2) microcapsule microparticles in which the hydrosilylation catalyst is contained as a core within a thermoplastic resin shell. Because component (D) has a structure in which the hydrosilylation catalyst is encapsulated or supported in a thermoplastic resin having a specific glass transition point, even when heated below the glass transition point, the hydrosilylation catalyst remains inactive and the curing reaction is inhibited. This allows the composition to be stably stored even when molded into a sheet or other form below that temperature. On the other hand, heating above the glass transition point rapidly melts the thermoplastic resin in component (D), activating the hydrosilylation catalyst and forming a cured product.

[0079] Examples of catalysts that can be used as component (D) include platinum catalysts, rhodium catalysts, palladium catalysts, and non-platinum metal catalysts such as iron, ruthenium, and iron / cobalt, but platinum catalysts are particularly preferred because they can significantly accelerate the curing of the composition. This platinum catalyst can be appropriately selected from known catalysts, but a representative example is a platinum (zero-valent)-alkenylsiloxane complex. The structure of the alkenylsiloxane is not limited, but 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is an example because of the good stability of the complex.

[0080] The thermoplastic resin constituting component (D) functions as a wall material that isolates the catalyst from the reaction system. Its glass transition temperature (Tg) is, for example, in the range of 110°C to 200°C, but may also be in the range of 120°C to 200°C or 130°C to 200°C. The glass transition temperature of the thermoplastic resin can be measured using a differential scanning calorimeter (DSC). Such thermoplastic resins may be selected from epoxy resins, acrylic resins, and polycarbonate resins, and particularly, acrylic resins or polycarbonate resins having the above Tg are exemplary. The thermoplastic resin and the microparticles of component (D) exhibit substantially the same behavior regardless of their softening points within the above range.

[0081] In the present invention, if the Tg of the thermoplastic resin constituting component (D) is less than the lower limit, the thermoplastic resin wall material may dissolve and the hydrosilylation catalyst may elute during the process of homogenizing and heat-molding the composition, which may impair the storage stability of the entire composition. On the other hand, if the Tg of the thermoplastic resin exceeds the upper limit, a high temperature exceeding 200°C is required for reaction activity, which may deteriorate the substrate or be unfavorable in terms of thermal processing.

[0082] The average particle size of the microparticles that are component (D) may be in the range of 0.1 to 500 μm, or may be in the range of 0.3 to 100 μm, because it is difficult to prepare microparticles with an average particle size below the lower limit of this range, while if the average particle size exceeds the upper limit of this range, dispersibility in the curable silicone resin composition decreases.

[0083] The method for preparing such component (D) is not limited, and examples include conventionally known chemical methods such as interfacial polymerization and in-situ polymerization, and physical / mechanical methods such as coacervation and submerged drying. Submerged drying and vapor-phase drying are particularly desirable because they allow for the relative ease with which microcapsule particles with a narrow particle size distribution can be obtained. While the particles obtained by these methods can be used as is, it is desirable to remove any platinum-based catalyst adhering to their surfaces by washing them with a known washing solvent such as methanol or a low-molecular-weight siloxane in order to obtain a curable silicone resin composition with excellent storage stability.

[0084] The content of the platinum-based catalyst-containing thermoplastic resin microparticles in the composition is not particularly limited, but may be an amount such that the platinum metal in the microparticles is 0.1 to 2,000 ppm, or 1 to 1,000 ppm, by mass, relative to the composition. This is because if the content of the platinum-based catalyst-containing thermoplastic resin microparticles is below the lower limit of the above range, sufficient curing will be difficult, while if it exceeds the upper limit of the above range, curing will not be significantly improved.

[0085] [Component (E)] Component (E) is a filler or pigment, and in the present invention, it is preferable to include a white or colored filler, particularly a white or colored inorganic filler, which may contain a wavelength conversion component such as a phosphor as part of it, or may contain fine particles having other functions such as electrical conductivity or thermal conductivity. In particular, the composition according to the present invention has hot-melt properties and is thermosetting, and therefore has the advantage that the curing reactivity is not inhibited even if a white or colored filler or pigment that blocks or reflects high-energy rays such as ultraviolet rays is used.

[0086] The function of the filler or pigment of component (E) is not particularly limited, but it can impart white or color to the resulting cured product, and is expected to improve the mechanical strength and hardness of the product. It may also impart optical functions such as wavelength conversion, or other functions such as thermal conductivity and electrical conductivity. Examples of component (E) include white pigments, black pigments, phosphors, metal powders, and other functional fillers. Components that impart white or colored cured products are particularly preferred. The shape of the filler or pigment of component (E) is not particularly limited, and it may be spherical, spindle-shaped, flat, acicular, irregular, or the like.

[0087] The white pigment is a component that imparts whiteness to the cured product and improves light reflectivity. By incorporating this component, the cured product obtained by curing the composition can be used as a light-reflecting material for light-emitting / optical devices. Examples of white pigments include metal oxides such as titanium oxide, aluminum oxide, zinc oxide, zirconium oxide, and magnesium oxide; hollow fillers such as glass balloons and glass beads; and other white pigments such as barium sulfate, zinc sulfate, barium titanate, aluminum nitride, boron nitride, and antimony oxide. Titanium oxide is preferred due to its high light reflectance and hiding power. Aluminum oxide, zinc oxide, and barium titanate are also preferred due to their high light reflectance in the UV region. The average particle size and shape of the white pigment are not limited, but the average particle size is preferably within the range of 0.05 to 10.0 μm, or 0.1 to 5.0 μm. The white pigment may also be surface-treated with a silane coupling agent, silica, aluminum oxide, or the like.

[0088] Black pigments are components that can impart blackness and light-shielding properties to a cured product, but needless to say, they may also have other functions such as electrical conductivity, as typified by carbon black and graphene. More specific examples of black pigments include carbon-based black pigments such as carbon black, graphite, activated carbon, and graphene; inorganic black pigments such as iron oxide, magnetite, chromium iron oxide, chromium iron nickel oxide, copper chromate, chromite, manganese ferrite, nickel manganese iron oxide, and composite metal oxides containing one or more metals selected from iron, cobalt, and copper; and organic black pigments such as aniline black, cyanine black, and perylene black.

[0089] The phosphor is a component that is blended to convert the wavelength of light emitted from a light source (optical semiconductor element) when the cured product is used as a wavelength conversion material. There are no particular limitations on the phosphor, and examples of this phosphor include yellow-, red-, green-, and blue-emitting phosphors that are widely used in light-emitting diodes (LEDs), such as oxide-based phosphors, oxynitride-based phosphors, nitride-based phosphors, sulfide-based phosphors, and oxysulfide-based phosphors.

[0090] The present composition may contain inorganic fillers other than those mentioned above, such as reinforcing fillers (e.g., silica) to improve the mechanical strength of the cured product, thermally conductive fillers, and electrically conductive fillers. Furthermore, for the purpose of stably incorporating component (E) into the present composition, component (E) may be surface-treated with one or more compounds selected from low-molecular-weight organosilicon compounds (e.g., silanes and silazanes), organosilicon polymers or oligomers, and other known surface treatment agents. The amount of the surface treatment agent used is not particularly limited, but is typically in the range of 0.1 to 2.0% by mass based on the total mass of component (E). Furthermore, component (E) may be compounded in advance with the other components (A) to (D) to form a masterbatch.

[0091] The content of component (E) may be within a range of 0.1 to 100 parts by mass, 0.5 to 90 parts by mass, 0.5 to 80 parts by mass, or 1.0 to 50 parts by mass, relative to the total (100 parts by mass) of components (A) to (D). If the amount added is less than this range, the coloring effect may not be sufficient, while if it is greater than this range, the melt viscosity of the resulting hot-melt composition may be too high. In addition, when produced by the method described below, it may be difficult to knead the entire composition uniformly, and the production equipment may be prone to wear, which may cause discoloration in the resulting composition or may prevent the desired color from being achieved.

[0092] In addition to the above components (A) to (E), the curable silicone composition of the present invention may also contain a cure retarder (F) from the standpoint of further improving practicality and storage stability.

[0093] There are no particular restrictions on the structure of the cure retarder, but it is preferable that it have a boiling point of at least 200°C under atmospheric pressure. This is because if a compound with a low boiling point is used as a retarding curing agent when the raw materials are melted and kneaded under reduced pressure in the production process for the curable silicone composition sheet, which will be described later, some or all of the cure retarder will volatilize during the production process for the composition of the present invention, and there is a risk that the desired cure-retarding effect for the curable silicone composition will not be achieved.

[0094] The cure retarder of the present invention is not particularly limited, but examples thereof include alkyne alcohols such as 2-methyl-3-butyn-2-ol, 3,5-dimethyl-1-hexyn-3-ol, 2-phenyl-3-butyn-2-ol, and 1-ethynyl-1-cyclohexanol; enyne compounds such as 3-methyl-3-penten-1-yne and 3,5-dimethyl-3-hexen-1-yne; alkenyl group-containing low molecular weight siloxanes such as tetramethyltetravinylcyclotetrasiloxane and tetramethyltetrahexenylcyclotetrasiloxane; and alkynyloxysilanes such as methyl-tris(1,1-dimethylpropynyloxy)silane and vinyl-tris(1,1-dimethylpropynyloxy)silane. Among these, it is particularly preferred to use compounds having a boiling point of 200°C or higher at atmospheric pressure (e.g., vinyl-tris(1,1-dimethylpropynyloxy)silane, etc.). The amount of cure retarder contained in the curable silicone composition is not particularly limited, but may be in the range of 1 to 10,000 ppm by mass relative to the composition.

[0095] [Adhesion Promoter] The composition of the present invention may contain a known adhesion promoter as an optional component, as long as it does not impair the object of the present invention. The adhesion promoter is not particularly limited, so long as it is a component that improves the adhesion to a substrate of the cured product obtained by curing the present composition. Suitable examples include silane compounds such as 3-glycidoxypropyltrimethoxysilane, which are listed as suitable components in the applicant's international patent application (PCT / JP2020 / 12027); organosiloxane oligomers; alkyl silicates; reaction mixtures of amino-containing organoalkoxysilanes and epoxy-containing organoalkoxysilanes disclosed in JP-B No. 52-8854 and JP-A No. 10-195085; carbasilatrane derivatives having a silicon-bonded alkoxy group or silicon-bonded alkenyl group per molecule; silatrane derivatives having an alkoxysilyl-containing organic group; and disilaalkane compounds such as 1,6-bis(trimethoxysilyl)hexane. Two or more components selected from these may also be used in combination. There are no limitations on the content of this adhesion promoter, but it can be used in the range of 0.01 to 10 parts by mass per 100 parts by mass of the total of the present composition.

[0096] [Other Additives] In addition to the components described above, the curable hot-melt silicone composition of the present invention may contain materials known in the art as additives that may be used in silicone compositions. For example, the composition may contain other optional components such as heat-resistant additives such as iron oxide (red iron oxide), cerium oxide, cerium dimethylsilanolate, fatty acid cerium salts, cerium hydroxide, and zirconium compounds; dyes, pigments other than white, and flame retardants.

[0097] [Sheet or Film] The present composition may be formed into a sheet or film for use. For example, a sheet or film made from the curable silicone composition of the present invention and having an average thickness of 10 to 1,000 μm has hot-melt properties and is heat-curable at high temperatures, resulting in excellent handling and melting properties, making it particularly advantageous for use in compression molding and the like. In this case, a composition containing all of components (A) to (F), including component (F), may be formed into a sheet or film.

[0098] Such sheet or film compositions can be prepared by first mixing all of the components in a single- or twin-screw continuous kneader to form a uniform mixture, and then passing the mixture through a twin-roll mill or similar to form a sheet or film of the desired thickness. Alternatively, the granular curable hot-melt silicone composition described below can be prepared, and then, if necessary, component (F) can be added, followed by kneading the mixture in a kneader to make it uniform, and then passing the mixture through a molding machine such as a twin-roll mill to produce a sheet or film of the desired thickness.

[0099] In particular, because this composition utilizes component (D) as a hydrosilylation reaction catalyst, a benefit is that, even if the entire composition is melt-kneaded within a temperature range of 50°C to the glass transition point (Tg) of the thermoplastic resin that makes up component (D) during molding into a sheet or film, the catalyst remains inactive and the curing reaction does not substantially proceed. This means that a curable silicone composition sheet or film with excellent storage stability can be obtained, even if the composition is melt-kneaded at a certain temperature during molding.

[0100] The sheet or film-like composition may be produced using organopolysiloxane resin microparticles as the raw material (Method A), or may be produced by dispersing a room-temperature solid organopolysiloxane resin and, optionally, a chain diorganopolysiloxane in an organic solvent, and then removing the organic solvent to obtain a hot-melt solid (hot-melt bulk method) (Method B). Specifically, the former (Method A) comprises the following steps: Step 1: mixing organopolysiloxane resin microparticles, a curing agent, and optionally a functional filler; Step 2: kneading the mixture obtained in Step 1 while heating and melting it at a temperature of 120°C or less; Step 3: laminating the mixture obtained in Step 2 after heating and melting and kneading it between two films, each having at least one release surface, to form a laminate; Step 4: stretching the mixture in the laminate obtained in Step 3 between rolls to form a curable hot-melt silicone sheet having a specific thickness.

[0101] On the other hand, the latter (Method B) is a production method comprising the following steps: Step 1: obtaining a hot-melt solid by removing the organic solvent at a temperature of 150°C or higher from a solution obtained by dispersing or dissolving an organopolysiloxane resin that is solid at room temperature, and optionally a linear diorganopolysiloxane, in an organic solvent; Step 2: adding all of the curing agents to the hot-melt solid obtained in Step 1, and then kneading the mixture while heating and melting it at a temperature of 120°C or lower; Step 3: laminating the heated and melted mixture obtained in Step 2 between two films, each of which has at least one release surface, to form a laminate; Step 4: 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.

[0102] In either manufacturing method (Method A or Method B), the kneading step in Step 2 is carried out at a temperature of 120°C or lower, which prevents component (D) from softening and the curing catalyst from activating, thereby enabling stable production of the composition. Steps 3 and 4 may be continuous and integrated steps. For example, the heated and melted mixture obtained in Step 2 may be laminated by being discharged or applied between films having at least one release surface directly below the rolls, and simultaneously stretched to a specific film thickness by adjusting the gap between the rolls. Thus, a manufacturing method in which Steps 3 and 4 are substantially integrated is also included within the scope of the above manufacturing method. That is, steps 3 and 4 may be carried out continuously and integrally by discharging or applying the mixture obtained in step 2 between two release films to sandwich the mixture between the two release films, for example, between two long release films, and then passing the resulting laminate consisting of the two release films and the mixture sandwiched between them between rolls to stretch and mold the mixture between the release films and adjust it to a predetermined film thickness to obtain the desired laminate. Such a method of carrying out steps 3 and 4 integrally is also included in the above-mentioned production method.

[0103] In step 3 of Method A or B, the step of laminating the heat-melted mixture between films is not particularly limited. It may be (i) a step in which the heat-melted mixture from step 2 is dispensed or applied onto a first release film having a release surface, and then a second release film is contacted with the surface of the mixture opposite the surface that contacts the first release film, thereby sandwiching the heat-melted mixture between the first and second release films, or (ii) a step in which the heat-melted mixture from step 2 is dispensed or applied between a first release film and a second release film having a release surface, thereby sandwiching the heat-melted mixture between the two release films. (ii) An example of a method in which the first and second release films are brought close together by an appropriate means, such as two rolls, and the mixture from step 2 is dispensed or applied to the area where the two release films are close together, thereby sandwiching the mixture between the two release films simultaneously or nearly simultaneously. Steps 3 and 4 above may be continuous steps.

[0104] With regard to these manufacturing methods, the applicants have proposed the entire process, including the manufacturing method and manufacturing equipment used therefor, for curable silicone sheets in Japanese Patent Application No. 2019-167832 and Japanese Patent Application No. 2019-167833, and their priority applications (including international patent applications). In the present invention, these methods and manufacturing equipment can also be applied to forming a sheet or film from a curable hot-melt silicone composition.

[0105] [Laminate containing curable hot-melt silicone composition and its use as film adhesive / sealant] This curable hot-melt silicone composition can be used in the form of a sheet or film, and in particular can be used as a laminate having a structure in which a sheet material made of the above-mentioned curable hot-melt silicone composition is sandwiched between two film substrates with a release layer.This film substrate with a release layer (generally called release film) can be peeled off from the sheet material made of the curable hot-melt silicone composition when the sheet material is used as an adhesive or sealant, etc.Hereinafter, this laminate will also be called a peelable laminate.

[0106] The method for producing the above-mentioned release laminate is not particularly limited, but one example includes the following steps: Step 1: Mixing the components of the curable hot-melt silicone composition; Step 2: Kneading the mixture obtained in Step 1 while heating and melting; Step 3: Laminating the heated and melted mixture obtained in Step 2 between two release films with at least one release surface, so that the mixture contacts the release surface, to form a laminate; Step 4: Pressuring the laminate obtained in Step 3 between rolls to roll out the mixture sandwiched between the two release films, thereby forming a curable hot-melt silicone composition sheet or film with a specific thickness. Optionally, a roll with a cooling or temperature-regulating function may be used in Step 4. Furthermore, a step of cutting the resulting laminate containing the curable hot-melt silicone composition sheet or film may be added after Step 4. The thickness of this release film is not particularly limited, and therefore includes what is generally called a film as well as what is called a sheet. However, in this specification, the term release film is used regardless of its thickness.

[0107] The temperature for the mixing step in step 1 is not particularly limited, but heating may be performed as necessary to ensure that the components are thoroughly mixed, and the heating temperature can be, for example, 50°C or higher.

[0108] By peeling the release film from the release laminate of the present invention, a sheet or film comprising a curable hot-melt silicone composition is obtained. Accordingly, the present invention also provides such a sheet or film. The sheet or film of the present invention may have a thickness of 10 to 1000 μm, and may be flat. "Flat" means that the thickness of the resulting sheet or film is within a range of ±100 μm or less, preferably within a range of ±50 μm or less, and more preferably within a range of ±30 μm or less.

[0109] The type of material for the substrate of the release film constituting the release laminate is not particularly limited, but for example, polyester film, polyolefin film, polycarbonate film, acrylic film, etc. can be used as appropriate. The sheet-like substrate may be non-porous. The release film is a film having a release layer formed by treating one or both sides of a film made of such a material to impart releasability, and such treatments are known in the art.

[0110] A layer having releasability provided on the surface of a release film is called a release layer. This release layer is designed to allow a sheet or film made of a curable silicone composition to be easily peeled from a film-like substrate, and is sometimes called a release liner, separator, release layer, or release coating layer. Preferably, the release layer can be formed as a release layer having release coating properties, such as a silicone-based release agent, a fluorine-based release agent, an alkyd-based release agent, or a fluorosilicone-based release agent. Alternatively, the film-like substrate surface may be physically provided with fine irregularities to reduce adhesion to the curable silicone composition, or the substrate may be made of a material that is less likely to adhere to a layer made of the curable hot-melt silicone composition of the present invention or its cured product. In particular, in the laminate of the present invention, it is preferable to use a release layer made by curing a fluorosilicone-based release agent as the release layer.

[0111] The above laminate can be used, for example, by peeling off one of the two release films that make up the laminate, applying an uncured sheet or film-like member made of the curable silicone composition that is not in contact with the release film to an adherend, and then peeling the uncured sheet or film-like member from the other film-like substrate, i.e., the release film.

[0112] The present curable silicone composition can be handled in the form of a sheet or film at room temperature, and is a non-flowable solid at 25°C. Here, "non-flowable" means that it does not deform and / or flow in the absence of an external force. Preferably, the present cured silicone composition, when molded into pellets, tablets, or the like, does not deform and / or flow at 25°C in the absence of an external force. Such non-flowability can be evaluated, for example, by placing the molded composition on a hot plate at 25°C and observing that the composition does not substantially deform and / or flow even when no external force is applied or a certain load is applied to the composition. Being non-flowable at 25°C means that the composition has good shape retention at that temperature and has low surface tack, allowing the composition to be easily handled even in an uncured state.

[0113] The softening point of the composition is preferably 100° C. or lower. This softening point refers to the temperature at which, when a 22 mm-high composition is pressed down on a hot plate with a load of 100 grams for 10 seconds, and the amount of deformation of the composition in the height direction is measured after the load is removed, the amount of deformation is 1 mm or more.

[0114] [Viscosity and Fluidity During Heat Melting] The viscosity of the present composition tends to decrease rapidly with increasing temperature under high temperature and pressure (i.e., for example, during the laminate manufacturing process described above). Therefore, a useful melt viscosity value for handling the composition may be a value measured under high temperature and pressure conditions similar to those under which the present composition is actually used. Therefore, the melt viscosity of the present composition may be measured under high pressure using a Koka-shiki flow tester (manufactured by Shimadzu Corporation) rather than using a rotational viscometer such as a rheometer. Specifically, the melt viscosity of the present composition at 150°C measured using a Koka-shiki flow tester may be 200 Pa·s or less, or 150 Pa·s or less. This is because the present composition has good adhesion to a substrate after being hot-melted (i.e., after being heated and melted) and cooled to 25°C.

[0115] [Curable Hot-Melt Silicone Composition Sheet] The curable hot-melt silicone composition sheet obtained by the production method of the present invention is a curable silicone composition containing the above-mentioned components (A) to (E) and, optionally, component (F), and has hot-melt properties. The curable hot-melt silicone composition sheet of the present invention can be used as a pressure-sensitive adhesive, sealant, and / or adhesive that has heat-melt properties. In particular, the curable hot-melt silicone composition sheet has excellent moldability, gap-filling properties, and adhesive strength, and can be used as a die-attach film or film adhesive. It can also be suitably used as a curable hot-melt silicone composition sheet for compression molding or press molding.

[0116] Specifically, after peeling the curable hot-melt silicone composition sheet obtained by the production method of the present invention from the release film, it is placed in the desired location on a semiconductor or the like, and a film adhesive layer that takes advantage of its gap-filling properties for unevenness and gaps is formed on and between the adherends, the adherends are temporarily fixed, positioned, and bonded together, and the curable hot-melt silicone composition layer is then heated to at least 120°C, especially at 150°C, to cure the layer, forming a cured product of the curable silicone sheet between the adherends, thereby bonding the adherends. The release film may be peeled off after the curable hot-melt silicone composition sheet has been heated to form a cured product, and the timing for peeling the release film from the curable silicone composition or the cured product obtained therefrom may be selected depending on the application and method of use of the curable silicone composition sheet.

[0117] In addition to being storage stable, the curable silicone composition and sheet / film thereof according to the present invention possess hot-melt properties that result in excellent fluidity and low viscosity at high temperatures. Therefore, by heating the sheet before final curing, the composition softens and fluidizes, and even if there are minute irregularities or gaps on the adherend surface, the composition can fill these irregularities and gaps without leaving any gaps, forming an adhesive surface for the adherend.

[0118] [Method of Forming a Cured Product] The curable hot-melt silicone composition can be cured by a method comprising at least the following steps (I) to (III): (I) a step of heating the composition to 120°C or higher to melt it; (II) a step of injecting the molten curable hot-melt silicone composition obtained in step (I) into a mold, or a step of spreading the molten curable hot-melt silicone composition obtained in step (I) throughout the mold by clamping the mold; and (III) a step of curing the curable hot-melt silicone composition injected into the mold in step (II).

[0119] In the above steps, a transfer molding machine, a compression molding machine, an injection molding machine, an auxiliary ram molding machine, a slide molding machine, a double ram molding machine, a low-pressure encapsulation molding machine, etc. In particular, the composition of the present invention is suitable for use in obtaining a cured product by transfer molding and compression molding.

[0120] Finally, in step (III), the curable silicone composition injected (applied) into the mold in step (II) is cured. This step can be carried out at low temperatures, as described below, and is therefore preferred.

[0121] The curable silicone composition of the present invention (or a semi-cured product thereof) can be cured by exposing the composition of the present invention (or a semi-cured product thereof) to a temperature of 120°C or higher, which activates the hydrosilylation catalyst (component (D)) and causes the hydrosilylation reaction in the composition to proceed. Furthermore, due to the properties of component (D), once the catalyst is activated by exposure to a temperature above its softening temperature, it is also possible to obtain a cured product at a temperature as low as 100°C.

[0122] [Uses of the Composition] The curable hot-melt silicone composition of the present invention has hot-melt properties, excellent handling and curing properties during melting (hot-melt), and excellent discoloration resistance at high temperatures in the cured product obtained by curing the composition. Therefore, it is useful for semiconductor components such as encapsulants for light-emitting / optical devices and light-reflecting materials, and for optical semiconductors containing the cured product. Furthermore, the cured product has excellent mechanical properties, making it suitable as an encapsulant for semiconductors; an encapsulant for power semiconductors such as SiC and GaN; and an adhesive, potting agent, protective agent, and coating agent for electrical and electronic applications. Furthermore, the curable hot-melt silicone composition of the present invention in sheet form is suitable as a material for sealing or adhering large-area substrates using press molding, compression molding, or a vacuum laminator. It is particularly suitable for use as an encapsulant for semiconductors that use overmolding during molding. Furthermore, sheets of the composition can be used as curable film adhesives or as a stress buffer layer between two substrates with different linear expansion coefficients.

[0123] Furthermore, the curable hot-melt silicone composition of the present invention, particularly a sheet-shaped curable hot-melt silicone composition, can be used for large-area sealing of semiconductor substrates (including wafers). Furthermore, sheets obtained by molding the curable hot-melt silicone composition of the present invention into a sheet can be used for die attach films, sealing of flexible devices, stress relief layers for bonding two different substrates, etc. In other words, the curable silicone composition of the present invention can be a sealant intended for single-sided sealing, or a sealant intended for double-sided sealing involving adhesion between two substrates, and has preferable properties suitable for these applications.

[0124] [Viscosity characteristics of the composition at high temperatures (thixotropy)] The curable silicone composition of the present invention has hot-melt properties, and is fluid at temperatures above 100°C, making it possible to measure its viscosity. Furthermore, its viscosity is highly dependent on the shear (shear force) applied during measurement, with the viscosity being high at low shear and low at high shear, making it thixotropic. Specifically, the shear rate of 1 s at 100°C and 150°C measured using a rheometer is－１ The viscosities at 100°C and 150°C are 5000 Pas or less and 1000 Pas or less, respectively, and when using a flow tester with a pressure of 2.5 MPa, which is considered to be the limiting shear rate, the viscosities are 500 Pas or less and 200 Pas or less, respectively. Such viscosity characteristics are advantageous in the process of pre-bonding the curable hot-melt silicone composition to a substrate using a vacuum laminator, vacuum low-pressure press, or the like, and then allowing it to stand and cure in an oven or the like. That is, during pre-bonding, pressure is applied instantaneously under constant temperature conditions to bond it to the substrate, and since pressure is applied at this time, the viscosity decreases, resulting in excellent gap filling properties for substrates with many irregularities. However, since no pressure is applied when the composition is subsequently left to stand and cure in an oven or the like, even when cured at temperatures of 150°C or higher, the viscosity is high and therefore dripping of the composition does not occur before curing begins.

[0125] [Curing Conditions of the Composition and Timing of Lamination] As described above, when the curable silicone composition of the present invention is exposed to a temperature higher than the Tg of component (D), the catalyst is activated, enabling rapid curing. Therefore, by adhering the composition to a substrate by thermocompression bonding or the like at a temperature below the Tg of component (D), it is possible to form a precursor of a laminate integrated with the substrate without any curing reaction. By exposing the precursor of this laminate to a temperature equal to or higher than the Tg of component (D), the composition of the present invention can be rapidly cured. Furthermore, by thermocompression bonding the substrate and the composition of the present invention at a temperature equal to or higher than the Tg of component (D), the catalyst can be activated during thermocompression bonding, making it possible to cure the composition simultaneously with thermocompression bonding or to cure the resulting precursor of the laminate at a lower temperature. This allows for flexible process selection depending on the structure of the device and the bonding areas, and allows the curing reaction to be carried out under desired conditions.

[0126] As an example, by using one or more means selected from a vacuum laminator, vacuum press, and compression molding to adhere at least one surface of a curable silicone composition sheet or film according to the present invention to part or all of a substrate (for example, an electronic component or its precursor), it is possible to obtain a laminate comprising an uncured, hot-melt curable silicone composition sheet or film according to the present invention on the substrate. If necessary, this laminate, in a state of adherence to other substrates, can be heated to or above the glass transition point (Tg) of the thermoplastic resin that constitutes component (D), whereby the curable silicone composition according to the present invention fills the fine irregularities and gaps on the substrate, and the curing reaction proceeds, forming a laminate comprising a cured product of the composition.

[0127] Furthermore, the lamination step of adhering at least one surface of a curable silicone composition sheet or film according to the present invention to all or part of a substrate by the above-mentioned means may be carried out simultaneously or in parallel with the step of heating to a temperature equal to or higher than the glass transition point (Tg) of the thermoplastic resin that constitutes component (D). Furthermore, when a cured product of the curable silicone composition according to the present invention is used as an adhesive layer or stress relief layer for two or more substrates, this step may be carried out while the cured product is in close contact with the other substrates.

[0128] [Light-shielding properties of the cured product] By selecting the component (E), the cured product of the present invention can be designed to have light-shielding or light-reflecting properties, and can be suitably used in optical applications similar to these. The cured product of the present invention has a parallel light transmittance of 50% or less, more preferably 30% or less, at a wavelength of 360 nm and an optical path length of 1 mm, measured in accordance with JIS K 7105.

[0129] [Hardness of the Cured Product] The suitable hardness of the cured product obtained by curing the curable hot-melt silicone composition of the present invention can be classified into two categories depending on its intended use. When both sides of a curable hot-melt silicone composition sheet of the present invention are to be bonded to an adherend, it is preferable that the Type A durometer hardness specified in JIS K 7215-1986 "Durometer Hardness Testing Method for Plastics" be 40 or more. This is because if the hardness is below the lower limit, the cured product tends to be too soft and brittle. On the other hand, if the intended use is to seal a substrate, it is preferable that the Type A durometer hardness be 60 or more. This is because if the hardness is below the lower limit, the surface of the cured product becomes sticky, reducing handleability.

[0130] [Uses of the cured product] The uses of the cured product obtained by curing the curable silicone composition of the present invention are not particularly limited. The composition of the present invention has hot-melt properties, exhibits excellent curing when triggered by a certain temperature, has excellent moldability and mechanical properties, and the cured product has little surface tack and is relatively hard. For this reason, the cured product obtained by curing this composition can be suitably used as a component for semiconductor devices, and can be suitably used as an encapsulant for semiconductor elements, IC chips, etc., or as an adhesive or bonding material for semiconductor devices.

[0131] There are no particular restrictions on the type of semiconductor device that includes a component made from a cured product obtained by curing the curable silicone composition of the present invention, but the composition of the present invention is particularly suitable for applications that require blocking or reflecting light, as it forms a cured product with light-shielding or light-reflecting properties. For example, light-emitting semiconductor devices that are light-emitting / optical devices, optical components for displays, and semiconductor devices where it is preferable that the interior is not visible, and in particular sealants or adhesive components for use in these devices, etc., are preferred.

[0132] The curable silicone composition of the present invention and its production method are described in detail below using examples and comparative examples. In the following description, Me, Vi, and Ph in the average unit formula represent methyl, vinyl, and phenyl groups, respectively. The softening point, curability, and storage stability of the curable silicone compositions of each example and comparative example were measured using the following methods. The results are shown in Table 1.

[0133] [Softening Point] The curable silicone composition was molded into a cylindrical pellet measuring φ14 mm x 22 mm. This pellet was placed on a hot plate set to 25°C to 100°C, and a 100 gram load was applied from above for 10 seconds. After the load was removed, the deformation of the pellet was measured. The temperature at which the deformation in the height direction reached 1 mm or more was taken as the softening point. [Melt Viscosity at 150°C] The melt viscosity of the curable silicone composition at 150°C was measured using a Koka-shiki Flow Tester CFT-500EX (manufactured by Shimadzu Corporation) under a pressure of 2.5 MPa using a nozzle with an outlet nozzle diameter of 1.0 mm. [Cure Properties] The curable silicone composition was vulcanized for 600 seconds at a predetermined temperature using a Curastometer (registered trademark) (PREMIER MDR manufactured by Alpha Technologies) according to the method specified in JIS K 6300-2:2001 "Unvulcanized rubber - Physical properties - Part 2: Determination of vulcanization properties using an oscillatory vulcanization tester," and the cure properties were measured. Examples 1 to 4 and Comparative Examples 2 to 8 were measured at 160°C, while Examples 5 and 6 and Comparative Example 1 were measured at 120°C. Furthermore, for Comparative Examples 2 to 4, ultraviolet light with a wavelength of 365 nm was irradiated at a dose of 10 J / cm. ２Measurements were then carried out after irradiation so that the curable hot-melt silicone composition reached a maximum value of 1 dNm. Approximately 5 g of the curable hot-melt silicone composition was weighed out, sandwiched between 50 μm-thick PET films, and placed on the lower die. Measurements were started when the upper die closed. A rubber R-type die was used, with an amplitude angle of 0.53°, a frequency of 100 rpm, and a maximum torque range of 230 kgf cm. The measurement results were recorded in minutes as the time (TS-1) required for the torque to exceed 1 dNm. The time (TC-90) required to reach 90% of the maximum torque was also recorded in minutes, and this was used as a guide for the time until the initial cure was nearly complete. [Storage Stability] The curable silicone composition was aged in an oven at 40°C for one week, and the curing characteristics were measured using the method described above, and the TS-1 value was recorded.

[0134] [Surface tackiness of cured products] The curable silicone compositions were vulcanized at a predetermined temperature for 10 minutes to produce cured products. Examples 1 to 4 and Comparative Examples 2 to 8 were cured at 160°C, while Examples 5 and 6 and Comparative Example 1 were cured at 120°C. Furthermore, Comparative Examples 2 to 4 were cured with ultraviolet light at a wavelength of 365 nm at an irradiation dose of 10 J / cm. ２ A PET film was pressed against the resulting cured product, and those that showed no sticking were rated as "no surface tack," and those that showed sticking were rated as "surface tack."

[0135] [Reflectance of the cured product] The curable silicone composition was vulcanized at a predetermined temperature for 10 minutes to produce a cured product having a thickness of 300 μm. Examples 1 to 4 and Comparative Examples 2 to 8 were cured at 160°C, while Examples 5 and 6 and Comparative Example 1 were cured at 120°C. For Comparative Examples 2 to 4, ultraviolet light with a wavelength of 365 nm was applied at an irradiation dose of 10 J / cm. ２ The reflectance of this cured product was measured using a UV-VIS spectrophotometer UV3100PC (manufactured by Shimadzu Corporation) to read the reflectance at a wavelength of 450 nm.

[0136] [Transmittance of cured product] The curable silicone composition was vulcanized at a specified temperature for 10 minutes to produce a cured product with a thickness of 300 μm. Examples 1 to 4 and Comparative Examples 2 to 8 were cured at 160°C, while Examples 5 and 6 and Comparative Example 1 were cured at 120°C. For Comparative Examples 2 to 4, ultraviolet light with a wavelength of 365 nm was irradiated at a dose of 10 J / cm. ２ The transmittance of this cured product was measured using a UV-VIS spectrophotometer UV3100PC (manufactured by Shimadzu Corporation) and the transmittance at a wavelength of 450 nm was read.

[0137] Mixtures of organopolysiloxane resin and linear organopolysiloxane having hot melt properties were prepared by the methods shown below in Reference Examples 1 to 3. Organopolysiloxane resin fine particles were also prepared by the methods shown in Reference Examples 4 and 5. Both preparation methods include a step of removing low-molecular-weight organopolysiloxane components, and the resulting raw material contains M ４ Q structures have been removed as much as possible.

[0138] [Reference Example 1: Hot-melt mixture 1] A white solid at 25°C, having the average unit formula: (Me ２ ViSiO １ / ２ ) ０.０５ (Me ３ SiO １ / ２ ) ０.３９ (SiO ４ / ２ ) ０.５６ (HO １ / ２ ) ０.０２ 2.40 kg of an organopolysiloxane resin (vinyl group content = 1.9 mass%), which is a white solid at 25°C and has the average unit formula: (Me ３ SiO １ / ２ ) ０.４４ (SiO ４ / ２ ) ０.５６ (HO １ / ２ ) ０.０２ 4.46 kg of an organopolysiloxane resin (vinyl group content = 0 mass%) represented by the formula: ViMe ２ SiO(Me ２ SiO) ８００ SiViMe ２2.69 kg of dimethylpolysiloxane (vinyl group content = 0.09% by mass) capped at both molecular chain ends with dimethylvinylsiloxy groups, represented by the formula (1), was dissolved in 4.00 kg of xylene using a Three-One motor in a pail. The resulting solution was fed into a twin-screw extruder with a maximum temperature set to 230°C, and the xylene and low-molecular-weight organopolysiloxane components were removed under a vacuum of -0.08 MPa, yielding hot-melt Mixture 1. Mixture 1 was received in a cylindrical pail and allowed to cool and solidify. The volatile content of this mixture was measured at 200°C for 1 hour, and was found to be 0.7% by mass.

[0139] [Reference Example 2: Hot-melt mixture 2] A white solid at 25°C, having the average unit formula: (Me ２ ViSiO １ / ２ ) ０.０５ (Me ３ SiO １ / ２ ) ０.３９ (SiO ４ / ２ ) ０.５６ (HO １ / ２ ) ０.０２ 3.09 kg of an organopolysiloxane resin (vinyl group content = 1.9 mass%) represented by the average unit formula: (Me ３ SiO １ / ２ ) ０.４４ (SiO ４ / ２ ) ０.５６ (HO １ / ２ ) ０.０２ 3.77 kg of an organopolysiloxane resin (vinyl group content = 0 mass%) represented by the formula: ViMe ２ SiO(Me ２ SiO) ８００ SiViMe ２2.69 kg of dimethylpolysiloxane (vinyl group content = 0.09% by mass) capped at both molecular chain ends with dimethylvinylsiloxy groups, represented by the formula (1), was dissolved in 4.00 kg of xylene using a Three-One motor in a pail. The resulting solution was fed into a twin-screw extruder with a maximum temperature set to 230°C, and the xylene and low-molecular-weight organopolysiloxane components were removed under a vacuum of -0.08 MPa, yielding a transparent hot-melt mixture 2. Mixture 2 was placed in a round-bottom pail and allowed to cool and solidify. The volatile content of this mixture was measured at 200°C for 1 hour, and was found to be 0.7% by mass.

[0140] [Reference Example 3: Hot-melt mixture 3] A white solid at 25°C, having the average unit formula: (Me ２ ViSiO １ / ２ ) ０.０５ (Me ３ SiO １ / ２ ) ０.３９ (SiO ４ / ２ ) ０.５６ (HO １ / ２ ) ０.０２ Organopolysiloxane resin (vinyl group content = 1.9 mass%) represented by the average unit formula: (Me ３ SiO １ / ２ ) ０.４４ (SiO ４ / ２ ) ０.５６ (HO １ / ２ ) ０.０２ 3.08 kg of an organopolysiloxane resin (vinyl group content = 0 mass%) represented by the formula: ViMe ２ SiO(Me ２ SiO) ８００ SiViMe ２2.56 kg of dimethylpolysiloxane (vinyl group content = 0.09% by mass) capped at both molecular chain ends with dimethylvinylsiloxy groups, represented by the formula (1), was dissolved in 4.00 kg of xylene using a Three-One motor in a pail. The resulting solution was fed into a twin-screw extruder with a maximum temperature set to 230°C, and the xylene and low-molecular-weight organopolysiloxane components were removed under a vacuum of -0.08 MPa, yielding a transparent hot-melt mixture 3. Mixture 3 was placed in a cylindrical pail and allowed to cool and solidify. The volatile content of this mixture was measured at 200°C for 1 hour, and was found to be 0.7% by mass.

[0141] [Reference Example 4: Silicone microparticles (1')] Average unit formula: (Me ２ Visio １ / ２ ) ０.０５ (Me ３ SiO １ / ２ ) ０.３９ (SiO ４ / ２ ) ０.５６ (HO １ / ２ ) ０.０２ A 55% by mass xylene solution of a resinous organopolysiloxane represented by the formula (I) was spray-dried at 50°C to microparticle while removing the xylene, to prepare spherical non-hot-melt silicone microparticles (1). When the microparticles were observed under an optical microscope, the particle diameter was found to be 5 to 10 μm, with an average particle diameter of 6.5 μm. The obtained silicone microparticles (1) were aged in an oven at 120°C for one week, and the M ４ This resulted in spherical non-hot melt silicone microparticles (1') from which component Q had been removed. The amount of volatile components in these microparticles was measured at 200°C for 1 hour and found to be 0.6 wt%.

[0142] [Reference Example 5: Silicone microparticles (2')] Average unit formula: (Me ３ SiO １ / ２ ) ０.４４ (SiO ４ / ２ ) ０.５６ (HO １ / ２ ) ０.０２A 55% by mass xylene solution of a resinous organopolysiloxane represented by the formula (I) was spray-dried at 50°C to microparticle while removing the xylene, to prepare spherical non-hot-melt silicone microparticles (2). When the microparticles were observed under an optical microscope, the particle diameter was found to be 5 to 10 μm, with an average particle diameter of 6.5 μm. The obtained silicone microparticles (2) were aged in an oven at 120°C for one week, and the M ４ This resulted in spherical non-hot melt silicone microparticles (2') from which component Q had been removed. The amount of volatile components in these microparticles was measured at 200°C for 1 hour and was found to be 0.7 wt%.

[0143] [Examples 1 to 6, Comparative Examples 1 to 7] In the present examples and comparative examples, the components of the above-mentioned Reference Example were used as the mixture (a+b) containing components (A) and (B), and the following component was also used: (b) Dimethylpolysiloxane capped at both molecular chain ends with dimethylvinylsiloxy groups ViMe ２ SiO(Me ２ SiO) ８００ SiViMe ２ (Vinyl group content = 0.09 mass%) (C) SiH siloxane (c-1) (PhSiO ３ / ２ ) ０.４ (HMe ２ SiO １ / ２ ) ０.６ (SiH group content = 0.6 mass%) (c-2) (HMe ２ SiO １ / ２ ) ０.５２ (Me ２ SiO ２／２ ) ０．１５ (SiO ４ / ２ ) ０.３３(SiH group content = 0.79 mass%) (D) Hydrosilylation reaction catalyst-containing microparticles (d-1) Thermoplastic polycarbonate resin microparticles containing 4000 ppm of platinum complex of Pt (0 valent) with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (Tg of thermoplastic resin = 145°C) (d-2) Thermoplastic acrylic resin microparticles containing 4000 ppm of platinum complex of Pt (0 valent) with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (Tg of thermoplastic resin = 115°C) (d') Average unit formula containing 400 ppm of platinum complex of Pt (0 valent) with 1,3-divinyl-1,1,3,3-tetramethyldisiloxane: (d'') (methylcyclopentadienyl)trimethylplatinum(IV) (d''') 1,3-divinyltetramethyldisiloxane solution of 1,3-divinyltetramethyldisiloxane complex of Pt(0 valent) (E) Filler or pigment (e1) Titanium oxide having an average particle size of 0.5 μm (SX-3103 manufactured by Sakai Chemical Industry Co., Ltd.) (e2) Carbon black having an average particle size of 35 nm (Denka Black Pressed product manufactured by Denka Co., Ltd.) (e3) Alumina having an average particle size of 0.44 μm (AES-12 manufactured by Sumitomo Chemical Co., Ltd.) (e4) Alumina having an average particle size of 3.0 μm (AL-M73A manufactured by Sumitomo Chemical Co., Ltd.) (e5) Alumina having an average particle size of 37.4 μm (AZ35-125 manufactured by Micron Company, Nippon Steel & Sumikin Materials Co., Ltd.) (F) Hardening retarder (f) Methyltris-1,1-dimethyl-2-propynyloxysilane

[0144] For Examples 1 to 7 and Comparative Examples 1 to 5, white or black curable hot-melt silicone compositions were prepared using the procedure shown below. For Comparative Examples 6 and 7, uniform granular curable silicone compositions were prepared by simultaneously adding all components to a small grinder using the following procedure. The composition, number of parts, and SiH / Vi ratio of the entire composition for each composition are shown in Tables 1 and 2. Furthermore, the softening viscosity, melt viscosity, TS-1 (initial and after aging at 40°C for one week), TC90, and physical properties of the cured product (surface tack, reflectance, and transmittance) for each composition are shown in Table 3.

[0145] Examples 1 to 7 and Comparative Examples 1 to 5 The hot-melt mixtures 1 to 3 obtained in Reference Examples 1 to 3 were fed into a twin-screw extruder via line 1 shown in FIG. 1 at 170°C using a hot melter for cylindrical pails (VersaPail melter manufactured by Nordson Corporation). Next, component (E) was added via line 3-a, and components (C) and (F) were added via line 3-b, each at a set temperature of 150°C. Next, component (D) diluted with component (B) was added via line 3-c at a set temperature of 80°C. The degree of vacuum in the extruder was -0.08 MPa, and degassing melt kneading was performed.

[0146] The outlet temperature of the twin-screw extruder was set to 80°C, and the mixture was in the form of a semi-solid softened material. A 330 mm wide, 125 μm thick release film (FL2-01, manufactured by Takaline Corporation) was conveyed at a speed of 1.0 m / min, and the mixture was fed onto the release film at a feed rate of 5 kg / hr. The mixture was sandwiched between two release films so that the release surface of the release film was in contact with the mixture, forming a laminate. The laminate was then pressed between rolls temperature-controlled at 90°C to stretch the mixture between the release films, forming a laminate in which a 300 μm thick curable hot-melt silicone composition sheet was sandwiched between two release films, and the entire laminate was then cooled by air cooling. The configuration of the production apparatus is shown in Figure 1.

[0147] Comparative Examples 6 and 7 The spherical non-hot-melt silicone microparticles (1') or (2') obtained in Reference Examples 4 and 5, components (B), (C), (D), (E), and (F) were all charged into a small grinder and stirred at room temperature (25°C) for 1 minute to prepare a uniform white curable granular silicone composition. The resulting granular silicone composition was then charged into a Brabender set to 90°C and melt-kneaded at 50 rpm for 3 minutes to obtain a uniformly mixed composition.

[0148] *In Examples 1 to 6 and Comparative Examples 1 to 6, a small amount of component (B) was used to dilute component (D).

[0149] [Summary] The curable silicone compositions of Examples 1 to 7 according to the present invention exhibited low viscosity and high fluidity when heated and melted without compromising storage stability, even when using white or colored fillers, and were capable of rapid curing at high temperatures above the glass transition point of the thermoplastic resin that constitutes component (D). Furthermore, the resulting cured silicone products had very little surface tackiness, making them suitable for use in protecting semiconductor elements and the like.

[0150] On the other hand, in Comparative Example 1, the softening point of the capsule-type catalyst used was not sufficiently high, so catalyst activation occurred during melt-kneading to obtain a uniform mixture, and the resulting composition did not exhibit sufficient storage stability. Furthermore, for Comparative Examples 2 to 4, a catalyst triggered by ultraviolet light was used, but when an inorganic filler that absorbs or reflects light in the ultraviolet range, as in the composition of the present invention, was contained, it was found that the catalyst could not be activated and sufficient curing properties could not be exhibited. On the other hand, in Comparative Examples 5 and 6, which used a conventional catalyst, an excessive amount of curing retarder was required to ensure sufficient storage stability, and using a large amount of curing retarder as in Comparative Example 5 inhibited curing properties. In Comparative Example 6, curing itself was possible, but despite the composition having a relatively slow curing rate, with an initial ts-1 of more than 2 minutes at 150 ° C., ts-1 decreased rapidly after storage at 40 ° C. for just one week compared to the Examples, and it was found that it was difficult to ensure the pot life of the resulting composition. Furthermore, when the amount of inorganic filler added is too large, as in Comparative Examples 7 and 8, the melt viscosity of the composition becomes too high, which raises concerns that the filling ability, particularly for small gaps and unevenness, will be insufficient, and at the same time, there is a concern that wear will occur easily during production, making it difficult to achieve the target color.

[0151] 1: Hot melter 2: Extruder 3-a: Powder feeder 3-b: Pump 3-c: Pump 3-d: Vacuum pump 4-a: Release sheet 4-b: Release sheet 5-a: Stretching roll (may optionally be equipped with a temperature control function) 5-b: Stretching roll (may optionally be equipped with a temperature control function) 6: Cooling roll 7: Film thickness gauge 8: Sheet cutter 9: Foreign body inspection machine

Claims

1. (A) 100 parts by mass of an organopolysiloxane resin containing the following components (A1) and (A2) in a mass ratio of 20:80 to 90:10, which exhibits a mass loss rate of 2.0% or less when exposed to 200°C for 1 hour: (A1) A curable polymer having a curable reactive functional group containing a carbon-carbon double bond in the molecule and SiO ４／２ an organopolysiloxane resin that is solid at 25°C and does not have hot melt properties by itself, and contains 20 mol% or more of siloxane units represented by the formula: (A2) A polymer having no curing reactive functional group containing a carbon-carbon double bond in the molecule and having SiO ４／２ an organopolysiloxane resin that is solid at 25°C and does not have hot melt properties by itself, and contains 20 mol% or more of siloxane units represented by the formula: (B) 10 to 100 parts by mass of a linear or branched organopolysiloxane that has at least two curing-reactive functional groups containing a carbon-carbon double bond in the molecule and is liquid or plastic at 25°C; (C) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in the molecule: in an amount such that the number of silicon-bonded hydrogen atoms per silicon-bonded alkenyl group contained in the entire composition is 0.5 to 20.0; (D) hydrosilylation catalyst-containing microparticles having a structure in which a hydrosilylation catalyst is encapsulated in a thermoplastic resin having a glass transition temperature (Tg) in the range of 110 to 200°C: the amount of platinum metal in the microparticles is 0.1 to 2,000 ppm by mass; (E) Fillers or pigments wherein the amount of component (E) is in the range of 0.01 to 100 parts by mass per 100 parts by mass of the sum of components (A) to (D), and the composition as a whole has hot-melt properties.

2. Furthermore, (F) a hydrosilylation reaction cure retarder having a boiling point of 200°C or higher under atmospheric pressure: in an amount of 1 to 5,000 ppm based on the total mass of the composition The curable silicone composition of claim 1 , comprising:

3. 2. The curable silicone composition of claim 1, wherein at least a portion of component (E) is a white or colored inorganic filler.

4. The component (A1) is (A1-1) a copolymer having the following average unit formula: (R １ ３ SiO １／２ ) ａ (R １ ２ SiO 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 are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, provided that all R １ 1 to 12 mol % of each R are alkenyl groups; ２ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; and a, b, c, d, and e are numbers that satisfy the following: 0.10≦a≦0.60, 0≦b≦0.70, 0≦c≦0.80, 0≦d≦0.65, 0≦e≦0.05, with the proviso that c+d>0.20 and a+b+c+d=1. is an organopolysiloxane resin represented by the formula: The component (A2) is (A2-1) a compound having the following average unit formula: (R ３ ３ SiO １／２ ) ｆ (R ３ ２ SiO ２／２ ) ｇ (R ３ SiO ３／２ ) ｈ (SiO ４／２ ) ｉ (R ２ O １／２）ｊ (In the formula, each R ３ are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms and no carbon-carbon double bonds; R ２ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; and f, g, h, i, and j are numbers that satisfy 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. is an organopolysiloxane resin represented by the formula: The component (B) is (B1) a compound represented by the following structural formula: R ４ ３ SiO(SiR ４ ２ O) ｋ SiR ４ ３ (In the formula, each R ４ are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, provided that R ４ at least two of the groups are alkenyl groups, and k is a number from 20 to 5,000. It is a linear diorganopolysiloxane represented by the formula: The curable silicone composition of claim 1.

5. A curable silicone composition sheet or film, in which the curable silicone composition according to any one of claims 1 to 4 is formed into a sheet or film having a thickness of 10 to 2000 µm.

6. A sheet or film adhesive comprising the curable silicone composition sheet or film according to claim 5.

7. A curable silicone composition sheet or film according to claim 5; A peelable laminate has a sheet or film-like substrate attached to one or both sides of the sheet or film, and the sheet or film has a release surface facing the sheet or film made of the curable silicone composition, and the curable silicone composition sheet or film can be peeled off from the sheet or film-like substrate with the release surface.

8. A laminate comprising a substrate that is an electronic component or a precursor thereof, and a curable silicone composition layer formed by adhering at least one surface of the curable silicone composition sheet or film according to claim 5 to part or all of the surface of the substrate, wherein the curable silicone composition is in an uncured state.

9. A cured product obtained by curing the curable silicone composition according to any one of claims 1 to 4 by heating it to a temperature equal to or higher than the glass transition temperature (Tg) of the thermoplastic resin that constitutes component (D) of the composition.

10. Use of the cured product according to claim 9 as a member for a semiconductor device or an optical semiconductor device.

11. A semiconductor device or optical semiconductor device comprising the cured product according to claim 9.

12. 6. A method for producing a curable silicone composition sheet or film according to claim 5, comprising the steps of melt-kneading the entire composition within a temperature range from 50°C to the glass transition point (Tg) of the thermoplastic resin that constitutes component (D), and then forming the composition into a sheet or film having a thickness of 10 to 2000 μm.

13. A method for producing the laminate described in claim 8, characterized in that at least one surface of the curable silicone composition sheet or film described in claim 5 is brought into close contact with part or all of a substrate that is an electronic component or a precursor thereof, using one or more means selected from the group consisting of a vacuum laminator, a vacuum press, and compression molding.

14. 10. A method for producing a laminate comprising the cured product according to claim 9, comprising the step of curing the uncured curable silicone composition by heating the laminate according to claim 8 to a temperature equal to or higher than the glass transition point (Tg) of the thermoplastic resin that constitutes component (D).

15. 10. A method for producing a laminate comprising the cured product of claim 9, comprising the steps of: using one or more means selected from the group consisting of a vacuum laminator, a vacuum press, and compression molding to adhere at least one surface of the curable silicone composition sheet or film of claim 5 to part or all of a substrate that is an electronic component or a precursor thereof; and heating the resulting sheet or film to a temperature equal to or higher than the glass transition point (Tg) of the thermoplastic resin that constitutes component (D), thereby curing the curable silicone composition sheet or film to form a laminate.