Curable silicone composition, cured product thereof, and laminate

Abstract

The present invention provides a hot-melt curable silicone composition and its use. The hot-melt curable silicone composition has excellent thermal dispensability and storage stability, can be cured by external energy stimulation, and its cured product has excellent adhesive properties and mechanical properties. A curable silicone composition, its cured product, and its use in semiconductor applications, etc., comprising (A) a non-hot-melt solid organopolysiloxane resin mixture, (B) a linear organopolysiloxane having curing-reactive functional groups that is liquid at 25°C, (C) an organohydrogenpolysiloxane, and (D) a hydrosilylation reaction catalyst that is inert at room temperature but activated by external energy stimulation, in a specific mass % range. The composition as a whole is hot-melt and has a melt viscosity at 100°C (measured by a flow meter) of 50 Pa·s or less. The composition is particularly suitable for use as an adhesive / sealant in hot-dispensing applications.

Description

Technical Field

[0001] The present invention relates to a hot-melt curable silicone composition, a cured product thereof, and a laminate containing the composition or cured product. The hot-melt curable silicone composition is solid at room temperature, but when heated to, for example, 50°C or higher, it can be dispensed using a dispenser or the like. Furthermore, at this dispensing temperature, curing reactivity is suppressed, and the composition exhibits excellent curability when triggered by external energy stimulation, such as irradiation with high-energy radiation or exposure to temperatures of 130°C or higher, resulting in a cured product having relatively high hardness and low viscosity. The present invention also relates to uses of the composition or cured product (particularly, semiconductor components such as semiconductor device components and optical semiconductor device components, and semiconductor devices containing the cured product), as well as methods for producing laminates using the composition. Background Art

[0002] Curable silicone compositions can be cured to form cured products with excellent heat resistance, cold resistance, electrical insulation, weather resistance, water resistance, and transparency, making them useful in a wide range of industrial fields. Cured products from these curable silicone compositions are generally less prone to discoloration than other organic materials and exhibit minimal degradation of physical properties over time, making them suitable as sealants or adhesives for optical materials and semiconductor devices.

[0003] In recent years, the popularity of hot-melt curable silicone compositions has been increasing due to their ease of handling and cost reduction. For example, Patent Documents 1 to 3 propose hot-melt curable silicone compositions in the form of flat plates or sheets. These curable silicone compositions exhibit excellent meltability, curability, and moldability as sealants. However, they present a challenge: in recent semiconductor production processes, adhesives and sealants for semiconductors and electronic components often require liquid dispensing or application using dispensers. However, in the case of flat plates, the curable silicone compositions cannot be flexibly applied to suit the bonding or sealing / sealing form.

[0004] On the other hand, Non-Patent Document 1 proposes a method for dispensing a hot melt curable silicone composition product (DOWSIL TM EA-4600 silicone adhesive) is sprayed for use. However, there are problems: this curable silicone composition product cures at room temperature, requiring approximately seven days to cure, making it insufficient for the short curing times required in semiconductor production processes or for the high-hardness, low-viscosity cured product. Furthermore, while hot-melt curable silicone compositions require a certain amount of heating to melt, the curing reaction begins with heating, making it difficult to achieve the desired cure time, leading to problems with reaction control.

[0005] Prior art literature

[0006] Patent Literature

[0007] [Patent Document 1] International Publication No. 2016 / 136243 Pamphlet

[0008] [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-009322

[0009] [Patent Document 3] Japanese Patent Publication No. 2017-512224

[0010] [Non-Patent Document 1] DOWSIL™ EA-4600 Silicone Adhesive for PCB Components Application Guide (Published by Dow Corning Toray Industries, Ltd., Form No. 11-3497-42-1120S2D, 2020) Summary of the Invention

[0011] Problems to be solved by the invention

[0012] The present invention has been made to solve the above-mentioned problems, and its object is to provide a hot-melt curable silicone composition, a cured product thereof, and uses thereof. The curable silicone composition is solid at room temperature but can be dispensed from a dispenser or the like by heating. On the other hand, the curing reactivity is suppressed between room temperature and the dispensing temperature, resulting in excellent reaction controllability and high-speed curing at a desired timing. The cured product thereof has practically sufficient adhesive and mechanical properties and exhibits relatively high hardness and low viscosity.

[0013] Solutions for solving problems

[0014] The present inventors have conducted intensive research and have found that the above-mentioned problems can be solved by the following curable silicone composition, its cured product, and its use in semiconductor applications, etc., thereby completing the present invention. The curable silicone composition comprises, in specific parts, an organopolysiloxane resin having a curing-reactive functional group containing a carbon-carbon double bond and an organopolysiloxane resin not having the curing-reactive functional group, an organopolysiloxane resin that is solid at 25°C, and an organopolysiloxane resin that is liquid at 25°C having the curing-reactive functional group. The composition comprises a linear organopolysiloxane, an organohydrogenpolysiloxane, and a hydrosilylation reaction catalyst (preferably selected from a photoactive hydrosilylation reaction catalyst and a catalyst containing thermoplastic resin microparticles) that is inert at room temperature but becomes active in the composition upon external energy stimulation. The composition as a whole is hot-melt and has a melt viscosity at 100°C (measured by a flow meter: nozzle diameter 1 mm, pressure 2.5 MPa) of 50 Pa·s or less. The composition may contain a substantially non-volatile hydrosilylation reaction curing retarder. Furthermore, the organopolysiloxane resin in the composition preferably has a mass loss rate of 2.0% by mass or less when exposed to 200°C for one hour in order to suppress surface tackiness of the cured product and provide a relatively hard cured product.

[0015] From the perspective of the technical effects of the present invention, the curable silicone composition is preferably used in the form of being filled in a dispensing box, barrel or tube, and the box, barrel or tube can be heated by a dispenser equipped with a heating portion and sprayed onto a substrate to form a laminate serving as a semiconductor precursor or an electronic component precursor.

[0016] Effects of the Invention

[0017] The present invention provides a hot-melt curable silicone composition, a cured product thereof, and uses thereof. The hot-melt curable silicone composition is solid at room temperature by selectively combining a hydrosilylation reaction catalyst having the property of being activated by external energy stimulation with the hot-melt curable silicone composition. However, by heating, for example, to 80°C or above, the composition can be stably dispensed from a dispenser or the like. On the other hand, since the curing reactivity is suppressed at this dispensing temperature, the reaction has excellent controllability. The composition can be cured at a high speed by triggering irradiation with high-energy rays such as ultraviolet rays and / or exposure to a temperature higher than the dispensing temperature (for example, 130°C or above). The cured product thereof has sufficient adhesive and mechanical properties for practical use and exhibits high hardness and low surface tack.

[0018] Here, when the above-mentioned hydrosilylation reaction catalyst is a photoactive hydrosilylation reaction catalyst that is activated by irradiation with high-energy rays, the composition after distribution can be cured at a high speed even at a low temperature of below 100°C by irradiation with high-energy rays. On the other hand, the composition to which black pigment or white pigment is added sometimes absorbs or reflects high-energy rays and cannot activate the reaction catalyst. In this case, by using thermoplastic resin particles containing a hydrosilylation reaction catalyst as a catalyst, it can be stably ejected at the distribution temperature, and on the other hand, it can be quickly cured by heating to a temperature above the melting point of the thermoplastic resin (preferably above 130°C). Needless to say, the type of hydrosilylation reaction catalyst and the energy stimulus used for activation of the catalyst can be appropriately selected according to the structure of the composition and the curing process, and the two can also be used in combination.

[0019] The hot-melt curable silicone composition of the present invention can be particularly preferably used as a sealant / sealing agent for protecting a substrate. In addition, it can also be used for bonding between substrates that require a harder adhesive layer (in the case of two substrates, double-sided bonding). In addition, by connecting a heatable slit die to the outlet of the dispenser, it can be sprayed out in a film-like or sheet-like shape controlled to the desired thickness and applied to the substrate, thereby achieving precision coating. Since the curable silicone composition of the present invention does not undergo a curing reaction at the time of heating and melting, it can be efficiently manufactured only through a simple mixing process, and can be provided in the desired shape, especially filled in a distribution box, barrel or tube. Furthermore, since the curable silicone composition of the present invention can be used in a heat dispensing process, it can be sprayed onto a substrate in a desired shape and cured by external energy stimulation (such as irradiation with high-energy rays such as ultraviolet rays or exposure to temperatures above 130°C). Therefore, it can be used as a sealant / sealant. If necessary, it can also be used as an adhesive layer between substrates by curing in a state of close contact (including pressure contact) with the substrate to be adhered. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 This is a schematic diagram of a twin-screw extruder used in Examples. DETAILED DESCRIPTION

[0021] The following describes the embodiments of the present invention in detail. In this specification, room temperature refers to the range of about 15 to 30°C, particularly 18 to 25°C, and atmospheric pressure refers to the atmospheric pressure in the environment in which the curable silicone composition of the present invention is handled in a laboratory or factory, and generally refers to about 1 atmosphere (1013.25 hPa). In addition, in the present invention, unless otherwise specified, "having hot melt properties" means that the composition as a whole is in a high viscosity (including a raw rubber state whose plasticity can be measured) or solid form at 25°C to a degree that allows it to maintain its shape, and has a melt viscosity in the range described below at 100°C, softens by heating, and has flowable properties. Conversely, "not having hot melt properties" means that the composition or its constituent components (solid organopolysiloxane resin, etc.) do not exhibit heat-melting behavior below 200°C alone. Specifically, it does not have a softening point or melt viscosity below 200°C.

[0022] [Curable silicone composition]

[0023] The curable silicone composition of the present invention is characterized by comprising:

[0024] (A) 100 parts by mass of an organopolysiloxane resin that is solid at 25°C and comprises the following components (A1) and (A2) in a mass ratio of 20:80 to 90:10, wherein each component alone does not have heat-fusibility;

[0025] (A1) having a curing-reactive functional group containing a carbon-carbon double bond in the molecule and containing at least 20 mol% or more of the total siloxane units RSiO 3 / 2 (R is a monovalent organic group, hydroxyl group or alkoxy group) or SiO 4 / 2 An organopolysiloxane resin having the siloxane units shown;

[0026] (A2) does not have a curing reactive functional group containing a carbon-carbon double bond in the molecule, and contains at least 20 mol% or more of the total siloxane units composed of SiO 4 / 2 An organopolysiloxane resin having the siloxane units shown;

[0027] (B) a linear organopolysiloxane having at least two curing-reactive functional groups containing carbon-carbon double bonds in its molecule and being liquid at 25°C;

[0028] (C) an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule;

[0029] (D) a hydrosilylation reaction catalyst having the property of being inert at room temperature but becoming active in the composition by external energy stimulation,

[0030] The composition as a whole has hot melt properties, and its melt viscosity at 100° C. (measured by a flow tester: outlet nozzle diameter 1 mm, pressure 2.5 MPa) is 50 Pa·s or less.

[0031] The composition may contain (E) a curing retarder for hydrosilylation reaction having a boiling point of 200° C. or higher at atmospheric pressure, and other additives may be formulated as long as they do not impair the technical effects of the present invention.

[0032] [Organopolysiloxane resin (A1) having a curing-reactive functional group]

[0033] The component (A1) is one of the main components of the present composition and has a curing reactive functional group containing a carbon-carbon double bond in the molecule and contains at least 20 mol% of SiO 4 / 2 The present invention relates to an organopolysiloxane resin comprising the siloxane units shown in FIG. 1 , wherein the component (A1) alone does not have heat-fusibility and is solid in a solvent-free state at 25°C. Here, R is a monovalent organic group, a hydroxyl group, or an alkoxy group, and is preferably selected from a curing-reactive group having a carbon-carbon double bond described below, a monovalent hydrocarbon group having 1 to 10 carbon atoms and not having a carbon-carbon double bond, a hydroxyl group, or an alkoxy group having 1 to 10 carbon atoms.

[0034] The curing-reactive group having a carbon-carbon double bond may also be a functional group having a carbon-carbon double bond, such as a (meth)acryloyloxy group, and is particularly preferably a hydrosilylation-reactive functional group. Such a functional group can form a cured product in the presence of the (C) organohydrogenpolysiloxane and (D) photoactive hydrosilylation catalyst described below. Examples of such curing-reactive groups include alkenyl groups having 2 to 10 carbon atoms, with vinyl and 1-hexenyl groups being particularly preferred.

[0035] Preferably, in component (A1), the proportion of alkenyl groups to all organic groups bonded to silicon atoms is 1 to 12 mol%, preferably 2 to 10 mol%. When the content of alkenyl groups is less than the lower limit of the range, the mechanical strength (hardness, etc.) of the resulting cured product may become insufficient. On the other hand, when the content of alkenyl groups is below the upper limit of the range, the composition containing this component can achieve good hot melt performance as the composition as a whole.

[0036] The (A1) component may also contain other functional groups that do not have a carbon-carbon double bond, and it is particularly preferred to contain a functional group selected from a monovalent hydrocarbon group having 1 to 10 carbon atoms and not having a carbon-carbon double bond, particularly a functional group selected from an alkyl group having 1 to 10 carbon atoms such as a methyl group. On the other hand, in the (A1) component, the proportion of aryl groups such as phenyl groups in all silicon-bonded organic groups is in the range of 0 to 5 mol%, more preferably in the range of 0 to 2 mol%, and most preferably, no aryl groups (=0 mol%). In the case of containing a large amount of aryl groups such as phenyl groups, the (A1) component itself becomes hot-melt, and in addition to sometimes failing to achieve the technical effect of the present invention, in the cured product, sometimes SiO 4 / 2 The group-specific effect of reinforcing the cured product is reduced.

[0037] Preferably, in component (A1), the functional group bonded to the silicon atom is a group selected from alkenyl groups such as methyl and vinyl. Preferably, 70 to 99 mol% of all organic groups bonded to silicon atoms are methyl groups, more preferably 80 to 98 mol% are methyl groups, and particularly preferably 88 to 98 mol% are methyl groups, and the remaining organic groups bonded to silicon atoms are alkenyl groups such as vinyl groups. Within this range, component (A1) alone does not have hot melt properties and is useful as a component that provides particularly excellent color resistance at high temperatures in the cured product obtained from the curable silicone composition of the present invention. It should be noted that component (A1) may also contain a small amount of hydroxyl or alkoxy groups.

[0038] The component (A1) contains SiO as a branching unit in an amount of at least 20 mol% or more of all siloxane units. 4 / 2 The siloxane units shown in the figure preferably contain at least 40 mol%, more preferably 50 mol%, and particularly preferably 50 to 90 mol%. It should be noted that R is preferably a monovalent organic group, and is particularly preferably a methyl group from the perspective of compatibility with other components. 4 / 2 When the content of the siloxane units is less than the lower limit, even if the organopolysiloxane resin contains a large amount of other branched siloxane units (such as RSiO 3 / 2 ), sometimes the technical effects of the present invention cannot be achieved.

[0039] Preferably, component (A1) is

[0040] (A1-1) an organopolysiloxane resin represented by the following average unit formula:

[0041] (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 )c (SiO 4 / 2 ) d (R 2 O 1 / 2 ) e

[0042] (In the formula, each R 1 are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, wherein all R 1 1 to 12 mol% are alkenyl groups; each R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; a, b, c, d and e are numbers satisfying the following: 0.10≤a≤0.60, 0≤b≤0.70, 0≤c≤0.80, 0.2≤d≤0.65, 0≤e≤0.05, wherein c+d>0.20 and a+b+c+d=1).

[0043] In the above average unit formula, each R 1 Each of the R groups is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, for example, an alkyl group having 1 to 10 carbon atoms, such as a methyl group, particularly preferably a methyl group; an alkenyl group having 2 to 10 carbon atoms, such as a vinyl group; an aryl group, such as a phenyl group; and an aralkyl group, such as a benzyl group. 1 2 to 45 mol% of the total number of R in one molecule is alkenyl. 1 2 to 35 mol% of the alkenyl group is an alkenyl group, and vinyl and / or 1-hexenyl are particularly preferred. When the content of the alkenyl group is less than the lower limit of the range, the mechanical strength (hardness, etc.) of the obtained cured product may become insufficient. On the other hand, if the content of the alkenyl group is below the upper limit of the range, the composition containing this component can form a cured product with excellent mechanical strength. It should be noted that each R 1 It is preferably a functional group selected from the alkyl and alkenyl groups. From the perspective of the technical effect of the present invention, R 1 It is preferred that no aromatic group such as a phenyl group is substantially contained.

[0044] In the above formula, R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. 2 The group R 2 O 1 / 2 This corresponds to the hydroxyl group or alkoxy group of the organopolysiloxane resin of the component (A1).

[0045] In the above formula, a represents the general formula: R 1 3SiO 1 / 2The ratio of the siloxane units is 0.1≤a≤0.90, preferably 0.15≤a≤0.85. When a is within this range, the curable silicone composition containing this component has good hot melt properties and can impart excellent adhesive properties and mechanical strength (hardness, elongation, etc.) to the cured product.

[0046] In the above formula, b represents the general formula: R 1 2SiO 2 / 2 b satisfies 0 ≤ b ≤ 0.70, and preferably satisfies 0 ≤ b ≤ 0.60. When b is below the upper limit of the range, the curable silicone composition containing this component has good hot melt properties and provides a composition with low blocking at room temperature. In the present invention, b can be 0, and b is preferably 0.

[0047] In the above formula, c represents the general formula: R 3 SiO 3 / 2 The ratio of siloxane units to the total weight of the composition is 0. c satisfies 0 ≤ c ≤ 0.80, and preferably satisfies 0 ≤ c ≤ 0.75. When c is below the upper limit of the range, the curable silicone composition containing this component has good hot melt properties and provides a composition with low surface viscosity and minimal adhesion at room temperature. In the present invention, c can be 0, and c is preferably 0.

[0048] In the above formula, d is the expression SiO 4 / 2 The ratio of the siloxane units in the composition should be 0.20≤d≤0.65, preferably 0.25≤d≤0.65, and particularly preferably 0.40≤d≤0.65. When d is within this numerical range, the composition containing this component can achieve good hot melt properties as a whole, and the cured product obtained by curing the composition is relatively hard and has sufficient flexibility for practical use.

[0049] In the present invention, in the above formula, c+d>0.20 is required. When the value of c+d is 0.20 or less, the composition as a whole may not achieve good hot melt performance, and the technical effects of the present invention may not be fully achieved.

[0050] In the above formula, e represents the general formula: R 2 O 1 / 2 The ratio of units of hydroxyl or alkoxy groups bonded to silicon atoms that may be present in the organopolysiloxane resin is represented by the formula (e). ...

[0051] Since component (A1) is solid at room temperature, it is preferably used in a state dissolved 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; organosilicones such as hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane; esters such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone in order to physically mix with component (B) described later. The solvent used here can be efficiently removed in the process described later. [Organopolysiloxane Resin (A2) Not Having a Curing-Reactive Functional Group]

[0052] Component (A2) is one of the main components of the present composition and does not have a curing reactive functional group containing a carbon-carbon double bond and contains at least 20 mol% or more of the total siloxane units composed of SiO 4 / 2 The siloxane units shown in FIG. 1 and FIG. 2 are organopolysiloxane resins that are solid in a solvent-free state at 25°C and do not have any heat-fusibility on their own. Component (A2) is used in combination with components (A1) and (B) within a specified amount range to achieve heat-fusibility in the curable silicone composition as a whole and excellent stress relaxation properties in the cured product obtained by curing the curable silicone composition.

[0053] Preferably, component (A2) does not contain curing-reactive functional groups containing carbon-carbon double bonds, such as alkenyl groups, in the molecule. On the other hand, it contains functional groups selected from monovalent hydrocarbon groups having 1 to 10 carbon atoms and not having carbon-carbon double bonds, particularly alkyl groups having 1 to 10 carbon atoms, such as methyl groups, and aryl groups. On the other hand, with respect to component (A2), the proportion of aryl groups such as phenyl groups in all silicon-bonded organic groups is preferably in the range of 0 to 5 mol%, more preferably in the range of 0 to 2 mol%, and most preferably contains no aryl groups at all (=0 mol%). When the content of aryl groups in component (A2) exceeds the upper limit, (in the case of containing a large amount of aryl groups such as phenyl groups, component (A2) itself sometimes becomes hot-melt and cannot achieve the technical effect of the present invention. In addition, in the cured product, sometimes SiO 4 / 2 The effect of reinforcing the cured product peculiar to the group decreases, and the coloring resistance of the cured product at high temperatures deteriorates.

[0054] Preferably, 70 to 100 mol% of the organic groups bonded to silicon atoms in component (A2) are methyl groups, more preferably 80 to 100 mol% are methyl groups, and particularly preferably 88 to 100 mol% are methyl groups. Within this range, component (A2) may be a component that does not exhibit thermal melting properties alone and contains SiO 4 / 2 The siloxane unit shown is a component that has a particularly excellent reinforcing effect on the cured product. Note that the organopolysiloxane resin of the component (A2) may also contain a small amount of hydroxyl groups or alkoxy groups.

[0055] The component (A2) is characterized in that it is an organopolysiloxane resin that is solid at 25°C in the absence of a solvent and contains at least 20 mol% or more of all siloxane units in the molecule as branched siloxane units composed of SiO 4 / 2 Preferably, in the organopolysiloxane of component (A2), SiO 4 / 2 The unit accounts for at least 40 mol % or more, preferably 50 mol % or more, and particularly in the range of 50 to 65 mol % of all siloxane units.

[0056] Preferably, the component (A2) has the following average unit formula (A2-1):

[0057] (R 3 3SiO 1 / 2 ) f (R 3 2SiO 2 / 2 ) g (R 3 SiO 3 / 2 ) h (SiO 4 / 2 ) i (R 2 O 1 / 2)j

[0058] (In the formula, each R 3 R is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms and not containing a carbon-carbon double bond; 2 An organopolysiloxane resin represented by: a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; f, g, h, i, and j are numbers satisfying the following: 0.35≤f≤0.55, 0≤g≤0.20, 0≤h≤0.20, 0.45≤i≤0.65, 0≤j≤0.05, and f+g+h+i=1).

[0059] In the above average unit formula, R 2 is the same group as above, preferably a hydrogen atom or a methyl group. 3 Each of the R groups is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms and not containing a carbon-carbon double bond, for example, an alkyl group such as a methyl group. 3 70 mol% or more, more preferably 88 mol% or more, of the alkyl groups having 1 to 10 carbon atoms, such as methyl groups, are particularly methyl groups. 3 It is preferred that an aryl group such as a phenyl group is not substantially contained.

[0060] In the above formula, f represents the general formula: R 3 3SiO 1 / 2The ratio of the siloxane units is 0.35≤f≤0.55, preferably 0.40≤f≤0.50. When f is within this range, the curable silicone composition containing this component has good hot melt properties and can impart excellent adhesive properties and mechanical strength (hardness, etc.) to the cured product.

[0061] In the above formula, g represents the general formula: R 1 2SiO 2 / 2 The ratio of siloxane units to the total weight of the composition is 0.000. g satisfies 0 ≤ g ≤ 0.20, and preferably satisfies 0 ≤ g ≤ 0.10. When g is below the upper limit of the range, the curable silicone composition containing this component has good hot melt properties and provides a composition with low blocking at room temperature. In the present invention, g may be 0, and preferably 0.000.

[0062] In the above formula, h represents the general formula: R 1 SiO 3 / 2 The ratio of siloxane units to the total weight of the composition is 0. h satisfies 0 ≤ h ≤ 0.20, and preferably satisfies 0 ≤ h ≤ 0.10. When h is below the upper limit of the range, the curable silicone composition containing this component has good hot melt properties and provides a composition with low surface viscosity and minimal adhesion at room temperature. In the present invention, h can be 0, and h is preferably 0.

[0063] In the above formula, i represents SiO 4 / 2 The ratio of the siloxane units is preferably 0.30 ≤ i ≤ 0.65, particularly preferably 0.50 ≤ i ≤ 0.65. Within this numerical range, the curable silicone composition containing this component can achieve excellent hot melt performance as the composition as a whole, and can achieve a cured product obtained by curing the curable silicone composition with excellent mechanical strength, no blocking as the composition as a whole, and good workability.

[0064] In the above formula, j represents the general formula: R 2 O 1 / 2 The ratio of units of hydroxyl or alkoxy groups bonded to silicon atoms that may be present in the organopolysiloxane resin is represented by the formula (j). j satisfies 0 ≤ j ≤ 0.05, preferably 0 ≤ j ≤ 0.03. It should be noted that in the above formula, the sum of f, g, h, and i, which is the sum of the siloxane units, is equal to 1.

[0065] Component (A2) is solid at room temperature and is preferably used in a dissolved state in a solvent or a solvent mixture in order to physically mix it with component (B) described below. The type of solvent is the same as that of the solvent in component (A1).

[0066] [(A) ingredient]

[0067] The curable silicone composition of the present invention comprises the components (A1) and (A2) as component (A) in a mass ratio of 20:80 to 90:10, preferably 35:65 to 90:10, and more preferably 50:50 to 90:10. Each component in component (A) alone does not have hot melt properties, but by using it in combination with the component (B) described below within a specified quantitative ratio range, the composition as a whole can achieve hot melt properties. In this composition, by combining components (A1) and (A2), the storage modulus and loss modulus of the cured product obtained by curing the curable composition, as well as tan δ calculated based on these ratios, can be adjusted to a certain extent, thereby achieving the preferred elastic modulus, flexibility, and stress relaxation properties of the cured product.

[0068] The mass reduction rate of the component (A) and the components (A1) and (A2) constituting the component (A) when exposed to 200°C for 1 hour is preferably 2.0 mass% or less. 3 3SiO 1 / 2 ) and Q unit (SiO 4 / 2 During the polymerization process, an organopolysiloxane resin composed of a volatile low-molecular-weight component, specifically, an M4Q structure, is produced as a byproduct. However, this structure significantly reduces the hardness of the cured product obtained from the curable silicone composition of the present invention. Furthermore, after the curable silicone composition containing the M4Q structure is integrally molded with a substrate such as a semiconductor, when the M4Q structure is removed by exposure to high temperatures, the volume of the cured product produced from the curable silicone composition may decrease, the hardness may increase significantly, and the molded product may change in size, warp, and increase the surface viscosity of the cured product. Furthermore, if a large amount of this M4Q structure remains in the composition or cured product, it may cause a significant increase in the hardness of the adhesive layer or sealant layer used for double-sided bonding, resulting in a significant change in the elastic modulus. Therefore, in order to use the curable silicone composition of the present invention for lamination with a substrate such as a semiconductor, it is preferable to remove the M4Q structure from the organopolysiloxane resin as early as possible before the raw materials are prepared before lamination with the substrate and curing the curable silicone composition.

[0069] However, the M4Q structure is highly compatible with the organopolysiloxane resin, making it difficult to remove volatile low-molecular-weight components, specifically the M4Q structure, from component (A) under drying conditions such as removal of the organic solvent. Therefore, since volatile components can be removed by treating the obtained crude raw material organopolysiloxane resin at a high temperature of approximately 200°C for a short period of time, the organic solvent and volatile components such as the M4Q structure are simultaneously removed from component (A1) or component (A2) using a twin-screw kneader set at a temperature of 200°C or higher. This allows the volatile low-molecular-weight components in component (A) to be removed at the raw material stage prior to preparing the curable silicone composition. The mass loss rate of component (A) after exposure to 200°C for one hour is preferably 2.0% by mass or less, and more preferably 1.0% by mass or less.

[0070] It should be noted that from the perspective of efficiently producing the curable hot-melt silicone composition of the present invention, it is preferable to perform the following process: add the component (B) described later to the component (A) dissolved in the organic solvent, mix them in a liquid state, and feed the resulting mixture to a twin-screw extruder set at 200°C or above to remove volatile components such as the M4Q structure along with the organic solvent. This method can produce a hot-melt mixture of components (A) and (B), which can be used for kneading with the remaining components constituting the curable silicone composition in the steps described below.

[0071] [(B) ingredient]

[0072] Component (B) is one of the main ingredients of this curable silicone composition. It is a linear organopolysiloxane that is liquid at 25°C and has at least two curing-reactive functional groups containing carbon-carbon double bonds within its molecule. This curing-reactive linear organopolysiloxane, when used in combination with the solid organopolysiloxane resin (component (A)), imparts hot-melt properties to the overall composition.

[0073] Component (B) needs to have a curing-reactive functional group containing a carbon-carbon double bond in the molecule. Such a curing-reactive functional group has hydrosilylation reactivity and forms a cured product through a cross-linking reaction with other components. Such a curing-reactive functional group is preferably an alkenyl group similar to the curing-reactive functional group possessed by component (A1), particularly a vinyl group or a hexenyl group.

[0074] Component (B) is a chain-like organopolysiloxane that is liquid or plastic at 25°C (room temperature) in the form of a raw rubber. It can be used in combination with component (A) to impart hot melt properties to the composition of the present invention. The chemical structure of the organopolysiloxane component (B) is linear or branched, and may have a polysiloxane structure branched by a small amount of T units or Q units, but is preferably

[0075] (B1) a linear polydiorganosiloxane represented by the following structural formula:

[0076] R 4 3SiO(SiR 4 2O) k SiR 4 3

[0077] (In the formula, each R 4 are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, wherein R 4 At least two of the groups are alkenyl groups, and k is a number from 20 to 1,000). Preferably, the polydiorganosiloxane has an alkenyl group at each end of the molecular chain, particularly a linear polydiorganosiloxane having a vinyl group.

[0078] 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, particularly preferably methyl; alkenyl groups such as vinyl, particularly preferably vinyl and / or hexenyl; aryl groups such as phenyl; and aralkyl groups such as benzyl. 4 At least two of R are alkenyl groups, preferably vinyl groups. 4 It is preferably a functional group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, such as a methyl group, and an alkenyl group, such as a vinyl group and a hexenyl group. It is preferred that all R 4 In each molecule, at least two are alkenyl groups, and the remaining R 4 It should be noted that, from the perspective of the technical effect of the invention, R 4 It is preferred that the phenyl group or other aromatic groups are substantially not contained. When a large number of phenyl groups or other aromatic groups are contained, the coloring resistance of the cured product obtained from the curable silicone composition at high temperature may be deteriorated. It is particularly preferred that the molecular chain has one vinyl group or other alkenyl group at each end, and the other R 4 It is a methyl group.

[0079] In the above formula, k is a number from 20 to 5,000, preferably from 30 to 3,000, and particularly preferably from 45 to 800. When k is at least the lower limit of the range, a curable silicone composition exhibiting minimal blocking at room temperature can be obtained. On the other hand, when k is at most the upper limit of the range, excellent hot melt performance can be achieved for the curable silicone composition as a whole.

[0080] The amount of component (B) added is in the range of 10 to 100 parts by mass, preferably 50 to 100 parts by mass, and more preferably 70 to 100 parts by mass, relative to 100 parts by mass of component (A). When the content of component (B) is within this range, the resulting curable silicone composition exhibits hot melt properties suitable for the heat dispensing process, has reduced tack at room temperature, and therefore has excellent workability. Furthermore, the mechanical strength of the cured product obtained by curing the composition is improved.

[0081] [(C) ingredient]

[0082] Component (C) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms in one molecule, and is a crosslinking agent that cures the composition by undergoing an addition reaction (hydrosilylation reaction) with the carbon-carbon double bonds in components (A1) and (B) in the presence of component (D).

[0083] The structure of the organohydrogen polysiloxane as a crosslinking agent is not particularly limited and may be linear, branched, cyclic or resinous. 1 / 2 The organohydrogensiloxy unit (D H unit, R is independently a monovalent organic group) as the main structural unit, having HR2SiO at its end 1 / 2 The diorganohydrogensiloxy unit (M H Unit, R is independently a monovalent organic group) organohydrogen polysiloxane, can also be composed of the D H Chain organohydrogen polysiloxane composed of units.

[0084] On the other hand, when the present curable silicone composition is used in a molding process, the content of the curing reactive functional group containing a carbon-carbon double bond in the present composition is small. Therefore, from the viewpoints of the curing speed, its moldability and curability, the organohydrogenpolysiloxane is preferably an organohydrogenpolysiloxane resin containing RSiO as a component thereof. 3 / 2 The single organosilyl alkoxy unit (T unit, R is a monovalent organic group or a silicon atom-bonded hydrogen atom) shown or the SiO 4 / 2 The branched unit of the siloxy unit (Q unit) shown in FIG, and the molecule has at least two HR2SiO 1 / 2 The diorganohydrogensiloxy unit (M H Unit, R is independently a monovalent organic group), the molecular end has M H unit.

[0085] The component (C) of the present invention is preferably an organohydrogen polysiloxane with low volatility. More specifically, it can be an organohydrogen polysiloxane having the following characteristics: after exposure to 100°C under atmospheric pressure for 1 hour, the mass reduction rate relative to the mass before exposure is 10% by mass or less, and the content of volatile low molecular weight is low. As described later, in the production process of filling the curable silicone composition of the present invention into the box, in order to obtain a composition without voids, etc., it is preferred 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. However, even with extremely short heating times, when a large amount of the components constituting the composition volatilize under such kneading conditions, it is sometimes impossible to obtain a composition with the characteristics as designed. In particular, since the amount of organohydrogenpolysiloxane added as a crosslinking agent is relatively small relative to the total mass of the curable silicone composition, the properties of the composition (curing characteristics, physical properties of the cured product, etc.) may vary significantly from the expected values ​​due to the volatilization of this component. Therefore, it is particularly preferable to select an organohydrogenpolysiloxane with low volatility for component (C), depending on its application and production method (especially filling into a box, bucket, or cartridge).

[0086] Particularly preferred organohydrogenpolysiloxanes are

[0087] From the following average unit formula (1):

[0088] (R 5 3SiO 1 / 2 ) l (R 6 2SiO 2 / 2 ) m (R 6 SiO 3 / 2 ) n (SiO 4 / 2 ) p (R 2 O 1 / 2 ) q

[0089] Represented organohydrogenpolysiloxane resin.

[0090] In the formula, each R 5 The same or different, is a monovalent hydrocarbon group with 1 to 10 carbon atoms or a hydrogen atom without aliphatic unsaturated carbon bonds, wherein at least two R 5 is a hydrogen atom. 5 The monovalent hydrocarbon group includes, for example, an alkyl group such as a methyl group; an aryl group such as a phenyl group; an aralkyl group such as a benzyl group; and other halogenated alkyl groups. From an industrial viewpoint, a methyl group or a phenyl group is preferred.

[0091] Where R 6It is a monovalent hydrocarbon group having 1 to 10 carbon atoms and having no aliphatic unsaturated carbon bond, and examples thereof include the same groups as those mentioned above. 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and examples thereof include the group consisting of: 2 Same group.

[0092] In the formula, l, m, n and p are 0.01≤l≤0.6, 0≤m, 0≤n≤0.9, 0≤p≤0.9 and l+m+n+p=1, and preferably 0≤q≤0.05, n+p≥0.2. More specifically, the organohydrogenpolysiloxane resin as component (C) includes M H MT resin, M H T resin, M H MTQ resin, M H MQ resin, M H DQ resin and M H Q resin, etc. In the description of the resin, M, D, T, Q represent M unit, D unit, T unit and Q unit respectively. H represents an M unit having a hydrogen atom.

[0093] The component (C) is preferably an organohydrogenpolysiloxane represented by the following average unit formula (2) and containing Q units.

[0094] Average unit formula (2):

[0095] (HR 6 2SiO 1 / 2 ) e (R 6 2SiO 2 / 2 ) f (SiO 4 / 2 ) g

[0096] Where R 6 Each independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and containing no aliphatic unsaturated bond, and e, f, and g are numbers that satisfy the conditions of 0.01≤e≤0.6, 0≤f≤0.9, 0.2≤g≤0.9, and e+f+g=1.

[0097] Specific examples of the monovalent hydrocarbon group are the same as those of R in the above average composition formula (1). 4 The specific examples of the monovalent hydrocarbon groups shown are the same as those shown in FIG. 6 Preferably, they are each independently selected from a methyl group and a phenyl group.

[0098] Similarly, the component (C) is preferably an organohydrogenpolysiloxane containing T units represented by the following average unit formula (3).

[0099] Average unit formula (3):

[0100] (HR 7 2SiO 1 / 2 ) h (R 7 2SiO 2 / 2 ) i (R 8 SiO 3 / 2 ) j

[0101] Where R 7 and R 8 are each independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms and not containing an aliphatic unsaturated bond, and all R 8 At least 10 mol% are aromatic groups, and h, i, and j are numbers satisfying the conditions of 0.01≤h≤0.6, 0≤i≤0.9, 0.2≤j≤0.9, and h+i+j=1.

[0102] Specific examples of the monovalent hydrocarbon group are the same as those shown as specific examples of the monovalent hydrocarbon group in the above average unit formula (1). 8 As a condition that at least 10 mol% of the phenyl groups are present, R 8 Preferably, they are each independently selected from a methyl group and a phenyl group.

[0103] The organohydrogenpolysiloxane resin represented by the above average unit formula (2) or (3) may be used alone or in combination.

[0104] The content of the organohydrogenpolysiloxane as component (C) in the curable silicone composition of the present invention is an amount sufficient for curing the curable silicone composition. The amount of silicon-bonded hydrogen atoms in the organohydrogenpolysiloxane as component (C) relative to the curing-reactive 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 bonded to silicon atoms contained in the entire curable silicone composition is 0.5 to 20.0, particularly preferably 1.0 to 10.

[0105] [(D) ingredient]

[0106] Component (D) is one of the characteristic features of the curable silicone composition of the present invention. It is a hydrosilylation reaction catalyst used to crosslink the curing-reactive functional groups containing carbon-carbon double bonds contained in components (A) / (B) with silicon-bonded hydrogen atoms (Si—H groups) contained in component (C) through a hydrosilylation reaction, thereby curing the curable silicone composition of the present invention. Specifically, the hydrosilylation reaction catalyst remains inactive at room temperature without external energy stimulation, but becomes active in the composition upon external energy stimulation. External energy stimulation includes external application of heat energy such as high-temperature exposure, light energy such as high-energy radiation, or physical energy such as vibration or impact to the composition. In the present invention, representative external energy stimulations include high-energy radiation exposure and high-temperature (preferably 130°C or higher) exposure, depending on the type of component (D). Preferably, these energy stimulations trigger the catalytic activity for the hydrosilylation reaction, thereby causing the curing reaction of the entire composition to proceed.

[0107] Component (D) is not particularly limited as long as it possesses the properties described above, but one or more hydrosilylation catalysts selected from (D1) a hydrosilylation catalyst that becomes active in the composition upon exposure to high-energy radiation and (D2) thermoplastic resin microparticles containing a hydrosilylation catalyst are particularly preferred for practical purposes. Component (D) can be appropriately selected based on the composition of the curable silicone composition of the present invention (e.g., whether the composition before curing contains a light-shielding or light-absorbing component) or the type of curing process, and both can be used in combination depending on the curing process.

[0108] Component (D1) is a form of component (D) and is known in the art as a high-energy ray-activated catalyst or photoactivated catalyst. The photoactive hydrosilylation reaction catalyst (component (D1)) is inactive even in a heated, molten state, unless exposed to high-energy radiation such as ultraviolet rays. On the other hand, after exposure to high-energy radiation, the curing reaction proceeds smoothly even at low temperatures, such as room temperature, without heating. Therefore, the composition of the present invention as a whole can be cured at low temperatures, triggered by irradiation with high-energy radiation. Furthermore, due to its excellent storage stability, it is preferably suitable for use in heat dispensing processes that require exposure to temperatures above 50°C. Furthermore, since the reaction is easily controlled, it can achieve excellent workability. Furthermore, component (D1) suppresses catalytic activity in a short period of time, even during the heating and melting process. Therefore, in the production process of filling the curable silicone composition of the present invention into a cartridge, the curable silicone composition can be melt-kneaded under reduced pressure within a temperature range of 50°C to 150°C and then filled into a dispenser cartridge, barrel, or cartridge without compromising its storage stability.

[0109] Furthermore, the component (D1) has a property of being uniformly compatible with the curable silicone composition, and can easily design a composition and a cured product having excellent transparency (=light transmittance).

[0110] Examples of high-energy rays include ultraviolet rays, gamma rays, X-rays, α-rays, and electron beams. In particular, ultraviolet rays, X-rays, and electron beams irradiated by commercially available electron beam irradiation devices are mentioned. Ultraviolet rays are preferred from the perspective of catalyst activation efficiency, and ultraviolet rays with a wavelength of 280 to 380 nm are preferred from the perspective of industrial utilization. The irradiation dose varies depending on the type of high-energy ray-activated catalyst. In the case of ultraviolet rays, the cumulative irradiation dose at a wavelength of 365 nm is preferably 100 mJ / cm 2 ~100J / cm 2 within the range.

[0111] Specific examples of the component (D1) include (methylcyclopentadienyl)trimethylplatinum (IV), (cyclopentadienyl)trimethylplatinum (IV), (1,2,3,4,5-pentamethylcyclopentadienyl)trimethylplatinum (IV), (cyclopentadienyl)dimethylethylplatinum (IV), (cyclopentadienyl)dimethylacetylplatinum (IV), (trimethylsilylcyclopentadienyl)trimethylplatinum (IV), (methoxycarbonylcyclopentadienyl)trimethylplatinum (IV), (dimethylphenylsilylcyclopentadienyl)trimethylcyclopentadienylplatinum (IV), trimethyl(acetylacetonate)platinum (IV), trimethyl(3,5-heptyl)platinum (IV), and trimethyl(3,5-heptyl)platinum (IV). diketonate) platinum (IV), trimethyl (methylacetoacetate) platinum (IV), bis(2,4-pentanedionate) platinum (II), bis(2,4-hexanedionate) platinum (II), bis(2,4-heptanedionate) platinum (II), bis(3,5-heptanedionate) platinum (II), bis(1-phenyl-1,3-butanedione) platinum (II), bis(1,3-diphenyl-1,3-propanedione) platinum (II), and bis(hexafluoroacetylacetonate) platinum (II). Among them, (methylcyclopentadienyl)trimethylplatinum (IV) and bis(2,4-pentanedionate) platinum (II) are preferred from the aspects of versatility and ease of acquisition.

[0112] Component (D2) is another form of component (D) and can also be microparticles in which a hydrosilylation catalyst, typically a platinum-based catalyst, is dissolved or dispersed in a thermoplastic resin, or microcapsule microparticles having a structure in which a platinum-based catalyst serves as a core within a thermoplastic resin shell. Here, the thermoplastic resin serves as the wall material for the hydrosilylation catalyst. At room temperature to low temperatures (around the dispensing temperature), this wall material renders the hydrosilylation catalyst in the particles inert, preventing it from dispersing in the system. However, at high temperatures (e.g., 130°C or higher), the thermoplastic resin serving as the wall material melts, dispersing and activating the hydrosilylation catalyst in the system, allowing the curing reaction based on the hydrosilylation reaction to proceed.

[0113] Examples of the platinum-based catalyst contained in the component (D2) include platinum black, platinum-supported carbon fine powder, platinum-supported silica fine powder, chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum olefin complexes, and platinum alkenylsiloxane complexes. The thermoplastic resin is not particularly limited as long as it substantially prevents the platinum-based catalyst from penetrating at least during storage and substantially does not dissolve in the organopolysiloxane, the main component of the present composition. Preferred examples include silicone resins, polysilane resins, acrylic resins, methylcellulose, and polycarbonate resins. The softening point or glass transition point of the thermoplastic resin is preferably within the range of 40 to 200°C. The softening point is the temperature at which the resin begins to flow due to its own weight or its own surface tension, and can be measured by observing the crushed particles under a microscope while increasing the temperature at a constant rate. The glass transition point can also be measured using a DSC (Differential Scanning Calorimeter). In the present invention, the curable silicone composition is briefly exposed to temperatures around 100°C in the production process described below. Therefore, either the softening point or the glass transition point is preferably within the range of 100°C to 200°C, more preferably within the range of 130°C to 200°C. This is because, when the softening point or glass transition point of the thermoplastic resin is less than 100°C, the catalyst tends to activate during production of the curable silicone composition, significantly reducing storage stability. On the other hand, when the temperature exceeds 200°C, sufficient heat curing speed tends to be inadequate. The average particle size of the platinum-based catalyst-containing thermoplastic microparticles is not limited, but is preferably within the range of 0.1 to 500 μm, more preferably within the range of 0.3 to 100 μm. This is because it is difficult to produce thermoplastic resin microparticles containing a hydrosilylation reaction catalyst with an average particle size below the lower limit of the aforementioned range. On the other hand, if the average particle size exceeds the upper limit of the aforementioned range, dispersibility in the curable silicone resin composition is reduced.

[0114] As component (D2) in the present invention, thermoplastic resin microparticles containing a hydrosilylation reaction catalyst are preferably used. These thermoplastic resin microparticles containing a hydrosilylation reaction catalyst are made of a thermoplastic resin having a softening point or glass transition point of 130°C or higher, preferably in the range of 130 to 200°C, for example, a thermoplastic resin at least partially comprising a polycarbonate resin. This is because, in this case, melting of the thermoplastic resin serving as the wall material is suppressed at temperatures below 130°C, thereby maintaining the hydrosilylation reaction catalyst in an inactive state during conventional melt-kneading processes and dispensing temperatures, resulting in particularly excellent storage stability and reaction controllability.

[0115] It should be noted that the thermoplastic resin fine particles (D2) containing a hydrosilylation reaction catalyst are substantially insoluble in the curable silicone composition, and a transparent composition cannot be obtained. Therefore, when using component (D2), it is sometimes difficult to design a composition with excellent transparency and light transmittance.

[0116] The method for preparing such thermoplastic resin microparticles containing a platinum-based catalyst is not limited; 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 preferred because they readily yield microcapsule microparticles with a narrow particle size distribution. Microparticles obtained by these methods can be used directly, but to obtain a curable silicone composition with excellent storage stability, it is desirable to wash the microparticles with an appropriate cleaning solvent to remove the platinum-based catalyst adhering to their surfaces. A suitable cleaning solvent is one that does not dissolve the thermoplastic resin but does dissolve the platinum-based catalyst. Examples of such cleaning solvents include alcohols such as methanol and ethanol, and low-molecular-weight organopolysiloxanes such as hexamethyldisiloxane. The ratio of the hydrosilylation reaction catalyst to the thermoplastic resin varies greatly depending on the method used to produce the pellets and cannot be specifically limited, but the platinum-based catalyst content is preferably 0.01% by mass or greater relative to the thermoplastic resin. This is because, when the content of the platinum-based catalyst is less than 0.01% by mass, the physical properties of the cured product are impaired by the composition unless a large amount of thermoplastic resin fine particles containing the platinum-based catalyst are contained in the composition.

[0117] As described above, component (D) can be appropriately selected based on the composition of the curable silicone composition of the present invention (e.g., whether the composition before curing contains a light-shielding or light-absorbing component) or the type of curing process. For example, when i) the composition itself contains a large amount of light-shielding / light-absorbing / reflecting components (e.g., white pigments or black pigments, UV shielding agents, etc.), ii) it is difficult to irradiate the composition with high-energy radiation during the curing process, and / or iii) transparency (= light transmittance) is not required for the composition and its cured product, it is preferable to select component (D2) as component (D) and cure it by high-temperature exposure.

[0118] On the other hand, if i) the curing process allows for a curing reaction triggered by irradiation with high-energy rays, ii) the substrate type (heat resistance, high-temperature deformation, etc.) or the curing process does not allow for high-temperature exposure, and / or iii) transparency (= light transmittance) is required for the composition and its cured product, it is preferable to select component (D1) and use irradiation with high-energy rays as a trigger for curing. It should be noted that a combination of the two can also be used to design a multi-stage curing process / step.

[0119] The amount of component (D) added is a catalytic amount. Specifically, the amount of metal atoms in component (D) is within a range of 1 to 500 ppm, more preferably 2 to 200 ppm, by mass relative to the entire composition.

[0120] The composition of the present invention may also contain other curing agents (e.g., peroxides, photopolymerization initiators, or photosensitizers) and hydrosilylation catalysts other than photoactive types, as arbitrarily selected, within the scope of not impairing the technical effects of the present invention. However, for the reasons mentioned above, such as preventing voids, these optional curing components are preferably substantially non-volatile.

[0121] [Hydrosilylation curing retardant]

[0122] The curable silicone composition of the present invention may contain, in addition to the above-mentioned components (A) to (D), a curing retarder for a hydrosilylation reaction. The structure of the curing retarder is not particularly limited, but from the perspective of the technical effect of the present invention, it is particularly preferred to use (E) a curing retarder for a hydrosilylation reaction having a boiling point of 200°C or above at atmospheric pressure. The reason for this is that in the production process of the curable silicone composition, when the raw materials are melt-kneaded under reduced pressure, if a compound with a low boiling point is used as a curing retarder, part or all of the curing retarder may volatilize during the melt-kneading process, thereby failing to obtain the target curing delay effect for the curable silicone composition.

[0123] The curing retarder of the present invention is not particularly limited. Examples thereof include alkynols 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-pentene-1-yne and 3,5-dimethyl-3-hexene-1-yne; low molecular weight siloxanes containing alkenyl groups such as tetramethyltetravinylcyclotetrasiloxane and tetramethyltetrahexenylcyclotetrasiloxane; and alkynoxysilanes such as methyl-tris(1,1-dimethylpropynyloxy)silane and vinyl-tris(1,1-dimethylpropynyloxy)silane. Among these, it is particularly preferred to use a curing retarder (E) having a boiling point of 200°C or higher at atmospheric pressure. For practical purposes, alkynoxysilanes such as methyl-tris(1,1-dimethylpropynyloxy)silane and vinyl-tris(1,1-dimethylpropynyloxy)silane are preferred. The content of the curing retardant in the curable silicone composition is not particularly limited, but is preferably within a range of 1 to 10,000 ppm by mass relative to the composition.

[0124] [(F) Other additives]

[0125] In addition to the aforementioned components (A) to (D) and any component (E), materials known in the art may be added to the curable silicone composition of the present invention as additives for the silicone composition. The following additives are listed as usable additives, but are not limited thereto. It should be noted that, in the technical effects of the present invention and in the production process of the curable silicone composition, when the raw materials are melt-kneaded under reduced pressure, the other additives are particularly preferably high-boiling-point or substantially non-volatile components.

[0126] [(F1) Functional fillers]

[0127] Functional fillers can be used as additives for the purpose of improving the mechanical properties of the cured product composed of the curable silicone composition of the present invention, or improving flame retardancy. As such functional fillers, inorganic fillers, organic fillers, and mixtures thereof are exemplified. As the inorganic filler, reinforcing fillers, pigments (particularly white pigments or black pigments), thermally conductive fillers, electrically conductive fillers, phosphors, and mixtures of at least two of these are exemplified. As the organic filler, silicone resin fillers, fluororesin fillers, and polybutadiene resin fillers are exemplified. It should be noted that the shape of these fillers is not particularly limited and may be spherical, spindle-shaped, flat, needle-shaped, amorphous, etc.

[0128] The type and amount of the functional filler are preferably selected within the range in which the curable silicone composition of the present invention can be melt-kneaded and within the range in which the influence on the technical effects of the present invention (e.g., curing characteristics, mechanical properties after curing, weather resistance, etc.) is tolerable.

[0129] A preferred embodiment of the curable silicone composition of the present invention is one that contains substantially no functional filler. In particular, when the aforementioned component (D1) is used and the curing reaction is triggered by irradiation with high-energy rays, if a large amount of light-shielding or light-absorbing / reflecting functional fillers, such as white pigments or black pigments, are contained, the high-energy rays may be shielded, absorbed, or reflected on the surface of the composition, thereby hindering the photoactivation of component (D1) and significantly deteriorating the curability of the composition.

[0130] On the other hand, when the curable silicone composition contains a light-shielding or light-absorbing / reflecting functional filler (e.g., a black pigment or a white pigment) as component (F1), it is preferable to use the thermoplastic resin microparticles containing a hydrosilylation reaction catalyst as component (D2) as a catalyst. This is because when such a filler is included, transparency or light transmittance is generally not required, and thus, the composition containing these pigments can be rapidly cured by exposure to high temperatures (e.g., 130°C or higher).

[0131] [(F2) Adhesion-imparting agent]

[0132] In the composition of the present invention, as long as the purpose of the present invention is not damaged, an adhesion-imparting agent may also be contained.Such adhesion-imparting agent is identical to the component preferably exemplified by the applicant in the international patent application (PCT / JP2020 / 12027), except for silane compounds such as 3-glycidoxypropyltrimethoxysilane, organosiloxane oligomers, and alkyl silicates, the reaction mixture of an organoalkoxysilane containing an amino group and an organoalkoxysilane containing an epoxy group disclosed in Japanese Patent Publication No. 52-8854 and Japanese Patent Application Laid-Open No. 10-195085 can be preferably utilized, in particular, a cyclic carbon nitrogen siloxane derivative having a silicon atom-bonded alkoxy group or a silicon atom-bonded alkenyl group in one molecule, a silatrane derivative having an organic group containing an alkoxysilyl group, etc. The content of the adhesion-imparting agent is not limited, but is preferably within the range of 0.01 to 10 parts by mass relative to a total of 100 parts by mass of the present composition.

[0133] [Other optional ingredients]

[0134] Furthermore, the present composition may contain, as other optional components, heat-resistant agents 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.

[0135] [Shape Retention and Melt Viscosity of Composition]

[0136] The curable silicone composition of the present invention is a solid with shape retention at 25°C. However, as mentioned above, it must be hot-melt, and in particular, its melt viscosity at 100°C (measured using a flow meter: nozzle diameter 1 mm, pressure 2.5 MPa) must be 50 Pa·s or less. Shape retention means that the composition exhibits virtually no deformation or fluidity in the absence of external force, but may be a solid or rubbery solid that exhibits measurable deformation or plasticity when an external force is applied.

[0137] The curable silicone composition of the present invention has the property of rapidly melting and decreasing in viscosity as the temperature rises under high temperature and high pressure during the manufacturing process of laminates, etc. Therefore, its melt viscosity is preferably measured under high pressure using a flow meter such as a Koka flow meter (manufactured by Shimadzu Corporation). Specifically, the melt viscosity of this composition at 100°C, measured using a Koka flow meter with an outlet nozzle diameter of 1 mm and a pressure of 2.5 MPa, is preferably 50 Pa·s or less, and more preferably 30 Pa·s or less. This is because a melt viscosity within this range improves dispensability at 100°C.

[0138] [Manufacturing method and filling form into box, barrel or tube]

[0139] The curable silicone composition of the present invention can be manufactured by heating and melting components (A) to (D) and component (E) and any other components and uniformly mixing the components, and then cooling as needed, but it is not limited to this method and the composition can be manufactured by any method. The mixer that can be used in this manufacturing method is not particularly limited, but as examples, there can be listed batch (batch) type heating and mixing devices such as kneaders, Banbury mixers, Henschel mixers, planetary mixers, double-roll mills, three-roll mills, Ross mixers, LABO PLASTOMILL, etc., and single-screw extruders and twin-screw extruders with heating and cooling functions. The curable silicone composition involved in the present invention is particularly suitable for use in the form of filling into a box, barrel or barrel, heating and spraying through a dispenser. Therefore, from the perspective of being able to continuously fill into the container, it is particularly preferred to use a single-screw or twin-screw continuous mixer for manufacturing.

[0140] The curable silicone composition of the present invention is particularly preferably used in a form filled into a box, bucket, or cartridge for dispensing. Such a box, bucket, or cartridge containing the curable silicone composition is obtained by continuously filling the container with the curable silicone composition using a production method comprising the following steps P1 and P2.

[0141] Step P1: A step of mixing the components of the curable hot-melt silicone composition at a temperature preferably above 50°C

[0142] Step P2: The heated and melted mixture obtained in step P1 is ejected from a nozzle and continuously filled into a box, barrel, or canister.

[0143] [Process P1]

[0144] Step P1 is a step for kneading the components of the composition of the present invention while heating and melting them. This process involves heating and kneading the heat-meltable mixture at a temperature above its softening point, preferably within a temperature range of 50°C to 200°C, until the entire composition is melted or softened, thereby achieving uniform mixing of the components contained in the mixture. The mixture obtained in Step P1 is a uniformly mixed composition, and thus can be filled into a box, barrel, or canister in Step P2 to produce a box, barrel, or canister containing a curable silicone composition for heat dispensing. On the other hand, if the temperature of the heated mixture is below the lower limit, the softening of the mixture may be insufficient, making it difficult to obtain a melted or softened mixture in which the components are uniformly mixed, even with the use of mechanical force. Even if such a mixture in which the components are not uniformly mixed is filled into the container in Step P2, a uniformly mixed curable silicone composition may not be obtained, and problems such as poor curing or poor melting may occur during use. On the other hand, when the temperature of the heated mixture exceeds the upper limit, undesirable side reactions such as the photoactive hydrosilylation catalyst or thermoplastic resin microparticles containing a platinum-based catalyst as component (D) may occur during mixing, causing the entire mixture to significantly thicken or solidify, lose its heat-melting properties, or form a cured product. This is not preferred. Furthermore, in order to suppress undesirable side reactions, methods such as adding component (D) after the mixture of the other components has been thoroughly mixed instead of mixing them from the beginning in step P1, or lowering the heating temperature within a kneadable range when adding component (D) can be used, and preferably are employed.

[0145] As described above, the kneading apparatus used in step P1 is not limited and can be selected based on the operating efficiency in terms of processing time and the ability to control shear heat generation. From the perspective of short processing time and high operating efficiency, a continuous heating kneading apparatus such as a single-screw extruder or a twin-screw extruder equipped with heating and cooling functions is particularly preferably used.

[0146] [Process P2]

[0147] Step P2 is the process of filling the dispensing container with the heated and molten mixture obtained in Step P1. Using a continuous kneading apparatus in Step P1 allows for continuous filling, thus achieving excellent production efficiency. In this case, a nozzle matching the inner diameter of the cartridge to be filled is installed at the outlet of the continuous kneading apparatus and then attached to the cartridge. This allows the cartridge to be automatically filled by the pressure of the uniformly mixed composition ejected from the nozzle. When the cartridge is completely filled, the nozzle is removed and subsequently attached to the next cartridge, allowing the filling process to be performed continuously, matching the ejection speed of the composition.

[0148] Step P2 can be performed manually or automatically. In the continuous method described above, the filling rate of the mixture obtained in step P1 in step P2 can be designed according to the production scale. As an example, the mixture obtained in step P1 can be continuously filled into the box at a supply rate of 1 to 10 kg / hour, but it goes without saying that the filling conditions are not limited to this. Alternatively, filling can be performed by directly charging the composition continuously discharged from the kneading machine into a barrel or drum.

[0149] [Dispensing box and its use]

[0150] The curable silicone composition of the present invention can be filled into a dispensing box in the above-mentioned step P2, etc., and is preferably used in hot dispensing. The box for dispensing used in step P2 can be and is preferably heat-resistant. The filling and dispensing steps are carried out at around 100°C, so a plastic box with heat resistance of around 120°C can be used. In addition, a metal box, such as an aluminum box, can also be used. On the other hand, when a box that is not heat-resistant is used, there is a possibility that the box will deform when used at a high temperature of more than 100°C during filling or during the hot dispensing described below. Similarly, it is also preferable to use a metal barrel and barrel for the barrel and barrel, and it is preferable to select a barrel and barrel of a type that can be used in the hot melt machine described later.

[0151] Dispensing cartridges filled with a curable silicone composition can be used with a commonly available dispenser equipped with a heating unit (temperature control unit). As described above, the curable silicone composition of the present invention is fusible at 50°C. Therefore, by heating the cartridge to a temperature of 50°C or higher, preferably 50-150°C, and preferably 80-120°C, using a temperature control unit, it can be smoothly dispensed at a discharge pressure of, for example, approximately 0.5 MPa, allowing for hot dispensing. On the other hand, in the case of barrels and cartridges, for example, a Nordson hot melt machine can be used to extrude the composition at high temperatures and dispense it from a heat-resistant hose.

[0152] [Other Forms of Composition and Modifications of Production Method]

[0153] The curable silicone composition of the present invention is preferably in the form of a dispenser filled in a box, bucket, or canister, but may also be in the form of a flat plate, granular, sheet, or film-shaped article, as needed. These articles, particularly sheets and films composed of the curable silicone composition, can be used in a manner such that at least one surface of an uncured sheet or film of the curable silicone composition is brought into close contact with a portion or all of a substrate serving as an electronic component or its precursor using one or more mechanisms selected from a vacuum laminator, a vacuum press, and compression molding, and then cured by irradiation with high-energy radiation.

[0154] In addition, the curable silicone composition involved in the present invention can be manufactured using organic polysiloxane resin microparticles as component (A) as raw materials in the above-mentioned step P1, etc. (Method A), or it can be manufactured by dispersing an organic polysiloxane resin that is solid at room temperature and any chain polydiorganosiloxane in an organic solvent and using the hot-melt solid component after removing the organic solvent as the raw material (hot-melt bulk method) (Method B).

[0155] Specifically, the former (method A) is a production method comprising the following steps:

[0156] Step PA1: a step of mixing organopolysiloxane resin fine particles and other raw materials (which may include a functional filler as appropriate, by arbitrary selection);

[0157] Step PA2: A step of kneading the mixture obtained in step PA1 while heating and melting it at a temperature of 120° C. or lower.

[0158] Likewise, the latter (method B) is a production method comprising the following steps:

[0159] Step PB1: A step of removing the organic solvent from a solution in which an organopolysiloxane resin (A) that is solid at room temperature and a chain-like organopolysiloxane (B) are dispersed or dissolved in an organic solvent at a temperature of 150° C. or higher to obtain a heat-melting solid component.

[0160] Step PB2: A step of adding a curing agent (C+D) component to the hot-melt solid component obtained in step PB1, and then kneading the mixture while heating and melting it at a temperature of 120° C. or lower.

[0161] The curable silicone composition obtained in the above step can be formed into a sheet or flat plate shape by, for example, ejecting it between releasable films, or can be filled into a dispensing container by ejecting the heated and melted mixture obtained in step PA2 or step PB2 from a nozzle and continuously filling it into the above container (step P2).

[0162] [Curing of Curable Silicone Composition and Production of Laminated Body]

[0163] In the curable silicone composition of the present invention, when a photoactive hydrosilylation reaction catalyst is used as component (D), it can be thermally cured by irradiation with high-energy rays as a trigger. However, several curing methods can be listed by combining the dispensing step and the high-energy ray irradiation step. In the dispensing step, the composition is heated to about 50 to 150°C, but by spraying the composition or irradiating high-energy rays immediately after applying it to the substrate, the composition can be thermally cured before cooling, and a certain degree of thermal curing can be performed before naturally cooling on the substrate. The curing speed of the composition can be precisely controlled by the amount of added catalyst and curing retardant and the irradiation amount of high-energy rays. This is preferably used when it is desired to cure the composition directly in the shape after spraying, and specifically, it can be applied to the sealing or sealing of the substrate. After the composition is sprayed and comes into close contact with the substrate, it is immediately cured to a certain extent, thereby achieving so-called instant curing and shape fixing of the material. If necessary, the obtained laminate can be post-cured by exposing it to a temperature of 10°C or above to form a completely cured product.

[0164] On the other hand, it is also possible to, after the composition of the present invention is ejected onto a substrate by a dispenser, irradiate high-energy rays after a period of time. In this case, the composition of the present invention has shape retentivity at 25 ° C, so that the material ejected does not drip or the like and changes in shape. In addition, by making the second substrate close contact with the substrate carrying the composition ejected (preferably pressing, that is, applying external force and close contact), the shape of the composition changes, and an adhesive layer joining two substrates can be formed. In the case where both substrates are opaque materials, it is necessary to irradiate high-energy rays before being crimped with the second substrate. On the other hand, in the case where any one of the two substrates is a light-transmitting substrate such as glass, it is also possible to irradiate high-energy rays after the two substrates are bonded.

[0165] When producing a laminate having a structure in which a part or all of at least two substrate surfaces are joined via a cured product composed of the composition of the present invention by these methods, a production method having the following steps is particularly preferred:

[0166] Step (I): heating the curable silicone composition of the present invention to 50° C. or higher using a dispenser equipped with a heating unit to impart fluidity, and then dispensing the composition onto a portion or the entire surface of at least one substrate;

[0167] Step (II): Simultaneously with step (I) or after step (I), a step of irradiating the curable silicone composition ejected from the dispenser directly or through another substrate with high energy rays; and

[0168] Step (III): After step (I) and before or after step (II), a step of bringing another substrate into close contact with the curable silicone composition ejected from the dispenser

[0169] . Here, in step (I), by connecting a heatable slit die to the outlet of the dispenser, it is possible to eject in the shape of a film or sheet of desired thickness, or by directly coating it into a substrate, thereby enabling precise coating. It should be noted that the curable silicone composition of the present invention after irradiation with high-energy rays forms a cured product by causing the curing reaction to proceed over time at room temperature or by heating. Therefore, the composition can be left at room temperature (around 25°C) or exposed to heat at a temperature of 10°C or above, preferably 50°C or above, and more preferably 100°C or above to cure.

[0170] The substrate used in the above-mentioned method of use and laminate is a component of an electronic component, a semiconductor device, or an optical semiconductor device. The substrate having a cured product composed of the curable silicone composition involved in the present invention (including a laminate having a structure in which at least two substrate surfaces are joined via the cured product) is useful as an electronic component, a semiconductor device, an optical semiconductor device, or a component thereof.

[0171] When the curable silicone composition of the present invention uses a photoactive hydrosilylation reaction catalyst (D1) as component (D), the catalyst is activated by irradiation with high-energy radiation such as ultraviolet rays, and a hydrosilylation reaction in the composition proceeds, thereby forming a cured product. The types of high-energy radiation are as described above. The irradiation dose varies depending on the type of high-energy radiation-activated catalyst. In the case of ultraviolet radiation, the cumulative irradiation dose at 365 nm is preferably 100 mJ / cm 2 ~100J / cm 2 In the range of 500mJ / cm 2 ~50J / cm 2 In the range of 500mJ / cm 2 ~20J / cm 2 In other words, the curable silicone composition of the present invention can initiate a curing reaction by irradiation with high-energy rays such as ultraviolet rays. Furthermore, the curing reaction rate can be controlled to some extent by varying the cumulative irradiation dose. It should be noted that once the hydrosilylation catalyst as component (D1) is activated, the curing reaction proceeds over time at room temperature or by heating, even after irradiation with high-energy rays is stopped, thereby forming a cured product.

[0172] The curing reaction can be cured in a low temperature region (15 to 100°C) including room temperature (25°C). It should be noted that, in an embodiment of the present invention, "low temperature" refers to, for example, 100°C or less, specifically, a temperature range of 15°C to 100°C, and a temperature of 80°C or less can also be selected. When the reaction of the composition of the present invention (including a semi-cured product) is carried out in a temperature range of 15 to 100°C, it is preferred that the composition be placed near room temperature (a temperature range that can be reached without heating or cooling, particularly including a temperature region of 20 to 25°C), or cooled to below room temperature and above 15°C, or heated to above room temperature and below 100°C. It should be noted that the time required for the curing reaction can be appropriately designed according to the irradiation amount and temperature of high-energy rays such as ultraviolet rays. In addition, depending on the allowability and needs in the process, heating exceeding 100°C can be temporarily performed.

[0173] When (D2) thermoplastic resin fine particles containing a platinum-based catalyst are used as the component (D) of the curable silicone composition of the present invention, the process is as described above, except that the catalyst is activated and the hydrosilylation reaction is initiated by exposure to a temperature above the melting point or glass transition point of the thermoplastic resin, for example, 130° C. or higher, instead of irradiation with high-energy rays.

[0174] When using component (D2), a molding process is listed as a characteristic method of use other than those mentioned in the method of using the photoactive catalyst-containing composition of component (D1). Molding liquid thermosetting compositions by transfer molding or compression molding is well known, but the heat dispensing composition of the present invention can be used in these molding processes as long as it has a heating unit. In these molding processes, since the liquid composition is directly dispensed into the molding machine, it is not suitable for using compositions that do not cure without high-energy radiation. However, the curable silicone composition containing component (D2) has the advantage of being preferably used in these molding processes because the hydrosilylation reaction catalyst is activated by exposure to high temperatures.

[0175] It should be noted that, in the component (D2), due to its nature, the curing reaction based on high temperature exposure and the adhesion to the adherend proceed simultaneously. Therefore, when producing a laminate having a structure in which a portion or all of the surfaces of at least two substrates are joined via a cured product composed of the composition of the present invention, when the component (D) of the curable silicone composition is (D2) thermoplastic resin fine particles containing a platinum-based catalyst, a production method comprising the following steps (I) to (III) is preferred.

[0176] Step (I): heating the curable silicone composition to 50° C. or higher using a dispenser equipped with a heating unit to impart fluidity, and then spraying the composition onto a portion or the entire surface of at least one substrate;

[0177] If necessary, step (II): after step (I), a step of bringing the curable silicone composition discharged from the dispenser into close contact with another substrate; and

[0178] Step (III): a step of heating the obtained integrated product of the substrate and the curable silicone composition to a temperature of 130° C. or higher.

[0179] [Usage form suitable for the hardness of the cured product]

[0180] The preferred hardness of the cured product obtained by curing the curable silicone composition of the present invention is divided into two categories depending on the application. When the curable silicone composition of the present invention is bonded to an adherend on both sides (i.e., used as an adhesive), the Type A durometer hardness specified in JIS K 7215-1986 "Durometer Hardness Test Methods for Plastics" is preferably 30 or higher. 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 application is to seal or seal a substrate (i.e., used as a sealant), the Type A durometer hardness is preferably 40 or higher. This is because if the hardness is below the lower limit, the surface of the cured product will stick, and workability will be reduced.

[0181] [Application of Composition / Cured Product]

[0182] In the above-mentioned curable silicone composition, the cured product has low viscosity and little surface adhesion. It is sprayed onto the surface of the substrate at a temperature of 50°C or above through a heat dispenser and cured by the above-mentioned method, so that it can be used as a sealant or sealant. In addition, before the sprayed composition cools, it is brought into close contact with other substrates (preferably by applying external force to press the substrate against the composition layer, thereby deforming the composition layer and making it close), and cured by the above-mentioned method, so that it can also be used as a bonding layer / adhesive layer between different substrates (components). That is, the curable silicone composition involved in the present invention is preferably used as a hot melt adhesive or hot melt sealant having the property of curing by irradiation with high-energy rays or temperature as a trigger. In particular, the uncured / semi-cured composition layer composed of the curable silicone composition involved in the present invention or the cured product obtained by curing it is useful as a component of an electronic component, a semiconductor device or an optical semiconductor device.

[0183] Specifically, since the curable silicone composition of the present invention has the above-mentioned hot melt properties, it has excellent workability and curing properties when melted (hot melt), and the cured product obtained by curing the present composition has excellent coloring resistance at high temperatures. Therefore, it is useful for semiconductor components such as sealing materials for light-emitting / optical devices, light-reflecting materials, and optical semiconductors having the cured product. Furthermore, the cured product has excellent mechanical properties, low viscosity and is relatively hard, so it is preferably used as a sealant for semiconductors; a sealant for power semiconductors such as SiC and GaN; an adhesive, potting agent, protective agent, coating agent, and sealing agent for electrical and electronic use. It is particularly preferably used as a sealant that needs to maintain the shape after distribution or a sealant for semiconductors that requires a thick layer. The present composition (uncured or semi-cured composition layer) is brought into close contact with the substrate, preferably a film-like substance that is flattened by external force between the two substrates. It can be used as an adhesive layer or a stress buffer layer between two substrates with different linear expansion coefficients. The curable silicone composition of the present invention may be a sealant for single-sided sealing or a sealant for double-sided sealing accompanied by bonding between two substrates, and has preferred properties suitable for these applications.

[0184] It should be noted that the curable silicone composition of the present invention can flexibly cope with desired applications and curing processes by selecting and optimizing component (D), and can therefore be applied to electronic components, semiconductor devices, optical semiconductor device members, or precursors thereof in accordance with a wide range of functional and process requirements.

[0185] The use of the cured product obtained by curing the curable silicone composition of the present invention is not particularly limited, but it can be preferably used as a member for electronic components, semiconductor devices, or optical semiconductor devices. It can be preferably used as a sealing material for semiconductor elements or IC chips, etc., and as an adhesive, bonding member, or sealing agent for semiconductor devices. It is particularly suitable for applications requiring high heat resistance or light resistance.

[0186] Semiconductor devices comprising a component composed of a cured product obtained by curing the curable silicone composition of the present invention are not particularly limited, but are preferably used, for example, as light-emitting semiconductor devices serving as light-emitting / optical devices, optical components for displays, components for solar panels, and particularly as sealing materials, housing materials, or adhesive components used in these devices. Furthermore, the cured product of the present invention exhibits excellent resistance to discoloration at high temperatures and can therefore be more preferably used as a sealing material, housing material, or adhesive component for electronic materials where transparency and light and heat resistance are important.

[0187] As described above, the curable silicone composition of the present invention can be in the form of a flat plate, pellet, sheet, or film-shaped molded product, and can be configured as a member for an electronic component, semiconductor device, or optical semiconductor device in a form other than thermal distribution and used by curing or molding.

[0188] Example

[0189] The curable silicone composition of the present invention and its production method are described in detail below using examples and comparative examples. It should be noted that in the following description, Me, Vi, and Ph in the average unit formula represent methyl, vinyl, and phenyl groups, respectively. Furthermore, the melt viscosity, dispensing properties, stability of the composition during dispensing, and hardness of the cured product of the curable silicone composition of each example and comparative example were measured using the following methods. The results are shown in Table 2.

[0190] [Melt viscosity at 100°C]

[0191] The melt viscosity of the curable silicone composition at 100° C. was measured using a high-pressure flow tester CFT-500EX (manufactured by Shimadzu Corporation) at a pressure of 2.5 MPa using a nozzle having an outlet nozzle diameter of 1.0 mm.

[0192] [Heat distribution (initial)]

[0193] A cartridge filled with a curable silicone composition was placed in a temperature control unit (THERMOMASTER TCU-02, manufactured by Musashi High-Tech Corporation) attached to a desktop coating robot (SHOTmini200Sx, manufactured by Musashi High-Tech Corporation). The temperature of the temperature control unit was set to 100°C to heat the cartridge. After the cartridge was fully heated, a test was conducted in which the composition was dispensed onto a glass plate at a pressure of 0.5 MPa using a digital dispenser (ML-606GX, manufactured by Musashi High-Tech Corporation). Successful dispensing was evaluated.

[0194] [Hot dispensing properties (after 100°C for 5 hours) / stability of the composition during dispensing]

[0195] A cartridge filled with a curable silicone composition was placed in a temperature control unit (THERMOMASTER TCU-02, manufactured by Musashi High-Tech Corporation) attached to a desktop coating robot (SHOTmini200Sx, manufactured by Musashi High-Tech Corporation). The temperature of the temperature control unit was set to 100°C and the cartridge was left as is for 5 hours. The cartridge was then tested by dispensing the composition onto a glass plate at a pressure of 0.5 MPa using a digital dispenser (ML-606GX, manufactured by Musashi High-Tech Corporation) to determine whether successful dispensing was successful.

[0196] [Hardness of cured product]

[0197] The curable silicone composition is cured under predetermined curing conditions to form a cured product. The hardness of the cured product can be measured using a type A durometer specified in JIS K 7215-1986 "Durometer hardness test methods for plastics."

[0198] [Reference Examples 1 to 7: Preparation of Hot-melt Silicone Mixture]

[0199] In each Reference Example, the organopolysiloxane resins (a1), (a2), and (a') shown below and the linear organopolysiloxanes (b) and (b') {hereinafter referred to as components (a1), (a2), (a'), (b), and (b')} were mixed to prepare a hot-melt silicone mixture (hereinafter referred to as mixtures 1 to 7). It should be noted that the low-molecular-weight organopolysiloxane components removed by the methods described in the Reference Examples include M4Q structures and the like.

[0200] ·Ingredients (a1):

[0201] It is a white solid at 25°C, with the average unit formula:

[0202] (Me2ViSiO 1 / 2 ) 0.05 (Me3SiO 1 / 2 ) 0.39 (SiO 4 / 2 ) 0.56 (HO 1 / 2 ) 0.02

[0203] The organopolysiloxane resin shown (vinyl content = 1.9 mass%)

[0204] Component (a2):

[0205] It is a white solid at 25°C, with the average unit formula:

[0206] (Me3SiO 1 / 2 ) 0.44 (SiO 4 / 2 ) 0.56 (HO 1 / 2 ) 0.02

[0207] The organopolysiloxane resin shown (vinyl content = 0 mass %)

[0208] ·Ingredients (a'):

[0209] It is a white solid at 25°C, with the average unit formula:

[0210] (Me3SiO 1 / 2 ) 0.44 (SiO 4 / 2 ) 0.56 (HO 1 / 2 ) 0.02

[0211] The organopolysiloxane resin shown

[0212] Component (b):

[0213] Formula: ViMe2SiO(Me2SiO) 800 SiViMe2

[0214] The molecular chain ends of the polydimethylsiloxane shown are terminated with dimethylvinylsiloxy groups (vinyl content = 0.09 mass%)

[0215] Component (b'):

[0216] From the formula (OMe)3SiO(Me2SiO) 800 Si(OMe)3

[0217] The molecular chain ends of the polydimethylsiloxane are terminated with trialkoxysiloxy groups

[0218] In each reference example, components (a1), (a2), (a'), (b), and (b') in the amounts (kg) shown in Table 1 below were dissolved in 4.00 kg of xylene in a drum using a Sany motor. The resulting solution was fed into a twin-screw extruder set to a maximum temperature of 230°C. The xylene and low-molecular-weight organopolysiloxane components were removed under a vacuum of -0.08 MPa, resulting in hot-melt, transparent mixtures 1-7. Mixtures 1-7 were placed in a cylindrical drum and directly cooled to solidify. The volatile content of each mixture was measured at 200°C for 1 hour, and the results are shown in Table 1 as "Volatile Content (mass %)."

[0219] [Table 1]

[0220]

[0221] [Examples 1 to 4, Comparative Examples 1 to 4]

[0222] In the following examples and comparative examples, in addition to the above mixtures 1 to 7 and component (b), the following compounds were used. Figure 1 Table 2 shows the properties of the curable silicone compositions obtained.

[0223] Component (c1):

[0224] From the formula: (PhSiO 3 / 2 ) 0.4 (HMe2SiO 1 / 2 ) 0.6 The organohydrogenpolysiloxane shown (the volatile content, i.e., the mass reduction rate, was 3.4% by mass when aged in an oven at 100° C. under atmospheric pressure for 1 hour)

[0225] Component (c2):

[0226] By formula: (HMe2SiO 1 / 2 ) 0.52 (Me2SiO 2 / 2 ) 0.15 (SiO 4 / 2 ) 0.33 The organohydrogenpolysiloxane shown (the volatile content, i.e., the mass reduction rate, was 2.9 mass % when aged in an oven at 100° C. under atmospheric pressure for 1 hour)

[0227] Component (c'):

[0228] Me3SiO(Me2SiO) 37 (MeHSiO) 37 SiMe3

[0229] The organohydrogenpolysiloxane shown (the volatile content, i.e., the mass reduction rate, was 2.6% by mass when aged in an oven at 100° C. under atmospheric pressure for 1 hour)

[0230] Component (c"):

[0231] Formula: Me3SiO(Me2SiO) 29 [Me(HSC3H6)SiO]3SiMe3

[0232] The organopolysiloxane containing 3-mercaptopropyl group shown

[0233] ·Ingredients (d1):

[0234] (Methylcyclopentadienyl)trimethylplatinum(IV) complex

[0235] Component (d2): Polycarbonate resin particles containing a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum at a platinum content of 4000 ppm

[0236] Component (d"):

[0237] Platinum 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in 1,3-divinyltetramethyldisiloxane solution

[0238] Ingredient (e):

[0239] Methyltris-1,1-dimethyl-2-propynyloxysilane (boiling point = 245°C (1013.25hPa))

[0240] ·Ingredients (f):

[0241] Carbon black (trade name: DENKABLACK 100% press, manufactured by DENKA Corporation)

[0242] ·Ingredients (f'):

[0243] Titanium oxide (SX-3103, manufactured by Sakai Chemical Industry Co., Ltd.)

[0244] [Example 1]

[0245] Through the hot melt machine for cylindrical barrels and cans (VersaPail hot melt machine manufactured by Nordson, Figure 1 The mixture 1 was fed to a twin-screw extruder ( Figure 1 2).

[0246] Next, a mixture consisting of 0.31 kg / hr of component (c1) and 500 ppm of component (e) relative to the entire composition was added. Figure 1 The pump 3-a is shown as supplying the liquid. The set temperature of the injection part is 150°C.

[0247] Next, a mixture consisting of 0.15 kg / hr of component (b) and component (d1) (in an amount of 10 ppm by mass as platinum metal relative to the entire composition) was added from Figure 1 The mixture was supplied by pump 3-b (the setting temperature of the input part was 80°C), and the vacuum degree in the extruder was -0.08 MPa, and degassing and melt kneading were carried out.

[0248] The outlet temperature of the twin-screw extruder was set at 80°C, at which the mixture was in a semi-solid, softened state. A nozzle with a diameter of 2.5 cm and a length of 13 cm was installed at the outlet of the twin-screw extruder, and the resulting mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, manufactured by Nordson Corporation).

[0249] [Example 2]

[0250] Through the hot melt machine for cylindrical barrels and cans (VersaPail hot melt machine manufactured by Nordson, Figure 1 The mixture 2 was fed to a twin-screw extruder ( Figure 1 2).

[0251] Next, a mixture consisting of 0.33 kg / hr of component (c2) and 500 ppm of component (e) relative to the entire composition was added. Figure 1 The pump 3-a is shown as supplying the liquid. The set temperature of the injection part is 150°C.

[0252] Next, a mixture consisting of 0.15 kg / hr of component (b) and component (d1) (in an amount of 10 ppm by mass as platinum metal relative to the entire composition) was added from Figure 1 The mixture was supplied by pump 3-b (the setting temperature of the input part was 80°C), and the vacuum degree in the extruder was -0.08 MPa, and degassing and melt kneading were carried out.

[0253] The outlet temperature of the twin-screw extruder was set at 80°C, at which the mixture was in a semi-solid, softened state. A nozzle with a diameter of 2.5 cm and a length of 13 cm was installed at the outlet of the twin-screw extruder, and the resulting mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, manufactured by Nordson Corporation).

[0254] [Example 3]

[0255] Through the hot melt machine for cylindrical barrels and cans (VersaPail hot melt machine manufactured by Nordson, Figure 1 The mixture 3 was fed to a twin-screw extruder ( Figure 1 2).

[0256] Next, a mixture consisting of 0.34 kg / hr of component (c1) and 500 ppm of component (e) relative to the entire composition was added. Figure 1 The pump 3-a is shown as supplying the liquid. The set temperature of the injection part is 150°C.

[0257] Next, a mixture consisting of 0.15 kg / hr of component (b) and component (d1) (in an amount of 10 ppm by mass as platinum metal relative to the entire composition) was added from Figure 1 The mixture was supplied by pump 3-b (the setting temperature of the input part was 80°C), and the vacuum degree in the extruder was -0.08 MPa, and degassing and melt kneading were carried out.

[0258] The outlet temperature of the twin-screw extruder was set at 80°C, at which the mixture was in a semi-solid, softened state. A nozzle with a diameter of 2.5 cm and a length of 13 cm was installed at the outlet of the twin-screw extruder, and the resulting mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, manufactured by Nordson Corporation).

[0259] [Example 4]

[0260] Through the hot melt machine for cylindrical barrels and cans (VersaPail hot melt machine manufactured by Nordson, Figure 1 The mixture 4 was fed to a twin-screw extruder ( Figure 1 2).

[0261] Next, a mixture consisting of 0.440 kg / hr of component (c2) and 500 ppm of component (e) relative to the entire composition was added. Figure 1 The pump 3-a is shown as supplying the liquid. The set temperature of the injection part is 150°C.

[0262] Next, a mixture consisting of 0.15 kg / hr of component (b) and component (d1) (in an amount of 10 ppm by mass as platinum metal relative to the entire composition) was added from Figure 1 The mixture was supplied by pump 3-b (the setting temperature of the input part was 80°C), and the vacuum degree in the extruder was -0.08 MPa, and degassing and melt kneading were carried out.

[0263] The outlet temperature of the twin-screw extruder was set at 80°C, at which the mixture was in a semi-solid, softened state. A nozzle with a diameter of 2.5 cm and a length of 13 cm was installed at the outlet of the twin-screw extruder, and the resulting mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, manufactured by Nordson Corporation).

[0264] [Example 5]

[0265] Through the hot melt machine for cylindrical barrels and cans (VersaPail hot melt machine manufactured by Nordson, Figure 1 The mixture 3 was fed to a twin-screw extruder ( Figure 1 2).

[0266] Next, a mixture consisting of 0.34 kg / hr of component (c1), 500 ppm of component (e) relative to the total amount of the present composition, and 0.1 kg / hr of component (f) was added from Figure 1 The pump 3-a is shown as supplying the liquid. The set temperature of the injection part is 150°C.

[0267] Next, a mixture consisting of 0.15 kg / hr of component (b), component (d2) (in an amount of 10 ppm by mass as platinum metal relative to the entire composition), and 0.1 kg / hr of component (f) was added from Figure 1 The mixture was supplied by pump 3-b (the setting temperature of the input part was 80°C), and the vacuum degree in the extruder was -0.08 MPa, and degassing and melt kneading were carried out.

[0268] The outlet temperature of the twin-screw extruder was set at 80°C, at which the mixture was in a semi-solid, softened state. A nozzle with a diameter of 2.5 cm and a length of 13 cm was installed at the outlet of the twin-screw extruder, and the resulting mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, manufactured by Nordson Corporation).

[0269] [Example 6]

[0270] Through the hot melt machine for cylindrical barrels and cans (VersaPail hot melt machine manufactured by Nordson, Figure 1 The mixture 4 was fed to a twin-screw extruder ( Figure 1 2).

[0271] Next, a mixture consisting of 0.085 kg / hr of component (b), 0.396 kg / hr of component (c2), 500 ppm of component (e) relative to the total amount of the present composition, and 1.0 kg / hr of component (f') was added. Figure 1 The pump 3-a is shown as supplying the liquid. The set temperature of the injection part is 150°C.

[0272] Next, a mixture consisting of 0.05 kg / hr of component (b) and component (d2) (in an amount of 10 ppm by mass as platinum metal relative to the entire composition) was added. Figure 1 The mixture was supplied by pump 3-b (the setting temperature of the input part was 80°C), and the vacuum degree in the extruder was -0.08 MPa, and degassing and melt kneading were carried out.

[0273] The outlet temperature of the twin-screw extruder was set at 80°C, at which the mixture was in a semi-solid, softened state. A nozzle with a diameter of 2.5 cm and a length of 13 cm was installed at the outlet of the twin-screw extruder, and the resulting mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, manufactured by Nordson Corporation).

[0274] [Comparative Example 1]

[0275] Through the hot melt machine for cylindrical barrels and cans (VersaPail hot melt machine manufactured by Nordson, Figure 1The mixture 5 was fed to a twin-screw extruder ( Figure 1 2).

[0276] Next, a mixture consisting of 0.450 kg / hr of component (c') and 500 ppm of component (e) relative to the entire composition was added. Figure 1 The pump 3-a is shown as supplying the liquid. The set temperature of the injection part is 150°C.

[0277] Next, a mixture consisting of 0.15 kg / hr of component (b) and component (d) (in an amount of 10 ppm by mass as platinum metal relative to the entire composition) was added from Figure 1 The mixture was supplied by pump 3-b (the setting temperature of the input part was 80°C), and the vacuum degree in the extruder was -0.08 MPa, and degassing and melt kneading were carried out.

[0278] The outlet temperature of the twin-screw extruder was set at 80°C, at which the mixture was in a semi-solid, softened state. A nozzle with a diameter of 2.5 cm and a length of 13 cm was installed at the outlet of the twin-screw extruder, and the resulting mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, manufactured by Nordson Corporation).

[0279] [Comparative Example 2]

[0280] Through the hot melt machine for cylindrical barrels and cans (VersaPail hot melt machine manufactured by Nordson, Figure 1 The mixture 1 was fed to a twin-screw extruder ( Figure 1 2).

[0281] Next, a mixture consisting of 0.310 kg / hr of component (c1) and 3500 ppm of component (e) relative to the entire composition was added. Figure 1 The pump 3-a is shown as supplying the liquid. The set temperature of the injection part is 150°C.

[0282] Next, a mixture consisting of 0.15 kg / hr of component (b) and component (d") (4 ppm by mass as platinum metal relative to the entire composition) was added. Figure 1 The mixture was supplied by pump 3-b (the setting temperature of the input part was 80°C), and the vacuum degree in the extruder was -0.08 MPa, and degassing and melt kneading were carried out.

[0283] The outlet temperature of the twin-screw extruder was set at 80°C, at which the mixture was in a semi-solid, softened state. A nozzle with a diameter of 2.5 cm and a length of 13 cm was installed at the outlet of the twin-screw extruder, and the resulting mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, manufactured by Nordson Corporation).

[0284] [Comparative Example 3]

[0285] Through the hot melt machine for cylindrical barrels and cans (VersaPail hot melt machine manufactured by Nordson, Figure 1 The mixture 6 was fed to a twin-screw extruder ( Figure 1 2).

[0286] Next, a mixture consisting of component (c') 0.150 kg / hr and 2-hydroxy-2-methylpropiophenone (1000 ppm by mass relative to the entire composition) was added. Figure 1 The pump 3-a is shown as supplying the liquid. The set temperature of the injection part is 150°C.

[0287] Next, a mixture consisting of 0.15 kg / hr of component (b) and 2,6-di-tert-butyl-4-methylphenol (100 ppm by mass relative to the entire composition) was added. Figure 1 The mixture was supplied by pump 3-b (the setting temperature of the input part was 80°C), and the vacuum degree in the extruder was -0.08 MPa, and degassing and melt kneading were carried out.

[0288] The outlet temperature of the twin-screw extruder was set at 80°C, at which the mixture was in a semi-solid, softened state. A nozzle with a diameter of 2.5 cm and a length of 13 cm was installed at the outlet of the twin-screw extruder, and the resulting mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, manufactured by Nordson Corporation).

[0289] [Comparative Example 4]

[0290] Through the hot melt machine for cylindrical barrels and cans (VersaPail hot melt machine manufactured by Nordson, Figure 1 The mixture 7 was fed to a twin-screw extruder ( Figure 1 2).

[0291] Next, the

[0292] (OMe)3SiO(Me2SiO) 800 Si(OMe)3

[0293] A mixture consisting of 0.15 kg / hr of polydimethylsiloxane having trimethoxysiloxy groups capped at both ends of the molecular chain, 0.110 kg / hr of isobutyltrimethoxysilane, and tetra-tertiary butyl titanium (800 ppm by mass as titanium metal relative to the entire composition) was added. Figure 1 The mixture was supplied by pump 3-b (the setting temperature of the input part was 80°C), and the vacuum degree in the extruder was -0.08 MPa, and degassing and melt kneading were carried out.

[0294] The outlet temperature of the twin-screw extruder was set at 80°C, at which the mixture was in a semi-solid, softened state. A nozzle with a diameter of 2.5 cm and a length of 13 cm was installed at the outlet of the twin-screw extruder, and the resulting mixture was continuously filled into a 30 ml heat-resistant cartridge (Unity HiTemp syringe, manufactured by Nordson Corporation).

[0295] [Table 2]

[0296]

[0297] (*) When the irradiation dose is 10 J / cm 2 The ultraviolet light with a wavelength of 365nm is irradiated in a manner.

[0298] [Summarize]

[0299] The curable silicone compositions of Examples 1-6 of the present invention utilize specific solid organopolysiloxane resins and chain organopolysiloxanes, employ a photoactive hydrosilylation reaction catalyst (Examples 1-4) or polycarbonate resin microparticles containing a hydrosilylation catalyst (Examples 5 and 6), and control their melt viscosity characteristics to achieve excellent thermal dispensability. While maintaining storage stability during dispensing, they also achieve excellent curability triggered by ultraviolet irradiation or high-temperature exposure. Furthermore, the resulting cured silicone material exhibits low surface tack and a relatively hard surface, making it expected to be particularly useful for applications such as protecting semiconductor devices.

[0300] Meanwhile, Comparative Example 1 is a curable silicone composition using a photoactive hydrosilylation catalyst, but its melt viscosity is too high, making it impossible to dispense at temperatures around 100°C. The curable silicone composition of Comparative Example 2 achieves excellent dispensing properties, but because it uses a conventional hydrosilylation catalyst, it is found to be extremely difficult to ensure storage stability during dispensing. Meanwhile, although the curable silicone compositions use a different curing system than the examples of Comparative Examples 3 and 4, it is found that the UV-curable Comparative Example 3 has difficulty forming a hard cured product, and the room-temperature moisture-curable Comparative Example 4 requires a long time to cure.

[0301] [Reference Examples 1 to 4]

[0302] The curable silicone compositions of Examples 5 and 6 contain (f) carbon black as a black pigment and (f') titanium oxide as a white pigment, respectively, to provide black and white cured products. They also contain a catalyst (d2) that has the property of being activated by high-temperature exposure as a hydrosilylation reaction catalyst, and can therefore be used in the following dispensing method and molding method.

[0303] [Reference Example 1 (Heat Distribution Method)]

[0304] The cartridge filled with the curable silicone composition obtained in Example 6 was placed in a temperature control unit (THERMO MASTER TCU-02, manufactured by Musashi High-Tech Corporation) mounted on a desktop coating robot (SHOTmini200Sx, manufactured by Musashi High-Tech Corporation). The temperature of the temperature control unit was set to 100°C, and the cartridge was heated. After the cartridge was fully heated, it was dispensed onto a glass plate using a digital dispenser (ML-606GX, manufactured by Musashi High-Tech Corporation) at a pressure of 0.5 MPa. The composition retained its shape as dispensed and did not drip. The resulting laminate was then exposed to 160°C for one hour to obtain a cured product. The resulting cured product adhered firmly to the glass substrate.

[0305] [Reference Example 2 (Heat Distribution Method)]

[0306] As in Reference Example 1, a curable silicone composition (Example 6) dispensed from a digital dispenser onto a glass plate was laminated to a second glass plate from above and manually spread. The resulting laminate was then exposed to 160°C for 1 hour to obtain a cured product. The resulting cured product firmly adhered to both glass substrates.

[0307] [Reference Example 3 (Transfer Molding Method)]

[0308] The box filled with the curable silicone composition obtained in Example 5 was placed in a temperature control unit (THERMO MASTER TCU-02, manufactured by Musashi High-Tech Corporation) attached to a desktop coating robot (SHOTmini200Sx, manufactured by Musashi High-Tech Corporation). The temperature of the temperature control unit was set to 100°C, and the box was heated. After the box was fully heated, the composition was applied to a transfer molding machine using a digital dispenser (ML-606GX, manufactured by Musashi High-Tech Corporation) at a pressure of 0.5 MPa. While a tetrafluoroethylene resin release film was interposed between the transfer molding machine and the mold, the composition was molded at 160°C for 10 minutes onto a 10 cm x 10 cm aluminum substrate. A beautiful molded article was obtained.

[0309] [Reference Example 4 (Compression Molding Method)]

[0310] As in Reference Example 3, the composition was applied from a digital dispenser into a compression molding machine, and while a release film made of tetrafluoroethylene resin was engaged between it and the mold, a 10 cm × 10 cm aluminum substrate was molded at a temperature of 160°C for 10 minutes, resulting in a beautiful molded body.

[0311] [Reference Example 5 (Heat Distribution + Slit Die Method)]

[0312] A slot die with a heatable outlet gap of 100 μm was installed on the top of the digital dispenser of Reference Example 1. The temperature of the die was set to 100°C, and the curable silicone composition obtained in Preparation Example 1 was sprayed and applied to a glass plate. The irradiation dose was 10 J / cm 2 The composition was irradiated with ultraviolet light of 365 nm wavelength and exposed at 100° C. for 1 hour to obtain a cured product. The cured product was firmly bonded to the glass substrate and had a film thickness of 100 μm after coating.

[0313] Description of Reference Numerals

[0314] 1: Hot melt machine

[0315] 2: Extruder

[0316] 3-a: Pump

[0317] 3-b: Pump

[0318] 3-c: Vacuum pump

[0319] 4: Spout (can be installed arbitrarily for the nozzle used to fill the box)

Claims

1. A curable silicone composition, wherein: contain: (A) 100 parts by mass of an organopolysiloxane resin that is solid at 25°C and comprises the following components (A1) and (A2) in a mass ratio of 20:80 to 90:10, wherein each component alone does not have heat-fusibility; (A1) has a curing reactive functional group containing a carbon-carbon double bond in the molecule, and contains at least 20 mol% or more of the total siloxane units composed of SiO 4 / 2 An organopolysiloxane resin having the siloxane units shown; (A2) does not have a curing reactive functional group containing a carbon-carbon double bond in the molecule, and contains at least 20 mol% or more of the total siloxane units composed of SiO 4 / 2 An organopolysiloxane resin having the siloxane units shown; (B) 10 to 100 parts by mass of a linear organopolysiloxane having a curing-reactive functional group containing at least two carbon-carbon double bonds in its molecule and being liquid at 25°C; (C) an amount of 0.5 to 20.0 silicon-bonded hydrogen atoms per silicon-bonded alkenyl group contained in the entire organohydrogenpolysiloxane composition having at least two silicon-bonded hydrogen atoms per molecule; (D) a catalytic amount of a hydrosilylation reaction catalyst having a property of being inert at room temperature but becoming active in the composition by external energy stimulation, wherein the component (D) is one or more hydrosilylation reaction catalysts selected from (D1) a hydrosilylation reaction catalyst that becomes active in the composition by irradiation with high-energy rays, and (D2) thermoplastic resin fine particles containing the hydrosilylation reaction catalyst, The composition as a whole is hot-melt, where "hot-melt" means that the composition as a whole is highly viscous or solid enough to retain its shape at 25°C, has a melt viscosity within the range described below at 100°C, softens upon heating, and exhibits flowability. Furthermore, as measured by a flow meter with an outlet nozzle diameter of 1 mm and a pressure of 2.5 MPa, the melt viscosity at 100°C is 50 Pa·s or less.

2. The curable silicone composition according to claim 1, wherein (E) a curing retardant for hydrosilylation reaction having a boiling point of 200° C. or higher under atmospheric pressure is further contained in an amount of 1 to 5000 ppm based on the mass of the entire composition.

3. The curable silicone composition according to any one of claims 1 to 2, wherein The mass reduction rate of the component (A) when exposed to atmospheric pressure at 200° C. for 1 hour is 2.0 mass % or less.

4. The curable silicone composition according to any one of claims 1 to 2, wherein The component (A1) is composed of the following average unit formula (A1-1): (R 1 3SiO 1 / 2 ) a (R 1 2SiO 2 / 2 ) b (R 1 SiO 3 / 2 ) c (SiO 4 / 2 ) d (R 2 O 1 / 2 ) e (In the formula, each R 1 are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, wherein all R 1 1 to 12 mol% of the group is alkenyl; each R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; a, b, c, d, and e are numbers satisfying the following: 0.10≤a≤0.60, 0≤b≤0.70, 0≤c≤0.80, 0.2≤d≤0.65, 0≤e≤0.05, wherein c+d>0.20, and a+b+c+d=1) As shown, the organopolysiloxane resin itself does not have thermal melt properties. The component (A2) is composed of the following average unit formula (A2-1): (R 3 3SiO 1 / 2 ) f (R 3 2SiO 2 / 2 ) g (R 3 SiO 3 / 2 ) h (SiO 4 / 2 ) i (R 2 O 1 / 2)j (In the formula, each R 3 R is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms and not containing a carbon-carbon double bond; 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; f, g, h, i, and j are numbers satisfying the following: 0.35≤f≤0.55, 0≤g≤0.20, 0≤h≤0.20, 0.45≤i≤0.65, 0≤j≤0.05, and f+g+h+i=1) As shown, the organopolysiloxane resin itself does not have thermal melt properties. The component (B) is represented by the following structural formula (B1): <h2 style=";text-align:left;direction:ltr">R<h2 style=";text-align:left;direction:ltr"> 4 <h2 style=";text-align:left;direction:ltr"> 3SiO(SiR<h2 style=";text-align:left;direction:ltr"> 4 <h2 style=";text-align:left;direction:ltr"> 2O)<h2 style=";text-align:left;direction:ltr"> k <h2 style=";text-align:left;direction:ltr"> SiR<h2 style=";text-align:left;direction:ltr"> 4 <h2 style=";text-align:left;direction:ltr"> 3 (In the formula, each R 4 are independently monovalent hydrocarbon groups having 1 to 10 carbon atoms, wherein R 4 At least two of the groups are alkenyl groups, and k is a number from 20 to 5,000) The linear polydiorganosiloxane shown.

5. A hot melt adhesive or hot melt sealant, wherein: The present invention is composed of the curable silicone composition according to claims 1 to 4.

6. A box containing a curable silicone composition, wherein: The present invention has a form in which the curable silicone composition according to claims 1 to 4 is filled in a dispensing box, barrel or cartridge.

7. A cured product, wherein It is formed by curing the curable silicone composition according to claims 1 to 4.

8. An electronic component, a semiconductor device or an optical semiconductor device, wherein: A cured product according to claim 7.

9. A laminated body, wherein: A substrate and a partially or entirely uncured portion or layer on the surface of the substrate composed of the curable silicone composition according to claims 1 to 4.

10. A laminated body, wherein: The method comprises two or more substrates, and has a structure in which a part or all of the surfaces of at least two substrates are joined via the cured product according to claim 7. The laminate according to claim 10 , wherein: The laminated body is one or more selected from electronic components, semiconductor devices, or optical semiconductor devices.

12. The method for producing a laminate according to claim 10, comprising: Step (I): heating the curable silicone composition according to claims 1 to 3 to 50° C. or higher using a dispenser equipped with a heating portion to impart fluidity, and spraying the composition onto a portion or the entire surface of at least one substrate; Step (II): simultaneously with step (I) or after step (I), irradiating the curable silicone composition discharged from the dispenser with high energy radiation directly or through another substrate; and, if necessary, Step (III): After step (I) and before or after step (II), a step of bringing another substrate into close contact with the curable silicone composition discharged from the dispenser.

13. The method for producing a laminate according to claim 10, comprising: Step (I): heating the curable silicone composition according to claims 1 to 4 to 50° C. or higher using a dispenser equipped with a heating portion to impart fluidity, and spraying the composition onto a portion or the entire surface of at least one substrate; If necessary, step (II): after step (I), a step of bringing the curable silicone composition discharged from the dispenser into close contact with another substrate; as well as Step (III): a step of heating the obtained integrated product of the substrate and the curable silicone composition to a temperature of 130° C. or higher.

14. The method for producing a laminate according to claim 12 or 13, wherein: In the above-mentioned step 1, a heatable slot die is connected to the outlet of the dispenser to discharge the material in the form of a film or sheet having a desired thickness.

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